WO2015198859A1 - Composé hétérocyclique condensé - Google Patents

Composé hétérocyclique condensé Download PDF

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Publication number
WO2015198859A1
WO2015198859A1 PCT/JP2015/066673 JP2015066673W WO2015198859A1 WO 2015198859 A1 WO2015198859 A1 WO 2015198859A1 JP 2015066673 W JP2015066673 W JP 2015066673W WO 2015198859 A1 WO2015198859 A1 WO 2015198859A1
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compound
group
formula
compounds
reaction
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PCT/JP2015/066673
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English (en)
Japanese (ja)
Inventor
貴將 田邊
亮太 前畑
綾香 長谷部
慎哉 西村
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住友化学株式会社
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • C07D401/14—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 three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the present invention relates to certain condensed heterocyclic compounds and their use for pest control.
  • An object of the present invention is to provide a compound having an excellent control effect against pests and a method for controlling pests using the compound.
  • the condensed heterocyclic compound represented by the following formula (1) has an excellent control effect against pests.
  • R 1 is a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C3 alkoxy group, a C2-C4 alkoxycarbonyl group, S (O) m R 2 , NR 3 R 4 represents a nitro group or a cyano group, R 2 represents a C1-C3 alkyl group, R 3 and R 4 each independently represents a hydrogen atom or a C1-C3 alkyl group, R 5 represents a C1-C3 perfluoroalkyl group or S (O) p —R 6 , R 6 represents a C1-C3 perfluoroalkyl group, n represents 0, 1 or 2, m represents 0, 1 or 2; p represents 0, 1 or 2.
  • a condensed heterocyclic compound represented by the following (hereinafter referred to as the present compound).
  • [2] The compound according to [1], wherein A is NCH 3 .
  • [3] The compound according to [1], wherein A is an oxygen atom.
  • R 1 is a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C3 alkoxy group, or S (O) m R 2 [1] ]
  • R 1 is a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C3 alkoxy group, or S (O) m R 2 [1] ]
  • S (O) m R 2 [1]
  • the compound of the present invention is useful as an active ingredient of a pest control agent because it has an excellent control activity against pests.
  • halogen atom means a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • examples of the “C1-C3 alkyl group” include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • the “C1-C3 alkyl group optionally having one or more halogen atoms” refers to a C1-C3 alkyl group in which at least one hydrogen atom may be substituted with a halogen atom.
  • Represents a C3 alkyl group for example, fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, dichloromethyl group, trifluoromethyl group, chlorodifluoromethyl group, bromodifluoromethyl group, trichloromethyl group, 2- Examples include fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group and heptafluoroisopropyl group. .
  • the “C1-C3 perfluoroalkyl group” represents a C1-C3 alkyl group in which all hydrogen atoms are substituted with fluorine atoms, specifically, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, A heptafluoroisopropyl group is mentioned.
  • examples of the “C1-C3 alkoxy group” include a methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group.
  • examples of the “C1-C3 alkylamino group” include a methylamino group, an ethylamino group, a propylamino group, and an isopropylamino group.
  • the “di (C1-C3 alkyl) amino group” includes N, N-dimethylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-diisopropylamino group, N-methyl-N-ethylamino group, N-methyl-N-propylamino group, N-methyl-N-isopropylamino group, N-ethyl-N-propylamino group, and N-ethyl-N-isopropylamino group Is mentioned.
  • C2-C4 alkoxycarbonyl group represents a group in which a C1-C3 alkoxy group and a carbonyl group are bonded, and represents a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, or an isopropoxycarbonyl group.
  • S (O) m R 2 represents a C1-C3 alkylsulfanyl group in which m is 0, an alkylsulfinyl group in which m is 1 and an alkylsulfonyl group in which m is 2.
  • the C1-C3 alkylsulfanyl group represents a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, and an isopropylsulfanyl group.
  • the C1-C3 alkylsulfinyl group represents a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, and an isopropylsulfinyl group.
  • the C1-C3 alkylsulfonyl group represents a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, and an isopropylsulfonyl group.
  • A is NCH 3
  • R 1 is a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, an amino group, or S (O) m R
  • A is NCH 3
  • R 1 is a hydrogen atom, a C1-C3 alkyl group, a halogen atom, an amino group, or S (O) m R 2
  • R 5 is CF 3 or S (O ) P CF 3 and n is 0, 1 or 2
  • A is NCH 3
  • R 1 is a hydrogen atom, a chlorine atom, a methyl group, an amino group, a methylsulfanyl group, a methylsulfinyl group, or a methylsulfony
  • A is an oxygen atom
  • R 1 is a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, an amino group, or S (O) m R A compound in which R 5 is a C1-C3 perfluoroalkyl group or S (O) p R 6 , and n is 0, 1 or 2;
  • A is an oxygen atom
  • R 1 is a hydrogen atom, a C1-C3 alkyl group, a halogen atom, an amino group, or S (O) m R 2
  • R 5 is CF 3 or S (O ) P CF 3 and n is 0, 1 or 2
  • A is an oxygen atom
  • R 1 is a hydrogen atom, a chlorine atom, a methyl group, an amino group, a methylsulfanyl group, a methylsulfinyl group, or a methylsulf
  • a compound which is in the formula (1) compounds wherein A is NCH 3 , R 1 is a methylsulfanyl group, a methylsulfinyl group or a methylsulfonyl group, and R 5 is a C1-C3 perfluoroalkyl group; In the formula (1), compounds wherein A is NCH 3 , R 1 is a methylsulfanyl group or a methylsulfonyl group, and R 5 is a C1-C3 perfluoroalkyl group; In the formula (1), compounds wherein A is NCH 3 , R 1 is NR 3 R 4 and R 5 is a C1-C3 perfluoroalkyl group; In the formula (1), A is NCH 3, R 1 is an amino group, C1-C3 alkylamino group, di is (C1-C3 alkyl) amino group or a nitro group, R 5 is C1-C3 perfluoroalkyl A compound which is a group; In
  • compounds wherein A is NCH 3 , R 1 is a C1-C3 alkyl group optionally having one or more halogen atoms, and R 5 is S (O) p CF
  • a compound which is in the formula (1) a compound wherein A is an oxygen atom, R 1 is a methylsulfanyl group, a methylsulfinyl group or a methylsulfonyl group, and R 5 is a C1-C3 perfluoroalkyl group;
  • A is an oxygen atom, R 1 is an amino group, a C1-C3 alkylamino group, a di (C1-C3 alkyl) amino group or a nitro group, and R 5 is a C1-C3 perfluoro
  • the compound of the present invention and the production intermediate compound can be produced, for example, by any of the production methods 1 to 11 described below.
  • the reaction is performed in the presence of a solvent.
  • a solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
  • the oxidizing agent used in the reaction include sodium periodate, m-chloroperbenzoic acid, and hydrogen peroxide.
  • a base or a catalyst may be added as necessary.
  • the base used for the reaction include sodium carbonate.
  • Examples of the catalyst used for the reaction include tungstic acid and sodium tungstate.
  • an oxidizing agent is usually used in a proportion of 1 to 1.2 mol.
  • the base is generally used at a ratio of 0.01 to 1 mol per 1 mol of the compound (1a) of the present invention.
  • the catalyst is generally used in a proportion of 0.01 to 0.5 mol per 1 mol of the compound (1a) of the present invention.
  • the reaction temperature is usually in the range of ⁇ 20 to 80 ° C.
  • the reaction time is usually in the range of 0.1 to 12 hours.
  • the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite and sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary.
  • a reducing agent for example, sodium sulfite and sodium thiosulfate
  • a base for example, sodium bicarbonate
  • the compound (1b) of the present invention can be isolated by drying and concentrating the washed organic layer.
  • the isolated compound (1b) of the present invention can be further purified by chromatography, recrystallization and the like.
  • the reaction is usually performed in the presence of a solvent.
  • a solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
  • the oxidizing agent used in the reaction include m-chloroperbenzoic acid and hydrogen peroxide.
  • a base or a catalyst may be added as necessary.
  • the base used for the reaction include sodium carbonate.
  • the catalyst used in the reaction include sodium tungstate.
  • the oxidizing agent is usually used at a ratio of 1 to 4 moles with respect to 1 mole of the compound (1b) of the present invention.
  • the oxidizing agent is used in a ratio of 1 to 2 moles relative to 1 mole of the compound (1b) of the present invention.
  • the base is generally used at a ratio of 0.01 to 1 mol per 1 mol of the compound (1b) of the present invention.
  • the catalyst is generally used in a proportion of 0.01 to 0.5 mol with respect to 1 mol of the compound (1b) of the present invention.
  • the reaction temperature is usually in the range of ⁇ 20 to 120 ° C.
  • the reaction time is usually in the range of 0.1 to 12 hours.
  • the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite and sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary.
  • a reducing agent for example, sodium sulfite and sodium thiosulfate
  • a base for example, sodium bicarbonate
  • the compound (1c) of the present invention can be isolated by drying and concentrating the organic layer.
  • the compound (1c) of the present invention can be further purified by chromatography, recrystallization and the like.
  • this invention compound (1c) can be manufactured by a one-step reaction (one pot) by making this invention compound (1a) and an oxidizing agent react.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
  • the oxidizing agent used in the reaction include m-chloroperbenzoic acid and hydrogen peroxide. When hydrogen peroxide is used as the oxidizing agent for the reaction, it is carried out in the presence of a base or a catalyst as necessary.
  • Examples of the base used for the reaction include sodium carbonate.
  • Examples of the catalyst used for the reaction include tungstic acid and sodium tungstate.
  • an oxidizing agent is usually used at a ratio of 2 to 5 moles.
  • the base is generally used at a ratio of 0.01 to 1 mol per 1 mol of the compound (1a) of the present invention.
  • the catalyst is generally used in a proportion of 0.01 to 0.5 mol per 1 mol of the compound (1a) of the present invention.
  • the reaction temperature of the reaction is usually in the range of 0 to 120 ° C.
  • the reaction time is usually in the range of 0.1 to 12 hours.
  • the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite and sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary.
  • a reducing agent for example, sodium sulfite and sodium thiosulfate
  • a base for example, sodium bicarbonate
  • the compound (1c) of the present invention can be isolated by drying and concentrating the organic layer.
  • the isolated compound (1c) of the present invention can be further purified by chromatography, recrystallization and the like.
  • the compound of the present invention comprises a compound represented by formula (M1) (hereinafter referred to as compound (M1)) and a compound represented by formula (M2) (hereinafter referred to as compound (M2)) as a base. It can manufacture by making it react in presence. [Wherein, X represents a halogen atom, and other symbols have the same meaning as in formula (1). ]
  • Compound (M2) is known or can be produced according to a known method.
  • the present compound (1a) to the present compound (1c) can be produced according to this reaction. The reaction is usually performed in the presence of a solvent.
  • solvent used in the reaction examples include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene.
  • ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether
  • halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene.
  • Aromatic hydrocarbons such as toluene, benzene, xylene, esters such as ethyl acetate and butyl acetate, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolid
  • Non-protic polar solvents such as non- and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
  • Examples of the base used in the reaction include alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride, alkali metal carbonates such as sodium carbonate and potassium carbonate, or triethylamine and diisopropylene. And organic bases such as propylethylamine, pyridine and 4-dimethylaminopyridine.
  • the compound (M1) is usually used in a proportion of 1 to 2 mol
  • the base is usually used in a proportion of 1 to 5 mol.
  • the reaction temperature of the reaction is usually in the range of 0 to 120 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture After completion of the reaction, the reaction mixture is added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered.
  • the compound of the present invention can be isolated by collecting by The isolated compound of the present invention can be further purified by recrystallization, chromatography or the like.
  • Manufacturing method 4 Compound (M1a) can be produced, for example, according to the following scheme. [Wherein the symbols have the same meaning as described above. ]
  • a compound represented by formula (M7) (hereinafter referred to as compound (M7)) is represented by a compound represented by formula (M6) (hereinafter referred to as compound (M6)), and two Xs represent the same halogen atom. ) And a chlorinating agent.
  • the compound (M6) include 3,6-difluoro-pyridine-2-carboxylic acid and 3,6-dichloro-pyridine-2-carboxylic acid, both of which are commercially available compounds.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include aromatic hydrocarbons such as toluene and xylene, aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, and mixtures thereof.
  • Examples of the chlorinating agent used in the reaction include thionyl chloride, oxalyl dichloride, phosphorus oxychloride and the like.
  • a chlorinating agent is usually used at a ratio of 1 to 15 mol with respect to 1 mol of the compound (M6).
  • the reaction temperature is usually in the range of 0 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours. After completion of the reaction, the compound (M7) can be isolated by removing the solvent.
  • a compound represented by formula (M9) (hereinafter referred to as compound (M9)) is obtained by reacting compound (M7) with a compound represented by formula (M8) (hereinafter referred to as compound (M8)).
  • compound (M8) a compound represented by formula (M8)
  • M8 N 1 -methyl-4-trifluoromethyl-benzene-1,2-diamine in which R 5 is CF 3 and A is NCH 3 is described in WO2010 / 125985 It can be manufactured by the method.
  • compound (M8) a compound (M8a) in which R 5 is CF 2 CF 3 , CF 2 CF 2 CF 3 , CF (CF 3 ) 2 , or SR 6 and A is NCH 3 (hereinafter referred to as compound (M8a )) Can be produced by the method described in Production Example 8.
  • Compound (M8b) in which R 5 is S (O) R 6 or S (O) 2 R 6 and A is NCH 3 in Compound (M8) (hereinafter referred to as Compound (M8b)) is described in Production Method 9. It can be manufactured by the method.
  • compound (M8) 2-amino-4-trifluoromethyl-phenol in which R 5 is CF 3 and A is an oxygen atom can be produced by the method described in US Pat. No. 5,780,483.
  • R 5 is R 5 is CF 2 CF 3 , CF 2 CF 2 CF 3 , CF (CF 3 ) 2 , SR 6 , S (O) R 6 , or S (O) 2 R 6
  • the compound (M8c) in which A is an oxygen atom (hereinafter referred to as the compound (M8c)) can be produced by the method described in Production Method 10. The reaction is usually performed in the presence of a solvent.
  • solvent used in the reaction examples include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene.
  • ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane
  • aliphatic hydrocarbons such as hexane, heptane, and octane
  • aromatics such as toluene and xylene.
  • Aprotic polarities such as aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide Examples include solvents and mixtures thereof.
  • a base may be added as necessary.
  • the base used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and N, N-diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
  • the compound (M7) is usually used in a proportion of 1 to 3 mol
  • the base is usually used in a proportion of 1 to 10 mol.
  • the reaction temperature is usually in the range of ⁇ 20 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (M9) can be isolated by post-treatment such as addition of water to the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M9) can be further purified by chromatography, recrystallization and the like.
  • Compound (M9) can also be produced in a one-step reaction (one pot) by reacting compound (M6) and compound (M8) in the presence of a condensing agent.
  • the reaction is performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene.
  • Hydrocarbons aromatic hydrocarbons such as toluene, benzene and xylene, esters such as ethyl acetate and butyl acetate, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazo Examples thereof include aprotic polar solvents such as lizinone and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
  • Examples of the condensing agent used in the reaction include carbodiimides such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (hereinafter referred to as EDCI) and 1,3-dicyclohexylcarbodiimide.
  • EDCI 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride
  • EDCI 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride
  • HOBt 1-hydroxybenzotriazole
  • the ratio of the compound (M6) is usually 1 to 2 moles
  • the condensing agent is usually 1 to 5 moles
  • the catalyst is usually 0.01 to 1 mole.
  • the reaction temperature of the reaction is usually in the range of 0 to 120 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture is added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered.
  • the compound (M9) can be isolated by collecting by The isolated compound (M9) can be further purified by recrystallization, chromatography or the like.
  • a compound represented by formula (M10) (hereinafter referred to as compound (M10).
  • Two Xs represent the same halogen atom) can be produced by intramolecular condensation of compound (M9).
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene.
  • Hydrogen aromatic hydrocarbons such as toluene, benzene and xylene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl- Examples include aprotic polar solvents such as 2-imidazolidinone and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
  • a condensing agent, an acid, a base, or a chlorinating agent may be added as necessary.
  • Examples of the condensing agent used in the reaction include acetic anhydride, trifluoroacetic anhydride, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, triphenylphosphine and base, and carbon tetrachloride or carbon tetrabromide. And mixtures of triphenylphosphine and azodiesters (eg diethyl azodicarboxylate).
  • Examples of the acid used for the reaction include sulfonic acids such as paratoluenesulfonic acid, carboxylic acids such as acetic acid, and polyphosphoric acid.
  • Examples of the base used in the reaction include pyridine, picoline, 2,6-lutidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5.
  • -Nitrogen-containing heterocyclic compounds such as nonene, tertiary amines such as triethylamine and N, N-diisopropylethylamine, and alkali metal carbonates such as tripotassium phosphate, potassium carbonate and sodium hydride.
  • Examples of the chlorinating agent used in the reaction include phosphorus oxychloride.
  • the ratio of the condensing agent is usually 1 to 5 mol, and when an acid is used, the acid is usually 0.1 mol to 5 mol.
  • the base is usually used in a proportion of 1 to 5 mol
  • the chlorinating agent is usually used in a proportion of 1 to 5 mol.
  • the reaction temperature of the reaction is usually in the range of 0 to 200 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture After completion of the reaction, the reaction mixture is added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered.
  • the compound (M10) can be isolated by collecting by The isolated compound (M10) can be further purified by recrystallization, chromatography or the like.
  • Compound (M1a) can be produced by reacting compound (M10) with ethyl mercaptan in the presence of a base.
  • the reaction is performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether, 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, acetonitrile, N, N-dimethylformamide. , N-methylpyrrolidone, aprotic polar solvents such as dimethyl sulfoxide, water, and mixtures thereof.
  • Examples of the base used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrides such as sodium hydride.
  • ethyl mercaptan is usually used in a proportion of 1 to 10 mol
  • base is usually used in a proportion of 1 to 10 mol.
  • ethyl mercaptan is used in a proportion of 1.0 to 1.1 mol
  • a base is used in a proportion of 1 to 2 mol with respect to 1 mol of compound (M11).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 ° C. to 150 ° C.
  • the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound (M1a) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (M1a) can be further purified by chromatography, recrystallization and the like.
  • the compound (1c) of the present invention can be produced, for example, according to the following scheme. [Wherein the symbols have the same meaning as described above. ]
  • a compound represented by formula (M20) (hereinafter referred to as compound (M20)) can be produced by reacting compound (M10) with ethyl mercaptan in the presence of a base.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether, 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, acetonitrile, N, N-dimethylformamide. , N-methylpyrrolidone, aprotic polar solvents such as dimethyl sulfoxide, water, and mixtures thereof.
  • Examples of the base used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrides such as sodium hydride.
  • ethyl mercaptan is usually used in a proportion of 2 to 10 mol
  • base is usually used in a proportion of 2 to 10 mol.
  • ethyl mercaptan is used in a proportion of 2.0 to 2.1 mol
  • a base is used in a proportion of 2 to 3 mol with respect to 1 mol of compound (M11).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 ° C. to 150 ° C.
  • the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound (M20) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (M20) can be further purified by chromatography, recrystallization and the like.
  • a compound represented by formula (M21) (hereinafter referred to as compound (M21)) can be produced by reacting compound (M20) with an oxidizing agent.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
  • the oxidizing agent used in the reaction include m-chloroperbenzoic acid and hydrogen peroxide. When hydrogen peroxide is used as the oxidizing agent for the reaction, it is carried out in the presence of a base or a catalyst as necessary.
  • Examples of the base used for the reaction include sodium carbonate.
  • Examples of the catalyst used for the reaction include tungstic acid and sodium tungstate.
  • the oxidizing agent is usually used at a ratio of 2 to 5 mol.
  • the base is generally used at a ratio of 0.01 to 1 mol with respect to 1 mol of the compound (20).
  • the catalyst is generally used in a proportion of 0.01 to 0.5 mol with respect to 1 mol of the compound (20).
  • the reaction temperature of the reaction is usually in the range of 0 to 120 ° C.
  • the reaction time is usually in the range of 0.1 to 12 hours.
  • reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite and sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary.
  • a reducing agent for example, sodium sulfite and sodium thiosulfate
  • a base for example, sodium bicarbonate
  • Compound (21) can be isolated by drying and concentrating this organic layer.
  • the isolated compound (M21) can be further purified by chromatography, recrystallization and the like.
  • the compound (1c) of the present invention can be produced by reacting the compound (M21) and the compound (M2) in the presence of a base.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene.
  • Aromatic hydrocarbons such as toluene, benzene, xylene, esters such as ethyl acetate and butyl acetate, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolid
  • Non-protic polar solvents such as non- and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
  • Examples of the base used in the reaction include alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride, alkali metal carbonates such as sodium carbonate and potassium carbonate, or triethylamine and diisopropylene. And organic bases such as propylethylamine, pyridine and 4-dimethylaminopyridine.
  • the compound (M2) is usually used in a proportion of 1 to 2 mol, and the base is usually used in a proportion of 1 to 5 mol.
  • the reaction temperature of the reaction is usually in the range of 0 to 120 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the present compound (1c) can be isolated by collecting the above.
  • the isolated compound (1c) of the present invention can be further purified by recrystallization, chromatography or the like.
  • the compound of the present invention in which R 1 is a C1-C3 alkoxy group (hereinafter referred to as the present compound (1m)) can be produced, for example, according to the following scheme.
  • R a represents a C1-C3 alkyl group
  • V represents a chlorine atom, a bromine atom, or an iodine atom, and other symbols have the same meaning as described above.
  • the compound represented by the formula (M3) (hereinafter referred to as the compound (M3)) can be produced by reacting the compound (M1) and semicarbazide hydrochloride in the presence of a base.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide.
  • Examples of the base used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine. It is done.
  • semicarbazide hydrochloride is usually used in a proportion of 1 to 3 mol
  • base is usually used in a proportion of 1 to 10 mol.
  • the reaction temperature is usually in the range of ⁇ 20 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture After completion of the reaction, the reaction mixture is added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered.
  • the compound (M3) can be isolated by collecting by The isolated compound (M3) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (M4) (hereinafter referred to as the compound (M4)) can be produced by reacting the compound (M3) with formic acid or trialkyl orthoformate.
  • the trialkyl orthoformate used in the reaction include trimethyl orthoformate and triethyl orthoformate.
  • the reaction is usually performed in the presence of a solvent.
  • Solvents used for the reaction include halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene, aromatic hydrocarbons such as toluene, benzene and xylene, N, N-dimethylformamide, N-methylpyrrolidone, 1, Examples include aprotic polar solvents such as 3-dimethyl-2-imidazolidinone and dimethyl sulfoxide, alcohol solvents such as methanol, ethanol and n-butanol, and mixtures thereof.
  • formic acid is usually used at a ratio of 1 to 10 mol per 1 mol of compound (M3).
  • trialkyl orthoformate When trialkyl orthoformate is used in the reaction, trialkyl orthoformate is usually used at a ratio of 1 to 10 moles with respect to 1 mole of compound (M3).
  • the reaction temperature is usually in the range of 0 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture is added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered.
  • the compound (M4) can be isolated by collecting by The isolated compound (M4) can be further purified by recrystallization, chromatography or the like.
  • the compound (1m) of the present invention can be produced by reacting the compound (M4) with a compound represented by the formula (M5) (hereinafter referred to as compound (M5)) in the presence of a base.
  • a compound represented by the formula (M5) hereinafter referred to as compound (M5)
  • Examples of the compound (M5) include iodomethane, bromomethane, iodoethane, chloroethane, 1-iodopropane, 2-iodopropane and the like.
  • the reaction is usually performed in the presence of a solvent.
  • solvent used in the reaction examples include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene.
  • Aprotic polar solvents such as hydrogen, aromatic hydrocarbons such as toluene, benzene, xylene, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like These mixtures are mentioned.
  • Examples of the base used in the reaction include alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride, alkali metal carbonates such as sodium carbonate and potassium carbonate, or triethylamine and diisopropylene. And organic bases such as propylethylamine, pyridine and 4-dimethylaminopyridine.
  • the compound (M5) is usually used in a proportion of 1 to 10 mol
  • the base is usually used in a proportion of 0.1 to 5 mol with respect to 1 mol of the compound (M4) of the present invention.
  • the reaction temperature is usually in the range of ⁇ 20 ° C. to 120 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture After completion of the reaction, the reaction mixture is added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered.
  • the present compound (1m) can be isolated by collecting by The isolated compound (1m) of the present invention can be further purified by chromatography, recrystallization and the like.
  • Manufacturing method 8 Compound (M8a) can be produced, for example, according to the following scheme.
  • a compound represented by formula (M11) (hereinafter referred to as compound (M11)) is obtained by reacting a compound represented by formula (M20) (hereinafter referred to as compound (M20)) with an acetylating agent. Can be manufactured.
  • the compound in which R 5 is CF 3 is a commercially available compound.
  • a compound in which R 5 is CF 2 CF 3 , CF 2 CF 2 CF 3 can be produced by the method described in International Publication No. 00/07998.
  • compound (M20) a compound in which R 5 is CF (CF 3 ) 2 can be produced by the method described in EP 1006102.
  • a compound in which R 5 is SCF 3 is a commercially available compound.
  • a compound in which R 5 is SCF 2 CF 3 , SCF 2 CF 2 CF 3 , or SCF (CF 3 ) 2 can be produced by the method described in JP-A-10-291973. The reaction is usually performed in the presence of a solvent.
  • solvent used in the reaction examples include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene.
  • ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether
  • halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene.
  • Hydrogen aromatic hydrocarbons such as toluene, benzene, xylene, esters such as ethyl acetate and butyl acetate, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolid
  • Non-protic polar solvents such as non- and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
  • a base may be added as necessary.
  • the base used in the reaction include organic bases such as triethylamine, diisopropylpyroethylamine, pyridine and 4-dimethylaminopyridine.
  • Examples of the acetylating agent used in the reaction include acetic anhydride and acetyl chloride.
  • the reaction may be performed using acetic anhydride, acetyl chloride or the like as a solvent.
  • an acetylating agent is usually used at a ratio of 1 to 3 moles per mole of 4-trifluoromethylsulfinyl-aniline.
  • the reaction temperature is usually in the range of ⁇ 30 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the base is usually used at a ratio of 0.01 to 3 mol per 1 mol of 4-trifluoromethylsulfinyl-aniline.
  • the compound (M11) can be isolated by performing post-treatment operations such as addition of the reaction mixture to water, extraction with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (M11) can be further purified by chromatography, recrystallization, and the like.
  • a compound represented by formula (M12) (hereinafter referred to as compound (M12)) can be produced by reacting compound (M11) with a nitrating agent.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include halogenated hydrocarbons such as dichloromethane and chloroform, acetic acid, concentrated sulfuric acid, concentrated nitric acid, water, and mixtures thereof.
  • An example of the nitrating agent used in the reaction is concentrated nitric acid.
  • the nitrating agent is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (M11).
  • the reaction temperature is usually in the range of ⁇ 10 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (M12) can be isolated by performing post-treatment operations such as addition of the reaction mixture to water, extraction with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (M12) can be further purified by chromatography, recrystallization and the like.
  • a compound represented by formula (M13) (hereinafter referred to as compound (M13)) can be produced by reacting compound (M12) with a methylating agent in the presence of a base.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene.
  • Aprotic polar solvents such as hydrogen, aromatic hydrocarbons such as toluene, benzene, xylene, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like These mixtures are mentioned.
  • the base used in the reaction include alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride, alkali metal carbonates such as sodium carbonate and potassium carbonate, or triethylamine and diisopropylene.
  • organic bases such as propylethylamine, pyridine and 4-dimethylaminopyridine.
  • the methylating agent used in the reaction examples include iodomethane and dimethyl sulfate.
  • the methylating agent is usually used at a ratio of 1 to 5 moles, and the base is usually used at a ratio of 0.1 to 5 moles.
  • the reaction temperature is usually in the range of ⁇ 20 ° C. to 120 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture is added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered.
  • the compound (M13) can be isolated by collecting by The isolated compound (M13) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by formula (M14) (hereinafter referred to as compound (M14)) can be produced by subjecting compound (M13) to a hydrolysis reaction in the presence of a base or an acid.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran and 1,4-dioxane, alcohols such as methanol and ethanol, water, and mixtures thereof.
  • the base used in the reaction include alkali metal carbonates such as sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate.
  • the acid used in the reaction include hydrochloric acid and sulfuric acid.
  • the reaction with respect to 1 mol of compound (13), when a base is used, the base is used in a proportion of 1 to 5 mol, and when an acid is used, the acid is used in a proportion of 0.1 to 5 mol.
  • the reaction temperature is usually in the range of ⁇ 20 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture is added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered.
  • the compound (M14) can be isolated by collecting by The isolated compound (M14) can be further purified by chromatography, recrystallization and the like.
  • Compound (M8a) can be produced by reacting compound (M14) with hydrogen in the presence of a hydrogenation catalyst.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, water And mixtures thereof.
  • the reaction is usually performed in a hydrogen atmosphere at 1 to 100 atm, usually in the presence of a solvent.
  • Examples of the hydrogenation catalyst used in the reaction include transition metal compounds such as palladium carbon, palladium hydroxide, Raney nickel, and platinum oxide.
  • hydrogen is usually used in a proportion of 3 to 100 mol
  • a hydrogenation catalyst is usually used in a proportion of 0.001 to 0.5 mol with respect to 1 mol of compound (M14).
  • the reaction temperature is usually in the range of ⁇ 20 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (M8a) can be isolated by performing post-treatment operations such as filtration of the reaction mixture, extraction with an organic solvent as necessary, and drying and concentration of the organic layer. The isolated compound (M8a) can be further purified by chromatography, recrystallization and the like.
  • Compound (M8a) can be produced by reacting compound (M14) with a reducing agent.
  • the reaction can be performed, for example, in the presence of a reducing agent, an acid such as hydrochloric acid or acetic acid, and water.
  • the reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, Examples thereof include aprotic polar solvents such as N, N-dimethylformamide (hereinafter referred to as DMF), N-methylpyrrolidone (hereinafter referred to as NMP), dimethyl sulfoxide (hereinafter referred to as DMSO), and mixtures thereof.
  • Examples of the reducing agent used in the reaction include metal powders such as iron powder, zinc powder, and tin dichloride.
  • the reducing agent is usually used in a proportion of 3 to 10 mol
  • the acid is usually used in a proportion of 0.01 to 0.5 mol
  • the water is used in a proportion of 3 mol or more. It is done.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (M8a) can be isolated by performing post-treatment operations such as addition of water to the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (M8a) can also be purified by chromatography, recrystallization, and the like.
  • Manufacturing method 9 Compound (M8b) can be produced, for example, according to the following scheme. [Wherein q represents 1 or 2. ]
  • a compound represented by formula (M16) (hereinafter referred to as compound (M16)) is obtained by reacting a compound represented by formula (M15) (hereinafter referred to as compound (M15)) with a chlorinating agent. Can be manufactured.
  • Compound (M15) can be produced according to the method of Production Method 10. The reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include aromatic hydrocarbons such as toluene and xylene, aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, and mixtures thereof.
  • the chlorinating agent used in the reaction include thionyl chloride, oxalyl dichloride, phosphorus oxychloride and the like.
  • a chlorinating agent is usually used at a ratio of 1 to 15 mol with respect to 1 mol of the compound (M15).
  • the reaction temperature is usually in the range of 0 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours. After completion of the reaction, the compound (M16) can be isolated by removing the solvent.
  • the compound represented by the formula (M17) (hereinafter referred to as the compound (M17)) can be produced by reacting the compound (M16) with methylamine.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene.
  • Aprotic polar solvents such as aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and the like
  • the methylamine used for the reaction may be in the form of a gas, an aqueous solution, or an alcohol solution. This reaction can also be performed in presence of a base as needed.
  • Examples of the base used in the reaction include alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride, alkali metal carbonates such as sodium carbonate and potassium carbonate, or triethylamine and diisopropylene. And organic bases such as propylethylamine, pyridine and 4-dimethylaminopyridine.
  • methylamine is usually used at a ratio of 1 to 10 moles and the base is used at a ratio of 0.01 to 10 moles.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (M17) can be isolated by post-treatment such as addition of water to the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (M17) can also be purified by chromatography, recrystallization, and the like.
  • Compound (M8b) or compound (M8c) can be produced by reacting compound (M17) with hydrogen in the presence of a hydrogenation catalyst.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, water And mixtures thereof.
  • the reaction is usually performed in a hydrogen atmosphere at 1 to 100 atm, usually in the presence of a solvent.
  • Examples of the hydrogenation catalyst used in the reaction include transition metal compounds such as palladium carbon, palladium hydroxide, Raney nickel, and platinum oxide.
  • hydrogen is usually used in a proportion of 3 to 100 mol
  • a hydrogenation catalyst is usually used in a proportion of 0.001 to 0.5 mol.
  • the reaction temperature is usually in the range of ⁇ 20 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (M8b) can be isolated by performing post-treatment operations such as filtration of the reaction mixture, extraction with an organic solvent as necessary, and drying and concentration of the organic layer. The isolated compound (M8b) can be further purified by chromatography, recrystallization and the like.
  • Compound (M8b) can be produced by reacting compound (M17) with a reducing agent.
  • the reaction can be performed, for example, in the presence of a reducing agent, an acid such as hydrochloric acid or acetic acid, and water.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, Examples include aprotic polar solvents such as DMF, NMP, DMSO, and mixtures thereof.
  • the reducing agent used in the reaction examples include metal powders such as iron powder, zinc powder, and tin dichloride.
  • the reducing agent is usually used in a proportion of 3 to 10 mol
  • the acid is usually used in a proportion of 0.01 to 0.5 mol
  • the water is used in a proportion of 3 mol or more. It is done.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (M8b) can be isolated by performing post-treatment operations such as addition of water to the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (M8b) can also be purified by chromatography, recrystallization, and the like.
  • Compound (M8c) can be produced, for example, according to the following scheme. [The symbols in the formula have the same meaning as in formula (1). ]
  • a compound represented by formula (M19) (hereinafter referred to as compound (M19)) is obtained by reacting a compound represented by formula (M18) (hereinafter referred to as compound (M18)) with a nitrating agent. Can be manufactured. The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, acetic acid, concentrated sulfuric acid, concentrated nitric acid, water, and mixtures thereof.
  • the nitrating agent used in the reaction examples include concentrated nitric acid.
  • the nitrating agent is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (M18).
  • the reaction temperature is usually in the range of ⁇ 10 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (M19) can be isolated by performing post-treatment operations such as addition of the reaction mixture to water, extraction with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (M19) can be further purified by chromatography, recrystallization and the like.
  • Compound (M8c) can be produced by reacting compound (M19) with hydrogen in the presence of a hydrogenation catalyst.
  • the reaction is usually performed in a hydrogen atmosphere at 1 to 100 atm, usually in the presence of a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, water And mixtures thereof.
  • the hydrogenation catalyst used in the reaction include transition metal compounds such as palladium carbon, palladium hydroxide, Raney nickel, and platinum oxide.
  • the reaction with respect to 1 mole of the compound (M19), hydrogen is usually used at a ratio of 3 moles, and the hydrogenation catalyst is usually used at a ratio of 0.001 to 0.5 moles.
  • the reaction temperature is usually in the range of ⁇ 20 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (M8c) can be isolated by performing post-treatment operations such as filtration of the reaction mixture, extraction with an organic solvent as necessary, and drying and concentration of the organic layer.
  • the isolated compound (M8c) can be further purified by chromatography, recrystallization, and the like.
  • Compound (M8c) can be produced by reacting compound (M19) with a reducing agent.
  • the reaction can be performed, for example, in the presence of a reducing agent, an acid such as hydrochloric acid or acetic acid, and water.
  • the reaction is usually performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, Examples include aprotic polar solvents such as DMF, NMP, DMSO, and mixtures thereof.
  • the reducing agent used in the reaction examples include metal powders such as iron powder, zinc powder, and tin dichloride.
  • the reducing agent is usually used in a proportion of 3 to 10 mol
  • the acid is usually used in a proportion of 0.01 to 0.5 mol
  • the water is used in a proportion of 3 mol or more. It is done.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (M8c) can be isolated by performing post-treatment operations such as addition of water to the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (M8c) can also be purified by chromatography, recrystallization, and the like.
  • Manufacturing method 11 Compound (M18b) in which R 5 is S (O) R 6 in formula (M18) (hereinafter referred to as compound (M18b)), and Compound in which R 5 is S (O) 2 R 6 in formula (M18) (M18c) (hereinafter referred to as compound (M18c)) is obtained by reacting compound (M18a) (hereinafter referred to as compound (M18a)) in which R 5 is SR 6 in compound (M18) with an oxidizing agent. Can be manufactured. The reaction is carried out according to the reaction described in Production Example 1 by substituting compound (M18a) for the present compound (1a) in production method 1 and compound (M18b) for the present compound (1b). can do.
  • Compound (M18) can be produced by reacting compound (M20) with a diazotizing agent in the presence of an acidic aqueous solution.
  • the reaction is performed in the presence of a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane, alcohols such as methanol and ethanol, aprotic polar solvents such as acetonitrile, DMF, NMP and DMSO, water And mixtures thereof.
  • the diazotizing agent used in the reaction include sodium nitrite.
  • the acidic aqueous solution used for the reaction examples include sulfuric acid, hydrochloric acid, acetic acid, and a mixture thereof.
  • the diazotizing agent is usually used in a proportion of 1 to 10 mol and the acid in a proportion of 1 to 100 mol.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (M18) can be isolated by performing post-treatment operations such as addition of water to the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (M18) can also be purified by chromatography, recrystallization, and the like.
  • R 5 is CF 3 , A is NCH 3 , and n and R 1 are combinations according to any one of [Table 1] to [Table 3].
  • R 5 is CF 2 CF 3 , A is NCH 3 , and n and R 1 are combinations according to any one of [Table 1] to [Table 3].
  • R 5 is CF 2 CF 2 CF 3 , A is NCH 3 , and n and R 1 are combinations according to any one of [Table 1] to [Table 3] Compound.
  • R 5 is CF (CF 3 ) 2 , A is NCH 3 , and n and R 1 are combinations according to any one of [Table 1] to [Table 3] Compound.
  • R 5 is S (O) CF 3 , A is NCH 3 , and n and R 1 are combinations according to any one of [Table 1] to [Table 3] Compound.
  • R 5 is S (O) 2 CF 3 , A is NCH 3 , and n and R 1 are combinations according to any one of [Table 1] to [Table 3] Invention compounds.
  • R 5 is SCF 2 CF 3 , A is NCH 3 , and n and R 1 are combinations according to any one of [Table 1] to [Table 3].
  • R 5 is S (O) CF 2 CF 3 , A is NCH 3 , and n and R 1 are combinations according to any one of [Table 1] to [Table 3] The compound of the present invention.
  • R 5 is S (O) 2 CF 2 CF 3 , A is NCH 3 , and n and R 1 are combinations according to any one of [Table 1] to [Table 3] A compound of the present invention.
  • R 5 is SCF 2 CF 2 CF 3 , A is NCH 3 , and n and R 1 are combinations according to any one of [Table 1] to [Table 3] Compound.
  • R 5 is S (O) CF 2 CF 2 CF 3 , A is NCH 3 , and n and R 1 are the combinations according to any one of [Table 1] to [Table 3] The compound of the present invention.
  • R 5 is S (O) 2 CF 2 CF 2 CF 3 , A is NCH 3 , and n and R 1 are described in any one of [Table 1] to [Table 3] The compound of the present invention which is a combination.
  • R 5 is SCF (CF 3 ) 2 , A is NCH 3 , and n and R 1 are combinations according to any one of [Table 1] to [Table 3] Compound.
  • R 5 is S (O) CF (CF 3 ) 2 , A is NCH 3 , and n and R 1 are the combinations according to any one of [Table 1] to [Table 3] The compound of the present invention.
  • R 5 is S (O) 2 CF (CF 3 ) 2 , A is NCH 3 , and n and R 1 are described in any one of [Table 1] to [Table 3] The compound of the present invention which is a combination.
  • R 5 is CF 3
  • A is an oxygen atom
  • n and R 1 are a combination described in any of [Table 1] to [Table 3].
  • R 5 is CF 2 CF 3
  • A is an oxygen atom
  • n and R 1 are combinations according to any one of [Table 1] to [Table 3].
  • R 5 is CF 2 CF 2 CF 3
  • A is an oxygen atom
  • n and R 1 are combinations according to any one of [Table 1] to [Table 3] Compound.
  • R 5 is CF (CF 3 ) 2 , A is an oxygen atom, and n and R 1 are combinations according to any one of [Table 1] to [Table 3] Compound.
  • the compound of the present invention in which, in the formula (1), R 5 is SCF 3 , A is an oxygen atom, and n and R 1 are a combination described in any one of [Table 1] to [Table 3].
  • R 5 is S (O) CF 3
  • A is an oxygen atom
  • n and R 1 are combinations according to any one of [Table 1] to [Table 3] Compound.
  • R 5 is S (O) 2 CF 3 , A is an oxygen atom, and n and R 1 are combinations described in any of [Table 1] to [Table 3] Invention compounds.
  • the compound of the present invention in which, in the formula (1), R 5 is SCF 2 CF 3 , A is an oxygen atom, and n and R 1 are combinations according to any one of [Table 1] to [Table 3].
  • R 5 is S (O) CF 2 CF 3 , A is an oxygen atom, and n and R 1 are combinations according to any one of [Table 1] to [Table 3] The compound of the present invention.
  • R 5 is S (O) 2 CF 2 CF 3 , A is an oxygen atom, and n and R 1 are combinations according to any one of [Table 1] to [Table 3] A compound of the present invention.
  • R 5 is SCF 2 CF 2 CF 3 , A is an oxygen atom, and n and R 1 are combinations according to any one of [Table 1] to [Table 3] Compound.
  • R 5 is S (O) CF 2 CF 2 CF 3 , A is an oxygen atom, and n and R 1 are the combinations according to any one of [Table 1] to [Table 3] The compound of the present invention.
  • R 5 is S (O) 2 CF 2 CF 2 CF 3 , A is an oxygen atom, and n and R 1 are any one of [Table 1] to [Table 3] The compound of the present invention which is a combination.
  • R 5 is SCF (CF 3 ) 2 , A is an oxygen atom, and n and R 1 are combinations according to any one of [Table 1] to [Table 3] Compound.
  • R 5 is S (O) CF (CF 3 ) 2 , A is an oxygen atom, and n and R 1 are the combinations according to any one of [Table 1] to [Table 3] The compound of the present invention.
  • R 5 is S (O) 2 CF (CF 3 ) 2 , A is an oxygen atom, and n and R 1 are any one of [Table 1] to [Table 3] The compound of the present invention.
  • R 5 is S (O) 2 CF (CF 3 ) 2 , A is an oxygen atom, and n and R 1 are any one of [Table 1]
  • A is NCH 3 , R 6 is CF 3 , and R 1 is a combination according to any one of Table 1 to Table 3.
  • A is NCH 3
  • R 6 is CF 2 CF 3
  • R 1 is a combination according to any one of [Table 1] to [Table 3].
  • A is NCH 3 , R 6 is CF (CF 3 ) 2 , and R 1 is a combination described in any of [Table 1] to [Table 3].
  • A is NCH 3 , R 6 is SCF 3 , and R 1 is a combination according to any one of [Table 1] to [Table 3].
  • A is NCH 3 , R 6 is S (O) CF 3 , and R 1 is a combination according to any one of Table 1 to Table 3.
  • A is NCH 3 , R 6 is S (O) 2 CF 3 , and R 1 is a combination according to any one of [Table 1] to [Table 3] .
  • A is NCH 3 , R 6 is SCF 2 CF 3 , and R 1 is a combination according to any one of [Table 1] to [Table 3].
  • A is NCH 3
  • R 6 is S (O) CF 2 CF 3
  • R 1 is a combination according to any one of [Table 1] to [Table 3] Compound.
  • A is NCH 3
  • R 6 is S (O) 2 CF 2 CF 3
  • R 1 is a combination described in any of [Table 1] to [Table 3] Invention compounds.
  • A is NCH 3
  • R 6 is SCF 2 CF 2 CF 3
  • R 1 is a combination according to any one of [Table 1] to [Table 3].
  • A is NCH 3
  • R 6 is S (O) CF 2 CF 2 CF 3
  • R 1 is a combination described in any of [Table 1] to [Table 3]
  • the compound of the present invention In the formula (1B), A is NCH 3 , R 6 is S (O) 2 CF 2 CF 2 CF 3 , and R 1 is a combination according to any one of [Table 1] to [Table 3] A compound of the present invention.
  • A is NCH 3
  • R 6 is SCF (CF 3 ) 2
  • R 1 is a combination according to any one of Table 1 to Table 3.
  • A is NCH 3
  • R 6 is S (O) CF (CF 3 ) 2
  • R 1 is a combination according to any one of [Table 1] to [Table 3]
  • the compound of the present invention in the formula (1B), A is NCH 3 , R 6 is S (O) 2 CF (CF 3 ) 2 , and R 1 is a combination according to any one of [Table 1] to [Table 3]
  • a compound of the present invention In the formula (1B), A is an oxygen atom, R 6 is CF 3 , and R 1 is a combination according to any one of Table 1 to Table 3.
  • A is an oxygen atom
  • R 6 is CF 2 CF 3
  • R 1 is a combination according to any one of Table 1 to Table 3.
  • A is an oxygen atom
  • R 6 is CF 2 CF 2 CF 3
  • R 1 is a combination according to any one of [Table 1] to [Table 3].
  • the compound of the present invention in which, in the formula (1B), A is an oxygen atom, R 6 is CF (CF 3 ) 2 , and R 1 is a combination described in any of [Table 1] to [Table 3].
  • A is an oxygen atom
  • R 6 is SCF 3
  • R 1 is a combination according to any one of [Table 1] to [Table 3].
  • A is an oxygen atom
  • R 6 is S (O) CF 3
  • R 1 is a combination described in any of [Table 1] to [Table 3].
  • A is an oxygen atom
  • R 6 is S (O) 2 CF 3
  • R 1 is a combination according to any one of [Table 1] to [Table 3] .
  • A is an oxygen atom
  • R 6 is SCF 2 CF 3
  • R 1 is a combination according to any one of [Table 1] to [Table 3].
  • A is an oxygen atom
  • R 6 is S (O) CF 2 CF 3
  • R 1 is a combination according to any one of [Table 1] to [Table 3] Compound.
  • A is an oxygen atom
  • R 6 is S (O) 2 CF 2 CF 3
  • R 1 is a combination described in any of [Table 1] to [Table 3] Invention compounds.
  • A is an oxygen atom
  • R 6 is SCF 2 CF 2 CF 3
  • R 1 is a combination according to any one of [Table 1] to [Table 3].
  • A is an oxygen atom
  • R 6 is S (O) CF 2 CF 2 CF 3
  • R 1 is a combination described in any of [Table 1] to [Table 3].
  • the compound of the present invention In the formula (1B), A is an oxygen atom, R 6 is S (O) 2 CF 2 CF 2 CF 3 , and R 1 is a combination according to any one of [Table 1] to [Table 3]
  • A is an oxygen atom
  • R 6 is SCF (CF 3 ) 2
  • R 1 is a combination according to any one of [Table 1] to [Table 3].
  • A is an oxygen atom
  • R 6 is S (O) CF (CF 3 ) 2
  • R 1 is a combination described in any of [Table 1] to [Table 3]
  • A is an oxygen atom
  • R 6 is S (O) 2 CF (CF 3 ) 2
  • R 1 is a combination according to any one of [Table 1] to [Table 3] A compound of the present invention.
  • A is NCH 3
  • R 6 is S (O) 2 CF 3
  • R 1 is a combination according to any one of [Table 1] to [Table 3] .
  • A is NCH 3
  • R 6 is S (O) CF 2 CF 3
  • R 1 is a combination according to any one of [Table 1] to [Table 3] Compound.
  • A is NCH 3
  • R 6 is S (O) 2 CF 2 CF 3
  • R 1 is a combination described in any of [Table 1] to [Table 3] Invention compounds.
  • A is NCH 3
  • R 6 is SCF 2 CF 2 CF 3
  • R 1 is a combination according to any one of [Table 1] to [Table 3].
  • A is NCH 3
  • R 6 is S (O) CF 2 CF 2 CF 3
  • R 1 is a combination described in any of [Table 1] to [Table 3] The compound of the present invention.
  • A is NCH 3
  • R 6 is S (O) 2 CF 2 CF 2 CF 3
  • R 1 is a combination according to any one of [Table 1] to [Table 3]
  • a compound of the present invention in which, in the formula (1C), A is NCH 3 , R 6 is SCF (CF 3 ) 2 and R 1 is a combination described in any of [Table 1] to [Table 3].
  • A is NCH 3
  • R 6 is S (O) CF (CF 3 ) 2
  • R 1 is a combination described in any of [Table 1] to [Table 3]
  • A is NCH 3
  • R 6 is S (O) 2 CF (CF 3 ) 2
  • R 1 is a combination according to any one of [Table 1] to [Table 3]
  • a compound of the present invention in the formula (1C), the compound of the present invention wherein A is an oxygen atom, R 6 is CF 3 , and R 1 is a combination described in any of [Table 1] to [Table 3].
  • A is an oxygen atom
  • R 6 is S (O) CF 3
  • R 1 is a combination described in any of [Table 1] to [Table 3].
  • A is an oxygen atom
  • R 6 is S (O) 2 CF 3
  • R 1 is a combination according to any one of [Table 1] to [Table 3] .
  • A is an oxygen atom
  • R 6 is S (O) CF 2 CF 3
  • R 1 is a combination described in any of [Table 1] to [Table 3] Compound.
  • A is an oxygen atom
  • R 6 is S (O) 2 CF 2 CF 3
  • R 1 is a combination described in any of [Table 1] to [Table 3] Invention compounds.
  • the compound of the present invention in which, in the formula (1C), A is an oxygen atom, R 6 is SCF 2 CF 2 CF 3 , and R 1 is a combination described in any of [Table 1] to [Table 3].
  • A is an oxygen atom
  • R 6 is S (O) CF 2 CF 2 CF 3
  • R 1 is a combination described in any one of [Table 1] to [Table 3]
  • the compound of the present invention In the formula (1C), A is an oxygen atom, R 6 is S (O) 2 CF 2 CF 2 CF 3 , and R 1 is a combination according to any one of [Table 1] to [Table 3] A compound of the present invention.
  • A is an oxygen atom
  • R 6 is S (O) CF (CF 3 ) 2
  • R 1 is a combination according to any one of [Table 1] to [Table 3]
  • A is an oxygen atom
  • R 6 is S (O) 2 CF (CF 3 ) 2
  • R 1 is a combination according to any one of [Table 1] to [Table 3]
  • pests for which the compounds of the present invention are effective include harmful arthropods such as harmful insects and harmful mites, and harmful linear animals such as nematodes. Specific examples of such pests include the following.
  • Hemiptera small brown planthopper (Laodelphax striatellus), brown planthopper (Nilaparvata lugens), planthoppers such as Sejirounka (Sogatella furcifera), green rice leafhopper (Nephotettix cincticeps), Taiwan green rice leafhopper (Nephotettix virescens), tea Roh green leafhopper such as leafhopper (Empoasca onukii) Cotton aphids (Aphis gossypi), peach aphids (Myus persicae), radish aphids (Brevicorine brassicae), aphid spiraecola, tulip beetle aphids (M) crosifum euphorbiae, potato beetle aphids (Auracorthum solani), wheat beetle aphids (Rhopalosiphum padi), citrus aphids (Toxopter
  • Stink bugs such as stink bugs (Riptortus clavetus), spider helicopter bugs (Leptocorisa chinensis), bark beetles (Eysarcoris parvus), winged beetle (Halyomorpha mista), and the like vaporariorum), sweetpotato whitefly (Bemisia tabaci), mandarin orange whitefly (Dialeurodes citri), whiteflies such as mandarin orange spiny whitefly (Aleurocanthus spiniferus), Acamar scale insects (Aonidiella aurantii), Sanho zero scale insects (Comstockaspis perniciosa), citrus snow scale (Unaspis citri ), Ruby Beetle (Ceroplastes rubens), Iceria scale insect (Icerya purchasi), Fujino scale insect (Pranococcus kraunhiae), Pseudococcus longispin (Pseudococcus longis
  • Lepidoptera rice stem borer (Chilo suppressalis), Sankameiga (Tryporyza incertulas), leaf roller (Cnaphalocrocis medinalis), Watanomeiga (Notarcha derogata), Indian meal moth (Plodia interpunctella), the European corn borer (Ostrinia furnacalis), high Madara Roh moth (Hellula undalis), Shibatsutoga (Pediasia teterrulus) and other moths, Spodoptera litura, Spodoptera exigua, Ayuyoto (Pseudaletia sepata), Madam Gritters such as Strassicae, Agrotis ipsilon, Tamanaginuwaba (Plusia nigrisigna), Trichopulsia, Heliotis, Helicoberpa, etc.
  • Thrips Frankliniella occidentalis, Thrips peri, Citrus dorsalis, and Thrips thrips.
  • Diptera Culex pipiens palens, Culex quaters, and other squids such as Culex quinquefasciaus, etc .; Houseflies such as Anopheles, Chironomidae, Musca domestica, Muscina stabulans, etc., Drosophila, Drosophila, Drosophila, Delaplata, Timaelae Ribae (Agromyza oryzae), rice Hime leafminer (Hydrellia griseola), tomato leafminer, (Liriomyza sativae), legume leafminer (Liriomyza trifolii), leafminer such as the pea (Chromatomyia horticola), chloropidae such as Inekimoguribae (Chlorops oryzae), melon fly (Dacus cucurbitae), fruit flies such as Ceratitis capitata, fruit flies such as Drosophila,
  • Coleoptera Western corn rootworm (Diabrotica virgifera virgifera), corn root worms such as Southern corn rootworm (Diabrotica undecimpunctata howardi), cupreous chafer (Anomala cuprea), rufocuprea (Anomala rufocuprea), beetles such as Japanese beetle (Popillia japonica) , Maysweville (Sytophilus zeamais), Rice weevil (Lissohoptrus oryzophilus), Azuki beetle (Callosobrchuchus Kunststoffsis), Green weevil (Echinocnemus squatium) omus grandis), weevils such as grass reed weevil (Sphenophorus venatus), Chai Loco Meno mealworm (Tenebrio molitor), mealworm such as red flour beetle (Tribolium castaneum), Inedorooimushi (Oulema or
  • Tosama grasshopper Locusta migratoria
  • Kera Gryllotalpa africana
  • Oxya yezoensis Species: Tosama grasshopper (Locusta migratoria), Kera (Gryllotalpa africana), Oxya yezoensis, Lobster (Oxya japonica), and crickets.
  • Lepidoptera Cat fleas (Ctenocephalides felis), dog fleas (Ctenocephalides canis), human fleas (Pulex irritans), keops mouse fleas (Xenopsilla cheopes) and the like. *
  • Anoplura body louse (Pediculus humanus corporis), head lice (Pediculus humanus humanus), crab louse (Phthirus pubis), Ushijirami (Haematopinus eurysternus), Hitsujijirami (Dalmalinia ovis), Butajirami (Haematopinus suis), Inujirami (Linognathus setosus) and the like. *
  • Lepidoptera sheep lice (Dalmalinia ovis), cattle lice (Dalmalinia bovis), chicken lice (Menonpon gallinae), dog lice (Trichodictes canis), cat wolf squirr
  • Hymenoptera Monomorium phalaosis, Formica fusca japonica, Ruriari (Ochetellus pungens), Psomylem puns, Pepperm sperm. Ants such as Argentine ants (Linepithema humile), wasps such as wasps, scallops, and wasps such as wasp (Athalia rosae) and Japanese bee (Athalia japonica).
  • Cockroaches German cockroaches (Blatella germanica), Black cockroaches (Periplaneta fligninosa), Cockroach cockroaches (Periplaneta americana), Japanese cockroaches (Periplaneta brunat)
  • Isoptera Yamato termite (Reticulitermes speratus), Formosan subterranean termite (Coptotermes formosanus), the United States drywood termites (Incisitermes minor), Daikoku termites (Cryptotermes domesticus), Taiwan termites (Odontotermes formosanus), Kou Shun termite (Neotermes koshunensis), Satsuma termites (Glyptotermes satsumensis), termites termites (Glyptotermes nakajimai), termites termites (Glyptotermes fuscus), termites termites (Glyptotermes kodamai) Termites (Glyptotermes kushimensis), giant termite (Hodotermopsis japonica), Kou Shu Ye termite (Coptotermes guangzhoensis), Amami termites (Reticulitermes miyatakei), R.
  • Mite order Tetanychus urticae, Tetanychus kanzawai, utani mite (Ponyychus urmi), mite mite (p) Rabbit mites (Aculops lycopersici), Rabbit mites (Calacarus carinatus), Rabbit mites (Acaphylla theavagrans), Scarlet mite (Eriophys chibaensis), Apple crustaceans (Aulus dachi) Dust mites, such as mites, Polyphagotarsonemus latus, Scots mites, Bremen spider mites, Hemiphysalis mites, Haemphysalis mite, Haemphysalis longis Dermacentor variabilis, Ixodes ovatus, Ixes persulcatus, Black legged tick (Ixodes scapularis), American larva tick (Amblyomama amer) canum), Boophilus microplus (Bo
  • pteronyssinus (Dermatophagoides ptrenyssnus) Lion mites, such as Cheyletus eruditus, Stag beetle tick (Cheyletus malaccensis), Scarlet tick (Cheyletus mooreii), Tiger tickle (Cheeletiell) mite mites such as a yasguri, mite mites (Octoectes cynotis), mites mites such as Sacroptes scabiei, mite mites such as Demodex canis, mite mites, b Species such as Ornithonysus sylvairum and Dermanyssus gallinae, and Tsutsugamushi such as Leptotrombidium akamushi.
  • Spider such as Chiracanthium japonicum and Latrodictus hasseltii Lip and limb class: Geeu (Thereunema hilgendorfi), Tobizukade (Scorpendra subspinipes) and the like. Double leg class: Oxidus gracilis, Nedyopus tambanus, etc. Isopods: Armadillium vulgare, etc. Gastropoda: Limax marginatus, Limax flavus, etc.
  • Nematodes rice Shin Galle nematode (Aphelenchoides besseyi), strawberry menu nematode (Nothotylenchus acris), sweet potato root-knot nematode (Meloidogyne incognita), northern root-knot nematode (Meloidogyne hapla), Java root-knot nematode (Meloidogyne javanica), soybean cyst nematode (Heterodera glycines), Potato cyst nematode (Globodera rostochiensis), southern nematode crested pea (Pratylenchus coffeae), barley nematode nematode (Pratylenchus neglectus).
  • Pests include pests that have reduced drug sensitivity to existing pesticides, that is, have acquired drug resistance.
  • the pest control agent of the present invention contains the compound of the present invention and an inert carrier.
  • the pest control agent of the present invention is usually a mixture of the compound of the present invention and an inert carrier such as a solid carrier, liquid carrier, gaseous carrier, etc.
  • the pest control agent of the present invention usually contains 0.01 to 95% by weight of the compound of the present invention.
  • solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, bentonite, fusami clay, acidic clay), synthetic hydrous silicon oxide, talc, ceramics, and other inorganic minerals (sericite, quartz, sulfur).
  • Polyester resins such as polyethylene terephthalate, nylon resins such as nylon-6, nylon-11, and nylon-66, polyamide resins, polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-propylene copolymers).
  • liquid carrier examples include water, alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, phenoxyethanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (Toluene, xylene, ethylbenzene, dodecylbenzene, phenylxylylethane, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, isopropyl myristate, Ethyl oleate, diisopropyl adipate, diisobutyl adipate, propylene glycol monomethyl ether acetate, etc.), n
  • Acid amides N, N-dimethylformamide, N, N-dimethylacetamide, etc.
  • halogenated hydrocarbons diichloromethane, trichloroethane, carbon tetrachloride, etc.
  • sulfoxides dimethylsulfoxide, etc.
  • propylene carbonate and vegetable oil Soybean oil, cottonseed oil, etc.
  • gaseous carrier examples include fluorocarbon, butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbon dioxide gas.
  • surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, and polyethylene glycol fatty acid ester, and anions such as alkyl sulfonate, alkyl benzene sulfonate, and alkyl sulfate. Surfactant is mentioned.
  • formulation adjuvants include sticking agents, dispersants, colorants, antifreezes and stabilizers, such as casein, gelatin, sugars (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin Derivatives, bentonite, synthetic water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids, etc.), glycerin, PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).
  • sticking agents such as casein, gelatin, sugars (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin Derivatives, bentonite, synthetic water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyacryl
  • the base material of the resin preparation examples include vinyl chloride polymers, polyurethanes, etc., and these base materials include phthalic acid esters (dimethyl phthalate, dioctyl phthalate, etc.) and adipic acid esters as necessary. Further, a plasticizer such as stearic acid may be added.
  • the resin formulation is obtained by kneading the compound in the base material using a normal kneading apparatus, and then molding by injection molding, extrusion molding, press molding, etc., and if necessary, through steps such as molding, cutting, It can be processed into resin preparations such as plate, film, tape, net, and string.
  • These resin preparations are processed, for example, as animal collars, animal ear tags, sheet preparations, attracting strings, or gardening supports.
  • the bait base include cereal flour, vegetable oil, sugar, crystalline cellulose and the like, and if necessary, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, and preservatives such as dehydroacetic acid.
  • antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid
  • preservatives such as dehydroacetic acid.
  • Additives for preventing accidental eating by children and pets such as pepper powder, pests such as cheese flavor, onion flavor and peanut oil are added.
  • the pest control method of the present invention is carried out by applying an effective amount of the compound of the present invention to pests directly and / or to pest habitats (plants, soil, households, animal bodies, etc.).
  • the pest control method of the present invention is usually used in the form of the pest control agent of the present invention.
  • salts formed by the compounds of the present invention with strong acids such as sulfuric acid, methanesulfonic acid and p-toluenesulfonic acid also have excellent control activity against pests.
  • the application amount is usually 1 to 10,000 g as the amount of the compound of the present invention per 10,000 m 2 .
  • the pest control agent of the present invention is formulated into an emulsion, a wettable powder, a flowable agent, etc., it is usually diluted with water so that the active ingredient concentration is 0.01 to 10,000 ppm. Granules, powders and the like are usually applied as they are.
  • preparations and water dilutions of the preparations may be applied directly to pests or plants such as plants to be protected from pests, and in order to control pests that inhabit cultivated soil. You may apply to.
  • the soil When applied to soil, the soil may be the soil where the plant is cultivated or the soil where the plant is to be cultivated.
  • the resin preparation processed into a sheet or string can also be used by a method such as wrapping around a crop, stretching it in the vicinity of the crop, or laying it on the stock soil.
  • Examples of the place where the pest control agent of the present invention is used include paddy field, upland field, tea garden, orchard, and non-agricultural land.
  • the pest control agent of the present invention can also be used in a seedling tray, a seedling box, a seedling culture soil, a seedling mat, and a hydroponic solution in a hydroponic farm.
  • the cultivation method of plants in paddy fields and upland fields may be plowing cultivation or non-plowing cultivation.
  • the amount applied is the amount of the compound of the present invention per area of 1 m 2 when applied on the surface, usually 0.01.
  • the amount of the compound of the present invention per 1 m 3 of space is usually 0.01 to 500 mg when applied to a space.
  • the pest control agent of the present invention is formulated into an emulsion, a wettable powder, a flowable agent, etc., it is usually diluted with water so that the active ingredient concentration is 0.1 to 10,000 ppm. Apply oils, aerosols, smoke, poison baits, etc. as they are.
  • the harmful arthropod control agent of the present invention When used to control ectoparasites of cattle, horses, pigs, sheep, goats, chickens, small animals such as dogs, cats, rats, mice, etc., it is well known in veterinary medicine. Can be used on animals.
  • systemic suppression for example, administration by tablet, feed mixing, suppository, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.) is intended for non-systemic suppression.
  • an oil agent or an aqueous liquid is sprayed, a pour-on treatment or a spot-on treatment is performed, the animal is washed with a shampoo preparation, or a resin preparation is attached to the animal with a collar or ear tag.
  • the amount of the compound of the present invention is usually in the range of 0.1 to 1,000 mg per 1 kg body weight of the animal.
  • the pest control agent of the present invention can be used in farmland where the following plants (hereinafter referred to as the present plant) are cultivated.
  • Cereals corn, rice, wheat, barley, rye, triticale, oats, sorghum, cotton, soybeans, peanuts, peanuts, cypress (green beans), lentils, azuki beans, cowpeas, mung bean, safflower beans, red bean, moss beans, tepareen, Broad bean, pea, chickpea, lentil, lupine, pigeon bean, buckwheat, sugar beet, rapeseed, sunflower, sugar cane, tobacco, etc.
  • Vegetables Eggplant vegetables (eggplants, tomatoes, peppers, peppers, bell peppers, potatoes, etc.), cucurbits vegetables (cucumbers, pumpkins, zucchini, watermelons, melons, etc.), cruciferous vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, mustard, broccoli, cauliflower, etc.), Asteraceae vegetables (burdock, garlic, artichoke, lettuce, etc.), liliaceae vegetables (eg, leek, onion, garlic, asparagus), celery family vegetables (carrot, parsley, celery) , American Bow Fu, etc.), Rubiaceae vegetables (spinach, chard, etc.), Lamiaceae vegetables (perilla, mint, basil, lavender, etc.), strawberry, sweet potato, yam, taro, etc.
  • cucurbits vegetables cucumbers, pumpkins, zucchini, watermelons, melons, etc.
  • cruciferous vegetables radish, turnip, horseradish,
  • Fruit trees berries (apples, pears, Japanese pears, quince, quince, etc.), nuclear fruits (peaches, plums, nectarines, ume, sweet cherry, apricots, prunes, etc.), citrus (satsuma mandarin, orange, lemon, lime, grapefruit) ), Nuts (chestnut, walnut, hazel, almond, pistachio, cashew nut, macadamia nut, etc.), berries (blueberry, cranberry, blackberry, raspberry, etc.), grape, oyster, olive, loquat, banana, coffee, Date palm, coconut palm, oil palm etc.
  • Trees other than fruit trees tea, mulberry, flowering trees (Satsuki, camellia, hydrangea, sasanqua, shikimi, sakura, yurinoki, crape myrtle, eustoma, etc.), roadside trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak) , Poplar, redwood, fu, sycamore, zelkova, blackfish, Japanese amberjack, moths, pine, pine, spruce, yew, elm, Japanese cypress, etc.), coral jug, dogwood, cedar, cypress, croton, masaki, kanamochi, etc.
  • the plant includes plants bred by hybrid technology.
  • the present plant includes a genetically modified plant prepared by a genetic recombination technique.
  • This plant also includes plants to which resistance to herbicides is imparted by genetic recombination techniques or classical breeding methods.
  • the plant further includes a plant imparted with an ability to produce a selective toxin against pests by a genetic recombination technique.
  • This plant includes a plant imparted with an ability to produce an anti-pathogenic substance by genetic recombination technology.
  • This plant includes plants to which useful traits such as oil component modification and amino acid content enhancing traits have been imparted.
  • the pest control agent of the present invention As a method of applying the pest control agent of the present invention to this plant to be protected from damage such as feeding by pests, specifically, application to the foliage, flower vases or ears of plants such as foliage spraying Application to seeds of plants or vegetative propagation organs (for example, seed buds, bulbs, tubers, bulbs, stem fragments, etc.); application to plant seedlings (including cuttings).
  • foliage spraying Application to seeds of plants or vegetative propagation organs (for example, seed buds, bulbs, tubers, bulbs, stem fragments, etc.); application to plant seedlings (including cuttings).
  • Examples of the method for applying the pest control agent of the present invention to the foliage, flower vases or ears of plants include application methods applied to the surface of plants such as foliage spray, trunk spray, etc., and before flowering, during flowering A method of spraying on the vase or the whole plant at the flowering time including after flowering is mentioned, and a method of spraying on the ear of the heading time or the whole plant when the plant is cereal.
  • Examples of the method for applying the pest control agent of the present invention to plant seeds or vegetative propagation organs include, for example, a method of coating, smearing or applying to seeds or vegetative propagation organs, and seeds or vegetative propagation organs in liquid formulations.
  • Examples thereof include a dipping method and a method of coating seeds or vegetative propagation organs (for example, a film coating method, a pellet coating method, etc.).
  • the amount of the compound of the present invention is usually applied in the range of 0.2 to 5,000 g, preferably 0.5 to 1,000 g per 100 kg of plant seeds or vegetative propagation organs.
  • Preferred dosage forms are aqueous liquid suspension preparations such as emulsions, wettable powders, flowables, and microcapsules.
  • Plants to which the method is applied include, among these plants, soybeans, corn, cotton, wheat, barley, rye, triticale, oats, rice, sorghum, peanuts, peanuts except soybeans and peanuts, sugar beet, rapeseed, It is preferably applied to sunflower, potato, sugar cane and vegetables. When applied to sugarcane, sugarcane stalk fragments may be used in sugarcane cultivation.
  • the pest control agent of the present invention can be mixed or used in combination with known insecticides, acaricides, nematicides, fungicides, plant growth regulators and synergists.
  • the pest control agent of the present invention can be used in combination with known herbicides. Examples of active ingredients of such insecticides, acaricides, nematicides, fungicides, herbicides and synergists are shown below.
  • Insecticides Organophosphorus Compounds Acephate, Aluminum Phosphide, Butathiofos, Cadosafos, Chlorethoxyfos, Chlorfenvinphos, Chlorfenvinphos (Chlorpyrifos), Chlorpyrifos-methyl (Chlorpyrifos-methyl), Cyanophos (Cyanophos: CYAP), Diazinon (Diazinon), DCIP (Dichlorodiisopropylene ether), Diclofenthion (V), Dichlorfenthion (V) ), Dimethoate, dimethylvinphos, disulfoton, EPN, etion, ethoprofos, etrimfos, fention (MPP), EP, Phosthiazate, formothion, hydrogen phosphide, isofenphos, isoxathion, malathion, methulfenfos, methulf
  • pyrethroid compounds acrinathrin, allethrin, benfluthrin, beta-cyfluthrin, bifenthrin, cycloprotorin, fluprothrin (cycloprothrin) , Cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucitrate lucytrinate, flufenprox, flumethrin, fluvalinate, halfenprox, imiprothrin, permethrin, praretrin, praretrin resmethrin, sigma-cypermethrin, silafluofen, tefluthrin, tralomethrin, transfluthrin, tetramethrin ethrin), phenothrin, cyphenothrin, alpha-cypermethrin, zeta-c
  • Neonicotinoid compounds imidacloprid (imidac1oprid), nitenpyram (nitenpyram), acetamiprid (acetamipride), thiamethoxam, thiacloprid (thiacloprid), dinoteurin (dinothurine) (6) Benzoylurea compound Chlorfluazuron, bistrifluron, diafenthiuron, diflubenzuron, fluazuron, flucycloxuron, flucyclolone (Flufenoxuron), hexaflumuron, lufenuron, novaluron, novifluuron, teflubenzuron, triflumuron, and triflumuron.
  • Phenylpyrazole compounds Acetoprole, etiprole, fipronil, vaniliprole, pyriprole, and pyrafluprole.
  • Bt toxin Live spores and produced crystal toxins derived from Bacillus thuringiensis, and mixtures thereof;
  • Hydrazine compounds Chromafenozide, halofenozide, methoxyphenozide, and tebufenozide.
  • Insecticide Active Ingredients Machine oil, nicotine-sulfate; avermectin, bromopropyrate, buprofezin, chlorfenapyr, chlorphenapyr Ritranol, cyromazine, DD (1,3-Dichloropropene), emamectin benzoate, fenazaquin, flupirroprene, flupyrazolen , Indoxacarb, methoxadiazone, milbemycin-A, pymetrozine, pyridalyl, pyriprosul, spiromidol, spinodulsulfide tolfenpyrad, triazamate, flubendiamide, repimectin, arsenous acid, benclothiaz, lime nitrogen calcium lime ulfide, chlordane, DDT, DSP, flufenerim, flonicamid, flurimfen, formatenate, metham-ammonium, metam-ammonium
  • Active ingredients of acaricides acequinocyl, amitraz, benzoximate, bifenaate, phenisobromolate (BS), chinomethionate (BS), chinomethionate (BS) chlorfenson, clofentezine, cyflumetofene, kelsen (dicofol), etoxazole, fenbutatin oxide (fenbutafen), fenothiocarbene roximate, fluacrylpyrim, fluproxyfen, hexythiazox, propargite (BPPS), polynactin complex (pyridene), pyridaben (pyriben) (Tetradifon), spirodiclofen, spiromesifen, spirotetramat, amidoflumet, and cenopyrafen.
  • BS phenisobromolate
  • BS chinomethionate
  • BS chinomethionate
  • Active ingredients of nematicides DCIP, fostiazate, levamisole hydrochloride, methylisothiocyanate, morantel tartrate, and imiciafos.
  • Active ingredients of fungicides Propiconazole, Prothioconazole, Triadimenol, Prochloraz, Penconazole, Tebuconazole, Tebuconazole, Tebuconazole , Bromuconazole, epoxiconazole, difenoconazole, cyproconazole, metconazole, triflumazole, triflumizole Tetraconazole, microbutanil, fenbuconazole, hexaconazole, fluquinconazole, triticonazole, triticonazole, triticonazole, triticonazole Azole fungicidal compounds such as flutriafol; Cyclic amine bactericidal compounds such as fenpropimorph, tridemorph, fenpropidin; Benzimidazole fungicidal compounds such as carbendezim, benomyl, thiabendazole, thiophanate-methyl; Procymid
  • Hydroxybenzonitrile herbicidal compounds bromoxynil and ioxynil.
  • Dinitroaniline herbicidal compounds pendimethalin, prodiamine, and trifluralin.
  • Organophosphorus herbicidal compounds amiprofos-methyl, butamifos, bensulide, piperophos, anilofos, glyphosate, glufosinate, glufosinate, glufosinate P (glufosinate-P), and bialaphos.
  • Carbamate herbicidal compounds di-allate, tri-allate, EPTC, butyrate, beniocarb, esprocarb, molinate, dimepiperate (Swep), chlorpropham, phenmedifam, phenisopham, piributicarb, and asuram.
  • Acid amide herbicidal compounds propanil, propyzamide, bromobutide, and etobanzanide.
  • Chloroacetanilide herbicidal compounds acetochlor, acechlor, butachlor, dimethenamide, propachlor, metazachlor, metrachlor or totrachlor pretilachlor), tenylchlor (theny1ch1or), and petoxamide.
  • Diphenyl ether herbicidal compounds aciflufen-sodium, bifenox, oxyfluorfen, lactofen, fomesafen, clomethoxythonifen, and chloromethoxypheny.
  • Trione oxime herbicidal compounds alloxydim-sodium, cetoxydim, butoxydim, crestodim, cloxydimim, cycloxidim, texydimym (Traxydim), and profoxydim.
  • a sulfonylurea herbicidal compound chlorsulfuron, sulfomethuron-methyl, metsulfuron-methyl, chlorimuron-ethyl, trivenuron methyl (18) tribenuron-methyl, trisulfuron, bensulfuron-methyl, thifensulfuron-methyl, pyrazosulfuron-methyl, urmisyl-uryl-uryl-uryl Nicosulfuron (nico) ulfuron, amidosulfuron, cinosulfuron, imazosulfuron, rimsulfuron, halosulfuron (thulfuron), prosulfuron (thulsulfuron), prosulfuron (thulsulfuron) , Triflusulfuron-methyl, flazasulfuron, cyclosulfamuron, flupirsulfuron, sulfosulfurium, sulfosulfurimuron Azulsulfur
  • the present compound 1 1 H-NMR (DMSO-D 6 ) ⁇ : 9.57 (1H, s), 8.74 (1H, d), 8.46 (1H, s), 8.31 (1H, d), 8.17 (1H, d ), 8.00 (1H, d), 7.76 (1H, dd), 3.97-3.88 (5H, m), 1.24 (3H, t).
  • the obtained reaction mixture was poured into 1N aqueous hydrochloric acid solution, and the precipitated solid was collected by filtration. The obtained solid was washed with water and dried to obtain 9.8 g of a solid G.
  • a mixture of 13 g of iron powder, 19 mL of acetic acid, 200 mL of tetrahydrofuran, and 28 mL of water was heated to 65 ° C., and a mixed solution of 14 g of solid G and 50 mL of tetrahydrofuran was added dropwise with stirring. After completion of dropping, the mixture was stirred at 65 ° C. for 3 hours. The resulting reaction mixture was filtered through Celite (registered trademark) and washed with tetrahydrofuran.
  • a part represents a weight part.
  • Formulation Example 1 10 parts of any one of the compounds 1 to 19 of the present invention are dissolved in a mixture of 35 parts of xylene and 35 parts of N, N-dimethylformamide, and 14 parts of polyoxyethylene styryl phenyl ether and calcium dodecylbenzenesulfonate are dissolved therein. Add 6 parts and mix to obtain each formulation.
  • Formulation Example 2 4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic silicon hydroxide fine powder and 54 parts of diatomaceous earth are mixed, and 20 parts of any one of the compounds 1 to 19 of the present invention are added and mixed. Get a wettable powder.
  • Formulation Example 3 1 part of synthetic silicon hydrous fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are mixed with 2 parts of any one of the compounds 1 to 19 of the present invention. Next, an appropriate amount of water is added to the mixture, and the mixture is further stirred, granulated with a granulator, and dried by ventilation to obtain each granule.
  • Formulation Example 4 1 part of any one of the compounds 1 to 19 of the present invention is dissolved in an appropriate amount of acetone, and 5 parts of a synthetic silicon hydroxide fine powder, 0.3 part of isopropyl acid phosphate and 93.7 parts of fusami clay are added, The mixture is thoroughly mixed and acetone is removed by evaporation to obtain each powder.
  • Formulation Example 5 35 parts of a mixture of polyoxyethylene alkyl ether sulfate ammonium salt and white carbon (weight ratio 19), 10 parts of any one of the compounds 1 to 19 of the present invention, and 55 parts of water are mixed and finely divided by a wet pulverization method. Each flowable agent is obtained by grinding.
  • Formulation Example 6 0.1 part of any one of the compounds 1 to 19 of the present invention is dissolved in a mixture of 5 parts of xylene and 5 parts of trichloroethane, and this is mixed with 89.9 parts of deodorized kerosene to obtain each oil agent.
  • Formulation Example 7 10 mg of any one of the compounds 1 to 19 of the present invention is dissolved in 0.5 ml of acetone, and this solution is added dropwise to 5 g of animal solid feed powder (solid feed powder CE-2 for breeding breeding, Nippon Claire Co., Ltd.). And mix evenly. Then acetone is evaporated to dryness to obtain each poisonous bait.
  • animal solid feed powder solid feed powder CE-2 for breeding breeding, Nippon Claire Co., Ltd.
  • Formulation Example 8 0.1 part of any one of the compounds 1 to 19 of the present invention and 49.9 parts of neothiozole (Chuo Kasei Co., Ltd.) are put in an aerosol can, and after mounting an aerosol valve, 25 parts of dimethyl ether and 25 parts of LPG are filled. Shake and attach an actuator to obtain an oil aerosol.
  • Formulation Example 9 0.6 part of any one of compounds 1 to 19 of the present invention, 0.01 part of BHT (2,6-di-tert-butyl-4-methylphenol), 5 parts of xylene, 3.39 parts of deodorized kerosene and emulsifier ⁇ Rheodor MO-60 (manufactured by Kao Corporation) ⁇ After mixing 1 part and 50 parts of distilled water into an aerosol container and attaching a valve, 40 parts of propellant (LPG) was added through the valve. Pressure filling to obtain an aqueous aerosol.
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • xylene 3.39 parts of deodorized kerosene and emulsifier ⁇ Rheodor MO-60 (manufactured by Kao Corporation) ⁇
  • LPG propellant
  • Formulation Example 10 0.1 g of any one of the compounds 1 to 19 of the present invention is mixed with 2 ml of propylene glycol, impregnated into a porous ceramic plate of 4.0 ⁇ 4.0 cm and thickness of 1.2 cm, and a heating smoke Get.
  • Formulation Example 11 5 parts of any one of the present compounds 1 to 19 and an ethylene-methyl methacrylate copolymer (ratio of methyl methacrylate in the copolymer: 10% by weight, ACRIFT (registered trademark) WD301, manufactured by Sumitomo Chemical Co., Ltd.) 95
  • the part is melt-kneaded with a closed pressure kneader (manufactured by Moriyama Seisakusho), and the resulting kneaded product is extruded from an extrusion molding machine through a molding die to obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm.
  • Formulation Example 12 5 parts of any one of the compounds 1 to 19 of the present invention and 95 parts of a soft vinyl chloride resin are melt-kneaded with a closed pressure kneader (manufactured by Moriyama Seisakusho), and the resulting kneaded product is passed from an extrusion molding machine through a molding die. To obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm.
  • Formulation Example 13 Any one of the compounds 1 to 19 of the present invention 100 mg, lactose 68.75 mg, corn starch 237.5 mg, microcrystalline cellulose 43.75 mg, polyvinylpyrrolidone 18.75 mg, sodium carboxymethyl starch 28.75 mg, and magnesium stearate Mix 2.5 mg and compress the resulting mixture to an appropriate size to obtain tablets.
  • Formulation Example 14 Any one of the compounds 1 to 19 of the present invention 25 mg, lactose 60 mg, corn starch 25 mg, carmellose calcium 6 mg, and 5% hydroxypropylmethylcellulose are mixed in an appropriate amount, and the resulting mixture is hard shell gelatin capsule or hydroxypropylmethylcellulose capsule To obtain capsules.
  • Formulation Example 15 Any one of the compounds 1 to 19 of the present invention 100 mg, fumaric acid 500 mg, sodium chloride 2000 mg, methylparaben 150 mg, propylparaben 50 mg, granule sugar 25000 mg, sorbitol (70% solution) 13000 mg, VeegumK (VanderbiltCo.) 100 mg, flavor 35 mg, And distilled water is added to 500 mg of the colorant so that the final volume becomes 100 ml, and mixed to obtain a suspension for oral administration.
  • VanderbiltCo. VeegumK
  • Formulation Example 16 5% by weight of any one of the compounds 1 to 19 of the present invention is dissolved in 5% by weight of polysorbate 85, 3% by weight of benzyl alcohol, and 30% by weight of propylene glycol, and the pH of this solution is 6.0 to 6.5. After adding a phosphate buffer so that it becomes, the remainder is added with water to obtain a solution for oral administration.
  • Formulation Example 17 5% by weight of aluminum distearate in 57% by weight of fractionated coconut oil and 3% by weight of polysorbate 85 is added and dispersed by heating. This is cooled to room temperature and 25% by weight of saccharin is dispersed in the oily vehicle. To this, 10% by weight of any one of the compounds 1 to 19 of the present invention is allocated to obtain a paste preparation for oral administration.
  • Formulation Example 18 5% by weight of any one of the compounds 1 to 19 of the present invention is mixed with 95% by weight of limestone powder, and granules for oral administration are obtained using a wet granulation method.
  • Formulation Example 19 5 parts of any one of the compounds 1 to 19 of the present invention are dissolved in 80 parts of diethylene glycol monoethyl ether, and 15 parts of propylene carbonate is mixed therewith to obtain a spot-on solution.
  • Formulation Example 20 10 parts of any one of the compounds 1 to 19 of the present invention are dissolved in 70 parts of diethylene glycol monoethyl ether, and 20 parts of 2-octyldodecanol is mixed with this to obtain a pour-on solution.
  • Formulation Example 22 Any one of the compounds 1 to 19 of the present invention 0.15% by weight, animal feed 95% by weight, and 4.85% by weight of a mixture comprising dicalcium phosphate, diatomaceous earth, Aerosil, and carbonate (or chalk) are sufficiently stirred. Mix to obtain animal feed premix.
  • Formulation Example 23 7.2 g of any one of the compounds 1 to 19 of the present invention and 92.8 g of Fosco (registered trademark) S-55 (manufactured by Maruishi Pharmaceutical Co., Ltd.) are dissolved and mixed at 100 ° C., poured into a suppository, and cooled. Solidify to obtain a suppository.
  • Fosco registered trademark
  • S-55 manufactured by Maruishi Pharmaceutical Co., Ltd.
  • a part represents a weight part.
  • Formulation Example 1A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the compound 1 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 2A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 2 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 3A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the compound 3 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 4A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 4 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 5A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 5 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 6A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of compound 6 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 7A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 7 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 8A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 8 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 9A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the compound 9 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 10A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 10 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 11A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 11 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 12A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 12 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 13A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 13 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 14A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the compound 14 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 15A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 15 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 16A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 16 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 17A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 17 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 18A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 18 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 19A 0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the compound 19 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 20A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of Compound 1 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 21A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 2 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 22A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 3 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 23A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 4 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 24A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of Compound 5 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 25A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 6 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 26A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 7 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 27A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of Compound 8 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 28A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 9 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 29A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of compound 10 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 30A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 11 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 31A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 12 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 32A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 13 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 33A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 14 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 34A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 15 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 35A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 16 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 36A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 17 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 37A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 18 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 38A 10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 19 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 39A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of Compound 1 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 40A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of compound 2 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 41A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of compound 3 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 42A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 4 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 43A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of Compound 5 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 44A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of compound 6 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 45A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 7 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 46A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 8 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 47A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 9 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 48A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 10 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 49A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 11 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 50A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 12 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 51A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of compound 13 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 52A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 14 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 53A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 15 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 54A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 16 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 55A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of compound 17 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 56A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 18 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Formulation Example 57A 4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 19 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
  • Test example 1 Each formulation of the present compound 2,3,4,5,11,12,13,14,15 and 16 obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 200 ppm, A test chemical solution was prepared. Meanwhile, about 30 Aphis gossypi (all stages) were inoculated into cucumber seedlings (first true leaf development stage) planted in plastic cups and left for 1 day. The seedlings were sprayed with 20 ml of the test chemical solution. Six days after spraying, the number of live cotton aphids that parasitized on the leaves of the cucumber was examined, and the control value was determined by the following formula.
  • Control value (%) ⁇ 1 ⁇ (Cb ⁇ Tai) / (Cai ⁇ Tb) ⁇ ⁇ 100
  • the character in a formula represents the following meaning.
  • Cb number of insects before treatment in the untreated group
  • Cai number of live parasites when observed in the untreated group
  • Tb number of insects before treatment in the treated group
  • Tai number of live parasitic insects during observation of the treated group
  • the group means a group in which a preparation containing no compound of the present invention in Preparation Example 5 was sprayed with a test chemical solution diluted with the same amount of water as the treatment group.
  • all of the treatment sections using the test chemical solutions of the compounds 2, 3, 4, 5, 11, 12, 13, 14, 15 and 16 of the present invention showed a control value of 90% or more.
  • Test example 2 Each formulation of the present compounds 11, 13, 14 and 16 obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 200 ppm, and a test drug solution was prepared.
  • cucumber seedlings planted in plastic cups were irrigated with 5 ml of the test chemical solution and kept in a greenhouse at 25 ° C. for 7 days. After inoculating about 30 Aphis gossypi (all stages) on the cucumber leaf surface and keeping it in the greenhouse for another 6 days, the number of live aphids on the cucumber leaf was investigated. The control value was calculated by the following formula.
  • Control value (%) ⁇ 1 ⁇ (Cb ⁇ Tai) / (Cai ⁇ Tb) ⁇ ⁇ 100
  • the character in a formula represents the following meaning.
  • Cai number of live parasites when observed in the untreated group
  • Tb number of insects before treatment in the treated group
  • Tai number of live parasitic insects during observation of the treated group
  • the group means a group in which a preparation containing no compound of the present invention in Preparation Example 5 was sprayed with a test chemical solution diluted with the same amount of water as the treatment group.
  • all of the treatment sections using the test chemical solutions of the compounds 11, 13, 14 and 16 of the present invention exhibited a control value of 90% or more.
  • Test example 3 Each formulation of the present compounds 3, 14 and 15 obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 200 ppm, respectively, to prepare a test drug solution. 10 ml of the test chemical solution is sprayed on rice seedlings in the second leaf development stage planted in a polyethylene cup. After air-drying, 20 3-4 instar larvae of Nilaparvata lugens are released and stored in a greenhouse at 25 ° C. Six days later, the number of surviving insects that were infested with rice was examined, and the control value was determined by the following formula.
  • Control value (%) ⁇ 1 ⁇ (Cb ⁇ Tai) / (Cai ⁇ Tb) ⁇ ⁇ 100
  • the character in a formula represents the following meaning.
  • Cai number of live parasites when observed in the untreated group
  • Tb number of insects before treatment in the treated group
  • Tai number of live parasitic insects during observation of the treated group
  • the group means a group in which a preparation containing no compound of the present invention in Preparation Example 5 was sprayed with a test chemical solution diluted with the same amount of water as the treatment group.
  • all of the treatment groups using the test chemical solutions of the compounds 3, 14 and 15 of the present invention showed a control value of 90% or more.
  • Test example 4 Each preparation of the compounds 2, 3, 11 and 14 of the present invention obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 200 ppm, and a test drug solution was prepared. On the other hand, 5 ml of the test drug solution was irrigated to rice seedlings planted in plastic cups (2 weeks after sowing, in the second leaf development stage) and kept in a 25 ° C. greenhouse for 7 days. After releasing 20 3-4 instar larvae of the green planthopper (Nilaparvata lugens) and keeping it in the greenhouse for another 6 days, the number of surviving insects parasitic on the rice leaves was investigated, and the control value was calculated by the following formula: Asked.
  • Control value (%) ⁇ 1 ⁇ (Cb ⁇ Tai) / (Cai ⁇ Tb) ⁇ ⁇ 100
  • the character in a formula represents the following meaning.
  • Cai number of live parasites when observed in the untreated group
  • Tb number of insects before treatment in the treated group
  • Tai number of live parasitic insects during observation of the treated group
  • the group means a group in which a preparation containing no compound of the present invention in Preparation Example 5 was sprayed with a test chemical solution diluted with the same amount of water as the treatment group.
  • all of the treatment groups using the test chemical solutions of the compounds 2, 3, 11 and 14 of the present invention showed a control value of 90% or more.
  • Test Example 5 Each preparation of the compound of the present invention obtained in Formulation Example 5 is diluted with water so that the active ingredient concentration is 200 ppm to prepare a test drug solution.
  • adult tobacco whitefly (Bemisia tabaci) is released on tomato seedlings (third true leaf development stage) planted in a polyethylene cup and allowed to lay eggs for about 72 hours.
  • the tomato seedlings are kept in a greenhouse for 8 days, and the test chemical is sprayed at a rate of 20 ml / cup to the place where the larva has hatched from the delivered eggs, and kept in the greenhouse at 25 ° C. Seven days later, the number of surviving larvae on the tomato leaves is examined to calculate the mortality rate.
  • Test Example 6 Each formulation of the compound of the present invention 2,3,4,5,11,12,13,14,15,16,17 and 18 obtained in Formulation Example 5 is mixed with water so that the active ingredient concentration is 200 ppm.
  • the test drug solution was prepared.
  • the test chemical solution was sprayed at a rate of 20 mL / cup on a three-leaf cabbage planted in a polyethylene cup. After the drug solution was dried, the foliage was cut out and accommodated in a 50 mL cup, and 5 second-instar larvae (Plutella xylostella) were released and capped. After storing at 25 ° C., the number of dead insects was counted after 5 days, and the death rate was calculated from the following formula.
  • Death rate (%) (Number of dead insects / number of test insects) ⁇ 100
  • Test Example 7 Each formulation of the compound of the present invention obtained in Formulation Example 5 is diluted with water so that the active ingredient concentration becomes 200 ppm, respectively, and a test spray solution is prepared.
  • an apple is planted in a plastic cup and grown until the seventh or eighth true leaf develops.
  • the apple is sprayed with the test chemical at a rate of 20 mL / cup. After the chemical solution is dried, 60 first-instar larvae of Adoxophys orana fascita are released, and the bottom is covered with a plastic cup with a cut-out filter paper. After 7 days, the number of dead insects is examined and the death rate is calculated.
  • Test Example 9 Each formulation of the present compounds 4, 5 and 14 obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 500 ppm, respectively, to prepare a test drug solution.
  • a filter paper of the same size is placed on the bottom of a polyethylene cup having a diameter of 5.5 cm, 0.7 ml of the test chemical solution is dropped on the filter paper, and 30 mg of sucrose is uniformly added as food.
  • Test Example 10 Each formulation of the present compound 4, 5, 14, 15, 16, 17, 18 and 19 obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 500 ppm, respectively, and a test drug solution was prepared. Prepared. 0.7 ml of the test chemical solution was added to 100 ml of ion-exchanged water (active ingredient concentration: 3.5 ppm). Twenty dead larvae of Culex pipiens pallens were released into the solution, and after 1 day, the viability was investigated, the number of dead worms was counted, and the mortality rate was determined.
  • Death rate (%) (Number of dead insects / number of test insects) ⁇ 100 As a result, all of the treatment groups using the test chemical solutions of the compounds 4, 5, 14, 15, 16, 17, 18 and 19 of the present invention showed a death rate of 95% or more.
  • Test Example 12 5 mg of the compound of the present invention is dissolved in 5 mL of propylene carbonate so as to be 0.1% w / v to prepare a test drug solution.
  • mice were inoculated with 30 test mites (Mite mite, young mite). Remove non-parasitic ticks before dripping.
  • 200 ⁇ L of the test drug solution is administered dropwise to the entire body surface of the mouse using a pipette.
  • 200 ⁇ L of propylene carbonate alone is administered to the control group. Repeat 3 times per group. Two days after the instillation, the lethality of the test mite is investigated, and the mortality is calculated.
  • the control agent of the present invention has a control effect on pests and is useful as an active ingredient of pests.

Abstract

La présente invention concerne un composé hétérocyclique condensé qui peut être représenté par la formule (1) (dans laquelle A représente NCH3 ou un atome d'oxygène; R1 représente un atome d'hydrogène, un groupe alkyle en C1 - 3 qui peut contenir un ou plusieurs atomes d'halogène, un atome d'halogène, un groupe alcoxy en C1 - 3, un groupe alcoxycarbonyle en C2 - 4, S(O)mR2, NR3R4, un groupe nitro, ou un groupe cyano; R2 représente un groupe alkyle en C1 - 3; R3 et R4 représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle en C1 - 3; R5 représente un groupe perfluoroalkyle en C1 - 3 ou S(O)p-R6; R6 représente un groupe perfluoroalkyle C1 - 3; n représente 0, 1 ou 2; m représente 0, 1 ou 2; et p représente 0, 1 ou 2) qui présente une excellente efficacité de lutte contre les nuisibles.
PCT/JP2015/066673 2014-06-26 2015-06-10 Composé hétérocyclique condensé WO2015198859A1 (fr)

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