JPWO2007026834A1 - Pyrazole derivatives and herbicides for agriculture and horticulture - Google Patents

Abstract

The present invention provides an agricultural and horticultural herbicide containing, as an active ingredient, a pyrazole derivative or a salt thereof that has no phytotoxicity to useful crops in paddy fields and upland fields and can control a wide range of weeds at a low dose. General Formula [I] [wherein A represents a phenyl group or an aromatic heterocyclic group, X represents a C3-C8 cycloalkyl group which may be substituted with a substituent group α, and Y represents a halogen atom or cyano. Represents a group, W represents an oxygen atom, a sulfur atom or CH2, L represents an oxygen atom or a sulfur atom, R represents a hydrogen atom or a C1-C8 alkyl group, R1 represents a hydrogen atom or a halogen atom, m Represents an integer of 1 to 5, and n represents an integer of 0 to 4. ] The plant control agent for agricultural and horticultural use containing the pyrazole derivative represented by these, or its salt as an active ingredient.

Description

  The present invention relates to a novel pyrazole derivative, a salt thereof, and an agricultural and horticultural herbicide containing the same as an active ingredient.

  In cultivation of agricultural and horticultural crops, a wide variety of herbicides have been put into practical use and widely used for weed control, which has required a great deal of labor. However, phytotoxicity to crops due to the use of herbicides, residue of chemicals, environmental pollution, safety to human body, etc. are problems, and there is no such problem, and it has excellent herbicidal activity at lower use amount The development of herbicides is a particularly important issue.

For example, Patent Document 1 reports that a specific pyrazole derivative has herbicidal activity. However, the activity of the pyrazole derivatives described in this publication is not satisfactory as the paddy herbicide and the upland field herbicide are strong and insufficient.
WO02 / 44173 Publication

  The present invention has been made in view of the above circumstances, and an object thereof is to use a pyrazole derivative that can control a wide range of weeds at a low dose without causing any phytotoxicity to useful crops in paddy fields and upland fields. It was to provide an agricultural and horticultural herbicide.

  As a result of intensive studies on pyrazole derivatives having an aryl group or an aromatic heterocyclic group, the present inventors have found that a novel pyrazole derivative having an aryl group or an aromatic heterocyclic ring substituted with a cycloalkyl group or the like has been developed. It has been found that it has a higher effect as a herbicide for horticulture and has higher safety, and has completed the present invention.

That is, the present invention
(1) General formula [I]

{Where,
A represents a phenyl group or an aromatic heterocyclic group,
X is substituent group α in the optionally substituted C ₃ -C ₈ cycloalkyl group, a substituted C ₃ -C ₈ optionally cycloalkyl C ₁ -C ₃ alkyl group with a substituent group α, or a substituted represents optionally substituted C ₃ -C ₈ cycloalkylcarbonyl group with a group group alpha,
Y is a halogen atom, a cyano group, a hydroxyl _group, C 1 -C ₆ alkyl _group, C 1 -C ₆ haloalkyl _group, C 2 -C ₆ alkenyl _group, C 2 -C ₆ alkynyl _group, C 1 -C ₆ alkoxy group , _C 1 -C ₆ haloalkoxy _group, C 1 -C ₆ alkylthio _group, C 1 -C ₆ alkylsulfinyl _group, C 1 -C ₆ alkylsulfonyl _group, C 1 -C ₆ haloalkylthio _group, C 1 -C ₆ It represents haloalkylsulfinyl _group, C 1 -C ₆ haloalkylsulfonyl _group, C 1 -C ₆ acyl group or a _C 1 -C ₆ alkyloxycarbonyl group,
W represents an oxygen atom, a sulfur atom or CH ₂ , L represents an oxygen atom or a sulfur atom,
R represents a hydrogen atom, a C _{1 to} C ₈ alkyl group, a C _{1 to} C ₈ haloalkyl group, a C _{3 to} C ₈ cycloalkyl group which may be substituted with a substituent group β, a C _{3 to} C ₈ cycloalkyl C ₁ to C ₃ alkyl group or a _C 3 -C ₈ halocycloalkyl _C 1 -C ₃ alkyl group,
R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₃ alkyl group, or a C ₁ -C ₃ haloalkyl group,
m represents an integer of 1 to 5,
n shows the integer of 0-4. }
The pyrazole derivative or salt represented by these.
`` Substituent group α ''
Halogen atom, cyano _group, C 1 -C ₃ alkyl group [said group may be substituted by a halogen atom or a hydroxyl _group], C 1 -C ₃ alkoxy _groups, C 1 -C ₃ acyl _group, C 1 -C ₃ alkyloxycarbonyl group, aminocarbonyl group, aminothiocarbonyl group, carboxyl group “substituent group β”
The pyrazole derivative or the salt thereof according to (1), wherein the halogen atom, C ₁ -C ₃ alkyl group (2) X is a C ₃ -C ₈ cycloalkyl group optionally substituted with a substituent group α.
(3) The pyrazole derivative or a salt thereof according to (2), wherein A is a phenyl group or a thienyl group.
(4) A is

で表される（３）記載のピラゾール誘導体又はその塩。
（５）前記（１）〜（４）のいずれかに記載のピラゾール誘導体又はその塩を有効成分として含有することを特徴とする農園芸用除草剤。
を提供するものである。

The pyrazole derivative or its salt as described in (3) represented by these.
(5) A herbicide for agricultural and horticultural use comprising the pyrazole derivative or salt thereof according to any one of (1) to (4) as an active ingredient.
Is to provide.

The compound of the present invention represented by the general formula [I] or a salt thereof includes annual weeds such as Tainubie, Inobie, Tamagayatsu, Koigi, etc., and Urikawa, Omodaka, Mitsugayatsuri, Krogwei, Inuhotarui, Taiwan Yamai, Firefly, Heramodaka Can control perennial weeds. In addition, various weeds that occur in the field, such as broad-leafed weeds such as giant beetle, aubiyu, whiteza, boxfish, chamomile, prickly beetle, American horned beetle, horned beetle, ragweed, daisy, morning glory, onamomi, yamgra, photokenosa, nogeshi; Perennial and annual perennial cyperaceae weeds such as yellow-headed, yellow-headed, cyper, and white-tailed clover; wide range of pre-emergence of pre-emergence of grasses such as barnyard millet, barnyard grass, green croaker, sparrow camellia, johnsongrass, spruce, wild oat Demonstrates herbicidal effect.
On the other hand, the herbicide of the present invention has high safety against crops, and particularly shows high safety against rice, wheat, barley, corn, grain sorghum, soybean, cotton, sugar beet, sugar cane and the like.

The symbols and terms described in this specification will be described.
The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The notation such as C _{1 to} C ₈ indicates that the subsequent substituent has 1 to 8 carbon atoms.
The C ₁ -C ₃ alkyl group means a linear or branched alkyl group having 1 to 3 carbon atoms, and includes methyl, ethyl, n-propyl, and isopropyl unless specifically limited.

The C ₁ -C ₆ alkyl group means a linear or branched alkyl group having 1 to 6 carbon atoms unless otherwise specified. For example, in addition to the above C ₁ -C ₃ alkyl group, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, , 1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1 , 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-hexyl, 1-ethyl Methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2 -Dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2 -Methylpropyl and the like can be mentioned.

The C _{1 to} C ₈ alkyl group means a linear or branched alkyl group having 1 to 8 carbon atoms unless otherwise limited. For example, in addition to the above C ₁ -C ₆ alkyl group, heptyl, 1-methylhexyl, 5-methylhexyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 4,4-dimethylpentyl, 1-ethyl Pentyl, 2-ethylpentyl, 1,1,3-trimethylbutyl, 1,2,2-trimethylbutyl, 1,3,3-trimethylbutyl, 2,2,3-trimethylbutyl, 2,3,3-trimethyl Butyl, 1-propylbutyl, 1,1,2,2-tetramethylpropyl, octyl, 1-methylheptyl, 3-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 5,5-dimethylhexyl, 2,4 , 4-trimethylpentyl, 1-ethyl-1-methylpentyl, and the like.

The C _{3 to} C ₈ cycloalkyl group means a cycloalkyl group having 3 to 8 carbon atoms unless specifically limited, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. .

The C ₁ -C ₃ haloalkyl group represents a linear or branched alkyl group having 1 to 6 carbon atoms, which is substituted with a halogen atom. For example, fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, bromodifluoromethyl, 2-fluoroethyl, 1-chloroethyl, 2-chloroethyl, 1-bromoethyl, 2-bromoethyl 2,2-difluoroethyl, 1,2-dichloroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 1,1,2,2-tetra Fluoroethyl, pentafluoroethyl, 2-bromo-2-chloroethyl, 2-chloro-1,1,2,2-tetrafluoroethyl, 1-chloro-1,2,2,2-tetrafluoroethyl, 1-chloro Propyl, 2-chloropropyl, 3-chloropropyl, 2-bromopropyl 3-bromopropyl, 2-bromo-1-methylethyl, 3-iodopropyl, 2,3-dichloropropyl, 2,3-dibromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloro Propyl, 3-bromo-3,3-difluoropropyl, 3,3-dichloro-3-fluoropropyl, 2,2,3,3-tetrafluoropropyl, 1-bromo-3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,2-trifluoro-1-trifluoromethylethyl, heptafluoropropyl, 1,2,2,2-tetrafluoro-1-trifluoromethyl Examples thereof include ethyl, 2,3-dichloro-1,1,2,3,3-pentafluoropropyl and the like.

The C ₁ -C ₆ haloalkyl group represents a linear or branched alkyl group having 1 to 6 carbon atoms, which is substituted with a halogen atom. For example, fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, bromodifluoromethyl, 2-fluoroethyl, 1-chloroethyl, 2-chloroethyl, 1-bromoethyl, 2-bromoethyl 2,2-difluoroethyl, 1,2-dichloroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 1,1,2,2-tetra Fluoroethyl, pentafluoroethyl, 2-bromo-2-chloroethyl, 2-chloro-1,1,2,2-tetrafluoroethyl, 1-chloro-1,2,2,2-tetrafluoroethyl, 1-chloro Propyl, 2-chloropropyl, 3-chloropropyl, 2-bromopropyl 3-bromopropyl, 2-bromo-1-methylethyl, 3-iodopropyl, 2,3-dichloropropyl, 2,3-dibromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloro Propyl, 3-bromo-3,3-difluoropropyl, 3,3-dichloro-3-fluoropropyl, 2,2,3,3-tetrafluoropropyl, 1-bromo-3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,2-trifluoro-1-trifluoromethylethyl, heptafluoropropyl, 1,2,2,2-tetrafluoro-1-trifluoromethyl Ethyl, 2,3-dichloro-1,1,2,3,3-pentafluoropropyl, 2-chlorobutyl, 3-chlorobutyl, 4-chlorobutyl, 2-chloro -1,1-dimethylethyl, 4-bromobutyl, 3-bromo-2-methylpropyl, 2-bromo-1,1-dimethylethyl, 2,2-dichloro-1,1-dimethylethyl, 2-chloro-1 -Chloromethyl-2-methylethyl, 4,4,4-trifluorobutyl, 3,3,3-trifluoro-1-methylpropyl, 3,3,3-trifluoro-2-methylpropyl, 2,3 , 4-trichlorobutyl, 2,2,2-trichloro-1,1-dimethylethyl, 4-chloro-4,4-difluorobutyl, 4,4-dichloro-4-fluorobutyl, 4-bromo-4,4 -Difluorobutyl, 2,4-dibromo-4,4-difluorobutyl, 3,4-dichloro-3,4,4-trifluorobutyl, 3,3-dichloro-4,4,4-trifluorobutyl, 4 − Bromo-3,3,4,4-tetrafluorobutyl, 4-bromo-3-chloro-3,4,4-trifluorobutyl, 2,2,3,3,4,4-hexafluorobutyl, 2, 2,3,4,4,4-hexafluorobutyl, 2,2,2-trifluoro-1-methyl-1-trifluoromethylethyl, 3,3,3-trifluoro-2-trifluoromethylpropyl, 2,2,3,3,4,4,4-heptafluorobutyl, 2,3,3,3-tetrafluoro-2-trifluoromethylpropyl, 1,1,2,2,3,3,4 4-octafluorobutyl, nonafluorobutyl, 4-chloro-1,1,2,2,3,3,4,4-octafluorobutyl, 5-fluoropentyl, 5-chloropentyl, 5,5-difluoropentyl 5,5-dichloro pliers , 5,5,5-trifluoro pentyl, may be mentioned 6,6,6-trifluoro-hexyl or 5,5,6,6,6- pentafluoro-hexyl and the like.

The C _{1 to} C ₈ haloalkyl group represents a linear or branched alkyl group having 1 to 8 carbon atoms, which is substituted with a halogen atom. In addition to the above C ₁ -C ₆ haloalkyl groups, for example, 6,6,7,7,7-pentafluoroheptyl, 8,8,8-trifluoroheptyl, 7,7,8,8,8-penta Fluorooctyl, 8,8,8-trifluorooctyl, etc. can be mentioned.

The C _{2 to} C ₆ alkenyl group means a straight or branched alkenyl group having 2 to 6 carbon atoms unless otherwise limited. For example, vinyl, 1-propenyl, isopropenyl, 2-propenyl, 1-butenyl, 1-methyl-1-propenyl, 2-butenyl, 1-methyl-2-propenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1,3-butadienyl, 1-pentenyl, 1-ethyl-2-propenyl, 2-pentenyl, 1-methyl-1-butenyl, 3-pentenyl, 1-methyl-2-butenyl, 4-pentenyl, 1-methyl-3-butenyl, 3-methyl-1-butenyl, 1,2-dimethyl-2-propenyl, 1,1-dimethyl-2-propenyl, 2-methyl-2-butenyl, 3- Methyl-2-butenyl, 1,2-dimethyl-1-propenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,3-pentadienyl, 1 Vinyl-2-propenyl, 1-hexenyl, 1-propyl-2-propenyl, 2-hexenyl, 1-methyl-1-pentenyl, 1-ethyl-2-butenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl 1-methyl-4-pentenyl, 1-ethyl-3-butenyl, 1- (isobutyl) vinyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-2-propenyl, 1- (Isopropyl) -2-propenyl, 2-methyl-2-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1,3-dimethyl-2-butenyl, 1,1-dimethyl-3- Butenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-3-butenyl, 1,1,2-to Examples include limethyl-2-propenyl, 1,5-hexadienyl, 1-vinyl-3-butenyl, 2,4-hexadienyl, and the like.

The C _{2 to} C ₆ alkynyl group means a linear or branched alkynyl group having 2 to 6 carbon atoms unless otherwise limited. For example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 1-ethyl-2-propynyl, 2-pentynyl, 3-pentynyl 1-methyl-2-butynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-hexynyl, 1- (n-propyl) -2-propynyl, 2-hexynyl, 1 -Ethyl-2-butynyl, 3-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 4-methyl-1-pentynyl, 3-methyl-1-pentynyl, 5-hexynyl, 1-ethyl -3-butynyl, 1-ethyl-1-methyl-2-propynyl, 1- (isopropyl) -2-propynyl, 1,1-dimethyl-2-butynyl or 2 2-dimethyl-3-butynyl and the like.

The C ₁ -C ₆ alkoxy group means an (alkyl) -O— group having 1 to 6 carbon atoms in which the alkyl portion has the above-mentioned meaning, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy and the like. .

A C ₁ -C ₆ haloalkoxy group is a straight or branched (haloalkyl)-having 1 to 6 carbon atoms in which the haloalkyl moiety is substituted with the same or different halogen atoms 1 to 13 having the above-mentioned meanings. O-group is shown. For example, chloromethoxy, difluoromethoxy, chlorodifluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy and the like can be mentioned.

The C ₁ -C ₆ alkylthio group means an (alkyl) -S-group having 1 to 6 carbon atoms in which the alkyl portion has the above meaning, and examples thereof include methylthio, ethylthio, n-propylthio, isopropylthio and the like. Can do.

The C ₁ -C ₆ alkylsulfinyl group means an (alkyl) -SO— group having 1 to 6 carbon atoms in which the alkyl portion has the above meaning, for example, methylsulfinyl, ethylsulfinyl, n-propylsulfinyl or isopropylsulfinyl. Etc.

The C ₁ -C ₆ alkylsulfonyl group means an (alkyl) -SO ₂ — group having 1 to 6 carbon atoms in which the alkyl portion has the above meaning, for example, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl or isopropyl A sulfonyl etc. can be mention | raise | lifted.

The C ₁ -C ₆ haloalkylthio group means a (haloalkyl) -S— group having 1 to 6 carbon atoms in which the haloalkyl moiety has the above meaning, and examples thereof include difluoromethylthio and trifluoromethylthio. .

The C ₁ -C ₆ haloalkylsulfinyl group refers to a (haloalkyl) -SO— group having 1 to 6 carbon atoms in which the haloalkyl moiety has the above meaning, such as chloromethylsulfinyl, difluoromethylsulfinyl, trifluoromethylsulfinyl, etc. Can give.

The C ₁ -C ₆ haloalkylsulfonyl group, carbon atoms haloalkyl moiety is the meaning of the above 1 to 6 (haloalkyl) -SO 2 _- represents a group, for example chloro methylsulfonyl, difluoromethyl sulfonyl or trifluoromethylsulfonyl Etc.

The C ₁ -C ₆ acyl group, a linear or branched aliphatic acyl group having from 1 to 6 carbon atoms, such as formyl, can be exemplified acetyl, propionyl or isopropionyl like.

The C ₁ -C ₆ alkyloxycarbonyl group refers to an (alkyl) -O (C═O) — group having 1 to 6 carbon atoms in which the alkyl portion has the above meaning. For example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl and the like can be mentioned.

The C ₃ -C ₈ cycloalkyl C ₁ -C ₃ alkyl group means a (cycloalkyl) alkyl group in which the cycloalkyl part and the alkyl part have the above-mentioned meanings unless otherwise specified. Examples thereof include cyclopropylmethyl, 1-cyclopropylethyl, 2-cyclopropylethyl, 1-cyclopropylpropyl, 2-cyclopropylpropyl, 3-cyclopropylpropyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl and the like. .

The C _{3 to} C ₈ cycloalkylcarbonyl group refers to a (cycloalkyl) -C (═O) — group having 3 to 8 carbon atoms in which the cycloalkyl portion has the above-mentioned meaning. For example, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl and the like can be mentioned.

A C _{3 to} C ₈ halocycloalkyl group means a cycloalkyl group having 3 to 8 carbon atoms substituted by a halogen atom unless specifically limited. For example, 2,2-dichlorocyclopropyl, 2,2-difluorocyclo Propyl and the like can be given.

The C ₃ -C ₈ halocycloalkyl C ₁ -C ₃ alkyl group means a (halocycloalkyl) alkyl group in which the halocycloalkyl part and the alkyl part have the above-mentioned meanings unless otherwise specified. For example, (2,2-dichlorocyclopropyl) methyl, (2,2-difluorocyclopropyl) methyl and the like can be mentioned.

  The aromatic heterocyclic group is a C3-C10 heterocyclic group having one or more heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen atoms which may be the same or different. For example, furyl, thienyl, pyrrolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, imidazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, triazolyl, oxadiazolyl, thiadiazolyl, benzofuryl, benzothienyl, indolyl, indazolyl, benzothiazolyl, Ril, benzoxazolyl, benzisoxazolyl, benzimidazolyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl or benzoyl And nzotriazinyl.

Next, specific examples of the compound of the present invention represented by the general formula [I] are shown in Tables 1 to 25. However, the compound of the present invention is not limited to these compounds.
The compound of the present invention represented by the general formula [I] has an asymmetric carbon in the molecule, and such a compound has an R / S isomer. Pure individual R-forms, S-forms and mixtures thereof are also included in the compounds of the present invention.

In the tables in this specification, c-Pr represents a cyclopropyl group, 2,2-Cl ₂ -c-Pr represents a 2,2-dichlorocyclopropyl group, and 2,2-Cl ₂ -1-CH ₃ -c-Pr represents a 2,2-dichloro-1-methylcyclopropyl group.

一般式［Ｉ］で示される本発明化合物の代表的な製造方法を以下に例示するが、これらの方法に限定されるものではない。

Although the typical manufacturing method of this invention compound shown by general formula [I] is illustrated below, it is not limited to these methods.

  <Manufacturing method 1>

（式中、Ａ、Ｘ、Ｙ、Ｗ、ｍ、ｎ、Ｒ及びＲ^１はそれぞれ前記と同じ意味を示し、Ｌ’は酸素原子を示す。）

(In the formula, A, X, Y, W, m, n, R and R ¹ each have the same meaning as described above, and L ′ represents an oxygen atom.)

(Process 1)
The compound of the present invention represented by the general formula [I ′] is a compound represented by the general formula [II] and a pyrazole derivative [III] in a solvent in the presence of a dialkylazodicarboxylate and a triarylphosphine. Or it can manufacture by making it react without a solvent.
What is necessary is just to select the usage-amount of the pyrazole derivative [III] used at this process suitably from the range of 0.5-10 mol with respect to 1 mol of compounds represented by general formula [II], Preferably it is 1-2. Is a mole.
Examples of the dialkyl azodicarboxylate that can be used in this step include diethyl azodicarboxylate.

The amount of dialkylazodicarboxylate used may be appropriately selected from the range of 0.1 mol to 10 mol, preferably 1 to 1.2 mol, relative to 1 mol of the compound represented by the general formula [II]. is there.
Examples of the triarylphosphine that can be used in this step include triphenylphosphine.
What is necessary is just to select the usage-amount of a triarylphosphine from the range to 0.1 mol-10 mol suitably with respect to 1 mol of compounds represented by general formula [II], Preferably it is 1-1.2 mol.

  As a solvent that can be used in this reaction, any solvent that does not inhibit the progress of this reaction may be used. For example, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, monoglyme or diglyme; halogenated hydrocarbons such as dichloromethane; aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene or toluene can be used. . Furthermore, these mixed solvents can also be used. The usage-amount of a solvent is 0-100L with respect to 1 mol of compounds represented by general formula [II], Preferably it is 1-10L.

What is necessary is just to select reaction temperature from the range of the boiling point range of the inert solvent used from -20 degreeC, Preferably it is the range of -20-100 degreeC.
The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 1 hour to 5 days.
The compound of the present invention represented by the general formula [I ′], which is the target of the reaction, is collected from the reaction system by a conventional method after the completion of the reaction. The obtained target product can be purified by operations such as column chromatography and recrystallization as necessary.

(Process 2)
The compound represented by the general formula [I ′] is obtained by mixing a mixture prepared by mixing a pyrazole derivative [III], thionyl chloride and diisopropylethylamine with a compound represented by the general formula [II] in a solvent. Or it can manufacture by making it react without a solvent.
What is necessary is just to select the usage-amount of the pyrazole derivative [III] used at this process suitably from the range of 0.5-10 mol with respect to 1 mol of compounds represented by general formula [II], Preferably it is 1-2. .5 moles.
What is necessary is just to select the usage-amount of thionyl chloride suitably from the range of 0.1 mol-10 mol with respect to 1 mol of compound [II], Preferably it is 1-2.5 mol.
What is necessary is just to select the usage-amount of diisopropyl ethylamine suitably from the range of 0.1 mol-10 mol with respect to 1 mol of compound [II], Preferably it is 2-5 mol.

As a solvent that can be used in this reaction, any solvent that does not inhibit the progress of this reaction may be used. For example, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, monoglyme or diglyme; halogenated hydrocarbons such as dichloromethane; aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene or toluene can be used. . Furthermore, these mixed solvents can also be used.
The usage-amount of a solvent is 0-100L with respect to 1 mol of compounds represented by general formula [II], Preferably it is 1-10L.

What is necessary is just to select reaction temperature from the range of the boiling point range of the inert solvent used from -20 degreeC, Preferably it is the range of -20-100 degreeC.
The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 1 hour to 5 days.
The compound of the present invention represented by the general formula [I], which is the target of the reaction, is collected from the reaction system by a conventional method after the completion of the reaction. The obtained target product can be purified by operations such as column chromatography and recrystallization as necessary.

  <Manufacturing method 2>

（式中、Ａ、Ｘ、Ｙ、Ｗ、ｍ、ｎ、Ｒ及びＲ^１はそれぞれ前記と同じ意味を示し、Ｌ’は酸素原子を示し、Ｑは塩素原子、臭素原子、ヨウ素原子、メチルスルホニルオキシ基又は４−メチルフェニルスルホニルオキシ基を示す。）

(In the formula, A, X, Y, W, m, n, R and R ¹ each have the same meaning as described above, L ′ represents an oxygen atom, Q represents a chlorine atom, a bromine atom, an iodine atom, methylsulfonyl) Represents an oxy group or a 4-methylphenylsulfonyloxy group.)

  The compound of the present invention represented by the general formula [I ′] reacts the compound represented by the general formula [IV] with the pyrazole derivative [III] in the presence or absence of a base in a solvent or without a solvent. By making it, it can manufacture.

  What is necessary is just to select the usage-amount of the pyrazole derivative [III] used at this process suitably from the range of 0.5-10 mol with respect to 1 mol of compounds represented by general formula [IV], Preferably it is 1-2. .5 moles.

Examples of the base that can be used in this step include triethylamine, N, N-diisopropylethylamine, pyridine, 4-dimethylaminopyridine, N, N-dimethylaniline, and 1,8-diazabicyclo [5.4.0] -7-undecene. Organic amines such as (DBU); metal carbonates such as sodium carbonate, potassium carbonate, magnesium carbonate or calcium carbonate; metal hydrogen carbonates such as sodium hydrogen carbonate or potassium hydrogen carbonate; sodium acetate, potassium acetate, calcium acetate or acetic acid Metal carboxylates represented by metal acetates such as magnesium; metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tertiary butoxide, potassium methoxide or potassium tertiary butoxide; sodium hydroxide, potassium hydroxide Arm, metal hydroxides such as calcium hydroxide or magnesium hydroxide; lithium hydride, sodium hydride, metal hydrides such as potassium hydride or calcium hydride and the like.
What is necessary is just to select the usage-amount of a base suitably from the range of 0-10 mol with respect to 1 mol of pyrazole derivatives [III], Preferably it is 0-2.5 mol.

  As a solvent that can be used in this reaction, any solvent that does not inhibit the progress of this reaction may be used. For example, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, monoglyme or diglyme; halogenated hydrocarbons such as dichloroethane, chloroform, carbon tetrachloride or tetrachloroethane; aromatic carbonization such as benzene, chlorobenzene, nitrobenzene or toluene Hydrogens; amides such as N, N-dimethylformamide or N, N-dimethylacetamide; imidazolinones such as 1,3-dimethyl-2-imidazolinone; sulfur compounds such as dimethyl sulfoxide; nitriles such as acetonitrile Water or the like can be used. Furthermore, these mixed solvents can also be used. The usage-amount of a solvent is 0-100L with respect to 1 mol of compounds represented by general formula [IV], Preferably it is 0-10L.

What is necessary is just to select reaction temperature from the range of the boiling point range of the inert solvent used from -20 degreeC, Preferably it is the range of -20-200 degreeC.
The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 1 hour to 5 days.
The compound of the present invention represented by the general formula [I ′], which is the target of the reaction, is collected from the reaction system by a conventional method after the completion of the reaction. The obtained target product can be purified by operations such as column chromatography and recrystallization as necessary.

  <Manufacturing method 3>

（式中、Ａ、Ｙ、Ｗ、ｎ、ｍ、Ｌ、Ｒ及びＲ^１はそれぞれ前記と同じ意味を示し、Ｚは塩素原子、臭素原子、ヨウ素原子又はトリフルオロメチルスルホニルオキシ基を示し、Ｘはシクロプロピル基を示す。）

(In the formula, A, Y, W, n, m, L, R and R ¹ each have the same meaning as described above; Z represents a chlorine atom, a bromine atom, an iodine atom or a trifluoromethylsulfonyloxy group; Represents a cyclopropyl group.)

The compound of the present invention represented by the general formula [I] is a tetrahedron letter (Tetrahedron).
Letter), Vol. 43, No. 39, pages 6987-6990 (2002), a compound represented by the general formula [V] and cyclopropylboronic acid in the presence of a palladium complex and a base. Thus, it can be produced by reacting.

  <Manufacturing method 4>

（式中、Ａ、Ｙ、Ｗ、ｎ、ｍ、Ｌ、Ｒ及びＲ^１はそれぞれ前記と同じ意味を示し、Ｑ^１、Ｑ^２及びＱ^３は独立して水素原子又はＣ_１〜Ｃ_３アルキル基を示し、Ｔ^１及びＴ^２はフッ素原子又は塩素原子を示す。）

(In the formula, A, Y, W, n, m, L, R and R ¹ each have the same meaning as described above, and Q ¹ , Q ² and Q ³ are independently a hydrogen atom or C ₁ -C ₃ alkyl. And T ¹ and T ² represent a fluorine atom or a chlorine atom.)

  The compounds of the present invention represented by the general formula [I-1] are disclosed in The Journal of Organic Chemistry, Vol. 29, pages 1379-1382 (1964) and Journal of Organic Chemistry. In accordance with the method described in Journal of the American Chemical Society, Vol. 95, pages 6655-6665 (1973), the compound represented by the general formula [VI] and [VII It can be produced by reacting a dihalocarbene generated by thermal decomposition.

  <Manufacturing method 5>

（式中、Ａ、Ｙ、Ｗ、ｎ、ｍ、Ｌ、Ｒ及びＲ^１はそれぞれ前記と同じ意味を示し、Ｑ^１、Ｑ^２及びＱ^３は独立して水素原子、フッ素原子、塩素原子、臭素原子、Ｃ_１〜Ｃ_３アルキル基又はＣ_１〜Ｃ_３アルコキシ基を示す。）

(In the formula, A, Y, W, n, m, L, R and R ¹ each have the same meaning as described above, and Q ¹ , Q ² and Q ³ are independently a hydrogen atom, a fluorine atom, a chlorine atom, bromine _atom, a C 1 -C ₃ alkyl or _C 1 -C ₃ alkoxy group.)

  The compound of the present invention represented by the general formula [I-2] is a compound represented by the general formula [VI] according to the method described in ORGANIC REACTIONS, Vol. 58, pages 1-731. And a carbene complex generated from a combination of zinc, copper and diiodomethane, a combination of diethylzinc and diiodomethane, a combination of diethylzinc, diiodomethane and trifluoroacetic acid, or the like.

The compounds represented by the general formula [II] and the general formula [IV] used as raw materials in the production method are, for example, WO 94/13652, WO 95/33719, WO 97/19920, WO 97/20838. , And can be easily produced according to the methods described in WO97 / 28138 and WO00 / 21928.
The compounds represented by the general formula [V] and the general formula [VI] can be easily produced according to the methods described in Patent Document 1 and the like.

  Pyrazole derivatives [III] are either commercially available or Comprehensive Heterocyclic Chemistry Vol. 5, pp. 167-304 (1984) and Journal of Heterocyclic Chemistry. (Journal of Heterocyclic Chemistry) Vol. 33, pp. 323-326 (1996), etc.

The herbicide for agricultural and horticultural use of the present invention can contain additive components that are usually used in agricultural chemical formulations as necessary.
As this additional component, a carrier such as a solid carrier or a liquid carrier, a surfactant, a binder or a tackifier, a thickener, a colorant, a spreading agent, a spreading agent, an antifreezing agent, an anti-caking agent, Examples include disintegrants and decomposition inhibitors. In addition, you may use a preservative, a plant piece, etc. for an additional component as needed. These additive components may be used alone or in combination of two or more.

The additive component will be described.
Examples of solid carriers include natural minerals such as quartz, clay, kaolinite, pyrophyllite, sericite, talc, bentonite, acid clay, attapulgite, zeolite, and diatomaceous earth; inorganic such as calcium carbonate, ammonium sulfate, sodium sulfate, and potassium chloride Salts: organic solid carriers such as synthetic silicic acid, synthetic silicates, starches, celluloses, plant powders; plastic carriers such as polyethylene, polypropylene and polyvinylidene chloride. These may be used alone or in combination of two or more.

  Examples of the liquid carrier include monohydric alcohols such as methanol, ethanol, propanol, isopropanol, and butanol, and polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, and glycerin. Alcohols roughly classified; Polyhydric alcohol derivatives such as propylene glycol ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone; Ethyl ether, dioxane, cellosolve, dipropyl ether, tetrahydrofuran, etc. Ethers; aliphatic hydrocarbons such as normal paraffin, naphthene, isoparaffin, kerosene, mineral oil; benzene, toluene, Aromatic hydrocarbons such as silene, solvent naphtha and alkylnaphthalene; halogenated hydrocarbons such as dichloroethane, chloroform and carbon tetrachloride; esters such as ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate and dimethyl adipate; Lactones such as γ-butyrolactone; Amides such as dimethylformamide, diethylformamide, dimethylacetamide, N-alkylpyrrolidinone; Nitriles such as acetonitrile; Sulfur compounds such as dimethylsulfoxide; Soybean oil, Rapeseed oil, Cottonseed oil, Castor oil And vegetable oils such as water; These may be used alone or in combination of two or more.

Examples of the surfactant include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene fatty acid diester, polyoxyethylene alkyl ether, polyoxyethylene Ethylene alkyl phenyl ether, polyoxyethylene dialkyl phenyl ether, polyoxyethylene alkyl phenyl ether formalin condensate, polyoxyethylene polyoxypropylene block polymer, alkyl polyoxyethylene polypropylene block polymer ether, polyoxyethylene alkylamine, polyoxyethylene fatty acid Amide, polyoxyethylene fatty acid bisphenyl ether, polyalkylene benzyl ester Nonionics such as nyl ether, polyoxyalkylene styryl phenyl ether, acetylene diol, polyoxyalkylene-added acetylene diol, polyoxyethylene ether type silicon, ester type silicon, fluorosurfactant, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil Surfactants; alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl benzene sulfonates, lignin sulfonates, alkyl sulfosuccinates, Naphthalene sulfonate, alkyl naphthalene sulfonate, salt of formalin condensate of naphthalene sulfonic acid, formalin condensation of alkyl naphthalene sulfonic acid Salt, fatty acid salt, polycarboxylate, N-methyl-fatty acid sarcosinate, resinate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkylphenyl ether phosphate, anionic surfactant; lauryl Cationic surfactants such as amine hydrochloride, stearylamine hydrochloride, oleylamine hydrochloride, stearylamine acetate, stearylaminopropylamine acetate, alkylamine salts such as alkyltrimethylammonium chloride and alkyldimethylbenzalkonium chloride; amino acid type Alternatively, amphoteric surfactants such as betaine type are listed.
One of these surfactants may be used, or two or more thereof may be used in combination.

  Examples of the binder and tackifier include carboxymethylcellulose and salts thereof, dextrin, water-soluble starch, xanthan gum, guar gum, sucrose, polyvinyl pyrrolidone, gum arabic, polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, and an average molecular weight of 6000. Examples include polyethylene glycol having ˜20,000, polyethylene oxide having an average molecular weight of 100,000 to 5,000,000, and phospholipids (for example, cephalin and lecithin).

  Examples of thickeners include xanthan gum, guar gum, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivatives, water-soluble polymers such as polysaccharides; inorganic fine powders such as high-purity bentonite and white carbon Can be given.

Examples of the colorant include inorganic pigments such as iron oxide, titanium oxide, and Prussian blue; organic dyes such as alizarin dyes, azo dyes, and metal phthalocyanine dyes.
Examples of the spreading agent include silicon surfactant, cellulose powder, dextrin, modified starch, polyaminocarboxylic acid chelate compound, crosslinked polyvinylpyrrolidone, maleic acid and styrenes, methacrylic acid copolymer, polyhydric alcohol polymer, Examples thereof include half esters with dicarboxylic acid anhydrides and water-soluble salts of polystyrene sulfonic acid.

  Examples of the spreading agent include various surfactants such as sodium dialkylsulfosuccinate, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, paraffin, terpene, polyamide resin, polyacrylate, Examples thereof include polyoxyethylene, wax, polyvinyl alkyl ether, alkylphenol formalin condensate, and synthetic resin emulsion.

Examples of the antifreezing agent include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin.
Examples of the anti-caking agent include polysaccharides such as starch, alginic acid, mannose, and galactose, polyvinyl pyrrolidone, white carbon, ester gum, and petroleum resin.

Examples of disintegrating agents include sodium tripolyphosphate, sodium hexametaphosphate, metal stearate, cellulose powder, dextrin, methacrylic acid ester copolymer, polyvinylpyrrolidone, polyaminocarboxylic acid chelate compound, sulfonated styrene / isobutylene / maleic anhydride Examples thereof include a copolymer and a starch / polyacrylonitrile graft copolymer.
Examples of the decomposition inhibitor include desiccants such as zeolite, quicklime, and magnesium oxide; antioxidants such as phenols, amines, sulfurs, and phosphoric acids; UV absorbers such as salicylic acid and benzophenone. It is done.

Examples of the preservative include potassium sorbate and 1,2-benzthiazolin-3-one.
Examples of plant pieces include sawdust, palm, corn cob, tobacco stem and the like.

  In the agricultural and horticultural herbicide of the present invention, when the above-mentioned additive component is contained, the content ratio is usually 5 to 95%, preferably 20 to 90% for the carrier, and usually 0.8 for the surfactant. 1 to 30%, preferably 0.5 to 10%, and other additives are selected in the range of 0.1 to 30%, preferably 0.5 to 10%.

  The herbicide for agricultural and horticultural use according to the present invention may be any liquid, emulsion, wettable powder, powder, oil, granule wettable powder, flowable powder, milk suspension, granule, jumbo drug, suspoemulsion, microcapsule, etc. It is formulated into a dosage form and used.

At the time of the formulation, a mixed composition with at least one other agrochemical such as other herbicides, insecticides, fungicides, plant growth regulators, fertilizers and the like can be used. In use, dilute to an appropriate concentration and spray or apply directly.
Here, other herbicides that can be mixed are exemplified.
Alkanamide compounds: diphenamide, napropamide anilide compounds: pentanochlor, propanyl, naproanilide arylaminopropionic acid compounds: flamprop M
Aryloxyalkanoic acid compounds: MCPA-thioethylaryloxyphenoxypropionic acid compounds: Clodinahop, cihalohop-butyl, diclohop-methyl, phenoxaprop-ethyl, phenoxaprop-P-ethyl, fenthiaprop-ethyl, fluazihop , Fluazifop-P, haloxyhop, haloxyhop-P, metamihop, propakizahop, quizalofop-ethyl, quizalofop-P-ethylbenzamide-based compound: isoxabenbenzenedicarboxylic acid-based compound: chlortal-dimethylbenzofuran-based compound: benfrecetate, etofumecetate Acid compounds: dicamba, 2,3,6-TBA
Benzonitrile compounds: Diclobenylbenzothiadiazinone compounds: Bentazone benzothiazolone compounds: Benazoline bipyridylium compounds: Diquat, paraquat carbamate compounds: ashram, carbetamid, chlorprofam, profam cyclohexanedione Oxime compounds: alloxidim, butroxidim, cretodim, cycloxydim, profoxydim, cetoxidim, teplaloxidim, tralcoxydim, chloroacetamide compounds: propachlor, dimetachlor, metazachlor, tenylchlor, alachlor, butachlor, pretilachlor, acetochlor, Propisochlor, metolachlor, S-metolachlor, dimethenamide, petoxamide dinitroaniline compounds: benflurali , Butralin, Etarufururarin, oryzalin, pendimethalin, trifluralin, Gini tiger Min-ji nitrophenol compounds: dinoterb, DNOC
Diphenyl ether compounds: acifluorfen, bifenox, fluoroglycophene, fomesafen, HC-252, lactofene, oxyfluorfen, acloniphen glycine compounds: glyphosate, glyphosate / trimesium salt hydroxybenzonitrile compounds: ioxynyl, bromoxynilimidazo Linone compounds: imazapyr, imazametabenz, imazaquin, imazetapill, imazamemetapyr (imazapic), imazamox isoxazole compound: isoxaflutol isoxazolidinone compound: chromamazone N-phenylphthalimide compound: sinidone ethyl, full Microlac pentyl, flumioxazin oxadiazole compounds: oxadiargyl, oxadiazone oxyacetamide Compound: flufenacet, mefenacet oxazolidinedione compound: pentoxazone phenoxycarboxylic acid compound: 2,4-D, 2,4-DB, chromeprop, dichloroprop, dichloroprop-P, MCPA, MCPB, mecoprop , Mecoprop-P
Phenyl carbamate compounds: desmedifam, phenmedifam phenylpyrazole compounds: pyraflufen / ethylphenylpyridazine compounds: pyridate phosphinic acid compounds: bialaphos, glufosinate phosphoramidate compounds: butamiphos phosphorodithioate compounds : Benthlide phthalate compound: Naptalam pyrazole compound: Benzophenap, pyrazolate (pyrazolinate), pyrazoxifene pyrazolium compound: Difenzo coated pyridazinone compound: Chloridazone, flufenpyr, norflurazon pyridine compound : Dithiopyr, thiazopyrpyridine carboxamide compounds: Diflufenican, picolinaphenepyridinecarboxylic acid compounds: Clopyralide, picloram, tri Lopyr, fluoxypyrpyrimidinedione compounds: Butaphenacylpyrimidinyloxy (thio) benzoic acid compounds: Pyrithiobac, Pyrithiobac sodium salt, Pyriminobac-methyl, Bispyribac, Bispyribac sodium salt, Pyribenzoxime, Pyriphthalidoquinoline carvone Acid compounds: quinchlorac, quinmerac semicarbazone compounds: diflufenzopyrsulfonylsulfonylcarbonylcarbonyltriazolinone compounds: flucarbazone sodium salt, propoxycarbazone sodium salt sulfonylurea compounds: amidosulfuron, azimusulfuron Bensulfuron methyl, Chlorimuron ethyl, Chlorsulfuron, Sinosulfuron, Cyclosulfamuron, Etamethsulfuron methyl, Ethoxysulfur , Flazasulfuron, flupirsulfuron, foramsulfuron, halosulfuron methyl, imazosulfuron, iodosulfuron, mesosulfuron methyl, metsulfuron methyl, nicosulfuron, oxasulfuron, primissulfuron, prosulfuron, pyrazosulfuron ethyl , Rimsulfuron, sulfometuron methyl, sulfosulfuron, thifensulfuron methyl, trisulfuron, tribenuron methyl, trifloxysulfuron, triflusulfuron methyl, tritosulfuron tetrazolinone compounds: fentrazamide thiadiazole series Compound: Fruthiaset / Methylthiocarbamate Compound: Pyributicarb, Butyrate, Cycloate, Dimepiperate, EPTC, Esprocarb, Molinate , Olvencarb, pebrate, prosulfocarb, thiobencarb, thiocarbazyl, triarate triazine compounds: amethrin, atrazine, cyanazine, dimetamethrin, prometon, promethrin, propazine, simazine, cimethrin, terbumethone, terbutyrazine, terbutridine, trietadine triazolopyrimidine : Chloranthram methyl, diclosram, flurosum ram, flumeturum, metoslam, penox slam triazinone compounds: hexazinone, metamitron, metribudine triazolinone compounds: amicarbazone, carfentrazone ethyl, sulfentrazone triazole compounds: fenfentrol Triketone compounds: mesotrione, sulcotrione, AVH-301
Uracil compounds: Bromasil, Renacil, Turbacil urea compounds: Chlorotolulone, Dimeflon, Diuron, fluometuron, Isoproturon, Isouron, Carbutyrate, Linuron, Metabenzthiazulone, Metobenzuron, Metoxuron, Monolinuron, Nebulon, Ciduron, Benzothuron , Cyclulon, Chloroxuron, Daimlone, Fluthiouron, Methyldaimuron, Thiazilazuron, Etizimuron, Thiazafluuron, Thiidiazuron and other compounds: Chlorfenac, Chlorfenprop-methyl, Cinmethineline, Endal, Fluridone, Flurochloridone, Flurtamone, Indanophan, Pinoxaden, quinoclamin, thiazimine, tridiphan, pyrimisulfurphan Pyroxasulfone, prohexadione-calcium salt.

The above herbicides are, for example, The Pesticide Manual 13th edition (published by British Crop Protection Council, 2004), Shibuya Index 10th edition, 11th edition ( SHIBUYA INDEX 10th Edition, 11th Edition, Publisher: SHIBUYA INDEX Study Group) or publicly known.
Further, the herbicide for agricultural and horticultural use according to the present invention may be in a form in which the above-mentioned arbitrary preparation is packaged with a water-soluble film. In this way, it contributes to labor saving and improves safety in the application. be able to.

The method for producing the agricultural and horticultural herbicide of the present invention is not particularly limited, but the following are usually used.
(1) A method of adding an appropriate amount of water to a mixture of all raw materials, kneading, extruding from a screen with a hole of a certain size, granulating and drying.
(2) A method in which an inventive compound and a surfactant are dissolved in an organic solvent and adsorbed on a carrier.
(3) A method of mixing and pulverizing a mixture of all raw materials with an appropriate pulverizer.

  The herbicide for agricultural and horticultural use of the present invention can be used by foliage application, soil application, water application, and the like. The blending ratio of the active ingredient is appropriately selected as necessary, but in the case of a powder or granule, it is appropriately 0.01 to 10% (weight), preferably 0.05 to 5% (weight). It is good to choose. In the case of using an emulsion, a wettable powder, etc., it is appropriate to select from the range of 1 to 50% (weight), preferably 5 to 30% (weight). Moreover, when making it a flowable agent etc., it is good to choose suitably from the range of 1-40% (weight), Preferably 5-30% (weight).

  The application rate of the herbicide for agricultural and horticultural use of the present invention varies depending on the type of the compound used, the target weed, the development tendency, the environmental conditions and the dosage form used. For example, when using it as it is like a powder agent, a granule, etc., it is good to choose suitably from the range of 1g-50kg per hectare as an active ingredient, Preferably it is 10g-10kg. In addition, when used in a liquid state as in the case of emulsions, wettable powders, flowables and the like, it may be appropriately selected from the range of 0.1 to 50,000 ppm, preferably 10 to 10,000 ppm.

  Hereinafter, although the manufacturing method of this invention compound shown by general formula [I], a formulation example, and a use are demonstrated in detail in the following Example, this invention is not restrict | limited at all to these Examples. In the following description, “%” represents a weight percentage.

Preparation of 1- [3- (2,2-difluorocyclopropyl) phenyl] -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone (Compound No. of the present invention) I-4)
To a solution of 3- (1,1-dimethylethyl) -1H-pyrazole (1.2 g, 9.66 mmol) in N, N-dimethylformamide (20 ml) was added sodium hydride (0.38 g, 60% dispersion, 9.50 mmol) was added and stirred at room temperature for 30 minutes. This mixture was added to a solution of 3-bromo-1- [3- (2,2-difluorocyclopropyl) phenyl] -2-pyrrolidone (3.0 g, 9.49 mmol) in N, N-dimethylformamide (30 ml). Added at room temperature and stirred for 24 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 30/70) to obtain 1.25 g of the title compound. (Yield 37%)
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.29 (9H, s), 1.65 (1H, m), 1.82 (1H, m), 2.712.82 (3H, m), 3.90 (1H, m), 4.07 (1H, m), 5.03 (1H, t), 6.16 (1H, d), 7.06 (1H, d), 7.35 (1H, t), 7.48 (1H, d), 7.50 (1H, s ), 7.68 (1H, d)

Preparation of 1- [4-chloro-3- (2,2-difluorocyclopropyl) phenyl] -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone ( Compound No. I-8)
To a solution of 3- (1,1-dimethylethyl) -1H-pyrazole (0.35 g, 2.85 mmol) in N, N-dimethylformamide (5 ml) at room temperature, sodium hydride (60% dispersion, 0.11 g, 2.85 mmol) was added and stirred at room temperature for 30 minutes. This mixture was mixed with 3-bromo-1- [4-chloro-3- (2,2-difluorocyclopropyl) phenyl] -2-pyrrolidone (1.0 g, 2.85 mmol) in N, N-dimethylformamide (10 ml). ) Added to the solution at room temperature and stirred for 24 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 30/70) to obtain 0.24 g of the title compound. (Yield 21%)
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.29 (9H, s), 1.66 (1H, m), 1.87 (1H, m), 2.71.93 (3H, m), 3.86 (1H, m), 4.06 (1H, m), 5.02 (1H, m), 6.16 (1H, s), 7.40-7.47 (3H, m), 7.75 (1H, d)

Preparation of 1- [3- (2,2-difluorocyclopropyl) -4-methylphenyl] -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone ( Compound No. I-9)
To a solution of 3- (1,1-dimethylethyl) -1H-pyrazole (0.78 g, 6.28 mmol) in N, N-dimethylformamide (10 ml) at room temperature sodium hydride (60% dispersion, 0.26 g, 6.50 mmol) was added and stirred at room temperature for 30 minutes. This mixture was mixed with 3-bromo-1- [3- (2,2-difluorocyclopropyl) -4-methylphenyl] -2-pyrrolidone (2.0 g, 6.06 mmol) of N, N-dimethylformamide (30 ml). ) At room temperature and stirred for 24 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 30/70) to obtain 0.79 g of the title compound. (Yield 35%)
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.29 (9H, s), 1.65 (1H, m), 1.82 (1H, m), 2.36 (1H, s), 2.66-2.82 (3H, m), 3.87 (1H, m), 4.04 (1H, m), 5.02 (1H, m), 6.15 (1H, s), 7.21 (1H, d), 7.35 (1H, m), 7.47 (1H, s )
7.65 (1H, d)

Production of 1- (3-cyclopropylphenyl) -3- [3- (1-methylpropyl) -1H-pyrazol-1-yl] -2-pyrrolidone (Compound No. I-2 of the present invention)
3-bromo-1- (3-cyclopropylphenyl) -2-pyrrolidone (0.50 g, 1.78 mmol), 3- (1-methylpropyl) -1H-pyrazole (0.44 g, 3.54 mmol), N , N-diisopropylethylamine (0.46 g, 3.56 mmol) and toluene (30 ml) were heated to reflux for 4 days. The reaction mixture was cooled to room temperature, washed with water, 10% hydrochloric acid and water in this order, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 30/70) to obtain 0.40 g of the title compound. (Yield 69%)
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 0.70 (2H, m), 0.85-0.99 (5H, m), 1.24 (3H, d), 1.52-1.68 (3H, m), 1.90 ( 1H, m), 2.70-2.82 (3H, m), 3.89 (1H, m), 3.98 (1H, m), 5.02 (1H, t), 6.10 (1H, d), 6.89 (1H, d), 7.23 -7.37 (2H, m), 7.47-7.51 (2H, m)

3- (3-Cyclopropylphenyl) -5- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -4-thiazolidinone (present compound number I-3) 3- ( 3-Bromophenyl) -5- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -4-thiazolidinone (0.85 g, 2.24 mmol), cyclopropylboronic acid (0.38 g) 4.42 mmol), tetrakis (triphenylphosphine) palladium (0.26 g, 0.225 mmol), potassium phosphate (1.7 g, 8.01 mmol), water (1 ml) and toluene (30 ml) Under an atmosphere, the mixture was heated and stirred at 100 ° C. for 3 hours. The reaction mixture was cooled to room temperature, water was added, insolubles were filtered off, and the filtrate was separated. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 20/80) to obtain 0.51 g of the title compound. (Yield 67%)
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 0.71 (2H, m), 0.98 (2H, m), 1.30 (9H, s), 1.91 (1H, m), 4.71 (1H, d) , 5.28 (1H, d), 5.97 (1H, s), 6.16 (1H, d), 7.01 (1H, d), 7.20-7.34 (3H, m), 7.44 (1H, d)

Preparation of 1- (3-cyclopropylphenyl) -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone (the present compound number I-1) 1- ( 3-Bromophenyl) -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone (0.99 g, 2.73 mmol), cyclopropylboronic acid (0.31 g) 3.61 mmol), palladium acetate (0.03 g, 0.137 mmol), tricyclohexylphosphine (0.09 g, 0.273 mmol, purity 85%), potassium phosphate (2.0 g, 9.56 mmol), water ( 1 ml) and toluene (15 ml) were heated and stirred at 100 ° C. for 5 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, water was added, insolubles were filtered off, the filtrate was separated, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 30/70) to obtain 0.58 g of the title compound. (Yield 66%)
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 0.71 (2H, m), 0.96 (2H, m), 1.29 (9H, s), 1.91 (1H, m), 2.70-2.82 (2H, m), 3.88 (1H, m), 4.05 (1H, m), 5.03 (1H, t), 6.15 (1H, d), 6.89 (1H, d), 7.23-7.37 (2H, m), 7.47-7.49 (2H, m)

1- [3- (2,2-dichlorocyclopropyl) phenyl] -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone (the present compound number I- 5) Preparation 3- [3- (1,1-Dimethylethyl) -1H-pyrazol-1-yl] -1- (3-vinylphenyl) -2-pyrrolidone (0.39 g, 1.26 mmol)
Of dimethoxyethane (20 ml) was heated to reflux, and a solution of sodium trichloroacetate (3.4 g, 18.3 mmol) in dimethoxyethane (60 ml) was added dropwise to the solution over 7 hours. The reaction solution was cooled to room temperature, insoluble material was filtered off, and the filtrate was concentrated under reduced pressure. The residue was diluted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 40/60) to obtain 0.19 g of the title compound. (Yield 38%)
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.29 (9H, s), 1.88 (1H, m), 1.98 (1H, m), 2.69-2.95 (3H, m), 3.92 (1H, m), 4.10 (1H, m), 5.04 (1H, t), 6.16 (1H, d), 7.08 (1H, d), 7.37 (1H, t), 7.48 (1H, d), 7.53 (1H, m ), 7.73 (1H, d)

1- (4-Cyclopropylpyrimidin-2-yl) -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone (the present compound number II-1)
3-Bromo-1- (4-cyclopropylpyrimidin-2-yl) -2-pyrrolidone (0.52 g, 1.84 mmol), 3- (1,1-dimethylethyl) -1H-pyrazole (0.46 g, 3.70 mmol), N, N-diisopropylethylamine (0.48 g, 3.71 mmol) and toluene (10 ml) were heated to reflux for 40 hours. The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 70/30) to obtain 0.27 g of the title compound. (Yield 45%)
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.11-1.20 (4H, m), 1.28 (9H, s), 1.98 (1H, m), 2.71 (1H, m), 3.96 (1H, m), 4.28 (1H, m), 5.08 (1H, t), 6.14 (1H, d), 6.93 (1H, d), 7.50 (1H, d), 8.47 (1H, d)

3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -1- [3- (1-methylcyclopropyl) phenyl] -2-pyrrolidone (the present compound number I-11) Preparation of 1.0 mol / l Diethylzinc in hexane solution (12.4 ml, 12.4 mmol) and dichloromethane (20 ml) under ice cooling (5 ° C. or lower) with trifluoroacetic acid (1.4 g, 12.3 mmol) ) In dichloromethane (10 ml) was added dropwise and stirred for 20 minutes under ice cooling. To this mixture, a solution of diiodomethane (3.3 g, 12.3 mmol) in dichloromethane (10 ml) was added dropwise under ice cooling (5 ° C. or lower) and stirred for 20 minutes under ice cooling. To this mixture was further added 3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] 1- (3-isopropenylphenyl) -2-pyrrolidone (1.0 g, 3.09 mmol). A dichloromethane (20 ml) solution was added dropwise under ice cooling (5 ° C. or lower), and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into a saturated aqueous ammonium chloride solution and separated, and the organic layer was washed with water and a saturated aqueous sodium bicarbonate solution in that order, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was washed with hexane to obtain 0.78 g of the title compound. (Yield 75%, melting point 127-128 ° C.)

Production of 1- (3-cyclobutylphenyl) -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone (Compound No. III-1 of the present invention)
Magnesium (0.90 g, 37.0 mmol) was added to tetrahydrofuran (2 ml), and a solution of cyclobutyl bromide (5.0 g, 37.0 mmol) in tetrahydrofuran (15 ml) was added dropwise to the mixture at 45 ° C., and the mixture was stirred at room temperature for 1 hour. Stir. The reaction mixture was added dropwise to a suspension of zinc bromide (8.3 g, 36.9 mmol) in tetrahydrofuran (30 ml) under ice cooling. Furthermore, 1- (3-bromophenyl) -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone (2.0 g, 5.52 mmol) was added to the reaction mixture. And 1,1′-bis (diphenylphosphino) ferrocene-palladium (II) dichloride-dichloromethane complex (0.20 g, 0.245 mmol) were added at −78 ° C., and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 30/70) to obtain 1.9 g of the title compound. (Yield 99%, melting point 154-155 ° C.)

Preparation of 3- (3-cyclopropylphenyl) -5- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -4-oxazolidinone (present compound number I-17) 3- ( 3-Bromophenyl) -5- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -4-oxazolidinone (0.50 g, 1.37 mmol), cyclopropylboronic acid (0.29 g 3.38 mmol), palladium acetate (0.03 g, 0.134 mmol), tricyclohexylphosphine (0.09 g, 0.273 mmol), potassium phosphate (1.0 g, 4.71 mmol), water (1 ml) and toluene (15 ml) of the mixture was heated and stirred at 100 ° C. for 5 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, water was added, insolubles were filtered off, the filtrate was separated, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 20/80) to obtain 0.30 g of the title compound. (Yield 67%, melting point 102-103 ° C.)

Production of 1- {3- {3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-oxopyrrolidin-1-yl} phenyl} cyclopropanecarbonitrile (compound of the present invention) Number I-10)
1- [3- (3-Bromo-2-oxopyrrolidin-1-yl) phenyl] cyclopropanecarbonitrile (2.0 g, 6.55 mmol), 3- (1,1-dimethylethyl) -1H-pyrazole ( A mixture of 2.4 g, 19.3 mmol) and toluene (6 ml) was heated to reflux for 6 hours. The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 50/50) to obtain 1.9 g of the title compound. (Yield 83%, melting point 148-150 ° C.)

Preparation of 1- {3- {3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-oxopyrrolidin-1-yl} phenyl} cyclopropanecarbothioamide (compound of the present invention) Number I-37)
1- {3- {3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-oxopyrrolidin-1-yl} phenyl} cyclopropanecarbonitrile (0.84 g, 2 .41 mmol), sodium hydrosulfide (0.05 g), and saturated ethanol solution of hydrogen sulfide (30 ml) were heated and stirred at 90 ° C. for 48 hours in a sealed tube. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 70/30) to obtain 0.80 g of the title compound. (Yield 87%, melting point 147-148 ° C.)

Production of 1- (3-cyclopropylphenyl) -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -pyrrolidine-2-thione (present compound number I-42) 1 A solution of-(3-cyclopropylphenyl) -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone (0.98 g, 3.03 mmol) in toluene (30 ml) Diisopropylethylamine (2.0 g, 15.2 mmol) and 2,4-bis- (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane 2,4-disulfide (6.13 g, 15. 2 mmol) was added and the mixture was heated and stirred at 90 ° C. After cooling the reaction mixture to room temperature, insolubles were filtered off, the filtrate was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 33/67) to give the title 0.88g of compound was obtained. (Yield 86%)
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 0.68-0.74 (2H, m), 0.95-1.00 (2H, m), 1.30 (9H, s), 1.90 (1H, m), 2.69- 2.86 (2H, m), 4.08 (1H, m), 4.48 (1H, m), 5.22 (1H, m), 6.13 (1H, d), 7.02 (1H, d), 7.21-7.36 (3H, m) 7.53 (1H, d)

1- (3-cyclopropyl-4-fluorophenyl) -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone (the present compound number I-22) Preparation 1- (3-Bromo-4-fluorophenyl) -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone (0.51 g, 1.34 mmol), Cyclopropylboronic acid (0.29 g, 3.35 mmol), palladium acetate (0.03 g, 0.134 mmol), 15% tricyclohexylphosphine in toluene (0.50 g, 0.268 mmol), potassium phosphate (1. 0 g, 4.69 mmol), water (2 ml) and toluene (40 ml) were heated and stirred at 100 ° C. for 6 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, water was added, insolubles were filtered off, the filtrate was separated, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 33/67) to obtain 0.38 g of the title compound. (Yield 83%)
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 0.71-0.77 (2H, m), 0.90-1.02 (2H, m), 1.29 (9H, s), 2.08 (1H, m), 2.64- 2.84 (2H, m), 3.84 (1H, m), 4.02 (1H, m), 5.01 (1H, t), 6.15 (1H, d), 7.00 (1H, t), 7.24-7.33 (2H, m) 7.46 (1H, d)

  Tables 26 to 29 show physical properties of the compounds obtained in Examples 1 to 15 and the compounds of the present invention produced by the same method as those examples.

For compound numbers I-3, I-13, I-18, I-19, I-23, I-24, I-27, I-35 and I-41, ¹ H-NMR data (CDCl 3 / TMS δ (Ppm)) values are shown below.
Compound No. I-3: 0.70-0.74 (2H, m), 0.95-1.02 (2H, m), 1.30 (9H, s), 1.93 (1H, m), 4.71 (1H, d), 5.28 (1H, d ), 5.97 (1H, s), 6.16 (1H, d), 7.01 (1H, d), 7.19-7.34 (3H, m), 7.44 (1H, d)
Compound No. I-13: 0.68-0.73 (2H, m), 0.95-1.01 (2H, m), 1.29 (9H, s), 1.88 (1H, m), 2.70-2.85 (2H, m), 3.82-4.07 (2H, m), 5.02 (1H, t), 6.16 (1H, d), 6.85 (1H, s), 7.40-7.42 (2H, m), 7.47 (1H, d)
Compound No. I-18: 0.73-0.77 (2H, m), 1.04-1.06 (2H, m), 1.29 (9H, s), 1.93 (1H, m), 2.75-2.86 (2H, m), 3.88 (1H , m), 4.06 (1H, m), 5.02 (1H, t), 6.16 (1H, d), 7.14 (1H, s), 7.46 (1H, d), 7.64 (1H, s), 7.81 (1H, s)
Compound No. I-19: 0.67-0.73 (2H, m), 0.92-0.98 (2H, m), 1.29 (9H, s), 1.88 (1H, m), 2.69-2.82 (2H, m), 3.79 (3H , sm), 3.82-4.06 (2H, m), 5.03 (1H, t), 6.16 (1H, d), 6.45 (1H, s), 6.95 (1H, s), 7.16 (1H, s), 7.47 ( 1H, d)
Compound No. I-23: 0.66-0.72 (2H, m), 0.91-0.97 (2H, m), 1.29 (9H, s), 1.85 (1H, m), 2.32 (3H, s), 2.69-2.76 (2H , m), 3.83-4.07 (2H, m), 5.02 (1H, t), 6.15 (1H, d), 6.72 (1H, s), 7.23 (1H, s), 7.48 (1H, d)
Compound No. I-24: 0.62-0.66 (2H, m), 0.92-0.96 (2H, m), 1.29 (9H, s), 1.86 (1H, m), 2.68-2.76 (2H, m), 3.86-4.02 (2H, m), 5.02 (1H, t), 6.15 (1H, d), 6.94-7.05 (2H, m), 7.16
(1H, d), 7.48 (1H, d)
Compound No. I-27: 0.67-0.73 (2H, m), 0.93-1.00 (2H, m), 1.29 (9H, s), 1.88 (1H, m), 2.67-2.84 (2H, m), 3.83-4.16 (2H, m), 5.02 (1H, t), 6.15 (1H, d), 6.55 (1H, d), 7.21-7.26
(2H, m), 7.46 (1H, d)
Compound No. I-35: 0.74-0.78 (2H, m), 1.00-1.05 (2H, m), 1.29 (9H, s), 2.11 (1H, m), 2.66-2.85 (2H, m), 3.81 (1H , m), 4.00 (1H, m), 4.99 (1H, t), 6.15 (1H, d), 7.02 (1H, br), 7.32 (1H, m), 7.45 (1H, d)
Compound Nos. I-41: 0.68-0.74 (2H, m), 0.95-1.00 (2H, m), 1.30 (9H, s), 1.90 (1H, m), 2.69-2.86 (2H, m), 4.08 (1H , m), 4.48 (1H, m), 5.22 (1H, m), 6.13 (1H, d), 7.02 (1H, d), 7.21-7.36 (3H, m), 7.53 (1H, d)

Next, a method for producing a production intermediate used in the production example will be described.
<Reference example>
(Production Intermediate Example 1) Production of 3-bromo-1- (3-cyclopropylphenyl) -2-pyrrolidone (1) Production of 3-cyclopropylaniline 3-Bromoaniline (6.5 g, 37.8 mmol), cyclo Propylboronic acid (4.2 g, 48.9 mmol), palladium acetate (0.42 g, 1.87 mmol), tricyclohexylphosphine (1.3 g, 3.94 mmol, purity 85%), potassium phosphate (28.1 g, 132 mmol), water (30 ml) and toluene (170 ml) were heated and stirred at 100 ° C. for 24 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, water was added, insoluble matters were filtered off, and the organic layer of the filtrate was separated. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 30/70) to obtain 4.5 g (yield 89%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 0.66 (2H, m), 0.90 (2H, m), 1.80 (1H, m), 3.58 (2H, br), 6.40 (1H, s) 6.46-6.50 (2H, m), 7.03 (1H, t)
(2) Preparation of 2,4-dibromo-N- (3-cyclopropylphenyl) butanamide 3-cyclopropylaniline (4.5 g, 33.8 mmol) and triethylamine (3.8 g, 37.6 mmol) in dichloromethane (100 ml) ) 2,4-Dibromobutyryl chloride (10.0 g, 34.0 mmol, purity 90%) was added dropwise to the solution under ice cooling. After stirring at room temperature for 1 hour, water was added to the reaction mixture and the phases were separated, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 15/85) to obtain 9.8 g (yield 80%) of the title compound.
(3) Preparation of 3-bromo-1- (3-cyclopropylphenyl) -2-pyrrolidone 2,4-dibromo-N- (3-cyclopropylphenyl) butanamide (9.8 g, 27.1 mmol) of N, To a solution of N-dimethylformamide (100 ml), sodium hydride (60% dispersion, 1.1 g, 27.5 mmol) was added at room temperature, and the mixture was stirred at room temperature for 1 hour. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 30/70) to obtain 6.0 g (yield 79%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 0.72 (2H, m), 0.97 (2H, m), 1.92 (1H, m), 2.45 (1H, m), 2.72 (1H, m) , 3.82 (1H, m), 4.58 (1H, m), 6.90 (1H, d), 7.27 (1H, t), 7.35 (1H, d), 7.43 (1H, s)

(Production Intermediate Example 2) Production of 1- [3- (3-bromo-2-oxopyrrolidin-1-yl) phenyl] cyclopropanecarbonitrile (1) Production of 1- (3-nitrophenyl) cyclopropanecarbonitrile 2- (3-Nitrophenyl) acetonitrile (5.0 g, 30.8 mmol), 1,2-dibromoethane (11.6 g, 61.7 mmol), tetrabutylammonium bromide (10.0 g, 31.0 mmol) in acetonitrile To the (20 ml) solution, 50% sodium hydroxide solution (12.0 g) was added dropwise under ice cooling. After stirring overnight at room temperature, the solvent was distilled off under reduced pressure. Water was added to the residue, acidified with 10% hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography eluting solvent: ethyl acetate / n-hexane = 25/75) to obtain 4.5 g (yield 78%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.52 (2H, m), 1.87 (2H, m), 7.58 (1H, t), 7.75 (1H, d) 8.06 (1H, s), 8.16 (1H, d)
(2) Production of 1- (3-aminophenyl) cyclopropanecarbonitrile 1- (3-Nitrophenyl) cyclopropanecarbonitrile (4.5 g, 23.9 mmol), acetic acid of 10% palladium on activated carbon (0.45 g) The ethyl (200 ml) solution was stirred under a hydrogen atmosphere for 3 hours. The reaction mixture was filtered through celite, and the filtrate was concentrated under reduced pressure to obtain 3.8 g (yield 99%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.37 (2H, m), 1.67 (2H, m), 3.73 (1H, br), 6.57-6.60 (2H, m), 6.67 (1H, s), 7.11 (1H, s)
(3) Preparation of 2,4-dibromo-N- [3- (1-cyanocyclopropyl) phenyl] butanamide 1- (3-aminophenyl) cyclopropanecarbonitrile (3.8 g, 24.0 mmol) and triethylamine ( 2,4-Dibromobutyryl chloride (7.4 g, 25.2 mmol, purity 90%) was added dropwise to a solution of 2.7 g, 26.7 mmol) in dichloromethane (50 ml) under ice cooling. After stirring at room temperature for 1 hour, the reaction mixture was washed successively with water and saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 9.5 g (yield 99%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.42-1.46 (2H, m), 1.72-1.77 (2H, m), 2.50-2.80 (2H, m), 3.59-3.64 (2H, m ), 4.69 (1H, m), 7.11 (1H, d), 7.34 (1H, t), 7.46 (1H, d), 7.52 (1H, s), 8.06 (1H, br)
(4) Preparation of-[3- (3-Bromo-2-oxopyrrolidin-1-yl) phenyl] cyclopropanecarbonitrile 2,4-Dibromo-N- [3- (1-cyanocyclopropyl) phenyl] butanamide To a solution of (9.5 g) in N, N-dimethylformamide (50 ml) was added sodium hydride (60% dispersion, 1.0 g, 25.0 mmol) at room temperature, and the mixture was stirred at room temperature for 3 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 30/70) to obtain 5.8 g (yield 79%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.43-1.48 (2H, m), 1.72-1.77 (2H, m), 2.46 (1H, m), 2.74 (1H, m), 3.85 ( 1H, m), 4.08 (1H, m), 4.59 (1H, m), 7.18 (1H, d), 7.35 (1H, t), 7.51 (1H, d), 7.66 (1H, s)

(Production Intermediate Example 3) Production of 1- [3- (3-bromo-2-oxopyrrolidin-1-yl) phenyl] cyclopropanecarbaldehyde (1) Production of 1- (3-nitrophenyl) cyclopropanecarbaldehyde Toluene (300 ml) solution of 1- (3-nitrophenyl) cyclopropanecarbonitrile (9.3 g, 49.4 mmol) in toluene solution of 1.0 mol / l diisobutylaluminum hydride at −70 ° C. to −65 ° C. (75 ml, 74.3 mmol) was added dropwise. After stirring at −70 ° C. for 1 hour, the reaction mixture was poured into a saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic layer was washed with 10% by weight hydrochloric acid, water and saturated aqueous sodium carbonate solution in that order, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 7.8 g (yield 83%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.50-1.53 (2H, m), 1.67-1.70 (2H, m), 7.55 (1H, t), 7.66 (1H, d), 8.15- 8.20 (2H, m), 9.06 (1H, s)
(2) Preparation of 1- [3- (3-bromo-2-oxopyrrolidin-1-yl) phenyl] cyclopropanecarbaldehyde 1- (3-nitrophenyl) cyclopropanecarbaldehyde (3.6 g, 18.8 mmol) ), Iron powder (6.3 g, 113 mmol), acetic acid (2 ml) in ethyl acetate (100 ml) and water (50 ml) were heated to reflux for 10 hours. The reaction mixture was cooled to room temperature, insoluble matters were filtered off, and the organic layer of the filtrate was separated. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was dissolved in dichloromethane (100 ml), triethylamine (2.3 g, 22.7 mmol) was added, and 2,4-dibromobutyryl chloride (5.1 g, 19.3 mmol, purity 90%) was cooled with ice. ) Was added dropwise. After stirring overnight at room temperature, the reaction mixture was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was dissolved in N, N-dimethylformamide (100 ml), sodium hydride (60% dispersion, 0.75 g, 18.8 mmol) was added under ice cooling, and the mixture was stirred overnight at room temperature. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 40/60) to obtain 3.3 g (yield 57%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.28-1.46 (2H, m), 1.58-1.61 (2H, m), 2.46 (1H, m), 2.73 (1H, m), 3.84 ( 1H, m), 4.08 (1H, m), 4.59 (1H, m), 7.16 (1H, d), 7.39 (1H, t), 7.52 (1H, d), 7.69 (1H, s), 9.21 (1H , s)

(Production Intermediate Example 4) Production of 3-bromo-1- (3,5-dicyclopropylphenyl) -2-pyrrolidone (1) Production of 3,5-dicyclopropylaniline 3,5-Dibromoaniline (2. 0 g, 7.97 mmol), cyclopropylboronic acid (1.8 g, 21.0 mmol), palladium acetate (0.18 g, 0.802 mmol), 15% tricyclohexylphosphine in toluene (3.0 g, 1.60 mmol, ), Potassium phosphate (11.8 g, 55.6 mmol), water (5 ml) and toluene (100 ml) were heated and stirred at 100 ° C. for 24 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, water was added, insoluble matters were filtered off, and the organic layer of the filtrate was separated. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 25/75) to obtain 1.0 g (yield 72%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 0.62-0.72 (4H, m), 0.80-0.92 (4H, m), 1.76 (2H, m)
3.53 (2H, br), 6.18 (2H, s), 6.26 (1H, s)
(2) Preparation of 3-bromo-1- (3,5-dicyclopropylphenyl) -2-pyrrolidone 3,5-dicyclopropylaniline (1.0 g, 5.77 mmol) and triethylamine (0.70 g, 6 .92 mmol) in dichloromethane (100 ml) was added dropwise 2,4-dibromobutyryl chloride (1.9 g, 6.47 mmol, purity 90%) under ice cooling. After stirring at room temperature for 1 hour, water was added to the reaction mixture and the phases were separated, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was dissolved in N, N-dimethylformamide (30 ml), sodium hydride (60% dispersion, 0.25 g, 6.25 mmol) was added at room temperature, and the mixture was stirred at room temperature for 2 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 25/75) to obtain 1.0 g (yield 54%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 0.67-0.71 (4H, m), 0.92-0.97 (4H, m), 1.88 (2H, m), 2.42 (1H, m), 2.71 ( 1H, m), 3.80 (1H, m), 4.02 (1H, m), 4.56 (1H, m), 6.63 (1H, s), 7.12 (2H, s)

(Production Intermediate Example 5) Production of 3-bromo-1- [3- (2,2-difluorocyclopropyl) phenyl] -2-pyrrolidone (1) 1- (2,2-difluorocyclopropyl) -3-nitrobenzene Preparation of 3-nitrostyrene (5.0 g, 33.5 mmol) in diethylene glycol dimethyl ether (45 ml) was heated to reflux, and sodium chlorodifluoroacetate (30.6 g, 201 mmol) in diethylene glycol dimethyl ether (250 ml) was heated to reflux. The solution was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was further heated to reflux for 1 hour. The reaction mixture was cooled to room temperature, insoluble material was filtered off, and the filtrate was concentrated under reduced pressure. The residue was diluted with ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 5/95) to obtain 5.5 g (yield 82%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.72 (1H, m), 1.96 (1H, m), 2.86 (1H, m), 7.50-7.58 (2H, m), 8.10 (1H, s), 8.14 (1H, d)
(2) Production of 3- (2,2-difluorocyclopropyl) aniline 1- (2,2-difluorocyclopropyl) -3-nitrobenzene (5.4 g, 27.1 mmol), iron powder (9.1 g, 163 mmol) ), Acetic acid (1 ml), ethyl acetate (100 ml) and water (50 ml) were heated to reflux for 10 hours. The reaction mixture was cooled to room temperature, insoluble matters were filtered off, and the organic layer of the filtrate was separated. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 4.6 g (yield 99%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.58 (1H, m), 1.76 (1H, m), 2.67 (1H, m), 3.65 (2H, br), 6.54-6.63 (3H, m), 7.11 (1H, t)
(3) Preparation of 2,4-dibromo-N- [3- (2,2-difluorocyclopropyl) phenyl] butanamide 3- (2,2-difluorocyclopropyl) aniline (4.6 g, 27.2 mmol) and 2,4-Dibromobutyryl chloride (8.8 g, 29.9 mmol, purity 90%) was added dropwise to a solution of triethylamine (3.3 g, 32.6 mmol) in dichloromethane (100 ml) under ice cooling. After further stirring at room temperature for 6 hours, the reaction mixture was washed with water, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 9.4 g (yield 87%) of the title compound.
(4) Preparation of 3-bromo-1- [3- (2,2-difluorocyclopropyl) phenyl] -2-pyrrolidone 2,4-dibromo-N- [3- (2,2-difluorocyclopropyl) phenyl ] To a solution of butanamide (9.4 g, 23.7 mmol) in N, N-dimethylformamide (100 ml), sodium hydride (0.95 g, 60% dispersion, 23.7 mmol) was added at room temperature and stirred at room temperature for 24 hours. did. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 30/70) to obtain 5.3 g (yield 71%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.65 (1H, m), 1.84 (1H, m), 2.46 (1H, m), 2.69-2.82 (2H, m), 3.83 (1H, m), 4.05 (1H, m), 4.59 (1H, m), 7.06 (1H, d), 7.35 (1H, t), 7.49 (1H, d), 7.62 (1H, s)

(Production Intermediate Example 6) Production of 3-bromo-1- [4-chloro-3- (2,2-difluorocyclopropyl) phenyl] -2-pyrrolidone (1) N- [3- (2,2-difluoro Preparation of cyclopropyl) phenyl] acetamide 3- (2,2-difluorocyclopropyl) aniline (4.5 g, 26.6 mmol) and triethylamine (3.0 g, 29.3 mmol) in dichloromethane (50 ml) Below, acetyl chloride (2.1 g, 26.6 mmol) was added dropwise. After stirring at room temperature for 24 hours, the reaction mixture was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was washed with n-hexane to obtain 5.5 g (yield 98%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.61 (1H, m), 1.80 (1H, m), 2.17 (3H, s), 2.72 (1H, m), 6.97 (1H, d) 7.26 (1H, t), 7.37-7.43 (3H, m)
(2) Preparation of N- [4-chloro-3- (2,2-difluorocyclopropyl) phenyl] acetamide N- [3- (2,2-difluorocyclopropyl) phenyl] acetamide (4.4 g, 20. To a solution of 8 mmol) in dichloromethane (100 ml), sulfinyl chloride (2.8 g, 20.8 mmol) was added dropwise under ice cooling. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 40/60) to give 4.1 g of the title compound ( Yield 80%).
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.63 (1H, m), 1.88 (1H, m), 2.17 (1H, s), 2.87 (1H, m), 7.20 (1H, br) , 7.33-7.39 (2H, m), 7.43 (1H, s)
(3) Preparation of 4-chloro-3- (2,2-difluorocyclopropyl) aniline N- [4-Chloro-3- (2,2-difluorocyclopropyl) phenyl] acetamide (4.1 g, 16.7 mmol) ) And 10 wt% hydrochloric acid (50 ml) were heated to reflux for 2 hours. The reaction mixture was cooled to room temperature, made alkaline with 25 wt% aqueous sodium hydroxide solution, and extracted with diethyl ether. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 2.4 g (yield 71%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.55 (1H, m), 1.84 (1H, m), 2.83 (1H, m), 3.66 (2H, br), 6.52-6.56 (2H, m), 7.15 (1H, d)
(4) Preparation of 2,4-dibromo-N- [4-chloro-3- (2,2-difluorocyclopropyl) phenyl] butanamide 4-chloro-3- (2,2-difluorocyclopropyl) aniline (2 0.5 g, 12.3 mmol) and triethylamine (1.5 g, 14.8 mmol) in dichloromethane (100 ml) under ice-cooling, 2,4-dibromobutyryl chloride (4.0 g, 13.5 mmol, purity 90%) ) Was added dropwise. After stirring at room temperature for 6 hours, the reaction mixture was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 15/85) to obtain 4.5 g (yield 85%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.65 (1H, m), 1.90 (1H, m), 2.55 (1H, m), 2.75 (1H, m), 2.89 (1H, m) 3.56-3.66 (2H, m), 4.68 (1H, m), 7.40 (2H, s), 7.49 (1H, s), 7.97 (1H, br)
(5) Preparation of 3-bromo-1- [4-chloro-3- (2,2-difluorocyclopropyl) phenyl] -2-pyrrolidone 2,4-dibromo-N- [4-chloro-3- (2 , 2-Difluorocyclopropyl) phenyl] butanamide in a solution of 4.5 g (10.4 mmol) of N, N-dimethylformamide (100 ml) at room temperature with sodium hydride (60% dispersion, 0.42 g, 10.4 mmol). In addition, the mixture was stirred at room temperature for 24 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 30/70) to obtain 3.5 g (yield 96%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.65 (1H, m), 1.91 (1H, m), 2.46 (1H, m), 2.74 (1H, m), 2.89 (1H, m) , 3.81 (1H, m), 4.03 (1H, m), 4.58
(1H, m), 7.40-7.49 (2H, m), 7.67 (1H, d)

(Production Intermediate Example 7) Production of 3-bromo-1- [3- (2,2-difluorocyclopropyl) -4-methylphenyl] -2-pyrrolidone (1) Production of 2-methyl-5-nitrostyrene Nitrogen Under atmosphere, 2-bromo-4-nitrotoluene (10.0 g, 46.3 mmol), tri-n-butyltin (14.7 g, 46.4 mmol), tetrakistriphenylphosphine palladium (1.1 g, 0.952 mmol) and toluene (100 ml) of the mixture was heated and stirred at 100 ° C. for 5 hours. The reaction mixture was cooled to room temperature, washed with an aqueous potassium fluoride solution, insoluble matters were filtered off, and the organic layer of the filtrate was separated. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (eluent: diethyl ether / n-hexane = 20/80) to obtain 7.2 g (yield 95%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 2.44 (3H, s), 5.48 (1H, d), 5.80 (1H, d), 6.91 (1H, dd), 7.30 (1H, d) , 8.01 (1H, d), 5.48 (1H, d), 8.31 (1H, s)
(2) Preparation of 2- (2,2-difluorocyclopropyl) -1-methyl-3-nitrobenzene Heating a solution of 2-methyl-5-nitrostyrene (5.5 g, 33.7 mmol) in diethylene glycol dimethyl ether (45 ml) The solution was refluxed, and a solution of sodium chlorodifluoroacetate (30.8 g, 202 mmol) in diethylene glycol dimethyl ether (200 ml) was added dropwise to this solution over 4 hours. After completion of the addition, the solution was further heated to reflux for 1 hour. The reaction solution was cooled to room temperature, insoluble material was filtered off, and the filtrate was concentrated under reduced pressure. The residue was diluted with ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 10/90) to obtain 6.3 g (yield 88%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.74 (1H, m), 1.95 (1H, m), 2.49 (1H, s), 2.75 (1H, m), 7.37 (1H, d) , 8.03-8.08 (2H, m)
(3) Preparation of 3- (2,2-difluorocyclopropyl) -4-methylaniline 2- (2,2-difluorocyclopropyl) -1-methyl-3-nitrobenzene (6.3 g, 29.6 mmol), A mixture of iron powder (9.9 g, 177 mmol), acetic acid (1 ml), ethyl acetate (200 ml) and water (100 ml) was heated to reflux for 8 hours. After cooling the reaction mixture to room temperature, insolubles were filtered off and separated. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 30/70) to obtain 4.0 g (yield 74%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.55 (1H, m), 1.77 (1H, m), 2.64 (1H, m), 3.54 (2H, br), 6.51-6.56 (2H, m), 6.97 (1H, d)
(4) Preparation of 2,4-dibromo-N- [3- (2,2-difluorocyclopropyl) -4-methylphenyl] butanamide 3- (2,2-difluorocyclopropyl) -4-methylaniline (4 0.02 g, 21.8 mmol) and triethylamine (2.4 g, 23.7 mmol) in dichloromethane (100 ml) under ice-cooling, 2,4-dibromobutyryl chloride (6.7 g, 23.1 mmol, purity 90%) ) Was added dropwise. After stirring at room temperature for 4 hours, water was added to the reaction mixture for liquid separation. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resulting residue was washed with n-hexane to obtain 8.5 g of the title compound (yield 95%).
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.63 (1H, m), 1.83 (1H, m), 2.05 (1H, s), 2.55 (1H, m), 2.72 (1H, m) 3.56-3.64 (2H, m), 4.67 (1H, m), 7.17 (1H, d), 7.31 (1H, br), 7.41 (1H, s), 7.94 (1H, br)
(5) Production of 3-bromo-1- [3- (2,2-difluorocyclopropyl) -4-methylphenyl] -2-pyrrolidone 2,4-dibromo-N- [3- (2,2-difluoro Cyclopropyl) -4-methylphenyl] butanamide (8.5 g, 20.7 mmol) in N, N-dimethylformamide (100 ml) at room temperature with sodium hydride (60% dispersion, 0.91 g, 22.8 mmol) And stirred at room temperature for 4 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 30/70) to obtain 5.6 g (yield 82%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.63 (1H, m), 1.84 (1H, m), 2.36 (1H, s), 2.45 (1H, m), 2.52-2.78 (2H, m), 3.81 (1H, m), 4.02 (1H, m), 4.58 (1H, m), 7.21 (1H, d), 7.36 (1H, m), 7.59 (1H, d)

(Production Intermediate Example 8) Production of 3-bromo-1- (4-cyclopropylpyrimidin-2-yl) -2-pyrrolidone (1) Production of 2-amino-4-cyclopropylpyrimidine 1-cyclopropylethanone ( A mixture of 9.3 g, 111 mmol) and dimethylformamide dimethyl acetal (50 ml) was heated to reflux for 17 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. To the obtained residue, guanidine carbonate (24.0 g, 133 mmol) and 2-ethoxyethanol (20 ml) were added, and the mixture was heated to reflux for 18 hours. The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 1.7 g (yield 7%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 0.95-1.07 (4H, m), 1.82 (1H, m), 4.90 (2H, br), 6.46 (1H, d), 8.06 (1H, d)
(2) Preparation of 3-bromo-1- (4-cyclopropylpyrimidin-2-yl) -2-pyrrolidone 1.1 g (8.14 mmol) of 2-amino-4-cyclopropylpyrimidine and triethylamine (0.99 g, To a solution of 9.78 mmol) in dichloromethane (50 ml), 2,4-dibromobutyryl chloride (2.6 g, 8.85 mmol, purity 90%) was added dropwise under ice cooling, and the mixture was stirred at room temperature for 2 hours. Water was added to the reaction mixture and the phases were separated, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was dissolved in N, N-dimethylformamide (30 ml), sodium hydride (60% dispersion, 0.36 g, 9.00 mmol) was added to this solution at room temperature, and the mixture was stirred at room temperature for 1 hour. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 30 / 70-50 / 50) to obtain 0.52 g (yield 23%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.06-1.20 (4H, m), 1.99 (1H, m), 2.38 (1H, m), 2.65 (1H, m), 4.07-4.19 ( 3H, m), 4.59 (1H, m), 6.94 (1H, d), 8.49 (1H, d)

(Production Intermediate Example 9) Production of 1- (3-bromo-4-fluorophenyl) -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone (1) Preparation of 2,4-dibromo-N- (3-bromo-4-fluorophenyl) butanamide 3-bromo-4-fluoroaniline (2.0 g, 10.5 mmol) and triethylamine (1.2 g, 11.6 mmol) 2,4-Dibromobutyryl chloride (3.1 g, 34.0 mmol, purity 90%) was added dropwise to a dichloromethane (50 ml) solution under ice cooling. After stirring at room temperature for 2 hours, water was added to the reaction mixture and the phases were separated, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 20/80) to obtain 4.8 g (yield 99%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 2.55 (1H, m), 2.75 (1H, m), 3.55-3.70 (2H, m), 4.68 (1H, m), 7.11 (1H, t), 7.43 (1H, m), 7.85 (1H, m), 7.97 (1H, br)
(2) Preparation of 3-bromo-1- (3-bromo-4-fluorophenyl) -2-pyrrolidone 2,4-dibromo-N- (3-bromo-4-fluorophenyl) butanamide (4.88 g) To a N, N-dimethylformamide (50 ml) solution was added sodium hydride (60% dispersion, 0.46 g, 11.6 mmol) at room temperature, and the mixture was stirred at room temperature for 3 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 30/70) to obtain 3.2 g (yield 91%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 2.47 (1H, m), 2.74 (1H, m), 3.80 (1H, m), 4.02 (1H, m), 4.58 (1H, m) 7.14 (1H, t), 7.60 (1H, m), 7.88 (1H, br)
(3) Production of 1- (3-bromo-4-fluorophenyl) -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone 3- (1,1 -Dimethylethyl) -1H-pyrazole (0.41 g, 3.26 mmol) in N, N-dimethylformamide (10 ml) was added sodium hydride (60% dispersion, 0.13 g, 3.26 mmol) at room temperature. And stirred at room temperature for 30 minutes. This mixture was added to a solution of 3-bromo-1- (3-bromo-4-fluorophenyl) -2-pyrrolidone (1.0 g, 2.97 mmol) in N, N-dimethylformamide (30 ml) at room temperature. Stir for 4 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate / n-hexane = 30/70) to obtain 0.65 g (yield 58%) of the title compound.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.30 (9H, s), 2.71-2.87 (2H, m), 3.85 (1H, m), 4.05 (1H, m), 5.09 (1H, t), 6.17 (1H, d), 7.14 (1H, t), 7.47 (1H, d), 7.61 (1H, m), 7.93 (1H, m)

(Production Intermediate Example 10) Production of 3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -1- (3-vinylphenyl) -2-pyrrolidone 1- (3-Bromophenyl ) -3- [3- (1,1-dimethylethyl) -1H-pyrazol-1-yl] -2-pyrrolidone 2.0 g (5.52 mmol), tri n-butyltin 2.1 g (6.62 mmol), Tetrakistriphenylphosphinepalladium (0.32 g, 0.277 mmol) and toluene (30 ml) were added, and the mixture was heated and stirred at 100 ° C. for 4 hours. The reaction mixture was cooled to room temperature, washed with an aqueous potassium fluoride solution, insoluble matters were filtered off, and the organic layer of the filtrate was separated. The organic layer was dried over anhydrous magnesium sulfate, the inorganic substance was filtered off, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (elution solvent: diethyl ether / n-hexane = 35/65), 1.4 g (yield 82%) of the title compound was obtained.
¹ H-NMR data (CDCl ₃ / TMS δ (ppm)): 1.29 (9H, s), 2.69-2.85 (2H, m), 3.90 (1H, m), 4.10 (1H, m), 5.04 (1H, t), 5.28 (1H, d), 5.77 (1H, d), 6.16 (1H, d), 6.71 (1H, dd), 7.25 (1H, d), 7.35 (1H, t), 7.48 (1H, d ), 7.53 (1H, d), 7.77 (1H, s)
Table 30 shows the physical property values of the compound obtained in Production Example 9 above and intermediate compounds produced in the same manner as in these examples.

次に代表的な製剤例をあげて製剤方法を具体的に説明する。化合物、添加剤の種類及び配合比率は、これのみに限定されることなく広い範囲で変更可能である。以下の説明において「部」は重量部を意味する。

Next, the preparation method will be specifically described with reference to typical preparation examples. The types and compounding ratios of the compounds and additives are not limited to these and can be changed in a wide range. In the following description, “parts” means parts by weight.

<Formulation Example 1> Wetting agent Compound No. (I-1) 50 parts, sodium alkylnaphthalenesulfonate 5 parts, sodium lauryl sulfate 5 parts, diatomaceous earth 10 parts, and clay 30 parts are mixed and pulverized using an impact pulverizer. This gave a wettable powder. Moreover, it was replaced with the compound number (I-1), and the wettable powder was able to be obtained similarly using the compound of the said Tables 1-29.

<Formulation example 2> Flowable agent Wet pulverized 5 parts of coarsely pulverized compound number (I-1), 15 parts of polyoxyethylene styrylphenyl ether sodium sulfate, 10 parts of propylene glycol, 0.2 part of xanthan gum and 69.8 parts of water A flowable agent was obtained by mixing and grinding glass beads as a grinding medium using a machine. In addition, a flowable agent could be obtained in the same manner using the compounds shown in Tables 1 to 29 instead of the compound number (I-1).

<Formulation Example 3> Emulsion Compound No. (I-1) 10 parts, polyoxyethylene styryl phenyl ether 10 parts, sodium dodecylbenzenesulfonate 5 parts, N-methyl-2-pyrrolidone 30 parts, xylene 45 parts are mixed and dissolved. An emulsion was obtained. Further, emulsions could be obtained in the same manner using the compounds shown in Tables 1 to 29 instead of the compound number (I-1).

<Formulation Example 4> Granules An appropriate amount of water was added to 2 parts of Compound No. (I-1), 3 parts of enzyme-modified dextrin, 1 part of sodium dodecylbenzenesulfonate, 25 parts of bentonite, and 69 parts of calcium carbonate and kneaded. Thereafter, the mixture was extruded and granulated from a screen having an opening diameter of 1 mm using an extrusion granulator, dried with a fluidized bed dryer at a product temperature of 60 ° C., and sieved to obtain granules. Moreover, it replaced with compound number (I-1) and the granule was able to be obtained similarly using the compound of the said Tables 1-29.

<Formulation Example 5> Granule wettable powder Compound No. (I-1) 50 parts, sodium alkylnaphthalenesulfonate 10 parts, diatomaceous earth 15 parts, clay 25 parts are mixed and pulverized using an impact pulverizer, and an appropriate amount of water is added. In addition, kneading. Thereafter, the mixture was extruded and granulated from a screen having an aperture diameter of 0.6 mm using an extrusion granulator, dried at a product temperature of 60 ° C. using a fluidized bed dryer, and sieved to obtain a granular wettable powder. Moreover, it was replaced with the compound number (I-1), and the granule wettable powder was able to be obtained similarly using the compound of the said Tables 1-29.

<Formulation Example 6> Floating diffusion granule Compound No. (I-1) 10 parts, enzyme-modified dextrin 2 parts, acetylene diol 3 parts, water-containing plastic hollow body 10 parts, anhydrous sodium sulfate 25 parts, urea 50 parts appropriate amount of water And kneaded. Then, after extrusion granulation from a screen with an opening diameter of 5 mm using an extrusion granulator and sizing to a length of 3 to 20 mm, it is dried in a fluidized bed dryer at a product temperature of 60 ° C., and is floated and diffused by sieving. A mold granule was obtained. Moreover, it could replace with a compound number (I-1) and the floating diffusion granule was able to be obtained similarly using the compound of the said Tables 1-29.

Next, effects of the compound of the present invention will be described with reference to test examples.
<Test Example 1> Herbicidal effect test by paddy field soil treatment Paddy field soil (Korean soil) was filled in a 100 cm ² plastic pot, and after seedling, seeds of barnyard grass and snapper were sown. Furthermore, rice (Ginnan style) grown to the second leaf stage using the seedling culture soil was cut to a length of 0.5 cm at the root, transplanted to a depth of 2 cm, and a depth of 3 cm. I was flooded. On the next day, the wettable powder prepared according to Formulation Example 1 was diluted with water and dropped on the surface of the water. The application rate was 1000 g per hectare of active ingredient. Then, it grew in the greenhouse and investigated the herbicidal effect and the phytotoxicity according to the standard of Table 31 on the 30th day after the treatment. The results are shown in Table 32. In addition, the control compound A, the control compound B, and the control compound C are Nos. Described in WO2002 / 44173, respectively. 3, no. 42, no. 111 compounds.

<Test Example 2> Herbicidal effect test by field soil treatment An 80 cm ² plastic pot was filled with field soil, and seeds of Enocologosa and Aogaeto were sown and covered with soil. The wettable powder prepared according to Formulation Example 1 was diluted with water so that the active ingredient per hectare was 1000 g, and a diluted solution equivalent to 1000 liters per hectare was uniformly sprayed on the soil surface with a small sprayer. . Then, it grew in the greenhouse and investigated the herbicidal effect according to the standard of Table 31 on the 28th day of the treatment. The results are shown in Table 33.

<Test Example 3> Herbicidal effect test by upland soil treatment A 336 cm ² plastic pot was filled with upland soil, and seeds of wheat, soybean, Inobie, Enocologosa, Giant Indode and Shiroza were sown and covered with soil. The wettable powder prepared according to Formulation Example 1 was diluted with water so that the active ingredient per hectare was 250 g, and a diluted solution equivalent to 1000 liters per hectare was evenly sprayed on the soil surface with a small sprayer. . Then, it grew in the greenhouse and investigated the herbicidal effect according to the standard of Table 31 on the 28th day of the treatment. The results are shown in Table 34.

The compound of the present invention or a salt thereof has an excellent herbicidal action against a wide range of weeds in paddy fields and upland fields at a low dosage. Moreover, it has little phytotoxicity against cultivated plants such as rice, wheat, barley, corn, soybean, cotton, grain sorghum, sugar beet, sugar cane, etc., and exhibits an excellent selective herbicidal effect, and the herbicidal effect lasts for a long time. In addition, it has low toxicity to mammals and fish and shellfish, and can be used very safely as a herbicide for paddy fields, fields, orchards or non-agricultural lands without polluting the environment. Furthermore, the compound of the present invention or a salt thereof is useful as a herbicide because it can be easily formulated as a herbicide.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2005-253249 filed on September 1, 2005 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (5)

Formula [I]

{Where,
A represents a phenyl group or an aromatic heterocyclic group,
X is substituent group α in the optionally substituted C ₃ -C ₈ cycloalkyl group, a substituted C ₃ -C ₈ optionally cycloalkyl C ₁ -C ₃ alkyl group with a substituent group α, or a substituted represents optionally substituted C ₃ -C ₈ cycloalkylcarbonyl group with a group group alpha,
Y is a halogen atom, a cyano group, a hydroxyl _group, C 1 -C ₆ alkyl _group, C 1 -C ₆ haloalkyl _group, C 2 -C ₆ alkenyl _group, C 2 -C ₆ alkynyl _group, C 1 -C ₆ alkoxy group , _C 1 -C ₆ haloalkoxy _group, C 1 -C ₆ alkylthio _group, C 1 -C ₆ alkylsulfinyl _group, C 1 -C ₆ alkylsulfonyl _group, C 1 -C ₆ haloalkylthio _group, C 1 -C ₆ It represents haloalkylsulfinyl _group, C 1 -C ₆ haloalkylsulfonyl _group, C 1 -C ₆ acyl group or a _C 1 -C ₆ alkyloxycarbonyl group,
W represents an oxygen atom, a sulfur atom or CH ₂ , L represents an oxygen atom or a sulfur atom, R represents a hydrogen atom, a C ₁ -C ₈ alkyl group, a C ₁ -C ₈ haloalkyl group, a substituent group β in optionally substituted _C 3 -C ₈ cycloalkyl _group, a C 3 -C ₈ cycloalkyl _C 1 -C ₃ alkyl or _C 3 -C ₈ halocycloalkyl _C 1 -C ₃ alkyl group,
R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₃ alkyl group, or a C ₁ -C ₃ haloalkyl group,
m represents an integer of 1 to 5,
n shows the integer of 0-4. } Or a salt thereof.
`` Substituent group α ''
Halogen atom, cyano _group, C 1 -C ₃ alkyl group [said group may be substituted by a halogen atom or a hydroxyl _group], C 1 -C ₃ alkoxy _groups, C 1 -C ₃ acyl _group, C 1 -C ₃ alkyloxycarbonyl group, aminocarbonyl group, aminothiocarbonyl group, carboxyl group “substituent group β”
Halogen _atom, C 1 -C ₃ alkyl group The pyrazole derivative or a salt thereof according to claim 1, wherein X is a C _{3 to} C ₈ cycloalkyl group optionally substituted with a substituent group α.   The pyrazole derivative or a salt thereof according to claim 2, wherein A is a phenyl group or a thienyl group. A is

The pyrazole derivative of Claim 3 represented by these, or its salt.   A herbicide for agricultural and horticultural use comprising the pyrazole derivative according to any one of claims 1 to 4 or a salt thereof as an active ingredient.