WO2015005408A1 - Composé d'hydrazide et son utilisation pour lutter contre les arthropodes nuisibles - Google Patents

Composé d'hydrazide et son utilisation pour lutter contre les arthropodes nuisibles Download PDF

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WO2015005408A1
WO2015005408A1 PCT/JP2014/068372 JP2014068372W WO2015005408A1 WO 2015005408 A1 WO2015005408 A1 WO 2015005408A1 JP 2014068372 W JP2014068372 W JP 2014068372W WO 2015005408 A1 WO2015005408 A1 WO 2015005408A1
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reaction
formula
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PCT/JP2014/068372
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Japanese (ja)
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彩乃 小綿
一哉 氏原
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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
    • A01N43/72—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
    • A01N43/80—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 1,2
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member

Definitions

  • the present invention relates to a hydrazide compound and its use for controlling harmful arthropods.
  • An object of the present invention is to provide a novel hydrazide compound having a controlling activity against harmful arthropods.
  • the present inventor As a result of studying to find a compound having control activity against harmful arthropods, the present inventor has found that a hydrazide compound represented by the following formula (1) (hereinafter referred to as the present compound) is against harmful arthropods. As a result, the present inventors have found that it has a controlling effect, and have reached the present invention. That is, the present invention is as follows. [1] Formula (1) Wherein, X 1 is a chlorine atom, R 1 is hydrogen atom, X 2 is chlorine atom or fluorine atom, if X 2 is a chlorine atom, R 2 is Shikuropurokiru group, X 2 Is a fluorine atom, R 2 is a 3,3,3-trifluoropropyl group.
  • the hydrazide compound represented by this [2] The compound according to [1], wherein R 2 is a cyclopropyl group. [3] The compound according to [1], wherein R 2 is a 3,3,3-trifluoropropyl group. [4] A harmful arthropod control agent comprising the hydrazide compound according to any one of [1] to [3] as an active ingredient. [5] A method for controlling harmful arthropods, which comprises applying an effective amount of the hydrazide compound according to any one of [1] to [3] to harmful arthropods or habitats of harmful arthropods .
  • the compounds of the present invention include isomers derived from asymmetric carbon atoms, but the present invention includes isomers having harmful arthropod controlling activity and isomer mixtures in any ratio.
  • the compound of the present invention can be produced by reacting the compound represented by the formula (2) with the compound represented by the formula (3).
  • X 1 , X 2 , R 1 and R 2 represent the same meaning as described above, and L represents a hydroxyl group or a chlorine atom.
  • the reaction is usually performed in a solvent.
  • the solvent used in the reaction include tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, ethers such as 1,4-dioxane, acid amides such as N, N-dimethylformamide, and nitriles such as acetonitrile.
  • Aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, sulfoxides such as dimethyl sulfoxide and sulfolane, halogenated hydrocarbons such as 1,2-dichloroethane, chloroform and chlorobenzene, and mixtures thereof.
  • L is a chlorine atom
  • the reaction is usually carried out in the presence of a base.
  • the base used in the reaction include alkali metal hydrides such as sodium hydride, carbonates such as potassium carbonate, alkali metal alkoxides such as potassium tert-butoxide, and organic amines such as triethylamine and pyridine.
  • the reaction is carried out in the presence of a condensing agent.
  • the condensing agent used in the reaction include dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
  • the amount of the reagent used in the reaction is usually 1 to 10 mol of the compound represented by the formula (3) with respect to 1 mol of the compound represented by the formula (2), and the base or condensing agent is usually 1 to 1 mol.
  • the ratio is 10 moles.
  • the reaction is further optionally carried out in an arbitrary ratio of 0.1 mol to 1 mol with respect to 1 mol of the compound represented by the formula (2). Etc. can also be added.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound of the present invention can also be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound of the present invention can be further purified by chromatography, recrystallization and the like.
  • the compound of the present invention can be produced by reacting the compound represented by the formula (4) with the acid (5).
  • the reaction is usually performed in a solvent.
  • the solvent used in the reaction include tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, ethers such as 1,4-dioxane, acid amides such as N, N-dimethylformamide, and nitriles such as acetonitrile.
  • Aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, sulfoxides such as dimethyl sulfoxide and sulfolane, halogenated hydrocarbons such as 1,2-dichloroethane, chloroform and chlorobenzene, and mixtures thereof.
  • Examples of the acid (5) used in the reaction include hydrochloric acid, acetic acid, trifluoroacetic acid and the like.
  • the amount of the reagent used for the reaction is usually 1 to 10 moles of the acid (5) with respect to 1 mole of the compound represented by the formula (4).
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound of the present invention can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound of the present invention can be further purified by chromatography, recrystallization and the like.
  • the compound of the present invention can also be produced by reacting a compound represented by formula (6) with a compound represented by formula (7).
  • X 1 , X 2 , R 1 and R 2 represent the same meaning as described above, and Z represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, and a trifluoro group.
  • the reaction is usually performed in a solvent.
  • solvent used in the reaction examples include tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, ethers such as 1,4-dioxane, acid amides such as N, N-dimethylformamide, and nitriles such as acetonitrile.
  • Aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, sulfoxides such as dimethyl sulfoxide and sulfolane, halogenated hydrocarbons such as 1,2-dichloroethane, chloroform and chlorobenzene, and mixtures thereof.
  • Aromatic hydrocarbons such as toluene and xylene
  • esters such as ethyl acetate
  • sulfoxides such as dimethyl sulfoxide and sulfolane
  • halogenated hydrocarbons such as 1,2-dichloroethan
  • the reaction is carried out in the presence of a base as necessary.
  • the base used in the reaction include alkali metal hydrides such as sodium hydride, carbonates such as potassium carbonate, alkali metal alkoxides such as potassium tert-butoxide, and organic amines such as triethylamine and pyridine.
  • the amount of the reagent used for the reaction is such that the compound represented by the formula (7) is usually 1 to 5 mol and the base is usually 1 to 5 mol per 1 mol of the compound represented by the formula (6). It is a ratio.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound of the present invention can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound of the present invention can be further purified by chromatography, recrystallization and the like.
  • the reaction is a coupling reaction using a general transition metal catalyst described in literature, for example, Org. Lett. 3, 3803-3805 (2001).
  • the compound represented by the formula (4) can be produced by reacting the compound represented by the formula (8) with the compound represented by the formula (3).
  • the reaction is usually performed in a solvent.
  • the solvent used in the reaction include tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, ethers such as 1,4-dioxane, acid amides such as N, N-dimethylformamide, and nitriles such as acetonitrile.
  • Aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, sulfoxides such as dimethyl sulfoxide and sulfolane, halogenated hydrocarbons such as 1,2-dichloroethane, chloroform and chlorobenzene, and mixtures thereof.
  • L is a chlorine atom
  • the reaction is usually carried out in the presence of a base.
  • the base used in the reaction include alkali metal hydrides such as sodium hydride, carbonates such as potassium carbonate, alkali metal alkoxides such as potassium tert-butoxide, and organic amines such as triethylamine and pyridine.
  • the reaction is carried out in the presence of a condensing agent.
  • the condensing agent used in the reaction include dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
  • the amount of the reagent used in the reaction is usually 1 to 10 mol of the compound represented by the formula (3) with respect to 1 mol of the compound represented by the formula (8), and the base or condensing agent is usually 1 to 1 mol.
  • the ratio is 10 moles.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (4) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound represented by the formula (4) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (8) can be produced by reacting the compound represented by the formula (9) with the nitrite compound (10) and then reacting with the reducing agent (11). [Wherein, X 1 and X 2 represent the same meaning as described above. ]
  • the reaction is usually carried out in a solvent.
  • solvent used in the reaction examples include water, tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethers such as ethylene glycol dimethyl ether and 1,4-dioxane, acid amides such as N, N-dimethylformamide, toluene, Aromatic hydrocarbons such as xylene, sulfoxides such as dimethyl sulfoxide and sulfolane, halogenated hydrocarbons such as 1,2-dichloroethane, chloroform and chlorobenzene, and mixtures thereof.
  • Examples of the nitrite compound (10) used in the reaction include nitrites such as sodium nitrite and nitrites such as ethyl nitrite.
  • Examples of the reducing agent (11) used in the reaction include sulfites such as sodium sulfite, metals such as zinc, tin (II) chloride and the like.
  • the amount of the reagent used in the reaction is usually 1 to 10 moles of the nitrite compound (10) and 1 to 10 moles of the reducing agent (11) with respect to 1 mole of the compound represented by the formula (9). The molar ratio.
  • the reaction temperature in the step of reacting the compound represented by the reaction formula (9) with the nitrite compound (10) is usually in the range of ⁇ 20 to 30 ° C., and the reaction time is usually in the range of 0.5 to 24 hours. is there.
  • the reaction mixture obtained in the step of reacting the compound represented by formula (9) and the nitrite compound (10) can be used as it is in the step of reacting with the reducing agent (11), and the reaction temperature in the step is usually It is in the range of ⁇ 20 to 50 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (8) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound represented by the formula (8) can be further purified by chromatography, recrystallization and the like. (Reference production method 3)
  • the compound represented by the formula (8) can also be produced by reacting the compound represented by the formula (9) with the aminating agent (12). [Wherein, X 1 and X 2 represent the same meaning as described above. ] The reaction is usually carried out in a solvent.
  • Examples of the solvent used in the reaction include water, tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethers such as ethylene glycol dimethyl ether and 1,4-dioxane, acid amides such as N, N-dimethylformamide, toluene, Aromatic hydrocarbons such as xylene, sulfoxides such as dimethyl sulfoxide and sulfolane, halogenated hydrocarbons such as 1,2-dichloroethane, chloroform and chlorobenzene, and mixtures thereof.
  • the reaction is usually performed in the presence of a base.
  • Examples of the base used in the reaction include alkali metal hydrides such as sodium hydride, carbonates such as potassium carbonate, alkali metal alkoxides such as potassium tert-butoxide, metal hydroxides such as sodium hydroxide and triethylamine, And organic amines such as pyridine.
  • Examples of the aminating agent (12) used in the reaction include chloramines such as chloramine, O-acylhydroxylamines such as O-mesitoylhydroxylamine, O-sulfonylhydroxylamines, and hydroxylamine-O-sulfonic acids. Can be mentioned.
  • the amount of the reagent used in the reaction is usually 1 to 10 mol of the aminating agent (12) and 1 to 10 mol of the base, based on 1 mol of the compound represented by the formula (9). is there.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (8) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration. The isolated compound represented by the formula (8) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (9) can also be produced by reacting the compound represented by the formula (13-1) with di-tert-butyl dicarbonate.
  • X 1 and X 2 represent the same meaning as described above.
  • the reaction is usually carried out in a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether and 1,4-dioxane, acid amides such as N, N-dimethylformamide, toluene, xylene and the like.
  • Aromatic hydrocarbons such as dimethyl sulfoxide and sulfolane, halogenated hydrocarbons such as 1,2-dichloroethane, chloroform and chlorobenzene, and mixtures thereof.
  • the reaction is usually performed in the presence of a base.
  • the base used in the reaction include organic amines such as triethylamine, carbonates such as sodium carbonate, and alkali metal hydroxides such as sodium hydroxide.
  • the amount of the reagent used in the reaction is usually 1 to 10 moles of di-tert-butyl dicarbonate and 1 to 10 moles of the base based on 1 mole of the compound represented by the formula (13-1). Is the ratio.
  • tetrabutylammonium bromide or the like is usually added at an arbitrary ratio from 0.05 mol to 0.10 mol with respect to 1 mol of the compound represented by formula (13-1). It can also be done.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (9) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration. The isolated compound represented by the formula (9) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (13-1) can be produced by reducing the compound represented by the formula (14) by any method shown in the following (i) to (iii). [Wherein, X 1 and X 2 represent the same meaning as described above. ]
  • (I) A method of reacting with hydrogen gas in the presence of a transition metal catalyst. The reaction is carried out in a solvent.
  • the solvent used in the reaction include esters such as ethyl acetate, alcohols such as ethanol and methanol, water, acetic acid, hydrochloric acid, and mixtures thereof.
  • the transition metal catalyst used in the reaction include Raney nickel, palladium-carbon, and platinum dioxide.
  • the amount of the transition metal catalyst used in the reaction is usually 0.01 to 0.5 mol with respect to 1 mol of the compound represented by the formula (14).
  • the reaction temperature is usually in the range of 0 to 80 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound represented by the formula (13-1) can be isolated by filtering the reaction mixture and performing post-treatment operations such as organic solvent extraction, drying, and concentration as necessary. .
  • the isolated compound represented by the formula (13-1) can be further purified by chromatography, recrystallization and the like.
  • (Ii) A method of reacting with hydrazine in the presence of a base. The reaction is carried out in a solvent.
  • Examples of the solvent used in the reaction include ethers such as diethylene glycol and triethylene glycol, water, and a mixture thereof.
  • Examples of the base used for the reaction include alkali metal hydroxides such as potassium hydroxide.
  • Examples of hydrazine used in the reaction include hydrazine hydrate.
  • the amount of the reagent used in the reaction is usually 1 to 10 moles of base and 1 to 10 moles of hydrazine to 1 mole of the compound represented by formula (14).
  • the compound represented by the formula (13-1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration. The isolated compound represented by the formula (13-1) can be further purified by chromatography, recrystallization and the like.
  • (Iii) A method of reacting with a metal in the presence of an acid.
  • the reaction is usually carried out in a solvent.
  • the solvent used in the reaction include alcohols such as ethanol, water, and a mixture thereof.
  • the metal used in the reaction include iron, tin, and tin (II) chloride.
  • the acid used for the reaction include acetic acid, hydrochloric acid, and sulfuric acid.
  • the amount of the reagent used in the reaction is usually 2 to 20 moles of metal and 0.1 to 10 moles of acid with respect to 1 mole of the compound represented by the formula (14).
  • the reaction temperature is usually in the range of 0 to 100 ° C.
  • the reaction time is usually in the range of 0.5 to 12 hours.
  • the compound represented by the formula (13-1) can be isolated by filtering the reaction mixture and performing post-treatment operations such as organic solvent extraction, drying, and concentration as necessary. .
  • the isolated compound represented by the formula (13-1) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (16) can be produced by reacting the compound represented by the formula (13-1) with trifluoroacetic anhydride.
  • X 1 and X 2 represent the same meaning as described above.
  • the reaction is usually carried out in a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether and 1,4-dioxane, acid amides such as N, N-dimethylformamide, toluene, xylene and the like.
  • Aromatic hydrocarbons such as dimethyl sulfoxide and sulfolane, halogenated hydrocarbons such as 1,2-dichloroethane, chloroform and chlorobenzene, and mixtures thereof.
  • the amount of the reagent used in the reaction is usually 1 to 10 moles of trifluoroacetic anhydride with respect to 1 mole of the compound represented by the formula (13-1).
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (16) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound represented by the formula (16) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (9) can also be produced by reacting the compound represented by the formula (18) with hydroxylamine and a base.
  • X 1 and X 2 represent the same meaning as described above.
  • the reaction is usually carried out in a solvent.
  • the solvent used in the reaction include tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, ethers such as 1,4-dioxane, acid amides such as N, N-dimethylformamide, and nitriles such as acetonitrile.
  • Hydrocarbons such as toluene, esters such as ethyl acetate, sulfoxides such as dimethyl sulfoxide, water, and mixtures thereof.
  • the hydroxylamine used in the reaction include hydroxylamine and mineral acid salt forms such as hydroxylamine hydrochloride and hydroxylamine sulfate, which can generate hydroxylamine in the reaction system.
  • the reaction is performed in the presence of a base.
  • the base used in this case include organic amines such as triethylamine, carbonates such as sodium carbonate, and alkali metal hydroxides such as sodium hydroxide.
  • the amount of the reagent used in the reaction is usually 1 to 10 moles of hydroxylamine per mole of the compound represented by formula (18), and is used when a salt of hydroxylamine and mineral acid is used.
  • the amount of the base to be obtained is usually 1 to 10 moles per mole of the salt of hydroxylamine and mineral acid.
  • a phase transfer catalyst such as tetrabutylammonium bromide is usually added at an arbitrary ratio from 0.1 mol to 1.0 mol with respect to 1 mol of the compound represented by the formula (18). It can also be done.
  • the reaction temperature is usually in the range of 0 to 80 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (9) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound represented by the formula (9) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (18) can also be produced by reacting the compound represented by the formula (19) and the compound represented by the formula (20) with a base and heating. [Wherein, X 1 and X 2 represent the same meaning as described above. ] The reaction is usually carried out in a solvent.
  • solvent used in the reaction examples include tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, ethers such as 1,4-dioxane, acid amides such as N, N-dimethylformamide, and nitriles such as acetonitrile.
  • Hydrocarbons such as toluene, esters such as ethyl acetate, sulfoxides such as dimethyl sulfoxide, and mixtures thereof.
  • Examples of the base used in the reaction include carbonates such as potassium carbonate, alkali metal alkoxides such as potassium tert-butoxide, and organic amines such as triethylamine and pyridine.
  • the amount of the reagent used in the reaction is usually 1 to 10 mol of the compound represented by the formula (20) and 1 to 10 mol of the base based on 1 mol of the compound represented by the formula (19). It is a ratio.
  • the reaction temperature of the reaction is usually in the range of 0 to 100 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (18) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound represented by the formula (18) can be further purified by chromatography, recrystallization or the like.
  • the compound represented by the formula (18) can also be produced by reacting the compound represented by the formula (21) with a dehydrating agent (22) and a base. [Wherein, X 1 and X 2 represent the same meaning as described above. ] The reaction is usually carried out in a solvent.
  • Examples of the solvent used in the reaction include tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, ethers such as 1,4-dioxane, acid amides such as N, N-dimethylformamide, and nitriles such as acetonitrile. , Hydrocarbons such as toluene, esters such as ethyl acetate, sulfoxides such as dimethyl sulfoxide, and mixtures thereof.
  • Examples of the dehydrating agent (22) used in the reaction include acid chlorides such as thionyl chloride and carboxylic acid anhydrides such as acetic anhydride.
  • Examples of the base used in the reaction include carbonates such as potassium carbonate, alkali metal alkoxides such as potassium tert-butoxide, and organic amines such as triethylamine and pyridine.
  • the amount of the reagent used in the reaction is usually 1 to 10 moles of the dehydrating agent (22) and 1 to 10 moles of the base with respect to 1 mole of the compound represented by the formula (21). .
  • the reaction temperature of the reaction is usually in the range of 0 to 200 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (18) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound represented by the formula (18) can be further purified by chromatography, recrystallization or the like.
  • the compound represented by the formula (21) can be produced by reacting the compound represented by the formula (19) and the compound represented by the formula (20) with a base. [Wherein, X 1 and X 2 represent the same meaning as described above. ] The reaction is usually carried out in a solvent.
  • solvent used in the reaction examples include tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, ethers such as 1,4-dioxane, acid amides such as N, N-dimethylformamide, and nitriles such as acetonitrile.
  • Hydrocarbons such as toluene, esters such as ethyl acetate, sulfoxides such as dimethyl sulfoxide, and mixtures thereof.
  • Examples of the base used in the reaction include carbonates such as potassium carbonate, alkali metal alkoxides such as potassium tert-butoxide, and organic amines such as triethylamine and pyridine.
  • the amount of the reagent used in the reaction is usually 1 to 10 mol of the compound represented by the formula (20) and 1 to 10 mol of the base based on 1 mol of the compound represented by the formula (19). It is a ratio.
  • the reaction temperature is usually in the range of 0 to 80 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (21) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration. The isolated compound represented by the formula (21) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (20) can be produced by reacting the compound represented by the formula (23) with a trifluoromethylating reagent (24) and a base.
  • a trifluoromethylating reagent (24) and a base.
  • X 2 represents the same meaning as described above
  • R 6 represents a C1-C6 alkyl group.
  • the reaction is usually carried out in a solvent.
  • the solvent used in the reaction include tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, ethers such as 1,4-dioxane, acid amides such as N, N-dimethylformamide, and nitriles such as acetonitrile.
  • Hydrocarbons such as toluene, esters such as ethyl acetate, sulfoxides such as dimethyl sulfoxide, and mixtures thereof.
  • examples of the trifluoromethylating agent (24) used in the reaction include trifluoromethyltrimethylsilyl.
  • Examples of the base used in the reaction include carbonates such as potassium carbonate, alkali metal alkoxides such as potassium tert-butoxide, and organic amines such as triethylamine and pyridine.
  • the amount of the reagent used in the reaction is usually 1 to 10 mol of the trifluoromethylating agent (24) and 1 to 10 mol of the base based on 1 mol of the compound represented by the formula (23). It is a ratio.
  • the reaction temperature of the reaction is usually in the range of 0 to 200 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (20) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound represented by the formula (20) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (20) can be produced by reacting the compound represented by the formula (25) with the Grignard reagent (26) and then reacting with the trifluoromethyl reagent (27). [Wherein, X 2 represents the same meaning as described above, and Y represents a halogen atom.
  • the reaction is usually carried out in a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, and 1,4-dioxane, hydrocarbons such as toluene, and mixtures thereof.
  • the Grignard reagent (26) used in the reaction include isopropyl magnesium bromide.
  • Examples of the trifluoromethylating reagent (27) used in the reaction include ethyl trifluoroacetate.
  • the amount of the reagent used for the reaction is usually 1 to 10 mol of Grignard reagent (26) and 1 to 1 of trifluoromethyl reagent (27) with respect to 1 mol of the compound represented by the formula (25).
  • the ratio is 10 moles.
  • the reaction temperature in the step of reacting the compound represented by the reaction formula (25) with the Grignard reagent (26) is usually in the range of ⁇ 20 to 30 ° C., and the reaction time is usually in the range of 0.5 to 24 hours. .
  • the reaction mixture obtained in the step of reacting the compound represented by the formula (25) with the Grignard reagent (26) can be used as it is in the step of reacting with the trifluoromethylating reagent (27), and the reaction temperature in this step is
  • the reaction time is usually in the range of ⁇ 20 to 50 ° C., and the reaction time is usually in the range of 0.5 to 12 hours.
  • the compound represented by the formula (20) can also be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound represented by the formula (20) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (25) can be produced by reacting the compound represented by the formula (28) with the diazotization reagent (29) and then reacting with the inorganic halogen reagent (30).
  • X 2 represents the same meaning as described above
  • Y represents a halogen atom.
  • the reaction is usually carried out in a solvent.
  • the solvent used in the reaction include water, acidic aqueous solutions such as hydrochloric acid and sulfuric acid, and mixtures thereof.
  • the diazotization reagent (29) used for the reaction include nitrites such as sodium nitrite.
  • potassium iodide As an inorganic halogen reagent (30) used for reaction, potassium iodide etc.
  • the amount of the reagent used in the reaction is usually 1 to 10 moles of the diazotizing reagent (29) and 1 to 1 mole of the inorganic halogen reagent (30) with respect to 1 mole of the compound represented by the formula (28).
  • the ratio is 10 moles.
  • the reaction temperature in the step of reacting the compound represented by the reaction formula (28) with the diazotization reagent (29) is usually in the range of ⁇ 20 to 30 ° C., and the reaction time is usually in the range of 0.5 to 24 hours. is there.
  • the reaction mixture obtained in the step of reacting the compound represented by formula (28) with the diazotization reagent (29) can be used in the step of reacting with the inorganic halogen reagent (30) as it is, and the reaction temperature in the step is as follows. Usually, it is in the range of ⁇ 20 to 50 ° C., and the reaction time is usually in the range of 0.5 to 12 hours.
  • the compound represented by the formula (25) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration. The isolated compound represented by the formula (25) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (20) can also be produced by reacting the compound represented by the formula (31) with ozone and then reacting with a reducing agent.
  • a reducing agent such as X 2 represents the same meaning as described above.
  • the reaction is usually performed in a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether and 1,4-dioxane, esters such as ethyl acetate, and halogenated hydrocarbons such as chloroform and dichloromethane. Alcohols such as methanol and ethanol, and mixtures thereof.
  • Examples of the reducing agent used in the reaction include dimethyl sulfide, triphenylphosphine, zinc, thiourea and the like.
  • the amount of the reagent used in the reaction is usually 1 to 10 moles of ozone and 1 to 10 moles of reducing agent per mole of the compound represented by formula (31).
  • the reaction temperature in the step of reacting the compound represented by the reaction formula (31) with ozone is usually in the range of ⁇ 100 to 0 ° C., and the reaction time is usually in the range of up to 24 hours.
  • the reaction mixture obtained in the step of reacting the compound represented by the formula (31) with ozone can be used as it is in the step of reacting with a reducing agent, and the reaction temperature in the step is usually in the range of ⁇ 78 to 30 ° C.
  • the reaction time is usually in the range of 0.5 to 12 hours.
  • the compound represented by the formula (20) can also be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound represented by the formula (20) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (31) can be produced by reacting the Wittig reagent (33) with a base and then reacting with the compound represented by the formula (20).
  • the reaction is usually performed in a solvent.
  • the solvent used for the reaction include tetrahydrofuran, dityl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, ethers such as 1,4-dioxane, acid amides such as N, N-dimethylformamide, and nitriles such as acetonitrile.
  • Hydrocarbons such as toluene, esters such as ethyl acetate, sulfoxides such as dimethyl sulfoxide, and mixtures thereof.
  • Examples of the Wittig reagent (33) used in the reaction include methyltriphenylphosphonium bromide.
  • Examples of the base used in the reaction include carbonates such as potassium carbonate, alkali metal alkoxides such as potassium tert-butoxide, organic lithiums such as butyl lithium, and organic amines such as triethylamine and pyridine.
  • the amount of the reagent used in the reaction is usually 1 to 10 moles of Wittig reagent (33) and 1 to 10 moles of base based on 1 mole of the compound represented by formula (20). .
  • the reaction temperature in the step of reacting the Wittig reagent (33) with the base is usually in the range of ⁇ 100 to 30 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the reaction mixture obtained in the step of reacting the Wittig reagent (33) with the base can be used as it is in the step of reacting with the compound represented by the formula (20), and the reaction temperature in this step is usually ⁇ 100 to It is in the range of 50 ° C., and the reaction time is usually in the range of 0.5 to 12 hours.
  • the compound represented by the formula (31) can also be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound represented by the formula (31) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (31) can be produced, for example, according to the method described in International Publication No. 2011/124998. [Wherein X 2 represents the same meaning as described above. ]
  • (Reference production method 17) The compound represented by the formula (6) can be produced by reacting the compound represented by the formula (34) with a base and then reacting the compound represented by the formula (31). [Wherein, X 1 , X 2 and Z represent the same meaning as described above. ] The reaction is usually carried out in a solvent.
  • solvent used in the reaction examples include tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, ethers such as 1,4-dioxane, acid amides such as N, N-dimethylformamide, and nitriles such as acetonitrile.
  • Hydrocarbons such as toluene, esters such as ethyl acetate, sulfoxides such as dimethyl sulfoxide, and mixtures thereof.
  • Examples of the base used in the reaction include alkali metal hydrides such as sodium hydride, carbonates such as potassium carbonate, alkali metal alkoxides such as potassium tert-butoxide, and organic amines such as triethylamine and pyridine. .
  • the amount of the reagent used for the reaction is usually 1 to 10 mol of the compound represented by the formula (31) and 1 to 10 mol of the base based on 1 mol of the compound represented by the formula (34). It is a ratio.
  • the reaction temperature in the step of reacting the compound represented by the reaction formula (34) with the base is usually in the range of 0 to 80 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the reaction mixture obtained in the step of reacting the compound represented by formula (34) with the base can be used as it is in the step of reacting with the compound represented by formula (31), and the reaction temperature in this step is usually 0. It is in the range of ⁇ 80 ° C, and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (6) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound represented by the formula (6) can be further purified by chromatography, recrystallization or the like.
  • the compound represented by the formula (34) can be produced by reacting the compound represented by the formula (35) with a chlorinating agent (36).
  • the reaction is usually carried out in a solvent.
  • the solvent used in the reaction include ethers such as tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether and 1,4-dioxane, hydrocarbons such as toluene, esters such as ethyl acetate, N, Examples include acid amides such as N-dimethylformamide, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, and mixtures thereof.
  • Examples of the chlorinating agent (36) used in the reaction include chlorine gas and N-chlorosuccinimide.
  • the amount of the reagent used for the reaction is usually 1 to 10 moles of the chlorinating agent (36) with respect to 1 mole of the compound represented by the formula (35).
  • the reaction temperature is usually in the range of ⁇ 20 to 80 ° C.
  • the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (34) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound represented by the formula (36) can be further purified by chromatography, recrystallization or the like.
  • the compound represented by the formula (35) can be produced by reacting the compound represented by the formula (37) with hydroxylamine. [Wherein, X 1 and Z represent the same meaning as described above. ] The reaction is usually carried out in a solvent.
  • Examples of the solvent used in the reaction include tetrahydrofuran, diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, ethers such as 1,4-dioxane, hydrocarbons such as toluene, esters such as ethyl acetate, N, Examples include acid amides such as N-dimethylformamide, alcohols such as ethanol and methanol, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, water, and mixtures thereof.
  • hydroxylamine used in the reaction examples include those capable of producing hydroxylamine in the reaction system in the form of a salt of hydroxylamine and mineral acid, such as hydroxylamine hydrochloride and hydroxylamine sulfate.
  • the reaction is carried out in the presence of a base.
  • the base used in this case include organic amines such as triethylamine, carbonates such as sodium carbonate, and alkali metal hydroxides such as sodium hydroxide.
  • the amount of the reagent used in the reaction is usually 1 to 10 moles of hydroxylamine per mole of the compound represented by formula (37), and a salt of hydroxylamine and mineral acid is used in the reaction.
  • the amount of the base used in is usually 1 to 10 moles per mole of the salt of hydroxylamine and mineral acid.
  • the reaction temperature is usually in the range of 0 to 80 ° C., and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (35) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration.
  • the isolated compound represented by the formula (35) can be further purified by chromatography, recrystallization and the like.
  • harmful arthropods for which the compound of the present invention is effective include harmful insects and harmful mites, and specific examples thereof 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 (Empoasca onukii) such as Leafhoppers, cotton aphids (Aphis gossypii), peach aphids (Myzus persicae), radish aphids (Brevicorine brassicae), snowy aphids (Aphis spiraecola), tulip beetle aphids iphum euphorbiae), potato beetle aphid (Aulacorthum solani), wheat pea aphid (Rhopalosiphum padi), citrus aphid (
  • 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), Japanese medusa such as Shibata toga (Pediasia teterrellus), Spodoptera litura, Spodoptera exigua, Ayuyotoga (Pseudaletia sepata), Atoga assicae), Agrotis ipsilon, Tamanaginawaba (Prusia nigrisigna), Trichopulsia, Heliotis, Helicoberpa, etc.
  • Thysanoptera western flower thrips (Frankliniella occidentalis), Minami thrips (Thrips peri), yellow tea thrips (Scirtothrips dorsalis), green onion thrips (Thrips tabaci), Hirazuhanaazamiuma (Frankliniella intonsa) thrips Diptera pests such as: housefly (Musca domestica), Culex popiens pallens, Cattle fly (Tabanus trigonus), Onion fly (Hyremya antiquaes), Hyaneya plateaus (Hilemya platerais) omyza oryzae), rice Hime leafminer (Hydrellia griseola), Inekimoguribae (Chlorops oryzae), melon fly (Dacus cucurbitae), Mediterranean fruit fly (Ceratitis capitata), legume leafminer (Liriomyza trifolii), tomato leafminer, (Liriomyza
  • Coleoptera beetle, Epilachna vigintioctopunctata (Epilachna vigintioctopunctata), cucurbit leaf beetle (Aulacophora femoralis), Kisujinomihamushi (Phyllotreta striolata), Inedorooimushi (Oulema oryzae), rice weevil (Echinocnemus squameus), rice water weevil (Lissorhoptrus oryzophilus), boll weevil (Anthonomus grandis), Azuki beetle (Callosobruchus chinensis), Shibahorusu weevil (Sphenophorus venatus), Japanese beetle (Popilia japonica), Douganebububu (Anomala cupre) ), Corn rootworm mate (Diabrotica spp.), Colorado potato beetle (Leptinotarsa decemlineat
  • Direct insect pests Tocusama grasshopper (Locusta migratoria), Kera (Gryllotalpa africana), Oxya yezoensis, Oyana japonica, etc.
  • Hymenopteran pests Athalia rosae, Achillyrmex spp., Fire ant (Solenopsis spp.) And the like.
  • Cockroach pests German cockroaches (Blatella germanica), Black cockroaches (Periplaneta furiginosa), American cockroaches (Periplaneta americana), Japanese cockroaches (Peripraneta brunet)
  • Mite order pests Taninychus urticae, Kantawa spider mite (Tetranychus kanzawai), citrus spider mite (Panonychus citri), mite spider mite (Pananycos ulmi), spider mite pistula mite (Panthonychus urmi), spider mite pistula mite (Panthonychus urmi), spider mite pistula mite (Panthonychus urmi); spider mite pistula mite (Panthonychus urmi); Tomato rustic mites (Aculops lycopersici), Chanosabi mites (Calacarus carinatus), Chanoagasabi
  • dust mites such as nemus latus, spider mites such as Brevipalpus phoenicis, spider mite, tick mite (Haemphysalis longicornis), mites Tick such as ticks (Ixodes persulcatus), bull ticks (Boophilus microplus), Rhipicephalus sanguineus, Typhophagus urticae (Tyrophagus pudensent) ophagus similis) grain mites such as, farinae (Dermatophagoides farinae), house dust mite such as pteronyssinus (Dermatophagoides ptrenyssnus), Hosotsumedani (Cheyletus eruditus), Stag Tsumedani (Cheyletus malaccensis), Tsumedani such as Minami Tsumedani (Cheyletus moorei), chicken mites such etc.
  • nemus latus spider mites
  • the harmful arthropod control agent of the present invention may be the compound of the present invention itself, but usually the compound of the present invention and an inert carrier such as a solid carrier, a liquid carrier, a gaseous carrier, etc. are mixed, if necessary, Add surfactants and other formulation adjuvants to prepare emulsions, oils, powders, granules, wettable powders, flowables, microcapsules, aerosols, smokers, poison baits, resin formulations, etc. It has become. These preparations usually contain 0.01 to 95% by weight of the compound of the present invention.
  • an inert carrier such as a solid carrier, a liquid carrier, a gaseous carrier, etc.
  • solid carrier used for formulation examples include clays (kaolin clay, diatomaceous earth, bentonite, fusami clay, acidic clay), synthetic hydrous silicon oxide, talc, ceramic, and other inorganic minerals (sericite, quartz, Sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), fine fertilizers such as chemical fertilizers (ammonium sulfate, phosphorous acid, ammonium nitrate, urea, ammonium chloride, etc.) and granular materials.
  • clays kaolin clay, diatomaceous earth, bentonite, fusami clay, acidic clay
  • synthetic hydrous silicon oxide talc
  • ceramic and other inorganic minerals
  • fine fertilizers such as chemical fertilizers (ammonium sulfate, phosphorous acid, ammonium nitrate, urea, ammonium chloride, etc.) and granular materials.
  • 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.), and aromatic carbonization.
  • alcohols methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, phenoxyethanol, etc.
  • ketones acetone, methyl ethyl ketone, cyclohexanone, etc.
  • aromatic carbonization examples include water, alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, phenoxyethanol, etc.
  • ketones acetone, methyl ethyl ketone
  • Hydrogen toluene, xylene, ethylbenzene, dodecylbenzene, phenylxylylethane, methylnaphthalene, etc.
  • aliphatic hydrocarbons hexane, cyclohexane, kerosene, light oil, etc.
  • esters ethyl acetate, butyl acetate, isopropyl myristate
  • nitriles acetonitrile, isobutyrate) Nitriles
  • ethers diisopropyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl
  • 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 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, polyethylene glycol fatty acid ester, and the like, alkyl sulfonate, alkyl benzene sulfonate, and alkyl sulfate.
  • Anionic surfactants may be mentioned.
  • Other adjuvants for preparation include sticking agents, dispersants, colorants and stabilizers, such as casein, gelatin, saccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite.
  • Synthetic water-soluble polymers polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.
  • PAP isopropyl acid phosphate
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • BHA 2,6-tert -Mixture of butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol
  • the method for controlling harmful arthropods of the present invention usually involves the harmful arthropod control agent of the present invention directly on the harmful arthropods or the place where the harmful arthropods live (plants, soil, indoors, animals, etc.) It is done by applying to.
  • the compound of the present invention can be used as it is in the method for controlling harmful arthropods of the present invention
  • the compound of the present invention is usually formulated in the form of the above-mentioned harmful arthropod control agent of the present invention, for example,
  • the method may be applied to harmful arthropods or habitats of harmful arthropods in the same manner as conventional harmful arthropod control agents, and the above-mentioned harmful arthropods are brought into contact with or ingested.
  • habitats for harmful arthropods in the present invention include paddy fields, fields, orchards, non-agricultural land, and houses.
  • Examples of such application methods include spraying treatment, soil treatment, seed treatment, and hydroponic liquid treatment.
  • the spraying treatment in the present invention specifically refers to, for example, a harmful arthropod by treating an active ingredient (the compound of the present invention) on the surface of the plant body such as foliage spraying, trunk spraying, etc. or the harmful arthropod itself.
  • a treatment method that exerts control efficacy against Soil treatment is, for example, by treating the active ingredient with soil or irrigation liquid to infiltrate and transfer from the roots to the inside of the plant body of the crop to be protected from damage such as feeding by harmful arthropods.
  • a treatment method for protecting the crop from damage caused by harmful arthropods is, for example, by treating the active ingredient with soil or irrigation liquid to infiltrate and transfer from the roots to the inside of the plant body of the crop to be protected from damage such as feeding by harmful arthropods.
  • planting treatment planting hole spraying, planting hole treatment soil mixing
  • plant source treatment stock source spraying, strain source
  • grooving treatment spreading grooving, mixing grooving soil
  • cropping treatment spreading, sprinkling soil mixing, sprinkling of growing season
  • sowing Temporary cropping treatment spraying at the time of sowing, mixing with soil at the time of sowing
  • full treatment spreading the entire soil, mixing with the whole soil
  • other soil spraying treatment spreading the growing leaves in the growing season, spraying under the crown or around the trunk
  • Other irrigation treatments irrigation, seedling stage irrigation, chemical solution injection treatment, subsurface irrigation, chemical drip irrigation, chemigation
  • nursery box treatment nursery box spraying, seed
  • the treatment method protects the crop from damage caused by harmful arthropods.
  • Specific examples include hydroponic liquid mixing and hydroponic liquid mixing.
  • the application amount is the amount of the compound of the present invention per 10,000 m 2 and is usually 1 to 10,000 g.
  • the harmful arthropod control agent of the present invention is formulated into an emulsion, a wettable powder, a flowable agent, etc., it is usually applied by diluting with water so that the active ingredient concentration becomes 0.01 to 10,000 ppm. Granules, powders and the like are usually applied as they are.
  • These preparations and water dilutions of these preparations may be applied directly to harmful arthropods or plants such as crops that should be protected from harmful arthropods, and harmful arthropods that inhabit cultivated land soil You may treat to this soil in order to control. Moreover, it can also process by the method of wrapping the resin formulation processed into the sheet form or the string form around the crop, stretching over the crop vicinity, and laying on the stock soil.
  • the application amount is 1 m 2 when treated on the surface.
  • the amount of the compound of the present invention per unit is usually 0.01 to 1000 mg, and when processing in a space, the amount of the compound of the present invention per 1 m 3 of the processing space is usually 0.01 to 500 mg.
  • the harmful arthropod control agent of the present invention is formulated into an emulsion, wettable powder, flowable agent, etc., it is usually diluted with water so that the active ingredient concentration is 0.1 to 1000 ppm, and applied. Apply oils, aerosols, smoke, poison baits, etc. as they are.
  • the compound of the present invention can be used as an insecticide for agricultural land such as fields, paddy fields, lawns, orchards, or non-agricultural land.
  • the compound of the present invention may be able to control pests on the farmland without causing any phytotoxicity on the farmland or the like where the following “crop” or the like is cultivated.
  • Agricultural crops corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, sugar beet, rapeseed, sunflower, sugarcane, tobacco, etc.
  • Vegetables Solanum vegetables (eggplants, tomatoes, peppers, peppers, potatoes, etc.), Cucurbitaceae vegetables (cucumbers, pumpkins, zucchini, watermelons, melons, etc.), Brassicaceae vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage) , Mustard, broccoli, cauliflower, etc.), asteraceae vegetables (burdock, shungiku, artichokes, lettuce, etc.), liliaceae vegetables (leek, onion, garlic, asparagus), celery family vegetables (carrot, parsley, celery, American scallop, etc.) ), Red crustacean vegetables (spinach, chard, etc.), persimmon vegetables (perilla, mint, basil, etc.), strawberry, sweet potato, yam, taro, etc.
  • Trees other than fruit trees Cha, mulberry, flowering trees, street trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak, poplar, redwood, fu, sycamore, zelkova, black bean, peach tree, Tsuga, rat, pine, Spruce, yew) etc.
  • crop has classic resistance to HPPD inhibitors such as isoxaflutol, ALS inhibitors such as imazetapyr and thifensulfuron methyl, EPSP synthase inhibitors, glutamine synthase inhibitors, and herbicides such as bromoxynil. Also included are crops granted by traditional breeding methods or genetic engineering techniques. Examples of “crop” tolerated by classical breeding methods include Clearfield® canola that is resistant to imidazolinone herbicides such as imazetapil, and sulfonylurea ALS-inhibiting herbicides such as thifensulfuron methyl For example, resistant STS soybeans.
  • crops that have been rendered tolerant by genetic engineering techniques include corn varieties that are resistant to glyphosate and glufosinate, and are already sold under trade names such as RoundupReady (registered trademark) and LibertyLink (registered trademark) .
  • the “crop” includes, for example, crops that can synthesize selective toxins known in the genus Bacillus using genetic recombination technology.
  • toxins expressed in such genetically modified plants include insecticidal proteins derived from Bacillus cereus and Bacillus popilie; Insecticidal proteins such as ⁇ -endotoxin, VIP1, VIP2, VIP3 or VIP3A; nematode-derived insecticidal proteins; toxins produced by animals such as scorpion toxin, spider toxin, bee toxin or insect-specific neurotoxin; Plant lectin; agglutinin; protease inhibitors such as trypsin inhibitor, serine protease inhibitor, patatin, cystatin, papain inhibitor; lysine, corn-RIP, abrin, ruffin, saporin, briodin, etc.
  • Ribosome inactivating protein RIP
  • steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glucosyltransferase, cholesterol oxidase; ecdysone inhibitor; HMG-COA reductase; sodium channel, calcium channel inhibitor, etc. Ion channel inhibitor; juvenile hormone esterase; diuretic hormone receptor; stilbene synthase; bibenzyl synthase; chitinase; glucanase and the like.
  • toxins expressed in such genetically modified crops hybrids of insecticidal proteins such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, ⁇ -endotoxin proteins, VIP1, VIP2, VIP3 or VIP3A Toxins, partially defective toxins, modified toxins are also included.
  • Hybrid toxins are produced by new combinations of different domains of these proteins using recombinant techniques.
  • Cry1Ab lacking a part Cry1Ab lacking a part of the amino acid sequence is known.
  • the modified toxin one or more amino acids of the natural toxin are substituted.
  • Examples of these toxins and recombinant plants capable of synthesizing these toxins are EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878. , WO 03/052073, and the like.
  • the toxins contained in these recombinant plants particularly confer resistance to Coleoptera pests, Diptera pests, and Lepidoptera pests.
  • genetically modified plants that contain one or more insecticidal pest resistance genes and express one or more toxins are already known and some are commercially available.
  • transgenic plants include YieldGard® (a corn variety that expresses Cry1Ab toxin), YieldGuard Rootworm® (a corn variety that expresses Cry3Bb1 toxin), YieldGard Plus® (Cry1Ab and Cry3Bb1) Corn varieties expressing toxin), Herculex I® (corn varieties expressing phosphinotricin N-astilyltransferase (PAT) to confer resistance to Cry1Fa2 toxin and glufosinate), NuCOTN33B® (Cotton variety expressing Cry1Ac toxin), Bollgard I (registered trademark) (cotton variety expressing Cry1Ac toxin), Bollgard II (registered trademark) (C Cotton varieties expressing y1Ac and Cry2Ab toxin), VIPCOT (registered trademark) (cotton varieties expressing VIP toxin), NewLeaf (registered trademark) (potato variety expressing Cry3A toxin),
  • the “crop” includes those given the ability to produce an anti-pathogenic substance having a selective action using a genetic recombination technique.
  • PR proteins and the like are known as examples of anti-pathogenic substances (PRPs, EP-A-0 392 225).
  • anti-pathogenic substances and genetically modified plants that produce them are described in EP-A-0 392 225, WO 95/33818, EP-A-0 353 191 and the like.
  • Examples of anti-pathogenic substances expressed in such genetically modified plants include, for example, sodium channel inhibitors, calcium channel inhibitors (KP1, KP4, KP6 toxins produced by viruses, etc.).
  • Ion channel inhibitor Ion channel inhibitor
  • stilbene synthase bibenzyl synthase
  • chitinase glucanase
  • PR protein PR protein
  • peptide antibiotics antibiotics having heterocycles, protein factors involved in plant disease resistance (referred to as plant disease resistance gene, WO03 / 000906)) and other anti-pathogenic substances produced by microorganisms.
  • the harmful arthropod control agent of the present invention includes other harmful arthropod control agents, acaricides, nematicides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil improvers. It may contain animal feed or the like. Further, the compound of the present invention and harmful arthropod control agents such as other types of insecticides, acaricides, nematicides or fungicides, plant hormone agents, plant growth regulators, herbicides, etc. (isomers) It is also possible to mix synergists, safeners, pigments, fertilizers, etc., and prepare mixed preparations as appropriate, and use them for spraying treatment, soil treatment and hydroponic liquid treatment. is there.
  • Examples of the active ingredients of the other harmful arthropod control agents, acaricides and / or nematicides include the following.
  • Organophosphorus compounds Acephate, aluminum phosphide, butathiofos, cadusafos, chlorethoxyphos, chlorfenvinphos, chlorpyvinphos, chlorpyvinphos Chlorpyrifos-methyl, cyanophos (CYAP), diazinon, DCIP (dichlorodipropionic ether), dichlorfenthion (ECP), dichlorvos (DichV) Dimethoate, dimethylvinphos, disulfoton, EPN, etion, ethoprofos, etrimfos, fenthion (MPP), fenitrothion (fethrothion) fothiazate, formothione, hydrogen phosphide, isofenphos, isoxathion, malathion, mesulfenfos, methidation Monocrotophos, Naled (BRP), Oxydeprofos (ESP), Parathion, Phosal
  • Phenylpyrazole compounds Acetoprole, etiprole, fipronil, vaniliprole, pyriprole, pyrafluprole, etc.
  • Bt toxin insecticide live spores and produced crystal toxins derived from Bacillus thuringiensis, and mixtures thereof
  • Hydrazine compounds Chromafenozide, halofenozide, methoxyphenozide, tebufenozide, etc.
  • Acaricides acequinocyl, amitraz, benzoximate, phenisobromolate, chinomethionate, chlorbenzilate, chlorbenzilate, cBS ), Kelsen (dicofol), etoxazole, fenbutatin oxide, phenothiocarb, fenpyroximate, fluacrylpyriproxyl roxyfen, hexythiazox, propargite (BPPS), polynactin complex (polyactin), pyridaben, dipymidifene, tebufenpyrad, tebufenpyrad, tebufenpyrad, tebufenpyrad, tebufenpyrad Amidoflumet, bifenazate, cyflumetofen, etc.
  • Nematicide (nematode active ingredient) DCIP, fostiazate, levamisole hydrochloride, methylisothio
  • Reference production example 1 ⁇ 2-Chloro-5- [5- (3,5-dichloro-4-fluorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl obtained by Reference Production Example 2 ⁇ 17.3 g of tert-butyl carbamate was dissolved in 96 mL of tetrahydrofuran, and 96 mL of 28% aqueous sodium hydroxide solution, 31 mL of aqueous ammonia, 10.5 g of ammonium chloride, and 1.7 g of trioctylmethylammonium chloride were added.
  • Reference production example 4 13.5 g of tert-butyl N- (5-acetyl-2-chlorophenyl) carbamate obtained in Reference Production Example 7 and 3 ′, 5′-dichloro-4′-fluoro-2 obtained in Reference Production Example 5 , 2,2-trifluoroacetophenone and 14.0 mL of triethylamine were dissolved in 100 mL of tetrahydrofuran and stirred at 60 ° C. for 1 hour and at 80 ° C. for 1 hour. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure and N- ⁇ 2-chloro-5- [3- (3,5-dichloro-4-fluorophenyl) -4,4,4-trifluoro-3-hydroxy.
  • Reference production example 6 19.2 g of sodium nitrite was dissolved in 280 mL of concentrated sulfuric acid, and a solution of 25.0 g of 3,5-dichloro-4-fluoroaniline in 280 mL of acetic acid was added under ice cooling. After stirring at the same temperature for 3 hours, the mixture was stirred at room temperature for 1 hour. A solution prepared by dissolving 96.9 g of potassium potassium in 500 mL of water was added under ice cooling, and the mixture was stirred at 70 ° C. for 1 hour. Cool to room temperature and extract the reaction mixture with dichloromethane and chloroform. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure.
  • Reference production example 12 N- ⁇ 2-chloro-5- [5- (3,4,5-trichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl obtained by Reference Production Example 8 ⁇ 500 mg of tert-butyl carbazate and 0.15 ml of triethylamine were dissolved in 1.8 ml of tetrahydrofuran, 0.08 ml of acetyl chloride was added dropwise under ice cooling, and the mixture was stirred at the same temperature for 5 minutes. After stirring at room temperature for 30 minutes, water was added to the reaction mixture and the mixture was extracted with ethyl acetate.
  • N′-acetyl-N- ⁇ 2-chloro-5- [5- (3,4,5-tri 480 mg of a crude product of tert-butyl chlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl ⁇ carbazate was obtained.
  • 0.88 mL of trifluoroacetic acid was added at room temperature, and the mixture was stirred at room temperature for 2 hours.
  • the reaction mixture was concentrated under reduced pressure, and the resulting residue was subjected to silica gel column chromatography to give N ′- ⁇ 2-chloro-5- [5- (3,4,5-trichlorophenyl) -5-trifluoromethyl.
  • comparative compound (a) 200 mg of -4,5-dihydroisoxazol-3-yl] phenyl ⁇ acetylhydrazide (hereinafter referred to as comparative compound (a)) was obtained.
  • a part represents a weight part.
  • Formulation Example 1 Nine parts of each of the compounds (1) to (2) of the present invention are dissolved in 37.5 parts of xylene and 37.5 parts of dimethylformamide, to which 10 parts of polyoxyethylene styrylphenyl ether and 6 parts of calcium dodecylbenzenesulfonate are added. And stirring well to obtain an emulsion.
  • Formulation Example 2 To 40 parts of each of the compounds (1) to (2) of the present invention, 5 parts of Solpol 5060 (registered trademark of Toho Chemical Co., Ltd.) was added and mixed well to prepare Carplex # 80 (registered trademark of Shionogi & Co., synthetic silicon hydroxide).
  • Fine powder 32 parts and 23 parts of 300 mesh diatomaceous earth are added and mixed with a juice mixer to obtain a wettable powder.
  • Formulation Example 3 Add 3 parts of each of the compounds (1) to (2) of the present invention, 5 parts of synthetic silicon hydroxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 57 parts of clay, and stir and mix well. An appropriate amount of water is added to the mixture, further stirred, granulated with a granulator, and dried by ventilation to obtain granules.
  • Formulation Example 4 Juice after thoroughly mixing 4.5 parts of each of the compounds (1) to (2) of the present invention, 1 part of a synthetic silicon hydroxide fine powder, 1 part of Doreles B (Sankyo Co., Ltd.) as a flocculant and 7 parts of clay in a mortar Stir and mix with a mixer. 86.5 parts of cut clay is added to the resulting mixture and mixed well with stirring to obtain a powder.
  • Formulation Example 5 Formulation by mixing 10 parts of each of the compounds (1) to (2) of the present invention, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt and 55 parts of water, and finely pulverizing them by a wet pulverization method. Get.
  • Formulation Example 6 0.5 parts of each of the compounds (1) to (2) of the present invention are dissolved in 10 parts of dichloromethane, and this is mixed with 89.5 parts of Isopar M (isoparaffin: Exxon Chemical Registration) to obtain an oil.
  • Formulation Example 7 0.1 part of each of the compounds (1) to (2) of the present invention and 49.9 parts of Neothiozole (Chuo Kasei Co., Ltd.) are placed in an aerosol can and fitted with an aerosol valve, followed by 25 parts of dimethyl ether and 25 parts of LPG. Is added, shaken, and an actuator is attached to obtain an oily aerosol.
  • Formulation Example 8 0.6 parts of each of the compounds (1) to (2) of the present invention, 0.01 part of BHT, 5 parts of xylene, 3.39 parts of deodorized kerosene and 1 part of an emulsifier ⁇ Atmos 300 (registered trademark of Atmos Chemical) ⁇
  • the dissolved one and 50 parts of distilled water are filled into an aerosol container, a valve part is attached, and 40 parts of propellant (LPG) is pressurized and filled through the valve to obtain an aqueous aerosol.
  • LPG propellant
  • test examples show that the compounds of the present invention are effective as active ingredients of harmful arthropod control compositions.
  • this invention compound is represented by the said compound number.
  • Test example 1 Each formulation of the present compounds (1) to (2) obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 500 ppm to prepare a test drug solution.
  • a filter paper of the same size was laid on the bottom of a polyethylene cup having a diameter of 5.5 cm, 0.7 ml of the test chemical solution was dropped onto the filter paper, and 30 mg of sucrose was uniformly added as a bait.
  • Ten female fly (Musca domestica) females were released into the polyethylene cup and capped. The life and death of the housefly was investigated 24 hours later, and the mortality rate was determined by the following formula.
  • Death rate (%) (Number of dead insects / number of test insects) ⁇ 100 As a result, the death rate was 90% or more in the treatments of the compound formulas (1) to (2) of the present invention.
  • Test example 3 Each formulation of the present compounds (1) to (2) obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 500 ppm to prepare a test drug solution. 20 mL of the test chemical solution was sprayed on cabbage (Brassicae oleracea) at the 3-4 leaf stage.
  • the above-ground part is cut off, stored in a polyethylene cup (capacity 100 mL) together with 5 second-ordered larvae (Plutella xylostella), stored at 25 ° C., and after 5 days, the number of surviving insects is investigated.
  • Test example 4 Each formulation of the present compounds (1) to (2) obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 500 ppm to prepare a test drug solution.
  • Artificial fodder Insector LF (Nippon Agricultural Industries) placed on the bottom of a 5.5 cm diameter polyethylene cup with the same size filter paper, sliced to 6 mm thickness and cut in half, and 2 mL of the above test chemical solution was irrigated. After the test dilution was air-dried, 5 4th instar larvae of Spodoptera litura were released and capped. Six days later, the number of surviving insects was examined, and the death rate was determined by the following formula.
  • Control value (%) ⁇ 1 ⁇ (Cb ⁇ Tai) / (Cai ⁇ Tb) ⁇ ⁇ 100
  • the character in a formula represents the following meaning.
  • Test Example 8 About this invention compound (1) and (2), the acetone solution was prepared so that it might become a dosage (mg / m ⁇ 2 >) as shown in Table 1 when processing on a glass surface. 0.2 mL of an acetone solution was uniformly applied to the inner wall of a glass screw tube and a lid (No. 5 manufactured by Marum Corp.). After drying, put a test tick (Tetula tick, non-blood-sucking young tick, 10 per group) in the screw tube, close the lid and seal, investigate the number of lethals two days later, and calculate the death rate by the following formula: Was calculated.
  • the compound of the present invention is useful as an active ingredient of a harmful arthropod control agent.

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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

L'invention concerne un composé d'hydrazide représenté par la formule (1) et exerçant un excellent effet de lutte contre des arthropodes nuisibles, un agent de lutte contre les arthropodes nuisibles contenant ledit composé en tant que principe actif, et une méthode de lutte contre les arthropodes nuisibles, dans laquelle une quantité efficace dudit composé est appliquée sur les arthropodes nuisibles ou sur l'habitat des arthropodes nuisibles.
PCT/JP2014/068372 2013-07-08 2014-07-03 Composé d'hydrazide et son utilisation pour lutter contre les arthropodes nuisibles WO2015005408A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022061914A1 (fr) * 2020-09-28 2022-03-31 台州臻挚生物科技有限公司 Procédé de préparation de 3,5-dihalogénotrifluoroacétophénone et d'un dérivé correspondant

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007105814A1 (fr) * 2006-03-10 2007-09-20 Nissan Chemical Industries, Ltd. Compose isoxazoline substitue et agent antiparasite
WO2010090344A1 (fr) * 2009-02-06 2010-08-12 Sumitomo Chemical Company, Limited Composés hydrazides et leur utilisation dans la protection phytosanitaire
JP2011178673A (ja) * 2010-02-26 2011-09-15 Nissan Chem Ind Ltd 非農園芸害虫の防除方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007105814A1 (fr) * 2006-03-10 2007-09-20 Nissan Chemical Industries, Ltd. Compose isoxazoline substitue et agent antiparasite
WO2010090344A1 (fr) * 2009-02-06 2010-08-12 Sumitomo Chemical Company, Limited Composés hydrazides et leur utilisation dans la protection phytosanitaire
JP2011178673A (ja) * 2010-02-26 2011-09-15 Nissan Chem Ind Ltd 非農園芸害虫の防除方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022061914A1 (fr) * 2020-09-28 2022-03-31 台州臻挚生物科技有限公司 Procédé de préparation de 3,5-dihalogénotrifluoroacétophénone et d'un dérivé correspondant

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