WO2020075706A1 - Pyridone compound and agricultural and horticultural fungicide having same as effective component thereof - Google Patents

Pyridone compound and agricultural and horticultural fungicide having same as effective component thereof Download PDF

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WO2020075706A1
WO2020075706A1 PCT/JP2019/039622 JP2019039622W WO2020075706A1 WO 2020075706 A1 WO2020075706 A1 WO 2020075706A1 JP 2019039622 W JP2019039622 W JP 2019039622W WO 2020075706 A1 WO2020075706 A1 WO 2020075706A1
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group
substituent
optionally substituted
formula
solvent
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PCT/JP2019/039622
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French (fr)
Japanese (ja)
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豪毅 梅谷
一樹 北嶌
健志 福元
良平 内藤
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三井化学アグロ株式会社
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Priority to JP2020551162A priority Critical patent/JP7397800B2/en
Publication of WO2020075706A1 publication Critical patent/WO2020075706A1/en

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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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • 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
    • C07D401/04—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 directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to a pyridone compound and an agrochemical containing the compound as an active ingredient.
  • Controlling diseases of agricultural and horticultural crops plays an important role in ensuring stable agricultural production. Therefore, various bactericides have been used, but new bactericides effective not only against drug-susceptible bacteria but also against drug-resistant bacteria have been earnestly desired.
  • 1,2,3,5-substituted-4-pyridone compounds are known.
  • 1,2,3,5-substituted-4-pyridone compounds having a carboxy group at the 5-position have been disclosed (for example, JP-A-53-65882 and JP-A-61-246163). Issue).
  • JP-A-53-65882 Japanese Patent Laid-Open No. 61-246163
  • JP-A-53-65882 and JP-A-61-246163 are all related to pharmaceuticals, and the technical field to which the agricultural and horticultural germicide of the present invention belongs Is different from.
  • An object of the present invention is to provide a novel pyridone compound which is effective as a fungicide for agricultural and horticultural use.
  • the present inventors have made extensive studies on a group of 1,2,3,5-substituted-4-pyridone compounds. As a result, they have found that a novel compound group in which a 5-membered heterocyclic substituent is introduced at the 1-position in the 4-pyridone skeleton exerts excellent control activity against plant diseases. Further, surprisingly, it was found that the pyridone compound group having the heterocyclic substituent has soil degradability, and it is possible to reduce the environmental load, thus completing the present invention.
  • R1 is Hydrogen atom, Cyano group, Halogen atom, A C1 to C6 alkyl group optionally substituted with a substituent A, A C1 to C6 haloalkyl group, A C3 to C8 cycloalkyl group which may be optionally substituted with a substituent A, A C2-C6 alkenyl group optionally substituted with a substituent A, A C2-C6 haloalkenyl group, A C2-C6 alkynyl group optionally substituted with a substituent A, A C2-C6 haloalkynyl group, A C1 to C6 alkoxy group optionally substituted with a substituent A, A C1 to C6 haloalkoxy group, A C3 to C8 cycloalkoxy group optionally substituted with a substituent A, A C2-C6 alkenyloxy group which may be optionally substituted with a substituent A, A C1 to C6 haloalkoxy group, A C3 to
  • R2 is Cyano group, Halogen atom, A C1 to C6 alkyl group optionally substituted with a substituent A, A C1 to C6 haloalkyl group, A C3 to C8 cycloalkyl group which may be optionally substituted with a substituent A, A C2-C6 alkenyl group optionally substituted with a substituent A, A C2-C6 haloalkenyl group, A C2-C6 alkynyl group optionally substituted with a substituent A, A C2-C6 haloalkynyl group, A C1 to C6 alkoxy group optionally substituted with a substituent A, A C1 to C6 haloalkoxy group, A C3 to C8 cycloalkoxy group optionally substituted with a substituent A, A C2-C6 alkenyloxy group which may be optionally substituted with a substituent A, A C2-C6 haloalkenyloxy group, A C3
  • Re represents an alkyl group
  • ReC ( ⁇ O) N (Rf) — wherein Re and Rf are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, C1 to C6).
  • n represents an integer of 0 to 5 (provided that when n is 2 or more, R3s are independent of each other); Z is A thienyl group which may be optionally substituted by 0 to 3 with R4 (however, in the case of 2 or more substituted R4, each is independent), A thiazolyl group which may be optionally substituted by 0 to 2 with R4 (however, in the case of R4 having 2 or more substitutions, each is independent), Thiadiazolyl group optionally substituted with R4 pyrazolyl group optionally substituted with 0 to 3 optionally with R4 (however, in the case of disubstituted R4, each is independent), Or, represents a tetrazolyl group optionally substituted by R4, R4 is Hydroxyl group, Cyano group, Nitro group, Halogen atom, A C1 to C6 alkyl group optionally substituted with a substituent C, A C1 to C6 haloalkyl group, A C
  • R1 is Hydrogen atom, Halogen atom, A C1 to C6 alkyl group optionally substituted with a substituent A, A C1 to C6 haloalkyl group, A C2-C6 alkenyl group optionally substituted with a substituent A, A C2-C6 alkynyl group optionally substituted with a substituent A, A C1 to C6 alkoxy group optionally substituted with a substituent A, A C1 to C6 haloalkoxy group, Alternatively, RgC ( ⁇ O) — (wherein, Rg represents a C1 to C6 alkyl group optionally substituted with the substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group.
  • R2 is Halogen atom, A C1 to C6 alkyl group optionally substituted with a substituent A, A C1 to C6 haloalkyl group, A C2-C6 alkenyl group optionally substituted with a substituent A, A C2-C6 alkynyl group optionally substituted with a substituent A, A C1 to C6 alkoxy group optionally substituted with a substituent A, A C1 to C6 haloalkoxy group, A C2-C6 alkenyloxy group which may be optionally substituted with a substituent A, Or represents a C3-C6 alkynyloxy group which may be optionally substituted with a substituent A;
  • X is an oxygen atom;
  • R3 is Hydroxyl group, Cyano group, Halogen atom, A C1 to C6 alkyl group optionally substituted with a substituent C, A C1 to C6 haloalkyl group, A C2-C6 alkenyl group optionallyl
  • R1 is Hydrogen atom, Halogen atom, Or represents a C1 to C6 alkyl group which may be optionally substituted with a substituent A
  • R2 is Halogen atom, A C1 to C6 alkyl group optionally substituted with a substituent A, Or represents a C1 to C6 alkoxy group which may be optionally substituted with a substituent A
  • R3 is Halogen atom, A C1 to C6 alkyl group optionally substituted with a substituent C, Or represents a C1 to C6 alkoxy group which may be optionally substituted with a substituent C
  • R4 is Halogen atom, A C1 to C6 alkyl group optionally substituted with a substituent C, A C1 to C6 haloalkyl group, Alternatively, RdC ( ⁇ O) — (wherein Rd is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent A
  • R3 is a fluorine atom, a chlorine atom, a bromine atom, a methyl group or a methoxy group.
  • R4 is chlorine atom, bromine atom, methyl group, formyl group or difluoromethyl group.
  • Z is a thienyl group which may be optionally substituted by R4 with 0 to 3 (provided that each is independent in the case of 2 or more substituted R4), and thiazolyl which is optionally substituted with R4 by R4.
  • Z represents a tetrazolyl group optionally substituted with R4.
  • Z is thiophen-3-yl group, 2-bromo-thiophen-3-yl group, 2-methyl-thiophen-3-yl group, thiazol-2-yl group, 4-bromo-5-methyl- Thiazol-2-yl group, 4-methyl-thiazol-2-yl group, 5-methyl-thiazol-2-yl group, 1,2,3-thiadiazol-5-yl group, 1,3,4-thiadiazole- 2-yl group, 5-bromo-1,3,4-thiadiazol-2-yl group, 1-methyl-pyrazol-3-yl group, 1-methyl-4-chloro-pyrazol-3-yl group, 1- Methyl-4-bromo-pyrazol-3-yl group, 1-methyl-4-methyl-pyrazol-3-yl group, 1-methyl-5-chloro-pyra
  • Z is a thiophen-3-yl group, a 2-bromo-thiophen-3-yl group, or a 2-methyl-thiophen-3-yl group. Or a salt thereof.
  • Z is a thiazol-2-yl group, a 4-bromo-5-methyl-thiazol-2-yl group, a 4-methyl-thiazol-2-yl group, or a 5-methyl-thiazol-2-yl group
  • [18] Z is a 1,2,3-thiadiazol-5-yl group, a 1,3,4-thiadiazol-2-yl group or a 5-bromo-1,3,4-thiadiazol-2-yl group A compound according to any one of [1] to [8], or a salt thereof.
  • Z is 1-methyl-pyrazol-3-yl group, 1-methyl-4-chloro-pyrazol-3-yl group, 1-methyl-4-bromo-pyrazol-3-yl group, 1-methyl -4-Methyl-pyrazol-3-yl group, 1-methyl-5-chloro-pyrazol-3-yl group, 1-methyl-5-difluoromethyl-pyrazol-3-yl group, 1-methyl-5-formyl
  • [1] to [8] which is a -pyrazol-3-yl group, a 1-methyl-pyrazol-4-yl group, or a 1-methyl-pyrazol-5-yl group, Or its salt.
  • a pesticide for agricultural and horticultural use which comprises the compound according to any one of [1] to [20] or a salt thereof as an active ingredient.
  • a method for controlling plant diseases which comprises applying the agricultural and horticultural pest control agent according to [22] to plants, plant seeds, or soil for cultivating plants.
  • a method for controlling plant diseases which comprises applying the agricultural / horticultural fungicide according to [23] to plants, plant seeds, or soil for cultivating plants.
  • DMF N, N-dimethylformamide
  • THF tetrahydrofuran
  • Me methyl group
  • Et ethyl group
  • Pr propyl group
  • Bu butyl group
  • Pent pentyl group
  • Hex hexyl group
  • Hept heptyl group
  • Oct Octyl group
  • Ac acetyl group
  • Ph phenyl group
  • Py pyridyl group
  • c cyclo
  • sec secondary
  • t tertiary
  • double bond
  • ⁇ triple bond
  • Cx to Cy means that it has x to y carbon atoms.
  • x and y represent integers, and it is understood that all integers present between x and y are also individually disclosed.
  • C1-C6 is 1, 2, 3, 4, 5, or 6 carbon atoms
  • C1-C5 is 1, 2, 3, 4, or 5 carbon atoms
  • C2-C6 is 2, 3, 4, 5, or 6 carbon atoms
  • C3-C8 is 3, 4, 5, 6, 7, or 8 carbon atoms
  • C3-C6 is 3, 4, 5 , Or 6 carbon atoms, respectively.
  • the term “may be appropriately substituted” means substituted or unsubstituted.
  • the number of substituents when the number of substituents is not specified, it indicates that the number of substituents is 1.
  • the number of substituents is designated as “optionally substituted by 0 to 5”, it is understood that all integers existing between 0 and 5 are also individually disclosed. To be done. That is, it means that the number of substituents is none, 1, 2, 3, 4, or 5 substituents.
  • substituents is none, 1, 2, 3, 4, or 5 substituents.
  • substituents in “optionally 0 to 4 substituted”, there is no substituent, and in 1, 2, 3, or 4 substituents, there is no in “optionally 0 to 3 substituted”.
  • the phrase “may be substituted with 0 to 2 as appropriate” having 1, 2, or 3 substituents means none, 1 or 2 substituents, respectively.
  • the C1 to C6 alkyl group may be linear or branched, and specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group.
  • Pentyl group isopentyl group, 1-methylbutyl group, 2-methylbutyl group, neopentyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3 -Methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group , 2,3-dimethylbutyl group, 2-ethylbutyl group, 1-isopropylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethyl Propyl group, and the like.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • C1 to C6 haloalkyl group refers to the above C1 to C6 alkyl group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent.
  • C1 to C6 haloalkyl group examples include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monochloromethyl group, a monobromomethyl group, a monoiodomethyl group, a chlorodifluoromethyl group, a bromodifluoromethyl group, and -Fluoroethyl group, 2-fluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group , Pentafluoroethyl group, 2,2,2-trichloroethyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, heptafluoropropyl group, heptafluoroisopropyl group, 2,2,2
  • C3 to C8 cycloalkyl group examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
  • the C2-C6 alkenyl group represents a linear or branched unsaturated hydrocarbon group having one or more double bonds.
  • the C2-C6 alkenyl group include vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 1-pentenyl group.
  • 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 2-methyl-1-butenyl group, 3-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4 -Hexenyl group, 5-hexenyl group, 3-methyl-2-pentenyl group, 4-methyl-3-pentenyl group and the like can be mentioned.
  • C2-C6 haloalkenyl group refers to the above-mentioned C2-C6 alkenyl group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent.
  • C2-C6 haloalkenyl group examples include 2-fluorovinyl group, 2,2-difluorovinyl group, 2,2-dichlorovinyl group, 3-fluoroallyl group, 3,3-difluoroallyl group, 3, Examples thereof include a 3-dichloroallyl group, a 4,4-difluoro-3-butenyl group, a 5,5-difluoro-4-pentenyl group, and a 6,6-difluoro-5-hexenyl group.
  • the C2-C6 alkynyl group represents a linear or branched unsaturated hydrocarbon group having one or two or more triple bonds.
  • Specific examples of the C2-C6 alkynyl group include ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group.
  • C2-C6 haloalkynyl group refers to the above-mentioned C2-C6 alkynyl group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent.
  • C2-C6 haloalkynyl group examples include 2-fluoroethynyl group, 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3,3-difluoro-1-propynyl group, 3-chloro.
  • C1 to C6 alkoxy group refers to the above C1 to C6 alkyl group bonded via an oxygen atom.
  • Specific examples of the C1 to C6 alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentyloxy group, isopentyloxy group, 1-methylbutoxy group, 2-methylbutoxy group, neopentyloxy group, 1-ethylpropyloxy group, 1,2-dimethylpropyloxy group, hexyloxy group, 1-methylpentyloxy group, 2-methylpentyloxy group , 3-methylpentyloxy group, 4-methylpentyloxy group, 1,1-dimethylbutoxy group, 2,2-dimethylbutoxy group, 3,3-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3 -Dimethylbutoxy group, 2,3-di
  • C1 to C6 haloalkoxy group refers to the above C1 to C6 alkoxy group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent.
  • Specific examples of the C1-C6 haloalkoxy group include difluoromethoxy group, trifluoromethoxy group, chlorodifluoromethoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2,2-difluoroethoxy group, 2,2,2.
  • the C3 to C8 cycloalkoxy group represents a group in which the C3 to C8 cycloalkyl group is bonded via an oxygen atom.
  • Specific examples of the C3 to C8 cycloalkoxy group include a cyclopropyloxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group and a cyclooctyloxy group.
  • C2-C6 alkenyloxy group refers to the C2-C6 alkenyl group bonded through an oxygen atom.
  • C2-C6 alkenyloxy group examples include vinyloxy group, 1-propenyloxy group, allyloxy group, 1-butenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 2-methyl-1-propenyloxy group, 1 -Pentenyloxy group, 2-pentenyloxy group, 3-pentenyloxy group, 4-pentenyloxy group, 2-methyl-1-butenyloxy group, 3-methyl-2-butenyloxy group, 1-hexenyloxy group, 2-hexenyl Examples thereof include an oxy group, a 3-hexenyloxy group, a 4-hexenyloxy group, a 5-hexenyloxy group, a 3-methyl-2-pentenyloxy group and a 4-methyl-3-pentenyloxy group.
  • C2-C6 haloalkenyloxy group refers to the above-mentioned C2-C6 alkenyloxy group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent.
  • C2-C6 haloalkenyloxy group examples include a 2-fluorovinyloxy group, a 2,2-difluorovinyloxy group, a 2,2-dichlorovinyloxy group, a 3-fluoroallyloxy group, and a 3,3-difluoro group.
  • Examples include allyloxy group, 3,3-dichloroallyloxy group, 4,4-difluoro-3-butenyloxy group, 5,5-difluoro-4-pentenyloxy group, and 6,6-difluoro-5-hexenyloxy group.
  • the C3 to C6 alkynyloxy group refers to the C2 to C6 alkynyl group in which the C3 to C6 alkynyl group is bonded via an oxygen atom.
  • Specific examples of the C3-C6 alkynyloxy group include propargyloxy group, 2-butynyloxy group, 3-butynyloxy group, 2-pentynyloxy group, 3-pentynyloxy group, 4-pentynyloxy group, 1,1. Examples thereof include a dimethyl-2-propynyloxy group, a 2-hexynyloxy group, a 3-hexynyloxy group, a 4-hexynyloxy group and a 5-hexynyloxy group.
  • the C3 to C6 haloalkynyloxy group refers to the above C3 to C6 alkynyloxy group in which a hydrogen atom is optionally substituted by one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent.
  • Specific examples of the C3-C6 haloalkynyloxy group include 1,1-difluoro-2-propynyloxy group, 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro-2-butynyloxy group.
  • the C2 to C6 alkoxyalkoxy group is one in which the hydrogen atom in the C1 to C5 alkoxy group among the above C1 to C6 alkoxy groups is optionally substituted with one or two or more C1 to C5 alkoxy groups.
  • Specific examples of the C2 to C6 alkoxyalkoxy group include methoxymethoxy group, ethoxymethoxy group, propyloxymethoxy group, isopropyloxymethoxy group, methoxyethoxy group, ethoxyethoxy group, propyloxyethoxy group, isopropyloxyethoxy group, methoxypropyl. Examples thereof include an oxy group, an ethoxypropyloxy group, a propyloxypropyloxy group and an isopropyloxypropyloxy group.
  • the pyridone compound of the present invention includes a compound represented by the following formula (1) and a salt thereof. (Hereinafter, also referred to as "the compound of the present invention”.)
  • R1 in the formula (1) is optionally substituted with a hydrogen atom, a cyano group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, or a substituent A.
  • C3 to C8 cycloalkyl group C2 to C6 alkenyl group optionally substituted with substituent A, C2 to C6 haloalkenyl group, C2 to C6 alkynyl optionally substituted with substituent A Group, C2-C6 haloalkynyl group, C1-C6 alkoxy group optionally substituted with substituent A, C1-C6 haloalkoxy group, C3-C8 cyclo group optionally substituted with substituent A Alkoxy group, C2-C6 alkenyloxy group optionally substituted with substituent A, C2-C6 haloalkenyloxy group, C3-C6 alkynyl optionally substituted with substituent A Alkoxy group, a halo alkynyloxy group C3 ⁇ C6, Rc-L- (wherein, Rc represents a haloalkyl group of alkyl or C1 ⁇ C6 of C1 ⁇ C6, L is S, SO, or SO 2
  • R1 is a hydrogen atom, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, a C2 to C6 alkenyl group optionally substituted with a substituent A , A C2 to C6 alkynyl group optionally substituted with a substituent A, a C1 to C6 alkoxy group optionally substituted with a substituent A, a C1 to C6 haloalkoxy group, or RgC ( ⁇ O) — (Wherein Rg has the same meaning as above), Particularly, R1 is preferably a hydrogen atom, a halogen atom, or a C1 to C6 alkyl group which may be appropriately substituted with a substituent A.
  • R1 in the formula (1) includes a hydrogen atom and a cyano group.
  • the halogen atom in R1 of the formula (1) has the same meaning as defined above, preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a chlorine atom or a bromine atom.
  • the C1 to C6 alkyl group of the “C1 to C6 alkyl group optionally substituted with the substituent A” in R1 of the formula (1) has the same meaning as defined above, and is preferably a methyl group or an ethyl group.
  • the hydrogen atom in the C1-C6 alkyl group is optionally substituted by the substituent A.
  • the “C1-C6 haloalkyl group” for R1 in formula (1) has the same meaning as defined above, and is preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, 2,2,2. -Trifluoroethyl group, 3,3-difluoropropyl group, or 3,3,3-trifluoropropyl group, and more preferably difluoromethyl group or trifluoromethyl group.
  • the C3 to C8 cycloalkyl group of the "C3 to C8 cycloalkyl group optionally substituted with the substituent A" in R1 of the formula (1) has the same meaning as defined above, and preferably a cyclopropyl group. , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group.
  • the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent A.
  • the C2-C6 alkenyl group of the "C2-C6 alkenyl group optionally substituted with the substituent A" in R1 of the formula (1) has the same meaning as defined above, preferably a vinyl group, 1- A propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, or a 3-butenyl group is more preferable, and a vinyl group, a 1-propenyl group, or an allyl group is more preferable.
  • the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent A.
  • the “C2-C6 haloalkenyl group” for R 1 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group, a 2,2-dichlorovinyl group. , 3-fluoroallyl group, 3,3-difluoroallyl group, or 3,3-dichloroallyl group, and more preferably 2-fluorovinyl group or 2,2-difluorovinyl group.
  • the C2-C6 alkynyl group of the "C2-C6 alkynyl group optionally substituted with the substituent A" in R1 of the formula (1) has the same meaning as defined above, preferably an ethynyl group, 1- A propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group is more preferable, and an ethynyl group, a 1-propynyl group, or a propargyl group is more preferable.
  • the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent A.
  • C2-C6 haloalkynyl group in R1 of the formula (1) has the same meaning as defined above, and is preferably a 3,3-difluoro-1-propynyl group or 3,3,3-trifluoro-1.
  • the C1 to C6 alkoxy group of the “C1 to C6 alkoxy group optionally substituted by the substituent A” in R1 of the formula (1) has the same meaning as defined above, and preferably a methoxy group or an ethoxy group. , A propyloxy group, or an isopropyloxy group, and more preferably a methoxy group or an ethoxy group.
  • the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent A.
  • the "C1-C6 haloalkoxy group" in R1 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2,2. 2-trifluoroethoxy group, 3,3-difluoropropyloxy group or 3,3,3-trifluoropropyloxy group, more preferably difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group Or a 2,2,2-trifluoroethoxy group.
  • the C3 to C8 cycloalkoxy group of the "C3 to C8 cycloalkoxy group optionally substituted by the substituent A" in R1 of the formula (1) has the same meaning as defined above, and preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group.
  • the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted by the substituent A.
  • the C2-C6 alkenyloxy group of the "C2-C6 alkenyloxy group optionally substituted with the substituent A" in R1 of the formula (1) has the same meaning as defined above, and preferably a vinyloxy group, It is a 1-propenyloxy group, an allyloxy group, a 1-butenyloxy group, a 2-butenyloxy group or a 3-butenyloxy group, more preferably a vinyloxy group, a 1-propenyloxy group or an allyloxy group.
  • the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent A.
  • the “C2-C6 haloalkenyloxy group” for R 1 in formula (1) has the same meaning as defined above, and is preferably 2-fluorovinyloxy group, 2,2-difluorovinyloxy group, 2,2- A dichlorovinyloxy group, a 3-fluoroallyloxy group, a 3,3-difluoroallyloxy group, or a 3,3-dichloroallyloxy group, more preferably a 2-fluorovinyloxy group or a 2,2-difluoro group. It is a vinyloxy group.
  • the C3-C6 alkynyloxy group of the "C3-C6 alkynyloxy group optionally substituted by the substituent A" in R1 of the formula (1) has the same meaning as defined above, and preferably a propargyloxy group. , 2-butynyloxy group, or 3-butynyloxy group, and more preferably propargyloxy group.
  • the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent A.
  • the "C3-C6 haloalkynyloxy group" in R1 of the formula (1) has the same meaning as defined above, and is preferably a 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro group.
  • Rc-L - in R1 of formula (1) (wherein, Rc represents a haloalkyl group of alkyl or C1 ⁇ C6 of C1 ⁇ C6, L represents S, SO, or SO 2.)
  • Rc represents a haloalkyl group of alkyl or C1 ⁇ C6 of C1 ⁇ C6, L represents S, SO, or SO 2.
  • Rc-L- is preferably a methylthio group, a methanesulfinyl group, a methanesulfonyl group, an ethylthio group, an ethanesulfinyl group, an ethanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, or a trifluoromethanesulfonyl group.
  • a methylthio group, a methanesulfinyl group, or a methanesulfonyl group is preferably a methylthio group, a methanesulfinyl group, or a methanesulfonyl group.
  • RgC ( ⁇ O) — in R1 of the formula (1) (wherein Rg is a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or C3 to C8) Represents a cycloalkyl group of) and has the same meaning as defined above.
  • Rg is a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or C3 to C8
  • C1 to C6 alkyl group optionally substituted with the substituent B in the case of having the substituent B, the hydrogen atom in the C1 to C6 alkyl group is optionally substituted with the substituent B.
  • RgC ( ⁇ O) — is preferably an acetyl group, a methoxyacetyl group, a cyanoacetyl group, a propionyl group, a difluoroacetyl group, a trifluoroacetyl group, or a cyclopropanecarbonyl group, more preferably an acetyl group. Or a propionyl group.
  • R2 in the formula (1) is a cyano group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, or a C3 optionally substituted with a substituent A.
  • R2 is a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, a C2 to C6 alkenyl group optionally substituted with a substituent A, a substituent C2 to C6 alkynyl group optionally substituted with A, C1 to C6 alkoxy group optionally substituted with substituent A, C1 to C6 haloalkoxy group, optionally substituted with substituent A
  • R2 is preferably a halogen atom, a C1-C6 alkyl group which may be optionally substituted with a substituent A, or a C1-C6 alkoxy group which is optionally substituted with a substituent A.
  • R2 in formula (1) includes a cyano group.
  • the halogen atom in R2 of the formula (1) has the same meaning as defined above, preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a chlorine atom or a bromine atom.
  • the C1 to C6 alkyl group of the “C1 to C6 alkyl group optionally substituted with the substituent A” in R2 of the formula (1) has the same meaning as defined above, and preferably a methyl group or an ethyl group.
  • the hydrogen atom in the C1-C6 alkyl group is optionally substituted by the substituent A.
  • the “C1-C6 haloalkyl group” in R2 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, 2,2,2.
  • the C3 to C8 cycloalkyl group of the "C3 to C8 cycloalkyl group optionally substituted with the substituent A" in R2 of the formula (1) has the same meaning as defined above, and is preferably a cyclopropyl group. , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group.
  • the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent A.
  • the C2-C6 alkenyl group in the "C2-C6 alkenyl group optionally substituted by the substituent A" in R2 of the formula (1) has the same meaning as defined above, preferably a vinyl group, 1- A propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, or a 3-butenyl group is more preferable, and a vinyl group, a 1-propenyl group, or an allyl group is more preferable.
  • the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent A.
  • C2-C6 haloalkenyl group for R2 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group, a 2,2-dichlorovinyl group. , 3-fluoroallyl group, 3,3-difluoroallyl group, or 3,3-dichloroallyl group, and more preferably 2-fluorovinyl group or 2,2-difluorovinyl group.
  • the C2-C6 alkynyl group of the "C2-C6 alkynyl group optionally substituted with the substituent A" in R2 of the formula (1) has the same meaning as defined above, preferably an ethynyl group, 1- A propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group is more preferable, and an ethynyl group, a 1-propynyl group, or a propargyl group is more preferable.
  • the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent A.
  • C2-C6 haloalkynyl group in R2 of the formula (1) has the same meaning as defined above, and is preferably a 3,3-difluoro-1-propynyl group or 3,3,3-trifluoro-1.
  • the C1 to C6 alkoxy group of the “C1 to C6 alkoxy group optionally substituted by the substituent A” in R2 of the formula (1) has the same meaning as defined above, and preferably a methoxy group or an ethoxy group. , A propyloxy group, or an isopropyloxy group, and more preferably a methoxy group, an ethoxy group, or a propyloxy group.
  • the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent A.
  • the "C1-C6 haloalkoxy group" in R2 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2,2. 2-trifluoroethoxy group, 3,3-difluoropropyloxy group or 3,3,3-trifluoropropyloxy group, more preferably difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group Or a 2,2,2-trifluoroethoxy group.
  • the C3 to C8 cycloalkoxy group of the "C3 to C8 cycloalkoxy group optionally substituted with the substituent A" in R2 of the formula (1) has the same meaning as defined above, and preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group.
  • the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted by the substituent A.
  • the C2-C6 alkenyloxy group in the "C2-C6 alkenyloxy group optionally substituted with the substituent A" in R2 of the formula (1) has the same meaning as defined above, and preferably a vinyloxy group, It is a 1-propenyloxy group, an allyloxy group, a 1-butenyloxy group, a 2-butenyloxy group or a 3-butenyloxy group, more preferably a vinyloxy group, a 1-propenyloxy group or an allyloxy group.
  • the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent A.
  • the “C2-C6 haloalkenyloxy group” in R2 of the formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyloxy group, a 2,2-difluorovinyloxy group or a 2,2- A dichlorovinyloxy group, a 3-fluoroallyloxy group, a 3,3-difluoroallyloxy group, or a 3,3-dichloroallyloxy group, more preferably a 2-fluorovinyloxy group or a 2,2-difluoro group. It is a vinyloxy group.
  • the C3-C6 alkynyloxy group of the "C3-C6 alkynyloxy group optionally substituted by the substituent A" in R2 of the formula (1) has the same meaning as defined above, and preferably a propargyloxy group. , 2-butynyloxy group, or 3-butynyloxy group, and more preferably propargyloxy group.
  • the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent A.
  • the “C3-C6 haloalkynyloxy group” in R2 of the formula (1) has the same meaning as defined above, and is preferably 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro group.
  • Rc and L of "Rc-L-" in R2 of the formula (1) have the same meaning as above.
  • "Rc-L-” is preferably a methylthio group, a methanesulfinyl group, a methanesulfonyl group, an ethylthio group, an ethanesulfinyl group, an ethanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, or a trifluoromethanesulfonyl group.
  • a methylthio group a methanesulfinyl group, or a methanesulfonyl group.
  • “RgC ( ⁇ O) —” is preferably an acetyl group, a methoxyacetyl group, a cyanoacetyl group, a propionyl group, a difluoroacetyl group, a trifluoroacetyl group, or a cyclopropanecarbonyl group, more preferably an acetyl group. Or a propionyl group.
  • X in the formula (1) is an oxygen atom or a sulfur atom, preferably an oxygen atom.
  • R3 in the formula (1) is appropriately substituted with a hydroxyl group, a cyano group, a nitro group, a halogen atom, a C1 to C6 alkyl group which may be optionally substituted with a substituent C, a C1 to C6 haloalkyl group, and a substituent C.
  • a quinyloxy group, a C3-C6 haloalkynyloxy group, RdC ( O)-(wherein Rd is a hydrogen atom, a C1-C6 alkyl group optionally substituted with a substituent B, a C1-C6 haloalkyl group Group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, or a C3 to C8 cycloalkoxy group), RdC ( ⁇ O) O— (wherein Rd Is as defined above, Rc-L- (wherein Rc and L are as defined above), RaRbN- (wherein Ra and Rb are each independently hydrogen atom).
  • Re and Rf are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, C1 To C6 alkoxy group, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group, or RaRbN- (wherein Ra and Rb are as defined above).
  • R3 is a hydroxyl group, a cyano group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, or a C2 to C6 optionally substituted with a substituent C.
  • R3 is preferably a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, or a C1 to C6 alkoxy group optionally substituted with a substituent C.
  • R3 in the formula (1) includes a hydroxyl group, a cyano group, and a nitro group.
  • the halogen atom in R3 of formula (1) has the same meaning as defined above, and is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • the C1 to C6 alkyl group of the “C1 to C6 alkyl group optionally substituted with a substituent C” in R3 of the formula (1) has the same meaning as defined above, and preferably a methyl group or an ethyl group.
  • the hydrogen atom in the C1 to C6 alkyl group is optionally substituted by the substituent C.
  • the “C1-C6 haloalkyl group” for R3 in formula (1) has the same meaning as defined above, and is preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, 2,2,2. -A trifluoroethyl group, a 3,3-difluoropropyl group, or a 3,3,3-trifluoropropyl group, more preferably a difluoromethyl group or a trifluoromethyl group.
  • the C3 to C8 cycloalkyl group of the "C3 to C8 cycloalkyl group optionally substituted by the substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably a cyclopropyl group. , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group.
  • the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent C.
  • the C2-C6 alkenyl group in the "C2-C6 alkenyl group optionally substituted with a substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably a vinyl group, 1- A propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, or a 3-butenyl group is more preferable, and a vinyl group, a 1-propenyl group, or an allyl group is more preferable.
  • the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent C.
  • the “C2-C6 haloalkenyl group” for R3 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group or a 2,2-dichlorovinyl group. , 3-fluoroallyl group, 3,3-difluoroallyl group, or 3,3-dichloroallyl group, and more preferably 2-fluorovinyl group or 2,2-difluorovinyl group.
  • the C2-C6 alkynyl group of the "C2-C6 alkynyl group optionally substituted by the substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably an ethynyl group, 1- A propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group is more preferable, and an ethynyl group, a 1-propynyl group, or a propargyl group is more preferable.
  • the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent C.
  • C2-C6 haloalkynyl group in R3 of the formula (1) has the same meaning as defined above, and is preferably a 3,3-difluoro-1-propynyl group or a 3,3,3-trifluoro-1 group.
  • the C1 to C6 alkoxy group of the "C1 to C6 alkoxy group optionally substituted with a substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably a methoxy group or an ethoxy group.
  • the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent C.
  • the “C1-C6 haloalkoxy group” in R3 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2,2. 2-trifluoroethoxy group, 3,3-difluoropropyloxy group or 3,3,3-trifluoropropyloxy group, more preferably difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group Or a 2,2,2-trifluoroethoxy group.
  • the C3 to C8 cycloalkoxy group of the "C3 to C8 cycloalkoxy group optionally substituted with a substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group.
  • the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted by the substituent C.
  • the C2-C6 alkenyloxy group of the "C2-C6 alkenyloxy group optionally substituted with a substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably a vinyloxy group, It is a 1-propenyloxy group, an allyloxy group, a 1-butenyloxy group, a 2-butenyloxy group or a 3-butenyloxy group, more preferably a vinyloxy group, a 1-propenyloxy group or an allyloxy group.
  • the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent C.
  • the “C2-C6 haloalkenyloxy group” for R3 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyloxy group, a 2,2-difluorovinyloxy group, or a 2,2- A dichlorovinyloxy group, a 3-fluoroallyloxy group, a 3,3-difluoroallyloxy group, or a 3,3-dichloroallyloxy group, more preferably a 2-fluorovinyloxy group or a 2,2-difluoro group. It is a vinyloxy group.
  • the C3 to C6 alkynyloxy group of the "C3 to C6 alkynyloxy group optionally substituted with a substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably a propargyloxy group.
  • the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent C.
  • C3-C6 haloalkynyloxy group for R3 in formula (1) has the same meaning as defined above, and is preferably a 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro group.
  • RdC O-in R3 of the formula (1) (wherein Rd is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, C3 to C8 Represents a cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, or a C3 to C8 cycloalkoxy group).)
  • Rd is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, C3 to C8 Represents a cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, or a C3 to C8 cycloalkoxy group).
  • RdC ( ⁇ O) — is preferably acetyl group, methoxyacetyl group, cyanoacetyl group, propionyl group, difluoroacetyl group, trifluoroacetyl group, cyclopropanecarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, 2 , 2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 3,3,3-trifluoropropyloxycarbonyl group, or cyclopropyloxycarbonyl group, more preferably acetyl group, methoxy It is an acetyl group, a cyanoacetyl group, a methoxy
  • Rc and L of "Rc-L-" in R3 of the formula (1) have the same meaning as above.
  • "Rc-L-” is preferably a methylthio group, a methanesulfinyl group, a methanesulfonyl group, an ethylthio group, an ethanesulfinyl group, an ethanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, or a trifluoromethanesulfonyl group.
  • a methylthio group a methanesulfinyl group, or a methanesulfonyl group.
  • Ra and RbN— are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6
  • Rb are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6
  • haloalkyl group or C3 to C8 cycloalkyl group has the same meaning as defined above.
  • RaRbN- is preferably an amino group, a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a (methoxymethyl) amino group, a (2-methoxyethyl) amino group, a (cyanomethyl) amino group, (2-Cyanoethyl) amino group, dimethylamino group, ethyl (methyl) amino group, methyl (propyl) amino group, isopropyl (methyl) amino group, (methoxymethyl) methylamino group, (2-methoxyethyl) methylamino group , (Cyanomethyl) methylamino group, (2-cyanoethyl) methylamino group, diethylamino group, ethyl (propyl) amino group, ethyl (isopropyl) amino group, ethyl (methoxymethyl) amino group, e
  • ReC ( ⁇ O) N (Rf) — in R3 of the formula (1) (wherein Re and Rf are independent of each other, and are a hydrogen atom or C1 to C6 optionally substituted with a substituent B).
  • Ethoxycarbonylamino group methoxycarbonyl (methyl) amino group, ethoxycarbonyl (methyl) amino group, methoxycarbonyl (ethyl) amino group, ethoxycarbonyl (ethyl) amino group, methoxycarbonyl (methoxy) amino group, ethoxycarbonyl (methoxy ) Amino group, methoxycarbonyl (ethoxy) amino group, or ethoxycarbonyl (ethoxy) amino group.
  • N in the formula (1) represents an integer of 0 to 5. At this time, all integers existing between 0 and 5 are individually disclosed. That is, n means 0, 1, 2, 3, 4, or 5. Further, when n is 2 or more, two or more substituted R3's each independently represent a substituent, which may be the same or different and can be arbitrarily selected.
  • Z in the formula (1) is a thienyl group which may be optionally substituted by 0 to 3 with R4 (however, in the case of 2 or more substituted R4, each is independent), and is appropriately substituted with 0 to 2 by R4.
  • Z is a thienyl group which may be appropriately substituted by R4 with 0 to 3 (provided that each is independent in the case of R4 having 2 or more substitutions), and a thiazolyl group which is optionally substituted with 0 to 2 by R4 ( However, in the case of 2-substituted or more R4, each is
  • nA represents an integer of 0, 1, 2, or 3, and when nA is 2 or more, R4s of 2 or more each independently represent a substituent. , May be the same or different, and can be arbitrarily selected.
  • the “thiazolyl group optionally substituted with 0 to 2 at R4” in Z of the formula (1) (however, in the case of disubstituted R4, each is independent) is represented by the formula (B-1), the formula ( B-2) or a partial structure represented by the formula (B-3) shown below.
  • nB represents an integer of 0, 1, or 2, and when nB is 2, the 2-substituted R4s are independent of each other. It represents a substituent and may be the same or different and can be arbitrarily selected.
  • the “thiadiazolyl group optionally substituted with R4” in Z in the formula (1) means the formula (C-1), the formula (C-2), the formula (C-3), the formula (C-4) and the formula (C-4) (C-5) or a partial structure represented by the formula (C-6) shown below.
  • nC is 0 or 1. Represents an integer.
  • the “pyrazolyl group which may be optionally substituted with 0 to 3 by R4” in Z of the formula (1) (however, in the case of disubstituted R4, each is independent) is represented by the formula (D-1), the formula ( D-2), the formula (D-3), the formula (D-4), the formula (D-5), or the formula (D-6) represents a partial structure shown below.
  • nD is 0, 1, Alternatively, it represents an integer of 2.
  • 2-substituted R4's each represent an independent substituent, which may be the same or different and can be arbitrarily selected.
  • the “tetrazolyl group optionally substituted with R4” in Z of the formula (1) means the formula (E-1), the formula (E-2), the formula (E-3), the formula (E-4) and the formula (E-4) It represents the partial structure shown below represented by formula (E-5) or formula (E-6).
  • R4 in the formula (1) is appropriately substituted with a hydroxyl group, a cyano group, a nitro group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, and a substituent C.
  • R4 is a hydroxyl group, a cyano group, a nitro group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, or a C2 optionally substituted with a substituent C.
  • R4 is a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, or RdC ( ⁇ O) — (wherein Rd is as defined above). Yes) is preferred.
  • R4 is preferably a halogen atom or a C1 to C6 alkyl group which may be optionally substituted with a substituent C, when Z represents "a thienyl group which may be optionally substituted with R4 from 0 to 3",
  • Z represents a “thiazolyl group which may be optionally substituted by R4 for 0 to 2”
  • a halogen atom or a C1 to C6 alkyl group which may be optionally substituted by a substituent C is preferable
  • Z is “R4 Is a halogen atom
  • Z represents a "pyrazolyl group optionally substituted with 0 to 3 at R4", a halogen atom or a substituent C
  • a C1 to C6 alkyl group optionally substituted with or a C1 to C6 haloalkyl group when Z represents a "tetrazolyl group optionally substituted with R4", it is optionally substituted with a substituent C.
  • R4 in the formula (1) includes a hydroxyl group, a cyano group, and a nitro group.
  • the halogen atom in R4 of the formula (1) has the same meaning as defined above, and is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • the C1 to C6 alkyl group in the "C1 to C6 alkyl group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and is preferably a methyl group or an ethyl group.
  • the hydrogen atom in the C1 to C6 alkyl group is optionally substituted by the substituent C.
  • the “C1-C6 haloalkyl group” for R4 in formula (1) has the same meaning as defined above, and is preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, 2,2,2. -Trifluoroethyl group, 3,3-difluoropropyl group, or 3,3,3-trifluoropropyl group, and more preferably difluoromethyl group or trifluoromethyl group.
  • the C3 to C8 cycloalkyl group of the "C3 to C8 cycloalkyl group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably a cyclopropyl group. , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group.
  • the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent C.
  • the C2-C6 alkenyl group of the "C2-C6 alkenyl group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably a vinyl group, 1- A propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, or a 3-butenyl group is more preferable, and a vinyl group, a 1-propenyl group, or an allyl group is more preferable.
  • the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent C.
  • the “C2-C6 haloalkenyl group” for R4 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group, a 2,2-dichlorovinyl group. , 3-fluoroallyl group, 3,3-difluoroallyl group, or 3,3-dichloroallyl group, and more preferably 2-fluorovinyl group or 2,2-difluorovinyl group.
  • the C2-C6 alkynyl group of the "C2-C6 alkynyl group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, preferably an ethynyl group, 1- A propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group is more preferable, and an ethynyl group, a 1-propynyl group, or a propargyl group is more preferable.
  • the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent C.
  • C2-C6 haloalkynyl group in R4 of the formula (1) has the same meaning as defined above, and is preferably a 3,3-difluoro-1-propynyl group or a 3,3,3-trifluoro-1 group.
  • the C1 to C6 alkoxy group of the "C1 to C6 alkoxy group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably a methoxy group or an ethoxy group.
  • the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent C.
  • the “C1-C6 haloalkoxy group” in R4 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2, 2-trifluoroethoxy group, 3,3-difluoropropyloxy group or 3,3,3-trifluoropropyloxy group, more preferably difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group Or a 2,2,2-trifluoroethoxy group.
  • the C3 to C8 cycloalkoxy group of the "C3 to C8 cycloalkoxy group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group.
  • the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted by the substituent C.
  • the C2-C6 alkenyloxy group of the "C2-C6 alkenyloxy group optionally substituted by the substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably a vinyloxy group, It is a 1-propenyloxy group, an allyloxy group, a 1-butenyloxy group, a 2-butenyloxy group or a 3-butenyloxy group, more preferably a vinyloxy group, a 1-propenyloxy group or an allyloxy group.
  • the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent C.
  • the “C2-C6 haloalkenyloxy group” for R4 in formula (1) has the same meaning as defined above, and is preferably 2-fluorovinyloxy group, 2,2-difluorovinyloxy group, 2,2- A dichlorovinyloxy group, a 3-fluoroallyloxy group, a 3,3-difluoroallyloxy group, or a 3,3-dichloroallyloxy group, more preferably a 2-fluorovinyloxy group or a 2,2-difluoro group. It is a vinyloxy group.
  • the C3 to C6 alkynyloxy group of the "C3 to C6 alkynyloxy group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably a propargyloxy group.
  • the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent C.
  • the “C3-C6 haloalkynyloxy group” for R4 in formula (1) has the same meaning as defined above, and is preferably a 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro group.
  • Rd is preferably a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, or a C1 to C6 haloalkyl group, more preferably a hydrogen atom or a substituent B as appropriate.
  • C1 to C6 alkyl groups which may be included.
  • RdC ( ⁇ O) — is preferably formyl group, acetyl group, methoxyacetyl group, cyanoacetyl group, propionyl group, difluoroacetyl group, trifluoroacetyl group, cyclopropanecarbonyl group, methoxycarbonyl group, ethoxycarbonyl.
  • “RdC ( ⁇ O) O—” is preferably formyloxy group, acetyloxy group, methoxyacetyloxy group, cyanoacetyloxy group, propionyloxy group, difluoroacetyloxy group, trifluoroacetyloxy group, cyclopropanecarbonyl.
  • Oxy group methoxycarbonyloxy group, ethoxycarbonyloxy group, 2,2-difluoroethoxycarbonyloxy group, 2,2,2-trifluoroethoxycarbonyloxy group, 3,3,3-trifluoropropyloxycarbonyloxy group, Alternatively, it is a cyclopropyloxycarbonyloxy group, more preferably a formyloxy group, or an acetyloxy group.
  • Rc and L of "Rc-L-" in R4 of the formula (1) have the same meaning as above.
  • "Rc-L-” is preferably a methylthio group, a methanesulfinyl group, a methanesulfonyl group, an ethylthio group, an ethanesulfinyl group, an ethanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, or a trifluoromethanesulfonyl group.
  • a methylthio group a methanesulfinyl group, or a methanesulfonyl group.
  • Ra and Rb of "RaRbN-" in R4 of the formula (1) are as defined above.
  • "RaRbN-" is preferably an amino group, a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a (methoxymethyl) amino group, a (2-methoxyethyl) amino group, a (cyanomethyl) amino group, (2-Cyanoethyl) amino group, dimethylamino group, ethyl (methyl) amino group, methyl (propyl) amino group, isopropyl (methyl) amino group, (methoxymethyl) methylamino group, (2-methoxyethyl) methylamino group , (Cyanomethyl) methylamino group, (2-cyanoethyl) methylamino group, diethylamino group, ethyl (propyl) amino group, eth
  • Ethoxycarbonylamino group methoxycarbonyl (methyl) amino group, ethoxycarbonyl (methyl) amino group, methoxycarbonyl (ethyl) amino group, ethoxycarbonyl (ethyl) amino group, methoxycarbonyl (methoxy) amino group, ethoxycarbonyl (methoxy ) Amino group, methoxycarbonyl (ethoxy) amino group, or ethoxycarbonyl (ethoxy) amino group.
  • the “substituent A” in the formula (1) means a hydroxyl group, a cyano group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, a C3 to C8 cycloalkoxy group, RaRbN. -(Wherein Ra and Rb have the same meanings as described above) and Rc-L- (wherein Rc and L have the same meanings as described above), and at least one member selected from the group consisting of: ..
  • the substituent A is preferably a cyano group, a C1-C6 alkoxy group or Rc-L- (wherein Rc and L have the same meanings as described above), Particularly, a cyano group or a C1-C6 alkoxy group is preferable.
  • substituent A a hydroxyl group; Cyano group; As a C3-C8 cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; A methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group as the C1 to C6 alkoxy group; As the C1 to C6 haloalkoxy group, difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 3,3-difluoropropyloxy group, and 3,3 , 3-trifluoropropyloxy group; As a C3-C8 cycloalkoxy group, a cyclopropyloxy group, a cyclobutoxy group, a cyclopentyloxy group, and
  • substituent A a hydroxyl group; Cyano group; As a C3 to C8 cycloalkyl group, a cyclopropyl group and a cyclobutyl group; As a C1-C6 alkoxy group, a methoxy group and an ethoxy group; As a C1-C6 haloalkoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, and a 2,2,2-trifluoroethoxy group; As a C3-C8 cycloalkoxy group, a cyclopropyloxy group and a cyclobutoxy group; RaRbN- (wherein Ra and Rb have the same meanings as defined above), as a dimethylamino group, an ethyl (methyl) amino group, and a diethylamino group; Further, examples of Rc-L- (wherein Rc
  • the “substituent B” in the formula (1) represents at least one selected from the group consisting of a cyano group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, and a C3 to C8 cycloalkoxy group. .
  • the substituent B is preferably a cyano group or a C1-C6 alkoxy group.
  • Each term of the substituent B has the same meaning as defined above.
  • substituent B a cyano group
  • As the C1 to C6 haloalkoxy group difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 3,3-difluoropropyloxy group, and 3,3 , 3-trifluoropropyloxy group
  • Examples of the C3 to C8 cycloalkoxy group include a cyclopropyloxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.
  • substituent B a cyano group; As a C1-C6 alkoxy group, a methoxy group and an ethoxy group; As a C1-C6 haloalkoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, and a 2,2,2-trifluoroethoxy group; Also, examples of the C3-C8 cycloalkoxy group include a cyclopropyloxy group and a cyclobutoxy group.
  • substituted C in the formula (1) means a hydroxyl group, a cyano group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, C2.
  • RaRbN- wherein Ra and Rb are as defined above
  • Rc-L- wherein Rc and L are as defined above
  • RdC ( ⁇ O) — wherein Rd has the same meaning as defined above
  • a cyano group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, Rc-L- (wherein Rc and L have the same meanings as described above), or RdC ( O)-(here.
  • Rd has the same meaning as above.) Is preferred.
  • substituent C a hydroxyl group; Cyano group; As a C3-C8 cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; A methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, and a t-butoxy group as the C1 to C6 alkoxy group; As the C1 to C6 haloalkoxy group, difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 3,3-difluoropropyloxy group, and 3,3 , 3-trifluoropropyloxy group; As a C3-C8 cycloalkoxy group, a cyclopropyloxy group
  • RdC ( O)-(wherein Rd has the same meaning as above), such as formyl group, acetyl group, methoxyacetyl group, cyanoacetyl group, propionyl group, difluoroacetyl group, trifluoroacetyl group, cyclo Propanecarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 3,3,3-trifluoropropyloxycarbonyl group, and cyclopropyloxy A carbonyl group may be mentioned.
  • substituent C a hydroxyl group; Cyano group; As a C3 to C8 cycloalkyl group, a cyclopentyl group and a cyclohexyl group; A methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group as the C1 to C6 alkoxy group; As a C1 to C6 haloalkoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, a 2,2,2-trifluoroethoxy group; As a C3-C8 cycloalkoxy group, a cyclopropyloxy group, a cyclobutoxy group; As a C2-C6 alkoxyalkoxy group, a methoxymethoxy group, an ethoxymethoxy group, a methoxyethoxy group, and an ethoxyeth
  • the compound represented by the formula (1) may have axial asymmetry.
  • the isomer ratio at this time is a single ratio or a mixing ratio of an arbitrary ratio, and is not particularly limited.
  • the compound represented by the formula (1) may contain an asymmetric atom.
  • the isomer ratio at this time is a single ratio or a mixing ratio of an arbitrary ratio, and is not particularly limited.
  • the compound represented by the formula (1) may include geometrical isomers.
  • the isomer ratio at this time is a single ratio or a mixing ratio of an arbitrary ratio, and is not particularly limited.
  • the compound represented by the formula (1) may be capable of forming a salt.
  • Acid salts such as hydrochloric acid, sulfuric acid, acetic acid, fumaric acid, and maleic acid, and metal salts such as sodium, potassium, and calcium are exemplified, but are not particularly limited as long as they can be used as agricultural and horticultural fungicides. There is no.
  • a specific compound of the present invention is represented by a combination of the structural formula shown in Table 1, the substituent (R3) on the phenyl group shown in Table 2, and Z shown in Table 3.
  • X in Table 1 represents an oxygen atom or a sulfur atom
  • Ph represents the following partial structure.
  • the method for producing the compound represented by the formula (1) is illustrated below.
  • the method for producing the compound of the present invention is not limited to the production methods A to AC.
  • R1a represents a halogen atom
  • HalR represents a halogenating agent
  • R3, X, Z and n have the same meanings as described above.
  • Production method A is a method of obtaining a production intermediate represented by formula (2b), and includes a method of reacting the compound represented by formula (2a) with a halogenating agent (HalR) in a solvent. It is a manufacturing method.
  • a halogenating agent HalR
  • selectrofluor N-fluoro-N'-triethylenediamine bis (tetrafluoroborate)
  • N-chlorosuccinimide N-bromosuccinimide
  • N-iodosuccinimide 1 , 3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, bromine, iodine and the like.
  • the amount of the halogenating agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (2a). It is 1 equivalent or more and 20 equivalents or less.
  • the amount of the halogenating agent containing hydantoin is not particularly limited as long as the intended reaction proceeds, as long as it is 0.5 equivalent or more, and is usually 1 equivalent or more and 10 equivalents or less.
  • the halogenating agent used in this reaction is an iodizing agent
  • inorganic acids such as hydrochloric acid and sulfuric acid
  • acids such as organic acids
  • acetic acid, trifluoroacetic acid, methanesulfonic acid and trifluoromethanesulfonic acid you can
  • the desired reaction proceeds.
  • the amount is not particularly limited as long as it is, but is usually 0.1 equivalent or more and 3 equivalents or less.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but acidic solvents such as sulfuric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, diethyl ether, etc. , Ether solvents such as diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran and dioxane, alcohol solvents such as methanol, ethanol and isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene.
  • acidic solvents such as sulfuric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, diethyl ether, etc.
  • Ether solvents such as diisopropyl
  • Ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitrile solvents such as acetonitrile, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide 1,3-dimethyl-2-urea-based solvent-imidazolidinone, dichloromethane, dichloroethane, chloroform, and halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less by weight with respect to the compound represented by the formula (2a). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
  • the water content of the reaction mixture containing the compound represented by the formula (2b) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (2b) obtained above can be distilled under reduced pressure to remove the solvent.
  • reaction mixture containing the compound represented by the formula (2b) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • Ox represents an oxidizing agent
  • R2a represents a hydrogen atom, a cyano group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, or a substituent A.
  • Production method B is a method for obtaining a compound represented by formula (1a), which comprises reacting the compound represented by formula (2c) with an oxidizing agent (Ox) in a solvent. is there.
  • oxidizing agent used in this reaction examples include peracids such as potassium peroxodisulfate, IBX (2-iodoxybenzoic acid), DMP (1,1,1-triacetoxy-1,1-dihydro-1,2-benz).
  • Hypervalent iodine compounds such as iodoxol-3 (1H) -one), halogens such as chlorine, bromine and iodine, azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), a radical initiator such as benzoyl peroxide and N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo- Combined with halogenating agents such as 5,5-dimethylhydantoin and 1,3-diiodo-5,5-dimethylhydantoin Metal oxides such as cancer, may be used benzoquinones such as 2,3-dichloro-5,6-dicyano -p- benzoquinone.
  • the oxidizing agent is a peracid.
  • potassium peroxodisulfate will be described.
  • the amount of potassium peroxodisulfate used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (2c). It is 1 equivalent or more and 10 equivalents or less.
  • the amount of the acid at that time is not particularly limited as long as the intended reaction proceeds if the amount of the acid is 2 equivalents for the monovalent acid with respect to potassium peroxodisulfate and 1 equivalent or more for the divalent acid. It will not be done.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but examples thereof include alcohol solvents such as methanol, ethanol and isopropanol, and nitrile solvents such as acetonitrile. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2c). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
  • the water content of the reaction mixture containing the compound represented by the formula (1a) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • a desiccant such as sodium sulfate or magnesium sulfate
  • reaction mixture containing the compound represented by the formula (1a) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
  • reaction mixture containing the compound represented by the formula (1a) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • the oxidizing agent is a hypervalent iodine compound, but here IBX is described.
  • the amount of the oxidizing agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (2c), but it is usually 1 It is equal to or more than 20 equivalents.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ester solvent such as ethyl acetate, isopropyl acetate or butyl acetate, a sulfur solvent system such as dimethyl sulfoxide or sulfolane. A solvent etc. are mentioned. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2c). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. In this reaction, a liquid separation operation is not essential.
  • the water content of the reaction mixture containing the compound represented by the formula (1a) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • a desiccant such as sodium sulfate or magnesium sulfate
  • reaction mixture containing the compound represented by the formula (1a) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
  • reaction mixture containing the compound represented by the formula (1a) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • the amount of the oxidizing agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (2c), but it is usually 1 It is equal to or more than 20 equivalents.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but acidic solvents such as acetic acid, benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc. , Halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • acidic solvents such as acetic acid
  • benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc.
  • Halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride.
  • the amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2c). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -10 ° C or higher and 150 ° C or lower, or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. In this reaction, a liquid separation operation is not essential.
  • the water content of the reaction mixture containing the compound represented by the formula (1a) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • a desiccant such as sodium sulfate or magnesium sulfate
  • reaction mixture containing the compound represented by the formula (1a) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
  • reaction mixture containing the compound represented by the formula (1a) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • the oxidizing agent is a combination of a radical initiator and a halogenating agent.
  • the amounts of the radical initiator and the halogenating agent used in this reaction are 0.01 equivalents or more and 1.0 equivalents or more, respectively, with respect to the compound represented by the formula (2c), and the desired reaction proceeds. There is no particular limitation as long as it does. Usually, the amount of the radical initiator is from 0.01 to 1 equivalent, and the amount of the halogenating agent is from 1 to 3 equivalents. However, the amount of the halogenating agent containing hydantoin is not particularly limited as long as the intended reaction proceeds, as long as it is 0.5 equivalent or more, and is usually 1 equivalent or more and 1.5 equivalents or less.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but halogenated benzene solvents such as chlorobenzene and dichlorobenzene, and ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate.
  • halogenated benzene solvents such as chlorobenzene and dichlorobenzene
  • ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate.
  • examples thereof include solvents, halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, and hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane.
  • solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2c). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 20 ° C. or higher and 150 ° C. or lower or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane and chloroform, a hydrocarbon solvent such as hexane, heptane, cyclohexane and methylcyclohexane, which is incompatible with water. It is possible.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
  • the water content of the reaction mixture containing the compound represented by the formula (1a) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • a desiccant such as sodium sulfate or magnesium sulfate
  • reaction mixture containing the compound represented by the formula (1a) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
  • reaction mixture containing the compound represented by the formula (1a) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • the oxidizing agent is a metal oxide.
  • manganese dioxide will be described.
  • the amount of the oxidizing agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (2c), but it is usually 1 It is equal to or more than 200 equivalents.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, dichloromethane, dichloroethane, chloroform, Examples thereof include halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2c). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.
  • a liquid separation operation can be performed by adding water or an appropriate aqueous solution to the reaction mixture.
  • an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate
  • An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. In this reaction, a liquid separation operation is not essential.
  • the water content of the reaction mixture containing the compound represented by the formula (1a) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • a desiccant such as sodium sulfate or magnesium sulfate
  • reaction mixture containing the compound represented by the formula (1a) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
  • reaction mixture containing the compound represented by the formula (1a) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • the oxidizing agent is a benzoquinone.
  • the amount of the oxidizing agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (2c), but it is usually 1 It is equal to or more than 20 equivalents.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, dichloromethane, dichloroethane, chloroform, Examples thereof include halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2c). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. In this reaction, a liquid separation operation is not essential.
  • the water content of the reaction mixture containing the compound represented by the formula (1a) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • a desiccant such as sodium sulfate or magnesium sulfate
  • reaction mixture containing the compound represented by the formula (1a) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
  • reaction mixture containing the compound represented by the formula (1a) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • R3a represents a halogen atom
  • R3b represents a C1 to C6 alkoxy group optionally substituted by a substituent C
  • a C1 to C6 haloalkoxy group optionally substituted by a substituent C.
  • the production method C is such that R3b is a C1 to C6 alkoxy group optionally substituted with a substituent C, a C1 to C6 haloalkoxy group, a C3 to C8 cycloalkoxy group optionally substituted with a substituent C, A C2 to C6 alkenyloxy group optionally substituted with a substituent C, a C2 to C6 haloalkenyloxy group, a C3 to C6 alkynyloxy group optionally substituted with a substituent C, or a C3 to C6 A method for obtaining a compound represented by formula (1c) which is a haloalkynyloxy group, the method comprising reacting the compound represented by formula (1b) with R3b-Q in a solvent. .
  • R3b-Q used in this reaction can be obtained as a commercial product or can be produced by a known method.
  • Preferred Q is a hydrogen atom or an alkali metal such as sodium or potassium.
  • the amount of R3b-Q used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more based on the compound represented by the formula (1b). It is 1 equivalent or more and 30 equivalents or less.
  • Q represents a hydrogen atom, it can be used as a solvent.
  • the base used in this reaction is preferably an inorganic base such as sodium carbonate, potassium carbonate, cesium carbonate or sodium hydride.
  • Q is an alkali metal, the use of a base is not essential.
  • the amount of the base used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1b), but usually 1 equivalent It is above 30 equivalents.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but an alcohol solvent represented by R3b-H (in the formula, R3b has the same meaning as above), Ether-based solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, benzene-based solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ethyl acetate, isopropyl acetate, butyl acetate
  • ester-based solvents nitrile-based solvents such as acetonitrile, amide-based solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone Urea-based solvent, dichlor
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (1b). is there.
  • the temperature at which this reaction is performed is not particularly limited as long as the desired reaction proceeds, but is usually 0 ° C or higher and 150 ° C or lower or the boiling point of the solvent or lower.
  • a liquid separation operation can be performed by adding water or an appropriate aqueous solution to the reaction mixture.
  • an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate or the like is dissolved, sodium thiosulfate or sulfite is used.
  • aqueous solution in which a salt containing a sulfur atom such as sodium is dissolved, a saline solution or the like can be optionally used.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- Ether-based solvents such as t-butyl ether, halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane that are not compatible with water. It is possible to add. In addition, these solvents can be used alone or as a benzene solvent such as tol
  • the water content of the reaction mixture containing the compound represented by the formula (1c) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (1c) obtained above can be distilled under reduced pressure to remove the solvent.
  • reaction mixture containing the compound represented by the formula (1c) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • R3c represents a C1 to C6 alkoxy group
  • R1, R2, R3, X, Z and o have the same meanings as described above.
  • Production method D is a method for obtaining a compound represented by formula (1e) having a hydroxyl group, which comprises obtaining the compound represented by formula (1d) and an acid in a solvent. Is the way.
  • the acids used in this reaction include boron halides such as boron trichloride and boron tribromide.
  • the amount of the acid used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1d), and is not particularly limited as long as the intended reaction proceeds, but it is usually 1 It is equal to or more than 10 equivalents.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is a benzene solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene, or dichlorobenzene, and a nitrile solvent such as acetonitrile.
  • benzene solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene, or dichlorobenzene
  • a nitrile solvent such as acetonitrile.
  • Halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride
  • hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane.
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (1d). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 100 ° C or lower, or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
  • the water content of the reaction mixture containing the compound represented by the formula (1e) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (1e) obtained above can be distilled under reduced pressure to remove the solvent.
  • reaction mixture containing the compound represented by the formula (1e) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • R3d is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, A C2 to C6 alkenyl group optionally substituted with a substituent C, a C2 to C6 haloalkenyl group, a C3 to C6 alkynyl group optionally substituted with a substituent C, a C3 to C6 haloalkynyl group, Alternatively, a method for obtaining a compound represented by the formula (1f), which is RdC ( ⁇ O)-(Rd has the same meaning as described above), comprising the step of reacting the compound represented by the formula (1e) with R3d-Lv. In a solvent in the presence of a base.
  • R3d-Lv used in this reaction can be obtained as a commercial product or can be produced by a known method.
  • the amount of R3d-Lv used in this reaction may be 1 equivalent or more relative to the compound represented by the formula (1e), and is not particularly limited as long as the intended reaction proceeds, but it is usually It is 1 equivalent or more and 10 equivalents or less.
  • inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate and sodium hydride
  • organic bases such as triethylamine, tributylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, collidine and lutidine Examples thereof include, but are not particularly limited as long as the desired reaction proceeds.
  • the amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1e) and is not particularly limited as long as the intended reaction proceeds, but it is usually 1 It is equal to or more than 10 equivalents.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Methanol, ethanol, alcohol solvents such as isopropanol, benzene, toluene, xylene, mesitylene, chlorobenzene, benzene solvents such as dichlorobenzene, ethyl acetate, isopropyl acetate, ester solvents such as butyl acetate, nitrile solvents such as acetonitrile, Amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, dichloromethane, dichloroethane,
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (1e). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -20 ° C or higher and 150 ° C or lower, or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
  • the water content of the reaction mixture containing the compound represented by the formula (1f) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (1f) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
  • reaction mixture containing the compound represented by the formula (1f) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • R2b represents a halogen atom
  • HalR, R1, X, Z, R3 and n have the same meanings as described above.
  • Production method F is a method for obtaining the compound represented by formula (1h), which comprises reacting the compound represented by formula (1g) with a halogenating agent (HalR) in a solvent. Is.
  • the production method F can be carried out according to the production method A.
  • Production method G is a method for obtaining the compound represented by formula (1j), which comprises reacting the compound represented by formula (1i) with a halogenating agent (HalR) in a solvent. Is.
  • the production method G can be carried out according to the production method A.
  • R1c represents a C1 to C6 alkyl group which may be optionally substituted with a substituent A, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group which may be optionally substituted with a substituent A, a substituent A C2 to C6 alkenyl group which may be appropriately substituted with A, a C2 to C6 haloalkenyl group, R1c-B represents an organic boronic acid, R2c is a hydrogen atom, or a substituent A may be appropriately substituted.
  • RgC ( O)-(wherein Rg has the same meaning as defined above)
  • the bond containing the broken line represents a single bond or a double bond
  • R1a, R3, X, Z And n are as defined above.
  • the combination including the broken line part means Represents a portion represented by.
  • R1c is a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent A
  • R1a is a chlorine atom, a bromine atom, or an iodine atom.
  • R1c-B used in this reaction represents an organic boronic acid such as an organic boronic acid or an organic boronic acid ester, which can be obtained as a commercial product or can be produced by a known method.
  • the amount of R1c-B used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (3a). It is 1 equivalent or more and 10 equivalents or less.
  • the transition metals used in this reaction are palladium, nickel, ruthenium, etc., and may have a ligand.
  • Preferred are palladium acetate, [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride and the like. Examples include palladiums.
  • the amount of the transition metal used in this reaction is usually 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (3a), but is not particularly limited as long as the intended reaction proceeds. It will not be done.
  • a phosphine ligand such as triphenylphosphine or tricyclohexylphosphine can be added to allow the reaction to proceed efficiently.
  • the amount of the phosphine ligand used in this reaction is usually 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (3a), but as long as the intended reaction proceeds, There is no limitation.
  • the bases used in this reaction are inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate and tripotassium phosphate, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide.
  • the amount of the base used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more relative to the compound represented by the formula (3a), but usually 1 equivalent It is above 50 equivalents.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether such as water solvent, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane.
  • the solvent include benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (3a). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 30 ° C. or higher and 200 ° C. or lower or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. It is also possible, but not essential, to remove insolubles by performing a filtration operation.
  • the water content of the reaction mixture containing the compound represented by the formula (3b) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (3b) obtained above can be distilled under reduced pressure to remove the solvent.
  • reaction mixture containing the compound represented by the formula (3b) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • R1d represents a C2-C6 alkynyl group which may be appropriately substituted with a substituent A, or a C2-C6 haloalkynyl group
  • R1a, R2c, R3, X, Z, n and the broken line portion are as described above. are synonymous.
  • Production Method I is a method for obtaining a compound represented by the formula (3c), wherein R1d is a C2-C6 alkynyl group optionally substituted with a substituent A, or a C2-C6 haloalkynyl group,
  • a production method comprising obtaining a compound represented by the formula (3a) and a terminal alkyne compound by Sonogashira coupling in which a compound is reacted in the presence of a transition metal and a base in a solvent.
  • R1a is a chlorine atom, a bromine atom, or an iodine atom.
  • the terminal alkyne compound used in this reaction can be obtained as a commercial product or can be produced by a known method. Trimethylsilylacetylene can also be used as the terminal alkyne compound. In this case, it is necessary to introduce a trimethylsilylethynyl group into the compound represented by the formula (3a) and then perform desilylation. For desilylation, see Journal of the American Chemical Society, Vol. 131, No. 2, pp. 634-643 (2009). And Journal of Organometallic Chemistry, 696, 25, 4039-4045 (2011). It can be performed with reference to non-patent documents such as the above.
  • the amount of the terminal alkyne compound used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (3a). It is 1 equivalent or more and 10 equivalents or less.
  • the transition metals used in this reaction may have a ligand, and include palladium acetate, [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris (dibenzylideneacetone) dipalladium, tetrakis ( Palladium compounds such as triphenylphosphine) palladium and bis (triphenylphosphine) palladium dichloride.
  • coppers such as copper chloride, copper bromide, and copper iodide are used at the same time.
  • the amount of the transition metal used in this reaction is usually 0.001 equivalent or more with respect to the compound represented by the formula (3a), such as palladium and copper, and the desired reaction There is no particular limitation as long as the process proceeds. Preferred amounts are 0.001 equivalent to 1 equivalent in both cases.
  • Examples of the base used in this reaction include organic amines such as triethylamine, tributylamine, isopropylamine, diethylamine, diisopropylamine and diisopropylethylamine, and inorganic bases such as sodium carbonate, potassium carbonate and cesium carbonate.
  • organic amines such as triethylamine, tributylamine, isopropylamine, diethylamine, diisopropylamine and diisopropylethylamine
  • inorganic bases such as sodium carbonate, potassium carbonate and cesium carbonate.
  • the amount of the base used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more relative to the compound represented by the formula (3a), but usually 1 equivalent It is above 50 equivalents.
  • an organic base in a liquid state can be used as a solvent.
  • a phosphine ligand such as tri-t-butylphosphine or 2-dicyclohexylphosphino-2'4'6'-triisopropylbiphenyl can be added to promote the reaction efficiently, but it is not essential. .
  • the amount of the phosphine ligand used in this reaction is usually 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (3a), but as long as the intended reaction proceeds, There is no limitation.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ester-based solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitrile-based solvents such as acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide , Amide solvents such as N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, halogen solvents such as dichloromethane, dichloroethane, chloroform and
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (3a). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. It is also possible, but not essential, to remove insolubles by performing a filtration operation.
  • the water content of the reaction mixture containing the compound represented by the formula (3c) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (3c) obtained above can be distilled under reduced pressure to remove the solvent.
  • reaction mixture containing the compound represented by the formula (3c) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • J represents an oxygen atom or a sulfur atom
  • R1e is a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, or a substituent A.
  • Production method J is a method wherein J represents an oxygen atom or a sulfur atom, and when J is an oxygen atom, R1e is a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, or a substituent which may be appropriately substituted with a substituent A.
  • a C3 to C8 cycloalkyl group optionally substituted with A, a C2 to C6 alkenyl group optionally substituted with a substituent A, a C2 to C6 haloalkenyl group, optionally substituted with a substituent A Represents a good C2 to C6 alkynyl group or a C2 to C6 haloalkynyl group, and when J is a sulfur atom, R1e is represented by the formula (3d) representing a C1 to C6 alkyl group or a C1 to C6 haloalkyl group.
  • a compound of formula (3a) and R1e-JQ in a solvent in the presence of a transition metal and a base It is a manufacturing method that includes.
  • R1a is chlorine atom, bromine atom or iodine atom.
  • R1e-JQ used in this reaction can be obtained as a commercial product or can be produced by a known method.
  • Preferred Q is a hydrogen atom or an alkali metal such as sodium or potassium.
  • R1e-JQ used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is at least 1 equivalent relative to the compound represented by the formula (3a).
  • Q is a hydrogen atom, it can be used also as a solvent.
  • the transition metals used in this reaction may have a ligand, and include palladium acetate, [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris (dibenzylideneacetone) dipalladium, tetrakis ( Palladium compounds such as triphenylphosphine) palladium and bis (triphenylphosphine) palladium dichloride.
  • the amount of the transition metal used in this reaction is usually 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (3a), but is not particularly limited as long as the intended reaction proceeds. It will not be done.
  • triphenylphosphine 1,1′-bis (diphenylphosphino) ferrocene, 2-dicyclohexylphosphino-2′4′6′-triisopropylbiphenyl, 2-di-t
  • a phosphine ligand such as -butylphosphino-2'4'6'-triisopropylbiphenyl can be added.
  • the amount of the phosphine ligand used in this reaction is usually 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (3a), but as long as the intended reaction proceeds, There is no limitation.
  • the bases used in this reaction include inorganic bases such as sodium carbonate, potassium carbonate and cesium carbonate, and organic bases such as triethylamine, tributylamine and diisopropylethylamine.
  • the amount of the base used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more relative to the compound represented by the formula (3a), but usually 1 equivalent It is above 50 equivalents.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but R1e-JH (wherein R1e has the same meaning as described above and J is an oxygen atom).
  • Alcohol solvent represented by diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, ether solvent such as dioxane, benzene solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc. Is mentioned.
  • These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (3a). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 30 ° C. or higher and 200 ° C. or lower or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. It is also possible, but not essential, to remove insolubles by performing a filtration operation.
  • the water content of the reaction mixture containing the compound represented by the formula (3d) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (3d) obtained above can be evaporated under reduced pressure as long as the compound does not decompose.
  • reaction mixture containing the compound represented by the formula (3d) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • R3e is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent C Represents a C2 to C6 alkenyl group which may be optionally substituted with, or a C2 to C6 haloalkenyl group, R3e-B represents an organic boronic acid, and R1, R2, R3, R3a, X, Z and o are as described above. Is synonymous with.
  • R3e is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent
  • a production method comprising obtaining a compound and an organic boronic acid (R3e-B) by Suzuki-Miyaura coupling in which a compound is reacted in the presence of a transition metal and a base in a solvent.
  • R3a is a chlorine atom, a bromine atom or an iodine atom.
  • R3e-B used in this reaction represents an organic boronic acid such as an organic boronic acid or an organic boronic acid ester, and can be obtained as a commercially available product or can be produced by a known method.
  • a production method according to the production method H by using the compound represented by the formula (3a) and R1c-B in the production method H instead of the compound represented by the formula (1b) and R3e-B, respectively. K can be carried out.
  • R4a represents a halogen atom
  • Z1 is a thienyl group which may be optionally substituted by 0 to 2 with R4 (however, in the case of 2 or more substitutions, each is independent)
  • R1 is appropriately substituted with R4.
  • HalR, R1, R2, R3, X and n are as defined above.
  • Production method L is a method for obtaining a compound represented by formula (1m), which comprises reacting the compound represented by formula (1l) with a halogenating agent (HalR) in a solvent.
  • a halogenating agent HalR
  • the production method L can be carried out according to the production method A.
  • R4b is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent C Represents an optionally substituted C2 to C6 alkenyl group or a C2 to C6 haloalkenyl group, R4b-B represents an organic boronic acid, and R1, R2, R3, R4a, X, Z1 and n are the above Is synonymous with.
  • R4b is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent
  • a production method comprising obtaining a compound and an organic boronic acid (R4b-B) by Suzuki-Miyaura coupling in which a compound is reacted in the presence of a transition metal and a base in a solvent.
  • preferred R4a is a chlorine atom, a bromine atom, or an iodine atom.
  • R4b-B used in this reaction represents an organic boronic acid such as an organic boronic acid or an organic boronic acid ester, which can be obtained as a commercially available product or can be produced by a known method.
  • a production method according to the production method H by using the compound represented by the formula (3a) and R1c-B in the production method H instead of the compound represented by the formula (1m) and R4b-B, respectively. M can be carried out.
  • R3f represents a C2-C6 alkynyl group which may be optionally substituted with a substituent C, or a C2-C6 haloalkynyl group
  • R1, R2, R3, R3a, X, Z and o have the same meanings as described above. Is.
  • the production method N is a method of obtaining a compound represented by the formula (1o), wherein R3f is a C2-C6 alkynyl group optionally substituted with a substituent C, or a C2-C6 haloalkynyl group,
  • a production method comprising obtaining a compound represented by the formula (1b) and a terminal alkyne compound by Sonogashira coupling in which a compound is reacted in the presence of a transition metal and a base in a solvent.
  • R3a is a chlorine atom, a bromine atom or an iodine atom.
  • the terminal alkyne compound used in this reaction can be obtained as a commercial product or can be produced by a known method. Further, trimethylsilylacetylene can also be used as the terminal alkyne compound.
  • the production method N can be carried out according to the production method I.
  • R4c represents a C2 to C6 alkynyl group which may be appropriately substituted with a substituent C, or a C2 to C6 haloalkynyl group
  • R1, R2, R3, R4a, X, Z1 and n have the same meanings as described above. Is.
  • Production method O is a method for obtaining a compound represented by the formula (1p) in which R4c is a C2-C6 alkynyl group optionally substituted with a substituent C, or a C2-C6 haloalkynyl group,
  • a production method which comprises obtaining a compound represented by the formula (1m) and a terminal alkyne compound by Sonogashira coupling in which a compound is reacted in the presence of a transition metal and a base in a solvent.
  • R4a is a chlorine atom, a bromine atom, or an iodine atom.
  • the terminal alkyne compound used in this reaction can be obtained as a commercial product or can be produced by a known method. Trimethylsilylacetylene can also be used as the terminal alkyne compound.
  • the production method O can be carried out according to the production method I.
  • R4d represents a C1-C6 alkoxy group
  • R1, R2, R3, X, Z1 and n have the same meanings as described above.
  • Production method P is a method for obtaining a compound represented by the formula (1r) having a hydroxyl group, which is obtained by reacting the compound represented by the formula (1q) with an acid in a solvent. Is the way.
  • the acids used in this reaction include boron halides such as boron trichloride and boron tribromide.
  • the production method P can be carried out according to the production method D.
  • R4e is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent C
  • R4e is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, A C2 to C6 alkenyl group optionally substituted with a substituent C, a C2 to C6 haloalkenyl group, a C3 to C6 alkynyl group optionally substituted with a substituent C, a C3 to C6 haloalkynyl group, Alternatively, a method of obtaining a compound represented by the formula (1s), which is RdC ( ⁇ O)-(Rd has the same meaning as described above), comprising the step of providing a compound represented by the formula (1r) and R4e-Lv. In a solvent in the presence of a base.
  • the production method Q is carried out according to the production method E. Can be carried out.
  • a method for obtaining the above-mentioned production intermediate which comprises reacting the compound represented by the formula (2d) with R2c-Lv in a solvent in the presence of a base.
  • the R2c-Lv used in this reaction can be obtained as a commercial product or can be produced by a known method.
  • the amount of R2c-Lv used in this reaction may be 1 equivalent or more relative to the compound represented by the formula (2d), and is not particularly limited as long as the intended reaction proceeds, but It is 1 equivalent or more and 50 equivalents or less.
  • metal hydrides such as sodium hydride, organic lithiums such as methyllithium, butyllithium, sec-butyllithium, t-butyllithium, and hexyllithium, lithium diisopropylamide, hexamethyldisilazane
  • metal amides such as lithium, sodium hexamethyldisilazane, and potassium hexamethyldisilazane.
  • the amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (2d) and is not particularly limited as long as the intended reaction proceeds, but it is usually 1 It is equal to or more than 20 equivalents.
  • Additives such as hexamethylphosphoric triamide, N, N'-dimethylurea, and tetramethylethylenediamine can be added in order to allow the reaction to proceed smoothly, but are not essential.
  • the amount of the additive used is 1 equivalent or more and 100 equivalents or less with respect to the compound represented by the formula (2d).
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Examples thereof include benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, and hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane
  • benzene-based solvents such as
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2d). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 100 ° C or lower, or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane and chloroform, a hydrocarbon solvent such as hexane, heptane, cyclohexane and methylcyclohexane, which is incompatible with water. It is possible.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
  • the water content of the reaction mixture containing the compound represented by the formula (2e) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (2e) obtained above can be distilled under reduced pressure to remove the solvent.
  • reaction mixture containing the compound represented by the formula (2e) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • R1f represents a hydrogen atom or a C1 to C6 alkyl group
  • R2d represents a hydrogen atom or a C1 to C6 alkyl group
  • Rx, Ry and Rz are each independently C1 to C6 Represents an alkyl group
  • Rw represents a C1-C6 alkoxy group or RaRbN- (wherein Ra and Rb have the same meanings as described above)
  • R3, Z and n have the same meanings as described above.
  • the wavy line in the formula represents geometrical isomerism, and represents only one of the E isomer and the Z isomer, or a mixture of the E isomer and the Z isomer at an arbitrary ratio.
  • Production method S is a method for obtaining a compound represented by the formula (2f) in which R1f represents a hydrogen atom or a C1 to C6 alkyl group, and R2d represents a hydrogen atom or a C1 to C6 alkyl group, A production method comprising reacting a compound represented by formula (4), a compound represented by formula (5) and a compound represented by formula (6) in a solvent.
  • the compound represented by the formula (4) used in this reaction can be obtained as a commercial product or can be produced by a known method.
  • the compound represented by the formula (5) used in this reaction can be obtained as a commercially available product or can be produced by a known method.
  • the amount of the compound represented by the formula (5) used in this reaction is not particularly limited as long as the reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (4). Usually, it is 1 equivalent or more and 1.5 equivalents or less.
  • the compound represented by the formula (6) used in this reaction can be obtained as a commercial product or can be produced by a known method. Further, when there are geometrical isomers, only one of E-form or Z-form or a mixture of E-form and Z-form at an arbitrary ratio may be used and is not particularly limited as long as the reaction proceeds.
  • the amount of the compound represented by the formula (6) used in this reaction is not particularly limited as long as the reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (4). Usually, it is 1 equivalent or more and 3 equivalents or less.
  • This reaction is not essential, but the reaction can be smoothly proceeded by adding an acid or a surfactant.
  • Tetrafluoroboric acid etc. can be illustrated as an acid to be used.
  • the amount of the acid used in this reaction may be a catalytic amount with respect to the compound represented by the formula (4) and is not particularly limited as long as the intended reaction proceeds, but usually 0.01 It is equal to or more than 1 equivalent.
  • sodium dodecyl sulfate etc. can be illustrated as a surfactant to be used.
  • the amount of the surfactant used in the reaction may be a catalytic amount with respect to the compound represented by the formula (4) and is not particularly limited as long as the intended reaction proceeds, but it is usually 0. It is from 1 equivalent to 1 equivalent.
  • the acid and the surfactant can be used at the same time or only one of them.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether system such as water, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane and the like.
  • Solvents alcohol solvents such as methanol, ethanol and isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitrile solvents such as acetonitrile Solvents, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, dichloromethane, dichloroethane Chloroform, and halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. In addition, a solvent is not essential for this reaction.
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (4). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 150 ° C or lower or the boiling point of the solvent or lower.
  • the compound represented by the formula (4), the compound represented by the formula (5) and the compound represented by the formula (6) can be reacted together. Further, the compound represented by the formula (4) and the compound represented by the formula (5) can be reacted in advance to convert into an imine, and then the compound represented by the formula (6) can be reacted.
  • the imine can be prepared by a known method. In this case, the compound represented by formula (4) and the compound represented by formula (5) can be replaced by the imine, and the method described above can be used.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
  • the water content of the reaction mixture containing the compound represented by the formula (2f) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (2f) obtained above can be distilled under reduced pressure to remove the solvent.
  • reaction mixture containing the compound represented by the formula (2f) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • R5 represents a hydroxyl group or a C1 to C6 alkoxy group
  • R3, Z and n have the same meanings as described above.
  • the production method T is a method for obtaining a production intermediate represented by the formula (7) in which R5 is a hydroxyl group or a C1 to C6 alkoxy group, and comprises a compound represented by the formula (4) and a formula (4) It is a production method which comprises reacting the compound represented by 5) in a solvent.
  • the compound represented by the formula (4) used in this reaction can be obtained as a commercial product or can be produced by a known method.
  • the compound represented by the formula (5) used in this reaction can be obtained as a commercially available product or can be produced by a known method.
  • the amount of the compound represented by the formula (5) used in this reaction is not particularly limited as long as the reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (4). Usually, it is 1 equivalent or more and 1.5 equivalents or less.
  • reaction is not essential, but the addition of an acid or a base allows the reaction to proceed smoothly.
  • the acid used include pyridinium paratoluenesulfonate.
  • the amount of the acid used in this reaction may be a catalytic amount with respect to the compound represented by the formula (4) and is not particularly limited as long as the intended reaction proceeds, but usually 0.01 It is equal to or more than 1 equivalent.
  • the base used include pyrrolidine and piperidine.
  • the amount of the base used in the reaction may be a catalytic amount with respect to the compound represented by the formula (4) and is not particularly limited as long as the intended reaction proceeds, but usually 0.01 equivalent It is above 1 equivalent.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Methanol, ethanol, alcohol solvents such as isopropanol, benzene, toluene, xylene, mesitylene, chlorobenzene, benzene solvents such as dichlorobenzene, ethyl acetate, isopropyl acetate, ester solvents such as butyl acetate, nitrile solvents such as acetonitrile, Examples thereof include halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. In addition, a solvent is not essential for
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (4). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 150 ° C or lower or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
  • the water content of the reaction mixture containing the compound represented by the formula (7) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (7) obtained above can be evaporated under reduced pressure as long as the compound does not decompose.
  • reaction mixture containing the compound represented by the formula (7) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • the production method U is a method for obtaining a production intermediate represented by the formula (2g), which comprises reacting the compound represented by the formula (7) with the compound represented by the formula (6) in a solvent. It is a manufacturing method including the above.
  • the compound represented by the formula (6) used in this reaction can be obtained as a commercial product or can be produced by a known method. Further, when there are geometrical isomers, only one of E-form or Z-form or a mixture of E-form and Z-form at an arbitrary ratio may be used and is not particularly limited as long as the reaction proceeds.
  • the amount of the compound represented by the formula (6) used in this reaction is not particularly limited as long as the reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (7). Usually, it is 1 equivalent or more and 3 equivalents or less.
  • This reaction is not essential, but the reaction can be smoothly proceeded by adding an acid or a surfactant.
  • Tetrafluoroboric acid etc. can be illustrated as an acid to be used.
  • the amount of the acid used in this reaction may be a catalytic amount with respect to the compound represented by the formula (7) and is not particularly limited as long as the intended reaction proceeds, but usually 0.01 It is equal to or more than 1 equivalent.
  • sodium dodecyl sulfate etc. can be illustrated as a surfactant to be used.
  • the amount of the surfactant used in the reaction may be a catalytic amount with respect to the compound represented by the formula (7) and is not particularly limited as long as the intended reaction proceeds, but it is usually 0. It is from 1 equivalent to 1 equivalent.
  • the acid and the surfactant can be used at the same time or only one of them.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether system such as water, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane and the like.
  • Solvents alcohol solvents such as methanol, ethanol and isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitrile solvents such as acetonitrile Solvents, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, dichloromethane, dichloroethane Chloroform, and halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. In addition, a solvent is not essential for this reaction.
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (7). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 150 ° C or lower or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
  • the water content of the reaction mixture containing the compound represented by the formula (2g) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (2g) obtained above can be evaporated under reduced pressure as long as the compound does not decompose.
  • reaction mixture containing the compound represented by the formula (2g) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • the compound represented by the formula (2g) has structural isomers.
  • the isomer ratio may be a single isomer or a mixture in an arbitrary ratio, and is not particularly limited as long as the reaction of the next step proceeds.
  • Z2 represents a pyrazolyl group which may be optionally substituted by 0 to 2 with R4 (however, in the case of 2 or more substituted R4, each is independent), and R1, R2, R3, X and n are It is synonymous with the above.
  • Production method V is a method for obtaining a compound represented by the formula (1u) having a formyl group, which comprises reacting the compound represented by the formula (1t) and N, N-dimethylformamide in the presence of a base in a solvent. It is a manufacturing method including reacting with.
  • the N, N-dimethylformamide used in this reaction can be obtained as a commercial product.
  • the amount of N, N-dimethylformamide used in this reaction is not particularly limited as long as the reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1t). It is 1 equivalent or more and 50 equivalents or less.
  • Examples of the base used in this reaction include organic lithiums such as methyllithium, butyllithium, sec-butyllithium, t-butyllithium, and hexyllithium, lithium diisopropylamide, hexamethyldisilazane lithium, hexamethyldisilazane sodium, and hexa
  • organic lithiums such as methyllithium, butyllithium, sec-butyllithium, t-butyllithium, and hexyllithium
  • lithium diisopropylamide lithium diisopropylamide
  • hexamethyldisilazane lithium hexamethyldisilazane sodium
  • metal amides such as potassium methyldisilazane.
  • the amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1t) and is not particularly limited as long as the intended reaction proceeds, but it is usually 1 It is equal to or more than 20 equivalents.
  • additives such as hexamethylphosphoric triamide, N, N'-dimethylurea) and tetramethylethylenediamine can be added, but they are not essential.
  • the amount of the additive used is 1 equivalent or more and 100 equivalents or less with respect to the compound represented by the formula (1t).
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Examples thereof include benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, and hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane
  • benzene-based solvents such as
  • the amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but is usually 3 times or more and 200 times or less by weight with respect to the compound represented by the formula (1t). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 100 ° C or lower, or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane and chloroform, a hydrocarbon solvent such as hexane, heptane, cyclohexane and methylcyclohexane, which is incompatible with water. It is possible.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
  • the water content of the reaction mixture containing the compound represented by the formula (1u) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (1u) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
  • reaction mixture containing the compound represented by the formula (1u) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • the production method W is a method for obtaining a compound represented by the formula (1v) having a difluoromethyl group, wherein the compound represented by the formula (1u) and the fluorinating agent (FR) are mixed in a solvent. It is a manufacturing method including a method of reacting.
  • DAST trifluoride-N, N-diethylaminosulfur
  • Deoxo-Fluor N, N-dimethoxyethylaminosulfur trifluoride
  • XtalFluor-E N, N-diethyl) -S, S-difluorosulfiliminium tetrafluoroborate
  • XtalFluor-M difluoro (morpholino) sulfonium tetrafluoroborate
  • FluoLead (4-t-butyl-2,6-dimethylphenylsulfurtolufluoride)
  • Ishikawa reagent N, N-diethyl-1,1,2,3,3,3-hexafluoropropylamine
  • DFI 2,2-difluoro-1,3-dimethylimidazolidine
  • the amount of the fluorinating agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1u), It is 1 equivalent or more and 20 equivalents or less.
  • an additive such as 1,8-diazabicyclo [5,4,0] undec-7-ene or triethylamine trihydrofluoride can be added, but it is not essential. Absent.
  • the amount of the additive used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more relative to the compound represented by the formula (1u). It is equal to or more than 20 equivalents.
  • the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but ether solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, etc., Benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ester-based solvents such as ethyl acetate, isopropyl acetate and butyl acetate, halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride. . These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (1u). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 100 ° C or lower, or the boiling point of the solvent or lower.
  • a liquid separation operation As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture.
  • an aqueous solution dissolve an alkaline aqueous solution in which the salts potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc., and salts containing sulfur atoms such as sodium thiosulfate, sodium sulfite, etc. are dissolved.
  • the aqueous solution, salt solution, etc. can be optionally used.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane and chloroform, a hydrocarbon solvent such as hexane, heptane, cyclohexane and methylcyclohexane, which is incompatible with water. It is possible.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
  • the water content of the reaction mixture containing the compound represented by the formula (1v) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (1v) obtained above can be distilled under reduced pressure to remove the solvent.
  • reaction mixture containing the compound represented by the formula (1v) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • the production method X is a method of obtaining a compound represented by the formula (3e) having a trifluoromethyl group, wherein the compound represented by the formula (3a) and methyl difluoro (fluorosulfonyl) acetate are used as transition metals. It is a production method comprising reacting in a solvent in the presence.
  • R1a is a chlorine atom, a bromine atom or an iodine atom.
  • the methyl difluoro (fluorosulfonyl) acetate used in this reaction can be obtained as a commercial product or can be produced by a known method.
  • the amount of methyl difluoro (fluorosulfonyl) acetate used in this reaction is not particularly limited as long as the intended reaction proceeds, provided that it is at least 1 equivalent with respect to the compound represented by formula (3a). However, it is preferably 1 equivalent or more and 50 equivalents or less.
  • transition metals used in this reaction are copper and the like.
  • copper bromide, copper iodide, or the like is used.
  • the amount of the transition metal used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (3a), and is not particularly limited as long as the intended reaction proceeds, It is preferably 1 equivalent or more and 50 equivalents or less.
  • additives such as ethyldiisopropylamine and hexamethylphosphoric triamide can be added, but it is not essential.
  • the amount of the additive used in this reaction is 50 equivalents or less with respect to the compound represented by the formula (3a), and is not particularly limited as long as the intended reaction proceeds.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, Examples thereof include sulfur-based solvents such as dimethyl sulfoxide and sulfolane. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (3a). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride or the like is dissolved
  • an alkaline aqueous solution in which ammonia, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved
  • An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium thiosulfate or sodium sulfite is dissolved can be optionally used.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. It is also possible, but not essential, to remove insolubles by performing a filtration operation.
  • the water content of the reaction mixture containing the compound represented by the formula (3e) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (3e) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
  • reaction mixture containing the compound represented by the formula (3e) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • Production method Y is the compound represented by the formula (1), a method of compound Lb contained in R1, R2, R3 and Z is represented by formula (Lb) is SO or SO 2, wherein In the compound represented by (1), the compound represented by the formula (La) in which La contained in R1, R2, R3 and Z is S and the oxidizing agent (Ox ′) are reacted in a solvent. It is a manufacturing method including.
  • oxidizing agent used in this reaction examples include hydrogen peroxide solution and peroxides such as meta-chloroperbenzoic acid. Also, transition metals such as sodium tungstate can be added.
  • the amount of the oxidizing agent used in this reaction is usually 1.0 equivalent or more and 1.2 equivalents or less with respect to the compound represented by the formula (La) when SO is produced, and SO 2 is produced. When doing, it is usually 2 equivalents or more and 10 equivalents or less. When adding transition metals, the amount is usually 0.001 equivalent or more and 1 equivalent or less.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it may be an aqueous solvent, an acidic solvent such as acetic acid, benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene or the like.
  • an acidic solvent such as acetic acid, benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene or the like.
  • examples thereof include benzene-based solvents, nitrile-based solvents such as acetonitrile, halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (La). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -10 ° C or higher and 120 ° C or lower or the boiling point of the solvent or lower.
  • an aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, etc. are dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc. are dissolved, sodium thiosulfate, sulfurous acid
  • An aqueous solution or a salt solution in which a salt containing a sulfur atom such as sodium is dissolved can be arbitrarily used.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
  • the water content of the reaction mixture containing the compound represented by the formula (Lb) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (Lb) obtained above can be distilled under reduced pressure to remove the solvent.
  • reaction mixture containing the compound represented by the formula (Lb) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • the production method Z is a method for obtaining a compound represented by the formula (3g) containing a sulfur atom, which comprises reacting the compound represented by the formula (3f) with a sulfurizing agent (SR) in a solvent. It is a manufacturing method including:
  • sulfurizing agent used in this reaction examples include Lawesson's reagent (2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide) and Berrie's reagent (2. 4-bis (4-phenoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide) and the like can be mentioned.
  • the amount of the sulfurizing agent used in this reaction may be 0.5 equivalent or more with respect to the compound represented by the formula (3f), and is not particularly limited as long as the intended reaction proceeds. Usually, it is 1 equivalent or more and 10 equivalents or less.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Examples thereof include benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (3f). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 50 ° C. or higher and 180 ° C. or lower or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. In this reaction, a liquid separation operation is not essential.
  • the water content of the reaction mixture containing the compound represented by the formula (3g) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (3 g) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
  • the reaction mixture containing the compound represented by the formula (3 g) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • the production method AA is a method for obtaining a compound represented by the formula (1w), which comprises reacting the compound represented by the formula (2h) with an oxidizing agent (Ox) in a solvent. is there.
  • the production method AA can be carried out according to the production method B.
  • OR represents an oxidizing agent
  • R1, R3, X, Z and n have the same meanings as described above.
  • the production method AB is a method for obtaining a compound represented by the formula (2i) containing a hydroxyl group, which comprises mixing the compound represented by the formula (2d) and an oxidizing agent (OR) in the presence of a base in a solvent. It is a manufacturing method including reacting with.
  • oxidizing agent used in this reaction examples include Davis reagent (3-phenyl-2-phenylsulfonyl-1,2-oxaziridine), (2R, 8aS)-(+)-(campharylsulfonyl) oxaziridine, (2S, 8aR )-( ⁇ )-(Camphorylsulfonyl) oxaziridine and other oxaziridines, hydrogen peroxide solution, meta-chloroperbenzoic acid, and peroxides such as dimethyldioxirane.
  • the amount of the oxidizing agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (2d), but it is usually 1 It is equal to or more than 10 equivalents.
  • metal hydrides such as sodium hydride, organic lithiums such as methyllithium, butyllithium, sec-butyllithium, t-butyllithium, and hexyllithium, lithium diisopropylamide, hexamethyldisilazane
  • metal amides such as lithium, sodium hexamethyldisilazane, and potassium hexamethyldisilazane.
  • the amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (2d) and is not particularly limited as long as the intended reaction proceeds, but it is usually 1 It is equal to or more than 20 equivalents.
  • additives such as hexamethylphosphoric triamide, N, N′-dimethylurea, tetramethylethylenediamine, chlorotrimethylsilane, chlorotriethylsilane, trifluoromethanesulfonic acid trimethylsilyl, trifluoromethanesulfonic acid, etc.
  • a silylating agent such as triethylsilyl can be added, but is not required. Further, these additives and the silylating agent can be used at the same time or only one of them can be used.
  • the amount of the additive used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 1 equivalent or more and 100 equivalents relative to the compound represented by the formula (2d). It is the following.
  • the amount of the silylating agent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 1 equivalent or more and 100 equivalents relative to the compound represented by the formula (2d). It is the following.
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Examples thereof include benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, and hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane
  • benzene-based solvents such as
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2d). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 100 ° C or lower, or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane and chloroform, a hydrocarbon solvent such as hexane, heptane, cyclohexane and methylcyclohexane, which is incompatible with water. It is possible.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
  • the water content of the reaction mixture containing the compound represented by the formula (2i) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (2i) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
  • reaction mixture containing the compound represented by the formula (2i) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • R2e is a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent A, a substituent A Represents a C2-C6 alkenyl group which may be optionally substituted with, a C2-C6 haloalkenyl group, a C2-C6 alkynyl group which may be optionally substituted with a substituent A, a C2-C6 haloalkynyl group, R1 , R3, X, Z, Lv and n are as defined above.
  • the production method AC is a method for obtaining a compound represented by the formula (2j) containing an alkoxy group, wherein the compound represented by the formula (2i) and R2e-Lv are reacted in the presence of a base in a solvent. It is a manufacturing method including that.
  • R2e-Lv used in this reaction can be obtained as a commercial product or can be produced by a known method.
  • the amount of R2e-Lv used in this reaction may be 1 equivalent or more relative to the compound represented by the formula (2j), and is not particularly limited as long as the intended reaction proceeds, but It is 1 equivalent or more and 50 equivalents or less.
  • Examples of the base used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, and silver oxide, as long as the intended reaction proceeds. There is no particular limitation in.
  • the amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (2j), and is not particularly limited as long as the intended reaction proceeds, but it is usually 1 It is equal to or more than 20 equivalents.
  • the amount of the additive used is 1 equivalent or more and 100 equivalents or less with respect to the compound represented by the formula (2j).
  • the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Methanol, ethanol, alcohol solvents such as isopropanol, benzene, toluene, xylene, mesitylene, chlorobenzene, benzene solvents such as dichlorobenzene, ethyl acetate, isopropyl acetate, ester solvents such as butyl acetate, nitrile solvents such as acetonitrile, Amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, dichloromethane, dichloroethane,
  • the amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2j). is there.
  • the temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 100 ° C or lower, or the boiling point of the solvent or lower.
  • aqueous solution an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved
  • an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved
  • thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily.
  • a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl-
  • an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane and chloroform, a hydrocarbon solvent such as hexane, heptane, cyclohexane and methylcyclohexane, which is incompatible with water. It is possible.
  • these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
  • the number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
  • the water content of the reaction mixture containing the compound represented by the formula (2j) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
  • reaction mixture containing the compound represented by the formula (2j) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
  • reaction mixture containing the compound represented by the formula (2j) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
  • the compound represented by the formula (1) can be produced by arbitrarily combining the production methods A to AC shown above. Alternatively, the compound represented by the formula (1) can be produced by optionally combining the known method and the production methods A to Z.
  • the compound of the present invention can control organisms harmful to plants, it can be used as a pesticide, especially as a pesticide for agricultural and horticultural use.
  • a pesticide especially as a pesticide for agricultural and horticultural use.
  • Specific examples include fungicides, insecticides, herbicides, plant growth regulators, and the like.
  • a bactericide is preferable.
  • the compound of the present invention can be used as a fungicide for agricultural and horticultural use for controlling plant diseases in fields, paddy fields, tea fields, orchards, meadows, lawns, forests, gardens, roadside trees and the like.
  • the plant diseases referred to in the present invention are crops, flowers, flowers, trees, wilting of plants such as trees, systemic abnormal pathological symptoms such as wilting, yellowing, atrophy, and captivity, or spots, leaf wilting, mosaic. , Partial morbidity such as cigar, wilting, root rot, root-knot, and hump are caused. That is, the plant becomes ill.
  • Pathogens causing plant diseases mainly include fungi, bacteria, spiroplasma, phytoplasma, viruses, viroids, parasitic higher plants, nematodes and the like.
  • the compound of the present invention is effective on fungi, but is not limited thereto.
  • the diseases caused by fungi are mainly fungal diseases.
  • fungi pathogens
  • pathogens include Aspergillus niger, Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and incomplete fungi.
  • fungus fungi root-knot fungus, powdery mildew fungus, sugar beet wilt fungus, oomycete, downy mildew, Pythium genus, Aphanomyces genus, zygomycetes Rhizopus genus, ascomycetes Fungi include peach leaf blight, corn sesame leaf blight, rice blast, powdery mildew, anthracnose, red mold, bacillus seedling, sclerotium, basidiomycetes, rust, smut, and purple print Fungi, blast fungus, sheath blight fungus, and imperfect fungi include gray mold, Alternaria, Fusarium, Penicillium, Rhizoctonia, and white silk.
  • the compound of the present invention is effective against various plant diseases.
  • specific examples of the disease name and the pathogen name will be shown.
  • Rice blast (Magnaporthe grisea), sheath blight (Thanatephorus cucumeris), brown rot (Ceratobasidium setariae), brown sclerotium (Waitea circinata), brown spot rot spelling bacterium (Therca erucorus phus) Sclerotium hydrophilum, red rot (Wairea circinata), black rot (Entyloma dactylidis), pneumococcal disease (Magnaporthe salvinii leaf blight, Ceratobosa sigma rot) Blight disease (Sphaerulina oryzina) , Frog seedling disease (Gibberella fujikuroi), seedling blight (Pythium spp., Fusarium spp., Trichoderma spp., Rhizopus spp., Rhizonia spore, Rhizoctonia spore, Rhizoptonia solipani, M
  • Pseudomonas syringae pv. syringae Red mold disease of corn (Gibberella zeae, etc.), Fusarium avenaceus (Pusillium spp, Pythium sp., Penicillium spp, Pythium spp, Pythium spp. ), Sesame leaf blight (Cochliobolus heterostrophus), smut (Ustilago maydis), anthrax (Colletotrichum graminicola), northern leaf spot (Cochliobolus carbonum), and brown stripe (Acivara vivaencia).
  • gray Blight (Botrytis cinerea), bud blight (Diaportthe medusaea), purple crest rot (Helicobasidium mompa), white crest rot (Rosellinia necatrix), root head cancer (Agrobacterium terrestris) (Agrobacterium terrestris).
  • Leaf blight (Crynebacterium, Crynebacterium). Tobacco leaf curl subgroup III geminivirus; powdery mildew of aubergine (Sphaerotheca fuliginea, etc.), scab (Mycovelothior porphyra rot), and plague (Phytophyta). C. ichorii), Bacterial stem blight (Pseudomonas corrugata), Stem rot bacterial disease (Erwinia chrysanthemi), Soft rot (Erwinia carotovora ssp. carotovera); Black rot (Xhanthomonas campestris pv.
  • Campestris Black spot bacterial disease (Pseudomonas syringae pv. Maculicola), White rot (Erwinia carotovora), Black spot (Erwinia carotovora); , Root rot (P oma lingam), clubroot (Plasmodiophora brassicae), downy mildew (Peronospora parasitica), black rot (Xhanthomonas campestris pv. campestris), black spot bacterial disease (Pseudomonas syringae pv. Maculicola), White rot (Erwinia carotovora), Black spot (Erwinia carotovora); , Root rot (P oma lingam), clubroot (Plasmodiophora brassicae), downy mildew (Peronospora parasitica), black rot (Xhanthomonas campestris pv. campestris), black spot
  • onion Canker (Curtobacterium flaccumfaciens), soft rot (Erwinia carotovora subsp carotovora), spot Bacterial (Pseudomonas syringae pv syringae), rot (Erwinia rhapontici), scale rot (Burkholderia gladioli), yellows Disease (Phytoplasma asteris); soft rot of garlic (Erwinia carotovora subsp. Carotovora), spring rot (Pseudomonas marginalis pv.
  • Glycinea Glycinea
  • anthracnose disease of green beans Coldetotrichum lanceumum
  • eudomonas syringae pv. Phaseolicola brown spot bacterial disease
  • Pseudomonas viridiflava leaf burn disease
  • Xhanthomonas campestris pv. phaseoli Powdery mildew (Erysiphe pisi), downy mildew (Peronospora pisi), bacterial wilt of vine (Pseudomonas syringae pv. Pisi), bacterial rot of vine (Xhanthomonas campestris pestis, pestis pv.
  • Plague (Phyto hthora nicotianae); Potato summer plague (Alternaria solani), black blight (Thanatephorus cucumeris), plague (Phytophthora infestaum varieties, dry scab (Helminthosporium fusiformus, dry rot), Helminthosporium fusiformus (Helminthosporium fusifolia) Disease (Spongospora subterranea), bacterial wilt (Ralstonia solanacearum), black wilt (Erwinia carotovora subsp. Atroseptica rot, scab (Streptomyces cerevisiae, Stabiles), scab. carotovora subsp.
  • scab Streptomyces sp.
  • Streptomyces sp. carotovora strawberry powdery mildew (Sphaerotheca aphanis var. aphanis), plague (Phytophthora nicotianae, etc.), anthrax (Glomerella ingulata, etc.), Fruit rot (Pythium ultimum), bacterial wilt (Ralstonia solanacearum), horn spot bacterial disease (Xhanthomonas campestris), bacterial blight (Pseudomonas marginalis pv.
  • Elsinoe leucospila Elsinoe leucospila
  • anthrax Colletotrichum theae-sinensis
  • ring spot disease Pestalotiopsis longiseta
  • red blight Pseudomonas pyrosanthe syringae pv.thea, pseudomonas syringae pv.thea). as sp.
  • Tobacco scab Alternaria alternata
  • powdery mildew Erysiphe cichoracearum
  • anthrax Colletotrichum gloeosporia porosaides
  • epidemic Phytophthora nuea
  • epidemics Phytophthora nuea
  • the compound of the present invention may be used as the present compound alone, but is preferably mixed with a solid carrier, a liquid carrier, a gas carrier, a surfactant, a fixing agent, a dispersant, a stabilizer, etc., and a powder or wettable powder.
  • a solid carrier e.g., a liquid carrier, a gas carrier, a surfactant, a fixing agent, a dispersant, a stabilizer, etc.
  • a powder or wettable powder e. wettable powder, aqueous solvent, granular aqueous solution, granule, emulsion, solution, microemulsion, aqueous suspension preparation, aqueous emulsion preparation, suspoemulsion preparation and the like.
  • the composition is not limited as long as the effect is exhibited.
  • composition containing the compound of the present invention an agricultural and horticultural pest control agent, an agricultural and horticultural fungicide, etc.
  • Examples of the method of applying the composition containing the compound of the present invention include a method of contacting with a plant or seed, or a method of adding the composition to cultivated soil and contacting with a root or rhizome of a plant.
  • any method of application as used by those skilled in the art will work well.
  • plant refers to a plant that performs photosynthesis and lives without exercise.
  • Specific examples include rice, wheat, barley, corn, coffee, banana, grape, apple, pear, peach, cherry, oyster, citrus, soybean, bean, cotton, strawberry, potato, cabbage, lettuce, tomato, cucumber, eggplant, Watermelon, sugar beet, spinach, snow pea, pumpkin, sugar cane, tobacco, bell pepper, sweet potato, taro, konjac, cotton, sunflower, rose, tulip, chrysanthemum, turf, etc. and their F1 varieties and the like can be mentioned.
  • it includes genetically modified crops that are produced by manipulating genes and the like and are not originally present in the natural world.For example, soybeans, corn, cotton, etc.
  • the “plant” in the present invention is a general term for all parts constituting the above-mentioned plant individual, and includes, for example, stems, leaves, roots, seeds, flowers, fruits and the like.
  • seed refers to a seed that stores nutrients for germination of young plants and is used for agricultural reproduction.
  • Specific examples include seeds of corn, soybeans, cotton, rice, sugar beet, wheat, barley, sunflower, tomato, cucumber, eggplant, spinach, snow peas, pumpkin, sugar cane, tobacco, peppers, oilseed rape, and their F1 varieties.
  • Examples include seeds, seed potatoes such as taro, potato, sweet potato, and konjac, edible lilies, bulbs such as tulips, seed balls such as rakkyo, and seeds and tubers of genetically modified crops.
  • the application rate and application concentration of the composition containing the compound of the present invention vary depending on the target crop, target disease, degree of disease occurrence, dosage form of the compound, application method and various environmental conditions, but when spraying or irrigating. Is suitably 0.1 to 10,000 g per hectare, and preferably 10 to 1,000 g per hectare. In the case of seed treatment, the amount used is 0.0001 to 1000 g, preferably 0.001 to 100 g, per 1 kg of seeds as the amount of active ingredient.
  • the composition containing the compound of the present invention is used as a foliage spraying treatment on a plant individual, a spraying treatment on a soil surface, an injection treatment into soil or a soil irrigation treatment, the composition is diluted with an appropriate carrier at an appropriate concentration.
  • the processing may be performed.
  • the composition containing the compound of the present invention When the composition containing the compound of the present invention is brought into contact with a plant seed, it may be diluted to an appropriate concentration and then immersed, dressed, sprayed or smeared on the plant seed before use.
  • the amount of the composition used in the case of dipping, dressing, spraying or smearing is usually about 0.05 to 50%, preferably 0.1 to 30% of the weight of dry plant seeds as the amount of active ingredient. Is suitable, but it may be appropriately set depending on the form of the composition and the kind of plant seed to be treated, and is not limited to these ranges.
  • composition containing the compound of the present invention if necessary, other pesticides, for example, fungicides, insecticides, acaricides, nematicides, herbicides, pesticides such as biological pesticides and plant growth regulators, nucleic acids.
  • pesticides for example, fungicides, insecticides, acaricides, nematicides, herbicides, pesticides such as biological pesticides and plant growth regulators, nucleic acids.
  • a disease controlling agent International Publication No. WO 2014/062775
  • soil conditioner or a fertilizing substance.
  • bactericide that can be used by mixing with the compound of the present invention are exemplified in the following group b, and include salts, isomers and N-oxides thereof.
  • the known disinfectants are not limited to these.
  • Group b b-1: Phenylamide fungicide As a phenylamide fungicide, [b-1.1]: benalaxyl (benalaxyl), [b-1.2] benalaxyl M or chiralaxyl (benalaxyl-M or chiralaxyl), [b -1.3] Furalaxyl, [b-1.4] Metalaxyl, [b-1.5] Metalaxyl M or Mephenoxam (Metalaxyl-M or mefenoxam), [b-1.6] Oxadixyl (-) oxadixyl), [b-1.7] off-race, and the like.
  • b-2 mitotic cell division and cell division inhibitor
  • mitotic cell division and cell division inhibitor As a mitotic cell division and cell division inhibitor, [b-2.1] benomyl, [b-2.2] carbendazim, [b- 2.3] fuberidazole, [b-2.4] thiabendazole, [b-2.5] thiophanate, [b-2.6] thiophanate-methyl, [b- 2.7] Diethofencarb, [b-2,8] zoxamide, [b-2.9] ethaboxam, [b-2.10] pencycuron, [b-2. 11] Full opico Lido (fluopicolide), [b-2.12] phenamacril and the like can be mentioned.
  • SDHI agent Succinate dehydrogenase inhibitor
  • b-4 Quinone external inhibitor (QoI agent) As a quinone external inhibitor (QoI agent), [b-4.1] azoxystrobin, [b-4.2] cumoxystrobin, [b-4.3] dimoxist Robin (dimoxystrobin), [b-4.4] enoxastrobin (enoxastrobin), [b-4.5] famoxadone, [b-4.6] fenamidone, [b-4.7.
  • quinone internal inhibitor examples include [b-5.1] cyazofamide and [b-5.2] amisulbrom.
  • b-6 Oxidative phosphorylation uncoupling inhibitor As an oxidative phosphorylation uncoupling inhibitor, [b-6.1] binapacryl (binapacryl), [b-6.2] meptyldinocap, [b-6.2] Examples thereof include b-6.3] dinocap and [b-6.4] fluazinam.
  • quinone external stigmaterin-binding subsite inhibitor examples include [b-7.1] amethoctrazine.
  • b-8 Amino acid biosynthesis inhibitor As an amino acid biosynthesis inhibitor, [b-8.1] cyprodinil, [b-8.2] mepanipyrim, and [b-8.3] pyrimethanil (pyrimethanil). ) And the like.
  • b-9 Protein biosynthesis inhibitor [b-9.1] streptomycin, [b-9.2] blasticidin S (blasticidin-S), [b-9. 3] Kasugamycin, [b-9.4] oxytetracycline and the like.
  • b-10 Signal transduction inhibitor As a signal transduction inhibitor, [b-10.1] fenpiclonil, [b-10.2] fludioxonil, [b-10.3] quinoxyphen, [B-10.4] proquinazid, [b-10.5] chlorozolinate, [b-10.6] dimethaclone, [b-10.7] iprodione, [b -10.8] procymidone, [b-10.9] vinclozoline and the like can be mentioned.
  • b-11 Lipid and Cell Membrane Biosynthesis Inhibitors [b-11.1] edifenphos, [b-11.2] iprobenphos, [b-11.3] as lipid and cell membrane biosynthesis inhibitors. ] Pyrazophos, [b-11.4] isoprothiolane, [b-11.5] biphenyl, [b-11.6] chloroneb, [b-11.7] dichlorane (Dicloran), [b-11. 8] quintozene, [b-11. 9] tecnazene, [b-11.10] tolclofos-methyl, [b-11.11]. Etridiazole (ec hlomezol or etridiazole), [b-11.12] iodocarb, [b-11.13] propamocarb, [b-11.14] prothiocarb, and the like.
  • Etridiazole ec hlomezol or etridiazole
  • DI agent Demethylation inhibitor
  • demethylation inhibitors include [b-12.1] azaconazole, [b-12.2] bitertanol, [b-12.3] bromuconazole, and [b-12.3] bromuconazole.
  • Fenbuconazole [b-12.12] fluquinconazole, [b-12.13] quinconazole, [b-12.14] flusilazole, [b-12] .15] Flutriafol, [b-12.16] hexaconazole, [b-12.17] imazalil, [b-12.18] imibenconazole, [B-12.19] ipconazole, [b-12.20] metconazole, [b-12.21] microbutanil , [B-12.22] nuarimol, [b-12.23] oxpoconazole, [b-12.24] oxpoconazole fumarate, [b- 12.25] pefurazoate, [b-12.26] penconazole, [b-12.27] prochloraz, [b-12.28] propiconazole, [b- 12.29] Prothioconazole, [b-12.30] Pyrifenox, [b-12.31] Pyriso
  • Triadimenol [b-12.37] triflumizole, [b-12.38] triforine, [b-12.39] triticonazole [b-12] .40] mefentrifluconazole, [b-12.41] ipfentrifluconazole, and the like.
  • b-13 Amine-based bactericide As amine-based bactericide, [b-13.1] aldimorph, [b-13.2] dodemorph, [b-13.3] fenpropimorph ), [B-13.4] tridemorph, [b-13.5] phenpropidin, [b-13.6] piperalin, [b-13.7] spiroxamine. ) And the like.
  • b-14 3-keto reductase inhibitor in C4 demethylation of sterol biosynthesis
  • b-15 Squalene epoxidase inhibitor for sterol biosynthesis
  • a squalene epoxidase inhibitor for sterol biosynthesis [b-15.1] pyributicarb (b-15.2) naphthifine (naftifine), [b] -15.3] Terbinafine and the like can be mentioned.
  • b-16 Cell wall biosynthesis inhibitor As a cell wall biosynthesis inhibitor, [b-16.1] polyoxins (polyoxins), [b-16.2] dimethomorph, [b-16.3] flumorph ( flumorph), [b-16.4] pyrimorph, [b-16.5] bench avalicarb, [b-16.6] bench avalicarb isopropyl (b). -16.7] iprovalicarb, [b-16.8] mandipropamide, [b-17.9] valifenalate and the like can be mentioned.
  • b-17 Melanin biosynthesis inhibitor As a melanin biosynthesis inhibitor, [b-17.1] phtalide or phthalide, [b-17.2] pyroquilon, [b-17.3] tricyclazole. (Tricylazole), [b-17.4] carpropamide, [b-17.5] diclocymet, [b-17.6] phenoxanil, [b-17.7] tolprocarb. ) And the like.
  • b-18 Host plant resistance inducer [b-18.1] acibenzolar S-methyl (acibenzalar-S-methyl), [b-18.2] probenazole (b), and [b-18.2] -18.3] thiazinyl (tiadinil), [b-18.4] isotianil, [b-18.5] laminarin and the like can be mentioned.
  • b-19 Dithiocarbamate fungicide
  • a dithiocarbamate fungicide [b-19.1] mancozeb or manzeb (mancozeb or manzeb), [b-19.2] manneb, [b-19.3].
  • Phthalimide bactericide As phthalimide bactericide, [b-20.1] captan (captan), [b-20.2] captafol (captafol), [b-20.3] folpet (folpet) ), [B-20.4] fluorofolpet and the like.
  • b-21 Guanidine fungicide As a guanidine fungicide, [b-21.1] guazatin, [b-21.2] iminoctadine, [b-21.3] iminoctadine albesylate (Imnoctadine albesilate), [b-21.4] iminoctadine triacetate and the like.
  • Multi-action point contact active type bactericide [b-22.1] basic copper chloride (copper oxychloride), [b-22.2] cupric hydroxide (Copper (II) hydroxide), [b-22.3] basic copper sulfate (copper hydroxide sulfate), [b-22.4] organic copper compound (organocopper compound), [b-22.5] dodecylbenzene sulfone Acid bisethylenediamine copper complex salt [II] (Dodecylbenzene sulphonic acid bisethylenediamineamine copper [II] salt, DBEDC), [b-22.6] sulphur, [b-22.7] fluorimide (fluorim).
  • b-23 Other fungicides As other fungicides, [b-23.1] diclobentiazox, [b-23.2] fenpicoxamide, [b-23.3]. ] Dipymetitron, [b-23.4] bupyrimate, [b-23.5] dimethirimol, [b-23.6] ethirimol, [b-23.7] acetic acid Triphenyl tin (fentin acetate), [b-23.8] triphenyl tin chloride (fentin chloride), [b-23.9] triphenyl tin hydroxide (fentin hydroxide), [b-23.10] oxolinic acid (Oxo linic acid), [b-23.11] hymexazol, [b-23.12] octilinone, [b-23.13] fosetyl, [b-23.14] phosphite.
  • A3 represents a hydrogen atom, a halogen atom, a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, or a cyano group
  • A4 represents a hydrogen atom, a C1 to C6 alkyl group, a C1 to C6 It represents a haloalkyl group or a C3-C8 cycloalkyl group.
  • m2 represents an integer of 0 to 6
  • A14 and A15 each independently represent a halogen atom, a cyano group, or a C1 to C6 alkyl group
  • A16 represents a hydrogen atom or a halogen atom.
  • A17 represents a halogen atom or a C1 to C6 alkoxy group
  • m2 is 2 or more, 2 or more A17's each independently represent a substituent, Can be different.
  • Expression (s20) [In the formula, A18 and A19 each independently represent a halogen atom, a cyano group, or a C1 to C6 alkyl group, and A20, A21, and A22 each independently represent a hydrogen atom, a halogen atom, Alternatively, it represents a C1 to C6 alkoxy group. (See WO 07/066601),
  • Expression (s24) or Expression (s25) [Wherein, m4 represents an integer of 0 to 5, A27 represents a C1 to C6 alkyl group, A28 represents a halogen atom, a cyano group, a C1 to C6 alkyl group, or a C1 to C6 haloalkyl group. And when m4 is 2 or more, two or more A28's each independently represent a substituent and may be the same or different, and A29 is a C1 to C6 alkyl group, a C2 to C6 alkenyl group, or C3. Represents a C6 alkynyl group. ] (See WO 13/037771),
  • Expression (s26) or Expression (s27) [Wherein, m5 represents an integer of 0 to 5, A30 represents a C1 to C6 alkyl group, A31 represents a halogen atom, a cyano group, a C1 to C6 alkyl group, or a C1 to C6 haloalkyl group. When m5 is 2 or more, 2 or more A31's each independently represent a substituent, and may be the same or different, and A32's are C1 to C6 alkyl groups, C2 to C6 alkenyl groups, or C3. Represents a C6 alkynyl group. ] (See WO 13/037771),
  • A41 represents a hydrogen atom, a sulfur group (-SH), a thiocyanate group (-SCN), or a C1 to C6 alkylthio group
  • A42, A43, A44 and A45 are each independently Represents a hydrogen atom or a halogen atom.
  • the compound represented by these (refer international publication 09/077443),
  • insecticide that can be used as a mixture with the compound of the present invention are exemplified in the following group c, and include salts, isomers and N-oxides thereof.
  • known insecticides are not limited to these.
  • Group c c-1: Carbamate acetylcholinesterase (AChE) inhibitor [C-1.1] phosphocarb, [c-1.2] alanycarb, [c-1.1] as a carbamate acetylcholinesterase (AChE) inhibitor -1.3] butocarboxim, [c-1.4] butoxycarboxim, [c-1.5] thiodicarb, [c-1.6] thiophanox ), [C-1.7] aldicarb, [c-1.8] bendiocarb, [c-1.9] benfuracarb, [c-1.10] carbaryl (carba).
  • AChE carbaryl
  • c-2 Organophosphorus acetylcholinesterase (AChE) inhibitor [c-2.1] acephate, [c-2.2] azamethiphos, as an organophosphorus acetylcholinesterase (AChE) inhibitor [C-2.3] Azinphos-methyl, [c-2.4] Azinphos-ethyl, [c-2.5] Ethephon, [c-2.6] ] Cadussafos, [c-2.7] chlorethoxyphos, [c-2.8] chlorfenvinphos, [c-2.9] chlormephos, [c- 2.10] Black Chlorpyrifos, [c-2.11] chlorpyrifos-methyl, [c-2.12] coumaphos, [c-2.13] cyanophos, [c-2.
  • GABAergic chloride ion blocker As GABAergic chloride ion blocker, [c-3.1] chlordane, [c-3.2] endosulfan, [c-3.3] ] Lindane, [c-3.4] dienochlor, [c-3.5] ethiprole, [c-3.6] fipronil, [c-3.7] acetate Examples include acetoprole and the like.
  • c-4 Sodium channel modulator As a sodium channel modulator, [c-4.1] acrinathrin, [c-4.2] allethrin [(1R) -isomer] (allethrin [(1R) -somer]), [C-4.3] bifenthrin, [c-4.4] bioallethrin, [c-4.5] bioallethrin S-cyclopentenyl isomer, [c- 4.6] bioresmethrin, [c-4.7] cycloprothrin, [c-4.8] cyfluthrin, [c-4.
  • c-5 Competitive modulator of nicotinic acetylcholine receptor (nAChR) As a competitive modulator of nicotinic acetylcholine receptor (nAChR), [c-5.1] acetamiprid, [c-5.2] clothianidin (clothianidin).
  • c-6 Nicotinic acetylcholine receptor (nAChR) allosteric modulator As a nicotinic acetylcholine receptor (nAChR) allosteric modulator, [c-6.1] spinosad, [c-6.2] spinetoram, etc. Is mentioned.
  • c-7 Glutamate agonist chloride ion channel (GluCl) allosteric modulator
  • glutamate agonist chloride ion channel (GluCl) allosteric modulator [c-7.1] abamectin, [c-7.2] emamectin benzoic acid Examples thereof include salt (emactin benzoate), [c-7.3] lepimectin, and [c-7.4] milbemectin.
  • c-8 Juvenile hormone analogs As juvenile hormone analogs, [c-8.1] hydroprene, [c-8.2] quinoprene, [c-8.3] methoprene (methoprene) ), [C-8.4] phenoxycarb, and [c-8.5] pyriproxyfen.
  • c-9 Non-specific (multi-site) inhibitor
  • a non-specific (multi-site) inhibitor As a non-specific (multi-site) inhibitor, [c-9.1] methyl bromide (meth-bromide), [c-9.2] chloropicrin , [C-9.3] cryolite, [c-9.4] sulfuryl fluoride, [c-9.5] borax, [c-9.6] boro Acid (boric acid), [c-9.7] octaborate disodium salt (disodium octoborate), [c-9.8] metaborate sodium salt (c-9.9) tartar (tartar) emetic), [c-9.10] dazomet, [c-9.11] metam (m etc., [c-9.12] carbam sodium salt, and the like.
  • chordal organ TRPV channel modulator examples include [c-10.1] pymetrozine and [c-10.2] pyrifluquinazon.
  • c-11 Mite growth inhibitor As a mite growth inhibitor, [c-11.1] clofentezine, [c-11.2] diflovidazin, [c-11.3] hexithiazox (Hexythiazox), [c-11.4] ethoxazole and the like.
  • c-12 Mitochondrial ATP synthase inhibitor As mitochondrial ATP synthase inhibitor, [c-12.1] diafenthiuron, [c-12.2] azocyclotin, [c-12. 3] Cyhexatin, [c-12.4] fenbutatin oxide, “c-12.5” propargite, “c-12.6” tetradiphone, etc. .
  • c-13 Oxidative phosphorylation uncoupling agent that perturbs proton gradient
  • oxidative phosphorylation uncoupling agent that perturbs proton gradient [c-13.1] chlorfenapyl and [c-13.2] DNOC (Dinitro-ortho-cresol), [c-13.3] vinapacryl, [c-13.4] sulfluramide and the like.
  • c-14 Nicotinic Acetylcholine Receptor (nAChR) Channel Blocker As a nicotinic acetylcholine receptor (nAChR) channel blocker, [c-14.1] bensultap, [c-14.2] cartap hydrochloride (cartap) hydrochloride), [c-14.3] thiocyclam, [c-14.4] monosultap and the like.
  • nAChR Nicotinic Acetylcholine Receptor
  • nAChR nicotinic acetylcholine receptor
  • c-15 Chitin biosynthesis inhibitor type 0
  • chitin biosynthesis inhibitor type 0 As the chitin biosynthesis inhibitor type 0, [c-15.1] bistrifluron (bistrifluron), [c-15.2] chlorfluazuron (chlorfluazuron), [c-15.3] diflubenzuron, [C-15.4] flucycloxuron, [c-15.5] fluphenoxuron, [c-15.6] hexaflumuron, [c-15.7] Lufenuron, [c-15.8] novaluron, [c-15.9] noviflumuron, [c-15.10] teflubenzuron, [c-15.11]. Rifurumuron (triflumuron), and the like.
  • c-16 chitin biosynthesis inhibitor type 1
  • Examples of the chitin biosynthesis inhibitor type 1 include [c-16.1] buprofezin and the like.
  • c-17 Insect molting inhibitor for fly flies
  • An insect molting inhibitor for fly flies includes [c-17.1] cyromazine and the like.
  • c-18 Molting hormone (ecdysone) receptor agonist
  • a molting hormone (ecdysone) receptor agonist [c-18.1] chromafenozide, [c-18.2] halofenozide, [c-18] .3] methoxyphenozide, [c-18.4] tebufenozide and the like.
  • Octopamine receptor agonist examples include [c-19.1] amitraz.
  • c-20 Mitochondrial electron transfer complex III inhibitor As a mitochondrial electron transfer complex III inhibitor, [c-20.1] hydramethylnon, [c-20.2] acequinocyl, Examples include [c-20.3] fluacrypyrim and [c-20.4] bifenazate.
  • c-21 Mitochondrial electron transport complex I inhibitor (METI) As a mitochondrial electron transport complex I inhibitor (METI), [c-21.1] fenazaquin, [c-21.2] fenpyroximate, [c-21.3] pyridaben, [C-21.4] pyrimidifen, [c-21.5] tebufenpyrad, [c-21.6] tolfenpyrad, [c-21.7] rotenone and the like.
  • METI Mitochondrial electron transport complex I inhibitor
  • c-22 Voltage-gated sodium channel blocker
  • Examples of the voltage-gated sodium channel blocker include [c-22.1] indoxacarb and [c-22.2] metaflumizone.
  • c-23 Acetyl CoA carboxylase inhibitor As an acetyl CoA carboxylase inhibitor, [c-23.1] spirodiclofen, [c-23.2] spiromesifen, [c-23.3]. ] Spirotetramat etc. are mentioned.
  • c-24 Mitochondrial electron transport complex IV inhibitor As a mitochondrial electron transport complex IV inhibitor, [c-24.1] aluminum phosphide, [c-24.2] calcium phosphide ( calcium phosphide, [c-24.3] phosphine, [c-24.4] zinc phosphide, [c-24.5] calcium cyanide, [c Examples include ⁇ 24.6] sodium cyanide and [c-24.7] potassium cyanide.
  • c-25 Mitochondrial electron transport complex II inhibitor [c-25.1] cyenopyrafen, [c-25.2] cyflumethofen, [c-25.1] as mitochondrial electron transport complex II inhibitor -25.3] Pyflubumide and the like.
  • ryanodine receptor modulator As a ryanodine receptor modulator, [c-26.1] chlorantraniliprole (chlanantraniprole), [c-26.2] cyantraniliprole, [c-26. 3] Flubendiamide and the like can be mentioned.
  • c-28 Other insecticides [c-28.1] azadirachtin, [c-28.2] benzoximate, [c-28.3] phenisobromo as other insecticides. Phenisobromolate, [c-28.4] quinomethionate, [c-28.5] dicofol, [c-28.6] pyridalyl, [c-28.7] bromopropyiate.
  • Soybean lettuce Soybean lecithin [c-28.91] starch (starch), [c-28.92] hydroxypropyl starch, [c-28.93] fatty acid glyceride (decanoyloctanoylglycerol), [c-28. 94] Propylene glycol monofatty acid ester, [c-28.95] diatomite, [c-28.96] afoxolaner, [c-28.97] fluazaind.
  • Lysine [c-28.98] afidopyropene, [c-28.99] cyhalodiamide cyhalodiamide
  • [c-28.100] thioxazaphen [c-28.101] fluhexafone, [c-28.102] fluralaner, [c-28.103] fluxamethamid (c-28.101). Fluxametamide), [c-28.104] tetrachlorantraniliprole, [c-28.105] sarolaner, [c-28.106] lotilaner, [c-28.107].
  • m10 represents an integer of 0 to 2
  • A61 represents a trifluoromethyl group, a trifluoromethylthio group, a trifluoromethylsulfinyl group, or a trifluoromethylsulfonyl group
  • A62 represents a hydrogen atom, or It represents a trifluoromethyl group
  • V6 represents a nitrogen atom or a carbon atom
  • V7 represents an oxygen atom or an N-methyl group.
  • A65 represents a hydrogen atom, a C1 to C6 alkyl group, or a C1 to C6 haloalkyl group
  • A66 represents a hydrogen atom, a halogen atom, or a C1 to C6 alkyl group
  • A67 and A68 represent A hydrogen atom, a C1 to C6 alkyl group optionally substituted with a cyano group, an alkyl group optionally substituted with a methoxy group, an alkyl group optionally substituted with an ethoxy group, Or represents a C3 to C8 cycloalkyl group
  • A69 represents a hydrogen atom, a cyano group, a C1-C6 haloalkyl group optionally substituted with a cyano group, a C1-C6 alkyl group, or a C3-C8 cycloalkyl group.
  • the compound represented by these (refer international publication 12/14
  • Expression (s53) or Expression (s54) [In the formula, A70 represents a methyl group, an ethyl group, an isopropyl group, a 2,2,2-trifluoroethyl group, or a phenyl group, and A71 represents A72 represents a partial structure selected from the group consisting of: V8 represents an oxygen atom, a sulfur atom, —CH 2 —, or —CH 2 CH 2 —. ] The compound represented by these (refer international publication 14/167084, international publication 16/055431),
  • m11 represents an integer of 0 to 1
  • A73 represents a chlorine atom, a bromine atom, a methyl group, or a trifluoromethyl group
  • A74 represents a hydrogen atom, a chlorine atom, a bromine atom, a cyano group, Or a trifluoromethyl group
  • A75 represents a hydrogen atom, a chlorine atom or a bromine atom
  • A76 and A77 each independently represent a C1 to C6 alkyl group, or a C3 to C8 cycloalkyl group
  • A78 represents a chlorine atom, a bromine atom, a cyano group, a nitro group, a difluoromethyl group, or a trifluoromethyl group.
  • a compound represented by the formula see International Patent Publication No.
  • the mixing ratio of the compound of the present invention and the other pesticide that can be used as a mixture according to the above need is not particularly limited as long as the effect is exhibited, but usually, to the compound of the present invention
  • the other pesticides have a weight ratio of 0.001 to 1000, preferably 0.01 to 100.
  • the obtained organic layer was washed successively with an aqueous sodium thiosulfate solution and saturated brine, and dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 55 mg as an orange-brown solid.
  • the obtained organic layer was washed with saturated saline and dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 67 mg of white amorphous.
  • the obtained organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 93 mg of a pale yellow amorphous.
  • the obtained organic layer was washed successively with aqueous sodium thiosulfate solution and saturated brine, dried over sodium sulfate, and the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography.
  • the compound was obtained as 440 mg as an ocher solid.
  • Step 1 Synthesis of 1- (2,4,6-trifluorophenyl) -N- (2-methyl-3-thienyl) methanimine 2,4,6-trifluorobenzaldehyde 2.03 g, 2-methyl-3- 20 ml of a dichloroethane solution containing 1.47 g of aminothiophene (synthesized by the method described in WO 2017/035360) and 1.53 g of magnesium sulfate was stirred at 80 ° C. for 2 hours. After cooling to room temperature, magnesium sulfate in the reaction mixture was removed by filtration, and the obtained filtrate was evaporated under reduced pressure. The obtained brown oily substance (3.24 g) was the title compound and was used in the next reaction without further purification.
  • Step 2 Synthesis of 3,5-dimethyl-1- (2-methyl-3-thienyl) -2- (2,4,6-trifluorophenyl) -2,3-dihydropyridin-4 (1H) -one 1 3.24 g of-(2,4,6-trifluorophenyl) -N- (2-methyl-3-thienyl) methanimine and ((1-methoxy-2-methylpenta-1,3-dien-3-yl) oxy ) 10 ml of an acetonitrile solution containing 1.13 g of trimethylsilane was ice-cooled, 200 mg of a 42 wt% tetrafluoroboric acid aqueous solution was added, and the mixture was stirred for 1 hour under ice-cooling.
  • Step 1 Synthesis of 1- (2-chloro-4-fluorophenyl) -N- (3-thienyl) methanimine 2-chloro-4-fluorobenzaldehyde 1.00 g, 3-aminothiophene oxalate 1.19 g and triethylamine 20 ml of a THF solution containing 1.27 g was stirred at room temperature for 4 hours. After removing solids in the reaction mixture by filtration, the obtained filtrate was evaporated under reduced pressure. The ocher solid 1.29 g obtained was the title compound and was used in the next reaction without further purification.
  • Step 2 Synthesis of 2- (2-chloro-4-fluorophenyl) -3,5-dimethyl-1- (3-thienyl) -2,3-dihydropyridin-4 (1H) -one 1- (2-chloro Acetonitrile solution containing 1.29 g of -4-fluorophenyl) -N- (3-thienyl) methanimine and 1.26 g of ((1-methoxy-2-methylpenta-1,3-dien-3-yl) oxy) trimethylsilane 20 ml was ice-cooled, 42 weight% tetrafluoroboric acid aqueous solution 268 mg was added, and it stirred under ice-cooling for 1 hour.
  • Step 1 Synthesis of 1- (2,4-difluorophenyl) -N- (3-thienyl) methanimine 2,4-difluorobenzaldehyde 5.00 g, 3-aminothiophene oxalate 6.66 g and triethylamine 7.12 g 100 ml of the THF solution containing the mixture was stirred at room temperature for 3 hours. The insoluble component in the reaction mixture was removed by filtration, and the obtained filtrate was evaporated under reduced pressure. The obtained black oily substance (1.28 g) was the title compound and was used in the next reaction without further purification.
  • Step 2 Synthesis of 2- (2,4-difluorophenyl) -1- (3-thienyl) -2,3-dihydropyridin-4 (1H) -one 1- (3-thienyl) -2 synthesized in Step 1 -(2,4-Difluorophenyl) -2,3-dihydropyridin-4 (1H) -one and ((1-methoxy-2-methylpenta-1,3-dien-3-yl) oxy) trimethylsilane 7.27 g After ice-cooling 50 ml of an acetonitrile solution containing the above, 1.50 g of a 42 wt% tetrafluoroboric acid aqueous solution was added, and the mixture was stirred under ice-cooling for 1 hour.
  • Step 1 Synthesis of N-((2,6-difluorophenyl) (ethoxy) methyl) -1,3,4-thiadiazol-2-amine 2,6-difluorobenzaldehyde 5.00 g, 2-amino-1,3 25 ml of an ethanol solution containing 2.97 g of 4-thiadiazole and 146 ⁇ l of piperidine was stirred at 75 ° C. for 5 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 6.60 g of a yellow solid. Used for the next reaction without further purification.
  • Step 2 1-((1,3,4-thiadiazol-2-yl) amino) -1- (2,6-difluorophenyl-5-methoxy-2,4-dimethylpenta-1,4-diene-3 Synthesis of N-one 6.60 g of N-((2,6-difluorophenyl) (ethoxy) methyl) -1,3,4-thiadiazol-2-amine obtained in Step 1 and ((1-methoxy-2- 132 ml of an acetonitrile solution containing 7.31 g of methylpenta-1,3-dien-3-yl) oxy) trimethylsilane was ice-cooled, 1.01 ml of a 42 wt% tetrafluoroboric acid aqueous solution was added, and the mixture was stirred at room temperature for 3 hours.
  • Step 1 Synthesis of N-o-toluyl-1- (2,4,6-trifluorophenyl) methanimine
  • 2.00 g of orthotoluidine and 1.40 g of magnesium sulfate 15 ml of a dichloroethane solution containing was stirred under reflux for 3 hours.
  • magnesium sulfate in the reaction mixture was removed by filtration, and the obtained filtrate was evaporated under reduced pressure. The resulting orange solid was the title compound and was used in the next reaction without further purification.
  • Step 2 Synthesis of 3,5-dimethyl-1- (o-toluyl) -2- (2,4,6-trifluorophenyl) -2,3-dihydropyridin-4 (1H) -one
  • Table 4 shows compounds represented by the formula (1) synthesized according to the above Examples, but the present invention is not limited thereto.
  • the compounds in Table 4 are represented by formula (A).
  • Table 1 shows their 1 H-NMR data.
  • the compound of the present invention is effective against plant diseases, but the present invention is not limited to these examples.
  • Test Example A Rice blast After sown with seeds of a test plant (rice variety: Kofu), it was cultivated until the second leaf developed.
  • the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution.
  • the obtained drug solution was sprayed on the test plant (2.5 ml / pot).
  • the plant after the drug solution was dried was inoculated with 1 to 2 ⁇ 10 5 cells / ml of a conidia suspension of the rice blast fungus (Magnaporthe grisea) by spraying.
  • the plant After inoculation, the plant was left in a moist chamber with a room temperature of 20 to 23 ° C. for about 24 hours to promote disease onset. The degree of disease onset 6 to 10 days after the inoculation was investigated to evaluate the effect of the drug solution.
  • Test Example B Tomato gray mold disease After sowing seeds of a test plant (tomato variety: large Fukuju), 3 to 5 true leaves were cultivated.
  • the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution.
  • the obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the drug solution was dried, the plants were spray-inoculated with a conidial suspension of 4-8 ⁇ 10 5 cells / ml of Botrytis cinerea. After inoculation, the plant was left in a wet room at a room temperature of 20 to 23 ° C. for about 48 hours to promote the onset of disease. The degree of disease onset 2 to 3 days after the inoculation was investigated to evaluate the effect of the drug solution.
  • Test Example C Cabbage black spot disease Seeds of a test plant (cabbage variety: four seasons harvest) were sown and then cultivated until cotyledons developed.
  • the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution.
  • the obtained drug solution was sprayed on the test plant (2.5 ml / pot).
  • the plants after the drug solution had been dried were spray-inoculated with a conidial suspension of 4-8 ⁇ 10 5 cells / ml of cabbage black scab (Alternia brassicicola).
  • the plant After inoculation, the plant was left in a wet room at a room temperature of 20 to 23 ° C. for about 48 hours to promote the onset of disease. The degree of disease onset 2 to 3 days after the inoculation was investigated to evaluate the effect of the drug solution.
  • Test Example D Barley powdery mildew After planting seeds of a test plant (barley variety: Akakami Riki), it was cultivated until the first leaf developed. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the chemical solution was dried, the conidia of barley powdery mildew (Blumeria graminis f.sp.hordei) were beaten and inoculated to the plants. The degree of illness was investigated 6 to 10 days after the inoculation, and its effect was evaluated.
  • Test Example E Wheat leaf rust Seeds of a test plant (wheat variety: Norin 61) were sown and then cultivated until the first leaves developed.
  • the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution.
  • the obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the drug solution was dried, the plants were inoculated with 1 to 2 ⁇ 10 5 pieces / ml of a spore suspension of Puccinia recondita.
  • the plant After inoculation, the plant was left in a moist chamber with a room temperature of 20 to 23 ° C. for about 24 hours to promote disease onset. The degree of disease onset 7 to 10 days after the inoculation was investigated to evaluate the effect of the drug solution.
  • Test Example F Cucumber anthracnose After seeding the seeds of a test plant (cucumber variety: Sagamihanjiro), it was cultivated until one true leaf developed.
  • the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution.
  • the obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the drug solution was dried, the plants were inoculated with 2 to 4 ⁇ 10 5 cells / ml of a conidia suspension of anthrax of Cucumber (Colletotrichum orbiculare) by spraying.
  • the plant After inoculation, the plant was left in a moist chamber with a room temperature of 20 to 23 ° C. for about 24 hours to promote disease onset. The degree of disease onset 6 to 10 days after the inoculation was investigated to evaluate the effect of the drug solution.
  • Test Example G Grape downy mildew After sowing seeds of a test plant (grape variety: Neo Muscat), the seedlings were cultivated until 3 to 4 true leaves were developed.
  • the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution.
  • the obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the drug solution was dried, the plants were spray-inoculated with a suspension of zoospores of Plasmopara viticola at 1 to 2 ⁇ 10 4 cells / ml.
  • the cells were allowed to stand in a wet room at room temperature of 20 ° C. for about 24 hours to promote the onset of the disease.
  • the degree of disease onset 7 to 10 days after the inoculation was investigated to evaluate the effect of the drug solution.
  • the behavior of the compound represented by the formula (1) in soil can be analyzed by a known method.
  • the analysis method is illustrated below, but the method is not limited to this.
  • Soil equivalent to 5 g of dry soil (Yasu soil: sandy loam soil) was put in a 50 mL container, water was added so as to be 50-60% of the maximum water capacity, and incubated in a thermostat at 20 ° C. for about 2 weeks.
  • the obtained test soil was treated with a methanol solution containing 20 ⁇ g / mL of the compound represented by the formula (1), and the decay was analyzed immediately after the treatment and 15, 30, 60 and 90 days later.
  • the concentration of the compound represented by formula (1) in the soil was calculated by adding hydrous acetonitrile to the soil, extracting the compound by ultrasonic dispersion, and analyzing the supernatant by high performance liquid chromatography. Table 6 shows the results.
  • the compounds in which Z is a thienyl group (Compound Nos. 2 and 4) decomposed in soil for 30 to 60% in 90 days.
  • the compound in which Z is a phenyl group (Comparative Example compound) obtained in Reference Example 13 was not observed to decompose in soil for 90 days. That is, the compound represented by the formula (1) in which a 5-membered heterocyclic substituent containing a hetero atom such as a sulfur atom is introduced into Z is more degradable in soil than the compound in which Z is a phenyl group. was found to be high. The compound group having such soil degradability is useful because the environmental load is reduced.
  • the pyridone compound of the present invention is a novel compound and can control plant diseases, it is useful as a pesticide, for example, an agricultural and horticultural pest control agent, particularly an agricultural and horticultural fungicide.

Abstract

Provided is a novel compound that controls plant disease. This pyridone compound is a novel compound that is capable of controlling plant disease.

Description

ピリドン化合物およびそれを有効成分とする農園芸用殺菌剤Pyridone compounds and agricultural and horticultural fungicides containing them as active ingredients
　本発明は、ピリドン化合物および該化合物を有効成分とする農薬に関するものである。 The present invention relates to a pyridone compound and an agrochemical containing the compound as an active ingredient.
　安定的な農業生産を確保する上で、農園芸作物の病害を防除することは重要な役割を果たす。そのため、様々な殺菌剤が使用されているが、薬剤感受性菌のみならず薬剤耐性菌に対しても有効な新規殺菌剤は切望され続けている。 Controlling diseases of agricultural and horticultural crops plays an important role in ensuring stable agricultural production. Therefore, various bactericides have been used, but new bactericides effective not only against drug-susceptible bacteria but also against drug-resistant bacteria have been earnestly desired.
　ところで、１，２，３，５－置換－４－ピリドン化合物に関する先行例が知られている。例えば、抗菌薬として、５位にカルボキシ基を有する１，２，３，５－置換－４－ピリドン化合物が開示されている（例えば、特開昭５３－６５８８２号公報および特開昭６１－２４６１６３号公報）。 By the way, precedent examples of 1,2,3,5-substituted-4-pyridone compounds are known. For example, as antibacterial agents, 1,2,3,5-substituted-4-pyridone compounds having a carboxy group at the 5-position have been disclosed (for example, JP-A-53-65882 and JP-A-61-246163). Issue).
特開昭５３－６５８８２号公報JP-A-53-65882 特開昭６１－２４６１６３号公報Japanese Patent Laid-Open No. 61-246163
　しかしながら、特開昭５３－６５８８２号公報および特開昭６１－２４６１６３号公報に記載されている化合物の用途は、いずれも医薬に関するものであり、本発明に係る農園芸用殺菌剤が属する技術分野とは相違する。 However, the uses of the compounds described in JP-A-53-65882 and JP-A-61-246163 are all related to pharmaceuticals, and the technical field to which the agricultural and horticultural germicide of the present invention belongs Is different from.
　本発明の課題は、農園芸用殺菌剤として有効である新規なピリドン化合物を提供することである。 An object of the present invention is to provide a novel pyridone compound which is effective as a fungicide for agricultural and horticultural use.
　本発明者らは、前記課題を解決すべく、１，２，３，５－置換－４－ピリドン化合物群について鋭意検討を行った。その結果、該４－ピリドン骨格において１位に５員環のヘテロ環式置換基を導入した新規な化合物群が、植物病害に対して優れた防除活性を発揮することを見出した。また、驚くべきことに、当該ヘテロ環式置換基を有するピリドン化合物群は土壌分解性を有しており、環境負荷の低減が可能であることが判明し、本発明を完成するに至った。 In order to solve the above-mentioned problems, the present inventors have made extensive studies on a group of 1,2,3,5-substituted-4-pyridone compounds. As a result, they have found that a novel compound group in which a 5-membered heterocyclic substituent is introduced at the 1-position in the 4-pyridone skeleton exerts excellent control activity against plant diseases. Further, surprisingly, it was found that the pyridone compound group having the heterocyclic substituent has soil degradability, and it is possible to reduce the environmental load, thus completing the present invention.
　すなわち、本発明は、以下の通りである。
［１］　式（１）
Figure JPOXMLDOC01-appb-C000002
［式中、Ｒ１は、
　　水素原子、
　　シアノ基、
　　ハロゲン原子、
　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
　　Ｃ１～Ｃ６のハロアルキル基、
　　置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、
　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
　　Ｃ２～Ｃ６のハロアルケニル基、
　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
　　Ｃ２～Ｃ６のハロアルキニル基、
　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
　　Ｃ１～Ｃ６のハロアルコキシ基、
　　置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基、
　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、
　　Ｃ２～Ｃ６のハロアルケニルオキシ基、
　　置換基Ａで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、
　　Ｃ３～Ｃ６のハロアルキニルオキシ基、
　　Ｒｃ－Ｌ－（ここで、Ｒｃは、Ｃ１～Ｃ６のアルキル基またはＣ１～Ｃ６のハロアルキル基を表し、Ｌは、Ｓ、ＳＯ、またはＳＯ２を表す。）、
　　または、ＲｇＣ（＝Ｏ）－（ここで、Ｒｇは、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表す。）を表し；
　Ｒ２は、
　　シアノ基、
　　ハロゲン原子、
　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
　　Ｃ１～Ｃ６のハロアルキル基、
　　置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、
　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
　　Ｃ２～Ｃ６のハロアルケニル基、
　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
　　Ｃ２～Ｃ６のハロアルキニル基、
　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
　　Ｃ１～Ｃ６のハロアルコキシ基、
　　置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基、
　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、
　　Ｃ２～Ｃ６のハロアルケニルオキシ基、
　　置換基Ａで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、
　　Ｃ３～Ｃ６のハロアルキニルオキシ基、
　　Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）、
　　または、ＲｇＣ（＝Ｏ）－（ここで、Ｒｇは、前記と同義である。）を表し；
　Ｘは、酸素原子または硫黄原子であり；
　Ｒ３は、
　　水酸基、
　　シアノ基、
　　ニトロ基、
　　ハロゲン原子、
　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
　　Ｃ１～Ｃ６のハロアルキル基、
　　置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、
　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
　　Ｃ２～Ｃ６のハロアルケニル基、
　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
　　Ｃ２～Ｃ６のハロアルキニル基、
　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
　　Ｃ１～Ｃ６のハロアルコキシ基、
　　置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基、
　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、
　　Ｃ２～Ｃ６のハロアルケニルオキシ基、
　　置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、
　　Ｃ３～Ｃ６のハロアルキニルオキシ基、
　　ＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、またはＣ３～Ｃ８のシクロアルコキシ基を表す。）、
　　ＲｄＣ（＝Ｏ）Ｏ－（ここで、Ｒｄは、前記と同義である。）、
　　Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）、
　　ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、それぞれ独立していて、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表す。）、
　　または、ＲｅＣ（＝Ｏ）Ｎ（Ｒｆ）－（ここで、ＲｅとＲｆは、それぞれ独立していて、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、Ｃ３～Ｃ８のシクロアルコキシ基、またはＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）を表す。）を表し；
　ｎは、０～５の整数（ただし、ｎが２以上の場合、Ｒ３はそれぞれ独立している。）を表し；
　Ｚは、
　　Ｒ４で適宜０～３置換されてもよいチエニル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）、
　　Ｒ４で適宜０～２置換されてもよいチアゾリル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）、
　　Ｒ４で適宜置換されてもよいチアジアゾリル基
　　Ｒ４で適宜０～３置換されてもよいピラゾリル基（ただし、２置換のＲ４の場合、それぞれ独立している。）、
　　または、Ｒ４で適宜置換されてもよいテトラゾリル基を表し、
　Ｒ４は、
　　水酸基、
　　シアノ基、
　　ニトロ基、
　　ハロゲン原子、
　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
　　Ｃ１～Ｃ６のハロアルキル基、
　　置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、
　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
　　Ｃ２～Ｃ６のハロアルケニル基、
　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
　　Ｃ２～Ｃ６のハロアルキニル基、
　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
　　Ｃ１～Ｃ６のハロアルコキシ基、
　　置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基、
　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、
　　Ｃ２～Ｃ６のハロアルケニルオキシ基、
　　置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、
　　Ｃ３～Ｃ６のハロアルキニルオキシ基、
　　ＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、前記と同義である。）、
　　ＲｄＣ（＝Ｏ）Ｏ－（ここで、Ｒｄは、前記と同義である。）、
　　Ｒｃ－Ｌ－（ここで、Ｒｃ、Ｌは、前記と同義である。）、
　　ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）、
　　または、ＲｅＣ（＝Ｏ）Ｎ（Ｒｆ）－（ここで、ＲｅおよびＲｆは、前記と同義である。）を表し；
　そして、置換基Ａは、水酸基、シアノ基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、Ｃ３～Ｃ８のシクロアルコキシ基、ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）、およびＲｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）からなる群から選択される少なくとも１種であり；
　置換基Ｂは、シアノ基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基およびＣ３～Ｃ８のシクロアルコキシ基からなる群から選択される少なくとも１種であり；
　置換基Ｃは、水酸基、シアノ基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、Ｃ３～Ｃ８のシクロアルコキシ基、Ｃ２～Ｃ６のアルコキシアルコキシ基、ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）、Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）、およびＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、前記と同義である。）からなる群から選択される少なくとも１種である。］
で表される化合物またはその塩。
［２］　Ｒ１は、
　　水素原子、
　　ハロゲン原子、
　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
　　Ｃ１～Ｃ６のハロアルキル基、
　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
　　Ｃ１～Ｃ６のハロアルコキシ基、
　　または、ＲｇＣ（＝Ｏ）－（ここで、Ｒｇは、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表す。）を表し；
　Ｒ２は、
　　ハロゲン原子、
　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
　　Ｃ１～Ｃ６のハロアルキル基、
　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
　　Ｃ１～Ｃ６のハロアルコキシ基、
　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、
　　または、置換基Ａで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基を表し；
　Ｘは、酸素原子であり；
　Ｒ３は、
　　水酸基、
　　シアノ基、
　　ハロゲン原子、
　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
　　Ｃ１～Ｃ６のハロアルキル基、
　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
　　Ｃ１～Ｃ６のハロアルコキシ基、
　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、
　　または、置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基を表し；
　Ｒ４は、
　　水酸基、
　　シアノ基、
　　ニトロ基、
　　ハロゲン原子、
　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
　　Ｃ１～Ｃ６のハロアルキル基、
　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
　　Ｃ１～Ｃ６のハロアルコキシ基、
　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、
　　置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、
　　または、ＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、またはＣ３～Ｃ８のシクロアルコキシ基を表す。）を表す、
［１］に記載の化合物またはその塩。
［３］　Ｒ１は、
　　水素原子、
　　ハロゲン原子、
　　または、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基を表し；
　Ｒ２は、
　　ハロゲン原子、
　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
　　または、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基を表し；
　Ｒ３は、
　　ハロゲン原子、
　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
　　または、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基を表し；
　Ｒ４は、
　　ハロゲン原子、
　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
　　Ｃ１～Ｃ６のハロアルキル基、
　　または、ＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、またはＣ３～Ｃ８のシクロアルコキシ基を表す。）を表す、
［２］に記載の化合物またはその塩。
［４］　Ｒ１が、水素原子、臭素原子、またはメチル基である、［１］～［３］のいずれか１つに記載の化合物、またはその塩。
［５］　Ｒ２が、塩素原子、メチル基、エチル基、またはメトキシ基である、［１］～［４］のいずれか１つに記載の化合物、またはその塩。
［６］　Ｘが、酸素原子である、［１］～［５］のいずれか１つに記載の化合物、またはその塩。
［７］　Ｒ３が、フッ素原子、塩素原子、臭素原子、メチル基、またはメトキシ基である、［１］～［６］のいずれか１つに記載の化合物、またはその塩。
［８］　Ｒ４が、塩素原子、臭素原子、メチル基、ホルミル基またはジフルオロメチル基である、［１］～［７］のいずれか１つに記載の化合物、またはその塩。
［９］　Ｚが、Ｒ４で適宜０～３置換されてもよいチエニル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）、Ｒ４で適宜０～２置換されてもよいチアゾリル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）、またはＲ４で適宜０～３置換されてもよいピラゾリル基（ただし、２置換のＲ４の場合、それぞれ独立している。）を表す、［１］～［８］のいずれか１つに記載の化合物、またはその塩。
［１０］　Ｚが、Ｒ４で適宜０～３置換されてもよいチエニル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）を表す、［１］～［８］のいずれか１つに記載の化合物、またはその塩。
［１１］　Ｚが、Ｒ４で適宜０～２置換されてもよいチアゾリル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）を表す、［１］～［８］のいずれか１つに記載の化合物、またはその塩。
［１２］　Ｚが、Ｒ４で適宜置換されてもよいチアジアゾリル基を表す、［１］～［８］のいずれか１つに記載の化合物、またはその塩。
［１３］　Ｚが、Ｒ４で適宜０～３置換されてもよいピラゾリル基（ただし、２置換のＲ４の場合、それぞれ独立している。）を表す、［１］～［８］のいずれか１つに記載の化合物、またはその塩。
［１４］　Ｚが、Ｒ４で適宜置換されてもよいテトラゾリル基を表す、［１］～［８］のいずれか１つに記載の化合物、またはその塩。
［１５］　Ｚが、チオフェン－３－イル基、２－ブロモ－チオフェン－３－イル基、２－メチル－チオフェン－３－イル基、チアゾール－２－イル基、４－ブロモ－５－メチル－チアゾール－２－イル基、４－メチル－チアゾール－２－イル基、５－メチル－チアゾール－２－イル基、１，２，３－チアジアゾール－５－イル基、１，３，４－チアジアゾール－２－イル基、５－ブロモ－１，３，４－チアジアゾール－２－イル基、１－メチル－ピラゾール－３－イル基、１－メチル－４－クロロ－ピラゾール－３－イル基、１－メチル－４－ブロモ－ピラゾール－３－イル基、１－メチル－４－メチル－ピラゾール－３－イル基、１－メチル－５－クロロ－ピラゾール－３－イル基、１－メチル－５－ジフルオロメチル－ピラゾール－３－イル基、１－メチル－５－ホルミル－ピラゾール－３－イル基、１－メチル－ピラゾール－４－イル基、１－メチル－ピラゾール－５－イル基、または１－メチル－テトラゾール－５－イル基である、［１］～［８］のいずれか１つに記載の化合物、またはその塩。
［１６］　Ｚが、チオフェン－３－イル基、２－ブロモ－チオフェン－３－イル基、または２－メチル－チオフェン－３－イル基である、［１］～［８］のいずれか１つに記載の化合物、またはその塩。
［１７］　Ｚが、チアゾール－２－イル基、４－ブロモ－５－メチル－チアゾール－２－イル基、４－メチル－チアゾール－２－イル基、または５－メチル－チアゾール－２－イル基である、［１］～［８］のいずれか１つに記載の化合物、またはその塩。
［１８］　Ｚが、１，２，３－チアジアゾール－５－イル基、１，３，４－チアジアゾール－２－イル基、または５－ブロモ－１，３，４－チアジアゾール－２－イル基である、［１］～［８］のいずれか１つに記載の化合物、またはその塩。
［１９］　Ｚが、１－メチル－ピラゾール－３－イル基、１－メチル－４－クロロ－ピラゾール－３－イル基、１－メチル－４－ブロモ－ピラゾール－３－イル基、１－メチル－４－メチル－ピラゾール－３－イル基、１－メチル－５－クロロ－ピラゾール－３－イル基、１－メチル－５－ジフルオロメチル－ピラゾール－３－イル基、１－メチル－５－ホルミル－ピラゾール－３－イル基、１－メチル－ピラゾール－４－イル基、または１－メチル－ピラゾール－５－イル基である、［１］～［８］のいずれか１つに記載の化合物、またはその塩。
［２０］　Ｚが、１－メチル－テトラゾール－５－イル基である、［１］～［８］のいずれか１つに記載の化合物、またはその塩。
［２１］　［１］～［２０］のいずれか１つに記載の化合物、またはその塩を有効成分として含有する農園芸用有害生物防除剤。
［２２］　［１］～［２０］のいずれか１つに記載の化合物、またはその塩を有効成分として含有する農園芸用殺菌剤。
［２３］　［２２］に記載の農園芸用有害生物防除剤を、植物、植物の種子、または植物を栽培する土壌に施用することを含む、植物病害を防除する方法。
［２４］　［２３］に記載の農園芸用殺菌剤を、植物、植物の種子、または植物を栽培する土壌に施用することを含む、植物病害を防除する方法。
［２５］　農園芸用有害生物防除剤としての［１］～［２０］のいずれか１つに記載の化合物の使用。
［２６］　農園芸用殺菌剤としての［１］～［２０］のいずれか１つに記載の化合物の使用。 That is, the present invention is as follows.
[1] Formula (1)
Figure JPOXMLDOC01-appb-C000002
[In the formula, R1 is
Hydrogen atom,
Cyano group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent A,
A C1 to C6 haloalkyl group,
A C3 to C8 cycloalkyl group which may be optionally substituted with a substituent A,
A C2-C6 alkenyl group optionally substituted with a substituent A,
A C2-C6 haloalkenyl group,
A C2-C6 alkynyl group optionally substituted with a substituent A,
A C2-C6 haloalkynyl group,
A C1 to C6 alkoxy group optionally substituted with a substituent A,
A C1 to C6 haloalkoxy group,
A C3 to C8 cycloalkoxy group optionally substituted with a substituent A,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent A,
A C2-C6 haloalkenyloxy group,
A C3-C6 alkynyloxy group which may be optionally substituted with a substituent A,
A C3 to C6 haloalkynyloxy group,
Rc-L- (wherein Rc represents a C1-C6 alkyl group or a C1-C6 haloalkyl group, and L represents S, SO, or SO 2 ),
Alternatively, RgC (═O) — (wherein, Rg represents a C1 to C6 alkyl group optionally substituted with the substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group. ) Represents;
R2 is
Cyano group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent A,
A C1 to C6 haloalkyl group,
A C3 to C8 cycloalkyl group which may be optionally substituted with a substituent A,
A C2-C6 alkenyl group optionally substituted with a substituent A,
A C2-C6 haloalkenyl group,
A C2-C6 alkynyl group optionally substituted with a substituent A,
A C2-C6 haloalkynyl group,
A C1 to C6 alkoxy group optionally substituted with a substituent A,
A C1 to C6 haloalkoxy group,
A C3 to C8 cycloalkoxy group optionally substituted with a substituent A,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent A,
A C2-C6 haloalkenyloxy group,
A C3-C6 alkynyloxy group which may be optionally substituted with a substituent A,
A C3 to C6 haloalkynyloxy group,
Rc-L- (wherein Rc and L are as defined above),
Or represents RgC (═O) — (wherein Rg has the same meaning as above);
X is an oxygen atom or a sulfur atom;
R3 is
Hydroxyl group,
Cyano group,
Nitro group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
A C3 to C8 cycloalkyl group optionally substituted with a substituent C,
A C2-C6 alkenyl group optionally substituted with a substituent C,
A C2-C6 haloalkenyl group,
A C2 to C6 alkynyl group optionally substituted with a substituent C,
A C2-C6 haloalkynyl group,
A C1 to C6 alkoxy group optionally substituted with a substituent C,
A C1 to C6 haloalkoxy group,
A C3 to C8 cycloalkoxy group optionally substituted with a substituent C,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent C,
A C2-C6 haloalkenyloxy group,
A C3-C6 alkynyloxy group optionally substituted with a substituent C,
A C3 to C6 haloalkynyloxy group,
RdC (= O)-(wherein Rd is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, a C1 to Represents a C6 alkoxy group, a C1 to C6 haloalkoxy group, or a C3 to C8 cycloalkoxy group),
RdC (= O) O- (wherein Rd is as defined above),
Rc-L- (wherein Rc and L are as defined above),
RaRbN- (wherein Ra and Rb are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group). Represents an alkyl group),
Alternatively, ReC (═O) N (Rf) — (wherein Re and Rf are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, C1 to C6). Haloalkyl group, C3-C8 cycloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C3-C8 cycloalkoxy group, or RaRbN- (wherein Ra and Rb have the same meanings as defined above). Represents)) represents);
n represents an integer of 0 to 5 (provided that when n is 2 or more, R3s are independent of each other);
Z is
A thienyl group which may be optionally substituted by 0 to 3 with R4 (however, in the case of 2 or more substituted R4, each is independent),
A thiazolyl group which may be optionally substituted by 0 to 2 with R4 (however, in the case of R4 having 2 or more substitutions, each is independent),
Thiadiazolyl group optionally substituted with R4 pyrazolyl group optionally substituted with 0 to 3 optionally with R4 (however, in the case of disubstituted R4, each is independent),
Or, represents a tetrazolyl group optionally substituted by R4,
R4 is
Hydroxyl group,
Cyano group,
Nitro group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
A C3 to C8 cycloalkyl group optionally substituted with a substituent C,
A C2-C6 alkenyl group optionally substituted with a substituent C,
A C2-C6 haloalkenyl group,
A C2 to C6 alkynyl group optionally substituted with a substituent C,
A C2-C6 haloalkynyl group,
A C1 to C6 alkoxy group optionally substituted with a substituent C,
A C1 to C6 haloalkoxy group,
A C3 to C8 cycloalkoxy group optionally substituted with a substituent C,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent C,
A C2-C6 haloalkenyloxy group,
A C3-C6 alkynyloxy group optionally substituted with a substituent C,
A C3 to C6 haloalkynyloxy group,
RdC (= O)-(wherein Rd is as defined above),
RdC (= O) O- (wherein Rd is as defined above),
Rc-L- (wherein Rc and L are as defined above),
RaRbN- (wherein Ra and Rb are as defined above),
Alternatively, ReC (═O) N (Rf)-(wherein Re and Rf have the same meanings as described above);
The substituent A is a hydroxyl group, a cyano group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, a C3 to C8 cycloalkoxy group, or a RaRbN- (here, Ra And Rb are as defined above.), And Rc-L- (wherein Rc and L are as defined above), and at least one selected from the group consisting of:
Substituent B is at least one selected from the group consisting of a cyano group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group and a C3-C8 cycloalkoxy group;
Substituent C is a hydroxyl group, a cyano group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, a C2-C6 alkoxyalkoxy group, RaRbN -(Wherein Ra and Rb are as defined above), Rc-L- (wherein Rc and L are as defined above), and RdC (= O)-(wherein Rd has the same meaning as described above.) And is at least one selected from the group consisting of ]
Or a salt thereof.
[2] R1 is
Hydrogen atom,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent A,
A C1 to C6 haloalkyl group,
A C2-C6 alkenyl group optionally substituted with a substituent A,
A C2-C6 alkynyl group optionally substituted with a substituent A,
A C1 to C6 alkoxy group optionally substituted with a substituent A,
A C1 to C6 haloalkoxy group,
Alternatively, RgC (═O) — (wherein, Rg represents a C1 to C6 alkyl group optionally substituted with the substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group. ) Represents;
R2 is
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent A,
A C1 to C6 haloalkyl group,
A C2-C6 alkenyl group optionally substituted with a substituent A,
A C2-C6 alkynyl group optionally substituted with a substituent A,
A C1 to C6 alkoxy group optionally substituted with a substituent A,
A C1 to C6 haloalkoxy group,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent A,
Or represents a C3-C6 alkynyloxy group which may be optionally substituted with a substituent A;
X is an oxygen atom;
R3 is
Hydroxyl group,
Cyano group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
A C2-C6 alkenyl group optionally substituted with a substituent C,
A C2 to C6 alkynyl group optionally substituted with a substituent C,
A C1 to C6 alkoxy group optionally substituted with a substituent C,
A C1 to C6 haloalkoxy group,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent C,
Or represents a C3 to C6 alkynyloxy group which may be optionally substituted with a substituent C;
R4 is
Hydroxyl group,
Cyano group,
Nitro group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
A C2-C6 alkenyl group optionally substituted with a substituent C,
A C2 to C6 alkynyl group optionally substituted with a substituent C,
A C1 to C6 alkoxy group optionally substituted with a substituent C,
A C1 to C6 haloalkoxy group,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent C,
A C3-C6 alkynyloxy group optionally substituted with a substituent C,
Alternatively, RdC (═O) — (wherein Rd is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, C1 to C6 alkoxy group, C1 to C6 haloalkoxy group, or C3 to C8 cycloalkoxy group).
The compound according to [1] or a salt thereof.
[3] R1 is
Hydrogen atom,
Halogen atom,
Or represents a C1 to C6 alkyl group which may be optionally substituted with a substituent A;
R2 is
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent A,
Or represents a C1 to C6 alkoxy group which may be optionally substituted with a substituent A;
R3 is
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
Or represents a C1 to C6 alkoxy group which may be optionally substituted with a substituent C;
R4 is
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
Alternatively, RdC (═O) — (wherein Rd is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, C1 to C6 alkoxy group, C1 to C6 haloalkoxy group, or C3 to C8 cycloalkoxy group).
The compound or salt thereof according to [2].
[4] The compound or salt thereof according to any one of [1] to [3], wherein R1 is a hydrogen atom, a bromine atom, or a methyl group.
[5] The compound or salt thereof according to any one of [1] to [4], wherein R2 is a chlorine atom, a methyl group, an ethyl group, or a methoxy group.
[6] The compound according to any one of [1] to [5], wherein X is an oxygen atom, or a salt thereof.
[7] The compound or salt thereof according to any one of [1] to [6], wherein R3 is a fluorine atom, a chlorine atom, a bromine atom, a methyl group or a methoxy group.
[8] The compound or salt thereof according to any one of [1] to [7], wherein R4 is chlorine atom, bromine atom, methyl group, formyl group or difluoromethyl group.
[9] Z is a thienyl group which may be optionally substituted by R4 with 0 to 3 (provided that each is independent in the case of 2 or more substituted R4), and thiazolyl which is optionally substituted with R4 by R4. Or a pyrazolyl group which may be optionally substituted by 0 to 3 with R4 (however, in the case of disubstituted R4, each is independent. ] The compound of any one of [1] to [8], or a salt thereof.
[10] Any of [1] to [8], wherein Z represents a thienyl group which may be optionally substituted by R4 with 0 to 3 (provided that each is independently substituted with 2 or more substituted R4). 1. The compound according to 1, or a salt thereof.
[11] Any one of [1] to [8], wherein Z represents a thiazolyl group which may be optionally substituted by 0 to 2 with R4 (in the case of disubstituted or more R4, each is independent). 1. The compound according to 1, or a salt thereof.
[12] The compound according to any one of [1] to [8], or a salt thereof, in which Z represents a thiadiazolyl group optionally substituted with R4.
[13] Any one of [1] to [8], wherein Z represents a pyrazolyl group which may be optionally substituted by R4 with 0 to 3 (in the case of disubstituted R4, each is independent). Or a salt thereof.
[14] The compound according to any one of [1] to [8], or a salt thereof, in which Z represents a tetrazolyl group optionally substituted with R4.
[15] Z is thiophen-3-yl group, 2-bromo-thiophen-3-yl group, 2-methyl-thiophen-3-yl group, thiazol-2-yl group, 4-bromo-5-methyl- Thiazol-2-yl group, 4-methyl-thiazol-2-yl group, 5-methyl-thiazol-2-yl group, 1,2,3-thiadiazol-5-yl group, 1,3,4-thiadiazole- 2-yl group, 5-bromo-1,3,4-thiadiazol-2-yl group, 1-methyl-pyrazol-3-yl group, 1-methyl-4-chloro-pyrazol-3-yl group, 1- Methyl-4-bromo-pyrazol-3-yl group, 1-methyl-4-methyl-pyrazol-3-yl group, 1-methyl-5-chloro-pyrazol-3-yl group, 1-methyl-5-difluoro Methyl-pyrazol-3-i Group, 1-methyl-5-formyl-pyrazol-3-yl group, 1-methyl-pyrazol-4-yl group, 1-methyl-pyrazol-5-yl group, or 1-methyl-tetrazol-5-yl The compound according to any one of [1] to [8], which is a group, or a salt thereof.
[16] Any one of [1] to [8], wherein Z is a thiophen-3-yl group, a 2-bromo-thiophen-3-yl group, or a 2-methyl-thiophen-3-yl group. Or a salt thereof.
[17] Z is a thiazol-2-yl group, a 4-bromo-5-methyl-thiazol-2-yl group, a 4-methyl-thiazol-2-yl group, or a 5-methyl-thiazol-2-yl group The compound according to any one of [1] to [8], or a salt thereof.
[18] Z is a 1,2,3-thiadiazol-5-yl group, a 1,3,4-thiadiazol-2-yl group or a 5-bromo-1,3,4-thiadiazol-2-yl group A compound according to any one of [1] to [8], or a salt thereof.
[19] Z is 1-methyl-pyrazol-3-yl group, 1-methyl-4-chloro-pyrazol-3-yl group, 1-methyl-4-bromo-pyrazol-3-yl group, 1-methyl -4-Methyl-pyrazol-3-yl group, 1-methyl-5-chloro-pyrazol-3-yl group, 1-methyl-5-difluoromethyl-pyrazol-3-yl group, 1-methyl-5-formyl A compound according to any one of [1] to [8], which is a -pyrazol-3-yl group, a 1-methyl-pyrazol-4-yl group, or a 1-methyl-pyrazol-5-yl group, Or its salt.
[20] The compound according to any one of [1] to [8], wherein Z is a 1-methyl-tetrazol-5-yl group, or a salt thereof.
[21] A pesticide for agricultural and horticultural use, which comprises the compound according to any one of [1] to [20] or a salt thereof as an active ingredient.
[22] A fungicide for agricultural and horticultural use containing the compound according to any one of [1] to [20] or a salt thereof as an active ingredient.
[23] A method for controlling plant diseases, which comprises applying the agricultural and horticultural pest control agent according to [22] to plants, plant seeds, or soil for cultivating plants.
[24] A method for controlling plant diseases, which comprises applying the agricultural / horticultural fungicide according to [23] to plants, plant seeds, or soil for cultivating plants.
[25] Use of the compound according to any one of [1] to [20] as a pesticide for agricultural and horticultural use.
[26] Use of the compound according to any one of [1] to [20] as a fungicide for agricultural and horticultural use.
　本発明によれば、農園芸用殺菌剤として有効である新規な化合物を提供することができる。 According to the present invention, it is possible to provide a novel compound which is effective as an agricultural / horticultural germicide.
　以下、本発明を実施するための形態について詳細に説明する。 Hereinafter, embodiments for carrying out the present invention will be described in detail.
　なお、特許請求の範囲および明細書中において用いられる各用語は、特に断らない限り、当該技術分野において一般的に用いられる定義によるものとする。 Unless otherwise specified, each term used in the claims and the specification is based on the definition generally used in the technical field.
　本明細書において、使用する略号を以下に説明する。
ＤＭＦ：Ｎ，Ｎ－ジメチルホルムアミド、ＴＨＦ：テトラヒドロフラン、Ｍｅ：メチル基、Ｅｔ：エチル基、Ｐｒ：プロピル基、Ｂｕ：ブチル基、Ｐｅｎｔ：ペンチル基、Ｈｅｘ：ヘキシル基、Ｈｅｐｔ：ヘプチル基、Ｏｃｔ：オクチル基、Ｎｏｎ：ノニル基、Ａｃ：アセチル基、Ｐｈ：フェニル基、Ｐｙ：ピリジル基、ｃ：シクロ、ｉ：イソ、ｓｅｃ：セカンダリ、ｔ：ターシャリ、＝：二重結合、≡：三重結合を表す。表のカラム中、Ｐｒ、Ｂｕ、Ｐｅｎｔ、Ｈｅｘ、Ｈｅｐｔ、ＯｃｔおよびＮｏｎに関しては、接頭辞がない場合は、ノルマルを意味する。 Abbreviations used in this specification are described below.
DMF: N, N-dimethylformamide, THF: tetrahydrofuran, Me: methyl group, Et: ethyl group, Pr: propyl group, Bu: butyl group, Pent: pentyl group, Hex: hexyl group, Hept: heptyl group, Oct: Octyl group, Non: nonyl group, Ac: acetyl group, Ph: phenyl group, Py: pyridyl group, c: cyclo, i: iso, sec: secondary, t: tertiary, =: double bond, ≡: triple bond. Represent Regarding Pr, Bu, Pent, Hex, Hept, Oct and Non in the columns of the table, when there is no prefix, it means normal.
　以下に、本明細書中に使用される用語の定義を説明する。 The definitions of terms used in this specification are explained below.
　Ｃｘ～Ｃｙとの記載は、ｘ個からｙ個の炭素原子を有することを表す。ここで、ｘ及びｙは整数を表し、また、ｘとｙとの間に存在する全ての整数も個別に開示されているものと理解される。例えば、Ｃ１～Ｃ６は、１、２、３、４、５、または６個の炭素原子を、Ｃ１～Ｃ５は、１、２、３、４、または５個の炭素原子を、Ｃ２～Ｃ６は、２、３、４、５、または６個の炭素原子を、Ｃ３～Ｃ８は、３、４、５、６、７、または８個の炭素原子を、Ｃ３～Ｃ６は、３、４、５、または６個の炭素原子を、それぞれ有することを意味する。 The description of Cx to Cy means that it has x to y carbon atoms. Here, x and y represent integers, and it is understood that all integers present between x and y are also individually disclosed. For example, C1-C6 is 1, 2, 3, 4, 5, or 6 carbon atoms, C1-C5 is 1, 2, 3, 4, or 5 carbon atoms, and C2-C6 is 2, 3, 4, 5, or 6 carbon atoms, C3-C8 is 3, 4, 5, 6, 7, or 8 carbon atoms, C3-C6 is 3, 4, 5 , Or 6 carbon atoms, respectively.
　用語「適宜置換されてもよい」とは、置換または無置換であることを意味する。この用語を用いる際、置換基の数が明示されていないときは、置換基の数は１であることを表す。一方で、例えば、「適宜０～５置換されてもよい」と置換基の数が指定されている場合、０と５との間に存在する全ての整数も個別に開示されているものと理解される。即ち、置換基が、無し、１、２、３、４、または５個の置換基数であることを意味する。同様に、「適宜０～４置換されてもよい」では、置換基が、なし、１、２、３、または４個の置換基数を、「適宜０～３置換されてもよい」では、なし、１、２、または３個の置換基数を、「適宜０～２置換されてもよい」では、なし、１、または２個の置換基数を、それぞれ有することを意味する。 The term “may be appropriately substituted” means substituted or unsubstituted. In using this term, when the number of substituents is not specified, it indicates that the number of substituents is 1. On the other hand, for example, when the number of substituents is designated as “optionally substituted by 0 to 5”, it is understood that all integers existing between 0 and 5 are also individually disclosed. To be done. That is, it means that the number of substituents is none, 1, 2, 3, 4, or 5 substituents. Similarly, in “optionally 0 to 4 substituted”, there is no substituent, and in 1, 2, 3, or 4 substituents, there is no in “optionally 0 to 3 substituted”. The phrase “may be substituted with 0 to 2 as appropriate” having 1, 2, or 3 substituents means none, 1 or 2 substituents, respectively.
　Ｃ１～Ｃ６のアルキル基とは、直鎖状または分岐状でよく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、ペンチル基、イソペンチル基、１－メチルブチル基、２－メチルブチル基、ネオペンチル基、１－エチルプロピル基、１，２－ジメチルプロピル基、ヘキシル基、１－メチルペンチル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基、１，１－ジメチルブチル基、２，２－ジメチルブチル基、３，３－ジメチルブチル基、１，２－ジメチルブチル基、１，３－ジメチルブチル基、２，３－ジメチルブチル基、２－エチルブチル基、１－イソプロピルプロピル基、１，１，２－トリメチルプロピル基、１，２，２－トリメチルプロピル基等が挙げられる。 The C1 to C6 alkyl group may be linear or branched, and specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group. , Pentyl group, isopentyl group, 1-methylbutyl group, 2-methylbutyl group, neopentyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3 -Methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group , 2,3-dimethylbutyl group, 2-ethylbutyl group, 1-isopropylpropyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethyl Propyl group, and the like.
　ハロゲン原子とは、具体的には、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。 Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
　Ｃ１～Ｃ６のハロアルキル基とは、前記のＣ１～Ｃ６のアルキル基における水素原子が１個または２個以上のハロゲン原子によって任意に置換されたものを表す。２個以上のハロゲン原子で置換される場合、それらのハロゲン原子は同一または異なっていてよく、その置換数は置換基として存在することができる限り特に制限はない。Ｃ１～Ｃ６のハロアルキル基の具体例として、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、モノクロロメチル基、モノブロモメチル基、モノヨードメチル基、クロロジフルオロメチル基、ブロモジフルオロメチル基、１－フルオロエチル基、２－フルオロエチル基、１，１－ジフルオロエチル基、２，２－ジフルオロエチル基、２，２，２－トリフルオロエチル基、１，１，２，２－テトラフルオロエチル基、ペンタフルオロエチル基、２，２，２－トリクロロエチル基、３，３－ジフルオロプロピル基、３，３，３－トリフルオロプロピル基、ヘプタフルオロプロピル基、ヘプタフルオロイソプロピル基、２，２，２－トリフルオロ－１－（トリフルオロメチル）エチル基、４，４－ジフルオロブチル基、４，４，４－トリフルオロブチル基、ノナフルオロブチル基、ノナフルオロ－ｓｅｃ－ブチル基、５，５－ジフルオロペンチル基、５，５，５－トリフルオロペンチル基、３，３，４，４，５，５，５－ヘプタフルオロペンチル基、ウンデカフルオロペンチル基、トリデカフルオロヘキシル基等が挙げられる。 The term “C1 to C6 haloalkyl group” refers to the above C1 to C6 alkyl group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent. Specific examples of the C1 to C6 haloalkyl group include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monochloromethyl group, a monobromomethyl group, a monoiodomethyl group, a chlorodifluoromethyl group, a bromodifluoromethyl group, and -Fluoroethyl group, 2-fluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group , Pentafluoroethyl group, 2,2,2-trichloroethyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, heptafluoropropyl group, heptafluoroisopropyl group, 2,2,2 -Trifluoro-1- (trifluoromethyl) ethyl group, 4,4-difluorobutyl group, 4,4 4-trifluorobutyl group, nonafluorobutyl group, nonafluoro-sec-butyl group, 5,5-difluoropentyl group, 5,5,5-trifluoropentyl group, 3,3,4,4,5,5,5 5-heptafluoropentyl group, undecafluoropentyl group, tridecafluorohexyl group and the like can be mentioned.
　Ｃ３～Ｃ８のシクロアルキル基とは、具体的には、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基等が挙げられる。 Specific examples of the C3 to C8 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
　Ｃ２～Ｃ６のアルケニル基とは、１個または２個以上の二重結合を有し、直鎖状または分岐状である不飽和炭化水素基のものを表す。また、幾何異性体がある場合、Ｅ体またはＺ体のどちらか一方のみ、あるいはＥ体とＺ体との任意の割合の混合物であり、指定される炭素数の範囲であれば、特に限定されることはない。Ｃ２～Ｃ６のアルケニル基の具体例として、ビニル基、１－プロペニル基、アリル基、１－ブテニル基、２－ブテニル基、３－ブテニル基、２－メチル－１－プロペニル基、１－ペンテニル基、２－ペンテニル基、３－ペンテニル基、４－ペンテニル基、２－メチル－１－ブテニル基、３－メチル－２－ブテニル基、１－ヘキセニル基、２－ヘキセニル基、３－ヘキセニル基、４－ヘキセニル基、５－ヘキセニル基、３－メチル－２－ペンテニル基、４－メチル－３－ペンテニル基等が挙げられる。 The C2-C6 alkenyl group represents a linear or branched unsaturated hydrocarbon group having one or more double bonds. In addition, when there is a geometric isomer, only one of the E-form or the Z-form, or a mixture of the E-form and the Z-form at an arbitrary ratio is used. Never. Specific examples of the C2-C6 alkenyl group include vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 1-pentenyl group. , 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 2-methyl-1-butenyl group, 3-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4 -Hexenyl group, 5-hexenyl group, 3-methyl-2-pentenyl group, 4-methyl-3-pentenyl group and the like can be mentioned.
　Ｃ２～Ｃ６のハロアルケニル基とは、前記のＣ２～Ｃ６のアルケニル基における水素原子が１個または２個以上のハロゲン原子によって任意に置換されたものを表す。２個以上のハロゲン原子で置換される場合、それらのハロゲン原子は同一または異なっていてよく、その置換数は置換基として存在することができる限り特に制限はない。Ｃ２～Ｃ６のハロアルケニル基の具体例として、２－フルオロビニル基、２，２－ジフルオロビニル基、２，２－ジクロロビニル基、３－フルオロアリル基、３，３－ジフルオロアリル基、３，３－ジクロロアリル基、４，４－ジフルオロ－３－ブテニル基、５，５－ジフルオロ－４－ペンテニル基、６，６－ジフルオロ－５－ヘキセニル基等が挙げられる。 The term “C2-C6 haloalkenyl group” refers to the above-mentioned C2-C6 alkenyl group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent. Specific examples of the C2-C6 haloalkenyl group include 2-fluorovinyl group, 2,2-difluorovinyl group, 2,2-dichlorovinyl group, 3-fluoroallyl group, 3,3-difluoroallyl group, 3, Examples thereof include a 3-dichloroallyl group, a 4,4-difluoro-3-butenyl group, a 5,5-difluoro-4-pentenyl group, and a 6,6-difluoro-5-hexenyl group.
　Ｃ２～Ｃ６のアルキニル基とは、１個または２個以上の三重結合を有し、直鎖状または分岐状である不飽和炭化水素基のものを表す。Ｃ２～Ｃ６のアルキニル基の具体例として、エチニル基、１－プロピニル基、プロパルギル基、１－ブチニル基、２－ブチニル基、３－ブチニル基、１－ペンチニル基、２－ペンチニル基、３－ペンチニル基、４－ペンチニル基、１，１－ジメチル－２－プロピニル基、１－ヘキシニル基、２－ヘキシニル基、３－ヘキシニル基、４－ヘキシニル基、５－ヘキシニル基等が挙げられる。 The C2-C6 alkynyl group represents a linear or branched unsaturated hydrocarbon group having one or two or more triple bonds. Specific examples of the C2-C6 alkynyl group include ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group. Group, 4-pentynyl group, 1,1-dimethyl-2-propynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group and the like.
　Ｃ２～Ｃ６のハロアルキニル基とは、前記のＣ２～Ｃ６のアルキニル基における水素原子が１個または２個以上のハロゲン原子によって任意に置換されたものを表す。２個以上のハロゲン原子で置換される場合、それらのハロゲン原子は同一または異なっていてよく、その置換数は置換基として存在することができる限り特に制限はない。Ｃ２～Ｃ６のハロアルキニル基の具体例として、２－フルオロエチニル基、２－クロロエチニル基、２－ブロモエチニル基、２－ヨードエチニル基、３，３－ジフルオロ－１－プロピニル基、３－クロロ－３，３－ジフルオロ－１－プロピニル基、３－ブロモ－３，３－ジフルオロ－１－プロピニル基、３，３，３－トリフルオロ－１－プロピニル基、４，４－ジフルオロ－１－ブチニル基、４，４－ジフルオロ－２－ブチニル基、４－クロロ－４，４－ジフルオロ－１－ブチニル基、４－クロロ－４，４－ジフルオロ－２－ブチニル基、４－ブロモ－４，４－ジフルオロ－１－ブチニル基、４－ブロモ－４，４－ジフルオロ－２－ブチニル基、４，４，４－トリフルオロ－１－ブチニル基、４，４，４－トリフルオロ－２－ブチニル基、５，５－ジフルオロ－３－ペンチニル基、５－クロロ－５，５－ジフルオロ－３－ペンチニル基、５－ブロモ－５，５－ジフルオロ－３－ペンチニル基、５，５，５－トリフルオロ－３－ペンチニル基、６，６－ジフルオロ－４－ヘキシニル基、６－クロロ－６，６－ジフルオロ－４－ヘキシニル基、６－ブロモ－６，６－ジフルオロ－４－ヘキシニル基、６，６，６－トリフルオロ－４－ヘキシニル基等が挙げられる。 The term “C2-C6 haloalkynyl group” refers to the above-mentioned C2-C6 alkynyl group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent. Specific examples of the C2-C6 haloalkynyl group include 2-fluoroethynyl group, 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3,3-difluoro-1-propynyl group, 3-chloro. -3,3-difluoro-1-propynyl group, 3-bromo-3,3-difluoro-1-propynyl group, 3,3,3-trifluoro-1-propynyl group, 4,4-difluoro-1-butynyl Group, 4,4-difluoro-2-butynyl group, 4-chloro-4,4-difluoro-1-butynyl group, 4-chloro-4,4-difluoro-2-butynyl group, 4-bromo-4,4 -Difluoro-1-butynyl group, 4-bromo-4,4-difluoro-2-butynyl group, 4,4,4-trifluoro-1-butynyl group, 4,4,4-trifluoro-2-butynyl group 5, 5-difluoro-3-pentynyl group, 5-chloro-5,5-difluoro-3-pentynyl group, 5-bromo-5,5-difluoro-3-pentynyl group, 5,5,5-trifluoro-3- Pentynyl group, 6,6-difluoro-4-hexynyl group, 6-chloro-6,6-difluoro-4-hexynyl group, 6-bromo-6,6-difluoro-4-hexynyl group, 6,6,6- Examples thereof include a trifluoro-4-hexynyl group.
　Ｃ１～Ｃ６のアルコキシ基とは、前記のＣ１～Ｃ６のアルキル基が酸素原子を介して結合したものを表す。Ｃ１～Ｃ６のアルコキシ基の具体例として、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブトキシ基、イソブトキシ基、ｓｅｃ－ブトキシ基、ｔ－ブトキシ基、ペンチルオキシ基、イソペンチルオキシ基、１－メチルブトキシ基、２－メチルブトキシ基、ネオペンチルオキシ基、１－エチルプロピルオキシ基、１，２－ジメチルプロピルオキシ基、ヘキシルオキシ基、１－メチルペンチルオキシ基、２－メチルペンチルオキシ基、３－メチルペンチルオキシ基、４－メチルペンチルオキシ基、１，１－ジメチルブトキシ基、２，２－ジメチルブトキシ基、３，３－ジメチルブトキシ基、１，２－ジメチルブトキシ基、１，３－ジメチルブトキシ基、２，３－ジメチルブトキシ基、２－エチルブトキシ基、１－イソプロピルプロピルオキシ基、１，１，２－トリメチルプロピルオキシ基、１，２，２－トリメチルプロピルオキシ基等が挙げられる。 The term “C1 to C6 alkoxy group” refers to the above C1 to C6 alkyl group bonded via an oxygen atom. Specific examples of the C1 to C6 alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentyloxy group, isopentyloxy group, 1-methylbutoxy group, 2-methylbutoxy group, neopentyloxy group, 1-ethylpropyloxy group, 1,2-dimethylpropyloxy group, hexyloxy group, 1-methylpentyloxy group, 2-methylpentyloxy group , 3-methylpentyloxy group, 4-methylpentyloxy group, 1,1-dimethylbutoxy group, 2,2-dimethylbutoxy group, 3,3-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3 -Dimethylbutoxy group, 2,3-dimethylbutoxy group, 2-ethylbutoxy group, 1-isop Pills propyl group, 1,1,2-trimethyl propyl group, 1,2,2-trimethyl propyl group, and the like.
　Ｃ１～Ｃ６のハロアルコキシ基とは、前記のＣ１～Ｃ６のアルコキシ基における水素原子が１個または２個以上のハロゲン原子によって任意に置換されたものを表す。２個以上のハロゲン原子で置換される場合、それらのハロゲン原子は同一または異なっていてよく、その置換数は置換基として存在することができる限り特に制限はない。Ｃ１～Ｃ６のハロアルコキシ基の具体例として、ジフルオロメトキシ基、トリフルオロメトキシ基、クロロジフルオロメトキシ基、ブロモジフルオロメトキシ基、２－フルオロエトキシ基、２，２－ジフルオロエトキシ基、２，２，２－トリフルオロエトキシ基、１，１，２，２－テトラフルオロエトキシ基、ペンタフルオロエトキシ基、２，２，２－トリクロロエトキシ基、３，３－ジフルオロプロピルオキシ基、３，３，３－トリフルオロプロピルオキシ基、ヘプタフルオロプロピルオキシ基、ヘプタフルオロイソプロピルオキシ基、２，２，２－トリフルオロ－１－（トリフルオロメチル）－エトキシ基、４，４－ジフルオロブトキシ基、４，４，４－トリフルオロブトキシ基、ノナフルオロブトキシ基、ノナフルオロ－ｓｅｃ－ブトキシ基、５，５－ジフルオロペンチルオキシ基、５，５，５－トリフルオロペンチルオキシ基、３，３，４，４，５，５，５－ヘプタフルオロペンチルオキシ基、ウンデカフルオロペンチルオキシ基、トリデカフルオロヘキシルオキシ基等が挙げられる。 The term “C1 to C6 haloalkoxy group” refers to the above C1 to C6 alkoxy group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent. Specific examples of the C1-C6 haloalkoxy group include difluoromethoxy group, trifluoromethoxy group, chlorodifluoromethoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2,2-difluoroethoxy group, 2,2,2. -Trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, pentafluoroethoxy group, 2,2,2-trichloroethoxy group, 3,3-difluoropropyloxy group, 3,3,3-tri Fluoropropyloxy group, heptafluoropropyloxy group, heptafluoroisopropyloxy group, 2,2,2-trifluoro-1- (trifluoromethyl) -ethoxy group, 4,4-difluorobutoxy group, 4,4,4 -Trifluorobutoxy group, nonafluorobutoxy group, nonafluoro-sec-but Si group, 5,5-difluoropentyloxy group, 5,5,5-trifluoropentyloxy group, 3,3,4,4,5,5, heptafluoropentyloxy group, undecafluoropentyloxy group , Tridecafluorohexyloxy group and the like.
　Ｃ３～Ｃ８のシクロアルコキシ基とは、前記のＣ３～Ｃ８のシクロアルキル基が酸素原子を介して結合したものを表す。Ｃ３～Ｃ８のシクロアルコキシ基の具体例として、シクロプロピルオキシ基、シクロブトキシ基、シクロペンチルオキシ基、シクロヘキシルオキシ基、シクロヘプチルオキシ基、シクロオクチルオキシ基等が挙げられる。 The C3 to C8 cycloalkoxy group represents a group in which the C3 to C8 cycloalkyl group is bonded via an oxygen atom. Specific examples of the C3 to C8 cycloalkoxy group include a cyclopropyloxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group and a cyclooctyloxy group.
　Ｃ２～Ｃ６のアルケニルオキシ基とは、前記のＣ２～Ｃ６のアルケニル基が酸素原子を介して結合したものを表す。また、幾何異性体がある場合、Ｅ体またはＺ体のどちらか一方のみ、あるいはＥ体とＺ体との任意の割合の混合物であり、指定される炭素数の範囲であれば、特に制限されることはない。Ｃ２～Ｃ６のアルケニルオキシ基の具体例として、ビニルオキシ基、１－プロペニルオキシ基、アリルオキシ基、１－ブテニルオキシ基、２－ブテニルオキシ基、３－ブテニルオキシ基、２－メチル－１－プロペニルオキシ基、１－ペンテニルオキシ基、２－ペンテニルオキシ基、３－ペンテニルオキシ基、４－ペンテニルオキシ基、２－メチル－１－ブテニルオキシ基、３－メチル－２－ブテニルオキシ基、１－ヘキセニルオキシ基、２－ヘキセニルオキシ基、３－ヘキセニルオキシ基、４－ヘキセニルオキシ基、５－ヘキセニルオキシ基、３－メチル－２－ペンテニルオキシ基、４－メチル－３－ペンテニルオキシ基等が挙げられる。 The term "C2-C6 alkenyloxy group" refers to the C2-C6 alkenyl group bonded through an oxygen atom. When there is a geometric isomer, only one of the E-form and the Z-form, or a mixture of the E-form and the Z-form at an arbitrary ratio, is not particularly limited as long as the number of carbon atoms is within a specified range. Never. Specific examples of the C2-C6 alkenyloxy group include vinyloxy group, 1-propenyloxy group, allyloxy group, 1-butenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 2-methyl-1-propenyloxy group, 1 -Pentenyloxy group, 2-pentenyloxy group, 3-pentenyloxy group, 4-pentenyloxy group, 2-methyl-1-butenyloxy group, 3-methyl-2-butenyloxy group, 1-hexenyloxy group, 2-hexenyl Examples thereof include an oxy group, a 3-hexenyloxy group, a 4-hexenyloxy group, a 5-hexenyloxy group, a 3-methyl-2-pentenyloxy group and a 4-methyl-3-pentenyloxy group.
　Ｃ２～Ｃ６のハロアルケニルオキシ基とは、前記のＣ２～Ｃ６のアルケニルオキシ基における水素原子が１個または２個以上のハロゲン原子によって任意に置換されたものを表す。２個以上のハロゲン原子で置換される場合、それらのハロゲン原子は同一または異なっていてよく、その置換数は置換基として存在することができる限り特に制限はない。Ｃ２～Ｃ６のハロアルケニルオキシ基の具体例として、２－フルオロビニルオキシ基、２，２－ジフルオロビニルオキシ基、２，２－ジクロロビニルオキシ基、３－フルオロアリルオキシ基、３，３－ジフルオロアリルオキシ基、３，３－ジクロロアリルオキシ基、４，４－ジフルオロ－３－ブテニルオキシ基、５，５－ジフルオロ－４－ペンテニルオキシ基、６，６－ジフルオロ－５－ヘキセニルオキシ基等が挙げられる。 The term “C2-C6 haloalkenyloxy group” refers to the above-mentioned C2-C6 alkenyloxy group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent. Specific examples of the C2-C6 haloalkenyloxy group include a 2-fluorovinyloxy group, a 2,2-difluorovinyloxy group, a 2,2-dichlorovinyloxy group, a 3-fluoroallyloxy group, and a 3,3-difluoro group. Examples include allyloxy group, 3,3-dichloroallyloxy group, 4,4-difluoro-3-butenyloxy group, 5,5-difluoro-4-pentenyloxy group, and 6,6-difluoro-5-hexenyloxy group. To be
　Ｃ３～Ｃ６のアルキニルオキシ基とは、前記のＣ２～Ｃ６のアルキニル基のうち、Ｃ３～Ｃ６のアルキニル基が酸素原子を介して結合したものを表す。Ｃ３～Ｃ６のアルキニルオキシ基の具体例として、プロパルギルオキシ基、２－ブチニルオキシ基、３－ブチニルオキシ基、２－ペンチニルオキシ基、３－ペンチニルオキシ基、４－ペンチニルオキシ基、１，１－ジメチル－２－プロピニルオキシ基、２－ヘキシニルオキシ基、３－ヘキシニルオキシ基、４－ヘキシニルオキシ基、５－ヘキシニルオキシ基等が挙げられる。 The C3 to C6 alkynyloxy group refers to the C2 to C6 alkynyl group in which the C3 to C6 alkynyl group is bonded via an oxygen atom. Specific examples of the C3-C6 alkynyloxy group include propargyloxy group, 2-butynyloxy group, 3-butynyloxy group, 2-pentynyloxy group, 3-pentynyloxy group, 4-pentynyloxy group, 1,1. Examples thereof include a dimethyl-2-propynyloxy group, a 2-hexynyloxy group, a 3-hexynyloxy group, a 4-hexynyloxy group and a 5-hexynyloxy group.
　Ｃ３～Ｃ６のハロアルキニルオキシ基とは、前記のＣ３～Ｃ６のアルキニルオキシ基における水素原子が１個または２個以上のハロゲン原子によって任意に置換されたものを表す。２個以上のハロゲン原子で置換される場合、それらのハロゲン原子は同一または異なっていてよく、その置換数は置換基として存在することができる限り特に制限はない。Ｃ３～Ｃ６のハロアルキニルオキシ基の具体例として、１，１－ジフルオロ－２－プロピニルオキシ基、４，４－ジフルオロ－２－ブチニルオキシ基、４－クロロ－４，４－ジフルオロ－２－ブチニルオキシ基、４－ブロモ－４，４－ジフルオロ－２－ブチニルオキシ基、４，４，４－トリフルオロ－２－ブチニルオキシ基、５，５－ジフルオロ－３－ペンチニルオキシ基、５－クロロ－５，５－ジフルオロ－３－ペンチニルオキシ基、５－ブロモ－５，５－ジフルオロ－３－ペンチニルオキシ基、５，５，５－トリフルオロ－３－ペンチニルオキシ基、６，６－ジフルオロ－４－ヘキシニルオキシ基、６－クロロ－６，６－ジフルオロ－４－ヘキシニルオキシ基、６－ブロモ－６，６－ジフルオロ－４－ヘキシニルオキシ基、６，６，６－トリフルオロ－４－ヘキシニルオキシ基等が挙げられる。 The C3 to C6 haloalkynyloxy group refers to the above C3 to C6 alkynyloxy group in which a hydrogen atom is optionally substituted by one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent. Specific examples of the C3-C6 haloalkynyloxy group include 1,1-difluoro-2-propynyloxy group, 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro-2-butynyloxy group. , 4-bromo-4,4-difluoro-2-butynyloxy group, 4,4,4-trifluoro-2-butynyloxy group, 5,5-difluoro-3-pentynyloxy group, 5-chloro-5,5 -Difluoro-3-pentynyloxy group, 5-bromo-5,5-difluoro-3-pentynyloxy group, 5,5,5-trifluoro-3-pentynyloxy group, 6,6-difluoro-4 -Hexynyloxy group, 6-chloro-6,6-difluoro-4-hexynyloxy group, 6-bromo-6,6-difluoro-4-hexynyloxy group, 6,6,6- Trifluoroacetic 4- hexynyloxy group.
　Ｃ２～Ｃ６のアルコキシアルコキシ基とは、前記のＣ１～Ｃ６のアルコキシ基のうちＣ１～Ｃ５のアルコキシ基における水素原子が、１個または２個以上のＣ１～Ｃ５アルコキシ基で任意に置換されたものを表す。炭素数の総和が指定される炭素数の範囲であれば、特に限定されることはない。Ｃ２～Ｃ６のアルコキシアルコキシ基の具体例として、メトキシメトキシ基、エトキシメトキシ基、プロピルオキシメトキシ基、イソプロピルオキシメトキシ基、メトキシエトキシ基、エトキシエトキシ基、プロピルオキシエトキシ基、イソプロピルオキシエトキシ基、メトキシプロピルオキシ基、エトキシプロピルオキシ基、プロピルオキシプロピルオキシ基、イソプロピルオキシプロピルオキシ基等が挙げられる。 The C2 to C6 alkoxyalkoxy group is one in which the hydrogen atom in the C1 to C5 alkoxy group among the above C1 to C6 alkoxy groups is optionally substituted with one or two or more C1 to C5 alkoxy groups. Represents There is no particular limitation as long as the sum of the carbon numbers is within the specified carbon number range. Specific examples of the C2 to C6 alkoxyalkoxy group include methoxymethoxy group, ethoxymethoxy group, propyloxymethoxy group, isopropyloxymethoxy group, methoxyethoxy group, ethoxyethoxy group, propyloxyethoxy group, isopropyloxyethoxy group, methoxypropyl. Examples thereof include an oxy group, an ethoxypropyloxy group, a propyloxypropyloxy group and an isopropyloxypropyloxy group.
　本発明のピリドン化合物は、下記式（１）で表される化合物とその塩を包含する。（以下、「本発明化合物」ともいう。）
Figure JPOXMLDOC01-appb-C000003
 The pyridone compound of the present invention includes a compound represented by the following formula (1) and a salt thereof. (Hereinafter, also referred to as "the compound of the present invention".)
Figure JPOXMLDOC01-appb-C000003
　以下、式（１）について説明する。 The formula (1) will be described below.
　式（１）中のＲ１は、水素原子、シアノ基、ハロゲン原子、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、Ｃ２～Ｃ６のハロアルキニル基、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、Ｃ２～Ｃ６のハロアルケニルオキシ基、置換基Ａで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、Ｃ３～Ｃ６のハロアルキニルオキシ基、Ｒｃ－Ｌ－（ここで、Ｒｃは、Ｃ１～Ｃ６のアルキル基またはＣ１～Ｃ６のハロアルキル基を表し、Ｌは、Ｓ、ＳＯ、またはＳＯ２を表す。）、またはＲｇＣ（＝Ｏ）－（ここで、Ｒｇは、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表す。）を表し、
　中でもＲ１は、水素原子、ハロゲン原子、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、またはＲｇＣ（＝Ｏ）－（ここで、Ｒｇは、前記と同義である。）が好ましく、
　特にＲ１は、水素原子、ハロゲン原子、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基が好ましい。 R1 in the formula (1) is optionally substituted with a hydrogen atom, a cyano group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, or a substituent A. C3 to C8 cycloalkyl group, C2 to C6 alkenyl group optionally substituted with substituent A, C2 to C6 haloalkenyl group, C2 to C6 alkynyl optionally substituted with substituent A Group, C2-C6 haloalkynyl group, C1-C6 alkoxy group optionally substituted with substituent A, C1-C6 haloalkoxy group, C3-C8 cyclo group optionally substituted with substituent A Alkoxy group, C2-C6 alkenyloxy group optionally substituted with substituent A, C2-C6 haloalkenyloxy group, C3-C6 alkynyl optionally substituted with substituent A Alkoxy group, a halo alkynyloxy group C3 ~ C6, Rc-L- (wherein, Rc represents a haloalkyl group of alkyl or C1 ~ C6 of C1 ~ C6, L is S, SO, or SO 2 Or RgC (═O) — (wherein Rg is a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group. Represents, and represents
Among them, R1 is a hydrogen atom, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, a C2 to C6 alkenyl group optionally substituted with a substituent A , A C2 to C6 alkynyl group optionally substituted with a substituent A, a C1 to C6 alkoxy group optionally substituted with a substituent A, a C1 to C6 haloalkoxy group, or RgC (═O) — (Wherein Rg has the same meaning as above),
Particularly, R1 is preferably a hydrogen atom, a halogen atom, or a C1 to C6 alkyl group which may be appropriately substituted with a substituent A.
　式（１）のＲ１には、水素原子およびシアノ基が含まれる。 R1 in the formula (1) includes a hydrogen atom and a cyano group.
　式（１）のＲ１におけるハロゲン原子は、前記の定義と同義であり、好ましくはフッ素原子、塩素原子、臭素原子、またはヨウ素原子であり、さらに好ましくは、塩素原子または臭素原子である。 The halogen atom in R1 of the formula (1) has the same meaning as defined above, preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a chlorine atom or a bromine atom.
　式（１）のＲ１における「置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基」のＣ１～Ｃ６のアルキル基は、前記の定義と同義であり、好ましくは、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、またはイソブチル基であり、さらに好ましくは、メチル基、またはエチル基である。置換基Ａを有する場合、Ｃ１～Ｃ６のアルキル基における水素原子が、置換基Ａによって任意に置換される。 The C1 to C6 alkyl group of the “C1 to C6 alkyl group optionally substituted with the substituent A” in R1 of the formula (1) has the same meaning as defined above, and is preferably a methyl group or an ethyl group. , A propyl group, an isopropyl group, a butyl group, or an isobutyl group, and more preferably a methyl group or an ethyl group. When it has a substituent A, the hydrogen atom in the C1-C6 alkyl group is optionally substituted by the substituent A.
　式（１）のＲ１における「Ｃ１～Ｃ６のハロアルキル基」は、前記の定義と同義であり、好ましくは、ジフルオロメチル基、トリフルオロメチル基、２，２－ジフルオロエチル基、２，２，２－トリフルオロエチル基、３，３－ジフルオロプロピル基、または３，３，３－トリフルオロプロピル基であり、さらに好ましくは、ジフルオロメチル基、またはトリフルオロメチル基である。 The “C1-C6 haloalkyl group” for R1 in formula (1) has the same meaning as defined above, and is preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, 2,2,2. -Trifluoroethyl group, 3,3-difluoropropyl group, or 3,3,3-trifluoropropyl group, and more preferably difluoromethyl group or trifluoromethyl group.
　式（１）のＲ１における「置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基」のＣ３～Ｃ８のシクロアルキル基は、前記の定義と同義であり、好ましくは、シクロプロピル基、シクロブチル基、シクロペンチル基、またはシクロヘキシル基であり、さらに好ましくは、シクロプロピル基、またはシクロブチル基である。置換基Ａを有する場合、Ｃ３～Ｃ８のシクロアルキル基における水素原子が、置換基Ａによって任意に置換される。 The C3 to C8 cycloalkyl group of the "C3 to C8 cycloalkyl group optionally substituted with the substituent A" in R1 of the formula (1) has the same meaning as defined above, and preferably a cyclopropyl group. , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group. When it has a substituent A, the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent A.
　式（１）のＲ１における「置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基」のＣ２～Ｃ６のアルケニル基は、前記の定義と同義であり、好ましくは、ビニル基、１－プロペニル基、アリル基、１－ブテニル基、２－ブテニル基、または３－ブテニル基であり、さらに好ましくは、ビニル基、１－プロペニル基、またはアリル基である。置換基Ａを有する場合、Ｃ２～Ｃ６のアルケニル基における水素原子が、置換基Ａによって任意に置換される。 The C2-C6 alkenyl group of the "C2-C6 alkenyl group optionally substituted with the substituent A" in R1 of the formula (1) has the same meaning as defined above, preferably a vinyl group, 1- A propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, or a 3-butenyl group is more preferable, and a vinyl group, a 1-propenyl group, or an allyl group is more preferable. When it has a substituent A, the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent A.
　式（１）のＲ１における「Ｃ２～Ｃ６のハロアルケニル基」は、前記の定義と同義であり、好ましくは、２－フルオロビニル基、２，２－ジフルオロビニル基、２，２－ジクロロビニル基、３－フルオロアリル基、３，３－ジフルオロアリル基、または３，３－ジクロロアリル基であり、さらに好ましくは、２－フルオロビニル基、または２，２－ジフルオロビニル基である。 The “C2-C6 haloalkenyl group” for R 1 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group, a 2,2-dichlorovinyl group. , 3-fluoroallyl group, 3,3-difluoroallyl group, or 3,3-dichloroallyl group, and more preferably 2-fluorovinyl group or 2,2-difluorovinyl group.
　式（１）のＲ１における「置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基」のＣ２～Ｃ６のアルキニル基は、前記の定義と同義であり、好ましくは、エチニル基、１－プロピニル基、プロパルギル基、１－ブチニル基、２－ブチニル基、または３－ブチニル基であり、さらに好ましくは、エチニル基、１－プロピニル基、またはプロパルギル基である。置換基Ａを有する場合、Ｃ２～Ｃ６のアルキニル基における水素原子が、置換基Ａによって任意に置換される。 The C2-C6 alkynyl group of the "C2-C6 alkynyl group optionally substituted with the substituent A" in R1 of the formula (1) has the same meaning as defined above, preferably an ethynyl group, 1- A propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group is more preferable, and an ethynyl group, a 1-propynyl group, or a propargyl group is more preferable. When it has a substituent A, the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent A.
　式（１）のＲ１における「Ｃ２～Ｃ６のハロアルキニル基」は、前記の定義と同義であり、好ましくは、３，３－ジフルオロ－１－プロピニル基、３，３，３－トリフルオロ－１－プロピニル基、４，４－ジフルオロ－１－ブチニル基、４，４－ジフルオロ－２－ブチニル基、４，４，４－トリフルオロ－１－ブチニル基、または４，４，４－トリフルオロ－２－ブチニル基であり、さらに好ましくは、３，３－ジフルオロ－１－プロピニル基、または３，３，３－トリフルオロ－１－プロピニル基である。 The "C2-C6 haloalkynyl group" in R1 of the formula (1) has the same meaning as defined above, and is preferably a 3,3-difluoro-1-propynyl group or 3,3,3-trifluoro-1. -Propinyl group, 4,4-difluoro-1-butynyl group, 4,4-difluoro-2-butynyl group, 4,4,4-trifluoro-1-butynyl group, or 4,4,4-trifluoro- It is a 2-butynyl group, more preferably a 3,3-difluoro-1-propynyl group or a 3,3,3-trifluoro-1-propynyl group.
　式（１）のＲ１における「置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基」のＣ１～Ｃ６のアルコキシ基は、前記の定義と同義であり、好ましくは、メトキシ基、エトキシ基、プロピルオキシ基、またはイソプロピルオキシ基であり、さらに好ましくは、メトキシ基、またはエトキシ基である。置換基Ａを有する場合、Ｃ１～Ｃ６のアルコキシ基における水素原子が、置換基Ａによって任意に置換される。 The C1 to C6 alkoxy group of the “C1 to C6 alkoxy group optionally substituted by the substituent A” in R1 of the formula (1) has the same meaning as defined above, and preferably a methoxy group or an ethoxy group. , A propyloxy group, or an isopropyloxy group, and more preferably a methoxy group or an ethoxy group. When it has a substituent A, the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent A.
　式（１）のＲ１における「Ｃ１～Ｃ６のハロアルコキシ基」は、前記の定義と同義であり、好ましくは、ジフルオロメトキシ基、トリフルオロメトキシ基、２，２－ジフルオロエトキシ基、２，２，２－トリフルオロエトキシ基、３，３－ジフルオロプロピルオキシ基、または３，３，３－トリフルオロプロピルオキシ基であり、さらに好ましくは、ジフルオロメトキシ基、トリフルオロメトキシ基、２，２－ジフルオロエトキシ基、または２，２，２－トリフルオロエトキシ基である。 The "C1-C6 haloalkoxy group" in R1 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2,2. 2-trifluoroethoxy group, 3,3-difluoropropyloxy group or 3,3,3-trifluoropropyloxy group, more preferably difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group Or a 2,2,2-trifluoroethoxy group.
　式（１）のＲ１における「置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基」のＣ３～Ｃ８のシクロアルコキシ基は、前記の定義と同義であり、好ましくは、シクロプロピルオキシ基、シクロブトキシ基、シクロペンチルオキシ基、またはシクロヘキシルオキシ基であり、さらに好ましくは、シクロプロピルオキシ基、またはシクロブトキシ基である。置換基Ａを有する場合、Ｃ３～Ｃ８のシクロアルコキシ基における水素原子が、置換基Ａによって任意に置換される。 The C3 to C8 cycloalkoxy group of the "C3 to C8 cycloalkoxy group optionally substituted by the substituent A" in R1 of the formula (1) has the same meaning as defined above, and preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group. When it has a substituent A, the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted by the substituent A.
　式（１）のＲ１における「置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基」のＣ２～Ｃ６のアルケニルオキシ基は、前記の定義と同義であり、好ましくは、ビニルオキシ基、１－プロペニルオキシ基、アリルオキシ基、１－ブテニルオキシ基、２－ブテニルオキシ基、または３－ブテニルオキシ基であり、さらに好ましくは、ビニルオキシ基、１－プロペニルオキシ基、またはアリルオキシ基である。置換基Ａを有する場合、Ｃ２～Ｃ６のアルケニルオキシ基における水素原子が、置換基Ａによって任意に置換される。 The C2-C6 alkenyloxy group of the "C2-C6 alkenyloxy group optionally substituted with the substituent A" in R1 of the formula (1) has the same meaning as defined above, and preferably a vinyloxy group, It is a 1-propenyloxy group, an allyloxy group, a 1-butenyloxy group, a 2-butenyloxy group or a 3-butenyloxy group, more preferably a vinyloxy group, a 1-propenyloxy group or an allyloxy group. When it has a substituent A, the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent A.
　式（１）のＲ１における「Ｃ２～Ｃ６のハロアルケニルオキシ基」は、前記の定義と同義であり、好ましくは、２－フルオロビニルオキシ基、２，２－ジフルオロビニルオキシ基、２，２－ジクロロビニルオキシ基、３－フルオロアリルオキシ基、３，３－ジフルオロアリルオキシ基、または３，３－ジクロロアリルオキシ基であり、さらに好ましくは、２－フルオロビニルオキシ基、または２，２－ジフルオロビニルオキシ基である。 The “C2-C6 haloalkenyloxy group” for R 1 in formula (1) has the same meaning as defined above, and is preferably 2-fluorovinyloxy group, 2,2-difluorovinyloxy group, 2,2- A dichlorovinyloxy group, a 3-fluoroallyloxy group, a 3,3-difluoroallyloxy group, or a 3,3-dichloroallyloxy group, more preferably a 2-fluorovinyloxy group or a 2,2-difluoro group. It is a vinyloxy group.
　式（１）のＲ１における「置換基Ａで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基」のＣ３～Ｃ６のアルキニルオキシ基は、前記の定義と同義であり、好ましくは、プロパルギルオキシ基、２－ブチニルオキシ基、または３－ブチニルオキシ基であり、さらに好ましくは、プロパルギルオキシ基である。置換基Ａを有する場合、Ｃ３～Ｃ６のアルキニルオキシ基における水素原子が、置換基Ａによって任意に置換される。 The C3-C6 alkynyloxy group of the "C3-C6 alkynyloxy group optionally substituted by the substituent A" in R1 of the formula (1) has the same meaning as defined above, and preferably a propargyloxy group. , 2-butynyloxy group, or 3-butynyloxy group, and more preferably propargyloxy group. When it has a substituent A, the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent A.
　式（１）のＲ１における「Ｃ３～Ｃ６のハロアルキニルオキシ基」は、前記の定義と同義であり、好ましくは、４，４－ジフルオロ－２－ブチニルオキシ基、４－クロロ－４，４－ジフルオロ－２－ブチニルオキシ基、４－ブロモ－４，４－ジフルオロ－２－ブチニルオキシ基、または４，４，４－トリフルオロ－２－ブチニルオキシ基であり、さらに好ましくは、４，４－ジフルオロ－２－ブチニルオキシ基、または４，４，４－トリフルオロ－２－ブチニルオキシ基である。 The "C3-C6 haloalkynyloxy group" in R1 of the formula (1) has the same meaning as defined above, and is preferably a 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro group. -2-butynyloxy group, 4-bromo-4,4-difluoro-2-butynyloxy group, or 4,4,4-trifluoro-2-butynyloxy group, more preferably 4,4-difluoro-2- It is a butynyloxy group or a 4,4,4-trifluoro-2-butynyloxy group.
　式（１）のＲ１における「Ｒｃ－Ｌ－」（ここで、Ｒｃは、Ｃ１～Ｃ６のアルキル基またはＣ１～Ｃ６のハロアルキル基を表し、Ｌは、Ｓ、ＳＯ、またはＳＯ２を表す。）の各用語は、前記の定義と同義である。「Ｒｃ－Ｌ－」として、好ましくは、メチルチオ基、メタンスルフィニル基、メタンスルホニル基、エチルチオ基、エタンスルフィニル基、エタンスルホニル基、トリフルオロメチルチオ基、トリフルオロメタンスルフィニル基、またはトリフルオロメタンスルホニル基であり、さらに好ましくは、メチルチオ基、メタンスルフィニル基、またはメタンスルホニル基である。 "Rc-L -" in R1 of formula (1) (wherein, Rc represents a haloalkyl group of alkyl or C1 ~ C6 of C1 ~ C6, L represents S, SO, or SO 2.) Each of the terms has the same meaning as defined above. "Rc-L-" is preferably a methylthio group, a methanesulfinyl group, a methanesulfonyl group, an ethylthio group, an ethanesulfinyl group, an ethanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, or a trifluoromethanesulfonyl group. , And more preferably, a methylthio group, a methanesulfinyl group, or a methanesulfonyl group.
　式（１）のＲ１における「ＲｇＣ（＝Ｏ）－」（ここで、Ｒｇは、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表す。）の各用語は、前記の定義と同義である。なお、「置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基」に関しては、置換基Ｂを有する場合、Ｃ１～Ｃ６のアルキル基における水素原子が、置換基Ｂによって任意に置換される。「ＲｇＣ（＝Ｏ）－」として、好ましくは、アセチル基、メトキシアセチル基、シアノアセチル基、プロピオニル基、ジフルオロアセチル基、トリフルオロアセチル基、またはシクロプロパンカルボニル基であり、さらに好ましくは、アセチル基、またはプロピオニル基である。 “RgC (═O) —” in R1 of the formula (1) (wherein Rg is a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or C3 to C8) Represents a cycloalkyl group of) and has the same meaning as defined above. Regarding the “C1 to C6 alkyl group optionally substituted with the substituent B”, in the case of having the substituent B, the hydrogen atom in the C1 to C6 alkyl group is optionally substituted with the substituent B. . “RgC (═O) —” is preferably an acetyl group, a methoxyacetyl group, a cyanoacetyl group, a propionyl group, a difluoroacetyl group, a trifluoroacetyl group, or a cyclopropanecarbonyl group, more preferably an acetyl group. Or a propionyl group.
　式（１）中のＲ２は、シアノ基、ハロゲン原子、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、Ｃ２～Ｃ６のハロアルキニル基、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、Ｃ２～Ｃ６のハロアルケニルオキシ基、置換基Ａで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、Ｃ３～Ｃ６のハロアルキニルオキシ基、Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）、またはＲｇＣ（＝Ｏ）－（ここで、Ｒｇは、前記と同義である。）を表し、
　中でもＲ２は、ハロゲン原子、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、または置換基Ａで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基が好ましく、
　特にＲ２は、ハロゲン原子、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基が好ましい。 R2 in the formula (1) is a cyano group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, or a C3 optionally substituted with a substituent A. To C8 cycloalkyl group, C2 to C6 alkenyl group optionally substituted with substituent A, C2 to C6 haloalkenyl group, C2 to C6 alkynyl group optionally substituted with substituent A, C2 To C6 haloalkynyl group, C1 to C6 alkoxy group optionally substituted with substituent A, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group optionally substituted with substituent A, A C2 to C6 alkenyloxy group optionally substituted with a substituent A, a C2 to C6 haloalkenyloxy group, a C3 to C6 alkynyloxy group optionally substituted with a substituent A, A 3-C6 haloalkynyloxy group, Rc-L- (wherein Rc and L are as defined above), or RgC (= O)-(wherein Rg is as defined above). ),
Among them, R2 is a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, a C2 to C6 alkenyl group optionally substituted with a substituent A, a substituent C2 to C6 alkynyl group optionally substituted with A, C1 to C6 alkoxy group optionally substituted with substituent A, C1 to C6 haloalkoxy group, optionally substituted with substituent A A C2-C6 alkenyloxy group or a C3-C6 alkynyloxy group optionally substituted with a substituent A is preferable,
Particularly, R2 is preferably a halogen atom, a C1-C6 alkyl group which may be optionally substituted with a substituent A, or a C1-C6 alkoxy group which is optionally substituted with a substituent A.
　式（１）のＲ２には、シアノ基が含まれる。 R2 in formula (1) includes a cyano group.
　式（１）のＲ２におけるハロゲン原子は、前記の定義と同義であり、好ましくはフッ素原子、塩素原子、臭素原子、またはヨウ素原子であり、さらに好ましくは、塩素原子、または臭素原子である。 The halogen atom in R2 of the formula (1) has the same meaning as defined above, preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a chlorine atom or a bromine atom.
　式（１）のＲ２における「置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基」のＣ１～Ｃ６のアルキル基は、前記の定義と同義であり、好ましくは、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、またはイソブチル基であり、さらに好ましくは、メチル基、エチル基、プロピル基、またはブチル基である。置換基Ａを有する場合、Ｃ１～Ｃ６のアルキル基における水素原子が、置換基Ａによって任意に置換される。 The C1 to C6 alkyl group of the “C1 to C6 alkyl group optionally substituted with the substituent A” in R2 of the formula (1) has the same meaning as defined above, and preferably a methyl group or an ethyl group. , A propyl group, an isopropyl group, a butyl group, or an isobutyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. When it has a substituent A, the hydrogen atom in the C1-C6 alkyl group is optionally substituted by the substituent A.
　式（１）のＲ２における「Ｃ１～Ｃ６のハロアルキル基」は、前記の定義と同義であり、好ましくは、ジフルオロメチル基、トリフルオロメチル基、２，２－ジフルオロエチル基、２，２，２－トリフルオロエチル基、３，３－ジフルオロプロピル基、または３，３，３－トリフルオロプロピル基であり、さらに好ましくは、ジフルオロメチル基、トリフルオロメチル基、２，２－ジフルオロエチル基、または２，２，２－トリフルオロエチル基である。 The “C1-C6 haloalkyl group” in R2 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, 2,2,2. A trifluoroethyl group, a 3,3-difluoropropyl group, or a 3,3,3-trifluoropropyl group, more preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, or It is a 2,2,2-trifluoroethyl group.
　式（１）のＲ２における「置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基」のＣ３～Ｃ８のシクロアルキル基は、前記の定義と同義であり、好ましくは、シクロプロピル基、シクロブチル基、シクロペンチル基、またはシクロヘキシル基であり、さらに好ましくは、シクロプロピル基、またはシクロブチル基である。置換基Ａを有する場合、Ｃ３～Ｃ８のシクロアルキル基における水素原子が、置換基Ａによって任意に置換される。 The C3 to C8 cycloalkyl group of the "C3 to C8 cycloalkyl group optionally substituted with the substituent A" in R2 of the formula (1) has the same meaning as defined above, and is preferably a cyclopropyl group. , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group. When it has a substituent A, the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent A.
　式（１）のＲ２における「置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基」のＣ２～Ｃ６のアルケニル基は、前記の定義と同義であり、好ましくは、ビニル基、１－プロペニル基、アリル基、１－ブテニル基、２－ブテニル基、または３－ブテニル基であり、さらに好ましくは、ビニル基、１－プロペニル基、またはアリル基である。置換基Ａを有する場合、Ｃ２～Ｃ６のアルケニル基における水素原子が、置換基Ａによって任意に置換される。 The C2-C6 alkenyl group in the "C2-C6 alkenyl group optionally substituted by the substituent A" in R2 of the formula (1) has the same meaning as defined above, preferably a vinyl group, 1- A propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, or a 3-butenyl group is more preferable, and a vinyl group, a 1-propenyl group, or an allyl group is more preferable. When it has a substituent A, the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent A.
　式（１）のＲ２における「Ｃ２～Ｃ６のハロアルケニル基」は、前記の定義と同義であり、好ましくは、２－フルオロビニル基、２，２－ジフルオロビニル基、２，２－ジクロロビニル基、３－フルオロアリル基、３，３－ジフルオロアリル基、または３，３－ジクロロアリル基であり、さらに好ましくは、２－フルオロビニル基、または２，２－ジフルオロビニル基である。 The "C2-C6 haloalkenyl group" for R2 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group, a 2,2-dichlorovinyl group. , 3-fluoroallyl group, 3,3-difluoroallyl group, or 3,3-dichloroallyl group, and more preferably 2-fluorovinyl group or 2,2-difluorovinyl group.
　式（１）のＲ２における「置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基」のＣ２～Ｃ６のアルキニル基は、前記の定義と同義であり、好ましくは、エチニル基、１－プロピニル基、プロパルギル基、１－ブチニル基、２－ブチニル基、または３－ブチニル基であり、さらに好ましくは、エチニル基、１－プロピニル基、またはプロパルギル基である。置換基Ａを有する場合、Ｃ２～Ｃ６のアルキニル基における水素原子が、置換基Ａによって任意に置換される。 The C2-C6 alkynyl group of the "C2-C6 alkynyl group optionally substituted with the substituent A" in R2 of the formula (1) has the same meaning as defined above, preferably an ethynyl group, 1- A propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group is more preferable, and an ethynyl group, a 1-propynyl group, or a propargyl group is more preferable. When it has a substituent A, the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent A.
　式（１）のＲ２における「Ｃ２～Ｃ６のハロアルキニル基」は、前記の定義と同義であり、好ましくは、３，３－ジフルオロ－１－プロピニル基、３，３，３－トリフルオロ－１－プロピニル基、４，４－ジフルオロ－１－ブチニル基、４，４－ジフルオロ－２－ブチニル基、４，４，４－トリフルオロ－１－ブチニル基、または４，４，４－トリフルオロ－２－ブチニル基であり、さらに好ましくは、３，３－ジフルオロ－１－プロピニル基、または３，３，３－トリフルオロ－１－プロピニル基である。 The "C2-C6 haloalkynyl group" in R2 of the formula (1) has the same meaning as defined above, and is preferably a 3,3-difluoro-1-propynyl group or 3,3,3-trifluoro-1. -Propinyl group, 4,4-difluoro-1-butynyl group, 4,4-difluoro-2-butynyl group, 4,4,4-trifluoro-1-butynyl group, or 4,4,4-trifluoro- It is a 2-butynyl group, more preferably a 3,3-difluoro-1-propynyl group or a 3,3,3-trifluoro-1-propynyl group.
　式（１）のＲ２における「置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基」のＣ１～Ｃ６のアルコキシ基は、前記の定義と同義であり、好ましくは、メトキシ基、エトキシ基、プロピルオキシ基、またはイソプロピルオキシ基であり、さらに好ましくは、メトキシ基、エトキシ基、またはプロピルオキシ基である。置換基Ａを有する場合、Ｃ１～Ｃ６のアルコキシ基における水素原子が、置換基Ａによって任意に置換される。 The C1 to C6 alkoxy group of the “C1 to C6 alkoxy group optionally substituted by the substituent A” in R2 of the formula (1) has the same meaning as defined above, and preferably a methoxy group or an ethoxy group. , A propyloxy group, or an isopropyloxy group, and more preferably a methoxy group, an ethoxy group, or a propyloxy group. When it has a substituent A, the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent A.
　式（１）のＲ２における「Ｃ１～Ｃ６のハロアルコキシ基」は、前記の定義と同義であり、好ましくは、ジフルオロメトキシ基、トリフルオロメトキシ基、２，２－ジフルオロエトキシ基、２，２，２－トリフルオロエトキシ基、３，３－ジフルオロプロピルオキシ基、または３，３，３－トリフルオロプロピルオキシ基であり、さらに好ましくは、ジフルオロメトキシ基、トリフルオロメトキシ基、２，２－ジフルオロエトキシ基、または２，２，２－トリフルオロエトキシ基である。 The "C1-C6 haloalkoxy group" in R2 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2,2. 2-trifluoroethoxy group, 3,3-difluoropropyloxy group or 3,3,3-trifluoropropyloxy group, more preferably difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group Or a 2,2,2-trifluoroethoxy group.
　式（１）のＲ２における「置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基」のＣ３～Ｃ８のシクロアルコキシ基は、前記の定義と同義であり、好ましくは、シクロプロピルオキシ基、シクロブトキシ基、シクロペンチルオキシ基、またはシクロヘキシルオキシ基であり、さらに好ましくは、シクロプロピルオキシ基、またはシクロブトキシ基である。置換基Ａを有する場合、Ｃ３～Ｃ８のシクロアルコキシ基における水素原子が、置換基Ａによって任意に置換される。 The C3 to C8 cycloalkoxy group of the "C3 to C8 cycloalkoxy group optionally substituted with the substituent A" in R2 of the formula (1) has the same meaning as defined above, and preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group. When it has a substituent A, the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted by the substituent A.
　式（１）のＲ２における「置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基」のＣ２～Ｃ６のアルケニルオキシ基は、前記の定義と同義であり、好ましくは、ビニルオキシ基、１－プロペニルオキシ基、アリルオキシ基、１－ブテニルオキシ基、２－ブテニルオキシ基、または３－ブテニルオキシ基であり、さらに好ましくは、ビニルオキシ基、１－プロペニルオキシ基、またはアリルオキシ基である。置換基Ａを有する場合、Ｃ２～Ｃ６のアルケニルオキシ基における水素原子が、置換基Ａによって任意に置換される。 The C2-C6 alkenyloxy group in the "C2-C6 alkenyloxy group optionally substituted with the substituent A" in R2 of the formula (1) has the same meaning as defined above, and preferably a vinyloxy group, It is a 1-propenyloxy group, an allyloxy group, a 1-butenyloxy group, a 2-butenyloxy group or a 3-butenyloxy group, more preferably a vinyloxy group, a 1-propenyloxy group or an allyloxy group. When it has a substituent A, the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent A.
　式（１）のＲ２における「Ｃ２～Ｃ６のハロアルケニルオキシ基」は、前記の定義と同義であり、好ましくは、２－フルオロビニルオキシ基、２，２－ジフルオロビニルオキシ基、２，２－ジクロロビニルオキシ基、３－フルオロアリルオキシ基、３，３－ジフルオロアリルオキシ基、または３，３－ジクロロアリルオキシ基であり、さらに好ましくは、２－フルオロビニルオキシ基、または２，２－ジフルオロビニルオキシ基である。 The “C2-C6 haloalkenyloxy group” in R2 of the formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyloxy group, a 2,2-difluorovinyloxy group or a 2,2- A dichlorovinyloxy group, a 3-fluoroallyloxy group, a 3,3-difluoroallyloxy group, or a 3,3-dichloroallyloxy group, more preferably a 2-fluorovinyloxy group or a 2,2-difluoro group. It is a vinyloxy group.
　式（１）のＲ２における「置換基Ａで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基」のＣ３～Ｃ６のアルキニルオキシ基は、前記の定義と同義であり、好ましくは、プロパルギルオキシ基、２－ブチニルオキシ基、または３－ブチニルオキシ基であり、さらに好ましくは、プロパルギルオキシ基である。置換基Ａを有する場合、Ｃ３～Ｃ６のアルキニルオキシ基における水素原子が、置換基Ａによって任意に置換される。 The C3-C6 alkynyloxy group of the "C3-C6 alkynyloxy group optionally substituted by the substituent A" in R2 of the formula (1) has the same meaning as defined above, and preferably a propargyloxy group. , 2-butynyloxy group, or 3-butynyloxy group, and more preferably propargyloxy group. When it has a substituent A, the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent A.
　式（１）のＲ２における「Ｃ３～Ｃ６のハロアルキニルオキシ基」は、前記の定義と同義であり、好ましくは、４，４－ジフルオロ－２－ブチニルオキシ基、４－クロロ－４，４－ジフルオロ－２－ブチニルオキシ基、４－ブロモ－４，４－ジフルオロ－２－ブチニルオキシ基、または４，４，４－トリフルオロ－２－ブチニルオキシ基であり、さらに好ましくは、４，４－ジフルオロ－２－ブチニルオキシ基、または４，４，４－トリフルオロ－２－ブチニルオキシ基である。 The “C3-C6 haloalkynyloxy group” in R2 of the formula (1) has the same meaning as defined above, and is preferably 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro group. -2-butynyloxy group, 4-bromo-4,4-difluoro-2-butynyloxy group, or 4,4,4-trifluoro-2-butynyloxy group, more preferably 4,4-difluoro-2- It is a butynyloxy group or a 4,4,4-trifluoro-2-butynyloxy group.
　式（１）のＲ２における「Ｒｃ－Ｌ－」のＲｃおよびＬは、前記と同義である。「Ｒｃ－Ｌ－」として、好ましくは、メチルチオ基、メタンスルフィニル基、メタンスルホニル基、エチルチオ基、エタンスルフィニル基、エタンスルホニル基、トリフルオロメチルチオ基、トリフルオロメタンスルフィニル基、またはトリフルオロメタンスルホニル基であり、さらに好ましくは、メチルチオ基、メタンスルフィニル基、またはメタンスルホニル基である。 Rc and L of "Rc-L-" in R2 of the formula (1) have the same meaning as above. "Rc-L-" is preferably a methylthio group, a methanesulfinyl group, a methanesulfonyl group, an ethylthio group, an ethanesulfinyl group, an ethanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, or a trifluoromethanesulfonyl group. , And more preferably, a methylthio group, a methanesulfinyl group, or a methanesulfonyl group.
　式（１）のＲ２における「ＲｇＣ（＝Ｏ）－」のＲｇは、前記と同義である。「ＲｇＣ（＝Ｏ）－」として、好ましくは、アセチル基、メトキシアセチル基、シアノアセチル基、プロピオニル基、ジフルオロアセチル基、トリフルオロアセチル基、またはシクロプロパンカルボニル基であり、さらに好ましくは、アセチル基、またはプロピオニル基である。 Rg of "RgC (= O)-" in R2 of the formula (1) has the same meaning as above. “RgC (═O) —” is preferably an acetyl group, a methoxyacetyl group, a cyanoacetyl group, a propionyl group, a difluoroacetyl group, a trifluoroacetyl group, or a cyclopropanecarbonyl group, more preferably an acetyl group. Or a propionyl group.
　式（１）中のＸは、酸素原子または硫黄原子であり、好ましくは、酸素原子である。
　式（１）中のＲ３は、水酸基、シアノ基、ニトロ基、ハロゲン原子、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、Ｃ２～Ｃ６のハロアルキニル基、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、Ｃ２～Ｃ６のハロアルケニルオキシ基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、Ｃ３～Ｃ６のハロアルキニルオキシ基、ＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、またはＣ３～Ｃ８のシクロアルコキシ基を表す。）、ＲｄＣ（＝Ｏ）Ｏ－（ここで、Ｒｄは、前記と同義である。）、Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）、ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、それぞれ独立していて、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表す。）、または、ＲｅＣ（＝Ｏ）Ｎ（Ｒｆ）－（ここで、ＲｅとＲｆは、それぞれ独立していて、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、Ｃ３～Ｃ８のシクロアルコキシ基、またはＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）を表す。）を表し、
　中でもＲ３は、水酸基、シアノ基、ハロゲン原子、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、または置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基が好ましく、
　さらにＲ３は、ハロゲン原子、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基が好ましい。 X in the formula (1) is an oxygen atom or a sulfur atom, preferably an oxygen atom.
R3 in the formula (1) is appropriately substituted with a hydroxyl group, a cyano group, a nitro group, a halogen atom, a C1 to C6 alkyl group which may be optionally substituted with a substituent C, a C1 to C6 haloalkyl group, and a substituent C. An optionally substituted C3 to C8 cycloalkyl group, a C2 to C6 alkenyl group optionally substituted with a substituent C, a C2 to C6 haloalkenyl group, a C2 to C6 optionally substituted with a substituent C Alkynyl group, C2 to C6 haloalkynyl group, C1 to C6 alkoxy group optionally substituted with a substituent C, C1 to C6 haloalkoxy group, C3 to C8 optionally substituted with a substituent C A cycloalkoxy group, a C2-C6 alkenyloxy group which may be optionally substituted with a substituent C, a C2-C6 haloalkenyloxy group, a C3-C6 group which may be optionally substituted with a substituent C. A quinyloxy group, a C3-C6 haloalkynyloxy group, RdC (= O)-(wherein Rd is a hydrogen atom, a C1-C6 alkyl group optionally substituted with a substituent B, a C1-C6 haloalkyl group Group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, or a C3 to C8 cycloalkoxy group), RdC (═O) O— (wherein Rd Is as defined above, Rc-L- (wherein Rc and L are as defined above), RaRbN- (wherein Ra and Rb are each independently hydrogen atom). Represents an optionally substituted C1 to C6 alkyl group, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group), or ReC (═O) N (Rf)- ( Here, Re and Rf are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, C1 To C6 alkoxy group, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group, or RaRbN- (wherein Ra and Rb are as defined above).
Among them, R3 is a hydroxyl group, a cyano group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, or a C2 to C6 optionally substituted with a substituent C. Alkenyl group, C2-C6 alkynyl group optionally substituted with substituent C, C1-C6 alkoxy group optionally substituted with substituent C, C1-C6 haloalkoxy group, optionally substituted with substituent C An optionally substituted C2 to C6 alkenyloxy group, or a C3 to C6 alkynyloxy group optionally substituted with a substituent C is preferable,
Further, R3 is preferably a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, or a C1 to C6 alkoxy group optionally substituted with a substituent C.
　式（１）のＲ３には、水酸基、シアノ基、およびニトロ基が含まれる。
　式（１）のＲ３におけるハロゲン原子は、前記の定義と同義であり、好ましくはフッ素原子、塩素原子、臭素原子、またはヨウ素原子である。 R3 in the formula (1) includes a hydroxyl group, a cyano group, and a nitro group.
The halogen atom in R3 of formula (1) has the same meaning as defined above, and is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
　式（１）のＲ３における「置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基」のＣ１～Ｃ６のアルキル基は、前記の定義と同義であり、好ましくは、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、またはイソブチル基であり、さらに好ましくは、メチル基、またはエチル基である。置換基Ｃを有する場合、Ｃ１～Ｃ６のアルキル基における水素原子が、置換基Ｃによって任意に置換される。 The C1 to C6 alkyl group of the “C1 to C6 alkyl group optionally substituted with a substituent C” in R3 of the formula (1) has the same meaning as defined above, and preferably a methyl group or an ethyl group. , A propyl group, an isopropyl group, a butyl group, or an isobutyl group, and more preferably a methyl group or an ethyl group. When it has a substituent C, the hydrogen atom in the C1 to C6 alkyl group is optionally substituted by the substituent C.
　式（１）のＲ３における「Ｃ１～Ｃ６のハロアルキル基」は、前記の定義と同義であり、好ましくは、ジフルオロメチル基、トリフルオロメチル基、２，２－ジフルオロエチル基、２，２，２－トリフルオロエチル基、３，３－ジフルオロプロピル基、または３，３，３－トリフルオロプロピル基であり、さらに好ましくは、ジフルオロメチル基、またはトリフルオロメチル基である。 The “C1-C6 haloalkyl group” for R3 in formula (1) has the same meaning as defined above, and is preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, 2,2,2. -A trifluoroethyl group, a 3,3-difluoropropyl group, or a 3,3,3-trifluoropropyl group, more preferably a difluoromethyl group or a trifluoromethyl group.
　式（１）のＲ３における「置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基」のＣ３～Ｃ８のシクロアルキル基は、前記の定義と同義であり、好ましくは、シクロプロピル基、シクロブチル基、シクロペンチル基、またはシクロヘキシル基であり、さらに好ましくは、シクロプロピル基、またはシクロブチル基である。置換基Ｃを有する場合、Ｃ３～Ｃ８のシクロアルキル基における水素原子が、置換基Ｃによって任意に置換される。 The C3 to C8 cycloalkyl group of the "C3 to C8 cycloalkyl group optionally substituted by the substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably a cyclopropyl group. , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group. When it has a substituent C, the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent C.
　式（１）のＲ３における「置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基」のＣ２～Ｃ６のアルケニル基は、前記の定義と同義であり、好ましくは、ビニル基、１－プロペニル基、アリル基、１－ブテニル基、２－ブテニル基、または３－ブテニル基であり、さらに好ましくは、ビニル基、１－プロペニル基、またはアリル基である。置換基Ｃを有する場合、Ｃ２～Ｃ６のアルケニル基における水素原子が、置換基Ｃによって任意に置換される。 The C2-C6 alkenyl group in the "C2-C6 alkenyl group optionally substituted with a substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably a vinyl group, 1- A propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, or a 3-butenyl group is more preferable, and a vinyl group, a 1-propenyl group, or an allyl group is more preferable. When it has a substituent C, the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent C.
　式（１）のＲ３における「Ｃ２～Ｃ６のハロアルケニル基」は、前記の定義と同義であり、好ましくは、２－フルオロビニル基、２，２－ジフルオロビニル基、２，２－ジクロロビニル基、３－フルオロアリル基、３，３－ジフルオロアリル基、または３，３－ジクロロアリル基であり、さらに好ましくは、２－フルオロビニル基、または２，２－ジフルオロビニル基である。 The “C2-C6 haloalkenyl group” for R3 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group or a 2,2-dichlorovinyl group. , 3-fluoroallyl group, 3,3-difluoroallyl group, or 3,3-dichloroallyl group, and more preferably 2-fluorovinyl group or 2,2-difluorovinyl group.
　式（１）のＲ３における「置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基」のＣ２～Ｃ６のアルキニル基は、前記の定義と同義であり、好ましくは、エチニル基、１－プロピニル基、プロパルギル基、１－ブチニル基、２－ブチニル基、または３－ブチニル基であり、さらに好ましくは、エチニル基、１－プロピニル基、またはプロパルギル基である。置換基Ｃを有する場合、Ｃ２～Ｃ６のアルキニル基における水素原子が、置換基Ｃによって任意に置換される。 The C2-C6 alkynyl group of the "C2-C6 alkynyl group optionally substituted by the substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably an ethynyl group, 1- A propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group is more preferable, and an ethynyl group, a 1-propynyl group, or a propargyl group is more preferable. When it has a substituent C, the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent C.
　式（１）のＲ３における「Ｃ２～Ｃ６のハロアルキニル基」は、前記の定義と同義であり、好ましくは、３，３－ジフルオロ－１－プロピニル基、３，３，３－トリフルオロ－１－プロピニル基、４，４－ジフルオロ－１－ブチニル基、４，４－ジフルオロ－２－ブチニル基、４，４，４－トリフルオロ－１－ブチニル基、または４，４，４－トリフルオロ－２－ブチニル基であり、さらに好ましくは、３，３－ジフルオロ－１－プロピニル基、または３，３，３－トリフルオロ－１－プロピニル基である。 The "C2-C6 haloalkynyl group" in R3 of the formula (1) has the same meaning as defined above, and is preferably a 3,3-difluoro-1-propynyl group or a 3,3,3-trifluoro-1 group. -Propinyl group, 4,4-difluoro-1-butynyl group, 4,4-difluoro-2-butynyl group, 4,4,4-trifluoro-1-butynyl group, or 4,4,4-trifluoro- It is a 2-butynyl group, more preferably a 3,3-difluoro-1-propynyl group or a 3,3,3-trifluoro-1-propynyl group.
　式（１）のＲ３における「置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基」のＣ１～Ｃ６のアルコキシ基は、前記の定義と同義であり、好ましくは、メトキシ基、エトキシ基、プロピルオキシ基、またはイソプロピルオキシ基であり、さらに好ましくは、メトキシ基、またはエトキシ基である。置換基Ｃを有する場合、Ｃ１～Ｃ６のアルコキシ基における水素原子が、置換基Ｃによって任意に置換される。 The C1 to C6 alkoxy group of the "C1 to C6 alkoxy group optionally substituted with a substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably a methoxy group or an ethoxy group. , A propyloxy group, or an isopropyloxy group, and more preferably a methoxy group or an ethoxy group. When it has a substituent C, the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent C.
　式（１）のＲ３における「Ｃ１～Ｃ６のハロアルコキシ基」は、前記の定義と同義であり、好ましくは、ジフルオロメトキシ基、トリフルオロメトキシ基、２，２－ジフルオロエトキシ基、２，２，２－トリフルオロエトキシ基、３，３－ジフルオロプロピルオキシ基、または３，３，３－トリフルオロプロピルオキシ基であり、さらに好ましくは、ジフルオロメトキシ基、トリフルオロメトキシ基、２，２－ジフルオロエトキシ基、または２，２，２－トリフルオロエトキシ基である。 The “C1-C6 haloalkoxy group” in R3 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2,2. 2-trifluoroethoxy group, 3,3-difluoropropyloxy group or 3,3,3-trifluoropropyloxy group, more preferably difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group Or a 2,2,2-trifluoroethoxy group.
　式（１）のＲ３における「置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基」のＣ３～Ｃ８のシクロアルコキシ基は、前記の定義と同義であり、好ましくは、シクロプロピルオキシ基、シクロブトキシ基、シクロペンチルオキシ基、またはシクロヘキシルオキシ基であり、さらに好ましくは、シクロプロピルオキシ基、またはシクロブトキシ基である。置換基Ｃを有する場合、Ｃ３～Ｃ８のシクロアルコキシ基における水素原子が、置換基Ｃによって任意に置換される。 The C3 to C8 cycloalkoxy group of the "C3 to C8 cycloalkoxy group optionally substituted with a substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group. When it has a substituent C, the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted by the substituent C.
　式（１）のＲ３における「置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基」のＣ２～Ｃ６のアルケニルオキシ基は、前記の定義と同義であり、好ましくは、ビニルオキシ基、１－プロペニルオキシ基、アリルオキシ基、１－ブテニルオキシ基、２－ブテニルオキシ基、または３－ブテニルオキシ基であり、さらに好ましくは、ビニルオキシ基、１－プロペニルオキシ基、またはアリルオキシ基である。置換基Ｃを有する場合、Ｃ２～Ｃ６のアルケニルオキシ基における水素原子が、置換基Ｃによって任意に置換される。 The C2-C6 alkenyloxy group of the "C2-C6 alkenyloxy group optionally substituted with a substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably a vinyloxy group, It is a 1-propenyloxy group, an allyloxy group, a 1-butenyloxy group, a 2-butenyloxy group or a 3-butenyloxy group, more preferably a vinyloxy group, a 1-propenyloxy group or an allyloxy group. When it has a substituent C, the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent C.
　式（１）のＲ３における「Ｃ２～Ｃ６のハロアルケニルオキシ基」は、前記の定義と同義であり、好ましくは、２－フルオロビニルオキシ基、２，２－ジフルオロビニルオキシ基、２，２－ジクロロビニルオキシ基、３－フルオロアリルオキシ基、３，３－ジフルオロアリルオキシ基、または３，３－ジクロロアリルオキシ基であり、さらに好ましくは、２－フルオロビニルオキシ基、または２，２－ジフルオロビニルオキシ基である。 The “C2-C6 haloalkenyloxy group” for R3 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyloxy group, a 2,2-difluorovinyloxy group, or a 2,2- A dichlorovinyloxy group, a 3-fluoroallyloxy group, a 3,3-difluoroallyloxy group, or a 3,3-dichloroallyloxy group, more preferably a 2-fluorovinyloxy group or a 2,2-difluoro group. It is a vinyloxy group.
　式（１）のＲ３における「置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基」のＣ３～Ｃ６のアルキニルオキシ基は、前記の定義と同義であり、好ましくは、プロパルギルオキシ基、２－ブチニルオキシ基、または３－ブチニルオキシ基であり、さらに好ましくは、プロパルギルオキシ基、または２－ブチニルオキシ基である。置換基Ｃを有する場合、Ｃ３～Ｃ６のアルキニルオキシ基における水素原子が、置換基Ｃによって任意に置換される。 The C3 to C6 alkynyloxy group of the "C3 to C6 alkynyloxy group optionally substituted with a substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably a propargyloxy group. , A 2-butynyloxy group, or a 3-butynyloxy group, and more preferably a propargyloxy group or a 2-butynyloxy group. When it has a substituent C, the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent C.
　式（１）のＲ３における「Ｃ３～Ｃ６のハロアルキニルオキシ基」は、前記の定義と同義であり、好ましくは、４，４－ジフルオロ－２－ブチニルオキシ基、４－クロロ－４，４－ジフルオロ－２－ブチニルオキシ基、４－ブロモ－４，４－ジフルオロ－２－ブチニルオキシ基、または４，４，４－トリフルオロ－２－ブチニルオキシ基であり、さらに好ましくは、４，４－ジフルオロ－２－ブチニルオキシ基、または４，４，４－トリフルオロ－２－ブチニルオキシ基である。 The "C3-C6 haloalkynyloxy group" for R3 in formula (1) has the same meaning as defined above, and is preferably a 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro group. -2-butynyloxy group, 4-bromo-4,4-difluoro-2-butynyloxy group, or 4,4,4-trifluoro-2-butynyloxy group, more preferably 4,4-difluoro-2- It is a butynyloxy group or a 4,4,4-trifluoro-2-butynyloxy group.
　式（１）のＲ３におけるＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、またはＣ３～Ｃ８のシクロアルコキシ基を表す。））の各用語は、前記の定義と同義である。なお、「置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基」に関しては、置換基Ｂを有する場合、Ｃ１～Ｃ６のアルキル基における水素原子が、置換基Ｂによって任意に置換される。「ＲｄＣ（＝Ｏ）－」として、好ましくは、アセチル基、メトキシアセチル基、シアノアセチル基、プロピオニル基、ジフルオロアセチル基、トリフルオロアセチル基、シクロプロパンカルボニル基、メトキシカルボニル基、エトキシカルボニル基、２，２－ジフルオロエトキシカルボニル基、２，２，２－トリフルオロエトキシカルボニル基、３，３，３－トリフルオロプロピルオキシカルボニル基、またはシクロプロピルオキシカルボニル基であり、さらに好ましくは、アセチル基、メトキシアセチル基、シアノアセチル基、メトキシカルボニル基、またはエトキシカルボニル基である。 RdC (= O)-in R3 of the formula (1) (wherein Rd is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, C3 to C8 Represents a cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, or a C3 to C8 cycloalkoxy group).)) Has the same meaning as defined above. Regarding the “C1 to C6 alkyl group optionally substituted with the substituent B”, in the case of having the substituent B, the hydrogen atom in the C1 to C6 alkyl group is optionally substituted with the substituent B. . “RdC (═O) —” is preferably acetyl group, methoxyacetyl group, cyanoacetyl group, propionyl group, difluoroacetyl group, trifluoroacetyl group, cyclopropanecarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, 2 , 2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 3,3,3-trifluoropropyloxycarbonyl group, or cyclopropyloxycarbonyl group, more preferably acetyl group, methoxy It is an acetyl group, a cyanoacetyl group, a methoxycarbonyl group, or an ethoxycarbonyl group.
　式（１）のＲ３における「ＲｄＣ（＝Ｏ）Ｏ－」のＲｄは、前記と同義である「ＲｄＣ（＝Ｏ）Ｏ－」として、好ましくは、アセチルオキシ基、メトキシアセチルオキシ基、シアノアセチルオキシ基、プロピオニルオキシ基、ジフルオロアセチルオキシ基、トリフルオロアセチルオキシ基、シクロプロパンカルボニルオキシ基、メトキシカルボニルオキシ基、エトキシカルボニルオキシ基、２，２－ジフルオロエトキシカルボニルオキシ基、２，２，２－トリフルオロエトキシカルボニルオキシ基、３，３，３－トリフルオロプロピルオキシカルボニルオキシ基、またはシクロプロピルオキシカルボニルオキシ基であり、さらに好ましくは、アセチルオキシ基、メトキシアセチルオキシ基、またはシアノアセチルオキシ基である。 Rd of "RdC (= O) O-" in R3 of the formula (1) is the same as defined above, "RdC (= O) O-", preferably acetyloxy group, methoxyacetyloxy group, cyanoacetyl group. Oxy group, propionyloxy group, difluoroacetyloxy group, trifluoroacetyloxy group, cyclopropanecarbonyloxy group, methoxycarbonyloxy group, ethoxycarbonyloxy group, 2,2-difluoroethoxycarbonyloxy group, 2,2,2- A trifluoroethoxycarbonyloxy group, a 3,3,3-trifluoropropyloxycarbonyloxy group, or a cyclopropyloxycarbonyloxy group, more preferably an acetyloxy group, a methoxyacetyloxy group, or a cyanoacetyloxy group. is there.
　式（１）のＲ３における「Ｒｃ－Ｌ－」のＲｃおよびＬは、前記と同義である。「Ｒｃ－Ｌ－」として、好ましくは、メチルチオ基、メタンスルフィニル基、メタンスルホニル基、エチルチオ基、エタンスルフィニル基、エタンスルホニル基、トリフルオロメチルチオ基、トリフルオロメタンスルフィニル基、またはトリフルオロメタンスルホニル基であり、さらに好ましくは、メチルチオ基、メタンスルフィニル基、またはメタンスルホニル基である。 Rc and L of "Rc-L-" in R3 of the formula (1) have the same meaning as above. "Rc-L-" is preferably a methylthio group, a methanesulfinyl group, a methanesulfonyl group, an ethylthio group, an ethanesulfinyl group, an ethanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, or a trifluoromethanesulfonyl group. , And more preferably, a methylthio group, a methanesulfinyl group, or a methanesulfonyl group.
　式（１）のＲ３における「ＲａＲｂＮ－」（ここで、ＲａおよびＲｂは、それぞれ独立していて、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表す。）の各用語は、前記の定義と同義である。「ＲａＲｂＮ－」として、好ましくは、アミノ基、メチルアミノ基、エチルアミノ基、プロピルアミノ基、イソプロピルアミノ基、（メトキシメチル）アミノ基、（２－メトキシエチル）アミノ基、（シアノメチル）アミノ基、（２－シアノエチル）アミノ基、ジメチルアミノ基、エチル（メチル）アミノ基、メチル（プロピル）アミノ基、イソプロピル（メチル）アミノ基、（メトキシメチル）メチルアミノ基、（２－メトキシエチル）メチルアミノ基、（シアノメチル）メチルアミノ基、（２－シアノエチル）メチルアミノ基、ジエチルアミノ基、エチル（プロピル）アミノ基、エチル（イソプロピル）アミノ基、エチル（メトキシメチル）アミノ基、エチル（２－メトキシエチル）アミノ基、（シアノメチル）エチルアミノ基、（２－シアノエチル）エチルアミノ基、２，２－ジフルオロエチルアミノ基、２，２，２－トリフルオロエチルアミノ基、シクロプロピルアミノ基、または（シクロプロピル）メチルアミノ基であり、さらに好ましくは、アミノ基、ジメチルアミノ基、エチル（メチル）アミノ基、またはジエチルアミノ基である。 “RaRbN—” in R3 of the formula (1) (wherein Ra and Rb are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 Each of the terms haloalkyl group or C3 to C8 cycloalkyl group) has the same meaning as defined above. "RaRbN-" is preferably an amino group, a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a (methoxymethyl) amino group, a (2-methoxyethyl) amino group, a (cyanomethyl) amino group, (2-Cyanoethyl) amino group, dimethylamino group, ethyl (methyl) amino group, methyl (propyl) amino group, isopropyl (methyl) amino group, (methoxymethyl) methylamino group, (2-methoxyethyl) methylamino group , (Cyanomethyl) methylamino group, (2-cyanoethyl) methylamino group, diethylamino group, ethyl (propyl) amino group, ethyl (isopropyl) amino group, ethyl (methoxymethyl) amino group, ethyl (2-methoxyethyl) amino group Group, (cyanomethyl) ethylamino group, (2- Anoethyl) ethylamino group, 2,2-difluoroethylamino group, 2,2,2-trifluoroethylamino group, cyclopropylamino group, or (cyclopropyl) methylamino group, more preferably an amino group, A dimethylamino group, an ethyl (methyl) amino group, or a diethylamino group.
　式（１）のＲ３における「ＲｅＣ（＝Ｏ）Ｎ（Ｒｆ）－」（ここで、ＲｅとＲｆは、それぞれ独立していて、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、Ｃ３～Ｃ８のシクロアルコキシ基、またはＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）を表す。）の各用語は、前記の定義と同義である。なお、「置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基」に関しては、置換基Ｂを有する場合、Ｃ１～Ｃ６のアルキル基における水素原子が、置換基Ｂによって任意に置換される。「ＲｅＣ（＝Ｏ）Ｎ（Ｒｆ）－」として、好ましくは、ホルミルアミノ基、アセチルアミノ基、メトキシアセチルアミノ基、シアノアセチルアミノ基、プロピオニルアミノ基、ジフルオロアセチルアミノ基、トリフルオロアセチルアミノ基、シクロプロパンカルボニルアミノ基、メトキシカルボニルアミノ基、エトキシカルボニルアミノ基、２，２－ジフルオロエトキシカルボニルアミノ基、２，２，２－トリフルオロエトキシカルボニルアミノ基、３，３，３－トリフルオロプロピルオキシカルボニルアミノ基、シクロプロピルオキシカルボニルアミノ基、アミノカルボニルアミノ基、メチルアミノカルボニルアミノ基、エチルアミノカルボニルアミノ基、（メトキシメチル）アミノカルボニルアミノ基、（２－メトキシエチル）アミノカルボニルアミノ基、（シアノメチル）アミノカルボニルアミノ基、（２－シアノエチル）アミノカルボニルアミノ基、ジメチルアミノカルボニルアミノ基、エチル（メチル）アミノカルボニルアミノ基、ジエチルアミノカルボニルアミノ基、（メトキシメチル）メチルアミノカルボニルアミノ基、（２－メトキシエチル）メチルアミノカルボニルアミノ基、（シアノメチル）メチルアミノカルボニルアミノ基、（２－シアノエチル）メチルアミノカルボニルアミノ基、２，２－ジフルオロエチルアミノカルボニルアミノ基、２，２，２－トリフルオロエチルアミノカルボニルアミノ基、シクロプロピルアミノカルボニルアミノ基、シクロプロピル（メチル）アミノカルボニルアミノ基、ピロリジニルカルボニルアミノ基、ピペリジニルカルボニルアミノ基、ホルミル（メチル）アミノ基、アセチル（メチル）アミノ基、メトキシアセチル（メチル）アミノ基、シアノアセチル（メチル）アミノ基、プロピオニル（メチル）アミノ基、ジフルオロアセチル（メチル）アミノ基、トリフルオロアセチル（メチル）アミノ基、シクロプロパンカルボニル（メチル）アミノ基、メトキシカルボニル（メチル）アミノ基、エトキシカルボニル（メチル）アミノ基、２，２－ジフルオロエトキシカルボニル（メチル）アミノ基、２，２，２－トリフルオロエトキシカルボニル（メチル）アミノ基、３，３，３－トリフルオロプロピルオキシカルボニル（メチル）アミノ基、シクロプロピルオキシカルボニル（メチル）アミノ基、アミノカルボニル（メチル）アミノ基、メチルアミノカルボニル（メチル）アミノ基、エチルアミノカルボニル（メチル）アミノ基、（メトキシメチル）アミノカルボニル（メチル）アミノ基、（２－メトキシエチル）アミノカルボニル（メチル）アミノ基、（シアノメチル）アミノカルボニル（メチル）アミノ基、（２－シアノエチル）アミノカルボニル（メチル）アミノ基、ジメチルアミノカルボニル（メチル）アミノ基、エチル（メチル）アミノカルボニル（メチル）アミノ基、ジエチルアミノカルボニル（メチル）アミノ基、（メトキシメチル）メチルアミノカルボニル（メチル）アミノ基、（２－メトキシエチル）メチルアミノカルボニル（メチル）アミノ基、（シアノメチル）メチルアミノカルボニル（メチル）アミノ基、（２－シアノエチル）メチルアミノカルボニル（メチル）アミノ基、２，２－ジフルオロエチルアミノカルボニル（メチル）アミノ基、２，２，２－トリフルオロエチルアミノカルボニル（メチル）アミノ基、シクロプロピルアミノカルボニル（メチル）アミノ基、シクロプロピル（メチル）アミノカルボニル（メチル）アミノ基、ピロリジニルカルボニル（メチル）アミノ基、ピペリジニルカルボニル（メチル）アミノ基、ホルミル（エチル）アミノ基、アセチル（エチル）アミノ基、メトキシアセチル（エチル）アミノ基、シアノアセチル（エチル）アミノ基、プロピオニル（エチル）アミノ基、ジフルオロアセチル（エチル）アミノ基、トリフルオロアセチル（エチル）アミノ基、シクロプロパンカルボニル（エチル）アミノ基、メトキシカルボニル（エチル）アミノ基、エトキシカルボニル（エチル）アミノ基、２，２－ジフルオロエトキシカルボニル（エチル）アミノ基、２，２，２－トリフルオロエトキシカルボニル（エチル）アミノ基、３，３，３－トリフルオロプロピルオキシカルボニル（エチル）アミノ基、シクロプロピルオキシカルボニル（エチル）アミノ基、アミノカルボニル（エチル）アミノ基、メチルアミノカルボニル（エチル）アミノ基、エチルアミノカルボニル（エチル）アミノ基、（メトキシメチル）アミノカルボニル（エチル）アミノ基、（２－メトキシエチル）アミノカルボニル（エチル）アミノ基、（シアノメチル）アミノカルボニル（エチル）アミノ基、（２－シアノエチル）アミノカルボニル（エチル）アミノ基、ジメチルアミノカルボニル（エチル）アミノ基、エチル（メチル）アミノカルボニル（エチル）アミノ基、ジエチルアミノカルボニル（エチル）アミノ基、（メトキシメチル）メチルアミノカルボニル（エチル）アミノ基、（２－メトキシエチル）メチルアミノカルボニル（エチル）アミノ基、（シアノメチル）メチルアミノカルボニル（エチル）アミノ基、（２－シアノエチル）メチルアミノカルボニル（エチル）アミノ基、２，２－ジフルオロエチルアミノカルボニル（エチル）アミノ基、２，２，２－トリフルオロエチルアミノカルボニル（エチル）アミノ基、シクロプロピルアミノカルボニル（エチル）アミノ基、シクロプロピル（メチル）アミノカルボニル（エチル）アミノ基、ピロリジニルカルボニル（エチル）アミノ基、ピペリジニルカルボニル（エチル）アミノ基、ホルミル（メトキシ）アミノ基、アセチル（メトキシ）アミノ基、メトキシアセチル（メトキシ）アミノ基、シアノアセチル（メトキシ）アミノ基、プロピオニル（メトキシ）アミノ基、ジフルオロアセチル（メトキシ）アミノ基、トリフルオロアセチル（メトキシ）アミノ基、シクロプロパンカルボニル（メトキシ）アミノ基、メトキシカルボニル（メトキシ）アミノ基、エトキシカルボニル（メトキシ）アミノ基、２，２－ジフルオロエトキシカルボニル（メトキシ）アミノ基、２，２，２－トリフルオロエトキシカルボニル（メトキシ）アミノ基、３，３，３－トリフルオロプロピルオキシカルボニル（メトキシ）アミノ基、シクロプロピルオキシカルボニル（メトキシ）アミノ基、アミノカルボニル（メトキシ）アミノ基、メチルアミノカルボニル（メトキシ）アミノ基、エチルアミノカルボニル（メトキシ）アミノ基、（メトキシメチル）アミノカルボニル（メトキシ）アミノ基、（２－メトキシエチル）アミノカルボニル（メトキシ）アミノ基、（シアノメチル）アミノカルボニル（メトキシ）アミノ基、（２－シアノエチル）アミノカルボニル（メトキシ）アミノ基、ジメチルアミノカルボニル（メトキシ）アミノ基、エチル（メチル）アミノカルボニル（メトキシ）アミノ基、ジエチルアミノカルボニル（メトキシ）アミノ基、（メトキシメチル）メチルアミノカルボニル（メトキシ）アミノ基、（２－メトキシエチル）メチルアミノカルボニル（メトキシ）アミノ基、（シアノメチル）メチルアミノカルボニル（メトキシ）アミノ基、（２－シアノエチル）メチルアミノカルボニル（メトキシ）アミノ基、２，２－ジフルオロエチルアミノカルボニル（メトキシ）アミノ基、２，２，２－トリフルオロエチルアミノカルボニル（メトキシ）アミノ基、シクロプロピルアミノカルボニル（メトキシ）アミノ基、シクロプロピル（メチル）アミノカルボニル（メトキシ）アミノ基、ピロリジニルカルボニル（メトキシ）アミノ基、ピペリジニルカルボニル（メトキシ）アミノ基、ホルミル（エトキシ）アミノ基、アセチル（エトキシ）アミノ基、メトキシアセチル（エトキシ）アミノ基、シアノアセチル（エトキシ）アミノ基、プロピオニル（エトキシ）アミノ基、ジフルオロアセチル（エトキシ）アミノ基、トリフルオロアセチル（エトキシ）アミノ基、シクロプロパンカルボニル（エトキシ）アミノ基、メトキシカルボニル（エトキシ）アミノ基、エトキシカルボニル（エトキシ）アミノ基、２，２－ジフルオロエトキシカルボニル（エトキシ）アミノ基、２，２，２－トリフルオロエトキシカルボニル（エトキシ）アミノ基、３，３，３－トリフルオロプロピルオキシカルボニル（エトキシ）アミノ基、シクロプロピルオキシカルボニル（エトキシ）アミノ基、アミノカルボニル（エトキシ）アミノ基、メチルアミノカルボニル（エトキシ）アミノ基、エチルアミノカルボニル（エトキシ）アミノ基、（メトキシメチル）アミノカルボニル（エトキシシ）アミノ基、（２－メトキシエチル）アミノカルボニル（エトキシ）アミノ基、（シアノメチル）アミノカルボニル（エトキシ）アミノ基、（２－シアノエチル）アミノカルボニル（エトキシ）アミノ基、ジメチルアミノカルボニル（エトキシ）アミノ基、エチル（メチル）アミノカルボニル（エトキシ）アミノ基、ジエチルアミノカルボニル（エトキシ）アミノ基、（メトキシメチル）メチルアミノカルボニル（エトキシ）アミノ基、（２－メトキシエチル）メチルアミノカルボニル（エトキシ）アミノ基、（シアノメチル）メチルアミノカルボニル（エトキシ）アミノ基、（２－シアノエチル）メチルアミノカルボニル（エトキシ）アミノ基、２，２－ジフルオロエチルアミノカルボニル（エトキシ）アミノ基、２，２，２－トリフルオロエチルアミノカルボニル（エトキシ）アミノ基、シクロプロピルアミノカルボニル（エトキシ）アミノ基、シクロプロピル（メチル）アミノカルボニル（エトキシ）アミノ基、ピロリジニルカルボニル（エトキシ）アミノ基、またはピペリジニルカルボニル（エトキシ）アミノ基であり、さらに好ましくは、アセチルアミノ基、アセチル（メチル）アミノ基、アセチル（エチル）アミノ基、アセチル（メトキシ）アミノ基、アセチル（エトキシ）アミノ基、メトキシカルボニルアミノ基、エトキシカルボニルアミノ基、メトキシカルボニル（メチル）アミノ基、エトキシカルボニル（メチル）アミノ基、メトキシカルボニル（エチル）アミノ基、エトキシカルボニル（エチル）アミノ基、メトキシカルボニル（メトキシ）アミノ基、エトキシカルボニル（メトキシ）アミノ基、メトキシカルボニル（エトキシ）アミノ基、またはエトキシカルボニル（エトキシ）アミノ基である。 “ReC (═O) N (Rf) —” in R3 of the formula (1) (wherein Re and Rf are independent of each other, and are a hydrogen atom or C1 to C6 optionally substituted with a substituent B). Alkyl group, C1 to C6 haloalkyl group, C3 to C8 cycloalkyl group, C1 to C6 alkoxy group, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group, or RaRbN- (wherein Ra And Rb have the same meanings as defined above.), And each of the terms)) has the same meaning as defined above. Regarding the “C1 to C6 alkyl group optionally substituted with the substituent B”, in the case of having the substituent B, the hydrogen atom in the C1 to C6 alkyl group is optionally substituted with the substituent B. . "ReC (= O) N (Rf)-" is preferably a formylamino group, an acetylamino group, a methoxyacetylamino group, a cyanoacetylamino group, a propionylamino group, a difluoroacetylamino group, a trifluoroacetylamino group, Cyclopropanecarbonylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, 2,2-difluoroethoxycarbonylamino group, 2,2,2-trifluoroethoxycarbonylamino group, 3,3,3-trifluoropropyloxycarbonyl Amino group, cyclopropyloxycarbonylamino group, aminocarbonylamino group, methylaminocarbonylamino group, ethylaminocarbonylamino group, (methoxymethyl) aminocarbonylamino group, (2-methoxyethyl) aminocarb Bonylamino group, (cyanomethyl) aminocarbonylamino group, (2-cyanoethyl) aminocarbonylamino group, dimethylaminocarbonylamino group, ethyl (methyl) aminocarbonylamino group, diethylaminocarbonylamino group, (methoxymethyl) methylaminocarbonylamino group , (2-methoxyethyl) methylaminocarbonylamino group, (cyanomethyl) methylaminocarbonylamino group, (2-cyanoethyl) methylaminocarbonylamino group, 2,2-difluoroethylaminocarbonylamino group, 2,2,2- Trifluoroethylaminocarbonylamino group, cyclopropylaminocarbonylamino group, cyclopropyl (methyl) aminocarbonylamino group, pyrrolidinylcarbonylamino group, piperidinylcarbo group Ruamino group, formyl (methyl) amino group, acetyl (methyl) amino group, methoxyacetyl (methyl) amino group, cyanoacetyl (methyl) amino group, propionyl (methyl) amino group, difluoroacetyl (methyl) amino group, trifluoro Acetyl (methyl) amino group, cyclopropanecarbonyl (methyl) amino group, methoxycarbonyl (methyl) amino group, ethoxycarbonyl (methyl) amino group, 2,2-difluoroethoxycarbonyl (methyl) amino group, 2,2,2 -Trifluoroethoxycarbonyl (methyl) amino group, 3,3,3-trifluoropropyloxycarbonyl (methyl) amino group, cyclopropyloxycarbonyl (methyl) amino group, aminocarbonyl (methyl) amino group, methylaminocarbonyl ( Me (Cyl) amino group, ethylaminocarbonyl (methyl) amino group, (methoxymethyl) aminocarbonyl (methyl) amino group, (2-methoxyethyl) aminocarbonyl (methyl) amino group, (cyanomethyl) aminocarbonyl (methyl) amino group , (2-cyanoethyl) aminocarbonyl (methyl) amino group, dimethylaminocarbonyl (methyl) amino group, ethyl (methyl) aminocarbonyl (methyl) amino group, diethylaminocarbonyl (methyl) amino group, (methoxymethyl) methylaminocarbonyl (Methyl) amino group, (2-methoxyethyl) methylaminocarbonyl (methyl) amino group, (cyanomethyl) methylaminocarbonyl (methyl) amino group, (2-cyanoethyl) methylaminocarbonyl (methyl) amino group, 2, -Difluoroethylaminocarbonyl (methyl) amino group, 2,2,2-trifluoroethylaminocarbonyl (methyl) amino group, cyclopropylaminocarbonyl (methyl) amino group, cyclopropyl (methyl) aminocarbonyl (methyl) amino group , Pyrrolidinylcarbonyl (methyl) amino group, piperidinylcarbonyl (methyl) amino group, formyl (ethyl) amino group, acetyl (ethyl) amino group, methoxyacetyl (ethyl) amino group, cyanoacetyl (ethyl) amino group , Propionyl (ethyl) amino group, difluoroacetyl (ethyl) amino group, trifluoroacetyl (ethyl) amino group, cyclopropanecarbonyl (ethyl) amino group, methoxycarbonyl (ethyl) amino group, ethoxycarbonyl (ethyl) ami Group, 2,2-difluoroethoxycarbonyl (ethyl) amino group, 2,2,2-trifluoroethoxycarbonyl (ethyl) amino group, 3,3,3-trifluoropropyloxycarbonyl (ethyl) amino group, cyclopropyl Oxycarbonyl (ethyl) amino group, aminocarbonyl (ethyl) amino group, methylaminocarbonyl (ethyl) amino group, ethylaminocarbonyl (ethyl) amino group, (methoxymethyl) aminocarbonyl (ethyl) amino group, (2-methoxy Ethyl) aminocarbonyl (ethyl) amino group, (cyanomethyl) aminocarbonyl (ethyl) amino group, (2-cyanoethyl) aminocarbonyl (ethyl) amino group, dimethylaminocarbonyl (ethyl) amino group, ethyl (methyl) aminocarbonyl ( ethyl) Amino group, diethylaminocarbonyl (ethyl) amino group, (methoxymethyl) methylaminocarbonyl (ethyl) amino group, (2-methoxyethyl) methylaminocarbonyl (ethyl) amino group, (cyanomethyl) methylaminocarbonyl (ethyl) amino group , (2-cyanoethyl) methylaminocarbonyl (ethyl) amino group, 2,2-difluoroethylaminocarbonyl (ethyl) amino group, 2,2,2-trifluoroethylaminocarbonyl (ethyl) amino group, cyclopropylaminocarbonyl (Ethyl) amino group, cyclopropyl (methyl) aminocarbonyl (ethyl) amino group, pyrrolidinylcarbonyl (ethyl) amino group, piperidinylcarbonyl (ethyl) amino group, formyl (methoxy) amino group, acetyl (methoxy) Amino group, methoxyacetyl (methoxy) amino group, cyanoacetyl (methoxy) amino group, propionyl (methoxy) amino group, difluoroacetyl (methoxy) amino group, trifluoroacetyl (methoxy) amino group, cyclopropanecarbonyl (methoxy) amino group Group, methoxycarbonyl (methoxy) amino group, ethoxycarbonyl (methoxy) amino group, 2,2-difluoroethoxycarbonyl (methoxy) amino group, 2,2,2-trifluoroethoxycarbonyl (methoxy) amino group, 3,3 , 3-trifluoropropyloxycarbonyl (methoxy) amino group, cyclopropyloxycarbonyl (methoxy) amino group, aminocarbonyl (methoxy) amino group, methylaminocarbonyl (methoxy) amino group, ethylamino Rubonyl (methoxy) amino group, (methoxymethyl) aminocarbonyl (methoxy) amino group, (2-methoxyethyl) aminocarbonyl (methoxy) amino group, (cyanomethyl) aminocarbonyl (methoxy) amino group, (2-cyanoethyl) amino Carbonyl (methoxy) amino group, dimethylaminocarbonyl (methoxy) amino group, ethyl (methyl) aminocarbonyl (methoxy) amino group, diethylaminocarbonyl (methoxy) amino group, (methoxymethyl) methylaminocarbonyl (methoxy) amino group, ( 2-methoxyethyl) methylaminocarbonyl (methoxy) amino group, (cyanomethyl) methylaminocarbonyl (methoxy) amino group, (2-cyanoethyl) methylaminocarbonyl (methoxy) amino group, 2,2-di Fluoroethylaminocarbonyl (methoxy) amino group, 2,2,2-trifluoroethylaminocarbonyl (methoxy) amino group, cyclopropylaminocarbonyl (methoxy) amino group, cyclopropyl (methyl) aminocarbonyl (methoxy) amino group, Pyrrolidinylcarbonyl (methoxy) amino group, piperidinylcarbonyl (methoxy) amino group, formyl (ethoxy) amino group, acetyl (ethoxy) amino group, methoxyacetyl (ethoxy) amino group, cyanoacetyl (ethoxy) amino group, Propionyl (ethoxy) amino group, difluoroacetyl (ethoxy) amino group, trifluoroacetyl (ethoxy) amino group, cyclopropanecarbonyl (ethoxy) amino group, methoxycarbonyl (ethoxy) amino group, ethoxy Rubonyl (ethoxy) amino group, 2,2-difluoroethoxycarbonyl (ethoxy) amino group, 2,2,2-trifluoroethoxycarbonyl (ethoxy) amino group, 3,3,3-trifluoropropyloxycarbonyl (ethoxy) Amino group, cyclopropyloxycarbonyl (ethoxy) amino group, aminocarbonyl (ethoxy) amino group, methylaminocarbonyl (ethoxy) amino group, ethylaminocarbonyl (ethoxy) amino group, (methoxymethyl) aminocarbonyl (ethoxysi) amino group , (2-methoxyethyl) aminocarbonyl (ethoxy) amino group, (cyanomethyl) aminocarbonyl (ethoxy) amino group, (2-cyanoethyl) aminocarbonyl (ethoxy) amino group, dimethylaminocarbonyl (ethoxy Amino group, ethyl (methyl) aminocarbonyl (ethoxy) amino group, diethylaminocarbonyl (ethoxy) amino group, (methoxymethyl) methylaminocarbonyl (ethoxy) amino group, (2-methoxyethyl) methylaminocarbonyl (ethoxy) amino group , (Cyanomethyl) methylaminocarbonyl (ethoxy) amino group, (2-cyanoethyl) methylaminocarbonyl (ethoxy) amino group, 2,2-difluoroethylaminocarbonyl (ethoxy) amino group, 2,2,2-trifluoroethyl Aminocarbonyl (ethoxy) amino group, cyclopropylaminocarbonyl (ethoxy) amino group, cyclopropyl (methyl) aminocarbonyl (ethoxy) amino group, pyrrolidinylcarbonyl (ethoxy) amino group, or piperidinyl Is a carbonyl (ethoxy) amino group, more preferably an acetylamino group, an acetyl (methyl) amino group, an acetyl (ethyl) amino group, an acetyl (methoxy) amino group, an acetyl (ethoxy) amino group, a methoxycarbonylamino group. , Ethoxycarbonylamino group, methoxycarbonyl (methyl) amino group, ethoxycarbonyl (methyl) amino group, methoxycarbonyl (ethyl) amino group, ethoxycarbonyl (ethyl) amino group, methoxycarbonyl (methoxy) amino group, ethoxycarbonyl (methoxy ) Amino group, methoxycarbonyl (ethoxy) amino group, or ethoxycarbonyl (ethoxy) amino group.
　式（１）中のｎは０～５の整数を表す。この際、０と５との間に存在する全ての整数も個別に開示されているものとする。すなわち、ｎは、０、１、２、３、４、または５を意味する。また、ｎが２以上の場合、２置換以上のＲ３はそれぞれ独立した置換基を表し、同一もしくは異なっていてよく、任意に選択することができる。 N in the formula (1) represents an integer of 0 to 5. At this time, all integers existing between 0 and 5 are individually disclosed. That is, n means 0, 1, 2, 3, 4, or 5. Further, when n is 2 or more, two or more substituted R3's each independently represent a substituent, which may be the same or different and can be arbitrarily selected.
　式（１）中のＺは、Ｒ４で適宜０～３置換されてもよいチエニル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）、Ｒ４で適宜０～２置換されてもよいチアゾリル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）、Ｒ４で適宜置換されてもよいチアジアゾリル基、Ｒ４で適宜０～３置換されてもよいピラゾリル基（ただし、２置換のＲ４の場合、それぞれ独立している。）、またはＲ４で適宜置換されてもよいテトラゾリル基を表し、
　中でもＺは、Ｒ４で適宜０～３置換されてもよいチエニル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）、Ｒ４で適宜０～２置換されてもよいチアゾリル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）、またはＲ４で適宜０～３置換されてもよいピラゾリル基（ただし、２置換のＲ４の場合、それぞれ独立している。）が好ましく、
　特にＺは、環境負荷の低減の観点から、Ｒ４で適宜０～３置換されてもよいチエニル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）が好ましい。 Z in the formula (1) is a thienyl group which may be optionally substituted by 0 to 3 with R4 (however, in the case of 2 or more substituted R4, each is independent), and is appropriately substituted with 0 to 2 by R4. May be a thiazolyl group (provided that each is independent in the case of 2 or more substituted R4), a thiadiazolyl group optionally substituted by R4, a pyrazolyl group optionally substituted by 0 to 3 with R4 (however, In the case of 2-substituted R4, each is independent), or represents a tetrazolyl group optionally substituted by R4,
Among them, Z is a thienyl group which may be appropriately substituted by R4 with 0 to 3 (provided that each is independent in the case of R4 having 2 or more substitutions), and a thiazolyl group which is optionally substituted with 0 to 2 by R4 ( However, in the case of 2-substituted or more R4, each is independent.), Or a pyrazolyl group optionally substituted by 0 to 3 in R4 (however, in the case of 2-substituted R4, each is independent). Preferably
In particular, Z is preferably a thienyl group which may be optionally substituted by 0 to 3 with R4 (in the case of R4 having 2 or more substitutions, each is independent) from the viewpoint of reducing the environmental load.
　式（１）のＺにおける「Ｒ４で適宜０～３置換されてもよいチエニル基」（ただし、２置換以上のＲ４の場合、それぞれ独立している。）は、式（Ａ－１）または式（Ａ－２）で表される下記に示した部分構造を表す。
Figure JPOXMLDOC01-appb-C000004
 In the Z of the formula (1), “a thienyl group optionally substituted by 0 to 3 with R 4” (however, in the case of 2 or more substituted R 4, each is independent) is the formula (A-1) or the formula The following partial structure represented by (A-2) is shown.
Figure JPOXMLDOC01-appb-C000004
　式（Ａ－１）、および式（Ａ－２）中、ｎＡは０、１、２、または３の整数を表し、ｎＡが２以上の場合、２以上のＲ４はそれぞれ独立した置換基を表し、同一もしくは異なっていてよく、任意に選択することができる。 In formulas (A-1) and (A-2), nA represents an integer of 0, 1, 2, or 3, and when nA is 2 or more, R4s of 2 or more each independently represent a substituent. , May be the same or different, and can be arbitrarily selected.
　式（１）のＺにおける「Ｒ４で適宜０～２置換されてもよいチアゾリル基」（ただし、２置換のＲ４の場合、それぞれ独立している。）は、式（Ｂ－１）、式（Ｂ－２）、または式（Ｂ―３）で表される下記に示した部分構造を表す。
Figure JPOXMLDOC01-appb-C000005
 The “thiazolyl group optionally substituted with 0 to 2 at R4” in Z of the formula (1) (however, in the case of disubstituted R4, each is independent) is represented by the formula (B-1), the formula ( B-2) or a partial structure represented by the formula (B-3) shown below.
Figure JPOXMLDOC01-appb-C000005
　式（Ｂ－１）、式（Ｂ－２）、および式（Ｂ―３）中、ｎＢは０、１、または２の整数を表し、ｎＢが２の場合、２置換のＲ４はそれぞれ独立した置換基を表し、同一もしくは異なっていてよく、任意に選択することができる。 In the formula (B-1), the formula (B-2), and the formula (B-3), nB represents an integer of 0, 1, or 2, and when nB is 2, the 2-substituted R4s are independent of each other. It represents a substituent and may be the same or different and can be arbitrarily selected.
　式（１）のＺにおける「Ｒ４で適宜置換されてもよいチアジアゾリル基」は、式（Ｃ－１）、式（Ｃ－２）、式（Ｃ－３）、式（Ｃ－４）、式（Ｃ－５）、または式（Ｃ－６）で表される下記に示した部分構造を表す。
Figure JPOXMLDOC01-appb-C000006
 The “thiadiazolyl group optionally substituted with R4” in Z in the formula (1) means the formula (C-1), the formula (C-2), the formula (C-3), the formula (C-4) and the formula (C-4) (C-5) or a partial structure represented by the formula (C-6) shown below.
Figure JPOXMLDOC01-appb-C000006
　式（Ｃ－１）、式（Ｃ－２）、式（Ｃ－３）、式（Ｃ－４）、式（Ｃ－５）、および式（Ｃ－６）中、ｎＣは０または１の整数を表す。 In the formula (C-1), formula (C-2), formula (C-3), formula (C-4), formula (C-5), and formula (C-6), nC is 0 or 1. Represents an integer.
　式（１）のＺにおける「Ｒ４で適宜０～３置換されてもよいピラゾリル基」（ただし、２置換のＲ４の場合、それぞれ独立している。）は、式（Ｄ－１）、式（Ｄ－２）、式（Ｄ－３）、式（Ｄ－４）、式（Ｄ－５）、または式（Ｄ－６）で表される下記に示した部分構造を表す。
Figure JPOXMLDOC01-appb-C000007
 The “pyrazolyl group which may be optionally substituted with 0 to 3 by R4” in Z of the formula (1) (however, in the case of disubstituted R4, each is independent) is represented by the formula (D-1), the formula ( D-2), the formula (D-3), the formula (D-4), the formula (D-5), or the formula (D-6) represents a partial structure shown below.
Figure JPOXMLDOC01-appb-C000007
　式（Ｄ－１）、式（Ｄ－２）、式（Ｄ－３）、式（Ｄ－４）、式（Ｄ－５）、および式（Ｄ－６）中、ｎＤは０、１、または２の整数を表す。ｎＤが２の場合、２置換のＲ４はそれぞれ独立した置換基を表し、同一もしくは異なっていてよく、任意に選択することができる。 In the formula (D-1), formula (D-2), formula (D-3), formula (D-4), formula (D-5), and formula (D-6), nD is 0, 1, Alternatively, it represents an integer of 2. When nD is 2, 2-substituted R4's each represent an independent substituent, which may be the same or different and can be arbitrarily selected.
　式（１）のＺにおける「Ｒ４で適宜置換されてもよいテトラゾリル基」は、式（Ｅ－１）、式（Ｅ－２）、式（Ｅ－３）、式（Ｅ－４）、式（Ｅ－５）、または式（Ｅ－６）で表される下記に示した部分構造を表す。
Figure JPOXMLDOC01-appb-C000008
 The “tetrazolyl group optionally substituted with R4” in Z of the formula (1) means the formula (E-1), the formula (E-2), the formula (E-3), the formula (E-4) and the formula (E-4) It represents the partial structure shown below represented by formula (E-5) or formula (E-6).
Figure JPOXMLDOC01-appb-C000008
　式（１）中のＲ４は、水酸基、シアノ基、ニトロ基、ハロゲン原子、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、Ｃ２～Ｃ６のハロアルキニル基、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、Ｃ２～Ｃ６のハロアルケニルオキシ基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、Ｃ３～Ｃ６のハロアルキニルオキシ基、ＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、前記と同義である。）、ＲｄＣ（＝Ｏ）Ｏ－（ここで、Ｒｄは、前記と同義である。）、Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）、ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）、またはＲｅＣ（＝Ｏ）Ｎ（Ｒｆ）－（ここで、ＲｅとＲｆは、前記と同義である。）を表す。 R4 in the formula (1) is appropriately substituted with a hydroxyl group, a cyano group, a nitro group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, and a substituent C. Optionally substituted C3 to C8 cycloalkyl group, optionally substituted C2 to C6 alkenyl group, C2 to C6 haloalkenyl group, optionally substituted C2 to C6 Alkynyl group, C2 to C6 haloalkynyl group, C1 to C6 alkoxy group optionally substituted with a substituent C, C1 to C6 haloalkoxy group, C3 to C8 optionally substituted with a substituent C A cycloalkoxy group, a C2-C6 alkenyloxy group optionally substituted with a substituent C, a C2-C6 haloalkenyloxy group, a C3-C6 optionally substituted with a substituent C Ruquinyloxy group, C3-C6 haloalkynyloxy group, RdC (= O)-(where Rd has the same meaning as above), RdC (= O) O- (where Rd has the same meaning as above) Rc-L- (wherein Rc and L have the same meanings as described above), RaRbN- (wherein Ra and Rb have the same meanings as described above), or ReC (= O). ) N (Rf)-(wherein Re and Rf have the same meanings as described above).
　中でもＲ４は、水酸基、シアノ基、ニトロ基、ハロゲン原子、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、またはＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、前記と同義である。）が好ましく、
　特にＲ４は、ハロゲン原子、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、または、ＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、前記と同義である。）が好ましい。 Among them, R4 is a hydroxyl group, a cyano group, a nitro group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, or a C2 optionally substituted with a substituent C. To C6 alkenyl group, C2 to C6 alkynyl group optionally substituted with substituent C, C1 to C6 alkoxy group optionally substituted with substituent C, C1 to C6 haloalkoxy group, substituent A C2-C6 alkenyloxy group optionally substituted with C, a C3-C6 alkynyloxy group optionally substituted with a substituent C, or RdC (= O)-(where Rd is Are synonymous with each other),
In particular, R4 is a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, or RdC (═O) — (wherein Rd is as defined above). Yes) is preferred.
　さらにＲ４は、Ｚが「Ｒ４で適宜０～３置換されてもよいチエニル基」を表す場合には、ハロゲン原子、または置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基が好ましく、Ｚが「Ｒ４で適宜０～２置換されてもよいチアゾリル基」を表す場合には、ハロゲン原子、または置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基が好ましく、Ｚが「Ｒ４で適宜置換されてもよいチアジアゾリル基」を表す場合には、ハロゲン原子が好ましく、Ｚが「Ｒ４で適宜０～３置換されてもよいピラゾリル基」を表す場合には、ハロゲン原子、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、またはＣ１～Ｃ６のハロアルキル基が好ましく、Ｚが「Ｒ４で適宜置換されてもよいテトラゾリル基」を表す場合には、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基が好ましい。 Further, R4 is preferably a halogen atom or a C1 to C6 alkyl group which may be optionally substituted with a substituent C, when Z represents "a thienyl group which may be optionally substituted with R4 from 0 to 3", When Z represents a “thiazolyl group which may be optionally substituted by R4 for 0 to 2”, a halogen atom or a C1 to C6 alkyl group which may be optionally substituted by a substituent C is preferable, and Z is “R4 Is a halogen atom, and when Z represents a "pyrazolyl group optionally substituted with 0 to 3 at R4", a halogen atom or a substituent C Preferably a C1 to C6 alkyl group optionally substituted with or a C1 to C6 haloalkyl group, and when Z represents a "tetrazolyl group optionally substituted with R4", it is optionally substituted with a substituent C. Alkyl group conversion which may be C1 ~ C6 are preferred.
　式（１）のＲ４には、水酸基、シアノ基、およびニトロ基が含まれる。 R4 in the formula (1) includes a hydroxyl group, a cyano group, and a nitro group.
　式（１）のＲ４におけるハロゲン原子は、前記の定義と同義であり、好ましくはフッ素原子、塩素原子、臭素原子、またはヨウ素原子である。 The halogen atom in R4 of the formula (1) has the same meaning as defined above, and is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
　式（１）のＲ４における「置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基」のＣ１～Ｃ６のアルキル基は、前記の定義と同義であり、好ましくは、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、またはイソブチル基であり、さらに好ましくは、メチル基、またはエチル基である。置換基Ｃを有する場合、Ｃ１～Ｃ６のアルキル基における水素原子が、置換基Ｃによって任意に置換される。 The C1 to C6 alkyl group in the "C1 to C6 alkyl group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and is preferably a methyl group or an ethyl group. , A propyl group, an isopropyl group, a butyl group, or an isobutyl group, and more preferably a methyl group or an ethyl group. When it has a substituent C, the hydrogen atom in the C1 to C6 alkyl group is optionally substituted by the substituent C.
　式（１）のＲ４における「Ｃ１～Ｃ６のハロアルキル基」は、前記の定義と同義であり、好ましくは、ジフルオロメチル基、トリフルオロメチル基、２，２－ジフルオロエチル基、２，２，２－トリフルオロエチル基、３，３－ジフルオロプロピル基、または３，３，３－トリフルオロプロピル基であり、さらに好ましくは、ジフルオロメチル基、またはトリフルオロメチル基である。 The “C1-C6 haloalkyl group” for R4 in formula (1) has the same meaning as defined above, and is preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, 2,2,2. -Trifluoroethyl group, 3,3-difluoropropyl group, or 3,3,3-trifluoropropyl group, and more preferably difluoromethyl group or trifluoromethyl group.
　式（１）のＲ４における「置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基」のＣ３～Ｃ８のシクロアルキル基は、前記の定義と同義であり、好ましくは、シクロプロピル基、シクロブチル基、シクロペンチル基、またはシクロヘキシル基であり、さらに好ましくは、シクロプロピル基、またはシクロブチル基である。置換基Ｃを有する場合、Ｃ３～Ｃ８のシクロアルキル基における水素原子が、置換基Ｃによって任意に置換される。 The C3 to C8 cycloalkyl group of the "C3 to C8 cycloalkyl group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably a cyclopropyl group. , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group. When it has a substituent C, the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent C.
　式（１）のＲ４における「置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基」のＣ２～Ｃ６のアルケニル基は、前記の定義と同義であり、好ましくは、ビニル基、１－プロペニル基、アリル基、１－ブテニル基、２－ブテニル基、または３－ブテニル基であり、さらに好ましくは、ビニル基、１－プロペニル基、またはアリル基である。置換基Ｃを有する場合、Ｃ２～Ｃ６のアルケニル基における水素原子が、置換基Ｃによって任意に置換される。 The C2-C6 alkenyl group of the "C2-C6 alkenyl group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably a vinyl group, 1- A propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, or a 3-butenyl group is more preferable, and a vinyl group, a 1-propenyl group, or an allyl group is more preferable. When it has a substituent C, the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent C.
　式（１）のＲ４における「Ｃ２～Ｃ６のハロアルケニル基」は、前記の定義と同義であり、好ましくは、２－フルオロビニル基、２，２－ジフルオロビニル基、２，２－ジクロロビニル基、３－フルオロアリル基、３，３－ジフルオロアリル基、または３，３－ジクロロアリル基であり、さらに好ましくは、２－フルオロビニル基、または２，２－ジフルオロビニル基である。 The “C2-C6 haloalkenyl group” for R4 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group, a 2,2-dichlorovinyl group. , 3-fluoroallyl group, 3,3-difluoroallyl group, or 3,3-dichloroallyl group, and more preferably 2-fluorovinyl group or 2,2-difluorovinyl group.
　式（１）のＲ４における「置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基」のＣ２～Ｃ６のアルキニル基は、前記の定義と同義であり、好ましくは、エチニル基、１－プロピニル基、プロパルギル基、１－ブチニル基、２－ブチニル基、または３－ブチニル基であり、さらに好ましくは、エチニル基、１－プロピニル基、またはプロパルギル基である。置換基Ｃを有する場合、Ｃ２～Ｃ６のアルキニル基における水素原子が、置換基Ｃによって任意に置換される。 The C2-C6 alkynyl group of the "C2-C6 alkynyl group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, preferably an ethynyl group, 1- A propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group is more preferable, and an ethynyl group, a 1-propynyl group, or a propargyl group is more preferable. When it has a substituent C, the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent C.
　式（１）のＲ４における「Ｃ２～Ｃ６のハロアルキニル基」は、前記の定義と同義であり、好ましくは、３，３－ジフルオロ－１－プロピニル基、３，３，３－トリフルオロ－１－プロピニル基、４，４－ジフルオロ－１－ブチニル基、４，４－ジフルオロ－２－ブチニル基、４，４，４－トリフルオロ－１－ブチニル基、または４，４，４－トリフルオロ－２－ブチニル基であり、さらに好ましくは、３，３－ジフルオロ－１－プロピニル基、または３，３，３－トリフルオロ－１－プロピニル基である。 The "C2-C6 haloalkynyl group" in R4 of the formula (1) has the same meaning as defined above, and is preferably a 3,3-difluoro-1-propynyl group or a 3,3,3-trifluoro-1 group. -Propinyl group, 4,4-difluoro-1-butynyl group, 4,4-difluoro-2-butynyl group, 4,4,4-trifluoro-1-butynyl group, or 4,4,4-trifluoro- It is a 2-butynyl group, more preferably a 3,3-difluoro-1-propynyl group or a 3,3,3-trifluoro-1-propynyl group.
　式（１）のＲ４における「置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基」のＣ１～Ｃ６のアルコキシ基は、前記の定義と同義であり、好ましくは、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブトキシ基、イソブトキシ基、またはペンチルオキシ基であり、さらに好ましくは、メトキシ基、またはエトキシ基である。置換基Ｃを有する場合、Ｃ１～Ｃ６のアルコキシ基における水素原子が、置換基Ｃによって任意に置換される。 The C1 to C6 alkoxy group of the "C1 to C6 alkoxy group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably a methoxy group or an ethoxy group. , A propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, or a pentyloxy group, and more preferably a methoxy group or an ethoxy group. When it has a substituent C, the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent C.
　式（１）のＲ４における「Ｃ１～Ｃ６のハロアルコキシ基」は、前記の定義と同義であり、好ましくは、ジフルオロメトキシ基、トリフルオロメトキシ基、２，２－ジフルオロエトキシ基、２，２，２－トリフルオロエトキシ基、３，３－ジフルオロプロピルオキシ基、または３，３，３－トリフルオロプロピルオキシ基であり、さらに好ましくは、ジフルオロメトキシ基、トリフルオロメトキシ基、２，２－ジフルオロエトキシ基、または２，２，２－トリフルオロエトキシ基である。 The “C1-C6 haloalkoxy group” in R4 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2, 2-trifluoroethoxy group, 3,3-difluoropropyloxy group or 3,3,3-trifluoropropyloxy group, more preferably difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group Or a 2,2,2-trifluoroethoxy group.
　式（１）のＲ４における「置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基」のＣ３～Ｃ８のシクロアルコキシ基は、前記の定義と同義であり、好ましくは、シクロプロピルオキシ基、シクロブトキシ基、シクロペンチルオキシ基、またはシクロヘキシルオキシ基であり、さらに好ましくは、シクロプロピルオキシ基、またはシクロブトキシ基である。置換基Ｃを有する場合、Ｃ３～Ｃ８のシクロアルコキシ基における水素原子が、置換基Ｃによって任意に置換される。 The C3 to C8 cycloalkoxy group of the "C3 to C8 cycloalkoxy group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group. When it has a substituent C, the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted by the substituent C.
　式（１）のＲ４における「置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基」のＣ２～Ｃ６のアルケニルオキシ基は、前記の定義と同義であり、好ましくは、ビニルオキシ基、１－プロペニルオキシ基、アリルオキシ基、１－ブテニルオキシ基、２－ブテニルオキシ基、または３－ブテニルオキシ基であり、さらに好ましくは、ビニルオキシ基、１－プロペニルオキシ基、またはアリルオキシ基である。置換基Ｃを有する場合、Ｃ２～Ｃ６のアルケニルオキシ基における水素原子が、置換基Ｃによって任意に置換される。 The C2-C6 alkenyloxy group of the "C2-C6 alkenyloxy group optionally substituted by the substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably a vinyloxy group, It is a 1-propenyloxy group, an allyloxy group, a 1-butenyloxy group, a 2-butenyloxy group or a 3-butenyloxy group, more preferably a vinyloxy group, a 1-propenyloxy group or an allyloxy group. When it has a substituent C, the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent C.
　式（１）のＲ４における「Ｃ２～Ｃ６のハロアルケニルオキシ基」は、前記の定義と同義であり、好ましくは、２－フルオロビニルオキシ基、２，２－ジフルオロビニルオキシ基、２，２－ジクロロビニルオキシ基、３－フルオロアリルオキシ基、３，３－ジフルオロアリルオキシ基、または３，３－ジクロロアリルオキシ基であり、さらに好ましくは、２－フルオロビニルオキシ基、または２，２－ジフルオロビニルオキシ基である。 The “C2-C6 haloalkenyloxy group” for R4 in formula (1) has the same meaning as defined above, and is preferably 2-fluorovinyloxy group, 2,2-difluorovinyloxy group, 2,2- A dichlorovinyloxy group, a 3-fluoroallyloxy group, a 3,3-difluoroallyloxy group, or a 3,3-dichloroallyloxy group, more preferably a 2-fluorovinyloxy group or a 2,2-difluoro group. It is a vinyloxy group.
　式（１）のＲ４における「置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基」のＣ３～Ｃ６のアルキニルオキシ基は、前記の定義と同義であり、好ましくは、プロパルギルオキシ基、２－ブチニルオキシ基、または３－ブチニルオキシ基であり、さらに好ましくは、プロパルギルオキシ基、または２－ブチニルオキシ基である。置換基Ｃを有する場合、Ｃ３～Ｃ６のアルキニルオキシ基における水素原子が、置換基Ｃによって任意に置換される。 The C3 to C6 alkynyloxy group of the "C3 to C6 alkynyloxy group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably a propargyloxy group. , A 2-butynyloxy group, or a 3-butynyloxy group, and more preferably a propargyloxy group or a 2-butynyloxy group. When it has a substituent C, the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent C.
　式（１）のＲ４における「Ｃ３～Ｃ６のハロアルキニルオキシ基」は、前記の定義と同義であり、好ましくは、４，４－ジフルオロ－２－ブチニルオキシ基、４－クロロ－４，４－ジフルオロ－２－ブチニルオキシ基、４－ブロモ－４，４－ジフルオロ－２－ブチニルオキシ基、または４，４，４－トリフルオロ－２－ブチニルオキシ基であり、さらに好ましくは、４，４－ジフルオロ－２－ブチニルオキシ基、または４，４，４－トリフルオロ－２－ブチニルオキシ基である。 The “C3-C6 haloalkynyloxy group” for R4 in formula (1) has the same meaning as defined above, and is preferably a 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro group. -2-butynyloxy group, 4-bromo-4,4-difluoro-2-butynyloxy group, or 4,4,4-trifluoro-2-butynyloxy group, more preferably 4,4-difluoro-2- It is a butynyloxy group or a 4,4,4-trifluoro-2-butynyloxy group.
　式（１）のＲ４における「ＲｄＣ（＝Ｏ）－」のＲｄは前記と同義である。Ｒｄとして、好ましくは、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、またはＣ１～Ｃ６のハロアルキル基であり、さらに好ましくは、水素原子、または置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基である。「ＲｄＣ（＝Ｏ）－」として、好ましくは、ホルミル基、アセチル基、メトキシアセチル基、シアノアセチル基、プロピオニル基、ジフルオロアセチル基、トリフルオロアセチル基、シクロプロパンカルボニル基、メトキシカルボニル基、エトキシカルボニル基、２，２－ジフルオロエトキシカルボニル基、２，２，２－トリフルオロエトキシカルボニル基、３，３，３－トリフルオロプロピルオキシカルボニル基、またはシクロプロピルオキシカルボニル基であり、さらに好ましくは、ホルミル基、またはアセチル基である。 Rd of "RdC (= O)-" in R4 of the formula (1) has the same meaning as above. Rd is preferably a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, or a C1 to C6 haloalkyl group, more preferably a hydrogen atom or a substituent B as appropriate. And C1 to C6 alkyl groups which may be included. “RdC (═O) —” is preferably formyl group, acetyl group, methoxyacetyl group, cyanoacetyl group, propionyl group, difluoroacetyl group, trifluoroacetyl group, cyclopropanecarbonyl group, methoxycarbonyl group, ethoxycarbonyl. Group, 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 3,3,3-trifluoropropyloxycarbonyl group, or cyclopropyloxycarbonyl group, more preferably formyl Group or acetyl group.
　式（１）のＲ４における「ＲｄＣ（＝Ｏ）Ｏ－」のＲｄは、前記と同義である。「ＲｄＣ（＝Ｏ）Ｏ－」として、好ましくは、ホルミルオキシ基、アセチルオキシ基、メトキシアセチルオキシ基、シアノアセチルオキシ基、プロピオニルオキシ基、ジフルオロアセチルオキシ基、トリフルオロアセチルオキシ基、シクロプロパンカルボニルオキシ基、メトキシカルボニルオキシ基、エトキシカルボニルオキシ基、２，２－ジフルオロエトキシカルボニルオキシ基、２，２，２－トリフルオロエトキシカルボニルオキシ基、３，３，３－トリフルオロプロピルオキシカルボニルオキシ基、またはシクロプロピルオキシカルボニルオキシ基であり、さらに好ましくは、ホルミルオキシ基、またはアセチルオキシ基である。 Rd of "RdC (= O) O-" in R4 of the formula (1) has the same meaning as above. “RdC (═O) O—” is preferably formyloxy group, acetyloxy group, methoxyacetyloxy group, cyanoacetyloxy group, propionyloxy group, difluoroacetyloxy group, trifluoroacetyloxy group, cyclopropanecarbonyl. Oxy group, methoxycarbonyloxy group, ethoxycarbonyloxy group, 2,2-difluoroethoxycarbonyloxy group, 2,2,2-trifluoroethoxycarbonyloxy group, 3,3,3-trifluoropropyloxycarbonyloxy group, Alternatively, it is a cyclopropyloxycarbonyloxy group, more preferably a formyloxy group, or an acetyloxy group.
　式（１）のＲ４における「Ｒｃ－Ｌ－」のＲｃおよびＬは、前記と同義である。「Ｒｃ－Ｌ－」として、好ましくは、メチルチオ基、メタンスルフィニル基、メタンスルホニル基、エチルチオ基、エタンスルフィニル基、エタンスルホニル基、トリフルオロメチルチオ基、トリフルオロメタンスルフィニル基、またはトリフルオロメタンスルホニル基であり、さらに好ましくは、メチルチオ基、メタンスルフィニル基、またはメタンスルホニル基である。 Rc and L of "Rc-L-" in R4 of the formula (1) have the same meaning as above. "Rc-L-" is preferably a methylthio group, a methanesulfinyl group, a methanesulfonyl group, an ethylthio group, an ethanesulfinyl group, an ethanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, or a trifluoromethanesulfonyl group. , And more preferably, a methylthio group, a methanesulfinyl group, or a methanesulfonyl group.
　式（１）のＲ４における「ＲａＲｂＮ－」のＲａおよびＲｂは、前記と同義である。「ＲａＲｂＮ－」として、好ましくは、アミノ基、メチルアミノ基、エチルアミノ基、プロピルアミノ基、イソプロピルアミノ基、（メトキシメチル）アミノ基、（２－メトキシエチル）アミノ基、（シアノメチル）アミノ基、（２－シアノエチル）アミノ基、ジメチルアミノ基、エチル（メチル）アミノ基、メチル（プロピル）アミノ基、イソプロピル（メチル）アミノ基、（メトキシメチル）メチルアミノ基、（２－メトキシエチル）メチルアミノ基、（シアノメチル）メチルアミノ基、（２－シアノエチル）メチルアミノ基、ジエチルアミノ基、エチル（プロピル）アミノ基、エチル（イソプロピル）アミノ基、エチル（メトキシメチル）アミノ基、エチル（２－メトキシエチル）アミノ基、（シアノメチル）エチルアミノ基、（２－シアノエチル）エチルアミノ基、２，２－ジフルオロエチルアミノ基、２，２，２－トリフルオロエチルアミノ基、シクロプロピルアミノ基、または（シクロプロピル）メチルアミノ基であり、さらに好ましくは、アミノ基、ジメチルアミノ基、エチル（メチル）アミノ基、またはジエチルアミノ基である。 Ra and Rb of "RaRbN-" in R4 of the formula (1) are as defined above. "RaRbN-" is preferably an amino group, a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a (methoxymethyl) amino group, a (2-methoxyethyl) amino group, a (cyanomethyl) amino group, (2-Cyanoethyl) amino group, dimethylamino group, ethyl (methyl) amino group, methyl (propyl) amino group, isopropyl (methyl) amino group, (methoxymethyl) methylamino group, (2-methoxyethyl) methylamino group , (Cyanomethyl) methylamino group, (2-cyanoethyl) methylamino group, diethylamino group, ethyl (propyl) amino group, ethyl (isopropyl) amino group, ethyl (methoxymethyl) amino group, ethyl (2-methoxyethyl) amino group Group, (cyanomethyl) ethylamino group, (2- Anoethyl) ethylamino group, 2,2-difluoroethylamino group, 2,2,2-trifluoroethylamino group, cyclopropylamino group, or (cyclopropyl) methylamino group, more preferably an amino group, A dimethylamino group, an ethyl (methyl) amino group, or a diethylamino group.
　式（１）のＲ４における「ＲｅＣ（＝Ｏ）Ｎ（Ｒｆ）－」のＲｅおよびＲｆは、前記と同義である。「ＲｅＣ（＝Ｏ）Ｎ（Ｒｆ）－」として、好ましくは、ホルミルアミノ基、アセチルアミノ基、メトキシアセチルアミノ基、シアノアセチルアミノ基、プロピオニルアミノ基、ジフルオロアセチルアミノ基、トリフルオロアセチルアミノ基、シクロプロパンカルボニルアミノ基、メトキシカルボニルアミノ基、エトキシカルボニルアミノ基、２，２－ジフルオロエトキシカルボニルアミノ基、２，２，２－トリフルオロエトキシカルボニルアミノ基、３，３，３－トリフルオロプロピルオキシカルボニルアミノ基、シクロプロピルオキシカルボニルアミノ基、アミノカルボニルアミノ基、メチルアミノカルボニルアミノ基、エチルアミノカルボニルアミノ基、（メトキシメチル）アミノカルボニルアミノ基、（２－メトキシエチル）アミノカルボニルアミノ基、（シアノメチル）アミノカルボニルアミノ基、（２－シアノエチル）アミノカルボニルアミノ基、ジメチルアミノカルボニルアミノ基、エチル（メチル）アミノカルボニルアミノ基、ジエチルアミノカルボニルアミノ基、（メトキシメチル）メチルアミノカルボニルアミノ基、（２－メトキシエチル）メチルアミノカルボニルアミノ基、（シアノメチル）メチルアミノカルボニルアミノ基、（２－シアノエチル）メチルアミノカルボニルアミノ基、２，２－ジフルオロエチルアミノカルボニルアミノ基、２，２，２－トリフルオロエチルアミノカルボニルアミノ基、シクロプロピルアミノカルボニルアミノ基、シクロプロピル（メチル）アミノカルボニルアミノ基、ピロリジニルカルボニルアミノ基、ピペリジニルカルボニルアミノ基、ホルミル（メチル）アミノ基、アセチル（メチル）アミノ基、メトキシアセチル（メチル）アミノ基、シアノアセチル（メチル）アミノ基、プロピオニル（メチル）アミノ基、ジフルオロアセチル（メチル）アミノ基、トリフルオロアセチル（メチル）アミノ基、シクロプロパンカルボニル（メチル）アミノ基、メトキシカルボニル（メチル）アミノ基、エトキシカルボニル（メチル）アミノ基、２，２－ジフルオロエトキシカルボニル（メチル）アミノ基、２，２，２－トリフルオロエトキシカルボニル（メチル）アミノ基、３，３，３－トリフルオロプロピルオキシカルボニル（メチル）アミノ基、シクロプロピルオキシカルボニル（メチル）アミノ基、アミノカルボニル（メチル）アミノ基、メチルアミノカルボニル（メチル）アミノ基、エチルアミノカルボニル（メチル）アミノ基、（メトキシメチル）アミノカルボニル（メチル）アミノ基、（２－メトキシエチル）アミノカルボニル（メチル）アミノ基、（シアノメチル）アミノカルボニル（メチル）アミノ基、（２－シアノエチル）アミノカルボニル（メチル）アミノ基、ジメチルアミノカルボニル（メチル）アミノ基、エチル（メチル）アミノカルボニル（メチル）アミノ基、ジエチルアミノカルボニル（メチル）アミノ基、（メトキシメチル）メチルアミノカルボニル（メチル）アミノ基、（２－メトキシエチル）メチルアミノカルボニル（メチル）アミノ基、（シアノメチル）メチルアミノカルボニル（メチル）アミノ基、（２－シアノエチル）メチルアミノカルボニル（メチル）アミノ基、２，２－ジフルオロエチルアミノカルボニル（メチル）アミノ基、２，２，２－トリフルオロエチルアミノカルボニル（メチル）アミノ基、シクロプロピルアミノカルボニル（メチル）アミノ基、シクロプロピル（メチル）アミノカルボニル（メチル）アミノ基、ピロリジニルカルボニル（メチル）アミノ基、ピペリジニルカルボニル（メチル）アミノ基、ホルミル（エチル）アミノ基、アセチル（エチル）アミノ基、メトキシアセチル（エチル）アミノ基、シアノアセチル（エチル）アミノ基、プロピオニル（エチル）アミノ基、ジフルオロアセチル（エチル）アミノ基、トリフルオロアセチル（エチル）アミノ基、シクロプロパンカルボニル（エチル）アミノ基、メトキシカルボニル（エチル）アミノ基、エトキシカルボニル（エチル）アミノ基、２，２－ジフルオロエトキシカルボニル（エチル）アミノ基、２，２，２－トリフルオロエトキシカルボニル（エチル）アミノ基、３，３，３－トリフルオロプロピルオキシカルボニル（エチル）アミノ基、シクロプロピルオキシカルボニル（エチル）アミノ基、アミノカルボニル（エチル）アミノ基、メチルアミノカルボニル（エチル）アミノ基、エチルアミノカルボニル（エチル）アミノ基、（メトキシメチル）アミノカルボニル（エチル）アミノ基、（２－メトキシエチル）アミノカルボニル（エチル）アミノ基、（シアノメチル）アミノカルボニル（エチル）アミノ基、（２－シアノエチル）アミノカルボニル（エチル）アミノ基、ジメチルアミノカルボニル（エチル）アミノ基、エチル（メチル）アミノカルボニル（エチル）アミノ基、ジエチルアミノカルボニル（エチル）アミノ基、（メトキシメチル）メチルアミノカルボニル（エチル）アミノ基、（２－メトキシエチル）メチルアミノカルボニル（エチル）アミノ基、（シアノメチル）メチルアミノカルボニル（エチル）アミノ基、（２－シアノエチル）メチルアミノカルボニル（エチル）アミノ基、２，２－ジフルオロエチルアミノカルボニル（エチル）アミノ基、２，２，２－トリフルオロエチルアミノカルボニル（エチル）アミノ基、シクロプロピルアミノカルボニル（エチル）アミノ基、シクロプロピル（メチル）アミノカルボニル（エチル）アミノ基、ピロリジニルカルボニル（エチル）アミノ基、ピペリジニルカルボニル（エチル）アミノ基、ホルミル（メトキシ）アミノ基、アセチル（メトキシ）アミノ基、メトキシアセチル（メトキシ）アミノ基、シアノアセチル（メトキシ）アミノ基、プロピオニル（メトキシ）アミノ基、ジフルオロアセチル（メトキシ）アミノ基、トリフルオロアセチル（メトキシ）アミノ基、シクロプロパンカルボニル（メトキシ）アミノ基、メトキシカルボニル（メトキシ）アミノ基、エトキシカルボニル（メトキシ）アミノ基、２，２－ジフルオロエトキシカルボニル（メトキシ）アミノ基、２，２，２－トリフルオロエトキシカルボニル（メトキシ）アミノ基、３，３，３－トリフルオロプロピルオキシカルボニル（メトキシ）アミノ基、シクロプロピルオキシカルボニル（メトキシ）アミノ基、アミノカルボニル（メトキシ）アミノ基、メチルアミノカルボニル（メトキシ）アミノ基、エチルアミノカルボニル（メトキシ）アミノ基、（メトキシメチル）アミノカルボニル（メトキシ）アミノ基、（２－メトキシエチル）アミノカルボニル（メトキシ）アミノ基、（シアノメチル）アミノカルボニル（メトキシ）アミノ基、（２－シアノエチル）アミノカルボニル（メトキシ）アミノ基、ジメチルアミノカルボニル（メトキシ）アミノ基、エチル（メチル）アミノカルボニル（メトキシ）アミノ基、ジエチルアミノカルボニル（メトキシ）アミノ基、（メトキシメチル）メチルアミノカルボニル（メトキシ）アミノ基、（２－メトキシエチル）メチルアミノカルボニル（メトキシ）アミノ基、（シアノメチル）メチルアミノカルボニル（メトキシ）アミノ基、（２－シアノエチル）メチルアミノカルボニル（メトキシ）アミノ基、２，２－ジフルオロエチルアミノカルボニル（メトキシ）アミノ基、２，２，２－トリフルオロエチルアミノカルボニル（メトキシ）アミノ基、シクロプロピルアミノカルボニル（メトキシ）アミノ基、シクロプロピル（メチル）アミノカルボニル（メトキシ）アミノ基、ピロリジニルカルボニル（メトキシ）アミノ基、ピペリジニルカルボニル（メトキシ）アミノ基、ホルミル（エトキシ）アミノ基、アセチル（エトキシ）アミノ基、メトキシアセチル（エトキシ）アミノ基、シアノアセチル（エトキシ）アミノ基、プロピオニル（エトキシ）アミノ基、ジフルオロアセチル（エトキシ）アミノ基、トリフルオロアセチル（エトキシ）アミノ基、シクロプロパンカルボニル（エトキシ）アミノ基、メトキシカルボニル（エトキシ）アミノ基、エトキシカルボニル（エトキシ）アミノ基、２，２－ジフルオロエトキシカルボニル（エトキシ）アミノ基、２，２，２－トリフルオロエトキシカルボニル（エトキシ）アミノ基、３，３，３－トリフルオロプロピルオキシカルボニル（エトキシ）アミノ基、シクロプロピルオキシカルボニル（エトキシ）アミノ基、アミノカルボニル（エトキシ）アミノ基、メチルアミノカルボニル（エトキシ）アミノ基、エチルアミノカルボニル（エトキシ）アミノ基、（メトキシメチル）アミノカルボニル（エトキシシ）アミノ基、（２－メトキシエチル）アミノカルボニル（エトキシ）アミノ基、（シアノメチル）アミノカルボニル（エトキシ）アミノ基、（２－シアノエチル）アミノカルボニル（エトキシ）アミノ基、ジメチルアミノカルボニル（エトキシ）アミノ基、エチル（メチル）アミノカルボニル（エトキシ）アミノ基、ジエチルアミノカルボニル（エトキシ）アミノ基、（メトキシメチル）メチルアミノカルボニル（エトキシ）アミノ基、（２－メトキシエチル）メチルアミノカルボニル（エトキシ）アミノ基、（シアノメチル）メチルアミノカルボニル（エトキシ）アミノ基、（２－シアノエチル）メチルアミノカルボニル（エトキシ）アミノ基、２，２－ジフルオロエチルアミノカルボニル（エトキシ）アミノ基、２，２，２－トリフルオロエチルアミノカルボニル（エトキシ）アミノ基、シクロプロピルアミノカルボニル（エトキシ）アミノ基、シクロプロピル（メチル）アミノカルボニル（エトキシ）アミノ基、ピロリジニルカルボニル（エトキシ）アミノ基、またはピペリジニルカルボニル（エトキシ）アミノ基であり、さらに好ましくは、アセチルアミノ基、アセチル（メチル）アミノ基、アセチル（エチル）アミノ基、アセチル（メトキシ）アミノ基、アセチル（エトキシ）アミノ基、メトキシカルボニルアミノ基、エトキシカルボニルアミノ基、メトキシカルボニル（メチル）アミノ基、エトキシカルボニル（メチル）アミノ基、メトキシカルボニル（エチル）アミノ基、エトキシカルボニル（エチル）アミノ基、メトキシカルボニル（メトキシ）アミノ基、エトキシカルボニル（メトキシ）アミノ基、メトキシカルボニル（エトキシ）アミノ基、またはエトキシカルボニル（エトキシ）アミノ基である。 Re and Rf of "ReC (= O) N (Rf)-" in R4 of the formula (1) are as defined above. "ReC (= O) N (Rf)-" is preferably a formylamino group, an acetylamino group, a methoxyacetylamino group, a cyanoacetylamino group, a propionylamino group, a difluoroacetylamino group, a trifluoroacetylamino group, Cyclopropanecarbonylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, 2,2-difluoroethoxycarbonylamino group, 2,2,2-trifluoroethoxycarbonylamino group, 3,3,3-trifluoropropyloxycarbonyl Amino group, cyclopropyloxycarbonylamino group, aminocarbonylamino group, methylaminocarbonylamino group, ethylaminocarbonylamino group, (methoxymethyl) aminocarbonylamino group, (2-methoxyethyl) aminocarb Bonylamino group, (cyanomethyl) aminocarbonylamino group, (2-cyanoethyl) aminocarbonylamino group, dimethylaminocarbonylamino group, ethyl (methyl) aminocarbonylamino group, diethylaminocarbonylamino group, (methoxymethyl) methylaminocarbonylamino group , (2-methoxyethyl) methylaminocarbonylamino group, (cyanomethyl) methylaminocarbonylamino group, (2-cyanoethyl) methylaminocarbonylamino group, 2,2-difluoroethylaminocarbonylamino group, 2,2,2- Trifluoroethylaminocarbonylamino group, cyclopropylaminocarbonylamino group, cyclopropyl (methyl) aminocarbonylamino group, pyrrolidinylcarbonylamino group, piperidinylcarbo group Ruamino group, formyl (methyl) amino group, acetyl (methyl) amino group, methoxyacetyl (methyl) amino group, cyanoacetyl (methyl) amino group, propionyl (methyl) amino group, difluoroacetyl (methyl) amino group, trifluoro Acetyl (methyl) amino group, cyclopropanecarbonyl (methyl) amino group, methoxycarbonyl (methyl) amino group, ethoxycarbonyl (methyl) amino group, 2,2-difluoroethoxycarbonyl (methyl) amino group, 2,2,2 -Trifluoroethoxycarbonyl (methyl) amino group, 3,3,3-trifluoropropyloxycarbonyl (methyl) amino group, cyclopropyloxycarbonyl (methyl) amino group, aminocarbonyl (methyl) amino group, methylaminocarbonyl ( Me (Cyl) amino group, ethylaminocarbonyl (methyl) amino group, (methoxymethyl) aminocarbonyl (methyl) amino group, (2-methoxyethyl) aminocarbonyl (methyl) amino group, (cyanomethyl) aminocarbonyl (methyl) amino group , (2-cyanoethyl) aminocarbonyl (methyl) amino group, dimethylaminocarbonyl (methyl) amino group, ethyl (methyl) aminocarbonyl (methyl) amino group, diethylaminocarbonyl (methyl) amino group, (methoxymethyl) methylaminocarbonyl (Methyl) amino group, (2-methoxyethyl) methylaminocarbonyl (methyl) amino group, (cyanomethyl) methylaminocarbonyl (methyl) amino group, (2-cyanoethyl) methylaminocarbonyl (methyl) amino group, 2, -Difluoroethylaminocarbonyl (methyl) amino group, 2,2,2-trifluoroethylaminocarbonyl (methyl) amino group, cyclopropylaminocarbonyl (methyl) amino group, cyclopropyl (methyl) aminocarbonyl (methyl) amino group , Pyrrolidinylcarbonyl (methyl) amino group, piperidinylcarbonyl (methyl) amino group, formyl (ethyl) amino group, acetyl (ethyl) amino group, methoxyacetyl (ethyl) amino group, cyanoacetyl (ethyl) amino group , Propionyl (ethyl) amino group, difluoroacetyl (ethyl) amino group, trifluoroacetyl (ethyl) amino group, cyclopropanecarbonyl (ethyl) amino group, methoxycarbonyl (ethyl) amino group, ethoxycarbonyl (ethyl) ami Group, 2,2-difluoroethoxycarbonyl (ethyl) amino group, 2,2,2-trifluoroethoxycarbonyl (ethyl) amino group, 3,3,3-trifluoropropyloxycarbonyl (ethyl) amino group, cyclopropyl Oxycarbonyl (ethyl) amino group, aminocarbonyl (ethyl) amino group, methylaminocarbonyl (ethyl) amino group, ethylaminocarbonyl (ethyl) amino group, (methoxymethyl) aminocarbonyl (ethyl) amino group, (2-methoxy Ethyl) aminocarbonyl (ethyl) amino group, (cyanomethyl) aminocarbonyl (ethyl) amino group, (2-cyanoethyl) aminocarbonyl (ethyl) amino group, dimethylaminocarbonyl (ethyl) amino group, ethyl (methyl) aminocarbonyl ( ethyl) Amino group, diethylaminocarbonyl (ethyl) amino group, (methoxymethyl) methylaminocarbonyl (ethyl) amino group, (2-methoxyethyl) methylaminocarbonyl (ethyl) amino group, (cyanomethyl) methylaminocarbonyl (ethyl) amino group , (2-cyanoethyl) methylaminocarbonyl (ethyl) amino group, 2,2-difluoroethylaminocarbonyl (ethyl) amino group, 2,2,2-trifluoroethylaminocarbonyl (ethyl) amino group, cyclopropylaminocarbonyl (Ethyl) amino group, cyclopropyl (methyl) aminocarbonyl (ethyl) amino group, pyrrolidinylcarbonyl (ethyl) amino group, piperidinylcarbonyl (ethyl) amino group, formyl (methoxy) amino group, acetyl (methoxy) Amino group, methoxyacetyl (methoxy) amino group, cyanoacetyl (methoxy) amino group, propionyl (methoxy) amino group, difluoroacetyl (methoxy) amino group, trifluoroacetyl (methoxy) amino group, cyclopropanecarbonyl (methoxy) amino group Group, methoxycarbonyl (methoxy) amino group, ethoxycarbonyl (methoxy) amino group, 2,2-difluoroethoxycarbonyl (methoxy) amino group, 2,2,2-trifluoroethoxycarbonyl (methoxy) amino group, 3,3 , 3-trifluoropropyloxycarbonyl (methoxy) amino group, cyclopropyloxycarbonyl (methoxy) amino group, aminocarbonyl (methoxy) amino group, methylaminocarbonyl (methoxy) amino group, ethylamino Rubonyl (methoxy) amino group, (methoxymethyl) aminocarbonyl (methoxy) amino group, (2-methoxyethyl) aminocarbonyl (methoxy) amino group, (cyanomethyl) aminocarbonyl (methoxy) amino group, (2-cyanoethyl) amino Carbonyl (methoxy) amino group, dimethylaminocarbonyl (methoxy) amino group, ethyl (methyl) aminocarbonyl (methoxy) amino group, diethylaminocarbonyl (methoxy) amino group, (methoxymethyl) methylaminocarbonyl (methoxy) amino group, ( 2-methoxyethyl) methylaminocarbonyl (methoxy) amino group, (cyanomethyl) methylaminocarbonyl (methoxy) amino group, (2-cyanoethyl) methylaminocarbonyl (methoxy) amino group, 2,2-di Fluoroethylaminocarbonyl (methoxy) amino group, 2,2,2-trifluoroethylaminocarbonyl (methoxy) amino group, cyclopropylaminocarbonyl (methoxy) amino group, cyclopropyl (methyl) aminocarbonyl (methoxy) amino group, Pyrrolidinylcarbonyl (methoxy) amino group, piperidinylcarbonyl (methoxy) amino group, formyl (ethoxy) amino group, acetyl (ethoxy) amino group, methoxyacetyl (ethoxy) amino group, cyanoacetyl (ethoxy) amino group, Propionyl (ethoxy) amino group, difluoroacetyl (ethoxy) amino group, trifluoroacetyl (ethoxy) amino group, cyclopropanecarbonyl (ethoxy) amino group, methoxycarbonyl (ethoxy) amino group, ethoxy Rubonyl (ethoxy) amino group, 2,2-difluoroethoxycarbonyl (ethoxy) amino group, 2,2,2-trifluoroethoxycarbonyl (ethoxy) amino group, 3,3,3-trifluoropropyloxycarbonyl (ethoxy) Amino group, cyclopropyloxycarbonyl (ethoxy) amino group, aminocarbonyl (ethoxy) amino group, methylaminocarbonyl (ethoxy) amino group, ethylaminocarbonyl (ethoxy) amino group, (methoxymethyl) aminocarbonyl (ethoxysi) amino group , (2-methoxyethyl) aminocarbonyl (ethoxy) amino group, (cyanomethyl) aminocarbonyl (ethoxy) amino group, (2-cyanoethyl) aminocarbonyl (ethoxy) amino group, dimethylaminocarbonyl (ethoxy Amino group, ethyl (methyl) aminocarbonyl (ethoxy) amino group, diethylaminocarbonyl (ethoxy) amino group, (methoxymethyl) methylaminocarbonyl (ethoxy) amino group, (2-methoxyethyl) methylaminocarbonyl (ethoxy) amino group , (Cyanomethyl) methylaminocarbonyl (ethoxy) amino group, (2-cyanoethyl) methylaminocarbonyl (ethoxy) amino group, 2,2-difluoroethylaminocarbonyl (ethoxy) amino group, 2,2,2-trifluoroethyl Aminocarbonyl (ethoxy) amino group, cyclopropylaminocarbonyl (ethoxy) amino group, cyclopropyl (methyl) aminocarbonyl (ethoxy) amino group, pyrrolidinylcarbonyl (ethoxy) amino group, or piperidinyl Is a carbonyl (ethoxy) amino group, more preferably an acetylamino group, an acetyl (methyl) amino group, an acetyl (ethyl) amino group, an acetyl (methoxy) amino group, an acetyl (ethoxy) amino group, a methoxycarbonylamino group. , Ethoxycarbonylamino group, methoxycarbonyl (methyl) amino group, ethoxycarbonyl (methyl) amino group, methoxycarbonyl (ethyl) amino group, ethoxycarbonyl (ethyl) amino group, methoxycarbonyl (methoxy) amino group, ethoxycarbonyl (methoxy ) Amino group, methoxycarbonyl (ethoxy) amino group, or ethoxycarbonyl (ethoxy) amino group.
　式（１）の「置換基Ａ」とは、水酸基、シアノ基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、Ｃ３～Ｃ８のシクロアルコキシ基、ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）およびＲｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）からなる群から選択される少なくとも１種を表す。 The “substituent A” in the formula (1) means a hydroxyl group, a cyano group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, a C3 to C8 cycloalkoxy group, RaRbN. -(Wherein Ra and Rb have the same meanings as described above) and Rc-L- (wherein Rc and L have the same meanings as described above), and at least one member selected from the group consisting of: ..
　中でも置換基Ａは、シアノ基、Ｃ１～Ｃ６のアルコキシ基またはＲｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）が好ましく、
　特に、シアノ基またはＣ１～Ｃ６のアルコキシ基が好ましい。 Of these, the substituent A is preferably a cyano group, a C1-C6 alkoxy group or Rc-L- (wherein Rc and L have the same meanings as described above),
Particularly, a cyano group or a C1-C6 alkoxy group is preferable.
　置換基Ａの各用語は前記の定義と同義である。 Each term of the substituent A has the same meaning as defined above.
　置換基Ａの好ましい具体例に関しては、水酸基；
　シアノ基；
Ｃ３～Ｃ８のシクロアルキル基として、シクロプロピル基、シクロブチル基、シクロペンチル基、およびシクロヘキシル基；
　Ｃ１～Ｃ６のアルコキシ基として、メトキシ基、エトキシ基、プロピルオキシ基、およびイソプロピルオキシ基；
　Ｃ１～Ｃ６のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、２，２－ジフルオロエトキシ基、２，２，２－トリフルオロエトキシ基、３，３－ジフルオロプロピルオキシ基、および３，３，３－トリフルオロプロピルオキシ基；
　Ｃ３～Ｃ８のシクロアルコキシ基として、シクロプロピルオキシ基、シクロブトキシ基、シクロペンチルオキシ基、およびシクロヘキシルオキシ基；
　ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）として、アミノ基、メチルアミノ基、エチルアミノ基、プロピルアミノ基、イソプロピルアミノ基、（メトキシメチル）アミノ基、（２－メトキシエチル）アミノ基、（シアノメチル）アミノ基、（２－シアノエチル）アミノ基、ジメチルアミノ基、エチル（メチル）アミノ基、メチル（プロピル）アミノ基、イソプロピル（メチル）アミノ基、（メトキシメチル）メチルアミノ基、（２－メトキシエチル）メチルアミノ基、（シアノメチル）メチルアミノ基、（２－シアノエチル）メチルアミノ基、ジエチルアミノ基、エチル（プロピル）アミノ基、エチル（イソプロピル）アミノ基、エチル（メトキシメチル）アミノ基、エチル（２－メトキシエチル）アミノ基、（シアノメチル）エチルアミノ基、（２－シアノエチル）エチルアミノ基、２，２－ジフルオロエチルアミノ基、２，２，２－トリフルオロエチルアミノ基、シクロプロピルアミノ基、および（シクロプロピル）メチルアミノ基；
　ならびにＲｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）として、メチルチオ基、メタンスルフィニル基、メタンスルホニル基、トリフルオロメチルチオ基、トリフルオロメタンスルフィニル基、およびトリフルオロメタンスルホニル基が挙げられる。 For preferred specific examples of the substituent A, a hydroxyl group;
Cyano group;
As a C3-C8 cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group;
A methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group as the C1 to C6 alkoxy group;
As the C1 to C6 haloalkoxy group, difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 3,3-difluoropropyloxy group, and 3,3 , 3-trifluoropropyloxy group;
As a C3-C8 cycloalkoxy group, a cyclopropyloxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group;
As RaRbN- (wherein Ra and Rb are as defined above), an amino group, a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a (methoxymethyl) amino group, (2-methoxy) Ethyl) amino group, (cyanomethyl) amino group, (2-cyanoethyl) amino group, dimethylamino group, ethyl (methyl) amino group, methyl (propyl) amino group, isopropyl (methyl) amino group, (methoxymethyl) methylamino Group, (2-methoxyethyl) methylamino group, (cyanomethyl) methylamino group, (2-cyanoethyl) methylamino group, diethylamino group, ethyl (propyl) amino group, ethyl (isopropyl) amino group, ethyl (methoxymethyl) Amino group, ethyl (2-methoxyethyl) amino group, (sia Methyl) ethylamino group, (2-cyanoethyl) ethylamino group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, cyclopropylamino group, and (cyclopropyl) methylamino group;
And Rc-L- (where Rc and L have the same meanings as defined above) include a methylthio group, a methanesulfinyl group, a methanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, and a trifluoromethanesulfonyl group. Can be mentioned.
　置換基Ａのさらに好ましい具体例に関しては、水酸基；
　シアノ基；
　Ｃ３～Ｃ８のシクロアルキル基として、シクロプロピル基、およびシクロブチル基；
　Ｃ１～Ｃ６のアルコキシ基として、メトキシ基、およびエトキシ基；
　Ｃ１～Ｃ６のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、２，２－ジフルオロエトキシ基、および２，２，２－トリフルオロエトキシ基；
　Ｃ３～Ｃ８のシクロアルコキシ基として、シクロプロピルオキシ基、およびシクロブトキシ基；
　ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）として、ジメチルアミノ基、エチル（メチル）アミノ基、およびジエチルアミノ基；
　ならびにＲｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）として、メチルチオ基、メタンスルフィニル基、およびメタンスルホニル基が挙げられる。 For more preferred specific examples of the substituent A, a hydroxyl group;
Cyano group;
As a C3 to C8 cycloalkyl group, a cyclopropyl group and a cyclobutyl group;
As a C1-C6 alkoxy group, a methoxy group and an ethoxy group;
As a C1-C6 haloalkoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, and a 2,2,2-trifluoroethoxy group;
As a C3-C8 cycloalkoxy group, a cyclopropyloxy group and a cyclobutoxy group;
RaRbN- (wherein Ra and Rb have the same meanings as defined above), as a dimethylamino group, an ethyl (methyl) amino group, and a diethylamino group;
Further, examples of Rc-L- (wherein Rc and L have the same meanings as described above) include a methylthio group, a methanesulfinyl group, and a methanesulfonyl group.
　式（１）の「置換基Ｂ」とは、シアノ基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基およびＣ３～Ｃ８のシクロアルコキシ基からなる群から選択される少なくとも１種を表す。 The “substituent B” in the formula (1) represents at least one selected from the group consisting of a cyano group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, and a C3 to C8 cycloalkoxy group. .
　中でも置換基Ｂは、シアノ基またはＣ１～Ｃ６のアルコキシ基が好ましい。
　置換基Ｂの各用語は前記の定義と同義である。 Among them, the substituent B is preferably a cyano group or a C1-C6 alkoxy group.
Each term of the substituent B has the same meaning as defined above.
　置換基Ｂの好ましい具体例に関しては、シアノ基；
　Ｃ１～Ｃ６のアルコキシ基として、メトキシ基、エトキシ基、プロピルオキシ基、およびイソプロピルオキシ基；
　Ｃ１～Ｃ６のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、２，２－ジフルオロエトキシ基、２，２，２－トリフルオロエトキシ基、３，３－ジフルオロプロピルオキシ基、および３，３，３－トリフルオロプロピルオキシ基；
　ならびにＣ３～Ｃ８のシクロアルコキシ基として、シクロプロピルオキシ基、シクロブトキシ基、シクロペンチルオキシ基、およびシクロヘキシルオキシ基が挙げられる。 For preferred specific examples of the substituent B, a cyano group;
A methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group as the C1 to C6 alkoxy group;
As the C1 to C6 haloalkoxy group, difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 3,3-difluoropropyloxy group, and 3,3 , 3-trifluoropropyloxy group;
Examples of the C3 to C8 cycloalkoxy group include a cyclopropyloxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.
　置換基Ｂのさらに好ましい具体例に関しては、シアノ基；
　Ｃ１～Ｃ６のアルコキシ基として、メトキシ基、およびエトキシ基；
　Ｃ１～Ｃ６のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、２，２－ジフルオロエトキシ基、および２，２，２－トリフルオロエトキシ基；
　ならびにＣ３～Ｃ８のシクロアルコキシ基として、シクロプロピルオキシ基、およびシクロブトキシ基が挙げられる。 For more preferred specific examples of the substituent B, a cyano group;
As a C1-C6 alkoxy group, a methoxy group and an ethoxy group;
As a C1-C6 haloalkoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, and a 2,2,2-trifluoroethoxy group;
Also, examples of the C3-C8 cycloalkoxy group include a cyclopropyloxy group and a cyclobutoxy group.
　式（１）の「置換基Ｃ」とは、水酸基、シアノ基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、Ｃ３～Ｃ８のシクロアルコキシ基、Ｃ２～Ｃ６のアルコキシアルコキシ基、ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）、およびＲｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）、ＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、前記と同義である。）からなる群から選択される少なくとも１種を表す。 The “substituent C” in the formula (1) means a hydroxyl group, a cyano group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, C2. To C6 alkoxyalkoxy groups, RaRbN- (wherein Ra and Rb are as defined above), and Rc-L- (wherein Rc and L are as defined above), RdC ( ═O) — (wherein Rd has the same meaning as defined above) and represents at least one species selected from the group consisting of:
　中でも置換基Ｃは、シアノ基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、Ｃ３～Ｃ８のシクロアルコキシ基、Ｃ２～Ｃ６のアルコキシアルコキシ基、Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）、またはＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、前記と同義である。）が好ましく、
　特に、シアノ基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）、またはＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、前記と同義である。）が好ましい。 Among them, the substituent C is a cyano group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, a C2-C6 alkoxyalkoxy group, Rc- L- (wherein Rc and L have the same meanings as described above) or RdC (= O)-(wherein Rd has the same meaning as above),
In particular, a cyano group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, Rc-L- (wherein Rc and L have the same meanings as described above), or RdC (= O)-(here. And Rd has the same meaning as above.) Is preferred.
　置換基Ｃの各用語は前記の定義と同義である。 Each term of the substituent C has the same meaning as defined above.
　置換基Ｃの好ましい具体例に関しては、水酸基；
　シアノ基；
　Ｃ３～Ｃ８のシクロアルキル基として、シクロプロピル基、シクロブチル基、シクロペンチル基、およびシクロヘキシル基；
　Ｃ１～Ｃ６のアルコキシ基として、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブトキシ基、イソブトキシ基、およびｔ－ブトキシ基；
　Ｃ１～Ｃ６のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、２，２－ジフルオロエトキシ基、２，２，２－トリフルオロエトキシ基、３，３－ジフルオロプロピルオキシ基、および３，３，３－トリフルオロプロピルオキシ基；
　Ｃ３～Ｃ８のシクロアルコキシ基として、シクロプロピルオキシ基、シクロブトキシ基、シクロペンチルオキシ基、およびシクロヘキシルオキシ基；
　Ｃ２～Ｃ６のアルコキシアルコキシ基として、メトキシメトキシ基、エトキシメトキシ基、メトキシエトキシ基、エトキシエトキシ基、およびメトキシプロピルオキシ基；
　ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）として、アミノ基、メチルアミノ基、エチルアミノ基、プロピルアミノ基、イソプロピルアミノ基、（メトキシメチル）アミノ基、（２－メトキシエチル）アミノ基、（シアノメチル）アミノ基、（２－シアノエチル）アミノ基、ジメチルアミノ基、エチル（メチル）アミノ基、メチル（プロピル）アミノ基、イソプロピル（メチル）アミノ基、（メトキシメチル）メチルアミノ基、（２－メトキシエチル）メチルアミノ基、（シアノメチル）メチルアミノ基、（２－シアノエチル）メチルアミノ基、ジエチルアミノ基、エチル（プロピル）アミノ基、エチル（イソプロピル）アミノ基、エチル（メトキシメチル）アミノ基、エチル（２－メトキシエチル）アミノ基、（シアノメチル）エチルアミノ基、（２－シアノエチル）エチルアミノ基、２，２－ジフルオロエチルアミノ基、２，２，２－トリフルオロエチルアミノ基、シクロプロピルアミノ基、および（シクロプロピル）メチルアミノ基；
　Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）として、メチルチオ基、メタンスルフィニル基、メタンスルホニル基、エチルチオ基、エタンスルフィニル基、エタンスルホニル基、トリフルオロメチルチオ基、トリフルオロメタンスルフィニル基、およびトリフルオロメタンスルホニル基；
　ならびにＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、前記と同義である。）として、ホルミル基、アセチル基、メトキシアセチル基、シアノアセチル基、プロピオニル基、ジフルオロアセチル基、トリフルオロアセチル基、シクロプロパンカルボニル基、メトキシカルボニル基、エトキシカルボニル基、２，２－ジフルオロエトキシカルボニル基、２，２，２－トリフルオロエトキシカルボニル基、３，３，３－トリフルオロプロピルオキシカルボニル基、およびシクロプロピルオキシカルボニル基が挙げられる。 For preferred specific examples of the substituent C, a hydroxyl group;
Cyano group;
As a C3-C8 cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group;
A methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, and a t-butoxy group as the C1 to C6 alkoxy group;
As the C1 to C6 haloalkoxy group, difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 3,3-difluoropropyloxy group, and 3,3 , 3-trifluoropropyloxy group;
As a C3-C8 cycloalkoxy group, a cyclopropyloxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group;
As a C2-C6 alkoxyalkoxy group, a methoxymethoxy group, an ethoxymethoxy group, a methoxyethoxy group, an ethoxyethoxy group, and a methoxypropyloxy group;
As RaRbN- (wherein Ra and Rb are as defined above), an amino group, a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a (methoxymethyl) amino group, (2-methoxy) Ethyl) amino group, (cyanomethyl) amino group, (2-cyanoethyl) amino group, dimethylamino group, ethyl (methyl) amino group, methyl (propyl) amino group, isopropyl (methyl) amino group, (methoxymethyl) methylamino Group, (2-methoxyethyl) methylamino group, (cyanomethyl) methylamino group, (2-cyanoethyl) methylamino group, diethylamino group, ethyl (propyl) amino group, ethyl (isopropyl) amino group, ethyl (methoxymethyl) Amino group, ethyl (2-methoxyethyl) amino group, (sia Methyl) ethylamino group, (2-cyanoethyl) ethylamino group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, cyclopropylamino group, and (cyclopropyl) methylamino group;
Rc-L- (wherein Rc and L have the same meanings as defined above) is a methylthio group, a methanesulfinyl group, a methanesulfonyl group, an ethylthio group, an ethanesulfinyl group, an ethanesulfonyl group, a trifluoromethylthio group, or trifluoro. A romethanesulfinyl group and a trifluoromethanesulfonyl group;
And RdC (= O)-(wherein Rd has the same meaning as above), such as formyl group, acetyl group, methoxyacetyl group, cyanoacetyl group, propionyl group, difluoroacetyl group, trifluoroacetyl group, cyclo Propanecarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 3,3,3-trifluoropropyloxycarbonyl group, and cyclopropyloxy A carbonyl group may be mentioned.
　置換基Ｃのさらに好ましい具体例に関しては、水酸基；
　シアノ基；
　Ｃ３～Ｃ８のシクロアルキル基として、シクロペンチル基、およびシクロヘキシル基；
　Ｃ１～Ｃ６のアルコキシ基として、メトキシ基、エトキシ基、プロピルオキシ基、およびイソプロピルオキシ基；
　Ｃ１～Ｃ６のハロアルコキシ基として、ジフルオロメトキシ基、トリフルオロメトキシ基、２，２－ジフルオロエトキシ基、２，２，２－トリフルオロエトキシ基；
　Ｃ３～Ｃ８のシクロアルコキシ基として、シクロプロピルオキシ基、シクロブトキシ基；
　Ｃ２～Ｃ６のアルコキシアルコキシ基として、メトキシメトキシ基、エトキシメトキシ基、メトキシエトキシ基、およびエトキシエトキシ基；
　ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）として、ジメチルアミノ基、エチル（メチル）アミノ基、およびジエチルアミノ基；
　Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）として、メチルチオ基、メタンスルフィニル基、およびメタンスルホニル基；
　ＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、前記と同義である。）として、アセチル基、メトキシアセチル基、シアノアセチル基、ジフルオロアセチル基、トリフルオロアセチル基、メトキシカルボニル基、およびエトキシカルボニル基が挙げられる。 For more preferred specific examples of the substituent C, a hydroxyl group;
Cyano group;
As a C3 to C8 cycloalkyl group, a cyclopentyl group and a cyclohexyl group;
A methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group as the C1 to C6 alkoxy group;
As a C1 to C6 haloalkoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, a 2,2,2-trifluoroethoxy group;
As a C3-C8 cycloalkoxy group, a cyclopropyloxy group, a cyclobutoxy group;
As a C2-C6 alkoxyalkoxy group, a methoxymethoxy group, an ethoxymethoxy group, a methoxyethoxy group, and an ethoxyethoxy group;
RaRbN- (wherein Ra and Rb have the same meanings as defined above), as a dimethylamino group, an ethyl (methyl) amino group, and a diethylamino group;
Rc-L- (wherein Rc and L are as defined above) as a methylthio group, a methanesulfinyl group, and a methanesulfonyl group;
RdC (= O)-(wherein Rd has the same meaning as above), and includes acetyl group, methoxyacetyl group, cyanoacetyl group, difluoroacetyl group, trifluoroacetyl group, methoxycarbonyl group, and ethoxycarbonyl group. Is mentioned.
　以上説明したＲ１、Ｒ２、Ｒ３、Ｒ４、Ｘ、Ｚ、ｎ、置換基Ａ、置換基Ｂ、および置換基Ｃにおける好ましい範囲を任意に組み合わせて得られる化合物の範囲も、本発明の式（１）で表される化合物の範囲として、本明細書に記載されているものとする。 The range of the compound obtained by arbitrarily combining the preferable ranges of R1, R2, R3, R4, X, Z, n, the substituent A, the substituent B, and the substituent C described above is also represented by the formula (1) of the present invention. ) Shall be described in the present specification as the range of the compound represented by.
　式（１）で表される化合物は、軸不斉を有することがある。この際の異性体比は、単独または任意の割合の混合比であり、特に限定されることはない。 The compound represented by the formula (1) may have axial asymmetry. The isomer ratio at this time is a single ratio or a mixing ratio of an arbitrary ratio, and is not particularly limited.
　式（１）で表される化合物は、不斉原子を含むことがある。この際の異性体比は、単独または任意の割合の混合比であり、特に限定されることはない。 The compound represented by the formula (1) may contain an asymmetric atom. The isomer ratio at this time is a single ratio or a mixing ratio of an arbitrary ratio, and is not particularly limited.
　式（１）で表される化合物は、幾何異性体を含むことがある。この際の異性体比は、単独または任意の割合の混合比であり、特に限定されることはない。 The compound represented by the formula (1) may include geometrical isomers. The isomer ratio at this time is a single ratio or a mixing ratio of an arbitrary ratio, and is not particularly limited.
　式（１）で表される化合物は、塩を形成できることがある。塩酸、硫酸、酢酸、フマル酸、マレイン酸のような酸塩や、ナトリウム、カリウム、カルシウムのような金属塩等が例示されるが、農園芸用殺菌剤として使用できる限り、特に限定されることはない。 The compound represented by the formula (1) may be capable of forming a salt. Acid salts such as hydrochloric acid, sulfuric acid, acetic acid, fumaric acid, and maleic acid, and metal salts such as sodium, potassium, and calcium are exemplified, but are not particularly limited as long as they can be used as agricultural and horticultural fungicides. There is no.
　次に、本発明の具体的な化合物は、表１に示す構造式と、表２に示すフェニル基上の置換基（Ｒ３）、および表３に示すＺとの組み合わせによって表される。なお、表１におけるＸは酸素原子または硫黄原子を表し、Ｐｈは下記部分構造
Figure JPOXMLDOC01-appb-C000009
を表す。 Next, a specific compound of the present invention is represented by a combination of the structural formula shown in Table 1, the substituent (R3) on the phenyl group shown in Table 2, and Z shown in Table 3. In addition, X in Table 1 represents an oxygen atom or a sulfur atom, and Ph represents the following partial structure.
Figure JPOXMLDOC01-appb-C000009
Represents
　これらの化合物は例示のためのものであり、本発明はこれらに限定されるものではない。 These compounds are merely examples, and the present invention is not limited to these.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
　以下に、式（１）で表される化合物の製造方法を例示する。本発明化合物の製造法は、製造方法Ａ～製造方法ＡＣに限定されるものではない。 The method for producing the compound represented by the formula (1) is illustrated below. The method for producing the compound of the present invention is not limited to the production methods A to AC.
［製造方法Ａ］
Figure JPOXMLDOC01-appb-C000037
　式中、Ｒ１ａはハロゲン原子を表し、ＨａｌＲはハロゲン化剤を表し、Ｒ３、Ｘ、Ｚおよびｎは前記と同義である。 [Production method A]
Figure JPOXMLDOC01-appb-C000037
In the formula, R1a represents a halogen atom, HalR represents a halogenating agent, and R3, X, Z and n have the same meanings as described above.
　製造方法Ａは、式（２ｂ）で表される製造中間体を得る方法であって、式（２ａ）で表される化合物とハロゲン化剤（ＨａｌＲ）とを、溶媒中で反応させる方法を含む製造方法である。 Production method A is a method of obtaining a production intermediate represented by formula (2b), and includes a method of reacting the compound represented by formula (2a) with a halogenating agent (HalR) in a solvent. It is a manufacturing method.
　本反応に使用する式（２ａ）で表される化合物は、例えば、シンセシス（ｓｙｎｔｈｅｓｉｓ）、４４巻、２１８１－２１８４頁（２０１２）．、オルガニック　レターズ（Ｏｒｇａｎｉｃ　Ｌｅｔｔｅｒｓ）、第４巻、１０号、３３０９－３３１１（２００２）．、またはテトラヘドロン　レターズ（Ｔｅｔｒａｈｅｄｒｏｎ　Ｌｅｔｔｅｒｓ）、第４０巻、７８３１－７８３４頁（１９９９）．等の非特許文献や参考例を参照にして入手することができる。 The compound represented by the formula (2a) used in this reaction is described in, for example, Synthesis, Vol. 44, pages 2181-2184 (2012). , Organic Letters, Volume 4, Issue 10, 3309-3311 (2002). , Or Tetrahedron Letters, 40, 7831-7834 (1999). Non-patent literatures such as the above and reference examples can be obtained.
　本反応に使用するハロゲン化剤としては、セレクトロフルオル（Ｎ－フルオロ－Ｎ’－トリエチレンジアミン　ビス（テトラフルオロボラート））、Ｎ－クロロスクシンイミド、Ｎ－ブロモスクシンイミド、Ｎ－ヨードスクシンイミド、１，３－ジクロロ－５，５－ジメチルヒダントイン、１，３－ジブロモ－５，５－ジメチルヒダントイン、１，３－ジヨード－５，５－ジメチルヒダントイン、臭素、ヨウ素等が挙げられる。 As the halogenating agent used in this reaction, selectrofluor (N-fluoro-N'-triethylenediamine bis (tetrafluoroborate)), N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 1 , 3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, bromine, iodine and the like.
　本反応に使用するハロゲン化剤の量は、式（２ａ）で表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に制限されることはないが、通常、１当量以上２０当量以下である。ただし、ヒダントインを含むハロゲン化剤の量は、０．５当量以上あれば、目的とする反応が進行する限りにおいて特に制限されることはなく、通常、１当量以上１０当量以下である。 The amount of the halogenating agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (2a). It is 1 equivalent or more and 20 equivalents or less. However, the amount of the halogenating agent containing hydantoin is not particularly limited as long as the intended reaction proceeds, as long as it is 0.5 equivalent or more, and is usually 1 equivalent or more and 10 equivalents or less.
　本反応に使用するハロゲン化剤がヨウ素化剤である場合、塩酸、硫酸等の無機酸類や、酢酸、トリフルオロ酢酸、メタンスルホン酸、トリフルオロメタンスルホン酸等の有機酸のような酸を加えることができる。 When the halogenating agent used in this reaction is an iodizing agent, add inorganic acids such as hydrochloric acid and sulfuric acid, and acids such as organic acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid and trifluoromethanesulfonic acid. You can
　本反応に使用するハロゲン化剤がヨウ素化剤である場合に使用する酸の量は、式（２ａ）で表される化合物に対して０．０１当量以上あれば、目的とする反応が進行する限りにおいて特に制限されることはないが、通常、０．１当量以上３当量以下である。 When the amount of the acid used when the halogenating agent used in this reaction is an iodizing agent is 0.01 equivalent or more with respect to the compound represented by the formula (2a), the desired reaction proceeds. The amount is not particularly limited as long as it is, but is usually 0.1 equivalent or more and 3 equivalents or less.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、硫酸、酢酸、トリフルオロ酢酸、メタンスルホン酸、トリフルオロメタンスルホン酸等の酸性系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、メタノール、エタノール、イソプロパノール等のアルコール系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、アセトニトリル等のニトリル系溶媒、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド系溶媒、１，３－ジメチル－２－イミダゾリジノン等のウレア系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but acidic solvents such as sulfuric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, diethyl ether, etc. , Ether solvents such as diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran and dioxane, alcohol solvents such as methanol, ethanol and isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene. , Ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitrile solvents such as acetonitrile, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide 1,3-dimethyl-2-urea-based solvent-imidazolidinone, dichloromethane, dichloroethane, chloroform, and halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（２ａ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less by weight with respect to the compound represented by the formula (2a). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、０℃以上１５０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（２ｂ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (2b) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（２ｂ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (2b) obtained above can be distilled under reduced pressure to remove the solvent.
　溶媒留去後に得られた式（２ｂ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (2b) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法Ｂ］
Figure JPOXMLDOC01-appb-C000038
　式中、Ｏｘは酸化剤を表し、Ｒ２ａは、水素原子、シアノ基、ハロゲン原子、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、Ｃ２～Ｃ６のハロアルキニル基、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、Ｒｃ－Ｌ－（ここで、ＲｃはおよびＬは、前記と同義である。）、またはＲｇＣ（＝Ｏ）－（ここで、Ｒｇは、前記と同義である。）を表し、Ｒ１、Ｒ３、Ｘ、Ｚおよびｎは前記と同義である。 [Production method B]
Figure JPOXMLDOC01-appb-C000038
In the formula, Ox represents an oxidizing agent, R2a represents a hydrogen atom, a cyano group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, or a substituent A. An optionally substituted C3 to C8 cycloalkyl group, an optionally substituted C2 to C6 alkenyl group, an optionally substituted C2 to C6 haloalkenyl group, an optionally substituted C2 To C6 alkynyl group, C2 to C6 haloalkynyl group, C1 to C6 alkoxy group optionally substituted with substituent A, Rc-L- (wherein Rc and L have the same meanings as described above). , Or RgC (═O) — (wherein Rg has the same meaning as described above), and R1, R3, X, Z and n have the same meanings as described above.
　製造方法Ｂは、式（１ａ）で表される化合物を得る方法であって、式（２ｃ）で表される化合物と酸化剤（Ｏｘ）とを、溶媒中で反応させることを含む製造方法である。 Production method B is a method for obtaining a compound represented by formula (1a), which comprises reacting the compound represented by formula (2c) with an oxidizing agent (Ox) in a solvent. is there.
　本反応に使用する酸化剤としては、ペルオキソ二硫酸カリウム等の過酸類、ＩＢＸ（２－ヨードキシ安息香酸）、ＤＭＰ（１，１，１－トリアセトキシ－１，１－ジヒドロ－１，２－ベンズヨードキソール－３（１Ｈ）－オン）等の超原子価ヨウ素化合物類、塩素、臭素、ヨウ素等のハロゲン類、アゾビスイソブチロニトリル、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、過酸化ベンゾイル等のラジカル開始剤とＮ－クロロスクシンイミド、Ｎ－ブロモスクシンイミド、Ｎ－ヨードスクシンイミド、１，３－ジクロロ－５，５－ジメチルヒダントイン、１，３－ジブロモ－５，５－ジメチルヒダントイン、１，３－ジヨード－５，５－ジメチルヒダントイン等のハロゲン化剤とを組み合わせたもの、二酸化マンガン等の金属酸化物類、２，３－ジクロロ－５，６－ジシアノ－ｐ－ベンゾキノン等のベンゾキノン類等を使用することができる。 Examples of the oxidizing agent used in this reaction include peracids such as potassium peroxodisulfate, IBX (2-iodoxybenzoic acid), DMP (1,1,1-triacetoxy-1,1-dihydro-1,2-benz). Hypervalent iodine compounds such as iodoxol-3 (1H) -one), halogens such as chlorine, bromine and iodine, azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), a radical initiator such as benzoyl peroxide and N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo- Combined with halogenating agents such as 5,5-dimethylhydantoin and 1,3-diiodo-5,5-dimethylhydantoin Metal oxides such as cancer, may be used benzoquinones such as 2,3-dichloro-5,6-dicyano -p- benzoquinone.
　以下、酸化剤が過酸類である方法について説明する。ここではペルオキソ二硫酸カリウムについて記載する。 The following explains the method in which the oxidizing agent is a peracid. Here, potassium peroxodisulfate will be described.
　本反応に使用するペルオキソ二硫酸カリウムの量は、式（２ｃ）で表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上１０当量以下である。 The amount of potassium peroxodisulfate used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (2c). It is 1 equivalent or more and 10 equivalents or less.
　本反応を実施する際には、塩酸、硫酸等の酸を加えることが必要である。その際の酸の量は、ペルオキソ二硫酸カリウムに対して、１価の酸であれば２当量、２価の酸であれば１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはない。 -When carrying out this reaction, it is necessary to add acids such as hydrochloric acid and sulfuric acid. The amount of the acid at that time is not particularly limited as long as the intended reaction proceeds if the amount of the acid is 2 equivalents for the monovalent acid with respect to potassium peroxodisulfate and 1 equivalent or more for the divalent acid. It will not be done.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、メタノール、エタノール、イソプロパノール等のアルコール系溶媒、アセトニトリル等のニトリル系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but examples thereof include alcohol solvents such as methanol, ethanol and isopropanol, and nitrile solvents such as acetonitrile. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（２ｃ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2c). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、０℃以上１５０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（１ａ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (1a) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（１ａ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (1a) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
　溶媒留去後に得られた式（１ａ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (1a) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
　以下、酸化剤が超原子価ヨウ素化合物類である方法について説明するが、ここではＩＢＸについて記載する。 The following describes the method in which the oxidizing agent is a hypervalent iodine compound, but here IBX is described.
　本反応に使用する酸化剤の量は、式（２ｃ）に表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上２０当量以下である。 The amount of the oxidizing agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (2c), but it is usually 1 It is equal to or more than 20 equivalents.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジメチルスルホキシド、スルホラン等の硫黄系溶媒系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ester solvent such as ethyl acetate, isopropyl acetate or butyl acetate, a sulfur solvent system such as dimethyl sulfoxide or sulfolane. A solvent etc. are mentioned. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（２ｃ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2c). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、０℃以上１５０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。また、本反応において、分液操作は必須ではない。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. In this reaction, a liquid separation operation is not essential.
　前記で得られた式（１ａ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (1a) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（１ａ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (1a) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
　溶媒留去後に得られた式（１ａ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (1a) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
　以下、酸化剤がハロゲン類である方法について説明する。 The following explains the method in which the oxidizing agent is a halogen.
　本反応に使用する酸化剤の量は、式（２ｃ）で表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上２０当量以下である。 The amount of the oxidizing agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (2c), but it is usually 1 It is equal to or more than 20 equivalents.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、酢酸等の酸性系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but acidic solvents such as acetic acid, benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc. , Halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（２ｃ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2c). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、－１０℃以上１５０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -10 ° C or higher and 150 ° C or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。また、本反応において、分液操作は必須ではない。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. In this reaction, a liquid separation operation is not essential.
　前記で得られた式（１ａ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (1a) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（１ａ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (1a) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
　溶媒留去後に得られた式（１ａ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (1a) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
　以下、酸化剤がラジカル開始剤とハロゲン化剤との組み合わせである方法について説明する。 Described below is the method in which the oxidizing agent is a combination of a radical initiator and a halogenating agent.
　本反応に使用するラジカル開始剤とハロゲン化剤の量は、それぞれ、式（２ｃ）で表される化合物に対して０．０１当量以上と１．０当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはない。通常、ラジカル開始剤が０．０１当量以上１当量以下であり、ハロゲン化剤が１当量以上３当量以下である。ただし、ヒダントインを含むハロゲン化剤の量は、０．５当量以上あれば、目的とする反応が進行する限りにおいて特に制限されることはなく、通常、１当量以上１．５当量以下である。 The amounts of the radical initiator and the halogenating agent used in this reaction are 0.01 equivalents or more and 1.0 equivalents or more, respectively, with respect to the compound represented by the formula (2c), and the desired reaction proceeds. There is no particular limitation as long as it does. Usually, the amount of the radical initiator is from 0.01 to 1 equivalent, and the amount of the halogenating agent is from 1 to 3 equivalents. However, the amount of the halogenating agent containing hydantoin is not particularly limited as long as the intended reaction proceeds, as long as it is 0.5 equivalent or more, and is usually 1 equivalent or more and 1.5 equivalents or less.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、クロロベンゼン、ジクロロベンゼン等のハロゲン化ベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but halogenated benzene solvents such as chlorobenzene and dichlorobenzene, and ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate. Examples thereof include solvents, halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, and hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（２ｃ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2c). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、２０℃以上１５０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 20 ° C. or higher and 150 ° C. or lower or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- It is possible to add an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane and chloroform, a hydrocarbon solvent such as hexane, heptane, cyclohexane and methylcyclohexane, which is incompatible with water. It is possible. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（１ａ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (1a) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（１ａ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (1a) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
　溶媒留去後に得られた式（１ａ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (1a) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
　以下、酸化剤が金属酸化物類である方法について説明する。ここでは二酸化マンガンについて記載する。 Hereafter, the method in which the oxidizing agent is a metal oxide will be described. Here, manganese dioxide will be described.
　本反応に使用する酸化剤の量は、式（２ｃ）に表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上２００当量以下である。 The amount of the oxidizing agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (2c), but it is usually 1 It is equal to or more than 200 equivalents.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, dichloromethane, dichloroethane, chloroform, Examples thereof include halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（２ｃ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2c). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、０℃以上１５０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、溶解していない金属類を濾過することにより除去することが可能である。さらに、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。また、本反応において、分液操作は必須ではない。 As a post-treatment of the reaction, it is possible to remove undissolved metals by filtering. Furthermore, a liquid separation operation can be performed by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. In this reaction, a liquid separation operation is not essential.
　前記で得られた式（１ａ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (1a) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（１ａ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (1a) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
　溶媒留去後に得られた式（１ａ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (1a) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
　以下、酸化剤がベンゾキノン類である方法について説明する。
　本反応に使用する酸化剤の量は、式（２ｃ）で表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上２０当量以下である。 Hereinafter, a method in which the oxidizing agent is a benzoquinone will be described.
The amount of the oxidizing agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (2c), but it is usually 1 It is equal to or more than 20 equivalents.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, dichloromethane, dichloroethane, chloroform, Examples thereof include halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（２ｃ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2c). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、０℃以上１５０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。また、本反応において、分液操作は必須ではない。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. In this reaction, a liquid separation operation is not essential.
　前記で得られた式（１ａ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (1a) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（１ａ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (1a) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
　溶媒留去後に得られた式（１ａ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (1a) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法Ｃ］
Figure JPOXMLDOC01-appb-C000039
　式中、Ｒ３ａはハロゲン原子を表し、Ｒ３ｂは置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、Ｃ２～Ｃ６のハロアルケニルオキシ基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、またはＣ３～Ｃ６のハロアルキニルオキシ基を表し、Ｑは水素原子または金属を表し、ｏは、０～４の整数（ただし、ｏが２以上の場合、Ｒ３はそれぞれ独立している。）を表し、Ｒ１、Ｒ２、Ｒ３、ＸおよびＺは前記と同義である。 [Production method C]
Figure JPOXMLDOC01-appb-C000039
In the formula, R3a represents a halogen atom, R3b represents a C1 to C6 alkoxy group optionally substituted by a substituent C, a C1 to C6 haloalkoxy group, a C3 to C8 optionally substituted by a substituent C. A cycloalkoxy group, a C2-C6 alkenyloxy group optionally substituted with a substituent C, a C2-C6 haloalkenyloxy group, a C3-C6 alkynyloxy group optionally substituted with a substituent C, Alternatively, it represents a C3 to C6 haloalkynyloxy group, Q represents a hydrogen atom or a metal, and o represents an integer of 0 to 4 (provided that when o is 2 or more, R3s are independent of each other). , R1, R2, R3, X and Z are as defined above.
　製造方法Ｃは、Ｒ３ｂが置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、Ｃ２～Ｃ６のハロアルケニルオキシ基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、またはＣ３～Ｃ６のハロアルキニルオキシ基である式（１ｃ）で表される化合物を得る方法であって、式（１ｂ）で表される化合物とＲ３ｂ－Ｑとを、溶媒中で反応させることを含む製造方法である。 The production method C is such that R3b is a C1 to C6 alkoxy group optionally substituted with a substituent C, a C1 to C6 haloalkoxy group, a C3 to C8 cycloalkoxy group optionally substituted with a substituent C, A C2 to C6 alkenyloxy group optionally substituted with a substituent C, a C2 to C6 haloalkenyloxy group, a C3 to C6 alkynyloxy group optionally substituted with a substituent C, or a C3 to C6 A method for obtaining a compound represented by formula (1c) which is a haloalkynyloxy group, the method comprising reacting the compound represented by formula (1b) with R3b-Q in a solvent. .
　本反応で使用されるＲ３ｂ－Ｑは、市販品として入手または公知の方法で製造できる。好ましいＱは、水素原子、またはナトリウム、カリウム等のアルカリ金属類である。 R3b-Q used in this reaction can be obtained as a commercial product or can be produced by a known method. Preferred Q is a hydrogen atom or an alkali metal such as sodium or potassium.
　本反応で使用されるＲ３ｂ－Ｑの量は、式（１ｂ）で表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上３０当量以下である。また、Ｑが水素原子を表すときは、溶媒として使用することができる。 The amount of R3b-Q used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more based on the compound represented by the formula (1b). It is 1 equivalent or more and 30 equivalents or less. When Q represents a hydrogen atom, it can be used as a solvent.
　本反応に使用する塩基は、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、水素化ナトリウム等の無機塩基類が好ましい。また、Ｑがアルカリ金属類のときは、塩基の使用は必須ではない。 The base used in this reaction is preferably an inorganic base such as sodium carbonate, potassium carbonate, cesium carbonate or sodium hydride. When Q is an alkali metal, the use of a base is not essential.
　本反応に使用する塩基の量は、式（１ｂ）で表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上３０当量以下である。 The amount of the base used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1b), but usually 1 equivalent It is above 30 equivalents.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、Ｒ３ｂ－Ｈ（式中、Ｒ３ｂは前記と同義である。）で表されるアルコール系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、アセトニトリル等のニトリル系溶媒、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド系溶媒、１，３－ジメチル－２－イミダゾリジノン等のウレア系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ジメチルスルホキシド、スルホラン等の硫黄系溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but an alcohol solvent represented by R3b-H (in the formula, R3b has the same meaning as above), Ether-based solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, benzene-based solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ethyl acetate, isopropyl acetate, butyl acetate Such as ester-based solvents, nitrile-based solvents such as acetonitrile, amide-based solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone Urea-based solvent, dichloromethane, dichloromethane Ethane, chloroform, halogenated solvents such as carbon tetrachloride, dimethyl sulfoxide, sulfur-based solvents such as sulfolane, acetone, methyl ethyl ketone, ketone solvents such as methyl isobutyl ketone. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（１ｂ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (1b). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、０℃以上１５０℃以下または溶媒の沸点以下である。
反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 The temperature at which this reaction is performed is not particularly limited as long as the desired reaction proceeds, but is usually 0 ° C or higher and 150 ° C or lower or the boiling point of the solvent or lower.
As a post-treatment of the reaction, a liquid separation operation can be performed by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate or the like is dissolved, sodium thiosulfate or sulfite is used. An aqueous solution in which a salt containing a sulfur atom such as sodium is dissolved, a saline solution or the like can be optionally used. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- Ether-based solvents such as t-butyl ether, halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane that are not compatible with water. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（１ｃ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (1c) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（１ｃ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (1c) obtained above can be distilled under reduced pressure to remove the solvent.
　溶媒留去後に得られた式（１ｃ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (1c) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法Ｄ］
Figure JPOXMLDOC01-appb-C000040
　式中、Ｒ３ｃはＣ１～Ｃ６のアルコキシ基を表し、Ｒ１、Ｒ２、Ｒ３、Ｘ、Ｚおよびｏは前記と同義である。 [Production method D]
Figure JPOXMLDOC01-appb-C000040
In the formula, R3c represents a C1 to C6 alkoxy group, and R1, R2, R3, X, Z and o have the same meanings as described above.
　製造方法Ｄは、水酸基を有する式（１ｅ）で表される化合物を得る方法であって、式（１ｄ）で表される化合物と酸とを、溶媒中で反応させることによって得ることを含む製造方法である。 Production method D is a method for obtaining a compound represented by formula (1e) having a hydroxyl group, which comprises obtaining the compound represented by formula (1d) and an acid in a solvent. Is the way.
　本反応に使用する酸として、三塩化ホウ素、三臭化ホウ素等のハロゲン化ホウ素類等が挙げられる。 The acids used in this reaction include boron halides such as boron trichloride and boron tribromide.
　本反応に使用する酸の量は、式（１ｄ）で表される化合物に対して１当量以上あればよく、目的とする反応が進行する限りにおいて特に制限されることはないが、通常、１当量以上１０当量以下である。 The amount of the acid used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1d), and is not particularly limited as long as the intended reaction proceeds, but it is usually 1 It is equal to or more than 10 equivalents.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、アセトニトリル等のニトリル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is a benzene solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene, or dichlorobenzene, and a nitrile solvent such as acetonitrile. , Halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, and hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（１ｄ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (1d). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、－８０℃以上１００℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 100 ° C or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（１ｅ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (1e) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（１ｅ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (1e) obtained above can be distilled under reduced pressure to remove the solvent.
　溶媒留去後に得られた式（１ｅ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (1e) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法Ｅ］
Figure JPOXMLDOC01-appb-C000041
　式中、Ｒ３ｄは、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニル基、Ｃ３～Ｃ６のハロアルキニル基、またはＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、前記と同義である。）を表し、Ｌｖはメタンスルホニル基、トリフルオロメタンスルホニル基、ｐ‐トルエンスルホニル基、ハロゲン原子等の脱離基を表し、Ｒ１、Ｒ２、Ｒ３、Ｘ、Ｚおよびｏは前記と同義である。 [Production method E]
Figure JPOXMLDOC01-appb-C000041
In the formula, R3d is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent A C2-C6 alkenyl group optionally substituted with C, a C2-C6 haloalkenyl group, a C3-C6 alkynyl group optionally substituted with a substituent C, a C3-C6 haloalkynyl group, or RdC (= O)-(wherein Rd has the same meaning as described above), Lv represents a leaving group such as a methanesulfonyl group, a trifluoromethanesulfonyl group, a p-toluenesulfonyl group and a halogen atom, and R1 , R2, R3, X, Z and o are as defined above.
　製造方法Ｅは、Ｒ３ｄが、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニル基、Ｃ３～Ｃ６のハロアルキニル基、またはＲｄＣ（＝Ｏ）－（Ｒｄは、前記と同義である。）である式（１ｆ）で表される化合物を得る方法であって、式（１ｅ）で表される化合物とＲ３ｄ－Ｌｖとを、塩基存在下、溶媒中で反応させることを含む製造方法である。 In the production method E, R3d is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, A C2 to C6 alkenyl group optionally substituted with a substituent C, a C2 to C6 haloalkenyl group, a C3 to C6 alkynyl group optionally substituted with a substituent C, a C3 to C6 haloalkynyl group, Alternatively, a method for obtaining a compound represented by the formula (1f), which is RdC (═O)-(Rd has the same meaning as described above), comprising the step of reacting the compound represented by the formula (1e) with R3d-Lv. In a solvent in the presence of a base.
　本反応に使用するＲ３ｄ－Ｌｖは、市販品として入手または公知の方法で製造できる。 R3d-Lv used in this reaction can be obtained as a commercial product or can be produced by a known method.
　本反応に使用するＲ３ｄ－Ｌｖの量は、式（１ｅ）で表される化合物に対して１当量以上あればよく、目的とする反応が進行する限りにおいて特に制限されることはないが、通常、１当量以上１０当量以下である。 The amount of R3d-Lv used in this reaction may be 1 equivalent or more relative to the compound represented by the formula (1e), and is not particularly limited as long as the intended reaction proceeds, but it is usually It is 1 equivalent or more and 10 equivalents or less.
　本反応に使用する塩基として、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、水素化ナトリウム等の無機塩基類や、トリエチルアミン、トリブチルアミン、ジイソプロピルエチルアミン、ピリジン、４－ジメチルアミノピリジン、コリジン、ルチジン等の有機塩基類が例示されるが、目的とする反応が進行する限りにおいて特に限定されることはない。 As the base used in this reaction, inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate and sodium hydride, and organic bases such as triethylamine, tributylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, collidine and lutidine Examples thereof include, but are not particularly limited as long as the desired reaction proceeds.
　本反応に使用する塩基の量は、式（１ｅ）で表される化合物に対して１当量以上あればよく、目的とする反応が進行する限りにおいて特に制限されることはないが、通常、１当量以上１０当量以下である。 The amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1e) and is not particularly limited as long as the intended reaction proceeds, but it is usually 1 It is equal to or more than 10 equivalents.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、メタノール、エタノール、イソプロパノール等のアルコール系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、アセトニトリル等のニトリル系溶媒、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド系溶媒、１，３－ジメチル－２－イミダゾリジノン等のウレア系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ジメチルスルホキシド、スルホラン等の硫黄系溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Methanol, ethanol, alcohol solvents such as isopropanol, benzene, toluene, xylene, mesitylene, chlorobenzene, benzene solvents such as dichlorobenzene, ethyl acetate, isopropyl acetate, ester solvents such as butyl acetate, nitrile solvents such as acetonitrile, Amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, dichloromethane, dichloroethane, Chloroform, halogenated solvents such as carbon tetrachloride, dimethyl sulfoxide, sulfur-based solvents such as sulfolane, acetone, methyl ethyl ketone, ketone solvents such as methyl isobutyl ketone. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（１ｅ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (1e). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、－２０℃以上１５０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -20 ° C or higher and 150 ° C or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（１ｆ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (1f) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（１ｆ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (1f) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
　溶媒留去後に得られた式（１ｆ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。
［製造方法Ｆ］
Figure JPOXMLDOC01-appb-C000042
　式中、Ｒ２ｂはハロゲン原子を表し、ＨａｌＲ、Ｒ１、Ｘ、Ｚ、Ｒ３およびｎは前記と同義である。 The reaction mixture containing the compound represented by the formula (1f) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
[Production method F]
Figure JPOXMLDOC01-appb-C000042
In the formula, R2b represents a halogen atom, and HalR, R1, X, Z, R3 and n have the same meanings as described above.
　製造方法Ｆは、式（１ｈ）で表される化合物を得る方法であって、式（１ｇ）で表される化合物とハロゲン化剤（ＨａｌＲ）とを、溶媒中で反応させる方法を含む製造方法である。 Production method F is a method for obtaining the compound represented by formula (1h), which comprises reacting the compound represented by formula (1g) with a halogenating agent (HalR) in a solvent. Is.
　製造方法Ａにおける式（２ａ）で表される化合物を、式（１ｇ）で表される化合物に代えて使用することにより、製造方法Ａに準じて製造方法Ｆを実施することができる。 By using the compound represented by the formula (2a) in the production method A instead of the compound represented by the formula (1g), the production method F can be carried out according to the production method A.
［製造方法Ｇ］
Figure JPOXMLDOC01-appb-C000043
　式中、ＨａｌＲ、Ｒ１ａ、Ｒ２、Ｒ３、Ｘ、Ｚおよびｎは前記と同義である。 [Production method G]
Figure JPOXMLDOC01-appb-C000043
In the formula, HalR, R1a, R2, R3, X, Z and n have the same meanings as described above.
　製造方法Ｇは、式（１ｊ）で表される化合物を得る方法であって、式（１ｉ）で表される化合物とハロゲン化剤（ＨａｌＲ）とを、溶媒中で反応させる方法を含む製造方法である。 Production method G is a method for obtaining the compound represented by formula (1j), which comprises reacting the compound represented by formula (1i) with a halogenating agent (HalR) in a solvent. Is.
　製造方法Ａにおける式（２ａ）で表される化合物を、式（１ｉ）で表される化合物に代えて使用することにより、製造方法Ａに準じて製造方法Ｇを実施することができる。 By using the compound represented by the formula (2a) in the production method A instead of the compound represented by the formula (1i), the production method G can be carried out according to the production method A.
［製造方法Ｈ］
Figure JPOXMLDOC01-appb-C000044
　式中、Ｒ１ｃは、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基を表し、Ｒ１ｃ－Ｂは有機ボロン酸類を表し、Ｒ２ｃは、水素原子、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、Ｃ２～Ｃ６のハロアルキニル基、Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）、またはＲｇＣ（＝Ｏ）－（ここで、Ｒｇは、前記と同義である。）を表し、破線部を含む結合は単結合または２重結合を表し、Ｒ１ａ、Ｒ３、Ｘ、Ｚおよびｎは前記と同義である。 [Production method H]
Figure JPOXMLDOC01-appb-C000044
In the formula, R1c represents a C1 to C6 alkyl group which may be optionally substituted with a substituent A, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group which may be optionally substituted with a substituent A, a substituent A C2 to C6 alkenyl group which may be appropriately substituted with A, a C2 to C6 haloalkenyl group, R1c-B represents an organic boronic acid, R2c is a hydrogen atom, or a substituent A may be appropriately substituted. A good C1 to C6 alkyl group, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent A, a C2 to C6 alkenyl group optionally substituted with a substituent A, A C2-C6 haloalkenyl group, a C2-C6 alkynyl group optionally substituted with a substituent A, a C2-C6 haloalkynyl group, Rc-L- (wherein Rc and L have the same meanings as defined above). Or RgC (= O)-(wherein Rg has the same meaning as defined above), the bond containing the broken line represents a single bond or a double bond, and R1a, R3, X, Z And n are as defined above.
　ここで、破線部を含む結合とは、
Figure JPOXMLDOC01-appb-C000045
で表される箇所を表す。 Here, the combination including the broken line part means
Figure JPOXMLDOC01-appb-C000045
Represents a portion represented by.
　製造方法Ｈは、Ｒ１ｃが、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基である式（３ｂ）で表される化合物を得る方法であって、式（３ａ）で表される化合物と有機ボロン酸類（Ｒ１ｃ－Ｂ）とを、遷移金属類および塩基の存在下、溶媒中で反応させる鈴木－宮浦カップリングによって得ることを含む製造方法である。 In the production method H, R1c is a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent A, A method for obtaining a compound represented by the formula (3b), which is a C2 to C6 alkenyl group and a C2 to C6 haloalkenyl group optionally substituted with a substituent A, which is represented by the formula (3a) It is a production method which comprises obtaining a compound and an organic boronic acid (R1c-B) by Suzuki-Miyaura coupling in which a transition metal and a base are reacted in a solvent.
　式（３ａ）中、好ましいＲ１ａは、塩素原子、臭素原子、またはヨウ素原子である。
　本反応に使用するＲ１ｃ－Ｂは、有機ボロン酸や有機ボロン酸エステル等の有機ボロン酸類を表し、市販品として入手または公知の方法で製造できる。 In formula (3a), preferred R1a is a chlorine atom, a bromine atom, or an iodine atom.
R1c-B used in this reaction represents an organic boronic acid such as an organic boronic acid or an organic boronic acid ester, which can be obtained as a commercial product or can be produced by a known method.
　本反応に使用するＲ１ｃ－Ｂの量は、式（３ａ）で表される化合物に対して、１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上１０当量以下である。 The amount of R1c-B used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (3a). It is 1 equivalent or more and 10 equivalents or less.
　本反応に使用する遷移金属類は、パラジウム、ニッケル、ルテニウム等であり、配位子を有してよい。好ましくは、酢酸パラジウム、［１，１’－ビス（ジフェニルホスフィノ）フェロセン］パラジウムジクロリド、トリス（ジベンジリデンアセトン）ジパラジウム、テトラキス（トリフェニルホスフィン）パラジウム、ビス（トリフェニルホスフィン）パラジウムジクロリド等のパラジウム類が挙げられる。 The transition metals used in this reaction are palladium, nickel, ruthenium, etc., and may have a ligand. Preferred are palladium acetate, [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride and the like. Examples include palladiums.
　本反応に使用する遷移金属類の量は、式（３ａ）で表される化合物に対して、通常、０．００１当量以上１当量以下であるが、目的とする反応が進行する限りにおいて特に限定されることはない。 The amount of the transition metal used in this reaction is usually 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (3a), but is not particularly limited as long as the intended reaction proceeds. It will not be done.
　本反応を効率的に進行させるために、トリフェニルホスフィン、トリシクロヘキシルホスフィン等のホスフィン配位子を添加することができる。 A phosphine ligand such as triphenylphosphine or tricyclohexylphosphine can be added to allow the reaction to proceed efficiently.
　本反応に使用するホスフィン配位子の量は、式（３ａ）で表される化合物に対して、通常、０．００１当量以上１当量以下であるが、目的とする反応が進行する限りにおいて特に限定されることはない。 The amount of the phosphine ligand used in this reaction is usually 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (3a), but as long as the intended reaction proceeds, There is no limitation.
　本反応に使用する塩基は、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、リン酸三カリウムのような無機塩基類やナトリウムメトキシド、ナトリウムエトキシド、カリウム　ｔ－ブトキシド等の金属アルコキシド類等である。 The bases used in this reaction are inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate and tripotassium phosphate, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide.
　本反応に使用する塩基の量は、式（３ａ）で表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上５０当量以下である。 The amount of the base used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more relative to the compound represented by the formula (3a), but usually 1 equivalent It is above 50 equivalents.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、水溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether such as water solvent, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane. Examples of the solvent include benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（３ａ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (3a). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、３０℃以上２００℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 30 ° C. or higher and 200 ° C. or lower or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。また、濾過操作を行うことにより、不溶物を除去することも可能であるが必須ではない。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. It is also possible, but not essential, to remove insolubles by performing a filtration operation.
　前記で得られた式（３ｂ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (3b) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（３ｂ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (3b) obtained above can be distilled under reduced pressure to remove the solvent.
　溶媒留去後に得られた式（３ｂ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (3b) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法Ｉ］
Figure JPOXMLDOC01-appb-C000046
　式中、Ｒ１ｄは置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、またはＣ２～Ｃ６のハロアルキニル基を表し、Ｒ１ａ、Ｒ２ｃ、Ｒ３、Ｘ、Ｚ、ｎおよび破線部は前記と同義である。 [Manufacturing method I]
Figure JPOXMLDOC01-appb-C000046
In the formula, R1d represents a C2-C6 alkynyl group which may be appropriately substituted with a substituent A, or a C2-C6 haloalkynyl group, and R1a, R2c, R3, X, Z, n and the broken line portion are as described above. Are synonymous.
　製造方法Ｉは、Ｒ１ｄが置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、またはＣ２～Ｃ６のハロアルキニル基である式（３ｃ）で表される化合物を得る方法であって、式（３ａ）で表される化合物と末端アルキン化合物とを、遷移金属類および塩基の存在下、溶媒中で反応させる薗頭カップリングによって得ることを含む製造方法である。 Production Method I is a method for obtaining a compound represented by the formula (3c), wherein R1d is a C2-C6 alkynyl group optionally substituted with a substituent A, or a C2-C6 haloalkynyl group, A production method comprising obtaining a compound represented by the formula (3a) and a terminal alkyne compound by Sonogashira coupling in which a compound is reacted in the presence of a transition metal and a base in a solvent.
　式（３ａ）中、好ましいＲ１ａは、塩素原子、臭素原子、またはヨウ素原子である。
　本反応に使用する末端アルキン化合物は、市販品として入手または公知の方法で製造することができる。また、末端アルキン化合物として、トリメチルシリルアセチレンも使用することができる。この場合は、式（３ａ）で表される化合物にトリメチルシリルエチニル基を導入後、脱シリル化を行う必要がある。脱シリル化については、ジャーナル　オブ　ザ　アメリカン　ケミカル　ソサエティー（Ｊｏｕｒｎａｌ　ｏｆ　ｔｈｅ　Ａｍｅｒｉｃａｎ　Ｃｈｅｍｉｃａｌ　Ｓｏｃｉｅｔｙ）、第１３１巻、２号、６３４－６４３頁（２００９）．およびジャーナル　オブ　オルガノメタリック　ケミストリー（Ｊｏｕｒｎａｌ　ｏｆ　Ｏｒｇａｎｏｍｅｔａｌｌｉｃ　Ｃｈｅｍｉｓｔｒｙ）、６９６巻、２５号、４０３９－４０４５頁（２０１１）．等の非特許文献を参考にして行うことができる。 In formula (3a), preferred R1a is a chlorine atom, a bromine atom, or an iodine atom.
The terminal alkyne compound used in this reaction can be obtained as a commercial product or can be produced by a known method. Trimethylsilylacetylene can also be used as the terminal alkyne compound. In this case, it is necessary to introduce a trimethylsilylethynyl group into the compound represented by the formula (3a) and then perform desilylation. For desilylation, see Journal of the American Chemical Society, Vol. 131, No. 2, pp. 634-643 (2009). And Journal of Organometallic Chemistry, 696, 25, 4039-4045 (2011). It can be performed with reference to non-patent documents such as the above.
　本反応に使用する末端アルキン化合物の量は、式（３ａ）で表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上１０当量以下である。 The amount of the terminal alkyne compound used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (3a). It is 1 equivalent or more and 10 equivalents or less.
　本反応に使用する遷移金属類は、配位子を有してよく、酢酸パラジウム、［１，１’－ビス（ジフェニルホスフィノ）フェロセン］パラジウムジクロリド、トリス（ジベンジリデンアセトン）ジパラジウム、テトラキス（トリフェニルホスフィン）パラジウム、ビス（トリフェニルホスフィン）パラジウムジクロリド等のパラジウム類等である。また、塩化銅、臭化銅、ヨウ化銅等の銅類も同時に使用する。 The transition metals used in this reaction may have a ligand, and include palladium acetate, [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris (dibenzylideneacetone) dipalladium, tetrakis ( Palladium compounds such as triphenylphosphine) palladium and bis (triphenylphosphine) palladium dichloride. In addition, coppers such as copper chloride, copper bromide, and copper iodide are used at the same time.
　本反応に使用する遷移金属類の量は、パラジウム類等および銅類が、それぞれ式（３ａ）で表される化合物に対して、通常、０．００１当量以上あればよく、目的とする反応が進行する限りにおいて特に制限されることはない。好ましい量は、双方ともに０．００１当量以上１当量以下である。 The amount of the transition metal used in this reaction is usually 0.001 equivalent or more with respect to the compound represented by the formula (3a), such as palladium and copper, and the desired reaction There is no particular limitation as long as the process proceeds. Preferred amounts are 0.001 equivalent to 1 equivalent in both cases.
　本反応に使用する塩基は、トリエチルアミン、トリブチルアミン、イソプロピルアミン、ジエチルアミン、ジイソプロピルアミン、ジイソプロピルエチルアミン等の有機アミン類や、炭酸ナトリウム、炭酸カリウム、炭酸セシウム等の無機塩基類等が挙げられる。 Examples of the base used in this reaction include organic amines such as triethylamine, tributylamine, isopropylamine, diethylamine, diisopropylamine and diisopropylethylamine, and inorganic bases such as sodium carbonate, potassium carbonate and cesium carbonate.
　本反応に使用する塩基の量は、式（３ａ）で表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上５０当量以下である。また、有機塩基で液体状のものに関しては、溶媒として使用することができる。 The amount of the base used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more relative to the compound represented by the formula (3a), but usually 1 equivalent It is above 50 equivalents. In addition, an organic base in a liquid state can be used as a solvent.
　本反応を効率的に進行させるために、トリｔ－ブチルホスフィン、２－ジシクロヘキシルホスフィノ－２’４’６’－トリイソプロピルビフェニル等のホスフィン配位子を添加することができるが、必須ではない。 A phosphine ligand such as tri-t-butylphosphine or 2-dicyclohexylphosphino-2'4'6'-triisopropylbiphenyl can be added to promote the reaction efficiently, but it is not essential. .
　本反応に使用するホスフィン配位子の量は、式（３ａ）で表される化合物に対して、通常、０．００１当量以上１当量以下であるが、目的とする反応が進行する限りにおいて特に限定されることはない。 The amount of the phosphine ligand used in this reaction is usually 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (3a), but as long as the intended reaction proceeds, There is no limitation.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、アセトニトリル等のニトリル系溶媒、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド系溶媒、１，３－ジメチル－２－イミダゾリジノン等のウレア系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、トリエチルアミン、トリブチルアミン、イソプロピルアミン、ジエチルアミン、ジイソプロピルアミン、ジイソプロピルエチルアミン等の有機アミン溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ester-based solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitrile-based solvents such as acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide , Amide solvents such as N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, halogen solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, triethylamine, Butylamine, isopropylamine, diethylamine, diisopropylamine, organic amine solvents such as diisopropylethylamine. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（３ａ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (3a). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、０℃以上１５０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。また、濾過操作を行うことにより、不溶物を除去することも可能であるが必須ではない。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. It is also possible, but not essential, to remove insolubles by performing a filtration operation.
　前記で得られた式（３ｃ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (3c) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（３ｃ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (3c) obtained above can be distilled under reduced pressure to remove the solvent.
　溶媒留去後に得られた式（３ｃ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (3c) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法Ｊ］
Figure JPOXMLDOC01-appb-C000047
　式中、Ｊは酸素原子または硫黄原子を表し、Ｊが酸素原子の場合、Ｒ１ｅは置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、またはＣ２～Ｃ６のハロアルキニル基を表し、Ｊが硫黄原子の場合、Ｒ１ｅはＣ１～Ｃ６のアルキル基またはＣ１～Ｃ６のハロアルキル基を表し、Ｑ、Ｒ１ａ、Ｒ２ｃ、Ｒ３、Ｘ、Ｚ、ｎおよび破線部は前記と同義である。 [Production method J]
Figure JPOXMLDOC01-appb-C000047
In the formula, J represents an oxygen atom or a sulfur atom, and when J is an oxygen atom, R1e is a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, or a substituent A. An optionally substituted C3 to C8 cycloalkyl group, an optionally substituted C2 to C6 alkenyl group, an optionally substituted C2 to C6 haloalkenyl group, an optionally substituted C2 To C6 alkynyl group or C2 to C6 haloalkynyl group, and when J is a sulfur atom, R1e represents a C1 to C6 alkyl group or a C1 to C6 haloalkyl group, and Q, R1a, R2c, R3, X, Z, n and the broken line portion have the same meaning as above.
　製造方法Ｊは、Ｊは酸素原子または硫黄原子を表し、Ｊが酸素原子の場合、Ｒ１ｅが置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、またはＣ２～Ｃ６のハロアルキニル基を表し、Ｊが硫黄原子の場合、Ｒ１ｅはＣ１～Ｃ６のアルキル基またはＣ１～Ｃ６のハロアルキル基を表す式（３ｄ）で表される化合物を得る方法であって、式（３ａ）で表される化合物とＲ１ｅ－Ｊ－Ｑとを、遷移金属類および塩基の存在下、溶媒中で反応させるカップリング反応によって得ることを含む製造方法である。 Production method J is a method wherein J represents an oxygen atom or a sulfur atom, and when J is an oxygen atom, R1e is a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, or a substituent which may be appropriately substituted with a substituent A. A C3 to C8 cycloalkyl group optionally substituted with A, a C2 to C6 alkenyl group optionally substituted with a substituent A, a C2 to C6 haloalkenyl group, optionally substituted with a substituent A Represents a good C2 to C6 alkynyl group or a C2 to C6 haloalkynyl group, and when J is a sulfur atom, R1e is represented by the formula (3d) representing a C1 to C6 alkyl group or a C1 to C6 haloalkyl group. And a compound of formula (3a) and R1e-JQ in a solvent in the presence of a transition metal and a base. It is a manufacturing method that includes.
　式（３ａ）で表される化合物中、好ましいＲ１ａは、塩素原子、臭素原子、またはヨウ素原子である。 In the compound represented by the formula (3a), preferable R1a is chlorine atom, bromine atom or iodine atom.
　本反応に使用するＲ１ｅ－Ｊ－Ｑは、市販品として入手または公知の方法で製造できる。好ましいＱは、水素原子、または、ナトリウム、カリウム等のアルカリ金属類である。 R1e-JQ used in this reaction can be obtained as a commercial product or can be produced by a known method. Preferred Q is a hydrogen atom or an alkali metal such as sodium or potassium.
　本反応に使用するＲ１ｅ－Ｊ－Ｑの量は、式（３ａ）で表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはない。Ｑが水素原子のときは、溶媒としても使用可能である。 The amount of R1e-JQ used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is at least 1 equivalent relative to the compound represented by the formula (3a). When Q is a hydrogen atom, it can be used also as a solvent.
　本反応に使用する遷移金属類は、配位子を有してよく、酢酸パラジウム、［１，１’－ビス（ジフェニルホスフィノ）フェロセン］パラジウムジクロリド、トリス（ジベンジリデンアセトン）ジパラジウム、テトラキス（トリフェニルホスフィン）パラジウム、ビス（トリフェニルホスフィン）パラジウムジクロリド等のパラジウム類等である。 The transition metals used in this reaction may have a ligand, and include palladium acetate, [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris (dibenzylideneacetone) dipalladium, tetrakis ( Palladium compounds such as triphenylphosphine) palladium and bis (triphenylphosphine) palladium dichloride.
　本反応に使用する遷移金属類の量は、式（３ａ）で表される化合物に対して、通常、０．００１当量以上１当量以下であるが、目的とする反応が進行する限りにおいて特に限定されることはない。 The amount of the transition metal used in this reaction is usually 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (3a), but is not particularly limited as long as the intended reaction proceeds. It will not be done.
　本反応を効率的に進行させるために、トリフェニルホスフィン、１，１’－ビス（ジフェニルホスフィノ）フェロセン、２－ジシクロヘキシルホスフィノ－２’４’６’－トリイソプロピルビフェニル、２－ジ－ｔ－ブチルホスフィノ－２’４’６’－トリイソプロピルビフェニル等のホスフィン配位子を添加することができる。 In order to proceed this reaction efficiently, triphenylphosphine, 1,1′-bis (diphenylphosphino) ferrocene, 2-dicyclohexylphosphino-2′4′6′-triisopropylbiphenyl, 2-di-t A phosphine ligand such as -butylphosphino-2'4'6'-triisopropylbiphenyl can be added.
　本反応に使用するホスフィン配位子の量は、式（３ａ）で表される化合物に対して、通常、０．００１当量以上１当量以下であるが、目的とする反応が進行する限りにおいて特に限定されることはない。 The amount of the phosphine ligand used in this reaction is usually 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (3a), but as long as the intended reaction proceeds, There is no limitation.
　本反応に使用する塩基は、炭酸ナトリウム、炭酸カリウム、炭酸セシウムのような無機塩基類やトリエチルアミン、トリブチルアミン、ジイソプロピルエチルアミン等の有機塩基類等である。 The bases used in this reaction include inorganic bases such as sodium carbonate, potassium carbonate and cesium carbonate, and organic bases such as triethylamine, tributylamine and diisopropylethylamine.
　本反応に使用する塩基の量は、式（３ａ）で表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上５０当量以下である。 The amount of the base used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more relative to the compound represented by the formula (3a), but usually 1 equivalent It is above 50 equivalents.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、Ｒ１ｅ－Ｊ－Ｈ（式中、Ｒ１ｅは前記と同義であり、Ｊは酸素原子である。）で表されるアルコール溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but R1e-JH (wherein R1e has the same meaning as described above and J is an oxygen atom). ) Alcohol solvent represented by), diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, ether solvent such as dioxane, benzene solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc. Is mentioned. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（３ａ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (3a). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、３０℃以上２００℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 30 ° C. or higher and 200 ° C. or lower or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。また、濾過操作を行うことにより、不溶物を除去することも可能であるが必須ではない。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. It is also possible, but not essential, to remove insolubles by performing a filtration operation.
　前記で得られた式（３ｄ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (3d) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（３ｄ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (3d) obtained above can be evaporated under reduced pressure as long as the compound does not decompose.
　溶媒留去後に得られた式（３ｄ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (3d) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法Ｋ］
Figure JPOXMLDOC01-appb-C000048
　式中、Ｒ３ｅは置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、またはＣ２～Ｃ６のハロアルケニル基を表し、Ｒ３ｅ－Ｂは有機ボロン酸類を表し、Ｒ１、Ｒ２、Ｒ３、Ｒ３ａ、Ｘ、Ｚおよびｏは前記と同義である。 [Production method K]
Figure JPOXMLDOC01-appb-C000048
In the formula, R3e is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent C Represents a C2 to C6 alkenyl group which may be optionally substituted with, or a C2 to C6 haloalkenyl group, R3e-B represents an organic boronic acid, and R1, R2, R3, R3a, X, Z and o are as described above. Is synonymous with.
　製造方法Ｋは、Ｒ３ｅが置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、またはＣ２～Ｃ６のハロアルケニル基である式（１ｋ）で表される化合物を得る方法であって、式（１ｂ）で表される化合物と有機ボロン酸類（Ｒ３ｅ－Ｂ）とを、遷移金属類および塩基の存在下、溶媒中で反応させる鈴木－宮浦カップリングによって得ることを含む製造方法である。 In the production method K, R3e is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent A method for obtaining a compound represented by formula (1k), which is a C2-C6 alkenyl group optionally substituted with a group C, or a C2-C6 haloalkenyl group, which is represented by formula (1b) A production method comprising obtaining a compound and an organic boronic acid (R3e-B) by Suzuki-Miyaura coupling in which a compound is reacted in the presence of a transition metal and a base in a solvent.
　式（１ｂ）中、好ましいＲ３ａは、塩素原子、臭素原子、またはヨウ素原子である。 In the formula (1b), preferable R3a is a chlorine atom, a bromine atom or an iodine atom.
　本反応に使用するＲ３ｅ－Ｂは、有機ボロン酸や有機ボロン酸エステル等の有機ボロン酸類を表し、市販品として入手または公知の方法で製造できる。 R3e-B used in this reaction represents an organic boronic acid such as an organic boronic acid or an organic boronic acid ester, and can be obtained as a commercially available product or can be produced by a known method.
　製造方法Ｈにおける式（３ａ）で表される化合物とＲ１ｃ－Ｂとを、それぞれ式（１ｂ）で表される化合物とＲ３ｅ－Ｂに代えて使用することにより、製造方法Ｈに準じて製造方法Ｋを実施することができる。 A production method according to the production method H by using the compound represented by the formula (3a) and R1c-B in the production method H instead of the compound represented by the formula (1b) and R3e-B, respectively. K can be carried out.
［製造方法Ｌ］
Figure JPOXMLDOC01-appb-C000049
　式中、Ｒ４ａはハロゲン原子を表し、Ｚ１はＲ４で適宜０～２置換されてもよいチエニル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）、Ｒ４で適宜置換されてもよいチアゾリル基、チアジアゾリル基、または、Ｒ４で適宜０～２置換されてもよいピラゾリル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）を表し、ＨａｌＲ、Ｒ１、Ｒ２、Ｒ３、Ｘおよびｎは前記と同義である。 [Production method L]
Figure JPOXMLDOC01-appb-C000049
In the formula, R4a represents a halogen atom, Z1 is a thienyl group which may be optionally substituted by 0 to 2 with R4 (however, in the case of 2 or more substitutions, each is independent), R1 is appropriately substituted with R4. Represents a thiazolyl group, a thiadiazolyl group, or a pyrazolyl group which may be optionally substituted by 0 to 2 with R4 (however, in the case of 2 or more substituted R4, each is independent), and HalR, R1, R2, R3, X and n are as defined above.
　製造方法Ｌは、式（１ｍ）で表される化合物を得る方法であって、式（１ｌ）で表される化合物とハロゲン化剤（ＨａｌＲ）とを、溶媒中で反応させる方法を含む製造方法である。 Production method L is a method for obtaining a compound represented by formula (1m), which comprises reacting the compound represented by formula (1l) with a halogenating agent (HalR) in a solvent. Is.
　製造方法Ａにおける式（２ａ）で表される化合物を、式（１ｌ）で表される化合物に代えて使用することにより、製造方法Ａに準じて製造方法Ｌを実施することができる。 By using the compound represented by the formula (2a) in the production method A instead of the compound represented by the formula (1l), the production method L can be carried out according to the production method A.
［製造方法Ｍ］
Figure JPOXMLDOC01-appb-C000050
　式中、Ｒ４ｂは置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、またはＣ２～Ｃ６のハロアルケニル基を表し、Ｒ４ｂ－Ｂは有機ボロン酸類を表し、Ｒ１、Ｒ２、Ｒ３、Ｒ４ａ、Ｘ、Ｚ１およびｎは前記と同義である。 [Manufacturing method M]
Figure JPOXMLDOC01-appb-C000050
In the formula, R4b is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent C Represents an optionally substituted C2 to C6 alkenyl group or a C2 to C6 haloalkenyl group, R4b-B represents an organic boronic acid, and R1, R2, R3, R4a, X, Z1 and n are the above Is synonymous with.
　製造方法Ｍは、Ｒ４ｂが置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、またはＣ２～Ｃ６のハロアルケニル基である式（１ｎ）で表される化合物を得る方法であって、式（１ｍ）で表される化合物と有機ボロン酸類（Ｒ４ｂ－Ｂ）とを、遷移金属類および塩基の存在下、溶媒中で反応させる鈴木－宮浦カップリングによって得ることを含む製造方法である。 In the production method M, R4b is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent A method for obtaining a compound represented by formula (1n), which is a C2-C6 alkenyl group optionally substituted with a group C, or a C2-C6 haloalkenyl group, which is represented by formula (1m) A production method comprising obtaining a compound and an organic boronic acid (R4b-B) by Suzuki-Miyaura coupling in which a compound is reacted in the presence of a transition metal and a base in a solvent.
　式（１ｍ）中、好ましいＲ４ａは、塩素原子、臭素原子、またはヨウ素原子である。 In the formula (1m), preferred R4a is a chlorine atom, a bromine atom, or an iodine atom.
　本反応に使用するＲ４ｂ－Ｂは、有機ボロン酸や有機ボロン酸エステル等の有機ボロン酸類を表し、市販品として入手または公知の方法で製造できる。 R4b-B used in this reaction represents an organic boronic acid such as an organic boronic acid or an organic boronic acid ester, which can be obtained as a commercially available product or can be produced by a known method.
　製造方法Ｈにおける式（３ａ）で表される化合物とＲ１ｃ－Ｂとを、それぞれ式（１ｍ）で表される化合物とＲ４ｂ－Ｂに代えて使用することにより、製造方法Ｈに準じて製造方法Ｍを実施することができる。 A production method according to the production method H by using the compound represented by the formula (3a) and R1c-B in the production method H instead of the compound represented by the formula (1m) and R4b-B, respectively. M can be carried out.
［製造方法Ｎ］
Figure JPOXMLDOC01-appb-C000051
　式中、Ｒ３ｆは置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、またはＣ２～Ｃ６のハロアルキニル基を表し、Ｒ１、Ｒ２、Ｒ３、Ｒ３ａ、Ｘ、Ｚおよびｏは前記と同義である。 [Manufacturing method N]
Figure JPOXMLDOC01-appb-C000051
In the formula, R3f represents a C2-C6 alkynyl group which may be optionally substituted with a substituent C, or a C2-C6 haloalkynyl group, and R1, R2, R3, R3a, X, Z and o have the same meanings as described above. Is.
　製造方法Ｎは、Ｒ３ｆが置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、またはＣ２～Ｃ６のハロアルキニル基である式（１ｏ）で表される化合物を得る方法であって、式（１ｂ）で表される化合物と末端アルキン化合物とを、遷移金属類および塩基の存在下、溶媒中で反応させる薗頭カップリングによって得ることを含む製造方法である。 The production method N is a method of obtaining a compound represented by the formula (1o), wherein R3f is a C2-C6 alkynyl group optionally substituted with a substituent C, or a C2-C6 haloalkynyl group, A production method comprising obtaining a compound represented by the formula (1b) and a terminal alkyne compound by Sonogashira coupling in which a compound is reacted in the presence of a transition metal and a base in a solvent.
　式（１ｂ）中、好ましいＲ３ａは、塩素原子、臭素原子、またはヨウ素原子である。 In the formula (1b), preferable R3a is a chlorine atom, a bromine atom or an iodine atom.
　本反応に使用する末端アルキン化合物は、市販品として入手または公知の方法で製造することができる。また、末端アルキン化合物として、トリメチルシリルアセチレンも使用することができる。 The terminal alkyne compound used in this reaction can be obtained as a commercial product or can be produced by a known method. Further, trimethylsilylacetylene can also be used as the terminal alkyne compound.
　製造方法Ｉにおける式（３ａ）で表される化合物を、式（１ｂ）で表される化合物に代えて使用することにより、製造方法Ｉに準じて製造方法Ｎを実施することができる。 By using the compound represented by the formula (3a) in the production method I instead of the compound represented by the formula (1b), the production method N can be carried out according to the production method I.
［製造方法Ｏ］
Figure JPOXMLDOC01-appb-C000052
　式中、Ｒ４ｃは置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、またはＣ２～Ｃ６のハロアルキニル基を表し、Ｒ１、Ｒ２、Ｒ３、Ｒ４ａ、Ｘ、Ｚ１およびｎは前記と同義である。 [Production method O]
Figure JPOXMLDOC01-appb-C000052
In the formula, R4c represents a C2 to C6 alkynyl group which may be appropriately substituted with a substituent C, or a C2 to C6 haloalkynyl group, and R1, R2, R3, R4a, X, Z1 and n have the same meanings as described above. Is.
　製造方法Ｏは、Ｒ４ｃが置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、またはＣ２～Ｃ６のハロアルキニル基である式（１ｐ）で表される化合物を得る方法であって、式（１ｍ）で表される化合物と末端アルキン化合物とを、遷移金属類および塩基の存在下、溶媒中で反応させる薗頭カップリングによって得ることを含む製造方法である。 Production method O is a method for obtaining a compound represented by the formula (1p) in which R4c is a C2-C6 alkynyl group optionally substituted with a substituent C, or a C2-C6 haloalkynyl group, A production method which comprises obtaining a compound represented by the formula (1m) and a terminal alkyne compound by Sonogashira coupling in which a compound is reacted in the presence of a transition metal and a base in a solvent.
　式（１ｍ）中、好ましいＲ４ａは、塩素原子、臭素原子、またはヨウ素原子である。
　本反応に使用する末端アルキン化合物は、市販品として入手または公知の方法で製造することができる。また、末端アルキン化合物として、トリメチルシリルアセチレンも使用することができる。 In formula (1m), preferred R4a is a chlorine atom, a bromine atom, or an iodine atom.
The terminal alkyne compound used in this reaction can be obtained as a commercial product or can be produced by a known method. Trimethylsilylacetylene can also be used as the terminal alkyne compound.
　製造方法Ｉにおける式（３ａ）で表される化合物を、式（１ｍ）で表される化合物に代えて使用することにより、製造方法Ｉに準じて製造方法Ｏを実施することができる。 By using the compound represented by the formula (3a) in the production method I in place of the compound represented by the formula (1m), the production method O can be carried out according to the production method I.
［製造方法Ｐ］
Figure JPOXMLDOC01-appb-C000053
　式中、Ｒ４ｄはＣ１～Ｃ６のアルコキシ基を表し、Ｒ１、Ｒ２、Ｒ３、Ｘ、Ｚ１およびｎは前記と同義である。 [Manufacturing method P]
Figure JPOXMLDOC01-appb-C000053
In the formula, R4d represents a C1-C6 alkoxy group, and R1, R2, R3, X, Z1 and n have the same meanings as described above.
　製造方法Ｐは、水酸基を有する式（１ｒ）で表される化合物を得る方法であって、式（１ｑ）で表される化合物と酸とを、溶媒中で反応させることによって得ることを含む製造方法である。 Production method P is a method for obtaining a compound represented by the formula (1r) having a hydroxyl group, which is obtained by reacting the compound represented by the formula (1q) with an acid in a solvent. Is the way.
　本反応に使用する酸として、三塩化ホウ素、三臭化ホウ素等のハロゲン化ホウ素類等が挙げられる。 The acids used in this reaction include boron halides such as boron trichloride and boron tribromide.
　製造方法Ｄにおける式（１ｄ）で表される化合物を、式（１ｑ）で表される化合物に代えて使用することにより、製造方法Ｄに準じて製造方法Ｐを実施することができる。 By using the compound represented by the formula (1d) in the production method D instead of the compound represented by the formula (1q), the production method P can be carried out according to the production method D.
［製造方法Ｑ］
Figure JPOXMLDOC01-appb-C000054
　式中、Ｒ４ｅは置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニル基、Ｃ３～Ｃ６のハロアルキニル基、またはＲｄＣ（＝Ｏ）－（Ｒｄは、前記と同義である。）を表し、Ｒ１、Ｒ２、Ｒ３、Ｘ、Ｚ１、Ｌｖおよびｎは前記と同義である。 [Production method Q]
Figure JPOXMLDOC01-appb-C000054
In the formula, R4e is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent C A C2-C6 alkenyl group optionally substituted with, a C2-C6 haloalkenyl group, a C3-C6 alkynyl group optionally substituted with a substituent C, a C3-C6 haloalkynyl group, or RdC ( ═O)-(Rd has the same meaning as described above), and R1, R2, R3, X, Z1, Lv and n have the same meaning as described above.
　製造方法Ｑは、Ｒ４ｅが、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基、置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニル基、Ｃ３～Ｃ６のハロアルキニル基、またはＲｄＣ（＝Ｏ）－（Ｒｄは、前記と同義である。）である式（１ｓ）で表される化合物を得る方法であって、式（１ｒ）で表される化合物とＲ４ｅ－Ｌｖとを塩基存在下、溶媒中で反応させることを含む製造方法である。 In the production method Q, R4e is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, A C2 to C6 alkenyl group optionally substituted with a substituent C, a C2 to C6 haloalkenyl group, a C3 to C6 alkynyl group optionally substituted with a substituent C, a C3 to C6 haloalkynyl group, Alternatively, a method of obtaining a compound represented by the formula (1s), which is RdC (═O)-(Rd has the same meaning as described above), comprising the step of providing a compound represented by the formula (1r) and R4e-Lv. In a solvent in the presence of a base.
　製造方法Ｅにおける式（１ｅ）で表される化合物とＲ３ｄ－Ｌｖとを、それぞれ式（１ｒ）で表される化合物とＲ４ｅ－Ｌｖに代えて使用することにより、製造方法Ｅ準じて製造方法Ｑを実施することができる。 By using the compound represented by the formula (1e) and R3d-Lv in the production method E instead of the compound represented by the formula (1r) and R4e-Lv, the production method Q is carried out according to the production method E. Can be carried out.
［製造方法Ｒ］
Figure JPOXMLDOC01-appb-C000055
　式中、Ｒ１、Ｒ２ｃ、Ｒ３、Ｘ、Ｚ、Ｌｖおよびｎは前記と同義である。 [Production method R]
Figure JPOXMLDOC01-appb-C000055
In the formula, R1, R2c, R3, X, Z, Lv and n are as defined above.
　製造方法Ｒは、Ｒ２ｃが、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、Ｃ２～Ｃ６のハロアルキニル基、Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）、またはＲｇＣ（＝Ｏ）－（ここで、Ｒｇは、前記と同義である。）である式（２ｅ）で表される製造中間体を得る方法であって、式（２ｄ）で表される化合物とＲ２ｃ－Ｌｖとを、塩基存在下、溶媒中で反応させること含む製造方法である。 In the production method R, R2c is a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent A, A C2 to C6 alkenyl group optionally substituted with a substituent A, a C2 to C6 haloalkenyl group, a C2 to C6 alkynyl group optionally substituted with a substituent A, a C2 to C6 haloalkynyl group, Rc-L- (wherein Rc and L are as defined above) or RgC (= O)-(where Rg is as defined above) represented by formula (2e). A method for obtaining the above-mentioned production intermediate, which comprises reacting the compound represented by the formula (2d) with R2c-Lv in a solvent in the presence of a base.
　本反応に使用するＲ２ｃ－Ｌｖは、市販品として入手または公知の方法で製造することができる。 The R2c-Lv used in this reaction can be obtained as a commercial product or can be produced by a known method.
　本反応に使用するＲ２ｃ－Ｌｖの量は、式（２ｄ）で表される化合物に対して１当量以上あればよく、目的とする反応が進行する限りにおいて特に制限されることはないが、通常、１当量以上５０当量以下である。 The amount of R2c-Lv used in this reaction may be 1 equivalent or more relative to the compound represented by the formula (2d), and is not particularly limited as long as the intended reaction proceeds, but It is 1 equivalent or more and 50 equivalents or less.
　本反応に使用する塩基として、水素化ナトリウム等の金属ヒドリド類、メチルリチウム、ブチルリチウム、ｓｅｃ－ブチルリチウム、ｔ－ブチルリチウム、ヘキシルリチウム等の有機リチウム類や、リチウムジイソプロピルアミド、ヘキサメチルジシラザンリチウム、ヘキサメチルジシラザンナトリウム、ヘキサメチルジシラザンカリウム等の金属アミド類が例示される。 As the base used in this reaction, metal hydrides such as sodium hydride, organic lithiums such as methyllithium, butyllithium, sec-butyllithium, t-butyllithium, and hexyllithium, lithium diisopropylamide, hexamethyldisilazane Examples are metal amides such as lithium, sodium hexamethyldisilazane, and potassium hexamethyldisilazane.
　本反応に使用する塩基の量は、式（２ｄ）で表される化合物に対して１当量以上あればよく、目的とする反応が進行する限りにおいて特に制限されることはないが、通常、１当量以上２０当量以下である。 The amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (2d) and is not particularly limited as long as the intended reaction proceeds, but it is usually 1 It is equal to or more than 20 equivalents.
　反応を円滑に進行させるために、ヘキサメチルリン酸トリアミド、Ｎ，Ｎ’－ジメチル尿素、テトラメチルエチレンジアミン等の添加剤を添加することができるが、必須ではない。 Additives such as hexamethylphosphoric triamide, N, N'-dimethylurea, and tetramethylethylenediamine can be added in order to allow the reaction to proceed smoothly, but are not essential.
　本反応に添加剤を使用する際、添加剤の使用量は、式（２ｄ）で表される化合物に対して、１当量以上１００当量以下である。 When the additive is used in this reaction, the amount of the additive used is 1 equivalent or more and 100 equivalents or less with respect to the compound represented by the formula (2d).
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Examples thereof include benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, and hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（２ｄ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2d). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、－８０℃以上１００℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 100 ° C or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- It is possible to add an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane and chloroform, a hydrocarbon solvent such as hexane, heptane, cyclohexane and methylcyclohexane, which is incompatible with water. It is possible. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（２ｅ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (2e) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（２ｅ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (2e) obtained above can be distilled under reduced pressure to remove the solvent.
　溶媒留去後に得られた式（２ｅ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (2e) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法Ｓ］
Figure JPOXMLDOC01-appb-C000056
　式中、Ｒ１ｆは水素原子、またはＣ１～Ｃ６のアルキル基を表し、Ｒ２ｄは水素原子、またはＣ１～Ｃ６のアルキル基を表し、Ｒｘ、ＲｙおよびＲｚは、それぞれ独立していて、Ｃ１～Ｃ６のアルキル基を表し、ＲｗはＣ１～Ｃ６のアルコキシ基または、ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）を表し、Ｒ３、Ｚおよびｎは前記と同義である。なお、式中の波線は幾何異性を表し、Ｅ体またはＺ体のどちらか一方のみ、あるいはＥ体とＺ体との任意の割合の混合物を表す。 [Manufacturing method S]
Figure JPOXMLDOC01-appb-C000056
In the formula, R1f represents a hydrogen atom or a C1 to C6 alkyl group, R2d represents a hydrogen atom or a C1 to C6 alkyl group, and Rx, Ry and Rz are each independently C1 to C6 Represents an alkyl group, Rw represents a C1-C6 alkoxy group or RaRbN- (wherein Ra and Rb have the same meanings as described above), and R3, Z and n have the same meanings as described above. The wavy line in the formula represents geometrical isomerism, and represents only one of the E isomer and the Z isomer, or a mixture of the E isomer and the Z isomer at an arbitrary ratio.
　製造方法Ｓは、Ｒ１ｆが水素原子、またはＣ１～Ｃ６のアルキル基を表し、Ｒ２ｄは水素原子、またはＣ１～Ｃ６のアルキル基を表す式（２ｆ）で表される化合物を得る方法であって、式（４）で表される化合物、式（５）で表される化合物および式（６）で表される化合物を、溶媒中で反応させることを含む製造方法である。 Production method S is a method for obtaining a compound represented by the formula (2f) in which R1f represents a hydrogen atom or a C1 to C6 alkyl group, and R2d represents a hydrogen atom or a C1 to C6 alkyl group, A production method comprising reacting a compound represented by formula (4), a compound represented by formula (5) and a compound represented by formula (6) in a solvent.
　本反応に使用する式（４）で表される化合物は、市販品として入手または公知の方法で製造することができる。 The compound represented by the formula (4) used in this reaction can be obtained as a commercial product or can be produced by a known method.
　本反応に使用する式（５）で表される化合物は、市販品として入手または公知の方法で製造することができる。 The compound represented by the formula (5) used in this reaction can be obtained as a commercially available product or can be produced by a known method.
　本反応に使用する式（５）で表される化合物の量は、式（４）で表される化合物に対して１当量以上あれば、反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上１．５当量以下である。 The amount of the compound represented by the formula (5) used in this reaction is not particularly limited as long as the reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (4). Usually, it is 1 equivalent or more and 1.5 equivalents or less.
　本反応に使用する式（６）で表される化合物は、市販品として入手または公知の方法で製造することができる。また、幾何異性体がある場合、Ｅ体またはＺ体のどちらか一方のみ、あるいはＥ体とＺ体との任意の割合の混合物でよく、反応が進行する限りにおいて特に限定されることはない。 The compound represented by the formula (6) used in this reaction can be obtained as a commercial product or can be produced by a known method. Further, when there are geometrical isomers, only one of E-form or Z-form or a mixture of E-form and Z-form at an arbitrary ratio may be used and is not particularly limited as long as the reaction proceeds.
　本反応に使用する式（６）で表される化合物の量は、式（４）で表される化合物に対して１当量以上あれば、反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上３当量以下である。 The amount of the compound represented by the formula (6) used in this reaction is not particularly limited as long as the reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (4). Usually, it is 1 equivalent or more and 3 equivalents or less.
　本反応は、必須ではないが、酸や界面活性剤を添加することにより、反応を円滑に進行させることができる。使用する酸として、テトラフルオロホウ酸等を例示することができる。本反応に使用する酸の量は、式（４）で表される化合物に対して触媒量でよく、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、０．０１当量以上１当量以下である。また、使用する界面活性剤として、ドデシル硫酸ナトリウム等を例示することができる。反応に使用する界面活性剤の量は、式（４）で表される化合物に対して触媒量でよく、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、０．０１当量以上１当量以下である。酸と界面活性剤は、同時、またはどちらか一方のみを使用することが可能である。 This reaction is not essential, but the reaction can be smoothly proceeded by adding an acid or a surfactant. Tetrafluoroboric acid etc. can be illustrated as an acid to be used. The amount of the acid used in this reaction may be a catalytic amount with respect to the compound represented by the formula (4) and is not particularly limited as long as the intended reaction proceeds, but usually 0.01 It is equal to or more than 1 equivalent. Moreover, sodium dodecyl sulfate etc. can be illustrated as a surfactant to be used. The amount of the surfactant used in the reaction may be a catalytic amount with respect to the compound represented by the formula (4) and is not particularly limited as long as the intended reaction proceeds, but it is usually 0. It is from 1 equivalent to 1 equivalent. The acid and the surfactant can be used at the same time or only one of them.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、水、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、メタノール、エタノール、イソプロパノール等のアルコール系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、アセトニトリル等のニトリル系溶媒、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド系溶媒、１，３－ジメチル－２－イミダゾリジノン等のウレア系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。また、本反応は、溶媒は必ずしも必須ではない。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether system such as water, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane and the like. Solvents, alcohol solvents such as methanol, ethanol and isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitrile solvents such as acetonitrile Solvents, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, dichloromethane, dichloroethane Chloroform, and halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. In addition, a solvent is not essential for this reaction.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（４）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (4). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、－８０℃以上１５０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 150 ° C or lower or the boiling point of the solvent or lower.
　本反応における反応の順序は、式（４）で表される化合物、式（５）で表される化合物および式（６）で表される化合物を一緒に反応させることが可能である。また、予め、式（４）で表される化合物および式（５）で表される化合物を反応させてイミンに変換した後に、式（６）で表される化合物を反応させることができる。なお、イミンの調製方法は公知の方法で実施することができる。この場合、式（４）で表される化合物および式（５）で表される化合物を該イミンに代えて、前記した方法で実施することができる。 Regarding the order of reactions in this reaction, the compound represented by the formula (4), the compound represented by the formula (5) and the compound represented by the formula (6) can be reacted together. Further, the compound represented by the formula (4) and the compound represented by the formula (5) can be reacted in advance to convert into an imine, and then the compound represented by the formula (6) can be reacted. The imine can be prepared by a known method. In this case, the compound represented by formula (4) and the compound represented by formula (5) can be replaced by the imine, and the method described above can be used.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（２ｆ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (2f) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（２ｆ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (2f) obtained above can be distilled under reduced pressure to remove the solvent.
　溶媒留去後に得られた式（２ｆ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (2f) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法Ｔ］
Figure JPOXMLDOC01-appb-C000057
　式中、Ｒ５は水酸基、またはＣ１～Ｃ６のアルコキシ基を表し、Ｒ３、Ｚおよびｎは前記と同義である。 [Manufacturing method T]
Figure JPOXMLDOC01-appb-C000057
In the formula, R5 represents a hydroxyl group or a C1 to C6 alkoxy group, and R3, Z and n have the same meanings as described above.
　製造方法Ｔは、Ｒ５が、水酸基またはＣ１～Ｃ６のアルコキシ基で表される式（７）で表される製造中間体を得る方法であって、式（４）で表される化合物と式（５）で表される化合物とを、溶媒中で反応させることを含む製造方法である。 The production method T is a method for obtaining a production intermediate represented by the formula (7) in which R5 is a hydroxyl group or a C1 to C6 alkoxy group, and comprises a compound represented by the formula (4) and a formula (4) It is a production method which comprises reacting the compound represented by 5) in a solvent.
　本反応に使用する式（４）で表される化合物は、市販品として入手または公知の方法で製造することができる。 The compound represented by the formula (4) used in this reaction can be obtained as a commercial product or can be produced by a known method.
　本反応に使用する式（５）で表される化合物は、市販品として入手または公知の方法で製造することができる。 The compound represented by the formula (5) used in this reaction can be obtained as a commercially available product or can be produced by a known method.
　本反応に使用する式（５）で表される化合物の量は、式（４）で表される化合物に対して１当量以上あれば、反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上１．５当量以下である。 The amount of the compound represented by the formula (5) used in this reaction is not particularly limited as long as the reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (4). Usually, it is 1 equivalent or more and 1.5 equivalents or less.
　本反応は、必須ではないが、酸や塩基を添加することにより、反応を円滑に進行させることができる。使用する酸として、パラトルエンスルホン酸ピリジニウム等を例示することができる。本反応に使用する酸の量は、式（４）で表される化合物に対して触媒量でよく、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、０．０１当量以上１当量以下である。また、使用する塩基として、ピロリジンやピペリジン等を例示することができる。反応に使用する塩基の量は、式（４）で表される化合物に対して触媒量でよく、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、０．０１当量以上１当量以下である。 -This reaction is not essential, but the addition of an acid or a base allows the reaction to proceed smoothly. Examples of the acid used include pyridinium paratoluenesulfonate. The amount of the acid used in this reaction may be a catalytic amount with respect to the compound represented by the formula (4) and is not particularly limited as long as the intended reaction proceeds, but usually 0.01 It is equal to or more than 1 equivalent. Examples of the base used include pyrrolidine and piperidine. The amount of the base used in the reaction may be a catalytic amount with respect to the compound represented by the formula (4) and is not particularly limited as long as the intended reaction proceeds, but usually 0.01 equivalent It is above 1 equivalent.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、メタノール、エタノール、イソプロパノール等のアルコール系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、アセトニトリル等のニトリル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。また、本反応は、溶媒は必ずしも必須ではない。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Methanol, ethanol, alcohol solvents such as isopropanol, benzene, toluene, xylene, mesitylene, chlorobenzene, benzene solvents such as dichlorobenzene, ethyl acetate, isopropyl acetate, ester solvents such as butyl acetate, nitrile solvents such as acetonitrile, Examples thereof include halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. In addition, a solvent is not essential for this reaction.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（４）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (4). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、－８０℃以上１５０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 150 ° C or lower or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（７）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (7) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（７）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (7) obtained above can be evaporated under reduced pressure as long as the compound does not decompose.
　溶媒留去後に得られた式（７）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (7) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法Ｕ］
Figure JPOXMLDOC01-appb-C000058
　式中、Ｒ１ｆ、Ｒ２ｄ、Ｒ３、Ｒ５、Ｒｗ、Ｒｘ、Ｒｙ、Ｒｚ、Ｘ、Ｚ、ｎおよび波線部は前記と同義である。 [Manufacturing method U]
Figure JPOXMLDOC01-appb-C000058
In the formula, R1f, R2d, R3, R5, Rw, Rx, Ry, Rz, X, Z, n and the wavy line portion are as defined above.
　製造方法Ｕは、式（２ｇ）で表される製造中間体を得る方法であって、式（７）で表される化合物と式（６）で表される化合物とを、溶媒中で反応させることを含む製造方法である。 The production method U is a method for obtaining a production intermediate represented by the formula (2g), which comprises reacting the compound represented by the formula (7) with the compound represented by the formula (6) in a solvent. It is a manufacturing method including the above.
　本反応に使用する式（６）で表される化合物は、市販品として入手または公知の方法で製造することができる。また、幾何異性体がある場合、Ｅ体またはＺ体のどちらか一方のみ、あるいはＥ体とＺ体との任意の割合の混合物でよく、反応が進行する限りにおいて特に限定されることはない。 The compound represented by the formula (6) used in this reaction can be obtained as a commercial product or can be produced by a known method. Further, when there are geometrical isomers, only one of E-form or Z-form or a mixture of E-form and Z-form at an arbitrary ratio may be used and is not particularly limited as long as the reaction proceeds.
　本反応に使用する式（６）で表される化合物の量は、式（７）で表される化合物に対して１当量以上あれば、反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上３当量以下である。 The amount of the compound represented by the formula (6) used in this reaction is not particularly limited as long as the reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (7). Usually, it is 1 equivalent or more and 3 equivalents or less.
　本反応は、必須ではないが、酸や界面活性剤を添加することにより、反応を円滑に進行させることができる。使用する酸として、テトラフルオロホウ酸等を例示することができる。本反応に使用する酸の量は、式（７）で表される化合物に対して触媒量でよく、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、０．０１当量以上１当量以下である。また、使用する界面活性剤として、ドデシル硫酸ナトリウム等を例示することができる。反応に使用する界面活性剤の量は、式（７）で表される化合物に対して触媒量でよく、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、０．０１当量以上１当量以下である。酸と界面活性剤は、同時、またはどちらか一方のみを使用することが可能である。 This reaction is not essential, but the reaction can be smoothly proceeded by adding an acid or a surfactant. Tetrafluoroboric acid etc. can be illustrated as an acid to be used. The amount of the acid used in this reaction may be a catalytic amount with respect to the compound represented by the formula (7) and is not particularly limited as long as the intended reaction proceeds, but usually 0.01 It is equal to or more than 1 equivalent. Moreover, sodium dodecyl sulfate etc. can be illustrated as a surfactant to be used. The amount of the surfactant used in the reaction may be a catalytic amount with respect to the compound represented by the formula (7) and is not particularly limited as long as the intended reaction proceeds, but it is usually 0. It is from 1 equivalent to 1 equivalent. The acid and the surfactant can be used at the same time or only one of them.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、水、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、メタノール、エタノール、イソプロパノール等のアルコール系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、アセトニトリル等のニトリル系溶媒、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド系溶媒、１，３－ジメチル－２－イミダゾリジノン等のウレア系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。また、本反応は、溶媒は必ずしも必須ではない。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether system such as water, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane and the like. Solvents, alcohol solvents such as methanol, ethanol and isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitrile solvents such as acetonitrile Solvents, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, dichloromethane, dichloroethane Chloroform, and halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. In addition, a solvent is not essential for this reaction.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（７）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (7). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、－８０℃以上１５０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 150 ° C or lower or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（２ｇ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (2g) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（２ｇ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (2g) obtained above can be evaporated under reduced pressure as long as the compound does not decompose.
　溶媒留去後に得られた式（２ｇ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (2g) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
　式（２ｇ）で表される化合物は、構造異性体を有する。その異性体比は、単独でも任意の割合の混合物でもよく、次工程の反応が進行する限りにおいて特に限定されることはない。 The compound represented by the formula (2g) has structural isomers. The isomer ratio may be a single isomer or a mixture in an arbitrary ratio, and is not particularly limited as long as the reaction of the next step proceeds.
［製造方法Ｖ］
Figure JPOXMLDOC01-appb-C000059
　式中、Ｚ２は、Ｒ４で適宜０～２置換されてもよいピラゾリル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）を表し、Ｒ１、Ｒ２、Ｒ３、Ｘおよびｎは前記と同義である。 [Manufacturing method V]
Figure JPOXMLDOC01-appb-C000059
In the formula, Z2 represents a pyrazolyl group which may be optionally substituted by 0 to 2 with R4 (however, in the case of 2 or more substituted R4, each is independent), and R1, R2, R3, X and n are It is synonymous with the above.
　製造方法Ｖは、ホルミル基を有する式（１ｕ）で表される化合物を得る方法であって、式（１ｔ）で表される化合物とＮ，Ｎ－ジメチルホルムアミドとを、塩基存在下、溶媒中で反応させること含む製造方法である。 Production method V is a method for obtaining a compound represented by the formula (1u) having a formyl group, which comprises reacting the compound represented by the formula (1t) and N, N-dimethylformamide in the presence of a base in a solvent. It is a manufacturing method including reacting with.
　本反応に使用するＮ，Ｎ－ジメチルホルムアミドは、市販品として入手することができる。 The N, N-dimethylformamide used in this reaction can be obtained as a commercial product.
　本反応に使用するＮ，Ｎ－ジメチルホルムアミドの量は、式（１ｔ）で表される化合物に対して１当量以上あれば、反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上５０当量以下である。 The amount of N, N-dimethylformamide used in this reaction is not particularly limited as long as the reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1t). It is 1 equivalent or more and 50 equivalents or less.
　本反応に使用する塩基として、メチルリチウム、ブチルリチウム、ｓｅｃ－ブチルリチウム、ｔ－ブチルリチウム、ヘキシルリチウム等の有機リチウム類や、リチウムジイソプロピルアミド、ヘキサメチルジシラザンリチウム、ヘキサメチルジシラザンナトリウム、ヘキサメチルジシラザンカリウム等の金属アミド類が例示される。 Examples of the base used in this reaction include organic lithiums such as methyllithium, butyllithium, sec-butyllithium, t-butyllithium, and hexyllithium, lithium diisopropylamide, hexamethyldisilazane lithium, hexamethyldisilazane sodium, and hexa Examples are metal amides such as potassium methyldisilazane.
　本反応に使用する塩基の量は、式（１ｔ）で表される化合物に対して１当量以上あればよく、目的とする反応が進行する限りにおいて特に制限されることはないが、通常、１当量以上２０当量以下である。 The amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1t) and is not particularly limited as long as the intended reaction proceeds, but it is usually 1 It is equal to or more than 20 equivalents.
　反応を円滑に進行させるために、ヘキサメチルリン酸トリアミド、Ｎ，Ｎ’－ジメチル尿素）、テトラメチルエチレンジアミン等の添加剤を添加することができるが、必須ではない。 In order to allow the reaction to proceed smoothly, additives such as hexamethylphosphoric triamide, N, N'-dimethylurea) and tetramethylethylenediamine can be added, but they are not essential.
　本反応に添加剤を使用する際、添加剤の使用量は、式（１ｔ）で表される化合物に対して、１当量以上１００当量以下である。 When the additive is used in this reaction, the amount of the additive used is 1 equivalent or more and 100 equivalents or less with respect to the compound represented by the formula (1t).
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Examples thereof include benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, and hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（１ｔ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but is usually 3 times or more and 200 times or less by weight with respect to the compound represented by the formula (1t). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、－８０℃以上１００℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 100 ° C or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- It is possible to add an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane and chloroform, a hydrocarbon solvent such as hexane, heptane, cyclohexane and methylcyclohexane, which is incompatible with water. It is possible. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（１ｕ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (1u) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（１ｕ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (1u) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
　溶媒留去後に得られた式（１ｕ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (1u) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法Ｗ］
Figure JPOXMLDOC01-appb-C000060
　式中、Ｒ１、Ｒ２、Ｒ３、Ｘ、Ｚ２およびｎは前記と同義である。 [Production method W]
Figure JPOXMLDOC01-appb-C000060
In the formula, R1, R2, R3, X, Z2 and n are as defined above.
　製造方法Ｗは、ジフルオロメチル基を有する式（１ｖ）で表される化合物を得る方法であって、式（１ｕ）で表される化合物とフッ素化剤（Ｆ－Ｒ）とを、溶媒中で反応させる方法を含む製造方法である。 The production method W is a method for obtaining a compound represented by the formula (1v) having a difluoromethyl group, wherein the compound represented by the formula (1u) and the fluorinating agent (FR) are mixed in a solvent. It is a manufacturing method including a method of reacting.
　本反応に使用するフッ素化剤としては、ＤＡＳＴ（三フッ化－Ｎ，Ｎ－ジエチルアミノ硫黄）、Ｄｅｏｘｏ－Ｆｌｕｏｒ（Ｎ，Ｎ－ジメトキシエチルアミノ硫黄トリフルオリド）、ＸｔａｌＦｌｕｏｒ－Ｅ（Ｎ，Ｎ－ジエチル－Ｓ，Ｓ－ジフルオロスルフィルイミニウムテトラフルオロボラート）、ＸｔａｌＦｌｕｏｒ－Ｍ（ジフルオロ（モルホリノ）スルホニウムテトラフルオロボラート）、ＦｌｕｏＬｅａｄ（４－ｔ－ブチル－２、６－ジメチルフェニルサルファートルフルオリド）、石川試薬（Ｎ，Ｎ－ジエチル－１，１，２，３，３，３－ヘキサフルオロプロピルアミン）、ＤＦＩ（２，２－ジフルオロ－１，３－ジメチルイミダゾリジン）等が挙げられる。 As the fluorinating agent used in this reaction, DAST (trifluoride-N, N-diethylaminosulfur), Deoxo-Fluor (N, N-dimethoxyethylaminosulfur trifluoride), XtalFluor-E (N, N-diethyl) -S, S-difluorosulfiliminium tetrafluoroborate), XtalFluor-M (difluoro (morpholino) sulfonium tetrafluoroborate), FluoLead (4-t-butyl-2,6-dimethylphenylsulfurtolufluoride) , Ishikawa reagent (N, N-diethyl-1,1,2,3,3,3-hexafluoropropylamine), DFI (2,2-difluoro-1,3-dimethylimidazolidine) and the like.
　本反応に使用するフッ素化剤の量は、式（１ｕ）で表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に制限されることはないが、通常、１当量以上２０当量以下である。 The amount of the fluorinating agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1u), It is 1 equivalent or more and 20 equivalents or less.
　本反応を円滑に進行させるために、１，８－ジアザビシクロ［５，４，０］ウンデカ－７－エン、トリエチルアミン三フッ化水素酸塩等のような添加剤を加えることができるが、必須ではない。 In order to make this reaction proceed smoothly, an additive such as 1,8-diazabicyclo [5,4,0] undec-7-ene or triethylamine trihydrofluoride can be added, but it is not essential. Absent.
　本反応に使用する添加剤の量は、式（１ｕ）で表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に制限されることはないが、通常、１当量以上２０当量以下である。 The amount of the additive used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more relative to the compound represented by the formula (1u). It is equal to or more than 20 equivalents.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but ether solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, etc., Benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ester-based solvents such as ethyl acetate, isopropyl acetate and butyl acetate, halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride. . These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（１ｕ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (1u). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、－８０℃以上１００℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 100 ° C or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When using an aqueous solution, dissolve an alkaline aqueous solution in which the salts potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc., and salts containing sulfur atoms such as sodium thiosulfate, sodium sulfite, etc. are dissolved. The aqueous solution, salt solution, etc. can be optionally used. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- It is possible to add an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane and chloroform, a hydrocarbon solvent such as hexane, heptane, cyclohexane and methylcyclohexane, which is incompatible with water. It is possible. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（１ｖ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (1v) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（１ｖ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (1v) obtained above can be distilled under reduced pressure to remove the solvent.
　溶媒留去後に得られた式（１ｖ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (1v) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法Ｘ］
Figure JPOXMLDOC01-appb-C000061
　式中、Ｒ１ａ、Ｒ２ｃ、Ｒ３、Ｘ、Ｚ、ｎおよび破線部は前記と同義である。 [Production method X]
Figure JPOXMLDOC01-appb-C000061
In the formula, R1a, R2c, R3, X, Z, n and the broken line portion have the same meanings as described above.
　製造方法Ｘは、トリフルオロメチル基を有する式（３ｅ）で表される化合物を得る方法であって、式（３ａ）で表される化合物とジフルオロ（フルオロスルホニル）酢酸メチルとを、遷移金属類存在下、溶媒中で反応させることを含む製造方法である。 The production method X is a method of obtaining a compound represented by the formula (3e) having a trifluoromethyl group, wherein the compound represented by the formula (3a) and methyl difluoro (fluorosulfonyl) acetate are used as transition metals. It is a production method comprising reacting in a solvent in the presence.
　式（３ａ）中、好ましいＲ１ａは、塩素原子、臭素原子、またはヨウ素原子である。 In the formula (3a), preferable R1a is a chlorine atom, a bromine atom or an iodine atom.
　本反応に使用するジフルオロ（フルオロスルホニル）酢酸メチルは、市販品として入手または公知の方法で製造できる。 The methyl difluoro (fluorosulfonyl) acetate used in this reaction can be obtained as a commercial product or can be produced by a known method.
　本反応に使用するジフルオロ（フルオロスルホニル）酢酸メチルの量は、式（３ａ）で表される化合物に対して、１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、好ましくは、１当量以上５０当量以下である。 The amount of methyl difluoro (fluorosulfonyl) acetate used in this reaction is not particularly limited as long as the intended reaction proceeds, provided that it is at least 1 equivalent with respect to the compound represented by formula (3a). However, it is preferably 1 equivalent or more and 50 equivalents or less.
　本反応に使用する遷移金属類は、銅類等である。好ましくは、臭化銅やヨウ化銅等が挙げられる。 The transition metals used in this reaction are copper and the like. Preferably, copper bromide, copper iodide, or the like is used.
　本反応に使用する遷移金属類の量は、式（３ａ）で表される化合物に対して、１当量以上あればよく、目的とする反応が進行する限りにおいて特に制限されることはないが、好ましくは、１当量以上５０当量以下である。 The amount of the transition metal used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (3a), and is not particularly limited as long as the intended reaction proceeds, It is preferably 1 equivalent or more and 50 equivalents or less.
　本反応を効率的に進行させるために、エチルジイソプロピルアミンやヘキサメチルリン酸トリアミド等の添加剤を加えることができるが、必須ではない。 In order to proceed this reaction efficiently, additives such as ethyldiisopropylamine and hexamethylphosphoric triamide can be added, but it is not essential.
　本反応に使用する添加剤の量は、式（３ａ）で表される化合物に対して５０当量以下であり、目的とする反応が進行する限りにおいて特に限定されることはない。 The amount of the additive used in this reaction is 50 equivalents or less with respect to the compound represented by the formula (3a), and is not particularly limited as long as the intended reaction proceeds.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド系溶媒、ジメチルスルホキシド、スルホラン等の硫黄系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, Examples thereof include sulfur-based solvents such as dimethyl sulfoxide and sulfolane. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（３ａ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (3a). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、０℃以上１５０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、アンモニア、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。また、濾過操作を行うことにより、不溶物を除去することも可能であるが必須ではない。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride or the like is dissolved, an alkaline aqueous solution in which ammonia, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like is dissolved, An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium thiosulfate or sodium sulfite is dissolved can be optionally used. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. It is also possible, but not essential, to remove insolubles by performing a filtration operation.
　前記で得られた式（３ｅ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (3e) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（３ｅ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (3e) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
　溶媒留去後に得られた式（３ｅ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (3e) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法Ｙ］
Figure JPOXMLDOC01-appb-C000062
　式中、ＬａはＳを表し、ＬｂはＳＯまたはＳＯ２を表し、Ｏｘ’は酸化剤を表す。 [Production method Y]
Figure JPOXMLDOC01-appb-C000062
In the formula, La represents S, Lb represents SO or SO 2 , and Ox ′ represents an oxidizing agent.
　製造方法Ｙは、式（１）で表される化合物中、Ｒ１、Ｒ２、Ｒ３およびＺに含まれるＬｂがＳＯまたはＳＯ２である式（Ｌｂ）で表される化合物の方法であって、式（１）で表される化合物中、Ｒ１、Ｒ２、Ｒ３およびＺに含まれるＬａがＳである式（Ｌａ）で表される化合物と酸化剤（Ｏｘ’）とを、溶媒中で反応させることを含む製造方法である。 Production method Y is the compound represented by the formula (1), a method of compound Lb contained in R1, R2, R3 and Z is represented by formula (Lb) is SO or SO 2, wherein In the compound represented by (1), the compound represented by the formula (La) in which La contained in R1, R2, R3 and Z is S and the oxidizing agent (Ox ′) are reacted in a solvent. It is a manufacturing method including.
　本反応に使用する酸化剤は、過酸化水素水、メタ－クロロ過安息香酸等の過酸化物類等が挙げられる。また、タングステン酸ナトリウムのような遷移金属類を添加することもできる。 Examples of the oxidizing agent used in this reaction include hydrogen peroxide solution and peroxides such as meta-chloroperbenzoic acid. Also, transition metals such as sodium tungstate can be added.
　本反応に使用する酸化剤の量は、ＳＯを製造する際には式（Ｌａ）で表される化合物に対して、通常、１．０当量以上１．２当量以下であり、ＳＯ２を製造する際には、通常、２当量以上１０当量以下である。また、遷移金属類を添加する際には、通常、０．００１当量以上１当量以下である。 The amount of the oxidizing agent used in this reaction is usually 1.0 equivalent or more and 1.2 equivalents or less with respect to the compound represented by the formula (La) when SO is produced, and SO 2 is produced. When doing, it is usually 2 equivalents or more and 10 equivalents or less. When adding transition metals, the amount is usually 0.001 equivalent or more and 1 equivalent or less.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、水溶媒、酢酸等の酸性系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、アセトニトリル等のニトリル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it may be an aqueous solvent, an acidic solvent such as acetic acid, benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene or the like. Examples thereof include benzene-based solvents, nitrile-based solvents such as acetonitrile, halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（Ｌａ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (La). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、－１０℃以上１２０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -10 ° C or higher and 120 ° C or lower or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When using an aqueous solution, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, etc. are dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc. are dissolved, sodium thiosulfate, sulfurous acid An aqueous solution or a salt solution in which a salt containing a sulfur atom such as sodium is dissolved can be arbitrarily used. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（Ｌｂ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (Lb) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（Ｌｂ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (Lb) obtained above can be distilled under reduced pressure to remove the solvent.
　溶媒留去後に得られた式（Ｌｂ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (Lb) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法Ｚ］
Figure JPOXMLDOC01-appb-C000063
　式中、Ｒ１、Ｒ２ａ、Ｒ３、Ｚ、ｎおよび破線部は前記と同義である。 [Production method Z]
Figure JPOXMLDOC01-appb-C000063
In the formula, R1, R2a, R3, Z, n and the broken line portion have the same meanings as described above.
　製造方法Ｚは、硫黄原子を含む式（３ｇ）で表される化合物を得る方法であって、式（３ｆ）で表される化合物と硫黄化剤（Ｓ－Ｒ）とを、溶媒中で反応させることを含む製造方法である。 The production method Z is a method for obtaining a compound represented by the formula (3g) containing a sulfur atom, which comprises reacting the compound represented by the formula (3f) with a sulfurizing agent (SR) in a solvent. It is a manufacturing method including:
　本反応に使用する硫黄化剤としては、ローソン試薬（２，４－ビス（４－メトキシフェニル）－１，３－ジチア－２，４－ジホスフェタン－２，４－ジスルフィド）、ベリュー試薬（２，４－ビス（４－フェノキシフェニル）－１，３－ジチア－２，４－ジホスフェタン－２，４－ジスルフィド）等が挙げられる。 Examples of the sulfurizing agent used in this reaction include Lawesson's reagent (2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide) and Berrie's reagent (2. 4-bis (4-phenoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide) and the like can be mentioned.
　本反応に使用する硫黄化剤の量は、式（３ｆ）で表される化合物に対して０．５当量以上あればよく、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上１０当量以下である。 The amount of the sulfurizing agent used in this reaction may be 0.5 equivalent or more with respect to the compound represented by the formula (3f), and is not particularly limited as long as the intended reaction proceeds. Usually, it is 1 equivalent or more and 10 equivalents or less.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Examples thereof include benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（３ｆ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (3f). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、５０℃以上１８０℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 50 ° C. or higher and 180 ° C. or lower or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水、もしくは適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。また、本反応においては、分液操作は必須ではない。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. In this reaction, a liquid separation operation is not essential.
　前記で得られた式（３ｇ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (3g) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（３ｇ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (3 g) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
　溶媒留去後に得られた式（３ｇ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (3 g) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法ＡＡ］
Figure JPOXMLDOC01-appb-C000064
　式中、Ｏｘ、Ｒ１、Ｒ２ａ、Ｒ３、Ｒｗ、Ｚ、ｎおよび波線部は前記と同義である。 [Production method AA]
Figure JPOXMLDOC01-appb-C000064
In the formula, Ox, R1, R2a, R3, Rw, Z, n and the wavy line portion have the same meanings as described above.
　製造方法ＡＡは、式（１ｗ）で表される化合物を得る方法であって、式（２ｈ）で表される化合物と酸化剤（Ｏｘ）とを、溶媒中で反応させることを含む製造方法である。 The production method AA is a method for obtaining a compound represented by the formula (1w), which comprises reacting the compound represented by the formula (2h) with an oxidizing agent (Ox) in a solvent. is there.
　製造方法Ｂにおける式（２ｃ）で表される化合物を、式（２ｈ）で表される化合物に代えて使用することにより、製造方法Ｂに準じて製造方法ＡＡを実施することができる。 By using the compound represented by the formula (2c) in the production method B instead of the compound represented by the formula (2h), the production method AA can be carried out according to the production method B.
［製造方法ＡＢ］
Figure JPOXMLDOC01-appb-C000065
　式中、Ｏ－Ｒは酸化剤を表し、Ｒ１、Ｒ３、Ｘ、Ｚおよびｎは前記と同義である。 [Production method AB]
Figure JPOXMLDOC01-appb-C000065
In the formula, OR represents an oxidizing agent, and R1, R3, X, Z and n have the same meanings as described above.
　製造方法ＡＢは、水酸基を含む式（２ｉ）で表される化合物を得る方法であって、式（２ｄ）で表される化合物と酸化剤（Ｏ－Ｒ）とを、塩基存在下、溶媒中で反応させることを含む製造方法である。 The production method AB is a method for obtaining a compound represented by the formula (2i) containing a hydroxyl group, which comprises mixing the compound represented by the formula (2d) and an oxidizing agent (OR) in the presence of a base in a solvent. It is a manufacturing method including reacting with.
　本反応に使用する酸化剤としては、Ｄａｖｉｓ試薬（３－フェニル－２－フェニルスルホニル－１、２－オキサジリジン）、（２Ｒ、８ａＳ）－（＋）－（カンファリルスルホニル）オキサジリジン、（２Ｓ、８ａＲ）－（－）－（カンファリルスルホニル）オキサジリジン等のオキサジリジン類、過酸化水素水、メタ－クロロ過安息香酸、ジメチルジオキシランなどの過酸化物類等が挙げられる。 Examples of the oxidizing agent used in this reaction include Davis reagent (3-phenyl-2-phenylsulfonyl-1,2-oxaziridine), (2R, 8aS)-(+)-(campharylsulfonyl) oxaziridine, (2S, 8aR )-(−)-(Camphorylsulfonyl) oxaziridine and other oxaziridines, hydrogen peroxide solution, meta-chloroperbenzoic acid, and peroxides such as dimethyldioxirane.
　本反応に使用する酸化剤の量は、式（２ｄ）で表される化合物に対して１当量以上あれば、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、１当量以上１０当量以下である。 The amount of the oxidizing agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (2d), but it is usually 1 It is equal to or more than 10 equivalents.
　本反応に使用する塩基として、水素化ナトリウム等の金属ヒドリド類、メチルリチウム、ブチルリチウム、ｓｅｃ－ブチルリチウム、ｔ－ブチルリチウム、ヘキシルリチウム等の有機リチウム類や、リチウムジイソプロピルアミド、ヘキサメチルジシラザンリチウム、ヘキサメチルジシラザンナトリウム、ヘキサメチルジシラザンカリウム等の金属アミド類が例示される。 As the base used in this reaction, metal hydrides such as sodium hydride, organic lithiums such as methyllithium, butyllithium, sec-butyllithium, t-butyllithium, and hexyllithium, lithium diisopropylamide, hexamethyldisilazane Examples are metal amides such as lithium, sodium hexamethyldisilazane, and potassium hexamethyldisilazane.
　本反応に使用する塩基の量は、式（２ｄ）で表される化合物に対して１当量以上あればよく、目的とする反応が進行する限りにおいて特に制限されることはないが、通常、１当量以上２０当量以下である。 The amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (2d) and is not particularly limited as long as the intended reaction proceeds, but it is usually 1 It is equal to or more than 20 equivalents.
　反応を円滑に進行させるために、ヘキサメチルリン酸トリアミド、Ｎ，Ｎ’－ジメチル尿素、テトラメチルエチレンジアミン等の添加剤や、クロロトリメチルシラン、クロロトリエチルシラン、トリフルオロメタンスルホン酸トリメチルシリル、トリフルオロメタンスルホン酸トリエチルシリル等のシリル化剤を添加することができるが、必須ではない。また、これらの添加剤およびシリル化剤は、同時、またはどちらか一方のみを使用することが可能である。本反応に使用する添加剤の使用量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（２ｄ）で表される化合物に対して、１当量以上１００当量以下である。本反応に使用するシリル剤の使用量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（２ｄ）で表される化合物に対して、１当量以上１００当量以下である。 In order to make the reaction proceed smoothly, additives such as hexamethylphosphoric triamide, N, N′-dimethylurea, tetramethylethylenediamine, chlorotrimethylsilane, chlorotriethylsilane, trifluoromethanesulfonic acid trimethylsilyl, trifluoromethanesulfonic acid, etc. A silylating agent such as triethylsilyl can be added, but is not required. Further, these additives and the silylating agent can be used at the same time or only one of them can be used. The amount of the additive used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 1 equivalent or more and 100 equivalents relative to the compound represented by the formula (2d). It is the following. The amount of the silylating agent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 1 equivalent or more and 100 equivalents relative to the compound represented by the formula (2d). It is the following.
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Examples thereof include benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, and hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（２ｄ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2d). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、－８０℃以上１００℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 100 ° C or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- It is possible to add an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane and chloroform, a hydrocarbon solvent such as hexane, heptane, cyclohexane and methylcyclohexane, which is incompatible with water. It is possible. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（２ｉ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (2i) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（２ｉ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (2i) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
　溶媒留去後に得られた式（２ｉ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (2i) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
［製造方法ＡＣ］
Figure JPOXMLDOC01-appb-C000066
　式中、Ｒ２ｅは置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、Ｃ２～Ｃ６のハロアルケニル基、置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、Ｃ２～Ｃ６のハロアルキニル基を表し、Ｒ１、Ｒ３、Ｘ、Ｚ、Ｌｖおよびｎは前記と同義である。 [Manufacturing method AC]
Figure JPOXMLDOC01-appb-C000066
In the formula, R2e is a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent A, a substituent A Represents a C2-C6 alkenyl group which may be optionally substituted with, a C2-C6 haloalkenyl group, a C2-C6 alkynyl group which may be optionally substituted with a substituent A, a C2-C6 haloalkynyl group, R1 , R3, X, Z, Lv and n are as defined above.
　製造方法ＡＣは、アルコキシ基を含む式（２ｊ）で表される化合物を得る方法であって、式（２ｉ）で表される化合物とＲ２ｅ－Ｌｖとを、塩基存在下、溶媒中で反応させること含む製造方法である。 The production method AC is a method for obtaining a compound represented by the formula (2j) containing an alkoxy group, wherein the compound represented by the formula (2i) and R2e-Lv are reacted in the presence of a base in a solvent. It is a manufacturing method including that.
　本反応に使用するＲ２ｅ－Ｌｖは、市販品として入手または公知の方法で製造することができる。 R2e-Lv used in this reaction can be obtained as a commercial product or can be produced by a known method.
　本反応に使用するＲ２ｅ－Ｌｖの量は、式（２ｊ）で表される化合物に対して１当量以上あればよく、目的とする反応が進行する限りにおいて特に制限されることはないが、通常、１当量以上５０当量以下である。 The amount of R2e-Lv used in this reaction may be 1 equivalent or more relative to the compound represented by the formula (2j), and is not particularly limited as long as the intended reaction proceeds, but It is 1 equivalent or more and 50 equivalents or less.
　本反応に使用する塩基として、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、水素化ナトリウム、酸化銀等の無機塩基類が例示されるが、目的とする反応が進行する限りにおいて特に限定されることはない。 Examples of the base used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, and silver oxide, as long as the intended reaction proceeds. There is no particular limitation in.
　本反応に使用する塩基の量は、式（２ｊ）で表される化合物に対して１当量以上あればよく、目的とする反応が進行する限りにおいて特に制限されることはないが、通常、１当量以上２０当量以下である。 The amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (2j), and is not particularly limited as long as the intended reaction proceeds, but it is usually 1 It is equal to or more than 20 equivalents.
　本反応に添加剤を使用する際、添加剤の使用量は、式（２ｊ）で表される化合物に対して、１当量以上１００当量以下である。 When an additive is used in this reaction, the amount of the additive used is 1 equivalent or more and 100 equivalents or less with respect to the compound represented by the formula (2j).
　本反応に使用する溶媒は、目的とする反応が進行する限りにおいて特に限定されることはないが、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル、ジメトキシエタン、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、メタノール、エタノール、イソプロパノール等のアルコール系溶媒、ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、アセトニトリル等のニトリル系溶媒、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド系溶媒、１，３－ジメチル－２－イミダゾリジノン等のウレア系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン系溶媒、ジメチルスルホキシド、スルホラン等の硫黄系溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒等が挙げられる。これらの溶媒は、単独または２種類以上を任意の割合で混合して使用することができる。 The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Methanol, ethanol, alcohol solvents such as isopropanol, benzene, toluene, xylene, mesitylene, chlorobenzene, benzene solvents such as dichlorobenzene, ethyl acetate, isopropyl acetate, ester solvents such as butyl acetate, nitrile solvents such as acetonitrile, Amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, dichloromethane, dichloroethane, Chloroform, halogenated solvents such as carbon tetrachloride, dimethyl sulfoxide, sulfur-based solvents such as sulfolane, acetone, methyl ethyl ketone, ketone solvents such as methyl isobutyl ketone. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.
　本反応に使用する溶媒量は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、式（２ｊ）で表される化合物に対して３重量倍以上２００重量倍以下である。 The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (2j). is there.
　本反応を行う際の温度は、目的とする反応が進行する限りにおいて特に限定されることはないが、通常、－８０℃以上１００℃以下または溶媒の沸点以下である。 The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 100 ° C or lower, or the boiling point of the solvent or lower.
　反応の後処理としては、反応混合物に対して、水または適当な水溶液を加えることにより、分液操作を行うことが可能である。水溶液を使用する場合は、塩酸、硫酸、塩化アンモニウム等を溶解した酸性水溶液、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を溶解したアルカリ水溶液、チオ硫酸ナトリウム、亜硫酸ナトリウム等の硫黄原子を含む塩を溶解した水溶液や食塩水等を任意に使用することができる。分液操作の際に、必要に応じて、トルエン、キシレン、ベンゼン、クロロベンゼン、ジクロロベンゼン等のベンゼン系溶媒、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系溶媒、ジエチルエーテル、ジイソプロピルエーテル、メチル－ｔ－ブチルエーテル等のエーテル系溶媒、ジクロロメタン、ジクロロエタン、クロロホルム等のハロゲン系溶媒、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の炭化水素系溶媒等の水と相溶することのない溶媒を追加することが可能である。また、これらの溶媒は、単独で使用することも、２種類以上で任意の割合で混合することも可能である。分液の回数は特に制限されることがなく、目的とする純度や収量に応じて実施することができる。 As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- It is possible to add an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane and chloroform, a hydrocarbon solvent such as hexane, heptane, cyclohexane and methylcyclohexane, which is incompatible with water. It is possible. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.
　前記で得られた式（２ｊ）で表される化合物を含む反応混合物は、硫酸ナトリウムや硫酸マグネシウム等の乾燥剤で水分を除去することができるが、必須ではない。 The water content of the reaction mixture containing the compound represented by the formula (2j) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.
　前記で得られた式（２ｊ）で表される化合物を含む反応混合物は、化合物が分解しない限りにおいて、減圧下で溶媒留去することが可能である。 The reaction mixture containing the compound represented by the formula (2j) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.
　溶媒留去後に得られた式（２ｊ）で表される化合物を含む反応混合物は、適当な溶媒により、洗浄、再沈殿、再結晶、カラムクロマトグラフィー等にて精製することができる。目的とする純度に応じて適宜設定すればよい。 The reaction mixture containing the compound represented by the formula (2j) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.
　以上に示した、製造方法Ａ～製造方法ＡＣを任意に組み合わせて、式（１）で表される化合物を製造することができる。もしくは、公知の方法と製造方法Ａ～製造方法Ｚとを任意に組み合わせても、式（１）で表される化合物を製造することができる。 The compound represented by the formula (1) can be produced by arbitrarily combining the production methods A to AC shown above. Alternatively, the compound represented by the formula (1) can be produced by optionally combining the known method and the production methods A to Z.
　本発明化合物は、植物に対して有害な生物を防除できるために、農薬、特に農園芸用有害生物防除剤として使用することができる。具体的には、殺菌剤、殺虫剤、除草剤、植物成長調整剤等が挙げられる。好ましくは、殺菌剤である。 Since the compound of the present invention can control organisms harmful to plants, it can be used as a pesticide, especially as a pesticide for agricultural and horticultural use. Specific examples include fungicides, insecticides, herbicides, plant growth regulators, and the like. A bactericide is preferable.
　本発明化合物は、植物病害の防除のために、畑地、水田、茶園、果樹園、牧草地、芝生、森林、庭園、街路樹等で農園芸用殺菌剤として使用することができる。　本発明でいう植物病害とは、農作物、花き、花木、樹木等の植物に萎ちょう、立枯れ、黄化、萎縮、徒長等の全身的な異常な病的症状、または斑点、葉枯れ、モザイク、葉巻、枝枯れ、根腐れ、根こぶ、こぶ等の部分的な病的症状が惹起されることである。即ち、植物が病気になることである。植物病害を引き起こす病原体として、主に、菌類、細菌、スピロプラズマ、ファイトプラズマ、ウイルス、ウイロイド、寄生性高等植物、線虫等が挙げられる。本発明化合物は菌類に有効であるが、これに限定されるものではない。 The compound of the present invention can be used as a fungicide for agricultural and horticultural use for controlling plant diseases in fields, paddy fields, tea fields, orchards, meadows, lawns, forests, gardens, roadside trees and the like. The plant diseases referred to in the present invention are crops, flowers, flowers, trees, wilting of plants such as trees, systemic abnormal pathological symptoms such as wilting, yellowing, atrophy, and captivity, or spots, leaf wilting, mosaic. , Partial morbidity such as cigar, wilting, root rot, root-knot, and hump are caused. That is, the plant becomes ill. Pathogens causing plant diseases mainly include fungi, bacteria, spiroplasma, phytoplasma, viruses, viroids, parasitic higher plants, nematodes and the like. The compound of the present invention is effective on fungi, but is not limited thereto.
　菌類によって引き起こされる病害は、主に菌類病である。菌類病を引き起こす菌類（病原体）として、ネコブカビ菌類、卵菌類、接合菌類、子のう菌類、担子菌類および不完全菌類が挙げられる。例えば、ネコブカビ菌類として、根こぶ病菌、ジャカイモ粉状そうか病菌、テンサイそう根病菌、卵菌類として疫病菌、べと病菌、Ｐｙｔｈｉｕｍ属菌、Ａｐｈａｎｏｍｙｃｅｓ属菌、接合菌類としてＲｈｉｚｏｐｕｓ属菌、子のう菌類としてモモ縮葉病菌、トウモロコシごま葉枯病菌、イネいもち病菌、うどんこ病菌、炭そ病菌、赤かび病菌、ばか苗病菌、菌核病菌、担子菌類としてさび病菌類、黒穂病菌類、紫紋羽病菌、もち病菌、紋枯病菌、不完全菌類として灰色かび病菌、Ａｌｔｅｒｎａｒｉａ属菌、Ｆｕｓａｒｉｕｍ属菌、Ｐｅｎｉｃｉｌｌｉｕｍ属菌、Ｒｈｉｚｏｃｔｏｎｉａ属菌、白絹病菌等が挙げられる。 The diseases caused by fungi are mainly fungal diseases. Examples of fungi (pathogens) that cause fungal diseases include Aspergillus niger, Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and incomplete fungi. For example, as fungus fungi, root-knot fungus, powdery mildew fungus, sugar beet wilt fungus, oomycete, downy mildew, Pythium genus, Aphanomyces genus, zygomycetes Rhizopus genus, ascomycetes Fungi include peach leaf blight, corn sesame leaf blight, rice blast, powdery mildew, anthracnose, red mold, bacillus seedling, sclerotium, basidiomycetes, rust, smut, and purple print Fungi, blast fungus, sheath blight fungus, and imperfect fungi include gray mold, Alternaria, Fusarium, Penicillium, Rhizoctonia, and white silk.
　本発明化合物は、各種の植物病害に対して有効である。以下に、病害名およびその病原菌名の具体例を示す。 The compound of the present invention is effective against various plant diseases. Hereinafter, specific examples of the disease name and the pathogen name will be shown.
　イネのいもち病（Ｍａｇｎａｐｏｒｔｈｅ　ｇｒｉｓｅａ）、紋枯病（Ｔｈａｎａｔｅｐｈｏｒｕｓ　ｃｕｃｕｍｅｒｉｓ）、褐色菌核病（Ｃｅｒａｔｏｂａｓｉｄｉｕｍ　ｓｅｔａｒｉａｅ）、褐色小粒菌核病（Ｗａｉｔｅａ　ｃｉｒｃｉｎａｔａ）、褐色紋枯病（Ｔｈａｎａｔｅｐｈｏｒｕｓ　ｃｕｃｕｍｅｒｉｓ）、球状菌核病（Ｓｃｌｅｒｏｔｉｕｍ　ｈｙｄｒｏｐｈｉｌｕｍ）、赤色菌核病（Ｗａｉｒｅａ　ｃｉｒｃｉｎａｔａ）、黒しゅ病（Ｅｎｔｙｌｏｍａ　ｄａｃｔｙｌｉｄｉｓ）、小球菌核病（Ｍａｇｎａｐｏｒｔｈｅ　ｓａｌｖｉｎｉｉ）、灰色菌核病（Ｃｅｒａｔｏｂａｓｉｄｉｕｍ　ｃｏｒｎｉｇｅｒｕｍ）、ごま葉枯病（Ｃｏｃｈｌｉｏｂｏｌｕｓ　ｍｉｙａｂｅａｎｕｓ）、条葉枯病（Ｓｐｈａｅｒｕｌｉｎａ　ｏｒｙｚｉｎａ）、ばか苗病（Ｇｉｂｂｅｒｅｌｌａ　ｆｕｊｉｋｕｒｏｉ）、苗立枯病（Ｐｙｔｈｉｕｍ　ｓｐｐ．、Ｆｕｓａｒｉｕｍ　ｓｐｐ．、Ｔｒｉｃｈｏｄｅｒｍａ　ｓｐｐ．、Ｒｈｉｚｏｐｕｓ　ｓｐｐ．、Ｒｈｉｚｏｃｔｏｎｉａ　ｓｏｌａｎｉ、Ｍｕｃｏｒ　ｓｐ．、Ｐｈｏｍａ　ｓｐ．）、苗腐病（Ｐｙｔｈｉｕｍ　ｓｐｐ．、Ａｃｈｌｙａ　ｓｐｐ．、Ｄｉｃｔｙｕｃｈｕｓ　ｓｐｐ．）、稲こうじ病（Ｃｌａｖｉｃｅｐｓ　ｖｉｒｅｎｓ）、墨黒穂病（Ｔｉｌｌｅｔｉａ　ｂａｒｃｌａｙａｎａ）、褐色米（Ｃｕｒｖｕｌａｒｉａ　ｓｐｐ．、Ａｌｔｅｒｎａｒｉａ　ｓｐｐ．）、黄化萎縮病（Ｓｃｌｅｒｏｐｈｔｈｏｒａ　ｍａｃｒｏｓｐｏｒａ）、白葉枯病（Ｘａｎｔｈｏｍｏｎａｓ　ｏｒｙｚａｅ　ｐｖ．　ｏｒｙｚａｅ）、褐条病（Ａｃｉｄｏｖｏｒａｘ　ａｖｅｎａｅ　ｓｕｂｓｐ．　ａｖｅｎａｅ）、内頴褐変病（Ｅｒｗｉｎｉａ　ａｎａｎａｓ）、苗立枯細菌病（Ｂｕｒｋｈｏｌｄｅｒｉａ　ｐｌａｎｔａｒｉｉ）、もみ枯細菌病（Ｂｕｒｋｈｏｌｄｅｒｉａ　ｇｌｕｍａｅ）、葉鞘褐変病（Ｐｓｅｕｄｏｍｏｎａｓ　ｆｕｓｃｏｖａｇｉｎａｅ）、かさ枯病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．ｏｒｙｚａｅ）、株腐病（Ｅｒｗｉｎｉａ　ｃｈｒｙｓａｎｔｈｅｍｉ）、黄萎病（Ｐｈｙｔｏｐｌａｓｍａ　ｏｒｙｚａｅ）、縞葉枯病（Ｒｉｃｅ　ｓｔｒｉｐｅ　ｔｅｎｕｉｖｉｒｕｓ）、萎縮病（Ｒｉｃｅ　ｄｗａｒｆ　ｒｅｏｖｉｒｕｓ）；ムギ類のうどんこ病（Ｂｌｕｍｅｒｉａ　ｇｒａｍｉｎｉｓ　ｆ．ｓｐ．ｈｏｒｄｅｉ；　ｆ．ｓｐ．ｔｒｉｔｉｃｉ）、さび病（Ｐｕｃｃｉｎｉａ　ｓｔｒｉｉｆｏｒｍｉｓ、　Ｐｕｃｃｉｎｉａ　ｇｒａｍｉｎｉｓ、Ｐｕｃｃｉｎｉａ　ｒｅｃｏｎｄｉｔａ、Ｐｕｃｃｉｎｉａ　ｈｏｒｄｅｉ）、斑葉病（Ｐｙｒｅｎｏｐｈｏｒａ　ｇｒａｍｉｎｅａ）、網斑病（Ｐｙｒｅｎｏｐｈｏｒａ　ｔｅｒｅｓ）、赤かび病（Ｇｉｂｂｅｒｅｌｌａ　ｚｅａｅ、Ｆｕｓａｒｉｕｍ　ｃｕｌｍｏｒｕｍ、Ｆｕｓａｒｉｕｍ　ａｖｅｎａｃｅｕｍ、Ｍｏｎｏｇｒａｐｈｅｌｌａ　ｎｉｖａｌｉｓ）、雪腐病（Ｔｙｐｈｕｌａ　ｉｎｃａｒｎａｔａ、Ｔｙｐｈｕｌａ　ｉｓｈｉｋａｒｉｅｎｓｉｓ、Ｍｏｎｏｇｒａｐｈｅｌｌａ　ｎｉｖａｌｉｓ）、裸黒穂病（Ｕｓｔｉｌａｇｏ　ｎｕｄａ）、なまぐさ黒穂病（Ｔｉｌｌｅｔｉａ　ｃａｒｉｅｓ、Ｔｉｌｌｅｔｉａ　ｃｏｎｔｒｏｖｅｒｓａ）、眼紋病（Ｐｓｅｕｄｏｃｅｒｃｏｓｐｏｒｅｌｌａ　ｈｅｒｐｏｔｒｉｃｈｏｉｄｅｓ）、株腐病（Ｃｅｒａｔｏｂａｓｉｄｉｕｍ　ｇｒａｍｉｎｅｕｍ）、雲形病（Ｒｈｙｎｃｈｏｓｐｏｒｉｕｍ　ｓｅｃａｌｉｓ）、葉枯病（Ｓｅｐｔｏｒｉａ　ｔｒｉｔｉｃｉ）、ふ枯病（Ｐｈａｅｏｓｐｈａｅｒｉａ　ｎｏｄｏｒｕｍ）、苗立枯病（Ｆｕｓａｒｉｕｍ　ｓｐｐ．、Ｐｙｔｈｉｕｍ　ｓｐｐ．、Ｒｈｉｚｏｃｔｏｎｉａ　ｓｐｐ．、Ｓｅｐｔｏｒｉａ　ｓｐｐ．、Ｐｙｒｅｎｏｐｈｏｒａ　ｓｐｐ．）、立枯病（Ｇａｅｕｍａｎｎｏｍｙｃｅｓ　ｇｒａｍｉｎｉｓ）、炭疽病（Ｃｏｌｌｅｔｏｔｒｉｃｈｕｍ　ｇｒａｍｉｎｉｃｏｌａ）、麦角病（Ｃｌａｖｉｃｅｐｓ　ｐｕｒｐｕｒｅａ）、斑点病（Ｃｏｃｈｌｉｏｂｏｌｕｓ　ｓａｔｉｖｕｓ）、黒節病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．　ｓｙｒｉｎｇａｅ）；トウモロコシの赤かび病（Ｇｉｂｂｅｒｅｌｌａ　ｚｅａｅ等）、苗立枯病（Ｆｕｓａｒｉｕｍ　ａｖｅｎａｃｅｕｍ、　Ｐｅｎｉｃｉｌｌｉｕｍ　ｓｐｐ、　Ｐｙｔｈｉｕｍ　ｓｐｐ．、Ｒｈｉｚｏｃｔｏｎｉａ　ｓｐｐ．）、さび病（Ｐｕｃｃｉｎｉａ　ｓｏｒｇｈｉ）、ごま葉枯病（Ｃｏｃｈｌｉｏｂｏｌｕｓ　ｈｅｔｅｒｏｓｔｒｏｐｈｕｓ）、黒穂病（Ｕｓｔｉｌａｇｏ　ｍａｙｄｉｓ）、炭疽病（Ｃｏｌｌｅｔｏｔｒｉｃｈｕｍ　ｇｒａｍｉｎｉｃｏｌａ）、北方斑点病（Ｃｏｃｈｌｉｏｂｏｌｕｓ　ｃａｒｂｏｎｕｍ）、褐条病（Ａｃｉｄｏｖｏｒａｘ　ａｖｅｎａｅ　ｓｕｂｓｐ．　ａｖｅｎａｅ）、条斑細菌病（Ｂｕｒｋｈｏｌｄｅｒｉａ　ａｎｄｒｏｐｏｇｏｎｉｓ）、倒伏細菌病（Ｅｒｗｉｎｉａ　ｃｈｒｙｓａｎｔｈｅｍｉ　ｐｖ．　ｚｅａｅ）、萎ちょう細菌病（Ｅｒｗｉｎｉａ　ｓｔｅｗａｒｔｉｉ）；ブドウのべと病（Ｐｌａｓｍｏｐａｒａ　ｖｉｔｉｃｏｌａ）、さび病（Ｐｈｙｓｏｐｅｌｌａ　ａｍｐｅｌｏｐｓｉｄｉｓ）、うどんこ病（Ｕｎｃｉｎｕｌａ　ｎｅｃａｔｏｒ）、黒とう病（Ｅｌｓｉｎｏｅ　ａｍｐｅｌｉｎａ）、晩腐病（Ｇｌｏｍｅｒｅｌｌａ　ｃｉｎｇｕｌａｔａ、　Ｃｏｌｌｅｔｏｔｒｉｃｈｕｍ　ａｃｕｔａｔｕｍ）、黒腐病（Ｇｕｉｇｎａｒｄｉａ　ｂｉｄｗｅｌｌｉｉ）、つる割病（Ｐｈｏｍｏｐｓｉｓ　ｖｉｔｉｃｏｌａ）、すす点病（Ｚｙｇｏｐｈｉａｌａ　ｊａｍａｉｃｅｎｓｉｓ）、灰色かび病（Ｂｏｔｒｙｔｉｓ　ｃｉｎｅｒｅａ）、芽枯病（Ｄｉａｐｏｒｔｈｅ　ｍｅｄｕｓａｅａ）、紫紋羽病（Ｈｅｌｉｃｏｂａｓｉｄｉｕｍ　ｍｏｍｐａ）、白紋羽病（Ｒｏｓｅｌｌｉｎｉａ　ｎｅｃａｔｒｉｘ）、根頭がんしゅ病（Ａｇｒｏｂａｃｔｅｒｉｕｍ　ｖｉｔｉｓ）；リンゴのうどんこ病（Ｐｏｄｏｓｐｈａｅｒａ　ｌｅｕｃｏｔｒｉｃｈａ）、黒星病（Ｖｅｎｔｕｒｉａ　ｉｎａｅｑｕａｌｉｓ）、斑点落葉病（Ａｌｔｅｒｎａｒｉａ　ｍａｌｉ）、赤星病（Ｇｙｍｎｏｓｐｏｒａｎｇｉｕｍ　ｙａｍａｄａｅ）、モニリア病（Ｍｏｎｉｌｉｎｉａ　ｍａｌｉ）、腐らん病（Ｖａｌｓａ　ｃｅｒａｔｏｓｐｅｒｍａ）、輪紋病（Ｂｏｔｒｙｏｓｐｈａｅｒｉａ　ｂｅｒｅｎｇｅｒｉａｎａ）、炭疽病（Ｃｏｌｌｅｔｏｔｒｉｃｈｕｍ　ａｃｕｔａｔｕｍ、Ｇｌｏｍｅｒｅｌｌａ　ｃｉｎｇｕｌａｔａ）、すす点病（Ｚｙｇｏｐｈｉａｌａ　ｊａｍａｉｃｅｎｓｉｓ）、すす斑病（Ｇｌｏｅｏｄｅｓ　ｐｏｍｉｇｅｎａ）、黒点病（Ｍｙｃｏｓｐｈａｅｒｅｌｌａ　ｐｏｍｉ）、紫紋羽病（Ｈｅｌｉｃｏｂａｓｉｄｉｕｍ　ｍｏｍｐａ）、白紋羽病（Ｒｏｓｅｌｌｉｎｉａ　ｎｅｃａｔｒｉｘ）、胴枯病（Ｐｈｏｍｏｐｓｉｓ　ｍａｌｉ、Ｄｉａｐｏｒｔｈｅ　ｔａｎａｋａｅ）、褐斑病（Ｄｉｐｌｏｃａｒｐｏｎ　ｍａｌｉ）、リンゴの火傷病（Ｅｒｗｉｎｉａ　ａｍｙｌｏｖｏｒａ）、根頭がんしゅ病（Ａｇｒｏｂａｃｔｅｒｉｕｍ　ｔｕｍｅｆａｃｉｅｎｓ）、毛根病（Ａｇｒｏｂａｃｔｅｒｉｕｍ　ｒｈｉｚｏｇｅｎｅｓ）；ナシの黒斑病（Ａｌｔｅｒｎａｒｉａ　ｋｉｋｕｃｈｉａｎａ）、黒星病（Ｖｅｎｔｕｒｉａ　ｎａｓｈｉｃｏｌａ）、赤星病（Ｇｙｍｎｏｓｐｏｒａｎｇｉｕｍ　ａｓｉａｔｉｃｕｍ）、輪紋病（Ｂｏｔｒｙｏｓｐｈａｅｒｉａ　ｂｅｒｅｎｇｅｒｉａｎａ　ｆ．ｓｐ．　ｐｉｒｉｃｏｌａ）、胴枯病（Ｐｈｏｍｏｐｓｉｓ　ｆｕｋｕｓｈｉｉ）、枝枯細菌病（Ｅｒｗｉｎｉａ　ｓｐ．）、根頭がんしゅ病（Ａｇｒｏｂａｃｔｅｒｉｕｍ　ｔｕｍｅｆａｃｉｅｎｓ）、さび色胴枯病（Ｅｒｗｉｎｉａ　ｃｈｒｙｓａｎｔｈｅｍｉ　ｐｖ．　ｃｈｒｙｓａｎｔｈｅｍｉ）、花腐細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．　ｓｙｒｉｎｇａｅ）；セイヨウナシの疫病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｃａｃｔｏｒｕｍ、　Ｐｈｙｔｏｐｈｔｈｏｒａ　ｓｙｒｉｎｇａｅ）、枝枯細菌病（Ｅｒｗｉｎｉａ　ｓｐ．）；モモの黒星病（Ｃｌａｄｏｓｐｏｒｉｕｍ　ｃａｒｐｏｐｈｉｌｕｍ）、ホモプシス腐敗病（Ｐｈｏｍｏｐｓｉｓ　ｓｐ．）、疫病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｓｐ．）、炭疽病（Ｃｏｌｌｅｔｏｔｒｉｃｈｕｍ　ｇｌｏｅｏｓｐｏｒｉｏｉｄｅｓ）、縮葉病（Ｔａｐｈｒｉｎａ　ｄｅｆｏｒｍａｎｓ）、穿孔細菌病（Ｘｈａｎｔｈｏｍｏｎａｓ　ｃａｍｐｅｓｔｒｉｓ　ｐｖ．　ｐｒｕｎｉ）、根頭がんしゅ病（Ａｇｒｏｂａｃｔｅｒｉｕｍ　ｔｕｍｅｆａｃｉｅｎｓ）；オウトウの炭疽病（Ｇｌｏｍｅｒｅｌｌａ　ｃｉｎｇｕｌａｔａ）、幼果菌核病（Ｍｏｎｉｌｉｎｉａ　ｋｕｓａｎｏｉ）、灰星病（Ｍｏｎｉｌｉｎｉａ　ｆｒｕｃｔｉｃｏｌａ）、根頭がんしゅ病（Ａｇｒｏｂａｃｔｅｒｉｕｍ　ｔｕｍｅｆａｃｉｅｎｓ）、樹脂細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．　ｓｙｒｉｎｇａｅ）；カキの炭疽病（Ｇｌｏｍｅｒｅｌｌａ　ｃｉｎｇｕｌａｔａ）、落葉病（Ｃｅｒｃｏｓｐｏｒａ　ｋａｋｉ；　Ｍｙｃｏｓｐｈａｅｒｅｌｌａ　ｎａｗａｅ）、うどんこ病（Ｐｈｙｌｌａｃｔｉｎｉａ　ｋａｋｉｋｏｒａ）、根頭がんしゅ病（Ａｇｒｏｂａｃｔｅｒｉｕｍ　ｔｕｍｅｆａｃｉｅｎｓ）；カンキツの黒点病（Ｄｉａｐｏｒｔｈｅ　ｃｉｔｒｉ）、緑かび病（Ｐｅｎｉｃｉｌｌｉｕｍ　ｄｉｇｉｔａｔｕｍ）、青かび病（Ｐｅｎｉｃｉｌｌｉｕｍ　ｉｔａｌｉｃｕｍ）、そうか病（Ｅｌｓｉｎｏｅ　ｆａｗｃｅｔｔｉｉ）、褐色腐敗病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｃｉｔｒｏｐｈｔｈｏｒａ）、かいよう病（Ｘｈａｎｔｈｏｍｏｎａｓ　ｃａｍｐｅｓｔｒｉｓ　ｐｖ．　ｃｉｔｒｉ）、褐斑細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．　ｓｙｒｉｎｇａｅ）、グリーニング病（Ｌｉｂｅｒｉｂａｃｔｏｒ　ａｓｉａｔｉｃｕｓ）、根頭がんしゅ病（Ａｇｒｏｂａｃｔｅｒｉｕｍ　ｔｕｍｅｆａｃｉｅｎｓ）；トマト、キュウリ、豆類、イチゴ、ジャガイモ、キャベツ、ナス、レタス等の灰色かび病（Ｂｏｔｒｙｔｉｓ　ｃｉｎｅｒｅａ）；トマト、キュウリ、豆類、イチゴ、ジャガイモ、ナタネ、キャベツ、ナス、レタス等の菌核病（Ｓｃｌｅｒｏｔｉｎｉａ　ｓｃｌｅｒｏｔｉｏｒｕｍ）；トマト、キュウリ、豆類、ダイコン、スイカ、ナス、ナタネ、ピーマン、ホウレンソウ、テンサイ等各種野菜の苗立枯病（Ｒｈｉｚｏｃｔｏｎｉａ　ｓｐｐ．、Ｐｙｔｈｉｕｍ　ｓｐｐ．、Ｆｕｓａｒｉｕｍ　ｓｐｐ．、Ｐｈｙｔｈｏｐｈｔｈｏｒａ　ｓｐｐ．、Ｓｃｌｅｒｏｔｉｎｉａ　ｓｃｌｅｒｏｔｉｏｒｕｍ等）；ナス科植物の青枯病（Ｒａｌｓｔｏｎｉａ　ｓｏｌａｎａｃｅａｒｕｍ）；ウリ類のべと病（Ｐｓｅｕｄｏｐｅｒｏｎｏｓｐｏｒａ　ｃｕｂｅｎｓｉｓ）、うどんこ病（Ｓｐｈａｅｒｏｔｈｅｃａ　ｆｕｌｉｇｉｎｅａ）、炭疽病（Ｃｏｌｌｅｔｏｔｒｉｃｈｕｍ　ｏｒｂｉｃｕｌａｒｅ）、つる枯病（Ｄｉｄｙｍｅｌｌａ　ｂｒｙｏｎｉａｅ）、つる割病（Ｆｕｓａｒｉｕｍ　ｏｘｙｓｐｏｒｕｍ）、疫病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｐａｒａｓｉｔｉｃａ、Ｐｈｙｔｏｐｈｔｈｏｒａ　ｍｅｌｏｎｉｓ、Ｐｈｙｔｏｐｈｔｈｏｒａ　ｎｉｃｏｔｉａｎａｅ、Ｐｈｙｔｏｐｈｔｈｏｒａ　ｄｒｅｃｈｓｌｅｒｉ、Ｐｈｙｔｏｐｈｔｈｏｒａ　ｃａｐｓｉｃｉ等）、褐斑細菌病（Ｘｈａｎｔｈｏｍｏｎａｓ　ｃａｍｐｅｓｔｒｉｓ　ｐｖ．ｃｕｃｕｒｂｉｔａｅ）、軟腐病（Ｅｒｗｉｎｉａ　ｃａｒｏｔｏｖｏｒａ　ｓｕｂｓｐ．　ｃａｒｏｔｏｖｏｒａ）、斑点細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．　ｌａｃｈｒｙｍａｎｓ）、
縁枯細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｍａｒｇｉｎａｌｉｓ　ｐｖ．　ｍａｒｇｉｎａｌｉｓ）、がんしゅ病（Ｓｔｒｅｐｔｏｍｙｃｅｓ　ｓｐ．）、毛根病（Ａｇｒｏｂａｃｔｅｒｉｕｍ　ｒｈｉｚｏｇｅｎｅｓ）、キュウリモザイクウィルス（Ｃｕｃｕｍｂｅｒ　ｍｏｓａｉｃ　ｖｉｒｕｓ）；トマトの輪紋病（Ａｌｔｅｒｎａｒｉａ　ｓｏｌａｎｉ）、葉かび病（Ｆｕｌｖｉａ　ｆｕｌｖａ）、疫病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｉｎｆｅｓｔａｎｓ）、萎凋病（Ｆｕｓａｒｉｕｍ　ｏｘｙｓｐｏｒｕｍ）、根腐病（Ｐｙｔｈｉｕｍ　ｍｙｒｉｏｔｙｌｕｍ、Ｐｙｔｈｉｕｍ　ｄｉｓｓｏｔｏｃｕｍ）、炭疽病（Ｃｏｌｌｅｔｏｔｒｉｃｈｕｍ　ｇｌｏｅｏｓｐｏｒｉｏｉｄｅｓ）、かいよう病（Ｃｌａｖｉｂａｃｔｅｒ　ｍｉｃｈｉｇａｎｅｎｓｉｓ）、茎えそ細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｃｏｒｒｕｇａｔａ）、黒斑細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｖｉｒｉｄｉｆｌａｖａ）、軟腐病（Ｅｒｗｉｎｉａ　ｃａｒｏｔｏｖｏｒａ　ｓｕｂｓｐ．　ｃａｒｏｔｏｖｏｒａ）、葉こぶ病（Ｃｒｙｎｅｂａｃｔｅｒｉｕｍ　ｓｐ．）、萎黄病（Ｐｈｙｔｏｐｌａｓｍａ　ａｓｔｅｒｉｓ）、黄化萎縮病（Ｔｏｂａｃｃｏ　ｌｅａｆ　ｃｕｒｌ　ｓｕｂｇｒｏｕｐ　ＩＩＩ　ｇｅｍｉｎｉｖｉｒｕｓ）；ナスのうどんこ病（Ｓｐｈａｅｒｏｔｈｅｃａ　ｆｕｌｉｇｉｎｅａ等）、すすかび病（Ｍｙｃｏｖｅｌｌｏｓｉｅｌｌａ　ｎａｔｔｒａｓｓｉｉ）、疫病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｉｎｆｅｓｔａｎｓ）、褐色腐敗病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｃａｐｓｉｃｉ）、褐斑細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｃｉｃｈｏｒｉｉ）、茎えそ細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｃｏｒｒｕｇａｔａ）、茎腐細菌病（Ｅｒｗｉｎｉａ　ｃｈｒｙｓａｎｔｈｅｍｉ）、軟腐病（Ｅｒｗｉｎｉａ　ｃａｒｏｔｏｖｏｒａ　ｓｕｂｓｐ．　ｃａｒｏｔｏｖｏｒａ）、斑点細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｐ．）；ナタネの黒斑病（Ａｌｔｅｒｎａｒｉａ　ｂｒａｓｓｉｃａｅ）、黒腐病（Ｘｈａｎｔｈｏｍｏｎａｓ　ｃａｍｐｅｓｔｒｉｓ　ｐｖ．　　ｃａｍｐｅｓｔｒｉｓ）、黒斑細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．　ｍａｃｕｌｉｃｏｌａ）、軟腐病（Ｅｒｗｉｎｉａ　ｃａｒｏｔｏｖｏｒａ）；アブラナ科野菜の黒斑病（Ａｌｔｅｒｎａｒｉａ　ｂｒａｓｓｉｃａｅ等）、白斑病（Ｃｅｒｃｏｓｐｏｒｅｌｌａ　ｂｒａｓｓｉｃａｅ）、根朽病（Ｐｈｏｍａ　ｌｉｎｇａｍ）、根こぶ病（Ｐｌａｓｍｏｄｉｏｐｈｏｒａ　ｂｒａｓｓｉｃａｅ）、べと病（Ｐｅｒｏｎｏｓｐｏｒａ　ｐａｒａｓｉｔｉｃａ）、黒腐病（Ｘｈａｎｔｈｏｍｏｎａｓ　ｃａｍｐｅｓｔｒｉｓ　ｐｖ．　　ｃａｍｐｅｓｔｒｉｓ）、黒斑細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．　ｍａｃｕｌｉｃｏｌａ）、軟腐病（Ｅｒｗｉｎｉａ　ｃａｒｏｔｏｖｏｒａ　ｓｕｂｓｐ．　ｃａｒｏｔｏｖｏｒａ）；キャベツの株腐病（Ｔｈａｎａｔｅｐｈｏｒｕｓ　ｃｕｃｕｍｅｒｉｓ）、萎黄病（Ｆｕｓａｒｉｕｍ　ｏｘｙｓｐｏｒｕｍ）、黒すす病（Ａｌｔｅｒｎａｒｉａ　ｂｒａｓｓｉｓｉｃｏｌａ）；ハクサイの尻腐病（Ｒｈｉｚｏｃｔｏｎｉａ　ｓｏｌａｎｉ）、黄化病（Ｖｅｒｔｉｃｉｌｌｉｕｍ　ｄａｈｌｉａｅ）；ネギのさび病（Ｐｕｃｃｉｎｉａ　ａｌｌｉｉ）、黒斑病（Ａｌｔｅｒｎａｒｉａ　ｐｏｒｒｉ）、白絹病（Ｓｃｌｅｒｏｔｉｕｍ　ｒｏｌｆｓｉｉ）、白色疫病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｐｏｒｒｉ）、黒腐菌核病（Ｓｃｌｅｒｏｔｉｕｍ　ｃｅｐｉｖｏｒｕｍ）；タマネギのかいよう病（Ｃｕｒｔｏｂａｃｔｅｒｉｕｍ　ｆｌａｃｃｕｍｆａｃｉｅｎｓ）、軟腐病（Ｅｒｗｉｎｉａ　ｃａｒｏｔｏｖｏｒａ　ｓｕｂｓｐ．　ｃａｒｏｔｏｖｏｒａ）、斑点細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．　ｓｙｒｉｎｇａｅ）、腐敗病（Ｅｒｗｉｎｉａ　ｒｈａｐｏｎｔｉｃｉ）、鱗片腐敗病（Ｂｕｒｋｈｏｌｄｅｒｉａ　ｇｌａｄｉｏｌｉ）、萎黄病（Ｐｈｙｔｏｐｌａｓｍａ　ａｓｔｅｒｉｓ）；ニンニクの軟腐病（Ｅｒｗｉｎｉａ　ｃａｒｏｔｏｖｏｒａ　ｓｕｂｓｐ．　ｃａｒｏｔｏｖｏｒａ）、春腐病（Ｐｓｅｕｄｏｍｏｎａｓ　ｍａｒｇｉｎａｌｉｓ　ｐｖ．ｍａｒｇｉｎａｌｉｓ）；ダイズの紫斑病（Ｃｅｒｃｏｓｐｏｒａ　ｋｉｋｕｃｈｉｉ）、黒とう病（Ｅｌｓｉｎｏｅ　ｇｌｙｃｉｎｅｓ）、黒点病（Ｄｉａｐｏｒｔｈｅ　ｐｈａｓｅｏｌｏｒｕｍ）、リゾクトニア根腐病（Ｒｈｉｚｏｃｔｏｎｉａ　ｓｏｌａｎｉ）、茎疫病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｓｏｊａｅ）、べと病（Ｐｅｒｏｎｏｓｐｏｒａ　ｍａｎｓｈｕｒｉｃａ）、さび病（Ｐｈａｋｏｐｓｏｒａ　ｐａｃｈｙｒｈｉｚｉ）、炭疽病（Ｃｏｌｌｅｔｏｔｒｉｃｈｕｍ　ｔｒｕｎｃａｔｕｍ等）、葉焼病（Ｘｈａｎｔｈｏｍｏｎａｓ　ｃａｍｐｅｓｔｒｉｓ　ｐｖ．　　ｇｌｙｃｉｎｅｓ）、斑点細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．　ｇｌｙｃｉｎｅａ）；インゲンの炭疽病（Ｃｏｌｌｅｔｏｔｒｉｃｈｕｍ　ｌｉｎｄｅｍｕｔｈｉａｎｕｍ）、青枯病（Ｒａｌｓｔｏｎｉａ　ｓｏｌａｎａｃｅａｒｕｍ）、かさ枯病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．　ｐｈａｓｅｏｌｉｃｏｌａ）、褐斑細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｖｉｒｉｄｉｆｌａｖａ）、葉焼病（Ｘｈａｎｔｈｏｍｏｎａｓ　ｃａｍｐｅｓｔｒｉｓ　ｐｖ．　ｐｈａｓｅｏｌｉ）；ラッカセイの黒渋病（Ｍｙｃｏｓｐｈａｅｒｅｌｌａ　ｂｅｒｋｅｌｅｙｉ）、褐斑病（Ｍｙｃｏｓｐｈａｅｒｅｌｌａ　ａｒａｃｈｉｄｉｓ）、青枯病（Ｒａｌｓｔｏｎｉａ　ｓｏｌａｎａｃｅａｒｕｍ）；エンドウのうどんこ病（Ｅｒｙｓｉｐｈｅ　ｐｉｓｉ）、べと病（Ｐｅｒｏｎｏｓｐｏｒａ　ｐｉｓｉ）、つる枯細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．ｐｉｓｉ）、つる腐細菌病（Ｘｈａｎｔｈｏｍｏｎａｓ　ｃａｍｐｅｓｔｒｉｓ　ｐｖ．　ｐｉｓｉ；ソラマメのべと病（Ｐｅｒｏｎｏｓｐｏｒａ　ｖｉｃｉａｅ）、疫病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｎｉｃｏｔｉａｎａｅ）；ジャガイモの夏疫病（Ａｌｔｅｒｎａｒｉａ　ｓｏｌａｎｉ）、黒あざ病（Ｔｈａｎａｔｅｐｈｏｒｕｓ　ｃｕｃｕｍｅｒｉｓ）、疫病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｉｎｆｅｓｔａｎｓ）、銀か病（Ｈｅｌｍｉｎｔｈｏｓｐｏｒｉｕｍ　ｓｏｌａｎｉ）、乾腐病（Ｆｕｓａｒｉｕｍ　ｏｘｙｓｐｏｒｕｍ、Ｆｕｓａｒｉｕｍ　ｓｏｌａｎｉ）、粉状そうか病（Ｓｐｏｎｇｏｓｐｏｒａ　ｓｕｂｔｅｒｒａｎｅａ）、青枯病（Ｒａｌｓｔｏｎｉａ　ｓｏｌａｎａｃｅａｒｕｍ）、黒あし病（Ｅｒｗｉｎｉａ　ｃａｒｏｔｏｖｏｒａ　ｓｕｂｓｐ．　ａｔｒｏｓｅｐｔｉｃａ）、そうか病（Ｓｔｒｅｐｔｏｍｙｃｅｓ　ｓｃａｂｉｅｓ、Ｓｔｒｅｐｔｏｍｙｃｅｓ　ａｃｉｄｉｓｃａｂｉｅｓ）、軟腐病（Ｅｒｗｉｎｉａ　ｃａｒｏｔｏｖｏｒａ　ｓｕｂｓｐ．　ｃａｒｏｔｏｖｏｒａ）、粘性腐敗病（Ｃｒｏｓｔｒｉｄｉｕｍ　ｓｐｐ．）、輪腐病（Ｃｌａｖｉｂａｃｔｅｒ　ｍｉｃｈｉｇａｎｅｎｓｉｓ　ｓｕｂｓｐ．ｓｅｐｅｄｏｎｉｃｕｓ）；サツマイモの立枯病（Ｓｔｒｅｐｔｏｍｙｃｅｓ　ｉｐｏｍｏｅａｅ）；テンサイの褐斑病（Ｃｅｒｃｏｓｐｏｒａ　ｂｅｔｉｃｏｌａ）、べと病（Ｐｅｒｏｎｏｓｐｏｒａ　ｓｃｈａｃｈｔｉｉ）、黒根病（Ａｐｈａｎｏｍｙｃｅｓ　ｃｏｃｈｉｏｉｄｅｓ）、蛇の目病（Ｐｈｏｍａ　ｂｅｔａｅ）、根頭がんしゅ病（Ａｇｒｏｂａｃｔｅｒｉｕｍ　ｔｕｍｅｆａｃｉｅｎｓ）、そうか病（Ｓｔｒｅｐｔｏｍｙｃｅｓ　ｓｃａｂｉｅｓ）、斑点細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．　ａｐｔａｔａ）；ニンジンの黒葉枯病（Ａｌｔｅｒｎａｒｉａ　ｄａｕｃｉ）、こぶ病（Ｒｈｉｚｏｂａｃｔｅｒ　ｄａｕｃｉ）、根頭がんしゅ病（Ａｇｒｏｂａｃｔｅｒｉｕｍ　ｔｕｍｅｆａｃｉｅｎｓ）、ストレプトミセスそうか病（Ｓｔｒｅｐｔｏｍｙｃｅｓ　ｓｐｐ．）、軟腐病（Ｅｒｗｉｎｉａ　ｃａｒｏｔｏｖｏｒａ　ｓｕｂｓｐ．　ｃａｒｏｔｏｖｏｒａ）；イチゴのうどんこ病（Ｓｐｈａｅｒｏｔｈｅｃａ　ａｐｈａｎｉｓ　ｖａｒ．　ａｐｈａｎｉｓ）、疫病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｎｉｃｏｔｉａｎａｅ等）、炭疽病（Ｇｌｏｍｅｒｅｌｌａ　ｃｉｎｇｕｌａｔａ等）、
果実腐敗病（Ｐｙｔｈｉｕｍ　ｕｌｔｉｍｕｍ）、青枯病（Ｒａｌｓｔｏｎｉａ　ｓｏｌａｎａｃｅａｒｕｍ）、角斑細菌病（Ｘｈａｎｔｈｏｍｏｎａｓ　ｃａｍｐｅｓｔｒｉｓ）、芽枯細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｍａｒｇｉｎａｌｉｓ　　ｐｖ．　ｍａｒｇｉｎａｌｉｓ）；チャの網もち病（Ｅｘｏｂａｓｉｄｉｕｍ　ｒｅｔｉｃｕｌａｔｕｍ）、白星病（Ｅｌｓｉｎｏｅ　ｌｅｕｃｏｓｐｉｌａ）、炭疽病（Ｃｏｌｌｅｔｏｔｒｉｃｈｕｍ　ｔｈｅａｅ－ｓｉｎｅｎｓｉｓ）、輪斑病（Ｐｅｓｔａｌｏｔｉｏｐｓｉｓ　ｌｏｎｇｉｓｅｔａ）、赤焼病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．ｔｈｅａｅ）、かいよう病（Ｘｈａｎｔｈｏｍｏｎａｓ　ｃａｍｐｅｓｔｒｉｓ　ｐｖ．　ｔｈｅｉｃｏｌａ）、てんぐ巣病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｐ．）；タバコの赤星病（Ａｌｔｅｒｎａｒｉａ　ａｌｔｅｒｎａｔａ）、うどんこ病（Ｅｒｙｓｉｐｈｅ　ｃｉｃｈｏｒａｃｅａｒｕｍ）、炭疽病（Ｃｏｌｌｅｔｏｔｒｉｃｈｕｍ　ｇｌｏｅｏｓｐｏｒｉｏｉｄｅｓ）、疫病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｎｉｃｏｔｉａｎａｅ）、野火病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．ｔａｂａｃｉ）、黄がさ細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．ｍｅｌｌｅａ）、空洞病（Ｅｒｗｉｎｉａ　ｃａｒｏｔｏｖｏｒａ　ｓｕｂｓｐ．　ｃａｒｏｔｏｖｏｒａ）、立枯病（Ｒａｌｓｔｏｎｉａ　ｓｏｌａｎａｃｅａｒｕｍ）、タバコモザイクウィルス（Ｔｏｂａｃｏ　ｍｏｓａｉｃ　ｖｉｒｕｓ）；コーヒーのさび病（Ｈｅｍｉｌｅｉａ　ｖａｓｔａｔｒｉｘ）；バナナの黒シガトガ病（Ｍｙｃｏｓｐｈａｅｒｅｌｌａ　ｆｉｊｉｅｎｓｉｓ）、パナマ病（Ｆｕｓａｒｉｕｍ　ｏｘｙｓｐｏｒｕｍ　ｆ．ｓｐ　ｃｕｂｅｎｓｅ）；ワタの立枯病（Ｆｕｓａｒｉｕｍ　ｏｘｙｓｐｏｒｕｍ）、白かび病（Ｒａｍｕｌａｒｉａ　ａｒｅｏｌａ）；ヒマワリの菌核病（Ｓｃｌｅｒｏｔｉｎｉａ　ｓｃｌｅｒｏｔｉｏｒｕｍ）、角点病（Ｘｈａｎｔｈｏｍｏｎａｓ　ｃａｍｐｅｓｔｒｉｓ　ｐｖ．ｍａｌｖａｃｅａｒｕｍ）、空洞病Ｅｒｗｉｎｉａ　ｃａｒｏｔｏｖｏｒａ　ｓｕｂｓｐ．　ｃａｒｏｔｏｖｏｒａ）、斑点細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｓｙｒｉｎｇａｅ　ｐｖ．ｈｅｌｉａｎｔｈｉ）；バラの黒星病（Ｄｉｐｌｏｃａｒｐｏｎ　ｒｏｓａｅ）、うどんこ病（Ｓｐｈａｅｒｏｔｈｅｃａ　ｐａｎｎｏｓａ等）、疫病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｍｅｇａｓｐｅｒｍａ）、べと病（Ｐｅｒｏｎｏｓｐｏｒａ　ｓｐａｒｓａ）、根頭がんしゅ病（Ａｇｒｏｂａｃｔｅｒｉｕｍ　ｔｕｍｅｆａｃｉｅｎｓ）；キクの褐斑病（Ｓｅｐｔｏｒｉａ　ｏｂｅｓａ）、白さび病（Ｐｕｃｃｉｎｉａ　ｈｏｒｉａｎａ）、疫病（Ｐｈｙｔｏｐｈｔｈｏｒａ　ｃａｃｔｏｒｕｍ）、斑点細菌病（Ｐｓｅｕｄｏｍｏｎａｓ　ｃｉｃｈｏｒｉｉ）、軟腐病（Ｅｒｗｉｎｉａ　ｃａｒｏｔｏｖｏｒａ　ｓｕｂｓｐ．　ｃａｒｏｔｏｖｏｒａ）、根頭がんしゅ病（Ａｇｒｏｂａｃｔｅｒｉｕｍ　ｔｕｍｅｆａｃｉｅｎｓ）、毛根病（Ａｇｒｏｂａｃｔｅｒｉｕｍ　ｒｈｉｚｏｇｅｎｅｓ）、緑化病（Ｐｈｙｔｏｐｌａｓｍａ　ａｕｒａｎｔｉｆｏｌｉａ）；芝のブラウンパッチ病（Ｒｈｉｚｏｃｔｏｎｉａ　ｓｏｌａｎｉ）、ダラースポット病（Ｓｃｌｅｒｏｔｉｎｉａ　ｈｏｍｏｅｏｃａｒｐａ）、カーブラリア葉枯病（Ｃｕｒｖｕｌａｒｉａ　ｓｐ．）、さび病　（Ｐｕｃｃｉｎｉａ　ｚｏｙｓｉａｅ）、ヘルミントスポリウム葉枯病（Ｃｏｃｈｌｉｏｂｏｌｕｓ　ｓｐ．）、雲形病（Ｒｈｙｎｃｈｏｓｐｏｒｉｕｍ　ｓｅｃａｌｉｓ）、立枯病（Ｇａｅｕｍａｎｎｏｍｙｃｅｓ　ｇｒａｍｉｎｉｓ）、炭疽病（Ｃｏｌｌｅｔｏｔｒｉｃｈｕｍ　ｓｐ．）、雪腐褐色小粒菌核病（Ｔｙｐｈｕｌａ　ｉｎｃａｒｎａｔａ）、雪腐黒色小粒菌核病（Ｔｙｐｈｕｌａ　ｉｓｈｉｋａｒｉｅｎｓｉｓ）、雪腐大粒菌核病（Ｍｙｒｉｏｓｃｌｅｒｏｔｉｎｉａ　ｂｏｒｅａｌｉｓ）、フェアリーリング病（Ｍａｒａｓｍｉｕｓ　ｏｒｅａｄｅｓ等）、ピシウム病（Ｐｙｔｈｉｕｍ　ａｐｈａｎｉｄｅｒｍａｔｕｍ等）、いもち病（Ｐｙｒｉｃｕｌａｒｉａ　ｇｒｉｓｅａ）等が挙げられる。 Rice blast (Magnaporthe grisea), sheath blight (Thanatephorus cucumeris), brown rot (Ceratobasidium setariae), brown sclerotium (Waitea circinata), brown spot rot spelling bacterium (Therca erucorus phus) Sclerotium hydrophilum, red rot (Wairea circinata), black rot (Entyloma dactylidis), pneumococcal disease (Magnaporthe salvinii leaf blight, Ceratobosa sigma rot) Blight disease (Sphaerulina oryzina) , Frog seedling disease (Gibberella fujikuroi), seedling blight (Pythium spp., Fusarium spp., Trichoderma spp., Rhizopus spp., Rhizonia spore, Rhizoctonia spore, Rhizoptonia solipani, Ms. Rhizotonia sol. Achlya spp., Dictyuchus spp.), Rice scab (Clavipesps virens), Black smut (Tilletia barclayana), Brown rice (Curvularia spp., Alternaria spp., Yellow wilt disease, Alternaria spp., Yellowing disease) Xanthomonas oryzae pv. Oryzae, brown streak (Acidovora) avenae subsp. oryzae), strain rot (Erwinia chrysanthemi), yellow rot (Phytoplasma oryzae), stripe leaf blight (Rice stripe tenuivirus), dwarf disease (Rice dwarf reovirlus radix) (Rice dwarf reovirlus); holdei; f. sp. tritici), rust (Puccinia striiformis, Puccinia graminis, Puccinia recondita, Puccinia hordei), Madarahabyo (Pyrenophora graminea), net blotch (Pyrenophora teres), Fusarium head blight (Gibberella zeae, Fusarium culmorum, Fusarium avenaceum, Monographella nivalis ), Snow rot (Typhula incarnata, Typhula ishikaririensis, Monographaella nivalis), bare smut (Ustilago nuda), stalk blight (Tilletia caries, Tilleretia) versa), eye blight (Pseudocercosporella herpotrichoides), stock rot (Ceratobasidium gramineum), foliar blight (Rhynchosporium spalus foliage), leaf blight (Septoria triatium aerial blight) , Pythium spp., Rhizoctonia spp., Septoria spp., Pyrenophora spp., Damping-off disease (Gaeumanomyces gramulis), anthracnose disease (Coletotrichum gravinica), anthracnose disease (Coletotrichum grachiolica). us), Pseudomonas syringae pv. syringae); Red mold disease of corn (Gibberella zeae, etc.), Fusarium avenaceus (Pusillium spp, Pythium sp., Penicillium spp, Pythium spp, Pythium spp. ), Sesame leaf blight (Cochliobolus heterostrophus), smut (Ustilago maydis), anthrax (Colletotrichum graminicola), northern leaf spot (Cochliobolus carbonum), and brown stripe (Acivara vivaencia). avenae), streak bacterial disease (Burkholderia andropogonis), lodging bacterial disease (Erwinia chrysanthemi pv. zeae), bacterial wilt disease (Erwinia pesola pialo pial, plaso pial, disease). This disease (Uncinula necator), black scab (Elsinoe ampelina), late rot (Glomerella gingulata, Colletotrichum acutatum), black rot (Guignardia zyolas), vine leaf sickness (Phoensis vulgaris), vine leaf clam (Phosophorus vulgaris). gray Blight (Botrytis cinerea), bud blight (Diaportthe medusaea), purple crest rot (Helicobasidium mompa), white crest rot (Rosellinia necatrix), root head cancer (Agrobacterium terrestris) (Agrobacterium terrestris). Podosphaera leucotricha), scab (Venturia inaequalis), leaf spot disease (Alternaria mali), gymnosporangium (Gymnosporangium yamadae), monilia disease (Monilinia mali), canker (Valsa ceratosperma), early blight (Botryosphaeria berengeriana), anthrax (Coletotrichum acu atum, Glomerella gingulata, soot spot disease (Zygophiala jamaicensis), soot spot disease (Gloeodes pomigena), black spot disease (Mycosphaerella white blight disease, Helicobasmaria, Rhizoma balsa disease) (Phomopsis mali, Diaporthe tanakae), brown spot (Diplocarpon mali), apple burns (Erwinia amylovora), root canker spot (Agrobacterium tumefaciens) (Agrobacterium tumefaciens root), (Agrobacterium tumefaciens root). kikuchuiana), black Disease (Venturia nashicola), gymnosporangium (Gymnosporangium asiaticum), early blight (Botryosphaeria berengeriana f. sp. piricola), blight (Phomopsis fukusii), bacterial wilt (Erwinia sp.), crown gall (Agrobacterium tumefaciens), rust blight (Erwinia chrysanthemip. Pseudomonas syringae pv. sp.), anthrax (Colletotrich) um gloeosporioides), leaf scab (Taphrina deformans), perforation bacterial disease (Xhanthomonas campestris pv. pruni), root canker disease (Agrobacterium tumefaciens), Agrobacterium tumefaciens (Agrobacterium tumefaciens); kusanoi), ash scab (Monilinia fructicola), crown gall (Agrobacterium tumefaciens), resinous bacterial disease (Pseudomonas syringa coerca pyl. syringa cv. wae), powdery mildew (Phyllactinia kakikora), crown gall (Agrobacterium tumefaciens); black spot of citrus (Diaportheicum citrus), green mold (Penicillium citrus disease) Elsinoe fawcettii), brown rot (Phytophthora citrophthora), scab (Xhanthomonas campestris piva. tumefaciens); gray mold disease (Botrytis cinerea) such as tomato, cucumber, beans, strawberry, potato, cabbage, eggplant, lettuce; sclerotial disease of tomato, cucumber, beans, strawberry, potato, rapeseed, cabbage, eggplant, lettuce, etc. (Sclerotinia sclerotiorum); Tomato, cucumber, beans, Japanese radish, watermelon, eggplant, rapeseed, bell pepper, spinach, sugar beet, and other vegetables (Rhizoctonia spp. , Pythium spp. , Fusarium spp. , Phythophthora spp. , Sclerotinia sclerotiorum, etc.); Ralstonia solanacearum); downy mildew (Pseudoperonospora uberis ulcer), powdery mildew (Sphaerotheca culinia), powdery mildew (Sphaerothecea ulifera) ), Fusarium oxysporum), plague (Phytophthora parasitica, Phytophthora melonis, Phytophthora nicotianae, Phytophthora drechsleri, Phytophthorai, Phytophthorai, Phytophthora) onas campestris pv.cucurbitae), soft rot (Erwinia carotovora subsp. carotovora), spot bacterial disease (Pseudomonas syringae pv. lachrymans),
Marginal bacterial disease (Pseudomonas marginalis pv. Marginalis), scab (Streptomyces sp.), Hairy root disease (Agrobacterium rhizogenes) or cucumber mosaic virus (Cucumber mosa) or tomato (Cucumber mosaric; tomato) Disease (Fulvia fulva), plague (Phytophthora infestans), wilt disease (Fusarium oxysporum), root rot (Pythium myriotilis oleum), Pythium disotocum (Anthracnose) Pseudomonas corrugata, Black spot bacterial disease (Pseudomonas viridiflava), Soft rot (Erwinia carotovora subsp. Carrotova), Leaf blight (Crynebacterium, Crynebacterium). Tobacco leaf curl subgroup III geminivirus; powdery mildew of aubergine (Sphaerotheca fuliginea, etc.), scab (Mycovelothior porphyra rot), and plague (Phytophyta). C. ichorii), Bacterial stem blight (Pseudomonas corrugata), Stem rot bacterial disease (Erwinia chrysanthemi), Soft rot (Erwinia carotovora ssp. carotovera); Black rot (Xhanthomonas campestris pv. Campestris), Black spot bacterial disease (Pseudomonas syringae pv. Maculicola), White rot (Erwinia carotovora), Black spot (Erwinia carotovora); , Root rot (P oma lingam), clubroot (Plasmodiophora brassicae), downy mildew (Peronospora parasitica), black rot (Xhanthomonas campestris pv. campestris), black spot bacterial disease (Pseudomonas syringae pv. Chinese cabbage bottom rot (Rhizoctonia solani), yellowing disease (Verticillium dahliae); green onion rust (Puccinia allii), black spot (Alteraria orphia porphyri), white scab (Sclerothia porphyri rolii) Black rot sclerosis (Scl rotium cepivorum);.. onion Canker (Curtobacterium flaccumfaciens), soft rot (Erwinia carotovora subsp carotovora), spot Bacterial (Pseudomonas syringae pv syringae), rot (Erwinia rhapontici), scale rot (Burkholderia gladioli), yellows Disease (Phytoplasma asteris); soft rot of garlic (Erwinia carotovora subsp. Carotovora), spring rot (Pseudomonas marginalis pv. Marginalis); Elsinoe glycines), black spot disease (Diaporthe phaseolorum), Rhizoctonia root rot (Rhizoctonia solani), stems late blight (Phytophthora sojae), downy mildew (Peronospora manshurica), rust (Phakopsora pachyrhizi), anthracnose (Colletotrichum truncatum, etc.), Leaf burn disease (Xhanthomonas campestris pv. Glycines), bacterial spot disease (Pseudomonas syringae pv. Glycinea); anthracnose disease of green beans (Coletotrichum lanceumum) eudomonas syringae pv. Phaseolicola), brown spot bacterial disease (Pseudomonas viridiflava), leaf burn disease (Xhanthomonas campestris pv. phaseoli); Powdery mildew (Erysiphe pisi), downy mildew (Peronospora pisi), bacterial wilt of vine (Pseudomonas syringae pv. Pisi), bacterial rot of vine (Xhanthomonas campestris pestis, pestis pv. Plague (Phyto hthora nicotianae); Potato summer plague (Alternaria solani), black blight (Thanatephorus cucumeris), plague (Phytophthora infestaum varieties, dry scab (Helminthosporium fusiformus, dry rot), Helminthosporium fusiformus (Helminthosporium fusifolia) Disease (Spongospora subterranea), bacterial wilt (Ralstonia solanacearum), black wilt (Erwinia carotovora subsp. Atroseptica rot, scab (Streptomyces cerevisiae, Stabiles), scab. carotovora subsp. carotovora), viscous rot (Crostridium spp.), ring rot (Claviobacter michiganensis subsp. sepedoricea); Peronospora schachtii, black root disease (Aphanomyces cochioides), snake eye disease (Poma betae), root canker disease (Agrobacterium tumefaciens bacillus), scab (Streptomyces bacillus disease) aptata); Black leaf blight of carrots (Alternaria dauci), downy mildew (Rhizobacterium dauci), root cancer scab (Agrobacterium tumefaciens sp. scab (Streptomyces sp.), Streptomyces sp. carotovora); strawberry powdery mildew (Sphaerotheca aphanis var. aphanis), plague (Phytophthora nicotianae, etc.), anthrax (Glomerella ingulata, etc.),
Fruit rot (Pythium ultimum), bacterial wilt (Ralstonia solanacearum), horn spot bacterial disease (Xhanthomonas campestris), bacterial blight (Pseudomonas marginalis pv. Elsinoe leucospila), anthrax (Colletotrichum theae-sinensis), ring spot disease (Pestalotiopsis longiseta), red blight (Pseudomonas pyrosanthe syringae pv.thea, pseudomonas syringae pv.thea). as sp.); Tobacco scab (Alternaria alternata), powdery mildew (Erysiphe cichoracearum), anthrax (Colletotrichum gloeosporia porosaides), epidemic (Phytophthora nuea), epidemics (Phytophthora nuea). (Pseudomonas syringae pv. Mellea), cavities (Erwinia carotovora subsp. Carotovora), wilt disease (Ralstonia solanaea varia; black and white), tobacco mosaic virus (Tobaco moria var. Sigatoga disease (Mycosphaerella fijiensis), Panama disease (Fusarium oxysporum f. Sp cubense); Fusarium wilt (Fusarium oxysporum), white scab (Ramularia areolita), and sunflower disease (Ramularia areolia) Xhanthomonas campestris pv. Malvacearum), cavernous disease Erwinia carotovora subsp. carotovora), spotted bacterial disease (Pseudomonas syringae pv. helianthi); rose scab (Diplocarpon rosae), powdery mildew (Sphaerothera speratophyta panhosa, etc.), plague (Pharmophyta) (Agrobacterium tumefaciens); Chrysanthemum leaf spot (Septoria obesa), white rust (Puccinia horicora bacterium), plague (Phytophthora crocodile rot) Head cancer Disease (Agrobacterium tumefaciens), hair root disease (Agrobacterium rhizogenes), green disease (Phytoplasma aurantifolia); brown patch of turf (Rhizoctonia solani), brown patch of turf (Rhizoctonia solani) (Puccinia zosiae), Helmintosporium leaf blight (Cochliobolus sp.), Cloud-shaped disease (Rhynchosporium secalis), damping-off (Gaeummannomyces gravinus brown rot, Colletotrichum spp.), Anthracnose (Coletotriculis sp.). incarna a), snow rot black small grain sclerotia (Typhula ishikariensis), snow rot large grain sclerotial disease (Myriosclerotinia borealis), fairy ring disease (Marasmius oreadrias), etc., Pythium aphanidaricatum, etc. Is mentioned.
　本発明化合物は、本化合物単体で使用してもよいが、好ましくは、固体担体、液体担体、気体担体、界面活性剤、固着剤、分散剤、安定剤等と混合し、粉剤、水和剤、顆粒水和剤、水溶剤、顆粒水溶剤、粒剤、乳剤、液剤、マイクロエマルション剤、水性懸濁製剤、水性乳濁製剤、サスポエマルション製剤等の組成物として使用することができる。効果が発揮される限りにおいて、それらの組成物に限定されることはない。 The compound of the present invention may be used as the present compound alone, but is preferably mixed with a solid carrier, a liquid carrier, a gas carrier, a surfactant, a fixing agent, a dispersant, a stabilizer, etc., and a powder or wettable powder. , Granule wettable powder, aqueous solvent, granular aqueous solution, granule, emulsion, solution, microemulsion, aqueous suspension preparation, aqueous emulsion preparation, suspoemulsion preparation and the like. The composition is not limited as long as the effect is exhibited.
　以下に具体的な製剤化例を示すが、これらに限定されるものではない。 Specific formulation examples are shown below, but the invention is not limited to these.
［製剤例１　フロアブル剤］
　本発明化合物（１０質量部）、ナフタレンスルホン酸のホルムアルデヒド縮合物ナトリウム塩（５質量部）、ポリオキシエチレンアリールフェニルエーテル（１質量部）、プロピレングリコール（５質量部）、シリコン系消泡剤（０．１質量部）、キサンタンガム（０．２質量部）、イオン交換水（７８．７質量部）を混合してスラリーとなし、さらにダイノミルＫＤＬで直径１．０ｍｍのガラスビーズを用いて湿式粉砕しフロアブル剤を得る。 [Formulation Example 1 Flowable]
Compound of the present invention (10 parts by mass), sodium salt of formaldehyde condensate of naphthalenesulfonic acid (5 parts by mass), polyoxyethylene arylphenyl ether (1 part by mass), propylene glycol (5 parts by mass), silicon-based antifoaming agent ( 0.1 parts by mass), xanthan gum (0.2 parts by mass), ion-exchanged water (78.7 parts by mass) to form a slurry, and further wet milling using glass beads having a diameter of 1.0 mm with Dynomill KDL. To obtain a flowable agent.
［製剤例２　乳剤］
　本発明化合物（５質量部）をキシレン（４０質量部）とシクロヘキサン（３５質量部）の混合溶液に溶解し、この溶液にＴｗｅｅｎ２０（２０質量部）を添加混合し、乳剤を得る。 [Formulation Example 2 Emulsion]
The compound of the present invention (5 parts by mass) is dissolved in a mixed solution of xylene (40 parts by mass) and cyclohexane (35 parts by mass), and Tween 20 (20 parts by mass) is added and mixed with the solution to obtain an emulsion.
［製剤例３　水和剤］
　本発明化合物（１０質量部）、ホワイトカーボン（１０質量部）、ポリビニルアルコール（２質量部）、ジオクチルスルホコハク酸ナトリウム塩（０．５質量部）、アルキルベンゼンスルホン酸ナトリウム塩（５質量部）、焼成珪藻土（１０質量部）およびカオリナイトクレー（６２．５質量部）を充分に混合し、エアーミルで粉砕し、水和剤を得る。 [Formulation Example 3 wettable powder]
Compound of the present invention (10 parts by mass), white carbon (10 parts by mass), polyvinyl alcohol (2 parts by mass), sodium salt of dioctylsulfosuccinate (0.5 part by mass), sodium salt of alkylbenzenesulfonic acid (5 parts by mass), calcining Diatomaceous earth (10 parts by mass) and kaolinite clay (62.5 parts by mass) are sufficiently mixed and pulverized with an air mill to obtain a wettable powder.
　以下、本発明化合物を含有する組成物（農園芸用有害生物防除剤、農園芸用殺菌剤など）の施用について説明する。 Hereinafter, application of a composition containing the compound of the present invention (an agricultural and horticultural pest control agent, an agricultural and horticultural fungicide, etc.) will be described.
　本発明化合物を含有する組成物の施用方法としては、植物体もしくは種子と接触させる方法、または、栽培土壌に含有させて、植物の根もしくは地下茎に接触させる方法が挙げられる。具体例として、組成物の植物個体への茎葉散布処理、注入処理、苗箱処理、セルトレー処理、植物種子への吹き付け処理、植物種子への塗沫処理、植物種子への浸漬処理、植物種子への粉衣処理、土壌表面への散布処理、土壌表面への散布処理後の土壌混和、土壌中への注入処理、土壌中での注入処理後の土壌混和、土壌潅注処理、土壌潅注処理後の土壌混和等が挙げられる。通常、当業者が利用するようないかなる施用方法を用いても十分な効力を発揮する。 Examples of the method of applying the composition containing the compound of the present invention include a method of contacting with a plant or seed, or a method of adding the composition to cultivated soil and contacting with a root or rhizome of a plant. As specific examples, foliage spraying treatment, injection treatment, seedling box treatment, cell tray treatment, spraying treatment on plant seeds, spray treatment on plant seeds, immersion treatment on plant seeds, immersion treatment on plant seeds on plant seeds of the composition Dressing, spraying on the soil surface, soil mixing after spraying on the soil surface, injection into the soil, soil mixing after injection in the soil, soil irrigation, after soil irrigation Soil mixing and the like. In general, any method of application as used by those skilled in the art will work well.
　本発明でいう「植物」とは、光合成をして運動せずに生活するものをいう。具体例として、稲、小麦、大麦、トウモロコシ、コーヒー、バナナ、ブドウ、リンゴ、ナシ、モモ、オウトウ、カキ、カンキツ、大豆、インゲン、ワタ、イチゴ、ジャガイモ、キャベツ、レタス、トマト、キュウリ、ナス、スイカ、テンサイ、ホウレンソウ、サヤエンドウ、カボチャ、サトウキビ、タバコ、ピーマン、サツマイモ、サトイモ、コンニャク、綿、ヒマワリ、バラ、チューリップ、キク、芝等およびそれらのＦ１品種等が挙げられる。また、遺伝子等を人工的に操作することにより生み出され、元来自然界に存在するものではない遺伝子組み換え作物も含み、例えば、除草剤耐性を付与した大豆、トウモロコシ、綿等、寒冷地適応したイネ、タバコ等、殺虫物質生産能を付与したトウモロコシ、綿等の農園芸作物等が挙げられる。さらに、マツ、トネリコ、イチョウ、カエデ、カシ、ポプラ、ケヤキ等の樹木等が挙げられる。また、本発明でいう「植物体」とは、前記の植物個体を構成する全ての部位を総称するものであり、例えば、茎、葉、根、種子、花、果実等が挙げられる。 The term “plant” as used in the present invention refers to a plant that performs photosynthesis and lives without exercise. Specific examples include rice, wheat, barley, corn, coffee, banana, grape, apple, pear, peach, cherry, oyster, citrus, soybean, bean, cotton, strawberry, potato, cabbage, lettuce, tomato, cucumber, eggplant, Watermelon, sugar beet, spinach, snow pea, pumpkin, sugar cane, tobacco, bell pepper, sweet potato, taro, konjac, cotton, sunflower, rose, tulip, chrysanthemum, turf, etc. and their F1 varieties and the like can be mentioned. In addition, it includes genetically modified crops that are produced by manipulating genes and the like and are not originally present in the natural world.For example, soybeans, corn, cotton, etc. that have been imparted with herbicide resistance, such as rice adapted to cold regions. And agricultural and horticultural crops, such as corn and cotton, to which insecticide-producing ability is imparted. Further, trees such as pine, ash, ginkgo, maple, oak, poplar, zelkova and the like can be mentioned. The “plant” in the present invention is a general term for all parts constituting the above-mentioned plant individual, and includes, for example, stems, leaves, roots, seeds, flowers, fruits and the like.
　本発明でいう「種子」とは、幼植物が発芽するための栄養分を蓄え、農業上繁殖に用いられるものをいう。具体例として、トウモロコシ、大豆、綿、稲、テンサイ、小麦、大麦、ヒマワリ、トマト、キュウリ、ナス、ホウレンソウ、サヤエンドウ、カボチャ、サトウキビ、タバコ、ピーマン、セイヨウアブラナ等の種子、それらのＦ１品種等の種子、サトイモ、ジャガイモ、サツマイモ、コンニャク等の種芋、食用ゆり、チューリップ等の球根、ラッキョウ等の種球、および遺伝子組み換え作物の種子ならびに塊茎等が挙げられる。 The term “seed” as used in the present invention refers to a seed that stores nutrients for germination of young plants and is used for agricultural reproduction. Specific examples include seeds of corn, soybeans, cotton, rice, sugar beet, wheat, barley, sunflower, tomato, cucumber, eggplant, spinach, snow peas, pumpkin, sugar cane, tobacco, peppers, oilseed rape, and their F1 varieties. Examples include seeds, seed potatoes such as taro, potato, sweet potato, and konjac, edible lilies, bulbs such as tulips, seed balls such as rakkyo, and seeds and tubers of genetically modified crops.
　本発明化合物を含有する組成物の施用量および施用濃度は、対象作物、対象病害、病害の発生程度、化合物の剤型、施用方法および各種環境条件等によって変動するが、散布または潅注する場合には、有効成分量としてヘクタール当たり０．１～１０，０００ｇが適当であり、好ましくは、ヘクタール当り１０～１，０００ｇである。また、種子処理の場合の使用量は、有効成分量として種子１ｋｇ当たり０．０００１～１０００ｇであり、好ましくは、０．００１～１００ｇである。本発明化合物を含有する組成物を植物個体への茎葉散布処理、土壌表面への散布処理、土壌中への注入処理または土壌潅注処理として使用する場合は、適当な担体に適当な濃度で希釈した後、処理を行ってもよい。本発明化合物を含有する組成物を植物種子に接触させる場合は、適当な濃度に希釈した後、植物種子に浸漬、粉衣、吹き付けまたは塗沫処理して用いてもよい。浸漬、粉衣、吹き付けまたは塗沫処理する場合の組成物使用量は、通常、有効成分量として、乾燥植物種子重量の０．０５～５０％程度であり、好ましくは、０．１～３０％が適当であるが、組成物の形態や処理対象となる植物種子の種類により適宜設定すればよく、これら範囲に限定されるものではない。 The application rate and application concentration of the composition containing the compound of the present invention vary depending on the target crop, target disease, degree of disease occurrence, dosage form of the compound, application method and various environmental conditions, but when spraying or irrigating. Is suitably 0.1 to 10,000 g per hectare, and preferably 10 to 1,000 g per hectare. In the case of seed treatment, the amount used is 0.0001 to 1000 g, preferably 0.001 to 100 g, per 1 kg of seeds as the amount of active ingredient. When the composition containing the compound of the present invention is used as a foliage spraying treatment on a plant individual, a spraying treatment on a soil surface, an injection treatment into soil or a soil irrigation treatment, the composition is diluted with an appropriate carrier at an appropriate concentration. Thereafter, the processing may be performed. When the composition containing the compound of the present invention is brought into contact with a plant seed, it may be diluted to an appropriate concentration and then immersed, dressed, sprayed or smeared on the plant seed before use. The amount of the composition used in the case of dipping, dressing, spraying or smearing is usually about 0.05 to 50%, preferably 0.1 to 30% of the weight of dry plant seeds as the amount of active ingredient. Is suitable, but it may be appropriately set depending on the form of the composition and the kind of plant seed to be treated, and is not limited to these ranges.
　本発明化合物を含有する組成物は、必要に応じて他の農薬、例えば、殺菌剤、殺虫剤、殺ダニ剤、殺線虫剤、除草剤、生物農薬および植物成長調節剤等の農薬、核酸を有効成分とする病害防除剤（国際公開第２０１４／０６２７７５号）、土壌改良剤または肥効物質と混用または併用することができる。本発明化合物と他の農薬を混合して使用する方法としては、本発明化合物と他の農薬とを一つの剤型に製剤化して使用する方法、それぞれが別々の剤型に製剤化された両者を使用前に混合して使用する方法、それぞれが別々の剤型に製剤化された両者を同時に使用する方法、または、それぞれが別々の剤型に製剤化された両者について、いずれか一方を使用した後に他方を使用する方法が挙げられる。 The composition containing the compound of the present invention, if necessary, other pesticides, for example, fungicides, insecticides, acaricides, nematicides, herbicides, pesticides such as biological pesticides and plant growth regulators, nucleic acids. Can be mixed with or used in combination with a disease controlling agent (International Publication No. WO 2014/062775), a soil conditioner, or a fertilizing substance. As a method of mixing and using the compound of the present invention and another pesticide, a method of formulating and using the compound of the present invention and another pesticide in one dosage form, and both methods in which each is formulated in a separate dosage form Are used before and after use, or both are separately formulated in separate dosage forms, or both are formulated in separate dosage forms. And then use the other.
　本発明化合物と混合して使用することができる殺菌剤に含まれる具体的な成分は、以下の群ｂで例示され、これらの塩、異性体およびＮ－オキシド体を含む。ただし、公知の殺菌剤はこれらに限定されるものではない。 Specific components contained in the bactericide that can be used by mixing with the compound of the present invention are exemplified in the following group b, and include salts, isomers and N-oxides thereof. However, the known disinfectants are not limited to these.
群ｂ：
ｂ－１：フェニルアミド系殺菌剤
　フェニルアミド系殺菌剤として、［ｂ－１．１］：ベナラキシル（ｂｅｎａｌａｘｙｌ）、［ｂ－１．２］ベナラキシルＭまたはキララキシル（ｂｅｎａｌａｘｙｌ－Ｍまたはｋｉｒａｌａｘｙｌ）、［ｂ－１．３］フララキシル（ｆｕｒａｌａｘｙｌ）、［ｂ－１．４］メタラキシル（ｍｅｔａｌａｘｙｌ）、［ｂ－１．５］メタラキシルＭまたはメフェノキサム（ｍｅｔａｌａｘｙｌ－Ｍまたはｍｅｆｅｎｏｘａｍ）、［ｂ－１．６］オキサジキシル（ｏｘａｄｉｘｙｌ）、［ｂ－１．７］オフラセ（ｏｆｕｒａｃｅ）等が挙げられる。 Group b:
b-1: Phenylamide fungicide As a phenylamide fungicide, [b-1.1]: benalaxyl (benalaxyl), [b-1.2] benalaxyl M or chiralaxyl (benalaxyl-M or chiralaxyl), [b -1.3] Furalaxyl, [b-1.4] Metalaxyl, [b-1.5] Metalaxyl M or Mephenoxam (Metalaxyl-M or mefenoxam), [b-1.6] Oxadixyl (-) oxadixyl), [b-1.7] off-race, and the like.
ｂ－２：有糸核分裂および細胞分裂阻害剤
　有糸核分裂および細胞分裂阻害剤として、［ｂ－２．１］ベノミル（ｂｅｎｏｍｙｌ）、［ｂ－２．２］カルベンダジム（ｃａｒｂｅｎｄａｚｉｍ）、［ｂ－２．３］フベリダゾール（ｆｕｂｅｒｉｄａｚｏｌｅ）、［ｂ－２．４］チアベンダゾール（ｔｈｉａｂｅｎｄａｚｏｌｅ）、［ｂ－２．５］チオファネート（ｔｈｉｏｐｈａｎａｔｅ）、［ｂ－２．６］チオファネートメチル（ｔｈｉｏｐｈａｎａｔｅ－ｍｅｔｈｙｌ）、［ｂ－２．７］ジエトフェンカルブ（ｄｉｅｔｈｏｆｅｎｃａｒｂ）、［ｂ－２，８］ゾキサミド（ｚｏｘａｍｉｄｅ）、［ｂ－２．９］エタボキサム（ｅｔｈａｂｏｘａｍ）、［ｂ－２．１０］ペンシクロン（ｐｅｎｃｙｃｕｒｏｎ）、［ｂ－２．１１］フルオピコリド（ｆｌｕｏｐｉｃｏｌｉｄｅ）、［ｂ－２．１２］フェナマクリル（ｐｈｅｎａｍａｃｒｉｌ）等が挙げられる。 b-2: mitotic cell division and cell division inhibitor As a mitotic cell division and cell division inhibitor, [b-2.1] benomyl, [b-2.2] carbendazim, [b- 2.3] fuberidazole, [b-2.4] thiabendazole, [b-2.5] thiophanate, [b-2.6] thiophanate-methyl, [b- 2.7] Diethofencarb, [b-2,8] zoxamide, [b-2.9] ethaboxam, [b-2.10] pencycuron, [b-2. 11] Full opico Lido (fluopicolide), [b-2.12] phenamacril and the like can be mentioned.
ｂ－３：コハク酸脱水素酵素阻害剤（ＳＤＨＩ剤）
　コハク酸脱水素酵素阻害剤（ＳＤＨＩ剤）として、［ｂ－３．１］ベノダニル（ｂｅｎｏｄａｎｉｌ）、［ｂ－３．２］ベンゾビンジフルピル（ｂｅｎｚｏｖｉｎｄｉｆｌｕｐｙｒ）、［ｂ－３．３］ビキサフェン（ｂｉｘａｆｅｎ）、［ｂ－３．４］ボスカリド（ｂｏｓｃａｌｉｄ）、［ｂ－３．５］カルボキシン（ｃａｒｂｏｘｉｎ）、［ｂ－３．６］フェンフラム（ｆｅｎｆｕｒａｍ）、［ｂ－３．７］フルオピラム（ｆｌｕｏｐｙｒａｍ）、［ｂ－３．８］フルトラニル（ｆｌｕｔｏｌａｎｉｌ）、［ｂ－３．９］フルキサピロキサド（ｆｌｕｘａｐｙｒｏｘａｄ）、［ｂ－３．１０］フラメトピル（ｆｕｒａｍｅｔｐｙｒ）、［ｂ－３．１１］イソフェタミド（ｉｓｏｆｅｔａｍｉｄ）、［ｂ－３．１２］イソピラザム（ｉｓｏｐｙｒａｚａｍ）、［ｂ－３．１３］メプロニル（ｍｅｐｒｏｎｉｌ）、［ｂ－３．１４］オキシカルボキシン（ｏｘｙｃａｒｂｏｘｉｎ）、［ｂ－３．１５］ペンチオピラド（ｐｅｎｔｈｉｏｐｙｒａｄ）、［ｂ－３．１６］ペンフルフェン（ｐｅｎｆｌｕｆｅｎ）、［ｂ－３．１７］ピジフルメトフェン（ｐｙｄｉｆｌｕｍｅｔｏｆｅｎ）、［ｂ－３．１８］セダキサン（ｓｅｄａｘａｎｅ）、［ｂ－３．１９］チフルザミド（ｔｈｉｆｌｕｚａｍｉｄｅ）、［ｂ－３．２０］ピラジフルミド（ｐｙｒａｚｉｆｌｕｍｉｄ）等が挙げられる。 b-3: Succinate dehydrogenase inhibitor (SDHI agent)
As a succinate dehydrogenase inhibitor (SDHI agent), [b-3.1] benodanil, [b-3.2] benzobindiflupyr, [b-3.3] bixaphen (bixafen) ), [B-3.4] boscalid, [b-3.5] carboxin, [b-3.6] fenfuram, [b-3.7] fluopyram. , [B-3.8] flutolanil, [b-3.9] fluxapyroxad, [b-3.10] furametpyr, [b-3.11] isofetamide (isofetamide). ), [B-3.12] isopyrazam (isop razam), [b-3.13] mepronil, [b-3.14] oxycarboxin, [b-3.15] penthiopyrad, [b-3.16] penflufen ( penflufen), [b-3.17] pydiflumethofen, [b-3.18] sedaxane, [b-3.19] thifluzamide, [b-3.20] pyradiflumide. (Pyraziflumid) and the like.
ｂ－４：キノン外部阻害剤（ＱｏＩ剤）
　キノン外部阻害剤（ＱｏＩ剤）として、［ｂ－４．１］アゾキシストロビン（ａｚｏｘｙｓｔｒｏｂｉｎ）、［ｂ－４．２］クモキシストロビン（ｃｏｕｍｏｘｙｓｔｒｏｂｉｎ）、［ｂ－４．３］ジモキシストロビン（ｄｉｍｏｘｙｓｔｒｏｂｉｎ）、［ｂ－４．４］エノキサストロビン（ｅｎｏｘａｓｔｒｏｂｉｎ）、［ｂ－４．５］ファモキサドン（ｆａｍｏｘａｄｏｎｅ）、［ｂ－４．６］フェンアミドン（ｆｅｎａｍｉｄｏｎｅ）、［ｂ－４．７］フェナミンストロビン（ｆｅｎａｍｉｎｓｔｒｏｂｉｎ）、［ｂ－４．８］フルフェノキシストロビン（ｆｌｕｆｅｎｏｘｙｓｔｒｏｂｉｎ）、［ｂ－４．９］フルオキサストロビン（ｆｌｕｏｘａｓｔｒｏｂｉｎ）、［ｂ－４．１０］クレソキシムメチル（ｋｒｅｓｏｘｉｍ－ｍｅｔｈｙｌ）、［ｂ－４．１１］マンデストロビン（ｍａｎｄｅｓｔｒｏｂｉｎ）、［ｂ－４．１２］メトミノストロビン（ｍｅｔｏｍｉｎｏｓｔｒｏｂｉｎ）、［ｂ－４．１３］オリサストロビン（ｏｒｙｓａｓｔｒｏｂｉｎ）、［ｂ－４．１４］ピコキシストロビン（ｐｉｃｏｘｙｓｔｒｏｂｉｎ）、［ｂ－４．１５］ピラクロストロビン（ｐｙｒａｃｌｏｓｔｒｏｂｉｎ）、［ｂ－４．１６］ピラメトストロビン（ｐｙｒａｍｅｔｏｓｔｒｏｂｉｎ）、［ｂ－４．１７］ピラオキシストロビン（ｐｙｒａｏｘｙｓｔｒｏｂｉｎ）、［ｂ－４．１８］ピリベンカルブ（ｐｙｒｉｂｅｎｃａｒｂ）、［ｂ－４．１９］トリクロピリカルブ（ｔｒｉｃｌｏｐｙｒｉｃａｒｂ）、［ｂ－４．２０］トリフロキシストロビン（ｔｒｉｆｌｏｘｙｓｔｒｏｂｉｎ）等が挙げられる。 b-4: Quinone external inhibitor (QoI agent)
As a quinone external inhibitor (QoI agent), [b-4.1] azoxystrobin, [b-4.2] cumoxystrobin, [b-4.3] dimoxist Robin (dimoxystrobin), [b-4.4] enoxastrobin (enoxastrobin), [b-4.5] famoxadone, [b-4.6] fenamidone, [b-4.7. ] Phenamine stroben, [b-4.8] fluphenoxystrobin, [b-4.9] fluoxastrobin, [b-4.10] kresoxim-methyl (kresoxim-me) hyl), [b-4.11] mandestrobin, [b-4.12] metaminostrobin, [b-4.13] orysastrobin, [b-4.14]. Picoxystrobin, [b-4.15] pyraclostrobin, [b-4.16] pyrametostrobin, [b-4.17] pyraoxystrobin , [B-4.18] pyribencarb, [b-4.19] triclopyricarb, [b-4.20] trifloxystrobin. obin), and the like.
ｂ－５：キノン内部阻害剤（ＱｉＩ剤）
　キノン内部阻害剤（ＱｉＩ剤）として、［ｂ－５．１］シアゾファミド（ｃｙａｚｏｆａｍｉｄ）、［ｂ－５．２］アミスルブロム（ａｍｉｓｕｌｂｒｏｍ）等が挙げられる。 b-5: quinone internal inhibitor (QiI agent)
Examples of the quinone internal inhibitor (QiI agent) include [b-5.1] cyazofamide and [b-5.2] amisulbrom.
ｂ－６：酸化的リン酸化脱共役阻害剤
　酸化的リン酸化脱共役阻害剤として、［ｂ－６．１］ビナパクリル（ｂｉｎａｐａｃｒｙｌ）、［ｂ－６．２］メプチルジノカップ（ｍｅｐｔｙｌｄｉｎｏｃａｐ）、［ｂ－６．３］ジノカップ（ｄｉｎｏｃａｐ）、［ｂ－６．４］フルアジナム（ｆｌｕａｚｉｎａｍ）等が挙げられる。 b-6: Oxidative phosphorylation uncoupling inhibitor As an oxidative phosphorylation uncoupling inhibitor, [b-6.1] binapacryl (binapacryl), [b-6.2] meptyldinocap, [b-6.2] Examples thereof include b-6.3] dinocap and [b-6.4] fluazinam.
ｂ－７：キノン外部スチグマテリン結合サブサイト阻害剤（ＱｏＳＩ剤）
　キノン外部スチグマテリン結合サブサイト阻害剤（ＱｏＳＩ剤）として、［ｂ－７．１］アメトクトラジン（ａｍｅｔｏｃｔｒａｄｉｎ）等が挙げられる。 b-7: quinone external stigmaterin-binding subsite inhibitor (QOSI agent)
Examples of the quinone external stigmaterin-binding subsite inhibitor (QOSI agent) include [b-7.1] amethoctrazine.
ｂ－８：アミノ酸生合成阻害剤
　アミノ酸生合成阻害剤として、［ｂ－８．１］シプロジニル（ｃｙｐｒｏｄｉｎｉｌ）、［ｂ－８．２］メパニピリム（ｍｅｐａｎｉｐｙｒｉｍ）、［ｂ－８．３］ピリメタニル（ｐｙｒｉｍｅｔｈａｎｉｌ）等が挙げられる。 b-8: Amino acid biosynthesis inhibitor As an amino acid biosynthesis inhibitor, [b-8.1] cyprodinil, [b-8.2] mepanipyrim, and [b-8.3] pyrimethanil (pyrimethanil). ) And the like.
ｂ－９：タンパク質生合成阻害剤
　タンパク質生合成阻害剤として、［ｂ－９．１］ストレプトマイシン（ｓｔｒｅｐｔｏｍｙｃｉｎ）、［ｂ－９．２］ブラストサイジンＳ（ｂｌａｓｔｉｃｉｄｉｎ－Ｓ）、［ｂ－９．３］カスガマイシン（ｋａｓｕｇａｍｙｃｉｎ）、［ｂ－９．４］オキシテトラサイクリン（ｏｘｙｔｅｔｒａｃｙｃｌｉｎｅ）等が挙げられる。 b-9: Protein biosynthesis inhibitor [b-9.1] streptomycin, [b-9.2] blasticidin S (blasticidin-S), [b-9. 3] Kasugamycin, [b-9.4] oxytetracycline and the like.
ｂ－１０：シグナル伝達阻害剤
　シグナル伝達阻害剤として、［ｂ－１０．１］フェンピクロニル（ｆｅｎｐｉｃｌｏｎｉｌ）、［ｂ－１０．２］フルジオキソニル（ｆｌｕｄｉｏｘｏｎｉｌ）、［ｂ－１０．３］キノキシフェン（ｑｕｉｎｏｘｙｆｅｎ）、［ｂ－１０．４］プロキナジド（ｐｒｏｑｕｉｎａｚｉｄ）、［ｂ－１０．５］クロゾリネート（ｃｈｌｏｚｏｌｉｎａｔｅ）、［ｂ－１０．６］ジメタクロン（ｄｉｍｅｔｈａｃｈｌｏｎｅ）、［ｂ－１０．７］イプロジオン（ｉｐｒｏｄｉｏｎｅ）、［ｂ－１０．８］プロシミドン（ｐｒｏｃｙｍｉｄｏｎｅ）、［ｂ－１０．９］ビンクロゾリン（ｖｉｎｃｌｏｚｏｌｉｎ）等が挙げられる。 b-10: Signal transduction inhibitor As a signal transduction inhibitor, [b-10.1] fenpiclonil, [b-10.2] fludioxonil, [b-10.3] quinoxyphen, [B-10.4] proquinazid, [b-10.5] chlorozolinate, [b-10.6] dimethaclone, [b-10.7] iprodione, [b -10.8] procymidone, [b-10.9] vinclozoline and the like can be mentioned.
ｂ－１１：脂質および細胞膜生合成阻害剤
　脂質および細胞膜生合成阻害剤として、［ｂ－１１．１］エジフェンホス（ｅｄｉｆｅｎｐｈｏｓ）、［ｂ－１１．２］イプロベンホス（ｉｐｒｏｂｅｎｆｏｓ）、［ｂ－１１．３］ピラゾホス（ｐｙｒａｚｏｐｈｏｓ）、［ｂ－１１．４］イソプロチオラン（ｉｓｏｐｒｏｔｈｉｏｌａｎｅ）、［ｂ－１１．５］ビフェニル（ｂｉｐｈｅｎｙｌ）、［ｂ－１１．６］クロロネブ（ｃｈｌｏｒｏｎｅｂ）、［ｂ－１１．７］ジクロラン（ｄｉｃｌｏｒａｎ）、［ｂ－１１．８］キントゼン（ｑｕｉｎｔｏｚｅｎｅ）、［ｂ－１１．９］テクナゼン（ｔｅｃｎａｚｅｎｅ）、［ｂ－１１．１０］トルクロホスメチル（ｔｏｌｃｌｏｆｏｓ－ｍｅｔｈｙｌ）、［ｂ－１１．１１］エトリジアゾール（ｅｃｈｌｏｍｅｚｏｌ　ｏｒ　ｅｔｒｉｄｉａｚｏｌｅ）、［ｂ－１１．１２］ヨードカルブ（ｉｏｄｏｃａｒｂ）、［ｂ－１１．１３］プロパモカルブ（ｐｒｏｐａｍｏｃａｒｂ）、［ｂ－１１．１４］プロチオカルブ（ｐｒｏｔｈｉｏｃａｒｂ）等が挙げられる。 b-11: Lipid and Cell Membrane Biosynthesis Inhibitors [b-11.1] edifenphos, [b-11.2] iprobenphos, [b-11.3] as lipid and cell membrane biosynthesis inhibitors. ] Pyrazophos, [b-11.4] isoprothiolane, [b-11.5] biphenyl, [b-11.6] chloroneb, [b-11.7] dichlorane (Dicloran), [b-11. 8] quintozene, [b-11. 9] tecnazene, [b-11.10] tolclofos-methyl, [b-11.11]. Etridiazole (ec hlomezol or etridiazole), [b-11.12] iodocarb, [b-11.13] propamocarb, [b-11.14] prothiocarb, and the like.
ｂ－１２：脱メチル化阻害剤（ＤＭＩ剤）
　脱メチル化阻害剤（ＤＭＩ剤）として、［ｂ－１２．１］アザコナゾール（ａｚａｃｏｎａｚｏｌｅ）、［ｂ－１２．２］ビテルタノール（ｂｉｔｅｒｔａｎｏｌ）、［ｂ－１２．３］ブロムコナゾール（ｂｒｏｍｕｃｏｎａｚｏｌｅ）、［ｂ－１２．４］シプロコナゾール（ｃｙｐｒｏｃｏｎａｚｏｌｅ）、［ｂ－１２．５］ジフェノコナゾール（ｄｉｆｅｎｏｃｏｎａｚｏｌｅ）、［ｂ－１２．６］ジニコナゾール（ｄｉｎｉｃｏｎａｚｏｌｅ）、［ｂ－１２．７］ジニコナゾールＭ（ｄｉｎｉｃｏｎａｚｏｌｅ－Ｍ）、［ｂ－１２．８］エポキシコナゾール（ｅｐｏｘｉｃｏｎａｚｏｌｅ）、［ｂ－１２．９］エタコナゾール（ｅｔａｃｏｎａｚｏｌｅ）、［ｂ－１２．１０］フェナリモル（ｆｅｎａｒｉｍｏｌ）、［ｂ－１２．１１］フェンブコナゾール（ｆｅｎｂｕｃｏｎａｚｏｌｅ）、［ｂ－１２．１２］フルキンコナゾール（ｆｌｕｑｕｉｎｃｏｎａｚｏｌｅ）、［ｂ－１２．１３］キンコナゾール（ｑｕｉｎｃｏｎａｚｏｌｅ）、［ｂ－１２．１４］フルシラゾール（ｆｌｕｓｉｌａｚｏｌｅ）、［ｂ－１２．１５］フルトリアホール（ｆｌｕｔｒｉａｆｏｌ）、［ｂ－１２．１６］ヘキサコナゾール（ｈｅｘａｃｏｎａｚｏｌｅ）、［ｂ－１２．１７］イマザリル（ｉｍａｚａｌｉｌ）、［ｂ－１２．１８］イミベンコナゾール（ｉｍｉｂｅｎｃｏｎａｚｏｌｅ）、［ｂ－１２．１９］イプコナゾール（ｉｐｃｏｎａｚｏｌｅ）、［ｂ－１２．２０］メトコナゾール（ｍｅｔｃｏｎａｚｏｌｅ）、［ｂ－１２．２１］ミクロブタニル（ｍｙｃｌｏｂｕｔａｎｉｌ）、［ｂ－１２．２２］ヌアリモール（ｎｕａｒｉｍｏｌ）、［ｂ－１２．２３］オキスポコナゾール（ｏｘｐｏｃｏｎａｚｏｌｅ）、［ｂ－１２．２４］オキスポコナゾールフマル酸塩（ｏｘｐｏｃｏｎａｚｏｌｅ　ｆｕｍａｒａｔｅ）、［ｂ－１２．２５］ペフラゾエート（ｐｅｆｕｒａｚｏａｔｅ）、［ｂ－１２．２６］ペンコナゾール（ｐｅｎｃｏｎａｚｏｌｅ）、［ｂ－１２．２７］プロクロラズ（ｐｒｏｃｈｌｏｒａｚ）、［ｂ－１２．２８］プロピコナゾール（ｐｒｏｐｉｃｏｎａｚｏｌｅ）、［ｂ－１２．２９］プロチオコナゾール（ｐｒｏｔｈｉｏｃｏｎａｚｏｌｅ）、［ｂ－１２．３０］ピリフェノックス（ｐｙｒｉｆｅｎｏｘ）、［ｂ－１２．３１］ピリソキサゾール（ｐｙｒｉｓｏｘａｚｏｌｅ）、［ｂ－１２．３２］シメコナゾール（ｓｉｍｅｃｏｎａｚｏｌｅ）、［ｂ－１２．３３］テブコナゾール（ｔｅｂｕｃｏｎａｚｏｌｅ）、［ｂ－１２．３４］テトラコナゾール（ｔｅｔｒａｃｏｎａｚｏｌｅ）、［ｂ－１２．３５］トリアジメホン（ｔｒｉａｄｉｍｅｆｏｎ）、［ｂ－１２．３６］トリアジメノール（ｔｒｉａｄｉｍｅｎｏｌ）、［ｂ－１２．３７］トリフルミゾール（ｔｒｉｆｌｕｍｉｚｏｌｅ）、［ｂ－１２．３８］トリホリン（ｔｒｉｆｏｒｉｎｅ）、［ｂ－１２．３９］トリチコナゾール（ｔｒｉｔｉｃｏｎａｚｏｌｅ）［ｂ－１２．４０］メフェントリフルコナゾール（ｍｅｆｅｎｔｒｉｆｌｕｃｏｎａｚｏｌｅ）、［ｂ－１２．４１］イプフェントリフルコナゾール（ｉｐｆｅｎｔｒｉｆｌｕｃｏｎａｚｏｌｅ）等が挙げられる。 b-12: Demethylation inhibitor (DMI agent)
Examples of demethylation inhibitors (DMI agents) include [b-12.1] azaconazole, [b-12.2] bitertanol, [b-12.3] bromuconazole, and [b-12.3] bromuconazole. [b-12.4] cyproconazole, [b-12.5] difenoconazole, [b-12.6] diniconazole, [b-12.7] diniconazole M (diniconazole-M) ), [B-12.8] epoxyconazole, [b-12.9] ethaconazole, [b-12.10] phenarimol, [b-12.11]. Fenbuconazole, [b-12.12] fluquinconazole, [b-12.13] quinconazole, [b-12.14] flusilazole, [b-12] .15] Flutriafol, [b-12.16] hexaconazole, [b-12.17] imazalil, [b-12.18] imibenconazole, [B-12.19] ipconazole, [b-12.20] metconazole, [b-12.21] microbutanil , [B-12.22] nuarimol, [b-12.23] oxpoconazole, [b-12.24] oxpoconazole fumarate, [b- 12.25] pefurazoate, [b-12.26] penconazole, [b-12.27] prochloraz, [b-12.28] propiconazole, [b- 12.29] Prothioconazole, [b-12.30] Pyrifenox, [b-12.31] Pyrisoxazole, [b-12.32] Cimeconazole, [b-12.33] tebuconazole, [b-12.34] tetraconazole, [b-12.35] triadimefone, [b-12.36]. Triadimenol, [b-12.37] triflumizole, [b-12.38] triforine, [b-12.39] triticonazole [b-12] .40] mefentrifluconazole, [b-12.41] ipfentrifluconazole, and the like.
ｂ－１３：アミン系殺菌剤
　アミン系殺菌剤として、［ｂ－１３．１］アルジモルフ（ａｌｄｉｍｏｒｐｈ）、［ｂ－１３．２］ドデモルフ（ｄｏｄｅｍｏｒｐｈ）、［ｂ－１３．３］フェンプロピモルフ（ｆｅｎｐｒｏｐｉｍｏｒｐｈ）、［ｂ－１３．４］トリデモルフ（ｔｒｉｄｅｍｏｒｐｈ）、［ｂ－１３．５］フェンプロピジン（ｆｅｎｐｒｏｐｉｄｉｎ）、［ｂ－１３．６］ピペラリン（ｐｉｐｅｒａｌｉｎ）、［ｂ－１３．７］スピロキサミン（ｓｐｉｒｏｘａｍｉｎｅ）等が挙げられる。 b-13: Amine-based bactericide As amine-based bactericide, [b-13.1] aldimorph, [b-13.2] dodemorph, [b-13.3] fenpropimorph ), [B-13.4] tridemorph, [b-13.5] phenpropidin, [b-13.6] piperalin, [b-13.7] spiroxamine. ) And the like.
ｂ－１４：ステロール生合成のＣ４位脱メチル化における３－ケト還元酵素阻害剤
　ステロール生合成のＣ４位脱メチル化における３－ケト還元酵素阻害剤として、［ｂ－１４．１］フェンヘキサミド（ｆｅｎｈｅｘａｍｉｄ）、［ｂ－１４．２］フェンピラザミン（ｆｅｎｐｙｒａｚａｍｉｎｅ）等が挙げられる。 b-14: 3-keto reductase inhibitor in C4 demethylation of sterol biosynthesis [b-14.1] phenhexamide as a 3-keto reductase inhibitor in C4 demethylation of sterol biosynthesis (Fenhexamid), [b-14.2] fenpyrazamine, and the like.
ｂ－１５：ステロール生合成のスクアレンエポキシダーゼ阻害剤
　ステロール生合成のスクアレンエポキシダーゼ阻害剤として、［ｂ－１５．１］ピリブチカルブ（ｐｙｒｉｂｕｔｉｃａｒｂ）、［ｂ－１５．２］ナフチフィン（ｎａｆｔｉｆｉｎｅ）、［ｂ－１５．３］テルビナフィン（ｔｅｒｂｉｎａｆｉｎｅ）等が挙げられる。 b-15: Squalene epoxidase inhibitor for sterol biosynthesis As a squalene epoxidase inhibitor for sterol biosynthesis, [b-15.1] pyributicarb (b-15.2) naphthifine (naftifine), [b] -15.3] Terbinafine and the like can be mentioned.
ｂ－１６：細胞壁生合成阻害剤
　細胞壁生合成阻害剤として、［ｂ－１６．１］ポリオキシン類（ｐｏｌｙｏｘｉｎｓ）、［ｂ－１６．２］ジメトモルフ（ｄｉｍｅｔｈｏｍｏｒｐｈ）、［ｂ－１６．３］フルモルフ（ｆｌｕｍｏｒｐｈ）、［ｂ－１６．４］ピリモルフ（ｐｙｒｉｍｏｒｐｈ）、［ｂ－１６．５］ベンチアバリカルブ（ｂｅｎｔｈｉａｖａｌｉｃａｒｂ）、［ｂ－１６．６］ベンチアバリカルブイソプロピル（ｂｅｎｔｈｉｖａｌｉｃａｒｂ－ｉｓｏｐｒｏｐｙｌ）、［ｂ－１６．７］イプロバリカルブ（ｉｐｒｏｖａｌｉｃａｒｂ）、［ｂ－１６．８］マンジプロパミド（ｍａｎｄｉｐｒｏｐａｍｉｄ）、［ｂ－１７．９］バリフェナレート（ｖａｌｉｆｅｎａｌａｔｅ）等が挙げられる。 b-16: Cell wall biosynthesis inhibitor As a cell wall biosynthesis inhibitor, [b-16.1] polyoxins (polyoxins), [b-16.2] dimethomorph, [b-16.3] flumorph ( flumorph), [b-16.4] pyrimorph, [b-16.5] bench avalicarb, [b-16.6] bench avalicarb isopropyl (b). -16.7] iprovalicarb, [b-16.8] mandipropamide, [b-17.9] valifenalate and the like can be mentioned.
ｂ－１７：メラニン生合成阻害剤
　メラニン生合成阻害剤として、［ｂ－１７．１］フサライド（ｐｈｔｈａｌｉｄｅ　ｏｒ　ｆｔｈａｌｉｄｅ）、［ｂ－１７．２］ピロキロン（ｐｙｒｏｑｕｉｌｏｎｅ）、［ｂ－１７．３］トリシクラゾール（ｔｒｉｃｙｃｌａｚｏｌｅ）、［ｂ－１７．４］カルプロパミド（ｃａｒｐｒｏｐａｍｉｄ）、［ｂ－１７．５］ジクロシメット（ｄｉｃｌｏｃｙｍｅｔ）、［ｂ－１７．６］フェノキサニル（ｆｅｎｏｘａｎｉｌ）、［ｂ－１７．７］トルプロカルブ（ｔｏｌｐｒｏｃａｒｂ）等が挙げられる。 b-17: Melanin biosynthesis inhibitor As a melanin biosynthesis inhibitor, [b-17.1] phtalide or phthalide, [b-17.2] pyroquilon, [b-17.3] tricyclazole. (Tricylazole), [b-17.4] carpropamide, [b-17.5] diclocymet, [b-17.6] phenoxanil, [b-17.7] tolprocarb. ) And the like.
ｂ－１８：宿主植物抵抗性誘導剤
　宿主植物抵抗性誘導剤として、［ｂ－１８．１］アシベンゾラルＳメチル（ａｃｉｂｅｎｚｏｌａｒ－Ｓ－ｍｅｔｈｙｌ）、［ｂ－１８．２］プロベナゾール（ｐｒｏｂｅｎａｚｏｌｅ）、［ｂ－１８．３］チアジニル（ｔｉａｄｉｎｉｌ）、［ｂ－１８．４］イソチアニル（ｉｓｏｔｉａｎｉｌ）、［ｂ－１８．５］ラミナリン（ｌａｍｉｎａｒｉｎ）等が挙げられる。 b-18: Host plant resistance inducer [b-18.1] acibenzolar S-methyl (acibenzalar-S-methyl), [b-18.2] probenazole (b), and [b-18.2] -18.3] thiazinyl (tiadinil), [b-18.4] isotianil, [b-18.5] laminarin and the like can be mentioned.
ｂ－１９：ジチオカーバメート系殺菌剤
　ジチオカーバメート系殺菌剤として、［ｂ－１９．１］マンコゼブまたはマンゼブ（ｍａｎｃｏｚｅｂ　ｏｒ　ｍａｎｚｅｂ）、［ｂ－１９．２］マンネブ（ｍａｎｅｂ）、［ｂ－１９．３］メチラム（ｍｅｔｉｒａｍ）、［ｂ－１９．４］プロピネブ（ｐｒｏｐｉｎｅｂ）、［ｂ－１９．５］チウラム（ｔｈｉｒａｍ）、［ｂ－１９．６］ジネブ（ｚｉｎｅｂ）、［ｂ－１９．７］ジラム（ｚｉｒａｍ）、［ｂ－１９．８］フェルバム（ｆｅｒｂａｍ）等が挙げられる。 b-19: Dithiocarbamate fungicide As a dithiocarbamate fungicide, [b-19.1] mancozeb or manzeb (mancozeb or manzeb), [b-19.2] manneb, [b-19.3]. ] Metiram, [b-19.4] propineb, [b-19.5] thiuram, [b-19.6] zineb, [b-19.7] ziram (Ziram), [b-19.8] ferbam and the like.
ｂ－２０：フタルイミド系殺菌剤
　フタルイミド系殺菌剤として、［ｂ－２０．１］キャプタン（ｃａｐｔａｎ）、［ｂ－２０．２］キャプタホール（ｃａｐｔａｆｏｌ）、［ｂ－２０．３］ホルペット（ｆｏｌｐｅｔ）、［ｂ－２０．４］フルオロホルペット（ｆｌｕｏｒｏｆｏｌｐｅｔ）等が挙げられる。 b-20: Phthalimide bactericide As phthalimide bactericide, [b-20.1] captan (captan), [b-20.2] captafol (captafol), [b-20.3] folpet (folpet) ), [B-20.4] fluorofolpet and the like.
ｂ－２１：グアニジン系殺菌剤
　グアニジン系殺菌剤として、［ｂ－２１．１］グアザチン（ｇｕａｚａｔｉｎｅ）、［ｂ－２１．２］イミノクタジン（ｉｍｉｎｏｃｔａｄｉｎｅ）、［ｂ－２１．３］イミノクタジンアルベシル酸塩（ｉｍｉｎｏｃｔａｄｉｎｅ　ａｌｂｅｓｉｌａｔｅ）、［ｂ－２１．４］イミノクタジン三酢酸塩（ｉｍｉｎｏｃｔａｄｉｎｅ　ｔｒｉａｃｅｔａｔｅ）等が挙げられる。 b-21: Guanidine fungicide As a guanidine fungicide, [b-21.1] guazatin, [b-21.2] iminoctadine, [b-21.3] iminoctadine albesylate (Imnoctadine albesilate), [b-21.4] iminoctadine triacetate and the like.
ｂ－２２：多作用点接触活性型殺菌剤
　多作用点接触活性型殺菌剤として、［ｂ－２２．１］塩基性塩化銅（ｃｏｐｐｅｒ　ｏｘｙｃｈｌｏｒｉｄｅ）、［ｂ－２２．２］水酸化第二銅（ｃｏｐｐｅｒ（ＩＩ）　ｈｙｄｒｏｘｉｄｅ）、［ｂ－２２．３］塩基性硫酸銅（ｃｏｐｐｅｒ　ｈｙｄｒｏｘｉｄｅ　ｓｕｌｆａｔｅ）、［ｂ－２２．４］有機銅化合物（ｏｒｇａｎｏｃｏｐｐｅｒ　ｃｏｍｐｏｕｎｄ）、［ｂ－２２．５］ドデシルベンゼンスルホン酸ビスエチレンジアミン銅錯塩［ＩＩ］（Ｄｏｄｅｃｙｌｂｅｎｚｅｎｅｓｕｌｐｈｏｎｉｃ　ａｃｉｄ　ｂｉｓｅｔｈｙｌｅｎｅｄｉａｍｉｎｅ　ｃｏｐｐｅｒ　［ＩＩ］　ｓａｌｔ、ＤＢＥＤＣ）、［ｂ－２２．６］硫黄（ｓｕｌｐｈｕｒ）、［ｂ－２２．７］フルオルイミド（ｆｌｕｏｒｏｉｍｉｄｅ）、［ｂ－２２．８］クロロタロニル（ｃｈｌｏｒｏｔｈａｌｏｎｉｌ）、［ｂ－２２．９］ジクロフルアニド（ｄｉｃｈｌｏｆｌｕａｎｉｄ）、［ｂ－２２．１０］トリルフルアニド（ｔｏｌｙｌｆｌｕａｎｉｄ）、［ｂ－２２．１１］アニラジン（ａｎｉｌａｚｉｎｅ）、［ｂ－２２．１２］ジチアノン（ｄｉｔｈｉａｎｏｎ）、［ｂ－２２．１３］キノメチオナート（ｃｈｉｎｏｍｅｔｈｉｏｎａｔ　ｏｒ　ｑｕｉｎｏｍｅｔｈｉｏｎａｔｅ）、［ｂ－２２．１４］ハウチワマメ苗木の子葉からの抽出物（ＢＬＡＤ）等が挙げられる。 b-22: Multi-action point contact active type bactericide [b-22.1] basic copper chloride (copper oxychloride), [b-22.2] cupric hydroxide (Copper (II) hydroxide), [b-22.3] basic copper sulfate (copper hydroxide sulfate), [b-22.4] organic copper compound (organocopper compound), [b-22.5] dodecylbenzene sulfone Acid bisethylenediamine copper complex salt [II] (Dodecylbenzene sulphonic acid bisethylenediamineamine copper [II] salt, DBEDC), [b-22.6] sulphur, [b-22.7] fluorimide (fluorim). de), [b-22.8] chlorothalonil, [b-22.9] diclofluanid, [b-22.10] tolylfluanid, [b-22.11]. Anilazine, [b-22.12] dithianon, [b-22.13] quinomethionate or quinomethionate, [b-22.14] extract from cotyledon of Japanese bean seedling (BLAD), etc. Is mentioned.
ｂ－２３：その他の殺菌剤
　その他の殺菌剤として、［ｂ－２３．１］ジクロベンチアゾクス（ｄｉｃｈｌｏｂｅｎｔｉａｚｏｘ）、［ｂ－２３．２］フェンピコキサミド（ｆｅｎｐｉｃｏｘａｍｉｄ）、［ｂ－２３．３］ジピメチトロン（ｄｉｐｙｍｅｔｉｔｒｏｎｅ）、［ｂ－２３．４］ブピリメート（ｂｕｐｉｒｉｍａｔｅ）、［ｂ－２３．５］ジメチリモール（ｄｉｍｅｔｈｉｒｉｍｏｌ）、［ｂ－２３．６］エチリモール（ｅｔｈｉｒｉｍｏｌ）、［ｂ－２３．７］酢酸トリフェニルスズ（ｆｅｎｔｉｎ　ａｃｅｔａｔｅ）、［ｂ－２３．８］塩化トリフェニルスズ（ｆｅｎｔｉｎ　ｃｈｌｏｒｉｄｅ）、［ｂ－２３．９］水酸化トリフェニルスズ（ｆｅｎｔｉｎ　ｈｙｄｒｏｘｉｄｅ）、［ｂ－２３．１０］オキソリニック酸（ｏｘｏｌｉｎｉｃ　ａｃｉｄ）、［ｂ－２３．１１］ヒメキサゾール（ｈｙｍｅｘａｚｏｌ）、［ｂ－２３．１２］オクチリノン（ｏｃｔｈｉｌｉｎｏｎｅ）、［ｂ－２３．１３］ホセチル（ｆｏｓｅｔｙｌ）、［ｂ－２３．１４］亜リン酸（ｐｈｏｓｐｈｏｒｏｕｓ　ａｃｉｄ）、［ｂ－２３．１５］亜リン酸のナトリウム塩（ｓｏｄｉｕｍ　ｐｈｏｓｐｈｉｔｅ）、［ｂ－２３．１６］亜リン酸のアンモニウム塩（ａｍｍｏｎｉｕｍ　ｐｈｏｓｐｈｉｔｅ）、［ｂ－２３．１７］亜リン酸のカリウム塩（ｐｏｔａｓｓｉｕｍ　ｐｈｏｓｐｈｉｔｅ）、［ｂ－２３．１８］テクロフタラム（ｔｅｃｌｏｆｔａｌａｍ）、［ｂ－２３．１９］トリアゾキシド（ｔｒｉａｚｏｘｉｄｅ）、［ｂ－２３．２０］フルスルファミド（ｆｌｕｓｕｌｆａｍｉｄｅ）、［ｂ－２３．２１］ジクロメジン（ｄｉｃｌｏｍｅｚｉｎｅ）、［ｂ－２３．２２］シルチオファム（ｓｉｌｔｈｉｏｆａｍ）、［ｂ－２３．２３］ジフルメトリム（ｄｉｆｌｕｍｅｔｏｒｉｍ）、［ｂ－２３．２４］メタスルホカルブ（ｍｅｔｈａｓｕｌｆｏｃａｒｂ）、［ｂ－２３．２５］シフルフェナミド（ｃｙｆｌｕｆｅｎａｍｉｄ）、［ｂ－２３．２６］メトラフェノン（ｍｅｔｒａｆｅｎｏｎｅ）、［ｂ－２３．２７］ピリオフェノン（ｐｙｒｉｏｆｅｎｏｎｅ）、［ｂ－２３．２８］ドジン（ｄｏｄｉｎｅ）、［ｂ－２３．２９］フルチアニル（ｆｌｕｔｉａｎｉｌ）、［ｂ－２３．３０］フェリムゾン（ｆｅｒｉｍｚｏｎｅ）、［ｂ－２３．３１］オキサチアピプロリン（ｏｘａｔｈｉａｐｉｐｒｏｌｉｎ）、［ｂ－２３．３２］テブフロキン（ｔｅｂｕｆｌｏｑｕｉｎ）、［ｂ－２３．３３］ピカルブトラゾクス（ｐｉｃａｒｂｕｔｒａｚｏｘ）、［ｂ－２３．３４］バリダマイシン類（ｖａｌｉｄａｍｙｃｉｎｓ）、［ｂ－２３．３５］シモキサニル（ｃｙｍｏｘａｎｉｌ）、［ｂ－２３．３６］キノフメリン（ｑｕｉｎｏｆｕｍｅｌｉｎ）、 b-23: Other fungicides As other fungicides, [b-23.1] diclobentiazox, [b-23.2] fenpicoxamide, [b-23.3]. ] Dipymetitron, [b-23.4] bupyrimate, [b-23.5] dimethirimol, [b-23.6] ethirimol, [b-23.7] acetic acid Triphenyl tin (fentin acetate), [b-23.8] triphenyl tin chloride (fentin chloride), [b-23.9] triphenyl tin hydroxide (fentin hydroxide), [b-23.10] oxolinic acid (Oxo linic acid), [b-23.11] hymexazol, [b-23.12] octilinone, [b-23.13] fosetyl, [b-23.14] phosphite. (Phosphorus acid), sodium salt of [b-23.15] phosphite (sodium phosphite), ammonium salt of [b-23.16] phosphite (ammonium phosphite), [b-23.17] phosphite. Potassium salt of acid (potassium phosphite), [b-23.18] tecloftalam, [b-23.19] triazoxide, [b-23.20] fursulfamide. [B-23.21] dichromezine, [b-23.22] silthiofam, [b-23.23] diflumetrim, [b-23.24] metasulphocarb, [B-23.25] cyflufenamide, [b-23.26] metrafenone, [b-23.27] pyriophenone, [b-23.28] dodine, [b] -23.29] flutianil, [b-23.30] ferrimzone, [b-23.31] oxathiapiproline, [b-23. 32] tebufloquine, [b-23.33] picarbutrazox, [b-23.34] validamycins, [b-23.35] cymoxanil, [b- 23.36] quinofumelin,
［ｂ－２３．３７］式（ｓ１）
Figure JPOXMLDOC01-appb-C000067
で表される化合物（国際公開第９８／０４６６０７号参照）、 [B-23.37] Expression (s1)
Figure JPOXMLDOC01-appb-C000067
(See WO 98/046607),
［ｂ－２３．３８］式（ｓ２）
Figure JPOXMLDOC01-appb-C000068
で表される化合物（国際公開第０８／１４８５７０号参照）、 [B-23.38] Expression (s2)
Figure JPOXMLDOC01-appb-C000068
(See WO 08/148570),
［ｂ－２３．３９］式（ｓ３）
Figure JPOXMLDOC01-appb-C000069
で表される化合物（国際公開第９２／０１２９７０号参照）、 [B-23.39] Expression (s3)
Figure JPOXMLDOC01-appb-C000069
(See WO 92/012970),
［ｂ－２３．４０］式（ｓ４）
Figure JPOXMLDOC01-appb-C000070
で表される化合物（国際公開第１２／０８４８１２号参照）、 [B-23.40] Expression (s4)
Figure JPOXMLDOC01-appb-C000070
A compound represented by the following formula (see International Publication No. 12/084812):
［ｂ－２３．４１］式（ｓ５）
Figure JPOXMLDOC01-appb-C000071
で表される化合物（ｇｏｕｇｅｒｏｔｉｎ）、 [B-23.41] Expression (s5)
Figure JPOXMLDOC01-appb-C000071
A compound (gougerotin) represented by
［ｂ－２３．４２］式（ｓ６）
Figure JPOXMLDOC01-appb-C000072
で表される化合物（ｎｉｎｇｎａｎｍｙｃｉｎ）、 [B-23.42] Expression (s6)
Figure JPOXMLDOC01-appb-C000072
A compound (ningnanmycin) represented by:
［ｂ－２３．４３］式（ｓ７）
Figure JPOXMLDOC01-appb-C000073
で表される化合物（国際公開第１０／１３６４７５号参照）、 [B-23.43] Expression (s7)
Figure JPOXMLDOC01-appb-C000073
(See WO 10/136475),
［ｂ－２３．４４］式（ｓ８）
Figure JPOXMLDOC01-appb-C000074
で表される化合物（国際公開第１４／０１０７３７号参照）、 [B-23.44] Expression (s8)
Figure JPOXMLDOC01-appb-C000074
(See WO 14/010737),
［ｂ－２３．４５］式（ｓ９）
Figure JPOXMLDOC01-appb-C000075
で表される化合物（国際公開第１１／０８５０８４号参照）、 [B-23.45] Expression (s9)
Figure JPOXMLDOC01-appb-C000075
(See WO 11/085084),
［ｂ－２３．４６］式（ｓ１０）
Figure JPOXMLDOC01-appb-C000076
で表される化合物（国際公開第１１／１３７００２号参照）、 [B-23.46] Expression (s10)
Figure JPOXMLDOC01-appb-C000076
(See WO 11/137002),
［ｂ－２３．４７］式（ｓ１１）
Figure JPOXMLDOC01-appb-C000077
で表される化合物（国際公開第１３／１６２０７２号参照）、 [B-23.47] Expression (s11)
Figure JPOXMLDOC01-appb-C000077
(See WO 13/162072),
［ｂ－２３．４８］式（ｓ１２）
Figure JPOXMLDOC01-appb-C000078
で表される化合物（国際公開第０８／１１０３１３号参照）、 [B-23.48] Expression (s12)
Figure JPOXMLDOC01-appb-C000078
(See WO 08/110313),
［ｂ－２３．４９］式（ｓ１３）
Figure JPOXMLDOC01-appb-C000079
で表される化合物（国際公開第０９／１５６０９８号参照）、 [B-23.49] Expression (s13)
Figure JPOXMLDOC01-appb-C000079
A compound represented by (see International Publication No. 09/156098),
［ｂ－２３．５０］式（ｓ１４）
Figure JPOXMLDOC01-appb-C000080
で表される化合物（国際公開第１２／０２５５５７号参照）、 [B-23.50] Expression (s14)
Figure JPOXMLDOC01-appb-C000080
(See WO 12/025557),
［ｂ－２３．５１］式（ｓ１５）
Figure JPOXMLDOC01-appb-C000081
で表される化合物（国際公開第１４／００６９４５号参照）、 [B-23.51] Expression (s15)
Figure JPOXMLDOC01-appb-C000081
(See WO 14/006945),
［ｂ－２３．５２］式（ｓ１６）
Figure JPOXMLDOC01-appb-C000082
［式中、Ａ３は、水素原子、ハロゲン原子、Ｃ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、またはシアノ基を表し、Ａ４は、水素原子、Ｃ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表す。］で表される化合物（国際公開第１４／０９５６７５号参照）、 [B-23.52] Expression (s16)
Figure JPOXMLDOC01-appb-C000082
[In the formula, A3 represents a hydrogen atom, a halogen atom, a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, or a cyano group, and A4 represents a hydrogen atom, a C1 to C6 alkyl group, a C1 to C6 It represents a haloalkyl group or a C3-C8 cycloalkyl group. (See WO 14/095675),
［ｂ－２３．５３］式（ｓ１７）
Figure JPOXMLDOC01-appb-C000083
［式中、ｍ１は、０～３の整数を表し、Ａ５およびＡ６は、それぞれ独立していて、ハロゲン原子、またはＣ１～Ｃ６のアルキル基を表し、Ａ７およびＡ８は、それぞれ独立していて、ハロゲン原子、またはＣ１～Ｃ６のアルコキシ基を表し、ｍ１が２以上の場合、２以上のＡ７は、それぞれ独立した置換基を表し、同一または異なっていてよい。］で表される化合物（国際公開第０９／１３７５３８号、国際公開第０９／１３７６５１号参照）、 [B-23.53] Expression (s17)
Figure JPOXMLDOC01-appb-C000083
[In the formula, m1 represents an integer of 0 to 3, A5 and A6 are each independently a halogen atom or a C1 to C6 alkyl group, and A7 and A8 are each independently, When a halogen atom or a C1 to C6 alkoxy group is represented, and m1 is 2 or more, 2 or more A7's each independently represent a substituent, which may be the same or different. ] The compound represented by these (refer international publication 09/137538, international publication 09/137651),
［ｂ－２３．５４］式（ｓ１８）
Figure JPOXMLDOC01-appb-C000084
［式中、Ａ９およびＡ１０は、それぞれ独立していて、水素原子、またはハロゲン原子を表し、Ａ１１は、ハロゲン原子を表し、Ａ１２は、ハロゲン原子、またはＣ１～Ｃ６のアルキル基を表し、Ａ１３は、ハロゲン原子、シアノ基、Ｃ１～Ｃ６のアルキル基、またはＣ１～Ｃ６のアルコキシ基を表す。］で表される化合物（国際公開第１２／０３１０６１号参照）、 [B-23.54] Expression (s18)
Figure JPOXMLDOC01-appb-C000084
[In the formula, A9 and A10 each independently represent a hydrogen atom or a halogen atom, A11 represents a halogen atom, A12 represents a halogen atom or a C1 to C6 alkyl group, and A13 represents Represents a halogen atom, a cyano group, a C1 to C6 alkyl group, or a C1 to C6 alkoxy group. ] (See WO 12/031061),
［ｂ－２３．５５］式（ｓ１９）
Figure JPOXMLDOC01-appb-C000085
［式中、ｍ２は、０～６の整数を表し、Ａ１４およびＡ１５は、それぞれ独立していて、ハロゲン原子、シアノ基、またはＣ１～Ｃ６のアルキル基を表し、Ａ１６は、水素原子、ハロゲン原子、またはＣ１～Ｃ６のアルコキシ基を表し、Ａ１７は、ハロゲン原子、またはＣ１～Ｃ６のアルコキシ基を表し、ｍ２が２以上の場合、２以上のＡ１７は、それぞれ独立した置換基を表し、同一または異なっていてよい。］で表される化合物（国際公開第０５／１２１１０４号参照）、 [B-23.55] Expression (s19)
Figure JPOXMLDOC01-appb-C000085
[In the formula, m2 represents an integer of 0 to 6, A14 and A15 each independently represent a halogen atom, a cyano group, or a C1 to C6 alkyl group, and A16 represents a hydrogen atom or a halogen atom. Or a C1 to C6 alkoxy group, A17 represents a halogen atom or a C1 to C6 alkoxy group, and when m2 is 2 or more, 2 or more A17's each independently represent a substituent, Can be different. (See WO 05/121104),
［ｂ－２３．５６］式（ｓ２０）
Figure JPOXMLDOC01-appb-C000086
［式中、Ａ１８およびＡ１９は、それぞれ独立していて、ハロゲン原子、シアノ基、またはＣ１～Ｃ６のアルキル基を表し、Ａ２０、Ａ２１およびＡ２２は、それぞれ独立していて、水素原子、ハロゲン原子、またはＣ１～Ｃ６のアルコキシ基を表す。］で表される化合物（国際公開第０７／０６６６０１号参照）、 [B-23.56] Expression (s20)
Figure JPOXMLDOC01-appb-C000086
[In the formula, A18 and A19 each independently represent a halogen atom, a cyano group, or a C1 to C6 alkyl group, and A20, A21, and A22 each independently represent a hydrogen atom, a halogen atom, Alternatively, it represents a C1 to C6 alkoxy group. (See WO 07/066601),
［ｂ－２３．５７］式（ｓ２１）
Figure JPOXMLDOC01-appb-C000087
［式中、Ａ２３およびＡ２４は、それぞれ独立していて、水素原子、ハロゲン原子、Ｃ１～Ｃ６のアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表し、Ｘは、酸素原子または硫黄原子を表す。］で表される化合物（国際公開第０７／０８７９０６号、国際公開第０９／０１６２２０号、国際公開第１０／１３０７６７号参照）、 [B-23.57] Expression (s21)
Figure JPOXMLDOC01-appb-C000087
[In the formula, A23 and A24 each independently represent a hydrogen atom, a halogen atom, a C1-C6 alkyl group, or a C3-C8 cycloalkyl group, and X represents an oxygen atom or a sulfur atom. ] A compound represented by the following (see International Publication No. 07/087906, International Publication No. 09/016220, International Publication No. 10/130767),
［ｂ－２３．５８］式（ｓ２２）
Figure JPOXMLDOC01-appb-C000088
［式中、ｍ３は、０～５の整数を表し、Ａ２５は、ハロゲン原子、Ｃ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、またはＣ３～Ｃ８のシクロアルキル基を表し、ｍ３が２以上の場合、２以上のＡ２５は、それぞれ独立した置換基を表し、同一または異なっていてよい。］で表される化合物（国際公開第１３／０９２２２４号参照）、 [B-23.58] Expression (s22)
Figure JPOXMLDOC01-appb-C000088
[Wherein, m3 represents an integer of 0 to 5, A25 represents a halogen atom, a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, Alternatively, when it represents a C3 to C8 cycloalkyl group, and m3 is 2 or more, 2 or more A25's each independently represent a substituent, which may be the same or different. (See WO 13/092224),
［ｂ－２３．５９］式（ｓ２３）
Figure JPOXMLDOC01-appb-C000089
［式中、Ａ２６は、水素原子、またはハロゲン原子を表し、Ｖ１およびＶ２は、それぞれ独立していて、酸素原子、または硫黄原子を表す。］で表される化合物（国際公開第１２／０２５４５０号参照）、 [B-23.59] Expression (s23)
Figure JPOXMLDOC01-appb-C000089
[In the formula, A26 represents a hydrogen atom or a halogen atom, and V1 and V2 each independently represent an oxygen atom or a sulfur atom. (See WO 12/025450),
［ｂ－２３．６０］式（ｓ２４）または式（ｓ２５）
Figure JPOXMLDOC01-appb-C000090
［式中、ｍ４は、０～５の整数を表し、Ａ２７は、Ｃ１～Ｃ６のアルキル基を表し、Ａ２８は、ハロゲン原子、シアノ基、Ｃ１～Ｃ６のアルキル基、またはＣ１～Ｃ６のハロアルキル基を表し、ｍ４が２以上の場合、２以上のＡ２８は、それぞれ独立した置換基を表し、同一または異なっていてよく、Ａ２９は、Ｃ１～Ｃ６のアルキル基、Ｃ２～Ｃ６のアルケニル基、またはＣ３～Ｃ６のアルキニル基を表す。］で表される化合物（国際公開第１３／０３７７１７号参照）、 [B-23.60] Expression (s24) or Expression (s25)
Figure JPOXMLDOC01-appb-C000090
[Wherein, m4 represents an integer of 0 to 5, A27 represents a C1 to C6 alkyl group, A28 represents a halogen atom, a cyano group, a C1 to C6 alkyl group, or a C1 to C6 haloalkyl group. And when m4 is 2 or more, two or more A28's each independently represent a substituent and may be the same or different, and A29 is a C1 to C6 alkyl group, a C2 to C6 alkenyl group, or C3. Represents a C6 alkynyl group. ] (See WO 13/037771),
［ｂ－２３．６１］式（ｓ２６）または式（ｓ２７）
Figure JPOXMLDOC01-appb-C000091
［式中、ｍ５は、０～５の整数を表し、Ａ３０は、Ｃ１～Ｃ６のアルキル基を表し、Ａ３１は、ハロゲン原子、シアノ基、Ｃ１～Ｃ６のアルキル基、またはＣ１～Ｃ６のハロアルキル基を表し、ｍ５が２以上の場合、２以上のＡ３１は、それぞれ独立した置換基を表し、同一または異なっていてよく、Ａ３２は、Ｃ１～Ｃ６のアルキル基、Ｃ２～Ｃ６のアルケニル基、またはＣ３～Ｃ６のアルキニル基を表す。］で表される化合物（国際公開第１３／０３７７１７号参照）、 [B-23.61] Expression (s26) or Expression (s27)
Figure JPOXMLDOC01-appb-C000091
[Wherein, m5 represents an integer of 0 to 5, A30 represents a C1 to C6 alkyl group, A31 represents a halogen atom, a cyano group, a C1 to C6 alkyl group, or a C1 to C6 haloalkyl group. When m5 is 2 or more, 2 or more A31's each independently represent a substituent, and may be the same or different, and A32's are C1 to C6 alkyl groups, C2 to C6 alkenyl groups, or C3. Represents a C6 alkynyl group. ] (See WO 13/037771),
［ｂ－２３．６２］式（ｓ２８）
Figure JPOXMLDOC01-appb-C000092
［式中、Ａ３３、Ａ３４、Ａ３５およびＡ３６は、それぞれ独立していて、水素原子、またはハロゲン原子を表し、Ａ３７は、水素原子、アセチル基、またはベンゾイル基を表す。］で表される化合物（国際公開第０６／０３１６３１号、国際公開第１０／０６９８８２号参照）、 [B-23.62] Expression (s28)
Figure JPOXMLDOC01-appb-C000092
[Wherein A33, A34, A35 and A36 are each independently a hydrogen atom or a halogen atom, and A37 represents a hydrogen atom, an acetyl group or a benzoyl group. ] (Refer to WO 06/031631, WO 10/069882),
［ｂ－２３．６３］式（ｓ２９）
Figure JPOXMLDOC01-appb-C000093
［式中、Ａ３８は、Ｃ１～Ｃ６のアルキル基、またはＣ１～Ｃ６のハロアルキル基を表し、Ａ３９およびＡ４０は、それぞれ独立していて、水素原子、またはハロゲン原子を表す。］で表される化合物（国際公開第１４／０４３３７６号参照）、 [B-23.63] Expression (s29)
Figure JPOXMLDOC01-appb-C000093
[In the formula, A38 represents a C1-C6 alkyl group or a C1-C6 haloalkyl group, and A39 and A40 each independently represent a hydrogen atom or a halogen atom. (See WO 14/043376),
［ｂ－２３．６４］式（ｓ３０）
Figure JPOXMLDOC01-appb-C000094
［式中、Ａ４１は、水素原子、水硫基（－ＳＨ）、チオシアン酸基（－ＳＣＮ）、またはＣ１～Ｃ６のアルキルチオ基を表し、Ａ４２、Ａ４３、Ａ４４およびＡ４５は、それぞれ独立していて、水素原子、またはハロゲン原子を表す。］で表される化合物（国際公開第０９／０７７４４３号参照）、 [B-23.64] Expression (s30)
Figure JPOXMLDOC01-appb-C000094
[In the formula, A41 represents a hydrogen atom, a sulfur group (-SH), a thiocyanate group (-SCN), or a C1 to C6 alkylthio group, and A42, A43, A44 and A45 are each independently Represents a hydrogen atom or a halogen atom. ] The compound represented by these (refer international publication 09/077443),
［ｂ－２３．６５］式（ｓ３１）または式（ｓ３２）
Figure JPOXMLDOC01-appb-C000095
［式中、Ａ４６は、水素原子、またはハロゲン原子を表し、Ａ４７は、Ｃ１～Ｃ６のアルキル基を表し、Ａ４８は、ハロゲン原子を表す。］で表される化合物（国際公開第１１／０７０７７１号参照）、 [B-23.65] Expression (s31) or Expression (s32)
Figure JPOXMLDOC01-appb-C000095
[In the formula, A46 represents a hydrogen atom or a halogen atom, A47 represents a C1-C6 alkyl group, and A48 represents a halogen atom. (See WO 11/070771),
［ｂ－２３．６６］式（ｓ３３）
Figure JPOXMLDOC01-appb-C000096
［式中、Ａ４９、Ａ５０およびＡ５１は、それぞれ独立していて、水素原子、またはハロゲン原子を表す。］で表される化合物（国際公開第１１／０８１１７４号参照）等が挙げられる。 [B-23.66] Expression (s33)
Figure JPOXMLDOC01-appb-C000096
[Wherein, A49, A50 and A51 each independently represent a hydrogen atom or a halogen atom. (See International Publication No. 11/081174).
　本発明化合物と混合して使用することができる殺虫剤に含まれる具体的な成分は、以下の群ｃで例示され、これらの塩、異性体およびＮ－オキシド体を含む。ただし、公知の殺虫剤はこれらに限定されるものではない。 Specific components contained in the insecticide that can be used as a mixture with the compound of the present invention are exemplified in the following group c, and include salts, isomers and N-oxides thereof. However, known insecticides are not limited to these.
群ｃ：
ｃ－１：カーバメート系アセチルコリンエステラーゼ（ＡＣｈＥ）阻害剤
　カーバメート系アセチルコリンエステラーゼ（ＡＣｈＥ）阻害剤として、［ｃ－１．１］ホスホカルブ（ｐｈｏｓｐｈｏｃａｒｂ）、［ｃ－１．２］アラニカルブ（ａｌａｎｙｃａｒｂ）、［ｃ－１．３］ブトカルボキシム（ｂｕｔｏｃａｒｂｏｘｉｍ）、［ｃ－１．４］ブトキシカルボキシム（ｂｕｔｏｘｙｃａｒｂｏｘｉｍ）、［ｃ－１．５］チオジカルブ（ｔｈｉｏｄｉｃａｒｂ）、［ｃ－１．６］チオファノックス（ｔｈｉｏｆａｎｏｘ）、［ｃ－１．７］アルジカルブ（ａｌｄｉｃａｒｂ）、［ｃ－１．８］ベンジオカルブ（ｂｅｎｄｉｏｃａｒｂ）、［ｃ－１．９］ベンフラカルブ（ｂｅｎｆｕｒａｃａｒｂ）、［ｃ－１．１０］カルバリル（ｃａｒｂａｒｙｌ）、［ｃ－１．１１］カルボフラン（ｃａｒｂｏｆｕｒａｎ）、［ｃ－１．１２］カルボスルファン（ｃａｒｂｏｓｕｌｆａｎ）、［ｃ－１．１３］エチオフェンカルブ（ｅｔｈｉｏｆｅｎｃａｒｂ）、［ｃ－１．１４］フェノブカルブ（ｆｅｎｏｂｕｃａｒｂ）、［ｃ－１．１５］ホルメタネート（ｆｏｒｍｅｔａｎａｔｅ）、［ｃ－１．１６］フラチオカルブ（ｆｕｒａｔｈｉｏｃａｒｂ）、［ｃ－１．１７］イソプロカルブ（ｉｓｏｐｒｏｃａｒｂ）、［ｃ－１．１８］メチオカルブ（ｍｅｔｈｉｏｃａｒｂ）、［ｃ－１．１９］メソミル（ｍｅｔｈｏｍｙｌ）、［ｃ－１．２０］オキサミル（ｏｘａｍｙｌ）、［ｃ－１．２１］ピリミカルブ（ｐｉｒｉｍｉｃａｒｂ）、［ｃ－１．２２］プロポキスル（ｐｒｏｐｏｘｕｒ）、［ｃ－１．２３］トリメタカルブ（ｔｒｉｍｅｔｈａｃａｒｂ）、［ｃ－１．２４］ＸＭＣ（３，５－ｘｙｌｙｌ　ｍｅｔｈｙｌｃａｒｂａｍａｔｅ）、［ｃ－１．２５］アリキシカルブ（ａｌｌｙｘｙｃａｒｂ）、［ｃ－１．２６］アルドキシカルブ（ａｌｄｏｘｙｃａｒｂ）、［ｃ－１．２７］ブフェンカルブ（ｂｕｆｅｎｃａｒｂ）、［ｃ－１．２８］ブタカルブ（ｂｕｔａｃａｒｂ）、［ｃ－１．２９］カーバノレート（ｃａｒｂａｎｏｌａｔｅ）、［ｃ－１．３０］メトルカルブ（ｍｅｔｏｌｃａｒｂ）、［ｃ－１．３１］キシルイルカルブ（ｘｙｌｙｌｃａｒｂ）、［ｃ－１．３２］フェノチオカルブ（ｆｅｎｏｔｈｉｏｃａｒｂ）、［ｃ－１．３３］キシリルカルブ（ｘｙｌｙｌｃａｒｂ）、［ｃ－１．３４］ベンダイオカルブ（ｂｅｎｄｉｏｃａｒｂ）等が挙げられる。 Group c:
c-1: Carbamate acetylcholinesterase (AChE) inhibitor [C-1.1] phosphocarb, [c-1.2] alanycarb, [c-1.1] as a carbamate acetylcholinesterase (AChE) inhibitor -1.3] butocarboxim, [c-1.4] butoxycarboxim, [c-1.5] thiodicarb, [c-1.6] thiophanox ), [C-1.7] aldicarb, [c-1.8] bendiocarb, [c-1.9] benfuracarb, [c-1.10] carbaryl (carba). ryl), [c-1.11] carbofuran, [c-1.12] carbosulfan, [c-1.13] ethiofencarb, [c-1.14] phenocarb. fenobcarb, [c-1.15] formetanate, [c-1.16] furatiocarb, [c-1.17] isoprocarb, [c-1.18] methiocarb. , [C-1.19] methomyl, [c-1.20] oxamyl, [c-1. 21] pirimicab, [c-1. 22] propoxur, c-1.23] trimetacarb, [c-1.24] XMC (3,5-xylyl methylcarbamate), [c-1.25] allyxycarb, [c-1.26] aldoxicarb (Aldoxycarb), [c-1.27] bufencarb, [c-1.28] butacarb, [c-1.29] carbanolate, [c-1.30] metolcarb. ), [C-1.31] xylylcarb (xylylcarb), [c-1.32] phenothiocarb, [c-1.33] xylylcarb, [c-1.34] bendiocarb. bendiocarb), and the like.
ｃ－２：有機リン系アセチルコリンエステラーゼ（ＡＣｈＥ）阻害剤
　有機リン系アセチルコリンエステラーゼ（ＡＣｈＥ）阻害剤として、［ｃ－２．１］アセフェート（ａｃｅｐｈａｔｅ）、［ｃ－２．２］アザメチホス（ａｚａｍｅｔｈｉｐｈｏｓ）、［ｃ－２．３］アジンホス－メチル（ａｚｉｎｐｈｏｓ－ｍｅｔｈｙｌ）、［ｃ－２．４］アジンホス－エチル（ａｚｉｎｐｈｏｓ－ｅｔｈｙｌ）、［ｃ－２．５］エセフォン（ｅｔｈｅｐｈｏｎ）、［ｃ－２．６］カズサホス（ｃａｄｕｓａｆｏｓ）、［ｃ－２．７］クロルエトキシホス（ｃｈｌｏｒｅｔｈｏｘｙｆｏｓ）、［ｃ－２．８］クロルフェンビンホス（ｃｈｌｏｒｆｅｎｖｉｎｐｈｏｓ）、［ｃ－２．９］クロルメホス（ｃｈｌｏｒｍｅｐｈｏｓ）、［ｃ－２．１０］クロルピリホス（ｃｈｌｏｒｐｙｒｉｆｏｓ）、［ｃ－２．１１］クロルピリホス－メチル（ｃｈｌｏｒｐｙｒｉｆｏｓ－ｍｅｔｈｙｌ）、［ｃ－２．１２］クマホス（ｃｏｕｍａｐｈｏｓ）、［ｃ－２．１３］シアノホス（ｃｙａｎｏｐｈｏｓ）、［ｃ－２．１４］デメトン－Ｓ－メチル（ｄｅｍｅｔｏｎ－Ｓ－ｍｅｔｈｙｌ）、［ｃ－２．１５］ダイアジノン（ｄｉａｚｉｎｏｎ）、［ｃ－２．１６］ジクロフェンチオン（ｄｉｃｈｌｏｆｅｎｔｈｉｏｎ）、［ｃ－２．１７］ジクロルボス（ｄｉｃｈｌｏｒｖｏｓ）、［ｃ－２．１８］ジクロトホス（ｄｉｃｒｏｔｏｐｈｏｓ）、［ｃ－２．１９］ジメトエート（ｄｉｍｅｔｈｏａｔｅ）、［ｃ－２．２０］ジメチルビンホス（ｄｉｍｅｔｈｙｌｖｉｎｐｈｏｓ）、［ｃ－２．２１］ジスルホトン（ｄｉｓｕｌｆｏｔｏｎ）、［ｃ－２．２２］Ｏ－エチル　Ｏ－４－ニトロフェニル　フェニルホスホノチオアート（Ｏ－ｅｔｈｙｌ　Ｏ－４－ｎｉｔｒｏｐｈｅｎｙｌ　ｐｈｅｎｙｌｐｈｏｓｐｈｏｎｏｔｈｉｏａｔｅ）、［ｃ－２．２３］エチオン（ｅｔｈｉｏｎ）、［ｃ－２．２４］エトプロホス（ｅｔｈｏｐｒｏｐｈｏｓ）、［ｃ－２．２５］ファムフール（ｆａｍｐｈｕｒ）、［ｃ－２．２６］フェナミホス（ｆｅｎａｍｉｐｈｏｓ）、［ｃ－２．２７］フェニトロチオン（ｆｅｎｉｔｒｏｔｈｉｏｎ）、［ｃ－２．２８］フェンチオン（ｆｅｎｔｈｉｏｎ）、［ｃ－２．２９］ホスチアゼート（ｆｏｓｔｈｉａｚａｔｅ）、［ｃ－２．３０］ヘプテノホス（ｈｅｐｔｅｎｏｐｈｏｓ）、［ｃ－２．３１］イソフェンホス－メチル（ｉｓｏｆｅｎｐｈｏｓ－ｍｅｔｈｙｌ）、［ｃ－２．３２］イソカルボホス（Ｉｓｏｃａｒｂｏｐｈｏｓ）、［ｃ－２．３３］イソキサチオン（ｉｓｏｘａｔｈｉｏｎ）、［ｃ－２．３４］マラチオン（ｍａｌａｔｈｉｏｎ）、［ｃ－２．３５］メカルバム（ｍｅｃａｒｂａｍ）、［ｃ－２．３６］メタミドホス（ｍｅｔｈａｍｉｄｏｐｈｏｓ）、［ｃ－２．３７］メチダチオン（ｍｅｔｈｉｄａｔｈｉｏｎ）、［ｃ－２．３８］メビンホス（ｍｅｖｉｎｐｈｏｓ）、［ｃ－２．３９］モノクロトホス（ｍｏｎｏｃｒｏｔｏｐｈｏｓ）、［ｃ－２．４０］ナレッド（ｎａｌｅｄ）、［ｃ－２．４１］オメトエート（ｏｍｅｔｈｏａｔｅ）、［ｃ－２．４２］オキシデメトン－メチル（ｏｘｙｄｅｍｅｔｏｎ－ｍｅｔｈｙｌ）、［ｃ－２．４３］パラチオン（ｐａｒａｔｈｉｏｎｓ）、［ｃ－２．４４］パラチオン－メチル（ｐａｒａｔｈｉｏｎ－ｍｅｔｈｙｌ）、［ｃ－２．４５］フェントエート（ｐｈｅｎｔｈｏａｔｅ）、［ｃ－２．４６］ホレート（ｐｈｏｒａｔｅ）、［ｃ－２．４７］ホサロン（ｐｈｏｓａｌｏｎｅ）、［ｃ－２．４８］ホスメット（ｐｈｏｓｍｅｔ）、［ｃ－２．４９］ホスファミドン（ｐｈｏｓｐｈａｍｉｄｏｎ）、［ｃ－２．５０］ホキシム（ｐｈｏｘｉｍ）、［ｃ－２．５１］ピリミホス－メチル（ｐｉｒｉｍｉｐｈｏｓ－ｍｅｔｈｙｌ）、［ｃ－２．５２］プロフェノホス（ｐｒｏｆｅｎｏｆｏｓ）、［ｃ－２．５３］プロペタンホス（ｐｒｏｐｅｔａｍｐｈｏｓ）、［ｃ－２．５４］プロチオホス（ｐｒｏｔｈｉｏｆｏｓ）、［ｃ－２．５５］ピラクロホス（ｐｙｒａｃｌｏｆｏｓ）、［ｃ－２．５６］ピリダフェンチオン（ｐｙｒｉｄａｐｈｅｎｔｈｉｏｎ）、［ｃ－２．５７］キナルホス（ｑｕｉｎａｌｐｈｏｓ）、［ｃ－２．５８］スルホテップ（ｓｕｌｆｏｔｅｐ）、［ｃ－２．５９］テブピリムホス（ｔｅｂｕｐｉｒｉｍｆｏｓ）、［ｃ－２．６０］テメホス（ｔｅｍｅｐｈｏｓ）、［ｃ－２．６１］テルブホス（ｔｅｒｂｕｆｏｓ）、［ｃ－２．６２］チオメトン（ｔｈｉｏｍｅｔｏｎ）、［ｃ－２．６３］トリアゾホス（ｔｒｉａｚｏｐｈｏｓ）、［ｃ－２．６４］トリクロルホン（ｔｒｉｃｈｌｏｒｆｏｎ）、［ｃ－２．６５］バミドチオン（ｖａｍｉｄｏｔｈｉｏｎ）、［ｃ－２．６６］クロルチオン（ｃｈｌｏｒｏｔｈｉｏｎ）、［ｃ－２．６７］ブロムフェンビンホス（ｂｒｏｍｆｅｎｖｉｎｆｏｓ）、［ｃ－２．６８］ブロモホス（ｂｒｏｍｏｐｈｏｓ）、［ｃ－２．６９］ブロモホス－エチル（ｂｒｏｍｏｐｈｏｓ－ｅｔｈｙｌ）、［ｃ－２．７０］ブタチオホス（ｂｕｔａｔｈｉｏｆｏｓ）、［ｃ－２．７１］カルボフェノチオン（ｃａｒｂｏｐｈｅｎｏｔｈｉｏｎ）、［ｃ－２．７２］クロルホキシム（ｃｈｌｏｒｐｈｏｘｉｍ）、［ｃ－２．７３］スルプロホス（ｓｕｌｐｒｏｆｏｓ）、［ｃ－２．７４］ジアミダホス（ｄｉａｍｉｄａｆｏｓ）、［ｃ－２．７５］テトラクロルビンホス（ｔｅｔｒａｃｈｌｏｒｖｉｎｐｈｏｓ）、［ｃ－２．７６］プロパホス（ｐｒｏｐａｐｈｏｓ）、［ｃ－２．７７］メスルフェンホス（ｍｅｓｕｌｆｅｎｆｏｓ）、［ｃ－２．７８］ジオキサベンゾホス（ｄｉｏｘａｂｅｎｚｏｆｏｓ）、［ｃ－２．７９］エトリムホス（ｅｔｒｉｍｆｏｓ）、［ｃ－２．８０］オキシデプロホス（ｏｘｙｄｅｐｒｏｆｏｓ）、［ｃ－２．８１］ホルモチオン（ｆｏｒｍｏｔｈｉｏｎ）、［ｃ－２．８２］フェンスルホチオン（ｆｅｎｓｕｌｆｏｔｈｉｏｎ）、［ｃ－２．８３］イサゾホス（ｉｓａｚｏｆｏｓ）、［ｃ－２．８４］イミシアホス（ｉｍｉｃｙａｆｏｓ）、［ｃ－２．８５］イサミドホス（ｉｓａｍｉｄｏｆｏｓ）、［ｃ－２．８６］チオナジン（ｔｈｉｏｎａｚｉｎ）、［ｃ－２．８７］ホスチエタン（ｆｏｓｔｈｉｅｔａｎ）等が挙げられる。 c-2: Organophosphorus acetylcholinesterase (AChE) inhibitor [c-2.1] acephate, [c-2.2] azamethiphos, as an organophosphorus acetylcholinesterase (AChE) inhibitor [C-2.3] Azinphos-methyl, [c-2.4] Azinphos-ethyl, [c-2.5] Ethephon, [c-2.6] ] Cadussafos, [c-2.7] chlorethoxyphos, [c-2.8] chlorfenvinphos, [c-2.9] chlormephos, [c- 2.10] Black Chlorpyrifos, [c-2.11] chlorpyrifos-methyl, [c-2.12] coumaphos, [c-2.13] cyanophos, [c-2. 14] demeton-S-methyl, [c-2.15] diazinon, [c-2.16] diclofenthion, [c-2.17] dichlorvos. , [C-2.18] dicrotophos, [c-2.19] dimethoate, [c-2.20] dimethylvinphos, [c-2. 21] disul. [C-2.22] O-ethyl O-4-nitrophenyl phenylphosphonothioate (O-ethyl O-4-nitrophenyl phenylphosphonothioate), [c-2.23] ethion, c-2.24] Ethoprophos, [c-2.25] famfur, [c-2.26] fenamiphos, [c-2.27] fenitrothion, [c- 2.28] fenthion, [c-2.29] fosthiazate, [c-2.30] heptenophos, [c-2.31] isofenphos-methyl isofenphos-methyl), [c-2.32] isocarbophos, [c-2.33] isoxathion, [c-2.34] malathion, [c-2.35] mecarbam ( mecarbam), [c-2.36] methamidophos, [c-2.37] methidathion, [c-2.38] mevinphos, [c-2.39] monocrotophos. ), [C-2.40] naled, [c-2.41] omethoate, [c-2.42] oxydemethon-methyl, [c-2.4]. ] Parathion (parathions), [c-2.44] parathion-methyl (parathion-methyl), [c-2.45] phentoate (c-2.46) phorate (crate), [c-2] .47] phosalone, [c-2.48] phosmet, [c-2.49] phosphamidon, [c-2.50] phoxim, [c-2.51] ] Pirimiphos-methyl, [c-2.52] profenofos, [c-2.53] propetanphos, [c-2.54] prothiophos, [c-2] .55] Pyraclofos, [c-2.56] pyridaphenthion, [c-2.57] quinalphos, [c-2.58] sulfotep, [c-2.59] tebupirimphos ( tebupirimfos), [c-2.60] temephos, [c-2.61] terbufos, [c-2.62] thiomethone, [c-2.63] triazophos. , [C-2.64] trichlorfon, [c-2.65] vamidthione, [c-2.66] chlorthion, [c-2.67] bromphene. Bromfenvinfos, [c-2.68] bromophos, [c-2.69] bromophos-ethyl, [c-2.70] butathiophos, [c-2. 71] Carbophenothion, [c-2.72] chlorphoxim, [c-2.73] sulprofos, [c-2.74] diamidaphos, [c-2. 75] Tetrachlorvinphos, [c-2.76] propaphos, [c-2.77] mesulfenfos, [c-2.78] dioxabenzo (Dioxabenzofos), [c-2.79] etrimfos, [c-2.80] oxydeprofos, [c-2.81] formothion (formation), [c-2.82]. Fensulfothion, [c-2.83] isazofos, [c-2.84] imicyafos, [c-2.85] isamidofos, [c-2.86] thionazine (f-sulfothion). and thionazin) and [c-2.87] fosthietan.
ｃ－３：ＧＡＢＡ作動性塩素イオンチャネルブロッカー
　ＧＡＢＡ作動性塩素イオンチャネルブロッカーとして、［ｃ－３．１］クロルデン（ｃｈｌｏｒｄａｎｅ）、［ｃ－３．２］エンドスルファン（ｅｎｄｏｓｕｌｆａｎ）、［ｃ－３．３］リンデン（ｌｉｎｄａｎｅ）、［ｃ－３．４］ジエノクロル（ｄｉｅｎｏｃｈｌｏｒ）、［ｃ－３．５］エチプロール（ｅｔｈｉｐｒｏｌｅ）、［ｃ－３．６］フィプロニル（ｆｉｐｒｏｎｉｌ）、［ｃ－３．７］アセトプロール（ａｃｅｔｏｐｒｏｌｅ）等が挙げられる。 c-3: GABAergic chloride ion blocker As GABAergic chloride ion blocker, [c-3.1] chlordane, [c-3.2] endosulfan, [c-3.3] ] Lindane, [c-3.4] dienochlor, [c-3.5] ethiprole, [c-3.6] fipronil, [c-3.7] acetate Examples include acetoprole and the like.
ｃ－４：ナトリウムチャネルモジュレーター
　ナトリウムチャネルモジュレーターとして、［ｃ－４．１］アクリナトリン（ａｃｒｉｎａｔｈｒｉｎ）、［ｃ－４．２］アレスリン［（１Ｒ）－アイソマー］（ａｌｌｅｔｈｒｉｎ［（１Ｒ）－ｉｓｏｍｅｒ］）、［ｃ－４．３］ビフェントリン（ｂｉｆｅｎｔｈｒｉｎ）、［ｃ－４．４］ビオアレスリン（ｂｉｏａｌｌｅｔｈｒｉｎ）、［ｃ－４．５］ビオアレスリン　Ｓ－シクロペンテニル　アイソマー（ｂｉｏａｌｌｅｔｈｒｉｎ　Ｓ－ｃｙｃｌｏｐｅｎｔｅｎｙｌ　ｉｓｏｍｅｒ）、［ｃ－４．６］ビオレスメトリン（ｂｉｏｒｅｓｍｅｔｈｒｉｎ）、［ｃ－４．７］シクロプロトリン（ｃｙｃｌｏｐｒｏｔｈｒｉｎ）、［ｃ－４．８］シフルトリン（ｃｙｆｌｕｔｈｒｉｎ）、［ｃ－４．９］ベータ－シフルトリン（ｂｅｔａ－ｃｙｆｌｕｔｈｒｉｎ）、［ｃ－４．１０］シハロトリン（ｃｙｈａｌｏｔｈｒｉｎ）、［ｃ－４．１１］ガンマ－シハロトリン（ｇａｍｍａ－ｃｙｈａｌｏｔｈｒｉｎ）、［ｃ－４．１２］ラムダ－シハロトリン（ｌａｍｂｄａ－ｃｙｈａｌｏｔｈｒｉｎ）、［ｃ－４．１３］シペルメトリン（ｃｙｐｅｒｍｅｔｈｒｉｎ）、［ｃ－４．１４］アルファ－シペルメトリン（ａｌｐｈａ－ｃｙｐｅｒｍｅｔｈｒｉｎ）、［ｃ－４．１５］ベータ－シペルメトリン（ｂｅｔａ－ｃｙｐｅｒｍｅｔｈｒｉｎ）、［ｃ－４．１６］セタ－シペルメトリン（ｔｈｅｔａ－ｃｙｐｅｒｍｅｔｈｒｉｎ）、［ｃ－４．１７］ゼダ－シペルメトリン（ｚｅｔａ－ｃｙｐｅｒｍｅｔｈｒｉｎ）、［ｃ－４．１８］シフェノトリン［（１Ｒ）－トランス－アイソマー］（ｃｙｐｈｅｎｏｔｈｒｉｎ［（１Ｒ）－ｔｒａｎｓ－ｉｓｏｍｅｒ］）、［ｃ－４．１９］デルタメトリン（ｄｅｌｔａｍｅｔｈｒｉｎ）、［ｃ－４．２０］エンペントリン［（ＥＺ）－（１Ｒ）－アイソマー］（ｅｍｐｅｎｔｈｒｉｎ［（ＥＺ）－（１Ｒ）－ｉｓｏｍｅｒ］）、［ｃ－４．２１］エスフェンバレレート（ｅｓｆｅｎｖａｌｅｒａｔｅ）、［ｃ－４．２２］エトフェンプロックス（ｅｔｈｏｆｅｎｐｒｏｘ）、［ｃ－４．２３］フェンプロパトリン（ｆｅｎｐｒｏｐａｔｈｒｉｎ）、［ｃ－４．２４］フェンバレレート（ｆｅｎｖａｌｅｒａｔｅ）、［ｃ－４．２５］フルシトリネート（ｆｌｕｃｙｔｈｒｉｎａｔｅ）、［ｃ－４．２６］フルメトリン（ｆｌｕｍｅｔｈｒｉｎ）、［ｃ－４．２７］タウ－フルバリネート（ｔａｕ－ｆｌｕｖａｌｉｎａｔｅ）、［ｃ－４．２８］ハルフェンプロックス（ｈａｌｆｅｎｐｒｏｘ）、［ｃ－４．２９］イミプロトリン（ｉｍｉｐｒｏｔｈｒｉｎ）、［ｃ－４．３０］メトトリン（ｍｅｔｈｏｔｈｒｉｎ）、［ｃ－４．３１］メトフルトリン（ｍｅｔｏｆｌｕｔｈｒｉｎ）、［ｃ－４．３２］イプシロン－メトフルトリン（ｅｐｓｉｌｏｎ－ｍｅｔｏｆｌｕｔｈｒｉｎ）、［ｃ－４．３３］モンフルオロトリン（ｍｏｍｆｌｕｏｒｏｔｈｒｉｎ）、［ｃ－４．３４］イプシロン－モンフルオロトリン（ｅｐｓｉｌｏｎ－ｍｏｍｆｌｕｏｒｏｔｈｒｉｎ）、［ｃ－４．３５］ペルメトリン（ｐｅｒｍｅｔｈｒｉｎ）、［ｃ－４．３６］フェノトリン［（１Ｒ）－トランス－アイソマー］（ｐｈｅｎｏｔｈｒｉｎ［（１Ｒ）－ｔｒａｎｓ－ｉｓｏｍｅｒ］）、［ｃ－４．３７］プラレトリン（ｐｒａｌｌｅｔｈｒｉｎ）、［ｃ－４．３８］レスメトリン（ｒｅｓｍｅｔｈｒｉｎ）、［ｃ－４．３９］カデトリン（ｋａｄｅｔｈｒｉｎ）、［ｃ－４．４０］シラフルオフェン（ｓｉｌａｆｌｕｏｆｅｎ）、［ｃ－４．４１］テフルトリン（ｔｅｆｌｕｔｈｒｉｎ）、［ｃ－４．４２］テトラメトリン（ｔｅｔｒａｍｅｔｈｒｉｎ）、［ｃ－４．４３］テトラメトリン［（１Ｒ）－アイソマー］（ｔｅｔｒａｍｅｔｈｒｉｎ［（１Ｒ）－ｉｓｏｍｅｒ］）、［ｃ－４．４４］トラロメトリン（ｔｒａｌｏｍｅｔｈｒｉｎ）、［ｃ－４．４５］トランスフルトリン（ｔｒａｎｓｆｌｕｔｈｒｉｎ）、［ｃ－４．４６］ＺＸＩ８９０１（３－（４－ｂｒｏｍｏｐｈｅｎｏｘｙ）ｐｈｅｎｙｌ］－ｃｙａｎｏｍｅｔｈｙｌ　４－（ｄｉｆｌｕｏｒｏｍｅｔｈｏｘｙ）－α－（１－ｍｅｔｈｙｌｅｔｈｙｌ）ｂｅｎｚｅｎｅａｃｅｔａｔｅ）、［ｃ－４．４７］バイオペルメトリン（ｂｉｏｐｅｒｍｅｔｈｒｉｎ）、［ｃ－４．４８］フラメトリン（ｆｕｒａｍｅｔｈｒｉｎ）、［ｃ－４．４９］プロフルトリン（ｐｒｏｆｌｕｔｈｒｉｎ）、［ｃ－４．５０］フルブロシトリネート（ｆｌｕｂｒｏｃｙｔｈｒｉｎａｔｅ）、［ｃ－４．５１］ジメフルトリン（ｄｉｍｅｆｌｕｔｈｒｉｎ）、［ｃ－４．５２］ＤＤＴ（ｄｉｃｈｌｏｒｏ－ｄｉｐｈｅｎｙｌ－ｔｒｉｃｈｌｏｒｏｅｔｈａｎｅ）、［ｃ－４．５３］メトキシクロル（ｍｅｔｈｏｘｙｃｈｌｏｒ）、［ｃ－４．５４］フェノトリン（ｐｈｅｎｏｔｈｒｉｎ）、［ｃ－４．５５］フルバリネート（ｆｌｕｖａｌｉｎａｔｅ）等が挙げられる。 c-4: Sodium channel modulator As a sodium channel modulator, [c-4.1] acrinathrin, [c-4.2] allethrin [(1R) -isomer] (allethrin [(1R) -somer]), [C-4.3] bifenthrin, [c-4.4] bioallethrin, [c-4.5] bioallethrin S-cyclopentenyl isomer, [c- 4.6] bioresmethrin, [c-4.7] cycloprothrin, [c-4.8] cyfluthrin, [c-4. ] Beta-cyfluthrin, [c-4.10] cyhalothrin, [c-4.11] gamma-cyhalothrin, [c-4.12] lambda-cyhalothrin (lambda) -Cyhalothrin), [c-4.13] cypermethrin, [c-4.14] alpha-cypermethrin, [c-4.15] beta-cypermethrin. , [C-4.16] ceta-cypermethrin, [c-4.17] zeda-cypermethrin, [c-4.18] cypheno Trin [(1R) -trans-isomer] (cyphenothrin [(1R) -trans-somer]), [c-4.19] deltamethrin, [c-4.20] Empentrin [(EZ)-(1R) ) -Isomer] (empthrin [(EZ)-(1R) -isomer]), [c-4.21] esfenvalerate, [c-4.22] etofenprox, [c- 4.23] fenpropathrin, [c-4.24] fenvalerate, [c-4.25] flucytrinate, [c-4.26] flumethrin , [C-4.27] tau-fluvalinate, [c-4.28] halfenprox, [c-4.29] imiprothrin, [c-4.30]. ] Methothrin, [c-4.31] Metofluthrin, [c-4.32] Epsilon-Metofluthrin, [c-4.33] Monfluorothrin, [c] -4.34] epsilon-monfluorothrin, [c-4.35] permethrin, [c-4.36] phenothrin [(1R) -trans-a] Somer] (phenothrin [(1R) -trans-somer]), [c-4.37] prallethrin, [c-4.38] resmethrin, [c-4.39] cadethrin. , [C-4.40] silafluofen, [c-4.41] tefluthrin, [c-4.42] tetramethrin, [c-4.43] tetramethrin [(1R)- Isomer] (tetramethrin [(1R) -isomer]), [c-4.44] tralomethrin, [c-4.45] transfluthrin, [c-4.46] ZXI8. 901 (3- (4-bromophenoxy) phenyl] -cyanomethyl 4- (difluoromethoxy) -α- (1-methylethyl) benzeneacetate), [c-4.47] biopermethrin, furamethrin, c-4.48. (Furamethrin), [c-4.49] profluthrin, [c-4.50] flubrocytrinate, [c-4.51] dimefluthrin, [c-4.52]. DDT (dichloro-diphenyl-trichloroethane), [c-4.53] methoxychlor, [c-4. 4] phenothrin (phenothrin), and the like [c-4.55] fluvalinate (fluvalinate).
ｃ－５：ニコチン性アセチルコリン受容体（ｎＡＣｈＲ）競合的モジュレーター
　ニコチン性アセチルコリン受容体（ｎＡＣｈＲ）競合的モジュレーターとして、［ｃ－５．１］アセタミプリド（ａｃｅｔａｍｉｐｒｉｄ）、［ｃ－５．２］クロチアニジン（ｃｌｏｔｈｉａｎｉｄｉｎ）、［ｃ－５．３］ジノテフラン（ｄｉｎｏｔｅｆｕｒａｎ）、［ｃ－５．４］イミダクロプリド（ｉｍｉｄａｃｌｏｐｒｉｄ）、［ｃ－５．５］ニテンピラム（ｎｉｔｅｎｐｙｒａｍ）、［ｃ－５．６］チアクロプリド（ｔｈｉａｃｌｏｐｒｉｄ）、［ｃ－５．７］チアメトキサム（ｔｈｉａｍｅｔｈｏｘａｍ）、［ｃ－５．８］ニコチン（ｎｉｃｏｔｉｎｅ）、［ｃ－５．９］硫酸ニコチン（ｎｉｃｏｔｉｎｅ　ｓｕｌｆａｔｅ）、［ｃ－５．１０］スルホキサフロル（ｓｕｌｆｏｘａｆｌｏｒ）、［ｃ－５．１１］フルピラジフロン（ｆｌｕｐｙｒａｄｉｆｕｒｏｎｅ）、［ｃ－５．１２］トリフルメゾピリム（ｔｒｉｆｌｕｍｅｚｏｐｙｒｉｍ）等が挙げられる。 c-5: Competitive modulator of nicotinic acetylcholine receptor (nAChR) As a competitive modulator of nicotinic acetylcholine receptor (nAChR), [c-5.1] acetamiprid, [c-5.2] clothianidin (clothianidin). ), [C-5.3] dinotefuran, [c-5.4] imidacloprid, [c-5.5] nitenpyram, [c-5.6] thiacloprid, [C-5.7] thiamethoxam, [c-5.8] nicotine, [c-5.9] nicotine sulfate, [c-5.10] sulphate Kisafuroru (sulfoxaflor), [c-5.11] Furupirajifuron (flupyradifurone), and the like [c-5.12] triflupromazine meso pyridinium beam (triflumezopyrim).
ｃ－６：ニコチン性アセチルコリン受容体（ｎＡＣｈＲ）アロステリックモジュレーター
　ニコチン性アセチルコリン受容体（ｎＡＣｈＲ）アロステリックモジュレーターとして、［ｃ－６．１］スピノサド（ｓｐｉｎｏｓａｄ）、［ｃ－６．２］スピネトラム（ｓｐｉｎｅｔｏｒａｍ）等が挙げられる。 c-6: Nicotinic acetylcholine receptor (nAChR) allosteric modulator As a nicotinic acetylcholine receptor (nAChR) allosteric modulator, [c-6.1] spinosad, [c-6.2] spinetoram, etc. Is mentioned.
ｃ－７：グルタミン酸作動性塩素イオンチャネル（ＧｌｕＣｌ）アロステリックモジュレーター
　グルタミン酸作動性塩素イオンチャネル（ＧｌｕＣｌ）アロステリックモジュレーターとして、［ｃ－７．１］アバメクチン（ａｂａｍｅｃｔｉｎ）、［ｃ－７．２］エマメクチン安息香酸塩（ｅｍａｍｅｃｔｉｎ　ｂｅｎｚｏａｔｅ）、［ｃ－７．３］レピメクチン（ｌｅｐｉｍｅｃｔｉｎ）、［ｃ－７．４］ミルベメクチン（ｍｉｌｂｅｍｅｃｔｉｎ）等が挙げられる。 c-7: Glutamate agonist chloride ion channel (GluCl) allosteric modulator As a glutamate agonist chloride ion channel (GluCl) allosteric modulator, [c-7.1] abamectin, [c-7.2] emamectin benzoic acid Examples thereof include salt (emactin benzoate), [c-7.3] lepimectin, and [c-7.4] milbemectin.
ｃ－８：幼若ホルモン類似剤
　幼若ホルモン類似剤として、［ｃ－８．１］ヒドロプレン（ｈｙｄｒｏｐｒｅｎｅ）、［ｃ－８．２］キノプレン（ｋｉｎｏｐｒｅｎｅ）、［ｃ－８．３］メトプレン（ｍｅｔｈｏｐｒｅｎｅ）、［ｃ－８．４］フェノキシカルブ（ｆｅｎｏｘｙｃａｒｂ）、［ｃ－８．５］ピリプロキシフェン（ｐｙｒｉｐｒｏｘｙｆｅｎ）等が挙げられる。 c-8: Juvenile hormone analogs As juvenile hormone analogs, [c-8.1] hydroprene, [c-8.2] quinoprene, [c-8.3] methoprene (methoprene) ), [C-8.4] phenoxycarb, and [c-8.5] pyriproxyfen.
ｃ－９：非特異的（マルチサイト）阻害剤
　非特異的（マルチサイト）阻害剤として、［ｃ－９．１］臭化メチル（ｍｅｔｈｙｌ　ｂｒｏｍｉｄｅ）、［ｃ－９．２］クロルピクリン（ｃｈｌｏｒｏｐｉｃｒｉｎ）、［ｃ－９．３］クリオライト（ｃｒｙｏｌｉｔｅ）、［ｃ－９．４］フッ化スルフリル（ｓｕｌｆｕｒｙｌ　ｆｌｕｏｒｉｄｅ）、［ｃ－９．５］ホウ砂（ｂｏｒａｘ）、［ｃ－９．６］ホウ酸（ｂｏｒｉｃ　ａｃｉｄ）、［ｃ－９．７］オクタホウ酸ニナトリウム塩（ｄｉｓｏｄｉｕｍ　ｏｃｔａｂｏｒａｔｅ）、［ｃ－９．８］メタホウ酸ナトリウム塩（ｓｏｄｉｕｍ　ｍｅｔａｂｏｒａｔｅ）［ｃ－９．９］吐酒石（ｔａｒｔａｒ　ｅｍｅｔｉｃ）、［ｃ－９．１０］ダゾメット（ｄａｚｏｍｅｔ）、［ｃ－９．１１］メタム（ｍｅｔａｍ）、［ｃ－９．１２］カーバムナトリウム塩（ｍｅｔｈａｍ　ｓｏｄｉｕｍ）等が挙げられる。 c-9: Non-specific (multi-site) inhibitor As a non-specific (multi-site) inhibitor, [c-9.1] methyl bromide (meth-bromide), [c-9.2] chloropicrin , [C-9.3] cryolite, [c-9.4] sulfuryl fluoride, [c-9.5] borax, [c-9.6] boro Acid (boric acid), [c-9.7] octaborate disodium salt (disodium octoborate), [c-9.8] metaborate sodium salt (c-9.9) tartar (tartar) emetic), [c-9.10] dazomet, [c-9.11] metam (m etc., [c-9.12] carbam sodium salt, and the like.
ｃ－１０：弦音器官ＴＲＰＶチャネルモジュレーター
　弦音器官ＴＲＰＶチャネルモジュレーターとして、［ｃ－１０．１］ピメトロジン（ｐｙｍｅｔｒｏｚｉｎｅ）、［ｃ－１０．２］ピリフルキナゾン（ｐｙｒｉｆｌｕｑｕｉｎａｚｏｎ）等が挙げられる。 c-10: Chordonic organ TRPV channel modulator Examples of the chordal organ TRPV channel modulator include [c-10.1] pymetrozine and [c-10.2] pyrifluquinazon.
ｃ－１１：ダニ類成長阻害剤
　ダニ類成長阻害剤として、［ｃ－１１．１］クロフェンテジン（ｃｌｏｆｅｎｔｅｚｉｎｅ）、［ｃ－１１．２］ジフロビダジン（ｄｉｆｌｏｖｉｄａｚｉｎ）、［ｃ－１１．３］ヘキシチアゾクス（ｈｅｘｙｔｈｉａｚｏｘ）、［ｃ－１１．４］エトキサゾール（ｅｔｏｘａｚｏｌｅ）等が挙げられる。 c-11: Mite growth inhibitor As a mite growth inhibitor, [c-11.1] clofentezine, [c-11.2] diflovidazin, [c-11.3] hexithiazox (Hexythiazox), [c-11.4] ethoxazole and the like.
ｃ－１２：ミトコンドリアＡＴＰ合成酵素阻害剤
　ミトコンドリアＡＴＰ合成酵素阻害剤として、［ｃ－１２．１］ジアフェンチウロン（ｄｉａｆｅｎｔｈｉｕｒｏｎ）、［ｃ－１２．２］アゾシクロチン（ａｚｏｃｙｃｌｏｔｉｎ）、［ｃ－１２．３］シヘキサチン（ｃｙｈｅｘａｔｉｎ）、［ｃ－１２．４］フェンブタチンオキシド（ｆｅｎｂｕｔａｔｉｎ　ｏｘｉｄｅ）、「ｃ－１２．５」プロパルギット（ｐｒｏｐａｒｇｉｔｅ）、「ｃ－１２．６」テトラジホン（ｔｅｔｒａｄｉｆｏｎ）等が挙げられる。 c-12: Mitochondrial ATP synthase inhibitor As mitochondrial ATP synthase inhibitor, [c-12.1] diafenthiuron, [c-12.2] azocyclotin, [c-12. 3] Cyhexatin, [c-12.4] fenbutatin oxide, “c-12.5” propargite, “c-12.6” tetradiphone, etc. .
ｃ－１３：プロトン勾配を撹乱する酸化的リン酸化脱共役剤
　プロトン勾配を撹乱する酸化的リン酸化脱共役剤として、［ｃ－１３．１］クロルフェナピル（ｃｈｌｏｒｆｅｎａｐｙｌ）、［ｃ－１３．２］ＤＮＯＣ（ｄｉｎｉｔｒｏ－ｏｒｔｈｏ－ｃｒｅｓｏｌ）、［ｃ－１３．３］ビナパクリル（ｂｉｎａｐａｃｒｙｌ）、［ｃ－１３．４］スルフルラミド（ｓｕｌｆｌｕｒａｍｉｄ）等が挙げられる。 c-13: Oxidative phosphorylation uncoupling agent that perturbs proton gradient As oxidative phosphorylation uncoupling agent that perturbs proton gradient, [c-13.1] chlorfenapyl and [c-13.2] DNOC (Dinitro-ortho-cresol), [c-13.3] vinapacryl, [c-13.4] sulfluramide and the like.
ｃ－１４：ニコチン性アセチルコリン受容体（ｎＡＣｈＲ）チャネルブロッカー
　ニコチン性アセチルコリン受容体（ｎＡＣｈＲ）チャネルブロッカーとして、［ｃ－１４．１］ベンスルタップ（ｂｅｎｓｕｌｔａｐ）、［ｃ－１４．２］カルタップ塩酸塩（ｃａｒｔａｐ　ｈｙｄｒｏｃｈｌｏｒｉｄｅ）、［ｃ－１４．３］チオシクラム（ｔｈｉｏｃｙｃｌａｍ）、［ｃ－１４．４］モノスルタップ（ｍｏｎｏｓｕｌｔａｐ）等が挙げられる。 c-14: Nicotinic Acetylcholine Receptor (nAChR) Channel Blocker As a nicotinic acetylcholine receptor (nAChR) channel blocker, [c-14.1] bensultap, [c-14.2] cartap hydrochloride (cartap) hydrochloride), [c-14.3] thiocyclam, [c-14.4] monosultap and the like.
ｃ－１５：キチン生合成阻害剤タイプ０
　キチン生合成阻害剤タイプ０として、［ｃ－１５．１］ビストリフルロン（ｂｉｓｔｒｉｆｌｕｒｏｎ）、［ｃ－１５．２］クロルフルアズロン（ｃｈｌｏｒｆｌｕａｚｕｒｏｎ）、［ｃ－１５．３］ジフルベンズロン（ｄｉｆｌｕｂｅｎｚｕｒｏｎ）、［ｃ－１５．４］フルシクロクスロン（ｆｌｕｃｙｃｌｏｘｕｒｏｎ）、［ｃ－１５．５］フルフェノクスロン（ｆｌｕｆｅｎｏｘｕｒｏｎ）、［ｃ－１５．６］ヘキサフルムロン（ｈｅｘａｆｌｕｍｕｒｏｎ）、［ｃ－１５．７］ルフェヌロン（ｌｕｆｅｎｕｒｏｎ）、［ｃ－１５．８］ノバルロン（ｎｏｖａｌｕｒｏｎ）、［ｃ－１５．９］ノビフルムロン（ｎｏｖｉｆｌｕｍｕｒｏｎ）、［ｃ－１５．１０］テフルベンズロン（ｔｅｆｌｕｂｅｎｚｕｒｏｎ）、［ｃ－１５．１１］トリフルムロン（ｔｒｉｆｌｕｍｕｒｏｎ）等が挙げられる。 c-15: Chitin biosynthesis inhibitor type 0
As the chitin biosynthesis inhibitor type 0, [c-15.1] bistrifluron (bistrifluron), [c-15.2] chlorfluazuron (chlorfluazuron), [c-15.3] diflubenzuron, [C-15.4] flucycloxuron, [c-15.5] fluphenoxuron, [c-15.6] hexaflumuron, [c-15.7] Lufenuron, [c-15.8] novaluron, [c-15.9] noviflumuron, [c-15.10] teflubenzuron, [c-15.11]. Rifurumuron (triflumuron), and the like.
ｃ－１６：キチン生合成阻害剤タイプ１
　キチン生合成阻害剤タイプ１として、［ｃ－１６．１］ブプロフェジン（ｂｕｐｒｏｆｅｚｉｎ）等が挙げられる。 c-16: chitin biosynthesis inhibitor type 1
Examples of the chitin biosynthesis inhibitor type 1 include [c-16.1] buprofezin and the like.
ｃ－１７：ハエ目昆虫脱皮阻害剤
　ハエ目昆虫脱皮阻害剤として、［ｃ－１７．１］シロマジン（ｃｙｒｏｍａｚｉｎｅ）等が挙げられる。 c-17: Insect molting inhibitor for fly flies An insect molting inhibitor for fly flies includes [c-17.1] cyromazine and the like.
ｃ－１８：脱皮ホルモン（エクダイソン）受容体アゴニスト
　脱皮ホルモン（エクダイソン）受容体アゴニストとして、［ｃ－１８．１］クロマフェノジド（ｃｈｒｏｍａｆｅｎｏｚｉｄｅ）、［ｃ－１８．２］ハロフェノジド（ｈａｌｏｆｅｎｏｚｉｄｅ）、［ｃ－１８．３］メトキシフェノジド（ｍｅｔｈｏｘｙｆｅｎｏｚｉｄｅ）、［ｃ－１８．４］テブフェノジド（ｔｅｂｕｆｅｎｏｚｉｄｅ）等が挙げられる。 c-18: Molting hormone (ecdysone) receptor agonist As a molting hormone (ecdysone) receptor agonist, [c-18.1] chromafenozide, [c-18.2] halofenozide, [c-18] .3] methoxyphenozide, [c-18.4] tebufenozide and the like.
ｃ－１９：オクトパミン受容体アゴニスト
　オクトパミン受容体アゴニストとして、［ｃ－１９．１］アミトラズ（ａｍｉｔｒａｚ）等が挙げられる。 c-19: Octopamine receptor agonist Examples of the octopamine receptor agonist include [c-19.1] amitraz.
ｃ－２０：ミトコンドリア電子伝達系複合体ＩＩＩ阻害剤
　ミトコンドリア電子伝達系複合体ＩＩＩ阻害剤として、［ｃ－２０．１］ヒドラメチルノン（ｈｙｄｒａｍｅｔｈｙｌｎｏｎ）、［ｃ－２０．２］アセキノシル（ａｃｅｑｕｉｎｏｃｙｌ）、［ｃ－２０．３］フルアクリピリム（ｆｌｕａｃｒｙｐｙｒｉｍ）、［ｃ－２０．４］ビフェナゼート（ｂｉｆｅｎａｚａｔｅ）等が挙げられる。 c-20: Mitochondrial electron transfer complex III inhibitor As a mitochondrial electron transfer complex III inhibitor, [c-20.1] hydramethylnon, [c-20.2] acequinocyl, Examples include [c-20.3] fluacrypyrim and [c-20.4] bifenazate.
ｃ－２１：ミトコンドリア電子伝達系複合体Ｉ阻害剤（ＭＥＴＩ）
　ミトコンドリア電子伝達系複合体Ｉ阻害剤（ＭＥＴＩ）として、［ｃ－２１．１］フェナザキン（ｆｅｎａｚａｑｕｉｎ）、［ｃ－２１．２］フェンピロキシメート（ｆｅｎｐｙｒｏｘｉｍａｔｅ）、［ｃ－２１．３］ピリダベン（ｐｙｒｉｄａｂｅｎ）、［ｃ－２１．４］ピリミジフェン（ｐｙｌｉｍｉｄｉｆｅｎ）、［ｃ－２１．５］テブフェンピラド（ｔｅｂｕｆｅｎｐｙｒａｄ）、［ｃ－２１．６］トルフェンピラド（ｔｏｌｆｅｎｐｙｒａｄ）、［ｃ－２１．７］ロテノン（ｒｏｔｅｎｏｎｅ）等が挙げられる。 c-21: Mitochondrial electron transport complex I inhibitor (METI)
As a mitochondrial electron transport complex I inhibitor (METI), [c-21.1] fenazaquin, [c-21.2] fenpyroximate, [c-21.3] pyridaben, [C-21.4] pyrimidifen, [c-21.5] tebufenpyrad, [c-21.6] tolfenpyrad, [c-21.7] rotenone and the like. To be
ｃ－２２：電位依存性ナトリウムチャネルブロッカー
　電位依存性ナトリウムチャネルブロッカーとして、［ｃ－２２．１］インドキサカルブ（ｉｎｄｏｘａｃａｒｂ）、［ｃ－２２．２］メタフルミゾン（ｍｅｔａｆｌｕｍｉｚｏｎｅ）等が挙げられる。 c-22: Voltage-gated sodium channel blocker Examples of the voltage-gated sodium channel blocker include [c-22.1] indoxacarb and [c-22.2] metaflumizone.
ｃ－２３：アセチルＣｏＡカルボキシラーゼ阻害剤
　アセチルＣｏＡカルボキシラーゼ阻害剤として、［ｃ－２３．１］スピロジクロフェン（ｓｐｉｒｏｄｉｃｌｏｆｅｎ）、［ｃ－２３．２］スピロメシフェン（ｓｐｉｒｏｍｅｓｉｆｅｎ）、［ｃ－２３．３］スピロテトラマト（ｓｐｉｒｏｔｅｔｒａｍａｔ）等が挙げられる。 c-23: Acetyl CoA carboxylase inhibitor As an acetyl CoA carboxylase inhibitor, [c-23.1] spirodiclofen, [c-23.2] spiromesifen, [c-23.3]. ] Spirotetramat etc. are mentioned.
ｃ－２４：ミトコンドリア電子伝達系複合体ＩＶ阻害剤
　ミトコンドリア電子伝達系複合体ＩＶ阻害剤として、［ｃ－２４．１］リン化アルミニウム（ａｌｕｍｉｎｕｍ　ｐｈｏｓｐｈｉｄｅ）、［ｃ－２４．２］リン化カルシウム（ｃａｌｃｉｕｍ　ｐｈｏｓｐｈｉｄｅ）、［ｃ－２４．３］リン化水素（ｐｈｏｓｐｈｉｎｅ）、［ｃ－２４．４］リン化亜鉛（ｚｉｎｃ　ｐｈｏｓｐｈｉｄｅ）、［ｃ－２４．５］シアン化カルシウム（ｃａｌｃｉｕｍ　ｃｙａｎｉｄｅ）、［ｃ－２４．６］シアン化ナトリウム（ｓｏｄｉｕｍ　ｃｙａｎｉｄｅ）、［ｃ－２４．７］シアン化カリウム（ｐｏｔａｓｓｉｕｍ　ｃｙａｎｉｄｅ）等が挙げられる。 c-24: Mitochondrial electron transport complex IV inhibitor As a mitochondrial electron transport complex IV inhibitor, [c-24.1] aluminum phosphide, [c-24.2] calcium phosphide ( calcium phosphide, [c-24.3] phosphine, [c-24.4] zinc phosphide, [c-24.5] calcium cyanide, [c Examples include −24.6] sodium cyanide and [c-24.7] potassium cyanide.
ｃ－２５：ミトコンドリア電子伝達系複合体ＩＩ阻害剤
　ミトコンドリア電子伝達系複合体ＩＩ阻害剤として、［ｃ－２５．１］シエノピラフェン（ｃｙｅｎｏｐｙｒａｆｅｎ）、［ｃ－２５．２］シフルメトフェン（ｃｙｆｌｕｍｅｔｏｆｅｎ）、［ｃ－２５．３］ピフルブミド（ｐｙｆｌｕｂｕｍｉｄｅ）等が挙げられる。 c-25: Mitochondrial electron transport complex II inhibitor [c-25.1] cyenopyrafen, [c-25.2] cyflumethofen, [c-25.1] as mitochondrial electron transport complex II inhibitor -25.3] Pyflubumide and the like.
ｃ－２６：リアノジン受容体モジュレーター
　リアノジン受容体モジュレーターとして、［ｃ－２６．１］クロラントラニリプロール（ｃｈｌｏｒａｎｔｒａｎｉｌｉｐｒｏｌｅ）、［ｃ－２６．２］シアントラニリプロール（ｃｙａｎｔｒａｎｉｌｉｐｒｏｌｅ）、［ｃ－２６．３］フルベンジアミド（ｆｌｕｂｅｎｄｉａｍｉｄｅ）等が挙げられる。 c-26: ryanodine receptor modulator As a ryanodine receptor modulator, [c-26.1] chlorantraniliprole (chlanantraniprole), [c-26.2] cyantraniliprole, [c-26. 3] Flubendiamide and the like can be mentioned.
ｃ－２７：標的部位未特定の弦音器官モジュレーター
　標的部位未特定の弦音器官モジュレーターとして、［ｃ－２７．１］フロニカミド（ｆｌｏｎｉｃａｍｉｄ）等が挙げられる。 c-27: Modulator of string sound organ with unspecified target site [c-27.1] flonicamid etc. are mentioned as a modulator of string sound organ with unspecified target site.
ｃ－２８：その他の殺虫剤
　その他の殺虫剤として、［ｃ－２８．１］アザジラクチン（ａｚａｄｉｒａｃｈｔｉｎ）、［ｃ－２８．２］ベンゾキシメート（ｂｅｎｚｏｘｉｍａｔｅ）、［ｃ－２８．３］フェニソブロモレート（ｐｈｅｎｉｓｏｂｒｏｍｏｌａｔｅ）、［ｃ－２８．４］キノメチオナート（ｃｈｉｎｏｍｅｔｈｉｏｎａｔ）、［ｃ－２８．５］ジコホル（ｄｉｃｏｆｏｌ）、［ｃ－２８．６］ピリダリル（ｐｙｒｉｄａｌｙｌ）、［ｃ－２８．７］ブロモプロピレート（ｂｒｏｍｏｐｒｏｐｙｌａｔｅ）、［ｃ－２８．８］トリアザメート（ｔｒｉａｚａｍａｔｅ）、［ｃ－２８．９］ジシクラニル（ｄｉｃｙｃｌａｎｉｌ）、［ｃ－２８．１０］ジノブトン（ｄｉｎｏｂｕｔｏｎ）、［ｃ－２８．１１］ジノカップ（ｄｉｎｏｃａｐ）、［ｃ－２８．１２］シアン化水素（ｈｙｄｒｏｇｅｎ　ｃｙａｎｉｄｅ）、［ｃ－２８．１３］ヨウ化メチル（ｍｅｔｈｙｌ　ｉｏｄｉｄｅ）、［ｃ－２８．１４］カランジン（ｋａｒａｎｊｉｎ）、［ｃ－２８．１５］塩化水銀（ｍｅｒｃｕｒｙ　ｃｈｌｏｒｉｄｅ）、［ｃ－２８．１６］メチルイソチオシアネート（ｍｅｔｈｙｌ　ｉｓｏｔｈｉｏｃｙａｎａｔｅ）、［ｃ－２８．１７］ペンタクロロフェノール（ｐｅｎｔａｃｈｌｏｒｏｐｈｅｎｏｌ）、［ｃ－２８．１８］ホスフィン（ｐｈｏｓｐｈｉｎｅ）、［ｃ－２８．１９］ピペロニル　ブトキシド（ｐｉｐｅｒｏｎｙｌ　ｂｕｔｏｘｉｄｅ）、［ｃ－２８．２０］ポリナクチン複合体（ｐｏｌｙｎａｃｔｉｎｓ）、［ｃ－２８．２１］サバディラ（ｓａｂａｄｉｌｌａ）、［ｃ－２８．２２］スルコフロン塩（スルコフロン－ナトリウム（ｓｕｌｃｏｆｕｒｏｎ－ｓｏｄｉｕｍ））、［ｃ－２８．２３］トリブホス（ｔｒｉｂｕｆｏｓ）、［ｃ－２８．２４］アルドリン（ａｌｄｒｉｎ）、［ｃ－２８．２５］アミジチオオン（ａｍｉｄｉｔｈｉｏｎ）、［ｃ－２８．２６］アミドチオエート（ａｍｉｄｏｔｈｉｏａｔｅ）、［ｃ－２８．２７］アミノカルブ（ａｍｉｎｏｃａｒｂ）、［ｃ－２８．２８］アミトン（ａｍｉｔｏｎ）、［ｃ－２８．２９］アラマイト（ａｒａｍｉｔｅ）、［ｃ－２８．３０］アチダチオン（ａｔｈｉｄａｔｈｉｏｎ）、［ｃ－２８．３１］アゾトエート（ａｚｏｔｈｏａｔｅ）、［ｃ－２８．３２］ポリスルフィドバリウム（ｂａｒｉｕｍ　ｐｏｌｙｓｕｌｐｈｉｄｅ）、［ｃ－２８．３３］ベンクロチアズ（ｂｅｎｃｌｏｔｈｉａｚ）、［ｃ－２８．３４］５－（１，３－ベンゾジオキソール－５－イル）－３－ヘキシルシクロヘキサ－２－エノン（５－（１，３－ｂｅｎｚｏｄｉｏｘｏｌｅ－５－ｙｌ）－３－ｈｅｘｙｌｃｙｃｌｏｈｅｘａ－２－ｅｎｏｎｅ）、［ｃ－２８．３５］１，１－ビス（４－クロロフェニル）－２－エトキシエタノール（１，１－ｂｉｓ（４－ｃｈｌｏｒｏｐｈｅｎｙｌ）－２－ｅｔｈｏｘｙｅｔｈａｎｏｌ）、［ｃ－２８．３６］ブトネート（ｂｕｔｏｎａｔｅ）、［ｃ－２８．３７］ブトピロノキシル（ｂｕｔｏｐｙｒｏｎｏｘｙｌ）、［ｃ－２８．３８］２－（２－ブトキシエトキシ）エチル　チオシアナート（２－（２－ｂｕｔｏｘｙｅｔｈｏｘｙ）ｅｔｈｙｌ　ｔｈｉｏｃｙａｎａｔｅ）、［ｃ－２８．３９］カンフェクロル（ｃａｍｐｈｅｃｈｌｏｒ）、［ｃ－２８．４０］クロルベンシド（ｃｈｌｏｒｂｅｎｓｉｄｅ）、［ｃ－２８．４１］クロルデコン（ｃｈｌｏｒｄｅｃｏｎｅ）、［ｃ－２８．４２］クロルジメホルム（ｃｈｌｏｒｄｉｍｅｆｏｒｍ）、［ｃ－２８．４３］クロルフェネトール（ｃｈｌｏｒｆｅｎｅｔｈｏｌ）、［ｃ－２８．４４］クロルフェンソン（ｃｈｌｏｒｆｅｎｓｏｎ）、［ｃ－２８．４５］フルアズロン（ｆｌｕａｚｕｒｏｎ）、［ｃ－２８．４６］メタアルデヒド（ｍｅｔａｌｄｅｈｙｄｅ）、［ｃ－２８．４７］ビアラホス（ｂｉａｌａｐｈｏｓ）、［ｃ－２８．４８］塩酸レバミゾール（ｌｅｖａｍｉｓｏｌ）、［ｃ－２８．４９］アミドフルメト（ａｍｉｄｏｆｌｕｍｅｔ）、［ｃ－２８．５０］ピラフルプロール（ｐｙｒａｆｌｕｐｒｏｌｅ）、［ｃ－２８．５１］ピリプロール（ｐｙｒｉｐｒｏｌｅ）、［ｃ－２８．５２］トラロピリル（ｔｒａｌｏｐｙｒｉｌ）、［ｃ－２８．５３］フルピラゾフォス（ｆｌｕｐｙｒａｚｏｆｏｓ）、［ｃ－２８．５４］ジオフェノラン（ｄｉｏｆｅｎｏｌａｎ）、［ｃ－２８．５５］クロルベンジレート（ｃｈｌｏｒｏｂｅｎｚｉｌａｔｅ）、［ｃ－２８．５６］フルフェンジン（ｆｌｕｆｅｎｚｉｎｅ）、［ｃ－２８．５７］ベンゾメート（ｂｅｎｚｏｍａｔｅ）、［ｃ－２８．５８］フルフェネリム（ｆｌｕｆｅｎｅｒｉｍ）、［ｃ－２８．５９］アルベンダゾール（ａｌｂｅｎｄａｚｏｌｅ）、［ｃ－２８．６０］オキシベンダゾール（ｏｘｉｂｅｎｄａｚｏｌｅ）、［ｃ－２８．６１］フェンベンダゾール（ｆｅｎｂｅｎｄａｚｏｌｅ）、［ｃ－２８．６２］メタム・ナトリウム（ｍｅｔａｍ－ｓｏｄｉｕｍ）、［ｃ－２８．６３］１，３－ジクロロプロペン（１，３－ｄｉｃｈｌｏｒｏｐｒｏｐｅｎｅ）、［ｃ－２８．６４］フロメトキン（ｆｌｏｍｅｔｏｑｕｉｎ）、［ｃ－２８．６５］シクラニリプロール（ｃｙｃｌａｎｉｌｉｐｒｏｌｅ）、［ｃ－２８．６６］テトラニリプロール（ｔｅｔｒａｎｉｌｉｐｒｏｌｅ）、［ｃ－２８．６７］ブロフラニリド（ｂｒｏｆｌａｎｉｌｉｄｅ）、［ｃ－２８．６８］ジクロロメゾチアズ（ｄｉｃｌｏｒｏｍｅｚｏｔｉａｚ）、［ｃ－２８．６９］エチレンジブロマイド（ｅｔｈｙｌｅｎｅ　ｄｉｂｒｏｍｉｄｅ）、［ｃ－２８．７０］アクリロニトリル（ａｃｒｙｌｏｎｉｔｒｉｌｅ）、［ｃ－２８．７１］ビス（２－クロロエチル）エーテル（ｂｉｓ（２－ｃｈｌｏｒｏｅｔｈｙｌ）ｅｔｈｅｒ）、［ｃ－２８．７２］１－ブロモ－２－クロロエタン（１－ｂｒｏｍｏ－２－ｃｈｌｏｒｏｅｔｈａｎｅ）、［ｃ－２８．７３］３－ブロモ－１－クロロプロパ－１－エン（３－ｂｒｏｍｏ－１－ｃｈｌｏｒｏｐｒｏｐ－１－ｅｎｅ）、［ｃ－２８．７４］ブロモシクレン（ｂｒｏｍｏｃｙｃｌｅｎ）、［ｃ－２８．７５］二硫化炭素（ｃａｒｂｏｎ　ｄｉｓｕｌｆｉｄｅ）、［ｃ－２８．７６］四塩化炭素（ｔｅｔｒａｃｈｌｏｒｏｍｅｔｈａｎｅ）、［ｃ－２８．７７］ネマデクチン（ｎｅｍａｄｅｃｔｉｎ）、［ｃ－２８．７８］シミアゾール（ｃｙｍｉａｚｏｌｅ）［ｃ－２８．７９］カルシウム　ポリスルフィド（ｃａｌｃｉｕｍ　ｐｏｌｙｓｕｌｆｉｄｅ）、［ｃ－２８．８０］サイトカイニン（ｃｙｔｏｋｉｎｉｎ）、［ｃ－２８．８１］２－（オクチルチオ）エタノール、［ｃ－２８．８２］オレイン酸カリウム（ｐｏｔａｓｓｉｕｍ　ｏｌｅａｔｅ）、［ｃ－２８．８３］オレイン酸ナトリウム（ｓｏｄｉｕｍ　ｏｌｅａｔｅ）、［ｃ－２８．８４］マシン油（ｍａｃｈｉｎｅ　ｏｉｌ）、［ｃ－２８．８５］タール油（ｔａｒ　ｏｉｌ）、［ｃ－２８．８６］アナバシン（ａｎａｂａｓｉｎｅ）、［ｃ－２８．８７］酒石酸モランテル（ｍｏｒａｎｔｅｌ　ｔａｒｔｒａｔｅ）、［ｃ－２８．８８］除虫菊（ｐｙｒｅｔｈｒｕｍ）、［ｃ－２８．８９］ナタネ油（ｒａｐｅ　ｓｅｅｄ　ｏｉｌ）、［ｃ－２８．９０］ダイズレチシン（ｓｏｙｂｅａｎ　ｌｅｃｉｔｈｉｎ）、［ｃ－２８．９１］デンプン（ｓｔａｒｃｈ）、［ｃ－２８．９２］ヒドロキシプロピルデンプン（ｈｙｄｒｏｘｙｐｒｏｐｙｌｓｔａｒｃｈ）、［ｃ－２８．９３］脂肪酸グリセリド（ｄｅｃａｎｏｙｌｏｃｔａｎｏｙｌｇｌｙｃｅｒｏｌ）、［ｃ－２８．９４］プロピレングリコールモノ脂肪酸エステル（ｐｒｏｐｙｌｅｎｅ　ｇｌｙｃｏｌ　ｆａｔｔｙ　ａｃｉｄ　ｅｓｔｅｒ）、［ｃ－２８．９５］ケイソウ土（ｄｉａｔｏｍｉｔｅ）、［ｃ－２８．９６］アフォキソラネル（ａｆｏｘｏｌａｎｅｒ）、［ｃ－２８．９７］フルアザインドリジン（ｆｌｕａｚａｉｎｄｏｌｉｚｉｎｅ）、［ｃ－２８．９８］アフィドピロペン（ａｆｉｄｏｐｙｒｏｐｅｎ）、［ｃ－２８．９９］シハロジアミド（ｃｙｈａｌｏｄｉａｍｉｄｅ）、［ｃ－２８．１００］チオキサザフェン（ｔｉｏｘａｚａｆｅｎ）、［ｃ－２８．１０１］フルヘキサフォン（ｆｌｕｈｅｘａｆｏｎ）、［ｃ－２８．１０２］フルララネル（ｆｌｕｒａｌａｎｅｒ）、［ｃ－２８．１０３］フルキサメタミド（ｆｌｕｘａｍｅｔａｍｉｄｅ）、［ｃ－２８．１０４］テトラクロラントラニリプロール（ｔｅｔｒａｃｈｌｏｒａｎｔｒａｎｉｌｉｐｒｏｌｅ）、［ｃ－２８．１０５］サロラネル（ｓａｒｏｌａｎｅｒ）、［ｃ－２８．１０６］ロチラネル（ｌｏｔｉｌａｎｅｒ）、［ｃ－２８．１０７］シクロキサプリド（ｃｙｃｌｏｘａｐｒｉｄ）、［ｃ－２８．１０８］フルエンスルホン（ｆｌｕｅｎｓｕｌｆｏｎｅ）、［ｃ－２８．１０９］ＴＰＩＣ（ｔｒｉｐｒｏｐｙｌ　ｉｓｏｃｙａｎｕｒａｔｅ）、［ｃ－２８．１１０］Ｄ－Ｄ（１，３－Ｄｉｃｈｌｏｒｏｐｒｏｐｅｎｅ）、［ｃ－２８．１１１］ペルオキソカルボナート（ｐｅｒｏｘｏｃａｒｂｏｎａｔｅ）、［ｃ－２８．１１２］ＭＢ－５９９（ｖｅｒｂｕｔｉｎ）、［ｃ－２８．１１３］ビス（２，３，３，３－テトラクロロプロピル）エーテル（ｂｉｓ（２，３，３，３－ｔｅｔｒａｃｈｌｏｒｏｐｒｏｐｙｌ）ｅｔｈｅｒ）、［ｃ－２８．１１４］ＤＣＩＰ（ｂｉｓ（２－ｃｈｌｏｒｏ－１－ｍｅｔｈｙｌｅｔｈｙｌ）ｅｔｈｅｒ）、［ｃ－２８．１１５］ＥＮＴ－８１８４（Ｎ－（２－Ｅｔｈｙｌｈｅｘｙｌ）ｂｉｃｙｃｌｏ［２．２．１］ｈｅｐｔ－５－ｅｎｅ－２，３－ｄｉｃａｒｂｏｘｉｍｉｄｅ）、［ｃ－２８．１１６］Ｂａｙｅｒ　２２４０８（Ｏ，Ｏ－ｄｉｅｔｈｙｌ　Ｏ－ｎａｐｈｔｈａｌｉｍｉｄｏ　ｐｈｏｓｐｈｏｒｏｔｈｉｏａｔｅ）、［ｃ－２８．１１７］Ｂａｙｅｒ　３２３９４（ｔｒｉｓ（１－ｄｏｄｅｃｙｌ－３－ｍｅｔｈｙｌ－２－ｐｈｅｎｙｌｂｅｎｚｉｍｉｄａｚｏｌｉｕｍ）ｈｅｘａｃｙａｎｏｆｅｒｒａｔｅ）、 c-28: Other insecticides [c-28.1] azadirachtin, [c-28.2] benzoximate, [c-28.3] phenisobromo as other insecticides. Phenisobromolate, [c-28.4] quinomethionate, [c-28.5] dicofol, [c-28.6] pyridalyl, [c-28.7] bromopropyiate. Brompropylate, [c-28.8] triazamate, [c-28.9] dicyclanil, [c-28.1] dinobuton, [c-28.11] zinocup ( din ocap), [c-28.12] hydrogen cyanide, [c-28.13] methyl iodide, [c-28.14] carangin, [c-28.15]. Mercury chloride, [c-28.16] methyl isothiocyanate, [c-28.17] pentachlorophenol, [c-28.18] phosphine, [c] -28.19] piperonyl butoxide, [c-28.20] polynactin complex, [c-28.21] sabadilla [C-28.22] sulcofuron salt (sulcofuron-sodium), [c-28.23] tribufos, [c-28.24] aldrin, [c-28.25]. ] Amidithione, [c-28.26] amidothioate, [c-28.27] aminocarb, [c-28.28] amiton, [c-28.29]. ] Aramite, [c-28.30] athidathion, [c-28.31] azothoate, [c-28.32] barium polysulfide, [c- 8.33] benclothiaz, [c-28.34] 5- (1,3-benzodioxol-5-yl) -3-hexylcyclohex-2-enone (5- (1,3- benzdioxole-5-yl) -3-hexylcyclohexa-2-enone), [c-28.35] 1,1-bis (4-chlorophenyl) -2-ethoxyethanol (1,1-bis (4-chlorophenyl)- 2-ethoxyethanol, [c-28.36] butonate, [c-28.37] butopyronoxyl, [c-28.38] 2- (2-butoxyethoxy) ethyl thiocyanate (2- ( 2-butoxyethoxy) ethyl thiocyan ate), [c-28.39] camphechlor, [c-28.40] chlorbenside, [c-28.41] chlordecone, [c-28.42] chlordimeform. , [C-28.43] chlorphenethol, [c-28.44] chlorfenson, [c-28.45] fluazuron, [c-28.46] methaaldehyde. (Metaldehyde), [c-28.47] bialaphos, [c-28.48] levamisole hydrochloride (levamisol), [c-28.49] amidoflumet (amidoflumet) , [C-28.50] pyrafluprole, [c-28.51] pyriprole, [c-28.52] tralopyril, [c-28.53] flupyrazofos , [C-28.54] diofenolan, [c-28.55] chlorobenzilate, [c-28.56] flufenzine, [c-28.57] benzomate. , [C-28.58] flufenerim, [c-28.59] albendazole, [c-28.60] oxybendazole. , [C-28.61] fenbendazole, [c-28.62] metam-sodium, [c-28.63] 1,3-dichloropropene (1,3-dichloropropene) ), [C-28.64] fromtoquin, [c-28.65] cyclaniliprole, [c-28.66] tetraniliprole, [c-28.67]. Broflanilide, [c-28.68] dichloromezotiaz, [c-28.69] ethylene dibromide, [c-28.70] acrylonitrile. acrylonitrile), [c-28.71] bis (2-chloroethyl) ether (bis (2-chloroethyl) ether), [c-28.72] 1-bromo-2-chloroethane (1-bromo-2-chloroethane) , [C-28.73] 3-bromo-1-chloroprop-1-ene (3-bromo-1-chloroprop-1-ene), [c-28.74] bromocyclen, [c-28. 75] carbon disulfide, [c-28.76] carbon tetrachloride, [c-28.77] nemadectin, [c-28.78] cymiazole [c- 28.79] Calcium polysulfide, [c-28.80] cytokinin, [c-28.81] 2- (octylthio) ethanol, [c-28.82] potassium oleate, [c] -28.83] Sodium oleate, [c-28.84] machine oil, [c-28.85] tar oil, [c-28.86] anabasine ( anabasine), [c-28.87] morantel tartrate, [c-28.88] pyrethrum, [c-28.89] rape seed oil, [c-28.90]. ] Soybean lettuce Soybean lecithin, [c-28.91] starch (starch), [c-28.92] hydroxypropyl starch, [c-28.93] fatty acid glyceride (decanoyloctanoylglycerol), [c-28. 94] Propylene glycol monofatty acid ester, [c-28.95] diatomite, [c-28.96] afoxolaner, [c-28.97] fluazaind. Lysine, [c-28.98] afidopyropene, [c-28.99] cyhalodiamide cyhalodiamide), [c-28.100] thioxazaphen, [c-28.101] fluhexafone, [c-28.102] fluralaner, [c-28.103] fluxamethamid (c-28.101). Fluxametamide), [c-28.104] tetrachlorantraniliprole, [c-28.105] sarolaner, [c-28.106] lotilaner, [c-28.107]. ] Cycloxapride, [c-28.108] fluensulfone, [c-28.109] TPIC (triprop) yl isocyanurate), [c-28.110] DD (1,3-Dichloropropene), [c-28.111] peroxocarbonate, [c-28.112] MB-599 (verbutin), [C-28.113] bis (2,3,3,3-tetrachloropropyl) ether (bis (2,3,3,3-tetrachloropropoxyl) ether), [c-28.114] DCIP (bis (2 -Chloro-1-methylethyl) ether), [c-28.115] ENT-8184 (N- (2-Ethylhexyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), c-28.116] Baye r 22408 (O, O-diethyl O-naphthalimido phosphorothioate), [c-28.117] Bayer 32394 (tris (1-dodecyl-3-methyl-2-phenylbenzimidozolinium) terephthalate).
［ｃ－２８．１１８］式（ｓ３４）
Figure JPOXMLDOC01-appb-C000097
で表される化合物（国際公開第１０／０５１９２６号参照）、 [C-28.118] Expression (s34)
Figure JPOXMLDOC01-appb-C000097
(See WO10 / 051926),
［ｃ－２８．１１９］式（ｓ３５）
Figure JPOXMLDOC01-appb-C000098
で表される化合物（国際公開第１３／１１５３９１号参照）、 [C-28.119] Expression (s35)
Figure JPOXMLDOC01-appb-C000098
A compound represented by (see International Publication No. 13/115391),
［ｃ－２８．１２０］式（ｓ３６）
Figure JPOXMLDOC01-appb-C000099
で表される化合物（国際公開第１２／０２９６７２号参照）、 [C-28.120] Expression (s36)
Figure JPOXMLDOC01-appb-C000099
A compound represented by the formula (see International Publication No. 12/029672):
［ｃ－２８．１２１］式（ｓ３７）
Figure JPOXMLDOC01-appb-C000100
で表される化合物（国際公開第０６／０５６１０８号参照）、 [C-28.121] Expression (s37)
Figure JPOXMLDOC01-appb-C000100
(See WO 06/056108),
［ｃ－２８．１２２］式（ｓ３８）
Figure JPOXMLDOC01-appb-C000101
で表される化合物（国際公開第１４／０５３４５０号、国際公開第１５／１４４６８３号参照）、 [C-28.122] Expression (s38)
Figure JPOXMLDOC01-appb-C000101
A compound represented by (see International Publication No. 14/053450, International Publication No. 15/144683),
［ｃ－２８．１２３］式（ｓ３９）
Figure JPOXMLDOC01-appb-C000102
で表される化合物（国際公開第１４／０５３４５０号、国際公開第１５／１４４６８３号参照）、 [C-28.123] Expression (s39)
Figure JPOXMLDOC01-appb-C000102
A compound represented by (see International Publication No. 14/053450, International Publication No. 15/144683),
［ｃ－２８．１２４］式（ｓ４０）
Figure JPOXMLDOC01-appb-C000103
で表される化合物（国際公開第１４／０５３４５０号、国際公開第１５／１４４６８３号参照）、 [C-28.124] Expression (s40)
Figure JPOXMLDOC01-appb-C000103
A compound represented by (see International Publication No. 14/053450, International Publication No. 15/144683),
［ｃ－２８．１２５］式（ｓ４１）
Figure JPOXMLDOC01-appb-C000104
［式中、ｍ６は、０～２の整数を表す。］で表される化合物（国際公開第１０／１２９４９７号参照）、 [C-28.125] Expression (s41)
Figure JPOXMLDOC01-appb-C000104
[In the formula, m6 represents an integer of 0 to 2. (See WO 10/129497),
［ｃ－２８．１２６］式（ｓ４２）
Figure JPOXMLDOC01-appb-C000105
［式中、ｍ７は、０～２の整数を表す。］で表される化合物（国際公開第１１／１５２３２０号参照）、 [C-28.126] Expression (s42)
Figure JPOXMLDOC01-appb-C000105
[In the formula, m7 represents an integer of 0 to 2. (See WO 11/152320),
［ｃ－２８．１２７］式（ｓ４３）
Figure JPOXMLDOC01-appb-C000106
［式中、ｍ８は、０～２の整数を表す。］で表される化合物（特開２０１５―１６０８１３号公報参照）、 [C-28.127] Expression (s43)
Figure JPOXMLDOC01-appb-C000106
[In the formula, m8 represents an integer of 0 to 2. ] (See JP-A-2015-160813),
［ｃ－２８．１２８］式（ｓ４４）
Figure JPOXMLDOC01-appb-C000107
［式中、Ａ５２は、水素原子、またはフッ素原子を表す。］で表される化合物（国際公開第１１／１３４９６４号、国際公開第１４／００５９８２号参照）、 [C-28.128] Expression (s44)
Figure JPOXMLDOC01-appb-C000107
[Wherein, A52 represents a hydrogen atom or a fluorine atom. (See WO 11/134964, WO 14/005982),
［ｃ－２８．１２９］式（ｓ４５）
Figure JPOXMLDOC01-appb-C000108
［式中、ｍ９は、０～２の整数を表し、Ａ５３は、フッ素原子、または塩素原子を表す。］で表される化合物（国際公開第１５／０２５８２６号参照）、
［ｃ－２８．１３０］式（ｓ４６）
Figure JPOXMLDOC01-appb-C000109
［式中、Ｖ３は、窒素原子、炭素原子、またはＣ－Ｆを表し、Ｖ４およびＶ５は、それぞれ独立していて、窒素原子、または炭素原子を表す。］で表される化合物（国際公開第１１／１３４９６４号、国際公開第１４／００５９８２号参照）、 [C-28.129] Expression (s45)
Figure JPOXMLDOC01-appb-C000108
[In the formula, m9 represents an integer of 0 to 2, and A53 represents a fluorine atom or a chlorine atom. (See WO 15/025826),
[C-28.130] Expression (s46)
Figure JPOXMLDOC01-appb-C000109
[In the formula, V3 represents a nitrogen atom, a carbon atom, or CF, and V4 and V5 each independently represent a nitrogen atom or a carbon atom. (See WO 11/134964, WO 14/005982),
［ｃ－２８．１３１］式（ｓ４７）
Figure JPOXMLDOC01-appb-C000110
［式中、Ａ５４は、水素原子、メチル基、メトキシ基、またはエトキシ基を表し、Ａ５５は、塩素原子、またはメチル基を表し、Ａ５６は、メチル基、またはエチル基を表す。］で表される化合物（国際公開第０９／０４９８５１号参照）、 [C-28.131] Expression (s47)
Figure JPOXMLDOC01-appb-C000110
[Wherein, A54 represents a hydrogen atom, a methyl group, a methoxy group, or an ethoxy group, A55 represents a chlorine atom or a methyl group, and A56 represents a methyl group or an ethyl group. (See WO09 / 049851),
［ｃ－２８．１３２］式（ｓ４８）
Figure JPOXMLDOC01-appb-C000111
［式中、Ａ５７は、水素原子、フッ素原子、または塩素原子を表し、Ａ５８は、
Figure JPOXMLDOC01-appb-C000112
からなる群から選択される１種の部分構造を表す。］で表される化合物（国際公開第１１／０６７２７２号参照）、 [C-28.132] Expression (s48)
Figure JPOXMLDOC01-appb-C000111
[Wherein, A57 represents a hydrogen atom, a fluorine atom, or a chlorine atom;
Figure JPOXMLDOC01-appb-C000112
Represents one kind of partial structure selected from the group consisting of: (See International Publication No. 11/067272),
［ｃ－２８．１３３］式（ｓ４９）
Figure JPOXMLDOC01-appb-C000113
［式中、Ａ５９は、水素原子、フッ素原子、または塩素原子を表し、Ａ６０は、
Figure JPOXMLDOC01-appb-C000114
からなる群から選択される部分構造を表す。］で表される化合物（国際公開第１０／０９０３４４号参照）、 [C-28.133] Expression (s49)
Figure JPOXMLDOC01-appb-C000113
[Wherein, A59 represents a hydrogen atom, a fluorine atom, or a chlorine atom;
Figure JPOXMLDOC01-appb-C000114
Represents a partial structure selected from the group consisting of (See WO 10/090344),
［ｃ－２８．１３４］式（ｓ５０）
Figure JPOXMLDOC01-appb-C000115
［式中、ｍ１０は、０～２の整数を表し、Ａ６１は、トリフルオロメチル基、トリフルオロメチルチオ基、トリフルオロメチルスルフィニル基、またはトリフルオロメチルスルホニル基を表し、Ａ６２は、水素原子、またはトリフルオロメチル基を表し、Ｖ６は、窒素原子、または炭素原子を表し、Ｖ７は、酸素原子、またはＮ－メチル基を表す。］で表される化合物（国際公開第１４／１０４４０７号参照）、 [C-28.134] Expression (s50)
Figure JPOXMLDOC01-appb-C000115
[In the formula, m10 represents an integer of 0 to 2, A61 represents a trifluoromethyl group, a trifluoromethylthio group, a trifluoromethylsulfinyl group, or a trifluoromethylsulfonyl group, and A62 represents a hydrogen atom, or It represents a trifluoromethyl group, V6 represents a nitrogen atom or a carbon atom, and V7 represents an oxygen atom or an N-methyl group. (See WO 14/104407),
［ｃ－２８．１３５］式（ｓ５１）
Figure JPOXMLDOC01-appb-C000116
［式中、Ａ６３は、水素原子、またはフッ素原子を表し、アミド基は４位、または５位に結合し、Ａ６４は、
Figure JPOXMLDOC01-appb-C000117
からなる群から選択される部分構造を表す。］で表される化合物（国際公開第１５／０３８５０３号、国際公開第１６／１４４３５１号、国際公開第１６／１４４６７８号参照）、 [C-28.135] Expression (s51)
Figure JPOXMLDOC01-appb-C000116
[Wherein, A63 represents a hydrogen atom or a fluorine atom, the amide group is bonded to the 4- or 5-position, and A64 is
Figure JPOXMLDOC01-appb-C000117
Represents a partial structure selected from the group consisting of ] The compound represented by these (refer to international publication 15/038503, international publication 16/144351, international publication 16/144678),
［ｃ－２８．１３６］式（ｓ５２）
Figure JPOXMLDOC01-appb-C000118
［式中、Ａ６５は、水素原子、Ｃ１～Ｃ６のアルキル基、またはＣ１～Ｃ６のハロアルキル基を表し、Ａ６６は、水素原子、ハロゲン原子、またはＣ１～Ｃ６のアルキル基を表し、Ａ６７およびＡ６８は、それぞれ独立していて、水素原子、シアノ基で適宜置換されてもよいＣ１～Ｃ６のアルキル基、メトキシ基で適宜置換されてもよいアルキル基、エトキシ基で適宜置換されてもよいアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表し、
Ａ６９は、水素原子、シアノ基、シアノ基で適宜置換されてもよいＣ１～Ｃ６のハロアルキル基、Ｃ１～Ｃ６のアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表す。］で表される化合物（国際公開第１２／１４３３１７号、国際公開第１６／０１６３６９号参照）、 [C-28.136] Expression (s52)
Figure JPOXMLDOC01-appb-C000118
[In the formula, A65 represents a hydrogen atom, a C1 to C6 alkyl group, or a C1 to C6 haloalkyl group, A66 represents a hydrogen atom, a halogen atom, or a C1 to C6 alkyl group, and A67 and A68 represent A hydrogen atom, a C1 to C6 alkyl group optionally substituted with a cyano group, an alkyl group optionally substituted with a methoxy group, an alkyl group optionally substituted with an ethoxy group, Or represents a C3 to C8 cycloalkyl group,
A69 represents a hydrogen atom, a cyano group, a C1-C6 haloalkyl group optionally substituted with a cyano group, a C1-C6 alkyl group, or a C3-C8 cycloalkyl group. ] The compound represented by these (refer international publication 12/143317, international publication 16/016369),
［ｃ－２８．１３７］式（ｓ５３）または式（ｓ５４）
Figure JPOXMLDOC01-appb-C000119
［式中、Ａ７０は、メチル基、エチル基、イソプロピル基、２，２，２－トリフルオロエチル基、またはフェニル基を表し、Ａ７１は、
Figure JPOXMLDOC01-appb-C000120
からなる群から選択される部分構造を表し、Ａ７２は、
Figure JPOXMLDOC01-appb-C000121
からなる群から選択される部分構造を表し、Ｖ８は、酸素原子、硫黄原子、－ＣＨ２－、または－ＣＨ２ＣＨ２－を表す。］で表される化合物（国際公開第１４／１６７０８４号、国際公開第１６／０５５４３１号参照）、 [C-28.137] Expression (s53) or Expression (s54)
Figure JPOXMLDOC01-appb-C000119
[In the formula, A70 represents a methyl group, an ethyl group, an isopropyl group, a 2,2,2-trifluoroethyl group, or a phenyl group, and A71 represents
Figure JPOXMLDOC01-appb-C000120
A72 represents a partial structure selected from the group consisting of:
Figure JPOXMLDOC01-appb-C000121
V8 represents an oxygen atom, a sulfur atom, —CH 2 —, or —CH 2 CH 2 —. ] The compound represented by these (refer international publication 14/167084, international publication 16/055431),
［ｃ－２８．１３８］式（ｓ５５）
Figure JPOXMLDOC01-appb-C000122
［式中、ｍ１１は、０～１の整数を表し、Ａ７３は、塩素原子、臭素原子、メチル基、またはトリフルオロメチル基を表し、Ａ７４は、水素原子、塩素原子、臭素原子、シアノ基、またはトリフルオロメチル基表し、Ａ７５は、水素原子、塩素原子または臭素原子を表し、Ａ７６およびＡ７７は、それぞれ独立していて、Ｃ１～Ｃ６のアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表し、Ａ７８は、塩素原子、臭素原子、シアノ基、ニトロ基、ジフルオロメチル基、またはトリフルオロメチル基を表す。］で表される化合物（国際公開第１３／０２４００９号参照）、 [C-28.138] Expression (s55)
Figure JPOXMLDOC01-appb-C000122
[In the formula, m11 represents an integer of 0 to 1, A73 represents a chlorine atom, a bromine atom, a methyl group, or a trifluoromethyl group, and A74 represents a hydrogen atom, a chlorine atom, a bromine atom, a cyano group, Or a trifluoromethyl group, A75 represents a hydrogen atom, a chlorine atom or a bromine atom, A76 and A77 each independently represent a C1 to C6 alkyl group, or a C3 to C8 cycloalkyl group, A78 represents a chlorine atom, a bromine atom, a cyano group, a nitro group, a difluoromethyl group, or a trifluoromethyl group. A compound represented by the formula (see International Patent Publication No.
［ｃ－２８．１３９］式（ｓ５６）
Figure JPOXMLDOC01-appb-C000123
［式中、Ａ７９、Ａ８０、Ａ８１およびＡ８２は、それぞれ独立していて、水素原子、ハロゲン原子、Ｃ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、Ｃ１～Ｃ６のアルコキシ基、またはＣ３～Ｃ８のシクロアルコキシ基を表す。］で表される化合物（国際公開第１２／０２７５２１号参照）、 [C-28.139] Expression (s56)
Figure JPOXMLDOC01-appb-C000123
[Wherein A79, A80, A81 and A82 are each independently a hydrogen atom, a halogen atom, a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, a C1 to C6 alkoxy group, or a C3 to C8 Represents a cycloalkoxy group. (See WO 12/027521),
［ｃ－２８．１４０］式（ｓ５７）
Figure JPOXMLDOC01-appb-C000124
［式中、ｍ１２は、０～２の整数を表し、Ａ８３は、水素原子、またはフッ素原子を表し、Ａ８４は、
Figure JPOXMLDOC01-appb-C000125
からなる群から選択される部分構造を表す。］で表される化合物（国際公開第１３／１６２７１５号参照）、 [C-28.140] Expression (s57)
Figure JPOXMLDOC01-appb-C000124
[In the formula, m12 represents an integer of 0 to 2, A83 represents a hydrogen atom or a fluorine atom, and A84 represents
Figure JPOXMLDOC01-appb-C000125
Represents a partial structure selected from the group consisting of (See WO 13/162715),
［ｃ－２８．１４１］アシノナピル（ａｃｙｎｏｎａｐｙｒ）、 [C-28.141] asynonapyr,
［ｃ－２８．１４２］式（ｓ５９）
Figure JPOXMLDOC01-appb-C000126
［Ａ９０は、ハロゲン原子、Ｃ１～Ｃ６のアルキル基、またはＣ１～Ｃ６のハロアルキル基を表し、Ａ９１は、Ｃ１～Ｃ６のハロアルキル基を表し、Ａ９２およびＡ９３は、それぞれ独立していて、水素原子、Ｃ１～Ｃ６のアルキル基、アセチル基、プロピオニル基、メタンスルホニルエチル基、メトキシカルボニル基、またはエトキシカルボニル基を表し、Ａ９４およびＡ９５は、それぞれ独立していて、水素原子、Ｃ１～Ｃ６のアルキル基、またはＣ１～Ｃ６のハロアルキル基を表す。］で表される化合物（国際公開第１２／１６４６９８号参照）等が挙げられる。 [C-28.142] Expression (s59)
Figure JPOXMLDOC01-appb-C000126
[A90 represents a halogen atom, a C1 to C6 alkyl group, or a C1 to C6 haloalkyl group, A91 represents a C1 to C6 haloalkyl group, and A92 and A93 are each independently a hydrogen atom, Represents a C1 to C6 alkyl group, an acetyl group, a propionyl group, a methanesulfonylethyl group, a methoxycarbonyl group, or an ethoxycarbonyl group, wherein A94 and A95 are each independently a hydrogen atom, a C1 to C6 alkyl group, Alternatively, it represents a C1-C6 haloalkyl group. And the like (see WO 12/1664698).
　本発明化合物と前述の必要に応じて混合して使用することができる他の農薬との混合比は、効果が発揮される限りにおいて特に制限されるものではないが、通常、本発明化合物に対して他の農薬は、重量比で０．００１～１０００の比率であり、好ましくは、０．０１～１００の比率である。 The mixing ratio of the compound of the present invention and the other pesticide that can be used as a mixture according to the above need is not particularly limited as long as the effect is exhibited, but usually, to the compound of the present invention The other pesticides have a weight ratio of 0.001 to 1000, preferably 0.01 to 100.
　以下に実施例により、本発明を更に詳細に示すが、本発明はこれらに限定されるものではない。 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these.
［合成例１］
　３，５－ジメチル－１－（２－メチル－３－チエニル）－２－（２，４，６－トリフルオロフェニル）ピリジン－４（１Ｈ）－オンの合成（化合物番号：１）
Figure JPOXMLDOC01-appb-C000127
 [Synthesis Example 1]
Synthesis of 3,5-dimethyl-1- (2-methyl-3-thienyl) -2- (2,4,6-trifluorophenyl) pyridin-4 (1H) -one (Compound No. 1)
Figure JPOXMLDOC01-appb-C000127
　参考例１で得られた３，５－ジメチル－１－（２－メチル－３－チエニル）－２－（２，４，６－トリフルオロフェニル）－２，３－ジヒドロピリジン－４（１Ｈ）－オン　８６０ｍｇ、ペルオキソ二硫酸カリウム（Ｋ２Ｓ２Ｏ８）　２．５４ｇと硫酸　９２２ｍｇを含むアセトニトリル溶液　１０ｍｌを、還流下で３．５時間撹拌した。反応混合物を室温まで冷却した後に、飽和炭酸水素ナトリウム水溶液と酢酸エチルを加えて分液した。得られた有機層をチオ硫酸ナトリウム水溶液および飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が５５ｍｇのオレンジ褐色固体として得られた。 3,5-Dimethyl-1- (2-methyl-3-thienyl) -2- (2,4,6-trifluorophenyl) -2,3-dihydropyridine-4 (1H) -obtained in Reference Example 1 10 ml of an acetonitrile solution containing 860 mg of ON, 2.54 g of potassium peroxodisulfate (K 2 S 2 O 8 ) and 922 mg of sulfuric acid was stirred under reflux for 3.5 hours. The reaction mixture was cooled to room temperature, saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added, and the layers were separated. The obtained organic layer was washed successively with an aqueous sodium thiosulfate solution and saturated brine, and dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 55 mg as an orange-brown solid.
［合成例２］
　３，５－ジメチル－１－（３－チエニル）－２－（２－クロロ－４－フルオロフェニル）ピリジン－４（１Ｈ）－オンの合成（化合物番号：１０）
Figure JPOXMLDOC01-appb-C000128
 [Synthesis Example 2]
Synthesis of 3,5-dimethyl-1- (3-thienyl) -2- (2-chloro-4-fluorophenyl) pyridin-4 (1H) -one (Compound No. 10)
Figure JPOXMLDOC01-appb-C000128
　参考例２で得られた２－（２－クロロ－４フルオロフェニル）－３，５－ジメチル－１－（３－チエニル）－２，３－ジヒドロピリジン－４（１Ｈ）－オンと３９重量％ＩＢＸ（２－ヨードキシ安息香酸）　４．４３ｇを含むジメチルスルホキシド溶液　１０ｍｌを、８０℃で２時間撹拌した。室温まで冷却した後に、反応混合物にチオ硫酸ナトリウム水溶液と酢酸エチルを加え、不溶成分をセライト濾過により除去した。得られた濾液を分液した後に、有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。減圧下にて溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が１１５ｍｇの淡黄色アモルファスとして得られた。 2- (2-chloro-4fluorophenyl) -3,5-dimethyl-1- (3-thienyl) -2,3-dihydropyridin-4 (1H) -one obtained in Reference Example 2 and 39 wt% IBX (2-Iodooxybenzoic acid) 10 ml of a dimethyl sulfoxide solution containing 4.43 g was stirred at 80 ° C. for 2 hours. After cooling to room temperature, an aqueous solution of sodium thiosulfate and ethyl acetate were added to the reaction mixture, and insoluble components were removed by Celite filtration. After separating the obtained filtrate, the organic layer was washed with saturated brine and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 115 mg of a pale yellow amorphous.
［合成例３］
　３，５－ジメチル－１－（３－チエニル）－２－（２，６－ジフルオロ－４－メトキシフェニル）ピリジン－４（１Ｈ）－オンの合成（化合物番号：３）
Figure JPOXMLDOC01-appb-C000129
　３，５－ジメチル－１－（３－チエニル）－２－（２，４，６－トリフルオロフェニル）ピリジン－４（１Ｈ）－オン　２０６ｍｇを含むメタノール溶液　５ｍｌに２８重量％ナトリウムメトキシドのメタノール溶液　１．１９ｇを加えて、還流下で４．５時間撹拌した。反応混合物を室温まで冷却した後に、水と酢酸エチルを加えて分液した。得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が６７ｍｇの白色アモルファスとして得られた。 [Synthesis example 3]
Synthesis of 3,5-dimethyl-1- (3-thienyl) -2- (2,6-difluoro-4-methoxyphenyl) pyridin-4 (1H) -one (Compound No. 3)
Figure JPOXMLDOC01-appb-C000129
Methanol solution containing 206 mg of 3,5-dimethyl-1- (3-thienyl) -2- (2,4,6-trifluorophenyl) pyridin-4 (1H) -one 28% by weight sodium methoxide methanol in 5 ml 1.19 g of the solution was added, and the mixture was stirred under reflux for 4.5 hours. The reaction mixture was cooled to room temperature, water and ethyl acetate were added, and the layers were separated. The obtained organic layer was washed with saturated saline and dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 67 mg of white amorphous.
［合成例４］
　５－ブロモ－３－クロロ－２－（２，４－ジフルオロフェニル）－１－（３－チエニル）ピリジン－４（１Ｈ）－オンの合成（化合物番号：３５）
Figure JPOXMLDOC01-appb-C000130
 [Synthesis Example 4]
Synthesis of 5-bromo-3-chloro-2- (2,4-difluorophenyl) -1- (3-thienyl) pyridin-4 (1H) -one (Compound No. 35)
Figure JPOXMLDOC01-appb-C000130
　参考例５で得られた５－ブロモ－２－（２，４－ジフルオロフェニル）－１－（３－チエニル）ピリジン－４（１Ｈ）－オン　８５ｍｇとＮ－クロロスクシンイミド　３３ｍｇを含むクロロホルム溶液　３ｍｌを室温で１９時間撹拌した。反応混合物に水と酢酸エチルを加えて分液した後に、得られた有機層をチオ硫酸ナトリウム水溶液および飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が８０ｍｇの白色固体として得られた。 3 ml of a chloroform solution containing 85 mg of 5-bromo-2- (2,4-difluorophenyl) -1- (3-thienyl) pyridin-4 (1H) -one obtained in Reference Example 5 and 33 mg of N-chlorosuccinimide was added. Stir at room temperature for 19 hours. After water and ethyl acetate were added to the reaction mixture for liquid separation, the obtained organic layer was washed successively with an aqueous sodium thiosulfate solution and saturated brine, and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 80 mg of white solid.
［合成例５］
　２－（２，４－ジフルオロフェニル）－３－エチル－１－（３－チエニル）ピリジン－４（１Ｈ）－オンの合成（化合物番号：１７）
Figure JPOXMLDOC01-appb-C000131
 [Synthesis example 5]
Synthesis of 2- (2,4-difluorophenyl) -3-ethyl-1- (3-thienyl) pyridin-4 (1H) -one (Compound No. 17)
Figure JPOXMLDOC01-appb-C000131
　１－（３－チエニル）－３－エチル－２－（２，４－ジフルオロフェニル）－２，３－ジヒドロピリジン－４（１Ｈ）－オン　１．６５ｇと３９重量％ＩＢＸ　４．４５ｇを含むジメチルスルホキシド溶液　１０ｍｌを、８０℃で２時間撹拌した。さらに、３９重量％ＩＢＸ　４．４５ｇを加えて、８０℃で１．５時間撹拌した。室温まで冷却した後に、反応混合物にチオ硫酸ナトリウム水溶液と酢酸エチルを加えて分液した。得られた有機層を飽和炭酸水素ナトリウム水溶液と飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥した。減圧下にて溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が９３ｍｇの淡黄色アモルファスとして得られた。 Dimethyl sulfoxide containing 1- (3-thienyl) -3-ethyl-2- (2,4-difluorophenyl) -2,3-dihydropyridin-4 (1H) -one 1.65 g and 39 wt% IBX 4.45 g 10 ml of the solution was stirred at 80 ° C. for 2 hours. Further, 4.45 g of 39 wt% IBX was added, and the mixture was stirred at 80 ° C. for 1.5 hours. After cooling to room temperature, an aqueous sodium thiosulfate solution and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 93 mg of a pale yellow amorphous.
［合成例６］
　５－ブロモ－２－（２，４－ジフルオロフェニル）－３－エチル－１－（３－チエニル）ピリジン－４（１Ｈ）－オンの合成（化合物番号：１８）
Figure JPOXMLDOC01-appb-C000132
 [Synthesis example 6]
Synthesis of 5-bromo-2- (2,4-difluorophenyl) -3-ethyl-1- (3-thienyl) pyridin-4 (1H) -one (Compound No. 18)
Figure JPOXMLDOC01-appb-C000132
　２－（２，４－ジフルオロフェニル）－３－エチル－１－（３－チエニル）ピリジン－４（１Ｈ）－オン　４０９ｍｇとＮ－ブロモスクシンイミド　２３０ｍｇを含むクロロホルム溶液　５ｍｌを、室温下で５．５時間撹拌した。反応混合物に水と酢酸エチルを加えて分液した後に、得られた有機層をチオ硫酸ナトリウム水溶液および飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が３７２ｍｇの赤褐色固体として得られた。 5 ml of a chloroform solution containing 409 mg of 2- (2,4-difluorophenyl) -3-ethyl-1- (3-thienyl) pyridin-4 (1H) -one and 230 mg of N-bromosuccinimide at 5.5 at room temperature Stir for hours. After water and ethyl acetate were added to the reaction mixture for liquid separation, the obtained organic layer was washed successively with an aqueous sodium thiosulfate solution and saturated brine, and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 372 mg of a reddish brown solid.
［合成例７］
　２－（２，４－ジフルオロフェニル）－３－エチル－５－メチル－１－（３－チエニル）ピリジン－４（１Ｈ）－オンの合成（化合物番号：３０）
Figure JPOXMLDOC01-appb-C000133
 [Synthesis example 7]
Synthesis of 2- (2,4-difluorophenyl) -3-ethyl-5-methyl-1- (3-thienyl) pyridin-4 (1H) -one (Compound No. 30)
Figure JPOXMLDOC01-appb-C000133
　５－ブロモ－２－（２，４－ジフルオロフェニル）－３－エチル－１－（３－チエニル）ピリジン－４（１Ｈ）－オン　２６６ｍｇ、メチルボロン酸１６０ｍｇ、酢酸パラジウム（ＩＩ）１５ｍｇ、リン酸三カリウム　４９９ｍｇとトリシクロヘキシルホスフィン　３８ｍｇを含むトルエン　１０ｍｌと水　１ｍｌの混合溶液を、８０℃で５時間撹拌した。室温まで冷却した後に、反応混合物に水と酢酸エチルを加えて分液した。得られた有機層を飽和食塩水で洗浄した後に、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が９８ｍｇの淡黄色アモルファスとして得られた。 5-Bromo-2- (2,4-difluorophenyl) -3-ethyl-1- (3-thienyl) pyridin-4 (1H) -one 266 mg, methylboronic acid 160 mg, palladium (II) acetate 15 mg, triphosphate A mixed solution of 10 ml of toluene and 1 ml of water containing 499 mg of potassium and 38 mg of tricyclohexylphosphine was stirred at 80 ° C. for 5 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was washed with saturated saline and then dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 98 mg of a pale yellow amorphous.
［合成例８］
　２－（２，６－ジフルオロフェニル）－３，５－ジメチル―１－（１－メチル－３－ピラゾリル）ピリジン－４（１Ｈ）－オンの合成（化合物番号：２０）
Figure JPOXMLDOC01-appb-C000134
 [Synthesis example 8]
Synthesis of 2- (2,6-difluorophenyl) -3,5-dimethyl-1- (1-methyl-3-pyrazolyl) pyridin-4 (1H) -one (Compound No. 20)
Figure JPOXMLDOC01-appb-C000134
　参考例７で得られた２－（２，６－ジフルオロフェニル）－３，５－ジメチル―１－（１－メチル－３－ピラゾリル）－２，３－ジヒドロピリジン－４（１Ｈ）－オン　４．６０ｇと臭素　７４７μｌを含む酢酸溶液　４６ｍｌを、１２０℃で２時間撹拌した。室温まで冷却した後に、反応混合物に水と酢酸エチルを加えて分液した。得られた有機層を炭酸カリウム水溶液、チオ硫酸ナトリウム水溶液および飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が２．４３ｇの白色固体として得られた。 2- (2,6-difluorophenyl) -3,5-dimethyl-1- (1-methyl-3-pyrazolyl) -2,3-dihydropyridin-4 (1H) -one obtained in Reference Example 4. 46 ml of acetic acid solution containing 60 g and 747 μl of bromine was stirred at 120 ° C. for 2 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was washed successively with an aqueous potassium carbonate solution, an aqueous sodium thiosulfate solution and a saturated saline solution, and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 2.43 g of a white solid.
［合成例９］
　２－（２，６－ジフルオロフェニル）－３，５－ジメチル―１－（５－ホルミル－１－メチル－３－ピラゾリル）ピリジン－４（１Ｈ）－オンの合成（化合物番号：５８）
Figure JPOXMLDOC01-appb-C000135
 [Synthesis example 9]
Synthesis of 2- (2,6-difluorophenyl) -3,5-dimethyl-1- (5-formyl-1-methyl-3-pyrazolyl) pyridin-4 (1H) -one (Compound No. 58)
Figure JPOXMLDOC01-appb-C000135
　２－（２，６－ジフルオロフェニル）－３，５－ジメチル―１－（１－メチル－３－ピラゾリル）ピリジン－４（１Ｈ）－オン　３００ｍｇを含むＴＨＦ溶液　５ｍｌに、２．７６ｍｏｌ／ｌのノルマルブチルリチウムのヘキサン溶液　４１４μｌを－７８℃で滴下し２時間撹拌した後に、ＤＭＦ　１８３μｌを加えて、－７８℃で５時間撹拌した。反応混合物に飽和塩化アンモニウム水溶液と酢酸エチルを加えて分液した後に、得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が１０１ｍｇの無色油状物質として得られた。 2- (2,6-difluorophenyl) -3,5-dimethyl-1- (1-methyl-3-pyrazolyl) pyridin-4 (1H) -one 300 ml THF solution containing 300 mg, 2.76 mol / l After 414 μl of a hexane solution of normal butyl lithium was added dropwise at −78 ° C. and stirred for 2 hours, 183 μl of DMF was added and stirred at −78 ° C. for 5 hours. A saturated ammonium chloride aqueous solution and ethyl acetate were added to the reaction mixture for liquid separation, and the obtained organic layer was washed with saturated brine and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 101 mg of a colorless oil.
［合成例１０］
　２－（２，６－ジフルオロフェニル）－３，５－ジメチル―１－（５－ジフルオロメチル－１－メチル－３－ピラゾリル）ピリジン－４（１Ｈ）－オンの合成（化合物番号：４３）
Figure JPOXMLDOC01-appb-C000136
 [Synthesis example 10]
Synthesis of 2- (2,6-difluorophenyl) -3,5-dimethyl-1- (5-difluoromethyl-1-methyl-3-pyrazolyl) pyridin-4 (1H) -one (Compound No. 43)
Figure JPOXMLDOC01-appb-C000136
　２－（２，６－ジフルオロフェニル）－３，５－ジメチル―１－（５－ホルミル－１－メチル－３－ピラゾリル）ピリジン－４（１Ｈ）－オン　１０１ｍｇとＤｅｏｘｏ－Ｆｌｕｏｒ（Ｎ，Ｎ－ジメトキシエチルアミノ硫黄トリフルオリド）　１６４μｌを含むジクロロメタン溶液　４ｍｌを、室温で６時間撹拌した。反応混合物に水を加えて分液した後に、得られた有機層を飽和炭酸水素ナトリウム水溶液と飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が８１．８ｍｇの白色固体として得られた。 2- (2,6-Difluorophenyl) -3,5-dimethyl-1- (5-formyl-1-methyl-3-pyrazolyl) pyridin-4 (1H) -one 101 mg and Deoxo-Fluor (N, N- 4 ml of a dichloromethane solution containing 164 μl of dimethoxyethylaminosulfur trifluoride) was stirred at room temperature for 6 hours. After water was added to the reaction mixture for liquid separation, the obtained organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 81.8 mg of a white solid.
［合成例１１］
　２－（２，６－ジフルオロフェニル）－３，５－ジメチル―１－（３－ブロモ－１－メチル－４－ピラゾリル）ピリジン－４（１Ｈ）－オンの合成（化合物番号：４５）
Figure JPOXMLDOC01-appb-C000137
 [Synthesis Example 11]
Synthesis of 2- (2,6-difluorophenyl) -3,5-dimethyl-1- (3-bromo-1-methyl-4-pyrazolyl) pyridin-4 (1H) -one (Compound No. 45)
Figure JPOXMLDOC01-appb-C000137
　２－（２，６－ジフルオロフェニル）－３，５－ジメチル―１－（１－メチル－４－ピラゾリル）－２，３－ジヒドロピリジン－４（１Ｈ）－オン　１．７５ｇと臭素　２８５μｌを含む酢酸溶液　１８ｍｌを、１２０℃で４時間撹拌した。室温まで冷却した後に、反応混合物に炭酸カリウム水溶液と酢酸エチルを加えて分液した。得られた有機層をチオ硫酸ナトリウム水溶液および飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が０．６４ｇの白色固体として得られた。 Acetic acid containing 1.75 g of 2- (2,6-difluorophenyl) -3,5-dimethyl-1- (1-methyl-4-pyrazolyl) -2,3-dihydropyridin-4 (1H) -one and 285 μl of bromine 18 ml of the solution was stirred at 120 ° C. for 4 hours. After cooling to room temperature, aqueous potassium carbonate solution and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was washed successively with an aqueous sodium thiosulfate solution and saturated brine, and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 0.64 g of a white solid.
［合成例１２］
　５－ブロモ－２－（２，６－ジフルオロフェニル）－３－メチル－１－（１－メチル－５－ピラゾリル）ピリジン－４（１Ｈ）－オンの合成（化合物番号：５１）
Figure JPOXMLDOC01-appb-C000138
 [Synthesis Example 12]
Synthesis of 5-bromo-2- (2,6-difluorophenyl) -3-methyl-1- (1-methyl-5-pyrazolyl) pyridin-4 (1H) -one (Compound No. 51)
Figure JPOXMLDOC01-appb-C000138
　参考例１０で得られた５－ブロモ－２－（２，６－ジフルオロフェニル）－３－メチル－１－（１－メチル－５－ピラゾリル）－２，３－ジヒドロピリジン－４（１Ｈ）－オン　７０ｍｇ、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）　６ｍｇとＮ－ブロモスクシンイミド　３４ｍｇを含む四塩化炭素溶液　２ｍｌを４０℃で１時間撹拌した。室温まで冷却した後に、チオ硫酸ナトリウム水溶液と酢酸エチルを加えて分液した。得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が３５ｍｇの白色固体として得られた。 5-Bromo-2- (2,6-difluorophenyl) -3-methyl-1- (1-methyl-5-pyrazolyl) -2,3-dihydropyridin-4 (1H) -one obtained in Reference Example 10 A carbon tetrachloride solution (2 ml) containing 70 mg, 6 mg of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 34 mg of N-bromosuccinimide was stirred at 40 ° C. for 1 hour. After cooling to room temperature, an aqueous sodium thiosulfate solution and ethyl acetate were added for liquid separation. The obtained organic layer was washed with saturated saline and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 35 mg white solid.
［合成例１３］
　２－（２，６－ジフルオロフェニル）－３，５－ジメチル－１－（１，３，４－チアジアゾール－２－イル）ピリジン－４（１Ｈ）－オンの合成（化合物番号：４２）
Figure JPOXMLDOC01-appb-C000139
 [Synthesis Example 13]
Synthesis of 2- (2,6-difluorophenyl) -3,5-dimethyl-1- (1,3,4-thiadiazol-2-yl) pyridin-4 (1H) -one (Compound No. 42)
Figure JPOXMLDOC01-appb-C000139
　参考例１１で得られた１－（（１，３，４－チアジアゾール－２－イル）アミノ）－１－（２，６－ジフルオロフェニル－５－メトキシ－２，４－ジメチルペンタ－１，４－ジエン－３－オン　２．３８ｇ、ペルオキソ二硫酸カリウム　３．６６ｇと硫酸　１．３３ｇを含むアセトニトリル溶液　７１ｍｌを、還流下で６．５時間撹拌した。反応混合物を室温まで冷却した後に、飽和炭酸水素ナトリウム水溶液と酢酸エチルを加えて分液した。得られた有機層をチオ硫酸ナトリウム水溶液および飽和食塩水で順次洗浄し、硫酸ナトリウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が７２０ｍｇの淡黄色固体として得られた。 1-((1,3,4-thiadiazol-2-yl) amino) -1- (2,6-difluorophenyl-5-methoxy-2,4-dimethylpenta-1,4 obtained in Reference Example 11 71 ml of an acetonitrile solution containing 2.38 g of -dien-3-one, 3.66 g of potassium peroxodisulfate and 1.33 g of sulfuric acid was stirred under reflux for 6.5 hours, and the reaction mixture was cooled to room temperature and then saturated carbonic acid was added. An aqueous solution of sodium hydrogen and ethyl acetate were added and the layers were separated, and the obtained organic layer was washed successively with an aqueous solution of sodium thiosulfate and saturated brine, dried over sodium sulfate, and obtained by evaporating the solvent under reduced pressure. The residue was purified by silica gel column chromatography to obtain the title compound as 720 mg of a pale yellow solid.
［合成例１４］
　１－（５－ブロモ－１，３，４－チアジアゾール－２－イル）－２－（２，６－ジフルオロフェニル）－３，５－ジメチルピリジン－４（１Ｈ）－オンの合成（化合物番号：４８）
Figure JPOXMLDOC01-appb-C000140
 [Synthesis Example 14]
Synthesis of 1- (5-bromo-1,3,4-thiadiazol-2-yl) -2- (2,6-difluorophenyl) -3,5-dimethylpyridin-4 (1H) -one (Compound No .: 48)
Figure JPOXMLDOC01-appb-C000140
　２－（２，６－ジフルオロフェニル）－３，５－ジメチル－１－（１，３，４－チアジアゾール－２－イル）ピリジン－４（１Ｈ）－オン　１２０ｍｇとＮ－ブロモスクシンイミド　２７８ｍｇを含むＤＭＦ溶液　１．２ｍｌを８０℃で１時間撹拌した。反応混合物を室温まで冷却した後に、水と酢酸エチルを加えて分液した。得られた有機層をチオ硫酸ナトリウム水溶液および飽和食塩水で順次洗浄し、硫酸ナトリウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が５４ｍｇの淡黄色固体として得られた。 DMF containing 120 mg of 2- (2,6-difluorophenyl) -3,5-dimethyl-1- (1,3,4-thiadiazol-2-yl) pyridin-4 (1H) -one and 278 mg of N-bromosuccinimide 1.2 ml of the solution was stirred at 80 ° C. for 1 hour. The reaction mixture was cooled to room temperature, water and ethyl acetate were added, and the layers were separated. The obtained organic layer was washed successively with an aqueous sodium thiosulfate solution and saturated brine, and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 54 mg of a pale yellow solid.
［合成例１５］
　１－（５－メチル－チアゾール－２－イル）－２－（２，６－ジフルオロフェニル）－３，５－ジメチルピリジン－４（１Ｈ）－オンの合成（化合物番号：４１）
Figure JPOXMLDOC01-appb-C000141
 [Synthesis Example 15]
Synthesis of 1- (5-methyl-thiazol-2-yl) -2- (2,6-difluorophenyl) -3,5-dimethylpyridin-4 (1H) -one (Compound No. 41)
Figure JPOXMLDOC01-appb-C000141
　１－（（５－メチル－チアゾール－２－イル）アミノ）－１－（２，６－ジフルオロフェニル－５－メトキシ－２，４－ジメチルペンタ－１，４－ジエン－３－オン　１．００ｇ、ペルオキソ二硫酸カリウム　１．６２ｇと硫酸　５８７ｍｇを含むアセトニトリル溶液　３０ｍｌを、還流下で７時間撹拌した。反応混合物を室温まで冷却した後に、飽和炭酸水素ナトリウム水溶液と酢酸エチルを加えて分液した。得られた有機層をチオ硫酸ナトリウム水溶液および飽和食塩水で順次洗浄し、硫酸ナトリウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が４４０ｍｇの黄土色固体として得られた。 1-((5-methyl-thiazol-2-yl) amino) -1- (2,6-difluorophenyl-5-methoxy-2,4-dimethylpenta-1,4-dien-3-one 1.00 g , 30 ml of an acetonitrile solution containing 1.62 g of potassium peroxodisulfate and 587 mg of sulfuric acid was stirred under reflux for 7 hours, and the reaction mixture was cooled to room temperature, and then saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added for liquid separation. The obtained organic layer was washed successively with aqueous sodium thiosulfate solution and saturated brine, dried over sodium sulfate, and the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The compound was obtained as 440 mg as an ocher solid.
［参考例１］
Figure JPOXMLDOC01-appb-C000142
　ステップ１：１－（２，４，６－トリフルオロフェニル）－Ｎ－（２－メチル－３－チ
エニル）メタンイミンの合成
　２，４，６－トリフルオロベンズアルデヒド　２．０３ｇ、２－メチル－３－アミノチオフェン（国際公開第２０１７／０３５３６０号に記載の方法にて合成）　１．４７ｇと硫酸マグネシウム　１．５３ｇを含むジクロロエタン溶液２０ｍｌを８０℃で２時間撹拌した。室温まで冷却した後に、反応混合物中の硫酸マグネシウムを濾過にて除去し、得られた濾液を減圧下で溶媒留去した。得られた褐色油状物質　３．２４ｇは表題の化合物であり、これ以上精製することなく、次の反応に使用した。 [Reference Example 1]
Figure JPOXMLDOC01-appb-C000142
Step 1: Synthesis of 1- (2,4,6-trifluorophenyl) -N- (2-methyl-3-thienyl) methanimine 2,4,6-trifluorobenzaldehyde 2.03 g, 2-methyl-3- 20 ml of a dichloroethane solution containing 1.47 g of aminothiophene (synthesized by the method described in WO 2017/035360) and 1.53 g of magnesium sulfate was stirred at 80 ° C. for 2 hours. After cooling to room temperature, magnesium sulfate in the reaction mixture was removed by filtration, and the obtained filtrate was evaporated under reduced pressure. The obtained brown oily substance (3.24 g) was the title compound and was used in the next reaction without further purification.
１Ｈ－ＮＭＲ　（ＣＤＣｌ３）　δ：　８．６３　（１Ｈ，　ｓ），　７．１２－７．１１　（２Ｈ，　ｍ），　６．７７－６．７５　（２Ｈ，　ｍ），　２．５７　（３Ｈ，　ｓ）． 1 H-NMR (CDCl3) δ: 8.63 (1H, s), 7.12-7.11 (2H, m), 6.77-6.75 (2H, m), 2.57 (3H, s).
　ステップ２：３，５－ジメチル－１－（２－メチル－３－チエニル）－２－（２，４，６－トリフルオロフェニル）－２，３－ジヒドロピリジン－４（１Ｈ）－オンの合成
　１－（２，４，６－トリフルオロフェニル）－Ｎ－（２－メチル－３－チエニル）メタンイミン　３．２４ｇと（（１－メトキシ－２－メチルペンタ－１，３－ジエン－３－イル）オキシ）トリメチルシラン　１．１３ｇを含むアセトニトリル溶液　１０ｍｌを氷冷し、４２重量％テトラフルオロホウ酸水溶液　２００ｍｇを加え、氷冷下１時間撹拌した。反応混合物に飽和炭酸水素ナトリウム水溶液と酢酸エチルを加えて分液した後に、得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が８６０ｍｇのオレンジ色油状物質として得られた。これ以上精製することなく、次の反応に使用した。 Step 2: Synthesis of 3,5-dimethyl-1- (2-methyl-3-thienyl) -2- (2,4,6-trifluorophenyl) -2,3-dihydropyridin-4 (1H) -one 1 3.24 g of-(2,4,6-trifluorophenyl) -N- (2-methyl-3-thienyl) methanimine and ((1-methoxy-2-methylpenta-1,3-dien-3-yl) oxy ) 10 ml of an acetonitrile solution containing 1.13 g of trimethylsilane was ice-cooled, 200 mg of a 42 wt% tetrafluoroboric acid aqueous solution was added, and the mixture was stirred for 1 hour under ice-cooling. A saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added to the reaction mixture for liquid separation, and the obtained organic layer was washed with saturated brine and dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 860 mg of an orange oil. Used for the next reaction without further purification.
［参考例２］
Figure JPOXMLDOC01-appb-C000143
　ステップ１：１－（２－クロロ－４－フルオロフェニル）－Ｎ－（３－チエニル）メタンイミンの合成
　２－クロロ－４－フルオロベンズアルデヒド　１．００ｇ、３－アミノチオフェンシュウ酸塩　１．１９ｇとトリエチルアミン　１．２７ｇを含むＴＨＦ溶液２０ｍｌを室温で４時間撹拌した。反応混合物中の固体を濾過にて除去した後に、得られた濾液を減圧下で溶媒留去した。得られた黄土色固体　１．２９ｇは表題の化合物であり、これ以上精製することなく、次の反応に使用した。 [Reference Example 2]
Figure JPOXMLDOC01-appb-C000143
Step 1: Synthesis of 1- (2-chloro-4-fluorophenyl) -N- (3-thienyl) methanimine 2-chloro-4-fluorobenzaldehyde 1.00 g, 3-aminothiophene oxalate 1.19 g and triethylamine 20 ml of a THF solution containing 1.27 g was stirred at room temperature for 4 hours. After removing solids in the reaction mixture by filtration, the obtained filtrate was evaporated under reduced pressure. The ocher solid 1.29 g obtained was the title compound and was used in the next reaction without further purification.
１Ｈ－ＮＭＲ　（ＣＤＣｌ３）　δ：　８．９４　（１Ｈ，　ｓ），　８．２５　（１Ｈ，　ｄｄ，　Ｊ　＝　８．４，　６．２　Ｈｚ），　７．３６－７．３４　（１Ｈ，　ｍ），　７．２４－７．２３　（２Ｈ，　ｍ），　７．１７　（１Ｈ，　ｄｄ，　Ｊ　＝　８．４，　２．６　Ｈｚ），　７．１０－７．０７　（１Ｈ，　ｍ）． 1 H-NMR (CDCl3) δ: 8.94 (1H, s), 8.25 (1H, dd, J = 8.4, 6.2 Hz), 7.36-7.34 (1H, m) , 7.24-7.23 (2H, m), 7.17 (1H, dd, J = 8.4, 2.6 Hz), 7.10-7.07 (1H, m).
　ステップ２：２－（２－クロロ－４－フルオロフェニル）－３，５－ジメチル－１－（３－チエニル）－２，３－ジヒドロピリジン－４（１Ｈ）－オンの合成
　１－（２－クロロ－４－フルオロフェニル）－Ｎ－（３－チエニル）メタンイミン　１．２９ｇと（（１－メトキシ－２－メチルペンタ－１，３－ジエン－３－イル）オキシ）トリメチルシラン　１．２６ｇを含むアセトニトリル溶液　２０ｍｌを氷冷し、４２重量％テトラフルオロホウ酸水溶液　２６８ｍｇを加え、氷冷下１時間撹拌した。反応混合物に飽和炭酸水素ナトリウム水溶液と酢酸エチルを加えて分液した後に、得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が２．１２ｇの黄色油状物質として得られた。これ以上精製することなく、次の反応に使用した。 Step 2: Synthesis of 2- (2-chloro-4-fluorophenyl) -3,5-dimethyl-1- (3-thienyl) -2,3-dihydropyridin-4 (1H) -one 1- (2-chloro Acetonitrile solution containing 1.29 g of -4-fluorophenyl) -N- (3-thienyl) methanimine and 1.26 g of ((1-methoxy-2-methylpenta-1,3-dien-3-yl) oxy) trimethylsilane 20 ml was ice-cooled, 42 weight% tetrafluoroboric acid aqueous solution 268 mg was added, and it stirred under ice-cooling for 1 hour. A saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added to the reaction mixture for liquid separation, and the obtained organic layer was washed with saturated brine and dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 2.12 g of a yellow oil. Used for the next reaction without further purification.
［参考例３］
Figure JPOXMLDOC01-appb-C000144
　ステップ１：１－（２，４－ジフルオロフェニル）－Ｎ－（３－チエニル）メタンイミンの合成
　２，４－ジフルオロベンズアルデヒド　５．００ｇ、３－アミノチオフェンシュウ酸塩　６．６６ｇとトリエチルアミン　７．１２ｇを含むＴＨＦ溶液１００ｍｌを室温で３時間撹拌した。反応混合物中の不溶成分を濾過にて除去し、得られた濾液を減圧下で溶媒留去した。得られた黒色油状物質　１．２８ｇは表題の化合物であり、これ以上精製することなく、次の反応に使用した。 [Reference Example 3]
Figure JPOXMLDOC01-appb-C000144
Step 1: Synthesis of 1- (2,4-difluorophenyl) -N- (3-thienyl) methanimine 2,4-difluorobenzaldehyde 5.00 g, 3-aminothiophene oxalate 6.66 g and triethylamine 7.12 g 100 ml of the THF solution containing the mixture was stirred at room temperature for 3 hours. The insoluble component in the reaction mixture was removed by filtration, and the obtained filtrate was evaporated under reduced pressure. The obtained black oily substance (1.28 g) was the title compound and was used in the next reaction without further purification.
１Ｈ－ＮＭＲ　（ＣＤＣｌ３）　δ：　８．８０　（１Ｈ，　ｓ），　８．１９－８．１７　（１Ｈ，　ｍ），　７．３５－７．３３　（１Ｈ，　ｍ），　７．２３－７．２１　（２Ｈ，　ｍ），　６．９８－６．９６　（１Ｈ，　ｍ），　６．９０－６．８４　（１Ｈ，　ｍ）． 1 H-NMR (CDCl3) δ: 8.80 (1H, s), 8.19-8.17 (1H, m), 7.35-7.33 (1H, m), 7.23-7. 21 (2H, m), 6.98-6.96 (1H, m), 6.90-6.84 (1H, m).
　ステップ２：２－（２，４－ジフルオロフェニル）－１－（３－チエニル）－２，３－ジヒドロピリジン－４（１Ｈ）－オンの合成
　ステップ１で合成した１－（３－チエニル）－２－（２，４－ジフルオロフェニル）－２，３－ジヒドロピリジン－４（１Ｈ）－オンと（（１－メトキシ－２－メチルペンタ－１，３－ジエン－３－イル）オキシ）トリメチルシラン　７．２７ｇを含むアセトニトリル溶液　５０ｍｌを氷冷した後に、４２重量％テトラフルオロホウ酸水溶液　１．５０ｇを加え、氷冷下で１時間撹拌した。反応混合物に飽和炭酸水素ナトリウム水溶液と酢酸エチルを加えて分液した後に、得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が６．６４ｇの橙色アモルファスとして得られた。これ以上精製することなく、次の反応に使用した。 Step 2: Synthesis of 2- (2,4-difluorophenyl) -1- (3-thienyl) -2,3-dihydropyridin-4 (1H) -one 1- (3-thienyl) -2 synthesized in Step 1 -(2,4-Difluorophenyl) -2,3-dihydropyridin-4 (1H) -one and ((1-methoxy-2-methylpenta-1,3-dien-3-yl) oxy) trimethylsilane 7.27 g After ice-cooling 50 ml of an acetonitrile solution containing the above, 1.50 g of a 42 wt% tetrafluoroboric acid aqueous solution was added, and the mixture was stirred under ice-cooling for 1 hour. A saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added to the reaction mixture for liquid separation, and the obtained organic layer was washed with saturated brine and dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 6.64 g of orange amorphous. Used for the next reaction without further purification.
１Ｈ－ＮＭＲ　（ＣＤＣｌ３）　δ：　７．６８　（１Ｈ，　ｄｄ，　Ｊ　＝　７．８，　１．０　Ｈｚ），　７．２８　（１Ｈ，　ｄｄ，　Ｊ　＝　５．４，　３．２　Ｈｚ），　７．２３－７．２１　（１Ｈ，　ｍ），　６．８８－６．８６　（２Ｈ，　ｍ），　６．８２－６．７７　（１Ｈ，　ｍ），　６．５３　（１Ｈ，　ｄｄ，　Ｊ　＝　３．２，　１．５　Ｈｚ），　５．５０　（１Ｈ，　ｄｄ，　Ｊ　＝　７．７，　２．６　Ｈｚ），　５．２６－５．２４　（１Ｈ，　ｍ），　３．２７　（１Ｈ，　ｄｄ，　Ｊ　＝　１６．５，　７．７　Ｈｚ），　２．７５－２．７１　（１Ｈ，　ｍ）． 1 H-NMR (CDCl3) δ: 7.68 (1H, dd, J = 7.8, 1.0 Hz), 7.28 (1H, dd, J = 5.4, 3.2 Hz), 7 .23-7.21 (1H, m), 6.88-6.86 (2H, m), 6.82-6.77 (1H, m), 6.53 (1H, dd, J = 3. 2, 1.5 Hz), 5.50 (1H, dd, J = 7.7, 2.6 Hz), 5.26-5.24 (1H, m), 3.27 (1H, dd, J = 16.5, 7.7 Hz), 2.75-2.71 (1H, m).
［参考例４］
　５－ブロモ―２－（２，４－ジフルオロフェニル）－１－（３－チエニル）－２，３－ジヒドロピリジン－４（１Ｈ）－オンの合成
Figure JPOXMLDOC01-appb-C000145
 [Reference Example 4]
Synthesis of 5-bromo-2- (2,4-difluorophenyl) -1- (3-thienyl) -2,3-dihydropyridin-4 (1H) -one
Figure JPOXMLDOC01-appb-C000145
　２－（２，４－ジフルオロフェニル）－１－（３－チエニル）－２，３－ジヒドロピリジン－４（１Ｈ）－オン　１．３９ｇとＮ－ブロモスクシンイミド　８４９ｍｇを含むクロロホルム溶液　２０ｍｌを室温で４０分間撹拌した。反応混合物に水と酢酸エチルを加えて分液した後に、得られた有機層をチオ硫酸ナトリウム水溶液および飽和食塩水で順次洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が１．５８ｇの黄色アモルファスとして得られた。 20 ml of a chloroform solution containing 2- (2,4-difluorophenyl) -1- (3-thienyl) -2,3-dihydropyridin-4 (1H) -one (1.39 g) and N-bromosuccinimide (849 mg) at room temperature for 40 minutes It was stirred. After water and ethyl acetate were added to the reaction mixture for liquid separation, the obtained organic layer was washed successively with an aqueous sodium thiosulfate solution and saturated brine, and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 1.58 g of a yellow amorphous.
１Ｈ－ＮＭＲ　（ＣＤＣｌ３）　δ：　８．０２－８．０２　（１Ｈ，　ｍ），　７．３０　（１Ｈ，　ｄｄ，　Ｊ　＝　５．４，　３．２　Ｈｚ），　７．２４－７．１７　（１Ｈ，　ｍ），　６．９０－６．８１　（３Ｈ，　ｍ），　６．６２　（１Ｈ，　ｄｄ，　Ｊ　＝　３．２，　１．７　Ｈｚ），　５．５３　（１Ｈ，　ｄｄ，　Ｊ　＝　７．６，　３．２　Ｈｚ），　３．３５　（１Ｈ，　ｄｄ，　Ｊ　＝　１６．６，　７．６　Ｈｚ），　３．０１－２．９６　（１Ｈ，　ｍ）． 1 H-NMR (CDCl3) δ: 8.02-8.02 (1H, m), 7.30 (1H, dd, J = 5.4, 3.2 Hz), 7.24-7.17 ( 1H, m), 6.90-6.81 (3H, m), 6.62 (1H, dd, J = 3.2, 1.7 Hz), 5.53 (1H, dd, J = 7. 6, 3.2 Hz), 3.35 (1H, dd, J = 16.6, 7.6 Hz), 3.01-2.96 (1H, m).
［参考例５］
　５－ブロモ―２－（２，４－ジフルオロフェニル）－１－（３－チエニル）ピリジン－４（１Ｈ）－オンの合成
Figure JPOXMLDOC01-appb-C000146
 [Reference Example 5]
Synthesis of 5-bromo-2- (2,4-difluorophenyl) -1- (3-thienyl) pyridin-4 (1H) -one
Figure JPOXMLDOC01-appb-C000146
　５－ブロモ―２－（２，４－ジフルオロフェニル）－１－（３－チエニル）－２，３－ジヒドロピリジン－４（１Ｈ）－オン　１．５６ｇと二酸化マンガン　５８．４ｇを含むトルエン溶液　１５ｍｌを、還流下で４時間撹拌した。室温まで冷却した後に、反応混合物中の不溶成分をセライト濾過により除去した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が８５．４ｍｇの白色固体として得られた。 15 ml of a toluene solution containing 1.56 g of 5-bromo-2- (2,4-difluorophenyl) -1- (3-thienyl) -2,3-dihydropyridin-4 (1H) -one and 58.4 g of manganese dioxide was added. , Stirred under reflux for 4 hours. After cooling to room temperature, insoluble components in the reaction mixture were removed by Celite filtration. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 85.4 mg as a white solid.
１Ｈ－ＮＭＲ　（ＣＤＣｌ３）　δ：　７．９９　（１Ｈ，　ｓ），　７．２５－７．２１　（２Ｈ，　ｍ），　７．１５－７．１４　（１Ｈ，　ｍ），　６．９０－６．８８　（１Ｈ，　ｍ），　６．７９　（１Ｈ，　ｄｔ，　Ｊ　＝　５．１，　１．１　Ｈｚ），　６．７１－６．６９　（１Ｈ，　ｍ），　６．５３　（１Ｈ，　ｓ）． 1 H-NMR (CDCl3) δ: 7.99 (1H, s), 7.25-7.21 (2H, m), 7.15-7.14 (1H, m), 6.90-6. 88 (1H, m), 6.79 (1H, dt, J = 5.1, 1.1 Hz), 6.71-6.69 (1H, m), 6.53 (1H, s).
［参考例６］
　２－（２，４－ジフルオロフェニル）－３－エチル－１－（３－チエニル）－２，３－ジヒドロピリジン－４（１Ｈ）－オンの合成
Figure JPOXMLDOC01-appb-C000147
 [Reference Example 6]
Synthesis of 2- (2,4-difluorophenyl) -3-ethyl-1- (3-thienyl) -2,3-dihydropyridin-4 (1H) -one
Figure JPOXMLDOC01-appb-C000147
　２－（２，４－ジフルオロフェニル）－１－（３－チエニル）－２，３－ジヒドロピリジン－４（１Ｈ）－オン　３．５０ｇ、ヨウ化エチル　９．６０ｍｌとヘキサメチルリン酸トリアミド　４．６４ｍｌを含むＴＨＦ溶液　５５ｍｌを－１５℃に冷却した。これに１．３ｍｏｌ／ｌのヘキサメチルジシラザンリチウムのＴＨＦ溶液　４．６４ｍｌを１０分かけて滴下した後に、－１５℃で１５分間撹拌した。反応混合物に飽和塩化アンモニウム水溶液と酢酸エチルを加えて分液した後に、得られた有機層を飽和食塩水で洗浄し、硫酸ナトリウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が３．４６ｇの赤色油状物質として得られた。 2- (2,4-difluorophenyl) -1- (3-thienyl) -2,3-dihydropyridin-4 (1H) -one 3.50 g, ethyl iodide 9.60 ml and hexamethylphosphoric triamide 4.64 ml 55 ml of a THF solution containing was cooled to -15 ° C. To this, 4.64 ml of a THF solution of 1.3 mol / l hexamethyldisilazane lithium was added dropwise over 10 minutes, and then the mixture was stirred at -15 ° C for 15 minutes. A saturated ammonium chloride aqueous solution and ethyl acetate were added to the reaction mixture for liquid separation, and the obtained organic layer was washed with saturated brine and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 3.46 g of a red oil.
１Ｈ－ＮＭＲ　（ＣＤＣｌ３）　δ：　７．６４　（１Ｈ，　ｄｄ，　Ｊ　＝　７．９，　１．１　Ｈｚ），　７．３０　（１Ｈ，　ｄｄ，　Ｊ　＝　５．１，　３．２　Ｈｚ），　７．２３－７．２１　（１Ｈ，　ｍ），　６．８８－６．８５　（２Ｈ，　ｍ），　６．８０－６．７６　（１Ｈ，　ｍ），　６．５３　（１Ｈ，　ｄｄ，　Ｊ　＝　３．２，　１．７　Ｈｚ），　５．２８　（１Ｈ，　ｓ），　５．１７　（１Ｈ，　ｄｄ，　Ｊ　＝　７．９，　１．１　Ｈｚ），　２．４４－２．４０　（１Ｈ，　ｍ），　１．８６－１．８０　（２Ｈ，　ｍ），　１．０９　（３Ｈ，　ｔ，　Ｊ　＝　７．４　Ｈｚ）． 1 H-NMR (CDCl3) δ: 7.64 (1H, dd, J = 7.9, 1.1 Hz), 7.30 (1H, dd, J = 5.1, 3.2 Hz), 7 .23-7.21 (1H, m), 6.88-6.85 (2H, m), 6.80-6.76 (1H, m), 6.53 (1H, dd, J = 3. 2, 1.7 Hz), 5.28 (1H, s), 5.17 (1H, dd, J = 7.9, 1.1 Hz), 2.44-2.40 (1H, m), 1.86-1.80 (2H, m), 1.09 (3H, t, J = 7.4 Hz).
［参考例７］
　２－（２，６－ジフルオロフェニル）－３，５－ジメチル―１－（１－メチル－３－ピラゾリル）－２，３－ジヒドロピリジン－４（１Ｈ）－オンの合成
Figure JPOXMLDOC01-appb-C000148
 [Reference Example 7]
Synthesis of 2- (2,6-difluorophenyl) -3,5-dimethyl-1- (1-methyl-3-pyrazolyl) -2,3-dihydropyridin-4 (1H) -one
Figure JPOXMLDOC01-appb-C000148
　２，６－ジフルオロベンズアルデヒド　２．１９ｇに１－メチル－３－アミノピラゾール　１．５０ｇを加えて、室温で２時間撹拌した。次いで、反応混合物にアセトニトリル　４０ｍｌと（（１－メトキシ－２－メチルペンタ－１，３－ジエン－３－イル）オキシ）トリメチルシラン　４．１２ｍｌを順次加えて氷冷した。これに４２重量％テトラフルオロホウ酸水溶液　４８９μｌを加え、氷冷下で６時間撹拌した。反応混合物に飽和炭酸水素ナトリウム水溶液と酢酸エチルを加えて分液した後に、得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が４．６０ｇの白色固体として得られた。これ以上精製することなく、次の反応に使用した。 1.50 g of 1-methyl-3-aminopyrazole was added to 2.19 g of 2,6-difluorobenzaldehyde, and the mixture was stirred at room temperature for 2 hours. Then, 40 ml of acetonitrile and 4.12 ml of ((1-methoxy-2-methylpenta-1,3-dien-3-yl) oxy) trimethylsilane were sequentially added to the reaction mixture, and the mixture was ice-cooled. To this, 489 μl of 42 wt% tetrafluoroboric acid aqueous solution was added, and the mixture was stirred under ice cooling for 6 hours. A saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added to the reaction mixture for liquid separation, and the obtained organic layer was washed with saturated brine and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 4.60 g of a white solid. It was used for the next reaction without further purification.
［参考例８］
　２－（２，６－ジフルオロフェニル）－１－（１－メチル－５－ピラゾリル）－２，３－ジヒドロピリジン－４（１Ｈ）－オンの合成
Figure JPOXMLDOC01-appb-C000149
 [Reference Example 8]
Synthesis of 2- (2,6-difluorophenyl) -1- (1-methyl-5-pyrazolyl) -2,3-dihydropyridin-4 (1H) -one
Figure JPOXMLDOC01-appb-C000149
　２，６－ジフルオロベンズアルデヒド　７８５ｍｇに１－メチル－５－アミノピラゾール　５３７ｍｇを加えて、室温で３０分間撹拌した。次いで、反応混合物にジクロロメタン　１０ｍｌと３－（ｔｅｒｔ－ブチルジメチルシリルオキシ）－Ｎ，Ｎ－ジメチル－１，３－ブタジエン－１－アミン　１．９８ｍｌを順次加えて、室温で７日間撹拌した。反応混合物を減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が１５６ｍｇの黄色固体として得られた。 To 785 mg of 2,6-difluorobenzaldehyde, 537 mg of 1-methyl-5-aminopyrazole was added, and the mixture was stirred at room temperature for 30 minutes. Then, 10 ml of dichloromethane and 1.98 ml of 3- (tert-butyldimethylsilyloxy) -N, N-dimethyl-1,3-butadiene-1-amine were sequentially added to the reaction mixture, and the mixture was stirred at room temperature for 7 days. The solvent was distilled off from the reaction mixture under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 156 mg as a yellow solid.
１Ｈ－ＮＭＲ　（ＣＤＣｌ３）　δ：　７．２４　（１Ｈ，　ｄ，　Ｊ　＝　２．０　Ｈｚ），　７．０６　（１Ｈ，　ｄｄ，　Ｊ　＝　７．９，　０．６　Ｈｚ），　６．８４－６．７９　（２Ｈ，　ｍ），　５．９２　（１Ｈ，　ｄ，　Ｊ　＝　２．０　Ｈｚ），　５．５３　（１Ｈ，　ｄｄ，　Ｊ　＝　１４．８，　４．９　Ｈｚ），　５．３７　（１Ｈ，　ｄｄ，　Ｊ　＝　７．９，　１．１　Ｈｚ），　３．７７　（３Ｈ，　ｓ），　３．４２－３．３４　（１Ｈ，　ｍ），　２．６６　（１Ｈ，　ｄｄｄ，　Ｊ　＝　１６．６，　４．９，　１．２　Ｈｚ）． 1 H-NMR (CDCl3) δ: 7.24 (1H, d, J = 2.0 Hz), 7.06 (1H, dd, J = 7.9, 0.6 Hz), 6.84-6 .79 (2H, m), 5.92 (1H, d, J = 2.0 Hz), 5.53 (1H, dd, J = 14.8, 4.9 Hz), 5.37 (1H, 1H, dd, J = 7.9, 1.1 Hz), 3.77 (3H, s), 3.42-3.34 (1H, m), 2.66 (1H, ddd, J = 16.6). 4.9, 1.2 Hz).
［参考例９］
　２－（２，６－ジフルオロフェニル）－３－メチル－１－（１－メチル－５－ピラゾリル）－２，３－ジヒドロピリジン－４（１Ｈ）－オンの合成
Figure JPOXMLDOC01-appb-C000150
 [Reference Example 9]
Synthesis of 2- (2,6-difluorophenyl) -3-methyl-1- (1-methyl-5-pyrazolyl) -2,3-dihydropyridin-4 (1H) -one
Figure JPOXMLDOC01-appb-C000150
　２－（２，６－ジフルオロフェニル）－１－（１－メチル－５－ピラゾリル）－２，３－ジヒドロピリジン－４（１Ｈ）－オン　４０５ｍｇ、ヨウ化メチル　１．７４ｍｌとヘキサメチルリン酸トリアミド　４８７μｌを含むＴＨＦ溶液　４ｍｌを－７８℃に冷却した。これに１．３ｍｏｌ／ｌのヘキサメチルジシラザンリチウムのＴＨＦ溶液　２．１５ｍｌを滴下して室温まで昇温した後に、４時間撹拌した。反応混合物に飽和塩化アンモニウム水溶液と酢酸エチルを加えて分液した後に、得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が３１２ｍｇの淡オレンジ色油状固体として得られた。 2- (2,6-difluorophenyl) -1- (1-methyl-5-pyrazolyl) -2,3-dihydropyridin-4 (1H) -one 405 mg, methyl iodide 1.74 ml and hexamethylphosphoric triamide 487 μl 4 ml of a THF solution containing was cooled to -78 ° C. To this, 2.15 ml of a 1.3 mol / l lithium hexamethyldisilazane THF solution was added dropwise, and the temperature was raised to room temperature, followed by stirring for 4 hours. A saturated ammonium chloride aqueous solution and ethyl acetate were added to the reaction mixture for liquid separation, and the obtained organic layer was washed with saturated brine and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 312 mg of a pale orange oily solid.
１Ｈ－ＮＭＲ　（ＣＤＣｌ３）　δ：　７．２３－７．２１　（２Ｈ，　ｍ），　７．０４　（１Ｈ，　ｄ，　Ｊ　＝　７．８　Ｈｚ），　６．８２－６．８０　（２Ｈ，　ｍ），　５．９２　（１Ｈ，　ｄ，　Ｊ　＝　２．０　Ｈｚ），　５．３８　（１Ｈ，　ｄ，　Ｊ　＝　７．８　Ｈｚ），　５．１５　（１Ｈ，　ｄ，　Ｊ　＝　１３．９　Ｈｚ），　３．７７　（３Ｈ，　ｓ），　３．２８－３．２５　（１Ｈ，　ｍ），　１．０４　（３Ｈ，　ｄ，　Ｊ　＝　６．８　Ｈｚ）． 1 H-NMR (CDCl3) δ: 7.23-7.21 (2H, m), 7.04 (1H, d, J = 7.8 Hz), 6.82-6.80 (2H, m) , 5.92 (1H, d, J = 2.0 Hz), 5.38 (1H, d, J = 7.8 Hz), 5.15 (1H, d, J = 13.9 Hz), 3 .77 (3H, s), 3.28-3.25 (1H, m), 1.04 (3H, d, J = 6.8 Hz).
［参考例１０］
　５－ブロモ－２－（２，６－ジフルオロフェニル）－３－メチル－１－（１－メチル－５－ピラゾリル）－２，３－ジヒドロピリジン－４（１Ｈ）－オンの合成
Figure JPOXMLDOC01-appb-C000151
 [Reference Example 10]
Synthesis of 5-bromo-2- (2,6-difluorophenyl) -3-methyl-1- (1-methyl-5-pyrazolyl) -2,3-dihydropyridin-4 (1H) -one
Figure JPOXMLDOC01-appb-C000151
　２－（２，６－ジフルオロフェニル）－３－メチル－１－（１－メチル－５－ピラゾリル）－２，３－ジヒドロピリジン－４（１Ｈ）－オン　３１２ｍｇとＮ－ブロモスクシンイミド　２０２ｍｇを含む四塩化炭素溶液　４ｍｌを室温で１時間撹拌した。反応混合物にチオ硫酸ナトリウム水溶液とジクロロメタンを加えて分液した後に、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が３４６ｍｇの無色油状物質として得られた。 2- (2,6-Difluorophenyl) -3-methyl-1- (1-methyl-5-pyrazolyl) -2,3-dihydropyridin-4 (1H) -one 312 mg and N-bromosuccinimide 202 mg tetrachloride 4 ml of carbon solution was stirred at room temperature for 1 hour. An aqueous sodium thiosulfate solution and dichloromethane were added to the reaction mixture to separate the layers, followed by drying over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 346 mg of colorless oil.
１Ｈ－ＮＭＲ　（ＣＤＣｌ３）　δ：　７．４８　（１Ｈ，　ｓ），　７．２４－７．２３　（２Ｈ，　ｍ），　６．８４－６．８１　（２Ｈ，　ｍ），　５．９６　（１Ｈ，　ｄ，　Ｊ　＝　２．１　Ｈｚ），　５．２２　（１Ｈ，　ｄ，　Ｊ　＝　１４．１　Ｈｚ），　３．７８　（３Ｈ，　ｓ），　３．４１－３．３５　（１Ｈ，　ｍ），　１．１１　（３Ｈ，　ｄ，　Ｊ　＝　７．０　Ｈｚ）． 1 H-NMR (CDCl3) δ: 7.48 (1H, s), 7.24-7.23 (2H, m), 6.84-6.81 (2H, m), 5.96 (1H, d, J = 2.1 Hz), 5.22 (1H, d, J = 14.1 Hz), 3.78 (3H, s), 3.41-3.35 (1H, m), 1. 11 (3H, d, J = 7.0 Hz).
［参考例１１］
Figure JPOXMLDOC01-appb-C000152
 [Reference Example 11]
Figure JPOXMLDOC01-appb-C000152
　ステップ１：Ｎ－（（２，６－ジフルオロフェニル）（エトキシ）メチル）－１，３，４－チアジアゾール－２－アミンの合成
　２，６－ジフルオロベンズアルデヒド　５．００ｇ、２－アミノ－１，３，４－チアジアゾール　２．９７ｇとピペリジン　１４６μｌを含むエタノール溶液　２５ｍｌを７５℃で５時間撹拌した。室温まで冷却した後に、減圧下で溶媒留去し、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が６．６０ｇの黄色固体として得られた。これ以上精製することなく、次の反応に使用した。 Step 1: Synthesis of N-((2,6-difluorophenyl) (ethoxy) methyl) -1,3,4-thiadiazol-2-amine 2,6-difluorobenzaldehyde 5.00 g, 2-amino-1,3 25 ml of an ethanol solution containing 2.97 g of 4-thiadiazole and 146 μl of piperidine was stirred at 75 ° C. for 5 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 6.60 g of a yellow solid. Used for the next reaction without further purification.
１Ｈ－ＮＭＲ　（ＣＤＣｌ３）　δ：　８．５０　（１Ｈ，　ｓ），　７．３３－７．３１　（１Ｈ，　ｍ），　６．９７－６．９５　（２Ｈ，　ｍ），　６．４３－６．４１　（１Ｈ，　ｍ），　３．８２－３．７８　（１Ｈ，　ｍ），　３．６６－３．６２　（１Ｈ，　ｍ），　１．２４　（３Ｈ，　ｔ，　Ｊ　＝　７．１　Ｈｚ）． 1 H-NMR (CDCl3) δ: 8.50 (1H, s), 7.33-7.31 (1H, m), 6.97-6.95 (2H, m), 6.43-6. 41 (1H, m), 3.82-3.78 (1H, m), 3.66-3.62 (1H, m), 1.24 (3H, t, J = 7.1 Hz).
　ステップ２：１－（（１，３，４－チアジアゾール－２－イル）アミノ）－１－（２，６－ジフルオロフェニル－５－メトキシ－２，４－ジメチルペンタ－１，４－ジエン－３－オンの合成
　ステップ１で得られたＮ－（（２，６－ジフルオロフェニル）（エトキシ）メチル）－１，３，４－チアジアゾール－２－アミン　６．６０ｇと（（１－メトキシ－２－メチルペンタ－１，３－ジエン－３－イル）オキシ）トリメチルシラン　７．３１ｇを含むアセトニトリル溶液　１３２ｍｌを氷冷し、４２重量％テトラフルオロホウ酸水溶液　１．０１ｍｌを加え、室温で３時間撹拌した。反応混合物に飽和炭酸水素ナトリウム水溶液と酢酸エチルを加えて分液した後に、得られた有機層を飽和食塩水で洗浄し、硫酸ナトリウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が１：１のジアステレオマー混合物の２．３８ｇの淡黄色固体として得られた。これ以上精製することなく、次の反応に使用した。 Step 2: 1-((1,3,4-thiadiazol-2-yl) amino) -1- (2,6-difluorophenyl-5-methoxy-2,4-dimethylpenta-1,4-diene-3 Synthesis of N-one 6.60 g of N-((2,6-difluorophenyl) (ethoxy) methyl) -1,3,4-thiadiazol-2-amine obtained in Step 1 and ((1-methoxy-2- 132 ml of an acetonitrile solution containing 7.31 g of methylpenta-1,3-dien-3-yl) oxy) trimethylsilane was ice-cooled, 1.01 ml of a 42 wt% tetrafluoroboric acid aqueous solution was added, and the mixture was stirred at room temperature for 3 hours. A saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added to the reaction mixture to separate the layers, and the obtained organic layer was washed with saturated brine and dried over sodium sulfate. After evaporation, the resulting residue was purified by silica gel column chromatography to give the title compound as a pale yellow solid, 2.38 g of a 1: 1 mixture of diastereomers, without further purification. , Used for the next reaction.
　１Ｈ－ＮＭＲ　（ＣＤＣｌ３）　δ：　８．４０　（０．５Ｈ，　ｓ），　８．３７　（０．５Ｈ，　ｓ），　７．３０－７．３０　（０．５Ｈ，　ｍ），　７．２６－７．２４　（０．５Ｈ，　ｍ），　６．９１－６．８９　（１Ｈ，　ｍ），　６．８５－６．８３　（１Ｈ，　ｍ），　６．４５－６．４４　（０．５Ｈ，　ｍ），　６．２９－６．２７　（０．５Ｈ，　ｍ），　５．３２－５．３０　（０．５Ｈ，　ｍ），　５．１０－５．０８　（０．５Ｈ，　ｍ），　３．８８　（１．５Ｈ，　ｓ），　３．８６　（１．５Ｈ，　ｓ），　３．８２－３．７８　（１Ｈ，　ｍ），　３．６６－３．６３　（１Ｈ，　ｍ），　１．７０　（１．５Ｈ，　ｓ），　１．５５　（１．５Ｈ，　ｓ），　１．３５－１．３５　（１．５Ｈ，　ｍ），　１．０５　（１．５Ｈ，　ｄ，　Ｊ　＝　６．７　Ｈｚ）． 1 H-NMR (CDCl3) δ: 8.40 (0.5H, s), 8.37 (0.5H, s), 7.30-7.30 (0.5H, m), 7.26- 7.24 (0.5H, m), 6.91-6.89 (1H, m), 6.85-6.83 (1H, m), 6.45-6.44 (0.5H, m) ), 6.29-6.27 (0.5H, m), 5.32-5.30 (0.5H, m), 5.10-5.08 (0.5H, m), 3.88. (1.5H, s), 3.86 (1.5H, s), 3.82-3.78 (1H, m), 3.66-3.63 (1H, m), 1.70 (1 .5H, s), 1.55 (1.5H, s), 1.35-1.35 (1.5H, m), 1.05 (1.5H, d, J = 6.7 Hz).
［参考例１２］
Figure JPOXMLDOC01-appb-C000153
 [Reference Example 12]
Figure JPOXMLDOC01-appb-C000153
　ステップ１：Ｎ－ｏ－トルイル－１－（２，４，６－トリフルオロフェニル）メタンイミンの合成
　２，４，６－トリフルオロベンズアルデヒド　３．００ｇに、オルトトルイジン　２．００ｇと硫酸マグネシウム　１．４０ｇを含むジクロロエタン溶液　１５ｍｌを、還流下で３時間撹拌した。室温まで冷却した後に、反応混合物中の硫酸マグネシウムを濾過にて除去し、得られた濾液を減圧下で溶媒留去した。得られた橙色固体は表題の化合物であり、これ以上精製することなく、次の反応に使用した。 Step 1: Synthesis of N-o-toluyl-1- (2,4,6-trifluorophenyl) methanimine To 3.00 g of 2,4,6-trifluorobenzaldehyde, 2.00 g of orthotoluidine and 1.40 g of magnesium sulfate. 15 ml of a dichloroethane solution containing was stirred under reflux for 3 hours. After cooling to room temperature, magnesium sulfate in the reaction mixture was removed by filtration, and the obtained filtrate was evaporated under reduced pressure. The resulting orange solid was the title compound and was used in the next reaction without further purification.
　１Ｈ－ＮＭＲ　（ＣＤＣｌ３）　δ：　８．５０　（１Ｈ，　ｓ），　７．２５－７．２１　（２Ｈ，　ｍ），　７．１７－７．１４　（１Ｈ，　ｍ），　６．９２　（１Ｈ，　ｄ，　Ｊ　＝　７．８　Ｈｚ），　６．７９－６．７７　（２Ｈ，　ｍ），　２．３６　（３Ｈ，　ｓ）． 1 H-NMR (CDCl3) δ: 8.50 (1H, s), 7.25-7.21 (2H, m), 7.17-7.14 (1H, m), 6.92 (1H, d, J = 7.8 Hz), 6.79-6.77 (2H, m), 2.36 (3H, s).
　ステップ２：３，５－ジメチル－１－（ｏ－トルイル）－２－（２，４，６－トリフルオロフェニル）－２，３－ジヒドロピリジン－４（１Ｈ）－オンの合成
　Ｎ－ｏ－トルイル－１－（２，４，６－トリフルオロフェニル）メタンイミン　５００ｍｇと（（１－メトキシ－２－メチルペンタ－１，３－ジエン－３－イル）オキシ）トリメチルシラン　３．０２ｍｌを含むアセトニトリル溶液　５ｍｌを氷冷し、４２重量％テトラフルオロホウ酸水溶液　８６ｍｇを加えた後に、氷冷下で１時間撹拌した。さらに、氷冷から室温まで昇温して１．５時間撹拌した。反応混合物に飽和炭酸水素ナトリウム水溶液と酢酸エチルを加えて分液した後に、得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が７０４ｍｇの無色油状物質として得られた。これ以上精製することなく、次の反応に使用した。 Step 2: Synthesis of 3,5-dimethyl-1- (o-toluyl) -2- (2,4,6-trifluorophenyl) -2,3-dihydropyridin-4 (1H) -one No-toluyl 5 ml of an acetonitrile solution containing 500 mg of 1- (2,4,6-trifluorophenyl) methanimine and 3.02 ml of ((1-methoxy-2-methylpenta-1,3-dien-3-yl) oxy) trimethylsilane was added. After cooling with ice and adding 86 mg of a 42 wt% tetrafluoroboric acid aqueous solution, the mixture was stirred under ice cooling for 1 hour. Furthermore, the temperature was raised from ice-cooling to room temperature and the mixture was stirred for 1.5 hours. A saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added to the reaction mixture for liquid separation, and the obtained organic layer was washed with saturated brine and dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 704 mg of a colorless oil. Used for the next reaction without further purification.
［参考例１３］
　３，５－ジメチル－１－（ｏ－トルイル）－２－（２，４，６－トリフルオロフェニル）ピリジン－４（１Ｈ）－オンの合成
Figure JPOXMLDOC01-appb-C000154
 [Reference Example 13]
Synthesis of 3,5-dimethyl-1- (o-toluyl) -2- (2,4,6-trifluorophenyl) pyridin-4 (1H) -one
Figure JPOXMLDOC01-appb-C000154
　参考例１２で得た３，５－ジメチル－１－（ｏ－トルイル）－２－（２，４，６－トリフルオロフェニル）－２，３－ジヒドロピリジン－４（１Ｈ）－オン　７０４ｍｇを含む酢酸溶液　７ｍｌに、臭素　１５５μｌを加えて８０℃で３０分間撹拌した。反応混合物を室温まで冷却した後に、飽和炭酸水素ナトリウム水溶液と酢酸エチルを加えて分液した。得られた有機層を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥した。減圧下で溶媒留去した後に、得られた残渣をシリカゲルカラムクロマトグラフィーにて精製した。表題の化合物が３８８ｍｇの白色固体として得られた。 Acetic acid containing 704 mg of 3,5-dimethyl-1- (o-toluyl) -2- (2,4,6-trifluorophenyl) -2,3-dihydropyridin-4 (1H) -one obtained in Reference Example 12 Bromine (155 μl) was added to the solution (7 ml), and the mixture was stirred at 80 ° C. for 30 minutes. The reaction mixture was cooled to room temperature, saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added, and the layers were separated. The obtained organic layer was washed with saturated saline and dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 388 mg as a white solid.
　１Ｈ－ＮＭＲ　（ＣＤＣｌ３）　δ：　７．３３　（１Ｈ,　ｄ,　Ｊ　＝　１．２　Ｈｚ）,　７．２０　（２Ｈ,　ｔｄｄ,　Ｊ　＝　８．８,　５．９,　１．９　Ｈｚ）,　７．１２－７．０５　（２Ｈ,　ｍ）,　６．５９－６．５７　（１Ｈ,　ｍ）,　６．５５－６．５１　（１Ｈ, ｍ）,　２．１４　（３Ｈ,　ｄ,　Ｊ　＝　１．２　Ｈｚ）,　２．１３　（３Ｈ,　ｄ,　Ｊ　＝　０．９　Ｈｚ）,　１．９１　（３Ｈ,　ｓ）. 1 H-NMR (CDCl3) δ: 7.33 (1H, d, J = 1.2 Hz), 7.20 (2H, tdd, J = 8.8, 5.9, 1.9 Hz), 7 .12-7.05 (2H, m), 6.59-6.57 (1H, m), 6.55-6.51 (1H, m), 2.14 (3H, d, J = 1. 2 Hz), 2.13 (3H, d, J = 0.9 Hz), 1.91 (3H, s).
　表４に前記の実施例に準じて合成した式（１）で表される化合物を示すが、本発明はこれらに限定されるものではない。なお、表４中における化合物は、式（Ａ）で表される。
Figure JPOXMLDOC01-appb-C000155
 Table 4 shows compounds represented by the formula (1) synthesized according to the above Examples, but the present invention is not limited thereto. The compounds in Table 4 are represented by formula (A).
Figure JPOXMLDOC01-appb-C000155
Figure JPOXMLDOC01-appb-T000156
Figure JPOXMLDOC01-appb-T000156
Figure JPOXMLDOC01-appb-T000157
Figure JPOXMLDOC01-appb-T000157
　次に、表４に記載の化合物に関して、表５にそれらの１Ｈ－ＮＭＲデータを示す。 Next, regarding the compounds described in Table 4, Table 1 shows their 1 H-NMR data.
Figure JPOXMLDOC01-appb-T000158
Figure JPOXMLDOC01-appb-T000158
Figure JPOXMLDOC01-appb-T000159
Figure JPOXMLDOC01-appb-T000159
Figure JPOXMLDOC01-appb-T000160
Figure JPOXMLDOC01-appb-T000160
　次に、本発明化合物が植物病害に有効であることを具体的に示すが、これらの例に限定されるものではない。 Next, it will be specifically shown that the compound of the present invention is effective against plant diseases, but the present invention is not limited to these examples.
　以下に示した試験例の発病程度について、無発病の植物の発病程度を０、薬剤無処理区の植物の発病程度を３として、０．０５ごとの発病程度の評価を行った。また、発病程度から以下の計算式に従って防除価を算出した。
＜防除価＞
　防除価＝１００｛１－（ｎ／３）｝
　ｎ＝各薬剤処理区の発病程度 With regard to the degree of disease occurrence in the test examples shown below, the degree of disease occurrence was evaluated for each 0.05, with the disease severity of plants having no disease as 0 and the disease severity of plants in the drug-untreated section as 3. Further, the control value was calculated from the degree of onset according to the following formula.
<Control value>
Control value = 100 {1- (n / 3)}
n = degree of illness in each drug treatment area
［試験例Ａ］　イネいもち病
　供試植物（イネ品種：幸風）の種子を播種後、第２葉が展開するまで栽培した。試験では、本発明化合物をジメチルスルホキシド－メタノール混合溶液（容積比：９／１）に溶解し、２５０ｐｐｍの濃度となるように井戸水で希釈して薬液を得た。得られた薬液を供試植物に散布した（２．５ｍｌ／ポット）。薬液が乾燥した後の植物に、１～２×１０５個／ｍｌのイネいもち病菌（Ｍａｇｎａｐｏｒｔｈｅ　ｇｒｉｓｅａ）の分生胞子懸濁液を噴霧接種した。接種後、室温が２０～２３℃の湿室に約２４時間放置し、発病を促した。接種６～１０日後の発病程度を調査し、薬液の効果を評価した。 [Test Example A] Rice blast After sown with seeds of a test plant (rice variety: Kofu), it was cultivated until the second leaf developed. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). The plant after the drug solution was dried was inoculated with 1 to 2 × 10 5 cells / ml of a conidia suspension of the rice blast fungus (Magnaporthe grisea) by spraying. After inoculation, the plant was left in a moist chamber with a room temperature of 20 to 23 ° C. for about 24 hours to promote disease onset. The degree of disease onset 6 to 10 days after the inoculation was investigated to evaluate the effect of the drug solution.
　その結果、以下に示した化合物が５０％より大きい防除価を示した。
化合物番号：１、２、３、４、８、９、１０、１９、２２、２３、２４、２５、２９、３０、３３．３４、３５、３７、３８、３９、４０、４１、４４、４５、４６、４８、５１、５２、５３ As a result, the compounds shown below showed a control value of more than 50%.
Compound number: 1, 2, 3, 4, 8, 9, 10, 19, 22, 23, 24, 25, 29, 30, 33.34, 35, 37, 38, 39, 40, 41, 44, 45 , 46, 48, 51, 52, 53
［試験例Ｂ］　トマト灰色かび病
　供試植物（トマト品種：大型福寿）の種子を播種後、本葉が３～５枚展開するまで栽培した。試験では、本発明化合物をジメチルスルホキシド－メタノール混合溶液（容積比：９／１）に溶解し、２５０ｐｐｍの濃度となるように井戸水で希釈して薬液を得た。得られた薬液を供試植物に散布した（２．５ｍｌ／ポット）。薬液が乾燥した後の植物に、４～８×１０５個／ｍｌの灰色かび病菌（Ｂｏｔｒｙｔｉｓ　ｃｉｎｅｒｅａ）の分生胞子懸濁液を噴霧接種した。接種後、室温が２０～２３℃の湿室に約４８時間放置し、発病を促した。接種２～３日後の発病程度を調査し、薬液の効果を評価した。 [Test Example B] Tomato gray mold disease After sowing seeds of a test plant (tomato variety: large Fukuju), 3 to 5 true leaves were cultivated. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the drug solution was dried, the plants were spray-inoculated with a conidial suspension of 4-8 × 10 5 cells / ml of Botrytis cinerea. After inoculation, the plant was left in a wet room at a room temperature of 20 to 23 ° C. for about 48 hours to promote the onset of disease. The degree of disease onset 2 to 3 days after the inoculation was investigated to evaluate the effect of the drug solution.
　その結果、以下に示した化合物が５０％より大きい防除価を示した。
化合物番号：１、２、３、４、５、６、８、９、１０、１１、１２、１４、１５、１６、１７、１８、１９、２０、２１、２２、２３、２４，２５、２９、３０、３１、３３、３４、３５、３６、３７、３８、３９、４０、４１、４２、４４、４５、５３、５５ As a result, the compounds shown below showed a control value of more than 50%.
Compound number: 1, 2, 3, 4, 5, 6, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 29 , 30, 31, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 44, 45, 53, 55.
［試験例Ｃ］　キャベツ黒すす病
　供試植物（キャベツ品種：四季穫）の種子を播種後、子葉が展開するまで栽培した。試験では、本発明化合物をジメチルスルホキシド－メタノール混合溶液（容積比：９／１）に溶解し、２５０ｐｐｍの濃度となるように井戸水で希釈して薬液を得た。得られた薬液を供試植物に散布した（２．５ｍｌ／ポット）。薬液が乾燥した後の植物に、４～８×１０５個／ｍｌのキャベツ黒すす病菌（Ａｌｔｅｒｎａｉａ　ｂｒａｓｓｉｃｉｃｏｌａ）の分生胞子懸濁液を噴霧接種した。接種後、室温が２０～２３℃の湿室に約４８時間放置し、発病を促した。接種２～３日後の発病程度を調査し、薬液の効果を評価した。 [Test Example C] Cabbage black spot disease Seeds of a test plant (cabbage variety: four seasons harvest) were sown and then cultivated until cotyledons developed. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). The plants after the drug solution had been dried were spray-inoculated with a conidial suspension of 4-8 × 10 5 cells / ml of cabbage black scab (Alternia brassicicola). After inoculation, the plant was left in a wet room at a room temperature of 20 to 23 ° C. for about 48 hours to promote the onset of disease. The degree of disease onset 2 to 3 days after the inoculation was investigated to evaluate the effect of the drug solution.
　その結果、以下に示した化合物が５０％より大きい防除価を示した。
化合物番号：１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２２、２３、２４、２５、２６、２８、２９、３０、３１、３２、３３、３４、３５、３６、３７、３８、３９、４０、４１、４３、４４、４５、４７、４８、４９、５０、５１、５２、５４、５５、５６、５７、５８ As a result, the compounds shown below showed a control value of more than 50%.
Compound number: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 22, 23, 24, 25, 26 , 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 43, 44, 45, 47, 48, 49, 50, 51, 52, 54, 55. , 56, 57, 58
［試験例Ｄ］　オオムギうどんこ病
　供試植物（オオムギ品種：赤神力）の種子を播種後、第１葉が展開するまで栽培した。試験では、本発明化合物をジメチルスルホキシド－メタノール混合溶液（容積比：９／１）に溶解し、２５０ｐｐｍの濃度となるように井戸水で希釈して薬液を得た。得られた薬液を供試植物に散布した（２．５ｍｌ／ポット）。薬液が乾燥した後の植物に、オオムギうどんこ病菌（Ｂｌｕｍｅｒｉａ　ｇｒａｍｉｎｉｓ　ｆ．ｓｐ．ｈｏｒｄｅｉ）の分生胞子を叩き落して接種した。接種後、６～１０日後の発病程度を調査し、その効果を評価した。 [Test Example D] Barley powdery mildew After planting seeds of a test plant (barley variety: Akakami Riki), it was cultivated until the first leaf developed. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the chemical solution was dried, the conidia of barley powdery mildew (Blumeria graminis f.sp.hordei) were beaten and inoculated to the plants. The degree of illness was investigated 6 to 10 days after the inoculation, and its effect was evaluated.
　その結果、以下に示した化合物が５０％より大きい防除価を示した。
化合物番号：１、２、３、４、１０、１７、１９、２４、２５、３０、３４、４０、４１、４４、４５ As a result, the compounds shown below showed a control value of more than 50%.
Compound number: 1, 2, 3, 4, 10, 17, 19, 24, 25, 30, 34, 40, 41, 44, 45
［試験例Ｅ］　コムギ赤さび病
　供試植物（コムギ品種：農林６１号）の種子を播種後、第１葉が展開するまで栽培した。試験では、本発明化合物をジメチルスルホキシド－メタノール混合溶液（容積比：９／１）に溶解し、２５０ｐｐｍの濃度となるように井戸水で希釈して薬液を得た。得られた薬液を供試植物に散布した（２．５ｍｌ／ポット）。薬液が乾燥した後の植物に、１～２×１０５個／ｍｌのコムギ赤さび病菌（Ｐｕｃｃｉｎｉａ　ｒｅｃｏｎｄｉｔａ）の夏胞子懸濁液を噴霧接種した。接種後、室温が２０～２３℃の湿室に約２４時間放置し、発病を促した。接種７～１０日後の発病程度を調査し、薬液の効果を評価した。 [Test Example E] Wheat leaf rust Seeds of a test plant (wheat variety: Norin 61) were sown and then cultivated until the first leaves developed. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the drug solution was dried, the plants were inoculated with 1 to 2 × 10 5 pieces / ml of a spore suspension of Puccinia recondita. After inoculation, the plant was left in a moist chamber with a room temperature of 20 to 23 ° C. for about 24 hours to promote disease onset. The degree of disease onset 7 to 10 days after the inoculation was investigated to evaluate the effect of the drug solution.
　その結果、以下に示した化合物が５０％より大きい防除価を示した。
化合物番号：１、２、３、４、５、６、８、９、１０、１１、１２、１６、１７、１８、１９、２２、２３、２４、２５、２７、２９、３０、３１、３４、３５、３６、３７、３８、３９、４０、４１、４４、４５、４９、５１、５２、５７ As a result, the compounds shown below showed a control value of more than 50%.
Compound number: 1, 2, 3, 4, 5, 6, 8, 9, 10, 11, 12, 16, 17, 18, 19, 22, 23, 24, 25, 27, 29, 30, 31, 34 , 35, 36, 37, 38, 39, 40, 41, 44, 45, 49, 51, 52, 57.
［試験例Ｆ］　キュウリ炭疽病
　供試植物（キュウリ品種：相模半白）の種子を播種後、本葉が１枚展開するまで栽培した。試験では、本発明化合物をジメチルスルホキシド－メタノール混合溶液（容積比：９／１）に溶解し、２５０ｐｐｍの濃度となるように井戸水で希釈して薬液を得た。得られた薬液を供試植物に散布した（２．５ｍｌ／ポット）。薬液が乾燥した後の植物に、２～４×１０５個／ｍｌのキュウリ炭疽病菌（Ｃｏｌｌｅｔｏｔｒｉｃｈｕｍ　ｏｒｂｉｃｕｌａｒｅ）の分生胞子懸濁液を噴霧接種した。接種後、室温が２０～２３℃の湿室に約２４時間放置し、発病を促した。接種６～１０日後の発病程度を調査し、薬液の効果を評価した。 [Test Example F] Cucumber anthracnose After seeding the seeds of a test plant (cucumber variety: Sagamihanjiro), it was cultivated until one true leaf developed. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the drug solution was dried, the plants were inoculated with 2 to 4 × 10 5 cells / ml of a conidia suspension of anthrax of Cucumber (Colletotrichum orbiculare) by spraying. After inoculation, the plant was left in a moist chamber with a room temperature of 20 to 23 ° C. for about 24 hours to promote disease onset. The degree of disease onset 6 to 10 days after the inoculation was investigated to evaluate the effect of the drug solution.
　その結果、以下に示した化合物が５０％より大きい防除価を示した。
化合物番号：１、２、３、４、６、１４、１５、１９、４１、４４、４７、４８ As a result, the compounds shown below showed a control value of more than 50%.
Compound number: 1, 2, 3, 4, 6, 14, 15, 19, 41, 44, 47, 48
［試験例Ｇ］　ブドウべと病
　供試植物（ブドウ品種：ネオマスカット）の種子を播種後、本葉が３～４枚展開するまで栽培した。試験では、本発明化合物をジメチルスルホキシド－メタノール混合溶液（容積比：９／１）に溶解し、２５０ｐｐｍの濃度となるように井戸水で希釈して薬液を得た。得られた薬液を供試植物に散布した（２．５ｍｌ／ポット）。薬液が乾燥した後の植物に、１～２×１０４個／ｍｌのブドウべと病菌（Ｐｌａｓｍｏｐａｒａ　ｖｉｔｉｃｏｌａ）の遊走子の懸濁液を噴霧接種した。接種後、室温が２０℃の湿室に約２４時間放置し、発病を促した。接種７～１０日後の発病程度を調査し、薬液の効果を評価した。 [Test Example G] Grape downy mildew After sowing seeds of a test plant (grape variety: Neo Muscat), the seedlings were cultivated until 3 to 4 true leaves were developed. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the drug solution was dried, the plants were spray-inoculated with a suspension of zoospores of Plasmopara viticola at 1 to 2 × 10 4 cells / ml. After the inoculation, the cells were allowed to stand in a wet room at room temperature of 20 ° C. for about 24 hours to promote the onset of the disease. The degree of disease onset 7 to 10 days after the inoculation was investigated to evaluate the effect of the drug solution.
　その結果、以下に示した化合物が５０％より大きい防除価を示した。
化合物番号：１、２、３、４、６、１４、１５、１９、４１、４４、４７、４８ As a result, the compounds shown below showed a control value of more than 50%.
Compound number: 1, 2, 3, 4, 6, 14, 15, 19, 41, 44, 47, 48
　式（１）で表される化合物の土壌中での動態は、公知の方法で分析できる。以下に分析方法を例示するが、この方法に限定されるものではない。 The behavior of the compound represented by the formula (1) in soil can be analyzed by a known method. The analysis method is illustrated below, but the method is not limited to this.
　乾燥土（野洲土壌：砂壌土）５ｇ相当の土壌を５０ｍＬ容器へ入れ、最大容水量の５０－６０％になるように水を添加し、２０℃の恒温器で約２週間インキュベートした。得られた試験土壌へ式（１）で表される化合物を２０μｇ／ｍＬ含有するメタノール溶液を処理し、処理直後、１５、３０、６０、９０日後の減衰を分析した。 Soil equivalent to 5 g of dry soil (Yasu soil: sandy loam soil) was put in a 50 mL container, water was added so as to be 50-60% of the maximum water capacity, and incubated in a thermostat at 20 ° C. for about 2 weeks. The obtained test soil was treated with a methanol solution containing 20 μg / mL of the compound represented by the formula (1), and the decay was analyzed immediately after the treatment and 15, 30, 60 and 90 days later.
　式（１）で表される化合物の土壌中濃度は、土壌に含水アセトニトリルを加えて超音波分散により化合物を抽出し、上澄み液を高速液体クロマトグラフィーで分析することで算出した。結果を表６に示す。 The concentration of the compound represented by formula (1) in the soil was calculated by adding hydrous acetonitrile to the soil, extracting the compound by ultrasonic dispersion, and analyzing the supernatant by high performance liquid chromatography. Table 6 shows the results.
Figure JPOXMLDOC01-appb-T000161
Figure JPOXMLDOC01-appb-T000161
　上記の方法を用いると、Ｚがチエニル基である化合物（化合物番号２と４）は、土壌中において９０日で３０～６０％分解した。一方で、参考例１３で得られたＺがフェニル基である化合物（比較例化合物）は、土壌中において９０日で分解が観測されなかった。すなわち、Ｚに硫黄原子等のヘテロ原子を含む５員環の複素環式置換基を導入した式（１）で表される化合物は、Ｚがフェニル基である化合物と比較して、土壌分解性が高いことが判明した。こうした土壌分解性を有する化合物群は、環境負荷が低減されため有用である。 Using the above method, the compounds in which Z is a thienyl group (Compound Nos. 2 and 4) decomposed in soil for 30 to 60% in 90 days. On the other hand, the compound in which Z is a phenyl group (Comparative Example compound) obtained in Reference Example 13 was not observed to decompose in soil for 90 days. That is, the compound represented by the formula (1) in which a 5-membered heterocyclic substituent containing a hetero atom such as a sulfur atom is introduced into Z is more degradable in soil than the compound in which Z is a phenyl group. Was found to be high. The compound group having such soil degradability is useful because the environmental load is reduced.
　本発明のピリドン化合物は新規な化合物であり、植物病害を防除することができるので、農薬、例えば、農園芸用有害生物防除剤、特に農園芸用殺菌剤としての利用価値がある。 Since the pyridone compound of the present invention is a novel compound and can control plant diseases, it is useful as a pesticide, for example, an agricultural and horticultural pest control agent, particularly an agricultural and horticultural fungicide.

Claims (7)

  1. Figure JPOXMLDOC01-appb-C000001
    ［式中、Ｒ１は、
    　　水素原子、
    　　シアノ基、
    　　ハロゲン原子、
    　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
    　　Ｃ１～Ｃ６のハロアルキル基、
    　　置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、
    　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
    　　Ｃ２～Ｃ６のハロアルケニル基、
    　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
    　　Ｃ２～Ｃ６のハロアルキニル基、
    　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
    　　Ｃ１～Ｃ６のハロアルコキシ基、
    　　置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基、
    　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、
    　　Ｃ２～Ｃ６のハロアルケニルオキシ基、
    　　置換基Ａで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、
    　　Ｃ３～Ｃ６のハロアルキニルオキシ基、
    　　Ｒｃ－Ｌ－（ここで、Ｒｃは、Ｃ１～Ｃ６のアルキル基またはＣ１～Ｃ６のハロアルキル基を表し、Ｌは、Ｓ、ＳＯ、またはＳＯ２を表す。）、
    　　または、ＲｇＣ（＝Ｏ）－（ここで、Ｒｇは、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表す。）を表し；
    　Ｒ２は、
    　　シアノ基、
    　　ハロゲン原子、
    　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
    　　Ｃ１～Ｃ６のハロアルキル基、
    　　置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、
    　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
    　　Ｃ２～Ｃ６のハロアルケニル基、
    　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
    　　Ｃ２～Ｃ６のハロアルキニル基、
    　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
    　　Ｃ１～Ｃ６のハロアルコキシ基、
    　　置換基Ａで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基、
    　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、
    　　Ｃ２～Ｃ６のハロアルケニルオキシ基、
    　　置換基Ａで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、
    　　Ｃ３～Ｃ６のハロアルキニルオキシ基、
    　　Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）、
    　　または、ＲｇＣ（＝Ｏ）－（ここで、Ｒｇは、前記と同義である。）を表し；
    　Ｘは、酸素原子または硫黄原子であり；
    　Ｒ３は、
    　　水酸基、
    　　シアノ基、
    　　ニトロ基、
    　　ハロゲン原子、
    　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
    　　Ｃ１～Ｃ６のハロアルキル基、
    　　置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、
    　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
    　　Ｃ２～Ｃ６のハロアルケニル基、
    　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
    　　Ｃ２～Ｃ６のハロアルキニル基、
    　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
    　　Ｃ１～Ｃ６のハロアルコキシ基、
    　　置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基、
    　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、
    　　Ｃ２～Ｃ６のハロアルケニルオキシ基、
    　　置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、
    　　Ｃ３～Ｃ６のハロアルキニルオキシ基、
    　　ＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、またはＣ３～Ｃ８のシクロアルコキシ基を表す。）、
    　　ＲｄＣ（＝Ｏ）Ｏ－（ここで、Ｒｄは、前記と同義である。）、
    　　Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）、
    　　ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、それぞれ独立していて、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表す。）、
    　　または、ＲｅＣ（＝Ｏ）Ｎ（Ｒｆ）－（ここで、ＲｅとＲｆは、それぞれ独立していて、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、Ｃ３～Ｃ８のシクロアルコキシ基、またはＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）を表す。）を表し；
    　ｎは、０～５の整数（ただし、ｎが２以上の場合、Ｒ３はそれぞれ独立している。）を表し；
    　Ｚは、
    　　Ｒ４で適宜０～３置換されてもよいチエニル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）、
    　　Ｒ４で適宜０～２置換されてもよいチアゾリル基（ただし、２置換以上のＲ４の場合、それぞれ独立している。）、
    　　Ｒ４で適宜置換されてもよいチアジアゾリル基
    　　Ｒ４で適宜０～３置換されてもよいピラゾリル基（ただし、２置換のＲ４の場合、それぞれ独立している。）、
    　　または、Ｒ４で適宜置換されてもよいテトラゾリル基を表し、
    　Ｒ４は、
    　　水酸基、
    　　シアノ基、
    　　ニトロ基、
    　　ハロゲン原子、
    　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
    　　Ｃ１～Ｃ６のハロアルキル基、
    　　置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルキル基、
    　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
    　　Ｃ２～Ｃ６のハロアルケニル基、
    　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
    　　Ｃ２～Ｃ６のハロアルキニル基、
    　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
    　　Ｃ１～Ｃ６のハロアルコキシ基、
    　　置換基Ｃで適宜置換されてもよいＣ３～Ｃ８のシクロアルコキシ基、
    　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、
    　　Ｃ２～Ｃ６のハロアルケニルオキシ基、
    　　置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、
    　　Ｃ３～Ｃ６のハロアルキニルオキシ基、
    　　ＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、前記と同義である。）、
    　　ＲｄＣ（＝Ｏ）Ｏ－（ここで、Ｒｄは、前記と同義である。）、
    　　Ｒｃ－Ｌ－（ここで、Ｒｃ、Ｌは、前記と同義である。）、
    　　ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）、
    　　または、ＲｅＣ（＝Ｏ）Ｎ（Ｒｆ）－（ここで、ＲｅおよびＲｆは、前記と同義である。）を表し；
    　そして、置換基Ａは、水酸基、シアノ基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、Ｃ３～Ｃ８のシクロアルコキシ基、ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）、およびＲｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）からなる群から選択される少なくとも１種であり；
    　置換基Ｂは、シアノ基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基およびＣ３～Ｃ８のシクロアルコキシ基からなる群から選択される少なくとも１種であり；
    　置換基Ｃは、水酸基、シアノ基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、Ｃ３～Ｃ８のシクロアルコキシ基、Ｃ２～Ｃ６のアルコキシアルコキシ基、ＲａＲｂＮ－（ここで、ＲａおよびＲｂは、前記と同義である。）、Ｒｃ－Ｌ－（ここで、ＲｃおよびＬは、前記と同義である。）、およびＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、前記と同義である。）からなる群から選択される少なくとも１種である。］で表される化合物またはその塩。
    Figure JPOXMLDOC01-appb-C000001
    [In the formula, R1 is
    Hydrogen atom,
    Cyano group,
    Halogen atom,
    A C1 to C6 alkyl group optionally substituted with a substituent A,
    A C1 to C6 haloalkyl group,
    A C3 to C8 cycloalkyl group which may be optionally substituted with a substituent A,
    A C2-C6 alkenyl group optionally substituted with a substituent A,
    A C2-C6 haloalkenyl group,
    A C2-C6 alkynyl group optionally substituted with a substituent A,
    A C2-C6 haloalkynyl group,
    A C1 to C6 alkoxy group optionally substituted with a substituent A,
    A C1 to C6 haloalkoxy group,
    A C3 to C8 cycloalkoxy group optionally substituted with a substituent A,
    A C2-C6 alkenyloxy group which may be optionally substituted with a substituent A,
    A C2-C6 haloalkenyloxy group,
    A C3-C6 alkynyloxy group which may be optionally substituted with a substituent A,
    A C3 to C6 haloalkynyloxy group,
    Rc-L- (wherein Rc represents a C1-C6 alkyl group or a C1-C6 haloalkyl group, and L represents S, SO, or SO 2 ),
    Alternatively, RgC (═O) — (wherein, Rg represents a C1 to C6 alkyl group optionally substituted with the substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group. ) Represents;
    R2 is
    Cyano group,
    Halogen atom,
    A C1 to C6 alkyl group optionally substituted with a substituent A,
    A C1 to C6 haloalkyl group,
    A C3 to C8 cycloalkyl group which may be optionally substituted with a substituent A,
    A C2-C6 alkenyl group optionally substituted with a substituent A,
    A C2-C6 haloalkenyl group,
    A C2-C6 alkynyl group optionally substituted with a substituent A,
    A C2-C6 haloalkynyl group,
    A C1 to C6 alkoxy group optionally substituted with a substituent A,
    A C1 to C6 haloalkoxy group,
    A C3 to C8 cycloalkoxy group optionally substituted with a substituent A,
    A C2-C6 alkenyloxy group which may be optionally substituted with a substituent A,
    A C2-C6 haloalkenyloxy group,
    A C3-C6 alkynyloxy group which may be optionally substituted with a substituent A,
    A C3 to C6 haloalkynyloxy group,
    Rc-L- (wherein Rc and L are as defined above),
    Or represents RgC (═O) — (wherein Rg has the same meaning as above);
    X is an oxygen atom or a sulfur atom;
    R3 is
    Hydroxyl group,
    Cyano group,
    Nitro group,
    Halogen atom,
    A C1 to C6 alkyl group optionally substituted with a substituent C,
    A C1 to C6 haloalkyl group,
    A C3 to C8 cycloalkyl group optionally substituted with a substituent C,
    A C2-C6 alkenyl group optionally substituted with a substituent C,
    A C2-C6 haloalkenyl group,
    A C2 to C6 alkynyl group optionally substituted with a substituent C,
    A C2-C6 haloalkynyl group,
    A C1 to C6 alkoxy group optionally substituted with a substituent C,
    A C1 to C6 haloalkoxy group,
    A C3 to C8 cycloalkoxy group optionally substituted with a substituent C,
    A C2-C6 alkenyloxy group which may be optionally substituted with a substituent C,
    A C2-C6 haloalkenyloxy group,
    A C3-C6 alkynyloxy group optionally substituted with a substituent C,
    A C3 to C6 haloalkynyloxy group,
    RdC (= O)-(wherein Rd is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, a C1 to Represents a C6 alkoxy group, a C1 to C6 haloalkoxy group, or a C3 to C8 cycloalkoxy group),
    RdC (= O) O- (wherein Rd is as defined above),
    Rc-L- (wherein Rc and L are as defined above),
    RaRbN- (wherein Ra and Rb are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group). Represents an alkyl group),
    Alternatively, ReC (═O) N (Rf) — (wherein Re and Rf are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, C1 to C6). Haloalkyl group, C3-C8 cycloalkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C3-C8 cycloalkoxy group, or RaRbN- (wherein Ra and Rb have the same meanings as defined above). Represents)) represents);
    n represents an integer of 0 to 5 (provided that when n is 2 or more, R3s are independent of each other);
    Z is
    A thienyl group which may be optionally substituted by 0 to 3 with R4 (however, in the case of 2 or more substituted R4, each is independent),
    A thiazolyl group which may be optionally substituted by 0 to 2 with R4 (however, in the case of R4 having 2 or more substitutions, each is independent),
    Thiadiazolyl group optionally substituted with R4 pyrazolyl group optionally substituted with 0 to 3 optionally with R4 (however, in the case of disubstituted R4, each is independent),
    Or, represents a tetrazolyl group optionally substituted by R4,
    R4 is
    Hydroxyl group,
    Cyano group,
    Nitro group,
    Halogen atom,
    A C1 to C6 alkyl group optionally substituted with a substituent C,
    A C1 to C6 haloalkyl group,
    A C3 to C8 cycloalkyl group optionally substituted with a substituent C,
    A C2-C6 alkenyl group optionally substituted with a substituent C,
    A C2-C6 haloalkenyl group,
    A C2 to C6 alkynyl group optionally substituted with a substituent C,
    A C2-C6 haloalkynyl group,
    A C1 to C6 alkoxy group optionally substituted with a substituent C,
    A C1 to C6 haloalkoxy group,
    A C3 to C8 cycloalkoxy group optionally substituted with a substituent C,
    A C2-C6 alkenyloxy group which may be optionally substituted with a substituent C,
    A C2-C6 haloalkenyloxy group,
    A C3-C6 alkynyloxy group optionally substituted with a substituent C,
    A C3 to C6 haloalkynyloxy group,
    RdC (= O)-(wherein Rd is as defined above),
    RdC (= O) O- (wherein Rd is as defined above),
    Rc-L- (wherein Rc and L are as defined above),
    RaRbN- (wherein Ra and Rb are as defined above),
    Alternatively, ReC (═O) N (Rf)-(wherein Re and Rf have the same meanings as described above);
    The substituent A is a hydroxyl group, a cyano group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, a C3 to C8 cycloalkoxy group, or a RaRbN- (here, Ra And Rb are as defined above.), And Rc-L- (wherein Rc and L are as defined above), and at least one selected from the group consisting of:
    Substituent B is at least one selected from the group consisting of a cyano group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group and a C3-C8 cycloalkoxy group;
    Substituent C is a hydroxyl group, a cyano group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, a C2-C6 alkoxyalkoxy group, RaRbN -(Wherein Ra and Rb are as defined above), Rc-L- (wherein Rc and L are as defined above), and RdC (= O)-(wherein Rd has the same meaning as described above.) And is at least one selected from the group consisting of Or a salt thereof.
  2. Ｒ１は、
    　　水素原子、
    　　ハロゲン原子、
    　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
    　　Ｃ１～Ｃ６のハロアルキル基、
    　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
    　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
    　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
    　　Ｃ１～Ｃ６のハロアルコキシ基、
    　　または、ＲｇＣ（＝Ｏ）－（ここで、Ｒｇは、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、またはＣ３～Ｃ８のシクロアルキル基を表す。）を表し；
    　Ｒ２は、
    　　ハロゲン原子、
    　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
    　　Ｃ１～Ｃ６のハロアルキル基、
    　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
    　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
    　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
    　　Ｃ１～Ｃ６のハロアルコキシ基、
    　　置換基Ａで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、
    　　または、置換基Ａで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基を表し；
    　Ｘは、酸素原子であり；
    　Ｒ３は、
    　　水酸基、
    　　シアノ基、
    　　ハロゲン原子、
    　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
    　　Ｃ１～Ｃ６のハロアルキル基、
    　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
    　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
    　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
    　　Ｃ１～Ｃ６のハロアルコキシ基、
    　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、
    　　または、置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基を表し；
    　Ｒ４は、
    　　水酸基、
    　　シアノ基、
    　　ニトロ基、
    　　ハロゲン原子、
    　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
    　　Ｃ１～Ｃ６のハロアルキル基、
    　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニル基、
    　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルキニル基、
    　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基、
    　　Ｃ１～Ｃ６のハロアルコキシ基、
    　　置換基Ｃで適宜置換されてもよいＣ２～Ｃ６のアルケニルオキシ基、
    　　置換基Ｃで適宜置換されてもよいＣ３～Ｃ６のアルキニルオキシ基、
    　　または、ＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、またはＣ３～Ｃ８のシクロアルコキシ基を表す。）を表す、請求項１に記載の化合物またはその塩。     R1 is
    Hydrogen atom,
    Halogen atom,
    A C1 to C6 alkyl group optionally substituted with a substituent A,
    A C1 to C6 haloalkyl group,
    A C2-C6 alkenyl group optionally substituted with a substituent A,
    A C2-C6 alkynyl group optionally substituted with a substituent A,
    A C1 to C6 alkoxy group optionally substituted with a substituent A,
    A C1 to C6 haloalkoxy group,
    Alternatively, RgC (═O) — (wherein, Rg represents a C1 to C6 alkyl group optionally substituted with the substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group. ) Represents;
    R2 is
    Halogen atom,
    A C1 to C6 alkyl group optionally substituted with a substituent A,
    A C1 to C6 haloalkyl group,
    A C2-C6 alkenyl group optionally substituted with a substituent A,
    A C2-C6 alkynyl group optionally substituted with a substituent A,
    A C1 to C6 alkoxy group optionally substituted with a substituent A,
    A C1 to C6 haloalkoxy group,
    A C2-C6 alkenyloxy group which may be optionally substituted with a substituent A,
    Or represents a C3-C6 alkynyloxy group which may be optionally substituted with a substituent A;
    X is an oxygen atom;
    R3 is
    Hydroxyl group,
    Cyano group,
    Halogen atom,
    A C1 to C6 alkyl group optionally substituted with a substituent C,
    A C1 to C6 haloalkyl group,
    A C2-C6 alkenyl group optionally substituted with a substituent C,
    A C2 to C6 alkynyl group optionally substituted with a substituent C,
    A C1 to C6 alkoxy group optionally substituted with a substituent C,
    A C1 to C6 haloalkoxy group,
    A C2-C6 alkenyloxy group which may be optionally substituted with a substituent C,
    Or represents a C3 to C6 alkynyloxy group which may be optionally substituted with a substituent C;
    R4 is
    Hydroxyl group,
    Cyano group,
    Nitro group,
    Halogen atom,
    A C1 to C6 alkyl group optionally substituted with a substituent C,
    A C1 to C6 haloalkyl group,
    A C2-C6 alkenyl group optionally substituted with a substituent C,
    A C2 to C6 alkynyl group optionally substituted with a substituent C,
    A C1 to C6 alkoxy group optionally substituted with a substituent C,
    A C1 to C6 haloalkoxy group,
    A C2-C6 alkenyloxy group which may be optionally substituted with a substituent C,
    A C3-C6 alkynyloxy group optionally substituted with a substituent C,
    Alternatively, RdC (═O) — (wherein Rd is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, The compound according to claim 1, or a salt thereof, which represents a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, or a C3 to C8 cycloalkoxy group.
  3. 　Ｒ１は、
    　　水素原子、
    　　ハロゲン原子、
    　　または、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基を表し；
    　Ｒ２は、
    　　ハロゲン原子、
    　　置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
    　　または、置換基Ａで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基を表し；
    　Ｒ３は、
    　　ハロゲン原子、
    　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
    　　または、置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルコキシ基を表し；
    　　Ｒ４は、
    　　ハロゲン原子、
    　　置換基Ｃで適宜置換されてもよいＣ１～Ｃ６のアルキル基、
    　　Ｃ１～Ｃ６のハロアルキル基、
    　　または、ＲｄＣ（＝Ｏ）－（ここで、Ｒｄは、水素原子、置換基Ｂで適宜置換されてもよいＣ１～Ｃ６のアルキル基、Ｃ１～Ｃ６のハロアルキル基、Ｃ３～Ｃ８のシクロアルキル基、Ｃ１～Ｃ６のアルコキシ基、Ｃ１～Ｃ６のハロアルコキシ基、またはＣ３～Ｃ８のシクロアルコキシ基を表す。）を表す、請求項１に記載の化合物またはその塩。     R1 is
    Hydrogen atom,
    Halogen atom,
    Or represents a C1 to C6 alkyl group which may be optionally substituted with a substituent A;
    R2 is
    Halogen atom,
    A C1 to C6 alkyl group optionally substituted with a substituent A,
    Or represents a C1 to C6 alkoxy group which may be optionally substituted with a substituent A;
    R3 is
    Halogen atom,
    A C1 to C6 alkyl group optionally substituted with a substituent C,
    Or represents a C1 to C6 alkoxy group which may be optionally substituted with a substituent C;
    R4 is
    Halogen atom,
    A C1 to C6 alkyl group optionally substituted with a substituent C,
    A C1 to C6 haloalkyl group,
    Alternatively, RdC (═O) — (where Rd is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, The compound or a salt thereof according to claim 1, which represents a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, or a C3 to C8 cycloalkoxy group.
  4. 　請求項１に記載の化合物、またはその塩を有効成分として含有する農園芸用有害生物防除剤。 An agricultural and horticultural pest control agent containing the compound according to claim 1 or a salt thereof as an active ingredient.
  5. 　請求項１に記載の化合物、またはその塩を有効成分として含有する農園芸用殺菌剤。 An agricultural / horticultural fungicide containing the compound according to claim 1 or a salt thereof as an active ingredient.
  6. 　請求項４に記載の農園芸用有害生物防除剤を、植物、植物の種子、または植物を栽培する土壌に施用することを含む、植物病害を防除する方法。 A method for controlling plant diseases, which comprises applying the agricultural and horticultural pest control agent according to claim 4 to plants, plant seeds, or soil in which the plants are grown.
  7. 　請求項５に記載の農園芸用殺菌剤を、植物、植物の種子、または植物を栽培する土壌に施用することを含む、植物病害を防除する方法。 A method for controlling plant diseases, which comprises applying the agricultural / horticultural fungicide according to claim 5 to plants, plant seeds, or soil in which plants are cultivated.
PCT/JP2019/039622 2018-10-09 2019-10-08 Pyridone compound and agricultural and horticultural fungicide having same as effective component thereof WO2020075706A1 (en)

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JPH01156918A (en) * 1987-09-04 1989-06-20 Kumiai Chem Ind Co Ltd Carcinostatic agent
JPH01163171A (en) * 1986-03-26 1989-06-27 Kumiai Chem Ind Co Ltd 4(1h)-pyridinone derivative and agricultural and horticultural germicide
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WO2018139560A1 (en) * 2017-01-26 2018-08-02 三井化学アグロ株式会社 Pyridone compound and bactericide for agricultural and horticultural use, which uses said compound as active ingredient

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JPS6345259A (en) * 1985-10-24 1988-02-26 Daicel Chem Ind Ltd Pyridine-3-carboxamide derivative
JPS62181204A (en) * 1986-02-06 1987-08-08 Kumiai Chem Ind Co Ltd Nonmedical germicide
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023088718A1 (en) 2021-11-19 2023-05-25 Basf Se Bicyclic compounds for the control of invertebrate pests

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