JPH07507781A - Herbicide pyrazole-(thio)-carboxamide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] 24. A herbicidally effective amount of the N-substituted pyrazole derivative of formula I according to claim 1 or is an agriculturally acceptable salt thereof and an agriculturally acceptable diluent or carrier and/or A herbicide composition comprising a surfactant as an active ingredient.

25 A method for controlling weed growth in a certain location, in which the amount effective for weeding is or an agriculturally acceptable N-substituted pyrazole derivative of formula I according to claim 1 of A method consisting of applying salt to the area.

Herbicide pyrazole-(thio)-carboxamide The present invention relates to N-substituted pyrazole derivatives. Conductor, method for producing the derivative, composition containing the derivative, and herbicide for the composition Regarding the use of.

Okajjma and Okada J, Het, Chem, vol. 27, 567-5. Page 74 is 4-N-7,,=carboxamide-5-methylthio-1,3- Describes the production of dimethylpyrazole. There is a patent application No. 3-119468. Disclosed is a method for producing species of 5-mercaptopyrazole compounds. french patent No. 2,337.997 is Huppatz J, L, Au5t, J, Che m, vol. 36, p. 135-147 (1982). Describes sol-carboxamide derivatives. U.S. Patent No. 4,620,865 No. 0151866 and European Patent No. 0151866 disclose that certain pyrazo- 4-carboxamide derivatives are disclosed.

The present invention relates to formula I: ■ [In the formula, R1 is Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; containing 3 to 6 carbon atoms, optionally one or more R6 groups; cycloalkyl group substituted with; -(CHl), -Ar group (where n is 0 or 1, Ar is optionally a halogen group) in, nitro, R--OH, -OR', -S (0), R' and -NR"R. phenyl group substituted with one or more groups selected from ): up to 6 carbons containing atoms, optionally one or more selected from halogen, R@ and -OR# a straight-chain or branched alkenyl or alkynyl group substituted with a group; or -5o, NR'lR'', -3O, R7+ and -CONR''R't. indicates a group; R2 represents -X-R1 group; R3 is hydrogen or halogen atom; Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; containing 3 to 6 carbon atoms, optionally containing one or more halogens; cycloalkyl group substituted with an atom or R6 group; cyano or nitro group D -S (0), R@ group; Optionally one or more selected from halogen, nitro, R', -OR@ and cyano phenyl substituted with the above group; or -CO, R'; R4 is Optionally halogen, nitro, R, -OR6, -3(0)@R7 and -NRIR phenyl substituted with one or more groups selected from '; or Optionally halogen, nitro, R6, -OR6, -8(0).

Pyridyl substituted with one or more groups selected from R7 and -NRaR' Show; R8 is a hydrogen atom or a straight or branched alkyl group containing up to 6 carbon atoms; Show; Y represents oxygen or sulfur atom; R6 contains up to 6 carbon atoms and is optionally substituted with one or more halogen atoms Represents a straight chain or branched alkyl group; R6I and R which may be the same or different each st contains up to 6 carbon atoms, optionally substituted with one or more halogen atoms represents a straight-chain or branched alkyl group containing up to 4 carbon atoms; R represents a straight or branched alkyl group optionally substituted with one or more halogen atoms; 7+ is Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; or optionally halogen, nitro, R6, -OR@, -5 (0).

phenyl substituted with one or more groups selected from R7 and -NR"R. Shows: R8 and R9, which may be the same or different, are each hydrogen or up to 6 carbons linear or branched chain atoms, optionally substituted with one or more halogen atoms; RIff represents a rukyl group, Optional nihalokene, nitro, R4, -OR", -S (0).

R1, substituted with one or more groups selected from -NHCOR@ and -NR"R. phenyl; Any dihalogen, nitro, R6, -OR', -8(0).

R7, substituted with one or more groups selected from -NHCOR' and -N R'R@ or pyridyl containing up to 10 carbon atoms and optionally one or more acids in the chain. It may contain an elementary atom, a sulfur atom, or a -NR'- group (and optional L halo). Gen, -OR"-5-3(0), R--NR8R", -Co, R', -0COR @, -NHCOR・, -CONRIR@, R1's, -COR", R" and Sif/ straight-chain or branched alkyl substituted with one or more groups selected from It represents an alkenyl or alkynyl group, and X is an oxygen atom, -NRII- or +; i- S (0), -4; R11 is hydrogen or contains up to 6 carbon atoms, optionally represents a straight-chain or branched alkyl group substituted with one or more halogen atoms; R12 contains 3 to 7 ring atoms, optionally selected from oxygen, sulfur and -NR'- Indicates a cycloalkyl group which may contain 1 to 3 selected heteroatoms in the ring. ;RI3 is 1 containing 3 to 6 carbon atoms and selected from halogen, Rs and -OR'' a cycloalkyl group substituted with one or more groups, or containing 5 or 6 carbon atoms, optionally selected from halogen, R@ and -OR' represents an alkenyl group substituted with one or more selected groups; m is 0, 1 or 2; p is 0.1 or 2; q is 0.1 or 2; ; Y represents oxygen, R1 represents methylthio or N-phenylamino, and R4 represents phenylamino. When R5 represents hydrogen, R1 and R3 do not represent methyl at the same time. N-substituted pyrazole derivatives having effective herbicidal properties and The present invention provides agriculturally acceptable salts.

The term “agriculturally acceptable salt” means that the cation is salts known and tolerated in the prior art for their composition. Preferably the salt is water soluble be. Salts with suitable bases include alkali metals (e.g. sodium and potassium), alkaline earth metals (e.g. calcium and magnesium), ammonium and Amines (e.g. jetanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine).

Suitable acid addition salts formed by compounds of formula I containing an amino group include inorganic acids and salts (e.g. hydrochlorides, sulfates, phosphates and nitrates) and organic wI (f!4 etc.) Contains salts such as acetic acid).

Certain compounds of formula I have been disclosed as having fungicidal properties. However, there is no mention that these compounds were actually synthesized. Other features of the invention According to the above-defined formula I, Y represents oxygen and R1 represents represents methyl, Rs represents trifluoromethyl, R5 represents hydrogen, and R2 represents Toxy, 2,2,2-trifluoroethoxy, ethylthio, N-propylamino and methanesulfonyl, and R4 is 2-trifluoromethane. tylphenyl, 2-chloro-4-nitrophenyl, 2-trifluoromethyl-4 -nitrophenyl, 2-bromo-4-nitrophenyl, 2-chloro-5-trif fluoromethylphenyl, 2,5-dichloro-4-nitrophenyl, 2.3,4. 5-tetrachlorophenyl, 2,6-dipromo 4-trifluoromethoxyphene Other than compounds exhibiting a group selected from nyl and pentafluorophenyl I will provide a.

In a first embodiment, the invention provides formula 1: [wherein R1 is Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; containing 3 to 6 carbon atoms, optionally one or more R6 groups; a cycloalkyl group substituted with; or (CH2) * A r group (where n is 0 or 1, and Δr is any L”) o-gen, nitro, R@, -OH, -OR・, -3(0), R' and -NR"R@ represents phenyl substituted with one or more groups selected from teeth, hydrogen or halogen atom; Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; containing 3 to 6 carbon atoms, optionally one or more R6 groups; Cycloalkyl group substituted with: N'Ano Group -S (0), R6 group; Optionally one or more selected from halogen, nitro, R', -OR' and cyano phenyl substituted with the above group; or -CO, R' group;

RIO is Any Nihalokene, Nitro, R@, -0RB, -3(0).

Substituted with one or more groups selected from R7, -NHCOR6 and -NR8R'' phenyl; or optionally halogen, nitro, R6, -OR', -3(0) .

R7, substituted with one or more groups selected from -NHCOR' and U-NR"R" The present invention provides an N-substituted pyrazole derivative represented by:

In this embodiment, X is preferably an oxygen or sulfur atom or a -N Rl group shows.

In a second embodiment, the present invention provides the formula ■: [wherein R1 is Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; containing 3 to 6 carbon atoms, optionally one or more R@ groups; a cycloalkyl group substituted with; or (CHri @ A r group (wherein, n is 0 or 1, and Ar is optionally a halogen group) in, nitro, R6, -OH, -0RI, -8(0), R' and -NR'R. represents phenyl substituted with one or more groups selected from hydrogen or halogen atom; Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; containing 3 to 6 carbon atoms, optionally one or more R6 groups; cycloalkyl group substituted with; Cyano or nitro group; -5(0), R' group; Optionally one or more selected from halogen, nitro, R., -〇R6 and cyano. phenyl substituted with the above group; or -Co! Represents an R' group; R18 contains up to 10 carbon atoms and the chain optionally contains one or more oxygen or sulfur atoms. May contain a yellow atom or -NR5- group, and optionally halogen, -0R8, -S (0), R', -NR"R@, -Co!R", -0COR', -NHCO one or more groups selected from R', -CONR''R@, RIS and cyano; represents a substituted straight-chain or branched alkyl, alkenyl or alkynyl group] N-substituted virazole derivatives are provided.

In a third embodiment, the invention provides compounds of formula I: [wherein R3 is Hydrogen or halogen atom: Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; containing 3 to 6 carbon atoms, optionally one or more R-groups; cycloalkyl group substituted with Diano or nitro group; -3(0), R' group.

Optionally one or more selected from halogen, nitro, R6, -〇R6 and cyano phenyl substituted with the above group; or -cotR' group: R111 contains up to 10 carbon atoms and the chain optionally contains one or more oxygen or It may contain a sulfur atom or a -NR8- group, and optionally a halogen, -0R- -S (0), R, -NRaR', -cotR Hatake, -0COR', -N Among HCOR・, -CONR@R・, RIS, -CORI, RIS and Cyano? Straight or branched alkyl, alkenyl substituted with one or more groups selected from or an alkynyl group] is provided.

A preferred type of compound of formula (1) is one in which Y represents an oxygen atom.

Another preferred type of compounds of formula I are those in which R1 represents methyl or ethyl. .

Another preferred type of compounds of formula I are those in which R1 represents methyl.

Compounds in which R3 represents trifluoromethyl are also preferred.

Compounds in which R4 represents 2,4-difluorophenyl are also preferred.

Formula I (wherein R4 is 2,4-difluorophenyl or 2.4, rhotrifluoro) Also preferred are the compounds (representing phenyl).

Compounds in which R8 represents a hydrogen atom are also preferred.

Another preferred type of compounds of formula I are those in which X represents a sulfur atom. Formula I (formula Among these, compounds in which X represents an oxygen atom are also preferred.

Another preferred type of compound of formula I is that RIO contains at least one halogen atom, preferably Preferably, it is a compound showing phenyl substituted with fluorine.

Another preferred type of compound of formula 1 is that R1. contains up to 4 carbon atoms and optionally Straight-chain or branched alkyl or alkenyl substituted with one or more halogen atoms It is a compound that shows a group.

Another preferred type of compound of formula It is a compound showing an alkenyl group containing a carbon atom).

Another preferred type of compound of formula I is that R16 is up to 6, preferably up to 5. Straight or branched chain containing carbon atoms optionally substituted with one or more halogen atoms A compound exhibiting an alkyl, alkenyl or alkynyl group.

R'' is a straight or branched alkyl group substituted with one or more RIS or R13 groups; When indicated, RIO preferably represents a -CH3R" or -CHtR" group.

Other preferred types of compounds of formula I are: R1 contains 1 or 2 carbon atoms, which may be the same or different R represents an alkyl group optionally substituted with a halogen (preferably fluorine) atom; 3 is up to 5 halogens, which may be the same or different, containing up to 3 carbon atoms an alkyl group optionally substituted with a (preferably fluorine or chlorine) atom: or -SM Indicates the e group.

1 where R4 is optionally selected from halogen, trifluoromethyl and methoxy represents phenyl substituted with ~3 groups; R6 represents a hydrogen atom or a methyl group; Y represents oxygen or sulfur atom; X represents an oxygen atom or -S (0), - group.

RIO is Optionally halogen, methoxy, hydroxy, -NHCOMe, NHtSMe, substituted phenyl or trifluoromethyl consisting of methyl and trifluoromethyl; is pyridyl.

a cycloalkyl group containing from 3 to 6 carbon atoms; or containing up to 6 carbon atoms; Optionally halogen, -CO.

selected from Et, cyano, cyclopropyl, methoxy and -CONHMe straight-chain or branched alkyl, alkenyl or indicates an alkynyl group.

p indicates 0 or 1 It is a compound.

Compounds of particular importance for their herbicidal properties are: 1.4-N-(2,4-diphthalate) fluorophenyl)carboxamide-5-(4-chlorophenylthio)-1-methy -3-trifluoromethylpyrazole, 2.4-N-(2,4-difluorophenyl)carboxamide-5-(4-meth xyphenylthio)-1-methyl-3-trifluoromethylpyrazole, 3.4-N-(2,4-difluorophenyl)carboxamide-5-(4-fluorophenyl) orophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4.4-N-(2,4-difluorophenyl)carboxamide-5-(4-bro mophenylthio)-1-methyl-3-trifluoromethylpyrazole, 5.4-N-(2,4-difluorophenyl)carboxamide-5-(4-hydro loxophenylthio)-1-methyl-3-trifluoromethylpyrazole, 6. 4-N-(2,4-difluorophenyl)carboxamide-5-(2-fluorophenyl) phenylthio)-1-methyl-3-trifluoromethylpyrazole, 7.4-N-(2,4-difluorophenyl)carboxamide-5-(3-fluorophenyl) orophenylthio)-1-methyl-3-trifluoromethylpyrazole, 8.4-N-(2,4-difluorophenyl)carboxamide-5-phenylthi o-1-methyl-3-trifluoromethylpyrazole, 9.4-N-(2,4-difluorophenyl)carboxamide-5-(4-acetyl) toamidophenylthio)-1-methyl-3-trifluoromethylpyrazole, 10.4-N-(2,4-difluorophenyl)carboxamide-5-(4-methyl tylphenylthio)-1-methyl-3-trifluoromethylpyrazole, 11.4-N-(3-1-lifluoromethylphenyl)carboxamide-5-( 4-methylphenylthio)-1-methyl-3-trifluoromethylpyrazole, 12.4-N-(4-methquinphenyl)carboxamide-5-(4-chlorophenyl) phenylthio)-1-methyl-3-trifluoromethylpyrazole, 13.4-N-(2,4-difluorophenyl)carboxamide-5-(3-k) lorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 14.4-N-(2,4-difluorophenyl)carboxamide-5-(4-to (lifluoromethylphenylthio)-1-methyl-3-trifluoromethylpyrazo 15.4-N-phenylcarboxamide-5-(3-trifluoromethyl phenylthio)-1,3-dimethylpyrazole, 16.4-N-(4-fluorophenyl)carboxamide-5-(4-chlorophenyl) phenylthio)-1,3-dimethylpyrazole, 17.4-N-(2,4-difluorophenyl)carboxamide-5-(4-k) lorophenylthio)-1,3-dimethylpyrazole, 18.4-N-(2,4-difluorophenyl)carboxamide-5-(3-k) lorophenylthio)-1,3-dimethylpyrazole, 19.4-N-(2,4-difluorophenyl)carboxamide 5-(4-phenyl) fluorophenoxy)-1-methyl-3-trifluoromethylpyrazole, 20.4-N-(4-fluorophenyl)carboxamide-5-(3-1-rif (fluoromethylphenoxy)-1-methyl-3-trifluoromethylpyrazole, 21.4-N-(2,4-difluorophenyl)carboxamide-5-(3-k) lorophenoxy)-1-methyl-3-trifluoromethylpyrazole, 22.4-N-phenylcarboxamide-5-(4-chlorophenoxy)-1, 3-dimethylpyrazole, 23.4-N-(4-fluorophenyl)carboxa mido-5-(4-chlorophenoxy)-1,3-dimethylpyrazole, 24.4-N-(2,4-difluorophenyl)carboxamide-5-(4-k) lorophenoxy)-1-methyl-3=trifluoromethylpyrazole, 25.4-N-(2,4-difluorophenyl)carboxamide-5-(n-butyl) tilthio)-1-methyl-3-trifluoromethylpyrazole, 26.4-N-(2,4-difluorophenyl)carboxamide-5-(2-propylene) (ropenylthio)-1-methyl-3-trifluoromethylpyrazole, 27.4-N-(2,4-difluorophenyl)carboxamide-5-isopro pythio-1-methyl-3-trifluoromethylpyrazole, 28.4-N-(2,4-difluorophenyl)carboxamide-5-ethylthi o-1-methyl-3-trifluoromethylpyrazole, 29.4-N-(2,4-difluorophenyl)carboxamide-5-(3-k lolopropylthio)-1-methyl-3-trifluoromethylpyrazole, 30.4-N-(2,4-difluorophenyl)carboxamide-5-methylthi o-1-methyl-3-trifluoromethylpyrazole, 31.4-N-(2,4-difluorophenyl)carboxamide-5-(2,2 ,2-trifluoroethoxy)-1-methyl-3-trifluoromethylpyrazo 32.4-N-(2,4-difluorophenyl)carboxamide-5-(ethyl) Toxycarbonylmethylthio)-1-methyl-3-trifluoromethylpyrazo 33.4-N-(2,4-difluorophenyl)carboxamide-1-methylene -5-(1-methylbutylthio)-3-trifluoromethylpyrazole, 34.4-N-(2,4-difluorophenyl)carboxamide-1-methyl- 5-(2-methylpropylthio)-3-trifluoromethylpyrazole, 35.4-N-(2,4-difluorophenyl)carboxamide-5-(n-to xylthio)-1-methyl-3-trifluoromethylpyrazole, 36.5-cyclopentylthio-4-N-(2,4-difluorophenyl)cal boxamide-1-methyl-3-trifluoromethylpyrazole, 37.4-N-(2,4-difluorophenyl)carboxamide-1-methyl- 5-(n-propylthio)-3-trifluoromethylpyrazole, 38.5-cyclohexylthio-4-N-(2,4-difluorophenyl)car boxamide-1-methyl-3-trifluoromethylpyrazole, 39.4-N-(2,4-difluorophenyl)carboxamide-1-methyl- 5-(1-methylpropylthio)-3-trifluoromethylpyrazole, 40.4-N-(2,4-difluorophenyl)carboxamide-1-methyl- 5-(3-methylbutylthio)-3-trifluoromethylpyrazole, 41.4-N-(2,4-difluorophenyl)carboxamide-5-(1,1 -dimethylethylthio)-1-methyl-3-trifluoromethylpyrazole, 4 2.4-N-(2,4-difluorophenyl)carboxamide-5-ethoxy- 1-methyl-3-trifluoromethylpyrazole, 43.4-N-(2,4-difluorophenyl)carboxamide-1-methyl- 5-(2-propynylthio)-3-trifluoromethylpyrazole, 44.5-(3-butenylthio)-4-N-(2,4-difluorophenyl)ka ruboxamide-1-methyl-3-trifluoromethylpyrazole, 45.5-(2-bromo-2-propenylthio)-4-N-(2,4-difluoro Lophenyl)carboxamide-1-methyl-3-trifluoromethylpyrazole , 46.5-(3-bromo-2-propenylthio)-4-N-(2,4-diflu (olophenyl)carboxamide-1-methyl-3-trifluoromethylpyrazo 47.5-(cyanomethylthio)-4-N-(2,4-difluorophenyl ) carboxamide-1-methyl-3-trifluoromethylpyrazole, 48.5-(3-methyl-2-butenylthio)-4-N-(2,4-difluoro phenyl)carboxamide-1-methyl-3-trifluoromethylpyrazole, 49.5-(Cyclopropylmethylthio)-4-N-(2゜4-difluorophore carboxamide-1-methyl-3-trifluoromethylpyrazole, 50.5-(3-butynylthio)-4-N-(2,4-difluorophenyl)ka ruboxamide-1-methyl-3-trifluoromethylpyrazole, 51.5-(2-chloropropylthio)-4-N-(2゜4-difluorophenyl ) carboxamide-1-methyl-3-trifluoromethylpyrazole, 52.4-N-(2,4-difluorophenyl)carboxamide-5-(2,2 -dimethoxyethylthio)-1-methyl-3-trifluoromethylpyrazole, Methyl-3-trifluoromethylpyrazole, 53.5-(2-butenylthio) -4-N-(2,4-difluorophenyl)carboxamide-1-methyl-3- trifluoromethylpyrazole, 54.4-N-(2,4-difluorophenyl)carboxamide-1-methyl- 5-(n-pentylthio)-3-trifluoromethylpyrazole, 55.4-N-(2,4-difluorophenyl)carboxamide-1-methyl- 5-(2-methylbutylthio)-3-trifluoromethylpyrazole, 56.4-N-(2,4-difluorophenyl)carboxamide-1-methyl- 5-(2-methyl-2-propenylthio)-3-trifluoromethylpyrazole , 57.5-(2-chloro-2-propenylthio)-4-N-(2,4-diph fluorophenyl)carboxamide-1-methyl-3-trifluoromethylpyrazo 58.4-N-(2,4-difluorophenyl)carboxamide-5-( 2-methoxyethyl)-1-methyl-3-trifluoromethylpyrazole, 59.5-(3-chloro-2-propenylthio)-4-N-(2,4-diflu (olophenyl)carboxamide-1-samido-1-methyl-5-(2-pyridyl thio)-3-thro0.5-ethylthio-1-ethyl-4-N-(2,4-diflu (olophenyl)carboxamide-3-trifluorolifluoromethylpyrazole , 67.5-(4-aminophenylthio)-4-N-(2゜methyl-3-triflu Olomethylpyrazole, 73.4-N-(3,4-difluorophenyl)carbo Xamide-5-(4-fluorophenylthio)-1-methyl-3-trifluoro Methylpyrazole, 74.5-(4-fluorophenylthio)-1-methyl-3 -trifluoromethyl-4-N-(2,4,5-trifluorophenyl)carbo Xamidopyrazole, 75.4-N-(2-fluorophenyl)carboxamide -5-(4-fluorophenylthio)-1-methyl-3-trifluoromethylpi Razor, 76.4-N-(4-chlorophenyl)carboxamide-5-(4-fluorophenyl) phenylthio)-1-methyl-3-trifluoromethylpyrazole, 77.4-N-(4-chloro-2-fluorophenyl)carboxamide-5-( 4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole , 78.5-(4-fluorophenylthio)-1-methyl-3-trifluorome Chil-4-N-(2,4,rotrifluorophenyl)carboxamide pyrazole 79.4-N-(2-chloro-4-fluorophenyl) force86.4-N-( 2,3-difluorophenyl)carboxylboxamide-5-(4-fluorophenyl) Nylthio)-1-methyl-3-trifluoromethylpyrazole, 80.4-N- (4-fluorophenyl)carboxamide-5-(4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole, 81.4-N-(2,4-dichlorophenyl)carboxamide-5-(4-flu orophenylthio)-1-methyl-3-trifluoromethylpyrazole, 82.5-(4-fluorophenylthio)-1-methyl-3-trifluoromethyl Ru-4-N-(2,3,4-trifluorophenyl)carboxamide pyrazole , 83.4-N-(4-bromo-2-fluorophenyl)carboxamide-5- (4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazo 84.5-(4-fluorophenylthio)-4-N-(2-fluoro-4- methylphenyl)carboxamide-1-methyl-3-trifluoromethylpyrazo 85.4-N-(3-fluorophenyl)carboxamide-5-(4-fluorophenyl) fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, -3-trifluoromethylpyrazole, samide 5-(4-fluorophenylthi e)-1-methyl-3-trifluoromethylpyrazole, 87.4-N-(2, 5-difluorophenyl)carboxamide-5-(4-fluorophenylthio) -1-methyl-3-trifluoromethylpyrazole, 88.4-N-(2,6- difluorophenyl)carboxamide-5-(4-fluorophenylthio)-1 -Methyl-3-trifluoromethylpyrazole, 89.4-N-(3,5-diph fluorophenyl)carboxamide-5-(4-fluorophenylthio)-1-mer Tyl-3-trifluoromethylpyrazole, 90.5-(4-fluorophenyl thio)-1-methyl-3-trifluoromethyl-4-N-(2,3, rotrif fluorophenyl)carboxamide pyrazole, 91.5-(4-fluorophenyl) (ruthio)-1-methyl-4-N-(phenyl)carboxamide-3-trifluoro lomethylpyrazole, 92.4-N-(2,4-difluorophenyl)carboxamide-1-methyl- 5-(4-methylthiophenylthio93.5-(4-fluorophenylthio)- 1-Methyl-4-N-methyl-N-(2,4-difluorophenyl)carboxa Mido-3-trifluoromethylpyrazole, 94.5-(4-chlorophenyl sulfinyl)-4-N-(2,4-difluorophenyl)carboxamide-1 -Methyl-3-trifluoromethylpyrazole, 95.4-N-(2,4-diph fluorophenyl)carboxamide-1-methyl-5-(n-propyloxy)- 3-trifluoromethylpyrazole, 96.4-N-(2,4-difluorophenyl)carboxamide-1-methyl- 5-(2-methylpropyloxy)-3-trifluoromethylpyrazole, 97 ．． 3-chlorodifluoromethyl-4-N-(2,4-difluorophenyl)cal Boxamide-1-methyl-5-(2-methylpropyloxy)pyrazole, 98 ．． 4-N-(2,4-difluorophenyl)carboxamide-1-ethyl-5- (2-methylpropylthio)-3-trifluoromethylpyrazole, ) 99.4-N-(2,4-difluorophenyl)carboxamide 1-ethyl -5-(2-propenylthio)-3-trifluoromethylpyrazole, 100.4-N-(2,4,rotrifluorophenyl)carboxamide-1- Ethyl-5-(2-methylpropylthio)-3-1-lifluoromethylpyrazole , 101.4-N-(2,3-difluorophenyl)carboxamide-1-methy -5-(2-methylpropylthio)-3-trifluoromethylpyrazole 1 02.4-N-(2,6-difluorophenyl)carboxamide-1-methyl- 5-(2-methylpropylthio)-3-trifluoromethylpyrazole, 103 ．． 4-N-(2,3,6-1lifluorophenyl)carboxamide-1-methyl -5-(2-methylpropylthio)-3-1-lifluoromethylpyrazole, 1 04.4-N-(2,4,rotrifluorophenyl)carboxamide-1-methane thyl-5-(2-methylpropylthio)-3-trifluoromethylpyrazole, 105.4-N-(2,5-difluorophenyl)carboxamide-1-methyl -5-(2-methylpropylthio)=3-trifluoromethylpyrazole, and 106.4-N-(2,4-difluorophenyl)carboxamide-1-methyl -5-(2-methylpropylthio)-3-pentafluoroethylpyrazole.

These compounds are numbered 1 to 106 for reference and identification below.

For example, known methods (i.e. those used to date or Compounds of formula I can be prepared by applying methods described in the scientific literature. Ru.

Unless symbols in a formula are specifically defined in the following description, those symbols are used in the present specification. Assume that it is “as defined” at the beginning.

In the following description of the manufacturing method, the steps may be carried out in a different order or as desired. It is understood that appropriate protecting groups may be required to obtain the compounds.

According to one feature of the invention, the compound of formula I is of the formula ■: I (wherein R1, R3, R4, R5 and Y are as defined above and Z is a leaving group ) is represented by 2m;R''-X' I[[ [wherein R2 is as defined above and Xl is hydrogen or an alkali metal (e.g. sodium or potassium)] can be manufactured by

The reaction is generally carried out optionally with a base (e.g. sodium hydride, potassium t-butyl In the presence of a toxide or preferably potassium carbonate, an inert solvent (e.g. reflux of solvent from room temperature in acetonitrile, dioxane or tetrahydrofuran) Perform at temperatures up to temp. Preferably the leaving group Z is a halogen atom (e.g. chlorine, bromine or fluorine).

According to another feature of the invention, compounds of the formula I, in which Y represents a sulfur atom, The corresponding compound represented by formula I (Y in the formula represents an oxygen atom) is prepared in an inert solvent. vulcanizing compound (eg Lawess) in (preferably toluene).

n reagent [2,4-bis(4-methquinphenyl)-1,3-dithia-2,4-di phosphetane-2,4-disulfide]) and the temperature from 50°C to the reflux temperature of the solvent. It can be produced by reacting at a temperature of

According to one feature of the invention, compounds of the formula I (wherein R6 is a straight chain or represents a branched alkyl group) is a base (e.g. potassium hydroxide). or potassium carbonate) in an inert solvent (e.g. tetrahydrofuran), The corresponding compound of formula I (in which R5 represents hydrogen) is treated with an alkylating agent (preferably or alkyl halides or alkyl sulfates) from room temperature to the reflux temperature of the solvent. It can be produced by reacting at temperature. This reaction may be accompanied by a phase transfer. of a catalyst (e.g. usually 0.01-0.1 mol% tetrabutylammonium bromide) It may be carried out in the presence of Alternatively, sodium or potassium salts of compound A compound represented by formula I (R5 in the formula represents hydrogen) is treated with a base (preferably (or sodium hydride) and then an alkylating agent. can be manufactured by

According to another feature of the invention, the compound of formula I, in which Y represents oxygen, , formula ■: 议1 ■v (wherein R1, R2 and R3 are as defined above) Reacts with a halogenating agent to produce an acid halide (which can be isolated in some cases) ), then convert this into formula V: H-NR’R’V (in which R4 and R8 are as defined above) It can be manufactured by Preferably the halogenating agent is a chlorinating agent (e.g. nitrogen chloride). onyl), and the acid halide production reaction may be carried out indoors in an inert solvent. It is carried out at temperatures from warm to reflux. Acid halides and amines of formula V The reaction with is generally carried out in an inert solvent in the presence of a base (preferably triethylamine). (e.g. tetrahydrofuran) at temperatures from 0°C to the reflux temperature of the solvent. .

According to another feature of the present invention, the compound represented by formula (In formula 17) R', R", R4, RISY and X are as defined above) A compound represented by the formula R1.-L (wherein R" is as defined above) and L is a leaving group). can be done. Preferably L is a halogen atom (more preferably chlorine or bromine), para-toluenesulfonyloxy or methylsulfonyloxy and (R1. is optional) (if optionally substituted phenyl or pyridyl) indicates nitro; reaction is general a base (e.g. sodium hydride) in an inert solvent (e.g. ethanol or methanol). thorium or sodium methoxide). Represented by formula (IVa) When reacting with salts of compounds, alkali metal salts or alkaline earth metal salts (e.g. Preference is given to using the sodium or potassium salts.

According to another feature of the invention, the X Rl e group (wherein R1' is (representing substituted phenyl or pyridyl), RIO is replaced with -NH2. The corresponding compound showing the substituted phenyl or pyridyl is diazotized and then treated in this way. The diazotized product obtained by It can be produced by reacting with a disulfide represented by anti The reaction is generally performed using a diazotizing reagent such as an alkyl nitrite (e.g. t-butyl nitrite). in an inert solvent (e.g. acetonitrile or dichloromethane) using It is carried out at temperatures from °C to reflux.

Intermediates used in the preparation of compounds of formula I can be prepared by known methods, such as those described below. It can be manufactured by applying the method described below.

Represented by the formula ■ (in the formula, Y represents oxygen and Z represents a leaving group (for example, 10 gen)) The compound represented by the formula ■:■ [wherein Z represents a residue (e.g. halogen)], for example, when by thionyl chloride in the presence of an inert solvent and at temperatures from room temperature to reflux temperature. reaction to convert it to an acid halide (preferably an acid chloride), followed by a base (preferably an acid chloride). or triethylamine) in the presence of an inert solvent (e.g. tetrahydrofuran). wherein said acid chloride (which may optionally be isolated) is combined with an amine of formula V. It can be produced by reacting at temperatures from 0°C to the reflux temperature of the solvent.

The compound represented by the formula ■ (in the formula, Y represents a sulfur atom) is prepared in an inert solvent (preferably is toluene), and the corresponding compound represented by the formula ■ (Y in the formula represents an oxygen atom) is Vulcanization compounds (e.g. Lawesson's reagent [2,4-bis(4-methoxyphene) 1,3-dithia-2,4-diphosphethane-2,4-disulfide) It can be produced by reacting with 50° C. to the reflux temperature of the solvent.

With the formula ■ [XI in the formula represents an alkali metal (e.g. sodium or potassium)] The represented compound can be prepared in an inert solvent (e.g. dioxane) by the formula ■ (wherein Xl is water). 2) with an alkali metal-containing base (e.g. NaH) It can be produced by reacting at temperatures from 0°C to the reflux temperature of the solvent.

The compound represented by the formula ■ (wherein R2 represents -5RH1 and XI represents hydrogen) is , a compound of the formula Rl1l-Br is prepared by a) sodium thiol in ethanol. or b) reaction with thiourea in ethanol and then the formula R1 thus obtained ・SC(=NH)　NHx・HB　r　The compound represented by te is mixed with water in ethanol. react with sodium oxide, or C) Potassium xanthate [EtOC(=S)S-K”] in ethanol The product thus obtained was then hydrolyzed with sodium hydroxide in a It can be manufactured by

The compound represented by formula m (wherein R'' represents -3RIO and x' represents hydrogen) is , using e.g. sodium borohydride in ethanol, the formula RIQs-SR1 It can also be produced by reducing a disulfide represented by 0.

Formula ■ [X in the formula is -S (0), a group other than - (p in the formula is 0 or 1) The compound represented by the formula I is prepared by [preparation of the compound of the formula I from the compound of the formula I described above]. [by construction procedure]ll The Z group of the compound represented by is substituted with the R1 group, and then [the compound of the formula [Procedure for preparing compounds of formula It can be manufactured by

The compound represented by formula (■a): (VIra) By hydrolyzing the ester represented by (R in the formula represents an alkyl group), can also be manufactured. This treatment can be carried out by conventional techniques, for example in an ethanol solvent. This can be done by reacting with potassium carbonate.

The compound represented by formula It can also be produced by reacting with a compound. This reaction is generally expressed by formula (n) The method explained in the reaction of the compound represented by the formula (DI) with the compound represented by the formula (DI) It will be held in

A compound represented by formula (rVa) or a salt thereof is a compound represented by formula It can be produced by reacting with a compound represented by -X'.

The compound represented by formula ■ can be prepared by using an oxidizing agent (preferably potassium permanganate), In the presence of a base (preferably sodium hydroxide) and in a solvent (preferably water), the formula ■ By oxidizing the corresponding aldehyde represented by at a temperature from room temperature to 100℃ can be manufactured.

The compound represented by the formula ■ is the compound represented by the formula ■: III By reacting 5-hydroxypyrazole represented by with a formylation reagent, can be manufactured. Simultaneously chlorinated to form a compound represented by the formula ■ (Z in the formula represents chlorine) When forming a compound, the formylating agent is phosphorus oxychloride and N,N-dimethylform. Preferably, it is a mixture with an amide. The reaction is generally carried out at a temperature of 0°C to 150°C. Do it with

5-Hydroxypyrazole represented by formula ■ is represented by formula ■: R3C(0) CH2C0 2A IX (A in the formula represents lower alkyl) β-ketoester represented by formula X; R'NHNHt x It can be produced by reacting with hydrazine represented by

The reaction is generally carried out in a solvent (preferably water) at a temperature between room temperature and reflux temperature. Ru. A mixture of isomeric products may be produced during this reaction. This mixture was prepared using conventional techniques. Separation may be performed by well known methods. The production of the above intermediates ①, ② and ② is described in (For example, J, Het, Chem 27° 243 (1990) L, F, Lee et al. ) is described in detail.

The compound represented by the formula ■ (R3 in the formula represents cyano) is a compound represented by the formula ■ (R3 in the formula represents - For example, phosphorus oxychloride is substituted with CONH2). dehydration at temperatures from room temperature to reflux, optionally in the presence of an inert solvent. or by refluxing in pyridine from 50°C using rose-toluenesulfonyl chloride. Dehydration at a temperature up to the flow temperature, followed by dehydration in alcohol at a temperature of 20-100°C. It can be produced by hydrolysis with sodium oxide.

The compound represented by the formula ■ (R3 in the formula is substituted with -CONH!) is a solvent (e.g. aqueous alcohol), preferably sodium hydroxide or potassium hydroxide Using a solution, the corresponding ester represented by the formula (R3 in the formula represents -CO2R') to produce the corresponding carboxylic acids at temperatures from 0°C to the reflux temperature of the solvent. for example with thionyl chloride (possibly in an inert solvent) from room temperature. It is converted to the corresponding acid chloride by reaction at temperatures up to reflux temperature, which can optionally be converted to the corresponding acid chloride. temperature from 0°C to reflux temperature in the presence of a suitable solvent (e.g. aqueous alcohol). The desired product can be prepared by treatment with ammonia at a time.

Alternatively, a compound represented by formula ■ (R3 in the formula is substituted with -CONH!) The corresponding ester represented by the formula (R3 in the formula represents -cozR6) is preferably Preferably, the ammonia is treated with ammonia at a temperature of 100 to 200°C in a closed container. It can be manufactured by rinsing.

Formula ■ (wherein R3 contains up to 6 carbon atoms, optionally one or more halogen atoms a straight-chain or branched alkyl group substituted with; optionally halogen, nitro, R', a phenyl group substituted with one or more groups selected from -OR' and anno; Cycloalkyl containing 3 to 6 carbon atoms and optionally substituted with one or more R groups A β-ketoester compound represented by a group; nitro or -CO, R. Well-known procedures, such as Beilstein 10. 682 (J, C, S, Sat 9. 447 Perkin, Be11enot) or N1ppon Kag aku Zasshi 82. 132 (1961) K, Hattori & Hl Nakano or Bull Soc, Chem Fr, (1964 ), 5. 945 G. Manufactured by the procedure described in Braar, M., Vilkas. It can be done.

The compound represented by the formula ■ (R3 in the formula represents -COIR') has the formula M= R'　Ot　CC=CCO2R@XI An acetylene-1,2-dialkoxycarbonyl compound represented by formula It can also be produced by reacting with hydrazine. This reaction is generally in an active solvent [preferably alcohol (e.g. methanol) from 0°C to reflux temperature. carried out at temperatures up to Formula xI: IN Under basic conditions, for example, sodium methoxy from 0°C to reflux temperature in a suitable solvent (e.g. methanol) using a Cyclize at degrees.

In some cases, base and solvent may be combined to perform both processes in one step. You may.

The compound represented by the formula ■ (Z in the formula represents halogen) is the compound represented by the formula I 1ll From an ester represented by (in the formula, R represents an alkyl group and Z represents a halogen) can be manufactured. This reaction uses a base (e.g. sodium hydroxide) and a solvent (preferably (preferably in aqueous alcohol) at temperatures from 0°C to 100°C.

The ester represented by 2XI or the ester represented by the formula RIO) is the formula x■:IV It can be produced by diazotizing the amine represented by

This reaction consists of sodium nitrite in a mineral acid (e.g. a mixture of concentrated sulfuric acid and acetic acid). at temperatures from 0°C to 60°C, and then (a) Copper halide (if an ester of formula XI is desired) or formula R+o5 + S Disulfide represented by Rto [Formula ■ (R2 in the formula represents -3RIO ) and a mineral acid, or aqueous potassium iodide. It may be reacted with the solution at a temperature of 0°C to 100°C. Alternatively, alkaline nitrite (e.g. t-butyl nitrite), (where the ester of formula XI is desired) (if applicable) a suitable halogenating agent (preferably bromoform or iodine or anhydrous) optionally in the presence of an inert solvent (preferably acetonitrile) or chloroform) at a temperature of 0 to 100°C.

A compound represented by the formula Xff (in which R3 is halogen, cyano or -SR) The object has the formula xv: X■ Diazotizing a compound represented by (R1 in the formula is as defined above) It can be manufactured by The reaction conditions for this reaction are as follows: As explained in the conversion to compound, in this case, instead of halogenating agent cyanide reagents (e.g. copper cyanide) or alkyl nitrites (e.g. t-nitrite). using a diazotization reagent such as butyl) and an inert solvent (e.g. acetonitrile or dichloromethane) at temperatures from -20°C to reflux temperature, then The solated intermediate may be treated with a disulfide of the formula R'5-SR'. this The reaction may be carried out selectively to diazotize at the 3-position of the pyrazole ring.

Perform at temperatures up to temp. Alkyl dicyanoacetate Formula represented by Xff The compound has the formula x:X (In the formula, B represents halogen (preferably chlorine), -OR' or -SR') can be prepared by reacting a compound represented by formula X with hydrazine represented by formula Ru. When B represents 10R6 or -SR', this reaction is generally carried out using an alcohol solvent. The process is carried out at temperatures ranging from room temperature to 200°C. B is halogen (preferably chlorine) ), the reaction is generally carried out in an inert solvent (preferably tetrahydrofuran). at reflux from 0°C, optionally in the presence of a base (e.g. triethylamine). Perform at temperatures up to temp.

The compound represented by formula XV is a hydrazine represented by formula RO,C-CH(CN)!　XI By reacting with an alkali metal salt of alkylzine acetate represented by can be manufactured by

Preference is given to using potassium ethyl cyanoacetate L).

The reaction is generally carried out from room temperature to reflux in the presence of an acid (eg, hydrochloric acid). Alkyl lithium The reagent is the potassium salt of lithium diisopropylamide in the presence of potassium hydroxide. A suitable alkyl chloroform in an inert solvent (preferably tetrahydrofuran) mate with malononitrile at temperatures ranging from 0°C to 100°C. can be manufactured.

-3 (○), R6, -5 (0), R7, -S (0), - or -5 (0), Compounds containing an R' group (in the formula m, p and q represent 1 or 2, for example, using loroperbenzoic acid and the corresponding compound in an inert solvent (e.g. chloroform) (m, p and q in the formula represent O or 1) at a temperature from -20°C to reflux temperature. It can be produced by oxidation.

Represented by formula (■a) (in the formula, R1 represents a group other than Ar, R2 represents -3RI6) The compound represented by the formula X: X'li/III (R1 in the formula represents a group other than Ar) is used as an alkyllithium reagent. and then the lithiated intermediate thus obtained has the formula RIOS 5R A compound that can be produced by treatment with a compound represented by IO or Rlo-8-CI It is preferable that The reaction is generally carried out in an aprotic solvent (e.g. tetrahydrocarbon (furan) at temperatures from -70°C to 0°C. Preferably RIO is left alone. Indicates an optionally substituted alkyl or alkenyl group.

The compound represented by formula IX A compound represented by the formula R1-X'' (wherein R1 is a group other than Ar, and X2 is It can be produced by reacting with a compound represented by (which is a degrouping). X2 is an example For example, it may represent a chlorine, bromine or iodine atom, or a tosyl or mesyl group. preferable. Suitable bases include potassium carbonate, sodium hydride and cesium carbonate. included. The reaction is generally carried out in a solvent (eg acetonitrile).

Are the compounds of formulas xr, xv+, X■ and Xff well known in the literature? Alternatively, it can be manufactured by applying a known method.

Agriculturally acceptable salts of N-substituted pyrazole derivatives of formula I can be prepared by known methods. can be manufactured by.

The examples below detail the preparation of compounds of formula I. In this specification, "b, p," Boiling point, "m, p," means melting point. After the symbol “NMR” is proton nuclear magnetism. Shows resonance spectral characteristics. Percentages are by weight unless otherwise noted. Ku.

Example 1 5-chloro-4-N-(2,4-difluorophenyl)carboxamide-1-methane Chil-3-trifluoromethylpyrazole (4.0g) and 4-chlorothiophene A mixture of alcohol (6 g) and potassium carbonate (2.4 g) was heated in dry acetonitrile. The mixture was stirred and heated at reflux temperature for 3 hours.

The solid was filtered off, washed with acetonitrile and the filtrate was evaporated under vacuum to give a solid. . Purified by chromatography eluting with hexane/dichloromethane to give 4 -N-(2゜4-difluorophenyl)carboxamide-5-(4-chlorophenylene) Nylthio)-1-methyl-3-trifluoromethylpyrazole (Compound 1; 5 ．． 15 g) as a white solid, m, p, 172-173°C.

The following compounds were also prepared from the appropriate starting materials by procedures similar to those described above. various notes The definitions of the numbers are as shown in the following table. Example 2 A suspension of sodium hydride in dry dioxane is stored in a room under an inert atmosphere. The mixture was stirred at room temperature and a dioxane solution of 4-fluorophenol (1.2 g) was added. . After 0.5 hours, 5-chloro-4-N-(2,4-difluorophenyl)carbo xamido-1-methyl-3-trifluoromethylpyrazole (2.47 g) A solution in oxane (25 mi') was added. Next, the mixture was heated under reflux conditions. Heat for 20 hours, cool and pour into ice water. Extract this with dichloromethane and The extracts were washed with water, dried (over anhydrous magnesium sulfate) and evaporated. obtained The yellow solid was purified by chromatography, eluting with ether/hexane; and recrystallized from ethyl acetate to obtain 4-N-(2,4 -difluorophenyl)carboxamide-5-(4-fluorophenoxy)-1 -Methyl-3-trifluoromethylpyrazole (Compound 19; 1.25g) was obtained. Ta.

Example 3 4-Carboxylic acid chloride-1-methyl-5-(3-trifluoromethylphenoxy )-3-trifluoromethylpyrazole (2.1g), 4-fluoroaniline (0,62g) and triethylamine (0,8mi’) in tetrahydrofuran. The added mixture was stirred at room temperature for about 2 hours. Dilute the mixture with water and filter the resulting solid. Separated, dehydrated and recrystallized, m, p, 4-N-(4-F fluorophenyl)carboxamide-5-(3-1-lifluoromethylphenoxy) )-1-methyl-3-trifluoromethylpyrazole (compound 20+ 2.1g ) was obtained.

By the same operation as above, m, p, 4-N-(2,4-diphthalate) at 131-132°C fluorophenyl)carboxamide-5-(3-chlorophenoxy)-1-methyl -3-Trifluoromethylpyrazole (Compound 21) was produced.

Example 4 4-Carboxylic acid chloride-5-(4-chlorophenoxy)-1,3-tumethylpyra Dissolve the sol in tetrahydrofuran, add aniline (0.6 g) and triethyl Added to a solution of the amine (0.9m6) in tetrahydrofuran. Reaction mixture at 2 hours Stir for a while, add water, filter off the resulting solid, dry and immerse in hexane/acetic acid ester. 4-N-phenylcarboxamide recrystallized from chill, m, p, 99-101°C. Do-5-(4-chlorophenoxy)-1,3-dimethylpyrazole (compound 22 : Ig) was obtained.

By the same operation as above, m, p, 4-N-(4-fluoro phenyl)carboxamide-5-(4-chlorophenoxy)-1,3-dimethyl Pyrazole (compound 23) was prepared.

Example 5 5-chloro-4-N-(2,4-difluorophenyl)carboxamide-1-methane Chil-3-trifluoromethylpyrazole (4.0g), 4-chlorophenol (2,16 g) and potassium [-butoxide (2,16 g) in t-butanol. The mixture was refluxed for about 72 hours. Add water, isolate the solid, and Purified by chromatography, eluting with San/ethyl acetate, m, p, 166 ~ ] 4-N-(2,4-difluorophenyl)carboxamide-5-( at 69°C 4-chlorophenoxy)-1-methyl-3-trifluoromethylpyrazole (chemical Compound 24 (1.45 g) was obtained.

Example 6 5-chloro-4-N-(2,4-difluorophenyl)carboxamide-1-methane An acetonitrile solution of thyl-3-trifluoromethylpyrazole (4.0 g) After cooling, sodium thiomethoxide (1.63 g) was added to it.

The resulting suspension was stirred for 2 days, refluxed for 1 hour, and filtered. Concentrate the filtrate and dilute Taken up in chloromethane and water.

The organic phase was dried (magnesium sulfate) and the solvent was evaporated to give 4-N-(2,4 -difluorophenyl)carboxamide-5-methylthio-1-methyl-3-to Lifluoromethylpyrazole (compound 30) m, p, white at 130-131℃ Obtained as a solid (3.46 g).

Example 7 5-chloro-4-N-(2,4-difluorophenyl)carboxamide-1-methane Chil-3-trifluoromethylpyrazole (1,5 g), potassium carbonate (0,9 15 g) and 2,2,2-trifluoroethanol (1.5 ml) were dissolved in acetonate. The suspension in the rill was heated at reflux temperature for 6 hours. Cool the reaction mixture; - It was installed in the evening. The reaction mixture is then filtered and the solvent removed from the filtrate, resulting in a brown color. A solid remained, which was purified by column chromatography to give 4-N-(2,4 -difluorophenyl) carboxamide 5- (2,2,2-trifluoroene m)-1-methyl-3-trifluoromethylpyrazole (compound 31) , p, 102-103° C. as a white solid (0.84 g).

The following compound was produced by the same operation as above.

4-N-(2,4-difluorophenyl)carboxamide-5-(n-butylthi e)-1-methyl-3-trifluoromethylpyrazole (compound 25); m, p, 69-70℃ 4-N-(2,4-difluorophenyl)carboxamide-5-(2-propenylate) ruthio)-1-methyl-3-trifluoromethylpyrazole (compound 26); m, p.

92-94℃ 4-N-(2,4-difluorophenyl)carboxamide-5-isopropylthi O-1-methyl-3-trifluoromethylpyrazole (compound 27); m, p , 106-107℃ 4-N-(2,4-difluorophenyl)carboxamide-5-ethylthio-1 -Methyl-3-trifluoromethylpyrazole (compound 28); m, p, 95 ~96.5℃ 4-N-(2,4-difluorophenyl)carboxamide-5-(3-chloropropylene) ropyruthio)-1-methyl-3-trifluoromethylpyrazole (compound 29) ;m.

p, 79-81℃ 4-N-(2,4-difluorophenyl)carboxamide-5-(ethoxycarboxylic acid) Bonylmethylthio)-1-methyl-3-trifluoromethylpyrazole (compound 32); m, p, 100-104°C 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 1-methylbutylthio)-3-trifluoromethylpyrazole (compound 33); m, p.

70-71℃ 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 2-methylpropylthio)-3-trifluoromethylpyrazole (compound 34) ;m.

p, 93-94℃ 4-N-(2,4-difluorophenyl)carboxamide-5-(n-hexyl thio)-1-methyl-3-trifluoromethylpyrazole (compound 35); m , p.

77-78℃ 5-Cyclopentylthio 4-N-(2,4-difluorophenyl)carboxa Mido-1-methyl-3-trifluoromethylpyrazole (compound 36): m, p.

112-114℃ 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( n-propylthio)-3-trifluoromethylpyrazole (compound 37): m , p.

89-90°C 5-Cyclohexylthio-4-N-(2,4-difluorophenyl)carboxa Mido-1-methyl-3-trifluoromethylpyrazole (compound 38); m, p, 92-94℃ 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 1-Methylpropylthio)-3-trifluoromethylpyrazole (Compound 39) ; m, p, 98-99°C 4-N-(2:4-difluorophenyl)carboxamide-1-methyl-5- (3-methylbutylthio)-3-trifluoromethylpyrazole (compound 40) ; m, p.

62-63℃ 4-N-(2,4-difluorophenyl)carboxamide-5-(1,1-dimethyl ethylthio)-1-methyl-3-trifluoromethylpyrazole (compound 4 1); m, p, 146-147°C 4-N-(2,4-difluorophenyl)carboxamide-5-ethoxy-1- Methyl-3-trifluoromethylpyrazole (compound 42); p, 108~ 109℃ 5-(N-methylaminocarbonylmethylthio)-4-N-(2,4-difluoro Lophenyl)carboxamide-1-methyl-3-trifluoromethylpyrazole (Compound 62); m, E), 129-131°C Example 8 Sodium 4-N-(2,4-difluorophenylluboxamide-1-methyl- Add 3-bromopropyne (0.6 1 g) to 3-trifluoromethylpyra and the mixture was stirred at room temperature for 3 hours. Then, the solvent is evaporated and the residue is dichloromethane. Partitioned between methane and water. The organic layer was dried and evaporated to give a white solid, which was recrystallized from cyclohexane to obtain 4-N-(2,4-difluorophenyl)carbonate. Ruboxamide-1-methyl-5-(2-propynylthio)-3-trifluorome Tilpyrazole (compound 43) m, p.

Obtained as an off-white needle-like solid (0.77 g) at 136-137°C.

The following compound was produced by the same operation as above.

5-(3-butenylthio)-4-N-(2,4-difluorophenyl)carboxy Samido-1-methyl-3-trifluoromethylpyrazole (compound 44); m , p.

93-95℃ 5-(2-bromo-2-propenylthio)-4-N-(2,4-difluorophe carboxamide-1-methyl-3-trifluoromethylpyrazole (compound Matter 45); m, p, 105-106°C 5-(3-bromo-2-propenylthio)-4-N-(2,4-difluorophe carboxamide-1-methyl-3-trifluoromethylpyrazole (compound Product 46); m, p, 111-113°C3-(anomethylthio)-4-N- (2,4-difluorophenyl)carboxamide-1-methyl-3-trifluoro Lomethylpyrazole (compound 47); m, p.

140-142℃ 5-(3-methyl-2-butenylthio)-4-N-(2゜4-difluorophenyl ) carboxamide-1-methyl-3-trifluoromethylpyrazole (compound 48); m, p, 122-123°C 5-(cyclopropylmethylthio)-4-N-(2,4-difluorophenyl) Carboxamide-1-methyl-3-trifluoromethylpyrazole (compound 49 );m.

p, 99-101℃ 5-(3-butynylthio)-4-N-(2,4-difluorophenyl)carboxy Samido-1-methyl-3-trifluoromethylpyrazole (compound 50); m , p.

107-108℃ 5-(2-chloropropylthio)-4-N-(2,4-difluorophenyl)ka ruboxamide-1-methyl-3-trifluoromethylpyrazole (compound 51) :m.

p, 75.5-76.5°C 4-N-(2,4-difluorophenyl)carboxamide-5-(2,2-dimethyl Doquinethylthio)-1-methyl-3-trifluoromethylpyrazole (compound 52); m, p, 118-119.5°C 5-(2-butenylthio)-4-N-(2,4-difluorophenyl)carboxy Samido-1-methyl-3-trifluoromethylpyrazole (compound 53): m , p.

95-97℃ 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( n-pentylthio)-3-)lifluoromethylpyrazole (compound 54); m , p.

87-89℃ 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 2-methylbutylthio)-3-trifluoromethylpyrazole (compound 55); m, p, 83-85℃ 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 2-Methyl-2-propenylthio)-3-trifluoromethylpyrazole (compound Matter 56); m, p, 107-109°C 5-(2-chloro-2-propenylthio)-4-N-(2,4-difluorophe carboxamide-1-methyl-3-trifluoromethylpyrazole (compound Material 57): m, p, 93-95°C 4-N-(2,4-difluorophenyl)carboxamide-5-(2-methoxy ethyl)-1-methyl-3-trifluoromethylpyrazole (compound 58); m, p.

88-90℃ 5-(3-chloro-2-propenylthio)-4-N-(2,4-difluorophe carboxamide-1-methyl-3-trifluoromethylpyrazole (compound Material 59): m, p, 95-96°C Example 9 5-ethylthio-1-ethyl-3-trifluoromethylpyrazole-4-carbo Add thionyl chloride (2.4ml) to a toluene solution of phosphoric acid (0.5g), The reaction mixture was refluxed for 3 hours. After cooling, remove the solvent and excess thionyl chloride under reduced pressure. It was removed. The residue was dissolved in dichloromethane and added with triethylamine (0 , 34yrt1), followed by the addition of 2.4-fluoroaniline (0.2ml) The mixture was stirred at room temperature for 2 hours. Pour the mixture into water, separate the organic layer and add HCI, saturated Washed with sodium carbonate and brine. Then, the organic phase was dehydrated and Mg5O< ), and evaporated under reduced pressure to give 5-ethylthio-1-ethyl-4-N-(2,4- difluorophenyl)carboxamide-3-trifluoromethylpyrazole(difluorophenyl)carboxamide-3-trifluoromethylpyrazole Compound 60) was obtained as a beige solid (0.54 g) with m, p, 91-93 °C. .

By the same operation as above, 5-ethylthio-1-ethyl-4-N-(2,4,6 -)lifluorophenyl)carboxamide-3-trifluoromethylpyrazole (Compound 61) was prepared as a beige solid at m, p, 94-96°C. (fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole-4- A mixture of carboxylic acid (2.0 g) and thionyl chloride (13.9 g) was added to dry toluene. (added to 30 mj), heated under reflux for 1.5 hours and evaporated under vacuum. -(4-fluorophenylthio)-1-methyl-3-trifluoromethylpyrazo The ru-4-carboxylic acid chloride was obtained as an oil. Dry this oil with tetrahydrofuran (20 ml) was added to a dry solution containing triethylamine (0.7 g). Stirring of aniline (0.64 g) dissolved in dry tetrahydrofuran (30 ml) added to the solution. The mixture was stirred overnight, the solids were filtered off and dissolved in ether (50 m/). Washed. The combined filtrates were evaporated under vacuum to give a brown solid, which was dissolved in toluene. 5-(4-fluorophenylthio) of compound 91 was obtained by recrystallization from chlorine/hexane. -1-methyl-4-N-(phenyl)carboxamide-3-trifluoromethyl Pyrazole (1.4 g) was obtained as a brown solid, m, p, 146-148°C.

The following compounds were prepared from the corresponding carboxylic acids by operations similar to those described above. symbol The definition of is shown in the table below.

Example 11 5-(4-aminophenylthio)-4-N-(2,4-difluorophenyl)ka Ruboxamide-1-methyl-3-trifluoromethylpyrazole (2.3g) dimethyl disulfide to a stirred suspension in dry dichloromethane (30 mA'). (1.0 g) followed by t-butylnitrile (1.1 g) dropwise over 5 minutes. I added it down. The mixture was stirred at 50° C. for 3 hours and poured into water after overnight at ambient temperature. . The organic layer was separated and the aqueous solution was extracted again with dichloromethane.

The combined organic layers were dried over anhydrous magnesium sulfate and evaporated under vacuum. I got oil. on silica gel, eluting with a mixture of dichloromethane and hexane. Purification by chromatography yielded 4-N-(2,4-difluoro) of compound 92. lophenyl)carboxamide-1-methyl-5-(4-methylthiophenylthio )-3-trifluoromethylpyrazole (0,9 g) m, p, 122-124 Obtained as a creamy solid at °C.

Example 12 4-N-(2,4-difluorophenyl)carboxamide-5-(4-fluoro phenylthio)-1-methyl-3-trifluoromethylvirazole (2.0g) , iodomethane (0.29ml), powdered potassium hydroxide (0.286g) and and tetrabutylammonium bromide (0.3 g) in tetrahydrofuran (5 m The suspension in l) was stirred at room temperature for 26 hours and the solids were filtered off. Strain the filtrate Evaporation in vacuo gave a residue to which dichloromethane and water were added. organic phase was washed with saturated brine solution, dried over anhydrous magnesium sulfate, and evaporated under vacuum. I made it emanate and got oil.

Trituration with ether gives a solid, which is Chromatography on silica gel eluting with ether/n-hexane (1:1) The 5-(4-fluorophenylthio)-1-methane of compound 93 was purified by Chyl-4-N-methyl-N-(2,4-difluorophenyl)carboxamide- 3-trifluoromethylpyrazole (1,48 g) at m, p, 99-100°C Obtained in the form of a white solid.

Example 13 5-(4-chlorophenylthio)-4-N-(2,4-difluorophenyl)ka Ruboxamide-1-methyl-3-trifluoromethylpyrazole (0,63g) A 30% hydrogen peroxide solution was added to a stirred suspension of The solution (0.19 mj) was added dropwise at 0°C. After 2 hours at 0°C, the mixture The mixture was warmed to room temperature over 2 hours and then poured into ice water (50 m/h). Collect the precipitate washed with water and dehydrated with phosphorus pentoxide in a dencator, then dissolved in hexane. By chromatography on silica gel eluting with ether (1:1) of Purification yielded compound 94, 5-(4-chlorophenylsulfinyl)-4-N-(2 ,4-difluorophenyl)carboxamide-1-methyl-3-trifluorome Chilpyrazole (0,426 g) as a white solid at m, p, 178-179°C. Obtained.

Reference example 1 4-carboxy-5-chloro-1-methyl-3-trifluoromethylpyrazole (20,54 g) and thionyl chloride in dry toluene at 80°C for 2 hours. Heat and stir for an hour, cool and evaporate. Add hexane to the residue and filter. The liquid was concentrated to obtain acid chloride (21.4 g).

This acid chloride was dissolved in dry tetrahydrofuran and 2゜4-difluoroanili (13.4 g) and triethylamine (17.46 ml) in dry tetrahydrochloride. Added to stirred solution in furan. The mixture was stirred at room temperature for 18 hours and filtered. The solid was washed with tetrahydrofuran. Reconcentrate the evaporated filtrate from toluene. Crystallized to give 5-chloro-4-N-(2,4-difluorophenyl)carboxamide do-1-methyl-3-trifluoromethylpyrazole (20.7 g) m, p, Obtained as an off-white solid at 138-140<0>C.

Follow the same operations as above, as appropriate! The following compounds were prepared from the converted starting materials.

4-carboxy-5-chloro-1-methyl-3-trifluoromethylpyrazole are L, F, Lee, F, M.

5chleppnikXR, W, 5alineider and H, Campb J, Het by e I I.

5-chloro-4-formyl-1,3-dimethylpyrazole (30g), permanganate A mixture of potassium phosphate (30 g) and potassium hydroxide was heated at 60°C for 1 hour. Stir for a while.

The cooled mixture was filtered, the filtrate was acidified (a hydrochloric acid solution), and the resulting precipitate was filtered off. , washed with water and dehydrated m, p.

4-carboxy-5-chloro-1,3=dimethylpyrazole at 197-201°C I got it.

The following compounds were prepared from appropriately substituted starting materials by operations similar to those described above.

4-Carboquine-5-10-1-methyl-3-chlorodifluoromethylpyrazo m, p, 153-155℃ 4-carboxy-5-chloro-1-methyl-3-(n-propyl)pyrazole; scold p, 130-131℃ 4-carboquine-5-chloro-1-(2,2,2-1 (lifluoroethyl)-3-)lifluoromethylpyrazole Reference example 3 1,3-dimethyl in a mixture of phosphorus oxychloride and N,N-dimethylformamide -5-hydroxypyrazole (60g) was added and the resulting mixture was Heated at 0°C for 16-18 hours. Pour the reaction mixture onto ice water and dilute (with ammonia solution) ) and the resulting precipitate was isolated and washed with water. For recrystallization from hexane Therefore, m, p, 5-chloro-4-formyl-1,3-dimethylpi Got Razor.

Reference example 4 Add methylhydrazine (25 g) to a mixture of ethyl acetoacetate (70 g) and water. was added. The reaction mixture was heated at 70°C for 0.5 h, then cooled and extracted with chlorine. roporum), dehydrated (anhydrous magnesium sulfate). Evaporating the solvent leaves a solid behind. This solid was recrystallized from hexane/ethyl acetate to give m, p, 123-124. C. 1,3-dimethyl-5-hydroxypyrazole was obtained.

Reference example 5 4-formyl-1-methyl-5-(3-)lifluoromethylphenoxy)-3- Trifluoromethylpyrazole (7g), potassium permanganate (3.1g) and An aqueous solution of potassium hydroxide (approximately 0.3 g) was heated at 60 to 80°C for 2 hours. profit The resulting solution was cooled, filtered, and the filtrate was acidified. The resulting precipitate was filtered and washed with water. Washed and dehydrated. Recrystallization of the solid yields 4-carboxy-1-methyl-5-(3 -trifluoromethylphenoxy)-3-trifluoromethylpyrazole, This was refluxed with thionyl chloride in toluene for 40 minutes. Cool the resulting solution. Cool and concentrate to give 4-carboxylic acid chloride-1-methyl-5-(3-trifluoro methylphenoxy)-3-trifluoromethylpyrazole was obtained as a colorless oil. .

By the same operation as above, 4-carboxylic acid chloride-1-methyl-5-(3-chloro lophenoxy)-3-trifluoromethylpyrazole and 4-carboxylic acid chloride -5-(4-chlorophenoxy)-1,3-dimethylpyrazole was produced.

Reference example 6 Add 3-trifluor to a warm solution of potassium t-butoxide in t-butanol. Olomethylphenol (6.9ml) was added. The resulting mixture is 0.5 Stir for 5-chloro-4-formyl-1-methyl-3-trifluoromethyl Pyrazole (12g) was added. The mixture was heated at reflux temperature for 3 hours and then cooled. , diluted with water and the resulting solid isolated and dried. m by recrystallization from hexane , p.

4-formyl-1-methyl-5-(3-trifluoromethylphene) at 81-82°C. Noxy)-3-1-lifluoromethylpyrazole (9.2 g) was obtained.

By the same operation as above, m, p, 4-formyl-1-methyl- 5-(3-chlorophenoxy)-3-trifluoromethylpyrazole and m, p , 4-formyl-1,3-dimethyl-5-(4-chlorophenokyl) at 74-75°C. ) pyrazole was produced.

Reference example 7 Sodium sulfide hydrate (42g) and sulfur (5,6g) in isopropanol 5-chloro-4-N-(2,4-difluorophenyl)carboxylate Add samido-1-methyl-3-trifluoromethylpyrazole (29.7g) did. The mixture was heated at reflux under an inert atmosphere for 1.75 hours. The cooled solution The liquid was decanted, treated with charcoal and filtered to obtain a bright yellow solution; This was concentrated, filtered and evaporated to dryness to remove sodium 1-methyl-4-N-( 2,4-difluorophenyl)carboxamide-3-trifluoromethylpyrazo Mol-5-thiolate (31,68 g) as a solid at m, p, 311-313°C. Ethyl 3-(trifluoromethyl)pyrazole-4-carboxylate (5g) , potassium carbonate (3.48g) and ethyl iodide (2.3ml) in acetonitrile The mixture was heated at reflux overnight. After cooling, add ethyl acetate and water. , the organic phase was separated. Extract the aqueous layer with ethyl acetate and combine the organic extracts. Dehydrate (magnesium sulfate) and evaporate under reduced pressure to obtain a yellow part, which is 4-ethoxycarbonyl-1-ethyl-3-tri Fluoromethylpyrazole was obtained as white crystals (3.65g). δ□(CDC Is): 1.25 (3H, t), 1.45 (3H, t), 4.10 ( 2H.

q), 4.20 (2H, Q), 7.90 (IH, s) diisopropyla n-butyllithium (2,5 m/) was added to a tetrahydrofuran solution of M; 3.5 ml) was added at 0° C. under an inert atmosphere. Solution at 0℃ Stir for 45 minutes and add 4-ethoxycarbonate at -78°C under an inert atmosphere. Tetrahydryl-1-ethyl-3-trifluoromethanepyrazole (1,76g) Transferred to Dorofuran solution. The deep orange solution was stirred at -78°C for 3.5 hours. , then ethyl disulfide (1.1 mj) was added. The solution was left stirring overnight. and warmed to room temperature. The precipitate was diluted with ether and the organic layer was diluted with a 2M solution of MCI. Washed. The aqueous layer was extracted again with ether. Dehydrate the combined organic extracts. and evaporated under reduced pressure to give ethyl 5-ethylthio-1- Ethyl-3-trifluoromethylpyrazole-4-carboxylate was added to a yellow oil ( 2g). δH (CDCIs): 1.25 (3H1t), 1.4 0 (6H, m), 3.0 (2H, q), 4, 40 (4H, m) pp m.

Reference example 10 Ethyl 5-ethylthio-1-ethyl-3-trifluoromethylpyrazole-4- Carboxylate (2g) dissolved in ethanol and potassium hydroxide added to water (1 g) was added. The reaction mixture was stirred at room temperature overnight. Add water and ethyl acetate and the organic layer was separated from the aqueous layer. The aqueous layer was acidified with concentrated HCl and Extracted with chill. The combined organic extracts were dehydrated (Mg504) and under reduced pressure. Evaporate to 5-ethylthio-1-ethyl-3-trifluoromethylpyrazole -4-carboxylic acid was obtained as a beige solid (1.42 g). δ, l(CDC Ig): 1.25 (3H, t), 1.45 (3H, t), 3.05 ( 2H.

q), 4.45 (2H, Q), 6.5 (IH, br 5) 5-chloro-4- N-(2,4-difluorophenyl)carboxamide-1-methyl-3-trif Fluoromethylpyrazole (3,0 g) was dissolved in dry toluene (110 ml’). Lawesson reagent [2,4-bis(4-methoxyphenyl)-1 ,3-dithia-2,4-diphosphethane-2,4-disulfide; 2.14g 1 was added and the mixture was heated at 80-85°C for 2 hours and then at reflux temperature for 1.50 hours. It was hot. Additional Lawesson reagent (3.57 g) was added and the mixture was further heated under reflux conditions. Heated for 9 hours. The solvent was evaporated under vacuum and the residue was dissolved in dichloromethane/hexane. Purified by chromatography on silica gel eluting with (1:1) 5-chloro-4-N-(2,4-difluorophenyl)thiocarboxamide-1 -Methyl-3-trifluoromethylpyrazole (2,49g) in yellow oil methyl 5 -(4-fluorophenylthio)-1-methyl-3-methylthiopyrazole-4 - Carboquinlate (1.0g), potassium hydroxide (0.4g), water (3m) 1) and methanol under reflux for 2.5 hours. under vacuum After evaporation at , the residue was dissolved in water and filtered, and the filtrate was acidified to pH 1 with hydrochloric acid. . The precipitated solid was filtered off and dehydrated with phosphorus pentoxide in a desiccator to give 5-(4 -fluorophenylthio)-1-methyl-3-methylthiopyrazole-4-cal Bonic acid (1.0 g) was obtained.

Reference example 13 Methyl 5-amino-1-methyl-3-methylthiopyrazole-4-carboxylene Add 4-fluorophenyl to a stirred solution of 2.0 g of Ludisulfide (5.1 g) was added. Distill t-butylnitrile (2.0g) Add a solution dissolved in chloromethane (5 ml) little by little over 20 minutes and mix. The mixture was stirred overnight. After evaporation under vacuum, the residue was dissolved in dichloromethane/hexane ( Chromatography on silica gel eluting with cyclohexane (1:1) Methyl 5-(4-fluorophenyl thio)-1-methyl-3-methylthiopyrazole-4-carboxylate methyl (1.2 g) was obtained.

Reference example 14 2-cyano-3,3-bismethylthiopropenoic acid methyl ester (10.1g) Acetic acid (20ml) was added to the methanol solution of 2.3 g) was added to -ff. The mixture was stirred overnight and evaporated under vacuum. Residue The distillate is triturated with water, the solid is filtered off and purified on silica gel, eluting with dichloromethane. Purification by chromatography at Obtained tilthiopyrazole-4-carboxylate (1,5 g) as a white solid. .

Reference example 15 5-chloro-1-methyl-3-trifluoromethylpyrazole-4-carboxylic acid (2,0g), 4-fluorothiophenol (1,66g), and anhydrous potassium carbonate. (3.26 g) was added to acetonitrile and refluxed with stirring for 4 hours. Heated under flow. After filtration, the filtrate was evaporated, acidified with dilute hydrochloric acid and extracted with ethyl acetate. I put it out. The combined extracts were dehydrated (anhydrous magnesium sulfate), filtered and vacuum Evaporated down. m, p, 190-1 by recrystallization from ether/hexane 5-(4-fluorophenylthio)-1-methyl-3-trifluoro at 93.7°C Lomethylpyrazole-4-carboxylic acid (0.98g) was mixed with a white solid and 5-chloro- 1-Methyl-3-trifluoromethylpyrazole-4-carboxylic acid (15.3g ), 2-methylpropanethiol (19,2ml) and anhydrous potassium carbonate (4ml) 0.5 g) in acetonitrile under an inert atmosphere and heated at reflux temperature for 68 hours. did. The reaction mixture was filtered hot and then evaporated to give a cream solid, which was It was suspended in 2M hydrochloric acid and extracted with dichloromethane. Combine the extracts and anhydrous Dried over magnesium sulphate, filtered and evaporated. Pour the resulting creamy solid into 1-Methyl-5-(2-methylpropylthio)-3-triflu by trituration with xane oromethylpyrazole-4-carboxylic acid (6.4 g) m.

p, 183-184°C as a white solid.

By the same operation as above, 1-methyl-5-(2-methylpropylthio)-3- Pentafluoroethylpyrazole-4-carboxylic acid was produced. δH(DM) S Od.) 20, 96 (d, 6H), 1.68 (m, IH), 2.85 ( d, 2H), 4.00 (s, 3H), 13.20 (s.

IH)ppm.

In one aspect, the present invention provides a method for controlling the growth of weeds (i.e., undesirable plants) in a given location. provides a method for controlling at least one species having formula I in said place. Applying an N-substituted virazole derivative or an agriculturally acceptable salt thereof in a herbicidally effective amount. including For applications such as those mentioned above, N-substituted pyrazole derivatives are usually used. For example, in the form of a herbicidal composition as described below (i.e. for use in a herbicidal composition). (with suitable compatible diluents or carriers and/or surfactants) .

Compounds of formula I are suitable for use in dicotyledonous (i.e. broad-leaved) weeds and monocotyledonous (e.g. Poaceae) weeds. demonstrating herbicide activity against weeds (of plants) by pre-emergence and/or post-emergence application. .

The term “pre-emergence application” refers to applications where weed seeds or seedlings are present in the soil. It refers to the application to the soil before it emerges from the soil. “Apply after appearance” The term means application to the aerial or exposed parts of weeds that have emerged from the soil. . The compound of formula ■ is, for example, Abutilon theophrasti, Amar anthus retroful-xus), Bidens p. i Iosa), Nroza (Chenopodium album), Yaemugura (Galium aparine), Ipomoea species, e.g. (Ipomoea pur-purea), 5esbania exaltat a, Sinapis arvensis, So. lanum nigrum) and Xantium strumar broad-leaved weeds such as Alopecurus myosuroides, oat (Avena f. atua), crabgrass (Digi-taria sanguinalis), E-chinochloa crus-galli, El eusine 1ndica) and 5eta-ria species, e.g. Insects such as Setaria faberii and Setaria vjridis Negative weeds, and Cyperaceae, such as Cyperus esculentus weed can be used to control the growth of

The amount of compound of formula I applied depends on the nature of the weed, the composition used, the time of application, the climatic conditions and the soil. Soil conditions and crops (if used to control weed growth within cropping areas) It varies depending on the nature of. When applied to crop-growing areas, the amount applied should be be sufficient to control weed growth without causing qualitatively permanent damage. Should. Usually, taking into account the factors mentioned above, the amount of active substance applied should be adjusted per hectare. Excellent results are obtained with 0.01 to 5 kg per tar.

However, depending on the particular problem at hand in weed control, more or less It should be understood that it is also possible to use lower dosages.

Compounds of formula I can be used, for example, in wheat, barley, oat, maize and rice. Which grains, soybeans, field beans and string beans, peas, beans, etc. Rufalfa, cotton, peanut, flax, onion, carrot, cabbage, horsefly Used in the cultivation of crops such as rana, sunflowers, sugar beets, etc. areas to be planted and evergreen grasslands or artificial grasslands n　grassland) before sowing crops or in areas where weeds are prevalent. is after, or before or after the emergence of the crop directly or indirectly before or after the emergence of the crop. For example, by direct or indirect spraying, e.g. It can be used to selectively control the growth of weed species. Cultivation of crops, e.g. Weeds are removed in areas used or to be used for cultivation where weeds are infested. For selective control of 0.01-4. Qkg, preferred An active substance application amount of 0.01 to 2.0 kg is particularly suitable.

Compounds of formula I can be used in established orchards and other arboricultural areas, such as forests, woodlands and public areas. gardens and plantations, such as sugarcane, Guinea oil palm and rubber. Weeds, especially those listed above, due to pre-emergence or regression in planchy/con. It can be used to control weed growth.

For this purpose, a compound of formula ■ may be added before or after tree planting or plantation construction. per hectare against weeds or on land where weeds are expected to grow. with an active substance application amount of 0.25 to 5.0 kg, preferably 0.5 to 4.0 kg per day. It may be applied directly or indirectly (eg by direct or indirect spraying).

Compounds of formula I are administered in areas that are not crop growing areas, but where it is desirable to control weeds. It can also be used to control the growth of weeds, especially those mentioned above.

Examples of non-crop growing areas include airfields, industrial sites, railways, roadsides, river edges, Irrigation canals and other waterways, bushland, and fallow or uncultivated land are particularly vulnerable to fire. Includes locations where it is desirable to control weed growth to reduce it.

Used for weed control in areas such as those mentioned above where general weed control is often desired. In cases where the active compound is usually used in higher amounts than when used in crop areas such as those mentioned above. apply to

The exact dosage will depend on the nature of the plants being treated and the desired effect.

For weed control in non-crop areas, 1.0-20.0 kg/ha; Preferably with an active substance application amount of 5.0 to 10.0 kg (e.g. by direct or indirect injection). (by fog) for pre-emergence or re-emergence, preferably Particularly suitable for on-the-spot applications.

The compounds of formula I when used for weed growth control by pre-emergence application are may be mixed into the soil.

The compound of formula 1 is used for retraction, i.e., the aerial parts or exposed parts of the weeds that have emerged. When used for weed growth control by application to soil, the compounds usually do not come into contact with the soil. Therefore, it is understood that pre-emergence control of weeds in the soil that germinate later can also be achieved.

Especially when weeds have to be controlled over a long period of time, the application of compounds of formula I is Can be repeated if necessary.

According to another feature of the invention, one or more N-substituted pyrazole derivatives having formula I or one or more agriculturally acceptable compatible diluents. or carriers and/or surfactants (i.e. suitable for use in herbicidal compositions). diluents or carriers generally accepted in the art as a surfactant compatible with the compound of formula I), preferably containing To provide a composition suitable for herbicidal use, containing the composition in a dispersed state. “Homogeneously minutes The term "dispersed" also applies to compositions in which the compound of formula I is dissolved in other ingredients. . The term "herbicidal composition" is used in a broad sense and is ready for use as a herbicide. It includes not only compositions, but also concentrates, which must be diluted before use. preferred Preferably, the compositions of the invention contain from 0.05% to 90% by weight of one or more Formula I compounds.

Herbicidal compositions include a diluent or carrier and a surfactant (e.g. wetting agent, dispersing agent or or an emulsifier). Interfaces that may be present in the herbicidal composition of the present invention The activator may be ionic or nonionic, e.g. salts, quaternary ammonium derivatives, ethylene oxide and nonyl or octyl fluoride. The main component is a condensate with alkyl or polyarylphenol such as phenol. products or ethers of free hydroxyl groups by condensation with ethylene oxide Anhydrosorbitol carboxylic acid ester, dino sulfuric acid esters and Alkali and alkaline earth metal salts of sulfonic acids, and sodium and calcium Murinosulfonate, and sodium and calcium alkylbenzene sulfonate alkali and alkaline earth metal salts of polymeric sulfonic acid derivatives, such as It can be.

The herbicidal composition according to the invention contains less than 10% by weight, for example from 0.05 to 10% by weight. The herbicidal compositions according to the invention suitably contain surfactants, if desired. It is also possible to contain higher proportions of surfactants, for example in emulsifying suspensions. Surface active content is 15% by weight or less in cloudy concentrates and 25% by weight or less in water-soluble concentrates. agents may be present.

Examples of suitable solid diluents or carriers include aluminum silicate, talc, calcined Magnesium, porous diatomaceous earth, trilime phosphate, cork powder, adsorbent carbon bra clays such as kaolin and bentonite. (Dust, granules, The solid composition (which may take the form of a wettable powder or a wettable powder) preferably contains a compound of formula I in a solid form. or by dissolving the compound of formula I in a volatile solvent. Impregnate the dissolved solution in a solid diluent or carrier, evaporate the solvent, and If necessary, the product is prepared by grinding it into a powder. granular composition The compound of formula I (dissolved in a suitable solvent, which may be volatile if desired) is granulated. in a solid diluent or carrier and, if desired, evaporate the solvent. or by granulating the powdered composition obtained as described above. Therefore, it can be prepared. Solid herbicidal compositions, especially wettable powders and granules (e.g. may contain wetting or dispersing agents (such as those mentioned in It may function as a diluent or carrier.

The liquid compositions according to the invention can be aqueous, organic or aqueous, which may contain surfactants. They can take the form of organic solutions, suspensions and emulsions. Contained in liquid composition Suitable liquid diluents include water, glycols, and tetrahydrofurfuryl alcohol. , acetophenone, cyclohexanone, isophorone, toluene, xylene, mineral oil , animal and vegetable oils, and light aromatic and naphthenic fractions of petroleum (and mixtures of these diluents). Surfactants that may be present in the liquid composition include: may be an ionic or nonionic surfactant (such as those listed above); If it is a liquid, it still functions as a diluent or carrier.

Compositions in the form of powders, dispersible granules, and liquid concentrates may be prepared using water or other suitable diluents. , for example mineral oil or especially in the case of liquid concentrates where the diluent or carrier is oil. By diluting with vegetable oil, a ready-to-use composition can be obtained.

If desired, the liquid composition containing the compound of formula I can be prepared by emulsifying the active substance. in the form of a self-emulsifying concentrate containing the active substance dissolved in an agent- or emulsifier-containing solvent. Such concentrates can be made into ready-to-use compositions by simply adding water. Become.

Liquid concentrates where the diluent or carrier is oil can be further diluted using electrostatic spraying techniques. It can be used without

The herbicidal composition according to the invention may optionally contain adhesives, protective colloids, thickeners. , penetrants, stabilizers, sequestrants, anti-caking agents, colorants and corrosion inhibitors Conventional additives such as agents may also be included. These additives are also carriers or diluents. functions as

Unless otherwise specified, the following percentages are by weight (preferred according to the invention). Herbicidal compositions contain 10-70% of one or more compounds of formula I and 2-70% of a surfactant. Aqueous suspension concentrate containing 10%, 0.1-5% thickener and 15-87.9% water , 10-90% of one or more compounds of formula I, 2-10% of surfactant, solid diluent or a wettable powder containing 8-88% carrier; 10-90% of one or more compounds of formula I, 2-40% of sodium carbonate, solid dilute Water-soluble or water-dispersible powder containing 0 to 88% diluent, 5 to 50% of one or more compounds of formula l, for example 10 to 30%, and 5 to 50% of a surfactant. 25%, a water-miscible solvent such as dimethylformamide, or a water-miscible solvent and water One or more water-soluble concentrates containing 25-90%, e.g. 45-85%, of a mixture of 10-70% of the compound of formula I above, 5-15% of the surfactant, and 0.1-70% of the thickener. 5%, an emulsifying suspension concentrate containing from 10 to 84.9% of organic solvent, one or more of formula I 1 to 90%, e.g. 2 to 10% of the compound, and 0.5 to 7% of the surfactant, e.g. 0.5-2%, 3-98.5%, e.g. 88-97.5%, particulate carrier. granules, and One or more compounds of formula I from 0.05 to 90%, preferably from 1 to 60%, surface active 0.01 to 10%, preferably 1 to 10% of the agent, and 9.99 to 99.9% of the organic solvent. 4%, preferably 39-98.99%.

Herbicidal compositions according to the invention contain a compound of formula I in combination with one or more other pesticidal active compounds. , and, if desired, one or more compatible and pesticide-acceptable diluents or additives. Preferably along with carriers, surfactants and conventional additives such as those listed above. It is also possible to contain them in a homogeneously dispersed state. Herbicide of the present invention Other pesticide activations that may be included in or used in conjunction with the composition. Examples of compounds include herbicides, e.g. lachlor[2-chloro-2,6'-diethyl-N-(methoxy-methyl)-a cetanilide], atrazine [2-chloro-4-ethylamino-6-itubrobi ruamino-1,3,5-triazine], bromoxynil [3,5-dibromo-4 -hydroxybenzonitrile], chlortoluron [N'-(3-chloro-4- methylphenyl)-N,N-dimethylurea], cyanazine [2-chloro-4- (1-cyano-1-methylethylamino)-6-ethylamino-1,3,5-t Riazinko, 2,4-D[2,4-dichlorophenoxyacetic acid, dicamba[3, 6-dichloro-2-methoxybenzoic acid], Difenzoquat [1,2-dimethybenzoic acid] -3,5-diphenyl-pyrazolium salt], flamprobumethyl [methyl N- 2-(N-benzoyl-3-chloro-4-fluoroanilino)-propionate ], Fluometuron [N'-(3-)lifluoromethylphenyl)-N, N- dimethylurea], isoprobone [N'-(4-isopropylphenyl)- N,N-dimethylurea], insecticides such as permethrin and dibermethrin Any synthetic pyrethroids as well as fungicides, such as methyl N-(1-butyl-cal) carbamates such as bamoyl-benzimidazol-2-yl) carbamate; 1-(4-chlorophenoquine)-3,3-dimethyl-1-(1,2,4-tri Triazoles such as azol-1-yl)-butan-2-one are included.

For example, as listed above, the herbicidal composition of the present invention may contain or Acids among agriculturally active compounds and other biologically active substances that may be used in conjunction with the compositions. Some may be used, if desired, with the usual derivatives, such as alkali metal salts and esters, as well as It can also be used in the form of amine salts and esters.

A further feature of the invention provides that the present invention provides a method for storing a small number of formulas (at least one type of or preferably at least one N-substituted pyrazole derivative of formula I - a herbicidal composition as mentioned above containing a substituted pyrazole derivative, preferably before use; a herbicide concentrate which must be diluted to The container and article provide a method of using the herbicide composition to control the growth of weeds. providing a product that includes logically combined instructions for use; The container is normally at normal ambient temperature. For storage of chemicals that are solid at high temperatures, and especially herbicidal compositions in the form of concentrates. of the type commonly used, e.g. made of metal that may be lacquered on the inside. , and cans and drums made of plastic materials, bottles made of glass and plastic materials , and if the contents of the container are solid, e.g. granular herbicide compositions, e.g. cardboard, A box or bag made of plastic material and metal. Containers are usually small (and 1 acre of land with enough water to treat it to control weed growth on the land. having a capacity sufficient to accommodate an amount of the N-substituted pyrazole derivative or herbicide composition. but not larger than that suitable for normal handling methods. Instructions for use may include, e.g. by printing directly on the container or on a label or tag that is fixed to the container. is physically coupled to the container. Instructions for use usually have a purpose as stated above. 1 hectare of the contents of the container, after dilution if necessary, as described above. Application for weed growth control at application rates of active substance from 0.01 to 20 kg per roll Show what to do.

Next, examples of herbicide compositions according to the present invention will be shown.

Composition example C1 soluble concentrate Active ingredient (Compound 1) 20%v/v 33% w/v solution of potassium hydroxide 10% V/V tetrahydrofurfurylal Coal (THFA) 10% V/V water up to 100 volume% THFA, active ingredient (compound 1), and 90% by volume of water were stirred and hydroxylated. Slowly add the potassium solution to stabilize the pH value at 7-8, then add the remaining water. Manufactured by adding.

Other formulas for N-substituted pyrazole (compound 1)! By replacing the compound with A soluble concentrate of can be produced by the method described above.

Composition example C2 wettable powder Blend these ingredients with each other and mill the resulting mixture in an air jet mill. Manufactured by crushing.

N-substituted pyrazoles (compound 1) can be other compounds of formula 1.

Composition example C3 water soluble powder Sodium bicarbonate 47% W/W From there, these ingredients are mixed and the resulting mixture is ground in a hammer mill. Manufacture more.

By replacing the N-substituted pyrazole (compound 1) with another compound of formula water-soluble powders can be produced by the method described above.

Representative compounds of formula I are used for herbicidal applications according to the following procedure: a) Common procedure The compound used for plant treatment is dissolved in acetone in an appropriate amount, and the amount of 4 per hectare is A solution corresponding to a test compound application amount (g/ha) of up to 1,000 g was obtained. This solution a standard spraying volume equivalent to 2901 sprays per hectare. The herbicide was applied from a laboratory herbicide sprayer.

b) Weed control: before emergence Seeds were sown on non-sterile surfaces in 70 mm square plastic pots with a depth of 75 mm.

The amount of seeds per pot was as follows.

Approximate number of seeds/pot ^butilon theophrasti 10^maranthus re troflexus 20Galium aparine 10 ■4■oea purpurea 10Sinapis arvensis 1 5Xanthiu+s 5trua+arium 22) Poaceae weeds ^1opecurus i*yosuroides 15Avena fatu a 10 Echinochloa crus-galli 15Setaria vir idis 203) Cyperaceae Cyperus esculentus 3 corn 2 The compounds of the invention were applied to the surface of the seeded soil as described in (a). Individual One pot of each crop and each weed was allocated to the treatment; a control without spraying; A control was also provided in which only acetone was sprayed.

After treatment, the pots were placed on a capillary mat placed in the greenhouse, and water was poured from above.

Crop damage was visually assessed 20-24 days after spraying. Results are control pot manifested as reduced growth rate or damage of crops or weeds compared to other plants .

C) Weed control: after emergence John Inn where weeds and crops were housed in 70mm square pots with a depth of 75mm Seed directly in es pot compost, except for Amaranthus at seedling stage. The plants were transplanted into pots one week before spraying. Plants in a greenhouse, used for plant treatment The compound was grown to the point where it could be sprayed.

The number of plants per pot was as follows.

Amaranthus retroflexus 4 1-2 leaves Galium aparine 3 - Harume Ipomoea purpurea 3 1-2 leaves 5 inapis arvensis 4 2 leaves Xantium struma rium 1 2-3 leaves Avena fatua 12-18 1-2 leaves Ech inochloa crus-galli 4 2-3 leaves 5etaria vi ridis 15-25 1-2 leaves ■) Broad leaves Compounds used to treat plants were applied to plants as described in (a). individual places Specifically, one pot of each crop and each weed was allocated, and a control, no spraying, and Controls were also provided in which only acetone and acetone were sprayed.

After treatment, the pots were placed on a capillary mat placed in the greenhouse and lifted once after 24 hours. Afterwards, water was supplied by controlled underground irrigation systems. 20-2 from spraying After 4 days, crop damage and weed control were visually assessed. The results show that the control pot Expressed as reduced growth rate or damage of crops or weeds compared to plants.

The compounds of the present invention used in amounts below 4 k g/h a were used in the experiments described above. It exhibits excellent levels of herbicidal activity against weeds and is also highly tolerated by crops. Ta.

Compounds 1-106 when applied before or after emergence in an amount of 4000 g/ha reduce the growth of one or more weed species by at least 70%, and these compounds also reduce the growth of one or more weed species by at least 70%. Showed selectivity for at least one crop species.

Continuation of front page (31) Priority claim number 9306180.2 (32) Priority mill March 1993 25th (33) Priority claim country: United Kingdom (GB) (81) Designated country: EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IE, IT, LU, NL, PT, SE), AU, BG, BR, CA, CZ, FI, HU, JP, KR, NZ , PL, R○, RU, SD, SK, UA, US Special Table Sen7-507781 (36) (72) Inventor: Ginger, Michael, UK, Essex CM 5.0 H.W., Ongar, Fyfield Road, Loughnoop. -Ran Agriculture Limited (no street address) (72) Inventor Hawkins, Dipid William Essex, England ・CM 5.0 H.W., Ongar, Fyfield Law Rhoneop-Lan Agriculture Limited (no street address) (72) Inventor: Richards, Raymond Dipid, Cornwall, UK R.P.L. 32.9 T.D., Camelford, Hillhead ・Gardens 2

Claims (25)

[Claims] 1. Formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▲I [In the formula, R1 is Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; containing 3 to 6 carbon atoms, optionally one or more R6 groups; cycloalkyl group substituted with; -(CH2)n-Ar group (where n is 0 or 1, Ar is optionally a halogen group) -N, nitro, R6, -OH, -OR6, -S(O)mR7 and -NR8R9 represents a phenyl group substituted with one or more groups selected from ); up to 6 carbons containing one or more atoms optionally selected from halogen, R6 and -OR6 a straight-chain or branched alkenyl or alkynyl group substituted with a group; or Select from -SO2NR61R62, -SO2R71 and -CONR61R62. Indicates the selected group; R2 represents -X-R10 group; R3 is hydrogen or halogen atom; Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; containing 3 to 6 carbon atoms, optionally containing one or more halogens; cycloalkyl group substituted with an atom or R6 group; cyano or nitro group ; -S(O)mR6 group; Optionally one or more selected from halogen, nitro, R6, -OR6 and cyano phenyl substituted with the above group; or -CO2R6 group; R4 is optionally halogen, nitro, R6, -OR6, -S(O)mR7 and -NR8R9 phenyl substituted with one or more groups selected from; or optionally halogen, nitro, R6, -OR6, -S(O)mR7 and -NR8R9 represents pyridyl substituted with one or more groups selected from; R5 is a hydrogen atom or a straight or branched alkyl group containing up to 6 carbon atoms; Show; Y represents oxygen or sulfur atom; R6 contains up to 6 carbon atoms and is optionally substituted with one or more halogen atoms Represents a straight chain or branched alkyl group; R61 and R which may be the same or different 62 each contain up to 6 carbon atoms, optionally substituted with one or more halogen atoms represents a straight-chain or branched alkyl group containing up to 4 carbon atoms; R represents a straight or branched alkyl group optionally substituted with one or more halogen atoms; 71 is Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; or optionally halogen, nitro, R6, -OR6, -S (O) A group substituted with one or more groups selected from mR7 and -NR8R9 phenyl; R8 and R9, which may be the same or different, are each hydrogen or up to 6 carbons linear or branched chain atoms, optionally substituted with one or more halogen atoms; Indicates a rukyl group; R10 is Optionally halogen, nitro, R6, -OR8, -S(O)mR7, -NHCOR6 and phenyl substituted with one or more groups selected from -NR8R9; Optionally halogen, nitro, R6, -OR6, -S(O)mR7, -NHCOR6 and pyridyl substituted with one or more groups selected from -NR8R9; or containing up to 10 carbon atoms, the chain optionally containing one or more oxygen, sulfur or may contain a -NR5- group, and optionally halogen, -OR6-, -S( O) qR6, -NR8R9, -CO2R8, -OCOR6, -NHCOR6, - 1 selected from CONR8R9, R12, -COR8, R13 and cyano Straight-chain or branched alkyl, alkenyl or aryl substituted with one or more groups Represents a ruquinyl group; X represents an oxygen atom, -NR11- or -S(O)m-; R11 is hydrogen or 6 straight-chain or straight-chain containing up to 1 carbon atoms, optionally substituted with one or more halogen atoms represents a branched alkyl group; R12 contains 3 to 7 ring atoms, optionally selected from oxygen, sulfur and -NR5-. Indicates a cycloalkyl group which may contain 1 to 3 selected heteroatoms in the ring. ;R13 is 1 containing 3 to 6 carbon atoms and selected from halogen, R8 and -OR8 a cycloalkyl group substituted with one or more groups; or containing 5 or 6 carbon atoms, optionally selected from halogen, R8 and -OR8 represents a cycloalkenyl group substituted with one or more selected groups; m is 0, 1 or 2; p is 0, 1 or 2; q is 0, 1 or 2; ; Y represents oxygen, R2 represents methylthio or N-phenylamino, and R4 represents phenylamino. When R5 represents hydrogen, R1 and R3 do not represent methyl at the same time. ] and its agriculturally acceptable N-substituted pyrazole derivatives salt. 2. R1 is Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; containing 3 to 6 carbon atoms, optionally one or more R6 groups; a cycloalkyl group substituted with; or -(CH2)n-Ar group (where n is 0 or 1, Ar is optionally a halogen group) -N, nitro, R6, -OH, -OR6, -S(O)mR7 and -NR8R9 represents phenyl substituted with one or more groups selected from hydrogen or halogen atom; Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; containing 3 to 6 carbon atoms, optionally one or more R8 groups; cycloalkyl group substituted with; Cyano group; -S(O)mR6 group; Optionally one or more selected from halogen, nitro, R6, -OR6 and cyano phenyl substituted with the above group; or -CO2R6 group; R10 is Optionally halogen, nitro, R6, -OR8, -S(O)mR7, -NHCOR8 and phenyl substituted with one or more groups selected from -NR8R9; or Optionally halogen, nitro, R6, -OR6, -S(O)mR7, -NHCOR6 and -NR8R9 represents pyridyl substituted with one or more groups selected from A compound according to claim 1. 3. The compound according to claim 2, wherein X represents an oxygen or sulfur atom or a -NR11 group. . 4. R1 is Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; containing 3 to 6 carbon atoms, optionally one or more R6 groups; a cycloalkyl group substituted with; or -(CH2)n-Ar group (where n is 0 or 1, Ar is optionally a halogen group) -N, nitro, R6, -OH, -OR6, -S(O)mR7 and -NR8R9 represents phenyl substituted with one or more groups selected from hydrogen or halogen atom; Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; containing 3 to 6 carbon atoms, optionally one or more R6 groups; cycloalkyl group substituted with; Cyano or nitro group; -S(O)mR6 group; Optionally one or more selected from halogen, nitro, R6, -OR6 and cyano phenyl substituted with the above group; or -CO2R6 group; R10 contains up to 10 carbon atoms and the chain optionally contains one or more oxygen or sulfur atoms. It may contain a yellow atom or a -NR5- group, and optionally a halogen, -OR8, -S(O)qR6, -NR8R9, -CO2R8, -OCOR6, -NHCOR 6, -CONR8 Substituted with one or more groups selected from R9, R12 and cyano represents a straight-chain or branched alkyl, alkenyl or alkynyl group A compound according to claim 1. 5. R3 is hydrogen or halogen atom; Straight-chain groups containing up to 6 carbon atoms and optionally substituted with one or more halogen atoms or a branched alkyl group; containing 3 to 6 carbon atoms, optionally one or more R6 groups; cycloalkyl group substituted with; Cyano or nitro group; -S(O)mR6 group; Optionally one or more selected from halogen, nitro, R4, -OR4 and cyano phenyl substituted with the above group; or -CO2R6 group; R10 contains up to 10 carbon atoms and the chain optionally contains one or more oxygen or sulfur atoms. It may contain a yellow atom or a -NR5- group, and optionally a halogen, -OR8, -S(O)qR6, -NR8R9, -CO2R8, -OCOR6, -NHCOR 6, selected from -CONR8R9, R12, -COR8, R13 and cyano straight-chain or branched alkyl, alkenyl or alkyl substituted with one or more groups 2. A compound according to claim 1, which exhibits a quinyl group. 6. A claim in which R10 represents phenyl substituted with at least one halogen atom 4. A compound according to any one of 1 to 3. 7. R10 contains up to 4 carbon atoms, optionally substituted with one or more halogen atoms of claims 1, 4 and 5, representing a straight chain or branched alkyl or alkenyl group. A compound according to any one of the items. 8. R2 is -SR10 (wherein R10 is an alkenyl group containing up to 4 carbon atoms) 6. The compound according to any one of claims 1, 4 and 5, which exhibits 9. R10 contains up to 6 carbon atoms, optionally substituted with one or more halogen atoms; Claims indicating straight-chain or branched alkyl, alkenyl or alkynyl groups that are substituted with A compound according to any one of 1, 4 and 5. 10. Claim 1 or 5, wherein R10 represents a -CH2R12 or -CH2R13 group. Compounds listed. 11. 11. The compound according to claim 1, wherein Y represents an oxygen atom. 12. according to any one of claims 1 to 11, wherein R1 represents methyl or ethyl Compound. 13. According to any one of claims 1 to 12, R3 represents trifluoromethyl. compound. 14. R4 is 2,4-difluorophenyl or 2,4,6-trifluorophenyl 14. A compound according to any one of claims 1 to 13, which exhibits a 15. 15. The compound according to any one of claims 1 to 14, wherein R5 represents a hydrogen atom. 16. 16. A compound according to any one of claims 1 to 15, wherein X represents a sulfur atom. 17. 17. A compound according to any one of claims 1 to 16, wherein X represents an oxygen atom. 18. R1 contains 1 or 2 carbon atoms and may be the same or different 1 represents an alkyl group optionally substituted with one or more halogen atoms; R3 is up to 5 halogens, which may be the same or different, containing up to 3 carbon atoms an alkyl group optionally substituted with atoms; or -SMe group; 1 where R4 is optionally selected from halogen, trifluoromethyl and methoxy represents phenyl substituted with ~3 groups; R5 represents a hydrogen atom or a methyl group; Y represents oxygen or sulfur atom; X represents an oxygen atom or -S(O)p- group; R10 is Optionally halogen, methoxy, hydroxy, -NHCOMe, -NH2-SMe, phenyl substituted with a group selected from methyl and trifluoromethyl; Pyridyl; a cycloalkyl group containing from 3 to 6 carbon atoms; or containing up to 6 carbon atoms; Optionally halogen, -CO2Et, cyano, cyclopropyl, methoxy and -CO Straight chain or branched chains substituted with one or more groups selected from NHMe represents alkyl, alkenyl or alkynyl group; p indicates 0 or 1 A compound according to claim 1. 19.4-N-(2,4-difluorophenyl)carboxamide-5-(4-k) lorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(4-methoxy phenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(4-fluoro phenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(4-bromophenyl) phenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(4-hydroxy Cyphenylthio)-1-methyl-3-trifluoromethylvirazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(2-fluorophenyl) phenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(3-fluoro phenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-phenylthio- 1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(4-acetoacetate) midophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(4-methylphenyl) phenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(3-trifluoromethylphenyl)carboxamide-5-(4-methyl ruphenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(4-methoxyphenyl)carboxamide-5-(4-chlorophenyl thio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(3-chlorophenyl) phenylthio)-1-methyl-3-trifluoromethylvirazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(4-trifluor (omethylphenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-phenylcarboxamide-5-(3-trifluoromethylphenylthio )-1,3-dimethylpyrazole, 4-N-(4-fluorophenyl)carboxy samido-5-(4-chlorophenylthio)-1,3-dimethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(4-chlorophenyl) phenylthio)-1,3-dimethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(3-chlorophenyl) phenylthio)-1,3-dimethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(4-fluoro phenoxy)-1-methyl-3-trifluoromethylvirazole, 4-N-(4-fluorophenyl)carboxamide-5-(3-trifluoromethane) tylphenoxy)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(3-chlorophenyl) phenoxy)-1-methyl-3-trifluoromethylpyrazole, 4-N-phenylcarboxamide-5-(4-chlorophenoxy)-1,3-di Methylvirazole, 4-N-(4-fluorophenyl)carboxamide-5-( 4-chlorophenoxy)-1,3-dimethylpyrazole, or 4-N-(2,4-difluorophenyl)carboxamide-5-(4-chlorophenyl) phenoxy)-1-methyl-3-trifluoromethylpyrazole, or an agriculturally acceptable salt thereof The compound according to claim 1. 20.4-N-(2,4-difluorophenyl)carboxamide-5-(n-butyl) tilthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(2-propenylate) (ruthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-isopropylthi o-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-ethylthio-1 -methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(3-chloropropylene) (lopylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-methylthio-1 -methyl-3-trifluoromethylpyrazole, or 4-N-(2,4-difluorophenyl)carboxamide-5-(2,2,2- trifluoroethoxy)-1-methyl-3-trifluoromethylpyrazole, or is its agriculturally acceptable salt The compound according to claim 1. 21.4-N-(2,4-difluorophenyl)carboxamide-5-(ethoxy cyclocarbonylmethylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 1-methylbutylthio)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 2-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(n-hexyl thio)-1-methyl-3-trifluoromethylpyrazole, 5-cyclopentylthio-4-N-(2,4-difluorophenyl)carboxa mido-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( n-propylthio)-3-trifluoromethylpyrazole, 5-Cyclohexylthio-4-N-(2,4-difluorophenyl)carboxa mido-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 1-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 3-methylbutylthio)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(1,1-dimethyl ethylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-ethoxy-1- methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 2-provinylthio)-3-trifluoromethylpyrazole, 5-(3-butenylthio)-4-N-(2,4-difluorophenyl)carboxy samido-1-methyl-3-trifluoromethylpyrazole, 5-(2-bromo-2-propenylthio)-4-N-(2,4-difluorophe carboxamide-1-methyl-3-trifluoromethylpyrazole, 5-(3-bromo-2-propenylthio)-4-N-(2,4-difluorophe carboxamide-1-methyl-3-trifluoromethylpyrazole, 5-(cyanomethylthio)-4-N-(2,4-difluorophenyl)carboxy samido-1-methyl-3-trifluoromethylpyrazole, 5-(3-methyl-2-butenylthio)-4-N-(2,4-difluorophenyl ) carboxamide-1-methyl-3-trifluoromethylpyrazole, 5-(cyclopropylmethylthio)-4-N-(2,4-difluorophenyl) carboxamide-1-methyl-3-trifluoromethylpyrazole, 5-(3-butynylthio)-4-N-(2,4-difluorophenyl)carboxy samido-1-methyl-3-trifluoromethylpyrazole, 5-(2-chloropropylthio)-4-N-(2,4-difluorophenyl)ka ruboxamide-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(2,2-dimethyl toxyethylthio)-1-methyl-3-trifluoromethylpyrazole, 5-(2-butenylthio)-4-N-(2,4-difluorophenyl)carboxy samido-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( n-pentylthio)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 2-methylbutylthio)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 2-Methyl-2-propenylthio)-3-trifluoromethylpyrazole, 5- (2-chloro-2-propenylthio)-4-N-(2,4-difluorophenyl ) carboxamide-1-methyl-3-trifluoromethylvirazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(2-methoxy ethyl)-1-methyl-3-trifluoromethylvirazole, 5-(3-chloro-2-propenylthio)-4-N-(2,4-difluorophe carboxamide-1-methyl-3-trifluoromethylpyrazole, 5-ethylthio-1-ethyl-4-N-(2,4-difluorophenyl)carbo xamide-3-trifluoromethylpyrazole, 5-ethylthio-1-ethyl-4-N-(2,4,6-trifluorophenyl) carboxamide-3-trifluoromethylvirazole, or 5-(N-methylaminocarbonylmethylthio)-4-N-(2,4-difluoro Lophenyl) carboxamide-1-methyl-3-trifluoromethylvirazole , or an agriculturally acceptable salt thereof The compound according to claim 1. 22.4-N-(2,4-difluorophenyl)-5-(4-fluorophenyl thio)-thiocarboxamide-1-methyl-3-trifluoromethylpyrazole , 3-chlorodifluoromethyl-5-(4-fluorophenylthio)-4-N- (2,4-difluorophenyl)carboxamide-1-methylvirazole, 3-chlorodifluoromethyl-5-(4-fluorophenylthio)-1-methyl -4-N-(2,4,6-trifluorophenyl)carboxamide virazole, 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 2-pyridylthio)-3-trifluoromethylpyrazole, 5-(4-aminophenylthio)-4-N-(2,4-difluorophenyl)ka ruboxamide-1-methyl-3-trifluoromethylpyrazole, 5-(3-chloro-4-fluorophenylthio)-4-N-(2,4-difluoro Lophenyl) carboxamide-1-methyl-trifluoromethylpyrazole, 4 -N-(2,4-difluorophenyl)carboxamide-5-(4-fluorophenyl) phenylthio)-1-methyl-3-(n-propyl)pyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(4-fluoro phenylthio)-1-(2,2,2-trifluoroethyl)-3-trifluoro methylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-5-(4-fluoro phenylthio)-1-methyl-3-methylthiovirazole, 4-N-(3-chloro-4-fluorophenyl)carboxamide-5-(4-fluorophenyl) (fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 4- N-(3,4-difluorophenyl)carboxamide-5-(4-fluorophenyl) nilthio)-1-methyl-3-trifluoromethylpyrazole, 5-(4-fluorophenylthio)-1-methyl-3-trifluoromethyl-4 -N-(2,4,5-trifluorophenyl)carboxamide pyrazole, 4- N-(2-fluorophenyl)carboxamide-5-(4-fluorophenylthi e)-1-methyl-3-trifluoromethylpyrazole, 4-N-(4-chlorophenyl)carboxamide-5-(4-fluorophenyl thio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(4-chloro-2-fluorophenyl)carboxamide-5-(4-fluorophenyl) (fluorophenylthio)-1-methyl-3-trifluoromethylpyrazole, 5- (4-fluorophenylthio)-1-methyl-3-trifluoromethyl-4-N -(2,4,6-trifluorophenyl)carboxamide pyrazole, 4-N- (2-chloro-4-fluorophenyl)carboxamide-5-(4-fluorophenyl) phenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(4 -fluorophenyl)carboxamide-5-(4-fluorophenylthio)-1 -methyl-3-trifluoromethylpyrazole, 4-N-(2,4-dichlorophenyl)carboxamide-5-(4-fluorophenyl) phenylthio)-1-methyl-3-trifluoromethylpyrazole, 5-(4-fluorophenylthio)-1-methyl-3-trifluoromethyl-4 -N-(2,3,4-trifluorophenyl)carboxamide pyrazole, 4- N-(4-bromo-2-fluorophenyl)carboxamide-5-(4-fluorophenyl) lophenylthio)-1-methyl-3-trifluoromethylpyrazole, 5-(4 -fluorophenylthio)-4-N-(2-fluoro-4-methylphenyl)ka ruboxamide-1-methyl-3-trifluoromethylpyrazole, 4-N-(3 -fluorophenyl)carboxamide-5-(4-fluorophenylthio)-1 -methyl-3-trifluoromethylpyrazole, 4-N-(2,3-difluorophenyl)carboxamide-5-(4-fluoro phenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,5-difluorophenyl)carboxamide-5-(4-fluoro phenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,6-difluorophenyl)carboxamide-5-(4-fluoro phenylthio)-1-methyl-3-trifluoromethylpyrazole, 4-N-(3,5-difluorophenyl)carboxamide-5-(4-fluoro phenylthio)-1-methyl-3-trifluoromethylpyrazole, 5-(4-fluorophenylthio)-1-methyl-3-trifluoromethyl-4 -N-(2,3,6-trifluorophenyl)carboxamide pyrazole, 5- (4-fluorophenylthio)-1-methyl-4-N-(phenyl)carboxa Mido-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 4-methylthiophenylthio)-3-trifluoromethylpyrazole, 5-(4-fluorophenylthio)-1-methyl-4-N-methyl-N-(2, 4-difluorophenyl)carboxamide-3-trifluoromethylpyrazole , 5-(4-chlorophenylsulfinyl)-4-N-(2,4-difluorof phenyl)carboxamide-1-methyl-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( n-propyloxy)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-1-methyl-5-( 2-methylpropyloxy)-3-trifluoromethylpyrazole, 3-chlorodifluoromethyl-4-N-(2,4-difluorophenyl)carbo xamido-1-methyl-5-(2-methylpropyloxy)pyrazole, 4-N-(2,4-difluorophenyl)carboxamide-1-ethyl-5-( 2-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,4-difluorophenyl)carboxamide-1-ethyl-5-( 2-propenylthio)-3-trifluoromethylpyrazole, 4-N-(2,4,6-trifluorophenyl)carboxamide-1-ethyl- 5-(2-methylpropylthio)-3-trifluoromethylvirazole, 4-N-(2,3-difluorophenyl)carboxamide-1-methyl-5-( 2-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,6-difluorophenyl)carboxamide-1-methyl-5-( 2-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,3,6-trifluorophenyl)carboxamide-1-methyl- 5-(2-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,4,6-trifluorophenyl)carboxamide-1-methyl- 5-(2-methylpropylthio)-3-trifluoromethylpyrazole, 4-N-(2,5-difluorophenyl)carboxamide-1-methyl-5-( 2-methylpropylthio)-3-trifluoromethylpyrazole, or 4- N-(2,4-difluorophenyl)carboxamide-1-methyl-5-(2- Methylpropylthio)-3-pentafluoroethylpyrazole or an agriculturally acceptable salt thereof The compound according to claim 1. 23. a)...Formula II: ▲There are mathematical formulas, chemical formulas, tables, etc.▲II (In the formula, Z indicates a leaving group, and other symbols As defined in claim 1), the compound represented by formula III: R2-X 1III (In the formula, R2 is as defined in claim 1, and X1 is hydrogen or an alkali metal. b) When Y represents a sulfur atom, a compound of formula I (formula The corresponding compound represented by (Y in it represents an oxygen atom) is reacted with a vulcanized compound, c) if R5 represents a straight-chain or branched alkyl group containing up to 6 carbon atoms, The corresponding compound of formula I (in which R5 represents hydrogen) is reacted with an alkylating agent. d) When Y represents oxygen, formula IV: ▲There are mathematical formulas, chemical formulas, tables, etc.▲IV (various symbols in the formula are defined in claim 1) Acid halides are produced by reacting the compound represented by and then convert this into formula V: H-NR4R5V (wherein R4 and R5 are as defined in claim 1) respond, e) Formula IVa: ▲There are mathematical formulas, chemical formulas, tables, etc. ▲IVa (various symbols in the formula are defined in claim 1) The compound represented by the formula R10-L (wherein R10 is as defined in claim 1, and L is a leaving group). let me, f) When R10 represents phenyl or pyridyl substituted with -SR7 group, the formula ( I) (R10 in the formula represents phenyl or pyridyl substituted with -NH2) diazotization of the corresponding compound, and then the diazotization product thus obtained is represented by the formula R7S-SR7 (R7 in the formula is as defined in claim 1) optionally the N-substituted pyrazo obtained in this way. 2. The method according to claim 1, comprising converting the alcohol derivative into an agriculturally acceptable salt thereof. A method for preparing N-substituted pyrazole derivatives of formula I. 24. a herbicidally effective amount of the N-substituted pyrazole derivative of formula I according to claim 1 or is an agriculturally acceptable salt thereof and an agriculturally acceptable diluent or carrier and/or A herbicide composition comprising a surfactant as an active ingredient. 25. A method for controlling weed growth in a location, the amount of which is effective to kill weeds. or an agriculturally acceptable N-substituted birazole derivative of formula I according to claim 1 of A method consisting of applying salt to the area.