JP2004262932A - Agricultural chemical containing 3-phenoxy-4-pyridazinol derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To discover a herbicide capable of exhibiting excellent herbicidal activity on a wide range of weed species in paddy fields even in a small amount, scarcely exhibiting phytotoxicity against paddy rice. <P>SOLUTION: An agricultural chemical contains a compound expressed by general formula (I) (R<SP>1</SP>is H, a halogen, an alkyl or the like; R<SP>2</SP>is H, a halogen, an alkyl or the like; R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, R<SP>6</SP>, and R<SP>7</SP>are each H, a halogen, an alkyl which may be substituted, an alkenyl which may be substituted, an alkynyl, a cycloalkyl which may be substituted or the like, or two of R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, R<SP>6</SP>, and R<SP>7</SP>adjacent to each other may combine with each other together with carbons bonding thereto and form a ring which may be substituted; and m and n are each 0 or 1), its salt, and its esterified derivative as active ingredients. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a 3-phenoxy-4-pyridazinol compound, a salt thereof, an ester derivative thereof, and an agrochemical containing the same as an active ingredient.

  Non-Patent Document 1 describes 3- (2-allylphenoxy) -6-chloro-4-methoxypyridazine, but describes a 3-phenoxy-4-pyridazinol compound having a hydroxyl group at the 4-position of pyridazine. There is no mention of herbicides.

  Non-Patent Document 2 describes 3- (2-hydroxyphenoxy) -4-methoxypyridazine and 6-chloro-3- (2-hydroxyphenoxy) -4-methoxypyridazine, but at the 4-position of pyridazine. A 3-phenoxy-4-pyridazinol compound having a hydroxyl group is not described, and there is no description about a herbicide.

  Patent Document 1 describes a 3- (substituted phenoxy) pyridazine compound having a haloalkylphenoxy group at the 4-position of pyridazine, but a 3-phenoxy-4-pyridazinol compound having a hydroxyl group at the 4-position of pyridazine Is not listed. In addition, 3- (optionally substituted phenoxy) pyridazine compounds having a haloalkylphenoxy group at the 4-position of pyridazine are clogged with a benzene ring at the oxygen atom bonded to the 4-position of pyridazine, and their herbicidal activity is insufficient. It was something.

  At present, many herbicides have been put to practical use as paddy field herbicides and are widely used as single agents and mixed agents. However, there are many kinds of paddy field weeds, and the weeds and the growth time of each weed are not uniform, and the generation of perennial weeds is particularly long. Therefore, it is very difficult to control all weeds with a single herbicide application. Therefore, as a herbicide, many kinds of weeds including annual and perennial weeds can be killed, that is, the herbicidal spectrum is wide, effective for weeds that have grown, and the herbicidal effect can be maintained for a certain period of time. In addition, the emergence of highly safe drugs in paddy rice is most demanded.

In addition, a large number of herbicides are currently marketed and used as field crop herbicides, but there are many types of weeds that are subject to control, and their occurrences are long-lasting. There is a need for herbicides that have a grass spectrum and do not cause crop damage problems.
US Pat. No. 5,559,080 Chemical Pharmaceutical Bulletin, 1972, Vol. 20, No. 10, p.2191-2203 Journal of the Chemical Society: Perkin Transaction I (1975), 6, pp. 534-538

  As a result of intensive studies on the pyridazine derivative having a phenoxy group at the 3-position, the present inventors have found that the compound having a 4-position hydroxyl group of the pyridazine ring shows little phytotoxicity to paddy rice and has been applied to a wide range of weed species in paddy fields. On the other hand, the inventors have found that excellent herbicidal activity is exhibited at a low dose, and thus completed the present invention. Furthermore, an ester derivative in which the bond between the oxygen atom at the 4-position of the pyridazine ring and the acyl group in the soil or in the plant is broken and converted into a compound in which a hydrogen atom is bonded to the oxygen atom is the same as the above. The present invention was completed by finding that it has herbicidal activity.

  The present invention provides a general formula

[In the formula, R ¹ represents a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₃ -C ₆ cycloalkyl group, C ₂ -C ₆ alkenyl group, a cyano group, A C ₂ -C ₇ alkylcarbonyl group, a di (C ₁ -C ₆ alkyl) carbamoyl group, an optionally substituted phenyl group (the substituent is a substituent selected from the following substituent group A), 5 or 6-membered heterocyclic group (the heterocyclic ring may contain one nitrogen atom, oxygen atom or sulfur atom, and may further contain 1 or 2 nitrogen atoms in the ring), C _1- . A C ₆ alkoxy group, an optionally substituted phenoxy group (the substituent is a substituent selected from the following substituent group A) or an optionally substituted 5- or 6-membered heterocyclic oxy group {the heterocyclic ring is Contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and one or two more Of nitrogen atoms. The substituent is a substituent selected from the group consisting of an optionally substituted benzoyl group (the substituent is a substituent selected from the following substituent group A) and a C _{1 to} C ₆ alkyl group. },

R ² represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a (C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkyl group, a benzoyl group which may be substituted (the substituent is the following substituent group) A substituent selected from A.), a C ₂ -C ₇ alkoxycarbonyl group, an optionally substituted phenoxy group (the substituent is a substituent selected from the following substituent group A), substituted. A good phenylthio group (the substituent is a substituent selected from the following substituent group A) or a tri (C ₁ -C ₆ alkyl) silicon group;

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom or an optionally substituted C ₁ -C ₆ alkyl group (the substituent is selected from the following substituent group B) A C ₂ -C ₆ alkenyl group which may be substituted (the substituent is a cyano group or a nitro group), a C ₂ -C ₆ alkynyl group, a C ₃ which may be substituted. -C ₆ cycloalkyl group (said substituent is a substituent selected from substituent group C.), C ₄ ~C ₁₀ bicycloalkyl group, a cyano group, a formyl group, C ₂ -C ₇ alkylcarbonyl group , A benzoyl group which may be substituted (the substituent is a substituent selected from the following substituent group A), a carboxyl group, a C ₂ -C ₇ alkoxycarbonyl group, a carbamoyl group, a di (C ₁ -C _6). Alkyl) carbamoyl group, optionally substituted phenyl A group (the substituent is a substituent selected from the following substituent group A), an optionally substituted 3- to 6-membered heterocyclic group (the heterocyclic ring includes one nitrogen atom, (It contains an oxygen atom or a sulfur atom, may further contain 1 to 2 nitrogen atoms, and may be condensed with a benzene ring. The substituent is a substituent selected from the following substituent group E.) , amino group which may be substituted (the substituent is a substituent selected from substituent group D.), a nitro group, a hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ haloalkoxy group, (C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkoxy group, optionally substituted phenoxy group (the substituent is substituted with a hydroxyl group or a substituent selected from a halogen atom and a C ₁ -C ₆ alkoxy group) A pyridazinyloxy group), which may be substituted; Ring oxy group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms. is a substituent selected from group E.), which may be substituted phenylsulfonyloxy group (the substituent is a substituent selected from substituent group a.), C ₁ ~C ₆ alkylthio group, A C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ alkylsulfonyl group or a tri (C ₁ -C ₆ alkyl) silicon group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are Two adjacent groups may be substituted together with the carbon atom to which each is bonded. The 3- to 6-membered cyclic hydrocarbon group (the cyclic hydrocarbon is selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom) Interrupted by one or two identical or different heteroatoms There. The substituents are halogen atom, C ₁ -C ₆ alkyl group, a hydroxy C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, a oxo group, hydroxyimino group or a C ₁ -C ₆ alkoxyimino group If the C ₁ -C ₆ alkyl group is substituted, it may form a new 3-membered ring with other C ₁ -C ₆ alkyl group or a carbon atom on the ring. )
m and n each independently represent 0 or 1,
Substituent Group A consists of halogen atoms, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₃ -C ₆ cycloalkyl group, a cyano group and a tri (C ₁ -C ₆ alkyl) silyl group A group,
Substituent group B, a halogen atom, C ₃ -C ₆ cycloalkyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a phenyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, consisting of C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₄ alkylenedioxy group, hydroxyimino group and C ₁ -C ₆ alkoxyimino group A group,
Substituent group C includes a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent is a substituent selected from the above substituent group B), a C ₃ -C ₆ cycloalkyl group, C ₂ -C ₆ alkenyl group, cyano group, C ₂ -C ₇ alkylcarbonyl group, a benzoyl group, a carboxyl group, C ₂ -C ₇ alkoxycarbonyl group, a carbamoyl group, a di (C ₁ -C ₆ alkyl) carbamoyl group, A phenyl group which may be substituted (the substituent is a substituent selected from the above substituent group A), a 5- or 6-membered heterocyclic group (the heterocyclic ring has one nitrogen atom in the ring; , An oxygen atom or a sulfur atom, and further may contain 1 to 2 nitrogen atoms.), An amino group which may be substituted (the substituent is a substituent selected from the following substituent group D) .), a nitro group, a hydroxyl group, C ₁ -C ₆ alkoxy Group, a C ₁ -C ₆ haloalkoxy group, a phenoxy group, C ₁ -C ₆ alkylthio group, a phenylthio group, C ₁ -C ₆ alkylsulfinyl group consisting Le group and C ₁ -C ₆ alkylsulfonyl group,
Substituent group D is, C ₁ -C ₆ alkyl group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a di (C ₁ -C ₆ alkyl) carbamoyl group and C ₁ -C ₆ alkyl A group consisting of a sulfonyl group,
Substituent group E includes a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a hydroxyl group, an optionally substituted phenylsulfonyl group (the substituent is a substituent selected from substituent group A above) And di (C ₁ -C ₆ alkyl) sulfamoyl groups. ]
Or a salt or ester derivative thereof,
Agrochemicals (preferably paddy field herbicide or field crop herbicide) containing them as active ingredients.

  The compound of the present invention has a herbicidal action and can be used as a herbicide in paddy fields, upland fields, orchards, pastures, turflands, forests or non-agricultural lands.

  The compounds of the present invention are a variety of weeds that are problematic in paddy fields, such as annual broadleaf weeds such as azena, azetope, kikashigusa, mizohakobe, oak, stinkweed, abnomome, himesoohagi; Weeds: annual cyperaceae weeds such as Cyperus crispula, Cyprinus crested weeds; perennial cyperids weeds such as pine birch, firefly, scorpion squirrel; or annual and perennial active weeds against weeds And it does not show any harmful phytotoxicity to rice.

  In addition, the compound of the present invention exhibits herbicidal activity against various weeds that are problematic in soil treatment and foliage treatment in field cultivation.

  Furthermore, it can be used not only in paddy fields and upland fields, but also in orchards, mulberry fields and non-agricultural land.

  In the present invention, the “halogen atom” is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a chlorine atom or a bromine atom. And even more preferred is a chlorine atom.

In the present invention, the “C ₁ -C ₆ alkyl group” is a linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl. , T-butyl, pentyl, isopentyl, 2-methylbutyl, neopentyl, 1-ethylpropyl, hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2 , 2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl or 2-ethylbutyl group, is four straight or branched chain alkyl group (C ₁ -C ₄ alkyl group), more preferably 1 to 3 carbon atoms straight or branched chain alkyl group (C ₁ -C ₃ alkyl Group), and even more preferably, 1 to 2 carbon atoms. An alkyl group (C ₁ -C ₂ alkyl group), particularly preferably a methyl group.

In the present invention, the “C ₁ -C ₆ haloalkyl group” is the “C ₁ -C ₆ alkyl group” substituted with 1 to 5 of the same or different “halogen atoms”, such as chloromethyl, Dichloromethyl, trichloromethyl, 1-chloroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 1-chloropropyl, 3-chloropropyl, 1-chlorobutyl, 4-chlorobutyl, fluoromethyl, difluoromethyl, trifluoromethyl 1-fluoroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, fluorochloromethyl, bromomethyl, 1-bromoethyl, 2-bromoethyl or iodomethyl groups, preferably fluorine atom, C ₁ -C ₃ alkyl group one to three substituents the same or different selected from the group consisting of chlorine atom and bromine atom is substituted There, more preferably, the same one to three, fluorine atoms C ₁ -C ₂ alkyl radical or a chlorine atom is substituted, further preferably more, fluoromethyl, difluoromethyl, trifluoromethyl or 2 2,2-trichloroethyl group, particularly preferably a trifluoromethyl group.

In the present invention, the “C ₃ -C ₆ cycloalkyl group” is a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl group, preferably a cyclopropyl or cyclobutyl group, and more preferably a cyclopropyl group. .

In the present invention, the “C ₂ -C ₆ alkenyl group” is a linear or branched alkenyl group having 2 to 6 carbon atoms, and examples thereof include vinyl, 1-methylvinyl, 1-propenyl, 1-methyl- 1-propenyl, 2-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-ethyl-2-propenyl, 2-butenyl, 1-methyl-2-butenyl, 2-methyl-2- Butenyl, 1-ethyl-2-butenyl, 3-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 1-ethyl-3-butenyl, 2-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 4-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 2- It may be a hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl group, preferably a C2-C4 linear or branched alkenyl group (C A ₂ -C ₄ alkenyl group), more preferably, vinyl, 1-methylvinyl, 2-propenyl or 1-methyl-2-propenyl group.

In the present invention, the “C ₂ -C ₇ alkylcarbonyl group” is a carbonyl group to which the “C ₁ -C ₆ alkyl group” is bonded, and examples thereof include acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, It may be a hexanoyl or heptanoyl group, preferably a carbonyl group (C2 to C5 alkylcarbonyl group) to which a linear or branched alkyl group having 1 to 4 carbon atoms is bonded, and even more preferably carbon. It is a carbonyl group (C ₂ -C ₄ alkylcarbonyl group) to which several 1 to 3 linear or branched alkyl groups are bonded, particularly preferably an acetyl, propionyl, valeryl or pivaloyl group, and most preferred Is an acetyl group.

In the present invention, the “di (C ₁ -C ₆ alkyl) carbamoyl group” is a carbamoyl group in which two identical or different “C ₁ -C ₆ alkyl groups” are bonded to a nitrogen atom. , Methylethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, dibutylcarbamoyl or dihexylcarbamoyl group, preferably a carbamoyl group in which the same two linear or branched alkyl groups having 1 to 3 carbon atoms are bonded {Di (C ₁ -C ₃ alkyl) carbamoyl group}, more preferably a dimethylcarbamoyl group or diethylcarbamoyl group, and still more preferably a dimethylcarbamoyl group.

In the present invention, the “tri (C ₁ -C ₆ alkyl) silicon group” is a silicon atom to which three identical or different “C ₁ -C ₆ alkyl groups” are bonded, and examples thereof include trimethylsilyl, triethylsilyl, It may be a triisopropylsilyl, dimethylisopropylsilyl, t-butyldimethylsilyl or trihexylsilyl group, preferably having the same or different 3 to 1 C 1-3 straight or branched alkyl groups attached thereto. A silicon atom {tri (C ₁ -C ₃ alkyl) silicon group}, more preferably a trimethylsilyl or dimethylisopropylsilyl group, and even more preferably a trimethylsilyl group.

In the present invention, “optionally substituted phenyl group (the substituent is a substituent selected from Substituent Group A)” means the “halogen atom”, the “C ₁ -C ₆ alkyl group”, the "C ₁ -C ₆ haloalkyl group", the "C ₃ -C ₆ cycloalkyl group", the same or different selected from the group consisting of cyano group and the "tri (C ₁ -C ₆ alkyl) silyl group" 1 to 5 substituents may be substituted phenyl groups, such as phenyl, fluorophenyl, difluorophenyl, trifluorophenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, fluorochlorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, Tetramethylphenyl, pentamethylphenyl, ethylphenyl, fluoro (methyl) phenyl, chloro Methyl) phenyl, bromo (methyl) phenyl, cyclopropylphenyl, cyclopropyl (fluoro) phenyl, chloro (cyclopropyl) phenyl, cyclopropyl (methyl) phenyl, (trifluoromethyl) phenyl or fluoro (trifluoromethyl) phenyl groups in and obtained, preferably a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, the same or different 1-3 selected from the group consisting of chlorine and bromine C ₁ -C ₃ alkyl group "substituted group is substituted, C ₃ -C ₄ cycloalkyl group, the same or different 1 to 3 selected from cyano group and a tri (C ₁ -C ₃ alkyl) group consisting of silicon group Is an optionally substituted phenyl group, more preferably phenyl, chlorophenyl, methylphenyl, trifluoro. Phenyl or cyanophenyl group.

  In the present invention, “5- or 6-membered heterocyclic group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms. Is a 5- to 6-membered heterocyclic group which contains one nitrogen atom, oxygen atom or sulfur atom as a hetero atom, and may further contain 1 to 2 nitrogen atoms, For example, it may be a furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, triazolyl, pyranyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl or triazinyl group, preferably a 5-membered heterocyclic group The ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring.), More preferably a furyl or thienyl group.

In the present invention, the “C ₁ -C ₆ alkoxy group” is a linear or branched alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s- Butoxy, t-butoxy, pentoxy, isopentoxy, 2-methylbutoxy, neopentoxy, 1-ethylpropoxy, hexyloxy, 4-methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, 1-methylpentoxy, 3 , 3-dimethylbutoxy, 2,2-dimethylbutoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,3-dimethylbutoxy or 2-ethylbutoxy group, Preferred is a straight or branched alkoxy group having 1 to 3 carbon atoms (C ₁ -C ₃ alkoxy group), more preferred is a methoxy or ethoxy group, and even more preferred. Is a methoxy group.

In the present invention, “optionally substituted phenoxy group (the substituent is a substituent selected from Substituent Group A)” means the “halogen atom”, the “C ₁ -C ₆ alkyl group”, The same or different selected from the group consisting of the “C ₁ -C ₆ haloalkyl group”, the “C ₃ -C ₆ cycloalkyl group”, the cyano group and the “tri (C ₁ -C ₆ alkyl) silicon group”. 1 to 5 substituents may be substituted phenoxy groups, such as phenoxy, fluorophenoxy, difluorophenoxy, trifluorophenoxy, chlorophenoxy, dichlorophenoxy, trichlorophenoxy, fluorochlorophenoxy, methylphenoxy, dimethylphenoxy, Trimethylphenoxy, tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, Oro (methyl) phenoxy, chloro (methyl) phenoxy, bromo (methyl) phenoxy, cyclopropylphenoxy, cyclopropyl (fluoro) phenoxy, chloro (cyclopropyl) phenoxy, cyclopropyl (methyl) phenoxy, (trifluoromethyl) phenoxy or It may be a fluoro (trifluoromethyl) phenoxy group, preferably a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, “identical selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom Or a C ₁ -C ₃ alkyl group substituted with 1 to 3 different substituents ”, a C ₃ -C ₄ cycloalkyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group. The same or different 1 to 3 substituents may be substituted, more preferably, Phenoxy, chlorophenoxy, methyl phenoxy, trifluoromethyl phenoxy or cyanophenoxy group.

In the present invention, “optionally substituted benzoyl group (the substituent is a substituent selected from Substituent Group A)” means the “halogen atom”, the “C ₁ -C ₆ alkyl group”, the "C ₁ -C ₆ haloalkyl group", the "C ₃ -C ₆ cycloalkyl group", the same or different selected from the group consisting of cyano group and the "tri (C ₁ -C ₆ alkyl) silyl group" 1 to 5 substituents may be substituted benzoyl groups, such as benzoyl, fluorobenzoyl, difluorobenzoyl, trifluorobenzoyl, chlorobenzoyl, dichlorobenzoyl, trichlorobenzoyl, fluorochlorobenzoyl, methylbenzoyl, dimethylbenzoyl, Trimethylbenzoyl, tetramethylbenzoyl, pentamethylbenzoyl, ethylbenzoyl, Oro (methyl) benzoyl, chloro (methyl) benzoyl, bromo (methyl) benzoyl, cyclopropylbenzoyl, cyclopropyl (fluoro) benzoyl, chloro (cyclopropyl) benzoyl, cyclopropyl (methyl) benzoyl, (trifluoromethyl) benzoyl or fluoro be a (trifluoromethyl) benzoyl group, preferably a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, the same selected from the group consisting of chlorine and bromine Or a C ₁ -C ₃ alkyl group substituted with 1 to 3 different substituents ”, a C ₃ -C ₄ cycloalkyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group. The same or different 1 to 3 substituents which may be substituted are benzoyl groups, more preferably Nzoiru, chlorobenzoyl, dichlorobenzoyl, methyl benzoyl, trifluoperazine Robben benzoyl or cyanobenzoyl group.

In the present invention, “optionally substituted 5- or 6-membered heterocyclic oxy group {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms The substituent may be a benzoyl group (the substituent is a substituent selected from Substituent Group A) and a C ₁ -C ₆ alkyl group which may be substituted. Is a substituent selected from the above-mentioned “benzoyl group which may be substituted (the substituent is a substituent selected from substituent group A)” and “C ₁ -C ₆ alkyl group”. May be substituted by the same or different 1 to 3 substituents selected from the group consisting of “as a hetero atom, containing one nitrogen atom, oxygen atom or sulfur atom, and further 1 to 2 nitrogen atoms A 5- to 6-membered heterocyclic oxy group which may contain Fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, C ₁ ~ in which one to three substituents the same or different selected from the group consisting of chlorine atom and bromine atom is substituted The same or different 1 to 3 substituents selected from the group consisting of “C ₃ alkyl group”, C ₃ -C ₄ cycloalkyl group, cyano group and tri (C ₁ -C ₃ alkyl) silicon group are substituted. Substituted with a good benzoyl group, as well as the same two C ₁ -C ₃ alkyl groups, “contains one nitrogen atom, oxygen atom or sulfur atom as a hetero atom, and one more nitrogen atom A 5-membered heterocyclic oxy group "which may contain, more preferably a benzoyl group substituted by two chlorine atoms and two C ₁ -C ₂ alkyl groups A pyrazolyloxy group;

In the present invention, the “(C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkyl group” is the “C ₁ -C ₆ alkyl group” substituted by _{one of the} “C ₁ -C ₆ alkoxy groups”. Yes, for example, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, s-butoxymethyl, t-butoxymethyl, pentyloxymethyl, hexyloxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, methoxy butyl, be a methoxypentyl or methoxyhexyl group, preferably a single C ₁ of -C ₃ C ₁ -C ₆ alkyl group which alkoxy group is substituted, more preferably, methoxyethyl, ethoxyethyl or An ethoxymethyl group.

In the present invention, the “C ₂ -C ₇ alkoxycarbonyl group” is a carbonyl group to which the “C ₁ -C ₆ alkoxy group” is bonded, and examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxy Carbonyl, isobutoxycarbonyl, s-butoxycarbonyl, t-butoxycarbonyl, pentoxycarbonyl, isopentoxycarbonyl, 2-methylbutoxycarbonyl, neopentoxycarbonyl, 1-ethylpropoxycarbonyl, hexyloxycarbonyl, 4-methylpen Toxicarbonyl, 3-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 1-methylpentoxycarbonyl, 3,3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 1,1-dimethylbutoxycarbonyl, 1, 2- Methyl-butoxycarbonyl, 1,3-dimethyl-butoxycarbonyl, 2,3-dimethylbutoxy be a carbonyl or 2-ethyl-butoxycarbonyl group, preferably, C ₁ -C ₃ carbonyl groups alkoxy group is bonded (C ₂ ~ a C ₄ alkoxycarbonyl group), more preferably a methoxycarbonyl or ethoxycarbonyl group, even more preferably more, a methoxycarbonyl group.

In the present invention, “optionally substituted phenylthio group (the substituent is a substituent selected from Substituent Group A)” means the “halogen atom”, the “C ₁ -C ₆ alkyl group”, The same or different selected from the group consisting of the “C ₁ -C ₆ haloalkyl group”, the “C ₃ -C ₆ cycloalkyl group”, the cyano group, and the “tri (C ₁ -C ₆ alkyl) silicon group”. 1 to 5 substituents may be substituted phenylthio groups, such as phenylthio, fluorophenylthio, difluorophenylthio, trifluorophenylthio, chlorophenylthio, dichlorophenylthio, trichlorophenylthio, fluorochlorophenylthio, methylphenyl Thio, dimethylphenylthio, trimethylphenylthio, tetramethylphenylthio, pentamethylphenol Ruthio, ethylphenylthio, fluoro (methyl) phenylthio, chloro (methyl) phenylthio, bromo (methyl) phenylthio, cyclopropylphenylthio, cyclopropyl (fluoro) phenylthio, chloro (cyclopropyl) phenylthio, cyclopropyl (methyl) phenylthio, It can be a (trifluoromethyl) phenylthio or fluoro (trifluoromethyl) phenylthio group, preferably a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, “from a fluorine atom, a chlorine atom and a bromine atom” C ₁ -C ₃ alkyl group "1-3 substituents selected same or different from the group is substituted composed, C ₃ -C ₄ cycloalkyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) 1 to 3 identical or different substitutions selected from the group consisting of silicon groups There substituted to or phenylthio group, and more preferably, phenylthio, a chlorophenylthio, methylphenylthio, trifluorophenyl thio or cyanophenylthio group.

In the present invention, the “C ₁ -C ₆ alkylthio group” is a linear or branched alkylthio group having 1 to 6 carbon atoms, such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, s -Butylthio, t-butylthio, pentylthio, isopentylthio, 2-methylbutylthio, neopentylthio, 1-ethylpropylthio, hexylthio, 4-methylpentylthio, 3-methylpentylthio, 2-methylpentylthio, 1 -Methylpentylthio, 3,3-dimethylbutylthio, 2,2-dimethylbutylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,3-dimethyl It is a butylthio or 2-ethylbutylthio group, preferably a straight-chain or branched alkylthio group having 1 to 3 carbon atoms (C ₁ -C ₃ alkylthio group), More preferred is a methylthio or ethylthio group, and even more preferred is a methylthio group.

In the present invention, "C ₁ -C ₆ alkylsulfinyl group" is a straight chain or branched chain alkylsulfinyl group having 1 to 6 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, propyl sulfinyl, isopropyl-sulfinyl, butyl Sulfinyl, isobutylsulfinyl, s-butylsulfinyl, t-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, 2-methylbutylsulfinyl, neopentylsulfinyl, 1-ethylpropylsulfinyl, hexylsulfinyl, 4-methylpentylsulfinyl, 3-methyl Pentylsulfinyl, 2-methylpentylsulfinyl, 1-methylpentylsulfinyl, 3,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethyl It can be a butylbutylsulfinyl, 1,3-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl or 2-ethylbutylsulfinyl group, preferably a linear or branched alkylsulfinyl group having 1 to 3 carbon atoms (C ₁ -C ₃ alkylsulfinyl group), more preferably a methylsulfinyl or ethylsulfinyl group, and even more preferably a methylsulfinyl group.

In the present invention, the “C ₁ -C ₆ alkylsulfonyl group” is a linear or branched alkylsulfonyl group having 1 to 6 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butyl Sulfonyl, isobutylsulfonyl, s-butylsulfonyl, t-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, 2-methylbutylsulfonyl, neopentylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 4-methylpentylsulfonyl, 3-methyl Pentylsulfonyl, 2-methylpentylsulfonyl, 1-methylpentylsulfonyl, 3,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3 -Dimethylbutylsulfo Le, be a 2,3-dimethyl-butylsulfonyl or 2-ethyl-butylsulfonyl group, preferably a linear or branched alkylsulfonyl group (C ₁ -C ₃ alkylsulfonyl group) having 1 to 3 carbon atoms And more preferably a methylsulfonyl or ethylsulfonyl group, and even more preferably a methylsulfonyl group.
In the present invention, the “C ₁ -C ₄ alkylenedioxy group” is a linear or branched alkylenedioxy group having 1 to 4 carbon atoms, such as methylenedioxy, ethylenedioxy, propylenedioxy. , Trimethylenedioxy or tetramethylenedioxy group, preferably an alkylenedioxy group having 1 to 2 carbon atoms, and more preferably a 1,2-ethylenedioxy group.

In the present invention, the “C ₁ -C ₆ alkoxyimino group” is a linear or branched alkoxyimino group having 1 to 6 carbon atoms, and examples thereof include methoxyimino, ethoxyimino, propoxyimino, isopropoxyimino, Butoxyimino, isobutoxyimino, s-butoxyimino, t-butoxyimino, pentoxyimino, isopentoxyimino, 2-methylbutoxyimino, neopentoxyimino, 1-ethylpropoxyimino, hexyloxyimino, 4-methylpentoxy Imino, 3-methylpentoxyimino, 2-methylpentoxyimino, 1-methylpentoxyimino, 3,3-dimethylbutoxyimino, 2,2-dimethylbutoxyimino, 1,1-dimethylbutoxyimino, 1,2 -Dimethylbutoxyimino, 1,3-dimethylbutoxyimino, 2,3-dimethylbutoxyimino or 2-ethylbut It is a Shiimino group, preferably a straight or branched alkoxyimino group having 1 to 3 carbon atoms (C ₁ -C ₃ alkoxyimino group), more preferably, methoxyimino or ethoxyimino group And even more preferred is a methoxyimino group.

In the present invention, the “substituted C ₁ -C ₆ alkyl group (the substituent is a substituent selected from Substituent Group B)” is the above “halogen atom” or “C ₃ -C ₆ cycloalkyl group ", a cyano group, wherein" C ₂ -C ₇ alkylcarbonyl group ", the" C ₂ -C ₇ alkoxycarbonyl group ", phenyl group, wherein" C ₁ -C ₆ alkoxy group ", the "C ₁ -C ₆ alkylthio group", the "C ₁ -C ₆ alkylsulfinyl group", the "C ₁ -C ₆ alkylsulfonyl group", the "C ₁ -C ₄ alkylenedioxy group", hydroxyimino group Or the “C ₁ -C ₆ alkyl group” which may be substituted by the “C ₁ -C ₆ alkoxyimino group”, for example, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trichloroethyl , Shik Ropropylmethyl, cyanomethyl, acetylmethyl, acetylethyl, methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, benzyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, methylthioethyl, ethylthio It may be methyl, ethylthioethyl, methylsulfinylmethyl, methylsulfonylmethyl, 2- (1,3-dioxolanyl), hydroxyiminomethyl or methoxyiminomethyl group, preferably consisting of fluorine atom, chlorine atom and bromine atom C ₁ -C ₃ alkyl group one to three substituents the same or different from selected from the group is substituted, or, C ₃ -C ₄ cycloalkyl group, a cyano group, C ₂ -C ₄ alkylcarbonyl group, C ₂ ~C ₄ alkoxy Carbonyl group, a phenyl group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ alkylthio group, C ₁ -C ₃ alkylsulfinyl group, C ₁ -C ₃ alkylsulfonyl groups, C ₁ -C ₂ alkylenedioxy group, A hydroxyimino group or a C ₁ -C ₃ alkyl group that may be substituted by a C ₁ -C ₃ alkoxyimino group, and more preferably the same 1 to 3 C ₁ substituted with fluorine atoms or chlorine atoms. -C ₂ alkyl group, or a cyclopropyl group, a cyano group, C ₂ -C ₃ alkylcarbonyl group, C ₂ -C ₃ alkoxycarbonyl group, a phenyl group, C ₁ -C ₂ alkoxy group, C ₁ -C ₂ alkylthio group, C ₁ -C ₂ alkylsulfinyl group, C ₁ -C ₂ alkylsulfonyl group, an ethylenedioxy group, hydroxyimino group or C ₁ -C ₂ alkoxyimino group may be substituted C ₁ ~C is a _2-alkyl group.

In the present invention, the “substituted C ₂ -C ₆ alkenyl group (the substituent is a cyano group or a nitro group)” refers to the “C ₂ -C ₆ alkenyl group substituted by a cyano group or a nitro group”. a ", preferably a C ₂ -C ₃ alkenyl group cyano group or a nitro group is substituted, more preferably a cyanovinyl or nitrovinyl group.

In the present invention, the “C ₂ -C ₆ alkynyl group” is a linear or branched alkynyl group having 2 to 6 carbon atoms, and examples thereof include ethynyl, 2-propynyl, 1-methyl-2-propynyl, 1 -Ethyl-2-propynyl, 2-butynyl, 1-methyl-2-butynyl, 1-ethyl-2-butynyl, 3-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-ethyl -3-butynyl, 2-pentynyl, 1-methyl-2-pentynyl, 1-ethyl-2-pentynyl, 3-pentynyl, 1-methyl-3-pentynyl, 2-methyl-3-pentynyl, 4-pentynyl, 1 -Methyl-4-pentynyl, 2-methyl-4-pentynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl or 5-hexynyl, preferably a straight or branched chain having 3 to 4 carbon atoms a-chain alkynyl groups (C ₃ -C ₄ alkynyl group), more preferably ethynyl, 1-propynyl or 2-propynyl is there.

In the present invention, “an amino group which may be substituted (the substituent is a substituent selected from Substituent Group D)” refers to the “C ₁ -C ₆ alkyl group” and the “C ₂ -C”. Selected from the group consisting of “ ₇ alkylcarbonyl group”, “C ₂ -C ₇ alkoxycarbonyl group”, “di (C ₁ -C ₆ alkyl) carbamoyl group” and “C ₁ -C ₆ alkylsulfonyl group”. An amino group which may be substituted by one or two identical or different substituents, for example, amino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, s-butylamino, t- Butylamino, pentylamino, isopentylamino, (2-methylbutyl) amino, neopentylamino, (1-ethylpropyl) amino, hexylamino, (4-methylpentyl ) Amino, (3-methylpentyl) amino, (2-methylpentyl) amino, (1-methylpentyl) amino, (3,3-dimethylbutyl) amino, (2,2-dimethylbutyl) amino, (1, 1-dimethylbutyl) amino, (1,2-dimethylbutyl) amino, (1,3-dimethylbutyl) amino, (2,3-dimethylbutyl) amino, (2-ethylbutyl) amino, dimethylamino, (methyl) (Ethyl) amino, diethylamino, dipropylamino, (methyl) (isopropyl) amino, diisopropylamino, dibutylamino, diisobutylamino, di-s-butylamino, di-t-butylamino, dipentylamino, diisopentylamino, di ( 2-methylbutyl) amino, dineopentylamino, di (1-ethylpropyl) amino, dihexylamino, di (4-methylpentyl) amino, di (3-methylpentyl) amino, di (2-methylpentyl) amino Di (1-methylpentyl) amino, di (3,3-dimethylbutyl) amino, di (2,2-dimethylbutyl) amino, di (1,1-dimethylbutyl) amino, di (1,2-dimethyl) Butyl) amino, di (1,3-dimethylbutyl) amino, di (2,3-dimethylbutyl) amino, di (2-ethylbutyl) amino, acetylamino, propionylamino, butanoylamino, (2-methylpropanoyl) ) Amino, pentanoylamino, (2,2-dimethylpropanoyl) amino, (2,2-dimethylpentanoyl) amino, (2-methylbutanoyl) amino, (3-methylbutanoyl) amino, hexanoylamino , Heptanoylamino, (3,3-dimethylbutanoyl) amino, methoxycarbonylamino, ethoxycarbonylamino, propoxycarbonylamino, isopropoxycarbonylamino, butoxycarbonylamino, isobutoxycal Bonylamino, s-butoxycarbonylamino, t-butoxycarbonylamino, pentoxycarbonylamino, isopentoxycarbonylamino, (2-methylbutoxycarbonyl) amino, neopentoxycarbonylamino, (1-ethylpropoxycarbonyl) amino, hexyl Oxycarbonylamino, (4-methylpentoxycarbonyl) amino, (3-methylpentoxycarbonyl) amino, (2-methylpentoxycarbonyl) amino, (1-methylpentoxycarbonyl) amino, (3,3-dimethyl) (Butoxycarbonyl) amino, (2,2-dimethylbutoxycarbonyl) amino, (1,1-dimethylbutoxycarbonyl) amino, (1,2-dimethylbutoxycarbonyl) amino, (1,3-dimethylbutoxycarbonyl) amino, ( 2,3-Dimethylbutoxycarbonyl) amino, (2-ethylbutoxycarbonyl) Mino, dimethylcarbamoylamino, (methylethylcarbamoyl) amino, diethylcarbamoylamino, dipropylcarbamoylamino, dibutylcarbamoylamino, dihexylcarbamoylamino, methylsulfonylamino, ethylsulfonylamino, propylsulfonylamino, isopropylsulfonylamino, butylsulfonylamino, be a t- butyl sulfonylamino, or hexyl sulfonylamino, preferably, identical or different one to two C ₁ -C ₃ alkyl group, or, C ₂ -C ₄ alkylcarbonyl group, C ₂ -C ₄ An amino group which may be substituted by an alkoxycarbonyl group, a di (C ₁ -C ₃ alkyl) carbamoyl group or a C ₁ -C ₃ alkylsulfonyl group, and more preferably methylamino, ethylamino, dimethylamino Mino, diethylamino, acetylamino, propionylamino, (2-methylpropanoyl) amino, (2,2-dimethylpropanoyl) amino, methoxycarbonylamino, ethoxycarbonylamino, dimethylcarbamoylamino, diethylcarbamoylamino, methylsulfonylamino or An ethylsulfonylamino group;

In the present invention, the “C ₁ -C ₆ haloalkoxy group” is the above-mentioned “C ₁ -C ₆ alkoxy group” substituted with 1 to 5 of the above “halogen atoms”, for example, chloromethoxy , Dichloromethoxy, trichloromethoxy, 1-chloroethoxy, 2-chloroethoxy, 2,2,2-trichloroethoxy, 1-chloropropoxy, 3-chloropropoxy, 1-chlorobutoxy, 4-chlorobutoxy, fluoromethoxy, difluoro Methoxy, trifluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, fluorochloromethoxy, bromomethoxy, 1-bromoethoxy, 2-bromoethoxy or iodomethoxy groups Preferably, the same or different selected from the group consisting of fluorine atom, chlorine atom and bromine atom A 1-3 C ₁ substituent is substituted -C ₃ alkoxy group, and more preferably, the same one to three, fluorine atom or a chlorine atom is located at C ₁ -C ₂ alkoxy group substituted Even more preferred is a fluoromethoxy, difluoromethoxy, trifluoromethoxy or 2,2,2-trichloroethoxy group, and particularly preferred is a trifluoromethoxy group.

In the present invention, the “substituted C ₃ -C ₆ cycloalkyl group (the substituent is a substituent selected from the substituent group C)” is the above-mentioned “halogen atom” and the above “substituted”. C ₁ -C ₆ alkyl group (the substituent is a substituent selected from Substituent Group B) ”, the“ C ₃ -C ₆ cycloalkyl group ”, and the“ C ₂ -C ₆ alkenyl group ”. , a cyano group, wherein "C ₂ -C ₇ alkylcarbonyl group", a benzoyl group, a carboxyl group, the "C ₂ -C ₇ alkoxycarbonyl group", carbamoyl group, the "di (C ₁ -C ₆ alkyl) carbamoyl group ", Said" optionally substituted phenyl group (the substituent is a substituent selected from substituent group A) "," the 5- or 6-membered heterocyclic group (the heterocyclic ring is in the ring, Contains one nitrogen, oxygen or sulfur atom Furthermore, it may contain 1 to 2 nitrogen atoms.) ”,“ The amino group which may be substituted (the substituent is a substituent selected from substituent group D) ”, nitro group, hydroxyl group the "C ₁ -C ₆ alkoxy group", the "C ₁ -C ₆ haloalkoxy group", a phenoxy group, wherein "C ₁ -C ₆ alkylthio group", a phenylthio group, wherein "C ₁ -C ₆ alkylsulfinyl The “C ₃ -C ₆ cycloalkyl group” substituted by the same or different 1 to 5 substituents selected from the group consisting of “group” and the “C ₁ -C ₆ alkylsulfonyl group”, for example, , Fluorocyclopropyl, difluorocyclopropyl, chlorocyclopropyl, dichlorocyclopropyl, bromocyclopropyl, dibromocyclopropyl, iodocyclopropyl, methylcyclopropyl, Tylcyclopropyl, propylcyclopropyl, isopropylcyclopropyl, butylcyclopropyl, t-butylcyclopropyl, hexylcyclopropyl, cyclopropylcyclopropyl, cyclobutylcyclopropyl, cyclopentylcyclopropyl, (fluoromethyl) cyclopropyl, (chloromethyl ) Cyclopropyl, (bromomethyl) cyclopropyl, (difluoromethyl) cyclopropyl, (trifluoromethyl) cyclopropyl, (trichloromethyl) cyclopropyl, (2,2,2-trifluoroethyl) cyclopropyl, (2,2 , 2-trichloroethyl) cyclopropyl, vinylcyclopropyl, (methoxymethyl) cyclopropyl, (ethoxymethyl) cyclopropyl, (isopropoxymethyl) cyclopropyl, (methylthiomethyl) ) Cyclopropyl, (ethylthiomethyl) cyclopropyl, (isopropylthiomethyl) cyclopropyl, (methylsulfinylmethyl) cyclopropyl, (ethylsulfinylmethyl) cyclopropyl, (methylsulfonylmethyl) cyclopropyl, (ethylsulfonylmethyl) cyclo Propyl, cyanocyclopropyl, (1-methoxyiminoethyl) cyclopropyl, acetylcyclopropyl, propionylcyclopropyl, benzoylcyclopropyl, carboxylcyclopropyl, methoxycarbonylcyclopropyl, ethoxycarbonylcyclopropyl, carbamoylcyclopropyl, (dimethylcarbamoyl) Cyclopropyl, (diethylcarbamoyl) cyclopropyl, phenylcyclopropyl, (fluorophenyl) cyclopropyl Pill, (chlorophenyl) cyclopropyl, tolylcyclopropyl, furylcyclopropyl, thienylcyclopropyl, pyridylcyclopropyl, aminocyclopropyl, (methylamino) cyclopropyl, (dimethylamino) cyclopropyl, (acetylamino) cyclopropyl, ( Methoxycarbonylamino) cyclopropyl, (3,3-dimethylureido) cyclopropyl, (methylsulfonylamino) cyclopropyl, nitrocyclopropyl, hydroxycyclopropyl, methoxycyclopropyl, ethoxycyclopropyl, (trifluoromethoxy) cyclopropyl, Phenoxycyclopropyl, methylthiocyclopropyl, ethylthiocyclopropyl, phenylthiocyclopropyl, methylsulfinylcyclopropyl, ethylsulfone Ynylcyclopropyl, methylsulfonylcyclopropyl, ethylsulfonylcyclopropyl, dimethylcyclopropyl, methyl (ethyl) cyclopropyl, diethylcyclopropyl, biscyanocyclopropyl, trimethylcyclopropyl, tetramethylcyclopropyl, pentamethylcyclopropyl, methyl It may be cyclobutyl, vinylcyclobutyl, cyanocyclobutyl, carboxylcyclobutyl, acetylcyclobutyl, methoxycarbonylcyclobutyl or aminocyclobutyl group, preferably a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₃ -C ₄ same or different 1 to 5 substituents selected from the group consisting of cycloalkyl group and a cyano group, or, selected from the group consisting of "fluorine atom, a chlorine atom and a bromine atom One or different 1 to 3 substituents are substituted C ₁ -C ₃ alkyl group, or, C ₃ -C ₄ cycloalkyl group, a cyano group, C ₂ -C ₄ alkylcarbonyl group, C ₂ -C ₄ alkoxycarbonyl group, a phenyl group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ alkylthio group, C ₁ -C ₃ alkylsulfinyl group, C ₁ -C ₃ alkylsulfonyl groups, C ₁ -C ₂ alkylenedioxy group , imino group or C ₁ -C ₃ alkyl group C ₁ -C ₃ alkoxyimino group is substituted ", C ₂ -C ₄ alkenyl group, C ₂ -C ₄ alkylcarbonyl group, a benzoyl group, a carboxyl group, C ₂ ~ C ₄ alkoxycarbonyl group, a carbamoyl group, a di (C ₁ -C ₃ alkyl) carbamoyl group, "a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group," a fluorine atom, a chlorine atom and a bromine atom 1-3 substituents selected same or different from the group consisting of the C ₁ -C ₃ alkyl group "substituted, C ₃ -C ₄ cycloalkyl group, a cyano group and a tri (C ₁ -C ₃ alkyl ) A phenyl group which may be substituted by the same or different 1 to 3 substituents selected from the group consisting of silicon groups ”, a 5-membered heterocyclic group (the heterocyclic ring is one nitrogen atom in the ring) Contains an oxygen atom or a sulfur atom. ), "The same or different 1-2 C ₁ -C ₃ alkyl group, or, C ₂ -C ₄ alkylcarbonyl group, C ₂ -C ₄ alkoxycarbonyl group, a di (C ₁ -C ₃ alkyl) carbamoyl group or C ₁ -C ₃ alkylsulfonyl amino group which may be substituted by a group ", a nitro group, a hydroxyl group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ haloalkoxy group, a phenoxy group, C ₁ -C ₃ alkylthio group, a phenylthio group, C ₁ -C ₃ alkylsulfinyl group or a C ₁ -C ₃ alkylsulfonyl group C ₃ -C ₄ cycloalkyl group substituted by, more preferably, a chlorine atom, a bromine atom, C ₁ -C ₂ alkyl group, the same or different 1 to 3 substituents selected from the group consisting of cyclopropyl group and cyano group, or the same selected from the group consisting of "a chlorine atom and a bromine atom 1-3 substituents is substituted with C ₁ -C ₂ alkyl group, or a cyclopropyl group, a cyano group, C ₂ -C ₃ alkylcarbonyl group, C ₂ -C ₃ alkoxycarbonyl group, a phenyl group, C ₁ -C ₂ alkoxy group, C ₁ -C ₂ alkylthio group, C ₁ -C ₂ alkylsulfinyl group, C ₁ -C ₂ alkylsulfonyl group, 1,2-ethylenedioxy group, an imino group or a C ₁ -C ₂ alkoxy C ₁ -C ₂ alkyl group "imino group is substituted, C ₂ -C ₃ alkenyl group, C ₂ -C ₃ alkylcarbonyl group, a benzoyl group, a carboxyl group, C ₂ -C ₃ alkoxycarbonyl group, a carbamoyl group, a di (C ₁ -C ₂ alkyl) carbamoyl group, “chlorine atom, bromine atom, C ₁ -C ₂ alkyl group,“ the same 1 to 3 C ₁ -C ₂ alkyl group substituted by fluorine atom or chlorine atom " Ropuropiru group, a cyano group and a tri (C ₁ -C ₂ alkyl) same or different 1 to 2 substituents may phenyl group substituted selected from the group consisting of silicon group ", a furyl group, a thienyl group," identical 1-2 C ₁ -C ₂ alkyl group, or, C ₂ -C ₃ alkylcarbonyl group, C ₂ -C ₃ alkoxycarbonyl group, a di (C ₁ -C ₂ alkyl) carbamoyl group or a C ₁ ~ C ₂ alkylsulfonyl amino group which may be substituted by a group ", a nitro group, a hydroxyl group, C ₁ -C ₂ alkoxy group, C ₁ -C ₂ haloalkoxy group, a phenoxy group, C ₁ -C ₂ alkylthio group, a phenylthio group, a cyclopropyl group which is substituted by C ₁ -C ₂ alkylsulfinyl group or C ₁ -C ₂ alkylsulfonyl group.

In the present invention, the “C ₄ -C ₁₀ bicycloalkyl group” is a bicyclic hydrocarbon having 4 to 10 carbon atoms, for example, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl. Or a bicyclodecyl group, preferably a bicyclohexyl or bicycloheptyl group, more preferably a bicyclo [3.1.0] hexyl or bicyclo [4.1.0] heptyl group, and even more preferably. , A bicyclo [3.1.0] hexane-6-yl group.

In the present invention, “optionally substituted phenylsulfonyl group (the substituent is a substituent selected from Substituent Group A)” means the “halogen atom” and the “C ₁ -C ₆ alkyl group”. the "C ₁ -C ₆ haloalkyl group", the "C ₃ -C ₆ cycloalkyl group", the same or different selected from the group consisting of cyano group and the "tri (C ₁ -C ₆ alkyl) silyl group" 1 to 5 substituents which may be substituted, such as phenylsulfonyl, fluorophenylsulfonyl, difluorophenylsulfonyl, trifluorophenylsulfonyl, chlorophenylsulfonyl, dichlorophenylsulfonyl, trichlorophenylsulfonyl, fluorochlorophenylsulfonyl , Methylphenylsulfonyl, dimethylphenylsulfo , Trimethylphenylsulfonyl, tetramethylphenylsulfonyl, pentamethylphenylsulfonyl, ethylphenylsulfonyl, fluoro (methyl) phenylsulfonyl, chloro (methyl) phenylsulfonyl, bromo (methyl) phenylsulfonyl, cyclopropylphenylsulfonyl, cyclopropyl (fluoro ) Phenylsulfonyl, chloro (cyclopropyl) phenylsulfonyl, cyclopropyl (methyl) phenylsulfonyl, (trifluoromethyl) phenylsulfonyl or fluoro (trifluoromethyl) phenylsulfonyl group, preferably fluorine atom, chlorine atom , bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, one to three substituents the same or different selected from the group consisting of chlorine and bromine is substituted C ₁ -C ₃ alkyl group ", C ₃ -C ₄ cycloalkyl group, one to three substituents the same or different selected from cyano group and a tri (C ₁ -C ₃ alkyl) group consisting of silicon group A phenylsulfonyl group which may be substituted, more preferably a phenylsulfonyl, chlorophenylsulfonyl, methylphenylsulfonyl, trifluorophenylsulfonyl or cyanophenylsulfonyl group.

In the present invention, “di (C ₁ -C ₆ alkyl) sulfamoyl group” is a sulfamoyl group in which two identical or different “substituents selected from C ₁ -C ₆ alkyl groups” are bonded to a nitrogen atom. For example, dimethylsulfamoyl, methylethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl or dihexylsulfamoyl, preferably two identical or different C It is a sulfamoyl group to which a _{1 to} C ₃ alkyl group is bonded, more preferably a dimethylsulfamoyl group or a diethylsulfamoyl group, and even more preferably a dimethylsulfamoyl group.

In the present invention, “a 3- to 6-membered heterocyclic group which may be substituted (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms. And may be condensed with a benzene ring. The substituent is a substituent selected from Substituent Group E.) ”is the“ halogen atom ”and the“ C ₁ -C ₆ alkyl group ”. And ₁ to 3 identical or different substituents selected from the group consisting of “C ₁ -C ₆ haloalkyl group”, or a hydroxyl group, the above “optionally substituted phenylsulfonyl group (the substituent is substituted Is a substituent selected from the group A.) ”or“ di (C ₁ -C ₆ alkyl) sulfamoyl group ”, and may be condensed with a benzene ring. Contains nitrogen, oxygen or sulfur atoms, and It may contain ~ 2 nitrogen atoms, a 3- to 6-membered heterocyclic group ", preferably a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group and" a fluorine atom, a chlorine atom and one to three identical substituents selected from the group consisting of C ₁ -C ₃ alkyl group "substituted or different one to two substituents the same or different selected from the group consisting of bromine, Or, a hydroxyl group, “a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group,“ the same or different 1 to 3 substituents selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom. ₁ to ₃ identical or different substitutions selected from the group consisting of “substituted C ₁ -C ₃ alkyl group”, C ₃ -C ₄ cycloalkyl group, cyano group and tri (C ₁ -C ₃ alkyl) silicon group A phenylsulfonyl group which may be substituted ”or Or different well two C ₁ -C ₃ sulfamoyl group which the alkyl group is attached "of substituted benzene ring fused may, as" heteroatom, one nitrogen atom, an oxygen atom or a sulfur atom A 3- to 6-membered heterocyclic group which may further contain one nitrogen atom, and more preferably a chlorine atom, a bromine atom, a methyl group, an ethyl group, and a trifluoromethyl group. The same 1 to 2 substituents selected from the group, or a hydroxyl group, phenylsulfonyl group, tolylsulfonyl group or dimethylsulfamoyl group, which may be substituted, aziridine, oxiranyl, oxetanyl, pyrrolyl, furyl, thienyl, pyrazolyl , Thiazolyl, pyridyl, benzimidazolyl or benzothiazolyl, and even more preferably from a chlorine atom, a methyl group and a trifluoromethyl group That the same or different 1 to 2 substituents may be substituted, thienyl, pyrazolyl, thiazolyl group.

In the present invention, “(C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkoxy group” is an alkoxy group having 1 to 6 carbon atoms to which an alkoxy group having 1 to 6 carbon atoms is bonded. Methoxy, ethoxymethoxy, propoxymethoxy, butoxymethoxy, s-butoxymethoxy, t-butoxymethoxy, pentyloxymethoxy, hexyloxymethoxy, methoxyethoxy, ethoxyethoxy, propoxyethoxy, butoxyethoxy, methoxypropoxy, methoxybutoxy, methoxypentyloxy Or a methoxyhexyloxy group, preferably an alkoxy group having 1 to 3 carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms, more preferably methoxyethoxy, ethoxyethoxy or ethoxymethoxy. It is a group.

In the present invention, “an optionally substituted phenoxy group (the substituent is a pyridazinyloxy group substituted by a hydroxyl group or a substituent selected from a halogen atom and a C ₁ -C ₆ alkoxy group)” Is a phenoxy group that may be substituted by one hydroxyl group, or ₁ to 3 identical or different substituents selected from the group consisting of the “halogen atom” and the “C ₁ -C ₆ alkoxy group”. phenoxy group substituted pyridazinyloxy group is substituted, preferably, hydroxy phenoxy group, or a fluorine atom, a chlorine atom, the same are selected from the group consisting of bromine and C ₁ -C ₃ alkoxy or It is a phenoxy group substituted by a pyridazinyloxy group substituted with 1 to 2 different substituents, and more preferably one chlorine atom and one methoxy or ethoxy group. Substituted pyridazinyloxy group is a phenoxy group substituted.

In the present invention, “a 5- to 6-membered heterocyclic oxy group which may be substituted (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and 1 to 2 nitrogen atoms). may contain an atom. the substituent is a substituent selected from substituent group E.), the "halogen atom", the "C ₁ -C ₆ alkyl group", the "C ₁ -C ₆ haloalkyl group ”, hydroxyl group, the above“ optionally substituted phenylsulfonyl group (the substituent is a substituent selected from substituent group A) ”and the“ di (C ₁ -C ₆ alkyl) sulfamoyl group ”. May be substituted by the same or different 1 to 2 substituents selected from the group consisting of “a hetero atom containing one nitrogen atom, oxygen atom or sulfur atom, and further 1 to 2 A 5-6 membered heterocyclic oxy group which may contain a nitrogen atom. Preferably, fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, one to three substituents the same or different from selected from the group consisting of chlorine and bromine substituted C ₁ -C ₃ alkyl group ", a hydroxyl group," a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, the same or different selected from the group consisting of chlorine and bromine identical to 1 to 3 substituents are selected from the group consisting of C ₁ -C ₃ alkyl group ", C ₃ -C ₄ cycloalkyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silyl group substituted with Or the same or different selected from the group consisting of “phenylsulfonyl group which may be substituted by 1 to 3 different substituents” and “sulfamoyl group to which two same or different C _{1 to} C ₃ alkyl groups are bonded”. 1 to 2 substituents A 5- to 6-membered heterocyclic oxy group which contains one nitrogen atom, oxygen atom or sulfur atom and may further contain one nitrogen atom as a hetero atom, which may be substituted; More preferably, 1 to 2 different groups selected from the group consisting of a chlorine atom, a bromine atom, a methyl group, an ethyl group, a trifluoromethyl group, a hydroxyl group, a phenylsulfonyl group, a tolylsulfonyl group, and a dimethylsulfamoyl group. The substituent may be a pyridyloxy, pyrrolyloxy, furyloxy, thienyloxy, pyrazolyloxy, thiazolyloxy, pyrimidyloxy, pyrazinyloxy or pyridazinyloxy group, and more preferably a chlorine atom and a hydroxyl group are substituted. A good pyridazinyloxy group.

In the present invention, the “optionally substituted phenylsulfonyloxy group (the substituent is a substituent selected from Substituent Group A)” refers to the “halogen atom” and the “C ₁ -C ₆ alkyl group”. ”, The“ C ₁ -C ₆ haloalkyl group ”, the“ C ₃ -C ₆ cycloalkyl group ”, the cyano group, and the“ tri (C ₁ -C ₆ alkyl) silicon group ”. Different 1 to 5 substituents are phenylsulfonyloxy groups which may be substituted, such as phenylsulfonyloxy, fluorophenylsulfonyloxy, difluorophenylsulfonyloxy, trifluorophenylsulfonyloxy, chlorophenylsulfonyloxy, dichlorophenylsulfonyloxy , Trichlorophenylsulfonyloxy, fluorochlorophenylsulfo Ruoxy, methylphenylsulfonyloxy, dimethylphenylsulfonyloxy, trimethylphenylsulfonyloxy, tetramethylphenylsulfonyloxy, pentamethylphenylsulfonyloxy, ethylphenylsulfonyloxy, fluoro (methyl) phenylsulfonyloxy, chloro (methyl) phenylsulfonyloxy, Bromo (methyl) phenylsulfonyloxy, cyclopropylphenylsulfonyloxy, cyclopropyl (fluoro) phenylsulfonyloxy, chloro (cyclopropyl) phenylsulfonyloxy, cyclopropyl (methyl) phenylsulfonyloxy, (trifluoromethyl) phenylsulfonyloxy or It may be a fluoro (trifluoromethyl) phenylsulfonyloxy group, preferably Fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, C ₁ ~ in which one to three substituents the same or different selected from the group consisting of chlorine atom and bromine atom is substituted The same or different 1 to 3 substituents selected from the group consisting of “C ₃ alkyl group”, C ₃ -C ₄ cycloalkyl group, cyano group and tri (C ₁ -C ₃ alkyl) silicon group are substituted. A good phenylsulfonyloxy group, more preferably a phenylsulfonyloxy, chlorophenylsulfonyloxy, methylphenylsulfonyloxy, trifluorophenylsulfonyloxy or cyanophenylsulfonyloxy group.

In R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ of the present invention, “the two adjacent groups may be formed together with the carbon atom to which each is bonded, which may be substituted 3 to 6 members. A cyclic hydrocarbon group (the cyclic hydrocarbon may be interrupted by one or two different heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. The substituent is a halogen atom, C ₁ -C ₆ alkyl group, a hydroxy C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, an oxo group, a hydroxyimino group or a C ₁ -C ₆ alkoxyimino group, C ₁ -C ₆ alkyl group Is substituted with another C ₁ -C ₆ alkyl group or a carbon atom on the ring to form a new three-membered ring.) ”Means“ halogen atom ”,“ C _1- C ₆ alkyl group ", said substituted by 1-2 hydroxy groups" C ₁ -C ₆ alkyl group ", the" C ₁ -C ₆ alkoxy group ", an oxo group, hydroxyimino group, and the" C ₁ -C ₆ alkoxyimino same or different 1 to 4 selected from the group consisting of group " Saturated or unsaturated 3- to 6-membered rings which may be substituted by one or two heteroatoms which may be substituted and may be substituted by the same or different heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur atoms It is a hydrocarbon group and may form a cyclopropane ring on the ring, and is preferably --CH _2- , --CH ₂ CH _2- , --CH ₂ CH ₂ CH _2- , --CH (CH ₃ ). CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH _2- , -C (CH ₃ ) ₂ CH ₂ CH _2- , -CH ₂ C (CH ₃ ) ₂ CH _2- , -CH (OCH ₃ ) CH ₂ CH _2- , -C (OCH ₃ ) ₂ CH ₂ CH _2- , -CH ₂ C (OCH ₃ ) ₂ CH _2- , -C (= O) CH ₂ CH _2- , -CH ₂ C (= O) CH _2- , -C (= NOCH ₃ ) CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH _2- , -CH (CH ₃ ) CH ₂ CH ₂ CH _2- , -C (CH ₃ ) ₂ CH ₂ CH ₂ CH _2- , -CH (OCH ₃ ) CH ₂ CH ₂ CH _2- , -C H = CH-CH = CH-, -OCH ₂ CH _2- , -OCH (CH ₃ ) CH _2- , -OCH ₂ CH (CH ₃ )-, -OC (CH ₃ ) ₂ CH _2- , -OCH = CH-, -OC (CH ₃ ) = CH-, -OCH = C (CH ₃ )-, -SCH = CH-, -N = CH-CH = CH-, -OCH ₂ O-, -OCH (CH ₃ ) O-, -OC (CH ₃ ) ₂ O-, -OCF ₂ O-, -OCH ₂ CH ₂ O-, -OCH = N-, -OC (CH ₃ ) = N-,

In a group represented by, more _{preferably, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, -CH = CH-CH = CH-, -OCH ₂ CH _2- , -OCH = CH-, -OCH = C (CH ₃ )-, -SCH = CH-, -N = CH-CH = CH- , -OCH ₂ O-, -OCH ₂ CH ₂ O-,

And even more preferably, —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ CH ₂ —, —OCH ₂ CH ₂ —, —OCH═CH— or

It is group represented by these.

  The compound (I) of the present invention can be converted into a salt used in ordinary agricultural chemicals, for example, an alkali metal salt, an alkaline earth metal salt or an ammonium salt, and a basic moiety in the molecule. If there is, for example, a salt such as sulfate, hydrochloride, nitrate, phosphate can be formed. As long as they can be used as herbicides for agriculture and horticulture, they are included in the present invention.

  In the present invention, the “alkali metal salt” can be, for example, a sodium salt, a potassium salt or a lithium salt, and is preferably a sodium salt or a potassium salt.

  In the present invention, the “alkaline earth metal salt” can be, for example, a calcium salt or a magnesium salt, and is preferably a calcium salt.

  Solvates of the compounds of the present invention are also encompassed by the present invention.

  Among the compounds of the present invention, there are compounds having an asymmetric carbon, and in this case, the present invention also includes a mixture of one kind of optically active substance and several kinds of optically active substances in an arbitrary ratio.

In the present invention, the “ester derivative” is a compound in which an acyl group or the like is bonded to the oxygen atom of the hydroxyl group bonded to the 4-position of the pyridazine ring. For example, the C _{2 to} C ₁₅ alkylcarbonyl group [substituent group, halogen atom, C ₁ -C ₆ alkoxy group, C ₂ -C ₇ alkoxycarbonyl group, may be substituted C ₂ -C ₆ alkenyloxycarbonyl group {said substituent group is C ₃ -C ₆ cycloalkyl group , a cyano group and which may be substituted benzoyl group (the substituent is a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ ~ The same or different 1 to 3 substituents selected from the group consisting of C ₃ alkylsulfonyl groups.) The same or different 1 to 3 substituents selected from the group consisting of . }, An optionally substituted C ₃ -C ₆ cycloalkenyloxycarbonyl group {the substituent is an oxo group and an optionally substituted benzoyl group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ A group consisting of ₁ to ₃ identical or different substituents selected from the group consisting of a -C ₃ haloalkyl group, a C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group. 1 to 2 substituents selected from the same or different. }, A 5- or 6-membered heterocyclic oxycarbonyl group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms May be included. The substituent is a halogen atom, a C ₁ -C ₆ alkyl group, an optionally substituted phenoxy group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, a C _3- The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1) to 3 or the same or different 1 to 3 substituents selected from the group consisting of: }, Which may be substituted phenyl group (said substituent is a halogen atom, C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, C ₁ -C ₆ alkoxy group and C ₂ -C ₇ alkoxycarbonyl group selected from the group consisting of the same or different 1 to 3 substituents.), is the same or different 1 to 3 substituents selected from the group consisting of phenoxy group, and C ₁ -C ₆ alkylthio group . ], C ₄ -C ₇ cycloalkylcarbonyl group, adamantyl group may be substituted C ₃ -C ₇ alkenylcarbonyl group (the substituent has the same or different selected from the group consisting of a halogen atom and a phenyl group 1 ˜2 substituents), a C ₃ -C ₇ alkynylcarbonyl group, an optionally substituted benzoyl group [the substituent is a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent Are the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a phenyl group.), A cyano group, a C ₂ -C ₇ alkylcarbonyl group, a C ₂ -C ₇ alkoxycarbonyl group, may be substituted C ₃ -C ₇ alkenyloxycarbonyl group {said substituents, C ₃ -C ₆ cycloalkyl group, a cyano group and which may be substituted benzoyl group (those該置Same substituent is selected from halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ group consisting of an alkylsulfonyl group Or 1 to 3 different substituents selected from the group consisting of 1 to 3 different substituents. }, An optionally substituted C ₄ -C ₇ cycloalkenyloxycarbonyl group {the substituent is an oxo group and an optionally substituted benzoyl group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ A group consisting of ₁ to ₃ identical or different substituents selected from the group consisting of a -C ₃ haloalkyl group, a C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group. 1 to 2 substituents selected from the same or different. }, A phenyl group, a nitro group, an optionally substituted C ₁ -C ₆ alkoxy group (the substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a phenyl group. ), A phenoxy group, an optionally substituted 5- or 6-membered heterocyclic oxycarbonyl group {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring; It may contain nitrogen atoms. The substituent is a halogen atom, a C ₁ -C ₆ alkyl group, an optionally substituted phenoxy group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, a C _3- C ₆ is the same or different 1 to 3 substituents selected from cycloalkyl group and C ₂ -C ₇ alkoxyalkyl group consisting carbonyl group.), 2,3-dihydro -1H- indenyl group and a substituted which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkyl sulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1) to 3 or the same or different 1 to 3 substituents selected from the group consisting of: } And a 5- or 6-membered heterocyclic oxysulfonyl group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms May be included. The substituent is a halogen atom, a C ₁ -C ₆ alkyl group, an optionally substituted phenoxy group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, a C _3- The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1) to 3 or the same or different 1 to 3 substituents selected from the group consisting of: } Are the same or different 1 to 3 substituents selected from the group consisting of: ], A naphthoyl group, an optionally substituted 3- to 8-membered heterocyclic carbonyl group [the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms It may contain atoms and may form a 5- to 6-membered spiro ring containing 1-2 oxygen atoms on any carbon atom in the heterocycle. The substituent is a halogen atom and an optionally substituted C ₁ -C ₆ alkyl group (the substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a phenyl group. ), A cyano group, a C ₂ -C ₇ alkylcarbonyl group, a C ₂ -C ₇ alkoxycarbonyl group, an optionally substituted phenyl group (the substituent is the same or different 1 to 3 halogen atoms). A 5- or 6-membered heterocyclic group which may be substituted (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom, and further contains 1 to 2 nitrogen atoms in the ring) The substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a C ₁ -C ₆ alkyl group.), Nitro group, hydroxyl group, C ₁ -C ₆ alkoxy Group, phenoxy group, oxo group, hydroxy Imino group, C ₁ -C ₆ alkoxyimino group, C ₁ -C ₆ alkylthio group, C ₂ -C ₆ alkenylthio group, a phenylthio group, which may be substituted 5 or 6-membered heterocyclic carbonyl group (said heterocyclic is in the ring, the one, nitrogen atom, contains an oxygen atom or a sulfur atom, may further contain one or two nitrogen atoms. the substituent is a halogen atom and a C ₁ -C ₆ alkyl group The same or different 1 to 3 substituents selected from the group consisting of: and a 5- or 6-membered heterocyclic oxycarbonyl group which may be substituted {the heterocyclic ring is one nitrogen atom in the ring; It contains atoms, oxygen atoms or sulfur atoms, and may contain 1 to 2 nitrogen atoms. The substituents are halogen atom, C ₁ -C ₆ alkyl group, which may be substituted phenoxy group (the substituent is halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₃ ~ C ₆ is the same or different 1 to 3 substituents selected from cycloalkyl group and C ₂ -C ₇ alkoxyalkyl group consisting carbonyl group.), 2,3-dihydro -1H- indenyl group and a substituted which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1) to 3 or the same or different 1 to 3 substituents selected from the group consisting of: } Are the same or different 1 to 3 substituents selected from the group consisting of: An optionally substituted 7 to 14-membered fused bi- or tricyclic heterocyclic carbonyl group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring; may contain two nitrogen atoms or oxygen atoms. the substituents are the same or different 1 to 3 substituents selected from the group consisting of halogen atom and C ₁ -C ₆ alkyl group.) 5- or 6-membered heterocyclic carbonylcarbonyl group (the heterocyclic ring may contain one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms). ) may be substituted C ₂ -C ₇ alkoxycarbonyl group (said substituent is a halogen atom, C ₁ -C ₆ same or different 1 to 3 substituents selected from the alkoxy group and the group consisting of phenyl group in a.), C ₃ ~C ₇ alkenyloxycarbonyl , Which may be substituted phenoxycarbonyl group (said substituent is a halogen atom, C ₁ -C ₆ alkyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ to 3 identical or different substituents selected from the group consisting of _{1 to} C ₆ alkoxy groups.), Condensed polycyclic hydrocarbon oxycarbonyl groups, optionally substituted 5 or 6 membered heterocyclic oxycarbonyls The group {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms. The substituent is a halogen atom, a C ₁ -C ₆ alkyl group, an optionally substituted phenoxy group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, a C _3- The same or different 1 to 3 substituents selected from the group consisting of a C ₆ cycloalkyl group and a C ₂ -C ₇ alkoxycarbonyl group.), 2,3-dihydro-1H-indenyloxy group and substitution which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1) to 3 or the same or different 1 to 3 substituents selected from the group consisting of: }, Which may be substituted carbamoyl group {said substituents may be substituted C ₁ -C ₆ alkyl group (said substituent is a halogen atom, C ₂ -C ₇ alkoxycarbonyl group, a cyano group, phenyl group and C ₁ to 3 substituents selected from the group consisting of _{1 to} C ₆ alkoxy groups), C _{3 to} C ₆ alkenyl groups, phenyl groups, optionally substituted 5 or 6 membered heterocyclic groups. (The heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms. The substituent includes a halogen atom and C _1. -C ₆ identical or different 1 to 3 substituents selected from the group consisting of alkyl group.), C ₂ ~C ₇ alkylcarbonyl group, C ₂ ~C ₇ alkoxycarbonyl group and C ₁ -C ₆ The same or selected from the group consisting of alkoxy groups 1 to 3 different substituents. }, (C ₁ -C ₆ alkylthio) carbonyl group, (C ₃ -C ₆ cycloalkylthio) carbonyl group, (phenylthio) carbonyl group, optionally substituted C ₁ -C ₈ alkylsulfonyl group (the substituents are the same) or different 1 to 3 halogen atoms.), which may be substituted phenylsulfonyl group [the substituent is a halogen atom, C ₁ -C ₆ alkyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group , C ₂ -C ₇ alkoxycarbonyl group, nitro group, C ₁ -C ₆ alkoxy group, may be substituted C ₂ -C ₆ alkenyloxy sulfonyl group {said substituents, C ₃ -C ₆ cycloalkyl group, a cyano group and which may be substituted benzoyl group (the substituent is a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, two B are the same or different 1 to 3 substituents selected from the group, and C ₁ -C ₃ group consisting of an alkylsulfonyl group.) The same or selected from the group consisting of different with 1-3 substituents is there. }, An optionally substituted C ₃ -C ₆ cycloalkenyloxysulfonyl group {the substituent is an oxo group and an optionally substituted benzoyl group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ A group consisting of ₁ to ₃ identical or different substituents selected from the group consisting of a -C ₃ haloalkyl group, a C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group. 1 to 2 substituents selected from the same or different. } And a 5- or 6-membered heterocyclic oxysulfonyl group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms May be included. The substituent is a halogen atom, a C ₁ -C ₆ alkyl group, an optionally substituted phenoxy group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, a C _3- C ₆ is the same or different 1 to 3 substituents selected from cycloalkyl group and C ₂ -C ₇ alkoxyalkyl group consisting carbonyl group.), 2,3-dihydro -1H- indenyl group and a substituted which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1) to 3 or the same or different 1 to 3 substituents selected from the group consisting of: } Are the same or different 1 to 3 substituents selected from the group consisting of: An optionally substituted 5- or 6-membered heterocyclic sulfonyl group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms) The substituent is the same or different 1 to 3 substituents selected from the group consisting of a halogen atom and a C _{1 to} C ₆ alkyl group. Ring oxysulfonyl group {The heterocyclic ring may contain one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms. The substituent is a halogen atom, a C ₁ -C ₆ alkyl group, an optionally substituted phenoxy group (the substituent is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₃ haloalkyl group, a C _3- C ₆ is the same or different 1 to 3 substituents selected from cycloalkyl group and C ₂ -C ₇ alkoxyalkyl group consisting carbonyl group.), 2,3-dihydro -1H- indenyl group and a substituted which may be a benzoyl group (the substituent is to be a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₃ haloalkyl group, C ₂ -C ₇ alkoxycarbonyl group, a nitro group and a C ₁ -C ₃ alkylsulfonyl group The same or different 1 to 3 substituents selected from the group consisting of: 1) to 3 or the same or different 1 to 3 substituents selected from the group consisting of: }, Di (C ₁ -C ₆ alkyl) sulfamoyl group, C ₁ -C ₆ alkoxysulfonyl group, di (C ₁ -C ₆ alkyl) phosphoryl group, tri (C ₁ -C ₆ alkyl) silicon group or triphenyl silicon give a compound group is bonded, preferably, C ₂ -C ₁₀ alkylcarbonyl group, which may be substituted benzoyl group (the substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group ₁ to 2 identical or different selected from the group consisting of C ₁ -C ₃ alkoxy group or 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yloxycarbonyl group is a substituent.), pyrrolidinylcarbonyl group, azetidinyloxyimino carbonyl group, morpholine group, may be substituted C ₂ -C ₅ alkoxycarbonyl group (the substituent is off Atom are the same or different 1 to 3 substituents selected from the group consisting of chlorine atom and bromine atom.), Di (C ₁ -C ₃ alkyl) carbamoyl group, (C ₁ -C ₃ alkyl) (C ₁ -C ₃ alkoxy) carbamoyl group may be substituted C ₁ -C ₃ alkylsulfonyl group (said substituents may be the same or different 1 to 3 selected from a fluorine atom, the group consisting of chlorine and bromine . a number of substituents) or substituted or a phenylsulfonyl group (the substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, 4- (2,4-dichlorobenzoyl) - 1,3-dimethyl-1H-pyrazol-5-yloxysulfonyl group and the same or different 1-2 substituents selected from the group consisting of nitro groups), and more preferably. , C ₂ -C ₄ alkylcarbonyl group, which may be substituted benzoyl group (the substituent is methyl or 4- (2,4-dichlorobenzoyl) -1,3-dimethyl--1H- pyrazol-5-yloxy is a carbonyl group.), 1-azetidinyloxyimino group, 4-morpholinylcarbonyl group, may be substituted C ₂ -C ₃ alkoxycarbonyl group (the substituent is a 1-3 chlorine atoms ), A dimethylcarbamoyl group, a methoxy (methyl) carbamoyl group, an optionally substituted C ₁ -C ₃ alkylsulfonyl group (the substituent is 1 to 3 fluorine atoms), or an optionally substituted phenylsulfonyl Group (the substituent is a chlorine atom, a methyl group, 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yloxysulfonyl) Group or nitro group. ) Is a bonded compound.

(A) In the present invention, R ¹ is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group (the halogen atom is 1 to a three fluorine atoms.), a cyclopropyl group, C ₂ -C ₃ alkenyl group, a cyano group, C ₂ -C ₄ alkylcarbonyl group, a di (C ₁ -C ₃ alkyl) carbamoyl group may be substituted phenyl group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, from the group consisting of chlorine and bromine is chosen the same or different 1 to 3 halogen atoms.), the same or different 1 to 2 selected from the group consisting of cyclopropyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silyl group Substituents The }, A furyl group, a thienyl group, C ₁ -C ₃ alkoxy group, which may be substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ A haloalkyl group (the halogen atom is 1 to 3 fluorine atoms), a cyclopropyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group selected from the same or different 1 Two substituents. } Or a substituted pyrazolyloxy group (the substituent is one benzoyl group and two C ₁ -C ₃ alkyl groups substituted by two chlorine atoms),
More preferably, a chlorine atom, a bromine atom, a trifluoromethyl group or a cyano group,
Even more preferably, a chlorine atom or a bromine atom,
Particularly preferred is a chlorine atom.

(B) In the present invention, R ² is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C ₁ -C ₃ alkyl group, or (C ₁ -C ₃ alkoxy) C ₁ -C. ₃ alkyl group, which may be substituted benzoyl group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is fluorine atom, chlorine selected from the group consisting of and bromine are the same or different 1 to 3 halogen atoms.), selected from the group consisting of cyclopropyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silyl group Or the same or different 1 to 2 substituents. }, C ₂ -C ₄ alkoxycarbonyl group, may be substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen The atoms are the same or different 1 to 3 halogen atoms selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom.), Cyclopropyl group, cyano group and tri (C ₁ -C ₃ alkyl) It is the same or different 1-2 substituents selected from the group consisting of silicon groups. }, Which may be substituted phenylthio group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, a chlorine atom and same selected from the group consisting of bromine or different 1 to 3 halogen atoms.), the same is selected from the group consisting of cyclopropyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silyl group Or it is 1 to 2 different substituents. } Or a tri (C ₁ -C ₃ alkyl) silyl group,
More preferably, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethoxycarbonyl group or a trimethylsilyl group,
Even more preferred is a hydrogen atom.

(C) In the present invention, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are preferably independently of each other a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a substituted atom. A good C ₁ -C ₄ alkyl group (the substituent is the same or different 1 to 3 substituents selected from the group consisting of fluorine atom, chlorine atom and bromine atom, or C ₃ -C ₄ cycloalkyl group) A C ₁ -C ₃ alkylthio group or a C ₁ -C ₃ alkoxyimino group), a C ₂ -C ₃ alkenyl group, a C ₂ -C ₃ alkynyl group, an optionally substituted C ₃ -C ₅ cycloalkyl group. (the substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₃ -C ₄ cycloalkyl group, a cyano group, C ₁ -C ₃ alkoxy groups and C ₁ -C ₃ alkylthio group 1 to 3 identical or different selected from the group consisting of Is a substituent.), C ₆ ~C ₇ bicycloalkyl group, a cyano group, C ₂ -C ₄ alkylcarbonyl group, C ₂ -C ₄ alkoxycarbonyl group, which may be substituted phenyl group {said substituent is fluorine atoms 1, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl or C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, the same or different selected from the group consisting of chlorine and bromine 3 halogen atoms). }, A 5- to 6-membered heterocyclic group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms. It's okay. The substituents are fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl and C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, selected from the group consisting of chlorine and bromine 1 to 3 halogen atoms which are the same or different. The same or different 1 to 2 substituents selected from the group consisting of: }, Nitro group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ haloalkoxy group (said halogen atom is a fluorine atom, 1-3 was selected same or different from the group consisting of chlorine and bromine of a halogen atom.), which may be substituted phenoxy group (the substituent is a fluorine atom, a chlorine atom, pyridazinium substituted with a substituent selected from bromine atom, and C ₁ -C ₃ alkoxy group Gini oxy is a group.) or a C ₁ -C ₃ alkylthio group, ^{or, R 3, R 4, R} 5, R 6 and R ^7, two adjacent is taken together with the carbon atoms bonded thereto _{Te, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH = CH-CH = CH- , -OCH ₂ CH _2- , -OCH = CH-, -OCH = C (CH ₃ )-, -SCH = CH-, -N = CH-CH = CH-, -OCH ₂ O-, -OCH ₂ CH ₂ O-,

で表される基であり、

A group represented by

More preferably, independently of one another, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, may be substituted C ₁ -C ₄ alkyl group (the substituent is one to three fluorine atoms, Or a C ₃ -C ₄ cycloalkyl group which may be substituted (the substituent is a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₂ alkyl group, a cyclopropyl group). the same 1-2 substituents selected from the group consisting of radicals and C ₁ -C ₂ alkoxy group.), a cyano group, C ₂ -C ₃ alkoxycarbonyl group, a nitro group, C ₁ -C ₃ alkoxy A group or a trifluoromethoxy group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ , together with the carbon atom to which two adjacent ones are bonded to each other, —CH ₂ CH ₂ CH _2- , -CH (CH ₃ ) CH ₂ CH _2- , -OCH ₂ CH _2- , -OCH = CH- or

で表される基であり、但し、Ｒ³は水素原子ではなく、

Wherein R ³ is not a hydrogen atom,

Even more preferably, independently of one another, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, C ₁ -C ₃ alkyl group may be substituted C ₃ -C ₄ cycloalkyl group (said substituent is the same 1 to 2 substituents selected from the group consisting of a chlorine atom and C ₁ -C ₂ alkyl group.), a cyano group or a C ₁ -C ₂ alkoxy group, or, R ^3, R ⁴ , R ⁵ , R ⁶ and R ⁷ are groups represented by —CH ₂ CH ₂ CH ₂ — or —OCH═CH—, in which two adjacent groups together with the carbon atom to which each is bonded. Provided that R ³ is not a hydrogen atom,
Particularly preferably, independently of each other, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an isopropyl group, an optionally substituted cyclopropyl group (the substituent is two A chlorine atom.) Or a methoxy group, or R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ , together with the carbon atom to which two adjacent groups are bonded, ₂ CH ₂ CH ₂ —, wherein R ³ is not a hydrogen atom,
Most preferably, R ³ is a fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, isopropyl group, cyclopropyl group or methoxy group, and R ⁷ is a hydrogen atom, fluorine atom , A chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an isopropyl group, a cyclopropyl group or a methoxy group, and R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group It is.

(D) In the present invention, m and n are preferably both 0.
The compound (I) of the present invention is preferably
(1a) R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group (the halogen atom is 1 to 3 fluorine atoms). ), cyclopropyl group, C ₂ -C ₃ alkenyl group, a cyano group, C ₂ -C ₄ alkylcarbonyl group, a di (C ₁ -C ₃ alkyl) carbamoyl group, which may be substituted phenyl group {said substituent, fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, and the same or different selected from the group consisting of chlorine and bromine 1 ˜3 halogen atoms), a cyclopropyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group are the same or different 1-2 substituents selected from the group consisting of. }, A furyl group, a thienyl group, C ₁ -C ₃ alkoxy group, which may be substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ A haloalkyl group (the halogen atom is 1 to 3 fluorine atoms), a cyclopropyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group selected from the same or different 1 Two substituents. } Or a substituted pyrazolyloxy group (the substituent is one benzoyl group and two C ₁ -C ₃ alkyl groups substituted by two chlorine atoms),
(1b) R ² may be substituted with a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C ₁ -C ₃ alkyl group, a (C ₁ -C ₃ alkoxy) C ₁ -C ₃ alkyl group, benzoyl group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, from the group consisting of chlorine and bromine The same or different 1 to 3 halogen atoms selected), the same or different 1 to 2 selected from the group consisting of a cyclopropyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silicon group. Substituents. }, C ₂ -C ₄ alkoxycarbonyl group, may be substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen The atoms are the same or different 1 to 3 halogen atoms selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom.), Cyclopropyl group, cyano group and tri (C ₁ -C ₃ alkyl) It is the same or different 1-2 substituents selected from the group consisting of silicon groups. }, Which may be substituted phenylthio group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, a chlorine atom and same selected from the group consisting of bromine or different 1 to 3 halogen atoms.), the same is selected from the group consisting of cyclopropyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silyl group Or it is 1 to 2 different substituents. } Or a tri (C ₁ -C ₃ alkyl) silyl group,
(1c) R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a C ₁ -C ₄ alkyl group which may be substituted. (The substituent is the same or different 1 to 3 substituents selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom, or a C _{3 to} C ₄ cycloalkyl group, a C _{1 to} C ₃ alkylthio group. Or a C ₁ -C ₃ alkoxyimino group.), A C ₂ -C ₃ alkenyl group, a C ₂ -C ₃ alkynyl group, an optionally substituted C ₃ -C ₅ cycloalkyl group (the substituent is a fluorine atom) , a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₃ -C ₄ cycloalkyl group, a cyano group, the same or are selected from C ₁ -C ₃ alkoxy groups and C ₁ -C ₃ alkylthio group different 1 to 3 substituents.), C ₆ ~ ₇ bicycloalkyl group, a cyano group, C ₂ -C ₄ alkylcarbonyl group, C ₂ -C ₄ alkoxycarbonyl group, which may be substituted phenyl group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ ~ A C ₃ alkyl group or a C ₁ -C ₃ haloalkyl group (the halogen atoms are the same or different 1 to 3 halogen atoms selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom). . }, A 5- to 6-membered heterocyclic group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms. It's okay. The substituents are fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl and C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, selected from the group consisting of chlorine and bromine 1 to 3 halogen atoms which are the same or different. The same or different 1 to 2 substituents selected from the group consisting of: }, Nitro group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ haloalkoxy group (said halogen atom is a fluorine atom, 1-3 was selected same or different from the group consisting of chlorine and bromine which is a halogen atom.), which may be substituted phenoxy group (the substituent is a fluorine atom, a chlorine atom, pyridazinium substituted with a substituent selected from bromine atom, and C ₁ -C ₃ alkoxy group Gini oxy Or a C ₁ -C ₃ alkylthio group, or R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ are bonded together with the carbon atom to which they are adjacent to each other. _{Te, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH = CH-CH = CH- , -OCH ₂ CH _2- , -OCH = CH-, -OCH = C (CH ₃ )-, -SCH = CH-, -N = CH-CH = CH-, -OCH ₂ O-, -OCH ₂ CH ₂ O-,

で表される基であり、

A group represented by

(1d) a compound in which m and n are both 0;
More preferably,
(2a) R ¹ is a chlorine atom, a bromine atom, a trifluoromethyl group or a cyano group,
(2b) R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethoxycarbonyl group or a trimethylsilyl group,
(2c) R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a C ₁ -C ₄ alkyl group which may be substituted. (The substituent is 1 to 3 fluorine atoms or one cyclopropyl group.) A C _{3 to} C ₄ cycloalkyl group which may be substituted (the substituent is a fluorine atom or a chlorine atom) , a bromine atom, a C ₁ -C ₂ alkyl group, the same one or two substituents selected from the group consisting of cyclopropyl group, and C ₁ -C ₂ alkoxy group.), a cyano group, C ₂ -C ₃ alkoxycarbonyl group, nitro group, C ₁ -C ₃ alkoxy group or trifluoromethoxy group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are bonded to each other. -CH ₂ CH ₂ CH _2- , -CH (CH ₃ ) CH ₂ CH _2- , -OCH ₂ C H _2- , -OCH = CH- or

で表される基であり、但し、Ｒ³は水素原子ではなく、

Wherein R ³ is not a hydrogen atom,

(2d) a compound in which m and n are both 0;
Even more preferably,
(3a) R ¹ is a chlorine atom or a bromine atom,
(3b) R ² is a hydrogen atom,
(3c) R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently of each other a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C ₁ -C ₃ alkyl group, A good C ₃ -C ₄ cycloalkyl group (the substituent is the same 1-2 substituents selected from the group consisting of a chlorine atom and a C ₁ -C ₂ alkyl group), a cyano group or C ₁ a -C ₂ alkoxy group, ^{or, R 3, R 4, R} 5, R 6 and R ^7, two adjacent, together with the carbon atoms bonded thereto, -CH ₂ CH ₂ CH ₂ — or —OCH═CH—, wherein R ³ is not a hydrogen atom, and (3d) is a compound in which m and n are both 0;
Particularly preferably,
(4a) R ¹ is a chlorine atom,
(4b) R ² is a hydrogen atom,
(4c) R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently of each other hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, isopropyl group, substituted A cyclopropyl group (the substituent is two chlorine atoms) or a methoxy group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are adjacent to each other, A group represented by —CH ₂ CH ₂ CH ₂ —, together with the carbon atoms to which each is bonded, provided that R ³ is not a hydrogen atom,
(4d) A compound in which m and n are both 0.

  Although the typical compound of this invention is illustrated in following Table 1, this invention is not limited to these compounds.

Hereinafter, the R ³ to R ⁷ "H" is ^{R 3, R 4, R 5} , R 6 and R ⁷ are all hydrogen atoms, in R ³ to R ⁷ "2-Cl" is R ³ is “Me” represents a methyl group, “Et” represents an ethyl group, “Pr” represents a propyl group, “iPr” represents an isopropyl group, “cPr” represents a cyclopropyl group, “Bu”. `` Is a butyl group, `` iBu '' is an isobutyl group, `` sBu '' is a sec-butyl group, `` tBu '' is a tert-butyl group, `` cBu '' is a cyclobutyl group, `` Pen '' is a pentyl group, “CPen” represents a cyclopentyl group, “neoPen” represents a neopentyl group, “Hx” represents a hexyl group, “cHx” represents a cyclohexyl group, and “2-CH ₂ CH ₂ CH ₂ -3” in R ^{3 to} R ⁷ Indicates that R ³ and R ⁴ are trimethylene groups and together with the carbon atoms to which they are bonded form a 5-membered ring, “= N-OMe” indicates a methoxyimino group, “= `` O '' represents a carbonyl group together with the carbon atom to which they are bonded, `` SO ₂ (Ph-4-Me) '' represents a p-tolylsulfonyl group, and `` cPr-1-F '' represents 1-fluorocyclopropyl The group `` cPr-cis-2- (CH ₂ ) ₃ -cis-3 '' has the formula

`` C (-CH ₂ CH ₂ -)-CH ₂ CH ₂ '' is a group represented by the formula

In the group represented by the formula “CH (CH ₂ ) CH—CH ₂ ”

In the group represented by the formula, “CH (OCH ₂ ) ₂ ” represents the formula

`` Fur '' is a furyl group, `` Thi '' is a thienyl group, `` Pyr '' is a pyridyl group, `` Azr '' is an aziridinyl group, `` Pyrd '' is a pyrrolidinyl group, `` Pyrr '' Is a pyrrolyl group, “Pyza” is a pyrazolyl group, “Thiz” is a thiazolyl group, “Pyzn” is a pyridazinyl group, “Np” is a naphthyl group, “1-Ad” is a 1-adamantyl group, “ "Ioxa" is an isoxazolyl group, "Tdia" is a 1,2,3-thiadiazolyl group, "Bfur" is a 1-benzofuranyl group, "Bthi" is a 1-benzothienyl group, "Bthia" is 1,3- Benzothiazolyl group, “Boxaz” is 1,3-benzodioxolyl group, “Iqu” is isoquinolyl group, “Azet” is azetidinyl group, “Ppri” is piperidyl group, “1-Ppri-4- OCH ₂ CH ₂ O-4 "has the formula

`` Ppra '' represents a piperazinyl group, `` Morp '' represents a morpholinyl group, `` Tmor '' represents a thiomorpholinyl group, `` Carb '' represents a carbazolyl group, `` Pthia '' represents a phenothiazinyl group, `` Thpy "the in-tetrahydro -2H- pyranyl group," Q ¹ "is oxiranyl group," Q ² "is benzoxazolyl group," Q ³ "is benzothiazolyl group," Q ⁴ "fluorenyl group," “Q ⁵ ” represents a 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl group, and “Q ⁶ ” represents 6-chloro-3- (2-methylphenoxy) -4 - a pyridazinyl group, a "Q ⁷ 'is 6-chloro-3- (2-isopropyl-phenoxy) -4-pyridazinyl group," Q ⁸ "is 6-chloro-3- (2-cyclopropyl-phenoxy) -4- pyridazinyl group, "Q ^9" is 6-chloro-3- (2,3-dihydro -1H Indene-4-yloxy) -4-pyridazinyl group, a "Q ^10" is 6-chloro-3- (2,6-dimethylphenoxy) -4-pyridazinyl group, "Q ^11" is 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl group, “Q ¹² ” is 4- [2-chloro-3- (methoxycarbonyl) -4- (methylsulfonyl) benzoyl] -1-ethyl- 1H-pyrazol-5-yl group, “Q ¹³ ” represents 4- (2,4-dichloro-3-methylbenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl group, “Q ¹⁴ ”. Represents 2- [2-chloro-4- (methylsulfonyl) benzoyl] -3-oxo-1-cyclohexen-1-yl group, “Q ¹⁵ ” represents 2- [4- (methylsulfonyl) -2-nitrobenzoyl ] -3-Oxo-1-cycl Hexene-1-yl group, "Q ^16" are 2-cyano-1-cyclopropyl-3- [2- (methylsulfonyl) -4- (trifluoromethyl) phenyl] -3-oxo-1-propenyl group and the "Q ^17" is 3- [4-chloro-2- (methylsulfonyl) phenyl] -2-cyano-1-cyclopropyl-3-oxo-1-propenyl group, "Q ^18" 3,4 -Dihydro-2 (1H) -isoquinolinyl group, “Q ¹⁹ ” represents a 1,3-oxazolidin-3-yl group, “Q ²⁰ ” represents a 2,5-dihydro-1H-pyrrol-1-yl group, “Q ²¹ ” represents a 3,6-dihydro-1 (2H) -pyridinyl group, “Q ²² ” represents a 1,4-oxazepan-4-yl group, and “Q ²³ ” represents 2,3-dihydro-1H— indol-1-yl group, "Q ^24" is 1,3-dihydro -2H- isoindole -2 - yl group, "Q ^25" is 3,4-dihydro -1 (2H) - quinolinyl group, the "Q ^26" is 2,3-dihydro-4H-1,4-benzoxazin-4-yl group , Respectively.

  Among the above exemplified compounds, suitable compounds are compound numbers 124, 125, 126, 127, 128, 130, 131, 132, 134, 136, 139, 140, 144, 145, 151, 163, 173, 202, 207. , 217, 226, 249, 264, 265, 266, 267, 269, 270, 271, 272, 273, 279, 280, 284, 287, 292, 300, 304, 305, 306, 307, 308, 309, 311 , 330, 334, 336, 339, 344, 359, 361, 362, 364, 365, 370, 377, 385, 386, 387, 390, 391, 400, 401, 403, 410, 412, 413, 417, 422 , 426,437,438,441,443,446,450,456,459,472,478,498,505,506,507,514,515,516,521,527,528,529,531,532,534 , 535,539,541,544,547,557,562,566,571,614,618,621,623,629,640,642,658,659,662,663,664,667,700,701,702 , 704, 707, 708, 710, 711, 712, 716, 717, 719, 728, 732, 733, 734, 735, 736, 737, 738, 740, 756, 758, 759, 760, 761, 762, 775 , 778,780,781,782,801,802,803,804,805,806,827,8 34, 844, 845, 846, 850, 890, 894, 896, 911, 914, 931, 964, 965, 979, 982, 987, 998, 1000, 1007, 1009, 1013, 1016, 1020, 1023, 1027, 1040, 1050, 1052, 1053, 1055, 1058, 1060, 1061, 1063, 1064, 1066, 1069, 1073, 1083, 1086, 1088, 1089, 1091, 1096, 1099, 1100, 1102, 1109, 1115, 1118, 1119, 1120, 1122, 1123, 1124, 1125, 1126, 1128, 1129, 1133, 1140, 1151, 1160, 1172, 1178, 1184, 1207, 1251, 1260, 1266, 1286, 1298, 1334, 1340, 1358, 1364, 1382, 1387, 1391, 1417, 1441, 1446, 1448, 1456, 1459, 1461, 1481, 1509, 1522, 1531, 1537, 1543, 1549, 1553, 1554, 1566, 1575, 1593, 1599, 1603, 1616, 1620, 1625, 1631, 1643, 1649, 1658, 1706, 1710, 1757, 1770, 1789, 1811, 1840, 1877, 1879, 1891, 1898, 1911, 1920, 1924, 1937, 1946, 1952, 1958, 1981, 1985, 2010, 2034, 2038, 2040, 2042, 2051, 2060, 2066, 2072, 2081, 2106, 2136, 2147, 2151, 2176, 2198, 2199, 2200, 221 2, 2220, 2221, 2222, 2224, 2225, 2263, 2265, 2287, 2289, 2300, 2309, 2315, 2321, 2327, 2333, 2411, 2431, 2453, 2519, 2529, 2540, 2542, 2547, 2548, 2551, 2555, 2556, 2565, 2568, 2570, 2571, 2572, 2574, 2576, 2577, 2585, 2587, 2589, 2592, 2596, 2597, 2599, 2600, 2601, 2603, 2605, 2606, 2607, 2608, 2609, 2614, 2662, 2671, 2677, 2697, 2703, 2709, 2715, 2721, 2727, 2733, 2739, 2746, 2752, 2758, 2764, 2770, 2776, 2782, 2788, 2805, 2814, 2820, 2826, 2827, 2838, 2850, 2856, 2862, 2868, 2874, 2880, 2900, 2906, 2918, 2924, 2930, 2961, 2970, 2976, 2982, 2988, 2994, 3001, 3016, 3022, 3028, 3034, 3040, 3046, 3052, 3058, 3064, 3070, 3076, 3082, 3088, 3094, 3100, 3106, 3112, 3129, 3138, 3144, 3150, 3156, 3162, 3168, 3185, 3194, 3200, 3217, 3226, 3243, 3252, 3258, 3264, 3270, 3276, 3282, 3288, 3294, 3300, 3306, 3312, 3318, 3324, 3330, 3336, 3342, 3348, 3354, 33 60, 3366, 3372, 3378, 3384, 3390, 3396, 3402, 3408, 3414, 3420, 3426, 3432, 3438, 3444, 3450, 3456, 3462, 3468, 3474, 3480, 3486, 3492, 3498, 3504, 3510, 3516, 3522, 3528, 3534, 3540, 3546, 3552, 3558, 3564, 3570, 3576, 3582, 3588, 3594, 3600, 3606, 3612, 3618, 3624, 3630, 3636, 3642, 3648, 3654, 3660, 3666, 3672, 3678, 3684, 3690, 3696, 3702, 3708, 3714, 3720, 3755, 3780, 3786, 3792, 3798, 3805, 3811, 3837, 3843, 3849, 3887, 3894, 3918, 3920, 3939, 3941, 3944, 3946, 3951, 3963, 3970, 4010, 4022, 4030, 4037, 4038, 4040, 4047, 4048, 4055, 4056, 4063, 4064, 4071, 4072, 4079, 4080, 4087, 4088, 4095, 4096, 4103, 4104, 4111, 4119, 4127, 4130, 4136, 4146, 4154, 4155, 4162, 4163, 4170, 4178, 4179, 4186, 4187, 4194, 4195, 4202, 4210, 4211, 4218, 4219, 4226, 4227, 4234 or 4235 compound,

  More preferably, compound numbers 124, 125, 126, 127, 128, 130, 132, 136, 139, 140, 144, 145, 151, 163, 173, 202, 217, 249, 264, 265, 266, 267 , 269,270,271,284,287,300,304,308,309,311,334,336,339,361,362,377,385,386,387,390,391,401,437,438,459 , 472, 505, 506, 507, 515, 516, 521, 528, 529, 531, 532, 534, 539, 541, 544, 547, 571, 621, 658, 659, 662, 663, 664, 667, 700 , 701, 702, 704, 707, 708, 711, 712, 717, 719, 732, 733, 734, 735, 736, 737, 738, 740, 756, 758, 759, 760, 762, 775, 778, 780 781, 782, 801, 802, 803, 806, 827, 834, 845, 846, 850, 896, 914, 931, 964, 965, 998, 1013, 1016, 1023, 1040, 1050, 1052, 1053, 1055 , 1058, 1060, 1061, 1063, 1064, 1066, 1069, 1073, 1086, 1088, 1089, 1091, 1096, 1099, 1100, 1102, 1109, 1115, 1118, 1119, 1120, 1123, 1124, 1125, 1126 , 1129, 1133, 1140, 1151, 1160, 1172, 1178, 1184, 1207, 1260, 1266, 1286, 1298, 1334, 1340, 1358, 1364, 1382, 1387, 1391, 1417, 1441, 1446, 1448, 1481, 1522, 1531, 1537, 1543, 1549, 1566, 1575, 1593, 1599, 1616, 1620, 1625, 1631, 1643, 1649, 1658, 1710, 1770, 1789, 1811, 1840, 1879, 1891, 1911, 1937, 1946, 1958, 1981, 1985, 2010, 2034, 2038, 2040, 2042, 2051, 2060, 2066, 2072, 2081, 2106, 2136, 2151, 2176, 2200, 2212, 2220, 2225, 2265, 2289, 2300, 2309, 2327, 2333, 2411, 2519, 2529, 2540, 2542, 2556, 2565, 2568, 2576, 2577, 2587, 2597, 2599, 2600, 2601, 2605, 2609, 2614, 2662, 2671, 2677, 2697, 2703, 2709, 2715, 2721, 2727, 2733, 2739, 2746, 2752, 2758, 2764, 2770, 2776, 2782, 2788, 2805, 2814, 2820, 2826, 2850, 2856, 2862, 2868, 2874, 2880, 2900, 2906, 2918, 2924, 2930, 2961, 2970, 2976, 2982, 2988, 2994, 3022, 3028, 3034, 3040, 3046, 3052, 3058, 3064, 3070, 3076, 3082, 3088, 3094, 3100 3106, 3112, 3129, 3138, 3144, 3162, 3168, 3185, 3194, 3200, 3217, 3226, 3243, 3252, 3258, 3264, 3270, 3276, 3282, 3288, 3294, 3300, 3306, 3312, 3318, 3324, 3330, 3336, 3342, 3348, 3354, 3360, 3366, 3372, 3378, 3384, 3390, 3396, 3402, 3408, 3414, 3420, 3426, 3432, 3438, 3444, 3450, 3456, 3462, 3468, 3474, 3480, 3486, 3492, 3498, 3504, 3510, 3516, 3528, 3534, 3540, 3546, 3552, 3558, 3564, 3570, 3576, 3582, 3588, 3594, 3600, 3606, 3612, 3618, 3624, 3630, 3636, 3642, 3648, 3654, 3660, 3666, 3672, 3678, 3684, 3690, 3696, 3702, 3708, 3714, 3720, 3755, 3780, 3786, 3792, 3798, 3805, 3811, 3837, 3843, 3849, 3887, 3894, 3918, 3920, 3939, 3941, 3944, 3946, 3951, 3963, 3970, 4010, 4022, 4030, 4037, 4038, 4040, 4047, 4048, 4055, 4056, 4063, 4064, 4071, 4072, 4079, 4080, 4087, 4088, 4103, 4104, 4111, 4119, 4127, 4130, 4136, 4146, 4154, 4155, 4162, 4163, 4170 4178,4179,4186,4187,4194,4195,4202,4210,4211,4218,4219,4226,4227,4234 or 4235 number is a compound,

  Even more preferably, compound numbers 125, 126, 127, 128, 130, 132, 139, 140, 144, 145, 151, 163, 217, 249, 264, 265, 266, 284, 304, 308, 387, 390, 391, 459, 472, 506, 507, 515, 516, 531, 539, 541, 621, 658, 659, 662, 700, 701, 702, 704, 711, 717, 719, 733, 734, 735, 740, 758, 759, 762, 775, 780, 781, 801, 802, 803, 806, 827, 834, 846, 850, 931, 964, 965, 1023, 1040, 1050, 1052, 1053, 1055, 1058, 1061, 1064, 1066, 1069, 1073, 1088, 1089, 1091, 1096, 1099, 1100, 1102, 1109, 1119, 1124, 1125, 1126, 1129, 1133, 1151, 1160, 1172, 1178, 1184, 1207, 1260, 1286, 1298, 1334, 1340, 1358, 1382, 1417, 1441, 1481, 1522, 1531, 1537, 1543, 1549, 1566, 1593, 1599, 1616, 1625, 1631, 1643, 1649, 1770, 1811, 1891, 1958, 2034, 2051, 2060, 2072, 2136, 2176, 2212, 2265, 2309, 2327, 2333, 2519, 2556, 2577, 2587, 2597, 2599, 2600, 2601, 2609, 2614, 2662, 2677, 2697, 2709, 2715, 2721, 2727, 2733, 2739, 2746, 2752, 2758, 2764, 2770, 2776, 2782, 2788, 2805, 2814, 2820, 2826, 2850, 2862, 2868, 2874, 2900, 2918, 2924, 2930, 2961, 2970, 2988, 2994, 3022, 3034, 3046, 3058, 3064, 3076, 3082, 3094, 3106, 3112, 3129, 3144, 3162, 3168, 3185, 3217, 3243, 3252, 3264, 3282, 3288, 3294, 3306, 3324, 3330, 3336, 3354, 3378, 3390, 3396, 3402, 3408, 3414, 3420, 3426, 3432, 3438, 3450, 3462, 3468, 3474, 3486, 3492, 3510, 3516, 3546, 3552, 3564, 3582, 3588, 3594, 3600, 3606, 3612, 3618, 3624, 3642, 3654, 3660, 3678, 3690, 3696, 3702, 3780, 3786, 3798, 3805, 3811, 3837, 3843, 3849, 3887, 3894, 3918, 3920, 3939, 3941, 3944, 3946, 3951, 3963, 3970, 4010, 4022, 4030, 4037, 4038, 4040, 4047, 4048, 4055, 4056, 4071, 4072, 4079, 4080, 4087, 4088, 4103, 4104, 4111, 4130, 4136, 4146, 4154, 4155, 4162, 4163, 4170, 4178, 4179, 4186 4187,4194,4195,4202,4210,4211,4218,4219,4226,4227,4234 or 4235 number is a compound,

  Particularly preferably, the compound numbers 127, 128, 132, 139, 144, 217, 265, 284, 304, 391, 472, 506, 507, 515, 516, 539, 541, 621, 658, 659, 662, 704 , 711, 717, 719, 733, 735, 740, 758, 759, 762, 780, 781, 801, 802, 803, 806, 827, 846, 850, 931, 964, 965, 1023, 1040, 1052, 1058 , 1061,1088,1089,1091,1096,1099,1100,1102,1109,1124,1125,1151,1160,1172,1184,1207,1286,1298,1334,1358,1417,1441,1481,1522,1531 , 1537, 1543, 1566, 1593, 1599, 1616, 1625, 1631, 1643, 1770, 1811, 1891, 1958, 2060, 2034, 2051, 2176, 2212, 2265, 2309, 2327, 2333, 2597, 2599, 2614 , 2662, 2677, 2727, 2733, 2739, 2746, 2752, 2805, 2814, 2850, 2862, 2900, 2918, 2961, 2994, 3022, 3046, 3064, 3094, 3129, 3144, 3168, 3185, 3217, 3243 , 3264, 3288, 3324, 3402, 3408, 3426, 3432, 3450, 3462, 3546, 3552, 3564, 3582, 3588, 3594, 3600, 3606, 3612, 3618, 3624, 3642, 3654 3660, 3678, 3690, 3696, 3702, 3805, 3811, 3894, 3918, 3920, 3939, 3941, 3944, 3946, 3951, 3963, 3970, 4010, 4022, 4030, 4037, 4047, 4055, 4071, 4072, No. 4087, 4103, 4111, 4130, 4146, 4154, 4162, 4170, 4178, 4186, 4194, 4195, 4202, 4210, 4218, 4219 or 4234,

Most preferably, 6-chloro-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 128), 6-chloro-3- (2-isopropylphenoxy) -4-pyridazinol (Compound No. 132) 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol (Compound No. 139), 6-chloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] -4-pyridazinol ( Compound No. 265), 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinol (Compound No. 506), 6-chloro-3- (2-cyclopropyl- 5-methylphenoxy) -4-pyridazinol (compound number 662), 6-chloro-3- (2-fluoro-6-isopropylphenoxy) -4-pyridazinol (compound number 717), 6-chloro-3- ( 2-chloro-6-cyclopropylphenoxy) -4-pyridazinol (Compound No. 740), 6-chloro-3- (2,6-dimethylphenoxy) -4-pyridazi (Compound No. 801), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol (Compound No. 806), 6-chloro-3- [2- (2,2 -Dichlorocyclopropyl) -6-methylphenoxy] -4-pyridazinol (Compound No. 827), 6-chloro-3- (2-cyclopropyl-3,5-dimethylphenoxy) -4-pyridazinol (Compound No. 1023) ), 6-chloro-3- (6-cyclopropyl-3-fluoro-2-methylphenoxy) -4-pyridazinol (Compound No. 1052), 6-chloro-3- (6-cyclopropyl-2,3- Dimethylphenoxy) -4-pyridazinol (Compound No. 1061), 6-chloro-3- (2,3,5,6-tetramethylphenoxy) -4-pyridazinol (Compound No. 1125), 6-chloro-3- (2-Cyclopropyl-6-methylphenoxy) -4-pyridazinyl acetate (Compound No. 1151), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4- Ridazinyl propionate (compound number 1160), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-methylpropanoate (compound number 1172), 6-chloro-3- ( 2-Cyclopropyl-6-methylphenoxy) -4-pyridazinyl pivalate (Compound No. 1207), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl cyclobutanecarboxylate (Compound No. 1286) ), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl cyclohexanecarboxylate (Compound No. 1298), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy)- 4-pyridazinyl 3-methyl-2-butenoate (compound number 1358), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl benzoate (compound number 1417), 6-chloro- 3- (2-Cyclopropyl-6-methyl) Ruphenoxy) -4-pyridazinyl 2-chlorobenzoate (Compound No. 1441), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-methylbenzoate (Compound No. 1481), 6 -Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-methoxybenzoate (Compound No. 1522), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4 -Pyridazinyl 3-methylbenzoate (compound number 1531), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-bromobenzoate (compound number 1543), 6-chloro-3 -(2-Cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methylbenzoate (Compound No. 1566), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- Methoxybenzoate (Compound No. 1599), 6-chloro-3- (2- Chloropropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl phthalate (Compound No. 1625), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl isophthalate (Compound No. 1631), 6- Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl isobutyl carbonate (Compound No. 1770), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl dimethyl Carbamate (Compound No. 1891), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl ethanesulfonate (Compound No. 2034), 6-chloro-3- (2-cyclopropyl-6) -Methylphenoxy) -4-pyridazinyl 1-propanesulfonate (Compound No. 2051) No.), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-propanesulfonate (Compound No. 2060), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) ) -4-pyridazinyl benzenesulfonate (Compound No. 2176), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-chlorobenzenesulfonate (No. 2212), 6-chloro- 3- (2-Cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2265), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methoxybenzenesulfonate (Compound No. 2309), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl- 1H-pyrazolyl-5-yl 1,2-benzenedisulfonate Compound No. 2327), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazole-5 -Yl 1,3-benzenedisulfonate (Compound No. 2333), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,3-dimethylbutanoate (Compound No. 2672) No.), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-methyl acrylate (Compound No. 2677), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) ) -4-pyridazinyl ethyl succinate (compound number 2727), bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] succinate (compound number 2733), 6-chloro- 3- (2-Cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pi Zol-5-yl pentanedioate (compound number 2739), bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] pentanedioate (compound number 2746), 6 -Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-bromobenzoate (Compound No. 2805), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4 -Pyridazinyl 2-nitrobenzoate (Compound No. 2850), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-fluorobenzoate (Compound No. 2862), 6-chloro-3- ( 2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-ethylbenzoate (Compound No. 2961), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-cyanobenzoate ( Compound No. 2994), 6-chloro-3- (2-cyclopropyl-6-methyl) Phenoxy) -4-pyridazinyl 2,3-dimethylbenzoate (Compound No. 3046), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,4-dimethylbenzoate (Compound No. 3094) 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,5-dimethylbenzoate (Compound No. 3129), 6-chloro-3- (2-cyclopropyl-6-methyl Phenoxy) -4-pyridazinyl 3-fluoro-4-methylbenzoate (compound number 3185), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,5-difluorobenzoate (compound No. 3217), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,5-dimethylbenzoate (Compound No. 3243), 6-chloro-3- (2-cyclopropyl) -6-Methylphenoxy) -4-pyridazinyl 3-methyl-2-thiophenecarboxy Rate (Compound No. 3324), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl methoxy (methyl) carbamate (Compound No. 3564), 6-chloro-3- (2-cyclo Propyl-6-methylphenoxy) -4-pyridazinyl bis (2-methoxyethyl) carbamate (Compound No. 3600), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-azeti Gin carboxylate (Compound No. 3612), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-morpholine carboxylate (Compound No. 3690), 6-chloro-3- ( 2,3,5,6-Tetramethylphenoxy) -4-pyridazinyl dimethylcarbamate (Compound No. 3894), 6-chloro-3- (2-chloro-6-methylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3944), 3- (2-Bromo-6-methylphenol) Noxy) -6-chloro-4-pyridazinyl 4-morpholine carboxylate (Compound No. 3946), 6-chloro-3- (2-ethyl-6-methylphenoxy) -4-pyridazinyl 4-morpholine carboxylate (Compound No. 3951), 6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3963), 6- Chloro-3- (2,3,5,6-tetramethylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3970), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1,3-oxazolidine-3-carboxylate (Compound No. 4010), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-cyano-1-piperazinecarboxyl Rate (Compound No. 4111), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,6-dihydro-1 (2H) -pyridinecarboxylate (Compound No. 4194), 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1,3- Dihydro-2H-isoindole-2-carboxylate (Compound No. 4218) and 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,3-dihydro-4H-1,4 -Benzoxazine-4-carboxylate (Compound No. 4234).

  The 3-phenoxy-4-pyridazinol compound and its ester derivative of the present invention can be produced by the methods of Steps A to N described below.

(Process A)

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above,
L represents a leaving group, for example, a halogen atom, a C _{1 to} C ₆ alkylsulfonyloxy group or a phenylsulfonyloxy group (the phenylsulfonyloxy group is the same or different 1 to 5 halogen atoms or C ₁ the -C ₆ alkyl group may be substituted.), and obtained,
X represents a hydrogen atom or an acyl group,
Y is other protective group of hydroxyl group besides X, and may be, for example, methyl group, methoxymethyl group, methoxyethoxymethyl group or benzyl group.

  In step A, the pyridazine compound represented by the general formula (II) is reacted with the phenol compound represented by the general formula (III), then chlorinated, and further reacted with an oxygen nucleophile, thereby producing the compound of the present invention. (Ia) or a process for producing a compound in which the hydroxyl group represented by formula (VII) is protected, and further a process for producing the compound (Ib) of the present invention by removing the protecting group of compound (VII). .

(Process A-1)
In step A-1, compound (II) is reacted with compound (III) in the presence or absence of a solvent, and optionally in the presence of a base, to convert a phenoxypyridazine compound represented by the general formula (IV). It is a manufacturing process.

  The base to be used is not particularly limited as long as it usually has a pH of 8 or more. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkalis such as sodium carbonate, potassium carbonate and cesium carbonate Metal carbonates; metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; alkali metals such as sodium and potassium; triethylamine and tributylamine Aliphatic tertiary amines such as diisopropylethylamine; 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) Aliphatic cyclic tertiary amines such as: pyridine, collidine Pyridines such as 4- (N, N-dimethylamino) pyridine; organometallic bases such as n-butyllithium, s-butyllithium, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide And is preferably an alkali metal hydroxide, alkali metal carbonate, metal alkoxide, alkali metal hydride or alkali metal, more preferably potassium carbonate, potassium t-butoxide, sodium hydride or Sodium.

  The amount of the base to be used is usually 0.5 to 5 mol, preferably 1 to 3 mol, relative to 1 mol of compound (II).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons such as: amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; or a mixed solvent thereof, preferably nitriles, halogenated hydrocarbons , Ethers, aromatic hydrocarbons An amide or a sulfoxide, and more preferably dioxane, toluene, dimethylformamide or dimethyl sulfoxide.

  The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is generally 5 minutes to 48 hours, preferably 15 minutes to 12 hours.

(Process A-2)
In step A-2, compound (IV) is chlorinated with a chlorinating agent in the presence or absence of a solvent to produce a compound in which a chlorine atom is introduced at the 4-position of the pyridazine ring represented by general formula (V) It is a process to do.

  The chlorinating agent to be used is not particularly limited as long as it chlorinates an aromatic ring, and examples thereof include chlorine, chlorine-iron chloride, sulfuryl chloride, copper chloride, N-chlorosuccinimide, and phosphorus pentachloride. Preferably, it is chlorine.

  The amount of the chlorinating agent to be used is usually 0.5 to 10 mol, preferably 1 to 2 mol, relative to 1 mol of compound (IV).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. Examples thereof include phosphorus oxychloride; water; alcohols such as methanol, ethanol and t-butanol; Halogenated hydrocarbons such as methylene, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene; amides such as dimethylformamide and dimethylacetamide; dimethyl sulfoxide Such sulfoxides; aliphatic hydrocarbons such as hexane, cyclohexane, heptane; or a mixed solvent thereof, preferably phosphorus oxychloride, water, halogenated hydrocarbons or ethers; More preferred is phosphorus oxychloride.

The reaction temperature varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 50 ° C.
The reaction time mainly varies depending on the reaction temperature, the raw material compound, the reaction reagent and the kind of the solvent used, but is usually 5 minutes to 24 hours, and preferably 15 minutes to 6 hours.

(Process A-3)
In step A-3, compound (V) is reacted with an oxygen nucleophile represented by general formula (VI) in the presence or absence of a solvent, and optionally in the presence of a base, to give compound (Ia) of the present invention. Or it is the process of manufacturing the compound by which the hydroxyl group represented by general formula (VII) was protected.

  The base to be used is not particularly limited as long as it is a base exhibiting a pH of 8 or higher. Examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; sodium carbonate, potassium carbonate and cesium carbonate. Alkali metal carbonates; metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide; alkali metal salts of organic acids such as sodium acetate, potassium acetate, sodium formate, potassium formate; sodium hydride, hydrogenation Alkali metal hydrides such as potassium; alkali metals such as sodium and potassium; aliphatic tertiary amines such as triethylamine, tributylamine and diisopropylethylamine; 1,4-diazabicyclo [2.2.2] octane (DABCO) ), 1,8-diazabicyclo 5.4.0] Aliphatic cyclic tertiary amines such as undec-7-ene (DBU); pyridines such as pyridine, collidine, 4- (N, N-dimethylamino) pyridine; butyllithium, s -Organic bases such as butyl lithium, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, preferably alkali metal hydroxides, alkali metal carbonates, metal alkoxides, Alkali metal salt of organic acid, alkali metal hydride or alkali metal, more preferably sodium hydroxide, potassium hydroxide, potassium carbonate, potassium t-butoxide, sodium acetate, sodium formate, sodium hydride or sodium is there.

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl Ketones such as ketones; Nitriles such as acetonitrile; Esters such as ethyl acetate; Halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Toluene Aromatic hydrocarbons such as: amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; or a mixed solvent thereof, preferably water, alcohols, nitriles, Ethers, amides or sulfoxides By weight, more preferably, water, methanol, acetonitrile, tetrahydrofuran, dioxane, dimethylformamide or dimethyl sulfoxide.

  The reaction temperature varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 100 ° C.

The reaction time mainly varies depending on the reaction temperature, the raw material compound, the reaction reagent and the kind of the solvent used, but is usually 5 minutes to 24 hours, and preferably 15 minutes to 6 hours.
In this step, compound (VI) can also be used in this step after previously reacting with a base to form a salt.

(Process A-4)
Step A-4 is a step for producing the compound (Ib) of the present invention by removing the protecting group for the hydroxyl group of the compound (VII).

  The protecting group used in this step is not particularly limited as long as it can be selectively removed from compound (VII) to give compound (Ib). For example, methyl, methoxymethyl, benzyloxymethyl, methoxy Ethoxymethyl group, 2- (trimethylsilyl) ethoxymethyl group, methylthiomethyl group, phenylthiomethyl group, 2,2-dichloro-1,1-difluoroethyl group, tetrahydropyranyl group, phenacyl group, p-bromophenacyl group, cyclo Propylmethyl group, allyl group, isopropyl group, cyclohexyl group, t-butyl group, benzyl group, 2,6-dimethylbenzyl group, 4-methoxybenzyl group, 2-nitrobenzyl group, 2,6-dichlorobenzyl group, 4 -(Dimethylaminocarbonyl) benzyl group, 9-anthrylmethyl group, 4-pico Group, heptafluoro-p-tolyl group or tetrafluoro-4-pyridyl group, preferably methyl group, methoxymethyl group, methoxyethoxymethyl group, methylthiomethyl group, tetrahydropyranyl group, phenacyl group, It is an allyl group or a benzyl group, and more preferably a methyl group.

  The method for removing the protecting group used in this step is not particularly limited as long as it can selectively remove the protecting group of the hydroxyl group, and a known method (for example, Protective Groups In -Organic Synthesis (Protective Groups in Organic Synthesis), 13th edition, Theodora W. Greene and Peter GM Wuts, the method described in JOHN WILEY & SONS, INC) or according to these methods. For example, when the protecting group is a methyl group, the removal of the methyl group can be accomplished, for example, by the potassium or sodium salt of 2-hydroxypyridine in dimethyl sulfoxide, the sodium salt of ethanethiol in dimethylformamide, or 3 in methylene chloride. It can be performed by the action of boron bromide. For example, when the protecting group is a methoxymethyl group, the removal of the methoxymethyl group can be performed, for example, by the action of trifluoroacetic acid. For example, when the protecting group is a methoxyethoxymethyl group, the removal of the methoxyethoxymethyl group can be performed by, for example, acting trifluoroacetic acid. For example, when the protecting group is a benzyl group, the benzyl group can be removed by catalytic hydrogenation.

上記式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｌ、Ｘ及びＹは、前記と同意義を示す。 (Process B)

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , L, X and Y are as defined above.

  In the step B, the pyridazine compound represented by the general formula (II) is oxidized, reacted with the phenol compound represented by the general formula (III), then chlorinated, and further reacted with an oxygen nucleophile. A step of producing a compound (Ia) or a compound in which the hydroxyl group represented by the general formula (VII) is protected, and further a step of producing the compound (Ib) of the present invention by removing the protecting group of the compound (VII). It is.

(Process B-1)
Step B-1 is a step of producing pyridazine N-oxide represented by the general formula (VIII) by oxidizing compound (II) with an oxidizing agent in the presence or absence of a solvent.

  The oxidizing agent used is not particularly limited as long as it converts amines to N-oxide. For example, m-chloroperbenzoic acid (mcpba), peracetic acid, pertrifluoroacetic acid, trifluoroacetic anhydride- Hydrogen peroxide, peroxydichloromaleic acid, dichloromaleic acid-hydrogen peroxide, peroxymaleic acid, maleic acid-hydrogen peroxide, t-butyl hydroperoxide, t-butyl hydroperoxide-vanadium oxyacetylacetonate, t-butyl hydroperoxide-peroxide such as molybdenum chloride, hydrogen peroxide; ozone; or oxygen, preferably m-chloroperbenzoic acid (mcpba), trifluoroacetic anhydride-hydrogen peroxide Or dichloromaleic acid-hydrogen peroxide.

  The amount of the oxidizing agent used in the reaction is usually 0.5 to 100 mol, preferably 1 to 2 mol, relative to 1 mol of compound (II).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; or a mixed solvent thereof, preferably halogenated hydrocarbons, more preferably Is methylene chloride.

  While the reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, it is generally -90 ° C to 200 ° C, preferably 0 ° C to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is generally 5 minutes to 24 hours, preferably 15 minutes to 6 hours.

  By this process, isomers in which other nitrogen atoms are oxidized may be by-produced.However, by purifying after completion of this process or by performing subsequent processes while mixing, purifying after completion of the process, The target pyridazine N-oxide can be obtained.

(Process B-2)
In step B-2, compound (VIII) is reacted with compound (III) in the presence or absence of a solvent, and optionally in the presence of a base, to produce a phenoxypyridazine compound represented by general formula (IX). It is a process to do.
This step can be performed according to step A-1.

(Process B-3)
Step B-3 is a step for producing compound (V) by reacting compound (IX) with phosphorus oxychloride in the presence or absence of a solvent.

  The amount of phosphorus oxychloride used in this step is usually 0.5 to 100 mol, preferably 1 to 5 mol, relative to 1 mol of compound (IX).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, ketones such as acetone and methyl isobutyl ketone; nitriles such as acetonitrile; ethyl acetate Esters such as; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene; dimethylformamide and dimethylacetamide Amides; Sulfoxides such as dimethyl sulfoxide; Aliphatic hydrocarbons such as hexane and cyclohexane; or a mixed solvent thereof, preferably halogenated hydrocarbons, and more preferably Methylene chloride or chloroform.

  While the reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, it is generally -90 ° C to 200 ° C, preferably 0 ° C to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is generally 5 minutes to 72 hours, and preferably 30 minutes to 24 hours.

(Process B-4)
In step B-4, the compound (V) is reacted with an oxygen nucleophile represented by the general formula (VI) in the presence or absence of a solvent, and optionally in the presence of a base, to give the compound of the present invention (Ia Or a hydroxyl group-protected compound represented by the general formula (VII).
This step is the same as step A-3.

(Process B-5)
Step B-5 is a step for producing the compound (Ib) of the present invention by removing the hydroxyl protecting group of the compound (VII).
This step is the same as step A-4.

(Process C)

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above.
In step C, the compound (IV) is oxidized, chlorinated, and then reacted with an oxygen nucleophile to produce a compound in which the hydroxyl group represented by the present compound (Ia) or general formula (VII) is protected. Furthermore, it is a step for producing the compound (Ib) of the present invention by removing the protecting group of the compound (VII).

(Process C-1)
Step C-1 is a step of producing pyridazine N-oxide represented by general formula (IX) by oxidizing compound (IV) with an oxidizing agent in the presence or absence of a solvent.
This process can be performed according to process B-1.

(Process C-2)
Step C-2 is a step of producing compound (V) by reacting compound (IX) with phosphorus oxychloride in the presence or absence of a solvent.
This step is the same as step B-3.

(Process C-3)
In Step C-3, the compound (V) is reacted with an oxygen nucleophile represented by the general formula (VI) in the presence or absence of a solvent, and optionally in the presence of a base, to give a compound of the present invention ( This is a process for producing a compound in which the hydroxyl group represented by Ia) or general formula (VII) is protected.
This step is the same as step A-3 or B-4.

(Process C-4)
Step C-4 is a step for producing the compound (Ib) of the present invention by removing the hydroxyl-protecting group of the compound (VII).
This step is the same as step A-4 or B-5.

(Process D)

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , L, X and Y are as defined above.
In the step D, the compound represented by the present invention (Ia) or the general formula (I) is reacted with a phenol represented by the general formula (III) by reacting the pyridazine compound represented by the general formula (X) with the oxygen functional group previously substituted. It is a step of producing a compound in which the hydroxyl group represented by VII) is protected, and further, a step of producing the compound (Ib) of the present invention by removing the protecting group of compound (VII).

(Process D-1)
In step D-1, compound (X) is reacted with compound (III) in the presence or absence of a solvent, optionally in the presence of a base, to give compound (Ia) or general formula (VII) of the present invention. This is a process for producing a compound in which the hydroxyl group represented is protected.
This process can be performed according to process A-1 or B-2.

(Process D-2)
Step D-2 is a step of producing the compound (Ib) of the present invention by removing the protecting group for the hydroxyl group of the compound (VII).
This step is the same as step A-4, B-5 or C-4.

(Process E)

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , L, X and Y are as defined above,
m ′ and n ′ represent 0 or 1, provided that m ′ and n ′ are not 0 at the same time.
In step E, the pyridazine compound previously substituted with an oxygen functional group represented by the general formula (X) is oxidized, and then reacted with the phenol represented by the general formula (III) to thereby react the present compound (Ic) or This is a step of producing a compound in which the hydroxyl group represented by the general formula (XII) is protected, and further, a step of producing the compound (Id) of the present invention by removing the protecting group of the compound (XII).

(Process E-1)
Step E-1 is a step of producing pyridazine N-oxide represented by general formula (XI) by oxidizing compound (X) with an oxidizing agent in the presence or absence of a solvent.
This step can be performed according to Step B-1 or C-1 when m ′ = 0 or n ′ = 0, and when m ′ = n ′ = 1, the amount of oxidizing agent is excessive. Or by using more severe conditions such as oxidizing with a more reactive oxidizing agent.

(Process E-2)
In step E-2, compound (XI) is reacted with compound (III) in the presence or absence of a solvent, optionally in the presence of a base, to give compound (Ic) or general formula (XII) of the present invention. This is a process for producing a compound in which the hydroxyl group represented is protected.
This process can be performed according to process A-1, B-2, or D-1.

(Process E-3)
Step E-3 is a step of producing the compound (Id) of the present invention by removing the protecting group for the hydroxyl group of the compound (XII).
This step is the same as step A-4, B-5, C-4 or D-2.

(Process F)

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X, Y, m ′ and n ′ are as defined above.
In Step F, the hydroxyl group represented by the compound (Ic) or the general formula (XII) is protected by oxidizing the compound (Ia) or the compound represented by the general formula (VII) in which the hydroxyl group is protected. And a step of producing the compound (Id) of the present invention by removing the protecting group of the compound (XII).

(Process F-1)
In Step F-1, the compound (Ia) or the compound (VII) of the present invention is oxidized with an oxidizing agent in the presence or absence of a solvent, and is represented by the compound (Ic) of the present invention or the general formula (XII). This is a production process for producing a compound in which a hydroxyl group is protected.
This step can be performed according to step E-1.

(Process F-2)
Step F-2 is a step of producing the compound (Id) of the present invention by removing the protecting group for the hydroxyl group of the compound (XII).
This step is the same as Step A-4, B-5, C-4, D-2 or E-3.

(Process G)

In the above formula, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above,
R ^2a has the same meaning as R ² except for a hydrogen atom.
In step G, the 5-position of the pyridazine ring of the compound (Ie) or the compound represented by the general formula (XIII) in which the hydroxyl group is protected is metalated, and then reacted with an electrophile to produce the compound ( If) is a step for producing a compound in which the hydroxyl group represented by formula (XIV) is protected, and further is a step for producing the compound (Ig) of the present invention by removing the protecting group of compound (XIV). .

(Process G-1)
In Step G-1, the compound of the present invention (Ie) or the compound represented by formula (XIII) in which the hydroxyl group is protected is reacted with a metallizing agent in the presence or absence of a solvent, This is a step of producing a compound in which the hydroxyl group represented by the present compound (If) or general formula (XIV) is protected by reacting.

  The metallizing agent to be used is not particularly limited as long as it can metallate an aromatic ring. For example, an organolithium compound such as methyl lithium, butyl lithium, sec-butyl lithium, t-butyl lithium, or phenyl lithium; Organomagnesium compounds such as magnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, phenylmagnesium bromide; Organometallic amides such as lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide; sodium methoxide, sodium Metal alkoxides such as ethoxide and potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; lithium, sodium and potassium Alkali metals such as beam; obtained an alkali earth metal such as magnesium, preferably an organolithium compound, more preferably a butyl lithium.

  The amount of the metallizing agent used in the reaction is usually 0.5 to 10 mol, preferably 1 to 2 mol, relative to 1 mol of compound (Ie) or compound (XIII).

  The electrophile used in the reaction is not particularly limited as long as it reacts with an organometallic compound. For example, silylating agents such as trimethylsilyl chloride, triethylsilyl chloride, t-butyldimethylsilyl chloride, trimethylsilyl trifluoromethanesulfonate, etc. Acylating agents such as acetyl chloride, benzoyl chloride, ethyl chlorocarbonate, methyl chlorocarbonate, N, N-dimethylformamide, methyl formate; carbonyl compounds such as acetaldehyde, benzaldehyde, acetone, cyclohexanone; methyl iodide, bromide Alkylating agents such as methyl and benzyl bromide; fluorine, chlorine, bromine, iodine, N-fluorobenzenesulfonamide, 1-fluoro-2,6-dichloropyridinium triflate, N-chlorosuccinimide (NCS) ), A halogenating agent such as N-bromosuccinimide (NBS); or carbon dioxide, preferably a silylating agent, acylating agent, alkylating agent or halogenating agent, more preferably Is trimethylsilyl chloride, benzoyl chloride, ethyl chlorocarbonate or methyl iodide.

  The amount of the electrophile used for the reaction is usually 0.5 to 10 mol, preferably 1 to 3 mol, relative to 1 mol of compound (Ie) or compound (XIII).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting materials to some extent. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane; diethyl ether, tetrahydrofuran, dioxane Ethers such as toluene; aromatic hydrocarbons such as toluene; aliphatic hydrocarbons such as hexane and cyclohexane; or a mixed solvent thereof, preferably ethers, more preferably Is tetrahydrofuran.

  While the reaction temperature varies depending on the raw material compound, the reaction reagent, and the type of solvent used, it is generally −90 ° C. to 100 ° C., and preferably −70 ° C. to 30 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is generally 5 minutes to 24 hours, preferably 30 minutes to 12 hours.

(Process G-2)
Step G-2 is a step of producing the compound (Ig) of the present invention by removing the protecting group for the hydroxyl group of the compound (XIV).
This step is the same as Step A-4, B-5, C-4, D-2, E-3 or F-2.

(Process H)

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above,
Xa has the same meaning as X except for a hydrogen atom.
Step H is a step of converting the ester derivative of the present invention represented by the general formula (Ih) into the hydroxy form of the present invention represented by the general formula (Ib).

(Process H-1)
Step H-1 is a step of producing the compound (Ib) of the present invention by reacting the compound (Ih) of the present invention with a nucleophile in the presence or absence of a solvent.
The nucleophile used is not particularly limited as long as it can nucleophilically attack an ester derivative and cleave the ester bond into an acid moiety and an alcohol moiety. For example, water; lithium hydroxide, sodium hydroxide Alkali metal hydroxides such as potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; sodium methoxide, sodium ethoxide, 2-hydroxypyridine potassium salt, 2- Metal alkoxides such as hydroxypyridine sodium salt; alkali metal salts of organic acids such as sodium acetate, potassium acetate, sodium formate and potassium formate; fluorides such as tetrabutylammonium fluoride and potassium fluoride; lithium chloride, chloride Chlorides such as sodium; lithium bromide, sodium bromide Bromides; iodides such as sodium iodide and potassium iodide; or metal salts of sulfur compounds such as methanethiol sodium salt and ethanethiol sodium salt, preferably water, alkali metal hydroxides , Metal alkoxides or alkali metal salts of organic acids, more preferably water, sodium hydroxide, potassium hydroxide or sodium acetate.

  The amount of the nucleophile to be used is usually 1 to 10 mol, preferably 1 to 5 mol, relative to 1 mol of compound (Ih).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide; or a mixed solvent thereof, preferably water, alcohols, nitriles, ethers Amides or sulfoxides , More preferably, water, methanol, ethanol, tetrahydrofuran, dioxane, dimethylformamide or dimethyl sulfoxide.

  While the reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, it is generally -90 ° C to 200 ° C, preferably 0 ° C to 100 ° C.

While the reaction time mainly varies depending on the reaction temperature, the raw material compound, the reaction reagent, and the type of solvent used, it is generally 5 minutes to 48 hours, and preferably 15 minutes to 12 hours.
In addition, this process can also use a well-known method as normal deprotection of a hydroxyl group.

(Process I)

In the above ^{formulas, R 1, R 2, R} 3, R 4, R 5, R 6, R 7 and Xa are as defined above.
Step I is a step of converting the hydroxy compound of the present invention represented by the general formula (Ib) into the ester derivative of the present invention represented by the general formula (Ih).

(Step I-1)
Step I-1 is a step of producing the present compound (Ih) by reacting the present compound (Ib) with an esterifying agent in the presence or absence of a solvent.
The esterifying agent used is not particularly limited as long as it esterifies a hydroxyl group. For example, acetyl chloride, acetyl bromide, acetic anhydride, trifluoroacetic anhydride, benzoyl chloride, methyl chlorocarbonate, ethyl chlorocarbonate, Acylating agents such as N, N-dimethylcarbamoyl chloride, methyl chlorothioformate; or methanesulfonyl chloride, propanesulfonyl chloride, p-toluenesulfonyl chloride, trifluoromethanesulfonic anhydride, N, N-dimethylsulfamoyl A sulfonylating agent such as chloride, preferably acetyl chloride, acetic anhydride, trifluoroacetic anhydride, benzoyl chloride, methyl chlorocarbonate, ethyl chlorocarbonate, methanesulfonyl chloride, propanesulfonyl chloride, p-toluenes A Honirukuroraido or triflic anhydride, more preferably benzoyl chloride, p- toluenesulfonyl chloride or trifluoromethanesulfonic anhydride.

  The amount of the esterifying agent used in the reaction is usually 0.5 to 10 mol, preferably 1 to 3 mol, relative to 1 mol of compound (Ib).

The reaction is preferably carried out in the presence of a base.
The base used is not particularly limited as long as it usually shows a pH of 8 or more. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkalis such as sodium carbonate, potassium carbonate and cesium carbonate Metal carbonates; metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aliphatic triions such as triethylamine, tributylamine and diisopropylethylamine Tertiary amines; aliphatic cyclic tertiary amines such as 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) Of pyridine, collidine, 4- (N, N-dimethylamino) pyridine Or pyridines; or organometallic bases such as n-butyllithium, sec-butyllithium, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, and preferably aliphatic Tertiary amines, aliphatic cyclic tertiary amines or pyridines, more preferably triethylamine, 1,4-diazabicyclo [2.2.2] octane (DABCO), pyridine or 4- (N, N -Dimethylamino) pyridine.

  The amount of the base used in the reaction is usually 0.5 to 20 mol, preferably 1 to 5 mol, relative to 1 mol of compound (Ib).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, ketones such as acetone and methyl isobutyl ketone; nitriles such as acetonitrile; ethyl acetate Esters such as; Halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons such as toluene; Aliphatics such as hexane and cyclohexane Hydrocarbons; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; or a mixed solvent thereof, preferably nitriles, halogenated hydrocarbons or ethers, More preferably, acetonitrile or salt It is methylene.

  The reaction temperature mainly varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 100 ° C.

While the reaction time mainly varies depending on the reaction temperature, the raw material compound, the reaction reagent, and the type of solvent used, it is generally 5 minutes to 48 hours, and preferably 15 minutes to 12 hours.
In addition, this process can also use a well-known method as protection of a normal hydroxyl group.

(Process J)

In the above formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above,
R ¹ a has the same meaning as R ¹ except for a hydrogen atom.
In Step J, the 6-chloropyridazine derivative represented by the general formula (IVa) is reduced, oxidized, metalated, and reacted with an electrophile to introduce a substituent at the 6-position of the pyridazine ring. Furthermore, it is a step of producing a compound in which the hydroxyl group represented by the present compound (Ii) or the general formula (XVIII) is protected by chlorination and a substitution reaction with an oxygen nucleophile. In this step, the protecting group is removed to produce the compound (Ij) of the present invention.

(Process J-1)
In Step J-1, compound (IVa) in which R1 is a chlorine atom in compound (IV) is reacted with a reducing agent in the presence or absence of a solvent, whereby R1 is a hydrogen atom in compound (IV). This is a step for producing a certain compound (IVb).

  The reducing agent used in the reaction is not particularly limited as long as it can reduce the chlorine atom on the aromatic ring. For example, it can be a reducing agent used in a normal hydrogenation reaction, preferably a hydrogen-palladium catalyst. It is.

  In the case of hydrogenation reaction in this step, the hydrogen pressure is usually 1 atm to 100 atm, and preferably 1 to 3 atm.

  The amount of palladium used in the hydrogenation reaction is usually 0.001 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of compound (IVa).

The hydrogenation reaction is preferably performed in the presence of a base.
The base used is not particularly limited as long as it usually shows a pH of 8 or more. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkalis such as sodium carbonate, potassium carbonate and cesium carbonate Metal carbonates; metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aqueous ammonia; triethylamine, tri-n-butylamine, diisopropylethylamine Fatty tertiary amines such as: 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) Group cyclic tertiary amines; pyridine, collidine, 4- (N, N-dimethyl) Pyridine) such as mino) pyridine; or organometallic bases such as butyllithium, sec-butyllithium, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, and the like. Is ammonia water or aliphatic tertiary amines, more preferably ammonia water or triethylamine.

  The amount of the base used in the reaction is usually 0.1 to 100 mol, preferably 1 to 3 mol, relative to 1 mol of compound (IVa).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; aliphatic hydrocarbons such as hexane and cyclohexane; or a mixed solvent thereof, preferably Is alcohol, yo Preferably methanol or ethanol.

  The reaction temperature mainly varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is usually 5 minutes to 48 hours, preferably 15 minutes to 12 hours.

(Process J-2)
Step J-2 is a step of producing pyridazine N-oxide represented by the general formula (XV) by oxidizing compound (IVb) with an oxidizing agent in the presence or absence of a solvent.
This process can be performed according to process B-1 or C-1.

(Process J-3)
Step J-3 is a step of producing the compound (XVI) of the present invention by reacting the compound (XV) with a metallating agent in the presence or absence of a solvent and then reacting with an electrophile. is there.
This process can be performed according to the process G-1.

(Process J-4)
Step J-4 is a step of producing compound (XVII) by reacting compound (XVI) with phosphorus oxychloride in the presence or absence of a solvent.
This step is the same as step B-3 or C-2.

(Process J-5)
In step J-5, compound (XVII) is reacted with an oxygen nucleophile represented by general formula (VI) in the presence or absence of a solvent, and optionally in the presence of a base, to give a compound of the present invention ( This is a step of producing a compound in which the hydroxyl group represented by Ii) or general formula (XVIII) is protected.
This step is the same as step A-3, B-4 or C-3.

(Process J-6)
Step J-6 is a step for producing the compound (Ij) of the present invention by removing the protecting group for the hydroxyl group of the compound (XVIII).
This step is the same as Step A-4, B-5, C-4, D-2, E-3, F-2 or G-2.

(Process K)

In the above formula, R ^1a , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above.
In step K, the 6-chloropyridazine derivative of the present invention represented by the general formula (Ik) or the 6-chloropyridazine derivative in which the hydroxyl group represented by the general formula (XIX) is protected is oxidized, dechlorinated, It is a step of producing a compound in which the hydroxyl group represented by the compound (Ii) or the general formula (XVIII) of the present invention is protected by introducing an electrophile after metalation and finally reducing the compound. This is a step for producing the compound (Ij) of the present invention by removing the protecting group of XVIII).

(Process K-1)
In step K-1, compound (Ik) or compound (XIX) is oxidized with an oxidizing agent in the presence or absence of a solvent, and the N-oxypyridazine compound represented by general formula (Il) or (XX) Is a process of manufacturing.
This process can be performed according to process B-1, C-1, or J-2.

(Process K-2)
In Step K-2, the pyridazine ring 6-position is reacted with a reducing agent in the presence or absence of a solvent in the N-oxide compound (Il) or (XX) in which the pyridazine ring 6-position is a chlorine atom. This is a step for producing an N-oxide compound (Im) or (XXI) which is a hydrogen atom.
This step can be performed according to step J-1.

(Process K-3)
In Step K-3, the compound (Im) or (XXI) is reacted with a metallizing agent in the presence or absence of a solvent and then reacted with an electrophile, whereby the compound (In) of the present invention or This is a step of producing a compound in which the hydroxyl group represented by formula (XXII) is protected.
This process can be performed according to the process G-1 or J-3.

(Process K-4)
Step K-4 comprises reacting an N-oxide derivative represented by the general formula (In) or (XXII) with phosphorus trichloride or phosphorus tribromide in the presence or absence of a solvent. This is a step for producing a compound in which the hydroxyl group represented by compound (Ii) or general formula (XVIII) is protected.

  The amount of phosphorus trichloride or phosphorus tribromide used is usually 0.5 to 100 mol, preferably 1 to 20 mol, per 1 mol of compound (In) or (XXII).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting materials to some extent. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane; diethyl ether, tetrahydrofuran, dioxane Ethers such as toluene; aromatic hydrocarbons such as toluene; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; aliphatic hydrocarbons such as hexane, cyclohexane and heptane; or These may be mixed solvents, preferably halogenated hydrocarbons, and more preferably chloroform.

  The reaction temperature mainly varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is generally 5 minutes to 24 hours, preferably 15 minutes to 6 hours.

(Process K-5)
Step K-5 is a step for producing the compound (Ij) of the present invention by removing the protecting group for the hydroxyl group of the compound (XVIII).
This step is the same as step A-4, B-5, C-4, D-2, E-3, F-2, G-2 or J-6.

(Process L)

In the above formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above,
R ¹ b has the same meaning as R ¹ except for a hydrogen atom and a halogen atom.
In step L, a 6-chloropyridazine derivative represented by the general formula (Ik) or (XIX) is reacted with an organometallic compound, whereby the hydroxyl group represented by the present compound (Io) or the general formula (XXIII). Is a step of producing a protected compound, and further is a step of producing the compound (Ip) of the present invention by removing the protecting group of compound (XXIII).

(Process L-1)
In step L-1, compound (Ik) or (XIX) is reacted with an organometallic compound in the presence or absence of a solvent and in the presence of a metal catalyst to give a compound of the present invention (Io) or general formula ( XXIII) is a step of producing a compound in which the hydroxyl group is protected.

The organometallic compound used is not particularly limited as long as it is used for the cross-coupling reaction in which the R ¹ b group is substituted with a chlorine atom. For example, methylmagnesium chloride, ethylmagnesium bromide, phenylmagnesium chloride, etc. Organomagnesium compounds; Organozinc compounds such as phenylzinc chloride; Organoaluminum compounds such as (diisobutyl) (1-hexenyl) aluminum; (Vinyl) trimethyltin, (1-ethoxyvinyl) tributyltin, (2-furyl) tributyltin Organotin compounds such as (2-thienyl) tributyltin; organoboron compounds such as phenylboronic acid; organosilicate compounds such as trimethylvinylsilicon-tris (dimethylamino) sulfonium difluorotrimethylsilicate It can be potassium cyanide, and acetylene compounds such as trimethylsilylacetylene and phenylacetylene can also be used in the reaction in the presence of amines such as triethylamine in the same manner as the above organometallic compounds, and are preferably organotin compounds or organoboron compounds. .

  The amount of the organometallic compound used in the reaction is usually 0.5 to 10 mol, preferably 1 to 2 mol, relative to 1 mol of compound (Ik) or (XIX).

  The metal catalyst used in this step is not particularly limited as long as it is used for the cross coupling reaction, and is, for example, a nickel catalyst or a palladium catalyst.

  The amount of the metal catalyst used in the reaction is usually 0.0001 to 10 mol, preferably 0.01 to 0.5 mol, relative to 1 mol of compound (Ik) or (XIX).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; aliphatic hydrocarbons such as hexane and cyclohexane; organic amines such as triethylamine and pyridine; or these Mixing Agents and are obtained, preferably ethers, aromatic hydrocarbons or amides, more preferably ether, tetrahydrofuran, toluene or dimethylformamide.

  The reaction temperature mainly varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 130 ° C.

  While the reaction time mainly varies depending on the raw material compound, the reaction reagent, and the type of solvent used, it is generally 5 minutes to 48 hours, and preferably 15 minutes to 24 hours.

(Process L-2)
Step L-2 is a step of producing the compound (Ip) of the present invention by removing the protecting group for the hydroxyl group of the compound (XXIII).
This step is the same as step A-4, B-5, C-4, D-2, E-3, F-2, G-2, J-6 or K-5.

(Process M)

In the above formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above.
Step M is represented by the present compound (Iq) or general formula (XXIV) by cyanating a 6-position unsubstituted pyridazine N-oxide derivative represented by general formula (Im) or (XXI). It is a step of producing a compound in which a hydroxyl group is protected, and further, a step of producing the compound (Ir) of the present invention by removing the protecting group of the compound (XXIV).

(Process M-1)
Step M-1 is represented by the present compound (Iq) or general formula (XXIV) by reacting compound (Im) or (XXI) with a cyanating agent in the presence or absence of a solvent. This is a process for producing a compound in which a hydroxyl group is protected.
This step can be performed according to a known Reissert-Henze reaction (JOC, 48, 1983, 1375 to 1377; Heterocycles, 15, 1981, 981 to 984; Synthesis, 1983, 316 to 319, etc.).

(Process M-2)
Step M-2 is a step for producing the compound (Ir) of the present invention by removing the protecting group for the hydroxyl group of the compound (XXIV).
This step is the same as steps A-4, B-5, C-4, D-2, E-3, F-2, G-2, J-6, K-5 or L-2.

(Process N)

In the above formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above.
In Step N, the 6-chloropyridazine derivative represented by the general formula (Ik) or (XIX) is dechlorinated to protect the hydroxyl group represented by the present compound (Is) or the general formula (XXV). This is a step for producing the present compound (It) by removing the protecting group of the compound (XXV).

(Process N-1)
In Step N-1, the compound (Ik) or (XIX) is reacted with a reducing agent in the presence or absence of a solvent to give a hydroxyl group represented by the present compound (Is) or the general formula (XXV). Is a process for producing a protected compound.
This process can be performed according to process J-1 or K-2.

(Process N-2)
Step N-2 is a step of producing the compound (It) of the present invention by removing the protecting group for the hydroxyl group of the compound (XXV).
This step is the same as step A-4, B-5, C-4, D-2, E-3, F-2, G-2, J-6, K-5, L-2 or M-2. It is.

(Process O)

In the above formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above.
In step O, the 3,4-dichloropyridazine derivative represented by the general formula (XXVI) is reacted with the catechol derivative represented by the general formula (XXVII), followed by hydrolysis to give the compound (Iu) of the present invention. It is a manufacturing process.

(Step O-1)
In step O-1, compound (XXVI) is reacted with compound (XXVII) in the presence or absence of a solvent, and optionally in the presence of a base, to produce a condensed compound represented by general formula (XXVIII). It is a process.

  This step can be carried out according to step A-1, B-2, D-1 or E-2, and the amount of the base used is usually 1 to 10 mol per 1 mol of compound (XXVI). Yes, preferably 2 to 6 mol.

(Process O-2)
Step O-2 is a step of producing the compound (Iu) of the present invention by hydrolyzing the compound (XXVIII).

  This step can be performed according to the case where Y is a hydrogen atom in Step A-3, B-4 or C-3, and the reaction temperature is preferably 80 ° C to 100 ° C.

(Process P)

In the above formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X and Y are as defined above.
In Step P, the 6-position of the 4,6-dichloropyridazine derivative represented by the general formula (Va) is selectively hydrolyzed to obtain a compound (XXIX), and then brominated at 4 and 6 positions with phosphorus oxybromide. Then, a process for producing a compound in which the hydroxyl group represented by the compound (Iv) or the general formula (XXXI) of the present invention is protected by selectively reacting an oxygen nucleophile at the 4-position, XXXI) is a step for producing the compound (Iw) of the present invention by removing the protecting group.

(Process P-1)
In Step P-1, the compound (Va) is hydrolyzed in the presence or absence of a solvent in the presence of an acid to selectively convert the 6-position chlorine atom to a hydroxyl group, and is represented by the general formula (XXIX). This is a process for producing a compound to be produced.

  The acid used is not particularly limited as long as it is an acid having a pH of 6 or less. For example, organic acids such as formic acid, acetic acid, succinic acid, propionic acid, succinic acid, maleic acid, fumaric acid, benzoic acid; hydrogen fluoride Mineral acids such as acids, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid; or Lewis acids such as aluminum chloride, iron chloride, titanium chloride, boron trifluoride, etc. Preferred are organic acids, and more preferred are formic acid or acetic acid.

This step is preferably performed in the presence of an acid metal salt.
The metal salt of the acid used is, for example, an alkali metal salt of an organic acid such as sodium formate, potassium formate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, sodium benzoate; magnesium formate, calcium formate, magnesium acetate, Alkaline earth metal salts of organic acids such as calcium acetate and magnesium benzoate; Alkali metal salts or alkaline earth metal salts of carbonic acid such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate; Sodium fluoride, potassium fluoride, sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate, magnesium sulfate, sodium phosphate, Binatto hydrogen phosphate Or alkali metal salts of mineral acids such as sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, etc., preferably alkali metals of organic acids A salt, more preferably sodium formate, potassium formate, sodium acetate or potassium acetate.

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide; organic acids such as formic acid, acetic acid and propionic acid; or a mixed solvent thereof, preferably , Water, nitriles, ethers, amino S, a sulfoxide or an organic acid, more preferably water, acetonitrile, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, formic acid or acetic acid.

  While the reaction temperature varies depending on the raw material compound, the reaction reagent, and the type of solvent used, it is generally −90 ° C. to 200 ° C., and preferably 0 ° C. to 150 ° C.

  The reaction time mainly varies depending on the reaction temperature, the raw material compound, the reaction reagent, and the type of solvent used, but is usually 5 minutes to 24 hours, and preferably 15 minutes to 12 hours.

(Process P-2)
Step P-2 is a step of producing compound (XXX) by reacting compound (XXIX) with phosphorus oxybromide in the presence or absence of a solvent.

  The amount of phosphorus oxybromide used in this step is usually 0.5 to 100 mol, preferably 1 to 10 mol, relative to 1 mol of compound (XXIX).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, ketones such as acetone and methyl isobutyl ketone; nitriles such as acetonitrile; ethyl acetate Esters such as; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene; dimethylformamide and dimethylacetamide Amides; Sulfoxides such as dimethyl sulfoxide; Aliphatic hydrocarbons such as hexane and cyclohexane; or a mixed solvent thereof, preferably halogenated hydrocarbons, and more preferably Methylene chloride and chloroform.

  While the reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, it is generally -90 ° C to 200 ° C, preferably 0 ° C to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the kind of solvent used, it is generally 5 minutes to 72 hours, preferably 30 minutes to 24 hours.

(Process P-3)
In Step P-3, the compound (XXX) is reacted with an oxygen nucleophile represented by the general formula (VI) in the presence or absence of a solvent, and optionally in the presence of a base, to give a compound of the present invention ( Iv) or a process for producing a compound in which a hydroxyl group represented by the general formula (XXXI) is protected.
This step is the same as step A-3, B-4, C-3 or J-5.

(Process P-4)
Step P-4 is a step for producing the compound (Iw) of the present invention by removing the protecting group for the hydroxyl group of the compound (XXXI).
This step is a step A-4, B-5, C-4, D-2, E-3, F-2, G-2, J-6, K-5, L-2, M-2 or N -2.

(Process Q)

In the above ^{formulas, R 1, R 2, R} 3, R 4, R 5, R 6 and R ⁷ are as defined above. The compound represented by the general formula (XXXII) represents an oxygen nucleophile, a sulfur nucleophile, and a nitrogen nucleophile. Z is a substituent obtained by removing a proton from an oxygen nucleophile, sulfur nucleophile or nitrogen nucleophile, and may be, for example, an alkoxy group, a thioalkoxy group, a dialkylamino group, or the like.
Step Q is a step of converting the hydroxy compound of the present invention represented by the general formula (Ib) into the ester derivative of the present invention represented by the general formula (Iy).

(Process Q-1)
Step Q-1 is a step of producing the compound (Ix) of the present invention by reacting the compound (Ib) of the present invention with phosgene in the presence or absence of a solvent.
The amount of phosgene used in the reaction is usually 0.5 to 10 mol, preferably 1 to 3 mol, relative to 1 mol of compound (Ib).

The reaction is preferably carried out in the presence of a base.
The base used is not particularly limited as long as it usually shows a pH of 8 or more. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkalis such as sodium carbonate, potassium carbonate and cesium carbonate Metal carbonates; metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aliphatic triions such as triethylamine, tributylamine and diisopropylethylamine Tertiary amines; aliphatic cyclic tertiary amines such as 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) Of pyridine, collidine, 4- (N, N-dimethylamino) pyridine Or pyridines; or organometallic bases such as n-butyllithium, sec-butyllithium, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, preferably alkali metals Hydroxides, alkali metal carbonates, aliphatic tertiary amines, aliphatic cyclic tertiary amines or pyridines, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate , Triethylamine, 1,4-diazabicyclo [2.2.2] octane (DABCO), pyridine or 4- (N, N-dimethylamino) pyridine.

  The amount of the base used in the reaction is usually 0.5 to 20 mol, preferably 1 to 5 mol, relative to 1 mol of compound (Ib).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water, acetone, ketones such as methyl isobutyl ketone; nitriles such as acetonitrile; acetic acid Esters such as ethyl; Halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons such as toluene; Hexane and cyclohexane Aliphatic hydrocarbons; Amides such as dimethylformamide and dimethylacetamide; Sulfoxides such as dimethylsulfoxide; or a mixed solvent thereof, preferably nitriles, halogenated hydrocarbons, ethers, Water-ester mixed solvent, water-halogenated Hydrogenated mixed solvent, water-ether mixed solvent, water-aromatic hydrocarbon mixed solvent or water-aliphatic hydrocarbon mixed solvent, more preferably acetonitrile, methylene chloride or water-toluene mixed solvent It is.

The reaction temperature mainly varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 100 ° C.
While the reaction time mainly varies depending on the reaction temperature, the raw material compound, the reaction reagent, and the type of solvent used, it is generally 5 minutes to 48 hours, and preferably 15 minutes to 12 hours.

(Process Q-2)
Step Q-2 comprises reacting the compound (Ix) of the present invention with a nucleophile represented by the general formula (XXXII) in the presence or absence of a solvent, and optionally in the presence of a base. This is a process for producing the inventive compound (Iy).

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water, acetone, ketones such as methyl isobutyl ketone; nitriles such as acetonitrile; acetic acid Esters such as ethyl; Halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons such as toluene; Hexane and cyclohexane Aliphatic hydrocarbons; Amides such as dimethylformamide and dimethylacetamide; Sulfoxides such as dimethylsulfoxide; or a mixed solvent thereof, preferably nitriles, halogenated hydrocarbons, ethers, Water-ester mixed solvent, water-halogenated Hydrogenated mixed solvent, water-ether mixed solvent, water-aromatic hydrocarbon mixed solvent or water-aliphatic hydrocarbon mixed solvent, more preferably acetonitrile, methylene chloride or water-toluene mixed solvent It is.

  The base used is not particularly limited as long as it usually shows a pH of 8 or more. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkalis such as sodium carbonate, potassium carbonate and cesium carbonate Metal carbonates; metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; alkali metal hydrides such as sodium hydride and potassium hydride; aliphatic triions such as triethylamine, tributylamine and diisopropylethylamine Tertiary amines; aliphatic cyclic tertiary amines such as 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) Of pyridine, collidine, 4- (N, N-dimethylamino) pyridine Or an organometallic base such as n-butyllithium, sec-butyllithium, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide, and preferably an alkali metal Hydroxides, alkali metal carbonates, aliphatic tertiary amines, aliphatic cyclic tertiary amines or pyridines, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate , Triethylamine, 1,4-diazabicyclo [2.2.2] octane (DABCO), pyridine or 4- (N, N-dimethylamino) pyridine.

  The amount of the base used in the reaction is usually 0.5 to 20 mol, preferably 1 to 5 mol, relative to 1 mol of compound (Ix).

  The nucleophile (XXXII) used in the reaction is not particularly limited as long as it replaces the chlorine atom of the chlorocarbonate (Ix). Examples of the oxygen nucleophile include methanol, ethanol, and propanol. Or alcohols such as phenol and 4-chlorophenol, and examples of sulfur nucleophiles include thiols such as methanethiol, ethanethiol and propanethiol; The nitrogen nucleophile can be, for example, methylamine, dimethylamine, diethylamine, methyl (t-butyl) amine, methyl (cyanomethyl) amine, methyl (ethoxycarbonylmethyl). Amine, bis (cyanomethyl) amine, bis (2-cyanoethyl) amine, Aliphatic chain amines such as bis (ethoxycarbonylmethyl) amine, bis (2-methoxyethyl) amine, bis (2-ethoxyethyl) amine, bis (2-chloroethyl) amine, N, O-dimethylhydroxylamine Aromatic amines such as methyl (phenyl) amine and methyl (pyridyl) amine; aziridine, azetidine, pyrrolidine, piperidine, morpholine, thiomorpholine, N-methylpiperazine, N-phenylpiperazine, 2-methoxycarbonylpyrrolidine, 3 -Hydroxypyrrolidine, 4-bromopiperidine, 4-methylpiperidine, 2,2,6,6-tetramethylpiperidine, 2-ethoxycarbonylpiperidine, 4-ethoxycarbonylpiperidine, 2,6-dimethylmorpholine, 1,2,3 , 4-Tetrahydro Aliphatic cyclic amines such as soquinoline; aromatic cyclic amines such as carbazole and 2,5-dimethylpyrrole, preferably methanol, ethanol, methanethiol, ethanethiol, methylamine, dimethylamine, methyl (Cyanomethyl) amine, methyl (ethoxycarbonylmethyl) amine, bis (cyanomethyl) amine, bis (2-cyanoethyl) amine, bis (ethoxycarbonylmethyl) amine, bis (2-methoxyethyl) amine, bis (2-ethoxyethyl) ) Amine, bis (2-chloroethyl) amine, N, O-dimethylhydroxylamine, methyl (pyridyl) amine, azetidine, pyrrolidine, piperidine, morpholine, thiomorpholine, N-methylpiperazine, 2-methoxycarbonylpyrrolidine, 3-hy Roxypyrrolidine, 2-ethoxycarbonylpiperidine, 4-ethoxycarbonylpiperidine, 2,6-dimethylmorpholine, 2,5-dimethylpyrrole, more preferably dimethylamine, methyl (cyanomethyl) amine, methyl (ethoxycarbonylmethyl) ) Amine, bis (cyanomethyl) amine, bis (ethoxycarbonylmethyl) amine, bis (2-methoxyethyl) amine, bis (2-ethoxyethyl) amine, N, O-dimethylhydroxylamine, azetidine, morpholine, thiomorpholine, N-methylpiperazine, 2-methoxycarbonylpyrrolidine, 3-hydroxypyrrolidine, 2-ethoxycarbonylpiperidine, 4-ethoxycarbonylpiperidine, 2,6-dimethylmorpholine.

  The amount of the nucleophile used for the reaction is usually 0.5 to 20 mol, preferably 1 to 5 mol, relative to 1 mol of compound (Ix).

  The reaction temperature mainly varies depending on the raw material compound, the reaction reagent, and the type of solvent used, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 100 ° C.

  While the reaction time mainly varies depending on the reaction temperature, raw material compound, reaction reagent and the type of solvent used, it is usually 5 minutes to 48 hours, preferably 15 minutes to 12 hours.

Note that after the completion of each reaction step, prior to the subsequent step, functional groups in R ¹ to R ⁷ of the target compound of each step, as long as it is within the scope of the definition of R ¹ to R ^7, according to a conventional method Functional group conversion is possible.

In Steps A-1, B-2, D-1 and E-2, when at least one of R ¹ and R ² is a chlorine atom, depending on the reaction conditions, R ¹ or R ² Of chlorine atom

Further, in Steps A-3, B-4, C-3 and J-5, when at least one of R ¹ and R ² is a chlorine atom, depending on the reaction conditions, In the process, the chlorine atom of R ¹ or R ² may be substituted by the group OY. Furthermore, in process P-3, when the bromine atom at the 6-position of the pyridazine ring or R ² is a chlorine atom, , The chlorine atom of R ² may be replaced by the group OY.

  The starting compound (II) of Steps A and B is either commercially available or, for example, Industrial Chemical Journal, 1971, 74, 7, 1490-1491; Tetrahedron, 1999 55, 52, 15067-15070; The Journal of Organic Chemistry, 1963, 28, 218-221, or according to these methods.

  Starting compounds (X) of Steps D and E are, for example, Helvetica Chimica Acta, 1956, 39, pp. 1755-1764; Monatshefte fur Chemie, 1968, 99, 15 -81 (in this description the letter u in Monatshefte fur Chemie represents u-umlaut); German Patent 1,912,472, filed November 12, 1970 (filed April 12, 1969) (Ger.Offen. 1,912,472 , 12 Nov 1970, Appl. 12 Mar 1969).

  As the phenol compound (III) used in Steps A, B, D and E, a commercially available product can be used, or it can be produced using a known method or according to a known method.

  2-isobutylphenol can be produced, for example, by the method described in Canadian Journal of Chemistry, 1956, 34, 851-854.

  2-pentylphenol can be produced, for example, by the method described in Tetrahedron Letters, 1989, Vol. 30, No. 35, pages 4741-4744.

  2-hexylphenol, for example, from the commercially available 1-methoxy-2-vinylbenzene, Journal of the Chemical Society: Parkin Transaction I (Journal of the Chemical Society: Parkin transaction I), 2000, vol. 7, pp. 1109-1116 (conversion of vinyl group to hexyl group) and Journal of Medicinal Chemistry, 1977, vol. 20, 10 No., pages 1317-1323 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-cyclopropylphenol can be produced, for example, by the method described in Bioorganic & Medicinal Chemistry, 1997, Vol. 5, No. 10, pp. 1959-1968.

  2- (1-methylcyclopropyl) phenol (2- (1-methylcyclopropyl) phenol) is, for example, from the commercially available 1- (2-methoxyphenyl) ethanone, the Journal of The method described in The Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications, 1985, 15, 10, 855-864 (conversion of carbonyl groups to olefins) Conversion, Wittg reaction) and Organic Reactions, 1973, 20, 1-131 or Journal of the American Chemical Society, 1975, 97, 3428 or Tetrahedron Letters, 1998, Vol. 39, pages 8621-8624 (construction of cyclopropyl groups, Simmons-Smith reaction), and biotechnology Science Biotechnology and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (Conversion of phenylmethyl ether to phenol, demethylation) Can be produced according to the following reaction.

  2- (1-ethylcyclopropyl) phenol is a commercially available 1- (2-methoxyphenyl) -1-propanone, for example. ) From The Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications, 1985, 15, 10, 855-864 ( (Conversion of carbonyl group to olefin, Wittg reaction) and Organic Reactions, 1973, 20, 1-131 or Journal of the American Chemical Society, 1975, 97, page 3428 or Tetrahedron Letters, 1998, 39, pages 8621-8624 (construction of cyclopropyl group, Simmons-Smith reaction), and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pp. 1572-1574 or JP-A-11-322755 (conversion, removal of phenylmethyl ether to phenol (Methylation reaction).

  2- (1-cyclopropylcyclopropyl) phenol is a commercially available 2,3-dihydro-4H-chromen-4-one (2,3-dihydro-4H-chromen), for example. -4-one), Journal of the Chemical Society: Parkin transaction I, 1990, pages 689-693, cyclopropyl (2-hydroxyphenyl) Methanone [cyclopropyl (2-hydroxyphenyl) methanone], Organic Synthesis, Collective Volume, Volume 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation) Reaction) and The Journal of Organic Chemistry, 1963, 28, 1128 or synthetic communication (Synthetic Communications), 1985, Vol. 15, No. 10, pages 855-864 (conversion of carbonyl group to olefin, Wittg reaction), Organic Reactions, 1973, Vol. 20, 1-131 or Journal of the American Chemical Society, 1975, 97, 3428 or Tetrahedron Letters, 1998, 39, 8621-8624 Methods (construction of cyclopropyl groups, Simmons-Smith reaction), and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11- It can be produced according to the method described in 322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  1- (2-hydroxyphenyl) cyclopropanecarbonitrile (Journal of the American Chemical Society), 2000, Vol. 122, No. 4, 1- (2-methoxyphenyl) cyclopropanecarbonitrile (1- (2-methoxyphenyl) cyclopropanecarbonitrile) is produced by the method described on pages 712-713, and organic synthesis, collective volume, Volume 5, pages 412-414, can be produced according to the method described in the above (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2- (1-phenylcyclopropyl) phenol is a commercially available 1- (2-methoxyphenyl) (phenyl) methanone, for example. ) From The Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications, 1985, 15, 10, 855-864 ( (Conversion of carbonyl group to olefin, Wittg reaction) and Organic Reactions, 1973, 20, 1-131 or Journal of the American Chemical Society, 1975, 97, 3428 or Tetrahedron Letters, 1998, 39, 8621-8624 (construction of cyclopropyl group, Simmons-Smith reaction) ), And the method described in Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP 11-322755 (to the phenol of phenyl methyl ether) Conversion, demethylation reaction).

  2- (2-methylcyclopropyl) phenol (2- (2-methylcyclopropyl) phenol) is, for example, from commercially available 1- (chloromethyl) -2-methoxybenzene, Journal of the American Chemical Society, 1973, Vol. 95, No. 2, pp. 581-582 (construction of cyclopropyl group) and bioscience Biotechnology and Biochemistry (Bioscience) , Biotechnology, and Biochemistry), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction) .

  2- (2,2-dimethylcyclopropyl) phenol is, for example, commercially available 1- (chloromethyl) -2-methoxybenzene [1- (chloromethyl) -2- methoxybenzene], Journal of the American Chemical Society, 1973, Vol. 95, No. 2, pages 581-582 (construction of cyclopropyl group), bioscience biotechnology and Biochemistry (Bioscience, Biotechnology, and Biochemistry), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction) It can be manufactured similarly.

  2-[(cis-2, cis-3-dimethyl) -ref-1-cyclopropyl] phenol (2-[(cis-2, cis-3-dimethyl) -ref-1-cyclopropyl] phenol) is, for example, From the commercial 1- (chloromethyl) -2-methoxybenzene, Journal of the American Chemical Society, 1973, volume 95, No. 2 581-582 (construction of cyclopropyl group) and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or It can be produced according to the method described in 11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-[(cis-2, trans-3-dimethyl) -ref-1-cyclopropyl] phenol (2-[(cis-2, trans-3-dimethyl) -ref-1-cyclopropyl] phenol) is, for example, From the commercial 1- (chloromethyl) -2-methoxybenzene, Journal of the American Chemical Society, 1973, volume 95, No. 2 581-582 (construction of cyclopropyl group) and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or It can be produced according to the method described in 11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-[(trans-2, trans-3-dimethyl) -ref-1-cyclopropyl] phenol (2-[(trans-2, trans-3-dimethyl) -ref-1-cyclopropyl] phenol) From the commercial 1- (chloromethyl) -2-methoxybenzene, Journal of the American Chemical Society, 1973, volume 95, No. 2 581-582 (construction of cyclopropyl group) and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or It can be produced according to the method described in 11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-[(ref-1, cis-5, cis-6) -bicyclo [3.1.0] hexa-6-yl] phenol (2-[(ref-1, cis-5, cis-6) -bicyclo [ 3.1.0] hex-6-yl] phenol), for example, from the commercial 1- (chloromethyl) -2-methoxybenzene, Journal of the American Chemical Society (Journal of the American Chemical Society), 1973, Vol. 95, No. 2, pages 581-582 (construction of cyclopropyl groups), and Bioscience, Biotechnology, and Biochemistry, 1993 No. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-[(ref-1, cis-5, trans-6) -bicyclo [3.1.0] hex-6-yl] phenol (2-[(ref-1, cis-5, trans-6) -bicyclo [ 3.1.0] hex-6-yl] phenol), for example, from the commercial 1- (chloromethyl) -2-methoxybenzene, Journal of the American Chemical Society (Journal of the American Chemical Society), 1973, Vol. 95, No. 2, pages 581-582 (construction of cyclopropyl groups), and Bioscience, Biotechnology, and Biochemistry, 1993 No. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-[(ref-1, cis-6, cis-7) -bicyclo [4.1.0] hept-7-yl] phenol {2-[(ref-1, cis-6, cis-7) -bicyclo [ 4.1.0] hept-7-yl] phenol} is, for example, from the commercially available 1- (chloromethyl) -2-methoxybenzene, Journal of the American Chemical Society (Journal of the American Chemical Society), 1973, Vol. 95, No. 2, pages 581-582 (construction of cyclopropyl groups), and Bioscience, Biotechnology, and Biochemistry, 1993 No. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-[(ref-1, cis-6, trans-7) -bicyclo [4.1.0] hept-7-yl] phenol (2-[(ref-1, cis-6, trans-7) -bicyclo [ 4.1.0] hept-7-yl] phenol), for example, from the commercially available 1- (chloromethyl) -2-methoxybenzene, Journal of the American Chemical Society (Journal of the American Chemical Society), 1973, Vol. 95, No. 2, pages 581-582 (construction of cyclopropyl groups), and Bioscience, Biotechnology, and Biochemistry, 1993 No. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-[(2,2, cis-3-trimethyl) -ref-1-cyclopropyl] phenol (2-[(2,2, cis-3-trimethyl) -ref-1-cyclopropyl] phenol) is, for example, From the commercial 1- (chloromethyl) -2-methoxybenzene, Journal of the American Chemical Society, 1973, volume 95, No. 2 581-582 (construction of cyclopropyl group) and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or It can be produced according to the method described in 11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-[(2,2, trans-3-trimethyl) -ref-1-cyclopropyl] phenol (2-[(2,2, trans-3-trimethyl) -ref-1cyclopropyl] phenol) is commercially available, for example. From 1- (chloromethyl) -2-methoxybenzene, Journal of the American Chemical Society, 1973, Vol. 95, No. 2, 581 -582 (construction of cyclopropyl group) and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11- It can be produced according to the method described in 322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-cyclobutylphenol can be produced, for example, by the method described in German Patent DE-2825388.

  1- (2-hydroxyphenyl) cyclobutanecarbonitrile (1- (2-hydroxyphenyl) cyclobutanecarbonitrile) is, for example, Pharmaceutical Chemistry Journal (English Translation), 1980, Volume 14 , No. 2, pages 114-118.

  1- (2-Hydroxyphenyl) cyclobutanecarboxylic acid (1- (2-hydroxyphenyl) cyclobutanecarboxylic acid) is, for example, Pharmaceutical Chemistry Journal (English Translation), 1980, 14 and No. 2, pages 114-118.

  2- (1-propynyl) phenol is, for example, Journal of the Chemical Society: Parkin transaction I, 1998, pages 477-484. It can manufacture by the method of description.

  2- (cyclopropylmethyl) phenol is a commercially available 2,3-dihydro-4H-chromen-4-one, for example. From the Journal of the Chemical Society: Parkin transaction I, 1990, pages 689-693, cyclopropyl (2-hydroxyphenyl) methanone (cyclopropyl (2- from hydroxyphenyl) methanone) according to the method described in Organic Reactions, 1941, Vol. 1, p. 155 (Clemmensen reduction).

  2- (methoxymethyl) phenol can be produced, for example, by the method described in Tetrahedron Letters, 1999, 40, 6049.

  2- (ethoxymethyl) phenol can be produced, for example, by the method described in Tetrahedron Letters, 1999, 40, 6049.

  2- (1,3-dioxolan-2-yl) phenol is, for example, Tetrahedron Letters, 1989, volume 30, 13 No., pages 1609-1612.

  1- (2-hydroxyphenyl) ethanone O-methyloxime is an example of commercially available 1- (2-hydroxyphenyl) ethanone (1- (2-hydroxyphenyl) ethanone). ) According to the method described in Journal of the American Chemical Society, 1986, Vol. 108, pages 6016-6023.

  3 '-(trifluoromethyl) [1,1'-biphenyl] -2-ol (3'-(trifluoromethyl) [1,1'-biphenyl] -2-ol) is an example of commercially available 2-iodophenol. From (2-iodophenol) and 3- (trifluoromethyl) phenylboronic acid, the method described in Chemical Reviews, 1995, Vol. 95, pages 2457-2483 (phenylation) Reaction, Suzuki-Miyaura coupling reaction).

  2- (1H-pyrrol-1-yl) phenol is, for example, The Journal of Antibiotics, 1994, 47, 5 No., pages 602-605.

  2- (2-thienyl) phenol can be obtained, for example, by the method described in Journal of Heterocyclic Chemistry, 1985, Vol. 22, pages 1667-1669. Can be manufactured.

  2- (3-thienyl) phenol can be obtained, for example, by the method described in Journal of Heterocyclic Chemistry, 1985, Vol. 22, pages 1667-1669. Can be manufactured.

  2- (1H-pyrazol-1-yl) phenol is, for example, Canadian Journal of Chemistry, 1963, 41, 2086-2092. It can be produced by the method described on the page.

  2- (3,5-dimethyl-1H-pyrazol-1-yl) phenol (2- (3,5-dimethyl-1H-pyrazol-1-yl) phenol) is described, for example, in Heterocycles, 1982 19th volume, No. 8, 1487-1495.

  2- [3- (trifluoromethyl) -1H-pyrazol-1-yl] phenol (2- [3- (trifluoromethyl) -1H-pyrazol-1-yl] phenol) is, for example, commercially available 1- (2 1- (2-methoxyphenyl) hydrazine hydrochloride (1- (2-methoxyphenyl) hydrazine hydrochloride), according to the method described in Journal of Fluorine Chemistry 1998, Vol. 92, p.23. ) -3- (Trifluoromethyl) -1H-pyrazole (1- (2-methoxyphenyl) -3- (trifluoromethyl) -1H-pyrazole), organic synthesis, collective volume, Volume 5, pages 412-414, can be produced according to the method described above (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2- [4- (trifluoromethyl) -1H-pyrazol-1-yl] phenol (2- [4- (trifluoromethyl) -1H-pyrazol-1-yl] phenol) is, for example, commercially available 1- (2 -Methoxyphenyl) hydrazine hydrochloride (1- (2-methoxyphenyl) hydrazine hydrochloride) was prepared according to the method described in Tetrahedron Letters, 1996, Vol. 37, No. 11, page 1829. Methoxyphenyl) -4- (trifluoromethyl) -1H-pyrazole (1- (2-methoxyphenyl) -4- (trifluoromethyl) -1H-pyrazole) is manufactured, Organic Synthesis, Collective Volume ), Vol. 5, pages 412-414 (conversion to phenylmethyl ether to phenol, demethylation reaction).

  2- [5- (trifluoromethyl) -1H-pyrazol-1-yl] phenol (2- [5- (trifluoromethyl) -1H-pyrazol-1-yl] phenol) is, for example, commercially available 1- (2 1- (2-methoxyphenyl) hydrazine hydrochloride (1- (2-methoxyphenyl) hydrazine hydrochloride) according to the method described in Journal of Fluorine Chemistry 1998, Vol. 92, p.23. ) -5- (Trifluoromethyl) -1H-pyrazole (1- (2-methoxyphenyl) -5- (trifluoromethyl) -1H-pyrazole), Organic Synthesis, Collective Volume, Volume 5, pages 412-414, can be produced according to the method described above (conversion of phenylmethyl ether to phenol, demethylation reaction).

  5- (2-hydroxyphenyl) -N, N-dimethyl-1H-pyrazole-1-sulfonamide (5- (2-hydroxyphenyl) -N, N-dimethyl-1H-pyrazole-1-sulfonamide) is, for example, From commercially available 4-chloro-2- (1H-pyrazol-5-yl) phenol, Journal of Medicinal Chemistry, 1998 5- (5-Chloro-2-hydroxyphenyl) -N, N-dimethyl-1H-pyrazole-1-sulfonamide (5), which can be produced according to the method described in Y. 41, No. 12, 2019-2028 -(5-chloro-2-hydroxyphenyl) -N, N-dimethyl-1H-pyrazole-1-sulfonamide), according to the method described in Experimental Chemistry Course 4th edition Volume 26 pages 251-266 (catalytic hydrogenation reaction) Can be manufactured.

  3- (2-hydroxyphenyl) -N, N-dimethyl-1H-pyrazole-1-sulfonamide (3- (2-hydroxyphenyl) -N, N-dimethyl-1H-pyrazole-1-sulfonamide) is, for example, From commercially available 4-chloro-2- (1H-pyrazol-5-yl) phenol, Journal of Medicinal Chemistry, 1998 3- (5-Chloro-2-hydroxyphenyl) -N, N-dimethyl-1H-pyrazole-1-sulfonamide (3), which can be produced according to the method described in Y., Vol. 41, No. 12, 2019-2028 -(5-chloro-2-hydroxyphenyl) -N, N-dimethyl-1H-pyrazole-1-sulfonamide), according to the method described in Experimental Chemistry Course 4th edition Volume 26 pages 251-266 (catalytic hydrogenation reaction) Can be manufactured.

  2- (4-methyl-1,3-thiazol-2-yl) phenol (2- (4-methyl-1,3-thiazol-2-yl) phenol) is, for example, commercially available 2-hydroxybenzonitrile ( Prepared from 2-hydroxybenzonitrile by the method described in JP-A-11-60552 (thioamidation reaction of cyano group) and the method described by Liebigs Annalen der Chemie, 1890, 259, 236 it can.

  2- (1,3-benzoxazol-2-yl) phenol is an example of The Journal of Organic Chemistry, 1970. 35, pages 3147-3149.

  2- (1,3-benzothiazol-2-yl) phenol is, for example, the Journal of Organic Chemistry, 1970 35, pages 3147-3149.

  2- (dimethylamino) phenol can be produced, for example, by the method described in Journal of Medicinal Chemistry, 1998, Vol. 41, pages 4800-4818.

  2- (2-methoxyethoxy) phenol (Journal of the Chemical Society: Parkin transaction, for example, from the commercially available pyrocatechol, Journal of the Chemical Society) I), 1980, can be produced according to the method described on pages 756-758.

  2- (isopropylsulfanyl) phenol can be produced, for example, by the method described in Tetrahedron, 1970, Vol. 26, pages 4449-4471.

  3-cyclopropylphenol is, for example, from commercially available 1-bromo-3-methoxybenzene, Tetrahedron Letters, 2000, 41, 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction) and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, 1572 -1574 or according to the method described in JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  3- (2-furyl) phenol is described in, for example, The Journal of Organic Chemistry, 1993, Vol. 58, No. 17, pages 4722-4726. 2- (3-methoxyphenyl) furan (Bioscience, Biotechnology, and Biochemistry), 1993, Vol. 57, 9 No., pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  4-cyclopropylphenol is, for example, from commercially available 1-bromo-4-methoxybenzene, Tetrahedron Letters, 2000, 41, 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction) and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, 1572 -1574 or according to the method described in JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-Bromo-3-methylphenol is an organic synthesis or collective from commercially available 2-methoxy-6-methylaniline, for example. The method described in Collective Volume, Volume 3, pages 185-187, or The Journal of Organic Chemistry, 1977, Volume 42, pages 242-2430. Conversion to benzene, Sandmeyer reaction, etc.) and the method described in Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 It can be produced according to (conversion of phenylmethyl ether to phenol, demethylation reaction).

3-Fluoro-2-methylphenol is a commercially available 3-fluoro-2-methylbenzaldehyde from Journal of the Chemical Society: Parkin Transaction I ( It can be produced according to the method described in Journal of the Chemical Society: Parkin transaction I), 1974, page 1353.
3-chloro-2-methylphenol is more organic than organic 1-chloro-3-methoxy-2-methylbenzene. Synthesis, Collective Volume, Vol. 5, pages 412-414 (conversion to phenyl methyl ether to phenol, demethylation reaction).

  3-methoxy-2-methylphenol is organic synthesis from commercially available 2-methyl-1,3-benzenediol (Organic Synthesis), It can be produced according to the method described in Collective Volume, Vol. 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction).

2-cyclopropyl-3-methylphenol is, for example, from commercially available 2-methoxy-6-methylaniline, organic synthesis, Collective Volume, Volume 3, pages 185-187, or The Journal of Organic Chemistry, 1977, Volume 42, pages 242-2430. Conversion to bromobenzene, Sandmeyer reaction, etc.) and the method described in Tetrahedron Letters, 1979, 20, 4159-4162, or Tetrahedron, 1997, 53, 43 No. 14599-14614 or Bulletin of the Chemical Society of Japan, 1971, 44, 2237-2248 (aromatic bromide) And the Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications, 1985, 15, 10 855-864 (conversion of carbonyl group to olefin, Wittg reaction) and Organic Reactions, 1973, 20, pp. 1-131 or Journal of the American Chemical Society (Journal of the American Chemical Society), 1975, 97, 3428 or Tetrahedron Letters, 1998, 39, 8621-8624 (construction of cyclopropyl group, Simmons-Smith reaction), And Bioscience, Biotechnology, and Biochemistry, 1993, Volume 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-cyclopropyl-3-methoxyphenol, for example, from the commercially available 2,6-dimethoxybenzaldehyde, the Journal of Organic Chemistry. ), 1963, 28, 1128 or Synthetic Communications, 1985, 15, 10, 855-864 (conversion of carbonyl group to olefin, Wittg reaction), and Organic Reactions, 1973, 20, 1-131 or Journal of the American Chemical Society, 1975, 97, 3428 or Tetrahedron Letters 1998, 39, 8621-8624 (construction of cyclopropyl group, Simmons-Smith reaction), and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pp. 1572-1574 or Japanese Patent Application Laid-Open No. 11-322755 (Methylation reaction).

  4-indanol is, for example, a method described in Organic Reactions, 1941, Vol. 1, page 155 from commercially available 4-hydroxy-1-indanone. It can be produced according to (Clemmensen reduction).

  3-methyl-4-indanol can be produced, for example, by the method described in Journal of Applied Chemistry, 1959, Vol. 9, pages 629,637.

  1-methyl-4-indanol can be produced, for example, by the method described in Journal of the Chemical Society, 1961, pages 2773-2777.

  2,2-dimethyl-4-indanol is described in, for example, Journal of Chemical Research Miniprint, 1985, Vol. 8, pages 2724-2747 It can manufacture by the method of.

  Spiro [cyclopropane-1,3 '-(2', 3'-dihydro-1'H-indene-4'-ol)] (spiro [cyclopropane-1,3 '-(2', 3'-dihydro- 1'H-inden-4'-ol)]), for example, from the commercially available 2,3-dihydro-4H-chromen-4-ol, Organic and Medicinal Chemistry, 1999, Vol. 7, No. 12, pp. 2801-2810 (synthesis of 7-hydroxy-1-indanone), and Organic Synthesis, Collective Volume, Volume 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation), and Journal of Organic Chemistry (The Journal of Organic Chemistry), 1963, 28, 1128, or Synthetic Communications, 1985 Vol. 15, No. 10, pages 855-864 (Conversion of carbonyl group to olefin, Wittg reaction) and Organic Reactions, 1973, 20, 1-131 or Journal of the American Chemical Society, 1975, 97, 3428 or Tetrahedron Letters, 1998, 39, 8621-8624 (construction of cyclopropyl group, Simmons-Smith reaction) and the method described in Bioscience, Biotechnology, and Biochemistry (Bioscience, Biotechnology, and Biochemistry), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 It can be produced according to the conversion of ether to phenol, demethylation reaction).

  7-hydroxy-2,3-dihydro-1H-inden-1-one O-methyloxime is, for example, commercially available 2 , 3-Dihydro-4H-chromen-4-ol (Bioorganic and Medicinal Chemistry), 1999, Vol. 7, No. 12, 2801-2810 (7-hydroxy-1-indanone synthesis), Organic Synthesis, Collective Volume Vol. 4, 836- 838 (conversion of phenol to phenyl methyl ether, methylation reaction) and Chemical Pharmaceutical Bulletin, 1988, Vol. 36, No. 8, pages 3134-3137 Method (conversion of carbonyl group to oxime) and bioscience The method described in IoTechnology and Biochemistry (Bioscience, Biotechnology, and Biochemistry), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 It can be produced according to (Reaction).

  2,3-dihydro-1-benzofuran-4-ol is, for example, Helvetica Chimica Acta, 1933, 16, 121-129. From 1-benzofuran-4-ol obtained by the method described in Journal of the Chemical Society, 1948, page 894 (reduction of olefins) Reaction).

  3-methyl-2,3-dihydro-1-benzofuran-4-ol is an example of Journal of the Chemical Society. Society, 1951, 3-methyl-1-benzofuran-4-ol, which can be produced by the method described on pages 3229-3234, Journal of the Chemical Society (Journal of the Chemical Society), 1948, page 894 (reduction reaction of olefin).

1-benzofuran-4-ol (1-benzofuran-4-ol) can be obtained, for example, by the method described in Helvetica Chimica Acta, 1933, Vol. 16, pages 121-129.
3-methyl-1-benzofuran-4-ol is described, for example, in Journal of the Chemical Society, 1951, pages 3229-3234. It can be manufactured by the method.

  1-benzothiophen-4-ol is a method described in, for example, Journal of the American Chemical Society, 1935, 57, 1611-1615. Can be manufactured.

  2-Methyl-1,3-benzoxazol-4-ol is, for example, Journal of Medicinal Chemistry, 1987, Volume 30, It can be produced according to the method described in No. 1, pages 62-67.

  2,3-dihydro-1-benzofuran-7-ol is an example of commercially available 7-methoxy-1-benzofuran (7-methoxy-1-benzofuran-7-ol). benzofuran), Journal of the Chemical Society, 1948, page 894 (hydrogenation reaction of benzofuran), and Bioscience, Biotechnology, and Biochemistry. ), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  1-benzofuran-7-ol, for example, is commercially available from 7-methoxy-1-benzofuran from Bioscience, Biotechnology and Biochemistry (Bioscience, Biotechnology, and Biochemistry), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  1,3-benzodioxol-4-ol is a chemical fur from commercially available 1,2,3-benzenetriol. It can be produced by the method described in Chemical Pharmaceutical Bulletin, 1981, Vol. 29, No. 10, pages 2893-2898.

  2,3-dihydro-1,4-benzodioxin-5-ol (2,3-dihydro-1,4-benzodioxin-5-ol) is, for example, commercially available 1,2,3-benzenetriol (1, 2,3-benzenetriol), Journal of the Chemical Society: Parkin transaction I, 1988, pages 511-520.

  2-methyl-1,3-benzoxazol-7-ol is, for example, commercially available 3-nitro-1,2-benzenediol (3-nitro- 1,2-benzenediol), the method described in Liebigs Annalen der Chemie, 1957, 608, 128 (reduction reaction of nitro group to amino group), and Journal of Medicinal Chemistry (Journal of Medicinal Chemistry), 1987, Vol. 30, No. 1, pp. 62-67.

  2-bromo-4-tert-butylphenol can be produced, for example, by the method described in Tetrahedron, 1999, Vol. 55, No. 28, pages 8377-8384. .

2-ethyl-4-iodophenol is a commercially available 2-ethylphenol, The Journal of Organic Chemistry, 1951, 16 volumes. , 1117-1120 pages.
4-Bromo-2-isopropylphenol can be obtained, for example, by the method described in Journal of Medicinal Chemistry, 1971, Vol. 14, No. 9, pages 789-792. Can be manufactured.

  2-cyclopropyl-4-methylphenol is, for example, from commercially available 2-bromo-1-methoxy-4-methylbenzene. , Tetrahedron Letters, 2000, 41, 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), and bioscience, biotechnology and biochemistry (Bioscience, Biotechnology, and Biochemistry), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  5- (dimethylamino) -2-methylphenol is a method described, for example, in Journal of the Chemical Society, 1947, pages 182-191. Can be manufactured.

  5-methoxy-2-methylphenol can be produced, for example, by the method described in Chemical Abstracts, 1938, page 2519.

  2-ethyl-5-methoxyphenol is a method described in, for example, Chemical and Pharmaceutical Bulletin, 1979, Vol. 27, No. 6, pp. 1490-1494 Can be manufactured.

  2,5-diisopropylphenol can be produced, for example, by the method described in The Journal of Organic Chemistry, 1980, Vol. 45, No. 22, pages 4326-4329.

  2-cyclopropyl-5-fluorophenol is, for example, from the commercially available 2-bromo-5-fluorophenol, Helvetica Chimica Acta ), 1992, 75, page 457 (conversion of phenol to phenylmethoxymethyl ether, methoxymethylation reaction), and Tetrahedron Letters, 2000, 41, 4251 4255 page (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction) and tetrahedron 1998, 54, 15861-15869 (phenol of phenylmethoxymethyl ether) Conversion to demethoxymethylation reaction).

  For example, 5-chloro-2-cyclopropylphenol is a commercially available 4-chloro-2-methoxyphenol from The Journal of Organic Chemistry (The Journal of Organic Chemistry), 1997, Vol. 62, No. 2, pp. 261-274, and Tetrahedron Letters, 2000, 41, 4251. -4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction) and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, 1572- It can be produced according to the method described in page 1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-cyclopropyl-5-methylphenol is, for example, from the commercially available 2-methoxy-4-methylphenol, The Journal of Organic Chemistry (The Journal of Organic Chemistry), 1997, Vol. 62, No. 2, pp. 261-274, and Tetrahedron Letters, 2000, 41, 4251. -4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction) and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, 1572- It can be produced according to the method described in page 1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-cyclopropyl-5-ethylphenol is, for example, from the commercially available 4-ethyl-2-methoxyphenol, the Journal of Organic Chemistry (The Journal of Organic Chemistry), 1997, Vol. 62, No. 2, pp. 261-274, and Tetrahedron Letters, 2000, 41, 4251. -4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction) and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, 1572- It can be produced according to the method described in page 1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-cyclopropyl-5-isopropylphenol is, for example, from commercially available 3-isopropylphenol, Tetrahedron Letters, 1998, Vol. 39, 2947 method (phenol bromination reaction) and Helvetica Chimica Acta 1992, 75, page 457 (conversion of phenol to phenylmethoxymethyl ether, methoxymethylation reaction) ) And Tetrahedron Letters, 2000, Vol. 41, pages 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), and tetrahedron (Tetrahedron), 1998, Vol. 54, pages 15861-15869 can be produced according to the method described above (conversion of phenylmethoxymethyl ether to phenol, demethoxymethylation reaction).

  4-cyclopropyl-3-hydroxybenzonitrile, for example, from the commercially available 4-hydroxy-3-methoxybenzonitrile, the Journal of Organic Chemistry. (The Journal of Organic Chemistry), 1997, Vol. 62, No. 2, pages 261-274 (phenol trifluoromethanesulfonylation) and Tetrahedron Letters, 2000, 41 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, 1572-1574 or according to the method described in JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction) Can build.

5-Fluoro-2-[(1E) -1-propenyl] phenol (5-fluoro-2-[(1E) -1-propenyl] phenol) is, for example, Journal of the Chemical Society: Parkin Transaction I (Journal of the Chemical Society: Parkin transaction I), 1994, pages 1823-1831 (synthesis of 4-fluoro-2-hydroxybenzaldehyde) and organic synthesis (Organic Synthesis) ), Collective Volume, Vol. 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation), and Synthetic Communications, 1985, 15 , No. 10, pages 855-864 (conversion of carbonyl group to olefin, Wittg reaction), bioscience, biotechnology and biochemistry (Bioscience, Biotechnology, and Biochemistry), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).
5-chloro-2-[(1E) -1-propenyl] phenol is an example of the Journal of Organic Chemistry. 1964, 29, pages 2693-2698 (synthesis of 4-chloro-2-hydroxybenzaldehyde), organic synthesis, collective volume (Collective) Volume), Vol. 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction), Synthetic Communications, 1985, Vol. 15, No. 10, pages 855-864 (Conversion of carbonyl group to olefin, Wittg reaction) and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, 1572-15 It can be produced according to the method described in page 74 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  4- (dimethylamino) -2-hydroxybenzaldehyde can be produced, for example, by the method described in German Patent (DE 105103).

  5-chloro-2-methoxyphenol is an organic synthesis or collective from commercially available 5-amino-2-methoxyphenol, for example. It can be produced according to the method described in Collective Volume, Vol. 2, pages 130-133 (conversion of anilines to chlorobenzene, Sandmeyer reaction, etc.).

  5-Bromo-2-methoxyphenol is an organic synthesis or collective from commercially available 5-amino-2-methoxyphenol, for example. The method described in Collective Volume, Volume 3, pages 185-187, or The Journal of Organic Chemistry, 1977, Volume 42, pages 242-2430. Conversion to benzene, Sandmeyer reaction, etc.).

  3-hydroxy-4-methoxybenzonitrile is synthesized from, for example, commercially available methyl 3,4-dimethoxybenzoate, Synthesis, 1998, 329. -It can be produced by the method described on page 332.

  2,5-dimethoxyphenol can be produced, for example, by the method described in The Journal of Organic Chemistry, 1987, Vol. 57, page 4485.

  2-bromo-6-fluorophenol is, for example, from commercially available 2-fluorophenol, Tetrahedron Letters, 1998, Vol. 39, 2947. It can be produced according to the method described on page (bromination reaction of phenol).

  2-Fluoro-6-propylphenol is, for example, from commercially available 2-fluorophenol, Organic Reactions, 1949, Vol. 2, 1-48 Page (allylation of phenol, Claisen transfer reaction) and the method described in Journal of the American Chemical Society, 1951, vol. 73, pages 4152-4156 (allyl group). To a propyl group, hydrogenation reaction).

  2-Fluoro-6-isopropylphenol is, for example, from commercially available 2-isopropyl-6-nitrophenol, Organic Synthesis, Collective Volume Vol. 4, 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction), Liebigs Annalen der Chemie, 1975, 608, 128 (method of nitro group) (Reduction reaction to amino group), Synthesis, 1989, method described on page 905 (conversion reaction of amino group to fluorine atom), and bioscience, biotechnology and biochemistry (Bioscience, Biotechnolory, and Biochemistry) 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (phenone of phenyl methyl ether) In accordance with the conversion to desulfurization, demethylation reaction).

  2-cyclopropyl-6-fluorophenol is, for example, from commercially available 2-fluorophenol, Tetrahedron Letters, 1998, Vol. 39, 2947 page (bromination reaction of phenol) and Helvetica Chemica Acta, 1992, vol. 75, page 457 (conversion of phenol to phenylmethoxymethyl ether, methoxymethylation) Reaction) and the method described in Tetrahedron Letters, 2000, 41, 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), and tetrahedron (Tetrahedron) 1998, 54, 15861-15869 (conversion to phenylmethoxymethyl ether phenol, demethoxymethylation reaction).

  2-chloro-6-iodophenol is described in, for example, The Journal of Organic Chemistry, 1988, Vol. 53, No. 22, pages 5281-5287. It can be manufactured by the method.

  2-chloro-6-ethylphenol is produced, for example, by the method described in Journal of Chemical and Engineering Data, 1969, Vol. 14, p. 392 it can.

  2-chloro-6-cyclopropylphenol is, for example, from commercially available 2-chlorophenol, Tetrahedron Letters, 1998, Vol. 39, 2947 page (bromination reaction of phenol) and Helvetica Chimica Acta, 1992, vol. 75, page 457 (conversion of phenol to phenylmethoxymethyl ether, methoxymethylation) Reaction) and the method described in Tetrahedron Letters, 2000, 41, 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), and tetrahedron (Tetrahedron) 1998, 54, 15861-15869 (conversion to phenylmethoxymethyl ether phenol, demethoxymethylation reaction).

  2-chloro-6- (2-methyl-2-propenyl) phenol is, for example, from commercially available 2-chlorophenol. , Organic Reactions, 1949, Vol. 2, pp. 1-48 (phenol allylation, Claisen rearrangement reaction).

2-Bromo-6-methylphenol can be produced, for example, by the method described in Tetrahedron Letters, 1998, Vol. 39, page 2947.
2-Bromo-6-ethylphenol is, for example, from commercially available 2-ethylphenol, Tetrahedron Letters, 1998, Vol. 39, 2947. It can be produced according to the method described on page (bromination reaction of phenol).

  2-Bromo-6-cyclopropylphenol (2-bromo-6-cyclopropylphenol), for example, from organic 2,6-dibromophenol, organic synthesis, collective volume (Collective) Volume), Volume 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction) and Tetrahedron Letters, 2000, 41, 4251-4255 The described method (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction) and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or It can be produced according to the method described in JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  3-bromo-2-hydroxybenzonitrile is, for example, a commercially available 2-hydroxybenzonitrile from Tetrahedron Letters, 1998, Vol. 39. , Page 2947 (the bromination reaction of phenol).

2-bromo-6-methoxyphenol (2-bromo-6-methoxyphenol) can be produced, for example, by the method described in Synthesis, 1999, Vol. 7, pages 1127-1134.
2-iodo-6-methylphenol is obtained, for example, by the method described in Australian Journal of Chemistry, 1997, Vol. 50, No. 7, pages 767-770. Can be manufactured.

  2-ethyl-6-iodophenol is from the commercially available 2-ethylphenol, Australian Journal of Chemistry, 1997, 50, It can be produced according to the method described in No. 7, pages 767-770 (iodination reaction of phenol).

  2-iodo-6-isopropylphenol is a commercially available 2-isopropylphenol, Australian Journal of Chemistry, 1997, 50 volumes, It can be produced according to the method described in No. 7, pages 767-770 (iodination reaction of phenol).

  2-Isopropyl-6-methylphenol is a method described in, for example, Bulletin de la Societe Chemique de France, 1962, pages 1700-1705. Can be manufactured.

  2-sec-butyl-6-methylphenol can be produced, for example, by the method described in Angewandte Chemie, 1957, 69, 699, 703 . Further, for example, from commercially available 2-methylphenol, Organic Reactions, 1949, Vol. 2, page 1-48 (phenol allylation, Claisen transfer reaction), Journal of the American It can also be produced according to the method described in Journal of the American Chemical Society, 1951, Vol. 73, pages 4152-4156 (conversion of allyl group to propyl group, hydrogenation reaction).

  2-cyclopropyl-6-methylphenol is, for example, from commercially available 2-hydroxy-3-methylbenzaldehyde, organic synthesis, Collective Volume, Volume 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction) and The Journal of Organic Chemistry, 1963 28, 1128 or Synthetic Communications, 1985, 15, 10, 855-864 (conversion of carbonyl group to olefin, Wittg reaction) and Organic Reactions ( Organic Reactions), 1973, 20, pp. 1-131, or Journal of the American Chemical Society (J ournal of the American Chemical Society), 1975, 97, 3428 or Tetrahedron Letters, 1998, 39, 8621-8624 (construction of cyclopropyl groups, Simmons-Smith reaction) ), And the method described in Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP 11-322755 (to the phenol of phenyl methyl ether) Conversion, demethylation reaction).

  2-methoxy-6-methylphenol is, for example, a synthetic communication from commercially available 1,2-dimethoxy-3-methylbenzene (Synthetic Communications). ), 1996, Vol. 26, No. 1, pp. 49-62.

  2,6-diethylphenol (2,6-diethylphenol) can be produced, for example, by the method described in Journal of Medicinal Chemistry, 1960, Vol. 2, pages 201-212.

2-cyclopropyl-6-ethylphenol is, for example, from commercially available 2-ethylphenol, Tetrahedron Letters, 1998, Vol. 39, The method described on page 2947 (bromination reaction of phenol) and the method described in Helvetica Chimica Acta, 1992, vol. 75, page 457 (conversion of phenol to phenylmethoxymethyl ether, methoxymethylation) Reaction), and the method described in Tetrahedron Letters, 2000, Vol. 41, pages 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), and tetrahedron (Tetrahedron) 1998, 54, 15861-15869 (conversion to phenylmethoxymethyl ether phenol, demethoxymethylation reaction).
2,6-dipropylphenol is a method described in, for example, Liebigs Annalen der Chemie, 1919, 418, 90-91 (2,6- Diallylphenol (synthesis of 2,6-diallylphenol) and the method described in Bulletin de la Societe Chemique de France, 1937, Vol. 5, No. 4, pages 1080-1083 (Conversion of allyl group to propyl group, hydrogenation reaction)

  2-cyclopropyl-6-isopropylphenol (Journal of the Chemical Society: Parkin transaction I), 1980, 1862-1865, for example Page (Synthesis of 2-hydroxy-3-isopropylbanzaldehyde) and Organic Synthesis, Collective Volume, Vol. 4, 836-838 Page (conversion of phenol to phenyl methyl ether, methylation reaction) and The Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications, 1985, Vol. 15, No. 10, pages 855-864 (carbonyl group (Conversion to olefin, Wittg reaction), and Organic Reactions, 1973, 20, 1-131 or Journal of the American Chemical Society, 1975, 97, 3428 or the method described in Tetrahedron Letters, 1998, Vol. 39, pages 8621-8624 (construction of cyclopropyl group, Simmons-Smith reaction), and bioscience Biotechnology and Biochemistry Biotechnology, and Biochemistry), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  3-tert-butyl-6-cyclopropylphenol is, for example, from commercially available 3-tert-butyl-2-hydroxybenzaldehyde. Organic Synthesis, Collective Volume, Vol. 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation), and Journal of Organic Chemistry (The Journal of Organic Chemistry), 1963, 28, 1128 or Synthetic Communications, 1985, 15, 10, 855-864 (Conversion of carbonyl group to olefin, Wittg reaction) ) And Organic Reactions, 1973, 20, pp. 1-131 or Journal of the American Chemical Saety (Journal of the American Chemical Society), 1975, 97, 3428 or Tetrahedron Letters, 1998, 39, 8621-8624 (construction of cyclopropyl group, Simmons- Smith reaction), and the method described in Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755. (Conversion to phenol, demethylation reaction).

  2,6-dicyclopropylphenol is a method described in, for example, Tetrahedron Letters, 1997, Vol. 38, No. 17, pages 3111-3114 (2-hydroxyisophthalate). Synthesis of aldehyde), and organic synthesis, collective volume, volume 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction), and The method described in The Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications, 1985, 15, 10, 855-864 (olefins of carbonyl group) Conversion, Wittg reaction), and Organic Reactions, 1973, 20, pp. 1-131 or journal The method described in the Journal of the American Chemical Society, 1975, 97, 3428 or Tetrahedron Letters, 1998, 39, 8621-8624. (Structure, Simmons-Smith reaction) and the method described in Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, 1572-1574 or JP-A-11-322755 It can be produced according to the conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-Cyclopropyl-6-methoxyphenol (Helvetica Chimica Acta) is available from, for example, commercially available 2-hydroxy-3-methoxybenzaldeyde. 1992, 75, page 457 (conversion of phenol to phenylmethoxymethyl ether, methoxymethylation reaction) and The Journal of Organic Chemistry, 1963, 28 1128 or Synthetic Communications, 1985, Vol. 15, No. 10, pages 855-864 (conversion of carbonyl group to olefin, Wittg reaction), and Organic Reactions (Organic Reactions), 1973, 20-1-131 or Journal of the Amer Society ican Chemical Society), 1975, 97, 3428 or Tetrahedron Letters, 1998, 39, 8621-8624 (construction of cyclopropyl groups, Simmons-Smith reaction), and , Tetrahedron, 1998, 54, 15861-15869 (conversion to phenylmethoxymethyl ether to phenol, demethoxymethylation reaction).

  2-cyclopropyl-6-ethoxyphenol (Organic Synthesis) from commercially available 3-ethoxy-2-hydroxybenzaldehyde, for example, Collective Volume, Volume 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction) and The Journal of Organic Chemistry, 1963 28, 1128 or Synthetic Communications, 1985, 15, 10, 855-864 (conversion of carbonyl group to olefin, Wittg reaction) and Organic Reactions ( Organic Reactions), 1973, 20, pp. 1-131 or Journal of the American Chemical Sosae (Journal of the American Chemical Society), 1975, 97, 3428 or Tetrahedron Letters, 1998, 39, 8621-8624 (construction of cyclopropyl group, Simmons- Smith reaction), and the method described in Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755. (Conversion to phenol, demethylation reaction).

  2,6-di [(1E) -1-propenyl] phenol (2,6-di [(1E) -1-propenyl] phenol) is, for example, Liebigs Annalen der Chemie, 1919. 418, 90-91 (Synthesis of 2,6-diallylphenol) and Journal of the American Chemical Society, 1956, 78, 1709-1713 It can be produced by the method described in the page (isomerization reaction).

  2,6-diallylphenol can be produced, for example, by the method described in Liebigs Annalen der Chemie, 1919, 418, 90-91.

  3,5-diisopropylphenol can be produced, for example, by the method described in US Pat. No. 2790010.

  2-Bromo-3,5-dimethylphenol (Bulletin of the Chemical Society of Japan) from commercial 3,5-dimethylphenol (Bulletin of the Chemical Society of Japan) the Chemical Society of Japan), 1993, 66, 1576 (phenol bromination reaction).

  3,5-dimethyl-2-propylphenol is an example of Bulletin of the Chemical Society of Japan, 1968, Vol. 41, No. 3. , 745-746.

  2-cyclopropyl-3,5-dimethylphenol, for example, is commercially available from Tetrahedron Letters than 3,5-dimethylphenol. ), 1998, 39, page 2947 (phenol bromination reaction), and organic synthesis, collective volume, volume 4, pages 836-838 ( (Phenol to phenylmethyl ether, methylation reaction) and the method described in Tetrahedron Letters, 1979, 20, 4159-4162 or Tetrahedron, 1997, 53 Vol. 43, pages 14599-14614 or Bulletin of the Chemical Society of Japan, 1971, vol. 44, pages 2237-2248 (aromatic Conversion reaction of bromide to aromatic aldehyde) and The Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications, 1985, 15, 10 855-864 (conversion of carbonyl group to olefin, Wittg reaction) and Organic Reactions, 1973, 20, pp. 1-131 or Journal of the American Chemical Society (Journal of the American Chemical Society), 1975, 97, 3428 or Tetrahedron Letters, 1998, 39, 8621-8624 (construction of cyclopropyl groups, Simmons-Smith reaction) Bioscience, Biotechnology, and Biochemistry ), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  3,5-dimethyl-2- (methylsulfanyl) phenol is, for example, Tetrahedron Letters, 1999, 40, 35, 6357. -6358 page.

  2-bromo-3,6-dimethylphenol is, for example, from Tetrahedron Letters from commercially available 3,6-dimethylphenol. 1998, Vol. 39, p. 2947 (production of phenol bromination).

  6-Bromo-3-fluoro-2-methylphenol is a journal from, for example, commercially available 3-fluoro-2-methylbenzaldehyde. Of the Chemical Society: Perfluorotransaction I (Journal of the Chemical Society: Parkin transaction I), 1974, page 1353, can be produced according to the method described in 3-fluoro-2-methylphenol (3-fluoro-2 -methylphenol) can be produced according to the method described in Tetrahedron Letters, 1998, Vol. 39, page 2947 (bromination reaction of phenol).

  6-bromo-3-chloro-2-methylphenol is a commercially available 1-chloro-3-methoxy-2-methylphenol (1-chloro-3-methoxy-2) -methylbenzene) can be produced according to the methods described in Organic Synthesis, Collective Volume, Vol. 5, pages 412-414 (conversion of phenylmethyl ether to phenol, demethylation reaction) Produced from 3-chloro-2-methylphenol according to the method described in Tetrahedron Letters, 1998, 39, 2947 (bromination of phenol) it can.

  3-chloro-6-cyclopropyl-2-methylphenol is a commercially available 1-chloro-3-methoxy-2-methylphenol. -2-methylbenzene) to organic synthesis, collective volume, volume 5, pages 412-414 (conversion of phenylmethyl ether to phenol, demethylation reaction) From 3-chloro-2-methylphenol that can be produced, the method described in Tetrahedron Letters, 1998, 39, 2947 (bromination reaction of phenol), Helvetica Chimica Acta, 1992, volume 75, page 457 (conversion of phenol to phenylmethoxymethyl ether, methoxymethylation reaction), and tetrahedron letters (Tetrahedron Lett ers), 2000, 41, 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), and Tetrahedron, 1998, 54, 15861-15869 (Conversion of phenylmethoxymethyl ether to phenol, demethoxymethylation reaction).

  6-Bromo-2,3-dimethylphenol is, for example, from the commercially available 2,3-dimethylphenol, Tetrahedron Letters 1998, vol. 39, page 2947 (phenol bromination reaction).

  6-cyclopropyl-2,3-dimethylphenol is, for example, from Tetrahedron Letters from 2,3-dimethylphenol, which is commercially available. , 1998, 39, page 2947 (phenol bromination reaction) and the method described in Helvetica Chimica Acta, 1992, 75, page 457 (phenol phenylmethoxymethyl). Conversion to ether, methoxymethylation reaction), and the method described in Tetrahedron Letters, 2000, 41, 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), Further, it can be produced according to the method described in Tetrahedron, 1998, Vol. 54, pages 15861-15869 (conversion of phenylmethoxymethyl ether to phenol, demethoxymethylation reaction).

  2-hydroxy-3,4-dimethylbenzaldehyde O-methyloxime is obtained from, for example, commercially available 2,3-dimethylphenol, Method described in Tetrahedron Letters, 1998, Vol. 39, page 2947 (bromination reaction of phenol) and method described in Helvetica Chimica Acta, 1992, vol. 75, page 457 (Conversion of phenol to phenylmethoxymethyl ether, methoxymethylation reaction) and the method described in Tetrahedron Letters, 1979, Vol. 20, pages 4159-4162, or Tetrahedron, 1997 Year, 53, 43, 14599-14614, or Bulletin of the Chemical Society of Japan, 1971, 44, 2237-2248 Described in (Conversion reaction of aromatic bromide to aromatic aldehyde) and Journal of the Chemical Society: Perkin transactions I, 1979, pages 643-645 And the method described in (Tetrahedron, 1998, 54, 15861-15869 (conversion of phenylmethoxymethyl ether to phenol, demethoxymethylation reaction) Can be manufactured.

  6-methoxy-2,3-dimethylphenol is, for example, from the commercially available 3,4-dimethylphenol, Tetrahedron Letters 1998, 39, page 2947 (phenol bromination reaction) and Tetrahedron Letters, 1979, 20, page 4159-4162 or tetrahedron (Tetrahedron) 1997, 53, 43, 14599-14614 or Bulletin of the Chemical Society of Japan, 1971, 44, 2237-2248 (Conversion reaction of aromatic bromide to aromatic aldehyde) and Journal of the Chemical Society: Parkin transaction I, 1974, page 1353 It can be prepared according to the method.

  6-bromo-3-methoxy-2-methylphenol is a commercially available 2-methyl-1,3-benzenediol 3-methoxy-, which can be produced according to the method described in Organic Synthesis, Collective Volume, Volume 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction) It can be produced from 2-methylphenol in accordance with the method described in Tetrahedron Letters, 1998, Vol. 39, page 2947 (bromination reaction of phenol).

  6-cyclopropyl-3-methoxy-2-methylphenol is a commercially available 2-methyl-1,3-benzenediol. ) Can be produced according to the method described in Organic Synthesis, Collective Volume, Vol. 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction). From 2-methoxyphenol (3-methoxy-2-methylphenol), the method described in Tetrahedron Letters, 1998, Vol. 39, page 2947 (phenol bromination reaction), and Helvetica Kimika Actor ( Helvetica Chimica Acta), 1992, volume 75, page 457 (conversion of phenol to phenylmethoxymethyl ether, methoxymethylation reaction), and Tetrahedron Letters, 200 0, 41, 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction) and Tetrahedron, 1998, 54, 15861-15869 It can be produced according to the method (conversion of phenylmethoxymethyl ether to phenol, demethoxymethylation reaction).

  2-cyclopropyl-3,6-dimethylphenol is, for example, Tetrahedron Letters rather than commercially available 2,5-dimethylphenol. 1998, vol. 39, page 2947 (phenol bromination reaction) and organic synthesis, collective volume, vol. 4, pages 836-838 (phenol) Conversion to phenylmethyl ether, methylation reaction) and the method described in Tetrahedron Letters, 1979, 20, 4159-4162 or Tetrahedron, 1997, 53 No. 43, pages 14599-14614, or Bulletin of the Chemical Society of Japan, 1971, vol. 44, pages 2237-2248 (aromatic And the Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications, 1985, 15, 10 855-864 (conversion of carbonyl group to olefin, Wittg reaction) and Organic Reactions, 1973, 20, pp. 1-131 or Journal of the American Chemical Society (Journal of the American Chemical Society), 1975, 97, 3428 or Tetrahedron Letters, 1998, 39, 8621-8624 (construction of cyclopropyl groups, Simmons-Smith reaction) Bioscience, Biotechnology, and Biochemistry 1993, Vol. 57, No. 9, (conversion of phenylmethyl ether phenol, demethylation reaction) 1572-1574 page or the method described in JP-A-11-322755 can be produced according to.

  2-allyl-6-ethyl-3-methoxyphenol is, for example, Chemical and Pharmaceutical Bulletin, 1979, Vol. 27, No. 6. From 2-ethyl-5-methoxyphenol, which can be produced by the method described on pages 1490-1494, Organic Reactions, 1949, Volume 2, pages 1-48 Can be produced according to the above method (phenol allylation reaction, Claisen rearrangement).

  3,6-dimethyl-2-[(methylsulfanyl) methyl] phenol is an example of the Journal of the American Chemical Society. 1966, Vol. 88, No. 24, pages 5855-5864.

  5-Bromo-4-indanol is, for example, from the commercially available 4-hydroxy-1-indanone, Journal of the American Chemical Society (Journal of the American Chemical Society), 1946, Vol. 68, page 2487 (reduction reaction of carbonyl group Wolff-Kishner reduction reaction), and Tetrahedron Letters, 1998, vol. 39, page 2947. It can be produced according to the method (bromination reaction of phenol).

  5-Methyl-4-indanol is, for example, from the commercially available 4-hydroxy-1-indanone, Journal of the American Chemical Society (Journal of the American Chemical Society), 1946, vol. 68, page 2487 (reduction of carbonyl group, Wolff-Kishner reduction) and Tetrahedron Letters, 1998, vol. 39, page 2947. The method (bromination reaction of phenol) and the method described in Helvetica Chimica Acta, 1992, vol. 75, page 457 (conversion of phenol to phenylmethoxymethyl ether, methoxymethylation reaction), and Helvetica Chimica Acta, 1990, Vol. 73, pages 417-425 (conversion reaction of bromo group to methyl group), and tetrahedron, 1998, vol. 54 , 15861- It can be produced according to the method described on page 15869 (conversion of phenylmethoxymethyl ether to phenol, demethoxymethylation reaction).

  5-ethyl-4-indanol, for example, is commercially available from 4-hydroxy-1-indanone, Journal of the American Chemical Society (Journal of the American Chemical Society), 1946, vol. 68, page 2487 (reduction of carbonyl group, Wolff-Kishner reduction) and Tetrahedron Letters, 1998, vol. 39, page 2947. The method (bromination reaction of phenol) and the method described in Helvetica Chimica Acta, 1992, vol. 75, page 457 (conversion of phenol to phenylmethoxymethyl ether, methoxymethylation reaction), and Helvetica chimica Acta, 1990, Vol. 73, pages 417-425 (conversion reaction of bromo group to ethyl group), and tetrahedron, 1998, vol. 54 , 15861- It can be produced according to the method described on page 15869 (conversion of phenylmethoxymethyl ether to phenol, demethoxymethylation reaction).

  5-cyclopropyl-4-indanol, for example, is commercially available from 4-hydroxy-1-indanone, Journal of the American Chemical Society (Journal of the American Chemical Society), 1946, vol. 68, page 2487 (reduction reaction of carbonyl group Wolff-Kishner reduction reaction) and Tetrahedron Letters, 1998, vol. 39, page 2947 And the method described in Organic Synthesis, Collective Volume, Vol. 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction) ) And Tetrahedron Letters, 2000, Vol. 41, pages 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (Conversion of phenylmethyl ether to phenol) , Demethylation reaction).

  6-methyl-2,3-dihydro-1-benzofuran-7-ol is, for example, tetrahedron letters, 1998 , Vol. 39, page 2947, from 2-methoxy-3-methylphenol, Journal of the Chemical Society: Perkin Transactions I (Journal of the Chemical Society : Perkin transactions I) 1988, method described on page 3029 (construction of benzofuran ring), and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, 1572-1574 Or 6-methyl-1-benzofuran (6-methyl-1-benzofuran) which can be produced according to the method described in JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction) -7-ol) It can be produced according to the method described in Journal of the Chemical Society, 1948, p. 894 (olefin reduction reaction).

  6-Bromo-1-benzofuran-7-ol is an example of a bioscience from a commercially available 7-methoxy-1-benzofuran. Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (Conversion of phenylmethyl ether to phenol, demethylation) Reaction) and the method described in Tetrahedron Letters, 1998, Vol. 39, page 2947 (bromination reaction of phenol).

  6-Methyl-1-benzofuran-7-ol is produced, for example, by the method described in Tetrahedron Letters, 1998, Vol. 39, page 2947. From 2-methoxy-3-methylphenol, Journal of the Chemical Society Perkin transactions I, 1988, page 3029 Method (construction of benzofuran ring) and the method described in Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 It can be produced according to (conversion of phenylmethyl ether to phenol, demethylation reaction).

  6-cyclopropyl-1-benzofuran-7-ol is, for example, biosynthetic from commercially available 7-methoxy-1-benzofuran (7-methoxy-1-benzofuran). Science Biotechnology and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (Conversion of phenylmethyl ether to phenol, demethylation) And the method described in Tetrahedron Letters, 1998, 39, 2947 (bromination reaction of phenol) and Helvetica Chimica Acta, 1992, 75 , Page 457 (conversion of phenol to phenylmethoxymethyl ether, methoxymethylation reaction) and Tetrahedron Letters, 2000, 41, 4251-4255 And the method described in Tetrahedron, 1998, 54, 15861-15869 (Phenylmethoxymethyl ether to phenol). Conversion, demethoxymethylation reaction).

  2,4-dicyclopropyl-6-fluorophenol is, for example, from commercially available 2-fluorophenol, Tetrahedron Letters, 1998 39, page 2947 (the bromination reaction of phenol) and the method described in Helvetica Chimica Acta, 1992, volume 75, page 457 (phenol to phenylmethoxymethyl ether) Conversion, methoxymethylation reaction), and the method described in Tetrahedron Letters, 2000, 41, 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), and tetra It can be produced according to the method described in Tetrahedron, 1998, Vol. 54, pages 15861-15869 (conversion of phenylmethoxymethyl ether to phenol, demethoxymethylation reaction).

  2,4-dibromo-3,6-dimethylphenol is a tetrahedron letter, for example, from commercially available 3,6-dimethylphenol. (Tetrahedron Letters), 1998, Vol. 39, p. 2947 (production of phenol bromination).

  2-Bromo-4,6-dimethylphenol is, for example, from the commercially available 2,4-dimethylphenol, Tetrahedron Letters 1998, vol. 39, page 2947 (phenol bromination reaction).

  2-ethyl-4,6-diiodophenol is more commercially available than 2-ethylphenol from the Australian Journal of Chemistry, 1997. , 50, No. 7, pp. 767-770 can be produced according to the method (iodination reaction of phenol).

  2-cyclopropyl-4,6-dimethylphenol is, for example, from the commercially available 2,4-dimethylphenol, Tetrahedron Letters , 1998, 39, page 2947 (phenol bromination reaction) and the method described in Helvetica Chimica Acta, 1992, 75, page 457 (phenol phenylmethoxymethyl). Conversion to ether, methoxymethylation reaction), and the method described in Tetrahedron Letters, 2000, 41, 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), Further, it can be produced according to the method described in Tetrahedron, 1998, Vol. 54, pages 15861-15869 (conversion of phenylmethoxymethyl ether to phenol, demethoxymethylation reaction).

  2-bromo-3,5,6-trimethylphenol (2-bromo-3,5,6-trimethylphenol) is, for example, from commercially available 2,3,5-trimethylphenol (2,3,5-trimethylphenol), It can be produced according to the method described in Tetrahedron Letters, 1998, Vol. 39, page 2947 (bromination reaction of phenol).

  5,6-dimethyl-4-indanol is, for example, commercially available 7-methyl-2H-chromen-2-one According to the method described in Journal of Chemical Society of Japan, 1974, pages 136-146, and the method described in Organic Reactions, 1941, Vol. 1, page 155 (Clemmensen reduction).

  1,2,3,5,6,7-hexahydro-s-indacene-4-ol (1,2,3,5,6,7-hexahydro-s-indacen-4-ol) is, for example, commercially available From Indane, Journal of the American Chemical Society, 1977, 99, pages 8007-8014, Organic Reactions, 1941, 1 155, page 155 (Clemmensen reduction) and The Journal of Organic Chemistry, 1977, Vol. 42, pages 3260-3264.

  3- (1,3-dioxolan-2-yl) phenol (3- (1,3-dioxolan-2-yl) phenol), for example, from 3-hydroxybenzaldehyde, tetrahedron letters ( Tetrahedron Letters), 1989, Vol. 30, No. 13, pages 1609-1612.

  3 '-(trifluoromethyl) [1,1'-biphenyl] -3-ol (3'-(trifluoromethyl) [1,1'-biphenyl] -3-ol) is an example of commercially available 3-iodophenol. From (3-iodophenol) and 3- (trifluoromethyl) phenylboronic acid, the method described in Chemical Reviews, 1995, Vol. 95, pages 2457-2483 (phenylation) Reaction, Suzuki-Miyaura coupling reaction).

  3-hydroxy-4-methylbenzonitrile can be produced, for example, by the method described in Monatshefte fur Chemie, 1957, 88, 228,230.

  Ethyl 3-hydroxy-4-methylbenzoate is a method described in, for example, The Journal of Organic Chemistry, 1961, Vol. 26, pages 1732-1734. Can be manufactured.

  3-hydroxy-4-methylbenzamide (3-hydroxy-4-methylbenzamide) is, for example, a phosphorous sulfur (3-hydroxy-4-methylbenzoic acid) Phosphorus and Sulfur), 1980, Vol. 9, pp. 155-164.

  3,6-dimethyl-2-propylphenol is described in, for example, Journal of Polymer Science, 1948, 3, 448, 452. It can be manufactured by the method.

  2-hydroxy-3,4,6-trimethylbenzaldehyde is, for example, Liebigs Annalen der Chemie, 1906, 347, 379. It can manufacture by the method of description.

  2-hydroxy-3,4,6-trimethylbenzaldehyde O-methyloxime is, for example, Liebigs Annalen der Chemie, 1906. 347, page 379 (synthesis of 2-hydroxy-3,4,6-trimethylbenzaldehyde) and Chemical Pharmaceutical Bulletin, 1988, Vol. 36, No. 8, It can be produced according to the method described on pages 3134-3137.

  2- [1- (methoxymethyl) cyclopropyl] phenol is an example of The Journal of Organic Chemistry, 1942, Vol. 7, 444. From 2-methoxy-1- (2-methoxyphenyl) ethanone, which can be produced by the method described on page -456, The Journal of Organic Chemistry ), 1963, 28, 1128 or Synthetic Communications, 1985, 15, 10, 855-864 (conversion of carbonyl group to olefin, Wittig reaction), and Organic Reactions, 1973, 20, pp. 1-131 or Journal of the American Chemical Society, 1975, 97 3428 or the method described in Tetrahedron Letters, 1998, Vol. 39, pages 8621-8624 (cyclopropyl group construction, Simmons-Smith reaction), and bioscience, biotechnology and biochemistry (Bioscience, Biotechnology, and Biochemistry), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2- (1-methoxycyclopropyl) phenol (2- (1-methoxycyclopropyl) phenol) is described in, for example, The Journal of Organic Chemistry, 1998, Vol. 63, pages 4632-4635. From 1-methoxy-2- (1-methoxyvinyl) benzene, which can be produced by the method, Organic Reactions, 1973, 20, 1-131 Or the method described in Journal of the American Chemical Society, 1975, 97, 3428 or Tetrahedron Letters, 1998, 39, 8621-8624 (cyclopropyl) Group construction, Simmons-Smith reaction), and Bioscience, Biotechnology, and Biochemistry, 1993, 57, 9, 1572-1574 Ku is (conversion to phenol phenyl ether, demethylation reaction) method described in JP-A-11-322755 can be produced according to.

  2- (2-hydroxyphenyl) cyclopropanecarbonitrile is described, for example, in Journal of Medicinal Chemistry, 1988, Vol. 31, No. 1, pages 37-54 From 3- (2-methoxyphenyl) acrylonitrile (Bioscience, Biotechnology, and Biochemistry), 1993, volume 57, 9 No., pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction), and Helvetica Chimica Acta, 1992, Vol. 75, 457 Page (conversion of phenol to phenylmethoxymethyl ether, methoxymethylation reaction) and The Journal of The method described in The Journal of Organic Chemistry, 1973, 38, 1793-1797 or The Journal of Organic Chemistry, 1970, 35, 374-379 (cyclopropane) And a method described in Tetrahedron, 1998, Vol. 54, pages 15861-15869 (conversion of phenylmethoxymethyl ether to phenol, demethoxymethylation reaction).

  2- (2-ethoxycyclopropyl) phenol can be produced, for example, by the method described in Heterocycles, 1998, Vol. 48, No. 7, pages 1373-1394. From [2- (methoxymethoxy) phenyl] methanol, the method described in The Journal of Organic Chemistry, 1981, 46, 5143-5147 ( (Conversion of benzyl alcohol to benzyl chloride) and the method described in Journal of the American Chemical Society, 1973, Vol. 95, No. 2, pages 581-582 (construction of cyclopropyl group) And according to the method described in Tetrahedron, 1998, 54, 15861-15869 (conversion of phenylmethoxymethyl ether to phenol, demethoxymethylation reaction) It can be granulated.

  2- (2,2-difluorocyclopropyl) phenol is, for example, Bulletin de la Societe Chemique de France, 1995, 850 -1- (2,2-difluorovinyl) -2-methoxybenzene (1- (2,2-difluorovinyl) -2-methoxybenzene), which can be produced by the method described on page 856, the Journal of Organic Chemistry (The Journal of Organic Chemistry), 1973, 38, 1793-1797 or The Journal of Organic Chemistry, 1970, 35, 374-379 (cyclopropanation reaction), and According to the method described in Organic Synthesis, Collective Volume, Volume 5, pages 412-414 (conversion of phenylmethyl ether to phenol, demethylation reaction) It can be produced.

  2- (2,2-dichlorocyclopropyl) phenol is described, for example, in Heterocycles, 1998, Vol. 48, No. 7, pages 1373-1394 From 2- (methoxymethoxy) benzaldehyde, which can be produced by the method of The Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications 1985, 15, 10, 855-864 (conversion of carbonyl group to olefin, Wittig reaction) and Synthetic Communications, 1999, 29, 23, 4101 -4112 (conversion of olefins to dichlorocyclopropane) and tetrahedron, 1998, 54, 15861-15869 Conversion to phenol of methoxy methyl ether, can be prepared analogously to demethoxylation methylation reaction).

  2- (2,2-dibromocyclopropyl) phenol (2- (2,2-dibromocyclopropyl) phenol) is synthetic, for example, from commercially available 1-methoxy-2-vinylbenzene. Synthetic Communications, 1999, 29, 23, pages 4101-4112 (using bromoform instead of chloroform, conversion of olefin to dibromocyclopropane), and organic synthesis It can be produced according to the method described in Collective Volume, Vol. 5, pages 412-414 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-isopropenylphenol is, for example, from the commercially available 1- (2-methoxyphenyl) ethanone, The Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications, 1985, 15, 15, 855-864 (conversion of carbonyl group to olefin, Wittig reaction) and bioscience Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (Conversion of phenylmethyl ether to phenol, demethylation) It can be produced according to (Reaction).

  3- (2-hydroxyphenyl) acrylonitrile is described in, for example, Journal of Medicinal Chemistry, 1988, Vol. 31, No. 1, pages 37-54 From 3- (2-methoxyphenyl) acrylonitrile that can be produced by the method, Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, It can be produced according to the method described in pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2-ethynylphenol is described in, for example, Canadian Journal of Chemistry, 1997, Vol. 75, No. 9, pages 1256-1263 from commercially available 1-benzofuran. It can manufacture by the method of.

  Bicyclo [4.2.0] octa-1,3,5-trien-2-ol is an example of The Journal of Organic Chemistry ( The Journal of Organic Chemistry), 1982, 47, 2393-2396, 5-methoxybicyclo [4.2.0] octa-1,3,5-trien-7-one (5-methoxybicyclo) [4.2.0] octa-1,3,5-trien-7-one), Organic Reactions, 1941, Volume 1, page 155 (Clemmensen reduction) and Bioscience Bio Bioscience, Biotechnology, and Biochemistry, 1993, 57, 9, 1572-1574 or JP-A-11-322755 or Organic Synthesis, Collective Volume, Volume 5. , 412-414 (conversion of phenyl methyl ether to phenol, Can be prepared analogously to the methylation reaction).

  2-Bromo-6-chlorophenol is, for example, from commercially available 2-chlorophenol, Tetrahedron Letters, 1998, Vol. 39, 2947. It can be produced according to the method described on page (bromination reaction of phenol).

  3-bromo-2-hydroxybenzonitrile is, for example, a commercially available 2-hydroxybenzonitrile from Tetrahedron Letters, 1998, Vol. 39. , Page 2947 (the bromination reaction of phenol).

  2- (2,2-dichlorocyclopropyl) -6-methylphenol (2- (2,2-dichlorocyclopropyl) -6-methylphenol) is, for example, commercially available 2-hydroxy-3-methylbenzaldehyde (2-hydroxy- 3-methylbenzaldehyde), organic synthesis, collective volume, volume 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction), and the The method described in The Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications, 1985, 15, 10, 855-864 (olefins of carbonyl group) Conversion, Wittig reaction) and the method described in Synthetic Communications, 1999, 29, 23, pages 4101-4112 (Conversion of olefin to dichlorocyclopropane) and organic synthesis, collective volume, Vol. 5, pages 412-414 (conversion of phenylmethyl ether to phenol, demethylation) Can be produced according to the following reaction.

  For example, 2-methyl-6-vinylphenol is an organic synthesis or collective from commercially available 2-hydroxy-3-methylbenzaldehyde. Collective Volume, Vol. 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction) and The Journal of Organic Chemistry, 1963 28, 1128 or Synthetic Communications, 1985, 15, 10, 855-864 (conversion of carbonyl group to olefin, Wittig reaction) and bioscience biotechnology And Biochemistry (Bioscience, Biotechnology, and Biochemistry), 1993, 57, 9, 1572-1574 or JP It can be produced according to the method described in Hei 11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  6-cyclopropyl-3-fluoro-2-methylphenol is, for example, from commercially available 3-fluoro-2-methylbenzaldehyde. , The Journal of Organic Chemistry, 1999, 64, 7921-7928 or Journal of the Chemical Society: Parkin transaction I, 1974, The method described on page 1353 (Baeyer-Villiger oxidation, conversion of aromatic aldehyde to phenol), and the method described in Tetrahedron Letters, 1998, Vol. 39, page 2947 (phenol bromination reaction) ) And Organic Synthesis, Collective Volume, Vol. 4, pages 836-838 Conversion to phenyl methyl ether, methylation reaction) and the method described in Tetrahedron Letters, 2000, 41, 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), And a method described in Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (Conversion of phenylmethyl ether to phenol) , Demethylation reaction).

  5-methyl-1-benzofuran-4-ol can be obtained, for example, by the method described in Tetrahedron, 1995, 51, 4009-4022. Can be produced from methyl 4-hydroxy-1-benzofuran-5-carboxylate, organic synthesis, collective volume, volume 4, 836 -838 (conversion of phenol to phenyl methyl ether, methylation reaction) and The Journal of Organic Chemistry, 2001, Vol. 66, pages 4965-4972. The method (reduction of ester to alcohol) and the method described in Journal of Medicinal Chemistry, 1999, Vol. 42, No. 6, pp. 1007-1017 (benzyl alcohol of benzyl alcohol) Conversion to tansulfonyl ester) and the method described in The Journal of Organic Chemistry, 1969, 34, 3923 or Synthetic Communications, 2001, 31, 9 No. 1373-1382 (reduction reaction of halogenated compounds, tosylate and mesylate) and Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, 1572 -1574 or according to the method described in JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  2- (2-chloro-2-fluorocyclopropyl) phenol is, for example, Heterocycles, 1998, Vol. 48, No. 7, 1373- From 2- (methoxymethoxy) benzaldehyde which can be produced by the method described on page 1394, Journal of Fluorine Chemistry 1983, Vol. 23, page 339-357 ( (Conversion of carbonyl group to chlorofluoroolefin) and The Journal of Organic Chemistry, 1973, 38, 1793-1797 or The Journal of Organic Chemistry, 1970 35, pages 374-379 (cyclopropanation reaction), organic synthesis, collective volume (Col lective Volume), Vol. 5, pp. 412-414, which can be produced according to the method (conversion of phenylmethyl ether to phenol, demethylation reaction).

  3- (benzyloxy) phenol can be obtained, for example, by the method described in The Journal of Organic Chemistry, 1997, Vol. 62, No. 10, pages 3062-3075. Can be manufactured.

  1-methyl-1H-indol-4-ol (1-methyl-1H-indol-4-ol) is, for example, commercially available 4-methoxy-1-methyl-1H-indole (4-methoxy-1-methyl- 1H-indole), the method described in Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755. (Conversion to phenol, demethylation reaction).

  1-methyl-1H-indol-7-ol (Journal of Medicinal Chemistry), 1992, Vol. 35, No. 1, 177- From 7-methoxy-1-methyl-1H-indole, which can be produced by the method described on page 184, Bioscience, Biotechnology, and Biochemistry 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction).

  1- (4-hydroxy-3-methylphenyl) ethanone O-methyloxime is, for example, commercially available 1- (4-hydroxy-3-methyl) Phenyl) ethanone (1- (4-hydroxy-3-methylphenyl) ethanone), according to the method described in Journal of the American Chemical Society, 1986, 108, 6016-6023 Can be manufactured.

  2-isopropenyl-6-methylphenol can be produced, for example, by the method described in Chemische Berichte, 1925, Vol. 58, p. 41. -3-methylphenyl) ethanone (1- (2-hydroxy-3-methylphenyl) ethanone), Organic Synthesis, Collective Volume, Volume 4, pages 836-838 ( Phenol to phenyl methyl ether, methylation reaction) and The Journal of Organic Chemistry, 1963, 28, 1128 or Synthetic Communications, 1985, 15 No. 10, pages 855-864 (conversion of carbonyl group to olefin, Wittig reaction), and bioscience biotechnology Biochemistry (Bioscience, Biotechnology, and Biochemistry), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction) It can be manufactured similarly.

  1,1-dimethyl-5-indanol, for example, Bulletin of the Chemical Society of Japan, 2000, Vol. 73, No. 12, From 5-methoxy-1,1-dimethylindane, which can be produced by the method described on pages 2779-2782, Organic Synthesis, Collective Volume, 5th Volume, pages 412-414, and can be produced according to the method described above (conversion of phenylmethyl ether to phenol, demethylation reaction).

  3-Bromo-6-cyclopropyl-2-methylphenol is more tetra-functional than commercially available 2-methyl-3-nitrophenol. The method described in Tetrahedron Letters, 1998, 39, 2947 (bromination of phenol), Organic Synthesis, Collective Volume, 4, 836-838 (Methods of conversion of phenol to phenyl methyl ether, methylation reaction) and modification of the method described in Organic Synthesis, Collective Volume, Vol. 1, pages 445-447 (Reduction reaction of nitrophenol to aniline; 8.5 equivalents of zinc powder and 25 equivalents of ammonium chloride to nitrophenol, reaction at room temperature) and Tetrahedron Letters (Tetrahedr on Letters), 2000, 41, 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), Organic Synthesis, Collective Volume, 3rd Vol., Methods described on pages 185-187 or The Journal of Organic Chemistry, 1977, vol. 42, pages 242-2430 (conversion of anilines to bromobenzene, Sandmeyer reaction, etc.) ) And the method described in Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (Phenyl methyl ether to phenol) Conversion, demethylation reaction).

  6-Cyclopropyl-2-methyl-3-nitrophenol is more tetrahedral than 2-methyl-3-nitrophenol which is commercially available. The method described in Tetrahedron Letters, 1998, 39, 2947 (bromination of phenol), Organic Synthesis, Collective Volume, 4, 836-838 (Methods of conversion of phenol to phenyl methyl ether, methylation reaction) and modification of the method described in Organic Synthesis, Collective Volume, Vol. 1, pages 445-447 (Reduction reaction of nitrophenol to aniline; 8.5 equivalents of zinc powder and 25 equivalents of ammonium chloride to nitrophenol, reaction at room temperature) and Tetrahedron Letters (Tetrahedr on Letters), 2000, 41, 4251-4255 (construction of cyclopropyl group, Suzuki-Miyaura coupling reaction), and bioscience, biotechnology and biochemistry (Bioscience, Biotechnology, and Biochemistry), 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (conversion of phenylmethyl ether to phenol, demethylation reaction) and tetrahedron, 1987 43, No. 8, pp. 1753-1758 (conversion of aniline derivative to nitrobenzene).

  5-methyl-1,3-dihydro-2-benzofuran-4-ol is an example of Journal of the American Chemical Society. American Chemical Society), 2000, vol. 122, pages 11553-11554.

  2-Fluoro-3,5,6-trimethylphenol is produced, for example, by the method described in Chemische Berichte, 1922, 55, 2384 From 2,3,5-trimethyl-6-nitrophenol (Organic Synthesis), Collective Volume, Vol. 4, pages 836-838 Or the method described in Liebigs Annalen der Chemie, 1957, 608, 128, or organic synthesis (Organic). Synthesis, Collective Volume, Volume 5, pages 829-833 (reduction reaction of nitro group to amino group), and Synthesis, 1989, pages 905-908 Method (fragrance (Conversion of amine to aromatic fluoride) and the method described in Organic Synthesis, Collective Volume, Vol. 5, pp. 412-414 (conversion, dehydration of phenylmethyl ether to phenol) (Methylation reaction).

  2-chloro-3,5,6-trimethylphenol (2-chloro-3,5,6-trimethylphenol) is, for example, from commercially available 2,3,5-trimethylphenol (2,3,5-trimethylphenol) According to a modification of the method described in Tetrahedron Letters, 1998, Vol. 39, p. 2947 (chlorination reaction of phenol; using N-chlorosuccinimide instead of N-bromosuccinimide) Can be manufactured.

  2-iodo-3,5,6-trimethylphenol (2-iodo-3,5,6-trimethylphenol) is, for example, from commercially available 2,3,5-trimethylphenol (2,3,5-trimethylphenol), According to a modification of the method described in Tetrahedron Letters, 1998, Vol. 39, page 2947 (iodination reaction of phenol; using N-iodosuccinimide instead of N-bromosuccinimide) Can be manufactured.

  2-ethyl-3,5,6-trimethylphenol is an example of chemical research in toxicology, 1997, Vol. 10, No. 3, 335. From 1- (2-hydroxy-3,4,6-trimethylphenyl) ethanone, which can be produced by the method described on page 343. It can be synthesized according to the method described in Journal of the American Chemical Society, 1946, vol. 68, page 2487 (reduction reaction of carbonyl group Wolff-Kishner reduction reaction).

  2-isopropenyl-3,5,6-trimethylphenol (Chemical Research in Toxicology), 1997, Vol. 10, No. 3, Organic synthesis from 1- (2-hydroxy-3,4,6-trimethylphenyl) ethanone that can be produced by the method described on pages 335-343 (Organic Synthesis), Collective Volume, Volume 4, pages 836-838 (conversion of phenol to phenyl methyl ether, methylation reaction), and The Journal of Organic Chemistry (The Journal of Organic Chemistry) Organic Chemistry), 1963, 28, 1128 or Synthetic Communications, 1985, 15, 10, 855-864 (conversion of carbonyl group to olefin, Wittig reaction) and the method described in Bioscience, Biotechnology, and Biochemistry, 1993, Vol. 57, No. 9, pages 1572-1574 or JP-A-11-322755 (Conversion to phenol, demethylation reaction).

  1- (2-hydroxy-3,4,6-trimethylphenyl) ethanone (1- (2-hydroxy-3,4,6-trimethylphenyl) ethanone) is, for example, Chemical Research in Toxicology, 1997, Vol. 10, No. 3, pages 335-343.

  2,3,5-trimethyl-6-nitrophenol is produced by the method described in Chemische Berichte, 1922, 55, 2384, for example. it can.

  2,4-dichloro-3,5,6-trimethylphenol (2,4-dichloro-3,5,6-trimethylphenol) is, for example, commercially available 2,3,5-trimethylphenol (2,3,5-trimethylphenol). trimethylphenol), a modification of the method described in Tetrahedron Letters, 1998, 39, 2947 (phenol chlorination reaction; N-chlorosuccinimide instead of N-bromosuccinimide) Use).

  Pentamethylphenol can be produced, for example, by the method described in Journal of the Chemical Society, 1949, page 624.

  2,3,5,6-tetramethylphenol (2,3,5,6-tetramethylphenol) is, for example, a tetrahedron from commercially available 2,3,5-trimethylphenol (2,3,5-trimethylphenol). It can be produced by the method described in Letters (Tetrahedron Letters), 1989, volume 30, page 5215.

  After completion of each reaction step, the target compound in each step can be collected from the reaction mixture according to a conventional method. For example, it can be obtained by neutralizing the reaction mixture as appropriate, or by removing insoluble matters by filtration, adding an organic solvent immiscible with water, washing with water, and distilling off the solvent. If necessary, the obtained target compound can be further purified by a conventional method such as recrystallization, reprecipitation or chromatography.

  The compound (I) of the present invention can be converted into a salt. These salts are included in the present invention as long as they can be used as herbicides for agriculture and horticulture.

  Salts of the compound (I) of the present invention include, for example, alkali metal salts such as lithium, sodium and potassium; alkaline earth metal salts such as magnesium and calcium; aluminum salts; transition metal salts such as iron and copper; ammonium and trimethylammonium Amine salts such as triethylammonium, tetramethylammonium and pyridinium; inorganic mineral salts such as hydrochloride, sulfate and phosphate; or organic acid salts such as formate, acetate, toluenesulfonate and oxalate It can be.

  When the pyridazine derivative becomes the acid component of the salt, the salt can be produced, for example, by mixing the pyridazine derivative and a base in the presence or absence of a solvent and distilling off the solvent.

  The base to be used is not particularly limited as long as it is a base exhibiting a pH of 8 or higher. Examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; sodium carbonate, potassium carbonate and cesium carbonate. Alkali metal carbonates; metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide; alkali metal salts of organic acids such as sodium acetate, potassium acetate, sodium formate, potassium formate; sodium hydride, hydrogenation Alkali metal hydrides such as potassium; alkali metals such as sodium and potassium; aliphatic tertiary amines such as triethylamine, tributylamine and diisopropylethylamine; 1,4-diazabicyclo [2.2.2] octane (DABCO) ), 1,8-diazabicyclo 5.4.0] Aliphatic cyclic tertiary amines such as undec-7-ene (DBU); pyridines such as pyridine, collidine, 4- (N, N-dimethylamino) pyridine; lithium amide, sodium Metal amides such as amides; or organometallic bases such as butyl lithium, s-butyl lithium, lithium diisopropylamide, sodium bis (trimethylsilyl) amide, lithium bis (trimethylsilyl) amide.

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons such as; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide; or a mixed solvent thereof.

  When the pyridazine derivative becomes the base component of the salt, the salt can be produced, for example, by mixing the pyridazine derivative and an acid in the presence or absence of a solvent and distilling off the solvent.

  The acid to be used is not particularly limited as long as it is an acid having a pH of 6 or less, for example, inorganic mineral acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid; It can be an organic acid such as sulfonic acid, succinic acid, benzoic acid.

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butanol; acetone, methyl isobutyl ketone Ketones such as acetonitrile; nitriles such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons such as; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; or a mixed solvent thereof.

  The compound (I) of the present invention can be used for various weeds that are problematic in paddy fields, for example, broad-leaved weeds such as azena, zepe pepper, staghorn, mizohakobe, abnomome, himesohagi, kogi; tamagamitsutsuri, firefly, matsubai, mizugayatsuri, shizui Cyperaceae weeds; and herbicidal weeds such as Urikawa, Omodaka and Heramodaka, and no phytotoxicity to rice.

  The compound (I) of the present invention is a variety of weeds that are problematic in the foliage treatment and soil treatment of field crops, such as black-bellied, chickweed, white-tailed, blue-headed beetle, field moth, nazuna, ichibibi, American stag beetle, field pansy, yamgra, tiger moth, It exhibits herbicidal activity against broad-leaved weeds such as photokenosa, white-bellied morning glory, physalis vulgaris, blue-billed beetle, and long-horned chamomile; It does not show any phytotoxicity that causes problems for major crops such as soybeans.

  The compound (I) of the present invention can be used not only in upland fields and paddy fields but also in orchards, mulberry fields and non-agricultural lands.

  The compound of the present invention is mixed with a carrier and other auxiliary agents (surfactants, etc.) as necessary, and is usually used as a herbicide, for example, powder, coarse powder, granule, granule, water It is prepared and used in a compatibilizer, an aqueous solvent, an emulsion, a liquid agent and the like. As used herein, a carrier refers to a synthetic or natural inorganic or organic substance mixed in a herbicide to help reach the plant of an active ingredient compound or to facilitate storage, transportation or handling of the active ingredient. means.

  Suitable solid carriers are, for example, clays represented by the kaolinite group, montmorillonite group, attapulgite group, etc .; talc, mica, phyllite, pumice, vermiculite, gypsum, dolomite, diatomaceous earth, magnesium lime, phosphorus lime , Zeolite, anhydrous silicic acid, synthetic calcium silicate, kaolin, bentonite, calcium carbonate and other inorganic substances; soy flour, tobacco powder, walnut powder, wheat flour, wood flour, starch, crystalline cellulose, and other plant organic substances; coumarone resin , Petroleum resins, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gums, copal gums, dammar gums, and other synthetic or natural polymer compounds; waxes such as carnauba wax, paraffin wax, beeswax; or urea possible.

  Suitable liquid carriers are, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene; carbon tetrachloride, Chlorinated hydrocarbons such as chloroform, trichloroethylene, monochlorobenzene and chlorotoluene; ethers such as dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone and isophorone; ethyl acetate, amyl acetate, ethylene glycol acetate , Esters such as diethylene glycol acetate, dibutyl maleate and diethyl succinate; methanol, hexanol, ethylene glycol, diethylene glycol, Rohekisanoru, alcohols such as benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, ether alcohols such as diethylene glycol butyl ether; dimethylformamide, polar solvents such as dimethyl sulfoxide; or, may be water.

Surfactants used for emulsification, dispersion, wetting, spreading, bonding, disintegration control, active ingredient stabilization, fluidity improvement, rust prevention, plant absorption promotion, etc. are ionic or nonionic But you can.
Suitable nonionic surfactants include, for example, fatty acid sucrose esters, lauryl alcohol, stearyl alcohol, ethylene oxide polymerization adducts of higher aliphatic alcohols such as oleyl alcohol, and ethylene oxide polymerization of alkylphenols such as isooctylphenol and nonylphenol. Oxidized ethylene polymerized adducts of adducts, alkyl naphthols such as butyl naphthol and octyl naphthol, oxidized ethylene polymerized adducts of higher fatty acids such as palmitic acid, stearic acid and oleic acid, and oxidation of mono- or dialkyl phosphoric acids such as stearyl phosphate Ethylene polymerized adducts, ethylene oxide polymerized adducts of higher aliphatic amines such as dodecylamine and stearamide, higher fatty acid esters of polyhydric alcohols such as sorbitan and ethylene oxide polymerized adducts thereof And it can be exemplified copolymers of ethylene oxide and propylene oxide.

  Suitable anionic surfactants include, for example, alkyl sulfate salts such as sodium lauryl sulfate and oleyl alcohol sulfate amine salt, fatty acid salts such as sodium dioctyl sulfosuccinate, sodium oleate and sodium stearate, isopropyl naphthalene, and the like. Examples thereof include alkylaryl sulfonates such as sodium sulfonate, sodium methylenebisnaphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzene sulfonate.

Examples of suitable cationic surfactants include higher aliphatic amines, quaternary ammonium salts, alkylpyridinium salts, and the like.
Furthermore, the herbicide of the present invention has other components such as gelatin, gum arabic, casein, albumin, glue, sodium alginate, polyvinyl alcohol, carboxymethylcellulose, for the purpose of improving the properties of the preparation and enhancing the biological effect. Polymer compounds such as methylcellulose and hydroxymethylcellulose, thixotropic agents such as sodium polyphosphate and bentonite, and other auxiliary agents can also be contained.

  For example, powders and coarse powders usually contain 0.1 to 25 parts by mass of an active ingredient, and the balance is a solid carrier.

  The wettable powder and the granular wettable powder, for example, usually contain 1 to 90 parts by mass of the active ingredient, and the balance is a solid carrier and a dispersion wetting agent. If necessary, a protective colloid, a thixotropic agent and an antifoaming agent Is added. These preparations are suspended and dispersed in water when stirred in water.

  Granules and fine granules usually contain, for example, 0.1 to 35 parts by mass of an active ingredient, and the balance is mostly a solid carrier. The active ingredient compound is uniformly mixed with the solid carrier, or is fixed or adsorbed uniformly on the surface of the solid carrier, and the particle diameter is usually 0.2 to 1.5 mm.

  The emulsion usually contains, for example, 1 to 70 parts by mass of the active ingredient compound, which contains 5 to 20 parts by mass of an emulsifier, and the remainder is a liquid carrier, and other components such as a rust inhibitor as required. Of supplements are added.

  An aqueous suspension or oil suspension is a suspension or emulsification dispersion of an active ingredient in water or an organic solvent with a high boiling point using an appropriate surfactant. To maintain stability over time.

  The paddy throwing agent is an active ingredient formulated into an appropriate dosage form such as powder, granule, tablet, emulsion, bulk tablet, etc., and if necessary, these are packaged in a water-soluble film or container. In use, several to several hundreds of these are used as they are in the paddy field.

  When the compound of the present invention thus prepared in various dosage forms is treated with soil before or after germination of weeds in paddy fields, for example, 1 g to 1000 g, preferably 10 g to 300 g as an active ingredient per 10 a. By processing, weeds can be controlled effectively.

  As a method for treating the compound of the present invention, it can be usually formulated and treated with soil, foliage or flooding before germination of weeds or within about one month after emergence. Soil treatment includes soil surface treatment, soil admixing treatment, etc., and foliage treatment includes treatment from the top of the plant body, extreme treatment that treats only weeds so as not to adhere to crops, The flooding treatment includes spraying of granules and flowables and irrigation treatment on the water surface.

  Other herbicides can be blended with the herbicide of the present invention in order to broaden the herbicidal spectrum. In particular, pyrazolate, pyrazoxifene, benzophenap, benzobicyclone and the like are effective.

  The herbicide of the present invention can be used by mixing with, for example, plant growth regulators, fungicides, insecticides, acaricides, nematicides or fertilizers.

  Examples, preparation examples and test examples of the present invention will be described below in detail, but the present invention is not limited to these. In the following formulation examples, “%” indicates mass%.

Example 1
6-Chloro-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 128)
(1) 3-Chloro-6- (2-methylphenoxy) pyridazine (Step A-1)
A mixture of 278.7 g (1.87 mol) of 3,6-dichloropyridazine, 202.3 g (1.87 mol) of 2-methylphenol and 259 g (1.87 mol) of potassium carbonate was heated and stirred at 160 ° C. for 6 hours. The reaction mixture was cooled to 70 ° C. and 2 L of ethyl acetate was added. The mixture was washed successively with 1 mol / L aqueous sodium hydroxide solution (4 × 500 mL), water (4 × 500 mL) and saturated brine (50 mL), and dried over anhydrous magnesium sulfate. The solvent was distilled off, and isopropyl ether was added to the residue for crystallization. Crystals were collected by filtration to obtain 234.2 g (1.06 mol, yield 56.7%) of 3-chloro-6- (2-methylphenoxy) pyridazine.

(2) 4,6-Dichloro-3- (2-methylphenoxy) pyridazine (Step A-2)
6-Chloro-3- (2-methylphenoxy) pyridazine (234.2 g, 1.06 mol) obtained by (1) was dissolved in phosphorus oxychloride (1.85 L), and chlorine gas 76.7 g (1.08 mol) was dissolved in this solution. Was blown in over 4 hours. Nitrogen gas was blown into the reaction mixture to remove excess chlorine gas, and then phosphorus oxychloride was distilled off. The residue was dissolved in ethyl acetate (1.5 L), washed successively with water (4 × 500 mL) and saturated brine (200 mL), and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was washed with 500 mL of hexane to obtain 193.1 g of a crude product. The crude product was recrystallized from a mixed solvent of hexane-ethyl acetate (400 mL-240 mL) to obtain 114.4 g (0.448 mol, yield 42.3%) of 4,6-dichloro-3- (2-methylphenoxy) pyridazine. It was.

(3) 6-chloro-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 128, Step A-3)
100.0 g (0.392 mol) of 4,6-dichloro-3- (2-methylphenoxy) pyridazine obtained by (2) was dissolved in 1,4-dioxane (1 L), and sodium hydroxide (purity 96 %, 19.6 g, 0.470 mol) aqueous solution (water 400 mL) and tetrabutylammonium chloride 1.09 g (4.78 mmol) were added and heated to reflux for 4 hours. The reaction mixture was concentrated under reduced pressure to a total volume of about 100 mL. To this residue, an aqueous sodium hydroxide solution (dissolved in 13.1 g of sodium hydroxide in 1.4 L of water) and 500 mL of ethyl acetate were added. The aqueous layer was washed with ethyl acetate (3 × 200 mL), and adjusted to pH 5 by adding concentrated hydrochloric acid under ice cooling. The precipitated solid was collected by suction filtration, washed with 1 L of water, and air-dried. The obtained solid was recrystallized from acetonitrile to obtain 34.4 g (0.145 mol, yield 37.0%) of 6-chloro-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 128). The organic layer was dried over magnesium sulfate and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (YMC GEL, SIL60, 350 / 250mesh, hexane-ethyl acetate, gradient), and 13.5 g of 6-chloro-3,4-bis (2-methylphenoxy) pyridazine was obtained. (0.0414 mol, yield 10.5%).
^{1 H-NMR (200MHz, DMSO} -d6) δppm: 7.35-7.08 (4H, m), 6.84 (1H, br.s), 2.11 (3H, s).
Melting point (° C): 211-213.

(Example 2)
3- (2-Methylphenoxy) -4-pyridazinol (Compound No. 5)
(1) 6-chloro-4-methoxy-3- (2-methylphenoxy) pyridazine (Step A-3)
3.00 g (11.8 mmol) of 4,6-dichloro-3- (2-methylphenoxy) pyridazine obtained in Example 1 (2) was dissolved in methanol (60 mL), and 95% sodium methoxide 1.00 was added to this solution at room temperature. g (17.6 mmol) was added and stirred at 60 ° C. for 4 hours. Further, 1.00 g (17.6 mmol) of 95% sodium methoxide was added and stirred at 60 ° C. for 1 hour, and then left overnight at room temperature. The reaction mixture was concentrated, ethyl acetate was added to the residue, and the mixture was washed successively with water and saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (eluted with hexane: ethyl acetate = 4: 1) to give 6-chloro-4-methoxy-3- ( 2.75 g (11.0 mmol, yield 93.2%) of 2-methylphenoxy) pyridazine was obtained.

(2) 4-Methoxy-3- (2-methylphenoxy) pyridazine (Step N-1)
Dissolve 2.00 g (7.98 mmol) of 6-chloro-4-methoxy-3- (2-methylphenoxy) pyridazine obtained in (1) in methanol (40 mL), and add 0.20 g of 5% palladium-carbon to this solution. The mixture was stirred for 4 hours under a hydrogen atmosphere (1 atm). The reaction mixture was filtered through celite and the filtrate was concentrated. The residue was purified by silica gel column chromatography (eluted with ethyl acetate and then dichloromethane: methanol = 5: 1), and 1.59 g (7.36 mmol, yield 92.2%) of 4-methoxy-3- (2-methylphenoxy) pyridazine Obtained.

(3) 3- (2-Methylphenoxy) -4-pyridazinol (Compound No. 5, Step N-2)
1.08 g (5.00 mmol) of 4-methoxy-3- (2-methylphenoxy) pyridazine obtained by (2), 0.24 g (6.0 mmol) of sodium hydroxide, water (5 mL) and 1,4-dioxane (5 mL) ) Was stirred overnight. The reaction mixture was washed with ethyl acetate, the aqueous layer was acidified with hydrochloric acid and extracted with ethyl acetate. The solvent was distilled off to obtain 0.21 g (10 mmol, yield 20%) of 3- (2-methylphenoxy) -4-pyridazinol (Compound No. 5).
¹ H-NMR (60MHz, DMF-d7) δppm: 8.30 (1H, d, J = 7.2Hz), 7.43-7.00 (5H, m), 6.43 (1H, d, J = 7.2Hz), 2.18 (3H, s).
Melting point (° C): 169-171.

(Example 3)
5-Chloro-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 45)
(1) 4,5-dichloro-3- (2-methylphenoxy) pyridazine
3- (2-Methylphenoxy) pyridazine {Agricultural and Biological Chemistry, 1968, 32, 1376 and Agricultural and Biological Chemistry, 1969, 33 Can be produced by the method described on page 96. } 16.4 g (88.2 mmol) and phosphorus oxychloride (200 mL) were mixed and the mixture was heated to 80 ° C. and 8.5 g (120 mmol) of chlorine gas was introduced. Phosphorous oxychloride was distilled off from the reaction mixture, and the residue was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Merck, 9385, hexane: ethyl acetate gradient) to obtain 6.61 g (25.9) of 4,5-dichloro-3- (2-methylphenoxy) pyridazine. Mmol, 29.4% yield), 8.14 g (36.9 mmol, 41.8% yield) 5-chloro-3- (2-methylphenoxy) pyridazine and 1.20 g 4-chloro-3- (2-methylphenoxy) pyridazine (5.44 mmol, yield 6.17%) was obtained.

(2) 5-chloro-4-methoxy-3- (2-methylphenoxy) pyridazine (Step A-3)
4.10 g (20.0 mmol) of 4,5-dichloro-3- (2-methylphenoxy) pyridazine obtained by (1) and methanol (70 mL) were mixed, and 0.46 g (20 mmol) of sodium was added to this mixture at -8 ° C. ) And stirred at −8 ° C. for 30 minutes and under ice cooling for 8 hours 30 minutes. Ice-cold water was added to the reaction mixture, and the mixture was adjusted to pH ₃ with hydrochloric acid and extracted with ethyl acetate. The organic layers were combined, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Merck, 9385, hexane: ethyl acetate gradient) to obtain 1.15 g of 5-chloro-4-methoxy-3- (2-methylphenoxy) pyridazine. (4.58 mmol, yield 22.9%) and 4.27 g (13.0 mmol, yield 65%) of 4-chloro-5-methoxy-3- (2-methylphenoxy) pyridazine were obtained.

(3) 5-chloro-3- (2-methylphenoxy) -4-pyridazinol (compound number 45, step A-4, etc.)
750 mg (2.99 mmol) of 5-chloro-4-methoxy-3- (2-methylphenoxy) pyridazine obtained by (2), 156 mg (3.9 mmol) of sodium hydroxide, 1,4-dioxane (5 mL) and water ( 10 mL) and the mixture was heated to reflux with stirring for 2 hours 30 minutes. The reaction mixture was poured into ice-cold water and acidified with hydrochloric acid. The precipitated solid was collected by filtration and washed with water and then hexane. 525 mg (2.22 mmol, yield 74.2%) of 5-chloro-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 45) was obtained.
¹ H-NMR (60 MHz, DMF-d7) δ ppm: 8.68 (1H, s), 7.38-6.80 (4H, m), 5.32 (1H, br.s), 2.13 (3H, s).
Melting point (° C): 238-243.

(Example 4)
5-chloro-3- (2-methylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 66, Step I-1)
5-Chloro-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 45) 237 mg (1.00 mmol) obtained in Example 3 and acetonitrile (8 mL) were mixed, and this mixture was stirred under 1, 4-Diazabicyclo [2.2.2] octane 112 mg (1.00 mmol) was added, then 4-methylbenzenesulfonyl chloride 191 mg (1.00 mmol) was added, and the mixture was stirred at room temperature for 1 hour 30 minutes. Water was added to the reaction mixture, acidified with hydrochloric acid, and extracted with ethyl acetate. The organic layers were combined, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-100, hexane: ethyl acetate = 3: 1) to give 5-chloro-3- (2-methylphenoxy) -4-pyridazinyl 4- 379 mg (0.969 mmol, yield 96.9%) of methylbenzenesulfonate (Compound No. 66) was obtained.
^{1 H-NMR (60MHz, CDCl} 3) δppm: 8.80 (1H, s), 7.77-6.75 (8H, m), 2.47 (3H, s), 1.98 (3H, s).
Melting point (° C): 140-143.

(Example 5)
6-chloro-3- (2-methylphenoxy) -4-pyridazinol 1-oxide (Compound No. 129, Step F-1)
135 mg (0.572 mmol) of 6-chloro-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 128) obtained according to Example 1 and methylene chloride (6 mL) were mixed, and this mixture was mixed with m-chloro. 247 mg of perbenzoic acid (purity 80%, 1.14 mmol) was added, and the mixture was stirred with heating under reflux for 16 hours. After standing at room temperature for 2 days, the reaction mixture was poured into a saturated aqueous sodium sulfite solution and washed with methylene chloride. The aqueous layer was acidified with hydrochloric acid, extracted with methylene chloride, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (eluting with YMC GEL, SIL60, 350 / 250mesh, ethyl acetate) to give 6-chloro-3- (2-methylphenoxy) -4- 32.6 mg (0.129 mmol, yield 22.6%) of pyridazinol 1-oxide (Compound No. 129) was obtained.
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.34 (1H, s), 7.34-7.10 (4H, m), 2.20 (3H, s).
Melting point (° C): 194-196.

(Example 6)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol (Compound No. 139)
(1) Mixture of 6-chloro-3- (2-cyclopropylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-cyclopropylphenoxy) pyridazine 1-oxide (step B-2)
25.3 g (189 mmol) of 2-cyclopropylphenol, 1,4-dioxane (120 mL) and dimethyl sulfoxide (120 mL) were mixed, and 23.2 g (207 mmol) of potassium tert-butoxide was added to this mixture under ice cooling. Stir for 10 minutes. To this mixture, 32.0 g (194 mmol) of 3,6-dichloropyridazine 1-oxide, which is a known compound, was added and left at room temperature for 5 days. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient) to give 6-chloro-3- (2-cyclopropylphenoxy) pyridazine 1-oxide and 3-chloro-6- ( 43.3 g (165 mmol, yield 87.3%) of a mixture of 2-cyclopropylphenoxy) pyridazine 1-oxide was obtained.

(2) 4,6-Dichloro-3- (2-cyclopropylphenoxy) pyridazine (Step B-3)
43.3 g (165 mmol) of a mixture of 6-chloro-3- (2-cyclopropylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-cyclopropylphenoxy) pyridazine 1-oxide obtained by (1) , Chloroform (30 mL) and phosphorus oxychloride 18.0 mL (194 mmol) were mixed and the mixture was heated to 60 ° C. to dissolve. This was stirred at room temperature overnight and concentrated. The residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient) to obtain 32.5 g (116 mmol, yield 70.3%) of 4,6-dichloro-3- (2-cyclopropylphenoxy) pyridazine.

(3) 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol (Compound No. 139, Step B-4)
Dissolve 3,2.5 g (116 mmol) of 4,6-dichloro-3- (2-cyclopropylphenoxy) pyridazine obtained in (2) in dimethyl sulfoxide (500 mL) and add 84 mL of 10% (W / V) aqueous sodium hydroxide solution. (210 mmol) was added and stirred at room temperature overnight. The reaction mixture was poured into ice-cold 1 mol / L aqueous sodium hydroxide and washed with ether. The aqueous layer was acidified with hydrochloric acid, and the precipitated solid was collected by filtration and washed with water. Acetonitrile was added to the obtained solid and heated. Allowed to cool overnight and the crystals were collected by filtration (14.04 g). The filtrate was concentrated and the residue was recrystallized from ethanol to obtain 2.64 g of crystals. These crystals were combined to obtain 16.7 g (63.5 mmol, yield 54.7%) of 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol (Compound No. 139).
^{1 H-NMR (200MHz, DMSO} -d6) δppm: 7.28-6.97 (4H, m), 6.82 (1H, s), 1.89-1.77 (1H, m), 0.87-0.73 (2H, m), 0.73-0.58 (2H, m).
Melting point (° C): 229-231.

(Example 7)
6-Chloro-3- [2- (1-fluorocyclopropyl) phenoxy] -4-pyridazinol (Compound No. 140)
(1) 2- (Methoxymethoxy) benzaldehyde Commercial salicylaldehyde (5.01 g, 41.1 mmol) was dissolved in N, N-dimethylformamide (20 mL), and this solution was dissolved in ice-cooled 60% sodium hydride (1.80 g, 45.0 mmol). After stirring for 10 minutes under ice cooling, 3.43 mL (45.2 mmol) of chloro (methoxy) methane was slowly added dropwise and stirred for 1 hour under ice cooling. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 6.54 g (39.4 mmol, yield 95.9) of 2- (methoxymethoxy) benzaldehyde. %)Obtained.

(2) 1- (methoxymethoxy) -2-vinylbenzene In a nitrogen atmosphere, 877 mg (21.9 mmol) of 60% sodium hydride washed with hexane was suspended in dry dimethyl sulfoxide (10 mL). After stirring with heating at 85 ° C. for 30 minutes, the solution was returned to room temperature and further a solution of 7.83 g (21.9 mmol) of methyl (triphenyl) phosphonium bromide in dry dimethyl sulfoxide (20 mL) was slowly added dropwise under ice cooling. After stirring at room temperature for 15 minutes, a solution of 3.02 g (18.2 mmol) of 2- (methoxymethoxy) benzaldehyde obtained in (1) in dry dimethyl sulfoxide (9 mL) was added dropwise and stirred at room temperature for 15 minutes. The reaction mixture was poured into water and extracted with diethyl ether. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 2.54 g (15.5 mmol) of 1- (methoxymethoxy) -2-vinylbenzene. Yield 85.2%).

(3) 1- (2-Bromo-1-fluoroethyl) -2- (methoxymethoxy) benzene
N, N, N-triethylamine Hydrofluoric acid (MEC-82) 1.47 g (9.13 mmol) in methylene chloride (10 mL) was added to 1- (methoxymethoxy) -2-vinylbenzene obtained in (2). A solution of 1.00 g (6.09 mmol) of methylene chloride (5 mL) was added dropwise, and 1.19 g (6.70 mmol) of N-bromosuccinimide was added under ice cooling. After stirring for 2 hours under ice cooling, the mixture was warmed to room temperature and further stirred for 30 minutes. The reaction mixture was poured into saturated aqueous sodium hydrogen carbonate solution and extracted with methylene chloride. The organic layer was washed successively with dilute hydrochloric acid, water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was subjected to preparative thin layer chromatography (development with 4: 1 MERCK 1.05717 ethyl acetate: hexane = 4: 1), and then preparative thin layer chromatography (MERCK) 1.05744 4 sheets were used and developed with ethyl acetate: hexane = 10: 1) to obtain 1.24 g of a crude product of 1- (2-bromo-1-fluoroethyl) -2- (methoxymethoxy) benzene.

(4) 1- (1-Fluorovinyl) -2- (methoxymethoxy) benzene 736.2 mg (11.15 mmol) of 85% potassium hydroxide was added to dry dimethyl sulfoxide (10 mL), and the mixture was stirred at room temperature for 1 hour and 30 minutes. A solution of 978.2 mg of a crude product of 1- (2-bromo-1-fluoroethyl) -2- (methoxymethoxy) benzene obtained in 1) in dry dimethyl sulfoxide (6 mL) was added dropwise and stirred for 2 hours, then 60 The mixture was stirred with heating at ° C for 2 hours. The reaction mixture was poured into water and extracted with hexane. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 632.7 mg of a crude product of 1- (1-fluorovinyl) -2- (methoxymethoxy) benzene.

(5) 1- (1-Fluorocyclopropyl) -2- (methoxymethoxy) benzene In a nitrogen atmosphere, put dry diethyl ether (5 mL) into a dry flask, and add 1.97 mL (1.97 mmol) of diethyl zinc (1M hexane solution). Then, a solution of 143.6 mg of the crude product of 1- (1-fluorovinyl) -2- (methoxymethoxy) benzene obtained in (4) in dry diethyl ether (3 mL) was added dropwise. After stirring at room temperature for 10 minutes, 0.19 mL (2.3 mmol) of diiodomethane was added dropwise, and the mixture was heated to reflux for 4 hours and 30 minutes. The reaction mixture was poured into a saturated aqueous ammonium chloride solution, a saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was stirred for a while and extracted with diethyl ether. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate: hexane = 4: 1), and 1- (1- 80.5 mg of a crude product of fluorocyclopropyl) -2- (methoxymethoxy) benzene was obtained.

(6) 2- (1-Fluorocyclopropyl) phenol 1- (1-Fluorocyclopropyl) -2- (methoxymethoxy) benzene obtained by (5) in a solution of 43.8 mg of methanol (6 mL) Concentrated hydrochloric acid (0.3 mL) was added dropwise, and the mixture was stirred with heating at 60 ° C. for 3 hr. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 42.8 mg of a crude product of 2- (1-fluorocyclopropyl) phenol.

(7) 6-chloro-3- [2- (1-fluorocyclopropyl) phenoxy] pyridazine 1-oxide (step B-2)
42.8 mg of the crude product of 2- (1-fluorocyclopropyl) phenol obtained in (6) was dissolved in a mixed solvent of 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL). -Butoxide 34.7 mg (0.310 mmol) was added, followed by 3,6-dichloropyridazine 1-oxide 46.4 mg (0.281 mmol) and stirred at room temperature overnight. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 2 plates used, developed with ethyl acetate: hexane = 2: 1), and 6-chloro-3 28.0 mg (0.0996 mmol) of-[2- (1-fluorocyclopropyl) phenoxy] pyridazine 1-oxide was obtained.

(8) 4,6-Dichloro-3- [2- (1-fluorocyclopropyl) phenoxy] pyridazine (Step B-3)
6-Chloro-3- [2- (1-fluorocyclopropyl) phenoxy] pyridazine 1-oxide 28.0 mg (0.0996 mmol) obtained in (7) was dissolved in phosphorus oxychloride (1 mL), and this solution was dissolved at room temperature. Stir overnight. Water and methylene chloride were added to the reaction solution, and the mixture was stirred for 30 minutes and extracted with methylene chloride. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (MERCK, 1.05744, used in 2 plates, developed with ethyl acetate: hexane = 2: 1), and 4,6-dichloro There was obtained 5.1 mg (0.017 mmol, 17% yield) of -3- [2- (1-fluorocyclopropyl) phenoxy] pyridazine.

(9) 6-Chloro-3- [2- (1-fluorocyclopropyl) phenoxy] -4-pyridazinol (Compound No. 140, Step B-4)
5.1 mg (0.017 mmol) of 4,6-dichloro-3- [2- (1-fluorocyclopropyl) phenoxy] pyridazine obtained by (8) was added to 1,4-dioxane (2 mL) and dimethyl sulfoxide (2 mL). This was dissolved in a mixed solvent, and 0.1 mL of a 2 mol / L aqueous sodium hydroxide solution was added to this solution, followed by stirring overnight at room temperature. The reaction mixture was poured into water, adjusted to pH 2 with dilute hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (MERCK, 1.05744, 1 plate used, developed with ethyl acetate), and 6-chloro-3- [2- (1 There was obtained 4.0 mg (0.014 mmol, yield 82%) of -fluorocyclopropyl) phenoxy] -4-pyridazinol (Compound No. 140).
¹ H-NMR (200MHz, CD3OD) δppm: 7.57-7.52 (1H, m), 7.39-7.31 (1H, m), 7.22-7.13 (1H, m), 7.00 (1H, d, J = 8.1Hz), 6.48 (1H, s), 1.32-1.22 (2H, m), 1.16-1.08 (2H, m).
Melting point (° C): 152-157.

(Example 8)
6-Chloro-3- {2- [1- (ethylsulfanyl) cyclopropyl] phenoxy} -4-pyridazinol (Compound No. 207)
(1) 1-methoxy-2-vinylbenzene Under a nitrogen atmosphere, 1.92 g (48.0 mmol) of 60% sodium hydride washed with hexane was suspended in dry dimethyl sulfoxide (15 mL). After heating and stirring for 30 minutes, the solution was returned to room temperature and further a solution of 17.2 g (48.2 mmol) of methyl (triphenyl) phosphonium bromide in dry dimethyl sulfoxide (35 mL) was slowly added dropwise under ice cooling. After stirring at room temperature for 20 minutes, 4.83 mL (40.1 mmol) of commercially available 2-methoxybenzaldehyde was added dropwise, stirred at room temperature for 1 hour, and then stirred at 65 ° C. for 3 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 3.29 g (24.5 mmol, yield) of 1-methoxy-2-vinylbenzene. 61.1%).

(2) 1- (2-Bromo-1-fluoroethyl) -2-methoxybenzene
To a solution of 3.60 g (22.4 mmol) of N, N, N-triethylamine hydrofluoric acid (MEC-82) in methylene chloride (20 mL) was added 2.01 g of 1-methoxy-2-vinylbenzene obtained in (1) ( A solution of 15.0 mmol) in methylene chloride (6 mL) was added dropwise, and 2.92 g (16.4 mmol) of N-bromosuccinimide was added under ice cooling. After stirring for 25 minutes under ice cooling, the mixture was warmed to room temperature and further stirred for 1 hour 30 minutes. The reaction mixture was poured into saturated aqueous sodium hydrogen carbonate solution and extracted with methylene chloride. The organic layer was washed successively with dilute hydrochloric acid, water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 1- (2-bromo-1-fluoroethyl) -2-methoxybenzene. 1.39 g of crude product of was obtained.

(3) 1- (1-Fluorovinyl) -2-methoxybenzene To dry dimethyl sulfoxide (10 mL), 1.28 g (19.4 mmol) of 85% potassium hydroxide was added and stirred at room temperature for 30 minutes. A solution of 1.50 g of the crude product of 1- (2-bromo-1-fluoroethyl) -2-methoxybenzene in dry dimethyl sulfoxide (10 mL) was added dropwise and stirred overnight. The reaction mixture was poured into water and extracted with hexane. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give a crude product of 1- (1-fluorovinyl) -2-methoxybenzene. 1.21 g was obtained.

(4) 1- (1-Fluorocyclopropyl) -2-methoxybenzene In a nitrogen atmosphere, dry diethyl ether (8 mL) is placed in a dry flask, and diethyl zinc (1 mol / L hexane solution) 19.88 mL (19.88 mmol) is added dropwise. Then, a solution of 1.21 g of the crude product of 1- (1-fluorovinyl) -2-methoxybenzene obtained in (3) in dry diethyl ether (8 mL) was added dropwise. After stirring at room temperature for 10 minutes, 1.92 mL (23.86 mmol) of diiodomethane was added dropwise and heated to reflux for 6 hours. After standing overnight at room temperature, the reaction mixture was poured into saturated aqueous ammonium chloride solution, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was stirred for a while and extracted with diethyl ether. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to produce crude 1- (1-fluorocyclopropyl) -2-methoxybenzene. 1.06 g of product was obtained.

(5) 2- [1- (Ethylsulfanyl) cyclopropyl] phenol Under nitrogen atmosphere, 765.3 mg (19.1 mmol) of 60% sodium hydride was suspended in dry N, N-dimethylformamide (8 mL). 1.46 mL (19.8 mmol) of ethanethiol was slowly added dropwise thereto and stirred for 15 minutes, and then 1.06 g of a crude product of 1- (1-fluorocyclopropyl) -2-methoxybenzene obtained in (4) was dried with N, N-dimethylformamide (5 mL) solution was added dropwise, and the mixture was stirred with heating at 160 ° C. for 5 hr. After allowing to cool, a 1 mol / L aqueous potassium hydroxide solution and diethyl ether were added to the reaction mixture. The aqueous layer was separated and washed with diethyl ether. Dilute hydrochloric acid was added to adjust to pH 2 and extracted with diethyl ether. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give a crude product of 2- [1- (ethylsulfanyl) cyclopropyl] phenol 0.26 g was obtained.

(6) 6-chloro-3- {2- [1- (ethylsulfanyl) cyclopropyl] phenoxy} pyridazine 1-oxide (step B-2)
Dissolve 0.26 g of the crude 2- [1- (ethylsulfanyl) cyclopropyl] phenol product obtained in (5) in a mixed solvent of 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL). Then, 265.5 mg (2.37 mmol) of potassium tert-butoxide was added, and then 390.3 mg (2.37 mmol) of 3,6-dichloropyridazine 1-oxide was added, followed by stirring at room temperature overnight. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate: hexane = 2: 1) to give 6-chloro-3 138.4 mg (0.428 mmol) of-{2- [1- (ethylsulfanyl) cyclopropyl] phenoxy} pyridazine 1-oxide was obtained.

(7) 4,6-Dichloro-3- {2- [1- (ethylsulfanyl) cyclopropyl] phenoxy} pyridazine (Step B-3)
138.4 mg (0.428 mmol) of 6-chloro-3- {2- [1- (ethylsulfanyl) cyclopropyl] phenoxy} pyridazine 1-oxide obtained by (6) was dissolved in phosphorus oxychloride (1 mL), and this solution Was stirred overnight at room temperature. Water and methylene chloride were added to the reaction solution, and the mixture was stirred for 30 minutes and extracted with methylene chloride. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (MERCK, using 1.05744 2 plates, developed with ethyl acetate: hexane = 4: 1), and 4,6-dichloro- 94.4 mg (0.277 mmol, yield 64.7%) of 3- {2- [1- (ethylsulfanyl) cyclopropyl] phenoxy} pyridazine was obtained.

(8) 6-chloro-3- {2- [1- (ethylsulfanyl) cyclopropyl] phenoxy} -4-pyridazinol (Compound No. 207, Step B-4)
9,4-Dichloro-3- {2- [1- (ethylsulfanyl) cyclopropyl] phenoxy} pyridazine 94.4 mg (0.277 mmol) obtained by (7) was added to 1,4-dioxane (1 mL) and dimethyl sulfoxide ( 1 mL) was dissolved in a mixed solvent, and 0.69 mL (1.38 mmol) of a 2 mol / L aqueous sodium hydroxide solution was added to the solution, followed by stirring overnight at room temperature. Water and ethyl acetate were added to the reaction solution, and the aqueous layer was separated and washed with ethyl acetate. Dilute hydrochloric acid was added to adjust to pH 2 and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, used in 2 plates, developed with ethyl acetate) to give 6-chloro-3- {2- [1 47.5 mg (0.147 mmol, 53.1% yield) of-(ethylsulfanyl) cyclopropyl] phenoxy} -4-pyridazinol (Compound No. 207) was obtained.
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.45-7.07 (4H, m), 6.69 (1H, s), 2.46 (2H, q, J = 7.3 Hz), 1.28-1.02 (9H, m).
Melting point (° C): 88.

Example 9
6-Chloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] -4-pyridazinol (Compound No. 265)
(1) 1- (2,2-Dichlorocyclopropyl) -2- (methoxymethoxy) benzene 305 mg (1.86 mmol) of 1- (methoxymethoxy) -2-vinylbenzene obtained in Example 7 (2) was mixed with chloroform. Into this solution, 5 mL (63 mmol) of 50% aqueous sodium hydroxide solution was added dropwise, followed by addition of 54.1 mg (0.237 mmol) of benzyl (triethyl) ammonium chloride and stirred overnight at room temperature. The reaction mixture was poured into water and extracted with chloroform. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, using 3 plates, developed with ethyl acetate: hexane = 1: 2), and 1- (2, 387 mg (1.57 mmol, yield 84.4%) of 2-dichlorocyclopropyl) -2- (methoxymethoxy) benzene was obtained.

(2) 2- (2,2-Dichlorocyclopropyl) phenol 1- (2,2-Dichlorocyclopropyl) -2- (methoxymethoxy) benzene 203 mg (0.822 mmol) obtained from (1) was added to methanol (5 mL In this solution, 0.1 mL of concentrated hydrochloric acid was added and stirred at 60 ° C. for 2 hours. After confirming the disappearance of the raw materials by thin layer chromatography, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 194 mg of a crude product of 2- (2,2-dichlorocyclopropyl) phenol.

(3) 6-chloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] pyridazine 1-oxide (step B-2)
The crude product of 2- (2,2-dichlorocyclopropyl) phenol obtained in (2), 194 mg, 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL) were mixed, and this mixture was cooled with ice. 118 mg (1.05 mmol) of potassium tert-butoxide was added, and the mixture was stirred for 10 minutes. Thereto was added 157 mg (0.952 mmol) of 3,6-dichloropyridazine 1-oxide, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate: hexane = 1: 2), and 6-chloro-3- [2 268 mg of a crude product of-(2,2-dichlorocyclopropyl) phenoxy] pyridazine 1-oxide was obtained.

(4) 4,6-Dichloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] pyridazine (Step B-3)
268 mg of the crude product of 6-chloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] pyridazine 1-oxide obtained by (3) and 3 mL of phosphorus oxychloride were mixed, and this mixture was mixed at room temperature. Stir overnight. Water and dichloromethane were added to the reaction mixture and stirred for 30 minutes. The mixture was separated, and the organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, using 3 plates, developed with ethyl acetate: hexane = 1: 2), and 4,6-dichloro-3- 162 mg (0.463 mmol, 3-step yield from 1- (2,2-dichlorocyclopropyl) -2- (methoxymethoxy) benzene, 56.3%) [2- (2,2-dichlorocyclopropyl) phenoxy] pyridazine Obtained.

(5) 6-chloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] -4-pyridazinol (Compound No. 265, Step B-4)
4,6-dichloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] pyridazine obtained by (4) 162 mg (0.463 mmol), 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL) To this mixture, 1.15 mL (2.30 mmol) of 2 mol / L aqueous sodium hydroxide solution was added and stirred overnight at room temperature. The reaction mixture was poured into water and acidified with dilute hydrochloric acid. This mixture was extracted with dichloromethane. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate) to give 6-chloro-3- [2- (2,2- 50.0 mg (0.151 mmol, yield 32.6%) of dichlorocyclopropyl) phenoxy] -4-pyridazinol (Compound No. 265) was obtained.
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.55-7.15 (4H, m), 6.69 (1H, s), 2.90 (1H, dd, J = 10.6, 8.8 Hz), 2.07-1.89 (2H, m).
Melting point (° C): 158-163.

(Example 10)
6-Chloro-3- (2-hydroxyphenoxy) -4-pyridazinol (Compound No. 384)
(1) 3-Chloro [1,4] benzodioxino [2,3-c] pyridazine (Step O-1)
3.49 g (80.0 mmol) of 55% sodium hydride was suspended in 1,4-dioxane (30 mL), and a solution of 4.40 g (40 mmol) of pyrocatechol in 1,4-dioxane (30 mL) and then 3,4,6-trichloropyridazine {Described in The Journal of Organic Chemistry, 1963, 28, 218-221. } A solution of 7.30 g (39.9 mmol) of 1,4-dioxane (30 mL) was added and heated to reflux for 2 hours. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed sequentially with 1 mol / L sodium hydroxide and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from methyl isobutyl ketone to obtain 6.15 g (27.8 mmol, yield 69.7%) of 3-chloro [1,4] benzodioxino [2,3-c] pyridazine.

(2) 6-chloro-3- (2-hydroxyphenoxy) -4-pyridazinol (Compound No. 384, Step O-2)
3-Chloro [1,4] benzodioxino [2,3-c] pyridazine obtained by (1) 5.52 g (25.0 mmol), 1.30 g of 96% sodium hydroxide (31.2 mmol), dimethyl sulfoxide (55 mL) and water (15 mL) of the mixture was stirred at 90 ° C. for 1 hour. The reaction mixture was poured into ice-cold water, acidified with hydrochloric acid, and extracted with ethyl acetate. The solvent was distilled off, and the residue was washed with isopropyl ether to obtain 4.90 g (20.5 mmol, yield 82.0%) of 6-chloro-3- (2-hydroxyphenoxy) -4-pyridazinol (Compound No. 384). .
¹ H-NMR (60 MHz, DMF-d7) δ ppm: 7.25-6.40 (5H, m).
Melting point (° C): 216-219.

(Example 11)
6-Chloro-3- [2- (methylsulfinyl) phenoxy] -4-pyridazinol (Compound No. 404)
(1) 6-chloro-3- [2- (methylsulfanyl) phenoxy] pyridazine 1-oxide (step B-2)
454 mg (3.24 mmol) of 2- (methylsulfanyl) phenol is dissolved in a mixed solvent of 1,4-dioxane (5 mL) and dimethyl sulfoxide (5 mL), and 519 mg (4.63 mmol) of potassium tert-butoxide is added to this solution for 35 minutes. Stir. To this mixture, 424 mg (2.57 mmol) of 3,6-dichloropyridazine 1-oxide was added and stirred for 3 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel chromatography (eluted with Wakogel C-100, hexane: ethyl acetate = 3: 1) to give 6-chloro-3- [2- (methylsulfanyl) phenoxy. There was obtained 391 mg (1.46 mmol, yield 56.8%) of pyridazine 1-oxide.

(2) 4,6-Dichloro-3- [2- (methylsulfanyl) phenoxy] pyridazine (Step B-3)
6-Chloro-3- [2- (methylsulfanyl) phenoxy] pyridazine 1-oxide 288 mg (1.07 mmol) and phosphorus oxychloride 1.00 mL (10.8 mmol) obtained by (1) were mixed and this mixture was mixed overnight. Stir. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (Merck, 1.05744, developed with hexane / ethyl acetate = 3/1), and 4,6-dichloro-3- [2- ( 118 mg (0.411 mmol, 38.4% yield) of methylsulfanyl) phenoxy] pyridazine were obtained.

(3) 4,6-dichloro-3- [2- (methylsulfinyl) phenoxy] pyridazine 118 mg (0.411 mmol) of 4,6-dichloro-3- [2- (methylsulfanyl) phenoxy] pyridazine obtained from (2) ) Was dissolved in 1,2-dichloroethane (4 mL), 96.3 mg (purity 80%, 0.446 mmol) of m-chloroperbenzoic acid was added to this solution, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into a 10% aqueous sodium sulfite solution, extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (Merck, 1.05744, hexane: ethyl acetate = 1: 1, then 3: 1, then developed 1: 1). 21.1 mg (0.0696 mmol, yield 16.9%) of 6-dichloro-3- [2- (methylsulfinyl) phenoxy] pyridazine was obtained.

(4) 6-chloro-3- [2- (methylsulfinyl) phenoxy] -4-pyridazinol (Compound No. 404, Step B-4)
21.1 mg (0.0696 mmol) of 4,6-dichloro-3- [2- (methylsulfinyl) phenoxy] pyridazine obtained by (3) was dissolved in 1,4-dioxane (0.5 mL), and 3 mol / 0.12 mL (0.36 mmol) of L sodium hydroxide aqueous solution was added and stirred for 45 minutes. Dimethyl sulfoxide (0.5 mL) was added to the mixture, stirred for 3 hours, poured into 10% hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (Merck, 1.05744, chloroform: methanol = 10: 1) to give 6-chloro-3- [2- (methylsulfinyl) 2.1 mg (0.0074 mmol, 11% yield) of phenoxy] -4-pyridazinol (Compound No. 404) was obtained.
¹ H-NMR (200MHz, CD3OD) δppm: 7.90-7.84 (1H, m), 7.60-7.42 (2H, m), 7.14 (1H, dd, J = 9.2, 1.1Hz), 6.62 (1H, s), 2.92 (3H, s).
Physical properties: amorphous.

Example 12
6-Chloro-3- [2- (methylsulfonyl) phenoxy] -4-pyridazinol (Compound No. 406)
(1) 6-chloro-3- [2- (methylsulfonyl) phenoxy] pyridazine 1-oxide 6-chloro-3- [2- (methylsulfanyl) phenoxy] pyridazine 1-oxide obtained in Example 11 (1) Oxide 208 mg (0.774 mmol) was dissolved in 1,2-dichloroethane (5 mL), 80% m-chloroperbenzoic acid 829 mg (3.84 mmol) was added to the solution, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was poured into 10% aqueous sodium sulfite and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (Merck, 1.05744, developed with hexane: ethyl acetate = 1: 1) to give 6-chloro-3- [2- 132 mg (0.439 mmol, 56.7% yield) of (methylsulfonyl) phenoxy] pyridazine 1-oxide were obtained.

(2) 4,6-Dichloro-3- [2- (methylsulfonyl) phenoxy] pyridazine (Step B-3)
6-Chloro-3- [2- (methylsulfonyl) phenoxy] pyridazine 1-oxide 111 mg (0.369 mmol) obtained in (1) and 1.00 mL (10.8 mmol) phosphorus oxychloride were mixed and the mixture was allowed to stand overnight. Stir. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with saturated sodium bicarbonate and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (Merck, 1.05744, developed with hexane: ethyl acetate = 1: 1), and 4,6-dichloro-3- [2- ( 70.8 mg (0.222 mmol, 60.2% yield) of methylsulfonyl) phenoxy] pyridazine was obtained.

(3) 6-chloro-3- [2- (methylsulfonyl) phenoxy] -4-pyridazinol (Compound No. 406, Step B-4)
70.8 mg (0.222 mmol) of 4,6-dichloro-3- [2- (methylsulfonyl) phenoxy] pyridazine obtained by (2) was dissolved in 1,4-dioxane (2.0 mL), and 3 mol / L Sodium hydroxide aqueous solution 0.45mL (1.4mmol) was added and stirred for 30 minutes. Dimethyl sulfoxide (2.0 mL) was added to the mixture, and the mixture was stirred overnight, poured into water and washed with a mixed solvent of hexane-ethyl acetate. The aqueous layer was acidified with 10% hydrochloric acid and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (Merck, 1.05744, developed with chloroform: methanol = 10: 1) to give 6-chloro-3- [2- ( 18.0 mg (0.0599 mmol, yield 27.0%) of methylsulfonyl) phenoxy] -4-pyridazinol (Compound No. 406) was obtained.
¹ H-NMR (200MHz, CD3OD) δppm: 8.00 (1H, dd, J = 7.7, 1.8Hz), 7.71 (1H, ddd, J = 7.7, 7.7, 1.8Hz), 7.43 (1H, ddd, J = 7.7 , 7.7, 1.1Hz), 7.32 (1H, br.d, J = 7.7Hz), 6.62 (1H, s), 3.36 (3H, s).
Physical properties: amorphous.

(Example 13)
6-chloro-3- (2-cyclopropyl-3-methoxyphenoxy) -4-pyridazinol (Compound No. 478)
(1) 6-chloro-3- (2-cyclopropyl-3-methoxyphenoxy) -4-methoxypyridazine (Step D-1)
190 mg (1.16 mmol) of 2-cyclopropyl-3-methoxyphenol was dissolved in a mixed solvent of 1,4-dioxane (2.5 mL) and dimethyl sulfoxide (2.5 mL), and 146 mg (1.30 mmol) of potassium tert-butoxide was added to this solution. In addition, the mixture was stirred for 10 minutes. To this mixture, 170 mg (0.950 mmol) of 3,6-dichloro-4-methoxypyridazine was added and left overnight. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 6-chloro-3- (2-cyclopropyl-3-methoxyphenoxy)- 90.1 mg (0.293 mmol, yield 30.8%) 4-methoxypyridazine and 114 mg (0.371 mmol, yield 39.1%) 3-chloro-6- (2-cyclopropyl-3-methoxyphenoxy) -4-methoxypyridazine Obtained.

(2) 6-chloro-3- (2-cyclopropyl-3-methoxyphenoxy) -4-pyridazinol (Compound No. 478, Step D-2)
24 mg (0.60 mmol) of 60% sodium hydride was suspended in dry N, N-dimethylformamide (DMF, 2 mL), and 0.05 mL (0.7 mmol) of ethanethiol was added dropwise to the suspension under ice cooling. For 10 minutes. To this mixture was added 60.0 mg (0.195 mmol) of 6-chloro-3- (2-cyclopropyl-3-methoxyphenoxy) -4-methoxypyridazine obtained in (1) with dry N, N-dimethylformamide (DMF, 1.5 mL) solution was added and heated to reflux for 2 hours. The reaction mixture was cooled, poured into ice-cooled 1 mol / L aqueous sodium hydroxide solution, and washed with ethyl acetate. Ice-cold concentrated hydrochloric acid was added to the aqueous layer to adjust to pH 4, and the mixture was extracted with ethyl acetate. The ethyl acetate extracts were combined, washed successively with water and saturated brine, and dried over sodium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (Merck, 1.05744, 3 plates used, developed with hexane: ethyl acetate = 1: 1), and 6-chloro-3 15.2 mg (0.0519 mmol, yield 26.6%) of-(2-cyclopropyl-3-methoxyphenoxy) -4-pyridazinol (Compound No. 478) was obtained.
¹ H-NMR (200 MHz, CDCl ₃ ) δ ppm: 7.19 (1H, dd, J = 8.1, 8.4 Hz), 6.76 (1H, d, J = 8.1 Hz), 6.69 (1H, d, J = 8.4 Hz), 6.60 (1H, s), 3.85 (3H, s), 1.55-1.35 (1H, m), 0.85-0.60 (4H, m).
Melting point (° C): 184-185.

(Example 14)
3- (1,1a, 6,6a-Tetrahydrocyclopropa [a] inden-2-yloxy) -6-chloro-4-pyridazinol (Compound No. 515)
(1) 7-Hydroxy-1-indanone 37.0 g (278 mmol) of aluminum chloride was mixed with 3.70 g (61.3 mmol) of sodium chloride, this mixture was heated and dissolved at 150 ° C., and dissolved by heating (50 ° C.). Of 2,3 dihydro-4H-chromen-4-one 6.40 g (43.2 mmol) was added and stirred at 200 ° C. for 20 minutes. The reaction mixture (gum-like) was cooled, added to ice-cooled hydrochloric acid (100 ml of concentrated hydrochloric acid and ice to make 200 ml) little by little, and stirred for 30 minutes. Methylene chloride was added to the mixture and the layers were separated. The aqueous layer was filtered and the filtrate was extracted with methylene chloride. The organic layers were combined, washed successively with water and saturated brine, and dried over sodium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to obtain 4.82 g (32.6 mmol, yield 75.2% of 7-hydroxy-1-indanone. )Obtained.

(2) 7- (Methoxymethoxy) -1-indanone 7-hydroxy-1-indanone 1.00 g (6.76 mmol) obtained from (1) was dissolved in N, N-dimethylformamide (DMF, 33 mL), and this solution The mixture was cooled on ice, and 0.330 g (8.25 mmol) of 60% sodium hydride was added in 4 portions and stirred for 30 minutes. To this mixture, 0.80 mL (11 mmol) of chloromethoxymethane was added dropwise and stirred at room temperature for 2 hours. The reaction mixture was poured into ice-cooled saturated aqueous ammonium chloride solution (100 mL) and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to obtain 1.04 g (5.42 mmol, 7- (methoxymethoxy) -1-indanone. Rate 80.2%).

(3) 7- (Methoxymethoxy) -1-indanol 7-Methoxymethoxy-1-indanone (1.04 g, 5.42 mmol) obtained from (2) was dissolved in methanol (20 mL). 164 mg (4.34 mmol) of sodium borohydride was added and stirred at room temperature for 4 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over sodium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to obtain 1.05 g (5.42 mmol, 7- (methoxymethoxy) -1-indanol. Rate 100%).

(4) Mixture of 4- (methoxymethoxy) -1H-indene and 7- (methoxymethoxy) -1H-indene 500 mg (2.58 mmol) of 7- (methoxymethoxy) -1-indanol obtained by (3) was chlorinated. This was dissolved in methylene (3 mL), the solution was ice-cooled, 0.50 mL (3.7 mmol) of triethylamine and 0.25 mL (3.3 mmol) of methanesulfonyl chloride were added, and the mixture was stirred for 2 hours. After adding 0.80 mL (5.7 mmol) of triethylamine and stirring for 1 hour, the mixture was poured into water and extracted with methylene chloride. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was dissolved in pyridine (3 mL) and heated to reflux for 4 hours. After standing at room temperature overnight, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 4- (methoxymethoxy) -1H-indene and 7- (methoxymethoxy)- 280 mg (1.59 mmol, 61.6% yield) of a mixture of 1H-indene was obtained.

(5) (2- (methoxymethoxy) -1,1a, 6,6a-tetrahydrocyclopropa [a] indene and 5- (methoxymethoxy) -1,1a, 6,6a-tetrahydrocyclopropa [a] indene mixture
Under a nitrogen stream, dry diethyl ether (5 mL) was added to a 30 mL eggplant flask and ice-cooled. Diethyl zinc (1.0 mol / L hexane solution) 6.3 mL (6.3 mmol) and diiodomethane 0.70 mL (8.5 mmol) were successively added dropwise thereto and stirred for 10 minutes. An ether solution (9 mL) of 250 mg (1.42 mmol) of the mixture of 4- (methoxymethoxy) -1H-indene and 7- (methoxymethoxy) -1H-indene obtained in (4) was slowly added dropwise to the mixture. The mixture was heated to reflux for 4 hours. The reaction mixture was cooled and poured into saturated aqueous ammonium chloride solution. The same volume of saturated aqueous sodium hydrogen carbonate solution was added thereto, followed by extraction with ether. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 2- (methoxymethoxy) -1,1a, 6,6a-tetrahydrocyclopropaline. 150 mg (0.789 mmol, yield 55.6%) of a mixture of [a] indene and 5- (methoxymethoxy) -1,1a, 6,6a-tetrahydrocyclopropa [a] indene was obtained.

(6) A mixture of 1,1a, 6,6a-tetrahydrocyclopropa [a] inden-2-ol and 1,1a, 6,6a-tetrahydrocyclopropa [a] inden-5-ol 150 mg of a mixture of 2- (methoxymethoxy) -1,1a, 6,6a-tetrahydrocyclopropa [a] indene and 5- (methoxymethoxy) -1,1a, 6,6a-tetrahydrocyclopropa [a] indene ( 0.789 mmol) was dissolved in methanol (6 mL), 2 drops of concentrated hydrochloric acid were added to this solution, and the mixture was stirred at room temperature for 1 hour and then stirred at 60 ° C. for 20 minutes. The reaction mixture was cooled, poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (Merck, 1.05744, developed with hexane: ethyl acetate = 2: 1), and 1,1a, 6,6a-tetrahydro 80.0 mg (0.548 mmol, 69.5% yield) of a mixture of cyclopropa [a] inden-2-ol and 1,1a, 6,6a-tetrahydrocyclopropa [a] inden-5-ol was obtained.

(7) 3- (1,1a, 6,6a-tetrahydrocyclopropa [a] inden-2-yloxy) -6-chloropyridazine 1-oxide and 3- (1,1a, 6,6a-tetrahydrocyclopropa [ a] A mixture of inden-5-yloxy) -6-chloropyridazine 1-oxide (step B-2)
Mixture of 1,1a, 6,6a-tetrahydrocyclopropa [a] inden-2-ol and 1,1a, 6,6a-tetrahydrocyclopropa [a] inden-5-ol obtained by (6) 80.0 mg (0.548 mmol) was dissolved in a mixed solvent of 1,4-dioxane (2 mL) and dimethyl sulfoxide (2 mL), and 85 mg (0.76 mmol) of potassium tert-butoxide was added to this solution and stirred for 10 minutes. To this, 82 mg (0.50 mmol) of 3,6-dichloropyridazine 1-oxide was added and stirred overnight at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (Merck, 1.05744, 4 plates used, developed with hexane: ethyl acetate = 2: 1), and 3- (1, 1a, 6,6a-Tetrahydrocyclopropa [a] inden-2-yloxy) -6-chloropyridazine 1-oxide and 3- (1,1a, 6,6a-tetrahydrocyclopropa [a] inden-5-yloxy) 75.0 mg (0.273 mmol, 49.8% yield) of a mixture of -6-chloropyridazine 1-oxide was obtained.

(8) 3- (1,1a, 6,6a-tetrahydrocyclopropa [a] inden-2-yloxy) -4,6-dichloropyridazine and 3- (1,1a, 6,6a-tetrahydrocyclopropa [a ] Inden-5-yloxy) -4,6-dichloropyridazine (Step B-3)
3- (1,1a, 6,6a-tetrahydrocyclopropa [a] inden-2-yloxy) -6-chloropyridazine 1-oxide and 3- (1,1a, 6,6a-) obtained by (7) A mixture of tetrahydrocyclopropa [a] inden-5-yloxy) -6-chloropyridazine 1-oxide 75.0 mg (0.273 mmol) was mixed with 0.30 mL (3.2 mmol) phosphorus oxychloride and the mixture was stirred overnight. The reaction mixture was concentrated under reduced pressure to remove phosphorous oxychloride, and the residue was preparative thin-layer chromatography (Merck, 1.05744, 3 plates used, hexane / ethyl acetate = 9/1 developed 4 times) 21.4 mg (0.0730 mmol, yield 26.7%) of 3- (1,1a, 6,6a-tetrahydrocyclopropa [a] inden-2-yloxy) -4,6-dichloropyridazine And 32.6 mg (0.111 mmol, yield 40.7%) of 3- (1,1a, 6,6a-tetrahydrocyclopropa [a] inden-5-yloxy) -4,6-dichloropyridazine was obtained.

(9) 3- (1,1a, 6,6a-tetrahydrocyclopropa [a] inden-2-yloxy) -6-chloro-4-pyridazinol (Compound No. 515, Step B-4)
3- (1,1a, 6,6a-tetrahydrocyclopropa [a] inden-2-yloxy) -4,6-dichloropyridazine 21.4 mg (0.0730 mmol) obtained in (8) in dimethyl sulfoxide (3 mL) Was added with 0.1 mL (0.2 mmol) of 2 mol / L sodium hydroxide aqueous solution and stirred at room temperature for 3 hours. The reaction mixture was poured into ice-cooled 1 mol / L aqueous sodium hydroxide solution and washed with ethyl acetate. The aqueous layer was separated, adjusted to pH 4 with concentrated hydrochloric acid under ice-cooling, and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over sodium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (Merck, 1.05744, 1 plate used, developed with chloroform: methanol = 10: 1), and 3- (1,1a , 6,6a-tetrahydrocyclopropa [a] inden-2-yloxy) -6-chloro-4-pyridazinol (Compound No. 515) was obtained in an amount of 10.3 mg (0.0375 mmol, yield 51.4%).
¹ H-NMR (200MHz, CD3OD) δppm: 7.08 (1H, t, J = 7.7Hz), 6.98 (1H, d, J = 7.7Hz), 6.84 (1H, d, J = 7.7Hz), 6.59 (1H , s), 3.20 (1H, dd, J = 17.2, 6.2Hz), 2.94 (1H, d, J = 17.2Hz), 2.30-2.15 (1H, m), 1.90-1.75 (1H, m), 1.05- 0.90 (1H, m).
Melting point (° C): 245-247.

(Example 15)
3- (1,1a, 6,6a-tetrahydrocyclopropa [a] inden-5-yloxy) -6-chloro-4-pyridazinol (Compound No. 516, Step B-4)
3- (1,1a, 6,6a-tetrahydrocyclopropa [a] inden-5-yloxy) -4,6-dichloropyridazine (32.6 mg, 0.111 mmol) obtained in Example 14 (8) was added to dimethyl sulfoxide ( 3 mL), and 0.1 mL (0.2 mmol) of a 2 mol / L sodium hydroxide aqueous solution was added to the solution, followed by stirring at room temperature for 4 hours. The reaction mixture was poured into ice-cooled 1 mol / L aqueous sodium hydroxide solution and washed with ethyl acetate. The aqueous layer was separated, adjusted to pH 4 with concentrated hydrochloric acid under ice-cooling, and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over sodium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (Merck, 1.05744, 1 plate used, developed with chloroform: methanol = 10: 1), and 3- (1,1a 1,6,6a-tetrahydrocyclopropa [a] inden-5-yloxy) -6-chloro-4-pyridazinol (Compound No. 516) was obtained in an amount of 13.4 mg (0.0487 mmol, yield 43.9%).
¹ H-NMR (200MHz, CD3OD) δppm: 7.25-7.05 (2H, m), 6.83 (1H, dd, J = 6.6, 2.6Hz), 6.67 (1H, s), 3.00 (1H, dd, J = 17.2 , 6.6Hz), 2.78 (1H, d, J = 17.2Hz), 2.50-2.35 (1H, m), 2.00-1.80 (1H, m), 1.15-1.00 (1H, m), 0.10-0.00 (1H, m).
Melting point (° C): 211-213.

(Example 16)
6-Chloro-3- (2-methoxy-5-methylphenoxy) -4-pyridazinol (Compound No. 704)
(1) 6-chloro-3- (2-methoxy-5-methylphenoxy) pyridazine 1-oxide (step B-2)
167.5 mg (1.21 mmol) of commercially available 2-methoxy-5-methylphenol was dissolved in a mixed solvent of 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL), and 142.8 mg (1.27 mmol) of potassium tert-butoxide was added to this solution. Then, 202.9 mg (1.23 mmol) of 3,6-dichloropyridazine 1-oxide was added and stirred overnight at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate: hexane = 2: 1) to give 6-chloro-3 226.5 mg (0.849 mmol, yield 70.2%) of-(2-methoxy-5-methylphenoxy) pyridazine 1-oxide was obtained.

(2) 4,6-Dichloro-3- (2-methoxy-5-methylphenoxy) pyridazine (Step B-3)
Dissolve 226.5 mg (0.849 mmol) of 6-chloro-3- (2-methoxy-5-methylphenoxy) pyridazine 1-oxide obtained in (1) in phosphorus oxychloride (1 mL) and stir this solution at room temperature overnight. did. Water and methylene chloride were added to the reaction solution, and the mixture was stirred for 30 minutes and extracted with methylene chloride. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate: hexane = 2: 1), and 4,6-dichloro 205.3 mg (0.720 mmol, yield 84.8%) of -3- (2-methoxy-5-methylphenoxy) pyridazine was obtained.

(3) 6-chloro-3- (2-methoxy-5-methylphenoxy) -4-pyridazinol (Compound No. 704, Step B-4)
205.3 mg (0.720 mmol) of 4,6-dichloro-3- (2-methoxy-5-methylphenoxy) pyridazine obtained in (2) was added to a mixed solvent of 1,4-dioxane (5 mL) and dimethyl sulfoxide (5 mL). Then, 1.8 mL (3.6 mmol) of a 2 mol / L aqueous sodium hydroxide solution was added to the solution, and the mixture was stirred overnight at room temperature. Water was added to the reaction mixture, diluted hydrochloric acid was added to adjust to pH 2, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate), and 6-chloro-3- (2-methoxy- 148.1 mg (0.555 mmol, yield 77.1%) of 5-methylphenoxy) -4-pyridazinol (Compound No. 704) was obtained.
^{1 H-NMR (200MHz, CD3OD} ) δppm: 7.04-6.91 (3H, m), 6.66 (1H, s), 3.70 (3H, s), 2.27 (3H, s).
Melting point (° C): 126-134.

(Example 17)
6-chloro-3- {2- [1- (ethylsulfanyl) ethyl] -6-fluorophenoxy} -4-pyridazinol (Compound No. 728)
(1) 3-Fluoro-2-methoxybenzaldehyde To a solution of 3.01 g (21.5 mmol) of commercially available 3-fluoro-2-hydroxybenzaldehyde in acetonitrile (50 mL), 5.92 g (42.8 mmol) of potassium carbonate and 6.66 mL of methyl iodide ( 107 mmol) was added and stirred at 90 ° C. for 3 hours. After standing overnight at room temperature, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to obtain 3.22 g of a crude product of 3-fluoro-2-methoxybenzaldehyde. .

(2) 1-Fluoro-2-methoxy-3-vinylbenzene In a nitrogen atmosphere, 273.2 mg (6.83 mmol) of 60% sodium hydride washed with hexane was suspended in dry dimethyl sulfoxide (3 mL). After heating and stirring at 85 ° C. for 30 minutes, the solution was returned to room temperature and further a solution of 2.44 g (6.83 mmol) of methyl (triphenyl) phosphonium bromide in dry dimethyl sulfoxide (8 mL) was slowly added dropwise under ice cooling. After stirring at room temperature for 30 minutes, a solution of 877.4 mg of the crude product of 3-fluoro-2-methoxybenzaldehyde obtained in (1) in dry dimethyl sulfoxide (5 mL) was added dropwise and stirred at room temperature for 30 minutes. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 0.38 g (2.5% of 1-fluoro-2-methoxy-3-vinylbenzene). Mmol).

(3) 1-Cyclopropyl-3-fluoro-2-methoxybenzene In a nitrogen atmosphere, put dry diethyl ether (5 mL) into a dry flask and add dropwise diethyl zinc (1 mol / L hexane solution) 9.20 mL (9.20 mmol). A solution of 0.56 g (3.7 mmol) of 1-fluoro-2-methoxy-3-vinylbenzene obtained in (2) in dry diethyl ether (10 mL) was added dropwise. After stirring at room temperature for 5 minutes, 1.48 mL (18.4 mmol) of diiodomethane was added dropwise and heated to reflux for 5 hours. After cooling to room temperature, 9.20 mL (9.20 mmol) of diethyl zinc (1 mol / L hexane solution) and 1.48 mL (18.4 mmol) of diiodomethane were added, and the mixture was heated to reflux again for 4 hours. After standing overnight at room temperature, the reaction mixture was poured into saturated aqueous ammonium chloride solution. A saturated aqueous sodium hydrogen carbonate solution was added thereto, and the mixture was stirred for 30 minutes and extracted with diethyl ether. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give a crude product of 1-cyclopropyl-3-fluoro-2-methoxybenzene 0.82 g was obtained.

(4) 6-chloro-3- {2- [1- (ethylsulfanyl) ethyl] -6-fluorophenoxy} pyridazine 1-oxide (step B-2)
Under a nitrogen atmosphere, 288.8 mg (7.22 mmol) of 60% sodium hydride was suspended in dry N, N-dimethylformamide (3 mL), and ethanethiol 0.55 mL (7.5 mmol) was slowly added dropwise thereto. After stirring for 15 minutes, a solution of 402.1 mg of the crude product of 1-cyclopropyl-3-fluoro-2-methoxybenzene obtained in (3) in dry N, N-dimethylformamide (6 mL) was added dropwise at 160 ° C. The mixture was heated and stirred for 5 hours. After standing overnight at room temperature, a 1 mol / L aqueous potassium hydroxide solution and diethyl ether were added to the reaction mixture. The aqueous layer was separated, washed with diethyl ether, and adjusted to pH 2 by adding dilute hydrochloric acid. This was extracted with diethyl ether, and the ether extracts were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (developed with ethyl acetate: hexane = 4: 1 using three 1.05744 manufactured by MERCK) to obtain 299.9 mg of a mixture.
152.7 mg of this mixture was dissolved in a mixed solvent of 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL), and 116.1 mg (1.03 mmol) of potassium tert-butoxide was added to this solution, and then 3,6-dichloropyridazine 1 162.6 mg (0.988 mmol) of oxide was added, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate: hexane = 2: 1), and 6-chloro-3 46.6 mg (0.144 mmol) of-{2- [1- (ethylsulfanyl) ethyl] -6-fluorophenoxy} pyridazine 1-oxide was obtained.

(5) 4,6-Dichloro-3- {2- [1- (ethylsulfanyl) ethyl] -6-fluorophenoxy} pyridazine (Step B-3)
6-Chloro-3- {2- [1- (ethylsulfanyl) ethyl] -6-fluorophenoxy} pyridazine 1-oxide 46.6 mg (0.144 mmol) obtained in (4) in phosphorus oxychloride (0.5 mL) Was stirred overnight at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (MERCK, 1.05744, 1 plate used, developed with ethyl acetate: hexane = 4: 1), and 4,6-dichloro 9.8 mg (0.028 mmol, 19% yield) of 3- {2- [1- (ethylsulfanyl) ethyl] -6-fluorophenoxy} pyridazine was obtained.

(6) 6-chloro-3- {2- [1- (ethylsulfanyl) ethyl] -6-fluorophenoxy} -4-pyridazinol (Compound No. 728, Step B-4)
9.8 mg (0.028 mmol) of 4,6-dichloro-3- {2- [1- (ethylsulfanyl) ethyl] -6-fluorophenoxy} pyridazine obtained by (5) was added to 1,4-dioxane (1 mL) and Dissolved in a mixed solvent of dimethyl sulfoxide (1 mL), to this solution was added 0.07 mL (0.14 mmol) of a 2 mol / L aqueous sodium hydroxide solution, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into water, adjusted to pH 2 with dilute hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 1 plate used, developed with ethyl acetate) to give 6-chloro-3- {2- [1 2.2 mg (0.0067 mmol, 24% yield) of-(ethylsulfanyl) ethyl] -6-fluorophenoxy} -4-pyridazinol (Compound No. 728) was obtained.
¹ H-NMR (200MHz, CD3OD) δppm: 7.42 (1H, d, J = 8.1Hz), 7.26-7.15 (1H, m), 7.07-6.97 (1H, m), 6.46 (1H, s), 4.33 ( 1H, q, J = 7.0Hz), 2.42-2.20 (2H, m), 1.43 (3H, d, J = 7.0Hz), 1.02 (3H, t, J = 7.0Hz).
Physical properties: amorphous.

(Example 18)
6-Chloro-3- (2-chloro-6-isopropylphenoxy) -4-pyridazinol (Compound No. 738)
(1) 1-Isopropyl-2-[(2-methoxyethoxy) methoxy] benzene
4.80 g (120 mmol) of 60% sodium hydride was suspended in dry tetrahydrofuran (60 mL). To this suspension, a solution of 13.6 g (100 mmol) of 2-isopropylphenol in dry tetrahydrofuran (80 mL) was added dropwise at 0 ° C. . After stirring at 0 ° C. for 10 minutes, a solution of 14.9 g (119 mmol) of 2-methoxyethoxymethyl chloride in dry tetrahydrofuran (80 mL) was added dropwise. The reaction mixture was stirred for 2 hours under ice cooling, poured into ice cold water (250 mL), and extracted with ethyl acetate. The organic layers were combined, washed successively with 1 mol / L aqueous sodium hydroxide solution and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (eluting with hexane: ethyl acetate = 50: 1), and 18.1 g (80.8 g) of 1-isopropyl-2-[(2-methoxyethoxy) methoxy] benzene was obtained. Mmol, yield 80.8%).

(2) 1-chloro-3-isopropyl-2-[(2-methoxyethoxy) methoxy] benzene 1-isopropyl-2-[(2-methoxyethoxy) methoxy] benzene 8.00 g (35.7 Mmol) was dissolved in dry ether (100 mL), and 34.4 mL (55.0 mmol) of n-butyllithium hexane solution (1.60 M) was added dropwise to the solution under ice cooling (reaction temperature 5-10 ° C.). Stir for 5 hours. Chlorine gas (2.51 g, 35.4 mmol) was blown into the reaction solution while maintaining the reaction solution temperature at 5-10 ° C. The reaction mixture was stirred for 1 hour under ice cooling, poured into 1 mol / L hydrochloric acid (300 mL), and extracted with ether. The organic layers were combined, dried over anhydrous sodium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluting with hexane: ethyl acetate = 100: 1), and 4.38 g (16.9 mmol, 16.9 mmol, 1-chloro-3-isopropyl-2-[(2-methoxyethoxy) methoxy] benzene) was obtained. Yield 47.3%).

(3) 2-Chloro-6-isopropylphenol 4.38 g (16.9 mmol) of 1-chloro-3-isopropyl-2-[(2-methoxyethoxy) methoxy] benzene obtained from (2) was added to dichloromethane (15 mL). After dissolution, 2.70 g (23.7 mmol) of trifluoroacetic acid was added to the solution and stirred overnight at room temperature. The reaction mixture was poured into 1 mol / L hydrochloric acid and extracted with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (eluted with hexane) to obtain 2.50 g (14.7 mmol, yield 87.0%) of 2-chloro-6-isopropylphenol.

(4) 3-Chloro-6- (2-chloro-6-isopropylphenoxy) pyridazine (Step A-1)
1.98 g (17.7 mmol) of potassium tert-butoxide, 2.50 g (14.7 mmol) of 2-chloro-6-isopropylphenol obtained in (3) and 1,4-dioxane (100 mL) were mixed, and the mixture was mixed at room temperature. For 20 minutes. To this, 2.18 g (14.6 mmol) of 3,6-dichloropyridazine was added and heated under reflux for 4 hours. To the reaction mixture, 0.50 g (4.5 mmol) of potassium tert-butoxide was added, and the mixture was further heated to reflux for 3 hours. The reaction mixture was allowed to cool, poured into 1N hydrochloric acid (100 mL), and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient) to give 3.18 g (11.2%) of 3-chloro-6- (2-chloro-6-isopropylphenoxy) pyridazine. Mmol, yield 76.2%).

(5) A mixture of 6-chloro-3- (2-chloro-6-isopropylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-chloro-6-isopropylphenoxy) pyridazine 1-oxide (Step C- 1)
3.17 g (11.2 mmol) of 3-chloro-6- (2-chloro-6-isopropylphenoxy) pyridazine obtained by (4) was dissolved in dry dichloromethane (90 mL), and 80-85% m-chloroperoxide was added to this solution. 2.90 g (13.4-14.3 mmol) of benzoic acid was added and heated to reflux for 13 hours. The reaction mixture was poured into 1N aqueous sodium hydroxide solution and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient) to give 6-chloro-3- (2-chloro-6-isopropylphenoxy) pyridazine 1-oxide and 3 2.82 g (9.43 mmol, yield 84.2%) of a mixture of -chloro-6- (2-chloro-6-isopropylphenoxy) pyridazine 1-oxide was obtained.

(6) Mixture of 4,6-dichloro-3- (2-chloro-6-isopropylphenoxy) pyridazine and 3,4-dichloro-6- (2-chloro-6-isopropylphenoxy) pyridazine (Step C-2)
Mixture of 6-chloro-3- (2-chloro-6-isopropylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-chloro-6-isopropylphenoxy) pyridazine 1-oxide obtained by (5) 2.80 g (9.36 mmol) was mixed with 17.5 mL (189 mmol) of phosphorus oxychloride and the mixture was heated to reflux for 2 hours 30 minutes. The reaction mixture was allowed to cool, poured into ice-cold water, and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1) to give 4,6-dichloro-3- (2-chloro-6-isopropylphenoxy) pyridazine. 0.850 g (2.67 mmol, mp90-91 ° C.), 4,6-dichloro-3- (2-chloro-6-isopropylphenoxy) pyridazine and 3,4-dichloro-6- (2-chloro-6-isopropylphenoxy) 1.78 g (5.60 mmol) of a pyridazine mixture was obtained.

(7) 6-chloro-3- (2-chloro-6-isopropylphenoxy) -4-methoxypyridazine and 3-chloro-6- (2-chloro-6-isopropylphenoxy) -4-methoxypyridazine (Step C- 3)
Sodium (0.080 g, 3.5 mmol) was added to methanol (10 mL), and the mixture was stirred at room temperature for 30 minutes. To this, 0.830 g (2.61 mmol) of 4,6-dichloro-3- (2-chloro-6-isopropylphenoxy) pyridazine obtained in (6) was added and stirred at room temperature for 2 hours. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1), washed with hexane to crystallize, and 6-chloro-3- (2-chloro-6-isopropylphenoxy) -4 0.720 g (2.30 mmol, yield 88.1%) of -methoxypyridazine was obtained. Meanwhile, 1.78 g (5.60 mmol) of a mixture of 4,6-dichloro-3- (2-chloro-6-isopropylphenoxy) pyridazine and 3,4-dichloro-6- (2-chloro-6-isopropylphenoxy) pyridazine By reacting in the same manner, 1.25 g (3.99 mmol, 71.3% yield) of 6-chloro-3- (2-chloro-6-isopropylphenoxy) -4-methoxypyridazine, 3-chloro-6- (2-chloro- 0.300 g (0.958 mmol, yield 17.1%) of 6-isopropylphenoxy) -4-methoxypyridazine was obtained.

(8) 6-chloro-3- (2-chloro-6-isopropylphenoxy) -4-pyridazinol (Compound No. 738, Step C-4)
1.46 g (4.66 mmol) of 6-chloro-3- (2-chloro-6-isopropylphenoxy) -4-methoxypyridazine obtained by (7) was dissolved in dimethyl sulfoxide (13 mL), and 2 mol / L water was added to this solution. 3 mL (6.0 mmol) of an aqueous sodium oxide solution was added and stirred at 80 ° C. for 3 hours. The reaction mixture was poured into water and acidified with hydrochloric acid. The precipitated solid was collected by filtration, washed with water and air dried. 1.33 g (4.45 mmol, 95.5% yield) of 6-chloro-3- (2-chloro-6-isopropylphenoxy) -4-pyridazinol (Compound No. 738) was obtained.
¹ H-NMR (60MHz, DMSO-d6) δppm: 7.40-7.05 (3H, m), 6.70 (1H, s), 2.98 (1H, septet, J = 6.2Hz), 1.13 (6H, d, J = 6.2Hz ).
Melting point (° C): 218-233.

(Example 19)
3- (2-Bromo-6-isopropylphenoxy) -6-chloro-4-pyridazinol (Compound No. 760)
(1) 1-Bromo-3-isopropyl-2-[(2-methoxyethoxy) methoxy] benzene 1-isopropyl-2-[(2-methoxyethoxy) methoxy] benzene 5.18 obtained in Example 18 (1) g (23.1 mmol) was dissolved in dry ether (100 mL), and 22.3 mL (35.7 mmol) of n-butyllithium hexane solution (1.60M) was added dropwise to the solution under ice cooling (reaction temperature 5-10 ° C.). The mixture was stirred for 5 hours under ice cooling. To this, 8.20 g (69.7 mmol) of 90% cyanogen bromide was added while keeping the reaction solution temperature at 5-10 ° C. The reaction mixture was stirred for 2 hours under ice cooling, poured into ice cold water (300 mL), and extracted with ether. The organic layers were combined, dried over anhydrous sodium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluted with hexane: ethyl acetate = 100: 1) to give 3.40 g (11.2 mmol, 1-bromo-3-isopropyl-2-[(2-methoxyethoxy) methoxy] benzene. Yield 48.5%).

(2) 2-Bromo-6-isopropylphenol 1.40 g (11.2 mmol) of 1-bromo-3-isopropyl-2-[(2-methoxyethoxy) methoxy] benzene obtained by (1) was added to dichloromethane (10 mL). After dissolution, 2.50 g (21.9 mmol) of trifluoroacetic acid was added to the solution and stirred overnight at room temperature. The reaction mixture was poured into 1 mol / L hydrochloric acid and extracted with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (eluted with hexane) to obtain 2.27 g (10.6 mmol, yield 94.6%) of 2-bromo-6-isopropylphenol.

(3) 3- (2-Bromo-6-isopropylphenoxy) -6-chloropyridazine (Step A-1)
Potassium tert-butoxide 1.52 g (13.6 mmol), 1,4-dioxane (60 mL) and 2.27 g (10.6 mmol) of 2-bromo-6-isopropylphenol obtained from (2) were mixed and the mixture was stirred at room temperature. Stir for 20 minutes. 3,6-dichloropyridazine (1.58 g, 10.6 mmol) was added thereto, and the mixture was heated to reflux for 7 hours and 20 minutes. The reaction mixture was allowed to cool, poured into ice-cold water (110 mL), and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was recrystallized (isopropyl ether) and then purified by silica gel column chromatography (hexane: ethyl acetate, gradient) to give 3- (2-bromo-6-isopropylphenoxy) -6 -2.68 g (8.17 mmol, yield 77.1%) of -chloropyridazine was obtained.

(4) A mixture of 3- (2-bromo-6-isopropylphenoxy) -6-chloropyridazine 1-oxide and 6- (2-bromo-6-isopropylphenoxy) -3-chloropyridazine 1-oxide (Step C- 1)
3.68 g (8.17 mmol) of 3- (2-bromo-6-isopropylphenoxy) -6-chloropyridazine obtained by (3) was dissolved in dry dichloromethane (35 mL), and 80-85% m-chloroperoxide was added to this solution. 2.12 g (9.80-10.4 mmol) of benzoic acid was added, and the mixture was heated to reflux for 12 hours and 30 minutes. The reaction mixture was poured into 1 mol / L aqueous sodium hydroxide solution and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 5: 1) to give 3- (2-bromo-6-isopropylphenoxy) -6-chloropyridazine 1-oxide. And 2.26 g (6.57 mmol, yield 80.4%) of a mixture of 6- (2-bromo-6-isopropylphenoxy) -3-chloropyridazine 1-oxide.

(5) Mixture of 3- (2-bromo-6-isopropylphenoxy) -4,6-dichloropyridazine and 6- (2-bromo-6-isopropylphenoxy) -3,4-dichloropyridazine (Step C-2)
Mixture of 3- (2-bromo-6-isopropylphenoxy) -6-chloropyridazine 1-oxide and 6- (2-bromo-6-isopropylphenoxy) -3-chloropyridazine 1-oxide obtained by (4) 2.14 g (6.22 mmol) was mixed with 11.6 mL (125 mmol) phosphorus oxychloride and the mixture was heated to reflux for 3 hours. The reaction mixture was allowed to cool, poured into ice-cold water, and extracted with ethyl acetate. The organic layers were combined, washed successively with 1 mol / L sodium hydroxide aqueous solution, water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1) to give 3- (2-bromo-6-isopropylphenoxy) -4,6-dichloropyridazine and There was obtained 2.22 g (6.13 mmol, yield 98.6%) of a mixture of 6- (2-bromo-6-isopropylphenoxy) -3,4-dichloropyridazine.

(6) 3- (2-Bromo-6-isopropylphenoxy) -6-chloro-4-methoxypyridazine (Step C-3)
Sodium (0.180 g, 7.8 mmol) was added to methanol (20 mL), and the mixture was stirred at room temperature for 30 minutes. Here, a mixture of 3- (2-bromo-6-isopropylphenoxy) -4,6-dichloropyridazine and 6- (2-bromo-6-isopropylphenoxy) -3,4-dichloropyridazine obtained by (5) 2.22 g (6.13 mmol) was added and stirred at room temperature for 4 hours. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 15: 1), washed with hexane to crystallize, and 3- (2-bromo-6-isopropylphenoxy) 1.48 g (4.13 mmol, yield 67.4%) of -6-chloro-4-methoxypyridazine was obtained. At the same time, 0.21 g (0.59 mmol, yield 9.6%) of 6- (2-bromo-6-isopropylphenoxy) -3-chloro-4-methoxypyridazine was obtained.

(7) 3- (2-Bromo-6-isopropylphenoxy) -6-chloro-4-pyridazinol (Compound No. 760, Step C-4)
3- (2-Bromo-6-isopropylphenoxy) -6-chloro-4-methoxypyridazine (0.72 g, 2.0 mmol) obtained in (6) was dissolved in dimethyl sulfoxide (10 mL), and this solution was dissolved in an aqueous sodium hydroxide solution. (100 mg of sodium hydroxide dissolved in 1.5 mL of water, 2.4 mmol) was added and stirred at 80 ° C. for 3 hours. The reaction mixture was poured into water and acidified with hydrochloric acid. The precipitated solid was collected by filtration, washed with water and air dried. 0.56 g (1.6 mmol, yield 80%) of 3- (2-bromo-6-isopropylphenoxy) -6-chloro-4-pyridazinol (Compound No. 760) was obtained.
¹ H-NMR (60MHz, DMF-d7) δppm: 7.70-7.00 (3H, m), 6.89 (1H, s), 2.94 (1H, septet, J = 7.0Hz), 1.16 (6H, d, J = 7.0 Hz).
Melting point (° C): 232-253 (dec.).

(Example 20)
3- (2-Bromo-6-tert-butylphenoxy) -6-chloro-4-pyridazinol (Compound No. 761)
(1) tert-Butyl-2-[(2-methoxyethoxy) methoxy] benzene
Suspend 60% sodium hydride (4.80 g, 120 mmol) in dry tetrahydrofuran (25 mL) and add dropwise a solution of 2-tert-butylphenol (15.0 g, 100 mmol) in dry tetrahydrofuran (80 mL) at 0 ° C. did. After stirring at 0 ° C. for 10 minutes, a solution of 14.9 g (119 mmol) of 2-methoxyethoxymethyl chloride in dry tetrahydrofuran (80 mL) was added dropwise. The reaction mixture was stirred for 4 hours 30 minutes under ice-cooling and left at room temperature overnight. To the reaction mixture, 1.20 g (30 mmol) of 60% sodium hydride and 3.8 g (30 mmol) of 2-methoxyethoxymethyl chloride were added at 0 ° C., and the mixture was stirred at 0 ° C. for 7 hours. The reaction mixture was poured into ice-cold water (250 mL) and extracted with ethyl acetate. The organic layers were combined, washed with 2N aqueous sodium hydroxide solution and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was purified by silica gel column chromatography (eluted with hexane: ethyl acetate = 20: 1), and 19.7 g (82.8 g) of tert-butyl-2-[(2-methoxyethoxy) methoxy] benzene was obtained. Mmol, yield 82.8%).

(2) 1-bromo-3-tert-butyl-2-[(2-methoxyethoxy) methoxy] benzene 10.0 g of tert-butyl-2-[(2-methoxyethoxy) methoxy] benzene obtained from (1) (42.0 mmol) was dissolved in dry ether (120 mL), and 42.1 mL (64.4 mmol) of n-butyllithium hexane solution (1.53 M) was added dropwise to the solution under ice cooling, followed by stirring for 3 hours under ice cooling. A solution of 14.8 g (126 mmol) of 90% cyanogen bromide in dry ether (20 mL) was added dropwise thereto. The reaction mixture was stirred for 3 hours under ice cooling, poured into ice cold water (300 mL), and extracted with ether. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (eluting with hexane: ethyl acetate = 20: 1) to give 1-bromo-3-tert-butyl-2-[(2-methoxyethoxy) methoxy] 8.48 g (26.8 mmol, yield 63.8%) of benzene was obtained.

(3) 2-Bromo-6-tert-butylphenol 8.38 g (26.4 mmol) of 1-bromo-3-tert-butyl-2-[(2-methoxyethoxy) methoxy] benzene obtained by (2) was added to dichloromethane (26.4 mmol). 30 mL), and a solution of 9.03 g (79.2 mmol) of trifluoroacetic acid in dichloromethane (20 mL) was added to this solution and stirred overnight at room temperature. The reaction mixture was poured into ice-cold 1 mol / L hydrochloric acid and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (eluted with hexane) to obtain 5.68 g (24.8 mmol, yield 93.9%) of 2-bromo-6-tert-butylphenol.

(4) 3- (2-Bromo-6-tert-butylphenoxy) -6-fluoropyridazine (Step A-1)
2-Bromo-6-tert-butylphenol 4.84 g (21.1 mmol) obtained in (3) was dissolved in 1,4-dioxane (40 mL), and potassium tert-butoxide 3.55 g (31.7 mmol) and 4-dioxane (40 mL) was added and stirred at room temperature for 15 minutes. To this, 2.45 g (21.1 mmol) of 3,6-difluoropyridazine was added and heated to reflux for 24 hours. The reaction mixture was allowed to cool, poured into ice-cold water, and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient) to obtain 1.70 g of 3- (2-bromo-6-tert-butylphenoxy) -6-fluoropyridazine. (5.23 mmol, yield 24.8%).

(5) 6- (2-Bromo-6-tert-butylphenoxy) -3-pyridazinol 1.70 g of 3- (2-bromo-6-tert-butylphenoxy) -6-fluoropyridazine obtained by (4) ( To a mixture of 5.23 mmol) and acetic acid (9 mL) was added 1.04 g (10.6 mmol) of potassium acetate, and the mixture was stirred at 130-140 ° C. for 3 hours. The reaction mixture was allowed to cool, poured into ice-cold water, and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the resulting residue was washed with benzene, and 1.54 g (4.77 mmol, 91.2% yield, mp 255-257) of 6- (2-bromo-6-tert-butylphenoxy) -3-pyridazinol. C).

(6) 3- (2-Bromo-6-tert-butylphenoxy) -6-chloropyridazine 1.54 g of 6- (2-bromo-6-tert-butylphenoxy) -3-pyridazinol obtained by (5) 4.77 mmol) was mixed with 15 mL (162 mmol) phosphorus oxychloride and the mixture was heated to reflux for 70 minutes. Phosphorus oxychloride was distilled off from the reaction mixture, poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 1.55 g (4.53 mmol, yield 95.0%) of 3- (2-bromo-6-tert-butylphenoxy) -6-chloropyridazine.

(7) Mixture of 3- (2-bromo-6-tert-butylphenoxy) -6-chloropyridazine 1-oxide and 6- (2-bromo-6-tert-butylphenoxy) -3-chloropyridazine 1-oxide (Process C-1)
1.42 g (4.15 mmol) of 3- (2-bromo-6-tert-butylphenoxy) -6-chloropyridazine obtained in (6) was dissolved in dry dichloromethane (20 mL), and 80% m-chloroperoxide was added to this solution. A solution of 1.08 g (4.99 mmol) of benzoic acid in dry dichloromethane (10 mL) was added, and the mixture was heated to reflux for 20 hours. To the reaction mixture was added 0.275 g (1.27 mmol) of 80% m-chloroperbenzoic acid, and the mixture was refluxed for 3 hours and 30 minutes, poured into a 1 mol / L aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1) to give 3- (2-bromo-6-tert-butylphenoxy) -6-chloropyridazine 1 0.704 g (1.97 mmol, yield 47.5%) of a mixture of 2-oxide and 6- (2-bromo-6-tert-butylphenoxy) -3-chloropyridazine 1-oxide was obtained.

(8) 3- (2-Bromo-6-tert-butylphenoxy) -4,6-dichloropyridazine and 6- (2-bromo-6-tert-butylphenoxy) -3,4-dichloropyridazine (Step C- 2)
3- (2-Bromo-6-tert-butylphenoxy) -6-chloropyridazine 1-oxide and 6- (2-bromo-6-tert-butylphenoxy) -3-chloropyridazine 1 obtained by (7) The 0.704 g (1.97 mmol) of the oxide mixture was mixed with 5 mL (54 mmol) phosphorus oxychloride and the mixture was heated to reflux for 2 hours. The reaction mixture was allowed to cool, poured into ice-cold water, and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1) to give 3- (2-bromo-6-tert-butylphenoxy) -4,6-dichloro 0.474 g (1.26 mmol, yield 64.0%) of pyridazine and 0.119 g (0.316 mmol, yield 16.0%) of 6- (2-bromo-6-tert-butylphenoxy) -3,4-dichloropyridazine were obtained.

(9) 3- (2-Bromo-6-tert-butylphenoxy) -6-chloro-4-methoxypyridazine (Step C-3)
3- (2-Bromo-6-tert-butylphenoxy) -4,6-dichloropyridazine obtained in (8) was dissolved in 0.443 g (1.18 mmol) of methanol (10 mL), and 28% sodium methoxy was dissolved in this solution. 0.545 g (2.83 mmol) of de-methanol solution and methanol (5 mL) were added, and the mixture was stirred at room temperature for 80 minutes. After adding 0.10 g (0.52 mmol) of 28% sodium methoxide-methanol solution to the reaction mixture and stirring at room temperature for 2 hours, 0.15 g (0.78 mmol) of 28% sodium methoxide-methanol solution was further added at room temperature. Stir overnight. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 0.428 g (1.15 mmol, yield 97.5%) of 3- (2-bromo-6-tert-butylphenoxy) -6-chloro-4-methoxypyridazine.

(10) 3- (2-Bromo-6-tert-butylphenoxy) -6-chloro-4-pyridazinol (Compound No. 761, Step C-4)
3- (2-Bromo-6-tert-butylphenoxy) -6-chloro-4-methoxypyridazine (0.395 g, 1.06 mmol) obtained in (9) was dissolved in dimethyl sulfoxide (5 mL), and the solution was hydroxylated. An aqueous sodium solution (prepared by dissolving 50.8 mg of sodium hydroxide in 3 mL of water, 1.27 mmol) was added, and the mixture was stirred at 80 ° C. for 3 hr. An aqueous sodium hydroxide solution (prepared by dissolving 42 mg of sodium hydroxide in 3 mL of water, 1.1 mmol) and dimethyl sulfoxide (10 mL) were added, and the mixture was further stirred at 80 ° C. for 5 hours. After allowing to cool, the reaction mixture was poured into ice-cold water and acidified with hydrochloric acid. The precipitated solid was collected by filtration, washed successively with water, hexane and isopropyl ether and air dried. 0.309 g (0.863 mmol, yield 81.4%) of 3- (2-bromo-6-tert-butylphenoxy) -6-chloro-4-pyridazinol (Compound No. 761) was obtained.
^{1 H-NMR (270MHz, CDCl} 3) δppm: 9.55 (1H, br.s), 7.47 (1H, dd, J = 8.1, 1.7Hz), 7.41 (1H, dd, J = 8.1, 1.7Hz), 7.08 (1H, t, J = 8.1Hz), 6.58 (1H, br.s), 1.34 (9H, s).
Melting point (° C): 240-247.

(Example 21)
6-Chloro-3- (2,6-dimethylphenoxy) -4-pyridazinol (Compound No. 801)
(1) 6-chloro-3- (2,6-dimethylphenoxy) pyridazine 1-oxide (step B-2)
268 mg (2.20 mmol) of 2,6-dimethylphenol, 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL) were mixed, and 270 mg (2.41 mmol) of potassium tert-butoxide was added to the mixture under ice cooling. Stir for minutes. Thereto was added 370 mg (2.24 mmol) of 3,6-dichloropyridazine 1-oxide, and the mixture was stirred at room temperature for 10 hours and allowed to stand for 2 days. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient), and 350 mg (1.39 mmol, 6-chloro-3- (2,6-dimethylphenoxy) pyridazine 1-oxide was collected. Rate 63.1%).

(2) 4,6-Dichloro-3- (2,6-dimethylphenoxy) pyridazine (Step B-3)
6-chloro-3- (2,6-dimethylphenoxy) pyridazine 1-oxide 330 mg (1.31 mmol) obtained by (1) was mixed with dichloromethane (0.6 mL) and phosphorus oxychloride 0.60 mL (6.5 mmol), The mixture was stirred for 1 hour and left for another 5 days. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient), and 322 mg (1.20 mmol, yield) of 4,6-dichloro-3- (2,6-dimethylphenoxy) pyridazine 91.6%).

(3) 6-chloro-3- (2,6-dimethylphenoxy) -4-pyridazinol (Compound No. 801, Step B-4)
300 mg (1.12 mmol) of 4,6-dichloro-3- (2,6-dimethylphenoxy) pyridazine obtained in (2) was dissolved in dimethyl sulfoxide (8 mL), and 10% (W / V) water was added to this solution. Sodium oxide aqueous solution 0.80mL (2.0 mmol) was added, and it stirred at room temperature overnight. Further, 0.80 mL (2.0 mmol) of 10% (W / V) aqueous sodium hydroxide solution was added. After disappearance of the raw materials, the reaction mixture was poured into ice-cold water. The mixture was acidified with hydrochloric acid and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient) and preparative thin layer chromatography (Merck, 1.05744, developed in dichloromethane: methanol = 9: 1), 128 mg (0.510 mmol, yield 45.5%) of 6-chloro-3- (2,6-dimethylphenoxy) -4-pyridazinol (Compound No. 801) was obtained.
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.18-7.05 (3H, m), 6.83 (1H, s), 2.05 (6H, s).
Melting point (° C): 214-215.

(Example 22)
3- (2-tert-Butyl-6-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 805)
(1) 3- (2-tert-butyl-6-methylphenoxy) -6-chloropyridazine (Step A-1)
17.5 g (107 mmol) of 2-tert-butyl-6-methylphenol, 11.9 g (106 mmol) of potassium tert-butoxide and 1,4-dioxane (250 mL) were mixed, and the mixture was stirred at room temperature for 30 minutes. To this was added 15.0 g (101 mmol) of 2,6-dichloropyridazine, and the mixture was stirred at 100 ° C. for 3 hours and 15 minutes. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was crystallized from isopropyl ether to obtain 15.3 g (55.2 mmol, yield 54.6%) of 3- (2-tert-butyl-6-methylphenoxy) -6-chloropyridazine.

(2) 3- (2-tert-butyl-6-methylphenoxy) -6-chloropyridazine 1-oxide (step C-1)
3- (2-tert-butyl-6-methylphenoxy) -6-chloropyridazine (8.00 g, 28.9 mmol) obtained by (1) was added to dry dichloromethane (200 mL) and 70% m-chloroperbenzoic acid (8.50 g) ( 34.4 mmol) and the mixture was stirred at room temperature for 4 days. The reaction mixture was poured into ice-cold saturated aqueous sodium sulfite and extracted with dichloromethane. The organic layers were combined, washed sequentially with water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was crystallized from an ether-hexane mixed solvent or purified by silica gel column chromatography, and 3- (2-tert-butyl-6-methylphenoxy) -6-chloropyridazine 1-oxide 7.04 g (24.0 mmol, yield 83.0%) was obtained.

(3) 3- (2-tert-butyl-6-methylphenoxy) -4,6-dichloropyridazine (Step C-2)
1.00 g (3.41 mmol) of 3- (2-tert-butyl-6-methylphenoxy) -6-chloropyridazine 1-oxide obtained by (2) was added to chloroform (10 mL) and 0.48 mL (5.2 mmol) of phosphorus oxychloride. And the mixture was stirred at reflux for 24 hours and at room temperature for 2 days. The reaction mixture was poured into ice cold water and extracted with dichloromethane. The organic layers were combined, washed successively with saturated aqueous sodium hydrogen carbonate solution, water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was crystallized from an ether-hexane mixed solvent. 0.767 g (2.47 mmol, yield 72.4%) of 3- (2-tert-butyl-6-methylphenoxy) -4,6-dichloropyridazine Got.

(4) 3- (2-tert-butyl-6-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 805, Step C-3)
354 mg (1.14 mmol) of 3- (2-tert-butyl-6-methylphenoxy) -4,6-dichloropyridazine obtained in (3), dimethyl sulfoxide (10 mL) and 1.6 mL of 1 mol / L aqueous sodium hydroxide solution (1.6 mmol) and the mixture was stirred at room temperature for 2 hours 30 minutes. The reaction mixture was poured into ice cold water and washed with ether. The aqueous layer was acidified with hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was crystallized with an ether-hexane mixed solvent, and 172 mg (0.587 mmol) of 3- (2-tert-butyl-6-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 805) was obtained. Yield 51.5%).
¹ H-NMR (90 MHz, CDCl ₃ ) δ ppm: 7.35-6.80 (3H, m), 6.50 (1H, s), 1.80 (3H, s), 1.18 (9H, s).
Melting point (° C): 135-136.

(Example 23)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol (Compound No. 806)
(1) 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-cyclopropyl-6-methylphenoxy) pyridazine 1-oxide (Step B- 2)
2-Cyclopropyl-6-methylphenol 221 mg (1.49 mmol) was mixed with 1,4-dioxane (2 mL) and dimethyl sulfoxide (2 mL), and potassium tert-butoxide 184 mg (1.64 mmol) was added to the mixture under ice cooling. Added and stirred for 10 minutes. Thereto was added 258 mg (1.56 mmol) of 3,6-dichloropyridazine 1-oxide, and the mixture was stirred at room temperature for 10 hours and allowed to stand for 3 days. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient) to give 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine 1-oxide and 3-chloro 222 mg (0.801 mmol, yield 53.8%) of a mixture of -6- (2-cyclopropyl-6-methylphenoxy) pyridazine 1-oxide was obtained.

(2) 4,6-Dichloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine (Step B-3)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-cyclopropyl-6-methylphenoxy) pyridazine 1-oxide obtained by (1) 210 mg (0.758 mmol) of this mixture was dissolved in chloroform (1 mL), and 0.106 mL (1.14 mmol) of phosphorus oxychloride was added to this solution. . Further, chloroform (2 mL) and 0.150 mL (1.62 mmol) of phosphorus oxychloride were added, and most of chloroform was distilled off with a nitrogen stream, followed by stirring for 3 hours. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was removed, the residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient), and 167 mg (0.566 mmol) of 4,6-dichloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine was obtained. Yield 74.7%).

(3) 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol (Compound No. 806, Step B-4)
150 mg (0.508 mmol) of 4,6-dichloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine obtained in (2) was dissolved in dimethyl sulfoxide (3 mL), and 10% (W / V ) A sodium hydroxide aqueous solution (0.37 mL, 0.925 mmol) was added, and the mixture was stirred at room temperature for 4 days. The reaction mixture was poured into ice-cold 5% aqueous sodium hydroxide and extracted with ether. The aqueous layer was acidified with hydrochloric acid and extracted with ether. The organic layer was dried and concentrated. The residue was purified by preparative thin layer chromatography (Merck, 1.05744, developed with dichloromethane: methanol = 20: 1), and 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4 114 mg (0.412 mmol, yield 81.1%) of pyridazinol (Compound No. 806) were obtained.
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.13-7.03 (2H, m), 6.84-6.79 (2H, m), 2.06 (3H, s), 1.83-1.68 (1H, m), 0.82-0.72 (2H, m), 0.64-0.51 (2H, m).
Melting point (° C): 201-202.

(Example 24)
6-Chloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] -4-pyridazinol (Compound No. 827)
(1) 1- (2,2-dichlorocyclopropyl) -2-methoxy-3-methylbenzene
2-Methoxy-1-methyl-3-vinylbenzene (304 mg, 2.05 mmol) was dissolved in chloroform (12 mL), and 50 mL of 50% aqueous sodium hydroxide solution (63 mmol) was added dropwise to the solution, followed by benzyl (triethyl) ammonium. 59.9 mg (0.263 mmol) of chloride was added and stirred at room temperature overnight. The reaction mixture was poured into water and extracted with chloroform. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with hexane: ethyl acetate = 4: 1), and 1- (2, 390 mg (1.69 mmol, yield 82.4%) of 2-dichlorocyclopropyl) -2-methoxy-3-methylbenzene was obtained.

(2) 2- (2,2-dichlorocyclopropyl) -6-methylphenol 102 mg (0.442 mmol) of 1- (2,2-dichlorocyclopropyl) -2-methoxy-3-methylbenzene obtained from (1) ) Was dissolved in dichloromethane (5 mL), the solution was ice-cooled, and 0.045 mL (0.47 mmol) of boron tribromide was added dropwise with stirring. The reaction mixture was stirred for 2 hours under ice-cooling, poured into water, and extracted with dichloromethane. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (MERCK, 1.05744, used in 2 plates, developed with hexane: ethyl acetate = 2: 1), and 2- (2, 76.9 mg (0.354 mmol, yield 80.1%) of 2-dichlorocyclopropyl) -6-methylphenol was obtained.

(3) 6-chloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] pyridazine 1-oxide (step B-2)
198 mg (0.912 mmol) of 2- (2,2-dichlorocyclopropyl) -6-methylphenol obtained by (2) was mixed with 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL). Under ice cooling, 113 mg (1.01 mmol) of potassium tert-butoxide was added and stirred for 10 minutes. Thereto was added 151 mg (0.915 mmol) of 3,6-dichloropyridazine 1-oxide, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed 3 times with hexane: ethyl acetate = 2: 1), and 6-chloro-3- 257 mg of a crude product of [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] pyridazine 1-oxide was obtained.

(4) 4,6-Dichloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] pyridazine (Step B-3)
The crude product of 6-chloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] pyridazine 1-oxide obtained in (3) was mixed with phosphorus oxychloride (3 mL). The mixture was stirred overnight at room temperature. Water and dichloromethane were added to the reaction mixture and stirred for 30 minutes. The mixture was separated, and the organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (MERCK, 1.05744, 3 plates used, developed with hexane: ethyl acetate = 2: 1), and 4,6-dichloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] pyridazine 209 mg (0.574 mmol, 2-step yield from 2- (2,2-dichlorocyclopropyl) -6-methylphenol, 62.9% )Obtained.

(5) 6-chloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] -4-pyridazinol (Compound No. 827, Step B-4)
209 mg (0.574 mmol) of 4,6-dichloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] pyridazine obtained by (4) was added to 1,4-dioxane (3 mL) and dimethyl The mixture was mixed with sulfoxide (3 mL), and 1.43 mL (2.86 mmol) of a 2 mol / L aqueous sodium hydroxide solution was added to the mixture and stirred overnight at room temperature. The reaction mixture was poured into water and acidified with dilute hydrochloric acid. This mixture was extracted with dichloromethane. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate) to give 6-chloro-3- [2- (2,2- 120 mg (0.349 mmol, yield 60.8%) of dichlorocyclopropyl) -6-methylphenoxy] -4-pyridazinol (Compound No. 827) was obtained.
¹ H-NMR (200MHz, CD3OD) δppm: 7.25 (1H, br.d, J = 6.3Hz), 7.16 (1H, t, J = 7.7Hz), 6.98 (1H, d, J = 7.7Hz), 6.72 (1H, s), 2.85 (1H, dd, J = 10.6, 8.8Hz), 2.22 (3H, s), 2.05-1.86 (2H, m).
Melting point (° C): 213-215.

(Example 25)
6-Chloro-3-[(5-methyl-1-benzofuran-4-yl) oxy] -4-pyridazinol (Compound No. 1109)
(1) 6,7-Dihydro-1-benzofuran-4 (5H) -one
11.2 g (0.100 mol) of 1,3-cyclohexanedione was dissolved in methanol (40 mL), and an aqueous solution (8 mL) of 6.60 g (0.100 mol) of 85% potassium hydroxide was added dropwise to this solution, followed by stirring at room temperature for 30 minutes. This mixture was iced, and 21.6 g (0.110 mol) of 40% aqueous chloroacetaldehyde solution was added with stirring, followed by stirring overnight at room temperature. A 2 mol / L hydrochloric acid aqueous solution was added dropwise to the reaction mixture, and the mixture was stirred at room temperature for 30 minutes, and then extracted with ether. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to obtain 6,7-dihydro-1-benzofuran-4 (5H) -one. 8.63 g (0.0635 mol, yield 63.5%) was obtained.

(2) Methyl 4-oxo-4,5,6,7-tetrahydro-1-benzofuran-5-carboxylate 6,7-dihydro-1-benzofuran-4 (5H) -one 3.00 obtained by (1) g (22.1 mmol) was dissolved in dry tetrahydrofuran (10 mL), and 48.5 mL (48.5 mmol) of lithium bis (trimethylsilyl) amide (1.0 M tetrahydrofuran solution) was added dropwise to this solution at −78 ° C. under a nitrogen stream. After stirring at −78 ° C. for 30 minutes, 1.87 mL (24.1 mmol) of methyl chlorocarbonate was added dropwise, and the reaction mixture was allowed to warm to room temperature and stirred for 10 minutes. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to obtain methyl 4-oxo-4,5,6,7-tetrahydro-1- 3.93 g (20.3 mmol, yield 91.9%) of benzofuran-5-carboxylate was obtained.

(3) Methyl 4-hydroxy-1-benzofuran-5-carboxylate 3.93 g of methyl 4-oxo-4,5,6,7-tetrahydro-1-benzofuran-5-carboxylate obtained from (2) (20.3 Mmol) was dissolved in 1,4-dioxane (100 mL). To this solution, 5.51 g (24.3 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was added and stirred at 120 ° C. for 3 hours. . The reaction mixture was allowed to cool, insoluble material was filtered off through celite, and the filtrate was concentrated. The residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to obtain 2.04 g (10.6 mmol, yield 52.2%) of methyl 4-hydroxy-1-benzofuran-5-carboxylate. It was.

(4) Methyl 4-methoxy-1-benzofuran-5-carboxylate Methyl 4-hydroxy-1-benzofuran-5-carboxylate obtained by (3) was added to a solution of 2.04 g (10.6 mmol) in acetonitrile (60 mL). Then, 2.53 g (18.3 mmol) of potassium carbonate and 2.85 mL (45.8 mmol) of methyl iodide were added, and the mixture was heated to reflux for 3 hours. After standing at room temperature overnight, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to obtain 2.01 g of methyl 4-methoxy-1-benzofuran-5-carboxylate ( 9.76 mmol, yield 92.1%).

(5) (4-Methoxy-1-benzofuran-5-yl) methanol A solution of 1.04 g (4.90 mmol) of methyl 4-methoxy-1-benzofuran-5-carboxylate obtained in (4) in dry tetrahydrofuran (20 mL) To the solution, 0.479 g (12.6 mmol) of lithium aluminum hydride was added little by little with stirring on ice. The reaction mixture was stirred for 2 hours under ice cooling, and ethyl acetate was added little by little. Subsequently, water (0.5 mL), 3N sodium hydroxide (0.5 mL), and water (1.5 mL) were sequentially added, and the mixture was stirred for 30 minutes. The mixture was filtered through celite, and the filtrate was concentrated to give 0.89 g of a crude product of (4-methoxy-1-benzofuran-5-yl) methanol.

(6) 4-Methoxy-5-methyl-1-benzofuran 0.65 g of the crude product of (4-methoxy-1-benzofuran-5-yl) methanol obtained from (5) was dissolved in dichloromethane (10 mL). To the solution, 0.56 mL (4.03 mmol) of triethylamine and 0.31 mL (3.99 mmol) of methanesulfonyl chloride were added dropwise with stirring under ice cooling, followed by stirring for 1 hour under ice cooling. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, dry dimethyl sulfoxide (20 mL) was added to the obtained residue, and 0.276 g (7.30 mmol) of sodium borohydride was added little by little. The mixture was stirred at room temperature for 1 hour, poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05717, 3 plates used, developed with hexane: ethyl acetate = 9: 1), and 4-methoxy-5 0.284 g (1.75 mmol, 48.9% yield from methyl 4-methoxy-1-benzofuran-5-carboxylate) was obtained.

(7) 5-Methyl-1-benzofuran-4-ol
268 mg (6.71 mmol) of 60% sodium hydride was suspended in dry N, N-dimethylformamide (11 mL), and 0.51 mL (6.9 mmol) of ethanethiol was added dropwise to the suspension under a nitrogen gas stream. Stir for minutes. To this was added a solution of 4-methoxy-5-methyl-1-benzofuran (362 mg, 2.23 mmol) obtained in (6) in N, N-dimethylformamide (7 mL), and the mixture was heated to reflux for 1 hour 30 minutes. The reaction mixture was allowed to cool, and 1 mol / L aqueous potassium hydroxide solution and diethyl ether were added. The aqueous layer was washed with diethyl ether and adjusted to pH 2 by adding dilute hydrochloric acid. This was extracted with diethyl ether, and the obtained organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (development using MERCK 1.05744, 3 hexanes: ethyl acetate = 2: 1), and 5-methyl-1-benzofuran- 276 mg (1.86 mmol, yield 83.4%) of 4-ol was obtained.

(8) 6-chloro-3-[(5-methyl-1-benzofuran-4-yl) oxy] pyridazine 1-oxide (Step B-2)
121 mg (0.818 mmol) of 5-methyl-1-benzofuran-4-ol obtained in (7) was mixed with 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL). 101 mg (0.902 mmol) of tert-butoxide was added and stirred for 10 minutes. Thereto was added 134 mg (0.812 mmol) of 3,6-dichloropyridazine 1-oxide, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (MERCK, 1.05744, 3 plates used, developed 3 times with hexane: ethyl acetate = 2: 1), and 6-chloro-3- 199 mg of a crude product of [(5-methyl-1-benzofuran-4-yl) oxy] pyridazine 1-oxide was obtained.

(9) 4,6-Dichloro-3-[(5-methyl-1-benzofuran-4-yl) oxy] pyridazine (Step B-3)
199 mg of a crude product of 6-chloro-3-[(5-methyl-1-benzofuran-4-yl) oxy] pyridazine 1-oxide obtained by (8) and 3 mL of phosphorus oxychloride were mixed, and this mixture was mixed. Stir at room temperature overnight. Water and dichloromethane were added to the reaction mixture and stirred for 30 minutes. The mixture was separated, and the organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was subjected to preparative thin layer chromatography (MERCK, 1.05744, 3 plates, hexane: ethyl acetate = 2: 1, developed 3 times, then MERCK, 1.05717, 2 plates) Use, hexane: ethyl acetate = 2: 1, developed three times), and 4,6-dichloro-3-[(5-methyl-1-benzofuran-4-yl) oxy] pyridazine 120 mg (0.407 mmol) 4-hydroxy-5-methyl-1-benzofuran, yield of 2 steps, 49.8%).

(10) 6-Chloro-3-[(5-methyl-1-benzofuran-4-yl) oxy] -4-pyridazinol (Compound No. 1109, Step B-4)
120 mg (0.407 mmol) of 4,6-dichloro-3-[(5-methyl-1-benzofuran-4-yl) oxy] pyridazine obtained by (9) was added to 1,4-dioxane (3 mL) and dimethyl sulfoxide ( 3 mL), 2 mol / L aqueous sodium hydroxide solution 1.01 mL (2.02 mmol) was added to the mixture, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into water and acidified with dilute hydrochloric acid. This mixture was extracted with dichloromethane. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 2 plates used, developed with ethyl acetate), and 6-chloro-3-[(5-methyl-1- 70.0 mg (0.253 mmol, 62.2% yield) of benzofuran-4-yl) oxy] -4-pyridazinol (Compound No. 1109) was obtained.
¹ H-NMR (200MHz, CD3OD) δppm: 7.65 (1H, d, J = 2.2Hz), 7.32 (1H, d, J = 8.8Hz), 7.18 (1H, d, J = 8.8Hz), 6.73 (1H , s), 6.60 (1H, dd, J = 2.2, 0.7 Hz), 2.23 (3H, s).
Melting point (° C): 222-225.

(Example 26)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl trifluoromethanesulfonate (Compound No. 2081, Step I-1)
50.3 mg (0.191 mmol) of 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol (Compound No. 139) obtained according to Example 6 was dissolved in methylene chloride (2 mL), and triethylamine 0.027 was dissolved in this solution. mL (0.19 mmol) was added dropwise, then 0.031 mL (0.19 mmol) of trifluoromethanesulfonic anhydride was added dropwise, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was directly purified by preparative thin-layer chromatography (MERCK, 1.05744, 2 plates used, developed with ethyl acetate: hexane = 2: 1) and 6-chloro-3- (2-cyclopropyl). 64.7 mg (0.164 mmol, yield 85.8%) of phenoxy) -4-pyridazinyl trifluoromethanesulfonate (Compound No. 2081) was obtained.
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.51 (1H, s), 7.26-7.19 (2H, m), 7.14-7.05 (2H, m), 1.89-1.81 (1H, m), 0.85-0.62 ( 4H, m).
Melting point (° C): 54-61.

(Example 27)
6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2225, Step I-1)
53.4 mg (0.203 mmol) of 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol (Compound No. 139) obtained according to Example 6 was dissolved in acetonitrile (3 mL). -Diazabicyclo [2.2.2] octane (23.1 mg, 0.206 mmol) was added, followed by 4-methylbenzenesulfonyl chloride (39.2 mg, 0.205 mmol), and the mixture was stirred at room temperature for 1 hour and 30 minutes. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by preparative thin layer chromatography (MERCK, 1.05744, developed with ethyl acetate: hexane = 2: 1) to give 6-chloro-3- (2- 68.8 mg (0.165 mmol, 81.3% yield) of cyclopropylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2225) was obtained.
^{1 H-NMR (200MHz, CDCl} 3) δppm: 7.87 (2H, d, J = 8.1Hz), 7.58 (1H, s), 7.36 (2H, d, J = 8.1Hz), 7.26-7.11 (2H, m ), 6.97-6.93 (1H, m), 6.74-6.70 (1H, m), 2.45 (3H, s), 1.67-1.59 (1H, m), 0.71-0.56 (4H, m).
Physical property: Oily substance.

(Example 28)
2-[(6-Chloro-4-{[(4-methylphenyl) sulfonyl] oxy} -3-pyridazinyl) oxy] phenyl 4-methylbenzenesulfonate (Compound No. 2233, Step I-1)
6-Chloro-3- (2-hydroxyphenoxy) -4-pyridazinol (Compound No. 384) 0.60 g (2.5 mmol), 4-methylbenzenesulfonyl chloride 1.06 g (5.5 mmol) obtained according to Example 10; 4-Diazabicyclo [2.2.2] octane (0.56 g, 5.0 mmol) and acetonitrile (30 mL) were mixed, and the mixture was stirred for 3 hours at room temperature with heating under reflux for 4 days. Acetonitrile was distilled off, water was added to the residue, and the mixture was extracted with ethyl acetate. The organic layers were combined, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was washed with a mixed solvent of hexane-ethyl acetate (3: 1) to give 2-[(6-chloro-4-{[(4-methylphenyl) sulfonyl] oxy} -3-pyridazinyl ) Oxy] phenyl 4-methylbenzenesulfonate (Compound No. 2233) was obtained in an amount of 1.0 g (1.8 mmol, yield 72%).
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 7.98-6.65 (13H, m), 2.40 (3H, s), 2.36 (3H, s).
Melting point (° C): 125.5-126.5.

(Example 29)
6-Chloro-5-methyl-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2372)
(1) 3-chloro-4-methyl-2,5-furandion and 3-chloro-4- (chloromethyl) -2,5-furandion
224 g (2.00 mol) of 3-methyl-2,5-furandione and 11.2 g (0.415 mol) of iron (III) chloride hexahydrate were mixed, and the mixture was heated to 140 ° C. and 346 g of chlorine gas was stirred. (4.88 mol) was blown in over 7 hours 30 minutes. The mixture was then heated at 175 ° C. for 3 hours 30 minutes. The reaction mixture was distilled under reduced pressure (5 mmHg) to collect a fraction at 80 ° C to 85 ° C. 223.5 g of crude product (including 3-chloro-4-methyl-2,5-furandion and 3-chloro-4- (chloromethyl) -2,5-furandion) was obtained.

(2) 4-chloro-5-methyl-1,2-dihydro-3,6-pyridazinedione and 4-chloro-5- (chloromethyl) -1,2-dihydro-3,6-pyridazinedione (1) 147 g (including 3-chloro-4-methyl-2,5-furandione and 3-chloro-4- (chloromethyl) -2,5-furandione) obtained by mixing with 400 ml of water, this mixture Was heated to reflux to give a solution. To this heated and refluxed solution, an aqueous solution of 116 g (1.10 mol) of hydrazine dihydrochloride (dissolved in 400 mL of water) was added dropwise over 40 minutes. Thereafter, the mixture was heated to reflux for 1 hour 30 minutes and allowed to cool. The precipitated crystals were collected by filtration and washed with hot water and then with ethyl acetate to obtain 81.8 g of 4-chloro-5-methyl-1,2-dihydro-3,6-pyridazinedione (mp305-310 ° C.). . On the other hand, the filtrate was extracted with ethyl acetate, and the organic layers were combined, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 8.06 g of a mixture containing 4-chloro-5- (chloromethyl) -1,2-dihydro-3,6-pyridazinedione as a residue.

(3) 3,4,6-Trichloro-5-methylpyridazine Oxygenate 24.1 g (0.150 mol) of 4-chloro-5-methyl-1,2-dihydro-3,6-pyridazinedione obtained from (2) The mixture was mixed with 250 mL (2.76 mol) of phosphorus chloride, and the mixture was heated to reflux for 1 hour and 40 minutes. Excess phosphorus oxychloride was distilled off from the reaction mixture, and the residue was mixed with ice water. The crystals were collected by filtration and extracted with ethyl acetate. The organic layer was washed with water and the solvent was distilled off. The obtained residue was distilled under reduced pressure (0.7 mmHg), and the fraction at 105 ° C to 110 ° C was collected, and 25.1 g (0.127 mol, yield 84.7%, mp67) of 3,4,6-trichloro-5-methylpyridazine was collected. .5-70 ° C).

(4) 3,6-dichloro-4-methoxy-5-methylpyridazine 3.90 g (40.1 mmol) of 3,4,6-trichloro-5-methylpyridazine obtained from (3) was mixed with methanol (100 mL). To this mixture was added dropwise a methanol solution (50 mL) of 0.92 g (40 mmol) of sodium under ice-cooling, and then the mixture was stirred for 1 hour under ice-cooling and heating for 15 minutes under reflux. Under ice cooling, 0.20 g (8.7 mmol) of sodium was added, and the mixture was further heated to reflux for 15 minutes. The reaction solution was allowed to cool and methanol was distilled off. The residue was mixed with ice water and extracted with ethyl acetate. The organic layers were combined and washed with water, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (eluted with Wakogel C-100, hexane: ethyl acetate = 5: 1) to obtain 5.1 g of a crude product. This was distilled under reduced pressure (0.07 mmHg), and a fraction at 125 ° C. was collected to obtain 4.50 g (23.3 mmol, yield 58.1%) of 3,6-dichloro-4-methoxy-5-methylpyridazine.

(5) Mixture of 3-chloro-5-methoxy-4-methyl-6- (2-methylphenoxy) pyridazine and 3-chloro-4-methoxy-5-methyl-6- (2-methylphenoxy) pyridazine (process D-1)
While stirring, 1.66 g (38.0 mmol) of 55% sodium hydride was gradually added to 30.8 g (285 mmol) of 2-methylphenol. After stirring at room temperature for 20 minutes, the mixture was heated to 90 ° C. to dissipate the sodium hydride solid. The mixture was cooled to 50 ° C., 3.69 g (19.1 mmol) of 3,6-dichloro-4-methoxy-5-methylpyridazine obtained in (4) was added, and the mixture was stirred at 110 ° C. for 3 hours 30 minutes. The reaction mixture was allowed to cool, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with 20% aqueous sodium hydroxide solution and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography to obtain 3-chloro-5-methoxy-4-methyl-6- (2-methylphenoxy) pyridazine and 3-chloro-4-methoxy-5-methyl-6- 1.38 g (5.21 mmol, yield 27.3%) of a mixture of (2-methylphenoxy) pyridazine was obtained.

(6) 6-chloro-5-methyl-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2372, Step D-2)
3-Chloro-5-methoxy-4-methyl-6- (2-methylphenoxy) pyridazine and 3-chloro-4-methoxy-5-methyl-6- (2-methylphenoxy) pyridazine obtained by (5) 1.38 g (5.21 mmol) of a mixture of the following was mixed with 1,4-dioxane (8 mL), and 0.282 g (6.78 mmol) of 96% sodium hydroxide in water (using 13 mL of water) was added to this mixture, and 4.5% at 110 ° C. Stir for hours. The reaction mixture was poured into water and extracted with ethyl acetate. The aqueous layer was acidified with hydrochloric acid, and the precipitated crystals were collected by filtration and 0.249 g (0-2) of 6-chloro-5-methyl-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2372) was collected.
.992 mmol, yield 19.0%, mp 209-213 ° C.).
¹ H-NMR (60 MHz, DMF-d7) δ ppm: 7.50-6.95 (4H, m), 2.28 (3H, m), 2.11 (3H, m).
Melting point (° C): 209-213.

  The crystals precipitated from the filtrate were collected by filtration to obtain 0.187 g (0.745 mmol, yield 14.3%) of 3-chloro-5-methyl-6- (2-methylphenoxy) -4-pyridazinol. On the other hand, after drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off to recover 0.57 g of raw material (41% recovery rate).

(Example 30)
6-Chloro-5- (methoxymethyl) -3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2378)
(1) 3,4,6-trichloro-5- (chloromethyl) pyridazine containing 4-chloro-5- (chloromethyl) -1,2-dihydro-3,6-pyridazinedione obtained in Example 29 To 7.8 g of the mixture, 50 mL of phosphorus oxychloride was added and heated to reflux for 1 hour. Excess phosphorus oxychloride was distilled off from the reaction mixture, and the residue was mixed with ice water. This mixture was extracted with ethyl acetate, and the organic layers were combined, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Merck, 9385, eluted with hexane: ethyl acetate = 10: 1) to obtain 3,4,6-trichloro-5- (chloro This gave 3.63 g (15.6 mmol, mp 102-104 ° C.) of methyl) pyridazine.

(2) 3,6-dichloro-4-methoxy-5- (methoxymethyl) pyridazine 2.32 g (10.0 mmol) of 3,4,6-trichloro-5- (chloromethyl) pyridazine obtained from (1) was methanolized. After being dissolved in (50 ml) by heating, the solution was cooled to −60 ° C. and a methanol solution of sodium methoxide (prepared from 0.23 g of sodium and 5 mL of methanol, 10.0 mmol) was added dropwise. The solution was stirred at −10 ° C. for 2 hours 30 minutes, and a methanol solution of sodium methoxide (prepared from 0.23 g of sodium and 5 mL of methanol, 10.0 mmol) was further added dropwise. After stirring at -10 ° C for 2 hours, the mixture was left overnight at room temperature. The reaction mixture was concentrated, and the residue was purified by silica gel column chromatography (Merck, 9385, eluted with hexane: ethyl acetate = 5: 1) to give 3,6-dichloro-4-methoxy-5- (methoxymethyl). ) 1.85 g (8.30 mmol, 83.0% yield, mp 28-32 ° C.) of pyridazine were obtained.

(3) 3-Chloro-5-methoxy-4- (methoxymethyl) -6- (2-methylphenoxy) pyridazine (Step D-1)
432 mg (4.00 mmol) of 2-methylphenol, methanol (20 mL) and 92 mg (4.0 mmol) of sodium were mixed and stirred at room temperature until sodium disappeared. Methanol was distilled off from this mixture, and 50 mL of toluene was added to the residue and heated to reflux. This mixture was ice-cooled, and a toluene solution (10 mL) of 3,6-dichloro-4-methoxy-5- (methoxymethyl) pyridazine obtained in (2) in 892 mg (4.00 mmol) was added dropwise and heated to reflux for 3 hours. . The reaction mixture was allowed to stand overnight at room temperature, washed with water and then with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was subjected to silica gel column chromatography (first time; elution with Merck, 9385, hexane: ethyl acetate = 5: 1, second time; Merck, 9385, hexane: ethyl acetate = 8: 1) and 0.487 g (1.65 mmol, 41.3% yield) of 3-chloro-5-methoxy-4- (methoxymethyl) -6- (2-methylphenoxy) pyridazine, 3-chloro-4 0.266 g (0.902 mmol, yield 22.6%) of -methoxy-5- (methoxymethyl) -6- (2-methylphenoxy) pyridazine was obtained.

(4) 6-chloro-5- (methoxymethyl) -3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2378, Step D-2)
3-Chloro-5-methoxy-4- (methoxymethyl) -6- (2-methylphenoxy) pyridazine obtained by (3) 0.354 g (1.20 mmol), 1,4-dioxane (2 mL), 96% water Sodium oxide (62 mg, 1.49 mmol) and water (8 mL) were mixed, and the mixture was stirred at room temperature for 2 days and further with heating under reflux for 3 hours. The reaction mixture was adjusted to pH 1 with hydrochloric acid, and extracted with ethyl acetate. The organic layers were combined, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 0.336 g (1.20 mmol, 100% yield) of 6-chloro-5- (methoxymethyl) -3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2378).
¹ H-NMR (60MHz, DMF-d7) δppm: 8.92 (1H, br.s), 7.45-6.80 (4H, m), 4.39 (2H, s), 3.25 (3H, s), 2.25 (3H, s ).
Melting point (° C): 123-126.

(Example 31)
Ethyl 6- (2-tert-butylphenoxy) -3-chloro-5-hydroxy-4-pyridazinecarboxylate (Compound No. 2386)
(1) 3- (2-tert-Butylphenoxy) -6-chloro-4-methoxypyridazine
2-tert-Butylphenol 5.87 g (39.1 mmol), dimethyl sulfoxide (80 mL) and potassium t-butoxide 4.38 g (39.0 mmol) were mixed and the mixture was stirred at room temperature for 20 minutes. To this mixture, 6.92 g (38.7 mmol) of a dimethyl sulfoxide solution (60 mL) of 3,6-dichloro-4-methoxypyridazine was added and stirred at room temperature for 40 minutes and at 80 ° C. for 45 minutes. The reaction mixture was poured into a saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic layers were combined, washed with water and then with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Merck, 9385, hexane: ethyl acetate, gradient) to give 3- (2-tert-butylphenoxy) -6-chloro-4-methoxypyridazine 2.66 g (9.09 mmol, yield 23.5%) and 6- (2-tert-butylphenoxy) -3-chloro-4-methoxypyridazine 1.82 g (6.22 mmol, yield 16.1%).

(2) Ethyl 6- (2-tert-butylphenoxy) -3-chloro-5-methoxy-4-pyridazinecarboxylate (Step G-1)
3- (2-tert-Butylphenoxy) -6-chloro-4-methoxypyridazine 783 mg (2.68 mmol) obtained in (1) was dissolved in dry tetrahydrofuran (26 mL), and the solution was cooled to -78 ° C. 1.20 mL (2.80 mmol) of n-butyllithium hexane solution (2.33M) was added and stirred for 20 minutes. To this was added 0.330 mL (3.45 mmol) of ethyl chlorocarbonate, and the mixture was stirred at the same temperature for 30 minutes. The reaction mixture was poured into saturated aqueous ammonium chloride and extracted with ether. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (eluted with hexane: ethyl acetate = 5: 1) and purified with ethyl 6- (2-tert-butylphenoxy) -3-chloro-5-methoxy. 603 mg (1.65 mmol, yield 61.6%) of 4-pyridazinecarboxylate was obtained.

(3) Ethyl 6- (2-tert-butylphenoxy) -3-chloro-5-hydroxy-4-pyridazinecarboxylate (Compound No. 2386, Step G-2)
Ethyl 6- (2-tert-butylphenoxy) -3-chloro-5-methoxy-4-pyridazinecarboxylate 419 mg (1.15 mmol) obtained from (2), 1,4-dioxane, 1 mol / L sodium hydroxide Aqueous solution (2.0 mL, 2.0 mmol) and dimethyl sulfoxide (2.0 mL) were mixed, and the mixture was stirred at room temperature for 2 hours 30 minutes and at 80 ° C. for 4 hours 30 minutes. After allowing to cool, the reaction mixture was acidified with hydrochloric acid and extracted with dichloromethane. The organic layers were combined, washed with brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography. Ethyl 6- (2-tert-butylphenoxy) -3-chloro-5-hydroxy-4-pyridazinecarboxylate (Compound No. 2386) (337 mg, 0.960) Mmol, yield 83.5%).
Physical properties: amorphous.

(Example 32)
3,6-bis (2-methylphenoxy) -4-pyridazinol (Compound No. 2395)
(1) 3-Chloro-5-methoxy-4,6-bis (2-methylphenoxy) pyridazine (Step D-1)
Dissolve 5.32 g (49.3 mmol) of 2-methylphenol in toluene (100 mL) and add 1.13 g (49.1 mmol) of sodium followed by 5.80 g (27.2 mmol) of 3,4,6-trichloro-5-methoxypyridazine to this solution. In addition, the mixture was stirred for 4 hours while heating under reflux. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient) and recrystallization from isopropyl ether to give 3-chloro-5-methoxy-4,6-bis (2-methylphenoxy). ) 3.0 g (8.4 mmol, 31% yield) of pyridazine was obtained.

(2) 6-chloro-3,5-bis (2-methylphenoxy) -4-pyridazinol (Compound No. 2395, Step D-2)
To a mixture of trimethylsilyl chloride 0.60 mL (4.7 mmol), sodium iodide 0.60 g (4.0 mmol) and acetonitrile (15 ml) 3-chloro-5-methoxy-4,6-bis (2-methyl) obtained by (1) 0.72 g (2.0 mmol) of phenoxy) pyridazine was added and stirred overnight. The reaction mixture was poured into ice cold water and extracted with methylene chloride. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (chloroform: methanol, gradient) to give 0.45 g of 6-chloro-3,5- (2-methylphenoxy) -4-pyridazinol (Compound No. 2395). (1.3 mmol, yield 65%).
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.32-7.05 (7H, m), 6.91 (1H, br.d, J = 7.3 Hz), 2.29 (3H, s), 2.19 (3H, s).
Melting point (° C): 110-115.

(Example 33)
3- (2-tert-Butylphenoxy) -6-chloro-5- (trimethylsilyl) -4-pyridazinol (Compound No. 2405)
(1) 3- (2-tert-Butylphenoxy) -6-chloro-4-methoxy-5- (trimethylsilyl) pyridazine (Step G-1)
498 mg (1.70 mmol) of 3- (2-tert-butylphenoxy) -6-chloro-4-methoxypyridazine obtained in Example 31 (1) was dissolved in dry tetrahydrofuran (15 mL), and the solution was brought to -78 ° C. After cooling, 1.10 mL (1.87 mmol) of n-butyllithium hexane solution (1.70 M) was added and stirred for 20 minutes. To this was added 0.370 mL (2.91 mmol) of trimethylsilyl chloride, and the mixture was stirred at the same temperature for 10 minutes. The reaction mixture was poured into saturated aqueous ammonium chloride and extracted with ether. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography to obtain 596 mg (1.63 mmol, 3- (2-tert-butylphenoxy) -6-chloro-4-methoxy-5- (trimethylsilyl) pyridazine. Yield 95.9%).

(2) 3- (2-tert-Butylphenoxy) -6-chloro-5- (trimethylsilyl) -4-pyridazinol (Compound No. 2405, Step G-2)
Sodium iodide (0.17 g, 1.1 mmol), trimethylsilyl chloride (0.14 mL, 1.1 mmol) and acetonitrile (3.5 mL) were mixed, and this mixture was stirred with 3- (2-tert-butylphenoxy obtained by (1). ) -6-chloro-4-methoxy-5- (trimethylsilyl) pyridazine (340 mg, 0.932 mmol) was added, and the mixture was stirred at room temperature for 1 hour and 35 minutes. The reaction mixture was poured into a saturated aqueous sodium sulfite solution and ice-cold dilute hydrochloric acid was added. This mixture was extracted with ethyl acetate, and the organic layers were combined and washed with saturated brine. The solvent was distilled off, the residue was purified by silica gel column chromatography, and 275 mg (0.783) of 3- (2-tert-butylphenoxy) -6-chloro-5- (trimethylsilyl) -4-pyridazinol (Compound No. 2405) was obtained. Mmol, yield 84.0%).
¹ H-NMR (90 MHz, CDCl ₃ ) δ ppm: 10.12 (1H, br.s), 7.39-6.75 (4H, m), 1.24 (9H, s), 0.31 (9H, s).
Melting point (° C): 160-163.

(Example 34)
6-Bromo-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2411)
(1) 5-Chloro-6- (2-methylphenoxy) -3-pyridazinol (Process P-1)
A mixture of 578 mg (2.27 mmol) of 4,6-dichloro-3- (2-methylphenoxy) pyridazine obtained in Example 1 (2), acetic acid (10 mL) and 0.45 g (4.6 mmol) of potassium acetate was heated for 5 hours. Refluxed. The reaction mixture was allowed to cool, 50 mL of water was added, and the mixture was extracted with ethyl acetate. The organic layers were combined and washed sequentially with water and saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off to obtain 461 mg (1.95 mmol, yield 85.9%) of 5-chloro-6- (2-methylphenoxy) -3-pyridazinol.

(2) 4,6-Dibromo-3- (2-methylphenoxy) pyridazine (Step P-2)
151 mg (0.637 mmol) of 5-chloro-6- (2-methylphenoxy) -3-pyridazinol obtained by (1), chloroform (3 mL) and 913 mg (3.18 mmol) of phosphorus oxybromide were mixed. Heated to reflux for 5 hours. The reaction mixture was allowed to cool, water and dichloromethane were added, and the mixture was stirred at room temperature for 1 hr. This mixture was extracted with dichloromethane. The organic layers were combined and washed sequentially with water and saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off. The obtained residue was purified by silica gel column chromatography to obtain 176 mg (0.512 mmol, yield 80.4%) of 4,6-dibromo-3- (2-methylphenoxy) pyridazine.

(3) 6-bromo-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2411, Step P-3)
114 mg (0.331 mmol) of 4,6-dibromo-3- (2-methylphenoxy) pyridazine obtained in (2) was dissolved in dimethyl sulfoxide (3 mL), and 0.8 mol (1.6 mol) of a 2 mol / L aqueous sodium hydroxide solution was added to this solution. Mmol) and stirred at room temperature for 3 hours. Water was added to the reaction mixture and washed with ethyl acetate. The aqueous layer was acidified with 4 mol / L hydrochloric acid and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was washed with an ethyl acetate-ether mixed solvent, and 56.0 mg (0.199 mmol, yield 60.1) of 6-bromo-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2411) was obtained. %)Obtained.
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.35-7.05 (4H, m), 6.82 (1H, br.s), 2.10 (3H, s).
Melting point (° C): 197-198.

(Example 35)
6-Cyclopropyl-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2423)
(1) 6-cyclopropyl-4-methoxy-3- (2-methylphenoxy) pyridazine (Step L-1)
To 2.94 mL (1.47 mmol) of 9-borabicyclo [3.3.1] nonane in tetrahydrofuran (0.5 mol / l) was added 87.5 mg (0.735 mmol) of propargyl bromide, and the mixture was heated to reflux for 2 hours. The reaction mixture was cooled to room temperature, 0.74 mL (2.2 mmol) of 3 mol / L sodium hydroxide aqueous solution was added, and the mixture was stirred at room temperature for 70 minutes. Here, 168 mg (0.669 mmol) of 6-chloro-4-methoxy-3- (2-methylphenoxy) pyridazine obtained in Example 2 (1) and 38.7 mg (0.00334 mmol) of tetrakis (triphenylphosphine) palladium were sequentially added. In addition, the mixture was heated to reflux overnight. The reaction mixture was allowed to cool, water was added, and the mixture was extracted with ethyl acetate. The organic layers were combined and washed sequentially with water and saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off. The obtained residue was purified by silica gel column chromatography to obtain 121 mg (0.473 mmol, yield 70.1%) of 6-cyclopropyl-4-methoxy-3- (2-methylphenoxy) pyridazine.

(2) 6-cyclopropyl-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2423, Step L-2)
25.6 mg (0.479 mmol) of 2-hydroxypyridine was dissolved in dimethyl sulfoxide (2 mL), and 53.8 mg (0.480 mmol) of potassium tert-butoxide was added to this solution at room temperature, followed by stirring at room temperature for 10 minutes. To this was added a solution of 112 mg (0.438 mmol) of 6-cyclopropyl-4-methoxy-3- (2-methylphenoxy) pyridazine obtained in (1) in dimethyl sulfoxide (1 mL), and 60 hours at 60 ° C. for 80 hours. Stir at 15 ° C. for 15 hours. Further, 45.6 mg (0.479 mmol) of 2-hydroxypyridine and 53.8 mg (0.480 mmol) of potassium tert-butoxide were added, followed by stirring at 80 ° C. for 4 hours and 30 minutes. The reaction mixture was allowed to cool, water was added, and the mixture was washed with ethyl acetate. The aqueous layer was acidified with 4 mol / L hydrochloric acid and extracted with ethyl acetate. The organic layers were combined and washed sequentially with water and saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off. The resulting residue was purified by preparative thin layer chromatography (Merck, 1.05744, developed with ethyl acetate) to give 6-cyclopropyl-3- (2-methylphenoxy) -4-pyridazinol (Compound No. 2423) 28.6 mg (0.118 mmol, yield 26.9%) was obtained.
¹ H-NMR (200MHz, CD3OD) δppm: 7.30-7.01 (4H, m), 6.19 (1H, s), 1.98-1.82 (1H, m), 1.23-1.12 (2H, m), 0.99-0.88 (2H , m).
Melting point (° C): 214-215.

(Example 36)
3- (2-Methylphenoxy) -6-vinyl-4-pyridazinol (Compound No. 2436)
(1) 4-Methoxy-3- (2-methylphenoxy) -6-vinylpyridazine (Step L-1)
123 mg (0.490 mmol) of 6-chloro-4-methoxy-3- (2-methylphenoxy) pyridazine obtained in Example 2 (1) was dissolved in toluene (2 mL), and this solution was dissolved in tributyl (vinyl) at room temperature. 246 mg (0.776 mmol) of tin and then 119 mg (0.103 mmol) of tetrakis (triphenylphosphine) palladium were sequentially added and heated to reflux for 3 hours. The reaction mixture was allowed to cool, ethyl acetate (5 mL), water (3 mL) and sodium fluoride were added, stirred for 30 minutes, and left overnight at room temperature. The mixture was filtered through celite, ethyl acetate was added to the filtrate, the organic layer was separated, and washed with saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (eluting with hexane: ethyl acetate = 1: 2), and 105 mg (0.434 mmol, 4-methoxy-3- (2-methylphenoxy) -6-vinylpyridazine was collected. Rate 88.6%).

(2) 3- (2-Methylphenoxy) -6-vinyl-4-pyridazinol (Compound No. 2436, Step L-2)
2-hydroxypyridine (33.7 mg, 0.354 mmol) was dissolved in dimethyl sulfoxide (1 mL), and potassium tert-butoxide (39.7 mg, 0.354 mmol) was added to the solution at room temperature, followed by stirring at room temperature for 10 minutes. To this was added a solution of 4-methoxy-3- (2-methylphenoxy) -6-vinylpyridazine obtained in (1) in 85.8 mg (0.354 mmol) in dimethyl sulfoxide (1 mL), and at 50 ° C. overnight at room temperature. For 4 hours 30 minutes. The reaction mixture was allowed to cool, water was added, and the mixture was washed with ethyl acetate. The aqueous layer was acidified with 4 mol / L hydrochloric acid and extracted with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate, and then the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (developed with hexane: ethyl acetate = 1: 4), and 51.7 mg of 3- (2-methylphenoxy) -6-vinyl-4-pyridazinol (Compound No. 2436) was obtained. (0.227 mmol, yield 64.1%).
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.35-7.03 (4H, m), 6.56-6.43 (2H, m), 6.16 (1H, d, J = 17.9Hz), 6.16 (1H, d, J = 11.4Hz), 2.11 (3H, s).
Melting point (° C): 195-197.

(Example 37)
3- (2-Methylphenoxy) -6- (1-propenyl) -4-pyridazinol (Compound No. 2442)
(1) 6-allyl-4-methoxy-3- (2-methylphenoxy) pyridazine (Step L-1)
200 mg (0.797 mmol) of 6-chloro-4-methoxy-3- (2-methylphenoxy) pyridazine obtained in Example 2 (1) was dissolved in toluene (4 mL), and this solution was dissolved in allyl (tributyl) at room temperature. Tin (305 mg, 0.921 mmol) and then tetrakis (triphenylphosphine) palladium (96.8 mg, 0.0838 mmol) were sequentially added, and the mixture was heated to reflux for 3 hours and 20 minutes. The reaction mixture was allowed to stand overnight at room temperature, and then ethyl acetate, water and sodium fluoride were added and stirred for 2 hours. The mixture was filtered through celite, ethyl acetate was added to the filtrate, the organic layer was separated, and washed successively with water and saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient), and 62.1 mg (0.243 mmol, yield 30.5%) of 6-allyl-4-methoxy-3- (2-methylphenoxy) pyridazine )Obtained.

(2) 3- (2-Methylphenoxy) -6- (1-propenyl) -4-pyridazinol (Compound No. 2442, Step L-2)
2-hydroxypyridine (25.3 mg, 0.267 mmol) was dissolved in dimethyl sulfoxide (2 mL), potassium tert-butoxide (29.9 mg, 0.267 mmol) was added to the solution at room temperature, and the mixture was stirred at room temperature for 10 minutes. To this was added 62.1 mg (0.243 mmol) of 6-allyl-4-methoxy-3- (2-methylphenoxy) pyridazine obtained in (1) in a dimethyl sulfoxide (3 mL) solution at 100 ° C. for 8 hours and 130 ° C. Stir at 5 ° C. for 5 hours 30 minutes. Further, 25.3 mg (0.267 mmol) of 2-hydroxypyridine and 29.9 mg (0.267 mmol) of potassium tert-butoxide were added, followed by stirring at 130 ° C. for 5 hours. The reaction mixture was allowed to cool, water was added, and the mixture was washed with ethyl acetate. The aqueous layer was acidified with 4 mol / L hydrochloric acid and extracted with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate, and then the solvent was distilled off. The obtained residue was purified by preparative thin layer chromatography (Merck, 1.05744, 3 plates used, developed with ethyl acetate), and 3- (2-methylphenoxy) -6- (1-propenyl) -4 -21.3 mg (0.0880 mmol, yield 36.2%) of pyridazinol (Compound No. 2442) was obtained.
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.32-7.03 (4H, m), 6.75-6.60 (1H, m), 6.44 (1H, s), 6.22-6.10 (1H, m), 2.10 (3H , s), 1.86 (3H, br.d, J = 6.6 Hz).
Melting point (° C): 208-210.

(Example 38)
6- (2,6-Dimethylphenoxy) -5-hydroxy-3-pyridazinecarbonitrile (Compound No. 2453)
(1) 6-chloro-3- (2,6-dimethylphenoxy) -4-methoxypyridazine 1-oxide (Step K-1)
6-chloro-3- (2,6-dimethylphenoxy) -4-methoxypyridazine 3.42 g (12.9 mmol), dichloromethane (110 mL) and 80% m-chloroperbenzoic acid 3.34 g (15.4 mmol) were mixed together. The mixture was stirred at room temperature for 16 days. The reaction mixture was poured into ice-cold saturated aqueous sodium sulfite and extracted with dichloromethane. The organic layers were combined, washed successively with saturated aqueous sodium hydrogen carbonate solution, water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was purified by silica gel column chromatography, and 2.06 g (7.33 mmol, yield 56.8%) of 6-chloro-3- (2,6-dimethylphenoxy) -4-methoxypyridazine 1-oxide. )Obtained.

(2) 3- (2,6-Dimethylphenoxy) -4-methoxypyridazine 1-oxide (Step K-2)
6-chloro-3- (2,6-dimethylphenoxy) -4-methoxypyridazine 1-oxide obtained from (1) 6.00 g (21.4 mmol), methanol (200 mL), triethylamine 3.0 mL, acetone (5 mL) and 0.5 g of 5% palladium on carbon was mixed, and this mixture was shaken using a Parr reducing apparatus at a hydrogen pressure of 3.5 atm for 2 hours. The reaction mixture was filtered and the filtrate was concentrated. Water was added to the residue and extracted with chloroform. The organic layers were combined, washed with brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was crystallized with a mixed solvent of ether-dichloromethane to obtain 4.32 g (17.6 mmol, yield 82.2%) of 3- (2,6-dimethylphenoxy) -4-methoxypyridazine 1-oxide. .

(3) 6- (2,6-Dimethylphenoxy) -5-methoxy-3-pyridazinecarbonitrile (Step M-1)
3- (2,6-Dimethylphenoxy) -4-methoxypyridazine 1-oxide 0.720 g (2.92 mmol) obtained in (2) was dissolved in dry N, N-dimethylformamide (15 mL) and trimethylsilyl cyanide was dissolved in this solution. 1.10 mL (8.25 mmol) of nido and 2.00 mL (14.4 mmol) of triethylamine were added and stirred at 90 ° C. for 1 hour 30 minutes. The reaction mixture was poured into a saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was purified by silica gel column chromatography, and 0.675 g (2.65 mmol, yield 90.8%) of 6- (2,6-dimethylphenoxy) -5-methoxy-3-pyridazinecarbonitrile was obtained. Obtained.

(4) 6- (2,6-Dimethylphenoxy) -5-hydroxy-3-pyridazinecarbonitrile (Compound No. 2453, Step M-2)
6- (2,6-Dimethylphenoxy) -5-methoxy-3-pyridazinecarbonitrile 0.500 g (1.96 mmol) obtained in (3) was dissolved in acetonitrile (5 mL), and trimethylsilyl chloride 0.300 mL ( 2.36 mmol) and 0.350 g (2.33 mmol) of sodium iodide were added and stirred at room temperature. 5 mL of acetonitrile was added and stirred for 1 hour, and then 3 mL of 1,4-dioxane was added and stirred overnight. The reaction mixture was poured into an aqueous sodium sulfite solution and acidified with 1 mol / L hydrochloric acid. Extracted with dichloromethane, washed with brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was purified by silica gel column chromatography, and 0.121 g (0.502 mmol, 6- (2,6-dimethylphenoxy) -5-hydroxy-3-pyridazinecarbonitrile (Compound No. 2453) was collected. Rate 25.6%).
¹ H-NMR (90 MHz, CDCl ₃ ) δ ppm: 11.3 (1H, br.s), 7.09-6.99 (4H, m), 1.90 (6H, s).
Physical properties: amorphous.

(Example 39)
1- [5-Hydroxy-6- (2-methylphenoxy) -3-pyridazinyl] ethanone (Compound No. 2455)
(1) 6- (1-Ethoxyvinyl) -4-methoxy-3- (2-methylphenoxy) pyridazine (Step L-1)
321 mg (1.28 mmol) of 6-chloro-4-methoxy-3- (2-methylphenoxy) pyridazine obtained in Example 2 (1) was dissolved in toluene (6.5 mL), and this solution was dissolved in (1- Ethoxyvinyl) (tributyl) tin (534 mg, 1.48 mmol) and tetrakis (triphenylphosphine) palladium (155.3 mg, 0.134 mmol) were sequentially added, and the mixture was heated to reflux for 3 hours and 20 minutes. The reaction mixture was allowed to stand overnight at room temperature, and then ethyl acetate, water and sodium fluoride were added and stirred for 2 hours. The mixture was filtered through celite, ethyl acetate was added to the filtrate, the organic layer was separated, and washed successively with water and saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate, gradient), and 51.8 mg (0.181 mmol) of 6- (1-ethoxyvinyl) -4-methoxy-3- (2-methylphenoxy) pyridazine was obtained. Yield 14.1%).

(2) 1- [5-Hydroxy-6- (2-methylphenoxy) -3-pyridazinyl] ethanone (Compound No. 2455, Step L-2)
2-Hydroxypyridine (18.4 mg, 0.194 mmol) was dissolved in dimethyl sulfoxide (2 mL), potassium tert-butoxide (21.7 mg, 0.194 mmol) was added to the solution at room temperature, and the mixture was stirred at room temperature for 10 minutes. To this was added a solution of 60.4- (1-ethoxyvinyl) -4-methoxy-3- (2-methylphenoxy) pyridazine obtained in (1) in 50.4 mg (0.176 mmol) in dimethyl sulfoxide (3 mL), and 100 ° C. And stirred at 130 ° C. for 5 hours and 30 minutes. Further, 18.4 mg (0.194 mmol) of 2-hydroxypyridine and 21.7 mg (0.194 mmol) of potassium tert-butoxide were added, and the mixture was stirred at 130 ° C. for 2 hours. The reaction mixture was allowed to cool, water was added, and the mixture was washed with ethyl acetate. The aqueous layer was acidified with 4 mol / L hydrochloric acid and extracted with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate, and then the solvent was distilled off. The obtained residue was purified by preparative thin layer chromatography (Merck, 1.05744, 3 plates used, developed with ethyl acetate), and 1- [5-hydroxy-6- (2-methylphenoxy) -3- 28.5 mg (0.117 mmol, 66.5% yield) of pyridazinyl] ethanone (Compound No. 2455) was obtained.
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.48-7.05 (5H, m), 2.58 (3H, s), 2.10 (3H, s).
Melting point (° C): 182-185.

(Example 40)
3- (2-Methylphenoxy) -6-phenyl-4-pyridazinol (Compound No. 2464)
(1) 4-Methoxy-3- (2-methylphenoxy) -6-phenylpyridazine (Step L-1)
210 mg (0.837 mmol) of 6-chloro-4-methoxy-3- (2-methylphenoxy) pyridazine obtained according to Example 2 (1), toluene (4 mL) and water (0.5 mL) were mixed, and this mixture was mixed. At room temperature, 161 mg (1.32 mmol) of phenylboronic acid, 365 mg (2.64 mmol) of potassium carbonate and 102 mg (0.0879 mmol) of tetrakis (triphenylphosphine) palladium were sequentially added, and the mixture was heated to reflux for 2 hours and 50 minutes. The reaction mixture was allowed to stand overnight at room temperature, and then the mixture was filtered through celite. Ethyl acetate and water were added to the filtrate. The organic layer was separated and washed with saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (eluting with hexane: ethyl acetate = 3: 1), and 146 mg (0.500 mmol, 4-methoxy-3- (2-methylphenoxy) -6-phenylpyridazine was collected. Rate 59.7%).

(2) 3- (2-Methylphenoxy) -6-phenyl-4-pyridazinol (Compound No. 2464, Step L-2)
91.9 mg (0.966 mmol) of 2-hydroxypyridine was dissolved in dimethyl sulfoxide (1.5 mL), and 95.4 mg (0.850 mmol) of potassium tert-butoxide was added to this solution at room temperature, followed by stirring at room temperature for 10 minutes. To this was added a solution of 8-2.8 mg (0.283 mmol) of 4-methoxy-3- (2-methylphenoxy) -6-phenylpyridazine obtained in (1) in dimethyl sulfoxide (1 mL), and the mixture was stirred at 60 ° C. for 3 hours. . The reaction mixture was allowed to cool, water was added, and the mixture was washed with ethyl acetate. The aqueous layer was acidified with 4 mol / L hydrochloric acid and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (Merck, 1.05744, 3 plates used, developed with ethyl acetate), and 3- (2-methylphenoxy) -6-phenyl 70.8 mg (0.255 mmol, 90.1% yield) of 4-pyridazinol (Compound No. 2464) was obtained.
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.78-7.66 (2H, m), 7.58-7.48 (3H, m), 7.35-7.08 (4H, m), 6.69 (1H, s), 2.15 (3H , s).
Melting point (° C): 236-237.

(Example 41)
3,6-bis (2-fluorophenoxy) -4-pyridazinol (Compound No. 2485)
(1) 3,6-bis (2-fluorophenoxy) pyridazine
2.69 g (24.0 mmol) of 2-fluorophenol was dissolved in dimethyl sulfoxide (20 mL), and 2.69 g (24.0 mmol) of potassium tert-butoxide was added to this solution at room temperature. To this, 1.49 g (10.0 mmol) of 2,6-dichloropyridazine was added and stirred at 100 ° C. for 3 hours. The reaction mixture was allowed to cool, poured into ice-cold water, and extracted with ethyl acetate. The organic layers were combined, washed successively with 1 mol / L sodium hydroxide aqueous solution, water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was washed with heated hexane and then heated isopropyl ether to obtain 1.71 g (5.70 mmol, yield 57.0%) of 3,6-bis (2-fluorophenoxy) pyridazine. It was.

(2) 3,6-bis (2-fluorophenoxy) pyridazine 1-oxide (step C-1)
3.14 g (13.8 mmol) of 3,6-bis (2-fluorophenoxy) pyridazine obtained by (1) was dissolved in dry dichloromethane (40 mL), and 3.19 g (14.8 mmol) of 80% m-chloroperbenzoic acid was added to this solution. ) And stirred at room temperature for 7 days. The reaction mixture was poured into ice-cold 1 mol / L sodium hydroxide aqueous solution and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (eluted with hexane: ethyl acetate = 3: 1) to obtain 2.24 g of 3,6-bis (2-fluorophenoxy) pyridazine 1-oxide. (7.09 mmol, yield 51.4%).

(3) 4-Chloro-3,6-bis (2-fluorophenoxy) pyridazine (Step C-2)
2,6-bis (2-fluorophenoxy) pyridazine 1-oxide (2.20 g, 6.96 mmol) obtained in (2) was mixed with 50 mL of phosphorus oxychloride, and the mixture was stirred at 90 ° C. for 1 hour. The reaction mixture was allowed to cool, poured into ice-cold water, and extracted with ethyl acetate. The organic layers were combined, washed successively with 1 mol / L sodium hydroxide aqueous solution, water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (hexane: ethyl acetate = 10: 1) to obtain 1.95 g of 4-chloro-3,6-bis (2-fluorophenoxy) pyridazine ( 5.82 mmol, yield 83.6%).

(4) 3,6-bis (2-fluorophenoxy) -4-methoxypyridazine (Step C-3)
1.44 g (4.30 mmol) of 4-chloro-3,6-bis (2-fluorophenoxy) pyridazine obtained by (3) was dissolved in methanol (20 mL), and 0.206 g (4.72 mmol) of 55% sodium hydride was dissolved in this solution. ) And stirred at 60 ° C. for 1 hour. The reaction mixture was allowed to cool, poured into ice-cold water, and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (eluted with hexane: ethyl acetate = 10: 1) to give 3,6-bis (2-fluorophenoxy) -4-methoxypyridazine as 1.03. g (3.12 mmol, yield 72.6%) was obtained.

(5) 3,6-bis (2-fluorophenoxy) -4-pyridazinol (Compound No. 2485, Step C-4)
3,6-bis (2-fluorophenoxy) -4-methoxypyridazine 450 mg (1.36 mmol), 96% sodium hydroxide 77 mg (1.85 mmol), dimethyl sulfoxide (5 mL) and water (1 mL) obtained by (4) And the mixture was stirred at 90 ° C. for 2 hours. The reaction mixture was poured into ice-cold water and acidified with hydrochloric acid. This was extracted with ethyl acetate, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 0.380 g (1.20 mmol, yield 88.2%) of 3,6-bis (2-fluorophenoxy) -4-pyridazinol (Compound No. 2485).
¹ H-NMR (60 MHz, DMSO-d6) δ ppm: 7.60-7.08 (8H, m), 6.34 (1H, br.s).
Melting point (° C): 228.

(Example 42)
(2,4-Dichlorophenyl) (5-{[5-hydroxy-6- (2-methylphenoxy) -3-pyridazinyl] oxy} -1,3-dimethyl-1H-pyrazol-4-yl) methanone (compound number 2506)
(1) (5-{[5-Chloro-6- (2-methylphenoxy) -3-pyridazinyl] oxy} -1,3-dimethyl-1H-pyrazol-4-yl) (2,4-dichlorophenyl) methanone
109 mg (0.382 mmol) of (2,4-dichlorophenyl) (5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl) methanone, 4,6-dichloro-3 obtained according to Example 1 (2) 1.62 g (6.35 mmol) of-(2-methylphenoxy) pyridazine and 107 mg (0.775 mmol) of potassium carbonate were mixed and the mixture was stirred at 130 ° C. for 14 hours. The reaction mixture was cooled to room temperature and purified by silica gel column chromatography (hexane: ethyl acetate, gradient) to give (5-{[5-chloro-6- (2-methylphenoxy) -3-pyridazinyl] oxy} -1 Thus, 155 mg (0.308 mmol, yield 80.6%) of 3,3-dimethyl-1H-pyrazol-4-yl) (2,4-dichlorophenyl) methanone was obtained.

(2) (2,4-Dichlorophenyl) (5-{[5-hydroxy-6- (2-methylphenoxy) -3-pyridazinyl] oxy} -1,3-dimethyl-1H-pyrazol-4-yl) methanone (Compound No. 2506, Step A-3)
(5-{[5-Chloro-6- (2-methylphenoxy) -3-pyridazinyl] oxy} -1,3-dimethyl-1H-pyrazol-4-yl) (2,4) obtained by (1) -Dichlorophenyl) methanone 12.3 mg (0.0244 mmol), dimethyl sulfoxide 0.2 mL and 10% (W / V) aqueous sodium hydroxide solution 0.012 mL were mixed and stirred overnight at room temperature. The reaction mixture was poured into ice-cold water, acidified with hydrochloric acid and extracted with ethyl acetate. The organic layers were combined and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (Merck, 1.05744, developed with dichloromethane: methanol = 10: 1), and (2,4-dichlorophenyl) (5-{[5 -Hydroxy-6- (2-methylphenoxy) -3-pyridazinyl] oxy} -1,3-dimethyl-1H-pyrazol-4-yl) methanone (Compound No. 2506) 3.2 mg (0.00784 mmol, 32% yield) ) And 4-[{[5-chloro-6- (2-methylphenoxy) -3-pyridazinyl] oxy} (2,4-dichlorophenyl) methylene] -2,5-dimethyl-2,4-dihydro- 10.5 mg (0.0208 mmol, yield 85.4%) of 3H-pyrazol-3-one was obtained.
Compound No. 2506:
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.36-7.04 (7H, m), 6.20 (1H, br.s), 3.64 (3H, s), 2.31 (3H, s), 2.20 (3H, s) .
Physical properties: amorphous.

  In addition, the following compounds were produced by or according to the methods of Examples 1-42 or Examples 622-646 described below.

(Example 43)
3-phenoxy-4-pyridazinol (Compound No. 1)
^{1 H-NMR (90MHz, DMSO} -d6) δppm: 12.66 (1H, br.s), 8.21 (1H, d, J = 6.6Hz), 7.09-7.54 (5H, m), 6.38 (1H, d, J = 6.6Hz).
Melting point (° C): 193.5.

(Example 44)
6-Chloro-3- {2- [1- (methoxymethyl) cyclopropyl] phenoxy} -4-pyridazinol (Compound No. 163)
¹ H-NMR (200MHz, CD3OD) δppm: 7.47-7.35 (1H, m), 7.32-7.02 (3H, m), 6.71 (1H, s), 3.47 (2H, s), 3.21 (3H, s), 0.80-0.70 (4H, m).
Melting point (° C): 187-190.

(Example 45)
3- (2-Isopropylphenoxy) -4-pyridazinol (Compound No. 6)
¹ H-NMR (90MHz, DMSO-d6) δppm: 12.65 (1H, br.s), 8.29 (2H, d, J = 6.6Hz), 7.49-6.98 (4H, m), 6.36 (1H, d, J = 6.6Hz), 3.20-2.89 (1H, m, J = 6.6Hz), 1.16 (6H, d, J = 6.6Hz).
Melting point (° C): 181.5-182.

(Example 46)
6-Chloro-3- [2- (1-methoxycyclopropyl) phenoxy] -4-pyridazinol (Compound No. 202)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.50-7.10 (4H, m), 6.67 (1H, s), 3.03 (3H, s), 1.00-0.85 (4H, m).
Melting point (° C): 157-165.

(Example 47)
2- {2-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] phenyl} cyclopropanecarbonitrile (Compound No. 226)
Trans form:
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.40-7.10 (4H, m), 6.75 (1H, s), 2.65-2.50 (1H, m), 1.65-1.45 (3H, m).
Melting point (° C): 203-207.
Cis body:
¹ H-NMR (200MHz, CD3OD) δppm: 7.40-7.15 (4H, m), 6.64 (1H, s), 2.59 (1H, q, J = 8.4Hz), 2.05-1.90 (1H, m), 1.67- 1.40 (2H, m).
Melting point (° C): 225-227.

(Example 48)
6-Chloro-3-phenoxy-4-pyridazinol (Compound No. 123)
¹ H-NMR (60 MHz, DMF-d7) δ ppm: 7.60-7.00 (5H, m), 6.87 (1H, s).
Melting point (° C): 222-224.

(Example 49)
6-Chloro-3- (2-fluorophenoxy) -4-pyridazinol (Compound No. 124)
¹ H-NMR (90 MHz, CD3OD) δ ppm: 7.50-7.05 (4H, m), 6.70 (1H, s).
Melting point (° C): 210-212.

(Example 50)
6-Chloro-3- (2-chlorophenoxy) -4-pyridazinol (Compound No. 125)
¹ H-NMR (60 MHz, DMF-d7) δ ppm: 7.70-7.10 (4H, m), 6.95 (1H, s).
Melting point (° C): 208-212.

(Example 51)
3- (2-Bromophenoxy) -6-chloro-4-pyridazinol (Compound No. 126)
¹ H-NMR (90 MHz, CD3OD) δ ppm: 7.68 (1H, dd, J = 7.5, 1.8 Hz), 7.53-7.10 (3H, m), 6.73 (1H, s).
Melting point (° C): 201-203.

(Example 52)
6-Chloro-3- (2-iodophenoxy) -4-pyridazinol (Compound No. 127)
¹ H-NMR (200MHz, CD3OD) δppm: 7.89 (1H, dd, J = 7.7, 1.5Hz), 7.45 (1H, td, J = 7.7, 1.5Hz), 7.22 (1H, dd, J = 7.7, 1.5 Hz), 7.04 (1H, td, J = 7.7, 1.5Hz), 6.74 (1H, s).
Melting point (° C): 216-217.

(Example 53)
6-Chloro-3- [2- (2-ethoxycyclopropyl) phenoxy] -4-pyridazinol (Compound No. 249)
¹ H-NMR (200MHz, CD3OD) δppm ： 7.26-7.05 (4H, m), 6.68 (1H, s), 3.46 (1H, q, J = 5.2Hz), 3.30-3.15 (2H, m), 2.17- 1.96 (1H, m), 1.10 (2H, dd, J = 5.2Hz, 8.5Hz), 0.93 (3H, t, J = 7.0Hz).
Melting point (° C): 145-152.

(Example 54)
6-Chloro-3- [2- (2,2-difluorocyclopropyl) phenoxy] -4-pyridazinol (Compound No. 264)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.40-7.15 (4H, m), 6.72 (1H, s), 2.85-2.65 (1H, m), 1.90-1.65 (2H, s).
Melting point (° C): 215-216.

(Example 55)
6-Chloro-3- (2-ethylphenoxy) -4-pyridazinol (Compound No. 130)
¹ H-NMR (200MHz, CD3OD) δppm: 7.35-7.15 (3H, m), 7.10-7.02 (1H, m), 6.70 (1H, s), 2.56 (2H, q, J = 7.7Hz), 1.17 ( 3H, t, J = 7.7Hz).
Melting point (° C): 217-218.

(Example 56)
6-Chloro-3- (2-propylphenoxy) -4-pyridazinol (Compound No. 131)
¹ H-NMR (60MHz, DMF-d7) δppm: 7.45-7.05 (4H, m), 6.90 (1H, s), 3.00-2.35 (2H, m), 1.95-1.26 (2H, m), 1.05-0.68 (3H, m).
Melting point (° C): 170-172.

(Example 57)
6-Chloro-3- (2-isopropylphenoxy) -4-pyridazinol (Compound No. 132)
¹ H-NMR (60MHz, DMF-d7) δppm: 7.60-7.00 (4H, m), 6.92 (1H, s), 3.11 (1H, septet, J = 7.0Hz), 1.18 (6H, d, J = 7.0 Hz).
Melting point (° C): 183.

(Example 58)
3- (2-Butylphenoxy) -6-chloro-4-pyridazinol (Compound No. 133)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 11.8 (1H, br.s), 7.30-6.70 (4H, m), 6.53 (1H, s), 2.60-2.00 (2H, m), 1.80-0.60 ( 7H, m).
Melting point (° C): 149.5-150.

(Example 59)
6-Chloro-3- (2-isobutylphenoxy) -4-pyridazinol (Compound No. 134)
¹ H-NMR (60MHz, CDCl ₃ ) δppm: 12.90 (1H, br.s), 7.40-6.85 (4H, m), 6.50 (1H, s), 2.25 (2H, d, J = 10.0Hz), 2.20 -1.45 (1H, m, J = 10.0Hz), 0.75 (6H, d, J = 10.0Hz).
Melting point (° C): 151.5-152.5.

(Example 60)
3- (2-sec-Butylphenoxy) -6-chloro-4-pyridazinol (Compound No. 135)
¹ H-NMR (60MHz, CDCl ₃ + DMF-d7) δppm: 7.35-6.80 (4H, m), 6.60 (1H, s), 3.05-2.50 (1H, m), 1.80-1.25 (2H, m), 1.13 (3H, d, J = 6.2Hz), 0.95-0.50 (3H, m).
Melting point (° C): 158-159.

(Example 61)
3- (2-tert-Butylphenoxy) -6-chloro-4-pyridazinol (Compound No. 136)
^{1 H-NMR (60MHz, DMF} -d7) δppm: 7.55-6.85 (4H, m), 6.91 (1H, s), 5.32 (1H, br.s), 1.35 (9H, s).
Melting point (° C): 215-216.

(Example 62)
6-Chloro-3- (2-pentylphenoxy) -4-pyridazinol (Compound No. 137)
^{1 H-NMR (60MHz, CDCl} 3) δppm: 11.70 (1H, br.s), 7.40-6.80 (4H, m), 6.50 (1H, s), 2.60-2.20 (2H, m), 1.80-0.60 ( 9H, m).
Melting point (° C): 151.5-152.5.

(Example 63)
6-Chloro-3- (2-hexylphenoxy) -4-pyridazinol (Compound No. 138)
^{1 H-NMR (60MHz, CDCl} 3) δppm: 7.40-6.70 (4H, m), 6.53 (1H, s), 2.70-2.20 (2H, m), 2.00-0.60 (11H, m).
Melting point (° C): 118-118.5.

(Example 64)
6-Chloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] -4-pyridazinol (Compound No. 265)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.55-7.15 (4H, m), 6.69 (1H, s), 2.90 (1H, dd, J = 11.0, 10.8 Hz), 2.05-1.85 (2H, m).
Melting point (° C): 158-163.

(Example 65)
6-Chloro-3- [2- (2,2-dibromocyclopropyl) phenoxy] -4-pyridazinol (Compound No. 266)
¹ H-NMR (200MHz, CD3OD) δppm: 7.41-7.36 (1H, m), 7.29-7.13 (3H, m), 6.71 (1H, s), 2.97-2.87 (1H, dd, J = 11.0, 8.4Hz ), 2.21-2.01 (2H, m).
Melting point (° C): 208-210 (decomposition).

Example 66
6-Chloro-3- [2- (1-methylcyclopropyl) phenoxy] -4-pyridazinol (Compound No. 144)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.40-7.35 (1H, m), 7.22-7.17 (2H, m), 6.99-6.94 (1H, m), 6.59 (1H, s), 1.25 (3H, s), 0.85-0.60 (2H, m), 0.60-0.45 (2H, m).
Melting point (° C): 196-198.

(Example 67)
6-Chloro-3- [2- (1-ethylcyclopropyl) phenoxy] -4-pyridazinol (Compound No. 145)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.35-7.10 (3H, m), 6.98 (1H, br.d, J = 7.3 Hz), 6.59 (1H, s), 1.50 (2H, q, J = 7.0Hz), 1.26 (3H, t, J = 7.0Hz), 0.67-0.50 (4H, m).
Melting point (° C): 162-165.

Example 68
6-Chloro-3- {2- [1- (cyclopropyl) cyclopropyl] phenoxy} -4-pyridazinol (Compound No. 151)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.35-7.29 (1H, m), 7.26-7.10 (2H m), 7.00-6.92 (1H, m), 6.58 (1H, s), 1.30-1.15 (1H , m), 0.60-0.40 (4H, m), 0.27-0.15 (2H, m), 0.07-0.00 (2H, m).
Melting point (° C): 180-182.

(Example 69)
1- {2-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] phenyl} cyclopropanecarbonitrile (Compound No. 173)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.55-7.15 (5H, m), 1.65-1.20 (4H, m).
Melting point (° C): 63-64.

(Example 70)
6-Chloro-3- [2- (1-phenylcyclopropyl) phenoxy] -4-pyridazinol (Compound No. 184)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.65-7.55 (1H, m), 7.28-7.20 (2H, m), 7.17-6.95 (6H, m), 6.41 (1H, s), 1.19 (4H, s).
Melting point (° C): 172-173.

(Example 71)
6-Chloro-3- (2-isopropenylphenoxy) -4-pyridazinol (Compound No. 304)
¹ H-NMR (200 MHz, CD3OD) δppm: 7.36-7.10 (4H, m), 6.66 (1H, s), 5.06 (1H, br.s), 5.02 (1H, br.s), 2.01 (3H, d , J = 1.5 Hz).
Melting point (° C): 187-188.

(Example 72)
6-Chloro-3- [2- (2-methylcyclopropyl) phenoxy] -4-pyridazinol (Compound No. 217)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.32-6.97 (4H, m), 6.82 (1H, br.s), 1.89-1.78 (0.8H, m), 1.52-1.43 (0.2H, m) , 1.05-0.60 (6H, m).
Melting point (° C): 192-208.

(Example 73)
6-Chloro-3- [2- (2-ethoxycyclopropyl) phenoxy] -4-pyridazinol (Compound No. 249)
¹ H-NMR (200MHz, CD3OD) δppm: 7.30-7.05 (4H, m), 6.68 (1H, s), 3.51-3.15 (3H, m), 2.07-1.95 (1H, m), 1.13-1.06 (2H , m), 0.93 (3H, t, J = 7.1Hz).
Melting point (° C): 145-152.

(Example 74)
(2E) -3- {2-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] phenyl} acrylonitrile (Compound No. 306)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.80-7.40 (3H, m), 7.35-7.15 (2H, m), 6.72 (1H, s), 6.30 (1H, d, J = 6.9 Hz).
Melting point (° C): 190-192.

(Example 75)
6-Chloro-3- [2- (2,2-dimethylcyclopropyl) phenoxy] -4-pyridazinol (Compound No. 267)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.30-7.10 (4H, m), 1.57 (1H, dd, J = 8.4, 6.2Hz), 0.91-0.85 (1H, m), 0.85 (3H, s ), 0.72-0.65 (1H, m), 0.65 (3H, s).
Melting point (° C): 187-188.

(Example 76)
6-chloro-3- {2-[(cis-2, cis-3-dimethyl) -ref-1-cyclopropyl] phenoxy} -4-pyridazinol (Compound No. 269)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.36-7.11 (4H, m), 6.68 (1H, s), 1.60 (1H, t, J = 8.4 Hz), 1.09-0.93 (8H, m).
Physical properties: amorphous.

(Example 77)
6-Chloro-3- {2-[(cis-2, trans-3-dimethyl) -ref-1-cyclopropyl] phenoxy} -4-pyridazinol (Compound No. 270)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.30-7.09 (4H, m), 6.80 (1H, br.s), 1.56-1.50 (1H, m), 1.10-0.95 (1H, m), 1.03 (3H, s), 0.80-0.67 (1H, m), 0.71 (3H, s).
Melting point (° C): 157-160.

(Example 78)
6-chloro-3- {2-[(trans-2, trans-3-dimethyl) -ref-1-cyclopropyl] phenoxy} -4-pyridazinol (Compound No. 271)
^{1 H-NMR (200MHz, CD3OD} ) δppm: 7.22-6.96 (4H, m), 6.70 (1H, s), 1.18-0.95 (9H, m).
Melting point (° C): 181-183.

(Example 79)
3- {2-[(ref-1, cis-5, cis-6) -bicyclo [3.1.0] hex-6-yl] phenoxy} -6-chloro-4-pyridazinol (Compound No. 272)
¹ H-NMR (200MHz, CD3OD) δppm: 7.40-7.05 (4H, m), 6.68 (1H, s), 2.05-1.60 (5H, m), 1.53 (2H, s), 1.35-1.20 (1H, m ), 0.25-0.05 (1H, m).
Melting point (° C): 215-240.

(Example 80)
3- {2-[(ref-1, cis-5, trans-6) -bicyclo [3.1.0] hex-6-yl] phenoxy} -6-chloro-4-pyridazinol (Compound No. 273)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.20-7.10 (2H, m), 7.10-6.90 (2H, m), 6.58 (1H, s), 1.80-1.40 (8H, m), 1.20-1.00 ( 1H, m).
Melting point (° C): 137-139.

(Example 81)
3- {2-[(ref-1, cis-6, cis-7) -bicyclo [4.1.0] hept-7-yl] phenoxy} -6-chloro-4-pyridazinol (Compound No. 274)
¹ H-NMR (200MHz, CD3OD) δppm: 7.44 (1H, br.d, J = 6.3Hz), 7.35-7.10 (3H, m), 6.66 (1H, s), 2.00-1.50 (5H, m), 1.20-1.00 (4H, m), 0.90-0.65 (2H, m).
Melting point (° C):> 260.

(Example 82)
3- {2-[(ref-1, cis-6, trans-7) -bicyclo [4.1.0] hept-7-yl] phenoxy} -6-chloro-4-pyridazinol (Compound No. 275)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.20-7.10 (2H, m), 7.05-6.85 (2H, m), 6.58 (1H, s), 1.90-1.70 (2H, m), 1.60-1.40 ( 3H, m), 1.30-1.05 (6H, m).
Melting point (° C): 191-193.

(Example 83)
6-Chloro-3- {2-[(2,2, cis-3-trimethyl) -ref-1-cyclopropyl] phenoxy} -4-pyridazinol (Compound No. 279)
¹ H-NMR (200 MHz, CDCl ₃ ) δ ppm: 7.30-7.00 (4H, m), 6.56 (1H, s), 1.42-1.22 (2H, m), 1.05-0.70 (9H, m).
Melting point (° C): 118-120.

(Example 84)
6-Chloro-3- {2-[(2,2, trans-3-trimethyl) -ref-1-cyclopropyl] phenoxy} -4-pyridazinol (Compound No. 280)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.26-7.06 (4H, m), 6.59 (1H, s), 1.70-1.50 (1H, m), 1.30-1.25 (1H, m), 1.09 (3H, s), 0.96 (3H, s), 0.75 (3H, s).
Melting point (° C): 160-162.

(Example 85)
6-Chloro-3- (2-cyclobutylphenoxy) -4-pyridazinol (Compound No. 284)
¹ H-NMR (200MHz, CD3OD) δppm: 7.43-7.30 (1H, m), 7.30-7.18 (2H, m), 7.08-6.98 (1H, m), 6.69 (1H, s), 3.68-3.50 (1H m), 2.25-1.70 (6H, m).
Melting point (° C): 188-189.

(Example 86)
1- {2-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] phenyl} cyclobutanecarbonitrile (Compound No. 287)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.50-7.20 (5H, m), 2.70-1.80 (6H, m).
Melting point (° C): 213-215.

(Example 87)
1- {2-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] phenyl} cyclobutanecarboxylic acid (Compound No. 288)
¹ H-NMR (200MHz, CD3OD) δppm: 7.42-7.35 (1H, m), 7.35-7.20 (2H, m), 7.08-7.03 (1H, m), 6.66 (1H, s), 2.80-2.45 (4H m), 2.22-1.95 (1H, m), 1.90-1.70 (1H, m).
Melting point (° C): 173-175.

(Example 88)
6-Chloro-3- (2-cyclopentylphenoxy) -4-pyridazinol (Compound No. 292)
¹ H-NMR (200MHz, CD3OD) δppm: 7.41-7.35 (1H, m), 7.25-7.17 (2H, m), 7.08-7.02 (1H, m), 6.70 (1H, s), 3.14-3.06 (1H , m), 1.98-1.52 (8H, m).
Melting point (° C): 178-180.

Example 89
6-Chloro-3- (2-cyclohexylphenoxy) -4-pyridazinol (Compound No. 293)
^{1 H-NMR (60MHz, CDCl} 3 + DMF-d7) δppm: 7.40-6.70 (4H, m), 6.55 (1H s), 2.75 (1H, br.s), 2.10-0.90 (10H, m).
Melting point (° C): 158-159.

(Example 90)
6-Chloro-3- [2- (trifluoromethyl) phenoxy] -4-pyridazinol (Compound No. 300)
^{1 H-NMR (90MHz, CD3OD} ) δppm: 7.76-7.27 (4H, m), 6.75 (1H, s), 5.47 (1H, s).
Melting point (° C): 188.

(Example 91)
6-Chloro-3- [2- (1-propenyl) phenoxy} -4-pyridazinol (Compound No. 305)
¹ H-NMR (60 MHz, DMF-d7) δ ppm: 7.70-6.90 (5H, m), 6.76 (1H, s), 6.50-6.20 (2H, m), 1.81 (3H, d, J = 5.0 Hz).
Melting point (° C): 204-206.

(Example 92)
3- (2-Allylphenoxy) -6-chloro-4-pyridazinol (Compound No. 307)
¹ H-NMR (60MHz, DMF-d7) δppm: 7.46-7.24 (4H, m), 6.96 (1H s), 6.20-5.60 (1H, m), 5.20-4.80 (2H, m), 3.46-3.26 ( 2H, m).
Melting point (° C): 200-202.5.

(Example 93)
6-Chloro-3- [2- (1-propynyl) phenoxy] -4-pyridazinol (Compound No. 309)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.43-7.32 (2H, m), 7.23-7.16 (2H, m), 6.73 (1H, s), 1.87 (3H, s).
Melting point (° C): 182-284.

(Example 94)
6-Chloro-3- [2- (cyclopropylmethyl) phenoxy] -4-pyridazinol (Compound No. 311)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.45 (1H, dd, J = 7.3, 1.8Hz), 7.31-7.17 (2H, m), 7.10 (1H, dd, J = 7.3, 1.8Hz), 2.38 (2H, d, J = 7.0Hz), 1.00-0.88 (1H, m), 0.50-0.40 (2H, m), 0.22-0.11 (2H, m).
Melting point (° C): 165-168.

(Example 95)
3- (2-Benzylphenoxy) -6-chloro-4-pyridazinol (Compound No. 315)
Melting point (° C): 185-187.

Example 96
6-Chloro-3- [2- (methoxymethyl) phenoxy] -4-pyridazinol (Compound No. 324)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.47 (1H, br.d, J = 7.7Hz), 7.42-7.20 (2H, m), 7.15 (1H, br.d, J = 7.7Hz), 6.83 (1H, br.s), 4.35 (2H, s), 3.23 (3H, s).
Melting point (° C): 211-212.

(Example 97)
6-Chloro-3- [2- (ethoxymethyl) phenoxy] -4-pyridazinol (Compound No. 325)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.47 (1H, br.d, J = 7.7Hz), 7.42-7.20 (2H, m), 7.16 (1H, br.d, J = 7.7Hz), 6.82 (1H, br.s), 4.38 (2H, s), 3.39 (2H, q, J = 7.0Hz), 1.03 (3H, t, J = 7.0Hz).
Melting point (° C): 173-174.

(Example 98)
6-Chloro-3- [2- (1,3-dioxolan-2-yl) phenoxy] -4-pyridazinol (Compound No. 329)
Melting point (° C): 143-145.

Example 99
1- {2-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] phenyl} ethanone O-methyloxime (Compound No. 334)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.47 (2H, t, J = 7.7Hz), 7.31 (1H, d, J = 7.7Hz), 7.24 (1H, d, J = 7.7Hz), 6.85 (1H, br.s), 3.76 (2.8H, s), 3.58 (0.2H, s), 2.02 (2.8H, s), 1.99 (0.2H, s).
Melting point (° C): 165-167.

(Example 100)
Methyl 2-[(6-chloro-4-hydroxy-3-pyridazinyl) oxy] benzoate (Compound No. 339)
¹ H-NMR (60 MHz, CDCl ₃ + DMF-d7) δ ppm: 8.10-7.18 (4H, m), 6.80 (1H, s), 5.75 (1H, br.s), 3.70 (3H, s).
Melting point (° C): 188-191.

(Example 101)
3-([1,1'-biphenyl] -2-yloxy) -6-chloro-4-pyridazinol (Compound No. 344)
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 7.30-6.70 (10H, m), 6.25 (1H, s).
Melting point (° C): 98-100.

(Example 102)
6-Chloro-3-{[3 '-(trifluoromethyl) [1,1'-biphenyl] -2-yl] oxy} -4-pyridazinol (Compound No. 348)
¹ H-NMR (200 MHz, CDCl ₃ ) δ ppm: 7.65-7.58 (2H, m), 7.51-7.26 (5H, m), 7.12-7.06 (1H, m), 6.41 (1H, br.s).
Physical properties: Pasty.

(Example 103)
6-Chloro-3-{[3 '-(trifluoromethyl) [1,1'-biphenyl] -2-yl] oxy} -4-pyridazinol (Compound No. 349)
¹ H-NMR (200 MHz, CDCl ₃ ) δ ppm: 7.71-7.64 (2H, m), 7.55-7.30 (5H, m), 7.20-7.13 (1H, m), 6.43 (1H, s).
Physical properties: Pasty.

(Example 104)
6-Chloro-3- [2- (1-pyrrolidinyl) phenoxy] -4-pyridazinol (Compound No. 355)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.19-6.73 (4H, m), 5.64 (1H, s), 3.32-3.25 (4H, m), 1.91-1.84 (4H, m).
Physical properties: amorphous.

(Example 105)
6-Chloro-3- [2- (1H-pyrrol-1-yl) phenoxy] -4-pyridazinol (Compound No. 356)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.41-7.27 (4H, m), 6.95-6.93 (2H, m), 6.46 (1H, m), 6.10-6.08 (2H, m).
Physical properties: amorphous.

(Example 106)
6-Chloro-3- [2- (2-thienyl) phenoxy] -4-pyridazinol (Compound No. 359)
¹ H-NMR (200 MHz, CDCl ₃ ) δ ppm: 7.68-7.60 (1H, m), 7.45-7.05 (5H, m), 7.01-6.95 (1H, m), 6.52 (1H, s).
Physical properties: amorphous.

(Example 107)
6-Chloro-3- [2- (3-thienyl) phenoxy] -4-pyridazinol (Compound No. 361)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.46-7.37 (3H, m), 7.30-7.15 (4H, m).
Melting point (° C): 207-209.

(Example 108)
6-Chloro-3- [2- (1H-pyrazol-1-yl) phenoxy] -4-pyridazinol (Compound No. 362)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 8.09 (1H, d, J = 2.2 Hz), 7.70 (1H, dd, J = 7.5, 2.4 Hz), 7.62 (1H, d, J = 2.2 Hz), 7.50 -7.27 (3H, m), 6.55 (1H, s), 6.39 (1H, t, J = 2.2Hz).
Physical properties: amorphous.

(Example 109)
6-Chloro-3- [2- (3,5-dimethyl-1H-pyrazol-1-yl) phenoxy] -4-pyridazinol (Compound No. 364)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.60-7.32 (4H, m), 6.52 (1H, s), 5.86 (1H, s), 2.17 (3H, s), 2.10 (3H, s).
Physical properties: amorphous.

(Example 110)
6-Chloro-3- {2- [3- (trifluoromethyl) -1H-pyrazol-1-yl] phenoxy} -4-pyridazinol (Compound No. 365)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.79 (1H, br.s), 7.70-7.35 (5H, m), 7.06 (1H, br.s), 6.68 (1H, s).
Physical properties: amorphous.

(Example 111)
6-chloro-3- {2- [4- (trifluoromethyl) -1H-pyrazol-1-yl] phenoxy} -4-pyridazinol (Compound No. 366)
¹ H-NMR (200MHz, DMSO-d6) δppm: 8.75 (1H, s), 8.11 (1H, s), 7.80-7.74 (1H, m), 7.58-7.38 (3H, m), 6.77 (1H, s ).
Physical property: Oily substance.

(Example 112)
6-chloro-3- {2- [5- (trifluoromethyl) -1H-pyrazol-1-yl] phenoxy} -4-pyridazinol (Compound No. 367)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 8.30 (1H, br.s), 7.83-7.72 (1H, m), 7.60-7.40 (3H, m), 6.91 (1H, br.d, J = 2.6Hz), 6.78 (1H, s).
Physical properties: amorphous.

(Example 113)
5- {2-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] phenyl} -N, N-dimethyl-1H-pyrazole-1-sulfonamide (Compound No. 369)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.87 (1H, d, J = 2.6Hz), 7.78 (1H, dd, J = 7.3, 1.8Hz), 7.65-7.35 (3H, m), 7.20 (1H , s), 7.03 (1H, d, J = 2.6 Hz), 2.86 (6H, s).
Melting point (° C): 151-152.

(Example 114)
3- {2-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] phenyl} -N, N-dimethyl-1H-pyrazole-1-sulfonamide (Compound No. 368)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 9.19 (1H, d, J = 2.9Hz), 8.12 (1H, s), 7.97 (1H, dd, J = 7.3, 2.2Hz), 7.61 (1H, d , J = 1.5Hz), 7.50-7.33 (2H, m), 6.98 (1H, d, J = 2.9Hz), 2.83 (6H, s).
Melting point (° C): 210-212.

(Example 115)
6-Chloro-3- [2- (4-methyl-1,3-thiazol-2-yl) phenoxy] -4-pyridazinol (Compound No. 370)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.17 (1H, d, J = 7.7Hz), 7.73 (1H, d, J = 7.7Hz), 7.47 (1H, t, J = 7.7Hz), 7.28 ( 1H, t, J = 7.7Hz), 7.02 (1H, s), 6.98 (1H, s), 2.56 (3H, s).
Physical properties: amorphous.

(Example 116)
3- [2- (1,3-Benzoxazol-2-yl) phenoxy] -6-chloro-4-pyridazinol (Compound No. 375)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 8.31 (1H, dd, J = 7.9, 1.6 Hz), 7.73-7.30 (7H, m), 6.78 (1H, s).
Melting point (° C): 165-167.

(Example 117)
3- [2- (1,3-Benzothiazol-2-yl) phenoxy] -6-chloro-4-pyridazinol (Compound No. 376)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.12 (1H, d, J = 7.7Hz), 8.00-7.84 (1H, m), 7.78 (1H, d, J = 7.7Hz), 7.62-7.30 (5H m), 7.05 (1H, br.s).
Melting point (° C): 215-217.

(Example 118)
6-Chloro-3- [2- (dimethylamino) phenoxy] -4-pyridazinol (Compound No. 379)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.17-6.96 (4H, m), 6.61 (1H, s), 2.75 (6H, s).
Physical properties: amorphous.

(Example 119)
6-Chloro-3- (2-nitrophenoxy) -4-pyridazinol (Compound No. 383)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 8.16 (1H, d, J = 6.0 Hz), 7.90-7.33 (3H, m), 6.78 (1H, s).
Melting point (° C): 99-100.

(Example 120)
6-Chloro-3- (2-ethynylphenoxy) -4-pyridazinol (Compound No. 308)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.57-7.41 (2H, m), 7.30-7.20 (2H, m), 6.71 (1H, s), 3.60 (1H, s).
Melting point (° C): 189-191.

(Example 121)
6-Chloro-3- (2-methoxyphenoxy) -4-pyridazinol (Compound No. 385)
¹ H-NMR (60 MHz, CDCl ₃ + DMF-d7) δ ppm: 7.30-6.80 (4H, m), 6.55 (1H, s), 3.69 (3H, s).
Melting point (° C): 191-194.

(Example 122)
6-Chloro-3- (2-ethoxyphenoxy) -4-pyridazinol (Compound No. 386)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.26-7.02 (2H, m), 6.98-6.85 (2H, m), 6.57 (1H, s), 5.35 (1H, br.s), 3.92 (2H, q, J = 7.0Hz), 1.18 (t, 3H, J = 7.0Hz).
Melting point (° C): 155-175.

(Example 123)
6-Chloro-3- (2-isopropoxyphenoxy) -4-pyridazinol (Compound No. 387)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.28-7.10 (3H, m), 6.97 (1H, td, J = 7.3, 2.3Hz), 6.83 (1H, br.s), 4.52 (1H, septet , J = 6.2Hz), 1.07 (6H, d, J = 6.2Hz).
Melting point (° C): 178-179.

(Example 124)
6-Chloro-3- [2- (difluoromethoxy) phenoxy] -4-pyridazinol (Compound No. 390)
¹ H-NMR (200 MHz, CDCl ₃ ) δ ppm: 7.40 (4H, s), 6.63 (1H, s), 6.53 (1H, t, J = 73.8 Hz).
Melting point (° C): 210-212.

(Example 125)
6-Chloro-3- [2- (trifluoromethoxy) phenoxy] -4-pyridazinol (Compound No. 391)
¹ H-NMR (200 MHz, CDCl ₃ + CD3OD) δ ppm: 7.38-7.20 (4H, m), 6.60 (1H, s).
Melting point (° C): 215.

(Example 126)
6-Chloro-3- [2- (2-methoxyethoxy) phenoxy] -4-pyridazinol (Compound No. 396)
¹ H-NMR (200MHz, CD3OD) δppm: 7.26-6.93 (4H, m), 6.62 (1H, s), 4.78-4.03 (2H, m), 3.55-3.50 (2H, m), 3.24 (3H, s ).
Physical properties: Pasty.

(Example 127)
6-Chloro-3- [2- (2-hydroxyphenoxy) phenoxy] -4-pyridazinol (Compound No. 399)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.27-6.75 (8H, m), 6.61 (1H, s).
Physical properties: amorphous.

(Example 128)
6-chloro-3- {2- {2-[(6-chloro-4-ethoxy-3-pyridazinyl) oxy] phenoxy} phenoxy} -4-pyridazinol (Compound No. 400)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.65-6.70 (8H, m), 6.63-6.59 (2H, m), 4.19 (2H, q, J = 7.0Hz), 1.50 (3H, t, J = 7.0Hz).
Physical properties: amorphous.

(Example 129)
6-Chloro-3- [2- (methylsulfanyl) phenoxy] -4-pyridazinol (Compound No. 401)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.43-7.11 (4H, m), 6.71 (1H, s), 2.40 (3H, s).
Melting point (° C): 174-175.

(Example 130)
6-Chloro-3- [2- (isopropylsulfanyl) phenoxy] -4-pyridazinol (Compound No. 403)
Melting point (° C): 176-177.

(Example 131)
6-Chloro-3- (2-cyanophenoxy) -4-pyridazinol (Compound No. 330)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.82-7.68 (2H, m), 7.46-7.34 (2H, m), 6.79 (1H, s).
Physical properties: amorphous.

(Example 132)
1- {2- [6-Chloro-4-hydroxy-3-pyridazinyl] oxy} phenyl} ethanone (Compound No. 336)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.88-7.85 (1H, m), 7.65-7.57 (1H, m), 7.43-7.26 (2H, m), 6.73 (1H, s), 2.50 (3H, br.s).
Melting point (° C): 186-189.

(Example 133)
6-Chloro-3- (3-chlorophenoxy) -4-pyridazinol (Compound No. 410)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.45-7.10 (5H, m), 6.72 (1H, s).
Melting point (° C): 217.

(Example 134)
6-Chloro-3- (3-iodophenoxy) -4-pyridazinol (Compound No. 412)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.64-7.53 (2H, m), 7.28-6.70 (3H, m).
Melting point (° C): 202-203.

(Example 135)
6-Chloro-3- (3-methylphenoxy) -4-pyridazinol (Compound No. 413)
¹ H-NMR (60 MHz, DMF-d7) δ ppm: 7.35-6.80 (4H, m), 6.95 (1H, s), 2.35 (3H, s).
Melting point (° C): 205-208.

(Example 136)
6-Chloro-3- (3-isopropylphenoxy) -4-pyridazinol (Compound No. 415)
Melting point (° C): 176-177.

(Example 137)
3- (3-tert-Butylphenoxy) -6-chloro-4-pyridazinol (Compound No. 416)
¹ H-NMR (60 MHz, DMSO-d6) δ ppm: 7.40-6.65 (4H, m), 6.67 (1H, s), 1.27 (9H, s).
Melting point (° C): 203-207.

(Example 138)
6-Chloro-3- (3-cyclopropylphenoxy) -4-pyridazinol (Compound No. 417)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.35-7.20 (1H, m), 6.98-6.85 (3H, m), 6.78 (1H, br.s), 2.00-1.88 (1H, m), 0.98 -0.87 (2H, m), 0.70-0.60 (2H, m).
Melting point (° C): 179-181.

(Example 139)
6-Chloro-3- [3- (trifluoromethyl) phenoxy] -4-pyridazinol (Compound No. 418)
¹ H-NMR (60 MHz, DMF-d7) δ ppm: 7.70-7.40 (4H, m), 6.95 (1H, s).
Melting point (° C): 213-216.

(Example 140)
6-Chloro-3- [3- (2-furyl) phenoxy] -4-pyridazinol (Compound No. 419)
¹ H-NMR (200 MHz, CDCl ₃ + CD3OD) δppm: 7.55-7.35 (4H, m), 7.08-7.02 (1H, m), 6.67 (1H, d, J = 3.3 Hz), 6.59 (1H, br. s), 6.48 (1H, dd, J = 3.3, 1.8 Hz).
Melting point (° C): 200-202.

(Example 141)
3-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] benzonitrile (Compound No. 420)
¹ H-NMR (90 MHz, CD3OD) δ ppm: 7.70-7.40 (4H, m), 6.75 (1H, s).
Melting point (° C): 226-229.

(Example 142)
3-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] benzaldehyde (Compound No. 421)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 9.96 (1H, s), 7.72-7.53 (3H, m), 7.46-7.41 (1H, m), 6.54 (1H, s).
Melting point (° C): 188-192.

(Example 143)
1- {3-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] phenyl} ethanone (Compound No. 422)
Melting point (° C): 195-198.

(Example 144)
Methyl 3-[(6-chloro-4-hydroxy-3-pyridazinyl) oxy] benzoate (Compound No. 423)
¹ H-NMR (90 MHz, CD3OD) δ ppm: 8.00-7.70 (2H, m), 7.70-7.30 (2H, m), 6.75 (1H, s), 3.30 (3H, s).
Melting point (° C): 207.

(Example 145)
6-Chloro-3- (3-nitrophenoxy) -4-pyridazinol (Compound No. 424)
¹ H-NMR (60 MHz, DMF-d7) δ ppm: 8.30-7.90 (2H, m), 7.90-7.70 (2H, m), 6.50 (1H, s), 5.80-5.15 (1H, br.s).
Melting point (° C): 217-219.

(Example 146)
6-Chloro-3- (3-methoxyphenoxy) -4-pyridazinol (Compound No. 425)
¹ H-NMR (60 MHz, CDCl ₃ + DMF-d7) δppm: 7.50-7.10 (1H, m), 6.90-6.60 (3H, m), 6.70 (1H, s), 5.88 (1H, br.s), 3.77 (3H, s).
Melting point (° C): 199-203.

(Example 147)
6-Chloro-3- (4-chlorophenoxy) -4-pyridazinol (Compound No. 427)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.45-7.38 (2H, m), 7.23-7.15 (2H, m), 6.70 (1H, s).
Melting point (° C): 226-231.

(Example 148)
6-Chloro-3- (4-methylphenoxy) -4-pyridazinol (Compound No. 430)
¹ H-NMR (60 MHz, DMSO-d6) δ ppm: 7.25-6.83 (4H, m), 6.68 (1H, s), 2.25 (3H, s).
Melting point (° C): 261-263.

(Example 149)
6-Chloro-3- (4-isopropylphenoxy) -4-pyridazinol (Compound No. 432)
Melting point (° C): 233-235.

(Example 150)
3- (4-tert-Butylphenoxy) -6-chloro-4-pyridazinol (Compound No. 433)
Melting point (° C): 224-225.

(Example 151)
6-Chloro-3- (4-cyclopropylphenoxy) -4-pyridazinol (Compound No. 434)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.15–7.02 (4H, m), 6.82 (1H, br.s), 2.01-1.90 (1H, m), 0.99-0.90 (2H, m), 0.70 -0.62 (2H, m)
Melting point (° C): 221-227.

(Example 152)
6-Chloro-3- (4-methoxyphenoxy) -4-pyridazinol (Compound No. 435)
¹ H-NMR (60 MHz, DMF-d7) δ ppm: 7.26-6.85 (4H, m), 6.80 (1H, br.s), 3.81 (3H, s).
Melting point (° C): 260-263.5.

(Example 153)
6-Chloro-3- [4- (trimethylsilyl) phenoxy] -4-pyridazinol (Compound No. 436)
Melting point (° C): 197-199.

(Example 154)
6-Chloro-3- (2,3-difluorophenoxy) -4-pyridazinol (Compound No. 437)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.24-7.05 (3H, m), 6.73 (1H, s).
Melting point (° C): 188-193.

(Example 155)
6-Chloro-3- (3-chloro-2-fluorophenoxy) -4-pyridazinol (Compound No. 438)
^{1 H-NMR (200MHz, CD3OD} ) δppm: 7.43-7.21 (3H, m), 6.75 (1H, s).
Melting point (° C): 187-195.

(Example 156)
6-Chloro-3- [2-fluoro-3- (trifluoromethyl) phenoxy] -4-pyridazinol (Compound No. 441)
^{1 H-NMR (200MHz, DMSO} -d6) δppm: 7.78-7.66 (2H, m), 7.48 (1H, t, J = 8.1Hz), 6.83 (1H, s).
Melting point (° C): 185-189.

(Example 157)
6-Chloro-3- (2,3-dichlorophenoxy) -4-pyridazinol (Compound No. 443)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.62-7.57 (1H, m), 7.50-7.37 (2H, m), 6.89 (1H, s).
Melting point (° C): 233-238.

(Example 158)
6-Chloro-3- [2-chloro-3- (trifluoromethyl) phenoxy] -4-pyridazinol (Compound No. 446)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.74-7.55 (3H, m), 6.76 (1H, s).
Melting point (° C): 170-200.

(Example 159)
3- (2-Bromo-3-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 450)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.35 (1H, t, J = 7.5Hz), 7.27 (1H, dd, J = 7.5, 2.2Hz), 7.16 (1H, dd, J = 7.5, 2.2 Hz), 6.87 (1H, br.s), 2.41 (3H, s).
Melting point (° C): 140-141.

(Example 160)
6-Chloro-3- (3-fluoro-2-methylphenoxy) -4-pyridazinol (Compound No. 453)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.30-7.15 (1H, m), 7.08-6.85 (2H, m), 6.73 (1H, s), 2.09 (3H, d, J = 1.8 Hz).
Melting point (° C): 242-244.

(Example 161)
6-Chloro-3- (3-chloro-2-methylphenoxy) -4-pyridazinol (Compound No. 454)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.39-7.12 (4H, m), 2.14 (3H, s).
Melting point (° C): 250-252.

(Example 162)
6-Chloro-3- (2,3-dimethylphenoxy) -4-pyridazinol (Compound No. 456)
¹ H-NMR (60 MHz, DMSO-d6) δ ppm: 7.22-6.98 (3H, m), 6.77 (1H, s), 2.30 (3H, s), 2.02 (3H, s).
Melting point (° C): 240-241.

(Example 163)
6-Chloro-3- (2-methyl-3-nitrophenoxy) -4-pyridazinol (Compound No. 458)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.89-7.84 (1H, m), 7.58-7.47 (2H, m), 6.90 (1H, br.s), 2.25 (3H, s).
Melting point (° C): 241-244.

(Example 164)
6-Chloro-3- (3-methoxy-2-methylphenoxy) -4-pyridazinol (Compound No. 459)
¹ H-NMR (200MHz, CD3OD) δppm: 7.14 (1H, t, J = 8.4Hz), 6.78 (1H, d, J = 8.4Hz), 6.63 (1H, d, J = 8.4Hz), 6.55 (1H , s), 3.83 (3H, s), 2.00 (3H, s).
Melting point (° C): 224-237.

(Example 165)
6-chloro-3- {3-[(6-chloro-4-hydroxy-3-pyridazinyl) oxy] -2-methylphenoxy} -4-pyridazinol (Compound No. 460)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.16 (1H, t, J = 8.4 Hz), 6.85 (2H, d, J = 8.4 Hz), 6.48 (2H, s), 2.15 (3H, s).
Melting point (° C):> 290.

(Example 166)
6-Chloro-3- (2-cyclopropyl-3-methylphenoxy) -4-pyridazinol (Compound No. 472)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.18 (1H, t, J = 7.7 Hz), 7.07 (1H, br.d, J = 7.7 Hz), 6.91 (1H, br.d, J = 7.7 Hz), 6.82 (1H, br.s), 2.40 (3H, s), 1.43-1.28 (1H, m), 0.79-0.68 (2H, m), 0.59-0.48 (2H, m).
Melting point (° C): 197-198.

(Example 167)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl tetrahydro-2H-pyran-4-carboxylate (Compound No. 3856)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.38 (1H, s), 7.15-7.04 (2H, m), 6.90-6.78 (1H, m), 4.10-3.95 (2H, m), 3.60-3.43 ( 2H, m), 3.03-2.86 (1H, m), 2.11 (3H, s), 2.06-1.90 (4H, m), 1.80-1.60 (1H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 168)
Methyl 2-[(6-chloro-4-hydroxy-3-pyridazinyl) oxy] -6-fluorobenzoate (Compound No. 491)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.62 (1H, td, J = 8.4, 5.6 Hz), 7.23 (1H, t, J = 8.4 Hz), 7.02 (1H, d, J = 8.4 Hz), 3.83 (3H, s).
Physical properties: amorphous.

(Example 169)
6-Chloro-3- (3-methyl-2-nitrophenoxy) -4-pyridazinol (Compound No. 498)
¹ H-NMR (200MHz, CD3OD) δppm: 7.48 (1H, t, J = 8.1Hz), 7.26 (1H, d, J = 8.1Hz), 7.19 (1H, d, J = 8.1Hz), 6.66 (1H , s), 2.37 (3H, s).
Melting point (° C): 191-200.

(Example 170)
6-Chloro-3- (2,3-dimethoxyphenoxy) -4-pyridazinol (Compound No. 503)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.14-6.78 (4H, m), 3.84 (3H, s), 3.61 (3H, s).
Melting point (° C): 199-201.

(Example 171)
6-Chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinol (Compound No. 506)
^{1 H-NMR (200MHz, DMSO} -d6) δppm: 7.20 (1H, t, J = 7.3Hz), 7.14 (1H, d, J = 7.3Hz), 6.92 (1H, d, J = 7.3Hz), 6.83 (1H, br.s), 2.92 (1H, t, J = 7.3Hz), 2.64 (1H, t, J = 7.3Hz), 2.00 (1H, quintet, J = 7.3Hz).
Melting point (° C): 230-232.

(Example 172)
6-Chloro-3-[(3-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinol (Compound No. 507)
¹ H-NMR (200MHz, CD3OD) δppm: 7.17 (1H, t, J = 7.7Hz), 7.08 (1H, d, J = 7.7Hz), 6.88 (1H, d, J = 7.7Hz), 6.69 (1H , s), 3.35-3.15 (1H, m), 3.10-2.70 (2H, m), 2.40-2.15 (1H, m), 1.80-1.55 (1H, m), 1.15 (3H, d, J = 7.0Hz )
Melting point (° C): 232.

(Example 173)
6-Chloro-3-[(1-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinol (Compound No. 510)
¹ H-NMR (200MHz, CD3OD) δppm: 7.21 (1H, dd, J = 8.1, 7.3Hz), 7.09 (1H, d, J = 7.3Hz), 6.91 (1H, d, J = 8.1Hz), 6.70 (1H, s), 3.30-3.05 (1H, m), 2.85-2.50 (2H, m), 2.40-2.20 (1H, m), 1.70-1.45 (1H, m), 1.29 (3H, d, J = 7.0Hz).
Melting point (° C): 228-230.

(Example 174)
6-Chloro-3-[(2,2-dimethyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinol (Compound No. 513)
¹ H-NMR (200MHz, CD3OD) δppm: 7.17 (1H, t, J = 7.7Hz), 7.05 (1H, d, J = 7.7Hz), 6.89 (1H, d, J = 7.7Hz), 6.69 (1H , s), 2.76 (2H, s), 2.53 (2H, s), 1.13 (6H, s).
Melting point (° C): 220-223.

(Example 175)
6-Chloro-3- {spiro [cyclopropane-1,3 '-(2', 3'-dihydro-1'H-indene)]-4'-yloxy} -4-pyridazinol (Compound No. 514)
¹ H-NMR (200MHz, CD3OD) δppm: 7.15-6.95 (2H, m), 6.75 (1H, dd, J = 6.6, 2.6Hz), 6.66 (1H, s), 3.02 (2H, dd, J = 7.7 , 7.3Hz), 2.15-1.95 (2H, m), 1.28-1.15 (2H, m), 0.80-0.70 (2H, m).
Physical properties: amorphous.

(Example 176)
6-Chloro-3- (4-fluorophenoxy) -4-pyridazinol (Compound No. 426)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.26-7.05 (4H, m), 6.70 (1H, s).
Melting point (° C): 241-248.

(Example 177)
3- (Bicyclo [4.2.0] octa-1,3,5-trien-2-yloxy) -6-chloro-4-pyridazinol (Compound No. 505)
¹ H-NMR (200MHz, CD3OD) δppm: 7.22 (1H, dd, J = 8.2, 7.3Hz), 6.96 (1H, d, J = 8.2Hz), 6.91 (1H, d, J = 7.3Hz), 6.69 (1H, s), 3.19-3.11 (2H, m), 3.10-3.00 (2H, m).
Melting point (° C): 145-155.

(Example 178)
7-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] -2,3-dihydro-1H-inden-1-one O-methyloxime (Compound No. 520)
¹ H-NMR (200MHz, CD3OD) δppm: 7.50-7.15 (2H, m), 7.07 (1H, dd, J = 8.1, 7.3Hz), 6.55 (0.4H, s), 5.77 (0.6H, s), 3.73 (1.8H, s), 3.67 (1.2H, s), 3.15-3.00 (2H, m), 2.90-2.73 (2H, m).
Melting point (° C):> 250.

(Example 179)
6-Chloro-3- (5,6,7,8-tetrahydro-1-naphthalenyloxy) -4-pyridazinol (Compound No. 521)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.14 (1H, t, J = 7.7Hz), 6.98 (1H, d, J = 7.7Hz), 6.89 (1H, d, J = 7.7Hz), 6.82 (1H, br.s), 2.80-2.70 (2H, m), 2.50-2.40 (2H, m), 1.85-1.70 (4H, m).
Melting point (° C): 232-237.

(Example 180)
6-Chloro-3- (1-naphthyloxy) -4-pyridazinol (Compound No. 527)
¹ H-NMR (60 MHz, DMSO-d6) δ ppm: 8.10-7.20 (7H, m), 6.85 (1H, s), 6.20 (1H, br.s).
Melting point (° C): 243-245.

(Example 181)
6-Chloro-3- (2,3-dihydro-1-benzofuran-4-yloxy) -4-pyridazinol (Compound No. 528)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.11 (1H, t, J = 8.1Hz), 6.65 (1H, s), 6.60 (1H, d, J = 8.1Hz), 6.56 (1H d, J = 8.1Hz), 4.53 (2H, t, J = 8.5Hz), 2.97 (2H, t, J = 8.5Hz).
Melting point (° C): 219-221.

(Example 182)
6-Chloro-3-[(3-methyl-2,3-dihydro-1-benzofuran-4-yl) oxy] -4-pyridazinol (Compound No. 529)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.15 (1H, t, J = 8.1 Hz), 6.85 (1H, br.s), 6.67 (1H, d, J = 8.1 Hz), 6.62 (1H, d, J = 8.1Hz), 4.65 (1H, t, J = 8.8Hz), 4.12-4.04 (1H, m), 3.50-3.39 (1H, m), 1.14 (3H, d, J = 7.0Hz).
Melting point (° C): 238-245.

(Example 183)
3- (1-Benzofuran-4-yloxy) -6-chloro-4-pyridazinol (Compound No. 531)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.99 (1H, d, J = 2.0Hz), 7.52 (1H, d, J = 7.8Hz), 7.35 (1H, t, J = 7.8Hz), 7.06 (1H, d, J = 7.8Hz), 6.87 (1H, s), 6.81 (1H, d, J = 2.0Hz).
Melting point (° C): 220-225.

(Example 184)
6-Chloro-3-[(3-methyl-1-benzofuran-4-yl) oxy] -4-pyridazinol (Compound No. 532)
¹ H-NMR (200MHz, CD3OD) δppm: 7.44 (1H, d, J = 1.5Hz), 7.33-7.20 (2H, m), 6.91 (1H, dd, J = 7.0, 1.5Hz), 6.61 (1H, s), 2.01 (3H, s).
Melting point (° C): 218-225.

(Example 185)
3- (1-Benzothienen-4-yloxy) -6-chloro-4-pyridazinol (Compound No. 534)
¹ H-NMR (200MHz, CD3OD) δppm: 7.75 (1H, d, J = 8.1Hz), 7.53 (1H, d, J = 5.5Hz), 7.35 (1H, dd, J = 8.1, 7.7Hz), 7.28 (1H, dd, J = 5.5, 0.7 Hz), 7.10 (1H, dd, J = 7.7, 0.7 Hz), 6.64 (1H, s).
Melting point (° C): 181-183.

(Example 186)
6-Chloro-3- (8-quinolinyloxy) -4-pyridazinol (Compound No. 535)
¹ H-NMR (200MHz, DMSO-d6) δppm: 8.80 (1H, dd, J = 4.0, 1.5Hz), 8.46 (1H, dd, J = 8.4, 1.5Hz), 7.93-7.87 (1H, m), 7.70-7.63 (2H, m), 7.57 (1H, dd, J = 8.4, 4.0Hz), 6.82 (1H, s).
Melting point (° C):> 200 (dec.).

(Example 187)
6-Chloro-3- (8-quinolinyloxy) -4-pyridazinol (Compound No. 536)
¹ H-NMR (200MHz, DMSO-d6) δppm: 8.81 (1H, dd, J = 4.0, 1.5Hz), 8.41 (1H, dd, J = 8.4, 1.5Hz), 7.81 (1H, d, J = 7.0 Hz), 7.62-7.52 (2H, m), 7.41 (1H, d, J = 7.7Hz), 6.43 (1H, s).
Melting point (° C):> 180 (dec.).

(Example 188)
6-Chloro-3-[(2-methyl-1,3-benzoxazol-4-yl) oxy] -4-pyridazinol (Compound No. 538)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.55-7.32 (2H, m), 7.22-7.10 (1H, m), 6.73 (1H, s), 2.59 (3H, s).
Melting point (° C): 221-222.

(Example 189)
6-Chloro-3- (2,3-dihydro-1-benzofuran-7-yloxy) -4-pyridazinol (Compound No. 539)
¹ H-NMR (200MHz, CD3OD) δppm: 7.13-7.08 (1H, m), 6.95 (1H, d, J = 7.3Hz), 6.85 (1H, dd, J = 8.1, 7.3Hz), 6.67 (1H, s), 4.54 (2H, t, J = 8.4Hz), 3.30-3.20 (2H, m).
Physical properties: amorphous.

(Example 190)
6-Chloro-3-[(2,2-dimethyl-2,3-dihydro-1-benzofuran-7-yl) oxy] -4-pyridazinol (Compound No. 540)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.08 (1H, d, J = 7.3Hz), 6.96 (1H, d, J = 8.1Hz), 6.87-6.79 (2H, m), 3.06 (2H, s), 1.37 (6H, s).
Melting point (° C): 228-229.5.

(Example 191)
3- (1-Benzofuran-7-yloxy) -6-chloro-4-pyridazinol (Compound No. 541)
¹ H-NMR (200MHz, CD3OD) δppm: 7.73 (1H, d, J = 2.2Hz), 7.53 (1H, dd, J = 7.7, 1.4Hz), 7.26 (1H, t, J = 7.7Hz), 7.15 (1H, dd, J = 7.7, 1.4Hz), 6.90 (1H, d, J = 2.2Hz), 6.76 (1H, s).
Melting point (° C): 201-202.

(Example 192)
3- (1,3-Benzodioxol-4-yloxy) -6-chloro-4-pyridazinol (Compound No. 544)
^{1 H-NMR (200MHz, DMSO} -d6) δppm: 6.94-6.75 (4H, m), 6.01 (2H, s).
Melting point (° C): 206-211.

(Example 193)
6-Chloro-3- (2,3-dihydro-1,4-benzodioxin-5-yloxy) -4-pyridazinol (Compound No. 547)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 6.90-6.72 (4H, m), 4.27-4.15 (4H, m).
Melting point (° C): 218-223.5.

(Example 194)
6-Chloro-3-[(2-methyl-1,3-benzoxazol-7-yl) oxy] -4-pyridazinol (Compound No. 549)
¹ H-NMR (200MHz, CD3OD) δppm: 7.52 (1H, dd, J = 8.1, 1.1Hz), 7.37 (1H, t, J = 8.1Hz), 7.21 (1H, dd, J = 8.1, 1.1Hz) , 6.76 (1H, s), 2.65 (3H, s).
Melting point (° C): 197-202.

(Example 195)
6-Chloro-3- (2,4-dichlorophenoxy) -4-pyridazinol (Compound No. 552)
¹ H-NMR (60 MHz, DMF-d7) δ ppm: 7.55 (1H, t, J = 1.8 Hz), 7.35 (2H, d, J = 1.8 Hz), 6.88 (1H, s).
Melting point (° C): 233-237.

(Example 196)
3- (2-Bromo-4-tert-butylphenoxy) -6-chloro-4-pyridazinol (Compound No. 556)
¹ H-NMR (60MHz, DMSO-d6) δppm: 7.61 (1H, d, J = 2.0Hz), 7.43 (1H, dd, J = 8.4, 2.0Hz), 7.17 (1H, d, J = 8.4Hz) , 6.73 (1H, s), 1.32 (9H, s).
Melting point (° C):> 202 (dec.).

(Example 197)
6-Chloro-3- (4-chloro-2-methylphenoxy) -4-pyridazinol (Compound No. 558)
¹ H-NMR (60 MHz, DMSO-d6 + CDCl ₃ ) δ ppm: 7.40-7.10 (3H, m), 6.65 (1H, s), 2.18 (3H, s).
Melting point (° C): 235-235.5.

(Example 198)
6-Chloro-3- (2,4-dimethylphenoxy) -4-pyridazinol (Compound No. 559)
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 7.17-6.98 (3H, m), 6.85 (1H, s), 2.29 (3H, s), 2.07 (3H, s).
Melting point (° C): 217.5.

(Example 199)
6-Chloro-3- (2-ethyl-4-iodophenoxy) -4-pyridazinol (Compound No. 562)
¹ H-NMR (200MHz, CD3OD) δppm: 7.59 (1H, d, J = 2.2Hz), 7.49 (1H, dd, J = 8.4, 2.2Hz), 6.75 (1H, d, J = 8.4Hz), 6.48 (1H, s), 2.65-1.95 (2H, m), 1.16 (3H, t, J = 7.7Hz).
Melting point (° C): 199-201.

(Example 200)
3- (4-Bromo-2-isopropylphenoxy) -6-chloro-4-pyridazinol (Compound No. 566)
¹ H-NMR (60MHz, DMSO-d6) δppm: 7.44 (1H, br.s), 7.37 (1H, dd, J = 8.0, 2.2Hz), 7.00 (1H, d, J = 8.0Hz), 6.73 ( 1H, s), 3.01 (1H, septet, J = 6.8Hz), 1.15 (6H, d, J = 6.8Hz).
Melting point (° C): 215-225.

(Example 201)
3- (2-tert-Butyl-4-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 567)
¹ H-NMR (90 MHz, CD3OD) δ ppm: 7.25 (1H, d, J = 2.0 Hz), 7.05 (1H, dd, J = 8.0, 2.0 Hz), 6.85 (1H, d, J = 8.0 Hz), 6.70 (1H, s), 2.30 (3H, s), 1.35 (9H, s).
Melting point (° C): 230-236.

(Example 202)
6-Chloro-3- (2-cyclopropyl-4-methylphenoxy) -4-pyridazinol (Compound No. 571)
¹ H-NMR (200MHz, CD3OD) δppm: 7.05-6.95 (1H, m), 6.96 (1H, s), 6.81 (1H, s), 6.68 (1H, m), 2.30 (3H, s), 1.90- 1.75 (1H, m), 0.90-0.70 (2H, m), 0.70-0.50 (2H, m).
Melting point (° C): 239.

(Example 203)
6-Chloro-3- (2-chloro-5-methylphenoxy) -4-pyridazinol (Compound No. 614)
¹ H-NMR (90MHz, CD3OD) δppm: 7.40 (1H, d, J = 8.5Hz), 7.15 (1H, s), 7.10 (1H, d, J = 8.5Hz), 6.70 (1H, s), 2.35 (3H, s).
Melting point (° C): 170.
(Example 204)
6-Chloro-3- (5-chloro-2-methylphenoxy) -4-pyridazinol (Compound No. 618)
^{1 H-NMR (200MHz, CD3OD} ) δppm: 7.28 (1H, d, J = 8.8Hz), 7.21-7.15 (1H, m), 7.16 (1H, s), 6.72 (1H, s), 2.15 (3H, s).
Melting point (° C): 174-180.

(Example 205)
6-Chloro-3- (2,5-dimethylphenoxy) -4-pyridazinol (Compound No. 621)
¹ H-NMR (90MHz, CD3OD) δppm: 7.16 (1H, d, J = 9.0Hz), 7.08 (1H, d, J = 9.0Hz), 6.90 (1H, s), 6.70 (1H, s), 2.30 (3H, s), 2.10 (3H, s).
Melting point (° C): 80-83.

(Example 206)
6-Chloro-3- (5-isopropyl-2-methylphenoxy) -4-pyridazinol (Compound No. 623)
¹ H-NMR (90MHz, CD3OD) δppm: 7.20 (1H, d, J = 7.5Hz), 7.15-6.98 (1H, m), 6.95 (1H, s), 6.70 (1H, s), 2.88 (1H, septet, J = 7.5Hz), 2.10 (3H, s), 1.23 (6H, d, J = 7.5Hz).
Melting point (° C): 168-169.

(Example 207)
3-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] -4-methylbenzoic acid (Compound No. 626)
Melting point (° C): 238-240.

(Example 208)
3- (5-Amino-2-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 627)
Melting point (° C):> 310.

(Example 209)
6-Chloro-3- [5- (dimethylamino) -2-methylphenoxy] -4-pyridazinol (Compound No. 628)
¹ H-NMR (200MHz, CD3OD) δppm: 7.08 (1H, d, J = 8.4Hz), 6.68 (1H, s), 6.61 (1H, dd, J = 8.4, 2.6Hz), 6.50 (1H, d, J = 2.6Hz), 2.88 (6H, s), 2.02 (3H, s).
Melting point (° C): 181-182.

(Example 210)
6-Chloro-3- (5-methoxy-2-methylphenoxy) -4-pyridazinol (Compound No. 629)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.16 (1H, d, J = 8.4 Hz), 6.78-6.67 (3H, m), 3.75 (3H, s), 2.07 (3H, s).
Melting point (° C): 170-172.

(Example 211)
6-Chloro-3- (2-ethyl-5-methoxyphenoxy) -4-pyridazinol (Compound No. 635)
¹ H-NMR (60MHz, DMF-d7) δppm: 7.15 (1H, br.d, J = 8.0Hz), 6.74 (1H, br.s), 6.73 (1H, br.d, J = 8.0Hz), 6.63 (1H, s), 3.73 (3H, s), 2.46 (2H, q, J = 7.0Hz), 1.10 (3H, t, J = 7.0Hz).
Melting point (° C): 124-126.

(Example 212)
6-Chloro-3- (2-isopropyl-5-methylphenoxy) -4-pyridazinol (Compound No. 640)
¹ H-NMR (60 MHz, CDCl ₃ + DMF-d7) δppm: 7.50-6.70 (3H, m), 6.58 (1H, s), 3.30-2.60 (1H, m), 2.26 (3H, s), 1.13 ( 6H, d, J = 6.60Hz).
Melting point (° C): 193-195.

(Example 213)
6-Chloro-3- (3,5-diisopropylphenoxy) -4-pyridazinol (Compound No. 642)
¹ H-NMR (60MHz, DMSO-d6) δppm: 7.25 (1H, d, J = 8.0Hz), 7.11 (1H, d, J = 1.8Hz), 6.92 (1H, dd, J = 8.0, 1.8Hz) , 6.73 (1H, s), 2.84 (2H, septet, J = 7.0Hz), 1.18 (6H, d, J = 7.0Hz), 1.12 (6H, d, J = 7.0Hz).
Melting point (° C): 231-235.

(Example 214)
3- (2-tert-Butyl-5-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 650)
¹ H-NMR (90MHz, CD3OD) δppm: 7.35 (1H, d, J = 8.0Hz), 6.95 (1H, dd, J = 8.0, 1.5Hz), 6.80 (1H, s), 6.70 (1H, s) , 2.27 (3H, s), 1.35 (9H, s).
Melting point (° C): 226.

(Example 215)
6-Chloro-3- (2,5-ditert-butylphenoxy) -4-pyridazinol (Compound No. 653)
¹ H-NMR (60MHz, DMF-d7) δppm: 7.50-7.10 (3H, m), 6.94 (1H, s), 4.98 (1H br.s), 1.37 (9H, s), 1.28 (9H, s) .
Melting point (° C): 249-258.

(Example 216)
6-Chloro-3- (2-cyclopropyl-5-fluorophenoxy) -4-pyridazinol (Compound No. 658)
¹ H-NMR (200MHz, CD3OD) δppm: 7.10-6.85 (3H, m), 6.72 (1H, s), 1.92-1.75 (1H, m), 0.85-0.70 (2H, m), 0.70-0.54 (2H , m).
Melting point (° C): 227-228.

(Example 217)
6-Chloro-3- (5-chloro-2-cyclopropylphenoxy) -4-pyridazinol (Compound No. 659)
¹ H-NMR (200MHz, CD3OD) δppm: 7.19 (1H, d, J = 7.7Hz), 7.16 (1H, s), 7.01 (1H, d, J = 7.7Hz), 6.72 (1H, s), 1.94 -1.79 (1H, m), 0.90-0.75 (2H, m), 0.75-0.58 (2H, m).
Melting point (° C): 194-195.

(Example 218)
6-Chloro-3- (2-cyclopropyl-5-methylphenoxy) -4-pyridazinol (Compound No. 662)
¹ H-NMR (200MHz, CD3OD) δppm: 6.96 (1H, d, J = 7.7Hz), 6.89 (1H, s), 6.87 (1H, d, J = 7.7Hz), 6.68 (1H, s), 2.28 (3H, s), 1.87-1.73 (1H, m), 0.80-0.51 (4H, m).
Melting point (° C): 150-159.

(Example 219)
6-Chloro-3- (2-cyclopropyl-5-ethylphenoxy) -4-pyridazinol (Compound No. 663)
¹ H-NMR (200MHz, CD3OD) δppm: 7.01 (1H, d, J = 8.0Hz), 6.92 (1H, s), 6.92 (1H, d, J = 8.0Hz), 6.69 (1H, s), 2.61 (2H, t, J = 7.7Hz), 1.88-1.72 (1H, m), 1.20 (3H, q, J = 7.7Hz), 0.82-0.66 (2H, m), 0.65-0.52 (2H, m).
Physical properties: amorphous.

(Example 220)
6-Chloro-3- (2-cyclopropyl-5-isopropylphenoxy) -4-pyridazinol (Compound No. 664)
¹ H-NMR (200MHz, CD3OD) δppm: 7.05 (1H, dd, J = 7.7, 1.8Hz), 7.00 (1H, br.s), 6.93 (1H, d, J = 7.7Hz), 6.70 (1H, s), 2.87 (1H, septet, J = 7.0Hz), 1.90-1.72 (1H, m), 1.22 (6H, d, J = 7.0Hz), 0.85-0.68 (2H, m), 0.68-0.52 (2H , m).
Melting point (° C): 211-212.

(Example 221)
3-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] -4-cyclopropylbenzonitrile (Compound No. 667)
¹ H-NMR (200MHz, CD3OD) δppm: 7.58-7.48 (2H, m), 7.15 (1H, d, J = 8.8Hz), 6.74 (1H, s), 2.10-1.90 (1H, m), 1.05- 0.93 (2H, m), 0.83-0.70 (2H, m).
Melting point (° C): 211-212.

(Example 222)
6-Chloro-3- [5-fluoro-2- (1-propenyl) phenoxy] -4-pyridazinol (Compound No. 679)
¹ H-NMR (200MHz, CD3OD) δppm: 7.61-7.53 (1H, m), 7.03-6.90 (2H, m), 6.72 (1H, s), 6.44-6.19 (2H, m), 1.80 (3H, d , J = 5.5Hz).
Melting point (° C): 210-217.

(Example 223)
6-Chloro-3- [5-chloro-2- (1-propenyl) phenoxy] -4-pyridazinol (Compound No. 680)
¹ H-NMR (200MHz, CD3OD) δppm: 7.55 (1H, d, J = 8.4Hz), 7.24-7.17 (2H, m), 6.72 (1H, s), 6.46-6.30 (2H, m), 1.81 ( 3H, d, J = 5.1Hz).
Melting point (° C): 221-224.

(Example 224)
2-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] -4- (dimethylamino) benzaldehyde (Compound No. 692)
¹ H-NMR (90MHz, DMSO-d6) δppm: 9.78 (1H, s), 7.69 (1H, d, J = 6.0Hz), 6.81 (1H, s), 6.78-6.46 (2H, m), 3.05 ( 6H, s).
Melting point (° C): 124-127.

(Example 225)
3- (5-Chloro-2-methoxyphenoxy) -6-chloro-4-pyridazinol (Compound No. 701)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.23-7.18 (2H, m), 7.05 (1H, d, J = 8.8 Hz), 6.66 (1H, s), 3.73 (3H, s).
Melting point (° C): 143-155.

(Example 226)
3- (5-Bromo-2-methoxyphenoxy) -6-chloro-4-pyridazinol (Compound No. 702)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.39-7.31 (2H, m), 7.02 (1H, d, J = 8.4 Hz), 6.67 (1H, s), 3.74 (3H, s).
Melting point (° C): 135-137.

(Example 227)
6-Chloro-3- (4-fluoro-2-methylphenoxy) -4-pyridazinol (Compound No. 557)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.14-6.88 (3H, m), 6.71 (1H, s), 2.16 (3H, s).
Melting point (° C): 249-250.

(Example 228)
3-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] -4-methoxybenzonitrile (Compound No. 707)
¹ H-NMR (200MHz, CD3OD) δppm: 7.66 (1H, dd, J = 8.4, 2.2Hz), 7.58 (1H, d, J = 2.2Hz), 7.26 (1H, d, J = 8.4Hz), 6.71 (1H, s), 3.85 (3H, s).
Melting point (° C): 187-192.

(Example 229)
6-Chloro-3- (2-methoxy-5-nitrophenoxy) -4-pyridazinol (Compound No. 708)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 8.18 (1H, dd, J = 9.2, 2.6 Hz), 8.04 (1H, d, J = 2.6 Hz), 7.27 (1H, d, J = 9.2 Hz), 6.59 (1H, s), 3.89 (3H, s).
Physical properties: amorphous.

(Example 230)
6-Chloro-3- (2,5-dimethoxyphenoxy) -4-pyridazinol (Compound No. 709)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.04-6.99 (1H, m), 6.81-6.78 (2H, m), 6.68 (1H, s), 3.76 (3H, s), 3.70 (3H, s).
Melting point (° C): 150-152.

(Example 231)
6-Chloro-3- (2,6-difluorophenoxy) -4-pyridazinol (Compound No. 710)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.54-7.20 (3H, m), 6.88 (1H, s).
Melting point (° C): 209-213.

(Example 232)
6-Chloro-3- (2-chloro-6-fluorophenoxy) -4-pyridazinol (Compound No. 711)
^{1 H-NMR (200MHz, CD3OD} ) δppm: 7.35-7.13 (3H, m), 6.61 (1H, s).
Melting point (° C): 235.

(Example 233)
3- (2-Bromo-6-fluorophenoxy) -6-chloro-4-pyridazinol (Compound No. 712)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.31-7.15 (3H, m), 6.65 (1H, s).
Physical properties: amorphous.

(Example 234)
6-Chloro-3- (2-fluoro-6-propylphenoxy) -4-pyridazinol (Compound No. 716)
Melting point (° C): 134-137.

(Example 235)
6-Chloro-3- (2-fluoro-6-isopropylphenoxy) -4-pyridazinol (Compound No. 717)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.35-7.15 (3H, m), 6.89 (1H, br.s), 3.02 (1H, septet, J = 7.0Hz), 1.14 (6H, J = 7.0 Hz).
Melting point (° C): 215-220.

(Example 236)
6-Chloro-3- (2-cyclopropyl-6-fluorophenoxy) -4-pyridazinol (Compound No. 719)
¹ H-NMR (200MHz, CD3OD) δppm: 7.22-6.96 (2H, m), 6.81-6.71 (1H, m), 6.72 (1H, s), 2.03-1.89 (1H, m), 0.93-0.80 (2H , m), 0.69-0.62 (2H, m).
Melting point (° C): 200-203.

(Example 237)
6-Chloro-3- {2- [1- (ethylsulfanyl) ethyl] -6-fluorophenoxy} -4-pyridazinol (Compound No. 728)
¹ H-NMR (200MHz, CD3OD) δppm: 7.42 (1H, d, J = 8.1 Hz), 7.26-7.15 (1H, m), 7.07-6.97 (1H, m), 6.46 (1H, s), 4.33 ( 1H, q, J = 7.0 Hz), 2.42-2.20 (2H, m), 1.43 (3H, d, J = 7.0 Hz), 1.02 (3H, t, J = 7.0 Hz).
Physical properties: amorphous.

(Example 238)
6-Chloro-3- (2-fluoro-6-nitrophenoxy) -4-pyridazinol (Compound No. 731)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 8.03-7.99 (1H, m), 7.78-7.53 (2H, m), 6.89 (1H, s).
Melting point (° C): 210 (sublimation).

(Example 239)
6-Chloro-3- (2-fluoro-6-methoxyphenoxy) -4-pyridazinol (Compound No. 732)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.26 (1H, dd, J = 15.0, 8.1 Hz), 7.02-6.91 (2H, m), 6.84 (1H, s), 3.75 (3H, s).
Melting point (° C): 190-194 (sublimation).

(Example 240)
6-Chloro-3- (2,6-dichlorophenoxy) -4-pyridazinol (Compound No. 733)
¹ H-NMR (90 MHz, DMSO-d6) δ ppm: 7.70-7.10 (3H, m), 6.80 (1H, s).
Melting point (° C): 265.

(Example 241)
6-Chloro-3- (2-chloro-6-iodophenoxy) -4-pyridazinol (Compound No. 735)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.90 (1H, d, J = 8.1Hz), 7.64 (1H, d, J = 8.1Hz), 7.12 (1H, t, J = 8.1Hz), 7.02 -6.80 (1H, br.m).
Melting point (° C): 262-264.

(Example 242)
6-Chloro-3- (2-chloro-6-methylphenoxy) -4-pyridazinol (Compound No. 736)
¹ H-NMR (90 MHz, CD3OD) δ ppm: 7.50-7.00 (3H, m), 6.75 (1H, s), 2.22 (3H, s).
Melting point (° C): 235.

(Example 243)
6-Chloro-3- (2-chloro-6-ethylphenoxy) -4-pyridazinol (Compound No. 737)
Melting point (° C): 194-195.

(Example 244)
6-Chloro-3- (5-fluoro-2-methoxyphenoxy) -4-pyridazinol (Compound No. 700)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.13-6.94 (3H, m), 6.71 (1H, s), 3.74 (1H, s).
Melting point (° C): 187-191.

(Example 245)
6-Chloro-3- (2-chloro-6-cyclopropylphenoxy) -4-pyridazinol (Compound No. 740)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.30 (1H, dd, J = 8.1, 1.5 Hz), 7.17 (1H, dd, J = 8.1, 7.7 Hz), 6.96 (1H, dd, J = 7.7, 1.5 Hz), 6.76 (1H, s), 2.00-1.84 (1H, m), 0.95-0.80 (2H, m), 0.70-0.60 (2H, m).
Melting point (° C): 224-225.

(Example 246)
6-Chloro-3- [2-chloro-6- (2-methyl-2-propenyl) phenoxy] -4-pyridazinol (Compound No. 746)
Melting point (° C): 198-200.

(Example 247)
6-Chloro-3- (2-chloro-6-nitrophenoxy) -4-pyridazinol (Compound No. 754)
¹ H-NMR (200MHz, CD3OD) δppm: 8.12 (1H, dd, J = 8.1, 1.5Hz), 7.95 (1H, dd, J = 8.1, 1.5Hz), 7.59 (1H, t, J = 8.1Hz) , 6.76 (1H, s).
Physical properties: amorphous.

(Example 248)
6-Chloro-3- (2,6-dibromophenoxy) -4-pyridazinol (Compound No. 756)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.65 (2H, d, J = 8.1 Hz), 7.11 (1H, t, J = 8.1 Hz), 6.74 (1H, br.s).
Melting point (° C): 274-278.

(Example 249)
3- (2-Bromo-6-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 758)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.56 (1H, br.d, J = 7.7Hz), 7.36 (1H, br.d, J = 7.7Hz), 7.16 (1H, t, J = 7.7 Hz), 6.92 (1H, br.s), 2.14 (3H, s).
Melting point (° C): 242-243.

(Example 250)
3- (2-Bromo-6-ethylphenoxy) -6-chloro-4-pyridazinol (Compound No. 759)
¹ H-NMR (200MHz, CD3OD) δppm: 7.49 (1H, dd, J = 7.9, 1.6Hz), 7.32 (1H, dd, J = 7.9, 1.6Hz), 7.14 (1H, t, J = 7.9Hz) , 6.75 (1H, s), 2.58 (2H, q, J = 7.5Hz), 1.18 (3H, t, J = 7.5Hz).
Melting point (° C): 215-217.

(Example 251)
3-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] -4-methoxybenzonitrile (Compound No. 707)
¹ H-NMR (200MHz, CD3OD) δppm: 7.66 (1H, dd, J = 8.4, 2.2Hz), 7.58 (1H, d, J = 2.2Hz), 7.26 (1H, d, J = 8.4Hz), 6.71 (1H, s), 3.85 (3H, s).
Melting point (° C): 187-192.

(Example 252)
3- (2-Bromo-6-chlorophenoxy) -6-chloro-4-pyridazinol (Compound No. 734)
¹ H-NMR (200MHz, CD3OD) δppm: 7.64 (1H, dd, J = 1.5Hz, 8.1Hz), 7.52 (1H, dd, J = 1.5Hz, 8.0Hz), 7.21 (1H, t, J = 8.1 Hz), 6.76 (1H, s).
Melting point (° C): 266-274.

(Example 253)
3- (2-Bromo-6-cyclopropylphenoxy) -6-chloro-4-pyridazinol (Compound No. 762)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.51 (1H, d, J = 7.8Hz), 7.14 (1H, t, J = 7.8Hz), 7.02 (1H, d, J = 7.8Hz), 6.89 (1H, s), 1,89-1.75 (1H, m), 0.88-0.75 (2H, m), 0.75-0.58 (2H, m).
Melting point (° C): 230-232.

(Example 254)
3-Bromo-2-[(6-chloro-4-hydroxy-3-pyridazinyl) oxy] benzonitrile (Compound No. 775)
¹ H-NMR (200MHz, CD3OD) δppm: 8.00 (1H, dd, J = 8.1, 1.5Hz), 7.82 (1H, dd, J = 8.1, 1.5Hz), 7.37 (1H, t, J = 8.1Hz) , 6.75 (1H, s).
Melting point (° C): 188 (dec.).

(Example 255)
3- (2-Bromo-6-methoxyphenoxy) -6-chloro-4-pyridazinol (Compound No. 778)
^{1 H-NMR (200MHz, CD3OD} ) δppm: 7.26-7.05 (3H, m), 6.70 (1H, s), 3.78 (3H, s).
Melting point (° C): 220-221.

(Example 256)
6-Chloro-3- (2-iodo-6-methylphenoxy) -4-pyridazinol (Compound No. 780)
¹ H-NMR (200MHz, CD3OD) δppm: 7.70 (1H, d, J = 7.7Hz), 7.29 (1H, d, J = 8.1Hz), 6.95 (1H, t, J = 7.7Hz), 6.76 (1H , s), 2.20 (3H, s).
Melting point (° C): 250-252.

(Example 257)
6-Chloro-3- (2-ethyl-6-iodophenoxy) -4-pyridazinol (Compound No. 781)
¹ H-NMR (200MHz, CD3OD) δppm: 7.72 (1H, dd, J = 7.7, 1.5Hz), 7.33 (1H, dd, J = 7.7, 1.5Hz), 7.00 (1H, t, J = 7.7Hz) , 6.76 (1H, s), 2.57 (2H, q, J = 7.7Hz), 1.17 (3H, t, J = 7.7Hz).
Melting point (° C): 242-244.

(Example 258)
6-Chloro-3- (2-iodo-6-isopropylphenoxy) -4-pyridazinol (Compound No. 782)
¹ H-NMR (200MHz, CD3OD) δppm: 7.70 (1H, dd, J = 8.0, 1.5Hz), 7.40 (1H, dd, J = 8.0, 1.5Hz), 7.03 (1H, t, J = 8.0Hz) , 6.76 (1H, s), 3.01 (1H, septet, J = 7.0Hz), 1.18 (6H, d, J = 7.0Hz).
Melting point (° C): 250-255.

(Example 259)
3-Bromo-2-[(6-chloro-4-hydroxy-3-pyridazinyl) oxy] benzonitrile (Compound No. 775)
¹ H-NMR (200MHz, CD3OD) δppm: 8.00 (1H, dd, J = 8.1, 1.5Hz), 7.82 (1H, dd, J = 8.1, 1.5Hz), 7.37 (1H, t, J = 8.1Hz) , 6.75 (1H, s).
Melting point (° C): 188 (dec.).

(Example 260)
6-Chloro-3- (2-ethyl-6-methylphenoxy) -4-pyridazinol (Compound No. 802)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.12-6.97 (3H, m), 6.52 (1H, s), 2.37 (2H, q, J = 7.6Hz), 1.95 (3H, s), 1.04 (3H , t, J = 7.6Hz).
Physical properties: amorphous.

(Example 261)
6-Chloro-3- (2-isopropyl-6-methylphenoxy) -4-pyridazinol (Compound No. 803)
¹ H-NMR (200MHz, CD3OD) δppm: 7.23-7.06 (3H, m), 6.72 (1H, s), 2.96 (1H, septet, J = 7.0Hz), 2.10 (3H, s), 1.16 (6H, d, J = 7.0 Hz).
Melting point (° C): 215-220.

(Example 262)
3- (2-sec-Butyl-6-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 804)
Melting point (° C): 187-189.

(Example 263)
6-Chloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] -4-pyridazinol (Compound No. 827)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.25 (1H, br.d, J = 6.2 Hz), 7.16 (1H, dd, J = 7.7, 7.3 Hz), 6.98 (1H, br.d, J = 7.7 Hz), 6.72 (1H, s), 2.85 (1H, dd, J = 11.0, 10.6 Hz), 2.22 (3H, s).
Melting point (° C): 213-215.

(Example 264)
6-Chloro-3- (2-methyl-6-vinylphenoxy) -4-pyridazinol (Compound No. 834)
¹ H-NMR (200MHz, CD3OD) δppm: 7.46 (1H, dd, J = 6.6, 2.6Hz), 7.25-7.05 (2H, m), 6.71 (1H, dd, J = 17.6, 11.4Hz), 6.70 ( 1H, s), 5.74 (1H, dd, J = 17.6, 1.5 Hz), 5.21 (1H, dd, J = 11.4, 1.5 Hz), 2.11 (3H, s).
Physical properties: amorphous.

(Example 265)
6-Chloro-3- (6-cyclopropyl-3-fluoro-2-methylphenoxy) -4-pyridazinol (Compound No. 1052)
^{1 H-NMR (200MHz, CD3OD} ) δppm: 6.92-6.70 (3H, m), 2.06 (3H, d, J = 2.2Hz), 1.85-1.70 (1H, m), 0.79-0.45 (4H, m).
Melting point (° C): 230-231.

(Example 266)
6-Chloro-3- (2-methyl-6-nitrophenoxy) -4-pyridazinol (Compound No. 844)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.95 (1H, d, J = 8.1Hz), 7.76 (1H, d, J = 7.7Hz), 7.45 (1H, dd, J = 8.1, 7.7Hz) , 6.80 (1H, s), 2.20 (3H, s).
Physical properties: Pasty.

(Example 267)
6-Chloro-3- (2-methoxy-6-methylphenoxy) -4-pyridazinol (Compound No. 845)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 7.10-7.01 (1H, m), 6.79-6.72 (2H, m), 6.55 (1H, s), 3.64 (3H, s), 2.08 (3H, s) .
Physical properties: amorphous.

(Example 268)
6-Chloro-3- (2,6-diethylphenoxy) -4-pyridazinol (Compound No. 846)
¹ H-NMR (60MHz, CDCl ₃ ) δppm: 10.21 (1H, br.s), 7.02 (3H, br.s), 6.47 (1H, s), 2.27 (4H, q, J = 7.6Hz), 0.98 (6H, t, J = 7.6Hz).
Melting point (° C): 181-185.

(Example 269)
6-Chloro-3- (2-cyclopropyl-6-ethylphenoxy) -4-pyridazinol (Compound No. 850)
¹ H-NMR (200MHz, CD3OD) δppm: 7.11 (2H, d, J = 4.8Hz), 6.85 (1H, t, J = 4.8Hz), 6.71 (1H, s), 2.52 (2H, q, J = 7.5Hz), 1.87-1.72 (1H, m), 1.16 (3H, t, J = 7.5Hz), 0.80-0.65 (2H, m), 0.65-0.50 (2H, m).
Physical properties: amorphous.

(Example 270)
6-Chloro-3- (2,6-dipropylphenoxy) -4-pyridazinol (Compound No. 890)
Melting point (° C): 191-193.

(Example 271)
6-Chloro-3- (2,6-diisopropylphenoxy) -4-pyridazinol (Compound No. 894)
¹ H-NMR (90MHz, DMSO-d6) δppm: 7.28 (3H, s), 6.80 (1H, s), 2.88 (2H, septet, J = 7.0Hz), 1.15 (12H, d, J = 7.0Hz) .
Melting point (° C):> 285.

(Example 272)
6-Chloro-3- (2-cyclopropyl-6-isopropylphenoxy) -4-pyridazinol (Compound No. 896)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.22-7.12 (2H, m), 6.83 (1H, br.s), 6.82 (1H, dd, J = 6.6, 2.2Hz), 2.91 (1H, septet , J = 7.0Hz), 1.74-1.63 (1H, m), 1.11 (6H, d, J = 7.0Hz), 0.75-0.71 (2H, m), 0.58-0.50 (2H, m).
Melting point (° C): 242-245.

(Example 273)
6-Chloro-3- (2-isopropyl-6-nitrophenoxy) -4-pyridazinol (Compound No. 911)
¹ H-NMR (200MHz, DMSO-d6) δppm: 8.00 (1H, d, J = 7.7Hz), 7.88 (1H, d, J = 7.7Hz), 7.54 (1H, t, J = 7.7Hz), 6.96 (1H, br.s), 3.07 (1H, septet, J = 7.0Hz), 1.16 (6H, d, J = 7.0Hz).
Melting point (° C): 205-209.

(Example 274)
3- (2-tert-Butyl-6-cyclopropylphenoxy) -6-chloro-4-pyridazinol (Compound No. 914)
¹ H-NMR (200MHz, CD3OD) δppm: 7.28 (1H, br.d, J = 8.1Hz), 7.10 (1H, dd, J = 8.1and 7.7Hz), 6.90 (1H, d, J = 7.7Hz) , 6.70 (1H, s), 1.80-1.55 (1H, m), 1.34 (9H, s), 0.85-0.60 (2H, m), 0.50-0.20 (2H, m).
Melting point (° C): 230-231.

(Example 275)
6-Chloro-3- (2,6-dicyclopropylphenoxy) -4-pyridazinol (Compound No. 931)
¹ H-NMR (200MHz, CD3OD) δppm: 7.08 (1H, t, J = 7.7Hz), 6.81 (2H, d, J = 7.7Hz), 6.71 (1H, s), 1.95-1.75 (2H, m) , 0.85-0.70 (4H, m), 0.70-0.50 (4H, m).
Melting point (° C): 232-234.

(Example 276)
6-Chloro-3- (2-cyclopropyl-6-methoxyphenoxy) -4-pyridazinol (Compound No. 964)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.13 (1H, t, J = 8.1 Hz), 6.92 (1H, d, J = 8.1 Hz), 6.81 (1H, br.s), 6.54 (1H, d, J = 8.1Hz), 3.68 (3H, s), 1.87-1.78 (1H, m), 0.87-0.78 (2H, m), 0.64-0.56 (2H, m).
Melting point (° C): 194-199.

(Example 277)
6-Chloro-3- (2-cyclopropyl-6-ethoxyphenoxy) -4-pyridazinol (Compound No. 965)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.07 (1H, t, J = 8.1 Hz), 6.84 (1H, dd, J = 8.4, 1.5 Hz), 6.71 (1H, s), 6.54 (1H, dd, J = 8.4, 1.5Hz), 3.97 (2H, q, J = 7.0Hz), 2.04-1.91 (1H, m), 1.18 (3H, t, J = 7.0Hz), 0.89-0.79 (2H, m), 0.66-0.60 (2H, m).
Melting point (° C): 174-179.

(Example 278)
6-Chloro-3- {2,6-di [(1E) -1-propenyl] phenoxy} -4-pyridazinol (Compound No. 979)
^{1 H-NMR (200MHz, CD3OD} ) δppm: 7.40 (2H, d, J = 7.8Hz), 7.15 (1H, t, J = 7.8Hz), 6.72 (1H, s), 6.34 (2H, d, J = 16.4Hz), 6.27 (2H, dd, J = 16.4, 4.9Hz), 1.79 (6H, d, J = 4.9Hz).
Melting point (° C): 163-164.

(Example 279)
6-Chloro-3- (2,6-diallylphenoxy) -4-pyridazinol (Compound No. 982)
¹ H-NMR (200MHz, CD3OD) δppm: 7.20-7.15 (3H, m), 6.70 (1H, s), 5.95-5.75 (2H, m), 5.02-4.87 (4H, m), 3.26 (4H, d , J = 6.8Hz).
Melting point (° C): 131-135.

(Example 280)
6-Chloro-3- (2,6-dimethoxyphenoxy) -4-pyridazinol (Compound No. 987)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.19 (1H t, J = 8.3 Hz), 6.79-6.75 (3H m), 3.71 (6H, s).
Melting point (° C): 199-201.

(Example 281)
6-Chloro-3- (3,5-dimethylphenoxy) -4-pyridazinol (Compound No. 998)
¹ H-NMR (60 MHz, DMSO-d6) δ ppm: 6.90-6.65 (4H, m), 2.27 (6H, s).
Melting point (° C): 178-182.

(Example 282)
6-Chloro-3- (3-isopropyl-5-methylphenoxy) -4-pyridazinol (Compound No. 1000)
¹ H-NMR (200MHz, CD3OD) δppm: 6.94 (1H, s), 6.84 (1H, s), 6.81 (1H, s), 6.69 (1H, s), 2.87 (1H, septet, J = 7.0Hz) , 2.32 (3H, s), 1.23 (6H, d, J = 7.0Hz).
Melting point (° C): 204-206.

(Example 283)
6-Chloro-3- (3,5-diisopropylphenoxy) -4-pyridazinol (Compound No. 1007)
¹ H-NMR (200MHz, CD3OD) δppm: 6.98 (1H, s), 6.87 (1H, s), 6.86 (1H, s), 6.68 (1H, s), 2.90 (2H, septet, J = 7.0Hz) , 1.24 (12H, d, J = 7.0Hz).
Melting point (° C): 249-253.

(Example 284)
3- [3,5-Bis (trifluoromethyl) phenoxy] -6-chloro-4-pyridazinol (Compound No. 1009)
¹ H-NMR (200 MHz, DMF-d7) δ ppm: 8.20-7.80 (3H, m), 6.94 (1H, s), 5.50-4.50 (1H, br.s).
Melting point (° C): 237-242.

(Example 285)
3- (2-Bromo-3,5-dimethylphenoxy) -6-chloro-4-pyridazinol (Compound No. 1013)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.11 (1H, s), 7.00 (1H, s), 6.86 (1H, br.s), 2.37 (3H, s), 2.27 (3H, s).
Melting point (° C): 240-244.

(Example 286)
6-Chloro-3- (2,3,5-trimethylphenoxy) -4-pyridazinol (Compound No. 1016)
¹ H-NMR (90 MHz, CD3OD) δ ppm: 6.90 (1H, s), 6.75 (1H, s), 6.70 (1H, s), 2.30 (6H, s), 2.02 (3H, s).
Melting point (° C): 223-224.

(Example 287)
6-Chloro-3- (3,5-dimethyl-2-propylphenoxy) -4-pyridazinol (Compound No. 1020)
¹ H-NMR (90MHz, DMSO-d6) δppm: 6.90 (1H, s), 6.81 (1H, s), 6.77 (1H, s), 2.29 (3H, s), 2.21 (3H, s), 2.53- 2.19 (2H, m), 1.57-1.29 (2H, m), 0.86 (3H, t, J = 6.6Hz).
Melting point (° C): 154.5.

(Example 288)
6-Chloro-3- (2-cyclopropyl-3,5-dimethylphenoxy) -4-pyridazinol (Compound No. 1023)
¹ H-NMR (200MHz, CD3OD) δppm: 6.89 (1H, s), 6.73 (1H, s), 6.69 (1H, s), 2.39 (3H, s), 2.26 (3H, s), 1.45-1.28 ( 1H, m), 0.78-0.67 (2H, m), 0.65-0.51 (2H, m).
Melting point (° C): 200-203.

Example 289
6-Chloro-3- [3,5-dimethyl-2- (methylsulfanyl) phenoxy] -4-pyridazinol (Compound No. 1027)
Melting point (° C): 213-214.

(Example 290)
3- (2-Bromo-3,6-dimethylphenoxy) -6-chloro-4-pyridazinol (Compound No. 1040)
¹ H-NMR (200MHz, CD3OD) δppm: 7.16 (1H, d, J = 7.9Hz), 7.10 (1H, d, J = 7.9Hz), 6.72 (1H, s), 2.38 (3H, s), 2.16 (3H, s).
Melting point (° C): 255-257.

(Example 291)
3- (6-Bromo-3-fluoro-2-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 1050)
¹ H-NMR (200MHz, CD3OD) δppm: 7.51 (1H, dd, J = 8.8, 5.9Hz), 7.00 (1H, t, J = 8.8Hz), 6.96 (1H, s), 2.13 (3H, d, J = 2.2Hz).
Physical properties: amorphous.

(Example 292)
3- (6-Bromo-3-chloro-2-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 1053)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.47 (1H, d, J = 8.1 Hz), 7.23 (1H, d, J = 8.1 Hz), 6.64 (1H, s), 2.24 (3H, s).
Melting point (° C): 254-260.

(Example 293)
6-Chloro-3- (3-chloro-6-cyclopropyl-2-methylphenoxy) -4-pyridazinol (Compound No. 1055)
¹ H-NMR (200MHz, CD3OD) δppm: 7.18 (1H, d, J = 8.4Hz), 6.81 (1H, d, J = 8.4Hz), 6.64 (1H, s), 2.17 (3H, s), 1.89 -1.76 (1H, m), 0.80-0.71 (2H, m), 0.68-0.51 (2H, m).
Melting point (° C): 233.

(Example 294)
3- (6-Bromo-2,3-dimethylphenoxy) -6-chloro-4-pyridazinol (Compound No. 1058)
^{1 H-NMR (200MHz, CD3OD} ) δppm: 7.34 (1H, d, J = 8.1Hz), 6.99 (1H, d, J = 8.1Hz), 6.71 (1H, s), 2.28 (3H, s), 2.12 (3H, s).
Melting point (° C): 263-268.

(Example 295)
6-Chloro-3- (2,3,6-trimethylphenoxy) -4-pyridazinol (Compound No. 1060)
¹ H-NMR (90 MHz, CD3OD) δ ppm: 7.00 (2H, s), 6.73 (1H, s), 2.27 (3H, s), 2.07 (3H, s), 2.03 (3H, s).
Melting point (° C): 228.

(Example 296)
6-Chloro-3- (6-cyclopropyl-2,3-dimethylphenoxy) -4-pyridazinol (Compound No. 1061)
¹ H-NMR (200MHz, CD3OD) δppm: 6.96 (1H, d, J = 8.1Hz), 6.72 (1H, d, J = 8.1Hz), 6.69 (1H, s), 2.24 (3H, s), 2.04 (3H, s), 1.85-1.70 (1H, m), 0.75-0.46 (4H, m).
Melting point (° C): 229-234.

(Example 297)
2-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] -3,4-dimethylbenzaldehyde O-methyloxime (Compound No. 1063)
¹ H-NMR (200MHz, CD3OD) δppm: 7.98 (1H, s), 7.50 (1H, d, J = 8.1Hz), 7.11 (1H, d, J = 8.1Hz), 6.69 (1H, s), 3.81 (3H, s), 2.32 (3H, s), 2.06 (3H, s).
Physical properties: amorphous.

(Example 298)
6-Chloro-3- (6-methoxy-2,3-dimethylphenoxy) -4-pyridazinol (Compound No. 1064)
¹ H-NMR (200MHz, CD3OD) δppm: 7.00 (1H, d, J = 8.4Hz), 6.78 (1H, d, J = 8.4Hz), 6.66 (1H, s), 3.69 (3H, s), 2.23 (3H, s), 2.08 (3H, s).
Physical properties: amorphous.

(Example 299)
3- (6-Bromo-3-methoxy-2-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 1066)
¹ H-NMR (200MHz, CD3OD) δppm: 7.42 (1H, d, J = 9.2Hz), 6.82 (1H, d, J = 9.2Hz), 6.69 (1H, s), 3.86 (3H, s), 2.05 (3H, s).
Melting point (° C): 246-253.

(Example 300)
6-Chloro-3- (6-cyclopropyl-3-methoxy-2-methylphenoxy) -4-pyridazinol (Compound No. 1069)
¹ H-NMR (200MHz, CD3OD) δppm: 6.83 (1H, d, J = 8.8Hz), 6.75 (1H, d, J = 8.8Hz), 6.66 (1H, s), 3.81 (3H, s), 1.99 (3H, s), 1.78-1.70 (1H, m), 0.69-0.63 (2H, m), 0.52-0.47 (2H, m).
Melting point (° C): 250-253.

(Example 301)
6-Chloro-3- (2-cyclopropyl-3,6-dimethylphenoxy) -4-pyridazinol (Compound No. 1073)
¹ H-NMR (200MHz, CD3OD) δppm: 7.20 (1H, d, J = 7.6Hz), 6.95 (1H, d, J = 7.6Hz), 6.68 (1H, s), 2.39 (3H, s), 2.10 (3H, s), 1.50-1.25 (1H, m), 0.90-0.70 (2H, m), 0.70-0.50 (2H, m).
Melting point (° C): 171-175.

(Example 302)
3- (2-Allyl-6-ethyl-3-methoxyphenoxy) -6-chloro-4-pyridazinol (Compound No. 1080)
¹ H-NMR (60MHz, DMF-d7) δppm: 7.11 (1H, d, J = 8.4Hz), 6.85 (1H, s), 6.83 (1H, d, J = 8.4Hz), 6.10-5.30 (1H, m), 5.00-4.60 (2H, m), 3.83 (3H, s), 3.30-3.10 (2H, m), 2.40 (2H, q, J = 7.6Hz), 1.10 (3H, t, J = 7.6Hz ).
Melting point (° C): 183-186.

Example 303
6-chloro-3- {3,6-dimethyl-2-[(methylsulfanyl) methyl] phenoxy} -4-pyridazinol (Compound No. 1083)
¹ H-NMR (90 MHz, CD3OD) δppm: 7.21-6.90 (2H, m), 6.71 (1H, s), 3.68 (2H, s), 2.38 (3H, s), 2.09 (3H, s), 2.00 ( 3H, s).
Physical properties: amorphous.

(Example 304)
3-[(5-Bromo-2,3-dihydro-1H-inden-4-yl) oxy] -6-chloro-4-pyridazinol (Compound No. 1086)
¹ H-NMR (200MHz, CD3OD) δppm: 7.39 (1H, d, J = 8.1Hz), 7.05 (1H, d, J = 8.1Hz), 6.71 (1H, s), 2.94 (2H, t, J = 7.3Hz), 2.79 (2H, t, J = 7.3Hz), 2.10-2.00 (2H, m).
Physical properties: amorphous.

(Example 305)
6-Chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinol (Compound No. 1088)
¹ H-NMR (200MHz, DMSO-d6) δppm: 7.11-7.01 (2H, m), 6.83 (1H, br.s), 2.88 (3H, t, J = 7.3Hz), 2.59 (3H, t, J = 7.3Hz), 2.06 (3H, s), 2.06-1.91 (2H, m).
Melting point (° C): 222-225.

(Example 306)
6-Chloro-3-[(5-ethyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinol (Compound No. 1089)
¹ H-NMR (200MHz, CD3OD) δppm: 7.06 (2H, s), 6.71 (1H, s), 2.91 (2H, t, J = 7.3Hz), 2.67 (2H, t, J = 7.3Hz), 2.51 (2H, q, J = 7.7Hz), 2.04 (2H, quintet, J = 7.3Hz), 1.13 (3H, t, J = 7.7Hz).
Melting point (° C): 193-196.

(Example 307)
6-Chloro-3-[(5-cyclopropyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinol (Compound No. 1091)
¹ H-NMR (200MHz, CD3OD) δppm: 7.02 (1H, d, J = 7.7Hz), 6.79 (1H, d, J = 7.7Hz), 6.71 (1H, s), 2.90 (2H, t, J = 7.3Hz), 2.72 (2H, t, J = 7.3Hz), 2.18-1.98 (2H, m), 1.92-1.75 (1H, m), 0.82-0.70 (2H, m), 0.60-0.47 (2H, m ).
Melting point (° C): 218-220.

(Example 308)
6-Chloro-3-[(6-methyl-2,3-dihydro-1-benzofuran-7-yl) oxy] -4-pyridazinol (Compound No. 1096)
¹ H-NMR (200MHz, CD3OD) δppm: 6.99 (1H, d, J = 7.7Hz), 6.72 (1H, d, J = 7.7Hz), 6.70 (1H, s), 4.53 (2H, t, J = 8.8Hz), 3.20 (2H, br.t, J = 8.8Hz), 2.15 (3H, s).
Melting point (° C): 217-219.

(Example 309)
3-[(6-Bromo-1-benzofuran-7-yl) oxy] -6-chloro-4-pyridazinol (Compound No. 1099)
¹ H-NMR (200MHz, CD3OD) δppm: 7.75 (1H, d, J = 2.2Hz), 7.48 (1H, d, J = 8.4Hz), 7.47 (1H, d, J = 8.4Hz), 6.92 (1H , d, J = 2.2Hz), 6.78 (1H, s).
Physical properties: amorphous.

(Example 310)
6-Chloro-3-[(6-methyl-1-benzofuran-7-yl) oxy] -4-pyridazinol (Compound No. 1100)
¹ H-NMR (200MHz, CD3OD) δppm: 7.65 (1H, d, J = 2.2Hz), 7.40 (1H, d, J = 8.1Hz), 7.14 (1H, d, J = 8.1Hz), 6.82 (1H , d, J = 2.2Hz), 6.75 (1H, s), 2.31 (3H, s).
Physical property: Oily substance.

(Example 311)
6-Chloro-3-[(6-cyclopropyl-1-benzofuran-7-yl) oxy] -4-pyridazinol (Compound No. 1102)
¹ H-NMR (200MHz, CD3OD) δppm: 7.65 (1H, d, J = 2.2Hz), 7.40 (1H, d, J = 8.1Hz), 6.87 (1H, d, J = 8.1Hz), 6.81 (1H , d, J = 2.2Hz), 6.75 (1H, s), 2.10-1.98 (1H, m), 0.98-0.80 (2H, m), 0.80-0.64 (2H, m).
Melting point (° C): 175-180.

(Example 312)
6-Chloro-3-[(5-methyl-1-benzofuran-4-yl) oxy] -4-pyridazinol (Compound No. 1109)
^{1 H-NMR (200MHz, CD3OD} ) δppm: 7.65 (1H, d, J = 2.2Hz), 7.32 (1H, d, J = 8.4Hz), 7.18 (1H, d, J = 8.4Hz), 6.73 (1H , s), 6.60 (1H, d, J = 2.2Hz), 2.23 (3H, s).
Melting point (° C): 222-225.

(Example 313)
6-Chloro-3- (2,4-dicyclopropyl-6-fluorophenoxy) -4-pyridazinol (Compound No. 1115)
¹ H-NMR (200MHz, CD3OD) δppm: 6.71-6.65 (2H, m), 6.54 (1H, s), 2.02-1.81 (2H, m), 1.01-0.72 (4H, m), 0.68-0.60 (4H , m).
Physical properties: amorphous.

(Example 314)
6-Chloro-3- (2,4-dibromo-3,6-dimethylphenoxy) -4-pyridazinol (Compound No. 1118)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.54 (1H, s), 6..71 (1H, s), 2.56 (3H, s), 2.16 (3H, s).
Melting point (° C): 241-248.

(Example 315)
3- (2-Bromo-4,6-dimethylphenoxy) -6-chloro-4-pyridazinol (Compound No. 1119)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.31 (1H, br.s), 7.10 (1H, br.s), 6.74 (1H, s), 2.31 (3H, s), 2.17 (3H, s).
Melting point (° C): 254-256.

(Example 316)
6-Chloro-3- (2-ethyl-4,6-diiodophenoxy) -4-pyridazinol (Compound No. 1120)
¹ H-NMR (200MHz, CD3OD) δppm: 8.03 (1H, d, J = 2.2Hz), 7.66 (1H, d, J = 2.2Hz), 6.74 (1H, s), 2.52 (2H, q, J = 7.7Hz), 1.17 (3H, t, J = 7.7Hz).
Melting point (° C): 142-144.

(Example 317)
6-Chloro-3- (2,4,6-trimethylphenoxy) -4-pyridazinol (Compound No. 1122)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 6.90 (2H, s), 6.71 (1H, s), 2.27 (3H, s), 2.07 (6H, s).
Melting point (° C): 235-239.

(Example 318)
6-Chloro-3- (2-cyclopropyl-4,6-dimethylphenoxy) -4-pyridazinol (Compound No. 1123)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 6.88 (1H, br.s), 6.69 (1H, s), 6.63 (1H, br.s), 2.26 (3H, s), 2.09 (3H, s), 1.85-1.70 (1H, m), 0.80-0.65 (2H, m), 0.65-0.50 (2H, m).
Melting point (° C): 215-217.

(Example 319)
3- (2-Bromo-3,5,6-trimethylphenoxy) -6-chloro-4-pyridazinol (Compound No. 1124)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.13 (1H, s), 6.88 (1H, br.s), 2.32 (3H, s), 2.23 (3H, s), 2.01 (3H, s).
Melting point (° C): 280-290.

(Example 320)
6-Chloro-3- (2,3,5,6-tetramethylphenoxy) -4-pyridazinol (Compound No. 1125)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 6.88 (1H, s), 6.69 (1H, s), 2.22 (6H, s), 1.98 (6H, s).
Melting point (° C): 278-283.

(Example 321)
6-Chloro-3-[(5,6-dimethyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinol (Compound No. 1129)
¹ H-NMR (200MHz, CD3OD) δppm: 6.72 (1H, s), 6.68 (1H, s), 2.88 (2H, t, J = 7.4Hz), 2.70 (2H, t, J = 7.4Hz), 2.24 (3H, s), 2.17 (3H, s), 2.05 (2H, quintet, J = 7.4Hz).
Melting point (° C): 210-213.

(Example 322)
6-Chloro-3- (1,2,3,5,6,7-hexahydro-s-indasen-4-yloxy) -4-pyridazinol (Compound No. 1133)
¹ H-NMR (200MHz, CD3OD) δppm: 7.95 (1H, s), 6.65 (1H, s), 2.88 (4H, t, J = 7.3Hz), 2.68 (4H, t, J = 7.3Hz), 2.20 -1.90 (4H, m).
Physical properties: amorphous.

(Example 323)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl acetate (Compound No. 1140)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.40 (1H, s), 7.26-6.98 (4H, m), 2.40 (3H, s), 1.93-1.76 (1H, m), 0.85-0.59 (4H, m).
Physical properties: amorphous.

(Example 324)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl acetate (Compound No. 1151)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.39 (1H, s), 7.15-7.00 (2H, m), 6.90-6.75 (1H, m), 2.42 (3H, s), 2.12 (3H, s) , 1.90-1.67 (1H, m), 0.85-0.50 (4H, m).
Melting point (° C): 98-101.

(Example 325)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl pivalate (Compound No. 1207)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.38 (1H, s), 7.15-7.05 (2H, m), 6.90-6.84 (1H, m), 2.13 (3H, s), 1.81-1.65 (1H, m), 1.41 (9H, s), 0.90-0.50 (4H, m).
Melting point (° C): 84-87.

(Example 326)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl decanoate (Compound No. 1251)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.38 (1H, s), 7.15-7.05 (2H, m), 6.93-6.80 (1H, m), 2.67 (2H, t, J = 7.3Hz), 2.12 (3H, s), 1.85-1.65 (3H, m), 1.55-1.10 (12H, m), 0.95-0.80 (3H, m), 0.80-0.65 (2H, m), 0.65-0.52 (2H, m) .
Physical property: Oily substance.

(Example 327)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl cyclopropanecarboxylate (Compound No. 1266)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.43 (1H, s), 7.22-6.98 (4H, m), 2.00-1.75 (2H, m), 1.30-1.08 (4H, m), 0.86-0.51 ( 4H, m).
Melting point (° C): 122-125.

(Example 328)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl benzoate (Compound No. 1387)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.23-8.18 (2H, m), 7.75-7.50 (3H, m), 7.60 (1H, s), 7.30-7.08 (4H, m), 2.18 (3H, s).
Physical property: Oily substance.

(Example 329)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl benzoate (Compound No. 1391)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.20 (2H, d, J = 7.3Hz), 7.74-7.50 (4H, m), 7.26-7.01 (3H, m), 6.98-6.97 (1H, m) , 1.91-1.80 (1H, m), 0.83-0.57 (4H, m).
Physical properties: amorphous.

(Example 330)
6-Chloro-3- [4- (trimethylsilyl) phenoxy] -4-pyridazinyl benzoate (Compound No. 1396)
Melting point (° C): 100-102.

(Example 331)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl benzoate (Compound No. 1417)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.24-8.20 (2H, m), 7.75-7.68 (2H, m), 7.67-7.52 (3H, m), 7.09-7.07 (2H, m), 6.87- 6.82 (1H, m), 2.16 (3H, s), 1.82-1.71 (1H, m), 0.75-0.71 (2H, m), 0.62-0.53 (2H, m).
Physical properties: amorphous.

(Example 332)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 2-methylbenzoate (Compound No. 1446)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 8.35-8.08 (2H, m), 7.59 (1H, s), 7.68-7.00 (6H, m), 2.70 (3H, s), 2.21 (3H, s) .
Melting point (° C): 91-93.

(Example 333)
6-Chloro-3- (2-isopropylphenoxy) -4-pyridazinyl 2-methylbenzoate (Compound No. 1448)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 8.15-8.00 (2H, m), 7.58 (1H, s), 7.75-6.90 (6H, m), 3.40-2.85 (1H, m), 2.69 (3H, s), 1.15 (6H, d, J = 7.0 Hz).
Refractive index: nD22 1.5709.

(Example 334)
3- (2-sec-Butylphenoxy) -6-chloro-4-pyridazinyl 2-methylbenzoate (Compound No. 1450)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 8.28-8.05 (1H, m), 7.60-7.05 (7H, m), 7.52 (1H, s), 3.05-2.60 (1H, m), 2.65 (3H, s), 1.70-1.00 (2H, m), 1.10 (3H, d, J = 7.0Hz), 0.90-0.50 (3H, m).
Physical properties: Pasty.

(Example 335)
6-Chloro-3- (2-cyclohexylphenoxy) -4-pyridazinyl 2-methylbenzoate (Compound No. 1455)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 8.30-7.00 (8H, m), 7.54 (1H, s), 2.68 (1H, br.s), 2.67 (3H, s), 2.00-1.00 (10H, m).
Melting point (° C): 89-91.

(Example 336)
3-([1,1'-biphenyl] -2-yloxy) -6-chloro-4-pyridazinyl 2-methylbenzoate (Compound No. 1456)
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 8.20-7.90 (1H, m), 7.60-7.10 (13H, m), 2.58 (3H, s).
Refractive index: nD28 1.6055.

(Example 337)
3- (3-tert-Butylphenoxy) -6-chloro-4-pyridazinyl 2-methylbenzoate (Compound No. 1457)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 8.28-8.02 (1H, m), 7.55 (1H, s), 7.65-6.85 (7H, m), 2.64 (3H, s), 1.28 (9H, s) .
Melting point (° C): 63-64.

(Example 338)
6-Chloro-3- (3-methoxyphenoxy) -4-pyridazinyl 2-methylbenzoate (Compound No. 1458)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 8.30-8.00 (1H, m), 7.70-7.10 (4H, m), 7.55 (1H, s), 6.90-6.60 (3H, m), 3.74 (3H, s), 2.64 (3H, s).
Melting point (° C): 66-67.

(Example 339)
6-Chloro-3- (2-isopropyl-5-methylphenoxy) -4-pyridazinyl 2-methylbenzoate (Compound No. 1459)
^{1 H-NMR (60MHz, CDCl} 3) δppm: 8.30-8.00 (1H, m), 7.54 (1H, s), 7.50-6.80 (6H, m), 3.30 -2.75 (1H, m), 2.65 (3H, s), 2.28 (3H, s), 1.15 (6H, d, J = 7.00Hz).
Melting point (° C): 95-97.

(Example 340)
6-Chloro-3- (1-naphthyloxy) -4-pyridazinyl 2-methylbenzoate (Compound No. 1461)
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 8.20-7.00 (12H, m), 2.65 (3H, s).
Melting point (° C): 133-134.

(Example 341)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 2-methoxybenzoate (Compound No. 1509)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 8.11-7.89 (2H, m), 7.70-6.80 (6H, m), 7.50 (1H, s), 3.84 (3H, s), 2.10 (3H, s) .
Melting point (° C): 114-116.

(Example 342)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 4-methylbenzoate (Compound No. 1553)
¹ H-NMR (60MHz, CDCl ₃ ) δppm: 8.07 (2H, d, J = 8.0Hz), 7.58 (1H, s), 7.40-7.03 (4H, m), 7.36 (2H, d, J = 8.0Hz ), 2.51 (3H, s), 2.23 (3H, s).
Melting point (° C): 105-108.

(Example 343)
6-Chloro-3- (2-isopropylphenoxy) -4-pyridazinyl 4-methylbenzoate (Compound No. 1554)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 8.28-7.82 (2H, m), 7.61 (1H, s), 7.51-6.90 (6H, m), 3.30-2.80 (1H, m), 2.46 (3H, s), 1.19 (6H, d, J = 7.0 Hz).
Refractive index: nD22 1.5731.

(Example 344)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 2,4-dichlorobenzoate (Compound No. 1603)
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 8.04 (1H, d, J = 8.4 Hz), 7.58 (1H, s), 7.58-6.92 (6H, m), 2.20 (3H, s).
Melting point (° C): 81-82.5.

(Example 345)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl methyl carbonate (Compound No. 1658)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.51 (1H, s), 7.23-6.98 (4H, m), 3.99 (3H, s), 1.91-1.82 (1H, m), 0.84-0.61 (4H, m).
Physical properties: amorphous.

(Example 346)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl ethyl carbonate (Compound No. 1706)
¹ H-NMR (60MHz, CDCl ₃ ) δppm: 7.51 (1H, s), 7.38-7.00 (4H, m), 4.40 (2H, q, J = 7.0Hz), 2.20 (3H, s), 1.40 (3H , t, J = 7.0Hz).
Melting point (° C): 73-74.

(Example 347)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl ethyl carbonate (Compound No. 1710)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.51 (1H s), 7.26-6.98 (4H, m), 4.40 (2H, q, J = 7.0Hz), 1.90-1.80 (1H, m), 1.41 ( 3H, t, J = 7.0Hz), 0.84-0.60 (4H, m).
Physical properties: amorphous.

(Example 348)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl isobutyl carbonate (Compound No. 1757)
¹ H-NMR (60MHz, CDCl ₃ ) δppm: 7.45 (1H, s), 7.30-7.00 (4H, m), 4.08 (2H, d, J = 5.8Hz), 2.16 (3H, s), 2.20-1.70 (1H, m), 0.96 (6H, d, J = 5.8Hz).
Melting point (° C): 46-47.

(Example 349)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 2,2,2-trichloroethyl carbonate (Compound No. 1789)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 7.52 (1H, s), 7.28-7.03 (4H, m), 4.94 (2H, s), 2.18 (3H, s).
Physical properties: amorphous.

(Example 350)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl phenyl carbonate (Compound No. 1840)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.58 (1H, s), 7.50-7.20 (5H, m), 7.20-7.05 (2H, m), 6.92-6.82 (1H, m), 2.16 (3H, s), 1.88-1.72 (1H, m), 0.80-0.55 (4H, m).
Physical property: Oily substance.

(Example 351)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl dimethyl carbamate (Compound No. 1877)
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 7.55 (1H, s), 7.40-6.92 (4H, m), 3.10 (3H, s), 3.01 (3H, s), 2.19 (3H, s).
Melting point (° C): 107-109.

(Example 352)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl dimethyl carbamate (Compound No. 1879)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.22-6.98 (4H, m), 3.13 (3H, s), 3.04 (3H, s), 1.97-1.80 (1H, m) , 0.85-0.63 (4H, m).
Melting point (° C): 137-138.

(Example 353)
6-Chloro-3- [3- (trifluoromethyl) phenoxy] -4-pyridazinyl dimethyl carbamate (Compound No. 1881)
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 7.60 (1H, s), 7.65-7.22 (4H, m), 3.11 (3H s), 3.05 (3H s).
Melting point (° C): 92-93.

(Example 354)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl diethylcarbamate (Compound No. 1898)
¹ H-NMR (60MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 7.40-6.92 (4H, m), 3.41 (4H, q, J = 6.2Hz), 2.20 (3H, s), 1.27 (6H , t, J = 6.2Hz).
Melting point (° C): 74-75.5.

(Example 355)
6-chloro-3- (2-methylphenoxy) -4-pyridazinyl 1-pyrrolidinecarboxylate (Compound No. 1924)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 7.58 (1H, s), 7.42-7.02 (4H, m), 3.67-3.37 (4H, m), 2.19 (3H, s), 2.07-1.72 (4H, m).
Melting point (° C): 126-127.

(Example 356)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl methanesulfonate (Compound No. 1981)
¹ H-NMR (200 MHz, CDCl ₃ ) δ ppm: 7.55 (1H, s), 7.33-7.06 (4H, m), 3.43 (3H, s), 2.20 (3H, s).
Physical property: Oily substance.

(Example 357)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl methanesulfonate (Compound No. 1985)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 7.26-7.23 (2H, m), 7.21-7.02 (2H, m), 3.44 (3H, s), 1.89-1.80 (1H, m), 0.86-0.61 (4H, m).
Melting point (° C): 162-172.

(Example 358)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl methanesulfonate (Compound No. 2010)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.56 (1H, s), 7.18-7.09 (2H, m), 6.91-6.86 (1H, m), 3.47 (3H, s), 2.16 (3H, s) , 1.82-1.68 (1H, m), 0.75-0.69 (2H, m), 0.67-0.55 (2H, m).
Physical properties: amorphous.

(Example 359)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 1-propanesulfonate (Compound No. 2038)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.34-7.05 (4H, m), 3.48 (2H, t, J = 7.7Hz), 2.20 (3H, s), 2.10 (2H , sixtet, J = 7.7Hz), 1.14 (3H, t, J = 7.7Hz).
Melting point (° C): 72-73.

(Example 360)
6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl 1-propanesulfonate (Compound No. 2040)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.28-7.15 (2H, m), 7.12-6.99 (2H, m), 3.52-3.45 (2H, m), 2.17-1.98 ( 2H, m), 1.92-1.78 (1H, m), 1.11 (3H, t, J = 7.3Hz), 0.85-0.73 (2H, m), 0.69-0.60 (2H, m).
Physical properties: Pasty.

(Example 361)
6-Chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinyl 1-propanesulfonate (Compound No. 2042)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.56 (1H, s), 7.26-7.14 (2H, m), 6.94 (1H, dd, J = 7.0, 1.8Hz), 3.50-3.42 (2H, m) , 2.98 (2H, t, J = 7.3Hz), 2.74 (2H, t, J = 7.3Hz), 2.17-1.98 (4H, m), 1.12 (3H, t, J = 7.3Hz).
Physical properties: Pasty.

(Example 362)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -5-iodo-4-pyridazinol (Compound No. 3849)
¹ H-NMR (200MHz, CD3OD) δppm: 7.08-7.05 (2H, m), 6.84-6.80 (1H, m), 2.14 (3H, s), 1.86-1.75 (1H, m), 0.81-0.65 (2H , m), 0.60-0.52 (2H, m).
Physical properties: amorphous.

(Example 363)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl trifluoromethanesulfonate (Compound No. 2106)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.52 (1H, s), 7.19-7.09 (2H, m), 6.96-6.89 (1H, m), 2.15 (3H, s), 1.81-1.67 (1H, m), 0.73-0.58 (4H, m).
Melting point (° C): 64-67.

(Example 364)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl benzenesulfonate (Compound No. 2147)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 8.10-7.83 (2H, m), 7.80-7.40 (3H, m), 7.59 (1H, s), 7.30-7.00 (3H, m), 6.90-6.60 ( 1H, m).
Melting point (° C): 91.5-92.

(Example 365)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl benzenesulfonate (Compound No. 2151)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.02-7.98 (2H, m), 7.78-7.70 (1H, m), 7.62-7.54 (2H, m), 7.58 (1H, s), 7.26-7.09 ( 2H, m), 6.98-6.93 (1H, m), 6.78-6.69 (1H, m), 1.68-1.54 (1H, m), 0.74-0.52 (4H, m).
Physical property: Oily substance.

(Example 366)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl benzenesulfonate (Compound No. 2176)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.07-8.01 (2H, m), 7.80-7.71 (1H, m), 7.65-7.56 (2H, m), 7.60 (1H, s), 7.11-6.99 ( 2H, m), 6.80 (1H, dd, J = 4.4, 2.4Hz), 1.93 (3H, s), 1.61-1.45 (1H, m), 0.65-0.45 (4H, m).
Melting point (° C): 105-106.

(Example 367)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 4-chlorobenzenesulfonate (Compound No. 2198)
¹ H-NMR (60MHz, CDCl ₃ ) δppm: 7.94 (2H, d, J = 8.4Hz), 7.60 (1H, s), 7.59 (2H, d, J = 8.4Hz), 7.23-7.09 (3H, m ), 6.90-6.60 (1H, m), 2.93 (3H, s).
Melting point (° C): 93-94.

(Example 368)
3- (2-Isopropylphenoxy) -4-pyridazinyl 4-chlorobenzenesulfonate (Compound No. 2199)
¹ H-NMR (60MHz, CDCl ₃ ) δppm: 7.91 (2H, d, J = 8.4Hz), 7.62 (1H, s), 7.55 (2H, d, J = 8.4Hz), 7.50-7.00 (3H, m ), 6.80-6.60 (1H, m), 3.20-2.50 (1H, m), 1.14 (6H, d, J = 7.0Hz).
Refractive index: nD22 1.5315.

(Example 369)
3- (2-tert-Butylphenoxy) -6-chloro-4-pyridazinyl 4-chlorobenzenesulfonate (Compound No. 2200)
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 8.05-7.05 (8H, m), 6.70-6.40 (1H, m), 1.26 (9H, s).
Melting point (° C): 83.5-84.5.

(Example 370)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2220)
^{1 H-NMR (60MHz, CDCl} 3) δppm: 7.83 (2H, d, J = 8.4Hz), 7.47 (2H, d, J = 8.4Hz), 7.32-6.95 (4H, m), 6.85-6.55 (1H m), 2.43 (3H, s), 1.98 (3H, s).
Melting point (° C): 102-104.

(Example 371)
6-Chloro-3- (2-ethylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2221)
Refractive index: nD28 1.5847.

(Example 372)
6-chloro-3- (2-isopropylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2222)
¹ H-NMR (60MHz, CDCl ₃ ) δppm: 8.00-6.50 (8H, m), 7.55 (1H, s), 2.85 (1H, septet, J = 7.0Hz), 2.42 (3H, s), 1.11 (6H , d, J = 7.0 Hz).
Melting point (° C): 99-100.

(Example 373)
3- (2-sec-Butylphenoxy) -6-chloro-4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2223)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 7.98-6.50 (8H, m), 7.52 (1H, s), 2.99-2.31 (1H, m), 2.41 (3H, s), 1.82-0.95 (2H, m), 1.08 (3H, d, J = 7.0 Hz), 0.90-0.35 (3H, m).
Melting point (° C): 65-66.

(Example 374)
3- (2-tert-Butylphenoxy) -6-chloro-4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2224)
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 7.98-7.00 (7H, m), 7.61 (1H s), 6.78-6.45 (1H, m), 2.40 (3H, s), 1.29 (9H, s).
Melting point (° C): 98-99.

(Example 375)
5,6-Dichloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol (Compound No. 3837)
¹ H-NMR (200MHz, CD3OD) δppm: 7.08-7.06 (2H, m), 6.85-6.80 (1H, m), 2,14 (3H, s), 1.87-1.78 (1H, m), 0.81-0.72 (2H, m), 0.64-0.52 (2H, m).
Physical properties: amorphous.

(Example 376)
6-Chloro-3- (2-cyclohexylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2230)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 8.00-6.50 (8H, m), 7.50 (1H, s), 2.50 (1H, br.s), 2.40 (3H, s), 2.00-0.90 (10H, m).
Melting point (° C): 120-121.

(Example 377)
3-([1,1'-biphenyl] -2-yloxy) -6-chloro-4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2231)
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 7.80-6.60 (14H, m), 2.42 (3H, s).
Melting point (° C): 106-108.

(Example 378)
6-Chloro-3- (2-methoxyphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2232)
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 8.00-6.70 (8H, m), 7.56 (1H, s), 3.62 (3H, s), 2.44 (3H, s).
Melting point (° C): 153-157.

(Example 379)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl propionate (Compound No. 1160)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.39 (1H, s), 7.14-7.05 (2H, m), 6.89-6.82 (1H, m), 2.72 (2H, q, J = 7.6Hz), 2.12 (3H, s), 1.82-1.68 (1H, m), 1.31 (3H, t, J = 7.6Hz), 0.74-0.53 (4H, m).
Melting point (° C): 75-77.

(Example 380)
6-chloro-3- (3-chlorophenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2234)
Refractive index: nD28 1.5970.

(Example 381)
3- (3-tert-Butylphenoxy) -6-chloro-4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2235)
¹ H-NMR (60MHz, CDCl ₃ ) δppm: 7.73 (2H, d, J = 8.2Hz), 7.49 (1H, s), 7.23 (2H, d, J = 8.2Hz), 7.14 (1H, d, J = 4.0Hz), 6.90-6.45 (3H, m), 2.38 (3H, s), 1.26 (9H, s).
Melting point (° C): 56-57.

(Example 382)
6-Chloro-3- [3- (trifluoromethyl) phenoxy] -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2236)
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 7.95-6.93 (9H, m), 2.40 (3H, s).
Refractive index: nD25.5 1.5556.

(Example 383)
6-Chloro-3- (3-cyanophenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2237)
¹ H-NMR (90 MHz, CDCl ₃ ) δ ppm: 7.85 (2H, d, J = 8.0 Hz), 7.70-7.00 (7H, m), 2.49 (3H, s).
Physical properties: Pasty.

(Example 384)
6-Chloro-3- (3-methoxyphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2238)
¹ H-NMR (60 MHz, CDCl ₃ ) δ ppm: 7.90-6.30 (8H, m), 7.47 (1H, s), 3.71 (3H, s), 2.40 (3H, s).
Melting point (° C): 89-90.

(Example 385)
6-Chloro-3- (1-naphthyloxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2240)
^{1 H-NMR (60MHz, CDCl} 3) δppm: 7.90-6.80 (12H, m), 2.38 (3H, s).
Melting point (° C): 92-94.

(Example 386)
3- (2-Bromo-4-tert-butylphenoxy) -6-chloro-4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2245)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 7.89 (2H, d, J = 8.4 Hz), 7.63 (1H, s), 7.62-7.18 (3H, m), 6.84 (2H, d, J = 8.4 Hz) ), 2.43 (3H, s), 1.29 (9H, s).
Melting point (° C): 110-112.

(Example 387)
6-Chloro-3- (4-chloro-2-methylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2246)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 7.95-7.75 (2H, m), 7.60-7.00 (5H, m), 6.80-6.60 (1H, m), 2.46 (3H, s), 2.00 (3H, s).
Melting point (° C): 115-116.

Example 388
6-Chloro-3- (2,4-dimethylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2247)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 7.94-7.78 (2H, m), 7.54 (1H, s), 7.41-7.23 (2H, m), 7.02-6.53 (3H, m), 2.46 (3H, s), 2.30 (3H, s), 1.96 (3H, s).
Melting point (° C): 80-81.

(Example 389)
3- (4-Bromo-2-isopropylphenoxy) -6-chloro-4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2248)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 7.80 (2H, d, J = 8.4 Hz), 7.51 (1H, s), 7.45-7.10 (3H, m), 6.56 (2H, d, J = 8.4 Hz) ), 2.85 (1H, septet, J = 6.8Hz), 2.43 (3H, s), 1.10 (6H, d, J = 6.8Hz).
Melting point (° C): 119-122.

(Example 390)
6-Chloro-3- (2-isopropyl-5-methylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2249)
¹ H-NMR (60 MHz, CDCl ₃ ) δppm: 8.00-6.80 (6H, m), 7.56 (1H, s), 6.46 (1H, br.s), 2.95-2.50 (1H, m), 2.44 (3H, s), 2.25 (3H, s), 1.09 (6H, d, J = 7.0 Hz).
Melting point (° C): 90-92.

(Example 391)
6-Chloro-3- (2,6-dimethylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2263)
Melting point (° C): 89-90.

(Example 392)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methylbenzenesulfonate (Compound No. 2265)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.90 (2H, d, J = 8.1Hz), 7.60 (1H, s), 7.38 (2H, d, J = 8.1Hz), 7.11-7.01 (2H, m ), 6.80 (1H, dd, J = 6.6, 2.6Hz), 2.47 (3H, s), 1.93 (3H, s), 1.59-1.46 (1H, m), 0.64-0.45 (4H, m).
Melting point (° C): 85-87.

(Example 393)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 4-nitrobenzenesulfonate (Compound No. 2287)
¹ H-NMR (60MHz, CDCl ₃ ) δppm: 8.41 (2H, d, J = 8.4Hz), 8.33 (2H, d, J = 8.4Hz), 7.61 (1H, s), 7.30-7.02 (3H, m ), 6.95-6.63 (1H, m), 2.03 (3H, s).
Melting point (° C): 166-169.

(Example 394)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl 4-nitrobenzenesulfonate (Compound No. 2289)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.39 (2H, d, J = 8.8Hz), 8.23 (2H, d, J = 8.8Hz), 7.59 (1H, s), 7.20-7.09 (2H, m ), 6.97-6.92 (1H, m), 6.77-6.73 (1H, m), 1.67-1.59 (1H, m), 0.78-0.54 (4H, m).
Melting point (° C): 158.

(Example 395)
6-Chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl dimethylsulfamate (Compound No. 2351)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 7.60 (1H, s), 7.26-7.01 (4H, m), 3.09 (6H, s), 1.95-1.78 (1H, m), 0.85-0.63 (4H, m).
Physical property: Oily substance.

(Example 396)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-methylpropanoate (Compound No. 1172)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.38 (1H, s), 7.14-7.05 (2H, m), 6.90-6.83 (1H, m), 2.93 (1H, septet, J = 7.0 Hz), 2.13 (3H, s), 1.80-1.66 (1H, m), 1.36 (6H, d, J = 7.0Hz), 0.78-0.56 (4H, m).
Melting point (° C): 38-39.

(Example 397)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl pentanoate (Compound No. 1178)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.38 (1H, s), 7.13-7.00 (2H, m), 6.90-6.77 (1H, m), 2.68 (2H, t, J = 7.3Hz), 2.12 (3H, s), 1.88-1.65 (3H, m), 1.60-1.35 (2H, m), 0.95 (3H, t, J = 7.3Hz), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 398)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-methylbutanoate (Compound No. 1184)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.37 (1H, s), 7.14-7.07 (2H, m), 6.89-6.82 (1H, m), 2.55 (2H, d, J = 7.0Hz), 2.27 (1H, br.septet, J = 6.8Hz), 2.12 (3H, s), 1.80-1.67 (1H, m), 1.07 (6H, d, J = 6.6Hz), 0.77-0.55 (4H, m).
Melting point (° C): 71-74.

(Example 399)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl pentadecanoate (Compound No. 1260)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.37 (1H, s), 7.10-7.00 (2H, m), 6.87-6.77 (1H, m), 2.66 (2H, t, J = 6.4Hz), 2.12 (3H, s), 1.85-1.65 (3H, m), 1.35-1.18 (22H, m), 0.95-0.82 (3H, m), 0.80-0.50 (4H, m).
Melting point (° C): 35-37.

(Example 400)
6-Chloro-3-phenoxy-5- (trimethylsilyl) -4-pyridazinol (Compound No. 2402)
¹ H-NMR (90 MHz, CDCl ₃ ) δ ppm: 12.0 (1H, br.s), 7.30-6.81 (5H, m), 0.28 (9H, s).
Melting point (° C): 119-120.

(Example 401)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl cyclobutanecarboxylate (Compound No. 1286)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.38 (1H, s), 7.14-7.05 (2H, m), 6.89-6.79 (1H, m), 3.58-3.40 (1H, m), 2.60-1.85 ( 6H, m), 2.13 (3H, s), 1.82-1.67 (1H, m), 0.80-0.67 (2H, m), 0.64-0.53 (2H, m).
Physical properties: Pasty.

(Example 402)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl cyclohexanecarboxylate (Compound No. 1298)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.37 (1H, s), 7.15-7.05 (2H, m), 6.90-6.80 (1H, m), 2.78-2.60 (1H, m), 2.12 (3H, s), 1.90-1.20 (10H, m), 0.80-0.50 (4H, m).
Melting point (° C): oily substance.

(Example 403)
3- (2-Isopropylphenoxy) -6-methyl-4-pyridazinol (Compound No. 2418)
¹ H-NMR (200MHz, CD3OD) δppm: 7.40-7.35 (1H, m), 7.25-7.16 (2H, m), 7.04-6.98 (1H, m), 6.43 (1H, s), 3.06 (1H, septet , J = 7.0Hz), 2.36 (3H, s), 1.18 (6H, d, J = 7.0Hz).
Melting point (° C): 259-260.

(Example 404)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-bromobutanoate (Compound No. 1334)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.44 (1H, s), 7.14-7.05 (2H, m), 6.90-6.83 (1H, m), 4.45 (1H, t, J = 7.6Hz), 2.22 (1H, dq, J = 7.3, 7.6Hz), 2.13 (3H, s), 1.81-1.69 (1H, m), 1.17 (3H, t, J = 7.3Hz), 0.74-0.69 (2H, m), 0.58-0.56 (2H, m).
Physical properties: Pasty.

(Example 405)
3- (2-Isopropylphenoxy) -6- (trifluoromethyl) -4-pyridazinol (Compound No. 2431)
¹ H-NMR (60MHz, CDCl ₃ ) δppm: 7.60-6.70 (4H, m), 6.87 (1H, s), 2.97 (1H, septet, J = 7.0Hz), 1.10 (6H, d, J = 7.0Hz ).
Melting point (° C): 126.5.

(Example 406)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-chlorobutanoate (Compound No. 1340)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.40 (1H, s), 7.14-7.05 (2H, m), 6.89-6.82 (1H, m), 3.68 (2H, t, J = 6.2Hz), 2.91 (2H, t, J = 7.0Hz), 2.31-2.18 (2H, m), 2.11 (3H, s), 1.79-1.65 (1H, m), 0.80-0.67 (2H, m), 0.63-0.53 (2H , m).
Physical properties: Pasty.

(Example 407)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-methyl-2-butenoate (Compound No. 1358)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.44 (1H, s), 7.12-7.05 (2H, m), 6.88-6.80 (1H, m), 5.99-5.97 (1H, m), 2.26 (3H, d, J = 1.1Hz), 2.13 (3H, s), 2.04 (3H, d, J = 1.1Hz), 1.83-1.70 (1H, m), 0.77-0.64 (2H, m), 0.60-0.53 (2H , m).
Physical properties: Pasty.

(Example 408)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl (2E) -3-phenyl-2-propenoate (Compound No. 1364)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.96 (1H, d, J = 16.0 Hz), 7.63-7.59 (2H, m), 7.53 (1H, s), 7.48-7.43 (3H, m), 7.09 -7.05 (2H, m), 6.86-6.81 (1H, m), 6.66 (1H, d, J = 16.0Hz), 2.16 (3H, s), 1.83-1.75 (1H, m), 0.79-0.54 (4H , m).
Physical properties Amorphous.

(Example 409)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl methyl succinate (Compound No. 1382)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.44 (1H, s), 7.08-7.02 (2H, m), 6.88-6.74 (1H, m), 3.69 (3H, s), 3.01 (2H, t, J = 7.3Hz), 2.78 (2H, t, J = 7.3Hz), 2.11 (3H, s), 1.85-1.65 (1H, m), 0.80-0.50 (4H, m).
Physical property: Oily substance.

(Example 410)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-chlorobenzoate (Compound No. 1441)
¹ H-NMR (200 MHz, CDCl ₃ ) δ ppm: 8.14 (1H, d, J = 8.8 Hz), 7.58 (1H, s), 7.59-7.39 (3H, m), 7.10-7.05 (2H, m), 6.88 -6.80 (1H, m), 2.16 (3H, s), 1.90-1.70 (1H, m), 0.85-0.50 (4H, m).
Physical property: Oily substance.

(Example 411)
3- (2-Methylphenoxy) -6- (2-thienyl) -4-pyridazinol (Compound No. 2478)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.56-7.48 (2H, m), 7.21-7.00 (4H, m), 6.97-6.90 (1H, m), 6.69 (1H, s), 2.11 (3H, s).
Melting point (° C): 86-87.

(Example 412)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-methylbenzoate (Compound No. 1481)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.20 (1H, d, J = 7.0Hz), 7.56 (1H, s), 7.52 (1H, d, J = 7.7Hz), 7.40-7.28 (2H, m ), 7.10-7.00 (2H, m), 6.90-6.88 (1H, m), 2.69 (3H, s), 2.16 (3H, s), 1.90-1.70 (1H, m), 0.82-0.65 (2H, m ), 0.65-0.50 (2H, m).
Physical property: Oily substance.

(Example 413)
3,6-Bis (2-methylphenoxy) -4-pyridazinol (Compound No. 2492)
¹ H-NMR (60 MHz, DMF-d7) δ ppm: 7.40-6.90 (8H, m), 5.79 (1H, s), 2.19 (6H, br.s).
Melting point (° C): 247-250.

(Example 414)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-methoxybenzoate (Compound No. 1522)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.09 (1H, dd, J = 7.9, 2.0Hz), 7.68-7.57 (1H, m), 7.59 (1H, s), 7.15-7.03 (4H, m) , 6.90-6.82 (1H, m), 3.96 (3H, s), 2.17 (3H, s), 1.96-1.72 (1H, m), 0.78-0.65 (2H, m), 0.65-0.51 (2H, m) .
Physical properties: Gummy.

(Example 415)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-methylbenzoate (Compound No. 1531)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.05-8.00 (2H, m), 7.58 (1H, s), 7.55-7.38 (2H, m), 7.10-7.05 (2H, m), 6.88-6.80 ( 1H, m), 2.46 (3H, s), 2.16 (3H, s), 1.90-1.68 (1H, m), 0.80-0.50 (4H, m).
Physical property: Oily substance.

(Example 416)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-chlorobenzoate (Compound No. 1537)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.16 (2H, d, J = 8.8Hz), 7.59 (1H, s), 7.54 (2H, d, J = 8.8Hz), 7.14-7.07 (2H, m ), 6.88-6.83 (1H, m), 2.15 (3H, s), 1.84-1.69 (1H, m), 0.80-0.70 (2H, m), 0.62-0.55 (2H, m).
Physical properties: amorphous.

(Example 417)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-bromobenzoate (Compound No. 1543)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.07 (2H, d, J = 8.6Hz), 7.70 (2H, d, J = 8.6Hz), 7.59 (1H, s), 7.12-7.03 (2H, m ), 6.89-6.82 (1H, m), 2.15 (3H, s), 1.83-1.67 (1H, m), 0.78-0.50 (4H, m).
Physical properties: amorphous.

(Example 418)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-iodobenzoate (Compound No. 1549)
¹ H-NMR (200 MHz, CDCl ₃ ) δ ppm: 7.94 (2H, s), 7.93 (1H, m), 7.62 (1H, s), 7.29 (1H, s), 7.12-7.09 (2H, m), 6.89 -6.87 (1H, m), 2.17 (3H, s), 1.84-1.73 (1H, m), 0.79-0.70 (2H, m), 0.62-0.55 (2H, m).
Physical properties: Pasty.

(Example 419)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methylbenzoate (Compound No. 1566)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.10 (2H, d, J = 8.1Hz), 7.60 (1H, s), 7.34 (2H, d, J = 8.1Hz), 7.12-7.03 (2H, m ), 6.88-6.81 (1H, m), 2.46 (3H, s), 2.15 (3H, s), 1.85-1.71 (1H, m), 0.78-0.65 (2H, m), 0.62-0.52 (2H, m ).
Melting point (° C): 77.5-78.

(Example 420)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-tert-butylbenzoate (Compound No. 1575)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.15 (2H, d, J = 8.8Hz), 7.59 (1H, s), 7.56 (2H, d, J = 8.8Hz), 7.09-7.06 (2H, m ), 6.86-6.82 (1H, m), 2.15 (3H, s), 1.37 (9H, s), 1.82-1.73 (1H, m), 0.76-0.69 (2H, m), 0.60-0.56 (2H, m ).
Melting point (° C): 139-142.

(Example 421)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-nitrobenzoate (Compound No. 1593)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.41 (4H, s), 7.61 (1H, s), 7.14-7.08 (2H, m), 6.89-6.83 (1H, m), 2.17 (3H, s) , 1.81-1.70 (1H, m), 0.80-0.71 (2H, m), 0.62-0.54 (2H, m).
Physical properties: amorphous.

(Example 422)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methoxybenzoate (Compound No. 1599)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.17 (2H, d, J = 8.8Hz), 7.60 (1H, s), 7.12-7.04 (2H, m), 7.01 (2H, d, J = 8.8Hz ), 6.88-6.82 (1H, m), 3.90 (1H, s), 2.16 (3H, s), 1.85-1.71 (1H, m), 0.78-0.69 (2H, m), 0.60-0.52 (2H, m ).
Physical properties: amorphous.

(Example 423)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,4-dichlorobenzoate (Compound No. 1616)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.11 (1H, d, J = 8.4Hz), 7.60-7.57 (2H, m), 7.42 (1H, dd, J = 8.4, 2.2Hz), 7.14-7.08 (2H, m), 6.89-6.83 (1H, m), 2.15 (3H, s), 1.85-1.72 (1H, m), 0.78-0.67 (2H, m), 0.63-0.54 (2H, m).
Physical properties: amorphous.

(Example 424)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl phthalate (Compound No. 1620)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.98-7.94 (1H, m), 7.88-7.84 (1H, m), 7.81-7.71 (2H, m), 7.57, (1H, s), 7.28-7.17 (6H, m), 7.08-7.03 (1H, m), 3.70 (3H, s), 2.26 (3H, s), 2.15 (3H, s).
Physical properties: amorphous.

(Example 425)
Potassium 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinolate (Compound No. 3811)
¹ H-NMR (200MHz, CD3OD) δppm: 7.05-6.95 (2H, m), 6.83-6.72 (1H, m), 6.47 (1H, s), 2.00-1.83 (1H, m), 0.80-0.64 (2H , m), 0.64-0.48 (2H, m).
Melting point (° C): 187-189.

(Example 426)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl isophthalate (Compound No. 1631)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.61 (1H, t, J = 1.5Hz), 8.54-8.47 (1H, m), 8.22-8.16 (1H, m), 7.71 (1H, t, J = 8.1Hz), 7.61 (1H, s), 7.15-6.96 (4H, m), 6.89-6.82 (1H, m), 3.67 (3H, s), 2.44 (3H, s), 2.17 (3H, s), 1.88-1.72 (1H, m), 0.83-0.71 (2H, m), 0.64-0.53 (2H, m).
Physical properties: amorphous.

(Example 427)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-furoate (Compound No. 1643)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.74–7.73 (1H, m), 7.56 (1H, s), 7.50 (1H, dd, J = 3.7, 0.7 Hz), 7.13-7.04 (2H, m) , 6.88-6.81 (1H, m), 6.65-6.63 (1H, m), 2.15 (3H, s), 1.85-1.71 (1H, m), 0.78-0.69 (2H, m), 0.62-0.52 (2H, m).
Physical properties: Pasty.

(Example 428)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-thiophenecarboxylate (Compound No. 1649)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.07-8.05 (1H, m), 7.78-7.75 (1H, m), 7,58 (1H, s), 7.24-7.20 (1H, m), 7.13- 7.06 (2H, m), 6.89-6.83 (1H, m), 2.16 (3H, s), 1.83-1.71 (1H, m), 0.80-0.70 (2H, m), 0.65-0.55 (2H, m).
Physical properties: amorphous.

(Example 429)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl isobutyl carbonate (Compound No. 1770)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.49 (1H, s), 7.15-7.05 (2H, m), 6.89-6.82 (1H, m), 4.13 (2H, d, J = 6.6Hz), 2.14 (3H, s), 2.09 (1H, br. Septet, J = 7.0Hz), 1.88-1.68 (1H, m), 1.01 (6H, d, J = 7.0Hz), 0.78-0.52 (4H, m).
Melting point (° C): 72-74.

(Example 430)
Allyl 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl carbonate (Compound No. 1811)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.50 (1H, s), 7.15-7.06 (2H, m), 6.89-6.82 (1H, m), 6.10-5.90 (1H, m), 5.51-5.35 ( 2H, m), 4.84-4.80 (2H, m), 2.14 (3H, s), 1.85-1.70 (1H, m), 0.78-0.53 (4H, m).
Physical property: Oily substance.

(Example 431)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl dimethyl carbamate (Compound No. 1891)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.56 (1H, s), 7.13-7.05 (2H, m), 6.89-6.82 (1H, m), 3.16 (3H, s), 3.05 (3H, s) , 2.15 (3H, s), 1.85-1.71 (1H, m), 0.78-0.54 (4H, m).
Melting point (° C): 136-138.

(Example 432)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl diethylcarbamate (Compound No. 1911)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.58 (1H, s), 7.10-7.07 (2H, m), 6.87-6.83 (1H, m), 3.48 (2H, q, J = 7.3Hz), 3.41 (2H, q, J = 7.0Hz), 2.15 (3H, s), 1.82-1.72 (1H, m), 1.29 (3H, t, J = 7.3Hz), 1.23 (3H, t, J = 7.0Hz) , 0.74-0.57 (4H, m).
Melting point (° C): 119-121.

(Example 433)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl diisopropylcarbamate (Compound No. 1920)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.61 (1H, s), 7.10-7.00 (2H, m), 6.90-6.85 (1H, m), 4.20-3.90 (2H, m), 2.14 (3H, s), 1.87-1.67 (1H, m), 1.45-1.20 (12H, m), 0.80-0.50 (4H, m).
Melting point (° C): 103-105.

(Example 434)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-thiophenesulfonate (Compound No. 3792)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.89-7.82 (2H, m), 7.58 (1H, s), 7.22-7.13 (1H, m), 7.13-7.02 (2H, m), 6.84-6.79 ( 1H, m), 1.99 (3H, s), 1.69-1.53 (1H, m), 0.70-0.48 (4H, m).
Physical properties: amorphous.

(Example 435)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl methyl (phenyl) carbamate (Compound No. 1946)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.40-7.25 (6H, m), 7.11-7.08 (2H, m), 6.87-6.82 (1H, m), 3.42 (3H, br.s), 2.15 ( 3H, br.s), 1.82-1.68 (1H, m), 0.71-0.56 (4H, m).
Physical properties: amorphous.

(Example 436)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl diphenylcarbamate (Compound No. 1952)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.45-7.28 (11H, m), 7.16-7.09 (2H, m), 6.87-6.82 (1H, m), 2.11 (3H, s), 1.79-1.66 ( 1H, m), 0.69-0.56 (4H, m).
Physical properties: amorphous.

(Example 437)
O- [6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] S-methyl thiocarbonate (Compound No. 1958)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.47 (1H, s), 7.13-7.06 (2H, m), 6.89-6.83 (1H, m), 2.49 (3H, s), 2.14 (3H, s) , 1.83-1.69 (1H, m), 0.78-0.65 (2H, m), 0.63-0.55 (2H, m).
Physical properties: Pasty.

(Example 438)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl ethanesulfonate (Compound No. 2034)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.58 (1H, s), 7.15-7.05 (2H, m), 6.92-6.82 (1H, m), 3.58 (2H, q, J = 7.4Hz), 2.15 (3H, s), 1.82-1.68 (1H, m), 1.64 (3H, t, J = 7.4Hz), 0.78-0.52 (4H, m).
Melting point (° C): 96-97.

(Example 439)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-propanesulfonate (Compound No. 2051)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.58 (1H, s), 7.18-7.05 (2H, m), 6.94-6.83 (1H, m), 3.53 (2H, t, J = 7.7Hz), 2.20 -2.00 (2H, m), 2.15 (3H, s), 1.82-1.67 (1H, m), 1.15 (3H, t, J = 7.7Hz), 0.80-0.50 (4H, m).
Melting point (° C): 70.5-71.5.

(Example 440)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-propanesulfonate (Compound No. 2060)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.59 (1H, s), 7.18-7.07 (2H, m), 6.93-6.82 (1H, m), 3.75 (1H, septet, 7.0Hz), 2.15 (3H , S), 1.85-1.65 (1H, m), 1.65 (6H, d, J = 7.0Hz), 0.78-0.50 (4H, m).
Physical property: Oily substance.

(Example 441)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-octanesulfonate (Compound No. 2066)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.15-7.07 (2H, m), 6.89-6.85 (1H, s), 3.60-3.50 (2H, m), 2.15 (3H, s), 2.15-1.98 (2H, m), 1.83-1.67 (1H, m), 1.58-1.15 (10H, m), 0.95-0.83 (3H, m), 0.80-0.68 (2H, m), 0.65- 0.55 (2H, m).
Physical properties: Pasty.

(Example 442)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl chloromethanesulfonate (Compound No. 2072)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.58 (1H, s), 7.18-7.09 (2H, m), 6.92-6.85 (1H, m), 5.02 (2H, s), 2.16 (3H, s) , 1.83-1.68 (1H, m), 0.80-0.68 (2H, m), 0.65-0.55 (2H, m).
Physical properties: Pasty.

(Example 443)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,2,2-trifluoroethanesulfonate (Compound No. 2136)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 7.19-7.05 (2H, m), 6.90 (1H, dd, J = 6.6, 2.9 Hz), 4.39 (2H, q, J = 8.2Hz), 2.15 (3H, s), 1.80-1.65 (1H, m), 0.80-0.50 (4H, m).
Physical properties: amorphous.

(Example 444)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-chlorobenzenesulfonate (Compound No. 2212)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.01-7.92 (2H, m), 7.62-7.53 (3H, m), 7.13-7.00 (2H, m), 6.85-6.77 (1H, m), 2.04 ( 3H, s), 1.58-1.45 (1H, m), 0.70-0.45 (4H, m).
Physical properties: Gummy.

(Example 445)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-nitrobenzenesulfonate (Compound No. 2300)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.50-8.39 (2H, m), 8.33-8.20 (2H, m), 7.59 (1H, s), 7.15-7.00 (2H, m), 6.85-6.75 ( 1H, m), 1.94 (3H, s), 1.65-1.45 (1H, m), 0.75-0.45 (4H, m).
Physical properties: Gummy.

(Example 446)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methoxybenzenesulfonate (Compound No. 2309)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.99-7.91 (2H, m), 7.61 (1H, s), 7.11-6.98 (4H, m), 6.80 (1H, dd, J = 2.6Hz, 6.6Hz ), 3.90 (3H, s), 1.95 (3H, s), 1.60-1.45 (1H, m), 0.70-0.45 (4H, m).
Physical properties: candy-like.

(Example 447)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,4,6-trimethylbenzenesulfonate (Compound No. 2315)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.59 (1H, s), 7.13-6.98 (4H, m), 6.85-6.75 (1H, m), 2.70 (6H, s), 2.32 (3H, s) , 2.04 (3H, s), 1.65-1.45 (1H, m), 0.78-0.44 (4H, m).
Physical properties: amorphous.

(Example 448)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,4,6-triisopropylbenzenesulfonate (Compound No. 2321)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.52 (1H, s), 7.28-7.20 (2H, m), 7.10-6.98 (2H, m), 6.85-6.75 (1H, m), 4.16 (2H, septet, J = 6.6Hz), 2.93 (1H, septet, J = 6.6Hz), 1.93 (3H, s), 1.75-1.50 (1H, m), 1.35-1.20 (18H, m), 0.75-0.45 (4H , m).
Physical properties: amorphous.

(Example 449)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazoyl-5-yl 1,2-benzene Disulfonate (Compound No. 2327)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.52-8.40 (1H, m), 8.15-8.07 (1H, m), 8.00-7.82 (2H, m), 7.63 (1H, s), 7.18 (2H, s), 7.15-6.97 (3H, m), 6.79 (1H, dd, J = 7.0, 2.6Hz), 3.84 (3H, s), 2.11 (3H, s), 1.99 (3H, s), 1.75-1.57 (1H, m), 0.74-0.45 (4H, m).
Physical properties: candy-like.

(Example 450)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-chloro-3-nitrobenzenesulfonate (Compound No. 3786)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.55 (1H, d, J = 2.2 Hz), 8.18 (1H, dd, J = 8.8, 2.2 Hz), 7.81 (1H, d, J = 8.8 Hz), 7.59 (1H, s), 7.13-7.06 (2H, m), 6.84-6.79 (1H, m), 1.98 (3H, s), 1.61-1.48 (1H, m), 0.68-0.52 (4H, m).
Physical properties: amorphous.

(Example 451)
6-Chloro-3- [2- (2-chloro-2-fluorocyclopropyl) phenoxy] -4-pyridazinol (Compound No. 2519)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.42-7.15 (4H, m), 6.70 (1H, s), 2.80-2.62 (1H, m), 2.18-1.65 (2H, m).
Melting point (° C): 175-177.

(Example 452)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,5-dichlorobenzenesulfonate (Compound No. 3780)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.09-8.08 (1H, m), 7.61-7.52 (3H, m), 7.12-7.01 (2H, m), 6.81-6.76 (1H, m), 1.98 ( 3H, s), 1.67-1.49 (1H, m), 0.82-0.60 (2H, m), 0.58-0.48 (2H, m).
Physical properties: amorphous.

(Example 453)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 10H-phenothiazine-10-carboxylate (Compound No. 3720)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.76-7.67 (3H, m), 7.49-7.40 (3H, m), 7.40-7.23 (3H, m), 7.20-7.10 (2H, m), 6.95- 6.83 (1H, m), 2.19 (3H, s), 1.88-1.70 (1H, m), 0.85-0.57 (4H, m).
Physical properties: amorphous.

(Example 454)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 9H-carbazole-9-carboxylate (Compound No. 3714)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.40 (2H, d, J = 7.4Hz), 8.02 (2H, d, J = 7.0Hz), 7.99 (1H, s), 7.60-7.35 (4H, m ), 7.13-7.03 (2H, m), 6.92-6.80 (1H, m), 2.19 (3H, s), 1.90-1.73 (1H, m), 0.84-0.50 (4H, m).
Melting point (° C): 157-159.

(Example 455)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,4-dihydro-2 (1H) -isoquinolinecarboxylate (Compound No. 3708)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.59 (1H, s), 7.32-7.02 (6H, m), 6.90-6.78 (1H, m), 4.86 (1H, s), 4.72 (1H, s) , 3.92 (1H, t, J = 5.9Hz), 3.81 (1H, t, J = 5.9Hz), 3.05-2.95 (2H, m), 2.14 (3H, s), 1.86-1.67 (1H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 456)
3- [3- (Benzyloxy) phenoxy] -6-chloro-4-pyridazinol (Compound No. 2547)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.48-7.25 (6H, m), 6.94-6.66 (4H, m), 5.07 (2H, s).
Melting point (° C): 184-185.

(Example 457)
3- [4- (Benzyloxy) phenoxy] -6-chloro-4-pyridazinol (Compound No. 2548)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.48-7.28 (5H, m), 7.12-6.96 (4H, m), 6.58 (1H, s), 5.07 (2H, s).
Melting point (° C): 170-180.

(Example 458)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-thiomorpholine carboxylate (Compound No. 3702)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.53 (1H, s), 7.15-7.04 (2H, m), 6.92-6.80 (1H, m), 4.05-3.78 (4H, m), 2.75-2.64 ( 4H, m), 2.13 (3H, s), 1.85-1.65 (1H, m), 0.80-0.54 (4H, m).
Physical properties: candy-like.

(Example 459)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,6-dimethyl-4-morpholinecarboxylate (Compound No. 3696)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.54 (1H, s), 7.18-7.05 (2H, m), 6.94-6.80 (1H, m), 4.17-3.97 (2H, m), 3.78-3.55 ( 2H, m), 2.95-2.60 (2H, m), 2.14 (3H, s), 1.85-1.67 (1H, m), 1.35-1.15 (6H, m), 0.80-0.54 (4H, m).
Physical properties: candy-like.

(Example 460)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3690)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.13-7.06 (2H, m), 6.90-6.83 (1H, m), 3.70-3.55 (8H, m), 2.14 (3H, s), 1.83-1.68 (1H, m), 0.80-0.65 (2H, m), 0.65-0.53 (2H, m).
Melting point (° C): 102.5-103.5.

(Example 461)
6-Chloro-3-[(1-methyl-1H-indol-4-yl) oxy] -4-pyridazinol (Compound No. 2565)
¹ H-NMR (200MHz, CD3OD) δppm: 7.29 (1H, d, J = 8.4Hz), 7.17 (1H, t, J = 7.7Hz), 7.13 (1H, d, J = 2.9Hz), 6.85 (1H , d, J = 7.7Hz), 6.72 (1H, s), 6.23 (1H, d, J = 2.9Hz), 4.87 (3H, s).
Melting point (° C): 203-206.

(Example 462)
6-Chloro-3-[(1-methyl-1H-indol-7-yl) oxy] -4-pyridazinol (Compound No. 2568)
^{1 H-NMR (200MHz, CD3OD} ) δppm: 7.42 (1H, d, J = 7.0Hz), 7.07 (1H, d, J = 2.9Hz), 6.99 (1H, t, J = 7.7Hz), 6.86 (1H , d, J = 6,6Hz), 6.74 (1H, s), 6.44 (1H, d, J = 2.9Hz), 3.80 (3H, s).
Melting point (° C): 219-221.

(Example 463)
1- {4-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] -3-methylphenyl} ethanone (Compound No. 2570)
^{1 H-NMR (200MHz, CD3OD} ) δppm: 7.94-7.86 (2H, m), 7.21-7.16 (1H, m), 6.75 (1H, s), 2.60 (3H, s), 2.25 (3H, s).
Melting point (° C): 182-284.

(Example 464)
1- {4-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] -3-methylphenyl} ethanone O-methyloxime (Compound No. 2571)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.59-7.51 (2H, m), 7.11-7.06 (1H, m), 6.71 (1H, s), 3.95 (3H, s), 2.20 (3H, s).
Melting point (° C): 189-192.

(Example 465)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-phenyl-1-piperazinecarboxylate (Compound No. 3684)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 7.60 (1H, s), 7.35-7.23 (2H, m), 7.13-7.04 (2H, m), 7.00-6.80 (4H, m), 3.95-3.84 ( 2H, m), 3.84-3.72 (2H, m), 3.31-3.18 (4H, m), 2.15 (3H, s), 1.86-1.66 (1H, m), 0.80-0.53 (4H, m).
Physical properties: candy-like.

(Example 466)
4-{[4- (Benzoyloxy) -6-chloro-3-pyridazinyl] oxy} -3-methylphenyl benzoate (Compound No. 3850)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.21-8.17 (4H, m), 7.72-7.48 (7H, m), 7.22-7.07 (3H, m), 2.21 (3H, s).
Melting point (° C): 118-120.

(Example 467)
Methyl 3-[(6-chloro-4-hydroxy-3-pyridazinyl) oxy] -4-methoxybenzoate (Compound No. 2574)
¹ H-NMR (200MHz, CD3OD) δppm: 7.95 (1H, dd J = 8.6, 2.2Hz), 7.78 (1H, d, J = 1.8Hz), 7.19 (1H, d, J = 8.8Hz), 6.71 ( 1H, s), 3.87 (3H, s), 3.84 (3H, s).
Melting point (° C): 115-123.

(Example 468)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methyl-1-piperazinecarboxylate (Compound No. 3678)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 7.59 (1H, s), 7.15-7.04 (2H, m), 6.90-6.80 (1H, m), 3.80-3.55 (4H, m), 2.54-2.40 ( 4H, m), 2.32 (3H, s), 2.14 (3H, s), 1.85-1.67 (1H, m), 0.80-0.52 (4H, m).
Physical properties: candy-like.

(Example 469)
6-Chloro-3- (2-isopropenyl-6-methylphenoxy) -4-pyridazinol (Compound No. 2577)
¹ H-NMR (200MHz, CD3OD) δppm: 7.20-7.10 (3H, m), 6.66 (1H, s), 5.01 (1H, m), 4.95 (1H, m), 2.15 (3H, s), 1.99 ( 3H, s).
Melting point (° C): 183-186.

(Example 470)
6-Chloro-3-[(1,1-dimethyl-2,3-dihydro-1H-inden-5-yl) oxy-4-pyridazinol (Compound No. 2585)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.15 (1H, d, J = 8.1 Hz), 6.95 (2H, br.d, J = 8.1 Hz), 6.68 (1H, s), 2.89 (2H, t, J = 7.3Hz), 1.96 (2H, t, J = 7.3Hz), 1.27 (6H, s).
Melting point (° C): 209-212.

(Example 471)
3- (3-Bromo-6-cyclopropyl-2-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 2587)
¹ H-NMR (200MHz, CD3OD) δppm: 7.38 (1H, d, J = 8.4Hz), 6.78 (1H, d, J = 8.4Hz), 6.72 (1H, s), 2.22 (3H, s), 1.85 -1.72 (1H, m), 0.85-0.72 (2H, m), 0.65-0.50 (2H, m).
Melting point (° C): 234-235.

(Example 472)
6-Chloro-3- (6-cyclopropyl-2-methyl-3-nitrophenoxy) -4-pyridazinol (Compound No. 2589)
¹ H-NMR (200MHz, CD3OD) δppm: 7.80 (1H, d, J = 8.4Hz), 7.02 (1H, d, J = 8.4Hz), 6.77 (1H, s), 2.32 (3H, s), 1.99 -1.88 (1H, m), 0.95-0.88 (2H, m), 0.74-0.70 (2H, m).
Melting point (° C): 140-143.

(Example 473)
6-Chloro-3-[(5-methyl-1,3-dihydro-2-benzofuran-4-yl) oxy] -4-pyridazinol (Compound No. 2592)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.20 (1H, d, J = 7.7 Hz), 7.08 (1H, d, J = 7.7 Hz), 5.06 (2H, br.s), 4.88 (2H, br. s), 2.16 (3H, s).
Melting point (° C): 188-200.

(Example 474)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,2,6,6-tetramethyl-1-piperidinecarboxylate (Compound No. 3672)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7,53 (1H, s), 7.14-7.03 (2H, m), 6.90-6.78 (1H, m), 2.13 (3H, s), 1.90-1.62 ( 7H, m), 1.55 (12H, s), 0.80-0.52 (4H, m).
Physical properties: candy-like.

(Example 475)
6-Chloro-3- (2-fluoro-3,5,6-trimethylphenoxy) -4-pyridazinol (Compound No. 2597)
¹ H-NMR (200MHz, CD3OD) δppm: 6.92 (1H, d, J = 7.0Hz), 6.73 (1H, s), 2.24 (3H, s), 2.21 (3H, s), 2.06 (3H, s) .
Melting point (° C): 258-260.

(Example 476)
6-Chloro-3- (2-chloro-3,5,6-trimethylphenoxy) -4-pyridazinol (Compound No. 2599)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 7.11 (1H, s), 6.86 (1H, br, s), 2.29 (3H, s), 2.24 (3H, s), 1.99 (3H, s).
Melting point (° C): 298-300.

(Example 477)
6-Chloro-3- (2-iodo-3,5,6-trimethylphenoxy) -4-pyridazinol (Compound No. 2600)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.06 (1H, s), 6.75 (1H, s), 2.40 (3H, s), 2.26 (3H, s), 2.09 (3H, s).
Melting point (° C): 235 (decomposition).

(Example 478)
6-Chloro-3- (2-ethyl-3,5,6-trimethylphenoxy) -4-pyridazinol (Compound No. 2601)
¹ H-NMR (200MHz, DMSO-d6) δppm: 6.95 (1H, s), 6.81 (1H, br.s), 2.32 (2H, q, J = 7.5Hz), 2.24 (3H, s), 2.12 ( 3H, s), 1.94 (3H, s), 1.04 (3H, t, J = 7.5Hz).
Melting point (° C): 188-195.

(Example 479)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1,4-dioxa-8-azaspiro [4.5] decane-8-carboxylate (Compound No. 3666)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.15-7.04 (2H, m), 6.92-6.80 (1H, m), 3.99 (4H, s), 3.85-3.62 (4H, m), 2.14 (3H, s), 1.85-1.65 (5H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 480)
6-Chloro-3- (2-isopropenyl-3,5,6-trimethylphenoxy) -4-pyridazinol (Compound No. 2605)
^{1 H-NMR (200MHz, CD3OD} ) δppm: 6.91 (1H, s), 6.58 (1H, s), 5.00-4.90 (2H, bm), 2.27 (3H, s), 2.20 (3H, s), 2.07 ( 3H, s), 1.96 (3H, s).
Physical properties: amorphous.

(Example 481)
1- [6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] 4-ethyl 1,4-piperidinedicarboxylate (Compound No. 3660)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.56 (1H, s), 7.13-7.04 (2H, m), 6.90-6.80 (1H, m), 4.30-4.00 (2H, m), 3.35-3.02 ( 2H, m), 2.65-2.45 (1H, m), 2.14 (3H, s), 2.10-1.93 (3H, m), 1.93-1.65 (4H, m), 1.25 (3H, t, J = 7.0Hz) , 0.80-0.54 (4H, m).
Physical properties: candy-like.

(Example 482)
1- {2-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] -3,4,6-trimethylphenyl} ethanone (Compound No. 2607)
^{1 H-NMR (200MHz, CD3OD} ) δppm: 7.55 (1H, s), 6.72 (1H, s), 2.45 (3H, s), 2.36 (3H, s), 2.29 (3H, s), 2.11 (3H, s).
Physical properties: amorphous.

(Example 483)
6-Chloro-3- (2,3,5-trimethyl-6-nitrophenoxy) -4-pyridazinol (Compound No. 2608)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.11 (1H, s), 6.65 (1H, s), 2.33 (3H, s), 2.28 (3H, s), 2.05 (3H, s).
Melting point (° C): 172-174.

(Example 484)
6-Chloro-3- (2,4-dichloro-3,5,6-trimethylphenoxy) -4-pyridazinol (Compound No. 2609)
¹ H-NMR (200 MHz, DMSO-d6) δ ppm: 6.91 (1H, s), 2.46 (3H, s), 2.36 (3H, s), 2.10 (3H, s).

(Example 485)
6-Chloro-3- (2,3,4,5,6-pentamethylphenoxy) -4-pyridazinol (Compound No. 2614)
¹ H-NMR (200 MHz, CD3OD) δ ppm: 6.69 (1H, s), 2.23 (3H, s), 2.21 (6H, s), 2.02 (6H, s).
Melting point (° C): 238-240 (decomposition).

(Example 486)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,3-dimethylbutanoate (Compound No. 2661)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.37 (1H, s), 7.13-7.05 (2H, s), 6.88-6.82 (1H, s), 2.55 (2H, s), 2.12 (3H, s) , 1.82-1.67 (1H, m), 1.15 (9H, s), 0.80-0.65 (2H, m), 0.63-0.52 (2H, m).
Melting point (° C): 91-92.

(Example 487)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-adamantanecarboxylate (Compound No. 2671)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.37 (1H, s), 7.12-7.05 (2H, m), 6.92-6.80 (1H, m), 2.13 (3H, s), 2.08 (9H, s) , 1.76 (7H, br.s), 0.85-0.45 (4H, m).
Physical property: Oily substance.

(Example 488)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-methyl acrylate (Compound No. 2677)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.48 (1H, s), 7.14-7.05 (2H, m), 6.89-6.83 (1H, m), 6.46 (1H, br.s), 5.91 (1H, br.s), 2.13 (3H, s), 2.09 (3H, s), 1.81-1.68 (1H, m), 0.78-0.53 (4H, m).
Melting point (° C): 98-100.

(Example 489)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-bromo-2-methylpropanoate (Compound No. 2697)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.47 (1H, s), 7.11-7.08 (2H, m), 6.89-6.85 (1H, m), 2.13 (3H, s), 2.10 (6H, s) , 1.77-1.69 (1H, m), 0.74-0.58 (4H, m).
Melting point (° C): 69-71.

(Example 490)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-chloro-2,2-dimethylpropanoate (Compound No. 2703)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.43 (1H, s), 7.13-7.05 (2H, m), 6.90-6.84 (1H, m), 3.76 (2H, s), 2.13 (3H, s) , 1.83-1.65 (1H, m), 1.50 (6H, s), 0.85-0.45 (4H, br. S).
Melting point (° C): 112-115.

(Example 491)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 5-bromopentanoate (Compound No. 2709)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.83 (1H, s), 7.11-7.05 (2H, m), 6.86-6.82 (1H, m), 3.43 (2H, d, J = 6.2Hz), 2.73 (2H, d, J = 7.0Hz), 2.12 (3H, s), 2.04-1.93 (4H, m), 1.77-1.69 (1H, m), 0.74-0.56 (4H, m).
Physical properties: candy-like.

(Example 492)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl hydratropate (Compound No. 2715)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.42-7.20 (5H, m), 7.32 (1H, s), 7.15-7.02 (2H, m), 6.86-6.75 (1H, m), 4.20-4.00 ( 1H, m), 2.04 (3H, s), 1.66 (3H, d, J = 7.0 Hz), 1.70-1.50 (1H, m), 0.70-0.42 (4H, m).
Physical property: Oily substance.

(Example 493)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl (4-methoxyphenyl) acetate (Compound No. 2721)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.37 (1H, s), 7.27 (2H, d, J = 8.2 Hz), 7.13-7.05 (2H, m), 6.89-6.80 (3H, m), 3.91 (2H, s), 3.76 (3H, s), 2.07 (3H, s), 1.73-1.60 (1H, m), 0.75-0.50 (4H, m).
Physical properties: Pasty.

(Example 494)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl ethyl succinate (Compound No. 2727)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.08-6.92 (2H, m), 6.85-6.68 (1H, m), 6.55 (1H, s), 4.14 (2H, br.q, J = 7.1Hz) , 3.00 (1H, t, J = 7.0Hz), 2.76 (1H, t, J = 7.0Hz), 2.61 (2H, br.s), 1.98 (3H, s), 1.78-1.60 (1H, m), 1.25 (3H, t, J = 7.1Hz), 0.75-0.40 (4H, m).
Physical properties: amorphous.

(Example 495)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methyl-1-piperidinecarboxylate (Compound No. 3654)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 7.56 (1H, s), 7.14-7.04 (2H, m), 6.90-6.80 (1H, m), 4.35-4.10 (2H, m), 3.15-2.80 ( 2H, m), 2.14 (3H, s), 1.85-1.50 (4H, m), 1.35-1.06 (2H, m), 0.96 (3H, d, J = 6.2Hz), 0.80-0.50 (4H, m) .
Physical properties: candy-like.

(Example 496)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-bromo-1-piperidinecarboxylate (Compound No. 3648)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 7.55 (1H, s), 7.15-7.04 (2H, m), 6.90-6.80 (1H, m), 4.54-4.38 (1H, m), 4.00-3.53 ( 4H, m), 2.30-1.90 (7H, m), 1.85-1.67 (1H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 497)
Bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] succinate (Compound No. 2733)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.32 (2H, s), 7.14-7.03 (4H, m), 6.88-6.81 (2H, m), 3.17 (4H, s), 2.10 (6H, s) , 1.80-1.65 (2H, m), 0.78-0.53 (8H, m).
Physical properties: candy-like.

(Example 498)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl methoxyacetate (Compound No. 2752)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.43 (1H, s), 7.15-7.04 (2H, m), 6.90-6.82 (1H, m), 4.41 (2H, s), 3.55 (3H, s) , 2.12 (3H, s), 1.82-1.67 (1H, m), 0.80-0.67 (2H, m), 0.64-0.55 (2H, m).
Physical properties: Pasty.

(Example 499)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl phenoxyacetate (Compound No. 2758)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.42 (1H, s), 7.29-7.25 (2H, m), 7.23-6.96 (5H, m), 6.89-6.83 (1H, m), 5.00 (2H, s), 2.08 (3H, s), 1.73-1.64 (1H, m), 0.71-0.54 (4H, m).
Physical properties: candy-like.

(Example 500)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-phenoxypropanoate (Compound No. 2764)
¹ H-NMR (200 MHz, CDCl ₃ ) δ ppm: 7.33 (1H, s), 7.25-7.19 (2H, m), 7.17-7.04 (2H, m), 7.00-6.91 (3H, m), 6.86-6.82 ( 1H, m), 5.09 (1H, q, J = 6.6Hz), 2.05 (3H, s), 1.84 (3H, d, J = 6.6Hz), 1.64-1.58 (1H, m), 0.68-0.52 (4H , m).
Physical properties: candy-like.

(Example 501)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl methoxy (phenyl) acetate (Compound No. 2770)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.56-7.51 (2H, m), 7.40-7.30 (4H, m), 7.12-7.02 (2H, m), 6.83-6.78 (1H, m), 5.10 ( 1H, s), 3.52 (3H, s), 2.01 (3H, s), 1.67-1.50 (1H, m), 0.70-0.43 (4H, m).
Physical properties: Pasty.

(Example 502)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3- (methylsulfanyl) propanoate (Compound No. 2776)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.42 (1H, s), 7.10-7.00 (2H, m), 6.90-6.77 (1H, m), 3.07-2.83 (4H, m), 2.17 (3H, s), 2.12 (3H, s), 1.85-1.65 (1H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 503)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl oxo (2-thienyl) acetate (Compound No. 2782)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.07 (1H, dd, J = 1.5Hz, 4.1Hz), 7.77 (1H, dd, J = 1.5Hz, 4.1Hz), 7.58 (1H, s), 7.22 (1H, t, J = 4.0Hz), 7.10-7.02 (2H, m), 6.90-6.77 (1H, m), 2.15 (3H, s), 1.90-1.70 (1H, m), 0.85-0.50 (4H , m).
Physical properties: candy-like.

(Example 504)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-fluorobenzoate (Compound No. 2788)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.17-8.09 (1H, m), 7.73-7.62 (1H, m), 7.57 (1H, s), 7.36-7.20 (2H, m), 7.09-7.07 ( 2H, m), 6.87-6.82 (1H, m), 2.16 (3H, s), 1.85-1.72 (1H, m), 0.76-0.56 (4H, m).
Physical properties: amorphous.

(Example 505)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-bromobenzoate (Compound No. 2805)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.20-8.05 (1H, m), 7.85-7.70 (1H, m), 7.59 (1H, s), 7.55-7.38 (2H, m), 7.15-7.00 ( 2H, m), 6.90-6.80 (1H, m), 2.17 (3H, s), 1.88-1.70 (1H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 506)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-iodobenzoate (Compound No. 2814)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.20-8.05 (2H, m), 7.60-7.44 (2H, m), 7.35-7.20 (1H, m), 7.13-7.00 (2H, m), 6.90- 6.78 (1H, m), 2.17 (3H, s), 1.90-1.72 (1H, m), 0.85-0.50 (4H, m).
Physical properties: candy-like.

(Example 507)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2- (trifluoromethyl) benzoate (Compound No. 2820)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.13-8.09 (1H, m), 7.91-7.86 (1H, m), 7.76-7.72 (2H, m), 7.55 (1H, s), 7.11-7.06 ( 2H, m), 6.88-6.83 (1H, m), 2.16 (3H, s), 1.86-1.71 (1H, m), 0.75-0.56 (4H, m).
Physical properties: candy-like.

(Example 508)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-benzylbenzoate (Compound No. 2826)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.22-8.18 (1H, d, J = 7.2 Hz), 7.62-7.54 (1H, t, J = 7.6 Hz), 7.44-7.06 (10H, m), 6.85 -6.81 (1H, m), 4.46 (1H, s), 2.11 (3H, s), 1.80-1.67 (1H, m), 0.75-0.64 (2H, m), 0.60-0.52 (2H, m).
Physical properties: Pasty.

(Example 509)
Bis [6-chloro-3- (2-methylphenoxy) -4-pyridazinyl] phthalate (Compound No. 2827)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.06 (2H, dd, J = 6.0, 3.4 Hz), 7.57 (2H, s), 7.25-7.15 (8H, m), 7.05-7.01 (2H, m) , 2.14 (6H, s).
Melting point (° C): 157-158.

(Example 510)
1- [6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] 2-methyl 1,2-piperidinedicarboxylate (Compound No. 3642)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.60 (0.5H, s), 7.59 (0.5H, s), 7.14-7.03 (2H, m), 6.92-6.80 (1H, m), 5.10-4.90 ( 1H, m), 4.32-4.06 (1H, m), 3.73 (1.5H, s), 3.71 (1.5H, s), 3.40-3.05 (1H, m), 2.43-2.20 (1H, m), 2.15 ( 1.5H, s), 2.13 (1.5H, s), 2.00-1.20 (6H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 511)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-nitrobenzoate (Compound No. 2850)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.15-8.05 (1H, m), 7.95-7.72 (3H, m), 7.65 (1H, s), 7.14-7.05 (2H, m), 6.90-6.80 ( 1H, m), 2.15 (3H, s), 1.85-1.70 (1H, m), 0.78-0.65 (2H, m), 0.65-0.50 (2H, m).
Physical property: Oily substance.

(Example 512)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-phenoxybenzoate (Compound No. 2856)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.35 (1H, dd, J = 8.2, 1.8Hz), 8.15 (1H, dd, J = 8.0, 1.8Hz), 7.74 (1H, dt, J = 7.0, 1.4Hz), 7.61-7.21 (5H, m), 7.15-6.98 (4H, m), 6.84-6.79 (1H, m), 2.09 (3H, s), 1.80-1.68 (1H, m), 0.70-0.61 (2H, m), 0.59-0.51 (2H, m).
Physical properties: Pasty.

(Example 513)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-chlorobenzoate (Compound No. 2868)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.18 (1H, d, J = 1.8Hz), 8.10 (1H, d, J = 8.1Hz), 7.68 (1H, br.d, J = 9.2Hz), 7.57 (1H, s), 7.50 (1H, t, J = 8.1Hz), 7.08 (1H, d, J = 5.8Hz), 7.07 (1H, d, J = 3.7Hz), 6.85 (1H, dd, J = 5.8, 3.7Hz), 2.15 (3H, s), 1.85-1.66 (1H, m), 0.80-0.50 (4H, m).
Physical properties: amorphous.

(Example 514)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-fluorobenzoate (Compound No. 2862)
¹ H-NMR (200 MHz, CDCl ₃ ) δ ppm: 8.02 (1H, dd, J = 6.2, 1.5 Hz), 7.89 (1H, br.d, J = 8.8 Hz), 7.60-7.34 (2H, m), 7.59 (1H, s), 7.13-7.04 (2H, m), 6.90-6.78 (1H, m), 2.15 (3H, s), 1.83-1.68 (1H, m), 0.80-0.50 (4H, m).
Physical property: Oily substance.

(Example 515)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-bromobenzoate (Compound No. 2874)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.33 (1H, s), 8.14 (1H, d, J = 8.0Hz), 7.82 (1H, d, J = 8.0Hz), 7.56 (1H, s), 7.43 (1H, t, J = 8.0Hz), 7.13-7.03 (2H, m), 6.90-6.80 (1H, m), 2.15 (3H, s), 1.85-1.68 (1H, m), 0.80-0.50 ( 4H, m).
Physical properties: candy-like.

(Example 516)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-iodobenzoate (Compound No. 2880)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.54 (1H, d, J = 1.8 Hz), 8.20-8.15 (1H, m), 8.03 (1H, d, J = 8.1 Hz), 7.56 (1H, s ), 7.34-7.26 (1H, m), 7.13-7.05 (2H, m), 6.89-6.82 (1H, m), 2.15 (3H, s), 1.83-1.71 (1H, m), 0.80-0.68 (2H , m), 0.65-0.52 (2H, m).
Physical properties: amorphous.

(Example 517)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3- (trifluoromethyl) benzoate (Compound No. 2900)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.47 (1H, s), 8.41 (1H, d, J = 7.7Hz), 7.96 (1H, d, J = 7.3Hz), 7.75-7.67 (1H, m ), 7.58 (1H, s), 7.12-7.06 (2H, m), 6.89-6.82 (1H, m), 2.16 (3H, s), 1.84-1.71 (1H, m), 0.80-0.53 (4H, m ).
Physical properties: candy-like.

(Example 518)
Bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] isophthalate (Compound No. 2906)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 9.02 (1H, s), 8.53 (2H, d, J = 8.2Hz), 7.78 (1H, t, J = 7.8Hz), 7.58 (2H, s), 7.08-7.06 (4H, m), 6.86-6.82 (2H, m), 2.14 (6H, s), 1.83-1.68 (2H, m), 0.78-0.69 (4H, m), 0.60-0.53 (4H, m ).
Physical properties: Pasty.

(Example 519)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-nitrobenzoate (Compound No. 2918)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 9.05-9.04 (1H, m), 8.59-8.52 (2H, m), 7.79 (1H, t, J = 7.7Hz), 7.59 (1H, s), 7.13 -7.07 (2H, m), 6.89-6.82 (1H, m), 2.15 (3H, s), 1.83-1.72 (1H, m), 0.80-0.54 (4H, m).
Physical properties: candy-like.

(Example 520)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-phenoxybenzoate (Compound No. 2924)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.95-7.90 (1H, m), 7.80-7.78 (1H, m), 7.57 (1H, s), 7.50 (1H, t, J = 8.0Hz), 7.40 -7.30 (3H, m), 7.17-7.10 (1H, m), 7.09-7.03 (3H, m), 7.07 (1H, s), 6.87-6.82 (1H, m), 2.13 (3H, s), 1.81 -1.67 (1H, m), 0.78-0.66 (2H, m). 0.59-0.54 (2H, m).
Physical properties: Pasty.

(Example 521)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-fluorobenzoate (Compound No. 2930)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.30-8.18 (2H. M), 7.59 (1H, s), 7.30-7.15 (2H, m), 7.15-7.02 (2H, m), 6.90-6.78 ( 1H, m), 2.15 (3H, s), 1.85-1.70 (1H, m), 0.80-0.50 (4H, m). 398 (M +), 370, 335, 275.
Physical properties: candy-like.

(Example 522)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-ethylbenzoate (Compound No. 2961)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.13 (2H, d, J = 8.5 Hz), 7.60 (1H, s), 7.36 (2H, d, J = 8.5 Hz), 7.12-7.04 (2H, m ), 6.88-6.81 (1H, m), 2.75 (2H, q, J = 7.6 Hz), 2.04 (3H, s), 1.85-1.71 (1H, m), 1.28 (3H, t, J = 7.6 Hz) , 0.79-0.65 (2H, m), 0.61-0.52 (2H, m).
Physical properties: Pasty.

(Example 523)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-propylbenzoate (Compound No. 2970)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.12 (2H, d, J = 8.4 Hz), 7.59 (1H, s), 7.34 (2H, d, J = 8.4 Hz), 7.12-7.05 (2H, m ), 6.88-6.81 (1H, m), 2.69 (2H, t, J = 7.3 Hz), 2.16 (3H, s), 1.85-1.60 (3H, m), 0.96 (3H, t, J = 7.3 Hz) , 0.80-0.68 (2H, m), 0.63-0.52 (2H, m).
Physical properties: Pasty.

(Example 524)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-isopropylbenzoate (Compound No. 2976)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.14 (2H, d, J = 8.4 Hz), 7.59 (1H, s), 7.40 (2H, d, J = 8.4 Hz), 7.12-7.05 (2H, m ), 6.90-6.82 (1H, m), 3.01 (1H, septet, J = 7.0 Hz), 2.15 (3H, s), 1.85-1.70 (1H, m), 1.29 (6H, d, J = 7.0 Hz) , 0.80-0.65 (2H, m), 0.63-0.52 (2H, m).
Physical properties: Pasty.

(Example 525)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-butylbenzoate (Compound No. 2982)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.12 (2H, d, J = 8.1 Hz), 7.59 (1H, s), 7.35 (2H, d, J = 8.1 Hz), 7.12-7.03 (2H, m ), 6.89-6.81 (1H, m), 2.72 (2H, t, J = 7.3 Hz), 2.16 (3H, s), 1.85-1.57 (3H, m), 1.47-1.22 (2H, m), 0.94 ( 3H, t, J = 7.3 Hz), 0.80-0.68 (2H, m), 0.65-0.55 (2H, m).
Physical properties: Pasty.

(Example 526)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (trifluoromethyl) benzoate (Compound No. 2988)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.34 (2H, d, J = 8.8Hz), 7.83 (2H, d, J = 8.8Hz), 7.60 (1H, s), 7.14-7.07 (2H, m ), 6.89-6.83 (1H, m), 2.15 (3H, s), 1.83-1.72 (1H, m), 0.79-0.71 (2H, m), 0.63-0.54 (2H, m).
Melting point (° C): 127-128.

(Example 527)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-cyanobenzoate (Compound No. 2994)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.33 (2H, d, J = 8.8Hz), 7.86 (2H, d, J = 8.8Hz), 7.60 (1H, s), 7.14-7.07 (2H, m ), 6.89-6.83 (1H, m), 2.14 (3H, s), 1.82-1.68 (1H, m), 0.79-0.53 (4H, m).
Physical properties: candy-like.

(Example 528)
Bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] terephthalate (Compound No. 3001)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.39 (4H, s), 7.62 (2H, s), 7.10-7.07 (4H, m), 6.87-6.83 (2H, m), 2.15 (6H, s) , 1.81-1.68 (2H, m), 0.78-0.70 (4H, m), 0.61-0.53 (4H, m).
Melting point (° C): 247-249.

(Example 529)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl [1,1'-biphenyl] -4-carboxylate (Compound No. 3016)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.31-8.23 (2H, m), 7.79-7.74 (2H, m), 7.67-7.62 (3H, m), 7.54-7.42 (3H, m), 7.09- 7.06 (2H, m), 6.87-6.82 (1H, m), 2.17 (3H, s), 1.84-1.75 (1H, m), 0.77-0.56 (4H, m).
Melting point (° C): 135-137.

(Example 530)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (trifluoromethoxy) benzoate (Compound No. 3022)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.28 (2H, d, J = 9.2Hz), 7.59 (1H, s), 7.38 (2H, d, J = 9.2Hz), 7.14-7.04 (2H, m ), 6.89-6.82 (1H, m), 2.15 (3H, s), 1.83-1.69 (1H, m), 0.78-0.65 (2H, m), 0.62-0.53 (2H, m).
Physical properties: Pasty.

(Example 531)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (benzyloxy) benzoate (Compound No. 3028)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.16 (2H, d, J = 9.2 Hz), 7.60 (1H, s), 7.50-7.30 (5H, m), 7.10-7.03 (4H, m), 6.89 -6.82 (1H, m), 5.17 (2H, s), 2.15 (3H, s), 1.85-1.72 (1H, m), 0.80-0.68 (2H, m), 0.65-0.53 (2H, m).
Physical properties: Pasty.

(Example 532)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,3-difluorobenzoate (Compound No. 3034)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.93-7.85 (1H, m), 7.57 (1H, s), 7.57-7.44 (1H, m), 7.32-7.21 (1H, m), 7.10-7.05 ( 2H, m), 6.87-6.82 (1H, m), 2.15 (3H, s), 1.81-1.73 (1H, m), 0.76-0.72 (2H, m), 0.60-0.56 (2H, m).
Physical properties: Pasty.

(Example 533)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-fluoro-3- (trifluoromethyl) benzoate (Compound No. 3040)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.36-8.28 (1H, m), 7.99-7.92 (1H, m), 7.56 (1H, s), 7.49-7.41 (1H, m), 7.13-7.05 ( 2H, m), 6.89-6.83 (1H, m), 2.15 (3H, s), 1.84-1.72 (1H, m), 0.80-0.54 (4H, m).
Physical properties: amorphous.

(Example 534)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,3-dimethylbenzoate (Compound No. 3046)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.00-7.96 (1H, m), 7.54 (1H, s), 7.45-7.41 (1H, m), 7.27-7.20 (1H, m), 7.14-7.05 ( 2H, m), 6.89-6.82 (1H, m), 2.57 (3H, s), 2.37 (3H, s), 2.16 (3H, s), 1.86-1.72 (1H, m), 0.79-0.69 (2H, m), 0.61-0.53 (2H, m).
Physical properties: Pasty.

(Example 535)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-chloro-2-methylbenzoate (Compound No. 3052)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.04 (1H, d, J = 8.1 Hz), 7.65 (1H, d, J = 8.1 Hz), 7.54 (1H, s), 7.33-7.25 (1H, m ), 7.13-7.06 (2H, m), 6.89-6.83 (1H, m), 2.73 (3H, s), 2.15 (3H, s), 1.83-1.71 (1H, m), 0.79-0.68 (2H, m ), 0.65-0.53 (2H, m).
Physical properties: amorphous.

(Example 536)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,4-difluorobenzoate (Compound No. 3058)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.23-8.12 (1H, m), 7.56 (1H, s), 7.10-6.94 (4H, m), 6.87-6.82 (1H, m), 2.15 (3H, s), 1.81-1.73 (1H, m), 0.75-0.56 (4H, m).
Physical properties: amorphous.

(Example 537)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-chloro-2-fluorobenzoate (Compound No. 3064)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.07 (1H, dd, J = 7.4Hz, 8.5Hz), 7.55 (1H, s), 7.38-7.22 (2H, m), 7.14-7.03 (2H, m ), 6.90-6.78 (1H, m), 2.15 (3H, s), 1.85-1.68 (1H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 538)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-fluoro-4- (trifluoromethyl) benzoate (Compound No. 3070)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.30-8.22 (1H, m), 7.61-7.52 (2H, m), 7.57 (1H, s), 7.14-7.05 (2H, m), 6.87-6.82 ( 1H, m), 2.15 (3H, m), 1.83-1.69 (1H, m), 0.78-0.70 (2H, m), 0.65-0.55 (2H, m).
Physical properties: Pasty.

(Example 539)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-chloro-4-fluorobenzoate (Compound No. 3076)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.25-8.18 (1H, m), 7.57 (1H, s), 7.34-7.29 (1H, m), 7.19-7.05 (3H, m), 6.89-6.82 ( 1H, m), 2.15 (3H, m), 1.84-1.70 (1H, m), 0.79-0.68 (2H, m), 0.64-0.53 (2H, m).
Physical properties: Pasty.

(Example 540)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-bromo-2-chlorobenzoate (Compound No. 3082)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.01 (1H, d, J = 8.4Hz), 7.76 (1H, d, J = 1.8Hz), 7.60-7.55 (2H, m), 7.10-7.07 (2H m), 6.87-6.83 (1H, m), 2.15 (3H, s), 1.83-1.71 (1H, m), 0.77-0.71 (2H, m), 0.62-0.56 (2H, m).
Physical properties: Pasty.

(Example 541)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-bromo-2-methylbenzoate (Compound No. 3088)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.05 (1H, d, J = 8.4Hz), 7.56-7.48 (3H, m), 7.09-7.07 (2H, m), 6.86-6.82 (1H, m) , 2.14 (3H, s), 2.04 (3H, s), 1.85-1.72 (1H, m), 0.79-0.71 (2H, m), 0.64-0.55 (2H, m).
Physical properties: Pasty.

(Example 542)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,4-dimethylbenzoate (Compound No. 3094)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.11 (1H, d, J = 8.9 Hz), 7.57 (1H, s), 7.16-7.13 (2H, m), 7.09-7.05 (2H, m), 6.88 -6.81 (1H, m), 2.65 (3H, s), 2.41 (3H, s), 2.15 (3H, s), 1.85-1.71 (1H, m), 0.80-0.68 (2H, m), 0.67-0.55 (2H, m).
Physical properties: Pasty.

(Example 543)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,5-dichlorobenzoate (Compound No. 3100)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.10 (1H, d, J = 2.2Hz), 7.60-7.45 (3H, m), 7.15-7.04 (2H, m), 6.90-6.78 (1H, m) , 2.15 (3H, s), 1.85-1.70 (1H, m), 0.80-0.50 (4H, m).
Melting point (° C): 128-130.

(Example 544)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 5-bromo-2-chlorobenzoate (Compound No. 3106)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.20 (1H, d, J = 2.2 Hz), 7.68 (1H, dd, J = 2.2 Hz, 8.4 Hz), 7.54 (1H, s), 7.43 (1H, d, J = 8.4Hz), 7.14-7.03 (2H, m), 6.92-6.80 (1H, m), 2.15 (3H, s), 1.87-1.70 (1H, m), 0.85-0.50 (4H, m) .
Physical properties: candy-like.

(Example 545)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-bromo-5-methoxybenzoate (Compound No. 3112)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.67-7.57 (3H, m), 7.12-7.00 (3H, m), 6.87-6.82 (1H, m), 3.85 (3H, s), 2.16 (3H, s), 1.87-1.75 (1H, m), 0.80-0.68 (2H, m), 0.65-0.55 (2H, m).
Physical properties: Pasty.

(Example 546)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,5-dimethylbenzoate (Compound No. 3129)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.99 (1H, s), 7.54 (1H, s), 7.37-7.30 (1H, m), 7.25-7.21 (1H, m), 7.13-7.05 (2H, m), 6.89-6.82 (1H, m), 2.63 (3H, s), 2.40 (3H, s), 2.16 (3H, s), 1.86-1.72 (1H, m), 0.80-0.70 (2H, m) , 0.62-0.54 (2H, m).
Physical property: Oily substance.

(Example 547)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,6-difluorobenzoate (Compound No. 3138)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.68-7.50 (2H, m), 7.15-7.00 (4H, m), 6.90-6.77 (1H, m), 2.15 (3H, s), 1.90-1.70 ( 1H, m), 0.85-0.50 (4H, m).
Physical properties: candy-like.

(Example 548)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-chloro-6-fluorobenzoate (Compound No. 3144)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.57-7.00 (5H, m), 6.90-6.78 (1H, m), 2.16 (3H, s), 1.90-1.75 (1H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 549)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,6-dichlorobenzoate (Compound No. 3150)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.58 (1H, s), 7.43-7.41 (3H, m), 7.11-7.08 (2H, m), 6.88-6.83 (1H, m), 2.17 (3H, s), 1.85-1.77 (1H, m), 0.74-0.56 (4H, m).
Physical properties: amorphous.

(Example 550)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,6-dimethylbenzoate (Compound No. 3156)
¹ H-NMR (200 MHz, CDCl ₃ ) δ ppm: 7.48 (1H, s), 7.32 (1H, dd, J = 8.4, 7.0 Hz), 7.15-7.07 (3H, m), 6.87-6.83 (1H, m) , 2.53 (6H, s), 2.16 (3H, s), 1.84-1.76 (1H, m), 0.75-0.69 (2H, m), 0.62-0.57 (2H, m).
Physical properties: Pasty.

(Example 551)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,6-dimethoxybenzoate (Compound No. 3162)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.59 (1H, s), 7.39 (1H, t, J = 8.8Hz), 7.09-7.07 (2H, m), 6.85-6.81 (1H, m), 6.62 (2H, d, J = 6.6Hz), 3.84 (6H, s), 2.17 (3H, s), 1.96-1.81 (1H, m), 0.74-0.55 (4H, m).
Melting point (° C): 127-128.

(Example 552)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,4-difluorobenzoate (Compound No. 3168)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.10-7.99 (2H, m), 7.58 (1H, s), 7.43-7.25 (1H, m), 7.15-7.02 (2H, m), 6.90-6.80 ( 1H, m), 2.15 (3H, s), 1.83-1.67 (1H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 553)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-fluoro-4-methylbenzoate (Compound No. 3185)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.90 (1H, d, J = 8.1 Hz), 7.83 (1H, d, J = 9.9 Hz), 7.59 (1H, s), 7.37 (1H, dd, J = 7.3Hz, 7.7Hz), 7.15-7.00 (2H, m), 6.90-6.78 (1H, m), 2.39 (3H, d, 1.5Hz), 2.15 (3H, s), 1.85-1.67 (1H, m ), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 554)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,4-dichlorobenzoate (Compound No. 3194)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.29 (1H, d, J = 1.8 Hz), 8.03 (1H, dd, J = 8.4, 2.2 Hz), 7.65 (1H, d, J = 8.4 Hz), 7.57 (1H, s), 7.15-7.02 (2H, m), 6.90-6.80 (1H, m), 2.15 (3H, s), 1.82-1.68 (1H, m), 0.78-0.47 (4H, m).
Physical properties: amorphous.

(Example 555)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-chloro-3-nitrobenzoate (Compound No. 3200)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.69 (1H, d, J = 1.8Hz), 8.33 (1H, dd, J = 8.4, 1.8Hz), 7.78 (1H, d, J = 8.4Hz), 7.57 (1H, s), 7.10-7.05 (2H, m), 6.87-6.82 (1H, m), 2.14 (3H, s), 1.77-1.69 (1H, m), 0.75-0.56 (4H, m).
Physical properties: amorphous.

(Example 556)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,5-difluorobenzoate (Compound No. 3217)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.80-7.65 (2H, m), 7.58 (1H, s), 7.32-7.00 (3H, m), 6.90-6.80 (1H, m), 2.15 (3H, s), 1.85-1.65 (1H, m), 0.80-0.50 (4H, m).
Physical properties: amorphous.

(Example 557)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,5-dichlorobenzoate (Compound No. 3226)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.07 (2H, d, J = 2.0 Hz), 7.69 (1H, t, J = 2.0 Hz), 7.55 (1H, s), 7.13-7.00 (2H, m ), 6.89-6.82 (1H, m), 2.15 (3H, s), 1.83-1.60 (1H, m), 0.80-0.70 (2H, m), 0.63-0.55 (2H, m).
Melting point (° C): 168-174.

(Example 558)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,5-dimethylbenzoate (Compound No. 3243)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.82 (2H, s), 7.56 (1H, s), 7.32 (1H, s,), 7.13-7.04 (2H, m), 6.89-6.82 (1H, m ), 2.41 (6H, s), 2.16 (3H, s), 1.85-1.72 (1H, m), 0.80-0.70 (2H, m), 0.63-0.53 (2H, m).
Melting point (° C): 117-119.

(Example 559)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,5-dimethoxybenzoate (Compound No. 3252)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.34 (1H, s), 7.33 (1H, s), 7.08-7.06 (2H, m), 6.87-6.82 (1H, m) , 6.78-6.75 (1H, m), 3.86 (6H, s), 2.16 (3H, s), 1.86-1.72 (1H, m), 0.80-0.72 (2H, m), 0.63-0.54 (2H, m) .
Physical properties: Pasty.

(Example 560)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,4,6-trichlorobenzoate (Compound No. 3258)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 7.46 (2H, s), 7.15-7.05 (2H, m), 6.90-6.82 (1H, m), 2.16 (3H, s) , 1.86-1.72 (1H, m), 0.78-0.67 (2H, m), 0.65-0.55 (2H, m).
Physical properties: Pasty.

(Example 561)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,4,5-trimethoxybenzoate (Compound No. 3264)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.45 (2H, s), 7.14-7.04 (2H, m), 6.89-6.83 (1H, m), 3.96 (3H, s) , 3.94 (6H, s), 2.16 (3H, s), 1.85-1.72 (1H, m), 0.80-0.67 (2H, m), 0.63-0.54 (2H, m).
Physical properties: amorphous.

(Example 562)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-naphthoate (Compound No. 3270)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 9.02 (1H, d, J = 8.4 Hz), 8.55 (1H, d, J = 7.3 Hz), 8.17 (1H, d, J = 8.0 Hz), 7.95 ( 1H, d, J = 8.0Hz), 7.75-7.54 (4H, m), 7.13-7.00 (2H, m), 6.90-6.80 (1H, m), 2.18 (3H, s), 1.93-1.75 (1H, m), 0.83-0.52 (4H, m).
Physical properties: amorphous.

(Example 563)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-naphthoate (Compound No. 3276)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.81 (1H, s), 8.18 (1H, dd, J = 1.5Hz, 8.5Hz), 8.05-7.87 (3H, m), 7.70-7.52 (3H, m ), 7.10-7.00 (2H, m), 6.90-6.77 (1H, m), 2.18 (3H, s), 1.90-1.73 (1H, m), 0.83-0.53 (4H, m).
Physical properties: amorphous.

(Example 564)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-methyl-1H-pyrrole-2-carboxylate (Compound No. 3282)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.25 (1H, s), 7.08-7.06 (2H, m), 6.96 (1H, s), 6.86-6.81 (1H, m) , 6.24-6.21 (1H, m), 3.97 (3H, s), 2.15 (3H, s), 1.87-1.72 (1H, m), 0.80-0.70 (2H, m), 0.63-0.52 (2H, m) .
Melting point (° C): 143-144.

(Example 565)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 5-bromo-2-furoate (Compound No. 3288)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.53 (1H, s), 7.43 (1H, d, J = 3.7Hz), 7.15-7.03 (2H, m), 6.90-6.78 (1H, m), 6.59 (1H, d, J = 3.7Hz), 2.15 (3H, s), 1.83-1.70 (1H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 566)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-furoate (Compound No. 3294)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.30 (1H, t, J = 0.7 Hz), 7.57-7.53 (1H, m), 7.55 (1H, s), 7.13-7.04 (2H, m), 6.92 -6.81 (2H, m), 2.15 (3H, s), 1.83-1.69 (1H, s), 0.80-0.53 (4H, m).
Physical properties: Pasty.

(Example 567)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 5-tert-butyl-2-methyl-3-furoate (Compound No. 3300)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.09-7.07 (2H, m), 6.87-6.83 (1H, m), 6.33 (1H, s), 2.64 (3H, s) , 2.15 (3H, s), 1.78-1.73 (1H, m), 1.29 (9H, s), 0.75-0.57 (4H, m).
Physical properties: candy-like.

(Example 568)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 5-methyl-2- (trifluoromethyl) -3-furoate (Compound No. 3306)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.53 (1H, s), 7.13-7.04 (2H, m), 6.89-6.82 (1H, m), 6.64 (1H, s), 2.42 (3H, s) , 2.13 (3H, s), 1.81-1.67 (1H, m), 0.78-0.68 (2H, m), 0.65-0.53 (2H, m).
Physical properties: Pasty.

(Example 569)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 5- (4-chlorophenyl) -2- (trifluoromethyl) -3-furoate (Compound No. 3312)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.70-7.66 (2H, m), 7.56 (1H, s), 7.47-7.42 (2H, m), 7.19 (1H, s), 7.14-7.05 (2H, m), 6.90-6.82 (1H, m), 2.14 (3H, s), 1.83-1.69 (1H, m), 0.80-0.68 (2H, m), 0.65-0.53 (2H, m).
Physical properties: Pasty.

(Example 570)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-chloro-2-thiophenecarboxylate (Compound No. 3318)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.68 (1H, d, J = 5.5Hz), 7.58 (1H, s), 7.14 (1H, d, J = 5.5Hz), 7.11-7.03 (2H, m ), 6.90-6.80 (1H, m), 2.16 (3H, s), 1.85-1.70 (1H, m), 0.85-0.50 (4H, m).
Physical properties: candy-like.

(Example 571)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-methyl-2-thiophenecarboxylate (Compound No. 3324)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.65-7.55 (2H, m), 7.13-6.95 (3H, m), 6.90-6.80 (1H, m), 2.63 (3H, s), 2.16 (3H, s), 1.90-1.70 (1H, m), 0.85-0.50 (4H, m).
Physical properties: amorphous.

(Example 572)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-ethoxy-2-thiophenecarboxylate (Compound No. 3330)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.62 (1H, s), 7.59 (1H, d, J = 5.5Hz), 7.08-7.06 (2H, m), 6.90 (1H, d, J = 5.5Hz ), 6.86-6.81 (1H, m), 4.26 (2H, q, J = 7.0Hz), 2.17 (3H, s), 1.86-1.75 (1H, m), 1.46 (3H, t, J = 7.0Hz) , 0.75-0.55 (4H, m).
Physical properties: candy-like.

(Example 573)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 5-chloro-2-thiophenecarboxylate (Compound No. 3336)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.86 (1H, d, J = 4.0 Hz), 7.57 (1H, s), 7.14-7.03 (3H, m), 6.90-6.83 (1H, m), 2.15 (3H, m), 1.83-1.68 (1H, m), 0.80-0.68 (2H, m), 0.65-0.53 (2H, m).
Physical properties: Pasty.

(Example 574)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 5-bromo-2-thiophenecarboxylate (Compound No. 3342)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.80 (1H, d, J = 4.0Hz), 7.57 (1H, s), 7.19 (1H, d, J = 4.0Hz), 7.10-7.00 (2H, m ), 6.90-6.80 (1H, m), 2.15 (3H, s), 1.85-1.65 (1H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 575)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 5-methyl-2-thiophenecarboxylate (Compound No. 3348)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.87 (1H, d, J = 3.7Hz), 7.57 (1H, s), 7.12-7.00 (2H, m), 6.93-6.87 (2H, m), 2.58 (3H, s), 2.15 (3H, s), 1.85-1.70 (1H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 576)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 5-acetyl-2-thiophenecarboxylate (Compound No. 3354)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.02 (1H, d, J = 4.0Hz), 7.72 (1H, d, J = 4.0Hz), 7.58 (1H, s), 7.10-7.07 (2H, m ), 6.87-6.83 (1H, m), 2.63 (3H, s), 2.15 (3H, s), 1.79-1.71 (1H, m), 0.75-0.56 (4H, m).
Physical properties: amorphous.

(Example 577)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 5-nitro-3-thiophenecarboxylate (Compound No. 3360)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.52 (1H, d, J = 1.8Hz), 8.43 (1H, d, J = 1.8Hz), 7.56 (1H, s), 7.13-7.05 (2H, m ), 6.90-6.80 (1H, m), 2.14 (3H, s), 1.85-1.65 (1H, m), 0.85-0.50 (4H, m).
Physical properties: amorphous.

(Example 578)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4,5-dibromo-2-thiophenecarboxylate (Compound No. 3366)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.84 (1H, s), 7.56 (1H, s), 7.14-7.05 (2H, m), 6.90-6.83 (1H, m), 2.14 (3H, s) , 1.83-1.69 (1H, m), 0.79-0.68 (2H, m), 0.65-0.55 (2H, m).
Physical properties: amorphous.

(Example 579)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-thiophenecarboxylate (Compound No. 3372)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.42-8.40 (1H, m), 7.70-7.66 (1H, m), 7.58 (1H, s), 7.47-7.41 (1H, m), 7.13-7.05 ( 2H, m), 6.88-6.82 (1H, m), 2.15 (3H, s), 1.84-1.70 (1H, m), 0.80-0.68 (2H, m), 0.64-0.55 (2H, m).
Physical properties: Pasty.

(Example 580)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methoxy-3-thiophenecarboxylate (Compound No. 3378)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.33 (1H, d, J = 3.5 Hz), 7.59 (1H, s), 7.09-7.06 (2H, m), 6.87-6.82 (1H, m), 6.38 (1H, d, J = 3.5Hz), 3.93 (3H, s), 2.16 (3H, s), 1.82-1.74 (1H, m), 0.75-0.56 (4H, m).
Melting point (° C): 146-149.

(Example 581)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-benzyl-3-tert-butyl-1H-pyrazole-5-carboxylate (Compound No. 3384)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.44 (1H, s), 7.21 (5H, s), 7.09-7.06 (2H, m), 6.98 (1H, s), 6.85-6.80 (1H, m) , 5.72 (2H, s), 2.08 (3H, s), 1.76-1.64 (1H, m), 1.36 (9H, s), 0.75-0.64 (2H, m), 0.59-0.50 (2H, m).
Physical properties: Pasty.

(Example 582)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 5-chloro-1,3-dimethyl-1H-pyrazole-4-carboxylate (Compound No. 3390)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.62 (1H, s), 7.09-7.07 (2H, m), 6.87-6.82 (1H, m), 3.86 (3H, s), 2.52 (3H, s) , 2.14 (3H, s), 1.84-1.77 (1H, m), 0.75-0.67 (2H, m), 0.60-0.53 (2H, m).
Physical properties: Pasty.

(Example 583)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3- (2-chlorophenyl) -5-methyl-4-isoxazolecarboxylate (Compound No. 3396)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.53 (1H, s), 7.48-7.42 (2H, m), 7.41-7.30 (2H, m), 7.08-7.06 (2H, m), 6.83-6.78 ( 1H, m), 2.89 (3H, s), 2.02 (3H, s), 1.67-1.53 (1H, m), 0.68-0.50 (4H, m).
Physical properties: amorphous.

(Example 584)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-methyl-1,2,3-thiadiazole-5-carboxylate (Compound No. 3402)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.15-7.05 (2H, m), 6.91-6.84 (1H, m), 3.08 (3H, s), 2.14 (3H, s) , 1.80-1.65 (1H, m), 0.80-0.72 (2H, m), 0.64-0.53 (2H, m).
Physical properties: Pasty.

(Example 585)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 6-methyl-2-pyridinecarboxylate (Compound No. 3408)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.12 (1H, d, J = 7.7Hz), 7.82 (1H, t, J = 7.7Hz), 7.55 (1H, s), 7.46 (1H, d, J = 7.7Hz), 7.12-7.02 (2H, m), 6.85-6.76 (1H, m), 2.71 (3H, s), 2.15 (3H, s), 1.87-1.74 (1H, m), 0.82-0.52 ( 4H, m).
Physical properties: candy-like.

(Example 586)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 5-butyl-2-pyridinecarboxylate (Compound No. 3414)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.67 (1H, br.s), 8.22 (1H, d, J = 7.7Hz), 7.74 (1H, br.d, J = 7.7Hz), 7.53 (1H , s), 7.08-7.05 (2H, m), 6.83-6.78 (1H, m), 2.75 (2H, t, J = 7.7Hz), 2.15 (3H, s), 1.84-1.59 (3H, m), 1.48-1.32 (2H, m), 0.95 (3H, t, J = 7.0Hz), 0.75-0.54 (4H, m).
Physical properties: candy-like.

(Example 587)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl nicotinate (Compound No. 3420)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 9.42-9.41 (1H, m), 8.91 (1H, dd, J = 4.8, 0.8 Hz), 8.50-8.44 (1H, m), 7.60 (1H, s) , 7.56-7.49 (1H, m), 7.13-7.04 (2H, m), 6.88-6.78 (1H, m), 2.15 (3H, s), 1.90-1.70 (1H, m), 0.81-0.70 (2H, m), 0.63-0.55 (2H, m).
Physical properties: Pasty.

(Example 588)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-chloronicotinate (Compound No. 3426)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.66 (1H, dd, J = 4.8, 2.0Hz), 8.45 (1H, dd, J = 7.7, 2.0Hz), 7.59 (1H, s), 7.45 (1H , dd, J = 7.7, 4.8Hz), 7.14-7.06 (2H, m), 6.89-6.83 (1H, m), 2.15 (3H, s), 1.84-1.70 (1H, m), 0.80-0.52 (4H , m).
Physical properties: candy-like.

(Example 589)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-methylnicotinate (Compound No. 3432)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.74 (1H, dd, J = 4.8, 1.5 Hz), 8,46 (1H, dd, J = 7.7, 1.5 Hz), 7.58 (1H, s), 7.34 (1H, dd, J = 7.7, 4.8 Hz), 7.13-7.05 (2H, m), 6.89-6.83 (1H, m), 2.93 (3H, s), 2.15 (3H, s), 1.83-1.67 (1H , m), 0.80-0.68 (2H, m), 0.65-0.55 (2H, m).
Physical properties: Pasty.

(Example 590)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-phenoxynicotinate (Compound No. 3438)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.50 (1H, dd, J = 7.8, 2.2 Hz), 8.39 (1H, dd, J = 4.8, 2.2 Hz), 7.61 (1H, s), 7.46-7.38 (2H, m), 7.29-7.20 (1H, m), 7.19-7.04 (5H, m), 6.86-6.81 (1H, m), 2.14 (3H, s), 1.85-1.72 (1H, m), 1.36 (9H, s), 0.75-0.65 (2H, m), 0.58-0.52 (2H, m).
Physical properties: Pasty.

(Example 591)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2- (methylsulfanyl) nicotinate (Compound No. 3444)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.70 (1H, dd, J = 4.9, 1.8 Hz), 8.47 (1H, dd, J = 7.7, 1.8 Hz), 7.63 (1H, s), 7.16 (1H , dd, J = 7.7, 4.8 Hz), 7.12-7.05 (2H, m), 6.89-6.82 (1H, m), 2.59 (3H, s), 2.16 (3H, s), 1.84-1.71 (1H, m ), 0.80-0.70 (2H, m), 0.65-0.53 (2H, m).
Physical properties: Pasty.

(Example 592)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2- (allylsulfanyl) nicotinate (Compound No. 3450)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.67 (1H, dd, J = 4.8, 1.8Hz), 8.46 (1H, dd, J = 8.2, 1.8Hz), 7.62 (1H, s), 7.16 (1H , dd, J = 8.2, 4.8Hz), 7.09-7.04 (2H, m), 6.89-6.82 (1H, m), 6.10-5.90 (1H, m), 5.33 (1H, dd, J = 16.8, 1.6Hz ), 5.12 (1H, dd, J = 11.0, 1.2Hz), 3.91 (1H, dd, J = 6.8, 1.2Hz), 2.15 (3H, s), 1.85-1.70 (1H, m), 0.78-0.71 ( 2H, m), 0.60-0.51 (2H, m).
Physical properties: Pasty.

(Example 593)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2- (phenylsulfanyl) nicotinate (Compound No. 3456)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.50 (1H, s), 8.47 (1H, d, J = 2.6Hz), 7.65 (1H, s), 7.59-7.51 (2H, m), 7.48-7.41 (3H, m), 7.17-7.05 (3H, m), 6.90-6.82 (1H, m), 2.18 (3H, s), 1.89-1.74 (1H, m), 0.82-0.70 (2H, m), 0.65 -0.54 (2H, m).
Physical properties: Pasty.

(Example 594)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (trifluoromethyl) nicotinate (Compound No. 3462)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 9.42 (1H, s), 9.08 (1H, d, J = 5.1 Hz), 7.79 (1H, d, J = 5.1 Hz), 7.57 (1H, s), 7.14-7.06 (2H, m), 6.90-6.84 (1H, m), 2.16 (3H, s), 1.84-1.72 (1H, m), 0.79-0.71 (2H, m), 0.63-0.55 (2H, m ).
Melting point (° C): 92-93.

(Example 595)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 6-chloronicotinate (Compound No. 3468)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 9.19 (1H, d, J = 2.0), 8.40 (1H, dd, J = 8.4, 2.6), 7.59 (1H, s), 7.54 (1H, d, J = 8.4Hz), 7.10-7.08 (1H, m), 7.07 (1H, s), 6.87-6.82 (1H, m), 2.14 (3H, s), 1.79-1.65 (1H, m), 0.79-0.70 ( 2H, m), 0.62-0.53 (2H, m).
Physical properties: Pasty.

(Example 596)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,6-dichloronicotinate (Compound No. 3474)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.46 (1H, d, J = 8.1 Hz), 7.67 (1H, s), 7.52 (1H, d, J = 8.1 Hz), 7.13-7.02 (2H, m ), 6.90-6.75 (1H, m), 2.14 (3H, s), 1.85-1.68 (1H, m), 0.85-0.48 (4H, m).
Physical properties: amorphous.

(Example 597)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-chloro-6-methylnicotinate (Compound No. 3480)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.37 (1H, d, J = 7.7 Hz), 7.58 (1H, s), 7.27 (1H, d, J = 7.7 Hz), 7.14-7.08 (2H, m ), 6.89-6.80 (1H, m), 2.65 (3H, s), 2.15 (3H, s), 1.83-1.69 (1H, m), 0.80-0.70 (2H, m), 0.68-0.55 (2H, m ).
Physical properties: Pasty.

(Example 598)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 5,6-dichloronicotinate (Compound No. 3486)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 9.07 (1H, d, J = 2.2Hz), 8.50 (1H, d, J = 2.2Hz), 7.57 (1H, s), 7.10-7.07 (2H, m ), 6.87-6.82 (1H, m), 2.13 (3H, s), 1.80-1.65 (1H, m), 0.75-0.70 (2H, m), 0.58-0.55 (2H, m).
Physical properties: Pasty.

(Example 599)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-chloroisonicotinate (Compound No. 3492)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.68 (1H, d, J = 5.0 Hz), 8.05 (1H, s), 7.95-7.92 (1H, m), 7.57 (1H, s), 7.10-7.07 (2H, m), 6.87-6.83 (1H, m), 2.14 (3H, s), 1.77-1.68 (1H, m), 0.75-0.71 (2H, m), 0.58-0.56 (2H, m).
Physical properties: Pasty.

(Example 600)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-benzofuran-2-carboxylate (Compound No. 3498)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 7.86-7.75 (2H, m), 7.68-7.51 (3H, m), 7.38 (1H, dd, J = 7.7, 7.0 Hz), 7.12-7.05 (2H, m), 6.89-6.80 (1H, m), 2.17 (3H, s), 1.86-1.73 (1H, m), 0.80-0.68 (2H, m), 0.64-0.55 (2H, m).
Physical properties: amorphous.

(Example 601)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-benzothiophene-2-carboxylate (Compound No. 3504)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.34 (1H, s), 7.94 (2H, m), 7.64 (1H, s), 7.59-7.42 (2H, m), 7.09-7.07 (2H, m) , 6.87-6.83 (1H, m), 2.18 (3H, s), 1.88-1.72 (1H, m), 0.77-0.71 (2H, m), 0.61-0.53 (2H, m).
Melting point (° C): 105-107.

(Example 602)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1,3-benzothiazole-6-carboxylate (Compound No. 3510)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 9.24 (1H, s), 8.89 (1H, d, J = 1.4 Hz), 8.36 (1H, dd, J = 8.4, 1.4 Hz), 8.28 (1H, d , J = 8.4 Hz), 7.65 (1H, s), 7.09-7.06 (2H, m), 6.87-6.82 (1H, m), 2.17 (3H, s), 1.86-1.73 (1H, m), 0.78- 0.72 (2H, m), 0.63-0.55 (2H, m).
Physical properties: amorphous.

(Example 603)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1,3-benzodioxol-5-carboxylate (Compound No. 3516)
¹ H-NMR (200 MHz, CDCl ₃ ) δ ppm: 7.85 (1H, dd, J = 8.4, 1.8 Hz), 7.60-7.59 (2H, m), 7.09-7.06 (2H, m), 6.93 (1H, d, J = 8.0Hz), 6.86-6.82 (1H, m), 6.10 (2H, s), 2.15 (3H, s), 1.86-1.74 (1H, m), 0.79-0.70 (2H, m), 0.62-0.53 (2H, m).
Physical properties: Pasty.

(Example 604)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-isoquinolinecarboxylate (Compound No. 3522)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.45 (1H, d, J = 8.1 Hz), 7.78-7.70 (2H, m), 7.61-7.53 (2H, m), 7.16 (1H, d, J = 7.7 Hz), 7.12-7.05 (2H, m), 6.90-6.83 (1H, m), 6.66 (1H, d, J = 7.3 Hz), 2.15 (3H, s), 1.81-1.66 (1H, m), 0.79-0.67 (2H, m), 0.63-0.53 (2H, m).
Physical properties: amorphous.

(Example 605)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl tert-butyl (methyl) carbamate (Compound No. 3528)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.51 (1H, s), 7.15-7.03 (2H, m), 6.90-6.80 (1H, m), 3.11 (3H, s), 2.14 (3H, s) , 1.85-1.70 (1H, m), 1.47 (9H, s), 0.80-0.50 (4H, m).
Melting point (° C): 113-115.

(Example 606)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl dibutylcarbamate (Compound No. 3534)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.58 (1H, s), 7.15-7.03 (2H, m), 6.90-6.78 (1H, m), 3.50-3.26 (4H, m), 2.13 (3H, s), 1.87-1.50 (5H, m), 1.50-1.15 (4H, m), 1.10-0.85 (6H, m), 0.80-0.54 (4H, m).
Physical properties: candy-like.

(Example 607)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl benzyl (methyl) carbamate (Compound No. 3540)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.58 (0.5H, s), 7.57 (0.5H, s), 7.40-7.20 (5H, m), 7.15-7.03 (2H, m), 6.92-6.80 ( 1H, m), 4.68 (1H, s), 4.57 (1H, s), 3.08 (1.5H, s), 3.02 (1.5H, s), 2.15 (1.5H, s), 2.13 (1.5H, s) , 1.85-1.65 (1H, m), 0.80-0.45 (4H, m).
Physical properties: candy-like.

(Example 608)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl cyanomethyl (methyl) carbamate (Compound No. 3546)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.59 (0.4H, s), 7.56 (0.6H, s), 7.15-7.04 (2H, m), 6.90-6.80 (1H, m), 4.42 (0.8H , s), 4.36 (1.2H, s), 3.30 (1.8H, s), 3.19 (1.2H, s), 2.14 (3H, s), 1.85-1.62 (1H, m), 0.80-0.53 (4H, m).
Physical properties: candy-like.

(Example 609)
Ethyl N-({[6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] oxy} carbonyl) -N-methylglycinate (Compound No. 3552)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.61 (0.5H, s), 7.60 (0.5H, s), 7.15-7.02 (2H, m), 6.90-6.80 (1H, m), 4.28-4.11 ( 4H, m), 3.23 (1.5H, s), 3.13 (1.5H, s), 2.15 (1.5H, s), 2.13 (1.5H, s), 1.85-1.65 (1H, m), 1.31-1.18 ( 3H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 610)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl methyl (2-pyridinyl) carbamate (Compound No. 3558)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.35-8.25 (1H, m), 7.70-7.55 (1H, m), 7.05-6.90 (5H, m), 6.85-6.74 (1H, m), 3.56 ( 3H, s), 2.03 (3H, s), 1.72-1.55 (1H, m), 0.75-0.45 (4H, m).
Melting point (° C): 140-147.

(Example 611)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-piperidinecarboxylate (Compound No. 3636)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.56 (1H, s), 7.15-7.03 (2H, m), 6.90-6.80 (1H, m), 3.70-3.60 (2H, m), 3.60-3.45 ( 2H, m), 2.15 (3H, s), 1.86-1.70 (1H, m), 1.70-1.50 (6H, m), 0.80-0.53 (4H, m).
Physical properties: candy-like.

(Example 612)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl bis (2-chloroethyl) carbamate (Compound No. 3570)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.58 (1H, s), 7.15-7.05 (2H, m), 6.92-6.82 (1H, m), 3.98-3.70 (8H, m), 2.13 (3H, s), 1.82-1.65 (1H, m), 0.80-0.50 (4H, m).
Melting point (° C): 166-167.

(Example 613)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl diallylcarbamate (Compound No. 3576)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.56 (1H, s), 7.12-7.04 (2H, m), 6.88-6.80 (1H, m), 6.00-5.70 (2H, m), 5.30-5.15 ( 4H, m), 4.10-3.93 (4H, m), 2.13 (3H, s), 1.85-1.68 (1H, m), 0.80-0.52 (4H, m).
Physical properties: candy-like.

(Example 614)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl bis (cyanomethyl) carbamate (Compound No. 3582)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.59 (1H, s), 7.18-7.05 (2H, m), 6.90-6.80 (1H, m), 4.54 (2H, s), 4.48 (2H, s) , 2.13 (3H, s), 1.80-1.65 (1H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 615)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl bis (2-cyanoethyl) carbamate (Compound No. 3588)
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.61 (1H, s), 7.18-7.05 (2H, m), 6.92-6.82 (1H, m), 3.91 (2H, t, J = 6.6Hz), 3.77 (2H, t, J = 6.2Hz), 2.85 (2H, t, J = 6.6Hz), 2.78 (2H, t, J = 6.2Hz), 2.13 (3H, s), 1.80-1.63 (1H, m) , 0.82-0.53 (4H, m).
Melting point (° C): 159-161.

(Example 616)
Ethyl N-({[6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] oxy} carbonyl) -N- (2-ethoxy-2-oxoethyl) glycinate (Compound No. 3594)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.65 (1H, s), 7.13-7.03 (2H, m), 6.90-6.80 (1H, m), 4.33-4.05 (8H, m), 2.12 (3H, s), 1.83-1.65 (1H, m), 1.28 (3H, t, J = 7.3Hz), 1.19 (3H, t, J = 7.3Hz), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 617)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl bis (2-methoxyethyl) carbamate (Compound No. 3600)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 7.59 (1H, s), 7.15-7.05 (2H, m), 6.90-6.80 (1H, m), 3.80-3.50 (8H, m), 3.32 (6H, s), 2.15 (3H, s), 1.86-1.69 (1H, m), 0.80-0.52 (4H, m).
Physical properties: candy-like.

(Example 618)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl bis (2-ethoxyethyl) carbamate (Compound No. 3606)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.15-7.03 (2H, m), 6.90-6.80 (1H, m), 3.78-3.55 (8H, m), 3.46 (4H, q, J = 6.9Hz), 2.14 (3H, s), 1.87-1.65 (1H, m), 1.15 (3H, t, J = 6.9Hz), 1.14 (3H, t, J = 6.9Hz), 0.80- 0.53 (4H, m).
Physical properties: candy-like.

(Example 619)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-azetidine carboxylate (Compound No. 3612)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.53 (1H, s), 7.13-7.02 (2H, m), 6.90-6.78 (1H, m), 4.38-4.05 (4H, m), 2.45-2.29 ( 2H, m), 2.15 (3H, s), 1.85-1.67 (1H, m), 0.80-0.50 (4H, m).
Melting point (° C): 134-136.

(Example 620)
1- [6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] 2-methyl 1,2-pyrrolidine dicarboxylate (Compound No. 3618)
^{1 H-NMR (200MHz, CDCl} 3) δppm: 7.65 (0.5H, s), 7.62 (0.5H, s), 7.15-7.02 (2H, m), 6.90-6.78 (1H, m), 4.63-4.57 ( 0.5H, m), 4.51-4.44 (0.5H, m), 3.91-3.55 (2H, m), 3.75 (1.5H, s), 3.65 (1.5H, s), 2.50-1.90 (4H, m), 2.15 (1.5H, s), 2.13 (1.5H, s), 1.90-1.69 (1H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 621)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-hydroxy-1-pyrrolidinecarboxylate (Compound No. 3624)
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.60 (1H, s), 7.13-7.03 (2H, m), 6.90-6.80 (1H, m), 4.65-4.52 (1H, m), 3.85-3.55 ( 4H, m), 2.14 (3H, s), 2.13-2.00 (2H, m), 1.87-1.70 (2H, m), 0.80-0.50 (4H, m).
Physical properties: candy-like.

(Example 622)
6-Chloro-3- (2-cyclopropyl-3,5,6-trimethylphenoxy) -4-pyridazinol (Compound No. 1126)
(1) 2,3,5-trimethylphenyl acetate
15.09 g (0.1108 mol) of 2,3,5-trimethylphenol was dissolved in dichloromethane (150 mL), 17.82 mL (0.2204 mol) of pyridine and then 20.78 mL (0.2202 mol) of acetic anhydride were added, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into water and extracted with dichloromethane. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-100, hexane: ethyl acetate, gradient) to give 20.08 g (0.1127 mol, quantitative yield) of 2,3,5-trimethylphenyl acetate. )Obtained.

(2) 1- (2-Hydroxy-3,4,6-trimethylphenyl) ethanone 13.83 g (77.60 mmol) of 2,3,5-trimethylphenyl acetate obtained in (1) was stirred under ice-cooling. While adding 20.69 g (155.2 mmol) of aluminum chloride, a little was added. The mixture was stirred overnight while heating to 100 ° C. After allowing to cool, the reaction mixture was added little by little to ice water. This mixture was extracted with dichloromethane, and the organic layers were combined, washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-100, hexane: ethyl acetate, gradient) to give 12.75 g of 1- (2-hydroxy-3,4,6-trimethylphenyl) ethanone. (71.55 mmol, yield 92.20%) was obtained.

(3) 1- (2-Methoxy-3,4,6-trimethylphenyl) ethanone 8.00 g (44.9 mmol) of 1- (2-hydroxy-3,4,6-trimethylphenyl) ethanone obtained from (2) Was dissolved in acetone (100 mL), 18.6 g (135 mmol) of potassium carbonate and then 8.40 mL (135 mmol) of methyl iodide were added, and the mixture was heated to reflux for 27 hours and 30 minutes. Further, 18.6 g (135 mmol) of potassium carbonate and 8.40 mL (135 mmol) of methyl iodide were added, and the mixture was heated to reflux for 6 hours. The reaction mixture was concentrated under reduced pressure, water (100 mL) was added to the residue, and the mixture was extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was purified by silica gel column chromatography (Daisogel 1001W, hexane: ethyl acetate, gradient), and 8.04 g (41.9 Mmol, yield 93.3%).

(4) 1- (2-methoxy-3,4,6-trimethylphenyl) ethanol 1- (2-methoxy-3,4,6-trimethylphenyl) ethanone obtained in (3) 5.01 g (26.1 mmol) Was dissolved in methanol (100 mL), 1.00 g (26.5 mmol) of sodium borohydride was added under ice cooling, and the mixture was stirred for 2 hours 30 minutes under ice cooling. The reaction mixture was poured into 400 mL of ice water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 4.35 g (22.4 mmol, yield 85.8%) of 1- (2-methoxy-3,4,6-trimethylphenyl) ethanol.

(5) 2- (1-Chloroethyl) -3-methoxy-1,4,5-trimethylbenzene 0.652 g of 1- (2-methoxy-3,4,6-trimethylphenyl) ethanol obtained from (4) While stirring, 0.150 mL (1.72 mmol) of oxalyl chloride was added dropwise and stirred at 100 ° C. for 2 hours. Next, dichloromethane (1 mL) and triethylamine (3 mL) were added to the reaction mixture, and the mixture was stirred at 100 ° C. for 3 hours. The reaction mixture was poured into 60 ml of ice water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 0.620 g (2.91 mmol, yield 86.6%) of 2- (1-chloroethyl) -3-methoxy-1,4,5-trimethylbenzene.

(6) 3-methoxy-1,2,5-trimethyl-4-vinylbenzene
Dissolve 0.620 g (2.91 mmol) of 2- (1-chloroethyl) -3-methoxy-1,4,5-trimethylbenzene obtained in (5) in N, N-dimethylformamide (DMF, 6 mL). Potassium 1.20 g (8.70 mmol) was added and heated to reflux for 9 hours. The reaction mixture was poured into 50 ml of ice water and extracted with hexane. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Daisogel 1001W, hexane: ethyl acetate, gradient) to give 0.360 g (2.05 mmol) of 3-methoxy-1,2,5-trimethyl-4-vinylbenzene. Yield 70.4%).

(7) 2-Cyclopropyl-3-methoxy-1,4,5-trimethylbenzene Add 3.07 mL (3.04 mmol) of diethylzinc (0.99 mol / L hexane solution) to dry dichloromethane (5 mL) and stir under ice cooling. Then, a solution of 0.23 mL (3.0 mmol) of trifluoroacetic acid in dichloromethane (2.5 mL) was slowly added dropwise. After completion of the addition, the mixture was stirred for 30 minutes under ice cooling, and 0.24 mL (3.0 mmol) of diiodomethane was added dropwise. Next, a solution of 0.268 g (1.52 mmol) of 3-methoxy-1,2,5-trimethyl-4-vinylbenzene obtained in (6) in dichloromethane (3 mL) was added dropwise and stirred for 1 hour under ice-cooling. The reaction mixture was poured into water, acidified with dilute hydrochloric acid, and extracted with dichloromethane. The organic layers were combined, washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05717, 2 plates used, developed with hexane: ethyl acetate = 25: 1), and 2-cyclopropyl- 0.212 g (1.12 mmol, yield 73.7%) of 3-methoxy-1,4,5-trimethylbenzene was obtained.

(8) 2-Cyclopropyl-3,5,6-trimethylphenol Under a nitrogen atmosphere, 134 mg (3.35 mmol) of 60% sodium hydride was suspended in dry N, N-dimethylformamide (5 mL). Ethanethiol 0.26 mL (3.5 mmol) was slowly added dropwise. After stirring for 30 minutes, a solution of 0.212 g (1.12 mmol) of 2-cyclopropyl-3-methoxy-1,4,5-trimethylbenzene obtained in (7) in dry N, N-dimethylformamide (5 mL) was added dropwise. And stirred at 160 ° C. for 5 hours. After cooling, the reaction mixture was poured into water, acidified with dilute hydrochloric acid, and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with ethyl acetate: hexane = 25: 1), and 2-cyclopropyl- 179 mg (1.02 mmol, yield 91.1%) of 3,5,6-trimethylphenol was obtained.

(9) 6-chloro-3- (2-cyclopropyl-3,5,6-trimethylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-cyclopropyl-3,5,6-trimethylphenoxy) Mixture of pyridazine 1-oxide (step B-2)
2-Cyclopropyl-3,5,6-trimethylphenol 179 mg (1.02 mmol), 1,4-dioxane (5 mL) and dimethyl sulfoxide (5 mL) were mixed, and potassium tert-butoxide 125 mg (1.12 mmol) was added to the mixture. Added and stirred for 10 minutes. To this mixture, 167 mg (1.01 mmol) of 3,6-dichloropyridazine 1-oxide was added and allowed to stand at room temperature for 3 days. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05717, using 2 copies, developed with hexane: ethyl acetate = 2: 1), and 6-chloro-3 263 mg of a mixture of 2- (2-cyclopropyl-3,5,6-trimethylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-cyclopropyl-3,5,6-trimethylphenoxy) pyridazine 1-oxide Obtained.

(10) 4,6-Dichloro-3- (2-cyclopropyl-3,5,6-trimethylphenoxy) pyridazine (Step B-3)
6-Chloro-3- (2-cyclopropyl-3,5,6-trimethylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-cyclopropyl-3,5,6) obtained by (9) -Trimethylphenoxy) pyridazine 1-oxide mixture (263 mg) and phosphorus oxychloride (3.0 mL, 32 mmol) were mixed and stirred overnight at room temperature. Dichloromethane and water were added to the reaction mixture, and the mixture was stirred and extracted with dichloromethane. The organic layers were combined, washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05717, 2 plates used, developed with hexane: ethyl acetate = 2: 1), and 4,6-dichloro 198 mg (0.613 mmol, 60.7% yield from 3,6-dichloropyridazine 1-oxide) of 3- (2-cyclopropyl-3,5,6-trimethylphenoxy) pyridazine was obtained. 43.8 mg of 3-chloro-6- (2-cyclopropyl-3,5,6-trimethylphenoxy) pyridazine 1-oxide (0.144 mmol, 14.2% yield from 3,6-dichloropyridazine 1-oxide) Obtained.

(11) 6-chloro-3- (2-cyclopropyl-3,5,6-trimethylphenoxy) -4-pyridazinol (Compound No. 1126, Steps A-3 and A-4)
198 mg (0.613 mmol) of 4,6-dichloro-3- (2-cyclopropyl-3,5,6-trimethylphenoxy) pyridazine obtained in (10) was dissolved in dimethyl sulfoxide (10 mL), and 251 mg of sodium acetate ( 3.06 mmol) was added and the mixture was stirred at 120 ° C. for 4 hours. The reaction mixture was cooled, poured into water and acidified with dilute hydrochloric acid. This mixture was extracted with ethyl acetate, and the organic layers were combined, washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05717, 2 plates used, developed with hexane: ethyl acetate = 1: 2), and 6-chloro-3 116 mg (0.380 mmol, yield 62.0%) of-(2-cyclopropyl-3,5,6-trimethylphenoxy) -4-pyridazinol (Compound 1126) was obtained.
¹ H-NMR (200MHz, CD3OD) δppm: 6.67 (1H, s), 6.62 (1H, s), 2.22 (3H, s), 2.16 (3H, s), 2.05 (3H, s), 1.85-1.65 ( 1H, m), 0.75-0.62 (2H, m), 0.60-0.45 (2H, m).
Melting point (° C): 212-219.

(Example 623)
6-Chloro-3- (2-methoxy-3,5,6-trimethylphenoxy) -4-pyridazinol (Compound No. 1128)
(1) 1- [2- (Benzyloxy) -3,4,6-trimethylphenyl] ethanone 1- (2-hydroxy-3,4,6-trimethylphenyl) ethanone obtained in Example 622 (2) 2.00 g (11.2 mmol) was dissolved in N, N-dimethylformamide (8 mL). To this solution was added 0.488 g (11.2 mmol) of 60% sodium hydride under ice-cooling, and the mixture was stirred as it was for 10 minutes under ice-cooling. Stir overnight. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 1- [2- (benzyloxy) -3,4,6-trimethyl. 2.36 g (8.81 mmol, 78.7% yield) of phenyl] ethanone were obtained.

(2) 2- (benzyloxy) -3,4,6-trimethylphenyl acetate 500 mg (1.87 mmol) of 1- [2- (benzyloxy) -3,4,6-trimethylphenyl] ethanone obtained from (1) ) Was dissolved in dichloromethane (3 mL), a solution of 921 mg of m-chloroperbenzoic acid (purity 70-75%, 3.73-3.99 mmol) in dichloromethane (6 mL) was added, and the mixture was stirred at room temperature for 2 days. The reaction mixture was poured into a saturated aqueous sodium sulfite solution and extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 560 mg of 2- (benzyloxy) -3,4,6-trimethylphenyl acetate.

(3) 2- (benzyloxy) -3,4,6-trimethylphenol 560 mg of 2- (benzyloxy) -3,4,6-trimethylphenyl acetate obtained in (2) was dissolved in ethanol (15 mL), 2N Aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature overnight and at 60 ° C. for 4 hours. The reaction mixture was cooled to room temperature and poured into water. The mixture was acidified with 1N hydrochloric acid and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 290 mg of 2- (benzyloxy) -3,4,6-trimethylphenol. (1.20 mmol, 64.2% yield from 1- [2- (benzyloxy) -3,4,6-trimethylphenyl] ethanone).

(4) 3- (benzyloxy) -2-methoxy-1,4,5-trimethylbenzene 2- (benzyloxy) -3,4,6-trimethylphenol 290 mg (1.20 mmol) obtained from (3) It was dissolved in acetone (3 mL), 350 mg (2.54 mmol) of potassium carbonate was added, and the mixture was stirred at room temperature for 15 minutes. Next, 0.180 mL (2.89 mmol) of methyl iodide was added, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (MERCK, 1.05744, 3 plates, developed with ethyl acetate: hexane = 10: 1), and 3- (benzyloxy 196 mg (0.766 mmol, 63.8% yield) of 2-methoxy-1,4,5-trimethylbenzene was obtained.

(5) 2-methoxy-3,5,6-trimethylphenol 180 mg (0.703 mmol) of 3- (benzyloxy) -2-methoxy-1,4,5-trimethylbenzene obtained in (4) was added to methanol (3 mL ), 5% palladium-carbon (0.10 g) was added to the solution, and the mixture was stirred under a hydrogen atmosphere (1 atm) for 4 hours. The reaction mixture was filtered through celite and the filtrate was concentrated. 90.7 mg (0.546 mmol, yield 77.7%) of 2-methoxy-3,5,6-trimethylphenol was obtained.

(6) 6-chloro-3- (2-methoxy-3,5,6-trimethylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-methoxy-3,5,6-trimethylphenoxy) pyridazine 1 -Oxide mixture (step B-2)
2-Methoxy-3,5,6-trimethylphenol (90.0 mg, 0.542 mmol), 1,4-dioxane (1.5 mL), and dimethyl sulfoxide (1.5 mL) obtained in (5) were mixed, and this mixture was mixed with potassium. 73.5 mg (0.656 mmol) of tert-butoxide was added, and the mixture was stirred for 15 minutes under ice cooling. To this mixture, 93.2 mg (0.565 mmol) of 3,6-dichloropyridazine 1-oxide was added and stirred at room temperature for 3 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with hexane: ethyl acetate = 2: 1), and 6-chloro-3 140 mg of a mixture of 2- (2-methoxy-3,5,6-trimethylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-methoxy-3,5,6-trimethylphenoxy) pyridazine 1-oxide was obtained. .

(7) 4,6-Dichloro-3- (2-methoxy-3,5,6-trimethylphenoxy) pyridazine (Step B-3)
6-Chloro-3- (2-methoxy-3,5,6-trimethylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-methoxy-3,5,6-trimethyl) obtained by (6) 140 mg of a mixture of phenoxy) pyridazine 1-oxide and 0.25 mL (2.7 mmol) of phosphorus oxychloride were mixed and stirred overnight at room temperature. The reaction mixture was poured into water and extracted with dichloromethane. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with hexane: ethyl acetate = 2: 1), and 4,6-dichloro 111 mg (0.355 mmol, yield 62.8% from 3,6-dichloropyridazine 1-oxide) of -3- (2-methoxy-3,5,6-trimethylphenoxy) pyridazine was obtained. In addition, 38.3 mg (0.130 mmol, yield 23.0% from 3,6-dichloropyridazine 1-oxide) of 3-chloro-6- (2-methoxy-3,5,6-trimethylphenoxy) pyridazine 1-oxide was obtained. It was.

(8) 6-chloro-3- (2-methoxy-3,5,6-trimethylphenoxy) -4-pyridazinol (Compound No. 1128, Step B-4)
The 2,6-dichloro-3- (2-methoxy-3,5,6-trimethylphenoxy) pyridazine obtained in (7) was added to a solution of 111 mg (0.355 mmol) of dimethyl sulfoxide (10 mL) with 2 mol / L sodium hydroxide. 0.3 mL (0.6 mmol) of an aqueous solution was added, and the mixture was stirred at room temperature for 2 hours and 30 minutes. The reaction mixture was poured into an ice-cooled 1 mol / L aqueous sodium hydroxide solution and extracted with ethyl acetate. The aqueous layer was separated, acidified with concentrated hydrochloric acid under ice cooling, and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over magnesium sulfate. The solvent was distilled off, and the resulting residue was washed with ether to give 38.9 mg of 6-chloro-3- (2-methoxy-3,5,6-trimethylphenoxy) -4-pyridazinol (Compound No. 1128). 0.132 mmol, yield 37.2%).
¹ H-NMR (200 MHz, CD3OD) δ ppm: 6.73 (1H, s), 6.67 (1H, s), 3.69 (3H, s), 2.29 (3H, s), 2.15 (3H, s), 2.09 (3H, s).
Melting point (° C): 209-210.

(Example 624)
6-chloro-3- [2- (1-isopropylvinyl) phenoxy] -4-pyridazinol (Compound No. 2529) and 6-chloro-3- [2- (1,2-dimethyl-1-propenyl) phenoxy]- 4-pyridazinol (Compound No. 2542)
(1) 1- [2- (methoxymethoxy) phenyl] ethanone 3.39 g (24.9 mmol) of commercially available 1- (2-hydroxyphenyl) ethanone was dissolved in N, N-dimethylformamide (25 mL), 1.52 g (38.0 mmol) of% sodium hydride was added, and the mixture was stirred for 20 minutes under ice cooling. To this, 3.00 mL (39.5 mmol) of chloro (methoxy) methane was slowly added dropwise and stirred overnight at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 4.33 g (24.1 g) of 1- [2- (methoxymethoxy) phenyl] ethanone. Mmol, yield 96.8%).

(2) 2- [2- (methoxymethoxy) phenyl] -3-methyl-2-butanol 1.00 g (5.56 mmol) of 1- [2- (methoxymethoxy) phenyl] ethanone obtained in (1) was dried in tetrahydrofuran. (3 mL) was dissolved, and 2.8 mL (5.6 mmol) of a 2 mol / L isopropylmagnesium bromide tetrahydrofuran solution was added dropwise under a nitrogen atmosphere and ice cooling. After completion of the dropwise addition, the reaction mixture was stirred at room temperature for 1 hour and 30 minutes. The reaction mixture was poured into water, acidified with dilute hydrochloric acid, and extracted with ether. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 2- [2- (methoxymethoxy) phenyl] -3-methyl-2. -0.522 g (2.33 mmol, yield 41.9%) of butanol was obtained.

(3) 6-chloro-3- [2- (1-isopropylvinyl) phenoxy] pyridazine 1-oxide and 6-chloro-3- [2- (1,2-dimethyl-1-propenyl) phenoxy] pyridazine 1- Mixture containing oxide, etc. 2- (2- (methoxymethoxy) phenyl] -3-methyl-2-butanol obtained in (2) was dissolved in 0.522 g (2.33 mmol) in dichloromethane (3 mL), and the mixture was cooled with ice. 0.50 mL (3.6 mmol) of triethylamine and then 0.25 mL (3.2 mmol) of methanesulfonyl chloride were added and stirred overnight at room temperature. The reaction mixture was poured into water and extracted with dichloromethane. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-100, hexane: ethyl acetate, gradient), and a crude product containing 2- (1,2-dimethyl-1-propenyl) phenol and the like 186 mg was obtained. 132 mg of this crude product was mixed with 1,4-dioxane (2 mL) and dimethyl sulfoxide (2 mL), and 100 mg (0.893 mmol) of potassium tert-butoxide was added to the mixture. Next, 119 mg (0.721 mmol) of 3,6-dichloropyridazine 1-oxide was added to the mixture, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane: ethyl acetate, gradient) to give 6-chloro-3- [2- (1-isopropylvinyl) phenoxy] 220 mg of a mixture containing pyridazine 1-oxide, 6-chloro-3- [2- (1,2-dimethyl-1-propenyl) phenoxy] pyridazine 1-oxide and the like was obtained.

(4) 4,6-dichloro-3- [2- (1-isopropylvinyl) phenoxy] pyridazine and 4,6-dichloro-3- [2- (1,2-dimethyl-1-propenyl) phenoxy] pyridazine ( Step B-3)
6-Chloro-3- [2- (1-isopropylvinyl) phenoxy] pyridazine 1-oxide and 6-chloro-3- [2- (1,2-dimethyl-1-propenyl) phenoxy obtained in (3) ] 200 mg of a mixture containing pyridazine 1-oxide and the like was dissolved in chloroform (0.4 mL), 0.40 mL (4.3 mmol) of phosphorus oxychloride was mixed, and the mixture was stirred at 70 ° C. for 2 hours. The reaction mixture was poured into water and extracted with dichloromethane. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed 3 times with hexane: acetone = 20: 1), and 4,6- Dichloro-3- [2- (1-isopropylvinyl) phenoxy] pyridazine (86% purity, containing 14% 4,6-dichloro-3- [2- (1,2-dimethyl-1-propenyl) phenoxy] pyridazine ) 23 mg, and 4,6-dichloro-3- [2- (1,2-dimethyl-1-propenyl) phenoxy] pyridazine (81% purity, 4,6-dichloro-3- [2- (1-isopropyl) 50 mg of vinyl) phenoxy] pyridazine (with 19%).

(5) 6-chloro-3- [2- (1-isopropylvinyl) phenoxy] -4-pyridazinol (Compound No. 2529, Steps A-3 and A-4)
4,6-dichloro-3- [2- (1-isopropylvinyl) phenoxy] pyridazine obtained in (4) (purity 86%, 4,6-dichloro-3- [2- (1,2-dimethyl- 23 mg of 1-propenyl) phenoxy] pyridazine (containing 14%) was dissolved in dimethyl sulfoxide (1 mL), 80 mg (0.98 mmol) of sodium acetate was added, and the mixture was stirred at 60 ° C. for 9 hours. The reaction mixture was cooled, poured into water and acidified with dilute hydrochloric acid. This mixture was extracted with ethyl acetate, and the organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 2 plates used, developed with hexane: ethyl acetate = 1: 1), and 6-chloro-3 -[2- (1-Isopropylvinyl) phenoxy] -4-pyridazinol (Compound 2529, 91% purity, 9% 6-chloro-3- [2- (1,2-dimethyl-1-propenyl) phenoxy]- 4.5 mg of 4-pyridazinol was obtained. Also, 77% pure 6-chloro-3- [2- (1-isopropylvinyl) phenoxy] -4-pyridazinol (23% 6-chloro-3- [2- (1,2-dimethyl-1-propenyl) 11.0 mg) containing phenoxy] -4-pyridazinol.
¹ H-NMR (200MHz, CD3OD) δppm: 7.40-7.05 (4H, m), 6.59 (1H, s), 5.90 (1H, s), 5.04 (1H, s), 2.71 (1H, septet, J = 6.9 Hz), 0.98 (6H, d, J = 6.9 Hz).
Physical properties: amorphous.

(6) 6-chloro-3- [2- (1,2-dimethyl-1-propenyl) phenoxy] -4-pyridazinol (Compound No. 2542, Steps A-3 and A-4)
4,6-dichloro-3- [2- (1,2-dimethyl-1-propenyl) phenoxy] pyridazine obtained in (4) (purity 81%, 4,6-dichloro-3- [2- (1 -Isopropylvinyl) phenoxy] pyridazine (19 mg) was dissolved in dimethyl sulfoxide (2 mL), sodium acetate 68 mg (0.83 mmol) was added, and the mixture was stirred at 50 ° C. for 11 hours. The reaction mixture was cooled, poured into water and acidified with dilute hydrochloric acid. This mixture was extracted with ethyl acetate, and the organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 2 plates used, developed with hexane: ethyl acetate = 2: 1), and 6-chloro-3 -[2- (1,2-Dimethyl-1-propenyl) phenoxy] -4-pyridazinol (Compound 2542, 86% purity, 14% 6-chloro-3- [2- (1-isopropylvinyl) phenoxy]- 40.2 mg of 4-pyridazinol was obtained. Also, 73% pure 6-chloro-3- [2- (1,2-dimethyl-1-propenyl) phenoxy] -4-pyridazinol (27% 6-chloro-3- [2- (1-isopropylvinyl) 3.7 mg)) containing phenoxy] -4-pyridazinol.
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.38-7.05 (4H, m), 6.59 (1H, s), 1.78 (3H, s), 1.62 (3H, s), 1.46 (3H, s).
Physical properties: amorphous.

(Example 625)
6-Chloro-3- [2- (2-methyl-1-propenyl) phenoxy] -4-pyridazinol (Compound No. 2540)
(1) 1- (2-Methoxyphenyl) -2-methyl-1-propanol To 1.01 g (7.43 mmol) of commercially available 2-methoxybenzaldehyde was added dry tetrahydrofuran (3 mL) in a nitrogen atmosphere, and the mixture was ice-cooled. To this was added dropwise 3.8 mL (7.6 mmol) of a 2 mol / L isopropylmagnesium bromide tetrahydrofuran solution. After completion of the dropwise addition, the reaction mixture was stirred for 1 hour under ice cooling. The reaction mixture was poured into water, acidified with dilute hydrochloric acid, and extracted with ether. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 1- (2-methoxyphenyl) -2-methyl-1-propanol. 1.00 g (5.56 mmol, yield 74.8%) was obtained.

(2) 1- (1-Chloro-2-methylpropyl) -2-methoxybenzene 630 mg (3.50 mmol) of 1- (2-methoxyphenyl) -2-methyl-1-propanol obtained in (1) After dissolving in dichloromethane (3 mL), 0.70 mL (5.0 mmol) of triethylamine and then 0.35 mL (4.5 mmol) of methanesulfonyl chloride were added and stirred for 1 hour. The reaction mixture was poured into water and extracted with dichloromethane. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 720 mg of 1- (1-chloro-2-methylpropyl) -2-methoxybenzene.

(3) 1-methoxy-2- (2-methyl-1-propenyl) benzene 410 mg of 1- (1-chloro-2-methylpropyl) -2-methoxybenzene obtained in (2) was dried N, N- Dissolved in dimethylformamide (8 mL), 395 mg (3.52 mmol) of potassium tert-butoxide was added thereto under ice cooling. The reaction mixture was heated to reflux for 2 hours, then cooled to room temperature and poured into water. Extraction with hexane was performed, and the obtained organic layers were combined and washed successively with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain 460 mg of 1-methoxy-2- (2-methyl-1-propenyl) benzene.

(4) 2- (2-Methyl-1-propenyl) phenol Under a nitrogen atmosphere, 60.0 mg (1.50 mmol) of 60% sodium hydride was suspended in dry N, N-dimethylformamide (3 mL). Under ice cooling, 0.11 mL (1.5 mmol) of ethanethiol was slowly added dropwise. After stirring for 10 minutes, a solution of 200 mg of 1-methoxy-2- (2-methyl-1-propenyl) benzene obtained in (3) in dry N, N-dimethylformamide (0.5 mL) was added dropwise for 2 hours 30 minutes. Heated to reflux. After allowing to cool, the reaction mixture was poured into water, acidified with dilute hydrochloric acid, and extracted with hexane. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 220 mg of 2- (2-methyl-1-propenyl) phenol.

(5) 6-chloro-3- [2- (2-methyl-1-propenyl) phenoxy] pyridazine 1-oxide and 3-chloro-6- [2- (2-methyl-1-propenyl) phenoxy] pyridazine 1 -Oxide mixture (step B-2)
200 mg of 2- (2-methyl-1-propenyl) phenol obtained in (4), 1,4-dioxane (2 mL) and dimethyl sulfoxide (2 mL) were mixed, and 151 mg of potassium tert-butoxide (1. 35 mmol) was added, and the mixture was stirred for 15 minutes under ice cooling. To this mixture was added 207 mg (1.25 mmol) of 3,6-dichloropyridazine 1-oxide, and the mixture was stirred for 15 minutes under ice cooling and then at room temperature for 4 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 6-chloro-3- [2- (2-methyl-1-propenyl). ) Phenoxy] pyridazine 1-oxide and 3-chloro-6- [2- (2-methyl-1-propenyl) phenoxy] pyridazine 1-oxide were mixed in 90.0 mg (0.325 mmol, 1- (2-methoxyphenyl)- Yield 41.2% from 2-methyl-1-propanol).

(6) 4,6-Dichloro-3- [2- (2-methyl-1-propenyl) phenoxy] pyridazine (Step B-3)
6-Chloro-3- [2- (2-methyl-1-propenyl) phenoxy] pyridazine 1-oxide and 3-chloro-6- [2- (2-methyl-1-propenyl) obtained in (5) 90.0 mg (0.325 mmol) of a phenoxy] pyridazine 1-oxide mixture was dissolved in chloroform (0.2 mL), 0.20 mL (2.2 mmol) of phosphorus oxychloride was mixed, and the mixture was stirred at 70 ° C. for 2 hours. The reaction mixture was poured into water and extracted with dichloromethane. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, developed with hexane: ethyl acetate = 9: 1), and 4,6-dichloro- 85.0 mg (0.288 mmol, yield 88.6%) of 3- [2- (2-methyl-1-propenyl) phenoxy] pyridazine was obtained.

(7) 6-chloro-3- [2- (2-methyl-1-propenyl) phenoxy] -4-pyridazinol (Compound No. 2540, Steps A-3 and A-4)
85.0 mg (0.288 mmol) of 4,6-dichloro-3- [2- (2-methyl-1-propenyl) phenoxy] pyridazine obtained in (6) was dissolved in dimethyl sulfoxide (3 mL), and 122 mg of sodium acetate ( 1.49 mmol) was added and the mixture was stirred at 120 ° C. for 2 hours. The reaction mixture was cooled to room temperature, poured into water and acidified with dilute hydrochloric acid. This mixture was extracted with ethyl acetate, and the organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by preparative thin layer chromatography (MERCK, 1.05744, used in 2 plates, developed with ethyl acetate) to give 6-chloro-3- [2- (2 39.6 mg (0.143 mmol, yield 49.7%) of -methyl-1-propenyl) phenoxy] -4-pyridazinol (Compound No. 2540) were obtained.
¹ H-NMR (200MHz, CD3OD) δppm: 7.35-7.15 (3H, m), 7.15-7.05 (1H, m), 6.65 (1H, s), 6.05 (1H, s), 1.76 (3H, s), 1.70 (3H, s).
Melting point (° C): 149-152.

(Example 626)
6-Chloro-3- (3-hydroxyphenoxy) -4-pyridazinol (Compound No. 2544)
(1) 1- {3-[(6-chloro-1-oxide-3-pyridazinyl) oxy] phenyl} ethanone and 1- {3-[(6-chloro-2-oxide-3-pyridazinyl) oxy] phenyl } Ethanone mixture
306 mg (2.25 mmol) of 1- (3-hydroxyphenyl) ethanone, 1,4-dioxane (6 mL) and dimethyl sulfoxide (6 mL) are mixed, and 297 mg (2.65 mmol) of potassium tert-butoxide is added to this mixture, and the mixture is ice-cooled. Stir for 15 minutes. To this mixture, 342 mg (2.07 mmol) of 3,6-dichloropyridazine 1-oxide was added under ice cooling, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 1- {3-[(6-chloro-1-oxide-3- 400 mg (1.51 mmol, 72.9% yield) of a mixture of pyridazinyl) oxy] phenyl} ethanone and 1- {3-[(6-chloro-2-oxide-3-pyridazinyl) oxy] phenyl} ethanone was obtained.

(2) A mixture of 3-[(6-chloro-1-oxide-3-pyridazinyl) oxy] phenyl acetate and 3-[(6-chloro-2-oxide-3-pyridazinyl) oxy] phenyl acetate (1) 1- {3-[(6-chloro-1-oxide-3-pyridazinyl) oxy] phenyl} ethanone and 1- {3-[(6-chloro-2-oxide-3-pyridazinyl) oxy] phenyl obtained } 400 mg (1.51 mmol) of a mixture of ethanone was dissolved in 3 mL of dichloromethane, to which was added a solution of 1.1 g of m-chloroperbenzoic acid (purity 70-75%, 4.5-4.8 mmol) in dichloromethane (3 mL) and at room temperature for 4 days. Stir. A saturated aqueous sodium sulfite solution was added to the reaction mixture, and the mixture was stirred and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient), and the raw material and 3-[(6-chloro-1-oxide-3-pyridazinyl ) Oxy] phenyl acetate and 330 mg of 3-[(6-chloro-2-oxide-3-pyridazinyl) oxy] phenyl acetate were obtained. 280 mg of this mixture was dissolved in dichloromethane (3 mL), and 1.1 g of m-chloroperbenzoic acid (purity 70-75%, 4.5-4.8 mmol) was added thereto, followed by stirring at room temperature overnight. The reaction mixture was poured into 10% aqueous sodium sulfite and extracted with dichloromethane. The organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was washed with hexane to give 3-[(6-chloro-1-oxide-3-pyridazinyl) oxy] phenyl acetate and 3-[(6-chloro-2-oxide- 310 mg of a mixture of 3-pyridazinyl) oxy] phenyl acetate was obtained.

(3) 3-[(4,6-Dichloro-3-pyridazinyl) oxy] phenyl acetate (Step B-3)
Mixture of 3-[(6-chloro-1-oxide-3-pyridazinyl) oxy] phenyl acetate and 3-[(6-chloro-2-oxide-3-pyridazinyl) oxy] phenyl acetate obtained in (2) 310 mg was mixed with chloroform (0.4 mL), 0.40 mL (4.3 mmol) of phosphorus oxychloride was mixed, and the mixture was stirred at 70 ° C. for 3 hours. The reaction mixture was poured into water, stirred, and extracted with dichloromethane. The organic layers were combined, washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 3-[(4,6-dichloro-3-pyridazinyl) oxy] phenyl 46.0 mg (0.154 mmol, 1- {3-[(6-chloro-1-oxide-3-pyridazinyl) oxy] phenyl} ethanone and 1- {3-[(6-chloro-2-oxide-3- Yield 9.6% from a mixture of pyridazinyl) oxy] phenyl} ethanone).

(4) 6-chloro-3- (3-hydroxyphenoxy) -4-pyridazinol (Compound No. 2544, Steps A-3 and A-4)
Dissolve 40.0 mg (0.134 mmol) of 3-[(4,6-dichloro-3-pyridazinyl) oxy] phenyl acetate obtained in (3) in dimethyl sulfoxide (1 mL) and add 56.0 mg (0.683 mmol) of sodium acetate. The mixture was heated and stirred at 120 ° C. for 1 hour. After cooling to room temperature, the reaction mixture was poured into 0.5 mol / L aqueous sodium hydroxide solution and washed with ethyl acetate. The aqueous layer was acidified with 4 mol / L hydrochloric acid and extracted with ethyl acetate. The organic layers were combined and washed sequentially with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain 30 mg (0.126 mmol, yield 94.0%) of 6-chloro-3- (3-hydroxyphenoxy) -4-pyridazinol (Compound No. 2544).
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.25-7.10 (1H, m), 6.70-6.57 (4H, m).
Melting point (° C): 248-251.

(Example 627)
6-Chloro-3- (2-iodo-3-methoxyphenoxy) -4-pyridazinol (Compound No. 2551)
(1) 1-methoxy-3- (methoxymethoxy) benzene 3.68 g (29.7 mmol) of commercially available 3-methoxyphenol was dissolved in N, N-dimethylformamide (50 mL), and under ice cooling, 1.81 g of 60% sodium hydride (45.4 mmol) was added and stirred for 20 minutes under ice cooling. Under ice cooling, 4.05 mL (53.3 mmol) of chloro (methoxy) methane was slowly added dropwise thereto, and the mixture was stirred overnight at room temperature. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient), and 4.81 g (28.6 mmol) of 1-methoxy-3- (methoxymethoxy) benzene was obtained. Yield 96.3%).

(2) 2-Iodo-1-methoxy-3- (methoxymethoxy) benzene 3.70 g (22.0 mmol) of 1-methoxy-3- (methoxymethoxy) benzene obtained in (1) was dissolved in dry ether (50 mL). The mixture was cooled to −78 ° C. under a nitrogen atmosphere, and 5.60 mL (37.2 mmol) of tetramethylethylenediamine was added followed by 22.0 mL (35.2 mmol) of n-butyllithium hexane solution (1.60 M). After stirring at -78 ° C for 30 minutes and then at 0 ° C for 30 minutes, the mixture was cooled to -78 ° C and 9.80 g (38.6 mmol) of iodine was added. The mixture was stirred at -78 ° C for 30 minutes, saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium thiosulfate solution and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 6.59 g of 2-iodo-1-methoxy-3- (methoxymethoxy) benzene.

(3) 2-iodo-3-methoxyphenol 6.59 g of 2-iodo-1-methoxy-3- (methoxymethoxy) benzene obtained in (2) was dissolved in methanol (70 mL), and concentrated hydrochloric acid (0.18 mL) was added. The mixture was added dropwise and stirred at 65 ° C. for 1 hour and 15 minutes. Concentrated hydrochloric acid (0.20 mL) was further added, and the mixture was heated with stirring at 65 ° C. for 2 hours and 40 minutes. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 4.61 g (18.4 mmol, 1- 1 mmol of 2-iodo-3-methoxyphenol). The yield from methoxy-3- (methoxymethoxy) benzene was 83.6%).

(4) A mixture of 6-chloro-3- (2-iodo-3-methoxyphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-iodo-3-methoxyphenoxy) pyridazine 1-oxide (Step B- 2)
2-Iodo-3-methoxyphenol 298 mg (1.19 mmol) 1,4-dioxane (2.5 mL) and dimethyl sulfoxide (2.5 mL) obtained in (3) were mixed, and potassium tert-butoxide 215 mg (1.92 Mmol) and stirred for 10 minutes under ice cooling. To this mixture, 196 mg (1.19 mmol) of 3,6-dichloropyridazine 1-oxide was added under ice cooling, and the mixture was stirred at room temperature for 3 days. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (hexane: ethyl acetate = 3: 1, then developed with hexane: ethyl acetate = 1: 1) to give 6-chloro- 324 mg (0.855 mmol, 71.8% yield) of a mixture of 3- (2-iodo-3-methoxyphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-iodo-3-methoxyphenoxy) pyridazine 1-oxide Obtained.

(5) 4,6-Dichloro-3- (2-iodo-3-methoxyphenoxy) pyridazine (Step B-3)
Mixture of 6-chloro-3- (2-iodo-3-methoxyphenoxy) pyridazine 1-oxide and 3-chloro-6- (2-iodo-3-methoxyphenoxy) pyridazine 1-oxide obtained in (4) To 324 mg (0.855 mmol), 1.0 mL (1.1 mmol) of phosphorus oxychloride was added and stirred overnight at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate = 5: 1) and 4,6-dichloro-3- (2-iodo-3-methoxyphenoxy) 225 mg (0.567 mmol, 66.3% yield) of pyridazine was obtained.

(6) 6-chloro-3- (2-iodo-3-methoxyphenoxy) -4-pyridazinol (Compound No. 2551, Steps A-3 and A-4)
105 mg (0.264 mmol) of 4,6-dichloro-3- (2-iodo-3-methoxyphenoxy) pyridazine obtained in (5) was dissolved in dimethyl sulfoxide (2 mL), and 118 mg (1.44 mmol) of sodium acetate was added. The mixture was heated and stirred at 120 ° C. for 1 hour and 30 minutes. After cooling to room temperature, 4 mol / L aqueous hydrochloric acid solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layers were combined and washed with saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the resulting residue was washed with isopropyl ether to give 6-chloro-3- (2-iodo-3-methoxyphenoxy) -4-pyridazinol (Compound No. 2551) Of 51.2 mg (0.135 mmol, yield 51.1%).
¹ H-NMR (200MHz, CD3OD) δppm: 7.39 (1H, t, J = 8.4Hz), 6.84 (2H, br.t, J = 8.4Hz), 6.73 (1H, s), 3.90 (3H, s) .
Melting point (° C): 231-234.

(Example 628)
6-chloro-3-{[7- (3-hydroxypropyl) bicyclo [4.2.0] octa-1,3,5-trien-2-yl] oxy} -4-pyridazinol (Compound No. 2555)
(1) 2-Iodo-3-methoxyphenyl trifluoromethanesulfonate 2.75 g (15.0 mmol) of 2-iodo-3-methoxyphenol obtained in Example 627 (3) was dissolved in dry dichloromethane, and 7.28 mL (90.0 mmol) of pyridine was dissolved. ) Was added. The mixture was cooled to −20 ° C., 5.40 mL (32.2 mmol) of trifluoromethanesulfonic anhydride was added, and the mixture was stirred for 3 hours and 50 minutes. The reaction mixture was poured into water and extracted with dichloromethane and then ethyl acetate. The organic layers were combined, washed successively with 4 mol / L hydrochloric acid, water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, the residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate = 10: 1), and 5.52 g (14.5 mmol, 2-iodo-3-methoxyphenyl trifluoromethanesulfonate) Yield 96.7%).

(2) tert-butyl [(8-methoxy-2,3,4,4a-tetrahydro-8bH-benzo [3,4] cyclobuta [1,2-b] pyran-8b-yl) oxy] dimethylsilane (1 ) 1.10 g (2.88 mmol) of 2-iodo-3-methoxyphenyl trifluoromethanesulfonate obtained in 1) was dissolved in dry tetrahydrofuran (15 mL), and commercially available tert-butyl (3,4-dihydro-2H-pyran was added under a nitrogen atmosphere. 1.00 mL (4.37 mmol) of -6-yloxy) dimethylsilane was added. The mixture was cooled to −78 ° C., 4.50 mL (7.20 mmol) of n-butyllithium hexane solution (1.60 M) was added, and the mixture was stirred for 20 minutes. The reaction mixture was poured into pH 7 buffer (prepared by dissolving 9.1 g KH2PO4 and 4.3 g Na2HPO4 in 1 L water) and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate = 50: 1), and tert-butyl [(8-methoxy-2,3,4,4a-tetrahydro There was obtained 0.897 g (2.79 mmol, yield 96.9%) of -8bH-benzo [3,4] cyclobuta [1,2-b] pyran-8b-yl) oxy] dimethylsilane.

(3) 8- (3-hydroxypropyl) -5-methoxybicyclo [4.2.0] octa-1,3,5-trien-7-one (2) tert-butyl [(8-methoxy- 2,3,4,4a-tetrahydro-8bH-benzo [3,4] cyclobuta [1,2-b] pyran-8b-yl) oxy] dimethylsilane dissolved in 897 mg (2.79 mmol) in acetonitrile (12 mL) Under ice-cooling, 0.30 mL (7.96-8.30 mmol) of 46-47% hydrofluoric acid aqueous solution was added and stirred for 30 minutes. The reaction mixture was poured into a saturated aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate = 7: 3), and 8- (3-hydroxypropyl) -5-methoxybicyclo [4.2.0] 446 mg (2.17 mmol, yield 77.8%) of octa-1,3,5-trien-7-one was obtained.

(4) 8- (3-Hydroxypropyl) -5-methoxybicyclo [4.2.0] octa-1,3,5-trien-7-one 8- (3-hydroxypropyl)-obtained from (3) 474 mg (2.30 mmol) of 5-methoxybicyclo [4.2.0] octa-1,3,5-trien-7-one was dissolved in dichloromethane (22 mL), and 467 mg (3.49 mmol) of N-chlorosuccinimide and tri Phenylphosphine 917 mg (3.5 mmol) was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into water, saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate = 20: 1), and 8- (3-chloropropyl) -5-methoxybicyclo [4.2.0] 409 mg (1.82 mmol, yield 79.1%) of octa-1,3,5-trien-7-one was obtained.

(5) 7- (3-Chloropropyl) -2-methoxybicyclo [4.2.0] octa-1,3,5-triene Melt chloride (HgCl ₂ ) 111 mg (0.408 mmol) with water (6 mL) and dissolve. Here, 4.00 g (6.12 mmol) of zinc powder was added, and the mixture was stirred at room temperature for 50 minutes. The supernatant was removed and the remaining solid was washed once with water. To this was slowly added water (6.0 mL), then concentrated hydrochloric acid (5.0 mL), and acetic acid (2.4 mL). Finally, 8- (3-chloropropyl) -5-methoxybicyclo obtained in (4) was added. [4.2.0] Octa-1,3,5-trien-7-one 409 mg (1.82 mmol) was dissolved in toluene (2 mL) and ethanol (2 mL) and added. The mixture was stirred at 115 ° C. overnight and cooled to room temperature. Toluene (20 mL) was added and stirred for 30 minutes, and the organic layer was separated. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate = 20: 1), 7- (3-chloropropyl) -2-methoxybicyclo [4.2.0] 304 mg (1.44 mmol, yield 79.1%) of octa-1,3,5-triene was obtained.

(6) 7- (3-chloropropyl) -2-methoxybicyclo obtained from 7- (3-chloropropyl) bicyclo [4.2.0] octa-1,3,5-trien-2-ol (5) [4.2.0] Octa-1,3,5-triene (304 mg, 1.44 mmol) was dissolved in dichloromethane (2.0 mL). Under ice-cooling, boron tribromide (0.50 mL, 5.32 mmol) was added and the mixture was ice-cooled. Stirred for 1 hour. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate = 4: 1), and 7- (3-chloropropyl) bicyclo [4.2.0] octa-1, 303 mg (1.54 mmol, quantitative yield) of 3,5-trien-2-ol was obtained.

(7) 6-chloro-3-{[7- (3-chloropropyl) bicyclo [4.2.0] octa-1,3,5-trien-2-yl] oxy} pyridazine 1-oxide and 3-chloro- 6-{[7- (3-Chloropropyl) bicyclo [4.2.0] octa-1,3,5-trien-2-yl] oxy} pyridazine 1-oxide mixture (step B-2)
7- (3-Chloropropyl) bicyclo [4.2.0] octa-1,3,5-trien-2-ol 303 mg (1.54 mmol), 1,4-dioxane (2.0 mL) obtained in (6) and Dimethyl sulfoxide (2.0 mL) was mixed, 275 mg (2.46 mmol) of potassium tert-butoxide was added to the mixture, and the mixture was stirred for 10 minutes under ice cooling. To this mixture, 254 mg (1.54 mmol) of 3,6-dichloropyridazine 1-oxide was added under ice cooling, and the mixture was stirred overnight at room temperature. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (developed with hexane: ethyl acetate = 3: 1) to give 6-chloro-3-{[7- (3-chloropropyl ) Bicyclo [4.2.0] octa-1,3,5-trien-2-yl] oxy} pyridazine 1-oxide and 3-chloro-6-{[7- (3-chloropropyl) bicyclo [4.2.0] 364 mg (1.12 mmol, yield 72.7%) of a mixture of octa-1,3,5-trien-2-yl] oxy} pyridazine 1-oxide was obtained.

(8) 4,6-Dichloro-3-{[7- (3-chloropropyl) bicyclo [4.2.0] octa-1,3,5-trien-2-yl] oxy} pyridazine (Step B-3)
6-chloro-3-{[7- (3-chloropropyl) bicyclo [4.2.0] octa-1,3,5-trien-2-yl] oxy} pyridazine 1-oxide obtained in (7) and 364 mg (1.12 mmol) of a mixture of 3-chloro-6-{[7- (3-chloropropyl) bicyclo [4.2.0] octa-1,3,5-trien-2-yl] oxy} pyridazine 1-oxide To the mixture, 1.0 mL (11 mmol) of phosphorus oxychloride was added and stirred at room temperature for 7 hours and 15 minutes. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (developed with hexane: ethyl acetate = 2: 1) to give 4,6-dichloro-3-{[7- (3-chloropropyl) 253 mg (0.735 mmol, 65.6% yield) of bicyclo [4.2.0] octa-1,3,5-trien-2-yl] oxy} pyridazine was obtained.

(9) 6-chloro-3-{[7- (3-hydroxypropyl) bicyclo [4.2.0] octa-1,3,5-trien-2-yl] oxy} -4-pyridazinol (Compound No. 2555, Steps A-3 and A-4)
4,6-dichloro-3-{[7- (3-chloropropyl) bicyclo [4.2.0] octa-1,3,5-trien-2-yl] oxy} pyridazine 253 mg obtained in (8) ( 0.735 mmol) was dissolved in dimethyl sulfoxide (5.0 mL), 250 mg (3.05 mmol) of sodium acetate was added, and the mixture was stirred with heating at 120 ° C. for 2 hr. After cooling to room temperature, 4 mol / L aqueous hydrochloric acid solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layers were combined and washed with saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (developed with hexane: ethyl acetate = 2: 1) to give 6-chloro-3-{[ 48.5 mg (0.158 mmol, yield 21.5%) of 7- (3-hydroxypropyl) bicyclo [4.2.0] octa-1,3,5-trien-2-yl] oxy} -4-pyridazinol (Compound No. 2555) )Obtained. Also 28.2 mg 6-chloro-3-{[7- (3-chloropropyl) bicyclo [4.2.0] octa-1,3,5-trien-2-yl] oxy} -4-pyridazinol and 3- A mixture of {2-[(6-chloro-4-hydroxy-3-pyridazinyl) oxy] bicyclo [4.2.0] octa-1,3,5-trien-7-yl} propyl acetate was obtained.
^{1 H-NMR (200MHz, CD3OD} ) δppm: 7.22-7.18 (1H, m), 6.98-6.94 (2H, m), 6.70 (1H, s), 3.62-3.56 (2H, m), 3.46 (1H, br .s), 3.34 (1H, br.s), 3.18 (1H, dd, J = 13.9, 5.5Hz), 2.62 (1H, dd, J = 13.9, 2.2Hz), 1.81-1.62 (4H, m).
Physical property: Oily substance.

(Example 629)
6-Chloro-3-[(7,7-dimethylbicyclo [4.2.0] octa-1,3,5-trien-2-yl) oxy] -4-pyridazinol (Compound No. 2556)
(1) 5-Methoxy-8,8-dimethylbicyclo [4.2.0] octa-1,3,5-trien-7-one 2-iodo-3-methoxyphenyl obtained by the method of Example 628 (1) Dissolve 723 mg (1.89 mmol) of trifluoromethanesulfonate in dry tetrahydrofuran (10 mL) and add 0.50 mL (2.47 mmol) of commercially available [(1-methoxy-2-methyl-1-propynyl) oxy] (trimethyl) silane under a nitrogen atmosphere. added. The mixture was cooled to −78 ° C., 2.70 mL (4.32 mmol) of n-butyllithium hexane solution (1.60 M) was added, and the mixture was stirred for 20 minutes. The reaction mixture was poured into pH 7 buffer (prepared by dissolving 9.1 g KH2PO4 and 4.3 g Na2HPO4 in 1 L water) and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated, tetrahydrofuran (2.0 mL), water (0.2 mL) and acetic acid (2.0 mL) were added to the residue, and the mixture was stirred at room temperature for 1 hr. Ether was added to the reaction mixture, which was washed successively with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (developed with hexane: ethyl acetate = 2: 1) to give 5-methoxy-8,8-dimethylbicyclo [4.2.0] octa-1 , 3,5-trien-7-one was obtained in an amount of 182 mg (1.03 mmol, yield 54.5%).

(2) 2-Methoxy-7,7-dimethylbicyclo [4.2.0] octa-1,3,5-triene Water (6 mL) was added to 109 mg (0.401 mmol) of mercury chloride (HgCl ₂ ) and dissolved. 3.98 g (6.09 mmol) of zinc powder was added and stirred at room temperature for 1 hour. The supernatant was removed and the remaining solid was washed once with water. Water (6.0 mL) and then concentrated hydrochloric acid (5.0 mL) were slowly added thereto, and acetic acid (2.4 mL) was finally added. Finally, 5-methoxy-8,8-dimethylbicyclo [4.2. 0] Octa-1,3,5-trien-7-one 182 mg (1.03 mmol) was dissolved in toluene (2 mL) and ethanol (2 mL) and added. The mixture was stirred at 115 ° C. overnight and cooled to room temperature. Toluene (20 mL) was added and stirred for 20 minutes, and the organic layer was separated. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (developed with hexane: ethyl acetate = 25: 1) to give 2-methoxy-7,7-dimethylbicyclo [4.2.0] octa-1 85.1 mg (0.525 mmol, yield 51.0%) of 3,3,5-triene was obtained.

(3) 7,7-dimethylbicyclo [4.2.0] octa-1,3,5-trien-2-ol 2-methoxy-7,7-dimethylbicyclo [4.2.0] octa obtained from (2) Dissolve 85.1 mg (0.525 mmol) of -1,3,5-triene in dichloromethane (5.0 mL), add 0.20 mL (2.12 mmol) of boron tribromide with stirring under ice cooling, and add 2 hours 10 minutes under ice cooling. Stir. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 97.6 mg of 7,7-dimethylbicyclo [4.2.0] octa-1,3,5-trien-2-ol.

(4) 6-chloro-3-[(7,7-dimethylbicyclo [4.2.0] octa-1,3,5-trien-2-yl) oxy] pyridazine 1-oxide and 3-chloro-6- [ (7,7-Dimethylbicyclo [4.2.0] octa-1,3,5-trien-2-yl) oxy] pyridazine 1-oxide (Step B-2)
7,7-dimethylbicyclo [4.2.0] octa-1,3,5-trien-2-ol 97.6 mg, 1,4-dioxane (1.5 mL) and dimethyl sulfoxide (1.5 mL) obtained in (3) Were mixed, 97.8 mg (0.873 mmol) of potassium tert-butoxide was added to the mixture, and the mixture was stirred for 10 minutes under ice cooling. To this mixture, 90.2 mg (0.547 mmol) of 3,6-dichloropyridazine 1-oxide was added under ice cooling, and the mixture was stirred overnight at room temperature. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (developed twice with hexane: ethyl acetate = 3: 1) to give 6-chloro-3-[(7,7-dimethyl Bicyclo [4.2.0] octa-1,3,5-trien-2-yl) oxy] pyridazine 1-oxide and 3-chloro-6-[(7,7-dimethylbicyclo [4.2.0] octa-1, 3,5-trien-2-yl) oxy] pyridazine 1-oxide mixture from 61.7 mg (0.223 mmol, 2-methoxy-7,7-dimethylbicyclo [4.2.0] octa-1,3,5-triene Yield 42.5%).

(5) 4,6-dichloro-3-[(7,7-dimethylbicyclo [4.2.0] octa-1,3,5-trien-2-yl) oxy] pyridazine (Step B-3)
6-Chloro-3-[(7,7-dimethylbicyclo [4.2.0] octa-1,3,5-trien-2-yl) oxy] pyridazine 1-oxide and 3-chloro obtained in (4) -6-[(7,7-Dimethylbicyclo [4.2.0] octa-1,3,5-trien-2-yl) oxy] pyridazine 1-oxide mixture 61.7mg (0.223mmol) to phosphorus oxychloride 0.50mL (5.4 mmol) was added and stirred at room temperature overnight. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (developed with hexane: ethyl acetate = 5: 1) to give 4,6-dichloro-3-[(7,7-dimethylbicyclo [4.2 .0] octa-1,3,5-trien-2-yl) oxy] pyridazine was obtained, 43.7 mg (0.148 mmol, 66.4% yield).

(6) 6-chloro-3-[(7,7-dimethylbicyclo [4.2.0] octa-1,3,5-trien-2-yl) oxy] -4-pyridazinol (Compound No. 2556, Step A- 3 and step A-4)
4,6-dichloro-3-[(7,7-dimethylbicyclo [4.2.0] octa-1,3,5-trien-2-yl) oxy] pyridazine 43.7 mg (0.148 mmol) obtained in (5) ) Was dissolved in dimethyl sulfoxide (2.0 mL), 63.1 mg (0.770 mmol) of sodium acetate was added, and the mixture was stirred with heating at 120 ° C. for 2 hr. After cooling to room temperature, 4 mol / L aqueous hydrochloric acid solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layers were combined and washed sequentially with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the resulting residue was washed with isopropyl ether to give 6-chloro-3-[(7,7-dimethylbicyclo [4.2.0] octa-1,3, There was obtained 31.6 mg (0.114 mmol, yield 77.0%) of 5-trien-2-yl) oxy] -4-pyridazinol (Compound No. 2556).
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.26-7.19 (1H, m), 6.97-6.89 (2H, m), 6.71 (1H, s), 2.81 (2H, s), 1.41 (6H, s).
Melting point (° C): 197-199.

(Example 630)
4-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] -3-methylphenyl acetate (Compound No. 2572)
(1) 1- {4-[(6-Chloro-1-oxide-3-pyridazinyl) oxy] -3-methylphenyl} ethanone and 1- {4-[(6-Chloro-2-oxide-3-pyridazinyl) ) Oxy] -3-methylphenyl} ethanone mixture (step B-2)
784 mg (5.23 mmol) of commercially available 1- (4-hydroxy-3-methylphenyl) ethanone, 1,4-dioxane (5 mL) and dimethyl sulfoxide (5 mL) were mixed, and 938 mg (8.38 mmol) of potassium tert-butoxide was added to this mixture. And stirred for 10 minutes under ice-cooling. To this mixture, 861 mg (5.22 mmol) of 3,6-dichloropyridazine 1-oxide was added under ice cooling, and the mixture was stirred overnight at room temperature. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate = 5: 1) to give 1- {4-[(6-chloro-1-oxide-3-pyridazinyl ) Oxy] -3-methylphenyl} ethanone and 1- {4-[(6-chloro-2-oxide-3-pyridazinyl) oxy] -3-methylphenyl} ethanone in a mixture of 758 mg (2.74 mmol, yield 52.5 %)Obtained.

(2) 4-[(6-Chloro-1-oxide-3-pyridazinyl) oxy] -3-methylphenyl acetate and 4-[(6-Chloro-2-oxide-3-pyridazinyl) oxy] -3-methyl 1- {4-[(6-Chloro-1-oxide-3-pyridazinyl) oxy] -3-methylphenyl} ethanone and 1- {4-[(6-chloro -2-oxide-3-pyridazinyl) oxy] -3-methylphenyl} ethanone mixture 758mg (2.74mmol) dissolved in 1,2-dichloroethane (13mL), 2.62g m-chloroperbenzoic acid (purity 70-75% 10.6-11.4 mmol), and the mixture was stirred at room temperature for 4 hours and 45 minutes. Further, 1.20 g of m-chloroperbenzoic acid (purity 70-75%, 4.86-5.20 mmol) was added, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into 10% aqueous sodium sulfite and extracted with ethyl acetate. The organic layer was washed successively with saturated aqueous sodium carbonate and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate = 5: 1) to obtain raw material 4-[(6-chloro-1-oxide-3-pyridazinyl) oxy 622 mg of a mixture of] -3-methylphenyl acetate and 4-[(6-chloro-2-oxide-3-pyridazinyl) oxy] -3-methylphenyl acetate was obtained. 30 mL of hydrogen peroxide solution (0.5 mL, 4.85 mmol) was mixed with 1,2-dichloroethane (2.2 mL), and 3.2 mL (22.7 mmol) of trifluoroacetic anhydride was added dropwise under ice cooling, followed by stirring at room temperature. This mixture was mixed with the raw material obtained earlier, 4-[(6-chloro-1-oxide-3-pyridazinyl) oxy] -3-methylphenyl acetate, and 4-[(6-chloro-2-oxide-3 -Pyridazinyl) oxy] -3-methylphenyl acetate (622 mg) was added to a solution of 1,2-dichloroethane (2.2 mL) under ice cooling, and the mixture was stirred under ice cooling for 1 hr and at room temperature overnight. The reaction mixture was poured into 10% aqueous sodium sulfite and extracted with ethyl acetate. The organic layer was washed successively with saturated aqueous sodium carbonate, water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate gradient) to give 4-[(6-chloro-1-oxide-3-pyridazinyl) oxy] -3- A mixture of methylphenyl acetate and 4-[(6-chloro-2-oxide-3-pyridazinyl) oxy] -3-methylphenyl acetate (413 mg, 1.40 mmol, yield 51.1%) was obtained.

(3) 4-[(4,6-Dichloro-3-pyridazinyl) oxy] -3-methylphenyl acetate (Step B-3)
4-[(6-Chloro-1-oxide-3-pyridazinyl) oxy] -3-methylphenyl acetate and 4-[(6-chloro-2-oxide-3-pyridazinyl) oxy] obtained in (2) 413 mg (1.40 mmol) of a mixture of -3-methylphenyl acetate was dissolved in chloroform (2 mL), and 2.0 mL (22 mmol) of phosphorus oxychloride was mixed and stirred at 80 ° C. for 3 hours. The reaction mixture was diluted with dichloromethane and poured into water. This mixture was extracted with dichloromethane and then with ethyl acetate. The organic layers were combined, washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane-ethyl acetate, hexane-ethyl acetate = 6: 1) to give 4-[(4,6-dichloro- There was obtained 336 mg (1.07 mmol, yield 76.4%) of 3-pyridazinyl) oxy] -3-methylphenyl acetate.

(4) 4-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] -3-methylphenyl acetate (Compound No. 2572, Step A-3 and Step A-4)
160 mg (0.511 mmol) of 4-[(4,6-dichloro-3-pyridazinyl) oxy] -3-methylphenyl acetate obtained in (3) was dissolved in dimethyl sulfoxide (1.5 mL), and 136 mg (1.66 mmol) of sodium acetate was dissolved. ) And heated and stirred at 120 ° C. for 2 hours. After cooling to room temperature, 4 mol / L aqueous hydrochloric acid solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layers were combined and washed sequentially with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the resulting residue was washed with isopropyl ether to give 4-[(6-chloro-4-hydroxy-3-pyridazinyl) oxy] -3-methylphenyl acetate ( Compound No. 2572) (37.3 mg, 0.126 mmol, yield 24.7%) was obtained.
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.13-6.94 (3H, m), 6.70 (1H, s), 2.27 (3H, s), 2.17 (3H, s).
Melting point (° C): 255 (dec.).

(Example 631)
6-Chloro-3- [2- (difluoromethyl) -6-methylphenoxy] -4-pyridazinol (Compound No. 2576)
(1) 2- (Methoxymethoxy) -3-methylbenzaldehyde
2.96 g (36.5 mmol) of 2-hydroxy-3-methylbenzaldehyde was dissolved in N, N-dimethylformamide (50 mL), and 2.19 g (54.6 mmol) of 60% sodium hydride was added under ice cooling, followed by stirring for 10 minutes. Under ice cooling, 3.59 mL (47.3 mmol) of chloro (methoxy) methane was added thereto and stirred at room temperature for 1 hour and 30 minutes. The reaction mixture was poured into a saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was purified by silica gel column chromatography (Daisogel 1001W, hexane: ethyl acetate = 50: 1), and 6.60 g (36.6 mmol, yield) of 2- (methoxymethoxy) -3-methylbenzaldehyde was obtained. 100%).

(2) 1- (Difluoromethyl) -2- (methoxymethoxy) -3-methylbenzene 589 mg (3.27 mmol) of 2- (methoxymethoxy) -3-methylbenzaldehyde obtained from (1) was added to dichloromethane (10 mL). In a nitrogen atmosphere, 0.863 mL (6.52 mmol) of (diethylamino) sulfur trifluoride (DAST) was added and stirred at room temperature for 3 hours. After standing at room temperature overnight, the reaction mixture was poured into water and extracted with dichloromethane. The organic layers were combined, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Daisogel 1001W, hexane: ethyl acetate = 10: 1) to give 229 mg of 1- (difluoromethyl) -2- (methoxymethoxy) -3-methylbenzene. (1.13 mmol, yield 34.6%).

(3) 2- (Difluoromethyl) -6-methylphenol 1- (Difluoromethyl) -2- (methoxymethoxy) -3-methylbenzene 229 mg (1.13 mmol) obtained in (2) was added to methanol (5 mL). Dissolved, 2 drops of concentrated hydrochloric acid were added at room temperature, and the mixture was stirred at 60 ° C. for 30 minutes. The reaction mixture was cooled to room temperature and the solvent was distilled off under reduced pressure. Ethyl acetate was added to the residue, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 135 mg (0.854 mmol, yield 75.6%) of 2- (difluoromethyl) -6-methylphenol.

(4) 6-chloro-3- [2- (difluoromethyl) -6-methylphenoxy] pyridazine 1-oxide and 3-chloro-6- [2- (difluoromethyl) -6-methylphenoxy] pyridazine 1-oxide (Process B-1)
135 mg (0.854 mmol) of 2- (difluoromethyl) -6-methylphenol obtained in (3) was dissolved in 1,4-dioxane (1.5 mL) and dimethyl sulfoxide (1.5 mL), and this mixture was ice-cooled. 115 mg (1.03 mmol) of potassium tert-butoxide was added and stirred for 5 minutes. To this mixture, 141 mg (0.855 mmol) of 3,6-dichloropyridazine 1-oxide was added under ice cooling, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was subjected to silica gel column chromatography (eluted with hexane: ethyl acetate = 2: 1) and preparative thin layer chromatography (MERCK 1.05744, 3 hexanes: ethyl acetate = 2 6-chloro-3- [2- (difluoromethyl) -6-methylphenoxy] pyridazine 1-oxide and 3-chloro-6- [2- (difluoromethyl) -6- 28.6 mg (0.0997 mmol, 11.7% yield) of a mixture of methylphenoxy] pyridazine 1-oxide was obtained.

(5) 4,6-Dichloro-3- [2- (difluoromethyl) -6-methylphenoxy] pyridazine (Step B-3)
6-Chloro-3- [2- (difluoromethyl) -6-methylphenoxy] pyridazine 1-oxide and 3-chloro-6- [2- (difluoromethyl) -6-methylphenoxy] obtained in (4) 28.6 mg (0.0997 mmol) of the pyridazine 1-oxide mixture was dissolved in chloroform (0.5 mL), 76.5 mg (0.50 mmol) of phosphorus oxychloride was added, and the mixture was heated to reflux for 8 hours. After leaving overnight at room temperature, water and dichloromethane were added to the reaction mixture and stirred for 30 minutes. This was extracted with dichloromethane, and the organic layers were combined, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (developed with MERCK 1.05744 hexane: ethyl acetate = 4: 1), and 4,6-dichloro-3- [2- (difluoromethyl ) -6-methylphenoxy] pyridazine (19.1 mg, 0.0626 mmol, yield 62.8%) was obtained.

(6) 6-chloro-3- [2- (difluoromethyl) -6-methylphenoxy] -4-pyridazinol (Compound No. 2576)
19.1 mg (0.0626 mmol) of 4,6-dichloro-3- [2- (difluoromethyl) -6-methylphenoxy] pyridazine obtained in (5) was dissolved in dimethyl sulfoxide (0.5 mL), and 25.7 mg of sodium acetate ( 0.313 mmol) was added and the mixture was stirred with heating at 120 ° C. for 2 hours. After cooling to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layers were combined and washed sequentially with water and saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (developed with MERCK 1.05744 ethyl acetate) to give 6-chloro-3- [2- ( 17.8 mg (0.0620 mmol, 99.0% yield) of difluoromethyl) -6-methylphenoxy-4-pyridazinol (Compound No. 2576) was obtained.
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.55-7.25 (3H, m), 6.83 (1H, t, J = 55.1 Hz). 2.15 (3H, s).
Melting point (° C): 204-205.

(Example 632)
6-Chloro-3- [2,4-dibromo-5- (ethylsulfanyl) phenoxy] -4-pyridazinol (Compound No. 2596)
(1) 4,6-dichloro-3- [2,4-dibromo-5- (ethylsulfanyl) phenoxy] pyridazine Commercially available 1-bromo-2-methoxy-4-nitrobenzene (2.05 g, 8.84 mmol) and water (200 mL) ), And then ammonium chloride 11.4 g (213 mmol) and then zinc powder 4.78 g (73.2 mmol) were added. The mixture was stirred at room temperature for 5 hours, filtered through celite, and the filtrate was extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 1.78 g of residue.
This residue was mixed with water (9 mL) and a 47% aqueous hydrobromic acid solution (3 mL), and an aqueous solution (3.6 mL) of sodium nitrite 655 mg (9.49 mmol) was added dropwise with stirring under ice cooling. After completion of the dropwise addition, the mixture was stirred for 10 minutes, and a solution of 973 mg (6.80 mmol) of cuprous bromide in 47% aqueous hydrobromic acid solution (3.6 mL) was added dropwise. The reaction mixture was stirred at 110 ° C. for 2 hours and 30 minutes, cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was subjected to silica gel column chromatography (Wakogel C-100, hexane: ethyl acetate = 10: 1) and preparative thin layer chromatography (MERCK, 1.05717 hexane: ethyl acetate = 4). To 1) (multiple development at 1) to obtain 751 mg of a crude product.
Under a nitrogen atmosphere, 339 mg (8.46 mmol) of 60% sodium hydride was suspended in dry N, N-dimethylformamide (5 mL), and 0.65 mL (8.78 mmol) of ethanethiol was slowly added dropwise to the suspension. After stirring for 30 minutes, a solution obtained by dissolving 751 mg of the above composition in N, N-dimethylformamide (8 mL) was added to this mixture, and the mixture was stirred at 160 ° C. for 5 hours. The reaction mixture was left at room temperature overnight, poured into water, acidified with dilute hydrochloric acid, and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, multiple development with hexane: ethyl acetate = 4: 1) to produce a crude phenolic product. 109 mg of product was obtained.
109 mg of the obtained phenolic crude product was mixed with 1,4-dioxane (3 mL) and dimethyl sulfoxide (3 mL), and 53.5 mg (0.478 mmol) of potassium tert-butoxide was added to this mixture, followed by stirring for 15 minutes under ice cooling. did. To this mixture, 71.2 mg (0.432 mmol) of 3,6-dichloropyridazine 1-oxide was added under ice cooling, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 3 plates used, multiple development with hexane: ethyl acetate = 2: 1) to produce a crude etheric product. 71.5 mg of product was obtained.
44.8 mg of ethereal crude product was dissolved in phosphorus oxychloride (3 mL) and stirred at 60 ° C. for 21 hours. Water and dichloromethane were added to the reaction mixture and stirred, followed by extraction with dichloromethane. The organic layers were combined, washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin-layer chromatography (MERCK, 1.05744, 2 plates used, developed with hexane: ethyl acetate = 2: 1), and 4,6-dichloro-3- 14.4 mg (0.0314 mmol, yield 0.567%) of [2,4-dibromo-5- (ethylsulfanyl) phenoxy] pyridazine was obtained.

(2) 6-chloro-3- [2,4-dibromo-5- (ethylsulfanyl) phenoxy] -4-pyridazinol (compound number 2596, steps A-3 and A-4)
33.4 mg (0.0728 mmol) of 4,6-dichloro-3- [2,4-dibromo-5- (ethylsulfanyl) phenoxy] pyridazine obtained in (1) was dissolved in dimethyl sulfoxide (3 mL), and sodium acetate 29.8 mg (0.363 mmol) was added, and the mixture was stirred with heating at 120 ° C. for 4 hr 30 min. After standing overnight at room temperature, water was added to the reaction mixture, acidified with dilute hydrochloric acid, and extracted with ethyl acetate. The organic layers were combined and washed sequentially with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (multiple development with MERCK 1.05744 ethyl acetate) to give 6-chloro-3- [2, 14.1 mg (0.0297 mmol, yield 40.8%) of 4-dibromo-5- (ethylsulfanyl) phenoxy] -4-pyridazinol (Compound No. 2596) was obtained.
¹ H-NMR (200MHz, CD3OD) δppm: 7.84 (1H, s), 7.21 (1H, s), 6.72 (1H, s), 2.97 (2H, q, J = 7.3Hz), 1.33 (3H, t, J = 7.3Hz).
Melting point (° C): 225-228.

(Example 633)
6-Chloro-3- (2,3,5-trimethyl-6-vinylphenoxy) -4-pyridazinol (Compound No. 2603)
(1) 1- (2-methoxy-3,4,6-trimethylphenyl) ethanone Produced by the method described in Chemical Research in Toxicology, 1997, Vol. 10, No. 3, pages 335-343 1- (2-hydroxy-3,4,6-trimethylphenyl) ethanone 2.00 g (11.2 mmol) can be dissolved in acetone (30 mL), potassium carbonate 3.10 g (22.4 mmol), then methyl iodide 1.40 mL (22.5 mmol) ) Was added and heated to reflux for 5 hours. After cooling to room temperature, the reaction mixture was concentrated and the residue was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-100, hexane: ethyl acetate gradient) to obtain 1.90 g of 1- (2-methoxy-3,4,6-trimethylphenyl) ethanone ( 9.90 mmol, yield 88.4%).

(2) 1- (2-methoxy-3,4,6-trimethylphenyl) ethanol 1.00 g (5.21 mmol) of 1- (2-methoxy-3,4,6-trimethylphenyl) ethanone obtained from (1) Was dissolved in methanol (8 mL), and 170 mg (4.50 mmol) of sodium borohydride was added little by little while stirring. After confirming the disappearance of the raw materials by analytical thin layer chromatography (TLC), the reaction mixture was poured into water and acidified with hydrochloric acid. This was extracted with hexane, the organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 1.0 g of 1- (2-methoxy-3,4,6-trimethylphenyl) ethanol.

(3) 2- (1-Chloroethyl) -3-methoxy-1,4,5-trimethylbenzene 1.0 g of 1- (2-methoxy-3,4,6-trimethylphenyl) ethanol obtained from (2) It melt | dissolved in the dichloromethane (10 mL), Triethylamine 1.10mL (7.91 mmol) and then methanesulfonyl chloride 0.56mL (7.21 mmol) were added with stirring under ice-cooling. The reaction mixture was stirred at room temperature for 20 minutes, poured into water and extracted with dichloromethane. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 1.2 g of 2- (1-chloroethyl) -3-methoxy-1,4,5-trimethylbenzene.

(4) 3-Methoxy-1,2,5-trimethyl-4-vinylbenzene 1.2 g of 2- (1-chloroethyl) -3-methoxy-1,4,5-trimethylbenzene obtained in (3) is dried. Dissolved in N, N-dimethylformamide (12 mL), 1.14 g (10.2 mmol) of potassium tert-butoxide was added with stirring under ice cooling. The reaction mixture was stirred at room temperature for 30 minutes and then stirred for 30 minutes under heating to reflux. After cooling to room temperature, it was poured into water and extracted with hexane. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 870 mg of 3-methoxy-1,2,5-trimethyl-4-vinylbenzene.

(5) 2,3,5-trimethyl-6-vinylphenol and 2- [1- (ethylsulfanyl) ethyl] -3,5,6-trimethylphenol 60% sodium hydride 270 mg (6.75 mmol) under nitrogen atmosphere Was suspended in dry N, N-dimethylformamide (8 mL), and 0.60 mL (8.10 mmol) of ethanethiol was slowly added dropwise to this suspension. After stirring for 15 minutes, 400 mg (2.27 mmol) of 3-methoxy-1,2,5-trimethyl-4-vinylbenzene obtained in (4) was added to dry N, N-dimethylformamide (1.5 mL). The dissolved one was added and heated to reflux for 1 hour. After cooling to room temperature, the reaction mixture was poured into water, acidified with hydrochloric acid, and extracted with hexane. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was subjected to silica gel column chromatography (Wakogel C-100, hexane: ethyl acetate = 20: 1) and preparative thin layer chromatography (MERCK, 1.05744 hexane: ethyl acetate = 8: 1). 2), 3,5-trimethyl-6-vinylphenol 63.0 mg (0.389 mmol, yield 16.2% from 1- (2-methoxy-3,4,6-trimethylphenyl) ethanone) And 2- [1- (ethylsulfanyl) ethyl] -3,5,6-trimethylphenol 330 mg (1.47 mmol, 61.4% yield from 1- (2-methoxy-3,4,6-trimethylphenyl) ethanone) Got.

(6) 6-chloro-3- (2,3,5-trimethyl-6-vinylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2,3,5-trimethyl-6-vinylphenoxy) pyridazine 1 -Oxide mixture (step B-2)
Dissolve 43.0 mg (0.265 mmol) of 2,3,5-trimethyl-6-vinylphenol obtained in (5) in 1,4-dioxane (0.4 mL) and dimethyl sulfoxide (0.4 mL). Then, 36.0 mg (0.321 mmol) of potassium tert-butoxide was added and stirred for 10 minutes. To this mixture, 47.6 mg (0.288 mmol) of 3,6-dichloropyridazine 1-oxide was added under ice cooling, followed by stirring at room temperature for 4 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (using MERCK 1.05744, 2 hexanes: ethyl acetate = 2: 1), and 6-chloro-3- (2 , 3,5-trimethyl-6-vinylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2,3,5-trimethyl-6-vinylphenoxy) pyridazine 1-oxide in a mixture of 27.6 mg (0.0949 mmol, Yield 35.8%).

(7) 4,6-Dichloro-3- (2,3,5-trimethyl-6-vinylphenoxy) pyridazine (Step B-3)
6-Chloro-3- (2,3,5-trimethyl-6-vinylphenoxy) pyridazine 1-oxide and 3-chloro-6- (2,3,5-trimethyl-6-vinyl obtained in (6) 0.02 mL (0.22 mmol) of phosphorus oxychloride was added to 27.6 mg (0.0949 mmol) of the phenoxy) pyridazine 1-oxide mixture, and the mixture was stirred at room temperature for 2 hours. Chloroform 0.4mL was added here, and it stirred at room temperature overnight. The reaction mixture was concentrated, 0.2 mL (2.2 mmol) of phosphorus oxychloride was added to the residue, and the mixture was stirred for 5 hours at room temperature. The reaction mixture was concentrated, and the residue was purified by preparative thin-layer chromatography (developed with hexane: ethyl acetate = 5: 1 using 1 piece of MERCK 1.05744), 4,6-dichloro-3- (2, 5.0 mg (0.016 mmol, 17% yield) of 3,5-trimethyl-6-vinylphenoxy) pyridazine was obtained.

(8) 6-chloro-3- (2,3,5-trimethyl-6-vinylphenoxy) -4-pyridazinol (Compound No. 2603, Step A-3 and Step A-4)
Dissolve 5.0 mg (0.016 mmol) of 4,6-dichloro-3- (2,3,5-trimethyl-6-vinylphenoxy) pyridazine obtained in (7) in dimethyl sulfoxide (1 mL), and add 10.3 mg of sodium acetate. (0.126 mmol) was added and stirred with heating at 120 ° C. for 2 hours. After cooling to room temperature, the reaction mixture was poured into water, acidified with hydrochloric acid, and extracted with ethyl acetate. The organic layers were combined and washed sequentially with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (developed with ethyl acetate, 1.05744 from MERCK) and 6-chloro-3- ( 1.5 mg (0.0052 mmol, 33% yield) of 2,3,5-trimethyl-6-vinylphenoxy) -4-pyridazinol (Compound No. 2603) was obtained.
¹ H-NMR (200MHz, CD3OD) δppm: 7.25 (1H, s), 6.67 (1H, dd, J = 11.0Hz, 17.6Hz), 6.56 (1H, s), 5.66 (1H, dd, J = 1.5Hz , 17.6Hz), 5.10 (1H, dd, J = 1.5Hz, 11.0Hz), 2.29 (3H, s), 2.20 (3H, s), 2.04 (3H, s).
Physical properties: amorphous.

(Example 634)
6-Chloro-3- {2- [1- (ethylsulfanyl) ethyl] -3,5,6-trimethylphenoxy} -4-pyridazinol (Compound No. 2606)
(1) 6-chloro-3- {2- [1- (ethylsulfanyl) ethyl] -3,5,6-trimethylphenoxy} -4-methoxypyridazine (Step D-1)
150 mg (0.670 mmol) of 2- [1- (ethylsulfanyl) ethyl] -3,5,6-trimethylphenol obtained in Example 633 (5) was added to 1,4-dioxane (2 mL) and dimethyl sulfoxide (2 mL). In an ice-cooled solution, 93 mg (0.83 mmol) of potassium tert-butoxide was added to the solution, and the mixture was stirred at room temperature for 20 minutes. This mixture was ice-cooled again, 120 mg (0.670 mmol) of 3,6-dichloro-4-methoxypyridazine was added, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was subjected to silica gel chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) and preparative thin layer chromatography (MERCK, 1.05744, 2 hexanes: ethyl acetate = 2 2-6 mg (0.0728 mmol, 0.0728 mmol, 6-chloro-3- {2- [1- (ethylsulfanyl) ethyl] -3,5,6-trimethylphenoxy} -4-methoxypyridazine). Yield 10.9%). In addition, 60.0 mg (0.163 mmol, yield 24.3%) of 3-chloro-6- {2- [1- (ethylsulfanyl) ethyl] -3,5,6-trimethylphenoxy} -4-methoxypyridazine was obtained.

(2) 6-chloro-3- {2- [1- (ethylsulfanyl) ethyl] -3,5,6-trimethylphenoxy} -4-pyridazinol (Compound No. 2606, Step D-2)
24.0 mg (0.358 mmol) of 2-hydroxypyridine was dissolved in dimethyl sulfoxide (1 mL), and 41.0 mg (0.366 mmol) of potassium tert-butoxide was added to this solution at room temperature, followed by stirring at room temperature for 20 minutes. To this, 26.7 mg (0.0728 mmol) of 6-chloro-3- {2- [1- (ethylsulfanyl) ethyl] -3,5,6-trimethylphenoxy} -4-methoxypyridazine obtained by (1) Of dimethyl sulfoxide (1 mL) was added and stirred at 60 ° C. After completion of the reaction, the reaction mixture was allowed to cool and poured into water. The mixture was acidified with hydrochloric acid and extracted with ethyl acetate. The organic layers were combined and washed sequentially with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off. The obtained residue was purified by preparative thin layer chromatography (Merck, 1.05744, developed with ethyl acetate) to give 6-chloro-3- {2- [1- (ethylsulfanyl) ethyl] -3,5 , 6-Trimethylphenoxy} -4-pyridazinol (Compound No. 2606) was obtained in an amount of 6.6 mg (0.019 mmol, yield 26%).
¹ H-NMR (200MHz, CD3OD) δppm: 7.20 (2H, s), 6.64 (1H, s), 2.40-2.15 (8H, m), 2.03 (3H, s), 1.40 (3H, d, J = 7.0 Hz), 1.24 (1H, m), 1.03 (3H, t, J = 7.3Hz).
Physical properties: amorphous.

(Example 635)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl phthalate (Compound No. 1625) ) And bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] phthalate (Compound No. 2838, Step I)
207 mg (0.726 mmol) of (2,4-dichlorophenyl) (5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl) methanone was suspended in acetonitrile (3 mL), and 1,4-diazabicyclo [2.2.2 ] 81.6 mg (0.729 mmol) of octane was added and stirred. To this was added 105 μL (0.729 mmol) of phthaloyl dichloride, and the mixture was stirred for 1 hour at room temperature. Then, 200 mg (0.722 mmol) of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol was added. And stirred at room temperature for 1 hour and 30 minutes. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Daisogel 1001W, hexane: ethyl acetate, gradient) to give 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4 -Pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl phthalate (Compound No. 1625) 28.0 mg (0.0405 mmol, 5.61% yield) and bis [6-chloro -3- (2-Cyclopropyl-6-methylphenoxy) -4-pyridazinyl] phthalate (Compound No. 2838) was obtained in an amount of 163 mg (0.238 mmol, yield 33.0%).
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl phthalate (Compound No. 1625) ):
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.01-7.96 (1H, m), 7.89-7.68 (3H, m), 7.57 (1H, s), 7.29-7.06 (5H, m), 6.90-6.83 ( 1H, m), 3.71 (3H, s), 2.27 (3H, s), 2.13 (3H, s), 1.82-1.68 (1H, m), 0.77-0.53 (4H, m).
Physical properties: amorphous.
Bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] phthalate (Compound No. 2838):
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.13-8.06 (2H, m), 7.84-7.78 (2H, m), 7.58 (2H, s), 7.15-7.06 (4H, m), 6.90-6.83 ( 2H, m), 2.13 (6H, s), 1.82-1.68 (2H, m), 0.73-0.52 (8H, m).
Physical properties: amorphous.

(Example 636)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl 1,3-benzene Disulfonate (Compound No. 2333) and bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] 1,3-benzenedisulfonate (Compound No. 3755, Step I)
122 mg (0.428 mmol) of (2,4-dichlorophenyl) (5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl) methanone was suspended in acetonitrile (4 mL), and 1,4-diazabicyclo [ 2.2.2] Octane 72.0 mg (0.643 mmol) and then 1,3-benzenedisulfonyl dichloride 117 mg (0.425 mmol) were added and stirred at room temperature for 30 minutes. The reaction mixture was ice-cooled, and 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol 100 mg (0.361 mmol) was further added, followed by stirring at room temperature for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane: ethyl acetate, gradient) to give 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) 4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl 1,3-benzenedisulfonate (Compound No. 2333) 135 mg (0.177 mmol, yield 49.0) %) And bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] 1,3-benzenedisulfonate (Compound No. 3755) 38.0 mg (0.0503 mmol, yield 13.9) %)Obtained.
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl 1,3-benzene Disulfonate (Compound No. 2333):
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.67 (1H, t, J = 1.9Hz), 8.40-8.34 (1H, m), 8.31-8.24 (1H, m), 7.86 (1H, t, J = 8.0Hz), 7.56 (1H, s), 7.37 (1H, d, J = 1.9Hz), 7.29-7.23 (1H, m), 7.15-7.00 (3H, m), 6.85-6.78 (1H, m), 3.81 (3H, s), 2.00 (3H, s), 1.94 (3H, s), 1.70-1.52 (1H, m), 0.73-0.45 (4H, m).
Physical properties: amorphous.
Bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] 1,3-benzenedisulfonate (Compound No. 3755):
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 8.77 (1H, dd, J = 1.8Hz, 1.8Hz), 8.41 (2H, dd, J = 7.7Hz, 1.8Hz), 7.88 (1H, t, J = 8.0Hz), 7.48 (2H, s), 7.15-6.95 (4H, m), 6.90-6.75 (2H, m), 1.97 (6H, s), 1.67-1.46 (2H, m), 0.75-0.44 (8H , m).
Physical properties: amorphous.

(Example 637)
Bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] pentanedioate (Compound No. 2746) and 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl pentandioate (Compound No. 2739)
241 mg (0.870 mmol) of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol is suspended in acetonitrile (8 mL), and 1,4-diazabicyclo [2.2.2] octane 139 mg under ice cooling (1.23 mmol), then 146 mg (0.864 mmol) of pentanedioyl dichloride and 244 mg (0.856 mmol) of (2,4-dichlorophenyl) (5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl) methanone In addition, it was stirred at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was subjected to silica gel column chromatography (Wakogel C-100, hexane: ethyl acetate, gradient) and preparative thin layer chromatography (MERCK, 1.05744, 2 hexanes: ethyl acetate = 2 1 or 1: 1) and bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] pentanedioate (Compound No. 2746) 42.0 mg ( 0.0646 mmol, yield 7.48%) and 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazole As a result, 35.0 mg (0.0532 mmol, yield 6.21%) of 5-yl pentanedioate (Compound No. 2739) was obtained.
Bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] pentanedioate (Compound No. 2746):
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.23 (2H, s), 7.14-7.02 (4H, m), 6.83 (2H, dd, J = 6.6, 2.9Hz), 2.89 (4H, t, J = 7.0Hz), 2.25 (2H, quintet, J = 7.0Hz), 2.10 (6H, s), 1.80-1.65 (2H, m), 0.78-0.52 (8H, m).
Physical properties: candy-like.
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl pentandioate (compound Number 2739):
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.45-7.17 (4H, m), 7.14-7.00 (2H, m), 6.90-6.75 (1H, m), 3.53 (3H, s), 2.83 (2H, t, J = 7.0Hz), 2.57 (2H, t, J = 7.0Hz), 2.20-2.00 (2H, m), 2.11 (3H, s), 2.10 (3H, s), 1.80-1.65 (1H, m ), 0.80-0.50 (4H, m).
Physical properties: amorphous.

(Example 638)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-pyrrolidinecarboxylate (Compound No. 1937)
200 mg (0.722 mmol) of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol was mixed with toluene (3 mL) and cooled on ice. While stirring in a nitrogen atmosphere, 60 μL (0.742 mmol) of pyridine and then 0.67 mL (0.724 mmol) of a 1.08 mol / L phosgenetoluene solution were added, and the mixture was stirred at room temperature for 15 minutes. The reaction mixture was ice-cooled, 60 μL (0.722 mmol) of pyridine and then 60 μL (0.719 mmol) of pyrrolidine were added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (using MERCK 1.05744 4 plates, developed with hexane: ethyl acetate = 2: 1), and 6-chloro-3- (2 190 mg (0.508 mmol, yield 70.7%) of -cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-pyrrolidinecarboxylate (Compound No. 1937) were obtained.
^{1 H-NMR (200MHz, CDCl} 3) δppm: 7.59 (1H, s), 7.15-7.03 (2H, m), 6.90-6.80 (1H, m), 3.62 (2H, dd, J = 6.6Hz, 6.9Hz ), 3.51 (2H, dd, J = 6.9Hz, 6.6Hz), 2.15 (3H, s), 2.05-1.90 (4H, m), 1.88-1.68 (1H, m), 0.80-0.50 (4H, m) .
Melting point (° C): 115-118.

(Example 639)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl methoxy (methyl) carbamate (Compound No. 3564)
200 mg (0.722 mmol) of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol was mixed with toluene (3 mL) and cooled on ice. While stirring in a nitrogen atmosphere, 60 μL (0.742 mmol) of pyridine and then 0.67 mL (0.724 mmol) of a 1.08 mol / L phosgenetoluene solution were added, and the mixture was stirred at room temperature for 15 minutes. The reaction mixture was ice-cooled, 120 μL (1.48 mmol) of pyridine and then 70.4 mg (0.722 mmol) of N, O-dimethylhydroxylamine hydrochloride were added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (Wakogel C-100, hexane: ethyl acetate, gradient) to give 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) 100 mg (0.275 mmol, yield 38.1%) of 4-pyridazinyl methoxy (methyl) carbamate (Compound No. 3564) was obtained.
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 7.53 (1H, s), 7.15-7.03 (2H, m), 6.90-6.82 (1H, m), 3.84 (3H, s), 3.35 (3H, s) , 2.15 (3H, s), 1.87-1.67 (1H, m), 0.80-0.52 (4H, m).
Melting point (° C): 63-64.5.

(Example 640)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,5-dimethyl-1H-pyrrole-1-carboxylate (Compound No. 3630)
37.4 mg (0.393 mmol) of 2,5-dimethyl-1H-pyrrole was mixed with toluene (1 mL) and stirred under ice-cooling, 40.0 μL (0.407 mmol) of pyridine, and then 0.34 mL (1.08 mol / L phosgene toluene solution) 0.367 mmol) was added and stirred for 1 hour. To this, 40.0 μL (0.407 mmol) of pyridine and then 100 mg (0.361 mmol) of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol were added and stirred for 3 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (using MERCK 1.05744, 2 hexanes: ethyl acetate = 2: 1), and 6-chloro-3- (2 24.0 mg (0.0603 mmol, 16.7% yield) of 2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,5-dimethyl-1H-pyrrole-1-carboxylate (Compound No. 3630) was obtained.
¹ H-NMR (200 MHz, CDCl ₃ ) δppm: 8.20-8.03 (1H, m), 7.63 (1H, s), 7.13-7.00 (2H, m), 6.90-6.80 (1H, m), 6.36 (1H, d, J = 2.9Hz), 2.55 (3H, s), 2.22 (3H, s), 2.15 (3H, s), 1.90-1.70 (1H, m), 0.80-0.50 (4H, m).
Melting point (° C): 208-210.

(Example 641)
4-{[4- (Benzoyloxy) -6-chloro-3-pyridazinyl] oxy} -3-methylphenyl benzoate (Compound No. 3850)
(1) 6-chloro-3- (4-hydroxy-2-methylphenoxy) -4-pyridazinol 4-[(4,6-dichloro-3-pyridazinyl) oxy]-obtained in Example 630 (3) Dissolve 173 mg (0.553 mmol) of 3-methylphenyl acetate in 1,4-dioxane (1.4 mL), add 0.7 mL (2.1 mmol) of 3 mol / L sodium hydroxide solution and dimethyl sulfoxide (2.8 mL) overnight at room temperature. Stir. A 4 mol / L aqueous hydrochloric acid solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layers were combined and washed sequentially with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off. The obtained residue was purified by preparative thin layer chromatography (developed with dichloromethane: methanol = 36: 1) to give 66.8-chloro-3- (4-hydroxy-2-methylphenoxy) -4-pyridazinol in 66.8. mg was obtained.

(2) 4-{[4- (Benzoyloxy) -6-chloro-3-pyridazinyl] oxy} -3-methylphenyl benzoate (Compound No. 3850)
66.8 mg of 6-chloro-3- (4-hydroxy-2-methylphenoxy) -4-pyridazinol obtained in (1) was dissolved in acetonitrile (1.0 mL), and 1,4-diazabicyclo [2.2.2] octane 60.0 was dissolved. mg (0.536 mmol) and then 61 μL (0.523 mmol) of benzoyl chloride were added and stirred at room temperature for 1 hour 30 minutes. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined and washed sequentially with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off. The obtained residue was purified by preparative thin layer chromatography (development with hexane: ethyl acetate = 5: 1), and 4-{[4- (benzoyloxy) -6-chloro-3-pyridazinyl] oxy} There was obtained 36.9 mg (0.0800 mmol, yield of 14.5% from 4-[(4,6-dichloro-3-pyridazinyl) oxy] -3-methylphenyl acetate) (3-methylphenyl benzoate (Compound No. 3850)).
^{1 H-NMR (200MHz, CDCl} 3) δppm: 8.21-8.17 (4H, m), 7.72-7.48 (7H, m), 7.22-7.07 (3H, m), 2.21 (3H, s).
Melting point (° C): 118-120.

(Example 642)
3- (2-Aminophenoxy) -3-chloro-4-pyridazinol (Compound No. 377)
(1) 2-[(6-Chloro-4-methoxy-3-pyridazinyl) oxy] aniline (Step D-1)
670 mg (6.15 mmol) of 2-aminophenol was dissolved in a mixed solvent of 1,4-dioxane (7 mL) and dimethyl sulfoxide (7 mL), and 690 mg (6.16 mmol) of potassium tert-butoxide was added to the solution under ice cooling. Stir for minutes. To this mixture was added 1000 mg (5.59 mmol) of 3,6-dichloro-4-methoxypyridazine, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into ice water, brine was added, and the mixture was extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off and the resulting residue was purified by silica gel chromatography (Wakogel C-100, hexane-ethyl acetate, gradient) to give 2-[(6-chloro-4-methoxy-3-pyridazinyl) oxy] 328 mg (1.30 mmol, 23.3% yield) of aniline and 2-[(6-chloro-4-methoxy-3-pyridazinyl) oxy] aniline and 2-[(6-chloro-5-methoxy-3-pyridazinyl) oxy 100 mg of a mixture of aniline was obtained.

(2) 3- (2-Aminophenoxy) -3-chloro-4-pyridazinol (Compound No. 377, Step D-2)
20.0 mg (0.198 mmol) of 2-[(6-chloro-4-methoxy-3-pyridazinyl) oxy] aniline obtained in (1) is dissolved in dimethyl sulfoxide (0.4 mL), and 2 mol / L aqueous sodium hydroxide solution is dissolved. (0.2 mL, 0.4 mmol) was added and stirred at room temperature for 5 hours. The reaction mixture was poured into saturated brine and extracted with tetrahydrofuran. The organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (developed with dichloromethane: methanol = 10: 1 using 2 MERCK 1.05744) and 3- (2-aminophenoxy) -3-chloro. 17.0 mg (0.0714 mmol, yield 36.1%) of 4-pyridazinol (Compound No. 377) was obtained.
¹ H-NMR (200 MHz, CD3OD) δ ppm: 7.50-6.94 (2H, m), 6.90-6.82 (1H, m), 6.85-6.63 (2H, m).
Melting point (° C): 249-250.

(Example 643)
N- {2-[(6-Chloro-4-hydroxy-3-pyridazinyl) oxy] phenyl} acetamide (Compound No. 380)
18.0 mg (0.0756 mmol) of 3- (2-aminophenoxy) -3-chloro-4-pyridazinol obtained in Example 641 was mixed with dichloromethane (0.8 mL), and 0.050 mL of triethylamine with stirring under ice-cooling ( 0.36 mmol) and then 0.010 mL (0.14 mmol) of acetyl chloride were added and stirred at room temperature for 3 hours. The reaction mixture was poured into saturated brine and extracted with tetrahydrofuran. The organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (developed with MERCK 1.05715 dichloromethane: methanol = 10: 1), and N- {2-[(6-chloro-4-hydroxy- Obtained 3.6 mg (0.0129 mmol, yield 17.1%) of 3-pyridazinyl) oxy] phenyl} acetamide (Compound No. 380).
¹ H-NMR (200 MHz, CD3OD) δ ppm: 8.10-8.00 (1H, m), 7.25-7.08 (3H, m), 6.60 (1H. S), 2.12 (3H, s).
Melting point (° C): 135.

(Example 644)
N, N, N-Tributyl-1-butananium 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinolate (Compound No. 3798)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol 105 mg (0.379 mmol) in ethanol (2 mL) was added to a 2 mol / L aqueous sodium hydroxide solution 0.19 mL (0.38 mmol), followed by 106 mg (0.381 mmol) of tetrabutylammonium chloride was added and stirred at 60 ° C. for 5 hours. The reaction mixture was left at room temperature overnight and the solid was removed by filtration. The filtrate was concentrated and 197 mg (0.380 mmol, yield) of N, N, N-tributyl-1-butananium 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinolate (Compound No. 3798) 100%).
¹ H-NMR (200MHz, CD3OD) δppm: 7.05-6.95 (2H, m), 6.80-6.73 (1H, m), 6.43 (1H, s), 3.30-3.15 (8H, m), 2.14 (3H, s ), 2.00-1.85 (1H, m), 1.76-1.53 (8H, m), 1.50-1.30 (8H, m), 1.02 (12H, t, J = 7.1Hz), 0.78-0.63 (2H, m), 0.63-0.48 (2H, m).
Melting point (° C): 113-114.

(Example 645)
Sodium 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinolate (Compound No. 3805)
To a solution of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol 100 mg (0.361 mmol) in ethanol (2 mL) was added 0.18 mL (0.36 mmol) of a 2 mol / L aqueous sodium hydroxide solution, and 50 Stir at 4 ° C. for 4 hours. The reaction mixture was concentrated to obtain 108 mg (0.361 mmol, 100% yield) of sodium 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinolate (Compound No. 3805).
¹ H-NMR (200MHz, CD3OD) δppm: 7.05-6.95 (2H, m), 6.77 (1H, dd, J = 6.4, 3.1Hz), 6.43 (1H, s), 2.14 (3H, s), 2.00- 1.82 (1H, m), 0.78-0.63 (2H, m), 0.63-0.48 (2H, m).
Melting point (° C):> 260.

(Example 646)
5-Bromo-6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol (Compound No. 3843)
To a solution of 157 mg (0.567 mmol) of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol in N, N-dimethylformamide (2 mL) was added 108 mg (0.607 mmol) of N-bromosuccinimide. The mixture was further stirred at room temperature for 3 hours and 30 minutes. Water and then a 4 mol / L aqueous hydrochloric acid solution were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by preparative thin layer chromatography (developed with MERCK 1.05744 hexane: ethyl acetate = 2: 1) to give 5-bromo-6-chloro-3- (2-cyclo 123 mg (0.346 mmol, 61.0% yield) of propyl-6-methylphenoxy) -4-pyridazinol (Compound No. 3843) was obtained.
¹ H-NMR (200MHz, CD3OD) δppm: 7.08-7.05 (2H, m), 6.85-6.80 (1H, m), 2.14 (3H, s), 1.88-1.76 (1H, m), 0.82-0.72 (2H , m), 0.60-0.56 (2H, m).
Physical properties: amorphous.

(Example 647)
3- (2-Allyl-6-methylphenoxy) -6-chloro-4-pyridazinol (Compound No. 835)
¹ H-NMR (270 MHz, CD3OD) δppm: 7.17-7.10 (3H, m), 6.71 (1H, s), 5.95-5.73 (1H, m), 5.00-4.90 (2H, m), 3.26 (1H, d , J = 7.0Hz), 2.12 (3H, s).
Melting point (° C): 126-128.

(Example 648)
6-Chloro-3- (2,6-dimethylphenoxy) -4-pyridazinyl dimethyl carbamate (Compound No. 1889)
¹ H-NMR (500 MHz, CDCl ₃ ) δ ppm: 7.56 (1H, s), 7.09 (3H, s), 3.15 (3H, s), 3.05 (3H, s), 2.13 (6H, s).
Melting point (° C): 149-150.

(Example 649)
6-Chloro-3- (2-methylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3685)
¹ H-NMR (500MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.29-7.22 (2H, m), 7.17 (1H, t, J = 7.6Hz), 7.09 (1H, d, J = 7.6Hz ), 3.77-3.70 (4H, m), 3.70-3.66 (2H, m), 3.62-3.57 (2H, m), 2.19 (3H, s).
Melting point (° C): 124.

(Example 650)
6-chloro-3- (2-isopropylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3686)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.43-7.33 (1H, m), 7.33-7.18 (2H, m), 7.12-7.02 (1H, m), 3.85-3.55 ( 8H, m), 3.08 (1H, m, J = 6.9Hz), 1.21 (6H, d, J = 6.9Hz).
Melting point (° C): 77-78.

(Example 651)
6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3687)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.58 (1H, s), 7.26-7.13 (2H, m), 7.13-7.05 (1H, m), 7.05-6.98 (1H, m), 3.79-3.63 ( 6H, m), 3.63-3.52 (2H, m), 1.92-1.81 (1H, m), 0.84-0.74 (2H, m), 0.72-0.61 (2H, m).
Physical properties: Pasty.

(Example 652)
6-Chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3688)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.19 (1H, t, J = 7.6 Hz), 7.13 (1H, d, J = 7.6 Hz), 6.94 (1H, d, J = 7.6Hz), 3.77-3.70 (4H, m), 3.70-3.66 (2H, m), 3.62-3.57 (2H, m), 2.97 (2H, t, J = 7.6Hz), 2.74 (2H, t, J = 7.6Hz), 2.06 (2H, quintet, J = 7.6Hz).
Melting point (° C): 136.

(Example 653)
6-chloro-3- (2,6-dimethylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3689)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.10 (3H, s), 3.80-3.70 (6H, m), 3.62-3.58 (2H, m), 2.12 (6H, s) .
Melting point (° C): 86-87.

(Example 654)
6-Chloro-3- (2,3,5,6-tetramethylphenoxy) -4-pyridazinyl dimethyl carbamate (Compound No. 3894)
¹ H-NMR (500MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 6.90 (1H, s), 3.15 (3H, s), 3.05 (3H, s), 2.23 (6H, s), 2.04 (6H , s).
Melting point (° C): 200 (sublimation).

(Example 655)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl ethoxy (methyl) carbamate (Compound No. 3918)
200 mg (0.722 mmol) of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol was mixed with toluene (2 mL). While stirring under a nitrogen atmosphere, 150 μL (1.86 mmol) of pyridine and then 0.68 mL (0.734 mmol) of a 1.08 mol / L phosgenetoluene solution were added and stirred at room temperature for 20 minutes. This mixture was mixed with 150 μL of pyridine (1.86 mmol), O-ethyl-N-methylhydroxylamine hydrochloride 80.0 mg {0.717 mmol, Bioorganic & Medicinal Chemistry Letters, 2001, Vol. 11, No. 13. In the mixture of toluene (2 mL), and stirred at room temperature for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (using MERCK 1.05744 4 plates, developed with hexane: ethyl acetate = 2: 1) to give 6-chloro-3- (2 96.0 mg (0.254 mmol, yield 35.4%) of -cyclopropyl-6-methylphenoxy) -4-pyridazinyl ethoxy (methyl) carbamate (Compound No. 3918) was obtained.
¹ H-NMR (200MHz, CDCl ₃ ) δppm: 7.54 (1H, s), 7.15-7.05 (2H, m), 6.90-6.80 (1H, m), 4.08 (2H, q, J = 7.0Hz), 3.35 (3H, s), 2.15 (3H, s), 1.84-1.65 (1H, m), 1.30 (3H, t, J = 7.0Hz), 0.80-0.55 (4H, m).
Melting point (° C): 82-83.

(Example 656)
6-chloro-3- (2-chlorophenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3920)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.67 (1H, s), 7.50-7.43 (1H, m), 7.36-7.18 (3H, m), 3.85-3.67 (6H, m), 3.67-3.55 ( 2H, m).
Melting point (° C): 108-113.

(Example 657)
6-Chloro-3- (2,5-dimethylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3939)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 7.14 (1H, d, J = 7.6 Hz), 6.98 (1H, d, J = 7.9 Hz), 6.90 (1H, s), 3.74-3.58 (8H, m), 2.31 (3H, s), 2.13 (3H, s).
Melting point (° C): 98-100.

(Example 658)
6-Chloro-3- (2-methoxy-5-methylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3941)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.62 (1H, s), 7.01 (1H, d, J = 8.2Hz), 7.00 (1H, s), 6.88 (1H, d, J = 8.2Hz), 3.85-3.65 (6H, m), 3.71 (3H, s), 3.65-3.55 (2H, m), 2.30 (3H, s).
Melting point (° C): 179-180.

(Example 659)
6-chloro-3- (2-chloro-6-methylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3944)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.65 (1H, s), 7.30-7.10 (3H, m), 3.75 (6H, s), 3.62 (2H, br.d, J = 4.6Hz), 2.23 (3H, s).
Melting point (° C): 90-92.

(Example 660)
3- (2-Bromo-6-methylphenoxy) -6-chloro-4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3946)
¹ H-NMR (500MHz, CDCl ₃ ) δppm: 7.67 (1H, s), 7.45 (1H, d, J = 7.6Hz), 7.23 (1H, d, J = 7.6Hz), 7.07 (1H, t, J = 7.6Hz), 3.80-3.73 (6H, m), 3.64-3.60 (2H, m), 2.24 (3H, s).
Physical properties: Pasty.

(Example 661)
6-Chloro-3- (2-ethyl-6-methylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3951)
¹ H-NMR (270MHz, CDCl ₃ ) δppm: 7.56 (1H, s), 7.20-7.07 (3H, m), 3.85-3.56 (8H, m), 2.47 (2H, q, J = 7.6Hz), 2.10 (3H, s), 1.14 (3H, t, J = 7.6Hz).
Melting point (° C): 110-115.

(Example 662)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3963)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.56 (1H, s), 7.05 (2H, s), 3.79-3.73 (4H, m), 3.73-3.67 (2H, m), 3.63-3.65 (2H, m), 2.92 (2H, t, J = 7.6 Hz), 2.67 (2H, t, J = 7.6 Hz), 2.14 (3H, s), 2.05 (2H, quintet, J = 7.6 Hz).
Physical properties: amorphous.

(Example 663)
6-Chloro-3- (2,3,5,6-tetramethylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 3970)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.56 (1H, s), 6.91 (1H, s), 3.78-3.68 (6H, m), 3.62-3.57 (2H, m), 2.23 (6H, s) , 1.98 (6H, s).
Melting point (° C): 185-189.

Example 664
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1,3-oxazolidine-3-carboxylate (Compound No. 4010)
100 mg (0.361 mmol) 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol was mixed with toluene (0.4 mL). While stirring, 0.20 mL (0.40 mmol) of 2 mol / L sodium hydroxide aqueous solution was added and stirred for 1 hour. Next, 0.35 mL (0.38 mmol) of a 1.08 mol / L phosgene toluene solution was added, and the mixture was stirred at room temperature for 1 hour. Further, 1,3-oxazolidine 50.0 mg {0.684 mmol, Agricultural and Biological Chemistry, 1991, 55, No. 1, can be produced by the method described on pages 37-43}, Stir at room temperature for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (using MERCK 1.05744, 2 hexanes: ethyl acetate = 2: 1), and 6-chloro-3- (2 52.7 mg (0.140 mmol, yield 38.8%) of -cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1,3-oxazolidine-3-carboxylate (Compound No. 4010) was obtained.
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.15-7.08 (2H, m), 6.90-6.83 (1H, m), 5.07 (1H, s), 4.99 (1H, s) , 4.18-4.10 (2H, m), 3.77-3.72 (1H, m), 3.66-3.61 (1H, m), 2.14 (3H, s), 1.81-1.70 (1H, m), 0.78-0.68 (2H, m), 0.65-0.55 (2H, m).
Melting point (° C): 97-98.

Example 665
6-Chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl dimethyl carbamate (Compound No. 3887)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 7.04 (2H, s), 3.14 (3H, s), 3.05 (3H, s), 2.92 (2H, t, J = 7.6 Hz ), 2.68 (2H, t, J = 7.6 Hz), 2.14 (3H, s), 2.07-2.01 (2H, m).
Melting point (° C): 168-170.

(Example 666)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 1,3-oxazolidine-3-carboxylate (Compound No. 4022)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 7.04 (2H, s), 5.05 (1H, s), 4.97 (1H, s), 4.14-4.09 (2H, m), 3.72 (1H, t, J = 6.5 Hz), 3.62 (1H, t, J = 6.2 Hz), 2.92 (2H, t, J = 7.2 Hz), 2.67 (2H, t, J = 7.6 Hz), 2.14 (3H , s), 2.07-2.01 (2H, m).
Melting point (° C): amorphous.

(Example 667)
6-Chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4-methylbenzoate (Compound No. 4030)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 8.08 (2H, d, J = 8.0 Hz), 7.57 (1H, s), 7.33 (2H, d, J = 8.0 Hz), 7.01 (2H, s), 2.90 (2H, t, J = 7.4 Hz), 2.69 (2H, t, J = 7.4 Hz), 2.45 (3H, s), 2.14 (3H, s), 2.08-1.97 (2H, m).
Melting point (° C): amorphous.

(Example 668)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-piperidinyl carbonate (Compound No. 4037)
¹ H-NMR (270MHz, CDCl ₃ ) δppm: 7.57 and 7.55 (1H, s), 7.12-7.06 (2H, m), 6.86-6.82 (1H, m), 3.87-3.28 (5H, m), 2.14 ( 3H, s), 1.93-1.58 (6H, m), 0.77-0.67 (2H, br. M), 0.62-0.53 (2H, br. M).
Melting point (° C): amorphous.

(Example 669)
6-Chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 3-piperidinyl carbonate (Compound No. 4038)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.55 and 7.53 (1H, s), 7.03 (2H, s), 3.87-3.24 (5H, m), 2.91 (2H, t, J = 7.4 Hz), 2.67 (2H, t, J = 7.4 Hz), 2.13 (3H, s), 2.09-1.80 (5H, m), 1.66-1.50 (2H, m).
Melting point (° C): amorphous.

(Example 670)
6-Chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl bis (cyanomethyl) carbamate (Compound No. 4040)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.58 (1H, s), 7.06 (2H, s), 4.46 (2H, s), 4.39 (2H, s), 2.92 (2H, t, J = 7.6 Hz ), 2.66 (2H, t, J = 7.2 Hz), 2.13 (3H, s), 2.07-2.01 (3H, m).
Melting point (° C): amorphous.

(Example 671)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-hydroxy-1-piperidinecarboxylate (Compound No. 4047)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.55-7.24 (1H, m), 7.12-7.05 (2H, m), 6.86-6.80 (1H, br. M), 4.95 (1H, s), 4.00 ( 1H, dd, J = 13.7, 5.3 Hz), 3.94-3.39 (4H, m), 2.14-2.04 (6H, m), 1.80-1.70 (2H, m), 0.74-0.64 (2H, br.m), 0.62-0.52 (2H, br. M).
Melting point (° C): amorphous.

(Example 672)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 3-hydroxy-1-piperidinecarboxylate (Compound No. 4048)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.53-7.20 (1H, m), 7.04-7.02 (2H, m), 4.94 (1H, br. S), 4.09-3.46 (5H, m), 2.97- 2.83 (2H, m), 2.70-2.63 (2H, m), 2.13-1.90 (8H, m), 1.76-1.60 (1H, m).
Melting point (° C): candy-like.

(Example 673)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-hydroxy-1-piperidinecarboxylate (Compound No. 4055)
Ethanol (2 ml) was added to 100.7 mg (0.251 mmol) of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-oxo-1-piperidinecarboxylate (Compound No. 4079) and iced. Chilled. To this mixture, 5.3 mg (0.14 mmol) of sodium borohydride was added and stirred for 1 hour under ice cooling. To the reaction mixture, brine was added under ice cooling, and the mixture was extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin layer chromatography (developed with MERCK, 1.05744, 2 hexanes: ethyl acetate = 5: 1), and 6-chloro-3- (2 91.7 mg (0.227 mmol, yield 90.5%) of -cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-hydroxy-1-piperidinecarboxylate (Compound No. 4055) was obtained.
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.10-7.06 (2H, m), 6.84 (1H, dd, J = 6.9, 3.4 Hz), 3.99-3.90 (2H, m) , 3.88-3.83 (1H, m), 3.48-3.42 (1H, m), 3.35-3.30 (1H, m), 2.14 (3H, s), 1.90-1.87 (2H, m), 1.78-1.72 (1H, m), 1.62-1.56 (2H, m), 0.76-0.68 (2H, br. m), 0.59-0.52 (2H, br. m).
Melting point (° C): amorphous.

(Example 674)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4-hydroxy-1-piperidinecarboxylate (Compound No. 4056)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 7.03 (2H, s), 4.00-3.82 (3H, m), 3.49-3.29 (2H, m), 2.91 (2H, t, J = 7.4 Hz), 2.67 (2H, t, J = 7.4 Hz), 2.14 (3H, s), 2.09-1.98 (2H, m), 1.96-1.86 (2H, m), 1.69-1.53 (2H, m ).
Melting point (° C): oil.

(Example 675)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (1-pyrrolidinyl) -1-piperidinecarboxylate (Compound No. 4063)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.563 and 7.561 (1H, s), 7.12-7.05 (2H, m), 6.89-6.81 (1H, m), 4.26-4.10 (2H, m), 3.24- 3.14 (1H, m), 3.11-3.00 (1H, m), 2.65-2.50 (4H, m), 2.36-2.18 (1H, m), 2.14 (3H, s), 2.02-1.92 (2H, m), 1.85-1.70 (5H, m), 1.67-1.52 (2H, m), 0.76-0.68 (2H, m), 0.61-0.53 (2H, m).
Melting point (° C.): Paste.

(Example 676)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4- (1-pyrrolidinyl) -1-piperidinecarboxylate (Compound No. 4064)
¹ H-NMR (270MHz, CDCl ₃ ) δppm: 7.55 and 7.54 (1H, s), 7.03 (2H, s), 4.25-4.08 (2H, m), 3.23-3.13 (1H, m), 3.10-3.00 ( 1H, m), 2.91 (2H, t, J = 7.4 Hz), 2.67 (1H, t, J = 7.4 Hz), 2.61-2.53 (4H, m), 2.32-2.21 (1H, m), 2.13 (3H , s), 2.08-1.90 (5H, m), 1.84-1.74 (4H, m), 1.67-1.52 (2H, m).
Melting point (° C.): Paste.

(Example 677)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (methoxyimino) -1-piperidinecarboxylate (Compound No. 4071)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-oxo-1-piperidinecarboxylate (Compound No. 4079) in 55.8 mg (0.139 mmol) to 1,4-dioxane (1 ml) , Methanol (1 ml) and water (0.6 ml) were added. To this mixture, 24.2 mg (0.29 mmol) of O-methyl-hydroxylamine hydrochloride was added and stirred at room temperature for 4 hours. Saturated brine was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off, and 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (methoxyimino) -1-piperidinecarboxylate ( 60.9 mg (0.141 mmol, yield 101%) of Compound No. 4071) was obtained.
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 7.11-7.06 (2H, m), 6.85 (1H, dd, J = 6.9, 2.7 Hz), 3.85 (3H, s), 3.83 (1H, t, J = 6.2 Hz), 3.78 (1H, t, J = 5.8 Hz), 3.71 (1H, t, J = 5.8 Hz), 3.67 (1H, t, J = 6.2 Hz), 2.70-2.67 (2H, m), 2.50-2.45 (2H, m), 2.14 (3H, s), 1.78-1.72 (1H, m), 0.72 (2H, br.d, J = 7.6 Hz), 0.58 (2H, br d, J = 4.1 Hz).
Melting point (° C): oil.

(Example 678)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4- (methoxyimino) -1-piperidinecarboxylate (Compound No. 4072)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.54 (1H, s), 7.04 (2H, s), 3.85 (3H, s), 3.81 (1H, t, J = 5.5 Hz), 3.76 (1H, t , J = 5.8 Hz), 3.71 (1H, t, J = 6.2 Hz), 3.66 (1H, t, J = 6.2 Hz), 2.92 (2H, t, J = 7.6 Hz), 2.68-2.65 (4H, m ), 2.47 (2H, q, J = 6.9 Hz), 2.14 (3H, s), 2.07-2.01 (2H, m).
Melting point (° C): oil.

(Example 679)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-oxo-1-piperidinecarboxylate (Compound No. 4079)
21-5.5 mg (0.779 mmol) 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol was mixed with toluene (3 mL). While stirring, 0.32 mL (0.96 mmol) of 3 mol / L sodium hydroxide aqueous solution was added and stirred for 30 minutes. Next, 0.82 mL (0.886 mmol) of a 1.08 mol / L phosgene toluene solution was added, and the mixture was stirred at room temperature for 30 minutes. Furthermore, a mixture of 196.2 mg (1.28 mmol) of 4-piperidinone hydrochloride monohydrate and 0.52 mL (1.6 mmol) of 3 mol / L aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 2 hours 30 minutes. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the resulting residue was purified by preparative thin-layer chromatography (development using MERCK 1.05717 4 hexanes: ethyl acetate = 1: 1) to give 6-chloro-3- (2 165.2 mg (0.411 mmol, yield 52.8%) of -cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-oxo-1-piperidinecarboxylate (Compound No. 4079) were obtained.
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.56 (1H, s), 7.13-7.06 (2H, m), 6.88-6.83 (1H, m), 4.01 (2H, t, J = 5.9 Hz), 3.90 (2H, t, J = 6.1 Hz), 2.58 (4H, t, J = 5.8 Hz), 2.14 (3H, s), 1.80-1.70 (1H, m), 0.77-0.69 (2H, br.m), 0.62-0.55 (2H, br. M).
Melting point (° C): oil.

(Example 680)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4-oxo-1-piperidinecarboxylate (Compound No. 4080)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 7.05 (2H, s), 3.99 (2H, t, J = 5.8 Hz), 3.89 (2H, t, J = 6.2 Hz), 2.92 (2H, t, J = 7.6 Hz), 2.67 (2H, t, J = 7.2 Hz), 2.57 (4H, q, J = 6.2 Hz), 2.14 (3H, s), 2.07-2.01 (2H, m ).
Melting point (° C): oil.

(Example 681)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-acetyl-1-piperazinecarboxylate (Compound No. 4081)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.57 and 7.53 (1H, s), 7.12-7.07 (2H, m), 6.86-6.84 (1H, m), 3.75-3.65 (4H, m), 3.63- 3.53 (4H, m), 2.14 (3H, s), 2.12 (3H, s), 1.77-1.71 (1H, m), 0.74-0.70 (2H, m), 0.60-0.55 (2H, m).
Melting point (° C.): Paste.

(Example 682)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4-acetyl-1-piperazinecarboxylate (Compound No. 4088)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.56 and 7.52 (1H, s), 7.04 (2H, s), 3.75-3.65 (4H, m), 3.63-3.55 (4H, m), 2.92 (2H, t, J = 7.2 Hz), 2.66 (2H, t, J = 7.6 Hz), 2.13 (3H, s), 2.11 (3H, s), 2.07-2.01 (2H, m).
Melting point (° C.): Paste.

(Example 683)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (4-morpholinylcarbonyl) -1-piperazinecarboxylate (Compound No. 4095)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.56 (1H, s), 7.13-7.08 (2H, m), 6.87-6.83 (1H, m), 3.77-3.61 (8H, m), 3.36-3.28 ( 8H, m), 2.14 (3H, s), 1.79-1.67 (1H, m), 0.78-0.68 (2H, br. M), 0.60-0.54 (2H, br. M).
Melting point (° C): 134-135.

(Example 684)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4- (4-morpholinylcarbonyl) -1-piperazinecarboxylate (compound Number 4096)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.54 (1H, s), 7.04 (2H, s), 3.70-3.60 (8H, m), 3.36-3.28 (8H, m), 2.92 (2H, t, J = 7.4 Hz), 2.66 (2H, t, J = 7.4 Hz), 2.13 (3H, s), 2.09-1.98 (2H, m).
Melting point (° C): amorphous.

Example 685
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinylethyl 1,4-piperazine dicarboxylate (Compound No. 4103)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 7.12-7.07 (2H, m), 6.85 (1H, dd, J = 6.9, 2.1 Hz), 4.17 (3H, q, J = 7.1 Hz), 3.74-3.67 (2H, br.m), 3.65-3.54 (6H, br.m), 2.14 (3H, s), 1.77-1.71 (1H, m), 1.28 (2H, t, J = 7.2 Hz), 0.75-0.69 (2H, br. M), 0.61-0.55 (2H, br.m).
Melting point (° C): oil.

(Example 686)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl ethyl 1,4-piperazine dicarboxylate (Compound No. 4104)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.53 (1H, s), 7.04 (2H, s), 4.17 (2H, q, J = 7.1 Hz), 3.73-3.63 (2H, br. M), 3.57 (6H, br. S), 2.92 (2H, t, J = 7.4 Hz), 2.66 (2H, t, J = 7.4 Hz), 2.13 (3H, s), 2.09-1.98 (2H, m), 1.28 ( 3H, t, J = 7.0 Hz).
Melting point (° C): amorphous.

(Example 687)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-cyano-1-piperazinecarboxylate (Compound No. 4111)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.53 (1H, s), 7.14-7.06 (2H, m), 6.87-6.83 (1H, m), 3.82 (2H, br. S), 3.71 (2H, br) s), 3.35-3.31 (4H, m), 2.13 (3H, s), 1.77-1.67 (1H, m), 0.76-0.68 (2H, br.m), 0.63-0.55 (2H, br. m) ).
Melting point (° C): 147-149.

Example 688 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl 1,4-piperazine dicarboxylate (Compound No. 4119)
While stirring a mixture of 1,4-piperazine dicarbonyl dichloride 111 mg (0.526 mmol) and acetonitrile (3 ml), (2,4-dichlorophenyl) (5-hydroxy-1,3-dimethyl-1H-pyrazole-4 -Il) methanone 151 mg (0.530 mmol) was added followed by 1,4-diazabicyclo [2.2.2] octane 60.0 mg (0.535 mmol) and the mixture was stirred at room temperature for 2 hours. To this mixture was added 147 mg (0.549 mmol) of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol, followed by 60.0 mg (0.535 mmol) of 1,4-diazabicyclo [2.2.2] octane And stirred at room temperature overnight. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was subjected to silica gel column chromatography (Daisogel 1001W, hexane (0.1 L) ⇒ hexane: ethyl acetate (1: 1, 1 L) ⇒ hexane: ethyl acetate (2: 3, 1 L) ⇒Elution with ethyl acetate (1 L) and fractionation into 197 fractions). Fractions 46 to 95 were combined and concentrated to give 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4- (2,4-dichlorobenzoyl) -1,3-dimethyl 168 mg (0.240 mmol, yield 45.6%) of 1H-pyrazol-5-yl 1,4-piperazine dicarboxylate (Compound No. 4119) was obtained.
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.56 and 7.54 (1H, s), 7.44 (1H, s), 7.32-7.25 (2H, m), 7.12-7.08 (2H, m), 6.88-6.84 ( 1H, m), 3.79 (2H, br.s), 3.68 (2H, br.s), 3.64 (3H, s), 3.59-3.55 (4H, m), 2.14 (3H, s), 2.13 (3H, s), 1.78-1.68 (1H, m), 0.75-0.70 (2H, br. m), 0.62-0.56 (2H, br. m).
Melting point (° C): amorphous.

Example 689
Bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] 1,4-piperazine dicarboxylate (Compound No. 4127)
While stirring a mixture of 1,4-piperazine dicarbonyl dichloride 111 mg (0.526 mmol) and acetonitrile (3 ml), (2,4-dichlorophenyl) (5-hydroxy-1,3-dimethyl-1H-pyrazole-4 -Il) methanone 151 mg (0.530 mmol) was added followed by 1,4-diazabicyclo [2.2.2] octane 60.0 mg (0.535 mmol) and the mixture was stirred at room temperature for 2 hours. To this mixture was added 147 mg (0.549 mmol) of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol, followed by 60.0 mg (0.535 mmol) of 1,4-diazabicyclo [2.2.2] octane And stirred at room temperature overnight. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layers were combined, washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was subjected to silica gel column chromatography (Daisogel 1001W, hexane (0.1 L) ⇒ hexane: ethyl acetate (1: 1, 1 L) ⇒ hexane: ethyl acetate (2: 3, 1 L) ⇒Elution with ethyl acetate (1 L) and fractionation into 197 fractions). Fractions 14 to 21 were combined and concentrated to give bis [6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl] 1,4-piperazine dicarboxylate (Compound No. 4127) 93.2 mg (0.135 mmol, yield 25.7%) was obtained.
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 7.53 (1H, s) 7.12-7.06 (4H, m), 6.86-6.83 (2H, m), 3.82 (4H, s), 3.70 (4H, s), 2.13 (6H, s), 1.76-1.69 (2H, m), 0.74-0.68 (4H, br. M), 0.61-0.53 (4H, br. M).
Melting point (° C): amorphous.

(Example 690)
3-[(5-Bromo-2,3-dihydro-1H-inden-4-yl) oxy] -6-chloro-4-pyridazinyl 4-morpholinecarboxylate (Compound No. 4130)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.66 (1H, s), 7.38 (1H, d, J = 8.2 Hz), 7.02 (1H, d, J = 8.2 Hz), 3.78-3.75 (6H, m ), 3.60 (2H, t, J = 4.5 Hz), 2.94 (2H, t, J = 7.6 Hz), 2.80 (2H, t, J = 7.2 Hz), 2.12-2.04 (2H, m).
Melting point (° C): amorphous.

(Example 691)
5,6-Dichloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4-morpholinecarboxylate (Compound No. 4136)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.14-7.06 (2H, m), 6.86-6.83 (1H, m), 3.80-3.70 (4H, m), 3.68-3.60 (4H, m), 2.14 ( 3H, s), 1.82-1.72 (1H, m), 0.80-0.72 (2H, br. M), 0.65-0.55 (2H, br. M).
Melting point (° C.): Gummy.

(Example 692)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-methyl-4-morpholinecarboxylate (Compound No. 4146)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 7.13-7.08 (2H, m), 6.87-6.83 (1H, m), 4.10-3.93 (3H, m), 3.71-3.59 ( 2H, m), 3.32-3.06 (1H, m), 2.92 and 2.76 (1H, t, J = 11.9 Hz), 2.14 (3H, s), 1.80-1.69 (1H, m), 1.22 (3H, d, J = 6.1 Hz), 0.77-0.67 (2H, br. M), 0.63-0.53 (2H, br. M).
Melting point (° C): oil.

(Example 693)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3-methyl-4-morpholinecarboxylate (Compound No. 4154)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.55 (1H, s), 7.13-7.06 (2H, m), 6.88-6.83 (1H, m), 4.25 (1H, br. S), 3.96-3.80 ( 2H, m), 3.76-3.66 (2H, m), 3.60-3.30 (2H, m), 2.14 (3H, s), 1.80-1.70 (1H, m), 1.41 (3H, br.s), 0.76- 0.68 (2H, br. M), 0.61-0.55 (2H, br. M).
Melting point (° C): oil.

(Example 694)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 3-methyl-4-morpholinecarboxylate (Compound No. 4155)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.54 (1H, s), 7.04 (2H, s), 4.24 (1H, br. S), 3.96-3.92 (2H, m), 3.75-3.65 (2H, m), 3.59-3.44 (2H, m), 2.92 (2H, t, J = 7.4 Hz), 2.67 (2H, t, J = 7.5 Hz), 2.14 (3H, s), 2.09-1.98 (2H, m ), 1.39 (3H, br. S).
Melting point (° C): oil.

(Example 695)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,2-dimethyl-1,3-oxazolidine-3-carboxylate (Compound No. 4162)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.95 and 7.83 (1H, s), 7.11-7.09 (2H, m), 6.89-6.84 (1H, m), 4.06 (2H, t, J = 6.3 Hz) , 3.82 and 3.68 (2H, t, J = 6.3 Hz), 2.12 (3H, s), 1.85-1.72 (1H, m), 1.70 and 1.57 (6H, s), 0.77-0.68 (2H, br. M) , 0.60-0.50 (2H, br. M).
Melting point (° C): oil.

(Example 696)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 2,2-dimethyl-1,3-oxazolidine-3-carboxylate (compound Number 4163)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.69 and 7.56 (1H, s), 7.04 (2H, s), 4.06 (2H, t, J = 6.3 Hz), 3.79 and 3.71 (2H, t, J = 6.3 Hz), 2.92 (2H, t, J = 7.3 Hz), 2.67 (2H, t, J = 7.3 Hz), 2.14 (3H, s), 2.09-1.98 (2H, m), 1.69 and 1.61 (6H, s).
Melting point (° C): amorphous.

(Example 697)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2-oxo-1,3-oxazolidine-3-carboxylate (Compound No. 4170)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.06-6.98 (2H, m), 6.83-6.74 (1H, m), 6.53 (1H, s), 4.51 and 4.41 (2H, t, J = 7.9 Hz) , 4.20 and 3.47 (2H, t, J = 7.9 Hz), 2.05 (3H, s), 1.82-1.72 (1H, m), 0.77-0.68 (2H, br.m), 0.58-0.48 (2H, m) .
Melting point (° C): amorphous.

(Example 698)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 4,4-dimethyl-1,3-oxazolidine-3-carboxylate (Compound No. 4178)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.70 and 7.56 (1H, s), 7.10-7.07 (2H, m), 6.89-6.82 (1H, m), 5.13 and 5.07 (2H, s), 3.88 and 3.84 (2H, s), 2.14 (3H, s), 1.80-1.70 (1H, m), 1.57 and 1.50 (6H, s), 0.77-0.67 (2H, br.m), 0.63-0.53 (2H, br m).
Melting point (° C): candy-like.

(Example 699)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 4,4-dimethyl-1,3-oxazolidine-3-carboxylate (compound Number 4179)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.67 and 7.55 (1H, s), 7.04 (2H, s), 5.11 and 5.06 (2H, s), 3.87 and 3.83 (2H, s), 2.92 (2H, t, J = 7.3 Hz), 2.67 (2H, t, J = 7.3 Hz), 2.14 (3H, s), 2.09-2.01 (2H, m), 1.55 and 1.50 (6H, s).
Melting point (° C): amorphous.

(Example 700)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,5-dihydro-1H-pyrrole-1-carboxylate (Compound No. 4186)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.60 (1H, s), 7.11-7.07 (2H, m), 6.85 (1H, dd, J = 6.2, 2.7 Hz), 5.88 (1H, dt, J = 6.2, 2.1 Hz), 5.85 (1H, dt, J = 6.2, 2.1 Hz), 4.45-4.42 (2H, m), 4.33-4.30 (2H, m), 2.15 (3H, s), 1.81-1.75 (1H m), 0.73 (2H, br. d, J = 8.2 Hz), 0.58 (2H, br. d, J = 4.8 Hz).
Melting point (° C): oil.

(Example 701)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 2,5-dihydro-1H-pyrrole-1-carboxylate (Compound No. 4187 )
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.59 (1H, s), 7.06-7.02 (2H, m), 5.86 (2H, dtd, J = 20.6, 4.5, 2.3 Hz), 4.43-4.40 (2H, m), 4.32-4.30 (2H, m), 2.92 (2H, t, J = 7.2 Hz), 2.68 (2H, t, J = 7.6 Hz), 2.15 (3H, s), 2.07-2.01 (2H, m ).
Melting point (° C): oil.

(Example 702)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,6-dihydro-1 (2H) -pyridinecarboxylate (Compound No. 4194)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.60 (1H, s), 7.11-7.07 (2H, m), 6.86-6.85 (1H, m), 5.94-5.87 (1H, m), 5.75-5.68 ( 1H, m), 4.19 (1H, t, J = 2.7 Hz), 4.06 (1H, t, J = 2.7 Hz), 3.78 (1H, t, J = 5.5 Hz), 3.66 (1H, t, J = 5.8 Hz), 2.30-2.23 (2H, br.m), 2.15 (3H, s), 1.79-1.73 (1H, m), 0.75-0.69 (2H, br.m), 0.60-0.55 (2H, br.m) ).
Melting point (° C): 93-96.

(Example 703)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 3,6-dihydro-1 (2H) -pyridinecarboxylate (Compound No. 4195 )
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.57 (1H, s), 7.03 (2H, s), 5.96-5.83 (1H, m), 5.74-5.66 (1H, m), 4.16 (1H, br. s), 4.04 (1H, br.s), 3.75 (1H, t, J = 5.7 Hz), 3.65 (1H, t, J = 5.7 Hz), 2.91 (2H, t, J = 7.3 Hz), 2.68 ( 2H, t, J = 7.3 Hz), 2.25 (2H, br. S), 2.14 (3H, s), 2.09-1.98 (2H, m).
Melting point (° C): candy-like.

(Example 704)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1,4-oxazepan-4-carboxylate (Compound No. 4202)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.55 and 7.54 (1H, s), 7.13-7.06 (2H, m), 6.87-6.83 (1H, m), 3.86-3.74 (6H, m), 3.72- 3.64 (2H, m), 2.14 (3H, s), 2.08-1.95 (2H, m), 1.81-1.70 (1H, m), 0.79-0.67 (2H, m), 0.62-0.53 (2H, m).
Melting point (° C.): Paste.

(Example 705)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1-indoline carboxylate (Compound No. 4210)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.85 (0.8H, d, J = 8.2 Hz), 7.80-7.75 (0.4H, m), 7.65 (0.8H, s), 7.27-7.05 (5H, m ), 6.87-6.83 (1H, m), 4.30 (1.6H, t, J = 8.2 Hz), 4.18 (0.4H, t, J = 8.2 Hz), 3.26-3.20 (2H, m), 2.16 (3H, s), 1.81-1.76 (1H, m), 0.75-0.70 (2H, m), 0.60-0.55 (2H, m).
Melting point (° C): 172-173.

(Example 706)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 1-indoline carboxylate (Compound No. 4211)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.86 (0.8H, d, J = 7.9 Hz), 7.78-7.72 (0.4H, m), 7.64 (0.8H, s), 7.28-7.02 (5H, m ), 4.28 (1.6H, t, J = 8.6 Hz), 4.18 (0.4H, t, J = 8.7 Hz), 3.25 (2H, t, J = 8.3 Hz), 2.91 (2H, t, J = 7.3 Hz) ), 2.69 (2H, t, J = 7.4 Hz), 2.15 (3H, s), 2.09-1.98 (2H, m).
Melting point (° C): 185-189.

(Example 707)
6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 1,3-dihydro-2H-isoindole-2-carboxylate (Compound No. 4218)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.66 and 7.65 (1H, s), 7.38-7.24 (4H, m), 7.13-7.06 (2H, m), 6.88-6.81 (1H, m), 4.99 ( 2H, s), 4.87 (2H, s), 2.17 (3H, s), 1.85-1.75 (1H, m), 0.79-0.70 (2H, m), 0.62-0.54 (2H, m).
Melting point (° C): amorphous.

(Example 708)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 1,3-dihydro-2H-isoindole-2-carboxylate (compound no. 4219)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.64 and 7.63 (1H, s), 7.34-7.25 (4H, m), 7.03 (2H, s), 4.97 (2H, s), 4.86 (2H, s) , 2.91 (2H, t, J = 7.4 Hz), 2.70 (2H, t, J = 7.4 Hz), 2.16 (3H, s), 2.09-1.98 (2H, m).
Melting point (° C.): Paste.

(Example 709)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 3,4-dihydro-1 (2H) -quinolinecarboxylate (Compound No. 4226)
¹ H-NMR (500 MHz, CDCl ₃ ) δppm: 7.78 (1H, br. S), 7.54 (1H, br. S), 7.19-7.14 (2H, m), 7.11-7.07 (3H, m), 6.85 ( 1H, dd, J = 6.2, 2.7 Hz), 3.94 (2H, br.s), 2.84 (2H, t, J = 6.5 Hz), 2.16 (3H, s), 2.06 (2H, quintet, J = 2.1 Hz ), 1.80-1.74 (1H, m), 0.72 (2H, br. D, J = 8.2 Hz), 0.58 (2H, br. D, J = 4.8 Hz).
Melting point (° C): amorphous.

(Example 710)
6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 3,4-dihydro-1 (2H) -quinolinecarboxylate (Compound No. 4227 )
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.75 (1H, br. S), 7.53 (1H, br. S), 7.21-7.04 (5H, m), 4.00-3.87 (2H, br. M), 2.92 (2H, t, J = 7.5 Hz), 2.84 (2H, t, J = 6.6 Hz), 2.69 (2H, t, J = 7.4 Hz), 2.15 (3H, s), 2.10-1.99 (4H, m ).
Melting point (° C): oil.

(Example 711)
6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinyl 2,3-dihydro-4H-1,4-benzoxazine-4-carboxylate (Compound No. 4234)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.96 (1H, br. S), 7.57 (1H, br. S), 7.13-7.05 (3H, m), 6.94-6.83 (3H, m), 4.36 ( 2H, t, J = 4.5 Hz), 4.10 (2H, br.s), 2.15 (3H, s), 1.80-1.70 (1H, m), 0.75-0.68 (2H, br.m), 0.60-0.54 ( 2H, br. M).
Melting point (° C): amorphous.

(Example 712)
6-Chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinyl 2,3-dihydro-4H-1,4-benzoxazine-4-carboxy Rate (Compound No. 4235)
¹ H-NMR (270 MHz, CDCl ₃ ) δppm: 7.96 (1H, br. S), 7.56 (1H, br. S), 7.11-7.04 (3H, m), 6.95-6.90 (2H, m), 4.36 ( 2H, t, J = 4.5 Hz), 4.16-4.08 (2H, m), 2.92 (2H, t, J = 7.5 Hz), 2.68 (2H, t, J = 7.4 Hz), 2.14 (3H, s), 2.10-1.99 (2H, m).
Melting point (° C): oil.

  Compound Nos. 1 and 6 can be produced according to the method of Example 2.

  Compound Nos. 123-127, 130-138, 144, 145, 151, 163, 173, 184, 202, 217, 226, 249, 264, 265, 266, 267, 269-275, 279, 280, 284, 287, 288, 292, 293, 300, 304, 305, 306, 307, 308, 309, 311, 315, 324, 325, 329, 330, 334, 336, 339, 344, 348, 349, 355, 356, 359, 361, 362, 364-370, 375, 376, 379, 383, 385-387, 390, 391, 396, 399-401, 403, 410, 412, 413, 415-425, 426, 427, 430, 432 438, 441, 443, 446, 450, 453, 454, 456, 58-460, 472, 491, 498, 503, 505, 506, 507, 510, 513, 514, 520, 521, 527-529, 531, 532, 534-536, 538-541, 544, 547, 549, 552, 556, 557, 558, 559, 562, 566, 567, 571, 614, 618, 621, 623, 626 to 629, 635, 640, 642, 650, 653, 658, 659, 662 to 664, 667, 679, 680, 692, 700, 701, 702, 707-712, 716, 717, 719, 731-733, 734, 735-737, 740, 746, 754, 756, 758, 759, 762, 775, 778, 780 to 782, 802 to 804, 834, 835, 844 to 846, 8 0, 890, 894, 896, 911, 914, 931, 964, 965, 979, 982, 987, 998, 1000, 1007, 1009, 1013, 1016, 1020, 1023, 1027, 1040, 1050, 1052, 1053, 1055, 1058, 1060, 1061, 1063, 1064, 1066, 1069, 1073, 1080, 1083, 1086, 1088, 1089, 1091, 1096, 1099, 1100, 1102, 1115, 1118-1120, 1122-1125, 1129, 1133, 2519, 2547, 2548, 2565, 2568, 2570, 2571, 2574, 2577, 2585, 2587, 2589, 2592, 2597, 2599, 2600, 2601, 2605, 260 The compounds of Nos. 7, 2608, 2609 and 2614 can be produced according to the method described in Example 1, Example 6, Example 13, Example 16, Example 21, Example 22 or Example 23.

  Compound Nos. 1140, 1151, 1160, 1172, 1178, 1184, 1207, 1251, 1260, 1266, 1286, 1298, 1334, 1340, 1358, 1364, 1382, 1387, 1391, 1396, 1417, 1441, 1446, 1448, 1450, 1455-1459, 1461, 1481, 1509, 1522, 1531, 1537, 1543, 1549, 1553, 1554, 1566, 1575, 1593, 1599, 1603, 1616, 1643, 1649, 1658, 1706, 1710, 1757, 1770, 1789, 1811, 1840, 1877, 1879, 1881, 1898, 1924, 1981, 1985, 2010, 2034, 2038, 2040, 2042, 205 2060, 2066, 2072, 2106, 2136, 2147, 2151, 2176, 2198-2200, 2212, 2220-2224, 2230-2232, 2234-2238, 2240, 2245-2249, 2263, 2265, 2287, 2289, 2300 , 2309, 2315, 2321, 2351, 2662, 2671, 2677, 2697, 2703, 2709, 2715, 2721, 2727, 2752, 2758, 2764, 2770, 2776, 2782, 2788, 2805, 2814, 2820, 2826, 2850 , 2856, 2862, 2868, 2874, 2880, 2900, 2906, 2918, 2924, 2930, 2961, 2970, 2976, 2982, 2988, 2994, 3 16, 3022, 3028, 3034, 3040, 3046, 3052, 3058, 3064, 3070, 3076, 3082, 3088, 3094, 3100, 3106, 3112, 3129, 3138, 3144, 3150, 3156, 3162, 3168, 3185, 3194, 3200, 3217, 3226, 3243, 3252, 3258, 3264, 3270, 3276, 3282, 3288, 3294, 3300, 3306, 3312, 3318, 3324, 3330, 3336, 3342, 3348, 3354, 3360, 3366, 3372, 3378, 3384, 3390, 3396, 3402, 3408, 3414, 3420, 3426, 3432, 3438, 3444, 3450, 3456, 3462, 3468, Compounds Nos. 3474, 3480, 3486, 3492, 3498, 3504, 3510, 3516, 3780, 3786, 3792, 3856 and 4030 can be prepared according to the method described in Example 26, Example 27 or Example 28. .

  The compound of Compound No. 2402 can be produced according to the method described in Example 33.

  Compounds Nos. 2418 and 2431 can be produced according to the method described in Example 1, Example 6 or Example 22.

  Compound No. 2478 can be produced according to the method described in Example 35, Example 36, Example 37, Example 39 or Example 40.

  The compound of Compound No. 2492 can be produced according to the method described in Example 41.

  Compounds Nos. 1620, 1631, 2827 and 3001 can be produced according to the method described in Example 635.

  Compound Nos. 1889, 1891, 1911, 1920, 1946, 1952, 1958, 3522, 3528, 3534, 3540, 3546, 3552, 3558, 3570, 3576, 3582, 3588, 3594, 3600, 3606, 3612, 3618, 3624, 3636, 3642, 3648, 3654, 3660, 3666, 3672, 3678, 3684-3690, 3696, 3702, 3708, 3714, 3720, 3877, 3894, 3920, 3939, 3944, 3944, 3946, 3951, 3963, 3970, 4022, 4037, 4038, 4040, 4047, 4048, 4055, 4056, 4063, 4064, 4071, 4072, 4080, 4087, 4088, 4095, 409 4103, 4104, 4111, 4130, 4146, 4154, 4155, 4162, 4163, 4170, 4178, 4179, 4186, 4187, 4194, 4195, 4202, 4210, 4211, 4218, 4219, 4226, 4227, 4234, 4235 Compound No. can be produced according to the method described in Example 26, Example 27, Example 28, Example 638, Example 639, Example 640, Example 655, Example 664 or Example 679.

  The compound of Compound No. 2327 can be produced according to the method described in Example 636.

  The compound of Compound No. 2733 can be produced according to the method described in Example 637.

  The compound of Compound No. 3811 can be produced according to the method described in Example 645.

  Compounds Nos. 3837, 3849 and 4136 can be produced according to the method described in Example 646.

  The compound of Compound No. 4056 can be produced according to the method described in Example 673.

  The compound of Compound No. 4072 can be produced according to the method described in Example 677.

In the following formulation examples, “%” indicates mass%.
(Formulation example 1)
Wettable compound of Example 1 (Compound No. 128) (10 parts by mass), Carplex # 80D (manufactured by Shionogi & Co., Ltd., 10 parts by mass), Gohsenol GL05 (manufactured by Nippon Synthetic Chemical Co., Ltd., 2 parts by mass) , New Coal 291PG (dioctylsulfosuccinate sodium salt, Nippon Emulsifier Co., Ltd., 0.5 parts by mass), Neogen Powder (Daiichi Kogyo Seiyaku Co., Ltd., 5 parts by mass), Radiolite # 200 (Showa Chemical Industry) Co., Ltd., 10 parts by mass) and H derivative (Keiwa Furnace Co., Ltd., 62.5 parts by mass) are thoroughly mixed and pulverized with EK sample mill KII-1 type (Fuji Powder Co., Ltd.). A wettable powder was obtained.

(Formulation example 2)
Granules Compound of Example 61 (Compound No. 136) (5 parts by mass), sodium tripolyphosphate (Mitsui Chemicals, 2 parts by mass), 1 (dextrin, manufactured by Nippon Starch Chemical Co., Ltd., 1.5 parts by mass), bentonite (manufactured by Toyoshun Mining Co., Ltd., 25 parts by mass) and calcium carbonate calfin 600 (manufactured by Adachi Lime Co., Ltd., 66.5 parts by mass) Is mixed in a kneader (Fuji Sangyo Co., Ltd., FM-NW-5 type), kneaded water (13 parts by mass) is added, and further mixed, Dome Gran (Fuji Powdar Co., Ltd., screen 1.0 mmφ) Was extruded and granulated. The obtained granulated product was dried with a shelf type dryer (manufactured by Tabai Co., Ltd., PERFECT OVEN PS-222 type, 60 ° C.) and then sieved to 600 to 1190 mm to obtain granules.

(Formulation example 3)
Granule wettable powder The compound of Example 7 (Compound No. 140) (80 parts by mass), Geropon SC / 213 (polycarboxylic acid type surfactant, manufactured by Rhodia Co., Ltd., 7 parts by mass), Neoperex No. 6F powder (dodecylbenzenesulfonate, Kao Corporation, 3 parts by mass) 1 (5 parts by mass) and titanium oxide (Sakai Chemical Industry Co., Ltd., 5 parts by mass) were mixed and pulverized by an air mill (SK-JET O MIZER model 0101, manufactured by Seishin Enterprise Co., Ltd.), then in a rotary mixer In addition, spray water to granulate. When most of the granules are 1.00 mm to 0.15 mm, the granules are taken out, dried by a shelf dryer, and sieved to obtain a granule wettable powder of 1.00 mm to 0.15 mm.

(Formulation example 4)
Aqueous Suspension Compound of Example 171 (Compound No. 506) (10 parts by mass), New Coal 291PG (1 part by mass), Pearl Rex CP (calcium lignin sulfonate, Nippon Paper Industries Co., Ltd., 10 parts by mass), Propylene glycol (manufactured by Nippon Emulsifier Co., Ltd., 10 parts by mass) and water (69 parts by mass) were mixed and pulverized together in an attritor (Mitsui Mining Co., Ltd.) until the solid particles had a diameter of 5 μm or less. To this pulverized slurry (90 parts by mass), 0.05% (W / W) xanthan gum aqueous solution (10 parts by mass) was added and mixed to obtain an aqueous suspension.

(Formulation example 5)
Compound (10 parts by mass) of wettable powder Example 23 (Compound No. 806), Compound A (10 parts by mass), Carplex # 80D (manufactured by Shionogi & Co., Ltd., 10 parts by mass), Gohsenol GL05-S (Japan) Synthetic Chemical Co., Ltd., 2 parts by mass), New Coal 291PG (dioctylsulfosuccinate sodium salt, Nippon Emulsifier Co., Ltd., 0.5 parts by mass), Neogen Powder (Daiichi Kogyo Seiyaku Co., Ltd., 5 parts by mass) ), Radiolite # 200 (manufactured by Showa Chemical Co., Ltd., 10 parts by mass) and H derivative (manufactured by Keiwa Furnace Co., Ltd., 52.5 parts by mass) were sufficiently mixed. The mixture was pulverized with an air mill (SK-JET O MIZER model 0101, manufactured by Seishin Enterprise Co., Ltd.) to obtain a mixed wettable powder of the compound of Example 23 (10%) and Compound A (10%).

(Test Example 1)
Test of herbicidal effect and phytotoxicity to transplanted paddy rice 1 / 10,000a pot was filled with paddy field soil, and the seeds of Tainubie, firefly and perennial broad-leaved weeds (Azena and Kikashigusa) that had become dormant were mixed in 1 cm surface layer. In addition, the tubers of the sprouted pearl millet were planted, and the rice seedlings at the 2.2th leaf stage were transplanted to be submerged and grown in a greenhouse. Three days after transplantation, the prescribed amount of wettable powder prepared according to Formulation Example 1 was diluted in water, the spray solution was treated with flooded soil, and the herbicidal effect and phytotoxicity to transplanted rice were measured 25 days after treatment. . Moreover, 3- (2-allylphenoxy) -6-chloro-4-methoxypyridazine described in Chemical Pharmaceutical Bulletin, 1972, Vol. 20, No. 10, pages 2191-2203 as a comparative compound Using. The results are shown in Table 2. The herbicidal effect and phytotoxicity to transplanted rice were determined according to the following criteria, and “-” in the table represents no test.
Criterion 0: Growth inhibition rate 0-10%
1: Growth suppression rate 11-30%
2: Growth inhibition rate 31-50%
3: Growth inhibition rate 51-70%
4: Growth inhibition rate 71-90%
5: Growth suppression rate 91-100%.

(Test Example 2)
Test of herbicidal effect (soil treatment)
The field soil was filled in 150 cm ² pot, seeded with Echinochloa crus-galli and mustard, and grown in a greenhouse. On the day after sowing, the prescribed amount of wettable powder prepared according to Formulation Example 1 was diluted with water and treated with soil. The herbicidal effect was determined according to the criteria of Test Example 21 21 days after the treatment, and the results are shown in Table 3.

(Test Example 3)
Test of herbicidal effect (stem and leaf treatment)
150 cm ² pots were filled with field soil, seeded with lobster, malva morning glory, mustard, physalis and blue-headed hawk and grown in a greenhouse. After weeds grew to about 10 to 15 cm, the prescribed amount of wettable powder prepared according to Formulation Example 1 was diluted with water containing 0.05% Gramine S and treated with foliage. 14 days after the treatment, the herbicidal effect was determined according to the criteria of Test Example 1, and the results are shown in Table 4. In the table, “-” indicates no test.

(Test Example 4)
Test of herbicidal effect and phytotoxicity to transplanted rice
A 1 / 5000a Wagner pot was filled with paddy soil, and dormant awakened Tainubie, firefly, and annual broad-leaved weeds (Azena and kikashigusa) seeds were mixed in a surface layer of 1 cm. In addition, a tuber of Mizugayatsuri, Urikawa and Krogwei awakened from dormancy was planted, and rice seedlings at 2.2 leaf stage were transplanted, submerged, and grown in a greenhouse. 3 days after transplantation, the prescribed amount of wettable powder prepared according to Formulation Example 5 was diluted in water and treated with flooded soil, and 25 days later, herbicidal effects and phytotoxicity to transplanted rice were determined according to the criteria of Test Example 1. The results are shown in Table 5. Compounds A, B, and C represent pyrazolate, pyrazoxifene, and benzophenap, respectively.

Claims (15)

General formula

[In the formula, R ¹ represents a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₃ -C ₆ cycloalkyl group, C ₂ -C ₆ alkenyl group, a cyano group, A C ₂ -C ₇ alkylcarbonyl group, a di (C ₁ -C ₆ alkyl) carbamoyl group, an optionally substituted phenyl group (the substituent is a substituent selected from the following substituent group A), 5 or 6-membered heterocyclic group (the heterocyclic ring may contain one nitrogen atom, oxygen atom or sulfur atom, and may further contain 1 or 2 nitrogen atoms in the ring), C _1- . A C ₆ alkoxy group, an optionally substituted phenoxy group (the substituent is a substituent selected from the following substituent group A) or an optionally substituted 5- or 6-membered heterocyclic oxy group {the heterocyclic ring is Contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and one or two more Of nitrogen atoms. The substituent is a substituent selected from the group consisting of an optionally substituted benzoyl group (the substituent is a substituent selected from the following substituent group A) and a C _{1 to} C ₆ alkyl group. },
R ² represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a (C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkyl group, a benzoyl group which may be substituted (the substituent is the following substituent group) A substituent selected from A.), a C ₂ -C ₇ alkoxycarbonyl group, an optionally substituted phenoxy group (the substituent is a substituent selected from the following substituent group A), substituted. A good phenylthio group (the substituent is a substituent selected from the following substituent group A) or a tri (C ₁ -C ₆ alkyl) silicon group;
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom or an optionally substituted C ₁ -C ₆ alkyl group (the substituent is selected from the following substituent group B) A C ₂ -C ₆ alkenyl group which may be substituted (the substituent is a cyano group or a nitro group), a C ₂ -C ₆ alkynyl group, a C ₃ which may be substituted. -C ₆ cycloalkyl group (said substituent is a substituent selected from substituent group C.), C ₄ ~C ₁₀ bicycloalkyl group, a cyano group, a formyl group, C ₂ -C ₇ alkylcarbonyl group , A benzoyl group which may be substituted (the substituent is a substituent selected from the following substituent group A), a carboxyl group, a C ₂ -C ₇ alkoxycarbonyl group, a carbamoyl group, a di (C ₁ -C _6). Alkyl) carbamoyl group, optionally substituted phenyl A group (the substituent is a substituent selected from the following substituent group A), an optionally substituted 3- to 6-membered heterocyclic group (the heterocyclic ring includes one nitrogen atom, (It contains an oxygen atom or a sulfur atom, may further contain 1 to 2 nitrogen atoms, and may be condensed with a benzene ring. The substituent is a substituent selected from the following substituent group E.) , amino group which may be substituted (the substituent is a substituent selected from substituent group D.), a nitro group, a hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ haloalkoxy group, (C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkoxy group, optionally substituted phenoxy group (the substituent is substituted with a hydroxyl group or a substituent selected from a halogen atom and a C ₁ -C ₆ alkoxy group) A pyridazinyloxy group), which may be substituted; Ring oxy group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 to 2 nitrogen atoms. is a substituent selected from group E.), which may be substituted phenylsulfonyloxy group (the substituent is a substituent selected from substituent group a.), C ₁ ~C ₆ alkylthio group, A C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ alkylsulfonyl group or a tri (C ₁ -C ₆ alkyl) silicon group, or R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are Two adjacent groups may be substituted together with the carbon atom to which each is bonded. The 3- to 6-membered cyclic hydrocarbon group (the cyclic hydrocarbon is selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom) Interrupted by one or two identical or different heteroatoms There. The substituents are halogen atom, C ₁ -C ₆ alkyl group, a hydroxy C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, a oxo group, hydroxyimino group or a C ₁ -C ₆ alkoxyimino group If the C ₁ -C ₆ alkyl group is substituted, it may form a new 3-membered ring with other C ₁ -C ₆ alkyl group or a carbon atom on the ring. )
m and n each independently represent 0 or 1,
Substituent Group A consists of halogen atoms, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₃ -C ₆ cycloalkyl group, a cyano group and a tri (C ₁ -C ₆ alkyl) silyl group A group,
Substituent group B, a halogen atom, C ₃ -C ₆ cycloalkyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a phenyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, consisting of C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₄ alkylenedioxy group, hydroxyimino group and C ₁ -C ₆ alkoxyimino group A group,
Substituent group C includes a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent is a substituent selected from the above substituent group B), a C ₃ -C ₆ cycloalkyl group, C ₂ -C ₆ alkenyl group, cyano group, C ₂ -C ₇ alkylcarbonyl group, a benzoyl group, a carboxyl group, C ₂ -C ₇ alkoxycarbonyl group, a carbamoyl group, a di (C ₁ -C ₆ alkyl) carbamoyl group, A phenyl group which may be substituted (the substituent is a substituent selected from the above substituent group A), a 5- or 6-membered heterocyclic group (the heterocyclic ring has one nitrogen atom in the ring; , An oxygen atom or a sulfur atom, and further may contain 1 to 2 nitrogen atoms.), An amino group which may be substituted (the substituent is a substituent selected from the following substituent group D) .), a nitro group, a hydroxyl group, C ₁ -C ₆ alkoxy Group, a C ₁ -C ₆ haloalkoxy group, a phenoxy group, C ₁ -C ₆ alkylthio group, a phenylthio group, C ₁ -C ₆ alkylsulfinyl group consisting Le group and C ₁ -C ₆ alkylsulfonyl group,
Substituent group D is, C ₁ -C ₆ alkyl group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a di (C ₁ -C ₆ alkyl) carbamoyl group and C ₁ -C ₆ alkyl A group consisting of a sulfonyl group,
Substituent group E includes a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a hydroxyl group, an optionally substituted phenylsulfonyl group (the substituent is a substituent selected from substituent group A above) And di (C ₁ -C ₆ alkyl) sulfamoyl groups. ]
A pesticide containing a compound represented by the formula: R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group (the halogen atom is 1 to 3 fluorine atoms), cyclo Propyl group, C ₂ -C ₃ alkenyl group, cyano group, C ₂ -C ₄ alkylcarbonyl group, di (C ₁ -C ₃ alkyl) carbamoyl group, optionally substituted phenyl group {the substituent is a fluorine atom, Chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (the halogen atom is the same or different 1 to 3 selected from the group consisting of fluorine atom, chlorine atom and bromine atom) ₁ or 2 substituents selected from the group consisting of a cyclopropyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group. }, A furyl group, a thienyl group, C ₁ -C ₃ alkoxy group, which may be substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ A haloalkyl group (the halogen atom is 1 to 3 fluorine atoms), a cyclopropyl group, a cyano group, and a tri (C ₁ -C ₃ alkyl) silicon group selected from the same or different 1 Two substituents. } Or substituted pyrazolyloxy group (the substituent is two one benzoyl group and two C ₁ -C ₃ alkyl group substituted by a chlorine atom.) Is, according to claim 1 Pesticides. The agricultural chemical according to claim 1, wherein R ¹ is a chlorine atom, a bromine atom, a trifluoromethyl group or a cyano group. The agrochemical according to claim 1, wherein R ¹ is a chlorine atom or a bromine atom. The agrochemical according to claim 1, wherein R ¹ is a chlorine atom. R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C ₁ -C ₃ alkyl group, a (C ₁ -C ₃ alkoxy) C ₁ -C ₃ alkyl group, an optionally substituted benzoyl group { The substituent is a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group (the halogen atom is selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom) 1 to 3 halogen atoms which are the same or different.), ₁ to 2 substituents which are the same or different and are selected from the group consisting of a cyclopropyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silicon group. It is a group. }, C ₂ -C ₄ alkoxycarbonyl group, may be substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen The atoms are the same or different 1 to 3 halogen atoms selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom.), Cyclopropyl group, cyano group and tri (C ₁ -C ₃ alkyl) It is the same or different 1-2 substituents selected from the group consisting of silicon groups. }, Which may be substituted phenylthio group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, a chlorine atom and same selected from the group consisting of bromine or different 1 to 3 halogen atoms.), the same is selected from the group consisting of cyclopropyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silyl group Or it is 1 to 2 different substituents. } Or the agrochemical according to claim 1, which is a tri (C ₁ -C ₃ alkyl) silicon group. The agricultural chemical according to any one of claims 1 to 5, wherein R ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethoxycarbonyl group, or a trimethylsilyl group. The agricultural chemical according to any one of claims 1 to 5, wherein R ² is a hydrogen atom. R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently of each other a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted C ₁ -C ₄ alkyl group The group is the same or different 1 to 3 substituents selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom, or a C _{3 to} C ₄ cycloalkyl group, a C _{1 to} C ₃ alkylthio group or C _1. -C is a ₃ alkoxyimino group.), C ₂ -C ₃ alkenyl group, C ₂ -C ₃ alkynyl group may be substituted C ₃ -C ₅ cycloalkyl group (said substituent is a fluorine atom, a chlorine atom , bromine atom, C ₁ -C ₃ alkyl group, C ₃ -C ₄ cycloalkyl group, the same or different 1 selected from the group consisting of cyano group, C ₁ -C ₃ alkoxy groups and C ₁ -C ₃ alkylthio group a to 3 substituents.), C ₆ ~C ₇ Bishiku Roarukiru group, cyano group, C ₂ -C ₄ alkylcarbonyl group, C ₂ -C ₄ alkoxycarbonyl group, which may be substituted phenyl group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group or a C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, a chlorine atom and one to three halogen atoms selected same or different from the group consisting of bromine atoms.) it is. }, A 5- to 6-membered heterocyclic group which may be substituted {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms. It's okay. The substituents are fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl and C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, selected from the group consisting of chlorine and bromine 1 to 3 halogen atoms which are the same or different. The same or different 1 to 2 substituents selected from the group consisting of: }, Nitro group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ haloalkoxy group (said halogen atom is a fluorine atom, 1-3 was selected same or different from the group consisting of chlorine and bromine which is a halogen atom.), which may be substituted phenoxy group (the substituent is a fluorine atom, a chlorine atom, pyridazinium substituted with a substituent selected from bromine atom, and C ₁ -C ₃ alkoxy group Gini oxy Or a C ₁ -C ₃ alkylthio group, or R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ are bonded together with the carbon atom to which they are adjacent to each other. _{Te, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH = CH-CH = CH- , -OCH ₂ CH _2- , -OCH = CH-, -OCH = C (CH ₃ )-, -SCH = CH-, -N = CH-CH = CH-, -OCH ₂ O-, -OCH ₂ CH ₂ O-,

The agricultural chemical according to any one of claims 1 to 8, which is a group represented by the formula: R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently of each other a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted C ₁ -C ₄ alkyl group The group is 1 to 3 fluorine atoms or one cyclopropyl group.) An optionally substituted C _{3 to} C ₄ cycloalkyl group (the substituent is a fluorine atom, a chlorine atom, or a bromine atom) a C ₁ -C ₂ alkyl group, the same one or two substituents selected from the group consisting of cyclopropyl group, and C ₁ -C ₂ alkoxy group.), a cyano group, C ₂ -C ₃ alkoxycarbonyl group, a nitro group, a C ₁ -C ₃ alkoxy group or a trifluoromethoxy group, or a carbon atom ^{R 3, R 4, R 5} , R 6 and R ^7, two adjacent is, that each bind -CH ₂ CH ₂ CH _2- , -CH (CH ₃ ) CH ₂ CH _2- , -OCH ₂ CH _2- , -OCH = CH- or

The agrochemical according to any one of claims 1 to 8, wherein R ³ is not a hydrogen atom. R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C ₁ -C ₃ alkyl group, or an optionally substituted C ₃ -C ₄ cycloalkyl group (said substituent is the same 1 to 2 substituents selected from the group consisting of a chlorine atom and C ₁ -C ₂ alkyl group.), a cyano group or a C ₁ -C ₂ an alkoxy group, ^{or, R 3, R 4, R} 5, R 6 and R ^7, two adjacent, together with the carbon atoms bonded thereto, -CH ₂ CH ₂ CH ₂ - or The agrochemical according to claim 1, which is a group represented by —OCH═CH—, wherein R ³ is not a hydrogen atom. R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, isopropyl group, or optionally substituted cyclo A propyl group (the substituent is two chlorine atoms) or a methoxy group, or R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ are bonded to each other. together with the carbon atoms to, -CH ₂ CH ₂ CH ₂ - or a group represented by the proviso, R ³ is not a hydrogen atom, pesticide according to any one of claims 1 to 8.   The pesticide according to any one of claims 1 to 12, wherein m and n are both 0. The agrochemical according to any one of claims 1 to 13, which is selected from the following compound group.
The compound group includes 6-chloro-3- (2-iodophenoxy) -4-pyridazinol, 6-chloro-3- (2-methylphenoxy) -4-pyridazinol, 6-chloro-3- (2-cyclopropylphenoxy) ) -4-pyridazinol, 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinol, 3- (1-benzofuran-7-yloxy) -6-chloro-4- Pyridazinol, 6-chloro-3- (2-methoxy-5-methylphenoxy) -4-pyridazinol, 6-chloro-3- (2-chloro-6-cyclopropylphenoxy) -4-pyridazinol, 3- (2- Bromo-6-methylphenoxy) -6-chloro-4-pyridazinol, 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol and 6-chloro-3- (2-cyclopropyl- 3,5-dimethylphenoxy) -4-pyridazinol. The agricultural chemical according to any one of claims 1 to 14, wherein the agricultural chemical is a paddy herbicide or a field crop herbicide.