WO2015198859A1

WO2015198859A1 - Condensed heterocyclic compound

Info

Publication number: WO2015198859A1
Application number: PCT/JP2015/066673
Authority: WO
Inventors: 貴將田邊; 亮太前畑; 綾香長谷部; 慎哉西村
Original assignee: 住友化学株式会社
Priority date: 2014-06-26
Filing date: 2015-06-10
Publication date: 2015-12-30

Abstract

A condensed heterocyclic compound that can be represented by formula (1) (in which A represents NCH₃ or an oxygen atom; R¹ represents a hydrogen atom, a C_1-3 alkyl group that may contain one or more halogen atoms, a halogen atom, a C_1-3 alkoxy group, a C_2-4 alkoxycarbonyl group, S(O)_mR², NR³R⁴, a nitro group, or a cyano group; R² represents a C_1-3 alkyl group; R³ and R⁴ each independently represent a hydrogen atom or a C_1-3 alkyl group; R⁵ represents a C_1-3 perfluoroalkyl group or S(O)_p-R⁶; R⁶ represents a C_1-3 perfluoroalkyl group; n represents 0, 1, or 2; m represents 0, 1, or 2; and p represents 0, 1 or 2) exhibits excellent pest-control efficacy.

Description

Fused heterocyclic compounds

The present invention relates to certain condensed heterocyclic compounds and their use for pest control.

So far, various compounds have been studied and put into practical use for the purpose of controlling pests.
Also, certain types of fused heterocyclic compounds (for example, see Patent Document 1) are known.

International Publication No. 2013/018928

An object of the present invention is to provide a compound having an excellent control effect against pests and a method for controlling pests using the compound.

As a result of studies to solve the above problems, the present inventors have found that the condensed heterocyclic compound represented by the following formula (1) has an excellent control effect against pests.

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

[Where:
A represents NCH ₃ or an oxygen atom,
R ¹ is a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C3 alkoxy group, a C2-C4 alkoxycarbonyl group, S (O) _m R ² , NR ³ R ⁴ represents a nitro group or a cyano group,
R ² represents a C1-C3 alkyl group,
R ³ and R ⁴ each independently represents a hydrogen atom or a C1-C3 alkyl group,
R ⁵ represents a C1-C3 perfluoroalkyl group or S (O) _p —R ⁶ ,
R ⁶ represents a C1-C3 perfluoroalkyl group,
n represents 0, 1 or 2,
m represents 0, 1 or 2;
p represents 0, 1 or 2. ]
A condensed heterocyclic compound represented by the following (hereinafter referred to as the present compound).
[2] The compound according to [1], wherein A is NCH ₃ .
[3] The compound according to [1], wherein A is an oxygen atom.
[4] R ¹ is a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C3 alkoxy group, or S (O) _m R ² [1] ] To [3] The compound according to any one of the above.
[5] Any of [1] to [3], wherein R ¹ is a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, a trifluoromethyl group, a methoxy group, a methylsulfanyl group, a methylsulfinyl group, or a methylsulfonyl group A compound according to 1.
[6] The compound according to any one of [1] to [5], wherein R ⁵ is a trifluoromethyl group or a S (O) _p —CF ₃ group.
[7] A pest control composition comprising the compound according to any one of [1] to [6] and an inert carrier.
[8] A method for controlling pests, which comprises applying an effective amount of the compound according to any one of [1] to [6] to a pest or a pest habitat.

The compound of the present invention is useful as an active ingredient of a pest control agent because it has an excellent control activity against pests.

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

In the compound of the present invention, examples of the “C1-C3 alkyl group” include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
In the compound of the present invention, the “C1-C3 alkyl group optionally having one or more halogen atoms” refers to a C1-C3 alkyl group in which at least one hydrogen atom may be substituted with a halogen atom. Represents a C3 alkyl group, for example, fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, dichloromethyl group, trifluoromethyl group, chlorodifluoromethyl group, bromodifluoromethyl group, trichloromethyl group, 2- Examples include fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group and heptafluoroisopropyl group. .

The “C1-C3 perfluoroalkyl group” represents a C1-C3 alkyl group in which all hydrogen atoms are substituted with fluorine atoms, specifically, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, A heptafluoroisopropyl group is mentioned.

In the compounds of the present invention, examples of the “C1-C3 alkoxy group” include a methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group.

In the compound of the present invention, examples of the “C1-C3 alkylamino group” include a methylamino group, an ethylamino group, a propylamino group, and an isopropylamino group.

In the compound of the present invention, the “di (C1-C3 alkyl) amino group” includes N, N-dimethylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-diisopropylamino group, N-methyl-N-ethylamino group, N-methyl-N-propylamino group, N-methyl-N-isopropylamino group, N-ethyl-N-propylamino group, and N-ethyl-N-isopropylamino group Is mentioned.

In the compound of the present invention, “C2-C4 alkoxycarbonyl group” represents a group in which a C1-C3 alkoxy group and a carbonyl group are bonded, and represents a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, or an isopropoxycarbonyl group.

In the compound of the present invention, “S (O) _m R ² ” represents a C1-C3 alkylsulfanyl group in which m is 0, an alkylsulfinyl group in which m is 1 and an alkylsulfonyl group in which m is 2.
The C1-C3 alkylsulfanyl group represents a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, and an isopropylsulfanyl group.
The C1-C3 alkylsulfinyl group represents a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, and an isopropylsulfinyl group.
The C1-C3 alkylsulfonyl group represents a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, and an isopropylsulfonyl group.

As an aspect of this invention compound, the following compounds are mentioned, for example.

A compound in which n = 0 in formula (1);
A compound wherein n = 1 in formula (1);
A compound wherein n = 2 in the formula (1);

In the formula (1), compounds wherein ^{R 5} is C1-C3 perfluoroalkyl group;
In the formula (1), compounds wherein R ⁵ is CF ₃ ;
In the formula (1), compounds wherein R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein R ⁵ is S (O) _p —CF ₃

In the formula (1), compounds wherein R ¹ is a hydrogen atom or a halogen atom;
In the formula (1), compounds wherein R ¹ is a hydrogen atom;
In the formula (1), compounds wherein R ¹ is a halogen atom;
In the formula (1), compounds wherein R ¹ is a chlorine atom;
In the formula (1), compounds wherein R ¹ is a C1-C3 alkyl group optionally having one or more halogen atoms;
In the formula (1), compounds wherein R ¹ is a C1-C3 alkyl group;
In the formula (1), compounds wherein R ¹ is a methyl group;
In the formula (1), compounds wherein R ¹ is S (O) _m R ² ;
In the formula (1), compounds wherein R ¹ is a C1-C3 alkylsulfanyl group, a C1-C3 alkylsulfinyl group, or a C1-C3 alkylsulfonyl group;
In the formula (1), compounds wherein R ¹ is a methylsulfanyl group, a methylsulfinyl group or a methylsulfonyl group;
In the formula (1), compounds wherein R ¹ is a methylsulfanyl group or a methylsulfonyl group;
In the formula (1), compounds wherein R ¹ is NR ³ R ⁴ ;
In the formula (1), compounds wherein R ¹ is an amino group, a C1-C3 alkylamino group, a di (C1-C3 alkyl) amino group or a nitro group;
In the formula (1), compounds wherein R ¹ is an amino group;

In the formula (1), compounds wherein A is NCH ₃ and n = 2;
In the formula (1), compounds wherein A is an oxygen atom and n = 2;

In the formula (1), compounds wherein R ⁵ is a C1-C3 perfluoroalkyl group and n = 2;
In the formula (1), compounds wherein R ⁵ is CF ₃ and n = 2;
In the formula (1), compounds wherein R ⁵ is S (O) _p —R ⁶ and n = 2;
In the formula (1), compounds wherein R ⁵ is S (O) _p —CF ₃ and n = 2

In the formula (1), compounds wherein A is NCH ₃ and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), compounds wherein A is NCH ₃ and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ and R ⁵ is S (O) p—R ⁶ ;
In the formula (1), compounds wherein A is NCH ₃ and R ⁵ is S (O) p-CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), compounds wherein A is an oxygen atom and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is an oxygen atom and R ⁵ is S (O) _p —CF ₃

In the formula (1), compounds wherein R ¹ is a hydrogen atom or a halogen atom, and A is NCH ₃ ;
In the formula (1), compounds wherein R ¹ is a hydrogen atom, and A is NCH ₃ ;
In the formula (1), compounds wherein R ¹ is a halogen atom and A is NCH ₃ ;
In the formula (1), compounds wherein R ¹ is a chlorine atom and A is NCH ₃ ;
In the formula (1), compounds wherein R ¹ is a C1-C3 alkyl group optionally having one or more halogen atoms, and A is NCH ₃ ;
In the formula (1), compounds wherein R ¹ is a C1-C3 alkyl group and A is NCH ₃ ;
In formula (1), ^{R 1} is a methyl group, compounds wherein A is NCH _3;
In the formula (1), compounds wherein R ¹ is S (O) _m R ² and A is NCH ₃ ;
In the formula (1), compounds wherein R ¹ is a C1-C3 alkylsulfanyl group, a C1-C3 alkylsulfinyl group, or a C1-C3 alkylsulfonyl group, and A is NCH ₃ ;
In formula (1), R ¹ is methylsulfanyl group, a methylsulfinyl group or a methylsulfonyl group, compounds wherein A is NCH _3;
In the formula (1), compounds wherein R ¹ is a methylsulfanyl group or a methylsulfonyl group, and A is NCH ₃ ;
In the formula (1), compounds wherein R ¹ is NR ³ R ⁴ and A is NCH ₃ ;
In the formula (1), compounds wherein R ¹ is an amino group, a C1-C3 alkylamino group, a di (C1-C3 alkyl) amino group or a nitro group, and A is NCH ₃ ;
In the formula (1), compounds wherein R ¹ is an amino group, and A is NCH ₃ ;

In the formula (1), compounds wherein R ¹ is a hydrogen atom or a halogen atom, and A is an oxygen atom;
In the formula (1), compounds wherein R ¹ is a hydrogen atom, and A is an oxygen atom;
In the formula (1), compounds wherein R ¹ is a halogen atom and A is an oxygen atom;
In the formula (1), compounds wherein R ¹ is a chlorine atom and A is an oxygen atom;
In the formula (1), compounds wherein R ¹ is a C1-C3 alkyl group optionally having one or more halogen atoms, and A is an oxygen atom;
In the formula (1), compounds wherein R ¹ is a C1-C3 alkyl group, and A is an oxygen atom;
In the formula (1), a compound in which R ¹ is a methyl group and A is an oxygen atom; in the formula (1), a compound in which R ¹ is S (O) _m R ² and A is an oxygen atom;
In the formula (1), compounds wherein R ¹ is a C1-C3 alkylsulfanyl group, a C1-C3 alkylsulfinyl group, or a C1-C3 alkylsulfonyl group, and A is an oxygen atom;
In the formula (1), compounds wherein R ¹ is a methylsulfanyl group, a methylsulfinyl group or a methylsulfonyl group, and A is an oxygen atom;
In the formula (1), compounds wherein R ¹ is a methylsulfanyl group or a methylsulfonyl group, and A is an oxygen atom;
In the formula (1), compounds wherein R ¹ is NR ³ R ⁴ and A is an oxygen atom;
In the formula (1), compounds wherein R ¹ is an amino group, a C1-C3 alkylamino group, a di (C1-C3 alkyl) amino group or a nitro group, and A is an oxygen atom;
In the formula (1), compounds wherein R ¹ is an amino group, and A is an oxygen atom;

In the formula (1), compounds wherein A is NCH ₃ , n = 2 and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , n = 2 and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, n = 2, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, n = 2, and R ⁵ is S (O) _p CF ₃ ;

In the formula (1), A is NCH ₃ , R ¹ is a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, an amino group, or S (O) _m R ^A compound wherein R ⁵ is a C1-C3 perfluoroalkyl group or S (O) _p R ⁶ and n is 0, 1 or 2;
In formula (1), A is NCH ₃ , R ¹ is a hydrogen atom, a C1-C3 alkyl group, a halogen atom, an amino group, or S (O) _m R ² , and R ⁵ is CF ₃ or S (O ) _P CF ₃ and n is 0, 1 or 2;
In Formula (1), A is NCH ₃ , R ¹ is a hydrogen atom, a chlorine atom, a methyl group, an amino group, a methylsulfanyl group, a methylsulfinyl group, or a methylsulfonyl group, and R ⁵ is CF ₃ or S ( O) _p CF ₃ and n = 2 compound;

In the formula (1), A is an oxygen atom, R ¹ is a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, an amino group, or S (O) _m R ^A compound in which R ⁵ is a C1-C3 perfluoroalkyl group or S (O) _p R ⁶ , and n is 0, 1 or 2;
In formula (1), A is an oxygen atom, R ¹ is a hydrogen atom, a C1-C3 alkyl group, a halogen atom, an amino group, or S (O) _m R ² , and R ⁵ is CF ₃ or S (O ) _P CF ₃ and n is 0, 1 or 2;
In Formula (1), A is an oxygen atom, R ¹ is a hydrogen atom, a chlorine atom, a methyl group, an amino group, a methylsulfanyl group, a methylsulfinyl group, or a methylsulfonyl group, and R ⁵ is CF ₃ or S ( O) _p CF ₃ and n = 2 compound;

In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a hydrogen atom or a halogen atom, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a hydrogen atom, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a halogen atom, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a chlorine atom, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a C1-C3 alkyl group optionally having one or more halogen atoms, and R ⁵ is a C1-C3 perfluoroalkyl group ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a C1-C3 alkyl group, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a methyl group, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is S (O) _m R ² , and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), A is NCH ₃ , R ¹ is a C1-C3 alkylsulfanyl group, a C1-C3 alkylsulfinyl group, or a C1-C3 alkylsulfonyl group, and R ⁵ is a C1-C3 perfluoroalkyl group. A compound which is
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a methylsulfanyl group, a methylsulfinyl group or a methylsulfonyl group, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a methylsulfanyl group or a methylsulfonyl group, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is NR ³ R ⁴ and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), A is NCH _3, ^{R 1} is an amino group, C1-C3 alkylamino group, di is (C1-C3 alkyl) amino group or a nitro group, ^{R 5} is C1-C3 perfluoroalkyl A compound which is a group;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is an amino group, and R ⁵ is a C1-C3 perfluoroalkyl group;

In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a hydrogen atom or a halogen atom, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a hydrogen atom, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a halogen atom, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a chlorine atom, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a C1-C3 alkyl group optionally having one or more halogen atoms, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a C1-C3 alkyl group, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a methyl group, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is S (O) _m R ² , and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a C1-C3 alkylsulfanyl group, a C1-C3 alkylsulfinyl group, or a C1-C3 alkylsulfonyl group, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a methylsulfanyl group, methylsulfinyl group or methylsulfonyl group, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a methylsulfanyl group or a methylsulfonyl group, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is NR ³ R ⁴ and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is an amino group, a C1-C3 alkylamino group, a di (C1-C3 alkyl) amino group or a nitro group, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is an amino group, and R ⁵ is CF ₃ ;

In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a hydrogen atom or a halogen atom, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a hydrogen atom, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a halogen atom, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a chlorine atom, and R ⁵ is S (O) _p —R ⁶ ;
In formula (1), A is NCH ₃ , R ¹ is a C1-C3 alkyl group optionally having one or more halogen atoms, and R ⁵ is S (O) _p —R ⁶ . Compound;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a C1-C3 alkyl group, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a methyl group, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is S (O) _m R ² , and R ⁵ is S (O) _p —R ⁶ ;
In Formula (1), A is NCH ₃ , R ¹ is a C1-C3 alkylsulfanyl group, a C1-C3 alkylsulfinyl group, or a C1-C3 alkylsulfonyl group, and R ⁵ is S (O) _p —R ⁶ is a compound;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a methylsulfanyl group, a methylsulfinyl group or a methylsulfonyl group, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a methylsulfanyl group or a methylsulfonyl group, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is NR ³ R ⁴ , and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), A is NCH ₃ , R ¹ is an amino group, a C1-C3 alkylamino group, a di (C1-C3 alkyl) amino group or a nitro group, and R ⁵ is S (O) _p −. The compound which is R ⁶ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is an amino group, and R ⁵ is S (O) _p —R ⁶ ;

In the formula (1), a compound wherein A is NCH ₃ , R ¹ is a hydrogen atom or a halogen atom, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a hydrogen atom, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a halogen atom, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a chlorine atom, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a C1-C3 alkyl group optionally having one or more halogen atoms, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a C1-C3 alkyl group, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), A is NCH _3, ^{R 1} is a methyl group, ^{R 5} is an S _(O) p CF _3;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is S (O) _m R ² , and R ⁵ is S (O) _p CF ₃ ;
In Formula (1), A is NCH ₃ , R ¹ is a C1-C3 alkylsulfanyl group, a C1-C3 alkylsulfinyl group, or a C1-C3 alkylsulfonyl group, and R ⁵ is S (O) _p CF ₃ A compound which is
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a methylsulfanyl group, a methylsulfinyl group or a methylsulfonyl group, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is a methylsulfanyl group or a methylsulfonyl group, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is NR ³ R ⁴ , and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), A is NCH ₃ , R ¹ is an amino group, a C1-C3 alkylamino group, a di (C1-C3 alkyl) amino group or a nitro group, and R ⁵ is S (O) _p CF ₃ is a compound;
In the formula (1), compounds wherein A is NCH ₃ , R ¹ is an amino group, and R ⁵ is S (O) _p CF ₃ ;

In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a hydrogen atom or a halogen atom, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), a compound wherein A is an oxygen atom, R ¹ is a hydrogen atom, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a halogen atom, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), a compound wherein A is an oxygen atom, R ¹ is a chlorine atom, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), a compound in which A is an oxygen atom, R ¹ is a C1-C3 alkyl group optionally having one or more halogen atoms, and R ⁵ is a C1-C3 perfluoroalkyl group ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a C1-C3 alkyl group, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), a compound wherein A is an oxygen atom, R ¹ is a methyl group, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is S (O) _m R ² and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), A is an oxygen atom, R ¹ is a C1-C3 alkylsulfanyl group, a C1-C3 alkylsulfinyl group, or a C1-C3 alkylsulfonyl group, and R ⁵ is a C1-C3 perfluoroalkyl group. A compound which is
In the formula (1), a compound wherein A is an oxygen atom, R ¹ is a methylsulfanyl group, a methylsulfinyl group or a methylsulfonyl group, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), a compound wherein A is an oxygen atom, R ¹ is a methylsulfanyl group or a methylsulfonyl group, and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is NR ³ R ⁴ and R ⁵ is a C1-C3 perfluoroalkyl group;
In the formula (1), A is an oxygen atom, R ¹ is an amino group, a C1-C3 alkylamino group, a di (C1-C3 alkyl) amino group or a nitro group, and R ⁵ is a C1-C3 perfluoroalkyl. A compound that is a group;
In the formula (1), a compound wherein A is an oxygen atom, R ¹ is an amino group, and R ⁵ is a C1-C3 perfluoroalkyl group;

In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a hydrogen atom or a halogen atom, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a hydrogen atom, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a halogen atom, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a chlorine atom, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a C1-C3 alkyl group optionally having one or more halogen atoms, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a C1-C3 alkyl group, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a methyl group, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is S (O) _m R ² , and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a C1-C3 alkylsulfanyl group, a C1-C3 alkylsulfinyl group or a C1-C3 alkylsulfonyl group, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a methylsulfanyl group, a methylsulfinyl group or a methylsulfonyl group, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a methylsulfanyl group or a methylsulfonyl group, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is NR ³ R ⁴ , and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is an amino group, a C1-C3 alkylamino group, a di (C1-C3 alkyl) amino group or a nitro group, and R ⁵ is CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is an amino group, and R ⁵ is CF ₃ ;

In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a hydrogen atom or a halogen atom, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a hydrogen atom, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a halogen atom, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a chlorine atom, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), A is an oxygen atom, R ¹ is a C1-C3 alkyl group optionally having one or more halogen atoms, and R ⁵ is S (O) _p —R ⁶ . Compound;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a C1-C3 alkyl group, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a methyl group, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is S (O) _m R ² , and R ⁵ is S (O) _p —R ⁶ ;
In Formula (1), A is an oxygen atom, R ¹ is a C1-C3 alkylsulfanyl group, a C1-C3 alkylsulfinyl group, or a C1-C3 alkylsulfonyl group, and R ⁵ is S (O) _p —R ⁶ is a compound;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a methylsulfanyl group, a methylsulfinyl group or a methylsulfonyl group, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a methylsulfanyl group or a methylsulfonyl group, and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is NR ³ R ⁴ , and R ⁵ is S (O) _p —R ⁶ ;
In the formula (1), A is an oxygen atom, R ¹ is an amino group, a C1-C3 alkylamino group, a di (C1-C3 alkyl) amino group or a nitro group, and R ⁵ is S (O) _p −. The compound which is R ⁶ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is an amino group, and R ⁵ is S (O) _p —R ⁶ ;

In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a hydrogen atom or a halogen atom, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), A is an oxygen atom, ^{R 1} is hydrogen atom, ^{R 5} is an S _(O) p CF _3;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a halogen atom, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), a compound wherein A is an oxygen atom, R ¹ is a chlorine atom, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a C1-C3 alkyl group optionally having one or more halogen atoms, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), compounds wherein A is an oxygen atom, R ¹ is a C1-C3 alkyl group, and R ⁵ is S (O) _p CF ₃ ;
In formula (1), a compound wherein A is an oxygen atom, R ¹ is a methyl group, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), a compound wherein A is an oxygen atom, R ¹ is S (O) _m R ² , and R ⁵ is S (O) _p CF ₃ ;
In Formula (1), A is an oxygen atom, R ¹ is a C1-C3 alkylsulfanyl group, a C1-C3 alkylsulfinyl group, or a C1-C3 alkylsulfonyl group, and R ⁵ is S (O) _p CF ₃ A compound which is
In formula (1), a compound wherein A is an oxygen atom, R ¹ is a methylsulfanyl group, a methylsulfinyl group or a methylsulfonyl group, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), a compound in which A is an oxygen atom, R ¹ is a methylsulfanyl group or a methylsulfonyl group, and R ⁵ is S (O) _p CF ₃ ;
In the formula (1), A is an oxygen atom, ^{R 1} is ^NR 3 ^{R 4,} ^{R 5} is an S _(O) p CF _3;
In the formula (1), A is an oxygen atom, R ¹ is an amino group, a C1-C3 alkylamino group, a di (C1-C3 alkyl) amino group or a nitro group, and R ⁵ is S (O) _p CF ₃ is a compound;
In formula (1), a compound wherein A is an oxygen atom, R ¹ is an amino group, and R ⁵ is S (O) _p CF ₃ ;

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

The compound of the present invention and the production intermediate compound can be produced, for example, by any of the production methods 1 to 11 described below.

Manufacturing method 1
The present compound (1b) in which n = 1 in the formula (1) (hereinafter referred to as the present compound (1b)), and the present compound (1c) in which n = 2 in the formula (1) (hereinafter referred to as the present compound). Inventive compound (1c) is prepared by reacting present compound (1a) (hereinafter referred to as present compound (1a)) in which n = 0 in formula (1) with an oxidizing agent. be able to.

[Wherein the symbols have the same meaning as in formula (1). ]

First, a method for producing the present compound (1b) from the present compound (1a) will be described.
The reaction is performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile, alcohols such as methanol and ethanol, acetic acid, water, and mixtures thereof.
Examples of the oxidizing agent used in the reaction include sodium periodate, m-chloroperbenzoic acid, and hydrogen peroxide.
When hydrogen peroxide is used as the oxidizing agent, a base or a catalyst may be added as necessary.
Examples of the base used for the reaction include sodium carbonate.
Examples of the catalyst used for the reaction include tungstic acid and sodium tungstate.
In the reaction, with respect to 1 mol of the compound (1a) of the present invention, an oxidizing agent is usually used in a proportion of 1 to 1.2 mol.
In the reaction, the base is generally used at a ratio of 0.01 to 1 mol per 1 mol of the compound (1a) of the present invention.
In the reaction, the catalyst is generally used in a proportion of 0.01 to 0.5 mol per 1 mol of the compound (1a) of the present invention.
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 and sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary. The compound (1b) of the present invention can be isolated by drying and concentrating the washed organic layer. The isolated compound (1b) of the present invention can be further purified by chromatography, recrystallization and the like.

Next, a method for producing the present compound (1c) from the present compound (1b) will be described.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile, 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 and hydrogen peroxide.
When hydrogen peroxide is used as the oxidizing agent, a base or a catalyst may be added as necessary.
Examples of the base used for the reaction include sodium carbonate.
Examples of the catalyst used in the reaction include sodium tungstate.
In the reaction, the oxidizing agent is usually used at a ratio of 1 to 4 moles with respect to 1 mole of the compound (1b) of the present invention. Preferably, the oxidizing agent is used in a ratio of 1 to 2 moles relative to 1 mole of the compound (1b) of the present invention.
In the reaction, the base is generally used at a ratio of 0.01 to 1 mol per 1 mol of the compound (1b) of the present invention.
In the reaction, the catalyst is generally used in a proportion of 0.01 to 0.5 mol with respect to 1 mol of the compound (1b) of the present invention.
The reaction temperature is usually in the range of −20 to 120 ° C. The reaction time is usually in the range of 0.1 to 12 hours.
After completion of the reaction, 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 and sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary. The compound (1c) of the present invention can be isolated by drying and concentrating the organic layer. The compound (1c) of the present invention can be further purified by chromatography, recrystallization and the like.

Moreover, this invention compound (1c) can be manufactured by a one-step reaction (one pot) by making this invention compound (1a) and an oxidizing agent react.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile, 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 and hydrogen peroxide.
When hydrogen peroxide is used as the oxidizing agent for the reaction, it is carried out in the presence of a base or a catalyst as necessary.
Examples of the base used for the reaction include sodium carbonate.
Examples of the catalyst used for the reaction include tungstic acid and sodium tungstate.
In the reaction, with respect to 1 mole of the compound (1a) of the present invention, an oxidizing agent is usually used at a ratio of 2 to 5 moles.
In the reaction, the base is generally used at a ratio of 0.01 to 1 mol per 1 mol of the compound (1a) of the present invention.
In the reaction, the catalyst is generally used in a proportion of 0.01 to 0.5 mol per 1 mol of the compound (1a) of the present invention.
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 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 and sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary. The compound (1c) of the present invention can be isolated by drying and concentrating the organic layer. The isolated compound (1c) of the present invention can be further purified by chromatography, recrystallization and the like.

Manufacturing method 2
The compound of the present invention comprises a compound represented by formula (M1) (hereinafter referred to as compound (M1)) and a compound represented by formula (M2) (hereinafter referred to as compound (M2)) as a base. It can manufacture by making it react in presence.

[Wherein, X represents a halogen atom, and other symbols have the same meaning as in formula (1). ]
Compound (M2) is known or can be produced according to a known method.
The present compound (1a) to the present compound (1c) can be produced according to this reaction.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene. Hydrogen, aromatic hydrocarbons such as toluene, benzene, xylene, esters such as ethyl acetate and butyl acetate, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolid Non-protic polar solvents such as non- and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, 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, alkali metal carbonates such as sodium carbonate and potassium carbonate, or triethylamine and diisopropylene. And organic bases such as propylethylamine, pyridine and 4-dimethylaminopyridine.
In the reaction, with respect to 1 mol of the compound (M1), the compound (M2) is usually used in a proportion of 1 to 2 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 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 added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered. The compound of the present invention can be isolated by collecting by The isolated compound of the present invention can be further purified by recrystallization, chromatography or the like.

Production method 3
Compound (M1b) where n = 1 in compound (M1) (hereinafter referred to as compound (M1b)), and Compound (M1c) where n = 2 in compound (M1) (hereinafter referred to as compound (M1c)) Can be produced by reacting a compound (M1a) in which n = 0 in the compound (M1) (hereinafter referred to as compound (M1a)) with an oxidizing agent.

[Wherein the symbols have the same meaning as described above. ]
This reaction is produced according to the reaction described in Production Example 1 by substituting compound (M1a) for the present compound (1a) in production method 1 or substituting (M1b) for the present compound (1b). be able to.

Manufacturing method 4
Compound (M1a) can be produced, for example, according to the following scheme.

[Wherein the symbols have the same meaning as described above. ]

A compound represented by formula (M7) (hereinafter referred to as compound (M7)) is represented by a compound represented by formula (M6) (hereinafter referred to as compound (M6)), and two Xs represent the same halogen atom. ) And a chlorinating agent.
Examples of the compound (M6) include 3,6-difluoro-pyridine-2-carboxylic acid and 3,6-dichloro-pyridine-2-carboxylic acid, both of which are commercially available compounds.
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, aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, and mixtures thereof.
Examples of the chlorinating agent used in the reaction include thionyl chloride, oxalyl dichloride, phosphorus oxychloride and the like.
In the reaction, a chlorinating agent is usually used at a ratio of 1 to 15 mol with respect to 1 mol of the compound (M6).
The reaction temperature is usually in the range of 0 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M7) can be isolated by removing the solvent.

A compound represented by formula (M9) (hereinafter referred to as compound (M9)) is obtained by reacting compound (M7) with a compound represented by formula (M8) (hereinafter referred to as compound (M8)). Can be manufactured.
In the compound (M8), N ¹ -methyl-4-trifluoromethyl-benzene-1,2-diamine in which R ⁵ is CF ₃ and A is NCH ₃ is described in WO2010 / 125985 It can be manufactured by the method.
In the compound (M8), a compound (M8a) in which R ⁵ is CF ₂ CF ₃ , CF ₂ CF ₂ CF ₃ , CF (CF ₃ ) ₂ , or SR ⁶ and A is NCH ₃ (hereinafter referred to as compound (M8a )) Can be produced by the method described in Production Example 8.
Compound (M8b) in which R ⁵ is S (O) R ⁶ or S (O) ₂ R ⁶ and A is NCH ₃ in Compound (M8) (hereinafter referred to as Compound (M8b)) is described in Production Method 9. It can be manufactured by the method.
In compound (M8), 2-amino-4-trifluoromethyl-phenol in which R ⁵ is CF ₃ and A is an oxygen atom can be produced by the method described in US Pat. No. 5,780,483.
In compound (M8), R ⁵ is R ⁵ is CF ₂ CF ₃ , CF ₂ CF ₂ CF ₃ , CF (CF ₃ ) ₂ , SR ⁶ , S (O) R ⁶ , or S (O) ₂ R ⁶ The compound (M8c) in which A is an oxygen atom (hereinafter referred to as the compound (M8c)) can be produced by the method described in Production Method 10.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as tetrahydrofuran, 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. Aprotic polarities such as aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide Examples include solvents and mixtures thereof.
In the reaction, a base may be added as necessary.
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 N, N-diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine. And the like.
In the reaction, with respect to 1 mol of the compound (M8), the compound (M7) 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 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 (M9) 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 (M9) can be further purified by chromatography, recrystallization and the like.

Compound (M9) can also be produced in a one-step reaction (one pot) by reacting compound (M6) and compound (M8) in the presence of a condensing agent.
The reaction is performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether, and halogenations such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene. Hydrocarbons, aromatic hydrocarbons such as toluene, benzene and xylene, esters such as ethyl acetate and butyl acetate, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazo Examples thereof include aprotic polar solvents such as lizinone and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
Examples of the condensing agent used in the reaction include carbodiimides such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (hereinafter referred to as EDCI) and 1,3-dicyclohexylcarbodiimide.
In the reaction, a catalyst may be added as necessary.
Examples of the catalyst used in the reaction include 1-hydroxybenzotriazole (hereinafter referred to as HOBt).
In the reaction, with respect to 1 mole of the compound (M8), the ratio of the compound (M6) is usually 1 to 2 moles, the condensing agent is usually 1 to 5 moles, and the catalyst is usually 0.01 to 1 mole. Used in
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 added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered. The compound (M9) can be isolated by collecting by The isolated compound (M9) can be further purified by recrystallization, chromatography or the like.

A compound represented by formula (M10) (hereinafter referred to as compound (M10). Two Xs represent the same halogen atom) can be produced by intramolecular condensation of compound (M9).
The reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene. Hydrogen, aromatic hydrocarbons such as toluene, benzene and xylene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl- Examples include aprotic polar solvents such as 2-imidazolidinone and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
In the reaction, a condensing agent, an acid, a base, or a chlorinating agent may be added as necessary.
Examples of the condensing agent used in the reaction include acetic anhydride, trifluoroacetic anhydride, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, triphenylphosphine and base, and carbon tetrachloride or carbon tetrabromide. And mixtures of triphenylphosphine and azodiesters (eg diethyl azodicarboxylate).
Examples of the acid used for the reaction include sulfonic acids such as paratoluenesulfonic acid, carboxylic acids such as acetic acid, and polyphosphoric acid.
Examples of the base used in the reaction include pyridine, picoline, 2,6-lutidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5. -Nitrogen-containing heterocyclic compounds such as nonene, tertiary amines such as triethylamine and N, N-diisopropylethylamine, and alkali metal carbonates such as tripotassium phosphate, potassium carbonate and sodium hydride.
Examples of the chlorinating agent used in the reaction include phosphorus oxychloride.
In the reaction, with respect to 1 mol of the compound (M9), when a condensing agent is used, the ratio of the condensing agent is usually 1 to 5 mol, and when an acid is used, the acid is usually 0.1 mol to 5 mol. When a base is used, the base is usually used in a proportion of 1 to 5 mol, and when a chlorinating agent is used, the chlorinating 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 200 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the reaction mixture is added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered. The compound (M10) can be isolated by collecting by The isolated compound (M10) can be further purified by recrystallization, chromatography or the like.

Compound (M1a) can be produced by reacting compound (M10) with ethyl mercaptan in the presence of a base.
The reaction is performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether, 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, acetonitrile, N, N-dimethylformamide. , N-methylpyrrolidone, aprotic polar solvents such as dimethyl sulfoxide, water, and mixtures thereof.
Examples of the base used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrides such as sodium hydride.
In the reaction, with respect to 1 mol of the compound (M10), ethyl mercaptan is usually used in a proportion of 1 to 10 mol, and base is usually used in a proportion of 1 to 10 mol. Preferably, ethyl mercaptan is used in a proportion of 1.0 to 1.1 mol and a base is used in a proportion of 1 to 2 mol with respect to 1 mol of compound (M11).
The reaction temperature of the reaction is usually in the range of −20 ° C. to 150 ° C. The reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (M1a) 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 (M1a) can be further purified by chromatography, recrystallization and the like.

Manufacturing method 5
The compound (1c) of the present invention can be produced, for example, according to the following scheme.

[Wherein the symbols have the same meaning as described above. ]

A compound represented by formula (M20) (hereinafter referred to as compound (M20)) can be produced by reacting compound (M10) with ethyl mercaptan 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 tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether, 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, acetonitrile, N, N-dimethylformamide. , N-methylpyrrolidone, aprotic polar solvents such as dimethyl sulfoxide, water, and mixtures thereof.
Examples of the base used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrides such as sodium hydride.
In the reaction, with respect to 1 mol of the compound (M10), ethyl mercaptan is usually used in a proportion of 2 to 10 mol, and base is usually used in a proportion of 2 to 10 mol. Preferably, ethyl mercaptan is used in a proportion of 2.0 to 2.1 mol and a base is used in a proportion of 2 to 3 mol with respect to 1 mol of compound (M11).
The reaction temperature of the reaction is usually in the range of −20 ° C. to 150 ° C. The reaction time is usually in the range of 0.5 to 24 hours.
After completion of the reaction, the compound (M20) 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 (M20) can be further purified by chromatography, recrystallization and the like.

A compound represented by formula (M21) (hereinafter referred to as compound (M21)) can be produced by reacting compound (M20) with an oxidizing agent.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, nitriles such as acetonitrile, 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 and hydrogen peroxide.
When hydrogen peroxide is used as the oxidizing agent for the reaction, it is carried out in the presence of a base or a catalyst as necessary.
Examples of the base used for the reaction include sodium carbonate.
Examples of the catalyst used for the reaction include tungstic acid and sodium tungstate.
In the reaction, with respect to 1 mol of the compound (M20), the oxidizing agent is usually used at a ratio of 2 to 5 mol.
In the reaction, the base is generally used at a ratio of 0.01 to 1 mol with respect to 1 mol of the compound (20).
In the reaction, the catalyst is generally used in a proportion of 0.01 to 0.5 mol with respect to 1 mol of the compound (20).
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 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 and sodium thiosulfate) and an aqueous solution of a base (for example, sodium bicarbonate) as necessary. Compound (21) can be isolated by drying and concentrating this organic layer. The isolated compound (M21) can be further purified by chromatography, recrystallization and the like.

The compound (1c) of the present invention can be produced by reacting the compound (M21) and the compound (M2) 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 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene. Hydrogen, aromatic hydrocarbons such as toluene, benzene, xylene, esters such as ethyl acetate and butyl acetate, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolid Non-protic polar solvents such as non- and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, 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, alkali metal carbonates such as sodium carbonate and potassium carbonate, or triethylamine and diisopropylene. And organic bases such as propylethylamine, pyridine and 4-dimethylaminopyridine.
In the reaction, with respect to 1 mol of the compound (M21), the compound (M2) is usually used in a proportion of 1 to 2 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 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 added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered. The present compound (1c) can be isolated by collecting the above. The isolated compound (1c) of the present invention can be further purified by recrystallization, chromatography or the like.

Manufacturing method 6
In the formula (1), the compound of the present invention in which R ¹ is a C1-C3 alkoxy group (hereinafter referred to as the present compound (1m)) can be produced, for example, according to the following scheme.

[Wherein, R ^a represents a C1-C3 alkyl group, V represents a chlorine atom, a bromine atom, or an iodine atom, and other symbols have the same meaning as described above. ]

The compound represented by the formula (M3) (hereinafter referred to as the compound (M3)) can be produced by reacting the compound (M1) and semicarbazide hydrochloride 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 aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide.
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 (M1), semicarbazide hydrochloride is usually used in a proportion of 1 to 3 mol, and base is usually used in a proportion of 1 to 10 mol.
The reaction temperature 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 reaction mixture is added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered. The compound (M3) can be isolated by collecting by The isolated compound (M3) can be further purified by chromatography, recrystallization and the like.

The compound represented by the formula (M4) (hereinafter referred to as the compound (M4)) can be produced by reacting the compound (M3) with formic acid or trialkyl orthoformate.
Examples of the trialkyl orthoformate used in the reaction include trimethyl orthoformate and triethyl orthoformate.
The reaction is usually performed in the presence of a solvent.
Solvents used for the reaction include halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene, aromatic hydrocarbons such as toluene, benzene and xylene, N, N-dimethylformamide, N-methylpyrrolidone, 1, Examples include aprotic polar solvents such as 3-dimethyl-2-imidazolidinone and dimethyl sulfoxide, alcohol solvents such as methanol, ethanol and n-butanol, and mixtures thereof.
When formic acid is used in the reaction, formic acid is usually used at a ratio of 1 to 10 mol per 1 mol of compound (M3).
When trialkyl orthoformate is used in the reaction, trialkyl orthoformate is usually used at a ratio of 1 to 10 moles with respect to 1 mole of compound (M3).
The reaction temperature is usually in the range of 0 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the reaction mixture is added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered. The compound (M4) can be isolated by collecting by The isolated compound (M4) can be further purified by recrystallization, chromatography or the like.

The compound (1m) of the present invention can be produced by reacting the compound (M4) with a compound represented by the formula (M5) (hereinafter referred to as compound (M5)) in the presence of a base.
Examples of the compound (M5) include iodomethane, bromomethane, iodoethane, chloroethane, 1-iodopropane, 2-iodopropane and the like.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene. Aprotic polar solvents such as hydrogen, aromatic hydrocarbons such as toluene, benzene, xylene, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like These mixtures are mentioned.
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, alkali metal carbonates such as sodium carbonate and potassium carbonate, or triethylamine and diisopropylene. And organic bases such as propylethylamine, pyridine and 4-dimethylaminopyridine.
In the reaction, the compound (M5) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 0.1 to 5 mol with respect to 1 mol of the compound (M4) of the present invention.
The reaction temperature is usually in the range of −20 ° C. 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 added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered. The present compound (1m) can be isolated by collecting by The isolated compound (1m) of the present invention can be further purified by chromatography, recrystallization and the like.

Manufacturing method 7
In the formula (1), the compound of the present invention (1r) in which n = 2, R ¹ is S (O) _m R ² and m is 2 (hereinafter referred to as the present compound (1r)), and the formula (1) In 1), the present compound (1q) (hereinafter referred to as the present compound (1q)) in which n = 2, R ¹ is S (O) _m R ² and m is 1 is represented by the formula (1) In the present invention, n = 2, R ¹ is S (O) _m R ² and m is 0, and the present compound (1o) (hereinafter referred to as the present compound (1o)) is reacted with an oxidizing agent. Can be manufactured.

[Wherein the symbols have the same meaning as described above. ]
This reaction is carried out by replacing the compound (1a) of the present invention in the production method 1 with the compound (1o) of the present invention and replacing the compound (1b) of the present invention with the compound (1q) of the present invention. It can be manufactured according to.

Manufacturing method 8
Compound (M8a) can be produced, for example, according to the following scheme.

A compound represented by formula (M11) (hereinafter referred to as compound (M11)) is obtained by reacting a compound represented by formula (M20) (hereinafter referred to as compound (M20)) with an acetylating agent. Can be manufactured.
In the compound (M20), the compound in which R ⁵ is CF ₃ is a commercially available compound.
In compound (M20), a compound in which R ⁵ is CF ₂ CF ₃ , CF ₂ CF ₂ CF ₃ can be produced by the method described in International Publication No. 00/07998.
In compound (M20), a compound in which R ⁵ is CF (CF ₃ ) ₂ can be produced by the method described in EP 1006102.
In the compound (M20), a compound in which R ⁵ is SCF ₃ is a commercially available compound.
In compound (M20), a compound in which R ⁵ is SCF ₂ CF ₃ , SCF ₂ CF ₂ CF ₃ , or SCF (CF ₃ ) ₂ can be produced by the method described in JP-A-10-291973.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene. Hydrogen, aromatic hydrocarbons such as toluene, benzene, xylene, esters such as ethyl acetate and butyl acetate, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolid Non-protic polar solvents such as non- and dimethyl sulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
In the reaction, a base may be added as necessary.
Examples of the base used in the reaction include organic bases such as triethylamine, diisopropylpyroethylamine, pyridine and 4-dimethylaminopyridine.
Examples of the acetylating agent used in the reaction include acetic anhydride and acetyl chloride.
The reaction may be performed using acetic anhydride, acetyl chloride or the like as a solvent.
In the reaction, an acetylating agent is usually used at a ratio of 1 to 3 moles per mole of 4-trifluoromethylsulfinyl-aniline.
The reaction temperature is usually in the range of −30 to 100 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
When a base is used in the reaction, the base is usually used at a ratio of 0.01 to 3 mol per 1 mol of 4-trifluoromethylsulfinyl-aniline.
After completion of the reaction, the compound (M11) 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 (M11) can be further purified by chromatography, recrystallization, and the like.

A compound represented by formula (M12) (hereinafter referred to as compound (M12)) can be produced by reacting compound (M11) with 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 (M11).
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 (M12) 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 (M12) can be further purified by chromatography, recrystallization and the like.

A compound represented by formula (M13) (hereinafter referred to as compound (M13)) can be produced by reacting compound (M12) with a methylating agent 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 1,4-dioxane, diethyl ether, tetrahydrofuran and tert-butyl methyl ether, and halogenated carbonization such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene. Aprotic polar solvents such as hydrogen, aromatic hydrocarbons such as toluene, benzene, xylene, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like These mixtures are mentioned.
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, alkali metal carbonates such as sodium carbonate and potassium carbonate, or triethylamine and diisopropylene. And organic bases such as propylethylamine, pyridine and 4-dimethylaminopyridine.
Examples of the methylating agent used in the reaction include iodomethane and dimethyl sulfate.
In the reaction, with respect to 1 mole of the compound (M12), the methylating agent is usually used at a ratio of 1 to 5 moles, and the base is usually used at a ratio of 0.1 to 5 moles.
The reaction temperature is usually in the range of −20 ° C. 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 added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered. The compound (M13) can be isolated by collecting by The isolated compound (M13) can be further purified by chromatography, recrystallization and the like.

The compound represented by formula (M14) (hereinafter referred to as compound (M14)) can be produced by subjecting compound (M13) to a hydrolysis reaction in the presence of a base or an acid.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as tetrahydrofuran and 1,4-dioxane, alcohols such as methanol and ethanol, water, and mixtures thereof.
Examples of the base used in the reaction include alkali metal carbonates such as sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate.
Examples of the acid used in the reaction include hydrochloric acid and sulfuric acid.
In the reaction, with respect to 1 mol of compound (13), when a base is used, the base is used in a proportion of 1 to 5 mol, and when an acid is used, the acid is used in a proportion of 0.1 to 5 mol.
The reaction temperature 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 reaction mixture is added to water and extracted with an organic solvent, and the organic layer is concentrated; the reaction mixture is added to water and the resulting solid is collected by filtration; or the solid produced in the reaction mixture is filtered. The compound (M14) can be isolated by collecting by The isolated compound (M14) can be further purified by chromatography, recrystallization and the like.

Compound (M8a) can be produced by reacting compound (M14) with hydrogen in the presence of a hydrogenation catalyst.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as tetrahydrofuran, 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.
The reaction is usually performed in a hydrogen atmosphere at 1 to 100 atm, usually in the presence of a solvent.
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 to 100 mol, and a hydrogenation catalyst is usually used in a proportion of 0.001 to 0.5 mol with respect to 1 mol of compound (M14).
The reaction temperature 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 (M8a) can be isolated by performing post-treatment operations such as filtration of the reaction mixture, extraction with an organic solvent as necessary, and drying and concentration of the organic layer. The isolated compound (M8a) can be further purified by chromatography, recrystallization and the like.

Compound (M8a) can be produced by reacting compound (M14) with a reducing agent.
The reaction can be performed, for example, in the presence of a reducing agent, 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 tetrahydrofuran, 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 aprotic polar solvents such as N, N-dimethylformamide (hereinafter referred to as DMF), N-methylpyrrolidone (hereinafter referred to as NMP), dimethyl sulfoxide (hereinafter referred to as DMSO), and mixtures thereof.
Examples of the reducing agent used in the reaction include metal powders such as iron powder, zinc powder, and tin dichloride.
In the reaction, with respect to 1 mol of the compound (M14), the reducing agent is usually used in a proportion of 3 to 10 mol, the acid is usually used in a proportion of 0.01 to 0.5 mol, and the water is used in a proportion of 3 mol or more. It is done.
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 (M8a) 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 (M8a) can also be purified by chromatography, recrystallization, and the like.

Manufacturing method 9
Compound (M8b) can be produced, for example, according to the following scheme.

[Wherein q represents 1 or 2. ]

A compound represented by formula (M16) (hereinafter referred to as compound (M16)) is obtained by reacting a compound represented by formula (M15) (hereinafter referred to as compound (M15)) with a chlorinating agent. Can be manufactured.
Compound (M15) can be produced according to the method of Production Method 10.
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, aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, and mixtures thereof.
Examples of the chlorinating agent used in the reaction include thionyl chloride, oxalyl dichloride, phosphorus oxychloride and the like.
In the reaction, a chlorinating agent is usually used at a ratio of 1 to 15 mol with respect to 1 mol of the compound (M15).
The reaction temperature is usually in the range of 0 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (M16) can be isolated by removing the solvent.

The compound represented by the formula (M17) (hereinafter referred to as the compound (M17)) can be produced by reacting the compound (M16) with methylamine.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as tetrahydrofuran, 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. Aprotic polar solvents such as aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and the like A mixture is mentioned.
The methylamine used for the reaction may be in the form of a gas, an aqueous solution, or an alcohol solution.
This reaction can also be performed in presence of a base as needed.
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, alkali metal carbonates such as sodium carbonate and potassium carbonate, or triethylamine and diisopropylene. And organic bases such as propylethylamine, pyridine and 4-dimethylaminopyridine.
In the reaction, with respect to 1 mole of the compound (M16), methylamine is usually used at a ratio of 1 to 10 moles and the base is used at a ratio of 0.01 to 10 moles.
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 (M17) 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 (M17) can also be purified by chromatography, recrystallization, and the like.

Compound (M8b) or compound (M8c) can be produced by reacting compound (M17) with hydrogen in the presence of a hydrogenation catalyst.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as tetrahydrofuran, 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.
The reaction is usually performed in a hydrogen atmosphere at 1 to 100 atm, usually in the presence of a solvent.
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 mol of the compound (M17), hydrogen is usually used in a proportion of 3 to 100 mol, and a hydrogenation catalyst is usually used in a proportion of 0.001 to 0.5 mol.
The reaction temperature 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 (M8b) can be isolated by performing post-treatment operations such as filtration of the reaction mixture, extraction with an organic solvent as necessary, and drying and concentration of the organic layer. The isolated compound (M8b) can be further purified by chromatography, recrystallization and the like.

Compound (M8b) can be produced by reacting compound (M17) with a reducing agent.
The reaction can be performed, for example, in the presence of a reducing agent, 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 tetrahydrofuran, 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 include aprotic polar solvents such as DMF, NMP, DMSO, and mixtures thereof.
Examples of the reducing agent used in the reaction include metal powders such as iron powder, zinc powder, and tin dichloride.
In the reaction, with respect to 1 mol of the compound (M17), the reducing agent is usually used in a proportion of 3 to 10 mol, the acid is usually used in a proportion of 0.01 to 0.5 mol, and the water is used in a proportion of 3 mol or more. It is done.
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 (M8b) 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 (M8b) can also be purified by chromatography, recrystallization, and the like.

Manufacturing method 10
Compound (M8c) can be produced, for example, according to the following scheme.

[The symbols in the formula have the same meaning as in formula (1). ]
A compound represented by formula (M19) (hereinafter referred to as compound (M19)) is obtained by reacting a compound represented by formula (M18) (hereinafter referred to as compound (M18)) with a nitrating agent. Can be manufactured.
The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform, acetic acid, concentrated sulfuric acid, concentrated nitric acid, water, and mixtures thereof.
Examples of the nitrating agent used in the reaction include 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 (M18).
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 (M19) 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 (M19) can be further purified by chromatography, recrystallization and the like.

Compound (M8c) can be produced by reacting compound (M19) with hydrogen in the presence of a hydrogenation catalyst.
The reaction is usually performed in a hydrogen atmosphere at 1 to 100 atm, usually in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as tetrahydrofuran, 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 (M19), 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.
The reaction temperature 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 (M8c) can be isolated by performing post-treatment operations such as filtration of the reaction mixture, extraction with an organic solvent as necessary, and drying and concentration of the organic layer. The isolated compound (M8c) can be further purified by chromatography, recrystallization, and the like.

Compound (M8c) can be produced by reacting compound (M19) with a reducing agent.
The reaction can be performed, for example, in the presence of a reducing agent, 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 tetrahydrofuran, 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 include aprotic polar solvents such as DMF, NMP, DMSO, and mixtures thereof.
Examples of the reducing agent used in the reaction include metal powders such as iron powder, zinc powder, and tin dichloride.
In the reaction, with respect to 1 mol of the compound (M19), the reducing agent is usually used in a proportion of 3 to 10 mol, the acid is usually used in a proportion of 0.01 to 0.5 mol, and the water is used in a proportion of 3 mol or more. It is done.
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 (M8c) 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 (M8c) can also be purified by chromatography, recrystallization, and the like.

Manufacturing method 11
Compound (M18b) in which R ⁵ is S (O) R ⁶ in formula (M18) (hereinafter referred to as compound (M18b)), and Compound in which R ⁵ is S (O) ₂ R ⁶ in formula (M18) (M18c) (hereinafter referred to as compound (M18c)) is obtained by reacting compound (M18a) (hereinafter referred to as compound (M18a)) in which R ⁵ is SR ⁶ in compound (M18) with an oxidizing agent. Can be manufactured.

The reaction is carried out according to the reaction described in Production Example 1 by substituting compound (M18a) for the present compound (1a) in production method 1 and compound (M18b) for the present compound (1b). can do.

Production method 12
Compound (M18) can be produced by reacting compound (M20) with a diazotizing agent in the presence of an acidic aqueous solution.

The reaction is performed in the presence of a solvent.
Examples of the solvent used in the reaction include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and 1,4-dioxane, alcohols such as methanol and ethanol, aprotic polar solvents such as acetonitrile, DMF, NMP and DMSO, water And mixtures thereof.
Examples of the diazotizing agent used in the reaction include sodium nitrite.
Examples of the acidic aqueous solution used for the reaction include sulfuric acid, hydrochloric acid, acetic acid, and a mixture thereof.
In the reaction, with respect to 1 mol of the compound (M20), the diazotizing agent is usually used in a proportion of 1 to 10 mol and the acid in a proportion of 1 to 100 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 (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.

Next, specific examples of the compound of the present invention are shown below.

The compound of the present invention in which in formula (1), R ⁵ is CF ₃ , A is NCH ₃ , and n and R ¹ are combinations described in [Table 1] to [Table 3].

The compound of the present invention in which, in the formula (1), R ⁵ is CF ₃ , A is NCH ₃ , and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3].
In the formula (1), R ⁵ is CF ₂ CF ₃ , A is NCH ₃ , and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3].
In the formula (1), R ⁵ is CF ₂ CF ₂ CF ₃ , A is NCH ₃ , and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] Compound.
In the formula (1), R ⁵ is CF (CF ₃ ) ₂ , A is NCH ₃ , and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] Compound.
The compound of the present invention in which in formula (1), R ⁵ is SCF ₃ , A is NCH ₃ , and n and R ¹ are a combination described in any of [Table 1] to [Table 3].
In the formula (1), R ⁵ is S (O) CF ₃ , A is NCH ₃ , and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] Compound.
In the formula (1), R ⁵ is S (O) ₂ CF ₃ , A is NCH ₃ , and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] Invention compounds.
In the formula (1), R ⁵ is SCF ₂ CF ₃ , A is NCH ₃ , and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3].
In the formula (1), R ⁵ is S (O) CF ₂ CF ₃ , A is NCH ₃ , and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] The compound of the present invention.
In the formula (1), R ⁵ is S (O) ₂ CF ₂ CF ₃ , A is NCH ₃ , and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] A compound of the present invention.
In the formula (1), R ⁵ is SCF ₂ CF ₂ CF ₃ , A is NCH ₃ , and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] Compound.
In Formula (1), R ⁵ is S (O) CF ₂ CF ₂ CF ₃ , A is NCH ₃ , and n and R ¹ are the combinations according to any ^one of [Table 1] to [Table 3] The compound of the present invention.
In the formula (1), R ⁵ is S (O) ₂ CF ₂ CF ₂ CF ₃ , A is NCH ₃ , and n and R ¹ are described in any ^one of [Table 1] to [Table 3] The compound of the present invention which is a combination.
In the formula (1), R ⁵ is SCF (CF ₃ ) ₂ , A is NCH ₃ , and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] Compound.
In formula (1), R ⁵ is S (O) CF (CF ₃ ) ₂ , A is NCH ₃ , and n and R ¹ are the combinations according to any ^one of [Table 1] to [Table 3] The compound of the present invention.
In Formula (1), R ⁵ is S (O) ₂ CF (CF ₃ ) ₂ , A is NCH ₃ , and n and R ¹ are described in any ^one of [Table 1] to [Table 3] The compound of the present invention which is a combination.

The compound of the present invention in which in formula (1), R ⁵ is CF ₃ , A is an oxygen atom, and n and R ¹ are a combination described in any of [Table 1] to [Table 3].
The compound of the present invention in which, in the formula (1), R ⁵ is CF ₂ CF ₃ , A is an oxygen atom, and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3].
In the formula (1), R ⁵ is CF ₂ CF ₂ CF ₃ , A is an oxygen atom, and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] Compound.
In the formula (1), R ⁵ is CF (CF ₃ ) ₂ , A is an oxygen atom, and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] Compound.
The compound of the present invention in which, in the formula (1), R ⁵ is SCF ₃ , A is an oxygen atom, and n and R ¹ are a combination described in any ^one of [Table 1] to [Table 3].
In the formula (1), R ⁵ is S (O) CF ₃ , A is an oxygen atom, and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] Compound.
In the formula (1), R ⁵ is S (O) ₂ CF ₃ , A is an oxygen atom, and n and R ¹ are combinations described in any of [Table 1] to [Table 3] Invention compounds.
The compound of the present invention in which, in the formula (1), R ⁵ is SCF ₂ CF ₃ , A is an oxygen atom, and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3].
In the formula (1), R ⁵ is S (O) CF ₂ CF ₃ , A is an oxygen atom, and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] The compound of the present invention.
In the formula (1), R ⁵ is S (O) ₂ CF ₂ CF ₃ , A is an oxygen atom, and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] A compound of the present invention.
In the formula (1), R ⁵ is SCF ₂ CF ₂ CF ₃ , A is an oxygen atom, and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] Compound.
In formula (1), R ⁵ is S (O) CF ₂ CF ₂ CF ₃ , A is an oxygen atom, and n and R ¹ are the combinations according to any ^one of [Table 1] to [Table 3] The compound of the present invention.
In the formula (1), R ⁵ is S (O) ₂ CF ₂ CF ₂ CF ₃ , A is an oxygen atom, and n and R ¹ are any ^one of [Table 1] to [Table 3] The compound of the present invention which is a combination.
In the formula (1), R ⁵ is SCF (CF ₃ ) ₂ , A is an oxygen atom, and n and R ¹ are combinations according to any ^one of [Table 1] to [Table 3] Compound.
In formula (1), R ⁵ is S (O) CF (CF ₃ ) ₂ , A is an oxygen atom, and n and R ¹ are the combinations according to any ^one of [Table 1] to [Table 3] The compound of the present invention.
In Formula (1), R ⁵ is S (O) ₂ CF (CF ₃ ) ₂ , A is an oxygen atom, and n and R ¹ are any ^one of [Table 1] to [Table 3] The compound of the present invention which is a combination.

Formula (1B)

Wherein A is NCH ₃ , R ⁶ is CF ₃ , and R ¹ is a combination according to any one of Table 1 to Table 3.
In the formula (1B), A is NCH ₃ , R ⁶ is CF ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3].
The compound of the present invention in which, in the formula (1B), A is NCH ₃ , R ⁶ is CF ₂ CF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
The compound of the present invention in which in formula (1B), A is NCH ₃ , R ⁶ is CF (CF ₃ ) ₂ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
In the formula (1B), A is NCH ₃ , R ⁶ is SCF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3].
In the formula (1B), A is NCH ₃ , R ⁶ is S (O) CF ₃ , and R ¹ is a combination according to any one of Table 1 to Table 3.
In the formula (1B), A is NCH ₃ , R ⁶ is S (O) ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] .
In the formula (1B), A is NCH ₃ , R ⁶ is SCF ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3].
In the formula (1B), A is NCH ₃ , R ⁶ is S (O) CF ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] Compound.
In the formula (1B), A is NCH ₃ , R ⁶ is S (O) ₂ CF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3] Invention compounds.
In the formula (1B), A is NCH ₃ , R ⁶ is SCF ₂ CF ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3].
In the formula (1B), A is NCH ₃ , R ⁶ is S (O) CF ₂ CF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3] The compound of the present invention.
In the formula (1B), A is NCH ₃ , R ⁶ is S (O) ₂ CF ₂ CF ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] A compound of the present invention.
In the formula (1B), A is NCH ₃ , R ⁶ is SCF (CF ₃ ) ₂ , and R ¹ is a combination according to any one of Table 1 to Table 3.
In the formula (1B), A is NCH ₃ , R ⁶ is S (O) CF (CF ₃ ) ₂ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] The compound of the present invention.
In the formula (1B), A is NCH ₃ , R ⁶ is S (O) ₂ CF (CF ₃ ) ₂ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] A compound of the present invention.
In the formula (1B), A is an oxygen atom, R ⁶ is CF ₃ , and R ¹ is a combination according to any one of Table 1 to Table 3.
In the formula (1B), A is an oxygen atom, R ⁶ is CF ₂ CF ₃ , and R ¹ is a combination according to any one of Table 1 to Table 3.
In the formula (1B), A is an oxygen atom, R ⁶ is CF ₂ CF ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3].
The compound of the present invention in which, in the formula (1B), A is an oxygen atom, R ⁶ is CF (CF ₃ ) ₂ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
In the formula (1B), A is an oxygen atom, R ⁶ is SCF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3].
The compound of the present invention in which, in the formula (1B), A is an oxygen atom, R ⁶ is S (O) CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
In the formula (1B), A is an oxygen atom, R ⁶ is S (O) ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] .
In the formula (1B), A is an oxygen atom, R ⁶ is SCF ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3].
In the formula (1B), A is an oxygen atom, R ⁶ is S (O) CF ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] Compound.
In the formula (1B), A is an oxygen atom, R ⁶ is S (O) ₂ CF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3] Invention compounds.
In the formula (1B), A is an oxygen atom, R ⁶ is SCF ₂ CF ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3].
In the formula (1B), A is an oxygen atom, R ⁶ is S (O) CF ₂ CF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3]. The compound of the present invention.
In the formula (1B), A is an oxygen atom, R ⁶ is S (O) ₂ CF ₂ CF ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] A compound of the present invention.
In the formula (1B), A is an oxygen atom, R ⁶ is SCF (CF ₃ ) ₂ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3].
In the formula (1B), A is an oxygen atom, R ⁶ is S (O) CF (CF ₃ ) ₂ , and R ¹ is a combination described in any of [Table 1] to [Table 3] The compound of the present invention.
In the formula (1B), A is an oxygen atom, R ⁶ is S (O) ₂ CF (CF ₃ ) ₂ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] A compound of the present invention.

Formula (1C)

Wherein A is NCH ₃ , R ⁶ is CF ₃ , and R ¹ is a combination according to any one of Table 1 to Table 3.
The compound of the present invention in which, in the formula (1C), A is NCH ₃ , R ⁶ is CF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
The compound of the present invention in which, in the formula (1C), A is NCH ₃ , R ⁶ is CF ₂ CF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
The compound of the present invention in which, in the formula (1C), A is NCH ₃ , R ⁶ is CF (CF ₃ ) ₂ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
The compound of the present invention in which, in the formula (1C), A is NCH ₃ , R ⁶ is SCF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
The compound of the present invention in which, in the formula (1C), A is NCH ₃ , R ⁶ is S (O) CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
In the formula (1C), A is NCH ₃ , R ⁶ is S (O) ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] .
The compound of the present invention in which, in the formula (1C), A is NCH ₃ , R ⁶ is SCF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
In the formula (1C), A is NCH ₃ , R ⁶ is S (O) CF ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] Compound.
In the formula (1C), A is NCH ₃ , R ⁶ is S (O) ₂ CF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3] Invention compounds.
In the formula (1C), A is NCH ₃ , R ⁶ is SCF ₂ CF ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3].
In the formula (1C), A is NCH ₃ , R ⁶ is S (O) CF ₂ CF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3] The compound of the present invention.
In the formula (1C), A is NCH ₃ , R ⁶ is S (O) ₂ CF ₂ CF ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] A compound of the present invention.
The compound of the present invention in which, in the formula (1C), A is NCH ₃ , R ⁶ is SCF (CF ₃ ) ₂ and R ¹ is a combination described in any of [Table 1] to [Table 3].
In the formula (1C), A is NCH ₃ , R ⁶ is S (O) CF (CF ₃ ) ₂ , and R ¹ is a combination described in any of [Table 1] to [Table 3] The compound of the present invention.
In the formula (1C), A is NCH ₃ , R ⁶ is S (O) ₂ CF (CF ₃ ) ₂ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] A compound of the present invention.
In the formula (1C), the compound of the present invention wherein A is an oxygen atom, R ⁶ is CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
The compound of the present invention in which, in the formula (1C), A is an oxygen atom, R ⁶ is CF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
The compound of the present invention in which, in the formula (1C), A is an oxygen atom, R ⁶ is CF ₂ CF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
The compound of the present invention in which, in the formula (1C), A is an oxygen atom, R ⁶ is CF (CF ₃ ) ₂ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
The compound of the present invention in which, in the formula (1C), A is an oxygen atom, R ⁶ is SCF ₃ and R ¹ is a combination according to any ^one of [Table 1] to [Table 3].
The compound of the present invention in which, in the formula (1C), A is an oxygen atom, R ⁶ is S (O) CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
In the formula (1C), A is an oxygen atom, R ⁶ is S (O) ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] .
The compound of the present invention in which, in the formula (1C), A is an oxygen atom, R ⁶ is SCF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
In the formula (1C), A is an oxygen atom, R ⁶ is S (O) CF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3] Compound.
In the formula (1C), A is an oxygen atom, R ⁶ is S (O) ₂ CF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3] Invention compounds.
The compound of the present invention in which, in the formula (1C), A is an oxygen atom, R ⁶ is SCF ₂ CF ₂ CF ₃ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
In Formula (1C), A is an oxygen atom, R ⁶ is S (O) CF ₂ CF ₂ CF ₃ , and R ¹ is a combination described in any ^one of [Table 1] to [Table 3] The compound of the present invention.
In the formula (1C), A is an oxygen atom, R ⁶ is S (O) ₂ CF ₂ CF ₂ CF ₃ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] A compound of the present invention.
The compound of the present invention in which, in the formula (1C), A is an oxygen atom, R ⁶ is SCF (CF ₃ ) ₂ , and R ¹ is a combination described in any of [Table 1] to [Table 3].
In the formula (1C), A is an oxygen atom, R ⁶ is S (O) CF (CF ₃ ) ₂ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] The compound of the present invention.
In the formula (1C), A is an oxygen atom, R ⁶ is S (O) ₂ CF (CF ₃ ) ₂ , and R ¹ is a combination according to any ^one of [Table 1] to [Table 3] A compound of the present invention.

Examples of pests for which the compounds of the present invention are effective include harmful arthropods such as harmful insects and harmful mites, and harmful linear animals such as nematodes. Specific examples of such pests include the following.

Hemiptera: small brown planthopper (Laodelphax striatellus), brown planthopper (Nilaparvata lugens), planthoppers such as Sejirounka (Sogatella furcifera), green rice leafhopper (Nephotettix cincticeps), Taiwan green rice leafhopper (Nephotettix virescens), tea Roh green leafhopper such as leafhopper (Empoasca onukii) Cotton aphids (Aphis gossypi), peach aphids (Myus persicae), radish aphids (Brevicorine brassicae), aphid spiraecola, tulip beetle aphids (M) crosifum euphorbiae, potato beetle aphids (Auracorthum solani), wheat beetle aphids (Rhopalosiphum padi), citrus aphids (Toxoptera citricidus), peach beetles, etc. Stink bugs such as stink bugs (Riptortus clavetus), spider helicopter bugs (Leptocorisa chinensis), bark beetles (Eysarcoris parvus), winged beetle (Halyomorpha mista), and the like vaporariorum), sweetpotato whitefly (Bemisia tabaci), mandarin orange whitefly (Dialeurodes citri), whiteflies such as mandarin orange spiny whitefly (Aleurocanthus spiniferus), Acamar scale insects (Aonidiella aurantii), Sanho zero scale insects (Comstockaspis perniciosa), citrus snow scale (Unaspis citri ), Ruby Beetle (Ceroplastes rubens), Iceria scale insect (Icerya purchasi), Fujino scale insect (Pranococcus kraunhiae), Pseudococcus longispin (Pseudococcus longispin) is), scale insects such as Pseudauracapaspis pentagona, bed bugs, bed bugs such as bedbugs (Cimex electularius), and cetaceans.

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), Shibatsutoga (Pediasia teterrulus) and other moths, Spodoptera litura, Spodoptera exigua, Ayuyoto (Pseudaletia sepata), Madam Gritters such as Strassicae, Agrotis ipsilon, Tamanaginuwaba (Plusia nigrisigna), Trichopulsia, Heliotis, Helicoberpa, etc. (Leguminivora, Glycinivolora), Azusa yamushiga (Matsumuraeses azukivivora), Apple wolfberry (Adoxophyes), Orana fasmoata (Adomophymomochia). Scallops of the genus Acer, the genus of the genus Cypridia, the genus of the genus, the genus of the genus, the genus of the genus, the moss of the genus moth, Doctors of the genus Limantria and Euproctinis, Sugas such as Plutella xylostella, Pterinophora gossypiella potato moth (Phthorimaea operculella), etc .; Chunea) and other tigers such as iga (Tinea translucens) and tiger bisselliella.

Thrips: Frankliniella occidentalis, Thrips parmi, Citrus dorsalis, and Thrips thrips.

Diptera: Culex pipiens palens, Culex quaters, and other squids such as Culex quinquefasciaus, etc .; Houseflies such as Anopheles, Chironomidae, Musca domestica, Muscina stabulans, etc., Drosophila, Drosophila, Drosophila, Delaplata, Timaelae Ribae (Agromyza oryzae), rice Hime leafminer (Hydrellia griseola), tomato leafminer, (Liriomyza sativae), legume leafminer (Liriomyza trifolii), leafminer such as the pea (Chromatomyia horticola), chloropidae such as Inekimoguribae (Chlorops oryzae), melon fly (Dacus cucurbitae), fruit flies such as Ceratitis capitata, fruit flies such as Drosophila, flea flies, Megaseria spiracularis, Clogmial butterflies, etc. S, sciaridae acids, blackfly acids, Abu such as gadfly (Tabanus trigonus), keds acids and stable flies such.

Coleoptera: Western corn rootworm (Diabrotica virgifera virgifera), corn root worms such as Southern corn rootworm (Diabrotica undecimpunctata howardi), cupreous chafer (Anomala cuprea), rufocuprea (Anomala rufocuprea), beetles such as Japanese beetle (Popillia japonica) , Maysweville (Sytophilus zeamais), Rice weevil (Lissohoptrus oryzophilus), Azuki beetle (Callosobrchuchus chiensis), Green weevil (Echinocnemus squatium) omus grandis), weevils such as grass reed weevil (Sphenophorus venatus), Chai Loco Meno mealworm (Tenebrio molitor), mealworm such as red flour beetle (Tribolium castaneum),
Inedorooimushi (Oulema oryzae), cucurbit leaf beetle (Aulacophora femoralis), Kisujinomihamushi (Phyllotreta striolata), beetles such as Colorado potato beetle (Leptinotarsa decemlineata), varied carpet beetle (Anthrenus verbasci), carpet beetle such as Hara Giro beetle (Dermestes maculates), cigarette beetle (Lasiderma serricorne) and the like, Epilachna vigintioctopuncta and other epilacunas, Lyctus brunneus and pine beetle (Pompicus) erda), bark beetles, leopard beetles, longhorn beetles (Anoprophora malasiaca), longhorn beetles (Agriotes spp.), and blue scallops (ed) p.

Species: Tosama grasshopper (Locusta migratoria), Kera (Gryllotalpa africana), Oxya yezoensis, Lobster (Oxya japonica), and crickets.

Lepidoptera: Cat fleas (Ctenocephalides felis), dog fleas (Ctenocephalides canis), human fleas (Pulex irritans), keops mouse fleas (Xenopsilla cheopes) and the like. *

Anoplura: body louse (Pediculus humanus corporis), head lice (Pediculus humanus humanus), crab louse (Phthirus pubis), Ushijirami (Haematopinus eurysternus), Hitsujijirami (Dalmalinia ovis), Butajirami (Haematopinus suis), Inujirami (Linognathus setosus) and the like. *

Lepidoptera: sheep lice (Dalmalinia ovis), cattle lice (Dalmalinia bovis), chicken lice (Menonpon gallinae), dog lice (Trichodictes canis), cat wolf squirr

Hymenoptera: Monomorium phalaosis, Formica fusca japonica, Ruriari (Ochetellus pungens), Psomylem puns, Pepperm sperm. Ants such as Argentine ants (Linepithema humile), wasps such as wasps, scallops, and wasps such as wasp (Athalia rosae) and Japanese bee (Athalia japonica).

Cockroaches: German cockroaches (Blatella germanica), Black cockroaches (Periplaneta fligninosa), Cockroach cockroaches (Periplaneta americana), Japanese cockroaches (Periplaneta brunat)

Isoptera: Yamato termite (Reticulitermes speratus), Formosan subterranean termite (Coptotermes formosanus), the United States drywood termites (Incisitermes minor), Daikoku termites (Cryptotermes domesticus), Taiwan termites (Odontotermes formosanus), Kou Shun termite (Neotermes koshunensis), Satsuma termites (Glyptotermes satsumensis), termites termites (Glyptotermes nakajimai), termites termites (Glyptotermes fuscus), termites termites (Glyptotermes kodamai) Termites (Glyptotermes kushimensis), giant termite (Hodotermopsis japonica), Kou Shu Ye termite (Coptotermes guangzhoensis), Amami termites (Reticulitermes miyatakei), R. flavipes (Reticulitermes flaviceps amamianus), Kang Mont termites (Reticulitermes sp.), Takasago termite (Nasutitermes takasagoensis) , Nitrobe termites (Pericapritermes nitobei), Musha termites (Sinocapritermes mushae), and the like.

Mite order: Tetanychus urticae, Tetanychus kanzawai, utani mite (Ponyychus urmi), mite mite (p) Rabbit mites (Aculops lycopersici), Rabbit mites (Calacarus carinatus), Rabbit mites (Acaphylla theavagrans), Scarlet mite (Eriophys chibaensis), Apple crustaceans (Aulus dachi) Dust mites, such as mites, Polyphagotarsonemus latus, Scots mites, Bremen spider mites, Hemiphysalis mites, Haemphysalis mite, Haemphysalis longis Dermacentor variabilis, Ixodes ovatus, Ixes persulcatus, Black legged tick (Ixodes scapularis), American larva tick (Amblyomama amer) canum), Boophilus microplus (Boophilus microplus), ticks such as Rhipicephalus sanguineus (Rhipicephalus sanguineus), Tyrophagus (Tyrophagus putrescentiae), grain mites such as Tyrophagus (Tyrophagus similis), farinae (Dermatophagoides farinae), D. pteronyssinus (Dermatophagoides ptrenyssnus) Leopard mites, such as Cheyletus eruditus, Stag beetle tick (Cheyletus malaccensis), Scarlet tick (Cheyletus mooreii), Tiger tickle (Cheeletiell) mite mites such as a yasguri, mite mites (Octoectes cynotis), mites mites such as Sacroptes scabiei, mite mites such as Demodex canis, mite mites, b Species such as Ornithonysus sylvairum and Dermanyssus gallinae, and Tsutsugamushi such as Leptotrombidium akamushi.
Spider: Spiders such as Chiracanthium japonicum and Latrodictus hasseltii
Lip and limb class: Geeu (Thereunema hilgendorfi), Tobizukade (Scorpendra subspinipes) and the like.
Double leg class: Oxidus gracilis, Nedyopus tambanus, etc.
Isopods: Armadillium vulgare, etc.
Gastropoda: Limax marginatus, Limax flavus, etc.

Nematodes: rice Shin Galle nematode (Aphelenchoides besseyi), strawberry menu nematode (Nothotylenchus acris), sweet potato root-knot nematode (Meloidogyne incognita), northern root-knot nematode (Meloidogyne hapla), Java root-knot nematode (Meloidogyne javanica), soybean cyst nematode (Heterodera glycines), Potato cyst nematode (Globodera rostochiensis), southern nematode crested pea (Pratylenchus coffeae), barley nematode nematode (Pratylenchus neglectus).

Pests include pests that have reduced drug sensitivity to existing pesticides, that is, have acquired drug resistance.

The pest control agent of the present invention contains the compound of the present invention and an inert carrier. The pest control agent of the present invention is usually a mixture of the compound of the present invention and an inert carrier such as a solid carrier, liquid carrier, gaseous carrier, etc. Emulsions, oils, powders, dry flowables, fine granules, granules, wettable powders, aqueous solvents, flowables, microcapsules, aerosols, smokers, poison baits, resin preparations, shampoos, pastes It is formulated into a pharmaceutical preparation, foam preparation, carbon dioxide preparation, tablet and the like. These preparations may be used after being processed into mosquito coils, electric mosquito mats, liquid mosquito traps, fumigants, fumigants, sheet preparations, spot-on agents, or oral treatments.
The pest control agent of the present invention usually contains 0.01 to 95% by weight of the compound of the present invention.

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

Examples of the liquid carrier include water, alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, phenoxyethanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (Toluene, xylene, ethylbenzene, dodecylbenzene, phenylxylylethane, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, isopropyl myristate, Ethyl oleate, diisopropyl adipate, diisobutyl adipate, propylene glycol monomethyl ether acetate, etc.), nitriles (acetonitrile, isobutyrate) Nitriles), ethers (diisopropyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, etc. ), Acid amides (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 gaseous carrier include fluorocarbon, butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbon dioxide gas.

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

Other formulation adjuvants include sticking agents, dispersants, colorants, antifreezes and stabilizers, such as casein, gelatin, sugars (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin Derivatives, bentonite, synthetic water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids, etc.), glycerin, PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).

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

The pest control method of the present invention is carried out by applying an effective amount of the compound of the present invention to pests directly and / or to pest habitats (plants, soil, households, animal bodies, etc.). The pest control method of the present invention is usually used in the form of the pest control agent of the present invention. In addition, salts formed by the compounds of the present invention with strong acids such as sulfuric acid, methanesulfonic acid and p-toluenesulfonic acid also have excellent control activity against pests.

When the pest control agent of the present invention is used for pest control in the agricultural field, the application amount is usually 1 to 10,000 g as the amount of the compound of the present invention per 10,000 m ² . When the pest control agent of the present invention is formulated into an emulsion, a wettable powder, a flowable agent, etc., it is usually diluted with water so that the active ingredient concentration is 0.01 to 10,000 ppm. Granules, powders and the like are usually applied as they are.

These preparations and water dilutions of the preparations may be applied directly to pests or plants such as plants to be protected from pests, and in order to control pests that inhabit cultivated soil. You may apply to. When applied to soil, the soil may be the soil where the plant is cultivated or the soil where the plant is to be cultivated.

The resin preparation processed into a sheet or string can also be used by a method such as wrapping around a crop, stretching it in the vicinity of the crop, or laying it on the stock soil.
Examples of the place where the pest control agent of the present invention is used include paddy field, upland field, tea garden, orchard, and non-agricultural land. The pest control agent of the present invention can also be used in a seedling tray, a seedling box, a seedling culture soil, a seedling mat, and a hydroponic solution in a hydroponic farm. The cultivation method of plants in paddy fields and upland fields may be plowing cultivation or non-plowing cultivation.

When the pest control agent of the present invention is used for controlling pests living in the house, the amount applied is the amount of the compound of the present invention per area of 1 m ² when applied on the surface, usually 0.01. The amount of the compound of the present invention per 1 m ^{3 of} space is usually 0.01 to 500 mg when applied to a space. When the pest control agent of the present invention is formulated into an emulsion, a wettable powder, a flowable agent, etc., it is usually diluted with water so that the active ingredient concentration is 0.1 to 10,000 ppm. Apply oils, aerosols, smoke, poison baits, etc. as they are.

When the harmful arthropod control agent of the present invention is used to control ectoparasites of cattle, horses, pigs, sheep, goats, chickens, small animals such as dogs, cats, rats, mice, etc., it is well known in veterinary medicine. Can be used on animals. As a specific method of use, for the purpose of systemic suppression, for example, administration by tablet, feed mixing, suppository, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.) is intended for non-systemic suppression. In this case, for example, an oil agent or an aqueous liquid is sprayed, a pour-on treatment or a spot-on treatment is performed, the animal is washed with a shampoo preparation, or a resin preparation is attached to the animal with a collar or ear tag. When administered to an animal body, the amount of the compound of the present invention is usually in the range of 0.1 to 1,000 mg per 1 kg body weight of the animal.

The pest control agent of the present invention can be used in farmland where the following plants (hereinafter referred to as the present plant) are cultivated.
Cereals: corn, rice, wheat, barley, rye, triticale, oats, sorghum, cotton, soybeans, peanuts, peanuts, cypress (green beans), lentils, azuki beans, cowpeas, mung bean, safflower beans, red bean, moss beans, tepareen, Broad bean, pea, chickpea, lentil, lupine, pigeon bean, buckwheat, sugar beet, rapeseed, sunflower, sugar cane, tobacco, etc.
Vegetables: Eggplant vegetables (eggplants, tomatoes, peppers, peppers, bell peppers, potatoes, etc.), cucurbits vegetables (cucumbers, pumpkins, zucchini, watermelons, melons, etc.), cruciferous vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, mustard, broccoli, cauliflower, etc.), Asteraceae vegetables (burdock, garlic, artichoke, lettuce, etc.), liliaceae vegetables (eg, leek, onion, garlic, asparagus), celery family vegetables (carrot, parsley, celery) , American Bow Fu, etc.), Rubiaceae vegetables (spinach, chard, etc.), Lamiaceae vegetables (perilla, mint, basil, lavender, etc.), strawberry, sweet potato, yam, taro, etc.
Fruit trees: berries (apples, pears, Japanese pears, quince, quince, etc.), nuclear fruits (peaches, plums, nectarines, ume, sweet cherry, apricots, prunes, etc.), citrus (satsuma mandarin, orange, lemon, lime, grapefruit) ), Nuts (chestnut, walnut, hazel, almond, pistachio, cashew nut, macadamia nut, etc.), berries (blueberry, cranberry, blackberry, raspberry, etc.), grape, oyster, olive, loquat, banana, coffee, Date palm, coconut palm, oil palm etc.
Trees other than fruit trees: tea, mulberry, flowering trees (Satsuki, camellia, hydrangea, sasanqua, shikimi, sakura, yurinoki, crape myrtle, eustoma, etc.), roadside trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak) , Poplar, redwood, fu, sycamore, zelkova, blackfish, Japanese amberjack, moths, pine, pine, spruce, yew, elm, Japanese cypress, etc.), coral jug, dogwood, cedar, cypress, croton, masaki, kanamochi, etc.
Lawn: Shiba (Nasis, Pleurotus, etc.), Bermudagrass (Neurodonidae, etc.), Bentgrass (Oleoptera, Hykonukagusa, Odonoptera, etc.), Bluegrass (Nagahagusa, Oosuzunokatabira, etc.), Fescue (Oonishi nokegusa, Drosophila, etc.) , Grass, etc.), ryegrass (rat, wheat, etc.), anemonefish, and blue whale.
Forage crops: alfalfa, etc.
Other: Flowers (Rose, Carnation, Chrysanthemum, Eustoma, Gypsophila, Gerbera, Marigold, Salvia, Petunia, Verbena, Tulip, Aster, Gentian, Lily, Pansy, Cyclamen, Orchid, Lily of the valley, Lavender, Stock, Habutton, Primula, Poinsettia, gladiolus, cattleya, daisy, symbidium, begonia, etc.), biofuel plants (Jatropha, Curcas, safflower, Amanazuna, switchgrass, Miscanthus, Kusanoshi, Danchiku, Kenaf, cassava, willow, algae, etc.), ornamental plants, etc. .

The plant includes plants bred by hybrid technology.
In addition, the present plant includes a genetically modified plant prepared by a genetic recombination technique.
This plant also includes plants to which resistance to herbicides is imparted by genetic recombination techniques or classical breeding methods.
The plant further includes a plant imparted with an ability to produce a selective toxin against pests by a genetic recombination technique.
This plant includes a plant imparted with an ability to produce an anti-pathogenic substance by genetic recombination technology.
This plant includes plants to which useful traits such as oil component modification and amino acid content enhancing traits have been imparted.

As a method of applying the pest control agent of the present invention to this plant to be protected from damage such as feeding by pests, specifically, application to the foliage, flower vases or ears of plants such as foliage spraying Application to seeds of plants or vegetative propagation organs (for example, seed buds, bulbs, tubers, bulbs, stem fragments, etc.); application to plant seedlings (including cuttings).

Examples of the method for applying the pest control agent of the present invention to the foliage, flower vases or ears of plants include application methods applied to the surface of plants such as foliage spray, trunk spray, etc., and before flowering, during flowering A method of spraying on the vase or the whole plant at the flowering time including after flowering is mentioned, and a method of spraying on the ear of the heading time or the whole plant when the plant is cereal.
Examples of the method for applying the pest control agent of the present invention to plant seeds or vegetative propagation organs include, for example, a method of coating, smearing or applying to seeds or vegetative propagation organs, and seeds or vegetative propagation organs in liquid formulations. Examples thereof include a dipping method and a method of coating seeds or vegetative propagation organs (for example, a film coating method, a pellet coating method, etc.). In the method, the amount of the compound of the present invention is usually applied in the range of 0.2 to 5,000 g, preferably 0.5 to 1,000 g per 100 kg of plant seeds or vegetative propagation organs. Preferred dosage forms are aqueous liquid suspension preparations such as emulsions, wettable powders, flowables, and microcapsules. Plants to which the method is applied include, among these plants, soybeans, corn, cotton, wheat, barley, rye, triticale, oats, rice, sorghum, peanuts, peanuts except soybeans and peanuts, sugar beet, rapeseed, It is preferably applied to sunflower, potato, sugar cane and vegetables. When applied to sugarcane, sugarcane stalk fragments may be used in sugarcane cultivation.

The pest control agent of the present invention can be mixed or used in combination with known insecticides, acaricides, nematicides, fungicides, plant growth regulators and synergists. The pest control agent of the present invention can be used in combination with known herbicides. Examples of active ingredients of such insecticides, acaricides, nematicides, fungicides, herbicides and synergists are shown below.

Active Ingredients of Insecticides (1) Organophosphorus Compounds Acephate, Aluminum Phosphide, Butathiofos, Cadosafos, Chlorethoxyfos, Chlorfenvinphos, Chlorfenvinphos (Chlorpyrifos), Chlorpyrifos-methyl (Chlorpyrifos-methyl), Cyanophos (Cyanophos: CYAP), Diazinon (Diazinon), DCIP (Dichlorodiisopropylene ether), Diclofenthion (V), Dichlorfenthion (V) ), Dimethoate, dimethylvinphos, disulfoton, EPN, etion, ethoprofos, etrimfos, fention (MPP), EP, Phosthiazate, formothion, hydrogen phosphide, isofenphos, isoxathion, malathion, methulfenfos, methulfenfos, methulfenfos MTP), monocrotophos, nared (BRP), oxydeprofos (ESP), parathion, fosarone, phosmet (PMP), pirimiphosmethyl (pirimifion) (Pyridafention), quinalphos, phentoate, profenofos, propafos, prothiofos, pyrachlorfos, sulthiophos, sulthiophos tebupirimfos), temephos (temephos), tetrachlorvinphos bottle phosphite (tetrach1orvinphos), terbufos (terbufos), thiometon (thiometon), trichlorfon (trichlorphon: DEP), vamidothion (vamidothion), folate (phorate), and cadusafos (cadusafos).
(2) Carbamate compounds alaniccarb, bendiocarb, benfuracarb, BPMC, carbaryl (carbary1), carbofuran, carbothofen, loecarb , Fenobucarb, phenothiocarb, phenoxycarb, furathiocarb, isoprocarb (MIPC), methocarb (metolcarb) hiocarb), NAC, oxamyl (oxamyl), pirimicarb (pirimicarb), propoxur (propoxur: PHC), XMC, thiodicarb (thiodicarb), xylylcarb (xylylcarb), and aldicarb (aldicarb).

(3) pyrethroid compounds acrinathrin, allethrin, benfluthrin, beta-cyfluthrin, bifenthrin, cycloprotorin, fluprothrin (cycloprothrin) , Cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucitrate lucytrinate, flufenprox, flumethrin, fluvalinate, halfenprox, imiprothrin, permethrin, praretrin, praretrin resmethrin, sigma-cypermethrin, silafluofen, tefluthrin, tralomethrin, transfluthrin, tetramethrin ethrin), phenothrin, cyphenothrin, alpha-cypermethrin, zeta-cypermethrin, lambda cihalothrin (lambda-halothrin) ), Furamethrin, tau-fluvalinate, methfluthrin, profluthrin, dimethylfluthrin, 2,3,5,6-tetrafluoro-4- (methoxymethyl) benzyl ( EZ)-(1RS, 3RS; 1RS, 3S ) -2,2-dimethyl-3-prop-1-enylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methylbenzyl (EZ)-(1RS, 3RS; 1RS, 3SR) -2 , 2-Dimethyl-3-prop-1-enylcyclopropanecarboxylate and 2,3,5,6-tetrafluoro-4- (methoxymethyl) benzyl (1RS, 3RS; 1RS, 3SR) -2,2- Dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4- (methoxymethyl) benzyl (EZ)-(1RS, 3RS; 1RS, 3SR)- 2,2-Dimethyl-3- (2-cyano-1-propenyl) cyclopropanecarboxylate.
(4) Nereistoxin compounds Cartap, bensultap, thiocyclam, monosultap, and bisultap.

(5) Neonicotinoid compounds imidacloprid (imidac1oprid), nitenpyram (nitenpyram), acetamiprid (acetamipride), thiamethoxam, thiacloprid (thiacloprid), dinoteurin (dinothurine)
(6) Benzoylurea compound Chlorfluazuron, bistrifluron, diafenthiuron, diflubenzuron, fluazuron, flucycloxuron, flucyclolone (Flufenoxuron), hexaflumuron, lufenuron, novaluron, novifluuron, teflubenzuron, triflumuron, and triflumuron.
(7) Phenylpyrazole compounds Acetoprole, etiprole, fipronil, vaniliprole, pyriprole, and pyrafluprole.
(8) Bt toxin Live spores and produced crystal toxins derived from Bacillus thuringiensis, and mixtures thereof;
(9) Hydrazine compounds Chromafenozide, halofenozide, methoxyphenozide, and tebufenozide.
(10) Organochlorine compounds Aldrin, dieldrin, dienochlor, endosulfan, and methoxychlor.

(11) Other Insecticide Active Ingredients Machine oil, nicotine-sulfate; avermectin, bromopropyrate, buprofezin, chlorfenapyr, chlorphenapyr Ritranol, cyromazine, DD (1,3-Dichloropropene), emamectin benzoate, fenazaquin, flupirroprene, flupyrazolen , Indoxacarb, methoxadiazone, milbemycin-A, pymetrozine, pyridalyl, pyriprosul, spiromidol, spinodulsulfide tolfenpyrad, triazamate, flubendiamide, repimectin, arsenous acid, benclothiaz, lime nitrogen calcium lime ulfide, chlordane, DDT, DSP, flufenerim, flonicamid, flurimfen, formatenate, metham-ammonium, metam-ammonium sodium, methyl bromide, potassium oleate, protrifenbute, spiromesifen, sulfoxafluor, sulfur, metafluon, sulfur ), Spirotetramat (sp rotetramat), pyrifluquinazon (pyrifluquinazone), spinetoram (spinetoram), chlorantraniliprole (chlorantraniliprole), Toraropiriru (tralopyril), cyan tiger Niri Prowl (cyantraniliprole),
Following formula (K)

[Where,
R ¹⁰⁰ represents a chlorine, bromine or trifluoromethyl group,
R ²⁰⁰ represents a chlorine, bromine or methyl group,
R ³⁰⁰ represents chlorine, bromine or a cyano group. ]
And a compound represented by the following formula (L)

[Where,
R ¹⁰⁰⁰ represents chlorine, bromine or iodine. ]
A compound represented by

Active ingredients of acaricides: acequinocyl, amitraz, benzoximate, bifenaate, phenisobromolate (BS), chinomethionate (BS), chinomethionate (BS) chlorfenson, clofentezine, cyflumetofene, kelsen (dicofol), etoxazole, fenbutatin oxide (fenbutafen), fenothiocarbene roximate, fluacrylpyrim, fluproxyfen, hexythiazox, propargite (BPPS), polynactin complex (pyridene), pyridaben (pyriben) (Tetradifon), spirodiclofen, spiromesifen, spirotetramat, amidoflumet, and cenopyrafen.

Active ingredients of nematicides DCIP, fostiazate, levamisole hydrochloride, methylisothiocyanate, morantel tartrate, and imiciafos.

Active ingredients of fungicides Propiconazole, Prothioconazole, Triadimenol, Prochloraz, Penconazole, Tebuconazole, Tebuconazole, Tebuconazole , Bromuconazole, epoxiconazole, difenoconazole, cyproconazole, metconazole, triflumazole, triflumizole Tetraconazole, microbutanil, fenbuconazole, hexaconazole, fluquinconazole, triticonazole, triticonazole, triticonazole, triticonazole Azole fungicidal compounds such as flutriafol;
Cyclic amine bactericidal compounds such as fenpropimorph, tridemorph, fenpropidin;
Benzimidazole fungicidal compounds such as carbendezim, benomyl, thiabendazole, thiophanate-methyl;
Procymidone; cyprodinil; pyrimethanil; dietofencarb; thiuram; fluazilonyl; Captan; mepanipyrim; fenpiclonil; fludioxonil; diclofluraned; folppet; cresoxime- azoxystrobin; trifloxystrobin; fluoxastrobin; picoxystrobin; pyracrostrobin; dimoxystrobin; dimoxystrobin; dimoxystrobin; Pyribencarb; spiroxamine; quinoxyfen; fenhexamid; famoxadone; fenamidone; samamide; samamide; iprovalicarb; benthiavaricarb; cyazofamid; mandipropamid; boscaliden; (Bifafen); cyflufenamide; proquinazid; isotianil and thiadinil.

Active ingredient of herbicide (1) Phenoxy fatty acid herbicidal compound 2,4-D, MCP, MCPB, phenthiol (phenothio1), mecoprop, fluroxypyr, triclopyr, clomeprop, Naproanilide.
(2) Benzoic acid herbicidal compound 2,3,6-TBA, dicamba, clopyralid, picloram, aminopyralid, quinclorac, and quinmerac.
(3) Urea herbicidal compounds diuron, linuron, chlortoluron, isoproturon, fluometuron, isouron, tebuthiuron, tebuthiuron, metabenthuron , Cumyluron, daimuron, and methyl-daimuron.
(4) Triazine herbicidal compounds atrazine, ametrine, cyanazine, simazine, propazine, simetrin, dimethamethrin (dimethymetrine) ), Triaziflam, and indaziflam.
(5) Bipyridinium herbicidal compound paraquat and diquat.

(6) Hydroxybenzonitrile herbicidal compounds bromoxynil and ioxynil.
(7) Dinitroaniline herbicidal compounds pendimethalin, prodiamine, and trifluralin.
(8) Organophosphorus herbicidal compounds amiprofos-methyl, butamifos, bensulide, piperophos, anilofos, glyphosate, glufosinate, glufosinate, glufosinate P (glufosinate-P), and bialaphos.
(9) Carbamate herbicidal compounds: di-allate, tri-allate, EPTC, butyrate, beniocarb, esprocarb, molinate, dimepiperate (Swep), chlorpropham, phenmedifam, phenisopham, piributicarb, and asuram.
(10) Acid amide herbicidal compounds propanil, propyzamide, bromobutide, and etobanzanide.

(11) Chloroacetanilide herbicidal compounds acetochlor, acechlor, butachlor, dimethenamide, propachlor, metazachlor, metrachlor or totrachlor pretilachlor), tenylchlor (theny1ch1or), and petoxamide.
(12) Diphenyl ether herbicidal compounds aciflufen-sodium, bifenox, oxyfluorfen, lactofen, fomesafen, clomethoxythonifen, and chloromethoxypheny.
(13) Cyclic imide herbicidal compounds oxadiazon, cinidon-ethyl, carfentrazone-ethyl, sulfentrazone, full-microlac-pentyl, flumi-lacyl-pentyl Oxazine (flumioxazin), pyraflufen-ethyl, oxadiargyl (oxadiargy1), pentoxazone (pentoxazone), fluthiacet-methyl (butafenzilben) zone), and saflufenacil (saflufenacil).
(14) Pyrazole herbicidal compounds benzofenap, pyrazolate, pyrazoxifene, topramzone, and pyrasulfotole.
(15) Triketone herbicidal compounds isoxaflutole, benzobicyclon, sulcotrione, mesotrione, tembotrione, and tefriltrione.
(16) Aryloxyphenoxypropionic acid herbicidal compound clodinafop-propargyl, cyhalofop-butyl, diclohop-methyl, phenoxaprop-ethyl, fenoxaprop-propyl Fluazifop-butyl, haloxyhop-methyl, quizalofop-ethyl, metamihop.
(17) Trione oxime herbicidal compounds alloxydim-sodium, cetoxydim, butoxydim, crestodim, cloxydimim, cycloxidim, texydimym (Traxydim), and profoxydim.

(18) A sulfonylurea herbicidal compound chlorsulfuron, sulfomethuron-methyl, metsulfuron-methyl, chlorimuron-ethyl, trivenuron methyl (18) tribenuron-methyl, trisulfuron, bensulfuron-methyl, thifensulfuron-methyl, pyrazosulfuron-methyl, urmisyl-uryl-uryl-uryl Nicosulfuron (nico) ulfuron, amidosulfuron, cinosulfuron, imazosulfuron, rimsulfuron, halosulfuron (thulfuron), prosulfuron (thulsulfuron), prosulfuron (thulsulfuron) , Triflusulfuron-methyl, flazasulfuron, cyclosulfamuron, flupirsulfuron, sulfosulfurium, sulfosulfurimuron Azulsulfuron, ethoxysulfuron, oxasulfuron, iodosulfuron-methyl-sodium, foramsulfuron, mesosulfuron, mesulfuron methyl Trisulfursulfuron, tritosulfuron, orthosulfamuron, flucetosulfuron, and propyrisulfuron.
(19) Imidazolinone herbicidal compounds imazametabenz-methyl, imazamethapyr, imazamox, imazapyr, imazapir, imazaquin (i)
(20) Sulfonamide herbicidal compounds flumetslam, metosulam, dicloslam, floraslam, chloransrammethyl, penoxsulox, penoxsulox, and penoxsulox.
(21) Pyrimidinyloxybenzoic acid herbicidal compound pyrithiobac-sodium, bispyribac-sodium, pyriminobac-methyl1, pyribenzoximpy, And pyrimisulfan.
(22) Other herbicidal compounds bentazon, bromacil, terbacil, chlorthiamid, isoxaben, dinoseb, amitrole, cinmethyline, cinmethyline (cinthyl) tripiphane, dalapon (da1apon), diflufenzopyr sodium (diflufenzopyr-sodium), dithiopyr (dithiopyr), thiazopyr (thiazopyr), sodium flucarbazone (proflubazone) Nasset (mefenacet), flufenacet (flufenacet), fentrazamide (fentrazamide), caffenstrole (cafenstrom), indanophan (indanofan), oxadichromemephone (oxaneclomefone), fidarate (benduresate) (Norflurazon), flurtamon, diflufenican, picolinafen, beflubutamide, clomazone, amicarbazone , Pinoxaden (pinoxaden), pyraclonil (pyraclonil), pyroxasulfone (pyroxasulfone), thien-carbazone methyl (thiencarbazone-methyl), amino cyclo Pila crawl (aminocyclopyrachlor), type phen carbazone (ipfencarbazone), and Mechiozorin (methiozolin).

Active ingredient of synergist piperonyl butoxide, sesamex, sulfoxide, N- (2-ethylhexyl) -8,9,10-trinorborn-5-ene-2,3-di Carboximide (MGK 264), N-decrimimidazole, WARF-anti-resistant, TBPT, TPP, IBP, PSCP, methyl iodide (CH ₃ I), t-phenyl butyl Tenon (t-phenylbutone), diethyl maleate, DMC, FDMC, ETP, and ETN.

Hereinafter, although this invention is demonstrated in more detail by a 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 invention compound.

(Production Example 1)
(1)
In a mixture of 3.6 g N ¹ -methyl-4-trifluoromethyl-benzene-1,2-diamine, 3.8 g 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 250 mg HOBt, and 37 mL pyridine Under ice cooling, 3.8 g of 3,6-dichloro-pyridine-2-carboxylic acid was added. The mixture was warmed to room temperature and stirred at room temperature for 12 hours. The reaction mixture was poured into water, and the precipitated solid was filtered. The obtained solid was washed with water and dried to obtain 7.3 g of solid A.
(2)
A mixture of 7.3 g of solid A and 40 mL of acetic acid was stirred with heating under reflux for 5 hours. The mixture was allowed to cool to room temperature and water was added. The precipitated solid was collected by filtration and dried under reduced pressure to obtain 6.3 g of the following compound B.

Compound B: ¹ H-NMR (CDCl ₃ ) δ: 8.17 (1H, d), 7.90 (1H, d), 7.64 (1H, dd), 7.54 (1H, d), 7.46 (1H, d), 3.92 ( 3H, s).
(3)
To a mixture of Compound B, 810 mg of sodium hydride (60%, oily), and 36 mL of tetrahydrofuran, 1.4 mL of ethyl mercaptan was added dropwise under ice cooling. The mixture was stirred for 3 hours under ice-cooling, water was added, and the mixture was extracted with ethyl acetate. The obtained organic layer was dried over anhydrous sodium sulfate, and then dried under reduced pressure to obtain 6.4 g of a mixture C.
To a mixture of 6.4 g of this mixture C and 61 mL of chloroform, 8.5 g of 75% m-chloroperbenzoic acid was added under ice cooling. After stirring for 12 hours under ice-cooling, the reaction mixture was added to a saturated aqueous multilayer solution and extracted with chloroform. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and dried under reduced pressure. The resulting residue was subjected to silica gel chromatography to obtain 3.4 g of compound D.

Compound D: ¹ H-NMR (CDCl ₃ ) δ: 8.46 (1H, d), 8.07 (1H, d), 7.70 (1H, d), 7.65 (1H, dd), 7.55 (1H, d), 3.87 ( 2H, q), 3.84 (3H, s), 1.37 (3H, t).
(4)
To a mixture of 300 mg of compound D, 36 mg of sodium hydride (60%, oily) and 1.5 mL of DMF, 77 mg of 1H-1,2,4-triazole was added under ice cooling. The reaction mixture was stirred for 4 hours under ice cooling, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was dried over anhydrous sodium sulfate and then dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 300 mg of the following present compound 1.

The present compound 1: ¹ H-NMR (DMSO-D ₆ ) δ: 9.57 (1H, s), 8.74 (1H, d), 8.46 (1H, s), 8.31 (1H, d), 8.17 (1H, d ), 8.00 (1H, d), 7.76 (1H, dd), 3.97-3.88 (5H, m), 1.24 (3H, t).

(Production Example 2)
The following present compound 2 of the present invention is obtained according to the method described in Production Example 1 (4) using 3-chloro-1H-1,2,4 triazole instead of 1H-1,2,4-triazole. It was.

Compound 2 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.06 (1H, s), 8.72 (1H, d), 8.21 (1H, d), 8.11 (1H, d), 7.69 (1H, dd), 7.59 (1H, d), 3.83-3.78 (5H, m), 1.37 (3H, t).

(Production Example 3)
The following compound 3 of the present invention is obtained according to the method described in Production Example 1 (4) using 3-methyl-1H-1,2,4 triazole instead of 1H-1,2,4-triazole. It was.

Compound 3 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.03 (1H, s), 8.66 (1H, d), 8.19 (1H, d), 8.10 (1H, d), 7.68 (1H, dd), 7.58 (1H, d), 3.83-3.77 (5H, m), 2.54 (3H, s), 1.37 (3H, t).

(Production Example 4)
(1)
To a mixture of 20 g of 4- (trifluoromethylthio) -aniline and 40 mL of chloroform, 20 mL of acetic anhydride was added dropwise under ice cooling. After completion of the dropwise addition, 40 mL of chloroform was added to the mixture and stirred at room temperature for 12 hours. 80 mL of hexane was added to the obtained reaction mixture, the precipitated solid was filtered, and the obtained solid was washed with hexane to obtain 23 g of the following compound E.

Compound ^{E: 1 H-NMR (CDCl} 3) δ: 8.28 (1H, d), 7.56 (1H, dd), 6.41 (1H, d), 5.44 (1H, s), 2.96 (3H, d).
(2)
A mixture of 22 g of Compound E and 96 mL of sulfuric acid was cooled to −10 ° C., and at the same temperature, a mixture of fuming nitric acid 7.2 mL and sulfuric acid 24 mL was added dropwise to reach 0 ° C. The reaction mixture was stirred for 6 hours under ice-cooling, and the reaction mixture was poured into water and extracted with chloroform. The organic layer was washed with water, dried over sodium sulfate, and then dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 10 g of the following compound F.

Compound F: ¹ H-NMR (CDCl ₃ ) δ: 10.46 (1H, s), 8.93 (1H, d), 8.53 (1H, d), 7.90 (1H, dd), 2.33 (3H, s).
(3)
To a mixture of 10 g of compound F and 121 mL of DMF, 1.6 g of sodium hydride (60%, oily) was added under ice cooling, and the mixture was cooled to 0 ° C. To this mixture, a mixed solution of 2.4 mL of iodomethane and 20 mL of DMF was added dropwise under ice cooling. After completion of dropping, the mixture was warmed to room temperature and stirred for 4 hours. The obtained reaction mixture was poured into 1N aqueous hydrochloric acid and extracted with ethyl acetate. The obtained organic layer was washed with a 0.5N aqueous hydrochloric acid solution and a saturated aqueous sodium chloride solution, dried over sodium sulfate, and then dried under reduced pressure.
The obtained residue was diluted with a mixed solution of 55 mL of methanol and 18 mL of water. To this solution was added 5.8 g of sodium hydroxide under ice cooling, and the mixture was stirred at room temperature for 12 hours. The obtained reaction mixture was poured into 1N aqueous hydrochloric acid solution, and the precipitated solid was collected by filtration. The obtained solid was washed with water and dried to obtain 9.8 g of a solid G.
(4)
A mixture of 13 g of iron powder, 19 mL of acetic acid, 200 mL of tetrahydrofuran, and 28 mL of water was heated to 65 ° C., and a mixed solution of 14 g of solid G and 50 mL of tetrahydrofuran was added dropwise with stirring. After completion of dropping, the mixture was stirred at 65 ° C. for 3 hours. The resulting reaction mixture was filtered through Celite (registered trademark) and washed with tetrahydrofuran. The obtained filtrate was dried under reduced pressure. The obtained residue was diluted with a saturated aqueous solution, and extracted with ethyl acetate. The obtained organic layer was dried over sodium sulfate and then dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain the following compound H13 g.

Compound H: ¹ H-NMR (CDCl ₃ ) δ: 7.16 (1H, dd), 6.98 (1H, d), 6.61 (1H, d), 3.78 (1H, s), 3.30 (2H, s), 2.89 ( 3H, s).
(5)
To a mixture of Compound H 5.0 g, 3,6-dichloro-pyridine-2-carboxylic acid 4.8 g, HOBt 300 mg, and pyridine 45 mL, EDCI 4.8 g was added under ice cooling. After stirring the reaction mixture at room temperature for 12 hours, the reaction mixture was poured into water. The precipitated solid was collected by filtration, washed with water and dried to obtain 8.0 g of solid I.
(6)
A mixture of 8.0 g of solid I and 20 mL of acetic acid was stirred with heating under reflux for 1.5 hours. The resulting reaction mixture was poured into water and extracted with ethyl acetate. The obtained organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated sodium chloride, dried over sodium sulfate, and then dried under reduced pressure. The obtained solid was washed with hexane and collected by filtration to obtain 7.0 g of the following compound J.

Compound J: ¹ H-NMR (CDCl ₃ ) δ: 8.22 (1H, d), 7.89 (1H, d), 7.66 (1H, dd), 7.49 (1H, d), 7.45 (1H, d), 3.90 ( 3H, s).
(7)
A mixture of Compound J (6.9 g), tetrahydrofuran (30 mL) and sodium hydride (60%, oily) 800 mg was cooled to −10 ° C., and a mixture of ethyl mercaptan (1.4 mL) and tetrahydrofuran (7 mL) was added dropwise thereto. After completion of dropping, the mixture was warmed to room temperature and stirred for 7 hours. The resulting reaction mixture was poured into a saturated aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. The obtained organic layer was dried over sodium sulfate and then dried under reduced pressure. The resulting residue was subjected to silica gel chromatography to obtain 770 mg of the following compound K.

Compound K: ¹ H-NMR (CDCl ₃ ) δ: 8.22 (1H, d), 7.72 (1H, d), 7.64 (1H, dd), 7.47 (1H, d), 7.38 (1H, d), 3.98 ( 3H, s), 2.95 (2H, q), 1.35 (3H, t).
(8)
To a mixture of 770 mg of Compound K and 8 mL of chloroform, 470 mg of m-chloroperbenzoic acid (75%) was added under ice cooling. After stirring for 1 hour under ice cooling, 320 mg of sodium hydrogen carbonate, 1 mL of water and 460 mg of m-chloroperbenzoic acid (75%) were sequentially added under ice cooling. After stirring for 5 hours under ice cooling, a saturated aqueous sodium hydrogen carbonate solution and sodium sulfite were added to the reaction mixture. This mixture was extracted with chloroform, and the resulting organic layer was dried over sodium sulfate and dried under reduced pressure. The obtained residue was subjected to silica gel chromatography, so as to obtain the following compound L550 mg.

Compound L: ¹ H-NMR (CDCl ₃ ) δ: 8.46 (1H, d), 8.12 (1H, d), 7.70 (1H, d), 7.67 (1H, dd), 7.50 (1H, d), 3.87 ( 2H, q), 3.82 (3H, s), 1.37 (3H, t).
(9)
To a mixture of Compound L270 mg, DMF 3 mL, and sodium hydride (60%, oily) 38 mg, 52 mg of 1H-1,2,4-triazole was added under ice cooling. The mixture was warmed to room temperature and stirred for 2 hours. Saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was dried over sodium sulfate and then dried under reduced pressure. The resulting residue was subjected to silica gel chromatography to obtain 280 mg of the following present compound 4.

Compound 4 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.15 (1H, s), 8.71 (1H, d), 8.28 (1H, d), 8.20 (1H, s), 8.16 (1H, d), 7.71 (1H, dd), 7.54 (1H, d), 3.85-3.79 (5H, m), 1.38 (3H, t).

(Production Example 5)
The following compound 5 of the present invention was obtained according to the method described in Production Example 4 (9) using 3-chloro-1H-1,2,4 triazole instead of 1H-1,2,4-triazole.

Compound 5 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.05 (1H, s), 8.71 (1H, d), 8.20 (1H, d), 8.15 (1H, d), 7.71 (1H, dd), 7.54 (1H, d), 3.84-3.77 (5H, m), 1.37 (3H, t).

(Production Example 6)
(1)
A mixture of 2.2 g of Compound J, 12 mL of DMF, and 510 mg of sodium hydride (60%, oily) was cooled to 0 ° C., and 0.90 mL of ethyl mercaptan was added dropwise at the same temperature. The reaction mixture was warmed to room temperature and stirred at room temperature for 12 hours. The obtained reaction mixture was poured into water, the precipitated solid was collected by filtration, and the obtained solid was washed with water and dried to obtain 2.3 g of the following compound M.

Compound M: ¹ H-NMR (CDCl ₃ ) δ: 8.22 (1H, d), 7.65-7.59 (2H, m), 7.47 (1H, dd), 7.24 (1H, d), 3.92 (3H, s), 3.16 (2H, q), 2.90 (2H, q), 1.35 (3H, t), 1.29 (3H, t).
(2)
To a mixture of 5.9 g of Compound M and 70 mL of chloroform, 12 g of m-chloroperbenzoic acid (70%) was added under ice cooling. The reaction mixture was warmed to room temperature and stirred for 12 hours. A saturated aqueous sodium hydrogen carbonate solution and sodium sulfite were added to the obtained reaction mixture, and the mixture was stirred at room temperature for 1 hour. This mixture was extracted with chloroform, and the resulting organic layer was washed with water and a saturated aqueous sodium chloride solution, dried over sodium sulfate, and then dried under reduced pressure. The resulting residue was subjected to silica gel chromatography to obtain 2.2 g of the following compound N.

Compound N: ¹ H-NMR (CDCl ₃ ) δ: 8.81 (1H, d), 8.43 (1H, d), 8.14 (1H, d), 7.71 (1H, dd), 7.54 (1H, d), 3.97 ( 2H, q), 3.85 (3H, s), 3.46 (2H, q), 1.41 (3H, t), 1.36 (3H, t).
(3)
To a mixture of 2.1 g of compound N and 22 mL of chloroform, 1.0 g of m-chloroperbenzoic acid (75%) was added under ice cooling. After stirring for 2 hours under ice cooling, 1.0 g of m-chloroperbenzoic acid (75%) was further added to the reaction mixture. After warming to room temperature and stirring for 12 hours, a saturated aqueous sodium hydrogen carbonate solution and sodium sulfite were added to the reaction mixture, and the mixture was extracted with chloroform. The obtained organic layer was dried over sodium sulfate and then dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 2.1 g of the following compound O.

Compound O: ¹ H-NMR (CDCl ₃ ) δ: 8.83 (1H, d), 8.46 (1H, d), 8.31 (1H, d), 7.83 (1H, dd), 7.73 (1H, d), 3.97 ( 2H, q), 3.90 (3H, s), 3.47 (2H, q), 1.46-1.33 (6H, m).
(4)
To a mixture of 350 mg of Compound O, 1.5 mL of DMF, and 53 mg of sodium hydride (60%, oily), 37 mg of 1H-1,2,4-triazole was added under ice cooling. The mixture was warmed to room temperature and stirred for 5 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the obtained reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was dried over sodium sulfate and then dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 260 mg of the following present compound 6.

The present invention Compound ^{6: 1 H-NMR (CDCl} 3) δ: 9.16 (1H, s), 8.72 (1H, d), 8.33-8.28 (2H, m), 8.20 (1H, s), 7.84 (1H, dd ), 7.73 (1H, d), 3.87 (3H, s), 3.82 (2H, q), 1.38 (3H, t).

(Production Example 7)
The following compound 7 of the present invention is obtained according to the method described in Production Example 6 (4) using 3-chloro-1H-1,2,4-triazole instead of 1H-1,2,4-triazole. It was.

Compound 7 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.06 (1H, s), 8.73 (1H, d), 8.31 (1H, s), 8.23 (1H, d), 7.84 (1H, d), 7.73 (1H, d), 3.86 (3H, s), 3.80 (2H, q), 1.38 (3H, t).

(Production Example 8)
(1)
A mixture of 2.3 g of Compound M, 25 mL of acetonitrile, and 330 mg of sodium tungstate dihydrate was heated to 60 ° C., and 8 mL of 30% aqueous hydrogen peroxide was added dropwise with stirring. After completion of dropping, the mixture was stirred at 60 ° C. for 7 hours. The resulting reaction mixture was allowed to cool to room temperature, saturated aqueous sodium hydrogen carbonate solution and sodium sulfite were added, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate, and then dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 1.5 g of the following compound P.

Compound P: ¹ H-NMR (DMSO-D ₆ ) δ: 8.89 (1H, d), 8.60 (1H, d), 8.56 (1H, d), 8.21 (1H, d), 8.13 (1H, dd), 3.96 (2H, q), 3.91 (3H, s), 3.60 (2H, q), 1.28-1.15 (6H, m).
(2)
To a mixture of 200 mg of Compound P, 1 mL of DMF, and 20 mg of sodium hydride (60%, oily), 33 mg of 1H-1,2,4-triazole was added under ice cooling. The mixture was warmed to room temperature and stirred for 5 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the obtained reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was dried over sodium sulfate and then dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 190 mg of the following present compound 8.

Present compound ^{8: 1 H-NMR (CDCl} 3) δ: 9.14 (1H, s), 8.72 (1H, d), 8.56 (1H, s), 8.32 (1H, d), 8.21 (1H, s), 8.07 (1H, d), 7.75 (1H, d), 3.88 (3H, d), 3.79 (2H, q), 1.39 (3H, t).

(Production Example 9)
The following compound 9 of the present invention is obtained according to the method described in Preparation Example 8 (2) using 3-chloro-1H-1,2,4-triazole instead of 1H-1,2,4-triazole. It was.

Compound 9 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.05 (1H, s), 8.73 (1H, d), 8.55 (1H, d), 8.25 (1H, d), 8.06 (1H, dd), 7.75 (1H, d), 3.88 (3H, s), 3.78 (2H, q), 1.39 (3H, t).

(Production Example 10)
To a mixture of 200 mg of Compound P, 0.8 mL of DMF, and 20 mg of sodium hydride (60%, oily), 57 mg of 3-methylthio-1H-1,2,4-triazole was added under ice cooling. The mixture was warmed to room temperature and stirred for 5 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the obtained reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was dried over sodium sulfate and then dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 120 mg of the following present compound 10.

Compound 10 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.04 (1H, s), 8.68 (1H, d), 8.56 (1H, s), 8.22 (1H, d), 8.07 (1H, d), 7.74 (1H, d), 3.86 (3H, s), 3.77 (2H, q), 2.71 (3H, s), 1.38 (3H, t).

(Production Example 11)
To a mixture of 120 mg of the present compound 10 and 5 mL of chloroform, 120 mg of m-chloroperbenzoic acid (75%) was added under ice cooling. The mixture was warmed to room temperature and stirred for 12 hours. A saturated aqueous sodium hydrogen carbonate solution and sodium sulfite were added to the obtained reaction mixture, and the mixture was extracted with chloroform. The obtained organic layer was dried over sodium sulfate and then dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 80 mg of the following present compound 11.

Compound 11 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.25 (1H, s), 8.80 (1H, d), 8.57 (1H, d), 8.42 (1H, d), 8.09 (1H, dd), 7.76 (1H, d), 3.88 (3H, s), 3.79 (2H, q), 3.39 (3H, s), 1.40 (3H, t).

(Production Example 12)
(1)
To a mixture of 2.7 g of 3,6-dichloro-pyridine-2-carboxylic acid and 27 mL of toluene, 2.0 mL of thionyl chloride and 1 drop of DMF were sequentially added at room temperature. The reaction mixture was heated to 100 ° C. and stirred for 1.5 hours, and then the reaction mixture was concentrated under reduced pressure. To the obtained residue, a mixture of 27 mL of tetrahydrofuran and 2.4 g of 2-amino-4-trifluoromethylphenol was added at room temperature, and the mixture was stirred at room temperature for 5 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then dried under reduced pressure to obtain 4.7 g of the following compound Q.

Compound Q: ¹ H-NMR (CDCl ₃ ) δ: 9.96 (1H, s), 8.82 (1H, s), 7.89 (1H, d), 7.62 (1H, d), 7.52 (1H, d), 7.44 ( 1H, dd), 7.14 (1H, d).
(2)
To a mixture of 3.7 g of compound Q, 3.3 g of triphenylphosphine, and 21 mL of tetrahydrofuran, 3.2 g of bis (2-methoxyethyl) azodicarboxylate was added under ice cooling, and the mixture was stirred at room temperature for 5 hours. To this mixture was added a saturated aqueous ammonium chloride solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 3.0 g of the following compound R.

Compound R: ¹ H-NMR (CDCl ₃ ) δ: 8.22 (1H, s), 7.92 (1H, d), 7.81 (1H, d), 7.75 (1H, d), 7.49 (1H, d).
(3)
To a mixture of 3.0 g of Compound R, 390 mg of sodium hydride (60%, oily), and 30 mL of tetrahydrofuran, 650 μL of ethyl mercaptan was added dropwise under ice cooling. After this mixture was stirred at room temperature for 1 hour, water was added to precipitate a solid. After filtering this solid, the obtained solid was washed with a mixed solvent of methyl tert-butyl ether: hexane = 1: 3 to obtain 2.9 g of the following compound S.

Compound ^{S: 1 H-NMR (CDCl} 3) δ: 8.23 (1H, d), 7.80 (1H, d), 7.74 (1H, d), 7.71 (1H, dd), 7.44 (1H, d).
(4)
A mixture of 2.9 g of compound S and 27 mL of chloroform was cooled to 0 ° C., and 3.9 g of metachloroperbenzoic acid was added thereto. The reaction mixture was stirred at room temperature for 3 hours, and then a saturated aqueous sodium sulfite solution and a saturated aqueous sodium hydrogen carbonate solution were added under ice cooling. This reaction mixture was extracted with chloroform, and the obtained organic layer was dried over anhydrous sodium sulfate and then dried under reduced pressure to obtain 3.0 g of the following compound T.

Compound T: ¹ H-NMR (CDCl ₃ ) δ: 8.53 (1H, d), 8.15 (1H, t), 7.80-7.76 (3H, m), 4.02 (2H, q), 1.44 (3H, t).
(5)
To a mixture of 2.0 g of Compound T and 20 mL of chloroform, 710 mg of 1,2,4-triazole, 1.8 mL of diisopropylethylamine, and 120 mg of N, N-dimethyl-4-aminopyridine were sequentially added at room temperature. The reaction mixture was heated to 70 ° C. and stirred for 15 hours, water was added, and the mixture was extracted with chloroform. The obtained organic layer was dried over anhydrous sodium sulfate and then dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 2.0 g of the following present compound 12.

Compound 12 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.30 (1H, s), 8.75 (1H, d), 8.30 (1H, d), 8.20-8.18 (2H, m), 7.84-7.81 (2H , m), 4.00 (2H, q), 1.45 (3H, t).

(Production Example 13)
(1)
To a mixture of 12 g of 3,6-dichloro-pyridine-2-carboxylic acid and 80 mL of tetrahydrofuran, 6.4 mL of oxalyl chloride and 1 drop of N, N-dimethylformamide were added and stirred at room temperature for 1 hour. The reaction mixture was concentrated and dissolved in 30 mL of tetrahydrofuran, and this was added dropwise to a mixture of 13 g of 2-amino-4- (trifluoromethylsulfanyl) phenol and 50 mL of tetrahydrofuran under ice cooling. After stirring at room temperature for 1 hour, the reaction mixture was added to a saturated aqueous multilayer solution and extracted with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and then dried under reduced pressure to obtain 23 g of the following compound U.

Compound U: ¹ H-NMR (DMSO-D ₆ ) δ: 11.14 (1H, s), 10.20 (1H, s), 8.54 (1H, d), 8.17 (1H, t), 7.77 (1H, d), 7.38 (1H, dd), 7.06 (1H, d).
(2)
A mixture of Compound U23g, p-toluenesulfonic acid monohydrate 2.3g, and xylene 70mL was stirred with heating under reflux for 2 hours. The mixture was allowed to cool to room temperature, added to a saturated aqueous multilayer solution, and extracted with ethyl acetate. The obtained organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and dried under reduced pressure. The obtained crude product was washed with hexane / isopropanol to obtain 17 g of the following compound V.

Compound V: ¹ H-NMR (CDCl ₃ ) δ: 8.25 (1H, s), 7.91 (1H, d), 7.79-7.72 (2H, m), 7.48 (1H, d).
(3)
A mixture of 17 g of Compound V, 2.1 g of sodium hydride (60%, oily), and 140 mL of tetrahydrofuran was cooled to 0 ° C., and 3.5 mL of ethyl mercaptan was added dropwise. The mixture was stirred for 3 hours under ice cooling, and then the reaction mixture was poured into water, and the precipitated solid was filtered. The obtained solid was washed with hexane / methyl-tert-butyl ether and dried to obtain 17 g of Compound W.

Compound W: ¹ H-NMR (CDCl ₃ ) δ: 8.26 (1H, s), 7.77-7.69 (3H, m), 7.44 (1H, d), 3.06 (2H, q), 1.47 (3H, t).
(4)
A mixture of 17 g of Compound W and 130 mL of chloroform was cooled to 0 ° C., 9.7 g of 75% m-chloroperbenzoic acid was added, and the mixture was stirred for 2 hours under ice cooling. To this mixture, 9.7 g of 75% m-chloroperbenzoic acid was further added under ice cooling, and the mixture was stirred for 1 hour under ice cooling. To this mixture was further added 10 g of 75% m-chloroperbenzoic acid under ice cooling, and the mixture was stirred for 19 hours under ice cooling. This reaction mixture was added to a saturated multilayer aqueous solution and extracted with chloroform. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain the following compound X3.0 g, compound Y14 g and compound Z0.6 g.
Compound X

Compound X: ¹ H-NMR (CDCl ₃ ) δ: 8.52 (1H, d), 8.18 (1H, d), 7.80-7.72 (3H, m), 4.03 (2H, q), 1.43 (3H, t).
Compound Y

Compound Y: ¹ H-NMR (CDCl ₃ ) δ: 8.53 (1H, d), 8.36 (1H, d), 7.94 (1H, dd), 7.89 (1H, d), 7.76 (1H, d), 4.01 ( 2H, q), 1.44 (3H, t).
Compound Z

Compound Z: ¹ H-NMR (CDCl ₃ ) δ: 8.59 (1H, d), 8.54 (1H, d), 8.18 (1H, dd), 7.98 (1H, d), 7.79 (1H, d), 3.98 ( 2H, q), 1.45 (3H, t).
(5)
To a mixture of 200 mg of Compound X and 1 mL of chloroform, 650 mg of 1,2,4-triazole, 0.16 mL of N, N-diisopropylethylamine, and 5.0 mg of N, N-dimethyl-4-aminopyridine were sequentially added. The reaction mixture was stirred at room temperature for 7 hours, water was added to the reaction mixture, and the mixture was extracted with chloroform. The obtained organic layer was dried over anhydrous sodium sulfate and then dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 200 mg of the following present compound 13.

Compound 13 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.29 (1H, s), 8.74 (1H, d), 8.29 (1H, d), 8.21 (2H, t), 7.82 (1H, dd), 7.77 (1H, d), 4.00 (2H, q), 1.45 (3H, t).

(Production Example 14)
A mixture of 260 mg of the present compound 13 and 5 mL of chloroform was cooled to 0 ° C., 140 mg of 75% m-chloroperbenzoic acid was added, and the mixture was stirred at room temperature for 16 hours. This reaction mixture was added to a saturated multilayer aqueous solution and extracted with chloroform. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and dried under reduced pressure. The obtained residue was subjected to silica gel chromatography to obtain 180 mg of the present compound 14 shown below.

Compound 14 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.29 (1H, s), 8.76 (1H, d), 8.39 (1H, s), 8.32 (1H, d), 8.21 (1H, s), 7.98 (1H, d), 7.93 (1H, d), 3.99 (2H, q), 1.46 (3H, t).

(Production Example 15)
Using Compound Z instead of Compound X, the following Compound 15 of the present invention was obtained according to the method described in Production Example 13 (5).

Compound 15 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.28 (1H, s), 8.76 (1H, d), 8.62 (1H, d), 8.34 (1H, d), 8.22 (2H, t), 8.02 (1H, dd), 3.96 (2H, q), 1.47 (3H, t).

(Production Example 16)
In accordance with the method described in Preparation Example 13 (5), using Compound Y instead of Compound X and 3-methyl-1H-1,2,4-triazole instead of 1H-1,2,4-triazole The following present compound 16 was obtained.

Compound 16 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.18 (1H, s), 8.71 (1H, d), 8.38 (1H, s), 8.24 (1H, d), 7.97 (1H, d), 7.93 (1H, d), 3.98 (2H, q), 2.55 (3H, s), 1.45 (3H, t).

(Production Example 17)
In accordance with the method described in Preparation Example 13 (5), using Compound Y instead of Compound X and 3-chloro-1H-1,2,4-triazole instead of 1H-1,2,4-triazole Thus, the following present compound 17 was obtained.

Compound 17 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.20 (1H, s), 8.77 (1H, d), 8.39 (1H, s), 8.25 (1H, d), 7.97 (1H, t), 7.93 (1H, d), 4.00 (2H, q), 1.46 (3H, t).

(Production Example 18)
In accordance with the method described in Preparation Example 13 (5), using Compound Z instead of Compound X, and 3-chloro-1H-1,2,4-triazole instead of 1H-1,2,4-triazole The following present compound 18 was obtained.

Compound 18 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 9.18 (1H, s), 8.77 (1H, d), 8.61 (1H, s), 8.27 (1H, d), 8.22 (1H, d), 8.01 (1H, d), 3.97 (2H, q), 1.47 (3H, t).

(Production Example 19)
In accordance with the method described in Preparation Example 13 (5), using Compound Y instead of Compound X and 3-amino-1H-1,2,4-triazole instead of 1H-1,2,4-triazole The following present compound 19 was obtained.

Compound 19 of the present invention: ¹ H-NMR (CDCl ₃ ) δ: 8.94 (1H, s), 8.65 (1H, d), 8.37 (1H, s), 8.03 (1H, d), 7.95 (1H, d), 7.91 (1H, d), 4.46 (2H, s), 3.95 (2H, q), 1.44 (3H, t).

Next, the formulation example of this invention compound is shown. In addition, a part represents a weight part.

Formulation Example 1
10 parts of any one of the compounds 1 to 19 of the present invention are dissolved in a mixture of 35 parts of xylene and 35 parts of N, N-dimethylformamide, and 14 parts of polyoxyethylene styryl phenyl ether and calcium dodecylbenzenesulfonate are dissolved therein. Add 6 parts and mix to obtain each formulation.

Formulation Example 2
4 parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic silicon hydroxide fine powder and 54 parts of diatomaceous earth are mixed, and 20 parts of any one of the compounds 1 to 19 of the present invention are added and mixed. Get a wettable powder.

Formulation Example 3
1 part of synthetic silicon hydrous fine powder, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are mixed with 2 parts of any one of the compounds 1 to 19 of the present invention. Next, an appropriate amount of water is added to the mixture, and the mixture is further stirred, granulated with a granulator, and dried by ventilation to obtain each granule.

Formulation Example 4
1 part of any one of the compounds 1 to 19 of the present invention is dissolved in an appropriate amount of acetone, and 5 parts of a synthetic silicon hydroxide fine powder, 0.3 part of isopropyl acid phosphate and 93.7 parts of fusami clay are added, The mixture is thoroughly mixed and acetone is removed by evaporation to obtain each powder.

Formulation Example 5
35 parts of a mixture of polyoxyethylene alkyl ether sulfate ammonium salt and white carbon (weight ratio 19), 10 parts of any one of the compounds 1 to 19 of the present invention, and 55 parts of water are mixed and finely divided by a wet pulverization method. Each flowable agent is obtained by grinding.

Formulation Example 6
0.1 part of any one of the compounds 1 to 19 of the present invention is dissolved in a mixture of 5 parts of xylene and 5 parts of trichloroethane, and this is mixed with 89.9 parts of deodorized kerosene to obtain each oil agent.

Formulation Example 7
10 mg of any one of the compounds 1 to 19 of the present invention is dissolved in 0.5 ml of acetone, and this solution is added dropwise to 5 g of animal solid feed powder (solid feed powder CE-2 for breeding breeding, Nippon Claire Co., Ltd.). And mix evenly. Then acetone is evaporated to dryness to obtain each poisonous bait.

Formulation Example 8
0.1 part of any one of the compounds 1 to 19 of the present invention and 49.9 parts of neothiozole (Chuo Kasei Co., Ltd.) are put in an aerosol can, and after mounting an aerosol valve, 25 parts of dimethyl ether and 25 parts of LPG are filled. Shake and attach an actuator to obtain an oil aerosol.

Formulation Example 9
0.6 part of any one of compounds 1 to 19 of the present invention, 0.01 part of BHT (2,6-di-tert-butyl-4-methylphenol), 5 parts of xylene, 3.39 parts of deodorized kerosene and emulsifier {Rheodor MO-60 (manufactured by Kao Corporation)} After mixing 1 part and 50 parts of distilled water into an aerosol container and attaching a valve, 40 parts of propellant (LPG) was added through the valve. Pressure filling to obtain an aqueous aerosol.

Formulation Example 10
0.1 g of any one of the compounds 1 to 19 of the present invention is mixed with 2 ml of propylene glycol, impregnated into a porous ceramic plate of 4.0 × 4.0 cm and thickness of 1.2 cm, and a heating smoke Get.

Formulation Example 11
5 parts of any one of the present compounds 1 to 19 and an ethylene-methyl methacrylate copolymer (ratio of methyl methacrylate in the copolymer: 10% by weight, ACRIFT (registered trademark) WD301, manufactured by Sumitomo Chemical Co., Ltd.) 95 The part is melt-kneaded with a closed pressure kneader (manufactured by Moriyama Seisakusho), and the resulting kneaded product is extruded from an extrusion molding machine through a molding die to obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm.

Formulation Example 12
5 parts of any one of the compounds 1 to 19 of the present invention and 95 parts of a soft vinyl chloride resin are melt-kneaded with a closed pressure kneader (manufactured by Moriyama Seisakusho), and the resulting kneaded product is passed from an extrusion molding machine through a molding die. To obtain a rod-shaped molded body having a length of 15 cm and a diameter of 3 mm.

Formulation Example 13
Any one of the compounds 1 to 19 of the present invention 100 mg, lactose 68.75 mg, corn starch 237.5 mg, microcrystalline cellulose 43.75 mg, polyvinylpyrrolidone 18.75 mg, sodium carboxymethyl starch 28.75 mg, and magnesium stearate Mix 2.5 mg and compress the resulting mixture to an appropriate size to obtain tablets.

Formulation Example 14
Any one of the compounds 1 to 19 of the present invention 25 mg, lactose 60 mg, corn starch 25 mg, carmellose calcium 6 mg, and 5% hydroxypropylmethylcellulose are mixed in an appropriate amount, and the resulting mixture is hard shell gelatin capsule or hydroxypropylmethylcellulose capsule To obtain capsules.

Formulation Example 15
Any one of the compounds 1 to 19 of the present invention 100 mg, fumaric acid 500 mg, sodium chloride 2000 mg, methylparaben 150 mg, propylparaben 50 mg, granule sugar 25000 mg, sorbitol (70% solution) 13000 mg, VeegumK (VanderbiltCo.) 100 mg, flavor 35 mg, And distilled water is added to 500 mg of the colorant so that the final volume becomes 100 ml, and mixed to obtain a suspension for oral administration.

Formulation Example 16
5% by weight of any one of the compounds 1 to 19 of the present invention is dissolved in 5% by weight of polysorbate 85, 3% by weight of benzyl alcohol, and 30% by weight of propylene glycol, and the pH of this solution is 6.0 to 6.5. After adding a phosphate buffer so that it becomes, the remainder is added with water to obtain a solution for oral administration.

Formulation Example 17
5% by weight of aluminum distearate in 57% by weight of fractionated coconut oil and 3% by weight of polysorbate 85 is added and dispersed by heating. This is cooled to room temperature and 25% by weight of saccharin is dispersed in the oily vehicle. To this, 10% by weight of any one of the compounds 1 to 19 of the present invention is allocated to obtain a paste preparation for oral administration.

Formulation Example 18
5% by weight of any one of the compounds 1 to 19 of the present invention is mixed with 95% by weight of limestone powder, and granules for oral administration are obtained using a wet granulation method.

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

Formulation Example 20
10 parts of any one of the compounds 1 to 19 of the present invention are dissolved in 70 parts of diethylene glycol monoethyl ether, and 20 parts of 2-octyldodecanol is mixed with this to obtain a pour-on solution.

Formulation Example 21
To 0.5 parts of any one of the compounds 1 to 19 of the present invention, 60 parts of Nikkor (registered trademark) TEALS-42 (42% aqueous solution of Nikko Chemicals lauryl sulfate triethanolamine) and 20 parts of propylene glycol were added, After sufficiently stirring and mixing until a uniform solution is obtained, 19.5 parts of water is added and further stirring and mixing is performed to obtain a shampoo agent of a uniform solution.

Formulation Example 22
Any one of the compounds 1 to 19 of the present invention 0.15% by weight, animal feed 95% by weight, and 4.85% by weight of a mixture comprising dicalcium phosphate, diatomaceous earth, Aerosil, and carbonate (or chalk) are sufficiently stirred. Mix to obtain animal feed premix.

Formulation Example 23
7.2 g of any one of the compounds 1 to 19 of the present invention and 92.8 g of Fosco (registered trademark) S-55 (manufactured by Maruishi Pharmaceutical Co., Ltd.) are dissolved and mixed at 100 ° C., poured into a suppository, and cooled. Solidify to obtain a suppository.

Moreover, the formulation example of the pest control agent containing this invention compound is shown. In addition, a part represents a weight part.

Formulation Example 1A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the compound 1 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 2A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 2 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 3A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the compound 3 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 4A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 4 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 5A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 5 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 6A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of compound 6 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 7A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 7 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 8A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 8 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 9A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the compound 9 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 10A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 10 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 11A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 11 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 12A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 12 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 13A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 13 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 14A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the compound 14 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 15A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 15 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 16A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 16 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 17A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 17 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 18A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the present compound 18 and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 19A
0.1 part of any one selected from the following compounds A1 to A100, 10 parts of the compound 19 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.

Formulation Example 20A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of Compound 1 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 21A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 2 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 22A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 3 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 23A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 4 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 24A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of Compound 5 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 25A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 6 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 26A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 7 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 27A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of Compound 8 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 28A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 9 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 29A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of compound 10 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 30A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 11 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 31A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 12 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 32A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 13 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 33A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 14 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 34A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 15 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 35A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 16 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 36A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 17 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 37A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 18 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 38A
10 parts of any one selected from the following compounds A1 to A100, 0.1 part of the compound 19 of the present invention and 89.9 parts of dimethyl sulfoxide are mixed to obtain each solution.

Formulation Example 39A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of Compound 1 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 40A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of compound 2 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 41A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of compound 3 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 42A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 4 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 43A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of Compound 5 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 44A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of compound 6 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 45A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 7 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 46A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 8 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 47A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 9 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 48A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 10 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 49A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 11 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 50A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 12 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 51A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of compound 13 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 52A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 14 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 53A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 15 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 54A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 16 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 55A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of compound 17 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 56A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 18 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.
Formulation Example 57A
4 parts of any one selected from the following compounds A1 to A100, 4 parts of the compound 19 of the present invention and 92 parts of dimethyl sulfoxide are mixed to obtain each solution.

Compounds A1 to A100 used in the above formulation examples are the compounds shown below.
Pyrethrin (compound A1); allethrin (compound A2); praretrin (compound A3); imiprothrin (compound A4); resmethrin (compound A5); tetramethrin (compound A6); phenothrin (compound A7); (Compound A9); Metofluthrin (Compound A10); Transfluthrin (Compound A11); Profluthrin (Compound A12); Dimefluthrin (Compound A13); Empentrin (Compound A14); Framethrin (Compound A15); Meperfluthrin (Compound A16); , 3,5,6-tetrafluoro-4- (methoxymethyl) benzyl = 2,2-dimethyl-3- (2-cyano-1-propenyl) -cyclopropanecarboxylate (Compound A17); , 6-Te Rafluoro-4- (methoxymethyl) benzyl = 2,2-dimethyl-3- (3,3,3-trifluoro-1-propenyl) -cyclopropanecarboxylate (compound A18); 2,3,5,6- Tetrafluoro-4-propargylbenzyl = 2,2,3,3-tetramethylcyclopropanecarboxylate (Compound A19); Acrinatrin (Compound A20); Bifenthrin (Compound A21); Cycloprotolin (Compound A22); Cyfluthrin (Compound) Beta-cyfluthrin (compound A24); cyhalothrin (compound A25); lambda cihalothrin (compound A26); gamma cyhalothrin (compound A27); cypermethrin (compound A28); alpha cypermethrin (compound A29); Betacypermethrin (Compound A 0); theta cypermethrin (compound A31); zeta cypermethrin (compound A32); deltamethrin (compound A33); etofenprox (compound A34); fenpropatoline (compound A35); fenvalerate (compound A36); Flucitrinate (compound A38); fulvalinate (compound A39); tau fluvalinate (compound A40); halfenprox (compound A41); permethrin (compound A42); silafluophene (compound A43); (Compound A44); Tralomethrin (Compound A45); Protrifen Bute (Compound A46); Fenitrothion (Compound A47); Dichlorvos (Compound A48); Propoxur (Compound A49); Clothipridine (compound A51); thiamethoxam (compound A52); dinotefuran (compound A53); acetamiprid (compound A54); thiacloprid (compound A55); nitenpyram (compound A56); ethiprole (compound A57); Compound A58); Acetoprole (Compound A59); Vaniliprole (Compound A60); Pyriprole (Compound A61); Pyrafluprolol (Compound A62); Abamectin (Compound A63); Emamectin (Compound A64); ); Milbemectin (Compound A66); Doramectin (Compound A67); Repimectin (Compound A68); Bistrifluron (Compound A69); Diflubenzuron (Compound A70); Hexaflumuron (Compound A72); Hydroprene (Compound A73); Metoprene (Compound A74); Ciromazine (Compound A75); Etoxazole (Compound A76); Nobiflumuron (Compound A77); Amitraz (Compound A78) ); Chlorfenapyr (Compound A79); methoxadiazone (Compound A80); amidoflumet (Compound A81); spirotetramat (Compound A82); sulfoxafurol (Compound A83); pymetrozine (Compound A84); Indoxacarb (Compound A87); Piperonyl butoxide (Compound A88); N- (2-ethylhexyl) -5-norbornene-2,3-dicarboximide (Compound A89) ;

Chlorantraniliprole (Compound A94); Cyantraniliprole (Compound A95); Flubendiamide (Compound A96); Triflumezopyrine (Compound A97);

Next, the pest control effect of the compound of the present invention is shown by test examples.

Test example 1
Each formulation of the present compound 2,3,4,5,11,12,13,14,15 and 16 obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 200 ppm, A test chemical solution was prepared.
Meanwhile, about 30 Aphis gossypi (all stages) were inoculated into cucumber seedlings (first true leaf development stage) planted in plastic cups and left for 1 day. The seedlings were sprayed with 20 ml of the test chemical solution.
Six days after spraying, the number of live cotton aphids that parasitized on the leaves of the cucumber was examined, and the control value was determined by the following formula.
Control value (%) = {1− (Cb × Tai) / (Cai × Tb)} × 100
In addition, the character in a formula represents the following meaning.
Cb: number of insects before treatment in the untreated group Cai: number of live parasites when observed in the untreated group Tb: number of insects before treatment in the treated group Tai: number of live parasitic insects during observation of the treated group The group means a group in which a preparation containing no compound of the present invention in Preparation Example 5 was sprayed with a test chemical solution diluted with the same amount of water as the treatment group.
As a result, all of the treatment sections using the test chemical solutions of the compounds 2, 3, 4, 5, 11, 12, 13, 14, 15 and 16 of the present invention showed a control value of 90% or more.

Test example 2
Each formulation of the present compounds 11, 13, 14 and 16 obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 200 ppm, and a test drug solution was prepared.
On the other hand, cucumber seedlings planted in plastic cups (second true leaf development stage) were irrigated with 5 ml of the test chemical solution and kept in a greenhouse at 25 ° C. for 7 days. After inoculating about 30 Aphis gossypi (all stages) on the cucumber leaf surface and keeping it in the greenhouse for another 6 days, the number of live aphids on the cucumber leaf was investigated. The control value was calculated by the following formula.
Control value (%) = {1− (Cb × Tai) / (Cai × Tb)} × 100
In addition, the character in a formula represents the following meaning.
Cb: number of insects before treatment in the untreated group Cai: number of live parasites when observed in the untreated group Tb: number of insects before treatment in the treated group Tai: number of live parasitic insects during observation of the treated group The group means a group in which a preparation containing no compound of the present invention in Preparation Example 5 was sprayed with a test chemical solution diluted with the same amount of water as the treatment group.
As a result, all of the treatment sections using the test chemical solutions of the compounds 11, 13, 14 and 16 of the present invention exhibited a control value of 90% or more.

Test example 3
Each formulation of the present compounds 3, 14 and 15 obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 200 ppm, respectively, to prepare a test drug solution.
10 ml of the test chemical solution is sprayed on rice seedlings in the second leaf development stage planted in a polyethylene cup. After air-drying, 20 3-4 instar larvae of Nilaparvata lugens are released and stored in a greenhouse at 25 ° C. Six days later, the number of surviving insects that were infested with rice was examined, and the control value was determined by the following formula.
Control value (%) = {1− (Cb × Tai) / (Cai × Tb)} × 100
In addition, the character in a formula represents the following meaning.
Cb: number of insects before treatment in the untreated group Cai: number of live parasites when observed in the untreated group Tb: number of insects before treatment in the treated group Tai: number of live parasitic insects during observation of the treated group The group means a group in which a preparation containing no compound of the present invention in Preparation Example 5 was sprayed with a test chemical solution diluted with the same amount of water as the treatment group.
As a result, all of the treatment groups using the test chemical solutions of the compounds 3, 14 and 15 of the present invention showed a control value of 90% or more.

Test example 4
Each preparation of the compounds 2, 3, 11 and 14 of the present invention obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 200 ppm, and a test drug solution was prepared.
On the other hand, 5 ml of the test drug solution was irrigated to rice seedlings planted in plastic cups (2 weeks after sowing, in the second leaf development stage) and kept in a 25 ° C. greenhouse for 7 days. After releasing 20 3-4 instar larvae of the green planthopper (Nilaparvata lugens) and keeping it in the greenhouse for another 6 days, the number of surviving insects parasitic on the rice leaves was investigated, and the control value was calculated by the following formula: Asked.
Control value (%) = {1− (Cb × Tai) / (Cai × Tb)} × 100
In addition, the character in a formula represents the following meaning.
Cb: number of insects before treatment in the untreated group Cai: number of live parasites when observed in the untreated group Tb: number of insects before treatment in the treated group Tai: number of live parasitic insects during observation of the treated group The group means a group in which a preparation containing no compound of the present invention in Preparation Example 5 was sprayed with a test chemical solution diluted with the same amount of water as the treatment group.
As a result, all of the treatment groups using the test chemical solutions of the compounds 2, 3, 11 and 14 of the present invention showed a control value of 90% or more.

Test Example 5
Each preparation of the compound of the present invention obtained in Formulation Example 5 is diluted with water so that the active ingredient concentration is 200 ppm to prepare a test drug solution.
On the other hand, adult tobacco whitefly (Bemisia tabaci) is released on tomato seedlings (third true leaf development stage) planted in a polyethylene cup and allowed to lay eggs for about 72 hours. The tomato seedlings are kept in a greenhouse for 8 days, and the test chemical is sprayed at a rate of 20 ml / cup to the place where the larva has hatched from the delivered eggs, and kept in the greenhouse at 25 ° C. Seven days later, the number of surviving larvae on the tomato leaves is examined to calculate the mortality rate.

Test Example 6
Each formulation of the compound of the present invention 2,3,4,5,11,12,13,14,15,16,17 and 18 obtained in Formulation Example 5 is mixed with water so that the active ingredient concentration is 200 ppm. The test drug solution was prepared.
On the other hand, the test chemical solution was sprayed at a rate of 20 mL / cup on a three-leaf cabbage planted in a polyethylene cup. After the drug solution was dried, the foliage was cut out and accommodated in a 50 mL cup, and 5 second-instar larvae (Plutella xylostella) were released and capped. After storing at 25 ° C., the number of dead insects was counted after 5 days, and the death rate was calculated from the following formula.
Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, all of the treatment groups using the test chemical solutions of the compounds 2, 3, 4, 5, 11, 12, 13, 14, 15, 16, 17 and 18 of the present invention showed a death rate of 80% or more. It was.

Test Example 7
Each formulation of the compound of the present invention obtained in Formulation Example 5 is diluted with water so that the active ingredient concentration becomes 200 ppm, respectively, and a test spray solution is prepared.
On the other hand, an apple is planted in a plastic cup and grown until the seventh or eighth true leaf develops. The apple is sprayed with the test chemical at a rate of 20 mL / cup. After the chemical solution is dried, 60 first-instar larvae of Adoxophys orana fascita are released, and the bottom is covered with a plastic cup with a cut-out filter paper. After 7 days, the number of dead insects is examined and the death rate is calculated.

Test Example 8
Each preparation of the compounds 4, 5, 14, 15, 17 and 19 of the present invention obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 500 ppm, and a test drug solution was prepared.
A filter paper of the same size was laid on the bottom of a polyethylene cup having a diameter of 5.5 cm, 0.7 ml of the test chemical solution was dropped onto the filter paper, and 30 mg of sucrose was uniformly added as a bait. Ten female fly (Musca domestica) females were released into the polyethylene cup and capped. After 24 hours, the life and death of the house fly was investigated, the number of dead insects was counted, and the death rate was calculated by the following formula.
Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, all of the treatment groups using the test chemical solutions of the compounds 4, 5, 14, 15, 17 and 19 of the present invention showed a death rate of 100%.

Test Example 9
Each formulation of the present compounds 4, 5 and 14 obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 500 ppm, respectively, to prepare a test drug solution.
A filter paper of the same size is placed on the bottom of a polyethylene cup having a diameter of 5.5 cm, 0.7 ml of the test chemical solution is dropped on the filter paper, and 30 mg of sucrose is uniformly added as food. Two adult male cockroaches (Blatella germanica) were released into the polyethylene cup and capped. Six days later, the death and death of German cockroaches were investigated, the number of dead insects was counted, and the death rate was calculated by the following formula.
Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, all of the treatment groups using the test chemical solutions 4, 5 and 14 of the compound of the present invention showed a death rate of 100%.

Test Example 10
Each formulation of the present compound 4, 5, 14, 15, 16, 17, 18 and 19 obtained in Formulation Example 5 was diluted with water so that the active ingredient concentration was 500 ppm, respectively, and a test drug solution was prepared. Prepared.
0.7 ml of the test chemical solution was added to 100 ml of ion-exchanged water (active ingredient concentration: 3.5 ppm). Twenty dead larvae of Culex pipiens pallens were released into the solution, and after 1 day, the viability was investigated, the number of dead worms was counted, and the mortality rate was determined.
Death rate (%) = (Number of dead insects / number of test insects) × 100
As a result, all of the treatment groups using the test chemical solutions of the compounds 4, 5, 14, 15, 16, 17, 18 and 19 of the present invention showed a death rate of 95% or more.

Test Example 11
A 2 mg sample of the compound 14 of the present invention was weighed into a screw tube (Marume No. 5; 27 × 55 mm), 0.2 mL of acetone was added, and the solution was covered and dissolved. The screw tube was rotated and inverted to coat the chemical solution so that the entire inner wall was uniform, and the lid was removed and air-dried for about 2 hours. Then, 5 groups of unsucked ticks of Haemaphysalis longicornis were released and capped. Two days later, the number of dead insects was counted, and the death rate was calculated by the following formula.
Death rate (%) = 100 x (number of dead insects / number of test insects)
As a result, the treatment group using the test chemical solution of the compound 14 of the present invention showed a death rate of 60% or more.

Test Example 12
5 mg of the compound of the present invention is dissolved in 5 mL of propylene carbonate so as to be 0.1% w / v to prepare a test drug solution.
On the day before the administration of the test drug solution, mice were inoculated with 30 test mites (Mite mite, young mite). Remove non-parasitic ticks before dripping.
200 μL of the test drug solution is administered dropwise to the entire body surface of the mouse using a pipette. In addition, 200 μL of propylene carbonate alone is administered to the control group. Repeat 3 times per group. Two days after the instillation, the lethality of the test mite is investigated, and the mortality is calculated.

The control agent of the present invention has a control effect on pests and is useful as an active ingredient of pests.

Claims

Formula (1)

[Where:
A represents NCH 3 or an oxygen atom,
R 1 is a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C3 alkoxy group, a C2-C4 alkoxycarbonyl group, S (O) m R 2 , NR 3 R 4 represents a nitro group or a cyano group,
R 2 represents a C1-C3 alkyl group,
R 3 and R 4 each independently represents a hydrogen atom or a C1-C3 alkyl group,
R 5 represents a C1-C3 perfluoroalkyl group or S (O) p —R 6 ,
R 6 represents a C1-C3 perfluoroalkyl group,
n represents 0, 1 or 2,
m represents 0, 1 or 2;
p represents 0, 1 or 2. ]
A condensed heterocyclic compound represented by
The compound of claim 1, wherein A is NCH 3 .
The compound according to claim 1, wherein A is an oxygen atom.
R 1 is a hydrogen atom, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C3 alkoxy group, or S (O) m R 2. Item 4. The compound according to any one of Items 3.
Wherein R 1 is a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, a trifluoromethyl group, a methoxy group, methylsulfanyl group, according to claims 1 to 3 any one is methylsulfinyl group, or methylsulfonyl group Compound.
The compound according to any one of claims 1 to 5 , wherein R 5 is a trifluoromethyl group or an S (O) p -CF 3 group.
A pest control composition comprising the compound according to any one of claims 1 to 6 and an inert carrier.
A method for controlling pests, wherein an effective amount of the compound according to any one of claims 1 to 6 is applied to pests or habitats of pests.