JP2017052702A - Pest control composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition showing excellent pest controlling effect.SOLUTION: The present invention provides a pest control composition comprising a condensed heterocyclic compound represented by formula (1), and one solvent selected from group (A) [Ris H, a C1-C3 alkyl group substituted/unsubstituted with a halogen atom or the like; n is 0-2], the group (A): methanol, ethanol, isopropyl alcohol, butanol, hexanol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, neothiozole, ethyl acetate, myristic acid isopropyl, adipic acid diisopropyl, acetophenone, N-methylpyrrolidone and N-octylpyrrolidone.SELECTED DRAWING: None

Description

  The present invention relates to a pest control composition and a control method.

  DESCRIPTION OF RELATED ART Conventionally, the insecticide which processed the insecticidal active compound is known (for example, refer nonpatent literature 1). However, since it may not always show a sufficient control effect, it has been desired to develop a composition having an excellent control effect against pests.

Insects 2014, 5, 832-848; doi: 10.3390 / insects5040832

  An object of the present invention is to provide a pest control composition having excellent efficacy.

  As a result of intensive studies, the present inventors have found that a composition containing a condensed heterocyclic compound represented by the following formula (1) and a specific solvent has an excellent control effect against pests. It came to.

That is, the present invention is as follows.
[1] Formula (1)

［式中、
Ｒ^１は、水素原子、１個以上のハロゲン原子を有していてもよいＣ１−Ｃ３アルキル基、ハロゲン原子、Ｃ１−Ｃ３アルコキシ基、Ｃ２−Ｃ４アルコキシカルボニル基、Ｓ（Ｏ）_ｍＲ^２、ＮＲ^３Ｒ^４、ニトロ基又はシアノ基を表し、
Ｒ^２は、Ｃ１−Ｃ３アルキル基を表し、
Ｒ^３およびＲ^４は同一または相異なり、水素原子又はＣ１−Ｃ３アルキル基を表し、
ｎは０，１又は２を表し、
ｍは０，１又は２を表す。］
で示される縮合複素環化合物と、下記群（Ａ）から選ばれる１種の溶媒とを含む有害生物防除組成物。
群（Ａ）：メタノール、エタノール、イソプロピルアルコール、ブタノール、ヘキサノール、エチレングリコール、プロピレングリコール、プロピレングリコールモノメチルエーテル、ノルマルパラフィン、酢酸エチル、ミリスチン酸イソプロピル、アジピン酸ジイソプロピル、アセトフェノン、N-メチルピロリドン及びN-オクチルピロリドンからなる群。
［２］ 式（１）で示される縮合複素環化合物において、
Ｒ^１が、水素原子、塩素原子、臭素原子、メチル基、トリフルオロメチル基、メトキシ基、メチルスルファニル基、メチルスルフィニル基、又はメチルスルホニル基であり、
ｎ＝２である、［１］に記載の有害生物防除組成物。
［３］ ［１］または［２］に記載の有害生物防除組成物を、有害生物または有害生物の生息場所に施用する、有害生物の防除方法。

[Where:
R ¹ is a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C3 alkoxy group, a C2-C4 alkoxycarbonyl group, S (O) _m R ² , NR ³ R ⁴ represents a nitro group or a cyano group,
R ² represents a C1-C3 alkyl group,
R ³ and R ⁴ are the same or different and each represents a hydrogen atom or a C1-C3 alkyl group,
n represents 0, 1 or 2,
m represents 0, 1 or 2. ]
A pest control composition comprising the condensed heterocyclic compound represented by the formula (1) and one solvent selected from the following group (A).
Group (A): methanol, ethanol, isopropyl alcohol, butanol, hexanol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, normal paraffin, ethyl acetate, isopropyl myristate, diisopropyl adipate, acetophenone, N-methylpyrrolidone and N- A group consisting of octylpyrrolidone.
[2] In the condensed heterocyclic compound represented by the formula (1),
R ¹ is a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, a trifluoromethyl group, a methoxy group, a methylsulfanyl group, a methylsulfinyl group, or a methylsulfonyl group;
The pest control composition according to [1], wherein n = 2.
[3] A method for controlling pests, which comprises applying the pest control composition according to [1] or [2] to a pest or a habitat of the pest.

  According to the present invention, pests can be controlled.

It is the figure which showed the positional relationship of the nesting place in a container, solid feed, water, and a paper impregnating agent in the insecticidal test by accidental contact with a paper impregnating agent (Test Example 3).

  The composition of the present invention contains a condensed heterocyclic compound represented by the formula (1) (hereinafter referred to as the present compound).

［式中、
Ｒ^１は、水素原子、１個以上のハロゲン原子を有していてもよいＣ１−Ｃ３アルキル基、ハロゲン原子、Ｃ１−Ｃ３アルコキシ基、Ｃ２−Ｃ４アルコキシカルボニル基、Ｓ（Ｏ）_ｍＲ^２、ＮＲ^３Ｒ^４、ニトロ基又はシアノ基を表し、
Ｒ^２は、Ｃ１−Ｃ３アルキル基を表し、
Ｒ^３およびＲ^４は同一または相異なり、水素原子又はＣ１−Ｃ３アルキル基を表し、
ｎは０，１又は２を表し、
ｍは０，１又は２を表す。］

[Where:
R ¹ is a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C3 alkoxy group, a C2-C4 alkoxycarbonyl group, S (O) _m R ² , NR ³ R ⁴ represents a nitro group or a cyano group,
R ² represents a C1-C3 alkyl group,
R ³ and R ⁴ are the same or different and each represents a hydrogen atom or a C1-C3 alkyl group,
n represents 0, 1 or 2,
m represents 0, 1 or 2. ]

  In the formula (1), “halogen atom” means a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the present compound, examples of the “C1-C3 alkyl group” include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
In the present compound, the “C1-C3 alkyl group optionally having one or more halogen atoms” means C1-C3 in which at least one hydrogen atom of the C1-C3 alkyl group may be substituted with a halogen atom. Represents an alkyl group, for example, fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, trifluoromethyl group, trichloromethyl group, 2-fluoroethyl group, 2,2,2-trifluoroethyl group, Examples include a pentafluoroethyl group and a heptafluoroisopropyl group.

  In the present compound, examples of the “C1-C3 alkoxy group” include a methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group.

  In the present compound, “C2-C4 alkoxycarbonyl group” represents a group in which a C1-C3 alkoxy group and a carbonyl group are bonded, and represents a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, or an isopropoxycarbonyl group.

In this compound, “S (O) _m R ² ” represents a C1-C3 alkylsulfanyl group in which m is 0, an alkylsulfinyl group in which m is 1, and an alkylsulfonyl group in which m is 2.
The C1-C3 alkylsulfanyl group represents a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, and an isopropylsulfanyl group.
The C1-C3 alkylsulfinyl group represents a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, and an isopropylsulfinyl group.
The C1-C3 alkylsulfonyl group represents a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, and an isopropylsulfonyl group.

In the compound (1), R ¹ is a hydrogen atom, a chlorine atom, a bromine atom, a trifluoromethyl group, a methoxy group, a methylsulfanyl group, a methylsulfinyl group, or a methylsulfonyl group, and n = 2 A certain compound is preferable, and a compound in which R ¹ is a hydrogen atom and n = 2 is more preferable.

  Next, the manufacturing method of this compound is demonstrated.

  This compound and its production intermediate compound can be produced, for example, by the following method.

Manufacturing method 1
In the formula (1), the compound (1b) where n = 1 and the compound (1c) where n = 2 are obtained by reacting the compound (1a) where n = 0 in the formula (1) with an oxidizing agent. Can be manufactured.

［式中、記号は式（１）と同じ意味を表す。］

[Wherein the symbols have the same meaning as in formula (1). ]

First, a method for producing compound (1b) from compound (1a) will be described.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include sodium periodate, m-chloroperbenzoic acid, and hydrogen peroxide.
When hydrogen peroxide water is used as the oxidizing agent, it can be carried out in the presence of a base or a catalyst as necessary.
Examples of the base used for the reaction include sodium carbonate.
Examples of the catalyst used for the reaction include tungstic acid and sodium tungstate.
In the reaction, the oxidizing agent is usually used in a proportion of 1 to 1.2 mol with respect to 1 mol of the compound (1a).
When a hydrogen peroxide solution is used for the reaction and a base is used, the hydrogen peroxide solution is usually in a proportion of 1 to 1.2 mol and the base is usually 0.01 to 1 with respect to 1 mol of the compound (1a). Used in molar proportions.
When a hydrogen peroxide solution is used in the reaction and a catalyst is used, the hydrogen peroxide solution is usually in a proportion of 1 to 1.2 mol and the catalyst is usually 0.01 to 0 per 1 mol of the compound (1a). Used in a proportion of 5 moles.
The reaction temperature of the reaction is usually in the range of -20 to 80 ° C. The reaction time is usually in the range of 0.1 to 12 hours.
After completion of the reaction, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite and sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary. Compound (1b) can be isolated by drying and concentrating the washed organic layer. The isolated compound (1b) can be further purified by chromatography, recrystallization and the like.

Next, a method for producing the compound (1c) from the compound (1b) will be described.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include m-chloroperbenzoic acid or hydrogen peroxide water.
The reaction can be carried out in the presence of a base or a catalyst as necessary.
Examples of the base used for the reaction include sodium carbonate.
Examples of the catalyst used in the reaction include sodium tungstate.
In the reaction, with respect to 1 mol of the compound (1b), the oxidizing agent is usually used at a ratio of 1 to 4 mol. Preferably, the oxidizing agent is used in a proportion of 1 to 2 moles relative to 1 mole of the compound (1b).
When hydrogen peroxide water is used in the reaction and a base is used, the hydrogen peroxide water is usually in a proportion of 1 to 4 mol and the base is usually 0.01 to 1 mol with respect to 1 mol of the compound (1b). Used in proportions.
When a hydrogen peroxide solution is used in the reaction and a catalyst is used, the hydrogen peroxide solution is usually in a proportion of 1 to 4 mol and the catalyst is usually 0.01 to 0.5 mol per 1 mol of the compound (1b). Used in molar proportions.
The reaction temperature of the reaction is usually in the range of -20 to 120 ° C. The reaction time is usually in the range of 0.1 to 12 hours.
After completion of the reaction, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite and sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary. Compound (1c) can be isolated by drying and concentrating the organic layer. Compound (1c) can be further purified by chromatography, recrystallization and the like.

Compound (1c) can be produced in a one-step reaction (one pot) by reacting compound (1a) with an oxidizing agent.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include m-chloroperbenzoic acid or hydrogen peroxide water.
When hydrogen peroxide is used as the oxidizing agent for the reaction, it is carried out in the presence of a base or a catalyst as necessary.
Examples of the base used for the reaction include sodium carbonate.
Examples of the catalyst used for the reaction include tungstic acid and sodium tungstate.
In the reaction, an oxidizing agent is usually used in a ratio of 2 to 5 mol with respect to 1 mol of the compound (1a).
When a hydrogen peroxide solution is used for the reaction and a base is used, the hydrogen peroxide solution is usually in a proportion of 2 to 5 mol and the base is usually 0.01 to 1 mol with respect to 1 mol of the compound (1a). Used in proportions.
When a hydrogen peroxide solution is used in the reaction and a catalyst is used, the hydrogen peroxide solution is usually in a ratio of 2 to 5 mol and the catalyst is usually 0.01 to 0.5 mol per 1 mol of the compound (1a). Used in molar proportions.
The reaction temperature of the reaction is usually in the range of 0 to 120 ° C. The reaction time is usually in the range of 0.1 to 12 hours.
After completion of the reaction, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite and sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary. By drying and concentrating this organic layer, compound (1c) can be isolated. The isolated compound (1c) can be further purified by chromatography, recrystallization and the like.

Manufacturing method 2
This compound comprises reacting a compound represented by the formula (M1) (hereinafter referred to as the compound (M1)) with a compound represented by the formula (M2) (hereinafter referred to as the compound (M2)). Can be manufactured.

［式中、Ｘはハロゲン原子を表し、その他の記号は式（１）と同じ意味を表す。］
化合物（Ｍ２）は公知であるか、公知の方法に準じて製造することができる。
化合物（１ａ）は、化合物（Ｍ１）においてｎ＝０である化合物（Ｍ１ａ）と化合物（Ｍ２）とを反応させることにより製造することができる。
化合物（１ｂ）は、化合物（Ｍ１）においてｎ＝１である化合物（Ｍ１ｂ）と化合物（Ｍ２）とを反応させることにより製造することができる。
化合物（１ｃ）は、化合物（Ｍ１）においてｎ＝２である化合物（Ｍ１ｃ）と化合物（Ｍ２）とを反応させることにより製造することができる。
該反応は、通常溶媒の存在下で行われる。
反応に用いられる溶媒としては、例えば１，４−ジオキサン、ジエチルエーテル、テトラヒドロフラン、ｔｅｒｔ−ブチルメチルエーテル等のエーテル類、ジクロロメタン、クロロホルム、四塩化炭素、１，２−ジクロロエタン、クロロベンゼン等のハロゲン化炭化水素類、トルエン、ベンゼン、キシレン等の芳香族炭化水素類、酢酸エチル、酢酸ブチル等のエステル類、アセトニトリル等のニトリル類、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルピロリドン、１，３−ジメチル−２−イミダゾリジノン、ジメチルスルホキシド等の非プロトン性極性溶媒、ピリジン、キノリン等の含窒素芳香族化合物類及びこれらの混合物が挙げられる。
反応に用いられる塩基としては、例えば水素化ナトリウム、水素化カリウム等のアルカリ金属の水素化物類、水素化カルシウム等のアルカリ土類金属の水素化物類、炭酸ナトリウム、炭酸カリウム等のアルカリ金属の炭酸塩類、又はトリエチルアミン、ジイソピロピルエチルアミン、ピリジン、４−ジメチルアミノピリジン等の有機塩基が挙げられる。
該反応には、化合物（Ｍ１）１モルに対して、化合物（Ｍ２）が通常１〜２モルの割合、塩基が通常１〜５モルの割合で用いられる。
該反応の反応温度は、通常、０〜１２０℃の範囲である。該反応の反応時間は、通常、０．１〜２４時間の範囲である。
反応終了後は、反応混合物を水に注加してから有機溶媒抽出し、有機層を濃縮する；反応混合物を水に注加して生じた固体を濾過により集める；又は、反応混合物中に生成した固体を濾過により集めることにより化合物を単離することができる。単離された化合物は、再結晶、クロマトグラフィー等により更に精製することもできる。

[Wherein, X represents a halogen atom, and other symbols have the same meaning as in formula (1). ]
Compound (M2) is known or can be produced according to a known method.
Compound (1a) can be produced by reacting compound (M1a) where n = 0 in compound (M1) with compound (M2).
Compound (1b) can be produced by reacting compound (M1b) where n = 1 in compound (M1) with compound (M2).
Compound (1c) can be produced by reacting compound (M1c) where n = 2 in compound (M1) with compound (M2).
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene. Hydrogen, aromatic hydrocarbons such as toluene, benzene and xylene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl- Examples include aprotic polar solvents such as 2-imidazolidinone and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
Examples of the base used in the reaction include alkali metal hydrides such as sodium hydride and potassium hydride, alkaline earth metal hydrides such as calcium hydride, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Examples thereof include salts, or organic bases such as triethylamine, diisopropylpyroethylamine, pyridine, 4-dimethylaminopyridine and the like.
In the reaction, with respect to 1 mol of the compound (M1), the compound (M2) is usually used at a ratio of 1 to 2 mol, and the base is usually used at a ratio of 1 to 5 mol.
The reaction temperature of the reaction is usually in the range of 0 to 120 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the reaction mixture is poured into water and extracted with an organic solvent and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture. The compound can be isolated by collecting the resulting solid by filtration. The isolated compound can be further purified by recrystallization, chromatography or the like.

Production method 3
The compound (M1b) in which n = 1 in the compound (M1) and the compound (M1c) in which n = 2 in the compound (M1) are combined with the compound (M1a) in which n = 0 in the compound (M1), an oxidizing agent, Can be made to react.

［式中、Ｘはハロゲン原子を表す。］
該反応は、製造法１における、化合物（１ａ）、化合物（１ｂ）および化合物（１ｃ）を、それぞれ化合物（Ｍ１ａ）、化合物（Ｍ１ｂ）、および化合物（Ｍ１ｃ）に代えることにより、製造法１に記載の反応に準じて行うことができる。

[Wherein X represents a halogen atom. ]
The reaction is carried out in Production Method 1 by replacing Compound (1a), Compound (1b) and Compound (1c) in Production Method 1 with Compound (M1a), Compound (M1b) and Compound (M1c), respectively. It can be carried out according to the reactions described.

Manufacturing method 4
Compound (M1a) in which n = 0 in compound (M1) can be produced, for example, according to the following scheme.

［式中、Ｘはハロゲン原子を表す。］

[Wherein X represents a halogen atom. ]

A compound represented by formula (M7) (hereinafter referred to as compound (M7)) is obtained by reacting a compound represented by formula (M6) (hereinafter referred to as compound (M6)) with a chlorinating agent. Can be manufactured.
Examples of the compound (M6) include 3,6-difluoropyridine-2-carboxylic acid and 3,6-dichloropyridine-2-carboxylic acid, both of which are commercially available compounds.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aromatic hydrocarbons such as toluene and xylene, aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, and mixtures thereof.
Examples of the chlorinating agent used in the reaction include thionyl chloride, oxalyl dichloride, phosphorus oxychloride and the like.
In the reaction, a chlorinating agent is usually used at a ratio of 1 to 15 mol with respect to 1 mol of the compound (M6).
The reaction temperature of the reaction is usually in the range of 0 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M7) can be isolated by removing the solvent.

A compound represented by formula (M9) (hereinafter referred to as compound (M9)) is obtained by reacting compound (M7) with a compound represented by formula (M8) (hereinafter referred to as compound (M8)). Can be manufactured.
N2-methyl-5- (trifluoromethyl) pyridine-2,3-diamine represented by the compound (M8) can be produced by the method described in WO 2010/125985.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Aprotic polarities such as aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide Examples include solvents and mixtures thereof.
In the reaction, a base may be added as necessary.
The base used in the reaction includes alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and N, N-diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine. And the like.
In the reaction, with respect to 1 mol of the compound (M8), the compound (M7) is usually used in a proportion of 1 to 3 mol, and the base is usually used in a proportion of 1 to 10 mol.
The reaction temperature of the reaction is usually in the range of -20 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M9) can be isolated by performing post-treatment operations such as pouring water into the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M9) can be further purified by chromatography, recrystallization and the like.

Compound (M9) can also be produced by reacting compound (M6) and compound (M8) in the presence of a condensing agent.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Hydrocarbons, aromatic hydrocarbons such as toluene, benzene, xylene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl Examples thereof include aprotic polar solvents such as -2-imidazolidinone and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
Examples of the condensing agent used in the reaction include carbodiimides such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 1,3-dicyclohexylcarbodiimide.
In the reaction, a catalyst may be added as necessary.
Examples of the catalyst used in the reaction include 1-hydroxybenzotriazole.
In the reaction, with respect to 1 mol of the compound (M8), the compound (M6) is usually in a proportion of 1 to 2 mol, the condensing agent is usually in a proportion of 1 to 5 mol, and the catalyst is usually in a proportion of 0.01 to 1 mol. Used in
The reaction temperature of the reaction is usually in the range of 0 to 120 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the reaction mixture is poured into water and extracted with an organic solvent and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture. The collected solid can be collected by filtration to isolate compound (M9). The isolated compound (M9) can be further purified by recrystallization, chromatography or the like.

The compound represented by the formula (M10) (hereinafter referred to as the compound (M10)) can be produced by intramolecular condensation of the compound (M9).
The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene. Hydrogen, aromatic hydrocarbons such as toluene, benzene and xylene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl- Examples include aprotic polar solvents such as 2-imidazolidinone and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
In the reaction, a condensing agent, an acid, a base, or a chlorinating agent may be added as necessary.
Examples of the condensing agent used in the reaction include acetic anhydride, trifluoroacetic anhydride, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, triphenylphosphine and base, and carbon tetrachloride or carbon tetrabromide. And mixtures of triphenylphosphine and azodiesters (eg diethyl azodicarboxylate).
Examples of the acid used for the reaction include sulfonic acids such as paratoluenesulfonic acid, carboxylic acids such as acetic acid, and polyphosphoric acid.
Examples of the base used in the reaction include pyridine, picoline, 2,6-lutidine, 1,8-diazabicyclo [5.4.0] -7-undecene (hereinafter referred to as DBU), 1,5-diazabicyclo [ 4.3.0] -5-nonene-containing heterocyclic compounds, triethylamine, tertiary amines such as N, N-diisopropylethylamine, inorganic bases such as tripotassium phosphate, potassium carbonate, sodium hydride Can be mentioned.
Examples of the chlorinating agent used in the reaction include phosphorus oxychloride.
In the reaction, with respect to 1 mol of the compound (M9), when a condensing agent is used, the proportion of the condensing agent is usually 1 to 5 mol, and when an acid is used, the acid is usually 0.1 mol to 5 mol. If a base is used, the base is usually used in a proportion of 1 mol to 5 mol, and if a chlorinating agent is used, the chlorinating agent is usually used in a proportion of 1 mol to 5 mol.
The reaction temperature of the reaction is usually in the range of 0 to 200 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the reaction mixture is poured into water and extracted with an organic solvent and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture. The collected solid can be collected by filtration to isolate compound (M10). The isolated compound (M10) can be further purified by recrystallization, chromatography or the like.

The compound represented by the formula (M1a) (hereinafter referred to as the compound (M1a)) can be produced by reacting the compound (M10) with ethyl mercaptan in the presence of a base.
The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, N, Examples include aprotic polar solvents such as N-dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide, water, and mixtures thereof.
Examples of the base used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrides such as sodium hydride.
In the reaction, with respect to 1 mol of the compound (M10), ethyl mercaptan is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 10 mol. Preferably, ethyl mercaptan is used in a proportion of 1.0 to 1.1 mol and a base is used in a proportion of 1 to 2 mol with respect to 1 mol of compound (M10).
The reaction temperature of the reaction is usually in the range of -20 ° C to 150 ° C. The reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (M1a) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M1a) can be further purified by chromatography, recrystallization and the like.

The composition of the present invention is one solvent selected from the group (A) (hereinafter referred to as this solvent). The group (A) is methanol, ethanol, isopropyl alcohol, butanol, hexanol, ethylene glycol, propylene glycol, propylene. It consists of glycol monomethyl ether, normal paraffin, ethyl acetate, isopropyl myristate, diisopropyl adipate, acetophenone, N-methylpyrrolidone and N-octylpyrrolidone.
As this solvent, any commercially available product or any one produced by a known method can be used.

The composition of the present invention can be obtained by mixing the present compound and the present solvent.
The composition of the present invention includes both the state in which the present compound is completely dissolved in the present solvent and the state in which it is not dissolved but dispersed.

  Content of this compound in this invention composition is 0.001 to 60%, Preferably it is 0.01 to 40%.

  The content of the present solvent in the composition of the present invention is 40 to 99.999%, preferably 60 to 99.99%.

  Examples of pests for which the composition of the present invention is effective include harmful arthropods such as harmful insects and harmful mites. Specific examples of such pests include the following.

  Hemiptera: stink bugs such as Halyomorpha mista, bed bugs such as bed bugs (Cimex electrarius), and whales

  Lepidoptera: Japanese medusa such as Plodia interpuntella, Hirosukoga such as iga (Tinea translucens), tiger bisselliella, etc.

  Diptera: Culex pipiens parallels, Culex tritaenorhyinchus, Culex quasias, etc. Anoferes, chironomids, houseflies (Musca domestica), house flies (Muscina stabulans), etc. , Fleas such as Megaselia spiracularis, butterflies such as Clogmia albuncutta, fly flies such as black fly flies, fly flies, flies such as Tabanus trigonus

Coleoptera: adzuki bean weevil (Callosobruchuys chienensis) weevils such as, Tenebrionidae such as red flour beetle (Tribolium castaneum), varied carpet beetle (Anthrenus verbasci), Hara Giro carpet beetle (Dermestes maculates) beetle such as, cigarette beetle (Lasioderma serricorne) And other bark beetles, such as Lyctus brunneus.

  Lepidoptera: Cat fleas (Ctenocephales felis), Dog fleas (Ctenocephalides canis), Human fleas (Pulex irritans), Keops mud mines (Xenopsylla cheopeis) and the like.

  Anoplura: body louse (Pediculus humanus corporis), head lice (Pediculus humanus humanus), crab louse (Phthirus pubis), Ushijirami (Haematopinus eurysternus), Hitsujijirami (Dalmalinia ovis), Butajirami (Haematopinus suis), Inujirami (Linognathus setosus) and the like.

  Hymenoptera: Monomorium phalaosis, Formica fusca japonica, Ochellelus gper, pristolmem pung. Ants such as Argentine ants (Linepithema humile) and wasps.

  Cockroaches: German cockroaches (Blatella germanica), Black cockroaches (Periplaneta furiginosa), American cockroaches (Periplaneta americana), Japanese cockroaches (Peripraneta brunea), British cockroaches (Briellata brent)

  Isoptera: Yamato termite (Reticulitermes speratus), Formosan subterranean termite (Coptotermes formosanus), the United States drywood termites (Incisitermes minor), Daikoku termites (Cryptotermes domesticus), Taiwan termites (Odontotermes formosanus), Kou Shun termite (Neotermes koshunensis), Satsuma termites (Glyptotermes satsumensis), termites termites (Glyptotermes nakajimai), termites termites (Glyptotermes fuscus), termites termites (Glyptotermes kodamai), swords Li (Glyptotermes kushimensis), giant termite (Hodotermopsis japonica), Kou Shu Ye termite (Coptotermes guangzhoensis), Amami termites (Reticulitermes amamianus), Miyatake termites (Reticulitermes miyatakei), Kang Mont termites (Reticulitermes kanmonensis), Takasago termite (Nasutitermes takasagoensis), Nitobe Termites (Pericapritermes nitobei), Musca termites (Sinocapriteres mushae) and the like.

Longicornis (Haemaphysalis longicornis), Yamatochimadani (Haemaphysalis flava), Taiwan Kaku ticks (Dermacentor taiwanicus), American dog Kaku ticks (Dermacentor variabilis), Ixodes ovatus (Ixodes ovatus), Schulz ticks (Ixodes persulcatus), black leg-de-tick (Ixodes scapularis) , Ticks such as Amblyomma americanum, Boophilus microplus, Rhipicephalus sanguineus, Typhophagus utrescentiae) grain mites such as, farinae (Dermatophagoides farinae), house dust mite such as pteronyssinus (Dermatophagoides ptrenyssnus), Hosotsumedani (Cheyletus eruditus), Stag Tsumedani (Cheyletus malaccensis), Minami Tsumedani (Cheyletus moorei), Inutsumedani (Cheyletiella yasguri) such as Ticks, mites, mites, mites, mites, mites, mites, mites, mites, orniformes (Orn) cucumbers such as itonynissus bacoti, ornithonysus sylvairum, vaccinia (Dermanysussus gallinae), and tsutsugamu such as Leptotrombidium akamusi.
Spider: Spiders such as Chiracanthium japonicum and Latrodictus hasseltii

The pest control method of the present invention can be controlled by applying the composition of the present invention directly to pests by spraying, spraying, dipping, application, or by applying it to the habitat of pests. This is a method for controlling a target pest (hereinafter referred to as the present control method). The composition of the present invention is diluted, or the composition of the present invention is mixed with an inert carrier such as a solid carrier, a liquid carrier, or a gaseous carrier, and a surfactant or other adjuvant for formulation is added as necessary. Then, it may be applied to a pest or a pest habitat.
In this specification, the habitat of a pest means the entire living sphere in which the pest is active, for example, a place including a pest nest, a feeding area, a path, and the like.

  Examples of the preparation containing the composition of the present invention include solutions, oils, emulsions, wettable powders, flowables (suspensions in water, suspensions in oil, microcapsules, etc.), aerosols, carbon dioxide preparations, piezos. Insecticide, resin kneading agent, cellulose kneading agent, paper impregnating agent, nonwoven fabric impregnating agent, knitted fabric impregnating agent, resin impregnating agent, cellulose impregnating agent, ULV (ultra low volume, high concentration trace spraying) agent, and poison bait Is mentioned. More preferably, a liquid agent, an oil agent, a flowable agent, an aerosol agent, a resin kneading agent, a cellulose kneading agent, a paper impregnation agent, a nonwoven fabric impregnation agent, a knitted fabric impregnation agent, a resin impregnation agent, and a cellulose impregnation agent are exemplified.

Examples of the solid carrier used in the preparation containing the composition of the present invention include clays (kaolin clay, diatomaceous earth, bentonite, fubasami clay, acidic clay), synthetic hydrous silicon oxide, talc, ceramic, and other inorganic minerals (sericite). , Quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), fine powders and granules of chemical fertilizers (ammonium sulfate, phosphorous acid, ammonium nitrate, urea, ammonium chloride, etc.), resins (natural resins, polyethylene, polypropylene, Polyester resin such as polyacrylonitrile, polymethyl methacrylate, polyethylene terephthalate, nylon resin such as nylon-6, nylon-11, nylon-66, polyamide resin, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-propylene copolymer, Polyurethane), cellulose, paper, cloth (cotton, hemp, silk, etc.), Cloth, and the like.
Resin kneading agent, cellulose kneading agent, paper impregnating agent, nonwoven fabric impregnating agent, knitted fabric impregnating agent, resin impregnating agent, cellulose impregnating agent, etc., as a substrate (natural resin, polyethylene, polypropylene, polyacrylonitrile, Polyester resins such as polymethyl methacrylate, polyethylene terephthalate, nylon resins such as nylon-6, nylon-11, nylon-66, polyamide resins, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-propylene copolymer, polyurethane, etc.) Cellulose, paper, cloth (cotton, hemp, silk, etc.), non-woven fabric and the like are preferable.

  Examples of the liquid carrier include water, ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.) Halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), sulfoxides (dimethyl sulfoxide, etc.), propylene carbonate, vegetable oil, and the like.

  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, and polyethylene glycol fatty acid ester, and anions such as alkyl sulfonate, alkyl benzene sulfonate, and alkyl sulfate. Surfactant is mentioned.

  Other formulation adjuvants include stickers, dispersants, colorants, antifreezes and stabilizers, such as casein, gelatin, sugars (starch, gum arabic, cellulose derivatives, alginic acid, etc.), cereals Powder, lignin derivative, bentonite, synthetic water-soluble polymer (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids, etc.), glycerin, PAP (isopropyl acid phosphate), nordihydroguaiaretic acid, BHT (2,6-di-) by children and pets such as tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), dehydroacetic acid, pepper powder, etc. Pest-attracting perfumes such as anti-fouling agent, cheese flavor, onion flavor peanut oil And the like.

As a preferred embodiment of the method for controlling the present invention, there is a method in which the composition of the present invention or the preparation containing the composition of the present invention is pretreated on the path of pests. When the composition of the present invention comes into contact with the body surface of the pest when passing through the place, the pest can be controlled.
Pests suitable for this embodiment include dwarf arthropods such as cockroaches, ants and spiders.
Formulations suitable for this embodiment include solutions, oils, emulsions, wettable powders, flowables (suspensions in water, suspensions in oil, microcapsules, etc.), aerosols and the like.
For liquids and oils, the composition of the present invention is mixed with dimethyl sulfoxide and the emulsion is mixed with the composition of the present invention and a surfactant such as polyoxyethylene styryl phenyl ether and calcium dodecylbenzenesulfonate. Can be prepared. The wettable powder is prepared by mixing the composition of the present invention with a solid simple substance such as a synthetic hydrous silicon oxide fine powder or diatomaceous earth, and a surfactant such as sodium lauryl sulfate or calcium lignin sulfonate. be able to. The flowable agent can be prepared by dispersing the composition of the present invention in an aqueous solution containing a surfactant such as polyoxyethylene alkyl ether sulfate ammonium salt using an emulsifier or a wet pulverizer. As for the aerosol agent, the composition of the present invention is used as it is, or a mixture of the composition of the present invention and an auxiliary solvent is put into an aerosol can, an aerosol valve is mounted, a gaseous carrier is filled, and an actuator is mounted. Can be prepared.

Further, as another preferred embodiment of the control method of the present invention, preparations such as a resin kneading agent, a cellulose kneading agent, a paper impregnating agent, a nonwoven fabric impregnating agent, a knitted fabric impregnating agent, a resin impregnating agent, and a cellulose impregnating agent are used as they are. Alternatively, it may be stored in a station where pests can enter (hereinafter referred to as the present extermination tool) and placed in a pest habitat, for example, in the vicinity of a pest nest or in a path. Specific examples of this extermination tool are structures having a structure resembling pest nests, feeding grounds, etc. For example, the structures disclosed in JP 2001-61395, JP 2004-313076, etc. are used. be able to.
Pests suitable for this embodiment include dwarf arthropods such as cockroaches, ants and spiders.
The resin kneading agent and the cellulose kneading agent go through a step of kneading the composition of the present invention or a preparation (solution, oil, etc.) containing the composition of the present invention on a substrate such as resin or cellulose using a normal kneading apparatus. It can be produced by molding by injection molding, extrusion molding, press molding or the like. Paper impregnating agent, non-woven fabric impregnating agent, knitted fabric impregnating agent, resin impregnating agent, cellulose impregnating agent is a composition of the present invention or a preparation containing the composition of the present invention (liquid agent, oil agent, flowable agent, etc.), paper, non-woven fabric, resin, Manufactured by processing into a plate shape, film shape, tape shape, sheet shape, net shape, string shape, etc., through a process of supporting (impregnating, applying) on a substrate such as cellulose, a step of molding or cutting, etc. be able to. In addition, these preparations may contain a target pest-inducing component.

A specific embodiment of the present extermination tool that can be used in the control method of the present invention is a structure having a doorway through which a pest can pass with a size that can be arranged in the vicinity of a pest nest or in a path, An extermination tool in which the composition of the present invention is treated on the inner surface of the structure may be mentioned. Examples of the external shape of the present removal tool include a rectangular parallelepiped, a hemisphere, a triangular pyramid, a quadrangular pyramid, a triangular prism, and the like. 0.5 to 5 cm, preferably 3 to 10 cm in length, 3 to 20 cm in width, and 0.5 to 3 cm in height. The size and number of doorways vary depending on the target pest, but if the target pest is a cockroach and the external shape of the extermination tool is a rectangular parallelepiped, the two places and one side in the longitudinal direction of the extermination tool are completely Or it is more preferable to set it as the shape opened partially. Although the material of this extermination tool is not specifically limited, Paper and resin are preferable from a viewpoint of economical efficiency or workability.
By passing through the control tool, the pest comes into contact with the composition of the present invention. Since the composition of the present invention has excellent efficacy, one or more parts of the pest body (eg, antennae, feet, mouth, etc.) are brought into contact with the composition of the present invention for a short time to control the pest. be able to.
The composition of the present invention can be used on surfaces where pests frequently appear inside and outside buildings. The control method of the present invention is suitable for controlling pests, particularly dwarf arthropods, inside, around and outdoors in buildings. Specifically, the present invention can be applied to a place where a pest is hidden (for example, the inside of a drawer, a pipe, a crack, or the like) and a place where a path for the pest is formed (for example, one corner, an edge, a cover plate, or the like). Yet another area of use is the entrance point to the building, such as a door or window.
In the control method of the present invention, the composition of the present invention is applied preferably in a linear or spot form. In the control method of the present invention, the composition of the present invention is preferably applied only to places where children and pets do not touch. In the pest control method of the present invention, it is preferable to apply to a plurality of different places in the space to be treated, instead of applying to only one place.

Processing amount of a formulation comprising the composition of the present invention and the present invention compositions include, but may also vary by pests of interest, 5000 mg / m ² in terms of the normal present compounds, preferably 10-5000 / m ² More preferably, it is 20 to 1000 mg / m ² .

  The composition of the present invention can be used in combination with or in combination with the present compound and known insecticides and synergists in addition to isoparaffin which is liquid at 25 ° C. under atmospheric pressure. Examples of active ingredients of such insecticides and synergists are shown below.

Active ingredient of insecticide (1) Organophosphorus compound Acephate, dichlorvos (DDVP), fenitrothion (MEP)
(2) Carbamate compounds Bendiocarb, fenobucarb, phenoxycarb, propoxur (PHC)

(3) Pyrethroid compounds acrinathrin, allethrin, benfluthrin, beta-cyfluthrin, bifenthrin, cycloprotorin, fluprothrin , Cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucitrate f lucytrinate, flufenprox, flumethrin, fluvalinate, halfenprox, imiprothrin, permethrin, praretrin, praretrin resmethrin), sigma-cypermethrin, silaflufen, tefluthrin, tralomethrin, transfluthrin, tetramethrin. thrin), phenothrin, cyphenothrin, alpha-cypermethrin, zeta-cypermethrin, lambda cihalothrin (lambda-cythhalothrin) ), Furamethrin, tau-fluvalinate, methfluthrin, profluthrin, dimethylfluthrin, 2,3,5,6-tetrafluoro-4- (methoxymethyl) benzyl EZ)-(1RS, 3RS; 1RS, 3S ) -2,2-dimethyl-3-prop-1-enylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methylbenzyl (EZ)-(1RS, 3RS; 1RS, 3SR) -2 , 2-dimethyl-3-prop-1-enylcyclopropanecarboxylate, and 2,3,5,6-tetrafluoro-4- (methoxymethyl) benzyl (1RS, 3RS; 1RS, 3SR) -2,2- Dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4- (methoxymethyl) benzyl (EZ)-(1RS, 3RS; 1RS, 3SR)- 2,2-Dimethyl-3- (2-cyano-1-propenyl) cyclopropanecarboxylate.
(4) Nereistoxin compounds Cartap, bensultap, thiocyclam, monosultap, and bisultap.

(5) Neonicotinoid compounds imidacloprid (imidac1oprid), nitenpyram (nitenpyram), acetamiprid (acetamipride), thiamethoxam, thiacloprid (thiacloprid), dinoteurin (dinothurine)
(6) Benzoylurea compound Chlorfluazuron, bistrifluron, diafenthiuron, diflubenzuron, fluazuron, flucycloxuron, flucyclolone (Flufenoxuron), hexaflumuron, lufenuron, novaluron, novifluuron, teflubenzuron, triflumuron, and triflumuron.
(7) Phenylpyrazole compounds Acetoprole, ethiprole, vaniliprole, pyriprole, and pyrafluprole.
(8) Bt toxin Live spores and produced crystal toxins derived from Bacillus thuringiensis, and mixtures thereof (9) Other insecticide active ingredients chlorfenapyr, cyantraniprole, cyromazine, Hydroprene, methoprene, indoxacarb, methoxadiazone, pyriproxyfen, spinosad, chlorantraniprolol ).

Active ingredient of synergist piperonyl butoxide, N- (2-ethylhexyl) -8,9,10-trinorborn-5-ene-2,3-dicarboximide (MGK 264).

  Hereinafter, the present invention will be described in more detail with reference to formulation examples and test examples, but the present invention is not limited to these examples.

Production Example 1
(1)
To a mixture of 50 g of 3,6-dichloro-pyridine-2-carboxylic acid, 1 mL of N, N-dimethylformamide, and 130 mL of toluene, 49 mL of thionyl chloride was added at room temperature. After stirring for 5 hours while heating under reflux, the reaction mixture was allowed to cool to room temperature. The reaction mixture was concentrated under reduced pressure to obtain 3,6-dichloro-pyridine-2-carbonyl chloride.
(2)
To a mixture of 50 g of N ² -methyl-5-trifluoromethyl-pyridine-2,3-diamine (synthesized by the method described in International Publication No. 2010/125985) and 90 mL of tetrahydrofuran, A mixture of the total amount of 6-dichloro-pyridine-2-carbonyl chloride and 90 mL of tetrahydrofuran was added dropwise under ice cooling. After stirring at room temperature for 5 hours, 200 mL of hexane was added to the reaction mixture. The precipitated solid was collected by filtration, put into a saturated aqueous sodium carbonate solution, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure to give 3,6-dichloro-pyridine-2-carboxylic acid (2-methylamino-5-trifluoromethyl-pyridine-3) described below. 105 g of -yl) -amide were obtained.

¹H-NMR (CDCl₃) δ: 9.17 (1H, s), 8.38 (1H, d), 7.88 (1H, d), 7.82 (1H, d), 7.50 (1H, d), 5.06 (1H, d), 3.08 (3H, d).
（３）
３，６−ジクロロ−ピリジン−２−カルボン酸（２−メチルアミノ−５−トリフルオロメチル−ピリジン−３−イル）−アミド１０５ｇ及び酢酸３５０ｍＬの混合物を、加熱還流下４時間撹拌した。この混合物を室温まで放冷した後、水を注加した。析出した固体を濾取し、減圧下乾燥することにより、以下に記す、２−（３，６−ジクロロ−ピリジン−２−イル）−３−メチル−６−トリフルオロメチル−３Ｈ−イミダゾ［４，５−ｂ］ピリジン８４ｇを得た。

¹ H-NMR (CDCl ₃ ) δ: 9.17 (1H, s), 8.38 (1H, d), 7.88 (1H, d), 7.82 (1H, d), 7.50 (1H, d), 5.06 (1H, d ), 3.08 (3H, d).
(3)
A mixture of 105 g of 3,6-dichloro-pyridine-2-carboxylic acid (2-methylamino-5-trifluoromethyl-pyridin-3-yl) -amide and 350 mL of acetic acid was stirred with heating under reflux for 4 hours. The mixture was allowed to cool to room temperature, and water was added. The precipitated solid was collected by filtration and dried under reduced pressure to give 2- (3,6-dichloro-pyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4] , 5-b] 84 g of pyridine was obtained.

¹H-NMR (CDCl₃) δ: 8.77 (1H, s), 8.40 (1H, d), 7.92 (1H, d), 7.49 (1H, d), 4.02 (3H, s).
（４）
２−（３，６−ジクロロ−ピリジン−２−イル）−３−メチル−６−トリフルオロメチル−３Ｈ−イミダゾ［４，５−ｂ］ピリジン５４ｇ、水素化ナトリウム（油状）６．９ｇ及びテトラヒドロフラン８００ｍＬの混合物に、氷冷下エチルメルカプタン１２ｍＬを滴下した。この反応混合物を氷冷下３時間撹拌した後、水を注加した。析出した固体を、水およびヘキサンで洗浄し、得られた固体を減圧下乾燥することにより、以下に記す、２−（６−クロロ−３−エチルスルファニル−ピリジン−２−イル）−３−メチル−６−トリフルオロメチル−３Ｈ−イミダゾ［４，５−ｂ］ピリジンの粗生成物５１gを得た。

¹ H-NMR (CDCl ₃ ) δ: 8.77 (1H, s), 8.40 (1H, d), 7.92 (1H, d), 7.49 (1H, d), 4.02 (3H, s).
(4)
2- (3,6-dichloro-pyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine 54 g, sodium hydride (oil) 6.9 g and tetrahydrofuran To an 800 mL mixture, 12 mL of ethyl mercaptan was added dropwise under ice cooling. The reaction mixture was stirred for 3 hours under ice cooling, and then water was added. The precipitated solid was washed with water and hexane, and the obtained solid was dried under reduced pressure to give 2- (6-chloro-3-ethylsulfanyl-pyridin-2-yl) -3-methyl described below. 51 g of a crude product of -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine was obtained.

¹H-NMR (CDCl₃) δ: 8.74 (1H, s), 8.40 (1H, s), 7.75 (1H, d), 7.42 (1H, d), 4.11 (3H, s), 2.97 (2H, q), 1.36 (3H, t).
（５）
２−（６−クロロ−３−エチルスルファニル−ピリジン−２−イル）−３−メチル−６−トリフルオロメチル−３Ｈ−イミダゾ［４，５−ｂ］ピリジンの粗生成物５０gおよびクロロホルム４５０ｍＬの混合物に、氷冷下７５％ｍ−クロロ過安息香酸６６ｇを加えた。氷冷下５時間撹拌した後、この反応混合物を飽和重層水溶液に加え、クロロホルムで抽出した。有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥した。得られた有機層を減圧下乾燥し、得られた残渣をクロロホルムおよびヘキサンから再結晶を行い、以下に記す２−（６−クロロ−３−エタンスルホニル−ピリジン−２−イル）−３−メチル−６−トリフルオロメチル−３Ｈ−イミダゾ［４，５−ｂ］ピリジン５０ｇを得た。

¹ H-NMR (CDCl ₃ ) δ: 8.74 (1H, s), 8.40 (1H, s), 7.75 (1H, d), 7.42 (1H, d), 4.11 (3H, s), 2.97 (2H, q ), 1.36 (3H, t).
(5)
Mixture of 50 g of crude product of 2- (6-chloro-3-ethylsulfanyl-pyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine and 450 mL of chloroform To the mixture, 66 g of 75% m-chloroperbenzoic acid was added under ice cooling. After stirring for 5 hours under ice-cooling, the reaction mixture was added to a saturated aqueous multilayer solution and extracted with chloroform. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The obtained organic layer was dried under reduced pressure, and the resulting residue was recrystallized from chloroform and hexane, and 2- (6-chloro-3-ethanesulfonyl-pyridin-2-yl) -3-methyl described below. 50 g of -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine was obtained.

¹H-NMR (CDCl₃) δ: 8.78 (1H, d), 8.48 (1H, d), 8.32 (1H, d), 7.73 (1H, d), 3.93 (3H, s), 3.86 (2H, q), 1.36 (3H, t).

¹ H-NMR (CDCl ₃ ) δ: 8.78 (1H, d), 8.48 (1H, d), 8.32 (1H, d), 7.73 (1H, d), 3.93 (3H, s), 3.86 (2H, q ), 1.36 (3H, t).

(6)
To a mixture of 400 mg of 2- (6-chloro-3-ethanesulfonyl-pyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine and 3 mL of pyridine at room temperature 1H-1,2,4-triazole 101 mg was added. After heating to 90 ° C. and stirring for 10 hours, water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The obtained organic layer was dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 160 mg of the present compound 1 described below.

Production Example 2
2- (6-Chloro-3-ethanesulfonyl-pyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine 500 mg, 60% sodium hydride (oil) To a mixture of 60 mg and 2.5 mL of N, N-dimethylformamide, 141 mg of 3-chloro-1H-1,2,4-triazole was added under ice cooling. After stirring for 2.5 hours under ice-cooling, a saturated multistory aqueous solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The obtained organic layer was dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 435 mg of the present compound 2 described below.

Production Example 3
2- (6-Chloro-3-ethanesulfonyl-pyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine 300 mg, potassium carbonate 133 mg, and N, N -To a mixture of 3 mL of dimethylformamide was added 132 mg of 3-bromo-1H-1,2,4-triazole under ice cooling. After stirring for 2.5 hours under ice-cooling, a saturated multistory aqueous solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The obtained organic layer was dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 370 mg of the present compound 3 described below.

Production Example 4
2- (6-Chloro-3-ethanesulfonyl-pyridin-2-yl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine 300 mg, 60% sodium hydride (oil) To a mixture of 36 mg and N, N-dimethylformamide 1.5 mL was added 3-trifluoromethyl-1H-1,2,4-triazole (the method described in US Patent Application Publication No. 2010/0063063) under ice-cooling. 112 mg) was added. After stirring for 2.5 hours under ice-cooling, a saturated multistory aqueous solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The obtained organic layer was dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 326 mg of the present compound 4 described below.

  Table 1 shows the physical properties of the present compounds described in the above production examples.

Formulation Example 1
44 mg of the present compound 1 and 10 mL of methanol [manufactured by Nacalai Tesque] were mixed to obtain the present composition A.

Formulation Example 2
44 mg of the present compound 1 and 10 mL of ethanol [manufactured by Nacalai Tesque] were mixed to obtain the present composition B.

Formulation Example 3
44 mg of the present compound 1 and 10 mL of isopropyl alcohol [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain the present composition C.

Formulation Example 4
44 mg of the present compound 1 and 10 mL of n-butanol [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain the present composition D.

Formulation Example 5
44 mg of the present compound 1 and 10 mL of n-hexanol [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain composition E of the present invention.

Formulation Example 6
44 mg of the present compound 1 and 10 mL of ethylene glycol [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain composition F of the present invention.

Formulation Example 7
44 mg of the present compound 1 and 10 mL of propylene glycol [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain composition G of the present invention.

Formulation Example 8
44 mg of this compound 1 and 10 mL of propylene glycol monomethyl ether [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain composition H of the present invention.

Formulation Example 9
44 mg of the present compound 1 and 10 mL of normal paraffin [Neothiozole: manufactured by Sanko Chemical Co., Ltd.] were mixed to obtain Composition I of the present invention.

Formulation Example 10
44 mg of the present compound 1 and 10 mL of ethyl acetate [manufactured by Nacalai Tesque] were mixed to obtain the composition J of the present invention.

Formulation Example 11
44 mg of the present compound 1 and 10 mL of isopropyl myristate [manufactured by Nikko Chemicals] were mixed to obtain composition K of the present invention.

Formulation Example 12
44 mg of the present compound 1 and 10 mL of diisopropyl adipate [manufactured by Tokyo Chemical Industry] are mixed to obtain the present composition L.

Formulation Example 13
44 mg of the present compound 1 and 10 mL of acetophenone [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain composition M of the present invention.

Formulation Example 14
44 mg of the present compound 1 and 10 mL of N-methylpyrrolidone [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain composition N of the present invention.

Formulation Example 15
44 mg of the present compound 1 and 10 mL of N-octylpyrrolidone [manufactured by Wako Pure Chemical Industries, Ltd.] were mixed to obtain the present composition O.

Formulation Example 16
44 mg of this compound 1 and 10 mL of acetone [manufactured by Nacalai Tesque] were mixed to obtain a comparative composition A.

Formulation Example 17
Indoxacarb 44 mg and acetone [manufactured by Nacalai Tesque] 10 mL were mixed to obtain this comparative composition B.
Formulation Example 18
Comparative composition C was obtained by mixing 44 mg of indoxacarb and 10 mL of isopropyl alcohol [manufactured by Wako Pure Chemical Industries, Ltd.].

Formulation Example 19
Indoxacarb 44 mg and propylene glycol monomethyl ether [manufactured by Wako Pure Chemical Industries, Ltd.] 10 mL were mixed to obtain Comparative Composition D.

Formulation Example 20
Any 5 g of the present compounds 1 to 4 is mixed with 40 g of isopropyl alcohol and 55 g of N, N-dimethylformamide to obtain a liquid agent.

Formulation Example 21
27 mg of the present compound 1 and 7 mL of isopropyl alcohol are mixed, and 0.7 mL of the mixture is dropped onto 6 × 9 cm cardboard. The cardboard is folded in three and formed into a cylindrical shape having a triangular cross section (2 cm on a side, 9 cm in length), and the outside is covered with vinyl tape to obtain a paper impregnating agent.

  Hereinafter, the present invention will be described in more detail with reference to test examples and the like, but the present invention is not limited to these examples.

Test Example 1 Contact test on German cockroach (Blattella germanica).
[Test method]
The present invention composition described in the formulation examples, comparative composition, 1 mL of isopropyl alcohol [manufactured by Wako Pure Chemical Industries], diisopropyl adipate [manufactured by Tokyo Chemical Industry] or acetophenone [manufactured by Wako Pure Chemical Industries] on a circular filter paper having a diameter of about 10 cm. The dripping process was performed uniformly. After being placed in a room (about 25 ° C., relative humidity about 60%) for about 1 hour, the filter paper was laid on the bottom of a plastic cup having a bottom diameter of about 10 cm and a height of about 7 cm. 10 adult German cockroaches (Blatella germanica) (5 males, 5 females) were released into the cup and contacted with the filter paper for 1 minute. The German cockroaches were collected in a new cup and fed with food and water. 25 ° C. and relative humidity of about 60%). Seven days after the test, the state of German cockroaches was observed, and the control rate calculated using the following formula is shown in Table 2.

  Control rate (%) = (Number of dead and moribund insects on day 7 / number of samples) × 100

Test Example 2 Spray treatment test.
The solution described in Preparation Example 20 is diluted with water to a predetermined concentration. The treatment solution (15 × 15 cm) such as a decorative board or a veneer board is sprayed with the water diluent from a distance of 10 to 100 cm with a sprayer, and the amount of the diluent attached to the treatment board is 10 to 500 mg / m ^2. Adjust so that A ring made of a plastic plate (diameter: about 14 cm, height: about 5 cm) is placed on a processing plate stored for 24 hours under indoor conditions, and 10 cockroaches in a group (5 males, 5 females). Release. Margarine is applied on the inner surface of the ring to prevent scooping up, and the cockroach is forcibly brought into contact with the processing plate. After 1 hour of contact, German cockroaches are collected in a clean cup and fed with food and water for storage. Seven days later, the state of German cockroaches is observed, and the control rate is calculated from the proportion of dead individuals using the following formula.

Control rate (%) = (number of dead individuals + number of moribund individuals) / number of test individuals x 100

Test Example 3 Insecticidal test by accidental contact with paper impregnating agent A large metal container (bottom about 180 x 120 cm, height about 15 cm), mouse solid feed, water, and 18 cm x 32 cm balls as nesting place A corrugated sheet prepared by folding a 32 cm side of the paper every 2 cm is installed as shown in FIG. After that, only one of the cockroaches, black-eyed cockroaches, and American cockroaches is released. The number of cockroaches released was 50 (25 males, 25 females) for German cockroaches, 20 (10 males, 10 females) for black cockroaches, and 20 (10 males, 10 females) for American cockroaches. Head). After allowing the test insect to acclimatize to the test environment for one day or longer, one paper impregnating agent obtained in Formulation Example 21 is placed in the container as shown in FIG. Under these conditions, the test insects can obtain everything necessary for survival near the corrugated plate, so that most of the test period is active near the corrugated plate. Seven days after the paper impregnating agent is installed, the state of cockroaches is observed, and the control rate is calculated by the following formula.

Control rate (%) = (number of dead individuals + number of moribund individuals) / number of test individuals x 100

  The composition of the present invention has an excellent control effect against pests and is useful.

Claims (3)

Formula (1)

[Where:
R ¹ is a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C3 alkoxy group, a C2-C4 alkoxycarbonyl group, S (O) _m R ² , NR ³ R ⁴ represents a nitro group or a cyano group,
R ² represents a C1-C3 alkyl group,
R ³ and R ⁴ are the same or different and each represents a hydrogen atom or a C1-C3 alkyl group,
n represents 0, 1 or 2,
m represents 0, 1 or 2. ]
A pest control composition comprising a condensed heterocyclic compound represented by the formula (1) and one solvent selected from the following group (A).
Group (A): methanol, ethanol, isopropyl alcohol, butanol, hexanol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, neothiozole, ethyl acetate, isopropyl myristate, diisopropyl adipate, acetophenone, N-methylpyrrolidone and N-octyl A group consisting of pyrrolidone. In the condensed heterocyclic compound represented by the formula (1),
R ¹ is a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, a trifluoromethyl group, a methoxy group, a methylsulfanyl group, a methylsulfinyl group, or a methylsulfonyl group;
The pest control composition according to claim 1, wherein n = 2.   A method for controlling pests, which comprises applying the pest control composition according to claim 1 or 2 to pests or habitats of pests.

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