JP5113531B2 - (3-Sulfur atom substituted phenyl) pyrazole derivatives - Google Patents

Description

  The present invention relates to a pesticide containing, as an active ingredient, a (3-sulfur atom-substituted phenyl) pyrazole derivative or a salt thereof, a substituted phenylpyrazole compound or a (3-sulfur atom-substituted phenyl) pyrazole derivative or a salt thereof as an intermediate for production thereof. Relates to the composition.

  Conventionally, as a (3-sulfur atom substituted phenyl) pyrazole derivative, for example, a 5- (3-sulfur atom substituted phenyl) pyrazole derivative in which a phenyl group is substituted from the 5-position carbon of pyrazole has been described as a herbicide use. (For example, see Patent Documents 1 and 2). However, the substituent at the 3-position of the corresponding pyrazole is limited to a substituent to which an oxygen or sulfur atom is directly bonded, and uses other than herbicides are not known at all.

  Further, 3- (3-sulfur atom substituted phenyl) pyrazole derivatives bonded from the 3-position of pyrazole are described (for example, see Patent Documents 3, 4, 5, 6 and 7). However, the substituent at the 1-position of pyrazole in the present application is limited to an aromatic group such as a phenyl group, and these patents are described only for pharmaceutical use, and are used as agricultural and horticultural pest control agents. No use is described.

Moreover, although the 1st-position of pyrazole, ie, the use as an insecticide of 1- (3-sulfur atom substituted phenyl) pyrazole derivative in which a phenyl group is bonded, is described (see Patent Document 8), 3-position, The 4-position or 5-position, that is, (3-sulfur atom-substituted phenyl) pyrazole derivative substituted from a carbon atom has not been described.
: US (US Patent) -5032165 : EP (European publication) -1464211 : US (US Patent) -5434178 : US (US Patent) -5756529 : US (US Patent) -5760068 : US (US Patent) -5466823 : US (US Patent) -5521207 : WO (International Publication) -99/55668

  In recent years, some of the commercially available insecticides and acaricides are restricted in use due to problems such as residue, accumulation, and environmental pollution. In addition, the use of the same insecticide / acaricide for a long period of time has caused a problem of generation of resistant pests. Therefore, development of an insecticidal acaricide having a novel molecular structure, which is considered to have an action different from that of commercially available insecticides, is desired. The present invention has been made under the above technical background, and an object thereof is to provide a novel compound exhibiting insecticidal and / or acaricidal activity.

  As a result of intensive research on the pyrazole derivatives, the present inventors have found that (3-sulfur atom-substituted phenyl) pyrazole derivatives have pest control activity, in particular, against mites such as urticae and citrus mites that are agricultural and horticultural pests. The present invention was completed by finding that it has extremely excellent acaricidal activity.

  The present invention relates to the following general formula (I)

[Where:
R ¹ is an optionally substituted C ₁ -C ₆ alkyl group (the substituent is 1-7 substituents selected from the group consisting of a halogen atom, a C ₃ -C ₆ cycloalkyl group and a cyano group) An optionally substituted C ₂ -C ₆ alkenyl group (the substituent is 1-7 substituents selected from the group consisting of a halogen atom and a cyano group) or C. It represents ₃ -C ₆ cycloalkyl group,
A is a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent is 1-7 substituents selected from the group consisting of a hydroxyl group and a halogen atom), substitution which may C ₂ -C be the ₆ alkenyl group (the substituent is a 1-7 substituents selected from the group consisting of halogen atom.), optionally substituted C ₂ -C ₆ An alkynyl group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms), an optionally substituted C ₃ -C ₆ cycloalkyl group (the substituent is a halogen atom) 1-6 substituents selected from the group consisting of atoms.), Formula —C (Y) ═NOR (wherein R represents a hydrogen atom or a C ₁ -C ₆ alkyl group, Y represents Represents a hydrogen atom or an amino group). A 5-6 membered heteroaryl group containing 1-3 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, which may be partially saturated, the substituent represents 1-3 is a substituent.), or a cyano group selected from the group consisting of halogen _atom, C 1 -C ₆ alkyl group and _C 1 -C ₆ alkoxy group,
X may be the same or different when m represents an integer of 2 or 3, and represents a halogen atom;
m represents an integer of 0 to 3,
n represents an integer of 0 or 1,
Q is the following general formula (Q-1), (Q-2) or (Q-3):

[Where:
R ² , R ⁵ and R ⁸ represent an optionally substituted C ₁ -C ₆ alkyl group (the substituent is 1-9 substituents selected from the group consisting of halogen atoms). Represent,
R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, or an optionally substituted C ₁ -C ₆ alkyl group (the substituent is a halogen atom) 1-9 substituents selected from the group consisting of atoms), an optionally substituted C ₁ -C ₆ alkoxy group (the substituent is 1- selected from the group consisting of halogen atoms). 7 substituents), an optionally substituted C ₁ -C ₆ alkylthio group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms) or An optionally substituted phenyl group [the substituent is a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent is 1-9 selected from the group consisting of halogen atoms] And may be substituted. _{1 to} 5 substituents selected from the group consisting of C ₁ -C ₆ alkoxy groups (the substituents are 1-7 substituents selected from the group consisting of halogen atoms) . ]. ]
Represents a group represented by ]
(3-sulfur atom-substituted phenyl) pyrazole derivative or a salt thereof.
When m is 0, Xm represents a hydrogen atom.

  Moreover, this invention is a manufacturing intermediate of the (3-sulfur atom substituted phenyl) pyrazole derivative represented by general formula (I), and is the following general formula (II)

[Wherein A, X, m and Q are as defined above, and X ¹ represents a hydrogen atom, a fluorine atom, an amino group, a nitro group, a mercapto group or a formula —S (C═Z) Ra (formula In the formula, Ra represents a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group or a halogen atom, and Z represents an oxygen atom or a sulfur atom. ]
It is a substituted phenyl pyrazole compound represented by these.

Furthermore, this invention is an agrochemical composition which contains the (3-sulfur atom substituted phenyl) pyrazole derivative represented by general formula (I), or its salt as an active ingredient.
Also, as used in the specification and the appended claims, the singular forms ("a", "an", and "the" in English) have other contexts that clearly indicate others. Unless otherwise indicated, the plural includes.

  The (3-sulfur atom-substituted phenyl) pyrazole derivative or a salt thereof of the present invention is, for example, a hemipod pest, a lepidopteran pest, a coleopteran pest, a diptera pest, a hymenopteran pest, a straight pest, a termite It exhibits an excellent control effect against a wide range of pests such as pests, thrips, spider mites, and plant parasitic nematodes, especially mites such as urticae and citrus mite that are agricultural and horticultural pests.

  Hereinafter, the present invention will be described in detail.

In the present invention, "optionally substituted C ₁ -C ₆ alkyl group", "optionally substituted C ₁ -C ₆ alkoxy group", "optionally substituted C ₁ -C ₆ alkylthio group “C ₁ -C ₆ alkyl moiety” such as “is a linear or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Isobutyl group, sec-butyl group, tert-butyl group, pentyl group, 2-methylbutyl group, 1-methylpentyl group, neopentyl group, 1-ethylpropyl group, hexyl group, 1-methylpentyl group, 3,3-dimethyl It may be a butyl group, a 2,2-dimethylbutyl group or a 1,1-dimethylbutyl group, and in R ¹ , a linear or branched alkyl group having 1 to 4 carbon atoms (C ₁ -C ₄ An alkyl group), more preferably a straight-chain or branched-chain alkyl group has 2 to 4 carbon atoms (C ₂ -C ₄ alkyl group), even more preferably, 2 to carbon atoms A linear or branched alkyl group (C ₂ -C ₃ alkyl group) that is _three , most preferably an ethyl group, and in others, it preferably has 1 to 4 carbon atoms. A linear or branched alkyl group (C ₁ -C ₄ alkyl group), more preferably a linear or branched alkyl group having 1 to 3 carbon atoms (C ₁ -C ₃ alkyl group). And even more preferably a methyl group or an ethyl group.
In the present invention, the “halogen atom” can be, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably in A , A chlorine atom or a bromine atom, and in other cases, a fluorine atom or a chlorine atom is more preferable.

In the present invention, "C ₃ -C ₆ cycloalkyl moiety" such as "optionally substituted C ₃ -C ₆ cycloalkyl group" has a carbon number of 3 to 6 cyclic alkyl groups, for example, It can be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group, preferably a cyclic alkyl group having 3 to 5 carbon atoms, more preferably a cyclopropyl group.

In the present invention, "C ₂ -C ₆ alkenyl moiety" in the "optionally substituted C ₂ -C ₆ alkenyl group", a straight-chain or branched alkenyl group having a carbon number of 2 to 6 For example, ethenyl group, 2-propenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-methyl-2-butenyl group, 1- It may be a methyl-2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 1-hexenyl group or a 2-hexenyl group, and preferably a straight chain having 2 to 4 carbon atoms Or a branched alkenyl group, more preferably a linear or branched alkenyl group having 3 or 4 carbon atoms (C ₃ -C ₄ alkenyl group), and even more preferably 2 -A propenyl group.
In the present invention, "C ₂ -C ₆ alkynyl moiety" such as "optionally substituted C ₂ -C ₆ alkynyl group" is a straight-chain or branched alkynyl group having a carbon number of 2 to 6 For example, ethynyl group, 2-propynyl group, 1-methyl-2-propynyl group, 1-butynyl group, 2-butynyl group, 1-methyl-2-butynyl group, 3-butynyl group, 1-pentynyl group, It may be a 2-pentynyl group, a 1-hexynyl group or a 2-hexynyl group, preferably a linear or branched alkynyl group having 2 to 4 carbon atoms, more preferably a carbon number. It is a linear or branched alkynyl group (C ₃ -C ₄ alkynyl group) that is ₃ or ₄ , more preferably 2-propynyl group.
In the present invention, “5-6 containing 1-3 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, which may be substituted or partially saturated,” The “5-6-membered heteroaryl moiety” of the “membered heteroaryl group” is, for example, a furyl group, a thienyl group, a pyrrolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group, an oxadiazolyl group. , Dihydrooxadiazolyl group, thiadiazolyl group, dihydrothiadiazolyl group, triazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group or pyridazinyl group, preferably furyl group, thienyl group, oxazolyl group, isoxazolyl group, Thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, o Sadiazolyl group, dihydrooxadiazolyl group, thiadiazolyl group, dihydrothiadiazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group or pyridazinyl group, more preferably isoxazolyl group, thiazolyl group, isothiazolyl group, oxadiazolyl group, dihydro An oxadiazolyl group, a thiadiazolyl group or a pyridyl group, still more preferably an isoxazolyl group, a thiazolyl group, an oxadiazolyl group, a dihydrooxadiazolyl group or a thiadiazolyl group, most preferably a thiazolyl group, an oxadiazolyl group or Dihydrooxadiazolyl group.

In the present invention, the “optionally substituted C ₁ -C ₆ alkyl group of R ¹ (the substituent is selected from the group consisting of a halogen atom, a C ₃ -C ₆ cycloalkyl group and a cyano group” 7 substituents.) ”Means, for example, the“ C ₁ -C ₆ alkyl group ”, fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group. 2-chloroethyl group, 2-bromoethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 2,3,3-trifluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, heptafluoropropyl group Lopyl group, 4-fluorobutyl group, 4-chlorobutyl group, 5-fluoropentyl group, 5-chloropentyl group, 6-fluorohexyl group, 6-chlorohexyl group, cyclopropylmethyl group, cyclobutylmethyl group, cyclopentyl Methyl group, cyclohexylmethyl group, 2-cyclopropylethyl group, 2-cyclobutylethyl group, 2-cyclopentylethyl group, 2-cyclohexylethyl group, 3-cyclopropylpropyl group, 3-cyclobutylpropyl group, 4-cyclo Propylbutyl group, 4-cyclobutylbutyl group, 5-cyclopropylpentyl group, 5-cyclobutylpentyl group, 6-cyclopropylhexyl group, 6-cyclobutylhexyl group, cyanomethyl group, 2-cyanoethyl group, 3- Cyanopropyl group, 4-cyanobutyl group, 5-cyanope It is a methyl group or a 6-cyano group, preferably, "optionally substituted _C 1 -C ₆ alkyl group (the substituent is 1-7 halogen atoms, one _C 3 -C ₆ cycloalkyl group or one cyano group.) ”, And more preferably, the“ C ₁ -C ₄ alkyl group ”, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group. 2-fluoroethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 2,3,3-trifluoropropyl group 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, heptafluoropropyl group, 4-fluoro Til group, 4-chlorobutyl group, cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, 2-cyclopropylethyl group, 2-cyclobutylethyl group, cyanomethyl group or 2-cyanoethyl group, and more preferably Are ethyl, propyl, butyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3-fluoropropyl, 3-chloropropyl, 2,3,3-trifluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 4-fluorobutyl group, cyclopropylmethyl group, cyclobutylmethyl group, 2-cyclopropylethyl group, 2-cyclobutylethyl A til group, a cyanomethyl group or a 2-cyanoethyl group, particularly preferably an ethyl group, a propyl group, a butyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a 3-fluoropropyl group, 3, 3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 4-fluorobutyl group, cyclopropylmethyl group, cyclobutyl A methyl group or a cyanomethyl group, most preferably an ethyl group, a propyl group, a butyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3-tetrafluoropropyl group or a cyclopropylmethyl group. It is.

In the present invention, “optionally substituted C ₂ -C ₆ alkenyl group of R ¹ (the substituent is 1-7 substituents selected from the group consisting of a halogen atom and a cyano group). Is, for example, the aforementioned “C ₂ -C ₆ alkenyl group”, 2-fluoroethenyl group, 2-chloroethenyl group, 2-bromoethenyl group, 3-fluoro-2-propenyl group, 2-chloro-2-propenyl group. 3-chloro-2-propenyl group, 3,3-difluoro-2-propenyl group, 3,3-dichloro-2-propenyl group, 2,3,3-trifluoro-2-propenyl group, 2-cyanoethenyl group Or a 3-cyano-2-propenyl group, preferably the “C ₂ -C ₄ alkenyl group”, 2-chloro-2-propenyl group, 3-chloro-2-propenyl group, 2-cyanoethenyl group. Or 3-cyano-2-propenyl group, and most preferably 3,3-difluoro-2-propenyl group, 3,3-dichloro-2-propenyl group or 2-propenyl group.

In the present invention, “an optionally substituted C ₁ -C ₆ alkyl group (the substituent is 1-7 substituents selected from the group consisting of a hydroxyl group and a halogen atom)” of A Is, for example, the aforementioned “C ₁ -C ₆ alkyl group”, fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 2,3,3-trifluoropropyl group, 3,3,3-trifluoropropyl group 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, heptafluoropropyl group, 4-fluorobuty Group, 4-chlorobutyl group, 5-fluoropentyl group, 5-chloropentyl group, 6-fluorohexyl group, 6-chlorohexyl group, hydroxymethyl group, 2-hydroxyroethyl group, 3-hydroxypropyl group, 4 -Hydroxybutyl group, 5-hydroxypentyl group or 6-hydroxyhexyl group, and preferably “an optionally substituted C ₁ -C ₆ alkyl group (the substituent is one hydroxyl group) Or 1-7 halogen atoms.) ”, And more preferably, the“ C ₁ -C ₃ alkyl group ”, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2 -Fluoroethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 3,3,3 A trifluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a methyl group, an ethyl group, a propyl group. , Fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, hydroxymethyl group, 1-hydroxyethyl group or 2-hydroxyethyl group, particularly preferably methyl group, ethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group or 2,2,2- A trifluoroethyl group, most preferably a methyl group, an ethyl group or a difluoromethyl group. .

In the present invention, “optionally substituted C ₂ -C ₆ alkenyl group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms)” of A is, for example, , “C ₂ -C ₆ alkenyl group”, 2-fluoroethenyl group, 2-chloroethenyl group, 2-bromoethenyl group, 3-fluoro-2-propenyl group, 2-chloro-2-propenyl group, 3-chloro -2-propenyl group, 3,3-difluoro-2-propenyl group, 3,3-dichloro-2-propenyl group or 2,3,3-trifluoro-2-propenyl group, A “C ₂ -C ₄ alkenyl group”, a 2-chloro-2-propenyl group or a 3-chloro-2-propenyl group, more preferably an ethenyl group, a 2-propenyl group or a 2-butenyl group, Suitable Is a 2-propenyl group.
In the present invention, “optionally substituted C ₂ -C ₆ alkynyl group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms)” of A is, for example, , Said “C ₂ -C ₆ alkynyl group”, 2-fluoroethynyl group, 2-chloroethynyl group, 2-bromoethynyl group, 3-fluoro-2-propynyl group or 3-chloro-2-propynyl group The “C ₂ -C ₄ alkynyl group” is preferable, and the ethynyl group is more preferable.
In the present invention, the “optionally substituted C ₃ -C ₆ cycloalkyl group (the substituent is 1-6 substituents selected from the group consisting of halogen atoms)” of A is “ For example, the “C ₃ -C ₆ cycloalkyl group”, fluorocyclopropyl group, difluorocyclopropyl group, chlorocyclopropyl group, dichlorocyclopropyl group, bromocyclopropyl group, dibromocyclopropyl group, iodocyclopropyl group, fluoro Cyclobutyl, chlorocyclobutyl, bromocyclobutyl, fluorocyclopentyl, difluorocyclopentyl, chlorocyclopentyl, dichlorocyclopentyl, bromocyclopentyl, dibromocyclopentyl, iodocyclopentyl, fluorocyclohexyl, difluorocyclo Hexyl group, a cyclohexyl group Kuroroshikuro, dichloro cyclohexyl group, a cyclohexyl group Buromoshikuro be a cyclohexyl group dibromo cyclohexyl group or Yodoshikuro, Preferably, the "C ₃ -C ₆ cycloalkyl group" refers to fluoro A cyclopropyl group, a difluorocyclopropyl group, a chlorocyclopropyl group, or a dichlorocyclopropyl group, and more preferably a cyclopropyl group or a cyclobutyl group.
In the present invention, it is represented by “Formula —C (Y) ═NOR (wherein R represents a hydrogen atom or a C ₁ -C ₆ alkyl group, and Y represents a hydrogen atom or an amino group)”. The “group” is preferably a group in which R is a hydrogen atom or a C ₁ -C ₄ alkyl group, more preferably a group in which R is a hydrogen atom, a methyl group or an ethyl group, Preferably, R is a hydrogen atom or a methyl group, and Y is a group that is a hydrogen atom.
In the present invention, “containing 5 1 to 3 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, which may be substituted and partially saturated,” of A. -6-membered ring heteroaryl group (said substituent is 1 to 3 substituents selected from the group consisting of halogen _atom, C 1 -C ₆ alkyl group and _C 1 -C ₆ alkoxy group.) " Is, for example, the above-mentioned “5-6-membered heteroaryl group”, chlorofuryl group, methylfuryl group, methoxyfuryl group, chlorothienyl group, methoxythienyl group, methylpyrrolyl group, chlorooxazolyl group, methyloxazolyl group Methoxyoxazolyl group, methylisoxazolyl group, ethylisoxazolyl group, chloroisoxazolyl group, methoxyisoxazolyl group, methylthiazolyl group, ethyl Thiazolyl group, chlorothiazolyl group, methoxythiazolyl group, chloroisothiazolyl group, methylisothiazolyl group, chloroimidazolyl group, methylimidazolyl group, methylpyrazolyl group, chloropyrazolyl group, fluoropyrazolyl group, chlorooxadiazolyl group, Methyloxadiazolyl group, ethyloxadiazolyl group, methyldihydrooxadiazolyl group, ethyldihydrooxadiazolyl group, chlorothiadiazolyl group, methylthiadiazolyl group, ethylthiadiazolyl group, methyldihydrothiadiazolyl group , Methyltriazolyl group, chlorotriazolyl group, chloropyridyl group, methylpyridyl group, methoxypyridyl group, ethylpyridyl group, chloropyrazinyl group, methylpyrazinyl group, methoxypyrazinyl group, chloropyrimidinyl group, Rupyrimidinyl group, methoxypyrimidinyl group, chloropyridazinyl group, methylpyridazinyl group or methoxypyridazinyl group, preferably furyl group, chlorofuryl group, methylfuryl group, methoxyfuryl group , Thienyl group, chlorothienyl group, methoxythienyl group, pyrrolyl group, methylpyrrolyl group, oxazolyl group, chlorooxazolyl group, methyloxazolyl group, methoxyoxazolyl group, isoxazolyl group, methylisoxazolyl group, chloro Isoxazolyl group, methoxyisoxazolyl group, thiazolyl group, methylthiazolyl group, chlorothiazolyl group, methoxythiazolyl group, isothiazolyl group, chloroisothiazolyl group, methylisothiazolyl group, imidazolyl group, chloroimidazolyl group, Methylimidazolyl group, pyrazolyl Group, methylpyrazolyl group, chloropyrazolyl group, fluoropyrazolyl group, oxadiazolyl group, chlorooxadiazolyl group, methyloxadiazolyl group, dihydrooxadiazolyl group, methyldihydrooxadiazolyl group, thiadiazolyl group, chlorothiadiazolyl group , Methylthiadiazolyl group, dihydrothiadiazolyl group, methyldihydrothiadiazolyl group, methyltriazolyl group, triazolyl group, chlorotriazolyl group, pyridyl group, chloropyridyl group, methylpyridyl group, methoxypyridyl group, Ethylpyridyl group, pyrazinyl group, chloropyrazinyl group, methylpyrazinyl group, methoxypyrazinyl group, pyrimidinyl group, chloropyrimidinyl group, methylpyrimidinyl group, methoxypyrimidinyl group, pyridazinyl group, chloropyridazinyl group Methylpyridazinyl group or methoxypyridazinyl group, more preferably furyl group, thienyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, pyrazolyl group, oxadiazolyl group, dihydroxyl group A diazolyl group, a thiadiazolyl group, a dihydrothiadiazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group or a pyridazinyl group, and even more preferably an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an oxadiazolyl group, a dihydrooxadiazolyl group , Thiadiazolyl group or pyridyl group, particularly preferably isoxazolyl group, thiazolyl group, oxadiazolyl group, dihydrooxadiazolyl group or thiadiazolyl group, most preferably thiazolyl group, oxadiazolyl group. A group or a dihydro-oxadiazolyl group.
In the present invention, “optionally substituted C ₁ -C ₆ alkyl groups such as R ² and R ⁴ (the substituents are ₁ to 9 substituents selected from the group consisting of halogen atoms). ) ”Is, for example, the above-mentioned“ C ₁ -C ₆ alkyl group ”, fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2- Bromoethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 3-chloropropyl group, 2,3,3-trifluoropropyl group, 3,3,3-trifluoro Propyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoro A til group, heptafluoropropyl group, 4-fluorobutyl group, 4-chlorobutyl group, nonafluorobutyl group, 5-fluoropentyl group, 5-chloropentyl group, 6-fluorohexyl group or 6-chlorohexyl group Preferably, the “C ₁ -C ₄ alkyl group”, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2,2,2 -Trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,3,3-trifluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl Group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group, hep Fluoropropyl group, 4-fluoro butyl group or a nonafluorobutyl group, for R ^2, R ⁵ and R ⁸ is more preferably a methyl group, an ethyl group, a propyl group, fluoromethyl group, chloromethyl group, A difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group or a 2,2,2-trifluoroethyl group, and even more preferably a methyl group, an ethyl group, a fluoromethyl group, a chloromethyl group, a difluoromethyl. A group, a trifluoromethyl group or a 2,2,2-trifluoroethyl group, most preferably a methyl group or an ethyl group, and R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁹ and R ^10. More preferably, methyl group, ethyl group, propyl group, butyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoro group are more preferable. Methyl group, 2-fluoroethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,3,3-trifluoropropyl group, 3,3 , 3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoro An ethyl group, a heptafluoropropyl group, a 4-fluorobutyl group or a nonafluorobutyl group, and more preferably a methyl group, an ethyl group, a propyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, 2 -Fluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,3,3-trifluoro Ropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2, 2,2-trifluoroethyl group, heptafluoropropyl group, 4-fluorobutyl group or nonafluorobutyl group, particularly preferably methyl group, ethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group 2,2,2-trifluoroethyl group, pentafluoroethyl group, 2,3,3-trifluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl Group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group or heptafluoropropylene. And most preferably a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group or a heptafluoropropyl group.
In the present invention, “optionally substituted C ₁ -C ₆ alkoxy group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms)” such as R ^4, etc. For example, the “C ₁ -C ₆ alkoxy group”, fluoromethoxy, chloromethoxy, bromomethoxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2,2,2 -Trifluoroethoxy, pentafluoroethoxy, 3-fluoropropoxy, 3-chloropropoxy, 2,3,3-trifluoropropoxy, 3,3,3-trifluoropropoxy, 2,2,3,3-tetrafluoropropoxy , Heptafluoropropoxy, 4-fluorobutoxy, 4-chlorobutoxy, 5-fluoropentoxy, 5- It may be a chloropenthioxy, 6-fluorohexyloxy or 6-chlorohexyloxy group, and is preferably “an optionally substituted C ₁ -C ₃ alkoxy group (the substituent is 1-7 fluorines) Or a halogen atom.), And more preferably a methoxy group, an ethoxy group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, or A pentafluoroethoxy group, most preferably a difluoromethoxy group or a trifluoromethoxy group.
In the present invention, “optionally substituted C ₁ -C ₆ alkylthio group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms)” such as R ^4, etc. For example, the “C ₁ -C ₆ alkylthio group”, fluoromethylthio, chloromethylthio, bromomethylthio, difluoromethylthio, trifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2, 2,2-trifluoroethylthio, pentafluoroethylthio, 3-fluoropropylthio, 3-chloropropylthio, 2,3,3-trifluoropropylthio, 3,3,3-trifluoropropylthio, 2, 2,3,3-tetrafluoropropylthio, heptafluoropropylthio, 4-fluorobutylthio, 4-chlorobut It can be a thiolthio, 5-fluoropentylthio, 5-chloropentylthio, 6-fluorohexylthio or 6-chlorohexylthio group, preferably “an optionally substituted C ₁ -C ₃ alkylthio group (in which The substituent is 1-7 fluorine atoms or 1 chlorine atom.) ”, And more preferably a methylthio group, an ethylthio group, a fluoromethylthio group, a difluoromethylthio group, a trifluoromethylthio group, 2 , 2,2-trifluoroethylthio group or pentafluoroethylthio group, most preferably a difluoromethylthio group or a 2,2,2-trifluoroethylthio group.
In the present invention, an optionally substituted phenyl group such as R ⁴ [the substituent is a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent is a group consisting of a halogen atom] And 1 to 9 substituents selected from the group consisting of halogen atoms, and optionally substituted C ₁ -C ₆ alkoxy groups. Is a 1 to 5 substituent selected from the group consisting of: a phenyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a chlorophenyl group, a dichlorophenyl group, Trichlorophenyl group, fluorochlorophenyl group, bromophenyl group, iodophenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenol Nyl group, fluoro (methyl) phenyl group, chloro (methyl) phenyl group, bromo (methyl) phenyl group, (trifluoromethyl) phenyl group, fluoro (trifluoromethyl) phenyl group, methoxyphenyl group, (difluoromethoxy) phenyl A group, (trifluoromethoxy) phenyl group, ethoxyphenyl group, (2,2,2-trifluoroethoxy) phenyl group, phlooxyphenyl group or (3,3,3-trifluoropropoxy) phenyl group, Preferably, “an optionally substituted phenyl group [the substituent is a halogen atom, an optionally substituted C ₁ -C ₃ alkyl group (the substituent is selected from the group consisting of halogen atoms] 1-7 substituents) and an optionally substituted C ₁ -C ₃ alkoxy group (the substituent is a halogen atom or 1 to 3 substituents selected from the group consisting of 1 to 7 substituents selected from the group consisting of 1 to 7 substituents], and more preferably “optionally substituted phenyl group”. [The substituent is a fluorine atom, a chlorine atom, a bromine atom, an optionally substituted C ₁ -C ₂ alkyl group (the substituent is selected from the group consisting of a fluorine atom and a chlorine atom. And a C ₁ -C ₂ alkoxy group which may be substituted (the substituent is 1-3 substituents selected from the group consisting of a fluorine atom and a chlorine atom). 1 to 3 substituents selected from the group]], and even more preferably, phenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl. Group Ruphenyl group, dimethylphenyl group, ethylphenyl group, (trifluoromethyl) phenyl group, methoxyphenyl group, (difluoromethoxy) phenyl group, (trifluoromethoxy) phenyl group or (2,2,2-trifluoroethoxy) phenyl Most preferably a chlorophenyl group, a (trifluoromethyl) phenyl group or a (trifluoromethoxy) phenyl group.

  The compound (I) of the present invention may form a salt with an acidic substance or a basic substance. For example, when there is a dissociable proton in the molecule, an alkali metal salt, an alkaline earth metal salt or ammonium The salt with an acidic substance may be a salt such as a sulfate, hydrochloride, nitrate, or phosphate. Those salts are included in the present invention as long as they can be used as an agrochemical composition such as an insecticidal composition.

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

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

In the general formula (I) of the present invention,
R ¹ is (1a) preferably an optionally substituted C ₁ -C ₄ alkyl group (the substituent is 1-7 halogen atoms, 1 C ₃ -C ₆ cycloalkyl group or 1 cyano group), an optionally substituted C ₂ -C ₄ alkenyl group (the substituent is 1-2 halogen atoms or 1 cyano group) or C _3- . A C ₆ cycloalkyl group,
Suitable than (1b), optionally substituted _C 2 -C ₄ alkyl group (the substituent is one to five fluorine atoms, one chlorine atom, one _C 3 -C ₄ cycloalkyl an alkyl group or one cyano _group.), and a C 2 -C ₄ alkenyl group or a _C 3 -C ₅ cycloalkyl group,
(1c) Even more preferably, an ethyl group, a propyl group, a butyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a 3-fluoropropyl group, a 3,3,3-trifluoropropyl group 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 4-fluorobutyl group, cyclopropylmethyl group, cyclobutylmethyl group, cyanomethyl group, 2- A propenyl group, a 2-methyl-2-propen-1-yl group or a cyclopentyl group,
(1d) Particularly preferably, an ethyl group, a propyl group, a butyl group, a 2,2,2-trifluoroethyl group, a cyclopropylmethyl group, or a 2-propenyl group,
(1e) Most preferably, it is a propyl group or a 2,2,2-trifluoroethyl group,
A is preferably (2a), halogen atom, optionally substituted _C 1 -C ₄ alkyl group (said substituent is one hydroxyl group or 1-5 halogen atoms.), An optionally substituted C ₂ -C ₄ alkenyl group (the substituent is one fluorine atom or a chlorine atom), an optionally substituted C ₂ -C ₄ alkynyl group (the substituent is 1 fluorine atom or chlorine atom), an optionally substituted C ₃ -C ₄ cycloalkyl group (the substituent is one fluorine atom or chlorine atom), a formula —C A group represented by (Y) = NOR (wherein R is a hydrogen atom or a C ₁ -C ₄ alkyl group, and Y is a hydrogen atom or an amino group), which may be substituted; Consisting of nitrogen, oxygen and sulfur atoms which may be partially saturated 5-6 membered heteroaryl group containing 1-3 heteroatoms selected from the group (the substituent is a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₂ alkyl group and a C ₁ -C) ₂ or 2 substituents selected from the group consisting of ₂ alkoxy groups) or a cyano group,
More preferably (2b), a chlorine atom, a bromine atom, an iodine _atom, C 1 -C ₃ alkyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2- Chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, hydroxyl methyl, 1-hydroxyethyl group, 2-hydroxyethyl _group, C 2 -C ₄ alkenyl group, 2-chloro-2-propenyl group, 3-chloro-2-propenyl _group, C 2 -C ₄ alkynyl group, 3 -Chloro-2-propynyl group, cyclopropyl group, cyclobutyl group, fluorocyclopropyl group, difluorocyclopropyl group, chloro Chloropropyl group, dichlorocyclopropyl group, (hydroxyimino) methyl group, (methoxyimino) methyl group, (ethoxyimino) methyl group, amino (hydroxyimino) methyl group, furyl group, thienyl group, oxazolyl group, isoxazolyl group, Thiazolyl group, isothiazolyl group, imidazolyl group, pyrazolyl group, oxadiazolyl group, dihydrooxadiazolyl group, thiadiazolyl group, dihydrothiadiazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group or cyano group,
(2c) Even more preferably, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2 , 2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, hydroxylmethyl group, 1-hydroxylethyl group, 2-hydroxylethyl group, 2-propenyl group, 2-butenyl group, ethynyl group, 1- Propynyl, 2-butynyl, cyclopropyl, cyclobutyl, (hydroxyimino) methyl, (methoxyimino) methyl, (ethoxyimino) methyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, dihydrooxa Diazolyl group, thiadiazolyl group, pyridyl group or An amino group,
(2d) Particularly preferably, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, a 2,2,2-trifluoroethyl group, 2-propenyl, ethynyl, cyclopropyl, cyclobutyl, (hydroxyimino) methyl, (methoxyimino) methyl, isoxazolyl, thiazolyl, oxadiazolyl, dihydrooxadiazolyl, thiadiazolyl or cyano Yes,
(2e) Most preferably, chlorine atom, bromine atom, methyl group, ethyl group, difluoromethyl group, cyclopropyl group, 2-propenyl group, (hydroxyimino) methyl group, thiazolyl group, oxadiazolyl group, dihydrooxadiazolyl Group or cyano group,
X is (3a) preferably a fluorine atom or a chlorine atom,
(3b) is more preferably a fluorine atom,
m is (4a) preferably an integer from 0 to 2,
(4b) More preferably, it is an integer of 0 or 1.
n is (5a) preferably an integer of 0;
Q is (6a) preferably a group represented by the formula (Q-1) or (Q-2),
(6b) More preferably, it is a group represented by the formula (Q-1), and R ² , R ⁵ and R ⁸ are (7a), preferably an optionally substituted C ₁ -C ₄ alkyl. A group (the substituent is 1-9 fluorine atoms or 1 halogen atom),
(7b) More preferably, methyl group, ethyl group, propyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group or 2,2,2-trifluoroethyl group And
(7c) Even more preferably, a methyl group, an ethyl group, a fluoromethyl group, a chloromethyl group, a difluoromethyl group, a trifluoromethyl group or a 2,2,2-trifluoroethyl group,
(7d) Most preferably, it is a methyl group or an ethyl group, and R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are (8a) preferably a hydrogen atom, a fluorine atom, a chlorine atom, A bromine atom, an optionally substituted C ₁ -C ₄ alkyl group (the substituent is 1-9 fluorine atoms or 1 chlorine atom), an optionally substituted C ₁ -C ₄ alkoxy group (the substituent is 1-7 fluorine atoms or 1 chlorine atom), an optionally substituted C ₁ -C ₄ alkylthio group (the substituent is 1-7 Or a phenyl group which may be substituted [the substituent is a halogen atom, an optionally substituted C ₁ -C ₃ alkyl group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms) and Conversion which may C ₁ -C be the ₃ alkoxy group (said substituent is 1-7 substituents selected from the group consisting of halogen atom.) 1-3 groups selected from the group consisting of Is a substituent. ],
More preferably (8b), a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₄ alkyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group 2-chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,3,3-trifluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group, heptafluoropropyl group, 4-fluorobutyl group, nonafluorobutyl group, methoxy group, ethoxy group, fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, 2 2,2-trifluoroethoxy group, pentafluoroethoxy group, methylthio group, ethylthio group, fluoromethylthio group, difluoromethylthio group, trifluoromethylthio group, 2,2,2-trifluoroethylthio group, pentafluoroethylthio group A phenyl group substituted with 1-2 substituents selected from the group consisting of a phenyl group or a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group and a methoxy group,
(8c) Even more preferably, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, a butyl group, a fluoromethyl group, a chloromethyl group, a difluoromethyl group, a trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,3,3-trifluoropropyl group, 3,3,3- Trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group, Heptafluoropropyl group, 4-fluorobutyl group, nonafluorobutyl group, difluoromethoxy group, trifluoromethoxy group, difluoromethylthio group, , 2,2-trifluoroethyl thio group, chlorophenyl group, a (trifluoromethyl) phenyl or (trifluoromethoxy) phenyl group,
(8d) Most preferably, R ³ , R ⁶ and R ⁹ are a hydrogen atom, a chlorine atom or a methyl group, and R ⁴ , R ⁷ and R ¹⁰ are a hydrogen atom, a difluoromethyl group or a trifluoromethyl group. , A pentafluoroethyl group, a heptafluoropropyl group, a difluoromethoxy group, a difluoromethylthio group or a 2,2,2-trifluoroethylthio group.
Also, R ¹ is selected from (1a)-(1e), A is selected from (2a)-(2e), X is selected from (3a)-(3b), and m is (4a)-(4b). ), N is selected from (5a), R ² etc. are selected from (7a)-(7d), R ³ etc. are selected from (8a)-(8d), and these are combined. Compounds are also suitable, and examples include the following.
(1A) R ¹ is an optionally substituted C ₁ -C ₄ alkyl group (the substituent is 1-7 halogen atoms, 1 C ₃ -C ₆ cycloalkyl group, or 1 cyano group) Group), an optionally substituted C ₂ -C ₄ alkenyl group (the substituent is 1-2 halogen atoms or 1 cyano group) or C ₃ -C ₆ cycloalkyl. Group,
A is a halogen atom, an optionally substituted C ₁ -C ₄ alkyl group (the substituent is one hydroxyl group or 1-5 halogen atoms), and optionally substituted C. _2- C ₄ alkenyl group (the substituent is one fluorine atom or chlorine atom), an optionally substituted C ₂ -C ₄ alkynyl group (the substituent is one fluorine atom or A chlorine atom), an optionally substituted C ₃ -C ₄ cycloalkyl group (the substituent is one fluorine atom or a chlorine atom), a formula —C (Y) = NOR (formula Wherein R is a hydrogen atom or a C ₁ -C ₄ alkyl group, and Y is a hydrogen atom or an amino group, which may be substituted or partially saturated. 1 selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom 3-6-membered heteroaryl group containing 3 heteroatoms (the substituent is a group consisting of a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₂ alkyl group and a C ₁ -C ₂ alkoxy group) 1 or 2 substituents selected from the above) or a cyano group,
X is a fluorine atom or a chlorine atom,
m is an integer from 0 to 2,
n is an integer of 0 or 1,
Q is a group represented by the formula (Q-1), (Q-2) or (Q-3),
R ² , R ⁵ and R ⁸ are optionally substituted C ₁ -C ₄ alkyl groups (the substituent is 1-9 fluorine atoms or 1 halogen atom);
R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an optionally substituted C ₁ -C ₄ alkyl group (the substituent is 1-9 fluorine atoms or 1 chlorine atom), an optionally substituted C ₁ -C ₄ alkoxy group (the substituent is 1-7 fluorine atoms or 1 chlorine atom) An optionally substituted C ₁ -C ₄ alkylthio group (the substituent is 1 to 7 fluorine atoms or 1 chlorine atom) or an optionally substituted phenyl group. [The substituent is a halogen atom, an optionally substituted C ₁ -C ₃ alkyl group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms) and substitution. An optionally substituted C ₁ -C ₃ alkoxy group (the substituent is a halogen atom) 1 to 7 substituents selected from the group consisting of atoms.) To 1 to 3 substituents selected from the group consisting of. A compound that is
(1B) R ¹ is an optionally substituted C ₂ -C ₄ alkyl group (the substituent is 1 to 5 fluorine atoms, 1 chlorine atom, 1 C ₃ -C ₄ cycloalkyl) Group or one cyano group), a C ₂ -C ₄ alkenyl group or a C ₅ -C ₆ cycloalkyl group,
A is a chlorine atom, a bromine atom, an iodine _atom, C 1 -C ₃ alkyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2, 2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, hydroxylmethyl group, 1- hydroxyethyl group, 2-hydroxyethyl _group, C 2 -C ₄ alkenyl group, 2-chloro-2-propenyl group, 3-chloro-2-propenyl _group, C 2 -C ₄ alkynyl group, 3-chloro-2 Propynyl, cyclopropyl, cyclobutyl, cyclopentyl, fluorocyclopropyl, difluorocyclopropyl, chloro Cyclopropyl group, dichlorocyclopropyl group, (hydroxyimino) methyl group, (methoxyimino) methyl group, (ethoxyimino) methyl group, amino (hydroxyimino) methyl group, furyl group, thienyl group, oxazolyl group, isoxazolyl group, Thiazolyl group, isothiazolyl group, imidazolyl group, pyrazolyl group, oxadiazolyl group, dihydrooxadiazolyl group, thiadiazolyl group, dihydrothiadiazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group or cyano group,
X is a fluorine atom or a chlorine atom,
m is an integer from 0 to 2,
n is an integer of 0 or 1,
Q is a group represented by the formula (Q-1), (Q-2) or (Q-3),
R ² , R ⁵ and R ⁸ are methyl, ethyl, propyl, fluoromethyl, chloromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl or 2,2,2-trifluoro An ethyl group,
R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are hydrogen atom, fluorine atom, chlorine atom, bromine atom, C ₁ -C ₄ alkyl group, fluoromethyl group, chloromethyl group, difluoromethyl group , Trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,3,3-trifluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2 -Trifluoroethyl group, heptafluoropropyl group, 4-fluorobutyl group, nonafluorobutyl group, methoxy group, ethoxy group, fluoromethoxy group, difluoromethoxy group, Trifluoromethoxy group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group, methylthio group, ethylthio group, fluoromethylthio group, difluoromethylthio group, trifluoromethylthio group, 2,2,2-trifluoroethylthio A phenyl group substituted with 1-2 substituents selected from the group consisting of a group, a pentafluoroethylthio group, a phenyl group or a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group and a methoxy group ,
(1C) R ¹ is ethyl, propyl, butyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3-fluoropropyl, 3,3,3-trifluoropropyl, 2 , 2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 4-fluorobutyl group, cyclopropylmethyl group, cyclobutylmethyl group, cyanomethyl group, 2-propenyl group 2-methyl-2-propen-1-yl group or cyclopentyl group,
A is a chlorine atom, bromine atom, methyl group, ethyl group, propyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl Group, pentafluoroethyl group, 3-fluoropropyl group, hydroxylmethyl group, 1-hydroxylethyl group, 2-hydroxylethyl group, 2-propenyl group, 2-butenyl group, ethynyl group, 1-propynyl group, 2-butynyl Group, cyclopropyl group, cyclobutyl group, (hydroxyimino) methyl group, (methoxyimino) methyl group, (ethoxyimino) methyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, oxadiazolyl group, dihydrooxadiazolyl group, thiadiazolyl group , A pyridyl group or a cyano group,
X is a fluorine atom or a chlorine atom,
m is an integer from 0 to 2,
n is an integer of 0 or 1,
Q is a group represented by the formula (Q-1) or (Q-2),
R ² , R ⁵ and R ⁸ are a methyl group, an ethyl group, a fluoromethyl group, a chloromethyl group, a difluoromethyl group, a trifluoromethyl group or a 2,2,2-trifluoroethyl group,
R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are hydrogen atom, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, butyl group, fluoromethyl group, chloromethyl group , Difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,3,3-tri Fluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2 , 2,2-trifluoroethyl group, heptafluoropropyl group, 4-fluorobutyl group, nonafluorobutyl group, difluoromethoxy group, trifluoromethoxy group, di A compound which is a fluoromethylthio group, a 2,2,2-trifluoroethylthio group, a chlorophenyl group, a (trifluoromethyl) phenyl group or a (trifluoromethoxy) phenyl group,
(1D) R ¹ is an ethyl group, a propyl group, a butyl group, a 2,2,2-trifluoroethyl group, a cyclopropylmethyl group, or a 2-propenyl group;
A is a chlorine atom, bromine atom, methyl group, ethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, 2-propenyl group, Ethynyl group, cyclopropyl group, cyclobutyl group, (hydroxyimino) methyl group, (methoxyimino) methyl group, isoxazolyl group, thiazolyl group, oxadiazolyl group, dihydrooxadiazolyl group, thiadiazolyl group or cyano group,
X is a fluorine atom or a chlorine atom,
m is an integer of 0 or 1,
n is an integer of 0 or 1,
Q is a group represented by the formula (Q-1),
R ² is a methyl group, an ethyl group, a fluoromethyl group, a chloromethyl group, a difluoromethyl group, a trifluoromethyl group or a 2,2,2-trifluoroethyl group,
R ³ and R ⁴ are the same or different and are a hydrogen atom, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, butyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoro Methyl group, 2-fluoroethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,3,3-trifluoropropyl group, 3,3 , 3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoro Ethyl group, heptafluoropropyl group, 4-fluorobutyl group, nonafluorobutyl group, difluoromethoxy group, trifluoromethoxy group, difluoromethyl Thio, 2,2,2-trifluoroethyl thio group, chlorophenyl group, compounds or (1E) ^{R 1} is (trifluoromethyl) phenyl or (trifluoromethoxy) phenyl group, a propyl group or a 2,2 , 2-trifluoroethyl group,
A is a chlorine atom, bromine atom, methyl group, ethyl group, difluoromethyl group, cyclopropyl group, 2-propenyl group, (hydroxyimino) methyl group, thiazolyl group, oxadiazolyl group, dihydrooxadiazolyl group or cyano group Yes,
X is a fluorine atom,
m is an integer of 0 or 1,
n is an integer of 0 or 1,
Q is a group represented by the formula (Q-1),
R ² is a methyl group or an ethyl group,
R ³ is a hydrogen atom, a chlorine atom or a methyl group, and R ⁴ is a hydrogen atom, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a difluoromethoxy group, a difluoromethylthio group or 2 , 2,2-trifluoroethylthio group.
X ¹ is preferably a hydrogen atom, a fluorine atom, an amino group, a nitro group, a mercapto group, a formula —S (C═O) Ra (wherein Ra is a C ₁ -C ₂ alkyl group). A group represented by the formula: —S (C═S) Ra (wherein Ra is a C ₁ -C ₂ alkoxy group) or a chlorosulfonyl group, and more preferably. Is a hydrogen atom, a fluorine atom, an amino group, a nitro group, a mercapto group, a group represented by the formula —S (C═S) Ra (wherein Ra is a C ₁ -C ₂ alkoxy group) or A chlorosulfonyl group, and even more preferably a hydrogen atom, a fluorine atom, an amino group, a nitro group or a mercapto group.
On the other hand, in the general formula (I) of the present invention,
R ¹ is preferably a C ₂ -C ₄ alkyl group optionally substituted with 1 to 7 halogens, a C ₁ -C ₂ alkyl group substituted with a C ₃ -C ₄ cycloalkyl group, or C 1 ₃ -C a ₄ alkenyl group, more preferably, ethyl group, propyl group, butyl group, 2,2,2-trifluoroethyl group, 2,3,3-trifluoroethyl group, 3,3,3 A trifluoroethyl group, a cyclopropylmethyl group, a cyclobutylmethyl group, a 2-propenyl group or a 2-methyl-2-propenyl group, and even more preferably a propyl group, 2,2,2-trifluoroethyl A group, a cyclopropylmethyl group or a 2-propenyl group.

A is preferably a C ₁ -C ₂ alkyl group, a halogen atom or a cyano group, more preferably a methyl group, an ethyl group, a chlorine atom or a cyano group, and even more preferably a methyl group. Or it is a cyano group.

  X is preferably a chlorine atom or a fluorine atom, and more preferably a fluorine atom.

  m is preferably 0 to 2, and more preferably 0 or 1.

  n is preferably 0.

  Q is preferably a group represented by the formula (Q-1) or (Q-2), and more preferably a group represented by the formula (Q-1).

R ² , R ⁵ and R ⁸ are preferably a methyl group, an ethyl group or a C ₁ -C ₂ halo (especially substituted with a fluorine atom or a chlorine atom) alkyl group, more preferably a methyl group Or it is an ethyl group.

R ³ is preferably a hydrogen atom, a C ₁ -C ₂ alkyl group or a C ₁ -C ₂ haloalkyl group, more preferably a hydrogen atom or a methyl group.

R ⁴ is preferably a C ₁ -C ₃ alkyl group or a C ₁ -C ₃ halo (particularly substituted with a fluorine atom or a chlorine atom) alkyl group, and more preferably a C ₁ -C ₂ An alkyl group or a C ₁ -C ₂ alkyl group substituted with a fluorine atom, and even more preferably a trifluoromethyl group or a pentafluoroethyl group.

R ⁶ is preferably a hydrogen atom, a C ₁ -C ₂ alkyl group or a C ₁ -C ₂ haloalkyl group, and more preferably a trifluoromethyl group.

R ⁷ is preferably a hydrogen atom, a C ₁ -C ₂ alkyl group or a C ₁ -C ₂ haloalkyl group, and more preferably a hydrogen atom.

R ⁹ and R ¹⁰ are a hydrogen atom, a halogen atom or a C ₁ -C ₂ haloalkyl group, and more preferably a hydrogen atom.

Preferred compound groups include, for example,
Q is a group represented by the formula (Q-1) or (Q-2),
R ¹ is a C ₂ -C ₄ alkyl group or a C ₃ -C ₄ cycloalkylmethyl group substituted with halogen,
A is a methyl group, a chlorine atom or a cyano group,
X is a hydrogen atom,
a group of compounds in which n is 0 or 1;
A more preferred group of compounds is, for example,
Q is a group represented by the formula (Q-1),
A is a chlorine atom, a methyl group or a cyano group,
R ¹ is a propyl group, a 2,2,2-trifluoroethyl group or a cyclopropylmethyl group,
In the compound group, n is 0 or 1.

  Representative compounds of the present invention are exemplified in the following table, but the present invention is not limited to these compounds.

  Hereinafter, “Me” represents a methyl group, “Et” represents an ethyl group, “nPr” represents a normal propyl group, “cPr” represents a cyclopropyl group, “nBu” represents a normal butyl group, and “tBu” represents a tert. -Butyl group, "cBu" is cyclobutyl group, "Ph" is phenyl group, "4,5-DH-1,2,4-OXZ-3" is 4,5-dihydro-1,2 , 4-oxadiazol-3-yl group, “1,2,4-OXZ-3” represents 1,2,4-oxadiazol-3-yl group, “1,3-TH-2 "Represents a 1,3-thiazol-2-yl group, respectively.

Among the above exemplary compounds, suitable compounds are
Compound No. 1-4: 1-methyl-5- [4-methyl-3- (propylsulfinyl) phenyl] -3- (trifluoromethyl) -1H-pyrazole,
Compound No. 1-15: 1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole,
Compound No. 1-16: 1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -3- (trifluoromethyl) -1H-pyrazole,
Compound No. 1-35: 5- {4-chloro-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole,
Compound No. 1-43: 4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2- (propylthio) benzonitrile,
Compound No. 1-55: 4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile,
Compound No. 1-56: 4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) sulfinyl] benzonitrile,
Compound No. 1-61: 4- [1-ethyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile,
Compound No. 1-65: 4- [1-methyl-3- (pentafluoroethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile,
Compound No. 1-66: 4- [1-Methyl-3- (pentafluoroethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) sulfinyl] benzonitrile,
Compound No. 1-67: 1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (pentafluoroethyl) -1H-pyrazole Compound No. 1 -68: 1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -3- (pentafluoroethyl) -1H-pyrazole,
Compound No. 1-69: 4- [3- (Heptafluoropropyl) -1-methyl-1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile,
Compound No. 1-70: 4- [3- (Heptafluoropropyl) -1-methyl-1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) sulfinyl] benzonitrile,
Compound No. 1-72: 3- (heptafluoropropyl) -1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -1H-pyrazole,
Compound No. 1-86: 5- {4-Bromo-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole Compound No. 1 -87: 5- {4-bromo-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole,
Compound No. 1-90: 5- {4-ethyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole,
Compound No. 1-91: 1-methyl-5- {4- (2-propenyl) -3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl)- 1H-pyrazole,
Compound No. 1-93: 4-chloro-1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H- Pyrazole,
Compound No. 1-97: 5- {4-cyclopropyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole,
Compound No. 1-99: 3- (difluoromethoxy) -1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1H-pyrazole,
Compound No. 1-100: 3-[(difluoromethyl) thio] -1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1H-pyrazole or Compound No. 1-109: 1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3-[(2,2,2-trifluoroethyl) Thio] -1H-pyrazole.

  The (3-sulfur atom substituted) pyrazole derivative (I) of the present invention can be produced by the steps A, B, C, D and E described below.

(Process A)
Step A comprises steps A-1a, A-1b, A-2a, A-2b and A-3, wherein n is 0 compound (Ia) of the invention and n is 1 compound of the invention ( This is a process for producing Ib).

In the above formula, R ¹ , A, X, m and Q are as defined above,
Y ¹ represents a halogen atom,
Y ² represents a halogen atom or a trifluoromethanesulfonyloxy group,
R ¹⁴ is a hydrogen atom or a C ₁ -C ₆ alkyl group (the substituent is two adjacent R ^{14 s} , —CH ₂ CH ₂ —, —C (CH ₃ ) ₂ —C (CH ₃ )) _2- or -CH ₂ CH ₂ CH _2- may be formed).

When Y ² is a bromine atom or an iodine atom, X preferably represents a fluorine atom or a chlorine atom.

  In step A-1a, a compound represented by general formula (III) is reacted with a compound represented by general formula (V) in the presence of a base and a solvent to produce a compound represented by general formula (IV). It is a process to do.

  The base used is not particularly limited as long as it usually has a pH of 8 or more. For example, alkali metal hydroxide such as sodium hydroxide and potassium hydroxide; alkaline earth such as calcium hydroxide and magnesium hydroxide. Metal hydroxides; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkali metal hydrides such as sodium hydride and potassium hydride; Alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide; or organometallics such as methyl lithium, butyl lithium, methyl magnesium bromide and lithium diisopropylamide, preferably alkali metal Carbonates, al Potassium metal bicarbonates, alkali metal hydrides or alkali metal alkoxides, more preferably sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or sodium hydride.

  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, ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; benzene, toluene, xylene and the like. Aromatic hydrocarbons such as chlorobenzene; Nitriles such as acetonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; Like dimethyl sulfoxide and sulfolane Sulfoxides; halogenated hydrocarbons such as methylene chloride and chloroform; esters such as ethyl acetate and ethyl propionate; or aliphatic hydrocarbons such as hexane, cyclohexane and heptane; or a mixed solvent thereof And preferably An ether, nitriles or amides, more preferably tetrahydrofuran, acetonitrile or N, N- dimethylformamide.

  The amount of the solvent used is usually 1.0 to 20 liters and preferably 1.0 to 10 liters with respect to 1 mol of compound (III).

  The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually from −40 ° C. to the reflux temperature in the reaction system, and preferably from 0 to 100 ° C.

  The reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, but is usually 6 minutes to 48 hours, preferably 10 minutes to 24 hours, and more preferably 15 minutes to 10 hours. It's time.

  Compound (III) used in this step is a commercially available product or is produced according to a known method (for example, the method described in J. Heterocycl. Chem., 1991, 28, 1357-1364, etc.).

  Compound (V) used in this step is available as a commercial product.

  In step A-2a, compound (IV) is reacted with a compound represented by general formula (VI) in the presence of a transition metal catalyst, a base and a solvent. In compound (I) of the present invention, n is 0. In this step, compound (Ia) is produced.

  The transition metal catalyst used can be palladium compounds such as, for example, palladium carbon, palladium acetate, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and tris (dibenzylideneacetone) dipalladium, Preferred is tetrakis (triphenylphosphine) palladium or tris (dibenzylideneacetone) dipalladium, and more preferred is tetrakis (triphenylphosphine) palladium.

  The base used is not particularly limited as long as it usually has a pH of 8 or more. For example, alkali metal hydroxide such as sodium hydroxide and potassium hydroxide; alkaline earth such as calcium hydroxide and magnesium hydroxide. Metal hydroxides; alkali metal carbonates such as sodium carbonate and potassium carbonate; or alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, preferably alkali metal carbonates or alkali metals Bicarbonates, more preferably sodium carbonate or potassium carbonate.

  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, propanol; diethyl ether, dimethoxyethane, tetrahydrofuran, and Ethers such as dioxane; or aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; or a mixed solvent thereof, preferably a mixture of alcohols, aromatic hydrocarbons and water Solvents or ethers, more preferably a mixed solvent of ethanol, toluene and water, or dimethoxyethane.

  The amount of the transition metal catalyst used is usually 0.01 to 1.0 mol, preferably 0.05 to 0.1 mol, relative to 1 mol of compound (IV).

  The amount of the base used is usually 1.0 to 10 mol, and preferably 1.0 to 5 mol with respect to 1 mol of compound (IV).

  The amount of the solvent used is usually 0.1 to 20 liters, preferably 1.0 to 10 liters per 1 mol of compound (IV).

  The reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, but is usually from −40 ° C. to the reflux temperature in the reaction system, and preferably from 0 to 120 ° C.

  While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 10 minutes to 48 hours, preferably 30 minutes to 24 hours.

  The compound (VI) used in this step is a commercially available product, or a known method (for example, EP 1108720; 2001, WO 200512254; 2005, J. Heterocycl. Chem., 2004, 41, 931-940 etc.) As described).

  Step A-1b is a step of producing a compound represented by the general formula (IIIa) by reacting compound (III) with compound (VI) in the presence of a transition metal catalyst, a base and a solvent.

  This step is performed in the same manner as Step A-2a.

  Step A-2b is a step of producing compound (Ia) in which n is 0 in compound (I) of the present invention by reacting compound (IIIa) with compound (V) in the presence of a base and a solvent. .

で表されるベンズアルデヒド体を、工程Ａ−1ａ及びＡ−２ａと同様に反応させることにより、製造される化合物を、それぞれ、塩化メチレン中、デオキソフローと、室温で、１５時間反応させさせること及び後記工程Ｄの工程Ｄ−１と同様に反応させることにより、製造される。
さらにまた、化合物（Ｉａ）において、Ｒ^３、Ｒ^４、Ｒ^６、Ｒ^７、Ｒ^９及び／又はＲ^１０が、置換されていてもよいフェニル基である化合物（Ｉａ−５）は、Ｒ^３、Ｒ^４、Ｒ^６、Ｒ^７、Ｒ^９及び／又はＲ^１０が、ハロゲン原子（好適には、臭素原子）である相当する化合物を、式 Ｒｃ−Ｂ（ＯＲ^１４）_２（式中、Ｒ^１４は、上記と同意義を表し、Ｒｃは、前記の置換されていてもよいフェニル基を表す。）で表されるボロン化合物と、前記工程Ａ−１ｂと同様に反応させることにより、製造される。This process is performed similarly to the said process A-1a.
In the compound (Ia), the compound (Ia-1) in which A is an optionally substituted alkenyl group or thiazolyl group is a compound in which A is a halogen atom (preferably a bromine atom). , wherein M 1 ^-Rb (in the formula, M ¹ is, represents the same meaning as described later, Rb represents. the above optionally substituted alkenyl group or thiazolyl group) with a compound represented by the below steps It is produced by reacting in the same manner as in step B-1 of B.
Furthermore, in the compound (Ia), A is a compound which is a 1-hydroxy-1-ethyl (Ia-2) is (preferably bromine) A halogen atom of the compound is of the formula M ¹ - Obtained by reacting a compound represented by C (OR ¹¹ ) ═CH ₂ (wherein, M ¹ and R ¹¹ have the same meaning as described later) in the same manner as in Process B-1 of Process B described later. After the compound is acid-treated, it is produced by reacting with a reducing agent (for example, sodium borohydride) in methanol at room temperature for 1 hour.
Furthermore, in the compound (Ia), A is a difluoromethyl group (Ia-3) and A is represented by the formula —CH═NOR (wherein R is as defined above). The compound (Ia-4) as a group has the formula

Are reacted with deoxoflow in methylene chloride at room temperature for 15 hours, respectively, and It is manufactured by reacting in the same manner as in step D-1 of step D.
Furthermore, in the compound (Ia), the compound (Ia-5) in which R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁹ and / or R ¹⁰ is an optionally substituted phenyl group is represented by R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁹ and / or R ¹⁰ is a corresponding compound represented by the formula Rc-B (OR ¹⁴ ) ₂ (wherein R ¹⁰ is a bromine atom) ¹⁴ represents the same meaning as described above, and Rc represents an optionally substituted phenyl group.) And is reacted by reacting in the same manner as in Step A-1b. The

  Step A-3 is a step for producing compound (Ib) wherein n is 1 in compound (I) of the present invention by reacting compound (Ia) with an oxidizing agent in the presence of a solvent.

  The oxidizing agent used is, for example, hydrogen peroxide, m-chloroperbenzoic acid, sodium periodate, oxone (trade name: OXONE, EIDuPont, trade name: potassium hydrogen peroxosulfate) or sodium dichlorite. Obtained, preferably m-chloroperbenzoic acid or hydrogen peroxide, and more preferably m-chloroperbenzoic acid. Here, in some cases, a catalyst (for example, sodium tungstate) may be added.

  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; carboxylic acids such as acetic acid and propionic acid; diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane. Ethers such as: aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; nitriles such as acetonitrile; N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone Amides such as: Sulfoxides such as dimethyl sulfoxide and sulfolane; Halogenated hydrocarbons such as methylene chloride and chloroform; or Aliphatic hydrocarbons such as hexane, cyclohexane and heptane; or a mixed solvent thereof Preferably, halo An emission hydrocarbons, more preferably methylene chloride.

  The amount of the oxidizing agent to be used is usually 0.7 to 2.0 mol, preferably 0.9 to 1.2 mol with respect to 1 mol of compound (Ia).

  The amount of the catalyst used is usually 0.01 to 1.0 mol, preferably 0.2 mol, relative to 1 mol of compound (Ia).

  The amount of the solvent used is usually 0.1 to 20 liters, preferably 1.0 to 10 liters per 1 mol of compound (Ia).

  The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually from −40 ° C. to the reflux temperature in the reaction system, and preferably from 0 to 100 ° C.

  While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 6 minutes to 48 hours, and preferably 30 minutes to 24 hours.

  The target product obtained in the above step is collected from the reaction mixture by a conventional method. For example, when the target product is precipitated as crystals in the reaction mixture, the target product is collected by filtration. If the reaction mixture contains an insoluble material, the insoluble material is filtered off as appropriate, and the reaction mixture is acidic or alkaline. If appropriate, neutralize and distill off the solvent under reduced pressure, or add water to the reaction mixture or the above solvent distilled off under reduced pressure and extract with a water-immiscible organic solvent, The target product can be obtained by drying the extract and evaporating the extraction solvent under reduced pressure. If necessary, the target product can be further purified by a conventional method such as recrystallization or column chromatography.

(Process B)
Step B consists of Steps B-1, B-2, B-3 and B-4. In the compound (I) of the present invention, Q is a compound represented by the formula Qa, which will be described later, and the general formula (Ic). This is a step for producing a compound represented by (VIIIa) [or a tautomer (VIIIb) thereof].

In the above formula, R ¹ , A, X, m, R ² and Y ² are as defined above,
R ¹² represents the same meaning as R ³ except a halogen atom,
R ^4a represents the same meaning as R ⁴ excluding a halogen atom,
Qa is the formula (Qa-1) or (Qa-2)

(Wherein R ² and R ^4a represent the same meaning as described above, R ^3a represents the same meaning as R ^12, and R ⁵ , R ^6a and R ^7a represent R ² , R ^3a and R ^4a , respectively. And the same meaning.)
Represents a group represented by
R ¹¹ represents a C ₁ -C ₆ alkyl group,
M ¹ represents tri (C ₁ -C ₆ alkyl) tin.

  Step B-1 is a step of producing a compound represented by the general formula (VII) by reacting the compound (IV) with a compound represented by the general formula (IX) in the presence of a transition metal catalyst and a solvent. .

  The transition metal catalyst used can be, for example, palladium compounds such as dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and tris (dibenzylideneacetone) dipalladium, preferably dichlorobis ( Triphenylphosphine) palladium.

  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, ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; benzene, toluene, xylene and the like. Aromatic hydrocarbons such as chlorobenzene; nitriles such as acetonitrile; or amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; or mixtures thereof It can be a solvent, preferably an aromatic hydrocarbon, and more preferably toluene.

  The amount of the transition metal catalyst used is usually 0.01 to 1.0 mol, preferably 0.05 to 0.1 mol, relative to 1 mol of compound (IV).

  The amount of the solvent used is usually 1.0 to 20 liters, preferably 1.0 to 10 liters per 1 mol of compound (IV).

  The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually from −40 ° C. to the reflux temperature in the reaction system, and preferably from 0 to 140 ° C.

  The reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, but is usually 10 minutes to 48 hours, preferably 20 minutes to 24 hours, and more preferably 30 minutes to 10 hours. It's time.

  Compound (IX) used in this step is a commercially available product, or is produced according to a known method (for example, a method described in US 5179088; 1993).

  In step B-2, compound (VII) is reacted with a compound represented by general formula (Xa) or a compound represented by general formula (Xb) in the presence of a base and a solvent, and represented by general formula (VIII). This is a process for producing a compound to be produced.

  The base used is not particularly limited as long as it usually has a pH of 8 or more. For example, alkali metal hydroxide such as sodium hydroxide and potassium hydroxide; alkaline earth such as calcium hydroxide and magnesium hydroxide. Metal hydroxides; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; or organics such as triethylamine, N, N-dimethylaniline and pyridine It can be a base, preferably an organic base, and more preferably pyridine.

  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, ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ethyl acetate and ethyl propionate Esters such as: aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; nitriles such as acetonitrile; N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone Amides such as: Sulfoxides such as dimethyl sulfoxide and sulfolane; Halogenated hydrocarbons such as methylene chloride and chloroform; or Aliphatic hydrocarbons such as hexane, cyclohexane and heptane; or a mixed solvent thereof And preferably Ethers are esters, aromatic hydrocarbons or halogenated hydrocarbons, and more preferably tetrahydrofuran, ethyl acetate, toluene or methylene chloride.

  The amount of the base used is usually 1.0 to 5.0 mol, preferably 1.0 to 2.0 mol, relative to 1 mol of compound (VII).

  The amount of the solvent used is usually 1.0 to 20 liters and preferably 1.0 to 10 liters with respect to 1 mol of compound (VII).

  The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually from −40 ° C. to the reflux temperature in the reaction system, and preferably from 0 to 100 ° C.

  While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 10 minutes to 48 hours, preferably 30 minutes to 24 hours.

  Compound (Xa) used in this step is a commercially available product, or is produced according to a known method (for example, the method described in Synthesis, 1989, 832-835, etc.).

  Compound (Xb) used in this step is commercially available.

  In step B-3, compound (VIII) is reacted with a compound represented by general formula (XI) in the presence of a solvent. In compound (I) of the present invention, compound (Ic) wherein Q is a group of formula Qa ).

  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; carboxylic acids such as acetic acid and propionic acid; alcohols such as methanol, ethanol and propanol Ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; nitriles such as acetonitrile; N, N-dimethylformamide, N, N Amides such as dimethylacetamide and N-methyl-2-pyrrolidone; Sulfoxides such as dimethyl sulfoxide and sulfolane; Halogenated hydrocarbons such as methylene chloride and chloroform; or Fats such as hexane, cyclohexane and heptane Hydrocarbons; or a mixed solvent thereof, preferably water, carboxylic acids, alcohols or aromatic hydrocarbons or a mixed solvent thereof, more preferably water, acetic acid, methanol. Ethanol or toluene or a mixed solvent thereof.

  The amount of the solvent used is usually 1.0 to 20 liters, preferably 1.0 to 10 liters per 1 mol of compound (VIII).

  The reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, but is usually from −40 ° C. to the reflux temperature in the reaction system, and preferably from 50 to 150 ° C.

  The reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, but is usually 10 minutes to 48 hours, preferably 20 minutes to 24 hours, and more preferably 1 hour to 10 hours. It's time.

Compound (XI) used in this step is commercially available.
Step B-4 is a step of reacting compound (VIII) with an acid in the presence of a solvent to produce a compound represented by general formula (VIIIa) [or a tautomer (VIIIb) thereof]. Compound (VIIIa) [or its tautomer (VIIIb)] can be reacted with compound (XI) in the same manner as in Step B-3 to give compound (Ic).
The acid to be used is not particularly limited as long as it usually shows pH 3 or lower, and for example, it can be a mineral acid such as hydrochloric acid and sulfuric acid, preferably hydrochloric 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, alcohols such as methanol, ethanol and propanol; diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane Ethers such as ethyl acetate and esters such as ethyl propionate; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; nitriles such as acetonitrile; N, N-dimethylformamide, N, N Amides such as dimethylacetamide and N-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide and sulfolane; halogenated hydrocarbons such as methylene chloride and chloroform; or such as hexane, cyclohexane and heptane Aliphatic hydrocarbons; or a mixed solvent thereof, preferably alcohols, esters, aromatic hydrocarbons or halogenated hydrocarbons, more preferably methanol, ethyl acetate, Toluene or methylene chloride.
The amount of the acid used is usually 0.1 to 5.0 mol, preferably 0.1 to 2.0 mol, relative to 1 mol of compound (VIII).
The amount of the solvent used is usually 1.0 to 20 liters and preferably 1.0 to 10 liters with respect to 1 mol of compound (VIII).
The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually from 0 ° C to the boiling point of the solvent, and preferably from 20 to 80 ° C.
While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 5 minutes to 48 hours, preferably 10 minutes to 24 hours.

  The target product obtained in the above step is collected from the reaction mixture by a conventional method. For example, when the target product is precipitated as crystals in the reaction mixture, the target product is collected by filtration. If the reaction mixture contains an insoluble material, the insoluble material is filtered off as appropriate, and the reaction mixture is acidic or alkaline. If appropriate, neutralize and distill off the solvent under reduced pressure, or add water to the reaction mixture or the above solvent distilled off under reduced pressure and extract with a water-immiscible organic solvent, The target product can be obtained by drying the extract and evaporating the extraction solvent under reduced pressure. If necessary, the target product can be further purified by a conventional method such as recrystallization or column chromatography.

(Process C)
Step C consists of Steps C-1 to C-8, and is a step for separately producing Compound (Ia) in which n is 0 in Compound (I) of the present invention.

In the above formula, R ¹ , A, Q, X, m, R ² , R ³ , R ⁴ , R ¹⁴ and Y ² represent the same meaning as described above,
Qb represents a group represented by the formula (Q-1) or (Q-2) (wherein R ⁵ , R ⁶ and R ⁷ correspond to R ² , R ³ and R ⁴ , respectively). Show
Y ³ represents a halogen atom or a trifluoromethanesulfonyloxy group,
Y ⁴ represents a halogen atom,
R ¹³ represents a C ₁ -C ₆ alkyl group,
M ² represents an alkali metal (preferably sodium or potassium).

In the step C-1, the compound represented by the general formula (XII) is reacted with the compound (VI) in the presence of a transition metal catalyst, a base and a solvent, and in the production intermediate (II) of the present invention, X ¹ is This is a process for producing a compound represented by the general formula (IIa) including a compound which is a hydrogen atom or a fluorine atom.

  This process is performed similarly to process A-2a of said A process.

Compound (XII) used in this step is commercially available.
In the compound (IIa), Q is a compound represented by the formula

Wherein R ² and R ³ are as defined above, and R ^4b represents the above-mentioned optionally substituted C ₁ -C ₆ alkoxy group. IIa-1) can also be produced by reacting the compound (XXII) obtained in Step E-1 of Step E, which will be described later, with Compound (XXIII) described later in the same manner as Step E-3b of Step E, which will be described later. .

In Step C-2, a compound represented by the general formula (XIII) is reacted with a compound represented by the general formula (XIV) in the presence of a transition metal catalyst, a base and a solvent, and the production intermediate (II ), Wherein X ¹ is a hydrogen atom or a fluorine atom, and the compound (IIa) is separately produced.

  The base used is not particularly limited as long as it usually has a pH of 8 or more. For example, alkali metal hydroxide such as sodium hydroxide and potassium hydroxide; alkaline earth such as calcium hydroxide and magnesium hydroxide. Metal hydroxides; alkali metal phosphates such as sodium phosphate and potassium phosphate; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate Alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide; or methyllithium, butyllithium, methylmagnesium bromide, lithium diisopropylamide And is preferably alkali metal carbonates, alkali metal bicarbonates or alkali metal phosphates, and more preferably sodium carbonate or potassium phosphate.

  The transition metal catalyst used can be, for example, palladium compounds such as dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and tris (dibenzylideneacetone) dipalladium, preferably tetrakis ( Triphenylphosphine) palladium.

  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, ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; benzene, toluene, xylene and the like. Aromatic hydrocarbons such as chlorobenzene; nitriles such as acetonitrile; or amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; or mixtures thereof It can be a solvent, preferably ethers or amides, more preferably dimethoxyethane, tetrahydrofuran, dioxane or N, N-dimethylformamide.

  The amount of the transition metal catalyst used is usually 0.01 to 1.0 mol, preferably 0.05 to 0.1 mol, relative to 1 mol of compound (XIII).

  The amount of the solvent used is usually 1.0 to 20 liters and preferably 1.0 to 10 liters with respect to 1 mol of compound (XIII).

  The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually from −40 ° C. to the reflux temperature in the reaction system, and preferably from 0 to 140 ° C.

  While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is usually 10 minutes to 48 hours, preferably 1 hour to 24 hours.

  Compound (XIV) used in this step is described in a known method (for example, J. Med. Chem., 2002, 45, 2994-3008, Eur. J. Org. Chem., 2002, 2913-2920, etc.) Manufactured in accordance with the above method).

  Compound (XIII) used in this step is commercially available.

In step C-3, the compound represented by the general formula (XV) is reacted with the compound (XI) in the presence of a solvent. In the production intermediate (II) of the present invention, X ¹ is a hydrogen atom or a fluorine atom. There is a step for producing a compound represented by the general formula (IIb) including a compound in which Q is a group of the formula Qb.

  This step is performed in the same manner as the step B-3 in the step B.

  Compound (XV) used in this step is produced according to a known method (for example, a method described in J. Org. Chem., 1990, 55, 1959-1964, etc.).

Step C-4 is a compound represented by the general formula (IIc) in which the compound (IIa) produced by Step C-1 and the like is nitrated, and in the production intermediate (II) of the present invention, X ¹ is a nitro group. This is a process for producing a compound.

  This step is a conventional method for nitrating a normal aromatic ring, for example, a method using a mixed acid of concentrated sulfuric acid-concentrated nitric acid, a method using potassium nitrate, or a method using cupric nitrate-acetic acid (. Acetic anhydride). Can be done according to.

  This step is performed in the presence or absence of a solvent (preferably in the absence of a solvent).

  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, carboxylic acids such as acetic acid and propionic acid or dichloromethane, chloroform and 1,2-dichloroethane can be used. Halogenated hydrocarbons, preferably acetic acid or chloroform.

  The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually from −90 ° C. to the reflux temperature in the reaction system, and preferably from −50 to 80 ° C.

［式中、Ｒ^２及びＲ^４は、前記と同意義を表し、Ｒ^３ｂは、ハロゲン原子（好適には、塩素原子又は臭素原子）を表す。］
で表される基である化合物（ＩＩｃ−１）は、Ｒ^３ｂが水素原子である相当する化合物を、ハロゲン化剤（例えば、Ｎ−ハロコハク酸イミド等）と反応させて、製造することもできる。
さらに、化合物（ＩＩｃ）において、Ａが、トリメチルシリルエチニル基である（ＩＩｃ−２）は、Ａがハロゲン原子（好適には、臭素原子）である相当する化合物を、トリメチルシリルアセチレンと、酢酸パラジウム、ヨウ化第一銅、トリフェニルホスフィン及びトリエチルアミンの存在下、反応させることにより製造され、この化合物を、工程Ｃ−５〜Ｃ−８と同様に反応させることにより、化合物（Ｉａ）において、Ａがエチニル基である化合物が製造される。While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 5 minutes to 24 hours, and preferably 30 minutes to 6 hours.
In addition, in the compound (IIc), Q is a formula

[Wherein, R ² and R ⁴ represent the same meaning as described above, and R ^3b represents a halogen atom (preferably a chlorine atom or a bromine atom). ]
Compound (IIc-1), which is a group represented by the following formula, can also be produced by reacting a corresponding compound in which R ^3b is a hydrogen atom with a halogenating agent (eg, N-halosuccinimide). .
Further, in the compound (IIc), (IIc-2) in which A is a trimethylsilylethynyl group represents a corresponding compound in which A is a halogen atom (preferably a bromine atom), trimethylsilylacetylene, palladium acetate, iodine It is produced by reacting in the presence of cuprous chloride, triphenylphosphine, and triethylamine. By reacting this compound in the same manner as in Steps C-5 to C-8, in compound (Ia), A is ethynyl. A group of compounds is produced.

Step C-5 is a step of reducing the nitro group of compound (IIc) to produce compound (IId) in which X ¹ is an amino group in the production intermediate (II) of the present invention.

  This step is usually performed, for example, a method of hydrogenation in the presence of a palladium carbon catalyst, a method using stannous chloride in the presence of concentrated hydrochloric acid, or a method using metal powder (for example, iron powder) -ammonium chloride. It can be carried out according to a conventional method for reducing a nitro group to an amino group (for example, the method described in J. Am. Chem. Soc., 1961, 83, 2489-2493, WO 2005023807; 2005, etc.).

  This step is performed in the presence or absence of a solvent (preferably in the presence of a solvent).

  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, water; alcohols such as methanol, ethanol and propanol; diethyl ether, dimethoxyethane, tetrahydrofuran and Ethers such as dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; Alternatively, there are sulfoxides such as dimethyl sulfoxide and sulfolane, preferably alcohols or ethers, and more preferably methanol or ethanol.

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

While the reaction time varies depending on the raw material compound, the reaction reagent, the solvent, the reaction temperature and the like, it is usually 5 minutes to 24 hours, and preferably 30 minutes to 12 hours.
In the compound (IId), the compound (IId-1) in which A is an ethyl group is the same as the compound (IIc) in which A is a halogen atom (preferably a bromine atom), trimethylsilylacetylene and acetic acid. It is also produced by reacting in the presence of palladium, cuprous iodide, triphenylphosphine and triethylamine, then removing the trimethylsilyl group with potassium carbonate / methanol and catalytic reduction using a Lindlar catalyst. .

  Step C-6 is a step of producing a compound represented by the general formula (XVII) by reacting a compound represented by the general formula (XVI) after making the amino group of the compound (IId) a diazonium salt. .

  In this step, for example, the reaction is carried out according to a conventional method for converting an amino group into a diazonium salt, such as a method using nitrous acid, nitrite (for example, sodium nitrite) or alkyl nitrite, The reaction can be performed by reacting the obtained diazonium salt with xanthate.

  The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, and may be, for example, nitriles such as water or acetonitrile, preferably water or acetonitrile. .

  The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually −70 ° C. to reflux temperature in the reaction system, and preferably −20 to 100 ° C.

  While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 10 minutes to 24 hours, preferably 30 minutes to 12 hours.

Step C-7 is a step of hydrolyzing compound (XVII) in the presence of a base and a solvent to produce compound (IIe) in which X ¹ is a mercapto group in the production intermediate (II) of the present invention. .

  The base 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; or alkalis such as calcium hydroxide and magnesium hydroxide. It can be an earth metal hydroxide, preferably sodium hydroxide or potassium hydroxide.

  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, propanol; or diethyl ether, dimethoxyethane, tetrahydrofuran And ethers such as dioxane; or a mixed solvent thereof, preferably a mixed solvent of alcohols and water, and more preferably a mixed solvent of methanol or ethanol and water.

  The amount of the base used is usually 1.0 to 10 mol, and preferably 1.0 to 3.0 mol with respect to 1 mol of compound (XVII).

  The amount of the solvent used is usually 1.0 to 20 liters and preferably 1.0 to 10 liters with respect to 1 mol of compound (XVII).

  The reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, but is usually from −40 ° C. to the reflux temperature in the reaction system, and preferably from 0 to 120 ° C.

While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 10 minutes to 48 hours, preferably 30 minutes to 24 hours.
In the compound (II), X ¹ is represented by the formula —S (C═Z) R′a (wherein Z represents the same meaning as described above, and R′a represents a C ₁ -C ₆ alkyl group or Compound (IIf) represented by C ₁ -C ₆ alkoxy group) is obtained by reacting compound (IIe) with a compound of the formula R in the presence of a base (eg, triethylamine) and a solvent (eg, ether, dichloromethane, etc.). a halo compound (preferably a chloro compound) represented by 'a-C (= Z) Y ¹ (wherein R'a, Y ¹ and Z are as defined above), and room temperature And produced by reacting for 30 minutes to 10 hours.

  In step C-8, compound (IIe) is reacted with a compound represented by general formula (XVIII) in the presence of a base and a solvent, and in compound (I) of the present invention, n is 0. Is a process of separately manufacturing.

  The base used is not particularly limited as long as it usually has a pH of 8 or more. For example, alkali metal hydroxide such as sodium hydroxide and potassium hydroxide; alkaline earth such as calcium hydroxide and magnesium hydroxide. Metal hydroxides; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkali metal hydrides such as sodium hydride and potassium hydride; Alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide; or organometallics such as methyl lithium, butyl lithium, methyl magnesium bromide, lithium diisopropylamide, preferably alkali metal Carbonates, Arca Li metal bicarbonates, alkali metal hydrides or alkali metal alkoxides, more preferably sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or sodium hydride.

  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; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; benzene, toluene, Aromatic hydrocarbons such as xylene and chlorobenzene; Nitriles such as acetonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; Dimethyl sulfoxide and sulfolane Sulfoxides such as: halogenated hydrocarbons such as methylene chloride and chloroform; or aliphatic hydrocarbons such as hexane, cyclohexane and heptane; or a mixed solvent thereof, preferably water, Ethers, halogenated hydrocarbons, aliphatic charcoal Hydrogen compound or aromatic hydrocarbons, or mixtures of these solvents, more preferably, water, tetrahydrofuran, dioxane, N, N-dimethylformamide or acetonitrile, or a mixed solvent thereof.

  The amount of the base to be used is usually 1.0 to 10 mol, preferably 1.0 to 3.0 mol, relative to 1 mol of compound (IIe).

  The amount of the solvent used is usually 1.0 to 20 liters and preferably 1.0 to 10 liters with respect to 1 mol of compound (IIe).

  The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually −40 ° C. to reflux temperature in the reaction system, and preferably 0 to 100 ° C.

  While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 6 minutes to 48 hours, and preferably 10 minutes to 24 hours.

上式中、Ｒ^１、Ｒ、Ａａ、Ｘ、ｍ及びＱは、前記と同意義を示し、
Ｒ^１５は、水素原子又はＣ_１−Ｃ_６アルキル基を示し、
Ｒ^１６は、Ｃ_１−Ｃ_６アルキル基を示す。
工程Ｄ−１は、溶媒及び塩基存在下、一般式（Ｉ’）で表されるシアノ化合物を、一般式（ＸＩＸ）で表される化合物又はその塩（例えば、硫酸塩、塩酸塩又は硝酸塩、好適には、塩酸塩）と反応させ、化合物（Ｉｄ）を製造する工程である。
使用される塩基は、通常ｐＨ８以上を示す塩基であれば特に限定はなく、例えば、水酸化ナトリウム及び水酸化カリウムのようなアルカリ金属水酸化物；水酸化カルシウム及び水酸化マグネシウムのようなアルカリ土類金属水酸化物；炭酸ナトリウム及び炭酸カリウムのようなアルカリ金属炭酸塩類；炭酸水素ナトリウム及び炭酸水素カリウムのようなアルカリ金属重炭酸塩類；トリエチルアミン、Ｎ，Ｎ−ジメチルアニリン及びピリジンのような有機塩基であり得、好適には、有機塩基であり、より好適には、トリエチルアミンである。
使用される溶媒は、反応を阻害せず、出発物質をある程度溶解するものであれば特に限定はなく、例えば、ジエチルエーテル、ジメトキシエタン、テトラヒドロフラン及びジオキサンのようなエーテル類；酢酸エチル及びプロピオン酸エチルのようなエステル類；ベンゼン、トルエン、キシレン及クロロベンゼンのような芳香族炭化水素類；アセトニトリルのようなニトリル類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド及びＮ−メチル−２−ピロリドンのようなアミド類；ジメチルスルホキシド及びスルホランのようなスルホキシド類；塩化メチレン及びクロロホルムのようなハロゲン化炭化水素類；又はヘキサン、シクロヘキサン及びヘプタンのような脂肪族炭化水素類；或はこれらの混合溶媒であり得、好適には、エーテル類であり、より好適には、ジオキサンである。
用いられる塩基の量は、化合物（Ｉ’）１ｍｏｌに対し、通常、１．０〜５．０ｍｏｌであり、好適には、１．０〜２.０ｍｏｌである。
用いられる溶媒の量は、化合物（Ｉ’）１ｍｏｌに対し、通常、１．０〜２０リットルであり、好適には、１．０〜１０リットルである。
反応温度は、原料化合物、反応試薬及び溶媒等により異なるが、通常、０〜１５０℃であり、好適には、６０〜１２０℃である。
反応時間は、原料化合物、反応試薬、溶媒及び反応温度等により異なるが、通常、５分間〜４８時間であり、好適には、１０分間〜２４時間である。
工程Ｄ−２は、酸及び溶媒存在下、化合物（Ｉｄ）において、Ｒが水素原子である化合物（Ｉｄ−１）を、一般式（ＸＸａ）で表される化合物又は一般式（ＸＸｂ）で表される化合物と反応させ、本発明の化合物（Ｉｅ）を製造する工程である。なお、化合物（ＸＸｂ）において、Ｒ^１５が水素原子である場合は、好適には、ホルマリン（含水ホルムアルデヒド）又はパラホルムアルデヒドとして、化合物（ＸＸｂ）を反応させることができる。
使用される酸は、通常ｐＨ５以下を示す酸であれば特に限定はなく、例えば、塩酸及び硫酸のような鉱酸類、酢酸、プロピオン酸、トリフルオロ酢酸及び安息香酸のようなカルボン酸類又はメタンスルホン酸、ベンゼンスルホン酸及びパラトルエンスルホン酸のようなスルホン酸類であり、化合物（ＸＸａ）との反応では、好適には、鉱酸類であり、より好適には、硫酸であり、化合物（ＸＸｂ）との反応では、好適には、カルボン酸類であり、より好適には、酢酸である。また、酢酸等は、溶媒を兼ねて、大過剰に使用することもできる。
使用される溶媒は、反応を阻害せず、出発物質をある程度溶解するものであれば特に限定はなく、例えば、水；酢酸及びプロピオン酸のようなカルボン酸類；メタノール、エタノール、プロパノールのようなアルコール類；ジエチルエーテル、ジメトキシエタン、テトラヒドロフラン及びジオキサンのようなエーテル類；ベンゼン、トルエン、キシレン及クロロベンゼンのような芳香族炭化水素類；アセトニトリルのようなニトリル類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド及びＮ−メチル−２−ピロリドンのようなアミド類；ジメチルスルホキシド及びスルホランのようなスルホキシド類；塩化メチレン及びクロロホルムのようなハロゲン化炭化水素類；又はヘキサン、シクロヘキサン及びヘプタンのような脂肪族炭化水素類；或はこれらの混合溶媒であり得、好適には、アルコール類又は芳香族炭化水素類であり、より好適には、メタノール、エタノール又はトルエンである。
用いられる酸の量は、化合物（Ｉｄ−１）１ｍｏｌに対し、通常、０．１〜５．０ｍｏｌであり、好適には、０．１〜１.０ｍｏｌである。
用いられる溶媒の量は、化合物（Ｉｄ−１）１ｍｏｌに対し、通常、１．０〜２０リットルであり、好適には、１．０〜１０リットルである。
反応温度は、原料化合物、反応試薬及び溶媒等により異なるが、通常、０℃〜反応系における還流温度であり、好適には、５〜１００℃である。
反応時間は、原料化合物、反応試薬、溶媒及び反応温度等により異なるが、通常、１時間〜９０時間であり、好適には、５時間〜７２時間である。
上記工程で得られた目的物は、常法により、反応混合物から採取される。例えば、反応混合物中に目的物が結晶として析出する場合、目的物を濾取することにより、反応混合物が不溶物を含む場合は、適宜、不溶物を濾去し、反応混合物が酸性又はアルカリ性の場合は、適宜、中和して、溶媒を減圧で留去することにより、又は、反応混合物又は上記の溶媒を減圧で留去したものに水を加え、水不混和性有機溶媒で抽出し、抽出液を乾燥し、抽出溶媒を減圧で留去することにより、目的物を得ることができる。また、必要に応じて、常法、例えば、再結晶法、カラムクロマトグラフィー等を用いて、目的物をさらに精製することができる。
（工程Ｅ）
工程Ｅは、工程Ｅ−１〜Ｅ−６からなり、本発明の化合物（Ｉ）において、Ｑが、式

The target product obtained in the above step is collected from the reaction mixture by a conventional method. For example, when the target product is precipitated as crystals in the reaction mixture, the target product is collected by filtration. If the reaction mixture contains an insoluble material, the insoluble material is filtered off as appropriate, and the reaction mixture is acidic or alkaline. If appropriate, neutralize and distill off the solvent under reduced pressure, or add water to the reaction mixture or the above solvent distilled off under reduced pressure and extract with a water-immiscible organic solvent, The target product can be obtained by drying the extract and evaporating the extraction solvent under reduced pressure. If necessary, the target product can be further purified by a conventional method such as recrystallization or column chromatography.
(Process D)
Step D consists of Steps D-1 and D-2, and in the compound (I) of the present invention, A represents the formula —C (NH ₂ ) ═NOR (wherein R represents the same meaning as described above). And the compound (Id) and A are groups Aa (where Aa is a 1,2,4-oxadiazolyl group optionally substituted with a C ₁ -C ₆ alkyl group, or It represents a dihydro-1,2,4-oxadiazolyl group.) A compound (Ie) is produced.

In the above formula, R ¹ , R, Aa, X, m and Q are as defined above,
R ¹⁵ represents a hydrogen atom or a C ₁ -C ₆ alkyl group,
R ¹⁶ represents a C ₁ -C ₆ alkyl group.
In step D-1, in the presence of a solvent and a base, the cyano compound represented by the general formula (I ′) is converted to the compound represented by the general formula (XIX) or a salt thereof (for example, sulfate, hydrochloride or nitrate, Preferably, it is a step of reacting with hydrochloride) to produce compound (Id).
The base used is not particularly limited as long as it usually has a pH of 8 or more. For example, alkali metal hydroxide such as sodium hydroxide and potassium hydroxide; alkaline earth such as calcium hydroxide and magnesium hydroxide. Metal hydroxides; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; organic bases such as triethylamine, N, N-dimethylaniline and pyridine Preferably, it is an organic base, more preferably triethylamine.
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, ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ethyl acetate and ethyl propionate Esters such as: aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; nitriles such as acetonitrile; N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone Amides such as: Sulfoxides such as dimethyl sulfoxide and sulfolane; Halogenated hydrocarbons such as methylene chloride and chloroform; or Aliphatic hydrocarbons such as hexane, cyclohexane and heptane; or a mixed solvent thereof And preferably An ether, more preferably, dioxane.
The amount of the base used is usually 1.0 to 5.0 mol, and preferably 1.0 to 2.0 mol with respect to 1 mol of compound (I ′).
The amount of the solvent used is usually 1.0 to 20 liters and preferably 1.0 to 10 liters with respect to 1 mol of compound (I ′).
The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent, and the like, but is usually 0 to 150 ° C, and preferably 60 to 120 ° C.
While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 5 minutes to 48 hours, preferably 10 minutes to 24 hours.
In Step D-2, in the presence of an acid and a solvent, in the compound (Id), the compound (Id-1) in which R is a hydrogen atom is represented by the compound represented by the general formula (XXa) or the general formula (XXb). In which the compound (Ie) of the present invention is produced. In the compound (XXb), when R ¹⁵ is a hydrogen atom, the compound (XXb) can be preferably reacted as formalin (hydrous formaldehyde) or paraformaldehyde.
The acid to be used is not particularly limited as long as it is usually an acid having a pH of 5 or less. For example, mineral acids such as hydrochloric acid and sulfuric acid, carboxylic acids such as acetic acid, propionic acid, trifluoroacetic acid and benzoic acid, or methanesulfone. Acids, sulfonic acids such as benzenesulfonic acid and paratoluenesulfonic acid, and in the reaction with compound (XXa), preferably a mineral acid, more preferably sulfuric acid, and compound (XXb) In this reaction, carboxylic acids are preferable, and acetic acid is more preferable. Acetic acid or the like can also be used in a large excess as a solvent.
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; carboxylic acids such as acetic acid and propionic acid; alcohols such as methanol, ethanol and propanol Ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; nitriles such as acetonitrile; N, N-dimethylformamide, N, N Amides such as dimethylacetamide and N-methyl-2-pyrrolidone; Sulfoxides such as dimethyl sulfoxide and sulfolane; Halogenated hydrocarbons such as methylene chloride and chloroform; or Fats such as hexane, cyclohexane and heptane Hydrocarbons; or can be a mixture of these solvents, preferably an alcohol or an aromatic hydrocarbon, more preferably a methanol, ethanol or toluene.
The amount of the acid used is usually 0.1 to 5.0 mol, preferably 0.1 to 1.0 mol, relative to 1 mol of compound (Id-1).
The amount of the solvent used is usually 1.0 to 20 liters and preferably 1.0 to 10 liters with respect to 1 mol of compound (Id-1).
The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent, and the like, but is usually 0 ° C. to reflux temperature in the reaction system, and preferably 5 to 100 ° C.
While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is usually 1 hour to 90 hours, preferably 5 hours to 72 hours.
The target product obtained in the above step is collected from the reaction mixture by a conventional method. For example, when the target product is precipitated as crystals in the reaction mixture, the target product is collected by filtration. If appropriate, neutralize and distill off the solvent under reduced pressure, or add water to the reaction mixture or the above solvent distilled off under reduced pressure and extract with a water-immiscible organic solvent, The target product can be obtained by drying the extract and evaporating the extraction solvent under reduced pressure. If necessary, the target product can be further purified by a conventional method such as recrystallization or column chromatography.
(Process E)
Step E consists of steps E-1 to E-6. In the compound (I) of the present invention, Q is a compound represented by the formula

上記式中、Ｒ^１、Ｒ^２、Ｘ、ｍ、Ａ、Ｒ^１８及びＹ^４は、前記と同意義を示し、
Ｙ^５は、ハロゲン原子を示し、
Ｒ^１７は、Ｃ_１−Ｃ_６アルキルを示し、
Ｒ^１８ａは、前記Ｒ^４における置換されていてもよいＣ_１−Ｃ_６アルキル基を表す。
工程Ｅ−１は、溶媒存在下、一般式（ＸＸＩ）で表される化合物を、化合物（ＸＩ）と反応させ、一般式（ＸＸＩＩ）で表される化合物を製造する工程である。
使用される溶媒は、反応を阻害せず、出発物質をある程度溶解するものであれば特に限定はなく、例えば、水；酢酸、プロピオン酸のようなカルボン酸類；メタノール、エタノール、プロパノールのようなアルコール類；ジエチルエーテル、ジメトキシエタン、テトラヒドロフラン及びジオキサンのようなエーテル類；ベンゼン、トルエン、キシレン及クロロベンゼンのような芳香族炭化水素類；アセトニトリルのようなニトリル類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド及びＮ−メチル−２−ピロリドンのようなアミド類；ジメチルスルホキシド及びスルホランのようなスルホキシド類；塩化メチレン及びクロロホルムのようなハロゲン化炭化水素類；又はヘキサン、シクロヘキサン及びヘプタンのような脂肪族炭化水素類；或はこれらの混合溶媒であり得、好適には、水又はアルコール類或はこれらの混合溶媒であり、より好適には、水又はエタノール或はこれらの混合溶媒である。
用いられる溶媒の量は、化合物（ＸＸＩ）１ｍｏｌに対し、通常、１．０〜２０リットルであり、好適には、１．０〜１０リットルである。
反応温度は、原料化合物、反応試薬及び溶媒等により異なるが、通常、−４０℃〜反応系における還流温度であり、好適には、０〜１００℃である。
反応時間は、原料化合物、反応試薬、溶媒及び反応温度等により異なるが、通常、５分間〜４８時間であり、好適には、１０分間〜２４時間である。
本工程に使用される化合物（ＸＸＩ）は、既知の方法（例えば、Synthesis, 1989, 217-218等）によって製造される。
工程Ｅ−２は、溶媒存在下、化合物（ＸＸＩＩ）を、ローソン試薬と反応させ、一般式（ＸＸＩＩａ）を有する化合物を製造する工程である。
使用される溶媒は、反応を阻害せず、出発物質をある程度溶解するものであれば特に限定はなく、例えば、ベンゼン、トルエン、キシレン及クロロベンゼンのような芳香族炭化水素類；又はヘキサン、シクロヘキサン及びヘプタンのような脂肪族炭化水素類；或はこれらの混合溶媒であり、好適には、芳香族炭化水素類であり、より好適には、トルエンである。
用いられる溶媒の量は、化合物（ＸＸＩＩ）１ｍｏｌに対し、通常、１．０〜２０リットルであり、好適には、１．０〜１０リットルである。
反応温度は、原料化合物、反応試薬及び溶媒等により異なるが、通常、０〜１５０℃であり、好適には、３０〜１４０℃である。
反応時間は、原料化合物、反応試薬、溶媒及び反応温度等により異なるが、通常、５分間〜４８時間であり、好適には、１０分間〜２４時間である。
工程Ｅ−３ａは、塩基及び溶媒存在下、化合物（ＸＸＩＩａ）を、一般式（ＸＸＩＩＩ）で表される化合物と反応させ、一般式（ＸＸＩＶ）で表される化合物において、Ｒ^１８が、前記の置換されていてもよいＣ_１−Ｃ_６アルキルチオ基である化合物（ＸＸＩＶａ）を製造する工程である。
本工程は、前記工程Ｃの工程Ｃ−８と同様に行われる。
工程Ｅ−３ｂは、化合物（ＸＸＩＩ）を、化合物（ＸＸＩＩＩ）と反応させ、化合物（ＸＸＩＶ）において、Ｒ^１８が、前記の置換されていてもよいＣ_１−Ｃ_６アルコキシ基である化合物（ＸＸＩＶｂ）及び、化合物（ＸＸＩＩ）を、ハロゲン化剤（例えば、オキシ塩化リン、五塩化リン、四塩化炭素−トリフェニルホスフィン、オキシ臭化リン、五臭化リン、四臭化炭素−トリフェニルホスフィン、オキシヨウ化リン等）を反応させ、化合物（ＸＸＩＶ）において、Ｒ^１８が、ハロゲン原子（好適には、塩素原子又は臭素原子）である化合物（ＸＸＩＶｃ）を製造する工程である。
化合物（ＸＸＩＩ）と化合物（ＸＸＩＩＩ）との反応は、前記Ｃ法工程Ｃ−８と同様に行われ、化合物（ＸＸＩＩ）とハロゲン化剤の反応は、溶媒の非存在下又は溶媒（例えば、クロロホルム及び四塩化炭素のようなハロゲン化炭化水素類等である。）の存在下（好適には、溶媒の非存在下）、１００〜２００℃で、５分間〜１２時間反応させることにより行われる。
工程Ｅ−４は、溶媒存在下又は非存在化、化合物（ＸＸＩＶ）とクロロスルホン酸を反応させ、一般式（ＸＸＶ）を有する化合物を製造する工程である。
使用される溶媒は、反応を阻害せず、出発物質をある程度溶解するものであれば特に限定はなく、例えば、塩化メチレン及びクロロホルムのようなハロゲン化炭化水素類であり得、好適には、クロロホルムである。
用いられる溶媒の量は、化合物（ＸＸＩＶ）１ｍｏｌに対し、通常、１．０〜２０リットルであり、好適には、１．０〜１０リットルである。
用いられるクロロスルホン酸の量は、化合物（ＸＸＩＶ）１ｍｏｌに対し、通常、１．０〜１０.０ｍｏｌであり、好適には、２．０〜５．０ｍｏｌである。
反応温度は、原料化合物、反応試薬及び溶媒等により異なるが、通常、−４０℃〜反応系における還流温度であり、好適には、０〜８０℃である。
反応時間は、原料化合物、反応試薬、溶媒及び反応温度等により異なるが、通常、５分間〜４８時間であり、好適には、１０分間〜２４時間である。
工程Ｅ−５は、溶媒存在下または非存在化、化合物（ＸＸＶ）のクロロスルホニル基を還元し、一般式（ＸＸＶＩ）を有する化合物を製造する工程である。
本工程は、例えば、酸存在下、亜鉛やスズを用いる方法のような、クロロスルホニル基をメルカプト基に還元する際の常法（例えば、J.Am.Chem.Soc.,1947,69,1925、Tetrahedron,1994,50,4775等に記載の方法）に従って行われる。
使用される溶媒は、反応を阻害せず、出発物質をある程度溶解するものであれば特に限定はなく、例えば、酢酸及びプロピオン酸のようなカルボン酸類；水；又はメタノール、エタノール、プロパノールのようなアルコール類；或はこれらの混合溶媒であり得、好適には、水又はアルコール類であり、より好適には、水又エタノールである。
用いられる酸は、例えば、硫酸、塩酸及び硝酸のような鉱酸であり得、好適には、硫酸又は塩酸である。
用いられる亜鉛と酸の量は、化合物（ＸＸＶ）１ｍｏｌに対し、通常、１．０〜５０.０ｍｏｌであり、好適には、１．０〜２０．０ｍｏｌである。
反応温度は、原料化合物、反応試薬及び溶媒等により異なるが、通常、−４０℃〜反応系における還流温度であり、好適には、０〜１５０℃である。
反応時間は、原料化合物、反応試薬、溶媒及び反応温度等により異なるが、通常、５分間〜４８時間であり、好適には、１０分間〜２４時間である。
また、本工程において、アシルチオ体（例えば、アセチルチオ体）が得られた場合には、該アシルチオ体を前記工程Ｃの工程Ｃ−７と同様に加水分解して、化合物（ＸＸＶ）に導くこともできる。
工程Ｅ−６は、塩基及び溶媒存在下、化合物（ＸＸＶＩ）と、化合物（ＸＶＩＩＩ）を反応させ、本発明の化合物（Ｉｆ）を製造する工程である。
本工程は、前記工程Ｃの工程Ｃ−８と同様に行われる。
上記工程で得られた目的物は、常法により、反応混合物から採取される。例えば、反応混合物中に目的物が結晶として析出する場合、目的物を濾取することにより、反応混合物が不溶物を含む場合は、適宜、不溶物を濾去し、反応混合物が酸性又はアルカリ性の場合は、適宜、中和して、溶媒を減圧で留去することにより、又は、反応混合物又は上記の溶媒を減圧で留去したものに水を加え、水不混和性有機溶媒で抽出し、抽出液を乾燥し、抽出溶媒を減圧で留去することにより、目的物を得ることができる。また、必要に応じて、常法、例えば、再結晶法、カラムクロマトグラフィー等を用いて、目的物をさらに精製することができる。Wherein, ^{R 2} represents the same meaning as defined ^{above, R 18} is a halogen atom, may be substituted at the ^{R 4} optionally _C 1 -C ₆ alkoxy group or a ^{R 4} be substituted at the It represents a C ₁ -C ₆ alkylthio group. ]
In this step, compound (If) is produced, wherein n is 0.

In the above formula, R ¹ , R ² , X, m, A, R ¹⁸ and Y ⁴ are as defined above,
Y ⁵ represents a halogen atom,
R ¹⁷ represents C ₁ -C ₆ alkyl;
R ¹⁸ a represents an optionally substituted C ₁ -C ₆ alkyl group in R ⁴ .
Step E-1 is a step of producing a compound represented by the general formula (XXII) by reacting a compound represented by the general formula (XXI) with the compound (XI) in the presence of a solvent.
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; carboxylic acids such as acetic acid and propionic acid; alcohols such as methanol, ethanol and propanol Ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; nitriles such as acetonitrile; N, N-dimethylformamide, N, N Amides such as dimethylacetamide and N-methyl-2-pyrrolidone; Sulfoxides such as dimethyl sulfoxide and sulfolane; Halogenated hydrocarbons such as methylene chloride and chloroform; or Fats such as hexane, cyclohexane and heptane Tribe Hydrogen like; be in, or mixed solvent thereof, preferably an aqueous or alcohol, or a mixture of these solvents, more preferably a water or ethanol or a mixed solvent thereof.
The amount of the solvent used is usually 1.0 to 20 liters and preferably 1.0 to 10 liters with respect to 1 mol of compound (XXI).
The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually from −40 ° C. to the reflux temperature in the reaction system, and preferably from 0 to 100 ° C.
While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 5 minutes to 48 hours, preferably 10 minutes to 24 hours.
Compound (XXI) used in this step is produced by a known method (for example, Synthesis, 1989, 217-218, etc.).
Step E-2 is a step of producing a compound having the general formula (XXIIa) by reacting the compound (XXII) with a Lawson reagent in the presence of a solvent.
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, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; or hexane, cyclohexane and Aliphatic hydrocarbons such as heptane; or a mixed solvent thereof, preferably aromatic hydrocarbons, and more preferably toluene.
The amount of the solvent used is usually 1.0 to 20 liters and preferably 1.0 to 10 liters with respect to 1 mol of compound (XXII).
The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually 0 to 150 ° C, and preferably 30 to 140 ° C.
While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 5 minutes to 48 hours, preferably 10 minutes to 24 hours.
In step E-3a, compound (XXIIa) is reacted with a compound represented by general formula (XXIII) in the presence of a base and a solvent, and in the compound represented by general formula (XXIV), R ¹⁸ is as defined above. In this step, the compound (XXIVa), which is an optionally substituted C ₁ -C ₆ alkylthio group, is produced.
This step is performed in the same manner as the step C-8 of the step C.
In step E-3b, compound (XXII) is reacted with compound (XXIII). In compound (XXIV), R ¹⁸ is an optionally substituted C ₁ -C ₆ alkoxy group (XXIVb And a compound (XXII) are converted into halogenating agents (eg, phosphorus oxychloride, phosphorus pentachloride, carbon tetrachloride-triphenylphosphine, phosphorus oxybromide, phosphorus pentabromide, carbon tetrabromide-triphenylphosphine, In this step, compound (XXIVc) in which R ¹⁸ is a halogen atom (preferably a chlorine atom or a bromine atom) in compound (XXIV) is reacted.
The reaction between compound (XXII) and compound (XXIII) is carried out in the same manner as in the above-mentioned Method C, step C-8, and the reaction between compound (XXII) and the halogenating agent is carried out in the absence of a solvent or a solvent (for example, chloroform And halogenated hydrocarbons such as carbon tetrachloride, etc.) (preferably in the absence of a solvent) at 100 to 200 ° C. for 5 minutes to 12 hours.
Step E-4 is a step of producing a compound having the general formula (XXV) by reacting compound (XXIV) with chlorosulfonic acid in the presence or absence of a solvent.
The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent, and may be, for example, halogenated hydrocarbons such as methylene chloride and chloroform. It is.
The amount of the solvent used is usually 1.0 to 20 liters and preferably 1.0 to 10 liters with respect to 1 mol of compound (XXIV).
The amount of chlorosulfonic acid to be used is usually 1.0 to 10.0 mol, and preferably 2.0 to 5.0 mol with respect to 1 mol of compound (XXIV).
The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent, and the like, but is usually from −40 ° C. to the reflux temperature in the reaction system, and preferably from 0 to 80 ° C.
While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 5 minutes to 48 hours, preferably 10 minutes to 24 hours.
Step E-5 is a step of producing a compound having the general formula (XXVI) by reducing the chlorosulfonyl group of the compound (XXV) in the presence or absence of a solvent.
This step is a conventional method for reducing a chlorosulfonyl group to a mercapto group, such as a method using zinc or tin in the presence of an acid (for example, J. Am. Chem. Soc., 1947, 69, 1925). , Tetrahedron, 1994, 50, 4775, etc.).
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, carboxylic acids such as acetic acid and propionic acid; water; or methanol, ethanol, propanol, etc. Alcohols; or a mixed solvent thereof, preferably water or alcohols, more preferably water or ethanol.
The acid used can be, for example, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, preferably sulfuric acid or hydrochloric acid.
The amount of zinc and acid to be used is usually 1.0 to 50.0 mol, preferably 1.0 to 20.0 mol, per 1 mol of compound (XXV).
The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent and the like, but is usually from −40 ° C. to the reflux temperature in the reaction system, and preferably from 0 to 150 ° C.
While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 5 minutes to 48 hours, preferably 10 minutes to 24 hours.
In addition, in this step, when an acylthio form (for example, acetylthio form) is obtained, the acylthio form may be hydrolyzed in the same manner as in Step C-7 of Step C to lead to compound (XXV). it can.
Step E-6 is a step of producing compound (If) of the present invention by reacting compound (XXVI) with compound (XVIII) in the presence of a base and a solvent.
This step is performed in the same manner as the step C-8 of the step C.
The target product obtained in the above step is collected from the reaction mixture by a conventional method. For example, when the target product is precipitated as crystals in the reaction mixture, the target product is collected by filtration. If appropriate, neutralize and distill off the solvent under reduced pressure, or add water to the reaction mixture or the above solvent distilled off under reduced pressure and extract with a water-immiscible organic solvent, The target product can be obtained by drying the extract and evaporating the extraction solvent under reduced pressure. If necessary, the target product can be further purified by a conventional method such as recrystallization or column chromatography.

  Compound (I) of the present invention is not an alkali metal salt, an alkaline earth metal salt or an ammonium salt as described above, but is salted with an acid in the presence of a solvent when a basic moiety is present in the molecule. be able to.

  When the compound (I) of the present invention is used as an active ingredient of an agricultural chemical composition, the compound (I) of the present invention may be used as it is, but is generally used for formulation as an agricultural chemical adjuvant. Incorporating carriers, surfactants and other adjuvants, for example, emulsions, suspensions, powders, granules, tablets, wettable powders, aqueous solvents, liquids, flowable powders, granular wettable powders, aerosols, pastes It can be formulated into various forms such as an agent, an oil agent and an emulsion. These blending ratios are usually 0.1 to 9.0 parts by mass of the active ingredient and 10 to 99.9 parts by mass of the agrochemical adjuvant.

  Carriers used in the formulation include, for example, animal and vegetable powders such as starch, activated carbon, soybean flour, wheat flour, wood flour, fish flour, milk powder, and talc, kaolin, bentonite, calcium carbonate, zeolite, diatomaceous earth, white carbon, Solid carriers such as mineral powders such as clay and alumina; or water, alcohols such as isopropyl alcohol and ethylene glycol, ketones such as cyclohexane and methyl ethyl ketone, ethers such as dioxane and tetrahydrofuran, fats such as kerosene and light oil Esters such as aromatic hydrocarbons, aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylbenzenemethylnaphthalene, and solvent naphtha, halogenated hydrocarbons such as chlorobenzene, acid amides such as dimethylacetamide, and glycerin esters of fatty acids S may be a liquid carrier such as nitriles and dimethylsulfoxide sulfur-containing compounds such as de as acetonitrile, preferably a solid carrier or liquid carrier.

  The surfactant used is, for example, alkylbenzene sulfonic acid metal salt, dinaphthylmethane disulfonic acid metal salt, alcohol sulfate ester salt, alkylaryl sulfonate, lignin sulfonate, polyoxyethylene glycol ether, polyoxyethylene alkylaryl It can be an ether or a polyoxyethylene sorbitan monoalkylate, preferably an alkylbenzene sulfonic acid metal salt, lignin sulfonate, polyoxyethylene alkylaryl ether or polyoxyethylene sorbitan monoalkylate.

  Other adjuvants include, for example, fixing agents or thickeners such as carboxydimethylcellulose, gum arabic, sodium alginate, xanthan gum, guar gum, tragacanth gum and polyvinyl alcohol; antifoaming agents such as metal soaps; or fatty acids, alkyl phosphates It can be a colorant such as silicone and paraffin, and is preferably guar gum or xanthan gum.

  These preparations can be used as they are in actual use, or can be used after diluting to a predetermined concentration with a diluent such as water. Application of various preparations containing the compound of the present invention or diluents thereof is usually performed by a general application method, that is, spraying (for example, spraying, misting, atomizing, dusting, dusting, water surface application). , Box application, etc.), soil application (eg, mixing, irrigation, etc.), surface application (eg, application, dressing, coating, etc.), immersion or poison bait. It is also possible to feed the livestock with the active ingredient in a feed to control the occurrence and growth of harmful insects, particularly harmful insects, in the excreta. It can also be applied by the so-called ultra-high concentration small quantity spraying method. In this method, it is possible to contain 100% of the active ingredient.

  The active ingredient concentration at the time of applying the agricultural chemical composition of the present invention is usually 0.1 to 50000 ppm, preferably 1 to 10000 ppm. However, the active ingredient concentration can be appropriately changed depending on the form of the preparation and the method of application, purpose, time, place and occurrence of pests. Therefore, the active ingredient concentration in water is smaller than the above.

  In the case of the soil admixing treatment, the amount of the agrochemical composition of the present invention is, for example, 0.1 to 5000 g per 10 are as an active ingredient compound, and preferably 1 to 1000 g.

  In addition, it goes without saying that the compound (I) of the present invention alone is sufficiently effective, but if necessary, fertilizers and other agricultural chemicals such as insecticides, acaricides, nematicides, fungicides, It can be used in combination with or combined with antiviral agents, attractants, herbicides, plant regulators, etc., and in this case, a more excellent effect may be exhibited.

  Other agricultural chemicals that can be used in combination with the compound (I) of the present invention are, for example, insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides or plant regulators. Preferably, it is an insecticide, acaricide, nematicide, fungicide or herbicide.

  The insecticides used can be, for example, organophosphorus and carbamate insecticides, pyrethroid insecticides or other insecticides.

  Organic phosphorus and carbamate insecticides include, for example, fenthion, fenitrothion, diazinon, chlorpyrifos, oxydephfos, bamidione, phentoate, dimethoate, formothion, malathion, trichlorfone, thiometone, phosmet, dichlorphos, acephate, EPBP, methylparathion, ethidimethone methyl , Dioxabenzophos, cyanophos, isoxathione, pyridafenthion, hosalon, methidathion, sulprophos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, disulfoton, profenofos, pyracrophos, monocrotophos, azinephosmethyl, aldicarb, mesomil , Thiodicarb, Carbofuran, Carbosulfan, Be Furacarb, furthiocarb, propoxul, fenobucarb, metorcarb, isoprocarb, carbaryl, pyrimicarb, ethiophene carb, diclofenthion, pirimiphosmethyl, quinalphos, chlorpyrifosmethyl, prothiophos, nared, EPN, XMC, bendiocarb, oxamyl, alanical carb, ethoxypyrazol It can be.

  Pyrethroid insecticides include, for example, permethrin, cypermethrin, deltamethrin, fenvalerate, phenpropatoline, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propraslin, phenothrin, protorin, fulvalinate, cyfluthrin, cyhalothrin, flucitrinate, eth It may be Fenprox, Cycloproton, Tralomethrin, Silafluophene, Tefluthrin, Bifenthrin or Acrinatrin.

  Other insecticides include, for example, diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, teflubenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, lufenuron, cyromazine, metoprene, endosulfan, diafenthiuron , Imidacloprid, fipronil, phenoxycarb, cartap, thiocyclam, bensultap, tebufenozide, chlorfenapyr, emamectin benzoate, acetamiprid, nitenpyram, pymetrozine, thiacloprid, spinosad, tebufenpyrad, tolfenpyrod, dinotetamnothithiodide Acetoprole, pyridalyl, Indoki Calve, spiromesifen, spiro tetra mat, flubendiamide, lepimectin, metaflumizone, sodium oleate, nicotine sulfate, rotenone, metaldehyde, machine oil, rapeseed oil, may be microbial pesticide such as a BT agent or an insect pathogenic virus.

  The acaricides used are, for example, chlorbenzilate, phenisobromolate, dicophor, amitraz, propargite, benzomate, hexothiazox, phenbutatin oxide, polynactin, quinomethionate, chlorfenson, tetradiphone, abamectin, milbemectin, It can be clofentezin, pyridaben, fenpyroximate, tebufenpyrad, pyrimidifen, phenothiocarb, dienochlor, etoxazole, halfenprox, spirodiclofen phenazate, cyflumethofen or fluacrylpylium.

  The nematicide used can be, for example, fenamifos, phostiazate, etoprofos, methylisothiocyanate, 1,3-dichloropropene or DCIP.

  The fungicides used are, for example, thiophanate methyl, benomyl, carbendazole, thiabendazole, phorvet, thiuram, ziram, dineb, mannebu, manzeb, polycarbamate, iprobenphos, edifenfos, fusalide, probenazole, isoprothiolane, chlorothalonil, captan, polyoxin. , Blasticidin S, kasugamycin, streptomycin, validamycin, tricyclazole, pyroxylone, phenazine oxide, mepronil, flutolanil, pencyclon, iprodione, hymexazole, metalaxyl, triflumizole, triphorin, triadimephone, viteltanol, fenarimol, propiconazole, simoxanil , Pefrazoate, hexaconazole, microbes Nil, dichromedin, teclophthalam, propineb, dithianon, fosetyl, vinclozoline, prosimidone, oxadixil, guazatine, propamocarb hydrochloride, fluazinam, oxolinic acid, hydroxyisoxazole, imibenconazole, mepanipyrim, bench avalib, silfenamide, ciazofamide, , Phenoxanyl, metolaphenone, nicobifen, picoxyslothobin, pyraclostrobin, cimeconazole, amisbrobrom, mandipropamide, flupicolide, penthiopyrad, boscalid, flumorph, floxastrobin, orisatrobin, proquinazide, prothioconazole or zoxamide.

  Herbicides used are, for example, diflufenican, propanyl, dichloropicolinic acid, dicamba, picoloram, 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP, triclopyr, diclohop-methyl, Phenoxaprop-ethyl, fluazifop-butyl, haloxyhop-methyl, quizalofop-ethyl, norflurazon, chlorbrofam, desmedifam, fenmedifam, profam, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor, propachlor, oryzalin, trifluralin, Acifluorfen, bifenox, fluorogligophene, fomesafen, halosulfene, lactofen, oxyfluorfen, chlortoluron, diuron, full Metulone, isoproturon, linuron, metabenzthiazulone, alloxidim, cretodim, cycloxidim, cetoxydim, tracoxidim, imazetapyr, imazametabenz, imazapyr, imazaquin, bromoxynyl, diclobenyl, ioxinyl, mefenacet, amidosulfuron-methyl, rimsulfuron-methyl , Chlorsulfuron, Sinosulfuron, Metosulfuron-methyl, Nicosulfuron, Pyrisulfuron, Pyrazosulfuron-ethyl, Thifensulfuron-methyl, Triasulfuron, Tribenuron-methyl, Butyrate, Cycloate, Giarate, EPTC, Esprocarp, Molinate, Prosulfocarp , Bench Ocalp, Trialate, Atrazine, Cyanazine, Simazine, Simmetry , Terbutrin, terbuthylazine, hexazinone, metamitron, metribudine, amitriazole, benfrate, bentazone, cinmethyline, clomazone, clopyralid, difenzoquat, dithiopyr, etofumecetate, fluorochloridone, glufosinate, isoxaben, pyroxalate, quinlodac, quincloc It can be sulfosate, tridiphane, caffon and roll, cyhalohop-butyl, indanophan, benzobicyclone, benzphendizone, butaphenacyl, fluazolate, fluthiaset, pyrazogyl, pyridahol, pyriftalide, fluphenazide or fentolazamide.

  The compound (I) of the present invention includes, for example, hemiptera pests, lepidopterous pests, coleopterous pests, diptera pests, hymenopterous pests, straight-eyed pests, termite pests, thrips pests, spider mites and the like Excellent control effect against plant parasitic nematodes. In addition, the compound (I) of the present invention exhibits an excellent control effect against other harmful animals, unpleasant animals, sanitary pests and parasites.

  The Hemiptera pests include, for example, Riptortus clavatus, Neraza viridula, Lygus sp., Phellinus sect. Leafhoppers such as Heteroptera, Nephotettix cinchetics, Emporska sp., Erythronia sp., Cirlifer sp. Planthoppers of ax striatellus), etc., Psylla sp. Whitefly (Bemisia tabaci), whitefly (Trialeurodes vaporariorum), whitefly aphid (Viteus vitifolia), peach aphid (Merica aphid) gossypii), Aphis fabae, Liphis erysimi, potato aphid (Aulacorthum solani), Aphidius cricket (C) It may be a scale insect such as Eroplastes rubens), San Jose scale insect (Comstockcaspis perniciosa), and scale insect (Rhodnius sp.).

  Lepidoptera, for example, Chahamaki (Homona magnanima), Kokakumonhamaki (Adoxophyes orana), Tenguhamaki (Sparganothis pilleriana), oriental fruit moth (Grapholitha molesta), soybean pod borer, Leguminivora glycinivorella (Leguminivora glycinivorella), codling moth (Laspeyresia pomonella), Eucosma sp. , Lobesia botrana, etc., Grape lobster (Eupoecilia ambiguella), etc., Bambalina sp. Minoga, such as Nempogon granellus, Hirosukoga, such as Tinea pellelloella, Clamidae, such as Lyonetia prunifoliella, Phyllonhitter, etc. Stag beetles such as scallops, Plutella xylostella, and Plays citri, Nokona vegale, Synanthedon sp. Such as Sashiba, cotton worm (Pectinophora gossypiella), potato (Phythromea operculella), Stomopteryx sp. Mosquito, such as Carposina nipponensis, moths such as Monema flavescens, Chilo suprasisalis haisariis, nascent moths, Helula undalis, honey moth (Galleria melonella), Elasmopalpus lignosellus, Loxotege tacticalis and other white moths, white butterflies (Pieris rapae) and other white butterflies Aria, etc., Kalehaga, such as Malacosoma neutria, Suzumegas, such as Manduca sexta, Euproctis pseudoconspersa, Miga (Lymantria), Trigger, etc. , Or tobacco worms (Heliothis virescens), ball worms (Helicoverpa zea), sirochimo jiyoto (Spodoptera armigera), helicoverpa armigera, buro sato (p) Moth (Agrotis ipsilon), it may be armyworm (Pseudaletia separata) and cabbage Kin looper (Trichoplusia ni) Noctuidae such as.

  Coleopterous pests include, for example, Anomala cuprea, Popularia japonica, Anomala rubocuprea, Euthelaruges sp. Click beetle such etc., the beetle, Epilachna vigintioctopunctata (Epilachna vigintioctopunctata), Ladybug such as kidney ladybird (Epilachna varivestis), mealworm such as red flour beetle (Tribolium castaneum), Gomadarakamikiri (Anoplophora malasiaca), Japanese pine sawyer (Monochamus alternatus), etc. Longhorn beetles (Acanthocelides obectus), Japanese beetle (Callosobruchus chinensis), weevil (Leptinotarsa decmlineata), corn rootworm brotica sp.), Inedorooimushi (Oulema oryzae), Ten site bi potato beetle (Chaetocnema concinna), Phaedon cochlearias, Oulema melanopus, beetle such as Dicladispa armigera, bombardier Cu Chi weevils such as Apion godmani, rice water weevil (Lissorhoptrus oryzophilus), boll weevil It can be a weevil such as (Anthonomus grandis), a weevil such as a weevil (Sitophilus zeamais), a bark beetle, a cutworm, or a beetle.

  The Diptera pests include, for example, Tipula aino, Chironomas oryzae, u sir eu, eu sigma flies, Oresolia oryzae, eu, and eu Fritz fries (Oscinella frit), rice flies (Chlorops oryzae), common beetle (Ophiomyia phaseioli), legume flies (Liriomyza trifolii), red-bellied flies Mufurai (Atherigona soccata), housefly (Musca domestica), stable flies (Gastrophilus sp.), Stable fly (Stomoxys sp.), Aedes aegypti (Aedes aegypti), Culex (Culex pipiens), in Anopheles sinensis (Anopheles slnensis) or Culex (Culex tritaeniorhynchus) possible.

  The Hymenoptera pests can be, for example, the hornets (Cephus sp.), The beetle (Harmorita sp.), The wasp (Athalia rosae), the wasp (Vespa mandrina) or the fire ant.

  The insects of the order Diptera are, for example, the German cockroach (Blatella germanica), the American cockroach (Periplaneta americana), the kerato (Glylottalpa africana), the grasshopper (Locusta migratory migratory or migratory migratory or migratory migratory).

  The termite pest can be, for example, a Yamato termite (Reticulitermes supertus), a termite (Coptopterformes formosanus), or a Cyptotermes domestius.

  Thysanoptera, for example, yellow tea thrips (Scirtothrips dorsalis), Thrips palmi (Thrips palmi), Croton thrips (Heliothrips haemorrhoidalis), may be a western flower thrips (Frankliniella occidentalis) or rice Kuda thrips (Haplothrips aculeatus).

  Spider mites include, for example, Tetanychus urticae, Tetanyychus kanzawai, Taniyus citrus, Panonychus ulmi, Texas, Emitranp ), Mites (Polyphagotarsonemus latus), Mite spider (Brevipalpus sp.), Robin tick (Rhizoglyphus robini) or Typhaphagus putrescentiae.

  Plant parasitic nematodes include, for example, Meloidogyne incognita, Pratylenchus sp. possible.

  Other harmful animals, unpleasant animals, sanitary pests and parasites include, for example, gastropods such as Pomacea canalicula, slugs (Inciliaria sp.), Achatina falica, armadillium (Armadillidium) sp.), Isopoda such as Warabimushi and Centipede (Isopoda), Liposcelis sp. Chatteramushi such as Ctenolepisma sp. Stains such as Pulex sp. Ctenocephalides sp. Fleas such as Trichodes sp. Lice, etc., Cimex sp. It is possible to be animal parasitic mites such as Bob ticks, Boophilus microplus, Haemaphysalis longicornis or leopard mites.

  Furthermore, the compound (I) of the present invention is also effective against pests that are resistant to organophosphorus compounds, carbamate compounds, synthetic pyrethroid compounds, acylurea compounds, or existing insecticides.

  Hereinafter, the compound of the present invention will be specifically described with reference to Examples, Formulation Examples and Test Examples, but the present invention is not limited thereto.

Example 1
4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1-55)
(1) 4-Bromo-2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Step A-1a)
To a solution of 60% sodium hydride (2.20 g, 55.0 mmol) in N, N-dimethylformamide (150 ml) was added 2,2,2-trifluoroethanethiol (4.90 g, 55.1 mmol) under ice cooling. The solution was added dropwise and stirred at room temperature for 50 minutes. Subsequently, a solution of 4-bromo-2-fluorobenzonitrile (10.00 g, 50.0 mmol) in N, N-dimethylformamide (150 ml) was added dropwise with cooling to −40 ° C., and the same temperature was maintained for 2.5 hours. Then, it was stirred at room temperature for 30 minutes. The reaction solution was poured into ice water and extracted with ethyl acetate. The extract was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (eluent: hexane / ethyl acetate = 6/1) to obtain the title compound (14.47 g, yield 97.7%).
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.81 (1H, s), 7.60-7.53 (2H, m), 3.58 (2H, q, J = 9.2 Hz).
(2) 4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1- 55, step A-2a)
[1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] boronic acid (7.08 g, 36.51 mmol), 4-bromo-2-[(2,2,2-trifluoroethyl) )] Thio] benzonitrile (10.81 g, 36.51 mmol) and sodium carbonate (11.61 g, 109.54 mmol) in a toluene-ethanol-water mixed solution (2/1/1, 184 ml) with tetrakistriphenylphosphine palladium. (2.11 g, 1.83 mmol) was added followed by heating at 90 ° C. for 18 hours. To the reaction solution was added saturated brine, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (eluent: hexane / ethyl acetate = 4/1) to obtain the title compound (7.93 g, yield 60.0%).
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.84 (1H, d, J = 7.9 Hz), 7.74 (1H, s), 7.50 (1H, d, J = 7.9 Hz), 6.65 (1H, s), 3.95 (3H, s), 3.61 (2H, q, J = 9.4 Hz).

Example 2
4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2- (propylthio) benzonitrile (Compound No. 1-43)
(1) 2-Fluoro-4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] benzonitrile (Compound No. 4-13, Step A-1b)
[1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] boronic acid (1.00 g, 5.16 mmol) and 4-bromo-2-fluorobenzonitrile (1.03 g, 5.15 mmol) ) Was dissolved in 1,2-dimethoxyethane (17 ml) and then 2M aqueous sodium carbonate (7.7 ml, 15.4 mmol) was added. Tetrakistriphenylphosphine palladium (298.2 mg, 0.26 mmol) was added, and the mixture was heated to reflux for 19 hours. Ethyl acetate was added and washed with saturated brine. After drying over magnesium sulfate and concentrating under reduced pressure, the residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 3/1) to give the title compound (975.4 mg, yield 70.4%). Got.
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.80-7.75 (1H, m), 7.37-7.26 (2H, m), 6.66 (1H, s), 3.98 (3H, s).
(2) 4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2- (propylthio) benzonitrile (Compound No. 1-43, Step A-2b)
To a solution of 1-propanethiol (51.0 μl, 0.56 mmol) in N, N-dimethylformamide (2.0 ml) was added 60% sodium hydride (23.1 mg, 0.58 mmol) under ice cooling, and at room temperature. Stir for 20 minutes. Subsequently, N, N- of 2-fluoro-4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] benzonitrile (100.4 mg, 0.37 mmol) under ice cooling. Dimethylformamide solution (1.0 ml) was added dropwise and stirred at room temperature for 1 day. The reaction solution was poured into ice water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by thin layer chromatography (developing solvent: chloroform / ethyl acetate = 20/1) to obtain the title compound (18.3 mg, yield 15.1%).
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.72 (1H, d, J = 7.9 Hz), 7.39 (1H, s), 7.27 (2H, d, J = 7.9 Hz), 6.62 (1H, s), 3.94 (3H, s), 3.04 (2H, t, J = 6.7 Hz), 1.82-1.72 (2H, m), 1.09 (3H, t, J = 7.3 Hz).

Example 3
4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) sulfinyl] benzonitrile (Compound No. 1-56, process A-3)
4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (115.3 mg, 0.32 mmol ) In methylene chloride (3.0 ml) was added 3-chloroperbenzoic acid (85.7 mg, 0.32 mmol) under ice-cooling and stirred at room temperature for 1 hour. Ethyl acetate was added to the reaction solution, washed successively with aqueous sodium sulfite solution, water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 2/1) to obtain the title compound (58.4 mg, yield 48.5%).
¹ H-NMR spectrum (CDCl ₃ ) δ: 8.23 (1H, d, J = 1.6 Hz), 7.95 (1H, d, J = 7.9 Hz), 7.76 (1H, dd, J = 7.9, 1.6 Hz), 6.75 (1H, s), 4.01 (3H, s), 3.88-3.60 (2H, m).
Furthermore, the compounds of Examples 4 to 12 below were produced using the method of Step A.

Example 4
2- (Ethylthio) -4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] benzonitrile (Compound No. 1-41, Step A-1b and Step A-2b)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.73 (1H, d, J = 7.9 Hz), 7.41 (1H, s), 7.27 (1H, d, J = 7.9 Hz), 6.62 (1H, s), 3.95 (3H, s), 3.10 (2H, q, J = 7.3 Hz), 1.41 (3H, t, J = 7.3 Hz).

Example 5
4- (1-Methyl-1H-pyrazol-5-yl) -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1-64, Step A-1a and Step A-2a )
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.80 (1H, d, J = 7.9 Hz), 7.74 (1H, d, J = 1.8 Hz), 7.55 (1H, d, J = 1.8 Hz), 7.50 (1H , dd, J = 7.9, 1.8 Hz), 6.41 (1H, d, J = 1.8 Hz), 3.92 (3H, s), 3.61 (2H, q, J = 9.4 Hz).

Example 6
4- [1-Methyl-3- (pentafluoroethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1-65, step) A-1a and step A-2a)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.84 (1H, d, J = 8.1 Hz), 7.74 (1H, s), 7.51 (1H, d, J = 8.1 Hz), 6.67 (1H, s), 3.96 (3H, s), 3.62 (2H, q, J = 9.2 Hz).

Example 7
4- [1-Methyl-3- (pentafluoroethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) sulfinyl] benzonitrile (Compound No. 1-66, process A-3)
¹ H-NMR spectrum (CDCl ₃ ) δ: 8.24 (1H, d, J = 1.6 Hz), 7.95 (1H, d, J = 7.9 Hz), 7.77 (1H, dd, J = 7.9, 1.6 Hz), 6.78 (1H, s), 4.03 (3H, s), 3.88-3.57 (2H, m).

Example 8
4- [3- (Heptafluoropropyl) -1-methyl-1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1- 69, step A-1a and step A-2a)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.84 (1H, d, J = 7.9 Hz), 7.75 (1H, d, J = 1.6 Hz), 7.52 (1H, dd, J = 7.9, 1.6 Hz), 6.66 (1H, s), 3.97 (3H, s), 3.62 (2H, q, J = 9.3 Hz).

Example 9
4- [3- (Heptafluoropropyl) -1-methyl-1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) sulfinyl] benzonitrile (Compound No. 1-70, Step A-3)
¹ H-NMR spectrum (CDCl ₃ ) δ: 8.24 (1H, d, J = 1.6 Hz), 7.95 (1H, d, J = 7.9 Hz), 7.77 (1H, dd, J = 7.9, 1.6 Hz), 6.77 (1H, s), 4.04 (3H, s), 3.81-3.61 (2H, m).

Example 10
4- [1,4-Dimethyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) sulfinyl] benzonitrile (Compound No. 1-74) Step A-3)
¹ H-NMR spectrum (CDCl ₃ ) δ: 8.13 (1H, d, J = 1.6 Hz), 7.97 (1H, d, J = 7.9 Hz), 7.65 (1H, dd, J = 7.9, 1.6 Hz), 3.84 (3H, s), 3.88-3.62 (2H, m), 2.11 (3H, s).

Example 11
4- [1,4-Dimethyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1-73) Step A-1a and Step A-2a)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.87 (1H, d, J = 7.9 Hz), 7.63 (1H, d, J = 1.6 Hz), 7.41 (1H, dd, J = 7.9, 1.6 Hz), 3.80 (3H, s), 3.62 (2H, q, J = 9.3 Hz), 2.07 (3H, s).

Example 12
4- (1-Methyl-1H-pyrazol-4-yl) -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 3-1, Step A-1a and Step A-2a)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.80 (1H, s), 7.75 (1H, d, J = 1.6 Hz), 7.71 (1H, s), 7.67 (1H, d, J = 8.0 Hz), 7.50 (1H, dd, J = 8.0, 1.6 Hz), 3.97 (3H, s), 3.58 (2H, q, J = 9.5 Hz).

Example 13
4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1-55) and 4- [1-Methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 2-1)
(1) 4- [1- (Ethoxy) ethenyl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Step B-1)
To a solution of 4-bromo-2-[(2,2,2-trifluoroethyl) thio] benzonitrile (101.5 mg, 0.34 mmol) in toluene (1.0 ml) was added tributyl (1-ethoxyvinyl) tin (0 .13 ml, 0.38 mmol) and bis (triphenylphosphine) palladium (II) chloride (2.8 mg, 0.0040 mmol) were added, followed by heating and stirring at 100 ° C. for 3 hours. Ethyl acetate was added to the reaction solution, and insoluble matters were removed by filtration. The filtrate was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 3/1) to obtain the title compound (85.5 mg, yield 86.8%).
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.92 (1H, s), 7.68-7.62 (2H, m), 4.78 (1H, d, J = 3.2 Hz), 4.39 (1H, d, J = 3.2 Hz) 3.94 (2H, q, J = 7.0 Hz), 3.57 (2H, q, J = 9.4 Hz), 1.44 (3H, t, J = 7.0 Hz).
(2) 4- (1-Ethoxy-4,4,4-trifluoro-3-oxo-1-butenyl) -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Step B- 2)
To a solution of trifluoroacetic anhydride (42.4 μl, 0.30 mmol) in methylene chloride (3.0 ml) under ice-cooling, 4- [1- (ethoxy) ethenyl] -2-[(2,2,2-tri A solution of (fluoroethyl) thio] benzonitrile (85.5 mg, 0.30 mmol) and pyridine (24.3 μl, 0.30 mmol) in methylene chloride (1.0 ml) was added and stirred overnight at room temperature. Ice water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 3/1) to obtain the title compound (75.6 mg, yield 66.3%).
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.76-7.72 (2H, m), 7.50 (1H, dd, J = 8.2, 1.6 Hz), 5.89 (1H, s), 4.21 (2H, q, J = 7.0 Hz), 3.59 (2H, q, J = 9.4 Hz), 1.50 (3H, t, J = 7.0 Hz).
(3) 4- [1-Methyl-3- (trifluoromethyl-1H-pyrazol-5-yl) -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1-55) Step B-3) and 4- [1-methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile ( Compound No. 2-1, Step B-3)
4- (1-Ethoxy-4,4,4-trifluoro-3-oxo-1-butenyl) -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (75.6 mg, 0.7. Methylhydrazine (10.6 μl, 0.20 mmol) was added to a solution of 20 mmol) in ethanol (2.0 ml), and the mixture was heated and stirred at 100 ° C. for 3 hours. After cooling to room temperature, the reaction solution was concentrated. Ethyl acetate was added to the residue for dissolution, and the residue was washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by thin layer chromatography (eluent: hexane / ethyl acetate = 2/1) to give compound No. 2-1 (11.5 mg, 16.0% yield) and Compound No. 1-55. The compound (37.3 mg, 51.8%) was obtained.
Compound No. 2-1
¹ H-NMR spectrum (CDCl ₃ ) δ: 8.09 (1H, d, J = 1.6 Hz), 7.81 (1H, dd, J = 7.9, 1.6 Hz), 7.73 (1H, d, J = 7.9 Hz), 6.96 (1H, s), 4.07 (3H, s), 3.61 (2H, q, J = 9.4 Hz).
The ¹ H-NMR spectrum of the compound of Compound No. 1-55 obtained in this step was consistent with that of the compound of Example 1 (2).
Furthermore, the compounds of Examples 14 to 16 below were produced using the method of Step B.

Example 14
4- [1-Ethyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1-61, Step B-1 to B-3)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.83 (1H, d, J = 7.9 Hz), 7.71 (1H, d, J = 1.6 Hz), 7.48 (1H, dd, J = 7.9, 1.6 Hz), 6.60 (1H, s), 4.19 (2H, q, J = 7.2 Hz), 3.61 (2H, q, J = 9.3 Hz), 1.45 (3H, t, J = 7.2 Hz).

Example 15
4- [1-Ethyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 2-3, process B-1 to B-3)
¹ H-NMR spectrum (CDCl ₃ ) δ: 8.10 (1H, s), 7.83 (1H, d, J = 7.9 Hz), 7.73 (1H, d, J = 7.9 Hz), 6.94 (1H, s), 4.34 (2H, q, J = 7.2 Hz), 3.62 (2H, q, J = 9.3 Hz), 1.55 (3H, t, J = 7.2 Hz).

Example 16
4- [1- (tert-butyl) -5- (trifluoromethyl) -1H-pyrazol-3-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 2 -9, steps B-1 to B-3)
¹ H-NMR spectrum (CDCl ₃ ) δ: 8.10 (1H, s), 7.85 (1H, d, J = 8.2 Hz), 7.72 (1H, d, J = 8.2 Hz), 7.05 (1H, s), 3.61 (2H, q, J = 9.4 Hz), 1.72 (9H, s).

Example 17
5- {3-[(Cyclopropylmethyl) thio] -4-methylphenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-9)
(1) 1-methyl-5- (4-methylphenyl) -3- (trifluoromethyl) -1H-pyrazole (Compound No. 4-1, Step C-1)
[1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] boronic acid (5.8 g, 30.0 mmol) and 4-iodotoluene (6.54 g, 30.0 mmol) in 1,4 -Dissolved in dioxane (50 ml) and then 2M aqueous sodium carbonate (45 ml, 90.0 mmol) was added. After adding tetrakistriphenylphosphine palladium (1.16 g, 1.0 mmol), the mixture was heated to reflux for 18 hours. Ethyl acetate was added and washed twice with saturated brine. After drying over magnesium sulfate and concentrating under reduced pressure, the residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 7/1) to give the title compound (3.11 g, yield 43.2%). Got.
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.30 (4H, s), 6.52 (1H, s), 3.91 (3H, s), 2.42 (3H, s).
(2) 1-methyl-5- (4-methylphenyl) -3- (trifluoromethyl) -1H-pyrazole (Compound No. 4-1, Step C-2)
4-methylphenylboronic acid (3.54 g, 26.0 mmol), 1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl trifluoromethanesulfonate (2.44 g, 30.0 mmol), phosphoric acid Tripotassium (5.52 g, 26.0 mmol) and potassium bromide (1.31 g, 11.0 mmol) are dissolved in 1,4-dioxane (20 ml) and then tetrakistriphenylphosphine palladium (924 mg, 0.8 mmol). ) And heated to reflux for 18 hours. After filtration through celite, ethyl acetate was added to the filtrate, washed twice with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 7/1) to obtain the title compound (1.77 g, yield 95.2%).
The ¹ H-NMR spectrum of the compound of Compound No. 4-1 obtained in this step was the same as that of the compound (1).
(3) 1-methyl-5- (4-methylphenyl) -3- (trifluoromethyl) -1H-pyrazole (Compound No. 4-1, Step C-3)
4,4,4-trifluoro-1- (4-methylphenyl) -1,3-butanedione (1.00 g, 4.3 mmol) was dissolved in toluene (10 ml), and methyl hydrazine (0.25 ml) was added at room temperature. 4.8 mmol) was added and heated to reflux for 3 hours. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 20/1) to obtain the title compound (254.8 mg, 24.7%).
The ¹ H-NMR spectrum of the compound of Compound No. 4-1 obtained in this step was the same as that of the compound (1).
(4) 1-methyl-5- (4-methyl-3-nitrophenyl) -3- (trifluoromethyl) -1H-pyrazole (Compound No. 4-2, Step C-4)
To a solution of 1-methyl-5- (4-methylphenyl) -3- (trifluoromethyl) -1H-pyrazole (1.41 g, 5.8 mmol) in concentrated sulfuric acid (2 ml) was added nitric acid (0. A mixture of 5 ml, 7.0 mmol) and concentrated sulfuric acid (0.5 ml) was added and stirred at room temperature for 2 hours. The reaction solution was poured into ice water and neutralized with sodium carbonate. The mixture was extracted with dichloromethane, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 5/1) to obtain the title compound (899 mg, yield 53.7%).
¹ H-NMR spectrum (CDCl ₃ ) δ: 8.05 (1H, d, J = 1.7 Hz), 7.57 (1H, dd, J = 8.2, 1.7 Hz), 7.50 (1H, d, J = 8.2 Hz), 6.63 (1H, s), 3.95 (3H, s), 2.68 (3H, s).
(5) 1-methyl-5- (4-methyl-3-aminophenyl) -3- (trifluoromethyl) -1H-pyrazole (Compound No. 4-3, Step C-5)
1-Methyl-5- (4-methyl-3-nitrophenyl) -3- (trifluoromethyl) -1H-pyrazole (833 mg) was dissolved in methanol (10 ml) and 7.5% palladium carbon (M-type, 90 mg) was added. Under a hydrogen atmosphere, the mixture was vigorously stirred at normal pressure and room temperature for 6 hours. After the reaction vessel was purged with nitrogen, the reaction solution was filtered through Celite, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 1/1) to obtain the title compound (701.1 mg, yield 94.1%).
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.14 (1H, d, J = 7.6 Hz), 6.72 (1H, dd, J = 7.6, 2.1 Hz), 6.68 (1H, d, J = 2.1 Hz), 6.49 (1H, s), 3.90 (3H, s), 3.76 (2H, br s), 2.22 (3H, s).
(6) O-ethyl S- {2-methyl-5- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] phenyl} dithiocarbonate (step C-6)
To 1-methyl-5- (4-methyl-3-aminophenyl) -3- (trifluoromethyl) -1H-pyrazole (616 mg, 2.4 mmol) was added water (3 ml) followed by concentrated hydrochloric acid (1 0.0 ml) was added. Under ice cooling, an aqueous solution (1 ml) of sodium nitrite (183 mg, 2.6 mmol) was slowly added, and the mixture was further stirred for 1 hour to prepare a mixture containing a diazonium salt.
To a separate flask was added water (3 ml), O-ethyl potassium dithiocarbonate (463 mg, 2.9 mmol) and sodium carbonate (306 mg, 2.9 mmol) and heated to 70 ° C. Into this, the mixture containing the diazonium salt prepared previously was added little by little. Then, it heated up at 90 degreeC and stirred for 1 hour. The reaction solution was extracted twice with dichloromethane, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 10/1) to obtain the title compound (354.4 mg, yield 40.8%).
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.55 (1H, d, J = 2.1 Hz), 7.46 (1H, d, J = 7.6 Hz), 7.42 (1H, dd, J = 7.6, 2.1 Hz), 6.57 (1H, s), 4.63 (2H, q, J = 7.1 Hz), 3.92 (3H, s), 2.49 (3H, s), 1.37 (3H, t, J = 7.1 Hz).
(7) 2-Methyl-5- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] benzenethiol (Compound No. 4-4, Step C-7)
O-ethyl S- {2-methyl-5- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] phenyl} dithiocarbonate (297 mg, 0.8 mmol) in methanol (3 ml) Dissolved, 2N sodium hydroxide (0.9 ml) was added at room temperature, and the mixture was heated to reflux for 1 hour. After allowing to cool, water (10 ml) and concentrated hydrochloric acid were added to make it acidic, followed by extraction with dichloromethane. The extract was dried over magnesium sulfate and concentrated under reduced pressure to give the title compound (220 mg, yield 98.7%).
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.32 (1H, d, J = 1.4 Hz), 7.27 (1H, d, J = 7.6 Hz), 7.11 (1H, dd, J = 7.6, 1.4 Hz), 6.52 (1H, s), 3.90 (3H, s), 3.40 (1H, s), 2.39 (3H, s).
(8) 5- {3-[(Cyclopropylmethyl) thio] -4-methylphenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-9, Step C-8)
N of 2-methyl-5- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] benzenethiol (61 mg, 0.2 mmol) and bromomethylcyclopropane (30 μl, 0.3 mmol) , N-dimethylformamide (1 ml) solution was added 60% sodium hydride (12 mg, 0.3 mmol), and the mixture was heated and stirred at 80 ° C. for 1 hour. After allowing to cool, water was added and the mixture was extracted with ethyl acetate. After drying over magnesium sulfate and concentrating under reduced pressure, the residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 5/1) to obtain the title compound (59 mg, yield 83.1%). It was.
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.30-7.25 (2H, m), 7.10 (1H, dd, J = 7.9, 1.8 Hz), 6.53 (1H, s), 3.90 (3H, s), 2.87 ( 2H, d, J = 6.7 Hz), 2.43 (3H, s), 1.12-1.03 (1H, m), 0.65-0.60 (2H, m), 0.28-0.31 (2H, m).
Furthermore, the compounds of Examples 18 to 40 below were produced using the method of Step C.

Example 18
1-methyl-5- [4-methyl-3- (propylthio) phenyl] -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-3, Steps C-2 and C-4 to C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.26 (1H, d, J = 7.6 Hz), 7.23 (1H, d, J = 2.1 Hz), 7.09 (1H, dd, J = 7.6, 2.1 Hz), 6.55 (1H, s), 3.93 (3H, s), 2.91 (2H, t, J = 7.2 Hz), 2.42 (3H, s), 1.73 (2H, td, J = 14.8, 7.6 Hz), 1.07 (3H, t, J = 7.6 Hz).

Example 19
5- (3-Butylthio-4-methylphenyl) -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-7, Steps C-1 and C-4 to C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.26 (1H, d, J = 7.9 Hz), 7.22 (1H, d, J = 1.7 Hz), 7.09 (1H, dd, J = 7.9, 1.7 Hz), 6.53 (1H, s), 3.91 (3H, s), 2.93 (2H, t, J = 7.6 Hz), 2.41 (3H, s), 1.68 (2H, q, J = 7.6 Hz), 1.49 (2H, q, J = 7.6 Hz), 0.95 (3H, t, J = 7.6 Hz).

Example 20
5- {3-[(Cyclopropylmethyl) thio] -4-methylphenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-9, Steps C-1 and C-4) ~ C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.30-7.25 (2H, m), 7.10 (1H, dd, J = 7.9, 1.8 Hz), 6.53 (1H, s), 3.90 (3H, s), 2.87 ( 2H, d, J = 6.7 Hz), 2.43 (3H, s), 1.12-1.03 (1H, m), 0.65-0.60 (2H, m), 0.28-0.31 (2H, m).

Example 21
5- {3-[(Cyclopropylmethyl) sulfinyl] -4-methylphenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-10, Steps C-1 and C-4) ~ C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 8.01 (1H, d, J = 1.8 Hz), 7.44 (1H, dd, J = 7.9, 1.8 Hz), 7.33 (1H, d, J = 7.9 Hz), 6.61 (1H, s), 3.95 (3H, s), 2.81 (1H, dd, J = 12.8, 7.3 Hz), 2.72 (1H, dd, J = 12.8, 7.3 Hz), 2.44 (3H, s), 1.16- 1.06 (1H, m), 0.73-0.61 (2H, m), 0.33-0.26 (2H, m).

Example 22
5- {3-[(Cyclobutylmethyl) thio] -4-methylphenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-11, Steps C-1 and C-4) ~ C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.25 (1H, d, J = 8.6 Hz), 7.22 (1H, d, J = 1.2 Hz), 7.09 (1H, dd, J = 7.3, 1.8 Hz), 6.53 (1H, s), 3.91 (3H, s), 2.99 (1H, d, J = 7.3 Hz), 2.60-2.54 (1H, m), 2.41 (3H, s), 2.18-2.12 (2H, m), 1.93-1.76 (4H, m).

Example 23
1-methyl-5- [4-methyl-3- (2-propenylthio) phenyl] -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-13, Steps C-1 and C-4 to C -8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.28-7.27 (2H, m), 7.12 (1H, dd, J = 7.3, 1.8 Hz), 6.51 (1H, s), 5.94-5.86 (1H, m), 5.22-5.13 (2H, m), 3.90 (3H, s), 3.58 (2H, dt, J = 6.7, 1.2 Hz), 2.42 (3H, s).

Example 24
1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-15, Step C) -1 and C-4 to C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.60 (1H, d, J = 2.1 Hz), 7.57 (1H, d, J = 8.2 Hz), 7.31 (1H, dd, J = 8.2, 2.1 Hz), 6.57 (1H, s), 3.91 (3H, s), 3.52 (2H, q, J = 9.4 Hz).

Example 25
1-methyl-5- {4-methyl-3-[(3,3,3-trifluoropropyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-17, Step C) -1 and C-4 to C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.32 (1H, d, J = 7.9 Hz), 7.31 (1H, d, J = 1.8 Hz), 7.19 (1H, dd, J = 7.9, 1.8 Hz), 6.54 (1H, s), 3.91 (3H, s), 3.08 (2H, dt, J = 8.4, 3.5 Hz), 2.45-2.42 (5H, m).

Example 26
1-methyl-5- {4-methyl-3-[(2,2,3,3-tetrafluoropropyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-19, Steps C-1 and C-4 to C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.47 (1H, d, J = 1.8 Hz), 7.34 (1H, d, J = 7.9 Hz), 7.23 (1H, dd, J = 7.9, 1.8 Hz), 6.54 (1H, s), 5.91 (1H, tt, J = 53.2, 2.4 Hz), 3.90 (3H, s), 3.41 (2H, tt, J = 15.9, 1.2 Hz), 2.53 (3H, s).

Example 27
5- [4-Chloro-3- (propylthio) phenyl] -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-23, Steps C-1 and C-4 to C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.47 (1H, d, J = 8.2 Hz), 7.23 (1H, d, J = 2.1 Hz), 7.11 (1H, dd, J = 8.2, 2.1 Hz), 6.55 (1H, s), 3.91 (3H, s), 2.94 (2H, t, J = 7.6 Hz), 1.76 (2H, td, J = 14.6, 7.1 Hz), 1.09 (3H, t, J = 7.2 Hz) .

Example 28
5- {4-Chloro-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-35, Step C) -1 and C-4 to C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.60 (1H, d, J = 2.1 Hz), 7.57 (1H, d, J = 8.2 Hz), 7.31 (1H, dd, J = 8.2, 2.1 Hz), 6.57 (1H, s), 3.91 (3H, s), 3.52 (2H, q, J = 9.4 Hz).

Example 29
1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (pentafluoroethyl) -1H-pyrazole (Compound No. 1-67, Step C) -1 and C-4 to C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.52 (1H, d, J = 1.8 Hz), 7.35 (1H, d, J = 7.9 Hz), 7.27 (2H, dd, J = 7.9, 1.8 Hz), 6.56 (1H, s), 3.93 (3H, s), 3.43 (2H, q, J = 9.6 Hz), 2.53 (3H, s).

Example 30
3- (Heptafluoropropyl) -1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1H-pyrazole (compound number 1-71, step C-1 and C-4 to C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.53 (1H, d, J = 1.8 Hz), 7.36 (1H, d, J = 7.3 Hz), 7.27 (1H, dd, J = 7.3, 1.8 Hz), 6.56 (1H, s), 3.93 (3H, s), 3.43 (2H, q, J = 9.6 Hz), 2.54 (3H, s).

Example 31
({2-Methyl-5- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] phenyl} thio) acetonitrile (Compound No. 1-75, Steps C-1 and C-4 to C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.56 (1H, d, J = 1.8 Hz), 7.40 (1H, d, J = 7.9 Hz), 7.33 (1H, dd, J = 7.9, 1.8 Hz), 6.57 (1H, s), 3.95 (3H, s), 3.59 (2H, s), 2.55 (3H, s).

Example 32
1-methyl-5- {4-methyl-3-[(2,2,3,3,3-pentafluoropropyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1- 76, Steps C-1 and C-4 to C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.50 (1H, d, J = 1.2 Hz), 7.35 (1H, d, J = 7.3 Hz), 7.26 (1H, dd, J = 7.3, 1.2 Hz), 6.54 (1H, s), 3.90 (3H, s), 3.43 (2H, t, J = 16.5 Hz), 2.54 (3H, s).

Example 33
5- [3- (Cyclopentylthio) -4-methylphenyl] -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-77, Steps C-1 and C-4 to C-8) )
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.29 (1H, d, J = 1.3 Hz), 7.25 (1H, d, J = 7.7 Hz), 7.09 (1H, dd, J = 7.7, 1.3 Hz), 6.52 (1H, s), 3.91 (3H, s), 3.68-3.56 (1H, m), 2.40 (3H, s), 2.19-1.58 (8H, m).

Example 34
1-methyl-5- {4-methyl-3-[(2-methyl-2-propenyl) thio] phenyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-78, Step C-1 and C-4 to C-8)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.29-7.24 (2H, m), 7.11 (1H, dd, J = 7.9, 1.8 Hz), 6.51 (1H, s), 4.88 (2H, s), 3.89 ( 3H, s), 3.53 (2H, s), 2.44 (3H, s), 1.88 (3H, s).

Example 35
5- (4-Chlorophenyl) -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 4-5, Step C-2)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.48 (2H, d, J = 8.9 Hz), 7.35 (2H, d, J = 8.9 Hz), 6.55 (1H, s), 3.91 (3H, s).

Example 36
5- (4-Bromo-3-nitrophenyl) -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 4-10, Steps C-3 and C-4)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.91 (1H, d, J = 2.1 Hz), 7.90 (1H, d, J = 8.2 Hz), 7.49 (1H, dd, J = 8.2, 2.1 Hz), 6.66 (1H, s), 3.96 (3H, s).

Example 37
1-methyl-3- (4-methylphenyl) -5- (trifluoromethyl) -1H-pyrazole (Compound No. 5-1, Step C-3)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.65 (2H, d, J = 7.6 Hz), 7.22 (2H, d, J = 7.6 Hz), 6.85 (1H, s), 4.02 (3H, s), 2.37 (3H, s).

Example 38
3- (4-Bromo-3-nitrophenyl) -1-methyl-5- (trifluoromethyl) -1H-pyrazole (Compound No. 5-10, Steps C-3 and C-4)
¹ H-NMR spectrum (CDCl ₃ ) δ: 8.25 (1H, d, J = 2.1 Hz), 7.82 (1H, dd, J = 8.9, 2.1 Hz), 7.77 (1H, d, J = 8.9 Hz), 6.94 (1H, s), 4.05 (3H, s).

Example 39
1-methyl-4- (4-methylphenyl) -3- (trifluoromethyl) -1H-pyrazole (Compound No. 6-1, Step C-2)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.45 (1H, s), 7.30-7.18 (4H, m), 3.97 (3H, s), 2.38 (3H, s).

Example 40
2-Methyl-5- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-4-yl] aniline (Compound No. 6-3, Steps C-4 and C-5)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.41 (1H, s), 7.05 (1H, d, J = 7.7 Hz), 6.74-6.70 (2H, m), 3.95 (3H, s), 3.64 (2H, s), 2.18 (3H, s).
Furthermore, the compounds of Examples 41 to 47 below were produced using the methods of Step C and Step A-3.

Example 41
1-methyl-5- [4-methyl-3- (propylsulfinyl) phenyl] -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-4, Step C-1, C-4 to C-8) And Step A-3)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.98 (1H, d, J = 1.7 Hz), 7.44 (1H, dd, J = 7.6, 1.7 Hz), 7.34 (1H, d, J = 7.6 Hz), 6.62 (1H, s), 3.95 (3H, s), 2.85-2.70 (2H, m), 2.44 (3H, s), 1.95-1.71 (2H, m), 1.09 (3H, t, J = 7.6 Hz).

Example 42
5- [3- (Butylsulfinyl) -4-methylphenyl] -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-8, Step C-1, C-4 to C-8 And Step A-3)
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.98 (1H, d, J = 1.7 Hz), 7.44 (1H, dd, J = 7.6, 1.7 Hz), 7.34 (1H, d, J = 7.6 Hz), 6.62 (1H, s), 3.95 (3H, s), 2.89-2.71 (2H, m), 2.44 (3H, s), 1.90-1.63 (2H, m), 1.57-1.41 (2H, m), 0.95 (3H , t, J = 7.2 Hz).

Example 43
5- {3-[(Cyclobutylmethyl) sulfinyl] -4-methylphenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-12, Steps C-1, C-4) To C-8 and step A-3).
¹ H-NMR spectrum (CDCl ₃ ) δ: 7.98 (1H, d, J = 1.8 Hz), 7.43 (1H, dd, J = 7.9, 1.8 Hz), 7.33 (1H, d, J = 7.9 Hz), 6.61 (1H, s), 3.95 (3H, s), 2.94-2.88 (3H, m), 2.44 (3H, s), 2.32-2.23 (1H, m), 2.09-1.68 (5H, m).

Example 44
1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-16, Step C) -1, C-4 to C-8 and step A-3)
¹ H-NMR spectrum (CDCl ₃ ) δ: 8.06 (1H, d, J = 1.7 Hz), 7.52 (1H, dd, J = 7.9, 1.7 Hz), 7.41 (1H, d, J = 7.9 Hz), 6.63 (1H, s), 3.95 (3H, s), 3.50-3.46 (2H, m), 2.47 (3H, s).

Example 45
1,3-Dimethyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -1H-pyrazole (Compound No. 1-63, Step C-2, C-4) To C-8 and step A-3).
¹ H-NMR spectrum (CDCl ₃ ) δ: 8.02 (1H, d, J = 1.2 Hz), 7.50 (1H, dd, J = 7.6, 1.5 Hz), 7.35 (1H, d, J = 7.9 Hz), 6.16 (1H, s), 3.84 (3H, s), 3.47 (2H, q, J = 10.0 Hz), 2.45 (3H, s), 2.30 (3H, s).

Example 46
1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -3- (pentafluoroethyl) -1H-pyrazole (Compound No. 1-68, Step C) -1, C-4 to C-8 and step A-3)
¹ H-NMR spectrum (CDCl ₃ ) δ: 8.07 (1H, d, J = 1.8 Hz), 7.53 (1H, dd, J = 7.9, 1.8 Hz), 7.41 (1H, d, J = 7.9 Hz), 6.65 (1H, s), 3.97 (3H, s), 3.48 (2H, q, J = 9.8 Hz), 2.47 (3H, s).

Example 47
3- (Heptafluoropropyl) -1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -1H-pyrazole (Compound No. 1-72, step) C-1, C-4 to C-8 and step A-3)
¹ H-NMR spectrum (CDCl _Three ) δ: 8.07 (1H, d, J = 1.4 Hz), 7.54 (1H, dd, J = 8.2, 1.4 Hz), 7.41 (1H, d, J = 8.2 Hz), 6.65 (1H, s), 3.97 ( 3H, s), 3.48 (2H, q, J = 9.9 Hz), 2.47 (3H, s).
Example 48
1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-15, Step B) -1, B-2, B-4 and B-3) and 1-methyl-3- {4-methyl-3-[(2,2,2-trifluoroethyl) phenyl] -5- (trifluoromethyl ) -1H-pyrazole (Compound No. 2-14, Steps B-1, B-2, B-4 and B-3)
(1) 4- (1-Ethoxyethenyl) -1-methyl-2-[(2,2,2-trifluoroethyl) thio] benzene (Step B-1)
To a toluene solution (5.0 ml) of 4-bromo-1-methyl-2-[(2,2,2-trifluoroethyl) thio] benzene (1.05 g, 3.68 mmol) was added tributyl (1-ethoxyvinyl). ) Tin (1.24 ml, 3.68 mmol) and bis (triphenylphosphine) palladium (II) chloride (0.129 g, 0.184 mmol) were added, and the mixture was heated and stirred at 100 ° C. for 3 hours. A saturated aqueous sodium hydrogen carbonate solution (5 ml) and a 10% aqueous potassium fluoride solution (5 ml) were added to the reaction solution, and the mixture was stirred at room temperature for 15 minutes, and then the reaction solution was filtered through celite. After separating the organic layer of the filtrate, the aqueous layer was extracted once with ethyl acetate. The organic layers were combined, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give the title compound as an oil.
This compound was used in the next step without further purification.
(2) 4-Ethoxy-1,1,1-trifluoro-4- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} but-3-en-2-one (Process B-2)
The total amount of the compound of (1) above was dissolved in tetrahydrofuran (10 ml), cooled to 0 ° C., pyridine (0.36 ml, 4.42 mmol) was added, followed by trifluoroacetic anhydride (0.52 ml, 3. 68 mmol) and stirred at the same temperature for 2 hours, followed by stirring at room temperature for 30 minutes. A saturated aqueous sodium hydrogen carbonate solution (5 ml) and a 10% aqueous potassium fluoride solution (5 ml) were added to the reaction solution, and the mixture was stirred at room temperature for 30 minutes, and then the reaction solution was filtered through celite. After separating the organic layer of the filtrate, the aqueous layer was extracted once with ethyl acetate. The organic layers were combined, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 10/1) to give the title compound (841.0 mg).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.66 (1H, d, J = 1.4 Hz), 7.36 (1H, dd, J = 7.6Hz, 1.4Hz), 7.27 (1H, d, J = 7.6Hz, 5.80 (1H, s), 4.18 ( 2H, q, J = 6.9Hz), 3.44 (2H, q, J = 9.6Hz), 2.51 (3H, s), 1.49 (3H, t, J = 6.9Hz).
(3) 1,1,1-trifluoro-4-hydroxy-4- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} but-3-en-2-one (Process B-4)
The above compound (2) (841.0 mg) was dissolved in methanol (9 ml), 2N hydrochloric acid (3.0 ml) was added, and the mixture was stirred at 50 ° C. for 3 hours. To the reaction solution were added saturated brine (10 ml) and water (10 ml), and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give the title compound (845.6 mg, 67% yield over 2 steps).
¹ H-NMR spectrum (CDCl _Three ) δ: 15.10 (1H, brd. s), 8.06 (1H, s), 7.76 (1H, d, J = 7.6Hz), 7.37 (1H, d, J = 7.6Hz), 6.53 (1H, s), 3.47 (1H, q, J = 8.9Hz), 2.55 (3H, s).
(4) 1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-15 Step B-3) and 1-methyl-3- {4-methyl-3-[(2,2,2-trifluoroethyl) phenyl] -5- (trifluoromethyl) -1H-pyrazole (Compound No. 2) -14, process B-3)
The compound of (3) (37.5 mg, 0.109 mmol) was dissolved in ethanol (1.0 ml), acetic acid (100 μl) and methylhydrazine (9 μl) were added, and the mixture was heated to reflux for 2 hours. After allowing to cool, water was added to the reaction mixture, and the mixture was extracted twice with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 1/5) to give compound No. 1-15 (11.7 mg, yield 30%) and compound No. 2-14. Of the compound (8.2 mg, 21% yield).
Compound No. 1-15
¹ H-NMR spectrum (CDCl _Three ) δ: 7.60 (1H, d, J = 2.1Hz), 7.57 (1H, d = 8.2H), 7.31 (1H, dd, J = 8.2, 2.1Hz), 6.57 (1H, s), 3.91 (3H, s), 3.52 (2H, q, J = 9.4Hz).
Compound No. 2-14
¹ H-NMR spectrum (CDCl _Three ) δ: 7.90 (1H, d, J = 1.4Hz), 7.59 (1H, dd, J = 7.6, 1.4Hz), 7.27 (1H, d, J = 7.6Hz), 6.86 (1H, s), 4.03 ( 3H, s), 3.45 (2H, q, J = 9.6Hz), 2.49 (3H, s).
Example 49
3- {4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] phenyl} -1, 2,4-oxadiazole (Compound No. 1-150, Steps D-1 and D-2)
(1) N′-hydroxy-4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] Benzenecarboximide (Step D-1)
4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1-55) ( Hydroxylamine hydrochloride (953.4 mg, 13.72 mmol) and triethylamine (1.9 ml, 13.63 mmol) were added to a solution of 1.00 g, 2.74 mmol) of 1,4-dioxane (10.0 ml) and stirred at 70 ° C. for 6 hours. Subsequently, it stirred at 120 degreeC for 2 hours. The reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (eluent: hexane / ethyl acetate = 1/1 to 1/4) to obtain the title compound (536.5 mg, yield 49.2%).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.63 (1H, d, J = 7.9 Hz), 7.60 (1H, d, J = 1.7 Hz), 7.40 (1H, dd, J = 7.9, 1.7 Hz), 6.89 (1H, br s), 6.59 (1H, s), 4.99 (2H, br s), 3.92 (3H, s), 3.54 (2H, q, J = 9.6 Hz).
(2) 3- {4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] phenyl} -1,2,4-oxadiazole (Compound No. 1-150, Step D-2)
To a solution of the compound (1) (102.1 mg, 0.26 mmol) in ethanol (2.6 ml) at room temperature was added ethyl orthoformate (0.26 ml, 1.56 mmol) and sulfuric acid (2 drops) at the same temperature for 6 days. Stir. The reaction solution was poured into a saturated sodium bicarbonate solution and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 1/2) to obtain the title compound (Compound No. 1-150, 32.1 mg, yield 30.7%).
¹ H-NMR spectrum (CDCl _Three ) δ: 8.87 (1H, s), 8.13 (1H, d, J = 7.9 Hz), 7.76 (1H, s), 7.52 (1H, d, J = 7.9 Hz), 6.65 (1H, s), 3.97 ( 3H, s), 3.61 (2H, q, J = 9.7 Hz).
Example 50
1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3-[(2,2,2-trifluoroethyl) thio] -1H-pyrazole (Compound No. 1-109, Steps E-1 to E-6)
(1) 1-methyl-5- (4-methylphenyl) -1H-pyrazol-3-ol (Step E-1)
To a mixed solution of ethyl 3- (4-methylphenyl) -2-propinoate (651.2 mg, 3.46 mmol) in ethanol (3.5 ml) and water (3.5 ml) was added methylhydrazine (0.2 ml, 3.76 mmol), and And stirred with heating for 7 hours. The reaction solution was concentrated under reduced pressure, ethyl acetate was added, and the mixture was filtered to obtain a solid. The obtained solid was washed with ethyl acetate and then dried to obtain the title compound (79.1 mg, yield 12.1%).
¹ H-NMR spectrum (DMSO-d ₆ ) δ: 9.60 (1H, s), 7.35 (2H, d, J = 8.0 Hz), 7.27 (2H, d, J = 8.0 Hz), 5.56 (1H, s), 3.59 (3H, s), 2.35 ( 3H, s).
(2) 1-methyl-5- (4-methylphenyl) -1H-pyrazole-3-thiol (step E-2)
Lawesson's reagent (502.5 mg, 1.24 mmol) was added to a toluene (4.8 ml) solution of the compound (1) (456.0 mg, 2.42 mmol), and the mixture was heated and stirred at 120 ° C. for 7 hours. The reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 3/1) to obtain the title compound (259.6 mg, yield 52.5%).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.61 (2H, d, J = 8.1 Hz), 7.18 (2H, d, J = 8.1 Hz), 6.67 (0.5H, s), 6.66 (0.5H, s), 3.80 (3H, s), 2.36 (3H, s).
(3) 1-methyl-5- (4-methylphenyl) -3-[(2,2,2-trifluoroethyl) thio] -1H-pyrazole (Step E-3)
To a solution of compound (2) (294.6 mg, 1.44 mmol) in 1,4-dioxane (8.0 ml) at room temperature, sodium hydroxide (385.6 mg, 9.64 mmol), water (3.1 ml) and 1,1,1, 1-Trifluoro-2-iodoethane (0.71 ml, 7.20 mmol) was added, and the mixture was heated with stirring at 65 ° C. for 6.5 hours. The reaction solution was poured into water and extracted with ether. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 3/1) to obtain the title compound (203.2 mg, yield 49.2%).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.64 (2H, d, J = 8.3Hz), 7.20 (2H, d, J = 8.3 Hz), 6.74 (1H, s), 3.99 (3H, s), 3.30 (2H, q, J = 9.6 Hz), 2.36 (3H, s).
(4) 2-Methyl-5- {1-methyl-3-[(2,2,2-trifluoroethyl) thio] -1H-pyrazol-5-yl} benzenesulfonyl chloride (Step E-4)
To the compound (30.7) (200.7 mg, 0.70 mmol) was added chlorosulfonic acid (0.70 ml, 10.53 mmol) under ice cooling, and the mixture was heated and stirred at 50 ° C. for 4 hours. The reaction solution was poured into ice water containing ethyl acetate and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give the title compound (323.4 mg).
¹ H-NMR spectrum (CDCl _Three ) δ: 8.41 (1H, d, J = 1.6 Hz), 8.00 (1H, dd, J = 7.9, 1.6 Hz), 7.44 (1H, d, J = 7.9 Hz), 6.83 (1H, s), 4.02 ( 3H, s), 3.33 (2H, q, J = 9.5 Hz), 2.81 (3H, s).
(5) 2-Methyl-5- {1-methyl-3-[(2,2,2-trifluoroethyl) thio] -1H-pyrazol-5-yl} benzenethiol (Step E-5)
Zinc (199.4 mg, 3.05 mmol) was added to an acetic acid solution (3.0 ml) of the above compound (4) (68.0 mg), and the mixture was heated to reflux for 3.5 hours. Ice water and ethyl acetate were added to the reaction solution, and insoluble matters were removed by filtration. The filtrate was extracted with ethyl acetate, and the extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 2/1) to obtain the title compound (31.6 mg, yield in 2 steps 67.4%).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.69 (1H, s), 7.43 (1H, d, J = 7.8 Hz), 7.17 (1H, d, J = 7.8 Hz), 6.73 (1H, s), 3.99 (3H, s), 3.37 ( 1H, s), 3.30 (2H, q, J = 9.6 Hz), 2.34 (3H, s).
(6) 1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3-[(2,2,2-trifluoroethyl) thio]- 1H-pyrazole (Compound No. 1-109, Step E-6)
To a solution of the above compound (5) (31.6 mg, 0.099 mmol) in N, N-dimethylformamide (3 ml), 1,1,1-trifluoro-2-iodoethane (15 μl, 0.15 mmol), potassium carbonate (15.2 mg) 0.11 mmol) and Rongalite (1.8 mg, 0.012 mmol) were added and stirred at room temperature overnight. The reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 3/1) to obtain the title compound (32.1 mg, yield 80.8%).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.87 (1H, s), 7.58 (1H, d, J = 7.7 Hz), 7.24 (1H, d, J = 7.7 Hz), 6.74 (1H, s), 4.00 (3H, s), 3.46 ( 2H, q, J = 9.6 Hz), 3.32 (2H, q, J = 9.5 Hz), 2.48 (3H, s).
Example 51
1-methyl-5- {4-methyl-3-[(trifluoromethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-158, Step C-8)
2-Methyl-5- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] benzenethiol and trifluoromethyl iodide as in Example 17 (8). Work up to give the title compound.
Furthermore, the compounds of Examples 52 to 86 below were produced using Steps A to E below.
Example 52
5- {2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1- 79)
The title compound was obtained using 3-fluoro-4-bromotoluene as a starting material and the reaction and post-treatment of Steps C-4 to C-8 and Step A-2a.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.52 (1H, d, J = 7.2 Hz), 7.13 (1H, d, J = 10.4 Hz), 6.57 (1H, s), 3.84 (3H, s), 3.34 (2H, q, J = 9.6 Hz), 2.56 (3H, s).
Example 53
5- [4-Methyl-3- (propylsulfinyl) phenyl] -1- (2,2,2-trifluoroethyl) -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-85)
4-acetyltoluene is reacted with 2,2,2-trifluoroethyl trifluoroacetate using a known method (for example, a method such as J. Org. Chem., 1990, vol. 55, 1959-1964). Using the obtained 1,1,1-trifluoro-4-hydroxy-4- (4-methylphenyl) but-3-en-2-one as a starting material, Steps C-3 to C-8 and Step A The title compound was obtained using -3 reaction and workup.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.93 (1H, d, J = 1.4 Hz), 7.42 (1H, dd, J = 7.6, 1.4 Hz), 7.37 (1H, d, J = 7.6 Hz), 6.66 (1H, s), 4.78- 4.69 (2H, m), 2.87-2.78 (1H, m), 2.74-2.67 (1H, m), 2.45 (3H, s), 1.97-1.85 (1H, m), 1.76-1.65 (1H, m), 1.08 (3H, t, J = 7.6 Hz).
Example 54
5- {4-Bromo-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-86)
4-acetyl-1-bromobenzene and 2,2,2-trifluoroethyl trifluoroacetate and known methods (for example, methods such as J. Org. Chem., 1990, vol. 55, 1959-1964)) And using the obtained 4- (4-bromophenyl) -1,1,1-trifluoro-4-hydroxybut-3-en-2-one as a starting material, steps C-3 to C- The title compound was obtained using reaction 8 and workup.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.75 (1H, d, J = 8.2 Hz), 7.58 (1H, d, J = 2.1 Hz), 7.21 (1H, dd, J = 8.2, 2.1 Hz), 6.57 (1H, s), 3.91 ( 3H, s), 3.53 (2H, q, J = 9.6 Hz).
Example 55
5- {4-Bromo-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-87)
Using Step A-3, the compound of Example 54 was oxidized to give the title compound.
¹ H-NMR spectrum (CDCl _Three ) δ: 8.04 (1H, d, J = 2.1 Hz), 7.77 (1H, d, J = 8.2 Hz), 7.51 (1H, dd, J = 8.2, 2.1 Hz), 6.66 (1H, s), 3.96 ( 3H, s), 3.91-3.81 (1H, m), 3.49-3.39 (1H, m).
Example 56
4- [3- (Difluoromethyl) -1-methyl-1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1-88)
The title compound was obtained by reacting difluoroacetic acid with oxalyl chloride and using the corresponding acid chloride obtained as a starting material and the reaction and post-treatment of Steps B-2 and B-3.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.82 (1H, d, J = 8.2 Hz), 7.73 (1H, 1.2 Hz), 7.50 (1H, dd, J = 8.2, 1.2 Hz), 6.70 (1H, t, J = 55.1 Hz), 6.61 (1H, s), 3.92 (3H, s), 3.61 (2H, q, J = 9.2 Hz).
Example 57
4- {1-methyl-3- [2,2,2-trifluoro-1- (trifluoromethyl) ethyl] -1H-pyrazol-5-yl} -2-[(2,2,2-trifluoro Ethyl) thio] benzonitrile (Compound No. 1-89)
2-Trifluoromethyl-3,3,3-trifluoropropionic acid is reacted with oxalyl chloride, and the corresponding acid chloride obtained is used as a starting material to carry out the reaction and post-treatment of steps B-2 and B-3. Used to give the title compound.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.82 (1H, d, J = 8.1 Hz), 7.75 (1H, d, J = 1.5 Hz), 7.52 (1H, dd, J = 8.1, 1.5 Hz), 6.54 (1H, s), 4.40- 4.28 (1H, m), 3.92 (3H, s), 3.62 (2H, q, J = 9.3 Hz).
Example 58
5- {4-Ethyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-90)
(1) 1-methyl-3- (trifluoromethyl) -5- [3-nitro-4- (2-trimethylsilylethynyl) phenyl] -1H-pyrazole
1-Methyl-3- (trifluoromethyl) -5- (4-bromophenyl) -1H-pyrazole was subjected to the reaction and post-treatment of Step C-4, and the resulting 1-methyl-3- (trifluoro) was obtained. To a solution of methyl) -5- (3-nitro-4-bromophenyl) -1H-pyrazole (3.42 g, 9.7 mmol) in triethylamine (20 ml) was added trimethylsilylacetylene (2.1 ml, 14.7 mmol), palladium acetate. (II) (22.4 mg, 0.1 mmol), triphenylphosphine (83.5 mg, 0.3 mmol) and cuprous iodide (12.3 mg, 0.06 mmol) were added, followed by 4 at 100 ° C. Stir with heating for hours. The reaction solution was cooled to room temperature and then concentrated under reduced pressure. Ethyl acetate was added to the residue, washed with saturated ammonium chloride solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 10/1) to obtain the title compound (2.72 g).
¹ H-NMR spectrum (CDCl _Three ) δ: 8.09 (1H, d, J = 1.7 Hz), 7.78 (1H, d, J = 7.7 Hz), 7.62 (1H, dd, J = 7.7, 1.7 Hz), 6.67 (1H, s), 3.97 ( 3H, s), 0.30 (9H, s).
(2) 5- (3-Nitro-4-ethynylphenyl) -1-methyl-3- (trifluoromethyl) -1H-pyrazole
To a solution of the compound (1) (1.10 g, 3.0 mmol) in methanol (10 ml) was added potassium carbonate (41.4 mg, 0.3 mmol), and the mixture was stirred at room temperature for 2 hours. Then, it concentrated under reduced pressure. Ethyl acetate was added to the residue, washed twice with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 7/1) to obtain the title compound (0.81 g).
¹ H-NMR spectrum (CDCl _Three ) δ: 8.13 (1H, d, J = 1.4 Hz), 7.83 (1H, d, J = 8.2 Hz), 7.66 (1H, dd, J = 8.2, 1.4 Hz), 6.68 (1H, s), 3.99 ( 3H, s), 3.65 (1H, s).
(3) 2-ethyl-5- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] aniline
To a solution of the compound (2) (0.79 g, 2.7 mmol) in methanol (10 ml) was added 5% Pd-CaCO. ₃ -PbO (100 mg) was added, and the mixture was stirred at room temperature for 3 hours under a hydrogen atmosphere. After replacing the reaction vessel with nitrogen, the reaction solution was filtered through celite, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 3/1) to obtain the title compound (0.26 g).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.16 (1H, d, J = 7.6 Hz), 6.76 (1H, dd, J = 7.6, 1.4 Hz), 6.69 (1H, d, J = 1.4 Hz), 6.49 (1H, s), 3.91 ( 3H, s), 3.77 (2H, br s), 2.56 (2H, q, J = 7.6 Hz), 1.30 (3H, t, J = 7.6 Hz).
(4) 5- {4-Ethyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-90) )
To a solution of the above compound (3) (260 mg, 0.9 mmol) in acetonitrile (2 ml), 2,2′-dithiobis (1,1,1-trifluoroethane) (331.5 mg, 1.4 mmol) and nitrous acid t-Butyl (140 μl, 1.2 mmol) was added and stirred at room temperature for 2 hours. Ethyl acetate was added to the reaction mixture, washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by reverse phase column chromatography (elution solvent: acetonitrile / water = 80/20) to obtain the title compound (26.0 mg).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.52 (1H, d, J = 1.7 Hz), 7.37 (1H, d, J = 8.2 Hz), 7.30 (1H, dd, J = 8.2, 1.7 Hz), 6.54 (1H, s), 3.91 ( 3H, s), 3.44 (2H, q, J = 9.6 Hz), 2.92 (2H, q, J = 7.6 Hz), 1.29 (3H, t, J = 7.6 Hz).
Example 59
1-methyl-5- {4- (2-propenyl) -3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-91)
To a solution of the compound of Example 54 (209 mg, 0.5 mmol) in toluene (2 ml) was added 2-propenyltributyltin (182 mg, 0.55 mmol), bisdibenzylideneacetone palladium (0) (14.4 mg, 0.025 mmol) and triphenyl. Phosphine (27.8 mg, 0. mmol) was added, and the mixture was heated and stirred at 130 ° C. for 4 hours under a nitrogen atmosphere. The reaction solution was cooled and then filtered through celite. The filtrate was washed twice with 10% aqueous ammonia, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 20/1) to obtain the title compound (113.4 mg).
1H-NMR spectrum (CDCl _Three ) δ: 7.57 (1H, d, J = 1.4 Hz), 7.38 (1H, d, J = 8.2 Hz), 7.32 (1H, dd, J = 7.6, 2.1 Hz), 6.56 (1H, s), 6.04- 5.95 (1H, m), 5.19-5.15 (1H, m), 5.11-5.05 (1H, m), 3.92 (3H, s), 3.69 (2H, d, J = 6.2 Hz), 3.43 (2H, q, J = 9.6 Hz).
Example 60
5- {4-ethenyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-92)
The title compound was obtained in the same manner as in Example 59 using the compound of Example 54 and tributylvinyltin.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.68 (1H, d, J = 8.2 Hz), 7.63 (1H, d, J = 1.4 Hz), 7.39 (1H, dd, J = 8.2, 1.4 Hz), 7.34 (1H, dd, J = 17.2 , 11.0 Hz), 6.58 (1H, s), 5.84 (1H, d, J = 17.2 Hz), 5.52 (1H, d, J = 11.0 Hz), 3.93 (3H, s), 3.36 (2H, q, J = 9.4 Hz).
Example 61
4-Chloro-1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1- 93)
(1) 4-chloro-1-methyl-5- (4-methyl-3-nitrophenyl) -3- (trifluoromethyl) -1H-pyrazole
4-Bromo-2-nitrotoluene was subjected to the reaction in Step C-1, and the resulting 1-methyl-5- (4-methyl-3-nitrophenyl) -3- (trifluoromethyl) -1H-pyrazole was obtained. N-chlorosuccinimide (144 mg) was added to a solution of (248.6 mg, 0.84 mmol) in N, N-dimethylformamide form (2.8 ml), and the mixture was stirred at 70 ° C. for 6 hours. After cooling to room temperature, the reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 1/1) to obtain the title compound (185.6 mg, yield 66.9%).
¹ H-NMR spectrum (CDCl _Three ) δ: 8.45 (1H, s), 8.13 (1H, d, J = 7.9 Hz), 7.95 (1H, d, J = 7.9 Hz), 3.97 (3H, s).
(2) 4-chloro-1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole (compound Number 1-93)
The above compound (1) was subjected to the reaction and post-treatment in Steps C-5 to C-8 to obtain the title compound.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.50 (1H, d, J = 1.6 Hz), 7.40 (1H, d, J = 7.7 Hz), 7.27-7.24 (1H, m), 3.84 (3H, s), 3.44 (2H, q, J = 9.5 Hz), 2.55 (3H, s).
Example 62
4- [4-Chloro-1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1 -94)
Using 4-bromo-2-fluorobenzonitrile as a starting material, the reaction was carried out in the same manner as in the former stage of Example 61, followed by post-treatment, and the resulting 1-methyl-4-chloro-5- (4-cyano-3-) was obtained. Fluorophenyl) -3- (trifluoromethyl) -1H-pyrazole was subjected to the reaction and workup of Step A-2b to give the title compound.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.89 (1H, d, J = 7.9 Hz), 7.74 (1H, s), 7.52 (1H, d, J = 7.9 Hz), 3.88 (3H, s), 3.62 (2H, q, J = 9.4 Hz).
Example 63
5- {4- (Difluoromethyl) -3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-95 )
4-Bromo-3-fluorobenzaldehyde was subjected to the reaction and post-treatment of steps A-1a and A-2a to give 4- [1-methyl-3- (trifluoromethyl) -1H-pyrazole-5. -Il] -2-[(2,2,2-trifluoroethyl) thio] benzaldehyde (189.1 mg, 0.51 mmol) was dissolved in methylene chloride (2 ml) and deoxoflow (0.14 ml) was added at room temperature. Stir for 15 hours. The reaction mixture was diluted with methylene chloride, washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 2/1) to obtain the title compound (62.4 mg, yield 30.8%).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.84 (1H, d, J = 7.9 Hz), 7.73 (1H, s), 7.55 (1H, d, J = 7.9 Hz), 7.19 (1H, t, J = 55.0 Hz), 6.62 (1H, s), 3.94 (3H, s), 3.44 (2H, q, J = 9.5 Hz).
Example 64
1-methyl-5- {4-propyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-96)
The title compound was obtained using 1-bromo-4-propylbenzene as a starting material and the reaction and post-treatment of Steps C-4 to C-8 and A-2a.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.52 (1H, d, J = 1.4 Hz), 7.34 (1H, d, J = 7.6 Hz), 7.28 (2H, dd, J = 7.6, 1.4 Hz), 6.54 (1H, s), 3.91 ( 3H, s), 3.44 (2H, q, J = 9.6 Hz), 2.86 (2H, t, J = 7.6 Hz), 1.69 (2H, tt, J = 7.6, 7.6 Hz), 1.02 (3H, t, J = 7.6 Hz).
Example 65
5- {4-Cyclopropyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-97)
(1) 4-Bromo-1-cyclopropyl-2-nitrobenzene
Copper nitrate trihydrate (3.14 g, 13.0 mmol) was dissolved in a solution of acetic acid (6 ml) and acetic anhydride (14 ml) in a mixed solution of acetic acid (4 ml) and acetic anhydride (10 ml) under ice cooling. 4-Bromocyclopropylbenzene (2.32 g, 11.8 mmol) was added and stirred at room temperature for 8 hours. The reaction mixture was poured into ice water and extracted with dichloromethane. The extract was washed with saturated aqueous ammonium chloride solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 30/1) to obtain the title compound (1.37 g).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.95 (1H, d, J = 2.0 Hz), 7.59 (1H, dd, J = 8.4, 2.0 Hz), 7.03 (1H, d, J = 8.4 Hz), 2.33 (1H, tt, J = 6.9 , 4.5 Hz), 1.11-1.03 (2H, m), 0.73-0.66 (2H, m).
(2) 5- {4-cyclopropyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1- 97)
Using the compound (1) as a starting material, the title compound was obtained using the reaction and post-treatment of Steps C-4 to C-8 and A-2a.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.53 (1H, d, J = 1.4 Hz), 7.26 (1H, dd, J = 8.2, 1.4 Hz), 7.01 (1H, d, J = 8.2 Hz), 6.53 (1H, s), 3.90 ( 3H, s), 3.48 (2H, q, J = 9.6 Hz), 2.48-2.41 (1H, m), 1.15-1.10 (2H, m), 0.81-0.77 (2H, m).
Example 66
4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzaldehyde O-methyloxime (Compound No. 1- 98)
4-Bromo-3-fluorobenzaldehyde was subjected to the reaction and post-treatment of steps A-1a and A-2a to give 4- [1-methyl-3- (trifluoromethyl) -1H-pyrazole- 5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzaldehyde (113.0 mg, 0.31 mmol) was dissolved in methanol (2 ml) and O-methylhydroxylamine (32.7 mg). And stirred at room temperature for 2 hours. Further, tetrahydrofuran (1 ml) was added, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 6/1) to obtain the title compound (26.5 mg, yield 20.8%).
¹ H-NMR spectrum (CDCl _Three ) δ: 8.69 (1H, s), 8.01 (1H, d, J = 7.8 Hz), 7.65 (1H, d, J = 1.7 Hz), 7.41 (1H, dd, J = 7.8, 1.7 Hz), 6.60 ( 1H, s), 4.04 (3H, s), 3.93 (3H, s), 3.37 (2H, q, J = 9.3 Hz).
Example 67
3- (Difluoromethoxy) -1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1H-pyrazole (Compound No. 1-99)
The compound of Example 68 (1) was reacted in the same manner as in Example 68 (3) and worked up to give 3-difluoroacetyl-1-methyl-5- (4-methylphenyl) -1H. The title compound was obtained using the reaction and post-treatment of Steps C-4 to C-8 starting from -pyrazole.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.49 (1H, s), 7.32 (1H, d, J = 7.9 Hz), 7.24 (2H, d, J = 7.9 Hz), 6.83 (1H, t, J = 73.6 Hz), 5.91 (1H, s), 3.75 (3H, s), 3.42 (2H, q, J = 9.6 Hz), 2.52 (3H, s).
Example 68
3-[(Difluoromethyl) thio] -1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1H-pyrazole (Compound No. 1-100)
(1) 3-hydroxy-1-methyl-5- (4-methylphenyl) -1H-pyrazole and 3-hydroxy-2-methyl-5- (4-methylphenyl) -1H-pyrazole
Ethyl 3- (4-methylphenyl) prop-2-inoate (6.03 g, 32.0 mmol) is dissolved in ethanol (32 ml) and water (32 ml) and methylhydrazine (1.9 ml, 35.2 mmol) is added. And stirred at 60 ° C. for 7 hours. After cooling to room temperature, the mixture was concentrated under reduced pressure, and the resulting crystals were collected by filtration. The crystals were washed with chilled ethyl acetate and then dried under reduced pressure. The resulting crystals (a mixture of pyrazolone regioisomer, 1-methyl and 2-methyl) were used in the next step without purification.
(2) 1-methyl-5- (4-methylphenyl) -1,2-dihydro-3H-pyrazole-3-thione
The above compound (1) (crude product: 456.0 mg) was added to toluene (4.8 ml), Lawesson's reagent (502.5 mg) was added, and the mixture was heated to reflux for 7 hours. The reaction solution was cooled to room temperature, poured into water, and extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 3/1) to give the title compound (259.6 mg, yield 52.5%).
(3) 3-[(Difluoromethyl) thio] -1-methyl-5- (4-methylphenyl) -1H-pyrazole
The above compound (2) (254.1 mg, 1.24 mmol) was dissolved in 1,4-dioxane (4.1 ml), and sodium hydroxide (261.9 mg, 5.3 mmol) was dissolved in water (1.6 ml). The solution was added and heated to 60-65 ° C. To this reaction liquid, chlorodifluoromethane gas was introduced for 2 minutes, and then stirred at the same temperature for 4 hours. The reaction solution was cooled to room temperature, poured into water, and extracted with diethyl ether. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 4/1) to obtain the title compound (99.5 mg, yield 31.5%).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.66 (2H, d, J = 7.9Hz), 7.20 (2H, d, J = 7.9Hz), 6.71 (1H, t, J = 56.5Hz), 4.00 (3H, s), 2.37 (3H, s).
(4) 3-Difluoromethylthio-1-methyl-5- (4-methyl-3-chlorosulfonylphenyl) -1H-pyrazole
The compound of (3) above was added to chlorosulfonic acid (233.4 mg, 2.0 mmol) under ice cooling, and the mixture was stirred at 50 ° C. for 2 hours. The reaction solution was cooled to room temperature, poured into water, and extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure to give the title compound (114.7 mg) as a crude product. This compound was subjected to the next step without further purification.
(5) S- (5- {3-[(Difluoromethyl) thio] -1-methyl-1H-pyrazol-5-yl} -2-methylphenyl) ethanethioate
The compound of (4) (114.7 mg) was dissolved in acetic acid (3 ml), sodium acetate (134.0 mg) and zinc powder (108.0 mg) were added, and the mixture was heated to reflux for 1 hour. The reaction solution was cooled to room temperature and then filtered through celite. The filtrate was poured into ice water, neutralized with aqueous ammonia, and the aqueous layer was extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 4/1) to obtain the title compound (75.9 mg, yield 71%).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.82 (1H, d, J = 1.4Hz), 7.73 (1H, d, J = 7.6, 1.4Hz), 7.34 (1H, d, J = 7.6Hz), 6.85 (1H, s), 6.71 ( 1H, t, J = 56.4Hz), 4.00 (3H, s), 2.43 (3H, s), 2.36 (3H, s).
(6) 5- {3-[(Difluoromethyl) thio] -1-methyl-1H-pyrazol-5-yl} -2-methylbenzenethiol
The compound of (5) (73.9 mg, 0.23 mmol) was dissolved in ethanol (3.0 ml), 6N aqueous sodium hydroxide solution (0.44 ml) was added, and the mixture was heated to reflux for 2 hours. After cooling to room temperature, water was added and extracted with ethyl acetate. Ice was added to the aqueous layer, and the mixture was acidified with 6N aqueous hydrochloric acid and extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure to give the title compound (63.3 mg, yield 98.2%) as a crude product.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.70 (1H, brd. s), 7.44 (1H, dd, J = 7.7, 1.6Hz), 7.17 (1H, d, J = 7.7Hz), 6.83 (1H, s), 6.71 (1H, t , J = 56.5Hz), 4.00 (3H, s), 3.38 (1H, s), 2.34 (3H, s).
(7) 3-[(Difluoromethyl) thio] -1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1H-pyrazole (Compound No. 1) -100)
The above compound (6) (63.3 mg, 0.22 mmol) was dissolved in N, N-dimethylformamide (2.0 ml) and sodium hydride (12.3 mg in 60% mineral oil) and 1, 1,1-trifluoro-2-iodoethane (28 μl) was added and stirred at 80 ° C. for 1 hour. The reaction solution was cooled to room temperature, poured into ice water, and extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 4/1) to obtain the title compound (38.2 mg, yield 46.9%).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.89 (1H, s), 7.60 (1H, d, J = 7.9 Hz), 7.25 (1H, d, J = 7.9 Hz), 6.85 (1H, s), 6.73 (1H, t, J = 56.4 Hz), 4.01 (3H, s), 3.45 (2H, q, J = 9.8 Hz), 2.48 (3H, s).
Example 69
1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3-[(2,2,2-trifluoroethyl) thio] -1H-pyrazole (Compound No. 1-109)
The reaction was conducted in the same manner as in Example 68 except that 1,1,1-trifluoro-2-iodoethane was used in place of chlorodifluoromethane, and post-treatment was performed to give the title compound.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.87 (1H, s), 7.58 (1H, d, J = 7.7 Hz), 7.24 (1H, d, J = 7.7 Hz), 6.74 (1H, s), 4.00 (3H, s), 3.50- 3.25 (4H, m), 2.48 (3H, s).
Example 70
5- {4-Methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1- (2,2,2-trifluoroethyl) -3- (trifluoromethyl) -1H- Pyrazole (Compound No. 1-145)
The reaction was conducted in the same manner as in Example 53 except that 1,1,1-trifluoro-2-iodoethyl was used in place of propyl bromide, followed by post-treatment to give the title compound.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.47 (1H, d, J = 1.7 Hz), 7.37 (1H, d, J = 8.2 Hz), 7.22 (1H, dd, J = 8.2, 1.7 Hz), 6.60 (1H, s), 4.67 ( 3H, q, J = 7.8 Hz), 3.42 (3H, q, J = 9.6 Hz), 2.54 (3H, s).
Example 71
3-Methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1- (2,2,2-trifluoroethyl) -1H-pyrazole (Compound No. 1-146)
(1) 3-Methyl-1- (2,2,2-trifluoroethyl) -1H-pyrazol-5-yl trifluoromethanesulfonate
Ethyl 3-oxobutanoic acid was subjected to the reaction and post-treatment of Step B-3, and the resulting 3-methyl-1- (2,2,2-trifluoroethyl) -1H-pyrazol-5-ol and 3 -To a solution of methyl-2- (2,2,2-trifluoroethyl) -1H-pyrazol-5-ol (3.60 g, 20.0 mmol) in dichloromethane (20 ml) under ice-cooling, triethylamine (2 .23 g, 22.0 mmol) and trifluoromethanesulfonic anhydride (6.21 g, 22.0 mmol) were added and stirred at the same temperature for 1 hour. The reaction mixture was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 7/1) to obtain the title compound (6.06 g).
¹ H-NMR spectrum (CDCl _Three ) δ: 6.05 (1H, s), 4.58 (2H, q, J = 8.0 Hz), 2.27 (3H, s).
(2) 3-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1- (2,2,2-trifluoroethyl) -1H-pyrazole (Compound No. 1-146)
The title compound was obtained using the reaction and post-treatment of Steps C-1 and C-4 to C-8 using the compound of (1) as a starting material.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.45 (1H, d, J = 2.1 Hz), 7.32 (1H, d, J = 8.2 Hz), 7.19 (1H, dd, J = 8.2, 2.1 Hz), 6.14 (1H, s), 4.55 ( 2H, q, J = 8.2 Hz), 3.42 (2H, q, J = 9.4 Hz), 2.51 (3H, s), 2.33 (3H, s).
Example 72
4- [1-Methyl-3- (nonafluorobutyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1-147) The reaction was conducted in the same manner as in Example 57 using fluoropentanoic acid as a starting material, and post-treatment was performed to give the title compound.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.84 (1H, d, J = 8.1 Hz), 7.75 (1H, s), 7.52 (1H, d, J = 8.1Hz), 6.67 (1H, s), 3.97 (3H, s), 3.62 ( 2H, q, J = 9.3 Hz).
Example 73
5- {4-Ethynyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole (Compound No. 1-148) 5- 5- (4-Bromo-3-nitrophenyl) was obtained by subjecting (4-bromophenyl) -1-methyl-3- (trifluoromethyl) -1H-pyrazole to the reaction and post-treatment of Step C-4. ) -1-Methyl-3- (trifluoromethyl) -1H-pyrazole was reacted in the same manner as in Example 58 (1) and worked up to give 5- [4- (2-trimethylsilyl) ethynyl- 3-Nitrophenyl] -1-methyl-3- (trifluoromethyl) -1H-pyrazole was used as a starting material, and the title compound was obtained using the reaction and post-treatment of Steps C-5 to C-8.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.66 (1H, d, J = 8.2 Hz), 7.58 (1H, d, J = 1.4 Hz), 7.33 (1H, dd, J = 8.2, 1.4 Hz), 6.59 (1H, s), 3.92 ( 3H, s), 3.59 (2H, q, J = 9.6 Hz), 3.59 (1H, s).
Example 74
3- {4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] phenyl} -4,5- Dihydro-1,2,4-oxadiazole (Compound No. 1-149)
(1) N′-hydroxy-4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzenecarboxy Midamide
4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1-55) ( 1.00 g, 2.74 mmol) are dissolved in 1,4-dioxane (10 ml), hydroxylamine hydrochloride (953.4 mg, 13.7 mmol) and triethylamine (1.9 ml, 13.7 mmol) are added and 70 ° C. The mixture was stirred for 6 hours with heating, and further stirred for 2 hours under reflux. The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 1/1 to 1/4) to give the title compound (536.5 mg, yield 49.2%).
(2) 3- {4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] phenyl} -4 , 5-Dihydro-1,2,4-oxadiazole (Compound No. 1-149)
The above compound (1) (248.3 mg, 0.62 mmol) was dissolved in acetonitrile (5.5 ml), 37% aqueous formaldehyde solution (0.26 ml) and acetic acid (0.1 ml) were added, and the mixture was stirred at room temperature for 30 minutes. The mixture was further heated and stirred for 1 hour under reflux. The reaction solution was cooled to room temperature, poured into a saturated aqueous sodium hydrogen carbonate solution, and extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 1/1) to obtain the title compound (29.7 mg, yield 11.6%).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.87 (1H, d, J = 8.1 Hz), 7.69 (1H, d, J = 1.7 Hz), 7.45 (1H, dd, J = 8.1, 1.7 Hz), 6.61 (1H, s), 5.54 ( 2H, d, J = 4.0 Hz), 5.16 (1H, br s), 3.94 (3H, s), 3.55 (2H, q, J = 9.5 Hz).
Example 75
3- {4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] phenyl} -1,2, 4-oxadiazole (Compound No. 1-150)
The compound of Example 74 (1) (102.1 mg, 0.26 mmol) was dissolved in ethanol (2.6 ml), ethyl orthoformate (0.26 ml, 1.56 mmol) and concentrated sulfuric acid (2 drops) were added at room temperature. And stirred overnight. The reaction solution was poured into a saturated aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 1/2) to obtain the title compound (32.1 mg, yield 30.7%).
¹ H-NMR spectrum (CDCl _Three ) δ: 8.87 (1H, s), 8.13 (1H, d, J = 8.0 Hz), 7.76 (1H, s), 7.52 (1H, d, J = 8.0 Hz), 6.65 (1H, s), 3.97 ( 3H, s), 3.61 (2H, q, J = 9.7 Hz).
Example 76
2- {4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] phenyl} -1,3- Thiazole (Compound No. 1-151)
5- [4-Bromo-3- (2,2,2-trifluoroethylthio) phenyl] -1-methyl-3- (trifluoromethyl) -1H-pyrazole was reacted in the same manner as in Example 59, followed by Treatment gave the title compound (39% yield).
¹ H-NMR spectrum (CDCl _Three ) δ: 8.13 (1H, d, J = 8.2 Hz), 8.01 (1H, d, J = 3.4 Hz), 7.73 (1H, d, J = 1.7 Hz), 7.54 (1H, d, J = 3.4 Hz) 7.48 (1H, dd, J = 8.2, 1.7 Hz), 6.64 (1H, s), 3.97 (3H, s), 3.46 (2H, q, J = 9.6 Hz).
Example 77
1- {4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] phenyl} ethanol (Compound No. 1 -152)
5- [4-Bromo-3- (2,2,2-trifluoroethylthio) phenyl] -1-methyl-3- (trifluoromethyl) -1H-pyrazole with (1-ethoxyethenyl) tributyltin React as in Example 59 and work up to give 1- {4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2 , 2-trifluoroethyl) thio] phenyl} ethanone (153 mg, 0.4 mmol) in methanol (5 ml) under ice-cooling, sodium borohydride (18.2 mg, 0.4 mmol) was added. Stir for hours. Ethyl acetate was added to the reaction mixture, washed twice with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by reverse phase column chromatography (elution solvent: acetonitrile / water = 60/40) to obtain the title compound (78.7 mg).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.75 (1H, d, J = 7.6 Hz), 7.55 (1H, d, J = 1.7 Hz), 7.41 (1H, dd, J = 7.6, 1.7 Hz), 6.57 (1H, s), 5.57- 5.50 (1H, m), 3.92 (3H, s), 3.53-3.44 (2H, m), 1.99 (1H, d, J = 4.1 Hz), 1.55 (3H, d, J = 6.2 Hz).
Example 78
4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzaldehyde oxime (Compound No. 1-153)
4-Bromo-2-fluorobenzaldehyde was subjected to the reaction of steps A-1a and A-2a, and the resulting 4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] was obtained. -2-[(2,2,2-trifluoroethyl) thio] benzaldehyde was subjected to the subsequent reaction and post-treatment of Example 66 to obtain the title compound.
¹ H-NMR spectrum (CDCl _Three ) δ: 8.77 (1H, s), 7.98-7.95 (2H, m), 7.67 (1H, d, J = 1.8 Hz), 7.43 (1H, dd, J = 8.0, 1.8 Hz), 6.61 (1H, s ), 3.95 (3H, s), 3.39 (2H, q, J = 9.5 Hz).
Example 79
3-Chloro-1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1H-pyrazole (Compound No. 1-154)
(1) 3-chloro-1-methyl-5- (4-methylphenyl) -1H-pyrazole
Phosphorus oxychloride (1.4 ml, 15.0 mmol) was added to the compound of Example 68 (1) (258.0 mg, 1.37 mmol), and heated in a shield tube at 180 ° C. for 5 minutes. The reaction solution was cooled to room temperature and poured into ice water. The reaction solution was neutralized with potassium carbonate, and extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 4/1) to obtain the title compound (127.5 mg, yield 45.0%).
¹ H-NMR spectrum (CDCl _Three ) δ: 7.61 (1H, d, J = 7.9 Hz), 7.19 (1H, d, J = 7.9 Hz), 6.46 (1H, s), 3.87 (3H, s), 2.36 (3H, s).
(2) 3-Chloro-1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1H-pyrazole (Compound No. 1-154)
The above compound (1) was subjected to the reaction and post-treatment of Steps E-4 to E-6 to obtain the title compound.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.85 (1H, d, J = 1.6 Hz), 7.55 (1H, dd, J = 7.9, 1.6 Hz), 7.24 (2H, d, J = 7.9 Hz), 6.47 (1H, s), 3.88 ( 3H, s), 3.44 (2H, q, J = 9.7 Hz), 2.48 (3H, s).
Example 80
3-Chloro-1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -1H-pyrazole (Compound No. 1-155)
The compound of Example 79 was subjected to the reaction and post-treatment in Step A-3 to obtain the title compound.
¹ H-NMR spectrum (CDCl _Three ) δ: 8.28 (1H, d, J = 1.6 Hz), 7.85 (1H, dd, J = 7.9, 1.6 Hz), 7.28 (1H, d, J = 7.9 Hz), 6.57 (1H, s), 3.89 ( 3H, s), 3.52-3.36 (2H, m), 2.41 (3H, s).
Example 81
3-Bromo-1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1H-pyrazole (Compound No. 1-156)
The title compound was obtained in the same manner as in Example 79 except that phosphorus oxybromide was used instead of phosphorus oxychloride.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.85 (1H, d, J = 1.6 Hz), 7.55 (1H, dd, J = 7.8, 1.6 Hz), 7.24 (2H, d, J = 7.8 Hz), 6.55 (1H, s), 3.92 ( 3H, s), 3.44 (2H, q, J = 9.7 Hz), 2.48 (3H, s).
Example 82
1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- [4- (trifluoromethyl) phenyl] -1H-pyrazole (Compound No. 1 -157)
The compound of Example 81 was subjected to the reaction and post-treatment of Step A-1b to obtain the title compound.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.95 (1H, s), 7.76-7.58 (5H, m), 7.29-7.26 (1H, m), 6.63 (1H, s), 3.95 (3H, s), 3.46 (2H, q, J = 9.8 Hz), 2.50 (3H, s).
Example 83
3- {4-Methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1- (2,2,2-trifluoroethyl) -5- (trifluoromethyl) -1H- Pyrazole (Compound No. 2-10)
The title compound was obtained in the same manner as in Example 70 using 4-acetyltoluene as a starting material.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.91 (1H, d, J = 1.7 Hz), 7.63 (1H, dd, J = 8.2, 1.7 Hz), 7.29 (1H, d, J = 8.2 Hz), 6.98 (1H, s), 4.84 ( 3H, q, J = 8.0 Hz), 3.45 (2H, q, J = 9.6 Hz), 2.50 (3H, s).
Example 84
3- {4-Bromo-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-5- (trifluoromethyl) -1H-pyrazole (Compound No. 2-11)
The title compound was obtained in the same manner as in Example 54 using 4-acetyl-1-bromobenzene as a starting material.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.96 (1H, d, J = 2.1 Hz), 7.65 (1H, d, J = 8.2 Hz), 7.55 (1H, dd, J = 8.2, 2.1 Hz), 6.88 (1H, s), 4.04 ( 3H, s), 3.55 (2H, q, J = 9.6 Hz).
Example 85
3- [4-Methyl-3- (propylthio) phenyl] -1- (2,2,2-trifluoroethyl) -5- (trifluoromethyl) -1H-pyrazole (Compound No. 2-12)
The title compound was obtained in the same manner as in Example 83 using 4-acetyltoluene as a starting material.
¹ H-NMR spectrum (CDCl _Three ) δ: 7.69 (1H, d, J = 1.4 Hz), 7.47 (1H, dd, J = 7.6, 1.4 Hz), 7.21 (1H, d, J = 7.6 Hz), 6.96 (1H, s), 4.84 ( 2H, q, J = 7.6 Hz), 2.95 (2H, t, J = 7.6 Hz), 2.39 (3H, s), 1.77-1.69 (2H, m), 1.07 (3H, t, J = 7.6 Hz).
Example 86
4- [5- (Difluoromethyl) -1-methyl-1H-pyrazol-3-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 2-13)
The title compound was obtained in the same manner as in Example 56 using difluoroacetic acid as a starting material.
¹ H-NMR spectrum (CDCl _Three ) δ: 8.09 (1H, d, J = 1.5 Hz), 7.81 (1H, dd, J = 8.2, 1.5 Hz), 7.72 (1H, d, J = 8.1 Hz), 6.82 (1H, s), 6.77 ( 1H, t, J = 53.7 Hz), 4.05 (3H, s), 3.61 (2H, q, J = 9.5 Hz).
Example 87
4- [1-Methyl-3- (trifluoromethyl-1H-pyrazol-5-yl) -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound Nos. 1-55) and 4 -[1-Methyl-5- (trifluoromethyl-1H-pyrazol-3-yl) -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 2-1)
(1) 2-[(2,2,2-trifluoroethyl) thio] -4- (4,4,4-trifluoro-1-hydroxy-3-oxo-1-butenyl) benzonitrile (Step B- 4)
4- (1-Ethoxy-4,4,4-trifluoro-3-oxo-1-butenyl) -2-[(2,2,2-trifluoroethyl) thio obtained in Example 13 (2) Benzonitrile (96.6 mg, 0.25 mmol) was dissolved in methanol (3 ml), 2N hydrochloric acid (1.0 ml) was added, and the mixture was stirred at 50 ° C. for 3 hr. Saturated brine and water were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain the title compound (87.2 mg, yield 97%).
¹ H-NMR spectrum (CDCl _Three ) δ: 8.19 (1H, d, J = 1.5Hz), 7.94 (1H, dd, J = 8.2, 1.5Hz), 7.84 (1H, d, J = 8.2Hz), 6.56 (1H, s), 3.63 ( 2H, q, J = 9.3Hz).
(2) 4- [1-Methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 1- 55, Step B-3) and 4- [1-Methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile (Compound No. 2-1, Step B-3)
The compound of the above (2) (55.4 mg, 0.16 mmol) was dissolved in ethanol (3.0 ml), acetic acid (150 μl) and methylhydrazine (13 μl) were added, and the mixture was heated to reflux for 2 hours. After allowing to cool, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by thin layer chromatography (developing solvent: hexane / ethyl acetate = 3/1) to give compound No. 1-55 (19.9 mg, 35% yield) and Compound No. 2-1. (1.9 mg, 3% yield) was obtained.
Compound No. 1-55
¹ H-NMR spectrum (CDCl _Three ) δ: 7.84 (1H, d, J = 7.9Hz), 7.74 (1H, s), 7.50 (1H, d, J = 7.9Hz), 6.65 (1H, s), 3.95 (3H, s), 3.61 ( 2H, q, J = 9.4Hz).
Compound No. 2-1
¹ H-NMR spectrum (CDCl _Three ) δ: 8.09 (1H, d, J = 1.6Hz), 7.81 (1H, dd, J = 7.9, 1.6Hz), 7.73 (1H, d, J = 7.9Hz), 6.96 (1H, s), 4.07 ( 3H, s), 3.61 (2H, q, J = 9.4Hz).

  In the following formulation examples, the types and blending ratios of the compound and the auxiliary agent are not limited to these and can be changed in a wide range. Moreover, in the following description,% shows a mass percentage.

Formulation Example 1
Emulsion 42.5% of xylene and 42.5% of dimethyl sulfoxide were added to 5% of the compound of Compound No. 1 and dissolved, and then mixed with polyoxyethylene castor oil ether and calcium alkylbenzenesulfonate (8: 2) 10% Were mixed to obtain an emulsion. This product is diluted with water and used as a spray.

Formulation Example 2
Hydrating Agent 5% of Compound No. 1 compound was mixed with 79% kaolin and 10% diatomaceous earth, and further mixed with 3% sodium lauryl sulfate and 3% sodium lignin sulfonate to obtain a wettable powder. . This product is diluted with water and used as a spray.

Formulation Example 3
Powder A mixture of talc and calcium carbonate (1: 1) 99% was added to 1% of the compound No. 1, and the mixture was pulverized to obtain a powder. Disperse this product as it is.

Formulation Example 4
Granule Compound 2% of Compound No. 1 is mixed with 30% bentonite fine powder, 66% talc, and 2% sodium lignin sulfonate, and then kneaded until water is evenly mixed. Next, the mixture was granulated through a granulator and passed through a granulator, a dryer, and a sieve to obtain granules having a particle size of 0.6 to 1.0 mm. This product should be sprayed on the soil surface as it is.

Formulation Example 5
Oil agent 0.1% of compound No. 1 compound was dissolved in white kerosene to obtain 100% oil as a whole.

Test example 1
Nite spider mite insecticide test A chemical solution containing 300 ppm of each compound of the present invention and 0.01% spreader added thereto was prepared. Primary leaves of cowpea (Vigna sinenis Savi) were inoculated with female adults of Tetanychus urticae. One day after the inoculation, 7 ml of the above chemical solution was sprayed on a Mizuho rotary spray tower so that the amount of sprayed liquid was 3.5 mg / cm ² leaves. After air drying, the cowpea leaves were stored in a constant temperature room at 25 ° C., and after 3 days, the life and death of adults were examined, and the death rate (%) was calculated.
As a result, the following compounds showed 100% mortality.
Compound No. 1-3, Compound No. 1-4, Compound No. 1-7, Compound No. 1-8, Compound No. 1-9, Compound No. 1-10, Compound No. 1-11, Compound No. 1-12, Compound No. 1-13, Compound No. 1-15, Compound No. 1-16, Compound No. 1-17, Compound No. 1-19, Compound No. 1-23, Compound No. 1-35, Compound No. 1-41, Compound No. 1- 43, compound number 1-55, compound number 1-56, compound number 1-61, compound number 1-64, compound number 1-65, compound number 1-66, compound number 1-67, compound number 1-68, Compound No. 1-69, Compound No. 1-70, Compound No. 1-71, Compound No. 1-72, Compound No. 1-73, Compound No. 1-74, Compound No. 1-75, Compound No. 1-76, Compound No. 1-7 Compound No. 1-78, Compound No. 1-79, Compound No. 1-86, Compound No. 1-87, Compound No. 1-88, Compound No. 1-89, Compound No. 1-90, Compound No. 1-91, Compound No. 1-92, Compound No. 1-93, Compound No. 1-94, Compound No. 1-95, Compound No. 1-96, Compound No. 1-97, Compound No. 1-98, Compound No. 1-99, Compound No. 1 -100, Compound No. 1-109, Compound No. 1-147, Compound No. 1-148, Compound No. 1-149, Compound No. 1-150, Compound No. 1-151, Compound No. 1-152, Compound No. 1-153 Compound No. 1-154, Compound No. 1-155, Compound No. 1-156, Compound No. 1-157, Compound No. 2-1, Compound No. 2-3, Compound No. 2-9, Object number 2-10, Compound No. 2-11, Compound No. 2-12 and Compound No. 2-13.

Test example 2
Citrus spider mite insecticide test The chemical | medical solution which added each compound of this invention 300ppm and added the spreading agent 0.01% to this was prepared. Mulberry (Morus bombysis) leaves were inoculated with adult females of Panonychus citri. One day after the inoculation, 7 ml of the above chemical solution was sprayed on a Mizuho rotary spray tower so that the amount of sprayed liquid was 3.5 mg / cm ² leaves. After air drying, the mulberry leaves were stored in a constant temperature room at 25 ° C., and after 3 days, the life and death of adults were examined, and the death rate (%) was calculated.
As a result, the following compounds showed 100% mortality.
Compound No. 1-3, Compound No. 1-4, Compound No. 1-7, Compound No. 1-8, Compound No. 1-9 Compound No., Compound No. 1-10, Compound No. 1-11, Compound No. 1-12, Compound No. 1-13, Compound No. 1-15, Compound No. 1-16, Compound No. 1-17, Compound No. 1-19, Compound No. 1-23, Compound No. 1-35, Compound No. 1-41 and Compound No. 1-43, compound number 1-55, compound number 1-56, compound number 1-61, compound number 1-63, compound number 1-64, compound number 1-65, compound number 1-66, compound number 1- 67, compound number 1-68, compound number 1-69, compound number 1-70, compound number 1-71, compound number 1-72, compound number 1-73, compound number 1-74, compound number 1-75, Compound No. 1-77, Compound No. 1-78, Compound No. 1-79, Compound No. 1-85, Compound No. 1-86, Compound No. 1-87, Compound No. 1-88, Compound No. 1-89, Compound No. 1 -90, compound number 1-91, compound number 1-92, compound number 1-93, compound number 1-94, compound number 1-95, compound number 1-96, compound number 1-97, compound number 1-98 Compound No. 1-99, Compound No. 1-100, Compound No. 1-109, Compound No. 1-145, Compound No. 1-146, Compound No. 1-147, Compound No. 1-149, Compound No. 1-150, Compound Compounds No. 1-154, No. 1-155, No. 1-156, No. 2-1, No. 2-3, No. 2-10 and No. 2-11.
Insecticidal rate (%) = number of dead insects / number of released insects x 100

  The (3-sulfur atom-substituted phenyl) pyrazole derivative of the present invention is, for example, a hemipod pest, a lepidopteran pest, a coleopteran pest, a diptera pest, a hymenopteran pest, a straight pest, a termite pest, or a thrips It exhibits excellent control effects against a wide range of pests such as eye pests, spider mites, and plant parasitic nematodes, and is useful as an agricultural and horticultural insecticide.

Claims (54)

The following general formula (I)

[Where:
R ¹ is an optionally substituted C ₁ -C ₆ alkyl group (the substituent is 1-7 substituents selected from the group consisting of a halogen atom, a C ₃ -C ₆ cycloalkyl group and a cyano group) An optionally substituted C ₂ -C ₆ alkenyl group (the substituent is 1-7 substituents selected from the group consisting of a halogen atom and a cyano group) or C. It represents ₃ -C ₆ cycloalkyl group,
A is a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent is 1-7 substituents selected from the group consisting of a hydroxyl group and a halogen atom), substitution which may C ₂ -C be the ₆ alkenyl group (the substituent is a 1-7 substituents selected from the group consisting of halogen atom.), optionally substituted C ₂ -C ₆ An alkynyl group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms), an optionally substituted C ₃ -C ₆ cycloalkyl group (the substituent is a halogen atom) 1-6 substituents selected from the group consisting of atoms.), Formula —C (Y) ═NOR (wherein R represents a hydrogen atom or a C ₁ -C ₆ alkyl group, Y represents Represents a hydrogen atom or an amino group). A 5-6 membered heteroaryl group containing 1-3 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, which may be partially saturated, the substituent represents 1-3 is a substituent.), or a cyano group selected from the group consisting of halogen _atom, C 1 -C ₆ alkyl group and _C 1 -C ₆ alkoxy group,
X may be the same or different when m represents an integer of 2 or 3, and represents a halogen atom;
m represents an integer of 0 to 3,
n represents an integer of 0 or 1,
Q is the following general formula (Q-1) or (Q-2) :

[Where:
R ² and R ⁵ represent an optionally substituted C ₁ -C ₆ alkyl group (the substituent is 1-9 substituents selected from the group consisting of halogen atoms);
R ³ , R ⁴ , 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 group consisting of halogen atoms) 1-9 substituents), an optionally substituted C ₁ -C ₆ alkoxy group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms). A C ₁ -C ₆ alkylthio group which may be substituted (the substituent is 1-7 substituents selected from the group consisting of halogen atoms), or may be substituted. Phenyl group [the substituent is a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent is 1-9 substituents selected from the group consisting of halogen atoms) and substituted _C 1 -C ₆ optionally a 1 to 5 substituents selected from the group consisting of a ruxoxy group (the substituent is 1 to 7 substituents selected from the group consisting of halogen atoms). ]. ]
Represents a group represented by ]
A (3 sulfur atom-substituted phenyl) pyrazole derivative represented by the formula (1) or a salt thereof as an active ingredient . R ¹ is an optionally substituted C ₁ -C ₄ alkyl group (the substituent is 1-7 halogen atoms, 1 C ₃ -C ₆ cycloalkyl group, or 1 cyano group). ), An optionally substituted C ₂ -C ₄ alkenyl group (the substituent is 1-2 halogen atoms or 1 cyano group) or a C ₃ -C ₆ cycloalkyl group. The acaricide according to claim 1. R ¹ is an optionally substituted C ₂ -C ₄ alkyl group (the substituent is 1-5 fluorine atoms, 1 chlorine atom, 1 C ₃ -C ₄ cycloalkyl group or 1 The miticide according to claim 1, which is a C ₂ -C ₄ alkenyl group or a C ₃ -C ₅ cycloalkyl group. R ¹ is ethyl, propyl, butyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3-fluoropropyl, 3,3,3-trifluoropropyl, 2,2, 3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 4-fluorobutyl group, cyclopropylmethyl group, cyclobutylmethyl group, cyanomethyl group, 2-propenyl group, 2- The acaricide according to claim 1, which is a methyl-2-propen-1-yl group or a cyclopentyl group. The acaricide according to claim ¹ , wherein R ¹ is an ethyl group, a propyl group, a butyl group, a 2,2,2-trifluoroethyl group, a cyclopropylmethyl group or a 2-propenyl group. The acaricide according to claim 1, wherein R ¹ is a propyl group or a 2,2,2-trifluoroethyl group. A is a halogen atom, an optionally substituted C ₁ -C ₄ alkyl group (the substituent is one hydroxyl group or 1-5 halogen atoms), and optionally substituted C. _2- C ₄ alkenyl group (the substituent is one fluorine atom or chlorine atom), an optionally substituted C ₂ -C ₄ alkynyl group (the substituent is one fluorine atom or A chlorine atom), an optionally substituted C ₃ -C ₄ cycloalkyl group (the substituent is one fluorine atom or a chlorine atom), a formula —C (Y) = NOR (formula Wherein R is a hydrogen atom or a C ₁ -C ₄ alkyl group, and Y is a hydrogen atom or an amino group, which may be substituted or partially saturated. 1 selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom 3-6-membered heteroaryl group containing 3 heteroatoms (the substituent is a group consisting of a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₂ alkyl group and a C ₁ -C ₂ alkoxy group) Or a cyano group. 7. The acaricide according to any one of claims 1 to 6, which is a cyano group. A is a chlorine atom, a bromine atom, an iodine _atom, C 1 -C ₃ alkyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2, 2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, hydroxylmethyl group, 1- hydroxyethyl group, 2-hydroxyethyl _group, C 2 -C ₄ alkenyl group, 2-chloro-2-propenyl group, 3-chloro-2-propenyl _group, C 2 -C ₄ alkynyl group, 3-chloro-2 Propynyl group, cyclopropyl group, cyclobutyl group, fluorocyclopropyl group, difluorocyclopropyl group, chlorocyclopropyl group Dichlorocyclopropyl group, (hydroxyimino) methyl group, (methoxyimino) methyl group, (ethoxyimino) methyl group, amino (hydroxyimino) methyl group, furyl group, thienyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, an imidazolyl group, a pyrazolyl group, oxadiazolyl group, dihydro oxadiazolyl group, thiadiazolyl group, dihydro thiadiazolyl group, a pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, or a cyano group, one of the claims 1 to 6 An acaricide according to claim 1 . A is a chlorine atom, bromine atom, methyl group, ethyl group, propyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl Group, pentafluoroethyl group, 3-fluoropropyl group, hydroxylmethyl group, 1-hydroxylethyl group, 2-hydroxylethyl group, 2-propenyl group, 2-butenyl group, ethynyl group, 1-propynyl group, 2-butynyl Group, cyclopropyl group, cyclobutyl group, (hydroxyimino) methyl group, (methoxyimino) methyl group, (ethoxyimino) methyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, oxadiazolyl group, dihydrooxadiazolyl group, thiadiazolyl group A pyridyl group or a cyano group. Or acaricide according to any one of 6. A is a chlorine atom, bromine atom, methyl group, ethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, 2-propenyl group, 2. An ethynyl group, a cyclopropyl group, a cyclobutyl group, a (hydroxyimino) methyl group, a (methoxyimino) methyl group, an isoxazolyl group, a thiazolyl group, an oxadiazolyl group, a dihydrooxadiazolyl group, a thiadiazolyl group, or a cyano group. The acaricide of any one of thru | or 6. A is a chlorine atom, bromine atom, methyl group, ethyl group, difluoromethyl group, cyclopropyl group, 2-propenyl group, (hydroxyimino) methyl group, thiazolyl group, oxadiazolyl group, dihydrooxadiazolyl group or cyano group The acaricide according to any one of claims 1 to 6. The acaricide according to any one of claims 1 to 11, wherein X is a fluorine atom or a chlorine atom. The acaricide according to any one of claims 1 to 11, wherein X is a fluorine atom. The acaricide according to any one of claims 1 to 13, wherein m is an integer of 0 to 2. The acaricide according to any one of claims 1 to 13, wherein m is an integer of 0 or 1. The acaricide according to any one of claims 1 to 15, wherein n is an integer of 0. The acaricide according to any one of claims 1 to 16, wherein Q is a group represented by the formula (Q-1) or (Q-2). The acaricide according to any one of claims 1 to 16, wherein Q is a group represented by the formula (Q-1). R ² and R ⁵ are each an optionally substituted C ₁ -C ₄ alkyl group (the substituent is 1-9 fluorine atoms or 1 halogen atom). 19. The acaricide according to any one of items 18. R ² and R ⁵ are methyl group, ethyl group, propyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group or 2,2,2-trifluoroethyl group. The acaricide according to any one of claims 1 to 18. 19. Any one of claims 1 to 18 , wherein R ² and R ⁵ are a methyl group, an ethyl group, a fluoromethyl group, a chloromethyl group, a difluoromethyl group, a trifluoromethyl group, or a 2,2,2-trifluoroethyl group. An acaricide according to claim 1 . The acaricide according to any one of claims 1 to 18 , wherein R ² and R ⁵ are a methyl group or an ethyl group. R ³ , R ⁴ , R ⁶ and R ⁷ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an optionally substituted C ₁ -C ₄ alkyl group (the substituent is 1-9 fluorine atoms) An atom or 1 chlorine atom), an optionally substituted C ₁ -C ₄ alkoxy group (the substituent is 1-7 fluorine atoms or 1 chlorine atom), substituted it is optionally C ₁ -C ₄ alkylthio group (said substituent is 1-7 fluorine atoms or one chlorine atom.) or an optionally substituted phenyl group [the substituent is A halogen atom, an optionally substituted C ₁ -C ₃ alkyl group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms) and an optionally substituted C ₁ -C ₃ alkoxy group (said substituent is either the group consisting of halogen atoms Is 1-7 substituents selected.) From 1 to 3 substituents selected from the group consisting of. 23. The acaricide according to any one of claims 1 to 22 , wherein R ³ , R ⁴ , R ⁶ and R ⁷ are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₄ alkyl group, a fluoromethyl group, a chloromethyl group, a difluoromethyl group, a trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,3,3-trifluoropropyl group, 3,3,3- Trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group, Heptafluoropropyl, 4-fluorobutyl, nonafluorobutyl, methoxy, ethoxy, fluoromethoxy, difluoromethoxy, trifluorometh Si group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group, methylthio group, ethylthio group, fluoromethylthio group, difluoromethylthio group, trifluoromethylthio group, 2,2,2-trifluoroethylthio group, A pentafluoroethylthio group, a phenyl group, or a phenyl group substituted with 1-2 substituents selected from the group consisting of a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, and a methoxy group, The acaricide according to any one of 1 to 22. R ³ , R ⁴ , R ⁶ and R ⁷ are hydrogen atom, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, butyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, tri Fluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,3,3-trifluoropropyl group, 3, 3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trimethyl Fluoroethyl group, heptafluoropropyl group, 4-fluorobutyl group, nonafluorobutyl group, difluoromethoxy group, trifluoromethoxy group, difluoromethyl group Group, 2,2,2-trifluoroethyl thio group, chlorophenyl group, a (trifluoromethyl) phenyl or (trifluoromethoxy) phenyl group, acaricides according to any one of claims 1 to 22 . R ³ and R ⁶ are a hydrogen atom, a chlorine atom or a methyl group, and R ⁴ and R ⁷ are a hydrogen atom, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a difluoromethoxy group. The acaricide according to any one of claims 1 to 22, which is a difluoromethylthio group or a 2,2,2-trifluoroethylthio group. The compound represented by the general formula (I) is:
1-methyl-5- [4-methyl-3- (propylsulfinyl) phenyl] -3- (trifluoromethyl) -1H-pyrazole,
1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole,
1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -3- (trifluoromethyl) -1H-pyrazole,
5- {4-chloro-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole,
4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2- (propylthio) benzonitrile,
4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile,
4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) sulfinyl] benzonitrile,
4- [1-ethyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile,
4- [1-methyl-3- (pentafluoroethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile,
4- [1-methyl-3- (pentafluoroethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) sulfinyl] benzonitrile,
1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (pentafluoroethyl) -1H-pyrazole 1-methyl-5- {4- Methyl-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -3- (pentafluoroethyl) -1H-pyrazole,
4- [3- (heptafluoropropyl) -1-methyl-1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile,
4- [3- (heptafluoropropyl) -1-methyl-1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) sulfinyl] benzonitrile,
3- (heptafluoropropyl) -1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -1H-pyrazole,
5- {4-Bromo-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole 5- {4-Bromo-3- [(2,2,2-trifluoroethyl) sulfinyl] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole,
5- {4-ethyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole,
1-methyl-5- {4- (2-propenyl) -3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole,
4-chloro-1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole,
5- {4-cyclopropyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole,
3- (difluoromethoxy) -1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1H-pyrazole,
3-[(Difluoromethyl) thio] -1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1H-pyrazole or 1-methyl-5 It is {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3-[(2,2,2-trifluoroethyl) thio] -1H-pyrazole. The described acaricide .   The following general formula (I)

[Where:
  R ¹ Is optionally substituted C ₁ -C ₆ An alkyl group (the substituent is a halogen atom, C ₃ -C ₆ 1-7 substituents selected from the group consisting of a cycloalkyl group and a cyano group. ), Optionally substituted C ₂ -C ₆ An alkenyl group (the substituent is 1-7 substituents selected from the group consisting of a halogen atom and a cyano group) or C ₃ -C ₆ Represents a cycloalkyl group,
  A is a halogen atom, C which may be substituted ₁ -C ₆ An alkyl group (the substituent is 1-7 substituents selected from the group consisting of a hydroxyl group and a halogen atom), an optionally substituted C; ₂ -C ₆ An alkenyl group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms), optionally substituted C ₂ -C ₆ An alkynyl group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms), optionally substituted C ₃ -C ₆ A cycloalkyl group (the substituent is 1-6 substituents selected from the group consisting of halogen atoms), a formula —C (Y) ═NOR (wherein R is a hydrogen atom or C ₁ -C ₆ Represents an alkyl group, and Y represents a hydrogen atom or an amino group. 5) containing 1 to 3 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, which may be substituted or partially saturated A 6-membered heteroaryl group (the substituent is a halogen atom, C ₁ -C ₆ Alkyl group and C ₁ -C ₆ 1 to 3 substituents selected from the group consisting of alkoxy groups. ) Or a cyano group,
  X may be the same or different when m represents an integer of 2 or 3, and represents a halogen atom;
  m represents an integer of 0 to 3,
  n represents an integer of 0 or 1,
  Q is the following general formula (Q-1) or (Q-2):

[In the formula (Q-1),
  R ² Is optionally substituted C ₁ -C ₆ Represents an alkyl group (the substituent is 1-9 substituents selected from the group consisting of halogen atoms);
  R ³ And R ⁴ Each independently represents a hydrogen atom, a halogen atom, or an optionally substituted C ₁ -C ₆ An alkyl group (the substituent is 1-9 substituents selected from the group consisting of halogen atoms), optionally substituted C ₁ -C ₆ An alkoxy group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms), optionally substituted C ₁ -C ₆ An alkylthio group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms) or an optionally substituted phenyl group [the substituent is a halogen atom, substituted Moyo C ₁ -C ₆ An alkyl group (the substituent is 1-9 substituents selected from the group consisting of halogen atoms) and optionally substituted C; ₁ -C ₆ 1 to 5 substituents selected from the group consisting of alkoxy groups (the substituent is 1-7 substituents selected from the group consisting of halogen atoms). ]. ]
Represents a group represented by
In formula (Q-2),
  R ⁵ Is optionally substituted C ₁ -C ₆ Represents an alkyl group (the substituent is 1-9 substituents selected from the group consisting of halogen atoms);
  R ⁶ Is optionally substituted C ₁ -C ₆ Represents an alkyl group (the substituent is 1-9 substituents selected from the group consisting of halogen atoms);
  R ⁷ Represents a hydrogen atom. ]
Represents a group represented by ]
(3-sulfur atom-substituted phenyl) pyrazole derivative represented by the formula:   R ¹ Is optionally substituted C ₁ -C ₄ An alkyl group (the substituent is 1-7 halogen atoms, 1 C ₃ -C ₆ A cycloalkyl group or one cyano group. ), Optionally substituted C ₂ -C ₄ An alkenyl group (the substituent is 1-2 halogen atoms or 1 cyano group) or C ₃ -C ₆ The (3-sulfur atom substituted phenyl) pyrazole derivative or a salt thereof according to claim 28, which is a cycloalkyl group.   R ¹ Is optionally substituted C ₂ -C ₄ An alkyl group (the substituent is 1-5 fluorine atoms, 1 chlorine atom, 1 C atom; ₃ -C ₄ A cycloalkyl group or one cyano group. ), C ₂ -C ₄ Alkenyl group or C ₃ -C ₅ The (3-sulfur atom substituted phenyl) pyrazole derivative or a salt thereof according to claim 28, which is a cycloalkyl group.   R ¹ Are ethyl, propyl, butyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3-fluoropropyl, 3,3,3-trifluoropropyl, 2,2,3, 3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 4-fluorobutyl group, cyclopropylmethyl group, cyclobutylmethyl group, cyanomethyl group, 2-propenyl group, 2-methyl- The (3-sulfur atom-substituted phenyl) pyrazole derivative or a salt thereof according to claim 28, which is a 2-propen-1-yl group or a cyclopentyl group.   R ¹ The (3-sulfur atom substituted phenyl) pyrazole derivative according to claim 28, wherein is an ethyl group, a propyl group, a butyl group, a 2,2,2-trifluoroethyl group, a cyclopropylmethyl group, or a 2-propenyl group. Its salt.   R ¹ The (3-sulfur atom substituted phenyl) pyrazole derivative or a salt thereof according to claim 28, wherein is a propyl group or a 2,2,2-trifluoroethyl group.   A is a halogen atom, optionally substituted C ₁ -C ₄ An alkyl group (the substituent is one hydroxyl group or 1-5 halogen atoms), optionally substituted C ₂ -C ₄ An alkenyl group (the substituent is one fluorine atom or a chlorine atom), an optionally substituted C ₂ -C ₄ An alkynyl group (the substituent is one fluorine atom or a chlorine atom), optionally substituted C ₃ -C ₄ A cycloalkyl group (wherein the substituent is one fluorine atom or a chlorine atom), a formula —C (Y) ═NOR (wherein R is a hydrogen atom or C ₁ -C ₄ An alkyl group, Y is a hydrogen atom or an amino group; 5) containing 1 to 3 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, which may be substituted or partially saturated -6-membered heteroaryl group (the substituent is fluorine atom, chlorine atom, bromine atom, C ₁ -C ₂ Alkyl group and C ₁ -C ₂ 1 to 2 substituents selected from the group consisting of alkoxy groups. 34) A (3-sulfur atom substituted phenyl) pyrazole derivative or a salt thereof according to any one of claims 28 to 33, which is a cyano group.   A is chlorine atom, bromine atom, iodine atom, C ₁ -C ₃ Alkyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoro Propyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, hydroxylmethyl group, 1-hydroxylethyl group, 2-hydroxylethyl group, C ₂ -C ₄ Alkenyl group, 2-chloro-2-propenyl group, 3-chloro-2-propenyl group, C ₂ -C ₄ Alkynyl group, 3-chloro-2-propynyl group, cyclopropyl group, cyclobutyl group, fluorocyclopropyl group, difluorocyclopropyl group, chlorocyclopropyl group, dichlorocyclopropyl group, (hydroxyimino) methyl group, (methoxyimino) Methyl group, (ethoxyimino) methyl group, amino (hydroxyimino) methyl group, furyl group, thienyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, pyrazolyl group, oxadiazolyl group, dihydrooxadiazolyl group 34. (3-sulfur atom substituted phenyl) pyrazole according to any one of claims 28 to 33, which is a thiadiazolyl group, dihydrothiadiazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group or cyano group. Derivative or a salt thereof.   A is a chlorine atom, bromine atom, methyl group, ethyl group, propyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl Group, pentafluoroethyl group, 3-fluoropropyl group, hydroxylmethyl group, 1-hydroxylethyl group, 2-hydroxylethyl group, 2-propenyl group, 2-butenyl group, ethynyl group, 1-propynyl group, 2-butynyl Group, cyclopropyl group, cyclobutyl group, (hydroxyimino) methyl group, (methoxyimino) methyl group, (ethoxyimino) methyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, oxadiazolyl group, dihydrooxadiazolyl group, thiadiazolyl group A pyridyl group or a cyano group. 8 to 33 any one of claims (3 sulfur atom-substituted phenyl) pyrazole derivative or a salt thereof.   A is a chlorine atom, bromine atom, methyl group, ethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, 2-propenyl group, The ethynyl group, cyclopropyl group, cyclobutyl group, (hydroxyimino) methyl group, (methoxyimino) methyl group, isoxazolyl group, thiazolyl group, oxadiazolyl group, dihydrooxadiazolyl group, thiadiazolyl group or cyano group 34. The (3-sulfur atom substituted phenyl) pyrazole derivative or a salt thereof according to any one of 1 to 33.   A is a chlorine atom, bromine atom, methyl group, ethyl group, difluoromethyl group, cyclopropyl group, 2-propenyl group, (hydroxyimino) methyl group, thiazolyl group, oxadiazolyl group, dihydrooxadiazolyl group or cyano group 34. The (3-sulfur atom-substituted phenyl) pyrazole derivative or a salt thereof according to claim 28 to 33.   The (3-sulfur atom-substituted phenyl) pyrazole derivative or a salt thereof according to any one of claims 28 to 38, wherein X is a fluorine atom or a chlorine atom.   The (3-sulfur atom substituted phenyl) pyrazole derivative or a salt thereof according to any one of claims 28 to 38, wherein X is a fluorine atom.   41. The (3-sulfur atom substituted phenyl) pyrazole derivative or a salt thereof according to any one of claims 28 to 40, wherein m is an integer of 0 to 2.   41. The (3-sulfur atom substituted phenyl) pyrazole derivative or a salt thereof according to any one of claims 28 to 40, wherein m is an integer of 0 or 1.   43. The (3-sulfur atom-substituted phenyl) pyrazole derivative or a salt thereof according to claim 28, wherein n is an integer of 0.   The (3-sulfur atom-substituted phenyl) pyrazole derivative or a salt thereof according to any one of claims 28 to 43, wherein Q is a group represented by the formula (Q-1).   R ² And R ⁵ Is optionally substituted C ₁ -C ₄ 45. The (3-sulfur atom-substituted phenyl) pyrazole derivative according to any one of claims 28 to 44, which is an alkyl group (the substituent is 1-9 fluorine atoms or 1 halogen atom). Or a salt thereof.   R ² And R ⁵ Is a methyl group, an ethyl group, a propyl group, a fluoromethyl group, a chloromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group or a 2,2,2-trifluoroethyl group. 45 to 44 (3-sulfur atom substituted phenyl) pyrazole derivative or a salt thereof.   R ² And R ⁵ 45 is a methyl group, ethyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group or 2,2,2-trifluoroethyl group. (3-Sulfur atom substituted phenyl) pyrazole derivatives or salts thereof.   R ² And R ⁵ The (3-sulfur atom-substituted phenyl) pyrazole derivative or a salt thereof according to any one of claims 28 to 44, wherein is a methyl group or an ethyl group.   R ³ And R ⁴ Is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an optionally substituted C ₁ -C ₄ An alkyl group (the substituent is 1-9 fluorine atoms or 1 chlorine atom), optionally substituted C; ₁ -C ₄ An alkoxy group (the substituent is 1-7 fluorine atoms or 1 chlorine atom), optionally substituted C ₁ -C ₄ An alkylthio group (the substituent is 1-7 fluorine atoms or 1 chlorine atom) or an optionally substituted phenyl group [the substituent is a halogen atom, an optionally substituted C ₁ -C ₃ An alkyl group (the substituent is 1-7 substituents selected from the group consisting of halogen atoms) and optionally substituted C; ₁ -C ₃ 1 to 3 substituents selected from the group consisting of alkoxy groups (the substituent is 1 to 7 substituents selected from the group consisting of halogen atoms). ] And R ⁶ Is optionally substituted C ₁ -C ₄ 49. The (3-sulfur atom-substituted phenyl) pyrazole derivative according to any one of claims 28 to 48, which is an alkyl group (the substituent is 1-9 fluorine atoms or 1 chlorine atom). Or a salt thereof.   R ³ And R ⁴ Is hydrogen atom, fluorine atom, chlorine atom, bromine atom, C ₁ -C ₄ Alkyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoro Propyl group, 2,3,3-trifluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoro Propyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group, heptafluoropropyl group, 4-fluorobutyl group, nonafluorobutyl group, methoxy group, ethoxy group, fluoromethoxy group, difluoromethoxy group, Trifluoromethoxy group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group, methylthio group, Tylthio group, fluoromethylthio group, difluoromethylthio group, trifluoromethylthio group, 2,2,2-trifluoroethylthio group, pentafluoroethylthio group, phenyl group or fluorine atom, chlorine atom, methyl group, trifluoromethyl group And a phenyl group substituted with 1-2 substituents selected from the group consisting of methoxy groups, and R ⁶ But ^, C ₁ -C ₄ Alkyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoro Propyl group, 2,3,3-trifluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoro 49. The method according to any one of claims 28 to 48, which is a propyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group, heptafluoropropyl group, 4-fluorobutyl group or nonafluorobutyl group. (3-Sulfur atom substituted phenyl) pyrazole derivatives or salts thereof.   R ³ And R ⁴ Are hydrogen atom, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, butyl group, fluoromethyl group, chloromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 2 -Chloroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,3,3-trifluoropropyl group, 3,3,3-trifluoropropyl group, 2, 2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group, heptafluoropropyl group, 4- Fluorobutyl group, nonafluorobutyl group, difluoromethoxy group, trifluoromethoxy group, difluoromethylthio group, 2,2,2-trifluoro Ethylthio group, chlorophenyl group, a (trifluoromethyl) phenyl or (trifluoromethoxy) phenyl radical, R ⁶ Are methyl, ethyl, propyl, butyl, fluoromethyl, chloromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trifluoro Ethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,3,3-trifluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2 , 2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group, heptafluoropropyl group, 4-fluorobutyl group or nonafluorobutyl group, 49. The (3-sulfur atom substituted phenyl) pyrazole derivative or a salt thereof according to any one of Items 28 to 48.   R ³ Is a hydrogen atom, a chlorine atom or a methyl group, and R ⁶ Is a methyl group and R ⁴ Is a hydrogen atom, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a difluoromethoxy group, a difluoromethylthio group, or a 2,2,2-trifluoroethylthio group. 48. (3-Sulfur atom substituted phenyl) pyrazole derivative or salt thereof.   The compound represented by the general formula (I) is:
  1-methyl-5- [4-methyl-3- (propylsulfinyl) phenyl] -3- (trifluoromethyl) -1H-pyrazole,
  1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole,
  1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -3- (trifluoromethyl) -1H-pyrazole,
  5- {4-chloro-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole,
  4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2- (propylthio) benzonitrile,
  4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile,
  4- [1-methyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) sulfinyl] benzonitrile,
  4- [1-ethyl-3- (trifluoromethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile,
  4- [1-methyl-3- (pentafluoroethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile,
  4- [1-methyl-3- (pentafluoroethyl) -1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) sulfinyl] benzonitrile,
  1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (pentafluoroethyl) -1H-pyrazole
  1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -3- (pentafluoroethyl) -1H-pyrazole,
  4- [3- (heptafluoropropyl) -1-methyl-1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) thio] benzonitrile,
  4- [3- (heptafluoropropyl) -1-methyl-1H-pyrazol-5-yl] -2-[(2,2,2-trifluoroethyl) sulfinyl] benzonitrile,
  3- (heptafluoropropyl) -1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -1H-pyrazole,
  5- {4-Bromo-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole
  5- {4-bromo-3-[(2,2,2-trifluoroethyl) sulfinyl] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole,
  5- {4-ethyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole,
  1-methyl-5- {4- (2-propenyl) -3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole,
  4-chloro-1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3- (trifluoromethyl) -1H-pyrazole,
  5- {4-cyclopropyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1-methyl-3- (trifluoromethyl) -1H-pyrazole,
  3- (difluoromethoxy) -1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1H-pyrazole,
  3-[(difluoromethyl) thio] -1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -1H-pyrazole or
  1-methyl-5- {4-methyl-3-[(2,2,2-trifluoroethyl) thio] phenyl} -3-[(2,2,2-trifluoroethyl) thio] -1H-pyrazole
The (3-sulfur atom substituted phenyl) pyrazole derivative according to claim 28 or a salt thereof.   An agrochemical composition comprising the (3-sulfur atom substituted phenyl) pyrazole derivative or a salt thereof according to any one of claims 28 to 53 as an active ingredient.