WO2020036133A1 - Dérivé d'amide d'acide 3-(1h-1,2,4-triazole-1-yl) benzoïque et agent de lutte contre des organismes nuisibles - Google Patents

Dérivé d'amide d'acide 3-(1h-1,2,4-triazole-1-yl) benzoïque et agent de lutte contre des organismes nuisibles Download PDF

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WO2020036133A1
WO2020036133A1 PCT/JP2019/031563 JP2019031563W WO2020036133A1 WO 2020036133 A1 WO2020036133 A1 WO 2020036133A1 JP 2019031563 W JP2019031563 W JP 2019031563W WO 2020036133 A1 WO2020036133 A1 WO 2020036133A1
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alkyl
cycloalkyl
substituted
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幸浩 榎本
大介 志鎌
皓祐 田中
啓二 鳥谷部
義浩 村松
阿部　晋
陽 高根澤
松田　武
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クミアイ化学工業株式会社
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing >N—S—C≡(Hal)3 groups
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/14—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to a novel 3- (1H-1,2,4-triazol-1-yl) benzoic acid amide derivative or an agriculturally acceptable salt thereof, and a pest control containing the derivative or its salt as an active ingredient. It relates to an agent and a production intermediate.
  • Patent Documents 1 and 2 describe 3- (1H-1,2,4-triazol-1-yl) benzoic acid amide derivatives having a pest control effect.
  • the compounds described in Patent Documents 1 and 2 are limited to compounds in which a 1H-pyrazol-5-yl group is bonded to the 3-position of a triazole ring bonded to the 3-position of benzoic acid amide.
  • Patent Document 3 describes a 3- (1H-1,2,4-triazol-1-yl) benzoic acid amide derivative having P2X3 or P2X2 / 3 receptor antagonist activity.
  • the compounds described in Patent Document 3 are limited to compounds in which a 5-methylpyridin-2-yl group is bonded to the 5-position of benzoic acid amide. Furthermore, Patent Document 3 has no description on insecticidal activity.
  • Patent Document 4 describes a benzoic acid amide derivative having P2X7 receptor inhibitory activity.
  • the compound described in Patent Document 4 is a compound in which a 4,5-dihydro-5-oxo-1H-1,2,4-triazol-1-yl group is bonded to the 3-position of benzoic acid amide, Limited to-(hydroxy-substituted cycloalkylalkyl) benzoic acid amides. Further, Patent Document 4 has no description on insecticidal activity.
  • Patent Document 5 describes a phenylsulfamoylcarboxamide derivative having herbicidal activity.
  • the compound described in Patent Document 5 is limited to a compound in which a 4,5-dihydro-5-oxo-1H-1,2,4-triazol-1-yl group is bonded to the 3-position of phenylsulfamoylcarboxamide. ing. Furthermore, Patent Document 5 has no description on insecticidal activity.
  • Patent Document 6 describes a 3- (1H-1,2,4-triazol-1-yl) benzoic acid amide derivative having factor Xa inhibitory activity.
  • the compounds described in Patent Document 6 are limited to compounds in which a phenylaminocarbonyl group, a pyridylaminocarbonyl group, and a pyrimidinylaminocarbonyl group are bonded to the 5-position of a triazole ring. Furthermore, Patent Document 6 has no description on insecticidal activity.
  • Pest control agents used for useful crops are desired to be applied to soil or foliage and show sufficient pest control effects at a low dose.
  • the demand for the safety of chemical substances and the effect on the environment has been increasing, and the development of safer pest control agents has been desired.
  • pesticides such as insecticides, acaricides, nematodes, etc. for many years, pests that have acquired resistance to the pesticides have emerged. It has become difficult to completely control pests.
  • the use of pesticides with high human toxicity is a problem in terms of safety for workers.
  • an object of the present invention is to solve the above-mentioned problems of a conventional pest control agent, and furthermore, to provide a pest excellent in safety, control effect, residual effect and the like.
  • An object of the present invention is to provide a controlling agent and a novel compound therefor.
  • the present inventors have synthesized various 3- (1H-1,2,4-triazol-1-yl) benzoic acid amide derivatives and developed their pest control agents having the above-mentioned preferable properties. We studied diligently about physiological activity. As a result, 3- (1H-1,2,4-triazol-1-yl) benzoic acid amide derivatives (hereinafter, also referred to as compounds of the present invention) represented by the following general formula [I] can be used for various pests.
  • the present invention has been found to have an excellent control effect on, and the present invention has been completed by further study.
  • R 11 is a C 1 -C 6 alkyl group, a C 1 -C 6 haloalkyl group, a C 1 -C 6 alkoxy C 1 -C 6 alkyl group, a C 1 -C 6 alkylthio C 1 -C 6 alkyl group, a cyano C A 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, a C 2 -C 6 haloalkenyl group, a C 2 -C 6 alkynyl group, a C 2 -C 6 haloalkynyl group, a C 3 -C 6 cycloalkyl group or A C 3 -C 6 halocycloalkyl group;
  • R 12 is a hydrogen atom, a cyano group, a C 1 -C 6 alkyl group, a C 1 -C 6 haloalkyl group, a C 2 -C
  • a 3- (1H-1,2,4-triazol-1-yl) benzoic acid amide derivative or an agriculturally acceptable salt thereof represented by the formula: (2) An agrochemical composition containing the 3- (1H-1,2,4-triazol-1-yl) benzoic acid amide derivative or the agriculturally acceptable salt thereof according to (1) as an active ingredient. (3) The pesticidal composition according to (2), wherein the pesticidal composition further contains a surfactant.
  • a pest control agent comprising the 3- (1H-1,2,4-triazol-1-yl) benzoic acid amide derivative or the agriculturally acceptable salt thereof according to the above (1) as an active ingredient.
  • the pest control agent according to the above (4) wherein the pest control agent is an insecticide, a nematicide, and an acaricide.
  • the harmful substance according to the above (5) which has a controlling effect on pests in paddy fields, fields, turf, orchards, non-agricultural lands, greenhouses, nursery facilities, and plant factories for cultivating agricultural and horticultural plants. Biocontrol agents.
  • K represents -OH, a C 1 -C 6 alkoxy group, a C 1 -C 6 haloalkoxy group, a phenyloxy group or a phenyl C 1 -C 6 alkoxy group which is unsubstituted or substituted by (Z) p 1 ;
  • R 11 is a C 1 -C 6 alkyl group, a C 1 -C 6 haloalkyl group, a C 1 -C 6 alkoxy C 1 -C 6 alkyl group, a C 1 -C 6 alkylthio C 1 -C 6 alkyl group, a cyano C A 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, a C 2 -C 6 haloalkenyl group, a C 2 -C 6 alkynyl group, a C 2 -C 6 haloalkynyl group, a C 3 -C 6 cycloalkyl group or A C 3 -C 6 halocycloalkyl group;
  • R 12 is a hydrogen atom, a cyano group, a C 1 -C 6 alkyl group, a C 1 -C 6 haloalkyl group, a C 2 -C
  • R 11 is a C 1 -C 6 alkyl group, a C 1 -C 6 haloalkyl group, a C 1 -C 6 alkoxy C 1 -C 6 alkyl group, a C 1 -C 6 alkylthio C 1 -C 6 alkyl group, a cyano C A 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, a C 2 -C 6 haloalkenyl group, a C 2 -C 6 alkynyl group, a C 2 -C 6 haloalkynyl group, a C 3 -C 6 cycloalkyl group or A C 3 -C 6 halocycloalkyl group;
  • R 12 is a hydrogen atom, a cyano group, a C 1 -C 6 alkyl group, a C 1 -C 6 haloalkyl group, a C 2 -C
  • a 1-phenyl-1H-1,2,4-triazole derivative or a salt thereof which is represented by the following formula: (16) The 3- (1H-1) according to (1), wherein the 1-phenyl-1H-1,2,4-triazole derivative or the salt thereof according to (15) is used as a raw material. , 2,4-triazol-1-yl) benzoic acid amide derivatives.
  • the compound represented by the general formula [I] of the present invention has an excellent pest control effect, and includes stink bugs, lepidoptera, pests, flies, pests, wasps, thrips, and thrips. It shows an excellent control effect on a wide range of pests such as eye pests, spider mites and plant parasitic nematodes, and can also control pests that have acquired drug resistance.
  • pest control agents containing the compound of the present invention spider mites, spider mites, Mandarin spider mites, spider mites, etc .; It is highly effective against nematodes such as representatives of the order Lepidoptera and root-knot nematodes, and insects of the order Lepidoptera such as Japanese moth, P. persica, and Tobacco. In addition, because of its excellent permeability, a safe and labor-saving application method by soil treatment is possible.
  • the term “pesticide” means animals such as agricultural and horticultural fields, livestock and pets, and insecticides, acaricides, nematocides, etc. for domestic or epidemic control.
  • halogen atom refers to a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the notation such as “C 1 -C 6 ” indicates that the number following the element symbol indicates the number of carbon atoms.
  • the number of carbon atoms may be any of 1 to 6 I have.
  • the “C 1 -C 6 alkyl group” refers to a linear or branched alkyl group having 1 to 6 carbon atoms, unless otherwise specified.
  • C 1 -C 6 haloalkyl group means a straight-chain or branched-chain C 1 -C 6 substituted with 1 to 13 halogen atoms which are the same or different, unless otherwise specified.
  • Represents a haloalkyl group for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, chlorodifluoromethyl, dichlorofluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, 1-chloroethyl, 2 -Chloroethyl, 1,1
  • C 3 -C 6 cycloalkyl group refers to a cycloalkyl group having 3 to 6 carbon atoms unless otherwise specified, and examples thereof include groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Can be.
  • C 3 -C 6 halocycloalkyl group refers to a cycloalkyl group having 3 to 6 carbon atoms, which is substituted with the same or different 1 to 11 halogen atoms, unless otherwise specified.
  • C 2 -C 6 alkenyl group refers to a linear or branched alkenyl group having 2 to 6 carbon atoms unless otherwise specified, and examples thereof include vinyl, 1-propenyl, isopropenyl, 2-propenyl, 1-butenyl, 1-methyl-1-propenyl, 2-butenyl, 1-methyl-2-propenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1, 3-butadienyl, 1-pentenyl, 1-ethyl-2-propenyl, 2-pentenyl, 1-methyl-1-butenyl, 3-pentenyl, 1-methyl-2-butenyl, 4-pentenyl, 1-methyl-3- Butenyl, 3-methyl-1-butenyl, 1,2-dimethyl-2-propenyl, 1,1-dimethyl-2-propenyl, 2-methyl-2-butenyl, 3-methyl-2 Butenyl, 1,2-dimethyl-1-
  • C 2 -C 6 haloalkenyl group means a linear or branched C 2 -C 6 substituted with 1 to 11 halogen atoms, which is the same or different, unless otherwise specified. And represents, for example, 1-fluorovinyl, 2-fluorovinyl, 1,2-difluorovinyl, 2,2-difluorovinyl, trifluorovinyl, 1-chlorovinyl, 2-chlorovinyl, 1,2-dichloro Vinyl, 2,2-dichlorovinyl, trichlorovinyl, 1,2-dibromovinyl, 2,2-dibromovinyl, tribromovinyl, 1,2-diiodomovinyl, 2,2-diiodovinyl, triiodovinyl, 1-fluoro- 2-propenyl, 2-fluoro-2-propenyl, 3-fluoro-2-propenyl, 2,3-difluor
  • C 2 -C 6 alkynyl group means a linear or branched alkynyl group having 2 to 6 carbon atoms, unless otherwise specified.
  • C 2 -C 6 haloalkynyl group means a straight-chain or branched-chain having 2 to 6 carbon atoms substituted with the same or different 1 to 9 halogen atoms, unless otherwise specified.
  • C 1 -C 6 alkoxy group means a (C 1 -C 6 alkyl) —O— group in which the alkyl portion has the above-mentioned meaning, unless otherwise specified, and includes, for example, methoxy, ethoxy, n -Propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1-ethylpropoxy, 1,1-dimethylpropoxy , 1,2-dimethylpropoxy or n-hexyloxy.
  • C 1 -C 6 haloalkoxy group means a (C 1 -C 6 haloalkyl) -O— group in which the haloalkyl moiety has the above-mentioned meaning, unless otherwise specified.
  • the “C 2 -C 6 alkenyloxy group” refers to a (C 2 -C 6 alkenyl) -O— group in which the alkenyl moiety has the above-mentioned meaning, unless otherwise specified.
  • 2-propenyloxy group 1-methyl-2-propenyloxy, 2-methyl-2-propenyloxy, 2-butenyloxy, 3-butenyloxy, 3-methyl-2-butenyloxy, 4-methyl-3-butenyloxy, 4-pentenyloxy or 5- Examples include hexenyloxy and the like.
  • C 2 -C 6 haloalkenyloxy group means a (C 2 -C 6 haloalkenyl) -O— group in which the haloalkenyl portion has the above-mentioned meaning, unless otherwise specified.
  • the “C 2 -C 6 alkynyloxy group” means a (C 2 -C 6 alkynyl) -O— group in which the alkynyl moiety has the above-mentioned meaning, unless otherwise specified.
  • 2-propynyloxy 1-methyl-2-propynyloxy, 1-ethyl-2-propynyloxy, 2-butynyloxy, 3-butynyloxy, 1-methyl-2-butynyloxy, 2-pentynyloxy, 4-pentynyloxy or 4,4 -Dimethyl-2-pentynyloxy and the like.
  • C 2 -C 6 haloalkynyloxy group means a (C 2 -C 6 haloalkynyl) —O— group in which the haloalkynyl moiety has the above-mentioned meaning, unless otherwise specified.
  • C 3 -C 6 cycloalkyloxy group means a (C 3 -C 6 cycloalkyl) -O— group in which the cycloalkyl moiety has the above-mentioned meaning, unless otherwise specified.
  • Examples include groups such as propoxy, cyclobutoxy, cyclopentyloxy or cyclohexyloxy.
  • C 3 -C 6 halocycloalkyloxy group means a (C 3 -C 6 halocycloalkyl) -O— group in which the halocycloalkyl moiety has the above-mentioned meaning, unless otherwise limited.
  • 2,2-difluorocyclopropoxy, 2,2-dichlorocyclopropoxy, 3,3-difluorocyclobutoxy, 3,3-dichlorocyclobutoxy, 3-fluorocyclopentyloxy, 3,3-difluorocyclopentyloxy, nonafluoro Examples include groups such as cyclopentyloxy, 3,3-dichlorocyclopentyloxy, 4,4-difluorocyclohexyloxy, and 4,4-dichlorocyclohexyloxy.
  • aromatic heterocyclic oxy group means a (aromatic heterocyclic) -O— group in which the aromatic heterocyclic moiety has the above-mentioned meaning, unless otherwise specified.
  • aromatic heterocyclic oxy group means a (aromatic heterocyclic) -O— group in which the aromatic heterocyclic moiety has the above-mentioned meaning, unless otherwise specified.
  • pyridin-2-yloxy Pyridin-3-yloxy, pyridin-4-yloxy, pyrazin-2-yloxy, pyridazin-3-yloxy, pyridazin-4-yloxy, pyrimidin-2-yloxy, pyrimidin-4-yloxy, pyrimidin-5-yloxy, thiazole Groups such as -2-yloxy, thiazol-4-yloxy or thiazol-5-yloxy.
  • the “saturated heterocyclic oxy group” refers to a (saturated heterocyclic) -O— group in which the saturated heterocyclic moiety has the above-mentioned meaning, unless otherwise specified.
  • oxetane-3-yloxy, tetrahydrofuran- Such as 2-yloxy, tetrahydrofuran-3-yloxy, (tetrahydro-2H-pyran-2-yl) oxy, (tetrahydro-2H-pyran-3-yl) oxy or (tetrahydro-2H-pyran-4-yl) oxy; Groups.
  • C 1 -C 6 alkylthio group refers to a (C 1 -C 6 alkyl) -S— group in which the alkyl portion has the above-mentioned meaning, unless otherwise specified.
  • Examples include groups such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl and hexylsulfinyl.
  • Examples include groups such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl and hexylsulfonyl.
  • the “C 1 -C 6 haloalkylthio group” refers to a (C 1 -C 6 haloalkyl) -S— group in which the haloalkyl moiety has the above-mentioned meaning, unless otherwise specified, and includes, for example, fluoromethylthio, difluoro Methylthio, trifluoromethylthio, trichloromethylthio, 2,2,2-trifluoroethylthio, pentafluoroethylthio, 2,2,2-trichloroethylthio, 3,3,3-trifluoropropylthio, 1,1, 2,3,3,3-hexafluoropropylthio, heptafluoropropylthio, 1,1,1,3,3,3-hexafluoropropan-2-ylthio, heptafluoropropan-2-ylthio or 4,4 Examples include groups such as 4-trifluorobutylthio
  • difluoromethylsulfonyl difluoromethylsulfonyl, trifluoromethylsulfonyl, trichloromethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, pentafluoroethylsulfonyl, 3,3,3-trifluoropropylsulfonyl, heptafluoropropylsulfonyl, or heptafluoro- Examples include groups such as 2-propylsulfonyl.
  • C 2 -C 6 alkenylthio group refers to a (C 2 -C 6 alkenyl) -S— group in which the alkenyl moiety has the above-mentioned meaning, unless otherwise specified.
  • 2-propenylthio group 2-butenylthio, 3-butenylthio, 2-pentenylthio, 3-pentenylthio, 4-pentenylthio, 2-methyl-2-butenylthio, 2,4-pentadienylthio, 2-hexenylthio, 3-hexenylthio , 4-hexenylthio, 5-hexenylthio or 2,4-hexadienylthio.
  • groups such as sulfonyl, 2-hexenylsulfonyl, 3-hexenylsulfonyl, 4-hexenylsulfonyl, 5-hexenylsulfonyl, and 2,4-hexadienylsulfonyl.
  • C 2 -C 6 haloalkenylthio group means a (C 2 -C 6 haloalkenyl) -S— group in which the alkenyl moiety has the above-mentioned meaning, unless otherwise specified.
  • 3-chloro-2-propenylsulfinyl 3,3-dichloro-2-propenylsulfinyl, 3,3-difluoro-2-propenylsulfinyl, 3,3,3-trifluoro-1-propenylsulfinyl, 2,3 , 3,3-tetrafluoro-1-propenylsulfinyl, 4,4,4-trifluoro-2-butenylsulfinyl, 3,4,4-trifluoro-3-butenylsulfinyl, 5-chloro-3-pentenyl
  • groups include groups such as sulfinyl and 6-fluoro-2-hexenylsulfinyl.
  • 3-chloro-2-propenylsulfonyl 3,3-dichloro-2-propenylsulfonyl, 3,3-difluoro-2-propenylsulfonyl, 3,3,3-trifluoro-1-propenylsulfonyl, 2, 3,3,3-tetrafluoro-1-propenylsulfonyl, 4,4,4-trifluoro-2-butenylsulfonyl, 3,4,4-trifluoro-3-butenylsulfonyl, 5-chloro-3- Examples include groups such as pentenylsulfonyl and 6-fluoro-2-hexenylsulfonyl.
  • C 2 -C 6 alkynylthio group means a (C 2 -C 6 alkynyl) -S— group in which the alkynyl moiety has the above-mentioned meaning, unless otherwise specified.
  • Groups such as -butyn-3-ylthio, 3-methyl-1-butyn-3-ylthio, 2-butynylthio, 3-butynylthio, 2-pentynylthio, 3-pentynylthio, 4-pentynylthio or 5-hexynylthio. .
  • C 3 -C 6 cycloalkylthio group means a (C 3 -C 6 cycloalkyl) -S— group in which the cycloalkyl moiety has the above-mentioned meaning, unless otherwise specified.
  • Groups such as thio, cyclobutylthio, cyclopentylthio or cyclohexylthio can be mentioned.
  • examples thereof include groups such as cyclopropylsulfinyl, cyclobutylsulfinyl, cyclopentylsulfinyl, and cyclohexylsulfinyl.
  • the “aromatic heterocyclic thio group” refers to a (aromatic heterocyclic) -S— group in which the aromatic heterocyclic moiety has the above-mentioned meaning, unless otherwise specified.
  • aromatic heterocyclic thio refers to a (aromatic heterocyclic) -S— group in which the aromatic heterocyclic moiety has the above-mentioned meaning, unless otherwise specified.
  • pyridin-2-ylthio Pyridin-3-ylthio, pyridin-4-ylthio, pyrazin-2-ylthio, pyridazin-3-ylthio, pyridazin-4-ylthio, pyrimidin-2-ylthio, pyrimidin-4-ylthio, pyrimidin-5-ylthio, thiazole
  • groups such as -2-ylthio, thiazol-4-ylthio or thiazol-5-ylthio.
  • -2-ylsulfinyl pyridin-3-ylsulfinyl, pyridin-4-ylsulfinyl, pyrazin-2-ylsulfinyl, pyridazin-3-ylsulfinyl, pyridazin-4-ylsulfinyl, pyrimidin-2-ylsulfinyl, pyrimidine- Examples include groups such as 4-ylsulfinyl, pyrimidin-5-ylsulfinyl, thiazol-2-ylsulfinyl, thiazol-4-ylsulfinyl, and thiazol-5-ylsulfinyl.
  • saturated heterocyclic thio group means a (saturated heterocyclic) -S— group in which the saturated heterocyclic moiety has the above-mentioned meaning, unless otherwise specified.
  • saturated heterocyclic thio group means a (saturated heterocyclic) -S— group in which the saturated heterocyclic moiety has the above-mentioned meaning, unless otherwise specified.
  • oxetane-3-ylthio, tetrahydrofuran- such as 2-ylthio, tetrahydrofuran-3-ylthio, (tetrahydro-2H-pyran-2-yl) thio, (tetrahydro-2H-pyran-3-yl) thio or (tetrahydro-2H-pyran-4-yl) thio Groups.
  • a “saturated heterocyclic sulfinyl group” means a (saturated heterocyclic) -S ((O) — group in which the saturated heterocyclic moiety has the above-mentioned meaning, unless otherwise specified.
  • oxetane-3- Ylsulfinyl tetrahydrofuran-2-ylsulfinyl, tetrahydrofuran-3-ylsulfinyl, (tetrahydro-2H-pyran-2-yl) sulfinyl, (tetrahydro-2H-pyran-3-yl) sulfinyl or (tetrahydro-2H-pyran- 4-yl) sulfinyl and the like.
  • saturated heterocyclic sulfonyl group means a (saturated heterocyclic) -S (OO) 2 — group in which the saturated heterocyclic moiety has the above-mentioned meaning, unless otherwise specified.
  • oxetane-3 -Ylsulfonyl tetrahydrofuran-2-ylsulfonyl, tetrahydrofuran-3-ylsulfonyl, (tetrahydro-2H-pyran-2-yl) sulfonyl, (tetrahydro-2H-pyran-3-yl) sulfonyl or (tetrahydro-2H-pyran -4-yl) sulfonyl and the like.
  • C 1 -C 6 alkoxy C 1 -C 6 alkyl group means that the alkoxy portion and the alkyl portion have the same meanings as described above, unless otherwise specified (C 1 -C 6 alkoxy)-(C 1 To C 6 alkyl) groups, for example, methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, tert-butoxymethyl, 1-methoxyethyl, 1-methoxy-1-methylethyl, 2-methoxyethyl, And groups such as -ethoxyethyl, 2-ethoxyethyl, 2-isopropoxyethyl, 3-methoxypropyl, 2-methoxypropyl, 3-ethoxypropyl, 4-methoxybutyl or 4-ethoxybutyl.
  • C 1 -C 6 alkylthio C 1 -C 6 alkyl group means, unless otherwise specified, an alkylthio moiety and an alkyl moiety having the above meaning (C 1 -C 6 alkylthio)-(C 1 -C 6 alkyl) group, for example, methylthiomethyl, 2- (methylthio) ethyl, 3- (methylthio) propyl, 4- (methylthio) butyl, ethylthiomethyl, propylthiomethyl, butylthiomethyl or pentylthiomethyl And the group of
  • the “cyano C 1 -C 6 alkyl group” means a (cyano)-(C 1 -C 6 alkyl) group in which the alkyl portion has the above-mentioned meaning, unless otherwise specified.
  • Groups such as -cyanoethyl, 2-cyanoethyl, 3-cyanopropyl, 2-cyanopropan-2-yl, 1-cyanobutyl, 4-cyanobutyl, 5-cyanopentyl or 6-cyanohexyl.
  • phenyl C 1 -C 6 alkyl group means a phenyl- (C 1 -C 6 alkyl) group in which the alkyl portion has the above-mentioned meaning, unless otherwise specified. Examples include groups such as ethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, and 6-phenylhexyl.
  • phenyl C 1 -C 6 alkoxy group means a phenyl- (C 1 -C 6 alkoxy) group in which the alkoxy moiety has the above-mentioned meaning, unless otherwise specified.
  • examples include groups such as phenylethyloxy, 2-phenylethyloxy, 3-phenylpropyloxy, 4-phenylbutyloxy, 5-phenylpentyloxy, and 6-phenylhexyloxy.
  • aromatic heterocyclic C 1 -C 6 alkyl group means an aromatic heterocyclic ring- (C 1 -C 6 alkyl) in which the aromatic heterocyclic ring and the alkyl portion have the above-mentioned meanings, unless otherwise specified.
  • the “saturated heterocyclic C 1 -C 6 alkyl group” means a saturated heterocyclic ring and a saturated heterocyclic- (C 1 -C 6 alkyl) group in which the alkyl portion has the above-mentioned meaning, unless otherwise specified.
  • “mono (C 1 -C 6 alkyl) amino group” means a (C 1 -C 6 alkyl) -NH— group in which the alkyl portion has the above-mentioned meaning, unless otherwise specified. Examples include groups such as amino, ethylamino or n-propylamino.
  • di (C 1 -C 6 alkyl) amino group means a (C 1 -C 6 alkyl) 2 —N— group in which the alkyl portion has the above-mentioned meaning, unless otherwise specified.
  • the alkyl groups may be different from each other and include, for example, groups such as dimethylamino, methylethylamino and methyl-n-propylamino.
  • examples thereof include groups such as methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, isopropylsulfonylamino and tert-butylsulfonylamino.
  • the term “di (C 1 -C 6 alkyl) aminocarbonyl group” means that the alkyl portion has the above-mentioned meaning (C 1 -C 6 alkyl) 2 —NC (CO), unless otherwise specified. )-, And the two alkyl groups may be different from each other, and examples thereof include groups such as dimethylaminocarbonyl, diethylaminocarbonyl and diisopropylaminocarbonyl.
  • the term “mono (C 1 -C 6 haloalkyl) aminocarbonyl group” means that the haloalkyl moiety has the above-mentioned meaning, unless otherwise specified.
  • (C 1 -C 6 haloalkyl) -NH—C ( O)
  • notations such as “C 1 -C 6 alkyl group optionally substituted by R 7 ” and “C 1 -C 6 alkyl group optionally substituted by R 13 ” refer to hydrogen bonded to a carbon atom.
  • any R 7 or R 13 represents a substituted alkyl group, the number of R 7 or R 13 are substituted are selected arbitrarily in the range of number of carbon atoms of each of the specified.
  • each R 7 or R 13 may be the same or different from each other.
  • the notation such as "C 1 ⁇ C 6 haloalkyl group optionally substituted by R 13" by any R 13 is a hydrogen atom bonded to a carbon atom, a substituted haloalkyl group, substituted
  • the number of R 13 is arbitrarily selected within the range of the specified number of carbon atoms.
  • each R 13 may be the same or different from each other.
  • the notation such as "C 3 ⁇ C 6 cycloalkyl group optionally substituted by R 8 'is, by any R 8 is a hydrogen atom bonded to a carbon atom, a substituted cycloalkyl group,
  • the number of substituted R 8 is arbitrarily selected within the range of each specified number of carbon atoms.
  • each R 8 may be the same or different from each other.
  • the notation such as "C 2 ⁇ C 6 alkenyl group optionally substituted by R 13" by any R 13 is hydrogen atoms bonded to carbon atoms, a substituted alkenyl group, substituted
  • the number of R 13 is arbitrarily selected within the range of the specified number of carbon atoms.
  • each R 13 may be the same as or different from each other.
  • the notation such as "C 2 ⁇ C 6 alkynyl group optionally substituted by R 13" by any R 13 is a hydrogen atom bonded to a carbon atom, a substituted alkynyl group optionally
  • the number of R 13 to be substituted is arbitrarily selected within the range of each specified number of carbon atoms.
  • each R 13 may be the same as or different from each other.
  • notations such as “C 1 -C 6 alkoxy group optionally substituted by R 7 ” and “C 1 -C 6 alkoxy group optionally substituted by R 13 ” refer to hydrogen bonded to a carbon atom. by atomic any R 7 or R 13, represents a substituted alkoxy group, the number of R 7 or R 13 are substituted are selected arbitrarily in the range of number of carbon atoms of each of the specified. When two or more substituents R 7 or R 13 on the alkoxy group are present, each R 7 or R 13 may be the same or different from each other.
  • the notation such as "C 1 ⁇ C 6 haloalkoxy group optionally substituted by R 13" are hydrogen atoms bonded to carbon atoms by any R 13, represents a substituted haloalkoxy group,
  • the number of R 13 to be substituted is arbitrarily selected within the range of each specified number of carbon atoms.
  • each R 13 may be the same or different from each other.
  • the notation such as "C 1 ⁇ C 6 alkylthio group optionally substituted by R 13" by any R 13 is a hydrogen atom bonded to a carbon atom, a substituted alkylthio group, substituted
  • the number of R 13 is arbitrarily selected within the range of the specified number of carbon atoms.
  • each R 13 may be the same or different from each other.
  • the notation such as "optionally substituted C 1 ⁇ C 6 alkylsulfinyl group by R 13" by any R 13 is a hydrogen atom bonded to a carbon atom, a substituted alkylsulfinyl group,
  • the number of R 13 to be substituted is arbitrarily selected within the range of each specified number of carbon atoms.
  • each R 13 may be the same as or different from each other.
  • the notation such as "C 1 ⁇ C 6 alkylsulfonyl group optionally substituted by R 13" by any R 13 is a hydrogen atom bonded to a carbon atom, a substituted alkylsulfonyl group,
  • the number of R 13 to be substituted is arbitrarily selected within the range of each specified number of carbon atoms.
  • each R 13 may be the same as or different from each other.
  • the notation such as "C 1 ⁇ C 6 haloalkylthio group optionally substituted by R 13" by any R 13 is a hydrogen atom attached to the carbon atom, a substituted haloalkylthio group,
  • the number of R 13 to be substituted is arbitrarily selected within the range of each specified number of carbon atoms.
  • each R 13 may be the same as or different from each other.
  • the notation such as "C 1 ⁇ C 6 haloalkylsulfinyl group optionally substituted by R 13" by any R 13 is a hydrogen atom bonded to a carbon atom, a substituted haloalkylsulfinyl group,
  • the number of R 13 to be substituted is arbitrarily selected within the range of each specified number of carbon atoms.
  • each R 13 may be the same as or different from each other.
  • the notation such as "optionally substituted C 1 ⁇ C 6 haloalkylsulfonyl group by R 13" by any R 13 is a hydrogen atom bonded to a carbon atom, a substituted haloalkylsulfonyl group,
  • the number of R 13 to be substituted is arbitrarily selected within the range of each specified number of carbon atoms.
  • each R 13 may be the same as or different from each other.
  • [R 1 and R 2 may be bonded to each other to form a C 2 to C 6 alkylene bond, wherein the alkylene bond may contain one oxygen atom, sulfur atom or nitrogen atom.
  • [R 9 and R 10 may combine with each other to form a C 2 -C 6 alkylene bond, wherein the alkylene bond may contain one oxygen atom, sulfur atom or nitrogen atom.
  • [R 11 and R 12 may combine with each other to form a C 2 -C 6 alkylene bond, in which case the alkylene bond may contain one oxygen atom, sulfur atom or nitrogen atom]
  • [R 12 and R 14 may be mutually bonded to form a C 2 -C 6 alkylene bond, in which case the alkylene bond may contain one oxygen atom, sulfur atom or nitrogen atom], and the like.
  • alkylene bond and the heterocyclic ring formed by the atom adjacent to the alkylene bond include, for example, aziridine, azetidine, pyrrolidine, oxazolidine, oxazoline, isoxazoline, thiazolidine, imidazolidine, piperidine, morpholine, thiomorpholine, thiomorpholine- Examples include groups such as 1-oxide, thiomorpholine-1,1-dioxide, piperazine, homopiperidine or heptamethyleneimine.
  • [R 14 and R 15 may be mutually bonded to form a C 2 -C 6 alkylene bond, wherein the alkylene bond may contain one oxygen atom, sulfur atom or nitrogen atom.
  • the heterocyclic ring formed by the alkylene bond and the atom adjacent to the alkylene bond such as 4,5-dihydroisoxazole, may be mentioned.
  • the notation such as [the C 2 -C 6 alkylene bond may be mono- or poly-substituted by a halogen atom or a C 1 -C 6 alkyl group] represents hydrogen bonded to a carbon atom constituting the alkylene bond.
  • atom represents a C 2 ⁇ C 6 alkylene linkage substituted by halogen atom or C 1 ⁇ C 6 alkyl group, the number of halogen atoms or C 1 ⁇ C 6 alkyl group is substituted, the substituent in the case of the mono-substituted Represents that any one of a halogen atom or a C 1 -C 6 alkyl group is substituted, and in the case of poly substitution, any one of two or more halogen atoms or a C 1 -C 6 alkyl group is substituted. Represents substitution. Also, when poly-substituted on the C 2 -C 6 alkylene bond (ie, when two or more substituents are present), each substituent may be the same as or different from each other.
  • agriculturally acceptable salts and salts refer to the compounds of the present invention represented by the general formula [I] when a hydroxyl group, a carboxyl group, an amino group or the like is present in the structure.
  • a salt with a metal or an organic base or a salt with a mineral acid or an organic acid examples of the metal include an alkali metal such as sodium or potassium or an alkaline earth metal such as magnesium or calcium; and an organic base such as triethylamine Or mineral acids such as hydrochloric acid, hydrobromic acid or sulfuric acid, and organic acids such as formic acid, acetic acid, methanesulfonic acid, 4-toluenesulfonic acid or Trifluoromethanesulfonic acid and the like can be mentioned.
  • Table 1 shows typical examples of compounds included in the 3- (1H-1,2,4-triazol-1-yl) benzoic acid amide derivative of the present invention represented by the general formula [I].
  • Table 25 show typical examples of compounds included in the 3- (1H-1,2,4-triazol-1-yl) benzoic acid derivative of the present invention represented by the general formula [II].
  • 26 to Table 55 Table 56 to Table 58 show typical compound examples of the compounds included in the 1-phenyl-1H-1,2,4-triazole derivative of the present invention represented by the general formula [III]. Show. However, the compounds included in the derivative of the present invention are not limited to these.
  • the compound numbers in the table will be referred to in the following description.
  • the compound included in the phenyl-1H-1,2,4-triazole derivative may have an E-form or a Z-form geometric isomer depending on the type of the substituent. -Forms, Z-forms or mixtures containing E-forms and Z-forms in any proportion.
  • the compounds included in the present invention may have optical isomers due to the presence of one or more asymmetric carbon atoms and asymmetric sulfur atoms, but the present invention relates to all optically active compounds. , Racemates or diastereomers.
  • the compound of the present invention represented by the general formula [I] can be produced according to the following production methods, but is not limited to these methods.
  • the compound represented by the general formula [I-1] and “the compound [I-1]” are synonymous.
  • the compound represented by the general formula [I-1] can be produced, for example, using a compound represented by the general formula [III-1] according to a method comprising the following reaction formula. Can be.
  • Step 1-1 That is, the compound represented by the general formula [I-1] is obtained by converting the compound represented by the general formula [III-1] and the compound [IV-1] or the compound [IV-2] into an appropriate base. It can be produced by reacting in an appropriate solvent below.
  • the amount of compound [IV-1] or compound [IV-2] used in this step may be appropriately selected from the range of 1 mol to the amount of solvent relative to 1 mol of compound [III-1], and is preferably used. Is 1.0 to 2.0 mol.
  • Bases that can be used in this step include, for example, hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide, Inorganic bases such as alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; metal hydrides such as sodium hydride and potassium hydride; sodium methoxy Metal salts of alcohols such as sodium, sodium ethoxide and potassium tert-butoxide, or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0 And organic bases such as -7-undecene.
  • alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide
  • alkaline earth metals such as calcium hydroxide and magnesium hydroxide
  • the amount of the base used may be appropriately selected from the range of 1 to 5 mol per 1 mol of the compound [III-1], and is preferably 1.0 to 3.0 mol.
  • the solvent that can be used in this step include ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; Aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone, methanol, ethanol , Alcohols such as 2-propanol, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, esters
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-10 liters, per 1 mol of compound [III-1].
  • the reaction temperature in this step may be selected from an arbitrary temperature range from 0 ° C. to the reflux temperature in the reaction system, and is preferably from 0 ° C. to 150 ° C.
  • the reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 15 minutes to 24 hours.
  • compound [I-1] can be isolated by performing operations such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture. The isolated compound [I-1] can be further purified by column chromatography, recrystallization, etc., if necessary.
  • Step 1-2 The compound represented by the general formula [I-1] is obtained by reacting the compound represented by the general formula [III-1] with an aminating agent. And then reacting the compound [III-2] with the compound [IV-3] or the compound [IV-4] in the presence or absence of a suitable base, in the presence or absence of a suitable acid catalyst. In a suitable solvent.
  • the aminating agent that can be used in this step include ammonia, aqueous ammonia, and the like.
  • the amount of the aminating agent may be appropriately selected from the range of 1 to 30 mol per 1 mol of the compound [III-1], and is preferably 1.0 to 25.0 mol.
  • solvents such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane
  • aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene
  • Nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone and the like
  • Aprotic polar solvents alcohols such as methanol, ethanol and 2-propanol, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, esters such as ethyl acetate, pentane, hexane, cyclohe
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-10 liters, per 1 mol of compound [III-1].
  • the reaction temperature in this step may be selected from an arbitrary temperature range from ⁇ 30 ° C. to the reflux temperature in the reaction system, and is preferably from ⁇ 10 ° C. to 100 ° C.
  • the reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 15 minutes to 24 hours.
  • compound [III-2] can be isolated by performing operations such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture. The isolated compound [III-2] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • Step 1-3 The amount of compound [IV-3] or compound [IV-4] used in this step may be appropriately selected from the range of 1 mol to the amount of solvent relative to 1 mol of compound [III-2], and is preferably used. Is 1.0 to 10.0 mol. However, compound [IV-4] can also be used as the above solvent.
  • usable acid catalysts include, for example, sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid, mineral acids such as hydrochloric acid, hydrobromic acid or sulfuric acid, acetic acid or trifluoroacetic acid. And the like.
  • the amount of the acid catalyst used may be appropriately selected from the range of 0.01 mol to 10 mol per 1 mol of the compound [III-2], and is preferably 0.05 to 1.0 mol.
  • usable bases include, for example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and alkaline earth metals such as calcium hydroxide and magnesium hydroxide.
  • alkali metal carbonates such as sodium carbonate and potassium carbonate
  • inorganic bases such as alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate
  • metals such as sodium hydride and potassium hydride
  • Metal salts of alcohols such as hydrides, sodium methoxide, sodium ethoxide, potassium tert-butoxide, or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo Organic bases such as [5,4,0] -7-undecene.
  • the amount of the base used may be appropriately selected from the range of 1 mol to the amount of solvent relative to 1 mol of compound [III-2], and is preferably from 1.0 to 1.5 mol.
  • the solvent that can be used in this step include ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; Nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone and the like
  • Aprotic polar solvents alcohols such as methanol, ethanol and 2-propanol, halogenated hydrocarbons such as dich
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-10 liters, per 1 mol of compound [III-2].
  • the reaction temperature in this step may be selected from an arbitrary temperature range from ⁇ 30 ° C. to the reflux temperature in the reaction system, and is preferably from ⁇ 10 ° C. to 100 ° C.
  • the reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 15 minutes to 24 hours.
  • compound [I-1] can be isolated by performing operations such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture. The isolated compound [I-1] can be further purified by column chromatography, recrystallization, etc., if necessary.
  • the compound represented by the general formula [I-1] and the compound represented by the general formula [I-2] can be obtained by using, for example, a compound represented by the general formula [III-3]. It can be produced according to a method comprising the following reaction formula.
  • L 3 is a halogen atom, a C 1 -C 6 alkoxy group, a C 1 -C 6 haloalkoxy group.
  • the compound represented by the general formula [I-1] includes the compound [IV-5], the compound [IV-6] derived from an acid halide and an acid anhydride, and the general formula [III-3].
  • the compound can be produced by reacting the compound represented with a suitable solvent in the presence or absence of a suitable acid in a suitable solvent.
  • the amount of compound [IV-6] used in this step may be appropriately selected from the range of 1 to 5 mol per 1 mol of compound [III-3], and is preferably 1.0 to 2.5 mol. It is.
  • examples of the acid that can be used include sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid, mineral acids such as hydrochloric acid, hydrobromic acid and sulfuric acid, and acetic acid and trifluoroacetic acid. And carboxylic acids.
  • the amount of the acid to be used may be appropriately selected from the range of 0.001 to 10 mol, preferably 0.001 to 3.0 mol, per 1 mol of compound [III-3].
  • solvents such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane
  • aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene
  • Nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone and the like
  • Aprotic polar solvents alcohols such as methanol, ethanol, 2-propanol, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and aliphatic carbons such as pentane, hexane, cyclohexane,
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-10 liters, per 1 mol of compound [III-3].
  • the reaction temperature in this step may be selected from an arbitrary temperature range from ⁇ 30 ° C. to the reflux temperature in the reaction system, and is preferably from ⁇ 10 ° C. to 100 ° C.
  • the reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 10 minutes to 20 hours.
  • compound [I-1] can be isolated by performing operations such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture. The isolated compound [I-1] can be further purified by column chromatography, recrystallization, etc., if necessary.
  • the compound represented by the general formula [I-2] includes a compound [IV-7], a compound [IV-8] derived from carbon disulfide, an alkyl halide and the like, and a compound [IV-3].
  • the compound can be produced by reacting the compound represented with the compound in a suitable solvent.
  • the amount of compound [IV-8] used in this step may be appropriately selected from the range of 1 to 10 mol per 1 mol of compound [III-3], and is preferably 1.0 to 1.5 mol. It is.
  • the solvent that can be used in this step for example, the same solvent as described in Step 3 can be exemplified.
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-10 liters, per 1 mol of compound [III-3].
  • the reaction temperature in this step may be selected from an arbitrary temperature range from ⁇ 30 ° C. to the reflux temperature in the reaction system, and is preferably from ⁇ 10 ° C. to 100 ° C.
  • the reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 10 minutes to 20 hours.
  • compound [I-2] can be isolated by performing operations such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture. Alternatively, compound [I-2] can also be isolated by concentrating the solvent from the reaction mixture. The isolated compound [I-2] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • the compound represented by the general formula [I-4], the compound represented by the general formula [I-5] and the compound represented by the general formula [I-6] include, for example, It can be produced using the compound represented by [I-3] according to a method comprising the following reaction formula.
  • R 3 , R 4 , R 6 , R 13 , R a , Z, p 1 and n have the same meaning as described above, M represents an alkali metal or an alkaline earth metal, and preferred alkali metals are can be exemplified sodium or potassium, substituted R 5a is C 1 ⁇ C 6 alkyl group, C 1 ⁇ C 6 haloalkyl group, C 1 ⁇ C 6 alkyl group optionally substituted by R 13, optionally by R 13 C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halo A cycloalkyl group, a phenyl group unsubstituted or substituted by (Z) p 1 , an aromatic heterocycle or a saturated heterocycle.) That is, the compound represented by the general
  • the amount of compound [IV-9] or compound [IV-10] used in this step may be appropriately selected from the range of 1 to 5 mol per 1 mol of compound [I-3], and is preferably 1 0.0 to 2.0 mol.
  • the solvent that can be used in this step include ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; Halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl
  • aprotic polar solvents such as sulfoxide, sulf
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-10 liters, per 1 mol of compound [I-3].
  • the reaction temperature in this step may be selected from an arbitrary temperature range from ⁇ 70 ° C. to the reflux temperature in the reaction system, and is preferably from ⁇ 20 ° C. to 100 ° C.
  • the reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually from 10 minutes to 24 hours.
  • compound [I-4] can be isolated by performing operations such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture. The isolated compound [I-4] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • Step 3-2 Examples of the copper halide that can be used in this step include copper (I) chloride, copper (I) bromide, copper (I) iodide, copper (II) chloride, copper (II) bromide, and the like. it can.
  • the amount of the copper halide to be used may be appropriately selected from the range of 0 to 5 mol per 1 mol of the compound [I-3], and is preferably 1.0 to 2.5 mol.
  • the solvent, reaction temperature, and reaction time that can be used in this step are the same as those in Step 3-1.
  • the reaction mixture is poured into water to neutralize, and then the precipitated solid is collected by filtration or extracted with an organic solvent and then concentrated to obtain the compound [I-5].
  • the isolated compound [I-5] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • Step 3-3 Examples of the solvent that can be used in this step include ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, nitriles such as acetonitrile and propionitrile, and N, N-dimethyl.
  • ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, nitriles such as acetonitrile and propionitrile, and N, N-dimethyl.
  • Aprotic polar solvents such as formamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone, and a mixed solvent thereof; .
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-30 liters, per 1 mol of compound [I-3].
  • the reaction temperature and reaction time in this step are the same as in Step 3-1.
  • compound [I-6] can be isolated by performing operations such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture. Alternatively, compound [I-6] can be isolated by concentrating the solvent from the reaction mixture. The isolated compound [I-6] can be further purified by column chromatography, recrystallization, or the like, if necessary.
  • the compound represented by the general formula [I-8] can be produced, for example, using a compound represented by the general formula [I-7] according to a method comprising the following reaction formula. it can.
  • oxidizing agent examples include hydrogen peroxide, m-chloroperbenzoic acid, sodium periodate, oxone (OXONE, trade name of EI DuPont; products containing potassium hydrogen peroxosulfate), N -Chlorosuccinimide, N-bromosuccinimide, tert-butyl hypochlorite, sodium hypochlorite and the like.
  • the amount of the oxidizing agent depends on the oxidation number m of the sulfur atom of the compound represented by the general formula [I-8], but is in the range of 1 to 5 mol per 1 mol of the compound [I-7]. And it may be appropriately selected from the above, preferably from 1.0 to 2.5 mol.
  • Examples of the catalyst that can be used in this reaction include sodium tungstate.
  • the amount of the catalyst to be used may be appropriately selected from the range of 0.01 to 1 mol, preferably 0.01 to 0.1 mol, per 1 mol of compound [I-7].
  • Solvents that can be used in this reaction include, for example, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide Aprotic polar solvents such as benzene, sulfolane, 1,3-dimethyl-2-imidazolidinone, alcohols such as methanol, ethanol and 2-propanol; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane And aliphatic hydrocarbons such as pentane, hexane, cyclohexane and
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-15 liters, per 1 mol of compound [I-7].
  • the reaction temperature of this reaction may be selected from an arbitrary temperature range usually from ⁇ 30 ° C. to the reflux temperature in the reaction system, and is preferably from ⁇ 10 ° C. to 100 ° C.
  • the reaction time of this reaction varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually from 10 minutes to 24 hours.
  • the compound [I-8] can be isolated by pouring the reaction mixture into water or the like, extracting the mixture with an organic solvent, and then concentrating the mixture. The isolated compound [I-8] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • the compound represented by the general formula [I-11] can be produced, for example, using a compound represented by the general formula [I-9] according to a method comprising the following reaction formula. it can.
  • R 3 , R 4 , R 6 , R a and n have the same meaning as described above, and R c represents a methyl group or a trifluoromethyl group.
  • the compound represented by the general formula [I-11] is produced by reacting the compound [I-9] with acetic anhydride or trifluoroacetic anhydride to produce the compound [I-10], and then producing the compound [I-11]. -10] in a suitable solvent in the presence of a suitable base or a suitable acid.
  • the amount of acetic anhydride or trifluoroacetic anhydride to be used in this reaction may be selected from the range of 1 mol to the amount of a solvent relative to 1 mol of compound [I-9], and is preferably from 1.0 to 7.0. 0 mol.
  • solvents such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane
  • aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene
  • Halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane
  • alcohols such as methanol, ethanol and 2-propanol
  • nitriles such as acetonitrile and propionitrile
  • esters such as ethyl acetate
  • pentane examples thereof include aliphatic hydrocarbons such as cyclohexane and heptane, water, and a mixed solvent thereof.
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-10 liters, per 1 mol of compound [I-9].
  • usable bases include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and alkaline earth metals such as calcium hydroxide and magnesium hydroxide.
  • inorganic bases such as alkali metal carbonates such as sodium carbonate and potassium carbonate, metal salts of alcohols such as sodium methoxide, sodium ethoxide and potassium tert-butoxide or triethylamine, N, N-dimethyl Organic bases such as aniline, pyridine, 4-N, N-dimethylaminopyridine, and 1,8-diazabicyclo [5.4.0] -7-undecene.
  • the amount of the base to be used may be appropriately selected from the range of 1 to 10 mol per 1 mol of compound [I-9], and is preferably 1.0 to 5.0 mol.
  • usable acids include, for example, mineral acids such as hydrochloric acid, hydrobromic acid and sulfuric acid, and carboxylic acids such as acetic acid and trifluoroacetic acid.
  • the amount of the acid to be used may be appropriately selected from the range of 1 to the amount of the solvent per 1 mol of the compound [I-9], and is preferably 1 to 100 mol.
  • the reaction temperature of this reaction may be selected from any temperature range from ⁇ 10 ° C. to the reflux temperature in the reaction system in any reaction, and is preferably performed in a temperature range of 0 ° C. to 50 ° C.
  • reaction time of this reaction varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like in each reaction, but is usually 5 minutes to 24 hours.
  • compound [I-11] can be isolated by pouring the reaction mixture into water or the like, extracting the mixture with an organic solvent, and then concentrating the mixture. The isolated compound [I-11] can be further purified by column chromatography, recrystallization, and the like, if necessary. In addition, compound [I-11] can be used for the next reaction (Production method 6) without isolation and purification.
  • the compound represented by the general formula [I-12] can be produced, for example, using a compound represented by the general formula [III-3] according to a method comprising the following reaction formula. Can be.
  • R 3 , R 4 , R 6 , R a , R b , L 1 , A and n have the same meaning as described above.
  • Step 6-1 That is, the compound represented by the general formula [I-12] is prepared by combining the compound represented by the general formula [III-3] with a cyanate or thiocyanate in a suitable solvent in the presence of a suitable acid. And converting the compound [III-4] to the compound [IV-3] or the compound [IV-4] in the presence of a suitable base. Alternatively, it can be produced by reacting in a suitable solvent in the presence of a suitable acid catalyst. Examples of the cyanate or thiocyanate that can be used in this reaction include sodium cyanate, potassium cyanate, ammonium cyanate, sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate.
  • the amount of the cyanate or thiocyanate to be used may be selected from the range of 1 mol to 10 mol per 1 mol of the compound [III-3], and is preferably 1.0 to 6.0 mol.
  • Examples of the acid that can be used in this step include mineral acids such as hydrochloric acid and hydrobromic acid.
  • the amount of the acid used may be appropriately selected from the range of 1 to the amount of the solvent based on 1 mol of the compound [III-4], and is preferably from 1.0 to 10.0 mol.
  • Examples of the solvent that can be used in this step include nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, Examples include aprotic polar solvents such as 3-dimethyl-2-imidazolidinone, alcohols such as methanol, ethanol and 2-propanol, water or a mixed solvent thereof.
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-10 liters, per 1 mol of compound [III-3].
  • the reaction temperature in this step may be selected from an arbitrary temperature range from ⁇ 30 ° C.
  • reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 10 minutes to 20 hours.
  • compound [I-12] can be isolated by performing an operation such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture. The isolated compound [I-12] can be further purified by column chromatography, recrystallization or the like, if necessary.
  • Step 6-2 The compound represented by the general formula [I-12] is produced by reacting the compound represented by the general formula [III-4] under the same conditions as in step 1-3 of production method 1. Can be.
  • the compound represented by the general formula [I-14] can be produced, for example, using a compound represented by the general formula [I-13] according to a method comprising the following reaction formula. Can be.
  • the amount of compound [IV-11] or compound [IV-12] used in this reaction may be appropriately selected from the range of 1 to 20 mol per 1 mol of compound [I-13], and is preferably 1 0.1 to 5.5 mol.
  • Bases that can be used in this reaction include, for example, hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide, Inorganic bases such as alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, metal hydrides such as sodium hydride and potassium hydride, sodium methoxide , Sodium ethoxide, potassium tert-butoxide and other metal salts of alcohols or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0
  • the amount of the base used may be appropriately selected from the range of 1 to 5 mol per 1 mol of the compound [I-13], and is preferably 1.0 to 2.0 mol.
  • organic bases such as triethylamine and pyridine can also be used as the solvent.
  • the radical initiator that can be used in this reaction include sulfurous acid, a sulfite, and a sulfurous acid adduct such as Rongalite (trade name, sodium formaldehyde sulfoxylate).
  • the amount of the radical initiator to be used may be appropriately selected from the range of 0.01 to 5 mol per 1 mol of the compound [I-13], and is preferably 0.01 to 1.2 mol.
  • solvents such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane
  • aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene
  • Halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl Aprotic polar solvents such as sulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone, alcohols such as methanol, ethanol, 2-propanol, esters such as ethyl acetate, pentane, hexane, cyclo
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-10 liters, per 1 mol of compound [I-13].
  • the reaction temperature of this reaction may be selected from an arbitrary temperature range from ⁇ 30 ° C. to the reflux temperature in the reaction system, and is preferably from 0 ° C. to 150 ° C.
  • the reaction time of this reaction varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 10 minutes to 20 hours.
  • compound [I-14] can be isolated by performing operations such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture. The isolated compound [I-14] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • the compound represented by the general formula [I-15], the compound represented by the general formula [I-16] and the compound represented by the general formula [I-17] include, for example, It can be produced using the compound represented by [I-2] according to a method comprising the following reaction formula.
  • R 3 , R 4 , R 5 , R a , M, L 1 and n have the same meanings as described above, and R 6a is a C 1 -C 6 alkyl group, a C 1 -C 6 haloalkyl group, Represents a 2 -C 6 alkenyl group, a C 2 -C 6 alkynyl group or a C 3 -C 6 cycloalkyl group.
  • Step 8-1) That is, the compound represented by the general formula [I-15] is produced by reacting the compound represented by the general formula [I-2] under the same conditions as in step 3-1 of the production method 3. can do.
  • Step 8-2 The compound represented by the general formula [I-16] is produced by reacting the compound represented by the general formula [I-2] under the same conditions as in step 3-2 of the production method 3. can do.
  • Step 8-3 Further, the compound represented by the general formula [I-17] is produced by reacting the compound represented by the general formula [I-2] under the same conditions as in Step 3-3 of Production Method 3. can do.
  • the compound represented by the general formula [I-1] can be produced, for example, using a compound represented by the general formula [I-2] according to a method comprising the following reaction formula. Can be.
  • the compound represented by the general formula [I-1] is prepared by combining the compound represented by the general formula [I-2] with a suitable electrophilic reagent in the presence or absence of a suitable solvent. It can be produced by reacting in the presence or absence of a base, in the presence or absence of a suitable acid, in the presence or absence of a suitable dehydrating condensing agent.
  • the amount of the electrophilic reagent used in this reaction may be appropriately selected from the range of 1 to the amount of the solvent, and preferably 1 to 150 mol, per 1 mol of compound [I-2].
  • usable bases include, for example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and alkaline earth metals such as calcium hydroxide and magnesium hydroxide.
  • Metal salts of alcohols such as hydrides, sodium methoxide, sodium ethoxide, potassium tert-butoxide or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [ Organic bases such as [5,4,0] -7-undecene.
  • the amount of the base used may be appropriately selected from the range of 0.01 to 5 mol, and preferably 0.1 to 3.0 mol, per 1 mol of compound [I-2]. It is.
  • the acid that can be used is a Lewis acid, for example, sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid, mineral acids such as hydrochloric acid, hydrobromic acid or sulfuric acid, and acetic acid. Or carboxylic acids such as trifluoroacetic acid.
  • the amount of the acid used may be appropriately selected from the range of 0.001 to 5 mol per 1 mol of the compound [I-2], and is preferably 0.01 to 2.0 mol.
  • examples of the dehydration condensing agent that can be used include N, N′-dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-ethyl- 3- (3-dimethylaminopropyl) carbodiimide, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate, 4- (4 Examples thereof include 6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride, 1-hydroxybenzotriazole, and a mixture thereof.
  • the amount of the dehydrating condensing agent to be used may be appropriately selected from the range of 1 to 3 mol per 1 mol of compound [I-2], and is preferably 1.0 to 1.2 mol, respectively.
  • the solvent that can be used in this reaction include ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; Nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone and the like Aprotic polar solvents, alcohols such as methanol, ethanol, 2-propanol, halogenated
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-20 liters, per 1 mol of compound [I-2].
  • the reaction temperature of this reaction may be selected from an arbitrary temperature range from ⁇ 20 ° C. to the reflux temperature in the reaction system, and is preferably from 0 ° C. to 150 ° C.
  • the reaction time of this reaction varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 15 minutes to 24 hours.
  • compound [I-1] can be isolated by performing operations such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture. The isolated compound [I-1] can be further purified by column chromatography, recrystallization, etc., if necessary.
  • the compound represented by the general formula [I-1] can be produced, for example, using a compound represented by the general formula [I-18] according to a method comprising the following reaction formula. Can be.
  • the compound of the present invention represented by the general formula [I-1] can be prepared by converting the compound represented by the general formula [I-18] and the compound [IV-15] in the presence or absence of a suitable base. In a suitable solvent.
  • the amount of compound [IV-15] used in this reaction may be appropriately selected from the range of 1 to the amount of solvent relative to 1 mol of compound [I-18], and is preferably 1.0 to 10.0. Is a mole.
  • usable bases include, for example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and alkaline earth metals such as calcium hydroxide and magnesium hydroxide.
  • alkali metal carbonates such as sodium carbonate and potassium carbonate
  • inorganic bases such as alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate
  • metals such as sodium hydride and potassium hydride
  • Metal salts of alcohols such as hydrides, sodium methoxide, sodium ethoxide, potassium tert-butoxide or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [ Organic bases such as [5,4,0] -7-undecene.
  • the amount of the base to be used may be appropriately selected from the range of 1 to 10 mol per 1 mol of compound [I-18], and is preferably 1.0 to 3.0 mol.
  • the solvent that can be used in this reaction include ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; Nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone and the like
  • Aprotic polar solvents alcohols such as methanol, ethanol, 2-propanol, halogenated hydrocarbons such as dichlorome
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-20 liters, per 1 mol of compound [I-18].
  • the reaction temperature of this reaction may be selected from an arbitrary temperature range from ⁇ 20 ° C. to the reflux temperature in the reaction system, and is preferably from ⁇ 10 ° C. to 150 ° C.
  • the reaction time of this reaction varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 15 minutes to 20 hours.
  • compound [I-1] can be isolated by performing operations such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture. The isolated compound [I-1] can be further purified by column chromatography, recrystallization, etc., if necessary.
  • the compound represented by the general formula [I-1] can be produced, for example, using a compound represented by the general formula [IV-16] according to a method comprising the following reaction formula. Can be.
  • L 6 represents a halogen atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, a nonafluorobutanesulfonyloxy A benzenesulfonyloxy group, a p-toluenesulfonyloxy group, a dimethylsulfamoyloxy group, a dihydroxyboryl group (B (OH) 2 ), or a pinacolatoboran-2-yl group.
  • the compound represented by the general formula [I-1] is obtained by converting the compound [IV-16] and the compound [IV-17] into International Patent Publication WO2006 / 043635 or European Patent Publication EP30022279.
  • the compound represented by the general formula [II-2] can be produced, for example, using a compound represented by the general formula [III-4] according to a method comprising the following reaction formula. Can be.
  • the compound represented by the general formula [II-2] can be obtained by cyanating the compound represented by the general formula [III-5] in a suitable solvent in the presence or absence of a suitable catalyst, in a suitable solvent. It can be produced by subjecting the compound represented by [III-6] to a hydrolysis reaction in a suitable solvent in the presence of a suitable acid or base.
  • Step 12-1 Examples of the cyan compound used in this step include sodium cyanide, potassium cyanide, ammonium cyanide, zinc cyanide, copper cyanide, and mixtures thereof.
  • the amount of the cyan compound to be used may be appropriately selected usually from the range of 1 to 100 mol per 1 mol of the compound [III-5], and is preferably 1.0 to 5.0 mol.
  • Examples of the catalyst used in this step include tetrakis (triphenylphosphine) palladium.
  • the amount of the catalyst to be used may be appropriately selected usually from the range of 0.001 to 0.5 mol per 1 mol of the compound [III-5], and is preferably from 0.01 to 0.1 mol.
  • solvents such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane
  • aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene
  • dichloromethane examples include ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane.
  • Chloroform halogenated hydrocarbons such as 1,2-dichloroethane, etc., nitriles such as acetonitrile, propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide , Sulfolane, aprotic polar solvents such as 1,3-dimethyl-2-imidazolidinone, alcohols such as methanol, ethanol and 2-propanol, esters such as ethyl acetate, pentane, hexane and cyclohexa , Aliphatic hydrocarbons such as heptane, pyridine, pyridine picoline, etc., can be mentioned water, or a mixed solvent thereof, or the like.
  • the amount of the solvent to be used is 0.1 to 500 liter, preferably 0.3 to 50 liter, per 1 mol of compound [III-5].
  • the reaction temperature in this step may be selected from an arbitrary temperature range from usually ⁇ 30 ° C. to the reflux temperature in the reaction system, and is preferably from 0 ° C. to 150 ° C.
  • the reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually from 10 minutes to 72 hours.
  • compound [III-6] is isolated by performing operations such as pouring the reaction mixture into water, and collecting the precipitated solid by filtration or extraction with an organic solvent and then concentration. be able to.
  • the isolated compound [III-6] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • Step 12-2 Examples of the acid that can be used in this step include mineral acids such as hydrochloric acid, hydrobromic acid and sulfuric acid, carboxylic acids such as acetic acid and trifluoroacetic acid, and sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid.
  • the amount of the acid to be used may be appropriately selected from the range of 1 to the equivalent of the amount of the solvent per 1 mol of the compound [III-6], and is preferably 1.0 to 100.0 mol.
  • Examples of the base that can be used in this step include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium hydrogen carbonate; And inorganic bases such as alkali metal bicarbonates such as potassium hydrogen.
  • the amount of the base used may be appropriately selected from the range of 0.1 to 50 mol per 1 mol of compound [III-6], and is preferably 0.5 to 20.0 mol.
  • Examples of the solvent that can be used in this step include ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; Nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone and the like
  • Examples include aprotic polar solvents, alcohols such as methanol, ethanol and 2-propanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, water, and mixed solvents thereof.
  • the amount of the solvent to be used is 0.1-500 liter, preferably 0.3-30 liter, per 1 mol of compound [III-6].
  • the reaction temperature in this step may be selected from an arbitrary temperature range from usually ⁇ 30 ° C. to the reflux temperature in the reaction system, and is preferably from 0 ° C. to 150 ° C.
  • the reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually from 10 minutes to 72 hours.
  • the reaction mixture is poured into water for neutralization, and the precipitated solid is collected by filtration or extracted with an organic solvent and then concentrated to obtain the compound [II-2]. Can be isolated.
  • the isolated compound [II-2] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • Step 12-3 The compound represented by the general formula [II-2] is described in J. Am. Organometal. Chem. 358, pp. 563 to 565 (1988) or by a CO insertion reaction using a transition metal catalyst such as palladium according to the method.
  • the compound represented by the general formula [II-2] is described in Chem. Rev .. 90, pages 879 to 933 (1990), or lithiated and then reacted with carbon dioxide gas according to the method.
  • Step 12-4 the compound represented by the general formula [II-2] is described in J. Am. Org. Chem. 39, pp. 3318-3326 (1974), or by a CO insertion reaction using a transition metal catalyst such as palladium according to the method described above, to obtain a compound represented by the general formula [II-1]. And then subjecting the compound to a hydrolysis reaction in a suitable solvent in the presence of a suitable acid or base.
  • Step 12-5 The acid, base, solvent, reaction temperature and reaction time that can be used in this step are the same as in Step 12-2. After completion of the reaction, the reaction mixture is poured into water for neutralization, and the precipitated solid is collected by filtration or extracted with an organic solvent and then concentrated to obtain the compound [II-2]. Can be isolated. The isolated compound [II-2] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • the compound represented by the general formula [I-19] can be produced, for example, using a compound represented by the general formula [II-2] according to a method comprising the following reaction formula. Can be.
  • Step 13-1) That is, the compound represented by the general formula [I-19] can be obtained by converting the compound represented by the general formula [II-2] and the compound [IV-18] in the presence of a suitable dehydrating condensing agent and a suitable base. Alternatively, it can be produced by reacting in a suitable solvent in the absence.
  • the amount of compound [IV-18] used in this step may be appropriately selected from the range of 1 to 10 mol per 1 mol of compound [II-2], and is preferably 1.0 to 5.0 mol. It is.
  • the dehydrating condensing agent that can be used in this step includes, for example, N, N′-dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-ethyl-3- (3-dimethylaminopropyl) Carbodiimide, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate, 4- (4,6-dimethoxy-1,3,5 -Triazin-2-yl) -4-methylmorpholinium chloride, 1-hydroxybenzotriazole or a mixture thereof.
  • the amount of the dehydrating condensing agent may be appropriately selected from the range of 1 to 5 moles per 1 mole of the compound [II-2], and is preferably 1.0 to 3.0 moles.
  • usable bases include, for example, triethylamine, 4-methylmorpholine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, pyridine, 4-N , N-dimethylaminopyridine, and organic bases such as 2,6-lutidine.
  • the amount of the base used may be appropriately selected from the range of 0.1 to 5 mol per 1 mol of compound [II-2], and is preferably 0.1 to 3.0 mol.
  • Examples of the solvent that can be used in this step include halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; esters such as ethyl acetate; Nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone Aprotic polar solvents, such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, and the like; and mixed solvents thereof.
  • halogenated hydrocarbons such as dichloromethane, chloroform,
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-50 liters, per 1 mol of compound [II-2].
  • This step can be performed in the presence of a catalyst, if necessary, and the catalyst can be appropriately selected from 4-N, N-dimethylaminopyridine and the like.
  • the amount of the catalyst used may be appropriately selected from the range of 0.001 to 1 mol per 1 mol of the compound [II-2], and is preferably 0.01 to 0.1 mol.
  • the reaction temperature in this step may be selected from an arbitrary temperature range from ⁇ 20 ° C. to the reflux temperature in the reaction system, and is preferably from 0 ° C. to 80 ° C.
  • reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 1 minute to 100 hours.
  • compound [I-19] can be isolated by performing an operation such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture.
  • the isolated compound [I-19] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • the compound of the present invention represented by the general formula [I-19] can be prepared by converting the compound represented by the general formula [II-2] in an appropriate solvent in the presence or absence of an appropriate catalyst in an appropriate solvent.
  • the compound is converted to a compound [II-3] which is an active derivative such as a halide or a mixed acid anhydride, and then reacted with a compound [IV-18] in a suitable solvent in the presence of a suitable base.
  • thionyl chloride or oxalyl chloride can be used.
  • a reagent to be converted into another active derivative isobutyl chlorocarbonate, methanesulfonyl chloride, trifluoromethanesulfonyl chloride, p-toluenesulfonyl chloride and the like can be used.
  • the amount of the reagent to be converted into the active derivative may be appropriately selected from the range of 0.5 to 5 mol per 1 mol of the compound [II-2], and is preferably 0.5 to 2.2 mol. is there.
  • usable catalysts include, for example, N, N-dimethylformamide and the like.
  • the amount of the catalyst to be used may be appropriately selected from the range of 0.01 to 1 mol per 1 mol of the compound [II-2], and is preferably 0.01 to 0.3 mol.
  • the solvent that can be used in this step include halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, pentane, hexane, cyclohexane and heptane.
  • Such as aliphatic hydrocarbons such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3 Aprotic polar solvents such as -dimethyl-2-imidazolidinone; ethers such as diethyl ether, cyclopentylmethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; and mixed solvents thereof. It can.
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-10 liters, per 1 mol of compound [II-2].
  • the reaction temperature in this step may be selected from an arbitrary temperature range from ⁇ 20 ° C. to the reflux temperature in the reaction system, and is preferably from 0 ° C. to 80 ° C.
  • the reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually from 1 minute to 48 hours.
  • compound [II-3] can be isolated by performing an operation such as concentration.
  • Step 13-3 Production of compound [I-19] by reacting compound [IV-18] with the obtained reaction solution containing compound [II-3] in the presence of a suitable base and in a suitable solvent.
  • the amount of compound [IV-18] used in this step may be appropriately selected from the range of 1 to 3 mol per 1 mol of compound [II-2], and is preferably 1.0 to 2.5 mol. It is.
  • Bases that can be used in this step include, for example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate, and hydrogen carbonate.
  • Inorganic bases such as bicarbonates of alkali metals such as potassium, metal hydrides such as sodium hydride and potassium hydride or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine; Organic bases such as 1,8-diazabicyclo [5,4,0] -7-undecene are exemplified.
  • the amount of the base used may be appropriately selected from the range of 1 to 5 mol per 1 mol of the compound [II-2], and is preferably 1.0 to 2.5 mol.
  • solvent examples include halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, pentane, hexane, cyclohexane, and heptane.
  • halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane
  • aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene
  • pentane hexane
  • cyclohexane cyclohexane
  • heptane examples include heptane.
  • Such as aliphatic hydrocarbons such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3 Aprotic polar solvents such as -dimethyl-2-imidazolidinone, ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; water; and mixed solvents thereof. be able to.
  • aliphatic hydrocarbons such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3 Aprotic polar solvents such as -dimethyl-2-imidazolidinone, ether
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-10 liters, per 1 mol of compound [II-2].
  • the reaction temperature in this step may be selected from an arbitrary temperature range from ⁇ 20 ° C. to the reflux temperature in the reaction system, and is preferably from 0 ° C. to 80 ° C.
  • the reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually from 1 minute to 48 hours.
  • compound [I-19] can be isolated by performing an operation such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture.
  • the isolated compound [I-19] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • the compound represented by the general formula [I] can be produced, for example, using a compound represented by the general formula [I-20] according to a method comprising the following reaction formula. .
  • L 8 represents a halogen atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, And a nonafluorobutanesulfonyloxy group, a benzenesulfonyloxy group, a p-toluenesulfonyloxy group, and the like.
  • the compound of the present invention represented by the general formula [I] can be obtained by converting the compound represented by the general formula [I-20] and the compound [IV-19] in the presence or absence of a suitable base.
  • the amount of compound [IV-19] to be used in this reaction may be appropriately selected from the range of 1 to 100 mol per 1 mol of compound [I-20], and is preferably 1.0 to 10.0 mol. It is.
  • usable bases include, for example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and alkaline earth metals such as calcium hydroxide and magnesium hydroxide.
  • alkali metal carbonates such as sodium carbonate and potassium carbonate
  • inorganic bases such as alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate
  • metals such as sodium hydride and potassium hydride
  • Metal salts of alcohols such as hydrides, sodium methoxide, sodium ethoxide, potassium tert-butoxide or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [ Organic bases such as [5,4,0] -7-undecene.
  • the amount of the base to be used may be appropriately selected from the range of 1 to 10 mol per 1 mol of compound [I-20], and is preferably 1.0 to 5.0 mol.
  • the solvent that can be used in this reaction include ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; Esters such as ethyl acetate, nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3-dimethyl- Aprotic polar solvents such as 2-imidazolidinone, alcohols such as methanol, ethanol and 2-propanol
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-20 liters, per 1 mol of compound [I-20].
  • the reaction temperature of this reaction may be selected from an arbitrary temperature range from ⁇ 20 ° C. to the reflux temperature in the reaction system, and is preferably from ⁇ 10 ° C. to 80 ° C.
  • the reaction time of this reaction varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 15 minutes to 48 hours.
  • the compound [I] can be isolated by pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture. The isolated compound [I] can be further purified by column chromatography, recrystallization or the like, if necessary.
  • the compound represented by the general formula [I-21] can be produced, for example, using a compound represented by the general formula [I-19] according to a method comprising the following reaction formula. Can be.
  • the compound represented by the general formula [I-21] can be prepared by combining the compound represented by the general formula [I-19] with a suitable thiocarbonylating agent in the presence or absence of a suitable base. It can be produced by reacting in the presence or absence of a suitable solvent.
  • the thiocarbonylating agent used in this reaction is diphosphorus pentasulfide or Lawesson's Reagent (2,4-bis (4-methoxyphenyl) -1,3,2,4-dithiadiphosphetane- 2,4-disulfide) and the like.
  • the amount of the thiocarbonylating agent to be used may be appropriately selected from the range of 0.5 to 100 mol, preferably 0.5 to 3.0 mol, per 1 mol of compound [I-19].
  • Addition of a base is not always necessary in this reaction, but when a base is used, examples of the usable base include inorganic bases such as alkali metal carbonates such as sodium carbonate and potassium carbonate, and triethylamine, N, N- Organic bases such as dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, and 1,8-diazabicyclo [5,4,0] -7-undecene are exemplified.
  • the amount of the base to be used may be appropriately selected from the range of 0.01 to 10 mol, and preferably 0.1 to 2.0 mol, per 1 mol of compound [I-19].
  • the solvent that can be used in this reaction include ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; Aprotic polar solvents such as dimethyl sulfoxide and sulfolane, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and heptane, or mixed solvents thereof Is mentioned.
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-15 liters, per 1 mol of compound [I-19].
  • the reaction temperature of this reaction may be selected from an arbitrary temperature range from 0 ° C. to the reflux temperature in the reaction system, and is preferably from 0 ° C. to 150 ° C.
  • the reaction time of this reaction varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually 15 minutes to 48 hours.
  • compound [I-19] can be isolated by performing an operation such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture.
  • the isolated compound [I-19] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • the compound represented by the general formula [III-3] can be produced, for example, using a compound represented by the general formula [III-7] according to a method comprising the following reaction formula.
  • Step 1'-1 That is, the compound represented by the general formula [III-8] is represented by the general formula [III-7] in accordance with “Reduced general term” in Vol. By reducing the nitro compound.
  • the compound [III-7] generally available reagents can be used, and the compound [III-7] can also be produced by a method described in International Publication WO2009 / 078481 or a method similar thereto.
  • Step 1'-2 The compound represented by the general formula [III-3] is prepared by reacting the compound represented by the general formula [III-8] with a nitrite in a suitable solvent in the presence of a suitable mineral acid. After being converted to a salt, it can be produced by reducing it with a metal reducing reagent such as zinc dust, sodium sulfite, tin chloride or the like.
  • Mineral acids that can be used in this step include hydrochloric acid, sulfuric acid and the like.
  • the amount of the mineral acid to be used may be appropriately selected from the range of 2 to 10 mol per 1 mol of the compound [III-8], and is preferably 2.0 to 5.0 mol.
  • the amount of the nitrite used in this step may be appropriately selected from the range of 1 to 5 mol per 1 mol of the compound [III-8], and is preferably 1.0 to 1.2 mol.
  • the amount of the metal reducing reagent that can be used in this step may be appropriately selected from the range of 1 to 20 mol per 1 mol of compound [III-8], and is preferably 1.0 to 5.0 mol.
  • Examples of the solvent that can be used in this step include water, hydrochloric acid, sulfuric acid, acetic acid, a mixed solvent thereof, and the like.
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-10 liters, per 1 mol of compound [III-8].
  • the reaction temperature in this step may be selected from an arbitrary temperature range from ⁇ 20 ° C. to the reflux temperature in the reaction system, and is preferably from ⁇ 5 ° C. to 20 ° C.
  • the reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 30 minutes to 5 hours.
  • compound [III-3] can be isolated by performing operations such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating the mixture. The isolated compound [III-3] can be further purified by column chromatography, recrystallization, and the like, if necessary.
  • the compound represented by the general formula [III-1] can be produced, for example, using a compound represented by the general formula [III-3] according to a method comprising the following reaction formula.
  • Step 2'-1 That is, the compound represented by the general formula [III-1] is obtained by converting the compound represented by the general formula [III-3] and the compound [IV-20] or the compound [IV-21] to a suitable acid catalyst.
  • the compound represented by the general formula [III-9] can be produced by reacting in a suitable solvent in the presence or absence of the compound, and then reacting with a halogenating agent.
  • the amount of compound [IV-20] or compound [IV-21] used in this step may be appropriately selected from the range of 1 to 5 mol per 1 mol of compound [III-3], and is preferably 1 0.0 to 1.2 mol.
  • Examples of the acid catalyst that can be used in this step include sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid, and Lewis acids such as titanium tetrachloride.
  • the amount of the acid catalyst to be used may be appropriately selected from the range of 0.001 to 5 mol, and preferably 0.01 to 1.2 mol, per 1 mol of compound [III-3].
  • solvents such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane
  • aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene
  • Nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone and the like
  • Aprotic polar solvents alcohols such as methanol, ethanol, 2-propanol isopropyl alcohol, aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, pyridines such as pyridine and picoline, or a
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-10 liters, per 1 mol of compound [III-3].
  • Examples of the halogenating agent used in this step include chlorine, N-chlorosuccinimide, N-bromosuccinimide, tert-butyl hypochlorite and the like.
  • the amount of the halogenating agent to be used may be appropriately selected from the range of 1 to 5 mol per 1 mol of the compound [III-9], and is preferably 1.0 to 1.1 mol.
  • the reaction temperature in this step may be selected from an arbitrary temperature range from ⁇ 70 ° C. to the reflux temperature in the reaction system, and is preferably from ⁇ 20 ° C. to 100 ° C.
  • reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 15 minutes to 24 hours.
  • compound [III-1] can be isolated by performing operations such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating the mixture. The isolated compound [III-1] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • the compound represented by the general formula [III-1] can be prepared by converting the compound represented by the general formula [III-3] and the compound [IV-22] in the presence or absence of a suitable base.
  • the compound represented by the general formula [III-10] can be produced by reacting with a suitable solvent and then reacting with a halogenating agent.
  • the amount of compound [IV-22] used in this step may be appropriately selected from the range of 1 to 15 mol per 1 mol of compound [III-3], and is preferably 1.0 to 7.0 mol. It is.
  • Bases that can be used in this step include, for example, hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide, Inorganic bases such as alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; metal hydrides such as sodium hydride and potassium hydride; sodium methoxy Metal salts of alcohols such as sodium, sodium ethoxide and potassium tert-butoxide, or triethylamine, N, N-dimethylaniline, pyridine, 4-N, N-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0 And organic bases such as -7-undecene.
  • alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide
  • alkaline earth metals such as calcium hydroxide and magnesium hydroxide
  • the amount of the base used may be appropriately selected from the range of 1 to 10 mol per 1 mol of compound [III-3], and is preferably 1.0 to 1.2 mol.
  • the solvent that can be used in this step include ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; Nitriles such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone and the like
  • Aprotic polar solvents alcohols such as methanol, ethanol and 2-propanol, halogenated hydrocarbons such as dichloromethane
  • the amount of the solvent to be used is 0.1-100 liters, preferably 0.3-10 liters, per 1 mol of compound [III-3].
  • the halogenating agent that can be used in this step include phosphorus trichloride, phosphorus tribromide, thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, triphenylphosphine / carbon tetrachloride, or triphenylphosphine / carbon tetrabromide.
  • the amount of the halogenating agent to be used may be appropriately selected from the range of 1 mol to the amount of the solvent relative to 1 mol of compound [III-10], and is preferably 1.0 to 5.0 mol.
  • the reaction temperature in this step may be selected from an arbitrary temperature range from ⁇ 70 ° C. to the reflux temperature in the reaction system, and is preferably from ⁇ 20 ° C. to 100 ° C.
  • the reaction time of this step varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 15 minutes to 24 hours.
  • compound [III-1] can be isolated by performing operations such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating the mixture. Alternatively, compound [III-1] can also be isolated by concentrating the solvent from the reaction mixture. The isolated compound [III-1] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • the compound represented by the general formula [III-5] can be produced, for example, using a compound represented by the general formula [III-11] according to a method comprising the following reaction formula.
  • the compound represented by the general formula [III-5] can be produced by reacting the compound represented by the general formula [III-11] with a halogenating agent in a suitable solvent.
  • Halogenating agents usable in this reaction include chlorine, sulfuryl chloride, N-chlorosuccinimide, bromine, N-bromosuccinimide, 1,3-dibromo-5,5-hydantoin, iodine, N-iodosuccinimide, 1,3-diiodo-5,5-hydantoin and the like can be mentioned.
  • the amount of the halogenating agent to be used may be appropriately selected from the range of 0.5 to 10 mol, preferably 0.5 to 2.0 mol, per 1 mol of compound [III-11].
  • the solvent that can be used in this reaction include halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; acetonitrile, propionitrile; Aprotic polar solvents such as nitriles, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone;
  • carboxylic acids such as acetic acid, propionic acid, and trifluoroacetic acid, sulfuric acid, water, and a mixed solvent thereof.
  • the amount of the solvent to be used is 0.1-300 liter, preferably 0.3-20 liter, per 1 mol of compound [III-11].
  • the reaction temperature of this reaction may be selected from an arbitrary temperature range from -70 ° C to the reflux temperature in the reaction system, and is preferably from -20 ° C to 100 ° C.
  • the reaction time of this reaction varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually from 10 minutes to 24 hours.
  • the compound [III-5] is isolated by performing operations such as pouring the reaction mixture into water, and collecting the precipitated solid by filtration or extraction with an organic solvent and concentration. be able to.
  • the isolated compound [III-5] can be further purified, if necessary, by column chromatography, recrystallization and the like.
  • the 3- (1H-1,2,4-triazol-1-yl) benzoic acid derivative represented by the general formula [II] of the present invention or an ester thereof is represented by the general formula [I] of the present invention.
  • the 1-phenyl-1H-1,2,4-triazole derivative represented by the general formula [III] of the present invention is a 3- (1H-1,2) represented by the general formula [II] of the present invention.
  • the pesticidal composition of the present invention comprises a 3- (1H-1,2,4-triazol-1-yl) benzoic acid amide derivative represented by the general formula [I] of the present invention or an agriculturally acceptable salt thereof. Contains as an active ingredient.
  • the pesticidal composition of the present invention can contain, if necessary, additional components (carriers) usually used in pesticide preparations.
  • the pest control agent of the present invention is a 3- (1H-1,2,4-triazol-1-yl) benzoic acid amide derivative represented by the general formula [I] of the present invention or an agriculturally acceptable salt thereof.
  • the pesticides of the present invention are typically insecticides, acaricides and nematocides.
  • the pest control agent of the present invention can contain, as necessary, an additive component (carrier) usually used in agricultural chemical formulations.
  • a carrier such as a solid carrier or a liquid carrier, a surfactant, a binder or a tackifier, a thickener, a coloring agent, a spreading agent, a spreading agent, an antifreezing agent, an anti-caking agent, Disintegrators, decomposition inhibitors and the like can be mentioned, and if necessary, preservatives, plant fragments and the like may be used as additional components.
  • a carrier such as a solid carrier or a liquid carrier, a surfactant, a binder or a tackifier, a thickener, a coloring agent, a spreading agent, a spreading agent, an antifreezing agent, an anti-caking agent, Disintegrators, decomposition inhibitors and the like can be mentioned, and if necessary, preservatives, plant fragments and the like may be used as additional components.
  • These additional components may be used alone or in combination of two or more.
  • Solid carriers include, for example, pyrophyllite clay, kaolin clay, silica clay, talc, diatomaceous earth, zeolite, bentonite, acid clay, activated clay, attapulgase clay, vermiculite, perlite, pumice, white carbon (synthetic silicic acid, Mineral carriers such as synthetic silicates) and titanium dioxide; vegetable carriers such as wood flour, corn stalk, walnut shell, fruit nucleus, peach, sawdust, bran, soy flour, powdered cellulose, starch, dextrin, saccharides and the like; Inorganic salt carriers such as calcium carbonate, ammonium sulfate, sodium sulfate, and potassium chloride; and polymer carriers such as polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, and urea-aldehyde resins. it can.
  • liquid carrier examples include monohydric alcohols such as methanol, ethanol, propanol, 2-propanol, butanol, and cyclohexanol; and polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, and glycerin.
  • monohydric alcohols such as methanol, ethanol, propanol, 2-propanol, butanol, and cyclohexanol
  • polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, and glycerin.
  • Polyhydric alcohol derivatives such as propylene glycol ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone and isophorone; ethyl ether, 1,4-dioxane, cellosolve, dipropyl ether; Ethers such as tetrahydrofuran; aliphatic hydrocarbons such as normal paraffin, naphthene, isoparaffin, kerosene and mineral oil; , C 9 -C 10 alkylbenzene, xylene, solvent naphtha, alkylnaphthalene, aromatic hydrocarbons such as high-boiling aromatic hydrocarbons; 1,2-dichloroethane, chloroform, halogenated hydrocarbons such as carbon tetrachloride, acetic acid Esters such as ethyl, diisopropyl phthalate,
  • the surfactant is not particularly limited, but is preferably one that gels in water or exhibits swelling properties, for example, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene Fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene fatty acid diester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene dialkyl phenyl ether, polyoxyethylene alkyl phenyl ether formalin condensate, polyoxyethylene poly Oxypropylene block polymer, alkyl polyoxyethylene polypropylene block polymer ether, polyoxyethylene alkylamine, polyoxyethylene Fatty acid amide, polyoxyethylene fatty acid bisphenyl ether, polyalkylene benzyl phenyl ether, polyoxyalkylene styryl phenyl ether, acetylene diol, polyoxyalkylene-added acetylene dio
  • binder and tackifier examples include carboxymethylcellulose and salts thereof, dextrin, water-soluble starch, xanthan gum, guar gum, sucrose, polyvinylpyrrolidone, gum arabic, polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, and an average molecular weight of 6,000 to Examples include polyethylene glycol having a molecular weight of 20,000, polyethylene oxide having an average molecular weight of 100,000 to 5,000,000, and natural phospholipids (eg, cephalic acid, lecithin, etc.).
  • carboxymethylcellulose and salts thereof examples include carboxymethylcellulose and salts thereof, dextrin, water-soluble starch, xanthan gum, guar gum, sucrose, polyvinylpyrrolidone, gum arabic, polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, and an average molecular weight of 6,000 to Examples include polyethylene glycol having a molecular weight of 20,000, polyethylene oxide having
  • thickener examples include water-soluble polymers such as xanthan gum, guar gum, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivative, and polysaccharide; inorganic fine powders such as high-purity bentonite and white carbon And the like.
  • coloring agent examples include inorganic pigments such as iron oxide, titanium oxide, and Prussian blue; and organic dyes such as alizarin dye, azo dye, and metal phthalocyanine dye.
  • the spreading agent examples include silicone surfactants, cellulose powder, dextrin, modified starch, polyaminocarboxylic acid chelate compounds, cross-linked polyvinyl pyrrolidone, maleic acid and styrenes, methacrylic acid copolymers, and polymers of polyhydric alcohols. And a diester of a dicarboxylic acid, and a water-soluble salt of polystyrenesulfonic acid.
  • the spreading agent examples include various surfactants such as sodium dialkyl sulfosuccinate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene fatty acid ester; paraffin, terpene, polyamide resin, polyacrylate , Polyoxyethylene, wax, polyvinyl alkyl ether, alkylphenol formalin condensate, synthetic resin emulsion and the like.
  • antifreeze examples include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin.
  • anti-caking agent examples include polysaccharides such as starch, alginic acid, mannose and galactose; polyvinylpyrrolidone, white carbon, ester gum, petroleum resin and the like.
  • disintegrating agent examples include sodium tripolyphosphate, sodium hexametaphosphate, metal stearate, cellulose powder, dextrin, a copolymer of methacrylic acid ester, polyvinylpyrrolidone, a polyaminocarboxylic acid chelate compound, and sulfonated styrene / isobutylene / maleic anhydride.
  • Acid copolymers and starch / polyacrylonitrile graft copolymers can be exemplified.
  • decomposition inhibitor examples include desiccants such as zeolite, quicklime, and magnesium oxide; phenol-based, amine-based, sulfur-based, and phosphoric acid-based antioxidants; and salicylic acid-based and benzophenone-based ultraviolet absorbers. Can be mentioned.
  • the content thereof is usually 5 to 95%, preferably 20 to 90% for a carrier such as a solid carrier or a liquid carrier on a mass basis.
  • the surfactant is usually selected in the range of 0.1% to 30%, preferably 0.5 to 10%, and the other additives are 0.1 to 30%, preferably 0.5 to 30%. It is selected in the range of 1010%.
  • the pest control agent of the present invention includes powders, powders and granules, granules, wettable powders, aqueous solvents, wettable granules, tablets, jumbo, emulsions, oils, liquids, flowables, emulsions, microemulsions , Suspoemulsion, microdispersion, microcapsule, smoke agent, aerosol, bait, paste and the like.
  • these preparations When these preparations are actually used, they can be used as they are or diluted to a predetermined concentration with a diluent such as water.
  • a diluent such as water.
  • the application of various preparations containing the compound of the present invention or a dilution thereof can be carried out by a commonly used application method, that is, spraying (eg, spraying, misting, atomizing, dusting, dusting, water application, box application) Application), soil application (for example, mixing, irrigation, etc.), surface application (for example, application, dressing, coating, etc.), seed treatment (for example, smearing, dressing, etc.), immersion, poison bait, smoke application And the like. It is also possible to feed the livestock with the above-mentioned active ingredient by mixing it with the feed to control the generation and growth of harmful insects, particularly harmful insects, in their excrement.
  • the pest control method of the present invention is a method for controlling a pest according to the above-mentioned application method, wherein the 3- (1H-1,2,4-triazol-1-yl) benzoic acid amide derivative represented by the general formula [I] of the present invention or a derivative thereof is used. It can be carried out by using an amount of an active ingredient of an agriculturally acceptable salt.
  • the mixing ratio (% by mass) of the active ingredient in the pest control agent of the present invention is appropriately selected as necessary.
  • a powder, a granule, a fine granule or the like it is appropriate to appropriately select from the range of 0.01 to 20%, preferably 0.05 to 10%. It is appropriate to appropriately select from the range of 30%, preferably from 0.5 to 20%, and in the case of a wettable powder, a wettable powder, etc., it is appropriately selected from the range of 1 to 70%, preferably 5 to 50%.
  • a water solvent or a liquid preparation it may be appropriately selected from the range of 1 to 95%, preferably 10 to 80%, and in the case of an emulsion or the like, 5 to 90%, preferably 10 to 80%. It is preferable to select an appropriate amount from the range.
  • it is appropriately selected from the range of 1 to 50%, preferably 5 to 30%. It is preferable to select an appropriate one from the range of 50%, and an emulsion, a microemulsion, In the case of a spoemulsion or the like, it is appropriate to appropriately select from the range of 5 to 70%, preferably 10 to 60%.
  • the pest control agent of the present invention When the pest control agent of the present invention is used after being diluted with a diluent, it is generally used at an active ingredient concentration of 0.1 to 5000 ppm. When the preparation is used as it is, the application rate per unit area is 0.1 to 5000 g per ha as the active ingredient compound, but is not limited thereto.
  • the pesticidal agent of the present invention is sufficiently effective even when the compound of the present invention is used alone as an active ingredient.
  • other fertilizers and pesticides for example, insecticides, pesticides, It can be mixed and used in combination with mites, nematicides, synergists, fungicides, antivirals, attractants, herbicides, plant growth regulators, etc., in which case even better effects may be exhibited. .
  • Insecticidal active ingredients Acrinathrin, azadirachtin, azamethiphos, acinonapyr, azinphos-acetyl, azinphos-acetyl, azinphos-acetyl, azinphos-acetyl, azinphos-acetate (Acetoprole), acephate, azocyclotin, abamectin, afidopyropen, afoxolaner, amideflumetrametrametrametrametamu , Alanycarb, aldicarb, aldoxycarb, allethrin [including d-cis-trans-form, d-trans-form], isazophos, isamiphos (isomidphos) Isocarbobophos, isoxathion, isocycloseram, isofenphos-methyl, isoprocarb, epsilon-methosulfon,
  • I Lumectin imiciafos, imidacloprid, imiprothrin, indoxacarb, indoxacarb, esfenvaleth, ethiophenocarb, ethiophenocarb ethifenfolate Ethylene dibromide, etoxazole, etofenprox, ethoprophos, ethofophos, etrimfos, emamectin, emamectin benzoate zoate, endosulfan, empenthrin, oxazosulfyl, oxamyl, oxamyl, oxydimetone-methyl, oxydeprotosate, oxydeprotos (fos) cadasufos, kappa-tefluthrin, kappa-bifenthrin, kappa-bifenthrin, kar
  • chlorfenapyr chlorfenvinphos, chlorfluazuron, chlormephos, chloropraresulin, sialopyrinopyrinopyrosine, sialopyrinopyrinopyrosine, and sialopyrinopyrinopyrosine, sialopyrinopyrocyranopyrinopyrosine, sialopyrinopyrinopyrophile, sialopyrinopyrinopyrinopyrinopyrinopyrinopyrinopyrinopyrinopyrinopyrnopyrophilin.
  • Liture-B aluminum phosphide (aluminium phosphide), zinc phosphide (zinc phosphide), hydrogen phosphide (phosphine), lufenuron (lufenuron), rescalure, resmethrin (resmethrin) epicinetin, rotenone, nuclear polyhedrosis virus embedding, fenbutatin oxide, calcium cyanide, organic tin compounds (organotins), nicotine sulfate (nicotine-sulphate), (nicotine-sulphate) 11-tetradecenyl acetate, (Z) -11-hexadecenal, (Z) -11-hexadecenyl acetate, (Z) -9,12-tetradecadienyl acetate, (Z) -9-tetradecen-1-ol , (Z, E) -9,11-tetradecadien
  • Fungicidal active ingredient Azaconazole, acibenzolar-S-methyl, azoxystrobin, anilazine, anisulbrom, amipyriffline, aminopyrifline, aminoprifectin aldimorph), isotianil, isopyrazam, isofetamide, isoflucipram, isoprothiolane, ipconifen, epuconazole, ipconazole, ipconazole, ipconazole, ipconazole, and ipconazole.
  • Fentriffluconazole ipfentrifluconazole
  • iprodione iprovalicarb
  • iprobenfos imazalilamine, iminotazine albecilate, iminoctazine albesilate (Imibenconazole), impirfluxam, imprimatin A, imprimatin B, edifenphos, etaconazol, ethaboxam aboxam), etirimol, ethoxyquin, ethridiazole, enestroburin, enoxastrobin, epoxiconil, oxyloxyxanol, oxyloxyl, oxyloxyl, oxyloxyl, oxyl, oxyl, oxyl, oxyl, oxyl, oxyl, xyloxyl, xyloxyl, xyloxyl, xyloxyl, xyloxyl, xyloxyl
  • Diflupir (benzovindiflupyr), benthiazole (benthiazole), benthiavalicarb-isopropyl, penthiopyrad, penflufen, scafylid, scafylid, scalido, scalido, scalido, scalide, boscalid, sc lcium, sodium, polyoxin, polycarbamate, bordeaux mixture, mancopper, mancozeb, mandeb, mandiopropamide Microbutanil, mineral oils, mildiomycin, methasulfocarb, metatam, metalaxyl, metalaxyl, metalaxyl, metalaxyl, metalaxyl, metalaxyl, metalaxyl Methyl tet Protol (metyltetraprole), metconazole (metconazole), methinostrobin (metaminostrobin), metrafenone (
  • Herbicidal active ingredients Ioxynil, acronifen, acrolein, azafenidin, azafenidin, acifluorfen (including salts with sodium and the like), azimsulfuron, azhamulace, ashramus (Acetochlor), atrazine (atrazine), anilofos (anilofos), amicarbazone, amidosulfuron, amitrolle, aminocyclopyrrol (amiclocyclopride), aminocyclopyracryloamidopyramylo, aminopyrrochloride, aminopyracryloamidopyramyl, aminopyrochloride, aminopyrochloride, aminopyracrylo, aminopyracrylo, aminopyracrylo, aminopyracrylamide ofos-methyl, ametrin, alachlor, alloxydim, ancymidol, isouron, isoxachlortole, isoxaflutoxol (Isoxaben), isodecyl alcohol
  • Salts such as isopropylamine No), imazametalsz (imazamethabenz-methyl), imazamox (imazamox), imazethapyr (imazethapyr), imazosulfuron (imazosulfuron), Indajifuramu (indaziflam), indanofan (indanofan), Egurinajin-ethyl (eglinazine-ethyl), esprocarb (esprocarb), Etame Tosulfuron-methyl, ethalfluralin, ethidimuron, ethoxysulfuron, ethoxyfen-ethyl, ethofumet sate), etobenzanide, endothal-disodium salt, oxadiazon, oxadiargyl, oxadiclomefone, oxazilfolon, oxasulfuron, oxasulfuron, o
  • esters such as heptanoic acid), bromophenoxime, bromobutide, florasulam, florpyrauxifen, florpyrauxifenhexyl, and florpyraxenixen-hexyl.
  • petoxamide (petoxamid), benazoline (benazolin), penoxsulam (penoxsulam), heptamaloxyloglucan (heptamaloxyloglucan), beflubutamate (beflubutamid), beflubutamate ), Bencarbazone, pendimethalin, benzfendizone, bensulide, bensulfuron-methyl, benzobicyclone, benzobicyclophenic acid Benzofenap, bentazone, pentanochlor, pentoxazone, pentoxazone, benfluralin, benfurasate, benfuresate, fosaforen, fomesafron, fomesaffen, fomesafen, formesafen Neuron (forchlorfenuron), mecoprop (including salts such as sodium, potassium, isopropylamine, triethanolamine, dimethylamine), mecoprop-P-potassium salt, mecosulfuron (mesosulf
  • Plant growth regulator 1-naphthylacetamide, 1-methylcyclopropene, 2,6-diisopropylnaphthalene, 2, oxo-4- (2-phenylethyl) aminobutyric acid, Chemical name, CAS registry number: 1083-55-2), 4-chlorophenoxyacetic acid (4-CPA), n-decyl alcohol (n-decanol), aviglycine, ancymidol, abscisic acid ( abscisic acid, inabenfide, indole acetic acid, indole butyric acid (indole butyric acid) id), uniconazole, uniconazole-P, unicozole-P, ecolist, ethiclozate, ethephon, ethephon, epocholeone, oxine sulfate, oxine sulfate ), Calcium formate (calcium formate), cloxyfonac (cloxyfonac
  • Isoxadifen isoxadifen-ethyl, oxabetrinil, cloquintcet-mexyl, dietholate, dimethoate, dimethoate Cyprosulfamide, naphthalic anhydride (1,8-Naphthalic @ Anhydride), fenchlorazole-O-ethyl, fenchlorim, furilazole, furixazole uxofenim), flurazole, benoxacor, mephenate, mefenpyr, mefenpyr-ethyl, mefenpyr-diethyl, mefenpyr-diethyl, lower alkyl, substituted lower alkyl, mefenpyr-diethyl 2-dichloro-N- (1,3-dioxan-2-ylmethyl) -N- (2-propenyl) acetamide (PPG-1292), 2-dichloromethyl-2-methyl-1,3-dioxan
  • the pest control agent of the present invention configured as described above includes grasshopper pests, thrips pests, stinkbug pests, crustacean pests, fly eye pests, lepidopteran pests, wasp order pests, coleoptera, pests Pests, cockroach pests, chapterae pests, whiteflies pests, lice pests, plant parasitic mites, plant parasitic nematodes, plant parasitic molluscs, other pests, unpleasant animals, sanitary pests, parasites It has an excellent control effect against pests such as Examples of such pests include the following species.
  • grasshopper pests include, for example, Ruspolia lineeosa of the family Grassicaceae, emerma crickets of the cricket family (Teleogrylus emma), and green worms (Truljalia hibinoni of the family Keragina (Galina), such as Kera (Galenta pallidae).
  • the Thysanoptera for example, of the thrips family Hirazuhanaazamiuma (Frankliniella intonsa), western flower thrips (Frankliniella occidentalis), yellow tea thrips (Scirtothrips dorsalis), southern thrips (Thrips palmi), green onion thrips (Thrips tabaci), Daizuusu Thrips thrips (Thrips @ setosus), Croton thrips (Heliothrips @ haemorrhoidalis), Rice thrips (Stenchaethotrips @ biformis), etc., of the family Thrips thrips (Thrips thrips).
  • Wasabi Kuda thrips Liothrips wasabiae
  • rice Kedah thrips Haplothrips aculeatus
  • stink bug pests include, for example, the cicada family, Iwaki-kami-semi (Mogannia @ minuta), the Aphid beetle family (Aphrophora @ intermedia), the sugarcane spitbug (Mahanarva @ fimbriata, and the like), and the like.
  • Leafhoppers of the leafhopper family (Arbordia @ apicalis), Leafhoppers (Empoasca @ onukii), Leafhoppers (Nephotettix @ cincticeps), and Leafhopper Leafhoppers (Nephotettix) ens), cross di leafhopper (Nephotettix nigropictus), Inazuma leafhopper (Recilia dorsalis), okra leaf hopper (Amrasca biguttula), mango leaf hopper (Idioscopus nitidulus, Idioscopus clypealis, Amritodus atkinsoni), Inazuma leafhopper (Recilia dorsalis), potato leaf hopper (Empoasca @ fabae), corn leaf hoppers (Dalbulus @ maidis), etc., and the brown planthopper (Pentastiridius @ apicalis), etc.
  • the family of the family Carnidae (Nissia acer), such as the family of the family Siracusa (Nissia), and the family of the family of the family Siracusa (Ricaceae), Bacillus serrata (Achirus @ flammeus), etc., Orosanga @ japonicus, etc., Aobahagoromo family, etc., Mimophantia @ maritima, etc .; ri) and others; Calophya mangiferae of the family Lamiaceae; Daktulosphaira vitifoliae of the family Philoxera; In the families, Aphirosiphon apisum, Aphis gossypii, Aphis gossypii, Aphispiraecola, Aphid aphisii, Aphis mosaic blossoms ersicae), wheat midge aphid (Schizzaphis @ graminum), wheat aphid (Rhopa
  • Leptocorisa chinensis Examples include the stink bug (Rhopalus maculatus), the lower bug stink bug (Scaptocoris @ castanea), the bed bug (Cimex @ lectularis), and the like.
  • the Coleoptera for example, cupreous chafer of Scarabaeidae (Anomara cuprea), rufocuprea (Anomara rufocuprea), Japanese beetle (Popillia japonica), core Oh flower chafer (Oxycetonia jucunda), Sakura Tsurukogane (Anomala geniculata), rhinoceros beetle (Oryctes rhinoceros) , (Heptophylla @ picea), Phyllophaga @ cuyabana, etc., of the family Beetle Beetle (Agriotes ogreas Aegeos ogreus).
  • Cryptocarpium scrophleus in the family Cuboptera scents such as Carpophilus hemipterus and Pollen beetle (Meligethes aeneus); Tentami (Epilachna @ varirivestis), T. japonica (Henosepilachna @ vigintioctopunctata), etc. of the Tenebrionidae family (Tenebrio molitor, etc.), etc.
  • Leaf beetles Colorado potato beetle Leaf beetle (Leptinotarsa decemlineata), Western corn root worm (Diabrotica virgifera virgifera), Northern corn root worm (Diabrotica barberi), Southern koa Rootworm (Diabrotica undecimpunctata howardi), cucurbit leaf beetle (Aulacophora femoralis), radish leaf beetle (Phaedon brassicae), Kamenokohamushi (Cassida nebulosa), Inedorooimushi (Oulema oryzae), Mexican beetle (Epilachna varivestis), Kisujinomihamushi (Phyllotreta striolata), Madara Kasahara beetle ( Demotina @ fasciculata, cabage stem flare beetle (Psyliodes @ chrysocephala), bean leaf beetle (Cer
  • Examples of pests of the order Fly flies include, for example, the swordfish (Tipula aino) and the fly fly bag (Plecia nearctica) and the mushroom fly larva (Execia shiitakevora) and the mosquito scallop and the like.
  • Bivalve mushrooms Pnyxia scabiei
  • Blysia mushrooms Blysia mushrooms (Bradysia agrestis), etc.
  • soybean flies Asphonylia yusimai
  • Hesian flies Mayetiola ⁇ st ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Culex pipiens (Culex @ pip ens @ pallens, etc .; Simulium @ takahashii, etc .; Chironomus @ oryzae, etc .; Afidae, Chrynobus @ suavis; ); Fly (Agromyza oryzae), eggplant leafminer (Liriomyza bryoniae), the pea (Chromatomyia horticola), green onion leafminer (Liriomyza chinensis), such as American cell pen Tin leaf minor
  • Lepidoptera pests include, but are not limited to, Endoclita excrescens, bats of the family bat, Endospila ⁇ ampelopsia of the family of the family bats, etc .; Sea oysters (Archips @ fuscocupreanus), apple lizards (Adoxophys ⁇ orana ⁇ fasciata), Nashihimesingui (Grapholita @ molesta), chahamaki (Homona @ magnaigina, L. monella), European grape vine moss (Lobesia botrana), etc., Grape Hosohamaki (Eupoecilia ambiguella), etc.
  • Geometridae family of Artemisia Eda Shakti (Ascotis selenaria), pine moth (Dendrolimus spectabilis of lasiocampidae), lackey moth (Malacosoma neustrium testaceum), etc., AGRIUS CONVOLVULI of sphingidae (Agrius convolvuli), etc., of Lymantriidae Arna Pseudoconspersa (Arna pseudoconspersa ), Orygiafur approximans, Lymantria dispar, and others, such as Hyphantria cunea, belonging to the family Noctuidae, and Agrotis ggigas, Agrotis gigas, from the family Noctuidae.
  • honey bee pests examples include, for example, the wasp-family spp. (Agephygana), the wasp-family chestnut wasp (Apethymus kuri), the squamf wasp (Athalia rosae ruficornis), and the bee-family Drikyuurusi (C.) Ants (Solenopsis @ invicta), such as the Japanese hornet (Vespa @ simillima @ xanthoptera), and the ant family (Solenopsis @ invicta), and the Argentine ant (Lineipithema @ humile), etc., can be mentioned.
  • Examples of the order Pests from the order of the order Tabanida include, for example, Bourletiella Hortensis of the family Martaviridae.
  • Lepidoptera As examples of the pests of Lepidoptera, there may be mentioned, for example, Lepidoptera saccharina (Lepidoptera) and Ctenolepisma (Vilosa).
  • cockroach pests for example, cockroaches (Periplaneta @americana), German cockroaches (Blattella @germanica), termites of the termite family (Odontotermes @ Formicidae), and termites of the termites of the genus Asterica sect. (Cryptotermes @ domesticus), termites of the family Termite (Copterotermes @ formosanus), and termites (Reticulitermes @ speratus).
  • insect pests of the order Psocoptera include, for example, Trochomium (Pulsatorium) of the family Papilionidae, and Usgrochatate (Liposcelis @ corrodens) of the family Papilionidae.
  • earwig pests include, for example, Laberadidae (Labobodura riparia) belonging to the family Parasitidae.
  • insects of the order Lepidoptera include, for example, chicks of the family Apocynidae, such as the chicks of the family Apocynidae, and the lice of the family Psyllidae, Damalinia bovis.
  • Examples of the lice pests include, for example, Haematopinus suis of the family Lamiidae, Pediculus humanus of the Laceae family, and the like and the genus Pis of the genus Pseudocephalus (Lingnathus tosetosus), such as the louse lice of the genus Lepidoptera, Licegrass. Can be.
  • acarid pests include, for example, the house dust mite (Penthaleus major), the dust mite Cyclamen mite (Phytonemus pallidus), the typhoid mite (Polyphagotarsononemus latus), and the species of the family Dermatophagidae: And other spider mites (Eotetranychus mite) (Panionychus mite), such as the red mite (Brevipalpus lewisi), the spider mite (Tuckerella pavoniformis), and the spider mite (Eotetranychus mite).
  • the plant parasitic nematodes include, for example, a grape nematode (Xipinema index) of the family Longidols, a paratrichodor nematode (Paratrichodorus minor) of the family Trichodulaceae, a species of the family Rhabditela sp.
  • tea pin nematodes of Paratirenkusu Department (Paratylenchus curvitatus), of Meroidogine Department of sweet potato root-knot nematode (Meloidogyne incognita), northern root-knot nematode (Meloidogyne hapla), Javanese root-knot nematode (Meloidogyne javanica), Columbia root-knot nematode (Meloidogyne chitwoodi), false Potato cyst nematodes (Globodera rostochiensis) of the family Heterodela, such as Colombian root knot nematodes (Meloidogyne fallax), potato cyst nematodes (Globodera pallida), soybean cysts Species of the family Psyllenchus (Psilenidae), such as the genus Psinus, Psylenchus (Hymenoptera), such as He
  • plant-parasitic molluscs examples include, for example, Pomicea canaliculata and the like of the family Papilionidae, Levicaulis @alte of the family Aphididae, and Achatina @flicica of the family Achamidae and the like.
  • Species of the family Agonaceae such as Schimuxia sect.
  • pests such as pests, unpleasant animals, sanitary pests, livestock pests, and parasites
  • examples of other pests include, for example, a crayfish of the order Crayfish (Procambarus @ clarkii), a porphyria of the order Coleoptera, Porcellio @ scaber, and the like.
  • Etc . Armadillidium vulgare
  • Chiracan spiders of the order Araneidae such as the redback spider (Therididae @ hasseltii) of the order Spiderae worms (Ascaris @ lumbricoides), etc.
  • the pest control agent of the present invention has a control effect on the pests and the like exemplified above, which have acquired resistance to the existing pest control agent.
  • the pesticidal composition of the present invention can also be used for plants that have acquired characteristics such as insect resistance, disease resistance, and herbicide resistance by genetic recombination, artificial crossing, and the like.
  • plant to which resistance has been imparted by a breeding method or a genetic recombination technique means not only resistance imparting by classical breeding and genetic conferring techniques, but also molecular biology Also include plants to which resistance has been imparted by a new breeding technique (New Plant Breeding Technologies, NBTs) that combines conventional techniques.
  • New breeding techniques are described in the book “Let's Understand New Plant Breeding Techniques” (International Literature Company, Ryo Osawa, Hiroshi Emen), review article “Genome Editing Tools” in Plants (Genes 2017, 8, 399, Tapan Kumar Moanta). Tufail, Bashir, Abeer, Hashem, Elsayed, Fathi, Abd_Allah, and Hanghong, Bae).
  • the melting point which is the physical property value of the compound of the present invention
  • the refractive index was measured using an Atago Abbe refractometer.
  • the 1 H NMR spectrum was measured using JNM-LA400 (400 MHz), JNM-LA300 (300 MHz) or JNM-ECS300 (300 MHz) manufactured by JEOL with tetramethylsilane (TMS) as an internal standard.
  • reaction mixture was concentrated under reduced pressure, and a 10% aqueous citric acid solution was added to the residue to acidify the reaction mixture, thereby depositing a solid.
  • the solid was filtered, washed with water, and dried to obtain 6.09 g of a crude target product (yield: 93%).
  • reaction mixture was concentrated under reduced pressure, and a 10% aqueous citric acid solution was added to the residue to acidify the reaction mixture, thereby depositing a solid.
  • the solid was filtered, washed with water, and dried to obtain 0.63 g (yield 91%) of a crude target product.
  • Ethyl 4-fluoro-2-methyl-5- [5-methyl-3- (trifluoromethyl) -1H-1,2,4-triazol-1-yl] benzoate (Compound No. of the present invention: Preparation of C-0109) Ethyl 5- [2- (1-amino-2,2,2-trifluoroethylidene) hydrazinyl] -4-fluoro-2-methylbenzoate 1.27 g (4.13 mmol) of N, To 10 mL of the N-dimethylacetamide solution was added 0.49 g (6.2 mmol) of acetyl chloride under ice-cooling, followed by stirring at 140 ° C. for 1 hour.
  • A-0212 of the present invention 5- [5-chloro-3- (trifluoromethyl) -1H-1,2,4-triazol-1-yl] -4-fluoro 0.23 g (1.7 mmol) of potassium carbonate was added to 20 mL of a methanol solution of 0.55 g (1.4 mmol) of -2-methyl-N- (2,2,2-trifluoroethyl) benzoic acid amide, and the mixture was added at room temperature. Stir for 4 hours.
  • A-2170 of the present invention (1) Production of di (2,2,2-trifluoroethyl) N-cyanodithiocarboxyimino acid
  • Trifluoromethanesulfonic acid 2,2,2 was added to 50 mL of a dimethyl sulfoxide solution of 7.00 g (36.0 mmol) of dipotassium N-cyanodithiocarboxyiminoate prepared according to the method described in Patent Publication WO 1994/026706 under ice-cooling. 20.06 g (86.43 mmol) of 2-trifluoroethyl was added, and the mixture was stirred at room temperature for 67 hours.
  • the solvent was distilled off under reduced pressure, and the residue was dissolved in 100 mL of methanol. Under ice-cooling, 17.12 g (123.9 mmol) of potassium carbonate was added, and the mixture was stirred at room temperature for 5.5 hours. After adjusting the pH to 5 by adding hydrochloric acid, saturated saline was added, and the mixture was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain a crude target product. This was used for the next step without purification.
  • reaction mixture was concentrated under reduced pressure, ethyl acetate was added to the residue, and the organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate and brine, and dried over anhydrous magnesium sulfate.
  • Example 13 5- [3-chloro-5-methyl-1H-1,2,4-triazol-1-yl] -4-fluoro-2-methyl-N- (2,2,2-trifluoroethyl) benzoic acid amide Preparation of (Compound No. A-2453 of the present invention) (1) 5- (3-chloro-5-methyl-1H-1,2,4-triazol-1-yl) -4-fluoro-2-methylbenzoic acid Of ethyl acetate (Compound No.
  • Formulation Example 4 Granules Compounds listed in Tables 1 to 25 and 59 to 70 5 parts Sodium salt of lauryl alcohol sulfate 2 parts Sodium lignin sulfonate 5 parts Carboxymethyl cellulose 2 parts Clay 86 parts It was mixed and ground. 20 parts of water was added to the mixture, and the mixture was kneaded, processed into granules of 14 to 32 mesh using an extrusion granulator, and dried to obtain granules.
  • Insecticidal insecticidal activity test A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm as an active ingredient. Cabbage leaves were immersed in the chemical solution, air-dried, and then placed in a plastic cup. 10 second instar larvae of the Japanese moth were released into it and covered. After that, it was placed in a constant temperature room at 25 ° C., and after 6 days, the number of dead insects was examined, and the mortality was calculated by the formula (1). The test was performed in a single system.
  • Test for insecticidal activity of brown planthoppers The wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm as an active ingredient. Rice sprouting paddy was immersed in the chemical solution and placed in a plastic cup. Ten plastic brown planthopper second-instar larvae were released into the plastic cup, and the lid was closed. After that, it was placed in a constant temperature room at 25 ° C., and after 6 days, the number of dead insects was examined, and the mortality was calculated by the formula (1). The test was performed in a single system.
  • 35 of the comparative compound (described in WO 2017/012970) showed no activity at a concentration of 500 ppm.
  • Test for controlling effects of spider mites A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm as an active ingredient. Soybean seedlings inoculated with 35 adult female spider mites were soaked in the chemical solution and air-dried. The soybean seedlings after the treatment were placed in a constant temperature room at 25 ° C., and after 13 days, the number of surviving female adult insects was examined, and the control value was calculated according to the equation (2). The test was performed in a single system.
  • 35 of the comparative compound (described in WO 2017/012970) showed no activity at a concentration of 500 ppm.
  • Test for controlling nematode activity of root-knot nematode of sweet potato The test compound was dissolved in N, N-dimethylformamide containing 1% of tween 20, and this solution was diluted with water to a concentration of 20 ppm as an active ingredient. 0.5 ml of the drug solution and 0.5 ml of a suspension containing about 30 second stage larvae of the root-knot nematode were mixed to give a concentration of 10 ppm as an active ingredient, and placed in a thermostatic chamber at 25 ° C. Five days later, the number of surviving nematodes was counted under a microscope, and the control activity of the nematodes was calculated by the formula of Equation 3. The test was performed in a two-part system.
  • 35 of the comparative compound (described in WO2017 / 012970) showed no activity at a concentration of 10 ppm.
  • the compound of the present invention represented by the general formula [I] or a salt thereof has an excellent pest control effect and is useful as an active ingredient such as an agricultural chemical or an insecticide. Further, the compound represented by the general formula [II] of the present invention and the compound represented by the general formula [III] of the present invention are useful as intermediates for producing the compound represented by the general formula [I].
  • the present invention has industrial applicability in these fields and the like.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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Abstract

Le problème à résoudre par la présente invention concerne la fourniture d'un agent de lutte contre des organismes nuisibles. L'invention concerne un dérivé d'amide d'acide 3-(1H-1,2,4-triazole-1-yl) benzoïque représenté par la formule générale [I] ou un sel acceptable sur le plan agrochimique de celui-ci, et un agent de lutte contre des organismes nuisibles caractérisé en ce qu'il comprend celui-ci en tant que composant actif (dans la formule, R1 représente un groupe alkyle en C1-C6, un groupe haloalkyle en C1-C6, un groupe cycloalkyle en C3-C6, ou similaire, R2 représente un atome d'hydrogène ou similaire, A représente un atome d'oxygène ou un atome de soufre, R3 représente un atome d'halogène, un groupe alkyle en C1-C6, ou similaire, n représente un nombre entier de 0 à 3, R4 représente un atome d'halogène, un groupe alkyle en C1-C6, ou similaire, R5 représente un groupe alkyle en C1-C6, un groupe haloalkyle en C1-C6, un groupe alcoxy en C1-C6, un groupe haloalcoxy en C1-C6, un groupe alkylthio en C1-C6, un groupe haloalkylthio en C1-C6, -NH2, -N(R12)R14, ou similaire, et R6 représente un atome d'hydrogène, un groupe alkyle en C1-C6, -NH2, -N(R12)R14, -N(R10)C(=O)R14, ou similaire).
PCT/JP2019/031563 2018-08-17 2019-08-09 Dérivé d'amide d'acide 3-(1h-1,2,4-triazole-1-yl) benzoïque et agent de lutte contre des organismes nuisibles WO2020036133A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021175822A1 (fr) 2020-03-02 2021-09-10 Syngenta Crop Protection Ag Composés amides d'acide benzoïque substitués par amidine pesticides
CN115093373A (zh) * 2022-08-24 2022-09-23 江苏省中国科学院植物研究所 一种1,5-二取代-3-氟烷基-1,2,4-三氮唑化合物及其制备方法和应用

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CN108373453A (zh) * 2018-04-03 2018-08-07 苏州大学张家港工业技术研究院 三氮唑衍生物及其制备方法

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JPH0776578A (ja) * 1992-11-12 1995-03-20 Bayer Ag 置換されたトリアゾリノン類
JPH0710843A (ja) * 1993-03-31 1995-01-13 Eisai Co Ltd 含窒素縮合複素環化合物
JPH08188563A (ja) * 1993-12-27 1996-07-23 Eisai Co Ltd アントラニル酸誘導体
WO1996016960A1 (fr) * 1994-11-30 1996-06-06 Zeneca Limited Derives quinazolines
JP2001509145A (ja) * 1996-12-23 2001-07-10 デュポン ファーマシューティカルズ カンパニー Ｘａ因子阻害剤としての窒素を含む複素環式芳香族化合物
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021175822A1 (fr) 2020-03-02 2021-09-10 Syngenta Crop Protection Ag Composés amides d'acide benzoïque substitués par amidine pesticides
CN115093373A (zh) * 2022-08-24 2022-09-23 江苏省中国科学院植物研究所 一种1,5-二取代-3-氟烷基-1,2,4-三氮唑化合物及其制备方法和应用

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