WO2016143650A1

WO2016143650A1 - 3-aminooxalylaminobenzamide compound and use for controlling harmful arthropod

Info

Publication number: WO2016143650A1
Application number: PCT/JP2016/056540
Authority: WO
Inventors: 政樹 ▲高▼橋
Original assignee: 住友化学株式会社
Priority date: 2015-03-06
Filing date: 2016-03-03
Publication date: 2016-09-15

Abstract

Provided is a compound that exhibits an excellent controlling effect against harmful arthropods. A 3-aminooxalylaminobenzamide compound represented by formula (1) has an excellent controlling effect against harmful arthropods.

Description

3-Aminooxalylaminobenzamide compounds and their use for controlling harmful arthropods

The present invention relates to certain 3-aminooxalylaminobenzamide compounds and their use for harmful arthropods.

So far, various compounds have been studied and put to practical use for the purpose of controlling harmful arthropods.

Also, certain compounds (for example, see Patent Document 1) are known.

Patent Document 1: International Publication No. 2012/164698

An object of the present invention is to provide a compound having an excellent controlling effect on harmful arthropods and a method for controlling harmful arthropods using the compound.

[1] Formula (1)

[Where:
G ¹ and G ⁵ each independently represent —CR ⁶ R ⁷ — or —C (O) —,
G ² , G ³ and G ⁴ each independently represent —CR ⁶ R ⁷ — or a single bond,
Q represents an oxygen atom, NR ⁸ , NC (O) R ⁹ or unsubstituted,
R ¹ and R ³ are each independently a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a —S (O) _p- (C1-C6 alkyl) group, a C1-C6 haloalkyl group, a C1-C6 A haloalkoxy group, a —S (O) _p — (C1-C6 haloalkyl) group, a halogen atom, a nitro group or a cyano group;
R ² represents a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group or a —S (O) _p — (C1-C6 haloalkyl) group,
R ⁴ and R ⁵ are each independently a hydrogen atom, a C1-C6 alkyl group, a (C1-C4 alkoxy) C1-C4 alkyl group, a (C1-C6 alkyl) carbonyl group, a (C1-C4 alkoxy) carbonyl group, C1 A —C6 haloalkyl group, a (C1-C6 haloalkyl) carbonyl group or a (C1-C4 haloalkoxy) carbonyl group,
R ⁶ and R ⁷ are each independently a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a —S (O) _p- (C1-C6 alkyl) group, a C1-C6 haloalkyl group, a C1-C6 halo. Represents an alkoxy group, —S (O) _p — (C1-C6 haloalkyl) group, halogen atom or cyano group,
R ⁸ represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group or a cyano group,
R ⁹ represents a C1-C6 alkyl group or a C1-C6 haloalkyl group,
Each X ^a independently represents a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group, a halogen atom or a cyano group;
Each ^Xb independently represents a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group, a halogen atom or a cyano group;
k represents 0 or 1,
m represents an integer of 0 to 4,
n represents an integer of 0 to 2,
p represents an integer of 0-2. ]
A 3-aminooxalylaminobenzamide compound represented by the following (hereinafter also referred to as the present compound).
[2] R ¹ and R ³ are each independently a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a —S (O) _p — (C1-C6 alkyl) group, a C1-C6 haloalkyl group, A C1-C6 haloalkoxy group, —S (O) _p — (C1-C6 haloalkyl) group or a halogen atom,
R ⁴ and R ⁵ are each independently a hydrogen atom, a C1-C6 alkyl group, a (C1-C6 alkyl) carbonyl group, a C1-C6 haloalkyl group or a (C1-C6 haloalkyl) carbonyl group,
R ⁶ and R ⁷ are each independently a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a halogen atom or a cyano group,
Each X ^a is independently a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group or a halogen atom;
[1] The compound according to [1], wherein each X ^b is independently a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group or a halogen atom. [3] G ¹ and G ⁵ are each independently —CR ⁶ R ⁷ —,
R ¹ and R ³ are each independently a hydrogen atom, a C1-C3 alkyl group, a C1-C3 alkoxy group, a —S (O) _p — (C1-C3 alkyl) group, a C1-C3 haloalkyl group, a C1-C3 A haloalkoxy group, a —S (O) _p — (C1-C3 haloalkyl) group or a halogen atom,
R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C3 alkyl group,
R ⁶ and R ⁷ are each independently a hydrogen atom, a C1-C3 alkyl group or a C1-C3 haloalkyl group,
R ⁸ is a hydrogen atom, a methyl group, an ethyl group or a cyano group,
R ⁹ is a methyl group, an ethyl group or a trifluoromethyl group,
Each X ^a is independently a C1-C3 alkyl group, a C1-C3 alkoxy group, a C1-C3 haloalkyl group, a C1-C3 haloalkoxy group or a halogen atom;
The compound according to [1] or [2], wherein X ^b is each independently a C1-C3 alkyl group, a C1-C3 alkoxy group, a C1-C3 haloalkyl group, a C1-C3 haloalkoxy group or a halogen atom.
[4] The compound according to any one of [1] to [3], wherein at least one of G ² , G ³ and G ⁴ is —CR ⁶ R ⁷ —.
[5] Either ^one of R ¹ and R ³ is a bromine atom, an iodine atom or a C1-C3 alkyl group, and the other is a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 haloalkoxy group, Or the compound according to any one of [1] to [4], which is a —S (O) _p — (C1-C3 haloalkyl) group.
[6] The compound according to any one of [1] to [5], wherein R ² is a C1-C6 haloalkyl group.
[7] The compound according to any one of [1] to [5], wherein R ² is a C1-C6 haloalkoxy group.
[8] The compound according to any one of [1] to [5], wherein R ² is a —S (O) _p — (C1-C6 haloalkyl) group.
[9] A harmful arthropod control composition comprising the compound according to any one of [1] to [8] and an inert carrier.
[10] A method for controlling harmful arthropods, which comprises applying an effective amount of the compound according to any one of [1] to [8] to harmful arthropods or harmful arthropod habitats.

Since the compound of the present invention has an excellent control activity against harmful arthropods, it is useful as an active ingredient of a harmful arthropod control agent.

Examples of groups used in the description of the present specification will be described below.

In the present invention, “C1-C6 alkyl group” includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and tert-butyl group. The “C1-C6 alkyl group” includes a “C1-C4 alkyl group” and further a “C1-C3 alkyl group”.

In the present invention, examples of the “C1-C6 alkoxy group” include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. The “C1-C6 alkoxy group” includes a “C1-C4 alkoxy group” and further a “C1-C3 alkoxy group”.

In the present invention, the “—S (O) _p — (C1-C6 alkyl) group” is a group in which the “C1-C6 alkyl group” is bonded to the sulfur atom of S (O) _p , for example, a methylsulfanyl group. Methanesulfinyl group, methanesulfonyl group, ethylsulfanyl group, ethanesulfinyl group, and ethanesulfonyl group.

In the present invention, the “C1-C6 haloalkyl group” is a group in which one or more hydrogen atoms of the “C1-C6 alkyl group” are substituted with a halogen atom, such as a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group. Group, chlorodifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, heptafluoroisopropyl group, 1,1,2,2,3,3-hexafluoropropyl group, Examples include 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group and trichloromethyl group.

In the present invention, the “C1-C6 haloalkoxy group” is a group in which one or more hydrogen atoms of the “C1-C6 alkoxy group” are substituted with a halogen atom, such as a fluoromethoxy group, a difluoromethoxy group, a trifluoro group. Methoxy group, chlorodifluoromethoxy group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group, heptafluoropropoxy group, heptafluoroisopropoxy group, 1,1,2,2,3,3-hexafluoropropoxy group And the groups 2,2,2-trifluoro-1- (trifluoromethyl) ethoxy and trichloromethoxy.

In the present invention, the “—S (O) _p — (C1-C6 haloalkyl) group” is a group in which the “C1-C6 haloalkyl group” is bonded to the sulfur atom of S (O) _p. Methyl) sulfanyl group, (trifluoromethane) sulfinyl group, (trifluoromethane) sulfonyl group, (pentafluoroethyl) sulfanyl group, (pentafluoroethane) sulfinyl group, (pentafluoroethane) sulfonyl group, (heptafluoroisopropyl) sulfanyl group , (Heptafluoroisopropane) sulfinyl group and (heptafluoroisopropane) sulfonyl group.

In the present invention, “Q represents no substitution” means that Q does not exist.

In the present invention, “halogen atom” represents a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The compound of the present invention may contain one or more asymmetric carbon atoms or asymmetric centers in its structural formula, and there may be two or more optical isomers. All of the optical isomers and a mixture containing them in an arbitrary ratio are also contained. The compound of the present invention may contain two or more geometric isomers derived from a carbon-carbon double bond, sulfur-nitrogen double bond, or cyclic structure in the structure. It also contains all geometric isomers and mixtures containing them in any proportion.

Examples of the compound of the present invention include the following compounds.

In the compounds of the present invention, a compound wherein G ¹ is —CR ⁶ R ⁷ —;
In the compounds of the present invention, G ¹ is —CR ⁶ R ⁷ —, and R ⁶ and R ⁷ are each independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group;
In the compounds of the present invention, a compound wherein G ¹ is —CH ₂ —;
In the compounds of the present invention, a compound wherein G ¹ is —CH (CH ₃ ) —;

In the compounds of the present invention, a compound wherein G ² is —CR ⁶ R ⁷ —;
In the compounds of the present invention, G ² is —CR ⁶ R ⁷ —, and R ⁶ and R ⁷ are each independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group;
In the compounds of the present invention, a compound wherein G ² is —CH ₂ —;
In the compounds of the present invention, a compound wherein G ² is —CH (CH ₃ ) —;
In the compounds of the present invention, a compound in which G ² is a single bond;

In the compounds of the present invention, a compound wherein G ³ is —CR ⁶ R ⁷ —;
In the compounds of the present invention, G ³ is —CR ⁶ R ⁷ —, and R ⁶ and R ⁷ are each independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group;
In the compounds of the present invention, a compound wherein G ³ is —CH ₂ —;
In the compounds of the present invention, a compound wherein G ³ is —CH (CH ₃ ) —;
In the compounds of the present invention, a compound in which G ³ is a single bond;

In the compounds of the present invention, a compound wherein G ⁴ is —CR ⁶ R ⁷ —;
In the compounds of the present invention, G ⁴ is —CR ⁶ R ⁷ —, and R ⁶ and R ⁷ are each independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group;
In the compounds of the present invention, a compound wherein G ⁴ is —CH ₂ —;
In the compounds of the present invention, a compound wherein G ⁴ is —CH (CH ₃ ) —;
In the compounds of the present invention, a compound in which G ⁴ is a single bond;

In the compound of the present invention, a compound in which at least one of G ² , G ³ and G ⁴ is —CR ⁶ R ⁷ —;
In the compound of the present invention, one of G ² , G ³ and G ⁴ is —CR ⁶ R ⁷ —, and the remaining two are single bonds;
In the compounds of the present invention, ^two of G ² , G ³ and G ⁴ are each independently —CR ⁶ R ⁷ —, and the remaining one is a single bond;
A compound of the present invention, wherein G ² , G ³ and G ⁴ are each independently —CR ⁶ R ⁷ —;

In the compound of the present invention, G ¹ and G ⁵ each independently represent —CHR ⁶ —,
G ² , G ³ and G ⁴ each independently represent —CHR ⁶ — or a single bond, and at least one of G ² , G ³ and G ⁴ is —CHR ⁶ —;
A compound in which each R ⁶ is independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group;
In the compound of the present invention, G ¹ , G ² and G ⁵ are —CHR ⁶ —,
G ³ and G ⁴ are each independently —CHR ⁶ — or a single bond,
R ⁶ is independently a hydrogen atom or a C1-C6 alkyl group;

In the compounds of the present invention, a compound wherein G ⁵ is —CR ⁶ R ⁷ —;
In the compounds of the present invention, G ⁵ is —CR ⁶ R ⁷ —, and R ⁶ and R ⁷ are each independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group;
In the compounds of the present invention, a compound wherein G ⁵ is —CH ₂ —;
In the compounds of the present invention, a compound wherein G ⁵ is —CH (CH ₃ ) —;

In the compounds of the present invention, a compound in which Q is an oxygen atom;
In the compounds of the present invention, Q is NR ⁸ and R ⁸ is a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group or a cyano group;
In the compounds of the present invention, Q is NR ⁸ and R ⁸ is a hydrogen atom, a C1-C6 alkyl group, or a cyano group;
In the compounds of the present invention, a compound wherein Q is NH;
In the compounds of the present invention, a compound wherein Q is NCN;
In the compounds of the present invention, Q is NC (O) R ⁹ and R ⁹ is a C1-C6 alkyl group or a C1-C6 haloalkyl group;
In the compounds of the present invention, a compound in which Q is NC (O) CH ₃ or NC (O) CF ₃ ;
In the compounds of the present invention, a compound in which Q is unsubstituted;

In the compounds of the present invention, a compound wherein R ¹ is a hydrogen atom;
In the compounds of the present invention, a compound wherein R ¹ is a C1-C6 alkyl group;
In the compounds of the present invention, a compound wherein R ¹ is a C1-C6 haloalkyl group;
In the compound of the present invention, R ¹ is a C1-C6 haloalkoxy group, —S— (C1-C6 haloalkyl) group, —S (O) — (C1-C6 haloalkyl) group, or —S (O) ₂ — ( A compound which is a C1-C6 haloalkyl) group;
In the compounds of the present invention, a compound wherein R ¹ is a halogen atom;
In the compounds of the present invention, a compound wherein R ¹ is a methyl group, an ethyl group, a propyl group, or an isopropyl group;
In the compounds of the present invention, a compound wherein R ¹ is a difluoromethoxy group, a trifluoromethoxy group, a trifluoromethyl group, or a trifluoromethylthio group;
In the compounds of the present invention, a compound wherein R ¹ is a bromine atom or an iodine atom;

In the compounds of the present invention, a compound wherein R ² is a C1-C6 haloalkyl group;
In the compounds of the present invention, a compound wherein R ² is a C1-C6 haloalkoxy group;
In the compounds of the present invention, a compound wherein R ² is a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, or a heptafluoroisopropyl group;
In the compound of the present invention, a compound wherein R ² is a trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoropropoxy group, or a heptafluoroisopropoxy group;

In the compounds of the present invention, a compound wherein R ³ is a hydrogen atom;
In the compounds of the present invention, a compound wherein R ³ is a C1-C6 alkyl group;
In the compounds of the present invention, a compound wherein R ³ is a C1-C6 haloalkyl group;
In the compounds of the present invention, a compound wherein R ³ is a C1-C6 haloalkoxy group;
In the compounds of the present invention, a compound wherein R ³ is a —S— (C1-C6 haloalkyl) group;
In the compounds of the present invention, a compound wherein R ³ is a —S (O) — (C1-C6 haloalkyl) group;
In the compounds of the present invention, a compound wherein R ³ is a —S (O) ₂ — (C1-C6 haloalkyl) group;
In the compounds of the present invention, a compound wherein R ³ is a halogen atom;
In the compounds of the present invention, a compound wherein R ³ is a methyl group, an ethyl group, a propyl group, or an isopropyl group;
In the compound of the present invention, a compound wherein R ³ is a difluoromethoxy group, a trifluoromethoxy group, a trifluoromethyl group, or a trifluoromethylthio group;
In the compounds of the present invention, a compound wherein R ³ is a bromine atom or an iodine atom;

In the compound of the present invention, either one of R ^{1 and} R ³ is a halogen atom or a C1-C6 alkyl group, and the other is a C1-C6 alkyl group, a C1-C6 alkoxy group, —S (O) _p — ( A compound that is a C1-C6 alkyl) group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group, or a —S (O) _p — (C1-C6 haloalkyl) group;
In the compound of the present invention, either R ¹ or R ³ is a bromine atom, an iodine atom or a C1-C3 alkyl group, and the other is a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 haloalkoxy group. Or a compound which is a —S (O) _p — (C1-C3 haloalkyl) group;

In the compounds of the present invention, a compound wherein R ⁴ is a hydrogen atom;
In the compounds of the present invention, a compound wherein R ⁵ is a hydrogen atom;

In the compounds of the present invention, compounds wherein X ^a is each independently a C1-C6 alkyl group or a C1-C6 haloalkyl group, and m is an integer of 0-4;
In the compounds of the present invention, compounds wherein X ^a is each independently a C1-C6 alkoxy group or a C1-C6 haloalkoxy group, and m is an integer of 0-4;
In the compounds of the present invention, X ^a is independently a halogen atom, and m is an integer of 0 to 4;

In the compounds of the present invention, a compound in which n is 0;
In the compounds of the present invention, a compound in which n is 0 and m is 0 or 1;
In the compounds of the present invention, a compound in which X ^a is a C1-C3 alkyl group, a C1-C3 alkoxy group, or a halogen atom, n is 0, and m is 0 or 1;
In the compound of the present invention, X ^a is a C1-C3 alkyl group, a C1-C3 alkoxy group, or a halogen atom, n is 0, m is 0 or 1,
Compounds wherein R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C6 alkyl group;
In the compound of the present invention, X ^a is a C1-C3 alkyl group, a C1-C3 alkoxy group, or a halogen atom, n is 0, m is 0 or 1,
R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C6 alkyl group,
R ¹ is a hydrogen atom, a C1-C6 alkyl group or a halogen atom,
A compound wherein R ³ is a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group, or a —S (O) _p — (C1-C6 haloalkyl) group;
In the compound of the present invention, X ^a is a C1-C3 alkyl group, a C1-C3 alkoxy group, or a halogen atom, n is 0, m is 0 or 1,
R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C6 alkyl group,
R ¹ is a hydrogen atom, a C1-C6 alkyl group or a halogen atom,
A compound in which R ³ is a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a C1-C6 haloalkoxy group;

In the compound of the present invention, G ¹ , G ² and G ⁵ are —CR ⁶ R ⁷ —,
G ³ and G ⁴ are each independently —CR ⁶ R ⁷ — or a single bond,
Q is absent or is an oxygen atom, NR ⁸ , or NC (O) R ⁹ ;
R ⁶ and R ⁷ are each independently a hydrogen atom, a C1-C6 alkyl group or a C1-C6 haloalkyl group,
R ¹ is a hydrogen atom, a C1-C6 alkyl group or a halogen atom,
R ³ is a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group, or a —S (O) _p — (C1-C6 haloalkyl) group,
R ⁴ and R ⁵ are each independently a hydrogen atom, a C1-C6 alkyl group or a (C1-C6 alkyl) carbonyl group,
R ⁸ is a hydrogen atom or a cyano group,
R ⁹ is a C1-C6 haloalkyl group,
A compound in which X ^a is a C1-C3 alkyl group, a C1-C3 alkoxy group, or a halogen atom, n is 0, and m is 0 or 1;

In the compound of the present invention, G ¹ , G ² and G ⁵ are —CHR ⁶ —,
G ³ and G ⁴ are each independently —CHR ⁶ — or a single bond,
Q is absent or is an oxygen atom, NR ⁸ , or NC (O) R ⁹ ;
Each R ⁶ is independently a hydrogen atom or a C1-C6 alkyl group;
R ¹ is a hydrogen atom, a C1-C6 alkyl group or a halogen atom,
R ² is a C1-C6 haloalkyl group or a C1-C6 haloalkoxy group,
R ³ is a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group, or a C1-C6 haloalkylsulfanyl group,
R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-C6 alkyl group,
R ⁸ is a cyano group,
R ⁹ is a C1-C6 haloalkyl group,
X ^a is a C1-C3 alkyl group, a C1-C3 alkoxy group, or a halogen atom,
a compound wherein n is 0 and m is 0 or 1;

A compound of the present invention in which k is 0;
In the compounds of the present invention, a compound wherein k is 1.

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 following production methods 1 to 10.

Manufacturing method 1
The compound of the present invention can be produced according to the following method.

[Wherein Z represents a C1-C4 alkyl group, and other symbols have the same meaning as in formula (1). ]
First, it describes about the method of manufacturing the compound (henceforth a compound (M2)) represented by a formula (M2) from the compound (henceforth a compound (M1)) represented by a formula (M1). .

Compound (M2) can be produced by reacting compound (M1) with a compound represented by formula (R1) (hereinafter referred to as compound (R1)) in the presence of a base. Compound (M1) can be produced according to the method described in International Publication No. 2005/073165. Compound (R1) is a commercially available compound.

The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform (hereinafter referred to as aliphatic halogenated hydrocarbons); nitriles such as acetonitrile (hereinafter referred to as nitriles). Ethers such as tetrahydrofuran (hereinafter referred to as THF), ethylene glycol dimethyl ether, methyl tert-butyl ether (hereinafter referred to as MTBE), 1,4-dioxane (hereinafter referred to as ethers); acetone, ethyl Ketones such as methyl ketone and isobutyl methyl ketone (hereinafter referred to as ketones); esters such as methyl acetate and ethyl acetate (hereinafter referred to as esters); aromatic hydrocarbons such as toluene and xylene ( Hereinafter referred to as aromatic hydrocarbons); dimethylformamide (hereinafter referred to as DMF) Be), N- methylpyrrolidone, aprotic polar solvents such as dimethyl sulfoxide (hereinafter, referred to as aprotic polar solvent);.. And mixtures thereof.

Examples of the base used in the reaction include organic bases such as triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene (hereinafter referred to as organic bases); Alkali metal carbonates such as sodium and potassium carbonate (hereinafter referred to as alkali metal carbonates); alkaline earth metal carbonates such as calcium carbonate (hereinafter referred to as alkaline earth metal carbonates); sodium hydrogen carbonate and the like Alkali metal hydrogen carbonates (hereinafter referred to as alkali metal hydrogen carbonates); alkali metal hydroxides such as sodium hydroxide and potassium hydroxide (hereinafter referred to as alkali metal hydroxides); Alkaline earth metal hydroxides such as calcium (hereinafter referred to as alkaline earth metal hydroxides); sodium metho Metal alkoxides such as Sid and sodium ethoxide (hereinafter, referred to as metal alkoxides.); Alkali metal hydrides such as sodium hydride (. Which hereinafter referred to as alkali metal hydrides) are exemplified.

The reaction can be performed by adding a catalyst as necessary. Examples of the catalyst used in the reaction include dimethylaminopyridine.

In the reaction, with respect to 1 mole of the compound (M1), the ratio of the compound (R1) is usually 1 to 2 moles, the base is usually 1 to 2 moles, and the catalyst is usually 0.01 to 0.5 moles Used in

The reaction temperature is usually in the range of −30 to 150 ° C. The reaction time is usually in the range of 0.1 to 12 hours.

After completion of the reaction, compound (M2) can be obtained by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer.

Next, a method for producing the compound of the present invention from the compound (M2) will be described.

The compound of the present invention can be produced by reacting the compound (M2) with a compound represented by the formula (R2) (hereinafter referred to as compound (R2)).

The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons, nitriles, ethers, ketones, esters, aromatic hydrocarbons, aprotic polar solvents, alcohols such as methanol, ethanol, and isopropanol. (Hereinafter referred to as alcohols), water and mixtures thereof.

The reaction can be performed by adding a base as necessary. Examples of the base used in the reaction include organic bases, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides, alkaline earth metal hydroxides, metal alkoxides. And alkali metal hydrides.

In the reaction, the compound (R2) is usually used in a proportion of 1 to 10 mol and the base is usually used in a proportion of 1 to 10 mol with respect to 1 mol of the compound (M2).

After completion of the reaction, the compound of the present invention can be obtained by post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration of the organic layer.

Manufacturing method 2
The compound of the present invention can also be produced according to the following method.

[Wherein the symbols have the same meaning as described above. ]
First, a method for producing a compound represented by formula (M3) from compound (M2) (hereinafter referred to as compound (M3)) will be described.

Compound (M3) can be produced by reacting compound (M2) in the presence of a base.

The reaction is usually performed in the presence of a solvent. Examples of the solvent used for the reaction include water and a mixture of alcohols and water.

Examples of the base used in the reaction include alkali metal hydroxides and alkaline earth metal hydroxides.

In the reaction, the base is usually used at a ratio of 1 to 10 mol per 1 mol of the compound (M2).

The reaction temperature is usually in the range of 0 to 150 ° C. The reaction time is usually in the range of 0.1 to 12 hours.

After completion of the reaction, compound (M3) can be obtained by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer.

Next, a method for producing the compound of the present invention from the compound (M3) will be described.

The compound of the present invention can be produced by reacting the compound (M3) and the compound (R2) in the presence of a condensing agent.

The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons, nitriles, ethers, ketones, esters, aromatic hydrocarbons, aprotic polar solvents, nitrogen-containing aromatics such as pyridine and quinoline. Examples thereof include compounds (hereinafter referred to as nitrogen-containing aromatic compounds), water, and mixtures thereof.

Examples of the condensing agent include carbodiimides such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 1,3-dicyclohexylcarbodiimide (hereinafter referred to as carbodiimides), N, N′-carbonyldi- Imidazoles such as imidazole (hereinafter referred to as imidazoles), 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorphonium chloride n hydrate, trifluoro Triazines such as romethanesulfonic acid (4,6-dimethoxy-1,3,5-triazin-2-yl)-(2-octoxy-2-oxoethyl) dimethylammonium (hereinafter referred to as triazines), 1H— Benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, Phosphoniums such as rotripyrrolidinophosphonium hexafluorophosphate (hereinafter referred to as phosphoniums), O- (7-azabenzotriazol-1-yl) -N, N, N ′, N′-tetramethyluro Nium hexafluorophosphate, O- (7-azabenzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate (hereinafter referred to as HATU), etc. Uroniums (hereinafter referred to as uroniums).

The reaction can be performed by adding a catalyst as necessary. Examples of the catalyst include 1-hydroxybenzotriazole (hereinafter referred to as HOBt) and 1-hydroxyazabenzotriol (hereinafter referred to as HOAt).

In the reaction, with respect to 1 mol of the compound (M3), the compound (R2) is usually 0.5 to 2 mol, the condensing agent is usually 1 to 5 mol, and the catalyst is usually 0.01 to 1 mol. Used in proportions.

The reaction temperature is usually in the range of 0 to 120 ° C. The reaction time is usually in the range of 0.1 to 24 hours.

Production method 3
The compound of the present invention can also be produced according to the following method.

[Wherein the symbols have the same meaning as described above. ]
First, a method for producing a compound represented by the formula (M5) from the compound (R2) (hereinafter referred to as the compound (M5)) will be described.

Compound (M5) can be produced by reacting compound (R2) with compound (R1) in the presence of a base.

The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons, nitriles, ethers, ketones, esters, aromatic hydrocarbons, aprotic polar solvents, and mixtures thereof.

Examples of the base used in the reaction include organic bases, alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides, alkaline earth metal hydroxides, metal alkoxides. And alkali metal hydrides.

In the reaction, with respect to 1 mol of compound (R2), compound (R1) is usually in a proportion of 1 to 2 mol, base is usually in a proportion of 1 to 2 mol, and catalyst is usually in a proportion of 0.01 to 0.5 mol. Used in

After completion of the reaction, compound (M5) can be obtained by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer.

Next, a method for producing a compound represented by formula (M6) from compound (M5) (hereinafter referred to as compound (M6)) will be described.

Compound (M6) can be produced by reacting compound (M5) in the presence of a base.

In the reaction, the base is usually used at a ratio of 1 to 10 mol per 1 mol of the compound (M5).

After completion of the reaction, the compound (M6) can be obtained by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent and drying and concentration of the organic layer.

Next, a method for producing the compound of the present invention from the compound (M6) will be described.

The compound of the present invention can be produced by reacting the compound (M6) and the compound (M1) in the presence of a condensing agent.

Examples of the condensing agent include carbodiimides, imidazoles, triazines, phosphoniums, and uroniums.

The reaction can be performed by adding a catalyst as necessary. Examples of the catalyst include HOBt and HOAt.

In the reaction, with respect to 1 mol of the compound (M6), the compound (M1) is usually 0.5 to 2 mol, the condensing agent is usually 1 to 5 mol, and the catalyst is usually 0.01 to 1 mol. Used in proportions.

After completion of the reaction, the compound of the present invention can be obtained by post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer.

Manufacturing method 4
The compound of the present invention can also be produced according to the following method.

[Wherein the symbols have the same meaning as in formula (1). ]
The compound of the present invention can be produced by reacting compound (M1) with compound (M7) in the presence of a base.

In the reaction, with respect to 1 mol of compound (M1), compound (M7) is usually in a proportion of 0.5 to 2 mol, base is usually in a proportion of 1 to 2 mol, and catalyst is usually in a proportion of 0.01 to 0.5 mol. It is used in the ratio.

Manufacturing method 5
Next, a method for producing formula (M7) from compound (M6) will be described.

[Wherein the symbols have the same meaning as in formula (1). ]
Compound (M7) can be produced by reacting compound (M6) with a chlorinating agent.

The reaction is performed in the presence or absence of a solvent. Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons, nitriles, ethers, ketones, esters, aromatic hydrocarbons, aprotic polar solvents, and mixtures thereof.

Examples of the chlorinating agent used in the reaction include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, and phosphorus pentachloride.

In the reaction, the chlorinating agent is usually used at a ratio of 1 to 100 mol per 1 mol of the compound (M6).

After completion of the reaction, the compound (M7) can be obtained by post-treatment such as adding water to the reaction mixture and concentrating.

Manufacturing method 6
A compound represented by formula (1b) (hereinafter referred to as compound (1b)) and a compound represented by formula (1c) (hereinafter referred to as compound (1c)) can be produced by the following scheme. .

[Wherein the symbols have the same meaning as in formula (1). ]
First, a method for producing the compound (1b) from the compound represented by the formula (1a) (hereinafter referred to as the compound (1a)) will be described.

Compound (1b) can be produced by reacting compound (1a) with an oxidizing agent.

The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons, nitriles, alcohols, acetic acid, water, and mixtures thereof.

Examples of the oxidizing agent used in the reaction include sodium periodate, m-chloroperbenzoic acid (hereinafter referred to as mCPBA), and hydrogen peroxide.

When hydrogen peroxide is used as the oxidizing agent, a base or a catalyst may be added as necessary.

As the base used in the reaction, sodium carbonate can be mentioned.

Examples of the catalyst used in the reaction include tungstic acid and sodium tungstate.

In the reaction, with respect to 1 mol of the compound (1a), the oxidizing agent is usually in a proportion of 1 to 1.2 mol, the base is usually in a proportion of 0.01 to 1 mol, and the catalyst is usually in a proportion of 0.01 to 0.5 mol. It is used in the ratio.

The reaction temperature is usually in the range of −20 to 80 ° C. The reaction time is usually in the range of 0.1 to 12 hours.

After completion of the reaction, water is added to the reaction mixture and extracted with an organic solvent, and the organic layer is extracted with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary. Wash. Compound (1b) can be obtained by drying and concentrating the organic layer.

Next, a method for producing the compound (1c) from the compound (1b) will be described.

Compound (1c) can be produced by reacting compound (1b) with an oxidizing agent.

Examples of the oxidizing agent used in the reaction include mCPBA and hydrogen peroxide. When hydrogen peroxide is used as the oxidizing agent, a base or a catalyst may be added as necessary.

As the base used in the reaction, sodium carbonate can be mentioned.

Examples of the catalyst used in the reaction include sodium tungstate.

In the reaction, with respect to 1 mol of compound (1b), the oxidizing agent is usually in a proportion of 1 to 4 mol, the base is usually in a proportion of 0.01 to 1 mol, and the catalyst is usually in a proportion of 0.01 to 0.5 mol. Used in

The reaction temperature is usually in the range of −20 to 120 ° C. The reaction time is usually in the range of 0.1 to 12 hours.

After completion of the reaction, water is added to the reaction mixture and extracted with an organic solvent, and the organic layer is extracted with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary. Wash. Compound (1c) can be obtained by drying and concentrating the organic layer.

Also, the compound (1c) can be produced in a one-step reaction (one pot) by reacting the compound (1a) with an oxidizing agent.

Examples of the oxidizing agent used in the reaction include mCPBA and hydrogen peroxide.

When hydrogen peroxide is used as the oxidant for the reaction, a base or a catalyst may be added as necessary.

As the base used in the reaction, sodium carbonate can be mentioned.

Examples of the catalyst used for the reaction include tungstic acid and sodium tungstate.

In the reaction, with respect to 1 mol of compound (1a), the oxidizing agent is usually in a proportion of 2 to 5 mol, the base is usually in a proportion of 0.01 to 1 mol, and the catalyst is usually in a proportion of 0.01 to 0.5 mol. Used in

The reaction temperature is usually in the range of 0 to 120 ° C. The reaction time is usually in the range of 0.1 to 12 hours.

Manufacturing method 7
A compound represented by formula (1e) (hereinafter referred to as compound (1e)) is produced by reacting a compound represented by formula (1d) (hereinafter referred to as compound (1d)) with an oxidizing agent. can do.

[Wherein the symbols have the same meaning as in formula (1). ]
The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons, nitriles, alcohols, acetic acid, water, and mixtures thereof.

Examples of the oxidizing agent used in the reaction include sodium periodate, mCPBA, and hydrogen peroxide.

As the base used in the reaction, sodium carbonate can be mentioned.

In the reaction, with respect to 1 mol of the compound (1d), the oxidizing agent is usually in a proportion of 1 to 1.2 mol, the base is usually in a proportion of 0.01 to 1 mol, and the catalyst is usually in a proportion of 0.01 to 0.5 mol. It is used in the ratio.

After completion of the reaction, water is added to the reaction mixture and extracted with an organic solvent, and the organic layer is extracted with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary. Wash. Compound (1e) can be obtained by drying and concentrating the organic layer.

Manufacturing method 8
The compound represented by the formula (1f) (hereinafter referred to as the compound (1f)) can be produced by the following scheme.

[Wherein Q ^a represents NR ⁸ or NC (O) R ⁹ , and other symbols represent the same meaning as in formula (1). ]
Compound (1f) was prepared using Compound (1a) from Organic Letters, Vol. 9, no. 19, 2007, 3809-3811.

Manufacturing method 9
The compound represented by the formula (1g) (hereinafter referred to as the compound (1g)) can be produced by the following scheme.

[Wherein, R ^1a and E each independently represent a chlorine atom, a bromine atom or an iodine atom, R ^2a represents a C1-C6 perfluoroalkyl group, and R ^4a and R ^5a each independently represent C1 —C6 alkyl group or C1-C6 haloalkyl group, and other symbols have the same meanings as described above. ]
The compound represented by the formula (M8) (hereinafter referred to as the compound (M8)) is described in Journal of the American Chemical Society, 1931, vol. 53, p. It can be produced according to the method described in 3143-3146.

A compound represented by formula (M9) (hereinafter referred to as compound (M9)) can be produced by reacting compound (M8) with a compound represented by formula (R3) in the presence of a base. it can. The reaction can be carried out according to the method described in, for example, International Publication No. 2003/024961.

The compound represented by the formula (M10) (hereinafter referred to as the compound (M10)) can be produced using the compound (M9) according to the method described in International Publication No. 2005/073165.

A compound represented by the formula (M11) (hereinafter referred to as compound (M11)) can be produced according to the method described in International Publication No. 2003/024961.

The compound represented by the formula (M12) (hereinafter referred to as the compound (M12)) is prepared according to the method for producing the compound (M2) from the compound (M1) described in the production method 1 using the compound (M11). Can be manufactured.

The compound represented by formula (M14) (hereinafter referred to as compound (M14)) can be produced according to the method described in production method 2 using compound (M12).

Next, a method for producing the compound (1 g) from the compound (M14) will be described.

Compound (1g) can be produced by reacting compound (M14) with a compound represented by formula (R5) (hereinafter referred to as compound (R5)) in the presence of an additive.

The reaction is usually performed in the presence of a solvent. Examples of the solvent used for the reaction include aprotic polar solvents.

Examples of the additive used in the reaction include copper powder activated by the method described in Journal of Fluorine Chemistry, 102 (2000) 293-300.

In the reaction, with respect to 1 mole of the compound (M14), the compound (R5) is usually used at a ratio of 1 to 10 moles, and the additive is usually used at a ratio of 1 to 10 moles.

The reaction temperature is usually in the range of 0 to 150 ° C. The reaction time is usually in the range of 0.1 to 48 hours.

After completion of the reaction, the additive is removed by filtration, water is added to the reaction mixture, extraction is performed with an organic solvent, and post-treatment operations such as drying and concentration of the organic layer are performed to obtain the compound (1 g). be able to.

Manufacturing method 10
Compound (1g) can be produced according to the following scheme.

[Wherein the symbols have the same meaning as in formula (1). ]
The compound represented by the formula (M15) (hereinafter referred to as the compound (M15)) is obtained from the compound (M3) described in the production method 2 using the compound (M6) and the compound represented by the formula (R6). It can be produced according to the method for producing the inventive compound.

The compound represented by formula (M16) (hereinafter referred to as compound (M16)) was prepared according to the method for producing compound (M3) from compound (M2) described in production method 2 using compound (M15). Can be manufactured.

The compound represented by the formula (M17) (hereinafter referred to as the compound (M17)) is obtained from the compound (M3) described in the production method 2 using the compound (M16) and the compound represented by the formula (R7). It can be produced according to the method for producing the inventive compound. The compound represented by the formula (R6) and the compound represented by the formula (R7) are commercially available compounds or can be produced according to known methods.

Next, a method for producing a compound represented by formula (M18) (hereinafter referred to as compound (M18)) from compound (M17) will be described.

Compound (M18) can be produced by reacting compound (M17) and compound (R5) in the presence of an additive.

Examples of the additive used in the reaction include dithionite such as sodium dithionite or zinc-sulfite water.

Examples of the base used in the reaction include organic bases, alkali metal carbonates, and alkali metal hydroxides.

In the reaction, a phase transfer catalyst can be used as necessary. Examples of the phase transfer catalyst used in the reaction include quaternary ammonium salts such as tetrabutylammonium hydrogen sulfate, organic phosphorus salts such as tetrabutylphosphonium bromide, and alkyl polyether alkylamine compounds such as tris (methoxyethoxyethyl) amine. Is mentioned.

In the reaction, with respect to 1 mol of compound (M17), compound (R5) is usually in a proportion of 1 to 10 mol, additive is usually in a proportion of 0.1 to 2 mol, base is usually in a proportion of 1 to 10 mol, A phase transfer catalyst is usually used at a ratio of 0.01 to 2 mol.

After completion of the reaction, the compound (M18) can be obtained by performing post-treatment operations such as adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer.

Next, a method for producing the compound (1 g) from the compound (M18) will be described.

Compound (1g) can be produced by reacting compound (M18) with a halogenating agent.

Examples of the halogenating agent used in the reaction include N-chlorosuccinimide (hereinafter referred to as NCS), chlorine, N-bromosuccinimide (hereinafter referred to as NBS), bromine, and N-iodosuccinic acid. Examples include imide (hereinafter referred to as NIS), iodine and the like.

In the reaction, the halogenating agent is usually used at a ratio of 1 to 10 mol per 1 mol of the compound (M18).

The reaction temperature is usually in the range of 0 to 100 ° C. The reaction time is usually in the range of 0.1 to 12 hours.

After completion of the reaction, the compound (1 g) can be obtained by adding water to the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer.

Compound represented by formula (R9) (hereinafter referred to as compound (R9)), compound represented by formula (R10) (hereinafter referred to as compound (R10)), compound represented by formula (R11) (hereinafter referred to as compound) (Denoted as R11) and a compound represented by formula (R12) (hereinafter referred to as compound (R12)) can be produced by the following scheme.

[Wherein the symbols have the same meaning as described above. ]
Compound (R9) can be produced according to the method described in production method 8 using the compound represented by formula (R8) (hereinafter referred to as compound (R8)).

Compound (R10) can be produced according to the method described in Production Method 7 using Compound (R9).

Compound (R11) and Compound (R12) can be produced according to the method described in Production Method 6 using Compound (R8).

Compound (R8) is a commercially available compound or can be produced according to a known method.

Compound (R8) to Compound (R12) are included in Compound (R2).

Next, although the specific example of this invention compound is shown below, this invention is not limited to this.
In the table, “Me” represents a methyl group, “Et” represents an ethyl group, “Ac” represents an acetyl group, “ ⁱ Pr _F ” represents a heptafluoroisopropyl group, and “−” does not exist. .
Formula (1-1)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^6a , R ^7a , R ^6b , R ^7b , R ^6c , R ^7c , R ^6d , R ^7d , Q and k are [Table 1] to The compound of the present invention which is a combination described in [Table 10].

Formula (1-2)

R ^6c , R ^7c , R ^6d and R ^7d are hydrogen atoms, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^6a , R ^7a , R ^6b , R ^7b , Q and k are The compounds of the present invention which are combinations described in [Table 11] to [Table 18].

Formula (1-3)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^6a , R ^7a , R ^6b , R ^7b , R ^6c , R ^7c , Q and k are described in [Table 19] to [Table 27] The compound of the present invention which is a combination of

Examples of harmful arthropods for which the compounds of the present invention are effective include harmful insects and harmful mites. Specific examples of such harmful arthropods include the following.

Hemiptera pests: Japanese brown planthoppers (Laodelphax striatellus), brown planthoppers (Nilaparvata lugens), white planthoppers (Sogatella furcifera), corn planters (Peregrinus maidis), etc. (Nephotettix nigropictus), Recipe dorsalis, Emporasca onukii, Potato reef hopper (Empoasca fabae), Corn leaf hopper (Dalbulus maidis), Sugarcane ugicine (Suhana) ), Leafhoppers (Cofana spectra), leafhoppers (Nephotettix nigropictus), leafhoppers (Recilia dorsalis), cotton aphids (Aphis gossypii), peach moa Aphids (Myzus persicae), radish aphids (Brevicoryne brassicae), snowy aphids (Aphis spiraecola), tulip beetle aphids (Macrosiphum euphorbiae), potato beetle aphids (Aulacorthum solani), hum ), Peach beetle (Hyalopterus pruni), soybean aphid (Aphis glycines Matsumura), corn aphid (Rhopalosiphum maidis), scallop aphid (Tetraneura nigriabdominalis), grape aphid (Viteusoxvitifiraeae, Pera (Phylloxera devastatrix Pergande), Pecan leaf phylloxera (Phylloxera notabilis pergande), Southern pecan leaf phylloxera (Phylloxera russellae Stoetzel) Stink bug (Scotinophara lurida), Malayan rice black bug (Scotinophara coarctata), blue beetle (Nezara antennata), bark beetle (Eysarcoris parvus), black beetle (Halyomorphastula メ vira) Euskistus heros), Southern green stink bug (Nezara viridula), Red banded stink bug (Piezodorus guildinii), Burrower brown bug (Scaptocoris castanea), Oebalus pugnax, Dichelops melacanthus, etc. Stinkbugs (Leptocorisa chinensis), Helicoptera helicopters (Leptocorisa acuta), Leptocorisa genus, etc. , Chinchi Bugs (Blissus leucopterus leucopterus) and other turtles, whitefly (Trialeurodes vaporariorum), tobacco whitefly (Bemisia tabaci), citrus whitefly (Dialeurodes citri), citrus whitefly (Aleurocanthus spiniferus San Jose scale insect (Comstockaspis perniciosa), citrus snow scale (Unaspis citri), ruby rot beetle (Ceroplastes rubens), Icerya scale insect (Icerya purchasi), Fujicona scale insect (Planococcus kraunhiae), staghorn beetle (Pseuocis) Pseudaulacaspis pentagona), scale insects such as Brevennia リー rehi, Diaphorina citri, psylla pyrisuga, potato topslide (Bacterice) larvae such as rca キ cockerelli), beetles such as Stephanitis 、 nasi, bed bugs such as Cimex lectularius, and Giant Cicada (Quesada。gigas).

Lepidoptera: Chilo suppressalis, Darkheaded stm borer (Chilo polychrysus), Sunpikeza (Tryporyza incertulas), Netloi (Chilo polychrysus), White-meicho (Scirpophaga innotata), Yellow stem borer (Scirpophaga incertulas) Sesamia inferens, Rupela albinella, Cnaphalocrocis medinalis, Marasmia patnalis, Marasmia exigna, Notarcha derogata, Plodia interpunctella, Odalian Hula isla teterrellus), rice case worm (Nymphula depunctalis), Marasmia spp., Hop vine borer (Hydraecia immanis), European corn borer (Ostrinia nubilalis), Lesser cornstalk borer (Elasmopalpus lignosellus), Bean Shoot Borane (Epinotiaapore, Epinotiaatraia) saccharalis), Giant Suga Common moths such as rcane borer (Telchin licus), Spodoptera litura, Spodoptera exigua, Pseudaletia separata, Mamestra brassicae, Sesamia inoptera, Suria inoptera Spodoptera frugiperda, Spodoptera exempta, Tamanayaga (Agrotis ipsilon), Tamanaginuwaba (Plusia nigrisigna), Soybean looper (Pseudoplusia includens), Trichopulsia, Heliothis virescens, etc. Goats such as Velvetbean caterpillar (Anticarsia gammatalis) and Cotton leafworm (Alabama argillacea), white butterflies such as Pieris rapae, genus Adoxofies, Grapholita molesta, Leguminivora glycinivorella , Azukisayamushiga (Matsumuraeses azukivora), apple Coca summer fruit tortrix (Adoxophyes orana fasciata), smaller tea tortrix (Adoxophyes honmai. ), Chamonaki (Homona magnanima), Midelekamonmon (Archips fuscocupreanus), Codialinga (Cydia pomonella), etc., Chanohosoga (Caloptilia theivora), Kinmonhosoga (Phyllonorycter ringoneella), moss borer
(Ecdytolopha aurantiana) and other common moths, Coffee Leaf miner (Leucoptera coffeela), Rionetia sp. ) Potatoes such as potato moth (Phthorimaea operculella) and hitorigers such as Hyphantria cunea.

Common pests: Citrus thrips (Frankliniella occidentalis), Thrips parmi, Scirtothrips dorsalis, Thrips tabaci Thrips such as Kapida thrips (Haplothrips aculeatus), Rice thrips (Stenchaetothrips biformis).

Diptera: Culex pipiens pallens, Culex tritaeniorhynchus, Culex quinquefasciatus and other mosquitoes, Aedes ophegos Genus Anopheles, Chironomid, Musca domestica, Muscina stabulans, etc. Agromyza oryzae), rice leaflet (Hydrellia griseola), tomato leaffly (Liriomyza sativae), beetle leaflet (Liriomyza trifolii), leafhopper (Chromatomyia horticola) and other leafhoppers (Chromatomyia horticola), ryzae and other fruit fly, Dacus cucurbitae, fruit fly such as Ceratitis capitata, Hydrellia philippina, and Fleas such as fleas (Megaselia spiracularis), butterflies such as Clogmia albipunctata, and black fly flies. Crane fly such as Hessian fly (Mayetiola destructor), Oreseolia oryzae, Crane fly such as Diopsis macrophthalma, Common cranefly (Tipula oleracea), European gantry such as Europeanopecranefly (Tipula paludosa).

Coleoptera: Western corn root worm (Diabrotica virgifera virgifera), Southern corn root worm (Diabrotica undecimpunctata howardi), Northern corn root worm (Diabrotica virgifera zeae), Banded cucumber beetle (Diabrotica virgifera zeae) , San Antonio beetle (Diabrotica speciosa), Cucurbit Beetle (Diabrotica speciosa), bean leaf beetle (Cerotoma trifurcata), cereal leaf beetle (Oulema melanopus), cucumber horn beetle (Aulacophora） femoralis), pheasant potato beetle (Phylolsa ラ decor) , Rice beetle (Oulema oryzae), grape colaspis (Colaspis brunnea), corn flare beetle (Chaetocnema pulicaria), potato flare beetle (Epitrix) cucumeris), rice beetle (Dicladispa armigera), Seedcorn beetle (Stenolophus lecontei), Slender seedcorn beetle (Clivinia impressifrons), etc. majalis) carrot beetle (Bothynus gibbosus), Grape Colaspis (Colaspis brunnea), southern Corn leaf beetle (Myochrous denticollis), Holotrichia genus, June beetle (Phyllophaga crinita) (Echinocnemus squameus), rice weevil (Lissorhoptrus oryzophilus), weevil (Sphenophorus venatus), weevil (Anthonomus grandis), Southern Corn Billbug (Sphenophorus scallus) subsignatus) and Sphenophorus levis and other weevil species such as the genus Sphenophorus; Beetles (Anoplophora malasiaca), beetles of Migdolus fryanus, Okinawa beetle (Melanotus okinawensis), spider moth (Agriotes ogurae fuscicollis), legis gris , Anchastus sp., Melanotus sp., Limonius sp., Conoderus sp., Ctenicera sp.), Aedes, Paederus fuscipes, and Coffee Barry Borer (Hypothenemus hampei).

Insect pests: Tosama locust (Locusta migratoria), Kera (Gryllotalpa africana), Moroccan flying grasshopper (Dociostaurus maroccanus), Australian flying grasshopper (Chortoicetes terminifera), Red-spotted grasshopper (Nomadacris septemfa ciaustal Locna, Loc) melanorhodon), Italian Locust (Calliptamus italicus), Differential grasshopper (Melanoplus differentialis), Twostriped grasshopper (Melanoplus bivittatus), Migratory grasshopper (Melanoplus sanguinipes), Red-Legged grasshopper (Melanoplus sanguinipes), Red-Legged grasshopper (Melanoplus sanguinipes) (Schistocerca gregaria), Yellow-winged locust (Gastrimargus musicus), Spur-throated locust (Austracris guttulosa), Coxenago (Oxya yezoensis), Oxya japonica, Taiwan Chicos (Patanga ucci) , House cricket (Acheta domesticus), and Enmakoorogi (Teleogryllus emma), Mormon cricket (Anabrus simplex) or the like crickets acids.

Hymenopteran pests: bees such as Athalia rosae and Japanese bee (Athalia japonica). Fire Ants. Hachiriari such as Brown leaf-cutting ant (Atta capiguara).

Cockroach eye insects: German cockroach (Blattella germanica), Black cockroach (Periplaneta fliginosa), American cockroach (Periplaneta americana), Great cockroach (Periplaneta brunnea), Great cockroach (Blatta orientalis).

Termite insect pests: Yamato termite (Reticulitermes speratus), termite (Coptotermes formosanus), American ant termite (Incisitermes minor), daiko termite (Cryptotermes domesticus), ant-white termite (Odontotermes formosaterm), ants Glyptotermes satsumensis), long term termite (Glyptotermes miyatakei), white termite (Reticulitermes flaviceps amamianus), common termite (Reticulitermes sp.), white termite (Nasutitermes takasagoensis), nitobeshi Lori (Pericapritermes nitobei), Mushy termite (Sinocapritermes mushae), Cornitermes cumulans, etc.

Acarid pests: Nite spider mite (Tetranychus urticae), Kanzawa spider mite (Tetranychus kanzawai), Scarlet spider mite (Panonychus citri), Apple spider mite (Panonychus ulmi), Oligonicus spp. , Phyllocoptruta citri, tomato rustic mite (Aculops lycopersici), green rustic mite (Calacarus carinatus), green rusted mite (Acaphylla theavagrans), green rust mite (Eriophyes schibalech), ali Dust mites (Polyphagotarsonemus latus), Mite spider mites (Brevipalpus phoenicis), Mite, Mites, Haemaphysalis longicornis, Haemaphysalis flav a), Dermacentor taiwanicus, Dermacentor variabilis, Yamato tick (Ixodes ovatus), Ixodes persulcatus, Black-legged tick (Ixodes scapularis), American thorny tick (Amblyomma america) Tick such as Boophilus microplus, Rhipicephalus sanguineus Kind.

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 (DMF, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), sulfoxides (dimethylsulfoxide, etc.), propylene carbonate and vegetable oils (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 in 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, a wettable powder, a flowable agent, etc., it is usually applied by diluting with water so that the active ingredient concentration becomes 0.01 to 10,000 ppm. Granules, powders and the like 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 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, a wettable powder, a flowable agent, etc., it is usually diluted with water so that the active ingredient concentration 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 in more detail with reference to production examples, reference production examples, formulation examples, and test examples, but the present invention is not limited to these examples.

First, reference production examples and production examples are shown for production of the compound of the present invention.

Reference production example 1
To a mixture of 5.0 g of thiomorpholine, 0.89 g of 4- (dimethylamino) pyridine, 10.1 mL of triethylamine and 50 mL of THF, 4.5 mL of methyl chloroglyoxylate was added dropwise under ice cooling, and the mixture was stirred at room temperature for 4 hours. Water was added to the reaction mixture, extracted with MTBE, and then dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the resulting residue was subjected to silica gel column chromatography to obtain 7.45 g of intermediate A shown below.
Intermediate A

¹ H-NMR (CDCl ₃ ) δ: 3.95-3.90 (5H, m), 3.72-3.68 (2H, m), 2.74-2.69 (4H, m).

Reference production example 2
A mixture of Intermediate A (7.45 g), 2N aqueous sodium hydroxide solution (8 mL) and ethanol (80 mL) was stirred at 60 ° C. for 4 hours. Water was added to the reaction mixture allowed to cool to room temperature, and the mixture was washed with MTBE. The aqueous layer was adjusted to pH 2-3 with 2N hydrochloric acid, extracted with MTBE, and dried over anhydrous magnesium sulfate. Concentration under reduced pressure yielded 5.35 g of intermediate B shown below.
Intermediate B

¹ H-NMR (CDCl ₃ ) δ: 4.42-4.37 (2H, m), 4.02-3.97 (2H, m), 2.81-2.74 (4H, m).

Reference production example 3
Instead of Intermediate A, 3-[(methoxyoxalyl) amino] -N- [2-bromo-6- (difluoromethoxy) -4- (heptafluoroisopropyl) phenyl] benzamide (hereinafter referred to as Intermediate C) In accordance with the method described in Reference Production Example 2, Intermediate D shown below was obtained.
Intermediate D

¹ H-NMR (CDCl ₃ ) δ: 9.25-9.21 (1H, m), 8.31-8.29 (1H, m), 7.94-7.90 (1H, m), 7.84-7.81 (2H, m), 7.75-7.71 ( 1H, m), 7.64-7.59 (1H, m), 7.55-7.53 (1H, m), 6.63 (1H, t).

Reference production example 4
1.37 mL of oxalyl chloride was added dropwise to a mixture of 2.74 g of 4-fluoro-3-nitrobenzoic acid, 0.1 mL of DMF and 30 mL of THF, and the mixture was stirred for 1 hour under reflux. The reaction mixture allowed to cool to room temperature was concentrated to give 4-fluoro-3-nitrobenzoyl chloride.

5.0 g of 2-bromo-6- (difluoromethoxy) -4- (heptafluoroisopropyl) aniline (hereinafter referred to as Intermediate E) and 1,3-dimethyl-2-imidazolidinone (hereinafter referred to as DMI) .) A mixture of the whole amount of 4-fluoro-3-nitrobenzoyl chloride obtained above and 5 mL of DMI was added dropwise to 30 mL of the mixture, followed by stirring at 100 ° C. for 5 hours. Water was added to the reaction mixture allowed to cool to room temperature, extracted with MTBE, and then dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the resulting residue was subjected to silica gel column chromatography to obtain 5.79 g of intermediate N1-1 shown below.
Intermediate N1-1

¹ H-NMR (CDCl ₃ ) δ: 8.67-8.63 (1H, m), 8.28-8.23 (1H, m), 7.83-7.80 (1H, m), 7.65-7.62 (1H, m), 7.53-7.47 ( 2H, m), 6.59 (1H, t).

Reference production example 5
A mixture of 1.97 g of intermediate N1-1, 0.95 g of potassium carbonate and 34 mL of methanol was stirred under reflux for 2 hours. Water was added to the reaction mixture allowed to cool to room temperature, extracted with MTBE, and then dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the resulting residue was subjected to silica gel column chromatography to obtain 1.68 g of intermediate N1-2 shown below.
Intermediate N1-2

¹ H-NMR (CDCl ₃ ) δ: 8.45-8.42 (1H, m), 8.20-8.15 (1H, m), 7.81-7.78 (1H, m), 7.63-7.60 (1H, m), 7.52-7.49 ( 1H, m), 7.27-7.22 (1H, m), 6.58 (1H, t), 4.07 (3H, s).

Reference production example 6
A mixture of 3.79 g of intermediate N1-1, 11.1 g of electrolytic iron powder, 10.6 g of ammonium chloride, 53 mL of ethanol and 13 mL of water was stirred at 80 ° C. for 5 hours. Water was added to the reaction mixture which was allowed to cool to room temperature, filtered through celite, and the residue was washed with MTBE. The filtrate was separated, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to obtain 3.48 g of intermediate N2-1 shown below. It was.
Intermediate N2-1

¹ H-NMR (CDCl ₃ ) δ: 7.79-7.77 (1H, m), 7.52-7.48 (2H, m), 7.40-7.37 (1H, m), 7.26-7.21 (1H, m), 7.14-7.08 ( 1H, m), 6.59 (1H, t), 3.97-3.94 (2H, m).

Reference production example 7
The intermediate N3-1 shown below was obtained according to the method described in Reference Production Example 1 using the intermediate N2-1 instead of thiomorpholine.
Intermediate N3-1

¹ H-NMR (CDCl ₃ ) δ: 9.25-9.21 (1H, m), 9.02-8.98 (1H, m), 7.88-7.82 (2H, m), 7.81-7.78 (1H, m), 7.52-7.49 ( 1H, m), 7.36-7.29 (1H, m), 6.60 (1H, t), 4.02 (3H, s).

Reference production example 8
Intermediate N4-1 shown below was obtained according to the method described in Reference Production Example 2 using Intermediate N3-1 instead of Intermediate A.
Intermediate N4-1

¹ H-NMR (CDCl ₃ ) δ: 9.35-9.30 (1H, m), 8.94-8.89 (1H, m), 7.88-7.73 (3H, m), 7.53-7.48 (1H, m), 7.38-7.31 ( 1H, m), 6.59 (1H, t).

Reference production example 9
To a mixture of 7.0 g of N- [2-bromo-6- (difluoromethoxy) -4- (heptafluoroisopropyl) phenyl] -3-nitrobenzamide and 70 mL of DMF was added 604 mg of 60% sodium hydride (oily) under ice-cooling. Added and stirred for 25 minutes. To this mixture, 2.15 g of methyl iodide was added, and the mixture was further stirred for 1 hour. The reaction mixture was added to ice water and extracted with MTBE, and then the organic layer was washed successively with water and saturated brine. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and then the resulting residue was subjected to silica gel column chromatography to obtain 6.0 g of intermediate N1-8 shown below.
Intermediate N1-8

¹ H-NMR (CDCl ₃ ) δ: 8.20-8.13 (2H, m), 7.73-7.70 (1H, m), 7.68-7.66 (1H, m), 7.43-7.37 (1H, m), 7.30-7.28 ( 1H, m), 6.76-6.39 (1H, m), (3.38 + 3.26) (1H, s).

Reference production example 10
To a mixture of 5.7 g of intermediate N1-8, tin (II) chloride and ethanol (63 mL), 12N hydrochloric acid (6.3 mL) was added and stirred under reflux for 1.5 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure. To this reaction mixture, 20 g of ice and 72 mL of 10% aqueous sodium hydroxide solution were added, followed by filtration through celite. The filtrate was extracted with MTBE, and the organic layer was washed successively with water and saturated brine. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 5.0 g of intermediate N2-8 shown below.
Intermediate N2-8

¹ H-NMR (CDCl ₃ ) δ: ((7.83-7.48) + (7.25-7.22) + (7.03-6.95) + (6.89-6.84) + (6.82-6.73) + (6.59-6.53) + (6.49- 6.12)) (7H, m), ((3.85-3.83) + (3.62-3.60)) (2H, m), (3.33 + 3.23) (3H, s).

Reference production example 11
2.39 g of N-bromosuccinimide was added to a mixture of 3.0 g of 4- (trifluoromethoxy) -2- (trifluoromethyl) aniline, 25 mL of ethyl acetate and 5 mL of DMF, and the mixture was stirred at room temperature for 2.5 hours. To this reaction mixture was added 20% aqueous sodium thiosulfate solution, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2-bromo-4- (trifluoromethoxy) -6- (trifluoromethyl) aniline 3 0.2 g was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.54-7.52 (1H, m), 7.33-7.31 (1H, m), 4.75 (2H, br s).
The compounds produced by the production method according to the method described in the above Reference Production Examples and their physical property values are shown in the table.
Formula (N1)

In which R ¹ , R ³ and X ^a are represented by [Table 28].

A compound represented by the formula (N1-8).

¹ H-NMR (CDCl ₃ ) δ: 8.78-8.75 (1H, m), 8.51-8.46 (1H, m), 8.31-8.26 (1H, m), 7.84-7.80 (1H, m), 7.80-7.74 ( 1H, m), 7.67-7.62 (1H, m), 7.61-7.59 (1H, m).
Formula (N2)

In which R ¹ , R ³ and X ^a are represented by [Table 29].

A compound represented by the formula (N2-8).

¹ H-NMR (CDCl ₃ ) δ: 7.80-7.76 (1H, m), 7.57-7.54 (1H, m), 7.51-7.47 (1H, m), 7.32-7.20 (3H, m), 6.91-6.87 ( 1H, m), 3.87 (2H, br s).
Formula (N3)

In which R ¹ , R ³ and X ^a are represented by [Table 30] and [Table 31].

Formula (N4)

Wherein R ¹ , R ³ and X ^a are represented by [Table 32] and [Table 33].

A compound represented by formula (N5-1):

¹ H-NMR (CDCl ₃ ) δ: 9.53-9.51 (1H, m), 8.29-8.25 (1H, m), 7.88-7.86 (1H, m), 7.76-7.74 (1H, m), 7.36-7.31 ( 2H, m), 4.44-4.34 (1H, m), 4.17 (3H, s), 3.70 (3H, s), 3.57-3.47 (1H, m), 1.31-1.20 (3H, m).
A compound represented by the formula (N5-2).

¹ H-NMR (CDCl ₃ ) δ: 9.37-9.35 (1H, m), 8.24-8.20 (1H, m), 7.87-7.85 (1H, m), 7.75-7.73 (1H, m), 7.37-7.31 ( 2H, m), 4.36-4.25 (1H, m), 4.07 (3H, s), 3.62-3.51 (1H, m), 1.30-1.25 (3H, m).
A compound represented by formula (N6-1):

¹ H-NMR (DMSO-D6) δ: 11.03-10.98 (1H, m), 10.49-10.45 (1H, m), 8.32-8.26 (2H, m), 7.95-7.90 (2H, m), 7.75-7.71 (1H, m), 7.56-7.49 (1H, m), 3.84 (3H, s).
A compound represented by the formula (N6-2).

¹ H-NMR (DMSO-D6) δ: 10.95-10.92 (1H, m), 10.49-10.47 (1H, m), 8.37-8.35 (1H, m), 8.32-8.30 (1H, m), 7.98-7.93 (2H, m), 7.76-7.72 (1H, m), 7.57-7.52 (1H, m).

Production Example 1
A mixture of 0.69 g of Intermediate E, 0.23 g of Intermediate B, 0.50 g of HATU, 0.23 mL of diisopropylethylamine and 26 mL of DMF was stirred at 50 ° C. for 4 hours. Water was added to the reaction mixture allowed to cool to room temperature, extracted with MTBE, and then dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the resulting residue was subjected to silica gel column chromatography to obtain 0.75 g of the present compound 1-1 shown below.
Compound 1-1 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.36-9.34 (1H, m), 8.27-8.25 (1H, m), 7.86-7.80 (2H, m), 7.77-7.74 (1H, m), 7.68-7.66 ( 1H, m), 7.58-7.52 (2H, m), 6.63 (1H, t), 4.48-4.44 (2H, m), 4.03-3.99 (2H, m), 2.84-2.75 (4H, m).

Production Example 2
0.24 g of mCPBA (purity 65% or more) was added to a mixture of the compound 1-1 of the present invention (0.47 g) and 14 mL of chloroform under ice cooling, followed by stirring at room temperature for 4 hours. A saturated aqueous sodium thiosulfate solution and a saturated aqueous sodium hydrogen carbonate solution were sequentially added to the reaction mixture, extracted with chloroform, and then dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the resulting residue was subjected to silica gel column chromatography to obtain 0.25 g of the present compound 1-2 shown below and 0.22 g of the present compound 1-3 shown below.
Compound 1-2 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.37-9.35 (1H, m), 8.28-8.26 (1H, m), 7.86-7.75 (4H, m), 7.60-7.53 (2H, m), 6.62 (1H, t), 5.24-5.16 (1H, m), 4.64-4.57 (1H, m), 4.37-4.27 (1H, m), 4.00-3.92 (1H, m), 3.04-2.91 (3H, m), 2.86- 2.77 (1H, m).
Compound 1-3 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.33-9.31 (1H, m), 8.27-8.25 (1H, m), 7.87-7.77 (3H, m), 7.75-7.73 (1H, m), 7.61-7.53 ( 2H, m), 6.62 (1H, t), 4.75-4.70 (2H, m), 4.27-4.23 (2H, m), 3.32-3.27 (2H, m), 3.22-3.17 (2H, m).

Production Example 3
A mixture of 1.4 g of Intermediate C, 0.41 g of 1,3-thiazolidine, 0.96 mL of triethylamine and 22 mL of methanol was stirred with heating under reflux for 14.5 hours. The reaction mixture allowed to cool to room temperature was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 0.52 g of the present compound 1-4 shown below.
Compound 1-4 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.63-9.59 (1H, m), 8.32-8.29 (1H, m), 7.88-7.75 (4H, m), 7.60-7.53 (2H, m), 6.63 (1H, t), 5.20-5.18 (1H, m), 4.76-4.75 (1H, m), 4.47-4.43 (1H, m), 4.03-3.98 (1H, m), 3.21-3.17 (1H, m), 3.09- 3.05 (1H, m).

Production Example 4
A mixture of 0.52 g of intermediate D, 0.10 g of 3-methylthiomorpholine, 0.33 g of HATU, 0.15 mL of diisopropylethylamine and 30 mL of DMF was stirred at 50 ° C. for 4 hours. Water was added to the reaction mixture allowed to cool to room temperature, extracted with MTBE, and then dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the resulting residue was subjected to silica gel column chromatography to obtain 0.54 g of the present compound 1-7 shown below.
Compound 1-7 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.30-9.23 (1H, m), 8.29-8.25 (1H, m), 7.86-7.80 (2H, m), 7.78-7.74 (1H, m), 7.69-7.67 ( 1H, m), 7.59-7.52 (2H, m), 6.63 (1H, t), ((5.62-5.53) + (5.14-5.06)) (1H, m), ((5.22-5.15) + (4.72- 4.65)) (1H, m), ((3.61-3.52) + (3.35-3.25)) (1H, m), 3.22-3.10 (1H, m), ((3.02-2.93) + (2.89-2.80)) (1H, m), 2.64-2.54 (1H, m), 2.52-2.45 (1H, m), ((1.62-1.57) + (1.52-1.49)) (3H, m).

Production Example 5
N-bromosuccinimide (59 mg) was added to a mixture of the compound of the present invention 1-1 (0.15 g), cyanamide (12 mg), tert-butoxypotassium (29 mg) and methanol (7 mL), and the mixture was stirred at room temperature for 5 hours. A saturated aqueous sodium thiosulfate solution was added to the reaction mixture, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. The obtained residue was subjected to silica gel column chromatography to obtain 0.13 g of the present compound 1-10 shown below.
Compound 1-10 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.35-9.32 (1H, m), 8.27-8.24 (1H, m), 7.89-7.77 (3H, m), 7.72-7.69 (1H, m), 7.62-7.53 ( 2H, m), 6.63 (1H, t), 5.11-5.03 (1H, m), 4.68-4.58 (1H, m), 4.54-4.46 (1H, m), 4.25-4.11 (2H, m), 3.35- 3.08 (3H, m).

Production Example 6
To a mixture of the compound of the present invention 1-10 (0.27 g), potassium carbonate 0.15 g and ethanol 12 mL, 0.14 g of mCPBA (purity 65% or more) was added under ice cooling, and the mixture was stirred at room temperature for 4 hours. A saturated aqueous sodium thiosulfate solution and a saturated aqueous sodium hydrogen carbonate solution were sequentially added to the reaction mixture, extracted with MTBE, and then dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the resulting residue was subjected to silica gel column chromatography to obtain 0.27 g of the present compound 1-11 shown below.
Compound 1-11 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.27-9.24 (1H, m), 8.26-8.23 (1H, m), 7.90-7.86 (1H, m), 7.84-7.78 (2H, m), 7.63-7.58 ( 2H, m), 7.56-7.53 (1H, m), 6.63 (1H, t), 5.39-5.30 (1H, m), 4.82-4.74 (1H, m), 4.25-4.15 (1H, m), 3.85- 3.58 (4H, m), 3.47-3.38 (1H, m).

Production Example 7
A mixture of the present compound 1-1 (0.3 g), 99 mg of trifluoroacetamide, 0.21 g of iodobenzene diacetate, 71 mg of magnesium oxide, 10 mg of dirhodium (II) tetraacetate and 9 mL of chloroform was stirred at room temperature for an hour. . The reaction mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 0.20 g of the present compound 1-18 shown below.
Compound 1-18 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.30-9.28 (1H, m), 8.26-8.24 (1H, m), 7.89-7.76 (3H, m), 7.66-7.53 (3H, m), 6.63 (1H, t), 5.40-5.33 (1H, m), 4.77-4.70 (1H, m), 4.29-4.20 (1H, m), 3.92-3.83 (1H, m), 3.54-3.45 (2H, m), 3.36- 3.26 (1H, m), 3.16-3.07 (1H, m).

Production Example 8
The present compound 1-19 shown below was obtained according to the method described in Production Example 7 using the present compound 1-2 instead of the present compound 1-1.
Compound 1-19 of the present invention

¹ H-NMR (CDCl ₃ ) δ: 9.33-9.30 (1H, m), 8.26-8.23 (1H, m), 7.90-7.87 (1H, m), 7.84-7.77 (2H, m), 7.68-7.66 ( 1H, m), 7.62-7.57 (1H, m), 7.56-7.53 (1H, m), 6.63 (1H, t), 5.10-5.01 (1H, m), 4.57-4.47 (2H, m), 4.08- 3.85 (3H, m), 3.70-3.62 (1H, m), 3.56-3.47 (1H, m).

Production Example 9
To a mixture of the compound 1-1 of the present invention (0.70 g) and 21 mL of DMF was added 60% sodium hydride (oil) under ice cooling, and the mixture was stirred for 30 minutes. To this mixture, 0.44 g of methyl iodide was added, and the mixture was further stirred at 40 ° C. for 2 hours. The mixture was allowed to cool to room temperature, water was added, and the mixture was extracted with MTBE. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 0.59 g of the present compound 3-1 shown below.
Compound 3-1 of the present invention

¹ H-NMR (CDCl ₃ ) δ: ((7.87-7.85) + (7.70-7.40) + (7.37-7.35) + (7.28-7.12)) (6H, m), 7.03-6.36 (1H, m), ((4.07-3.21) + (2.80-2.40)) (14H, m).
The compounds described in the above production examples, the compounds produced by the production methods according to the methods described in the above production examples, and physical properties thereof are shown in the table.
A compound represented by formula (1-a).

T in the formula represents a substituent described in [Table 34] to [Table 36] below.

A compound represented by formula (1-b).

R ¹ , R ³ , X ¹ and n in the formula represent the combinations described in the following [Table 37] to [Table 40].

A compound represented by formula (1-c).

R ⁴ , R ⁵ and n in the formula represent the combinations described in [Table 41] below.

A compound represented by the formula (1-d).

X ^a in the formula represents a combination described in [Table 42].

Compound represented by formula (1-e) (hereinafter referred to as the present compound 5-1).

¹ H-NMR (CDCl ₃ ) δ: 9.56-9.50 (1H, m), 8.29-8.24 (1H, m), 7.87-7.85 (1H, m), 7.75-7.72 (1H, m), ((7.47- 7.37) + (7.31-7.26) + (7.17-7.14)) (2H, m), ((4.49-4.38) + (4.07-3.99) + (3.81-3.73) + (3.55-3.39) + (3.05-2.97 ) + (2.78-2.63) + (2.56-2.49)) (10H, m), (4.25 + 4.11) (3H, s), ((1.91-1.86) + (1.31-1.19)) (3H, m).
Compound represented by formula (1-f) (hereinafter referred to as the present compound 6-1).

¹ H-NMR (CDCl ₃ ) δ: 9.32-9.30 (1H, m), 8.25-8.23 (1H, m), 7.87-7.81 (2H, m), 7.77-7.73 (1H, m), 7.64-7.54 ( 3H, m), 4.49-4.45 (2H, m), 4.03-4.00 (2H, m), 2.85-2.81 (2H, m), 2.80-2.76 (2H, m).
Next, the formulation example of this invention compound is shown. In addition, a part represents a weight part.

Formulation Example 1
10 parts of any one of compounds 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 of the present invention In a mixture of 35 parts of xylene and 35 parts of DMF, 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate are added and mixed to obtain each preparation.

Formulation Example 2
4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of a synthetic silicon hydroxide fine powder and 54 parts of diatomaceous earth are mixed, and the compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3 20 parts of any one of -1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 are added and mixed to obtain each wettable powder.

Formulation Example 3
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 Then, 1 part of synthetic silicon hydrous 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
One part of any one of the compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 Dissolve in an appropriate amount of acetone, add 5 parts of synthetic hydrous hydroxide fine powder, 0.3 part of isopropyl acid phosphate and 93.7 parts of fusami clay, stir and mix thoroughly, and evaporate and remove acetone to remove each powder. Get.

Formulation Example 5
35 parts of a mixture of polyoxyethylene alkyl ether sulfate ammonium salt and white carbon (weight ratio 1: 1), and the compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7 Each flowable agent is obtained by mixing 10 parts of any one of 4-1 to 4-4, 5-1, and 6-1 and 55 parts of water and finely pulverizing them by a wet pulverization method.

Formulation Example 6
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 0.1 1 part is dissolved in a mixture of 5 parts xylene and 5 parts trichloroethane, and this is mixed with 89.9 parts kerosene to obtain each oil.

Formulation Example 7
10 mg of any one of the compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 in acetone Dissolve in 0.5 mL and drop this solution into 5 g of animal solid feed powder (solid feed powder CE-2 for breeding, product of Nippon Claire Co., Ltd.) and mix uniformly. Then acetone is evaporated to dryness to obtain each poisonous bait.

Formulation Example 8
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 0.1 Part, neothiozole (manufactured by Chuo Kasei Co., Ltd.) 49.9 parts in an aerosol can, and after mounting an aerosol valve, 25 parts of dimethyl ether and 25 parts of LPG are added, shaken, and an actuator aerosol is attached by attaching an actuator. obtain.

Formulation Example 9
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 0.6 Parts, BHT (2,6-di-tert-butyl-4-methylphenol) 0.01 part, xylene 5 parts, kerosene 3.39 parts and emulsifier {Rheodor MO-60 (manufactured by Kao Corporation)} 1 part After the mixture and 50 parts of distilled water are filled in an aerosol container and a valve is mounted, 40 parts of propellant (LPG) is pressurized and filled through the valve to obtain an aqueous aerosol.

Formulation Example 10
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 0.1 g 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
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 5 parts Melt 95 parts of ethylene-methyl methacrylate copolymer (ratio of methyl methacrylate in the copolymer: 10% by weight, ACLIFT (registered trademark) WD301, manufactured by Sumitomo Chemical Co., Ltd.) with a closed pressure kneader (Moriyama Seisakusho) 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
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 5 parts 95 parts of a soft vinyl chloride resin is 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 to obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm. obtain.

Formulation Example 13
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 100 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 2.5 mg are mixed and the resulting mixture is Compress to size to obtain tablets.

Formulation Example 14
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 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 to obtain a capsule.

Formulation Example 15
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 100 mg, fumar Distilled to 500 mL of acid, 2000 mg of sodium chloride, 150 mg of methylparaben, 50 mg of propylparaben, 25000 mg of granular sugar, 13000 mg of sorbitol (70% solution), 100 mg of VeegumK (VanderbiltCo.), 35 mg of fragrance, and 500 mg of colorant to a final volume of 100 mL Add water and mix to obtain a suspension for oral administration.

Formulation Example 16
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 5% by weight Is dissolved in 5% by weight of polysorbate 85, 3% by weight of benzyl alcohol and 30% by weight of propylene glycol, and a phosphate buffer solution is added so that the pH of this solution is 6.0 to 6.5. Water is added as the balance to obtain a solution for oral administration.

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, any one of the compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 10 Distribute the weight percentage to obtain a paste preparation for oral administration.

Formulation Example 18
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 5% by weight Is mixed with 95% by weight of limestone powder to obtain granules for oral administration using the wet granulation method.

Formulation Example 19
5 parts of any one of compounds 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 of the present invention Dissolve in 80 parts of diethylene glycol monoethyl ether and mix with 15 parts of propylene carbonate to obtain a spot-on solution.

Formulation Example 20
10 parts of any one of compounds 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 of the present invention Dissolve in 70 parts of diethylene glycol monoethyl ether and mix with 20 parts of 2-octyldodecanol to obtain a pour-on solution.

Formulation Example 21
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 0.5 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 the resulting mixture, and the mixture was stirred and mixed until a homogeneous solution was obtained. Add 5 parts and further stir and mix to obtain a shampoo of a uniform solution.

Formulation Example 22
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 0.15 The animal feed premix is obtained by sufficiently stirring and mixing 4.85% by weight of a mixture consisting of dilute calcium phosphate, diatomaceous earth, Aerosil, and carbonate (or chalk).

Formulation Example 23
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1, and 6-1 7.2 g , 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 form, cooled and solidified to obtain a suppository.

Next, the efficacy of the compound of the present invention against harmful arthropods is shown by test examples.

Test example 1
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-3, 2-7 to 2-9, 2-11 to 2-31, 3-1 to 3-7 obtained by Formulation Example 5 Formulations 4-1 to 4-3, 5-1, and 6-1 were each diluted with water so that the concentration of the compound of the present invention 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. The seedling was sprayed with 20 mL of the diluted solution.

6 days after spraying, the number of live cotton aphids that parasitized on the cucumber leaves 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 section Cai: number of parasitic live insects at the time of investigation in the untreated section Tb: number of insects before the treatment in the treated section Tai: number of parasitic live insects at the time of survey in the treated section 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, a control value of 90% or more was exhibited in all treatment sections where the compounds of the present invention were tested.

Test example 2
Compounds of the present invention 1-1 to 1-3, 1-5 to 1-8, 1-10, 1-12 to 1-14, 1-16, 1-20, 2-1 to 2-3, 2-7 to 2-9, 2-11, 2-12, 2-14, 2-15, 2-17 to 2-19, 2-21 to 2-25, 2-27 to 2- The preparations of 29, 3-1 to 3-7, 4-2, 5-1 and 6-1 were diluted with water so that the concentration of the compound of the present invention was 200 ppm, respectively, 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. 20 mL each of the diluted solution was sprayed on the seedlings.

Test example 3
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-4, 2-7 to 2-11 to 2-31, 3-1 to 3-7, 4-1 to 4 The preparations 4-3 and 5-1 were each diluted with water so that the concentration of the compound of the present invention 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, and 5 second-instar larvae (Plutella xylostella) 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 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 4
Compounds of the present invention 1-1 to 1-10, 1-12 to 1-15, 1-18, 1-20, 2-1 to 2-4, 2-7 to 2-9 obtained by Formulation Example 5 Formulations 2-11 to 2-19, 2-21 to 2-23, 2-25 to 2-29, 3-1 to 3-7, 4-1 to 4-3, and 5-1 are respectively represented in the present invention. It diluted with water so that the density | concentration of a compound might be 200 ppm, and the dilution liquid was obtained.

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, and 5 second-instar larvae (Plutella xylostella) 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 from the following formula.

Test Example 5
Compounds of the present invention 1-1 to 1-18, 2-20, 2-1 to 2-4, 2-7 to 2-9, 2-11 to 2-19, 2-21 to Formulations 2-29, 3-1 to 3-7, 4-1, 4-2 and 5-1 were each diluted with water so that the concentration of the compound of the present invention 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, in-sector LF (Nihon Nosan Co., Ltd.) sliced into 6 mm thickness and cut in half was placed, and 2 mL of the diluted solution was irrigated. After air drying, 5 third instar larvae of Spodoptera litura were released and covered. Six days later, the number of dead insects was counted, and the death rate was obtained from the following formula.

Test Example 6
Compounds of the present invention 1-1 to 1-18, 1-20, 2-1 to 2-3, 2-7 to 2-9, 2-11 to 2-29, 2-31 obtained by Formulation Example 5 The preparations of 3-1 to 3-7, 4-1 to 4-3, and 5-1 were each diluted with water so that the concentration of the compound of the present invention was 200 ppm to obtain a diluted solution.

The diluted solution was sprayed at a rate of 20 mL / cup on 5-6 leaf cabbage (Brassicae oleracea) planted in a polyethylene cup. After spraying, the plants were air-dried, covered with a polyethylene cup (capacity 400 mL), 10 4th instars of Spodoptera litura were released, and capped with Tetorongose. After storing at 25 ° C., the number of surviving insects was counted after 6 days, and the death rate was determined from the following formula.

Test Example 7
Compounds of the present invention 1-1 to 1-3, 1-5 to 1-10, 1-13, 1-14, 1-16, 1-17, 2-1, 2-2 obtained by Formulation Example 5 2-7 to 2-9, 2-11, 2-12, 2-17 to 2-19, 2-21, 2-23, 2-24, 2-26, 2-27 and 3-1 to 3- Each of the preparations 7 was diluted with water so that the concentration of the compound of the present invention was 500 ppm to obtain a diluted solution.

About 40 adult spider mite (Tetranychus urticae) females were inoculated on the seedling seedlings in the primary leaf development stage planted in a polyethylene cup, and 30 mL of the diluted solution was sprayed one day after the inoculation.

After 13 days of spraying, the number of surviving ticks on the leaves of the periwinkle was investigated, and the control rate was calculated by the following formula.

Control rate (%) = 100 × {1− (number of surviving ticks in treated area) / (number of surviving ticks in untreated area)}
As a result, a control rate of 90% or more was exhibited in all the treatment sections where the compounds of the present invention were tested.

Test Example 8
Compounds of the present invention 1-1 to 1-18, 2-1 to 2-3, 2-7 to 2-31, 3-1 to 3-3, 3-5, 3-6 obtained by Formulation Example 5 Formulations 4-1 to 4-3 and 5-1 were each diluted with water so that the concentration of the compound of the present invention 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, 0.7 mL of the diluted solution was dropped on 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 covered. One day later, 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 death rate was 100% in all the treatment sections where the compound of the present invention was tested.

Test Example 9
Compounds of the present invention 1-1 to 1-20, 2-1 to 2-31, 3-1 to 3-7, 4-1 to 4-4, 5-1 and 6-1 obtained by Formulation Example 5 Each preparation was diluted with water so that the concentration of the compound of the present invention was 500 ppm to obtain a diluted solution.

The diluted solution (0.7 mL) was added to ion-exchanged water (100 mL) (active ingredient concentration: 3.5 ppm). Twenty instar larvae of Culex pipiens pallens were released into the solution, and the number of dead insects was counted one day later, and the death rate was determined.

Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, the mortality rate of 91% or more was shown in all the treatment sections where the compounds of the present invention were tested.

Test Example 10
Compound 1-2 of the present invention obtained by Formulation Example 5, 1-4 to 1-7, 1-9, 1-12 to 1-14, 1-18, 1-20, 2-1 to 2-3, 2-7 to 2-9, 2-11, 2-12, 2-14 to 2-16, 2-18, 2-19, 2-21, 2-22, 2-24 to 2-27, 3- The preparations 1 to 3-3, 3-5 to 3-7, 4-1, and 5-1 were each diluted with water so that the concentration of the compound of the present invention 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, 0.7 mL of the diluted solution was dropped on the filter paper, and 30 mg of sucrose was uniformly added as food. Two adult male cockroaches (Blattalla germanica) were released into the polyethylene cup and covered. One day later, the number of dead insects was counted to determine the death rate.

Next, comparative examples of the compounds of the present invention and the compounds described in International Publication No. 2012/164698 are shown below.

Comparative Test Example 1
The compound 1-4 of the present invention and the compound 1-22 described in International Publication No. 2012/164698 were tested in accordance with the method described in Test Example 1 above, and control when the compound 1-4 of the present invention was used was tested. The control value when using compound 1-22 was 29% or less, whereas the value was 100%.
Compound 1-4 of the present invention

Compound 1-22 described in International Publication No. 2012/164698

Comparative test example 2
The compound 1-7 of the present invention and the compound 1-25 described in International Publication No. 2012/164698 were tested according to the method described in Test Example 1 except that the concentration of the active compound was 50 ppm. The control value when using the inventive compound 1-7 was 90% or more, whereas the control value when using the compound 1-25 was 29% or less.
Compound 1-7 of the present invention

Compound 1-25 described in International Publication No. 2012/164698

The compound of the present invention exhibits an excellent control effect against harmful arthropods.

Claims

Formula (1)

[Where:
G 1 and G 5 each independently represent —CR 6 R 7 — or —C (O) —,
G 2 , G 3 and G 4 each independently represent —CR 6 R 7 — or a single bond,
Q represents an oxygen atom, NR 8 , NC (O) R 9 or unsubstituted,
R 1 and R 3 are each independently a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a —S (O) p- (C1-C6 alkyl) group, a C1-C6 haloalkyl group, a C1-C6 A haloalkoxy group, a —S (O) p — (C1-C6 haloalkyl) group, a halogen atom, a nitro group or a cyano group;
R 2 represents a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group or a —S (O) p — (C1-C6 haloalkyl) group,
R 4 and R 5 are each independently a hydrogen atom, a C1-C6 alkyl group, a (C1-C4 alkoxy) C1-C4 alkyl group, a (C1-C6 alkyl) carbonyl group, a (C1-C4 alkoxy) carbonyl group, C1 A —C6 haloalkyl group, a (C1-C6 haloalkyl) carbonyl group or a (C1-C4 haloalkoxy) carbonyl group,
R 6 and R 7 are each independently a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a —S (O) p- (C1-C6 alkyl) group, a C1-C6 haloalkyl group, a C1-C6 halo. Represents an alkoxy group, —S (O) p — (C1-C6 haloalkyl) group, halogen atom or cyano group,
R 8 represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group or a cyano group,
R 9 represents a C1-C6 alkyl group or a C1-C6 haloalkyl group,
Each X a independently represents a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group, a halogen atom or a cyano group;
Each Xb independently represents a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group, a halogen atom or a cyano group;
k represents 0 or 1,
m represents an integer of 0 to 4,
n represents an integer of 0 to 2,
p represents an integer of 0-2. ]
A 3-aminooxalylaminobenzamide compound represented by:
R 1 and R 3 are each independently a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a —S (O) p- (C1-C6 alkyl) group, a C1-C6 haloalkyl group, a C1-C6 A haloalkoxy group, a —S (O) p — (C1-C6 haloalkyl) group or a halogen atom,
R 4 and R 5 are each independently a hydrogen atom, a C1-C6 alkyl group, a (C1-C6 alkyl) carbonyl group, a C1-C6 haloalkyl group or a (C1-C6 haloalkyl) carbonyl group,
R 6 and R 7 are each independently a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a halogen atom or a cyano group,
Each X a is independently a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group or a halogen atom;
2. The compound according to claim 1, wherein each Xb is independently a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkyl group, a C1-C6 haloalkoxy group or a halogen atom.
G 1 and G 5 are each independently —CR 6 R 7 —,
R 1 and R 3 are each independently a hydrogen atom, a C1-C3 alkyl group, a C1-C3 alkoxy group, a —S (O) p — (C1-C3 alkyl) group, a C1-C3 haloalkyl group, a C1-C3 A haloalkoxy group, a —S (O) p — (C1-C3 haloalkyl) group or a halogen atom,
R 4 and R 5 are each independently a hydrogen atom or a C1-C3 alkyl group,
R 6 and R 7 are each independently a hydrogen atom, a C1-C3 alkyl group or a C1-C3 haloalkyl group,
R 8 is a hydrogen atom, a methyl group, an ethyl group or a cyano group,
R 9 is a methyl group, an ethyl group or a trifluoromethyl group,
Each X a is independently a C1-C3 alkyl group, a C1-C3 alkoxy group, a C1-C3 haloalkyl group, a C1-C3 haloalkoxy group or a halogen atom;
The compound according to claim 1 or 2, wherein each Xb is independently a C1-C3 alkyl group, a C1-C3 alkoxy group, a C1-C3 haloalkyl group, a C1-C3 haloalkoxy group or a halogen atom.
A compound according to any one of the is claims 1 to 3 - G 2, G 3 and at least one of G 4 -CR 6 R 7.
One of R 1 and R 3 is a bromine atom, an iodine atom or a C1-C3 alkyl group, and the other is a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 haloalkoxy group, or —S The compound according to any one of claims 1 to 4, which is (O) p- (C1-C3 haloalkyl) group.
The compound according to any one of claims 1 to 5, wherein R 2 is a C1-C6 haloalkyl group.
The compound according to any one of claims 1 to 5, wherein R 2 is a C1-C6 haloalkoxy group.
The compound according to any one of claims 1 to 5, wherein R 2 is -S (O) p- (C1-C6 haloalkyl) group.
A harmful arthropod control composition comprising the compound according to any one of claims 1 to 8 and an inert carrier.
A method for controlling harmful arthropods, which comprises applying an effective amount of the compound according to any one of claims 1 to 8 to harmful arthropods or habitats of harmful arthropods.