WO1999001436A1 - 3-(substituted phenyl)-4-halopyridazine derivatives, pesticides containing the same as the active ingredient, and intermediates thereof - Google Patents

Abstract

New 3-(substituted phenyl)-4-halopyridazine derivatives useful as pesticides, particularly herbicides.

Description

 Specification

3-monosubstituted 4-vinyl-4-halopyridazine derivatives, pesticides containing the same as an active ingredient, and intermediates for producing the same

 The present invention resides in a novel 3-substituted phenyl-4,018-opening pyridazine derivative and an agricultural chemical containing the same as an active ingredient, and particularly provides an agricultural chemical effective as a herbicide.

 Traditionally, many herbicides have been used in the cultivation of important crops such as wheat, corn, soybean, rice and the like. Desirable herbicide conditions include a high herbicidal effect at low doses, a broad herbicidal spectrum, a moderate residual effect, and sufficient crop safety. Currently, many herbicides do not sufficiently meet these requirements.

 On the other hand, 3-substituted phenyl-4-halopyridazines, such as 4-chloro-3-phenyl-6,7-dihydro-5H-cyclopentyl [c] pyridazine and 4-chloro-3-phenylphenyl 5, The method for synthesizing 6,7,8-tetrahydrocinnoline is described in Tetrarahedron Letters, 37, 1351 (1996). 6,7-Dihydro-5H-cyclopenta [c] pyridazine ゃ 4-chloro-3-3-phenyl5,6,7,8-tetrahydrocinnoline has no mention of herbicidal activity . Further, there is no description of a compound having a substituent at the phenyl group at the 3-position of a pyridazine ring or a cinnoline ring.

The synthesis method and herbicidal activity of 3-substituted funyurpyridazines are described in US Pat. No. 5,623,072 and US Pat. No. 5,616,789. However, in the above literature, the substituent of the phenyl group at the 3-position of the pyridazine ring is a hydrogen atom at the 2-position, Which has a hydrogen atom, a nitro group, or an amino group at the 4-position, and a herbicidal activity of a compound in which the phenyl group at the 3-position of the pyridazine ring has a halogen or cyano group at the 4-position. It has not been. Disclosure of the invention

 The present inventors have conducted intensive studies on the synthesis and herbicidal activity of 3-substituted phenyl 4-halopyridazine derivatives in order to solve the above-mentioned problems of the herbicides. As a result, the phenyl group at the 3-position of the pyridazine ring was obtained. 3-substituted phenyl-4,18-opening pyridazine derivatives having a halogen or cyano group at the 4-position of the plant have not only high herbicidal activity but also sufficient safety for some important crops. Thus, the present invention has been completed.

 That is, the gist of the present invention resides in a 3-substituted fuirin-4-halopyridazine derivative represented by the following general formula [I] and a pesticide containing the same as an active ingredient, particularly a herbicide.

[In the above formula, χ represents a halogen atom,

 Υ represents a hydrogen atom or a Hagen atom,

 Ζ represents a Haguchigen atom or a cyano group,

 η and m each independently represent 0 or 1,

R ′ represents a hydrogen atom, a halogen atom, a C 1 -C ₆ alkyl group or a C, 1 C ₆ haloalkyl group,

R ² is a hydrogen atom, an alkyl group of C, C ₆ , or R ′ —— K—L—M— (where I i, CR ⁴ R ⁵ , CR ⁴ R ⁵ CR ⁶ R ⁷ , an oxygen atom , A sulfur atom or a nitrogen atom substituted with a C, -Cs alkyl group, L is CR ⁸ R ⁹ , oxygen Atom, a sulfur atom or d - represents nitrogen atom substituted with an alkyl group of C _6, M represents a CR R ¹¹ oxygen atom, a sulfur atom or C, the nitrogen atom substituted with an alkyl group having -C ₆ (above Each of the substituents R ⁴ to shaku ¹¹ independently represents a hydrogen atom or a d-C ₆ alkyl group. However, K, L and Μ are not simultaneously oxygen atoms, sulfur atoms or nitrogen atoms substituted by C, -C ₆ alkyl groups. ) To form a ring represented by

R ³ is a hydrogen atom, a nitro group or a QR ¹² (wherein Q is an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group or —NR ¹³ — (wherein, R ¹³ is a hydrogen atom, C, -C ₆ Alkyl group, C ₂ -C ₆ alkenyl group, C ₂ -C ₆ alkynyl group, C -C haloalkyl group, C ₂ -C haloalkenyl group, C ₂ -C alkoxyalkyl group, c ₂ - Ashiru group C ₆ - alkylsulfonyl group c _6, - C haloalkylsulfonyl group, - § Luque sulfonyl sulfonyl Le group C _6, C ₂ - alkoxycarbonyl group C _6, Fuweniru group or Fuweniru group replacement d-in -. hydrogen atom, C, represents an alkyl group of C ₃₎ indicates, R ^'2 is -.. C, alkyl, C ₂ alkenyl groups, C ₂ -. alkynyl group , a cycloalkyl group _{c 3 -c 8, C 4 -} . C, Shikuroa alkyl group substituted by an alkyl group c ₄ -. the (cycloalkyl) alkyl group, Shikuroa alkenyl groups _{c 3 -c 8, C i -} . C, Ha port alkyl group, C ₂ -. C, haloalkenyl group,

C - halocycloalkyl group C a, Shianoarukiru group of _{C 2 -C 7, C 2 -} C,. An alkoxyalkyl group of C ₂ —C i. An alkylthioalkyl group, C ₂ -C,. Alkylsulfonylalkyl group, C ₂ —C ₆ acyl group, C ₃ —C ₆ oxoalkyl group, —C alkylsulfonyl group, Ct—Ce haloalkylsulfonyl group, C ₂ —c ₆ alkenyl sulfonyl group, Fuweniru groups, C substituted with Fuweniru group, an alkyl group of one C _3, 3- 6-membered Hajime Tamaki (said ring, 1 one two oxygen atoms, sulfur atoms and or nitrogen atom A C, -C ₃ alkyl group substituted with a 3-6 membered heterocyclic group (the ring contains 1-2 oxygen, sulfur and Z or nitrogen atoms) General formula [Π]

Or a group represented by the following general formula [m]

(Wherein, R represents a hydrogen atom or a C ₄ alkyl group; W is an oxygen atom, a sulfur atom or —NR ′ ⁶ — (wherein, R ′ ⁶ is a hydrogen atom or a C 1, C ₄ alkyl group) R ¹⁵ is a hydrogen atom, a C 1, —C ₆ alkyl group, a C ₂ —C ₆ alkenyl group, a C ₂ —C ₆ alkynyl group, a C ₃ —C ₆ cycloalkyl group, . C ₄ one CI cycloalkyl group substituted with an alkyl group, C ₃ - Shikuroa alkenyl group C _6, - haloalkyl group C 6, C 2 - haloalkenyl group C 6, c ₃ - halo C ₆ Cycloalkyl group, c ₂ —c ₅ cyanoalkyl group, c _2-

C 6 alkoxyalkyl group, C ₂ -Ce alkylthioalkyl group, C ₂ —Ce alkylsulfonylalkyl group, C ₃ —C ₆ oxoalkyl group, C ₃ —

A C ₇ -acyloxyalkyl group, a C ₃ -C ₇ alkoxycarbonylalkyl group, a phenyl group, a C 1 -C ₃ alkyl group substituted with a phenyl group, a 3- to 6-membered heterocyclic group ( The ring contains 1-2 oxygen, sulfur and nitrogen or nitrogen atoms) or a 3- to 6-membered heterocyclic group (the ring consists of 12 oxygen atoms, sulfur atoms C substituted with you and containing Z or a nitrogen atom), - an alkyl group of C _3. R ′ ⁵ is a 5- to 6-membered heterocyclic group containing 1 to 2 nitrogen atoms and / or 0 to 1 oxygen atom together with W when W represents —NR ′ ⁶ — May be formed. ) Represents a group represented by.

R ¹² , R ¹³ or R ¹⁵ phenyl group, C 1 -C ₃ alkyl group substituted by phenyl group, 3- to 6-membered heterocyclic group (the ring is composed of 12 oxygen atoms, sulfur atom You Or a 3- to 6-membered heterocyclic group (the ring contains 1-2 oxygen, sulfur and Z or nitrogen atoms) When a C, 1 C ₃ alkyl group is represented, the same group or heterocyclic group may be 1 to 3 identical or different halogen atoms, C, —C ₄ alkyl group, trifluoromethyl group, d—C Substituted with ₄ alkoxy groups, C ₂ -C ₅ acyloxy groups, -C ₄ alkylthio groups, C, 1 C ₄ alkylsulfonyl groups, nitro groups, cyano groups or C ₂ -C ₅ alkoxycarbonyl groups You may. ). BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in more detail.

 In the present invention, the 3-substituted phenyl-4-halopyridazine derivative used as a herbicide is represented by the above general formula [I].

 In the above general formula [I],

 X includes a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, of which a chlorine atom is preferable.

 Examples of Y include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Of these, a chlorine atom or a fluorine atom is preferable, and a fluorine atom is particularly preferable.

 Examples of Z include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; and a cyano group, with a chlorine atom being preferred.

 n and m are each independently 0 or 1, preferably m = 0, particularly preferably 11 = 0 or 111 = 0.

R ¹ represents a hydrogen atom; a fluorine atom, a chlorine atom, a bromine atom, or a halogen atom such as an iodine atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group; t-butyl group, pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 2_methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,3-dimethylpropyl group Hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3- Dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methyl D—C ₆ alkyl group such as propyl group;

Fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 1 , 1,2,2,2-pentanofluoroethyl, 2-fluoropropyl, 2-chloropropyl, 2-bromopropyl, 3-fluoropropyl, 3-chloropropyl, 3-bromopropyl , 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 2,2,2-trifluoro-1-methyl C, -C ₆ haloalkyl groups such as ruethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 4-bromobutyl group, 2,2,3,3,4,4,4, -heptafluorobutyl group And preferably a hydrogen atom, an alkyl group or It is a haloalkyl group.

R ² represents a hydrogen atom; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, t-pentyl , 1_methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, 1,3-dimethylpropyl, hexyl, isohexyl, 1-methylpentyl, 2-methylbutyl Methyl pentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-methylbutyl group Echirubuchiru group, 1, 1, 2-trimethyl-propyl, 1 - Echiru - 1 - methylpropyl group, 1 - Echiru - 2-d such methylpropyl group - C ₆ alkyl group can be mentioned.

Further, R ′ and R ² may combine to form a ring represented by 1 K 1 L 1 M—. This In the formula, K is a group represented by CR ⁴ R ⁵ or CR ⁴ R ⁵ CR ⁶ R ⁷ ; an oxygen atom; a sulfur atom; or a C, 1 C ₆ such as a methyl group, an ethyl group, a propyl group, and an isopropyl group. L represents a nitrogen atom substituted by an alkyl group; L represents a group represented by CR ⁸ R ⁹ ; an oxygen atom; a sulfur atom; or a C, -C ₆ alkyl group such as a methyl group, an ethyl group, a propyl group, and an isopropyl group. in a substituted nitrogen atom, M is a group formula represented by CR ^ID R ^U; oxygen atom; a sulfur atom; or a methyl group, Echiru group, propyl groups, C or isopropyl group, an alkyl group having -C ₆ Represents a nitrogen atom substituted with

Examples of the substituent R ⁴ to R ^U, independently represent a hydrogen atom; a methyl group, E Ji group, a propyl group, an isopropyl group, butyl group, isobutyl group, sec- butyl group, t- butyl group, a pentyl group , Isopentyl group, neopentyl group, t-pentyl group,

1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, 1,3-dimethylpropyl, hexyl, isohexyl, 1-methylpentyl, 2-methyl Pentyl group, 3-methylpentyl group, 1,

1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,

2-trimethylpropyl, 1-ethyl-1 -methylpropyl, 1-ethyl-

And C- and Ce-alkyl groups such as 2-methylpropyl group.

When R ¹ and R ² combine to form a ring represented by 1 K-1 L—M—, K is preferably a group represented by CR ⁴ R ⁵ or CR ⁴ R ⁵ CR ⁶ R ⁷ ; or an oxygen atom Wherein L is a group or an oxygen atom represented by CR ⁸ R ⁹ , and M is a group or an oxygen atom represented by CR R ′ ¹ , and particularly preferably K is CR ⁴ R ⁵ or CR ⁴ is a group represented by R ⁵ CR ⁶ R ^7, a group L is represented by CR ⁸ R ^9, ring members 5-6 hydrocarbon group is a group M is represented by CR ¹ ° R ^u And more preferably K, L and L are each a methylene group.

R ³ is a hydrogen atom, a nitro group or a group represented by QR ¹² .

In —QR ¹² , Q represents an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, or a group represented by —NR ¹³ —, and an oxygen atom or a group represented by —NR ¹³ — Preferred, particularly preferred is an oxygen atom.

R ¹³ in NR ' ³ — is a hydrogen atom; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl , T-pentyl, 1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, 1,3-dimethylpropyl, hexyl, isohexyl, 1-methylpentyl Group,

2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl,

1 - Echirubuchiru group, 2-Echirubuchiru group, 1, 1, 2-trimethyl-propyl, 1 - Echiru - 1 - methylpropyl group, 1 - Echiru - 2 - alkyl group of d -C ₆ such as methyl propyl group;

 Vinyl, aryl, 1-propenyl, isopropyl, 1-butenyl,

2-butenyl, 3-butenyl, 1-methylaryl, 2-methylaryl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 1 -Methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,

1-dimethylaryl, 1-ethylaryl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 4-methyl-

C ₂ -C ₆ alkenyl groups such as 3-pentenyl group, 1-propylaryl group, 1-ethyl-1-methylaryl group;

 Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2_propynyl, 1-pentynyl,

2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3 -C ₂ -Ce alkynyl groups such as hexynyl, 4-hexynyl and 5-hexynyl;

Fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromo Moethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 2-fluoropropyl group, 2-chloropropyl group, 2-bromopropyl group, 3-fluoropropyl group Group, 3-chloropropyl group, 3-bromopropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoro Propyl group, 2,2,2-trifluoro-1-methylethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 4-bromobutyl group, 2,2,3,3,4,4,4-heptaful C! Such as o-butyl group A C ₆ haloalkyl group;

A C ₂ -C ₆ haloalkenyl group such as a 3,3-dichloroallyl group;

 Methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, 2-methoxyxyl, 2-ethoxyquinethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl Group,

A C ₂ -C ₆ alkoxyalkyl group such as a 3-methoxypropyl group, a 4-methoxybutyl group, or a 5-methoxypentyl group;

 Acetyl, pyropionyl, butyryl, isoptyryl, valeryl, isovaleryl, 2-methylbutyryl, hexanoyl, 2,2-dimethylbutyryl, diethylbutyryl, 2-methylvaleryl, 3-methylvaleryl,

C ₂ -C ₆ acyl group such as 4-methylvaleryl group;

 -Ce alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, pentylsulfonyl, and hexylsulfonyl;

Triflate Ruo B C such as methylsulfonyl group, haloalkylsulfonyl group -Ce; vinylsulfonyl groups, C ₂ etc. Arirusuruhoniru group - C of Arukenirusuruho sulfonyl group;

A C ₂ -C alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propyloxycarbonyl group, an isopropylcarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group;

Phenyl, 4-chlorophenyl, 3-chlorophenyl, 2-chlorophen A phenyl group such as a phenyl group;

Or an alkyl group of c ₃ substituted with a phenyl group such as a benzyl group or a phenyl group.

Preferred are a hydrogen atom, a C ₂ —C ₆ acyl group, a c, —c ₆ alkylsulfonyl group and a C ₂ —C ₆ alkoxycarbonyl group, particularly preferably a hydrogen atom, alkylsulfonyl group or a C ₂ - is alkoxycarbonyl two Le group C _6.

In one QR ^12, as R ¹² is a hydrogen atom; a methyl group, Echiru group, a propyl group, an isopropyl group, butyl group, isobutyl group, sec- butyl group, t- butyl group, pentyl group, isopentyl group, neopentyl group , T-pentyl, 1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, 1,3-dimethylpropyl, hexyl, isohexyl, 1-methylpentyl Group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group , 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, d, such as a group. Alkyl group of vinyl; vinyl, aryl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methylaryl, 2-methylaryl, 1-pentenyl Group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-1-butenyl group, 1-methyl-3-butenyl group, 2-methyl-3-butenyl group, 3-methyl-2- Butenyl group, 3-methyl-3-butenyl group, 1,1-dimethylaryl group, 1-ethylaryl group, 1-hexenyl group, 2_hexenyl group, 3-hexenyl group, 4_hexenyl group, 5 - hexenyl group, 4-methyl - 3 - pentenyl, 1 - Puropiruariru group, 1 - Echiru - 1 - Mechiruariru group, C ₂ such geranyl group - alkenyl C _{l ();}

Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1_pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3 -C ₂ -C alkynyl groups such as hexynyl, 4-hexynyl and 5-hexynyl;

A C ₃ -C ₈ cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group;

1-methylcyclopropyl, 2-methylcyclopropyl, 1,2-dimethylcyclopropyl, 2,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1,2,2,3-tetramethylcyclopropyl, 1-methylcyclobutyl , 2 _methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl , 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methyl Rucyclopentyl group, 1,2-dimethylcyclopentyl group, 1,3-dimethylcyclopentyl group, 2,2-dimethylcyclopentyl group, 2,3-dimethylcyclopentyl group, 3,3-dimethylcyclopentyl group, 1-ethylcyclopentyl Group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group 1,4-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 3,3-dimethylcyclohexyl C ₄ -C, such as a 3,4-dimethylcyclohexyl group, a 4,3-dimethylcyclohexyl group, and a 1-ethylcyclohexyl group. A cycloalkyl group substituted with an alkyl group;

(Cyclopropyl) methyl group, (cyclobutyl) methyl group, (cyclopentyl) methyl group, (cyclohexyl) methyl group, (cycloheptyl) methyl group, Methyl group, (cyclopropyl) ethyl group, (cyclobutyl) ethyl group, (cyclopentyl) ethyl group, (cyclohexyl) ethyl group, (cycloheptyl) ethyl group, (cyclooctyl) ethyl group, (cyclopropyl) propyl C ₄ one C, such group, (cyclobutyl) Purochiru group, (cyclopentyl) Purochiru group, Purochiru group (carboxymethyl Le cyclohexane), (heptyl cyclohexylene) Puroru group. (Cycloalkyl) alkyl group;

2 Shikuropuro Bae group, 2 - cyclobutenyl group, 2 - cyclopentenyl group, 3 - cyclopentenyl group, 2 - cyclohexenyl group cycloheteroalkyl, 3 - cycloalkenyl group C ₈ - C _3, such as a cyclohexenyl group cyclohexylene;

 Fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, '2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2-pentafluoroethyl, 2-fluoropropyl, 2-chloropropyl, 2-bromopropyl, 3-fluoropropyl, 3-chloropropyl, 3-bromopropyl, 3-bromopropyl , 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 2,2,2-trifluoro-1-methyl C, 1C haloanolequinole groups such as ruethyl group, 4-fluorobutyl group, 4-chlorobutyl group, 4-bromobutyl group, 2,2,3,3,4,4,4, -heptafluorobutyl group;

C ₂ — C, such as a 3,3-dichloroallyl group. A haloalkenyl group;

2, 2 - difluoromethyl O b C _3, such as cyclopentyl group - halocycloalkyl group C 8;

A cyanomethyl group, a 1-cyanoethyl group, a 2-cyanoethyl group, a 1-cyanopropyl group, a 2-cyanopropyl group, a 3-cyanopropyl group, a 1-cyanobutyl group, a 2-cyanobutyl group, a 3-cyanobutyl group, a 4-cyanobutyl group, etc. A C ₂ -C ₇ cyanoalkyl group;

Methoxymethyl group, ethoxyquinmethyl group, propoxymethyl group, isopropoxymethyl group, butoxymethyl group, 2-methoxyhexyl group, 2-ethoxyhexyl group, 2 - Puropokishechiru group, 2 - isopropoxide shell ethyl group, 2 - Butokinechiru group, 3 - main Tokishipuropiru group, 4 - main Tokishibuchiru group, 5 - C ₂ such main Tokishipenchiru group. An alkoxyalkyl group of

Methylthiomethyl, ethylthiomethyl, propylthiomethyl, isopropylthiomethyl, butylthiomethyl, 2- (methylthio) ethyl, 2- (ethylthio) ethyl, 2- (propylthio) ethyl, 2- ( C ₂ — C> such as isopropylthio) ethyl group, 2- (butylthio) ethyl group, 3- (methylthio) propyl group, 4- (methylthio) butyl group, and 5- (methylthio) pentyl group. An alkylthioalkyl group;

Methylsulfonylmethyl, ethylsulfonylmethyl, propylsulfonylmethyl, isopropylsulfonylmethyl, butylsulfonylmethyl, 2- (methylsulfonyl) ethyl, 2- (ethylsulfonyl) ethyl, 2- (propyl Sulfonyl) ethyl group, 2- (isopropylsulfonyl) ethyl group, 2- (butylsulfonyl) ethyl group, 3- (methylsulfonyl) propyl group, 4- (methylsulfonyl) butyl group, 5- (methylsulfonyl) pentyl group, etc. C ₂ — C,. An alkylsulfonylalkyl group of

Acetyl, pyropionyl, butyryl, isoptyryl, valeryl, isovaleryl, 2-methylbutyryl, hexanoyl, 2,2-dimethylbutyryl, 2-ethylbutyryl, 2-methylvaleryl, 3-methylvaleryl A C ₂ -C ₆ acyl group such as, 4-methylvaleryl group;

 C-C oxoalkyl groups such as 2-oxopropyl group, 1-methyl-2-oxopropyl group, 1-methyl-2-oxobutyl group, 1-ethyl-2-oxobutyl group, 1-propyl-2-oxopropyl group, etc. ;

Methylsulfonyl group, Echirusuruhoniru group, propylsulfonyl group, isopropenyl Pirusuruhoniru group, butylsulfonyl group, an alkylsulfonyl group having C, -C ₆ such Kishirusuru Honiru group pentylsulfonyl group to;

A C, -C haloalkylsulfonyl group such as a trifluoromethylsulfonyl group; A C ₂ -C e alkenylsulfonyl group such as a vinylsulfonyl group and an arylsulfonyl group;

 Phenyl groups such as phenyl group, 4-chlorophenyl group, 3-chlorophenyl group and 2-chlorophenyl group;

Or a C ₃ alkyl group substituted with a phenyl group such as a benzyl group or a phenyl group;

 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 1-furyl, 2-furyl, 1-viranyl, 2-viranyl, 3-viranyl, 1-dihydro Furyl, 2-dihydrofuryl, 1-dihydrovinylyl, 2-dihydroviranyl, 3-dihydroviranyl, 1-tetrahydrofuryl, 2-tetrafuryl, 1-tetrahydrofuranyl, 2-tetrahydrofuranyl A 3- to 6-membered heterocyclic group such as a tetrahydrobilanyl group or a 3-tetrahydrobilanyl group (the ring contains 12 oxygen atoms, sulfur atoms and Z or nitrogen atoms);

C, monosubstituted by a 3- to 6-membered heterocyclic group such as 1-tetrahydromethyl group and 2-tetrahydromethyl group, which ring contains 12 oxygen, sulfur and / or nitrogen atoms A C ₃ alkyl group;

 Groups represented by the following general formula [Π], such as 1-abtyrolactonyl group and 2-abtyloractonyl;

To 〇

 —〇 [Π]

 -3

Or a group represented by the following general formula [ΠΙ],

-In the general formula “ΠΙ”, R ¹⁴ is a hydrogen atom; or a methyl group, an ethyl group, And C 1 -C ₄ alkyl groups such as benzyl, isopropyl, butyl, isobutyl, sec-butyl and tributyl, and W is represented by oxygen, sulfur or —NR ¹⁶ — Represents a group.

One NR ¹⁶ - as for R ^'6 is a hydrogen atom; or a methyl group, Echiru group, a propyl group, an isopropyl group, butyl group, isobutyl group, sec- butyl group, a a t- butyl group and the like C ■ -C ₄ It is an alkyl group.

The R ^'5, hydrogen atom; a methyl group, Echiru group, a propyl group, an isopropyl group, butyl group, isobutyl group, sec- butyl group, Bok butyl group, a pentyl group, Isopenchi group, neopentyl group, t-pentyl group , 1-methylbutyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, 1,3-dimethylpropyl, hexyl, isohexyl, 1-methylpentyl, 2- Methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, A C, -C 6 alkyl group such as a 2-ethylbutyl group, a 1,1,2-trimethylpropyl group, a 1-ethyl-1-methylpropyl group, a 1-ethyl-2-methylpropyl group;

 Vinyl, aryl, 1-propenyl, isopropyl, 1-butenyl,

2-butenyl, 3-butenyl, 1-methylaryl, 2-methylaryl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 1 -Methyl-3-butenyl, 2-methyl-3-butenyl, 3_methyl-2-butenyl, 3-methyl-3-butenyl, 1,

1-dimethylaryl, 1-ethylaryl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 4-methyl-

C ₂ _Cs alkenyl groups such as 3-pentenyl group, 1-propylaryl group, 1-ethyl-1-methylaryl group and the like;

 Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl,

2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butane Ethynyl group, 1, 1 - dimethyl - 2-propynyl group, 1 - to hexynyl group, 2-to key Shin Il group, 3 - to hexynyl group, 4 - to hexynyl group, 5 - to hexynyl group, etc. C ₂ - C 6 An alkynyl group of

A C ₃ -C ₆ cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group;

1-methylcyclopropyl, 2-methylcyclopropyl, 1,2-dimethylcyclopropyl, 2,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1,2,2,3-tetramethylcyclopropyl, 1-methylcyclopropyl Butyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl Butyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl Butyl, 1,2-dimethylcyclopentyl, 1,3-dimethylcyclopentyl, 2,2-dimethylcyclopentyl, 2,3-dimethylcyclopentyl, 3,3-dimethylcyclopentyl, 1-ethylcyclopentyl , 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 3, 4 - dimethyl cyclohexyl group, 4, 3 - dimethyl cyclohexyl group, 1 - Echirushikuro C ₄ one such as a cyclohexyl group. A cycloalkyl group substituted with an alkyl group;

A C3-C6 cycloalkenyl group such as a 2-cyclopropenyl group, a 2-cyclobutenyl group, a 2-cyclopentenyl group, a 3-cyclopentenyl group, a 2-cyclohexenyl group, or a _3- cyclohexenyl group; Fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 1 , 1,2,2,2-pentafluoroethyl, 2-fluoropropyl, 2-chloropropyl, 2-bromopropyl, 3-fluoropropyl, 3-chloropropyl, 3-bromopropyl, 3-bromopropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,2,2,3,3,3-heptafluoropropyl, 2,2,2-trifluoro-1-methylethyl Haloalkyl group of C, —C ₆ such as group, 4-fluorobutyl group, 4-chlorobutyl group, 4-bromobutyl group, 2, 2, 3, 3, 4, 4, 4, -heptafluorobutyl group;

3, 3 - haloalkenyl group C 6 - C ₂ such dichloro allyl group;

2, 2 - difluoromethyl O b C _3, such as cyclopentyl group - halons black alkyl C 6;

 Cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group, 1-cyanopropyl group, 2-cyanopropyl group, 3-cyanopropyl group, 1-cyanobutyl group,

A C ₂ -C ₅ cyanoalkyl group such as a 2-cyanobutyl group, a 3-cyanobutyl group or a 4-cyanobutyl group;

 Methoxymethyl group, ethoxyquinmethyl group, propoxymethyl group, isopropoxymethyl group, butoxymethyl group, 2-methoxethyl group, 2-ethoxyquinethyl group, 2-propoxyethyl group, 2-isopropoxyethyl group, 2-butoxyethyl group ,

A C ₂ -C ₆ alkoxyalkyl group such as a 3-methoxypropyl group, a 4-methoxybutyl group, or a 5-methoxypentyl group;

Methylthiomethyl, ethylthiomethyl, propylthiomethyl, isopropylthiomethyl, butylthiomethyl, 2- (methylthio) ethyl, 2- (ethylthio) ethyl, 2- (propylthio) ethyl, 2- ( C ₂ -C ₆ alkylthioalkyl such as isopropylthio) ethyl group, 2- (butylthio) ethyl group, 3- (methylthio) propyl group, 4- (methylthio) butyl group and 5- (methylthio) pentyl group A kill group; Methylsulfonylmethyl, ethylsulfonylmethyl, propylsulfonylmethyl, isopropylsulfonylmethyl, butylsulfonylmethyl, 2- (methylsulfonyl) ethyl, 2- (ethylsulfonyl) ethyl, 2- (propyl Sulfonyl) ethyl group, 2- (isopropylsulfonyl) ethyl group, 2- (butylsulfonyl) ethyl group, 3- (methylsulfonyl) propyl group, 4- (methylsulfonyl) butyl group, 5- (methylsulfonyl) pentyl group, etc. A C ₂ -C 6 alkyl sulfonylalkyl group;

C ₃ -Ce oxoalkyl groups such as 2-oxopropyl group, 1-methyl-2-oxopropyl group, 1-methyl-2-oxobutyl group, 1-ethyl-2-oxobutyl group, 1-propyl-2-oxopropyl group, etc. ;

2- (acetyloxy) ethyl group, 2- (propionyloxy) ethyl group, 2- (butyryloxy) ethyl group, 2- (isobutyryloxy) ethyl group, 2- (valeryloxy) ethyl group, 2 _ ( Isovaleryloxy) ethyl group, 2- (Bivaloyloxy) ethyl group, 2- (Acryloyloxy) ethyl group, 2- (Propioloyloxy) ethyl group, 2- (Methacryloyloxy) ethyl group , 2 - (black Tonoiruokishi) E butyl group, 3 _ (Asechiruokishi) propyl group, 4 - (Asechiruokishi) butyl group, 5 - (Asechiruokishi) C ₃ such as pentyl - § Sil O alkoxyalkyl groups C _7; menu Toxoxycarbonylmethyl group, ethoxyquincarbonylmethyl group, propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, butoxycarbonylmethyl group, isobutyl Xycarbonylmethyl group, sec-butoxycarbonylmethyl group, t-butynecarbonylmethyl group, pentyloxycarbonylmethyl group, isopentyloxycarbonylmethyl group, hexyloxycarbonylmethyl group, 2- (methoxycarbonyl) Ethyl group, 2- (ethoxyquincarbonyl) ethyl group, 2- (propoxycarbonyl) ethyl group, 2- (isopropoxycarbonyl) ethyl group, 2- (butoxycarbonyl) ethyl group, 2- (isobutoxycarbonyl) ethyl Group, 2- (sec-butoxycarbonyl) ethyl group, 2- (t-butoxycarbonyl) ethyl group, 2- (pentyloxycarbonyl) ethyl group, 2- (isopentyloxycarbonyl) ethyl group, 1 -(Methoxycarbonyl) ethyl group, 1- (ethoxycarbonyl) ethyl group, 1- (propoxycarbonyl) ethyl group, 1- (isopropoxycarbonyl) ethyl group, 1- (butoxycarbonyl) ethyl group, 1- (isobutoxycarbonyl) ethyl group, 1- (sec-butoxycarbonyl) ethyl group, 1 -(t-butoxycarbonyl) ethyl group, 1- (pentyloxycarbonyl) ethyl group, 1- (isopentyloxycarbonyl) ethyl group, 3- (methoxycarbonyl) propyl group, 3- (ethoxy) Carbonyl, propyl, 3- (propoxycarbonyl) propyl, 3- (isopropoxycarbonyl) propyl, 3- (butoxycarbonyl) propyl, 1- (methoxycarbonyl) propyl, 1- (ethoxy) Carbonyl) propyl group, 1- (propoxycarbonyl) propyl group, 1- (isopropoxycarbonyl) propyl group, 1- (butyl 1- (methoxycarbonyl) -1-methylethyl group, 1- (ethoxycarbonyl) -1-methylethyl group, 1-methyl-1- (propoquincarbonyl) ethyl group, 1 -(Isopropoxycarbonyl) -1-methylethyl group, 1- (butoxycarbonyl) -1-methylethyl group, 4- (methoxycarbonyl) butyl group, 4- (ethoxycarbonyl) butyl group, 4-( A C ₃ -C ₇ alkoxycarbonylalkyl group such as a propoxycarbonyl) butyl group and a 3- (isopropoxycarbonyl) butyl group;

 A phenyl group;

 A C, -C3 alkyl group such as a methyl group, an ethyl group, a propyl group, or an isopropyl group substituted with a phenyl group;

 1- 3 to 6-membered heterocyclic group containing two oxygen, sulfur and / or nitrogen atoms;

Or 1 one 2 oxygen atoms, sulfur atoms and or containing a nitrogen atom 3-6 membered heterocyclic ring substituted methyl group group, Echiru group, a propyl group, d and isopropyl groups - alkyl C ₃ Is mentioned.

Examples of the 3- to 6-membered heterocyclic group containing one or two oxygen atoms, sulfur atoms and / or nitrogen atoms include an oxylanyl group, an oxetanyl group, a tetrahydrofuryl group, a furyl group, a chenyl group, a pyrrolyl group, a pyrrolidinyl group, Oxazolyl, thiazolyl, imidazolyl, isooxazolyl, isothiazolyl, pyrazolyl Groups, tetrahydroviranyl group, pyridyl group, piperidyl group, pyrimidinyl group, pyridazinyl group, morpholinyl group, piperazinyl group, and these may have a substituent.

R ¹⁵ may form a ring together with W when W represents —NR ¹⁶ —. And if R ¹⁵ to form a W and ring, 5 R ¹⁵ contains 1 one two nitrogen atoms Contact preliminary or 0- 1 oxygen atoms with W - to form a 6-membered heterocyclic group Is shown. 1-Pyrrolidinyl, 1-pyrrolyl, 2-isoxazolidinyl, 1-virazolyl are 5- to 6-membered heterocyclic groups containing one or two nitrogen atoms and zero or one oxygen atom. Group, 1-imidazolyl group, 1-piperidyl group, 4-morpholinyl group, perhydro-1,2-oxazine-2-yl group, 1-piperazinyl group and the like. May be.

R ¹² , R ′ ³ or R ¹⁵ force phenyl group, C 1 -C ₃ alkyl group substituted with a phenyl group, 3- to 6-membered heterocyclic group (the ring is composed of 12 oxygen atoms , Containing a sulfur atom and / or a nitrogen atom) or a 3- to 6-membered heterocyclic group containing 1 to 2 oxygen atoms, a sulfur atom and a Z or nitrogen atom In the case where the C 1 -C ₃ alkyl group is represented, the phenyl group and the heterocyclic group may have a substituent. Specific examples of the substituent include 13 identical or different halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. , sec - Bed butyl group, a a t- butyl group and the like C, - alkyl C _4; triflate Ruo Russia methyl; main DOO alkoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, Isobuto alkoxy group, alkoxy groups such as sec-butoxy group and t-butoxy group; acetyloxy group, propionyloxy group, ptyryloxy group, isoptyryloxy group, valeryloxy group, isovaleryloxy group, vivaloyloxy group, acryloyloxy group, propio Roiruokin group, methacryloyloxy Ruo alkoxy group, Ashiruokishi group of C ₂ -C _5, such as black Tonoiruo alkoxy group; Chiruchio group, Echiruchio group, propyl thio group, an isopropylthio group, Puchiruchio group, Isopuchiruchio group, sec- butyl Chiomoto, C etc. t- butylthio group, - alkylthio group C 4; methylsulfonyl group, C, -d alkylsulfonyl groups such as ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, t-butylsulfonyl; nitro; cyano; Or a C ₂ -C ₅ alkyl such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, t-butoxycarbonyl, etc. Coxycarbyl groups and the like.

Among them, R ³ is preferably a hydrogen atom, a nitro group or one QR ' ² [wherein Q is an oxygen atom or one NR' ³ — (R ' ³ is a hydrogen atom, a C ₂ -C ₆ acryl group, ,

-Represents an alkylsulfonyl group of Ce or an alkoxycarbonyl group of C ₂ -Ce), and R ¹² is a hydrogen atom; An alkyl group of C ₂ —C ,. Alkenyl group, C ₂ —d. Alkynyl group, C ₃ - cycloalkyl group C _8, C ₃ - cycloalkenyl group _{C 8, C, - C,} . Haguchi alkyl group, C ₂ — C ,. Haloalkenyl group of C ₂ —C,. A halonchloroalkyl group, a C ₂ —C ₇ cyanoalkyl group,

C one C,. An alkoxyalkyl group, a C ₃ -C oxoalkyl group, d

C alkylsulfonyl group, c is substituted with Fuweniru group, - C ₃ alkyl group,

3-to 6-membered heterocyclic group (the ring contains 112 oxygen atoms), 3- to 6-membered heterocyclic group (the ring contains 112 oxygen atoms) A C, 1 C ₃ alkyl group substituted with a group represented by the following general formula [Π],

Q,

 -〇 [π]

 -3 or a group represented by the following general formula [ΙΠ]

(Wherein, R ¹⁴ represents a hydrogen atom or a C, C ₄ alkyl group; W is an oxygen atom or a NR ¹⁶ — (wherein, R ′ ⁶ is a hydrogen atom or C, -C 4 alkyl) R ′ ⁵ represents a hydrogen atom or a C, —C ₆ alkyl group. 〕 Out.

Particularly preferably, R ³ is a hydrogen atom, a nitro group or —QR ¹² [wherein Q is an oxygen atom or —NR ¹³ — (R ¹³ is a hydrogen atom, d-Ce alkylsulfonyl group or C ₂ -Ce alkoxy R ′ ² is a hydrogen atom, C 1 -C, An alkyl group of C ₂ —. An alkenyl group, C ₂ . Alkynyl group, C ₃ -C 8 cycloalkyl group, C, — C,. A C ₂ -C ₁₀ haloalkenyl group; a C ₂ -CT cyanoalkyl group; C ₂ . An alkoxyalkyl group of c ₃ -C _6, an oxoalkyl group of c ₃ -C _6, an alkylsulfonyl group of d-c ₆ , a C-, C ₃ -alkyl group substituted by a phenyl group, a 3- to 6-membered heterocyclic group (the ring is A C 1, 1 C ₃ alkyl group substituted with a 3-6 membered heterocyclic group (containing 12 oxygen atoms), a 3-6 membered heterocyclic group (containing 12 oxygen atoms), And a group represented by the above general formula [Π] or a group represented by the above general formula [示 す]. More preferably, R ³ is one QR ¹² [wherein Q represents an oxygen atom, R ¹² is —C _ID alkyl group, C ₂ —C ,. An alkenyl group, C ₂ _C ,. Alkynyl group, a cycloalkyl group of C ₃ -C ₈ of, C! — C,. Haguchi alkyl group, C ₂ — d. A haloalkenyl group; a C ₂ -C ₇ cyanoalkyl group; C ₂ . A C ₃ -C ₆ oxoalkyl group, a 3-6 membered heterocyclic group (the ring contains 112 oxygen atoms), a 3-6 membered heterocyclic group (the ring shows one one two C substituted by an oxygen atom containing), a group shown by the group or the general formula -C ₃ [Π]. ].

Further, as a combination of substituents, R ′ and R ² are preferably bonded together to form a ring, and R ³ is a hydrogen atom, a nitro group or a QR ¹² [wherein Q is an oxygen atom or a nitrogen atom. NR ¹³ — (wherein, R ¹³ represents a hydrogen atom, C, a C ₆ alkylsulfonyl group or a C ₂ -C ₆ alkoxycarbonyl group), and R ′ ² represents a hydrogen atom, C , One C,. An alkyl group of C ₂ —. An alkenyl group, C ₂ —C ,. Archi Nyl group, C ₃ —C ₈ cycloalkyl group, C,. C ₂ —C ₁₀ haloalkenyl group, C ₂ —C ₇ cyanoalkyl group, C ₂ —C. An alkoxyalkyl group, a C ₃ -C ₆ oxoalkyl group, a C, -Ce alkylsulfonyl group, a d-C ₃ alkyl group substituted by a phenyl group, a 3-6 membered heterocyclic group (the ring is A C ₃ alkyl group substituted by a 3- to 6-membered heterocyclic group containing 1 to 2 oxygen atoms (the ring contains 112 oxygen atoms); A group represented by the formula [Π],

Or a group represented by the following general formula [m]

(Wherein R ¹⁴ represents a hydrogen atom or an alkyl group of C, —C ₄ , W is an oxygen atom or one NR ¹⁶ — (wherein, R ¹⁶ is a hydrogen atom or a d-C 4 alkyl group) And R ¹⁵ represents a hydrogen atom or an alkyl group of C or -C ₆ . ], And

Particularly preferably, R ′ and R ² are bonded together to form a carbocycle, and R ³ is —QR ¹² (wherein Q represents an oxygen atom, and an alkyl group of R ′ d —C ,. An alkenyl group of ₂ — C,., An alkynyl group of C ₂ _C,., A cycloalkyl group of C ₃ — c ₈ , a haloalkyl group of d — C _{1 (),} a haloalkenyl group of C ₂ — C. ₂ - Shianoarukiru group _{c 7, C 2 -. C} i alkoxyalkyl group, c ₃ - Okiso alkyl group c _6, the 3-6 membered Hajime Tamaki (said ring, one one two oxygen atoms A C ₃ -C ₃ alkyl group substituted by a 3-6 membered heterocyclic group (the ring contains 112 oxygen atoms) or a group represented by the above general formula [Π] Is shown.] Is the case.

 Of these, Y is more preferably a halogen atom.

The compound represented by the above general formula [I] may form a salt at the pyridazine ring portion and, when the substituent R ³ contains a hydroxyl group or a nitrogen atom, the portion. Specifically, alkali metal salts such as sodium salt, potassium salt, or calcium salt, or alkaline earth metal salts, hydrofluoride, hydrochloride, hydrobromide, hydroiodide, etc. Inorganic acid salts such as nitrates, perchlorates, sulfates and phosphates; sulfonates such as methanesulfonate, trifluoromethanesulfonate and P-toluenesulfonate Is mentioned.

 Also, the following general formula [V] or [V ']

(Wherein, Y, Z, R ′, R ² and R ³ are the same as defined in claim 1) are important intermediates for synthesizing the compound [I] of the present invention. Yes, a new compound.

 Compounds [V] and [V '] are structural isomers, and are easily isomerized in the presence of acid or alkali. For example, when chlorinated with a reagent such as phosphorus oxychloride, the reaction proceeds via compound [V], and when alkylation is performed in the presence of a base such as sodium hydride, [V ′] is used. The reaction proceeds via.

Next, methods for producing the novel 3-substituted phenyl-4-halopyridazines and derivatives thereof of the present invention, and intermediates thereof will be described. The compound of the present invention represented by the general formula [I] can be produced, for example, by any one of the following production methods (1) and (13). Manufacturing method (1)

(In the above reaction formula, X, Y, Z, R ', R 2 are as defined above. R ^3' are water atom, a nitro group, an alkoxy group, an alkylthio group, this reaction and such dialkylamino groups It is an inert group that is not affected by the synthesis of the following raw materials [] .R ¹⁷ represents a lower alkyl group such as a methyl group or an ethyl group.

 The above reaction is carried out without solvent or in a solvent in the presence of a base, usually at a temperature of 0 to 200 ° C, preferably 50 to 100 ° C. The amount of the compound to be used in the reaction is usually 1 to 1 equivalent of [VII], 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents, and 1.0 to 1.5 equivalents of base. 3.0 equivalents, preferably 1.0 to 1.5 equivalents o

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform). Form, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc., ethers (eg, ethyl ether, tetrahydrofuran, dioxane), esters (eg, ethyl acetate, butyl acetate), ketones (eg, acetone, methyl) Aprotic polar solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetonitrile, etc.), alcohols (methanol, ethanol, _2- propanol, etc.), Organic acids (formic acid, acetic acid, etc.), water, and mixtures thereof It is below.

Bases used include triethylamine, diisopropylethylamine, pyridine, picoline, N, N-getylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,01-7- ゥ decene, 1, 5-diazabicyclo [4,3,0] -5-none Organic bases such as 1,4-diazabicyclo [2,2,2] octane, sodium hydride, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and carbonate Inorganic bases such as sodium hydrogen hydride, sodium bicarbonate, sodium acetate, potassium acetate, sodium fluoride, potassium fluoride and the like.

Manufacturing method (2)

(In the above reaction formula, X, Y, Z, R ′, and R ² are the same as defined above. R ³ ″ represents a hydrogen atom, a nitro group, an alkoxy group, an alkylthio group, a dialkylamino group, etc. It is an inert group that is not affected by the synthesis of the intermediate [V] shown below:) The above reaction is carried out in the absence of a solvent or in a solvent, usually in the presence of a halogenating agent, usually from 0 to 200 ° C. The reaction is preferably carried out at a temperature in the range of 10 to 100 ° C. The amount of the compound used in the reaction is usually 1.0 to 3 with respect to 1 equivalent of [V]. 0.0 equivalents, preferably 1.5 to 2.0 equivalents.

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform). Examples include form, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc., ethers (eg, getyl ether, tetrahydrofuran, dioxane), and mixtures thereof. The halogenating agents used include phosphorus trichloride, phosphorus oxychloride, phosphorus pentachloride, hydrogen chloride, phosphorus tribromide, hydrogen bromide, sulfate trifluoride, getylamine complex, and tetrabutylammonium. Examples include mufluoride and hydrogen fluoride. Manufacturing method (3)

[la] [lb]

(In the above reaction formula, X, Y, Z, R ', R 2, and Q are same as defined above. (Wherein, R in [I a]' ^2, except for hydrogen atom.))

 The above reaction is carried out without a solvent or in a solvent, in the presence of an acid, usually at a temperature in the range of 120 to 200 ° C, preferably 10 to 10 ° C. When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, Chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.), ethers (getyl ether, tetrahydrofuran, dioxane, etc.), non-protonic polar solvents (N, N-dimethylformamide, Examples include N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetonitrile, etc., alcohols (eg, methanol, ethanol, 2-propanol), water, and mixtures thereof.

Examples of the acid used include acids such as formic acid, acetic acid, trifluoroacetic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, methanesulfonic acid, and P-toluenesulfonic acid. The starting material [Ia] can be synthesized by the above-mentioned production method (1) or (2). [I a] in R ^'2 is an alkyl group, a cycloalkyl group, Ashiru group or an alkoxyalkyl group, and the like are preferable.

When R ¹² is expected to affect the cyclization reaction described in the above production method (1) as in the above general formula [ΠΙ], the compound obtained in the above production method (3) is prepared by the following production method. It can be produced by derivatization according to (4) or (5). Manufacturing method (4)

[lb] [la]

(In the above reaction formula, X, Y, Z, R ', R 2, R' 2 and Q are the same in the aforementioned definition. (However, R ^'2 is a hydrogen atom is excluded.) V is chlorine A halogen atom such as an atom, a bromine atom or an iodine atom; a lower alkylsulfonyloxy group such as a methylsulfonyloxy group; or an arylsulfonyloxy group such as a P-toluenesulfonyloxy group.

The above reaction is carried out without solvent or in a solvent in the presence of a base, usually at a temperature of 0 to 200 ° C, preferably 10 to 100 ° C. The amount of the compound used in the reaction is usually to [I b] is 1 equivalent, R ¹² -. V is 1.0 to 3 0 equivalents, preferably 1! ) To 1.5 equivalents, and the base is 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents.

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform). Form, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.), ethers (eg, ethyl ether, tetrahydrofuran, dioxane), esters (eg, ethyl acetate, butyl acetate), ketones (eg, acetone, methyl) Ethyl ketone), non-protonic polar solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, acetonitrile, etc.), alcohols (methanol, ethanol, 2-propanol) ), Organic acids (formic acid, acetic acid, etc.), water, and mixtures thereof It is below. Examples of bases used include triethylamine, pyridine, picoline, N, N-ethylylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,0] -7-indene. Organic bases such as 1,5-diazabicyclo [4,3,0] -5-nonene and 1,4-diazabicyclo [2,2,2] octane, and sodium hydride, lithium hydride, and hydroxide Inorganic bases such as sodium, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium acetate, potassium acetate, sodium fluoride, and lithium fluoride.

Manufacturing method (5)

(In the above reaction formula, X, Y, Z, R ', R 2, R' 2 and Q are defined the aforementioned same. (However, R ¹² is a hydrogen atom is excluded.) R ¹⁸ is methyl And a lower alkyl group such as an ethyl group, etc.) The above reaction is carried out in the absence of a solvent or in a solvent in the presence of triphenylphosphine and dialkyl azodicarboxylate, usually at 0 to 100 ° C., preferably at 0 to 100 ° C. It is performed in a temperature range of 50 ° C. The amount of the compound used in the reaction is usually to [I b] is 1 equivalent, R ^'2 -. OH is from 1.0 to 3 0 equivalents, preferably 1.0 to 1.5 equivalents, Application Benefits The phenylphosphine is 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents, and the dialkyl azodialkyl arbonate is 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents. .

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform). Form, 1,2-dichloroethane, black benzene, dichlorobenzene, etc.), ethers (getyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (aceton, Non-protonic polar solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetone) And a mixture thereof.

Manufacturing method (6)

 [Ic] [Id]

(In the above reaction formula, X, Y, Z, R ¹ and R ² are the same as defined above.) The above reaction is carried out without solvent or in a solvent, usually at 110 to 150 ° C., preferably. Is carried out in a temperature range of 20 to 60 ° C. The amount of compound used in the reaction is usually

The ditrophy agent is used in an amount of 1.0 to 3.0 equivalents, preferably 1.5 to 2.0 equivalents, based on 1 equivalent of [Ic].

 When a solvent is used, suitable solvents include inorganic acids (such as sulfuric acid and hydrochloric acid), organic acids (such as formic acid and acetic acid), and organic anhydrides (such as acetic anhydride). Mixtures of inorganic acids (sulfuric acid, hydrochloric acid) and nitric acid or nitrate (sodium nitrate, potassium nitrate, etc.), nitric acid, nitrodimethyltetrafluoroborate And ditronium trifluoromethanesulfonate.

Manufacturing method (7)

 [Id] [Ie]

(In the above reaction formula, X, Y, Z, R ′ and R ² are the same as defined above.) The above reduction reaction is carried out in the absence of a solvent or in a solvent, usually in the presence of a metal or metal compound, and an acid. Is performed in a temperature range of 50 to 100 ° C. Used metal, or The amount of the metal compound is usually 1 to 20 equivalents, preferably 2 to 10 equivalents, based on 1 equivalent of [Id]. The amount of the acid used is usually from 0.01 to 20 equivalents, preferably from 0.01 to 10 equivalents, for 1 equivalent of [Id].

 When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform). Form, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.), ethers (getyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl) Ethyl ketone), non-protonic polar solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetonitrile, etc.), organic acids (formic acid, acetic acid), water, and And the like. The amount of solvent used is usually 1 to 100 times, preferably 1 to 20 times the weight of [Id]. Examples of the metal or metal compound used include iron, zinc, tin, tin (II) chloride and the like. Examples of the acid used include hydrochloric acid, sulfuric acid, and acetic acid. In the above reaction, sodium sulfide, sodium hydroxide sulfide, sodium dithionite, ammonium sulfide, hydrogen Z metal catalyst (palladium-carbon, platinum-carbon, rhodium-alumina, platinum, Raney nickel) were used as reducing agents. Etc.) can also be used.

Manufacturing method (8)

[If] [Ig]

(In the above reaction formula, X, Y, Z, R ¹ , R ² , R ¹² and R ′ ³ are the same as defined above. (However, R ¹² excludes a hydrogen atom.) V is a chlorine atom Halogen atoms such as bromine atom and iodine atom; lower alkylsulfonyl groups such as methylsulfonyloxy group Roxy group; or arylsulfonyloxy group such as P-toluenesulfonyloxy group. )

The above reaction is carried out without solvent or in a solvent in the presence of a base, usually at a temperature of 0 to 200 ° C, preferably 10 to 100 ° C. The amount of the compound used in the reaction is usually such that R ¹³ — V is 1.0 to 3.0 equivalents, preferably 1.5 to 2.0 equivalents, relative to 1 equivalent of [If]. The base is 1.0 to 3.0 equivalents, preferably 1.5 to 2.0 equivalents.

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform). Form, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.), ethers (getyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl) Non-protonic polar solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetonitrile, etc.), alcohols (methanol, ethanol, 2-propanol, etc.) , Organic acids (formic acid, acetic acid, etc.), water, and mixtures thereof It is below. Examples of bases used include triditylamine, pyridine, picoline, N, N-getylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,0] -7-indene, 1,5-diazabicyclo [4,3,0] -Organic bases such as 5-nonene and 1,4-diazabicyclo [2,2,2] octane, and sodium hydride, potassium hydride, sodium hydroxide, hydrating power, and carbonic acid Inorganic bases such as sodium carbonate, sodium hydrogen carbonate, sodium hydrogencarbonate, sodium hydrogen carbonate, sodium acetate, sodium acetate, sodium fluoride, potassium fluoride, and the like. Manufacturing method (9)

[Ih] [Ii]

(In the above reaction formula, X, Y, R ′, R ² , R ³ are the same as defined above, X ′ represents a halogen atom, and Met represents a metal atom.)

 The above reaction is carried out without a solvent or in a solvent, usually at a temperature of 0 to 250 ° C, preferably 100 to 200 ° C. Usually, the amount of the compound used in the reaction is 1.0 to 3.0 equivalents, preferably 1.5 to 2.0 equivalents of the cyanating agent (Met-CN) per 1 equivalent of [Ih]. Is equivalent.

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform). Form, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.), ethers (eg, methyl ether, tetrahydrofuran, dioxane), esters (eg, ethyl acetate, butyl acetate), ketones (acetone, methyl) Non-protonic polar solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetonitrile, etc.), alcohols (methanol, ethanol, 2-propanol, etc.) , Organic acids (formic acid, acetic acid, etc.), water, and mixtures thereof And the like. Examples of the cyanating agent used include copper cyanide, potassium cyanide, and sodium cyanide. Manufacturing method (10)

 [I] [ij]

(In the above reaction formula, X, Y, Z, R ¹ , R ² , R ³ , n and m are the same as defined above, provided that n + m> 0)

 The above reaction is carried out without solvent or in a solvent, in the presence of an oxidizing agent, in the presence or absence of a metal or a metal complex, ordinarily at 0 to 200 ° C., preferably at 10 to 100 ° C. Performed in a temperature range. The amount of the compound used in the reaction is usually 1.0 to 3.0 equivalents, preferably 1.5 to 2.5 equivalents, relative to 1 equivalent of [I], and is preferably a metal or metal. When a complex is required, it is used in an amount of 0.05 to 1.5 equivalents, preferably 0.1 to 1.0 equivalent.

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform). Form, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.), aprotic polar solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetate nitril) Etc.), alcohols (methanol, ethanol, 2-propanol, etc.), organic acids (formic acid, acetic acid, etc.), water, and mixtures thereof. Examples of the oxidizing agent include m-chlorobenzoic acid, peracetic acid, hydrogen peroxide, and t-butylhydroxide baroxide. Examples of the metal or metal complex to be used include vanadium, molybdenum, titanium tetraisopropoxide titanate diisopropyl complex and the like. Manufacturing method (1 1)

[I] [Ik]

(In the above reaction formula, X, Y, Z, R ¹ , R ² , and R ³ are the same as defined above, c H—U is an acid that forms a salt with the compound of the present application, and specifically, Hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, and hydroiodic acid; inorganic acids such as nitric acid, perchloric acid, sulfuric acid, and phosphoric acid; methanesulfonic acid, trifluoromethanesulfone Acid, sulfonic acid such as p-toluenesulfonic acid.)

 The above reaction is carried out without solvent or in a solvent in the presence of H—U, usually at a temperature of 0 to 200 ° C., preferably 10 to 100 ° C. The amount of the compound used in the reaction is usually 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents of H—U to 1 equivalent of [I].

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform). Form, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.), ethers (eg, methyl ether, tetrahydrofuran, dioxane), esters (eg, ethyl acetate, butyl acetate), ketones (acetone, methyl) Aprotic polar solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetonitrile, etc.), alcohols (methanol, ethanol, 2-propanol, etc.), And water and mixtures thereof. Manufacturing method (1 2)

(In the above reaction formula, X, Y, Z, R ′, R ² , and R ³ are the same as defined above. X ′ represents a halogen atom, and P represents one B (OH) ₂ or one Met′— X〃 (Me t 'represents a metal such as magnesium or zinc, and X〃 represents a halogen atom).) The above reaction is carried out in the absence or presence of a metal or metal complex in a solvent or in a solvent. The reaction is carried out at a temperature of 0 to 200 ° C., preferably 10 to 100 ° C. The amount of the compound used in the reaction is usually [IX] to 1 equivalent, [X] to 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents. It is 0.01 to 1 equivalent, preferably 0.05 to 5 equivalents.

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform). Form, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.), ethers (eg, ethyl ether, tetrahydrofuran, dioxane), aprotic polar solvents (N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, acetate nitrile, etc.), and mixtures thereof. When a metal or metal complex is used, suitable metals or metal complexes include nickel, iron, ruthenium, cobalt, orifice, iridium, palladium, platinum, and other metals, and tetrakis (triphenylphosphine) palladium. , Tris (dibenzylideneaceton) dipalladium, dichloromethane bis (triphenylphosphine) palladium, dichloro [1,3-bis (diphenylphosphino) prononone] nickel, bis (acetylacetonate) ) Nigger, dichloro [1, 1'-bis (diphenylphosphino) The aforementioned metals such as dimethyl, or chlorides of the aforementioned metals and triphenylphosphine, tri (0-tolyl) phosphine, 1,2-bis (diphenylphosphine) ethane, 1,2-bis (diphne) And metal complexes formed with ligands such as 1,1'-bis (diphenylphosphino) phenene, dibenzylideneacetone, and acetylacetone.

Manufacturing method (1 3)

(In the above reaction formula, X, Y, Z, R ¹ , R ² , and R ³ are the same as defined above. W is a halogen atom such as a chlorine atom, a bromine atom, and an iodine atom; a methylsulfonyloxy group and the like. A lower alkylsulfonyloxy group; a lower haloalkylsulfonyloxy group such as trifluoromethylsulfonyloxy group; or an arylsulfonyloxy group such as P-toluenesulfonyloxy group.

 The reaction is carried out in the absence or presence of a base, in the presence or absence of a metal or metal complex in the presence or absence of a solvent, at a temperature of 50 to 200 ° C, preferably 0 to 100 ° C. Done in a range. The amount of the compound used in the reaction is usually [ΧΠ] to 1 equivalent, [XI] to 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents, and base to 1.0 equivalent. 33.0 equivalents, preferably 1.0 05 equivalents, and the metal or metal complex is 0.01 11.0 equivalents, preferably 0.05 50.5 equivalents.

When a solvent is used, suitable solvents include aliphatic hydrocarbons (hexane, heptane, etc.), aromatic hydrocarbons (benzene, toluene, quinylene, etc.), and halogenated hydrocarbons (dichloromethane, chloroform). Form, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.), ethers (eg, methyl ether, tetrahydrofuran, dioxane, etc.), non-protonic polar solvents (N, N-dimethylforma) Mid, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, acetonitrile, etc.), and mixtures thereof. Examples of bases used include triethylamine, pyridine, picoline, N, N-ethylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,0] -7-indene, 1,5-diazabicyclo Organic bases such as [4,3,0] -5-nonene, 1,4-diazabicyclo [2,2,2] octane, and sodium hydride, potassium hydride, butyllithium, sec-butyllithium, t-butyl Lithium, phenyllithium, sodium methoxide, potassium methoxide, sodium ethkind, potassium ethoxide, lithium diisopropylamide, potassium t-butoxide, sodium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, hydrogen carbonate Sodium, hydrogen bicarbonate, sodium acetate, potassium acetate, sodium fluoride, Tsu and potassium of inorganic bases. Examples of the metal or metal complex used include copper chloride, copper bromide, copper iodide, iron chloride, iron bromide, and iron iodide.

 The starting compound [W] in the above-mentioned production method (1) can be produced, for example, according to the following reaction formula.

 [IX] [X] [VII]

(In the above reaction formula, X, Y, Z, R ³ and R ′ ⁷ are the same as defined above.)

Further, the starting compound [V] in the production method (2) can be produced, for example, according to the following reaction formula.

(In the above reaction formula, X, Y, Z, R ¹ , R ² , and R ³ are the same as defined above. V and W are the same or different, and are halogen atoms such as chlorine, bromine, and iodine. The compound of the present invention has isomers such as optical isomers and diastereomers depending on its structure, and the compound of the present invention includes all of these. When the compound of the present invention is used as a herbicide, each isomer separated according to a known method may be used alone, or may be used as a mixture of isomers.

When the compound of the present invention is used as a herbicide, the compound of the present invention (hereinafter sometimes referred to as “the drug substance”) may be applied as it is, but usually, an appropriate adjuvant, Used in the form of granules, emulsions, flowables, etc. Examples of adjuvants include solid carriers such as kaolin, bentonite, talc, diatomaceous earth, white carbon, starch; water, alcohols (methanol, ethanol, propanol, butanol, ethylene glycol, etc.), ketones (acetone, Methylethyl ketone, cyclohexanone, etc.), ethers (eg, methyl ether, dioxane, cellosolves), aliphatic hydrocarbons (eg, kerosene, kerosene), aromatic hydrocarbons (eg, benzene, toluene, xylene) , Solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (dichloroethane, carbon tetrachloride, trichlorobenzene, etc.), acid amide Solvents (eg, dimethylformamide), esters (eg, ethyl acetate, butyl acetate, glyceryl fatty acid esters), and nitriles (eg, acetonitrile); nonionic surfactants (eg, polyoxyethylene) Alkyl ethers, polyoxyethylene sorbitan monolaurate, etc., cationic surfactants (alkyldimethylbenzylammonium chloride, alkylpyridinium chloride, etc.), anionic surfactants (alkylbenzene sulfone) Surfactants such as acid salts, lignin sulfonates, higher alcohol sulfates, etc.) and amphoteric surfactants (alkyl dimethyl betaine, dodecylaminoethyl glycine, etc.). These solid carriers, solvents, surfactants and the like are each used as a single kind or as a mixture of two or more kinds as necessary.

 The application rate of the compound of the present invention varies depending on conditions such as the structure of the compound, the target weed, the treatment time, the treatment method, and the properties of the soil. Usually, the amount of the active ingredient per hectare is 2 to 200,000. Grams, preferably in the range of 5 to 1000 grams, are suitable. The target weeds of the compound of the present invention are, for example, in the field, for example, Shiroza, Akaza, Inutade, Hartade, Inoubu, Aobu, Hakobe, Hotokenoza, Ichibi, Ona Momi, Wild Asagao, Dwarf Asagao, Wild Karasina, Yaemada Usumire, Orosagigiku, Kosendangsa, Mehishiba, Ohishiba, Inubie, Enokorogusa and the like.

 In paddy fields, for example, Kikasigusa, Azena, Konagi, Abnome, Mizohakobe, Heramodaka, Tainubie, Tamagayari, Perica, Omodaka, Hotaru, Mizugayari and the like. The compound of the present invention can control the above weeds both in the pre-emergence soil treatment and in the foliage treatment during the growing season. In addition, the compound of the present invention has little effect on cultivated crops such as corn, wheat, barley, rice, soybean and the like in both pre-emergence soil treatment and growing foliage treatment, and is used as a selective herbicide. can do.

The herbicide containing the compound of the present invention as an active ingredient can be mixed and applied with other pesticides used in the same field, for example, insecticides, fungicides, plant growth regulators, and fertilizers. It is also possible to stabilize the herbicidal effect by mixing and applying other herbicides. It is possible. When the compound of the present invention and another herbicide are mixed and applied, the respective preparations may be mixed at the time of application, or may be applied as a preparation containing both in advance. Examples of the herbicides that can be suitably mixed and applied with the compound of the present invention include the following.

Carbamate herbicides:

 2-chloroallyl getyl dithiocarbamate,

 S- 2,3-dichloroallyl disopropylthiocarbamate,

 S-2,2,3-tricole loallyl diisopropylthio force,

 S-Ethyl dipropyl thiocarbamate,

 S-ethyl diisobutyl thiocarbamate,

 S-benzyl 1,2-dimethylpropyl (ethyl) thiocarbamate,

 S- 4-cloth benzyl getyl thiocarbamate,

 S-ethylethyl dolazepine-1-thiocarboxylate,

 S-isopropyl para-Droazepine-1-thiocarboxylate,

 S-1-methyl-1-phenylethylpiperidine-1-thiocarboquinate,

 0-3-1-Butylphenyl 6-methoxy-2-pyridyl (methyl) thiocarbamate,

3-(Methoxycarbonylamino) phenyl 3'-methylphenylcarbamate, isopropyl 3'-chlorophenylcarbamate,

 Methyl (4-aminophenylsulfonyl) carbamate, etc.

Urea herbicides:

 3-(3,4-dichlorophenol) -1, trimethylperyl,

 3-(3,4-dichlorophenyl) -trimethoxy-1-methylperyl,

 1, tridimethyl-3- [3- (trifluoromethyl) phenyl] rare,

 3-[4- (4-methoxyphenoxy) phenyl] -1,1-dimethylperyl,

 1- (1-Methyl-1-phenylethyl) -3-P-tolylrea,

 3- (4-isopropylphenyl) -1,1-dimethylperyl,

 3- (5-t-butylisoxazol-3-yl) -1,1-dimethylperyl,

1- (5-1-butyl-1,3,4-thiadiazol-2-yl) -1,3-dimethylperyl, 1- (benzothiazol-2-yl) -1,3-dimethylperyl, etc.

Amide herbicides:

 2 -Black mouth-2 ', 6, -Jetyl-N- (methoxymethyl) acetanilide,

 N- (butoxymethyl) -2-chloro-2,6,-getylacetanilide,

 2-black mouth-2 ', 6, -Jetyl-N- (2-propoxyshetyl) acetanilide,

 2-chloro-N- (ethoxymethyl) -6, -ethylacetate-0-toluidide,

 2-chloro-6'-ethyl-N- (2-methoxy-1-methylethyl) aceto-0-toluzide, 2-chloro-N- (3-methoxy-2-thenyl) -2 ', 6 '-Dimethylacetanilide,

 N- (Chloroacetyl) -N- (2,6-getylphenyl) glycine ethyl ester, 2-chloro-N- (2,4-dimethyl-3-phenyl) -N- (2-Methoxy-1-methylethyl) Case Amid,

 3 ', 4'-dichloropropionanilide,

 2 ', 4'-Difluoro-2- [3- (trifluoromethyl) phenoxy] nicotinanilide,

2- (1,3-benzothiazole-2-yloxy) -N-methylacetanilide,

 2-bromo-N- (a, a-dimethylbenzyl) -3,3-dimethylbutylamide,

 N- [3- (Tretyl-1-methylpropyl) isoxazole-5-yl] -2,6-Dimethoxybenzamide, etc.

Dinitroaniline herbicides:

 2,6-dinitro-Ν, Ν-dipropyl-4--(trifluoromethyl) aniline,

 Ν-butyl-Ν-ethyl-2,6-dinitro-4- (trifluoromethyl) aniline,

2, 6-Hee Bok port - New ^1, dipropyl in New - 4-(triflate Ruo ii methyl)-m-Fuwenirenjia Min,

 4-(dipropylamino) -3,5-dinitrobenzenesulfonamide,

 N-sec-butyl-4-t-butyl-2,6-dinitroaniline,

 N- (l-ethylpropyl) -2,6-dinitro-3,4-xylidine, etc.

Carboxylic acid herbicides:

 (2,4-dichlorophenoxy) acetic acid and its derivatives,

(2,4,5-trichlorophenoxy) acetic acid and its derivatives, (4-chloro-2-methylphenoxy) acetic acid and its derivatives,

 2- (2,4-dichlorophenoxy) propionic acid and its derivatives,

 4- (2,4-dichlorophenoxy) butyric acid and its derivatives,

 2, 3, 6-trichloro mouth benzoic acid and its derivatives,

 3, 6-dichloro-2-methoxybenzoic acid and its derivatives,

 3,7-dichloroquinoline-8-sulfonic acid,

 7-cloth-3-methylquinoline-8-carboxylic acid,

 3,6-dichloropyridine-2-hydroxysulfonic acid and its salts,

 4-amino-3,5,6-trichloropyridine-2-carboxylic acid and salts thereof,

 (3,5,6-trichlopen-2-pyridyloxy) acetic acid and its derivatives,

 (4-amino-3,5-dichloro-6-fluoro-2-pyridyloxy) acetic acid and derivatives thereof,

 (4-chloro-2-oxobenzothiazoline-3-yl) acetic acid and its derivatives,

 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid and its derivatives, 2- [4- [5- (trifluoromethyl) -2-pyridyloxy] phenoxy] propionic acid and its derivatives ,

 2- [4- [3-chloro-5- (trifluoromethyl) -2-pyridyloxy] phenoxy] propionic acid and its derivatives,

 2- [4- (6-chloro-1,3-benzoxazol-2-yloxy) phenoxy] propionic acid and derivatives thereof,

 2- [4- (6-chloroquinoxaline-2-yloxy) phenoxy] propionic acid and its derivatives,

 2- [4- (4-cyano-2-fluorophenoxy) phenoxy] propionic acid and its derivatives, etc.

Phenolic herbicides:

 3,5-dibromo-4-hydroxybenzonitrile and salts thereof,

 4 -hydroxy-3,5-jodobenzonitrile and its salts,

2-1-butyl-4,6-dinitrophenol and its salts, etc. Cyclohexanedione herbicides:

 Methyl 3- [1- (aryloxyimino) butyl] -4-hydroxy-6,6-dimethyl-2-oxo-3-cyclohexene-1-carboquinate and salts thereof,

 2- [1- (ethoxyimino) butyl] -5- [2- (ethylthio) propyl] -3-hydroxy-2-cyclohexen-1-one,

 2- [1- (ethoxyimino) butyl] -3-hydroxy-5- (thian-3-yl) -2-cyclohexen-1-one,

 2- [1- (Ethoxyimino) propyl] -3-hydroxy-5- (2,4,6-trimethylphenyl) -2-cyclohexene; I-one,

 2- [1- (3-chloroallyloxyimino) propyl] -5- [2- (ethylthio) propyl]-

3-hydroxy-2-cyclohexenone,

 2- [2-chloro-4- (methylsulfonyl) benzoyl] cyclohexane-1,3-dione, etc.

Diphenyl ether herbicide:

 4-nitrophenyl 2,4,6-trichlorophenyl ether,

 2- (2,4-dichlorophenoxy) -2-nitroanisole,

 2-chloro-4- (trifluoromethyl) phenyl 3-ethoxy-4--2-nitrophenyl—ter,

 Methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate,

 5- [2-chloro-4-4- (trifluoromethyl) phenoxy] -2-nitrobenzoic acid and its salts,

 0- [5- [2-Chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoyl] ethyl glycolate,

 0_ [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoyl]-DL-lactate,

 5- [2-chloro_4- (trifluoromethyl) phenoxy] -N- (methylsulfonyl) -2-2-nitrobenzamide,

2-chloro mouth-6-nitro-3-phenyloxydiline, etc. Sulfonylarea herbicides:

 2- (4-chloro-6-methoxypyrimidin-2-ylcarbamoylsulfamyl) benzoate

 Methyl 2- (4,6-dimethylpyrimidine-2-ylcarbamoylsulfamoyl) benzoate,

 Methyl 2- [4,6-bis (difluoromethoxy) pyrimidine-2-ylcarbamoyls rufamoinole] benzoate,

 Methyl 2- (4,6-dimethoxypyrimidine-2-ylcarbamoylsulfamoylmethyl) benzoate,

 1- (2-chlorophenylsulfonyl) -3- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) ゥ rea,

 Methyl 2- (4-methoxy-6-methyl-1,3,5-triazine-2-ylcarbamoylsulfamoinole) benzoate,

 Methyl 2- [4-methoxy-6-methyl-1,3,5-triazin-2-yl (methinole) carbamoylsulfamoyl] benzoate,

 1- [2- (2-chloroethoxy) phenylsulfonyl] -3- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) ゥ rea,

 1- (4,6-dimethoxy-1,3,5-triazine-2-yl) -3- [2- (2-methoxyethoxy) phenylsulfonyl] ゥ rea,

 Methyl 2- [4-ethoxy-6- (methylamino) -1,3,5-triazine-2-ylcarbamoylsulfamoyl] benzoate,

 Methyl 3- (4-methoxy-6-methyl-1,3,5-triazine-2-ylcarbamoylsulfamoyl) thiophene-2-carboxylate,

 Ethyl 5- (4,6-dimethoxypyrimidine-2-ylcarbamoylsulfamoyl) -trimethylpyrazole-4-carboxylate,

 Methyl 3-chloro-5- (4,6-dimethoxypyrimidine-2-ylcarbamoylsulfamoyl) -1-methylbirazol-4-carboxylate,

1- (4,6-dimethylquinpyrimidin-2-yl) -3- [3_ (trifluoromethyl) -2-pyridyl Rusulfonyl] ゥ rare,

 1- (4,6-Dimethoxypyrimidin-2-yl) -3- [3- (ethylsulfonyl) -2-pyridylsulfonyl] ゥ rea,

 2-(4,6-Dimethoxypyrimidine-2-ylcarbamoylsulfamoyl) -N, N-dimethylnicotinamino,

 1- (2-chloroimidazo [l, 2-a] pyridin-3-ylsulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) ゥ rea,

 [2- (cyclopropylcarbonyl) phenylsulfamoyl] -3- (4,6-dimethylmethoxypyrimidin-2-yl) ゥ rea,

 Tri (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -3- [2- (3,3,3-trifluoromethyl) phenylsulfonyl] ニ ル rea, etc.

Vibilidinum herbicides:

 1, Γ-dimethyl-4,4'-biviridinium dichloride,

 1, 1'-Ethylene-2, 2'-Bipyridinium Jib mouth, etc.

Pyrazole herbicides:

 4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yltoluene-4 -snolephonate,

 2- [4- (2,4-dichlorobenzoyl) 1,3-dimethylpyrazole-5-yloxy] acetophenone,

 2- [4- (2,4-dimethoxy-3-methylbenzoyl) -1,3-dimethylpyrazol-5-yloxy] -4'-methylacetophenone, etc.

Triazine herbicides:

6-chloro-N ² , N ⁴ -getyl-1,3,5-triazine-2,4-diamine,

6-Chloro-N ² -ethyl-N ⁴ -isopropyl-1,3,5-triazine-2,4-diamine, 2_ [4-chloro-6- (ethylamino) -1,3,5-triazine-2 -Ylamino]-2-methylpione

N ² , N getyl-6- (methylthio) -1,3,5-triazine-2,4-diamine;

N ² - (l, 2-dimethyl-propyl) - N ⁴ - Echiru 6- (methylthio) - 1, 3, 5-triazine - 2, 4-Jiamin,

 4-Amino-6-l-butyl-3- (methylthio) -1,2,4-triazine-5 (4H) -one, etc. Imidazolinone herbicides:

 Methyl 2- (4-isopropyl-4-methyl-5-oxo-2-imidazoline-2-yl) -4 (5) -methylbenzoate,

 2- (4-isopropyl-4-methyl-5-oxo-2-imidazoline-2-yl) pyridine-3--3-carboxylic acid and salts thereof,

 2- (4-isopropyl-4-methyl-5-oxo-2-imidazoline-2-yl) quinoline-3-carboxylic acid and salts thereof,

 5-ethyl-2- (4-isopropyl-4-methyl-5-oxo-2-imidazoline-2-yl) pyridin-3-carboxylic acid and salts thereof,

 2- (4-isopropyl-4-methyl-5-oxo-2-imidazoline-2-yl) -5- (methoxymethyl) pyridine-3-carboxylic acid and its salts, etc.

Other herbicides: 1-methyl-3-phenyl-5- [3- (trifluoromethyl) phenyl] -4-pyridone,

3 -chloro- 4- (clomethyl) -1- [3- (trifluoromethyl) phenyl] -2-pyrrolidinone,

 5- (methylamino) -2-phenyl-4- [3- (trifluoromethyl) phenyl] furan-3 (2H) -one,

 4-chloro-5- (methylamino) -2- 2- [3- (trifluoromethyl) phenyl] virazine-3 (2H) -one,

 N, N-Getyl-3- (2,4,6-trimethylphenylsulfonyl) -1H-1,2,4-triazole-1-carboxamide,

 N- [2,4-dichloro-5- [4- (difluoromethyl) -4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole-tril] phenyl] Methanesulfonamide,

 [4-chloro-3- (2,2,3,3,3-pentafluoropropoxymethyl) phenyl] -5-phenyl-1H-1,2,4-triazole-3-carboxamide ,

2- (benzyl) -4,4-dimethylisoxazolidin-3-one, 5-cyclopropyl-4- [2- (methylsulfonyl) -4- (trifluoromethyl) benzoyl] isoxazole,

 5- 1-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxaziazol-2 (3H) -one,

 Ethyl [2-chloro-5- [4-chloro-5- (difluoromethoxy) -1-methylbiazol-3-yl] -4-fluorophenoxy] acetate,

 S, S'-dimethyl 2- (difluoromethyl) -4-isobutyl-6- (trifluoromethyl) pyridine-3,5-dicarbothioate,

 Methyl 2- (difluoromethyl) -5- (4,5-dihydro_1,3-thiazol-2-yl) -4--isobutyl-6- (trifluoromethyl) pyridine-3-carboxylate,

 2-chloro-6- (4,6-dimethoxypyrimidine-2-ylthio) benzoic acid and its salt, methyl 2- (4,6-dimethoxypyrimidine-2-yloxy) -6- [1- (me Toxiimino) ethyl] benzoate,

 2,6-bis (4,6-dimethoxypyrimidine-2-yloxy) benzoic acid and its salt, 5-bromo-3-sec-butyl-6-methylpyrimidine-2,4 (1H, 3H) -dione,

 3-t-butyl-5-chloro-6-methylpyrimidine-2,4 (1H, 3H) -dione,

 3-cyclohexyl-1,5,6,7-tetrahydrocyclopentenepyrimidine-2,4 (3H) -dione,

 Isopropyl 2-chloro-5- [1,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4-((trifluoromethyl) pyrimidin-1-yl] benzoate;

 Trimethyl-4-isopropyl-2-[(2-methylphenyl) methoxy] -7-oxabisic mouth [2.2.1] heptane,

 N- (4-chlorophenyl) -3,4,5,6-tetrahydrophthalimid,

 Pentyl [2-chloro-4--4-fluoro-5- (1,3,4,5,6,7-hexahydro-1,3-dioxo-2H-isoindole-2-yl) phenyloxy] acetate To

 2- [7-Fluoro-3,4-dihydro-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazin-6-yl] -4,5,6,7-tetrahi Dro-1H-isoindole-1,3 (2H) -dione,

N- (2,6-difluorophenyl) -5-methyl [1,2,4] triazolo [1,5-a] pyrimidine- 2-sulfonamide,

 N- (2,6-dichloro-3-methylphenyl) -5,7-dimethoxy [1,2,4] triazolo [1,5-a] pyrimidine-2-sulfonamide,

 2,3-dihydro-3,3-dimethylbenzofuran-5-ylethanesulfonate 2-ethoxy-2,3-dihydro-3,3-dimethylbenzofuran-5-ylmethanesulfonate

 Methyl [[2-chloro-4--4-fluoro-5-[(tetrahydro-3-oxo-1H, 3H- [1,3,4] thiadiazolo [3,4a] pyridazine-1-ylidene) amino] phenyl] Chio] acetate,

2- [2- (3-chlorophenyl) -2,3-epoxypropyl] -2-ethylindan-1,3-dione, etc. Examples

 Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

Reference example 1

 Ethyl 1- "4-chloro 5- (cyclopentyloxy) -2-fluorophenyl] ethylidenecarbazate

The mixture of 6.1 g of 4'-chloro-5 '-(cyclopentyloxy) -2'-fluoroacetophenone, 2.5 g of ethyl carbazate, and 20 mL of toluene was heated to reflux for 10 hours while the ester was heated. Water is constantly removed from the system using a tube. After standing overnight, the mixture was concentrated to obtain a crude product. Column chromatography (Developing solvent hexane: ethyl acetate / 7: 1) to give 4.2 g of the title compound. The physical property values and NMR spectrum data are as follows.

_{Ή-NR (CDC1 3) 6} (ppm): 7.93 (1H, br), 7.22 (1H, d, J_ = 6.0 Hz), 7.10 (1H, d, 10.5 Hz), 4.84 (1H, m), 4.32 ( 2H, q, J_ = 6.9 Hz), 2.22 (3H, s), 1.98-1.80 (4H, m), 1.75-1.59 (2H, m),

 1.35 (3H, t, J = 6.9 Hz).

Reference example 2

 2,2,2-Trichloro-1- [4-chloro-5- (cyclopentyl ^^)-2-fluorophenyl] ethylidene carbazate

Ethyl 1- [4-chloro5- (cyclopentyloxy) -2-fluorophenyl] ethylidenecarbazetate obtained in Reference Example 1 1.8 g, N-chlorosuccinimide 2.4 g, tetrachloride Heat a mixture of 30 mL of carbon to reflux for 28 hours. Leave at room temperature overnight, filter off the precipitated crystals, and wash the crystals with ethyl acetate. The obtained filtrate was concentrated to obtain 2.6 g of ethyl 2,2-dichlorotoluene [4-chloro5- (cyclopentyloxy) -2-fluorophenyl] ethylidenecarbazetate. A mixture of this crude product and sulfuryl chloride 4.5 is stirred at 50 ° C for 17 hours. Thereafter, the reaction solution is dropped into the stirred ice water. The precipitated crystals were separated by filtration, dissolved in ethyl acetate, washed with saturated saline, dried over anhydrous sodium sulfate, filtered and concentrated. The obtained crystals were filtered, washed with hexane and dried to obtain 1.8 g of the title compound. Physical property values and NMR spectrum data are as follows.

 m. p. 230.0-231.0. C

 Ή-NMR (CDCh) δ (ppm): 7.58 (1H, br), 7.32 (1H, d, J = 9.3 Hz),

5 o 6.94 (1H, d, J_ = 5.7 Hz), 4.75 (1H, m), 4.29 (2H, q, J_ = 6.9 Hz), 1.98-1.80 (4H , M), 1.75-1.59 (2H, m), 1.33 (3H, t, J_ = 6.9 Hz). IR (KBr) v (cm- '): 2965, 1630, 1490, 1450, 1402, 1341, 1190.

Reference example 3

 Ethyl-4-chloro-5-cyclopentyloxy-2-fluorophenylglycoxylate

A stirrer bar was placed in a lOOmL four-necked flask, and a gym-mouth condenser tube and a thermometer were installed. A mixture of 0.49 g of metallic magnesium, a piece of iodine, and 2 mL of THF was stirred under a nitrogen stream for 15 minutes until the color of iodine disappeared to activate magnesium. Then, a solution of 2.0 g of tribromo-4-chloro-5-cyclopentyloxy-2-fluorobenzene in 0.1 mL of dibromoethane in 6 mL of THF was heated to an internal temperature of 35 ° C or less over 15 minutes. It was dripped slowly while keeping. After completion of the dropwise addition, a solution of 0.1 mL of dibromoethane in 2 mL of THF was slowly added dropwise over 5 minutes while maintaining the internal temperature at 35 ° C or lower to prepare a Grignard reagent.

A stirrer bar was placed in a 2000 mL four-necked flask, and a gym-mouth-one cooling tube and a thermometer were installed. A mixture of 30.0 g of metallic magnesium, 1 spatula of iodine, and 150 mL of THF was stirred under a nitrogen stream for 15 minutes until the iodine color disappeared to activate magnesium. The Grignard reagent prepared above was added thereto by syringe, and after adding 220 mL of THF, 181.94 g of tribromo-4-chloro-5-cyclopentyloxy-2-fluorobenzene, 181.94 g of dibromoethane, and 10.8 g of dibromoethane were added. A 180 mL solution of THF was slowly added dropwise over 2 hours while maintaining the internal temperature at 30 to 36 ° C. After dropping, add 2.7 mL of dibromoethane in 15 mL of THF solution slowly over 30 minutes while maintaining the internal temperature at 35 ° C or less. O

 A stirrer bar was placed in a 3000 mL four-necked flask, and a gym-mouth-one cooling tube and a thermometer were installed. Thereto was added a solution of 184.0 g of getyl oxalate in 800 mL of ether, and the mixture was cooled to -30 ° C under a nitrogen stream. The Grignard reagent prepared above was slowly added dropwise over 1.5 hours while maintaining the temperature at -30 ° C or lower. The temperature was further raised to −20 ° C., and the mixture was stirred for 1 hour. A saturated aqueous solution of ammonium chloride was slowly added to the reaction mixture to terminate the reaction, and the temperature was raised to room temperature. The reaction mixture was extracted with ethyl acetate, and the obtained organic phase was washed with saturated saline, dried over anhydrous sodium sulfate, filtered and concentrated. Unreacted getyl oxalate in the crude product was distilled off at a bath temperature of 70 ° C. with 0.5 mL Hg, and the obtained crude product was subjected to flash column chromatography (developing solvent hexane). : Ethyl acetate 20: 1-15: 1) to give 101.1 g of the title compound. Physical properties and NMR spectrum data are as follows.

 m.p. 54.5-55.1 ° C

 Ή-NMR (CDCh) δ (ppm): 7.40 (1H, d, J_ = 6.0 Hz),

 7.22 (1H, d, J 10.2 Hz), 4.85 (1H, m), 4.43 (2H, q, J_-6.9 Hz), 1.98-1.80 (4H, m), 1.75-1.59 (2H, m), 1.40 (3H, t, J_ = 6.9 Hz).

 4-Chloro-5-cyclopentyloxy-2-fluorophenylglyoxylic acid

A mechanical stirrer and a thermometer were installed in a 2000 mL three-necked flask, and 40.00 g of sodium hydroxide and 500 mL of water were added thereto to prepare a 2N aqueous sodium hydroxide solution. After cooling to room temperature, 109.8 g of ethyl 4-chloro-5-cyclopentyloxy-2-fluorophenylglycoxylate obtained in Reference Example 3 was slowly added, and the mixture was stirred for 1.5 hours. After completion of the reaction, slowly add 1000 mL of 1N hydrochloric acid aqueous solution. To make the reaction solution acidic. The reaction mixture was extracted three times with ether, and the obtained organic phase was washed twice with saturated saline, dried over anhydrous sodium sulfate, filtered and concentrated to obtain 99.8 g of the title compound. Physical properties and NMR spectrum data are as follows. mp 94.2-96.7 ° C

 Ή-NR (CDC13) δ (ppm): 7.99 (1H, t, J_ = 7.8 Hz),

 7.33 (1H, dd, J_ = 1.5, 8.4 Hz), 7.26 (1H, dd, J_ = 1.5, 9.9 Hz),

 7. 03 (1H, br).

 IR (KBr) v (cm- '): 2985, 1720, 1692, 1606, 1408, 1250, 1215, 1080, 990, 900, 861, 540.

Example 1

 3- (4-chloro-2-fluoro-5-cyclopentyloxyphenyl) -6,7-dihydro-4--4-hydroquine- [5H] -cyclopenta [c] pyridazine

A 100 mL flask was equipped with a stirrer bar, a salt tube and an alkali trap. Thereto, 99.8 g of 4-chloro-5-cyclopentyloxy-2-fluorophenyldalioxylic acid obtained in Reference Example 4 and 122.0 mL of thionyl chloride were added, and 2.5 at 60 ° C. The mixture was heated and stirred for hours. Thereafter, a distillation set was installed, and the bath temperature was raised to 110 ° C, and unreacted thionyl chloride was distilled off. Further, 120 mL of benzene was added and distilled off together with the remaining thionyl chloride, followed by drying under reduced pressure with a vacuum pump to obtain crude glyoxylic acid chloride.

A stirrer bar, a salt tube and a thermometer were installed in a 2000 mL four-necked flask. Then, 54.2 g of N- (1-cyclopentene-tolyl) -morpholine, 66.6 g of triethylamine and 500 mL of methylene chloride are added, and the mixture is cooled to -5 ° C under a nitrogen stream. Then, the previously prepared solution of glyoxylic acid chloride in methylene chloride (200 mL) was added for 1 hour. The solution was dripped slowly while keeping the temperature of the solution below rc. Further, the reaction mixture was stirred at 1-10 ° C for 1 hour. The reaction mixture was filtered and the residue (triethylamine hydrochloride) was washed with 150 mL of methylene chloride. The filtrate was transferred to a 2000 mL flask, 500 mL of 2-propanol was added, hydrazine hydrate 19.8 was added dropwise with stirring, the mixture was stirred at room temperature for 1 hour, and then left standing for one hour. The reaction mixture was concentrated under reduced pressure, and the residue was suspended in ethanol. The suspension was filtered, and the residue was washed with ethanol and hexane and dried under reduced pressure to obtain 55.5 g of the title compound. The residue obtained by concentrating the filtrate under reduced pressure was suspended again in ethanol, filtered, washed and dried in the same manner to obtain 13.6 g of the title compound. The physical property values and NMR spectrum data are as follows.

 m.p. 300 ° C over

 Ή-NMR (DMS0-d6) δ (ppm): 7.23 (1H, d, J_ = 6.3 Hz),

 7.18 (1H, d, J = 9.6 Hz), 4.79 (1H, m), 3.05 (2H, t, J_ = 7.5 Hz), 2.96 (2H, t, J = 7.5 Hz), 2.17 (2H, qui, J_- 7.5 Hz),

 1.95-1.53 (8H, m).

IR (KBr) (cm- ¹ ): 3050, 2920, 1580, 1560, 1492, 1465, 1401, 1187.

Example 2

 4-Chloro-3- [4-chloro-5- (pentyloxy) -2-fluorophenyl] -6,7-dihydric mouth -5H-cyclopentyl [c] pyridazine

Ethyl 2,2,2-trichloro-1- [4-chloro-5- (cyclopentyloxy) -2-fluorophenyl) ethylidenecarbazetate obtained in Reference Example 2. 1.50 g of dichloromethane in 10 mL 0.42 g of triethylamine is slowly added dropwise to the solution. The mixture 0.64 g) of 1-morpholino-1-cyclopentene is added thereto, and the mixture is refluxed for 7 hours. After standing overnight, the reaction mixture is extracted with ethyl acetate, washed successively with a saturated aqueous solution of ammonium chloride, a saturated aqueous solution of sodium bicarbonate and then with a saturated saline solution, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was purified by flash column chromatography (hexane: ethyl acetate Z9: l-3: 1) to obtain 0.50 g of the title compound (Table-1, No. 18).

Example 3

 4- (3-chloro-2-fluoro-5-hydroxyphenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine

75% sulfuric acid 4mU 4-chloro-3_ (4-chloro5-cyclopentyloxy-2-fluorophenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine 2.4 g of methylene chloride Slowly add 2 mL solution dropwise. After stirring at room temperature for 30 minutes, the reaction mixture is dropped into crushed ice water and extracted with ethyl acetate. After neutralizing the aqueous layer with saturated aqueous sodium hydrogen carbonate, extract with ethyl acetate. The combined organic layer is washed with a saturated saline solution, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was washed with a small amount of ethyl acetate and hexane to give 1.68 g of the title compound (Table 1, o. 12) as crystals.

Example 4

2- (2-chloro-4--4-fluoro-5- (4-chloro-6,7-dihydro-5H-cyclopentane [c] pyridazine-3-yl) phenoxy] propionate .丄 C0 ₂ C ₂ H ₅

4-chloro-3- (4-chloro-2-fluoro-5-hydroxyphenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine 0.40 g, ethyl bromopropionate 0 A mixture of 29 g, 0.22 g of potassium carbonate and 5 mL of acetone was heated to reflux for 5 hours with stirring. The reaction solution was cooled to room temperature, a saturated aqueous ammonia solution was added, and the mixture was extracted with ethyl acetate. The organic phase was washed with brine and dried over sodium sulfate. The crude product obtained by concentration under reduced pressure was purified by flash column chromatography (hexane-ethyl acetate Z2: 1) to obtain 0.44 g of the title compound (Table-2, No. 54).

Example 5

 4-Chloro-3-[4-chloro-2-fluoro-5- (trimethyl-2-propynyloxy) phenyl] -6,7-dihydro-5'-cyclopenta [c] pyridazine

4_Chloro-3- (4-chloro-2-fluoro-5-hydroxyphenyl) -6,7-dihydro-5H-cyclopenta [C] pyridazine 0.61 g and triphenylphosphine (TPP) To a solution of 0.67 g of tobuten-3-ol 0.21 in 5 mL of tetrahydrofuran, gently add getyl azodicarboxylate (DEAD) 0.44 dropwise. Then, stir at room temperature overnight. The reaction solution was concentrated under reduced pressure, and the obtained crude product was purified by flash column chromatography (hexane-ethyl acetate Z3: 1). The obtained crystals were washed with hot water and the title compound (Table 1, No. 24) 0.46 g was obtained. Example 6

 4-Chloro-3- [4-cyclopentyl 5- (cyclopentyloxy) -2-fluorophenyl] -6,7-dihydro-5H-cyclopenta [c] pyridazine

3- (4-Couguchi-2-fluoro-5-cyclopentyloxyphenyl) -6,7-dihydroxy-4-hydroxy- "5i-cyclopenta [c] pyridazine obtained in Example 1 A toluene solution (10 mL) of 1.45 g and phosphorus oxychloride (3.00 g) was stirred for 1 hour at room temperature, and the reaction mixture was added to ice-cold water (100 mL) and extracted with ethyl acetate. The obtained organic phase was washed with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated.The obtained crude product was purified by flash column chromatography (hexane-ethyl acetate // 2: 1) to give 1.50 g of the title compound (Table-1, No. 18).

Example 7

 4-bromo-3- [4-chloro-5- (pentyloxy) -2-fluorophenyl] -6,7-dihydro-5H-cyclopenta [c] pyridazine

-(4-Chloro-2-fluoro-5-cyclopentyloxyphenyl) -6,7-dihydroxyl-4-hydroxy- "5ΗΊ-cyclopenta [obtained in Example 1 The 30 mL solution of phosphorus tribromide was heated and stirred for 2 hours at 80-90 ° C. After the reaction was completed, it was cooled to room temperature, the reaction mixture was poured into ice water, and extracted with chloroform. The extract was washed with a saturated aqueous solution of sodium bicarbonate and then with a saturated saline solution, and dried over anhydrous sodium sulfate. After filtration, the mixture was concentrated. The crude product was purified by flash column chromatography (developing solvent hexane: ethyl acetate Z3: 1-5: 2) to obtain 3.00 g of the title compound. Example 8

 4-Chloro-3- (4-oct-5--2-to-2-fluorophenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine

4-7.4- (4-chloro-2-fluorophenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine To 7.4 g of 35 g of concentrated sulfuric acid, add 7 mL of concentrated sulfuric acid. Stir while cooling to make a homogeneous system. A mixed acid (2.5 mL of concentrated sulfuric acid, 2.5 mL of 60% nitric acid) is slowly added dropwise to the mixture at 6-12 ° C over 10 minutes. The reaction mixture is poured into ice water (400 mL), extracted with ethyl acetate, and the obtained organic layer is washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was purified by flash column chromatography (hexane-ethyl acetate Z2: 1) to obtain 5.12 g of the title compound (Table 1, No. 8).

Example 9

 4-Chloro-3- (5-amino-4-chloro-2-fluorophenyl) -6,7-dihydro-5H-cyclopenta [c] pyridazine

A mixture of 6.0 g of iron powder, 6 m of water and 1.5 mL of acetic acid was heated to reflux for 30 minutes. After cooling to room temperature, add isopropanol (20 mL) and heat to 70 ° C. -3- (4-chloro-2--2-fluoro-5-nitrophenyl) -6,7-dihydro-5H-cyclopentene [c] pyridazine 5.05 g of N-methylpyrrolidone (NMP) solution Add 20 mL slowly. Then, heat and stir at 80 ° C for 1.5 hours, cool to room temperature, and add potassium carbonate solution

(1.25 g potassium carbonate, 10 mL water). The mixture is filtered through celite and the residue is washed with ethyl acetate. The filtrate is concentrated, and the obtained crude product is extracted with ethyl acetate. The obtained organic layer is washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was purified by flash column chromatography (hexane-ethyl acetate Z2: 1) to obtain 4.59 g of the title compound (Table-1, o. 61).

Example 10

 Ethinole N- [4-chloro-5- (4-chloro-6,7-dihydro-5H-cyclopenta [c] pyridazin-3-yl) -2-fluorophenyl] capitarum

4-chloro-3- (5-amino-4-cyclo-2--2-fluorophenyl) -6,7-dihydro-5H-cyclopentene [c] pyridazine 1.50 g, ethyl ethyl formate 0. A 57 g pyridine solution (15 mL) was stirred for 8 hours. The reaction mixture was extracted with ethyl acetate, and the organic layer was washed successively with a 1N aqueous hydrochloric acid solution, a saturated aqueous sodium bicarbonate solution and a saturated saline solution, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was purified by flash column chromatography (hexane-ethyl acetate 2: 1) to obtain 1.10 g of the title compound (Table-1, No. 63). Example 1 1

N- [4-chloro mouth-5- (4-chloro mouth-6,7-dihydro-5H-cyclopenta [c] pyridazine-3-yl) -2-fluorophenyl] -N-propargyl force Rubama

 0.12 g of sodium hydride was washed with hexane, and after removing oil, it was suspended in 5 mL of dimethylformamide. In the solution, ethyl N- [4-chloro-5- (4-chloro-6-7-dihydro-5H-cyclopenta [c] pyridazin-3-yl) -2-fluorophenyl] After adding 1.0 g of olebamate and stirring at room temperature for 30 minutes, 0.35 g of propargyl promide was added and the mixture was further stirred for 2 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with a saturated aqueous solution of ammonium chloride, a saturated aqueous solution of sodium bicarbonate, and a saturated saline solution, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was purified by flash column chromatography (hexane-ethylamine 2: 1) to obtain 0.75 g of the title compound (Table-1, No. 68).

Example 1 2

 N- “4-chloro-5- (4-chloro-6-7-dihide-5H-cyclopenta [^ pyridazine-3-yl) -2-fluorophenyl] propanesulfonamide

4-Chloro-3- (5-amino-4-chloro-2-fluorophenyl) -6 7-dihydro-5H-cyclopenta [c] pyridazine 3.00 g n-propanesulfonyl chloride 2.10 g, A solution of 1.6 g of lysine in 20 mL of methylene chloride was stirred for 7 hours. The reaction mixture was extracted with ethyl acetate, and the organic layer was washed successively with a 1N aqueous hydrochloric acid solution, a saturated aqueous sodium hydrogen carbonate solution and a saturated saline solution, dried over anhydrous sodium sulfate, filtered and concentrated. The crude product was purified by flash column chromatography (hexane-ethyl acetate Z2: 1) to give the title compound. (Table-1, No. 64) 2.95 g was obtained.

Example 13

 N- [5- (4-chloro-6,7-dihydro-5H-cy ^ penta [c] pyridan-3-yl) -4--4-ano-2-fluorophenyl] ethanesulfonamide

N- [4-bromo-5- (4-chloro-6,7-dihydro-5H-cyclopenta [c] pyridazine-3-yl) -2-fluorophenyl] ethanesulfonamide 3.69 g, cyan Heat 10 mL of a solution of copper chloride 0.91 in dimethylformamide under reflux for 2.5 hours. Then, the mixture is cooled to room temperature, an aqueous solution of iron chloride (3.5 g of FeCl ₃ , 4 mL of water) is added, and the mixture is further stirred at room temperature for 20 minutes. Water was added to the reaction mixture, and the mixture was extracted three times with ethyl acetate. The obtained organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was purified by flash column chromatography (hexane-ethyl acetate Z2: 1) to obtain 0.32 g of the title compound (Table-1, No. 86).

Example 14

 4-Chloro-3- (4-chloro-2-fluoro-5-cyclopentyloxyphenyl) -6, m-hydroxy-2-oxy- [5H] -cyclopentene [c] pyridazine

4-chloro-3- (4-chloro-2-fluoro-5-pentyloxyphenyl) -6,7-dihydro-1H-cyclopenta [c] pyridazine 1.12 g, m-chloro A solution of 0.90 g of perbenzoic acid (mCPBA) in 10 mL of chloroform was stirred at room temperature for 3 hours. 15 mL saturated aqueous sodium bicarbonate Was added to terminate the reaction. The reaction mixture was extracted with ethyl acetate, and the obtained organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, filtered, and concentrated. Flash column chromatography of crude product (hexane-ethyl acetate)

/ 1: 1) to give 0.52 g of the title compound (Table-1, No. 93).

Example 15

 4-chloro-3- (4-chloro-2-fluoro-5-cyclopentyloxyphenyl) -6,7-dihydro- [5H] -cyclopenta [c] pyridazine hydrochloride

4-chloro-3- (4-chloro-2-fluoro-5-cyclopentyloxyphenyl) -6,7-dihydro-1H-cyclopenta [c] pyridazine 0.60 g of 5% hydrochloric acid The methanol solution (2.00 g) was stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure, and the obtained crystals were filtered. The crystals were washed with hexane and dried to obtain (Table-1, No. 88) 0.59.

Other compounds described in Tables 1 to 5 can also be produced according to any of the methods of Examples 1 to 15. The structure of the obtained compound was confirmed by all various spectra. Table 16 shows the physical properties of the compounds described in Tables 1 to 5 and spectral data.

table 1

Rem 4½

XYZR 'R ² R ³ No.

1 CI H CI-(CH ₂ ) ₃ --H

2 CI H CI-(CH ₂ ) ₄ --H

3 CI F CI-(CH ₂ ) ₃ --H

4 CI F CI-(CH ₂ ) ₄ --H

5 CI CI CI-(CH ₂ ) ₃ --H

6 CI F Br-(CH ₂ ) ₃ --H

7 Br F. CI-(CH ₂ ) ₃ --H

8 CI F CI-(CH ₂ ) ₃ --N02

9 CI F CI-(CH ₂ ) ₄ --N02

 1 U 1 1 1 '2 ノ 3 -ΜΠ

 1 1 CI F Br -fCH 4) NO 3--N02

1 2 CI F CI-(CH

1 3 CI F CI - (CH 2) 3 - -0-C 2 H s

_{1 CI F CI - (CH 2} ) 3 - -0-nC 3 H 7

1 5 CI F CI - (CH 2) 3 - -0 - / - C 3 H 7

1 6 CI F CI - (CH 2) 3 - -0-sec-C 4 H 9

1 7 CI F CI - (CH 2) 3 - -0 - / - C 4 H 9

1 8 CI F CI-(CH ₂ ) _3-

1 9 CI F CI "(CH ₂ ) _3-

2 0 CI F CI-(CH ₂ ) ₃ --O-Allyl

2 1 CI F CI - (CH 2) 3 - -0-CH 2 C (CH 3) = CH 2

S 9

6Z0 / 86JfAi: W 9 10/66 OAV 9 9

_Sl ^y , M ri XH

 ϋ

^ 6Z0 / 86dfAL:> d [9 10/66 OAV

Compound

XYZR ² R ' ³

No.

6 1 CI F CI-(CH ₂ ) ₃ --H -H

6 2 CI F CI-(CH ₂ ) ₃ --H -C0 ₂ CH ₃

6 3 CI F CI-(CH ₂ ) ₃ --H -C〇 ₂ C ₂ H _S

6 4 CI F CI-(CH ₂ ) ₃ --H -S0 ₂ C ₂ H _s

6 5 CI F CI-(CH ₂ ) ₃ --H -S0 ₂ nC ₃ H ₇

6 6 CI F CI-(CH ₂ ) ₃ --H -S0 ₂ nC ₄ H ₉

6 7 CI F CI-(CH ₂ ) ₃ --Propargyl -C0 ₂ CH ₃

6 8 CI F CI-(CH ₂ ) ₃ --Propargyl -C0 ₂ C ₂ H _s

6 9 CI F CI - (CH 2) 3 - -Bn -C0 2 C 2 H s

7 0 CI F CI-(CH ₂ ) ₃ --/-C ₃ H ₅ -S0 ₂ nC ₃ H ₇

7 1 CI F CI "(CH ₂ ) ₃ --Propargyl -S. ₂ C ₂ H ₅

7 2 CI F CI-(CH ₂ ) ₃ --Propargyl -S0 ₂ nC ₃ H ₇

7 3 CI F CI-(CH ₂ ) ₃ --Propargyl -S0 ₂ nC ₄ H ₉

7 4 CI F CI - (CH 2) 3 - -CH 2 OC 2 H s -S0 2 nC 4 H 9

7 5 CI F CI-(CH ₂ ) ₃ --S0 ₂ CH ₃ -S0 ₂ CH ₃

7 6 CI F CI-(CH ₂ ) ₄ --H -H

7 7 CI F CI-(CH ₂ ) ₄ --H -C0 ₂ C ₂ H _s

7 8 CI F CI-(CH ₂ ) ₄ --H -S0 ₂ nC ₃ H ₇

7 9 CI CI CI-(CH ₂ ) ₃ --H -H

8 0 CI CI CI-(CH ₂ ) ₃ --H -C0 ₂ C ₂ H _s 01436

3 (continued)

Compound

XYZR ¹ R ² R ' ²

 No.

8 1 CI CI CI-(CH ₂ ) ₃ --H -S0 ₂ C ₂ H _s

8 2 CI CI CI - (CH 2) 3 - -CH3 -C0 2 C 2 H s

8 3 CI F Br-(CH ₂ ) ₃ --H -H

8 4 CI F Br - (CH 2) 3 - -H -S0 2 C 2 H s

8 5 CI F CN-(CH ₂ ) ₃ --H -H

8 6 CI F CN-(CH ₂ ) ₄ --H -S0 ₂ C ₂ H _s

Table-4

Table-5

-6 Physical Properties Table

Table-6 Physical Properties Table (Continued)

Compound

 Physical properties H-NMR (6, ppm / CDCb) IR (cm, VKBror NaCI)

No.

 10.40 br), 7.45 (IH, d, J = 6.3 Hz), 7.20

 (IH, d, 7 = 9.3 Hz) .3.41 (2H.t, J = 7.8 Hz).

 12 m.p.> 300 "C 1423, 1191, 810.

 3.12 (2H.1, J = 15 Hz), 2.29 (2H, qui, J = 7.8

 Hz).

 7.25 (IH, d, 7 = 8.4 Hz), 7.06 (IH.d, 7 = 6.0

 Hz) .4.12 (2H.¾ J = 7.0 Hz), 3.37 (2H, t, J-

13 Glassy

 7.8 Hz) .3.12 (2H, t, 7 = 7.5 Hz) .2.22-2.33

 (2H, m), 1.47 (3H, t, 7 = 7.0Hz).

 7.25 (IH, 4 ^ = 9.0 Hz), 7.06 (IH.d> zo = 6.3

 Hz), 4.00 (2H.t, J = 6.5 Hz), 3.37 (2H, t, J =

 14 m.p. 68.2-70.1'C 7.8 Hz), 3.12 (2H, t, 7 = 7.5 Hz), 2.22-2.33

 (2H.m), 1.80-1.92 (2H.m), 1.06 (IH, t. / =

 73 Hz).

 7.25 (IH, d> Z = 9.3 Hz) .7.09 (IH, d, J = 6.6 2980, 1740, 1610, 1585.Hz) .4.53 (IH, scp, J = 6.3 Hz), 3.37 (2H, t, J 1490, 1420, 1370, 1310.

15 viscous

 3.12 (2H, t, J = 7.5 Hz). 2.27 (2H, 1245. 1190, 1110, 1055, qui, J = 7.8 Hz), 138 (6H, d, J = 63 Hz). 1000 , 938.915, 850, 800.

7.25 (IH.d, 7 = 9.6 Hz), 7.07 (IH, d, J = 6.0

 Hz), 432 (IH, tq, J = 6.0, 6.0 Hz), 337 (2H, t,

 J = 7.8 Hz), 3.12 (2H, t, zo = 7.8 Hz), 2.28 2980, 1750, 1491, 1421,

16 viscous

 (2H, qui, zo = 7.8 Hz), 1.88-1.64 (2H, m) .1370, 1242, 1190.

 1.33 PH.d, J = 6.0 Hz), 1.00 βΗ. I. J = 6.0

 Hz).

 7.25 (IH, J = 9.0 Hz) .7.05 (IH.d, i = 6.0

 Hz), 3.80 (2H, d, J = 6.6 Hz), 3.37 (2H, t, 7 =

 17 Viscosity 7.8Hz), 3.11 (2H, t, J = 7.5 Hz), 2.22-2.32

 (2H, m), 2.07-2.24 (IH, ra), 1.05 (6H, d, J

 = 6.9 Hz).

 7.24 (IH.ά, J = 9.0 Hz) .7.05 (IH.d, 7 = 6.3

 2970, 1740, 1610, 1580.Hz), 4.80 (IH.m), 3.37 (2H, t, 7 = 7.8 Hz),

 18 m.p. 86.0-86.2 "C 1055, 1000, 970, 918.

 3.12 (2H.t, J = 7.5 Hz), 2.27 (2H.qui, J = 7.8

 860.810.

 Hz), 1.98-1.80 (4H.m) .1.75-1.59 (2H, m).

 7.24 (IH.d, ^ = 9.0 Hz), 7.08 (IH, d, = 6.3

 Hz) .4.33-4.19 (IH, m), 3.37 (2H, t, 7 = 7.8

 19 m.p. 104. 1-105.8 'C

 Hz) .3.1 1 (2H, t.J = 7.5 Hz), 2.27 (2H.qui, J =

7.8 Hz), 2.00-1.35 (11H, m). Table-6 Physical Properties Table (Continued)

Compound

Physical Properties ¹ H-NMR (6, ppm / CDCb) IR (v.cm'VKBror aCI)

 7.26 (IH, d, 7 = 8.7 Hz), 7.06 (ia d, 7 = 6.0

 Hz), 6.00-6.13 (IH, m), 5.29-5.50 (2H, m).

 20 76.9-77.4'C

 4.61-4.64 (2H.m) .3.37 (2H, t, zo = 7.8 Hz).

 3.12 (2H, t, 7 = 7.5 Hz), 2.22-233 (2H, m).

 21 80.7-81.9'C

 7.25 (IH.d, 7 = 8.7 Hz), 7.09 (IH.d, 7 = 2.0

 Hz), 5.51 (IH, 6.3 Hz), 5.08 (IH, t.i =

 2975, 2930, 1495, 1422, 6.0 Hz), 4.62 (2H, d, 7 = 6.3 Hz), 3.38 (2H, t,

 22 Viscosity adjustment 1375, 1262, 1190, 1059.

 = 7.8 Hz), 3.12 (2H, t, J = 7.5 Hz), 2.28 (2H,

 974 »

 ί, zo = 7.8 Hz), 2.18-2.05 (4H, m) 1.71 (3H,

 s), 1.67 (3H.s), 1.60 (3H, s).

 7.28 (IH, d, ^ = 9.6 Hz), 7.24 (IH, d, = 6.3

 1

 Hz), 4.79 (2H, d, 7 = 2.4 Hz), 3.38 (2H, t, zo =

 23 m.p. 161.6-162.3'C 1390. 1375, 1364, 1195,

 7.8 Hz), 3.12 (2H, 7.8 Hz), 2.54 (IH, t.

 872, 828.

 = 2.4 Hz) 2.26 (2H, qui. = 7.8 Hz).

 7.32 (IH, d.7 = 6.3 Hz), 7.27 (IH, d, J = 9.0

 Hz), 4.88 (IH, dq, 7 = 1.8, 6.6 Hz), 3.38 (2H,

 3170, 2115. 1495, 1421,

24 m.p. 11S.2- 119.8 * C t, = 7.8 Hz), 3.12 (2H, t, 7 = 7.5 Hz), 2.50

 1193,865,803.

 (IH, d.J = 1.8 Hz), 2.28 (2H, qui, J = 7.8 Hz),

 1.73 (3H, d, J = 6.6 Hz).

 7.27 (IH, d, / = 9.0 Hz), 7.21 (IH, d, 7 = 6.0

 Hz), 3.38 (2H, t, J = 7.8 Hz), 3.12 (2H, t, zo =

 25 m.p. 117.6- 118.5'C

 7.5 Hz), 2.23-2.33 (2H, m), 1.84 (3H, t,

 2.1 Hz).

 7.26 (IH, d, i = 8.7 Hz), 7.09 (IH, d, i = 6.0

 Hz). 4.69 (2H, d, J = 47.1.5.7 Hz) 4.18 (2H.t.

 26 m.p. 102.7-103.3'C

 J = 6.0 Hz) .3.37 (2H, t, J = 7.8Hz) .3.12 (2H, t,

 (J = 7.5 Hz) 2.14-233 (4H.m).

 7.28 (IH, d, J = 9.0 Hz), 7.08 (IH, d, 7 = 6.0

 Hz), 5.67 (IH, dt), 5.47 (IH, d) .4.65 (2H, d).

 27 m.p.1J8.1-118.7'C

 3.37 (2H.t, zo = 7.8 Hz), 3.12 (2H, t = 7.5 Hz.)

, 2.22-2.33 (2H, m). Physical property table (continued)

Compound

Physical Properties ¹ H-NMR (6, ppm / CDCb) IRiv.cm-V Br a a)

No.

 7.31-7.48 (6H.m), 7.15 (IH, d, 7 = 6.3 Hz).

 28 m.p. 104.8-105.4 'C 5.15 (2H.s) .337 (2H, t.J = 7.8 Hz) .3.11 (2H.

 t, 7 = 7.5 Hz) .2.22-232 (2H, m).

 7.26 (IH, d, 7 = 9.3 Hz), 7.02 (IH, d, = 6.0

 Hz), 4.95 (IH, m), 4.03-3.39 (4H, m) 3.38

 29 m.p. 144.0-145.5 'C

 C2H.t, J = 7.8 Hz), 3.12 (2H, t. 7 = 7.5 Hz),

 2.28 (2H, qui, J = 7.8 Hz), 2.25-2.13 (2H, m).

 7.25 (IH, d, 7 = 9.0 Hz), 7.09 (IH.d, 7 = 6.3

 Hz), 4.29-4.37 (IH.m), 4.05 (H, d, 7 = 4.5

 30 126.8-127.5 'C Hz), 3.80-3.99 (2H, m), 3.37 (2H, t, J = 7.8

 Hz), 3.11 (2H, t, zo = 7.5 Hz), 2.22-2.32 (2H,

 m), 1.81 -2.15 (4H, m).

 7.30 (IH, d, J = 9.0 Hz), 6.95 (IH, d, 7 = 6.0

 Hz), 4.65 (IH, q, J = 6.9 Hz), 3.37 (2H.t, J =

 31 viscous

 7.8 Hz), 3.11 (2H, t.7 = 7.5 Hz) 2.29 (3H.s),

 2.22-233 (2H, m), 1.54 (3H, d, J = 6.9 Hz).

 7.42 (IH, d, 7 = 6.3 Hz), 7.27 (IH, d, 7 = 9.0

 Hz), 4.96 (IH.t, J = 7.6 Hz), 4.52-4.60 (1H,

 32 glassy m), 4.31-4.39 (IH, m), 3.37 (2H, t, 7 = 7.8

 Hz), 3.11 (2H, t, J = 7.5 Hz), 2.54-2.80 (2H,

 m), 2.22-233 (2H, m).

 7.33 (IH, d, J = 6.0 Hz), 7.20 (IH, d = 9.0 2970, 1738, 1615, 1585, Hz), 3.41 (IH.q, J = 6.6 Hz), 3.38 (2H.I, J = 1492, 1420, 1370, 1260,

33 viscous

 995, 7.8 Hz), 3.12 (2H, t, J = 7.5 Hz), 2.26 (2H, 1190, 1093, 1060, 1040, qui, J = 7.8 Hz), 1.86 (3H, d, zo = 6.6 Hz). 910, 870, 812.

 7.32 (IH, d, 7 = 6.6 Hz), 7.31 (IH, d, 7 = 8.4

 Hz), 4.80 (IH, t, J = 6.0 Hz), 3.38 (2H.t, zo D =

 34 Viscosity 7.8 Hz), 3.13 (2H, t, J = 7.5 Hz), 2.86 (2H,

 sep, J = 7.5 Hz), 2.17 (2H.dq, J = 7.5, 7.5

 Hz), 1.24 (3H.t, J = 7.5 Hz).

 7.44 (IH, d, i = 6.6 Hz), 7.20 (IH, d, J = 9.3

 35 m.p. 205 C dec.Hz), 3.25 (2H, t, JO = 5.7 Hz), 2.89 (2H.t, i =

 5.7 Hz) .2.00- 1.85 (4H, m).

 2950, 1615, 1555, 1500.

7.24 (IH, d, J = 9.0 Hz), 7.08 (IH, d, J = 6.3

 1430, 1379, 1295, 1260, Hz), 4.52 (IH, sep, J = 6.3 Hz), 3.21 (2H, t, J

 36 m.p. 104.0-104.8'C 1190, 1140, 1110, 1090,

 = 5.7 Hz), 2.88 (2H, t, J = 5.7 Hz) .2.00-1.85

 1062, 1027, 983, 959, (4H, m), 1.38 (6H, d, J = 6.3 Hz).

931,855,798,759.

Table-6 Physical Properties Table (Continued)

Compound

Physical Properties ¹ H-NMR (6, ppm / CDCl3) IR (v, cm "VKBr or NaCI)

No.

 7.53 (IH, s), 7.19 (IH.s), 4.87 (IH.d¾ 7 =

 3185, 2110, 1585, 1478, 1.8.6.6 Hz). 3.39 C2H, t, J = 7.8 Hz), 3.12

 1418.1360, 1321, 1245.

45 m.p. 148.8-150.3 'C (2H.t, J = 7.8 Hz). 2.49 (IH.d./ = 1.8 Hz),

 1148.1088, 1035, 932. 2.29 (2H, ςμί, 7 = 7.8 Hz), 1.73 (3H, d, 7 =

 870, 738.

 6.6 Hz).

 7.60 (IH.s), 7.19 (IH, s), 4.91 (IH, q. = 6.9

 Hz), 3.40 (2H.t, J = 7.8 Hz), 3.13 (2H t, Z = 1480, 1412, 1237.1150,

46 m.p. 146.2-148.9 'C

 2.29 (2H, qtri, J = 7.8 Hz), 1.86 (3H, 1095.

 d, J = 6.9 Hz).

 10.17 (IH.br), 7.43 (IH.s), 7.21 (IH, s), 3.26 2955, 1742, 1593.1516,

47 m.p. 165.1-167.0 'C (2H, m), 2.94-2.80 (2H, m), 2.00-1.85 (4H, 1420. 1350, 1083, 898, m) .858.

 7.51 (IH, s), 6.96 (IH, s) .4.54 (IH, sep, J =

 6.0Hz), 3.25-3.15 (2H, m), 2.92-2.85 (2H.

 48 viscous

 m), 2.00-1.85 (4H, m). 1.38 (6H.d, J =

 6.0Hz).

 7.53 (IH, s). 7.19 (IH, s), 4.86 (IH, dq, / =

 3185, 2950, 2115, 1505.1.5, 6.6 Hz). 3.24 (2H.t, J = 5.4 Hz), 2.88

 49 m.p. 181.2-183.3 * C 1480, 1418, 1324, 1248,

 (2H.m), 2.49 (IH, d> Z = 1.5 Hz), 2.00-1.85

 1220, 1089, 1036, 872. (4H, m), 1.72 (3H, d, J = 6.6 Hz).

 7.38 (IH, d> Z = 6.6 Hz), 7.18 (IH, d> Z = 9.0 Hz)

 50 m.p.> 300 * C Hz), 3.43 (2H, t, J = 7.8 Hz), 3.09 (2H, t, ZO =

 7.5 Hz), 2.28 (2H, qui, J = 7.8 Hz).

 7.24 (IH.d, 7 = 6.3 Hz), 7.05 (IH.d, 7 = 6.3

 2990, 1495, 1418, 1368, Hz), 4.52 (IH.sep.J = 6.0 Hz), 3.40 (2H, t, zo =

 51 Viscosity 1250, 1190, 1108, 933,

 7.8 Hz), 3.08 (2H.i, J = 7.5 Hz), 2.27 (2H, qpi.

 902.879, 850, 798.J = 7.8 Hz), 1.38 (6H, ά, J = 6.0 Hz).

 7.23 (IH, d, i = 8.7 Hz) .7.01 (IH, d, 7 = 6.3

 Hz), 4.79 (IH, m), 3.40 (2H, t, i = 7.8 Hz), 3.08

 52 Viscosity adjustment

 (2H.i, J = 7.5 Hz), 2.27 (2H, qui, zo = 7.8 Hz),

 1.95-1.55 (8H.m).

 7.27 (IH, d, i = 8.4 Hz), 7.20 (IH, d, 7 = 6.3

 3225, 2130, 1500, 1422, Hz), 4.79 (2H, d, ^ = 2.1 Hz), 3.41 (2H, t, zo =

 53 m.p. 161.0-163.0 'C 1390, 1263, 1195, 870.

 7.8 Hz), 3.09 (2H, t. 7 = 7.5 Hz) .2.54 (IH, t, J

 Nu 3.

= 2.1 Hz), 2.27 (2H.qui, J = 7.8 Hz).

Table-6 Physical Properties Table (Continued)

Compound

 Physical properties π-NMH (o, ppm DCI3) IR (v, cm * VKBr or aCI)

No.

 7.15 (ia d, = 9.0 Hz) .6.91 (1H.d.7 = 6.3 3450, 3325, 3200, 1632, Hz), 4.01 (2H, br), 3.36 (2H> t, J ~ 7.8 Hz), 1608 , 1598. 1500, 1440.

61 m.p. 174.6-174.9'C

 3.10 (2H.t, J = 7 Hz), 2.26 (2H.qui.J = 7.8 1380.1200, 1050.992.Hz) .880.870, 808.

 8.33 (1H, d, / = 6.6 Hz), 7.26 (1H, d, 7 = 8.7

 3260, 1742, 1538, 1436, Hz). 7.10 (1H, br), 3.79 (3H.s), 3.38 (2H, t.J

 62 m.p. 173.0-174.5 * C 1368, 1281, 1250, 1237,

 = 7.8 Hz), 3.11 C2H, q.J = 7.5 Hz), 2.27 (2H,

 1080, 891, 558.

 qui, 7 = 7.8 Hz).

 o.J.) 1 il, a, J =: t} .y HZ), I.o (In, a, J = K.4

 Hz), 7.06 (1H, br), 4.23 (2H, q, J = 7.2 Hz),

 63 m.p. 13 & 4-138.8 * C 3.37 (2H.t, / = 7.8 Hz) .3.11 (2H.q, ZO = 7.5

 Hz). 2.27 (2H, qui, J = 7.8 Hz), 132 (3H.t,

 J = 7.2 Hz).

 ΙΛΔ ltl, a, J = o.J tiZ), l.iJ. (1H, d, J = o. /

 Hz), 6.82 (1H.br), 3.36 (2H, t, J = 7.8 Hz),

 3100, 1500, 1430, 1340,

64 m.p. 145.9-148.7 * C 3.19 (2H, q. 7 = 7.5 Hz), 3.12 (2H, t, zo = 7.8

 1155, 910.

 Hz), 2.29 (2H, qui, 7 = 7.8 Hz), 1.41 (3H, t.

 = 7.5 Hz).

Hz). 6.80 (1H.br), 3.38 (2H.J = 7.8 Hz),

 65 m.p. 132.7-133.6 ° C 3.12 (4H.q, J = 7.5 Hz). 2.28 (2H, qui, J =

 (7.8 Hz), 1.88 (2H, tq, J = 7.5, 7.2 Hz), 1.05

 (3H, t, = 7.2Hz).

Hz). 6.78 (1H, br), 3.38 (2H.t, Z = 7.8 Hz), 3080, 2970, 2945, 2885,

66 m.p. 173.0-173.5 * C 3.16-3.09 (4H, m), 2.28 (2H, qui, 7 = 7.5 1500, 1421, 1350, 1338,

 1.82 (2H, U J = 7.5, 7.5Hz L44 (2H, lq, 1 158, 917, 858, 560, 493. J = 7.5, 7.5 Hz), 0.92 (3H, tq, J = 7.5 Hz).

 Hz), 4.79 (1H, cM, J = 17.7, 2.1 Hz), 4.09 (1H, 1490, 1450, 1430, 1380,

67 m.p. 122.7-123.2 'C di 7 = 17.7, 2.1 Hz), 3.70 (3H.s), 3.38 (2H.t, 1294, 1240, 1193. 1 138,

 J = 7.8 Hz), 3.12 (2H.q, J = 7.5 Hz), 2.28 1091, 1002, 973, 901, (2H.qui, 7 = 7.8 Hz), 2.17 (IH.t, = 2.1 Hz). .

 7.58 (1H, d, 7 = 6.9 Hz), 7.35 (1H, ά, J = 9.0

 Hz), t¾.73 (1H, d, J = 17.4Hz), 4.30-4.06

 68 m.p. 134. 1-135.4 'C QH, m). 3.38 (2H, I, J = 7.8 Hz), 3.12 (2H, q,

 J = 7.5 Hz), 2.28 (2H, qui, 7 = 7.8 Hz). 2.17

(lH.t. = 2.1 Hz), 1.18 (3H, t. 7 = 6.9 Hz). Table- B Physical properties table (continued)

Compound

Physical Properties ¹ HNR (6, ppm / CDCb) IR (v.cm'VKBror NaCI)

No.

 U ^ lrl, a, «= .J /. D ^ H« S, /.Uo

 (IH.d, 7 = 6.9 Hz), 5.16 (IH, d, 7 = 14.7 Hz),

 4.42 (IH, d, J = 14.7 Hz), 4.30-4.06 (2H, m).

 69 viscous

 3.35 (2H, t. 7 = 7.8 Hz), 3.08 (2H, q, 7 = 7.5

 Hz). 2.26 (2H, qui. 7 = 7.8 Hz), 2.17 (IH, t, J

 = 2.1 Hz). 1.17 (3H, l, J = 6.9 Hz).

 7.57 (IH, d. 7 = 6.9 Hz), 7.39 (IH, d. 7 = 9.0

 Hz) .4.41 (IH, sep, J = 6.6 Hz), 3.38 (2H.t, 7

 2980.1612, 1490, 1410, = 7.8 Hz), 3.21-3.22 (4H, m), 2.28 (2H.qn,

 70 Amorphous solid 1367. 1340, 1159, 111 ?,

 J = 7.5 Hz) .2.00-1.88 (2H, m) .134 (3H.d,

 1027, 895, 750.

 J = 6.6Hz), 1.22 PH, d, J = 6.6Hz), 1.06 C3H,

 t, J = 7.5Hz).

 7.78 (IH, 4Z = 7.2 Hz), 7.39 (IH, d, = 8.7 3280, 2980, 1738, 1617, Hz), 5.00-4.00 (2H, br), 3.38 (2H, t, J = 7.8 1590. 1492, 1420, 1350,

3.24 (2H, q, J = 7.2 Hz), 3.13 (2H.q, 7 = 1190, 1155. 1092, 1051, 71 amorphous solid Hz).

 7.2 Hz), 2.36 (IH, t, J = 2.1 Hz). 2.29 (2H. 920, 858, 729.

 qui, J = 7.8 Hz), 1.47 (3H, t, J = 7.2 Hz). 502:

 One H 7 — ゥ PV \ 7 7 _ on

 Hz), 4.80-4.10 (2H, br), 3.38 (2H.t, 7 = 7.8

 72 Viscosity Hz), 3.38-3.10 (4H, m), 2.36 (IH.t, J = 2.1

 Hz), 2.29 (2H, qui, J-7.8 Hz). 1.96 (2H, tq, J

 = 7.5, 7.5 Hz), 1.07 (3H, t, J = 7.5Hz).

 7.78 (IH, d, 7 = 6.9 Hz), 7.39 (IH, d, J = 9.0

Hz), 3.23-3.20 (2H.m), 3.13 (2H, t, zo = 7.5

 3030, 1495, 1421, 1358,

73 viscous Hz), 2.36 (IH, l, J = 2.1 Hz), 2.29 (2H.qai, J

 1220, 1 158, 760.

 = 7.5 Hz), 1.89 (2H.tt, J = 7.5, 7.5Hz), 1.47

 (2H.tq, i = 7.5, 7.5 Hz), 0.95 (3H, tq, J = 7.5

 Hz).

 7.70 (IH.d_z = 7.2 Hz). 7.38 (IH.d.J = 8.7

 Hz), 5.24 (IH.br), 4.82 (IH, br), 3.66 (2H, br),

 3.36 (2H, t, J = 7.8 Hz), 3.17-3.08 (4H, m) .2980, 1740, 1610, 1490,

74 viscous

 2.28 (2H, qui, = 7.5 Hz), 1.96-1.70 (2H, 1420, 1350, 1200, 1160.m). 1.20 (2H, t, 7 = 7.2 Hz), 1.06 (3H, t, ZO =

7.5Hz). Table-6 Physical Properties Table (Continued)

Table-6 Physical Properties Table (Continued)

Compound

Physical properties ¹ H-NMR (6, ppm / CDCb) IR (v, cm-VKBror aCI)

No.

 7.22 (IH, d.7 = 8.4 Hz), 6.90 (IH.d, 7 = 5.7

 3435, 3355, 3250.2225, Hz), 4.45 (2H.br). 3.36 (2H, t, J = 7.8 Hz).

 0 m.p. 1 0.0-1 / 8.O 1640, 1503, 14 <M, 1435,

 3.12 (2H, t.y = 7.5 Hz) 2.28 (2H, qui, J = 7.5

 1385, 890, 520, 420.Hz)

 7.87 (IH, d, 7 = 6.0 Hz), 7.46 (IH, d, J = 8.1

 3070, 2225, 1590, 1518, Hz), 3.41 (2H, t, 7 = 7.8 Hz), 3.27 (2H, q, J =

 06 m.p. 174.0- 176.0 then 1430, 1335, 1155, 908,

 7.5 Hz), 3.14 (2H, t. 7 = 7.5 Hz), 2.30 (2H,

 509.

 qui, J = 7.5 Hz), 1.46 (3H.t, zo = 7.5 Hz).

 7.29 (IH.d, = 9.3 Hz), 7.15 (IH.d, 7 = 5.1

 3400, 2990, 2350, 1980, Hz), 4.54 (IH, sep, J = 6.0 Hz), 3.82 (2H, t, J =

 Q m.p.65.0-67.0 "C

 f 149, 1422, 1190, (60.0 · <: moisture absorption 7.5 Hz), 3.34 (2H, t, zo = 7.5 Hz), 2.52 (2H,

 1112 »948, 860, 800.qui, = 7.8 Hz), 137 (6H, d, J = 6.0 Hz).

 7.28 (IH, d, 7 = 8.4 Hz), 7.09 (IH, d, J = 6.0

 3450, 2970, 2350, 1990, m.p. 96.0-98.0 'C Hz), 4.77 (lH> m), 3.81 (2H, t, zo = 7.8 Hz), 333

 88 1498, 1420, 1260, 1192, (absorb moisture at 89.0 'C) (2H.t, zo = 7.5 Hz), 2.51 (IH, t.zo = 2.1 Hz),

 1163, 880.

 1.95- 1.58 (8H, m).

 (δ, ppm 1 DMSO- ^): 9.80-9.00 (2H, br), 8.43

 (IH, d.7 = 6.6 Hz). 8.11 (IH, d. J = 9.6 Hz).

 89 m.p. 172.2-173.1 "C

 3.28 (2H, t, Z = 7.5 Hz), 3.09 (2H, l, J = 7.8

 Hz), 2.18 (2H, qui, J-7.5 Hz).

 (δ, ppm / DMSO-ds): 8.43 (IH, d.J = 6.9 Hz),

 90 m.p. 214.4 -215.1 * C 8.11 (IH, d, J = 8.7 Hz), 3.11 (2H.m), 2.84

 (2H, m), 2.48 (4H, m).

 (6, ppm / D SO-4): 8.38 (IH, d, J = 6.6 Hz),

 8.22 (IH, d, 7 = 9.3 Hz), 3.28 (2H.t, J = 7.5 1430, 1620, 1540, 1490,

91 m.p. 149.2-150.8 'C

 Hz), 3.09 (2H, t, 7 = 7.5 Hz), 2.18 (2H, qui, J 1373, 1222, 970, 891. = 7.5 Hz).

 7.24 (IH, d, 7 = 9.0 Hz), 7.01 (IH, d, 7 = 6.6

 Hz), 4.52 (IH, sep, J = 6.0 Hz) 3.28 (2H, t, zo = 1550, 1500, 1427, 1350,

92 m.p. 101.6-102.8 'C

 7.8 Hz), 3.18 (2H, t, J = 7.5 Hz), 2.32 (2H. 1188, 1103, 852.

 qui, J = 7.8 Hz), 1.37 (6H, d, J = 6.0 Hz).

3450, 2980, 1560 ₍ 1550,

7.23 (IH.d. = 9.0 Hz), 6.97 (IH, d, J = 6.3

 1500, 1435.1370, 1340, Hz), 4.78 (lH_m), 3.29 (2H, t, zo = 7.8 Hz) 3.17

 93 m.p. 161.5-163.0 'C 1315, 1265, 1192, 1170,

 (2H, t, J = 7.5 Hz), 2.32 (IH, t, J = 2.1 Hz),

1045, 973, 908, «60. 1.95- 1.58 (8H, m). Next, Formulation Examples of the compound of the present invention are shown. Hereinafter, "parts" and "%" mean "parts by weight" and "% by weight", respectively.

Formulation Example 1 wettable powder

 40 parts of the compound of the present invention described in Tables 1 and 2; Carblex # 80 (trade name, Shionogi & Co., Ltd.) 20 parts; Riki Olin clay (trade name, Tsuchiya Kaolin Co., Ltd.) 35 parts; and higher alcohol sulfates After 5 parts of Solbor 8070 (trade name, Toho Chemical Co., Ltd.) surfactant was blended, the mixture was uniformly mixed and pulverized to obtain a wettable powder containing 40% of active ingredient. Formulation Example 2 Emulsion

 After dissolving 20 parts of the compound of the present invention from the compounds described in Tables 1 to 5 in a mixed solvent consisting of 35 parts of xylene and 30 parts of N, N-dimethylformamide, the mixture was dissolved in a polyoxyethylene surfactant. 15 parts of Solpol 3005X (trade name, manufactured by Toho Chemical Co., Ltd.) to obtain an emulsion containing 20% of the active ingredient.

Formulation Example 3 Flowable

 8 parts of ethylene glycol and 5 parts of Solpol AC3020 (trade name, Toho Kagaku) premixed with 30 parts of the compound of the present invention described in Tables 1 to 5 are mixed with 0.1 part of xanthan gum and water. 56. After mixing and dispersing in 9 parts, the slurry mixture is wet-pulverized with a Dino Mill (trade name, Shinmaru Enterprises) to obtain the active ingredient.

A flowable containing 30% was obtained.

Formulation Example 4 Granules

 1 part of the compound of the present invention described in Tables 1 to 5, 1 part of clay (manufactured by Nippon Talc), 43 parts of bentonite (manufactured by Toyoko Yoko Co., Ltd.), 55 parts, and succinate surfactant Yearol CT-1 (trademark) 1 part), mixed and pulverized, and added 20 parts of water to make the mixture. Further, this was extruded from a hole having a diameter of 0.6 mm using an extrusion granulator, dried at 60 ° C for 2 hours, cut into 1-2 female lengths, and granules containing 1% of active ingredient were extruded. Agent was obtained.

Next, test examples of the compound of the present invention will be described.

Test example 1 Flooded soil treatment test

Fill an alluvial clay loam in a ²⁰⁰ cm2 resin pot, apply fertilizer, and add an appropriate amount of water. Weed seeds were mixed into a 0.5 cm layer from the soil surface, such as Nobie, Konagi, Kikashigusa and Firefly. After that, water was introduced, and the flooding depth was maintained at 3.5 cm.

 Weed seeding On the 5th day, dilute and adjust the flowable agent containing the compound of the present invention obtained in Formulation Example 3 as an active ingredient with water, and adjust the amount of the active ingredient to be 10 g per 1 are. Was dropped onto the flooded surface.

 After that, cultivation management was continued in the greenhouse, and the herbicidal effect was investigated on the 28th day after the chemical treatment. Table 7 shows the results. (The compound No. in Table 7 corresponds to the compound No. in Tables 1 to 5 in Tables 1 to 5.) The herbicidal effect was evaluated using the above-ground live weight of weeds in the treatment plot.

 1 X 100 = Y (%) The above-ground fresh weight of the weeds in the untreated plot was determined and expressed as the herbicidal effect coefficient according to the following criteria. Weeding efficiency coefficient Y (%

 0 0-5

 1 6 to 30

 2 3 5 5 0

 3 5 1 ~ 7 0

 4 7 1 to 9 0

5 9 1 to 1 0 0

Table 7

 Killing compound Active ingredient Herbicidal effect

 No. σ / a Nohe'e Konaki Kikasiku

1 10 5 5 5

 2 10 4 5 5

 3 10 5 5 5

 4 10 5 5 5

 5 10 5 5 5

 6 10 5 5 5

 7 10 5 5 5

 8 10 4 5 5 4

9 10 5 5 5 5

10 10 3 5 5 4

11 10 5 5 5 4

12 10 5 5 5 5

13 10 5 5 5 5

14 10 5 5 5 5

15 10 5 5 5 5

16 10 5 5 5 5

17 10 5 5 5 5

18 10 5 5 5 5

19 10 5 5 5 4

20 10 5 5 5 5

21 10 5 5 5 5

22 10 5 5 5 4

23 10 5 5 5 5

24 10 5 5 5

 25 10 5 5 5

 26 i n 5 5 5 ς i n 5 5 5

 28 i n 5 5

 20 i n 5 5 5

 30 in 5 5 5 5

31 10 5 5 5 5

32 10 5 5 5 3

33 10 5 5 5 5

34 10 5 5 5 5

35 10 5 5 5 5

36 10 5 5 5 5

37 10 5 5 5 5

38 10 5 5 5 5

39 10 5 5 5 5

40 10 5 5 5 4

41 10 5 5 5 5

42 10 5 5 5 5

43 10 5 5.5 .5 5

44 10 5 5 5 5

45 10 5 5 5 5 'Ki)

Test compound Active ingredient

 No. g / a Nohi'e Konaki, Kinkaku * Sa Firefly

46 10 5 5 5 5

47 10 5 5 5 3

48 10 5 5 5 5

49 10 5 5 5 5

50 10 5 5 5 3

51 10 5 5 5 5

52 10 5 5 5 5

53 10 5 5 5 5

54 10 5 5 5 5

55 10 5 5 5 5

56 10 5 5 5 5

57 10 5 5 5 5

58 10 5 5 5 4

59 10 5 5 5 5

60 10 5 5 5 5

61 10 5 5 5 5

62 10 5 5 5 5

63 10 5 5 5 5

64 10 5 5 5 5

65 10 5 5 5 5

66 10 5 5 5 5

67 10 5 5 5 5

68 10 5 5 5 5

69 10 5 5 5 4

70 10 5 5 5 5

71 10 5 5 5 5

72 10 5 5 5 5

73 10 5 5 5 5

74 10 5 5 5 4

75 10 5 5 5 5

76 10 5 5 5 5

77 10 5 5 5 5

78 10 5 5 5 5

79 10 3 5 5 4

80 10 4 5 5 4

81 10 3 5 5 5

82 10 4 5 5 3

83 10 5 5 5 5

84 10 5 5 5 5

85 10 5 5 5 5

86 10 5 5 5 5

87 10 5 5 5 5

88 10 5 5 5 5

89 10 5 5 5 5

90 10 5 5 5 5 Table 1 7 (continued)

 Test compound Active ingredient Herbicidal effect

 No. g / a Novier Konaki 'Kinkunk' Sa Firefly

91 10 5 5 5 4

92 10 5 5 5 5

93 10 5 5 5 4

Test example 2 Upland soil treatment test

A field of volcanic ash soil was filled in a resin bag with an area of 200 cm ² , and after fertilization, the soil was uniformly mixed with the seeds of weeds such as crabgrass, enocologza, shiroza, and oota, and Formulation Example 1 The wettable powder containing the compound of the present invention as an active ingredient obtained by the above was diluted with water and adjusted to obtain a treatment amount of the active ingredient of 10 g per are with a small power pressurized sprayer. Was sprayed uniformly.

 After that, cultivation management was continued in the greenhouse, and the herbicidal effect was investigated on the 28th day after the chemical treatment. The results are shown in Table-8. (The compound No. in Table 8 corresponds to the compound No. described in Tables 1 to 5.)

The evaluation of the herbicidal effect was expressed in the same manner as in the criteria of Test Example 1.

Table 1 8

 Test compound Active ingredient Herbicidal effect

 No, g / a ♦ ♦ ♦ ♦ ノ ノ ノ ゥ ゥ t

1 10 3 4 3 5

3 10 5 4 5 5

4 10 5 5 5 5

6 10 5 4 5 5

7 10 5 4 5 5

10 10 4 3 5 5

13 10 5 5 5

14 10 5 5 5 5

15 10 5 5 5 5

16 10 5 5 5 5

17 10 4 5 5 5

18 10 5 5 5 5

19 10 4 5 5 5

20 10 5 5 5 5

21 10 5 5 5 5

22 10 5 4 5 3

23 10 5 5 5 5

24 10 5 5 5 5

25 10 5 5 5 5

26 10 5 5 5 5

27 10 5 5 5 5

28 10 .5 5 5 5

29 10 5 5 5 5

30 in 5 5 5 5 in A 5 5 .10 5 5 5

■ 3 i n 5 5

 4 5 i n ς 5 i n 5 5 i n 5 5 5

¾Q i n 5 5

 1 Ω 5 5

42 10 5 5 5 5

43 10 5 4 5 5

44 10 5 5 5 5

45 10 5 4 5 5

46 10 5 5 5 5

48 10 5 5 5 5

49 10 5 3 5 5

51 10 5 5 5 5

52 10 5 5 5 5

53 10 5 5 5 5

54 10 5 5 5 5

55 10 5 3 5 5

Test example 3 Upland foliage treatment test

Upland volcanic ash soil was filled into a resin-made batt having an area of 20 O cm ² , and after fertilization, seeds of mustard, Maruba-asagao, inubie and suzumenotsubo were sowed and covered uniformly. Thereafter, cultivation management was continued in the greenhouse, and when the growth leaf age of the test weeds reached the 1.0 to 2.0 leaf stage, the wettable powder comprising the compound of the present invention obtained in Formulation Example 1 as an active ingredient was used. The dilution was adjusted with water, and a predetermined amount was uniformly sprayed with a small power pressurized sprayer so that the treatment amount of the active ingredient was 10 g per are. On the 21st day after the chemical treatment, the herbicidal effect was investigated.

 Table 9 shows the results. (The compound No. in Table 9 corresponds to the compound No. described in Tables 1 to 5.)

The evaluation of the herbicidal effect was expressed in the same manner as in the criteria of Test Example 1.

u continued)

Test compound Active ingredient Herbicidal effect

 No. g / a

64 10 5 5 4 3

65 10 5 5 5 5

66 10 5 5 5 3

68 10 5 5 5 5

70 10 5 5 5 5

71 10 5 4 5 4

72 10 5 5 5 5

73 10 5 5 5 5

74 10 5 5 5 5

75 10 5 4 5 4

77 10 5 5 5 5

78 10 5 5 5 5

81 10 4 4 5 5

84 10 5 5 5 5

85 10 4 3 5 5

86 10 4 4 4 5

87 10 5 5 5 5

88 10 5 5 5 5

92 10 5 5 5 5

93 10 5 5 5 5

Industrial applicability

 The compound of the present invention exhibits a high herbicidal effect at a low dose and has few problems such as phytotoxicity and is useful as a herbicide.

Claims

1. 3-substituted phenyl-4-halopyridazine derivative represented by the following general formula [I] c

5 blue

 of

 [In the above formula, X represents a halogen atom,

 Example

 Y represents a hydrogen atom or a Hagen atom,

 Z represents a halogen atom or a cyano group,

 n and m each independently represent 0 or 1,

R ¹ represents a hydrogen atom, a halogen atom, a C, —C ₆ alkyl group or a C, —C ₆ haloalkyl group,

R ² is a hydrogen atom, — an alkyl group of C ₆ or, together with R ¹ , K 1 L 1 M 1 (where K is CR ⁴ R ⁵ , CR ⁴ R ⁵ CR ⁶ R ⁷ , oxygen atom, sulfur L represents a nitrogen atom substituted by an atom or d_C ₆ alkyl group, L represents a CR ⁸ R ⁹ , an oxygen atom, a sulfur atom or a nitrogen atom substituted by a C, -Ce alkyl group, and M represents a CR atom R ¹¹ represents a nitrogen atom substituted by an oxygen atom, a sulfur atom or a C, -Ce alkyl group (the above substituents R ^{4 to} R ″ each independently represent a hydrogen atom or a C, -C ₆ However, K, L and Μ do not simultaneously represent an oxygen atom, a sulfur atom or a nitrogen atom substituted by a C, -C ₆ alkyl group.) Indicates that

R ³ is a hydrogen atom, a nitro group or a QR ¹² (wherein Q is an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group or —NR ′ ³ — (wherein, R ¹³ is a hydrogen atom,

- alkyl C _6, C ₂ - alkenyl group C _6, C ₂ - alkynyl group C _6, C 1 - haloalkyl group C _6, C ₂ - haloalkenyl group C _6, C ₂ - to C ₆ A Alkoxyalkyl group, C ₂ — Ce sacyl group, C, 1 C ₆ alkylsulfonyl group, C, -C ₆ haloalkylsulfonyl group, C ₂ —c ₆ alkenylsulfonyl group, C ₂ — And represents a C ₆ -C ₃ alkyl group substituted with a C ₆ alkoxycarbonyl group, a phenyl group or a phenyl group. ) Indicates that R ¹² is a hydrogen atom, C, one C An alkyl group of C ₂ — C,. An alkenyl group of c ₂ — C,. Alkynyl group, C ₃ -, cycloalkyl groups C _8, C ₄ one C. Shikuroa alkyl group substituted with an alkyl group, c ₄ one d. (Cyclo) alkyl group, c ₃ - Shikuroa alkenyl group c _8, C! — C1. Haguchi alkyl group, C 2 -C 1,. Shianoarukiru group, C ₂ of the C ₇ - - C, haloalkenyl, halocycloalkyl group c ₃ -c _8, C ₂ of. An alkoxyalkyl group of C ₂ —C,. An alkylthioalkyl group of C ₂ —C,. Alkylsulfonylalkyl group, Ashiru group C ₂ -C _6, C ₃ - O Kisoarukiru group C _6, C, one Cs alkylsulfonyl group, C, - Ce of Haroaruki Rusuruhoniru group, § of C ₂ -Ce Alkenylsulfonyl group, phenyl group, d-C ₃ alkyl group substituted with phenyl group, 3- to 6-membered heterocyclic group (The ring contains 1_2 oxygen, sulfur, and nitrogen or nitrogen atoms. to), the heterocyclic group (the ring of 3-6 membered, 1 - 2 oxygen atoms, sulfur atom and Z or you contain a nitrogen atom) d is substituted with - C ₃ alkyl group, following general Expression [Π]

Q ゝ

 -〇 [π]

 : -3 or the following general formula [ΙΠ]

(Wherein, R ¹⁴ represents a hydrogen atom or an alkyl group of C, — C ₄ , W is an oxygen atom, a sulfur atom or —NR ¹⁶ — (wherein, R ′ ⁶ is a hydrogen atom or a C, _ C ₄ Alkyl Represents a group. R ¹⁵ is a hydrogen atom, —C ₆ alkyl group, C ₂ —C ₆ alkenyl group, C ₂ —C ₆ alkynyl group, C ₃ —C ₆ cycloalkyl group,

C ₄ —C !. Cycloalkyl group substituted with an alkyl group, C ₃ -Ce of Shikuroa alkenyl groups, c, - haloalkyl group C 6, C ₂ - haloalkenyl group C _6, halocycloalkyl group C ₃ -C _6, C ₂ — C ₅ cyanoalkyl group, C _2-

C 6 alkoxyalkyl group, C ₂ —c ₆ alkylthioalkyl group, c _2-

Ce alkylsulfonyl alkyl, C ₃ - Okisoarukiru group Ce, Ca - § Sil O alkoxyalkyl group c _7, alkoxycarbonylalkyl group c ₃ -c _7, phenyl group, d -C substituted with Fuweniru group _3- alkyl group, 3- to 6-membered heterocyclic group (the ring contains 1-2 oxygen, sulfur and Z or nitrogen atoms), or 3- to 6-membered heterocyclic group ( The ring represents a C, 1 C ₃ alkyl group substituted with 1-2 oxygen, sulfur and nitrogen or nitrogen atoms). R ′ ⁵ is a 5- to 6-membered heterocyclic group containing 1 to 2 nitrogen atoms and / or 0 to 1 oxygen atom together with W when W represents 1 NR ′ ⁶ — May be formed. ) Represents a group represented by.

R ¹² , R ¹³ or R ′ ⁵ , a phenyl group, a C-, C ₃ -alkyl group substituted by a phenyl group, a 3- to 6-membered heterocyclic group (the ring is composed of 12 oxygen atoms , Containing a sulfur atom and / or a nitrogen atom) or a 3- to 6-membered heterocyclic group (the ring contains 112 oxygen atoms, a sulfur atom and a nitrogen atom or a nitrogen atom) When it represents a substituted C, 1 C ₃ alkyl group, the phenyl group and the heterocyclic group may be 1 to 3 identical or different halogen atoms, C, —C ₄ alkyl groups, trifluoromethyl groups, d —C ₄ alkoxy group, C ₂ —C ₅ acyloxy group, C i —C ₄ alkylthio group, C, -C alkylsulfonyl group, nitro group, cyano group or C ₂ -C ₅ alkoxycarbonyl group It may be substituted. ). ]

2. R ¹ is a hydrogen atom, C, - an alkyl or Haroaruki Le group d -C ₆ of C _6, R ² is a hydrogen atom, C, alkyl group having one C _6, or, together with R '- KLM -(Where K is CR ⁴ R ⁵ , CR ⁴ R ⁵ CR ⁶ R ⁷ , oxygen atom, sulfur L represents CR ⁸ R ⁹ , an oxygen atom, a sulfur atom or a nitrogen atom substituted by a C, -C ₆ alkyl group, and M represents an atom or a nitrogen atom substituted with a d-C ₆ alkyl group. CR ^{1 D} R ″, an oxygen atom, a sulfur atom or d — a nitrogen atom substituted with an alkyl group of C ₆ (the above substituents R ^{4 to} R ′ ″ each independently represent a hydrogen atom or d -Represents an alkyl group of C ₆ ). However, K, L and Μ are not oxygen atoms, sulfur atoms or nitrogen atoms substituted with d-Ce alkyl groups at the same time. 3. The 3-substituted phenyl-4,18-opening pyridazine derivative according to claim 1, which forms a ring represented by the formula:

3. R ² together with R ¹ — K-L— M— (where K represents CR ⁴ R ⁵ , CR ⁴ R ⁵ CR ⁶ R ⁷ or an oxygen atom, and L represents CR ⁸ R ⁹ or an oxygen atom. And M represents CR ^ R ¹¹ or an oxygen atom (the substituents R ^{4 to} R ^U each independently represent a hydrogen atom or a C 1, C ₆ alkyl group), provided that K, 3. The 3-substituted phenyl-4-halopyridazine derivative according to claim 1, wherein L and Μ are not oxygen atoms at the same time.

4. one K-L-.mu. (wherein together R ² is R ', kappa represents a CR ⁴ R ⁵ or ^{CR 4 R 5 CR 6 R 7} , L represents a CR ⁸ R ^9,! ^! Haji (The above substituents R ^{4 to} R ^U each independently represent a hydrogen atom or an alkyl group of C or -C _6. ).) The 3-substituted pyrene 4-halopyridazine derivative according to claim 1, which is characterized in that:

5. R ³ is a hydrogen atom, in a nitro group or a QR ¹² (wherein, Q is an oxygen atom or -NR ¹³ - (In the formula, R ^'3 represents a hydrogen atom, C ₂ - Ashiru group C _6, C, - C ₆ Al alkylsulfonyl group, or a C ₂ - C shows a) shows the alkoxycarbonyl two Le group _6, R ^'2 represents a hydrogen atom, d -. C ,. alkyl group, C ₂ - C alkenyl group , C ₂ - C ,. alkynyl group, C ₃ - Ca cycloalkyl group, C ₃ - of a cycloalkyl Kenyir group, C, -. C, Ha port alkyl group, C ₂ - haloalkenyl group C !. , C ₂ _ C,. Halonchloroalkyl group, C ₂ _C ₇ cyanoalkyl group, C ₂ —C ,. alkoxyalkyl group, C ₃ —C ₆ oxoalkyl group, — C ₆ alkylsulfonyl group, phenyl C, -C 3 alkyl group substituted with 3 to 6 members C, C substituted with an elementary ring group (the ring contains 12 oxygen atoms) and a 36-membered heterocyclic group (the ring contains 12 oxygen atoms) Alkyl group of ₃ , the following general formula [Π]

Or a group represented by the following general formula [m]

(Wherein, R "represents a hydrogen atom or d—C ₄ alkyl group; W is an oxygen atom or one NR ' ⁶ — (wherein, R ¹⁶ represents a hydrogen atom or d—C ₄ alkyl group) And R ¹⁵ represents a hydrogen atom or an alkyl group of C, -C _6. ) Represents a group represented by))), wherein R ¹⁵ represents a hydrogen atom or an alkyl group of C, -C ₆ . 4-halo pyridazine derivatives.

6. R ³ Chikaraku, hydrogen atom, in a nitro group or a QR ¹² (wherein, Q is an oxygen atom or -NR ¹³ - (In the formula, R ¹³ is a hydrogen atom, C, alkylsulfonyl group, or C one C _{6 2} - C shows ₆₎ indicating the alkoxy galvo two Le group, R ¹² is a hydrogen atom, C, primary alkyl groups, C ₂ alkenyl _{groups, C 2 -... C} ,. alkynyl group, C ₃ cycloalkyl groups -C _8, C, one C,. Ha port alkyl group, C ₂ - C Roarukeniru groups _{C l (), C 2 -} . Shianoarukiru group C _7, C ₂ of Arukokishiaru kill group, Okisoarukiru group of C ₃ -C _6, C, - alkylsulfonyl group C _6, C substituted with Fuweniru group, an alkyl group of one C _3, 3- 6-membered Hajime Tamaki (said ring, 1 one 2 C, 1 C ₃ alkyl group substituted by a 3-6 membered heterocyclic group (the ring contains 12 oxygen atoms); General formula [Π] [π]

Or a group represented by the following general formula [m]

(Wherein, R ^M represents a hydrogen atom or a C, C ₄ alkyl group; W is an oxygen atom or — NR ¹⁶ — (wherein, R ¹⁶ is a hydrogen atom or a C, -C ₄ alkyl group) R ¹⁵ represents a hydrogen atom or an alkyl group of C, -Ce.) Represents a group represented by). 2. The 3-substituted phenyl-4-halo pyridazine derivative according to claim 1, wherein

7. R ³ is - in QR ¹² (wherein, Q is an oxygen atom, R ^'2 is C, alkylene Le groups, C ₂ -.. C,. Alkenyl groups, C ₂ alkynyl group, C ₃ -. C of a cycloalkyl group, C, one C, Ha port alkyl group, C ₂ - haloalkenyl group C _10, C - C of Shianoarukiru groups, C ₂ - C !. alkoxyalkyl group, C ₃ A C ₆ oxoalkyl group, a 3- to 6-membered heterocyclic group (the ring contains 12 oxygen atoms), a 3- to 6-membered heterocyclic group (the ring An alkyl group of C, — C ₃ substituted with an oxygen atom) or the following general formula [Π]

Represents a group represented by 3. The 3-substituted phenyl- _4- halopyridazine derivative according to claim 1, wherein

8. R ² is R 'one K-L-M- (wherein together, K is shown a CR ⁴ R ⁵ or ^{CR 4 R 5 CR 6 R 7} , L represents a CR ⁸ R ^9, M is CR' shows the oR ^'1. where (as is the location substituent R ⁴ to R ^M, a hydrogen atom or a C independently, - shows the alkyl Le group C ₆₎₎ forms a carbocyclic ring represented by,

R ³ is a hydrogen atom, in a nitro group or a QR ¹² (wherein, Q is an oxygen atom or - NR ¹³ - (wherein, R ^'3 represents a hydrogen atom, C, - alkylsulfonyl group C ₆ or C ₂

-Represents an alkoxycarbonyl group of Ce. R ¹² is a hydrogen atom, d-

C,. An alkyl group of C ₂ — C,. An alkenyl group of C ₂ —C,. Alkynyl group, c ₃ -C ₈ cycloalkyl group, C, —C. Haguchi alkyl group, C ₂ — C ,. A haloalkenyl group; a C ₂ —C ₇ cyanoalkyl group; C ₂ —C; An alkoxyalkyl group, a C ₃ -C ₆ oxoalkyl group, a C, 1 C ₆ alkylsulfonyl group, a C, —C ₃ alkyl group substituted with a phenyl group, a 3-6 membered heterocyclic group The ring is a C, _C ₃ alkyl substituted with a 1- or 2-oxygen atom or a 3- to 6-membered heterocyclic group (the ring contains a 1-2 oxygen atom). Group, the following general formula [Π] [Π]

Or a group represented by the following general formula [m]

(Wherein, ^RM represents a hydrogen atom or an alkyl group of C, —C ₄ , W represents an oxygen atom or —NR ¹⁶ — (wherein, R ¹⁶ represents a hydrogen atom or an alkyl group of C, —) And R ¹⁵ represents a hydrogen atom or a C or -C ₆ alkyl group. 2. The 3-substituted fluoro-418-pyridazine derivative according to claim 1, wherein

9. R ² together with R ¹ K— L— M— (where K indicates CR ⁴ R ⁵ or CR ⁴ R ⁵ CR ⁶ R ⁷ , L indicates CR ⁸ R ⁹ , M indicates CR ′ R '' (wherein the substituents R ^{4 to} R ^M each independently represent a hydrogen atom or a C, 1 C ₆ alkyl group). R ³ is —QR ¹² (wherein Q represents an oxygen atom, R ′ id —Ci. Alkyl group, C ₂ .alkenyl group, C ₂ .alkynyl group, C ₃ —C ₈ Cycloalkyl group, —C ₁₀ haloalkyl group, C ₂ —C, haloalkenyl group, C ₂ —C ₇ cyanoalkyl group, C ₂ -C, .alkoxyalkyl group, C ₃ —C ₆ Oxoalkyl groups, 3-6 membered heterocyclic groups (the ring contains 12 oxygen atoms), 3-6 membered heterocyclic groups (the ring contains 1-2 oxygen atoms) ) Substituted with a C, -C ₃ alkyl group or Expression [Π]

Represents a group represented by 3. The 3-substituted phenyl-14-halopyridazine derivative according to claim 1, wherein

 10. The 3-substituted phenyl-4-halopyridazine derivative according to any one of claims 1 to 9, wherein Y is a halogen atom.

1 1. 3-substituted phenyl-4-hydroxypyridazine derivative or 3-substituted phenylpyridazine-one-one-year derivative represented by the following general formula [V] or [V '] c

[In the above formulas, Y, Z, R ', R 2 and R ³ are as defined in claim 1, wherein. ]

1 2. A 3-substituted phenyl-2,4-hydroxypyridazine derivative or a 3-substituted phenylpyridazine-4,1-one derivative represented by the following general formula [VI] or [VT].

[In the above formula, k represents 1-2, R ³ is a hydrogen atom, a nitro group, or QR ¹² (wherein Q is an oxygen atom or —NR ′ ³ — (wherein, R ¹³ is a hydrogen atom, And a C, -C ₆ alkylsulfonyl group or a C ₂ -C ₆ alkoxycarbonyl group.), Wherein R ¹² is a hydrogen atom, a C, 1 alkyl group, or a C ₂ —C, alkenyl. Group, C 1 -C ,. alkynyl group, C ₃ -C ₈ cycloalkyl group, C, 1 -C, .Haguchi alkyl group, C ₂ _C,. Haloalkenyl group, C ₂ -C ₇ cyanoalkyl Group,

C one. An alkoxyalkyl group, a C ₃ -C oxoalkyl group, d —

A C alkylsulfonyl group, a C ₃ -C ₃ alkyl group substituted with a phenyl group, a 31-6 membered heterocyclic group (the ring contains 12 oxygen atoms), a 3-6 membered A C, 1 C ₃ alkyl group substituted with a heterocyclic group (the ring contains 12 oxygen atoms). ). ]

 13. The tri-substituted phenyl-14-hydroxypyridazine derivative or the 3-substituted phenylbiridazin-4-one derivative according to claim 11, wherein Y is a halogen atom.

 1 4. An agricultural chemical comprising the 3-substituted phenyl-4-halopyrridazine derivative according to any one of claims 1 to 10 as an active ingredient.

 15. The pesticide according to claim 14, which is a herbicide.

 1 6. The pesticide according to claim 14, which is a herbicide for paddy rice.