WO2013187426A1

WO2013187426A1 - Pest control method for harmful arthropods

Info

Publication number: WO2013187426A1
Application number: PCT/JP2013/066134
Authority: WO
Inventors: 竜也鈴木; 岩田　淳; 吉彦野倉
Original assignee: 住友化学株式会社
Priority date: 2012-06-15
Filing date: 2013-06-05
Publication date: 2013-12-19

Abstract

A pest control method for harmful arthropods uses a compound represented by formula (1) [in the formula, each symbol indicates the definition provided in the description] to treat plant seeds. Provided is a pest control method for harmful arthropods that exhibits a superior pest control effect against harmful arthropods.

Description

How to control harmful arthropods

The present invention relates to a method for controlling harmful arthropods.

Conventionally, many compounds have been known as active ingredients used in methods for controlling harmful arthropods (see, for example, Non-Patent Document 1).

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

As a result of studying to find a method for controlling harmful arthropods having an excellent control effect on harmful arthropods, the present inventors have found that harmful effects can be obtained by treating plant seeds with a compound represented by the following formula (1). It has been found that arthropods can be controlled.

The present invention provides the following [1] to [4].
[1] Formula (1)

[Where:
A1 represents -NR6-, an oxygen atom or a sulfur atom,
A2 represents a nitrogen atom or = CH-,
R 1, R 2, R 3 and R 4 are the same or different and each have one or more atoms or groups selected from C1-C3 chain hydrocarbon group optionally having one or more halogen atoms and group Z An optionally substituted phenyl group, a 6-membered heterocyclic group optionally having one or more atoms or groups selected from group Z, -OR7, -S (O) mR7, a halogen atom, or a hydrogen atom; (However, at least two of R1, R2, R3 and R4 represent a hydrogen atom.),
R5 represents a C1-C3 chain hydrocarbon group which may have one or more atoms or groups selected from group X, -OR7, -S (O) mR7, or a halogen atom;
R6 is a C1-C3 chain hydrocarbon group which may have one or more atoms or groups selected from group W, and C3 which may have one or more atoms or groups selected from group W. -C6 represents an alicyclic hydrocarbon group or a hydrogen atom,
R7 represents a C1-C3 chain hydrocarbon group which may have one or more halogen atoms or a hydrogen atom,
m represents 0, 1 or 2, and n represents 0, 1 or 2.
Here, in -S (O) mR7, when m is 1 or 2, R7 does not represent a hydrogen atom.
Group X: C1-C3 alkoxy group optionally having one or more halogen atoms, C2-C3 alkenyloxy group optionally having one or more halogen atoms, having one or more halogen atoms An optionally substituted C2-C3 alkynyloxy group, a C1-C3 alkylsulfanyl group optionally having one or more halogen atoms, a C1-C3 alkylsulfinyl optionally having one or more halogen atoms A group consisting of a group, a C1-C3 alkylsulfonyl group optionally having one or more halogen atoms, a cyano group, a hydroxy group, and a halogen atom;
Group Z: C1-C3 chain hydrocarbon group optionally having one or more halogen atoms, C1-C3 alkoxy group optionally having one or more halogen atoms, one or more halogen atoms A C1-C3 alkylsulfanyl group optionally having one or more, a C1-C3 alkylsulfinyl group optionally having one or more halogen atoms, a C1-C3 optionally having one or more halogen atoms A group consisting of an alkylsulfonyl group, a cyano group, a nitro group and a halogen atom.
Group W: C1-C3 alkoxy group optionally having one or more halogen atoms, C2-C3 alkenyloxy group optionally having one or more halogen atoms, having one or more halogen atoms A group consisting of a C2-C3 alkynyloxy group, a halogen atom and a hydroxy group, which may be ] The control method of the harmful arthropod which treats a plant seed with the compound shown by this.

[2] Formula (1)

[Where:
A1 represents -NR6-, an oxygen atom or a sulfur atom,
A2 represents a nitrogen atom or = CH-,
R 1, R 2, R 3 and R 4 are the same or different and each have one or more atoms or groups selected from C1-C3 chain hydrocarbon group optionally having one or more halogen atoms and group Z An optionally substituted phenyl group, a 6-membered heterocyclic group optionally having one or more atoms or groups selected from group Z, -OR7, -S (O) mR7, a halogen atom, or a hydrogen atom; (However, at least two of R1, R2, R3 and R4 represent a hydrogen atom.),
R5 represents a C1-C3 chain hydrocarbon group which may have one or more atoms or groups selected from group X, -OR7, -S (O) mR7, or a halogen atom;
R6 is a C1-C3 chain hydrocarbon group which may have one or more atoms or groups selected from group W, and C3 which may have one or more atoms or groups selected from group W. -C6 represents an alicyclic hydrocarbon group or a hydrogen atom,
R7 represents a C1-C3 chain hydrocarbon group which may have one or more halogen atoms or a hydrogen atom,
m represents 0, 1 or 2, and n represents 0, 1 or 2.
Here, in -S (O) mR7, when m is 1 or 2, R7 does not represent a hydrogen atom.
Group X: C1-C3 alkoxy group optionally having one or more halogen atoms, C2-C3 alkenyloxy group optionally having one or more halogen atoms, having one or more halogen atoms An optionally substituted C2-C3 alkynyloxy group, a C1-C3 alkylsulfanyl group optionally having one or more halogen atoms, a C1-C3 alkylsulfinyl optionally having one or more halogen atoms A group consisting of a group, a C1-C3 alkylsulfonyl group optionally having one or more halogen atoms, a cyano group, a hydroxy group, and a halogen atom;
Group Z: C1-C3 chain hydrocarbon group optionally having one or more halogen atoms, C1-C3 alkoxy group optionally having one or more halogen atoms, one or more halogen atoms A C1-C3 alkylsulfanyl group optionally having one or more, a C1-C3 alkylsulfinyl group optionally having one or more halogen atoms, a C1-C3 optionally having one or more halogen atoms A group consisting of an alkylsulfonyl group, a cyano group, a nitro group and a halogen atom.
Group W: C1-C3 alkoxy group optionally having one or more halogen atoms, C2-C3 alkenyloxy group optionally having one or more halogen atoms, having one or more halogen atoms A group consisting of a C2-C3 alkynyloxy group, a halogen atom and a hydroxy group, which may be ] The plant seed processed by the compound shown by this.
[3] The method for controlling harmful arthropods according to [1], wherein 0.01 to 1000 g of the compound represented by the formula (1) is used per 10 kg of plant seeds.
[4] The method for controlling harmful arthropods according to [1] or [3], wherein the plant seed is a seed of corn, cotton, soybean, sugar beet, rapeseed, radish or rice.

The method of the present invention is represented by the formula (1)

[Where:
A1 represents -NR6-, an oxygen atom or a sulfur atom,
A2 represents a nitrogen atom or = CH-,
R 1, R 2, R 3 and R 4 are the same or different and each have one or more atoms or groups selected from C1-C3 chain hydrocarbon group optionally having one or more halogen atoms and group Z An optionally substituted phenyl group, a 6-membered heterocyclic group optionally having one or more atoms or groups selected from group Z, -OR7, -S (O) mR7, a halogen atom, or a hydrogen atom; (However, at least two of R1, R2, R3 and R4 represent a hydrogen atom.),
R5 represents a C1-C3 chain hydrocarbon group which may have one or more atoms or groups selected from group X, -OR7, -S (O) mR7, or a halogen atom;
R6 is a C1-C3 chain hydrocarbon group which may have one or more atoms or groups selected from group W, and C3 which may have one or more atoms or groups selected from group W. -C6 represents an alicyclic hydrocarbon group or a hydrogen atom,
R7 represents a C1-C3 chain hydrocarbon group which may have one or more halogen atoms or a hydrogen atom,
m represents 0, 1 or 2, and n represents 0, 1 or 2.
Here, in -S (O) mR7, when m is 1 or 2, R7 does not represent a hydrogen atom.
Group X: C1-C3 alkoxy group optionally having one or more halogen atoms, C2-C3 alkenyloxy group optionally having one or more halogen atoms, having one or more halogen atoms An optionally substituted C2-C3 alkynyloxy group, a C1-C3 alkylsulfanyl group optionally having one or more halogen atoms, a C1-C3 alkylsulfinyl optionally having one or more halogen atoms A group consisting of a group, a C1-C3 alkylsulfonyl group optionally having one or more halogen atoms, a cyano group, a hydroxy group, and a halogen atom;
Group Z: C1-C3 chain hydrocarbon group optionally having one or more halogen atoms, C1-C3 alkoxy group optionally having one or more halogen atoms, one or more halogen atoms A C1-C3 alkylsulfanyl group optionally having one or more, a C1-C3 alkylsulfinyl group optionally having one or more halogen atoms, a C1-C3 optionally having one or more halogen atoms A group consisting of an alkylsulfonyl group, a cyano group, a nitro group and a halogen atom.
Group W: C1-C3 alkoxy group optionally having one or more halogen atoms, C2-C3 alkenyloxy group optionally having one or more halogen atoms, having one or more halogen atoms A group consisting of a C2-C3 alkynyloxy group, a halogen atom and a hydroxy group, which may be The plant seed is treated with a compound represented by formula (hereinafter referred to as the present condensed heterocyclic compound).

The substituents used in the description of this specification will be described below with examples.

In the present specification, the expression “C1-C3 chain hydrocarbon group” represents a linear or branched saturated or unsaturated hydrocarbon group having 1 to 3 carbon atoms, such as a methyl group, C1-C3 alkyl groups such as ethyl group, propyl group and isopropyl group; C2-C3 alkenyl groups such as vinyl group, 1-propenyl group, 2-propenyl group and 1-methylvinyl group; ethynyl group, propargyl group, 2- A C2-C3 alkynyl group such as a butynyl group may be mentioned. The expression “C1-C2 chain hydrocarbon group” represents a methyl group, an ethyl group, a vinyl group, or an ethynyl group.

In the present specification, the expression “C1-C3 alkyl group” represents a linear or branched alkyl group having 1 to 3 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group. Is mentioned. The expression “C1-C2 alkyl group” represents a methyl group or an ethyl group.

In this specification, the expression “C2-C3 alkenyl group” is linear or branched having 2 to 3 carbon atoms, and has one or more double bonds in the molecule. Represents an unsaturated hydrocarbon group, and examples thereof include a vinyl group, a 1-propenyl group, a 2-propenyl group, and a 1-methylvinyl group.

In this specification, the expression “C2-C3 alkynyl group” refers to a linear or branched chain having 2 to 3 carbon atoms and having one or more triple bonds in the molecule. A saturated hydrocarbon group is represented, and examples thereof include an ethynyl group and a propargyl group.

In the present specification, the expression “C1-C3 alkoxy group” represents a group represented by a linear or branched alkyl-O— having 1 to 3 carbon atoms, such as a methoxy group or an ethoxy group. , A propyloxy group, and an isopropyloxy group.

In this specification, the expression “C2-C3 alkenyloxy group” refers to a linear or branched chain having 2 to 3 carbon atoms, and one or more double bonds in the molecule. Represents a group represented by alkenyl-O-, and examples thereof include a vinyloxy group, a 1-propenyloxy group, a 2-propenyloxy group, and a 1-methylvinyloxy group.

In the present specification, the expression “C2-C3 alkynyloxy group” is linear or branched having 2 to 3 carbon atoms, and has one or more triple bonds in the molecule. It represents a group represented by alkynyl-O—, and examples thereof include an ethynyloxy group and a propargyloxy group.

In the present specification, the expression “C1-C3 alkylsulfanyl group” represents a group represented by linear or branched alkyl-S— having 1 to 3 carbon atoms, such as a methylsulfanyl group, Examples thereof include an ethylsulfanyl group, a propylsulfanyl group, and an isopropylsulfanyl group.

In the present specification, the expression “C1-C3 alkylsulfinyl group” represents a group represented by linear or branched alkyl-S (O) — having 1 to 3 carbon atoms. Examples thereof include a sulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, and an isopropylsulfinyl group.

In the present specification, the expression “C1-C3 alkylsulfonyl group” represents a group represented by a linear or branched alkyl-S (O) 2- having 1 to 3 carbon atoms, for example, Examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, and an isopropylsulfonyl group.

In the present specification, the “C3-C6 alicyclic hydrocarbon group” represents a cyclic non-aromatic hydrocarbon group having 3 to 6 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, C3-C6 cycloalkyl group such as cyclohexyl group; C3-C6 cycloalkenyl group such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group and the like can be mentioned.

In this specification, the expression “C3-C6 cycloalkyl group” represents a cyclic alkyl group having 3 to 6 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

In the present specification, the expression “which may have one or more atoms or groups selected from group X” means that when it has two or more atoms or groups selected from group X, The atoms or groups selected from group X may be the same as or different from each other.

In the present specification, the expression “may have one or more atoms or groups selected from group Z” means that when it has two or more atoms or groups selected from group Z, The atoms or groups selected from group Z may be the same as or different from each other.

In the present specification, the expression “may have one or more atoms or groups selected from group W” means that when it has two or more atoms or groups selected from group W, those The atoms or groups selected from group W may be the same as or different from each other.

In the present specification, the expression “may have one or more halogen atoms” means that when two or more halogen atoms are present, these halogen atoms may be the same or different from each other. May be.

In the present specification, the expression “6-membered heterocyclic group” is a 6-membered heterocyclic compound containing one or more atoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom in addition to the carbon atom in the ring structure. Represents a residue, and examples thereof include a 6-membered aromatic heterocyclic group and a 6-membered non-aromatic heterocyclic group.
Examples of the “6-membered aromatic heterocyclic group” include a pyrazinyl group, a pyrimidinyl group, a pyridyl group, and a pyridazinyl group.
Examples of the “6-membered non-aromatic heterocyclic group” include a piperidyl group, a morpholinyl group, a piperazinyl group, and a thiomorpholinyl group.

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

In the present condensed heterocyclic compound, examples of the “C1-C3 chain hydrocarbon group optionally having one or more atoms or groups selected from group X” include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Methoxymethyl group, ethoxymethyl group, propyloxymethyl group, isopropyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-propyloxyethyl group, 2-isopropyloxyethyl group, difluoromethyl group, tri Fluoromethyl group, trichloromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 1,2,2,2-tetrafluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group , 2-chloro-1,1,1,3,3,3-hexafluoropropan-2-yl group (—C (Cl) (C 3) 1) selected from group X such as 2), heptafluoropropyl group, heptafluoroisopropyl group, methylsulfanylethyl group, ethylsulfanylethyl group, methylsulfinylethyl group, methylsulfonylethyl group, methoxycarbonylmethyl group, cyanomethyl group A C1-C3 alkyl group optionally having one or more atoms or groups; vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 1,1-difluoroallyl group, pentafluoroallyl group A C2-C3 alkenyl group optionally having one or more atoms or groups selected from the group X such as; having one or more atoms or groups selected from the group X such as an ethynyl group or a propargyl group; C2-C3 alkynyl group which may be mentioned is mentioned.

In the present condensed heterocyclic compound, examples of the “C1-C3 chain hydrocarbon group optionally having one or more halogen atoms” include a methyl group, an ethyl group, a propyl group, an isopropyl group, a trifluoromethyl group, It has one or more halogen atoms such as trichloromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoroisopropyl group, etc. Optionally a C1-C3 alkyl group;
C2-C3 alkenyl optionally having one or more halogen atoms such as vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 1,1-difluoroallyl group and pentafluoroallyl group Group; C2-C3 alkynyl group which may have one or more halogen atoms of ethynyl group and propargyl group.

Examples of the “C1-C3 alkyl group optionally having one or more halogen atoms” in the present condensed heterocyclic compound include a methyl group, an ethyl group, a propyl group, an isopropyl group, a trifluoromethyl group, and a trichloromethyl group. 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoroisopropyl group and the like.

In the present condensed heterocyclic compound, examples of the “phenyl group optionally having one or more atoms or groups selected from group Z” include a phenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, 4- Fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl Group, 2,3,4,5,6-pentafluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2-trifluoromethylphenyl group, 3-trifluoro Oromethylphenyl group, 4-trifluoromethylphenyl group, 2-trifluoromethoxyphenyl group, 3-trifluoromethoxyphenyl group, 4-trifluoromethoxyphenyl group, 2-trifluoromethylsulfanylphenyl group, 3-trifluoro Methylsulfanylphenyl group, 4-trifluoromethylsulfanylphenyl group, 4-methoxycarbonylphenyl group, 4-nitrophenyl group, 4-cyanophenyl group, 4-methylaminophenyl group, 4-dimethylaminophenyl group, 4-methyl A sulfinylphenyl group and a 4-methylsulfonylphenyl group are mentioned.

In the present condensed heterocyclic compound, examples of the “6-membered heterocyclic group optionally having one or more atoms or groups selected from group Z” include group Z such as piperidyl group, morpholyl group, and thiomorpholyl group. A 6-membered non-aromatic heterocyclic group optionally having one or more atoms or groups selected from: a pyrazinyl group, a 2-pyrimidinyl group, a 4-pyrimidinyl group, a 5-pyrimidinyl group, a 2-pyridyl group, 3 -Pyridyl group, 4-pyridyl group, 3-fluoro-2-pyridyl group, 4-fluoro-2-pyridyl group, 5-fluoro-2-pyridyl group, 6-fluoro-2-pyridyl group, 2-pyrimidinyl group, 6-membered ring which may have one or more atoms or groups selected from group Z such as 4-trifluoromethylpyridin-2-yl group and 5-trifluoromethylpyridin-2-yl group It includes family heterocyclic group.

In the present condensed heterocyclic compound, examples of the “C1-C3 chain hydrocarbon group optionally having one or more atoms or groups selected from group W” include a methyl group, an ethyl group, a propyl group, and an isopropyl group. , Trifluoromethyl group, trichloromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, methoxymethyl group, ethoxymethyl group, propyloxy Group W such as methyl group, isopropyloxymethyl group, methoxyethyl group, ethoxyethyl group, propyloxyethyl group, isopropyloxyethyl group, methylsulfanylethyl group, ethylsulfanylethyl group, methylsulfinylethyl group, and methylsulfonylethyl group Having one or more atoms or groups selected from And it may be C1-C3 alkyl group;
C2-C3 alkenyl which may have one or more atoms or groups selected from the group W such as vinyl group, 1-propenyl group, 2-propenyl group, 1,1-difluoroallyl group, pentafluoroallyl group, etc. Group;
C2-C3 alkynyl group which may have one or more atoms or groups selected from group W such as ethynyl group and propargyl group.

In the present condensed heterocyclic compound, “C3-C6 alicyclic hydrocarbon group optionally having one or more atoms or groups selected from group W” includes cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl Group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group and 3-cyclohexenyl group.

Examples of the “C1-C3 alkylsulfanyl group optionally having one or more halogen atoms” in the present condensed heterocyclic compound include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, and trifluoromethyl. Examples thereof include a sulfanyl group, a 2,2,2-trifluoroethylsulfanyl group, and a pentafluoroethylsulfanyl group.

Examples of the “C1-C3 alkylsulfinyl group optionally having one or more halogen atoms” in the present condensed heterocyclic compound include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, and trifluoromethyl. Examples thereof include a sulfinyl group, a 2,2,2-trifluoroethylsulfinyl group and a pentafluoroethylsulfinyl group.

Examples of the “C1-C3 alkylsulfonyl group optionally having one or more halogen atoms” in the present condensed heterocyclic compound include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, and trifluoromethyl. Examples include a sulfonyl group, a 2,2,2-trifluoroethylsulfonyl group, and a pentafluoroethylsulfonyl group.

Examples of the “C1-C3 alkoxy group optionally having one or more halogen atoms” in the present condensed heterocyclic compound include a methoxy group, a trifluoromethoxy group, an ethoxy group, and 2,2,2-trifluoroethoxy. Group, propyloxy group and isopropyloxy group.

In the present condensed heterocyclic compound, examples of the “C2-C3 alkenyloxy group optionally having one or more halogen atoms” include 2-propenyloxy group, 2-methyl-2-propenyloxy group, 3, 3 -A difluoroallyloxy group and a 3, 3- dichloroallyloxy group are mentioned.

Examples of the “C2-C3 alkynyloxy group optionally having one or more halogen atoms” in the present condensed heterocyclic compound include a propargyloxy group.

In the present condensed heterocyclic compound, “one or more” means one or more and the maximum number to which atoms or groups can be bonded, unless otherwise specified.

Examples of the present condensed heterocyclic compound include the following compounds.
In formula (1), A1 is -NR6-, an oxygen atom or a sulfur atom, and R5 is a C1-C3 having one C1-C3 alkoxy group which may have one or more halogen atoms. A chain hydrocarbon group, a compound which is a C1-C3 chain hydrocarbon group optionally having one or more halogen atoms;
In formula (1), a compound wherein A1 is -NR6- or a sulfur atom, and R5 is a C1-C3 chain hydrocarbon group optionally having one or more halogen atoms;
In the formula (1), A1 is —NR6-, an oxygen atom or a sulfur atom, A2 is N, and R5 has one C1-C3 alkoxy group which may have one or more halogen atoms. A C1-C3 chain hydrocarbon group, a compound which is a C1-C3 chain hydrocarbon group optionally having one or more halogen atoms;
In formula (1), a compound wherein A1 is -NR6- or a sulfur atom, A2 is N, and R5 is a C1-C3 chain hydrocarbon group optionally having one or more halogen atoms;
In formula (1), A1 is -NR6-, an oxygen atom or a sulfur atom, and R5 is a C1-C3 having one C1-C3 alkoxy group which may have one or more halogen atoms. A chain hydrocarbon group, a C1-C3 chain hydrocarbon group optionally having one or more halogen atoms, and a compound wherein R6 is a methyl group;
In the formula (1), A1 is —NR 6 — or a sulfur atom, R 5 is a C1-C3 chain hydrocarbon group optionally having one or more halogen atoms, and R 6 is a methyl group ;
In the formula (1), A1 is —NR6-, an oxygen atom or a sulfur atom, A2 is N, and R5 has one C1-C3 alkoxy group which may have one or more halogen atoms. A C1-C3 chain hydrocarbon group, a C1-C3 chain hydrocarbon group optionally having one or more halogen atoms, and R6 is a methyl group;
In Formula (1), A1 is -NR6- or a sulfur atom, A2 is N, R5 is a C1-C3 chain hydrocarbon group which may have one or more halogen atoms, R6 A compound wherein is a methyl group;
In formula (1), A1 is —NR6-, A2 is N, R5 is a C1-C2 chain hydrocarbon group optionally having one or more halogen atoms, and R6 is a methyl group. A compound which is
In the formula (1), compounds wherein A1 is -NR6- or a sulfur atom, R5 is -S (O) mR7, and R7 is a C1-C3 chain hydrocarbon group optionally having a halogen atom ;
In Formula (1), A1 is -NR6- or a sulfur atom, A2 is N, R5 is -S (O) mR7, and R7 may have one or more halogen atoms. A compound which is a C3 chain hydrocarbon group;
In Formula (1), A1 is -NR6- or a sulfur atom, R5 is -S (O) mR7, R6 is a methyl group, and R7 may have one or more halogen atoms. A compound which is a C1-C3 chain hydrocarbon group;
In Formula (1), A1 is —NR6- or a sulfur atom, A2 is N, R5 is —S (O) mR7, R6 is a methyl group, and R7 is one or more halogen atoms. A compound which is a C1-C3 chain hydrocarbon group optionally having;
In Formula (1), A1 is a sulfur atom, A2 is N, R5 is -S (O) mR7, R6 is a methyl group, and R7 has one or more halogen atoms. A compound which is a good C1-C2 chain hydrocarbon group;
In the formula (1), R2, R3 and R4 are the same or different and each is a C1-C3 chain hydrocarbon group optionally having one or more halogen atoms, -OR7, a halogen atom or a hydrogen atom, A compound wherein R5 is a C1-C3 chain hydrocarbon group optionally having one or more halogen atoms, -OR7, or a halogen atom;
In the formula (1), R2, R3 and R4 are the same or different and may have one or more halogen atoms or a C1-C2 alkyl group which may have one or more halogen atoms. A membered heterocyclic group or a hydrogen atom, and R5 is a 6-membered heterocyclic group optionally having one or more halogen atoms or a C1-C2 alkyl group optionally having one or more halogen atoms. A compound;
In the formula (1), R2, R3 and R4 are the same or different and are a methyl group, an ethyl group, a trifluoromethyl group, a trifluoromethoxy group or a hydrogen atom, and R5 is a methyl group, an ethyl group or a trifluoromethyl group. Or a compound which is a trifluoromethoxy group;
In the formula (1), R2, R3 and R4 are the same or different and are a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a hydrogen atom, and R5 is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom ;
In the formula (1), R2, R3 and R4 are the same or different and are a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a trifluoromethyl group, a trifluoromethoxy group, a pentafluoroethyl group or a hydrogen atom, and R5 A compound in which is a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a trifluoromethyl group, a trifluoromethoxy group or a pentafluoroethyl group;
In the formula (1), compounds wherein A1 is -NR6-;
In the formula (1), compounds wherein A1 is an oxygen atom;
In the formula (1), compounds wherein A1 is a sulfur atom;
In the formula (1), compounds wherein A2 is a nitrogen atom;
In the formula (1), compounds wherein A2 is ═CH—;
In the formula (1), compounds wherein R1, R3 and R4 are the same or different and are a halogen atom or a hydrogen atom;
In the formula (1), R2 may be a C1-C3 alkyl group optionally having one or more halogen atoms, a C1-C3 alkoxy group optionally having one or more halogen atoms, one or more A 6-membered aromatic heterocyclic group optionally having a C1-C3 alkyl group having a halogen atom, a halogen atom or a hydrogen atom;
In the formula (1), R1, R3 and R4 are the same or different and are a halogen atom or a hydrogen atom, and R2 may have one or more halogen atoms, a C1-C3 alkyl group, one or more A C1-C3 alkoxy group optionally having a halogen atom, a 6-membered aromatic heterocyclic group optionally having a C1-C3 alkyl group having one or more halogen atoms, a halogen atom or a hydrogen atom. Compound;

Formula (1A)

[Where:
A1A represents -NR6A-, an oxygen atom or a sulfur atom,
A2A represents a nitrogen atom or = CH-,
R1A, R3A and R4A are the same or different and represent a halogen atom or a hydrogen atom (provided that at least two of R1A, R3A and R4A represent a hydrogen atom), and R2A has one or more halogen atoms A C1-C3 alkyl group which may have one, a C1-C3 alkoxy group which may have one or more halogen atoms, and a C1-C3 alkyl group which has one or more halogen atoms 6 Represents a membered aromatic heterocyclic group, a halogen atom or a hydrogen atom,
R5A represents a C1-C3 alkyl group optionally having one or more halogen atoms, or -S (O) mR7A;
R6A represents a C1-C3 alkyl group or a C3-C6 cycloalkyl group,
R7A represents a C1-C3 alkyl group optionally having one or more halogen atoms,
m represents 0, 1 or 2, and n represents 0, 1 or 2. ] The compound shown by
In the formula (1A), compounds wherein A1A is —NR6A—;
In the formula (1A), compounds wherein A1A is an oxygen atom;
In the formula (1A), compounds wherein A1A is a sulfur atom;
In the formula (1A), compounds wherein A2A is a nitrogen atom;
In the formula (1A), compounds wherein A2A is ═CH—;

Formula (1B)

[Where:
A1B represents -NR6B-, an oxygen atom or a sulfur atom,
A2B represents a nitrogen atom or = CH-,
R1B, R3B and R4B are the same or different and represent a fluorine atom, a chlorine atom or a hydrogen atom (provided that at least two of R1B, R3B and R4B represent a hydrogen atom),
R2B is a C1-C3 alkyl group (particularly a methyl group, ethyl group or isopropyl group), a C1-C3 alkyl group having one or more halogen atoms (particularly a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, A heptafluoropropyl group, etc.) a C1-C3 alkoxy group having at least one halogen atom (especially a trifluoromethoxy group, etc.), a nitrogen-containing 6-membered aromatic heterocyclic group (especially 2-, 3- or 4- A pyridyl group, a 2-pyrimidinyl group, etc.), a halogen atom (especially a fluorine atom, a chlorine atom, a bromine atom, etc.) or a hydrogen atom,
R5B is a C1-C3 alkyl group having one or more halogen atoms (in particular, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2-chloro-1,1,1,3,3,3-hexafluoro A propan-2-yl group (-C (Cl) (CF3) 2), heptafluoroisopropyl group, etc.), or -S (O) mR7B,
R6B represents a C1-C3 alkyl group (methyl group, ethyl group, propyl group or isopropyl group, particularly methyl group),
R7B represents a C1-C3 alkyl group having one or more halogen atoms (a trifluoromethyl group, a pentafluoroethyl group, etc., particularly a trifluoromethyl group),
m represents 0, 1 or 2, and n represents 0, 1 or 2. ] The compound shown by
In the formula (1B), compounds wherein A1B is —NR6B—;
In the formula (1B), compounds wherein A1B is an oxygen atom;
In the formula (1B), compounds wherein A1B is a sulfur atom;
In the formula (1B), compounds wherein A2B is a nitrogen atom;
In the formula (1B), compounds wherein A2B is ═CH—.
The compounds represented by the general formulas (1A) and (1B) are included in the compound represented by the general formula (1).

Next, a method for producing the present condensed heterocyclic compound will be described.

The present condensed heterocyclic compound can be produced, for example, by the following (Production Method A) to (Production Method F).

(Production method A)
This condensed heterocyclic compound (1) can be produced by reacting the compound (M1) with the compound (M2). Alternatively, it can be produced by reacting the compound (M1) and the compound (M2) to produce the compound (M3) and cyclizing the compound (M3).

[Wherein, R 1, R 2, R 3, R 4, R 5, A 1, A 2 and n represent the same meaning as described above. ]

(Production method B)
This condensed heterocyclic compound (1) can be produced by reacting the compound (M1) with the compound (M4). Alternatively, it can be produced by reacting the compound (M1) and the compound (M4) to produce the compound (M3) and cyclizing the compound (M3).

(Production method C)
This fused heterocyclic compound (1) can be produced by reacting compound (M1) with compound (M5). Alternatively, it can be produced by reacting the compound (M1) and the compound (M5) to produce the compound (M6) and cyclizing the compound (M6).

[Wherein, R 1, R 2, R 3, R 4, R 5, A 1, A 2 and n represent the same meaning as described above. ]
(Production Method D)
Compound (2) in which A1 is a sulfur atom in formula (1) can be produced by reacting compound (M7) with a sulfurizing agent.

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]

(Production method E)
Compound (3) in which n is 0 in formula (1) can be produced, for example, by the following method.

[Wherein R1, R2, R3, R4, R5, A1 and A2 represent the same meaning as described above, and V2 represents a fluorine atom or a chlorine atom. ]

(Production Method F)
Compound (3) in which n is 0 in formula (1) can be produced, for example, by the following method.

[Wherein, R 1, R 2, R 3, R 4, R 5, A 1, A 2 and V 2 represent the same meaning as described above. ]

The production methods (Production Method A) to (Production Method F) of the present condensed heterocyclic compound will be described in more detail below. In addition, a production method from the present condensed heterocyclic compound to another condensed heterocyclic compound will be described. The present condensed heterocyclic compound can be produced, for example, by the following (Production Method 1) to (Production Method 23).

(Production Method 1) (Step (C-1))
Compound (4) in which A1 is -NR6- in formula (1) can be produced by reacting compound (M12) and compound (M5) according to step (C-1).

[Wherein, R 1, R 2, R 3, R 4, R 5, R 6, A 2 and n represent the same meaning as described above. ]
The reaction is usually carried out in the presence of a base, acid, sulfite or disulfite. The reaction is usually performed in the presence of a solvent.
Examples of the base used for the reaction include bicarbonates such as sodium bicarbonate and potassium bicarbonate, carbonates such as sodium carbonate and potassium carbonate, and mixtures thereof.
Examples of the acid used for the reaction include sulfonic acids such as p-toluenesulfonic acid and carboxylic acids such as acetic acid.
Examples of the sulfite used in the reaction include sodium sulfite and potassium sulfite.
Examples of the disulfite used in the reaction include sodium disulfite and potassium disulfite.
Examples of the solvent used in the reaction include ethers such as tetrahydrofuran (hereinafter referred to as THF), ethylene glycol dimethyl ether, tert-butyl methyl ether, 1,4-dioxane, and aliphatic hydrocarbons such as hexane, heptane, and octane. , Aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, N, N-dimethylformamide (hereinafter referred to as DMF) ), Acid amides such as N-methylpyrrolidone (hereinafter referred to as NMP), sulfoxides such as dimethyl sulfoxide (hereinafter referred to as DMSO), nitrogen-containing aromatic compounds such as pyridine and quinoline, and the like. A mixture is mentioned.
The reaction can be carried out by adding an oxidizing agent as necessary.
Examples of the oxidizing agent used in the reaction include oxygen, copper (II) chloride, 2,3-dichloro-5,6-dicyano-p-benzoquinone, and the like.
In the reaction, with respect to 1 mol of the compound (M12), the compound (M5) is usually 1 to 3 mol, the base is usually 1 to 5 mol, the acid is usually 1 to 5 mol, sulfite Is usually used in a proportion of 1 to 5 mol, disulfite is usually used in a proportion of 1 to 5 mol, and oxidizing agent is usually used in a proportion of 1 to 5 mol.
The reaction temperature of the reaction is usually in the range of 30 to 200 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4) can be isolated 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. The isolated compound (4) can be further purified by chromatography, recrystallization and the like.

(Production Method 2) (Step A-1)
Compound (4) in which A1 is —NR6- in formula (1) is produced by reacting compound (M12) and compound (M2) in the presence of a dehydration condensing agent according to step (A-1). can do.

[Wherein, R 1, R 2, R 3, R 4, R 5, R 6, A 2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, tert-butyl methyl ether, ethylene glycol dimethyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, pyridine and quinoline Examples thereof include nitrogen-containing aromatic compounds and mixtures thereof.
Examples of the dehydrating condensing agent used in the reaction include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (hereinafter referred to as WSC), carbodiimides such as 1,3-dicyclohexylcarbodiimide, (benzotriazole- 1-yloxy) tris (dimethylamino) phosphonium hexafluorophosphate (hereinafter referred to as BOP reagent) and the like.
This reaction can also be performed by adding a catalyst as needed.
Examples of the catalyst used in the reaction include 1-hydroxybenzotriazole (hereinafter referred to as HOBt).
In the reaction, with respect to 1 mol of the compound (M12), the compound (M2) is usually in a proportion of 1 to 3 mol, the dehydrating condensing agent is usually in a proportion of 1 to 5 mol, and the catalyst is usually in a proportion of 0.01 to 0.1. Used in molar proportions.
The reaction temperature of the reaction is usually in the range of 30 to 200 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4) can be isolated 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. The isolated compound (4) can be further purified by chromatography, recrystallization and the like.
Moreover, according to the step (B-1), the compound (M4) can be used instead of the compound (M2), and the compound (4) can be produced according to the above method.
When the compound (M4) is used, it is usually carried out without adding a dehydrating condensation agent. A base can be added as necessary.
Examples of the base include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
In the reaction, with respect to 1 mol of the compound (M12), the compound (M4) is usually used in a proportion of 1 to 3 mol, and the base is usually used in a proportion of 1 to 10 mol.

(Production Method 3) (Step (A-3), Step (B-3))
Compound (4) in which A1 is -NR6- in formula (1) can be produced by dehydrating condensation of compound (M13) according to step (A-3) or step (B-3).

[Wherein, R 1, R 2, R 3, R 4, R 5, R 6, A 2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, methanol, ethanol, propanol , Alcohols such as butanol and pentanol, and mixtures thereof.
In the reaction, an acid or a dehydrating agent can be used as necessary. Examples of the acid used in the reaction include sulfonic acids such as p-toluenesulfonic acid, and carboxylic acids such as acetic acid. Examples of the dehydrating agent used in the reaction include phosphorus oxychloride, acetic anhydride, trifluoroacetic anhydride, and the like. Can be mentioned.
In the reaction, with respect to 1 mol of the compound (M13), an acid or a dehydrating agent is usually used at a ratio of 1 mol to 10 mol.
The reaction temperature of the reaction is usually in the range of 30 to 200 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4) can be further purified by chromatography, recrystallization and the like.

(Production Method 4) (Step (A-3), Step (B-3))
Compound (4) in which A1 is -NR6- in formula (1) is produced by reacting compound (M13) in the presence of a base according to step (A-3) or step (B-3). Can do.

[Wherein, R 1, R 2, R 3, R 4, R 5, R 6, A 2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, methanol, ethanol, propanol , Butanol, tert-butanol, pentanol and the like, and mixtures thereof.
Examples of the base used for the reaction include tripotassium phosphate.
In the reaction, the base is generally used at a ratio of 1 mol to 10 mol with respect to 1 mol of the compound (M13).
The reaction temperature of the reaction is usually in the range of 30 to 200 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4) can be further purified by chromatography, recrystallization and the like.

(Production method 5)
Compound (4) in which A1 is -NR6- in formula (1) can be produced by reacting compound (5) with compound (M14) in the presence of a base.

[Wherein R 1, R 2, R 3, R 4, R 5, A 2 and n represent the same meaning as described above, and L represents a chlorine atom, bromine atom, iodine atom, trifluoromethylsulfonyloxy group, methylsulfonyloxy group, etc. And R6 represents a C1-C3 chain hydrocarbon group which may have one or more atoms or groups selected from group W. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, DMF, Examples include acid amides such as NMP, sulfoxides such as DMSO, and mixtures thereof.
Examples of the base used in the reaction include alkali metal or alkali metal hydrides such as sodium hydride, potassium hydride and calcium hydride, inorganic bases such as sodium carbonate and potassium carbonate, or organic bases such as triethylamine. Is mentioned.
In the reaction, compound (M14) is usually used at a ratio of 1 to 5 mol per 1 mol of compound (5).
In the reaction, the base is usually used at a ratio of 1 to 3 mol with respect to 1 mol of the compound (5).
The reaction temperature of the reaction is usually in the range of 0 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (4) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (4) can be further purified by chromatography, recrystallization and the like.

(Manufacturing method 6) (Process (A-1))
Compound (6) in which A1 is an oxygen atom in formula (1) can be produced by reacting compound (M15) and compound (M2) in the presence of an acid according to step (A-1). it can.

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence or absence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, and mixtures thereof.
Examples of the acid used for the reaction include polyphosphoric acid and trimethylsilyl polyphosphate.
The reaction is usually carried out without a solvent when polyphosphoric acid is used as the acid, but it may be carried out in a solvent.
In the reaction, with respect to 1 mol of the compound (M15), the compound (M2) is usually used in a proportion of 1 to 3 mol, and the acid is usually used in a proportion of 1 to 10 mol.
The reaction temperature of the reaction is usually in the range of 50 to 200 ° C. The reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (6) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (6) can be further purified by chromatography, recrystallization and the like.
Moreover, it can replace with a compound (M2) and can use a compound (M4) and can manufacture a compound (6) according to the said method according to a process (B-1).
When the compound (M4) is used, it is usually carried out without adding a dehydrating condensation agent. A base can be added as necessary.
Examples of the base include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
In the reaction, with respect to 1 mol of the compound (M15), the compound (M4) is usually used in a proportion of 1 to 3 mol, and the base is usually used in a proportion of 1 to 10 mol.

(Manufacturing method 7) (Process (C-3))
Compound (6) in which A1 is an oxygen atom in formula (1) can be produced by subjecting compound (M16) to an oxidation reaction according to step (C-3).

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, nitriles such as acetonitrile, and acid amides such as DMF and NMP , Sulfoxides such as DMSO, acetic acid and mixtures thereof.
Examples of the oxidizing agent used in the reaction include metal oxidizing agents such as lead (IV) acetate and lead (IV) oxide, hypervalent iodine compounds such as iodobenzene diacetate, and the like.
In the reaction, with respect to 1 mol of the compound (M16), the oxidizing agent is usually used at a ratio of 1 to 3 mol.
The reaction temperature of the reaction is usually in the range of 0 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (6) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (6) can be further purified by chromatography, recrystallization and the like.

(Production Method 8) (Step (A-3), Step (B-3))
Compound (6) in which A1 is an oxygen atom in formula (1) is produced by reacting compound (M17) in the presence of a dehydration condensing agent according to step (A-3) or step (B-3). be able to.

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, dichloromethane, chloroform, carbon tetrachloride, Examples include halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, and mixtures thereof. Of these, carbon tetrachloride can also be used as a dehydrating condensing agent.
Examples of the dehydrating condensing agent used in the reaction include a mixture of triphenylphosphine, a base, and carbon tetrachloride or carbon tetrabromide, a mixture of triphenylphosphine and an azodiester such as azodicarboxylic acid diethyl ester, and the like.
Examples of the base used in the reaction include tertiary amines such as triethylamine and diisopropylethylamine.
In the reaction, the dehydrating condensing agent is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (M17). When a base is used, the base is usually used at a ratio of 1 to 5 mol with respect to 1 mol of the compound (M17).
The reaction temperature is usually in the range of −30 to 100 ° C. The reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (6) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (6) can be further purified by chromatography, recrystallization and the like.

(Production Method 9) (Step (A-3), Step (B-3))
Compound (6) in which A1 is an oxygen atom in formula (1) can be produced by reacting compound (M17) in the presence of an acid according to step (A-3) or step (B-3). it can.

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, and halogens such as dichloromethane, chloroform, and chlorobenzene. Hydrocarbons and mixtures thereof.
Examples of the acid include sulfonic acids such as p-toluenesulfonic acid, polyphosphoric acid, and the like.
In the reaction, an acid is usually used at a ratio of 0.1 to 3 mol with respect to 1 mol of the compound (M17).
The reaction temperature of the reaction is usually in the range of 50 to 200 ° C. The reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the compound (6) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (6) can be further purified by chromatography, recrystallization and the like.

(Manufacturing method 10) (Process (C-1))
Compound (2) in which A1 is a sulfur atom in formula (1) can be produced by reacting compound (M18) and compound (M5) according to step (C-1).

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
The reaction is usually carried out in the presence of a base, acid, sulfite or disulfite. Examples of the base used in the reaction include hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, carbonates such as sodium carbonate and potassium carbonate, and mixtures thereof.
Examples of the acid used for the reaction include sulfonic acids such as p-toluenesulfonic acid and carboxylic acids such as acetic acid.
Examples of the sulfite used in the reaction include sodium sulfite and potassium sulfite.
Examples of the disulfite used in the reaction include sodium disulfite and potassium disulfite.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and halogenation such as chlorobenzene. Hydrocarbons, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF, N- and NMP, sulfoxides such as DMSO, and aromatic hydrocarbons such as toluene, xylene and nitrobenzene And mixtures thereof.
The reaction can be carried out by adding an oxidizing agent as necessary.
Examples of the oxidizing agent used in the reaction include oxygen, copper (II) chloride, 2,3-dichloro-5,6-dicyano-p-benzoquinone, and the like.
In the reaction, with respect to 1 mole of the compound (M18), the ratio of the compound (M5) is usually 1 to 3 moles, the base is 1 to 5 moles, the acid is usually 1 to 5 moles, and the sulfite is added. Usually, 1 to 5 moles, disulfite is usually used in 1 to 5 moles, and oxidizing agent is usually used in 1 to 5 moles.
The reaction temperature of the reaction is usually in the range of 50 to 200 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (2) can be isolated by performing post-treatment operations such as addition of the reaction mixture to water, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (2) can also be purified by chromatography, recrystallization and the like.

(Manufacturing method 11) (Process (C-1))
Compound (2) in which A1 is a sulfur atom in formula (1) can be produced by reacting hydrochloride of compound (M18) with compound (M5) according to step (C-1).

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
The reaction is carried out in the presence of a base and usually in the presence of a solvent.
Examples of the base used in the reaction include tertiary amines such as diisopropylethylamine and triethylamine.
Examples of the solvent used in the reaction include sulfoxides such as DMSO, aromatic hydrocarbons such as nitrobenzene, and mixtures thereof.
In the reaction, the compound (M5) is usually used at a ratio of 0.5 to 3 moles and the base is usually used at a ratio of 1 to 2 moles relative to 1 mole of the compound (M18).
The reaction temperature of the reaction is usually in the range of 50 to 200 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (2) can be isolated by performing post-treatment operations such as addition of the reaction mixture to water, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (2) can also be purified by chromatography, recrystallization and the like.

(Production method 12)
Compound (8) in which R5 in formula (1) is a cyano group or a C1-C3 alkyl group is obtained by reacting compound (7) with a cyanating agent or di (C1-C3 alkyl) zinc in the presence of a palladium compound. Can be manufactured.

[Wherein R1, R2, R3, R4, A1, A2 and n represent the same meaning as described above, V1 represents a leaving group such as a bromine atom or an iodine atom, and R5z represents a cyano group or a C1-C3 alkyl group. Represents. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, alcohols such as methanol and ethanol, acid amides such as DMF and NMP, sulfoxides such as DMSO, and mixtures thereof.
Examples of the cyanating agent used in the reaction include zinc cyanide, and examples of the di (C1-C3 alkyl) zinc include dimethyl zinc, diethyl zinc, and diisopropyl zinc.
Examples of the palladium compound used for the reaction include tetrakis (triphenylphosphine) palladium.
In the reaction, with respect to 1 mol of the compound (7), the cyanating agent or di (C1-C3 alkyl) zinc is usually in a proportion of 1 to 5 mol, and the palladium compound is usually in a proportion of 0.01 to 0.5 mol. Used in
The reaction temperature of the reaction is usually in the range of 50 to 200 ° C. The reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (8) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (8) can be further purified by chromatography, recrystallization and the like.

(Production method 13)
Compound (9) in which R5 is a C1-C3 perfluoroalkyl group in formula (1) can be produced by reacting compound (7) and compound (M19) in the presence of copper iodide. .

[Wherein R1, R2, R3, R4, A1, A2, n and V1 represent the same meaning as described above, and Rf represents a C1-C3 perfluoroalkyl group. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aromatic hydrocarbons such as toluene and xylene, acid amides such as DMF and NMP, and mixtures thereof.
In the reaction, with respect to 1 mol of the compound (7), the compound (M19) is usually used in a proportion of 1 to 10 mol, and copper iodide is usually used in a proportion of 1 to 5 mol.
The reaction temperature of the reaction is usually in the range of 50 to 200 ° C. The reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (9) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (9) can be further purified by chromatography, recrystallization and the like.

(Manufacturing method 14) (Process (E-4))
Compound (3) in which n is 0 in formula (1) can be produced by reacting compound (M10) and compound (M20) in the presence of a base according to step (E-4). .

[Wherein, R 1, R 2, R 3, R 4, R 5, A 1, A 2 and V 2 represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include water, THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, ethers such as 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol and ethanol. Nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, and mixtures thereof.
Examples of the base used for the reaction include alkali metal hydrides such as sodium hydride.
In the reaction, with respect to 1 mol of the compound (M10), the compound (M20) 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.
The reaction temperature of the reaction is usually in the range of 0 to 150 ° C. The reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (3) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (3) can be further purified by chromatography, recrystallization and the like.

(Manufacturing method 15) (Process (F-2))
Compound (3) in which n is 0 in formula (1) can be produced by reacting compound (M11) and compound (M21) in the presence of a base according to step (F-2).

[Wherein R 1, R 2, R 3, R 4, R 5, A 1, A 2 and L represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, DMF, Examples include acid amides such as NMP, sulfoxides such as DMSO, and mixtures thereof.
Examples of the base used in the reaction include alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride, inorganic bases such as sodium carbonate and potassium carbonate, and organic bases such as triethylamine. Can be mentioned.
In the reaction, with respect to 1 mol of the compound (M11), the base is usually used at a ratio of 1 to 3 mol, and the compound (M21) is usually used at a ratio of 1 to 3 mol.
The reaction temperature of the reaction is usually in the range of 0 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours. After completion of the reaction, the compound (3) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (3) can be further purified by chromatography, recrystallization and the like.

(Production Method 16)
Compound (10) in which n is 1 in formula (1) can be produced by subjecting compound (3) to an oxidation reaction.

[Wherein R 1, R 2, R 3, R 4, R 5, A 1 and A 2 represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include sodium periodate and m-chloroperbenzoic acid.
In the reaction, an oxidizing agent is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (3). Preferably, the oxidizing agent is used in a proportion of 1 to 1.2 mol with respect to 1 mol of compound (3).
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, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried, The compound (10) can be isolated by performing post-treatment operations such as concentration. The isolated compound (10) can be further purified by chromatography, recrystallization and the like.

(Production Method 17)
Compound (11) wherein n is 2 in formula (1) can be produced by reacting compound (3) in the presence of an oxidizing agent.

[Wherein, R1, R2, R3, R4, R5, A1 and A2 represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include m-chloroperbenzoic acid or hydrogen peroxide water.
In the reaction, an oxidizing agent is usually used in a ratio of 2 to 5 mol with respect to 1 mol of the compound (3). Preferably, the oxidizing agent is used in a ratio of 2 to 3 moles with respect to 1 mole of the compound (3).
The reaction temperature of the reaction 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, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried, Compound (11) can be isolated by performing post-treatment operations such as concentration. The isolated compound (11) can be further purified by chromatography, recrystallization and the like.

(Production method 18)
Compound (11) in which n is 2 in formula (1) can be produced by reacting compound (10) in the presence of an oxidizing agent.

[Wherein, R1, R2, R3, R4, R5, A1 and A2 represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include m-chloroperbenzoic acid or hydrogen peroxide water.
In the reaction, the oxidizing agent is usually used at a ratio of 1 to 4 moles relative to 1 mole of the compound (10). Preferably, the oxidizing agent is used in a ratio of 1 to 2 moles relative to 1 mole of the compound (10).
The reaction temperature of the reaction 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, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried, Compound (11) can be isolated by performing post-treatment operations such as concentration. The isolated compound (11) can be further purified by chromatography, recrystallization and the like.

(Production Method 19) (Step (A-3), Step (B-3))
Compound (2) in which A1 is a sulfur atom in formula (1) can be produced by reacting compound (M22) in the presence of an acid according to step (A-3) or step (B-3). it can.

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, and halogens such as dichloromethane, chloroform, and chlorobenzene. Hydrocarbons and mixtures thereof.
Examples of the acid used for the reaction include sulfonic acids such as p-toluenesulfonic acid and polyphosphoric acid.
In the reaction, an acid is usually used at a ratio of 0.1 to 3 mol with respect to 1 mol of the compound (M22).
The reaction temperature of the reaction is usually in the range of 50 to 200 ° C. The reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the compound (2) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (2) can be further purified by chromatography, recrystallization and the like.

(Production method 20)
In formula (1), compound (12-a) wherein R5 is represented by -SH, compound (12-b) which is a disulfide compound of compound (12-a), compound (13) wherein R5 is represented by -SR7 The compound (14) wherein R5 is -S (O) mR7 can be produced, for example, by the following method.

[Wherein R1, R2, R3, R4, R7, A1, A2, n, m, V1 and L represent the same meaning as described above. ]
Step (22-1)
Compound (12-a) and / or compound (12-b) can be produced by reacting compound (7) with a thiolating agent in the presence of a catalyst.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aromatic hydrocarbons such as toluene and xylene, acid amides such as DMF and NMP, sulfoxides such as DMSO, and mixtures thereof.
Examples of the thiolating agent used in the reaction include sodium sulfide, sodium sulfide nonahydrate, and thiourea.
Examples of the catalyst used in the reaction include copper (I) chloride, copper (I) bromide, and copper (I) iodide.
This reaction can also be performed in presence of a base as needed.
Examples of the base used in the reaction include potassium carbonate, cesium carbonate, tripotassium phosphate, and triethylamine.
In the reaction, with respect to 1 mol of the compound (7), the thiolating agent is usually used in a proportion of 1 to 10 mol, and the catalyst is usually used in a proportion of 0.1 to 5 mol.
The reaction temperature of the reaction is usually in the range of 50 to 200 ° C. The reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (12-a) and / or the compound (12-b) is isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. be able to. The isolated compound (12-a) and / or compound (12-b) can be further purified by chromatography, recrystallization and the like.

Step (22-2)
Compound (13) can be produced by reacting compound (12-a) and / or compound (12-b) with compound (M23) 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 alcohols such as methanol and ethanol, ethers such as 1,4-dioxane, diethyl ether, THF and tert-butyl methyl ether, dichloromethane, chloroform, carbon tetrachloride, and 1,2. -Halogenated hydrocarbons such as dichloroethane and chlorobenzene, aromatic hydrocarbons such as toluene, benzene and xylene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, DMF, NMP, 1,3-dimethyl Examples thereof include aprotic polar solvents such as 2-imidazolidinone and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, water, and mixtures thereof.
Examples of the base used in the reaction include pyridine, picoline, 2,6-lutidine, diazabicycloundecene (hereinafter referred to as DBU), 1,5-diazabicyclo [4.3.0] -5-nonene, and the like. And nitrogen-containing heterocyclic compounds, tertiary amines such as triethylamine and N-ethyldiisopropylamine, and inorganic bases such as tripotassium phosphate, potassium carbonate, sodium hydride, sodium hydroxide and potassium hydroxide.
In the reaction, with respect to 1 mol of the compound (12-a) and / or the compound (12-b), the compound (M23) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 5 mol. It is done.
The reaction temperature of the reaction is usually in the range of 0 to 120 ° C. The reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (13) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (13) can be further purified by chromatography, recrystallization and the like.

Step (22-3)
In compound (14), a compound wherein m is 1 or 2 can be produced by subjecting compound (13) to an oxidation reaction.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include m-chloroperbenzoic acid or hydrogen peroxide water.
The reaction can be carried out in the presence of a catalyst as necessary.
Examples of the catalyst used in the reaction include sodium tungstate.
In the reaction, with respect to 1 mole of the compound (13), the oxidizing agent is usually used at a ratio of 1 to 5 moles.
The reaction temperature of the reaction 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, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried, Compound (14) can be isolated by post-treatment such as concentration. The isolated compound (14) can be further purified by chromatography, recrystallization and the like.

(Production method 21)
In the formula (1), the compound (15) in which R5 is —OR7 can be produced, for example, by the following method.

[Wherein, R1, R2, R3, R4, R7, A1, A2, V1, and n represent the same meaning as described above. ]
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, DMF, Examples include acid amides such as NMP, sulfoxides such as DMSO, and mixtures thereof.
Examples of the base used in the reaction include alkali metal or alkaline earth metal hydrides such as sodium hydride, potassium hydride and calcium hydride, inorganic bases such as sodium carbonate, potassium carbonate and cesium carbonate, or triethylamine. An organic base is mentioned.
This reaction can also be performed by adding a copper compound as necessary.
Examples of the copper compound used for the reaction include copper, copper (I) iodide, copper (I) bromide, and copper (I) chloride.
In the reaction, the compound (M24) is usually used in a proportion of 1 to 5 mol and the base is usually used in a proportion of 1 to 3 mol with respect to 1 mol of the compound (7).
The reaction temperature of the reaction is usually in the range of 20 to 250 ° C. The reaction time is usually in the range of 0.1 to 48 hours. After completion of the reaction, the reaction mixture is poured into water and then extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture The collected solid can be collected by filtration to isolate compound (15). The isolated compound (15) can be further purified by recrystallization, chromatography or the like.

(Manufacturing method 22) (Process (A-1))
Compound (2) in which A1 is a sulfur atom in formula (1) can be produced by reacting compound (M18) and compound (M2) according to step (A-1).

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, tert-butyl methyl ether, ethylene glycol dimethyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, pyridine, quinoline and the like Examples thereof include nitrogen-containing aromatic compounds and mixtures thereof.
Examples of the dehydrating condensing agent used in the reaction include WSC, carbodiimides such as 1,3-dicyclohexylcarbodiimide, BOP reagent and the like.
This reaction can also be performed by adding a catalyst as needed.
Examples of the catalyst used in the reaction include HOBt.
In the reaction, with respect to 1 mole of the compound (M18), the compound (M2) is usually in a proportion of 1 to 3 moles, the dehydrating condensing agent is usually in a proportion of 1 to 5 moles, and the catalyst is usually in a range of 0.01 to 0.1. Used in molar proportions.
The reaction temperature of the reaction is usually in the range of 30 to 200 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (2) can be isolated 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. The isolated compound (2) can be further purified by chromatography, recrystallization and the like.
Moreover, it can replace with a compound (M2) and can use a compound (M4) and can manufacture a compound (2) according to the said method according to a process (B-1).
When the compound (M4) is used, it is usually carried out without adding a dehydrating condensation agent. A base can be added as necessary.
Examples of the base include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
In the reaction, with respect to 1 mol of the compound (M18), the compound (M4) is usually used in a proportion of 1 to 3 mol, and the base is usually used in a proportion of 1 to 10 mol.

(Production Method 23) (Production Method D)
Compound (2) in which A1 is a sulfur atom in formula (1) can be produced by reacting compound (M7) with a sulfurizing agent according to (Production Method D).

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
The reaction is performed in the presence or absence of a solvent.
Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, tert-butyl methyl ether, and diglyme, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Examples thereof include hydrocarbons, hydrocarbons such as toluene, benzene and xylene, nitriles such as acetonitrile, pyridines such as pyridine, picoline and lutidine, and mixtures thereof.
Examples of the sulfurizing agent used in the reaction include nilin pentasulfide, Lawesson's reagent (2,4-bis- (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide) and the like. Can be mentioned.
The amount of the sulfiding agent used for the reaction is usually 1 mol or more per 1 mol of the compound (M7).
The reaction temperature of the reaction is usually in the range of 0 ° C. to 200 ° C., and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, the reaction mixture is poured into water and then extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture The collected solid can be collected by filtration to isolate compound (2). The isolated compound (2) can be further purified by recrystallization, chromatography or the like.

The intermediate of the present invention can be produced, for example, by the following method.
(Intermediate production method 1)
Compound (M12) can be produced by the following method.

[Wherein R5, R6 and A2 represent the same meaning as described above. ]
(Process 1)
Compound (M26) can be produced by reacting compound (M25) in the presence of a nitrating agent.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include halogenated hydrocarbons such as dichloromethane and chloroform, acetic acid, concentrated sulfuric acid, concentrated nitric acid, water, and mixtures thereof.
An example of the nitrating agent used in the reaction is concentrated nitric acid.
In the reaction, the nitrating agent is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (M25).
The reaction temperature is usually in the range of −10 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M26) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M26) can be further purified by chromatography, recrystallization and the like.

(Process 2)
Compound (M12) can be produced by reacting compound (M26) with hydrogen in the presence of a hydrogenation catalyst.
The reaction is usually performed in the presence of a solvent under a hydrogen atmosphere of 1 to 100 atm.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, water And mixtures thereof.
Examples of the hydrogenation catalyst used in the reaction include transition metal compounds such as palladium carbon, palladium hydroxide, Raney nickel, and platinum oxide.
In the reaction, with respect to 1 mole of the compound (M26), hydrogen is usually used at a ratio of 3 moles, and the hydrogenation catalyst is usually used at a ratio of 0.001 to 0.5 moles.
This reaction can also be carried out by adding an acid (such as a base) as necessary.
The reaction temperature of the reaction is usually in the range of −20 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M12) can be isolated by performing post-treatment operations such as filtration of the reaction mixture, extraction with an organic solvent, if necessary, and drying and concentration of the organic layer. The isolated compound (M12) can be further purified by chromatography, recrystallization and the like.

(Intermediate Production Method 2) (Step (A-2))
Compound (M13) can be produced by reacting compound (M12) and compound (M2) in the presence of a dehydration condensing agent according to step (A-2).

[Wherein, R 1, R 2, R 3, R 4, R 5, R 6, A 2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, pyridine, quinoline and the like Examples thereof include nitrogen-containing aromatic compounds and mixtures thereof.
Examples of the dehydrating condensing agent used in the reaction include WSC, carbodiimides such as 1,3-dicyclohexylcarbodiimide, and BOP reagent.
In the reaction, with respect to 1 mol of the compound (M12), the compound (M2) is usually used in a proportion of 1 to 3 mol, and the dehydrating condensing agent is usually used in a proportion of 1 to 5 mol.
The reaction temperature of the reaction is usually in the range of 0 to 140 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M13) can be isolated by performing post-treatment operations such as pouring water into the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M13) can be further purified by chromatography, recrystallization and the like.

(Intermediate Production Method 3) (Step (B-2))
Compound (M13) can be produced by reacting compound (M12) and compound (M4) in the presence of a base according to step (B-2).

[Wherein, R 1, R 2, R 3, R 4, R 5, R 6, A 2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, and mixtures thereof It is done.
Examples of the base include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
In the reaction, with respect to 1 mol of the compound (M12), the compound (M4) is usually used in a proportion of 1 to 3 mol, and the base is usually used in a proportion of 1 to 10 mol.
The reaction temperature of the reaction is usually in the range of −20 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M13) can be isolated by performing post-treatment operations such as pouring water into the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M13) can be further purified by chromatography, recrystallization and the like.

(Intermediate production method 4)
Compound (M15) can be produced by the following method.

[Wherein R5 and A2 represent the same meaning as described above. ]
(Process 1)
Compound (M28) can be produced by reacting compound (M27) in the presence of a nitrating agent.
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 chloroform, acetic acid, concentrated sulfuric acid, concentrated nitric acid, water, and mixtures thereof.
An example of the nitrating agent used in the reaction is concentrated nitric acid.
In the reaction, the nitrating agent is usually used at a ratio of 1 to 3 moles relative to 1 mole of the compound (M27).
The reaction temperature is usually in the range of −10 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M28) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M28) can be further purified by chromatography, recrystallization and the like.

(Process 2)
Compound (M15) can be produced by reacting compound (M28) with hydrogen in the presence of a hydrogenation catalyst.
The reaction is usually performed in the presence of a solvent under a hydrogen atmosphere of 1 to 100 atm.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, water And mixtures thereof.
Examples of the hydrogenation catalyst used in the reaction include transition metal compounds such as palladium carbon, palladium hydroxide, Raney nickel, and platinum oxide.
In the reaction, hydrogen is usually used in a proportion of 3 mol and a hydrogenation catalyst is usually used in a proportion of 0.001 to 0.5 mol with respect to 1 mol of the compound (M28).
This reaction can also be carried out by adding an acid (such as a base) as necessary.
The reaction temperature of the reaction is usually in the range of −20 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M15) can be isolated by performing post-treatment operations such as filtration of the reaction mixture, extraction with an organic solvent, if necessary, and drying and concentration of the organic layer. The isolated compound (M15) can be further purified by chromatography, recrystallization and the like.

(Intermediate Production Method 5) (Step (C-2))
Compound (M16) can be produced by reacting compound (M15) with compound (M5) according to step (C-2).

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include alcohols such as methanol and ethanol, ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, and the like. These mixtures are mentioned.
In the reaction, compound (M5) is usually used at a ratio of 1 to 3 mol per 1 mol of compound (M15).
This reaction can also be performed by adding an acid, a base, or the like, if necessary.
The reaction temperature of the reaction is usually in the range of 0 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M16) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, drying and concentration. The isolated compound (M16) can be further purified by chromatography, recrystallization and the like.

(Intermediate Production Method 6) (Step (A-2))
Compound (M17) can be produced by reacting compound (M15) and compound (M2) in the presence of a dehydration condensing agent according to step (A-2).

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, pyridine, quinoline and the like Examples thereof include nitrogen-containing aromatic compounds and mixtures thereof.
Examples of the dehydrating condensing agent used in the reaction include WSC, carbodiimides such as 1,3-dicyclohexylcarbodiimide, and BOP reagent.
In the reaction, with respect to 1 mol of the compound (M15), the compound (M2) is usually used in a proportion of 1 to 3 mol, and the dehydrating condensing agent is usually used in a proportion of 1 to 5 mol.
The reaction temperature of the reaction is usually in the range of 0 to 140 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M17) can be isolated by performing post-treatment operations such as pouring water into the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M17) can be further purified by chromatography, recrystallization and the like.

(Intermediate Production Method 7) (Step (B-2))
Compound (M17) can be produced by reacting compound (M15) and compound (M4) in the presence of a base according to step (B-2).

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, and mixtures thereof It is done.
Examples of the base used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine. It is done.
In the reaction, with respect to 1 mol of the compound (M15), the compound (M4) is usually used in a proportion of 1 to 3 mol, and the base is usually used in a proportion of 1 to 10 mol.
The reaction temperature of the reaction is usually in the range of −20 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M17) can be isolated by performing post-treatment operations such as pouring water into the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M17) can be further purified by chromatography, recrystallization and the like.

(Intermediate production method 8)
Compound (M18) can be produced by the following method.

[Wherein R5 and A2 represent the same meaning as described above. ]
(Process 1)
Compound (M30) can be produced by reacting compound (M29) with thiourea 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 alcohols such as methanol and ethanol, water, and mixtures thereof.
Examples of the base used for the reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
In the reaction, with respect to 1 mol of the compound (M29), thiourea is usually used in a proportion of 0.5 to 3 mol, and the base is usually used in a proportion of 1 to 10 mol.
The reaction temperature of the reaction is usually in the range of 0 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M30) can be isolated by post-treatment such as addition of an acid to the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M30) can also be purified by chromatography, recrystallization and the like.

(Process 2)
Compound (M18) can be produced by subjecting compound (M30) to a reduction reaction.
The reduction reaction can be performed in the presence of a reducing agent such as iron powder or zinc powder; an acid such as hydrochloric acid or acetic acid; and water.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, Examples thereof include acid amides such as DMF and NMP, and mixtures thereof.
In the reaction, the reducing agent is usually used in a proportion of 3 to 10 mol per 1 mol of the compound (M30).
The reaction temperature is usually in the range of 0 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M18) can be isolated by performing post-treatment operations such as addition of water to the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M18) can also be purified by chromatography, recrystallization, and the like.

(Intermediate production method 9)
In compound (M10), compound (M33) wherein A1 is -NR6- can be produced by reacting compound (M12) with compound (M31) in the presence of a base.

[Wherein R 1, R 2, R 3, R 4, R 5, R 6, A 2 and V 2 represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the base used in the reaction include hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, carbonates such as sodium carbonate and potassium carbonate, sulfites such as sodium sulfite and potassium sulfite, and mixtures thereof.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, pyridine, quinoline and the like Examples thereof include nitrogen-containing aromatic compounds and mixtures thereof.
In the reaction, with respect to 1 mol of the compound (M12), the compound (M31) is usually used in a proportion of 1 to 3 mol, and the base is usually used in a proportion of 1 to 5 mol.
The reaction temperature of the reaction is usually in the range of 30 to 200 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M33) can be isolated by performing post-treatment operations such as pouring water into the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M33) can be further purified by chromatography, recrystallization and the like.

(Intermediate Production Method 10) (Step (E-1))
In compound (M10), compound (M33) in which A1 is —NR6- is obtained by reacting compound (M12) and compound (M8) in the presence of a dehydration condensing agent according to step (E-1). Can be manufactured.

[Wherein R 1, R 2, R 3, R 4, R 5, R 6, A 2 and V 2 represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, tert-butyl methyl ether, ethylene glycol dimethyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, pyridine, quinoline and the like Examples thereof include nitrogen-containing aromatic compounds and mixtures thereof.
Examples of the dehydrating condensing agent used in the reaction include WSC, carbodiimides such as 1,3-dicyclohexylcarbodiimide, BOP reagent and the like.
This reaction can also be performed by adding a catalyst as needed.
Examples of the catalyst used in the reaction include HOBt.
In the reaction, with respect to 1 mol of the compound (M12), the compound (M8) is usually in a proportion of 1 to 3 mol, the dehydrating condensing agent is usually in a proportion of 1 to 5 mol, and the catalyst is usually in a proportion of 0.01 to 0.1. Used in molar proportions.
The reaction temperature of the reaction is usually in the range of 30 to 200 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M33) can be isolated by performing post-treatment operations such as pouring water into the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M33) can be further purified by chromatography, recrystallization and the like.

(Intermediate Production Method 11) (Step (E-3))
In compound (M10), compound (M33) wherein A1 is -NR6- can be produced by subjecting compound (M32) to dehydration condensation according to step (E-3).

[Wherein R 1, R 2, R 3, R 4, R 5, R 6, A 2 and V 2 represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, methanol, ethanol, propanol , Alcohols such as butanol and pentanol, and mixtures thereof.
In the reaction, an acid or a dehydrating agent can be used as necessary. Examples of the acid used in the reaction include sulfonic acids such as p-toluenesulfonic acid, and carboxylic acids such as acetic acid. Examples of the dehydrating agent used in the reaction include phosphorus oxychloride, acetic anhydride, trifluoroacetic anhydride, and the like. Can be mentioned.
In the reaction, with respect to 1 mol of the compound (M32), an acid or a dehydrating agent is usually used at a ratio of 1 mol to 10 mol.
The reaction temperature of the reaction is usually in the range of 30 to 200 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M33) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M33) can be further purified by chromatography, recrystallization and the like.

(Intermediate production method 12) (Step (E-3))
In compound (M10), compound (M33) in which A1 is —NR6- can be produced by reacting compound (M32) in the presence of a base according to step (E-3).

[Wherein R 1, R 2, R 3, R 4, R 5, R 6, A 2 and V 2 represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, methanol, ethanol, propanol , Butanol, tert-butanol, pentanol and the like, and mixtures thereof.
Examples of the base used for the reaction include tripotassium phosphate.
In the reaction, with respect to 1 mol of the compound (M32), the base is generally used at a ratio of 1 mol to 10 mol.
The reaction temperature of the reaction is usually in the range of 30 to 200 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M33) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M33) can be further purified by chromatography, recrystallization and the like.

(Intermediate production method 13) (Step (E-2))
Compound (M32) can be produced by reacting compound (M12) and compound (M8) in the presence of a dehydration condensing agent according to step (E-2).

[Wherein R 1, R 2, R 3, R 4, R 5, R 6, A 2 and V 2 represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, pyridine, quinoline and the like Examples thereof include nitrogen-containing aromatic compounds and mixtures thereof.
Examples of the dehydrating condensing agent used in the reaction include WSC, carbodiimides such as 1,3-dicyclohexylcarbodiimide, and BOP reagent.
In the reaction, with respect to 1 mol of the compound (M12), the compound (M8) is usually used in a proportion of 1 to 3 mol, and the dehydrating condensing agent is usually used in a proportion of 1 to 5 mol.
The reaction temperature of the reaction is usually in the range of 0 to 140 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M32) can be isolated by performing post-treatment operations such as pouring water into the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M32) can be further purified by chromatography, recrystallization and the like.

(Intermediate production method 14)
Compound (M32) can be produced by reacting compound (M12) with compound (M34) in the presence of a base.

[Wherein R 1, R 2, R 3, R 4, R 5, R 6, A 2 and V 2 represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, and mixtures thereof It is done.
Examples of the base include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
In the reaction, with respect to 1 mol of the compound (M12), the compound (M34) is usually used in a proportion of 1 to 3 mol, and the base is usually used in a proportion of 1 to 10 mol.
The reaction temperature of the reaction is usually in the range of −20 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M32) can be isolated by performing post-treatment operations such as pouring water into the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M32) can be further purified by chromatography, recrystallization and the like.

(Intermediate production method 15)
Among compounds (M5), compound (M37) in which n is 0 can be produced by the following method.

[Wherein, R1, R2, R3, R4 and V2 represent the same meaning as described above. ]
(Step I15-1)
Compound (M36) can be produced by reacting compound (M35) with compound (M20) 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 ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, DMF, Examples include acid amides such as NMP, sulfoxides such as DMSO, and mixtures thereof.
Examples of the base used for the reaction include alkali metal hydrides such as sodium hydride.
In the reaction, with respect to 1 mol of the compound (M35), the compound (M20) 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.
The reaction temperature of the reaction is usually in the range of 0 to 150 ° C. The reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (M36) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M36) can be further purified by chromatography, recrystallization and the like.

(Step I15-2)
Compound (M37) can be produced by subjecting compound (M36) to a reduction reaction.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, and halogenated carbonization such as dichloromethane and chloroform. Examples include hydrogens and mixtures thereof.
Examples of the reducing agent used in the reaction include diisobutylaluminum hydride.
In the reaction, the reducing agent is usually used at a ratio of 1 to 2 moles relative to 1 mole of the compound (M36).
The reaction temperature of the reaction is usually in the range of −20 to 100 ° C. The reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (M37) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M37) can be further purified by chromatography, recrystallization and the like.

(Intermediate Production Method 16)
Among compounds (M5), compound (M37) in which n is 0 can be produced by reacting compound (M38) and compound (M20) in the presence of a base.

[Wherein R1, R2, R3, R4 and V2 represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, DMF, Examples thereof include acid amides such as NMP, sulfoxides such as DMSO, and mixtures thereof.
Examples of the base used for the reaction include alkali metal hydrides such as sodium hydride.
In the reaction, with respect to 1 mol of the compound (M38), the compound (M20) 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.
The reaction temperature of the reaction is usually in the range of 0 to 150 ° C. The reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (M37) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M37) can be further purified by chromatography, recrystallization and the like.

(Intermediate Production Method 17)
Among the compounds (M2), the compound (M39) in which n is 0 can be produced by hydrolyzing the compound (M36) in the presence of a base, and the compound (M41) in which n is 1 or 2. ) Can be produced by the following method.

[Wherein R 1, R 2, R 3 and R 4 represent the same meaning as described above, and r represents 1 or 2. ]
(Step I17-1)
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, alcohols such as methanol and ethanol, water, and a mixture thereof.
Examples of the base used for the reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
In the reaction, the base is generally used at a ratio of 1 to 10 mol per 1 mol of the compound (M36).
The reaction temperature of the reaction is usually in the range of 0 to 120 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M39) can be isolated by performing post-treatment operations such as acidification of the reaction mixture, extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. . The isolated compound (M39) can be further purified by chromatography, recrystallization and the like.

(Process I17-2)
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include m-chloroperbenzoic acid or hydrogen peroxide water.
The reaction can be carried out in the presence of a catalyst as necessary.
Examples of the catalyst used for the reaction include sodium tungstate.
In the reaction, with respect to 1 mole of the compound (M36), the oxidizing agent is usually used at a ratio of 1 to 5 moles.
The reaction temperature of the reaction 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, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried, The compound (M40) can be isolated by performing post-treatment operations such as concentration. The isolated compound (M40) can be further purified by chromatography, recrystallization and the like.

(Step I17-3)
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, alcohols such as methanol and ethanol, water, and a mixture thereof.
Examples of the base used for the reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
In the reaction, the base is usually used at a ratio of 1 to 10 mol per 1 mol of the compound (M40).
The reaction temperature of the reaction is usually in the range of 0 to 120 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the reaction mixture is acidified, and then the compound (M41) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. . The isolated compound (M41) can be further purified by chromatography, recrystallization, and the like.

(Process I17-4)
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include halogenated hydrocarbons such as dichloromethane and chloroform, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include m-chloroperbenzoic acid or hydrogen peroxide water.
The reaction can be carried out in the presence of a catalyst as necessary.
Examples of the catalyst used for the reaction include sodium tungstate.
In the reaction, with respect to 1 mol of the compound (M39), the oxidizing agent is usually used at a ratio of 1 to 5 mol.
The reaction temperature of the reaction 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, the reaction mixture is extracted with an organic solvent, and the organic layer is washed with an aqueous solution of a reducing agent (for example, sodium sulfite, sodium thiosulfate) or an aqueous solution of a base (for example, sodium bicarbonate) as necessary, dried, The compound (M41) can be isolated by performing post-treatment operations such as concentration. The isolated compound (M41) can be further purified by chromatography, recrystallization, and the like.

(Intermediate Production Method 18)
Among compounds (M2), compound (M39) in which n is 0 can be produced by subjecting compound (M36) to a hydrolysis reaction in the presence of an acid.

[Wherein R1, R2, R3 and R4 have the same meaning as described above. ]
The reaction is usually carried out using an aqueous acid solution as a solvent.
Examples of the acid used for the reaction include mineral acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid, and carboxylic acids such as acetic acid and trifluoroacetic acid.
The reaction temperature of the reaction is usually in the range of 0 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M39) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M39) can be further purified by chromatography, recrystallization and the like.

(Intermediate Production Method 19)
Compound (M4) can be produced by chlorinating compound (M2) in the presence of a chlorinating agent.

[Wherein R1, R2, R3, R4 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, and halogenated carbonization such as dichloromethane and chloroform. Examples include hydrogens and mixtures thereof.
Examples of the chlorinating agent used in the reaction include thionyl chloride and oxalyl dichloride.
In the reaction, the chlorinating agent is usually used at a ratio of 1 to 5 mol per 1 mol of the compound (M2).
The reaction temperature of the reaction is usually in the range of 0 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M4) can be isolated by removing the solvent.

(Intermediate production method 20)
Among the compounds (M12), the compound (M45) in which A2 is a nitrogen atom can be produced, for example, by the following method.

[Wherein, R5 and R6 represent the same meaning as described above, and Xg represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom. ]
(Process I20-1)
Compound (M43) can be produced by reacting compound (M42) with compound (M46).
The reaction is usually performed in the presence or absence of a solvent.
Examples of the solvent used in the reaction include water, alcohols such as methanol and ethanol, ethers such as 1,4-dioxane, diethyl ether and THF, esters such as ethyl acetate and butyl acetate, dichloromethane, chloroform and tetrachloride. Examples include carbon, halogenated hydrocarbons such as 1,2-dichloroethane, nitriles such as acetonitrile, aprotic polar solvents such as DMF, NMP, and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof. It is done.
This reaction can also be performed by adding a base as necessary.
Examples of the base used in the reaction include nitrogen-containing heterocyclic compounds such as pyridine, picoline, 2,6-lutidine, DBU, 1,5-diazabicyclo [4.3.0] -5-nonene, triethylamine, and N-ethyl. Tertiary amines such as diisopropylamine, and inorganic bases such as potassium carbonate, cesium carbonate, sodium hydroxide and the like.
The compound (M46) is usually used at a ratio of 1 to 5 mol per 1 mol of the compound (M42).
The reaction temperature of the reaction is usually in the range of 0 to 200 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the reaction mixture is poured into water and then extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture The collected solid can be collected by filtration to isolate the compound (M43). The isolated compound (M43) can be further purified by recrystallization, chromatography or the like.

(Process I20-2)
Compound (M44) can be produced by reacting compound (M43) with a halogenating agent.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used for the reaction include water, acetic acid, 1,4-dioxane, diethyl ether, THF and other ethers, ethyl acetate, butyl acetate and other esters, dichloromethane, chloroform, carbon tetrachloride, 1,2- Examples thereof include halogenated hydrocarbons such as dichloroethane, nitriles such as acetonitrile, aprotic polar solvents such as DMF and NMP, and mixtures thereof.
Examples of the halogenating agent used in the reaction include chlorinating agents such as N-chlorosuccinimide and chlorine, brominating agents such as N-bromosuccinimide and bromine, and chlorinating agents such as N-iodosuccinimide and iodine.
The halogenating agent is usually used in a proportion of 1 to 3 mol per 1 mol of the compound (M43).
The reaction temperature of the reaction is usually in the range of −10 to 100 ° C., and the reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the reaction mixture is poured into water and then extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture The collected solid can be collected by filtration to isolate the compound (M44). The isolated compound (M44) can be further purified by recrystallization, chromatography or the like.

(Process I20-3)
Compound (M45) can be produced by reacting compound (M44) with an aminating agent in the presence of a copper compound.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include water, alcohols such as methanol and ethanol, ethers such as 1,4-dioxane, diethyl ether and THF, esters such as ethyl acetate and butyl acetate, dichloromethane, chloroform and tetrachloride. Carbon, halogenated hydrocarbons such as 1,2-dichloroethane, nitriles such as acetonitrile, aprotic polar solvents such as DMF, NMP, and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof Can be mentioned.
Examples of the aminating agent used in the reaction include ammonia, aqueous ammonia, and lithium amide.
Examples of the copper compound used in the reaction include copper, copper (I) iodide, copper (I) oxide, copper (II) oxide, acetylacetone copper (II), copper acetate (II), and copper (II) sulfate. It is done.
This reaction can also be performed by adding a ligand as necessary.
Examples of the ligand used in the reaction include acetylacetone, salen, and phenanthroline.
This reaction can also be performed by adding a base as necessary.
Examples of the base used in the reaction include nitrogen-containing heterocyclic compounds such as pyridine, picoline, 2,6-lutidine, DBU, 1,5-diazabicyclo [4.3.0] -5-nonene, triethylamine, and N-ethyl. Examples include tertiary amines such as diisopropylamine, and inorganic bases such as tripotassium phosphate, potassium carbonate, cesium carbonate, and sodium hydroxide.
The aminating agent is usually used in a proportion of 1 to 5 mol, and the copper compound is usually used in a proportion of 0.02 to 0.5 mol per 1 mol of the compound (M44). Is used in a proportion of 0.02 to 2 mol, and a base is used in a proportion of 1 to 5 mol if necessary.
The reaction temperature of the reaction is usually in the range of 30 to 200 ° C., and the reaction time is usually in the range of 0.1 to 48 hours.
After completion of the reaction, the reaction mixture is poured into water and then extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is poured into water and the resulting solid is collected by filtration; or formed in the reaction mixture The collected solid can be collected by filtration to isolate compound (M45). The isolated compound (M45) can be further purified by recrystallization, chromatography or the like.

(Intermediate Production Method 21) (Step (A-2))
Compound (M22) can be produced by reacting compound (M18) and compound (M2) in the presence of a dehydration condensing agent according to step (A-2).

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, pyridine, quinoline and the like Examples thereof include nitrogen-containing aromatic compounds and mixtures thereof.
Examples of the dehydrating condensing agent used in the reaction include WSC, carbodiimides such as 1,3-dicyclohexylcarbodiimide, and BOP reagent.
In the reaction, with respect to 1 mol of the compound (M18), the compound (M2) is usually used in a proportion of 1 to 3 mol, and the dehydrating condensing agent is usually used in a proportion of 1 to 5 mol.
The reaction temperature of the reaction is usually in the range of 0 to 140 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M22) can be isolated by performing post-treatment operations such as water addition to the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M22) can be further purified by chromatography, recrystallization and the like.

(Intermediate Production Method 22) (Step (B-2))
Compound (M22) can be produced by reacting compound (M18) and compound (M4) in the presence of a base according to step (B-2).

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, and mixtures thereof It is done.
Examples of the base used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine. It is done.
In the reaction, with respect to 1 mol of the compound (M18), the compound (M4) is usually used in a proportion of 1 to 3 mol, and the base is usually used in a proportion of 1 to 10 mol.
The reaction temperature of the reaction is usually in the range of −20 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M22) can be isolated by performing post-treatment operations such as water addition to the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M22) can be further purified by chromatography, recrystallization and the like.

(Intermediate Production Example 23) (Step (E-1))
Compound (M47) in which A1 is an oxygen atom in compound (M10) can be produced by reacting compound (M15) with compound (M8) according to step (E-1).

[Wherein R 1, R 2, R 3, R 4, R 5, A 2, n and V 2 represent the same meaning as described above. ]
Compound (M47) can be produced according to the method described in (Production Method 6) using compound (M8) in place of compound (M2).

(Intermediate Production Example 24) (Step (E-2))
Compound (M48) in which A1 is an oxygen atom in compound (M9) can be produced by reacting compound (M15) with compound (M8) according to step (E-2). In addition, compound (M49) in which A1 is a sulfur atom in compound (M9) can be produced by reacting compound (M18) with compound (M8).

[Wherein, R1, R2, R3, R4, R5, A2 and V2 represent the same meaning as described above. ]
Compound (M48) can be produced according to the method described in (Intermediate Production Method 6) using Compound (M8) instead of Compound (M2).
Compound (M49) can be produced according to the method described in (Intermediate Production Method 21) using Compound (M8) instead of Compound (M2).

(Intermediate Production Example 25) (Step (E-3))
Compound (M47) wherein A1 is an oxygen atom in compound (M10) can be produced by cyclizing compound (M48) according to step (E-3). Moreover, the compound (M50) in which A1 is a sulfur atom in the compound (M10) can be produced by cyclizing the compound (M49) according to the step (E-3).

[Wherein, R1, R2, R3, R4, R5, A2 and V2 represent the same meaning as described above. ]
Using compound (M48) instead of compound (M17), compound (M47) can be produced according to the method described in (Production Method 8) or (Production Method 9).
The compound (M50) can be produced according to the method described in (Production Method 21) using the compound (M49) instead of the compound (M22).

(Intermediate Production Method 26) (Step (F-1))
Compound (M11) can be produced by reacting compound (M10) with sodium sulfide, sodium hydrogen sulfide or hydrogen sulfide according to step (F-1).

[Wherein, R 1, R 2, R 3, R 4, R 5, A 1, A 2 and V 2 represent the same meaning as described above. ]
Compound (M11) can be produced according to the method described in (Production Process 16) using sodium sulfide, sodium hydrogen sulfide or hydrogen sulfide instead of compound (M20).
When sodium sulfide or sodium hydrogen sulfide is used, it is usually carried out without adding a base.

(Intermediate Production Method 27) (Production Method D)
Compound (M7) can be produced by reacting compound (M51) with compound (M2).

[Wherein, R1, R2, R3, R4, R5, A2 and n represent the same meaning as described above. ]
(Process I27-1)
Compound (M51) can be produced by subjecting compound (M29) to a reduction reaction.
The reduction reaction can be performed in the presence of a reducing agent such as iron powder or zinc powder; an acid such as hydrochloric acid or acetic acid; and water.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, esters such as ethyl acetate and butyl acetate, alcohols such as methanol and ethanol, Examples thereof include acid amides such as DMF and NMP, and mixtures thereof.
In the reaction, the reducing agent is usually used in a proportion of 3 to 10 mol per 1 mol of the compound (M29).
The reaction temperature is usually in the range of 0 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M51) can be isolated by post-treatment such as addition of water to the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M51) can also be purified by chromatography, recrystallization, and the like.
(Process I27-2)
The reaction is usually performed in the presence or absence of a solvent.
Examples of the solvent used in the reaction include ethers such as THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aliphatic hydrocarbons such as hexane, heptane, and octane, and aromatics such as toluene and xylene. Group hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, acid amides such as DMF and NMP, sulfoxides such as DMSO, pyridine, quinoline and the like Examples thereof include nitrogen-containing aromatic compounds and mixtures thereof.
Examples of the dehydrating condensing agent used in the reaction include WSC, carbodiimides such as 1,3-dicyclohexylcarbodiimide, and BOP reagent.
In the reaction, with respect to 1 mol of the compound (M51), the compound (M2) is usually used in a proportion of 1 to 3 mol, and the dehydrating condensing agent is usually used in a proportion of 1 to 5 mol.
The reaction temperature of the reaction is usually in the range of 0 to 140 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M7) can be isolated by performing post-treatment operations such as pouring water into the reaction mixture, extraction with an organic solvent, and drying and concentration of the organic layer. The isolated compound (M7) can be further purified by chromatography, recrystallization and the like.
Moreover, it can replace with a compound (M2) and a compound (M4) can be used, and a compound (M7) can also be manufactured according to the said method.
When the compound (M4) is used, it is usually carried out without adding a dehydrating condensing agent. A base can be added as necessary.
Examples of the base include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
In the reaction, with respect to 1 mol of the compound (M51), the compound (M4) is usually used in a proportion of 1 to 3 mol, and the base is usually used in a proportion of 1 to 10 mol.

(Intermediate Production Method 28)
Compound (M1) can be produced by reacting compound (M52) with an aminating agent.

[Wherein, Xg, R5, A1 and A2 represent the same meaning as described above. ]
Compound (M1) can be produced according to the method described in Step (I20-3) of (Intermediate Production Method 20) using Compound (M52) instead of Compound (M44).

Next, specific examples of the present condensed heterocyclic compound are shown below. In the table, R1 to R5, A1, A2, and n represent symbols in the compound represented by the formula (1).

(In the above [Table 1] to [Table 4], Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, and CycPr represents a cyclopropyl group.)

In the present invention, the fused heterocyclic compound can be used as it is, but usually, the fused heterocyclic compound and an inert carrier are mixed, and if necessary, a surfactant or other formulation adjuvant. Is added to an emulsion, flowable agent, wettable powder, powder or the like.
The amount of the present condensed heterocyclic compound in the preparation containing the present condensed heterocyclic compound is usually in the range of 01% to 70% by weight, preferably 1 to 60% by weight, more preferably 5 to 50% by weight.

Examples of the inert carrier used for formulation include a solid carrier and a liquid carrier. Examples of the solid support include clays (kaolin clay, diatomaceous earth, bentonite, fusami clay, acidic clay), synthetic hydrous silicon oxide, talc, ceramic, 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, polyethylene terephthalate, etc.) Polyester resin, nylon resin such as nylon-6, nylon-11, nylon-66, polyamide resin, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-propylene copolymer).

Examples of liquid carriers 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 (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), sulfoxides (dimethylsulfoxide, etc.), propylene carbonate and vegetable oil (Soybean oil, cottonseed oil, etc.).

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

Examples of other formulation adjuvants 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).

The harmful arthropod that can be controlled by the method of the present invention is a plant seed treated with the present condensed heterocyclic compound or a pest that damages the plant body after the plant seed germinates. Examples of such harmful arthropods include harmful insects, and specifically include the following.

Hemiptera pests: Loondelphax striatellus, Japanese brown planthopper (Nilaparvata lugens), Japanese green planthopper (Sogellaella fursifera), etc .; ), Radish aphids (Brevicoryne brassicae), tulip beetle aphids (Macrosiphum euphorbiae), potato beetle aphids (Aulacorthum solani), wheat beetle aphids (Rhopalosiphumpa) Shi class, order Hemiptera (Nezara antennata), bombardier helicopter stink bug (Riptortus clavetus), spider helicopter bug (Leptocorisa chinensis), thorns Shirahoshi bug (Eysarcoris parvus), stink bugs such as brown marmorated stink bug (Halyomorpha mista), greenhouse whitefly (Trialeurodes vaporariorum ), Whiteflies such as tobacco whitefly (Bemisia tabaci).

Lepidoptera: rice stem borer (Chilo suppressalis), Sankameiga (Tryporyza incertulas), leaf roller (Cnaphalocrocis medinalis), Watanomeiga (Notarcha derogata), Indian meal moth (Plodia interpunctella), the European corn borer (Ostrinia furnacalis), high Madara Roh moth (Hellula undalis), etc. Japanese medusa, Spodoptera litra, Spodoptera exigua, Pseudoteria sepata, Mamestra brassicae, Atamara tis ipsilon, Tamiaginuawaba (Plusia nigrisigna), Trichopulsia spp., Heliotis spp., Helicoberpa spp. Suga, such as Ponella xylostella.

Thrips of the order Thrips thrips (Franklinella occidentalis), Thrips palmi, etc.

Diptera: seedcorn maggot (Delia platura), onion maggot (Delia antiqua) Anthomyiidae such as, rice leafminer (Agromyza oryzae), rice Hime leafminer (Hydrellia griseola), tomato leafminer, (Liriomyza sativae), legume leafminer (Liriomyza trifolii) , Leafworms such as Chlamatomya horticola, and leafworms such as Chlorops oryzae.

Coleoptera pests: Western Corn Rootworm (Diabrotica virgifera virgifera), corn rootworm such as southern corn rootworm (Diabrotica undecimpunctata howardi), cupreous chafer (Anomala cuprea), rufocuprea (Anomala rufocuprea), chafers such as Japanese beetle (Popillia japonica) Weevil such as weevil (Sitophilus zeamais), rice weevil (Lissohoptrus oryzophilus), weevil (Echinocnemus squameus), weevil (Anthonomus grandis), etc. Worms (Oulema oryzae), cucurbit leaf beetle (Aulacophora femoralis), Kisujinomihamushi (Phyllotreta striolata), Chrysomelidae such as Colorado potato beetle (Leptinotarsa decemlineata), click beetles such (Agriotes spp.), And Aoba ants backlash Staphylinidae (Paederus fuscipes).

In the present invention, seeds of the following “crop” can be treated with the present condensed heterocyclic compound.
Agricultural crops: corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, sugar beet, rapeseed, sunflower, tobacco, etc.
Vegetables: Solanum vegetables (eggplants, tomatoes, peppers, peppers, potatoes, etc.), Cucurbitaceae vegetables (cucumbers, pumpkins, zucchini, watermelons, melons, etc.), cruciferous vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage) , Mustard, broccoli, cauliflower, etc.), asteraceae vegetables (burdock, shungiku, artichoke, lettuce, etc.), liliaceae vegetables (leek, onion, garlic, asparagus), celeryaceae vegetables (carrot, parsley, celery, American scallop, etc.) ), Red crustacean vegetables (spinach, chard, etc.), perilla vegetables (perilla, mint, basil).

“Crop” includes genetically modified crops.

In the present invention, a plant seed treated with the present condensed heterocyclic compound retains an effective amount of the present condensed heterocyclic compound in the interior or surface of the plant seed or a coating formed on the periphery of the plant seed. ing. The plant seed treatment method may take various forms, for example, a spraying process in which the present condensed heterocyclic compound is sprayed on the seed surface, a smearing process in which the present condensed heterocyclic compound is applied to the seed, an immersion process, A film coat process and a pellet coat process are mentioned. In addition, in this invention, a plant seed means the seed of the plant of the state before sowing to soil or the culture medium to grow.

The amount of the present condensed heterocyclic compound used for such plant seeds can vary depending on the type of plant, the type and occurrence of harmful arthropods to be controlled, the form of preparation, sowing time, weather conditions, etc. Is usually 0.01 to 1000 g, preferably 0.2 to 200 g, more preferably 1 to 10 g. The amount is usually 0.01 to 1000 mg, preferably 0.1 to 100 mg, per 100 plant seeds.
In the present invention, the present fused heterocyclic compound can be mixed with one or more compounds selected from the following group (A) and treated to plant seeds.
Group (A)
A-1: Neonicotinoid imidacloprid, clothianidin, thiamethoxam, dinotefuran, acetamiprid, thiacloprid and nitenpyram A-2: synthetic pyrethroid acrinathrin, bifenthrin, cycloprotorin, cyfluthrin, beta-cyfluthrin, cihalothrin, lambda cihalothrin, cancer Masihalothrin, cypermethrin, alpha cypermethrin, beta cypermethrin, theta cypermethrin, zetacypermethrin, deltamethrin, etofenprox, fenpropatoline, fenvalerate, esfenvalerate, flucitrinate, fulvalinate, taufulvalinate , Halfenprox, Permethrin, Silafluophene, Tefluthrin, Tralomethrin and Protrifen Butte A 3: phenylpyrazole etiprole, fipronil, acetoprole, vaniliprole, pyriprole and pyrafluprolol A-4: macrolide abamectin, emamectin, emamectin benzoate, milbemectin, doramectin and lepimectin A-5: diamide fulvendiamide and the following formula ( Compound formula (2) represented by 2)

[In the formula (2), R1 is a methyl group or bromine atom, R2 is a bromine atom, chlorine atom or cyano group, R3 is a methyl group, 1-cyclopropylethyl group or methoxycarbonylamino group, R4 is a hydrogen atom or ethyl group Indicates. ]
A-6: Other insecticides Pymetrozine, pyridalyl, pyriproxyfen, spirotetramat, sulfoxafurol and flupiradifurone A-7: azoletebuconazole, metconazole, difenoconazole, triticonazole, imazalyl, triadimenol, fluquinconazole, prochloraz, prochiraz Oconazole, diniconazole, diniconazole M, cyproconazole, tetraconazole, ipconazole, trifolin, pyrifenox, phenarimol, nuarimol, oxpoconazole fumarate, pefazoate, triflumizole, azaconazole, vitertanol, bromconazole, Epoxyconazole, fenbuconazole, flusilazole, flutriazole, hexaconazole, imibenconazole, micro Butanyl, penconazole, propiconazole, cimeconazole, and triazimephone A-8: strobilurin resoxime methyl, azoxystrobin, pyraclostrobin, picoxystrobin, enestrobine, trifloxystrobin, dimoxystrobin, floxastrobin, orizastrobin , Famoxadone, phenamidon, metminostrobin, and a compound represented by the following formula (3)

A-9: Phenylamide metalaxyl, metalaxyl-M, furaxyl-M, benalaxyl, benalaxyl-M, off race and oxadixyl A-10: rice blast control compound probenazole, thiazinyl, tricyclazole, pyroxylone, kasugamycin hydrochloride, felimzone, isothianyl , Fusalide and tebufloquine A-11: rice blight control compound pencyclon, furametopil and validamycin A-12: carboxamido carboxin, flutolanil, penthiopyrad, fluopyram, penflufen, sedaxane, fluxapilox and the following formula (4) Compound formula (4)

[Where,
R1 represents a hydrogen atom or a methyl group,
R2 represents a methyl group, a difluoromethyl group or a trifluoromethyl group. ]
Compound A-13 represented by: Other fungicides fludioxonil, ethaboxam, tolcrofosmethyl and captan A-14: Other compounds 4-oxo-4-[(2-phenylethyl) amino] -butyric acid,

Hereinafter, although this invention is demonstrated in more detail by a manufacture example, a reference manufacture example, a formulation example, a test example, etc., this invention is not limited only to these examples.
First, a manufacture example is shown about manufacture of this condensed heterocyclic compound.

Hereinafter, production examples of the present condensed heterocyclic compound will be shown, but the present condensed heterocyclic compound is not limited to these examples.

Production Example 1
N2- methyl-5-trifluoromethyl-2,3-diamine 1.0 g, 2-ethylsulfanyl benzaldehyde 0.96 g, a mixture of sodium bisulfite 1.80g and 10 ml of DMF, and stirred for 5 hours at 160 ° C.. The reaction mixture was ice-cooled, water was added, and the precipitated crystals were collected by filtration, and washed with water and then hexane. The obtained crystals were dried under reduced pressure to give 2- (2-ethylsulfanylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound). 1)) 1.09 g was obtained.
This condensed heterocyclic compound 1

1H-NMR (CDCl3) δ: 8.72-8.70 (1H, m), 8.33-8.31 (1H, m), 7.56-7.49 (2H, m), 7.47 -7.43 (1H, m), 7.39-7.34 (1H, m), 3.77 (3H, s), 2.87 (2H, q), 1.24 (3H, t)

Production Example 2
2- (2-ethylsulfanylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine 0.25 g, sodium periodate 0.24 g, methanol 6 ml, water 2 ml and THF0 .8 ml of the mixture was stirred at room temperature for 20 minutes, then heated to 50 ° C., and further heated and stirred for 1.5 hours. Water was added to the ice-cooled reaction mixture, and the precipitated crystals were collected by filtration. The crystals collected by filtration were dissolved in ethyl acetate, washed successively with saturated aqueous sodium thiosulfate solution, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then the organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was washed with hexane, and 2- (2-ethylsulfinylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 2). 0.20 g was obtained.
This condensed heterocyclic compound 2

1H-NMR (CDCl3) δ: 8.76-8.74 (1H, m), 8.32-8.30 (1H, m), 8.27-8.24 (1H, m), 7.86 -7.81 (1H, m), 7.72-7.68 (1H, m), 7.62-7.59 (1H, m), 3.89 (3H, s), 3.42-3 .31 (1H, m), 3.02-2.92 (1H, m), 1.31 (3H, t)

Production Example 3
2-Chloroperbenzoic acid was added to a mixture of 0.25 g of 2- (2-ethylsulfanylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine and 3 ml of chloroform under ice cooling. After adding 0.43 g (purity 65% or more), the mixture was warmed to room temperature and stirred for 1 hour. Chloroform was added to the reaction mixture under ice-cooling, saturated aqueous sodium thiosulfate solution was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and then with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained crystals were washed with hexane and then with methyl-tert-butyl ether to give 2- (2-ethylsulfonylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as “(2-ethylsulfonylphenyl) -3-methyl-tert-butyl ether)” This is referred to as the present condensed heterocyclic compound 3.) 0.27 g was obtained.
This condensed heterocyclic compound 3

1H-NMR (CDCl3) δ: 8.75-8.73 (1H, m), 8.29-8.27 (1H, m), 8.25-8.21 (1H, m), 7.87 -7.79 (2H, m), 7.58-7.55 (1H, m), 3.72 (3H, s), 3.42 (2H, q), 1.26 (3H, t)

Production Example 4
To a mixture of 700 mg of N2-ethyl-5-trifluoromethylpyridine-2,3-diamine, 690 mg of 2-ethylsulfanylbenzoic acid and 20 ml of pyridine, 720 mg of WSC was added at room temperature. did. Saturated aqueous sodium carbonate solution was added to the reaction mixture cooled to room temperature, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure.
The obtained residue was dissolved in 20 ml of xylene, and 1.6 g of p-toluenesulfonic acid monohydrate was added. The mixture was heated to 170 ° C. and stirred with heating for 9.5 hours. A saturated aqueous sodium hydrogen carbonate solution was poured into the reaction mixture cooled to room temperature, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 3-ethyl-2- (2-ethylsulfanylphenyl) -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed complex). This is referred to as ring compound 4.) 295 mg was obtained.
This condensed heterocyclic compound 4

1H-NMR (CDCl3) δ: 8.70 (1H, s), 8.32 (1H, s), 7.60-7.30 (4H, m), 4.25 (2H, q), 2. 89 (2H, q), 1.35-1.30 (3H, m), 1.27-1.21 (3H, m)

Production Examples 5 and 6
Instead of 2- (2-ethylsulfanyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 3-ethyl-2- (2-ethylsulfanylphenyl) ) -6-Trifluoromethyl-3H-imidazo [4,5-b] pyridine and 2- (2-ethylsulfinylphenyl) -3-ethyl-6 according to the methods described in Preparation Examples 32 and 33 -Trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 5) 140 mg, and 2- (2-ethylsulfonylphenyl) -3-ethyl-6-trifluoro 60 mg of methyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 6) was obtained.
This condensed heterocyclic compound 5

1H-NMR (CDCl3) δ: 8.75 (1H, d), 8.31 (1H, d), 8.24 (1H, dd), 7.84 (1H, dt), 7.70 (1H, dt), 7.58 (1H, dd), 4.35 (2H, q), 3.43-3.30 (1H, m), 3.06-2.94 (1H, m), 1.41 (3H, t), 1.30 (3H, t)
This condensed heterocyclic compound 6

1H-NMR (CDCl3) δ: 8.71 (1H, d), 8.32 (1H, d), 7.56-7.47 (2H, m), 7.43 (1H, dd), 7. 39-7.31 (1H, m), 4.25 (2H, q), 2.89 (2H, q), 1.32 (3H, t), 1.25 (3H, t)

Production Example 7
According to the method described in Preparation Example 4, using N2-isopropyl-5-trifluoromethyl-pyridine-2,3-diamine instead of N2-ethyl-5-trifluoromethyl-pyridine-2,3-diamine, 130 mg of 2- (2-ethylsulfanylphenyl) -3-isopropyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 7) was obtained.
This condensed heterocyclic compound 7

1H-NMR (CDCl3) δ: 8.68 (1H, d), 8.28 (1H, d), 7.55-7.47 (2H, m), 7.39-7.31 (2H, m ), 4.40-4.33 (1H, m), 2.91 (2H, q), 1.77-1.66 (6H, m), 1.25 (3H, t)

Production Examples 8 and 9
Instead of 2- (2-ethylsulfanyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 2- (2-ethylsulfanylphenyl) -3- 2- (2-Ethylsulfinylphenyl) -3-isopropyl-6-, using isopropyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, according to the methods described in Preparation Examples 32 and 33 60 mg of trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 8), and 2- (2-ethylsulfonylphenyl) -3-isopropyl-6-trifluoromethyl 55 mg of -3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 9) was obtained.
This condensed heterocyclic compound 8

1H-NMR (CDCl3) δ: 8.73 (1H, d), 8.28 (1H, d), 8.22 (1H, dd), 7.83 (1H, td), 7.69 (1H, td), 7.50 (1H, dd), 4.60-4.48 (1H, m), 3.38-3.26 (1H, m), 3.05-2.95 (1H, m) , 1.77-1.71 (6H, m), 1.27 (3H, t)
This condensed heterocyclic compound 9

1H-NMR (CDCl3) δ: 8.71 (1H, d), 8.24-8.22 (2H, m), 7.85-7.78 (2H, m), 7.55-7.52 (1H, m), 4.33-4.26 (1H, m), 3.72-3.62 (1H, m), 3.44-3.34 (1H, m), 1.77-1 .69 (6H, m), 1.28 (3H, t)

Production Example 10
In accordance with the method described in Preparation Example 4, using N2-cyclopropyl-5-trifluoromethyl-pyridine-2,3-diamine instead of N2-ethyl-5-trifluoromethyl-pyridine-2,3-diamine , 280 mg of 3-cyclopropyl-2- (2-ethylsulfanylphenyl) -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 10) was obtained. .
The present condensed heterocyclic compound 10

1H-NMR (CDCl3) δ: 8.74 (1H, s), 8.31 (1H, s), 7.53-7.47 (3H, m), 7.39-7.31 (1H, m ), 3.55-3.49 (1H, m), 2.90 (2H, q), 1.25 (3H, t), 1.01-0.94 (2H, m), 0.93- 0.86 (2H, m)

Production Examples 11 and 12
Instead of 2- (2-ethylsulfanyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 3-cyclopropyl-2- (2-ethylsulfanyl) 3-cyclopropyl-2- (2-ethylsulfinylphenyl)-using phenyl) -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine according to the methods described in Preparation Examples 32 and 33 114 mg of 6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 11), and 3-cyclopropyl-2- (2-ethylsulfonylphenyl) -6- 109 mg of trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 12) was obtained.
This condensed heterocyclic compound 11

1H-NMR (CDCl3) δ: 8.77 (1H, d), 8.29-8.26 (2H, m), 7.85-7.79 (2H, m), 7.72-7.67 (1H, m), 3.57-3.51 (1H, m), 3.49-3.39 (1H, m), 3.09-2.95 (1H, m), 1.34 (3H , T), 1.29-1.16 (1H, m), 1.09-0.92 (2H, m), 0.80-0.65 (1H, m)
This condensed heterocyclic compound 12

1H-NMR (CDCl3) δ: 8.76 (1H, s), 8.27-8.22 (2H, m), 7.87-7.78 (2H, m), 7.65 (1H, dd) ), 3.60 (2H, brs), 3.39-3.33 (1H, m), 1.29 (3H, t), 1.11-1.11 (2H, m), 0.93 ( 2H, brs).

Production Example 13
To a mixture of 2- (2-ethylsulfanylphenyl) -3-methyl-3H-imidazo [4,5-b] pyridine-6-carbaldehyde 122 mg and chloroform 3 ml was added bis (2-methoxyethyl) amino under ice cooling. 700 μl of sulfatrifluoride was added. The mixture was warmed to room temperature and stirred for 3 hours. Saturated aqueous sodium hydrogen carbonate solution was poured into the reaction mixture, and the mixture was extracted successively with chloroform and ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 6-difluoromethyl-2- (2-ethylsulfanylphenyl) -3-methyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic ring). It is described as Compound 13.) 49 mg was obtained.
This condensed heterocyclic compound 13

1H-NMR (CDCl3) δ: 8.59 (1H, s), 8.23 (1H, s), 7.56-7.43 (3H, m), 7.38-7.33 (1H, m ), 6.88 (1H, t), 3.77 (3H, s), 2.87 (2H, q), 1.23 (3H, t)

Production Examples 14 and 15
Instead of 2- (2-ethylsulfanyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 6-difluoromethyl-2- (2-ethylsulfanyl) Using phenyl) -3-methyl-3H-imidazo [4,5-b] pyridine, according to the methods described in Preparation Examples 32 and 33, 6-difluoromethyl-2- (2-ethylsulfinylphenyl) -3- 110 mg of methyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 14) and 6-difluoromethyl-2- (2-ethylsulfonylphenyl) -3-methyl-3H-imidazo 101 mg of [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 15) was obtained.
The present condensed heterocyclic compound 14

1H-NMR (CDCl3) δ: 8.62 (1H, s), 8.26-8.23 (2H, m), 7.83 (1H, td), 7.70 (1H, td), 7. 62 (1H, dd), 6.90 (1H, t), 3.89 (3H, s), 3.42-3.32 (1H, m), 3.02-2.92 (1H, m) , 1.30 (3H, t)
This condensed heterocyclic compound 15

1H-NMR (CDCl3) δ: 8.61 (1H, s), 8.24-8.19 (2H, m), 7.87-7.78 (2H, m), 7.58 (1H, dd) ), 6.89 (1H, t), 3.71 (3H, s), 3.43 (2H, q), 1.25 (3H, t)

Production Example 16
6-bromo-2- (2-ethylsulfanylphenyl) -3-methyl-3H-imidazo [4,5-b] pyridine 500 mg, NMP 24 ml, xylene 10 ml, copper iodide 1.1 g and sodium pentafluoropropionate a mixture of 1g was heated to 170 ° C., the mixture was heated with stirring for 3 days. To the reaction mixture cooled to room temperature, a saturated aqueous sodium hydrogen carbonate solution was poured, and the mixture was extracted with tert-butyl methyl ether. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfanylphenyl) -3-methyl-6-pentafluoroethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed complex). referred to as cyclic compound 16.) was obtained 43 mg.
The present condensed heterocyclic compound 16

1H-NMR (CDCl3) δ: 8.66 (1H, d), 8.30 (1H, d), 7.56-7.49 (2H, m), 7.47-7.43 (1H, m ), 7.38-7.34 (1H, m), 3.78 (3H, s), 2.88 (2H, q), 1.24 (3H, t)

Production Example 17
A mixture of 1.64 g of 2-ethylsulfanyl-N- (2-methylamino-5-trifluoromethylphenyl) -benzamide, 1.76 g of p-toluenesulfonic acid monohydrate and 50 ml of xylene at 150 ° C. for 1 hour, Stir with heating to reflux. To the reaction mixture cooled to room temperature, a saturated aqueous sodium hydrogen carbonate solution was poured, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfanylphenyl) -1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter referred to as the present condensed heterocyclic compound 17). 1.40 g was obtained.
The present condensed heterocyclic compound 17

1H-NMR (CDCl3) δ: 8.12-8.10 (1H, m), 7.61-7.58 (1H, m), 7.53-7.44 (4H, m), 7.38 −7.32 (1H, m), 3.69 (3H, s), 2.84 (2H, q), 1.22 (3H, t)

Production Example 18
Instead of 2- (2-ethylsulfanylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 2- (2-ethylsulfanylphenyl) -1-methyl-5 Using trifluoromethyl-1H-benzimidazole, 2- (2-ethylsulfinylphenyl) -1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter, this condensation) according to the method described in Production Example 2 This is referred to as heterocyclic compound 18.) 0.30 g was obtained.
The present condensed heterocyclic compound 18

1H-NMR (CDCl3) δ: 8.24-8.20 (1H, m), 8.10-8.07 (1H, m), 7.83-7.78 (1H, m), 7.70 -7.62 (2H, m), 7.57-7.51 (2H, m), 3.79 (3H, s), 3.36-3.26 (1H, m), 2.98-2 .88 (1H, m), 1.26 (3H, t)

Production Example 19
Instead of 2- (2-ethylsulfanylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 2- (2-ethylsulfanylphenyl) -1-methyl-5 Using trifluoromethyl-1H-benzimidazole, 2- (2-ethylsulfonylphenyl) -1-methyl-5-trifluoromethyl-1H-benzimidazole (hereinafter, this condensation) according to the method described in Production Example 3 This is referred to as heterocyclic compound 19.) 0.24 g was obtained.
The present condensed heterocyclic compound 19

1H-NMR (CDCl3) δ: 8.24-8.20 (1H, m), 8.07-8.05 (1H, m), 7.84-7.77 (2H, m), 7.64 -7.61 (1H, m), 7.57-7.54 (1H, m), 7.53-7.49 (1H, m), 3.63 (3H, s), 3.46-3 .34 (2H, m), 1.23 (3H, t)

Production Example 20
A mixture of 0.97 g of 2-amino-4-trifluoromethyl-phenol, 1.10 g of 2-ethylsulfanylbenzoic acid, 1.27 g of WSC, 37 mg of HOBt and 5 ml of pyridine was stirred at 115 ° C. for 2.5 hours with heating under reflux. After leaving still overnight, the mixture was again stirred at 115 ° C. for 6 hours with heating under reflux. Water was poured into the reaction mixture cooled to room temperature, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure.
A mixture of the obtained residue, 2.09 g of p-toluenesulfonic acid monohydrate and 50 ml of xylene was stirred at 153 ° C. for 2 hours with heating under reflux. To the reaction mixture cooled to room temperature, a saturated aqueous sodium hydrogen carbonate solution was poured, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution, water, 10% citric acid solution, water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 0.98 g of 2- (2-ethylsulfanylphenyl) -5-trifluoromethylbenzoxazole (hereinafter referred to as the present condensed heterocyclic compound 20).
The present condensed heterocyclic compound 20

1H-NMR (CDCl3) δ: 8.19-8.15 (2H, m), 7.71-7.67 (1H, m), 7.66-7.63 (1H, m), 7.52 -7.47 (1H, m), 7.45-7.42 (1H, m), 7.31-7.27 (1H, m), 3.06 (2H, q), 1.44 (3H , T)

Production Example 21
Instead of 2- (2-ethylsulfanylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 2- (2-ethylsulfanylphenyl) -5-trifluoromethylbenz Using oxazole, 0.27 g of 2- (2-ethylsulfinylphenyl) -5-trifluoromethylbenzoxazole (hereinafter referred to as the present condensed heterocyclic compound 21) was obtained according to the method described in Production Example 2. .
This condensed heterocyclic compound 21

1H-NMR (CDCl3) δ: 8.35-8.30 (2H, m), 8.12-8.10 (1H, m), 7.85-7.79 (1H, m), 7.75 -7.66 (3H, m), 3.48-3.38 (1H, m), 3.00-2.90 (1H, m), 1.41 (3H, t)

Production Example 22
Instead of 2- (2-ethylsulfanylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 2- (2-ethylsulfanylphenyl) -5-trifluoromethylbenz Using oxazole, 0.24 g of 2- (2-ethylsulfonylphenyl) -5-trifluoromethylbenzoxazole (hereinafter referred to as the present condensed heterocyclic compound 22) was obtained according to the method described in Production Example 3. .
The present condensed heterocyclic compound 22

1H-NMR (CDCl3) δ: 8.28-8.24 (1H, m), 8.11-8.09 (1H, m), 7.99-7.95 (1H, m), 7.85 -7.77 (2H, m), 7.72-7.70 (2H, m), 3.82 (2H, q), 1.40 (3H, t)

Production Example 23
A mixture of 0.92 g of 2-ethylsulfanylphenyl-N- (2-hydroxy-5-trifluoromethylpyridin-3-yl) -benzamide and 5 ml of phosphorus oxychloride was heated to 120 ° C. and stirred with heating under reflux. The reaction mixture cooled to room temperature was left overnight. The temperature was raised again to 120 ° C., and the mixture was stirred for 2 hours under reflux. Water was poured into the reaction mixture cooled to room temperature, and the precipitated solid was collected by filtration, washed with water and hexane, dried, and 2- (2-ethylsulfanylphenyl) -6-trifluoromethyloxazolo. 0.53 g of [5,4-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 23) was obtained.
The present condensed heterocyclic compound 23

1H-NMR (CDCl3) δ: 8.67 (1H, s), 8.40 (1H, s), 8.25 (1H, d), 7.53 (1H, t), 7.45 (1H, d), 7.32 (1H, t), 3.08 (2H, q), 1.45 (3H, t)

Production Example 24
Instead of 2- (2-ethylsulfanylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 2- (2-ethylsulfanylphenyl) -6-trifluoromethyloxa 2- (2-ethylsulfinylphenyl) -6-trifluoromethyloxazolo [5,4-b] pyridine (hereinafter, referred to as “Production Example 2”) using zolo [5,4-b] pyridine. This is referred to as the present condensed heterocyclic compound 24.) 0.17 g was obtained.
The present condensed heterocyclic compound 24

1H-NMR (CDCl3) δ: 8.73-8.72 (1H, m), 8.41-8.38 (2H, m), 8.36-8.33 (1H, m), 7.90 -7.84 (1H, m), 7.74-7.69 (1H, m), 3.45-3.35 (1H, m), 3.00-2.90 (1H, m), 1 .40 (3H, t)

Production Example 25
Instead of 2- (2-ethylsulfanylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 2- (2-ethylsulfanylphenyl) -6-trifluoromethyloxa 2- (2-ethylsulfonylphenyl) -6-trifluoromethyloxazolo [5,4-b] pyridine (hereinafter, referred to as “Production Example 3”) using zolo [5,4-b] pyridine. This is referred to as the present condensed heterocyclic compound 25.) 0.19 g was obtained.
This condensed heterocyclic compound 25

1H-NMR (CDCl3) δ: 8.75-8.73 (1H, m), 8.40-8.37 (1H, m), 8.29-8.26 (1H, m), 8.05 -8.02 (1H, m), 7.89-7.81 (2H, m), 3.81 (2H, q), 1.43 (3H, t)

Production Example 26
A mixture of 1.08 g of 2-amino-4-trifluoromethylbenzenethiol hydrochloride, 1.04 g of 2-ethylsulfanylbenzoic acid chloride and 10 mL of THF was stirred at room temperature for 3 hours. To the reaction mixture, 0.43 g of sodium hydrogen carbonate was added and stirred at room temperature for 8 hours. Saturated aqueous sodium hydrogen carbonate solution was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 0.50 g of 2- (2-ethylsulfanylphenyl) -5-trifluoromethylbenzothiazole (hereinafter referred to as the present condensed heterocyclic compound 26).
The present condensed heterocyclic compound 26

1H-NMR (CDCl3) δ: 8.41-8.39 (1H, m), 8.06-8.00 (2H, m), 7.66-7.62 (1H, m), 7.55 -7.51 (1H, m), 7.48-7.42 (1H, m), 7.37-7.32 (1H, m), 2.96 (2H, q), 1.33 (3H , T)

Production Example 27
Instead of 2- (2-ethylsulfanylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 2- (2-ethylsulfanylphenyl) -5-trifluoromethylbenzo Using thiazole, 0.25 g of 2- (2-ethylsulfinylphenyl) -5-trifluoromethylbenzothiazole (hereinafter referred to as the present condensed heterocyclic compound 27) was obtained according to the method described in Production Example 2. .
This condensed heterocyclic compound 27

1H-NMR (CDCl3) δ: 8.36-8.32 (1H, m), 8.32-8.30 (1H, m), 8.08-8.05 (1H, m), 7.97 -7.94 (1H, m), 7.80-7.75 (1H, m), 7.71-7.68 (1H, m), 7.66-7.61 (1H, m), 3 .56-3.45 (1H, m), 3.02-2.93 (1H, m), 1.46 (3H, t)

Production Example 28
Instead of 2- (2-ethylsulfanylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 2- (2-ethylsulfanylphenyl) -5-trifluoromethylbenzo Using thiazole, 0.30 g of 2- (2-ethylsulfonylphenyl) -5-trifluoromethylbenzothiazole (hereinafter referred to as the present condensed heterocyclic compound 28) was obtained according to the method described in Production Example 3. .
The present condensed heterocyclic compound 28

1H-NMR (CDCl3) δ: 8.33-8.31 (1H, m), 8.26-8.23 (1H, m), 8.10-8.06 (1H, m), 7.81 -7.69 (4H, m), 3.75 (2H, q), 1.36 (3H, t)

Production Examples 29 and 30
2- (2-ethylsulfanyl-4-phenyl) -3 instead of 2- (2-ethylsulfanyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine Using 2-methyl-6-pentafluoroethyl-3H-imidazo [4,5-b] pyridine, according to the method described in Preparation Examples 32 and 33, 2- (2-ethylsulfinyl-phenyl) -3-methyl- 27 mg of 6-pentafluoroethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 29) and 2- (2-ethylsulfonylphenyl) -3-methyl-6-pentafluoro 31 mg of ethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 30) was obtained.
This condensed heterocyclic compound 29

1H-NMR (CDCl3) δ: 8.70 (1H, d), 8.29 (1H, d), 8.27 (1H, d), 7.84 (1H, t), 7.71 (1H, t), 7.60 (1H, d), 3.90 (3H, s), 3.43-3.33 (1H, m), 3.04-2.94 (1H, m), 1.31 (3H, t)
This condensed heterocyclic compound 30

1H-NMR (CDCl3) δ: 8.69 (1H, s), 8.25 (1H, s), 8.23-8.22 (1H, m), 7.88-7.79 (2H, m ), 7.59-7.52 (1H, m), 3.72 (3H, s), 3.43 (2H, q), 1.26 (3H, t)

Production Example 31
A mixture of 1.14 g N2-methyl-5-trifluoromethylpyridine-2,3-diamine, 1.44 g 2-ethylsulfanyl-4-fluorobenzoic acid, 1.02 g WSC and 12 ml pyridine was added at 120 ° C. Stir for hours. Water was poured into the reaction mixture cooled to room temperature, and the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure.
To the obtained residue, 3.42 g of p-toluenesulfonic acid, 10 ml of xylene and 2 ml of NMP were added, and the mixture was stirred while heating under reflux at 150 ° C. for 4.5 hours while removing water using a Dean-Stark apparatus. Water was poured into the reaction mixture cooled to room temperature, and the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfanyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as “(2-ethylsulfanyl-4-fluorophenyl) -3-methyl-6H-imidazo [4,5-b] pyridine”). This is referred to as the present condensed heterocyclic compound 31.) 1.05 g was obtained.
This condensed heterocyclic compound 31

1H-NMR (CDCl3) δ: 8.70-8.68 (1H, m), 8.31-8.28 (1H, m), 7.43-7.38 (1H, m), 7.17 -7.13 (1H, m), 7.04-6.98 (1H, m), 3.75 (3H, s), 2.89 (2H, q), 1.26 (3H, t)

Production Examples 32 and 33
To a mixture of 2- (2-ethylsulfanyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (0.85 g) and chloroform (12 ml) was added 3- After adding 0.81 g of chloroperbenzoic acid (purity 65% or more), the mixture was warmed to room temperature and stirred for 30 minutes. Saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium thiosulfate solution were added to the reaction mixture, and the mixture was extracted with chloroform. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfinyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as “(2-ethylsulfinyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine”). This is referred to as the present condensed heterocyclic compound 32.) 0.33 g, and 2- (2-ethylsulfonyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (Hereinafter referred to as the present condensed heterocyclic compound 33.) 0.52 g was obtained.
The present condensed heterocyclic compound 32

1H-NMR (CDCl3) δ: 8.76-8.75 (1H, m), 8.31-8.30 (1H, m), 8.01-7.98 (1H, m), 7.65 -7.61 (1H, m), 7.41-7.36 (1H, m), 3.90 (3H, s), 3.47-3.37 (1H, m), 3.04-2 .94 (1H, m), 1.33 (3H, t)
This condensed heterocyclic compound 33

1H-NMR (CDCl3) δ: 8.76-8.74 (1H, m), 8.29-8.27 (1H, m), 7.97-7.94 (1H, m), 7.60 -7.51 (2H, m), 3.72 (3H, s), 3.44 (2H, q), 1.28 (3H, t)

Production Example 34
To a mixture of 0.35 g of ethyl mercaptan sodium salt (80%) and 9 ml of DMF was added 2- (2-fluoro-4-trifluoromethylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [ 4,5-b] DMF solution of 1.0 g of pyridine was dropped, and then the mixture was warmed to room temperature and stirred at room temperature for 30 minutes. Saturated aqueous sodium hydrogen carbonate solution was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfanyl-4-trifluoromethylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine. (Hereinafter referred to as the present condensed heterocyclic compound 34) 1.10 g was obtained.
The present condensed heterocyclic compound 34

1H-NMR (CDCl3) δ: 8.75-8.73 (1H, m), 8.35-8.33 (1H, m), 7.70-7.68 (1H, m), 7.62 -7.56 (2H, m), 3.79 (3H, s), 2.95 (2H, q), 1.28 (3H, t)

Production Example 35
2- (2-Ethylsulfanyl-phenyl) -6-iodo-3-methyl-3H-imidazo [4,5-b] pyridine 311 mg, copper iodide 1.5 g, sodium heptafluorobutyrate 1.8 g, NMP 5 mL and xylene 25 mL of the mixture was heated and stirred at 150 ° C. for 12 hours. To the reaction mixture cooled to room temperature, a saturated aqueous sodium hydrogen carbonate solution and 28% aqueous ammonia were added, and the mixture was extracted with tert-butyl methyl ether. The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (2-ethylsulfanyl-phenyl) -6-heptafluoropropyl-3-methyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound). 35.) 118 mg was obtained.
This condensed heterocyclic compound 35

1H-NMR (CDCl3) δ: 8.65 (1H, d), 8.29 (1H, d), 7.56-7.51 (2H, m), 7.48-7.43 (1H, m ), 7.38-7.34 (1H, m), 3.78 (3H, s), 2.89 (2H, q), 1.25 (3H, t)

Production Examples 36 and 37
Instead of 2- (2-ethylsulfanyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 2- (2-ethylsulfanyl-phenyl) -6 2- (2-Ethylsulfinyl-phenyl) -6-heptafluoro using -heptafluoropropyl-3-methyl-3H-imidazo [4,5-b] pyridine according to the method described in Production Examples 32 and 33 Propyl-3-methyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 36) and 2- (2-ethylsulfonylphenyl) -6-heptafluoropropyl-3-methyl -3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 37) was obtained.
The present condensed heterocyclic compound 36

1H-NMR (CDCl3) δ: 8.68 (1H, d), 8.29-8.24 (2H, m), 7.87-7.81 (1H, m), 7.74-7.68 (1H, m), 7.61 (1H, dd), 3.91 (3H, s), 3.43-3.32 (1H, m), 3.05-2.94 (1H, m), 1.31 (3H, t)
The present condensed heterocyclic compound 37

1H-NMR (CDCl3) δ: 8.67 (1H, d), 8.26-8.22 (2H, m), 7.87-7.81 (2H, m), 7.59-7.55 (1H, m), 3.73 (3H, s), 3.43 (2H, q), 1.26 (3H, t).

Production Examples 38 and 39
Instead of 2- (2-ethylsulfanyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 2- (2-ethylsulfanyl-4-trifluoro 2- (2-Ethylsulfinyl-4-methyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine was used according to the methods described in Preparation Examples 32 and 33. Trifluoromethylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 38) 0.51 g, and 2- (2- Ethylsulfonyl-4-trifluoromethylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as this condensed heterocyclic compound) 39 and referred to.) Was obtained 0.26g.
The present condensed heterocyclic compound 38

1H-NMR (CDCl3) δ: 8.79-8.78 (1H, m), 8.57-8.55 (1H, m), 8.35-8.34 (1H, m), 7.97 -7.94 (1H, m), 7.77 (1H, d), 3.94 (3H, s), 3.53-3.43 (1H, m), 3.07-2.98 (1H) , M), 1.36 (3H, t)
The present condensed heterocyclic compound 39

1H-NMR (CDCl3) δ: 8.78-8.76 (1H, m), 8.51-8.49 (1H, m), 8.31-8.30 (1H, m), 8.12 -8.09 (1H, m), 7.74 (1H, d), 3.74 (3H, s), 3.48 (2H, q), 1.29 (3H, t)

Production Example 40
A mixture of 0.56 g of 3-amino-5- (trifluoromethyl) pyridine-2-thiol, 0.52 g of 2-ethylsulfanylbenzoic acid, 0.80 g of WSC, 39 mg of HOBt and 6 ml of pyridine was stirred at 60 ° C. for 2 hours. Water was poured into the reaction mixture allowed to cool, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
A mixture of the obtained residue, p-toluenesulfonic acid monohydrate 0.65 g and N-methylpyrrolidinone 5 mL was stirred with heating at 150 ° C. for 2 hours. Water was poured into the reaction mixture allowed to cool, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfanylphenyl) -6- (trifluoromethyl) thiazolo [5,4-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 40). .) 0.38 g was obtained.
The present condensed heterocyclic compound 40

1H-NMR (CDCl3) δ: 8.86 (1H, d), 8.57 (1H, d), 8.03 (1H, dd), 7.55 (1H, dd), 7.48 (1H, td), 7.36 (1H, td), 2.98 (2H, q), 1.34 (3H, t).

Production Examples 41 and 42
Instead of 2- (2-ethylsulfanyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 2- (2-ethylsulfanylphenyl) -6- 2- (2-Ethylsulfinylphenyl) -6- (trifluoromethyl) thiazolo [5, using (trifluoromethyl) thiazolo [5,4-b] pyridine according to the method described in Production Examples 32 and 33 4-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 41) 0.13 g, and 2- (2-ethylsulfonylphenyl) -6- (trifluoromethyl) thiazolo [5,4-b] pyridine ( Hereinafter, this is referred to as the present condensed heterocyclic compound 42.) 0.14 g was obtained.
The present condensed heterocyclic compound 41

1H-NMR (CDCl3) δ: 8.90 (1H, d), 8.49 (1H, d), 8.37 (1H, dd), 7.99 (1H, dd), 7.81 (1H, td), 7.67 (1H, td), 3.52-3.42 (1H, m), 3.01-2.92 (1H, m), 1.45 (3H, t).
The present condensed heterocyclic compound 42

1H-NMR (CDCl3) δ: 8.92 (1H, d), 8.52 (1H, d), 8.25 (1H, dd), 7.84-7.71 (3H, m), 3. 73 (2H, q), 1.37 (3H, t).

Production Examples 43 and 44
2- (2-ethylsulfanyl-4-phenyl) -3 instead of 2- (2-ethylsulfanyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine 2- (2-ethylsulfonylphenyl) -6-trifluoro-methyl-6-trifluoromethylsulfanyl-3H-imidazo [4,5-b] pyridine was used according to the method described in Preparation Examples 32 and 33. Methylsulfanyl-3-methyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 43) and 2- (2-ethylsulfinyl-phenyl) -6-trifluoromethylsulfanyl- 3-methyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 44) was obtained.
The present condensed heterocyclic compound 43

1H-NMR (CDCl3) δ: 8.68 (1H, d), 8.36 (1H, d), 8.21 (1H, dd), 7.87-7.77 (2H, m), 7. 59 (1H, dd), 3.71 (3H, s), 3.44 (2H, q), 1.24 (3H, t)
The present condensed heterocyclic compound 44

1H-NMR (CDCl3) δ: 8.69 (1H, d), 8.38 (1H, d), 8.25 (1H, dd), 7.86-7.80 (1H, m), 7. 72-7.67 (1H, m), 7.60 (1H, dd), 3.88 (3H, s), 3.43-3.31 (1H, m), 3.03-2.92 ( 1H, m), 1.31 (3H, t)

Production Examples 45 and 46
Instead of 2- (2-ethylsulfanyl-4-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine, 2- (2-ethylsulfonylphenyl) -6- 2- (2-Ethylsulfonylphenyl) -6-trifluoromethyl using trifluoromethylsulfanyl-3-methyl-3H-imidazo [4,5-b] pyridine according to the methods described in Preparation Examples 32 and 33 Sulfinyl-3-methyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 45) and 2- (2-ethylsulfonylphenyl) -6-trifluoromethylsulfonyl 3-methyl -3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 46) was obtained.
The present condensed heterocyclic compound 45

1H-NMR (CDCl3) δ: 8.77 (1H, d), 8.55 (1H, d), 8.24 (1H, dd), 7.90-7.83 (2H, m), 7. 61 (1H, dd), 3.75 (3H, s), 3.43 (2H, q), 1.26 (3H, t)
The present condensed heterocyclic compound 46

1H-NMR (CDCl3) δ: 9.05 (1H, d), 8.65 (1H, d), 8.26-8.23 (1H, m), 7.90-7.85 (2H, m ), 7.61-7.57 (1H, m), 3.77 (3H, s), 3.41 (2H, q), 1.27 (3H, t)

Production Example 47
2- [2-Fluoro-4- (trifluoromethyl) phenyl] -6- (trifluoromethyl) thiazolo [5,4-b] pyridine (0.18 g) and DMF (2 ml) were mixed with sodium thiomethoxide under ice-cooling. 63 mg was added and stirred at room temperature for 4 hours. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- [2-ethylsulfanyl-4- (trifluoromethyl) phenyl] -6- (trifluoromethyl) thiazolo [5,4-b] pyridine (hereinafter, This is referred to as the present condensed heterocyclic compound 47.) 0.11 g was obtained.
The present condensed heterocyclic compound 47

1H-NMR (CDCl3) δ: 8.90 (1H, d), 8.61 (1H, d), 8.14 (1H, d), 7.75 (1H, s), 7.58 (1H, d), 3.04 (2H, q), 1.38 (3H, t).

Production Example 48
3-Chloroperbenzoic acid was added to a mixture of 0.11 g of 2- [2-ethylsulfanyl-4- (trifluoromethyl) phenyl] -6- (trifluoromethyl) thiazolo [5,4-b] pyridine and 3 ml of chloroform. After adding 0.13 g (purity 65% or more), the mixture was stirred at room temperature for 12 hours. The reaction mixture was diluted with chloroform, washed successively with 10% aqueous sodium thiosulfate solution and saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, and 2- [2-ethylsulfonyl 4- (trifluoromethyl) phenyl] -6- (trifluoromethyl) thiazolo [5,4-b] pyridine (hereinafter referred to as the present). This is referred to as a condensed heterocyclic compound 48.) 0.11 g was obtained.
This condensed heterocyclic compound 48

1H-NMR (CDCl3) δ: 8.95 (1H, s), 8.55 (1H, s), 8.52 (1H, s), 8.07 (1H, d), 7.88 (1H, d), 3.77 (2H, q), 1.40 (3H, t).

Production Example 49
To a mixture of 535 mg 2- (2-ethylsulfanyl-phenyl) -3-methyl-3H-imidazo [4,5-b] pyridine-6-thiol, 166 μL iodomethane and 5 mL ethanol, 200 mg potassium hydroxide was added at room temperature for 5 hours. Stir. To this reaction mixture was added saturated aqueous ammonium chloride solution, and the mixture was extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfanyl-phenyl) -3-methyl-6-methylsulfanyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 49). 515 mg was obtained.
This condensed heterocyclic compound 49
1H-NMR (CDCl3) δ: 8.46 (1H, d), 8.10 (1H, d), 7.52-7.42 (3H, m), 7.37-7.26 (1H, m ), 3.73 (3H, s), 2.86 (2H, q), 2.54 (3H, s), 1.22 (3H, t)

Production Example 50
To a mixture of 363 mg of 2- (2-ethylsulfanyl-phenyl) -3-methyl-6-methylsulfanyl-3H-imidazo [4,5-b] pyridine and 5 mL of chloroform was added 69-75% 3-chloroperoxide under ice-cooling. 1.13 g of benzoic acid was added. The mixture was warmed to room temperature and stirred for 5 hours, and then a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium thiosulfate solution were added thereto, and the mixture was extracted with chloroform. The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfonylphenyl) -6-methylsulfonyl-3-methyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 50). ) 356 mg was obtained.
This condensed heterocyclic compound 50

1H-NMR (CDCl3) δ: 9.02 (1H, d), 8.58 (1H, d), 8.23 (1H, dd), 7.90-7.81 (2H, m), 7. 59 (1H, dd), 3.74 (3H, s), 3.42 (2H, q), 3.19 (3H, s), 1.26 (3H, t).

Production Example 51
2- (2-ethylsulfanyl-4-trifluoromethylphenyl) -6 instead of 2- (2-ethylsulfanyl-phenyl) -6-iodo-3-methyl-3H-imidazo [4,5-b] pyridine Compound 301A was obtained according to the method described in Production Example 103 using iodo-3-methyl-3H-imidazo [4,5-b] pyridine.
A mixture of 0.94 g of Compound 301A and 13 ml of DMF was cooled to −50 ° C., CF 3 I gas was bubbled in excess and dissolved in DMF. 1.2 ml of tetrakisdimethylaminoethylenediamine was added dropwise at a rate such that the internal temperature did not exceed -40 ° C. Then, it heated up to -10 degreeC over 1 hour, and also stirred at -10 degreeC for 1 hour. Water was poured into the reaction mixture, and the mixture was warmed to room temperature and extracted with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfanyl-4-trifluoromethylphenyl) -3-methyl-6-trifluoromethylsulfanyl-3H-imidazo [4,5-b]. 0.68 g of pyridine (hereinafter referred to as the present condensed heterocyclic compound 51) was obtained.
This condensed heterocyclic compound 51

1H-NMR (CDCl3) δ: 8.66 (1H, d) 8.39 (1H, d), 7.67-7.64 (1H, m), 7.59-7.52 (2H, m) , 3.75 (3H, s), 2.94 (2H, q), 1.27 (3H, t).

Production Example 52
To a mixture of 2- (2-ethylsulfanyl-4-trifluoromethylphenyl) -3-methyl-6-trifluoromethylsulfanyl-3H-imidazo [4,5-b] pyridine and 5 ml of chloroform was added 69. After adding 1.05 g of% 3-chloroperbenzoic acid, the mixture was warmed to room temperature and stirred for 1.5 hours. Thereafter, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium thiosulfate solution were added, and the mixture was extracted with chloroform. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfonyl-4-trifluoromethylphenyl) -3-methyl-6-trifluoromethylsulfanyl-3H-imidazo [4,5-b]. 0.20 g of pyridine (hereinafter referred to as the present condensed heterocyclic compound 52) was obtained.
The present condensed heterocyclic compound 52

1H-NMR (CDCl3) δ: 8.71-8.70 (1H, m), 8.50-8.49 (1H, m), 8.38-8.36 (1H, m), 8.12 -8.08 (1H, m), 7.74-7.71 (1H, m), 3.72 (3H, s), 3.49 (2H, q), 1.29 (3H, t).

Production Example 53
2- (2-ethylsulfonyl-4-trifluoromethylphenyl) -3-methyl-6-trifluoromethylsulfinyl-3H-imidazo [4,5-b] pyridine 0.26 g, sodium tungstate dihydrate 36 mg Then, a mixture of 1 ml of 30% aqueous hydrogen peroxide and 5 ml of acetonitrile was stirred for 4.5 hours while heating under reflux. Water was poured into the reaction mixture cooled to room temperature, and the mixture was extracted with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfonyl-4-trifluoromethylphenyl) -3-methyl-6-trifluoromethylsulfonyl-3H-imidazo [4,5-b]. 0.24 g of pyridine (hereinafter referred to as the present condensed heterocyclic compound 53) was obtained.
This condensed heterocyclic compound 53

1H-NMR (CDCl3) δ: 9.08-9.07 (1H, m), 8.68-8.66 (1H, m), 8.52-8.50 (1H, m), 8.16 -8.12 (1H, m), 7.76-7.73 (1H, m), 3.78 (3H, s), 3.46 (2H, q), 1.30 (3H, t)

Production Example 54
To a mixture of 552 mg of 4- (1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl) -benzene-1,2-diamine, 401 mg of 2-ethylsulfanylbenzoic acid and 27 mL of pyridine, 422 mg of ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 27 mg of 1-hydroxybenzotriazole were added. After 5 hours at room temperature, the reaction mixture was diluted with water and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The obtained residue was dissolved in a mixed solution of 7.5 mL of DMF and 30 mL of toluene, and 837 mg of p-toluenesulfonic acid was added at room temperature. The mixture was heated and stirred at 130 ° C. for 8 hours, and then allowed to cool to room temperature. Saturated aqueous sodium hydrogen carbonate solution was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography. This is referred to as the present condensed heterocyclic compound 54.) 97 mg was obtained.
The present condensed heterocyclic compound 54

1H-NMR (CDCl3) δ: 12.08-11.87 (1H, m), 8.31 (1H, s), 8.12-7.44 (4H, m), 7.42-7.30 (2H, m), 2.86 (2H, q), 1.22 (3H, t).

Production Example 55
To a mixture of 0.63 g of ethyl mercaptan sodium salt (80%) and 10 ml of DMF was added 2- (4-bromo-2-fluorophenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4, under ice cooling. 5-b] 2.08 g of DMF in pyridine was added dropwise, and the mixture was warmed to room temperature and stirred for 30 minutes. Saturated aqueous sodium hydrogen carbonate solution was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (4-bromo-2-ethylsulfanylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as “(2-bromo-4-ethylsulfanylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine”). This is referred to as the present condensed heterocyclic compound 55.) 1.57 g was obtained.
The present condensed heterocyclic compound 55

1H-NMR (CDCl3) δ: 8.73-8.71 (1H, m), 8.33-8.32 (1H, m), 7.59 (1H, d), 7.50-7.47 (1H, m), 7.30 (1H, d), 3.77 (3H, s), 2.91 (2H, q), 1.27 (3H, t).

Production Examples 56 and 57
To a mixture of 2- (4-bromo-2-ethylsulfanylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (0.40 g) and chloroform (5 ml) was added 3- After adding 0.29 g of chloroperbenzoic acid (purity 65% or more), the mixture was warmed to room temperature and stirred for 2 hours. Saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium thiosulfate solution were added to the reaction mixture, and the mixture was extracted with chloroform. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, and 2- (4-bromo-2-ethylsulfinylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as “(2-bromo-4-ethylsulfinylphenyl) -3-methyl)” And this condensed heterocyclic compound 56.) 0.26 g and 2- (4-bromo-2-ethylsulfonylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] 0.17 g of pyridine (hereinafter referred to as the present condensed heterocyclic compound 57) was obtained.
The present condensed heterocyclic compound 56

1H-NMR (CDCl3) δ: 8.77-8.75 (1H, m), 8.39 (1H, d), 8.32-8.31 (1H, m), 7.84-7.81 (1H, m), 7.49 (1H, d), 3.91 (3H, s), 3.50-3.40 (1H, m), 3.06-2.96 (1H, m), 1.35 (3H, t).
The present condensed heterocyclic compound 57

1H-NMR (CDCl3) δ: 8.77-8.75 (1H, m), 8.37 (1H, d), 8.31-8.29 (1H, m), 7.9-7.96. (1H, m), 7.44 (1H, d), 3.72 (3H, s), 3.44 (2H, q), 1.28 (3H, t).

Production Example 58
2- (4-Bromo-2-ethylsulfonylphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine 0.20 g, 2-tributylstannylpyrimidine 0.17 g, tetrakis A mixture of 27 mg of triphenylphosphine palladium and 5 ml of toluene was heated to reflux under a nitrogen atmosphere for 5.5 hours. After cooling to room temperature, 0.17 g of 2-tributylstannylpyrimidine and 27 mg of tetrakistriphenylphosphine palladium were added, and the mixture was further stirred for 8 hours with heating under reflux. After cooling to room temperature, water was added and extracted with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography, and 2- [2-ethylsulfonyl-4- (pyrimidin-2-yl) -phenyl] -3-methyl-6-trifluoromethyl-3H-imidazo [4, 5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 58) 0.20 g was obtained.
The present condensed heterocyclic compound 58

1H-NMR (CDCl3) δ: 8.77-8.74 (1H, m), 8.38-8.36 (1H, m), 8.30-8.27 (1H, m), 8.00 -7.95 (1H, m), 7.63-7.55 (1H, m), 7.43 (1H, d), 7.41-7.30 (2H, m), 3.72 (3H , S), 3.44 (2H, q), 1.28 (3H, t).

Production Example 59-1
To a mixture of 65 g of 5-trifluoromethyl-pyridin-2-ylamine and 100 mL of chloroform, 71 g of N-bromosuccinimide was added in 5 portions under cooling with ice water. After heating up to room temperature and stirring for 1 hour, it heated to 80 degreeC and heated and stirred for 30 minutes. After cooling to room temperature, a saturated aqueous sodium thiosulfate solution and a saturated aqueous sodium hydrogen carbonate solution were added, and the mixture was extracted with chloroform. The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 96 g of 3-bromo-5-trifluoromethyl-pyridin-2-ylamine.
3-Bromo-5-trifluoromethyl-pyridin-2-ylamine

1H-NMR (CDCl3) δ: 8.27 (1H, d), 7.86 (1H, d), 5.38 (2H, brs).

Production Example 59-2
3-Bromo-5-trifluoromethyl-pyridin-2-ylamine 40 g, acetylacetone copper (II) 2.2 g, acetylacetone 6.6 g, cesium carbonate 59 g, and NMP 105 mL were added to an autoclave reactor, and 28% aqueous ammonia solution was cooled with ice. 25 mL was added. After sealing, the temperature was raised to 110 ° C. and heated and stirred for 12 hours. After cooling to room temperature with ice, the reaction mixture was diluted with water and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 15 g of 5-trifluoromethyl-pyridine-2,3-diamine. 5-Trifluoromethyl-pyridine-2,3-diamine

1H-NMR (CDCl3) δ: 7.93 (1H, d), 7.04 (1H, d), 4.71 (2H, brs), 3.46 (2H, brs).

Production Example 59-3
7.35 g of sodium ethanethiolate (90%) was added to a mixture of 15.1 g of 2-fluoro-4-trifluoromethylbenzaldehyde and 61 ml of DMF, and the mixture was stirred at room temperature for 6 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 11.8 g of 2-formyl-5-trifluoromethylphenylethyl sulfide.
2-Formyl-5-trifluoromethylphenyl ethyl sulfide

1H-NMR (CDCl3) δ: 10.41 (1H, s), 7.94 (1H, d), 7.63 (1H, s), 7.53 (1H, d), 3.04 (2H, q), 1.41 (3H, t).

Production Example 59-4
To a mixture of 8.6 g of 5-trifluoromethyl-pyridine-2,3-diamine, 11 g of 2-formyl-5-trifluoromethylphenylethyl sulfide, and 67 mL of DMF, 6.1 g of sodium bisulfite was added at room temperature. . After heating and stirring at 100 ° C. for 3 hours, 1 g of copper (II) chloride dihydrate was added, and the mixture was further heated and stirred at 100 ° C. for 1 hour. After cooling to room temperature, this reaction mixture was added to water and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain a yellow powdered solid. This was washed with hot hexane to give 2- (2-ethylsulfanyl-4-trifluoromethyl-phenyl) -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocycle). This is referred to as compound 59.) 12 g were obtained.
This condensed heterocyclic compound 59

1H-NMR (CDCl3) δ: 12.79 (1H, brs), 8.72 (1H, brs), 8.49-8.34 (2H, m), 7.79 (1H, s), 7. 64 (1H, d), 3.00 (2H, q), 1.31 (3H, t).

Production Example 60
To a mixture of 12 g of 2- (2-ethylsulfanyl-4-trifluoromethyl-phenyl) -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine and 111 mL of chloroform was added 69 to 75% 3 under ice cooling. -8.0 g of chloroperbenzoic acid was added. The mixture was warmed to room temperature and stirred for 0.5 hour, and then a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium thiosulfate solution were added, and the mixture was extracted with chloroform. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and 2- (2-ethylsulfonyl-4-trifluoromethyl-phenyl) -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed complex). 9.1 g was obtained.
The present condensed heterocyclic compound 60

1H-NMR (DMSO-D6) δ: 14.15 (1H, brs), 8.83 (1H, s), 8.58 (1H, s), 8.41 (1H, d), 8.37 ( 1H, s), 8.19 (1H, d), 3.97 (2H, q), 1.23 (3H, t).

Production Example 61
A mixture of 200 mg of N- (2-amino-5-trifluoromethylpyridin-3-yl) -2-ethylsulfanyl-benzamide, 1 ml of tert-butyl alcohol and 9 ml of THF was heated and stirred at 80 ° C., and 60% 56 mg of sodium hydride (oily) was added. The mixture was heated and stirred at 80 ° C. for 2 hours, and 56 mg of 60% sodium hydride (oily) was added. Furthermore, after stirring with heating at the same temperature for 2 hours, 56 mg of 60% sodium hydride (oily) was added, and the mixture was heated with stirring at the same temperature for 2 hours. The reaction mixture was cooled to room temperature, the solvent was evaporated, saturated aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfanylphenyl) -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine (hereinafter referred to as the present condensed heterocyclic compound 61 and 132 mg was obtained.
The present condensed heterocyclic compound 61

1H-NMR (CDCl3) δ: 8.67 (1H, d), 8.51-8.48 (1H, m), 8.33 (1H, d), 7.66-7.61 (1H, m ), 7.51-7.46 (2H, m), 2.93 (2H, q), 1.27 (3H, t)

Production Example 62
To a mixture of 2.28 g of 2- (2-ethylsulfanylphenyl) -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine and 20 ml of chloroform was added 69-75% 3-chloroperbenzoic acid under ice cooling. 8.0 g of acid was added. The mixture was warmed to room temperature and stirred for 0.5 hour, and then a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium thiosulfate solution were added, and the mixture was extracted with chloroform. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, and the resulting crystals were washed with hexane to give 2- (2-ethylsulfonyl-phenyl) -6-trifluoromethyl-3H-imidazo [4,5-b] pyridine. (Hereinafter referred to as the present condensed heterocyclic compound 62.) 2.5 g was obtained.
The present condensed heterocyclic compound 62

1H-NMR (CDCl3) δ: 8.63 (1H, s), 8.35 (1H, s), 8.24 (1H, d), 8.09 (1H, d), 7.83 (1H, t), 7.76 (1H, t), 3.33 (2H, q), 0.88 (3H, t).

Production Examples 63 and 64
To a mixture of 0.31 g of ethyl mercaptan sodium salt (80%) and 9 ml of DMF was added ice-cooled 2- (2-fluoro-4-trifluoromethoxyphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [ After adding 1.05 g of 4,5-b] pyridine, the mixture was warmed to room temperature and stirred for 2 hours. Saturated aqueous sodium hydrogen carbonate solution was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfanyl-4-trifluoromethoxyphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine. And 0.82 g of a mixture (approximately 3: 1) of 2- (2-fluoro-4-trifluoromethoxyphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine It was.
After adding 0.45 g of 3-chloroperbenzoic acid (purity 65% or more) to the mixture of the obtained mixture and 4 ml of chloroform under ice cooling, the mixture was warmed to room temperature and stirred for 2 hours. Saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium thiosulfate solution were added to the reaction mixture, and the mixture was extracted with chloroform. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfinyl-4-trifluoromethoxyphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine. (Hereinafter referred to as the present condensed heterocyclic compound 63.) 0.47 g, 2- (2-ethanesulfonyl-4-trifluoromethoxyphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5 -B] 0.14 g of pyridine (hereinafter referred to as the present condensed heterocyclic compound 64) was obtained.
The present condensed heterocyclic compound 63

1H-NMR (CDCl3) δ: 8.78-8.76 (1H, m), 8.33-8.31 (1H, m), 8.14-8.12 (1H, m), 7.68 (1H, d), 7.54-7.50 (1H, m), 3.93 (3H, s), 3.49-3.39 (1H, m), 3.06-2.96 (1H , M), 1.33 (3H, t).
The present condensed heterocyclic compound 64

1H-NMR (CDCl3) δ: 8.77-8.75 (1H, m), 8.30-8.28 (1H, m), 8.09-8.07 (1H, m), 7.70 −7.66 (1H, m), 7.63 (1H, d), 3.74 (3H, s), 3.46 (2H, q), 1.28 (3H, t).

Production Example 65
2- (2-Ethylsulfinyl-4-trifluoromethoxyphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine 0.34 g, zirconium chloride 0.36 g, sodium iodide A mixture of 0.47 g and 8 ml of acetonitrile was stirred with heating under reflux for 2 hours. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfanyl-4-trifluoromethoxyphenyl) -3-methyl-6-trifluoromethyl-3H-imidazo [4,5-b] pyridine. (Hereinafter referred to as the present condensed heterocyclic compound 65.) 0.29 g was obtained.
This condensed heterocyclic compound 65

1H-NMR (CDCl3) δ: 8.74-8.72 (1H, m), 8.33-8.32 (1H, m), 7.48 (1H, d), 7.29-7.27 (1H, m), 7.21-7.17 (1H, m), 3.79 (3H, s), 2.92 (2H, q), 1.29 (3H, t).
Production Example 66-1
A mixture of 0.50 g of 2-amino-4-trifluoromethylphenol, 0.71 g of 2-ethylsulfanyl-4-trifluoromethylbenzoic acid, 0.65 g of WSC and 6 ml of chloroform was stirred at room temperature for 3.5 hours. Saturated aqueous ammonium chloride solution was poured into the reaction mixture, and the mixture was extracted with chloroform. The organic layer was washed with a saturated aqueous sodium bicarbonate solution and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 0.57 g of 2-ethylsulfanyl-4-trifluoromethyl-N- [2-hydroxy-5-trifluoromethylphenyl] benzamide.
2-Ethylsulfanyl-4-trifluoromethyl-N- [2-hydroxy-5-trifluoromethylphenyl] benzamide

¹ H-NMR (CDCl ₃ ) δ: 9.33 (1H, brs), 8.87 (1H, s), 8.03 (1H, d), 7.75 (1H, s), 7.62 ( 1H, d), 7.57 (1H, s), 7.44 (1H, d), 7.14 (1H, d), 3.05 (2H, q), 1.36 (3H, t)
Production Example 66-2
2-ethylsulfanyl-4-trifluoromethyl-N- [2-hydroxy-5-trifluoromethylphenyl] benzamide 0.56 g, di-2-methoxyethyl azodicarboxylate (hereinafter referred to as DMEAD) 0.40 g A mixture of 0.39 g of triphenylphosphine and 15 ml of THF was stirred at room temperature for 30 minutes and at 50 ° C. for 1 hour. The reaction mixture allowed to cool to room temperature was concentrated under reduced pressure, water was poured, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 0.52 g of 2- (2-ethylsulfanyl-4-trifluoromethylphenyl) -5-trifluoromethylbenzoxazole.
2- (2-Ethylsulfanyl-4-trifluoromethylphenyl) -5-trifluoromethylbenzoxazole
¹ H-NMR (CDCl ₃ ) δ: 8.29 (1H, d), 8.19 (1H, d), 7.75-7.66 (2H, m), 7.63 (1H, s), 7.51 (1H, dd), 3.10 (2H, q), 1.47 (3H, t).
Production Example 66-3
To a mixture of 2- (2-ethylsulfanyl-4-trifluoromethylphenyl) -5-trifluoromethylbenzoxazole 0.35 g and chloroform 10 ml, m-chloroperbenzoic acid (purity 65% or more) 0 After adding .46 g, the mixture was stirred at room temperature for 1.5 hours. A 10% aqueous sodium sulfite solution was added to the reaction mixture, and the mixture was extracted with chloroform. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 2- (2-ethylsulfonyl-4-trifluoromethylphenyl) -5-trifluoromethylbenzoxazole (hereinafter referred to as the present condensed heterocyclic compound 130). .34 g was obtained.
The present condensed heterocyclic compound 130

¹ H-NMR (CDCl ₃ ) δ: 8.54 (1H, s), 8.18-8.12 (2H, m), 8.08 (1H, dd), 7.77-7.74 (2H M), 3.90 (2H, q), 1.44 (3H, t).
Production Example 67-1
To a mixture of 1.2 g of 2-ethylsulfanylbenzoic acid, 10 ml of chloroform and 0.1 ml of DMF, 1.1 ml of oxalyl chloride was added and stirred at room temperature for 1 hour. The reaction mixture was concentrated under reduced pressure, and 10 ml of THF was added to the reaction mixture. This was added to a mixture of 1.38 g of 2-amino-4- (trifluoromethylsulfanyl) phenol and 15 ml of THF under ice cooling, and the mixture was stirred at room temperature for 2 hours. Water was added to the reaction mixture, and the mixture was extracted with chloroform. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 2-ethylsulfanyl-N- [2-hydroxy-5- (trifluoromethylsulfanyl). 1.78 g of phenyl] benzamide were obtained.
2-Ethylsulfanyl-N- [2-hydroxy-5- (trifluoromethylsulfanyl) phenyl] benzamide

¹ H-NMR (CDCl ₃ ) δ: 9.89 (1H, s), 9.71 (1H, s), 8.05 (1H, dd), 7.58 (1H, dd), 7.51 ( 1H, ddd), 7.48-7.41 (3H, m), 7.12 (1H, d), 2.99 (2H, q), 1.31 (3H, t).
Production Example 67-2
A mixture of 1.78 g of 2-ethylsulfanyl-N- [2-hydroxy-5- (trifluoromethylsulfanyl) phenyl] benzamide, 1.79 g of DMEAD, 1.88 g of triphenylphosphine and 20 ml of THF is stirred for 30 minutes at room temperature and 50 ° C. For 1 hour. The reaction mixture allowed to cool to room temperature was concentrated under reduced pressure, water was poured, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 1.33 g of 2- (2-ethylsulfanylphenyl) -5- (trifluoromethylsulfanyl) benzoxazole.
2- (2-Ethylsulfanylphenyl) -5- (trifluoromethylsulfanyl) benzoxazole

¹ H-NMR (CDCl ₃ ) δ: 8.21 (1H, d), 8.17 (1H, dd), 7.67 (1H, dd), 7.64 (1H, d), 7.52- 7.46 (1H, m), 7.43 (1H, dd), 7.31-7.27 (1H, m), 3.07 (2H, q), 1.45 (3H, t).
Production Example 67-3
To a mixture of 1.15 g of 2- (2-ethylsulfanylphenyl) -5- (trifluoromethylsulfanyl) benzoxazole and 25 ml of chloroform, 2.04 g of m-chloroperbenzoic acid (purity 65% or more) was added under ice cooling. After the addition, the mixture was stirred at room temperature for one and a half days. A 10% aqueous sodium sulfite solution was added to the reaction mixture, and the mixture was extracted with chloroform. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 0.38 g of 2- (2-ethylsulfonylphenyl) -5- (trifluoromethylsulfanyl) benzoxazole and 2- (2-ethylsulfonylphenyl) -5- ( 0.55 g of trifluoromethylsulfinyl) benzoxazole (hereinafter referred to as the present condensed heterocyclic compound 131) was obtained.
2- (2-Ethylsulfonylphenyl) -5- (trifluoromethylsulfanyl) benzoxazole

¹ H-NMR (CDCl ₃ ) δ: 8.28-8.24 (1H, m), 8.16-8.13 (1H, m), 7.9-7.95 (1H, m), 7 .85-7.76 (2H, m), 7.73 (1H, dd), 7.66 (1H, d), 3.83 (2H, q), 1.40 (3H, t).
This condensed heterocyclic compound 131

¹ H-NMR (CDCl ₃ ) δ: 8.30-8.25 (2H, m), 8.01-7.97 (1H, m), 7.87-7.79 (4H, m), 3 .82 (2H, q), 1.41 (3H, t).

Hereinafter, 1H-NMR data of the present condensed heterocyclic compounds described in Table 3 and Table 4 are shown.
The present condensed heterocyclic compound 66
1H-NMR (CDCl3) δ: 8.51 (1H, s), 8.22 (1H, s), 7.55-7.50 (2H, m), 7.47-7.43 (1H, m ), 7.38-7.32 (1H, m), 5.81 (1H, dq), 3.76 (3H, s), 2.88 (2H, q), 1.24 (3H, t) .
The present condensed heterocyclic compound 67
1H-NMR (CDCl3) δ: 8.55 (1H, d), 8.26 (1H, d), 8.21 (1H, d), 7.83 (1H, t), 7.69 (1H, t), 7.60 (1H, d), 5.84 (1H, dq), 3.88 (3H, s), 3.42-3.30 (1H, m), 3.03-2.91. (1H, m), 1.33-1.25 (3H, m).
This condensed heterocyclic compound 68
1H-NMR (CDCl3) δ: 8.53 (1H, s), 8.26-8.16 (2H, m), 7.88-7.78 (2H, m), 7.59-7.53 (1H, m), 5.82 (1H, dq), 3.70 (3H, s), 3.44 (2H, q), 1.26 (3H, t).
This condensed heterocyclic compound 69
1H-NMR (CDCl3) δ: 8.68 (1H, d), 8.29 (1H, d), 7.74-7.68 (1H, m), 7.49-7.40 (2H, m ), 3.73 (3H, s), 2.74 (2H, q), 1.06 (3H, t).
The present condensed heterocyclic compound 70
1H-NMR (CDCl3) δ: 8.64 (1H, s), 8.24 (1H, s), 7.65 (1H, d), 7.58 (1H, t), 7.39 (1H, d), 3.72 (3H, s), 3.63-3.47 (1H, m), 3.37-3.22 (1H, m), 1.38-1.30 (3H, m) .
The present condensed heterocyclic compound 71
1H-NMR (CDCl3) δ: 8.74-8.72 (1H, m), 8.33-8.32 (1H, m), 7.52-7.49 (1H, m), 7.47 -7.43 (2H, m), 3.79 (3H, s), 2.85 (2H, q), 1.23 (3H, t).
The present condensed heterocyclic compound 72
1H-NMR (CDCl3) δ: 8.78-8.76 (1H, m), 8.33-8.31 (1H, m), 8.20 (1H, d), 7.81-7.78 (1H, m), 7.60 (1H, d), 3.93 (3H, s), 3.42-3.32 (1H, m), 3.02-2.92 (1H, m), 1.31 (3H, t).
This condensed heterocyclic compound 73
1H-NMR (CDCl3) δ: 8.76-8.75 (1H, m), 8.29-8.28 (1H, m), 8.16 (1H, d), 7.80-7.77 (1H, m), 7.57 (1H, d), 3.75 (3H, s), 3.40 (2H, q), 1.26 (3H, t).
The present condensed heterocyclic compound 74
1H-NMR (CDCl3) δ: 8.74-8.72 (1H, m), 8.33-8.31 (1H, m), 7.51-7.45 (1H, m), 7.36 -7.31 (2H, m), 3.75 (3H, s), 2.78 (2H, q), 1.10 (3H, t).
This condensed heterocyclic compound 75
1H-NMR (CDCl3) δ: 8.73-8.71 (1H, m), 8.29-8.27 (1H, m), 7.70-7.64 (1H, m), 7.44 −7.38 (1H, m), 7.33 (1H, d), 3.81 (3H, s), 3.53-3.43 (1H, m), 3.42 to 3.31 (1H) , M), 1.33 (3H, t).
The present condensed heterocyclic compound 76
1H-NMR (CDCl3) δ: 8.73-8.72 (1H, m), 8.28-8.26 (1H, m), 7.84-7.78 (1H, m), 7.55 -7.49 (1H, m), 7.38-7.35 (1H, m), 3.77 (3H, s), 3.50-3.34 (2H, m), 1.34 (3H , T).
This condensed heterocyclic compound 77
1H-NMR (CDCl3) δ: 8.74-8.72 (1H, m), 8.37-8.35 (1H, m), 7.54-7.48 (1H, m), 7.27 -7.24 (1H, m), 7.09-7.03 (1H, m), 3.77 (3H, d), 2.93 (2H, q), 1.28 (3H, t).
The present condensed heterocyclic compound 78
1H-NMR (CDCl3) δ: 8.79-8.76 (1H, m), 8.35-8.32 (1H, m), 8.03 (1H, d), 7.87-7.80 (1H, m), 7.43 (1H, t), 3.84 (3H, d), 3.51-3.40 (1H, m), 3.13-3.02 (1H, m), 1.33 (3H, t).
This condensed heterocyclic compound 79
1H-NMR (CDCl3) δ: 8.77-8.75 (1H, m), 8.32-8.30 (1H, m), 8.07-8.04 (1H, m), 7.86 -7.80 (1H, m), 7.62-7.57 (1H, m), 3.76 (3H, s), 3.69-3.58 (1H, m), 3.41-3 .31 (1H, m), 1.29 (3H, t).
This condensed heterocyclic compound 80
1H-NMR (CDCl3) δ: 8.71-8.69 (1H, m), 8.31-8.30 (1H, m), 7.35-7.31 (2H, m), 7.19 -7.15 (1H, m), 3.76 (3H, s), 2.85 (2H, q), 2.46 (3H, s), 1.22 (3H, t).
This condensed heterocyclic compound 81
1H-NMR (CDCl3) δ: 8.74-8.73 (1H, m), 8.30-8.28 (1H, m), 8.06-8.05 (1H, m), 7.49 -7.48 (2H, m), 3.88 (3H, s), 3.42 -3.32 (1H, m), 3.00-2.90 (1H, m), 2.58 (3H) , S), 1.32 (3H, t).
This condensed heterocyclic compound 82
1H-NMR (CDCl3) δ: 8.74-8.72 (1H, m), 8.27-8.26 (1H, m), 8.03-8.02 (1H, m), 7.64 -7.61 (1H, m), 7.44 (1H, d), 3.70 (3H, s), 3.41 (2H, q), 2.59 (3H, s), 1.26 ( 3H, t).
This condensed heterocyclic compound 83
1H-NMR (CDCl3) δ: 8.75-8.74 (1H, m), 8.35-8.34 (1H, m), 7.66-7.65 (1H, m), 7.61 -7.55 (2H, m), 3.80 (3H, s), 2.95 (2H, q), 1.28 (3H, t).
This condensed heterocyclic compound 84
1H-NMR (CDCl3) δ: 8.80-8.78 (1H, m), 8.54-8.53 (1H, m), 8.35-8.34 (1H, m), 7.95 -7.91 (1H, m), 7.79 (1H, d), 3.95 (3H, s), 3.52-3.41 (1H, m), 3.09-2.99 (1H) , M), 1.33 (3H, t).
The present condensed heterocyclic compound 85
1H-NMR (CDCl3) δ: 8.78-8.76 (1H, m), 8.47-8.46 (1H, m), 8.31-8.30 (1H, m), 8.10 -8.07 (1H, m), 7.76 (1H, d), 3.76 (3H, s), 3.48 (2H, q), 1.28 (3H, t).
The present condensed heterocyclic compound 86
1H-NMR (CDCl3) δ: 8.51 (1H, d), 8.19 (1H, d), 7.53-7.42 (3H, m), 7.38-7.29 (1H, m ), 3.73 (3H, s), 2.97-2.83 (4H, m), 1.33-1.19 (6H, m).
The present condensed heterocyclic compound 87
1H-NMR (CDCl3) δ: 8.96 (1H, d), 8.54 (1H, d), 8.28-8.18 (1H, m), 7.91-7.80 (2H, m ), 7.63-7.55 (1H, m), 3.74 (3H, s), 3.43 (2H, q), 3.24 (2H, q), 1.38 (3H, t) , 1.26 (3H, t).
This condensed heterocyclic compound 88
1H-NMR (CDCl3) δ: 8.53 (1H, d), 8.23 (1H, d), 7.54-7.42 (3H, m), 7.38-7.29 (1H, m ), 3.74 (3H, s), 3.33-3.22 (1H, m), 2.87 (2H, q), 1.30 (6H, d), 1.24 (3H, t) .
This condensed heterocyclic compound 89
1H-NMR (CDCl3) δ: 8.92 (1H, d), 8.51 (1H, d), 8.22 (1H, dd), 7.92-7.81 (2H, m), 7. 62 (1H, dd), 3.75 (3H, s), 3.43 (2H, q), 3.36-3.26 (1H, m), 1.38 (6H, d), 1.26 (3H, t).
The present condensed heterocyclic compound 90
1H-NMR (CDCl3) δ: 8.69-8.68 (1H, m), 8.33-8.31 (1H, m), 7.70-7.68 (1H, m), 7.62 -7.55 (2H, m), 3.79 (3H, s), 2.97 (2H, q), 1.29 (3H, t).
The present condensed heterocyclic compound 91
1H-NMR (CDCl3) δ: 8.93 (1H, d), 8.52 (1H, d), 8.25 (1H, d), 7.78 (1H, dd), 7.67 (1H, d), 3.76 (2H, q), 1.40 (3H, t).
This condensed heterocyclic compound 92
1H-NMR (CDCl3) δ: 8.89 (1H, d), 8.56 (1H, d), 7.56-7.42 (3H, m), 7.39-7.33 (1H, m ), 3.77 (3H, s), 2.89 (2H, q), 1.25 (3H, t).
This condensed heterocyclic compound 93
1H-NMR (CDCl3) δ: 8.93 (1H, d), 8.53 (1H, d), 8.26 (1H, dd), 7.84 (1H, td), 7.71 (1H, td), 7.60 (1H, dd), 3.89 (3H, s), 3.42-3.32 (1H, m), 3.05-2.96 (1H, m), 1.31 (3H, t).
This condensed heterocyclic compound 94
1H-NMR (CDCl3) δ: 8.91 (1H, d), 8.50 (1H, d), 8.23 (1H, dd), 7.87-7.80 (2H, m), 7. 56 (1H, dd), 3.71 (3H, s), 3.45 (2H, q), 1.26 (3H, t).
This condensed heterocyclic compound 95
1H-NMR (CDCl3) δ: 8.72-8.70 (1H, m), 8.51-8.49 (1H, m), 8.29-8.27 (1H, m), 8.13 -8.09 (1H, m), 7.74-7.71 (1H, m), 3.74 (3H, s), 3.49 (2H, q), 1.29 (3H, t).
The present condensed heterocyclic compound 96
1H-NMR (CDCl3) δ: 8.09 (1H, s), 7.59-7.42 (5H, m), 7.37-7.31 (1H, m), 3.69 (3H, s) ), 2.85 (2H, q), 1.23 (3H, t).
This condensed heterocyclic compound 97
1H-NMR (CDCl3) δ: 8.22 (1H, d), 8.07 (1H, s), 7.80 (1H, t), 7.67 (1H, t), 7.62-7. 52 (3H, m), 3.79 (3H, s), 3.37-3.26 (1H, m), 3.01-2.89 (1H, m), 1.27 (3H, t) .
This condensed heterocyclic compound 98
1H-NMR (CDCl3) δ: 8.20-8.18 (1H, m), 8.06 (1H, s), 7.82-7.74 (2H, m), 7.59-7.52 (3H, m), 3.61 (3H, s), 3.43 (2H, brs), 1.22 (3H, t).
This condensed heterocyclic compound 99
1H-NMR (CDCl3) δ: 8.65-8.64 (1H, m), 8.29-8.28 (1H, m), 7.35-7.31 (2H, m), 7.18 -7.15 (1H, m), 3.76 (3H, s), 2.86 (2H, q), 2.46 (3H, s), 1.23 (3H, t).
The present condensed heterocyclic compound 100
1H-NMR (CDCl3) δ: 8.69-8.68 (1H, m), 8.28-8.26 (1H, m), 8.07-8.05 (1H, m), 7.50 -7.48 (2H, m), 3.89 (3H, s), 3.44-3.33 (1H, m), 3.01-2.92 (1H, m), 2.58 (3H , S), 1.32 (3H, t).
This condensed heterocyclic compound 101
1H-NMR (CDCl3) δ: 8.68-8.66 (1H, m), 8.25-8.23 (1H, m), 8.04-8.02 (1H, m), 7.65 -7.61 (1H, m), 7.45-7.42 (1H, m), 3.71 (3H, s), 3.47-3.38 (2H, m), 2.59 (3H , S), 1.26 (3H, t).
The present condensed heterocyclic compound 102
1H-NMR (CDCl3) δ: 8.81 (1H, d), 8.55 (1H, d), 8.07-8.00 (1H, m), 7.59-7.53 (1H, m ), 7.52-7.45 (1H, m), 7.41-7.33 (1H, m), 2.99 (2H, q), 1.35 (3H, t).
This condensed heterocyclic compound 103
1H-NMR (CDCl3) δ: 8.85 (1H, d), 8.59 (1H, d), 8.15 (1H, d), 7.75 (1H, s), 7.59 (1H, d), 3.05 (2H, q), 1.38 (3H, t).
The condensed heterocyclic compound 104
1H-NMR (CDCl3) δ: 8.87 (1H, d), 8.50 (1H, d), 8.28-8.22 (1H, m), 7.85-7.76 (2H, m ), 7.74-7.70 (1H, m), 3.74 (2H, q), 1.37 (3H, t).
The present condensed heterocyclic compound 105
1H-NMR (CDCl3) δ: 8.90 (1H, s), 8.57-8.49 (2H, m), 8.07 (1H, d), 7.88 (1H, d), 3. 77 (2H, q), 1.40 (3H, t).
This condensed heterocyclic compound 106
1H-NMR (CDCl3) δ: 8.93 (1H, d), 8.61 (1H, d), 7.45-7.34 (3H, m), 2.91 (2H, q), 1. 27 (3H, t).
The present condensed heterocyclic compound 107
1H-NMR (CDCl3) δ: 8.95 (1H, d), 8.55 (1H, d), 8.14 (1H, dd), 7.86 (1H, dd), 7.73 (1H, t), 3.40 (2H, q), 1.28 (3H, t).
The present condensed heterocyclic compound 108
1H-NMR (CDCl3) δ: 8.74-8.72 (1H, m), 8.28-8.26 (1H, m), 8.05-8.03 (1H, m), 7.67 −7.64 (1H, m), 7.46 (1H, d), 3.71 (3H, s), 3.41 (2H, q), 2.88 (2H, q), 1.37 ( 3H, t), 1.26 (3H, t).
The present condensed heterocyclic compound 109
1H-NMR (CDCl3) δ: 8.78-8.76 (1H, m), 8.46-8.44 (1H, m), 8.31-8.30 (1H, m), 8.09 -8.05 (1H, m), 7.76 (1H, d), 3.75 (3H, s), 3.48 (2H, q), 1.27 (3H, t).
The present condensed heterocyclic compound 110
1H-NMR (CDCl3) δ: 8.69 (1H, s), 8.33 (1H, s), 8.25 (1H, dd), 8.21 (1H, dd), 7.73-7. 58 (2H, m), 3.47-3.36 (1H, m), 3.13-3.01 (1H, m), 1.57-0.71 (3H, m).
This condensed heterocyclic compound 111
1H-NMR (CDCl3) δ: 8.76 (1H, d), 8.51 (1H, d), 8.29 (1H, d), 8.10 (1H, dd), 7.74 (1H, d), 4.22 (2H, q), 3.55 (2H, q), 1.42 (3H, t), 1.30 (3H, t).
This condensed heterocyclic compound 112
1H-NMR (CDCl3) δ: 8.13 (1H, s), 7.67 (1H, s), 7.62 (1H, d), 7.59-7.57 (2H, m), 7. 52 (1H, d), 3.70 (3H, s), 2.92 (2H, q), 1.27 (3H, t).
This condensed heterocyclic compound 113
1H-NMR (CDCl3) δ: 8.53 (1H, s), 8.10 (1H, s), 7.93 (1H, d), 7.75 (1H, d), 7.65 (1H, d), 7.57 (1H, d), 3.85 (3H, s), 3.52-3.41 (1H, m), 3.05-2.95 (1H, m), 1.32 (3H, t).
This condensed heterocyclic compound 114
1H-NMR (CDCl3) δ: 8.48 (1H, s), 8.10-8.05 (2H, m), 7.74 (1H, d), 7.62 (1H, d), 7. 53 (1H, d), 3.63 (3H, s), 3.47 (2H, q), 1.25 (3H, t).
This condensed heterocyclic compound 115
1H-NMR (CDCl3) δ: 8.83-8.74 (3H, m), 8.54 (1H, dd), 8.31-8.29 (1H, m), 7.95-7.86 (2H, m), 7.68 (1H, d), 7.41-7.37 (1H, m), 3.75 (3H, s), 3.49 (2H, q), 1.30 ( 3H, t).
The present condensed heterocyclic compound 116
1H-NMR (CDCl3) δ: 8.74-8.72 (1H, m), 8.28-8.25 (1H, m), 8.07-8.05 (1H, m), 7.69 -7.66 (1H, m), 7.47 (1H, d), 3.72 (3H, s), 3.41 (2H, q), 3.18-3.10 (1H, m), 1.37 (6H, d), 1.26 (3H, t).
The present condensed heterocyclic compound 117
1H-NMR (CDCl3) δ: 8.77-8.75 (1H, m), 8.38-8.36 (1H, m), 8.31-8.29 (1H, m), 8.02 -7.99 (1H, m), 7.69 (1H, d), 6.85 (1H, t), 3.73 (3H, s), 3.54-3.33 (2H, m), 1.28 (3H, t).
This condensed heterocyclic compound 118
1H-NMR (CDCl3) δ: 8.68-8.66 (1H, m), 8.31-8.30 (1H, m), 7.48 (1H, d), 7.29-7.26 (1H, m), 7.21-7.17 (1H, m), 3.80 (3H, s), 2.93 (2H, q), 1.29 (3H, t).
This condensed heterocyclic compound 119
1H-NMR (CDCl3) δ: 8.72-8.71 (1H, m), 8.30-8.29 (1H, m), 8.14-8.12 (1H, m), 7.68 (1H, d), 7.55-7.51 (1H, m), 3.93 (3H, s), 3.50-3.40 (1H, m), 3.08-2.98 (1H , M), 1.33 (3H, t).
The present condensed heterocyclic compound 120
1H-NMR (CDCl3) δ: 8.71-8.69 (1H, m), 8.27-8.26 (1H, m), 8.09-8.07 (1H, m), 7.70 −7.66 (1H, m), 7.62 (1H, d), 3.74 (3H, s), 3.47 (2H, q), 1.28 (3H, t).
This condensed heterocyclic compound 121
1H-NMR (CDCl3) δ: 8.11 (1H, s), 7.67 (1H, s), 7.61-7.56 (3H, m), 7.53 (1H, d), 3. 70 (3H, s), 2.93 (2H, q), 1.28 (3H, t).
The present condensed heterocyclic compound 122
1H-NMR (CDCl3) δ: 8.53 (1H, d), 8.09 (1H, s), 7.93 (1H, dd), 7.74 (1H, d), 7.64 (1H, d), 7.59 (1H, d), 3.85 (3H, s), 3.51-3.40 (1H, m), 3.06-2.97 (1H, m), 1.32 (3H, t).
This condensed heterocyclic compound 123
1H-NMR (CDCl3) δ: 8.49 (1H, d), 8.10-8.04 (2H, m), 7.73 (1H, d), 7.60 (1H, d), 7. 55 (1H, d), 3.64 (3H, s), 3.47 (2H, q), 1.25 (3H, t).
The condensed heterocyclic compound 124
1H-NMR (CDCl3) δ: 9.06-9.04 (1H, m), 8.87 (1H, d), 8.77-8.75 (1H, m), 8.59 (1H, dd ), 8.31-8.30 (1H, m), 8.14-8.11 (1H, m), 8.07-8.04 (1H, m), 7.72 (1H, d), 3.76 (3H, s), 3.51 (2H, q), 1.31 (3H, t).
This condensed heterocyclic compound 125
1H-NMR (CDCl3) δ: 8.67-8.66 (1H, m), 8.40-8.39 (1H, m), 7.47 (1H, d), 7.29-7.26 (1H, m), 7.21-7.16 (1H, m), 3.78 (3H, s), 2.93 (2H, q), 1.29 (3H, t).
The present condensed heterocyclic compound 126
1H-NMR (CDCl3) δ: 8.71 (1H, d), 8.39 (1H, d), 8.13-8.12 (1H, m), 7.67 (1H, d), 7. 54-7.50 (1H, m), 3.91 (3H, s), 3.49-3.39 (1H, m), 3.06-2.96 (1H, m), 1.33 ( 3H, t).
The present condensed heterocyclic compound 127
1H-NMR (CDCl3) δ: 8.70 (1H, d), 8.36 (1H, d), 8.09-8.07 (1H, m), 7.70-7.66 (1H, m ), 7.62 (1H, d), 3.72 (3H, s), 3.46 (2H, q), 1.28 (3H, t).
This condensed heterocyclic compound 128
¹ H-NMR (CDCl ₃ ) δ: 8.53 (1H, s), 8.19-8.13 (2H, m), 8.07 (1H, dd), 7.77 (1H, dd), 7.69 (1H, d), 3.91 (2H, q), 1.44 (3H, t).
The present condensed heterocyclic compound 129
¹ H-NMR (CDCl ₃ ) δ: 8.54 (1H, s), 8.33 (1H, s), 8.17 (1H, d), 8.10 (1H, d), 7.89 ( 2H, s), 3.91 (2H, q), 1.45 (3H, t).

Next, formulation examples are shown.

Formulation Example 1
20 parts of one of the condensed heterocyclic compounds 1-131, 35 parts of a mixture of white carbon and polyoxyethylene alkyl ether sulfate ammonium salt (weight ratio 1: 1) and water are mixed to make a total amount of 100 parts. Each preparation is obtained by finely pulverizing by a wet pulverization method.

Formulation Example 2
After mixing 40 parts of this condensed heterocyclic compound 1-131, 1.5 parts of sorbitan trioleate and 28 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and finely pulverizing them by a wet pulverization method, An aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate is added to make a total amount of 90 parts, and further 10 parts of propylene glycol is added and mixed by stirring to obtain each preparation.

Formulation Example 3
By thoroughly pulverizing and mixing 10 parts of one of the condensed heterocyclic compounds 1-131, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and the remainder of the synthetic silicon hydroxide, 100 parts of each wettable powder Get.

Next, application examples of the present condensed heterocyclic compound to plant seeds will be shown.

Application example 1
Each flowable formulation prepared in Formulation Example 1 or 2 was subjected to 200 ml of smear treatment using a rotary seed treatment machine (seed dresser, manufactured by Hans-Ulrich Hege GmbH) for 100 kg of dried sorghum seeds, respectively. Obtain treated seeds.

Application example 2
Each of the flowable preparations prepared in Preparation Example 1 or 2 is subjected to 10 ml smearing treatment for each 10 kg of dried corn seed using a rotary seed processing machine (seed dresser, Hans-Ulrich Hege GmbH). Obtain treated seeds.

Application example 3
Each flowable preparation produced in Formulation Example 1 or 2 is subjected to 40 ml of smear treatment using a rotary seed treatment machine (seed dresser, manufactured by Hans-Ulrich Hege GmbH) for 10 kg of dried corn seeds, respectively. Obtain treated seeds.

Application example 4
Each flowable preparation produced in Formulation Example 1 or 2 is subjected to 100 ml smearing treatment for each 10 kg of dried corn seed using a rotary seed processing machine (seed dresser, Hans-Ulrich Hege GmbH). Obtain treated seeds.

Application example 5
Each wettable powder prepared in Formulation Example 3 is treated with 50 g of powder for 10 kg of dried corn seed to obtain treated seeds.

Application example 6
Each of the flowable preparations prepared in Preparation Example 1 or 2 was subjected to a 20 ml smearing treatment for each 10 kg of dried soybean seeds using a rotary seed processing machine (seed dresser, Hans-Ulrich Hege GmbH). Obtain treated seeds.

Application example 7
Each of the flowable preparations prepared in Preparation Example 1 or 2 is treated with 100 ml of each seed by using a rotary seed treatment machine (seed dresser, manufactured by Hans-Ulrich Hege GmbH) on 10 kg of dried soybean seeds. Get seeds.

Application Example 8
Each flowable preparation prepared in Formulation Example 1 or 2 was subjected to 50 ml smearing treatment on a dry seed 10 kg using a rotary seed treatment machine (seed dresser, Hans-Ulrich Hege GmbH). Obtain treated seeds.

Application Example 9
Each flowable preparation produced in Formulation Example 1 or 2 was subjected to 50 ml smearing treatment on a dry seed of rapeseed 10 kg using a rotary seed treatment machine (seed dresser, Hans-Ulrich Hege GmbH). Obtain treated seeds.

Application Example 10
Each of the flowable preparations prepared in Formulation Example 1 or 2 is subjected to 10 ml of smear treatment using a rotary seed treatment machine (seed dresser, manufactured by Hans-Ulrich Hege GmbH) for 10 kg of rapeseed dry seeds, respectively. Obtain treated seeds.

Next, the harmful arthropod controlling effect of the method of the present invention will be shown by test examples.

Test example 1
This condensed heterocyclic compound 3, 31, 39, 41, 42, 46, 48, 51, 56, 58, 64, 69, 72, 74, 78, 83, 91, 97, 104, 105, 107, 108, 109 , 120, 127, and 131 are dissolved in acetone (manufactured by Wako Pure Chemical Industries) containing 5% (W / V) Sorgen TW-20 (Daiichi Kogyo Seiyaku Co., Ltd.) so as to have a predetermined concentration. Was prepared.
Nine radish seeds (Raphanus sativas var. Longipinnatus) (total weight of about 0.16 g) were placed in a 2 ml polypropylene microtube (manufactured by ASONE), and 18 μL of the above test chemical was added thereto, followed by a stirrer (trade name) : VORTEX-GENIE2, manufactured by Scientific industries), the seeds in the microtube were shaken and stirred. After the chemical solution was evenly distributed throughout the seeds, the seeds were air-dried.
5 ml of water was added to a 90 ml plastic cup filled with 10 g of cultivated soil (trade name: Aina Ichigo, manufactured by Katakura Chikkarin), and three seeds were seeded there.
Four days after sowing, ten third instar larvae (Plutella xylostella) were released per cup and covered with nylon goose. This is called a processing zone.
On the other hand, except that this fused heterocyclic compound was not dissolved in acetone (manufactured by Wako Pure Chemical Industries, Ltd.) containing 5% (W / V) of Sorgen TW-20 (Daiichi Kogyo Seiyaku) After seeding radish and releasing larvae, they were covered. This is called an untreated section.
Two days after release, larvae were observed for viability, and the mortality rate was calculated from the observation results using Equation 1). The test was repeated twice. The average values are shown in Table 5, Table 6 and Table 7.
Formula 1): Death rate (%) = (number of test insects−number of surviving insects) / number of test insects × 100

According to the method for controlling harmful arthropods of the present invention, harmful arthropods can be controlled.

Claims

Formula (1)

[Where:
A1 represents -NR6-, an oxygen atom or a sulfur atom,
A2 represents a nitrogen atom or = CH-,
R 1, R 2, R 3 and R 4 are the same or different and each have one or more atoms or groups selected from C1-C3 chain hydrocarbon group optionally having one or more halogen atoms and group Z An optionally substituted phenyl group, a 6-membered heterocyclic group optionally having one or more atoms or groups selected from group Z, -OR7, -S (O) mR7, a halogen atom, or a hydrogen atom; (However, at least two of R1, R2, R3 and R4 represent a hydrogen atom.),
R5 represents a C1-C3 chain hydrocarbon group which may have one or more atoms or groups selected from group X, -OR7, -S (O) mR7, or a halogen atom;
R6 is a C1-C3 chain hydrocarbon group which may have one or more atoms or groups selected from group W, and C3 which may have one or more atoms or groups selected from group W. -C6 represents an alicyclic hydrocarbon group or a hydrogen atom,
R7 represents a C1-C3 chain hydrocarbon group which may have one or more halogen atoms or a hydrogen atom,
m represents 0, 1 or 2, and n represents 0, 1 or 2.
Here, in -S (O) mR7, when m is 1 or 2, R7 does not represent a hydrogen atom.
Group X: C1-C3 alkoxy group optionally having one or more halogen atoms, C2-C3 alkenyloxy group optionally having one or more halogen atoms, having one or more halogen atoms An optionally substituted C2-C3 alkynyloxy group, a C1-C3 alkylsulfanyl group optionally having one or more halogen atoms, a C1-C3 alkylsulfinyl optionally having one or more halogen atoms A group consisting of a group, a C1-C3 alkylsulfonyl group optionally having one or more halogen atoms, a cyano group, a hydroxy group, and a halogen atom;
Group Z: C1-C3 chain hydrocarbon group optionally having one or more halogen atoms, C1-C3 alkoxy group optionally having one or more halogen atoms, one or more halogen atoms A C1-C3 alkylsulfanyl group optionally having one or more, a C1-C3 alkylsulfinyl group optionally having one or more halogen atoms, a C1-C3 optionally having one or more halogen atoms A group consisting of an alkylsulfonyl group, a cyano group, a nitro group and a halogen atom.
Group W: C1-C3 alkoxy group optionally having one or more halogen atoms, C2-C3 alkenyloxy group optionally having one or more halogen atoms, having one or more halogen atoms A group consisting of a C2-C3 alkynyloxy group, a halogen atom and a hydroxy group, which may be ]
A method for controlling harmful arthropods, which comprises treating plant seeds with a compound represented by
Formula (1)

[Where:
A1 represents -NR6-, an oxygen atom or a sulfur atom,
A2 represents a nitrogen atom or = CH-,
R 1, R 2, R 3 and R 4 are the same or different and each have one or more atoms or groups selected from C1-C3 chain hydrocarbon group optionally having one or more halogen atoms and group Z An optionally substituted phenyl group, a 6-membered heterocyclic group optionally having one or more atoms or groups selected from group Z, -OR7, -S (O) mR7, a halogen atom, or a hydrogen atom; (However, at least two of R1, R2, R3 and R4 represent a hydrogen atom.),
R5 represents a C1-C3 chain hydrocarbon group which may have one or more atoms or groups selected from group X, -OR7, -S (O) mR7, or a halogen atom;
R6 is a C1-C3 chain hydrocarbon group which may have one or more atoms or groups selected from group W, and C3 which may have one or more atoms or groups selected from group W. -C6 represents an alicyclic hydrocarbon group or a hydrogen atom,
R7 represents a C1-C3 chain hydrocarbon group which may have one or more halogen atoms or a hydrogen atom,
m represents 0, 1 or 2, and n represents 0, 1 or 2. Here, in -S (O) mR7, when m is 1 or 2, R7 does not represent a hydrogen atom.
Group X: C1-C3 alkoxy group optionally having one or more halogen atoms, C2-C3 alkenyloxy group optionally having one or more halogen atoms, having one or more halogen atoms An optionally substituted C2-C3 alkynyloxy group, a C1-C3 alkylsulfanyl group optionally having one or more halogen atoms, a C1-C3 alkylsulfinyl optionally having one or more halogen atoms A group consisting of a group, a C1-C3 alkylsulfonyl group optionally having one or more halogen atoms, a cyano group, a hydroxy group, and a halogen atom;
Group Z: C1-C3 chain hydrocarbon group optionally having one or more halogen atoms, C1-C3 alkoxy group optionally having one or more halogen atoms, one or more halogen atoms A C1-C3 alkylsulfanyl group optionally having one or more, a C1-C3 alkylsulfinyl group optionally having one or more halogen atoms, a C1-C3 optionally having one or more halogen atoms A group consisting of an alkylsulfonyl group, a cyano group, a nitro group and a halogen atom.
Group W: C1-C3 alkoxy group optionally having one or more halogen atoms, C2-C3 alkenyloxy group optionally having one or more halogen atoms, having one or more halogen atoms A group consisting of a C2-C3 alkynyloxy group, a halogen atom and a hydroxy group, which may be ] The plant seed processed by the compound shown by this.
The method for controlling harmful arthropods according to claim 1, wherein 0.01 to 1000 g of the compound represented by the formula (1) is used per 10 kg of plant seeds.
The method for controlling harmful arthropods according to claim 1 or 3, wherein the plant seeds are seeds of corn, cotton, soybean, sugar beet, rapeseed, radish or rice.