WO2011049232A1

WO2011049232A1 - Diaryltriazole derivative as insecticide, miticide, nematicide or soil pesticide

Info

Publication number: WO2011049232A1
Application number: PCT/JP2010/068792
Authority: WO
Inventors: Kenichi Nakamoto; Taku Hamamoto; Yuko Nishihama; Tatsuya Kani; Tatsuya Shimada
Original assignee: Ishihara Sangyo Kaisha, Ltd.
Priority date: 2009-10-21
Filing date: 2010-10-19
Publication date: 2011-04-28
Also published as: TW201127291A; AR078605A1; JP2011105700A

Abstract

To provide a novel insecticide, miticide, nematicide or soil pesticide. The present invention provides an insecticide, miticide, nematicide or soil pesticide containing a diaryltriazole derivative of the formula (I) or its salt, as an active ingredient: wherein R¹ is alkyl which may be substituted by halogen, alkenyl which may be substituted by halogen, or alkynyl which may be substituted by halogen; R² is phenyl which may be substituted by X, or pyridyl which may be substituted by X; X is halogen, alkyl, haloalkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, alkylthio, amino, nitro or cyano; each of R³ and R⁴ which are independent of each other, is a hydrogen atom, halogen, alkyl, alkenyl, alkynyl or cyano; R⁵ is alkyl which may be substituted by A, alkenyl which may be substituted by A, or alkynyl which may be substituted by A; A is halogen, cyano or cycloalkyl; and n is 0, 1 or 2.

Description

DESCRIPTION

DIARYLTRIAZOLE DERIVATIVE AS INSECTICIDE, MITICIDE, NEMATICIDE OR SOIL PESTICIDE

TECHNICAL FIELD

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

BACKGROUND ART

Patent Document 1 discloses a phenyltriazole derivative useful as an insecticide or miticide, which is, however, different from the compound of the present invention with respect to the substituent corresponding to R² in the after-mentioned formula (I). Further, Patent Document 2 discloses a (3-sulfur atom-substituted phenyl)heteroaryl derivative useful as an insecticide or miticide, which is, however, different from the compound of the present invention with respect to the position of phenyl substituted on a triazole ring.

Patent Document 1 : WO99/55668

Patent Document 2: JP-A-2008-308448

DISCLOSURE OF THE INVENTION

OBJECT TO BE ACCOMPLISHED BY THE INVENTION

For many years, many insecticides, miticides, nematicides or soil pesticides have been used, but many of them have various problems such that the effects are inadequate, their use is restricted as insects, etc. have acquired resistance, etc.

Accordingly, it is desired to develop a novel insecticide, miticide, nematicide or soil pesticide substantially free from such problems. MEANS TO ACCOMPLISH THE OBJECT

The present inventors have conducted various studies on phenyltriazole derivatives in an effort to find a superior insecticide, miticide, nematicide or soil pesticide. As a result, they have found that a novel diaryltriazole derivative has a very high controlling effect particularly against spider mite at a low dose and at the same time has safety to crop plants, natural enemies of insects, etc. or mammals, and have accomplished the present invention.

That is, the present invention relates to a diaryltriazole derivative represented by the formula (I) or its salt:

wherein R is alkyl which may be substituted by halogen, alkenyl which may be substituted by halogen, or alkynyl which may be substituted by halogen; R² is phenyl which may be substituted by X, or pyridyl which may be substituted by X; X is halogen, alkyl, haloalkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, alkylthio, amino, nitro or cyano; each of R³ and R⁴ which are independent of each other, is a hydrogen atom, halogen, alkyl, alkenyl, alkynyl or cyano; R⁵ is alkyl which may be substituted by A, alkenyl which may be substituted by A, or alkynyl which may be substituted by A; A is halogen, cyano or cycloalkyl; and n is 0, 1 or 2. Further, the present invention relates to an insecticide, miticide, nematicide or soil pesticide containing the diaryltriazole derivative of the formula (I) or its salt, as an active ingredient, a method for controlling insects, mites, nematicides or soil pests by applying it, and a process for its production.

ADVANTAGEOUS EFFECTS OF THE INVENTION

An insecticide, miticide, nematicide or soil pesticide containing the diaryltriazole derivative of the above formula (I) or its salt as an active ingredient has a very high controlling effect against insects, mites, nematodes or soil pests at a low dose.

BEST MODE FOR CARRYING OUT THE INVENTION

As the halogen in the formula (I) or the halogen as a substituent, an atom of fluorine, chlorine, bromine or iodine may be mentioned. The number of halogens as the substituents may be 1 or more, and if more, the respective halogens may be the same or different. Further, the positions for substitution of such halogens may be any positions.

The alkyl in the formula (I) may be linear or branched. As its specific examples, Ci_-6 alkyl such as methyl, ethyl, propyl, isopropy, butyl, tert-butyl, pentyl or hexyl may be mentioned.

As the cycloalkyl in the formula (I), C₃-e cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl may, for example, be mentioned.

The alkenyl in the formula (I) may be linear or branched. As its specific examples, C₂-6 alkenyl such as vinyl, 1 -propenyl, allyl, isopropenyl, 1 -butenyl, 1 ,3- butadienyl or 1-hexenyl may be mentioned.

The alkynyl in the formula (I) may be linear or branched. As its specific examples, C₂-6 alkynyl such as ethynyl, 2-butynyl, 2-pentynyl, 3-methyl-1 -butynyl, 2- penten-4-ynyl or 3-hexynyl may be mentioned.

The pyridyl represented by R² in the formula (I) may, for example, be 2-pyridyl, 3- pyridyl or 4-pyridyl. Among them, 2-pyridyl is preferred. Further, in a case where the pyridyl is substituted by substituents X, the plurality of X may be the same or different, and the number of substituents is from 1 to 4.

In a case where the phenyl represented by R² in the formula (I) is substituted by substituents X, a plurality of X may be the same or different, and the number of the substituents is from 1 to 5.

The salt of the diaryltriazole derivative of the above formula (I) includes all kinds so long as they are acceptable in this technical field. For example, an ammonium salt such as a dimethylammonium salt or a triethylammonium salt; an inorganic acid salt such as a hydrochloride, a perchlorate, a sulfate or a nitrate; or an organic acid salt such as an acetate or a methanesulfonate, may be mentioned.

The diaryltriazole derivative of the above formula (I) may have isomers such as optical isomers or geometrical isomers, and such isomers and mixtures thereof are both included in the present invention. In this specification, isomers are in the form of a mixture, unless otherwise specified. Further, in the present invention, various isomers other than those mentioned above, may be included within the scope of the common knowledge in this technical field. Further, depending upon the type of the isomer, it may have a chemical structure different from the above formula (I), but for those skilled in the art it can sufficiently be recognized that it is in an isomeric relationship and falls within the scope of the present invention.

The diaryltriazole derivative of the above formula (I) or its salt (hereinafter referred to simply as the compound of the present invention) can be produced by the following Processes [1] to [6] and in accordance with a usual process for producing a salt. However, the present invention is by no means limited to such processes.

PROCESS [1]

In the above formulae, R¹, R², R³, R⁴, R⁵ and n are as defined above. The Process [1] is a process for producing a compound of the formula (I), which comprises reacting a compound of the formula (II) with a compound of the formula (III) to obtain a compound of the formula (IV) and subjecting it to dehydrogenation, and it comprises the above steps 1-1 and 1-2. The respective reaction steps will be described in detail.

The reaction in the step 1-1 can usually be carried out in the presence of an acid and a solvent. As the acid, one or more may suitably be selected from e.g. acetic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid and p-toluenesulfonic acid. The acid may be used in an amount of from 0.05 to 2 times by mol, preferably from 0.1 to 1 time by mol, to the compound of the formula (II).

The solvent is not particularly limited so long as the reaction thereby proceeds, and one or more may suitably be selected from e.g. ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane and dimethoxyethane; halogenated

hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and dichloroethylene; aromatic hydrocarbons such as benzene, toluene and xylene; and aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane.

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

After completion of the reaction of the step 1 -1 , the reaction of the step 1 -2 may be carried out after isolating the obtained compound of the formula (IV) or continuously without such isolation. When the compound of the formula (IV) is isolated, the reaction of the step 1 -2 is usually carried out in the presence of a base or an oxidizing agent. In a case where the compound of the formula (IV) is not isolated, depending upon the type of the compound of the formula (III) to be used, the reaction may proceed even without using a base or an oxidizing agent.

As the base, one or more may suitably be selected from e.g. amines such as trimethylamine, triethylamine, triisopropylamine, diisopropylamine, pyridine, 2-picoline, 3-picoline, 4-picoline, 4-dimethylaminopyridine, 2,6-dimethylpyridine, 4- pyrollidinopyridine, N-methylmorpholine, N,N-dimethylaniline, Ν,Ν-diethylaniline, N- ethyl-N-methylaniline, 1 ,8-diazabicyclo[5.4.0]-7-undecene and 1 ,4- diazabicyclo[2.2.2]octane. The base can be used in an amount of from 0.1 to 5 times by mol, preferably from 1 to 3 times by mol, to the compound of the formula (IV).

As the oxidizing agent, one or more may suitably be selected from e.g. 2,3- dichloro-5,6-dicyano-1 ,4-benzoquinone, chloranil, o-chloranil, hydrogen peroxide, ammonium peroxydisulfate, sodium peroxydisulfate, potassium peroxydisulfate, potassium permanganate, OXONE (tradename, manufactured by E.I. DuPont;

containing potassium hydrogen peroxosulfate), sodium hypochlorite, sodium chlorite, benzoyl peroxide, tert-butyl hydroperoxide, oxygen, etc. The oxidizing agent may be used in an amount of from 1 to 10 times by mol, preferably from 1 to 4 times by mol, to the compound of the formula (IV).

The reaction in the step 1 -2 is usua y carried out in the presence of a solvent. The solvent is not particularly limited so long as the reaction thereby proceeds, and the same one as in the above step 1 -1 may be used. Further, in addition thereto, one or more may suitably be selected from e.g. polar aprotic solvents such as acetonitrile, propiononitrile, N,N-dimethylformamide, N,N~dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulfolane and N-methyl-2-pyrrolidone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol; organic acids such as acetic acid and propionic acid; water; and esters such as methyl acetate and ethyl acetate.

The reaction in the step 1 -2 may be carried out usually from -20 to 250°C, preferably from 0 to 150°C, and the reaction time is usually from about 0.5 to 48 hours, preferably from about 1 to 30 hours.

PROCESS [2]

(Π) 0⁾

In the above formulae, R¹, R², R³, R⁴, R⁵ and n are as defined above. The Process [2] is a process for producing a compound of the formula (I), which comprises reacting a compound of the formula (II) with a compound of the formula (V), and it will be described in detail.

The reaction of the Process [2] can be carried out usually in the presence of a base and a solvent. As the base, the same one as in the step 1 -2 of the Process [1 ] may be used. The base may be used in an amount of from 0.5 to 5 times by mol, preferably from 1 to 2 times by mol, to the compound of the formula (II).

The solvent is not particularly limited so long as the reaction thereby proceeds, and for example, the one exemplified in the step 1 -1 of the Process [1] may be used.

The reaction of the Process [2] may be carried out usually from - 20 to 250°C, preferably from 0 to 150°C, and the reaction time is usually from about 0.5 to 48 hours, preferably from about 3 to 12 hours.

In the above formulae, R¹, R², R³, R⁴ and R⁵ are as defined above, and nb is 1 or 2. The Process [3] is a process for producing a compound of the formula (l-b), which comprises oxidizing a compound of the formula (l-a), and it will be described in detail.

The oxidation reaction of the Process [3] may be carried out in the presence of an oxidizing agent. As the oxidizing agent, one or more may suitably be selected from e.g. m-chloroperbenzoic acid, hydrogen peroxide, sodium periodate, OXONE (tradename, manufactured by E.I. DuPont; containing potassium hydrogen

peroxosulfate), tert-butyl hypochlorite and sodium hypochlorite. Among such oxides, m-chloroperbenzoic acid and/or hydrogen peroxide is preferred, and m- chloroperbenzoic acid is further preferred. The oxidizing agent may be used in an amount of from 1 to 10 times by mol, preferably from 1 to 6 times by mol, to the compound of the formula (l-a).

The reaction of the Process [3] may be carried out usually in the presence of a solvent. The solvent is not particularly limited so long as the reaction thereby proceeds, and one or more may suitably be selected from e.g. ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane and dimethoxyethane; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and dichloroethylene; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; polar aprotic solvents such as acetonitrile, propiononitrile, Ν,Ν-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulfolane and N-methyl-2- pyrrolidone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol; organic acids such as acetic acid and propionic acid; water; and ketones such as acetone, methyl ethyl ketone and cyclohexanone.

The reaction of the Process [3] may be carried out usually from -30°C to a refluxing temperature in the reaction system, preferably from -10°C to 100°C, and the reaction time is usually from about 0.1 to 48 hours, preferably from about 0.5 to 24 hours.

In the above formulae, R¹, R², R³, R⁴ and n are as defined above, R^5c is alkyl which may be substituted by A¹, alkenyl which may be substituted by A¹, or alkynyl which may be substituted by A¹; R^5d is haloalkyl which may be substituted by A², haloalkenyl which may be substituted by A², or haloalkynyl which may be substituted by A²; A¹ is halogen, cyano or cycloalkyl; and A² is cyano or cycloalkyl. The Process [4] is a process for producing a compound of the formula (l-d), which comprises halogenating a compound of the formula (l-c), and it will be described in detail.

The halogenation reaction of the Process [4] can be carried out in the presence of a halogenating agent. As the halogenating agent, one or more may suitably be selected from e.g. chlorine, bromine, chloramine, N-chlorosuccinimide, N- bromosuccinimide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, thionyl chloride and thionyl bromide.

The halogenation reaction of the Process [4] may be carried out usually in the presence of a solvent. The solvent is not particularly limited so long as the reaction thereby proceeds, and one or more may suitably be selected from e.g. ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane and dimethoxyethane;

halogenated hydrocarbons such as chlorobenzene, dichlorobenzene,

dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and dichloroethylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; polar aprotic solvents such as acetonitrile, propiononitrile, N,N- dimethylformamide, Ν,Ν-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulfolane and N-methyl-2-pyrrolidone; organic acids such as acetic acid and propionic acid; water; and esters such as methyl acetate and ethyl acetate.

The halogenation reaction of the Process [4] may be carried out usually from -100 to 150°C, preferably from -10 to 110°C, and the reaction time is usually from about 0.1 to 48 hours, preferably from about 0.5 to 24 hours.

PROCESS [5]

In the above formulae, R¹, R², R³, R⁴ and R⁵ are as defined above, and L¹ is a leaving group. The Process [5] is a process for producing a compound of the formula (l-a), which comprises reacting a compound of the formula (VI) or (XIV) with a compound of the formula (VII), and it will be described in detail.

The reaction of the Process [5] may be carried out usually in the presence of a base and/or a reaction initiator. The base may be any base so long as it exhibits a pH of at least 8, and one or more may suitably be selected from e.g. alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium hydrogencarbonate (another name: sodium bicarbonate) and potassium hydrogencarbonate; alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide; and organic metals such as methyl lithium, butyl lithium, methyl magnesium bromide and lithium diisopropylamide. Among these bases, alkali metal carbonates, alkali metal bicarbonates, alkali metal hydrides or alkali metal alkoxides are preferred, and sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate or sodium hydride is further preferred. The base may be used in an amount of from 1 to 10 times by mol, preferably from 1 to 3 times by mol, to the compound of the formula (VI).

The leaving group L¹ is not particularly limited so long as the reaction thereby proceeds, and it may, for example, be halogen or a tosyl.

As the reaction initiator, one or more may suitably be selected from e.g. sulfurous acid, sulfites and Rongalit (tradename for sodium -formaldehyde-sulfoxylate). The reaction initiator may be used in an amount of from 0.05 to 5 times by mol, preferably from 0.1 to 1.2 times by mol, to the compound of the formula (VI) or (XIV).

The reaction of the Process [5] may be carried out usually in the presence of a solvent. As the solvent, one or more may suitably be selected from e.g. ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane and dimethoxyethane; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene,

dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and dichloroethylene; aromatic hydrocarbons such as benzene, toluene and xylene;

aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; polar aprotic solvents such as acetonitrile, propiononitrile, N,N-dimethylformamide, Ν,Ν-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulfolane and N-methyl-2-pyrrolidone; and water.

The reaction of the Process [5] may be carried out usually from -40°C to a refluxing temperature in the reaction system, preferably from 0°C to 100°C, and the reaction time is usually from about 10 minutes to 24 hours, preferably from about 0.5 to 20 hours.

The compound of the formula (XIV) may be produced by reducing the compound of the formula (VI) by a usual method. The compound of the formula (VI) and the compound of the formula (XIV) are mutually convertible by an oxidation reduction reaction, and the compound of the formula (VI) may readily be oxidized by oxygen in air to form the compound of the formula (XIV).

PROCESS [6]

(i-f) (I-g)

In the above formulae, R¹, R³, R⁴ and R⁵ are as defined above, and Q is a benzene ring or a pyridine ring. The Process [6] is a process for producing a compound of the formula (l-g), which comprises reducing a compound of the formula (l-f), and it will be described in detail.

The reduction reaction of the Process [6] is a reaction of the compound of the formula (l-f) with a reducing agent. The reduction reaction may, for example, be the following catalytic hydrogenation reaction or a reduction reaction by a metal or metal salt, and by either reaction, it is possible to produce the compound of the formula (l-g).

The reducing agent for the catalytic hydrogenation reaction is hydrogen. The catalytic hydrogenation reaction may be carried out usually in the presence of a catalyst and a solvent. As the catalyst, one or more may suitably be selected from palladium carbon, Raney nickel and platinum oxide. The catalyst may be used in an amount of from 0.0001 to 10 times by mol, preferably from 0.001 to 1 time by mol, to the compound of the formula (l-f).

The solvent is not particularly limited so long as the reaction thereby proceeds, and one or more may suitably be selected from e.g. ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane and dimethoxyethane; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; polar aprotic solvents such as acetonitrile, propiononitrile, N,N-dimethylformamide, Ν,Ν-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulfolane and N-methyl-2-pyrrolidone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol; organic acids such as acetic acid and propionic acid; esters such as methyl acetate and ethyl acetate; and pyridines such as pyridine and picoline.

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

The reducing agent for the reduction reaction by a metal or a metal salt is a metal or a metal salt, and one or more may suitably be selected from e.g. zinc, tin, tin chloride, iron, etc. The metal or metal salt may be used in an amount of from 1 to 100 times by mol, preferably from 1 to 10 times by mol, to the compound of the formula (I- f).

The reduction reaction by a metal or metal salt may be carried out in the presence of an acid or base, as the case requires. As the acid, one or more may suitably be selected from e.g. organic acids such as acetic acid and propionic acid; and inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid. As the base, one or more may suitably be selected from e.g. alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; and alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide. The acid or base may be used in an amount of from 0.1 to 1 ,000 times by mol, preferably from 1 to 100 times by mol, to the compound of the formula (l-f).

The reduction reaction by a metal or metal salt may be carried out usually in the presence of a solvent. The solvent is not particularly limited so long as the reaction thereby proceeds, and for example, one exemplified in the above catalytic

hydrogenation reaction may be used. Further, in addition thereto, one or more may suitably be selected from e.g. halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and dichloroethylene; and water.

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

[Process for producing intermediate]

The compound of the formula (VI) as a starting material of the Process [5] may be produced, for example, by three step reactions comprising (1) a first step of subjecting a compound of the formula (VIII) and a compound of the formula (IX) to a coupling reaction to obtain a compound of the formula (X), (2) a second step of halosulfonylating the compound of the formula (X) to obtain a compound of the formula (XI) and (3) a third step of reducing the compound of the formula (XI) to obtain a compound of the formula (VI). The process will be described in detail. In the following formulae, R¹, R², R³ and R⁴ are as defined above, and X is halogen.

The coupling reaction is carried out usually in the presence of a copper catalyst. The copper catalyst may be any copper catalyst so long as the coupling reaction can thereby be carried out, and one or more may suitably be selected from e.g. copper (metal copper), copper(ll) sulfate, copper(l) sulfate, copper(ll) oxide, copper(l) oxide, copper(ll) chloride, copper(l) chloride, copper(ll) acetate and copper(l) acetate. The copper catalyst may be used in an amount of from 0.001 to 1 time by mol, preferably from 0.01 to 0.5 time by mol, to the compound of the formula (X).

The coupling reaction may be carried out in the presence of a base and a solvent, as the case requires. As the base, the same one as in the step 1-2 of the _{1 Q}

Process [1] may be used. The base may be used in an amount of from 0.1 to 10 times by mol, preferably from 1 to 2 times by mol, to the compound of the formula (VIII). The solvent is not particularly limited so long as the reaction thereby proceeds, and one or more may suitably be selected from e.g. ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane and dimethoxyethane; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; and polar aprotic solvents such as acetonitrile, propiononitrile, Ν,Ν-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulfolane and N-methyl-2- pyrrolidone. The coupling reaction may be carried out usually from 0°C to a refluxing temperature in the reaction system, preferably from 10°C to 150°C, and the reaction time is usually from about 1 to 30 hours.

The halosulfonylation reaction may be carried out in the presence of a

halosulfonylation agent. As the halosulfonylation agent, one or more may suitably be selected from e.g. halosulfonic acid compounds such as chlorosulfonic acid and bromosulfonic acid. Among these sulfonylation agents, it is preferred to use chlorosulfonic acid. The halosulfonylation agent may be used in an amount of from 1 to 100 times by mol, preferably from 1 to 10 times by mol, to the compound of the formula (X).

The halosulfonylation reaction may be carried out in the presence of a solvent, as the case requires. The solvent is not particularly limited so long as the reaction thereby proceeds, and one or more may suitably be selected from e.g. ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane and dimethoxyethane;

halogenated hydrocarbons such as chlorobenzene, dichlorobenzene,

dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and dichloroethylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; and organic acids such as acetic acid and propionic acid.

The halosulfonylation reaction may be carried out usually at from -10°C to a refluxing temperature in the reaction system, preferably from 10°C to 150°C, and the reaction time is usually from about 1 to 48 hours, preferably from about 1 to 24 hours.

The reduction reaction may be carried out in the presence of a reducing agent. As the reducing agent, one or more may suitably be selected from e.g. metal compounds such as zinc, tin and iron; phosphorus compounds such as red

phosphorus and triphenylphosphine; and halogen compounds such as potassium iodide and iodine. The reducing agent may be used in an amount of from 1 to 100 times by mol, preferably from 1 to 0 times by mol, to the compound of the formula (XI).

The reduction reaction may be carried out in the presence of an acid, as the case requires. As the acid, one or more may suitably be selected from e.g. 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; and solid acids such as montmorillonite K-10. The acid may be used in an amount of from 0.066 to 200 times by mol, preferably from 2 to 20 times by mol, to the compound of the formula (XI).

The reduction reaction may be carried out in the presence of a solvent, as the case requires. The solvent is not particularly limited so long as the reaction thereby proceeds, and one or more may suitably be selected from e.g. ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane and dimethoxyethane; aromatic - hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol; and nitriles such as acetonitrile and propiononitrile.

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

The compound of the formula (X) obtainable in the first step (1) of the above "Process for producing intermediate" may be produced also by the following Process [A] or [B].

PROCESS [A]

In the Process [A], R , R², R³ and R⁴ are as defined above. The Process [A] is a process for producing the compound of the formula (X), which comprises reacting a compound of the formula (XII) with a compound of the formula (III) to obtain a compound of the formula (XIII), and subjecting it to dehydrogenation, and it comprises the above steps A-1 and A-2. The Process [A] may be carried out in accordance with the above Process [1].

PROCESS [B]

(Xii) (X)

In the Process [B], R¹, R², R³ and R⁴ are as defined above. The Process [B] is a process for producing the compound of the formula (X), which comprises reacting a compound of the formula (XII) with a compound of the formula (V). The Process [B] may be carried out in accordance with the above Process [2].

The compound of the formula (XII) as the starting material for the above Process [A] or [B] may be produced, for example, in accordance with the following Process [C]. PROCESS [C]

In the Process [C], R , R³ and R⁴ are as defined above. The Process [C] is a process for producing a compound of the formula (XII), which comprises reacting a compound of the formula (XV) with a compound of the formula (XVI) to obtain a compound of the formula (XVII), halogenating it to obtain a compound of the formula (XVIII), and further reacting the compound of the formula (XVIII) with aqueous ammonia, and it comprises the above steps C-1 , C-2 and C-3. Here, in the above step C-1 , instead of the compound of the formula (XVI), an acetal form or a hemiacetal form of the compound of the formula (XVI) may be used. The respective reaction steps will be described in detail.

The reaction of the step C-1 may be carried out in the presence of an acid, as the case requires. As the acid, one or more may suitably be selected from acetic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, etc. The acid may be used in an amount of from 0.05 to 2 times by mol, preferably from 0.1 to 1 time by mol, to the compound of the formula (XV).

The compound of the formula (XV) may be a salt. In a case where a salt of the compound of the formula (XV) is to be used, the reaction of the step C-1 may be carried out in the presence of a base, as the case requires. As the base, one or more may suitably be selected from e.g. alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium

hydrogencarbonate and potassium hydrogencarbonate; acetates such as sodium acetate and potassium acetate; and organic bases such as triethylamine and pyridine.

The reaction of the step C-1 may be carried out usually in the presence of a solvent. The solvent is not particularly limited so long as the reaction thereby proceeds, and the same one as for the reduction reaction in the above "Process for producing intermediate" may be used.

The reaction of the step C-1 may be carried out usually at from - 70°C to a refluxing temperature in the reaction system, preferably from -20°C to 150°C, and the reaction time is usually from about 10 minutes to 24 hours, preferably from about 30 minutes to 12 hours.

The halogenation reaction of the step C-2 may be carried out in the presence of a halogenating agent. As the halogenating agent, one or more may suitably be selected from e.g. chlorine, bromine, chloramine, N-chlorosuccinimide, N- bromosuccinimide, hypochlorous acid and tert-butyl hypochlorite.

After completion of the reaction of the step C-1 , the reaction of the step C-2 may be carried out after isolating the obtained compound of the formula (XVII) or

continuously without such isolation. In a case where the compound of the formula (XVII) is isolated, the reaction of the step C-2 may be carried out usually in the presence of a solvent. The solvent is not particularly limited so long as the reaction thereby proceeds, and the same one as for the coupling reaction in the above "Process for producing intermediate" may be used.

The halogenation reaction of the step C-2 may be carried out usually at from -70°C to a refluxing temperature in the reaction system, preferably from -20°C to 150°C, and the reaction time is usually from about 10 minutes to 24 hours, preferably from about 30 minutes to 12 hours.

The reaction of the step C-3 may be carried out usually in the presence of a solvent. The solvent is not particularly limited so long as the reaction thereby proceeds, and one or more may suitably be selected from e.g. ethers such as diethyl ether, butyl methyl ether, tetrahydrofuran, dioxane and dimethoxyethane; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and dichloroethylene; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; polar aprotic solvents such as acetonitrile, propiononitrile, Ν,Ν-dimethylformamide, N,N-dimethylacetamide, dimethy!sulfoxide, hexamethylphosphoric triamide, sulfolane and N-methyl-2- pyrrolidone; water; esters such as methyl acetate and ethyl acetate; ketones such as acetone, methyl ethyl ketone and cyclohexanone; and pyridines such as pyridine and picoline.

The reaction of the step C-3 may be carried out usually at from -30°C to a refluxing temperature in the reaction system, preferably from -10°C to 100°C, and the reaction time is usually from about 10 minutes to 24 hours, preferably from about 30 minutes to 12 hours.

Preferred embodiments of the insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention will be described below. The insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention is useful, for example, as an agent to control insects, mites, nematodes or soil pests which become problematic in the agricultural and horticultural fields, i.e. as an agricultural and horticultural insecticide, miticide, nematicide or soil pesticide or as an agent to control insects or mites parasitic on animals i.e. as an agent to control parasites on animals.

The compound of the present invention is useful as an agricultural and

horticultural insecticide, miticide, nematicide or soil pesticide. Specifically, it is effective to control insects, e.g. aphids such as green peach aphid (Mvzus persicae) and cotton aphid (Aphis qossvpii); agricultural insect pests such as diamondback moth (Plutella xylostella), cabbage armyworm (Mamestra brassicae), common cutworm

(Spodoptera litura), codling moth (Cvdia pomonella), bollwormfHeliothis zea), tobacco budworm (Heliothis virescens), gypsy moth (Lvmantria dispar), rice leafroller

(Cnaphalocrocis medinalis), smaller tea tortrix (Adoxophves sp.), Colorado potato beetle (Leptinotarsa decemlineata), cucurbit leaf beetle (Aulacophora femoralis), boll weevil (Anthonomus grandis), planthoppers, leafhoppers, scales, bugs, whiteflies, thrips, grasshoppers, anthomyiid flies, scarabs, black cutworm (Agrotis ipsilon), cutworm (Agrotis segetum) and ants; gastropods such as slugs and snails; hygienic insect pests such as tropical rat mite (Ornithonvssus bacoti), cockroaches, housefly (Musca domestical and house mosquito (Culex pipiensV. stored grain insect such as angoumois grain moth (Sitotroga cerealella), adzuki bean weevil (Callosobruchus chinensis), red flour beetle (Tribolium castaneum) and mealworms; and household goods insect pests such as casemaking clothes moth (Tinea pellionella), black carpet beetle (Attagenus iaponicus) and subterranean termites; mites, e.g. plant parasitic mites such as two-spotted spider mite (Tetranvchus urticae), carmine spider mite (Tetranychus cinnabarinus), kanzawa spider mite (Tetranvchus kanzawai), citrus red mite (Panonvchus citri), European red mite (Panonychus ulmi), broad mite

(Polyphagotarsonemus latus), pink citrus rust mite (Aculops pelekassi) and bulb mite (Rhizoglyphus echinopus); and domestic mites such as mold mite (Tyrophagus putrescentiae), Dermatophagoides farinae, Chelacaropsis moorei; nematodes, e.g. plant parasitic nematodes such as root-knot nematodes, cyst nematodes, root-lesion nematodes, white-tip nematode (Aphelenchoides bessevQ, strawberry bud nematode (Nothotylenchus acris), and pine wood nematode (Bursaphelenchus xylophilus); and soil pests, e.g. isopods such as pillbugs (Armadillidium vulgare) and pillbugs (Porcellio scaber). Among them, the agricultural and horticultural insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention is particularly effective for controlling plant parasitic mites, agricultural insect pests, plant parasitic nematodes or the like. Particularly, it is more effective for controlling plant parasitic mites and agricultural insect pests, and accordingly it is useful as an

insecticide or miticide. Further, it is effective against insect pests having acquired resistance to organophosphorus, carbamate, synthetic pyrethroid and/or neomicotinoid insecticides. Moreover, the compound of the present invention has excellent systemic properties, and by the application of the agricultural and horticultural insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention to soil treatment, not only noxious insects, noxious mites, noxious nematodes, noxious gastropods and noxious isopods in soil but also foliage pests can be controlled.

Another preferred embodiments of the insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention may be agricultural and horticultural insecticides, miticides, nematicides or soil pesticides which collectively control the above-mentioned plant parasitic mites, agricultural insect pests, plant parasitic nematodes, gastropods and soil pests.

The agricultural and horticultural insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention, is usually formulated by mixing the compound with various agricultural adjuvants and used in the form of a formulation such as a dust, granules, water-dispersible granules, a wettable powder, a water- based suspension concentrate, an oil-based suspension concentrate, water soluble granules, a water soluble powder, an emulsifiable concentrate, a soluble concentrate, a paste, an aerosol or an ultra low-volume formulation. However, so long as it is suitable for the purpose of the present invention, it may be formulated into any type of formulation which is commonly used in this field. Such agricultural adjuvants include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaoline, bentonite, kaolinite, sericite, clay, sodium carbonate, sodium

bicarbonate, mirabilite, zeolite and starch; solvents such as water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethylsulfoxide, N,N-dimethylformamide, Ν,Ν-dimethylacetamide, N- methyl-2-pyrrolidone, and alcohol; anionic surfactants such as a salt of fatty acid, a benzoate, an alkylsulfosuccinate, a dialkylsulfosuccinate, a polycarboxylate, a salt of alkylsulfuric acid ester, an alkyl sulfate, an alkylaryl sulfate, an alkyl diglycol ether sulfate, a salt of alcohol sulfuric acid ester, an alkyl sulfonate, an alkylaryl sulfonate, an aryl sulfonate, a lignin sulfonate, an alkyldiphenyl ether disulfonate, a polystyrene sulfonate, a salt of alkylphosphoric acid ester, an alkylaryl phosphate, a styrylaryl phosphate, a salt of polyoxyethylene alkyl ether sulfuric acid ester, a polyoxyethylene alkylaryl ether sulfate, a salt of polyoxyethylene alkylaryl ether sulfuric acid ester, a polyoxyethylene alkyl ether phosphate, a salt of polyoxyethylene alkylaryl phosphoric acid ester, and a salt of a condensate of naphthalene sulfonate with formaldehyde; nonionic surfactants such as a sorbitan fatty acid ester, a glycerin fatty acid ester, a fatty acid polyglyceride, a fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, an oxyalkylene block polymer, a polyoxyethylene alkyl ether, a polyoxyethylene alkylaryl ether, a polyoxyethylene styrylaryl ether, a polyoxyethylene glycol alkyl ether, a polyethylene glycol, a polyoxyethylene fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene glycerin fatty acid ester, a polyoxyethylene hydrogenated castor oil, and a polyoxypropylene fatty acid ester; vegetable and mineral oils such as olive oil, kapok oil, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, tung oil, and liquid paraffins; and so on. Each of the components as such adjuvants may be one or more suitably selected for use, so long as the purpose of the present invention can thereby be accomplished. Further, other than the above-mentioned adjuvants, some among those known in this field may suitably be selected for use. For example, various adjuvants which are commonly used, such as a filler, a thickener, an anti-settling agent, an anti-freezing agent, a dispersion stabilizer, a phytotoxicity reducing agent, an anti-mold agent, and so on, may also be employed.

The weight ratio of the compound of the present invention to the various agricultural adjuvants is usually from 0.001 :99.999 to 95:5, preferably from

0.005:99.995 to 90:10.

In the actual application of such a formulation, it may be used as it is, or may be diluted to a predetermined concentration with a diluent such as water, and various spreaders e.g. surfactants, vegetable oils or mineral oils may be added thereto, as the case requires.

The application of the agricultural and horticultural insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention cannot generally be defined, as it varies depending upon the weather conditions, the type of the formulation, the application season, the application site or the types or degree of outbreak of the pest insects. However, it is usually applied in a concentration of the active ingredient being from 0.05 to 800,000 ppm, preferably from 0.5 to 500,000 ppm, and the dose per unit area is such that the compound of the present invention is from 0.05 to 50,000 g, preferably from 1 to 30,000 g, per hectare. Further, the present invention includes such a method for controlling insects, mites, nematodes or soil pests, particularly for controlling plant parasitic mites, agricultural insect pests or plant parasitic nematodes by such applications.

Various formulations of the agricultural and horticultural insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention or their diluted compositions may be applied by conventional methods for application which are commonly employed, such as spraying (e.g. jetting, misting, atomizing, powder or grain scattering or dispersing in water), soil application (e.g. mixing or drenching), surface application (e.g. coating, powdering or covering) or impregnation to obtain poisonous feed. Further, it is possible to feed domestic animals with a food

containing the above active ingredient and to control the outbreak or growth of pests, ₆

particularly insect pests, with their excrements. Furthermore, the active ingredient may also be applied by a so-called ultra low-volume application method. In this method, the composition may be composed of 100% of the active ingredient.

Further, the agricultural and horticultural insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention may be mixed with or may be used in combination with other agricultural chemicals, fertilizers or phytotoxicity- reducing agents, whereby synergistic effects or activities may sometimes be obtained. Such other agricultural chemicals include, for example, a herbicide, an insecticide, a miticide, a nematicide, a soil pesticide, a fungicide, an antivirus agent, an attractant, an antibiotic, a plant hormone, a plant growth regulating agent, and so on. Especially, with an insecticidal, miticidal, nematicidal or soil pesticidal composition having a compound of the present invention mixed with or used in combination with one or more active compounds of other agricultural chemicals, the application range, the application time, the pesticidal activities, etc. may be improved to preferred directions. The compound of the present invention and the active compounds of other agricultural chemicals may separately be formulated so that they may be mixed for use at the time of application, or they may be formulated together. The present invention includes such an insecticidal, miticidal, nematicidal or soil pesticidal composition.

The mixing ratio of the compound of the present invention to the active

compounds of other agricultural chemicals can not generally be defined, since it varies depending upon the weather conditions, the types of formulations, the application time, the application site, the types or degree of outbreak of insect pests, etc., but it is usually within a range of from 1 :300 to 300: 1 , preferably from 1 : 100 to 100: 1 , by weight. Further, the dose for the application is such that the total amount of the active

compounds is from 0.1 to 50,000 g, preferably from 1 to 30,000 g, per hectare. The present invention includes a method for controlling insects, mites, nematodes or soil pests by an application of such an insecticidal, miticidal, nematicidal or soil pesticidal composition.

The active ingredient compounds of an insect pest control agents, such as the insecticide, the miticide, the nematicide or the soil insect pesticide in the above- mentioned other agricultural chemicals, include, for example, (by common names, some of them are still in an application stage, or test codes of Japan Plant Protection Association):

organic phosphate compounds, such as profenofos, dichlorvos, fenamiphos, fenitrothion, EPN, diazinon, chlorpyrifos, chlorpyrifos-methyl, acephate, prothiofos, fosthiazate, cadusafos, disulfoton, isoxathion, isofenphos, ethion, etrimfos, quinalphos, dimethylvinphos, dimethoate, sulprofos, thiometon, vamidothion, pyraclofos,

pyridaphenthion, pirimiphos-methyl, propaphos, phosalone, formothion, malathion, tetrachlorvinphos, chlorfenvinphos, cyanophos, trichlorfon, methidathion, phenthoate, ESP, azinphos-methyl, fenthion, heptenophos, methoxychlor, parathion, phosphocarb, demeton-S-methyl, monocrotophos, methamidophos, imicyafos, parathion-methyl, terbufos, phosphamidon, phosmet and phorate;

carbamate compounds, such as carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, ethiofencarb, pirimicarb, fenobucarb, carbosulfan, benfuracarb, bendiocarb, furathiocarb, isoprocarb, metolcarb, xylylcarb, XMC and fenothiocarb;

nereistoxin derivatives, such as cartap, thiocyclam, bensultap and thiosultap- sodium; organic chlorine compounds, such as dicofol, tetradifon, endosulfan, dienochlor and dieldrin;

organic metal compounds, such as fenbutatin oxide and cyhexatin;

pyrethroid compounds, such as fenvalerate, permethrin, cypermethrin,

deltamethrin, cyhalothrin, tefluthrin, ethofenprox, flufenprox, cyfluthrin, fenpropathrin, flucythrinate, fluvalinate, cycloprothrin, lambda-cyhalothrin, pyrethrins, esfenvalerate, tetramethrin, resmethrin, protrifenbute, bifenthrin, zeta-cypermethrin, acrinathrin, alpha-cypermethrin, allethrin, gamma-cyhalothrin, theta-cypermethrin, tau-fluvalinate, tralomethrin, profluthrin, beta-cypermethrin, beta-cyfluthrin, metofluthrin, phenothrin and flumethrin;

benzoylurea compounds, such as diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, lufenuron, novaluron, triflumuron, hexaflumuron, bistrifluron,

noviflumuron and fluazuron;

juvenile hormone-like compounds, such as methoprene, pyriproxyfen, fenoxycarb and diofenolan;

pyridazinone compounds, such as pridaben;

pyrazole compounds, such as fenpyroximate, fipronil, tebufenpyrad, ethiprole, tolfenpyrad, acetoprole, pyrafluprole and pyriprole;

neonicotinoids, such as imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, nidinotefuran, dinotefuran and nithiazine;

hydrazine compounds, such as tebufenozide, methoxyfenozide, chromafenozide and halofenozide;

pyridine compounds, such as pyridalyl and flonicamid;

cyclic keto-enol compounds, such as spirodiclofen; spiromesifen and

spirotetramat;

strobilurin compounds, such as fluacrypyrim;

pyrimidinamine compounds, such as flufenerim;

dinitro compounds; organic sulfur compounds; urea compounds; triazine compounds; hydrazone compounds;

other compounds, such as buprofezin, hexythiazox, amitraz, chlordimeform, silafluofen, triazamate, pymetrozine, pyrimidifen, chlorfenapyr, indoxacarb,

acequinocyl, etoxazole, cyromazine, 1 ,3-dichloropropene, diafenthiuron, benclothiaz, bifenazate, propargite, clofentezine, metaflumizone, flubendiamide, cyflumetofen, chlorantraniliprole, cyenopyrafen, pyrifluquinazon, fenazaquin, amidoflumet,

sulfluramid, hydramethylnon, metaldehyde, HGW-86, ryanodine and verbutin; and the like. Further, it may be used in combination with or together with microbial agricultural chemicals, such as insecticidal crystal proteins produced by Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis israelensis, Bacillus thuringiensis japonensis, Bacillus thuringiensis tenebrionis or Bacillus thuringiensis, insect viruses, etomopathogenic fungi, and nematophagous fungi; antibiotics or semisynthetic antibiotics, such as avermectin, emamectin benzoate, milbemectin, milbemycin, spinosad, ivermectin, lepimectin, DE-175, abamectin, emamectin and spinetoram; natural products, such as azadirachtin and rotenone; and repellents, such as deet.

The active ingredient compounds of the fungicide in the above-mentioned other agricultural chemicals include, for example, (by common names, some of them are still in an application stage, or test codes of Japan Plant Protection Association):

anilinopyrimidine compounds, such as mepanipyrim, pyrimethanil, and cyprodinil; triazoropyrimidine compounds, such as 5-chloro-7-(4-methylpiperidin-1-yl)-6- (2,4,6-trifluorophenyl)[1 ,2,4Jtriazolo[ ,5-a]pyrimidine;

pyridinamine compounds, such as fluazinam;

azole compounds, such as triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, myclobutanil, cyproconazole, tebuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole, epoxiconazole,

tetraconazole, oxpoconazole fumarate, sipconazole, prothioconazole, triadimenol, flutriafol, difenoconazole, fluquinconazole, fenbuconazole, bromuconazole,

diniconazole, tricyclazole, probenazole, simeconazole, pefurazoate, ipconazole and imibenconazole;

quinoxaline compounds, such as quinomethionate;

dithiocarbamate compounds, such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb and thiram;

organic chlorine compounds, such as fthalide, chlorothalonil and quintozene; imidazole compounds, such as benomyl, cyazofamid, thiophanate-methyl, carbendazim, thiabendazole and fuberiazole;

cyanoacetamide compounds, such as cymoxanil;

anilide compounds, such as metalaxyl, metalaxyl-M, mefenoxam, oxadixyl, ofurace, benalaxyl, benalaxyl-M (another name: kiralaxyl, chiralaxyl), furalaxyl, cyprofuram, carboxin, oxycarboxin, thifluzamide, boscalid, bixafen, isotianil, tiadinil and sedaxane;

suifamide compounds, such as dichlofluanid;

copper compounds, such as cupric hydroxide and oxine copper;

isoxazole compounds, such as hymexazol;

organophosphorus compounds, such as fosetyl-AI, tolclofos-methyl, S-benzyl

0,0-diisopropyIphosphorothioate, O-ethyl S,S-diphenylphosphorodithioate, aluminum ethylhydrogen phosphonate, edifenphos, and iprobenfos;

phthalimide compounds, such as captan, captafol and folpet;

dicarboximide compounds, such as procymidone, iprodione and vinclozolin; benzanilide compounds, such as flutolanil and mepronil;

amide compounds, such as penthiopyrad, mixture of 3-(difluoromethyl)-1-methyl- N[(1 RS,4SR,9SR)-1 ,2,3,4-tetrahydro-9-isopropyl-1 ,4-methanonaphthalen-5- yl]pyrazole-4-carboxamide and 3-(difluoromethyl)-1 -methyl-N-[(1 RS,4SR,9SR)-1 ,2,3,4- tetrahydro-9-isopropyl-1 ,4-methanonaphthalen-5-yl]pyrazole-4-carboxamide

(isopyrazam), silthiopham and fenoxanil;

benzamide compounds, such as fluopyram and zoxamide;

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 compounds, such as pencycuron;

cinnamic acid compounds, such as dimethomorph and flumorph;

phenylcarbamate compounds, such as diethofencarb;

cyanopyrrole compounds, such as fludioxonil and fenpiclonil; strobilurin compounds, such as azoxystrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, picoxystrobin, oryzastrobin, dimoxystrobin, pyraclostrobin, and fluoxastrobin;

oxazolidinone compounds, such as famoxadone;

thiazolecarboxamide compounds, such as ethaboxam;

valinamide compounds, such as iprovalicarb and benthiavalicarb-isopropyl;

acylamino acid compounds, such as methyl N-(isopropoxycarbonyl)-L-valyl- (3RS)-3-(4-chlorophenyl)-p-alaninate (valiphenalate);

imidazolinone compounds, such as fenamidone;

hydroxyanilide compounds, such as fenhexamid;

benzenesulfonamide compounds, such as flusulfamide;

oxime ether compounds, such as cyflufenamid;

anthraquinone compounds;

crotonic compounds;

antibiotics, such as validamycin, kasugamycin and polyoxins;

guanidine compounds, such as iminoctadine and dodine;

quinoline compounds, such as 6-tert-butyl-8-fluoro-2,3-dimethylquinolin- 4-yl acetate (tebufloquin);

thiazolidine compounds, such as (z)-2-(2-fluoro-5-(trifluromethyl)phenylthio)-2-(3- (2-methoxyphenyl)thiazolidin-2-yliden)acetonitrile (flutianil);

and other compounds, such as pyribencarb, isoprothiolane, pyroquilon, diclomezine, quinoxyfen, propamocarb hydrochloride, chloropicrin, dazomet, metam- sodium, nicobifen, metrafenone, UBF-307, diclocymet, proquinazid, amisulbrom

(another name: amibromdole), pyriofenone, mandipropamid, fluopicolide, carpropamid, meptyldinocap, ferimzone, spiroxamine, S-2188 (fenpyrazamine), S-2200, ZF-9646, BCF-051 , BCM-061 and BCM-062.

Further, agricultural chemicals which may be used in admixture with or in combination with the compounds of the present invention, may , for example, be the active ingredient compounds in the herbicides as disclosed in The Pesticide

Manual(15th edition), particularly those of soil treatment type.

The pesticides against parasites on animals are effective for controlling e.g.

harmful external parasites which are parasitic on the body surface of host animals (such as the back, the axilla, the lower abdomen or inside of the thigh) or harmful internal parasites which are parasitic in the body of host animals (such as the stomach, the intestinal tract, the lung, the heart, the liver, the blood vessels, the subcutis or lymphatic tissues), but they are particularly effective for controlling the external parasites.

The external parasites may, for example, be animal parasitic acarus or fleas. Their species are so many that it is difficult to list all of them, and therefore, their typical examples will be given.

The animal parasitic acarus may, for example, be ticks such as Boophilus microplus, Rhipicephalus sanguineus, Haemaphvsalis lonqicornis, Haemaphvsalis fla a, Haemaphvsalis campanulata, Haemaphvsalis concinna, Haemaphvsalis japonica, Haemaphvsalis kitaokai, Haemaphvsalis ias, Ixodes ovatus, Ixodes

nipponensis, Ixodes persulcatus, Amblvomma testudinarium, Haemaphvsalis

meqaspinosa, Dermacentor reticulatus, and Dermacentor taiwanesis: red mite

(Dermanvssus allinae); northern fowl mites such as Omithonvssus sylviarum, and Ornithonvssus bursa; trombiculidae such as Eutrombicula wichmanni, _2Q

Leptotrombidium akamushi, Leptotrombidium pallidum, Leptotrombidium fujj,

Leptotrombidium tosa, Neotrombicula autumnalis, Eutrombicula alfredduqesi, and

Helenicula miyagawai; cheyletidae such as Cheyletiella yasquri, Cheyletiella

parasitivorax, and Cheyletiella blakei; sarcoptic mange mites such as Psoroptes cuniculi, Chorioptes bovis, Otodectes cynotis, Sarcoptes scabiei, and Notoedres cati; and Demodicidae such as Demodex canis. The pesticides against parasites on animals, containing the compounds of the present invention, are particularly effective for the control of ticks among them.

The animal parasitic fleas may, for example, be externally parasitic wingless insects belonging to Siphonaptera, more specifically, fleas belonging to Pulicidae,

Ceratephyllus, etc. Fleas belonging to Pulicidae may for example, be

Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Echidnophaqa qallinacea, Xenopsylla cheopis, Leptopsylla seqnis, Nosopsyllus fasciatus, and Monopsyllus anisus. The pesticides against parasites on animals, containing the compounds of the present invention, are particularly effective for the control of fleas belonging to

Pulicidae, particularly Ctenocephalides canis and Ctenocephalides felis, among them.

Other external parasites may, for example, be sucking lice (Anoplura) such as shortnosed cattle louse (Haematopinus eurvsternus), horse sucking louse

(Haematopinus asini), sheep louse, longnosed cattle louse (Linoqnathus vituli), and head louse (Pediculus capitis); biting lice such as dog biting louse (Trichodectes canis); and blood-sucking dipterous insects such as horsefly (Tabanus triqonus), biting midges (Culicoides schultzei), and blackfly (Simulium ornatum). Further, the internal parasites may, for example, be nematodes such as lung worms, whipworms (Trichuris), tuberous worms, gastric parasites, ascaris, and filarioidea; cestoda such as Spirometra erinacei, Diphyllobothrium latum, Dipylidium caninum, Taenia multiceps, Echinococcus granulosus, and Echinococcus multilocularis; trematoda such as Schistosoma japonicum and Fasciola hepatica; and protozoa such as coccidia, malaria parasites (Plasmodium malariae), intestinal sarcocyst, toxoplasma, and Cryptosporidium.

The host animals may, for example, be pet animals, domestic animals, and poultry, such as dogs, cats, mice, rats, hamsters, guinea pigs, squirrels, rabbits, ferrets, birds (such as pigeons, parrots, hill mynas, Java sparrows, honey parrots, lovebirds and canaries), cows, horses, pigs, sheep, ducks and chickens. The pesticides against parasites on animals, containing the compounds of the present invention, are particularly effective for the control of pests parasitic on pet animals or domestic animals, especially for the control of external parasites, among them. Among pet animals or domestic animals, they are effective particularly for dogs and cats, cows and horses.

When the compound of the present invention is used as a pesticide against parasites on animals, it may be used as it is or may be used together with suitable adjuvants, as formulated into various formulations such as a dust, granules, tablets, a powder, capsules, a soluble concentrate, an emulsifiable concentrate, a water-based suspension concentrate and an oil-based suspension concentrate. In addition to such formulations, it may be formulated into any type of formulation which is commonly used in this field, so long as it is suitable for the purpose of the present invention. The adjuvants to be used for formulations may, for example, be anionic surfactants or nonionic surfactants exemplified above as adjuvants for formulation of agricultural and horticultural insecticide, miticide, nematicide or soil pesticides; a cationic surfactant such as cetyl trimethylammonium bromide; a solvent such as water, acetone, acetonitrile, N-methylacetamide, Ν,Ν-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, diethylene glycol monoethyl ether, diethylene glycol n- butyl ether, dipropylene glycol monomethyl ether, or dipropylene glycol n-butyl ether; an antioxidant such as butylhydroxyanisole, butylhydroxytoluene, ascorbic acid, sodium hydrogenmetasulfite, propyl gallate or sodium thiosulfate; a coating film- forming agent such as polyvinylpyrrolidone, polyvinyl alcohol, or a copolymer of vinyl acetate and vinyl pyrrolidone; the vegetable oils and mineral oils as exemplified above as adjuvants for formulation of agricultural and horticultural insecticide, miticide, nematicide or soil pesticides; a carrier such as lactose, sucrose, glucose, starch, wheat flour, corn powder, soybean cake and meal, defatted rice bran, calcium carbonate or other commercially available feed materials; and so on. One or more of the

respective components of these adjuvants may be suitably selected for use, so long as such will not depart from the purpose of the present invention. Further, other than the above-mentioned adjuvants, some among those known in this field may suitably be selected for use, and still further, some among the above-mentioned various adjuvants to be used in the agricultural and horticultural field may suitably be selected for use.

The blend ratio of the compound of the present invention to various adjuvants is usually from 0.1 :99.9 to 90:10, by weight. In the actual use of such a formulation, it may be used as it is, or may be diluted to a predetermined concentration with a diluent such as water, and various spreaders (e.g. surfactants, vegetable oils or mineral oils) may be added thereto, as the case requires.

Administration of the compound of the present invention to a host animal is carried out orally or parenterally. As an oral administration method, a method of administering a tablet, a liquid agent, a capsule, a wafer, a biscuit, a minced meat or other feed, containing the compound of the present invention, may be mentioned. As a parenteral administration method, there may, for example, be mentioned a method wherein the compound of the present invention is formulated into a suitable formulation and then taken into the body by e.g. intravenous administration, intramuscular administration, intradermal administration, hypodermic administration, etc.; a method wherein it is administered on the body surface by spot-on treatment, pour-on treatment or spray treatment; or a method of embedding a resin fragment or the like containing the compound of the present invention under the skin of the host animal.

The dose of the compound of the present invention to a host animal varies depending upon the administration method, the purpose of administration, the

deceased symptom, etc., but it is usually administered in a proportion of from 0.01 mg to 100 g, preferably from 0.1 mg to 10 g, per 1 kg of the body weight of the host animal.

The present invention also includes a method for controlling a pest by the above- mentioned administration method or by the above-mentioned dose, particularly a method for controlling external parasites or internal parasites.

Further, in the present invention, by controlling pests parasitic on animals as described above, it is possible to prevent or cure various diseases of the host animal thereby caused in some cases. Thus, the present invention also includes a

preventive or therapeutic agent for an animal disease caused by parasites, containing the compound of the present invention as an active ingredient, and a method for preventing or curing an animal disease caused by parasites.

When the compound of the present invention is used as a pesticide against parasites on animals, various vitamins, minerals, amino acids, nutrients, enzymes, antipyretics, sedatives, antiphlogistics, fungicides, colorants, aromatic substances, preservatives, etc., may be used in admixture with or in combination with the adjuvants. Further, as the case requires, other animal drugs or agricultural chemicals, such as vermicides, anti-coccidium agents, insecticides, miticides, pulicides, nematicides, bactericides or antibacterial agents, may be mixed or combined for use, whereby improved effects may sometimes be obtained. The present invention includes such a mixed pesticidal composition having the above-mentioned various components mixed or combined for use, and further a method for controlling a pest by using it, particularly a method for controlling external parasites or internal parasites.

Now, preferred embodiments of the compound of the above formula (I) will be described, but it should be understood that the present invention is by no means thereby restricted.

(1) The compound of the above formula (I) or its salt.

(2) The diaryltriazole derivative or its salt according to the above (1), wherein R¹ is alkyl which may be substituted by halogen; R² is phenyl which may be substituted by X, or pyridyl which may be substituted by X; X is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, nitro or cyano; each of R³ and R⁴ which are independent of each other, is a hydrogen atom, halogen, alkyl or cyano; R⁵ is alkyl which may be substituted by A, or alkenyl which may be substituted by A.

(3) The diaryltriazole derivative or its salt according to (2), wherein each of R³ and R⁴ which are independent of each other, is halogen, alkyl or cyano; and R⁵ is alkyl which may be substituted by A.

(4) The diaryltriazole derivative or its salt according to (2), wherein each of R³ and R⁴ which are independent of each other, is a hydrogen atom, halogen or alkyl; and R⁵ is alkyl which may be substituted by A.

(5) The diaryltriazole derivative or its salt according to the above (1), (2), (3) or (4), wherein R² is pyridyl which may be substituted by X.

(6) The diaryltriazole derivative or its salt according to the above (5), wherein the pyridyl which may be substituted by X is 2-pyridyl which may be substituted by X.

(7) The diaryltriazole derivative or its salt according to the above (5), wherein the pyridyl which may be substituted by X is 2-pyridyl.

(8) The diaryltriazole derivative or its salt according to the above (1) to (7), wherein n is 0.

(9) An insecticide, miticide, nematicide or soil pesticide containing the diaryltriazole derivative or its salt as defined in the above (1), as an active ingredient.

(10) The insecticide, miticide, nematicide or soil pesticide according to the above (9), wherein the insecticide, miticide, nematicide or soil pesticide containing the

diaryltriazole derivative or its salt, as an active ingredient, is for agricultural and horticultural use.

(11 ) The insecticide or miticide for agricultural and horticultural use, containing the diaryltriazole derivative or its salt, as an active ingredient, according to the above (10). (12) The insecticide or miticide according to the above (9), wherein the insecticide, miticide, nematicide or soil pesticide containing the diaryltriazole derivative or its salt, as an active ingredient, is for controlling animal parasitic insects or mites.

(13) A method for controlling insects, mites, nematodes or soil pests, which comprises applying an effective amount of the diaryltriazole derivative or its salt as defined in the above (1).

EXAMPLES

Now, the present invention will be described in further detail with reference to

Examples, but it should be understood that the present invention is by no means thereby restricted. Firstly, Preparations Examples for the compounds of the present invention will be described.

PREPARATION EXAMPLE 1

Preparation of 2-(1 -(2-f luoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl)-3- (trifluoromethyl)-1 H-1 ,2,4-triazol-5-yl)pyridine (Compound No. 32)

0.10 g of p-toluenesulfonic acid monohydrate was added to a mixed solution comprising 1.0 g of 2,2,2-trifluoro-N'-(2-fluoro-4-methyl-5-(2,2,2- trifluoroethylthio)phenyl)acetohydrazonamide, 0.34 g of 2-pyridinecarboxyaldehyde and 20 mL of toluene, followed by heating and refluxing for 1 hour by means of an azeotropic dehydration apparatus. The reactor was taken out from an oil bath and cooled to room temperature, and then a mixed solution of 0.59 g of triethylamine and 2 mL of toluene, was added, followed by a reaction for 20 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. 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 the desired product as a solid. PREPARATION EXAMPLE 2

Preparation of 2-(1 -(2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfonyl)phenyl)-3- (trifluoromethyl)-l H-1 ,2,4-triazol-5-yl)pyridine (Compound No. 34)

0.30 g of m-chloroperbenzoic acid was added in three additions to a mixed solution comprising 0.18 g of 2-(1 -(2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl- 3-(trifluoromethyl)-1 H,1 ,2,4-triazol-5-yl)pyridine (Compound No. 32) and 5 mL of chloroform, followed by a reaction at room temperature for 24 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with an aqueous sodium bicarbonate solution, water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. 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 the desired product as a solid.

PREPARATION EXAMPLE 3

Preparation of 2-(1 -(2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl)-3- (trifluoromethyl)-1 H-1 ,2,4-triazol-5-yl)benzonitrile (Compound No. 21)

0.016 g of p-toluenesulfonic acid monohydrate was added to a mixed solution comprising 0.15 g of 2,2,2-trifluoro-N'-(2-fluoro-4-methyl-5-(2,2,2- trifluoroethylthio)phenyl)acetohydrazonamide, 0.11 g of 2-cyanobenzaldehyde and 5 mL of toluene, followed by heating and refluxing for 4 hours by means of an azeotropic dehydration apparatus. Then, 0.008 g of p-toluenesulfonic acid monohydrate was further added, followed by heating and refluxing for 14 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. 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 desired product as an oil. PREPARATION EXAMPLE 4

Preparation of 1 -(2-fluoro-4-methyl-5-(2,2,2-trif luoroethylthio)phenyl)-5-(2-nitrophenyl)- 3-(trifluoromethyl)-1 H-1 ,2,4-triazole (Compound No. 25)

0.044 g of p-toluenesulfonic acid monohydrate was added to a mixed solution comprising 0.40 g of 2,2,2-trifluoro-N'-(2-fluoro-4-methyl-5-(2,2,2- trifluoroethylthio)phenyl)acetohydrazonamide, 0.35 g of 2-nitrobenzaldehyde and 10 mL of toluene, followed by heating and refluxing for 2 hours by means of an azeotropic dehydration apparatus. The reactor was taken out from an oil bath and cooled to room temperature. Then, 0.23 g of triethylamine was added, followed by a reaction for 22 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. 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 desired product as an oil.

PREPARATION EXAMPLE 5

Preparation of 2-(1 -(2-fluoro-4-methyl-5-(2,2,2-trif luoroethylthio)phenyl)-3- (trifluoromethyl)-l H-1 ,2,4-triazol-5-yl)aniline (Compound No. 26)

0.050 g of 5% palladium carbon was added to a mixed solution comprising 0.27 g of 1-(2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl)-5-(2-nitrophenyl)-3- (trifluoromethyl)-1 H-1 ,2,4-triazole (Compound No. 25) and 10 mL of methanol, and the interior of the reaction system was replaced with hydrogen, followed by a reaction 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. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. 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 the desired product as a solid.

PREPARATION EXAMPLE 6

Preparation of 5-(2-chlorophenyl)-1 -(2-fluoro-4-methyl-5-(2,2,2- trifluoroethylthio)phenyl)-3-(trifluoromethyl)-1 H-1 ,2,4-triazole (Compound No. 10)

0.002 mL of Ν,Ν-dimethylformamide was added to a mixed solution comprising

0.14 g of 2-chlorobenzoic acid, 2 mL of tetrahydrofuran and 0.10 mL of oxalyl chloride. After a reaction at room temperature for 1 hour, the reaction mixture was concentrated under reduced pressure to obtain 2-chlorobenzoic acid chloride. In a separate reactor, 0.30 g of 2,2,2-trifluoro-N'-(2-fluoro-4-methyl-5-(2,2,2- trifluoroethylthio)phenyl)acetohydrazonamide, 5 mL of 1 ,4-dioxane 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 dropwise added, followed by heating and refluxing for 6 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. 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 desired product as an oil. ₂

PREPARATION EXAMPLE 7

Preparation of 4-chloro-2-(1 -(2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl)-3- (trifluoromethyl)-1 H-1 ,2,4-triazol-5-yI)pyridine (Compound No. 39)

0.002 mL of Ν,Ν-dimethylformamide was added to a mixed solution comprising 0.15 g of 4-chloropico!inic acid, 2mL of tetrahydrofuran and 0.10 mL of oxalyl chloride. After a reaction at room temperature for 1 hour, the reaction mixture was concentrated under reduced pressure to obtain 4-chloropicolinic acid chloride. In a separate reactor, 0.30 g of 2,2,2-trifluoro-N'-(2-fluoro-4-methyl-5-(2_>2,2- trifluoroethylthio)phenyl)acetohydrazonamide, 5 mL of 1 ,4-dioxane 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 dropwise added, followed by heating and refluxing for 6 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. 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 the desired product as a solid. PREPARATION EXAMPLE 8

Preparation of 2-(1 -(5-(1 -chloro-2,2,2-trifluoroethylthio)-2-fluoro-4-methylphenyl)-3- (trifluoromethyl)-1 H-1 ,2,4-triazol-5-yl)pyridine (Compound No. 64)

0. 8 g of N-chlorosuccinimide was added to a mixed solution comprising 0.30 g of 2-(1 -(2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl)-3-(trifluoromethyl)-1 H- 1 ,2,4-triazol-5-yl)pyridine (Compound No. 32) and 5 mL of N,N-dimethylformamide, followed by a reaction at room temperature for 16 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. 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 the desired product as a solid. PREPARATION EXAMPLE 9

Preparation of 2-(1-(4-methyl-3-(2,2,2-trifluoroethylthio)phenyl)-3-(trifluoromethyl)-1 H- 1 ,2,4-triazol-5-yl)pyridine (Compound No. 131)

(1 ) A mixture of 8.40 g of p-tolylhydrazine hydrochloride, 9.10 g of

trifluoroacetaldehyde hemiethylacetal, 4.33 g of sodium acetate and 100 mL of ethanol, was heated and refluxed for 2 hours. The reaction solution was cooled to room temperature, and then, water was added to the reaction solution, followed by extraction with ethyl acetate. The organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. Then, the solvent was distilled off under reduced pressure to obtain 1-(p-tolyl)-2-(2,2,2- trifluoroethylidene)hydrazine.

(2) To the entire amount of 1-(p-tolyl)-2-(2,2,2-trifluoroethylidene)hydrazine obtained in (1), 50 mL of Ν,Ν-dimethylformamide and 9.4 g of N-bromosuccinimide were added, followed by a reaction at room temperature for 30 minutes. Water was added to the reaction solution, followed by extraction with ethyl acetate. The organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. Then, the solvent was distilled off under reduced pressure to obtain 2,2,2-trifluoro-N'-(p-tolyl)acetohydrazonoyl bromide.

(3) To the entire amount of 2,2,2-trifluoro-N'-(p-tolyl)acetohydrazonoyl bromide obtained in (2), 120 mL of chloroform and 60 mL of 28% aqueous ammonia were added, followed by a reaction at room temperature for 1.5 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. The organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. Then, the solvent was distilled off under reduced pressure to obtain 2,2,2-trifluoro-N'-(p-tolyl)acetohydrazonamide. ¹H-NMR data of this product [measured by ¹H-Nuclear Magnetic Resonance Spectroscopy, δ is a chemical shift] are as follows.

¹H-NMR (solvent: (D₃ C)₂ S=O/400MHz ) 6(ppm): 8.31 (1 H,s), 6.97(2H,d), 6.81 (2H,d), 6.33(2H,brs), 2.16(3H,s)

(4) To the entire amount of 2,2,2-trifluoro-N'-(p-tolyl)acetohydrazonamide obtained in (3), 00 mL of toluene, 6.02 g of 2-pyridinecarboxyaldehyde and 1.94 g of p- toluenesulfonic acid monohydrate were added, followed by heating and refluxing for 1 hour by means of an azeotropic dehydration apparatus. The reactor was taken out from an oil bath and cooled to room temperature, and then, 10.3 g of triethylamine was added, followed by a reaction for 20 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. 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 9.09 g of 2-(1-(p-tolyl)-3-(trifluoromethyl)-1 H-1 ,2,4-triazol- 5-yl)pyridine (melting point: 92.4°C). ¹H-NMR data of this product are as follows. ¹H-NMR (solvent: CDCI₃ /400MHz) 5(ppm): 8.48(1 H,dd), 7.94(1 H,dd), 7.79(1 H,dt), 7.35-7.30(1 H,m), 7.26(2H,d), 7.21 (2H,d), 2.40(3H,s)

(5) Under cooling with ice, to 17.8 mL of chlorosulfonic acid, 9.09 g of 2-(1 -(p-tolyl)- 3-(trifluoromethyl)-1 H-1 ,2,4-triazol-5-yl)pyridine obtained in (4) was gradually added, followed by a reaction at 20°C for 3 hours. The reaction solution was cooled to room temperature and then added to ice water, followed by extraction with ethyl acetate. The organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. Then, the solvent was distilled off under reduced pressure to obtain 2-methyl-5-(5-(pyridin-2-yl)-3-(trifluoromethyl)-1 H- 1 ,2,4-triazol-1 -yl)benzene-1 -sulfonyl chloride.

(6) A mixture comprising the entire amount of 2-methyl-5-(5-(pyridin-2-yl)-3- (trifluoromethyl)-l H-1 , 2,4-triazol-1-yl)benzene-1 -sulfonyl chloride obtained in (5), 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, followed by filtration to remove a solid 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 obtain 4.82 g of 2-methyl-5-(5-(pyridin-2-yl)-3-(trifluoromethyl)-1 H-1 ,2,4-triazol-1 -yl)benzenethiol (melting point: 111.7°C).

(7) To a mixture comprising 0.20 g of 2-methyl-5-(5-(pyridin-2-yl)-3-(trifluoromethyl)- 1 H-1 ,2,4-triazol-1-yl)benzenethiol, 0.12 g of potassium carbonate, 0.07 g of Rongalit and 3 mL of Ν,Ν-dimethylformamide, a mixed solution of 0.19 g of 1 ,1 ,1 -trifluoro-2- iodoethane and 1 mL of Ν,Ν-dimethylformamide, was dropwise added, followed by a reaction at room temperature for 16 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. 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 the desired product as a solid.

Typical examples of the compound of the above formula (I) will be given in Table 1. These compounds can be prepared based on the above-described Preparation Examples or the above-described various processes for the production of the compounds of the present invention. In Table 1 , No. represents the compound No., Me methyl, Et ethyl, n-Pr normal-propyl, i-Pr isopropyl, c-Pr cyclopropyl, t-Bu tertiary- butyl, i-Bu isobutyl, Ph phenyl, and Py pyridyl, and the temperature shown as the physical properties is the melting point. Further, with respect to some compounds of the above formula (I), ¹H-NMR data [measured by ¹H-Nuclear Magnetic Resonance Spectroscopy, δ is a chemical shift] are shown in Table 2.

3

TABLE 1 (continued)

Physical

No. R¹ R² R³ R⁴ R⁵ n

properties

98 CF₃ 2-CI-Ph CN Me CH₂CF₃ 0

99 CF₃ 2-CI-Ph CN CI CH₂CF₃ 0

100 CF₃ 2-CI-Ph CN Br CH₂CF₃ 0

101 CF₃ 2-CI-Ph F CN CH₂CF₃ 0

102 CF₃ 2-CI-Ph F CI CH₂CF₃ 0

103 CF₃ 2-CI-Ph F Br CH₂CF₃ 0

104 CF₃ 2-CI-Ph CI Me CH₂CF₃ 0 Oil

105 CF₃ 2-CI-Ph CI CN CH₂CF₃ 0

106 CF₃ 2-CI-Ph CI CI CH₂CF₃ 0

107 CF₃ 2-CI-Ph CI Br CH₂CF₃ 0

108 CF₃ 2-CI-Ph Br Me CH₂CF₃ 0

109 CF₃ 2-CI-Ph Br CN CH₂CF₃ 0

110 CF₃ 2-CI-Ph Br CI CH₂CF₃ 0

111 CF₃ 2-CI-Ph Br Br CH₂CF₃ 0

112 CF₃ 2-CN-Ph Me Me CH₂CF₃ 0 100.9°C

113 CF₃ 2-CN-Ph Me CN CH₂CF₃ 0

114 CF₃ 2-CN-Ph Me CI CH₂CF₃ 0

115 CF₃ 2-CN-Ph Me Br CH₂CF₃ 0

116 CF₃ 2-CN-Ph Me I CH₂CF₃ 0

117 CF₃ 2-CN-Ph CN Me CH₂CF₃ 0

118 CF₃ 2-CN-Ph CN CI CH₂CF₃ 0

119 CF₃ 2-CN-Ph CN Br CH₂CF₃ 0

120 CF₃ 2-CN-Ph F CN CH₂CF₃ 0

121 CF₃ 2-CN-Ph F CI CH₂CF₃ 0

122 CF₃ 2-CN-Ph F Br CH₂CF₃ 0

123 CF₃ 2-CN-Ph CI Me CH₂CF₃ 0 Oil

124 CF₃ 2-CN-Ph CI CN CH₂CF₃ 0

125 CF₃ 2-CN-Ph CI CI CH₂CF₃ 0

126 CF₃ 2-CN-Ph CI Br CH₂CF₃ 0

127 CF₃ 2-CN-Ph Br Me CH₂CF₃ 0

128 CF₃ 2-CN-Ph Br CN CH₂CF₃ 0

129 CF₃ 2-CN-Ph Br CI CH₂CF₃ 0

130 CF₃ 2-CN-Ph Br Br CH₂CF₃ 0

131 CF₃ 2-Py H Me CH₂CF₃ 0 85.3°C

132 CF₃ 2-Py Me Me CH₂CF₃ 0 84.9°C

133 CF₃ 2-Py Me CN CH₂CF₃ 0

TABLE 1 (continued)

Physical

No. R R² R³ R⁴ R⁵ n

properties

170 CF₃ 3-OMe-2-Py F Me CH₂CF₃ 0

171 CF₃ 2-OEt-Ph F Me CH₂CF₃ 0 Oil

172 CF₃ 3,4-CI₂-Ph F Me CH₂CF₃ 0 Oil

173 CF₃ 3,5-CI₂-Ph F Me CH₂CF₃ 0 Oil

174 CF₃ 2,3,4-CI₃-Ph F Me CH₂CF₃ 0

175 CF₃ 2,3,5-CI₃-Ph F Me CH₂CF₃ 0 Oil

176 CF₃ 2,3,6-CI₃-Ph F Me CH CF₃ 0 Oil

177 CF₃ 2,4,5-Cla-Ph F Me CH₂CF₃ 0 Oil

178 CF₃ 2,4,6-Cls-Ph F Me CH₂CF₃ 0

179 CF₃ 5-C!-3-Py F Me CH₂CF₃ 0 Oil

180 CF₃ 6-CI-3-Py F Me CH₂CF₃ 0 Oil

181 CF₃ 2-CI-4-Py F Me CH₂CF₃ 0 Oil

182 CF₃ 2-OMe-Ph Me Me CH₂CF₃ 0 107.3°C

183 CF₃ 2-OMe-Ph Me CN CH₂CF₃ 0

184 CF₃ 2-OMe-Ph Me CI CH₂CF₃ 0

185 CF₃ 2-OMe-Ph Me Br CH₂CF₃ 0

86 CF₃ 2-OMe-Ph Me I CH CF₃ 0

187 CF₃ 2-OMe-Ph ON Me CH₂CF₃ 0

188 CF₃ 2-OMe-Ph CN CI CH₂CF₃ 0

189 CF₃ 2-OMe-Ph ON Br CH₂CF₃ 0

190 CF₃ 2-OMe-Ph F CN CH₂CF₃ 0

191 CF₃ 2-OMe-Ph F CI CH₂CF₃ 0

192 CF₃ 2-OMe-Ph F Br CH₂CF₃ 0

193 CF₃ 2-OMe-Ph CI Me CH₂CF₃ 0 81.0°C

194 CF₃ 2-OMe-Ph CI CN CH₂CF₃ 0

195 CF₃ 2-OMe-Ph CI CI CH₂CF₃ 0

196 CF₃ 2-OMe-Ph CI Br CH₂CF₃ 0

197 CF₃ 2-OMe-Ph Br Me CH₂CF₃ 0

198 CF₃ 2-OMe-Ph Br CN CH₂CF₃ 0

199 CF₃ 2-OMe-Ph Br CI CH₂CF₃ 0

200 CF₃ 2-OMe-Ph Br Br CH₂CF₃ 0

201 CF₃ 2,4-CI₂-Ph Me Me CH₂CF₃ 0

202 CF₃ 2,4-CI₂-Ph Me CN CH₂CF₃ 0

203 CF₃ 2,4-CI₂-Ph Me CI CH₂CF₃ 0

204 CF₃ 2,4-CI₂-Ph Me Br CH₂CF₃ 0

205 CF₃ 2,4-CI₂-Ph Me I CH CF₃ 0 3

TABLE 1 (continued)

Physical

No. R R² R³ R⁴ R⁵ n

properties

206 CF₃ 2,4-CI₂-Ph CN Me CH CF₃ 0

207 CF₃ 2,4-CI₂-Ph CN CI CH₂CF₃ 0

208 CF₃ 2,4-CI₂-Ph CN Br CH CF₃ 0

209 CF₃ 2,4-CI₂-Ph F CN CH₂CF₃ 0

210 CF₃ 2,4-CI₂-Ph F CI CH CF₃ 0

21 1 CF₃ 2,4-CI₂-Ph F Br CH₂CF₃ 0

212 CF₃ 2,4-CI₂-Ph CI Me CH₂CF₃ 0

213 CF₃ 2,4-CI₂-Ph CI CN CH₂CF₃ 0

214 CF₃ 2,4-CI₂-Ph CI CI CH₂CF₃ 0

215 CF₃ 2,4-CI₂-Ph CI Br CH₂CF₃ 0

216 CF₃ 2,4-CI₂-Ph Br Me CH₂CF₃ 0

217 CF₃ 2,4-CI₂-Ph Br CN CH₂CF₃ 0

218 CF₃ 2,4-CI₂-Ph Br CI CH₂CF₃ 0

219 CF₃ 2,4-CI₂-Ph Br Br CH₂CF₃ 0

220 CF₃ 2,5-CI₂-Ph Me Me CH₂CF₃ 0

221 CF₃ 2,5-CI₂-Ph Me CN CH CF₃ 0

222 CF₃ 2,5-CI₂-Ph Me CI CH CF₃ 0

223 CF₃ 2,5-CI₂-Ph Me Br CH₂CF₃ 0

224 CF₃ 2,5-CI₂-Ph Me I CH₂CF₃ 0

225 CF₃ 2,5-CI₂-Ph CN Me CH₂CF₃ 0

226 CF₃ 2,5-CI₂-Ph CN CI CH CF₃ 0

227 CF₃ 2,5-CI₂-Ph CN Br CH₂CF₃ 0

228 CF₃ 2,5-CI₂-Ph F CN CH₂CF₃ 0

229 CF₃ 2,5-CI₂-Ph F CI CH₂CF₃ 0

230 CF₃ 2,5-CI₂-Ph F Br CH₂CF₃ 0

231 CF₃ 2,5-CI₂-Ph CI Me CH₂CF₃ 0

232 CF₃ 2,5-CI₂-Ph CI CN CH₂CF₃ 0

233 CF₃ 2,5-CI₂-Ph CI CI CH₂CF₃ 0

234 CF₃ 2,5-CI₂-Ph CI Br CH₂CF₃ 0

235 CF₃ 2,5-CI₂-Ph Br Me CH CF₃ 0

236 CF₃ 2,5-CI₂-Ph Br CN CH₂CF₃ 0

237 CF₃ 2,5-CI₂-Ph Br CI CH₂CF₃ 0

38 CF₃ 2,5-CI₂-Ph Br Br CH₂CF₃ 0

239 CF₃ 4-CI-3-Py Me Me CH CF₃ 0

240 CF₃ 4-CI-3-Py Me CN CH₂CF₃ 0 TABLE 1 (continued)

Physical

No. R¹ R² R³ R⁴ R⁵ n

properties

241 CF₃ 4-CI-3-Py Me CI CH₂CF₃ 0

242 CF₃ 4-CI-3-Py Me Br CH₂CF₃ 0

243 CF₃ 4-CI-3-Py Me I CH₂CF₃ 0

244 CF₃ 4-CI-3-Py CN Me CH₂CF₃ 0

245 CF₃ 4-CI-3-Py CN CI CH₂CF₃ 0

246 CF₃ 4-CI-3-Py CN Br CH₂CF₃ 0

247 CF₃ 4-CI-3-Py F CN CH₂CF₃ 0

248 CF₃ 4-CI-3-Py F CI CH₂CF₃ 0

249 CF₃ 4-CI-3-Py F Br CH₂CF₃ 0

250 CF₃ 4-CI-3-Py CI Me CH CF₃ 0

251 CF₃ 4-CI-3-Py CI CN CH₂CF₃ 0

252 CF₃ 4-CI-3-Py CI CI CH₂CF_S 0

253 CF₃ 4-CI-3-Py CI Br CH₂CF₃ 0

254 CF₃ 4-CI-3-Py Br Me CH₂CF₃ 0

255 CF₃ 4-CI-3-Py Br CN CH₂CF₃ 0

256 CF₃ 4-CI-3-Py Br CI CH₂CF₃ 0

257 CF₃ 4-CI-3-Py Br Br CH₂CF₃ 0

258 CF₃ 3-CI-4-Py Me Me CH₂CF₃ 0

259 CF₃ 3-CI-4-Py Me CN CH₂CF₃ 0

260 CF₃ 3-CI-4-Py Me CI CH₂CF₃ 0

261 CF₃ 3-CI-4-Py Me Br CH₂CF₃ 0

262 CF₃ 3-CI-4-Py Me I CH₂CF₃ 0

263 CF₃ 3-CI-4-Py CN Me CH₂CF₃ 0

264 CF₃ 3-CI-4-Py CN CI CH₂CF₃ 0

265 CF₃ 3-CI-4-Py CN Br CH₂CF₃ 0

266 CF₃ 3-CI-4-Py F CN CH₂CF₃ 0

267 CF₃ 3-CI-4-Py F CI CH₂CF₃ 0

268 CF₃ 3-CI-4-Py F Br CH₂CF₃ 0

269 CF₃ 3-CI-4-Py CI Me CH₂CF₃ 0

70 CF₃ 3-CI-4-Py CI CN CH₂CF₃ 0

271 CF₃ 3-CI-4-Py CI CI CH₂CF₃ 0

272 CFs 3-CI-4-Py CI Br CH₂CF₃ 0

73 CF₃ 3-CI-4-Py Br Me CH₂CF₃ 0

274 CFs 3-CI-4-Py Br CN CH₂CF₃ 0

275 CF₃ 3-CI-4-Py Br CI CH₂CF₃ 0

TABLE 1 (continued)

Physical

No. R¹ R² R³ R⁴ R⁵ n jDroperties

311 CF2CF3 2-Py H Me CH₂CF₃ 0 68.1 °C

312 CH₂CF₃ 2-Py H Me CH₂CF₃ 0 62.7°C

313 CF₃ 2-Py H Et CH₂CF₃ 0 83.7°C

314 CF₃ 2-Py H CI CH₂CF₃ 0 123.7°C

315 CF₃ 2-Py H Me Me 0 83.5°C

316 CF₃ 2-Py H Me Et 0 101.2°C

317 CF₃ 2-Py H Me n-Pr 0 56.9°C

318 CF₃ 2-Py H Me i-Pr 0 Oil

319 CF₃ 2-Py H Me n-Bu 0 39.7°C

320 CF₃ 2-Py H Me i-Bu 0 67.4°C

321 CF₃ 2-Py H Me i-Bu 1 127.3°C

322 CF₃ 2-Py H Me CH₂(c-Pr) 0 77.0°C

323 CF₃ 2-Py H Me CH₂CH₂F 0 78.6°C

324 CF₃ 2-Py H Me CH₂CH₂CI 0 95.3°C

325 CF₃ 2-Py H Me Ch^Ch^Br 0 101.8°C

326 CF₃ 2-Py H Me CH₂CF₃ 1 136.5°C

327 CF₃ 2-Py H Me CF₂CF₂H 0 58.0°C

328 CF₃ 2-Py H Me CH₂CH₂CF₃ 0 82.0°C

329 CF₃ 2-Py H Me CH₂CH₂CF₃ 1 124.4°C

330 CF₃ Ph H Me CH₂CF₃ 0 68.7°C

331 CF₃ Ph H Me CH₂CF₃ 1 152.9°C

332 CF₃ 2-CI-Ph H Me CH₂CF₃ 0 Oil

333 CF₃ 2-CI-Ph H Me CH₂CF₃ 1 Oil

334 CF₃ 2-CN-Ph H Me CH₂CF₃ 0 Oil

335 CF₃ 2-CN-Ph H Me CH₂CF₃ 1 Oil

336 CF₃ 2-OMe-Ph H Me CH₂CF₃ 0 Oil

337 CF₃ 2-O e-Ph H Me CH₂CF₃ 1 Oil

338 CF₃ 2-CI-Ph CI Me CH₂CF₃ 1 Oil

339 CF₃ 2-OMe-Ph CI Me CH₂CF₃ 1 Oil

340 CF₃ 2-CN-Ph CI Me CH₂CF₃ 1 Oil

341 CFg 2-Py Me Me CH₂CN 0 126.5°C

342 CF₃ 2-CI-Ph Me Me CH₂CF₃ 1 Oil

343 CF₃ 2-OMe-Ph Me Me CH₂CF₃ 1 Oil

344 CF₃ 2-CN-Ph Me Me CH₂CF₃ 1 Oil

345 CF₃ 2-Py CI Me CH₂CF₃ 1 131.8°C

346 CF₃ 2-Py H Me CH₂CH₂CCI₃ 0 Oil 8

_Λη

TABLE 2 (continued)

Now, Test Examples will be described.

TEST EXAMPLE 1

Test on adults of two-spotted spider mite ( Tetranvchus urticae )

An insecticidal solution was prepared to bring the concentration of the compound of the present invention to 200ppm. A kidney bean having only one primordial leaf left, was transplanted to a pot ( diameter: 8 cm, height: 7cm ), and 20 adults of two-spotted spider mite were released thereon. Together with the kidney bean leaf, they were dipped in the above insecticidal solution, dried in air and then left in a constant temperature chamber at 25°C with lightening. On the second or third day after the treatment, the number of dead adults were counted, and the mortality of adults was calculated by the following equation. Adults that dropped from the leaf or were moribund were included in the number of dead. The test was carried out with respect to the above-mentioned Compound Nos.1 , 2, 6, 7, 10, 14-16, 20, 21 , 25, 26, 28, 29, 32, 33, 35, 37, 39, 44, 46, 51 -55, 87, 131 , 132, 143, 171 , 177, 179, 181 , 31 1 -314, 317, 322-324, 326, 328, 330, 332-337, whereby all compounds showed a mortality of adults of at least 90%.

Mortality of adults (%) = (The number of dead two-spotted spider mites/The number of treated two-spotted spider mites ) x 100

TEST EXAMPLE 2

Test on controlling effects against brown planthopper (Nilaparvata lugens)

Rice seedling was dipped for about 10 seconds in an insecticidal solution adjusted to bring the concentration of the compound of the present invention to 200 ppm and then dried in air, its root was wrapped with a wet absorbent cotton, and the seedling was put into a test tube. Then, 0 second-third instar nymphs of brown planthopper were released therein, and the test tube was covered with a gauze and left in a constant temperature chamber at 25°C with lightening. On the 5th day after the release, the number of dead nymphs were counted, and the mortality was calculated by the following equation.

The test was carried out with respect to the above-mentioned Compound Nos. 48,

131 , 326, whereby all compounds showed a mortality of at least 90%.

Mortality (%)=(The number of dead insects/The number of released insects)x100 TEST EXAMPLE 3

Test on knocked down effects/miticidal effects against Haemaphysalis longicornis

On filter paper set in a petri dish, 1 ml_ of an acetone solution of the compound of the present invention (concentration: 10 mg/mL, 1 mg/mL, 0.1 mg/mL, 0.01 mg/mL, 0.001 mg/mL) is dropped by a micropipette. After the filter paper is dried, 100 larval ticks (Haemaphysalis longicornis) are put in the petri dish and covered by a

polyethylene sheet for sealing. After 10, 30, 60 and 240 minutes from putting the larval ticks, the number of knocked down larval ticks is recorded as the time passes. Further, after 24, 48 and 72 hours from putting the larval ticks, the number of dead larval ticks is recorded as the time passes. The test is repeated twice.

TEST EXAMPLE 4

Pesticidal test against Haemaphysalis longicornis employing a dog

A gelatin capsule containing the compound of the present invention at a dose of

10 mg/kg weight is applied to a dog (Beagle, 8 months old), and immediately after the application, about 50 young mites of Haemaphysalis longicornis are released on the auricle of the dog and artificially parasitized. After the treatment, observation is carried out to inspect the parasitic number, the fallen number and the mortality of the fallen Haemaphysalis longicornis. As a result, the compound of the present invention is effective to have the parasitized Haemaphysalis longicornis fallen or dead.

TEST EXAMPLE 5

Pesticidal test against cat flea (Ctenocephalides felis) employing a dog

A gelatin capsule containing the compound of the present invention at a dose of 10 mg/kg weight is applied to a dog (Beagle, 8 months old), and immediately after the application, about 00 non-bloodsucked adults of cat flea are released on the dorsal fur of the dog and artificially parasitized. After the treatment, the cat flea is recovered by means of a flea catching comb, and the parasitized number is counted. As a result, the compound of the present invention is effective to control the parasitizing of cat flea.

Now, Formulation Examples are described below.

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

The above components are uniformly mixed to obtain 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 part by weight

The above components are uniformly mixed to obtain a dust. 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 dodecylbenzene sulfonate 2 parts by weight

(5) Xylene 48 parts by weight

The above components are uniformly mixed and dissolved to obtain an emulsifiable concentrate.

FORMULATION EXAMPLE 4

(1) Clay 68 parts by weight

(2) Sodium lignin sulfonate 2 parts by weight

(3) Polyoxyethylenealkylaryl sulfate 5 parts by weight

(4) White carbon 25 parts by weight

The mixture of the above components is mixed with compound of the present invention in a weight ratio of 4:1 to obtain a wettable powder.

FORMULATION EXAMPLE 5

(1) Compound of the present invention 50 parts by weight

(2) Sodium alkylnaphthalene sulfonate condensation product of formaldehyde

2 parts by weight

(3) Silicone oil 0.2 part by weight

(4) Water 47.8 parts by weight

The above components are uniformly mixed and pulverized to obtain a base liquid, and

(5) Sodium polycarboxylate 5 parts by weight

(6) Anhydrous sodium sulfate 42.8 parts by weight

are added, and the mixture is uniformly mixed, granulated and dried to obtain water- dispersible granules.

FORMULATION EXAMPLE 6

(1 ) Compound of the present invention 5 parts by weight

(2) Polyoxyethyleneoctylphenyl ether 1 part by weight

(3) Polyoxyethylene alkyl ether phosphoric acid esterO.1 part by weight

(4) Granular calcium carbonate 93.9 parts by weight

The above components (1) to (3) are preliminarily uniformly mixed and diluted with a proper amount of acetone, and then the mixture is sprayed onto the component (4), and acetone is removed to obtain 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

The above components are uniformly mixed and dissolved to obtain an ultra low volume formulation.

FORMULATION EXAMPLE 8

(1 ) Compound of the present invention 40 parts by weight

(2) Potassium polyoxyethylene tristyryl phenyl

ether 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 parts by weight (6) Water 50.7 parts by weight

The above components are uniformly mixed and pulverized to obtain a water- based suspension concentrate.

FORMULATION EXAMPLE 9

(1 ) Compound of the present invention 10 parts by weight

(2) Diethylene glycol monoethyl ether 80 parts by weight

(3) Polyoxyethylenealkyl ether 10 parts by weight

The above components are uniformly mixed to obtain a soluble concentrate.

The entire disclosure of Japanese Patent Application No. 2009-242123 filed on October 21 , 2009 including specification, claims and summary is incorporated herein by reference in its entirety.

Claims

CLAIMS:

rivative represented by the formula (I) or its salt:

wherein R¹ is alkyi which may be substituted by halogen, alkenyl which may be substituted by halogen, or alkynyl which may be substituted by halogen; R² is phenyl which may be substituted by X, or pyridyl which may be substituted by X; X is halogen, alkyi, haloalkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, alkylthio, amino, nitro or cyano; each of R³ and R⁴ which are independent of each other, is a hydrogen atom, halogen, alkyi, alkenyl, alkynyl or cyano; R⁵ is alkyi which may be substituted by A, alkenyl which may be substituted by A, or alkynyl which may be substituted by A; A is halogen, cyano or cycloalkyl; and n is 0, 1 or 2.

2. The diaryltriazole derivative represented by the formula (I) or its salt according to Claim 1 , wherein R¹ is alkyi which may be substituted by halogen; R² is phenyl which may be substituted by X, or pyridyl which may be substituted by X; X is halogen, alkyi, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, nitro or cyano; each of R³ and R⁴ which are independent of each other, is a hydrogen atom, halogen, alkyi or cyano; R⁵ is alkyi which may be substituted by A, or alkenyl which may be substituted by A.

3. The diaryltriazole derivative represented by the formula (I) or its salt according to Claim 2, wherein each of R³ and R⁴ which are independent of each other, is halogen, alkyi or cyano; and R⁵ is alkyi which may be substituted by A.

4. The diaryltriazole derivative represented by the formula (I) or its salt according to Claim 1 , wherein R² is pyridyl which may be substituted by X.

5. The diaryltriazole derivative represented by the formula (I) or its salt according to Claim 4, wherein the pyridyl which may be substituted by X, is 2-pyridyl which may be substituted by X.

6. The diaryltriazole derivative represented by the formula (I) or its salt according to Claim 1 , wherein n is 0.

7. An insecticide, miticide, nematicide or soil pesticide containing the diaryltriazole derivative or its salt as defined in Claim 1 , as an active ingredient.

8. The insecticide, miticide, nematicide or soil pesticide according to Claim 7, wherein the insecticide, miticide, nematicide or soil pesticide containing the

9. The insecticide or miticide for agricultural and horticultural use, containing the diaryltriazole derivative or its salt, as an active ingredient, according to Claim 8.

10. The insecticide or miticide according to Claim 7, wherein the insecticide, miticide, nematicide or soil pesticide containing the diaryltriazole derivative or its salt, as an active ingredient, is for controlling animal parasitic insects or mites.

11. A method for controlling insects, mites, nematodes or soil pests, which comprises applying an effective amount of the diaryltriazole derivative or its salt as defined in Claim 1 thereto.

12. A process for producing a diaryltriazole derivative represented by the formula (I) or its salt:

wherein R¹ is alkyl which may be substituted by halogen, alkenyl which may be substituted by halogen, or aikynyl which may be substituted by halogen; R² is phenyl which may be substituted by X, or pyridyl which may be substituted by X; X is halogen, alkyl, haloalkyl, alkenyl, aikynyl, alkoxy, haloalkoxy, alkylthio, amino, nitro or cyano; each of R³ and R⁴ which are independent of each other, is a hydrogen atom, halogen, alkyl, alkenyl, aikynyl or cyano; R⁵ is alkyl which may be substituted by A, alkenyl which may be substituted by A, or aikynyl which may be substituted by A; A is halogen, cyano or cycloalkyl; and n is 0, 1 or 2, which comprises

(1) reacting a compound represented by the formula (II):

(II) wherein R¹, R³, R⁴, R⁵ and n are as defined above, with a compound represented by the formula (III): R²CHO, wherein R² is as defined above, to obtain a compound represented by the formula (IV):

(IV)

wherein R¹, R², R³, R⁴, R⁵ and n are as defined above, and subjecting it to dehydrogenation; or

(2) reacting the compound of the formula (II) with a compound represented by the formula (V): R²COCI, wherein R² is as defined above; or

izing a compound represented by the formula (l-a):

(I-a)

wherein R¹, R², R³, R⁴ and R⁵ are as defined above; or

(4) halogenating a compound represented by the formula (l-c):

(I-c) wherein R¹, R² R³, R⁴ and n are as defined above; R^5c is alkyl which may be substituted by A¹, alkenyl which may be substituted by A¹, or alkynyl which may be substituted by A¹; and A¹ is halogen, cyano or cycloalkyl; or

cting a compound represented by the formula (VI):

(VI) wherein R¹, R², R³ and R⁴ are as defined above, or a compound represented by the formula (XIV):

wherein R¹, R², R³ and R⁴ are as defined above, with a compound represented by the formula (VII): R⁵L¹, wherein R⁵ is as defined above, and L¹ is a leaving group.