WO2015005408A1 - Hydrazide compound, and use thereof for controlling harmful arthropods - Google Patents

Abstract

Provided are a hydrazide compound represented by formula (1) and exerting an excellent effect of controlling harmful arthropods, a harmful arthropod control agent containing said compound as an active ingredient, and a method for controlling harmful arthropods in which an effective amount of said compound is applied to harmful arthropods or to the habitat of harmful arthropods.

Description

Hydrazide compounds and their use for controlling harmful arthropods

The present invention relates to a hydrazide compound and its use for controlling harmful arthropods.

Conventionally, compounds having control activity against harmful arthropods have been found and developed as active ingredients of harmful arthropod control agents.
Also, certain hydrazide compounds are known as active ingredients of harmful arthropod control agents (see, for example, Patent Document 1 and Patent Document 2).

International Publication No. 2010/032437 International Publication No. 2010/090344

An object of the present invention is to provide a novel hydrazide compound having a controlling activity against harmful arthropods.

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 production of the compound of the present invention will be described below.

(Production method 1)
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).

[Wherein, 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.
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. , 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. Can be mentioned.
When L is a chlorine atom, the reaction is usually carried out 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, and organic amines such as triethylamine and pyridine.
When L is a hydroxyl group, the reaction is carried out in the presence of a condensing agent.
Examples of 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.
In the case where L is a hydroxyl group, 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.
After completion of the reaction, 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.
(Production method 2)
The compound of the present invention can be produced by reacting the compound represented by the formula (4) with the acid (5).

[Wherein, X ¹ , X ² and R ² represent the same meaning as [1]. ]
The reaction is usually performed 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. , 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. Can be mentioned.
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.
After completion of the reaction, 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.

(Production method 3)
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).

[Wherein, 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. Represents a leaving group such as a lomethanesulfonyloxy group. ]
The reaction is usually performed 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. , 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. Can be mentioned.
The reaction is carried out in the presence of a base as necessary.
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 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.
After completion of the reaction, 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.
In addition, the reaction is a coupling reaction using a general transition metal catalyst described in literature, for example, Org. Lett. 3, 3803-3805 (2001).

Next, the manufacturing method of the intermediate body used for manufacture of this invention compound is demonstrated.

(Reference production method 1)
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).

[Wherein, X ¹ , X ² , R ² and L represent the same meaning as described above. ]
The reaction is usually performed 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. , 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. Can be mentioned.
When L is a chlorine atom, the reaction is usually carried out 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, and organic amines such as triethylamine and pyridine.
When L is a hydroxyl group, the reaction is carried out in the presence of a condensing agent.
Examples of 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.
After completion of the reaction, 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.
(Reference production method 2)
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.
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.
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.
After completion of the reaction, 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.
After completion of the reaction, 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 4)
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.

[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 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, 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 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. In the reaction, if necessary, 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.
After completion of the reaction, 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.
(Reference production method 5)
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.
Examples of 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.
Examples of 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., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, 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).
After completion of the reaction, 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.
Examples of the solvent used in the reaction include alcohols such as ethanol, water, and a mixture thereof.
Examples of the metal used in the reaction include iron, tin, and tin (II) chloride.
Examples of 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., and the reaction time is usually in the range of 0.5 to 12 hours.
After completion of the reaction, 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.

(Reference production method 6)
The compound represented by the formula (16) can be produced by reacting the compound represented by the formula (13-1) with trifluoroacetic anhydride.

[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 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, sulfoxides 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.
After completion of the reaction, 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.
(Reference production method 7)
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.

[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, water, and mixtures thereof.
Examples of 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. In such a case, the reaction is performed in the presence of a base. Examples of 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.
In the reaction, if necessary, 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.
After completion of the reaction, 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.
(Reference production method 8)
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.
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 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.
After completion of the reaction, 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.
(Reference production method 9)
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.
After completion of the reaction, 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.
(Reference production method 10)
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.
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 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.
After completion of the reaction, 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.

(Reference production method 11)
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.

[Wherein, X ² represents the same meaning as described above, and R ⁶ represents a C1-C6 alkyl group. ]
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 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.
After completion of the reaction, 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.
(Reference production method 12)
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.
Examples of 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.
Examples of 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.
After completion of the reaction, 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.
(Reference production method 13)
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).

[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.
Examples of the solvent used in the reaction include water, acidic aqueous solutions such as hydrochloric acid and sulfuric acid, and mixtures thereof.
Examples of the diazotization reagent (29) used for the reaction include nitrites such as sodium nitrite.
As an inorganic halogen reagent (30) used for reaction, potassium iodide etc. are mentioned, for example.
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.
After completion of the reaction, 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.
(Reference production method 14)
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.

[Wherein X ² represents the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of 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.
After completion of the reaction, 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.
(Reference production method 15)
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).

[Wherein X ² represents the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of 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.
After completion of the reaction, 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.
(Reference production method 16)
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.
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 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.
After completion of the reaction, 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.
(Reference production method 18)
The compound represented by the formula (34) can be produced by reacting the compound represented by the formula (35) with a chlorinating agent (36).

[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 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.
After completion of the reaction, 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.
(Reference production method 19)
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.
Examples of hydroxylamine used in the reaction 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. Examples of 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.
After completion of the reaction, 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.

Examples of 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 (Tomoptera citricidus), peach beetle (Homoptera) Stink bugs such as stink bugs (Riptortus clavetus), spider helicopter bugs (Leptocorina chinensis), bark beetles (Eysarcoris parvus), winged bugs (Haryomorpha mista) m), tobacco whitefly (Bemisia tabaci), silverleaf whitefly (Bemisia argentifolii), 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 purchasi, Fujino scale (Pranococcus kraunhiae), Pseudococcidae dura coccus longispinis), scale insects such as white peach scale (Pseudaulacaspis pentagona), tingidae class, psyllid, and the like.
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. Leguminova glycinnivorella), Azusa yamashiga (Matsumuraeses azukivivora), Apple wolfberry (Adoxophyces orana moss), Adenophymata (Adoxophane). Fuscocuprenus, Cydia pomonella, and other genus of the genus Cypridaria, Eugenes of the genus Cyprus Species of the genus and other species, Suga such as Plutella xylostella, Cotton moth (Pectinophora gossypiella) Potato moth such as Phthorimaea operculella (Hyphantia, Hyphantriguri) nslucens), webbing clothes moth (Tineola bisselliella) Hirozukoga such as such.
Thysanoptera: western flower thrips (Frankliniella occidentalis), Minami thrips (Thrips parmi), 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 sativae), the pea (Chromatomyia horticola) etc.
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 decemlineata), beetle beetle (Agriotes spp.), Tobacco beetle (Lasiderma serricorne), reverb worm Oyster beetle (Lyctus bruneus), Japanese beetle beetle (Anoprophora malasiaca), pine beetle (Tomicus pinipeda) and the like.
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); Tomato rustic mites (Aculops lycopersici), Chanosabi mites (Calacarus carinatus), Chanoagasabi mite (Acaphylla theavagrans), Phytophorid mites (Eriophys chibaensis), etc. 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.

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.

Examples of the solid carrier used for formulation 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. Examples of the liquid carrier 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. Hydrogen (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.), 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 ether, 3-methoxy-3-methyl-1-butanol, etc. ), Acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), sulfoxides (dimethylsulfoxide, etc.), propylene carbonate and vegetable oil (Soybean oil, cottonseed oil, etc.).
Examples of the gaseous carrier include fluorocarbon, butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbon dioxide gas.
Examples of the surfactant 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-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.

In addition, although 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.
Examples of 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. Is 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. Specifically, for example, planting treatment (planting hole spraying, planting hole treatment soil mixing), plant source treatment (stock source spraying, strain source) Soil admixture, strainer irrigation, seedling treatment in the latter half of the seedling season), 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) , Soil surface spraying, soil surface mixing, sowing hole spraying, buttocks land surface spraying, inter-strain dispersion ), Other irrigation treatments (soil irrigation, seedling stage irrigation, chemical solution injection treatment, subsurface irrigation, chemical drip irrigation, chemigation), nursery box treatment (nursery box spraying, seedling box irrigation), seedling tray treatment (nursery tray spraying) , Nursery tray irrigation), nursery treatment (seed bed spraying, nursery bed irrigation, water seedling surrogate seedbed spraying, seedling soaking), bed soil blending treatment (floor soil blending, floor soil blending before sowing), other treatments (culture soil blending, seeding, Topsoil blending, raindrops soil blending, planting position treatment, granule inflorescence spraying, paste fertilizer blending)
Seed treatment is, for example, control of harmful arthropods by treating the active ingredients directly or in the vicinity of seeds, seed pods or bulbs of crops to be protected from damage such as feeding by harmful arthropods. It is a treatment method that expresses efficacy, and specifically includes, for example, spraying treatment, smearing treatment, dipping treatment, impregnation treatment, coating treatment, film coating treatment, pellet coating treatment,
Hydroponic liquid treatment is, for example, by treating active ingredients in hydroponic liquid etc. in order to infiltrate and transfer from inside the plant body of crops to be protected from damage such as feeding by harmful arthropods The treatment method protects the crop from damage caused by harmful arthropods. Specific examples include hydroponic liquid mixing and hydroponic liquid mixing.

When the harmful arthropod control agent of the present invention is used for controlling harmful arthropods in the agricultural field, 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. When 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.

When the harmful arthropod control agent of the present invention is used for controlling harmful arthropods (eg, flies, mosquitoes, cockroaches) living in the house, 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. When 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.
Bridegroom,
Foliage plant,
Fruit trees; pears (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, 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.

The above "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. Examples of 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.
Examples of toxins expressed in such genetically modified plants include insecticidal proteins derived from Bacillus cereus and Bacillus popilie; Insecticidal proteins such as δ-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.
In addition, as toxins expressed in such genetically modified crops, hybrids of insecticidal proteins such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, δ-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. As a toxin lacking a part, Cry1Ab lacking a part of the amino acid sequence is known. In 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.
In addition, 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. Examples of these 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), NatureGard (registered trademark) Agurisure (registered trademark) (Trademark) GT Advantage (GA21 glyphosate resistant trait), Agurisure (registered trademark) CB Advantage (Bt11 corn borer (CB) trait), Protecta (registered trademark), and the like.
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). Such 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; stilbene synthase; bibenzyl synthase; chitinase; glucanase; 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.

(1) 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, Phosalone, Phosmet: PMP, Pirimiphosentyl, pyrimiphosentylthiol Quinalphos, phentoate (PAP), profenofos, propopafos, prothiofos, pyrachlorfos, salithion, sulprofos sulprofos upirimfos), temephos (temephos), tetra-chloro bottles host (tetrachlorvinphos), terbufos (terbufos), thiometon (thiometon), trichlorfon (trichlorphon: DEP), vamidothion (vamidothion), etc.,
(2) Carbamate compounds alaniccarb, bendiocarb, benfuracarb, BPMC, carbaryl, carbofuran, carbothofen, carbotophene ), Fenobucarb, phenothiocarb, phenoxycarb, furathiocarb, isoprocarb (MIPC), metocarbyl, metocarbyl thiocarb), NAC, oxamyl, spirimicarb, propoxur (PHC), XMC, thiodicarb, xylylcarb, etc.
(3) Synthetic pyrethroid compounds Acrinathrin, Allethrin, Benfluthrin, Beta-Cyfluthrin, Bifenthrin, Cycloprothrin, Cycloprothrin (Cycloprothrin) cyhalothrin, cypermethrin, deltamethrin, esfenvalerate, ethofenprox, fenpropathrin, fenvalerate, fenvalerate (Flucytrinate), flufenprox, flumethrin, fluvalinate, halfenprox, imiprothrin, permethrin, p, methrerin, p Resmethrin, sigma-cypermethrin, silafluofen, tefluthrin, tralomethrin, transfluthrin 5, transfluthrin 6, transfluthrin 6, transfluthrin 6, Fluoro-4- (methoxymethyl) benzyl (EZ)-(1RS, 3RS; 1RS, 3SR) -2,2-dimethyl-3-prop-1-enylcyclopropanecarboxylate, 2,3,5,6-tetra Fluoro-4-methylbenzyl (EZ)-(1RS, 3RS; 1RS, 3SR) -2,2-dimethyl-3-prop-1-enylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4 -(Methoxymethyl) benzyl (1RS, 3RS; 1RS, 3SR) -2,2dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate, etc.
(4) Nereistoxin compounds Cartap, bensultap, thiocyclam, monosultap, bisultap, etc.
(5) Neonicotinoid compounds Imidacloprid, nitenpyram, acetamiprid, thiamethoxam, thiacloprid, dinoteurine, dinotefur
(6) Benzoylurea compounds Chlorfluazuron, bistrifluron, diafenthiuron, diflubenzuron, fluazuron, flucycloxuron, flucycloxuron Flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuuron, triflumulon, etc.
(7) Phenylpyrazole compounds Acetoprole, etiprole, fipronil, vaniliprole, pyriprole, pyrafluprole, etc.
(8) Bt toxin insecticide, live spores and produced crystal toxins derived from Bacillus thuringiensis, and mixtures thereof,
(9) Hydrazine compounds Chromafenozide, halofenozide, methoxyphenozide, tebufenozide, etc.,
(10) Organochlorine compounds Aldrin, dieldrin, dienochlor, endosulfan, methoxychlor, etc.
(11) Natural pesticide machine oil, nicotine sulfate, etc.
(12) Other insecticides avermectin (vermectin-B), bromopropyrate, buprofezin, chlorfenapyr, cyromazine, D-D (1, ro-dictin) emamectin-benzoate, phenazaquin, flupyrazofos, hydroprene, indoxacarb, methoxadiazone, tetroylamine, milbemycin A, z (Pyridalyl), pyriproxyfen, spinosad, sulfuramide, tolfenpyrad, triazamate, flubendamide, flubendamide, flubendamide Arsenicacid, Benclothiaz, Calcium cyanoamide, Calcium polysulfide, Chlordane, DDT, DSP, flufenem, flufenamide flurimfen, formatenate, metham-ammonium, metham-sodium, methyl bromide, nidinotefuran, potassium oleate, pitolephenate Butto (protrifenbute), spiromesifen (spiromesifen), sulfur (Sulfur), metaflumizone (spiratetrazone), spirotetramat, 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, methylisothiocyanate, morantel tartrate and the like.

Next, specific examples of the optically active substance of the compound of the present invention are shown.
N ′-{2-chloro-5-[(R) -5- (3,4,5-trichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} cyclopropane Carbohydrazide,
N ′-{2-chloro-5-[(S) -5- (3,4,5-trichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} cyclopropane Carbohydrazide,
N ′-{2-chloro-5-[(R) -5- (3,5-dichloro-4-fluorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} -4,4,4-trifluorobutyrohydrazide,
N ′-{2-chloro-5-[(S) -5- (3,5-dichloro-4-fluorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} -4,4,4-trifluorobutyrohydrazide.

Hereinafter, although this invention is demonstrated in more detail by a manufacture example, a formulation example, a test example, etc., this invention is not limited to these examples.

First, the manufacture example of this invention compound is shown below.
Production Example 1
N- {2-chloro-5- [5- (3,5-dichloro-4-fluorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} carbazate tert-butyl 350 mg and 0.11 ml of triethylamine were dissolved in 1.3 ml of tetrahydrofuran, 0.09 ml of 4,4,4-trifluorobutyryl chloride was added dropwise thereto at room temperature, and the mixture was stirred at room temperature for 5 minutes. Water was added to the reaction mixture and the mixture was extracted with tert-butyl methyl ether and ethyl acetate. The organic layer was concentrated under reduced pressure, and N′-4,4,4-trifluorobutyryl-N- {2-chloro-5- 387 mg of a crude product of tert-butyl [5- (3,5-dichloro-4-fluorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} carbazate was obtained. N′-4,4,4-trifluorobutyryl-N- {2-chloro-5- [5- (3,5-dichloro-4-fluorophenyl) -5-trifluoromethyl-4, To a crude product of tert-butyl 5-dihydroisoxazol-3-yl] phenyl} carbazate was added 0.65 mL of trifluoroacetic acid at room temperature, and the mixture was stirred at the same temperature for 1.5 hours. To the reaction mixture was added tert-butyl methyl ether and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, and N ′-{2-chloro-5- [5- (3,5-dichloro-4-fluorophenyl) -5-trifluoromethyl-4,5-dihydro 305 mg of isoxazol-3-yl] phenyl} -4,4,4-trifluorobutyrohydrazide (hereinafter referred to as the present compound (1)) was obtained.
Compound (1) of the present invention

¹ H-NMR (CDCl ₃ ) δ: 7.56 (2H, d, J = 6.0 Hz), 7.36 (1H, d, J = 8.2 Hz), 7.25 (1H, d, J = 2.1 Hz), 7.21-7.17 (1 H, m), 7.01 (1 H, dd, J = 8.2, 2.1 Hz), 6.51 (1 H, d, J = 2.8 Hz) ), 4.02 (1H, d, J = 17.2 Hz), 3.62 (1H, d, J = 17.2 Hz), 2.75-2.46 (4H, m).

Production Example 2
N- {2-chloro-5- [5- (3,5-dichloro-4-fluorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} carbazate tert-butyl Instead of N- {2-chloro-5- [5- (3,4,5-trichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazole-3- N ′-{2-chloro-5- [5- (3,4,5-trichlorophenyl) -5-trifluoro] by the same method as in Production Example 1 using tert-butyl yl] phenyl} carbazate Methyl-4,5-dihydroisoxazol-3-yl] phenyl} cyclopropanecarbohydrazide (hereinafter referred to as the present compound (2)) was obtained.
Compound 2 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 7.65-7.36 (4H, m), 7.33 (1H, d, J = 8.4 Hz), 6.94 (1H, dd, J = 8. 4, 2.0 Hz), 6.54 (1 H, br s), 4.04 (1 H, d, J = 17.6 Hz), 3.64 (1 H, d, J = 17.6 Hz), 1.53 (1H, m), 1.07 (2H, m), 0.91 (2H, m).

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. To this mixed solution, 96 mL of 5% aqueous sodium hypochlorite solution was added dropwise at room temperature over 25 minutes. After stirring at the same temperature for 15 minutes, tert-butyl methyl ether was added to the reaction mixture, the organic layer was separated, and a 10% aqueous sodium sulfite solution was added for extraction again. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, and N- {2-chloro-5- [5- (3,5-dichloro-4-fluorophenyl) -5-trifluoromethyl-4,5-dihydroiso 9.00 g of tert-butyl oxazol-3-yl] phenyl} carbazate was obtained.
N- {2-chloro-5- [5- (3,5-dichloro-4-fluorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} carbazate tert-butyl

¹ H-NMR (CDCl ₃ ) δ: 7.61 (1H, d, J = 2.1 Hz), 7.58 (2H, d, J = 6.2 Hz), 7.56-7.52 (1H, m), 7.48 (1H, d, J = 8.5 Hz), 4.56-4.52 (2H, m), 4.07 (1H, d, J = 17.2 Hz), 3.71- 3.61 (1H, m), 1.57 (9H, s).
Reference production example 2
N- {2-chloro-5- [3- (3,5-dichloro-4-fluorophenyl) -4,4,4-trifluoro-2-butenoyl] phenyl} carbamic acid obtained in Reference Production Example 3 17.0 g of tert-butyl and 3.6 g of tetrabutylammonium bromide were dissolved in 66 mL of tert-butyl methyl ether, and 4.6 g of hydroxylamine hydrochloride and 5.6 g of sodium hydroxide were dissolved in 27 mL of water under ice cooling. The solution was added dropwise and stirred at room temperature for 1 hour. The reaction mixture was neutralized with 3N hydrochloric acid, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized to give N- {2-chloro-5- [5- (3,5-dichloro-4-fluorophenyl) -5-trifluoromethyl-4. , 5-Dihydroisoxazol-3-yl] phenyl} carbamate 17.3 g of tert-butyl was obtained.
N- {2-chloro-5- [5- (3,5-dichloro-4-fluorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} carbamate tert-butyl

¹ H-NMR (CDCl ₃ ) δ: 8.39 (1H, d, J = 1.8 Hz), 7.59 (2H, d, J = 6.2 Hz), 7.46 (1H, dd, J = 8.4, 1.7 Hz), 7.39 (1 H, d, J = 8.5 Hz), 7.13-7.07 (1 H, m), 4.12 (1 H, d, J = 17.2 Hz) ), 3.71 (1H, d, J = 17.4 Hz), 1.55 (9H, s).
Reference production example 3
N- {2-chloro-5- [3- (3,5-dichloro-4-fluorophenyl) -4,4,4-trifluoro-3-hydroxybutanoyl] phenyl} obtained in Reference Production Example 4 27.0 g of tert-butyl carbamate, 14.0 mL of triethylamine, and 610 mg of N, N-dimethyl-4-aminopyridine were dissolved in 50 mL of toluene, and 4.7 mL of acetic anhydride was added dropwise thereto at room temperature, and the mixture was stirred at 50 ° C. for 3 hours. Stir. Water was added to the reaction mixture cooled to room temperature, and the mixture was extracted with tert-butyl methyl ether. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, and N- {2-chloro-5- [3- (3,5-dichloro-4-fluorophenyl) -4,4,4-trifluoro-2-butenoyl ] 17.1 g of tert-butyl phenyl} carbamate was obtained.
Tert-Butyl N- {2-chloro-5- [3- (3,5-dichloro-4-fluorophenyl) -4,4,4-trifluoro-2-butenoyl] phenyl} carbamate

¹ H-NMR (CDCl ₃ ) δ: 8.70 (1H, s), 7.44-7.41 (1H, m), 7.34-7.31 (1H, m), 7.29-7 .28 (1H, m), 7.07-7.03 (1H, m), 1.57 (9H, s).
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. 27.0 g of a crude product of tert-butyl butanoyl] phenyl} carbamate was obtained.
N- {2-chloro-5- [3- (3,5-dichloro-4-fluorophenyl) -4,4,4-trifluoro-3-hydroxybutanoyl] phenyl} carbamate tert-butyl

¹ H-NMR (CDCl ₃ ) δ: 8.81 (1H, s), 7.60 (2H, d, J = 6.2 Hz), 7.53 (1H, dd, J = 8.5, 2. 1 Hz), 7.47-7.38 (1 H, m), 7.15 (1 H, s), 5.75 (1 H, s), 3.95 (1 H, d, J = 17.6 Hz), 3 .68 (1H, d, J = 17.6 Hz), 1.56 (9H, s)
Reference production example 5
29.6 g of 1,3-dichloro-2-fluoro-5-iodobenzene produced in Reference Production Example 6 was dissolved in 55 mL of degassed tetrahydrofuran, and 60 mL of isopropylmagnesium chloride was added dropwise over 20 minutes under ice cooling. After stirring at the same temperature for 1 hour, 15.8 mL of ethyl trifluoroacetate was added dropwise over 20 minutes. After stirring at the same temperature for 1.5 hours, 1N hydrochloric acid was added to the reaction mixture, and the mixture was extracted with THF and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was distilled under reduced pressure to obtain 15.5 g of 3 ′, 5′-dichloro-4′-fluoro-2,2,2-trifluoroacetophenone.
3 ′, 5′-dichloro-4′-fluoro-2,2,2-trifluoroacetophenone

¹ H-NMR (CDCl ₃ ) δ: 8.05 (2H, dd, J = 6.1, 0.8 Hz).
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. The obtained residue was dissolved in tert-butyl methyl ether, liquid-separated with an aqueous sodium thiosulfate solution, and sodium bicarbonate water was added to the organic layer, followed by liquid separation. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 29.7 g of 1,3-dichloro-2-fluoro-5-iodobenzene.
1,3-dichloro-2-fluoro-5-iodobenzene

¹ H-NMR (CDCl ₃ ) δ: 7.64 (2H, dd, J = 6.2, 0.7 Hz).
Reference production example 7
To 50.0 g of 5-acetyl-2-chloroaniline, 4.75 g of tetrabutylammonium bromide and 96.5 g of di-tert-butyl dicarbonate were added and heated to 90 degrees. After stirring at the same temperature for 5.5 hours, the reaction mixture was concentrated under reduced pressure. To the obtained residue, 100 mL of methanol and 61.0 g of potassium carbonate were added, and the mixture was stirred at room temperature for 1 hour. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was recrystallized to obtain 54.9 g of tert-butyl N- (5-acetyl-2-chlorophenyl) carbamate.
Tert-Butyl N- (5-acetyl-2-chlorophenyl) carbamate

¹ H-NMR (CDCl ₃ ) δ: 8.79 (1H, d, J = 1.8 Hz), 7.58 (1H, dd, J = 8.5, 2.1 Hz), 7.43 (1H, d, J = 8.5 Hz), 7.12-7.02 (1H, br), 2.62 (3H, s), 1.56 (9H, s).
Reference production example 8
Replaced with tert-butyl {2-chloro-5- [5- (3,5-dichloro-4-fluorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} carbamate Tert-butyl N- {2-chloro-5- [5- (3,4,5-trichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} carbamate In the same manner as in Reference Production Example 1, N- {2-chloro-5- [5- (3,4,5-trichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazole- Obtained tert-butyl 3-yl] phenyl} carbazate.
N- {2-chloro-5- [5- (3,4,5-trichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} carbazate tert-butyl

¹ H-NMR (CDCl ₃ ) δ: 7.63-4.47 (5H, m), 4.54 (2H, s), 4.08 (1H, d, J = 17.6 Hz), 3.68 (1H, d, J = 17.6 Hz), 1.40 (9H, s).
Reference production example 9
N- {2-chloro-5- [3- (3,5-dichloro-4-fluorophenyl) -4,4,4-trifluoro-2-butenoyl] phenyl} carbamate instead of tert-butyl N- Using tert-butyl {2-chloro-5- [3- (3,4,5-trichlorophenyl) -4,4,4-trifluoro-2-butenoyl] phenyl} carbamate, In a similar manner, N- {2-chloro-5- [5- (3,4,5-trichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} carbamic acid Tert-butyl was obtained.
N- {2-chloro-5- [5- (3,4,5-trichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} carbamate tert-butyl

¹ H-NMR (CDCl ₃ ) δ: 8.39 (1H, d, J = 2.0 Hz), 7.65 (2H, s), 7.47 (1H, dd, J = 8.6, 2. 0 Hz), 7.39 (1 H, d, J = 8.6 Hz), 7.10 (1 H br s), 4.12 (1 H, d, J = 17.6 Hz), 3.70 (1 H, d, J = 17.6 Hz), 1.55 (9H, s).
Reference production example 10
Instead of tert-butyl N- {2-chloro-5- [3- (3,5-dichloro-4-fluorophenyl) -4,4,4-trifluoro-3-hydroxybutanoyl] phenyl} carbamate Using tert-butyl N- {2-chloro-5- [3- (3,4,5-trichlorophenyl) -4,4,4-trifluoro-3-hydroxybutanoyl] phenyl} carbamate for reference In the same manner as in Production Example 3, N- {2-chloro-5- [3- (3,4,5-trichlorophenyl) -4,4,4-trifluoro-2-butenoyl] phenyl} carbamic acid tert -Butyl was obtained.
N- {2-chloro-5- [3- (3,4,5-trichlorophenyl) -4,4,4-trifluoro-2-butenoyl] phenyl} carbamate tert-butyl

_{^{1 H-NMR (CDCl 3)}} δ: 8.69 (1H, s), 7.44-7.33 (5H, m), 7.05 (1H, s), 1.56 (9H, s).
Reference production example 11
Reference was made by using 3 ′, 4 ′, 5′-trichloro-2,2,2-trifluoroacetophenone instead of 3 ′, 5′-dichloro-4′-fluoro-2,2,2-trifluoroacetophenone. In the same manner as in Production Example 4, N- {2-chloro-5- [3- (3,4,5-trichloro-4-fluorophenyl) -4,4,4-trifluoro-3-hydroxybutanoyl Tert-butyl phenyl} carbamate was obtained.
N- {2-chloro-5- [3- (3,4,5-trichloro-4-fluorophenyl) -4,4,4-trifluoro-3-hydroxybutanoyl] phenyl} carbamate tert-butyl

¹ H-NMR (CDCl ₃ ) δ: 7.79 (1H, dd, J = 8.4, 2.0 Hz), 7.66 (1H, d, J = 2.0 Hz), 7.59 (1H, d, J = 8.4 Hz), 7.41 (1H, s), 7.31 (2H, s), 2.67 (3H, s), 1.37 (9H, s).
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. After concentration under reduced pressure, 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. N'-acetyl-N- {2-chloro-5- [5- (3,4,5-trichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl obtained } To 480 mg of a crude product of tert-butyl carbamate, 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. 200 mg of -4,5-dihydroisoxazol-3-yl] phenyl} acetylhydrazide (hereinafter referred to as comparative compound (a)) was obtained.
Comparative compound (a)

¹ H-NMR (CDCl ₃ ) δ: 7.64-7.61 (2H, m), 7.35 (1H, d, J = 8.2 Hz), 7.32 (1H, d, J = 2. 0 Hz), 7.22-7.19 (1 H, m), 6.95 (1 H, dd, J = 8.2, 2.0 Hz), 6.52-6.50 (1 H, m), 4. 04 (1H, d, J = 17.0 Hz), 3.63 (1 H, d, J = 17.2 Hz), 2.14 (3H, s).

Next, formulation examples are shown. In addition, 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.

Next, test examples show that the compounds of the present invention are effective as active ingredients of harmful arthropod control compositions. In addition, 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 treatment with the compounds (1) and (2) of the present invention showed a mortality rate of 100%.
Test example 2
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. 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 liquid, and their viability was investigated after 8 days, 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. After the test chemical solution is dried, 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. The mortality rate was calculated by the following formula.
Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the treatment with the compounds (1) and (2) of the present invention showed a mortality rate of 100%.

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.
Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the treatment with the compounds (1) and (2) of the present invention showed a mortality rate of 100%.
Test Example 5
The preparation of Compound (1) of the present invention 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: Silk Mate 2S (Nippon Agricultural Industry) sliced to a thickness of 2 mm is placed on the bottom of a 5.5 cm diameter polyethylene cup, and 1 mL of the test chemical solution (500 ppm) is irrigated. did. After the test dilution was air-dried, a filter paper having a diameter of 5.5 cm was placed on the artificial feed, and 30 first-instar larvae of Adox ophyces orana were released on the artificial feed and capped. Seven days later, the number of surviving insects was examined, and the death rate was calculated according to the following formula.
Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the death rate was 100% in the treatment with the compound (1) of the present invention.
Test Example 6
The preparation of the compound (1) of the present invention obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 500 ppm to prepare a test spray solution. On the other hand, a cucumber was planted in a polyethylene cup and allowed to grow until the first true leaf developed, and about 20 cotton aphids were infested there. One day later, the test spray solution was sprayed onto the cucumber at a rate of 20 ml / cup. Six days after spraying, the number of cotton aphids was investigated, and the control value was determined by the following formula.
Control value (%) = {1− (Cb × Tai) / (Cai × Tb)} × 100
In addition, the character in a formula represents the following meaning.
Cb: number of insects before treatment in the untreated group Cai: number of insects when observed in the untreated group Tb: number of insects before treatment of the treated group Tai: number of insects during observation of the treated group As a result, the compound of the present invention (1 ) Showed a death rate of 90% or more.

Test Example 7
An acetone solution of the present compound (1) having a predetermined concentration of 0.125% (w / v) was prepared. After 1 μl of the acetone solution was dropped on the chest abdominal surface of adult German cockroach (Blatella germanica), the test worm was transferred to a plastic cup having a diameter of about 9 cm and a height of about 4.5 cm, and left at 25 ° C. with food and water. did. Seven days later, the number of surviving insects was examined, and the death rate was calculated according to the following formula.
Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the death rate was 100% in the treatment with the compound (1) of the present invention.
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.
Death rate (%) = 100 x (number of dead ticks / number of test ticks)
Moreover, the comparative compound (a) obtained by Reference Production Example 12 as a comparative control
And the following formula

N ′-{2-chloro-5- [5- (3,5-dichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} cyclopropanecarbohydrazide (Present Compound (13) described in Japanese Unexamined Patent Publication No. 2010-090344, hereinafter referred to as Comparative Compound (b).)
And the following formula

N ′-{2-chloro-5- [5- (3,5-dichlorophenyl) -5-trifluoromethyl-4,5-dihydroisoxazol-3-yl] phenyl} -4,4,4 -Trifluorobutyrohydrazide (Present Compound (17) described in JP 2010-090344 A, hereinafter referred to as Comparative Compound (c)) was similarly tested.
The results are shown in [Table 1].

The compound of the present invention is useful as an active ingredient of a harmful arthropod control agent.

Claims (5)

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 claim 1, wherein R ² is a cyclopropyl group.
3. The compound according to claim 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 claims 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 claims 1 to 3 to harmful arthropods or habitats of harmful arthropods.