WO2016125622A1 - Benzoxazole compound, and use thereof for noxious arthropod control - Google Patents

Abstract

A benzoxazole compound represented by formula (I) (in the formula: A represents nitrogen or CR⁵; one from among R^A and R^B represents -OSO₂CF₃, and the other represents hydrogen; R¹ represents a C1-C4 alkyl group, a cyclopropyl group, or a cyclopropylmethyl group; R² and R³ each independently represent hydrogen or a halogen; R⁴ and R⁵ each independently represent hydrogen, -S(O)_mR⁶ {m represents 0, 1, or 2}, or a C3-C6 cycloalkyl group which may have at least one halogen; and n represents 0, 1, or 2) exhibits excellent control efficacy against noxious arthropods.

Description

Benzoxazole compounds and their use for controlling harmful arthropods

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

So far, various compounds have been studied for the purpose of controlling harmful arthropods (see, for example, Patent Documents 1 and 2).

International Publication No. 2012/086848 International Publication No. 2013/018928

An object of the present invention is to provide a compound having an excellent control effect against harmful arthropods.

As a result of studies to solve the above-mentioned problems, the present inventors have found that the benzoxazole compound represented by the following formula (I) has an excellent control effect against harmful arthropods, leading to the present invention. .

The present invention is as follows.
[1] Formula (I)

[Where:
A represents a nitrogen atom or CR ⁵ ,
One of R ^A and R ^B represents —OSO ₂ CF ₃ , the other represents a hydrogen atom,
R ¹ represents a C1-C4 alkyl group, a cyclopropyl group or a cyclopropylmethyl group,
R ² and R ³ each independently represent a hydrogen atom or a halogen atom,
R ⁴ and R ⁵ each independently represents a hydrogen atom, —S (O) _m R ⁶ {m represents 0, 1, or 2. } C3-C6 cycloalkyl group optionally having one or more halogen atoms, (C1-C6 alkoxy) optionally having one or more halogen atoms, C1-C6 alkyl group having one or more halogen atoms (C3-C6 cycloalkyl) C1-C6 alkyl group, —R ⁷ , —OR ⁷ , —NR ⁸ R ⁹ , —C (O) R ¹⁰ , —COOR ¹⁰ , —C (O) NR ⁸ R ⁹ , a phenyl group, a 5- to 6-membered heteroaryl group (provided that the phenyl group and the 5- to 6-membered heteroaryl group may have one or more atoms or substituents selected from group X; When it has two or more atoms or substituents, these atoms and substituents may be the same or different. }, Nitro group, cyano group, hydroxy group, sulfanyl group, halogen atom, —NR ¹⁰ C (O) R ⁶ , —NR ¹⁰ CO ₂ R ⁶ , —NR ¹⁰ SO ₂ R ⁶ , —NR ¹⁰ (OR ⁶ ) Or —N═S (O) _p R ⁶ R ¹¹ {p represents 0 or 1; },
R ⁶ and R ¹¹ each independently represents a C1-C6 alkyl group which may have one or more halogen atoms,
R ⁷ represents a C1-C6 chain hydrocarbon group which may have one or more halogen atoms,
R ⁸ and R ⁹ each independently represents a hydrogen atom or a C1-C6 chain hydrocarbon group which may have one or more halogen atoms, or R ⁸ and R ⁹ are bonded to each other, Represents a C2-C6 alkanediyl group optionally having the above halogen atom,
n represents 0, 1, or 2;
Group X is a group consisting of —R ⁶ , —OR ⁶ , —S (O) _m R ⁶ , —C (O) R ⁶ , —COOR ⁶ , —NR ¹⁰ R ¹² , a cyano group, a nitro group, and a halogen atom. Represents
R ¹⁰ and R ¹² each independently represents a hydrogen atom or a C1-C6 alkyl group which may have one or more halogen atoms. ]
(Hereinafter, the compound represented by the formula (I) may be referred to as the present compound).
[2] R ¹ is a C1-C3 alkyl group,
R ⁴ and R ⁵ each independently represents one or more selected from a hydrogen atom, —R ⁶ , —S (O) _m R ⁶ , —OR ⁶ , —NR ⁸ R ⁹ , —COOR ⁶ , group X An optionally substituted 5- to 6-membered heteroaryl group, a halogen atom, —NR ¹⁰ C (O) R ⁶ , —NR ¹⁰ CO ₂ R ⁶ , —NR ¹⁰ (OR ⁶ ), or —N The benzoxazole compound according to [1], wherein = S (O) _p R ⁶ R ¹¹ .
[3] The benzoxazole compound according to [1] or [2], wherein R ^A is —OSO ₂ CF ₃ and R ^B is a hydrogen atom.
[4] R ¹ is an ethyl group,
R ² and R ³ are both hydrogen atoms,
R ⁴ is a hydrogen atom, a halogen atom, a C1-C3 alkyl group that may have one or more halogen atoms, or a C1-C3 alkoxy group that may have one or more halogen atoms,
The benzoxazole compound according to [3], wherein R ⁵ is a hydrogen atom or a halogen atom.
[5] The benzoxazole compound according to any one of [1] to [4], wherein A is a nitrogen atom.
[6] The benzoxazole compound according to any one of [1] to [4], wherein A is CR ⁵ .
[7] A harmful arthropod control agent comprising the benzoxazole compound according to any one of [1] to [6] and an inert carrier.
[8] A method for controlling harmful arthropods, which comprises applying an effective amount of the benzoxazole compound according to any one of [1] to [6] to harmful arthropods or their habitat.

The compound of the present invention has excellent control activity against harmful arthropods.

The substituent in the present invention will be described.
In the present specification, “may have one or more halogen atoms”, when having two or more halogen atoms, these halogen atoms may be the same or different from each other.
In this specification, for example, the expression “C1-C4” means that the number of carbon atoms is 1 to 4.
As used herein, “C1-C6 chain hydrocarbon group” means a C1-C6 alkyl group, a C2-C6 alkenyl group, and a C2-C6 alkynyl group.

A halogen atom is a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the C1-C6 alkyl group optionally having one or more halogen atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a hexyl group, a fluoromethyl group, a trifluoromethyl group, a chlorodifluoromethyl group, Examples include 2-bromoethyl group, 1,1-difluoroethyl group, 2,2,2-trifluoroethyl group, and pentafluoroethyl group.
Examples of the C2-C6 alkenyl group which may have one or more halogen atoms include a vinyl group, an allyl group, a 3-methyl-2-butenyl group, a 2,2-dichlorovinyl group, and a 1,1-difluoroallyl group. Groups and pentafluoroallyl groups.
Examples of the C2-C6 alkynyl group which may have one or more halogen atoms include ethynyl group, 1-propynyl group, 2-propynyl group, chloroethynyl group, 1-bromo-2-hexynyl group and 1- ( A trifluoro) -2-butynyl group.
Examples of the C3-C6 cycloalkyl group optionally having one or more halogen atoms include a cyclopropyl group, a 1-fluorocyclopropyl group, a 2,2-dichlorocyclopropyl group, and a 3,3-dibromocyclobutyl group. And a cyclohexyl group.
The (C1-C6 alkoxy) C1-C6 alkyl group which may have one or more halogen atoms means that the C1-C6 alkoxy group which may have one or more halogen atoms has one or more halogen atoms Means a group bonded to an optionally substituted C1-C6 alkyl group, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a 1- (trifluoromethoxy) ethyl group, and a 3-fluoro-6- (hexyloxy) hexyl group. It is done.
The (C3-C6 cycloalkyl) C1-C6 alkyl group which may have one or more halogen atoms is a C1-C6 cycloalkyl group which may have one or more halogen atoms. Means a group bonded to a C1-C6 alkyl group which may have, for example, cyclopropylmethyl group, 1-cyclopropylethyl group, 4- (2,2-difluorocyclopropyl) butyl group and 6-cyclohexyl-1 -Fluorohexyl group.
Examples of the C2-C6 alkanediyl group which may have one or more halogen atoms include ethane-1,2-diyl group, 2,2,3,3-tetrafluorobutane-1,4-diyl group, Examples include pentane-2,5-diyl group, 3- (trifluoromethyl) pentane-1,5-diyl group, and hexane-1,6-diyl group.
The 5- to 6-membered heteroaryl group means, for example, a 5- or 6-membered aromatic heterocyclic group containing up to 3 atoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. Furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,4 -Oxadiazolyl group, 1,3,4-oxadiazolyl group, 1,2,5-oxadiazolyl group, 1,2,3-thiadiazolyl group, 1,2,4-thiadiazolyl group, 1,3,4-thiadiazolyl group, 1 , 2,5-thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,2,3-triazinyl and 1,2,4- Riajiniru group, and the like.

As this invention compound, the following compounds are mentioned, for example.
[Aspect 1] Formula (Ia)

[Wherein the symbols have the same meaning as described above. ] The compound shown.
[Aspect 2] A compound according to Aspect 1, wherein A is a nitrogen atom.
[Aspect 3] In aspect 2, R ¹ is a C1-C4 alkyl group,
R ⁴ is a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally having one or more halogen atoms, or a 5- to 6-membered hetero atom optionally having one or more atoms or substituents selected from group X A compound that is an aryl group.
[Aspect 4] A compound according to Aspect 3, wherein R ⁴ is a hydrogen atom, a halogen atom, or a C1-C6 alkyl group optionally having one or more halogen atoms.
[Aspect 5] A compound according to Aspect 1, wherein A is CH.
[Aspect 6] In Aspect 5, R ¹ is a C1-C4 alkyl group,
R ⁴ is a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally having one or more halogen atoms, or a 5- to 6-membered hetero atom optionally having one or more atoms or substituents selected from group X A compound that is an aryl group.
[Aspect 7] A compound according to Aspect 6, wherein R ⁴ is a hydrogen atom, a halogen atom, or a C1-C6 alkyl group optionally having one or more halogen atoms.
[Aspect 8] Formula (Ib)

[Wherein the symbols have the same meaning as described above. ] The compound shown.
[Aspect 9] A compound according to Aspect 8, wherein A is a nitrogen atom.
[Aspect 10] In Aspect 9, R ¹ is a C1-C4 alkyl group,
R ⁴ is a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally having one or more halogen atoms, or a 5- to 6-membered hetero atom optionally having one or more atoms or substituents selected from group X A compound that is an aryl group.
[Aspect 11] A compound according to Aspect 10, wherein R ⁴ is a hydrogen atom, a halogen atom, or a C1-C6 alkyl group optionally having one or more halogen atoms.
[Aspect 12] A compound according to Aspect 8, wherein A is CH.
[Aspect 13] In aspect 12, R ¹ is a C1-C4 alkyl group,
R ⁴ is a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally having one or more halogen atoms, or a 5- to 6-membered hetero atom optionally having one or more atoms or substituents selected from group X A compound that is an aryl group.
[Aspect 14] A compound according to Aspect 13, wherein R ⁴ is a hydrogen atom, a halogen atom, or a C1-C6 alkyl group optionally having one or more halogen atoms.

[Aspect 15-1] In the compound of the present invention, R ^A is a hydrogen atom, R ^B is —OSO ₂ CF ₃ , A is a nitrogen atom, R ¹ is a C1-C4 alkyl group, R ² And R ³ is a hydrogen atom, and R ⁴ is a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally having one or more halogen atoms, or a 1,2,4-triazolyl group.
[Aspect 15-2] The compound according to Aspect 15-1, wherein R ⁴ is a hydrogen atom.

[Aspect 16-1] In the compound of the present invention, R ^A is —OSO ₂ CF ₃ , R ^B is a hydrogen atom, A is a nitrogen atom, R ¹ is a C1-C4 alkyl group, and R ² And R ³ is a hydrogen atom, and R ⁴ is a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally having one or more halogen atoms, or a 1,2,4-triazolyl group.
[Aspect 16-2] A compound in which R ⁴ is a hydrogen atom, a C1-C6 alkyl group optionally having one or more halogen atoms, or a 1,2,4-triazolyl group in Aspect 16-1.

[Aspect 17-1] In the compound of the present invention, R ^A is —OSO ₂ CF ₃ , R ^B is a hydrogen atom, A is CH, R ¹ is a C1-C4 alkyl group, R ² and A compound in which R ³ is a hydrogen atom, and R ⁴ is a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally having one or more halogen atoms, or a 1,2,4-triazolyl group.
[Aspect 17-2] A compound according to Aspect 17-1, wherein R ⁴ is a hydrogen atom, a halogen atom, or a C1-C6 alkyl group optionally having one or more halogen atoms.

[Aspect 18] A compound according to Aspect 2, wherein R ⁴ is a hydrogen atom.
[Aspect 19] A compound according to Aspect 2, wherein R ⁴ is a halogen atom.
[Aspect 20] A compound according to Aspect 2, wherein R ⁴ is a C1-C6 alkyl group optionally having one or more halogen atoms.
[Aspect 21] The compound according to Aspect 9, wherein R ⁴ is a hydrogen atom.
[Aspect 22] The compound according to Aspect 9, wherein R ⁴ is a 1,2,4-triazolyl group.
[Aspect 23] In the compound of the present invention, R ¹ is a C1-C4 alkyl group, R ⁴ is a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally having one or more halogen atoms, or 1,2 , 4-triazolyl group.
[Aspect 24] In the compound of the present invention, R ¹ is an ethyl group and R ⁴ is a hydrogen atom, a halogen atom, a C1-C6 alkyl group optionally having one or more halogen atoms, or 1,2,4- A compound that is a triazolyl group.

Next, a method for producing the compound of the present invention will be described.

The compound of the present invention and the intermediate compound can be produced, for example, according to the methods described in the following production methods 1 to 5 and reference production methods 1 to 4.

Manufacturing method 1
Among the compounds of the present invention, a compound represented by the formula (Inn1) (hereinafter referred to as the compound (Inn1)) is a compound represented by the formula (Inn0) (hereinafter referred to as the compound (Inn0)). It can be produced by oxidizing.

[Wherein the symbols have the same meaning as described above. ]
The reaction is usually performed in a solvent. Examples of the solvent include halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene (hereinafter referred to as halogenated hydrocarbons), nitriles such as acetonitrile (hereinafter referred to as nitriles), and alcohols such as methanol and ethanol. (Hereinafter referred to as alcohols), esters such as ethyl acetate and butyl acetate (hereinafter referred to as esters), acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent include peracetic acid, m-chloroperbenzoic acid (hereinafter referred to as mCPBA), and aqueous hydrogen peroxide.
When hydrogen peroxide is used as the oxidizing agent, a base or a catalyst may be added as necessary.
Examples of the base used for the reaction include sodium carbonate.
Examples of the catalyst used for the reaction include tungstic acid and sodium tungstate.
In the reaction, with respect to 1 mol of compound (In0), the oxidizing agent is usually used at a ratio of 1 to 1.2 mol.
In the reaction, a base is usually used in an amount of 0.01 to 1 mol with respect to 1 mol of the compound (In0).
In the reaction, the catalyst is generally used in an amount of 0.01 to 0.5 mol per 1 mol of the compound (In0).
The reaction temperature is usually in the range of −50 to 50 ° C. The reaction time is usually in the range of 0.1 to 12 hours.

Manufacturing method 2
Among the compounds of the present invention, the compound represented by the formula (In2) (hereinafter referred to as the compound (In2)) is the compound represented by the formula (In3) (hereinafter referred to as the compound (In3)). It can be produced by oxidizing.

[Wherein, r represents 0 or 1 and other symbols have the same meaning as described above. ]
In this reaction, compound (In3) is used in place of compound (In0), and the oxidizing agent is 2 to 10 mol when r is 0 with respect to 1 mol of compound (In3), and r is 1 In this case, compound (In2) can be obtained according to the method described in Production Method 1 using 1 to 10 moles.

Production method 3
The compound of the present invention can be produced by dehydrating a compound represented by the formula (M1) (hereinafter referred to as compound (M1)).

[Wherein the symbols have the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran (hereinafter referred to as THF), tert-butyl methyl ether (hereinafter referred to as MTBE) (hereinafter referred to as ether). ), Halogenated hydrocarbons, aromatic hydrocarbons such as toluene, benzene, and xylene (hereinafter referred to as aromatic hydrocarbons), esters, nitriles, and mixtures thereof.
In the reaction, a condensing agent or an acid can be used.
Examples of the condensing agent used in the reaction include organic bases such as triphenylphosphine, triethylamine and pyridine (hereinafter referred to as organic bases) and a mixture of carbon tetrachloride, azodiesters such as triphenylphosphine and diethyl azodicarboxylate. A mixture of the like.
Examples of the acid used for the reaction include sulfonic acids such as paratoluenesulfonic acid.
In the reaction, with respect to 1 mol of the compound (M1), when a condensing agent is used, the condensing agent is usually in a proportion of 1 to 5 mol, and when an acid is used, the acid is usually in a proportion of 0.1 to 5 mol. Used in
The reaction temperature of the reaction is usually in the range of 0 to 200 ° C. The reaction time is usually in the range of 0.1 to 24 hours.

Manufacturing method 4
The compound of the present invention can be produced by the method shown below.

[Wherein the symbols have the same meaning as described above. ]
A compound represented by formula (M23) (hereinafter referred to as compound (M23)) is a compound represented by formula (M2) (hereinafter referred to as compound (M2)) and a compound represented by formula (M3) ( Hereinafter, it can be produced by reacting with compound (M3).
The reaction is usually performed in the presence of a solvent. Examples of the solvent used for the reaction include aromatic hydrocarbons.
In the reaction, compound (M3) is usually used at a ratio of 1 to 1.2 mol with respect to 1 mol of compound (M2).
The reaction temperature of the reaction is usually in the range of 50 to 150 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
Compound (M3) can be produced according to the method described in International Publication No. 2012/0886848 or International Publication No. 2013/018928.

The compound of the present invention can be produced by reacting the compound (M23) with an oxidizing agent.
The reaction is usually performed in the presence of a solvent. Examples of the solvent used for the reaction include aromatic hydrocarbons.
An example of the oxidizing agent used in the reaction is iodine.
In the reaction, with respect to 1 mol of the compound (M23), the oxidizing agent is usually used in a ratio of 2 to 5 mol.
The reaction temperature of the reaction is usually in the range of 50 to 150 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
The compound of the present invention can be produced in one pot from the compound (M2) without isolating the compound (23).

Manufacturing method 5
The compound of the present invention is produced by reacting a compound represented by the formula (M4) (hereinafter referred to as compound (M4)) with trifluoromethanesulfonic anhydride or trifluoromethanesulfonyl chloride in the presence of a base. Can do.

[Wherein, one of R ^D and R ^E represents a hydroxyl group, the other represents a hydrogen atom, and the other symbols represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include aliphatic hydrocarbons such as ethers, hexane and heptane (hereinafter referred to as aliphatic hydrocarbons), aromatic hydrocarbons, halogenated hydrocarbons, esters, and nitriles. , Aprotic polar solvents and mixtures thereof.
Examples of the base used for the reaction include organic bases.
The reaction is carried out at a ratio of usually 0.8 to 1.5 mol of trifluoromethanesulfonic anhydride or trifluoromethanesulfonic acid chloride and usually 0.8 to 1.5 mol of base with respect to 1 mol of compound (M4). It is used in the ratio.
The reaction temperature is usually in the range of −78 to 50 ° C. The reaction time is usually in the range of 0.1 to 24 hours.

Reference manufacturing method 1
Compound (M1) can be produced by reacting compound (M2) with a compound represented by formula (M5) (hereinafter referred to as compound (M5)).

[Wherein, X represents a hydroxyl group or a chlorine atom, and other symbols have the same meaning as described above. ]
This reaction can be carried out according to the method described in International Publication No. 2013/018928.
Compound (M5) can be produced according to the method described in International Publication No. 2012/088684 or International Publication No. 2013/018928.

Reference production method 2
Compound (M2) can be produced by the method shown below.

[Wherein the symbols have the same meaning as described above. ]
The step of producing a compound represented by formula (M7) (hereinafter referred to as compound (M7)) from a compound represented by formula (M6) can be carried out according to the method described in Production Method 5. The base is preferably added after completion of the reaction.
The step of producing a compound represented by formula (M8) by nitrating compound (M7) (hereinafter referred to as compound (M8)) should be carried out according to the method described in International Publication No. 2013/018928. Can do.
The step of producing compound (M2) by reducing compound (M8) is a method of using metallic iron described in New Experimental Chemistry Course 15 Oxidation and Reduction [II] (Maruzen) as a reducing reagent, or a method analogous thereto Can be implemented.

Reference manufacturing method 3
Compound (M4) can be produced by reacting a compound represented by formula (M9) (hereinafter referred to as compound (M9)) with iodotrimethylsilane.

[Wherein, one of R ^F and R ^G represents a methoxy group, the other represents a hydrogen atom, and the other symbols represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent. Nitriles are mentioned as a solvent used for reaction.
Instead of iodotrimethylsilane used in the reaction, a mixture of chlorotrimethylsilane and sodium iodide can also be used.
The reaction is carried out at a ratio of usually 1 to 10 moles of iodotrimethylsilane, usually 1 to 10 moles of chlorotrimethylsilane, and usually 1 to 10 moles of sodium iodide with respect to 1 mole of compound (M9). Used.
The reaction temperature of the reaction is usually in the range of 20 to 100 ° C. The reaction time is usually in the range of 1 to 48 hours.

Reference production method 4
Compound (M9) can be produced by the method shown below.

[Wherein the symbols have the same meaning as described above. ]
The step of producing a compound represented by the formula (M11) by reacting the compound represented by the formula (M10) with the compound (M5) (hereinafter referred to as the compound (M11)) is the method described in Reference Production Method 1. It can implement according to. The step of producing compound (M9) by reacting compound (M11) with a condensing agent or acid can be carried out according to the method described in Production Method 3.
The compound represented by the formula (M10) is a known product or can be produced by a known method.

After completion of the reactions of the above production methods 1 to 5 and reference production methods 1 to 4, the reaction mixture is poured into water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is poured into water. The resulting solid is collected by filtration; or by performing post-treatment operations such as collecting the solid produced in the reaction mixture by filtration, the compound of the present invention, compound (M1), compound (M7), compound (M8) , Compound (M2), Compound (M4), Compound (M11) or Compound (M9) can be isolated. The isolated compound of the present invention, compound (M1), compound (M7), compound (M8), compound (M2), compound (M4), compound (M11) or compound (M9) is recrystallized, chromatographed, etc. Can be further purified by

Specific examples of the compound of the present invention that can be produced according to the methods described in the above production methods 1 to 5 are shown below.
In this specification, Me means a methyl group, Tr means a 1,2,4-triazol-1-yl group, and Pz means a pyrazol-1-yl group.
1) The following formula (A)

A compound in which A, R ⁴ and n are any one of those listed in List 1.

Listing 1:
[A; R ⁴ ; n] = [CH; H; 0], [CH; H; 1], [CH; H; 2], [CH; F; 0], [CH; F; 1], [ CH; F; 2], [CH; Cl; 0], [CH; Cl; 1], [CH; Cl; 2], [CH; Br; 0], [CH; Br; 1], [CH; Br; 2], [CH; Me; 0], [CH; Me; 1], [CH; Me; 2], [CH; CF ₃ ; 0], [CH; CF ₃ ; 1], [CH; CF ₃ ; 2], [CH; CF ₂ CF ₃ ; 0], [CH; CF ₂ CF ₃ ; 1], [CH; CF ₂ CF ₃ ; 2], [CH; OMe; 0], [CH; OMe; 1], [CH; OMe; 2], [CH; OCF ₃ ; 0], [CH; OCF ₃ ; 1], [CH; OCF ₃ ; 2], [CH; SCF ₃ ; 0], [ CH; SCF ₃ ; 1], [CH; SCF ₃ ; 2], [CH; S (O) CF ₃ ; 0], [CH; S (O) CF ₃ ; 1], [CH; S (O) CF ₃ ; 2], [CH; S (O) ₂ CF ₃ ; 0], [CH; S (O) ₂ CF ₃ ; 1], [CH; S (O) ₂ CF ₃ ; 2], [N ; H; 0], [N; H; 1], [N; H; 2], [N; F; 0], [N; F; 1], [N; F; 2], [N; Cl 0], [N; Cl; 1], [N; Cl; 2], [N; Br; 0], [N; Br; 1], [N; Br; 2], [N; Me; 0 ], [N; Me; 1] [N; Me; 2], [N; CF _3; 0], [N; CF _3; 1), (N; CF _3; 2), (N; CF ₂ CF _3; 0], [N; CF ₂ CF ₃ ; 1], [N; CF ₂ CF ₃ ; 2], [N; OMe; 0], [N; OMe; 1], [N; OMe; 2]

2) The following formula (B)

A compound in which A, R ⁴ and n are any one of those listed in List 1.

3) The following formula (C)

A compound in which A, R ⁴ and n are any one of those listed in List 2.

Listing 2:
[A; R ⁴ ; n] = [CH; F; 0], [CH; F; 1], [CH; F; 2], [CH; Cl; 0], [CH; Cl; 1], [ CH; Cl; 2], [CH; Br; 0], [CH; Br; 1], [CH; Br; 2], [CH; Me; 0], [CH; Me; 1], [CH; Me; 2], [CH; CF ₃ ; 0], [CH; CF ₃ ; 1], [CH; CF ₃ ; 2], [CH; CF ₂ CF ₃ ; 0], [CH; CF ₂ CF ₃ ; 1], [CH; CF ₂ CF ₃ ; 2], [CH; OMe; 0], [CH; OMe; 1], [CH; OMe; 2], [CH; OCF ₃ ; 0], [CH ; OCF ₃ ; 1], [CH; OCF ₃ ; 2], [CH; SCF ₃ ; 0], [CH; SCF ₃ ; 1], [CH; SCF ₃ ; 2], [CH; S (O) CF ₃ ; 0], [CH; S (O) CF ₃ ; 1], [CH; S (O) CF ₃ ; 2], [CH; S (O) ₂ CF ₃ ; 0], [CH; S (O) ₂ CF ₃ ; 1], [CH; S (O) ₂ CF ₃ ; 2], [N; Cl; 0], [N; Cl; 1], [N; Cl; 2], [N ; Br; 0], [N; Br; 1], [N; Br; 2], [N; Me; 0], [N; Me; 1], [N; Me; 2], [N; CF ₃ ; 0], [N; CF ₃ ; 1], [N; CF ₃ ; 2], [N; OMe; 0], [N; OMe; 1], [N; OMe; 2], [N; NH ₂ ; 0 ], [N; NH ₂ ; 1], [N; NH ₂ ; 2], [N; NHMe; 0], [N; NHMe; 1], [N; NHMe; 2], [N; NH (CH ₂ CF ₃ ); 0], [N; NH (CH ₂ CF ₃ ); 1], [N; NH (CH ₂ CF ₃ ); 2], [N; NMe ₂ ; 0], [N; NMe ₂ ; 1], [N; NMe ₂ ; 2], [N; Tr; 0], [N; Tr; 1], [N; Tr; 2], [N; Pz; 0], [N; Pz; 1], [N; Pz; 2]

3) The following formula (D)

A compound in which A, R ⁴ and n are any one of those listed in List 2.

Examples of pests for which the compounds of the present invention are effective include harmful animals such as harmful insects and harmful mites. Specific examples of such harmful animals include, but are not limited to, the following.

Hemiptera pests: Japanese green planthopper (Laodelphax striatellus), Japanese green planthopper (Nilaparvata lugens), white planthopper (Sogatella furcifera), corn planter (Peregrinus maidis), etc .; (Nephotettix nigropictus), Incospider (Recilia dorsalis), Emporasca onukii, Empoasca fabae, Cornleaf Hopper (Dalbulus maidis), White-leafed beetle Mahanarva posticata, Mahanarva fimbriolata, etc .; Aphis goss ii, Aphis spiraecola, Myzus persicae, Japanese radish aphid (Br evicoryne brassicae), lipstick aphid (Lipaphis erysimi), tulip beetle aphid (Macrosiphum euphorbiae), potato beetle aphid (Aulacorthum solani), lettuce beetle aphid (Nasonovia ribisnigri), hum ), Peach beetle (Hyalopterus pruni), soybean aphid (Aphis glycines), corn aphid (Rhopalosiphum maidis), sugar beetle aphid (Tetraneuraabnigriabdominalis), scorpion aphid (Ceratovacuna lanigera), rio rotoma Vine grape aphids (Daktulosphaira vitifoliae), Pecan phylloxera (Phylloxera devastatrix), Pecan leaf phylloxera (Phylloxera notabilis), Southern pecan leaf phylloxera (Phyll) oxera russellae) and other aphids; Adelges tsugae, Adelges piceae, Aphrastasia pectinatae and other aphids; Scotinophara lurida, Malayan Blue-headed beetle (Nezara antennata), White-headed beetle (Eysarcoriseneaeneus), White-headed beetle (Eysarcoris lewisi), White-headed beetle (Eysarcorisralventralis), Purple-headed beetle (Eysarcoris memashimina) (Nezara viridula), Brown stink bug (Euschistus heros), Red banded stink bug (Piezodorus guildinii), stink bugs such as Oebalus pugnax, Dichelops melacanthus; Burrower brown bug (Scaptocoris caste , Spider helicopters (Leptocorisa chinensis), spider helicopters (Leptocorisa acuta), etc .; (Togo hemipterus), American bug beetle (Blissus leucopterus), etc .; Mosquito bugs such as Trileurodes vaporariorum, Tobacco whitefly (Bemisia tabaci), Citrus whitefly (Dialeurodes citri), Citrus whitefly (Aleurocanthus spiniferus), Chattoge whitefly (Al whitefly, such as eurocanthus camelliae; aphid beetle (Abidi moth), Aonidiella aurantii, diaspidiotus perniciosus, Pseudaulacaspis Scale insects such as scale insects (Unaspis citri), etc .; Scale insects such as ruby beetles (Ceroplastes rubens); ), Pseudodococcus longispinus, Brattlenia rehi, and other species; Diaphorina citri, Cacopsylla pyrisuga, Chi Whales such as Cacopsylla chinensis and Bactericera cockerelli; Corythucha marmorata, Stepiusitis nashi, exander Bed bugs such as Giant Cicada (Quesada gigas).

Lepidopterous insects: Chilo ニ suppressalis, Darkheaded stem borer (Chilo polychrysus), White stem borer (Scirpophaga innotata), Scirpophaga incertulas, Rupela albina, Cai halopatia cis (Marasmia exigua), cotton moth (Notarcha derogata), green eel (Ostrinia furnacalis), European corn borer (Ostrinia nubilalis), yellow moth (Hellula undalis), Shibatatsuga (Pediasia teterum (Pediasia teterum) Diatraea saccharalis), etc .; Sorgoptera メ イ litura, Spodoptera imexnagua, Spodoptera imexna rata), mushroom (Mamestra brassicae), rice mushroom (Sesamia inferens), white-footed mushroom (Spodoptera mauritia), frangipaya (Naranga aenescens), tsumoji-royo (Spodoptera frugiperda), exotica pod Tamanaginwowa (Autographa nigrisigna), rice kinawaba (Plusia festucae), Soybean looper (Chrysodeixis includens), Trichopulsia genus, Heliothis virescens, etc. Cotton leafworm (Alabama argillacea), Hop vine borer (Hydraecia immanis) and other moths; White butterflies such as Pieris rapae; Nasihimeshinmoi (Grapholita molesta), Sumohimeshini (Grapholita dimorph) a), leguminous moth (Leguminivora 、 glycinivorella), Azuki beetle (Matsumuraeses azukivora), apple wolfberry (Adoxophyes orana fasciata), tea wolfberry (Adoxophyes honmai), chamonaki (Homona magnancos), (Cydia pomonella), Tetramoera schistaceana, Bean Shoot Borer (Epinotia aporema), Citrus fruit borer (Ecdytolopha aurantiana), etc .; Sinkigas (Carposina sasakii); Coffee Leaf miner (Leucoptera coffeela), Anemone genus such as Rionetia; Limantria genus such as Lymantria dispar, Euproctis pseudoconspersa, etc. Species of the genus, such as Spodoptera (Plutella xylostella), etc licus); celery butterflies, such as Parnara guttata.

Common pests: Citrus thrips (Frankliniella occidentalis), Thrips palmi, Scirtothrips dorsalis, Thrips tabaci, Thrips tabaci, Thrips tabaci, Thrips tabaci, Thrips tabaci Thrips: The Thrips such as Haplothrips aculeatus.

Diptera: insect fly, Delia platura, Delia qua antiqua, etc .; sugar beet root maggot (Tetanops myopaeformis), etc .; (Liriomyza trifolii), leafhoppers (Chromatomyia horticola), etc .; leafhoppers (Chlorops oryzae); Fruit flies such as Ceratitis capitata; sand flies such as Hydrellia griseola, Hydrellia philippina, Hydrellia sasakii; Drosophila; flies such as Megaselia spiracularis; flies such as Clogmia albipunctata; black fly flies; Mayetiola destructor; Streptococcus such as Diopsis macrophthalma; Crane fly such as European ジ cranefly (Tipula palracosa), Common cranefly (Tipula oleracea), European cranefly (Tipula paludosa)

Coleoptera: Western corn root worm (Diabrotica virgifera virgifera), Southern corn root worm (Diabrotica undecimpunctata howardi), Northern corn root worm (Diabrotica barberi), Mexican corn root worm (Diabrotica virgifera zeae), Banded cumber rot balte (ab) , Cucurbit Beetle (Diabrotica speciosa), Bean Leaf Beetle (Cerotoma trifurcata), Bark beetle Beetle (Oulema melanopus), Root beetle (Aulacophora femoralis), Kibushi horn beetle (Phyllotreta striolata), Colorado potato beetle (De , Grapes colaspis (Colaspis brunnea), corn flare beetle (Chaetocnema pulicaria), potato flare beetle (Epitrix cucumeris), rice beetle (Dicladispa armigera) Grape Colaspis (Colaspis brunnea), southern beetles such as southern corn leaf beetle (Myochrous denticollis); Seedcorn beetle (Stenolophus lecontei), slender seedcorn beetle (Clivina impressifrons), etc .; , Anomala albopilosa, Bean squirrel (Popillia japonica), Nagachakogane (Heptophylla picea), European Chafer (Rhizotrogus majalis), Black marsh moth (Tomarus gibbosus), Holotrichia genus Weevil (Sitophilus zeamais), rice weevil (Echinocnemus squameus), rice weevil (Lissorhoptrus oryzophilus), white weevil (Rhabdoscelus lineatocollis), cotton weevil (Anthonomus grandophus scorpion) natus), Southern Corn Billbug (Sphenophorus callosus), Soybean stalk weevil (Sternechus S subsignatus), Sgarcane wiivil (Sphenophorus levis), Sabihyo weevil (Scepticus griseus), Toburo Weevil such as Coffee Berry Borer (Hypothenemus hampei); Long-horned beetles; leopard beetles; longhorn beetles (Anoplophora malasiaca), longhorn beetles such as Migdolus fryanus; Okinawa beetle (Melanotus okinawensis), Agriotes scous s), beetles such as Melanotusnotlegatus (Agriotes sp., Aelous sp., Anchastus sp., Melanotus sp., Limonius sp., Connoderus sp., Ctenicera sp.); Scallops.

Insect pests: Locusta migratoria, Moroccan grasshopper (Dociostaurus maroccanus), Australian grasshopper (Chortoicetes terminifera), red locust (Nomadacris septemfasciata), Brown Locust (Locustana parust Calliptamus italicus), Differential grasshopper (Melanoplus differentialis), Two striped grasshopper (Melanoplus bivittatus), Migratory grasshopper (Melanoplus sanguinipes), Red-Legged grasshopper (Melanoplus femurrubrum), Grasshoppers such as Yellow-winged locust (Gastrimargus musicus), Spur-throated locust (Austracris コ guttulosa), Cobaineago (Oxya yezoensis), Red-tailed hawk (Oxya japonica), Thai winged chinook (Patanga succincta); Kellys such as ryllotalpa africana); Crickets such as European crickets (Acheta domesticus) and Enma crickets (Teleogryllus emma); Grasshoppers such as Mormon cricket (Anabrus simplex).

Hymenopteran pests: bees such as Athalia rosae and Athalia japonica; fire ants; ants such as Brown leaf-cutting ant (Atta capiguara)
Cockroach insects: German cockroaches such as the German cockroach (Blattella germanica); cockroaches such as the black cockroach (Periplaneta fuliginosa), the American cockroach (Periplaneta americana), the black cockroach (Periplaneta brunnea), and the American cockroach (Blatta orientalis).

Termite pests: Yamato termites (Reticulitermes speratus), termites (Coptotermes formosanus), American ants termites (Incisitermes minor), stag termites (Cryptotermes domesticus), ants, termites (Odontotermes eoformosaterm), ants Glyptotermes Reticulitermes kanmonensis), Takasago termites (Nasutitermes takasagoensis), Nitobe termites (Pericapritermes nitobei), Mushy termites (Sinocapritermes mushae), Cornitermes cumulans like.

Mites: Spider mites (Tetranychus urticae), spider mites (Tetranychus kanzawai), red spider mites (Panonychus ulmi), apple spider mites (Panonychus ulmi), spider mites (Aculops pelekassi), red mite Pistrum (copper) Tomato rustic mites (Aculops lycopersici), Chinese radish mites (Calacarus carinatus), Chinese radish mites (Acaphylla theavagrans), Green rustic mites (Eriophyes chibaensis), Apple ticks (Aculus schlechtendali), etc .; Toad spider mites (Brevipalpus phoenicis) and other spider mites; Toxid spider mites (Haemaphysalis longicornis), tossed tick (Haemaphysalis flava), tortoise tick (Dermacentor taiwanensis), to the American cattle bear Dermacentor variabilis, Ixodes ovatus, Ixodes persulcatus, Black-legged tick (Ixodes scapularis), Amblyomma americanum, Boophilus microplus, R. Tick such as: Tyrophagus putrescentiae, spiny mite (Tyrophagus similis), etc .; mite mite (Dermatophagoides pteronyssinus); , Mites (Cheyletus moorei), crayfish mites (Cheyletiella yasguri); mite mites (Otodectes cynotis), mite mites (Sarcoptes scabiei), etc .; Acne mites such as emodex canis; Carp mites; House crabs; Hornets such as Ornithonyssus sylviarum; Etc.
Spiders: Common spiders such as Cheracanthium japonicum; Brown spiders such as Latrodectus hasseltii.
Lip and leg class: Geges such as Gezi (Thereuonema hilgendorfi); Barley pods such as Scolopendra subspinipes.
Double-legged class: zelkova (Oxidus gracilis), zelkova (Nedyopus tambanus), etc.
Isopods: Rubber beetles such as Armadillidium vulgare.
Gastropoda: Coleoptera such as Limax marginatus and Limax flavus; Apple mussels such as Pomacea canaliculata; Monoaragai such as Austropeplea ollula.

Nematodes: Aphelenchoides besseyi, such as Aphelenchoides besseyi; Minaminegusaresenchu (Pratylenchus coffeae), Pratylenchus brachyurus, Pratylenchus neglectus 等, Radsimus Cucumber species: Javaloid nematode Me (Meloidogyne javanica), Sweet potato nematode Me (Meloidogyne incognita), Kitaenbu nematode Me (Meloidogyne hapla), soybean cyst nematode (Heterodera glycines), potato cyst nematode (Globodera Heterodera; Hopro-Rimes such as Rotylenchulus reniformis; Anguinas such as Nothotylenchus acris and Ditylenchus dipsaci; Tirenkurusu such as Luz Semi penetrometer transformer (Tylenchulus semipenetrans); Torikodorusu such; grape giant harisen (Xiphinema index) Rongidorusu such as para Sita affection Ren box such as pine wood nematode (Bursaphelenchus xylophilus), and the like.

The target harmful insects and harmful ticks may be insects and ticks that have reduced drug sensitivity to insecticides / acaricides or have developed drug resistance. However, when the drug sensitivity is greatly reduced or the drug resistance is greatly developed, it is desirable to use the composition of the present invention containing an insecticide / acaricide other than the target insecticide / acaricide.

The compounds of the present invention can also be used to protect plants from plant diseases caused by insect-borne viruses.

Examples of plant diseases caused by insect-borne viruses having the control effect of the compound of the present invention include the following.

Rice dwarf disease (Rice waika virus), Tundra disease (Rice tungro spherical virus, Rice tungro bacilliform virus), Rice grassy stunt disease, Rice ragged stunt virus, Rice striped leaf blight Diseases (Rice stripe virus), rice black streaked dwarf virus, rice southern black-streaked dwarf virus, rice gall dwarf virus, rice leaf blight ( Rice hoja blanca virus), White leaf desease of rice, Yellow dwarf virus, Red disease (Rice penyakit merah virus), Rice yellow stunt virus, Transition yellowing Disease (Rice transitory yellowing virus), Rice yellow mottle virus, Rice necrosis mosaic virus, Rice dwarf stunt virus, North wheat mosaic disease Northern Cereal Mosaic Virus), barley yellowing atrophy disease (Barley Yellow Dwarf Virus), wheat yellow leaves disease (Wheat yellow dwarf virus), Oat sterile dwarf (Oat sterile dwarf virus), Wheat streak mosaic (Wheat streak mosaic virus)
Maize dwarf mosaic virus, Maize stripe disease (maize stripe tenuivirus), Maize chlorotic dwarf (Maize chlorotic dwarf virus), Maize chlorotic mottle (maize chlorotic mottle virus), Maize rayado fino (maize rayado fino marafivirus), Corn stunt (Corn stunt spiroplasma), Maize bushy stunt (Maize bushy stunt phytoplasma), sugarcane mosaic disease (Sugarcane mosaic virus),
Soybean mild mosaic virus, Mosaic disease (Alfalfa Mosaic Virus, Bean yellow-spot mosaic virus, Soybean mosaic virus, Bean yellow mosaic virus, Cowpea severe mosaic virus), Soybean virus disease (Broad bean wilt virus, Bean common mosaic virus, Peanut stunt virus, Southern bean mosaic virus), soybean dwarf luteovirus, Milk-vetch dwarf luteovirus, Bean-pod mottle (Bean-pod mottle virus), Brazilian bud blight (Tobbaco streak virus) ), Cowpea chlorotic mottle (Cowpea chlorotic mottle), Mung bean yellow mosaic (Mung bean yellow mosaic virus), Peanut stripe (Peanut stripe mottle), Soybean crinkle leaf (Soybean crinkle leaf virus), Soybean severe stunt (Soybean severe stunt virus) Tomato chlorosis virus, Tomato spotted wilt virus, Tomato yellow leaf curl virus, Melon yellow wilt (Melon) yellow spot virus), pumpkin mosaic disease, Cucumber mosaic virus, Zucchini yellow mosaic virus, turnip mosaic virus, cucurbit yellowing disease ( Cucurbit chlorotic yellows virus), Capsicum chlorosis virus, Beet pseudo yellows virus, Chrysanthemum stem necrosis virus, Impatiens necrotic spot virus , Iris yellow spot virus, Sweet potato internal cork virus, Sweet potato shukuyo mosaic virus, Polymixa or Olpidium genus Viral disease.

The harmful arthropod control agent of the present invention contains the compound of the present invention and an inert carrier. The harmful arthropod control agent of the present invention is usually a mixture of the compound of the present invention and an inert carrier such as a solid carrier, a liquid carrier, a gaseous carrier, etc., and if necessary, a surfactant and other adjuvants for formulation. Emulsions, oils, powders, granules, wettable powders, flowables, microcapsules, aerosols, smokers, poisonous baits, resin preparations, shampoos, pastes, foams, carbon dioxide It is formulated into preparations, tablets and the like. These preparations may be used after being processed into mosquito coils, electric mosquito mats, liquid mosquito traps, fumigants, fumigants, sheet preparations, spot-on agents, or oral treatments. Moreover, the harmful arthropod control agent of the present invention can be mixed with other insecticides, acaricides, nematicides, fungicides, plant growth regulators, herbicides and synergists.
The harmful arthropod control agent of the present invention usually contains 0.01 to 95% by weight of the compound of the present invention.

Examples of solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, bentonite, fusami clay, acidic clay), synthetic hydrous silicon oxide, talc, ceramics, and other inorganic minerals (sericite, quartz, sulfur). , Activated carbon, calcium carbonate, hydrated silica, etc.), fine powders and granules of chemical fertilizers (ammonium sulfate, phosphorous acid, ammonium nitrate, urea, ammonium chloride, etc.), and synthetic resins (polypropylene, polyacrylonitrile, polymethyl methacrylate) Polyester resins such as polyethylene terephthalate, nylon resins such as nylon-6, nylon-11, and nylon-66, polyamide resins, polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-propylene copolymers).

Examples of the liquid carrier include water, alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, phenoxyethanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (Toluene, xylene, ethylbenzene, dodecylbenzene, phenylxylylethane, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, isopropyl myristate, Ethyl oleate, diisopropyl adipate, diisobutyl adipate, propylene glycol monomethyl ether acetate, etc.), nitriles (acetonitrile, isobutyrate) Nitriles), ethers (diisopropyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, etc. ), Acid amides (dimethylformamide (hereinafter referred to as DMF), dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), sulfoxides (dimethylsulfoxide, etc.), propylene carbonate and vegetable oil ( Soybean oil, cottonseed oil, etc.).

Examples of the gaseous carrier include fluorocarbon, butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbon dioxide gas.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, and polyethylene glycol fatty acid ester, and anions such as alkyl sulfonate, alkyl benzene sulfonate, and alkyl sulfate. Surfactant is mentioned.

Examples of other adjuvants for preparation include fixing agents, dispersants, colorants and stabilizers, such as casein, gelatin, saccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, Synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert- And a mixture of butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).

Examples of the base material of the resin preparation include vinyl chloride polymers, polyurethanes, etc., and these base materials include phthalic acid esters (dimethyl phthalate, dioctyl phthalate, etc.) and adipic acid esters as necessary. Further, a plasticizer such as stearic acid may be added. The resin formulation is obtained by kneading the compound in the base material using a normal kneading apparatus, and then molding by injection molding, extrusion molding, press molding, etc., and if necessary, through steps such as molding, cutting, It can be processed into resin preparations such as plate, film, tape, net, and string. These resin preparations are processed, for example, as animal collars, animal ear tags, sheet preparations, attracting strings, or gardening supports.
Examples of the bait base include cereal flour, vegetable oil, sugar, crystalline cellulose and the like, and if necessary, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, and preservatives such as dehydroacetic acid. Additives for preventing accidental eating by children and pets such as pepper powder, pests such as cheese flavor, onion flavor and peanut oil are added.

In the method for controlling harmful arthropods of the present invention, an effective amount of the compound of the present invention is applied directly to harmful arthropods and / or to the place where the harmful arthropods live (plants, soil, households, animal bodies, etc.). Is done. The harmful arthropod control method of the present invention is usually used in the form of the harmful arthropod control agent of the present invention.

When the harmful arthropod control agent of the present invention is used for controlling harmful arthropods in the agricultural field, the application amount is usually 1 to 10,000 g as the amount of the compound of the present invention per 10,000 m ² . When the harmful arthropod control agent of the present invention is formulated into an emulsion, wettable powder, flowable agent, etc., it is usually diluted with water so that the concentration of the compound of the present invention becomes 0.01 to 10,000 ppm. Applied, granules, powders, etc. are usually applied as they are.

These preparations and water dilutions of these preparations may be sprayed directly on harmful arthropods or plants such as crops to be protected from harmful arthropods, and harmful arthropods that inhabit the soil of cultivated land. You may treat to this soil in order to control.

Also, it can be treated by methods such as wrapping a resin preparation processed into a sheet or string around the crop, stretching it around the crop, or laying it on the stock soil.

When the harmful arthropod control agent of the present invention is used for controlling harmful arthropods that live in the house, the amount applied is usually the amount of the compound of the present invention per 1 m ² of treatment area when treated on the surface. 0.01 to 1000 mg, and when processing in a space, the amount of the compound of the present invention per 1 m ³ of the processing space is usually 0.01 to 500 mg. When the harmful arthropod control agent of the present invention is formulated into an emulsion, wettable powder, flowable agent, etc., it is usually diluted with water so that the concentration of the compound of the present invention is 0.1 to 10,000 ppm. Apply oils, aerosols, smoke, poison baits, etc. as they are.

When the harmful arthropod control agent of the present invention is used to control ectoparasites of cattle, horses, pigs, sheep, goats, chickens, small animals such as dogs, cats, rats, mice, etc., it is well known in veterinary medicine. Can be used on animals. As a specific method of use, for the purpose of systemic suppression, for example, administration by tablet, feed mixing, suppository, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.) is intended for non-systemic suppression. In this case, for example, an oil agent or an aqueous liquid is sprayed, a pour-on treatment or a spot-on treatment is performed, the animal is washed with a shampoo preparation, or a resin preparation is attached to the animal with a collar or ear tag. The amount of the compound of the present invention when administered to an animal body is usually in the range of 0.1 to 1000 mg per 1 kg body weight of the animal.

Hereinafter, the present invention will be described more specifically with reference to production examples, formulation examples, and test examples. However, the present invention is not limited to these examples.
In the examples, room temperature usually indicates 10 to 30 ° C. ¹ H NMR represents a proton nuclear magnetic resonance spectrum, tetramethylsilane was used as an internal standard, and chemical shift (δ) was expressed in ppm.

Production Example 1 (1)
After slowly adding 4.2 g of 65% nitric acid at room temperature to a mixture of 10.5 g of 4-hydroxyphenyl = trifluoromethanesulfonate and 35 mL of acetic acid, the mixture was stirred at room temperature for 1 hour. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate, and then the organic layer was concentrated under reduced pressure to obtain 10.99 g of a compound represented by the following formula (hereinafter referred to as intermediate (1-1)).

¹ H-NMR (CDCl ₃ ) δ: 10.60 (1H, s), 8.07 (1H, d), 7.53 (1H, dd), 7.29 (1H, d).

Production Example 1 (2)
A mixture of intermediate (1-1) 5.44 g, iron powder 6.09 g, acetic acid 7 mL, water 7 mL and ethyl acetate 21 mL was stirred under reflux for 1 hour. The reaction mixture was filtered, water was added to the filtrate, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure. N-Hexane and chloroform were added to the obtained residue, and the precipitated solid was collected by filtration to obtain 3.53 g of a compound represented by the following formula (hereinafter referred to as intermediate (1-2)).

¹ H-NMR (CDCl ₃ ) δ: 6.71 (1H, d), 6.64 (1H, d), 6.54 (1H, dd), 4.95 (1H, br s), 3.90 (2H, br s).

Production Example 1 (3)
A mixture of 320 mg of 2- (ethylsulfanyl) -4- (trifluoromethyl) benzoic acid, 0.16 mL of oxalyl dichloride, 1 drop of DMF and 5 mL of chloroform was stirred at room temperature for 1 hour and concentrated under reduced pressure. A mixture of the obtained residue and 5 mL of THF was added to a mixture of 329 mg of Intermediate (1-2) and 8 mL of THF under ice-cooling, and the mixture was brought to room temperature and stirred at room temperature for 1 hour. Saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the organic layer was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, so as to obtain 316 mg of a compound represented by the following formula (hereinafter referred to as intermediate (1-3)).

¹ H-NMR (CDCl ₃ ) δ: 9.31 (1H, s), 8.15 (1H, s), 8.03 (1H, d), 7.74 (1H, s), 7.62 (1H, d), 7.41 (1H, s ), 7.11-7.06 (2H, m), 3.05 (2H, q), 1.36 (3H, t).

Production Example 1 (4)
A mixture of 310 mg of the intermediate (1-3), 260 mg of bis (2-methoxyethyl) azodicarboxylate, 282 mg of triphenylphosphine and 8 mL of THF was stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 1 hour. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the organic layer was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 212 mg of a compound represented by the following formula (hereinafter referred to as compound (2)).

¹ H-NMR (CDCl ₃ ) δ: 8.28 (1H, d), 7.84 (1H, d), 7.68 (1H, d), 7.62 (1H, s), 7.51 (1H, d), 7.35 (1H, dd ), 3.11 (2H, q), 1.47 (3H, t).

The compounds produced according to the method described in Production Example 1 (4) and their physical properties are shown below.
Formula (1-c)

Wherein the combination of A and R ⁴ is represented by [Table 1].

Compound (8): ¹ H-NMR (CDCl ₃ ) δ: 8.80-8.77 (1H, m), 7.94 (1H, d), 7.90 (1H, d), 7.80-7.76 (1H, m), 7.40 (1H , dd), 3.11 (2H, q), 1.51 (3H, t).

Formula (1-d)

Wherein the combination of A and R ⁴ is represented by [Table 2].

Compound (10): ¹ H-NMR (CDCl ₃ ) δ: 9.28 (1H, s), 8.74 (1H, d), 8.30 (1H, d), 8.20 (1H, s), 7.83 (1H, d), 7.81-7.77 (1H, m), 7.45 (1H, dd), 3.97 (2H, q), 1.45 (3H, t).

Production Example 2
To a mixture of 212 mg of compound (2) and 5 mL of chloroform, 228 mg of mCPBA (purity 65% or more) was added under ice cooling, and the mixture was stirred at room temperature for 3 hours. A sodium thiosulfate aqueous solution was added to the reaction mixture, and the mixture was extracted with chloroform. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and dried over anhydrous sodium sulfate, and then the organic layer was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 208 mg of a compound represented by the following formula (hereinafter referred to as compound (3)).

¹ H-NMR (CDCl ₃ ) δ: 8.53 (1H, d), 8.14 (1H, d), 8.08 (1H, dd), 7.79 (1H, d), 7.71 (1H, d), 7.40 (1H, dd ), 3.89 (2H, q), 1.44 (3H, t).

The compounds produced according to the method described in Production Example 2 and their physical properties are shown below.
Formula (1-e)

A compound in which A and R ⁴ are represented by [Table 3].

Compound (1):
¹ H-NMR (CDCl ₃ ) δ: 8.26 (1H, d), 7.94 (1H, d), 7.79 (1H, dd), 7.75 (1H, d), 7.68 (1H, d), 7.37 (1H, dd ), 3.87 (2H, q), 1.43 (3H, t).
Compound (7): ¹ H-NMR (CDCl ₃ ) δ: 8.41 (1H, d), 7.96 (1H, dd), 7.86 (1H, d), 7.75 (1H, d), 7.68 (1H, d), 7.37 (1H, dd), 3.87 (2H, q), 1.43 (3H, t).
Compound (9): ¹ H-NMR (CDCl ₃ ) δ: 9.25 (1H, d), 8.84 (1H, d), 7.83 (1H, d), 7.79 (1H, d), 7.45 (1H, dd), 4.08 (2H, q), 1.47 (3H, t).

Formula (1-f)

A compound in which A and R ⁴ are represented by [Table 4].

Compound (12): ¹ H-NMR (CDCl ₃ ) δ: 9.03 (1H, dd), 8.60 (1H, dd), 7.91 (1H, d), 7.75 (1H, dd), 7.66 (1H, d), 7.39 (1H, dd), 4.00 (2H, q), 1.43 (3H, t).

Production Example 3 (1)
In place of 4-hydroxyphenyl = trifluoromethanesulfonate, 3-hydroxyphenyl = trifluoromethanesulfonate was used, and a compound represented by the following formula (hereinafter referred to as an intermediate) according to the method described in Production Example 1 (1) (Denoted as (3-1)).

¹ H-NMR (CDCl ₃ ) δ: 10.73 (1H, s), 8.25 (1H, d), 7.13 (1H, d), 6.95 (1H, dd).

Production Example 3 (2)
In place of intermediate (1-1), intermediate (3-1) was used, and a compound represented by the following formula (hereinafter referred to as intermediate (3-2) was prepared according to the method described in Production Example 1 (2). )).

¹ H-NMR (CDCl ₃ ) δ: 6.76-6.67 (3H, m), 5.26 (1H, br s), 3.76 (2H, br s).

Production Example 3 (3)
To a mixture of 25 g of 2-bromo-3-fluoropyridine, 6.25 g of sodium hydride (60% oily) and 100 mL of DMF, 10.5 mL of ethanethiol was added over 1 hour under ice-cooling, and the mixture was brought to room temperature. Stir overnight. The reaction mixture was poured into water and extracted with MTBE. The organic layer was dried over anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 21.3 g of a compound represented by the following formula (hereinafter referred to as intermediate (3-3)).

¹ H-NMR (CDCl ₃ ) δ: 8.13 (1H, dd), 7.46 (1H, dd), 7.23 (1H, dd), 2.96 (2H, q), 1.40 (3H, t).

Production Example 3 (4)
To a mixture of 1.75 g of intermediate (3-3), 10 mL of THF and 25 mL of diethyl ether, 5.7 mL of n-butyllithium (1.55M) was added at −78 ° C., and the mixture was stirred at −78 ° C. for 1 hour. To the reaction mixture was added DMF 0.41 mL at −78 ° C., and the mixture was stirred at −78 ° C. for 30 minutes, and then warmed to room temperature. Water was added to the reaction mixture and extracted with MTBE. The organic layer was dried over anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, so as to obtain 941 mg of a compound represented by the following formula (hereinafter, referred to as intermediate (3-4)).

¹ H-NMR (CDCl ₃ ) δ: 10.18 (1H, s), 8.53 (1H, dd), 7.75-7.67 (1H, m), 7.41 (1H, dd), 2.98 (2H, q), 1.43 (3H , t).

Production Example 3 (5)
A mixture of 550 mg of intermediate (3-2), 357 mg of intermediate (3-4) and 2.5 mL of xylene was stirred under reflux for 1 hour. 1 g of iodine was further added to the reaction mixture, and the mixture was stirred for 1 hour under reflux. A 10% aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 48 mg of a compound represented by the following formula (hereinafter referred to as compound (11)).

¹ H-NMR (CDCl ₃ ) δ: 8.59 (1H, dd), 7.97 (1H, d), 7.79 (1H, dd), 7.64 (1H, d), 7.43 (1H, dd), 7.35 (1H, dd ), 3.07 (2H, q), 1.47 (3H, t).

The compounds produced according to the method described in Production Example 3 (5) and their physical properties are shown below.
Formula (1-g)

In which A and R ⁴ are represented by [Table 5].

Compound (6): ¹ H-NMR (CDCl ₃ ) δ: 8.03 (1H, d), 7.80 (1H, d), 7.64 (1H, d), 7.52 (1H, d), 7.41 (1H, dd), 7.32 (1H, dd), 3.06 (2H, q), 1.47 (3H, t).

Production Example 4 (1)
A mixture of 500 mg of 3-ethylsulfanylpyridine-2-carboxylic acid, 0.5 mL of thionyl chloride, 1 drop of DMF and 5 mL of toluene was stirred at 100 ° C. for 2 hours and concentrated under reduced pressure. A mixture of the obtained residue and 6 mL of THF was added to a mixture of 380 mg of 2-amino-4-methoxyphenol and 6 mL of THF under ice-cooling, and the mixture was brought to room temperature and stirred at room temperature for 1 hour. Saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure. The obtained residue was washed with a mixed solution of n-hexane: ethyl acetate = 3: 1 to obtain 650 mg of a compound represented by the following formula (hereinafter referred to as intermediate (4-1)).

¹ H-NMR (CDCl ₃ ) δ: 10.31 (1H, s), 8.35 (1H, dd), 8.09 (1H, s), 7.73 (1H, dd), 7.43 (1H, dd), 6.98 (1H, d ), 6.87 (1H, d), 6.72 (1H, dd), 3.78 (3H, s), 2.95 (2H, q), 1.44 (3H, t).

Production Example 4 (2)
A mixture of 643 mg of the intermediate (4-1), 804 mg of paratoluenesulfonic acid monohydrate and 10 mL of xylene was stirred under reflux for 2 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, so as to obtain 261 mg of a compound represented by the following formula (hereinafter referred to as intermediate (4-2)).

¹ H-NMR (CDCl ₃ ) δ: 8.57 (1H, dd), 7.76 (1H, dd), 7.58-7.54 (1H, m), 7.41 (1H, d), 7.38 (1H, dd), 7.02 (1H , dd), 3.88 (3H, s), 3.05 (2H, q), 1.47 (3H, t).

Production Example 4 (3)
Using the intermediate (4-2) instead of the compound (2), a compound represented by the following formula (hereinafter referred to as the intermediate (4-3)) is obtained according to the method described in Production Example 2. It was.

¹ H-NMR (CDCl ₃ ) δ: 8.79-8.54 (2H, m), 7.87-7.53 (2H, m), 7.33-7.24 (1H, m), 7.12-7.02 (1H, m), 4.09 (2H, q), 3.90 (3H, s), 1.42 (3H, t)

Production Example 4 (4)
A mixture of 520 mg of intermediate (4-3), 1.04 mL of chlorotrimethylsilane, 1.23 g of sodium iodide and 20 mL of acetonitrile was stirred under reflux for 21 hours. A 10% aqueous sodium thiosulfate solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, so as to obtain 375 mg of a compound represented by the following formula (hereinafter referred to as intermediate (4-4)).

¹ H-NMR (CDCl ₃ ) δ: 9.01 (1H, dd), 8.59 (1H, dd), 7.70 (1H, dd), 7.52 (1H, d), 7.25 (1H, d), 6.97 (1H, dd ), 5.24 (1H, s), 4.06 (2H, q), 1.42 (3H, t).

Production Example 4 (5)
To a mixture of 195 mg of Intermediate (4-4), 73 μL of pyridine and 3.5 mL of chloroform, 140 μL of trifluoromethanesulfonic anhydride was added at room temperature, and the mixture was stirred at room temperature for 2 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 190 mg of a compound represented by the following formula (hereinafter referred to as compound (4)).

¹ H-NMR (CDCl ₃ ) δ: 9.03 (1H, dd), 8.60 (1H, dd), 7.80 (1H, d), 7.78-7.73 (2H, m), 7.41 (1H, dd), 4.01 (2H , q), 1.43 (3H, t).

The compounds produced according to the method described in Production Example 4 (5) and their physical properties are shown below.
Formula (1-h)

A compound in which A and R ⁴ are represented by [Table 6].

Compound (5): ¹ H-NMR (CDCl ₃ ) δ: 8.29-8.23 (1H, m), 7.99-7.93 (1H, m), 7.86-7.77 (2H, m), 7.75 (1H, d), 7.67 (1H, d), 7.36 (1H, dd), 3.81 (2H, q), 1.40 (3H, t).

Next, formulation examples are shown. In addition, a part represents a weight part.

Formulation Example 1
10 parts of any one of compounds 1 to 12 are dissolved in a mixture of 35 parts of xylene and 35 parts of DMF, and 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate are added and mixed. Each formulation is obtained.

Formulation Example 2
4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic silicon hydroxide fine powder and 54 parts of diatomaceous earth are added, and 20 parts of any one of compounds 1 to 12 are added and mixed to each water. Get a glaze.

Formulation Example 3
To 2 parts of any one of compounds 1 to 12, 1 part of a synthetic hydrous silicon oxide fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are added and mixed. Next, an appropriate amount of water is added to the mixture, and the mixture is further stirred, granulated by a granulator, and dried by ventilation to obtain each granule.

Formulation Example 4
1 part of any one of compounds 1 to 12 is dissolved in an appropriate amount of acetone, and 5 parts of a synthetic silicon hydroxide fine powder, 0.3 part of isopropyl acid phosphate and 93.7 parts of fusami clay are added to the resulting mixture and stirred sufficiently. Mix and evaporate off the acetone to obtain each powder.

Formulation Example 5
35 parts of a mixture of polyoxyethylene alkyl ether sulfate ammonium salt and white carbon (weight ratio 1: 1), 10 parts of any one of compounds 1 to 12, and 55 parts of water are mixed and finely divided by a wet grinding method. Each flowable agent is obtained by grinding.

Formulation Example 6
0.1 part of any one of compounds 1 to 12 is dissolved in a mixture of 5 parts of xylene and 5 parts of trichloroethane, and this is mixed with 89.9 parts of kerosene to obtain each oil.

Formulation Example 7
10 mg of any one of compounds 1 to 12 is dissolved in 0.5 mL of acetone, and this solution is added dropwise to 5 g of animal solid feed powder (bred breeding solid feed powder CE-2, Nippon Claire Co., Ltd.). Mix evenly. Then acetone is evaporated to dryness to obtain each poisonous bait.

Formulation Example 8
0.1 part of any one of compounds 1 to 12 and 49.9 parts of neothiozole (manufactured by Chuo Kasei Co., Ltd.) are placed in an aerosol can, and after mounting an aerosol valve, 25 parts of dimethyl ether and 25 parts of LPG are filled and shaken. Finally, an oil aerosol is obtained by mounting the actuator.

Formulation Example 9
0.6 part of any one of compounds 1 to 12, 0.01 part of BHT (2,6-di-tert-butyl-4-methylphenol), 5 parts of xylene, 3.39 parts of kerosene and an emulsifier {Rheidol MO -60 (manufactured by Kao Corporation)} 1 part mixed and 50 parts distilled water are filled into an aerosol container, and after the valve is mounted, 40 parts of propellant (LPG) is pressure filled through the valve. To obtain an aqueous aerosol.

Formulation Example 10
0.1 g of any one of compounds 1 to 12 is mixed with 2 mL of propylene glycol and impregnated into a porous ceramic plate of 4.0 × 4.0 cm and a thickness of 1.2 cm to obtain a heating smoke. .

Formulation Example 11
5 parts of any one of compounds 1 to 12 and 95 parts of ethylene-methyl methacrylate copolymer (ratio of methyl methacrylate in the copolymer: 10% by weight, ACRIFT (registered trademark) WD301, manufactured by Sumitomo Chemical Co., Ltd.) The mixture is melt-kneaded with a closed pressure kneader (manufactured by Moriyama Seisakusho), and the resulting kneaded product is extruded from an extruder through a molding die to obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm.

Formulation Example 12
5 parts of any one of compounds 1 to 12 and 95 parts of a soft vinyl chloride resin are melt-kneaded with a closed pressure kneader (manufactured by Moriyama Seisakusho), and the resulting kneaded product is extruded from an extrusion molding machine through a molding die. A rod-shaped molded body having a length of 15 cm and a diameter of 3 mm is obtained.

Formulation Example 13
Any one of Compounds 1-12 100 mg, lactose 68.75 mg, corn starch 237.5 mg, microcrystalline cellulose 43.75 mg, polyvinylpyrrolidone 18.75 mg, sodium carboxymethyl starch 28.75 mg, and magnesium stearate 5 mg is mixed and the resulting mixture is compressed to an appropriate size to obtain tablets.

Formulation Example 14
Any one of compounds 1 to 12 25 mg, lactose 60 mg, corn starch 25 mg, carmellose calcium 6 mg, and 5% hydroxypropylmethylcellulose are mixed in an appropriate amount, and the resulting mixture is filled into a hard shell gelatin capsule or hydroxypropylmethylcellulose capsule And a capsule is obtained.

Formulation Example 15
Any one of Compounds 1-12 100 mg, fumaric acid 500 mg, sodium chloride 2000 mg, methylparaben 150 mg, propylparaben 50 mg, granule sugar 25000 mg, sorbitol (70% solution) 13000 mg, VeegumK (VanderbiltCo.) 100 mg, flavor 35 mg, and coloring Distilled water is added to 500 mg of the preparation so that the final volume becomes 100 mL, and mixed to obtain a suspension for oral administration.

Formulation Example 16
5% by weight of any one of compounds 1 to 12 is dissolved in 5% by weight of polysorbate 85, 3% by weight of benzyl alcohol, and 30% by weight of propylene glycol, and the pH of this solution becomes 6.0 to 6.5. Thus, after adding a phosphate buffer solution, water is added as the remainder, and the liquid agent for oral administration is obtained.

Formulation Example 17
5% by weight of aluminum distearate in 57% by weight of fractionated coconut oil and 3% by weight of polysorbate 85 is added and dispersed by heating. This is cooled to room temperature and 25% by weight of saccharin is dispersed in the oily vehicle. To this, 10% by weight of any one of compounds 1 to 12 is allocated to obtain a paste preparation for oral administration.

Formulation Example 18
5% by weight of any one of compounds 1 to 12 is mixed with 95% by weight of limestone powder, and granules for oral administration are obtained using a wet granulation method.

Formulation Example 19
5 parts of any one of compounds 1 to 12 are dissolved in 80 parts of diethylene glycol monoethyl ether, and 15 parts of propylene carbonate are mixed with this to obtain a spot-on solution.

Formulation Example 20
10 parts of any one of compounds 1 to 12 are dissolved in 70 parts of diethylene glycol monoethyl ether, and 20 parts of 2-octyldodecanol is mixed with it to obtain a pour-on solution.

Formulation Example 21
To 0.5 parts of any one of compounds 1 to 12, 60 parts of Nikkor (registered trademark) TEALS-42 (42% aqueous solution of Nikko Chemicals lauryl sulfate triethanolamine) and 20 parts of propylene glycol were added to form a homogeneous solution. Then, 19.5 parts of water is added and further stirred and mixed to obtain a uniform solution shampoo agent.

Formulation Example 22
Any one of compounds 1 to 12 0.15% by weight, animal feed 95% by weight, and 4.85% by weight of a mixture composed of dicalcium phosphate, diatomaceous earth, Aerosil, and carbonate (or chalk) are sufficiently stirred and mixed. Obtain a premix for animal feed.

Formulation Example 23
7.2 g of any one of compounds 1 to 12 and 92.8 g of Fosco (registered trademark) S-55 (manufactured by Maruishi Pharmaceutical Co., Ltd.) are dissolved and mixed at 100 ° C., poured into a suppository, and solidified by cooling. To obtain a suppository.

Next, the harmful arthropod controlling efficacy of the compound of the present invention is shown by test examples.

Test example 1
The preparation of Compound 1, 3, 4, 5, 7, 9, 10 or 12 obtained in Formulation Example 5 was diluted with water so that the concentration of each compound was 500 ppm to obtain a diluted solution.
On the other hand, about 30 Aphis gossypi (all stages) were inoculated into cucumber seedlings (first true leaf development stage) planted in plastic cups, and left for 1 day. Scattered.
Six days after spraying, the number of live cotton aphids that parasitized on the leaves of the cucumber was examined, and the control value was determined by the following formula.
Control value (%) = {1− (Cb × Tai) / (Cai × Tb)} × 100
In addition, the character in a formula represents the following meaning.
Cb: number of insects before treatment in the untreated group Cai: number of live parasites when observed in the untreated group Tb: number of insects before treatment in the treated group Tai: number of live parasitic insects during observation of the treated group The group refers to a group in which a preparation diluted with the same amount of water as the treatment group was sprayed on the preparation not containing the compound of the present invention in Preparation Example 5.
As a result, the control value of 90% or more was exhibited in all the treatment sections where the compounds of the present invention were tested.

Test example 2
The preparation of Compound 4 or 5 obtained in Preparation Example 5 was diluted with water so that the concentration of each compound was 500 ppm to obtain a diluted solution.
10 mL of the diluted solution was sprayed on rice seedlings in the second leaf development stage planted in a polyethylene cup. After air drying, 20 3-4 instar larvae of the green planthopper (Nilaparvata lugens) were released and stored in a greenhouse at 25 ° C. Six days later, the number of brown planthopper infested with rice was investigated, and the control value was determined by the following formula.
Control value (%) = {1− (Cb × Tai) / (Cai × Tb)} × 100
In addition, the character in a formula represents the following meaning.
Cb: number of insects before treatment in the untreated group Cai: number of insects at the time of observation in the untreated group Tb: number of insects before the treatment in the treated group Tai: number of insects at the time of observation in the treated group In Formulation Example 5, this refers to a group in which a preparation containing no compound of the present invention was sprayed with a solution diluted with the same amount of water as the treatment group.
As a result, the control value of 90% or more was exhibited in all the treatment sections where the compounds of the present invention were tested.

Test example 3
The formulation of Compound 4 obtained in Formulation Example 5 was diluted with water so that the concentration of Compound 4 was 200 ppm to obtain a diluted solution.
On the other hand, 5 mL of the diluted solution was irrigated to rice seedlings planted in plastic cups (2 weeks after sowing, the second leaf development stage) and kept in a 25 ° C. greenhouse for 7 days. After releasing 20 3-4 instar larvae of the green planthopper (Nilaparvata lugens) and keeping it in the greenhouse for another 6 days, the number of surviving insects parasitic on the rice leaves was investigated, and the control value was calculated by the following formula: Asked.
Control value (%) = {1− (Cb × Tai) / (Cai × Tb)} × 100
In addition, the character in a formula represents the following meaning.
Cb: number of insects before treatment in the untreated group Cai: number of live parasites when observed in the untreated group Tb: number of insects before treatment in the treated group Tai: number of live parasitic insects during observation of the treated group The group refers to a group in which a preparation diluted with the same amount of water as the treatment group was sprayed on the preparation not containing the compound of the present invention in Preparation Example 5.
As a result, the treatment section in which Compound 4 was tested showed a control value of 100%.

Test example 4
The preparation of Compound 1, 3, 4, 5, 7, 9, 10 or 12 obtained in Formulation Example 5 was diluted with water so that the concentration of each compound was 500 ppm to obtain a diluted solution.
On the other hand, the diluted solution was sprayed at a rate of 20 mL / cup on a three-leaf cabbage planted in a polyethylene cup. After spraying, the plants were air-dried, the stems and leaves were cut out and accommodated in a 50 mL cup, 5 larvae of Plutella xylostella were released and covered. After storing at 25 ° C., the number of dead insects was counted after 5 days, and the death rate was calculated from the following formula.
Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the death rate was 80% or more in all the treatment areas where the compounds of the present invention were tested.

Test Example 5
The formulation of Compound 4 obtained in Formulation Example 5 was diluted with water so that the concentration of the compound was 500 ppm to obtain a diluted solution.
A filter paper of the same size was laid on the bottom of a polyethylene cup having a diameter of 5.5 cm, and 0.7 mL of the diluted solution was dropped onto the filter paper, and 30 mg of sucrose was uniformly added as food. Ten female fly (Musca domestica) females were released into the polyethylene cup and capped. After 24 hours, the life and death of the house fly was investigated, the number of dead insects was counted, and the death rate was calculated by the following formula.
Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the treatment group in which Compound 4 was tested showed a death rate of 100%.

Test Example 6
The preparation of Compound 3 or 9 obtained in Formulation Example 5 was diluted with water so that the concentration of each compound was 500 ppm to obtain a diluted solution.
A filter paper of the same size was laid on the bottom of a polyethylene cup having a diameter of 5.5 cm, and 0.7 mL of the diluted solution was dropped onto the filter paper, and 30 mg of sucrose was uniformly added as food. Two adult male cockroaches (Blatella germanica) were released into the polyethylene cup and capped. Six days later, the death and death of German cockroaches were investigated, the number of dead insects was counted, and the death rate was calculated according to the following formula.
Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the death rate was 100% in all treatments where the compounds of the present invention were tested.

Test Example 7
The preparation of Compound 1, 4, 5, 7, 9, or 10 obtained in Formulation Example 5 was diluted with water so that the concentration of each compound was 500 ppm to obtain a diluted solution.
0.7 ml of the diluted solution was added to 100 mL of ion exchange water (concentration: 3.5 ppm). 30 larvae of Culex pipiens parallels were released into the liquid, and after 1 day, the viability was investigated and the number of dead insects was counted to determine the death rate.
Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the mortality rate was 91% or more in all the treatment groups where the compounds of the present invention were tested.

Test Example 8
The preparation of Compound 1, 3, 4, 5, 7, 9, 10 or 12 obtained in Formulation Example 1 was diluted with water so that the concentration of each compound was 500 ppm to obtain a diluted solution.
On the other hand, the diluted solution was sprayed at a rate of 30 mL / cup on the trilobal cucumber planted in a polyethylene cup. After spraying, the plants were air-dried, the second leaf was cut out and placed in a 200 mL cup, 10 larvae of Auricophora femorialis were released and capped. After storing at 25 ° C., the number of dead insects was counted after 5 days, and the death rate was calculated by the following formula.
Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the death rate was 80% or more in all the treatment areas where the compounds of the present invention were tested.

The compound of the present invention has a controlling effect on harmful arthropods and is useful as an active ingredient of a harmful arthropod controlling agent.

Claims (8)

1. Formula (I)
   

   

   [Where:
   A represents a nitrogen atom or CR ⁵ ,
   One of R ^A and R ^B represents —OSO ₂ CF ₃ , the other represents a hydrogen atom,
   R ¹ represents a C1-C4 alkyl group, a cyclopropyl group or a cyclopropylmethyl group,
   R ² and R ³ each independently represent a hydrogen atom or a halogen atom,
   R ⁴ and R ⁵ each independently represents a hydrogen atom, —S (O) _m R ⁶ {m represents 0, 1, or 2. } C3-C6 cycloalkyl group optionally having one or more halogen atoms, (C1-C6 alkoxy) optionally having one or more halogen atoms, C1-C6 alkyl group having one or more halogen atoms (C3-C6 cycloalkyl) C1-C6 alkyl group, —R ⁷ , —OR ⁷ , —NR ⁸ R ⁹ , —C (O) R ¹⁰ , —COOR ¹⁰ , —C (O) NR ⁸ R ⁹ , a phenyl group, a 5- to 6-membered heteroaryl group (provided that the phenyl group and the 5- to 6-membered heteroaryl group may have one or more atoms or substituents selected from group X; When it has two or more atoms or substituents, these atoms and substituents may be the same or different. }, Nitro group, cyano group, hydroxy group, sulfanyl group, halogen atom, —NR ¹⁰ C (O) R ⁶ , —NR ¹⁰ CO ₂ R ⁶ , —NR ¹⁰ SO ₂ R ⁶ , —NR ¹⁰ (OR ⁶ ) Or —N═S (O) _p R ⁶ R ¹¹ {p represents 0 or 1; },
   R ⁶ and R ¹¹ each independently represents a C1-C6 alkyl group which may have one or more halogen atoms,
   R ⁷ represents a C1-C6 chain hydrocarbon group which may have one or more halogen atoms,
   R ⁸ and R ⁹ each independently represents a hydrogen atom or a C1-C6 chain hydrocarbon group which may have one or more halogen atoms, or R ⁸ and R ⁹ are bonded to each other, Represents a C2-C6 alkanediyl group optionally having the above halogen atom,
   n represents 0, 1, or 2;
   Group X is a group consisting of —R ⁶ , —OR ⁶ , —S (O) _m R ⁶ , —C (O) R ⁶ , —COOR ⁶ , —NR ¹⁰ R ¹² , a cyano group, a nitro group, and a halogen atom. Represents
   R ¹⁰ and R ¹² each independently represents a hydrogen atom or a C1-C6 alkyl group which may have one or more halogen atoms. ]
   A benzoxazole compound represented by:
2. R ¹ is a C1-C3 alkyl group,
   R ⁴ and R ⁵ each independently represents one or more selected from a hydrogen atom, —R ⁶ , —S (O) _m R ⁶ , —OR ⁶ , —NR ⁸ R ⁹ , —COOR ⁶ , group X An optionally substituted 5- to 6-membered heteroaryl group, a halogen atom, —NR ¹⁰ C (O) R ⁶ , —NR ¹⁰ CO ₂ R ⁶ , —NR ¹⁰ (OR ⁶ ), or —N The benzoxazole compound according to claim 1, which is = S (O) _p R ⁶ R ¹¹ .
3. The benzoxazole compound according to claim 1 or 2, wherein R ^A is -OSO ₂ CF ₃ and R ^B is a hydrogen atom.
4. R ¹ is an ethyl group,
   R ² and R ³ are both hydrogen atoms,
   R ⁴ is a hydrogen atom, a halogen atom, a C1-C3 alkyl group that may have one or more halogen atoms, or a C1-C3 alkoxy group that may have one or more halogen atoms,
   The benzoxazole compound according to claim 3, wherein R ⁵ is a hydrogen atom or a halogen atom.
5. The benzoxazole compound according to any one of claims 1 to 4, wherein A is a nitrogen atom.
6. The benzoxazole compound according to any one of claims 1 to 4, wherein A is CR ⁵ .
7. A harmful arthropod control agent comprising the benzoxazole compound according to any one of claims 1 to 6 and an inert carrier.
8. A method for controlling harmful arthropods, which comprises applying an effective amount of the benzoxazole compound according to any one of claims 1 to 6 to harmful arthropods or their habitats.