JP2011105700A - Diaryltriazole derivative or salt thereof, insecticide, miticide, nematicide or soil pesticide containing the same and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insecticide, miticide, nematicide or soil pesticide. <P>SOLUTION: A diaryltriazole derivative represented by formula (I) [wherein R<SP>1</SP>is alkyl, alkenyl or the like; R<SP>2</SP>is phenyl or pyridyl; R<SP>3</SP>and R<SP>4</SP>are each independently a hydrogen atom, halogen, alkyl, alkenyl, cyano or the like; R<SP>5</SP>is alkyl, alkenyl or the like ; and n is 0, 1 or 2] or a salt thereof is provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an insecticide, acaricide, nematicide or soil insecticide containing a novel diaryltriazole derivative or a salt thereof as an active ingredient.

Patent Document 1 describes phenyltriazole derivatives that are useful as insecticides and acaricides, but the substituents corresponding to R ² in formula (I) below are different from those of the compounds of the present invention. Patent Document 2 describes (3-sulfur atom-substituted phenyl) heteroaryl derivatives useful as insecticides and acaricides, but the phenyl substitution position on the triazole ring is different from that of the compound of the present invention. .

International Publication WO 99/55668 JP 2008-308448 A

  Over the years, many insecticides, acaricides, nematicides or soil pesticides have been used, but their effectiveness is insufficient, pests gain resistance and their use is limited. There are many that have the problem of. Therefore, it is desired to develop a novel insecticide, acaricide, nematicide or soil insecticide with few such disadvantages.

  The present inventors have made various studies on phenyltriazole derivatives in order to find a better insecticide, acaricide, nematicide or soil insecticide. As a result, it has been found that the novel diaryltriazole derivative has an extremely high control effect particularly against spider mites at a low dosage, and also has safety against natural enemies such as crops, pests, or mammals. Completed the invention.

  That is, the present invention relates to the formula (I):

Wherein R ¹ is alkyl optionally substituted with halogen, alkenyl optionally substituted with halogen, or alkynyl optionally substituted with halogen; R ² is phenyl optionally substituted with X or X X is halogen, alkyl, haloalkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, alkylthio, amino, nitro, or cyano; R ³ and R ⁴ are each independently a hydrogen atom, halogen, Alkyl, alkenyl, alkynyl or cyano; R ⁵ is alkyl optionally substituted with A, alkenyl optionally substituted with A or alkynyl optionally substituted with A; A is halogen, cyano or cycloalkyl And n is 0, 1 or 2], or a salt thereof. To. The present invention also provides an insecticide, acaricide, nematicide or soil insecticide containing a diaryltriazole derivative of the formula (I) or a salt thereof as an active ingredient, pests, mites, nematodes by applying them. The present invention also relates to a method for controlling soil pests and a method for producing them.

  The insecticide, acaricide, nematicide or soil insecticide containing the diaryltriazole derivative of the formula (I) or a salt thereof as an active ingredient is a low dose against insects, mites, nematodes or soil insects. And has a very high control effect.

Examples of the halogen in formula (I) or the halogen as a substituent include fluorine, chlorine, bromine or iodine atoms. The number of halogens as a substituent may be 1 or 2 or more, and in the case of 2 or more, each halogen may be the same or different. Further, the halogen substitution position may be any position.
The alkyl in formula (I) may be linear or branched, and specific examples thereof include C ₁ such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl. _{-6 and} the like.
Examples of cycloalkyl in formula (I) include C _3-6 such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The alkenyl in the formula (I) may be linear or branched, and specific examples thereof include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 1,3-butadienyl, 1 - those like the _{C 2-6,} such as hexenyl.
The alkynyl in the formula (I) may be linear or branched, and specific examples thereof include ethynyl, 2-butynyl, 2-pentynyl, 3-methyl-1-butynyl, 2-pentene- Examples include C _2-6 such as 4-ynyl and 3-hexynyl.

Examples of the pyridyl represented by R ² in the formula (I) include 2-pyridyl, 3-pyridyl, and 4-pyridyl. Of these, 2-pyridyl is preferred. Moreover, when pyridyl is substituted with the substituent X, X may be the same or different, and the number of substitutions is 1-4.

When phenyl represented by R ² in the formula (I) is substituted with a substituent X, X may be the same or different, and the number of substitutions is 1 to 5.

  Examples of the salt of the diaryltriazole derivative of the formula (I) include any salt as long as it is acceptable in the technical field. For example, ammonium salts such as dimethylammonium salt and triethylammonium salt; Examples thereof include inorganic acid salts such as perchlorate, sulfate and nitrate; organic acid salts such as acetate and methanesulfonate.

  The diaryltriazole derivative of the formula (I) may have an isomer such as an optical isomer or a geometric isomer, but the present invention includes both isomers and isomer mixtures. In the present specification, unless otherwise specified, isomers are described as a mixture. The present invention also includes various isomers other than those described above within the scope of technical common sense in the technical field. Depending on the type of isomer, there may be a chemical structure different from that of the formula (I). However, since those skilled in the art can fully recognize that they are related to isomers, the scope of the present invention. It is clear that it is within.

The diaryltriazole derivative of the above formula (I) or a salt thereof (hereinafter abbreviated as the compound of the present invention) can be produced according to the following production methods [1] to [6] and usual salt production methods. It is not limited to the method.
Manufacturing method [1]

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n are as described above. Production method [1] is a method of producing a compound of formula (I) by reacting a compound of formula (II) with a compound of formula (III) to obtain a compound of formula (IV), which is dehydrogenated. Yes, consisting of the above steps 1-1 and 1-2. Each reaction step is described in detail below.

  The reaction in Step 1-1 can usually be performed in the presence of an acid and a solvent. As an acid, 1 type (s) or 2 or more types can be suitably selected from an acetic acid, hydrochloric acid, a sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, etc. The acid can be used in an amount of 0.05 to 2 times, preferably 0.1 to 1 times the mol of the compound of formula (II).

  The solvent is not particularly limited as long as the reaction proceeds. For example, ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane, dimethoxyethane; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, Halogenated hydrocarbons such as trichloroethane and dichloroethylene; aromatic hydrocarbons such as benzene, toluene and xylene; one or two from aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane The above can be selected as appropriate.

  The reaction in Step 1-1 can be usually carried out at 20 to 250 ° C., preferably 20 to 150 ° C., and the reaction time is usually about 0.5 to 24 hours, preferably about 1 to 20 hours. Can do.

  The reaction of Step 1-2 may be performed after the reaction of Step 1-1 is completed, after isolation of the obtained compound of formula (IV), or may be continued without isolation. When the compound of formula (IV) is isolated, the reaction of step 1-2 is usually performed in the presence of a base or an oxidizing agent. When the compound of the formula (IV) is not isolated, the reaction may proceed without using a base or an oxidizing agent depending on the type of the compound of the formula (III) used.

  Examples of the base include trimethylamine, triethylamine, triisopropylamine, diisopropylethylamine, pyridine, 2-picoline, 3-picoline, 4-picoline, 4-dimethylaminopyridine, 2,6-dimethylpyridine, 4-pyrrolidinopyridine, N -Methylmorpholine, N, N-dimethylaniline, N, N-diethylaniline, N-ethyl-N-methylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [ 2.2.2] One or more of amines such as octane can be appropriately selected. A base is 0.1-5 times mole with respect to the compound of Formula (IV), Preferably 1-3 times mole can be used.

  Examples of the oxidizing agent include 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, chloranil, o-chloranil, hydrogen peroxide, ammonium peroxide disulfate, sodium peroxide disulfate, potassium peroxide disulfate. , Potassium permanganate, oxone (OXONE, trade name of EI DuPont; potassium hydrogen peroxosulfate), sodium hypochlorite, sodium chlorite, benzoyl peroxide, tert-butyl hydroperoxide, oxygen, etc. 1 type or 2 types or more can be selected suitably. The oxidizing agent can be used in an amount of 1 to 10 times mol, preferably 1 to 4 times mol for the compound of formula (IV).

  The reaction in Step 1-2 is usually performed in the presence of a solvent. The solvent is not particularly limited as long as the reaction proceeds, and the same solvent as in Step 1-1 may be used. In addition, polarities such as acetonitrile, propiononitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, and N-methyl-2-pyrrolidone From aprotic solvents; alcohols such as methanol, ethanol, normal propanol, isopropanol, normal butanol, and tertiary butanol; organic acids such as acetic acid and propionic acid; water; esters such as methyl acetate and ethyl acetate One type or two or more types can be appropriately selected.

The reaction in step 1-2 can be carried out usually at -20 to 250 ° C, preferably 0 to 150 ° C, and the reaction time is usually about 0.5 to 48 hours, preferably about 1 to 30 hours. be able to.
Manufacturing method [2]

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n are as described above. Production method [2] is a method for producing a compound of formula (I) by reacting a compound of formula (II) with a compound of formula (V), which will be described in detail below.

  The reaction of the production process [2] can usually be performed in the presence of a base and a solvent. As the base, those similar to the production method [1] step 1-2 can be used. The base can be used in an amount of 0.5 to 5 times mol, preferably 1 to 2 times mol for the compound of formula (II).

  The solvent is not particularly limited as long as the reaction proceeds. For example, those exemplified in the production process [1] step 1-1 can be used.

The reaction of the production method [2] can be carried out usually at -20 to 250 ° C, preferably 0 to 150 ° C, and the reaction time is usually about 0.5 to 48 hours, preferably about 3 to 12 hours. be able to.
Manufacturing method [3]

In the above formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as described above, and nb is 1 or 2. Production method [3] is a method for producing a compound of formula (Ib) by oxidizing a compound of formula (Ia), which will be described in detail below.

  The oxidation reaction of the production method [3] can be performed in the presence of an oxidizing agent. Examples of the oxidizing agent include m-chloroperbenzoic acid, hydrogen peroxide, sodium periodate, oxone (OXONE, trade name of EI DuPont, potassium peroxohydrogensulfate), tert-butyl hypochlorite. One type or two or more types can be appropriately selected from sodium hypochlorite and the like. Among these oxidizing agents, m-chloroperbenzoic acid and / or hydrogen peroxide is desirable, and m-chloroperbenzoic acid is more desirable. The oxidizing agent can be used in an amount of 1 to 10 moles, preferably 1 to 6 moles compared to the compound of the formula (Ia).

  The reaction of the production method [3] can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as the reaction proceeds. For example, ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane, dimethoxyethane; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, Halogenated hydrocarbons such as trichloroethane and dichloroethylene; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; acetonitrile, propiononitrile, Polar aprotic such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, N-methyl-2-pyrrolidone Solvent; alcohols such as methanol, ethanol, normal propanol, isopropanol, normal butanol, and tertiary butanol; organic acids such as acetic acid and propionic acid; water; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; Or 2 or more types can be selected suitably.

The reaction of the production process [3] can be carried out usually at -30 ° C to the reflux temperature in the reaction system, preferably -10 ° C to 100 ° C, and the reaction time is usually about 0.1 to 48 hours, preferably 0. About 5 to 24 hours.
Manufacturing method [4]

In the above ^{formulas, R 1, R 2, R} 3, R 4 and n are as defined above, R ^5c is alkyl which may be substituted with ^{A 1,} with an alkenyl or ^{A 1} may be substituted by ^{A 1} substituted be also good alkynyl; R ^5d is an haloalkynyl may be substituted by A haloalkyl may be substituted by ^2, A ² may be substituted by haloalkenyl or A ^2; A ¹ is a halogen , Cyano or cycloalkyl; A ² is cyano or cycloalkyl. Production method [4] is a method for producing a compound of formula (Id) by halogenating a compound of formula (IC), which will be described in detail below.

  The halogenation reaction of the production method [4] can be performed in the presence of a halogenating agent. Examples of the halogenating agent include one or two of chlorine, bromine, chloramine, N-chlorosuccinimide, N-bromosuccinimide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, thionyl chloride, thionyl bromide and the like. The above can be selected as appropriate.

  The halogenation reaction of the production method [4] can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as the reaction proceeds. For example, ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane, dimethoxyethane; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane Halogenated hydrocarbons such as dichloroethylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane; acetonitrile, propiononitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl Polar aprotic solvents such as sulfoxide, hexamethylphosphoric triamide, sulfolane, N-methyl-2-pyrrolidone; organic acids such as acetic acid and propionic acid; water; methyl acetate Esters such as ethyl acetate; suitably selected one or more from such.

The halogenation reaction in the production method [4] can be carried out usually at −100 to 150 ° C., preferably −10 to 110 ° C., and the reaction time is usually about 0.1 to 48 hours, preferably 0.5 to It can be about 24 hours.
Manufacturing method [5]

In the above formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as described above, and L ¹ is a leaving group. Production method [5] is a method for producing a compound of formula (Ia) by reacting a compound of formula (VI) or formula (XIV) with a compound of formula (VII), which will be described in detail below.

The reaction of the production process [5] can usually be performed in the presence of a base and / or a reaction initiator. The base may be any as long as it exhibits a pH of 8 or more. For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; an alkaline earth metal water such as calcium hydroxide or magnesium hydroxide. Oxides; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as sodium hydrogen carbonate (also known as sodium bicarbonate) and potassium hydrogen carbonate; Alkali metals such as sodium hydride and potassium hydride Hydrides; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide; organic metals such as methyllithium, butyllithium, methylmagnesium bromide, lithium diisopropylamide; The above can be selected as appropriate. Among these bases, alkali metal carbonates, alkali metal bicarbonates, alkali metal hydrides or alkali metal alkoxides are desirable, and sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or sodium hydride is more desirable. The base can be used in an amount of 1 to 10 times mol, preferably 1 to 3 times mol for the compound of formula (VI).
The leaving group L ¹ is not particularly limited as long as the reaction proceeds, and examples thereof include halogen and tosyl.

  As a reaction initiator, 1 type (s) or 2 or more types can be suitably selected from a sulfurous acid, a sulfite, Rongalit (Rongalit * a brand name, sodium formaldehyde sulfoxylate), etc., for example. The reaction initiator can be used in an amount of 0.05 to 5 times mol, preferably 0.1 to 1.2 times mol for the compound of formula (VI) or formula (XIV).

  The reaction of the production process [5] can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as the reaction proceeds. For example, ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane, dimethoxyethane; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, Halogenated hydrocarbons such as trichloroethane and dichloroethylene; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; acetonitrile, propiononitrile, Polar aprotic such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, N-methyl-2-pyrrolidone The solvent; water; one or more may be suitably selected from such.

  The reaction of the production process [5] can be carried out usually at −40 ° C. to the reflux temperature in the reaction system, preferably 0 ° C. to 100 ° C., and the reaction time is usually about 10 minutes to 24 hours, preferably 0.5 It can be about ~ 20 hours.

The compound of the formula (XIV) can be produced by reducing the compound of the formula (VI) by a conventional method. The compound of the formula (VI) and the compound of the formula (XIV) can be converted into each other by a redox reaction, and the compound of the formula (VI) is easily oxidized by oxygen in the air, and the compound of the formula (XIV) It may become the compound of.
Manufacturing method [6]

In the above formula, R ¹ , R ³ , R ⁴ and R ⁵ are as described above, and Q is a benzene ring or a pyridine ring. Production method [6] is a method for producing a compound of formula (Ig) by reducing a compound of formula (If), and will be described in detail below.

  The reduction reaction of the production method [6] is a reaction between the compound of formula (If) and a reducing agent. Examples of the reduction reaction include a catalytic hydrogenation reaction shown below or a reduction reaction with a metal or a metal salt, and the compound of the formula (Ig) can be produced by any reaction.

  The reducing agent for the catalytic hydrogenation reaction is hydrogen. The catalytic hydrogenation reaction can usually be performed in the presence of a catalyst and a solvent. As a catalyst, 1 type (s) or 2 or more types can be suitably selected from palladium carbon, Raney nickel, platinum oxide, etc., for example. The catalyst can be used in an amount of 0.0001 to 10 times mol, preferably 0.001 to 1 times mol, of the compound of formula (If).

The solvent is not particularly limited as long as the reaction proceeds, and examples thereof include ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane and dimethoxyethane; aromatic hydrocarbons such as benzene, toluene and xylene; pentane , Hexane, heptane, octane, cyclohexane; acetonitrile, propiononitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, N- Polar aprotic solvents such as methyl-2-pyrrolidone; alcohols such as methanol, ethanol, normal propanol, isopropanol, normal butanol and tertiary butanol; acetic acid and propionic acid Methyl acetate, esters such as ethyl acetate; organic acids such as pyridine, pyridines such as picoline; can be selected one from such or more suitably.

  The catalytic hydrogenation reaction can usually be carried out at -20 to 150 ° C, preferably 0 to 100 ° C, and the reaction time is usually about 30 minutes to 48 hours, preferably about 1 to 24 hours. .

  The reducing agent for the reduction reaction with a metal or a metal salt is a metal or a metal salt, and can be appropriately selected from one or more of zinc, tin, tin chloride, iron and the like. The metal or metal salt can be used in an amount of 1 to 100 times mol, preferably 1 to 10 times mol for the compound of formula (If).

  The reduction reaction with a metal or metal salt can be carried out in the presence of an acid or a base, if desired. As an acid, 1 type (s) or 2 or more types can be suitably selected from organic acids like acetic acid and propionic acid; inorganic acids like hydrochloric acid, sulfuric acid, and phosphoric acid; Examples of the base include one or two or more kinds of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; You can choose. The acid or base can be used in an amount of 0.1 to 1000 mol, desirably 1 to 100 mol per mol of the compound of formula (If).

  The reduction reaction with a metal or metal salt can usually be carried out in the presence of a solvent. The solvent is not particularly limited as long as the reaction proceeds. For example, those exemplified in the catalytic hydrogenation reaction may be used. In addition to this, one or more kinds of halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, dichloroethylene; water; it can.

  The reaction of the production method [6] can be carried out usually at -50 to 150 ° C, preferably -10 to 100 ° C, and the reaction time is usually about 30 minutes to 48 hours, preferably about 1 to 24 hours. be able to.

[Intermediate manufacturing method]
The compound of formula (VI) which is the starting material of the production method [5] is, for example, (1) a compound of formula (VIII) and a compound of formula (IX) are subjected to a coupling reaction to give a compound of formula (X) A first step to obtain, (2) a second step to halosulfonylate the compound of formula (X) to obtain a compound of formula (XI), (3) a reduction of the compound of formula (XI) of formula (VI) It can be prepared by a reaction consisting of a third step to obtain a compound. Details will be described below. In the following formula, R ¹ , R ² , R ³ and R ⁴ are as described above, and X is halogen.

  The coupling reaction is usually performed in the presence of a copper catalyst. The copper catalyst may be any one as long as a coupling reaction is possible. For example, copper (metal copper), copper sulfate (II), copper sulfate (I), copper oxide (II), copper oxide ( One type or two or more types can be appropriately selected from I), copper chloride (II), copper chloride (I), copper acetate (II), copper acetate (I) and the like. A copper catalyst is 0.001-1 times mole with respect to the compound of Formula (X), Preferably 0.01-0.5 times mole can be used.

  The coupling reaction can be performed in the presence of a base and a solvent, if desired. As the base, those similar to the production method [1] step 1-2 can be used. The base can be used in an amount of 0.1 to 10 moles, preferably 1 to 2 moles based on the compound of the formula (VIII). The solvent is not particularly limited as long as the reaction proceeds, and examples thereof include ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane and dimethoxyethane; aromatic hydrocarbons such as benzene, toluene and xylene; pentane Aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane; acetonitrile, propiononitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, N 1 type or 2 types or more can be suitably selected from polar aprotic solvents such as -methyl-2-pyrrolidone; The coupling reaction can be carried out usually at 0 ° C. to the reflux temperature in the reaction system, desirably 10 ° C. to 150 ° C., and the reaction time can usually be about 1 to 30 hours.

  The halosulfonylation reaction can be performed in the presence of a halosulfonylating agent. As the halosulfonylating agent, for example, one kind or two or more kinds can be appropriately selected from halosulfonic acid compounds such as chlorosulfonic acid and bromosulfonic acid. Among these sulfonylating agents, it is desirable to use chlorosulfonic acid. The halosulfonylating agent can be used in an amount of 1 to 100 times mol, preferably 1 to 10 times mol for the compound of formula (X).

  The halosulfonylation reaction can be carried out in the presence of a solvent, if desired. The solvent is not particularly limited as long as the reaction proceeds. For example, ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane, dimethoxyethane; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane Halogenated hydrocarbons such as dichloroethylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane; one or more can be appropriately selected from organic acids such as acetic acid and propionic acid .

  The halosulfonylation reaction can be usually performed at −10 ° C. to the reflux temperature in the reaction system, preferably 10 ° C. to 150 ° C., and the reaction time is usually about 1 to 48 hours, preferably about 1 to 24 hours. can do.

  The reduction reaction can be performed in the presence of a reducing agent. Examples of the reducing agent include one or more kinds of metal compounds such as zinc, tin and iron; phosphorus compounds such as red phosphorus and triphenylphosphine; halogen compounds such as potassium iodide and iodine; It can be selected as appropriate. The reducing agent can be used in an amount of 1 to 100 times mol, desirably 1 to 10 times mol for the compound of formula (XI).

  The reduction reaction can be performed in the presence of an acid, if desired. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; Lewis acids such as aluminum chloride and polyphosphoric acid; organic acids such as acetic acid and propionic acid; solid acids such as montmorillonite K-10 1 type (s) or 2 or more types can be selected as appropriate from the above. The acid can be used in an amount of 0.066 to 200-fold mol, preferably 2 to 20-fold mol based on the compound of formula (XI).

  The reduction reaction can be performed in the presence of a solvent, if desired. The solvent is not particularly limited as long as the reaction proceeds, and examples thereof include ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane and dimethoxyethane; aromatic hydrocarbons such as benzene, toluene and xylene; pentane Aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; alcohols such as methanol, ethanol, normal propanol, isopropanol, normal butanol and tertiary butanol; nitriles such as acetonitrile and propiononitrile; etc. 1 type or 2 types or more can be selected suitably.

  The reduction reaction can be carried out usually at 0 ° C. to the reflux temperature in the reaction system, preferably 0 ° C. to 100 ° C., and the reaction time is usually about 1 to 48 hours, preferably about 1 to 24 hours. it can.

The compound of the formula (X) obtained in the first step (1) of the [intermediate production method] can also be produced by the production method [A] or the production method [B] shown below.
Manufacturing method [A]

In the production method [A], R ¹ , R ² , R ³ and R ⁴ are as described above.
In the production method [A], a compound of formula (XIII) is reacted with a compound of formula (III) to obtain a compound of formula (XIII), which is dehydrogenated to produce a compound of formula (X). Yes, consisting of the above step A-1 and step A-2. The production method [A] can be carried out according to the production method [1].
Manufacturing method [B]

In the production process [B], R ¹ , R ² , R ³ and R ⁴ are as described above.
Production method [B] is a method for producing a compound of formula (X) by reacting a compound of formula (XII) with a compound of formula (V). The production method [B] can be carried out according to the production method [2].

The compound of the formula (XII) which is the starting material of the production method [A] or the production method [B] can be produced, for example, according to the production method [C] shown below.
Manufacturing method [C]

In the production process [C], R ¹ , R ³ and R ⁴ are as described above. In the production method [C], a compound of the formula (XVII) is reacted with a compound of the formula (XVI) to obtain a compound of the formula (XVII), which is halogenated to obtain a compound of the formula (XVIII). This is a method for producing a compound of the formula (XII) by reacting a compound of (XVIII) with aqueous ammonia, comprising the above steps C-1, C-2 and C-3. In Step C-1, the acetal or hemiacetal form of the compound of formula (XVI) may be used instead of the compound of formula (XVI). Each reaction step is described in detail below.

  The reaction in Step C-1 can be performed in the presence of an acid, if desired. As an acid, 1 type (s) or 2 or more types can be suitably selected from an acetic acid, hydrochloric acid, a sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, etc. The acid can be used in an amount of 0.05 to 2 mols, preferably 0.1 to 1 mols per mol of the compound of formula (XV).

  The compound of formula (XV) may be a salt. When using a salt of the compound of formula (XV), the reaction of step C-1 can be carried out in the presence of a base, if desired. Examples of the base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; acetates such as sodium acetate and potassium acetate; triethylamine and pyridine 1 type (s) or 2 or more types can be appropriately selected from such organic bases.

  The reaction of step C-1 can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as the reaction proceeds, and the same solvent as the reduction reaction in [Intermediate production method] can be used.

  The reaction in Step C-1 can be carried out usually at -70 ° C to the reflux temperature in the reaction system, preferably -20 ° C to 150 ° C, and the reaction time is usually about 10 minutes to 24 hours, preferably 30 minutes. It can be about ~ 12 hours.

  The halogenation reaction in Step C-2 can be performed in the presence of a halogenating agent. As the halogenating agent, for example, one or more kinds may be appropriately selected from chlorine, bromine, chloramine, N-chlorosuccinimide, N-bromosuccinimide, hypochlorous acid, tert-butyl hypochlorite and the like. it can.

  The reaction in Step C-2 may be performed after the completion of the reaction in Step C-1 after the obtained compound of the formula (XVII) is isolated, or may be continued without being isolated. When the compound of the formula (XVII) is isolated, the reaction in Step C-2 can usually be performed in the presence of a solvent. The solvent is not particularly limited as long as the reaction proceeds, and the same solvent as the coupling reaction in [Intermediate production method] can be used.

  The halogenation reaction in Step C-2 can be carried out usually at -70 ° C to the reflux temperature in the reaction system, preferably -20 ° C to 150 ° C, and the reaction time is usually about 10 minutes to 24 hours, preferably It can be about 30 minutes to 12 hours.

  The reaction in Step C-3 can be usually performed in the presence of a solvent. The solvent is not particularly limited as long as the reaction proceeds. For example, ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane, dimethoxyethane; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, Halogenated hydrocarbons such as trichloroethane and dichloroethylene; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; acetonitrile, propiononitrile, Polar aprotic such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, N-methyl-2-pyrrolidone The solvent; water; esters such as methyl acetate, ethyl acetate; acetone, methyl ethyl ketone, ketones such as cyclohexanone; pyridine, pyridines such as picoline; can be appropriately selected one or more from such

  The reaction in Step C-3 can be carried out usually at -30 ° C to the reflux temperature in the reaction system, preferably -10 ° C to 100 ° C, and the reaction time is usually about 10 minutes to 24 hours, preferably 30 minutes. It can be about ~ 12 hours.

  Desirable embodiments of the insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention will be described below. Insecticides, acaricides, nematicides or soil pesticides containing the compounds of the present invention are, for example, pests, mites, nematodes or soil pests that are problematic in the field of agriculture and horticulture, that is, agricultural and horticultural insecticides. It is useful as an agent, an acaricide, a nematicide or a soil insecticide, or an animal parasitic insect or mite control agent, that is, an animal parasite control agent.

  The compounds of the present invention are useful as agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides. Specifically, aphids such as peach aphids, cotton aphids, etc .; Caterpillar, Lotus moth, Codling moth, Ball worm, Tobacco bud worm, Potato moth, Cochno medulla, Chanokoku kakumonhamakiki, Colorado potato beetle, cucumber moth beetle, ball weevil, planthopper, leafhopper, scale insect, stink bug, whitefly, thrips, thrips Pests, such as slugs, cockroaches, house flies, mosquitoes; sanitary pests, such as house dust mites, cockroaches, house flies, mosquitoes, etc .; Such as weevil, beetle, beetle, etc. Pests of stored grains; clothing such as moths, swordworms, termites, etc., house pests; pests such as spider mites, spider mites, spider mites, spider mites, apple spider mites, prickly mites, citrus mites, tick mites, etc. Indoor dusty mites, such as Staghorn mite, Pleurotus mite, Southern mite, etc .; such as mites, root-knot nematodes, cyst nematodes, nesting nematodes, rice nesting nematodes, strawberry nematodes, pine wood nematodes, etc. It is effective for the control of soil pests such as plant parasitic nematodes; The agricultural and horticultural insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention is particularly effective for controlling plant parasitic mites, agricultural pests, plant parasitic nematodes and the like. is there. Among them, it is very useful as an insecticide or acaricide because it shows a further excellent effect in controlling plant parasitic mites and agricultural pests. In addition, agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides containing the compounds of the present invention are various resistances against drugs such as organophosphorus agents, carbamate agents, synthetic pyrethroid agents, neonicotinoid agents, etc. It is also effective for controlling pests. Furthermore, since the compound of the present invention has an excellent osmotic transfer property, the agricultural or horticultural insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention is treated on the soil. By this, it is possible to control pests in the foliage at the same time as the control of soil harmful insects, mites, nematodes, gastropods, and isopods.

  As another desirable embodiment of the insecticide, acaricide, nematicide or soil insecticide containing the compound of the present invention, the above plant parasitic mites, agricultural pests, plant parasitic nematodes, gastropods And agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides that comprehensively control soil pests and the like.

  Agricultural and horticultural insecticides, acaricides, nematicides or soil pesticides containing the compounds of the present invention are usually prepared by mixing the compound with various agricultural adjuvants, powders, granules, granulated water Although it is formulated and used in various forms such as a powder, a wettable powder, an aqueous suspension, an oily suspension, a granular aqueous solvent, an aqueous solvent, an emulsion, a liquid, a paste, an aerosol, As long as it meets the object of the present invention, it can be made into any pharmaceutical form usually used in the art. Adjuvants used in the formulation include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite, sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, starch; water , Toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, alcohol, etc. Solvent; fatty acid salt, benzoate, alkylsulfosuccinate, dialkylsulfosuccinate, polycarboxylate, alkylsulfate, alkylsulfate, alkylarylsulfate, alkyldiglycolethersulfate, alcohol Sulfate ester salt, alkyl sulfonate salt, alkyl aryl sulfonate salt, aryl sulfonate salt, lignin sulfonate salt, alkyl diphenyl ether disulfonate salt, polystyrene sulfonate salt, alkyl phosphate ester salt, alkyl aryl phosphate salt, styryl aryl Phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate , Anionic surfactants such as naphthalenesulfonate formaldehyde condensate; sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid polyglyceride, fat Fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, oxyalkylene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyethylene glycol, polyoxy Nonionic surfactants such as ethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxypropylene fatty acid ester; olive oil, kapok oil, castor oil, palm oil , Coconut oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, Riabura, vegetable oils and mineral oils such as liquid paraffin; and the like. Each component of these adjuvants can be used by appropriately selecting one or two or more types without departing from the object of the present invention. In addition to the above-mentioned adjuvants, it can be used by appropriately selecting from those known in the art. For example, a bulking agent, a thickening agent, an anti-settling agent, an antifreezing agent, a dispersion stabilizer, a phytotoxicity reduction. Various commonly used adjuvants such as agents, antifungal agents and the like can also be used. The compounding ratio (weight ratio) of the compound of the present invention and various adjuvants is 0.001: 99.999 to 95: 5, preferably 0.005: 99.995 to 90:10. In actual use of these preparations, use them as they are or dilute them to a predetermined concentration with a diluent such as water, and add various spreading agents (surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.

  Application of agricultural and horticultural insecticides, acaricides, nematicides or soil pesticides containing the compound of the present invention is different in weather conditions, formulation form, application time, application location, types of pests and occurrences, etc. However, it is generally carried out at an active ingredient concentration of 0.05 to 800,000 ppm, preferably 0.5 to 500,000 ppm, and the application amount per unit area is 0.05 to 50,000 g of the present compound per hectare, preferably 1 ~ 30,000g. The present invention also includes a method for controlling pests, mites, nematodes or soil pests by such an application method, particularly a method for controlling plant parasitic mites, agricultural pests, and plant parasitic nematodes.

  Application of various preparations or dilutions of agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides containing the compounds of the present invention, or dilutions thereof, is generally a commonly used application method, ie spraying. (For example, spraying, misting, atomizing, dusting, water surface application, etc.), soil application (mixing, irrigation, etc.), surface application (application, powder coating, coating, etc.), immersion poison bait, etc. It is also possible to feed livestock with the above-mentioned active ingredient mixed with feed to inhibit the occurrence and growth of harmful insects, particularly harmful insects, in the excreta. It can also be applied by the so-called ultra low volume application method. In this method, it is possible to contain 100% of the active ingredient.

  In addition, agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides containing the compounds of the present invention can be mixed or used in combination with other agricultural chemicals, fertilizers, safeners, etc. In some cases, even better effects and functions may be exhibited. Other pesticides include herbicides, insecticides, acaricides, nematicides, soil insecticides, fungicides, antiviral agents, attractants, antibiotics, plant hormones, plant growth regulators, etc. It is done. In particular, an insecticidal composition, an acaricidal composition, a nematicidal composition or a composition for soil-killing insect pests in which the compound of the present invention and one or more active ingredient compounds of other agricultural chemicals are mixed or used in combination. The product can improve the application range, the timing of chemical treatment, the control activity, and the like in a preferable direction. The compound of the present invention and the other active ingredient compounds of other agricultural chemicals may be prepared separately and mixed at the time of spraying, or both may be used together. The present invention includes such an insecticidal composition, an acaricidal composition, a nematicidal composition or a soil-killing insect pest composition.

  The mixing ratio (weight ratio) between the compound of the present invention and the active ingredient compound of other pesticides cannot be defined unconditionally due to differences in weather conditions, formulation form, application time, application location, type of pests and occurrence, etc. 1: 300 to 300: 1, preferably 1: 100 to 100: 1. In addition, the appropriate amount to be applied is 0.1 to 50,000 g, preferably 1 to 30,000 g as the total active ingredient compound amount per hectare. The present invention also includes a method for controlling pests, mites, nematodes or soil pests by the application method of such insecticidal compositions, acaricidal compositions, nematicidal compositions or soil-killing insect pests. It is.

In the above-mentioned other agricultural chemicals, as an active ingredient compound of an insecticide, acaricide, nematicide or soil pesticide (generic name; including some pending applications or Japan Plant Protection Association test code), for example Profenofos, dichlorvos, fenamiphos, fenitrothion, EPN, diazinon, chlorpyrifos, chlorpyrifos-methyl, acephate, prothiophos, prothiophos, prothiophos Fosthiazate, cadusafos, disulfoton, isoxathion, isofenphos, ethion, etrimfos, quinalphos, dimethylvinphos, dimethoate ), Sulprofos, thiomethos (thiometon), bamidothion, pyraclofos, pyridaphenthion, pirimiphos-methyl, propaphos, phosalone, formothion, malathion, tetrachlorvinphos (tetrachlorvinphos), chlorfenvinphos, cyanophos, trichlorfon, methidathion, phenthoate, ESP, azinphos-methyl, fenthion, heptenophos , Methoxychlor, parathion, phosphocarb, demeton-S-methyl, monocrotophos, metamidophos, imicyafos, parathion-methyl -methyl), terbufos ( terbufos), organophosphate compounds such as phosphamidon, phosmet, phorate;
Carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, ethiofencarb, pirimicarb, fenobucarb, fenobucarb Carbamates such as carbosulfan, benfuracarb, bendiocarb, furathiocarb, isoprocarb, metolcarb, xylylcarb, XMC, fenothiocarb Compound;
Nereistoxin derivatives such as cartap, thiocyclam, bensultap, sodium thiosultap-sodium;
Organochlorine compounds such as dicophor, tetradifon, endosulfan, dienochlor, dieldrin;
Organometallic compounds such as fenbutatin oxide and cyhexatin;
Fenvalerate, permethrin, cypermethrin, deltamethrin, cyhalothrin, tefluthrin, etofenprox, flufenprox, cyfluthrin , Fenpropathrin, flucytrinate, fluvalinate, cycloprothrin, lambda-cyhalothrin, pyrethrin, esfenvalerate, tetramethrin (Tetramethrin), resmethrin, protrifenbute, bifenthrin, zeta-cypermethrin, acrinathrin, alpha-cypemethrin (alpha-cype) rmethrin), allethrin, gamma-cyhalothrin, theta-cypermethrin, tau-fluvalinate, tralomethrin, profluthrin, beta-si Pyrethroid compounds such as per-methrin (beta-cypermethrin), beta-cyfluthrin, mettofluthrin, phenothrin, flumethrin;
Diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, lufenuron, novaluron, triflumuron, hexaflumuron, hexaflumuron Benzoylurea compounds such as (bistrifluron), nobifluuron, fluazuron;
Juvenile hormone-like compounds such as metoprene, pyriproxyfen, fenoxycarb, diofenolan;
Pyridazinone compounds such as pyridaben;
Pyrazole compounds such as fenpyroximate, fipronil, tebufenpyrad, ethiprole, tolfenpyrad, acetoprole, pyrafluprole, pyriprole;
Imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, nidinotefuran, dinotefuranit, dinotefuranit A noid compound;
Hydrazine compounds such as tebufenozide, methoxyfenozide, chromafenozide, halofenozide;
Pyridine compounds such as Pyridalyl and flonicamid;
Cyclic ketoenol compounds such as spirodiclofen, spiromesifen, spirotetramat;
Strobilurin-based compounds such as fluacrypyrim;
Pyrimidinamine compounds such as flufenerim;
Dinitro compounds, organic sulfur compounds, urea compounds, triazine compounds, hydrazone compounds, and other compounds include buprofezin, hexythiazox, amitraz, chlordimeform, silafluofen ), Triazamate, pymetrozine, pyrimidifen, chlorfenapyr, indoxacarb, acequinocyl, etoxazole, cyromazine, 1,3-dichloropropene (1,3-dichloropropene), diafenthiuron, benclothiaz, bifenazate, propargite, clofentezine, metaflumizone metaflumizone, flubendiamide, cyflumetofen, chlorantraniliprole, cyenopyrafen, pyrifluquinazon, fenazaquin, fenazaquin, amidoflumet, sulfid And compounds such as nona (hydramethylnon), metaldehyde, HGW-86, ryanodine, verbutin; and the like. Furthermore, Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis israelensis, Bacillus thuringiensis japonensis, Bacillus thuringiensis tenebrionis or crystalline protein toxins produced by Bacillus thuringiensis, entomopathogenic fungi, nematode pathogenic fungi, etc. Microbial pesticides such as: avermectin, emamectin benzoate, milbemectin, milbemycin, spinosad, ivermectin, lepimectin, DE-175, abamectin ), Antibiotics such as emamectin, spinetoram and semi-synthetic antibiotics; natural products such as azadirachtin and rotenone; repellents such as deet; etc. And mixed use It is also possible to.

In the above-mentioned other pesticides, as an active ingredient compound (generic name; including partial application or Japanese Plant Protection Association test code), for example, mepanipyrim, pyrimethanil, cyprodinil Anilinopyrimidine compounds such as
Tria such as 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) [1,2,4] triazolo [1,5-a] pyrimidine Zolopyrimidine compounds;
Pyridinamine compounds such as fluazinam;
Triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, microbutanil, cyproconazole cyproconazole), tebuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole, epoxiconazole, tetraconazole, o Oxpoconazole fumarate, sipconazole, prothioconazole, triadimenol, flutriafol, difenoconazole , Fluquinconazole, fenbuconazole, bromuconazole, diniconazole, tricyclazole, probenazole, cimeconazole, pefurazoate, ipconazole, ipconazole ), Azole compounds such as imibenconazole;
Quinoxaline compounds such as quinomethionate;
Dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb, thiram;
Organochlorine compounds such as fthalide, chlorothalonil, quintozene;
Imidazole compounds such as benomyl, cyazofamid, thiophanate-methyl, carbendazim, thiabendazole, and fuberiazole;
Cyanoacetamide compounds such as cymoxanil;
Metalaxyl, metalaxyl-M, mefenoxam, oxadixyl, offurace, benalaxyl, benalaxyl-M, also known as kiralaxyl, chiax ), Fluralaxyl, cyprofuram, carboxin, oxycarboxin, thifluzamide, boscalid, isothianil, bixafen, thiadinyl, Anilide compounds such as sedaxane;
Sulfamide-type compounds such as dichlofluanid;
Copper-based compounds such as cupric hydroxide and oxine copper;
Isoxazole compounds such as hymexazol;
Fosetyl-Al, tolclofos-Methyl, S-benzyl O, O-diisopropyl phosphorothioate, O-ethyl S, S-diphenyl phosphorodithioate, aluminum ethyl hydrogen phosphonate, edifenphos, iprobenphos Organophosphorus compounds such as (iprobenfos);
Phthalimide compounds such as captan, captafol, folpet;
Dicarboximide compounds such as procymidone, iprodione, vinclozolin;
Benzanilide compounds such as flutolanil and mepronil;
Penthiopyrad, 3- (difluoromethyl) -1-methyl-N-[(1RS, 4SR, 9RS) -1,2,3,4-tetrahydro-9-isopropyl-1,4-methanonaphthalen-5-yl ] Pyrazole-4-carboxamide and 3- (difluoromethyl) -1-methyl-N-[(1RS, 4SR, 9SR) -1,2,3,4-tetrahydro-9-isopropyl-1,4-methanonaphthalene-5 Amide compounds such as -yl] pyrazole-4-carboxamide mixtures (isopyrazam), silthiopham, fenoxanil;
Benzamide compounds such as fluopyram and zoxamid;
Piperazine compounds such as triforine;
Pyridine compounds such as pyrifenox;
Carbinol compounds such as fenarimol;
Piperidine compounds such as fenpropidin;
Morpholine compounds such as fenpropimorph and Tridemorph;
Organotin compounds such as fentin hydroxide and fentin acetate;
Urea-based compounds such as pencycuron;
Synamic acid compounds such as dimethomorph, flumorph;
Phenyl carbamate compounds such as dietofencarb;
Cyanopyrrole compounds such as fludioxonil and fenpiclonil;
Azoxystrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, picoxystrobin, oryzastrobin, dimoxystrobin ( strobilurin compounds such as dimoxystrobin), pyraclostrobin, fluoxastrobin;
Oxazolidinone compounds such as famoxadone;
Thiazole carboxamide compounds such as ethaboxam;
Valinamide compounds such as iprovalicarb, benchthiavalicarb-isopropyl;
Acylamino acid compounds such as methyl N- (isopropoxycarbonyl) -L-valyl- (3RS) -3- (4-chlorophenyl) -β-valaniphenate;
Imidazolinone compounds such as fenamidone;
Hydroxyanilide compounds such as fenhexamid;
Benzenesulfonamide compounds such as flusulfamide;
Oxime ether compounds such as cyflufenamid;
Anthraquinone compounds;
Crotonic acid compounds;
Antibiotics such as validamycin, kasugamycin, polyoxins;
Guanidine compounds such as iminoctadine and dodine;
Quinoline compounds such as 6-tertiarybutyl-8-fluoro-2,3-dimethylquinolin-4-yl acetate (tebufloquin)
Thiazolidines such as (Z) -2- (2-fluoro-5- (trifluoromethyl) phenylthio) -2- (3- (2-methoxyphenyl) thiazolidine-2-ylidene) acetonitrile (flutianil) Compound;
Other compounds include pyribencarb, isoprothiolane, pyroquilon, diclomezine, quinoxyfen, propamocarb hydrochloride, chloropicrin, dazomet, metam Sodium salt (metam-sodium), nicobifen, metrafenone, UBF-307, diclocymet, proquinazid, amisulbrom (aka amibromdole), pyriofenone (manipropamide) mandipropamid), fluopicolide, carpropamid, meptyldinocap, ferimzone, spiroxamine, S-2188 (fenpyrazamine), S- 2200, ZF-9646, BCF-051, BCM-061 and BCM-062 and the like.

  Other pesticides that can be used in combination with or combined with the compounds of the present invention include, for example, active compound compounds of herbicides such as those described in The Pesticide Manual (15th edition), especially those treated with soil. There is.

  Specific examples of animal parasite control agents include harmful ectoparasites that parasitize on the body surface of the host animal (back, armpit, lower abdomen, inner thigh, etc.) and the host animal body (stomach, intestinal tract, It is effective in controlling harmful endoparasites that parasitize the lungs, heart, liver, blood vessels, subcutaneous, lymphoid tissue, etc., and in particular, it is effective in controlling ectoparasites.

  Examples of ectoparasites include animal parasitic mites and fleas. There are so many of these types that it is difficult to list them all.

The animal parasitic mites, for example Boophilus microplus (Boophilus microplus), Rhipicephalus sanguineus (Rhipicephalus sanguineus), Haemaphysalis longicornis (Haemaphysalis longicornis), Haemaphysalis flava (Haemaphysalis flava), Adenophora chima tick (Haemaphysalis campanulata), Isukachimadani (Haemaphysalis concinna), Yamatochimadani (Haemaphysalis japonica), H. kitaokai (Haemaphysalis kitaokai), Iyasuchimadani (Haemaphysalis ias), Ixodes ovatus (Ixodes ovatus), I. nipponensis (Ixodes nipponensis), Schulze ticks (Ixodes persulcatus), Takasago testudinarium (Amblyomma testudinarium), Ootogechimadani (Haemaphysalis megaspinosa ), tick such as Dermacentor reticulatus , Dermacentor taiwanesis ; duck ( Dermanyssus gallinae ); Shidani (Ornithonyssus sylviarum), Torisashidani, such as Southern tri sand mite (Ornithonyssus bursa); Nan iodine tsutsugamushi (Eutrombicula wichmanni), red mites (Leptotrombidium akamushi), L. pallidum (Leptotrombidium pallidum), Fuji chiggers (Leptotrombidium fuji), Tosa mites ( Leptotrombidium tosa), Europe Aki mites (Neotrombicula autumnalis), the United States chiggers (Eutrombicula alfreddugesi), chiggers, such as Miyagawa Tama chiggers (Helenicula miyagawai); Inutsumedani (Cheyletiella yasguri), rabbit Tsumedani (Cheyletiella parasitivorax), Nekotsumedani (Cheyletiella blakei) Tsumedani, such as; rabbits 9,000 mite (Psoroptes cuniculi), Ushishokuhidani (Chorioptes bovis), dog ear mites (Otodectes cynotis), mange mites (Sar coptes scabiei ), mite mites like Notoedres cati, mite mites like Demodex canis , and the like. Among them, the animal parasite control agent containing the compound of the present invention is particularly effective for controlling ticks and the like.

Examples of animal parasitic fleas include ectoparasite worms belonging to the order Flea ( Siphonaptera ), and more specifically, fleas belonging to the family Flea family ( Pulicidae ), Nagano family ( Ceratephyllus ) and the like. Examples of fleas belonging to the family flea family include, for example, dog fleas ( Ctenocephalides canis ), cat fleas ( Ctenocephalides felis ), human fleas ( Purex irritans ), elephant fleas ( Echidnophaga gallinacea ), keops mouse fleas ( Xenopsylla cheopis ) Leptopsylla segnis ), European mud minnow ( Nosopsyllus fasciatus ), Yamato mud mink ( Monopsyllus anisus ); and the like. Among them, the animal parasite control agent containing the compound of the present invention is effective for controlling fleas belonging to the family Flea, especially dog fleas, cat fleas and the like.

  Other ectoparasites include, for example, lice such as bovine lice, foal lice, sheep lice, bovine white lice, head lice; lice such as dog lice; . In addition, examples of endoparasites include nematodes such as lungworm, benthic, nodular worms, gastric parasites, roundworms, and filamentous worms; Tapeworms such as real tapeworms, multi-headed tapeworms, single-banded tapeworms, multi-banded tapeworms; Japanese schistosomiasis, fluke like liver fluke; coccidium, malaria parasite, intestinal granulocyst, toxoplasma, chestnut Protozoa such as Ptosporidium, and the like.

  Examples of host animals include various pet animals, livestock, poultry, and the like. More specifically, dogs, cats, mice, rats, hamsters, guinea pigs, squirrels, rabbits, ferrets, birds (eg, pigeons, parrots, (E.g., nine-bird, bird, parakeet, juvenile pine, canary, etc.), cattle, horses, pigs, sheep, ducks, chickens, etc. Among them, the animal parasite control agent containing the compound of the present invention is effective for controlling pests or ticks that are externally parasitic on pet animals or livestock. Among pet animals or domestic animals, it is particularly effective for dogs, cats, cows or horses.

  When the compound of the present invention is used as an animal parasite control agent, it may be used as it is, and together with suitable adjuvants, powders, granules, tablets, powders, capsules, liquid agents, emulsions, aqueous suspensions, It can also be formulated and used in various forms such as an oily suspension. In addition to the above-mentioned preparation forms, any preparation forms used in the normal field can be used as long as the object of the present invention is met. As an adjuvant to be used in the preparation, the anionic surfactants and nonionic surfactants exemplified as the above-mentioned preparation adjuvant for agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides. Surfactant; cationic surfactant such as cetyltrimethylammonium bromide; water, acetone, acetonitrile, N-methylacetamide, N, N-dimethylacetamide, N, N-dimethylformamide, 2-pyrrolidone, N- Methyl-2-pyrrolidone, kerosene, triacetin, methanol, ethanol, isopropanol, benzyl alcohol, ethylene glycol, propylene glycol, polyethylene glycol, liquid polyoxyethylene glycol, butyl diglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, di Solvents such as tylene glycol monoethyl ether, diethylene glycol normal butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol normal butyl ether; butylhydroxyanisole, butylhydroxytoluene, ascorbic acid, sodium metabisulfite, propyl gallate, sodium thiosulfate Antioxidants such as: polyvinyl pyrrolidone, polyvinyl alcohol, film forming agents such as vinyl acetate and vinyl pyrrolidone copolymers; formulations of the aforementioned agricultural and horticultural insecticides, acaricides, nematicides or soil insecticides Vegetable oils and mineral oils exemplified as adjuvants for milk; lactose, sucrose, glucose, starch, wheat flour, corn flour, soybean oil cake, defatted rice bran, calcium carbonate, and other carriers such as commercially available feed ingredients; That. Each component of these adjuvants can be used by appropriately selecting one or two or more types without departing from the object of the present invention. In addition to the above-mentioned adjuvants, it can be used by appropriately selecting from those known in the field, and further, selected from various adjuvants used in the above-mentioned agricultural and horticultural fields. You can also

  The blending ratio (weight ratio) of the compound of the present invention and various adjuvants is usually about 0.1: 99.9 to 90:10. In actual use of these preparations, use them as they are or dilute them to a predetermined concentration with a diluent such as water, and add various spreading agents (surfactants, vegetable oils, mineral oils, etc.) as necessary. Can be used.

  Administration of the compound of the present invention to the host animal is performed orally or parenterally. Examples of the oral administration method include a method of administering tablets, liquid agents, capsules, wafers, biscuits, minced meat, and other feeds containing the compound of the present invention. As a parenteral administration method, for example, the compound of the present invention is prepared into an appropriate preparation and then taken into the body by intravenous administration, intramuscular administration, intradermal administration, subcutaneous administration, etc .; spot-on And a method of administering to the body surface by treatment, pour-on treatment, spray treatment, etc .; a method of embedding a resin piece containing the compound of the present invention under the skin of a host animal, and the like.

  The dose of the compound of the present invention to the host animal varies depending on the administration method, administration purpose, disease symptoms, etc., but is usually 0.01 mg to 100 g, preferably 0.1 mg to 10 g, relative to 1 kg body weight of the host animal. Is suitable for administration.

  The present invention also includes a method for controlling animal parasites, particularly a method for controlling ectoparasites or endoparasites by the administration method or dosage as described above.

  In the present invention, by controlling harmful animal parasites as described above, various host animal diseases caused by them may be prevented or treated. Thus, the present invention includes a prophylactic or therapeutic agent for parasitic animal diseases containing the compound of the present invention as an active ingredient, and a method for preventing or treating parasitic animal diseases.

  When using the compound of the present invention as an animal parasite control agent, various vitamins, minerals, amino acids, nutrients, enzyme preparations, antipyretics, sedatives, anti-inflammatory agents, bactericides, coloring agents, fragrances, It can be mixed with or used in combination with preservatives and the like. In addition, if necessary, other animal drugs and agricultural chemicals such as anthelmintics, anticoccidials, insecticides, acaricides, fleas, nematicides, fungicides, antibacterials, etc. In this case, a more excellent effect may be exhibited. The present invention includes a composition for controlling animal parasites in which various components as described above are mixed or used together, and a method for controlling animal parasites using the composition, in particular, control of ectoparasites or endoparasites. A method is also included.

Desirable embodiments of the compound of the formula (I) are as follows. However, the present invention is not limited to these.
(1) The compound of the above formula (I) or a salt thereof.
(2) R ¹ is alkyl optionally substituted with halogen; R ² is phenyl optionally substituted with X or pyridyl optionally substituted with X; X is halogen, alkyl, haloalkyl, alkoxy, Haloalkoxy, alkylthio, amino, nitro or cyano; R ³ and R ⁴ are each independently a hydrogen atom, halogen, alkyl or cyano; R ⁵ is optionally substituted with alkyl or A The diaryltriazole derivative or the salt thereof according to (1), which is a good alkenyl.
(3) The diaryltriazole derivative or the salt thereof according to (2), wherein R ³ and R ⁴ are each independently halogen, alkyl, or cyano; and R ⁵ is alkyl optionally substituted with A.
(4) The diaryltriazole derivative or a salt thereof according to (2), wherein R ³ and R ⁴ are each independently a hydrogen atom, halogen or alkyl; and R ⁵ is alkyl optionally substituted with A.
(5) The diaryltriazole derivative or a salt thereof according to (1), (2), (3) or (4), wherein R ² is pyridyl optionally substituted with X.
(6) The diaryltriazole derivative or the salt thereof according to (5), wherein the pyridyl optionally substituted with X is 2-pyridyl optionally substituted with X.
(7) The diaryltriazole derivative or the salt thereof according to (5), wherein the pyridyl optionally substituted with X is 2-pyridyl.
(8) The diaryltriazole derivative or the salt thereof according to (1) to (7), wherein n is 0.
(9) An insecticide, acaricide, nematicide or soil insecticide containing the diaryltriazole derivative or salt thereof according to (1) as an active ingredient.
(10) An insecticide, acaricide, wherein the insecticide, acaricide, nematicide or soil insecticide containing the diaryltriazole derivative or salt thereof according to (9) as an active ingredient is for agricultural or horticultural use Agent, nematicide or soil-killing pesticide.
(11) An agricultural or horticultural insecticide or acaricide containing the diaryltriazole derivative or salt thereof as an active ingredient according to (10) above.
(12) An insecticide, acaricide, nematicide or soil insecticide containing the diaryltriazole derivative or salt thereof according to (9) as an active ingredient is used for controlling animal parasitic pests or mites. Some insecticide or acaricide.
(13) A method for controlling pests, mites, nematodes or soil pests by applying an effective amount of the diaryltriazole derivative or salt thereof according to (1).

  Next, examples of the present invention will be described, but the present invention is not limited thereto. First, the synthesis example of this invention compound is described.

Synthesis example 1
2- (1- (2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) -3- (trifluoromethyl) -1H-1,2,4-triazole-5 -Yl) Synthesis of Pyridine (Compound No. 32) 2,2,2-trifluoro-N '-(2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) aceto 0.10 g of p-toluenesulfonic acid monohydrate was added to a mixed solution of 1.0 g of hydrazone amide, 0.34 g of 2-pyridinecarboxaldehyde and 20 mL of toluene, and the mixture was heated to reflux for 1 hour using an azeotropic dehydrator. After removing the reaction vessel from the oil bath and cooling to room temperature, a mixed solution of 0.59 g of triethylamine and 2 mL of toluene was added and reacted for 20 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/0 to 9/1) to obtain 0.84 g of a solid target product.

Synthesis example 2
2- (1- (2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylsulfonyl) phenyl) -3- (trifluoromethyl) -1H-1,2,4-triazole-5 Synthesis of 2-yl) pyridine (Compound No. 34) 2- (1- (2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) -3- (trifluoromethyl) -1H-1,2,4-triazol-5-yl) pyridine (Compound No. 32) 0.18 g and chloroform 5 mL mixed solution, m-chloroperbenzoic acid 0.30 g was added in three portions, The reaction was allowed to proceed for 24 hours at room temperature. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogen carbonate, water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/0 to 6/4) to obtain 0.11 g of a solid target product.

Synthesis example 3
2- (1- (2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) -3- (trifluoromethyl) -1H-1,2,4-triazole-5 -Yl) Synthesis of benzonitrile (Compound No. 21) 2,2,2-trifluoro-N '-(2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) 0.016 g of p-toluenesulfonic acid monohydrate was added to a mixed solution of 0.15 g of acetohydrazone amide, 0.11 g of 2-cyanobenzaldehyde and 5 mL of toluene, and the mixture was heated to reflux for 4 hours using an azeotropic dehydrator. Thereafter, 0.008 g of p-toluenesulfonic acid monohydrate was further added and heated to reflux for 14 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/0 to 4/1) to obtain 0.058 g of the oily desired product.

Synthesis example 4
1- (2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) -5- (2-nitrophenyl) -3- (trifluoromethyl) -1H-1,2 , 4-Triazole (Compound No. 25) 2,2,2-trifluoro-N ′-(2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) aceto 0.044 g of p-toluenesulfonic acid monohydrate was added to a mixed solution of 0.40 g of hydrazone amide, 0.35 g of 2-nitrobenzaldehyde and 10 mL of toluene, and the mixture was heated to reflux for 2 hours using an azeotropic dehydrator. After removing the reaction vessel from the oil bath and cooling to room temperature, 0.23 g of triethylamine was added and reacted for 22 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/0 to 1/1) to obtain 0.38 g of the oily desired product.

Synthesis example 5
2- (1- (2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) -3- (trifluoromethyl) -1H-1,2,4-triazole-5 -Yl) Synthesis of aniline (Compound No. 26) 1- (2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) -5- (2-nitrophenyl) -3 After adding 0.050 g of 5% palladium carbon to a mixed solution of 0.27 g of (trifluoromethyl) -1H-1,2,4-triazole (Compound No. 25) and 10 mL of methanol, and purging the reaction system with hydrogen And allowed to react at room temperature for 22 hours. After the reaction, water was added to the reaction mixture, followed by filtration. The obtained filtrate was extracted with ethyl acetate, and then the organic layer was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/0 to 3/1) to obtain 0.20 g of a solid target product.

Synthesis Example 6
5- (2-Chlorophenyl) -1- (2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) -3- (trifluoromethyl) -1H-1,2, Synthesis of 4-triazole (Compound No. 10) To a mixed solution of 0.14 g of 2-chlorobenzoic acid, 2 mL of tetrahydrofuran and 0.10 mL of oxalyl chloride, 0.002 mL of N, N-dimethylformamide was added. After reacting at room temperature for 1 hour, the reaction mixture was concentrated under reduced pressure to obtain 2-chlorobenzoic acid chloride. In a separate reaction vessel, 0.30 g of 1,2,2-trifluoro-N '-(2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) acetohydrazone amide and 1 , 4-Dioxane 5 mL and 0.075 g of pyridine were added. To this mixed solution, the previously prepared mixed solution of 2-chlorobenzoic acid chloride and 2 mL of 1,4-dioxane was added dropwise and heated to reflux for 6 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/0 to 1/1) to obtain 0.060 g of the oily desired product.

Synthesis example 7
4-chloro-2- (1- (2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) -3- (trifluoromethyl) -1H-1,2,4 -Synthesis of triazol-5-yl) pyridine (Compound No. 39) To a mixed solution of 0.15 g of 4-chloropicolinic acid, 2 mL of tetrahydrofuran and 0.10 mL of oxalyl chloride was added 0.002 mL of N, N-dimethylformamide. After reacting at room temperature for 1 hour, the reaction mixture was concentrated under reduced pressure to obtain 4-chloropicolinic acid chloride. In a separate reaction vessel, 0.30 g of 1,2,2-trifluoro-N '-(2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) acetohydrazone amide and 1 , 4-Dioxane 5 mL and 0.075 g of pyridine were added. To this mixed solution, the previously prepared mixed solution of 4-chloropicolinic acid chloride and 3 mL of 1,4-dioxane was added dropwise and heated to reflux for 6 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/0 to 1/1) to obtain 0.14 g of a solid target product.

Synthesis Example 8
2- (1- (5- (1-Chloro-2,2,2-trifluoroethylthio) -2-fluoro-4-methylphenyl) -3- (trifluoromethyl) -1H-1,2,4 Synthesis of -triazol-5-yl) pyridine (Compound No. 64) 2- (1- (2-Fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl) -3- ( (Trifluoromethyl) -1H-1,2,4-triazol-5-yl) pyridine (Compound No. 32) 0.30 g and N, N-dimethylformamide 5 mL were mixed with 0.18 g of N-chlorosuccinimide. The mixture was further reacted at room temperature for 16 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/0 to 1/1) to obtain 0.13 g of a solid target product.

Synthesis Example 9
2- (1- (4-Methyl-3- (2,2,2-trifluoroethylthio) phenyl) -3- (trifluoromethyl) -1H-1,2,4-triazol-5-yl) pyridine Synthesis of (Compound No. 131)
(1) A mixture of 8.40 g of p-tolylhydrazine hydrochloride, 9.10 g of trifluoroacetaldehyde hemiethyl acetal, 4.33 g of sodium acetate, and 100 mL of ethanol was heated to reflux for 2 hours. After cooling the reaction solution to room temperature, the reaction solution was added to water and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give 1- (p-tolyl) -2- (2,2,2-trifluoroethylidene. ) Hydrazine was obtained.
(2) Add 50 mL of N, N-dimethylformamide and 9.4 g of N-bromosuccinimide to the total amount of 1- (p-tolyl) -2- (2,2,2-trifluoroethylidene) hydrazine obtained in (1). And reacted at room temperature for 30 minutes. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to give 2,2,2-trifluoro-N ′-(p-tolyl) acetohydrazono. Irbromide was obtained.
(3) 120 mL of chloroform and 60 mL of 28% aqueous ammonia were added to the total amount of 2,2,2-trifluoro-N ′-(p-tolyl) acetohydrazonoyl bromide obtained in (2), and 1.5 hours at room temperature. Reacted. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give 2,2,2-trifluoro-N '-(p-tolyl) acetohydrazone amide. Got.
Measured by The ¹ H-NMR data ^[1 H- nuclear magnetic resonance spectroscopy of this compound (Nuclear Magnetic Resonance Spectroscopy). δ is a chemical shift value. ] Is as follows.
¹ H-NMR (solvent: (D ₃ C) ₂ S = O / 400 MHz) δ (ppm): 8.31 (1H, s), 6.97 (2H, d), 6.81 (2H, d), 6.33 (2H, brs ), 2.16 (3H, s)
(4) To the total amount of 2,2,2-trifluoro-N ′-(p-tolyl) acetohydrazone amide obtained in (3), 100 mL of toluene, 6.02 g of 2-pyridinecarboxaldehyde, and p-toluenesulfonic acid monohydrate 1.94 g of the Japanese product was added, and the mixture was heated to reflux for 1 hour using an azeotropic dehydrator. After removing the reaction vessel from the oil bath and cooling to room temperature, 10.3 g of triethylamine was added and allowed to react for 20 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/0 to 9/1) to give 2- (1- (p-tolyl)- 9.09 g of 3- (trifluoromethyl) -1H-1,2,4-triazol-5-yl) pyridine (melting point: 92.4 ° C.) was obtained. The ¹ H-NMR data of this product are as follows.
¹ H-NMR _{(solvent: CDCl 3 / 400MHz) δ (} ppm): 8.48 (1H, dd), 7.94 (1H, dd), 7.79 (1H, dt), 7.35-7.30 (1H, m), 7.26 (2H , d), 7.21 (2H, d), 2.40 (3H, s)
(5) 2- (1- (p-Tolyl) -3- (trifluoromethyl) -1H-1,2,4-triazole- obtained in (4) was added to 17.8 mL of chlorosulfonic acid under ice cooling. After adding 9.09 g of 5-yl) pyridine little by little, the mixture was reacted at 120 ° C. for 3 hours. The reaction mixture was cooled to room temperature, added to ice water, and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give 2-methyl-5- (5- (pyridin-2-yl) -3- ( Trifluoromethyl) -1H-1,2,4-triazol-1-yl) benzene-1-sulfonyl chloride was obtained.
(6) 2-Methyl-5- (5- (pyridin-2-yl) -3- (trifluoromethyl) -1H-1,2,4-triazol-1-yl) benzene- obtained in (5) A mixture of the total amount of 1-sulfonyl chloride, 30 mL of acetic acid, 1.58 g of red phosphorus and 0.25 g of iodine was reacted at 100 ° C. for 1.5 hours. The reaction mixture was cooled to room temperature and then filtered to remove solids from the reaction mixture. The obtained filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 7/3 to 0/10) to give 2-methyl-5- (5- (5- ( 4.82 g of pyridin-2-yl) -3- (trifluoromethyl) -1H-1,2,4-triazol-1-yl) benzenethiol (melting point 111.7 ° C.) was obtained.
(7) 2-methyl-5- (5- (pyridin-2-yl) -3- (trifluoromethyl) -1H-1,2,4-triazol-1-yl) benzenethiol 0.20 g and potassium carbonate A mixture of 0.19 g of 1,1,1-trifluoro-2-iodoethane and 1 mL of N, N-dimethylformamide is added to a mixture of 0.12 g, 0.07 g of Rongalit and 3 mL of N, N-dimethylformamide. The solution was added dropwise and reacted at room temperature for 16 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/0 to 9/1) to obtain 0.18 g of a solid target product.

Representative examples of the compounds of formula (I) are listed in Table 1. These compounds can be produced based on the above-mentioned synthesis examples or various methods for producing the above-described compounds of the present invention. In Table 1, No. indicates compound No., Me is methyl, Et is ethyl, n-Pr is normal propyl, i-Pr is isopropyl, c-Pr is cyclopropyl, and t-Bu is Tertiary butyl, i-Bu represents isobutyl, Ph represents phenyl, Py represents pyridyl, and the temperatures shown as physical properties are melting points. Further, for some of the compounds of the formula (I), ¹ H-NMR data [measured by ¹ H-nuclear magnetic resonance spectroscopy. δ is a chemical shift value] is shown in Table 2.

Next, test examples are described.
Test Example 1 Nile spider mite insecticide test A chemical solution was prepared so that the concentration of the compound of the present invention was 200 ppm. Only one primary bean leaf was left and transplanted to a pot (diameter: 8 cm, height: 7 cm), and 20 adult spider mites were released. This was dipped in the above chemical solution together with green beans, air-dried, and left in a constant temperature room at 25 ° C. with illumination. Life or death was determined on the second or third day after the treatment, and the killing rate was determined by the following formula. The detached adults and abnormal insects were regarded as dead. Compound No. 1, 2, 6, 7, 10, 14-16, 20, 21, 25, 26, 28, 29, 32, 33, 35, 37, 39, 44, 46, 51-55, 87, When 131, 132, 143, 171, 177, 179, 181, 311-314, 317, 322-324, 326, 328, 330, 332-337 were tested, all compounds had an insecticidal rate of 90% or more. showed that.
Morbidity rate (%) = (number of dead ticks / number of treated ticks) × 100

Test Example 2 Effect test on green planthopper Rice seedlings were immersed for about 10 seconds in a chemical solution prepared so that the concentration of the compound of the present invention was 200 ppm. After the chemical solution was air-dried, the root was wrapped with wet absorbent cotton and placed in a test tube. Ten 10-year-old larvae were released into this, and the tube mouth was covered with gauze and left in a constant temperature room at 25 ° C. Five days after the insect release, the dead planthopper was judged to be alive or dead, and the mortality rate was determined by the following formula. The compounds No. 48, 131, and 326 were tested, and showed a death rate of 90% or more.
Death rate (%) = (Number of dead insects / Number of dead insects) × 100

Test Example 3 Knockdown (rollover) effect / acaricidal effect test for Phytophthora tick 1 mL of acetone solution of the compound of the present invention (concentration: 10 mg / mL, 1 mg / mL, 0.1 mg / mL, 0.01 mg) on filter paper installed in the petri dish After the filter paper has dried, place 100 juvenile ticks (spotted ticks) in a petri dish, cover with a polyethylene sheet, and seal. Record the number of ticks knocked down after 10, 30, 60, and 240 minutes over time, and record the number of ticks that died 24, 48, and 72 hours over time after placing ticks. Repeat twice.

Test Example 4 Medicinal Efficacy Test Using Dogs for Phytophthora tick Dogs (beagle, 8 months old) were administered a gelatin capsule containing 10 mg / kg body weight of the compound of the present invention. Let go through and artificially infest. After the treatment, observe the number of infestations, the number of drops, and the life and death of the fallen spider mites. As a result, the compound of the present invention drops or kills the parasitic spider mite.

Test Example 5 Medicinal Efficacy Test Using a Dog against a Cat Flea A gelatin capsule containing 10 mg / kg body weight of the compound of the present invention was administered to a dog (beagle, 8 months old), and immediately after that about 100 cat flea non-blood-sucking adults were covered in the back Let go on and let it infest. After the treatment, collect the cat fleas using a flea removal comb and count the number of fixings. As a result, the compound of the present invention suppresses cat flea infestation.

Next, formulation examples are described.
Formulation Example 1
(1) Compound of the present invention 20 parts by weight (2) Clay 70 parts by weight (3) White carbon 5 parts by weight (4) Sodium polycarboxylate 3 parts by weight (5) Sodium alkylnaphthalene sulfonate 2 parts by weight or more To make a wettable powder.

Formulation Example 2
(1) Compound of the present invention 5 parts by weight (2) Talc 60 parts by weight (3) Calcium carbonate 34.5 parts by weight (4) Liquid paraffin 0.5 parts by weight or more are uniformly mixed to obtain a powder.

Formulation Example 3
(1) Compound of the present invention 20 parts by weight (2) N, N-dimethylacetamide 20 parts by weight (3) Polyoxyethylene tristyryl phenyl ether 10 parts by weight (4) Calcium dodecylbenzenesulfonate 2 parts by weight (5) Xylene 48 A mixture of more than parts by weight is uniformly mixed and dissolved to obtain an emulsion.

Formulation Example 4
(1) Clay 68 parts by weight (2) Sodium lignin sulfonate 2 parts by weight (3) Polyoxyethylene alkylaryl sulfate 5 parts by weight (4) White carbon 25 parts by weight A mixture of each component and the present compound Mix at a weight ratio of 4: 1 to make a wettable powder.

Formulation Example 5
(1) Compound of the present invention 50 parts by weight (2) Sodium alkylnaphthalene sulfonate formaldehyde condensate 2 parts by weight (3) Silicone oil 0.2 parts by weight (4) Water 47.8 parts by weight or more uniformly mixed (5) 5 parts by weight of sodium polycarboxylate (6) 42.8 parts by weight of anhydrous sodium sulfate are further added to the crushed stock solution, and the mixture is uniformly mixed, granulated and dried to obtain a granulated wettable powder.

Formulation Example 6
(1) Compound of the present invention 5 parts by weight (2) Polyoxyethylene octylphenyl ether 1 part by weight (3) Polyoxyethylene alkyl ether phosphate 0.1 part by weight (4) Granular calcium carbonate 93.9 parts by weight (1 ) To (3) are uniformly mixed in advance and diluted with an appropriate amount of acetone, and then sprayed onto (4) to remove acetone and form granules.

Formulation Example 7
(1) Compound of the present invention 2.5 parts by weight (2) N, N-dimethylacetamide 2.5 parts by weight (3) Soybean oil 95.0 parts by weight or more are uniformly mixed and dissolved to give a trace amount of spray ( ultra low volume formulation).

Formulation Example 8
(1) Compound of the present invention 40 parts by weight (2) Polyoxyethylene tristyryl phenyl ether potassium phosphate 4 parts by weight (3) Silicone oil 0.2 part by weight (4) Xanthan gum 0.1 part by weight (5) Ethylene glycol 5 Part by weight (6) Water 50.7 parts by weight or more are uniformly mixed and pulverized to obtain an aqueous suspension.

Formulation Example 9
(1) Compound of the present invention 10 parts by weight (2) Diethylene glycol monoethyl ether 80 parts by weight (3) Polyoxyethylene alkyl ether 10 parts by weight or more of ingredients are mixed uniformly to obtain a liquid agent.

Claims (12)

Formula (I):

Wherein R ¹ is alkyl optionally substituted with halogen, alkenyl optionally substituted with halogen, or alkynyl optionally substituted with halogen; R ² is phenyl optionally substituted with X or X X is halogen, alkyl, haloalkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, alkylthio, amino, nitro, or cyano; R ³ and R ⁴ are each independently a hydrogen atom, halogen, Alkyl, alkenyl, alkynyl or cyano; R ⁵ is alkyl optionally substituted with A, alkenyl optionally substituted with A or alkynyl optionally substituted with A; A is halogen, cyano or cycloalkyl And n is 0, 1 or 2.] A diaryltriazole derivative represented by the formula: R ¹ is alkyl optionally substituted with halogen; R ² is phenyl optionally substituted with X or pyridyl optionally substituted with X; X is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, Alkylthio, amino, nitro or cyano; R ³ and R ⁴ are each independently a hydrogen atom, halogen, alkyl or cyano; R ⁵ is alkyl optionally substituted with A or alkenyl optionally substituted with A 2. The diaryltriazole derivative or a salt thereof according to claim 1, wherein The diaryltriazole derivative or a salt thereof according to claim 2, wherein R ³ and R ⁴ are each independently halogen, alkyl or cyano; and R ⁵ is alkyl optionally substituted with A. The diaryltriazole derivative or a salt thereof according to claim 1, wherein R ² is pyridyl which may be substituted with X. The diaryltriazole derivative or a salt thereof according to claim 4, wherein the pyridyl which may be substituted with X is 2-pyridyl which may be substituted with X. The diaryltriazole derivative or a salt thereof according to claim 1, wherein n is 0. An insecticide, acaricide, nematicide or soil insecticide containing the diaryltriazole derivative or salt thereof according to claim 1 as an active ingredient. The insecticide, acaricide, nematicide or soil insecticide containing the diaryltriazole derivative or salt thereof according to claim 7 as an active ingredient is an insecticide, acaricide, Nematode or soil killing pesticide. An agricultural or horticultural insecticide or acaricide containing the diaryltriazole derivative or salt thereof according to claim 8 as an active ingredient. Insecticide, wherein the insecticide, acaricide, nematicide or soil insecticide containing the diaryltriazole derivative or salt thereof according to claim 7 as an active ingredient is for controlling animal parasitic pests or mites Agent or acaricide. A method for controlling pests, mites, nematodes or soil pests by applying an effective amount of the diaryltriazole derivative or salt thereof according to claim 1. Formula (I):

Wherein R ¹ is alkyl optionally substituted with halogen, alkenyl optionally substituted with halogen, or alkynyl optionally substituted with halogen; R ² is phenyl optionally substituted with X or X X is halogen, alkyl, haloalkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, alkylthio, amino, nitro, or cyano; R ³ and R ⁴ are each independently a hydrogen atom, halogen, Alkyl, alkenyl, alkynyl or cyano; R ⁵ is alkyl optionally substituted with A, alkenyl optionally substituted with A or alkynyl optionally substituted with A; A is halogen, cyano or cycloalkyl And n is 0, 1 or 2.] of the diaryltriazole derivative represented by A manufacturing method,
(1) Formula (II):

(Wherein R ¹ , R ³ , R ⁴ , R ⁵ and n are as defined above) and formula (III): R ² CHO (wherein R ² is as defined above) A compound represented by formula (IV):

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and n are as described above), and this is dehydrogenated,
(2) reacting the compound of the formula (II) with a compound represented by the formula (V): R ² COCl (wherein R ² is as defined above),
(3) Formula (Ia):

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as described above) or
(4) Formula (Ic):

^{(Wherein, R 1, R 2, R} 3, R 4 and n are as defined above, R ^5c is alkyl which may be substituted with ^{A 1,} with an alkenyl or ^{A 1} may be substituted by ^{A 1} Alkynyl which may be substituted; A ¹ is halogen, cyano or cycloalkyl) or (5) Formula (VI):

(Wherein R ¹ , R ² , R ³ and R ⁴ are as described above) or the formula (XIV):

(Wherein R ¹ , R ² , R ³ and R ⁴ are as described above) and formula (VII): R ⁵ L ¹ (wherein R ⁵ is as described above). , L ¹ is a leaving group), and a method for producing a diaryltriazole derivative or a salt thereof.