TW201522331A - Condensed heterocyclic compound and its use in pest control - Google Patents

Abstract

The present invention is to provide a condensed heterocyclic compound represented by the formula (1), or its N-Oxide, which is effective in pest control and removal and is suitable as an active ingredient of pest control agents. [in the formula, R1 is C1–C4 alkyl, cyclopropyl , or cyclopropyl methyl; R2 is C1–C3 alkyl, C1–C3 haloalkyl, OR-6, halogen atom, or hydrogen atom; R<3> represents the C1 – C3 alkyl group, halogen atom, or hydrogen atom; R4 is C1–C3 alkyl or –S(O)mR7; R5 is C1–C3 alkyl, C1–C3 haloalkyl, -OR8, halogen atom, or hydrogen atom, wherein n is 0,1, or 2].

Description

Fused heterocyclic compounds and their pest control applications

This invention relates to a fused heterocyclic compound and its pest control use.

Various fused heterocyclic compounds are known to exhibit activity as pharmaceuticals (for example, refer to Journal of Medicinal Chemistry, 8(3), 305 (1965)). Further, for the purpose of controlling pests, various compounds are being studied (for example, refer to WO2013/018928).

The present invention provides a method for controlling a compound having excellent control efficacy against harmful organisms and a pest using the same.

The present invention is as follows.

[1] a fused heterocyclic compound represented by the formula (1), or an N-oxide thereof (Oxide), Wherein R ¹ represents C1-C4 alkyl, cyclopropyl or cyclopropylmethyl, and R ² represents C1-C3 alkyl, C1-C3 haloalkyl, -OR ⁶ , halogen or hydrogen, R ³ represents a C1-C3 alkyl group, a halogen atom or a hydrogen atom, R ⁴ represents a C1-C3 haloalkyl group or -S(O) _m R ⁷ , and R ⁵ represents a C1-C3 alkyl group, a C1-C3 haloalkyl group, OR ⁸ , a halogen atom or a hydrogen atom, R ⁶ and R ⁸ are the same or different and each represents a C1-C3 alkyl group or a C1-C3 haloalkyl group, R ⁷ represents a C1-C3 haloalkyl group, and n represents 0, 1 or 2 , m means 0, 1 or 2].

(The fused heterocyclic compound represented by the formula (1) and its N-oxide are hereinafter referred to as the compound of the present invention).

[2] a compound represented by the formula (1-1), or an N-oxide thereof, ^Wherein R ^2a represents a C1-C3 perfluoroalkyl group, -OR ^6a , a halogen atom or a hydrogen atom, R ^3a represents a C1-C3 alkyl group, a halogen atom or a hydrogen atom, and R ^4a represents a C1-C3 perfluoroalkyl group. , or -S(O) _m R ^7a , R ^5a represents a C1-C3 alkyl group, -OR ^8a , a halogen atom or a hydrogen atom, and R ^6a or R ^8a are the same or different and each represents a C1-C3 alkyl group, and R ^7a represents C1-C3 perfluoroalkyl, n represents 0, 1 or 2, and m represents 0, 1 or 2].

[3] a compound represented by the formula (1-2), or an N-oxide thereof, ^Wherein R ^2a represents a C1-C3 perfluoroalkyl group, a halogen atom or a hydrogen atom, R ^3a represents a C1-C3 alkyl group, a halogen atom or a hydrogen atom, and R ^4a represents a C1-C3 perfluoroalkyl group or a -S ( O) _m R ^7a , R ^7a represents a C1-C3 perfluoroalkyl group, n represents 0, 1 or 2, and m represents 0, 1 or 2].

[4] a compound of the formula (1-3), or an N-oxide thereof, ^Wherein R ^2a represents a C1-C3 perfluoroalkyl group, a halogen atom or a hydrogen atom, R ^3a represents a C1-C3 alkyl group, a halogen atom or a hydrogen atom, and R ^4a represents a C1-C3 perfluoroalkyl group or a -S ( O) _m R ^7a , R ^7a represents a C1-C3 perfluoroalkyl group, n represents 0, 1 or 2, and m represents 0, 1 or 2].

[5] The compound according to any one of [1] to [4] wherein R ² or R ^2a is a hydrogen atom.

[6] The compound according to any one of [1] to [4] wherein R ² or R ^2a is a trifluoromethyl group.

[7] The compound according to any one of [1] to [4] wherein R ³ or R ^3a is a hydrogen atom.

[8] The compound according to any one of [1] to [4] wherein R ⁴ or R ^4a is a trifluoromethyl group.

[9] A pest control agent comprising the compound according to any one of [1] to [8] and an inert carrier.

[10] A method for controlling a pest, which comprises administering an effective amount of the compound according to any one of [1] to [8] to a pest or a habitat thereof.

In the present specification, specific examples of the bases indicated by the symbols will be described below.

Examples of the "C1-C4 alkyl group" in the compound of the present invention include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group. Tert-butyl.

The expression "C1-C3 haloalkyl" of the compound of the present invention means one or more hydrogen atoms bonded to a carbon atom, and the number of carbon atoms substituted by a halogen atom is 1 to 3 linear or A branched chain alkyl group having a C1-C3 haloalkyl group having two or more halogen atoms may be the same or different from each other.

Examples of the "C1-C3 haloalkyl group" include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, a dichloromethyl group, a trifluoromethyl group, and a chlorodifluoromethyl group. Bromodifluoromethyl, trichloromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, five Fluoroethyl, heptafluoropropyl and heptafluoroisopropyl.

The expression of the Ca-Cb perfluoroalkyl group in the present specification means that the hydrogen atom bonded to the carbon atom is an alkyl group having a total of ab linear or branched chains substituted by a fluorine atom. .

Examples of the "C1-C3 perfluoroalkyl group" include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a heptafluoroisopropyl group.

Examples of the "C1-C3 alkyl group" in the compound of the present invention include a methyl group, an ethyl group, a propyl group and an isopropyl group.

The "halogen atom" of the compound of the present invention is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

As the compound of the present invention, for example, the following compounds can be mentioned.

In the formula (1), R ¹ is a C1-C4 alkyl compound; in the formula (1), R ¹ is a compound of an ethyl group, a cyclopropylmethyl group or a cyclopropyl group; in the formula (1), R ¹ is a compound of an ethyl group; in the formula (1), R ² is a compound of a C1-C3 perfluoroalkyl group; in the formula (1), a compound wherein R ² is a trifluoromethyl group; and in the formula (1), R ² is - a compound of OR ⁸ ; a compound of the formula (1) wherein R ² is a methoxy group; in the formula (1), a compound wherein R ² is an ethoxy group; and a compound of the formula (1) wherein R ² is a propoxy group; In the formula (1), a compound wherein R ² is an isopropoxy group; a compound of the formula (1) wherein R ² is a halogen atom or a hydrogen atom; and a compound of the formula (1) wherein R ² is a fluorine atom; ), R ² is a chlorine atom of the compound is; of formula (1), R ² is bromine atoms; formula (1), R ² is a hydrogen atoms; formula (1), R ³ is C1- a compound of a C3 alkyl group; a compound of the formula (1) wherein R ³ is a methyl group; in the formula (1), a compound wherein R ³ is a methyl group, a halogen atom or a hydrogen atom; and in the formula (1), R ³ is a halogen. the compound atom or a hydrogen atom; in formula (1), R ³ of the compound is a chlorine atom; formula (1), R ³ is bromine atoms; formula (1), R ³ is a hydrogen atom of the compound ; Of formula (1), the compound C1-C3 perfluoroalkyl group of R ⁴ is; trifluoromethyl compound of formula (1), R ⁴ is; of formula (1), R ⁴ is a pentafluoroethyl group of a compound; in the formula (1), R ⁴ is a compound of -S(O) _m R ⁷ ; in the formula (1), R ⁴ is a compound of trifluoromethylsulfonyl; in the formula (1), R ⁴ is a compound of a trifluoromethylsulfinyl group; in the formula (1), R ⁴ is a compound of trifluoromethylsulfonyl (Sulfonyl); in the formula (1), R ⁴ is pentafluoroethylsulfonate. a compound of sulfanyl; in the formula (1), R ⁴ is a compound of pentafluoroethylsulfinyl; in the formula (1), R ⁴ is a compound of pentafluoroethylsulfonyl (Sulfonyl); In the formula (1), R ⁵ is a C1-C3 alkyl compound; in the formula (1), R ⁵ is a methyl compound; in the formula (1), R ⁵ is a compound of -OR ⁸ ; Wherein R ⁵ is a methoxy compound; in the formula (1), R ⁵ is an ethoxy group compound; in the formula (1), R ⁵ is a propoxy group; in the formula (1), R ⁵ is a compound of isopropoxy group; a compound of the formula (1) wherein R ⁵ is a halogen atom or a hydrogen atom; in the formula (1), a compound wherein R ⁵ is a fluorine atom; and in the formula (1), R ⁵ is a chlorine atom; Compound; in formula (1) R ⁵ bromine atoms is; of formula (1), R ⁵ is a hydrogen atom ratio of; of formula (1), n represents 0 it is; of formula (1), n is the compound of 1; of formula (1) Wherein n is a compound of 2; a compound of formula (1-1), or an N-oxide thereof; ^Wherein R ^2a represents a C1-C3 perfluoroalkyl group, -OR ^6a , a halogen atom or a hydrogen atom, R ^3a represents a C1-C3 alkyl group, a halogen atom or a hydrogen atom, and R ^4a represents a C1-C3 perfluoroalkyl group. , or -S(O) _m R ^7a , R ^5a represents a C1-C3 alkyl group, -OR ^8a , a halogen atom or a hydrogen atom, R ^6a or R ^{8a are the} same or different and each represents a C1-C3 alkyl group, and R ^7a represents a C1 group. -C3 perfluoroalkyl, n represents 0, 1 or 2, and m represents 0, 1 or 2].

a compound of the formula (1-2), or an N-oxide thereof; ^Wherein R ^2a represents a C1-C3 perfluoroalkyl group, a halogen atom or a hydrogen atom, R ^3a represents a C1-C3 alkyl group, a halogen atom or a hydrogen atom, and R ^4a represents a C1-C3 perfluoroalkyl group, or -S (O) _m R ^7a , R ^7a represents a C1-C3 perfluoroalkyl group, n represents 0, 1 or 2, and m represents 0, 1 or 2].

a compound of the formula (1-3), or an N-oxide thereof; ^Wherein R ^2a represents a C1-C3 perfluoroalkyl group, a halogen atom or a hydrogen atom, R ^3a represents a C1-C3 alkyl group, a halogen atom or a hydrogen atom, and R ^4a represents a C1-C3 perfluoroalkyl group, or -S (O) _m R ^7a , R ^7a represents a C1-C3 perfluoroalkyl group, n represents 0, 1 or 2, and m represents 0, 1 or 2].

Next, the production method of the compound of the present invention will be described.

The compound of the present invention and the intermediate compound can be produced, for example, by the following (Production Method 1) to (Production Method 10).

(Manufacturing Method 1)

The compound of the present invention (1-n0) wherein n is 0 in the formula (1) can be produced by the following scheme.

[wherein, V ¹ represents a halogen atom, V ² represents a chlorine atom or a bromine atom, and other symbols have the same meanings as in the formula (1)].

The intermediate compound (M3) can be produced by reacting the intermediate compound (M1) with the compound (M2).

The intermediate compound (M1) can also be used as the hydrochloride or hydrobromide salt in the reaction.

This reaction is usually carried out in a solvent. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride, alcohols such as methanol and ethanol, diethyl ether, tetrahydrofuran (hereinafter referred to as THF), and ethylene glycol. Ethers such as ether, tert-butyl methyl ether and 1,4-dioxane, N,N-dimethylformamide (hereinafter referred to as DMF), N-methylpyrrolidone (hereinafter referred to as NMP) An aprotic polar solvent such as 1,3-dimethyl-2-imidazolidinone (hereinafter referred to as DMI) or dimethyl sulfoxide (hereinafter referred to as DMSO), water, and a mixture thereof.

This reaction can also be carried out in the presence of a base if necessary. Examples of the base include inorganic bases such as sodium hydrogencarbonate, sodium carbonate, and potassium carbonate; and organic bases such as triethylamine.

The reaction is usually in the ratio of 1 to 2 moles per mole of the intermediate compound (M1), and the ratio of the base is usually 1 to 5 moles. use.

The reaction temperature is usually in the range of 0 to 150 °C. The reaction time is usually in the range of 0.1 to 24 hours.

After completion of the reaction, the intermediate compound (M3) can be isolated by performing a usual post-treatment operation. The isolated intermediate compound (M3) can be further purified by chromatography, recrystallization, or the like.

The compound of the present invention (1-n0) wherein n is 0 can be produced by reacting the intermediate compound (M3) with the compound (M4) in the presence of a base. Examples of the base include alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrides such as sodium hydride.

This reaction is usually carried out in a solvent. Examples of the solvent include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; and nitriles such as acetonitrile. , aprotic polar solvents such as DMF, NMP, DMSO, etc., water, and mixtures thereof.

In the reaction, the compound (M4) is usually used in a ratio of from 1 to 10 mols, and the base is usually used in a ratio of from 1 to 10 mols, based on 1 mol of the intermediate compound (M3).

The reaction temperature is usually in the range of -50 to 100 °C. The reaction time is usually in the range of 0.1 to 12 hours.

After completion of the reaction, the compound of the present invention (1-n0) wherein n is 0 can be isolated by performing a usual post-treatment operation. The compound of the present invention (1-n0) which is isolated by n is further purified by chromatography, recrystallization or the like.

As the V ¹ in the reaction, a fluorine atom or a chlorine atom is preferred.

(Manufacturing Method 2)

The compound (1) of the present invention can be produced by reacting the intermediate compound (M5) with the compound (M2).

[wherein, V ³ represents a chlorine atom or a bromine atom, and other symbols have the same meanings as in the formula (1)].

The reaction (M5) can also be used as the hydrochloride or hydrobromide salt.

The compound (1) of the present invention can be produced by substituting the intermediate compound (M1) with the intermediate compound (M5) according to the method of Production Method 1.

(Manufacturing Method 3)

The compound of the present invention (1-n0) wherein n in the formula (1) is 0 can be produced by the following scheme.

Wherein R represents a methyl group or an ethyl group, L ¹ represents a chlorine atom or a bromine atom, and L ² represents a B(OH) ₂ group or a B(OR ^f ) ₂ group (wherein two R ^f are bonded to each other to form a bond; -C(CH ₃ ) ₂ C(CH ₃ ) ₂ -yl) or a triol borate, V ⁴ represents a chlorine atom or a bromine atom, V ⁵ represents a bromine atom or an iodine atom, and V ⁶ represents a fluorine atom, a chlorine atom or A halogen atom such as a bromine atom, and other symbols have the same meaning as in the formula (1).

The intermediate compound (M7) can be produced by reacting the compound (M2) with the compound (M6).

The reaction is carried out in a solvent or in the absence of a solvent. Examples of the solvent include alcohols such as methanol and ethanol, and ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, and aromatics such as toluene and xylene. Hydrocarbons and mixtures of these.

In the reaction, the compound (M6) is usually used in a ratio of from 1 to 10 mols based on 1 mol of the compound (M2).

The reaction temperature is usually in the range of 0 to 200 °C. Reaction time usually It is within the range of 0.1 to 24 hours.

After completion of the reaction, the intermediate compound (M7) can be isolated by performing a usual post-treatment operation. The isolated intermediate compound (M7) can be further purified by recrystallization or the like.

The intermediate compound (M8) can be produced by reacting the intermediate compound (M7) with phosphorus oxychloride or phosphorus oxybromide.

The reaction is carried out in a solvent or in the absence of a solvent. Examples of the solvent include nitriles such as acetonitrile and propionitrile, aromatic hydrocarbons such as toluene and xylene, and mixtures thereof.

In the reaction, phosphorus oxychloride or phosphorus oxybromide is usually used in an amount of from 1 to 10 mols based on 1 mol of the intermediate compound (M7).

The reaction temperature is usually in the range of 60 to 120 °C. The reaction time is usually in the range of 0.1 to 24 hours.

After completion of the reaction, the intermediate compound (M8) can be isolated by performing a usual post-treatment operation. The isolated intermediate compound (M8) can be further purified by recrystallization, chromatography or the like.

The intermediate compound (M10) can be produced by reacting the compound (M9) with the compound (M4) in the presence of a base. Examples of the base include a hydrogenated product of an alkali metal or an alkaline earth metal such as sodium hydride, potassium hydride or calcium hydride, an inorganic base such as sodium carbonate or potassium carbonate, and an organic base such as triethylamine.

This reaction is usually carried out in a solvent. Examples of the solvent include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, alcohols such as methanol and ethanol, and aromatics such as toluene and xylene. A nitrile such as a hydrocarbon or acetonitrile, an aprotic polar solvent such as DMF, NMP, DMI or DMSO, water or a mixture thereof.

In the reaction, the compound (M4) is usually used in a ratio of 0.8 to 1.2 mol, and the base is usually used in a ratio of 0.8 to 1.2 mol, based on 1 mol of the compound (M9).

The reaction temperature is usually in the range of 0 to 100 °C. The reaction time is usually in the range of 0.1 to 24 hours.

After completion of the reaction, the intermediate compound (M10) can be isolated by performing a usual post-treatment operation. The intermediate compound (M10) can be further purified by chromatography, recrystallization, or the like.

As the V ⁶ in the reaction, a fluorine atom or a chlorine atom is preferred.

L ² is an intermediate compound of a B(OH) ₂ group or a B(OR ^f ) ₂ group (wherein two R ^{f are} bonded to form a -C(CH ₃ ) ₂ C(CH ₃ ) ₂ - group) group (M11), after reacting the intermediate compound (M10) with an alkyllithium compound, reacting the resulting reaction intermediate with pinacol isopropoxide, or reacting the resulting reaction intermediate with boric acid After the trialkyl ester is reacted, it can be produced by carrying out hydrolysis. Examples of the alkyllithium compound include butyllithium (n-, sec- or tert-). Examples of the trialkyl borate include trimethyl borate, triethyl borate, and triisopropyl borate.

This reaction is usually carried out in a solvent. Examples of the solvent include ethers such as diethyl ether, THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, and aromatic hydrocarbons such as toluene and xylene. a mixture of these.

In the reaction, relative to the intermediate compound (M10) 1 mole, alkyl The lithium compound is usually used in a ratio of 1 mole, but can be appropriately changed.

In the reaction, the 1 mol of the intermediate compound (M10), the pinacol isopropoxide borate or the trialkyl borate are usually used in a ratio of 1 mol, but may be appropriately changed.

The reaction temperature of the reaction of the intermediate compound (M10) with the alkyllithium compound is usually in the range of -78 to 20 ° C, and the reaction time is usually in the range of 0.1 to 12 hours.

The reaction temperature of the reaction intermediate with the propranol boron isopropoxide or the trialkyl borate is usually in the range of from -78 ° C to 40 ° C, and the reaction time is usually from 0.1 to 24 hours. Inside.

After completion of the reaction, the intermediate compound (M11) can be isolated by performing a usual post-treatment operation. The isolated intermediate compound (M11) can be further purified by recrystallization, chromatography or the like.

L ² is an intermediate compound (M11) in which a B(OR ^f ) ₂ group (wherein two R ^f are bonded to each other to form a -C(CH ₃ ) ₂ C(CH ₃ ) ₂ - group), in a catalyst In the presence of a base, it can be produced by reacting an intermediate compound (M10) with bis(pinacolate) diboron. Examples of the catalyst include bismuth (triphenylphosphine) palladium, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium dichloromethane complex, and bis(phenylene). Palladium catalyst such as diacetone (0). As a base, potassium acetate is mentioned, for example.

This reaction is usually carried out in a solvent. Examples of the solvent include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; and mixtures thereof.

This reaction may also be added as a ligand for the catalyst if necessary. As The ligand may, for example, be tricyclohexylphosphine.

In the reaction, relative to the intermediate compound (M10) 1 mole, bis(pinacol ester) diboron is usually coordinated at a ratio of from 1 to 2 moles, and palladium catalyst at a ratio of from 0.0001 to 0.1 moles. The base is usually used in a ratio of from 0.000 to 0.2 mol, and the base is usually used in a ratio of from 1 to 5 mol.

The reaction temperature is usually in the range of 50 to 120 °C. The reaction time is usually in the range of 0.1 to 24 hours.

After completion of the reaction, the intermediate compound (M11) can be isolated by performing a usual post-treatment operation. The isolated intermediate compound (M11) can be further purified by recrystallization, chromatography or the like.

L ² is an intermediate compound (M11) of a triol borate, which can be obtained by reacting a reaction intermediate formed by reacting an intermediate compound (M10) with an alkyllithium compound with a trialkyl borate. The alkoxy borate is produced by reacting with a triol.

Examples of the alkyllithium compound used for the reaction include butyllithium (n-, sec- or tert-). Examples of the trialkyl borate used for the reaction include trimethyl borate and triisopropyl borate. As a triol used for the reaction, for example, gin (hydroxymethyl)ethane can be mentioned.

These reactions are usually carried out in a solvent. Examples of the solvent include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; and mixtures thereof.

In the reaction, the alkyllithium compound is usually used in a ratio of 1 mol per mol of the intermediate compound (M10), but may be appropriately changed.

In the reaction, the trialkyl borate is usually used in a ratio of 1 mol with respect to 1 mol of the intermediate compound (M10), but may be appropriately changed.

In the reaction, the triol is usually used in a ratio of 1 mol with respect to 1 mol of the intermediate compound (M10), but may be appropriately changed.

The reaction temperature of the reaction of the intermediate compound (M10) with the alkyllithium compound is usually in the range of -78 to 20 ° C, and the reaction time is usually in the range of 0.1 to 12 hours.

The reaction temperature in the reaction of the reaction intermediate with the trialkyl borate is usually in the range of from -78 ° C to 40 ° C, and the reaction time is usually in the range of from 0.1 hour to 24 hours.

The reaction temperature in the reaction of the organotrialkoxyborate with the triol is usually in the range of from -20 ° C to 40 ° C, and the reaction time is usually in the range of from 0.1 hour to 24 hours.

After completion of the reaction, the intermediate compound (M11) can be isolated by concentrating the reaction mixture.

The compound (1-n0) of the present invention wherein n is 0 in the formula (1) can be produced by reacting the intermediate compound (M8) with the intermediate compound (M11) in the presence of a catalyst. L ² is an intermediate compound using a B(OH) ₂ group or a B(OR ^f ) ₂ group (wherein 2 R ^f bonds to form a -C(CH ₃ ) ₂ C(CH ₃ ) ₂ - group) In the case of (M11), the reaction is carried out in the presence of a base. Examples of the catalyst include bismuth (triphenylphosphine) palladium, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium dichloromethane complex, and bis(phenylene). Palladium catalyst such as diacetone (0) or palladium acetate. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, cesium carbonate, potassium tert-butoxide, potassium phosphate, and the like, and organic acid salts such as sodium acetate and potassium acetate. .

This reaction is usually carried out in a solvent. Examples of the solvent include an ether such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether or 1,4-dioxane, an aromatic hydrocarbon such as toluene or xylene, or an aprotic such as DMF. Sexual polar solvents, water and mixtures of these.

This reaction may also be added as a ligand for the catalyst if necessary. Examples of the ligand include tricyclohexylphosphine, triphenylphosphine, X-Phos (2-dicyclohexylphosphino-2', 4',6'-triisopropylbiphenyl, John Phos ( (2-biphenyl)di-tert-butylphosphine).

This reaction is necessary, and copper (I) iodide may also be added.

In the reaction, the intermediate compound (M13) is usually in a ratio of 1 to 3 moles with respect to the intermediate compound (M9), and the palladium catalyst is in a ratio of from 0.0001 to 0.1 mole. The ratio of 0.0002 to 0.2 mol, copper iodide (I) is used in a ratio of from 0.01 to 0.4 mol, and the base is usually used in a ratio of from 1 to 10 mol.

The reaction temperature is usually in the range of 50 to 150 °C. The reaction time is usually in the range of 0.1 to 24 hours.

After completion of the reaction, the compound (1-n0) of the present invention can be isolated by performing a usual post-treatment operation. The compound (1-n0) of the present invention which is isolated may be further purified by recrystallization, chromatography or the like.

(Manufacturing Method 4)

The compound of the present invention wherein n is 1 or 2 in the formula (1) can be produced by oxidizing the compound of the present invention wherein n is 0.

[In the formula, the symbol system has the same meaning as the formula (1)].

The compound (1-n1) of the present invention wherein n is 1 in the formula (1) can be produced by reacting the compound (1-n0) of the present invention wherein n is 0 with an oxidizing agent. Examples of the oxidizing agent include sodium periodate and m-chloroperoxybenzoic acid.

This reaction is usually carried out in a solvent. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, esters such as ethyl acetate, acetic acid, water, and the like.

In the reaction, the oxidizing agent is usually used in a ratio of 1 to 3 moles relative to the compound (1-n0) 1 mole of the present invention. Preferably, the oxidizing agent is used in an amount of from 1 to 1.2 mol per mol of the compound (1-n0) of the present invention.

The reaction temperature is usually in the range of -50 to 50 °C. The reaction time is usually in the range of 0.1 to 12 hours.

After the reaction is completed, 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, sodium thiosulfate), an aqueous solution of a base (for example, sodium hydrogencarbonate), and dried. After the treatment, concentration, etc., the treatment can be carried out separately from the compound (1-n1) of the present invention. The compound (1-n1) of the present invention which is isolated may be further purified by chromatography, recrystallization or the like.

The compound (1-n2) of the present invention wherein n is 2 in the formula (1) can be produced by reacting the compound (1-n1) of the present invention wherein n is 1 with an oxidizing agent. As Examples of the oxidizing agent include m-chloroperoxybenzoic acid, hydrogen peroxide solution or potassium persulfate (Potassium peroxymonosulphate, registered trademark of E-I DuPont).

This reaction is usually carried out in a solvent. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, esters such as ethyl acetate, nitriles such as acetonitrile, acetic acid, water, and the like.

This reaction can also be carried out in the presence of a catalyst if necessary. Examples of the catalyst include tungstic acid, sodium tungstate, and potassium tungstate.

In the reaction, the oxidizing agent is usually used in a ratio of from 1 to 4 mol, and the catalyst is usually used in a ratio of from 0.01 to 0.5 mol, based on the compound (1-n1)1 mol of the present invention. Preferably, it is used in an amount of from 1 to 2 moles per mole of the catalyst of the present invention (1-n1), and the catalyst is used in a ratio of from 0.05 to 0.2 moles.

The reaction temperature is usually in the range of -50 to 100 °C. The reaction time is usually in the range of 0.1 to 12 hours.

After the reaction is completed, 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, sodium thiosulfate), an aqueous solution of a base (for example, sodium hydrogencarbonate), and dried. After the treatment, concentration, etc., the treatment can be carried out separately from the compound (1-n2) of the present invention. The compound (1-n2) of the present invention can be further purified by chromatography, recrystallization or the like.

Further, the compound of the present invention (1-n2) wherein n is 2 in the formula (1) can be reacted in one step by reacting the compound of the present invention (1-n0) wherein n is 0 with an oxidizing agent. (One-pot) manufacturing. Examples of the oxidizing agent include m-chloroperoxybenzoic acid, a hydrogen peroxide solution, and potassium hydrogen persulfate (Potassium peroxymonosulphate, registered trademark of E-I DuPont).

This reaction is usually carried out in a solvent. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, esters such as ethyl acetate, nitriles such as acetonitrile, acetic acid, water, and the like.

This reaction can also be carried out in the presence of a catalyst if necessary. Examples of the catalyst include tungstic acid, sodium tungstate, and potassium tungstate.

In the reaction, the oxidizing agent is usually used in a ratio of 2 to 5 moles, and the catalyst is usually used in a ratio of 0.01 to 0.5 moles, relative to the compound (1-n0) 1 mole of the present invention. Preferably, it is used in an amount of from 2 to 3 moles with respect to the compound (1-n0) of the present invention, and the catalyst is used in a ratio of from 0.05 to 0.2 moles.

The reaction temperature 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 the reaction is completed, 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, sodium thiosulfate), an aqueous solution of a base (for example, sodium hydrogencarbonate), and dried. After the treatment, concentration, etc., the treatment can be carried out separately from the compound (1-n2) of the present invention. The compound (1-n2) of the present invention which is isolated may be further purified by chromatography, recrystallization or the like.

(Manufacturing Method 5)

The compound (P1) of the present invention wherein R ³ is a chlorine atom, a bromine atom or an iodine atom in the formula (1) can be carried out by reacting the compound (1-n2) of the present invention wherein n is 2 in the formula (1) with a halogenating agent. The reaction is made.

[wherein, R ^{3 '} represents a chlorine atom, a bromine atom or an iodine atom, and other symbols have the same meanings as in the formula (1)].

Examples of the halogenating agent include chlorine, bromine, iodine, N-chloroammonium imine, N-bromosinium imine, N-iodosuccinimide, and halonium.

This reaction is usually carried out in a solvent. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile, and aprotic polar solvents such as DMF, NMP and DMSO, and mixtures thereof.

In the reaction, the halogenating agent is usually used in a ratio of 1 to 2 moles relative to the compound (1-n2) 1 mole of the present invention.

The reaction temperature is usually in the range of 0 to 150 °C. The reaction time is usually in the range of 0.1 to 24 hours.

After completion of the reaction, the compound (P1) of the present invention can be isolated by performing a usual post-treatment operation. The compound (P1) of the present invention which is isolated may be further purified by chromatography, recrystallization or the like.

(Manufacturing Example 6)

The compound of the present invention (1-n2m1) or the compound of the present invention (1-n2m2) wherein R ⁴ is -S(O) _m R ⁷ , n is 2, m is 1 or 2, and can be oxidized by R The compound of the present invention (1-n2m0) wherein ⁴ is -S(O) _m R ⁷ , n is 2, and m is 0.

[In the formula, the symbol system has the same meaning as the formula (1)].

The compound of the present invention (1-n2m1) wherein R ⁴ is -S(O) _m R ⁷ , n is 2, m is 1, and R ⁴ is -S(O) _m R ⁷ , The compound of the present invention (1-n2m0) wherein n is 2 and m is 0 is produced by reacting with an oxidizing agent. Examples of the oxidizing agent include sodium periodate, m-chloroperoxybenzoic acid, a hydrogen peroxide solution, and potassium hydrogen persulfate (Potassium peroxymonosulphate, registered trademark of EI DuPont).

This reaction is usually carried out in a solvent. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, esters such as ethyl acetate, nitriles such as acetonitrile, acetic acid, water, and the like.

This reaction can also be carried out in the presence of a catalyst if necessary. Examples of the catalyst include tungstic acid, sodium tungstate, and potassium tungstate.

In the reaction, the oxidizing agent is usually used in a ratio of 1 to 3 moles, and the catalyst is usually used in a ratio of 0.01 to 0.5 moles, relative to the compound (1-n2m0)1 mole of the present invention. Preferably, it is used in an amount of from 1 to 1.2 mol per mol of the compound of the present invention (1-n2m0), and the catalyst is used in a ratio of from 0.05 to 0.2 mol.

The reaction temperature is usually in the range of -50 to 100 °C. The reaction time is usually in the range of 0.1 to 12 hours.

After the reaction is completed, 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, sodium thiosulfate), an aqueous solution of a base (for example, sodium hydrogencarbonate), and dried. After the treatment, concentration, etc., the treatment can be carried out separately from the compound of the present invention (1-n2m1). The compound of the present invention (1-n2m1) which is isolated can be further purified by chromatography, recrystallization or the like.

In the formula (1), the compound of the present invention (1-n2m2) wherein R ⁴ is -S(O) _m R ⁷ , n is 2, and m is 2, and R ⁴ is -S(O) _m R ⁷ , The compound of the present invention (1-n2m1) wherein n is 2 and m is 1, is produced by reacting with an oxidizing agent. Examples of the oxidizing agent include m-chloroperoxybenzoic acid, a hydrogen peroxide solution, and potassium persulfate (Potassium peroxymonosulphate, registered trademark).

This reaction is usually carried out in a solvent. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, esters such as ethyl acetate, nitriles such as acetonitrile, acetic acid, water, and the like.

This reaction can also be carried out in the presence of a catalyst if necessary. Examples of the catalyst include tungstic acid, sodium tungstate, and potassium tungstate.

In the reaction, the oxidizing agent is usually used in a ratio of from 1 to 4 mols, and the catalyst is usually used in a ratio of from 0.01 to 0.5 mol per mol of the compound (1-n2m1) of the present invention. Preferably, it is used in an amount of from 1 to 2 mol based on the compound of the present invention (1-n2m1), and the catalyst is used in a ratio of from 0.05 to 0.2 mol.

The reaction temperature is usually in the range of -50 to 100 °C. The reaction time is usually in the range of 0.1 to 12 hours.

After the reaction is completed, 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, sodium thiosulfate), an aqueous solution of a base (for example, sodium hydrogencarbonate), and dried. After the treatment, concentration, etc., the treatment can be carried out separately from the compound of the present invention (1-n2m2). The compound of the present invention (1-n2m2) can be further purified by chromatography, recrystallization or the like.

Further, in the formula (1), R ⁴ is -S(O) _m R ⁷ , n is 2, and m is 2, the compound of the present invention (1-n2m2) can be made by making R ⁴ -S(O) _m R ^7. The compound of the present invention (1-n2m0) wherein n is 2 and m is 0 is reacted with an oxidizing agent to produce a one-pot. Examples of the oxidizing agent include m-chloroperoxybenzoic acid, a hydrogen peroxide solution, and potassium hydrogen persulfate (Potassium peroxymonosulphate, registered trademark of EI DuPont).

This reaction is usually carried out in a solvent. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, esters such as ethyl acetate, nitriles such as acetonitrile, acetic acid, water, and the like.

This reaction can also be carried out in the presence of a catalyst if necessary. As a catalyst, For example, tungstic acid, sodium tungstate, and potassium tungstate can be cited.

In the reaction, the oxidizing agent is usually used in a ratio of 2 to 5 moles, and the catalyst is usually used in a ratio of 0.01 to 0.5 moles, relative to the compound (1-n2m0)1 mole of the present invention. Preferably, it is used in an amount of from 2 to 3 moles per mole of the catalyst of the present invention (1-n2m0), and the catalyst is used in a ratio of from 0.05 to 0.2 moles.

The reaction temperature 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 the reaction is completed, 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, sodium thiosulfate), an aqueous solution of a base (for example, sodium hydrogencarbonate), and dried. After the treatment, concentration, etc., the treatment can be carried out separately from the compound of the present invention (1-n2m2). The compound of the present invention (1-n2m2) which is isolated may be further purified by chromatography, recrystallization or the like.

(Manufacturing Method 7)

The compound of the present invention (1-n2m1) or the compound of the present invention (1-n2m2) wherein R ⁴ is -S(O) _m R ⁷ , n is 2, m is 1 or 2, and can be oxidized by R The compound of the present invention (1-n0m0) wherein ⁴ is -S(O) _m R ⁷ , n is 0, and m is 0.

[In the formula, the symbol system has the same meaning as the formula (1)].

The compound of the present invention (1-n2m1) wherein R ⁴ is -S(O) _m R ⁷ , n is 2, m is 1, and R ⁴ is -S(O) _m R ⁷ , The compound of the present invention (1-n0m0) wherein n is 0 and m is 0 is reacted with an oxidizing agent to produce a one-pot. Examples of the oxidizing agent include m-chloroperoxybenzoic acid, a hydrogen peroxide solution, or potassium hydrogen persulfate (Potassium peroxymonosulphate, registered trademark of EI DuPont).

This reaction is usually carried out in a solvent. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, esters such as ethyl acetate, nitriles such as acetonitrile, acetic acid, water, and the like.

This reaction can also be carried out in the presence of a catalyst if necessary. Examples of the catalyst include tungstic acid, sodium tungstate, and potassium tungstate.

In the reaction, the oxidizing agent is usually used in a ratio of 3 to 10 moles, and the catalyst is usually used in a ratio of 0.01 to 0.5 moles, relative to the compound (1-n0m0)1 mole of the present invention. Preferably, it is relative to the compound (1-n0m0) of the present invention, the oxidizing agent is in a ratio of 3 to 5 moles, and the catalyst is 0.05 to 0.2 moles. Proportional use.

The reaction temperature 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 the reaction is completed, 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, sodium thiosulfate), an aqueous solution of a base (for example, sodium hydrogencarbonate), and dried. After the treatment, concentration, etc., the treatment can be carried out separately from the compound of the present invention (1-n2m1). The compound of the present invention (1-n2m1) which is isolated can be further purified by chromatography, recrystallization or the like.

In the formula (1), the compound of the present invention (1-n2m2) wherein R ⁴ is -S(O) _m R ⁷ , n is 2, and m is 2, and R ⁴ is -S(O) _m R ⁷ , The compound of the present invention (1-n0m0) wherein n is 0 and m is 0 is reacted with an oxidizing agent to produce a one-pot. Examples of the oxidizing agent include m-chloroperoxybenzoic acid, a hydrogen peroxide solution, and potassium hydrogen persulfate (Potassium peroxymonosulphate, registered trademark of EI DuPont).

This reaction is usually carried out in the presence of a solvent.

Examples of the solvent to be used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, esters such as ethyl acetate, nitriles such as acetonitrile, acetic acid, and water. a mixture of such.

This reaction can also be carried out in the presence of a catalyst if necessary. Examples of the catalyst include tungstic acid, sodium tungstate, and potassium tungstate.

In the reaction, the oxidizing agent is usually used in a ratio of 4 to 15 moles, and the catalyst is usually used in a ratio of 0.01 to 0.5 moles, relative to the compound (1-n0m0)1 mole of the present invention. Preferably, it is relative to the compound of the present invention (1-n0m0) The ear, the oxidant is used in a ratio of 4 to 5 moles, and the catalyst is used in a ratio of 0.05 to 0.2 moles.

The reaction temperature 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 the reaction is completed, 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, sodium thiosulfate), an aqueous solution of a base (for example, sodium hydrogencarbonate), and dried. After the treatment, concentration, etc., the treatment can be carried out separately from the compound of the present invention (1-n2m2). The compound of the present invention (1-n2m2) which is isolated may be further purified by chromatography, recrystallization or the like.

(Manufacturing Method 8)

The compound (P3) of the present invention wherein R ² is -OR ^{6 in} the formula (1) can be produced by reacting the compound (P2) of the present invention wherein R ² is a halogen atom with the compound (M12) in the presence of a base. Examples of the base include alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrides such as sodium hydride.

[In the formula, R ^{2 '} represents a halogen atom, and other symbols have the same meanings as in the formula (1)].

This reaction is usually carried out in a solvent. Examples of the solvent include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; and nitriles such as acetonitrile. , aprotic polar solvents such as DMF, NMP, DMSO, etc., water, and mixtures thereof.

In the reaction, the compound (M12) is usually used in a ratio of from 1 to 10 mols, and the base is usually used in a ratio of from 1 to 10 mols, based on 1 mol of the compound (P2) of the present invention.

The reaction temperature is usually in the range of -50 to 100 °C. The reaction time is usually in the range of 0.1 to 12 hours.

After completion of the reaction, the compound (P3) of the present invention wherein R ² is -OR ⁶ can be isolated by performing a usual post-treatment operation. The compound (P3) of the present invention which is isolated may be further purified by chromatography, recrystallization or the like.

In the reaction, as R ^{2 '} , a fluorine atom or a chlorine atom is preferred.

(Manufacturing Method 9)

The compound (P4) of the present invention wherein R ² is -OR ⁶ and n is 2 in the formula (1) can be produced by the following scheme.

[In the formula, V ⁷ and V ^{8 are the} same or different and each represents a halogen atom, and the other symbols have the same meanings as in the formula (1)].

Intermediate (M13) in the presence of a base, may be by making V ⁸ is a halogen atom of the intermediate compound (M3 ^') is reacted with a compound (M4) is manufactured. Examples of the base include alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrides such as sodium hydride.

This reaction is usually carried out in a solvent. Examples of the solvent include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; and nitriles such as acetonitrile. , aprotic polar solvents such as DMF, NMP, DMSO, etc., water, and mixtures thereof.

In the reaction, the compound (M4) is usually used in a ratio of 2 to 10 moles, and the base is usually used in a ratio of 2 to 10 moles, relative to the intermediate compound (M3 ^' )1 mole.

The reaction temperature is usually in the range of -50 to 100 °C. The reaction time is usually in the range of 0.1 to 12 hours.

After completion of the reaction, the intermediate (M13) can be isolated by performing a usual post-treatment operation. The isolated intermediate (M13) can be further purified by chromatography, recrystallization, or the like.

In the reaction, V ⁷ and V ^{8 are} preferably the same or different from each other as a fluorine atom or a chlorine atom.

The intermediate compound (M14) can be produced by reacting the intermediate compound (M13) with an oxidizing agent. As the oxidizing agent, for example, m-chloro Peroxybenzoic acid, hydrogen peroxide solution and potassium persulfate (Oxone) (Potassium peroxymonosulphate, registered trademark of E-I DuPont).

This reaction is usually carried out in a solvent. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, esters such as ethyl acetate, nitriles such as acetonitrile, acetic acid, water, and the like.

This reaction can also be carried out in the presence of a catalyst if necessary. Examples of the catalyst include tungstic acid, sodium tungstate, and potassium tungstate.

In the reaction, the oxidizing agent is usually used in a ratio of 4 to 20 moles, and the catalyst is usually used in a ratio of 0.01 to 0.5 moles, based on 1 mol of the intermediate compound (M13). Preferably, it is used in an amount of from 4 to 6 moles relative to the intermediate compound, and the catalyst is used in a ratio of from 0.05 to 0.2 moles.

The reaction temperature is usually in the range of -50 to 100 °C. The reaction time is usually in the range of 0.1 to 12 hours.

After the reaction is completed, 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, sodium thiosulfate) or an aqueous solution of a base (for example, sodium hydrogencarbonate), and dried. After the concentration and the like, the treatment operation can be carried out separately from the intermediate compound (M14). The intermediate compound (M14) can be further purified by chromatography, recrystallization or the like.

The compound (P4) of the present invention wherein R ² is -OR ⁶ and n is 2 in the formula (1) can be produced by reacting the intermediate compound (M14) with the compound (M12) in the presence of a base.

The compound (P4) of the present invention can be produced by substituting the intermediate compound (M14) in place of the compound (P2) of the present invention wherein R ² is a halogen atom.

(Manufacturing Law 10)

The intermediate compound (M1) and the intermediate compound (M5) can be produced according to the following scheme.

Wherein Y represents a nitrile group or an N-methoxy-N-methylaminecarbamyl group, V ¹ represents a halogen atom, V ² represents a chlorine atom or a bromine atom, V ³ represents a chlorine atom or a bromine atom, and L ³ Represents a chlorine atom, a bromine atom or an iodine atom, Z ¹ represents a methyl group, an ethyl group or an isopropyl group, and Z ² represents a methyl group, an ethyl group, an isopropyl group or a tert-butyl group, and other symbols are the same as those of the formula (1) significance].

The intermediate compound (M17) can be produced by reacting the compound (M15) with the compound (M16).

The intermediate compound (M20) can be produced by reacting the compound (M19) with the compound (M16).

Examples of the solvent used for the reaction include THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, ethers such as 1,4-dioxane, and aromatic hydrocarbons such as toluene and xylene. Classes and mixtures of these.

In the reaction, the compound (M16) is usually used in a ratio of from 0.9 to 1.5 mol per mol of the compound (M15) or the compound (M19).

The reaction temperature is usually in the range of -20 to 100 °C. The reaction time is usually in the range of 0.1 to 24 hours.

After completion of the reaction, the intermediate compound (M17) or the intermediate compound (M20) may be isolated by performing a usual post-treatment operation. The intermediate compound (M17) or the intermediate compound (M20) can be further purified by chromatography, recrystallization or the like.

The intermediate compound (M1) or the intermediate compound (M5) can be produced by reacting the intermediate compound (M17) or the intermediate compound (M20) with a chlorinating agent or a brominating agent. Examples of the chlorinating agent include chlorine and N-chlorosuccinimide. Examples of the brominating agent include bromine, N-bromosuccinimide, tetrabutylammonium tribromide, and pyridinium bromide. Compound bromide and phenyltrimethylammonium tribromide.

This reaction is usually carried out in a solvent. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride, and methanol and B. Alcohols such as alcohols, diethyl ether, THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, nitriles such as acetonitrile, ethers such as 1,4-dioxane, DMF, NMP, DMSO An aprotic polar solvent, acetic acid, water, and mixtures thereof.

This reaction may also be added with aluminum chloride or hydrogen bromide if necessary.

In the reaction, a chlorinating agent or a brominating agent is usually used in a ratio of from 0.9 to 1.2 mol per mol of the intermediate compound (M17) or the intermediate compound (M20).

The reaction temperature is usually in the range of 0 to 150 °C. The reaction time is usually in the range of 0.1 to 24 hours.

After completion of the reaction, the intermediate compound (M1) or the intermediate compound (M5) may be isolated by performing a usual post-treatment operation.

The reaction may also be carried out separately from the intermediate compound (M1) or the intermediate compound (M5) as the hydrochloride or hydrobromide salt.

The intermediate compound (M18) or the intermediate compound (M21) can be produced by reacting the intermediate compound (M17) or the intermediate compound (M20) with a Silylation agent in the presence of a base. Examples of the decylating agent include triisopropyl sulfonium trifluoromethanesulfonate, tert-butyl dimethyl decyl trifluoromethanesulfonate, and tert-butyl dimethyl chlorodecane. Examples of the base include, for example, a base. Triethylamine, N,N-diisopropylethylamine.

This reaction is usually carried out in a solvent. Examples of the solvent include aliphatic halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; nitriles such as acetonitrile; aromatic hydrocarbons such as toluene and xylene; and aprotic such as DMF, NMP and DMSO. Sexual polar solvents and mixtures of these.

The reaction may also be added to a catalytic amount of sodium iodide if necessary.

In the reaction, relative to the intermediate compound (M17) or the intermediate compound (M20) 1 mole, the alkylating agent is usually in a ratio of 0.9 to 1.2 moles, and the base is in a ratio of 1 to 2 moles, sodium iodide. Use 0.1 to 0.5 moles.

The reaction temperature is usually in the range of 0 to 150 °C. The reaction time is usually in the range of 0.1 to 24 hours.

After completion of the reaction, the intermediate compound (M18) or the intermediate compound (M21) can be isolated by performing a usual post-treatment operation.

Substituting the intermediate compound (M17) or the intermediate compound (M20), using the intermediate compound (M18) or the intermediate compound (M21), the intermediate compound (M1) or the intermediate compound can be produced according to the method of the production method 9. (M5).

(Manufacturing Law 11)

In the compound of the present invention and the above intermediate compound, N-oxidation of the nitrogen atom by oxidation can be carried out by reacting a compound having a nitrogen-containing heterocyclic group having an isolated electron pair with an oxidizing agent on a nitrogen atom. Things.

The nitrogen-containing heterocyclic group may, for example, be a pyridine ring.

The reaction can be carried out by a known method, for example, a halogenated hydrocarbon such as dichloromethane, chloroform or chlorobenzene, an alcohol such as methanol or ethanol, a nitrile such as acetonitrile, acetic acid, water or the like. It is carried out using an oxidizing agent such as m-chloroperoxybenzoic acid or hydrogen peroxide.

Next, specific examples of the compound of the present invention are shown below.

In formula (1-2), R ⁴ is a trifluoromethyl group, and R ² , R ³ and n are the compounds of the present invention in the combinations shown in [Table 1] to [Table 2].

In the formula (1-2), R ⁴ is a pentafluoroethyl group, and R ² , R ³ and n are the compounds of the invention in the combinations described in [Table 1] to [Table 2].

In the formula (1-2), R ⁴ is a trifluoromethylsulfonyl group, and R ² , R ³ and n are the compounds of the present invention in the combinations described in [Table 1] to [Table 2].

In the formula (1-2), R ⁴ is a trifluoromethylsulfinyl group, and R ² , R ³ and n are the compounds of the present invention in the combinations described in [Table 1] to [Table 2].

In the formula (1-2), R ⁴ is a trifluoromethylsulfonyl group (Sulfonyl), and R ² , R ³ and n are the compounds of the present invention in the combination of [Table 1] to [Table 2].

In formula (1-3),

R ⁴ is a trifluoromethyl group, and R ² , R ³ and n are the compounds of the present invention in the combinations shown in [Table 1] to [Table 2].

In the formula (1-3), R ⁴ is a pentafluoroethyl group, and R ² , R ³ and n are the compounds of the invention in the combinations described in [Table 1] to [Table 2].

In the formula (1-3), R ⁴ is a trifluoromethylsulfonyl group, and R ² , R ³ and n are the compounds of the present invention in the combinations described in [Table 1] to [Table 2].

In the formula (1-3), R ⁴ is a trifluoromethylsulfinyl group, and R ² , R ³ and n are the compounds of the present invention in the combinations described in [Table 1] to [Table 2].

In the formula (1-3), R ⁴ is a trifluoromethylsulfonyl group, and R ² , R ³ and n are the compounds of the invention in the combinations shown in [Table 1] to [Table 2].

The compound of the present invention is a harmful organism having efficacy, and examples thereof include harmful arthropods and harmful nematodes such as harmful insects or harmful mites. Specific examples of the pest include the following.

Hemipteran pests: Laodelphax striatella, Nilaparvata lugens, Sogatella furcifera, etc. Nepenthes, Nephotettix cincticeps, Nephotettix virescens, Empoasca onukii, Aphis gossypii, Myzus Persicae), Brevicoryne brassicae, Aphis spiraecola, Macrosiphum euphorbiae, Aulacorthum solani, Rhopalosiphum padi, Toxoptera citricidus, peach Aphids such as Hyolapterus pruni, Nezara antennata, Eysarcoris parvus, Halyomorpha mista, Riptortus clavetus, Zhonghua rice Leptocorisa chinensis and other species of the genus Mosquito, Trigonotylus caelestialium, Stenotus rubrovittatus, Trialeurodes vaporariorum, Tobacco whitefly Bemisia tabaci), Dialeurodes citri, Aleurocanthus spiniferus, Aonidiella aurantii, pear Comstockaspis perniciosa, Unaspis citri, Ceroplastes rubens, Icerya purchasi, Planococcus kraunhiae, long tail powder scale insect ( Pseudococcus longispinis), psyllids such as Pseudaulacaspis pentagona, diatoms such as Diaphorina citri, Psylla pyrisuga, and Bactericerca cockerelli Nets, such as Stephanitis nasi, bed bugs (Cimex) Leptoids such as lectularius).

Lepidopteran pests: Chilo suppressalis, Tryporyza incertulas, Cnaphalocrocis medinalis, Notarcha derogata, Plodia interpunctella, Asia Ostrichia furnacalis, Hellula undalis, Pediasia teterrellus, Spodoptera litura, Spodoptera exigua, Musca domestica (Pseudaletia separata), Mamestra brassicae, Agrotis ipsilon, Plusia nigrisigna, Helicoverpa genus, Helicoverpa armigera, Helicoverpa genus White butterflies, such as moths and Pieris rapae, Adoxophyes, Gramholita molesta, Leguminivora glycinivorella, Matsumuraeses azukivora, apple small Adoxophyes orana fasciata, Adoxophyes honmai., Homona magnanima, Archips fuscocupreanus, Cydia pomonella, etc. Leaf moth, Caloptilia theivora, the fine moth of the Phyllonycter ringoneella, the apple leaf moth, such as Carposina niponensis, the leaf moth of the Rionetia genus, the Rimantoria genus, A genus of the genus Euproctis, such as the genus Moth, Plutella xylostella, Pectophora gossypiella, Phthorimaea operculella, etc. Tiger moths such as Hyphantria cunea, and moths such as Tinea translucens and Tineola bisselliella.

Thysanoptera pests: Frankliniella occidentalis, Thrips palmi, Scirtothrips dorsalis, Thrips tabaci, Frankliniella intonsa, etc. Hummer.

Diptera pests: Culex pipiens pallens, Culex tritaeniorhynchus, Culex quinquefasciatus, Aedes aegypti, Aedes albopictus ) such as Aedes, Anopheles sinensis, Aedes, Chironomia, Musca domestica, Muscina stabulans, house flies, green fly, meat Flies, summer flies, Delia platura, Delia antiqua, etc., Drosophila, Agromyza oryzae, Hydrellia griseola, tomato smear Liriomyza sativae, Liriomyza trifolii, Chromatomyia horticola, Liriomyza, such as Chlorops oryzae, and Phytophthora Dacus cucurbitae), fruit flies such as Ceratitis capitata, fruit flies, scorpion flies such as Megaselia spiracularis, butterfly flies such as Clogmia albipunctata, and black-winged hawksbill Anthraquinones, mites, burdocks (Tabanus trigonus) Flies and lice sting flies.

Coleoptera pest: corn rootworm (Diabrotica virgifera Virgifera), southern broccoli (Diabrotica undecimpunctata howardi), Oulema oryzae, Aulacophora femoralis, Phyllotreta striolata, Leptinotarsa decemlineata, etc. Flower worms, Anomala cuprea, Anomala rufocuprea, Japanese chafer (Popillia japonica), chafer, Sitophilus zeamais, Echinocnemus squameus, rice water elephant trunk Beans like noses such as Lisorhoptrus oryzophilus, Sphenophorus venatus, Elephant larvae such as Anthonomus grandis, and Elephant porpoise (Callosobruchuys chienensis) Insects, beetles (Tenebrio molitor), Tribolium castaneum, etc., such as walking insects, Anthrenus verbasci, Dermestes maculatus, etc. (Lasioderma serricorne), such as aphids, Epilachna vigintioctopunctata, etc., Lyctus brunneus, Small locusts such as Tomicus piniperda, long locusts, specimens of round mites, Anoplophora malasiaca, etc., Agriotes ogurae fuscicollis, etc. Agriotes spp., and genus of the genus Paederus fuscipes.

Orthoptera pests: Locusta migratoria, Gryllotalpa africana, Oxya yezoensis, day This rice blast (Oxya japonica), and mites.

Thysanoptera pests: Ctenocephalides felis, Ctenocephalides canis, Pulex irritans, Xenopsylla cheopis, and the like.

Pseudomonas: Pediculus humanus corporis, Pediculus humanus humanus, Phthirus pubis, Haematopinus eurysternus, Dalmalinia ovis, Haematopinus Suis), shit (Linognathus setosus) and so on.

Pestivorous pests: Dalmalinia ovis, Dalmalinia bovis, Menopon gallinae, Trichodectes canis, Felicola subrostrata, etc.

Hymenoptera pests: Monomorium pharaosis, Formica fusca japonica, Ochetellus glaber, Pristomyrmex pungens, Pheidole Noda), Acromyrmex spp., Solenopsis spp., Linepithema humile, ants, wasps, ant bees, and Athalia rosae, Leaf bees of the genus Athalia japonica.

Nematodes: Aphelenchoides besseyi, Nothotylenchus acris, Meloidogyne incognita, Meloidogyne hapla, Meloidogyne javanica, Soybean cysts Heterodera glycines, Globodera rostochiensis, Pratylenchus coffeae, Pratylenchus neglectus, and the like.

Obsidian pests: (Blattella germanica, Periplaneta fuliginosa, Periplaneta americana, Periplaneta brunnea, Blata orientalis, etc.).

Isoptera pests: Reticulitermes speratus, Coptotermes formosanus, Incisitermes minor, Cryptotermes domesticus, Odontotermes formosanus, Neotermes koshunensis ), Glyptotermes satsumensis, Glyptotermes nakajimai, Glyptotermes fuscus, Glyptotermes kodamai, Glyptotermes kushimensis, Hodotermopsis japonica, Coptotermes guangzhoensis ), Reticulitermes miyatakei, Reticulitermes flaviceps amamianus, Reticulitermes sp., Nasutitermes takasagoensis, Pericapritermes nitobei, Sinocapritermes mushae )Wait.

Pseudomonas: Tetranychus urticae, Tetranychus kanzawai, Panonychus citri, Panonychus ulmi, Oligonychus Acupuncture, Aculops pelekassi, Phyllocoptruta citri, Aculops lycopersici, Calacarus carinatus, Acaphylla Pseudomonas such as theavagrans), Eriophyes chibaensis, Aculus schlechtendali, etc., dust mites such as Polyphagotarsonemus latus, and pseudonyms of Brevipalpus phoenicis Leaf mites, Duke mites, Haemaphysalis longicornis, Haemaphysalis flava, Dermacentor taiwanicus, Dermacentor variabilis, Ixodes Ovalus), Ixodes persulcatus, Ixodes scapularis, Amblyomma americanum, Boophilus microplus, Rhipicephalus sanguineus, etc. House dust mites such as Tyrophagus putrescentiae, Tyrophagus similis, Dermatophagoides farinae, and Dermatophagoides ptrenyssnus , Cheyletus eruditus, Cheyletus malaccensis, Cheyletus moorei, Cheyletiella yasguri, etc., Octodectes cynotis, Bovine aphids (Sacroptes scabiei), such as the mites, canine mites (Demodex canis), etc., hair follicles, mites, mites, Oribatid, Ornithonyssus bacoti, apple locust (Ornithonyssus sylvairum), chicken skin hedgehog (Dermanyssus gallinae), such as chicken mites, red mites (Leptotrombidium akamushi) and the like.

Arachnid pests: spiders such as Chiracanthium japonicum and Latrodectus hasseltii.

Lip and foot classes: Thereuonema hilgendorfi, Scolopendra subspinipes, etc.

Foot-types: Oxidus gracilis, Nedyopus tambanus, etc.

Waiting for the foot: Armadillidium vulgare and so on.

Gastropods: Limax marginatus, Limax flavus, etc.

The pest control agent of the present invention contains the compound of the present invention and an inert carrier. The pest control agent of the present invention is usually an inert carrier which mixes the compound of the present invention with a solid carrier, a liquid carrier, a gaseous carrier, etc., if necessary, a surfactant, an auxiliary agent for other preparations, and is formulated into an emulsion or an oil agent. , powders, granules, hydrating agents, suspending agents, microcapsules, aerosols, fumigants, baits, resin preparations, shampoos, paste preparations, foaming agents, carbonic acid gas preparations, tablets, and the like. These preparations are also processed into mosquito coils, electric mosquito tablets, liquid mosquito killing agents, fumigants, fumigants, sheet preparations, spot-on agents, oral treatments, and the like.

The pest control agent of the present invention usually contains 0.01 to 95% by weight of the compound of the present invention.

In the present invention, the compound of the present invention will contain a surfactant dispersed The pest control agent which is made of water is usually mixed with the compound of the present invention and a surfactant and water, and if necessary, an auxiliary agent for other preparations is added, and it is formulated into a suspending agent or a microcapsule.

The pest control agent usually contains 0.01 to 95% by weight of the compound of the present invention.

The term "dispersed in water" means that the compound of the present invention is in an opaque state and suspended in water.

Examples of the surfactant include a nonionic surfactant and/or an anionic surfactant. Examples of the nonionic surfactant include a polyoxyalkylene alkyl ether, a polyoxyalkylene alkyl aryl ether, and a polyethylene glycol fatty acid ester. Examples of the anionic surfactant include an alkyl sulfonate and an alkane. A benzenesulfonate, an alkyl sulfate, a polyoxyalkylene aryl phenyl ether sulfate, a polyoxyalkylene aryl phenyl ether phosphate, and the like.

Examples of the auxiliary agent for other preparations include a fixing agent, a dispersing agent, a coloring agent, a thickening agent, a preservative, an antifoaming agent, an antifreezing agent, a stabilizer, etc., specifically, casein, gelatin, starch, gum arabic. , cellulose derivatives, alginic acid, lignin derivatives, synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, etc.), PAP (isopropyl acid phosphate), BHT (2, 6-Di-tert-butyl-4-methylphenol), BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).

As an effective method for controlling pests in the agricultural field of the present invention, an effective amount of the compound of the present invention (for example, any of the compounds 1 to 18 of the present invention) can be applied to the soil of the stems and leaves of the plants or the cultivated plants. square Specific examples of the method include treatment of plant stems and leaves such as stems and leaves, treatment of plants such as soil treatment and hydroponic treatment, and the like. The number of applications may be one or more times.

Specific examples of the treatment of the stems and leaves of the plant include a method of applying to the surface of the plant, such as stem and leaf spreading, and trunk spreading.

Examples of the soil treatment include soil distribution, soil mixing, and chemical liquid perfusion (drug irrigation, soil injection, and chemical drip). As a place for treatment, for example, planting, sputum, and planting are mentioned. Near the hole, near the sputum, the comprehensive cultivation area, the plant edge, the plant, the trunk, the trunk, the soil, the nursery box, the seedling tray, the seedbed, etc., as the treatment period, it can be enumerated before sowing, sowing, and sowing immediately. After, during seedling, before planting, at the time of planting, and after the planting period.

Examples of the hydroponic treatment include injection of irrigation equipment (tubes, irrigation pipes, water sprayers, etc.), mixing of dip aqueous immersion liquids, and mixing of hydroponic liquids.

The pest control method of the present invention is generally used in the form of the pest control agent of the present invention.

When the pest control agent of the present invention is used for pest control in the agricultural field, the amount of the compound of the present invention per 10,000 m ² is usually from 1 to 10,000 g. When the pest control agent of the present invention is formulated into an emulsion, a hydrating agent, a suspending agent, or the like, the concentration of the active ingredient is usually diluted with water so as to be 0.01 to 10,000 ppm, and the granules, powders, and the like are usually directly applied.

When the pest control agent of the present invention is applied to a nursery box of a leech, The application amount of the compound of the present invention is usually 0.1 to 10 g per seedling box. When the pest control agent of the present invention is formulated into an emulsion, a hydrating agent, a suspending agent or the like, the compound of the present invention is usually applied by dilution with water in a form of 0.01 to 10000 ppm, and the granules, powders, and the like are directly applied in an amount of 1 to 500 g. Inventive compound.

The aqueous dilution of such preparations or preparations can be directly distributed from pests or pests to plants such as crops to be protected, and in order to control pests in the soil of the cultivated land, the soil can also be treated.

Further, the resin preparation processed into a sheet shape or a string shape (rope shape) may be wound up in a crop, pulled in the vicinity of the crop, and applied to the soil of the plant head to be treated.

In the present invention, the pest control agent containing the compound of the present invention and a feeding carrier is usually a compound in which a compound of the present invention and a feeding carrier (e.g., water, or a nutrient such as a sugar, a protein, or a lipid) are mixed.

Examples of the edible carrier include sugars such as sucrose, glucose, granulated granulated sugar, fructose, lactose, maltose, black granulated sugar, red granulated sugar, soft brown sugar, dextrin, arabinose, galactose, sorbose, molasses, honey, and the like; Dairy products such as skim milk, skimmed milk powder, cheese, etc.; starch from corn, potato, sweet potato, etc.; grain flour of flour, rice flour, corn flour, potato powder, etc.; animal powder or insect of cattle, pig, seafood, insects, etc. Vegetable oils such as coconut oil, cocoa butter, corn oil, sesame oil, peanut oil, salad oil, etc.; animal oils such as oils derived from body fats, milk fats, birds, reptiles, amphibians, insects, etc. of mammals; sauces Seasonings such as soy sauce, and if necessary, adding dibutylhydroxytoluene, reducing dihydrogen An antioxidant such as Nordichydroguaiaretic acid, a preservative such as dehydroacetic acid, an anti-feeding agent such as paprika, or a pest-preventing agent such as a cheese flavor or an onion spice peanut oil.

The form of the poison bait composition of the present invention is not particularly limited, and may be, for example, various forms such as a pellet form, a block form, a tablet form, a liquid form, a semi-paste form, and a gel form.

In the method for controlling pests in the field of epidemic prevention according to the present invention, in the place where the pests are easily aggregated, (1) when the composition of the poison bait of the present invention is a solid matter such as a powder, a granule, a lump, or a lozenge shape, The composition of the poison bait according to the present invention is set to be placed in an open container, (2) when the composition of the poison bait of the present invention is liquid, the composition of the poison bait of the present invention is applied, and (3) the composition of the poison bait of the present invention is gelatinous or In the case of a semi-paste, the bait composition of the present invention is injected into the space using a bait gun or the like, or adhered to the like, and the ingested bait composition of the present invention is taken up.

In the present invention, the pest control agent containing the compound, solvent and jet gas of the present invention is usually obtained by placing the compound of the present invention together with a solvent in a spray can, and after installing a spray valve, by mounting a driver for filling the gas.

Examples of the solvent include water, alcohol (methanol, ethanol, isopropanol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, phenoxyethanol, etc.), and ketones (acetone, methyl ethyl b). Alkyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (toluene, xylene, ethylbenzene, dodecylbenzene, phenyldimethylphenylethane, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, Cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, isopropyl myristate, oleic acid) Ethyl ester, diisopropyl adipate, diisobutyl adipate, propylene glycol monomethyl ether acetate, etc., nitriles (acetonitrile, isobutyronitrile, etc.), 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-methyl Oxy-3-methyl-1-butanol, etc.), acid amides (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloro Methane, trichloroethane, carbon tetrachloride, etc.), anthraquinones (dimethyl hydrazine, etc.), propylene carbonate and vegetable oils (soybean oil, cottonseed oil, etc.).

Examples of the injection gas include fluorocarbon, butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbonic acid gas.

The spray valve is not particularly limited, but a push-down spray valve is generally used.

In the present invention, the pest control agent containing the compound of the present invention and a gas generating agent is usually obtained by mixing the compound of the present invention and a gas generating agent.

Examples of the gas generating agent include azobisformamide, 4,4'-oxybis(phenylsulfonium), dinitropentamethylenearomatic tetraamine, and 2,2'-azobis. Nitrile, p-toluenesulfonate, and the like.

When the pest control agent of the present invention is used in the field of epidemic prevention, the amount of the compound of the present invention per 1 m ² of the treatment area when the surface is applied to the surface is usually 0.01 to 1000 mg, and when treated in a space, the treatment space is used. The amount of the compound of the invention of 1 m ³ is usually from 0.01 to 500 mg. When the pest control agent of the present invention is formulated into an emulsion, a hydrating agent, a suspending agent, etc., the concentration of the active ingredient is usually diluted with water to be 0.1 to 10000 ppm, and the oil agent, the aerosol agent, the smoke agent, and the poison bait agent are applied. The application is carried out without dilution. When the aerosol of the present invention is sprayed on a habitat of a pest or a pest, the amount of the compound of the present invention per 1 m ² of the treated area is usually 0.01 to 1000 mg when it is treated on the surface, and when it is treated in a space, The amount of the compound of the present invention per 1 m ³ of the treatment space is usually from 0.01 to 500 mg.

When the pest control agent of the present invention is used in the field of epidemic prevention, a method of applying the pest to the surface of the animal body, or applying the pest to the surface of the animal body for oral administration can be mentioned. Specifically, when used in the prevention of external parasites in small animals such as cattle, horses, pigs, sheep, goats, chickens, dogs, cats, rats, mice, etc., they are used in livestock or in a veterinary known manner. Small animals. When the systemic inhibition is used as a specific method of use, for example, when a tablet, a feed is mixed, a drug is administered, an injection (intramuscular, subcutaneous, intravenous, intraperitoneal, or the like) is administered, and non-systemic inhibition is used as an object, for example, Spray oil or aqueous liquid, Pour-on treatment or spot-on treatment, wash the animal with shampoo preparation or make the first round of the resin preparation or ear attached to livestock or small animals. Method used. The amount of the compound of the present invention when administered to the surface of an animal body is usually in the range of 0.1 to 1000 mg with respect to 1 kg of the body weight of livestock or small animals. The amount of the compound of the present invention when the animal is orally administered is usually in the range of 0.1 to 1000 mg with respect to 1 kg of the body weight of livestock or small animals.

The pest control agent of the present invention can be used for cultivating agricultural land of the following crops.

Crops: corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybeans, peanuts, buckwheat, sugar beet, rapeseed, sunflower, sugar cane, tobacco, etc.

Vegetables; Solanaceae vegetables (eggplant, tomato, green pepper, pepper, potato, etc.), Cucurbitaceae vegetables (cucumber, pumpkin, zucchini, watermelon, melon, etc.), cruciferous vegetables (radish, turnip, western wasabi, stalk, cabbage , kale, mustard, broccoli, broccoli, etc.), chrysanthemum vegetables (burdock, chrysanthemum, artichoke, lettuce, etc.), liliaceae vegetables (onions, onions, garlic, asparagus), umbelliferous vegetables (carrots, parsley, celery) , parsnips, etc.), leeks (spinach, leaf beet, etc.), mint vegetables (Japanese basil, mint, basil, etc.), strawberries, sweet potatoes, yam, taro, etc.

Fruit trees: pome fruit (apple, pear, Japanese pear, rosewood, alfalfa, etc.), stone fruit (peach, peach, nectarine, plum, cherry, apricot, sour plum, etc.), citrus (Wenzhou mandarin, citrus, Lemon, lime, grapefruit, etc., nuts (chestnuts, walnuts, hazelnuts, almonds, pistachios, cashews, macadamia nuts, etc.), berries (blueberries, cranberries, blackberries, raspberries, etc.), grapes, persimmons Olives, alfalfa, bananas, coffee, dates, coconuts, oil palms, etc.

Trees other than fruit trees: tea, mulberry, flower and wood (azalea, camellia, hydrangea, camellia, anise, cherry, tulip, crape myrtle, osmanthus, etc.), street trees (ash, birch, hawthorn, eucalyptus, ginkgo, Clove, maple, oak, poplar, bauhinia, sweetgum, sycamore, eucalyptus, thuja, fir, hemlock, juniper, pine, spruce, yew, eucalyptus, horse chestnut, etc.), coral tree, arhat Pine, cedar, cypress, croton, Big leaf boxwood, light leaf heather, and so on.

Grassland: grasses (knot, grass, stalks, etc.), Bermuda grasses (Berda grass, etc.), cockroaches (糠 草 grass, 匍匐翦 stock, Xia 糠 草 grass, etc.), bluegrass (P. gracilis, C. serrata, etc.), fescue (high fescue, purple fescue, tall fescue, etc.), ryegrass (rat, ryegrass, etc.), Dactylis sylvestris, and sage.

Others: flowers (roses, carnations, chrysanthemums, bellflowers, gypsophila, gerbera, marigold, sage, petunia, verbena, tulip, astor, gentian, lily, pansy, celery Kelai, orchid, lily of the valley, lavender, violet flower, kale, primrose, poinsettia, gladioli, garland, chrysanthemum, orchid, begonia, etc., biofuel plants (jatropha, tung tree, safflower oil tree, Flaxseed, switchgrass, miscanthus, grass, ruthenium, kenaf, cassava, willow, algae, etc.), foliage plants, etc.

In the present application, the term crop is also used to include genetically modified crops.

The pest control agent of the invention may be mixed with or used in combination with other insecticides, acaricides, nematicides, fungicides, plant growth regulators, herbicides and synergists. Examples of the active ingredients of the insecticide, acaricide, nematicide, bactericide, herbicide, and synergist are shown below.

Active ingredient of insecticide

(1) Organic phosphorus compounds

Acephate, Aluminium phosphide, butathiofos, cadusafos, oxyphosphonate (chlorethoxyfos), chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, cyanophos (CYAP), diazinon, dichlorodiisopropyl ether ), deichlofenthion (ECP), dichlorvos (DDVP), dimethoate, dimethylvinphos, disulfoton, EPN, ethion ), ethoprophos, etrimfos, fenthion (MPP), fenitrothion (MEP), fosthiazate, formothion, phosphine (Hydrogen phosphide), isofenphos, isoxathion, malathion, mesulfenfos, methidathion (DMTP), monocrotophos, narcissus (naled: BRP), oxydeprofos (ESP), parathion, phosalone, phosmet (PMP), pirimiphos-methyl, bifen Pyridafenthion, quinalphos, phenthoate (PAP), bupros (prof) Enofos), propaphos, prothiofos, pyraclorfos, salithion, sulprofos, tebupirimfos, and alepicon ( Temephos), tetrachlorvinphos, terbufos, thiometon, trichlorphon (DEP), vamidothion, and phorate.

(2) Carbamate compounds

Alanycarb, bendiocarb, benfuracarb, BPMC, carbaryl, carbofuran, carbosulfan, cloethocarb , ethiofencarb, fenobucarb, fenothiocarb, fenoxycarb, furathiocarb, isoprocarb (MIPC), bifenfen (metolcarb), methomyl, methiocarb, NAC, oxamyl, pirimicarb, propoxur (PHC), XMC, thiodicarb , xylylcarb, and aldicarb.

(3) Pyrethroid compounds

Acrinathrin, allethrin, benfluthrin, beta-cyfluthrin bifenthrin, cycloprothrin, cyfluthrin, Cyhalothrin, cypermethrin, deltamethrin, esfenvalerate, ethofenprox, fenpropathrin, fenvalerate, escort Flucythrinate, flufenoprox, flumethrin, fluvalinate, halfenprox, imiprothrin, permethrin ), prallethrin, pyrethrins, resmethrin, sigma-cypermethrin, silafluofen, tefluthrin, four Bromomethrin (tralomethrin), transfluthrin, tetramethrin, phenothrin, cyphenothrin, alpha-cypermethrin, Jay-Syrene (zeta-cypermethrin), lambda-cyhalothrin, gamma-cyhalothrin, furamethrin, tau-fluvalinate, metofluthrin , profluthrin (profluthrin), dimefluthrin, 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl (EZ)-(1RS, 3RS; 1RS,3SR)-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-alkenyl)cyclopropanecarboxylate, 2,3,5,6-tetrafluoro -4-(Methoxymethyl)benzyl (EZ)-(1RS, 3RS; 1RS, 3SR)-2,2-dimethyl-3-(2-cyano-1-alkenyl)cyclopropanecarboxylate Acid ester.

(4) Neretoxin compound

Cartap, bensultap, thiocyclam, monosultap, and bisultap.

(5) Nicotinoid compounds

Imidacloprid, nitenpyram, acetamiprid, thiamethoxam, thiacloprid, dinotefuran, and clothianidin .

(6) Benzamidine urea compound

Chlorfluazuron, bistrifluron, diafenthiuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, Hexaflumuron, lufenuron, novaluron, noififlumuron, teflubenzuron, triflumuron, and triazuron.

(7) Phenylpyrazole compound

Acetoprole, ethiprole, fipronil, vaniliprole, pyriprole, and pyrafluprole.

(8) Bt toxin

From the spores of Bacillus thuringiensis and the production of crystalline toxins, and mixtures thereof;

(9) bismuth compound

Chromofozide, halofenozide, methoxyfenozide, and tebufenozide.

(10) organochlorine compounds

Aldrin, dieldrin, dienochlor, endosulfan, and methoxychlor.

(11) Other active ingredients of pesticides

Machine oil, nicotine-sulfate; avermectin-B, new bromopropylate, buprofezin, chlorphenapyr, race Cyromazine, 1,3-Dichloropropene, emamectin-benzoate, fenazaquin, flupyrazofos, olefin Hydroprene, methoprene, indoxacarb, metoxadiazone, milbemycin-A, pymetrozine, acetamiprid ( Pyridalyl), pyriproxyfen, spinosad, sulfluramid, tolfenpyrad, triazamate, lepimectin, arsenite (Arsenic acid), benclothiaz, calcium cyanamide, calcium polysulfide, chlordane, DDT, DSP, flufenerim, flonicamid ), flurimfen, formetanate, metam-ammonium, metam-sodium, methyl bromide (Methyl br) Omide), Potassium oleate, (protrifenbute), spiromesifen, sulfoxaflor, sulfur, metaflumizone, spirotetramat , new quinazoline (pyrazine), pyretoram, tramopyril, flupyradifurone, chlorantraniliprole ), cyantraniliprole, flubendiamide, a compound represented by the following formula (K); Wherein R ¹⁰⁰ represents chlorine, bromine or trifluoromethyl, R ²⁰⁰ represents chlorine, bromine or methyl, and R ³⁰⁰ represents chlorine, bromine or cyano.

And a compound represented by the following formula (L); [wherein R ¹⁰⁰⁰ represents a chlorine atom, a bromine atom or an iodine atom].

Active ingredient of acaricide

Acequinocyl, amitraz, benzoximate, bifenazate, bromopropylate, chinomethionat, chlorobenzene (chlorobenzilate), eucalyptus CDS (chlorfenson), clofentezine, cyflumetofen, kelusan (difofol), etoxazole, fenbutatin oxide ), fenothiocarb, fenpyroximate, fluacrypyrim, fluproxyfen, hexythiazox, propargite (BPPS), liuyangmycin complex Polynactins, pyridaben, Pyrimidifen, tebufenpyrad, tetradifon, spirodiclofen, spiromesifen, spirochetes Spirotetramat, amidoflumet, and cyenopyrafen.

Active ingredient of nematicide

DCIP, fosthiazate, levamisol hydrochloride, methyl isothiocyanate, morantel tartarate, and imicyafos.

Active ingredient of fungicide

(1) azole compound

Triforine, imazalil, pefurazoate, prochloraz, triflumizole, bitertanol, bromuconazole, ring gram Block (cyproconazole), waiting for Klee (difenoconazole), diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flurifaol, Fickley (hexaconazole), ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, tebuconazole , tetraconazole, triadimenol, triticonazole, etc.;

(2) Strobilurin compound

Azoxystrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, inseczobin Enestrobin), dimoxystrobin, oressastrobin, fluoxastrobin, famoxadone, fenamidone, pyribencarb, etc.;

(3) Other fungicide active ingredients

Carbendazim, benomyl, thiabendazole, thiophanate-methyl, zoxamide, diethofencarb, pentosan ( Pencycuron), fluopicolide, carboxin, frutolanil, frametpyr, thifluzamide, boscalid, penthiol (penthiopyrad), fluopyram, bixafen, isopyrazam, penflufen, sedaxan, flurazia Fluxapyroxad, fluazinam, ferimzone, silthiofam, procymidone, iprodione, vinclozolin, chlordane Metalaxyl, benalaxyl, pyrimethanil, mepanipyrim, cyprodinil, quinoxyfen, proquinazid, seed dressing (fenpiclonil), fludioxonil, fenhexamid, fenpropimorph, tridemorph, fenpropidin, spiroxamine, thiura Thiuram, ziram, mancozeb, chlorothalonil, dichlofluanid, captan, folpet, iminoctadine ), ethaboxam, metrafenone, dodine, fthalide, tricyclazole, praziquantel ( Pyroquilon), carpropamid, diclocymet, fenoxanil, dimethomorph, iprovalicarb, benthiavalicarb , mandipropamid, tolclofos-methyl, quintozene, cyazofamid, amisulbrom, ametoctradin, cyprofamine (cyflufenamid), validamycin A, polyoxin B, blasticidin-S, kasugamycin, oxolinic acid )Wait;

(4) Resistance-inducing compounds

Acibenzolar-S-methyl, probenazole, isotianil, and tiadinil.

Herbicidal active ingredient

(1) phenoxy fatty acid herbicidal compound

2,4-PA, MCP, MCPB, phenothiol, mecoprop, fluroxypyr, triclopyr, clomeprop, and chlorpyrifos Dan (naproanilide).

(2) benzoic acid herbicidal compounds

2,3,6-TBA, dicamba, clopyralid, picloram, aminopyralid, quinclorac, and chloroquinolinic acid Quinmerac).

(3) Urea herbicidal compound

Diuron, linuron, chlortoluron, isoproturon, fluometuron, isouron, tebuthiuron, thiazolyl Methabenzthiazuron), cumyluron, daimuron, and methyl-daimuron.

(4) Triazine herbicidal compounds

Atrazine,ametoryn, cyanazine, simazine, propazine, simetryn, dimethametryn, flutter Prometryn, metribuzin, triaziflam, and indaziflam.

(5) Bipyridyl herbicide compounds

Paraquat, and diquat.

(6) hydroxybenzonitrile herbicidal compound

Bromoxynil, and ioxynil.

(7) Dinitroaniline herbicidal compound

Pendimethalin, prodiamine, and trifluralin.

(8) Organophosphorus herbicidal compounds

Amyprofos-methyl, butamifos, bensulide, piperophos, anilofos, glyphosate, sessile grass Glufosinate), glufosinate-P, and bialaphos.

(9) Carbamate herbicidal compounds

Di-allate, tri-allate, EPTC, butarate, benthiocarb, esprocarb, molinate, piperacine Dimepiperate, swep, chlorpropham, phenmedipham, phenisopham, pyributicarb, and asulam.

(10) acid amide herbicidal compound

Propanil, propyzamide, bromobutide, and etobenzanid.

(11) chloroacetamide benzene herbicidal compound

Acetochlor, alachlor, butachlor, dimethenamid, propachlor, metazachlor, metolachlor, Pretilachlor, thenylchlor, and pethoxamid.

(12) Diphenyl ether herbicidal compound

Acifluorfen-sodium, bifenox, oxyfluorfen, lactofen, fomesafen, chlomethoxynil , and alexifen (aclonifen).

(13) cyclic quinone imine herbicidal compound

Oxadizon, cinidon-ethyl, carfentrazone-ethyl, sulfentrazone, flumiclorac-pentyl, flufenacetamide (flumioxazin), pyraflufen-ethyl, oxadiargyl, pentoxazone, fluthiacet-methyl, butafenacil, Benzfendizone, bencarbazone, and saflufenacil.

(14) Pyrazole herbicidal compounds

Benzofenap, pyrazolate, benzoxazol (pyrazoxyfen), oxacillin (topramezone), and sulfosyl pyrazole (pyrasulfotole).

(15) Triketone herbicidal compound

Isoxaflutole, benzobicyclon, sulcotrione, mesotrione, tembotrione, and tefuryltrione.

(16) aryloxyphenoxypropionic acid herbicidal compound

Clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, A Base haloxyfop-methyl, and quizalofop-ethyl, metamifop.

(17) Triketone oxime herbicidal compound

Alloxydim-sodium, sethoxydim, butroxydim, clethodim, cloproxydim, cycloxydim, Tepraloxydim, tralkoxydim, and profoxydim.

(18) sulfonylurea herbicidal compound

Chlorsulfuron, sulfometuron-methyl, metsulfuron-methyl, chlorimuron-ethyl, tribenuron-methyl, ether benzene Triasulfuron, bensulfuron-methyl, chlorothiophene sulfonate Thifensulfuron-methyl, pyrazosulfuron-ethyl, primisulfuron-methyl, nicosulfuron, amidosulfuron, cinosulfuron, Izosulfuron, rimsulfuron, halosulfuron-methyl, prosulfuron, ethametsulfuron-methyl, triflusulfuron -methyl), flazasulfuron, cyclosulfamuron, flupyrsulfuron, sulfosulfuron, azimsulfuron, ethoxysulfuron , oxasulfuron, iodosulfuron-methyl-sodium, foramsulfuron, mesosulfuron-methyl, trifloxysulfuron, Tritosulfuron, orthosulfamuron, flucetosulfuron, and propyrisulfuron.

(19) Imidazoline herbicidal compounds

Imazamethabenz-methyl, imazamethapyr, imazamox, imazapyr, imazaquin, and imazethapyr.

(20) indole herbicidal compound

Flumetsulam, metosulam, diclosulam, florasulam, cloransulam-methyl, penoxsulam, Acesulfame (pyroxsulam).

(21) pyrimidineoxybenzoic acid herbicidal compound

Pyrithiobac-sodium, bispyribac-sodium, pyriminobac-methyl, pyribenzoxim, pyrifalid, and pyrimisulfan ).

(22) Other herbicidal compounds

Bentazon, bromacil, terbacil, chlorthiamid, isoxaben, dinoseb, amitrol, Cinmethylin, tridiphane, dalapon, diflufenzopyr-sodium, dithiopyr, thiazopyr, flurazepam Flucarbazone-sodium, propoxycarbazone-sodium, mefenacet, flufenacet, fentrazamide, cafenstrole, humulone (indanofan), oxaziclomefone, benfuresate, ACN, pyridate, chloridazon, norflurazon, flurtamone, pyridoxine Diflufenican, picolinafen, beflubutamid, clomazone, amicarbazone, pinoxaden, oxalox Nitrile (pyraclonil), pyroxasulfone, thiencarbazone-methyl, aminocyclopyrachlor, AI Pakistan hydrazone (ipfencarbazone), and metisozolin.

Active ingredient of synergist

Piperonyl butoxide, sesamex, sulfoxide, N-(2-ethylhexyl)-8,9,10-three norborn-5-ene-2,3 -Dicarboxy quinone imine (MGK 264), N-declyimidazole, WARF-antiresistant, TBPT, TPP, IBP, PSCP, methyl iodide (CH ₃ I), t-phenylbutenone (t-phenylbutenone), diethylmaleate, DMC, FDMC, ETP, and ETN.

Example

Hereinafter, the present invention will be further described in detail with reference to Production Examples, Reference Production Examples, Preparation Examples, Test Examples, and the like, but the present invention is not limited thereto.

First, a production example is shown for the production of the compound of the present invention.

Manufacturing Example 1 (1)

0.48 ml of bromine was added dropwise at 85 ° C to a mixture of 1.21 g of 1-(3-chloropyridin-2-yl)ethanone, 3 ml of a 25% hydrogen bromide-acetic acid solution, 5 ml of acetic acid and 2.5 ml of water, and at 85 ° C. Stir for 1 hour. The reaction mixture was allowed to cool to room temperature and the precipitated solid was filtered. The obtained solid was washed with tert-butyl methyl ether, and then dried to give 1. <RTIgt; </RTI> <RTIgt; </RTI> 2-bromo-1-(3-chloropyridin-2-yl)-ethanone hydrobromide.

2-bromo-1-(3-chloropyridin-2-yl)ethanone hydrobromide

¹ H-NMR (DMSO-D ₆ ) δ: 8.68 (1H, dd), 8.14 (1H, dd), 7.70 (1H, dd), 4.96 (2H, s).

Manufacturing Example 1 (2)

A mixture of 700 mg of 2-bromo-1-(3-chloropyridin-2-yl)ethanone hydrobromide, 360 mg of 2-amino-5-trifluoromethylpyridine, 187 mg of sodium hydrogencarbonate and 4 ml of ethanol was refluxed 3 hour. To the reaction mixture was added 187 mg of sodium hydrogencarbonate and refluxed for 1 hour. Water was added to the reaction mixture which was allowed to cool to room temperature and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate The obtained residue was subjected to silica gel column chromatography to give 426 mg of 2-(3-chloropyridin-2-yl)-6-trifluoromethylimidazo[1,2-a]pyridine.

2-(3-chloropyridin-2-yl)-6-trifluoromethylimidazo[1,2-a]pyridine

¹ H-NMR (CDCl ₃ ) δ: 8.74 (1H, dd), 8.59-8.56 (1H, m), 8.52 (1H, s), 7.87-7.81 (2H, m), 7.37 (1H, dd), 7.29 -7.24 (1H, m).

Manufacturing Example 1 (3)

A mixture of 40 mg of sodium hydride (60% oily) and 1 ml of DMF was added to 63 μl of ethanethiol under ice cooling, followed by the addition of 2-(3-chloropyridin-2-yl)-6-trifluoromethylimidazole dissolved in 1.5 ml of DMF. And [1,2-a]pyridine 213 mg. After the reaction mixture was stirred at room temperature for 30 minutes, water was added and extracted with tert-butyl methyl ether. The organic layer was washed with water, dried over anhydrous magnesium sulfate The obtained solid was washed with a solution of tert-butyl methyl ether:hexane = 2:1, and dried to give 2-(3-ethylthiopyridin-2-yl)-6-trifluoromethyl Imidazo[1,2-a]pyridine (hereinafter referred to as Compound 1 of the present invention) was 155 mg.

Compound 1 of the invention

¹ H-NMR (CDCl ₃ ) δ: 8.57-8.51 (2H, m), 8.43 (1H, s), 7.83 (1H, d), 7.71 (1H, dd), 7.34 (1H, dd), 7.27-7.22 (1H, m), 2.99 (2H, q), 1.37 (3H, t).

Manufacturing Example 2

A mixture of the compound 1 (155 mg) of the present invention and 2 ml of chloroform was added to 265 mg of 3-chloroperoxybenzoic acid (purity: 65% or more) under ice cooling, and stirred at room temperature for 1 hour. Add 10% sodium thiosulfate water solution to the reaction mixture The solution was extracted with chloroform. The organic layer was washed with saturated aqueous sodium hydrogen sulfate and dried over anhydrous magnesium sulfate. The obtained solid was washed with a solution of tert-butyl methyl ether:hexane = 2:1, and dried to give 2-(3-ethylsulfonylpyridin-2-yl)-6-trifluoromethyl 131 mg of imidazo[1,2-a]pyridine (hereinafter referred to as Compound 2 of the present invention).

Compound 2 of the invention

¹ H-NMR (CDCl ₃ ) δ: 8.92 (1H, dd), 8.59-8.52 (2H, m), 8.33 (1H, s), 7.75 (1H, d), 7.54 (1H, dd), 7.39 (1H) , dd), 3.81 (2H, q), 1.31 (3H, t).

Manufacturing Example 3

A mixture of the compound 2 (180 mg) of the present invention, 68 mg of N-chlorosuccinimide, 2 ml of DMF and 0.5 ml of acetonitrile was stirred at 50 ° C for 30 minutes, and then stirred at 70 ° C for 1 hour. A saturated aqueous solution of sodium carbonate was added to the mixture and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate The obtained solid was washed with a solution of tert-butyl methyl ether:hexane = 2:1, and dried to give 3-chloro-2-(3-ethylsulfonylpyridin-2-yl)-6 - 196 mg of trifluoromethylimidazo[1,2-a]pyridine (hereinafter referred to as Compound 3 of the present invention).

Compound 3 of the invention

¹ H-NMR (CDCl ₃ ) δ: 8.96 (1H, dd), 8.55-8.50 (2H, m), 7.72 (1H, d), 7.61 (1H, dd), 7.45 (1H, dd), 3.91 (2H) , q), 1.36 (3H, t).

Manufacturing Example 4

A mixture of 4-chloro-5-trifluoromethylsulfonylpyridine 4 g, sodium azide 1.22 g and NMP 10 ml was stirred at 50 ° C for 3 hours, at 80 ° C for 3 hours, and then at 90 ° C for 3 hours. . Water was added to the reaction mixture, and extracted with tert-butyl methyl ether. The organic layer was washed with water, dried over anhydrous sodium sulfate The obtained residue was subjected to chromatography on a silica gel column to obtain 894 mg of 2-azido-5-trifluoromethylsulfonylpyridine.

2-azido-5-trifluoromethylsulfonylpyridine

¹ H-NMR (CDCl ₃ ) δ: 9.20-9.17 (1H, m), 8.12 (1H, dd), 7.86 (1H, dd).

Manufacturing Example 4 (2)

A mixture of 894 mg of 2-azido-5-trifluoromethylsulfonylpyridine, 1.12 g of triphenylphosphine, 6 ml of THF and 0.6 ml of water was stirred at room temperature for 1 hour and then stirred at 50 ° C for 2 hours. 5 ml of 2N hydrochloric acid was added to the reaction mixture, and the mixture was stirred at room temperature for 4 hours. After 1 N hydrochloric acid was added to the reaction mixture, and the mixture was washed with toluene, and then, aqueous layer was added to the aqueous layer, and the mixture was neutralized with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and evaporated to drynessiel

2-amino-5-trifluoromethylsulfonylpyridine

¹ H-NMR (CDCl ₃ ) δ: 8.28 (1H, d), 7.65 (1H, dd), 6.51 (1H, d), 4.77 (2H, brs).

Manufacturing Example 4 (3)

567 mg of 2-amino-5-trifluoromethylsulfonylpyridine, 1.05 g of 2-bromo-1-(3-fluoropyridin-2-yl)ethanone hydrobromide, 294 mg of sodium hydrogencarbonate and 4 ml of ethanol The mixture was refluxed for 2 hours. To the reaction mixture were added 178 mg of 2-bromo-1-(3-fluoropyridin-2-yl)ethanone hydrobromide and 49 mg of sodium hydrogencarbonate, and refluxed for 80 minutes. To the cooled reaction mixture was added saturated aqueous sodium bicarbonate and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate The obtained residue was subjected to chromatography on a silica gel column to obtain 2-(3-fluoropyridin-2-yl)-6-trifluoromethylsulfonyl imidazole. [1,2-a]pyridine 665 mg.

2-(3-Fluoropyridin-2-yl)-6-trifluoromethylsulfonylimidazo[1,2-a]pyridine

¹ H-NMR (CDCl ₃ ) δ: 8.67-8.60 (1H, m), 8.57-8.53 (1H, m), 8.30-8.25 (1H, m), 7.80-7.74 (1H, m), 7.59-7.50 ( 1H, m), 7.43-7.36 (1H, m), 7.35-7.29 (1H, m).

Manufacturing Example 4 (4)

A mixture of 0.19 ml of ethanethiol, 118 mg of sodium hydride (60% oily) and 2 ml of DMF was added to 2-(3-fluoropyridin-2-yl)-6-trifluoromethylsulfonyl imidazole [1] under ice cooling. A mixture of 657 mg of 2-a]pyridine and 2 ml of DMF was stirred at room temperature for 1 hour. The reaction mixture was poured into water, and the precipitated solid was filtered. The obtained solid was washed with water and hexane, and dried to give 2-(3-ethylthiopyridin-2-yl)-6-trifluoromethylsulfonyl-imidazo[1,2 -a] pyridine (hereinafter referred to as compound 11 of the present invention) 616 mg.

Compound 11 of the invention

¹ H-NMR (CDCl ₃ ) δ: 8.54 - 8.51 (2H, m), 8.37 (1H, d), 7.77- 7.73 (1H, m), 7.70 (1H, dd), 7.36 (1H, dd), 7.24 (1H, dd), 2.99 (2H, q), 1.38 (3H, t).

Manufacturing Example 5

A mixture of the compound 11 (616 mg) of the present invention and 20 ml of ethyl acetate was added, and 797 mg of m-chloroperoxybenzoic acid (purity: 65% or more) was added under ice cooling, and the mixture was stirred at room temperature for 3 hours. An aqueous solution of sodium thiosulfate and a saturated aqueous solution of sodium hydrogencarbonate were added and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen sulfate solution, dried over anhydrous sodium sulfate and evaporated.]]]~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ Sulfonimidoimidazo[1,2-a]pyridine (hereinafter referred to as compound 12 of the present invention) 642 mg.

Compound 12 of the invention

1H-NMR (CDCl ₃ ) δ: 8.91 (1H, dd), 8.57-8.53 (2H, m), 8.28 (1H, d), 7.67 (1H, d), 7.54 (1H, dd), 7.41 (1H, Dd), 3.86 (2H, q), 1.32 (3H, t).

The compounds produced by the methods described in the above-mentioned production examples and the production methods described in the above-mentioned production examples are shown in the table.

a compound represented by the formula (1A).

In the formula, R ² , R ³ , R ⁴ , R ⁵ and n represent the combinations described in [Table 3].

a compound represented by the formula (1B).

In the formula, R ² , R ³ , R ⁴ and n represent the combinations described in [Table 4].

a compound of the formula (1-3).

In the formula, R ² , R ³ , R ⁴ and n represent the combinations described in [Table 5].

The ¹ H-NMR data of the compound of the present invention described in [Table 3] to [Table 5] are shown below.

Compound 4 of the invention

¹ H-NMR (CDCl ₃ ) δ: 8.96 (1H, dd), 8.59-8.57 (1H, m), 8.52 (1H, dd), 7.72 (1H, d), 7.62 (1H, dd), 7.46 (1H) , dd), 3.88 (2H, q), 1.35 (3H, t).

Compound 5 of the invention

¹ H-NMR (CDCl ₃ ) δ: 8.71 (1H, s), 8.58 (1H, s), 8.48 (1H, s), 7.87-7.82 (2H, m), 7.38 (1H, dd), 3.05 (2H) , q), 1.43 (3H, t).

Compound 6 of the invention

¹ H-NMR (CDCl ₃ ) δ: 9.12 (1H, d), 8.78 (1H, d), 8.59 (1H, d), 8.40 (1H, s), 7.76 (1H, d), 7.41 (1H, dd ), 4.05 (2H, q), 1.38 (3H, t).

Compound 7 of the invention

¹ H-NMR (CDCl ₃ ) δ: 8.56-8.54 (1H, m), 8.44 (1H, d), 8.38 (1H, s), 7.82 (1H, d), 7.63 (1H, d), 7.35 (1H) , dd), 3.00 (2H, q), 1.41 (3H, t).

Compound 8 of the invention

¹ H-NMR (CDCl ₃ ) δ: 8.84 (1H, d), 8.56 (1H, d), 8.53 (1H, d), 8.31 (1H, s), 7.74 (1H, d), 7.39 (1H, dd ), 3.91 (2H, q), 1.35 (3H, t).

Compound 16 of the invention

¹ H-NMR (CDCl ₃ ) δ: 8.56 (1H, d), 8.35 (1H, d), 8.23 (1H, s), 7.73 (1H, d), 7.37 (1H, dd), 6.88 (1H, d ), 4.05 (3H, s), 3.87 (2H, q), 1.32 (3H, t).

Next, a formulation example of the compound of the present invention is shown. Also, the parts represent parts by weight.

Formulation Example 1

10 parts of any one of the present compounds 1 to 18, dissolved in a mixture of 35 parts of xylene and 35 parts of N,N-dimethylformamide, and 14 parts of polyoxyethylene styrylphenyl ether and twelve 6 parts of calcium alkylbenzenesulfonate was mixed to obtain various emulsions.

Formulation Example 2

4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of cerium oxide micropowder and 54 parts of diatomaceous earth, and further added to 20 parts of any one of the compounds 1 to 18 of the present invention, and mixed to obtain various kinds. Hydrating agent.

Formulation Example 3

To 2 parts of any of the compounds 1 to 18 of the present invention, 1 part of a fine powder of cerium oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and 65 parts of kaolin were mixed and mixed. Next, an appropriate amount of water is added to the mixture, and further stirred to granulate the granules, and air-dried to obtain various granules.

Formulation Example 4

1 part of any one of the present compounds 1 to 18 is dissolved in an appropriate amount of acetone, and 5 parts of cerium oxide micropowder, 0.3 parts of PAP and leaves are added thereto. 93.7 parts of wax stone, mixed well, and evaporated to remove acetone to obtain various powders.

Formulation Example 5

35 parts of a mixture of polyoxyethylene alkyl ether sulfate ammonium sulfate and white carbon (weight ratio 1:1), 10 parts of any one of the present compounds 1 to 18, and 55 parts of water, which are micro-milled by wet pulverization It is pulverized to obtain various suspending agents.

Formulation Example 6

0.1 part of any one of the present compounds 1 to 18 was dissolved in 5 parts of xylene and 5 parts of trichloroethane, and this was mixed with 89.9 parts of deodorizing lamp oil to obtain various oil agents.

Formulation Example 7

10 mg of any one of the present compounds 1 to 18 was dissolved in acetone (0.5 ml), and the solution was treated with 5 g of solid feed powder for animals (solid feed for feed breeding CE-2, product of CLEA Co., Japan), and uniformly mixed. . The acetone was then evaporated to obtain various baits.

Formulation Example 8

0.1 part of any one of the present compounds 1 to 18 and 49.9 parts of Neothiozole (Central Chemicals Co., Ltd.) were placed in a spray can, and after installing a spray valve, 25 parts of dimethyl ether and 25 parts of LPG were filled and vibration was added thereto. Install the driver to get the oil aerosol.

Formulation Example 9

0.6 parts of any one of the present compounds 1 to 18, 0.01 parts of BHT (2,6-di-tert-butyl-4-methylphenol), 5 parts of xylene, 3.39 parts of deodorized lamp oil, and an emulsifier are dissolved and dissolved. {RHEODOL MO-60 (manufactured by Kao Co., Ltd.)} One part was filled in an aerosol container with 50 parts of distilled water, and after installing a valve, 40 parts of a propellant (LPG) was pressurized and filled by the valve to obtain an aqueous aerosol.

Formulation Example 10

0.1 g of any one of the present compounds 1 to 18 was dissolved in 2 ml of propylene glycol, and impregnated into a porous ceramic plate of 4.0 × 4.0 cm and a thickness of 1.2 cm to obtain a heated fumigation agent.

Formulation Example 11

5 parts of any one of the present compounds 1 to 18 and ethylene-methyl methacrylate copolymer (methyl methacrylate ratio in copolymer: 10% by weight, Acryft WD 301, manufactured by Sumitomo Chemical Co., Ltd.) 95 parts in a closed form The kneaded kneader (manufactured by Moriyama Seisakusho Co., Ltd.) was melt-kneaded, and the obtained kneaded product was extruded through a molding die by an extrusion molding machine to obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm.

Formulation Example 12

5 parts of any one of the present compounds 1 to 18 and 95 parts of a soft vinyl chloride resin were melt-kneaded in a closed pressure kneading machine (manufactured by Moriyama Seisakusho Co., Ltd.), and the obtained kneaded product was passed through a molding die from an extrusion molding machine. The bar was molded to obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm.

Formulation Example 13

100 mg of any one of the present compounds 1 to 18, 68.75 mg of lactose, 237.5 mg of corn starch, 43.75 mg of microcrystalline cellulose, 18.75 mg of polyvinylpyrrolidone, 28.75 mg of sodium carboxymethyl starch, and magnesium stearate 2.5 mg, the resulting mixture was compressed to an appropriate size to obtain a tablet.

Formulation Example 14

Mixing 25 mg of any of the present compounds 1 to 18, 60 mg of lactose, 25 mg of corn starch, 6 mg of croscarmyl calcium, and 5% of hydroxypropylmethylcellulose, and filling the obtained mixture into hard shell gelatin capsules Or a hydroxypropyl methylcellulose capsule to obtain a capsule.

Formulation Example 15

1000 mg of any of the present compounds 1 to 18, 500 mg of fumaric acid, 2000 mg of sodium chloride, 150 mg of methyl hydroxybenzoate, 50 mg of propyl propyl benzoate (Propylparaben), 25,000 mg of granulated sugar, and 70% of sorbitol (70%) Solution) 13,000 mg, Veegum K (Vanderbilt Co.) 100 mg, fragrance 35 mg, and coloring material 500 mg, with a final capacity of 100 ml Distilled water was added thereto and mixed to obtain an orally administered suspension.

Formulation Example 16

5 wt% of any one of the present compounds 1 to 18 is dissolved in 85 wt% of polysorbate, 3 wt% of benzyl alcohol, and 30 wt% of propylene glycol, and phosphate is added in such a manner that the pH of the solution becomes 6.0 to 6.5. After the buffer solution, water was added to the final capacity to obtain an oral administration medicinal solution.

Formulation Example 17

In 57 wt% of fraction coconut oil and 853 wt% of polysorbate, it was dispersed by heating 5 wt% of aluminum distearate. This was cooled to room temperature to disperse 25% by weight of the saccharin in the oily vehicle. Here, 10% by weight of any one of the present compounds 1 to 18 is dispensed, and an orally administered pharmaceutically acceptable paste preparation is obtained.

Formulation Example 18

5% by weight of any of the present compounds 1 to 18 and 95% by weight of limestone powder were mixed, and an orally administered granule was obtained by a wet granule formation method.

Formulation Example 19

5 parts of any one of the present compounds 1 to 18 is dissolved in 80 parts of diethylene glycol monoethyl ether, and 15 parts of propylene carbonate is mixed thereto to obtain a neck drop. Liquid agent.

Formulation Example 20

10 parts of any one of the present compounds 1 to 18 was dissolved in 70 parts of diethylene glycol monoethyl ether, and 20 parts of 2-octyldodecanol was mixed thereto to obtain a pouring liquid.

Formulation Example 21

In 0.5 parts of any one of the present compounds 1 to 18, 60 parts of Nikkol TEALS-42 (42% aqueous solution of Daylight Chemicals. Triethanolamine sulfate) and 20 parts of propylene glycol were added, and the mixture was thoroughly stirred and mixed to obtain a homogeneous solution, and then water was added. The mixture is further thoroughly stirred and mixed to obtain a uniform solution of the shampoo.

Formulation Example 22

Mixing and mixing 0.15% by weight of any of the compounds 1 to 18 of the present invention, 95% by weight of animal feed, and from the second calcium phosphate, diatomaceous earth, aerosil (Aerosil), and carbonate (or chalk) The mixture was composed of 4.85 wt%, and a feed premix (Premix) for animals was obtained.

Formulation Example 23

7.2 g of any one of the present compounds 1 to 18 and 92.8 g of Hosuko S-55 (manufactured by Maruishi Pharmaceutical Co., Ltd.) were dissolved and mixed at 100 ° C, poured into a suppository form, and solidified by cooling to obtain a suppository.

Formulation Example 24

10 parts of any one of the compounds 1 to 18 of the present invention, 2 parts of polyoxyalkylene arylphenyl ether phosphate, 5 parts of propylene glycol, 0.2 part of a decane defoaming agent, and 58.5 parts of water were mixed by a wet pulverization method. Finely pulverized to obtain a suspension. To the suspension, a mixture of 0.4 parts of magnesium aluminum silicate, 0.2 parts of xanthan gum, 0.2 parts of a preservative, and 23.5 parts of water was added and mixed to obtain various suspending agents.

Formulation Example 25

A mixture of 10 parts of the compound 1 to 18 of the present invention and a mixture of 20 parts of an aromatic hydrocarbon (Solvesso 200ND, manufactured by Exxon Mobil Chemical Co., Ltd.) in an aqueous solution of polyvinyl alcohol prepared by dissolving 3 parts of polyvinyl alcohol in 43.5 parts of water. The emulsion was obtained by stirring using a stirrer. To the emulsion, 0.3 parts of aluminum magnesium citrate, 0.15 parts of xanthan gum, 0.2 parts of preservative and 17.65 parts of water, 5 parts of propylene glycol, and 0.2 parts of a decane defoaming agent were added and mixed to obtain various kinds. Suspending agent.

Formulation Example 26

A mixture of 3.6 parts of each of the compounds 1 to 18 of the present invention and 14.3 parts of acetone was added to obtain a solution. Here, 0.2 parts of zinc oxide, 1.0 part of α-starch, and 42.8 parts of azobisformamide were added, and 38.1 parts of water was added thereto, followed by kneading, and the mixture was formed into pellets and dried. The upper space of the container which is divided by the aluminum partition wall in the central portion, which contains the particles of the aforementioned compound of the present invention, 50 g of calcium oxide was contained in the lower space of the container to obtain a fumigant.

Formulation Example 27

0.5 parts of zinc oxide, 2 parts of α-starch, and 97.5 parts of azobisformamide were mixed, and water was added thereto for kneading, and the kneaded product was extruded into pellets to obtain granules. 2 g of the granules containing 0.58 g of each of the compounds of the present invention 1 to 18 were uniformly impregnated, and dried to obtain various particles containing the compounds 1 to 18 of the present invention. In the upper space of the container which is divided by the aluminum partition in the center, the particles of the compound of the present invention are contained, and 50 g of calcium oxide is contained in the lower space of the container to obtain a fumigant.

Next, the pest control efficacy of the compound of the present invention is shown by a test example.

Test example 1

The test compound liquids were prepared by diluting the preparations of the compounds 2, 3, 4, 6, 12, and 16 of the present invention obtained in Formulation Example 5 with water at a concentration of 500 ppm.

In addition, about 30 cucumbers (Aphis gossypii) (all stages) were inoculated in a plastic cup of cucumber seedlings (the first leaf development period), and they were placed for one day. In the seedling, 20 ml of the aforementioned test solution was dispensed.

After 6 days of spreading, the number of surviving insects parasitized on the leaves of the cucumber was investigated, and the value of the control was obtained by the following formula.

The control value (%) = {1 - (Cb × Tai) / (Cai × Tb)} × 100, and the characters in the formula indicate the following meanings.

Cb: number of insects before treatment without treatment

Cai: Number of insects in the observation area without treatment

Tb: number of insects before treatment in the treatment area

Tai: Number of insects in the observation area

The term "no treatment zone" as used herein means a formulation containing no compound of the present invention in the preparation example 5, and a zone of the test drug solution diluted with the same amount of water as the treatment zone is dispersed.

As a result, the treatment area of the test liquid using the compounds 2, 3, 4, 6, 12 and 16 of the present invention showed a control value of 90% or more.

Test example 2

The test compound liquids were prepared by diluting the preparations of the present compounds 2, 3, 4 and 6 of the present invention obtained in the preparation example 5 with water at a concentration of 500 ppm as water.

In addition, the cucumber seedlings (the second leaf development period) which were planted in a plastic cup were infused with 5 ml of the above test solution on the plants, and kept in a greenhouse at 25 ° C for 7 days. About 30 eggs of Aphis gossypii (all stages) were inoculated on the surface of cucumber leaves, and after being kept in the greenhouse for 6 days, the number of living insects parasitized on the leaves of the cucumber was investigated by the following formula. Get the value of prevention.

The control value (%) = {1 - (Cb × Tai) / (Cai × Tb)} × 100, and the characters in the formula indicate the following meanings.

Cb: number of insects before treatment without treatment

Cai: Number of insects in the observation area without treatment

Tb: number of insects before treatment in the treatment area

Tai: Number of insects in the observation area

The term "no treatment zone" as used herein means a formulation containing no compound of the present invention in the preparation example 5, and a zone of the test drug solution diluted with the same amount of water as the treatment zone is dispersed.

As a result, the treatment area of the test liquid using the compounds 2, 3, 4 and 6 of the present invention showed a control value of 90% or more.

Test Example 3

The test compound liquids were prepared by diluting the preparations of the compounds 2 and 12 of the present invention obtained in Preparation Example 5 with water at various concentrations of the active ingredient at 500 ppm.

The rice seedlings planted in the second leaf development stage of the polyethylene cup were dispersed in 10 ml of the test liquid. After air drying, 20 larvae of 3 to 4 infested by Nilaparvata lugens were placed in a greenhouse at 25 °C. After 6 days, the number of brown planthoppers parasitized in rice was investigated, and the value of the control was obtained by the following formula.

Control value (%) = {1 - (Cb × Tai) / (Cai × Tb)} × 100 Moreover, the characters in the formula indicate the following meanings.

Cb: number of insects before treatment without treatment

Cai: Number of insects in the observation area without treatment

Tb: number of insects before treatment in the treatment area

Tai: Number of insects in the observation area

The term "no treatment zone" as used herein means a formulation containing no compound of the present invention in the preparation example 5, and a zone of the test drug solution diluted with the same amount of water as the treatment zone is dispersed.

As a result, the treatment area of the test drug solution using the compounds 2 and 12 of the present invention showed a control value of 90% or more.

Test Example 4

The test compound liquid was prepared by diluting the preparation of the compound 2 of the present invention obtained in Formulation Example 5 with water at a concentration of various active ingredients at 500 ppm.

In addition, 5 ml of the test drug solution was poured into the plant on the rice seedlings planted in a plastic cup (after 2 weeks of sowing, and after the 2nd leaf development period), and kept in a greenhouse at 25 ° C for 7 days. Twenty larvae of 3 to 4 instars of Nilaparvata lugens were placed and stored in a greenhouse at 25 ° C for 6 days. The number of living insects of the brown planthopper, which was parasitic on the leaves of rice, was investigated, and the control value was obtained by the following formula.

Control value (%) = {1 - (Cb × Tai) / (Cai × Tb)} × 100 Moreover, the characters in the formula indicate the following meanings.

Cb: number of insects before treatment without treatment

Cai: Number of insects in the observation area without treatment

Tb: number of insects before treatment in the treatment area

Tai: Number of insects in the observation area

The term "no treatment zone" as used herein means a formulation containing no compound of the present invention in the preparation example 5, and a zone of the test drug solution diluted with the same amount of water as the treatment zone is dispersed.

As a result, the treatment area of the test drug solution using the compound 2 of the present invention showed a control value of 90% or more.

Test Example 5

The preparation for the compound of the present invention obtained in Formulation Example 5 was diluted with water so as to have a concentration of various active ingredients of 500 ppm to prepare a test drug solution.

In addition, the tomato seedlings (the third leaf development period) planted in a polyethylene cup were placed in adult beetles of Bemisia tabaci, and they were laid for about 72 hours. The tomato seedlings were kept in a greenhouse for 8 days, and when the larvae were hatched from the eggs which were laid, the test liquid was spread at a ratio of 20 ml/cup and kept in a greenhouse at 25 °C. After 7 days, the number of larvae living on the tomato leaves was investigated, and the value of the control was obtained by the following formula.

Control value: (%) = {1-(Cb × Tai) / (Cai × Tb)} × 100 Moreover, the characters in the formula indicate the following meanings.

Cb: number of insects before treatment without treatment

Cai: Number of insects in the observation area without treatment

Tb: number of insects before treatment in the treatment area

Tai: Number of insects in the observation area

The term "no treatment zone" as used herein means a formulation containing no compound of the present invention in the preparation example 5, and a zone of the test drug solution diluted with the same amount of water as the treatment zone is dispersed.

As a result, the treatment area of the test drug solution using the compound of the present invention showed a control value of 90% or more.

Test Example 6

The test compound liquids were prepared by diluting the preparations of the present compounds 2, 3, 4, 6, 12, and 16 of the present invention obtained in Formulation Example 5 with water at a concentration of 500 ppm.

Further, the above-mentioned test drug solution was dispersed at a ratio of 20 mL/cup in the 3-leaf stage cabbage planted in a polyethylene cup. After the drug solution was dried, the stems and leaves were cut into a 50 mL cup, and 5 second-instar larvae of Plutella xylostella were placed and covered. Store at 25 ° C, calculate the number of living insects after 5 days, and determine the mortality rate from the following formula.

Dead insect rate (%) = (number of dead insects / number of test insects) × 100 As a result, the test using the compounds 2, 3, 4, 6, 12 and 16 of the present invention The treatment area of the drug solution shows that the mortality rate is over 80%.

Test Example 7

The preparation of the compounds 2 and 6 of the present invention obtained in Preparation Example 5 was diluted with water so as to have a concentration of various active ingredients of 500 ppm to prepare a test dispersion liquid.

In addition, apples are planted in plastic cups and spread to the 7th leaf or the 8th leaf. The above test solution was spread by the apple at a ratio of 20 mL/cup. After the drug solution was dried, 60 early larvae of the apple leaf curler (Adoxophyes orana fasciata) were placed, the bottom surface was hollowed out, and the plastic cup attached with the filter paper was placed back and covered. After 7 days, the number of living insects was counted, and the mortality rate was determined by the following formula.

Dead insect rate (%) = (number of dead insects / number of test insects) × 100 As a result, the treatment area of the test liquid using the compounds 2 and 6 of the present invention showed a mortality rate of 90% or more.

Test Example 8

The test compound liquid was prepared by diluting the preparation of the compounds 2 and 6 of the present invention obtained in Preparation Example 5 with water at a concentration of various active ingredients at 500 ppm.

Apply the same size filter paper to the bottom of the polyethylene cup with a diameter of 5.5 cm, and drop 0.7 ml of the above test solution onto the filter paper, and evenly add the sucrose. 30mg as a bait. Ten adult females (Musca domestica) were placed in the polyethylene cup and covered. After 24 hours, the life and death of the housefly was investigated, and the mortality rate was determined by the following formula.

Dead insect rate (%) = (number of dead insects / number of test insects) × 100 The results are shown in the treatment of the compounds 2 and 6 of the present invention, and the mortality rate is 100%.

Test Example 9

Each of the preparations of the compound of the present invention obtained in Formulation Example 5 was diluted with water so as to have an active ingredient concentration of 500 ppm to prepare a test drug solution.

A filter paper of the same size was applied to a polyethylene cup bottom having a diameter of 5.5 cm, 0.7 ml of the above test solution was dropped on the filter paper, and 30 mg of sucrose was uniformly added as a bait. Two German male cockroaches (Blattella germanica) were placed in the polyethylene cup and covered. After 6 days, the life and death of German cockroaches were investigated, and the mortality rate was obtained by the following formula.

Dead insect rate (%) = (number of dead insects / number of test insects) × 100 The results are shown in the treatment of the compound of the present invention, and the mortality rate is 100%.

Test Example 10

Each of the preparations of the compounds 2, 3, 6, 12, and 16 of the present invention obtained in Formulation Example 5 was diluted with water so as to have an active ingredient concentration of 500 ppm to prepare a test drug solution.

0.7 ml of the above test solution was added to 100 ml of ion-exchanged water (active ingredient concentration: 3.5 ppm). Twenty larvae of Culex pipiens pallens were placed in the solution, and the life and death of the Culex pipiens pallens were investigated one day later. The mortality rate was determined by the following formula.

Dead insect rate (%) = (number of dead insects / number of test insects) × 100 The results are shown in the treatment of the compounds 2, 3, 6, 12 and 16 of the present invention, and the mortality rate is 95% or more.

Test Example 11

Each 2 mg of the compound of the present invention was weighed by a threaded tube (marum (registered trademark) No. 5; 27 × 55 mm), and 0.2 mL of acetone was added thereto to cover and dissolve. Rotate the threaded tube. In the reverse rotation, the chemical solution is applied so that the entire inner wall becomes uniform. After taking off the lid for about 2 hours and allowing it to air dry, 5 long-horned blood scorpions (Haemaphysalis longicornis) were placed in a group that was not vamped and covered. The number of deaths was investigated after 2 days, and the mortality rate was calculated by the following formula.

Dead insect rate (%) = 100 × (number of deaths / number of test defects), the result of which is the treatment area of the test drug solution using the compound of the present invention, The mortality rate is 100%.

Industrial availability

The compound of the present invention has an controlling effect against harmful organisms and is suitable as an active ingredient of a pest control agent.

Claims (10)

a fused heterocyclic compound represented by the formula (1), or an N-oxide thereof (Oxide), Wherein R ¹ represents C1-C4 alkyl, cyclopropyl or cyclopropylmethyl, and R ² represents C1-C3 alkyl, C1-C3 haloalkyl, -OR ⁶ , halogen or hydrogen, R ³ represents a C1-C3 alkyl group, a halogen atom or a hydrogen atom, R ⁴ represents a C1-C3 haloalkyl group or -S(O) _m R ⁷ , and R ⁵ represents a C1-C3 alkyl group, a C1-C3 haloalkyl group, OR ⁸ , a halogen atom or a hydrogen atom, R ⁶ and R ⁸ are the same or different and each represents a C1-C3 alkyl group or a C1-C3 haloalkyl group, R ⁷ represents a C1-C3 haloalkyl group, and n represents 0, 1 or 2 , m means 0, 1 or 2]. a compound of the formula (1-1), or an N-oxide thereof, ^Wherein R ^2a represents a C1-C3 perfluoroalkyl group, -OR ^6a , a halogen atom or a hydrogen atom, R ^3a represents a C1-C3 alkyl group, a halogen atom or a hydrogen atom, and R ^4a represents a C1-C3 perfluoroalkyl group. , or -S(O) _m R ^7a , R ^5a represents a C1-C3 alkyl group, -OR ^8a , a halogen atom or a hydrogen atom, and R ^6a or R ^8a are the same or different and each represents a C1-C3 alkyl group, and R ^7a represents C1-C3 perfluoroalkyl, n represents 0, 1 or 2, and m represents 0, 1 or 2]. a compound of the formula (1-2), or an N-oxide thereof, ^Wherein R ^2a represents a C1-C3 perfluoroalkyl group, a halogen atom or a hydrogen atom, R ^3a represents a C1-C3 alkyl group, a halogen atom or a hydrogen atom, and R ^4a represents a C1-C3 perfluoroalkyl group or a -S ( O) _m R ^7a , R ^7a represents a C1-C3 perfluoroalkyl group, n represents 0, 1 or 2, and m represents 0, 1 or 2]. a compound of the formula (1-3), or an N-oxide thereof, ^Wherein R ^2a represents a C1-C3 perfluoroalkyl group, a halogen atom or a hydrogen atom, R ^3a represents a C1-C3 alkyl group, a halogen atom or a hydrogen atom, and R ^4a represents a C1-C3 perfluoroalkyl group or a -S ( O) _m R ^7a , R ^7a represents a C1-C3 perfluoroalkyl group, n represents 0, 1 or 2, and m represents 0, 1 or 2]. The compound according to any one of claims 1 to 4, wherein R ² or R ^2a is a hydrogen atom. The compound according to any one of claims 1 to 4, wherein R ² or R ^2a is a trifluoromethyl group. The compound according to any one of claims 1 to 4, wherein R ³ or R ^3a is a hydrogen atom. The compound of any one of claims 1 to 4, wherein R ⁴ or R ^4a is a trifluoromethyl group. A pest control agent comprising the compound according to any one of claims 1 to 8 and an inert carrier. A pest control method for administering an effective amount of a compound according to any one of claims 1 to 8 to a pest or a habitat thereof.