WO2020075704A1

WO2020075704A1 - Pyridone compound, and agricultural and horticultural fungicide containing same as active ingredient

Info

Publication number: WO2020075704A1
Application number: PCT/JP2019/039619
Authority: WO
Inventors: 英明生島; 豪毅梅谷
Original assignee: 三井化学アグロ株式会社
Priority date: 2018-10-09
Filing date: 2019-10-08
Publication date: 2020-04-16
Also published as: JP7291151B2; JPWO2020075704A1

Abstract

Provided is a novel compound that controls plant diseases. A pyridone compound according to the present invention is a novel compound and can control plant diseases.

Description

Pyridone compounds and agricultural and horticultural fungicides containing them as active ingredients

The present invention relates to a pyridone compound and an agrochemical containing the compound as an active ingredient.

Controlling diseases of agricultural and horticultural crops plays an important role in ensuring stable agricultural production. For this reason, various fungicides are used, but the use of fungicides over the years has led to the emergence of drug-resistant bacteria. Have been.

By the way, regarding 1,3,5,6-substituted-2-pyridone compounds, for example, 1,3,5,6-substituted-2 having an aryl group or a heteroaryl group at the 3-position as a GABA alpha-2 / 3 ligand -Pyridone compounds have been disclosed (see, for example, WO 98/55480). In addition, 1,3,5,6-substituted-2-pyridone compounds having a carboxyl group at the 3-position have been disclosed as therapeutic agents for bacterial infections (for example, see European Patent No. 0308020).

International Publication No. 98/55480 European Patent No. 0308020

However, the uses of the compounds described in WO 98/55480 and EP 0308020 are all related to pharmaceuticals, which is different from the technical field to which the agricultural and horticultural fungicide according to the present invention belongs. To do.

An object of the present invention is to provide a novel compound which is effective as a fungicide for agricultural and horticultural use.

In order to solve the above-mentioned problems, the inventors of the present invention have conducted diligent studies on a group of 1,3,5,6-substituted-2-pyridone compounds, and as a result, have found that thiazole and thiadiazole are associated with the 5-position in the 2-pyridone skeleton. A novel compound group having a 5-membered heterocyclic group having a sulfur atom and a nitrogen atom, and introducing an aryl group having a substituent at the ortho position with respect to the 6-position in the 2-pyridone skeleton, They have found that they exert an excellent controlling activity against plant diseases and have completed the present invention.

That is, the present invention is as follows.

[1] Formula (1)

[In the formula, R1 is
Hydroxyl group,
Cyano group,
A C1 to C6 alkyl group optionally substituted with a substituent A,
A C1 to C6 haloalkyl group,
A C3 to C8 cycloalkyl group which may be optionally substituted with a substituent A,
A C2-C6 alkenyl group optionally substituted with a substituent A,
A C2-C6 haloalkenyl group,
A C2-C6 alkynyl group optionally substituted with a substituent A,
A C2-C6 haloalkynyl group,
A C1 to C6 alkoxy group optionally substituted with a substituent A,
A C1 to C6 haloalkoxy group,
A C3 to C8 cycloalkoxy group optionally substituted with a substituent A,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent A,
A C2-C6 haloalkenyloxy group,
A C3-C6 alkynyloxy group which may be optionally substituted with a substituent A,
A C3 to C6 haloalkynyloxy group,
Or RaRbN— (wherein Ra and Rb are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 Or a Ra and Rb together with the nitrogen atom to which they are attached form an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidinyl group, a homopiperidinyl group, or an azocanyl group. Representation; R2 is
Hydrogen atom,
Nitro group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent A,
A C1 to C6 haloalkyl group,
A C3 to C8 cycloalkyl group which may be optionally substituted with a substituent A,
A C2-C6 alkenyl group optionally substituted with a substituent A,
A C2-C6 haloalkenyl group,
A C2-C6 alkynyl group optionally substituted with a substituent A,
A C2-C6 haloalkynyl group,
A C1 to C6 alkoxy group optionally substituted with a substituent A,
A C1 to C6 haloalkoxy group,
A C3 to C8 cycloalkoxy group optionally substituted with a substituent A,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent A,
A C2-C6 haloalkenyloxy group,
A C3-C6 alkynyloxy group which may be optionally substituted with a substituent A,
A C3 to C6 haloalkynyloxy group,
Rc-L- (wherein Rc represents a C1-C6 alkyl group or a C1-C6 haloalkyl group, and L represents S, SO, or SO ₂ ),
Or Rx1C (═O) — (wherein Rx1 is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, C1 To C6 alkoxy group, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group, or RaRbN— (wherein Ra and Rb have the same meanings as described above);
Het,
Represents a 5-membered heterocyclic group containing a sulfur atom and a nitrogen atom,
In the 5-membered heterocyclic group containing a sulfur atom and a nitrogen atom, R3 is appropriately substituted with 0 to 2 (provided that when there is disubstituted R3, R3 represents an independent substituent).
R3 is
Hydroxyl group,
Cyano group,
Nitro group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
A C3 to C8 cycloalkyl group optionally substituted with a substituent C,
A C2-C6 alkenyl group optionally substituted with a substituent C,
C2-C6 haloalkenyl group,
A C2 to C6 alkynyl group optionally substituted with a substituent C,
A C2-C6 haloalkynyl group,
A C1 to C6 alkoxy group optionally substituted with a substituent C,
A C1 to C6 haloalkoxy group,
A C3 to C8 cycloalkoxy group optionally substituted with a substituent C,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent C,
A C2-C6 haloalkenyloxy group,
A C3-C6 alkynyloxy group optionally substituted with a substituent C,
A C3 to C6 haloalkynyloxy group,
RaRbN- (wherein Ra and Rb are as defined above),
Rc-L- (wherein Rc and L are as defined above),
Rx1C (= O)-(where Rx1 is as defined above),
Rx1C (= O) O- (where Rx1 is as defined above),
Or Rx2C (═O) N (Rx3)-(wherein Rx2 is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group). An alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, or RaRbN- (wherein Ra and Rb have the same meanings as described above), and Rx3 is , A hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group).
R4 is
Hydroxyl group,
Cyano group,
Nitro group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
A C3 to C8 cycloalkyl group optionally substituted with a substituent C,
A C2-C6 alkenyl group optionally substituted with a substituent C,
C2-C6 haloalkenyl group,
A C2 to C6 alkynyl group optionally substituted with a substituent C,
A C2-C6 haloalkynyl group,
A C1 to C6 alkoxy group optionally substituted with a substituent C,
A C1 to C6 haloalkoxy group,
A C3 to C8 cycloalkoxy group optionally substituted with a substituent C,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent C,
A C2-C6 haloalkenyloxy group,
A C3-C6 alkynyloxy group optionally substituted with a substituent C,
A C3 to C6 haloalkynyloxy group,
RaRbN- (wherein Ra and Rb are as defined above),
Rc-L- (wherein Rc and L are as defined above),
Rx1C (= O)-(where Rx1 is as defined above),
Rx1C (= O) O- (where Rx1 is as defined above),
Or Rx2C (= O) N (Rx3)-(wherein Rx2 and Rx3 have the same meanings as defined above);
R5 has the same meaning as R4 described above;
n represents an integer of 0 to 4;
X represents an oxygen atom or a sulfur atom;
A bond containing a broken line represents a double bond or a single bond;
The substituent A is a hydroxyl group, a cyano group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, a C3 to C8 cycloalkoxy group, or a RaRbN- (here, Ra And Rb are as defined above.), And Rc-L- (wherein Rc and L are as defined above), and at least one selected from the group consisting of:
Substituent B is at least one selected from the group consisting of a cyano group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, and a C3-C8 cycloalkoxy group;
Substituent C is a hydroxyl group, a cyano group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, a C2-C6 alkoxyalkoxy group, RaRbN -(Wherein Ra and Rb are as defined above), Rc-L- (wherein Rc and L are as defined above), Rx1C (= O)-(wherein Rx1) Is the same as defined above.) And 3 to 6 membered ring group containing 1 to 2 oxygen atoms. Or a salt thereof.
[2]
Het,
Represents a thiazolyl group, an isothiazolyl group, a thiadiazolyl group, or a thiatriazolyl group,
In the thiazolyl group, the isothiazolyl group, the thiadiazolyl group, or the thiatriazolyl group, R3 is appropriately substituted by 0 to 2 (provided that when there is disubstituted R3, R3 represents each independent substituent).
The compound according to [1] or a salt thereof.
[3]
R1 is
A C1 to C6 alkyl group optionally substituted with a substituent A,
Or represents a C1-C6 haloalkyl group;
R2 is
Hydrogen atom,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent A,
A C1 to C6 haloalkyl group,
A C2-C6 alkynyl group optionally substituted with a substituent A,
Or represents a C1-C6 alkoxy group which may be optionally substituted with a substituent A;
Het,
Represents a thiazolyl group or a thiadiazolyl group,
In the thiazolyl group or the thiadiazolyl group, R3 is appropriately substituted by 0 to 2 (provided that when there is disubstituted R3, R3 represents each independent substituent).
R3 is
Cyano group,
Nitro group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
A C3 to C8 cycloalkyl group optionally substituted with a substituent C,
A C2-C6 alkenyl group optionally substituted with a substituent C,
A C2 to C6 alkynyl group optionally substituted with a substituent C,
A C1 to C6 alkoxy group optionally substituted with a substituent C,
RaRbN- (wherein Ra and Rb are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group). Or an alkyl group, or Ra and Rb represent an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidinyl group, a homopiperidinyl group, or an azocanyl group together with the nitrogen atom to which they are attached.
Or Rx2C (═O) N (Rx3)-(wherein Rx2 is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group). An alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, or RaRbN- (wherein Ra and Rb have the same meanings as described above), and Rx3 is , A hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group).
R4 is
Cyano group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
A C1 to C6 alkoxy group optionally substituted with a substituent C,
Or represents a C1-C6 haloalkoxy group;
R5 is
Hydroxyl group,
Cyano group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
A C2-C6 alkenyl group optionally substituted with a substituent C,
A C2 to C6 alkynyl group optionally substituted with a substituent C,
A C1 to C6 alkoxy group optionally substituted with a substituent C,
A C1 to C6 haloalkoxy group,
Or Rc-L- (wherein Rc represents a C1-C6 alkyl group or a C1-C6 haloalkyl group, and L represents S, SO, or SO ₂ ).
The compound or salt thereof according to [2].
[4]
R1 is
Represents a C1-C6 alkyl group which may be optionally substituted with a substituent A;
R2 is
Hydrogen atom,
Halogen atom,
Or represents a C1 to C6 alkyl group which may be optionally substituted with a substituent A;
R3 is
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
Or RaRbN— (wherein Ra and Rb are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 Or a Ra and Rb together with the nitrogen atom to which they are attached form an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidinyl group, a homopiperidinyl group, or an azocanyl group. Representation;
R4 is
Halogen atom,
Or represents a C1 to C6 alkyl group which may be optionally substituted with a substituent C;
R5 is
Cyano group,
Halogen atom,
Or represents a C1 to C6 alkoxy group which may be optionally substituted with a substituent C,
The compound or salt thereof according to [3].
[5]
R1 is
Represents a C1 to C6 alkyl group;
R2 is
Represents a halogen atom;
Het,
Represents a thiazolyl group or a thiadiazolyl group,
R3 of the thiazolyl group or the thiadiazolyl group is appropriately substituted,
R3 is
Halogen atom,
C1 to C6 alkyl group,
A C1 to C6 haloalkyl group,
Or RaRbN— (wherein Ra and Rb are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 Or a Ra and Rb together with the nitrogen atom to which they are attached form an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidinyl group, a homopiperidinyl group, or an azocanyl group. Representation;
R4 is
Represents a halogen atom;
R5 is
Represents a halogen atom;
n represents an integer of 0 to 2;
X represents an oxygen atom;
A bond including a broken line portion represents a double bond,
The compound or salt thereof according to [4].
[6] An agricultural and horticultural pest control agent containing the compound or salt thereof according to [1] as an active ingredient.
[7] An agricultural and horticultural fungicide containing the compound according to [1] or a salt thereof as an active ingredient.
[8] A method for controlling plant diseases, which comprises applying the agricultural and horticultural pest control agent according to [6] to plants, plant seeds, or soil for cultivating plants.
[9] A method for controlling plant diseases, which comprises applying the agricultural / horticultural fungicide according to [7] to plants, plant seeds, or soil in which plants are cultivated.

According to the present invention, it is possible to provide a novel compound which is effective as an agricultural / horticultural germicide.

Hereinafter, embodiments for carrying out the present invention will be described in detail.

Unless otherwise specified, each term used in the claims and the specification is based on the definition generally used in the technical field.

The abbreviations used in this specification are explained below.

DMF: N, N-dimethylformamide, THF: tetrahydrofuran, Me: methyl group, Et: ethyl group, Pr: propyl group, Bu: butyl group, Ac: acetyl group, Ph: phenyl group, i: iso, sec: secondary. , T: tertiary, =: double bond, ≡: triple bond. Regarding Pr and Bu in the columns of the table, when there is no prefix, it means normal.

The definitions of terms used in this specification are explained below.

The description of Cx to Cy means that it has x to y carbon atoms. Here, x and y represent integers, and it is understood that all integers present between x and y are also individually disclosed. For example, C1-C6 is 1, 2, 3, 4, 5, or 6 carbon atoms, C2-C6 is 2, 3, 4, 5, or 6 carbon atoms, and C3-C8 is 3, 4, 5, 6, 7, or 8 carbon atoms, C3-C6 is 3, 4, 5, or 6 carbon atoms, C1-C3 is 1, 2, or 3 It means having each carbon atom of.

The term “may be appropriately substituted” means substituted or unsubstituted. In using this term, when the number of substituents is not specified, it indicates that the number of substituents is 1. On the other hand, for example, when the number of substituents is designated as “optionally substituted by 0 to 3”, it is understood that all integers existing between 0 and 3 are also individually disclosed. To be done. That is, it means that the number of substituents is none, 1, 2, or 3 substituents. Similarly, “optionally substituted by 0 to 2” means having none, one, or two substituents, respectively.

The C1-C6 alkyl group may be linear or branched, and is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl. Group, 2-methylbutyl group, neopentyl group, 1-ethylpropyl group, hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group , 2,2-dimethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 1-isopropylpropyl group Group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group and the like.

The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

The term “C1 to C6 haloalkyl group” refers to the above C1 to C6 alkyl group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent. Specific examples of the C1 to C6 haloalkyl group include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monochloromethyl group, a monobromomethyl group, a monoiodomethyl group, a chlorodifluoromethyl group, a bromodifluoromethyl group, 1 -Fluoroethyl group, 2-fluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group , Pentafluoroethyl group, 2,2,2-trichloroethyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, heptafluoropropyl group, heptafluoroisopropyl group, 2,2,2 -Trifluoro-1- (trifluoromethyl) ethyl group, nonafluorobutyl group, nonafluoro sec- butyl group, 3,3,4,4,5,5,5-heptafluoro-pentyl group, undecyl decafluoropentyl, tridecafluorohexyl group, and the like.

Examples of the C3-C8 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like.

The C2-C6 alkenyl group represents a linear or branched unsaturated hydrocarbon group having one or more double bonds. In addition, when there is a geometric isomer, only one of the E-form or the Z-form, or a mixture of the E-form and the Z-form at an arbitrary ratio is used. Never. Specific examples of the C2 to C6 alkenyl group include vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group. Group, 4-pentenyl group, 3-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 4-methyl-3-pentenyl group, Examples thereof include 3-methyl-2-pentenyl group.

The term “C2-C6 haloalkenyl group” refers to the above-mentioned C2-C6 alkenyl group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent. Specific examples of the C2-C6 haloalkenyl group include 2-fluorovinyl group, 2,2-difluorovinyl group, 2,2-dichlorovinyl group, 3-fluoroallyl group, 3,3-difluoroallyl group, 3, Examples thereof include a 3-dichloroallyl group, a 4,4-difluoro-3-butenyl group, a 5,5-difluoro-4-pentenyl group, and a 6,6-difluoro-5-hexenyl group.

The C2-C6 alkynyl group represents a linear or branched unsaturated hydrocarbon group having one or two or more triple bonds. Specific examples of the C2-C6 alkynyl group include ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group. Group, 4-pentynyl group, 1,1-dimethyl-2-propynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group and the like.

The term “C2-C6 haloalkynyl group” refers to the above-mentioned C2-C6 alkynyl group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent. Specific examples of the C2-C6 haloalkynyl group include 2-fluoroethynyl group, 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3,3-difluoro-1-propynyl group, 3-chloro. -3,3-difluoro-1-propynyl group, 3-bromo-3,3-difluoro-1-propynyl group, 3,3,3-trifluoro-1-propynyl group, 4,4-difluoro-1-butynyl Group, 4,4-difluoro-2-butynyl group, 4-chloro-4,4-difluoro-1-butynyl group, 4-chloro-4,4-difluoro-2-butynyl group, 4-bromo-4,4 -Difluoro-1-butynyl group, 4-bromo-4,4-difluoro-2-butynyl group, 4,4,4-trifluoro-1-butynyl group, 4,4,4-trifluoro-2-butynyl group 5, 5-difluoro-3-pentynyl group, 5-chloro-5,5-difluoro-3-pentynyl group, 5-bromo-5,5-difluoro-3-pentynyl group, 5,5,5-trifluoro-3- Pentynyl group, 6,6-difluoro-4-hexynyl group, 6-chloro-6,6-difluoro-4-hexynyl group, 6-bromo-6,6-difluoro-4-hexynyl group, 6,6,6- Examples thereof include a trifluoro-4-hexynyl group.

The term “C1 to C6 alkoxy group” refers to the above C1 to C6 alkyl group bonded via an oxygen atom. Specific examples of the C1 to C6 alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentyloxy group, isopentyloxy group. Group, 1-methylbutoxy group, 2-methylbutoxy group, neopentyloxy group, 1-ethylpropyloxy group, 1,2-dimethylpropyloxy group, hexyloxy group, 1-methylpentyloxy group, 2-methylpentyl group Oxy group, 3-methylpentyloxy group, 4-methylpentyloxy group, 1,1-dimethylbutoxy group, 2,2-dimethylbutoxy group, 3,3-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1 , 3-dimethylbutoxy group, 2,3-dimethylbutoxy group, 2-ethylbutoxy group, 1-a Propyl propyl group, 1,1,2-trimethyl propyl group, 1,2,2-trimethyl propyl group, and the like.

The term “C1 to C6 haloalkoxy group” refers to the above C1 to C6 alkoxy group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent. Specific examples of the C1 to C6 haloalkoxy group include difluoromethoxy group, trifluoromethoxy group, chlorodifluoromethoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2,2-difluoroethoxy group, 2,2,2. -Trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, pentafluoroethoxy group, 2,2,2-trichloroethoxy group, 3,3-difluoropropyloxy group, 3,3,3-tri Fluoropropyloxy group, heptafluoropropyloxy group, heptafluoroisopropyloxy group, 2,2,2-trifluoro-1- (trifluoromethyl) -ethoxy group, nonafluorobutoxy group, nonafluoro-sec-butoxy group, 3 , 3,4,4,5,5,5-heptafluoropentyloxy group Undecafluoro pentyloxy group, tridecafluorohexyl group, and the like.

The C3 to C8 cycloalkoxy group represents a group in which the C3 to C8 cycloalkyl group is bonded via an oxygen atom. Specific examples of the C3 to C8 cycloalkoxy group include a cyclopropyloxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group and a cyclooctyloxy group.

The term "C2-C6 alkenyloxy group" refers to the C2-C6 alkenyl group bonded through an oxygen atom. When there is a geometric isomer, only one of the E-form and the Z-form, or a mixture of the E-form and the Z-form at an arbitrary ratio, is not particularly limited as long as the number of carbon atoms is within a specified range. Never. Specific examples of the C2-C6 alkenyloxy group include vinyloxy group, 1-propenyloxy group, allyloxy group, 1-butenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 1-pentenyloxy group, 2-pentenyloxy group. , 3-pentenyloxy group, 4-pentenyloxy group, 3-methyl-2-butenyloxy group, 1-hexenyloxy group, 2-hexenyloxy group, 3-hexenyloxy group, 4-hexenyloxy group, 5-hexenyloxy group Group, 4-methyl-3-pentenyloxy group, 3-methyl-2-pentenyloxy group and the like.

The term “C2-C6 haloalkenyloxy group” refers to the above-mentioned C2-C6 alkenyloxy group in which a hydrogen atom is optionally substituted with one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent. Specific examples of the C2-C6 haloalkenyloxy group include a 2-fluorovinyloxy group, a 2,2-difluorovinyloxy group, a 2,2-dichlorovinyloxy group, a 3-fluoroallyloxy group, and a 3,3-difluoro group. Examples include allyloxy group, 3,3-dichloroallyloxy group, 4,4-difluoro-3-butenyloxy group, 5,5-difluoro-4-pentenyloxy group, and 6,6-difluoro-5-hexenyloxy group. To be

The C3-C6 alkynyloxy group refers to the C2-C6 alkynyl group in which the C3-C6 alkynyl group is bonded via an oxygen atom. Specific examples of the C3-C6 alkynyloxy group include propargyloxy group, 2-butynyloxy group, 3-butynyloxy group, 2-pentynyloxy group, 3-pentynyloxy group, 4-pentynyloxy group, 1,1. Examples thereof include a dimethyl-2-propynyloxy group, a 2-hexynyloxy group, a 3-hexynyloxy group, a 4-hexynyloxy group and a 5-hexynyloxy group.

The C3 to C6 haloalkynyloxy group refers to the above C3 to C6 alkynyloxy group in which a hydrogen atom is optionally substituted by one or two or more halogen atoms. When substituted with two or more halogen atoms, those halogen atoms may be the same or different, and the number of substitution is not particularly limited as long as it can be present as a substituent. Specific examples of the C3-C6 haloalkynyloxy group include 1,1-difluoro-2-propynyloxy group, 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro-2-butynyloxy group. , 4-bromo-4,4-difluoro-2-butynyloxy group, 4,4,4-trifluoro-2-butynyloxy group, 5,5-difluoro-3-pentynyloxy group, 5-chloro-5,5 -Difluoro-3-pentynyloxy group, 5-bromo-5,5-difluoro-3-pentynyloxy group, 5,5,5-trifluoro-3-pentynyloxy group, 6,6-difluoro-4 -Hexynyloxy group, 6-chloro-6,6-difluoro-4-hexynyloxy group, 6-bromo-6,6-difluoro-4-hexynyloxy group, 6,6,6- Trifluoroacetic 4- hexynyloxy group.

The C2 to C6 alkoxyalkoxy group is one in which the hydrogen atom in the C1 to C5 alkoxy group among the above C1 to C6 alkoxy groups is optionally substituted with one or two or more C1 to C5 alkoxy groups. Represents There is no particular limitation as long as the sum of the carbon numbers is within the specified carbon number range. Specific examples of the C2 to C6 alkoxyalkoxy group include methoxymethoxy group, ethoxymethoxy group, propyloxymethoxy group, isopropyloxymethoxy group, methoxyethoxy group, ethoxyethoxy group, propyloxyethoxy group, isopropyloxyethoxy group, methoxypropyl. Examples thereof include an oxy group, an ethoxypropyloxy group, a propyloxypropyloxy group and an isopropyloxypropyloxy group.

Specific examples of the 3- to 6-membered ring group containing 1 to 2 oxygen atoms include 1,2-epoxyetanyl group, oxetanyl group, oxolanyl group, oxanyl group, 1,3-dioxolanyl group, 1,3- Examples thereof include dioxanyl group and 1,4-dioxanyl group.

The pyridone compound of the present invention includes a compound represented by the following formula (1) and a salt thereof.

The formula (1) will be described below.

R1 in the formula (1) is a hydroxyl group, a cyano group, a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, or a C3 to C8 optionally substituted with a substituent A. Cycloalkyl group, C2-C6 alkenyl group optionally substituted with substituent A, C2-C6 haloalkenyl group, C2-C6 alkynyl group optionally substituted with substituent A, C2-C6 Haloalkynyl group, C1 to C6 alkoxy group optionally substituted with substituent A, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group optionally substituted with substituent A, substituent A C2-C6 alkenyloxy group optionally substituted with A, a C2-C6 haloalkenyloxy group, a C3-C6 alkynyloxy group optionally substituted with a substituent A, A 3-C6 haloalkynyloxy group, or RaRbN- (wherein Ra and Rb are each independently a hydrogen atom, a C1-C6 alkyl group optionally substituted with a substituent B, a C1-C6 Represents a haloalkyl group or a C3 to C8 cycloalkyl group, or Ra and Rb together with the nitrogen atom to which they are attached are an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidinyl group, a homopiperidinyl group, or an azocanyl group. Represents that which forms).

Among them, R1 is preferably a C1 to C6 alkyl group which may be appropriately substituted with a substituent A, or a C1 to C6 haloalkyl group,

Particularly, a C1-C6 alkyl group which may be appropriately substituted with the substituent A is preferable.

R1 in the formula (1) includes a hydroxyl group and a cyano group.

The C1 to C6 alkyl group of the “C1 to C6 alkyl group optionally substituted with the substituent A” in R1 of the formula (1) has the same meaning as defined above, and is preferably a methyl group or an ethyl group. , A propyl group, an isopropyl group, a butyl group, or an isobutyl group, more preferably a methyl group, an ethyl group, or a propyl group, and particularly preferably an ethyl group. When it has a substituent A, the hydrogen atom in the C1-C6 alkyl group is optionally substituted by the substituent A.

The “C1-C6 haloalkyl group” for R1 in formula (1) has the same meaning as defined above, and is preferably a 2-fluoroethyl group, a 2,2-difluoroethyl group or a 2,2,2-trifluoro group. It is an ethyl group, a 3,3-difluoropropyl group, or a 3,3,3-trifluoropropyl group, more preferably a 2-fluoroethyl group, a 2,2-difluoroethyl group, or a 2,2,2- It is a trifluoroethyl group.

The C3 to C8 cycloalkyl group of the "C3 to C8 cycloalkyl group optionally substituted with the substituent A" in R1 of the formula (1) has the same meaning as defined above, and preferably a cyclopropyl group. , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group. When it has a substituent A, the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent A.

The C2-C6 alkenyl group of the "C2-C6 alkenyl group optionally substituted with the substituent A" in R1 of the formula (1) has the same meaning as defined above, preferably a vinyl group, 1- It is a propenyl group or an allyl group, more preferably a vinyl group or an allyl group. When it has a substituent A, the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent A.

The “C2-C6 haloalkenyl group” for R1 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group, a 3-fluoroallyl group, or It is a 3,3-difluoroallyl group, more preferably a 2-fluorovinyl group or a 2,2-difluorovinyl group.

The C2-C6 alkynyl group of the "C2-C6 alkynyl group optionally substituted by the substituent A" in R1 of the formula (1) has the same meaning as defined above, preferably a propargyl group, 2- It is a butynyl group or a 3-butynyl group, and more preferably a propargyl group. When it has a substituent A, the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent A.

The “C2-C6 haloalkynyl group” for R 1 in formula (1) has the same meaning as defined above, and is preferably a 4,4-difluoro-2-butynyl group or 4-chloro-4,4-difluoro- 2-butynyl group, 4-bromo-4,4-difluoro-2-butynyl group, or 4,4,4-trifluoro-2-butynyl group, and more preferably 4,4-difluoro-2-butynyl group. Or a 4,4,4-trifluoro-2-butynyl group.

The C1 to C6 alkoxy group of the “C1 to C6 alkoxy group optionally substituted by the substituent A” in R1 of the formula (1) has the same meaning as defined above, and is preferably a methoxy group or an ethoxy group. , A propyloxy group, an isopropyloxy group, a butoxy group, or an isobutoxy group, and more preferably a methoxy group or an ethoxy group. When it has a substituent A, the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent A.

The "C1-C6 haloalkoxy group" in R1 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2,2. 2-trifluoroethoxy group, 3,3-difluoropropyloxy group or 3,3,3-trifluoropropyloxy group, more preferably difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group Or a 2,2,2-trifluoroethoxy group.

The C3 to C8 cycloalkoxy group of the "C3 to C8 cycloalkoxy group optionally substituted by the substituent A" in R1 of the formula (1) has the same meaning as defined above, and preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group. When it has a substituent A, the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted by the substituent A.

The C2-C6 alkenyloxy group in the "C2-C6 alkenyloxy group optionally substituted with the substituent A" in R1 of the formula (1) has the same meaning as defined above, and preferably a vinyloxy group, It is a 1-propenyloxy group or an allyloxy group, and more preferably an allyloxy group. When it has a substituent A, the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent A.

The “C2-C6 haloalkenyloxy group” for R 1 in formula (1) has the same meaning as defined above, and is preferably 2-fluorovinyloxy group, 2,2-difluorovinyloxy group, 3-fluoro. An allyloxy group or a 3,3-difluoroallyloxy group, more preferably a 2-fluorovinyloxy group or a 2,2-difluorovinyloxy group.

The C3-C6 alkynyloxy group of the "C3-C6 alkynyloxy group optionally substituted by the substituent A" in R1 of the formula (1) has the same meaning as defined above, and preferably a propargyloxy group. , 2-butynyloxy group, or 3-butynyloxy group, and more preferably propargyloxy group. When it has a substituent A, the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent A.

The "C3-C6 haloalkynyloxy group" for R1 in formula (1) has the same meaning as defined above, and is preferably a 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4- It is a difluoro-2-butynyloxy group, a 4-bromo-4,4-difluoro-2-butynyloxy group, or a 4,4,4-trifluoro-2-butynyloxy group, and more preferably 4,4-difluoro-2. A butynyloxy group or a 4,4,4-trifluoro-2-butynyloxy group.

“RaRbN—” in R1 of formula (1) (wherein Ra and Rb are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 A haloalkyl group, or a C3-C8 cycloalkyl group, or Ra and Rb together with the nitrogen atom to which they are attached are an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidinyl group, a homopiperidinyl group, or an azocanyl group. Each of the terms, which represents what is formed, is as defined above. Regarding the “C1 to C6 alkyl group optionally substituted with the substituent B”, in the case of having the substituent B, the hydrogen atom in the C1 to C6 alkyl group is optionally substituted with the substituent B. . As Ra and Rb, a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, a pyrrolidinyl group, or a piperidinyl group is preferable. And more preferably a hydrogen atom or a C1-C6 alkyl group optionally substituted with a substituent B. "RaRbN-" is preferably an amino group, a methylamino group, an ethylamino group, a (methoxymethyl) amino group, a (2-methoxyethyl) amino group, a (cyanomethyl) amino group, a (2-cyanoethyl) amino group, Dimethylamino group, ethylmethylamino group, diethylamino group, (methoxymethyl) methylamino group, (2-methoxyethyl) methylamino group, (cyanomethyl) methylamino group, (2-cyanoethyl) methylamino group, 2,2- A difluoroethylamino group, a 2,2,2-trifluoroethylamino group, a cyclopropylamino group, a (cyclopropyl) methylamino group, a pyrrolidinyl group, or a piperidinyl group, more preferably an amino group, a methylamino group, Dimethylamino group, ethylmethylamino group, or diethyl Is an amino group.

R2 in the formula (1) is appropriately substituted with a hydrogen atom, a nitro group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, or a substituent A. C3 to C8 cycloalkyl group, C2 to C6 alkenyl group optionally substituted with substituent A, C2 to C6 haloalkenyl group, C2 to C6 alkynyl optionally substituted with substituent A Group, C2 to C6 haloalkynyl group, C1 to C6 alkoxy group optionally substituted with substituent A, C1 to C6 haloalkoxy group, C3 to C8 cyclo group optionally substituted with substituent A Alkoxy group, C2-C6 alkenyloxy group optionally substituted with substituent A, C2-C6 haloalkenyloxy group, C3-C6 alkynyl optionally substituted with substituent A Alkoxy group, a C3 ~ C6 haloalkynyl group, Rc-L-(wherein, Rc represents an alkyl group or a C1 ~ C6 haloalkyl group, a C1 ~ C6, L is S, SO or SO _2, Or Rx1C (═O) — (wherein Rx1 is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 A cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, a C3 to C8 cycloalkoxy group, or RaRbN- (wherein Ra and Rb are as defined above). Represent

Among them, R2 is a hydrogen atom, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, a C2 to C6 alkynyl optionally substituted with a substituent A Group, or a C1 to C6 alkoxy group optionally substituted with a substituent A is preferable,
Particularly, a hydrogen atom, a halogen atom, or a C1 to C6 alkyl group which may be appropriately substituted with the substituent A is preferable.

R2 in the formula (1) includes a hydrogen atom and a nitro group.

The halogen atom in R2 of the formula (1) is as defined above, preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom or a bromine atom.

The C1 to C6 alkyl group of the “C1 to C6 alkyl group optionally substituted with the substituent A” in R2 of the formula (1) has the same meaning as defined above, and preferably a methyl group or an ethyl group. , A propyl group, an isopropyl group, a butyl group, or an isobutyl group, and more preferably a methyl group or an ethyl group. When it has a substituent A, the hydrogen atom in the C1-C6 alkyl group is optionally substituted by the substituent A.

The “C1-C6 haloalkyl group” in R2 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, 2,2,2. A trifluoroethyl group, a 3,3-difluoropropyl group, or a 3,3,3-trifluoropropyl group, more preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, or It is a 2,2,2-trifluoroethyl group.

The C3 to C8 cycloalkyl group of the "C3 to C8 cycloalkyl group optionally substituted with the substituent A" in R2 of the formula (1) has the same meaning as defined above, and is preferably a cyclopropyl group. , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group. When it has a substituent A, the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent A.

The C2-C6 alkenyl group in the "C2-C6 alkenyl group optionally substituted by the substituent A" in R2 of the formula (1) has the same meaning as defined above, preferably a vinyl group, 1- A propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, or a 3-butenyl group is more preferable, and a vinyl group, a 1-propenyl group, or an allyl group is more preferable. When it has a substituent A, the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent A.

The "C2-C6 haloalkenyl group" for R2 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group, a 2,2-dichlorovinyl group. , 3-fluoroallyl group, 3,3-difluoroallyl group, or 3,3-dichloroallyl group, and more preferably 2-fluorovinyl group or 2,2-difluorovinyl group.

The C2-C6 alkynyl group of the "C2-C6 alkynyl group optionally substituted with the substituent A" in R2 of the formula (1) has the same meaning as defined above, preferably an ethynyl group, 1- A propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group is more preferable, and an ethynyl group, a 1-propynyl group, or a propargyl group is more preferable. When it has a substituent A, the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent A.

The "C2-C6 haloalkynyl group" in R2 of the formula (1) has the same meaning as defined above, and is preferably a 3,3-difluoro-1-propynyl group or 3,3,3-trifluoro-1. -Propinyl group, 4,4-difluoro-1-butynyl group, 4,4-difluoro-2-butynyl group, 4,4,4-trifluoro-1-butynyl group, or 4,4,4-trifluoro- It is a 2-butynyl group, more preferably a 3,3-difluoro-1-propynyl group or a 3,3,3-trifluoro-1-propynyl group.

The C1 to C6 alkoxy group of the “C1 to C6 alkoxy group optionally substituted with the substituent A” in R2 of the formula (1) has the same meaning as defined above, and is preferably a methoxy group or an ethoxy group. , A propyloxy group, an isopropyloxy group, a butoxy group, or an isobutoxy group, and more preferably a methoxy group, an ethoxy group, a propyloxy group, or an isopropyloxy group. When it has a substituent A, the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent A.

The "C1-C6 haloalkoxy group" in R2 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2,2. 2-trifluoroethoxy group, 3,3-difluoropropyloxy group or 3,3,3-trifluoropropyloxy group, more preferably difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group Or a 2,2,2-trifluoroethoxy group.

The C3 to C8 cycloalkoxy group of the "C3 to C8 cycloalkoxy group optionally substituted with the substituent A" in R2 of the formula (1) has the same meaning as defined above, and preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group. When it has a substituent A, the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted by the substituent A.

The C2-C6 alkenyloxy group in the "C2-C6 alkenyloxy group optionally substituted with the substituent A" in R2 of the formula (1) has the same meaning as defined above, and preferably a vinyloxy group, It is a 1-propenyloxy group, an allyloxy group, a 1-butenyloxy group, a 2-butenyloxy group or a 3-butenyloxy group, more preferably a vinyloxy group, a 1-propenyloxy group or an allyloxy group. When it has a substituent A, the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent A.

The “C2-C6 haloalkenyloxy group” in R2 of the formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyloxy group, a 2,2-difluorovinyloxy group or a 2,2- A dichlorovinyloxy group, a 3-fluoroallyloxy group, a 3,3-difluoroallyloxy group, or a 3,3-dichloroallyloxy group, more preferably a 2-fluorovinyloxy group or a 2,2-difluoro group. It is a vinyloxy group.

The C3-C6 alkynyloxy group of the "C3-C6 alkynyloxy group optionally substituted by the substituent A" in R2 of the formula (1) has the same meaning as defined above, and preferably a propargyloxy group. , 2-butynyloxy group, or 3-butynyloxy group, and more preferably propargyloxy group. When it has a substituent A, the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent A.

The “C3-C6 haloalkynyloxy group” in R2 of the formula (1) has the same meaning as defined above, and is preferably 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro group. -2-butynyloxy group, 4-bromo-4,4-difluoro-2-butynyloxy group, or 4,4,4-trifluoro-2-butynyloxy group, more preferably 4,4-difluoro-2- It is a butynyloxy group or a 4,4,4-trifluoro-2-butynyloxy group.

“Rc-L—” in R2 of the formula (1) (wherein Rc represents a C1-C6 alkyl group or a C1-C6 haloalkyl group, and L represents S, SO, or SO ₂ ). Each term of) is synonymous with the above. "Rc-L-" is preferably a methylthio group, a methanesulfinyl group, a methanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, or a trifluoromethanesulfonyl group, more preferably a methylthio group or a methanesulfinyl group. Or a methanesulfonyl group.

“Rx1C (═O) —” in R2 of the formula (1) (wherein Rx1 is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, C3 To C8 cycloalkyl group, C1 to C6 alkoxy group, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group, or RaRbN— (wherein Ra and Rb are as defined above). .) Is synonymous with the above definition. Regarding the “C1 to C6 alkyl group optionally substituted with the substituent B”, in the case of having the substituent B, the hydrogen atom in the C1 to C6 alkyl group is optionally substituted with the substituent B. . Rx1 is preferably a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C1 to C6 alkoxy group, more preferably a hydrogen atom, It is a C1-C6 alkyl group which may be optionally substituted with a substituent B, or a C1-C6 alkoxy group. “Rx1C (═O) —” includes formyl group, acetyl group, methoxyacetyl group, cyanoacetyl group, propionyl group, difluoroacetyl group, trifluoroacetyl group, cyclopropanecarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, 2 , 2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 3,3,3-trifluoropropyloxycarbonyl group, cyclopropyloxycarbonyl group, aminocarbonyl group, methylaminocarbonyl group, ethylamino Carbonyl group, (methoxymethyl) aminocarbonyl group, (2-methoxyethyl) aminocarbonyl group, (cyanomethyl) aminocarbonyl group, (2-cyanoethyl) aminocarbonyl group, dimethylaminocarbonyl group, ethylmethyl Minocarbonyl group, diethylaminocarbonyl group, (methoxymethyl) methylaminocarbonyl group, (2-methoxyethyl) methylaminocarbonyl group, (cyanomethyl) methylaminocarbonyl group, (2-cyanoethyl) methylaminocarbonyl group, 2,2- Examples include difluoroethylaminocarbonyl group, 2,2,2-trifluoroethylaminocarbonyl group, cyclopropylaminocarbonyl group, (cyclopropyl) methylaminocarbonyl group, pyrrolidinylcarbonyl group, piperidinylcarbonyl group, and the like. . “Rx1C (═O) —” is preferably a formyl group, acetyl group, methoxyacetyl group, cyanoacetyl group, propionyl group, difluoroacetyl group, trifluoroacetyl group, methoxycarbonyl group, or ethoxycarbonyl group, and Preferred are formyl group, acetyl group, methoxyacetyl group, cyanoacetyl group, methoxycarbonyl group, and ethoxycarbonyl group.

In the formula (1), Het represents a 5-membered heterocyclic group containing a sulfur atom and a nitrogen atom.

In the 5-membered heterocyclic group containing the sulfur atom and the nitrogen atom, R3 is appropriately substituted with 0 to 2. (However, when 2-substituted R3 is present, each R3 represents an independent substituent.)

Specific examples of the 5-membered heterocyclic group containing a sulfur atom and a nitrogen atom include a thiazolyl group, an isothiazolyl group, a thiadiazolyl group, and a thiatriazolyl group.

Among them, Het is preferably a thiazolyl group or a thiadiazolyl group.

R3 of the thiazolyl group or the thiadiazolyl group is appropriately substituted with 0 to 2. (However, when 2-substituted R3 is present, each R3 represents an independent substituent.)

R3 is a hydroxyl group, a cyano group, a nitro group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, or a C3 optionally substituted with a substituent C A C8 cycloalkyl group, a C2-C6 alkenyl group optionally substituted with a substituent C, a C2-C6 haloalkenyl group, a C2-C6 alkynyl group optionally substituted with a substituent C, C2-C6 Haloalkynyl group, C1 to C6 alkoxy group optionally substituted with substituent C, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group optionally substituted with substituent C, substituent C2-C6 alkenyloxy group optionally substituted by C, C2-C6 haloalkenyloxy group, C3-C6 alkynyloxy optionally substituted by substituent C Group, C3 to C6 haloalkynyloxy group, RaRbN- (wherein Ra and Rb have the same meanings as described above), Rc-L- (wherein Rc and L have the same meanings as described above). , Rx1C (= O)-(where Rx1 is as defined above), Rx1C (= O) O- (where Rx1 is as defined above), or Rx2C (= O). N (Rx3)-(wherein Rx2 is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, C1 to C6 Represents an alkoxy group, a C1 to C6 haloalkoxy group, a C3 to C8 cycloalkoxy group, or RaRbN— (wherein Ra and Rb have the same meanings as defined above), and Rx3 represents a hydrogen atom or a substituent. Appropriately replaced by B Alkyl group which may C1 ~ C6, represent a representative.) A cycloalkyl group of haloalkyl group having C1 ~ C6 or C3 ~ C8,.

Among them, R3 is a cyano group, a nitro group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, or a C3 to optionally substituted with a substituent C. A C8 cycloalkyl group, a C2-C6 alkenyl group optionally substituted with a substituent C, a C2-C6 alkynyl group optionally substituted with a substituent C, a substituent C optionally substituted C1 to C6 alkoxy group, RaRbN- (wherein Ra and Rb are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group) , Or a C3-C8 cycloalkyl group, or Ra and Rb together with the nitrogen atom to which they are attached are an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, Represents a peridinyl group, a homopiperidinyl group, or an azocanyl group.), Or Rx2C (= O) N (Rx3)-(wherein Rx2 is a hydrogen atom or C1 optionally substituted with a substituent B). To C6 alkyl group, C1 to C6 haloalkyl group, C3 to C8 cycloalkyl group, C1 to C6 alkoxy group, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group, or RaRbN- (wherein , Ra and Rb are as defined above.), And Rx3 is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or C3 to C8. Represents a cycloalkyl group of),

In particular, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, or RaRbN- (wherein Ra and Rb are each independently a hydrogen atom, Represents a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group which may be optionally substituted with a substituent B, or Ra and Rb together with the nitrogen atom to which they are attached; And an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidinyl group, a homopiperidinyl group, or an azocanyl group is preferable.).

R3 in the formula (1) includes a hydroxyl group, a cyano group, and a nitro group.

The halogen atom in R3 of the formula (1) has the same meaning as defined above, preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and particularly preferably a chlorine atom or a bromine atom.

The C1 to C6 alkyl group in the “C1 to C6 alkyl group optionally substituted with a substituent C” in R3 of the formula (1) has the same meaning as defined above, and preferably a methyl group or an ethyl group. , A propyl group, an isopropyl group, a butyl group, or an isobutyl group, more preferably a methyl group, an ethyl group, or a propyl group, and particularly preferably a methyl group or an ethyl group. When it has a substituent C, the hydrogen atom in the C1 to C6 alkyl group is optionally substituted by the substituent C.

The “C1-C6 haloalkyl group” for R3 in formula (1) has the same meaning as defined above, and is preferably a monofluoromethyl group, a monochloromethyl group, a monobromomethyl group, a difluoromethyl group, a trifluoromethyl group. , 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 3,3-difluoropropyl group, or 3,3,3-trifluoropropyl group, more preferably monobromomethyl group , A difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, or a 2,2,2-trifluoroethyl group.

The C3 to C8 cycloalkyl group of the "C3 to C8 cycloalkyl group optionally substituted by the substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably a cyclopropyl group. , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group. When it has a substituent C, the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent C.

The C2-C6 alkenyl group in the "C2-C6 alkenyl group optionally substituted with a substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably a vinyl group, 1- A propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, or a 3-butenyl group is more preferable, and a vinyl group, a 1-propenyl group, or an allyl group is more preferable. When it has a substituent C, the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent C.

The “C2-C6 haloalkenyl group” for R3 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group or a 2,2-dichlorovinyl group. , 3-fluoroallyl group, 3,3-difluoroallyl group, or 3,3-dichloroallyl group, and more preferably 2-fluorovinyl group or 2,2-difluorovinyl group.

The C2-C6 alkynyl group of the "C2-C6 alkynyl group optionally substituted by the substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably an ethynyl group, 1- A propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group is more preferable, and an ethynyl group, a 1-propynyl group, or a propargyl group is more preferable. When it has a substituent C, the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent C.

The "C2-C6 haloalkynyl group" in R3 of the formula (1) has the same meaning as defined above, and is preferably a 3,3-difluoro-1-propynyl group or a 3,3,3-trifluoro-1 group. -Propinyl group, 4,4-difluoro-1-butynyl group, 4,4-difluoro-2-butynyl group, 4,4,4-trifluoro-1-butynyl group, or 4,4,4-trifluoro- It is a 2-butynyl group, more preferably a 3,3-difluoro-1-propynyl group or a 3,3,3-trifluoro-1-propynyl group.

The C1 to C6 alkoxy group of the “C1 to C6 alkoxy group optionally substituted with a substituent C” in R3 of the formula (1) has the same meaning as defined above, and preferably a methoxy group or an ethoxy group. , A propyloxy group, an isopropyloxy group, a butoxy group, or an isobutoxy group, and more preferably a methoxy group, an ethoxy group, a propyloxy group, or an isopropyloxy group. When it has a substituent C, the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent C.

The “C1-C6 haloalkoxy group” in R3 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2,2. 2-trifluoroethoxy group, 3,3-difluoropropyloxy group or 3,3,3-trifluoropropyloxy group, more preferably difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group Or a 2,2,2-trifluoroethoxy group.

The C3 to C8 cycloalkoxy group of the "C3 to C8 cycloalkoxy group optionally substituted with a substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group. When it has a substituent C, the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted by the substituent C.

The C2-C6 alkenyloxy group of the "C2-C6 alkenyloxy group optionally substituted with a substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably a vinyloxy group, It is a 1-propenyloxy group, an allyloxy group, a 1-butenyloxy group, a 2-butenyloxy group or a 3-butenyloxy group, more preferably a vinyloxy group, a 1-propenyloxy group or an allyloxy group. When it has a substituent C, the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent C.

The “C2-C6 haloalkenyloxy group” for R3 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyloxy group, a 2,2-difluorovinyloxy group, or a 2,2- A dichlorovinyloxy group, a 3-fluoroallyloxy group, a 3,3-difluoroallyloxy group, or a 3,3-dichloroallyloxy group, more preferably a 2-fluorovinyloxy group or a 2,2-difluoro group. It is a vinyloxy group.

The C3 to C6 alkynyloxy group of the "C3 to C6 alkynyloxy group optionally substituted with a substituent C" in R3 of the formula (1) has the same meaning as defined above, and preferably a propargyloxy group. , 2-butynyloxy group, or 3-butynyloxy group, and more preferably propargyloxy group. When it has a substituent C, the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent C.

The "C3-C6 haloalkynyloxy group" for R3 in formula (1) has the same meaning as defined above, and is preferably a 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro group. -2-butynyloxy group, 4-bromo-4,4-difluoro-2-butynyloxy group, or 4,4,4-trifluoro-2-butynyloxy group, more preferably 4,4-difluoro-2- It is a butynyloxy group or a 4,4,4-trifluoro-2-butynyloxy group.

Ra and Rb of "RaRbN-" in R3 of the formula (1) are as defined above. As Ra and Rb, a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, a pyrrolidinyl group, or a piperidinyl group is preferable. And more preferably a hydrogen atom or a C1-C6 alkyl group optionally substituted with a substituent B. Preferred as “RaRbN—” is amino group, methylamino group, ethylamino group, (methoxymethyl) amino group, (2-methoxyethyl) amino group, (cyanomethyl) amino group, (2-cyanoethyl) amino group, dimethyl group. Amino group, ethylmethylamino group, diethylamino group, (methoxymethyl) methylamino group, (2-methoxyethyl) methylamino group, (cyanomethyl) methylamino group, (2-cyanoethyl) methylamino group, 2,2-difluoro It is an ethylamino group, a 2,2,2-trifluoroethylamino group, a cyclopropylamino group, a (cyclopropyl) methylamino group, a pyrrolidinyl group, or a piperidinyl group, more preferably an amino group, a methylamino group, or dimethyl. Amino group, ethylmethylamino group, or diethyl group An amino group, particularly preferably an amino group.

Rc and L of "Rc-L-" in R3 of the formula (1) have the same meaning as above. "Rc-L-" is preferably a methylthio group, a methanesulfinyl group, a methanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, or a trifluoromethanesulfonyl group, and more preferably a methylthio group or a methanesulfinyl group. Or a methanesulfonyl group.

Rx1 of "Rx1C (= O)-" in R3 of the formula (1) has the same meaning as defined above. Rx1 is preferably a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C1 to C6 alkoxy group, more preferably a hydrogen atom, It is a C1-C6 alkyl group which may be optionally substituted with a substituent B, or a C1-C6 alkoxy group. “Rx1C (═O) —” is preferably formyl group, acetyl group, methoxyacetyl group, cyanoacetyl group, propionyl group, difluoroacetyl group, trifluoroacetyl group, cyclopropanecarbonyl group, methoxycarbonyl group, ethoxycarbonyl. Group, 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 3,3,3-trifluoropropyloxycarbonyl group, cyclopropyloxycarbonyl group, aminocarbonyl group, methylaminocarbonyl group , Ethylaminocarbonyl group, (methoxymethyl) aminocarbonyl group, (2-methoxyethyl) aminocarbonyl group, (cyanomethyl) aminocarbonyl group, (2-cyanoethyl) aminocarbonyl group, dimethylaminocarbonyl group, Cylmethylaminocarbonyl group, diethylaminocarbonyl group, (methoxymethyl) methylaminocarbonyl group, (2-methoxyethyl) methylaminocarbonyl group, (cyanomethyl) methylaminocarbonyl group, (2-cyanoethyl) methylaminocarbonyl group, 2, 2-difluoroethylaminocarbonyl group, 2,2,2-trifluoroethylaminocarbonyl group, cyclopropylaminocarbonyl group, (cyclopropyl) methylaminocarbonyl group, pyrrolidinylcarbonyl group, or piperidinylcarbonyl group , And more preferably formyl group, acetyl group, methoxyacetyl group, cyanoacetyl group, propionyl group, difluoroacetyl group, trifluoroacetyl group, methoxycarbonyl group, ethoxycarbonyl group.

Rx1 of "Rx1C (= O) O-" in R3 of the formula (1) has the same meaning as defined above. “Rx1C (═O) O—” is preferably formyloxy group, acetyloxy group, methoxyacetyloxy group, cyanoacetyloxy group, propionyloxy group, difluoroacetyloxy group, trifluoroacetyloxy group, cyclopropanecarbonyl. Oxy group, methoxycarbonyloxy group, ethoxycarbonyloxy group, 2,2-difluoroethoxycarbonyloxy group, 2,2,2-trifluoroethoxycarbonyloxy group, 3,3,3-trifluoropropyloxycarbonyloxy group, Cyclopropyloxycarbonyloxy group, aminocarbonyloxy group, methylaminocarbonyloxy group, ethylaminocarbonyloxy group, (methoxymethyl) aminocarbonyloxy group, (2-methoxyethyl) aminocarbonyl group Oxy group, (cyanomethyl) aminocarbonyloxy group, (2-cyanoethyl) aminocarbonyloxy group, dimethylaminocarbonyloxy group, ethylmethylaminocarbonyloxy group, diethylaminocarbonyloxy group, (methoxymethyl) methylaminocarbonyloxy group, ( 2-methoxyethyl) methylaminocarbonyloxy group, (cyanomethyl) methylaminocarbonyloxy group, (2-cyanoethyl) methylaminocarbonyloxy group, 2,2-difluoroethylaminocarbonyloxy group, 2,2,2-trifluoro Ethylaminocarbonyloxy group, cyclopropylaminocarbonyloxy group, (cyclopropyl) methylaminocarbonyloxy group, pyrrolidinylcarbonyloxy group, or piperidinylcarbonyl group An alkoxy group, more preferably a formyloxy group, an acetyloxy group or trifluoroacetyl group.

"Rx2C (= O) N (Rx3)-" in R3 of the formula (1) (wherein Rx2 is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 A haloalkyl group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, a C3 to C8 cycloalkoxy group, or RaRbN- (wherein Ra and Rb have the same meanings as defined above). Rx3 represents a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group). The terms are synonymous with the above definitions. Regarding the “C1 to C6 alkyl group optionally substituted with the substituent B”, in the case of having the substituent B, the hydrogen atom in the C1 to C6 alkyl group is optionally substituted with the substituent B. . Rx2 is preferably a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C1 to C6 alkoxy group, or RaRbN— (wherein Ra and Rb Is the same as defined above.), And more preferably a C1-C6 alkyl group optionally substituted by the substituent B. Rx3 is preferably a hydrogen atom, a C1 to C6 alkyl group which may be appropriately substituted with a substituent B, or a C1 to C6 haloalkyl group, and more preferably a hydrogen atom. Specific examples of Rx2 are preferably hydrogen atom, methyl group, methoxymethyl group, cyanomethyl group, ethyl group, difluoromethyl group, trifluoromethyl group, cyclopropyl group, methoxy group, ethoxy group and 2,2-difluoroethoxy. Group, 2,2,2-trifluoroethoxy group, cyclopropyloxy group, amino group, methylamino group, ethylamino group, (methoxymethyl) amino group, (2-methoxyethyl) amino group, (cyanomethyl) amino group , (2-cyanoethyl) amino group, dimethylamino group, ethylmethylamino group, diethylamino group, (methoxymethyl) methylamino group, (2-methoxyethyl) methylamino group, (cyanomethyl) methylamino group, (2-cyanoethyl ) Methylamino group, 2,2-difluoroethylamino group, 2, , 2-trifluoroethylamino group, cyclopropylamino group, (cyclopropyl) methylamino group, pyrrolidinyl group, or piperidinyl group, and more preferably hydrogen atom, methyl group, methoxymethyl group, cyanomethyl group, difluoromethyl group. A group, a trifluoromethyl group, a methoxy group, an ethoxy group, an amino group, a dimethylamino group, an ethylmethylamino group, or a diethylamino group. In addition, specific examples of Rx3 are preferably hydrogen atom, methyl group, methoxymethyl group, ethoxymethyl group, cyanomethyl group, ethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-cyanoethyl group, propyl group. , 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, or cyclopropyl group, and more preferably hydrogen atom, methyl group, methoxymethyl group, cyanomethyl group, ethyl group, 2-methoxy. It is an ethyl group, a 2,2-difluoroethyl group, or a 2,2,2-trifluoroethyl group. Further, “Rx2C (═O) N (Rx3) —” is preferably an acetylamide group, a 2,2,2-trifluoroacetylamide group, a methylcarbamate group, or an ethylcarbamate group, and more preferably It is an acetylamide group.

The Het in the formula (1) will be described in detail below.

When Het is a thiazolyl group, an isothiazolyl group, a thiadiazolyl group, or a thiatriazolyl group, Het has the formula (a-1)

Or formula (a-2)

(Wherein R3 is as defined above, G1, G2, and G3 are each independently a carbon atom or a nitrogen atom, and at least G1, G2, and G3) One represents a nitrogen atom, and ma represents an integer of 0 to 2).

When ma in the formula (a-1) and the formula (a-2) is 2, two R3's each represent an independent substituent, which may be the same or different and can be arbitrarily selected.

Specific examples of the partial structure of the formula (a-1) are shown below.

Preferred specific examples of the partial structure of the formula (a-1) are shown below.

More preferable specific examples of the partial structure of the formula (a-1) are shown below.

Specific examples of the partial structure of the formula (a-2) are shown below.

Preferred specific examples of the partial structure of the formula (a-2) are shown below.

More preferable specific examples of the partial structure of the formula (a-2) are shown below.

R4 in the formula (1) is optionally substituted with a hydroxyl group, a cyano group, a nitro group, a halogen atom, a C1 to C6 alkyl group which may be optionally substituted with a substituent C, a C1 to C6 haloalkyl group, and a substituent C. Optionally a C3 to C8 cycloalkyl group, a C2 to C6 alkenyl group optionally substituted with a substituent C, a C2 to C6 haloalkenyl group, a C2 to C6 alkynyl optionally substituted with a substituent C Group, C2 to C6 haloalkynyl group, C1 to C6 alkoxy group optionally substituted with substituent C, C1 to C6 haloalkoxy group, C3 to C8 cyclo optionally substituted with substituent C Alkoxy group, C2-C6 alkenyloxy group optionally substituted with substituent C, C2-C6 haloalkenyloxy group, C3-C6 optionally substituted with substituent C Alkynyloxy group, C3-C6 haloalkynyloxy group, RaRbN- (wherein Ra and Rb are as defined above), Rc-L- (wherein Rc and L are as defined above). .), Rx1C (= O)-(where Rx1 is as defined above), Rx1C (= O) O- (where Rx1 is as defined above), or Rx2C (=. O) N (Rx3)-(wherein Rx2 and Rx3 are as defined above).

Among them, R4 is a cyano group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C1 to C6 alkoxy optionally substituted with a substituent C. A group or a C1-C6 haloalkoxy group is preferred,
Particularly, R4 is preferably a halogen atom or a C1 to C6 alkyl group which may be appropriately substituted with a substituent C.

R4 in the formula (1) includes a hydroxyl group, a cyano group, and a nitro group.

The halogen atom in R4 of the formula (1) has the same meaning as defined above, preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom or a bromine atom. And particularly preferably a fluorine atom.

The C1 to C6 alkyl group in the "C1 to C6 alkyl group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and is preferably a methyl group or an ethyl group. , A propyl group, or an isopropyl group, and more preferably a methyl group, an ethyl group, or a propyl group. When it has a substituent C, the hydrogen atom in the C1 to C6 alkyl group is optionally substituted by the substituent C.

The “C1-C6 haloalkyl group” for R4 in formula (1) has the same meaning as defined above, and is preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, 2,2,2. -Trifluoroethyl group, 3,3-difluoropropyl group, or 3,3,3-trifluoropropyl group, and more preferably difluoromethyl group or trifluoromethyl group.

The C3 to C8 cycloalkyl group of the "C3 to C8 cycloalkyl group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably a cyclopropyl group. , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group. When it has a substituent C, the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent C.

The C2-C6 alkenyl group in the "C2-C6 alkenyl group optionally substituted by the substituent C" in R4 of the formula (1) has the same meaning as defined above, and is preferably a vinyl group, 1- It is a propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, or a 3-butenyl group, and more preferably a vinyl group. When it has a substituent C, the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent C.

The “C2-C6 haloalkenyl group” for R4 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group, a 2,2-dichlorovinyl group. , 3-fluoroallyl group, 3,3-difluoroallyl group, or 3,3-dichloroallyl group, and more preferably 2-fluorovinyl group or 2,2-difluorovinyl group.

The C2-C6 alkynyl group of the "C2-C6 alkynyl group optionally substituted by the substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably an ethynyl group, 1- It is a propynyl group or a propargyl group, more preferably an ethynyl group. When it has a substituent C, the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent C.

The "C2-C6 haloalkynyl group" in R4 of the formula (1) has the same meaning as defined above, and is preferably a 3,3-difluoro-1-propynyl group or a 3,3,3-trifluoro-1 group. -Propinyl group, 4,4-difluoro-1-butynyl group, 4,4-difluoro-2-butynyl group, 4,4,4-trifluoro-1-butynyl group, or 4,4,4-trifluoro- It is a 2-butynyl group, more preferably a 3,3-difluoro-1-propynyl group or a 3,3,3-trifluoro-1-propynyl group.

The C1 to C6 alkoxy group of the "C1 to C6 alkoxy group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and is preferably a methoxy group or an ethoxy group. , A propyloxy group, or an isopropyloxy group, and more preferably a methoxy group or an ethoxy group. When it has a substituent C, the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent C.

The “C1-C6 haloalkoxy group” in R4 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2, A 2-trifluoroethoxy group, a 3,3-difluoropropyloxy group, or a 3,3,3-trifluoropropyloxy group is more preferable, and a difluoromethoxy group or a trifluoromethoxy group is more preferable.

The C3 to C8 cycloalkoxy group of the "C3 to C8 cycloalkoxy group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group. When it has a substituent C, the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted by the substituent C.

The C2-C6 alkenyloxy group of the "C2-C6 alkenyloxy group optionally substituted by the substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably a vinyloxy group, It is a 1-propenyloxy group or an allyloxy group, and more preferably an allyloxy group. When it has a substituent C, the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent C.

The “C2-C6 haloalkenyloxy group” for R4 in formula (1) has the same meaning as defined above, and is preferably 2-fluorovinyloxy group, 2,2-difluorovinyloxy group, 2,2- A dichlorovinyloxy group, a 3-fluoroallyloxy group, a 3,3-difluoroallyloxy group, or a 3,3-dichloroallyloxy group, more preferably a 2-fluorovinyloxy group or a 2,2-difluoro group. It is a vinyloxy group.

The C3 to C6 alkynyloxy group of the "C3 to C6 alkynyloxy group optionally substituted with a substituent C" in R4 of the formula (1) has the same meaning as defined above, and preferably a propargyloxy group. , 2-butynyloxy group, or 3-butynyloxy group, and more preferably propargyloxy group. When it has a substituent C, the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent C.

The “C3-C6 haloalkynyloxy group” for R4 in formula (1) has the same meaning as defined above, and is preferably a 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro group. -2-butynyloxy group, 4-bromo-4,4-difluoro-2-butynyloxy group, or 4,4,4-trifluoro-2-butynyloxy group, more preferably 4,4-difluoro-2- It is a butynyloxy group or a 4,4,4-trifluoro-2-butynyloxy group.

Ra and Rb of "RaRbN-" in R4 of the formula (1) are as defined above. Preferred as “RaRbN—” is amino group, methylamino group, ethylamino group, (methoxymethyl) amino group, (2-methoxyethyl) amino group, (cyanomethyl) amino group, (2-cyanoethyl) amino group, dimethyl group. Amino group, ethylmethylamino group, diethylamino group, (methoxymethyl) methylamino group, (2-methoxyethyl) methylamino group, (cyanomethyl) methylamino group, (2-cyanoethyl) methylamino group, 2,2-difluoro It is an ethylamino group, a 2,2,2-trifluoroethylamino group, a cyclopropylamino group, a (cyclopropyl) methylamino group, a pyrrolidinyl group, or a piperidinyl group, more preferably an amino group, a dimethylamino group, or ethyl. It is a methylamino group or a diethylamino group.

Rc and L of "Rc-L-" in R4 of the formula (1) have the same meaning as above. "Rc-L-" is preferably a methylthio group, a methanesulfinyl group, a methanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, or a trifluoromethanesulfonyl group, and more preferably a methylthio group or a methanesulfinyl group. Or a methanesulfonyl group.

Rx1 of "Rx1C (= O)-" in R4 of the formula (1) has the same meaning as defined above. “Rx1C (═O) —” is preferably an acetyl group, a methoxyacetyl group, a cyanoacetyl group, a propionyl group, a difluoroacetyl group, a trifluoroacetyl group, a cyclopropanecarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, 2 , 2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 3,3,3-trifluoropropyloxycarbonyl group, cyclopropyloxycarbonyl group, aminocarbonyl group, methylaminocarbonyl group, ethylamino Carbonyl group, (methoxymethyl) aminocarbonyl group, (2-methoxyethyl) aminocarbonyl group, (cyanomethyl) aminocarbonyl group, (2-cyanoethyl) aminocarbonyl group, dimethylaminocarbonyl group, ethylmethyl Minocarbonyl group, diethylaminocarbonyl group, (methoxymethyl) methylaminocarbonyl group, (2-methoxyethyl) methylaminocarbonyl group, (cyanomethyl) methylaminocarbonyl group, (2-cyanoethyl) methylaminocarbonyl group, 2,2- A difluoroethylaminocarbonyl group, a 2,2,2-trifluoroethylaminocarbonyl group, a cyclopropylaminocarbonyl group, a (cyclopropyl) methylaminocarbonyl group, a pyrrolidinylcarbonyl group, or a piperidinylcarbonyl group, and Preferably, acetyl group, methoxyacetyl group, cyanoacetyl group, difluoroacetyl group, trifluoroacetyl group, methoxycarbonyl group, ethoxycarbonyl group, aminocarbonyl group, dimethylaminocarbonyl. , Ethyl-methylaminocarbonyl group or diethylamino group.

Rx1 of "Rx1C (= O) O-" in R4 of the formula (1) has the same meaning as defined above. “Rx1C (═O) O—” is preferably acetyloxy group, methoxyacetyloxy group, cyanoacetyloxy group, propionyloxy group, difluoroacetyloxy group, trifluoroacetyloxy group, cyclopropanecarbonyloxy group, methoxy. Carbonyloxy group, ethoxycarbonyloxy group, 2,2-difluoroethoxycarbonyloxy group, 2,2,2-trifluoroethoxycarbonyloxy group, 3,3,3-trifluoropropyloxycarbonyloxy group, cyclopropyloxycarbonyl Oxy group, aminocarbonyloxy group, methylaminocarbonyloxy group, ethylaminocarbonyloxy group, (methoxymethyl) aminocarbonyloxy group, (2-methoxyethyl) aminocarbonyloxy group, (sia Methyl) aminocarbonyloxy group, (2-cyanoethyl) aminocarbonyloxy group, dimethylaminocarbonyloxy group, ethylmethylaminocarbonyloxy group, diethylaminocarbonyloxy group, (methoxymethyl) methylaminocarbonyloxy group, (2-methoxyethyl ) Methylaminocarbonyloxy group, (cyanomethyl) methylaminocarbonyloxy group, (2-cyanoethyl) methylaminocarbonyloxy group, 2,2-difluoroethylaminocarbonyloxy group, 2,2,2-trifluoroethylaminocarbonyloxy group A group, a cyclopropylaminocarbonyloxy group, a (cyclopropyl) methylaminocarbonyloxy group, a pyrrolidinylcarbonyloxy group, or a piperidinylcarbonyloxy group, Preferably, acetyloxy group, methoxyacetyloxy group, cyanoacetyloxy group, difluoroacetyloxy group, trifluoroacetyloxy group, methoxycarbonyloxy group, ethoxycarbonyloxy group, aminocarbonyloxy group, dimethylaminocarbonyloxy group, It is an ethylmethylaminocarbonyloxy group or a diethylaminocarbonyloxy group.

“Rx2C (═O) N (Rx3) —” in R4 of the formula (1) (wherein Rx2 is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 A haloalkyl group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, a C3 to C8 cycloalkoxy group, or RaRbN- (wherein Ra and Rb have the same meanings as defined above). Rx3 represents a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group). The terms are synonymous with the above definitions. Regarding the “C1 to C6 alkyl group optionally substituted with the substituent B”, in the case of having the substituent B, the hydrogen atom in the C1 to C6 alkyl group is optionally substituted with the substituent B. . Rx2 is preferably hydrogen atom, methyl group, methoxymethyl group, cyanomethyl group, ethyl group, difluoromethyl group, trifluoromethyl group, cyclopropyl group, methoxy group, ethoxy group, 2,2-difluoroethoxy group, 2 , 2,2-trifluoroethoxy group, cyclopropyloxy group, amino group, methylamino group, ethylamino group, (methoxymethyl) amino group, (2-methoxyethyl) amino group, (cyanomethyl) amino group, (2 -Cyanoethyl) amino group, dimethylamino group, ethylmethylamino group, diethylamino group, (methoxymethyl) methylamino group, (2-methoxyethyl) methylamino group, (cyanomethyl) methylamino group, (2-cyanoethyl) methylamino group Group, 2,2-difluoroethylamino group, 2,2,2- Rifluoroethylamino group, cyclopropylamino group, (cyclopropyl) methylamino group, pyrrolidinyl group, or piperidinyl group, more preferably hydrogen atom, methyl group, methoxymethyl group, cyanomethyl group, difluoromethyl group, trifluoromethyl group, It is a fluoromethyl group, a methoxy group, an ethoxy group, an amino group, a dimethylamino group, an ethylmethylamino group, or a diethylamino group. Further, Rx3 is preferably hydrogen atom, methyl group, methoxymethyl group, ethoxymethyl group, cyanomethyl group, ethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-cyanoethyl group, propyl group, 2, 2-difluoroethyl group, 2,2,2-trifluoroethyl group, or cyclopropyl group, more preferably hydrogen atom, methyl group, methoxymethyl group, cyanomethyl group, ethyl group, 2-methoxyethyl group, It is a 2,2-difluoroethyl group or a 2,2,2-trifluoroethyl group.

R5 in formula (1) has the same meaning as R4 described above. That is, a hydroxyl group, a cyano group, a nitro group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, and a C3 to C8 optionally substituted with a substituent C. A cycloalkyl group, a C2 to C6 alkenyl group optionally substituted with a substituent C, a C2 to C6 haloalkenyl group, a C2 to C6 alkynyl group optionally substituted with a substituent C, a C2 to C6 Haloalkynyl group, C1 to C6 alkoxy group optionally substituted with substituent C, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group optionally substituted with substituent C, substituent C A C2-C6 alkenyloxy group optionally substituted with, a C2-C6 haloalkenyloxy group, a C3-C6 alkynyloxy optionally substituted with a substituent C Group, C3 to C6 haloalkynyloxy group, RaRbN- (wherein Ra and Rb have the same meanings as described above), Rc-L- (wherein Rc and L have the same meanings as described above). , Rx1C (= O)-(where Rx1 is as defined above), Rx1C (= O) O- (where Rx1 is as defined above), or Rx2C (= O). N (Rx3)-(wherein Rx2 and Rx3 have the same meanings as described above).

Among them, R5 is a hydroxyl group, a cyano group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, or a C2 to C6 optionally substituted with a substituent C. Alkenyl group, a C2-C6 alkynyl group optionally substituted with a substituent C, a C1-C6 alkoxy group optionally substituted with a substituent C, a C1-C6 haloalkoxy group, or Rc-L -(Wherein Rc represents a C1-C6 alkyl group or a C1-C6 haloalkyl group, and L represents S, SO, or SO ₂ ),
Particularly, a cyano group, a halogen atom, or a C1 to C6 alkoxy group which may be appropriately substituted with a substituent C is preferable.

R5 in the formula (1) includes a hydroxyl group, a cyano group, and a nitro group.

The halogen atom in R5 of the formula (1) has the same meaning as defined above, preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom or a chlorine atom, and particularly preferably Preferred is a fluorine atom.

The C1 to C6 alkyl group of the “C1 to C6 alkyl group optionally substituted by the substituent C” in R5 of the formula (1) has the same meaning as defined above, and preferably a methyl group or an ethyl group. , A propyl group, an isopropyl group, a butyl group, or an isobutyl group, and more preferably a methyl group or an ethyl group. When it has a substituent C, the hydrogen atom in the C1 to C6 alkyl group is optionally substituted by the substituent C.

The “C1-C6 haloalkyl group” in R5 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, 2,2,2. A trifluoroethyl group, a 3,3-difluoropropyl group, or a 3,3,3-trifluoropropyl group, more preferably a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, or It is a 2,2,2-trifluoroethyl group.

The C3 to C8 cycloalkyl group of the "C3 to C8 cycloalkyl group optionally substituted with the substituent C" in R5 of the formula (1) has the same meaning as defined above, and preferably a cyclopropyl group. , A cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group or a cyclobutyl group. When it has a substituent C, the hydrogen atom in the C3-C8 cycloalkyl group is optionally substituted by the substituent C.

The C2-C6 alkenyl group in the "C2-C6 alkenyl group optionally substituted with a substituent C" in R5 of the formula (1) has the same meaning as defined above, and preferably a vinyl group, 1- A propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, or a 3-butenyl group is more preferable, and a vinyl group, a 1-propenyl group, or an allyl group is more preferable. When it has a substituent C, the hydrogen atom in the C2-C6 alkenyl group is optionally substituted by the substituent C.

The “C2-C6 haloalkenyl group” for R5 in the formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyl group, a 2,2-difluorovinyl group or a 2,2-dichlorovinyl group. , 3-fluoroallyl group, 3,3-difluoroallyl group, or 3,3-dichloroallyl group, and more preferably 2-fluorovinyl group or 2,2-difluorovinyl group.
The C2-C6 alkynyl group of the "C2-C6 alkynyl group optionally substituted with a substituent C" in R5 of the formula (1) has the same meaning as defined above, and preferably an ethynyl group, 1- A propynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, or a 3-butynyl group is more preferable, and an ethynyl group, a 1-propynyl group, or a propargyl group is more preferable. When it has a substituent C, the hydrogen atom in the C2-C6 alkynyl group is optionally substituted by the substituent C.

The "C2-C6 haloalkynyl group" for R5 in formula (1) has the same meaning as defined above, and is preferably a 3,3-difluoro-1-propynyl group or 3,3,3-trifluoro-1. -Propinyl group, 4,4-difluoro-1-butynyl group, 4,4-difluoro-2-butynyl group, 4,4,4-trifluoro-1-butynyl group, or 4,4,4-trifluoro- It is a 2-butynyl group, more preferably a 3,3-difluoro-1-propynyl group or a 3,3,3-trifluoro-1-propynyl group.

The C1 to C6 alkoxy group of the "C1 to C6 alkoxy group optionally substituted with a substituent C" in R5 of the formula (1) has the same meaning as defined above, and preferably a methoxy group or an ethoxy group. , A propyloxy group, an isopropyloxy group, a butoxy group, or an isobutoxy group, and more preferably a methoxy group, an ethoxy group, a propyloxy group, or an isopropyloxy group. When it has a substituent C, the hydrogen atom in the C1-C6 alkoxy group is optionally substituted by the substituent C. The substituent C is preferably a cyano group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, a C2 to C6 alkoxyalkoxy group, or Rc-L- (wherein Rc And L are as defined above, and more preferably a cyano group, a C1 to C6 alkoxy group, or Rc-L- (wherein Rc and L are as defined above). is there. The C1-C6 alkoxy group substituted with the substituent C is preferably a cyanomethoxy group, a cyanoethoxy group, a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, or an ethoxyethoxy group, and more preferably cyanomethoxy group. A group, a methoxymethoxy group, or a methoxyethoxy group.

The "C1-C6 haloalkoxy group" in R5 of the formula (1) has the same meaning as defined above, and is preferably a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, 2,2,2. 2-trifluoroethoxy group, 3,3-difluoropropyloxy group or 3,3,3-trifluoropropyloxy group, more preferably difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group Or a 2,2,2-trifluoroethoxy group.

The C3-C8 cycloalkoxy group of the "C3-C8 cycloalkoxy group optionally substituted with a substituent C" in R5 of the formula (1) has the same meaning as defined above, and preferably cyclopropyloxy Group, a cyclobutoxy group, a cyclopentyloxy group, or a cyclohexyloxy group, and more preferably a cyclopropyloxy group or a cyclobutoxy group. When it has a substituent C, the hydrogen atom in the C3-C8 cycloalkoxy group is optionally substituted by the substituent C.

The C2-C6 alkenyloxy group of the "C2-C6 alkenyloxy group optionally substituted with a substituent C" in R5 of the formula (1) has the same meaning as defined above, and preferably a vinyloxy group, 1-propenyloxy group, allyloxy group, 1-butenyloxy group, 2-butenyloxy group or 3-butenyloxy group, more preferably vinyloxy group, 1-propenyloxy group or allyloxy group, particularly preferably, It is an allyloxy group. When it has a substituent C, the hydrogen atom in the C2-C6 alkenyloxy group is optionally substituted by the substituent C.

The “C2-C6 haloalkenyloxy group” for R5 in formula (1) has the same meaning as defined above, and is preferably a 2-fluorovinyloxy group, a 2,2-difluorovinyloxy group, or a 2,2- A dichlorovinyloxy group, a 3-fluoroallyloxy group, a 3,3-difluoroallyloxy group, or a 3,3-dichloroallyloxy group, more preferably a 2-fluorovinyloxy group or a 2,2-difluoro group. It is a vinyloxy group.

The C3 to C6 alkynyloxy group of the "C3 to C6 alkynyloxy group optionally substituted with a substituent C" in R5 of the formula (1) has the same meaning as defined above, and preferably a propargyloxy group. , 2-butynyloxy group, or 3-butynyloxy group, more preferably propargyloxy group, or 2-butynyloxy group, and particularly preferably propargyloxy group. When it has a substituent C, the hydrogen atom in the C3-C6 alkynyloxy group is optionally substituted by the substituent C.

The “C3-C6 haloalkynyloxy group” for R5 in formula (1) has the same meaning as defined above, and is preferably 4,4-difluoro-2-butynyloxy group, 4-chloro-4,4-difluoro group. -2-butynyloxy group, 4-bromo-4,4-difluoro-2-butynyloxy group, or 4,4,4-trifluoro-2-butynyloxy group, more preferably 4,4-difluoro-2- It is a butynyloxy group or a 4,4,4-trifluoro-2-butynyloxy group.

Ra and Rb of "RaRbN-" in R5 of the formula (1) are as defined above. As Ra and Rb, a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, a pyrrolidinyl group, or a piperidinyl group is preferable. And more preferably a hydrogen atom, a C1-C6 alkyl group optionally substituted with a substituent B, a pyrrolidinyl group, or a piperidinyl group. Preferred as “RaRbN—” is amino group, methylamino group, ethylamino group, (methoxymethyl) amino group, (2-methoxyethyl) amino group, (cyanomethyl) amino group, (2-cyanoethyl) amino group, dimethyl group. Amino group, ethylmethylamino group, diethylamino group, (methoxymethyl) methylamino group, (2-methoxyethyl) methylamino group, (cyanomethyl) methylamino group, (2-cyanoethyl) methylamino group, 2,2-difluoro It is an ethylamino group, a 2,2,2-trifluoroethylamino group, a cyclopropylamino group, a (cyclopropyl) methylamino group, a pyrrolidinyl group, or a piperidinyl group, more preferably an amino group, a methylamino group, or dimethyl. Amino group, ethylmethylamino group, diethylamino group A pyrrolidinyl group or piperidines lysinyl group.

Rc and L of "Rc-L-" in R5 of the formula (1) have the same meaning as above. Rc is preferably a C1-C6 alkyl group. L is preferably S. "Rc-L-" is preferably a methylthio group, a methanesulfinyl group, a methanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, or a trifluoromethanesulfonyl group, and more preferably a methylthio group or a methanesulfinyl group. Or a methanesulfonyl group.

Rx1 of "Rx1C (= O)-" in R5 of the formula (1) has the same meaning as defined above. “Rx1C (═O) —” is preferably an acetyl group, a methoxyacetyl group, a cyanoacetyl group, a propionyl group, a difluoroacetyl group, a trifluoroacetyl group, a cyclopropanecarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, 2 , 2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 3,3,3-trifluoropropyloxycarbonyl group, cyclopropyloxycarbonyl group, aminocarbonyl group, methylaminocarbonyl group, ethylamino Carbonyl group, (methoxymethyl) aminocarbonyl group, (2-methoxyethyl) aminocarbonyl group, (cyanomethyl) aminocarbonyl group, (2-cyanoethyl) aminocarbonyl group, dimethylaminocarbonyl group, ethylmethyl Minocarbonyl group, diethylaminocarbonyl group, (methoxymethyl) methylaminocarbonyl group, (2-methoxyethyl) methylaminocarbonyl group, (cyanomethyl) methylaminocarbonyl group, (2-cyanoethyl) methylaminocarbonyl group, 2,2- A difluoroethylaminocarbonyl group, a 2,2,2-trifluoroethylaminocarbonyl group, a cyclopropylaminocarbonyl group, a (cyclopropyl) methylaminocarbonyl group, a pyrrolidinylcarbonyl group, or a piperidinylcarbonyl group, and Preferably, acetyl group, methoxyacetyl group, cyanoacetyl group, difluoroacetyl group, trifluoroacetyl group, methoxycarbonyl group, ethoxycarbonyl group, aminocarbonyl group, dimethylaminocarbonyl. , Ethyl-methylaminocarbonyl group or diethylamino group.

Rx1 of "Rx1C (= O) O-" in R5 of the formula (1) has the same meaning as defined above. Rx1 is preferably a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 halo. It is an alkoxy group, a C3-C8 cycloalkoxy group, or RaRbN- (wherein Ra and Rb have the same meanings as defined above), and more preferably a C1-C6 optionally substituted with a substituent B. It is an alkyl group, a C1 to C6 haloalkyl group, a C1 to C6 alkoxy group, or RaRbN— (wherein Ra and Rb are as defined above). “Rx1C (═O) O—” is preferably acetyloxy group, methoxyacetyloxy group, cyanoacetyloxy group, propionyloxy group, difluoroacetyloxy group, trifluoroacetyloxy group, cyclopropanecarbonyloxy group, methoxy. Carbonyloxy group, ethoxycarbonyloxy group, 2,2-difluoroethoxycarbonyloxy group, 2,2,2-trifluoroethoxycarbonyloxy group, 3,3,3-trifluoropropyloxycarbonyloxy group, cyclopropyloxycarbonyl Oxy group, aminocarbonyloxy group, methylaminocarbonyloxy group, ethylaminocarbonyloxy group, (methoxymethyl) aminocarbonyloxy group, (2-methoxyethyl) aminocarbonyloxy group, (sia Methyl) aminocarbonyloxy group, (2-cyanoethyl) aminocarbonyloxy group, dimethylaminocarbonyloxy group, ethylmethylaminocarbonyloxy group, diethylaminocarbonyloxy group, (methoxymethyl) methylaminocarbonyloxy group, (2-methoxyethyl ) Methylaminocarbonyloxy group, (cyanomethyl) methylaminocarbonyloxy group, (2-cyanoethyl) methylaminocarbonyloxy group, 2,2-difluoroethylaminocarbonyloxy group, 2,2,2-trifluoroethylaminocarbonyloxy group A group, a cyclopropylaminocarbonyloxy group, a (cyclopropyl) methylaminocarbonyloxy group, a pyrrolidinylcarbonyloxy group, or a piperidinylcarbonyloxy group, Preferably, acetyloxy group, methoxyacetyloxy group, cyanoacetyloxy group, difluoroacetyloxy group, trifluoroacetyloxy group, methoxycarbonyloxy group, ethoxycarbonyloxy group, aminocarbonyloxy group, dimethylaminocarbonyloxy group, It is an ethylmethylaminocarbonyloxy group or a diethylaminocarbonyloxy group.

“Rx2C (═O) N (Rx3) —” in R5 of the formula (1) (wherein Rx2 is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 A haloalkyl group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, a C3 to C8 cycloalkoxy group, or RaRbN- (wherein Ra and Rb have the same meanings as defined above). Rx3 represents a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group). The terms are synonymous with the above definitions. Regarding the “C1 to C6 alkyl group optionally substituted with the substituent B”, in the case of having the substituent B, the hydrogen atom in the C1 to C6 alkyl group is optionally substituted with the substituent B. . Rx2 is preferably hydrogen atom, methyl group, methoxymethyl group, cyanomethyl group, ethyl group, difluoromethyl group, trifluoromethyl group, cyclopropyl group, methoxy group, ethoxy group, 2,2-difluoroethoxy group, 2 , 2,2-trifluoroethoxy group, cyclopropyloxy group, amino group, methylamino group, ethylamino group, (methoxymethyl) amino group, (2-methoxyethyl) amino group, (cyanomethyl) amino group, (2 -Cyanoethyl) amino group, dimethylamino group, ethylmethylamino group, diethylamino group, (methoxymethyl) methylamino group, (2-methoxyethyl) methylamino group, (cyanomethyl) methylamino group, (2-cyanoethyl) methylamino group Group, 2,2-difluoroethylamino group, 2,2,2- Rifluoroethylamino group, cyclopropylamino group, (cyclopropyl) methylamino group, pyrrolidinyl group, or piperidinyl group, more preferably hydrogen atom, methyl group, methoxymethyl group, cyanomethyl group, difluoromethyl group, trifluoromethyl group, It is a fluoromethyl group, a methoxy group, an ethoxy group, an amino group, a dimethylamino group, an ethylmethylamino group, or a diethylamino group. Further, Rx3 is preferably hydrogen atom, methyl group, methoxymethyl group, ethoxymethyl group, cyanomethyl group, ethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-cyanoethyl group, propyl group, 2, 2-difluoroethyl group, 2,2,2-trifluoroethyl group, or cyclopropyl group, more preferably hydrogen atom, methyl group, methoxymethyl group, cyanomethyl group, ethyl group, 2-methoxyethyl group, It is a 2,2-difluoroethyl group or a 2,2,2-trifluoroethyl group.

Hereinafter, the phenyl group having R4 and R5 in the formula (1) will be described in detail.

The phenyl group having R4 and R5 has the formula (Y)

(Wherein R4 and R5 have the same meanings as described above, and n represents an integer of 0 to 4).

N in the formula (Y) represents an integer of 0 to 4.

When n in the formula (Y) is 2 or more, two or more R 5 s each represent an independent substituent, may be the same or different, and can be arbitrarily selected.

In the present specification, the ortho position of the phenyl group means the position of the phenyl group having the substituent R4, as shown in the formula (Y).

The phenyl group in which the substituent R4 is located at the ortho position is a feature of the present invention.

A preferred combination of the substituents of the formula (Y) is 2-R4-phenyl group, 2-R4-6-R5-phenyl group, 2-R4-4-R5-phenyl group, 2-R4-4-R5-6. A -R5-phenyl group, a 2-R4-3-R5-phenyl group, or a 2-R4-3-R5-4-R5-6-R5-phenyl group, and a more preferable combination of substituents is 2-R4. A phenyl group, a 2-R4-6-R5-phenyl group, a 2-R4-4-R5-phenyl group and a 2-R4-4-R5-6-R5-phenyl group. Here, for example, a “2-R4-6-R5-phenyl group” means a disubstituted phenyl group having a substituent R4 at the 2-position and a substituent R5 at the 6-position, and the following description is also the same.

X in the formula (1) represents an oxygen atom or a sulfur atom. Preferred X is an oxygen atom.

The bond including the broken line part in the equation (1) is

Represents a portion represented by.

The bond containing the broken line in formula (1) represents a double bond or a single bond.

When the bond containing the dashed line in Formula (1) is a double bond, Formula (1a)

(In the formula, R1, R2, R4, R5, Het, X, and n have the same meanings as in formula (1).) Or a salt thereof.

In the case where the bond including the broken line in the formula (1) is a single bond, the formula (1b)

When R2 in the formula (1b) is a substituent other than a hydrogen atom, it is either the R isomer or the S isomer, or a mixture of the R isomer and the S isomer at an arbitrary ratio.

The “substituent A” in the formula (1) is a hydroxyl group, a cyano group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, a C3 to C8 cycloalkoxy group, RaRbN— (Wherein Ra and Rb have the same meanings as described above) and Rc-L- (wherein Rc and L have the same meanings as described above). .

Among them, the substituent A is preferably a cyano group, a C1-C6 alkoxy group, or Rc-L- (wherein Rc and L have the same meanings as described above),
Particularly, a cyano group or a C1-C6 alkoxy group is preferable.

For preferred specific examples of the substituent A, a hydroxyl group; a cyano group;
As a C3-C8 cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group;
A methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group as the C1 to C6 alkoxy group;
As the C1 to C6 haloalkoxy group, difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 3,3-difluoropropyloxy group, and 3,3 , 3-trifluoropropyloxy group;
As a C3-C8 cycloalkoxy group, a cyclopropyloxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group;
As RaRbN- (wherein Ra and Rb have the same meanings as described above), an amino group, a methylamino group, an ethylamino group, a (methoxymethyl) amino group, a (2-methoxyethyl) amino group, (cyanomethyl) Amino group, (2-cyanoethyl) amino group, dimethylamino group, ethylmethylamino group, diethylamino group, (methoxymethyl) methylamino group, (2-methoxyethyl) methylamino group, (cyanomethyl) methylamino group, (2 -Cyanoethyl) methylamino group, 2,2-difluoroethylamino group, 2,2,2-trifluoroethylamino group, cyclopropylamino group, (cyclopropyl) methylamino group, pyrrolidinyl group, and piperidinyl group;
And Rc-L- (wherein Rc and L are as defined above) as a methylthio group, a methanesulfinyl group, a methanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, and a trifluoromethanesulfonyl group. is there.

For more preferred specific examples of the substituent A, a hydroxyl group; a cyano group;
As a C3 to C8 cycloalkyl group, a cyclopropyl group and a cyclobutyl group,
As a C1 to C6 alkoxy group, a methoxy group and an ethoxy group,
As the C1 to C6 haloalkoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, and a 2,2,2-trifluoroethoxy group,
As a C3-C8 cycloalkoxy group, a cyclopropyloxy group, and a cyclobutoxy group,
RaRbN- (wherein Ra and Rb are as defined above), a dimethylamino group, an ethylmethylamino group, and a diethylamino group,
And Rc-L- (wherein Rc and L have the same meanings as described above), a methylthio group, a methanesulfinyl group, and a methanesulfonyl group.

The “substituent B” in the formula (1) represents at least one selected from the group consisting of a cyano group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, and a C3 to C8 cycloalkoxy group. .

Among them, the substituent B is preferably a cyano group or a C1-C6 alkoxy group.

For preferred specific examples of the substituent B, a cyano group;
A methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group as the C1 to C6 alkoxy group;
As the C1 to C6 haloalkoxy group, difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 3,3-difluoropropyloxy group, and 3,3 , 3-trifluoropropyloxy group;
Further, the C3-C8 cycloalkoxy group is a cyclopropyloxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

For more preferred specific examples of the substituent B, a cyano group;
As a C1-C6 alkoxy group, a methoxy group and an ethoxy group;
As a C1-C6 haloalkoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, and a 2,2,2-trifluoroethoxy group;
Also, examples of the C3-C8 cycloalkoxy group include a cyclopropyloxy group and a cyclobutoxy group.

The “substituent C” in the formula (1) means a hydroxyl group, a cyano group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, C2. To C6 alkoxyalkoxy group, RaRbN- (wherein Ra and Rb are as defined above), Rc-L- (wherein Rc and L are as defined above), Rx1C (= O)-(wherein Rx1 has the same meaning as described above), and at least one selected from the group consisting of a group of 3 to 6 membered ring containing 1 to 2 oxygen atoms,
Among them, the substituent C is a cyano group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, a C2 to C6 alkoxyalkoxy group, Rc-L- (where Rc and L is as defined above, Rx1C (═O) — (wherein Rx1 has the same meaning as above), or a 3- to 6-membered ring group containing 1 to 2 oxygen atoms. Preferably
Particularly, a cyano group, a C1-C6 alkoxy group, or Rc-L- (wherein Rc and L have the same meanings as described above) is preferable.

For preferred specific examples of the substituent C, a hydroxyl group; a cyano group;
As a C3-C8 cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group;
A methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, and a t-butoxy group as the C1 to C6 alkoxy group;
As the C1 to C6 haloalkoxy group, difluoromethoxy group, trifluoromethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 3,3-difluoropropyloxy group, and 3,3 , 3-trifluoropropyloxy group;
As a C3-C8 cycloalkoxy group, a cyclopropyloxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group;
As a C2-C6 alkoxyalkoxy group, a methoxymethoxy group, an ethoxymethoxy group, a methoxyethoxy group, an ethoxyethoxy group, and a methoxypropyloxy group;
As RaRbN- (wherein Ra and Rb have the same meanings as described above), an amino group, a methylamino group, an ethylamino group, a (methoxymethyl) amino group, a (2-methoxyethyl) amino group, (cyanomethyl) Amino group, (2-cyanoethyl) amino group, dimethylamino group, ethylmethylamino group, diethylamino group, (methoxymethyl) methylamino group, (2-methoxyethyl) methylamino group, (cyanomethyl) methylamino group, (2 -Cyanoethyl) methylamino group, 2,2-difluoroethylamino group, 2,2,2-trifluoroethylamino group, cyclopropylamino group, (cyclopropyl) methylamino group, pyrrolidinyl group, and piperidinyl group;
Rc-L- (wherein Rc and L have the same meanings as described above) as a methylthio group, a methanesulfinyl group, a methanesulfonyl group, a trifluoromethylthio group, a trifluoromethanesulfinyl group, and a trifluoromethanesulfonyl group;
Rx1C (= O)-(wherein Rx1 has the same meaning as above), a formyl group, an acetyl group, a methoxyacetyl group, a cyanoacetyl group, a propionyl group, a difluoroacetyl group, a trifluoroacetyl group, and cyclopropane. Carbonyl group, methoxycarbonyl group, ethoxycarbonyl group, 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 3,3,3-trifluoropropyloxycarbonyl group, cyclopropyloxycarbonyl group , Aminocarbonyl group, methylaminocarbonyl group, ethylaminocarbonyl group, (methoxymethyl) aminocarbonyl group, (2-methoxyethyl) aminocarbonyl group, (cyanomethyl) aminocarbonyl group, (2-cyanoethyl) aminocarbonyl group, dime Ruaminocarbonyl group, ethylmethylaminocarbonyl group, diethylaminocarbonyl group, (methoxymethyl) methylaminocarbonyl group, (2-methoxyethyl) methylaminocarbonyl group, (cyanomethyl) methylaminocarbonyl group, (2-cyanoethyl) methylamino Carbonyl group, 2,2-difluoroethylaminocarbonyl group, 2,2,2-trifluoroethylaminocarbonyl group, cyclopropylaminocarbonyl group, (cyclopropyl) methylaminocarbonyl group, pyrrolidinylcarbonyl group, and piperidi Nylcarbonyl group;
In addition, examples of the 3- to 6-membered ring group containing 1 to 2 oxygen atoms include an oxolanyl group, an oxanyl group, a 1,3-dioxolanyl group, and a 1,3-dioxanyl group.

For more preferable examples of the substituent C, a hydroxyl group; a cyano group;
As a C3 to C8 cycloalkyl group, a cyclopropyl group and a cyclobutyl group;
As a C1-C6 alkoxy group, a methoxy group and an ethoxy group;
As a C1-C6 haloalkoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 2,2-difluoroethoxy group, and a 2,2,2-trifluoroethoxy group;
As a C3-C8 cycloalkoxy group, a cyclopropyloxy group and a cyclobutoxy group;
As a C2-C6 alkoxyalkoxy group, a methoxymethoxy group, an ethoxymethoxy group, a methoxyethoxy group, and an ethoxyethoxy group;
RaRbN- (wherein Ra and Rb have the same meanings as described above), as a dimethylamino group, an ethylmethylamino group, and a diethylamino group;
Rc-L- (wherein Rc and L are as defined above) as a methylthio group, a methanesulfinyl group, and a methanesulfonyl group;
Rx1C (═O) — (wherein Rx1 has the same meaning as above) is a formyl group, acetyl group, methoxyacetyl group, cyanoacetyl group, difluoroacetyl group, trifluoroacetyl group, methoxycarbonyl group, ethoxy. A carbonyl group, an aminocarbonyl group, a dimethylaminocarbonyl group, an ethylmethylaminocarbonyl group, and a diethylaminocarbonyl group;
And a 3- to 6-membered ring group containing 1 to 2 oxygen atoms are a 1,3-dioxolanyl group and a 1,3-dioxanyl group.

The compound represented by the formula (1) may have one or two axial chirality. The isomer ratio at this time is a single ratio or a mixing ratio of an arbitrary ratio, and is not particularly limited.

The compound represented by the formula (1) may contain an asymmetric atom. The isomer ratio at this time is a single ratio or a mixing ratio of an arbitrary ratio, and is not particularly limited.

The compound represented by the formula (1) may include geometrical isomers. The isomer ratio at this time is a single ratio or a mixing ratio of an arbitrary ratio, and is not particularly limited.

The compound represented by the formula (1) may be capable of forming a salt. Acid salts such as hydrochloric acid, sulfuric acid, acetic acid, fumaric acid, and maleic acid, and metal salts such as sodium, potassium, and calcium are exemplified, but are not particularly limited as long as they can be used as agricultural and horticultural fungicides. There is no.

All compounds obtained by arbitrarily combining the preferred ranges of R1, R2, Het, R3, R4, R5, X, n, the bond including the broken line portion, the substituent A, the substituent B, and the substituent C described above. The range of is also described as the range of the formula (1) of the present invention.

Next, specific compounds of the present invention are represented by structural formulas P-1 to P-28 shown in Table 1 (where X in Table 1 is an oxygen atom or a sulfur atom, and a bond including a broken line is Represents a double bond or a single bond) and the structural formula (Y-1 to Y-216) of Y shown in Table 2 (wherein Y represents a phenyl group having R4 and R5), It is represented by a combination with Het shown in Table 3 (where Het has the same meaning as above) (Het-1 to Het-260). These compounds are for illustration only and the invention is not limited thereto.

The method for producing the compound represented by the formula (1) of the present invention is shown below. The method for producing the compound of the present invention is not limited to the production methods A to AL.

[Production method A]

In the formula, Y is

(Wherein R4, R5 and n are as defined above), Z1 is Het (where Het is as defined above) or a C1 to C6 alkyl group, and R6 is hydrogen. Represents an atom or a C1 to C6 alkyl group, and R2, X and Y have the same meanings as defined above.

The production method A is a method for producing a compound represented by the formula (5), which is an intermediate for producing the compound of the present invention, comprising a compound represented by the formula (3) and a compound represented by the formula (4). In a solvent in the presence of a base.

In the compound represented by the formula (3) used in this reaction, the compound in which Z1 is a C1 to C6 alkyl group is obtained as a commercial product, or produced by using a reference example or a known method. be able to.

Among the compounds represented by the formula (3) used in this reaction, the compound in which Z1 is Het can be obtained as a commercial product or can be produced by a known method. Also, Green Chemistry, Vol. 41, pp. 580-585, and The Journal of Organic Chemistry, Vol. 65, No. 20, 6458-6461 (2000). Alternatively, it can be synthesized by referring to US Pat. No. 5,922,718 and the like.

The compound represented by the formula (4) used in this reaction can be obtained as a commercial product or can be produced by a known method.

The amount of the compound represented by the formula (4) used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (3). However, it is usually 1 equivalent or more and 3 equivalents or less.

Bases used in this reaction include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, and tripotassium phosphate, and metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide, and potassium t-butoxide. Etc.

The amount of the base used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 0.01 equivalent or more and 3 equivalents or less with respect to the compound represented by the formula (3). Is.

The solvent used in this reaction is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, a benzene solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene or dichlorobenzene, Ester solvents such as ethyl acetate, isopropyl acetate, butyl acetate, nitrile solvents such as acetonitrile, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl -2-Urea-based solvents such as imidazolidinone, halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, sulfur-based solvents such as dimethyl sulfoxide and sulfolane, acetone, methyl ethyl ketone, methyl Ketone solvents such as Sobuchiruketon like. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (3). is there.

The temperature for carrying out this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually -50 ° C or higher and 150 ° C or lower, or the boiling point of the solvent or lower.

As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- Solvents that are incompatible with water, such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, hydrocarbon solvents such as hexane, heptane, cyclohexane and methylcyclohexane. Can be added. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.

The water content of the reaction mixture containing the compound represented by the formula (5) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (5) obtained above can be distilled under reduced pressure to remove the solvent.

The reaction mixture containing the compound represented by the formula (5) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Production method B]

In the formula, R6a represents a C1 to C6 alkyl group, and R2, X, Y and Z1 have the same meanings as described above.

The production method B is a method for obtaining a production intermediate represented by the formula (5b) among the compounds represented by the formula (5), wherein the compound represented by the formula (5a) is treated under an acidic condition or a base. The production method comprises reacting in a solvent under sexual conditions.

First, I will explain the reaction under acidic conditions.

Examples of the acid used in this reaction include inorganic acids such as hydrochloric acid, hydrobromic acid and phosphoric acid, and organic acids such as acetic acid, methanesulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid. There is no particular limitation as long as the desired reaction proceeds.

The amount of the acid used in this reaction may be a catalytic amount and is not particularly limited as long as the intended reaction proceeds, but is usually 0.01 with respect to the compound represented by the formula (5a). Equivalent or more. Further, a liquid acid can be used as a solvent.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an aqueous solvent, an acidic solvent such as acetic acid or methanesulfonic acid, diethyl ether, diisopropyl ether, methyl-t- Butyl ether, dimethoxyethane, tetrahydrofuran, ether solvents such as dioxane, alcohol solvents such as methanol, ethanol, isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ethyl acetate, isopropyl acetate, acetic acid Ester solvents such as butyl, nitrile solvents such as acetonitrile, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, etc. U A solvent, dichloromethane, dichloroethane, chloroform, and halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (5a). is there.

The temperature for carrying out this reaction is not particularly limited as long as the desired reaction proceeds, but it is usually 0 ° C. or higher and 180 ° C. or lower, or the boiling point of the solvent or lower.

Next, I will explain the reaction under basic conditions.

Examples of the base used in this reaction include inorganic bases such as lithium hydroxide, sodium hydroxide and potassium hydroxide, but the base is not particularly limited as long as the intended reaction proceeds.

The amount of the base used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (5a), but usually 1 equivalent It is above 30 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether such as water solvent, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane. -Based solvents, alcohol-based solvents such as methanol, ethanol and isopropanol, benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ester-based solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitriles such as acetonitrile -Based solvent, amide-based solvent such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea-based solvent such as 1,3-dimethyl-2-imidazolidinone, dichloromethane, dichloroe Down, chloroform, and halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -20 ° C or higher and 180 ° C or lower, or the boiling point of the solvent or lower.

After the reaction, the reaction under acidic condition and the reaction under basic condition can be performed by the common method. Separation operation can be performed by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- Solvents that are incompatible with water, such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, hydrocarbon solvents such as hexane, heptane, cyclohexane and methylcyclohexane. Can be added. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.

The water content of the reaction mixture containing the compound represented by the formula (5b) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (5b) obtained above can be distilled under reduced pressure to remove the solvent.

The reaction mixture containing the compound represented by the formula (5b) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

The compound represented by the formula (5b) is represented by the formula (5b ′)

(In the formula, R2, X, Y and Z1 are as defined above.)
The isomer represented by is also included.

The compound represented by the formula (5b ′) can be treated in the same manner as the compound represented by the formula (5b), and can be applied to, for example, the production method C. Further, the compound represented by the formula (5b ') contains an asymmetric carbon, and the mixing ratio of the isomers may be singly or a mixture having an arbitrary ratio. Further, it may be a mixture of the compound represented by the formula (5b) and the compound represented by the formula (5b '), and the isomer mixture ratio thereof may be a single or a mixture in an arbitrary ratio.

[Production method C]

In the formula, R7 is a hydrogen atom, a hydroxyl group, a cyano group, a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, a C3 to optionally substituted with a substituent A C8 cycloalkyl group, C2-C6 alkenyl group optionally substituted with substituent A, C2-C6 haloalkenyl group, C2-C6 alkynyl group optionally substituted with substituent A, C2- C6 haloalkynyl group, C1 to C6 alkoxy group optionally substituted with substituent A, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group optionally substituted with substituent A, substituted A C2-C6 alkenyloxy group optionally substituted with a group A, a C2-C6 haloalkenyloxy group, a C3-C6 alkynyloxy group optionally substituted with a substituent A, C ~ Haloalkynyloxy group C6, or RaRbN- (wherein, Ra and Rb have the same meanings as defined above.) Represent, R2, R6, X, Y and Z1 are as defined above.

Production method C is a method for obtaining a compound represented by the formula (6), which is a production intermediate of the compound of the present invention, wherein the compound represented by the formula (5) is reacted with R7NH ₂ in the presence of an acid. It is a manufacturing method including the following.

R7NH ₂ used in this reaction can be obtained as a commercial product or can be produced by a known method. R7NH ₂ may be in the form of a salt with an acidic compound such as hydrochloric acid or acetic acid, and is not particularly limited as long as the desired reaction proceeds.

The amount of R7NH ₂ used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (5), and is not particularly limited as long as the intended reaction proceeds, but it is usually It is 1 equivalent or more and 200 equivalents or less.

Examples of the acid used in this reaction include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid, methanesulfonic acid and p-toluenesulfonic acid, and are not particularly limited as long as the intended reaction proceeds. No, but preferably acetic acid. When a salt of R7NH ₂ and an acidic compound is used, the use of an acid is not essential.

The amount of the acid used in this reaction may be 1 equivalent or more based on R7NH ₂ and is not particularly limited as long as the desired reaction proceeds, but is usually 1 equivalent to 200 equivalents. . When the acid used is a liquid, it can be used as a solvent.

A solvent can be used in this reaction, but it is not always essential.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an acidic solvent such as acetic acid or methanesulfonic acid, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxy. Ether-based solvents such as ethane, tetrahydrofuran, dioxane, alcohol-based solvents such as methanol, ethanol, isopropanol, benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, ethyl acetate, isopropyl acetate, butyl acetate, etc. Ester-based solvents, nitrile-based solvents such as acetonitrile, amide-based solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and urea-based solvents such as 1,3-dimethyl-2-imidazolidinone Melting , Dichloromethane, dichloroethane, chloroform, and halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The solvent is preferably an acidic solvent, and more preferably acetic acid.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (5). is there.

The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 50 ° C. or higher and 180 ° C. or lower or the boiling point of the solvent or lower.

The water content of the reaction mixture containing the compound represented by the formula (6) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The solvent of the reaction mixture containing the compound represented by the formula (6) obtained above can be distilled off under reduced pressure as long as the compound is not decomposed.

The reaction mixture containing the compound represented by the formula (6) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Production method D]

In the formula, Lv represents a leaving group such as a methanesulfonyl group, a trifluoromethanesulfonyl group, a p-toluenesulfonyl group, a halogen atom and the like, and R1, R2, X, Y and Z1 are as defined above.

Production method D is a method for obtaining a compound represented by formula (6b) which is an intermediate for producing the compound of the present invention, wherein the compound represented by formula (6a) and R1-Lv are added in the presence of a base, It is a production method including reacting in a solvent.

The compound represented by the formula (6a), which is a raw material of the present invention, is prepared by non-patent documents such as the production method C and Journal of Heterocyclic Chemistry, Volume 20, Item 65-67 (1983). Can be synthesized into a reference.

R1-Lv used in this reaction can be obtained as a commercial product or can be produced by a known method.

Examples of the base used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate and sodium hydride, but are not particularly limited as long as the intended reaction proceeds. It will not be done.

The amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (6a), and is not particularly limited as long as the intended reaction proceeds, but it is usually 1 It is equal to or more than 10 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Methanol, ethanol, alcohol solvents such as isopropanol, benzene, toluene, xylene, mesitylene, chlorobenzene, benzene solvents such as dichlorobenzene, ethyl acetate, isopropyl acetate, ester solvents such as butyl acetate, nitrile solvents such as acetonitrile, Amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, dichloromethane, dichloroethane, Chloroform, halogenated solvents such as carbon tetrachloride, dimethyl sulfoxide, sulfur-based solvents such as sulfolane, acetone, methyl ethyl ketone, ketone solvents such as methyl isobutyl ketone. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (6a). is there.

The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0 ° C. or higher and 150 ° C. or lower, or the boiling point of the solvent or lower.

The water content of the reaction mixture containing the compound represented by the formula (6b) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (6b) obtained above can be evaporated under reduced pressure as long as the compound does not decompose.

The reaction mixture containing the compound represented by the formula (6b) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Production method E]

In the formula, SR represents a sulfurizing agent, and R1, R2, Y and Z1 are as defined above.

The production method E is a method for obtaining the compound represented by the formula (6b-2) among the compounds represented by the formula (6b), wherein the compound represented by the formula (6b-1) and the sulfurizing agent are (SR) is a production method including reacting with (SR) in a solvent.

Examples of the sulfurizing agent used in this reaction include Lawesson's reagent (2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetan-2,4-disulfide).

The amount of the sulfurizing agent used in this reaction may be 0.5 equivalent or more with respect to the compound represented by the formula (6b-1), and is not particularly limited as long as the intended reaction proceeds. However, it is usually 1 equivalent or more and 10 equivalents or less.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Examples thereof include benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 3 times or more and 200 times or more the weight of the compound represented by the formula (6b-1). It is the following.

As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- Solvents that are incompatible with water, such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, hydrocarbon solvents such as hexane, heptane, cyclohexane and methylcyclohexane. Can be added. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. In this reaction, a liquid separation operation is not essential.

The water content of the reaction mixture containing the compound represented by the formula (6b-2) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (6b-2) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.

The reaction mixture containing the compound represented by the formula (6b-2) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Production method F]

In the formula, R2a represents a C1 to C6 alkyl group optionally substituted by the substituent A, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted by the substituent A, a substituent A C2-C6 alkenyl group optionally substituted with A, a C2-C6 haloalkenyl group, a C2-C6 alkynyl group optionally substituted with a substituent A, a C2-C6 haloalkynyl group, or Rx1C (= O)-(wherein Rx1 has the same meaning as described above), and R1, X, Y, Z1 and Lv have the same meaning as described above.

Production method F is the compound represented by formula (6b) in which R2a is optionally substituted with a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, or a substituent A. Optionally substituted C3 to C8 cycloalkyl group, optionally substituted C2 to C6 alkenyl group, C2 to C6 haloalkenyl group, optionally substituted C2 to C6 Is a alkynyl group of C2 to C6, or Rx1C (═O) — (where Rx1 has the same meaning as described above), and a compound represented by the formula (6b-4) Which is a production method comprising reacting a compound represented by the formula (6b-3) with R2a-Lv in a solvent in the presence of a base.

R2a-Lv used in this reaction can be obtained as a commercial product or can be produced by a known method.

The amount of R2a-Lv used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (6b-3), and is not particularly limited as long as the intended reaction proceeds. Usually, it is 1 equivalent or more and 1.8 equivalents or less.

As the base used in this reaction, metal hydrides such as sodium hydride, organic lithiums such as methyllithium, butyllithium, sec-butyllithium, t-butyllithium, and hexyllithium, lithium diisopropylamide, hexamethyldisilazane Examples are metal amides such as lithium, sodium hexamethyldisilazane, and potassium hexamethyldisilazane.

The amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (6b-3), and is not particularly limited as long as the intended reaction proceeds, but is usually It is 1 equivalent or more and 10 equivalents or less.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Examples thereof include benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, and hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 3 times or more and 200 times or more the weight of the compound represented by the formula (6b-3). It is the following.

The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -80 ° C or higher and 100 ° C or lower, or the boiling point of the solvent or lower.

As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- Add solvents that are not compatible with water, such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform, and hydrocarbon solvents such as hexane, heptane, cyclohexane, and methylcyclohexane. Is possible. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.

The water content of the reaction mixture containing the compound represented by the formula (6b-4) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (6b-4) obtained above can be distilled under reduced pressure to remove the solvent.

The reaction mixture containing the compound represented by the formula (6b-4) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Production method G]

In the formula, Ox represents an oxidizing agent, and R1, R2, X, Y and Z1 are as defined above.

The production method G is a method for obtaining a compound represented by the formula (7) which is an intermediate for producing the compound of the present invention, wherein the compound represented by the formula (6b) and the oxidizing agent (Ox) are mixed in a solvent. It is a manufacturing method including reacting with.

Examples of the oxidizing agent used in this reaction include metal oxides such as manganese dioxide, benzoquinones such as 2,3-dichloro-5,6-dicyano-p-benzoquinone, azobisisobutyronitrile and benzoyl peroxide. Radical initiator of N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3- A combination of a halogenating agent such as diiodo-5,5-dimethylhydantoin and the like can be used.

Hereafter, the method in which the oxidizing agent is a metal oxide will be described.

The amount of the oxidizing agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (6b), but it is usually 1 It is equal to or more than 200 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, dichloromethane, dichloroethane, chloroform, Examples thereof include halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but is usually 3 times or more and 200 times or less by weight with respect to the compound represented by the formula (6b). is there.

As a post-treatment of the reaction, it is possible to remove undissolved metals by filtering. Furthermore, a liquid separation operation can be performed by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- Solvents that are incompatible with water, such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, hydrocarbon solvents such as hexane, heptane, cyclohexane and methylcyclohexane. Can be added. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. In this reaction, a liquid separation operation is not essential.

The water content of the reaction mixture containing the compound represented by the formula (7) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (7) obtained above can be evaporated under reduced pressure as long as the compound does not decompose.

The reaction mixture containing the compound represented by the formula (7) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

The following describes the method in which the oxidant is a benzoquinone.

The amount of the oxidizing agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more relative to the compound represented by the formula (6b), but it is usually 1 It is equal to or more than 20 equivalents.

Described below is the method in which the oxidizing agent is a combination of a radical initiator and a halogenating agent.

If the amounts of the radical initiator and the halogenating agent used in this reaction are 0.01 equivalents or more and 1.0 equivalents or more, respectively, with respect to the compound represented by the formula (6b), the desired reaction proceeds. There is no particular limitation as long as it does. Usually, the amount of the radical initiator is from 0.01 to 1 equivalent, and the amount of the halogenating agent is from 1 to 3 equivalents.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but halogenated benzene solvents such as chlorobenzene and dichlorobenzene, and ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate. Examples thereof include solvents, halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, and hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 20 ° C. or higher and 150 ° C. or lower or the boiling point of the solvent or lower.

[Production method H]

In the formula, R2b represents a halogen atom, HalR represents a halogenating agent, and R1, Z1, X and Y have the same meanings as described above.

Production method H is a method for obtaining a compound represented by formula (7b) in which R2b represents a halogen atom, wherein the compound represented by formula (7a) and a halogenating agent (HalR) are used in a solvent. It is a manufacturing method including reacting.

As the halogenating agent used in this reaction, selectfluor (N-fluoro-N'-chloromethyl-triethylenediamine bis (tetrafluoroborate)), N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, bromine, iodine and the like.

The amount of the halogenating agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (7a). It is 1 equivalent or more and 10 equivalents or less. However, the amount of the halogenating agent containing hydantoin is not particularly limited as long as the desired reaction proceeds, as long as it is 0.5 equivalent or more, and is usually 1 equivalent to 5 equivalents.

When the halogenating agent used in this reaction is an iodizing agent, add inorganic acids such as hydrochloric acid and sulfuric acid, and acids such as organic acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid and trifluoromethanesulfonic acid. You can

When the amount of the acid used when the halogenating agent used in this reaction is an iodizing agent is 0.01 equivalent or more with respect to the compound represented by the formula (7a), the desired reaction proceeds. The amount is not particularly limited as long as it is, but usually 0.1 equivalent or more and 3 equivalents or less.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but acidic solvents such as sulfuric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, diethyl ether, etc. , Ether solvents such as diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran and dioxane, alcohol solvents such as methanol, ethanol and isopropanol, benzene solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene. , Ester solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitrile solvents such as acetonitrile, amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide 1,3-dimethyl-2-urea-based solvent-imidazolidinone, dichloromethane, dichloroethane, chloroform, and halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (7a). is there.

The water content of the reaction mixture containing the compound represented by the formula (7b) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (7b) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.

The reaction mixture containing the compound represented by the formula (7b) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Manufacturing method I]

In the formula, Z2 represents a halogen atom, and HalR, R1, R2, X and Y have the same meanings as described above.

Production method I is a method for obtaining a compound represented by formula (7d) in which Z2 is a halogen atom, wherein a compound represented by formula (7c) is added to a radical initiator and a halogenating agent (HalR). It is a production method including subjecting it to a reaction used.

In the formula (7d), preferable Z2 is a chlorine atom, a bromine atom or an iodine atom.

The radical initiator used in this reaction includes azobisisobutyronitrile, benzoyl peroxide and the like.

The amount of the radical initiator used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 0.01 equivalent or more and 1 equivalent to the compound represented by the formula (7c). It is not more than 0.0 equivalent.

The halogenating agent used in this reaction is N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin. , 1,3-diiodo-5,5-dimethylhydantoin and the like.

The amount of the halogenating agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 2 equivalents or more with respect to the compound represented by the formula (7c). It is 2 equivalents or more and 2.8 equivalents or less.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (7c). is there.

The water content of the reaction mixture containing the compound represented by the formula (7d) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (7d) obtained above can be distilled under reduced pressure to remove the solvent.

The reaction mixture containing the compound represented by the formula (7d) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Production method J]

In the formula, R1, R2, X, Y and Z2 are as defined above.

Production method J is a method for obtaining a compound represented by the formula (7e) which is a production intermediate of the compound of the present invention, and comprises hydrolyzing the compound represented by the formula (7d) in the presence of water. It is a manufacturing method.

-Water is essential for this reaction. Further, silver nitrate can be used in order to make the reaction proceed smoothly.

The amount of water used in this reaction is not limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (7d). Water can be used as a solvent.

The amount of silver nitrate used in this reaction is not limited as long as the intended reaction proceeds, as long as it is 2 equivalents or more based on the compound represented by the formula (7d), and usually 2 equivalents or more 10 It is below the equivalent.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether such as water solvent, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane. Examples include system solvents and nitrile solvents such as acetonitrile. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (7d). is there.

The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -10 ° C or higher and 100 ° C or lower or the boiling point of the solvent or lower.

As a post-treatment of the reaction, it is possible to remove undissolved metals by filtering. Furthermore, a liquid separation operation can be performed by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- Solvents that are incompatible with water, such as ether solvents such as t-butyl ether, halogen solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, hydrocarbon solvents such as hexane, heptane, cyclohexane and methylcyclohexane. Can be added. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.

The water content of the reaction mixture containing the compound represented by the formula (7e) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (7e) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.

The reaction mixture containing the compound represented by the formula (7e) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Production method K]

In the formula, Z3 is a hydrogen atom, a cyano group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, or a C3 optionally substituted with a substituent C A C8 cycloalkyl group, a C2-C6 alkenyl group optionally substituted with a substituent C, a C2-C6 haloalkenyl group, a C2-C6 alkynyl group optionally substituted with a substituent C, C2-C6 Haloalkynyl group, C1 to C6 alkoxy group optionally substituted with substituent C, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group optionally substituted with substituent C, substituent A C2-C6 alkenyloxy group optionally substituted by C, a C2-C6 haloalkenyloxy group, a C3-C6 alkynyloxy group optionally substituted by a substituent C, Haloalkynyloxy group of 3 ~ C6 or Rc-L-(wherein, Rc and L have the same meanings as defined above.), Represents, R1, R2, X and Y are as defined above.

In the production method K, Z3 may be optionally substituted with a hydrogen atom, a cyano group, a halogen atom, a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, or a substituent C. A C3 to C8 cycloalkyl group, a C2 to C6 alkenyl group optionally substituted with a substituent C, a C2 to C6 haloalkenyl group, a C2 to C6 alkynyl group optionally substituted with a substituent C, C2 To C6 haloalkynyl group, C1 to C6 alkoxy group optionally substituted with substituent C, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group optionally substituted with substituent C, C2-C6 alkenyloxy group optionally substituted with substituent C, C2-C6 haloalkenyloxy group, C3-C6 alkynyl optionally substituted with substituent C A method for obtaining a compound represented by the formula (7f) which is an oxy group, a C3-C6 haloalkynyloxy group, or Rc-L- (wherein Rc and L have the same meanings as defined above). , A compound represented by the formula (7e) and an organometallic reagent are reacted in a solvent.

Examples of the organometallic reagent used in this reaction include organomagnesium halides (Z3-CH2-Mg-Hal: where Hal represents a halogen atom and Z3 has the same meaning as above) and organolithium reagents (Z3- CH2-Li: Here, Z3 has the same meaning as above.), Organomagnesium halide-zinc (II) ate complex reagent ([(Z3-CH2) 3-Zn]-[Mg-Hal] + [Mg- (Hal) 2] 2: Here, Z3 and Hal have the same meanings as described above. These organometallic reagents can be obtained as commercial products or can be produced by known methods.

The amount of the organometallic reagent used in this reaction may be 1 equivalent or more with respect to the formula (7e) and is not particularly limited as long as the intended reaction proceeds, Usually, it is 1 equivalent or more and 10 equivalents or less.

The solvent used in the reaction is not particularly limited as long as the desired reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, hexane, etc. , Hydrocarbon solvents such as heptane, cyclohexane and methylcyclohexane. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (7e). is there.

As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- It is possible to add an ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane and chloroform, a hydrocarbon solvent such as hexane, heptane, cyclohexane and methylcyclohexane, which is incompatible with water. It is possible. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.

The water content of the reaction mixture containing the compound represented by the formula (7f) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (7f) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.

The reaction mixture containing the compound represented by the formula (7f) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Production method L]

In the formula, Ox ′ represents an oxidizing agent, and R1, R2, X, Y and Z3 have the same meanings as described above.

Production method L is a method for obtaining a compound represented by formula (7g), which comprises reacting the compound represented by formula (7f) with an oxidizing agent (Ox ′) in a solvent. Is.

This production method should be carried out by an oxidation method commonly used by those skilled in the art, such as Dess-Martin oxidation, Swern oxidation, and Parich-Doering oxidation. You can The oxidation reaction is not particularly limited as long as the desired reaction proceeds. Here, the method of the Parrick-Daling oxidation using dimethyl sulfoxide, pyridine-sulfur trioxide complex and a base in a solvent is described.

The amount of dimethyl sulfoxide used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (7f), and it is also used as a solvent. You can also do it.

The amount of the pyridine-sulfur trioxide complex used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (7f). Usually, it is 1 equivalent or more and 20 equivalents or less.

The base used in this reaction includes organic amines such as triethylamine, tributylamine, diisopropylethylamine and the like.

The amount of the base used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (7f), and usually 1 equivalent or more. It is 50 equivalents or less.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but dichloromethane, dichloroethane, chloroform, halogen-based solvents such as carbon tetrachloride, sulfur-based solvents such as dimethyl sulfoxide, etc. Can be mentioned. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (7f). is there.

The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -10 ° C or higher and 150 ° C or lower, or the boiling point of the solvent or lower.

The water content of the reaction mixture containing the compound represented by the formula (7 g) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (7 g) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.

The reaction mixture containing the compound represented by the formula (7 g) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Manufacturing method M]

In the formula, Z4 represents a p-toluenesulfonyl group, a methyl ester group, or an ethyl ester group, and R1, R2, X, Y, and Z3 have the same meanings as described above.

The production method M is a method for obtaining the compound represented by the formula (7h), and the compound represented by the formula (7g) and NH ₂ NH-Z4 (wherein Z4 has the same meaning as described above). The production method includes reacting in a solvent in the presence of an acid.

NH ₂ NH-Z4 used in this reaction can be obtained as a commercially available product or can be produced by a known method. NH ₂ NH-Z4 may be a salt formed with an acidic compound such as hydrochloric acid or sulfuric acid, or NH ₂ NH-Z4 can be used after desalting by a known method in advance. .

The amount of NH ₂ NH-Z4 used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (7g). Usually, it is 1 equivalent or more and 20 equivalents or less.

The acids used in this reaction include organic acids such as acetic acid, methanesulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid.

The amount of the acid used in this reaction may be a catalytic amount and is not particularly limited as long as the intended reaction proceeds, but is usually 0.1 with respect to the compound represented by the formula (7g). Equivalent or more. Further, a liquid acid can be used as a solvent.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Methanol, ethanol, alcohol solvents such as isopropanol, benzene, toluene, xylene, mesitylene, chlorobenzene, benzene solvents such as dichlorobenzene, ethyl acetate, isopropyl acetate, ester solvents such as butyl acetate, nitrile solvents such as acetonitrile, Amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, dichloromethane, dichloroethane, Chloroform, and halogen solvents such as carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (7g). is there.

As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, thiosulfate An aqueous solution or salt solution in which a salt containing a sulfur atom such as sodium or sodium sulfite is dissolved can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.

The water content of the reaction mixture containing the compound represented by the formula (7h) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (7h) obtained above can be distilled under reduced pressure to remove the solvent.

The reaction mixture containing the compound represented by the formula (7h) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Manufacturing method N]

In the formula, R1, R2, X, Y, Z3 and Z4 are as defined above.

The production method N is a method of obtaining the compound represented by the formula (1-a) among the compounds of the present invention represented by the formula (1), wherein the compound represented by the formula (7h) and thionyl chloride are It is a production method including reacting in a solvent.

The amount of thionyl chloride used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 2 equivalents or more based on the compound represented by the formula (7h), but it is usually 2 It is equal to or more than 20 equivalents. Also, thionyl chloride can be used as a solvent.

The amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but is usually 3 times or more and 200 times or less by weight with respect to the compound represented by the formula (7h). is there.

The water content of the reaction mixture containing the compound represented by the formula (1-a) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (1-a) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.

The reaction mixture containing the compound represented by the formula (1-a) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Production method O]

In the formula, Z5 represents a halogen atom, and R1, R2, Z3, X, Y and HalR are as defined above.

Production method O is a method for obtaining a compound represented by formula (7i) in which Z5 represents a halogen atom, wherein the compound represented by formula (7g) and a halogenating agent (HalR) are present in the presence of an acid. , A production method including reacting in a solvent.

The amount of the halogenating agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (7g). It is 1 equivalent or more and 10 equivalents or less. However, the amount of the halogenating agent containing hydantoin is not particularly limited as long as the desired reaction proceeds, as long as it is 0.5 equivalent or more, and is usually 1 equivalent to 5 equivalents.

Examples of the acid used in this reaction include inorganic acids such as hydrochloric acid and sulfuric acid, and acids such as organic acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid and trifluoromethanesulfonic acid.

The water content of the reaction mixture containing the compound represented by the formula (7i) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (7i) obtained above can be evaporated under reduced pressure as long as the compound does not decompose.

The reaction mixture containing the compound represented by the formula (7i) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Manufacturing method P]

In the formula, R1, R2, Z3, Z5, X, and Y have the same meanings as described above.

The production method P is a method for obtaining the compound represented by the formula (1-b) among the compounds of the present invention represented by the formula (1), wherein the compound represented by the formula (7i) and thiourea are combined. , A production method including reacting in a solvent.
The amount of thiourea used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more relative to the compound represented by the formula (7i), but usually 1 equivalent It is above 10 equivalents.

This reaction can be performed in the presence of acid.

The amount of the acid used in this reaction may be a catalytic amount and is not particularly limited as long as the intended reaction proceeds, but is usually 0.1 with respect to the compound represented by the formula (7i). Equivalent or more. Further, a liquid acid can be used as a solvent.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (7i). is there.

The water content of the reaction mixture containing the compound represented by the formula (1-b) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (1-b) obtained above can be evaporated under reduced pressure as long as the compound does not decompose.

The reaction mixture containing the compound represented by the formula (1-b) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Production method Q]

In the formula, Z7 represents a hydrogen atom, a cyano group, or a halogen atom, and R1, R2, Z3, X, and Y have the same meanings as described above.

The production method Q is a method of obtaining the compound represented by the formula (1-c) among the compounds of the present invention represented by the formula (1), A production method comprising reacting sodium nitrate or nitrite with a solvent in the presence of an acid.
First, a method for producing a compound represented by formula (1-c) in which Z7 is a hydrogen atom will be described.
This reaction can be carried out in the presence of an acid, using a combination of sodium nitrite and phosphinic acid.
The amount of sodium nitrite used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1-b). Usually, it is 1 equivalent or more and 10 equivalents or less.

The amount of phosphinic acid used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1-b). It is 1 equivalent or more and 20 equivalents or less.
Examples of the acid used in this reaction include inorganic acids such as hydrochloric acid and sulfuric acid, and acids such as organic acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid and trifluoromethanesulfonic acid.

The amount of the acid used in this reaction may be a catalytic amount and is not particularly limited as long as the intended reaction proceeds, but it is usually 1 with respect to the compound represented by the formula (1-b). Equivalent or more. Further, a liquid acid can be used as a solvent.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is generally 3 times or more and 200 times or more the weight of the compound represented by the formula (1-b). It is the following.

The water content of the reaction mixture containing the compound represented by the formula (1-c) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (1-c) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.

The reaction mixture containing the compound represented by the formula (1-c) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

Next, of the compounds represented by the formula (1-c), Z7 is a hydrogen atom, a production method using nitrites will be described.

Nitrite used in this reaction is not particularly limited as long as the intended reaction proceeds, methyl nitrite, ethyl nitrite, isoamyl nitrite, isobutyl nitrite, isopropyl nitrite, nitrite Examples thereof include t-butyl nitrate, n-propyl nitrite and n-butyl nitrite.

The amount of nitrites used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1-b). Usually, it is 1 equivalent or more and 20 equivalents or less.

Further, a method for producing a compound represented by the formula (1-c) in which Z7 is a cyano group or a halogen atom will be described.
This reaction can be carried out in the presence of an acid, using a combination of sodium nitrite and a copper reagent or an inorganic salt.
The amount of sodium nitrite used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1-b). Usually, it is 1 equivalent or more and 10 equivalents or less.

The copper reagent used in this reaction is a copper reagent containing a halogen atom such as copper chloride, copper bromide, and copper iodide when Z7 is a halogen atom, and a cyano group such as copper cyanide when Z7 is a cyano group. Copper reagents containing groups are mentioned.

The amount of the copper reagent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1-b). It is 1 equivalent or more and 20 equivalents or less.
When Z7 is a halogen atom, inorganic salts used in this reaction include halogen atoms such as sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, and potassium iodide, and Z7 is cyano. In the case of groups, inorganic salts containing a cyano group such as sodium cyanide or potassium cyanide can be mentioned.

The amount of the inorganic salt used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1-b). It is 1 equivalent or more and 20 equivalents or less.

[Production method R]

In the formula, Z6 is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent A C2-C6 alkenyl group optionally substituted with C, a C2-C6 haloalkenyl group, a C2-C6 alkynyl group optionally substituted with a substituent C, or a C2-C6 haloalkynyl group, R1, R2, X and Y are as defined above.

In the production method R, Z6 is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent A C2-C6 alkenyl group optionally substituted with a group C, a C2-C6 haloalkenyl group, a C2-C6 alkynyl group optionally substituted with a substituent C, or a C2-C6 haloalkynyl group. A method for obtaining the compound represented by the formula (7k), which is a production method comprising reacting the compound represented by the formula (7j) with an organometallic reagent in a solvent.

The compound represented by the formula (7j) used in this reaction can be obtained by referring to Reference Examples.

The organometallic reagent used in this reaction includes organomagnesium halides (Z6-Mg-Hal: where Hal represents a halogen atom and Z6 has the same meaning as described above) and organolithium reagents (Z6-Li: Here, Z6 is as defined above.), Organomagnesium halide-zinc (II) ate complex reagent ([(Z6) 3-Zn]-[Mg-Hal] + [Mg- (Hal) 2] 2 : Here, Z6 and Hal have the same meanings as described above.) And the like. These organometallic reagents can be obtained as commercial products or can be produced by known methods.

The amount of the organometallic reagent used in this reaction may be 1 equivalent or more with respect to the formula (7j), and is not particularly limited as long as the intended reaction proceeds, Usually, it is 1 equivalent or more and 10 equivalents or less.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (7j). is there.

The water content of the reaction mixture containing the compound represented by the formula (7k) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (7k) obtained above can be distilled under reduced pressure to remove the solvent.

The reaction mixture containing the compound represented by the formula (7k) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Manufacturing method S]

In the formula, Ox ″ represents an oxidizing agent, and R1, R2, X, Y and Z6 have the same meanings as described above.

Production method S is a method for obtaining a compound represented by the formula (7L), which comprises reacting the compound represented by the formula (7k) with an oxidizing agent (Ox ″) in a solvent. Is the way.

This production method should be carried out by an oxidation method commonly used by those skilled in the art, such as Dess-Martin oxidation, Swern oxidation, and Parich-Doering oxidation. You can The oxidation reaction is not particularly limited as long as the desired reaction proceeds.
By using the compound represented by the formula (7f) in the production method L instead of the compound represented by the formula (7k), the production method S can be carried out according to the production method L.

[Manufacturing method T]

In the formula, R1, R2, X, Y, Z4 and Z6 are as defined above.

The production method T is a method for obtaining the compound represented by the formula (7m), wherein the compound represented by the formula (7L) and NH ₂ NH-Z4 (wherein Z4 has the same meaning as described above). The production method includes reacting in a solvent in the presence of an acid.

The amount of NH ₂ NH—Z4 used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (7L). Usually, it is 1 equivalent or more and 20 equivalents or less.

By using the compound represented by the formula (7g) in the production method M in place of the compound represented by the formula (7L), the production method T can be carried out according to the production method M.

[Manufacturing method U]

In the formula, R1, R2, X, Y, Z4 and Z6 are as defined above.

The production method U is a method for obtaining the compound represented by the formula (1-d) among the compounds of the present invention represented by the formula (1), wherein the compound represented by the formula (7m) and thionyl chloride are It is a production method including reacting in a solvent.

The amount of thionyl chloride used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 2 equivalents or more based on the compound represented by the formula (7m), but usually 2 It is equal to or more than 20 equivalents. Also, thionyl chloride can be used as a solvent.

By using the compound represented by the formula (7h) in the production method N in place of the compound represented by the formula (7m), the production method U can be carried out according to the production method N.

[Manufacturing method V]

In the formula, R1, R2, Z5, Z6, X, Y and HalR are as defined above.

Production method V is a method for obtaining a compound represented by formula (7n), in which Z5 represents a halogen atom, wherein the compound represented by formula (7L) and a halogenating agent (HalR) are present in the presence of an acid. , A production method including reacting in a solvent.

By using the compound represented by the formula (7g) in the production method O instead of the compound represented by the formula (7L), the production method V can be carried out according to the production method O.

[Production method W]

In the formula, R1, R2, Z5, Z6, X, and Y have the same meanings as described above.

The production method W is a method for obtaining the compound represented by the formula (1-e) among the compounds of the present invention represented by the formula (1), wherein the compound represented by the formula (7n) and thiourea are combined. , A production method including reacting in a solvent.

By using the compound represented by the formula (7i) in the production method P instead of the compound represented by the formula (7n), the production method W can be carried out according to the production method P.

[Production method X]

In the formula, R1, R2, Z6, Z7, X, and Y have the same meanings as described above.

The production method X is a method of obtaining the compound represented by the formula (1-f) among the compounds of the present invention represented by the formula (1), and the compound represented by the formula (1-e) is A production method comprising reacting sodium nitrate or nitrite with a solvent in the presence of an acid.

By using the compound represented by formula (1-b) in production method Q in place of the compound represented by formula (1-e), production method X can be carried out according to production method Q. it can.

[Production method Y]

In the formula, J represents an oxygen atom or a sulfur atom, and when J is an oxygen atom, R2c is a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, or a substituent A. An optionally substituted C3 to C8 cycloalkyl group, an optionally substituted C2 to C6 alkenyl group, an optionally substituted C2 to C6 haloalkenyl group, an optionally substituted C3 To C6 alkynyl group or C3 to C6 haloalkynyl group, when J is a sulfur atom, R2c represents a C1 to C6 alkyl group or a C1 to C6 haloalkyl group, and Q represents a hydrogen atom or a metal. , R1, Het, R2b, X and Y are as defined above.

Production method Y is a compound represented by formula (1a), wherein J represents an oxygen atom or a sulfur atom, and when J is an oxygen atom, R2c is a C1 to C6 which may be optionally substituted with a substituent A. An alkyl group, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent A, a C2 to C6 alkenyl group optionally substituted with a substituent A, a C2 to C6 halo. An alkenyl group, a C3 to C6 alkynyl group which may be optionally substituted with a substituent A, or a C3 to C6 haloalkynyl group, and when J is a sulfur atom, R2c is a C1 to C6 alkyl group or C1 to C6 In the presence of a transition metal and a base, wherein R2c-JQ and a compound represented by formula (1-g) are represented by the formula (1-h) Under the solvent Is a manufacturing method comprising obtained by a coupling reaction that.

In the compound represented by the formula (1-g), preferable R2b is chlorine atom, bromine atom or iodine atom.

R2c-JQ used in this reaction can be obtained as a commercial product or can be produced by a known method. Preferred Q is a hydrogen atom or an alkali metal such as sodium or potassium.

The amount of R2c-JQ used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is at least 1 equivalent relative to the compound represented by the formula (1-g). . When Q is a hydrogen atom, it can be used also as a solvent.

The transition metals used in this reaction may have a ligand, and include palladium acetate, [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris (dibenzylideneacetone) dipalladium, tetrakis ( Palladium compounds such as triphenylphosphine) palladium and bis (triphenylphosphine) palladium dichloride.

The amount of transition metal used in this reaction is 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (1-g), but is not particularly limited as long as the intended reaction proceeds. There is no such thing.

In order to proceed this reaction efficiently, triphenylphosphine, 1,1′-bis (diphenylphosphino) ferrocene, 2-dicyclohexylphosphino-2′4′6′-triisopropylbiphenyl, 2-di-t A phosphine ligand such as -butylphosphino-2'4'6'-triisopropylbiphenyl can be added.

The amount of the phosphine ligand used in this reaction is 0.001 equivalent or more and 1 equivalent or less with respect to the compound represented by the formula (1-g), but is not particularly limited as long as the intended reaction proceeds. It will not be done.

The bases used in this reaction include inorganic bases such as sodium carbonate, potassium carbonate and cesium carbonate, and organic bases such as triethylamine, tributylamine and diisopropylethylamine.

The amount of the base used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1-g), but is preferably It is 1 equivalent or more and 50 equivalents or less.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but R2c-JH (wherein R2c has the same meaning as described above and J is an oxygen atom). ) Alcohol solvent represented by), diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran, ether solvent such as dioxane, benzene solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc. Is mentioned. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 3 times or more and 200 times or more the weight of the compound represented by the formula (1-g). It is the following.

The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 30 ° C. or higher and 200 ° C. or lower or the boiling point of the solvent or lower.

As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When using an aqueous solution, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, or a saline solution Etc. can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. It is also possible, but not essential, to remove insolubles by performing a filtration operation.

The water content of the reaction mixture containing the compound represented by the formula (1-h) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (1-h) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.

The reaction mixture containing the compound represented by the formula (1-h) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Production method Z]

In the formula, R2d is a C1 to C6 alkyl group optionally substituted with a substituent A, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent A, a substituent A Represents a C2-C6 alkenyl group which may be optionally substituted with, or a C2-C6 haloalkenyl group, R2d-B represents an organic boronic acid, and R1, Het, R2b, X and Y have the same meanings as described above. ..

Production method Z is a compound represented by formula (1a) in which R2d is optionally substituted with a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, and a substituent A, which may be optionally substituted with a substituent A. A C3 to C8 cycloalkyl group, a C2 to C6 alkenyl group optionally substituted with a substituent A, or a C2 to C6 haloalkenyl group represented by the formula (1-i): A synthetic method, which is obtained by Suzuki-Miyaura coupling in which a compound represented by the formula (1-g) and an organic boronic acid (R2d-B) are reacted in a solvent in the presence of a transition metal and a base. It is a manufacturing method including the above.

In formula (1-g), preferred R2b is chlorine atom, bromine atom, or iodine atom.

R2d-B used in this reaction represents an organic boronic acid such as an organic boronic acid or an organic boronic acid ester, and can be obtained as a commercial product or can be produced by a known method.

The amount of R2d-B used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more relative to the compound represented by the formula (1-g). , And preferably 1 equivalent or more and 10 equivalents or less.

The transition metals used in this reaction are palladium, nickel, ruthenium, etc., and may have a ligand. Preferred are palladium acetate, [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride and the like. Examples include palladiums.

A phosphine ligand such as triphenylphosphine or tricyclohexylphosphine can be added to allow the reaction to proceed efficiently.

The bases used in this reaction are inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate and tripotassium phosphate, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether such as water solvent, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane. Examples of the solvent include benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The water content of the reaction mixture containing the compound represented by the formula (1-i) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (1-i) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.

The reaction mixture containing the compound represented by the formula (1-i) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Production method AA]

In the formula, R2e represents a C2-C6 alkynyl group which may be appropriately substituted with the substituent A, or a C2-C6 haloalkynyl group, and R1, Het, R2b, X and Y have the same meanings as described above.

The production method AA is performed by synthesizing a compound represented by the formula (1a) in which R2e is a C2-C6 alkynyl group optionally substituted by a substituent A, or a C2-C6 haloalkynyl group. j) a method of synthesizing a compound represented by formula (1-g) and a terminal alkyne compound in a solvent in the presence of a transition metal and a base, a Sonogashira coupling It is a manufacturing method including obtaining.

In formula (1-j), preferred R2b is chlorine atom, bromine atom, or iodine atom.

The terminal alkyne compound used in this reaction can be obtained as a commercial product or can be produced by a known method. Further, trimethylsilylacetylene can also be used as the terminal alkyne compound. In this case, it is necessary to introduce a trimethylsilylethynyl group into the compound represented by formula (1a-b) and then perform desilylation. Regarding desilylation, Journal of the American Chemical Society, Vol. 131, No. 2, pp. 634-643 (2009). And Journal of Organometallic Chemistry, Vol. 696, No. 25, pp. 4039-4045 (2011). And the like.

The amount of the terminal alkyne compound used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1-g). It is preferably 1 equivalent or more and 10 equivalents or less.

The transition metals used in this reaction may have a ligand, and include palladium acetate, [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride, tris (dibenzylideneacetone) dipalladium, tetrakis ( Palladium compounds such as triphenylphosphine) palladium and bis (triphenylphosphine) palladium dichloride. In addition, coppers such as copper chloride, copper bromide, and copper iodide are used at the same time.

The amount of transition metals used in this reaction may be 0.001 equivalent or more of palladium and copper and the compound represented by the formula (1a-b), respectively, so that the desired reaction proceeds. There is no particular limitation as long as it does. Preferred amounts are 0.001 equivalent to 1 equivalent in both cases.

Examples of the base used in this reaction include organic amines such as triethylamine, tributylamine, isopropylamine, diethylamine, diisopropylamine and diisopropylethylamine, and inorganic bases such as sodium carbonate, potassium carbonate and cesium carbonate.

The amount of the base used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1-g), but is preferably It is 1 equivalent or more and 50 equivalents or less. In addition, an organic base in a liquid state can be used as a solvent.

A phosphine ligand such as tri-t-butylphosphine or 2-dicyclohexylphosphino-2'4'6'-triisopropylbiphenyl can be added to promote the reaction efficiently, but it is not essential. .

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxyethane, tetrahydrofuran or dioxane, Benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ester-based solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitrile-based solvents such as acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide , Amide solvents such as N, N-dimethylacetamide, urea solvents such as 1,3-dimethyl-2-imidazolidinone, halogen solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, triethylamine, Butylamine, isopropylamine, diethylamine, diisopropylamine, organic amine solvents such as diisopropylethylamine. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, or a saline solution is optional. Can be used for During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield. It is also possible, but not essential, to remove insolubles by performing a filtration operation.

The water content of the reaction mixture containing the compound represented by the formula (1-j) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (1-j) obtained above can be distilled under reduced pressure to remove the solvent.

The reaction mixture containing the compound represented by the formula (1-j) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Production method AB]

In the formula, Rya represents a C1 to C6 alkoxy group, Het1 represents a 5-membered heterocyclic group containing a sulfur atom and a nitrogen atom, and the 5-membered heterocyclic group containing a sulfur atom and a nitrogen atom is R3. Are appropriately substituted, and R1, R2, X, Y and the broken line portion have the same meanings as described above.

Production method AB is a method for synthesizing a compound represented by the formula (1-L) having a hydroxyl group among the compounds represented by the formula (1), wherein Rya is a C1 to C6 alkoxy group ( 1-k) is a production method which comprises obtaining a compound represented by 1-k) and an acid in a solvent.

The acids used in this reaction include boron halides such as boron trichloride and boron tribromide.

The amount of the acid used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1-k) and is not particularly limited as long as the intended reaction proceeds, but is preferably Is 1 equivalent or more and 10 equivalents or less.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is a benzene solvent such as benzene, toluene, xylene, mesitylene, chlorobenzene, or dichlorobenzene, and a nitrile solvent such as acetonitrile. , Halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride, and hydrocarbon-based solvents such as hexane, heptane, cyclohexane and methylcyclohexane. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 3 times or more and 200 times or more the weight of the compound represented by the formula (1-k). It is the following.

As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When using an aqueous solution, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, ammonium chloride, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, or a saline solution Etc. can be used arbitrarily. During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.

The water content of the reaction mixture containing the compound represented by the formula (1-L) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (1-L) obtained above can be evaporated under reduced pressure as long as the compound is not decomposed.

The reaction mixture containing the compound represented by the formula (1-L) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Manufacturing method AC]

In the formula, Ryb is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent A C2-C6 alkenyl group optionally substituted with C, a C2-C6 haloalkenyl group, a C3-C6 alkynyl group optionally substituted with a substituent C, a C3-C6 haloalkynyl group, or Rx1C (= O)-(Rx1 has the same meaning as described above), and Lv, R1, R2, Het1, X, Y and the broken line have the same meaning as described above.

The production method AC is a compound represented by the formula (1), in which Ryb—O— may be optionally substituted with a substituent C, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, and a substituent C Optionally substituted with a C3 to C8 cycloalkoxy group, a C2 to C6 alkenyloxy group optionally substituted with a substituent C, a C2 to C6 haloalkenyloxy group, a substituent C optionally substituted with Or a C3-C6 alkynyloxy group, a C3-C6 haloalkynyloxy group, or Rx1C (= O) O- (Rx1 is as defined above) and represented by formula (1-m). A method for synthesizing a compound, which comprises reacting the compound represented by the formula (1-L) with Ryb-Lv in a solvent in the presence of a base.

Ryb-Lv used in this reaction can be obtained as a commercial product or can be produced by a known method.

The amount of Ryb-Lv used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1-L), and is not particularly limited as long as the intended reaction proceeds. , And preferably 1 equivalent or more and 10 equivalents or less.

As the base used in this reaction, inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate and sodium hydride, and organic bases such as triethylamine, tributylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, collidine and lutidine Examples thereof include, but are not particularly limited as long as the desired reaction proceeds.

The amount of the base used in this reaction may be 1 equivalent or more with respect to the compound represented by the formula (1-L), and is not particularly limited as long as the intended reaction proceeds, but is preferably Is 1 equivalent or more and 10 equivalents or less.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 3 times or more and 200 times or more the weight of the compound represented by the formula (1-L). It is the following.

The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -20 ° C or higher and 150 ° C or lower, or the boiling point of the solvent or lower.

The water content of the reaction mixture containing the compound represented by the formula (1-m) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (1-m) obtained above can be evaporated under reduced pressure as long as the compound does not decompose.

The reaction mixture containing the compound represented by the formula (1-m) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Manufacturing method AD]

In the formula, Ryc represents a halogen atom, Ryd represents a C1 to C6 alkyl group optionally substituted by a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 optionally substituted by a substituent C. Represents a cycloalkyl group, a C2-C6 alkenyl group which may be optionally substituted with a substituent C, or a C2-C6 haloalkenyl group, Ryd-B represents an organic boronic acid, and R1, R2, Het1, X , Y and the broken line portion have the same meanings as described above.

The production method AD is a compound represented by the formula (1) in which Ryd is appropriately substituted with a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, and a substituent C which may be optionally substituted with a substituent C. A C3 to C8 cycloalkyl group, a C2 to C6 alkenyl group optionally substituted with a substituent C, or a C2 to C6 haloalkenyl group represented by the formula (1-o) A synthetic method, which is obtained by Suzuki-Miyaura coupling in which a compound represented by the formula (1-n) and an organic boronic acid (Ryd-B) are reacted in a solvent in the presence of a transition metal and a base. It is a manufacturing method including the above.

In the compound represented by the formula (1-n), preferable Ryc is a chlorine atom, a bromine atom or an iodine atom.

Ryd-B used in this reaction represents an organic boronic acid such as an organic boronic acid or an organic boronic acid ester, and can be obtained as a commercial product or can be produced by a known method.

Production Method Z by using the compound represented by Formula (1-g) and R2d-B in Production Method Z instead of the compound represented by Formula (1-n) and Ryd-B, respectively. The manufacturing method AD can be carried out according to.

[Manufacturing method AE]

In the formula, Rye represents a C2 to C6 alkynyl group which may be appropriately substituted with a substituent C, or a C2 to C6 haloalkynyl group, and Ryc, R1, R2, X, Y, Het1 and the broken line portion are as described above. Are synonymous.

The production method AE is a compound represented by the formula (1) wherein Rye is a C2-C6 alkynyl group optionally substituted with a substituent C, or a C2-C6 haloalkynyl group. p) a method for synthesizing a compound represented by formula (1-n) and a terminal alkyne compound in the presence of a transition metal and a base in a solvent, Sonogashira coupling It is a manufacturing method including obtaining.

By using the compound represented by the formula (1-g) in the production method AA instead of the compound represented by the formula (1-n), the production method AE can be carried out according to the production method AA. .

[Manufacturing method AF]

In the formula, Ryf represents a halogen atom, Het2 represents a 5-membered heterocyclic group containing a sulfur atom and a nitrogen atom, and the 5-membered heterocyclic group containing a sulfur atom and a nitrogen atom is substituted with R3 as appropriate. , HalR, R1, R2, X, Y and the broken line portion are as defined above.

The production method AF is a production method for obtaining a compound represented by the formula (1-r) in which Ryf is a halogen atom among the compounds represented by the formula (1), wherein at least one substituent is substituted for Het2. It is a production method which comprises reacting the compound represented by the formula (1-q) having a hydrogen atom with a halogenating agent (HalR) in a solvent.

As the halogenating agent used in this reaction, selectrofluor (N-fluoro-N'-triethylenediamine bis (tetrafluoroborate)), N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 1 , 3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, bromine, iodine and the like.

The amount of the halogenating agent used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1-q). It is preferably 1 equivalent or more and 10 equivalents or less. However, the amount of the halogenating agent containing hydantoin is not particularly limited as long as the desired reaction proceeds as long as the amount is 0.5 equivalent or more, and is preferably 1 equivalent to 5 equivalents.

When the amount of the acid used when the halogenating agent used in this reaction is an iodizing agent is 0.01 equivalent or more relative to the compound represented by the formula (1-q), the desired reaction It is not particularly limited as long as it proceeds, but it is preferably 0.1 equivalent or more and 3 equivalents or less.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 3 times or more and 200 times or more the weight of the compound represented by the formula (1-q). It is the following.

The water content of the reaction mixture containing the compound represented by the formula (1-r) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (1-r) obtained above can be evaporated under reduced pressure as long as the compound does not decompose.

The reaction mixture containing the compound represented by the formula (1-r) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Manufacturing method AG]

In the formula, R5c represents a halogen atom, and R5a may be optionally substituted with a cyano group, a C1 to C6 alkoxy group optionally substituted with a substituent C, a C1 to C6 haloalkoxy group, or a substituent C. A C3 to C8 cycloalkoxy group, a C2 to C6 alkenyloxy group optionally substituted with a substituent C, a C2 to C6 haloalkenyloxy group, a C3 to C6 alkynyl optionally substituted with a substituent C An oxy group, a C3-C6 haloalkynyloxy group, RaRbN- (wherein Ra and Rb are as defined above), or Rc-L- (wherein Rc and L are as defined above). , And R1, R2, R4, Het, Q, X and the broken line portion have the same meanings as described above.

Production method AG is a compound represented by formula (1) in which R5a is a cyano group, a C1 to C6 alkoxy group optionally substituted with a substituent C, a C1 to C6 haloalkoxy group, a substituent C Optionally substituted with a C3 to C8 cycloalkoxy group, a C2 to C6 alkenyloxy group optionally substituted with a substituent C, a C2 to C6 haloalkenyloxy group, a substituent C optionally substituted with C3 to C6 alkynyloxy group, C3 to C6 haloalkynyloxy group, RaRbN- (wherein Ra and Rb have the same meanings as described above), or Rc-L- (herein, Rc and L). Is the same as defined above.) In the method of synthesizing a compound represented by the formula (1-t), wherein the compound represented by the formula (1-s) and R5a-Q are optionally a base. In the presence of A production method comprising reacting.

R5a-Q used in this reaction can be obtained as a commercial product. Preferred Q is a hydrogen atom or an alkali metal such as sodium or potassium.

The amount of R5a-Q used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is at least 1 equivalent to the compound represented by the formula (1-s). , And preferably 1 equivalent or more and 30 equivalents or less. When Q represents a hydrogen atom, it can be used as a solvent.

In some cases, the base used in this reaction is preferably an inorganic base such as sodium carbonate, potassium carbonate, cesium carbonate or sodium hydride. When Q is an alkali metal, the use of a base is not essential.

In some cases, the amount of the base used in this reaction is not particularly limited as long as the intended reaction proceeds, as long as it is 1 equivalent or more with respect to the compound represented by the formula (1-s). It is preferably 1 equivalent or more and 30 equivalents or less.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is an alcohol solvent represented by R5a-H, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dimethoxy. Ether-based solvents such as ethane, tetrahydrofuran and dioxane, benzene-based solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene, ester-based solvents such as ethyl acetate, isopropyl acetate and butyl acetate, nitrile-based solvents such as acetonitrile, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and other amide solvents, 1,3-dimethyl-2-imidazolidinone and other urea solvents, dichloromethane, dichloroethane, chloroform, carbon tetrachloride etc Halogenated solvents, dimethylsulfoxide, sulfur-based solvents such as sulfolane, acetone, methyl ethyl ketone, ketone solvents such as methyl isobutyl ketone. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually 3 times or more and 200 times or more by weight that of the compound represented by the formula (1-s). It is the following.

As a post-treatment of the reaction, it is possible to carry out a liquid separation operation by adding water or an appropriate aqueous solution to the reaction mixture. When an aqueous solution is used, an acidic aqueous solution in which hydrochloric acid, sulfuric acid, or the like is dissolved, an alkaline aqueous solution in which potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like is dissolved, or a saline solution is optional. Can be used for During the liquid separation operation, if necessary, a benzene solvent such as toluene, xylene, benzene, chlorobenzene, dichlorobenzene, an ester solvent such as ethyl acetate, isopropyl acetate, butyl acetate, diethyl ether, diisopropyl ether, methyl- An ether solvent such as t-butyl ether, a halogen solvent such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, a hydrocarbon solvent such as hexane, heptane, cyclohexane, methylcyclohexane, etc. It is possible to add. In addition, these solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio. The number of liquid separations is not particularly limited, and can be carried out according to the desired purity and yield.

The water content of the reaction mixture containing the compound represented by the formula (1-t) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (1-t) obtained above can be evaporated under reduced pressure as long as the compound does not decompose.

The reaction mixture containing the compound represented by the formula (1-t) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

[Production method AH]

In the formula, R5aa represents a C1 to C6 alkoxy group which may be appropriately substituted with a substituent C, and R1, R2, R4, X, Het and the broken line have the same meanings as described above.

The production method AH is a method for synthesizing a compound represented by the formula (1-v) having a hydroxyl group among the compounds represented by the formula (1), wherein R5aa is a C1 to C6 alkoxy group ( 1-u) is a production method which comprises obtaining the compound represented by 1-u) by reacting with an acid in a solvent.

By using the compound represented by formula (1-k) in production method AB instead of the compound represented by formula (1-u), production method AH can be carried out according to production method AB. .

[Manufacturing method AI]

In the formula, R5b is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent C An optionally substituted C2-C6 alkenyl group, a C2-C6 haloalkenyl group, an optionally substituted C3-C6 alkynyl group, a C3-C6 haloalkynyl group, or Rx1C ( = O)-(Rx1 has the same meaning as described above), and Lv, R1, R2, R4, Het, X and the broken line have the same meaning as described above.

The production method AI is a compound represented by the formula (1), in which R5b-O- is a C1 to C6 alkoxy group, C1 to C6 haloalkoxy group or a substituent C in which R5b-O- may be appropriately substituted with a substituent C. Optionally substituted with a C3 to C8 cycloalkoxy group, a C2 to C6 alkenyloxy group optionally substituted with a substituent C, a C2 to C6 haloalkenyloxy group, a substituent C optionally substituted with Or a C3 to C6 alkynyloxy group, a C3 to C6 haloalkynyloxy group, or Rx1C (═O) O— (Rx1 has the same meaning as defined above). A method for synthesizing a compound, which comprises reacting a compound represented by the formula (1-v) with R5b-Lv in a solvent in the presence of a base.

The R5b-Lv used in this reaction can be obtained as a commercial product or can be produced by a known method.

By using the compound represented by formula (1-L) in production method AC instead of the compound represented by formula (1-v), production method AI can be carried out according to production method AC. .

[Manufacturing method AJ]

In the formula, R5d is a C1 to C6 alkyl group optionally substituted with a substituent C, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group optionally substituted with a substituent C, a substituent C Represents a C2 to C6 alkenyl group which may be optionally substituted with, or a C2 to C6 haloalkenyl group, R5d-B represents an organic boronic acid, R1, R2, R4, R5c, X, Het and a broken line part It is synonymous with the above.

The production method AJ is a compound represented by the formula (1) in which R5d is appropriately substituted with a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, and a substituent C which may be optionally substituted with a substituent C. A C3 to C8 cycloalkyl group, a C2 to C6 alkenyl group optionally substituted with a substituent C, or a C2 to C6 haloalkenyl group represented by the formula (1-x): A synthetic method, which is obtained by Suzuki-Miyaura coupling in which a compound represented by the formula (1-s) and an organic boronic acid (R5d-B) are reacted in a solvent in the presence of a transition metal and a base. It is a manufacturing method including the above.

In the compound represented by the formula (1-s), preferable R5c is a chlorine atom, a bromine atom or an iodine atom.

By using the compound represented by formula (1-n) in production method AD instead of the compound represented by formula (1-x), production method AJ can be carried out according to production method AD. .

[Manufacturing method AK]

In the formula, R5e represents a C2 to C6 alkynyl group which may be appropriately substituted with a substituent C, or a C2 to C6 haloalkynyl group, and R1, R2, R4, R5c, X, Het and the broken line portion are as described above. Are synonymous.

The production method AK is a compound represented by the formula (1-) in which R5e is a C2-C6 alkynyl group which may be optionally substituted with a substituent C, or a C2-C6 haloalkynyl group in the compound represented by the formula (1). y) a method for synthesizing a compound represented by the formula (1-s), wherein Sonogashira coupling is carried out by reacting the compound represented by the formula (1-s) with a terminal alkyne compound in the presence of a transition metal and a base. It is a manufacturing method including obtaining.

By using the compound represented by formula (1-n) in production method AE instead of the compound represented by formula (1-s), production method AK can be carried out according to production method AE. .

[Manufacturing method AL]

In the formula, La represents S, Lb represents SO or SO ₂ , and Ox ′ ″ represents an oxidizing agent.

The production method AL is represented by the formula (Lb) in which Rb contained in R2, R3, R4, R5, the substituent A and the substituent C in the compound represented by the formula (1) is SO or SO _2. A method for producing a compound, which is represented by formula (La) in which R contained in the compound represented by formula (1) is R2, R3, R4, R5, Substituent A and Substituent C is S. A production method comprising reacting a compound and an oxidizing agent (Ox ′ ″) in a solvent.

Examples of the oxidizing agent used in this reaction include hydrogen peroxide solution and peroxides such as meta-chloroperbenzoic acid. Also, transition metals such as sodium tungstate can be added.

The amount of the oxidizing agent used in this reaction is usually 1.0 equivalent or more and 1.2 equivalents or less with respect to the compound represented by the formula (La) when SO is produced, and SO ₂ is produced. When doing, it is usually 2 equivalents or more and 10 equivalents or less. When adding transition metals, the amount is usually 0.001 equivalent or more and 1 equivalent or less.

The solvent used in this reaction is not particularly limited as long as the intended reaction proceeds, but it may be an aqueous solvent, an acidic solvent such as acetic acid, benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene or the like. Examples thereof include benzene-based solvents, nitrile-based solvents such as acetonitrile, halogen-based solvents such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride. These solvents can be used alone or as a mixture of two or more kinds at an arbitrary ratio.

The amount of the solvent used in this reaction is not particularly limited as long as the desired reaction proceeds, but is usually 3 times or more and 200 times or less the weight of the compound represented by the formula (La). is there.

The temperature for carrying out this reaction is not particularly limited as long as the intended reaction proceeds, but it is usually -10 ° C or higher and 120 ° C or lower or the boiling point of the solvent or lower.

The water content of the reaction mixture containing the compound represented by the formula (Lb) obtained above can be removed with a desiccant such as sodium sulfate or magnesium sulfate, but it is not essential.

The reaction mixture containing the compound represented by the formula (Lb) obtained above can be distilled under reduced pressure to remove the solvent.

The reaction mixture containing the compound represented by the formula (Lb) obtained after evaporation of the solvent can be purified by washing, reprecipitation, recrystallization, column chromatography and the like with an appropriate solvent. What is necessary is just to set suitably according to the objective purity.

The compounds represented by the formula (1) can be produced by arbitrarily combining the production methods A to AL shown above. Alternatively, the compound represented by the formula (1) can be produced by arbitrarily combining the known method and the production methods A to AL.

Since the compound of the present invention can control organisms harmful to plants, it can be used as an agricultural chemical. Specific examples include fungicides, insecticides, herbicides, plant growth regulators, and the like. A bactericide is preferable.

The compound of the present invention can be used as a fungicide for agricultural and horticultural use for controlling plant diseases in fields, paddy fields, tea fields, orchards, meadows, lawns, forests, gardens, roadside trees and the like.

The plant diseases referred to in the present invention are crops, flowers, flowers, trees, wilting of plants such as trees, systemic abnormal pathological symptoms such as wilting, yellowing, atrophy, and captivity, or spots, leaf wilting, mosaic. , Partial morbidity such as cigar, wilting, root rot, root-knot, and hump are caused. That is, the plant becomes ill. Pathogens causing plant diseases mainly include fungi, bacteria, spiroplasma, phytoplasma, viruses, viroids, parasitic higher plants, nematodes and the like. The compound of the present invention is effective on fungi, but is not limited thereto.

The diseases caused by fungi are mainly fungal diseases. Fungi (pathogens) which cause fungal diseases include fungus fungi, oomycetes, zygomycetes, ascomycetes, basidiomycetes and incomplete fungi. For example, as fungus fungi, root-knot fungus, powdery mildew fungus, sugar beet wilt fungus, oomycete, downy mildew, Pythium genus, Aphanomyces genus, zygomycetes Rhizopus genus, ascomycetes Fungi include peach leaf blight, corn sesame leaf blight, rice blast, powdery mildew, anthracnose, red mold, bacillus seedling, sclerotium, basidiomycetes, rust, smut, and purple print Fungi, blast fungus, sheath blight fungus, and imperfect fungi include gray mold, Alternaria, Fusarium, Penicillium, Rhizoctonia, and white silk.

The compound of the present invention is effective against various plant diseases. Hereinafter, specific examples of the disease name and the pathogen name will be shown.

Rice blast (Magnaporthe grisea), sheath blight (Thanatephorus cucumeris), brown rot (Ceratobasidium setariae), brown sclerotium (Waitea circinata), brown spot rot spelling bacterium (Therca erucorus phus) Sclerotium hydrophilum, red rot (Wairea circinata), black rot (Entyloma dactylidis), pneumococcal disease (Magnaporthe salvinii leaf blight, Ceratobosa sigma rot) Blight disease (Sphaerulina oryzina) , Frog seedling disease (Gibberella fujikuroi), seedling blight (Pythium spp., Fusarium spp., Trichoderma spp., Rhizopus spp., Rhizonia spore, Rhizoctonia spore, Rhizoptonia solipani, Ms. Rhizotonia sol. Achlya spp., Dictyuchus spp.), Rice scab (Clavipesps virens), Black smut (Tilletia barclayana), Brown rice (Curvularia spp., Alternaria spp., Yellow wilt disease, Alternaria spp., Yellowing disease) Xanthomonas oryzae pv. Oryzae, brown streak (Acidovora) avenae subsp. oryzae), strain rot (Erwinia chrysanthemi), yellow dwarf (Phytoplasma oryzae), Rice stripe tenuivirus, dwarf disease (Rice dwarf revirus);
Powdery mildew of wheat (Blumeria graminis f. Sp. Hordei; f. Sp. Tritici), rust (Puccinia striiformis, Puccinia graminis, Puccinia reconitia, Puccinia reconia, Puccinia reconia, Puccinia reconitia, Puccinia reno) disease Pyrenophora teres), Fusarium zeae, Fusarium culmorum, Fusarium avenaceum, Monographella nivalis, Snow rot (Typhula incarina, Typhula inicarina, Typhula iniganeis raisulai sushi) nuda), fishy smell smut (Tilletia caries, Tilletia controversa), Memonbyo (Pseudocercosporella herpotrichoides), stock rot (Ceratobasidium gramineum), scald (Rhynchosporium secalis), leaf blight (Septoria tritici), glume blotch (Phaeosphaeria nodorum), Fusarium spp., Pythium spp., Rhizoctonia spp., Septoria spp., Pyrenophora spp.), Wilt blight (Gaeumanomyces gramminolitis) Ergot (Claviceps purpurea), Leaf spot (Cochliobolus sativus), Black spot (Pseudomonas syringae pv. Syringae);
Fusarium aveneum, Penicillium spp., Pythium spp., Rhizoctonia spp., Pustinia sprouts, Pustinia sorghum blight, Puccinia sorghum blight (Puccinia sorghum) (Utilago maydis), Anthrax (Colletotrichum graminicola), Northern spot (Cochliobolus carbonum), Brown streak (Acidovorax avenae ssp. ), Fusarium wilt disease (Erwinia stewartii); Grape downy mildew (Plasmopara viticola), rust (Physopella ampelopsidis), powdery mildew (Uncinula necrotor, Elus erin aelin erin aelin erin aelin ell erin ella melin elsa) , Colletotrichum acutatum, black rot (Guignardia bidwellii), vine disease (Phomopsis viticola), soybean spot disease (Zygophiala jamaicensis), gray mold disease (Broterisea stomach disease) Helicobasidium mompa), white crest Disease (Rosellinia necatrix), apical carcinoma disease (Agrobacterium vitis); powdery mildew of apples (Podosphaera leucotricha), scab (Venturia inaealia, red leaf sprouts (Alternaria ganaria nymph) Diseases (Monilinia mali), rot (Valsa ceratosperma), ring spot (Botryosphaeria berengeriana), anthrax (Colletotrichum acutatum espodia, gomaella singula sigma, swelling) ena), black spot disease (Mycosphaerella pomi), purple root rot (Helicobasium momopa), white root rot (Rosellinia necatrix), blight disease (Phomopsis mali, Diaporthe tanako papaya tanako papaya) Injury and disease (Erwinia amylovora), apical carcinoma (Agrobacterium tumefaciens), hairy root disease (Agrobacterium rhizogenes);
Pear black spot (Alternaria kikuchiana), scab (Venturia nasicola), scab (Gymnosporangium asiaticum), ring spot (Botryosphaeria wisp, sclerosis, sclerosis, sclerosis, and so on). Erwinia sp.), Apical carcinoma (Agrobacterium tumefaciens), rust blight (Erwinia chrysanthemi pv. Chrysanthemi), and flower rot bacterial disease (Pseudomonas syringa. s ringae), bacterial wilt disease (Erwinia sp.); peach scab (Cladosporium carpophilum), homopsis rot (Phomopsis sp.), plague (Phytophthora spp.), and anthrax (Colletotrophithosporium). deformans), perforated bacterial disease (Xhanthomonas campestris pv. pruni), apical carcinoma disease (Agrobacterium tumefaciens); cherry anthracnose (Glomerella singulata), and germ fungus sclerosis (Milica koniota milion) ), Apical carcinoma (Agrobacter) um tumefaciens, resinous bacterial disease (Pseudomonas syringae pv. syringae); oyster anthracnose (Glomerella singulata), deciduous disease (Cercospora kaki, sickness of Mycosphaerakaya kana; tumefaciens; citrus black spot (Diaporthe citri), green mold (Penicillium digitatum), blue mold (Penicillium italicum), scab (Elsinoe thawthophthia, brown rot, phthophtha, and rot) omonas campestris pv. citri), brown spot bacterial disease (Pseudomonas syringae pv. syringae), greening disease (Liberactor asiaticus), apical carcinoma (Agrobacterium tumefaciens);
Botrytis cinerea such as tomato, cucumber, beans, strawberries, potatoes, cabbage, eggplant, lettuce; sclerotinia sclerotium such as tomato, cucumber, beans, strawberry, potato, rapeseed, cabbage, eggplant, lettuce ); Tomato, cucumber, legumes, radish, watermelon, eggplant, rapeseed, bell pepper, spinach, sugar beet, and various other types of seedling wilt (Rhizoctonia spp., Pythium spp., Fusarium spp., Phylophthroprosa sp., Etc.) Rustonia solanacearum of Solanaceae; downy mildew of cucurbits (Pseudoperonospora cubens); s), powdery mildew (Sphaerotheca fuliginea), anthracnose (Colletotrichum orbiculare), vine blight (Didymella bryoniae), Fusarium disease (Fusarium oxysporum), plague (Phytophthora parasitica, Phytophthora melonis, Phytophthora nicotianae, Phytophthora drechsleri, Phytophthora capsici Etc.), brown spot bacterial disease (Xhanthomonas campestris pv. Cucurbitae), soft rot (Erwinia carotovora subsp. Carotovora), spot bacterial disease (Pseudomonas syri) ... Gae pv lachrymans), edges bacterial grain rot (Pseudomonas marginalis pv marginalis), temple petitioner disease (Streptomyces sp), root disease (Agrobacterium rhizogenes), cucumber mosaic virus (Cucumber mosaic virus);
Tomato ring rot (Alternaria solani), leaf mold (Fulvia fulva), plague (Phytophthora infestans), wilt (Fusarium oxysporum), root rot (Pythium myriotium sulcus) Diseases (Claviobacter michiganensis), Stem Necrotic Bacterial Disease (Pseudomonas corrugata), Black Spot Bacterial Disease (Pseudomonas viridiflava), Soft Rot (Erwinia carrotova sp. ytoplasma asteris), yellow dwarf (Tobacco leaf curl subgroup III geminivirus); Brown spot bacterial disease (Pseudomonas cichorii), stem nematode bacterial disease (Pseudomonas corrugata), stem rot bacterial disease (Erwinia chrysanthemi), soft rot (Erwinia carotovora spores, spores of spores, spores, spores, spores, spores, spores and germs). Black rot (Alternaria brassicae), black rot (Xhanthomonas campestris pv. Campestris), black rot (Pseudomonas syringae pv. Eravia kuroa eroa var. Etc.), white spot disease (Cercosporella brassicae), root rot disease (Pharma lingam), clubroot disease (Plasmodiophora brassicae), downy mildew (Peronospora sarcoma, black rot sampa sampa samposa, black rot) Pseudomonas sy ringae pv. maculicola), soft rot (Erwinia carotovora subsp. carotovora);
Cabbage plant rot (Thanatephorus cucumeris), yellow rot (Fusarium oxysporum), black scab (Alternaria brassicicola); Chinese cabbage rot (Rhizotnia sulnia erutia succinata) ), Black leaf spot (Alternaria porri), white silk spot (Sclerotium rolfsii), white plague (Phytophthora porri), black rot fungus (Sclerotium sepivorum); Carot vora), spot bacterial disease (Pseudomonas syringae pv. syringae), rot (Erwinia rhapontici), scale rot (Burkholderia gladioli rot), and yellow rot (Phytoplasa saunia rot). Disease (Pseudomonas marginalis pv. Marginalis); soybean purpura (Cercospora kikuchii), black rot (Elsinoe glycines), black spot (Diaporthe phasoolz, rhizopha spores and lysophia rotoh rotoh rotonia sarcopodium) e), downy mildew (Peronospora manshurica), rust (Phakopsora pachyrhizi), anthrax (Colletotrichum truncatum, etc.), leaf blight (Xanthomonas camps pesgos pest. Anthrax (Colletotrichum lindemutianum), bacterial wilt (Ralstonia solanacearum), scab (Pseudomonas syringae pv. Phaseolicola), brown spot bacterial disease (Pseudomonas visamrais virions virion virion virion virion sv. . phaseoli);
Peanut black spot (Mycosphaerella berkeleyi), brown spot (Mycosphaerella arachidis), bacterial wilt (Ralstonia solanacearum); pea powdery mildew (Erysiphe psi), porphyra spermosis, downy mildew (Personia alba) syringae pv. pisi), vine rot (Xhanthomonas campestris pv. pisi); downy mildew (Peronospora viciae), plague (Phytophthora nicotianae); , Plague (Phyt ophthora infestans, silver scab (Helminthosporium solani), dry rot (Fusarium oxysporum, Fusarium solani), sponge scab (Spongospora serrata serrata), and bacterial wilt (Ralson scrotum). ), Scab (Streptomyces scabies, Streptomyces acidiscabies), soft rot (Erwinia carotovora subsp. sp. sepedonicus); Streptomyces ipomoea; Streptomyces leaf spot (Cercospora beticola), downy mildew (Peronospora schaecchia), Black root (Aphanomyces eschariis). Agrobacterium tumefaciens, Streptomyces scabies, Pseudomonas syringae pv. Aptata;
Bacterial leaf blight of carrots (Alternaria dauci), club scab (Rhizobacter dauci), apical carcinoma (Agrobacterium tumefaciens), Streptomyces scab (Streptomyces spop. Strawberry powdery mildew (Sphaerotheca aphanis var. Aphanis), plague (Phytophthora nicotianae, etc.), anthrax (Glomerella singulata, etc.), fruit rot (Pythium ultimum), bacterial rot (Stithium ultimum), Xanthomonas sclera campestris), Bacterial blight (Pseudomonas marginalis pv. Marginalis); tea leaf blast (Exobasidium reticulatus red scabies), anthracnose (Elsinoe leucospilatus vulgaris) syringae pv.theae), scab (Xhanthomonas campestris pv.theicola), witches' broom (Pseudomonas sp.); tobacco scab (Alternaria alternae), powdery mildew (Ericorrhea) hum gloeosporioides), late blight (Phytophthora nicotianae), Wildfire Disease (Pseudomonas syringae pv.tabaci), Huang and bacterial diseases (Pseudomonas syringae pv.mellea), cavity disease (Erwinia carotovora subsp. carotovora), damping off (Ralstonia solanacearum) , Tobacco mosaic virus;
Rust of coffee (Hemileia vastatrix); Black sigatoga disease of banana (Mycosphaerella fijiensis), Panama disease (Fusarium oxysporum f. Sp cubense); Cotton wilt disease (Fusaria moria, R. sarcoa) Sclerotinia sclerotiorum, Xanthomonas campestris pv. Malvacearum, Scab disease (Erwinia carotovora subsp. Fusarium sickness (Sphaerotheca pannosa, etc.), plague (Phytophthora megasperma), downy mildew (Peronospora sparsa), root carcinoma (Agrobacterium tumefaciens), chrysanthemum spore spore spore spore spore spore spore spore spore spore spore spore spore spore spore spore spore sb. ), Plague (Phytophthora actorum), spot bacterial disease (Pseudomonas ichorii), soft rot (Erwinia carotovora subsp. ifolia); turf brown patch disease (Rhizoctonia solani), dollar spot disease (Sclerotinia homoeocarpa), curvularia leaf blight (Curvularia sp.), rust (Puccinia zoysia sp. , Scallops (Rynchosporium secalis), wilt (Gaeumannomyces graminis), anthrax (Colletotrichum sp.), Snow rot brown sclerotia (Typhula incarnata), snow rot black sclerophyll sari shirahi shira shira shira shira shira shira shira shira shira shira shira shira shira shikotsuka Bacterial bacterial rot (Myriosclerotinia borealis), fairy ring disease Marasmius Oreades etc.), Pythium disease (Pythium aphanidermatum, etc.), blast (Pyricularia grisea), and the like.

The compound of the present invention may be used as the present compound alone, but is preferably mixed with a solid carrier, a liquid carrier, a gas carrier, a surfactant, a fixing agent, a dispersant, a stabilizer, etc., and a powder or wettable powder. , Granule wettable powder, aqueous solvent, granular aqueous solution, granule, emulsion, solution, microemulsion, aqueous suspension preparation, aqueous emulsion preparation, suspoemulsion preparation and the like. The composition is not limited as long as the effect is exhibited.

Specific formulation examples are shown below, but the invention is not limited to these.

[Formulation Example 1 Flowable]
Compound of the present invention (10 parts by mass), sodium salt of formaldehyde condensate of naphthalenesulfonic acid (5 parts by mass), polyoxyethylene arylphenyl ether (1 part by mass), propylene glycol (5 parts by mass), silicon-based antifoaming agent ( 0.1 parts by mass), xanthan gum (0.2 parts by mass), ion-exchanged water (78.7 parts by mass) to form a slurry, and further wet milling using glass beads having a diameter of 1.0 mm with Dynomill KDL. To obtain a flowable agent.

[Formulation Example 2 Emulsion]
The compound of the present invention (5 parts by mass) is dissolved in a mixed solution of xylene (40 parts by mass) and cyclohexane (35 parts by mass), and Tween 20 (20 parts by mass) is added and mixed with the solution to obtain an emulsion.

[Formulation Example 3 wettable powder]
Compound of the present invention (10 parts by mass), white carbon (10 parts by mass), polyvinyl alcohol (2 parts by mass), sodium salt of dioctylsulfosuccinate (0.5 part by mass), sodium salt of alkylbenzenesulfonic acid (5 parts by mass), calcining Diatomaceous earth (10 parts by mass) and kaolinite clay (62.5 parts by mass) are sufficiently mixed and pulverized with an air mill to obtain a wettable powder.

The application of the composition of the present invention (agricultural / horticultural pest control agent, agricultural / horticultural fungicide) will be described below.

Examples of the method of applying the composition containing the compound of the present invention include a method of contacting with a plant or seed, or a method of adding the composition to cultivated soil and contacting with a root or rhizome of a plant. As specific examples, foliage spraying treatment, injection treatment, seedling box treatment, cell tray treatment, spraying treatment on plant seeds, spray treatment on plant seeds, immersion treatment on plant seeds, immersion treatment on plant seeds on plant seeds of the composition Dressing, spraying on the soil surface, soil mixing after spraying on the soil surface, injection into the soil, soil mixing after injection in the soil, soil irrigation, after soil irrigation Soil mixing and the like. In general, any method of application as used by those skilled in the art will work well.

The term “plant” as used in the present invention refers to a plant that performs photosynthesis and lives without exercise. Specific examples include rice, wheat, barley, corn, coffee, banana, grape, apple, pear, peach, cherry, oyster, citrus, soybean, bean, cotton, strawberry, potato, cabbage, lettuce, tomato, cucumber, eggplant, Watermelon, sugar beet, spinach, snow pea, pumpkin, sugar cane, tobacco, bell pepper, sweet potato, taro, konjac, cotton, sunflower, rose, tulip, chrysanthemum, turf, etc. and their F1 varieties and the like can be mentioned. In addition, it includes genetically modified crops that are produced by manipulating genes and the like and are not originally present in the natural world.For example, soybeans, corn, cotton, etc. that have been imparted with herbicide resistance, such as rice adapted to cold regions. And agricultural and horticultural crops, such as corn and cotton, to which insecticide-producing ability is imparted. Further, trees such as pine, ash, ginkgo, maple, oak, poplar, zelkova and the like can be mentioned. The “plant” in the present invention is a general term for all parts constituting the above-mentioned plant individual, and includes, for example, stems, leaves, roots, seeds, flowers, fruits and the like.

The term “seed” as used in the present invention refers to a seed that stores nutrients for germination of young plants and is used for agricultural reproduction. Specific examples include seeds of corn, soybeans, cotton, rice, sugar beet, wheat, barley, sunflower, tomato, cucumber, eggplant, spinach, snow peas, pumpkin, sugar cane, tobacco, peppers, oilseed rape, and their F1 varieties. Examples include seeds, seed potatoes such as taro, potato, sweet potato, and konjac, edible lilies, bulbs such as tulips, seed balls such as rakkyo, and seeds and tubers of genetically modified crops.

The application rate and application concentration of the composition containing the compound of the present invention vary depending on the target crop, target disease, degree of disease occurrence, dosage form of the compound, application method and various environmental conditions, but when spraying or irrigating. Is suitably 0.1 to 10,000 g per hectare, and preferably 10 to 1,000 g per hectare. In the case of seed treatment, the amount used is 0.0001 to 1000 g, preferably 0.001 to 100 g, per 1 kg of seeds as the amount of active ingredient. When the composition containing the compound of the present invention is used as a foliage spraying treatment on a plant individual, a spraying treatment on a soil surface, an injection treatment into soil or a soil irrigation treatment, the composition is diluted with an appropriate carrier at an appropriate concentration. Thereafter, the processing may be performed. When the composition containing the compound of the present invention is brought into contact with a plant seed, it may be diluted to an appropriate concentration and then immersed, dressed, sprayed or smeared on the plant seed before use. The amount of the composition used in the case of dipping, dressing, spraying or smearing is usually about 0.05 to 50%, preferably 0.1 to 30% of the weight of dry plant seeds as the amount of active ingredient. Is suitable, but it may be appropriately set depending on the form of the composition and the kind of plant seed to be treated, and is not limited to these ranges.

The composition containing the compound of the present invention, if necessary, other pesticides, for example, fungicides, insecticides, acaricides, nematicides, herbicides, pesticides such as biological pesticides and plant growth regulators, nucleic acids. It can be used as a mixture with a disease controlling agent (International Publication No. 2014/062775) containing as an active ingredient, a soil conditioner or a fertilizer. As a method of mixing and using the compound of the present invention and another pesticide, a method of formulating and using the compound of the present invention and another pesticide in one dosage form, and both methods in which each is formulated in a separate dosage form Are used before and after use, or both are separately formulated in separate dosage forms, or both are formulated in separate dosage forms. And then use the other.

Specific components contained in the bactericide that can be used by mixing with the compound of the present invention are exemplified in the following group b, and include salts, isomers and N-oxides thereof. However, the known disinfectants are not limited to these.

Group b:
b-1: Phenylamide fungicide As a phenylamide fungicide, [b-1.1]: benalaxyl (benalaxyl), [b-1.2] benalaxyl M or chiralaxyl (benalaxyl-M or chiralaxyl), [b -1.3] Furalaxyl, [b-1.4] Metalaxyl, [b-1.5] Metalaxyl M or Mephenoxam (Metalaxyl-M or mefenoxam), [b-1.6] Oxadixyl (-) oxadixyl), [b-1.7] off-race, and the like.

b-2: mitotic cell division and cell division inhibitor As a mitotic cell division and cell division inhibitor, [b-2.1] benomyl, [b-2.2] carbendazim, [b- 2.3] fuberidazole, [b-2.4] thiabendazole, [b-2.5] thiophanate, [b-2.6] thiophanate-methyl, [b- 2.7] Diethofencarb, [b-2.8] zoxamide, [b-2.9] ethaboxam, [b-2.10] pencycuron, [b-2. 11] Full opico Lido (fluopicolide), [b-2.12] phenamacril and the like can be mentioned.

b-3: Succinate dehydrogenase inhibitor (SDHI agent)
As a succinate dehydrogenase inhibitor (SDHI agent), [b-3.1] benodanil, [b-3.2] benzobindiflupyr, [b-3.3] bixaphen (bixafen) ), [B-3.4] boscalid, [b-3.5] carboxin, [b-3.6] fenfuram, [b-3.7] fluopyram. , [B-3.8] flutolanil, [b-3.9] fluxapyroxad, [b-3.10] furametpyr, [b-3.11] isofetamide (isofetamide). ), [B-3.12] isopyrazam (isop razam), [b-3.13] mepronil, [b-3.14] oxycarboxin, [b-3.15] penthiopyrad, [b-3.16] penflufen ( penflufen), [b-3.17] pydiflumethofen, [b-3.18] sedaxane, [b-3.19] thifluzamide, [b-3.20] pyradiflumide. (Pyraziflumid) and the like.

b-4: Quinone external inhibitor (QoI agent)
As a quinone external inhibitor (QoI agent), [b-4.1] azoxystrobin, [b-4.2] cumoxystrobin, [b-4.3] dimoxist Robin (dimoxystrobin), [b-4.4] enoxastrobin (enoxastrobin), [b-4.5] famoxadone, [b-4.6] fenamidone, [b-4.7. ] Phenamine stroben, [b-4.8] fluphenoxystrobin, [b-4.9] fluoxastrobin, [b-4.10] kresoxim-methyl (kresoxim-me) hyl), [b-4.11] mandestrobin, [b-4.12] metaminostrobin, [b-4.13] orysastrobin, [b-4.14]. Picoxystrobin, [b-4.15] pyraclostrobin, [b-4.16] pyrametostrobin, [b-4.17] pyraoxystrobin , [B-4.18] pyribencarb, [b-4.19] triclopyricarb, [b-4.20] trifloxystrobin. obin), and the like.

b-5: quinone internal inhibitor (QiI agent)
Examples of the quinone internal inhibitor (QiI agent) include [b-5.1] cyazofamide and [b-5.2] amisulbrom.

b-6: Oxidative phosphorylation uncoupling inhibitor As an oxidative phosphorylation uncoupling inhibitor, [b-6.1] binapacryl (binapacryl), [b-6.2] meptyldinocap, [b-6.2] Examples thereof include b-6.3] dinocap and [b-6.4] fluazinam.

b-7: quinone external stigmaterin-binding subsite inhibitor (QOSI agent)
Examples of the quinone external stigmaterin-binding subsite inhibitor (QOSI agent) include [b-7.1] amethoctrazine.

b-8: Amino acid biosynthesis inhibitor As an amino acid biosynthesis inhibitor, [b-8.1] cyprodinil, [b-8.2] mepanipyrim, and [b-8.3] pyrimethanil (pyrimethanil). ) And the like.

b-9: Protein biosynthesis inhibitor [b-9.1] streptomycin, [b-9.2] blasticidin S (blasticidin-S), [b-9. 3] Kasugamycin, [b-9.4] oxytetracycline and the like.

b-10: Signal transduction inhibitor As a signal transduction inhibitor, [b-10.1] fenpiclonil, [b-10.2] fludioxonil, [b-10.3] quinoxyphen, [B-10.4] proquinazid, [b-10.5] chlorozolinate, [b-10.6] dimethaclone, [b-10.7] iprodione, [b -10.8] procymidone, [b-10.9] vinclozoline and the like can be mentioned.

b-11: Lipid and Cell Membrane Biosynthesis Inhibitors [b-11.1] edifenphos, [b-11.2] iprobenphos, [b-11.3] as lipid and cell membrane biosynthesis inhibitors. ] Pyrazophos, [b-11.4] isoprothiolane, [b-11.5] biphenyl, [b-11.6] chloroneb, [b-11.7] dichlorane (Dicloran), [b-11. 8] quintozene, [b-11. 9] tecnazene, [b-11.10] tolclofos-methyl, [b-11.11]. Etridiazole (ec hlomezol or etridiazole), [b-11.12] iodocarb, [b-11.13] propamocarb, [b-11.14] prothiocarb, and the like.

b-12: Demethylation inhibitor (DMI agent)
Examples of demethylation inhibitors (DMI agents) include [b-12.1] azaconazole, [b-12.2] bitertanol, [b-12.3] bromuconazole, and [b-12.3] bromuconazole. [b-12.4] cyproconazole, [b-12.5] difenoconazole, [b-12.6] diniconazole, [b-12.7] diniconazole M (diniconazole-M) ), [B-12.8] epoxyconazole, [b-12.9] ethaconazole, [b-12.10] phenarimol, [b-12.11]. Fenbuconazole, [b-12.12] fluquinconazole, [b-12.13] quinconazole, [b-12.14] flusilazole, [b-12] .15] Flutriafol, [b-12.16] hexaconazole, [b-12.17] imazalil, [b-12.18] imibenconazole, [B-12.19] ipconazole, [b-12.20] metconazole, [b-12.21] microbutanil , [B-12.22] nuarimol, [b-12.23] oxpoconazole, [b-12.24] oxpoconazole fumarate, [b- 12.25] pefurazoate, [b-12.26] penconazole, [b-12.27] prochloraz, [b-12.28] propiconazole, [b- 12.29] Prothioconazole, [b-12.30] Pyrifenox, [b-12.31] Pyrisoxazole, [b-12.32] Cimeconazole, [b-12.33] tebuconazole, [b-12.34] tetraconazole, [b-12.35] triadimefone, [b-12.36]. Triadimenol, [b-12.37] triflumizole, [b-12.38] triforine, [b-12.39] triticonazole [b-12] .40] mefentrifluconazole, [b-12.41] ipfentrifluconazole, and the like.

b-13: Amine-based bactericide As amine-based bactericide, [b-13.1] aldimorph, [b-13.2] dodemorph, [b-13.3] fenpropimorph ), [B-13.4] tridemorph, [b-13.5] phenpropidin, [b-13.6] piperalin, [b-13.7] spiroxamine. ) And the like.

b-14: 3-keto reductase inhibitor in C4 demethylation of sterol biosynthesis [b-14.1] phenhexamide as a 3-keto reductase inhibitor in C4 demethylation of sterol biosynthesis (Fenhexamid), [b-14.2] fenpyrazamine, and the like.

b-15: Squalene epoxidase inhibitor for sterol biosynthesis As a squalene epoxidase inhibitor for sterol biosynthesis, [b-15.1] pyributicarb (b-15.2) naphthifine (naftifine), [b] -15.3] Terbinafine and the like can be mentioned.

b-16: Cell wall biosynthesis inhibitor As a cell wall biosynthesis inhibitor, [b-16.1] polyoxins (polyoxins), [b-16.2] dimethomorph, [b-16.3] flumorph ( flumorph), [b-16.4] pyrimorph, [b-16.5] bench avalicarb, [b-16.6] bench avalicarb isopropyl (b). -16.7] iprovalicarb, [b-16.8] mandipropamide, [b-17.9] valifenalate and the like can be mentioned.

b-17: Melanin biosynthesis inhibitor As a melanin biosynthesis inhibitor, [b-17.1] phtalide or phthalide, [b-17.2] pyroquilon, [b-17.3] tricyclazole. (Tricylazole), [b-17.4] carpropamide, [b-17.5] diclocymet, [b-17.6] phenoxanil, [b-17.7] tolprocarb. ) And the like.

b-18: Host plant resistance inducer [b-18.1] acibenzolar S-methyl (acibenzalar-S-methyl), [b-18.2] probenazole (b), and [b-18.2] -18.3] thiazinyl (tiadinil), [b-18.4] isotianil, [b-18.5] laminarin and the like can be mentioned.

b-19: Dithiocarbamate fungicide As a dithiocarbamate fungicide, [b-19.1] mancozeb or manzeb (mancozeb or manzeb), [b-19.2] manneb, [b-19.3]. ] Metiram, [b-19.4] propineb, [b-19.5] thiuram, [b-19.6] zineb, [b-19.7] ziram (Ziram), [b-19.8] ferbam and the like.

b-20: Phthalimide bactericide As phthalimide bactericide, [b-20.1] captan (captan), [b-20.2] captafol (captafol), [b-20.3] folpet (folpet) ), [B-20.4] fluorofolpet and the like.

b-21: Guanidine fungicide As a guanidine fungicide, [b-21.1] guazatin, [b-21.2] iminoctadine, [b-21.3] iminoctadine albesylate (Imnoctadine albesilate), [b-21.4] iminoctadine triacetate and the like.

b-22: Multi-action point contact active type bactericide [b-22.1] basic copper chloride (copper oxychloride), [b-22.2] cupric hydroxide (Copper (II) hydroxide), [b-22.3] basic copper sulfate (copper hydroxide sulfate), [b-22.4] organic copper compound (organocopper compound), [b-22.5] dodecylbenzene sulfone Acid bisethylenediamine copper complex salt [II] (Dodecylbenzene sulphonic acid bisethylenediamineamine copper [II] salt, DBEDC), [b-22.6] sulphur, [b-22.7] fluorimide (fluorim). de), [b-22.8] chlorothalonil, [b-22.9] diclofluanid, [b-22.10] tolylfluanid, [b-22.11]. Anilazine, [b-22.12] dithianon, [b-22.13] quinomethionate or quinomethionate, [b-22.14] extract from cotyledon of Japanese bean seedling (BLAD), etc. Is mentioned.

b-23: Other fungicides As other fungicides, [b-23.1] diclobentiazox, [b-23.2] fenpicoxamide, [b-23.3]. ] Dipymetitron, [b-23.4] bupyrimate, [b-23.5] dimethirimol, [b-23.6] ethirimol, [b-23.7] acetic acid Triphenyl tin (fentin acetate), [b-23.8] triphenyl tin chloride (fentin chloride), [b-23.9] triphenyl tin hydroxide (fentin hydroxide), [b-23.10] oxolinic acid (Oxo linic acid), [b-23.11] hymexazol, [b-23.12] octilinone, [b-23.13] fosetyl, [b-23.14] phosphite. (Phosphorus acid), sodium salt of [b-23.15] phosphite (sodium phosphite), ammonium salt of [b-23.16] phosphite (ammonium phosphite), [b-23.17] phosphite. Potassium salt of acid (potassium phosphite), [b-23.18] tecloftalam, [b-23.19] triazoxide, [b-23.20] fursulfamide. [B-23.21] dichromezine, [b-23.22] silthiofam, [b-23.23] diflumetrim, [b-23.24] metasulphocarb, [B-23.25] cyflufenamide, [b-23.26] metrafenone, [b-23.27] pyriophenone, [b-23.28] dodine, [b] -23.29] flutianil, [b-23.30] ferrimzone, [b-23.31] oxathiapiproline, [b-23. 32] tebufloquine, [b-23.33] picarbutrazox, [b-23.34] validamycins, [b-23.35] cymoxanil, [b- 23.36] quinofumelin,

[B-23.37] Expression (s1)

(See WO 98/046607),

[B-23.38] Expression (s2)

(See WO 08/148570),

[B-23.39] Expression (s3)

(See WO 92/012970),

[B-23.40] Expression (s4)

A compound represented by the following formula (see International Publication No. 12/084812):

[B-23.41] Expression (s5)

A compound (gougerotin) represented by

[B-23.42] Expression (s6)

A compound (ningnanmycin) represented by:

[B-23.43] Expression (s7)

(See WO 10/136475),

[B-23.44] Expression (s8)

(See WO 14/010737),

[B-23.45] Expression (s9)

(See WO 11/085084),

[B-23.46] Expression (s10)

(See WO 11/137002),

[B-23.47] Expression (s11)

(See WO 13/162072),

[B-23.48] Expression (s12)

(See WO 08/110313),

[B-23.49] Expression (s13)

A compound represented by (see International Publication No. 09/156098),

[B-23.50] Expression (s14)

(See WO 12/025557),

[B-23.51] Expression (s15)

(See WO 14/006945),

[B-23.52] Expression (s16)

[In the formula, A3 represents a hydrogen atom, a halogen atom, a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, or a cyano group, and A4 represents a hydrogen atom, a C1 to C6 alkyl group, a C1 to C6 It represents a haloalkyl group or a C3-C8 cycloalkyl group. (See WO 14/095675),

[B-23.53] Expression (s17)

[In the formula, m1 represents an integer of 0 to 3, A5 and A6 are each independently a halogen atom or a C1 to C6 alkyl group, and A7 and A8 are each independently, When a halogen atom or a C1 to C6 alkoxy group is represented, and m1 is 2 or more, 2 or more A7's each independently represent a substituent, which may be the same or different. (See WO09 / 137538 and WO09 / 137651),

[B-23.54] Expression (s18)

[In the formula, A9 and A10 each independently represent a hydrogen atom or a halogen atom, A11 represents a halogen atom, A12 represents a halogen atom or a C1 to C6 alkyl group, and A13 represents Represents a halogen atom, a cyano group, a C1 to C6 alkyl group, or a C1 to C6 alkoxy group. ] (See WO 12/031061),

[B-23.55] Expression (s19)

[In the formula, m2 represents an integer of 0 to 6, A14 and A15 each independently represent a halogen atom, a cyano group, or a C1 to C6 alkyl group, and A16 represents a hydrogen atom or a halogen atom. Or a C1 to C6 alkoxy group, A17 represents a halogen atom or a C1 to C6 alkoxy group, and when m2 is 2 or more, 2 or more A17's each independently represent a substituent, Can be different. (See WO 05/121104),

[B-23.56] Expression (s20)

[In the formula, A18 and A19 each independently represent a halogen atom, a cyano group, or a C1 to C6 alkyl group, and A20, A21, and A22 each independently represent a hydrogen atom, a halogen atom, Alternatively, it represents a C1 to C6 alkoxy group. (See WO 07/066601),

[B-23.57] Expression (s21)

[In the formula, A23 and A24 each independently represent a hydrogen atom, a halogen atom, a C1-C6 alkyl group, or a C3-C8 cycloalkyl group, and X represents an oxygen atom or a sulfur atom. (See WO 07/087906, WO 09/016220, WO 10/130767),

[B-23.58] Expression (s22)

[Wherein, m3 represents an integer of 0 to 5, A25 represents a halogen atom, a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, Alternatively, when it represents a C3 to C8 cycloalkyl group, and m3 is 2 or more, 2 or more A25's each independently represent a substituent, which may be the same or different. (See WO 13/092224),

[B-23.59] Expression (s23)

[In the formula, A26 represents a hydrogen atom or a halogen atom, and V1 and V2 each independently represent an oxygen atom or a sulfur atom. (See WO 12/025450),

[B-23.60] Expression (s24) or Expression (s25)

[Wherein, m4 represents an integer of 0 to 5, A27 represents a C1 to C6 alkyl group, A28 represents a halogen atom, a cyano group, a C1 to C6 alkyl group, or a C1 to C6 haloalkyl group. And when m4 is 2 or more, two or more A28's each independently represent a substituent and may be the same or different, and A29 is a C1 to C6 alkyl group, a C2 to C6 alkenyl group, or C3. Represents a C6 alkynyl group. ] (See WO 13/037771),

[B-23.61] Expression (s26) or Expression (s27)

[Wherein, m5 represents an integer of 0 to 5, A30 represents a C1 to C6 alkyl group, A31 represents a halogen atom, a cyano group, a C1 to C6 alkyl group, or a C1 to C6 haloalkyl group. When m5 is 2 or more, 2 or more A31's each independently represent a substituent, and may be the same or different, and A32's are C1 to C6 alkyl groups, C2 to C6 alkenyl groups, or C3. Represents a C6 alkynyl group. ] (See WO 13/037771),

[B-23.62] Expression (s28)

[Wherein A33, A34, A35 and A36 are each independently a hydrogen atom or a halogen atom, and A37 represents a hydrogen atom, an acetyl group or a benzoyl group. (See WO 06/031631, WO 10/069882),

[B-23.63] Expression (s29)

[In the formula, A38 represents a C1-C6 alkyl group or a C1-C6 haloalkyl group, and A39 and A40 each independently represent a hydrogen atom or a halogen atom. (See WO 14/043376),

[B-23.64] Expression (s30)

[In the formula, A41 represents a hydrogen atom, a sulfur group (-SH), a thiocyanate group (-SCN), or a C1 to C6 alkylthio group, and A42, A43, A44 and A45 are each independently Represents a hydrogen atom or a halogen atom. ] The compound represented by these (refer international publication 09/077443),

[B-23.65] Expression (s31) or Expression (s32)

[In the formula, A46 represents a hydrogen atom or a halogen atom, A47 represents a C1-C6 alkyl group, and A48 represents a halogen atom. (See WO 11/070771),

[B-23.66] Expression (s33)

[Wherein, A49, A50 and A51 each independently represent a hydrogen atom or a halogen atom. (See International Publication No. 11/081174).

Specific components contained in the insecticide that can be used as a mixture with the compound of the present invention are exemplified in the following group c, and include salts, isomers and N-oxides thereof. However, known insecticides are not limited to these.

Group c:
c-1: Carbamate acetylcholinesterase (AChE) inhibitor [C-1.1] phosphocarb, [c-1.2] alanycarb, [c-1.1] as a carbamate acetylcholinesterase (AChE) inhibitor -1.3] butocarboxim, [c-1.4] butoxycarboxim, [c-1.5] thiodicarb, [c-1.6] thiophanox ), [C-1.7] aldicarb, [c-1.8] bendiocarb, [c-1.9] benfuracarb, [c-1.10] carbaryl (carba). ryl), [c-1.11] carbofuran, [c-1.12] carbosulfan, [c-1.13] ethiofencarb, [c-1.14] phenocarb. fenobcarb, [c-1.15] formetanate, [c-1.16] furatiocarb, [c-1.17] isoprocarb, [c-1.18] methiocarb. , [C-1.19] methomyl, [c-1.20] oxamyl, [c-1. 21] pirimicab, [c-1. 22] propoxur, c-1.23] trimetacarb, [c-1.24] XMC (3,5-xylyl methylcarbamate), [c-1.25] allyxycarb, [c-1.26] aldoxicarb (Aldoxycarb), [c-1.27] bufencarb, [c-1.28] butacarb, [c-1.29] carbanolate, [c-1.30] metolcarb. ), [C-1.31] xylylcarb (xylylcarb), [c-1.32] phenothiocarb, [c-1.33] xylylcarb, [c-1.34] bendiocarb. bendiocarb), and the like.

c-2: Organophosphorus acetylcholinesterase (AChE) inhibitor [c-2.1] acephate, [c-2.2] azamethiphos, as an organophosphorus acetylcholinesterase (AChE) inhibitor [C-2.3] Azinphos-methyl, [c-2.4] Azinphos-ethyl, [c-2.5] Ethephon, [c-2.6] ] Cadussafos, [c-2.7] chlorethoxyphos, [c-2.8] chlorfenvinphos, [c-2.9] chlormephos, [c- 2.10] Black Chlorpyrifos, [c-2.11] chlorpyrifos-methyl, [c-2.12] coumaphos, [c-2.13] cyanophos, [c-2. 14] demeton-S-methyl, [c-2.15] diazinon, [c-2.16] diclofenthion, [c-2.17] dichlorvos. , [C-2.18] dicrotophos, [c-2.19] dimethoate, [c-2.20] dimethylvinphos, [c-2. 21] disul. [C-2.22] O-ethyl O-4-nitrophenyl phenylphosphonothioate (O-ethyl O-4-nitrophenyl phenylphosphonothioate), [c-2.23] ethion, c-2.24] Ethoprophos, [c-2.25] famfur, [c-2.26] fenamiphos, [c-2.27] fenitrothion, [c- 2.28] fenthion, [c-2.29] fosthiazate, [c-2.30] heptenophos, [c-2.31] isofenphos-methyl isofenphos-methyl), [c-2.32] isocarbophos, [c-2.33] isoxathion, [c-2.34] malathion, [c-2.35] mecarbam ( mecarbam), [c-2.36] methamidophos, [c-2.37] methidathion, [c-2.38] mevinphos, [c-2.39] monocrotophos. ), [C-2.40] naled, [c-2.41] omethoate, [c-2.42] oxydemethon-methyl, [c-2.4]. ] Parathion (parathions), [c-2.44] parathion-methyl (parathion-methyl), [c-2.45] phentoate (c-2.46) phorate (crate), [c-2] .47] phosalone, [c-2.48] phosmet, [c-2.49] phosphamidon, [c-2.50] phoxim, [c-2.51] ] Pirimiphos-methyl, [c-2.52] profenofos, [c-2.53] propetanphos, [c-2.54] prothiophos, [c-2] .55] Pyraclofos, [c-2.56] pyridaphenthion, [c-2.57] quinalphos, [c-2.58] sulfotep, [c-2.59] tebupirimphos ( tebupirimfos), [c-2.60] temephos, [c-2.61] terbufos, [c-2.62] thiomethone, [c-2.63] triazophos. , [C-2.64] trichlorfon, [c-2.65] vamidthione, [c-2.66] chlorthion, [c-2.67] bromphene. Bromfenvinfos, [c-2.68] bromophos, [c-2.69] bromophos-ethyl, [c-2.70] butathiophos, [c-2. 71] Carbophenothion, [c-2.72] chlorphoxim, [c-2.73] sulprofos, [c-2.74] diamidaphos, [c-2. 75] Tetrachlorvinphos, [c-2.76] propaphos, [c-2.77] mesulfenfos, [c-2.78] dioxabenzo (Dioxabenzofos), [c-2.79] etrimfos, [c-2.80] oxydeprofos, [c-2.81] formothion (formation), [c-2.82]. Fensulfothion, [c-2.83] isazofos, [c-2.84] imicyafos, [c-2.85] isamidofos, [c-2.86] thionazine (f-sulfothion). and thionazin) and [c-2.87] fosthietan.

c-3: GABAergic chloride ion blocker As GABAergic chloride ion blocker, [c-3.1] chlordane, [c-3.2] endosulfan, [c-3.3] ] Lindane, [c-3.4] dienochlor, [c-3.5] ethiprole, [c-3.6] fipronil, [c-3.7] acetate Examples include acetoprole and the like.

c-4: Sodium channel modulator As a sodium channel modulator, [c-4.1] acrinathrin, [c-4.2] allethrin [(1R) -isomer] (allethrin [(1R) -somer]), [C-4.3] bifenthrin, [c-4.4] bioallethrin, [c-4.5] bioallethrin S-cyclopentenyl isomer, [c- 4.6] bioresmethrin, [c-4.7] cycloprothrin, [c-4.8] cyfluthrin, [c-4. ] Beta-cyfluthrin, [c-4.10] cyhalothrin, [c-4.11] gamma-cyhalothrin, [c-4.12] lambda-cyhalothrin (lambda) -Cyhalothrin), [c-4.13] cypermethrin, [c-4.14] alpha-cypermethrin, [c-4.15] beta-cypermethrin. , [C-4.16] ceta-cypermethrin, [c-4.17] zeda-cypermethrin, [c-4.18] cife Trin [(1R) -trans-isomer] (cyphenothrin [(1R) -trans-somer]), [c-4.19] deltamethrin, [c-4.20] Empentrin [(EZ)-(1R) ) -Isomer] (empthrin [(EZ)-(1R) -isomer]), [c-4.21] esfenvalerate, [c-4.22] etofenprox, [c- 4.23] fenpropathrin, [c-4.24] fenvalerate, [c-4.25] flucytrinate, [c-4.26] flumethrin ), [C-4.27] tau-fluvalinate, [c-4.28] halfenprox, [c-4.29] imiprothrin, [c-4. 30] Methothrin, [c-4.31] Metofluthrin, [c-4.32] Epsilon-Metofluthrin, [c-4.33] Monfluorothrin, [c-4.33] c-4.34] epsilon-monfluorothrin, [c-4.35] permethrin, [c-4.36] phenothrin [(1R) -trans-a] Somer] (phenothrin [(1R) -trans-somer]), [c-4.37] prallethrin, [c-4.38] resmethrin, [c-4.39] cadethrin. , [C-4.40] silafluofen, [c-4.41] tefluthrin, [c-4.42] tetramethrin, [c-4.43] tetramethrin [(1R)- Isomer] (tetramethrin [(1R) -isomer]), [c-4.44] tralomethrin, [c-4.45] transfluthrin, [c-4.46] ZXI. 901 (3- (4-bromophenoxy) phenyl] -cyanomethyl 4- (difluoromethoxy) -α- (1-methylethyl) benzeneacetate), [c-4.47] biopermethrin, [c-4.48] (c-4.48). furamethrin), [c-4.49] profluthrin, [c-4.50] flubrocytrinate, [c-4.51] dimefluthrin, [c-4.52] DDT. (Dichloro-diphenyl-trichloroethane), [c-4.53] methoxychlor, [c-4. 4] phenothrin (phenothrin), and the like [c-4.55] fluvalinate (fluvalinate).

c-5: Competitive modulator of nicotinic acetylcholine receptor (nAChR) As a competitive modulator of nicotinic acetylcholine receptor (nAChR), [c-5.1] acetamiprid, [c-5.2] clothianidin (clothianidin). ), [C-5.3] dinotefuran, [c-5.4] imidacloprid, [c-5.5] nitenpyram, [c-5.6] thiacloprid, [C-5.7] thiamethoxam, [c-5.8] nicotine, [c-5.9] nicotine sulfate, [c-5.10] sulphate Kisafuroru (sulfoxaflor), [c-5.11] Furupirajifuron (flupyradifurone), and the like [c-5.12] triflupromazine meso pyridinium beam (triflumezopyrim).

c-6: Nicotinic acetylcholine receptor (nAChR) allosteric modulator As a nicotinic acetylcholine receptor (nAChR) allosteric modulator, [c-6.1] spinosad, [c-6.2] spinetoram, etc. Is mentioned.

c-7: Glutamate agonist chloride ion channel (GluCl) allosteric modulator As a glutamate agonist chloride ion channel (GluCl) allosteric modulator, [c-7.1] abamectin, [c-7.2] emamectin benzoic acid Examples thereof include salt (emactin benzoate), [c-7.3] lepimectin, and [c-7.4] milbemectin.

c-8: Juvenile hormone analogs As juvenile hormone analogs, [c-8.1] hydroprene, [c-8.2] quinoprene, [c-8.3] methoprene (methoprene) ), [C-8.4] phenoxycarb, and [c-8.5] pyriproxyfen.

c-9: Non-specific (multi-site) inhibitor As a non-specific (multi-site) inhibitor, [c-9.1] methyl bromide (meth-bromide), [c-9.2] chloropicrin , [C-9.3] cryolite, [c-9.4] sulfuryl fluoride, [c-9.5] borax, [c-9.6] boro Acid (boric acid), [c-9.7] octaborate disodium salt (disodium octoborate), [c-9.8] metaborate sodium salt (sodium metaborate), [c-9.9] tartar ( tartar emetic, [c-9.10] dazomet, [c-9.11] metam ( metam), [c-9.12] carbam sodium salt, and the like.

c-10: Chordonic organ TRPV channel modulator Examples of the chordal organ TRPV channel modulator include [c-10.1] pymetrozine and [c-10.2] pyrifluquinazon.

c-11: Mite growth inhibitor As a mite growth inhibitor, [c-11.1] clofentezine, [c-11.2] diflovidazin, [c-11.3] hexithiazox (Hexythiazox), [c-11.4] ethoxazole and the like.

c-12: Mitochondrial ATP synthase inhibitor As a mitochondrial ATP synthase inhibitor, [c-12.1] diafenthiuron, [c-12.2] azocyclotin, [c-12. 3] Cyhexatin, [c-12.4] fenbutatin oxide, [c-12.5] propargite, [c-12.6] tetradiphone and the like. .

c-13: Oxidative phosphorylation uncoupling agent that perturbs proton gradient As oxidative phosphorylation uncoupling agent that perturbs proton gradient, [c-13.1] chlorfenapyl and [c-13.2] DNOC (Dinitro-ortho-cresol), [c-13.3] vinapacryl, [c-13.4] sulfluramide and the like.

c-14: Nicotinic Acetylcholine Receptor (nAChR) Channel Blocker As a nicotinic acetylcholine receptor (nAChR) channel blocker, [c-14.1] bensultap, [c-14.2] cartap hydrochloride (cartap) hydrochloride), [c-14.3] thiocyclam, [c-14.4] monosultap and the like.

c-15: Chitin biosynthesis inhibitor type 0
As the chitin biosynthesis inhibitor type 0, [c-15.1] bistrifluron (bistrifluron), [c-15.2] chlorfluazuron (chlorfluazuron), [c-15.3] diflubenzuron, [C-15.4] flucycloxuron, [c-15.5] fluphenoxuron, [c-15.6] hexaflumuron, [c-15.7] Lufenuron, [c-15.8] novaluron, [c-15.9] noviflumuron, [c-15.10] teflubenzuron, [c-15.11]. Rifurumuron (triflumuron), and the like.

c-16: chitin biosynthesis inhibitor type 1
Examples of the chitin biosynthesis inhibitor type 1 include [c-16.1] buprofezin and the like.

c-17: Insect molting inhibitor for fly flies An insect molting inhibitor for fly flies includes [c-17.1] cyromazine and the like.

c-18: Molting hormone (ecdysone) receptor agonist As a molting hormone (ecdysone) receptor agonist, [c-18.1] chromafenozide, [c-18.2] halofenozide, [c-18] .3] methoxyphenozide, [c-18.4] tebufenozide and the like.

c-19: Octopamine receptor agonist Examples of the octopamine receptor agonist include [c-19.1] amitraz.

c-20: Mitochondrial electron transfer complex III inhibitor As a mitochondrial electron transfer complex III inhibitor, [c-20.1] hydramethylnon, [c-20.2] acequinocyl, Examples include [c-20.3] fluacrypyrim and [c-20.4] bifenazate.

c-21: Mitochondrial electron transport complex I inhibitor (METI)
As a mitochondrial electron transport complex I inhibitor (METI), [c-21.1] fenazaquin, [c-21.2] fenpyroximate, [c-21.3] pyridaben, [C-21.4] pyrimidifen, [c-21.5] tebufenpyrad, [c-21.6] tolfenpyrad, [c-21.7] rotenone and the like. To be

c-22: Voltage-gated sodium channel blocker Examples of the voltage-gated sodium channel blocker include [c-22.1] indoxacarb and [c-22.2] metaflumizone.

c-23: Acetyl CoA carboxylase inhibitor As an acetyl CoA carboxylase inhibitor, [c-23.1] spirodiclofen, [c-23.2] spiromesifen, [c-23.3]. ] Spirotetramat etc. are mentioned.

c-24: Mitochondrial electron transport complex IV inhibitor As a mitochondrial electron transport complex IV inhibitor, [c-24.1] aluminum phosphide, [c-24.2] calcium phosphide ( calcium phosphide, [c-24.3] phosphine, [c-24.4] zinc phosphide, [c-24.5] calcium cyanide, [c Examples include −24.6] sodium cyanide and [c-24.7] potassium cyanide.

c-25: Mitochondrial electron transport complex II inhibitor [c-25.1] cyenopyrafen, [c-25.2] cyflumethofen, [c-25.1] as mitochondrial electron transport complex II inhibitor -25.3] Pyflubumide and the like.

c-26: ryanodine receptor modulator As a ryanodine receptor modulator, [c-26.1] chlorantraniliprole (chlanantraniprole), [c-26.2] cyantraniliprole, [c-26. 3] Flubendiamide and the like can be mentioned.

c-27: Modulator of string sound organ with unspecified target site [c-27.1] flonicamid etc. are mentioned as a modulator of string sound organ with unspecified target site.

c-28: Other insecticides [c-28.1] azadirachtin, [c-28.2] benzoximate, [c-28.3] phenisobromo as other insecticides. Phenisobromolate, [c-28.4] quinomethionate, [c-28.5] dicofol, [c-28.6] pyridalyl, [c-28.7] bromopropyiate. Brompropylate, [c-28.8] triazamate, [c-28.9] dicyclanil, [c-28.1] dinobuton, [c-28.11] zinocup ( din ocap), [c-28.12] hydrogen cyanide, [c-28.13] methyl iodide, [c-28.14] caranjin, [c-28.15] chloride. Mercury Chloride, [c-28.16] Methyl Isothiocyanate, [c-28.17] Pentachlorophenol, [c-28.18] Phosphine, [c- 28.19] piperonyl butoxide, [c-28.20] polynactin complex, [c-28.21] sabadilla, [C-28.22] sulcofuron salt (sulcofuron-sodium), [c-28.23] tribufos, [c-28.24] aldrin, [c-28.25]. ] Amidithione, [c-28.26] amidothioate, [c-28.27] aminocarb, [c-28.28] amiton, [c-28.29]. ] Alamite, [c-28.30] atidathion, [c-28.31] azothoate, [c-28.32] barium polysulfide, [c-2] 8.33] benclothiaz, [c-28.34] 5- (1,3-benzodioxol-5-yl) -3-hexylcyclohex-2-enone (5- (1,3- benzdioxol-5-yl) -3-hexylcyclohexa-2-enone), [c-28.35] 1,1-bis (4-chlorophenyl) -2-ethoxyethanol (1,1-bis (4-chlorophenyl)- 2-ethoxyethanol, [c-28.36] butonate, [c-28.37] butopyronoxyl, [c-28.38] 2- (2-butoxyethoxy) ethyl thiocyanate (2- ( 2-butoxyethyloxy) ethyl thiocyana e), [c-28.39] camphechlor, [c-28.40] chlorbenside, [c-28.41] chlordecone, [c-28.42] chlordimeform. , [C-28.43] chlorphenethol, [c-28.44] chlorfenson, [c-28.45] fluazuron, [c-28.46] methaaldehyde. (Metaldehyde), [c-28.47] bialaphos, [c-28.48] levamisole hydrochloride (levamisol), [c-28.49] amidoflumet, [C-28.50] pyrafluprole, [c-28.51] pyriprole, [c-28.52] tralopyril, [c-28.53] flupyrazofos, [C-28.54] diofenolan, [c-28.55] chlorobenzilate, [c-28.56] flufenzine, [c-28.57] benzomate (benzomate), [C-28.58] flufenerim, [c-28.59] albendazole, [c-28.60] oxybendazole, c-28.61] fenbendazole, [c-28.62] metam-sodium, [c-28.63] 1,3-dichloropropene (1,3-dichloropropene), [C-28.64] flometoquin, [c-28.65] cyclaniliprole, [c-28.66] tetraniliprole, [c-28.67] brofuranilide (c-28.65) cyclaniliprole broflanilide), [c-28.68] dichloromezotiaz, [c-28.69] ethylene dibromide, [c-28.70] acrylonitrile (a). rylonitril), [c-28.71] bis (2-chloroethyl) ether (bis (2-chloroethyl) ether), [c-28.72] 1-bromo-2-chloroethane (1-bromo-2-chloroethane) , [C-28.73] 3-bromo-1-chloroprop-1-ene (3-bromo-1-chloroprop-1-ene), [c-28.74] bromocyclen, [c-28. 75] carbon disulfide, [c-28.76] carbon tetrachloride, [c-28.77] nemadectin, [c-28.78] cymiazole, [c] -28.79] Cal Calcium polysulfide, [c-28.80] cytokinin, [c-28.81] 2- (octylthio) ethanol (2- (octylthio) ethanol), [c-28.82] oleic acid. Potassium oleate, [c-28.83] sodium oleate, [c-28.84] machine oil, [c-28.85] tar oil, [c-28.85] c-28.86] anabasine, [c-28.87] morantel tartrate, [c-28.88] pyrethrum, [c-28.89] rapeseed (rape seed). d oil), [c-28.90] soybean lecithin, [c-28.91] starch (starch), [c-28.92] hydroxypropyl starch, [c-28.93]. Fatty acid glyceride (decanoyloctanoylglycerol), [c-28.94] propylene glycol monofatty acid ester (propyrene glycol fatty acid ester), [c-28.95] diatomite (diatomite), [c-28.96] afoxolanel (faxoranel). , [C-28.97] fluazaindolidine, [c-28.98] afidopyropen (afidopyro) en), [c-28.99] cyhalodiamide, [c-28.100] thioxazaphen, [c-28.101] fluhexafone, [c-28.102] fluralaner ( fluuralaner), [c-28.103] fluxamethamide, [c-28.104] tetrachlorantraniliprole, [c-28.105] saroraner, [c-28.106]. ] Rotilaner, [c-28.107] cycloxapride, [c-28.108] fluensulfone, c-28.109] TPIC (tripropyl isocyanaurate), [c-28.110] DD (1,3-Dichloropropene), [c-28.111] peroxocarbonate, [c-28.112]. ] MB-599 (verbutin), [c-28.113] bis (2,3,3,3-tetrachloropropyl) ether (bis (2,3,3,3-tetrachloropropoxyl) ether), [c-28 .114] DCIP (bis (2-chloro-1-methylethyl) ether), [c-28.115] ENT-8184 (N- (2-Ethylhexyl) bicyclo [2.2.1] hept-5-ene- 2,3-dicarbo imide), [c-28.116] Bayer 22408 (O, O-diethyl O-naphthalimidophosphorothioate), [c-28.117] Bayer 32394 (tris (1-dodecyl-3-methyl-2-phenylbenzimidazolium) hexacyanoferrate),

[C-28.118] Expression (s34)

(See WO10 / 051926),

[C-28.119] Expression (s35)

A compound represented by (see International Publication No. 13/115391),

[C-28.120] Expression (s36)

A compound represented by the formula (see International Publication No. 12/029672):

[C-28.121] Expression (s37)

(See WO 06/056108),

[C-28.122] Expression (s38)

(See WO 14/053450, WO 15/144683);

[C-28.123] Expression (s39)

(See WO 14/053450, WO 15/144683);

[C-28.124] Expression (s40)

(See WO 14/053450, WO 15/144683);

[C-28.125] Expression (s41)

[In the formula, m6 represents an integer of 0 to 2. (See WO 10/129497),

[C-28.126] Expression (s42)

[In the formula, m7 represents an integer of 0 to 2. (See WO 11/152320),

[C-28.127] Expression (s43)

[In the formula, m8 represents an integer of 0 to 2. ] (See JP-A-2015-160813),

[C-28.128] Expression (s44)

[Wherein, A52 represents a hydrogen atom or a fluorine atom. (See WO 11/134964, WO 14/005982),

[C-28.129] Expression (s45)

[In the formula, m9 represents an integer of 0 to 2, and A53 represents a fluorine atom or a chlorine atom. (See WO 15/025826),

[C-28.130] Expression (s46)

[In the formula, V3 represents a nitrogen atom, a carbon atom, or CF, and V4 and V5 each independently represent a nitrogen atom or a carbon atom. (See WO 11/134964, WO 14/005982),

[C-28.131] Expression (s47)

[Wherein, A54 represents a hydrogen atom, a methyl group, a methoxy group, or an ethoxy group, A55 represents a chlorine atom or a methyl group, and A56 represents a methyl group or an ethyl group. (See WO09 / 049851),

[C-28.132] Expression (s48)

[Wherein, A57 represents a hydrogen atom, a fluorine atom, or a chlorine atom;

Represents one kind of partial structure selected from the group consisting of: (See International Publication No. 11/067272),

[C-28.133] Expression (s49)

[Wherein, A59 represents a hydrogen atom, a fluorine atom, or a chlorine atom;

Represents a partial structure selected from the group consisting of (See WO 10/090344),

[C-28.134] Expression (s50)

[In the formula, m10 represents an integer of 0 to 2, A61 represents a trifluoromethyl group, a trifluoromethylthio group, a trifluoromethylsulfinyl group, or a trifluoromethylsulfonyl group, and A62 represents a hydrogen atom, or It represents a trifluoromethyl group, V6 represents a nitrogen atom or a carbon atom, and V7 represents an oxygen atom or an N-methyl group. (See WO 14/104407),

[C-28.135] Expression (s51)

[Wherein, A63 represents a hydrogen atom or a fluorine atom, the amide group is bonded to the 4- or 5-position, and A64 is

Represents a partial structure selected from the group consisting of (See WO 15/038503, WO 16/144351, WO 16/144678),

[C-28.136] Expression (s52)

[In the formula, A65 represents a hydrogen atom, a C1 to C6 alkyl group, or a C1 to C6 haloalkyl group, A66 represents a hydrogen atom, a halogen atom, or a C1 to C6 alkyl group, and A67 and A68 represent A hydrogen atom, a C1 to C6 alkyl group optionally substituted with a cyano group, an alkyl group optionally substituted with a methoxy group, an alkyl group optionally substituted with an ethoxy group, Or represents a C3 to C8 cycloalkyl group,
A69 represents a hydrogen atom, a cyano group, a C1-C6 haloalkyl group optionally substituted with a cyano group, a C1-C6 alkyl group, or a C3-C8 cycloalkyl group. (See WO 12/143317, WO 16/016369),

[C-28.137] Expression (s53) or Expression (s54)

[In the formula, A70 represents a methyl group, an ethyl group, an isopropyl group, a 2,2,2-trifluoroethyl group, or a phenyl group, and A71 represents

A72 represents a partial structure selected from the group consisting of:

V8 represents an oxygen atom, a sulfur atom, —CH ₂ —, or —CH ₂ CH ₂ —. (See WO 14/167084, WO 16/055431),

[C-28.138] Expression (s55)

[In the formula, m11 represents an integer of 0 to 1, A73 represents a chlorine atom, a bromine atom, a methyl group, or a trifluoromethyl group, and A74 represents a hydrogen atom, a chlorine atom, a bromine atom, a cyano group, Or a trifluoromethyl group, A75 represents a hydrogen atom, a chlorine atom or a bromine atom, A76 and A77 each independently represent a C1 to C6 alkyl group, or a C3 to C8 cycloalkyl group, A78 represents a chlorine atom, a bromine atom, a cyano group, a nitro group, a difluoromethyl group, or a trifluoromethyl group. A compound represented by the formula (see International Patent Publication No.

[C-28.139] Expression (s56)

[Wherein A79, A80, A81 and A82 are each independently a hydrogen atom, a halogen atom, a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, a C1 to C6 alkoxy group, or a C3 to C8 Represents a cycloalkoxy group. (See WO 12/027521),

[C-28.140] Expression (s57)

[In the formula, m12 represents an integer of 0 to 2, A83 represents a hydrogen atom or a fluorine atom, and A84 represents

Represents a partial structure selected from the group consisting of (See WO 13/162715),

[C-28.141] asynonapyr,

[C-28.142] Expression (s59)

[A90 represents a halogen atom, a C1 to C6 alkyl group, or a C1 to C6 haloalkyl group, A91 represents a C1 to C6 haloalkyl group, and A92 and A93 are each independently a hydrogen atom, Represents a C1 to C6 alkyl group, an acetyl group, a propionyl group, a methanesulfonylethyl group, a methoxycarbonyl group, or an ethoxycarbonyl group, wherein A94 and A95 are each independently a hydrogen atom, a C1 to C6 alkyl group, Alternatively, it represents a C1-C6 haloalkyl group. And the like (see WO 12/1664698).

The mixing ratio of the compound of the present invention and the pest controlling agent is not particularly limited as long as the effect is exerted, but the pest controlling agent is usually 0.001 to 0.001 by weight based on the compound of the present invention. The ratio is 1000, preferably 0.01 to 100.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Reference Examples, and Test Examples, but the present invention is not limited thereto.

[Synthesis Example 1]
Synthesis of 3-bromo-6- (2,6-difluorophenyl) -1-ethyl-5- (5-methyl-1,2,3-thiadiazol-4-yl) pyridin-2 (1H) -one (compound Number: 1)

Ethyl 2- (1- (5-bromo-2- (2,6-difluorophenyl) -1-ethyl-6-oxo-1,6-dihydropyridin-3-yl) propylidene) hydrazine-synthesized in Reference Example 9 To 10 ml of a dichloroethane solution containing 604 mg of 1-carboxylate, 0.44 ml of thionyl chloride was added at room temperature, and the mixture was stirred at the same temperature for 3.5 hours. A saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was washed with saturated saline and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 110 mg as a brown solid.

[Synthesis Example 2]
Step 1: Synthesis of 5- (2-amino-5-methylthiazol-4-yl) -3-bromo-6- (2,6-difluorophenyl) -1-ethylpyridin-2 (1H) -one (Compound (Number: 13)

Contains 217 mg of 3-bromo-5- (2-bromopropanoyl) -6- (2,6-difluorophenyl) -1-ethylpyridin-2 (1H) -one synthesized in Reference Example 10 and 73.1 mg of thiourea 3 ml of acetic acid solution was stirred at 60 ° C for 1 hour. The reaction mixture was further heated to 100 ° C. and stirred at the same temperature for 3 hours. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain 275 mg of a yellow solid containing the title compound.

Step 2: Synthesis of 5- (2-amino-5-methylthiazol-4-yl) -3-bromo-6- (2,6-difluorophenyl) -1-ethylpyridin-2 (1H) -one (Compound Number: 4)

5- (2-amino-5-methylthiazol-4-yl) -3-bromo-6- (2,6-difluorophenyl) -1-ethylpyridin-2 (1H) -one in 10 ml of THF solution containing 235 mg. 97.5 μl of tert-butyl nitrite was added dropwise, and the mixture was stirred at 50 ° C. for 1.5 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 74 mg of a tan solid.

[Synthesis example 3]
Synthesis of 3-bromo-6- (2,6-difluorophenyl) -1-ethyl-5- (1,2,3-thiadiazol-5-yl) pyridin-2 (1H) -one (Compound No. 3)

Ethyl 2- (2- (5-bromo-2- (2,6-difluorophenyl) -1-ethyl-6-oxo-1,6-dihydropyridin-3-yl) ethylidene) hydrazine-synthesized in Reference Example 13 To 10 ml of dichloroethane solution containing 315 mg of 1-carboxylate, 0.15 ml of thionyl chloride was added at room temperature, and the mixture was stirred at the same temperature for 2 hours. A saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was washed with saturated saline and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 185 mg of white solid.

[Synthesis Example 4]
Step 1: Synthesis of 5- (2-amino-4-methylthiazol-5-yl) -3-bromo-6- (2,6-difluorophenyl) -1-ethylpyridin-2 (1H) -one (Compound (Number: 14)

118 mg of 3-bromo-5- (1-bromo-2-oxopropyl) -6- (2,6-difluorophenyl) -1-ethylpyridin-2 (1H) -one synthesized in Reference Example 16 and 30 mg of thiourea were added. The acetic acid solution containing 2 ml was stirred at 60 ° C. for 1.5 hours. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain 108 mg of a yellow oily substance containing the title compound.

Step 2: Synthesis of 3-bromo-6- (2,6-difluorophenyl) -1-ethyl-5- (4-methylthiazol-5-yl) pyridin-2 (1H) -one (Compound No. 6)

10 ml of THF solution containing 108 mg of 5- (2-amino-4-methylthiazol-5-yl) -3-bromo-6- (2,6-difluorophenyl) -1-ethylpyridin-2 (1H) -one , Tert-butyl nitrite, 46.6 μl were added dropwise, and the mixture was stirred at 50 ° C. for 1.5 hours. After cooling to room temperature, saturated aqueous ammonium chloride solution and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 39 mg of a tan oil.

[Reference Example 1]

Step 1: Synthesis of 1- (2,6-difluorophenyl) -N-phenylpropane-1-imine Chloride containing 23.91 g of titanium tetrachloride in 100 ml of methylene chloride solution containing 11.74 g of aniline and 17.01 g of triethylamine 50 ml of methylene solution was added dropwise under ice cooling. After 30 ml of a methylene chloride solution containing 14.30 g of 1- (2,6-difluorophenyl) propan-1-one was added dropwise to the reaction solution, the temperature was raised from ice cooling to room temperature and the mixture was stirred overnight. 1N Hydrochloric acid was added to the obtained reaction mixture, the layers were separated, and dried over sodium sulfate. After evaporating the solvent under reduced pressure, 21.10 g of a dark green oil containing the title compound was obtained. Used for the next reaction without further purification.

Step 2: Synthesis of 6- (2,6-difluorophenyl) -5-methyl-3,4-dihydropyridin-2 (1H) -one 1- (2,6-difluorophenyl) -N obtained in Step 1 6.57 g of acrylamide monomer was added to 200 ml of a dioxane solution containing 21.10 g of -phenylpropane-1-imine and 12.33 g of aluminum chloride, and the mixture was stirred at 90 ° C for 3 hours. After distilling off the solvent of the reaction mixture under reduced pressure to about half the volume, 1N hydrochloric acid and ethyl acetate were added to carry out liquid separation. The obtained organic layer was washed with a saturated saline solution and dried with sodium sulfate. After evaporating the solvent under reduced pressure, the obtained residue was purified by silica gel column chromatography. The obtained solid was washed with isopropyl ether to give the title compound as a white solid (11.65 g).

¹ H-NMR (CDCl ₃ ) δ: 7.36-7.34 (1H, m), 6.97-6.94 (2H, m), 6.52 (1H, br s), 2.61- 2.59 (2H, m), 2.48-2.47 (2H, m), 1.63 (3H, s).

[Reference Example 2]
Synthesis of 6- (2,6-difluorophenyl) -1-ethyl-5-methyl-3,4-dihydropyridin-2 (1H) -one

50-120 ml of DMF solution containing 12.40 g of 6- (2,6-difluorophenyl) -5-methyl-3,4-dihydropyridin-2 (1H) -one, 54.30 g of cesium carbonate and 25.99 g of ethyl iodide. Stirred at 3.5 ° C. for 3.5 hours. Next, after adding 27.15 g of cesium carbonate and 13.01 g of ethyl iodide, the mixture was stirred at 50 ° C. for 2 hours and further at 60 ° C. for 1.5 hours. After cooling to room temperature, the insoluble material was removed by filtering the reaction mixture. After the solvent of the filtrate was distilled off under reduced pressure, ethyl acetate and water were added to separate the layers. The obtained organic layer was washed successively with an aqueous sodium thiosulfate solution and saturated brine, and dried over sodium sulfate. After evaporating the solvent under reduced pressure, the obtained solid was washed with isopropyl ether. The title compound was obtained as 11.98 g of a white solid.

¹ H-NMR (CDCl ₃ ) δ: 7.38-7.35 (1H, m), 6.97-6.96 (2H, m), 3.33 (2H, q, J = 7.1 Hz). ), 2.60-2.58 (2H, m), 2.38-2.36 (2H, m), 1.59 (3H, s), 0.91 (3H, t, J = 7.1). Hz).

[Reference Example 3]
Synthesis of 6- (2,6-difluorophenyl) -1-ethyl-5-methylpyridin-2 (1H) -one

11.98 g of 6- (2,6-difluorophenyl) -1-ethyl-5-methyl-3,4-dihydropyridin-2 (1H) -one and 2,3-dichloro-5,6-dicyano-p-benzoquinone 170 ml of a toluene solution containing 21.65 g was stirred at 120 ° C. for 1.5 hours. After cooling to room temperature, the insoluble material was removed by filtering the reaction mixture. The solvent was distilled off from the filtrate under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The obtained solid was washed with isopropyl ether to give the title compound as a light yellow solid (9.34 g).

¹ H-NMR (CDCl ₃ ) δ: 7.50-7.49 (1H, m), 7.27 (2H, d, J = 9.5 Hz), 7.09-7.06 (2H, m) ), 6.63 (1H, d, J = 9.5 Hz), 3.83 (2H, q, J = 7.1 Hz), 1.80 (3H, s), 1.10 (3H, t). , J = 7.1 Hz).

[Reference Example 4]
Synthesis of 3-chloro-6- (2,6-difluorophenyl) -1-ethyl-5-methylpyridin-2 (1H) -one

110 ml of a DMF solution containing 11.36 g of 6- (2,6-difluorophenyl) -1-ethyl-5-methylpyridin-2 (1H) -one and 6.69 g of N-chlorosuccinimide was stirred at 70 ° C. for 50 minutes . After cooling to room temperature, the reaction mixture was evaporated under reduced pressure. After ethyl acetate and water were added to the mixture for liquid separation, the obtained organic layer was washed successively with an aqueous sodium thiosulfate solution and saturated saline, and dried over sodium sulfate. After evaporating the solvent under reduced pressure, the obtained solid was washed with isopropyl ether. The title compound was obtained as 11.41 g of a white solid.

¹ H-NMR (CDCl ₃ ) δ: 7.53-7.49 (1H, m), 7.50 (1H, s), 7.09-7.07 (2H, m), 3.88 (2H). , Q, J = 7.1 Hz), 1.81 (3H, s), 1.12 (3H, t, J = 7.1 Hz).

[Reference Example 5]
Synthesis of 3-chloro-5- (dibromomethyl) -6- (2,6-difluorophenyl) -1-ethylpyridin-2 (1H) -one

230 ml of chlorobenzene solution containing 12.65 g of 3-chloro-6- (2,6-difluorophenyl) -1-ethyl-5-methylpyridin-2 (1H) -one, 16.67 g of N-bromosuccinimide and azobis 366 mg of isobutyronitrile was added, and the mixture was stirred at 110 ° C for 50 minutes. After cooling to room temperature, water and dichloromethane were added to the reaction mixture to separate it. The obtained organic layer was washed with an aqueous sodium thiosulfate solution and dried over sodium sulfate. After evaporating the solvent under reduced pressure, the obtained solid was washed with isopropyl ether. The title compound was obtained as 16.88 g of a light brown solid.

¹ H-NMR (CDCl ₃ ) δ: 8.13 (1H, s), 7.65-7.63 (1H, m), 7.18 (2H, dd, J = 8.5, 6.8 Hz ), 5.96 (1H, s), 3.82 (2H, q, J = 7.1 Hz), 1.13 (3H, t, J = 7.1 Hz).

[Reference Example 6]
Synthesis of 5-chloro-2- (2,6-difluorophenyl) -1-ethyl-6-oxo-1,6-dihydropyridine-3-carbaldehyde

190 ml of an aqueous solution containing 21.87 g of silver nitrate in 380 ml of acetonitrile containing 18.95 g of 3-chloro-5- (dibromomethyl) -6- (2,6-difluorophenyl) -1-ethylpyridin-2 (1H) -one Was added and the mixture was stirred at room temperature for 15 minutes. The insoluble material was removed by filtering the obtained reaction mixture. After the solvent was distilled off from the filtrate under reduced pressure, water and ethyl acetate were added to separate the layers. The obtained organic layer was washed with 1N hydrochloric acid and saturated brine, and dried over sodium sulfate. After evaporating the solvent under reduced pressure, the obtained solid was washed with isopropyl ether. The title compound was obtained as 11.37 g as a pale yellow solid.

¹ H-NMR (CDCl ₃ ) δ: 9.19 (1H, t, J = 1.0 Hz), 8.13 (1H, s), 7.67-7.63 (1H, m), 7. 18-7.16 (2H, m), 3.94 (2H, q, J = 7.1 Hz), 1.19 (3H, t, J = 7.1 Hz).
1.25 (3H, t, J = 7.2 Hz).

[Reference Example 7]
Synthesis of 3-bromo-6- (2,6-difluorophenyl) -1-ethyl-5- (1-hydroxypropyl) pyridin-2 (1H) -one

THF containing 1.00 g of 5-bromo-2- (2,6-difluorophenyl) -1-ethyl-6-oxo-1,6-dihydropyridine-3-carbaldehyde synthesized with reference to Reference Examples 1 to 6 1.73 ml of a 2 mol / l solution of ethylmagnesium chloride in THF was added dropwise to 10 ml of the solution at 0 ° C., and the mixture was stirred for 30 minutes. The reaction solution was heated to room temperature and stirred for 2 hours. A saturated aqueous ammonium chloride solution and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was washed successively with 1N aqueous hydrochloric acid and saturated brine and dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1.09 g of a yellow oily substance containing the title compound. It was used for the next reaction without further purification.

[Reference Example 8]
Synthesis of 3-bromo-6- (2,6-difluorophenyl) -1-ethyl-5-propynylpyridin-2 (1H) -one

30 ml of a dichloromethane solution containing 1.09 g of 3-bromo-6- (2,6-difluorophenyl) -1-ethyl-5- (1-hydroxypropyl) pyridin-2 (1H) -one obtained in Reference Example 7 1.23 g of Dess-Martin periodinane (1,1,1-triacetoxy-1,1-dihydro-1,2-benzoiodoxol-3- (1H) -one) was added to and 30 minutes at room temperature. It was stirred. Ethyl acetate was added to the reaction mixture and the mixture was filtered through Celite. The solvent was distilled off from the organic layer under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 653 mg white solid.

¹ H-NMR (CDCl3) δ: 8.26 (1H, s), 7.53 (1H, tt, J = 8.4, 6.4 Hz), 7.09-7.03 (2H, m) , 3.93 (2H, q, J = 7.1 Hz), 2.64 (2H, q, J = 7.1 Hz), 1.15 (3H, t, J = 7.1 Hz), 1 .02 (3H, t, J = 7.1 Hz).

[Reference Example 9]
Synthesis of ethyl 2- (1- (5-bromo-2- (2,6-difluorophenyl) -1-ethyl-6-oxo-1,6-dihydropyridin-3-yl) propylidene) hydrazine-1-carboxylate

Includes 450 mg of 3-bromo-6- (2,6-difluorophenyl) -1-ethyl-5-propynylpyridin-2 (1H) -one, 188 mg of ethyl carbazate and 104 mg of p-toluenesulfonic acid monohydrate. 3 ml of acetic acid solution was stirred at 65 ° C for 6 hours. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was washed with saturated saline and dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain 604 mg of a yellow oil containing the title compound. It was used for the next reaction without further purification.

[Reference Example 10]
Synthesis of 3-bromo-5- (2-bromopropanoyl) -6- (2,6-difluorophenyl) -1-ethylpyridin-2 (1H) -one

3-Bromo-6- (2,6-difluorophenyl) -1-ethyl-5-propynylpyridin-2 (1H) -one 200 mg and N-bromosuccinimide 105 mg and p-toluenesulfonic acid monohydrate 92.3 mg 4 ml of an acetonitrile solution containing was stirred at 70 ° C. for 3 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was washed successively with a 1% aqueous sodium thiosulfate solution and saturated brine, and dried over sodium sulfate. The solvent was distilled off from the organic layer under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 217 mg of a clear oil.

¹ H-NMR (CDCl3) δ: 8.24 (1H, s), 7.54 (1H, tt, J = 8.5, 6.4 Hz), 7.08-7.06 (2H, m) , 4.87 (1H, q, J = 6.6 Hz), 3.98-3.91 (2H, m), 1.69 (3H, d, J = 6.6 Hz), 1.16 ( 3H, t, J = 7.2 Hz).

[Reference Example 11]
Synthesis of 3-bromo-6- (2,6-difluorophenyl) -1-ethyl-5- (2-methoxyvinyl) pyridin-2 (1H) -one

To a 10 ml THF solution containing 1.25 g of (methoxymethyl) triphenylphosphonium chloride, 408 mg of potassium tert-butoxide was added at 0 ° C., and the mixture was stirred for 40 minutes. 5-Bromo-2- (2,6-difluorophenyl) -1-ethyl-6-oxo-1,6-dihydropyridine-3-carbohydrate synthesized according to Reference Examples 1 to 6 was added to the obtained reaction mixture. 4 ml of a THF solution containing 420 mg of aldehyde was added at 0 ° C. The reaction mixture was warmed to room temperature and stirred for 2 hours. A saturated aqueous ammonium solution and ethyl acetate were added to the reaction mixture to separate it. The organic layer was washed with saturated saline and dried over sodium sulfate. The solvent was distilled off from the organic layer under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 400 mg of a clear oil.

¹ H-NMR (CDCl3) δ: 8.62 (1H, s, major), 7.88 (1H, s, minor), 7.54-7.49 (1H, m, mixture), 7.09- 7.06 (2H, m), 6.68 (1H, d, J = 12.7 Hz, major), 5.88 (1H, d, J = 7.1 Hz, minor), 4.99 (1H) , D, J = 12.7 Hz, major), 4.32 (1H, d, J = 7.1 Hz, minor), 3.88 (2H, q, J = 7.2 Hz, mixture), 3. .72 (3H, s, major), 3.46 (3H, s, minor), 1.13-1.11 (3H, m, mixture).

[Reference Example 12]
Synthesis of 2- (5-bromo-2- (2,6-difluorophenyl) -1-ethyl-6-oxo-1,6-dihydropyridin-3-yl) acetaldehyde

4 ml of THF solution containing 360 mg of 3-bromo-6- (2,6-difluorophenyl) -1-ethyl-5- (2-methoxyvinyl) pyridin-2 (1H) -one and 2 ml of 4N hydrochloric acid water at 70 ° C. And stirred for 4 hours. After cooling to room temperature, water and ethyl acetate were added to separate the layers. The obtained organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over sodium sulfate. The solvent was distilled off from the organic layer under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 251 mg of a clear oil.

¹ H-NMR (CDCl3) δ: 9.51 (1H, s), 7.72 (1H, s), 7.56 (1H, tt, J = 8.4, 6.4 Hz), 7.13 -7.08 (2H, m), 3.89 (2H, q, J = 7.2 Hz), 3.16 (2H, d, J = 1.7 Hz), 1.14 (3H, t, J = 7.2 Hz).

[Reference Example 13]
Synthesis of ethyl 2- (2- (5-bromo-2- (2,6-difluorophenyl) -1-ethyl-6-oxo-1,6-dihydropyridin-3-yl) ethylidene) hydrazine-1-carboxylate

2- (5-Bromo-2- (2,6-difluorophenyl) -1-ethyl-6-oxo-1,6-dihydropyridin-3-yl) acetaldehyde 251 mg and ethyl carbazate 145 mg and p-toluenesulfonic acid 3 ml of acetic acid solution containing 24 mg of monohydrate was stirred at 60 ° C. for 2 hours. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was washed with saturated saline and dried over sodium sulfate. The solvent was distilled off under reduced pressure to obtain 315 mg of a pale yellow oil containing the title compound. It was used for the next reaction without further purification.

¹ H-NMR (CDCl3) δ: 7.77-7.75 (2H, m), 7.55 (1H, tt, J = 8.6, 6.4 Hz), 7.14-7.05 ( 2H, m), 6.96 (1H, br s), 4.25-4.21 (2H, m), 3.87 (2H, q, J = 7.0 Hz), 3.09-3. 08 (2H, m), 1.28-1.26 (3H, m), 1.13 (3H, d, J = 7.0 Hz).

[Reference Example 14]
Synthesis of 3-bromo-6- (2,6-difluorophenyl) -1-ethyl-5- (2-hydroxypropyl) pyridin-2 (1H) -one

2- (5-Bromo-2- (2,6-difluorophenyl) -1-ethyl-6-oxo-1,6-dihydropyridin-3-yl) acetaldehyde 3 ml / l methyl in 16 ml THF solution containing 795 mg 0.81 ml of a THF solution of magnesium chloride was added dropwise at 0 ° C., and the mixture was stirred for 20 minutes. A saturated aqueous ammonium chloride solution and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was washed with saturated saline and dried over sodium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 490 mg as a yellow oil.

¹ H-NMR (CDCl3) δ: 7.83 (1H, s), 7.55-7.53 (1H, m), 7.10-7.07 (2H, m), 3.87-3. 82 (2H, m), 2.20 (1H, d, J = 1.5 Hz), 1.92-1.85 (1H, m), 1.74-1.71 (1H, m), 1 0.51-1.50 (1H, m), 1.12 (3H, t, J = 7.1 Hz), 1.07 (3H, d, J = 6.1 Hz).

[Reference Example 15]
Synthesis of 3-bromo-6- (2,6-difluorophenyl) -1-ethyl-5- (2-hydroxypropyl) pyridin-2 (1H) -one

10 ml of a dichloromethane solution containing 490 mg of 3-bromo-6- (2,6-difluorophenyl) -1-ethyl-5- (2-hydroxypropyl) pyridin-2 (1H) -one obtained in Reference Example 14 was added to a dessert solution. -554 mg of martin periodinane (1,1,1-triacetoxy-1,1-dihydro-1,2-benzoiodoxol-3- (1H) -one) was added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was filtered through Celite and washed with dichloromethane. The solvent was distilled off from the organic layer under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 320 mg as a clear oil.

¹ H-NMR (CDCl3) δ: 7.71 (1H, s), 7.55 (1H, tt, J = 8.6, 6.4 Hz), 7.11-7.09 (2H, m) , 3.88 (2H, q, J = 7.1 Hz), 3.17 (2H, s), 2.01 (3H, s), 1.13 (3H, t, J = 7.1 Hz) ．

[Reference Example 16]
Synthesis of 3-bromo-5- (1-bromo-2-oxopropyl) -6- (2,6-difluorophenyl) -1-ethylpyridin-2 (1H) -one

205 mg of 3-bromo-6- (2,6-difluorophenyl) -1-ethyl-5- (2-hydroxypropyl) pyridin-2 (1H) -one and 108 mg of N-bromosuccinimide and 1 water of p-toluenesulfonic acid 4 ml of an acetonitrile solution containing 94.6 mg of a Japanese product was stirred at 60 ° C. for 2 hours. After cooling to room temperature, saturated aqueous sodium hydrogen carbonate solution and ethyl acetate were added to the reaction mixture to separate it. The obtained organic layer was washed successively with a 1% aqueous sodium thiosulfate solution and saturated brine, and dried over sodium sulfate. The solvent was distilled off from the organic layer under reduced pressure, and the obtained residue was purified by silica gel column chromatography. The title compound was obtained as 118 mg of a clear oil.

¹ H-NMR (CDCl3) δ: 7.96 (1H, s), 7.63 (1H, tt, J = 8.4, 6.4 Hz), 7.19-7.16 (2H, m) , 4.76 (1H, s), 3.87-3.83 (2H, m), 2.25 (3H, s), 1.14-1.12 (3H, m).

Table 4 shows compounds synthesized according to the above-mentioned examples, but the present invention is not limited thereto.

In Table 4, structure A shows the following.

In Table 4, Structure B shows the following.

In Table 4, structure C shows the following.

In Table 4, structure D shows the following.

In the structural formulas A to D, Y is the formula (Y)

(Wherein R4 and R5 have the same meanings as described above, and n represents an integer of 0 to 4), and R1, R2, and Het have the same meanings as described above.

N in the formula (Y) represents an integer of 0 to 4.

In Table 4, Ph in Y represents a phenyl group.

For example, in Table 4, the description of "2,6-di-F-Ph" of Y means a phenyl group having a fluorine atom bonded to the 2- and 6-positions, and other description is also applicable. It is the same.

Next, regarding the compounds described in Table 4, Table ¹ shows their ¹ H-NMR data.

Next, it will be specifically shown that the compound of the present invention is effective against plant diseases, but the present invention is not limited to these examples.

Further, Tables 6 to 9 show comparative examples of the compounds of the present invention and compounds having another heterocycle at the 5-position. Comparative compounds C1, C2, and C3 are described below as comparative control compounds.
The comparative compound C1, the comparative compound C2, and the comparative compound C3 can be synthesized by referring to the methods described in the production methods A to H in the present specification or by combining them with known methods.

Comparative compound C1: 3-Bromo-6- (2,6-difluorophenyl) -1-ethyl-5- (4-methylthiophen-3-yl) pyridin-2 (1H) -one

Comparative compound C2: 3-chloro-6- (2-chloro-4-fluorophenyl) -1-ethyl-5- (4-methyloxazol-5-yl) pyridin-2 (1H) -one

Comparative compound C3: 3-chloro-6- (2,6-difluorophenyl) -1-ethyl-5- (oxazol-5-yl) pyridin-2 (1H) -one

Regarding the severity of disease in the test examples shown below, the severity of disease was evaluated every 0.05, with the severity of disease of plants having no disease as 0 and the severity of disease of plants in the drug-untreated area as 3. Further, the control value was calculated from the degree of onset according to the following formula.

<Control value>
Control value = 100 {1- (n / 3)}
n = degree of illness in each drug treatment area

[Test Example A] Rice blast After sown with seeds of a test plant (rice variety: Kofu), it was cultivated until the second leaf developed. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). The plant after the drug solution was dried was inoculated with 1 to 2 × 10 ⁵ cells / ml of a conidia suspension of the rice blast fungus (Magnaporthe grisea) by spraying. After inoculation, the plant was left in a moist chamber with a room temperature of 20 to 23 ° C. for about 24 hours to promote disease onset. The degree of disease onset 6 to 10 days after the inoculation was investigated to evaluate the effect of the drug solution.

As a result, the compounds shown below showed a control value of more than 50%.
Compound number: 3, 4, 5, 6, 8, 9, 10, 12

The results of a comparative test conducted between the compounds of the present invention 3, 4, 5, 6, 8, 9, 10, and 12 and the comparative compounds C2 and C3 are shown in the same manner as above except that the chemical concentration is 50 ppm. 6 shows.

As a result, the compounds of the present invention having a sulfur atom and a nitrogen atom in the hetero ring showed higher control value than the comparative compounds C2 and C3.

[Test Example B] Tomato gray mold disease After sowing seeds of a test plant (tomato variety: large Fukuju), 3 to 5 true leaves were cultivated. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the drug solution was dried, the plants were spray-inoculated with a conidial suspension of 4-8 × 10 ⁵ cells / ml of Botrytis cinerea. After inoculation, the plant was left in a wet room at a room temperature of 20 to 23 ° C. for about 48 hours to promote the onset of disease. The degree of disease onset 2 to 3 days after the inoculation was investigated to evaluate the effect of the drug solution.

As a result, the compounds shown below showed a control value of more than 50%.
Compound number: 1, 2, 3, 4, 5, 6, 8, 9, 10, 12

Comparative tests of the compounds of the present invention 2, 3, 4, 5, 6, 8, 9, 10, and 12 with the comparative compounds C1 and C2 were conducted in the same manner as described above except that the chemical concentration was 50 ppm or 250 ppm. The results are shown in Table 7.

As a result, the compounds of the present invention having a sulfur atom and a nitrogen atom in the heterocycle showed a higher control value than the comparative compounds C1 and C2.

[Test Example C] Cabbage black spot disease Seeds of a test plant (cabbage variety: four seasons harvest) were sown and then cultivated until cotyledons developed. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). The plants after the drug solution had been dried were spray-inoculated with a conidial suspension of 4-8 × 10 ⁵ cells / ml of cabbage black scab (Alternia brassicicola). After inoculation, the plant was left in a wet room at a room temperature of 20 to 23 ° C. for about 48 hours to promote the onset of disease. The degree of disease onset 2 to 3 days after the inoculation was investigated to evaluate the effect of the drug solution.

As a result, the compounds shown below showed a control value of more than 50%.
Compound number: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12

[Test Example D] Barley powdery mildew After planting seeds of a test plant (barley variety: Akakami Riki), it was cultivated until the first leaf developed. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the chemical solution was dried, the conidia of barley powdery mildew (Blumeria graminis f.sp.hordei) were beaten and inoculated to the plants. The degree of illness was investigated 6 to 10 days after the inoculation, and its effect was evaluated.

As a result, the compounds shown below showed a control value of more than 50%.
Compound number: 4, 6, 8

Table 8 shows the results of a comparative test conducted between the present compounds 4, 6, and 8 and the comparative compounds C1, C2, and C3 in the same manner as described above except that the chemical concentration was 50 ppm or 250 ppm.

As a result, the compounds of the present invention having a sulfur atom and a nitrogen atom in the heterocycle showed a higher control value than the comparative compounds C1, C2 and C3.

[Test Example E] Wheat leaf rust Seeds of a test plant (wheat variety: Norin 61) were sown and then cultivated until the first leaves developed. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the drug solution was dried, the plants were inoculated with 1 to 2 × 10 ⁵ pieces / ml of a spore suspension of Puccinia recondita. After inoculation, the plant was left in a moist chamber with a room temperature of 20 to 23 ° C. for about 24 hours to promote disease onset. The degree of disease onset 7 to 10 days after the inoculation was investigated to evaluate the effect of the drug solution.

[Test Example F] Tomato plague After sowing seeds of a test plant (tomato variety: large Fukuju), 3 to 5 true leaves were cultivated. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). The plants after the drug solution had been dried were spray-inoculated with 4 to 8 × 10 ³ / ml of zoosporangia suspension of Phytophthora infestans. After the inoculation, the cells were allowed to stand in a wet room at room temperature of 20 ° C. for about 24 hours to promote the onset of the disease. The degree of disease onset 5 to 10 days after the inoculation was investigated to evaluate the effect of the drug solution.

[Test Example G] Grape downy mildew After sowing seeds of a test plant (grape variety: Neo Muscat), the seedlings were cultivated until 3 to 4 true leaves were developed. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the drug solution was dried, the plants were inoculated by spraying with 1 to 2 × 10 ⁴ / ml of zoosporangia suspension of Plasmopara viticola. After the inoculation, the cells were allowed to stand in a wet room at room temperature of 20 ° C. for about 24 hours to promote the onset of the disease. The degree of disease onset 7 to 10 days after the inoculation was investigated to evaluate the effect of the drug solution.

[Test Example H] Cucumber Anthrax Disease Seeds of a test plant (cucumber variety: Sagami Hanjiro) were sown, and then cultivated until one true leaf developed. In the test, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1) and diluted with well water to a concentration of 250 ppm to obtain a chemical solution. The obtained drug solution was sprayed on the test plant (2.5 ml / pot). After the drug solution was dried, the plants were inoculated with 2 to 4 × 10 ⁵ cells / ml of a conidia suspension of anthrax of Cucumber (Colletotrichum orbiculare) by spraying. After inoculation, the plant was left in a moist chamber with a room temperature of 20 to 23 ° C. for about 24 hours to promote disease onset. The degree of disease onset 6 to 10 days after the inoculation was investigated to evaluate the effect of the drug solution.

As a result, the compounds shown below showed a control value of more than 50%.
Compound number: 2, 3, 4, 5, 6, 8, 9, 10, 12

Results of a comparative test of the compounds of the present invention 2, 3, 5, 6, 8, 10, and 12 and the comparative compounds C1, C2, and C3 in the same manner as described above except that the chemical concentration is 50 ppm or 250 ppm. Is shown in Table 9.

From the comparative tests shown in Tables 6 to 9, it was found that the compounds of the present invention having a sulfur atom and a nitrogen atom in the heterocycle show a high controlling effect against a wide range of plant diseases.

Since the pyridone compound of the present invention is a novel compound and can control plant diseases, it is useful as a pesticide, for example, an agricultural and horticultural pest control agent, particularly an agricultural and horticultural fungicide.

All publications, patent applications, and technical standards mentioned herein are to the same extent as if specifically and individually stated that the individual publications, patent applications, and technical standards are incorporated by reference, Incorporated herein by reference.

Claims

Equation (1)

[In the formula, R1 is
Hydroxyl group,
Cyano group,
A C1 to C6 alkyl group optionally substituted with a substituent A,
A C1 to C6 haloalkyl group,
A C3 to C8 cycloalkyl group which may be optionally substituted with a substituent A,
A C2-C6 alkenyl group optionally substituted with a substituent A,
A C2-C6 haloalkenyl group,
A C2-C6 alkynyl group optionally substituted with a substituent A,
A C2-C6 haloalkynyl group,
A C1 to C6 alkoxy group optionally substituted with a substituent A,
A C1 to C6 haloalkoxy group,
A C3 to C8 cycloalkoxy group optionally substituted with a substituent A,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent A,
A C2-C6 haloalkenyloxy group,
A C3-C6 alkynyloxy group which may be optionally substituted with a substituent A,
A C3 to C6 haloalkynyloxy group,
Or RaRbN— (wherein Ra and Rb are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 Or a Ra and Rb together with the nitrogen atom to which they are attached form an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidinyl group, a homopiperidinyl group, or an azocanyl group. Representation; R2 is
Hydrogen atom,
Nitro group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent A,
A C1 to C6 haloalkyl group,
A C3 to C8 cycloalkyl group which may be optionally substituted with a substituent A,
A C2-C6 alkenyl group optionally substituted with a substituent A,
A C2-C6 haloalkenyl group,
A C2-C6 alkynyl group optionally substituted with a substituent A,
A C2-C6 haloalkynyl group,
A C1 to C6 alkoxy group optionally substituted with a substituent A,
A C1 to C6 haloalkoxy group,
A C3 to C8 cycloalkoxy group optionally substituted with a substituent A,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent A,
A C2-C6 haloalkenyloxy group,
A C3-C6 alkynyloxy group which may be optionally substituted with a substituent A,
A C3 to C6 haloalkynyloxy group,
Rc-L- (wherein Rc represents a C1-C6 alkyl group or a C1-C6 haloalkyl group, and L represents S, SO, or SO 2 ),
Or Rx1C (═O) — (wherein Rx1 is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, C1 To C6 alkoxy group, C1 to C6 haloalkoxy group, C3 to C8 cycloalkoxy group, or RaRbN— (wherein Ra and Rb have the same meanings as described above);
Het,
Represents a 5-membered heterocyclic group containing a sulfur atom and a nitrogen atom,
In the 5-membered heterocyclic group containing a sulfur atom and a nitrogen atom, R3 is appropriately substituted with 0 to 2 (provided that when there is disubstituted R3, R3 represents an independent substituent).
R3 is
Hydroxyl group,
Cyano group,
Nitro group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
A C3 to C8 cycloalkyl group optionally substituted with a substituent C,
A C2-C6 alkenyl group optionally substituted with a substituent C,
C2-C6 haloalkenyl group,
A C2 to C6 alkynyl group optionally substituted with a substituent C,
A C2-C6 haloalkynyl group,
A C1 to C6 alkoxy group optionally substituted with a substituent C,
A C1 to C6 haloalkoxy group,
A C3 to C8 cycloalkoxy group optionally substituted with a substituent C,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent C,
A C2-C6 haloalkenyloxy group,
A C3-C6 alkynyloxy group optionally substituted with a substituent C,
A C3 to C6 haloalkynyloxy group,
RaRbN- (wherein Ra and Rb are as defined above),
Rc-L- (wherein Rc and L are as defined above),
Rx1C (= O)-(where Rx1 is as defined above),
Rx1C (= O) O- (where Rx1 is as defined above),
Or Rx2C (═O) N (Rx3)-(wherein Rx2 is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group). An alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, or RaRbN- (wherein Ra and Rb have the same meanings as described above), and Rx3 is , A hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group).
R4 is
Hydroxyl group,
Cyano group,
Nitro group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
A C3 to C8 cycloalkyl group optionally substituted with a substituent C,
A C2-C6 alkenyl group optionally substituted with a substituent C,
C2-C6 haloalkenyl group,
A C2 to C6 alkynyl group optionally substituted with a substituent C,
A C2-C6 haloalkynyl group,
A C1 to C6 alkoxy group optionally substituted with a substituent C,
A C1 to C6 haloalkoxy group,
A C3 to C8 cycloalkoxy group optionally substituted with a substituent C,
A C2-C6 alkenyloxy group which may be optionally substituted with a substituent C,
A C2-C6 haloalkenyloxy group,
A C3-C6 alkynyloxy group optionally substituted with a substituent C,
A C3 to C6 haloalkynyloxy group,
RaRbN- (wherein Ra and Rb are as defined above),
Rc-L- (wherein Rc and L are as defined above),
Rx1C (= O)-(where Rx1 is as defined above),
Rx1C (= O) O- (where Rx1 is as defined above),
Or Rx2C (= O) N (Rx3)-(wherein Rx2 and Rx3 have the same meanings as defined above);
R5 has the same meaning as R4 described above;
n represents an integer of 0 to 4;
X represents an oxygen atom or a sulfur atom;
A bond containing a broken line represents a double bond or a single bond;
The substituent A is a hydroxyl group, a cyano group, a C3 to C8 cycloalkyl group, a C1 to C6 alkoxy group, a C1 to C6 haloalkoxy group, a C3 to C8 cycloalkoxy group, or a RaRbN- (here, Ra And Rb are as defined above.), And Rc-L- (wherein Rc and L are as defined above), and at least one selected from the group consisting of:
Substituent B is at least one selected from the group consisting of a cyano group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, and a C3-C8 cycloalkoxy group;
Substituent C is a hydroxyl group, a cyano group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, a C2-C6 alkoxyalkoxy group, RaRbN -(Wherein Ra and Rb are as defined above), Rc-L- (wherein Rc and L are as defined above), Rx1C (= O)-(wherein Rx1) Is the same as defined above.) And 3 to 6 membered ring group containing 1 to 2 oxygen atoms. Or a salt thereof.
Het,
Represents a thiazolyl group, an isothiazolyl group, a thiadiazolyl group, or a thiatriazolyl group,
In the thiazolyl group, the isothiazolyl group, the thiadiazolyl group, or the thiatriazolyl group, R3 is appropriately substituted by 0 to 2 (provided that when there is disubstituted R3, R3 represents each independent substituent).
The compound according to claim 1 or a salt thereof.
R1 is
A C1 to C6 alkyl group optionally substituted with a substituent A,
Or represents a C1-C6 haloalkyl group;
R2 is
Hydrogen atom,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent A,
A C1 to C6 haloalkyl group,
A C2-C6 alkynyl group optionally substituted with a substituent A,
Or represents a C1-C6 alkoxy group which may be optionally substituted with a substituent A;
Het,
Represents a thiazolyl group or a thiadiazolyl group,
In the thiazolyl group or the thiadiazolyl group, R3 is appropriately substituted by 0 to 2 (provided that when there is disubstituted R3, R3 represents each independent substituent).
R3 is
Cyano group,
Nitro group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
A C3 to C8 cycloalkyl group optionally substituted with a substituent C,
A C2-C6 alkenyl group optionally substituted with a substituent C,
A C2 to C6 alkynyl group optionally substituted with a substituent C,
A C1 to C6 alkoxy group optionally substituted with a substituent C,
RaRbN- (wherein Ra and Rb are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group). Or an alkyl group, or Ra and Rb represent an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidinyl group, a homopiperidinyl group, or an azocanyl group together with the nitrogen atom to which they are attached.
Or Rx2C (═O) N (Rx3)-(wherein Rx2 is a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group). An alkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C8 cycloalkoxy group, or RaRbN- (wherein Ra and Rb have the same meanings as described above), and Rx3 is , A hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 cycloalkyl group).
R4 is
Cyano group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
A C1 to C6 alkoxy group optionally substituted with a substituent C,
Or represents a C1-C6 haloalkoxy group;
R5 is
Hydroxyl group,
Cyano group,
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
A C2-C6 alkenyl group optionally substituted with a substituent C,
A C2 to C6 alkynyl group optionally substituted with a substituent C,
A C1 to C6 alkoxy group optionally substituted with a substituent C,
A C1 to C6 haloalkoxy group,
Or Rc-L- (wherein Rc represents a C1-C6 alkyl group or a C1-C6 haloalkyl group, and L represents S, SO, or SO 2 ).
The compound according to claim 2 or a salt thereof.
R1 is
Represents a C1-C6 alkyl group which may be optionally substituted with a substituent A;
R2 is
Hydrogen atom,
Halogen atom,
Or represents a C1 to C6 alkyl group which may be optionally substituted with a substituent A;
R3 is
Halogen atom,
A C1 to C6 alkyl group optionally substituted with a substituent C,
A C1 to C6 haloalkyl group,
Or RaRbN— (wherein Ra and Rb are each independently a hydrogen atom, a C1 to C6 alkyl group optionally substituted with a substituent B, a C1 to C6 haloalkyl group, or a C3 to C8 Or a Ra and Rb together with the nitrogen atom to which they are attached form an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidinyl group, a homopiperidinyl group, or an azocanyl group. Representation;
R4 is
Halogen atom,
Or represents a C1 to C6 alkyl group which may be optionally substituted with a substituent C;
R5 is
Cyano group,
Halogen atom,
Or represents a C1 to C6 alkoxy group which may be optionally substituted with a substituent C,
The compound according to claim 3 or a salt thereof.
An agricultural and horticultural pest control agent containing the compound according to claim 1 or a salt thereof as an active ingredient.
An agricultural and horticultural fungicide containing the compound according to claim 1 or a salt thereof as an active ingredient.
A method for controlling plant diseases, which comprises applying the agricultural and horticultural pest control agent according to claim 5 to plants, plant seeds, or soil in which plants are cultivated.
A method for controlling plant diseases, which comprises applying the agricultural / horticultural fungicide according to claim 6 to plants, plant seeds, or soil in which plants are cultivated.