TW201930267A - N-methoxyamide compound or salt thereof, and agricultural and horticultural fungicide containing same - Google Patents

Abstract

Provided is an agricultural and horticultural fungicide manifesting a high control effect against a wide range of plant pathogens. The compound represented by formula (1): (in the formula, each symbol is as described in the specification) or a salt thereof.

Description

N-methoxyindoleamine compound or salt thereof and agricultural and horticultural fungicide containing the same

The present invention relates to an N-methoxyindoleamine compound or a salt thereof and a horticultural fungicide containing the same.

Compounds having a certain structure of benzamidine methylguanamine are known to be useful for the control of a wide variety of pests. For example, in Patent Documents 1 and 2, a compound having a structure of benzamidine methyl guanamine useful as an insecticide, an acaricide or a nematicide is described, and Patent Documents 3 and 4 are described as having agricultural and horticultural use. A fungicide useful as a compound of benzamidine methylamine. However, in these documents, the compound of the formula (1) described below, that is, a compound having a methoxy group-modified N-methoxyguanamine structure and a R ^B- substituted heterocyclic group, has a nitrogen atom of a guanamine. It is not described with specific examples.

Patent Document 5 describes a agricultural and horticultural fungicide having a pyrazole ring substituted with a methoxy group or an ethoxy group, but does not have "-C(O)-C(Me) ₂ -" of the formula (1) described later. structure.
[Previous Technical Literature]
[Patent Literature]

[Patent Document 1] International Publication WO 01/60783
[Patent Document 2] International Publication WO03/27059
[Patent Document 3] International Publication WO2006/016708
[Patent Document 4] International Publication WO2007/069777
[Patent Document 5] International Publication WO2007/060164

[Questions to be solved by the invention]

Since the past, most agricultural and horticultural fungicides provided for the prevention of plant diseases have their own characteristics in their spectrum or plant pathogen control effects. However, for a specific plant disease, the effect is insufficient, or the treatment effect is slightly deteriorated compared with the preventive effect, or the residual effect of the rain resistance deterioration is relatively short, and the application scene is only practical for the plant pathogenic bacteria. The situation is not enough to prevent the effect. Accordingly, efforts have been made to create agricultural and horticultural fungicides that do not have a high degree of control effect on a wide range of plant pathogenic bacteria.

[Means to solve the problem]

In order to solve the above-mentioned problems, the inventors of the present invention have found that the compound represented by the formula (1) or a salt thereof, which exhibits an excellent control effect against various plant diseases, has been completed.

That is, the present invention relates to a compound represented by the formula (1) or a salt thereof (hereinafter, also referred to as a compound of the present invention), a horticultural fungicide containing the compound of the present invention as an active ingredient, and a compound of the present invention applied to a plant. Or the method of controlling soil diseases in the soil.

[Wherein, A is the substituted phenyl is substituted with the R ^A or R ^A pyridyl,
B is a heterocyclic group substituted by R ^B (the heterocyclic group may be further substituted by 1 to 3 R ^B' ),
R ^A may be the same or different in a halogen atom, an alkyl group which may be substituted by G ¹ , an alkenyl group, an alkynyl group which may be substituted by G ² , a cyclic group, a nitro group, a cyano group or -L ^A -Y ^A , or Two R ^A can be bonded to form a ring that can be substituted by Z ¹ .
R ^B is -L ^B -Y ^B ,
R ^{B '} is a halogen atom, an alkyl group, a haloalkyl group, an alkoxyalkyl group, a cycloalkyl group or a cyano group.
L ^A is O, S, C(=O), C(=O)O, C(=O)N(R ¹ ), OC(=O), OC(=O)O, N(R ¹ ), N(R ¹ )C(=O), N(R ¹ )C(=O)O, C(=NR ² ), SO, SO ₂ or SO ₂ N(R ¹ ),
Y ^A is a hydrogen atom, an alkyl group which may be substituted by Z ² , an alkenyl group or a cyclic group which may be substituted by Z ³ .
L ^B is O, S, C(=O), C(=O)O, C(=O)N(R ³ ), OC(=O), N(R ³ ), N(R ³ )C( =O), N(R ³ )C(=O)O, C(=NR ⁴ ), SO, SO ₂ or SO ₂ N(R ³ ),
Y ^B is a hydrogen atom, an alkyl group which may be substituted by Z ⁴ , an alkenyl group, a cycloalkyl group, a phenyl group which may be substituted by Z ⁵ or a heterocyclic group which may be substituted by Z ⁵ ,
R ¹ is a hydrogen atom or an alkyl group,
R ² is a hydrogen atom, an alkyl group or an alkoxy group.
R ³ is a hydrogen atom or an alkyl group,
R ⁴ is a hydrogen atom, an alkyl group or an alkoxy group.
G ¹ is a halogen atom or an alkoxy group,
G ² is a cycloalkyl group or a halogen atom,
Z ¹ is a halogen atom, an alkyl group, an alkoxy group or a cycloalkyl group.
Z ² is a halogen atom, a cyano group, a cycloalkyl group or an alkoxy group.
Z ³ is a halogen atom or a haloalkyl group,
Z ⁴ is a halogen atom, a cycloalkyl group or an alkoxy group.
Z ⁵ is a halogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group or an alkoxy group].

[Effect of the invention]

The compound of the present invention is useful as a fungicide for agricultural and horticultural use because it exhibits an excellent plant disease control effect and osmotic transfer property as compared with a similar conventional compound.

In the present specification, the number of R ^A which is a substituent of a phenyl group or a pyridyl group may be one or two or more (for example, two, three, four, etc.). When there are two or more, R ^A may be the same or different.

In the present specification, examples of the halogen atom or a halogen atom as a substituent include each atom of fluorine, chlorine, bromine or iodine. The number of halogen atoms as a substituent may be 1 or 2 or more, and when it is 2 or more, each halogen atom may be the same or different.
Further, the substitution position of the halogen atom may be any position.

In the present specification, examples of the alkyl group or the alkyl moiety include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and an n- group. a linear or branched chain C ₁ -C ₁₂ group of a pentyl, neopentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl or dodecyl group.

In the present specification, examples of the alkenyl or alkenyl moiety include a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 2-methyl-1-propenyl group, and a 1-methyl-1- group. Propylene, 2-methyl-2-propenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentyl Straight chain or branch of alkenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-hexenyl, 2,3-dimethyl-2-butenyl A chain of C ₂ -C ₆ groups.

In the present specification, examples of the alkynyl group or alkynyl group include, for example, an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, and 1 -methyl-2-propynyl, 2-methyl-3-butynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl a linear or branched chain C ₂ -C ₆ group of 3,3-dimethyl-1-butynyl.

In the present specification, examples of the cycloalkyl or cycloalkyl moiety include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, and a bicyclo[1,1,1] pentyl group. Based on the basis of C ₃ -C ₁₀ .

In the present specification, the term "cyclic group" means a saturated or unsaturated carbocyclic group or a heterocyclic group. The carbocyclic group is a cyclic group containing only a carbon atom as a ring atom, and examples thereof include a cycloalkyl group (for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, and a bicyclic ring). [1,1,1]pentyl, etc.) and a C ₃ -C ₁₀ group of an aryl group (e.g., phenyl, naphthyl, anthracenyl, indanyl, etc.). Examples of the heterocyclic group include a monocyclic heterocyclic group having 3 to 6 members of one to four atoms selected from the group consisting of O, S and N (for example, epoxy B) a 3-membered heterocyclic group of an alkyl group, a thiiranyl group, or an azetidinyl group; a 4-membered heterocyclic group such as an oxetanyl group, a thietanyl group, or a fluorenyl group; a furyl group; , tetrahydrofuranyl, thienyl, pyrrolyl, oxazolyl, pyridyl, dioxolanyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, imidazolinyl, imidazolidinyl a 5-membered heterocyclic group such as pyrazolyl, pyrazolinyl, pyrazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, etc.; pyranyl, pyridyl, piperidinyl , dioxoalkyl, oxazinyl, morpholinyl, thiazinyl, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyl, triazinyl, thiopyranyl, dihydrothiopyranyl, oxathia a 6-membered heterocyclic group such as oxathiinyl or the like, and a condensed heterocyclic group having 1 to 4 atoms selected from at least one selected from the group consisting of O, S and N (for example, benzoyl) Furanyl, isobenzofuranyl, dihydrobenzofuran , dihydroisobenzofuranyl, benzothienyl, isobenzothiophenyl, dihydrobenzothiophenyl, dihydroisobenzothiophenyl, tetrahydrobenzothiophenyl, fluorenyl, isoindole Benzo, benzoxazolyl, benzothiazolyl, oxazolyl, benzimidazolyl, benzodioxolanyl, benzodioxyl, benzopyranyl, benzodihydrogen Piperyl, isobenzopyrano, chromonyl, chromanonyl, quinolinyl, isoquinolyl, porphyrinyl, pyridazinyl, quinazolinyl, Quinoxalinyl, indolizinyl, quinazolyl, imidazopyridyl, naphthyridinyl, pteridinyl, dihydrobenzoxazinyl, dihydrobenzoxazolone, dihydrobenzo Benzoxazinonyl, Benzothioxanyl, etc.).

As the heterocyclic group represented by B in the formula (1), the same as the heterocyclic group exemplified as the above cyclic group can be used. It is preferably a heterocyclic group of 5 to 6 members containing at least one atom selected from the group consisting of O, S and N, and more specifically, the following.
Select freestyle (B-1) ~ formula (B-18):

[In the formula, any one of R ^B1 to R ^B3 , any one of R ^B4 to R ^B6 , any one of R ^B7 to R ^B9 , any one of R ^B10 to R ^B12 , and R ^B13 to R ^B15 Any one of R ^B16 to R ^B18 and any one of R ^B19 to R ^B20 is -L ^B -Y ^B , and the residue is a halogen atom, an alkyl group, a haloalkyl group, an alkoxyalkyl group, or a ring. The alkyl group or the cyano group, the L ^B and Y ^B groups are as described above, * represents a 5-membered heterocyclic group represented by a bonding position], and the formula (B-101) to the formula (B-128):

[In the formula, any one of R ^B101 to R ^B104 , any one of R ^B105 to R ^B108 , any one of R ^B109 to R ^B111 , and any one of R ^B112 to R ^B114 is -L ^B -Y ^B The residue is a halogen atom, an alkyl group, a haloalkyl group, an alkoxyalkyl group, a cycloalkyl group or a cyano group, and L ^B and Y ^B are as defined above, and * represents a 6-membered heterocyclic group represented by a bonding position] Heterocyclic groups in the group.

The heterocyclic group represented by B may have a substituent in the atom adjacent to the atom to which the "*" is bonded.

In the formula (1), as ^{A in} which a ring is formed by bonding two R ^A groups, a benzodioxanyl group, a benzodioxanyl group, a benzothiazolyl group which may be substituted by Z ¹ may be mentioned. Dihydrobenzoxene hexenyl (benzoxathiinyl) and the like. Here, two Z ¹ bonded to the same carbon atom may be bonded to form a spiro ring, and examples of A in the case of forming a spiro ring include a spiro ring [benzo[d][1,3]dioxacyclohexane. Dioxol-2,1'-cyclopentan]-5-yl, spiro[benzo[d][1,3]dioxole-2,1'-cyclobutane Alkyl]-5-yl and the like.

The salt of the compound of the formula (1), if it is acceptable for agriculture, includes, for example, an alkali metal salt such as a sodium salt or a potassium salt; an alkaline earth metal salt such as a magnesium salt or a calcium salt; A mineral acid salt of a hydrochloride, a perchlorate, a sulfate or a nitrate; an organic acid salt such as an acetate or a methanesulfonate.

In the compound of the present invention, although various isomers such as optical isomers, geometric isomers and the like are present, the present invention includes both the isomers and the mixture of isomers. Further, among the compounds of the present invention, various isomers other than the above are also included within the scope of the technical knowledge in the technical field.

Further, there are cases in which a chemical structure different from the structural formula described above is caused by the type of the isomer, but if it is a general knowledge in the field of the present invention, the relationship of these isomers is Fully understood, it is well within the scope of the invention.

Although the compound of the present invention can be produced by the following methods for producing the reactions A to K and the usual salts, the method for obtaining the compound of the present invention is not limited thereto. For example, the compounds of the present invention may also be subjected to various substituent conversion reactions (e.g., hydrolysis) in the art by virtue of substituents on the phenyl or pyridyl group of A and/or substituents on the heterocyclic group of B. , oxidation, reduction, esterification, guanidine, alkylation, etc.). Further, in the production of the compound of the present invention, the protection and deprotection reactions which are usually used can be applied in the art if necessary.

Reaction A
Reaction A is a method of obtaining a compound of the formula (1) by methylating a compound of the formula (2).

The symbols in the formula are as described above.

The reaction A can be carried out under the usual methylation reaction conditions, and can usually be carried out in the presence of a methylating agent, a base and a solvent.

Examples of the methylating agent include methyl iodide, methyl bromide, dimethyl sulfate, and trimethyldecyl diazomethane. The methylating agent may be used in an amount of from 1 to 20 equivalents per 1 equivalent of the compound of the formula (2), and is desirably from 1 to 10 equivalents (the equivalent is a molar equivalent, the same applies hereinafter).
As the base, for example, an alkali metal such as sodium or potassium; an alkali metal alkoxide such as sodium methoxide, sodium ethoxide or potassium butanolate; a carbonate such as sodium carbonate or potassium carbonate; sodium hydrogencarbonate or potassium hydrogencarbonate; a hydrogencarbonate; a metal hydroxide such as sodium hydroxide or potassium hydroxide; a metal hydride such as sodium hydride or potassium hydride; such as monomethylamine, dimethylamine, triethylamine, diisopropyl An amine of ethylamine; a pyridine such as pyridine or 4-dimethylaminopyridine; such as methyl lithium, n-butyl lithium, lithium diisopropyl decylamine, lithium hexamethyldiazepine One or two or more kinds of organic lithium compounds and the like are appropriately selected. The base may be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (2).
The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, methyl chloride, chloroform, dichloromethane, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane; such as methyl acetate, acetic acid Esters of ethyl esters; such as methanol, ethanol, propanol, tert-butanol alcohols; such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl acetamide, N, N-dimethylformamide And a polar aprotic solvent of N-methylpyrrolidone, pyridine, acetonitrile or propionitrile; a ketone such as acetone or methyl ethyl ketone; and one or more selected from water and the like.

The reaction temperature is usually -78 to 100 ° C, desirably 0 to 80 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 0.1 to 24 hours.

The compound of the formula (2) used in the reaction A can be produced by the reaction 1-1 described later.

Reaction B
Reaction B is a method of reacting a compound of the formula (3) with a compound of the formula (4) to give a compound of the formula (1).

In the formula, T is a hydroxyl group, an alkoxy group, an aryloxy group or a halogen, and other symbols are as described above.

Reaction B can usually be carried out in the presence of a base and a solvent. The compound of the formula (4) can be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (3).

The base may be, for example, an alkali metal such as sodium or potassium; an alkali metal alkoxide such as sodium methoxide, sodium ethoxide or potassium butoxide; a carbonate such as sodium carbonate or potassium carbonate; for example, sodium hydrogencarbonate or potassium hydrogencarbonate. a hydrogen hydride; a metal hydroxide such as sodium hydroxide or potassium hydroxide; a metal hydride such as sodium hydride or potassium hydride; such as monomethylamine, dimethylamine, triethylamine, diisopropyl An amine of a base; a pyridine such as pyridine or 4-dimethylaminopyridine; an organic lithium compound such as methyl lithium, n-butyl lithium or lithium diisopropyl decylamine, or the like 2 or more types. The base may be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (3).
The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, methyl chloride, chloroform, dichloromethane, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane; such as methyl acetate, acetic acid Ester of ethyl ester; such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl acetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, propionitrile A protic solvent, such as acetone or a ketone of methyl ethyl ketone, may be appropriately selected from one or two or more.

The reaction B can be carried out in the presence of a dehydrating condensing agent if necessary. The dehydrating condensing agent may, for example, be N,N'-dicyclohexylcarbodiimide, chlorosulfonyl isocyanate, N,N'-carbonyldiimidazole or trifluoroacetic anhydride. The dehydrating condensing agent may be used in an amount of from 1 to 5 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (3).

The reaction temperature is usually 0 to 100 ° C, desirably 0 to 50 ° C, and the reaction time is usually about 0.5 to 48 hours, and is desirably about 1 to 24 hours.

The compound of the formula (3) used in the reaction B can be produced by the reaction 1-2 or the reaction 1-3 described later. The compound of the formula (4) can be produced by the following reaction 2-1 or a known method, or a commercially available product can be used.

Reaction C
Reaction C is a method in which a compound of the formula (5) is reacted with a compound of the formula (6) to give a compound of the formula (1).

In the formula, X is a chlorine atom, a bromine atom or an iodine atom, and other symbols are as described above.

The reaction C can usually be carried out in the presence of a base and a solvent. The compound of the formula (6) can be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (5).

As the base, for example, an alkali metal such as sodium or potassium; an alkali metal alkoxide such as sodium methoxide, sodium ethoxide or potassium butoxide; a carbonate such as sodium carbonate or potassium carbonate; such as sodium hydrogencarbonate or hydrogen carbonate; a hydrogen carbonate of potassium; a metal hydroxide such as sodium hydroxide or potassium hydroxide; a metal hydride such as sodium hydride or potassium hydride; such as monomethylamine, dimethylamine, triethylamine, diisopropyl One or two or more kinds of the amines of the ethyl ethylamine are appropriately selected. The base can be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, based on the compound of the formula (5).
The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, methyl chloride, chloroform, dichloromethane, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane; such as methyl acetate, acetic acid Esters of ethyl esters; such as methanol, ethanol, propanol, tert-butanol alcohols; such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl acetamide, N, N-dimethylformamide And a polar aprotic solvent of N-methylpyrrolidone, pyridine, acetonitrile or propionitrile; a ketone such as acetone or methyl ethyl ketone; and one or more selected from water and the like.

The reaction temperature is usually from 0 to 100 ° C, desirably from 20 to 80 ° C, and the reaction time is usually from about 0.1 to 48 hours, and is desirably from about 1 to 24 hours.

The compound of the formula (5) used in the reaction C can be produced according to the reactions 1 to 9 described later. The compound of the formula (6) can be produced by a known method, or a commercially available product can be used.

Reaction D
Reacting a compound of formula D line (7), the R of A ^{1 A} from a compound of formula (1-1) of fluorine, the method is converted into R ^{A A 2} of the formula (1-2) of the hydroxyl groups of the compound.

In the formula, A ¹ is a phenyl group substituted by fluorine or a pyridyl group substituted by fluorine, and A ² is a phenyl group substituted by a hydroxy group or a pyridyl group substituted by a hydroxy group, and other symbols are as described above.

Reaction D can usually be carried out in the presence of a base and a solvent. The compound of the formula (7) can be used in an amount of from 1 to 10 equivalents, preferably from 1 to 5 equivalents, per equivalent of the compound of the formula (1-1).

The base may be, for example, an alkali metal such as sodium or potassium; an alkali metal alkoxide such as sodium methoxide, sodium ethoxide or potassium butoxide; a carbonate such as sodium carbonate or potassium carbonate; for example, sodium hydrogencarbonate or potassium hydrogencarbonate. a hydrogen hydride; a metal hydroxide such as sodium hydroxide or potassium hydroxide; a metal hydride such as sodium hydride or potassium hydride; such as monomethylamine, dimethylamine, triethylamine, diisopropyl An amine of a base; a pyridine such as pyridine or 4-dimethylaminopyridine; an organic lithium compound such as methyl lithium, n-butyl lithium or lithium diisopropyl decylamine, or the like 2 or more types. The base may be used in an amount of from 1 to 10 equivalents, preferably from 1 to 5 equivalents, per equivalent of the compound of the formula (1-1).
The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, methyl chloride, chloroform, dichloromethane, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane; such as methyl acetate, acetic acid Ester of ethyl ester; such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl acetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, propionitrile A protic solvent, such as acetone or a ketone of methyl ethyl ketone, may be appropriately selected from one or two or more.

The reaction temperature is usually 0 to 150 ° C, desirably 50 to 100 ° C, and the reaction time is usually about 1 to 24 hours, and is desirably about 1 to 12 hours.

Reaction E
Reacting a compound of formula E series (8) or the formula (9), the R ^{A A 2} of the compound of formula (1-2) is converted into the hydroxyl groups of ^A R A ³ is of formula (1 -OY ^A1 of -3) Method of compound.

Wherein, A ³ is a substituent of the substituted phenyl or -OY ^A1-pyridinyl -OY ^A1, Y ^A1 Z ² which may be substituted with the alkyl group, alkenyl group, or Z ³ may be substituted with the cyclic group, other The symbol is as described above.

The reaction E can usually be carried out in the presence of a compound of the formula (8), a base and a solvent. Or, according to a general photo-stretching reaction, it can carry out in the presence of the compound of the formula (9), triphenylphosphine, azodicarboxylic acid diester, and a solvent. The compound of the formula (8) or the compound of the formula (9) may be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (1-2). Triphenylphosphine may be used in an amount of from 1 to 3 equivalents, preferably from 1 to 1.5 equivalents, per equivalent of the compound of the formula (1-2). The azodicarboxylate diester may be used in an amount of from 1 to 3 equivalents, preferably from 1 to 1.5 equivalents, per equivalent of the compound of the formula (1-2).

The base may, for example, be an alkali metal alkoxide such as sodium methoxide, sodium ethoxide or potassium butylate; a carbonate such as sodium carbonate or potassium carbonate; a hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate; a metal hydroxide of potassium hydroxide; a metal hydride such as sodium hydride or potassium hydride; an amine such as monomethylamine, dimethylamine, triethylamine or diisopropylethylamine; One or two or more kinds of pyridines such as 4-dimethylaminopyridine are appropriately selected. The base can be used in an amount of from 1 to 2 equivalents, and desirably from 1 to 1.5 equivalents, based on the compound of the formula (1-2).
The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, methyl chloride, chloroform, dichloromethane, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane; such as methyl acetate, acetic acid Ester of ethyl ester; such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl acetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, polar aprotic solvent; A nitrile of acetonitrile, propionitrile or acrylonitrile; a ketone of acetone or methyl ethyl ketone; one or more selected from water and the like.
As the azodicarboxylic acid diester, for example, diethyl azodicarboxylate or the like can be used.

The reaction temperature is usually -30 to 100 ° C, desirably 0 to 50 ° C, and the reaction time is usually about 0.1 to 24 hours, and is desirably about 0.1 to 12 hours.

The compound of the formula (8) and the formula (9) used in the reaction E can be produced by a known method, or a commercially available product can be used.

Reaction F
Reacting a compound of formula F line (10) or of formula (11), the R ^{A A 4} of the compound of formula (1-4) of the X into ^A R A ⁵ R ^A2 of a particular of the formula ( The method of the compound of 1-5).

Wherein, A ⁴ is a substituent of the phenyl group substituted by X or X-pyridyl, A ⁵ is substituted with the substituent of R ^A2 R ^A2 pyridyl or phenyl, R ^A2 is alkyl, haloalkyl, alkenyl, Alkyl group, alkynyl group, cyclic group, cyano group or -L ^A1 -Y ^A , L ^A1 is O, S, C(=O), C(=O)O, C(=O)N(R ¹ ), N(R ¹ ), N(R ¹ )C(=O)O, SO, SO ₂ or SO ₂ N(R ¹ ), M is a metal atom such as magnesium or zinc or a salt thereof, or boric acid or an ester thereof Residues, other symbols are as described above.

The reaction F can be usually carried out by using a compound of the formula (1-4) in the presence of a transition metal catalyst, a solvent and an inert gas, if necessary, adding a base, a compound of the formula (10) or a compound of the formula (11). The reaction is carried out.

The compound of the formula (10) or the compound of the formula (11) is not particularly limited as long as it can be reacted, and it can be prepared by a known method, or a commercially available product can be used. The compound of the formula (10) or the compound of the formula (11) may be used in an amount of from 1 to 10 equivalents, preferably from 1 to 5 equivalents, per equivalent of the compound of the formula (1-4).

Examples of the transition metal catalyst include a catalyst containing a transition metal such as palladium, copper, rhodium, ruthenium, nickel, cobalt, or molybdenum. As the transition metal catalyst, various known structures used for the cross-coupling reaction of the organohalide can be used, and a transition metal catalyst containing palladium in the present reaction is particularly useful. Examples of the transition metal catalyst containing palladium include palladium-carbon, palladium chloride, palladium acetate, dichlorobis(acetonitrile)palladium, bis(dibenzylideneacetone)palladium, and dichlorobis(triphenyl). Palladium, ruthenium (triphenylphosphine) palladium, dichlorobis(1,4-bis(diphenylphosphino)butane)palladium, and the like. Further, a third-stage phosphine or a third-order phosphite may be used as a ligand if necessary. As the third-stage phosphine or the third-order phosphite, triphenylphosphine, phenyldimethylphosphine, tri-o-tolylphosphine, tri-p-tolylphosphine, 1,2-bis (two) Phenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino) Ferrocene, triphenyl phosphite, and the like. The transition metal catalyst may be used in an amount of from 0.001 to 0.5 equivalents, preferably from 0.05 to 0.2 equivalents, per equivalent of the compound of the formula (1-4). Further, the ligand is usually used in an amount of from 1 to 50 equivalents, preferably from 1 to 10 equivalents, per equivalent of the transition metal catalyst. However, amounts outside this range may also be used depending on the reaction conditions.

As the base, for example, an alkali metal carbonate such as sodium carbonate, potassium carbonate or cesium carbonate; an alkali metal alkoxide such as sodium methoxide, sodium ethoxide or potassium butylate; a hydrogencarbonate such as an alkali metal of sodium hydrogencarbonate; a salt; a carbonate of an alkaline earth metal such as calcium carbonate; a metal hydroxide such as sodium hydroxide or potassium hydroxide; a metal hydride such as sodium hydride or potassium hydride; such as triethylamine, diisopropylethyl An amine, pyridine, 4-(N,N-dimethylamino)pyridine, an organic amine of imidazole, and the like. The base may be used in an amount of from 1 to 20 equivalents, preferably from 1 to 10 equivalents, per equivalent of the compound of the formula (1-4).

The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, methyl chloride, chloroform, dichloromethane, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane; such as methyl acetate, acetic acid Ester of ethyl ester; such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl acetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, polar aprotic solvent; a nitrile of acetonitrile, propionitrile or acrylonitrile; a ketone such as acetone or methyl ethyl ketone; an alcohol such as methanol, ethanol, propanol or tert-butanol; and one or more selected from water and the like. .

As the inert gas, for example, a nitrogen gas, an argon gas or the like can be used.

The reaction temperature is usually -100 to 200 ° C, desirably -78 to 100 ° C, and the reaction time is usually about 0.5 to 96 hours, and is desirably about 1 to 48 hours.

Reaction G
The reaction G is obtained by reacting a compound of the formula (1-6) with a (halo)alkylating agent, a oximation agent or an alkoxycarbonylating agent, or a alkylation reaction of a light-reacting reaction or a reduction to obtain a formula (1) 7) The method of the compound.

In the formula, B ¹ is a heterocyclic group substituted with a hydroxyl group or an amine group (the heterocyclic group may be further substituted by RB ^' ), and B ² is a heterocyclic group substituted with -L ^B1 -Y ^B1 (the heterocyclic group) Can be further substituted by R ^{B '} ), L ^B1 is O, OC(=O), OC(=O)O, N(R ³ ), N(R ³ )C(=O) or N(R ³ )C (=O)O, Y ^B1 is an alkyl group, an alkenyl group or a cycloalkyl group which may be substituted by Z ⁴ , and other symbols are as described above.

In the reaction G, the reaction of the (halo)alkylating agent, the deuterating agent or the alkoxycarbonylating agent can be carried out usually in the presence of a base and a solvent. The (halo)alkylating agent, the halogenating agent or the alkoxycarbonylating agent may be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (1-6).
Alternatively, the reaction G can be carried out in the presence of an aldehyde, a reducing agent, an acid, and a solvent according to a general Mitsunobu reaction or a general reduction alkylation reaction.

As the base and the solvent, those used in the above reaction E can be used.
Examples of the (halo)alkylating agent include halogenated alkyl groups such as methyl iodide and methane bromide; dialkyl sulfates such as dimethyl sulfate; trimethylsulfonyl diazomethane; and chlorodifluoromethane. , sodium chlorodifluoroacetate, and the like.
Examples of the halogenating agent include acid chlorides such as mercapto chloride; acid anhydrides such as acetic anhydride; and the like.
Examples of the alkoxycarbonylating agent include chloroformate such as methyl chloroformate.

The reaction temperature is usually -30 to 100 ° C, desirably 0 to 50 ° C, and the reaction time is usually about 0.1 to 24 hours, and is desirably about 0.1 to 12 hours.

The smoothing reaction can be carried out in accordance with the aforementioned reaction E.

As the aldehyde in the reduction alkylation reaction, for example, formaldehyde, acetaldehyde or the like can be used. The aldehyde may be used in an amount of from 1 to 10 equivalents, preferably from 1 to 5 equivalents, per equivalent of the compound of the formula (1-6).
As the reducing agent, for example, one type or two or more types may be appropriately selected from sodium cyanoborohydride, sodium triethoxy borohydride, and the like. The reducing agent may be used in an amount of from 1 to 5 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (1-6).
As the acid, for example, acetic acid or the like can be used. The acid may be used in an amount of from 1 to 30 equivalents, preferably from 1 to 10 equivalents, per equivalent of the compound of the formula (1-6).
As the solvent, any solvent may be used as a solvent inert to the reaction, for example, a nitrile such as acetonitrile or propionitrile; an ether such as dioxane, tetrahydrofuran, diethyl ether or dimethoxyethane. For example, alcohols such as methanol, ethanol, propanol, and tert-butanol; and one or more selected from water and the like.
The reaction temperature is usually 0 to 80 ° C, desirably 0 to 50 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 0.5 to 24 hours.

Reaction H
The reaction H is a method of obtaining a compound of the formula (1-6) by reacting a compound of the formula (1-8) with an acid or a fluoride or by contact reduction.

Wherein B ³ is a heterocyclic group substituted by -L ^B2 -Y ^B2 (the heterocyclic group may be further substituted by RB ^' ), L ^B2 is O or N(R ³ ), Y ^B2 is an alkyl group, three Alkylalkyl, alkoxyalkyl, arylalkyl, alkoxycarbonyl or arylalkoxycarbonyl, the other symbols are as described above.

The reaction H can usually be carried out by reacting a compound of the formula (1-8) in the presence of a solvent with an acid or a fluoride. Or, it can be carried out by a general contact reduction in a hydrogen atmosphere by using platinum, platinum oxide, platinum black, Raney nickel, palladium, palladium carbon, rhodium, ruthenium-alumina or the like as a catalyst.

The solvent is not particularly limited as long as it can be reacted, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; fats such as hexane, heptane, petroleum ether, petroleum ether, and cyclohexane. a hydrocarbon; a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride or 1,2-dichloroethane; an ether such as diethyl ether, tetrahydrofuran or dioxane; methyl acetate, An ester of ethyl acetate; one or two or more selected from the group consisting of methanol, ethanol, propanol, tert-butanol alcohol, water, and the like.
The acid is not particularly limited as long as it can be reacted, and examples thereof include a Lewis acid such as boron tribromide; a Bronsted acid such as hydrochloric acid or trifluoroacetic acid; and the like. The acid is used in an amount of from 1 to 10 equivalents, preferably from 1 to 3 equivalents, per equivalent of the compound of the formula (1-8).
The fluoride is not particularly limited as long as it can be reacted, and examples thereof include tetra-n-butylammonium fluoride and cesium fluoride. The fluoride may be used in an amount of from 1 to 10 equivalents, preferably from 1 to 3 equivalents, per equivalent of the compound of the formula (1-8).

The reaction temperature is usually -30 to 200 ° C, desirably 0 to 100 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 0.1 to 24 hours.

Reaction I
Alkylation reaction system I R ^{A A 6} by the reaction of a compound of an alkylating agent or acylation agent, (halo) formula (1-9) of the group is, or reduced, converted into R ^A A method of a compound of the formula (1-10) of -L ^A2 -Y ^A1 .

In the formula, A ⁶ is a phenyl group substituted by an amine group or a pyridyl group substituted by an amine group, and A ⁷ is a phenyl group substituted by -L ^A2 -Y ^A1 or a pyridyl group substituted by -L ^A2 -Y ^A1 , L ^A2 is N(R ¹ ), N(R ¹ )C(=O) or N(R ¹ )C(=O)O, and other symbols are as described above.

In Reaction I, the reaction of a (halo)alkylating agent or a halogenating agent can be carried out usually in the presence of a base and a solvent. Further, the alkylation reaction of the reduction in the reaction I can be carried out in the presence of an aldehyde, a reducing agent, an acid and a solvent in accordance with a general reduction alkylation reaction.

In the reaction I, the reaction of the (halo)alkylating agent or the deuterating agent and the alkylation reaction of the reduction can be carried out according to the above reaction G, respectively.

Reaction J
Reaction J is a method of converting a compound of the formula (1-11) into a compound of the formula (1-12).

In the formula, A ⁸ is a phenyl group substituted with two hydroxyl groups bonded to an adjacent carbon atom, and A ⁹ is a benzodioxocyclopentyl group which may be substituted by Z ¹ , and other symbols are as described above.

The reaction J can usually be carried out in the presence of a ketone, an aldehyde or an orthoester, with an acid or a dehydrating agent and a solvent. The ketone, aldehyde or orthoester may be used in an amount of from 1 to 50 equivalents, preferably from 1 to 5 equivalents, per equivalent of the compound of the formula (1-11).
Or the reaction J can be carried out in the presence of 1,1-dibromoethane or dibromodifluoromethane, a base and a solvent. 1,1-Dibromoethane and dibromodifluoromethane may be used in an amount of from 1 to 10 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (1-11).

The ketone, the aldehyde or the orthoester may be appropriately selected depending on the desired Z ¹ , and examples thereof include a ketone such as acetone, methyl ethyl ketone or cyclopentanone; an aldehyde such as acetaldehyde or isobutyl aldehyde; Such as ethyl orthoformate, the original acid ester of ethyl acetate.
Examples of the acid include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, and the like. Examples of the dehydrating agent include phosphorus pentaoxide and the like. The base may, for example, be a metal hydroxide such as sodium hydroxide or potassium hydroxide; or a carbonate such as sodium carbonate, potassium carbonate or cesium carbonate. The acid may be used in an amount of 0.01 to 5 equivalents, preferably 0.05 to 1 equivalent, per equivalent of the compound of the formula (1-11). The dehydrating agent or base may be used in an amount of from 1 to 10 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (1-11).
The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, methyl chloride, chloroform, dichloromethane, An aliphatic hydrocarbon of dichloroethane, trichloroethane, hexane or cyclohexane; an alcohol such as methanol, ethanol, propanol or tert-butanol; a nitrile such as acetonitrile, propionitrile or acrylonitrile; One or more selected from the group consisting of a polar aprotic solvent such as dimethyl sulfoxide, cyclobutyl hydrazine, dimethyl acetamide, N, N-dimethylformamide or N-methylpyrrolidone .

The reaction temperature is usually 0 to 150 ° C, desirably 20 to 100 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 1 to 24 hours.

Reaction K
Reaction K is a method of converting a compound of the formula (1-13) into a compound of the formula (1-14).

In the formula, A ¹⁰ is a phenyl group substituted by an alkenyl group or an alkynyl group or a pyridyl group substituted by an alkenyl group or an alkynyl group, and A ¹¹ is a phenyl group substituted by an alkyl group or a pyridyl group substituted by an alkyl group, and other symbols are As mentioned above.

The reaction K can be carried out by a general contact reduction, and is carried out by using platinum, platinum oxide, platinum black, Raney nickel, palladium, palladium carbon, rhodium, ruthenium-alumina or the like as a catalyst in a hydrogen atmosphere.

The reaction K can be carried out by contact reduction described in the above reaction H.

The method for producing the compound used in the reactions A to K is described below, but is not limited thereto. These compounds can be produced by a known method, or a commercially available product can be used.

Reaction 1-1
Reaction 1-1 is a method of reacting a compound of the formula (100) with a compound of the formula (4) to give a compound of the formula (2). Further, a compound of the formula (2) can be obtained by hydrolyzing a compound of the formula (101) which is obtained together with the compound of the formula (2).

The symbols in the formula are as described above.

In Reaction 1-1, the reaction of the compound of the formula (100) with the compound of the formula (4) can be carried out usually in the presence of a base and a solvent, or, if necessary, in the presence of a dehydrating condensing agent.
The base, the solvent, and the dehydrating condensing agent can be used in the above-mentioned reaction B. The compound of the formula (4) can be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (100). The base may be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (100).

The reaction temperature is usually 0 to 100 ° C, desirably 0 to 50 ° C, and the reaction time is usually about 0.5 to 48 hours, and is desirably about 1 to 24 hours.

In the reaction 1-1, the compound of the formula (2) can be introduced by hydrolyzing the compound of the formula (101) which is obtained together with the compound of the formula (2).
The hydrolysis can be carried out under the usual hydrolysis reaction conditions, usually in the presence of an acid or a base and a solvent.

Examples of the acid include hydrochloric acid, sulfuric acid, and the like. Examples of the base include metal hydroxides such as sodium hydroxide and potassium hydroxide. The acid or base may be used in an amount of from 1 to 10 equivalents, preferably from 1 to 5 equivalents, per equivalent of the compound of the formula (100).
If the solvent is a solvent inert to the reaction, any solvent may be used, for example, an alcohol such as methanol, ethanol, propanol or tert-butanol; a nitrile such as acetonitrile, propionitrile or acrylonitrile; for example, acetone, A A ketone of a ketone group; one or two or more types are appropriately selected from water and the like.

The reaction temperature for the hydrolysis is usually from 0 to 100 ° C, desirably from 20 to 80 ° C, and the reaction time is usually from about 0.1 to 12 hours, preferably from about 0.1 to about 1 hour.

The compound of the formula (100) used in the reaction 1-1 can be produced by the following Reaction 1-4 or Reaction 1-5. The compound of the formula (4) can be produced by the following reaction 2-1 or a known method, or a commercially available product can be used.

Reaction 1-2
Reaction 1-2 is a method of obtaining a compound of the formula (3) by methylating a compound of the formula (100).

The symbols in the formula are as described above.

The reaction 1-2 can be carried out in accordance with the aforementioned reaction A.

Reaction 1-3
Reaction 1-3 is a method of reacting a compound of the formula (5) with O-methylhydroxylamine hydrochloride to obtain a compound of the formula (3).

The symbols in the formula are as described above.

The reaction 1-3 can be carried out in accordance with the reaction C. The O-methylhydroxylamine hydrochloride can be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (5).

Reaction 1-4
Reaction 1-4 is a method of reducing a compound of the formula (102) to give a compound of the formula (100).

The symbols in the formula are as described above.

As a reduction reaction, for example, it can be reduced by contact with platinum oxide, Raney nickel, palladium-carbon, ruthenium or the like as a catalyst in a hydrogen atmosphere; in a metal such as iron, zinc, and, for example, hydrochloric acid, acetic acid, chlorination The reduction of the reaction system composed of the ammonium acid is carried out.

Reactions 1-4 can generally be carried out in the presence of a solvent. The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene or xylene; an aliphatic hydrocarbon such as hexane or cyclohexane; such as dioxane or tetrahydrofuran. Ether of diethyl ether or dimethoxyethane; such as esters of methyl acetate and ethyl acetate; such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl acetamide, N, N- a polar aprotic solvent of dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile or propionitrile; ketones such as acetone and methyl ethyl ketone; such as methanol, ethanol, propanol, tert-butanol One or two or more kinds of alcohols are appropriately selected from water and the like.

The reaction temperature is usually 0 to 150 ° C, desirably 0 to 80 ° C, and the reaction time is usually about 0.5 to 96 hours, and is desirably about 0.5 to 48 hours.

The compound of the formula (102) used in the above Reaction 1-4 can be produced by the following Reaction 1-6 or Reaction 1-8.

Reaction 1-5
Reaction 1-5 is a method of reacting a compound of the formula (5) with a hydroxylamine hydrochloride to obtain a compound of the formula (100).

The symbols in the formula are as described above.

The reaction 1-5 can be carried out in accordance with the reaction C. The hydroxylamine hydrochloride can be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (5).

The reaction temperature is usually from 0 to 100 ° C, desirably from 20 to 80 ° C, and the reaction time is usually from about 0.1 to 48 hours, and is desirably from about 1 to 24 hours.

Reaction 1-6
The reaction of 1-6 is a method of oxidizing a compound of the formula (103) to give a compound of the formula (102).

The symbols in the formula are as described above.

Examples of the oxidation reaction include oxidation of a reaction system composed of chromic acid, sulfuric acid, pyridine, and pyridinium salts; oxidation of a reaction system composed of dimethyl sulfoxide and chlorophyll chloride; Oxidation of a reaction system consisting of tetrapropylammonium acid with a co-oxidant such as N-methylmorpholine-N-oxide; oxidation by Dess-Martin Periodinane; by manganese dioxide Oxidation and the like.

Reactions 1-6 can generally be carried out in the presence of a solvent. The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene or xylene; for example, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, trichloro An aliphatic hydrocarbon of ethane, hexane or cyclohexane; an ether such as dioxane, tetrahydrofuran, diethyl ether or dimethoxyethane; an ester such as methyl acetate or ethyl acetate; a polar aprotic solvent such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl acetamide, N,N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile or propionitrile; A ketone of methyl ethyl ketone; an alcohol such as methanol, ethanol, propanol or tert-butanol; and one or more selected from water and the like.

The reaction temperature is usually -78 to 150 ° C, desirably -50 to 80 ° C, and the reaction time is usually about 0.5 to 96 hours, and is desirably about 0.5 to 48 hours.

The compound of the formula (103) used in the reaction 1-6 can be produced by the following reaction 1-7.

Reaction 1-7
Reaction 1-7 is a method of reacting a compound of the formula (104) with 2-nitropropane to give a compound of the formula (103).

The symbols in the formula are as described above.

The reaction 1-7 can be carried out according to a general nitroalcohol reaction, usually in the presence of a base, if necessary in the presence of a solvent. The 2-nitropropane may be used in an amount of from 1 to 30 equivalents, preferably from 1 to 10 equivalents, per equivalent of the compound of the formula (104).

As the base, for example, an alkali metal such as sodium or potassium; an alkali metal alkoxide such as sodium methoxide, sodium ethoxide or potassium butoxide; a carbonate such as sodium carbonate or potassium carbonate; such as sodium hydrogencarbonate or hydrogen carbonate; a hydrogen carbonate of potassium; a metal hydroxide such as sodium hydroxide or potassium hydroxide; a metal hydride such as sodium hydride or potassium hydride; such as monomethylamine, dimethylamine, triethylamine, diisopropyl Amines of ethyl ethylamine; such as 1,8-diazabicyclo[5.4.0]undec-7-ene; such as tetramethylguanidine, 1,5,7-triazabicyclo[4.4 .0] One or two or more kinds of hydrazine-5-ene are appropriately selected. The base may be used in an amount of 0.1 to 2 equivalents, preferably 0.1 to 1 equivalent, per equivalent of the compound of the formula (104).
If the solvent is a solvent inert to the reaction, any solvent may be used, for example, an alcohol such as methanol, ethanol, propanol or tert-butanol; a nitrile such as acetonitrile, propionitrile or acrylonitrile; for example, acetone, A a ketone of ketoethyl ketone; an aliphatic hydrocarbon such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, trichloroethane, hexane or cyclohexane; such as dioxane, tetrahydrofuran, An ether of ethyl ether or dimethoxyethane; such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl acetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine The polar aprotic solvent; one or two or more kinds are appropriately selected from water and the like.

The reaction temperature is usually 0 to 100 ° C, desirably 20 to 50 ° C, and the reaction time is usually about 0.1 to 168 hours, and is desirably about 1 to 24 hours.

The compound of the formula (104) used in the reaction 1-7 can be produced by a known method, or a commercially available product can be used.

Reaction 1-8
The reaction 1-8 is a method of nitrating a compound of the formula (5) to give a compound of the formula (102).

The symbols in the formula are as described above.

Reactions 1-8 can generally be carried out in the presence of a nitrating agent and a solvent.

As the nitrating agent, for example, one type or two or more types may be appropriately selected from sodium nitrite and potassium nitrite. The nitrating agent may be used in an amount of from 1 to 2 equivalents, preferably from 1 to 1.5 equivalents, per equivalent of the compound of the formula (5).
The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, chloroform, dichloromethane, dichloroethane An aliphatic hydrocarbon such as trichloroethane, hexane or cyclohexane; an ether such as dioxane, tetrahydrofuran, diethyl ether or dimethoxyethane; an ester such as methyl acetate or ethyl acetate a polar aprotic solvent such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl acetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile or propionitrile; For example, a ketone of acetone or methyl ethyl ketone; an alcohol such as methanol, ethanol, propanol or tert-butanol; and one or more selected from water and the like.

The reaction temperature is usually 0 to 150 ° C, desirably 20 to 50 ° C, and the reaction time is usually about 0.1 to 96 hours, and is desirably about 0.5 to 24 hours.

Reaction 1-9
Reaction 1-9 is a method of halogenating a compound of formula (105) to give a compound of formula (5).

The symbols in the formula are as described above.

The reaction 1-9 can be carried out in the presence of a base in the presence of a halogenating agent (for example, a chlorinating agent, a brominating agent or an iodinating agent) and a solvent. The halogenating agent may be used in an amount of from 1 to 2 equivalents, preferably from 1 to 1.5 equivalents, per equivalent of the compound of the formula (105).

As the chlorinating agent, for example, one or two or more kinds of chlorine, N-chlorosuccinimide, and the like can be appropriately selected, and as the brominating agent, for example, bromine, sulfonium imine bromide, or trimethyl group can be used. One or two or more kinds are appropriately selected from the group consisting of phenyl tribromide and the like. The iodinating agent can be appropriately selected from the group consisting of iodine and N-iodosuccinimide, for example, one or two or more.
If the solvent is a solvent inert to the reaction, any solvent may be used, for example, from carbon tetrachloride, methyl chloride, chloroform, dichloromethane, dichloroethane, trichloroethane, hexane, cyclohexane. Aliphatic hydrocarbons; such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane ethers; such as methyl acetate, ethyl acetate esters; such as dimethyl hydrazine, cyclobutyl hydrazine a polar aprotic solvent of dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone or pyridine; an organic acid such as acetic acid or propionic acid; one of water or the like 2 or more types.
Examples of the base include lithium diisopropyl decylamine and the like. The base may be used in an amount of from 1 to 2 equivalents, and desirably from 1 to 1.2 equivalents, based on the compound of the formula (105).
When it is carried out in the presence of a base, the solvent can be appropriately selected from one or two or more selected from the group consisting of ethers such as tetrahydrofuran and diethyl ether.
Reactions 1-9 If necessary, an organic acid such as acetic acid, propionic acid or a Lewis acid such as aluminum chloride can be used as a catalyst. Further, it is possible to use as an organic acid as a catalyst in excess, and also serve as a solvent.

The reaction temperature is usually -100 to 150 ° C, desirably -78 to 110 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 0.5 to 24 hours. When it is carried out in the presence of a base, the reaction temperature is usually -100 to 0 ° C, desirably -78 to -20 ° C, the reaction time is usually about 0.1 to 12 hours, and it is desirably about 0.5 to 6 hours, and further, in the acid In the presence of the reaction, the reaction temperature is usually from 0 to 150 ° C, desirably from 20 to 110 ° C, and the reaction time is usually from about 0.1 to 48 hours, preferably from about 1 to 24 hours.

The compound of the formula (105) used in the reaction 1-9 can be produced by the following Reaction 1-10 to Reaction 1-19.

Reaction 1-10
The reaction 1-10 is a method of obtaining a compound of the formula (105) by a Friedel-Crafts reaction of a compound of the formula (106) and a compound of the formula (107).

In the formula, A' corresponds to the ring of A, and other symbols are as described above.

The reaction 1-10 can be carried out according to the general Friedel-Crafts reaction, usually in the presence of an acid and a solvent. The compound of the formula (107) can be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (106).
As the acid, for example, an inorganic acid such as hydrochloric acid or sulfuric acid; an organic acid such as p-toluenesulfonic acid or trifluoromethanesulfonic acid; or a Lewis such as aluminum chloride, iron chloride, zinc chloride or boron trifluoride etherate. One or two or more kinds are appropriately selected from the group consisting of acids and the like. The acid may be used in an amount of 0.1 to 3 equivalents, and desirably 1 to 2 equivalents based on the compound of the formula (106).
The solvent may be any solvent if it is a solvent inert to the reaction, for example, a nitrile such as acetonitrile, propionitrile or acrylonitrile; for example, carbon tetrachloride, chloroform, dichloromethane, dichloroethane or trichloroethane. An aliphatic hydrocarbon of alkane, hexane or cyclohexane; an ether such as dioxane, tetrahydrofuran, diethyl ether or dimethoxyethane; such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl One or two or more kinds are appropriately selected from the group consisting of acetamide, N,N-dimethylformamide, N-methylpyrrolidone, and a polar aprotic solvent of pyridine.

The reaction temperature is usually 0 to 100 ° C, desirably 0 to 80 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 1 to 24 hours.

The compound of the formula (106) and the formula (107) used in the reaction 1-10 can be produced by a known method, or a commercially available product can be used.

Reaction 1-11
Reaction 1-11 comprises the step of chlorinating or hydrazating a compound of formula (108) to give a compound of formula (109), and reacting a compound of formula (109) with a compound of formula (110) to give A method of the second step of the compound of formula (105).

In the formula, U is a chlorine atom, a dialkylamino group (e.g., dimethylamino group, diethylamino group) or N-methoxy-N-methylamino group, and the other symbols are as described above.

The first step of the first step is chlorination, which can be carried out in the presence of a chlorinating agent and a solvent. In the case of guanidation, it can be used in a dialkylamine (for example, dimethylamine) or N-methoxy-N. It is carried out in the presence of a methylamine, a dehydrating condensing agent, a base and a solvent.

As the chlorinating agent, for example, one type or two or more types may be appropriately selected from the group consisting of sulfinium chloride, grass chloroform, and phosphorus pentachloride. The chlorinating agent may be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (108).
The dehydrating condensing agent, the base, and the solvent can be used in the above-mentioned reaction B. The dehydrating condensing agent may be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (108). The base can be used in an amount of from 1 to 10 equivalents, and desirably from 1 to 5 equivalents, based on the compound of the formula (108).

The reaction temperature is usually 0 to 100 ° C, desirably 0 to 80 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 1 to 24 hours.

The second step, the second step, can usually be carried out in the presence of a solvent, if necessary in the presence of an inert gas. The compound of the formula (110) can be used in an amount of from 1 to 3 equivalents, preferably from 1 to 1.5 equivalents, per equivalent of the compound of the formula (108) or the formula (109).

The solvent may be any solvent if it is a solvent which is inert to the reaction. For example, one or two or more kinds may be appropriately selected from, for example, an ether such as dioxane, tetrahydrofuran or diethyl ether. The inert gas can be appropriately selected, for example, from a nitrogen gas, an argon gas or the like.

The reaction temperature is usually -20 to 100 ° C, desirably 0 to 50 ° C, and the reaction time is usually about 1 to 48 hours, and is desirably about 1 to 20 hours.

The compound of the formula (108) and the formula (110) used in the reaction 1-11 can be produced by a known method, or a commercially available product can be used.

Reaction 1-12
Reaction 1-12 is a method of reacting a compound of the formula (111) with a compound of the formula (110) to give a compound of the formula (105).

The symbols in the formula are as described above.

The reaction 1-12 can be carried out usually in the presence of a solvent, if necessary in the presence of a catalyst and an inert gas. The compound of the formula (110) can be used in an amount of from 1 to 3 equivalents, preferably from 1 to 1.5 equivalents, per equivalent of the compound of the formula (111). The catalyst may be used in an amount of from 0.001 to 1 equivalent, and preferably from 0.01 to 0.5 equivalent, per equivalent of the compound of the formula (111).

Examples of the catalyst include copper iodide (I) and the like.
The solvent and inert gas can be used in the second step of the aforementioned Reactions 1-11.

The reaction temperature is usually -20 to 100 ° C, desirably 0 to 50 ° C, and the reaction time is usually about 1 to 48 hours, and is desirably about 1 to 20 hours.

The compound of the formula (111) used in the reaction 1-12 can be produced by a known method, or a commercially available product can be used.

Reaction 1-13
Reaction 1-13 is a method of reacting a compound of the formula (112) with a compound of the formula (113) to give a compound of the formula (105).

Wherein V is a bromine atom or an iodine atom, and G is a leaving group (for example, a halogen such as a chlorine atom or a bromine atom; an alkoxy group such as a methoxy group or an epoxy group; such as a dimethylamino group or a diethylamine; A dialkylamino group; an aziridine group which may be substituted with an N-methoxy-N-methylamino group or an alkyl group, and the other symbols are as described above.

The reaction 1-13 can be carried out usually in the presence of an organometallic reagent and a solvent, or in the presence of a magnesium metal, an activating agent and a solvent, if necessary in the presence of an inert gas. The compound of the formula (113) can be used in an amount of from 1 to 3 equivalents, preferably from 1 to 1.5 equivalents, per equivalent of the compound of the formula (112).
The organometallic reagent can be appropriately selected from one or two or more selected from the group consisting of an organic lithium compound such as methyllithium or n-butyllithium; a grammatic compound such as isopropylmagnesium chloride. The organometallic reagent may be used in an amount of from 1 to 2 equivalents, preferably from 1 to 1.5 equivalents, per equivalent of the compound of the formula (112).
The metal magnesium may be used in an amount of from 1 to 3 equivalents, preferably from 1 to 1.5 equivalents, per equivalent of the compound of the formula (112). Examples of the activator include iodine and 1,2-dibromoethane. The activator may be used in an amount of 0.01 to 1 equivalent, and preferably 0.05 to 0.5 equivalent, based on 1 equivalent of the compound of the formula (112).
If the solvent is a solvent inert to the reaction, any solvent may be used, for example, an aliphatic hydrocarbon such as hexane or cyclohexane; an ether such as dioxane, tetrahydrofuran or diethyl ether; Kind or more than two.
The inert gas can be appropriately selected, for example, from a nitrogen gas, an argon gas or the like.

The reaction temperature is usually -100 to 100 ° C, desirably -78 to 80 ° C, and the reaction time is usually about 1 to 48 hours, and is desirably about 1 to 20 hours.

The compound of the formula (112) and the formula (113) used in the reaction 1-13 can be produced by a known method, or a commercially available product can be used.

Reaction 1-14
The reaction 1-14 comprises a first step of reacting a compound of the formula (104) with a compound of the formula (110) to obtain a compound of the formula (114), and a compound of the formula (114) to give a formula (105). The method of the second step of the compound.

The symbols in the formula are as described above.

The first step of the first step can be carried out in accordance with the second step of the above reaction 1-11.

The second step and the second step can be carried out in accordance with the above Reactions 1-6.

Reaction 1-15
Reaction 1-15 is a reaction of a compound of formula (105-1) wherein R ^A of A ¹² is -L ^A3 -Y ^A2 with a (halo)alkylating agent, a oximation agent or an alkoxycarbonylating agent, A method of alkylation of a light-extension reaction or reduction to a compound of the formula (105-2) wherein A ^{13 has} a R ^A of -L ^A4 -Y ^A2 .

Wherein A ¹² is a phenyl group substituted by -L ^A3 -Y ^A2 or
-L ^A3 -Y ^A2 substituted pyridyl group, L ^A3 is O, S or N(R ¹ ), A ¹³ is
-L ^A4 -Y ^A2 substituted phenyl or pyridyl group substituted by -L ^A4 -Y ^A2 , L ^A4 is O, OC(=O), OC(=O)O, S, N(R ¹ ), N (R ¹ )C(=O) or N(R ¹ )C(=O)O, and other symbols are as described above.

The reaction 1-15 can be carried out according to the reaction G.

Reaction 1-16
Reaction 1-16 comprises a Friedel-Crafts reaction of a compound of formula (106) and a compound of formula (115) to give a first step of the compound of formula (116), and a methylation formula (116) a compound obtained by the method of the second step of the compound of the formula (105).

The symbols in the formula are as described above.

The first step can be carried out in accordance with the aforementioned Reaction 1-10.

The second step can be carried out in accordance with the aforementioned reaction A.

Reaction 1-17
Reaction 1-17 comprises the first step of reacting a compound of formula (112) with a compound of (117) to give a compound of formula (114), and a compound of formula (114) to give a compound of formula (105) The method of the second step.

The first step of the first step can be carried out in accordance with the aforementioned reaction 1-13.

The second step and the second step can be carried out in accordance with the above Reactions 1-6.

Reaction 1-18
Reaction 1-18 comprises the first step of reacting a compound of formula (104) with a compound of formula (118) to provide a compound of formula (119), oxidizing a compound of formula (119) to provide a compound of formula (120) The method of the second step, and the method of reducing the compound of the formula (120), to obtain the third step of the compound of the formula (105).

The symbols in the formula are as described above.

The first step of the first step can be carried out in accordance with the second step of the above reaction 1-11.

The second step and the second step can be carried out in accordance with the above Reactions 1-6.

The third step of the third step can be carried out by contact reduction described in the above reaction H.

Reaction 1-19
The reaction 1-19 R ^{A A 14-based} compounds of the formula (105-3) of the hydroxyl groups, R ^{A A 15} into the compound of formula (105-4) or the mercapto group of a method.

In the formula, A ¹⁴ is a phenyl group substituted by a hydroxy group or a pyridyl group substituted by a hydroxy group, and A ¹⁵ is a phenyl group substituted with a mercapto group or an amine group or a pyridyl group substituted with a mercapto group or an amine group, and other symbols are as described above.

Reactions 1-19 can be carried out according to the general Froberg Schönberg reaction. The compound of the formula (105-3) can be usually reacted with dimethylthioamine formazan chloride in the presence of a base and a solvent, followed by a rearrangement reaction and hydrolysis to obtain a compound of the formula (105-4). The dimethyl thiocarbamidine chloride may be used in an amount of from 1 to 5 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (105-3).
Or reactions 1-19 can be carried out according to the general Smiles rearrangement reaction. The compound of the formula (105-3) can be usually reacted with 2-bromoisobutylguanamine in the presence of a base and a solvent, followed by a rearrangement reaction and hydrolysis to obtain a compound of the formula (105-4). The 2-bromoisobutylguanamine can be used in an amount of from 1 to 10 equivalents, preferably from 1 to 3 equivalents, per equivalent of the compound of the formula (105-3).
The rearrangement reaction can be carried out in the presence of a solvent, and the hydrolysis can be carried out in accordance with the above reaction 1-1.

In Reactions 1-19, as a base, it can be used in the above-mentioned reactions 1-7. The base may be used in an amount of from 1 to 5 equivalents, preferably from 1 to 3 equivalents, per equivalent of the compound of the formula (105-3).
The solvent may be any solvent if it is a solvent inert to the reaction, for example, a nitrile such as acetonitrile, propionitrile or acrylonitrile; for example, carbon tetrachloride, chloroform, dichloromethane, dichloroethane or trichloroethane. An aliphatic hydrocarbon of alkane, hexane or cyclohexane; an ether such as dioxane, tetrahydrofuran, diethyl ether or dimethoxyethane; such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl A polar aprotic solvent of acetamide, N,N-dimethylformamide, N-methylpyrrolidone or pyridine; and one or more selected from the group consisting of N,N-dimethylaniline and the like.

The reaction temperature is usually 0 to 200 ° C, desirably 20 to 150 ° C, and the reaction time is usually about 1 to 48 hours, and is desirably about 1 to 20 hours.

Reaction 2-1
Reaction 2-1 is a compound of the formula (4) wherein a compound of the formula (4) is brominated or chlorinated with T as a hydroxyl group to obtain a compound of the formula (4-2) wherein T is a bromine atom or a chlorine atom. Methods.

In the formula, B ¹¹ is a heterocyclic group substituted by R ^B or a nitro group (the heterocyclic group may be further substituted by RB ^' ), and T ¹ is a bromine atom or a chlorine atom, and other symbols are as described above.

Reaction 2-1 can usually be carried out by reacting a compound of the formula (4-1) in the presence of a solvent with a brominating agent or a chlorinating agent.

The solvent is not particularly limited as long as it can be reacted, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; fats such as hexane, heptane, petroleum ether, petroleum ether, and cyclohexane. a hydrocarbon; a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane; an ether such as diethyl ether, tetrahydrofuran, dioxane, etc. and a mixture thereof One type or two or more types are appropriately selected from the solvent and the like.
The brominating agent is not particularly limited as long as it can carry out the reaction, and examples thereof include phosphorus ruthenium bromide. The chlorinating agent is not particularly limited as long as it can be reacted, and examples thereof include grass chlorochloride, sulfinium chloride, and phosphonium chloride. The brominating agent or the chlorinating agent may be used in an amount of from 1 to 10 equivalents, preferably from 1 to 3 equivalents, per equivalent of the compound of the formula (4-1).

Reaction 2-1 can also be carried out by adding N,N-dimethylformamide. N,N-dimethylformamide is used in an amount of 0.01 to 3 equivalents, and preferably 0.05 to 0.3 equivalents, based on 1 equivalent of the compound of the formula (4-1).

The reaction temperature is usually 0 to 200 ° C, desirably 0 to 100 ° C, and the reaction time is usually about 0.1 to 12 hours.

The compound of the formula (4-1) can be produced by a known method or by a method described later, or a commercially available product can be used. As a known method, for example, International Publication No. WO 1993/11117, U.S. Patent No. 5,093,347, and the like are not limited thereto, and various kinds of documents can be used if they have ordinary knowledge in the field of the invention. The general synthetic methods described or the appropriate combinations thereof are suitable for use in the present invention.

Reaction 2-2
Reaction 2-2 is a method of reacting a compound of the formula (4-3) wherein T ² is an alkoxy group or an aryloxy group with an acid or a base to give a compound of the formula (4-1).

In the formula, B ¹¹ is a heterocyclic group substituted by R ^B or a nitro group (the heterocyclic group may be further substituted by RB ^' ), and T ² is an alkoxy group or an aryloxy group, and other symbols are as described above.

The reaction 2-2 can usually be carried out by reacting a compound of the formula (4-3) with an acid or a base in the presence of a solvent.

The acid is not particularly limited as long as it can be reacted. For example, hydrochloric acid, sulfuric acid, trifluoroacetic acid, p-toluenesulfonic acid or the like can be used. The base is not particularly limited as long as it can be reacted, and examples thereof include alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; alkali metal hydrogencarbonates such as sodium hydrogencarbonate; and alkaline earth metals such as calcium carbonate. a carbonate; a metal hydroxide such as sodium hydroxide or potassium hydroxide. The acid or base can be used in an amount of 0.1 to 20 equivalents, and desirably 0.1 to 10 equivalents, per equivalent of the compound of the formula (4-3).
The solvent is not particularly limited as long as it can be reacted, and examples thereof include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as hexane and heptane; diethyl ether, tetrahydrofuran, dioxane, and the like. Ethers; alcohols such as methanol and ethanol; halogenated hydrocarbons such as chloroform, dichloroethane, and carbon tetrachloride; and one or more selected from the group consisting of water and a mixed solvent thereof.

The reaction temperature is usually 0 to 200 ° C, desirably 0 to 100 ° C, and the reaction time is usually about 1 to 48 hours.

The compound of the formula (4-3) can be produced by a known method or by a method described later, or a commercially available product can be used. As a known method, for example, International Publication No. WO2001/23358, Journal of the American Chemical Society, Vol. 128, pp. 5310 to 5311 (2006), U.S. Patent No. 5,093,347, U.S. Patent No. 5,223,526, etc., but The present invention is not limited thereto, and those having ordinary knowledge in the field of the invention may be applied to the present invention by a general synthesis method described in various documents or an appropriate combination thereof.

Reaction 2-3
Reaction 2-3 is a method of reacting a compound of the formula (200) with an acid or a base to obtain a compound of the formula (4-1).

The symbols in the formula are as described above.

The reaction 2-3 can usually be carried out by reacting a compound of the formula (200) with an acid or a base in the presence of a solvent.

As the acid, the base and the solvent, those used in the above reaction 2-2 can be used. The acid or base may be used in an amount of from 1 to 20 equivalents, and desirably from 1 to 10 equivalents, per equivalent of the compound of the formula (200).

The reaction temperature is usually 0 to 200 ° C, desirably 0 to 100 ° C, and the reaction time is usually about 1 to 48 hours.

The compound of the formula (200) can be produced by a known method, or a commercially available product can be used.

Reaction 2-4
Reaction 2-4 is a method of obtaining a compound of the formula (4-1) by oxidizing a compound of the formula (201).

The symbols in the formula are as described above.

The reaction 2-4 can usually be carried out by reacting a compound of the formula (201) with an oxidizing agent in the presence of a solvent.

The oxidizing agent is not particularly limited as long as it can be reacted, and examples thereof include sodium chlorite, chromium oxide, pyridinium dichromate, and potassium permanganate. The oxidizing agent may be used in an amount of 0.01 to 20 equivalents, and preferably 0.1 to 10 equivalents, per equivalent of the compound of the formula (201).
The solvent is not particularly limited as long as it can be reacted, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; fats such as hexane, heptane, petroleum ether, petroleum ether, and cyclohexane. a hydrocarbon; a halogenated hydrocarbon such as chloroform, dichloromethane, carbon tetrachloride or 1,2-dichloroethane; an alcohol such as ethanol, methanol or butanol; water and a mixed solvent thereof; One type or two or more types are appropriately selected.

The reaction temperature is usually -100 to 100 ° C, desirably -80 to 50 ° C, and the reaction time is usually about 1 to 48 hours.

The compound of the formula (201) can be produced by a known method, or a commercially available product can be used.

Reaction 2-5
Reaction 2-5 is a method of converting a compound of the formula (202) into a compound of the formula (203).

Wherein B ⁴ is a heterocyclic group substituted by X (the heterocyclic group may be further substituted by R ^{B1 '} ), and B ⁵ is a heterocyclic group substituted by Q ¹ (the heterocyclic group may be further substituted by R ^{B1 ')} And Q ¹ is an alkoxy group, an arylalkoxy group, a haloalkoxy group, an alkylthio group, an alkylamino group, a dialkylamino group or an arylalkylamino group, and R ^C is a hydrogen atom or an alkoxy group. Or an alkoxy group, R ^{B1 '} is an alkyl group, a haloalkyl group, an alkoxyalkyl group, a cycloalkyl group or a cyano group, and the other symbols are as described above.

The reaction 2-5 can be carried out according to the reaction F.

The compound of the formula (202) can be produced by a known method, or a commercially available product can be used.

Reaction 2-6
Reaction 2-6 is a method of converting a compound of formula (204) to a compound of formula (205).

Wherein B ⁶ is a heterocyclic group substituted by R ^B and Q ² (the heterocyclic group may be further substituted by RB ^' ), and B ⁷ is substituted by R ^B and a monofluoroalkyl or alkoxyalkyl group. a heterocyclic group (which may be further substituted by RB ^' ), Q ² is an alkyl group substituted by Q ³ , and Q ³ is a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, a nitro group, an alkyl sulfonate Or fluorosulfonate, other marks are as described above.

The reaction 2-6 can usually be carried out by reacting with an alkylating agent and a fluorinating agent in the presence of a base and a solvent.

The alkylating agent is not particularly limited as long as it can be reacted, and examples thereof include a dialkyl sulfate such as methyl iodide or a halogenated alkyl group of methyl bromide, and a dimethyl sulfate. Nitrogen methane, etc.
The fluorinating agent is not particularly limited as long as it can carry out the reaction, and examples thereof include a fluoride salt of cesium fluoride; a quaternary ammonium salt such as tetra-n-butylammonium fluoride; and a defluorinated fluorine such as CRYSTAL FLUOR. Chemical agent, etc.
As the base, for example, an alkali metal alkoxide such as sodium methoxide, sodium ethoxide, potassium butoxide of the third stage; a carbonate such as sodium carbonate or potassium carbonate; a hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate; a metal hydroxide of sodium oxide or potassium hydroxide; a metal hydride such as sodium hydride or potassium hydride; an amine such as monomethylamine, dimethylamine, triethylamine or diisopropylethylamine; For example, one or two or more selected from the group consisting of pyridine and 4-dimethylaminopyridine pyridine; and an organic lithium compound such as methyllithium, n-butyllithium or lithium diisopropylguanamine. The alkylating agent, the fluorinating agent or the base may be used in an amount of from 1 to 20 equivalents, preferably from 1 to 10 equivalents, per equivalent of the compound of the formula (204).
The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, methyl chloride, chloroform, dichloromethane, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane; such as methanol, ethanol, C Alcohol, tert-butanol alcohols; such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl acetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, C The polar aprotic solvent of the nitrile; one or more selected from the group consisting of water and a mixed solvent thereof.

The reaction temperature is usually 0 to 100 ° C, desirably 0 to 80 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 0.1 to 24 hours.

The compound of the formula (204) can be produced by a known method, or a commercially available product can be used.

Reaction 2-7
The reaction 2-7 is a method of obtaining a compound of the formula (207) having a fluorine atom.

Wherein B ⁸ is a group which may be substituted by Q ^{5 and} substituted by R ^B (the heterocyclic group may be further substituted by R ^{B1 '} ), and B ⁹ is a heterocyclic group substituted by R ^B and fluorine, Q ⁵ R- ⁷ is hydrogen, alkoxy, aryloxy, arylalkoxy, in the case of a detachment group (for example, chlorine, bromine, iodine, nitro, alkyl sulfonate or fluorosulfonate, etc.), an amine group or a hydroxyl group. , hydroxyl or halogen, other symbols are as described above.

In the reaction 2-7, when Q ⁵ is a leaving group, the compound of the formula (207) can be obtained by reacting a compound of the formula (206) with a fluorinating agent usually in the presence of a solvent.
The fluorinating agent is not particularly limited as long as it can be reacted, and examples thereof include a fluoride salt of cesium fluoride; a quaternary ammonium salt such as tetramethylammonium fluoride or tetra-n-butylammonium fluoride; . The fluorinating agent may be used in an amount of from 1 to 20 equivalents, preferably from 1 to 10 equivalents, per equivalent of the compound of the formula (206).
The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, methyl chloride, chloroform, dichloromethane, An aliphatic hydrocarbon of dichloroethane, trichloroethane, hexane or cyclohexane; an ether such as dioxane, tetrahydrofuran, diethyl ether or dimethoxyethane; such as dimethyl hydrazine Suitable for polar aprotic solvents such as cyclobutyl hydrazine, dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile and propionitrile, and mixed solvents thereof. One or two or more types are selected.
The reaction temperature is usually 0 to 200 ° C, desirably 20 to 150 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 0.1 to 24 hours.

In the reaction 2-7, when Q ⁵ is an amine group, the compound of the formula (207) can be obtained by a Balz-Seaman reaction. In this case, the compound of the formula (206) is usually reacted with sodium nitrite and tetrafluoroboric acid in the presence of a solvent. Sodium nitrite and tetrafluoroboric acid may be used in an amount of from 1 to 20 equivalents, preferably from 1 to 10 equivalents, per equivalent of the compound of the formula (206).
The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, methyl chloride, chloroform, dichloromethane, An aliphatic hydrocarbon of dichloroethane, trichloroethane, hexane or cyclohexane; an ether such as dioxane, tetrahydrofuran, diethyl ether or dimethoxyethane; such as dimethyl hydrazine Suitable for polar aprotic solvents such as cyclobutyl hydrazine, dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile and propionitrile, and mixed solvents thereof. One or two or more types are selected.
The reaction temperature is usually 0 to 200 ° C, desirably 20 to 150 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 0.1 to 24 hours.

In the case of the reaction 2-7, Q ⁵ is a hydroxy group, the compound of the formula (206), usually in the presence of a solvent, if necessary in the presence of a fluoride salt, can be reacted by a deoxygenated fluorinating agent. The compound of formula (207) is obtained.
The deoxidizing fluorinating agent is not particularly limited as long as it can react, and examples thereof include PhenoFluor. The deoxidizing fluorinating agent may be used in an amount of from 1 to 20 equivalents, and desirably from 1 to 10 equivalents, per equivalent of the compound of the formula (206).
Examples of the fluoride salt include potassium fluoride and cesium fluoride. The fluoride salt may be used in an amount of from 1 to 10 equivalents, preferably from 1 to 5 equivalents, per equivalent of the compound of the formula (206).
The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, methyl chloride, chloroform, dichloromethane, An aliphatic hydrocarbon of dichloroethane, trichloroethane, hexane or cyclohexane; an ether such as dioxane, tetrahydrofuran, diethyl ether or dimethoxyethane; such as dimethyl hydrazine Suitable for polar aprotic solvents such as cyclobutyl hydrazine, dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile and propionitrile, and mixed solvents thereof. One or two or more types are selected.
The reaction temperature is usually 0 to 200 ° C, desirably 20 to 150 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 0.1 to 24 hours.

In the case of the reaction 2-7, B ⁸ is a heterocyclic group which may be substituted by Q ⁵ , usually in the presence of a solvent, if necessary in the presence of a base, by reacting an electrophilic fluorinating agent. a compound of formula (207).
The electrophilic fluorinating agent is not particularly limited as long as it can react, and examples thereof include a fluorine reagent (Selectfluor) and N-fluorobenzenesulfonimide. The electrophilic fluorinating agent may be used in an amount of from 1 to 20 equivalents, and desirably from 1 to 10 equivalents, per equivalent of the compound of the formula (206).
The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, methyl chloride, chloroform, dichloromethane, An aliphatic hydrocarbon of dichloroethane, trichloroethane, hexane or cyclohexane; an ether such as dioxane, tetrahydrofuran, diethyl ether or dimethoxyethane; such as dimethyl hydrazine Suitable for polar aprotic solvents such as cyclobutyl hydrazine, dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile and propionitrile, and mixed solvents thereof. One or two or more types are selected.
The base can be appropriately selected from one or two or more selected from the group consisting of lithium diisopropyl decylamine and lithium hexamine hexamethyl amide. The base may be used in an amount of from 1 to 5 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (206).
The reaction temperature is usually -100 to 200 ° C, desirably -78 to 150 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 0.1 to 24 hours.

The compound of the formula (206) can be produced by a known method, or a commercially available product can be used. Further, the compound of the formula (206) can also be used, for example, in Journal of the American Chemical Society, Vol. 139, pp. 1452-1455 (2017), Journal of Organic Chemistry, Vol. 80, pages 12137 to 12145 (2015), Organic Process. The method described in Research & Development, Vol. 18, pp. 1041 - 1044 (2014), or the like.

Reaction 2-8
Reaction of a 2-8 (halo)alkylated or cycloalkylated compound of formula (208) to a compound of formula (209).

Wherein B ¹⁰ is a heterocyclic group having NH substituted by R ^B (the heterocyclic group may be further substituted by RB ^' ), and B ¹¹ is substituted by R ^B and (halo)alkyl or cycloalkyl A heterocyclic group of N (the heterocyclic group may be further substituted by RB ^' ), and other symbols are as described above.

The reaction 2-8 can be carried out usually by reacting a (halo)alkylating agent or a cycloalkylating agent with a compound of the formula (208) in the presence of a base and a solvent. Further, the reaction can also be carried out by reacting a compound of the formula (208) with a metal-based reagent in the presence of a transition metal reagent and a solvent, if necessary, by adding a base.

As the (halo)alkylating agent, those used in the above reaction G can be used.
As the base, for example, an alkali metal alkoxide such as sodium methoxide, sodium ethoxide, potassium butoxide of the third stage; a carbonate such as sodium carbonate or potassium carbonate; a hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate; a metal hydroxide of sodium oxide or potassium hydroxide; a metal hydride such as sodium hydride or potassium hydride; an amine such as monomethylamine, dimethylamine, triethylamine or diisopropylethylamine; For example, one or two or more selected from the group consisting of pyridine and 4-dimethylaminopyridine pyridine; and an organic lithium compound such as methyllithium, n-butyllithium or lithium diisopropylguanamine. The (halo)alkylating agent or base may be used in an amount of from 1 to 20 equivalents, desirably from 1 to 10 equivalents, per equivalent of the compound of the formula (208).
The organic metal reagent is not particularly limited as long as it can be reacted, and examples thereof include an organic boron compound. The organometallic reagent can be prepared by a known method, or a commercially available product can be used. The organometallic reagent may be used in an amount of from 1 to 10 equivalents, preferably from 1 to 5 equivalents, per equivalent of the compound of the formula (208).
As the transition metal reagent, various known structures used in the cross-coupling reaction can be used, and a transition metal reagent containing copper in the reaction is particularly useful. For example, copper (II) acetate or the like can be mentioned. Further, a diamine can be used as a ligand if necessary. Examples of the diamine include N,N,N',N'-tetramethylethylenediamine, 2,2'-bipyridyl group and the like. The transition metal reagent may be used in an amount of 0.1 to 5 equivalents, preferably 0.5 to 1.5 equivalents, per equivalent of the compound of the formula (208). Further, the ligand is usually used in an amount of from 1 to 10 equivalents, preferably from 1 to 5 equivalents, per equivalent of the transition metal catalyst. However, amounts outside this range may also be used depending on the reaction conditions.
The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, methyl chloride, chloroform, dichloromethane, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane; such as methanol, ethanol, C Alcohol, tert-butanol alcohols; such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl acetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, C The polar aprotic solvent of the nitrile; one or more selected from the group consisting of water and a mixed solvent thereof.

The reaction temperature is usually 0 to 100 ° C, desirably 0 to 80 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 0.1 to 24 hours.

The compound of the formula (208) can be produced by a known method, or a commercially available product can be used.

Reaction 2-9
Reaction 2-9 (halo)alkylation, oximation, alkoxyalkylation, alkoxycarbonylation or aryl alkoxycarbonylation of a compound of formula (210), converted to formula (211) Method of compound.

Wherein B ¹² is a heterocyclic group which may be substituted by -L ^B2 -Y ^B3 (the heterocyclic group may be further substituted by RB ^' ), and Y ^B3 is an alkyl group, a haloalkyl group, a trialkyl decyl group, an alkane An oxyalkyl group, an alkoxycarbonyl group or an arylalkoxycarbonyl group, the other symbols are as described above.

Reactions 2-9 can be obtained by the (halo)alkylating agent, the oximation alkylating agent, the alkoxyalkylating agent, the alkoxycarbonyl group by the compound of the formula (210) in the presence of a base and a solvent. The reaction is carried out by reacting a reagent or an aryl alkoxycarbonylating agent. The (halo)alkylating agent, the oximation alkylating agent, the alkoxyalkylating agent or the base may be used in an amount of from 1 to 20 equivalents, preferably from 1 to 10 equivalents, per equivalent of the compound of the formula (210). The alkoxycarbonylating agent or the arylalkoxycarbonylating agent may be used in an amount of from 1 to 3 equivalents, preferably from 1 to 2 equivalents, per equivalent of the compound of the formula (210).

As the (halo)alkylating agent, those used in the above reaction G can be used.
Examples of the oximation alkylating agent include chlorotriethyl decane and chlorotriisopropyl decane.
Examples of the alkoxyalkylating agent include chloromethyl methyl ether and the like.
As the base, for example, an alkali metal alkoxide such as sodium methoxide, sodium ethoxide, potassium butoxide of the third stage; a carbonate of sodium carbonate or potassium carbonate; a hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate; a metal hydroxide of sodium or potassium hydroxide; a metal hydride such as sodium hydride or potassium hydride; an amine such as monomethylamine, dimethylamine or triethylamine; such as pyridine or 4-dimethylamine The pyridine of the pyridine is one or more selected from the group consisting of an organic lithium compound such as methyllithium, n-butyllithium or lithium diisopropylamine.
Examples of the alkoxycarbonylating agent include di-tert-butyl dicarbonate, and examples of the aryl alkoxycarbonylating agent include benzyl chloroformate.
The solvent may be any solvent if it is a solvent inert to the reaction, for example, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; for example, carbon tetrachloride, methyl chloride, chloroform, dichloromethane, Aliphatic hydrocarbons of dichloroethane, trichloroethane, hexane, cyclohexane; ethers such as dioxane, tetrahydrofuran, diethyl ether, dimethoxyethane; such as methanol, ethanol, C Alcohol, tert-butanol alcohols; such as dimethyl hydrazine, cyclobutyl hydrazine, dimethyl acetamide, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, C The polar aprotic solvent of the nitrile; one or more selected from the group consisting of water and a mixed solvent thereof.

The reaction temperature is usually 0 to 100 ° C, desirably 0 to 80 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 0.1 to 24 hours.

The compound of the formula (210) can be produced by a known method, or a commercially available product can be used.

Reaction 2-10
Reaction 2-10 is a method of oxidizing a compound of formula (212) to give a compound of formula (213).

Wherein B ¹³ is a heterocyclic group substituted with an amine group (the heterocyclic group may be further substituted by RB ^' ), and B ¹⁴ is a heterocyclic group substituted with a nitro group (the heterocyclic group may be further substituted by R ^{B '} Instead, the other marks are as described above.

The reaction 2-10 can usually be carried out in the presence of an oxidizing agent, an acid and a solvent.

As the oxidizing agent, one or two or more kinds may be appropriately selected from a boron compound such as sodium perborate; a metal oxide such as vanadium pentoxide or titanium dioxide; or hydrogen peroxide. The oxidizing agent may be used in an amount of from 0.01 to 10 equivalents, preferably from 0.1 to 5 equivalents, per equivalent of the compound of the formula (212).
The acid is not particularly limited as long as it can be reacted. For example, hydrochloric acid, sulfuric acid, trifluoroacetic acid, p-toluenesulfonic acid or the like can be used. The acid may be used in an amount of from 1 to 50 equivalents, preferably from 1 to 20 equivalents, per equivalent of the compound of the formula (212).
As the solvent, those used in the above reactions 1-6 can be used.

The reaction temperature is usually -20 to 100 ° C, desirably 0 to 80 ° C, and the reaction time is usually about 0.1 to 48 hours, and is desirably about 0.1 to 24 hours.

The compound of the formula (212) can be produced by a known method, or a commercially available product can be used.

The compound of the present invention is useful as an active ingredient of a agricultural and horticultural fungicide which can prevent harmful fungi in a low dose. When used as a fungicide for agricultural and horticultural use, the compound of the present invention can prevent harmful fungi belonging to the genus Oomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes, among them, The control of harmful fungi such as Ascomycetes and Deuteromycetes is particularly effective.

More specific examples of the above-mentioned harmful fungi include, for example, the following.
Examples of the oomycetes include Phytophthora infestans, Phytophthora capsici Phytophthora genus, and Pseudoperonospora cubensis genus Pseudoperonospora. Such as Plasmopara viticola genus Plasmopara; such as Pythium graminicola, Pythium iwayamai Pythium genus.

Examples of the ascomycetes include Erysiphe genus such as Erysiphe graminis; Sphaerotheca fuliginea; Sphaerotheca humuli; Sphaerotheca genus; The genus Uncinula of Uncinula necator; such as the genus Podosphaera of the genus Podosphaera leucotricha; such as Mycosphaerella pinodes, Mycosphaerella pomi ), Mycosphaerella musicola, Mycosphaerella nawae, Mycosphaerella fragariae, Mycosphaerella; such as Venturia inaequalis, pear black Venturia nashicola of the genus Venturia; such as Pyrenophora teres, Pyrenophora graminea, Pyrenophora; such as Mung sclerotium, Cucumber Nuclear bacterium, Brassica oleracea, Brassica chinensis, S. sclerotium, S. chinensis or Onion Sclerotium Various Sclerotinia sclerotiorum, such as Sclerotinia borealis, Sclerotinia minor, Sclerotinia trifoliorum, Sclerotinia; For example, Botryolinia genus of Botryolinia arachidis; such as the genus Cochliobolus of Cochliobolus miyabeanus; such as the subdivision of the genus Didymella bryoniae Genus of the genus Didymella; for example, Gibberella genus of Gibberella fujikuroi; such as Elsinoe ampelina, Elsinoe fawcettii, Elsinoe Such as Diaporthe citri, Diaporthe sp. between the genus Diaporthe; such as the genus of Monilinia mali and Monilinia fructicola Genus of the genus Monilinia; such as the genus Glomerella of the genus Glomerella cingulata.

Examples of the Basidiomycetes include Rhizoctonia solani Rhizoctonia genus; such as Ustilago nuda, Ustilago genus; such as Oats crown rust fungus ( Puccinia coronata), Puccinia recondita, Puccinia striiformis genus Puccinia; such as Phakopsora pachyrhizi Phakopsora; such as wheat or The genus Typhula of Typhula incarnata (Typhula ishikariensisis) of the barley genus Typhula.

Examples of incomplete fungi include, for example, Septoria nodorum, Septoria tritici, and Septoria; such as Botrytis cinerea, Botrytis cinerea, and Botrytis cinerea , Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Peanut Botrytis, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea Allii), a genus of Botrytis causing leaf blight caused by Botrytis cinerea (Botrytis squamosa, Botrytis byssoidea, Botrytis tulipae); such as Fusarium graminearum, Cucumber (Fusarium oxysporum) of the genus Fusarium, Pyricularia oryzae, Pyricularia; such as Cercospora beticola , Cercospora genus of Cercospora kakivola; Colletotrichum genus such as Colletotrichum orbiculare; such as Alternaria alternata apple pathotype, pear Alternaria alternata Japanese pear pathotype, potato early blight or Alternaria solani, cabbage or Alternaria brassicae, Alternaria brassicola, onion or onion (Alternaria porri) of the genus Alternaria; such as the genus Phoma genus of Phoma lingam; for example, Pseudocercosporella of Pseudocercosporella herpotrichoides Such as Pseudocercospora vitis Pseudocercospora genus; Rhynchosporium secalis Rhynchosporium genus; such as Cladosporium carpophilum Cladosporium carpophilum (Cladosporium) genus; such as Phomopsis sp. Such as Gloeosporium kaki, Gloeosporium; such as Fulvia fulva; Fulvia; such as the rod of Corynespora cassiicola Corynespora genus and the like.

Since the compound of the present invention can prevent various harmful fungi mentioned above, it can prevent or treat various diseases prophylactically or therapeutically. In particular, the compounds of the present invention are various diseases which are problematic in the field of agriculture and horticulture, such as rice blast caused by Pseudomonas, red deer caused by Fusarium, sesame spot caused by Helminthosporium, and sclerotia Diseases of rice such as blight; powdery mildew caused by powdery mildew, scab caused by Fusarium or crown rot, rust caused by rust fungus, brown snow rot caused by rot fungi, naked by black powder Head disease caused by smut, cephalosporin, leaf blight caused by Helminthosporium or blight, and scab caused by Fusarium oxysporum Disease caused by disease, rust caused by rust fungus, coal smut caused by Setosphaeria, sesame spot caused by Helminthosporium, root rot caused by Pythium, smut caused by smut, black smut; black Smut caused by smut, bursal disease caused by S. cerevisiae, rust caused by rust fungus, spoilage caused by Gibberella, dusty path caused by Caldariomyces, leaf blight caused by Pseudomonas aeruginosa, etc. Diseases of rice crops such as diseases of sugar cane; egg mold Powdery mildew caused by bacteria, rust caused by layer rust, downy mildew caused by toad bacillus, blight caused by Phytophthora, anthracnose caused by S. anthracis, Sclerotium caused by Sclerotinia, Grape Diseases of leguminous crops caused by spores, gray rot, root rot or blight caused by Fusarium; blight caused by Fusarium, downy mildew caused by tomb bacillus, spores Diseases caused by bacteria such as black spot disease, root disease caused by stem mold, etc.; downy mildew caused by mold, mildew caused by pathogens, gray mold caused by botrytis, nuclear disk The disease of the Compositae crop caused by the bacterium caused by the bacterium, the rust caused by the rust fungus, the rot disease caused by the bacillus, the leaf mold caused by the leaf mold, the blight caused by the pathogen, the Botrytis Caused by gray mold, powdery mildew caused by egg mold, wilt caused by Fusarium, coal rot caused by Pseudomonas aeruginosa; disease caused by early blight caused by bacteria and pathogen , Sclerotinia sclerotiorum caused by Sclerotinia sclerotiorum, dry rot caused by Fusarium Diseases of Solanaceae crops such as the disease of the potato; anthracnose caused by the genus Aspergillus, the powdery mildew caused by the Phytophthora capsici, the vine blight caused by the genus Didymella, and the bacterium Diseases caused by downy mildew, blight caused by Phytophthora, brown spot caused by Corynebacterium solani, and tsutake crops caused by Fusarium oxysporum; downy mildew and plague caused by toad bacillus Diseases caused by the disease, gray mold caused by Botrytis, sclerotinia caused by Sclerotinia, rust caused by rust fungus, etc.; black leaf blight or black spot caused by Alternaria , the disease of Umbelliferae caused by Botrytis cinerea, Sclerotinia sclerotiorum caused by Sclerotinia, Powdery mildew caused by powdery mildew, Spot disease caused by Cercospora; Bacterial blight caused by Botrytis Diseases caused by plague-causing bacteria, stem blight caused by Pseudomonas sp., etc.; downy mildew caused by toad bacillus, powdery mildew caused by powdery mildew, blight caused by Rhizoctonia The disease of the cockroach crop; the cockroach caused by Fusarium The disease caused by the black spot disease caused by bacteria, the buckwheat crop caused by Streptomyces; the downy mildew caused by the toadstool, the blight caused by the pathogen, the gray mold caused by the botrytis, the nucleus Diseases caused by sclerotium caused by sclerotium, powdery mildew caused by egg mold, brown spot disease caused by cercospora, etc.; black acne caused by sputum bacillus, phlegm caused by sputum Powdery mildew caused by powdery mildew, downy mildew caused by uniptery mildew, gray mold caused by Botrytis, brown spot caused by Pseudomonas aeruginosa, and grape planty caused by bacterial blight Diseases; the disease caused by powdery mildew caused by powdery mildew, the gray mold caused by Botrytis, the anthracnose caused by Fusarium oxysporum, the dry rot caused by Fusarium; the sclerotium Candidiasis, powdery mildew caused by S. monocytogenes, spotted deciduous disease caused by Alternaria alternata, black spot disease caused by black bacillus, anthracnose caused by S. anthracis, brown caused by brown spot Spot disease, ring disease caused by grapevine, and coal spots caused by mold , the disease caused by the coal leaf spot caused by Gloeodes, the black spot disease caused by the bacterium, the black spot disease caused by the black spot, the black spot caused by the bacillus, and the needle shell Pests caused by powdery mildew, blight caused by pathogens, fruit spoilage caused by Fusarium, etc.; gray disease caused by Sclerotinia sclerotiorum, black spot disease caused by Cladosporium, and Pseudomonas spp. a disease of a Rosaceae crop such as a peach disease such as a Pseudomonas sp., a black spot disease caused by a blight fungus, a scab caused by a sputum sac, a Fusarium blight caused by Fusarium, etc. Diseases of fragrant crops such as citrus diseases; anthracnose caused by Helminthosporium, deciduous disease caused by Cercospora, powdery mildew caused by Phytophthora, and coal oleracea caused by mold The disease of the crop; the anthracnose caused by the genus Anthraquinone, the rot disease caused by the genus Trichosporon, the red burning caused by Pseudomonas, the cake caused by the Camellia, etc.; The control of plant diseases is effective.
In addition, scab caused by Fusarium or crown rot, anthracnose caused by Fusarium oxysporum, smut caused by black powder fungus, naked smut caused by smut, black bacillus The disease caused by the leaf spot disease, the blight caused by the genus Aspergillus, the sesame spot caused by the genus Helminthosporium, the anthracnose caused by the genus Aspergillus, and the seedlings caused by Fusarium Diseases of corn such as diseases; diseases of rice crops such as red rot caused by Phytophthora anthracis, black rot caused by moldy mold, and downy mildew caused by Phytophthora; Purple spot disease caused by bacteria, downy mildew caused by toadstool bacteria, blight caused by Fusarium, brown streak caused by Helminthosporium, black spot caused by Fusarium oxysporum, Diseases of legumes caused by the diseases of soybeans such as anthracnose, sleeping sickness caused by Septogloeum bacteria; black spot caused by the fungus Brassica fungus, black smoke caused by Alternaria alternata Disease, toadstool caused by downy mildew, black spot bacterial disease caused by Pseudomonas, Xanthomonas The disease caused by black rot, root disease caused by stem mold, radish caused by bacillus, black spot caused by Fusarium, blight caused by Fusarium, black rot caused by Xanthomonas Diseases; diseases of cruciferous crops such as black spot disease caused by Alternaria, black rot caused by Xanthomonas, yellow cabbage caused by fungus, etc.; Diseases of tomatoes such as ring rot, ulcer disease caused by Corynebacterium, spotted bacterial disease caused by Xanthomonas; disease of eggplant caused by brown spot disease caused by Alternaria alternata, brown streak caused by Pseudomonas spp. Diseases of Solanaceae crops caused by Streptomyces caused by Streptomyces, Mycelium caused by Fusarium oxysporum, Powdery sores caused by Spongospora, and blacks caused by Alternaria Diseases of Cucurbitaceae crops such as spot disease, spotted bacterial disease caused by Pseudomonas, brown spot bacterial disease caused by Xanthomonas, etc.; Black spot caused by Alternaria alternata, Botrytis Gray rot or mycelial spoilage, dry rot caused by Fusarium Diseases of onion crops such as onion diseases caused by downy mildew pathogens; black leaf blight or black spot disease caused by A. oxysporum, spotted bacterial disease caused by Xanthomonas; celery Diseases of Umbelliferae such as leaf blight caused by Phytophthora, Sclerotinia sclerotiorum caused by Sclerotinia, Carrot bacteria caused by Pseudomonas, etc.; The disease caused by downy mildew, the wilt caused by Fusarium, the disease of spinach such as anthracnose caused by Fusarium oxysporum, etc.; and the seed infectious disease is also effective.
Further, it is effective to prevent soil diseases caused by harmful fungi such as Fusarium, Pythium, Rhizoctonia, Fungi, Rhizopus, and Rhizomus.

The plant which can be protected by the present invention from various harmful fungi is not particularly limited as long as it is agriculturally useful, and examples thereof include rice crops (rice, wheat, barley, oats, rye, corn, sugar cane, etc.). ), legume crops (soybeans, kidney beans, red beans, etc.), cruciferous crops (cabbage, cabbage, radish, turnip, broccoli, broccoli, rape, rape, etc.), compositae (lettuce, burdock, chrysanthemum, etc.) , Solanaceae crops (potato, eggplant, tomatoes, green peppers, tobacco, etc.), Cucurbitaceae crops (cucumber, pumpkin, melon, watermelon, etc.), onion crops (onions, leeks, alfalfa, garlic, etc.), Umbelliferous crops ( Celery, carrots, parsley, etc.), lily crops (lilies, tulips, asparagus, etc.), medlar (buckwheat, etc.), Convolvulaceae (sweet potato, etc.), sorghum crops (spinach, beets, etc.), grape crops ( Grapes, etc., Rosaceae crops (roses, strawberries, apples, pears, peaches, alfalfa, almonds, etc.), Rutaceae crops (citrus, lemon, orange, etc.), persimmon crops (persimmons, etc.), Camellia crops (tea Etc., Oleaceae crops (olive, jasmine, etc.), Kwai crops (cotton, cocoa, okra, etc.), musa crops (bananas, etc.), ginger crops (ginger, etc.), valerian crops (coffee trees, etc.) or bromeliad crops (banai, pineapple (Ananas), etc.) .

Further, the compound of the present invention is resistant to various harmful harmful fungi of the agents such as benzimidazole, styrene, dimethyl sulfoxide, phenyl decylamine, ergosterol biosynthesis inhibitor, and the like. Also effective.

Further, since the compound of the present invention has excellent osmotic transfer property, the agricultural and horticultural fungicide containing the compound of the present invention can be applied to the soil, and the harmful fungi in the soil can be prevented, and the harmful fungi of the stem and leaf portions can be prevented. .

The compound of the present invention can be usually mixed with the compound of the present invention and various agricultural adjuvants, and is formulated into a powder, a granule, a granule wettable powder, a wettable powder, an aqueous suspension, an oily suspension, an aqueous solvent, an emulsion. Although various forms such as a liquid preparation, a paste, an aerosol, and a microdispersion agent are used, any formulation form which is generally used in the field can be used as long as it can be suitably used for the purpose of the present invention. Examples of the adjuvant used in the preparation include diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite and sericite mixture, clay, sodium carbonate, sodium hydrogencarbonate, thenardite, zeolite, and starch. Solid carrier; water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl hydrazine, N a solvent such as N-dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or an alcohol; for example, a fatty acid salt, a benzoate, an alkyl sulfosuccinate, a dioxane Sulfosuccinate, polycarboxylate, alkyl sulfate, alkyl sulfate, alkyl aryl sulfate, alkyl diglycol ether sulfate, alcohol sulfate, alkyl sulfonate, Alkyl aryl sulfonate, aryl sulfonate, lignosulfonate, alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate salt, alkyl aryl phosphate Styryl aryl phosphate, polyoxyethylene alkyl ether sulfate salt, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl An anionic surfactant or spreading agent of a sulfate salt, a polyoxyethylene alkyl ether phosphate, a polyoxyethylene alkyl aryl phosphate, a salt of a formalin condensate of naphthalene sulfonate; such as sorbose Alcohol fatty acid esters, glycerin fatty acid esters, fatty acid polyglycerides, fatty acid alcohol polyglycol ethers, acetylene glycols, acetylene alcohols, alkylene oxide block polymers, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl groups Ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyethylene glycol, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester Polyoxyethylene hardened castor oil, nonionic surfactant or spreading agent of polyoxypropylene fatty acid ester; olive oil, kapok oil, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, Vegetable oil or mineral oil such as rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, tung oil, liquid paraffin, and the like. The components of the above-mentioned auxiliary agents can be used singly or in combination of two or more kinds as long as they do not deviate from the object of the present invention. Further, in addition to the aforementioned adjuvants, it may be appropriately selected from those known in the art, for example, an extender, a tackifier, a precipitant, an antifreeze, a dispersion stabilizer, a protective agent, and an anti-fouling agent may also be used. A variety of adjuvants commonly used for molds and the like. The blending ratio of the compound of the present invention and various adjuvants is from 0.001:99.999 to 95:5, and is desirably from 0.005:99.995 to 90:10. When the preparations are actually used, they may be used as they are, or diluted with a diluent such as water to a specified concentration, and if necessary, various spreading agents (surfactants, vegetable oils, mineral oils, etc.) may be added.

The application of the compound of the present invention cannot be generally prescribed due to meteorological conditions, formulation form, target crop, application period, application site, type or occurrence of harmful fungi, type of disease or occurrence state, but generally speaking, The stem and leaf treatment may be applied in an amount of 0.1 to 10,000 ppm, and is desirably 1 to 2,000 ppm, and the compound of the present invention may be used in an amount of 0.1 to 50,000 g per 1 hectare, and desirably about 1 to 30,000 g. In the case of soil treatment, generally, from 1 to 100,000 g, preferably from 200 to 20,000 g, per 1 hectare of the compound of the present invention can be applied. In the case of seed treatment, in general, the seed may be administered in an amount of 0.001 to 10 g per 1 kg of the compound of the present invention, and desirably 0.01 to 1 g.

Administration of various formulations of the compounds of the invention, or dilutions thereof, is generally the usual method of administration, that is, by dispersion (eg, dispersion, spray, misting, atomizing, loosening, Water surface application, etc.), soil application (mixing, infusion, etc.), surface application (coating, powder coating, coating, etc.), etc. Alternatively, it can be applied by a so-called ultra low volume. In this method, it may contain 100% of the active ingredient.

The compound of the present invention can be used in combination with other pesticides, fertilizers, protective agents, and the like, and in some cases, it may exhibit more excellent effects and workability. Examples of other pesticides include herbicides, insecticides, acaricides, nematicides, soil-killing insecticides, bactericides, antiviral agents, attractants, antibiotics, plant hormones, plant growth regulators, and the like. In particular, a mixed bactericidal composition of one or more of the compounds of the present invention and other bactericidal active ingredient compounds may be used in combination, and the application range, the period of the drug treatment, and the control activity may be improved in a preferred direction. . Further, the compound of the present invention and the active ingredient compound of the other bactericidal agent may be used in combination if they are used by mixing each of the separate preparations. The mixed bactericidal composition as described above is also included in the present invention.

The mixing ratio of the compound of the present invention and other bactericidal active ingredient compounds may not be uniform due to meteorological conditions, formulation form, target crop, application period, application site, type or occurrence of harmful fungi, type of disease, or occurrence state. The regulation is generally 1:300 to 300:1, and is expected to be 1:100 to 100:1. Further, the amount of the total active ingredient compound per one hectare applied may be 0.1 to 70,000 g, and preferably 1 to 30,000 g. In the present invention, a method of controlling plant diseases by application of such a mixed bactericidal composition is also included.

By the application of the compound of the present invention, other pesticides such as fungicides, insecticides, acaricides, nematicides, soil-killing agents, antiviral agents, attractants, herbicides, plant growth regulators, etc. may be further combined. deal with.

The active ingredient compound (general name or Japanese Plant Epidemic Prevention Association test code) which is a bactericide of the above-mentioned other pesticides can be suitably selected, for example, from the following group of compounds. Even if it is not specifically described, when such a compound has various structural isomers such as a salt, an alkyl ester or an optical isomer, it is of course included.
An anilinopyrimidine compound such as mepanipyrim, pyrimethanil or cyprodinil;
Such as amidocradin triazolopyrimidine compound;
a pyridylamine compound such as fluazinam;
Such as triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, Myclobutanil, cyproconazole, tebuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole , epoxiconazole, tetraconazole, oxpoconazole fumarate, prothioconazole, triadimenol, flurifaol, benzene Difenoconazole, fluquinconazole, fenbuconazole, bromuconazole, diniconazole, tricyclazole, simeconazole, Pefurazoate, ipconazole, imibenconazole, azaconazole, triticonazole, imazalil, ipfentrifluconazole, flufenoxazole Mefentrifluconazole) azole compound;
Such as quinomethionate quinoxaline compound;
Such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb, thiram ( Thiram) dithiocarbamate-based compound;
Such as tetrachlorophenyl fluorene (fthalide), chlorothalonil, quintozene organochlorine compounds;
Such as benomyl (beta), thiophanate-methyl, carbendazim, thiabendazole, fuberiazole imidazole compounds;
a cyanoacetamide compound such as cymoxanil;
Such as metalaxyl, metalaxyl-M (mefenoxam), oxadixyl, ofurace, benaxyl, a sulfhydryl acid compound of benazoxyl-M, kiralaxyl, chiralaxyl, furalaxyl, valifenalate;
Such as cyprofuram, carboxin, oxycarboxin, thifluzamide, boscalid, fenhexamid, isothiazem An aniline compound of the like, isotianil, tiadinil, Pyraziflumid;
a sulfonamide compound such as diflulofluanid;
Such as cupric hydroxide, oxine copper, anhydrous copper sulfate, copper nonylphenol sulfonate, copper hydroxyquinolate, dodecylbenzene sulfonic acid bisethylenediamine copper complex salt (II ) (alias DBEDC) copper compound;
Such as fosetyl-Al, tolclofos-methyl, edifenphos, iprobenfos organophosphorus compounds;
a phthalic acid imine compound such as captan, captafol and folpet;
Such as procymidone, iprodione, vinclozolin dicarbodiimide compound;
Such as flutolanil, mepronil, benodanil, benzanilide-based compounds;
Such as carpropamid, diclocymet, silthiopham, fenoxanil amide compound;
Such as benzovindiflupyr, bixafen, fluindapyr, fluxapyroxad, furametpyr, isopyrazam , penflufen, penthiopyrad, pydiflumetofen, sedaxane, isoflucypram, inpyrfluxam, pyrapropoyne pyrazole Carboxyamide compound;
Such as fluopicolide, fluopyram, zoxamide, fluopimomide benzoguanamine compounds;
a furanilide-based compound such as fenfuram;
a thiopheneamine compound such as isofetamid;
Such as the piperazine compound of triforine;
Such as pyrifenox, pyrisoxazole, aminopyrifen pyridine compounds;
Pyrimidine-based compounds such as fenarimol, ferimzone, and nuarimol;
a piperidine compound such as fenpropidin;
a morpholine-based compound such as fenpropimorph or tridemorph;
An organotin-based compound such as fentin hydroxide or fentin acetate;
a urea compound such as pencycuron;
Such as dimethomorph, flumorph, pyrimorph, iprovalicarb, benthiavalicarb-isopropyl, mandipropamid carboxylic acid Amidoxime compound;
Such as phenylcarbamate (Carbamate) compound of Diethofencarb;
a cyanopyrrole compound such as fludioxonil or fenpiclonil;
Such as azoxystrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, picoxystrobin, oryzastrobin, azoxystrobin Amine (dimoxystrobin), pyraclostrobin, fluoxastrobin, Enestroburin, Pyraoxystrobin, Pyrametostrobin, coumoxystrobin, sub Enoxastrobin, fenaminstrobin, flufenoxystrobin, triclopyricarb, mandestrobin methoxy acrylate (Strobilurin) compound;
Such as famoxadone, oxathiapiprolin oxazolidinone compound;
a thiazole carboamide compound such as ethaboxam;
An imidazolinone compound such as fenamidone;
a benzenesulfonamide compound such as flusulfamide;
An oxime ether compound such as cyflufenamid;
An anthraquinone compound such as dithianon;
a crotonic acid compound such as meptyldinocap;
For example, anti-biomass of validamycin, kasugamycin, streptomycin, and polyoxins;
Such as guanidine (iminoctadine), dodine (dodine) lanthanide compounds;
Such as tebufloquin (tebufloquin), quinoxyfen, quinofumelin, ipflufenoquin quinoline compound;
Such as flutianil tetrahydrothiazole compound;
Such as propamocarb hydrochloride, pyrabencarb, tolprocarb carbamate compound;
Such as picarbutrazox, tetrazole compound of metyltetraprole;
a sulfonamide compound such as amisulbrom or cyazofamiid;
An allyl phenyl ketone compound such as metrafenone or pyrofenone;
Such as benzothiazole-based compounds of probenazole and dichlobentiazox;
a phenylpyrazole compound such as fenpyrazamine;
a dithiolane compound such as isoprothiolane;
Such as fenpicoxamid, florylpicoxamid, a pyridylamine compound;
Such as sulfur (Sulfur), sulfur-based sulfur compounds;
As other compounds, such as pyroquilon, diclomezine, chloropicrin, dazomet, metam-sodium, proquinazid, snail Spiroxamine, dipymetitrone, etc.;
Microbial bactericides such as Bacillus amyloliqefaciens strain QST713, Bacillus amyloliqefaciens strain FZB24, Bacillus amyloliqefaciens strain MBI600, Bacillus amyloliqefaciens strain D747, Pseudomonas fluorescens, Bacillus subtilis, Trichoderma atroviride SKT-1; and plant extracts such as tea tree oil .

As an insecticide, acaricide, nematicide or soil-killing insecticide in the above other pesticides, that is, an active ingredient compound (general name or Japanese Plant Epidemic Prevention Association test code) for killing insecticides, for example, from the following Appropriate selection in the compound group. Even if it is not specifically described, when such a compound has various structural isomers such as a salt, an alkyl ester or an optical isomer, it is of course included.
Such as profenofos, dichlorvos, fenamiphos, fenitrothion, EPN ((RS)-(O-ethyl O-4-nitrophenyl phenylphosphonothioate), diazinon ), chlorpyrifos, chlorpyrifos-methyl, acephate, prothiofos, fosthiazate, cadusafos, disulfoton , isoxathion, isfenfens, ethion, etrimfos, quinalphos, dimethylvinphos, dimethoate , sulprofos, thiometon, vamidothion, pyraclofos, pyridaphenthion, pirimiphos-methyl, propylidene Propaphos), phosalone, formothion, malathion, tetrachlorvinphos, chlorfenvinphos, cyanophos, trichlorfon , methidathion, phenthoate, oxydeprofos, ESP), azinphos-methyl, fenthion, heptenophos, methoxychlor, parathion, phosphocarb, and letosone - S-methyl ester (demeton-S-methyl), monocrotophos, methamidophos, imicyafos, parathion-methyl, tossone Tertifofos), phosphamidon, phosmet, phorate organophosphate compounds;
Such as carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methodyl, oxamyl, ethyl sulphide Ethiofencarb, pirimicarb, fenobucarb, carbosulfan, benfuracarb, bendiocarb, furathiocarb ), isoprocarb, metolcarb, xylylcarb, XMC (3,5-xylyl methylcarbamate), fenothiocarb (Carbamate) compounds ;
Such as cartap, thiocyclam, thiocyclam oxalate, thiocyclam hydrochloride, bensultap, thiosultap, kill Monosultap; thiosultap-monosodium, bisultap; thiosultap-disodium, polythialan;
Such as dicofol, tetradifon, endosulufan, dienochlor, dieldrin organochlorine compounds;
Such as fenbutatin oxide, organometallic compounds of cyhexatin;
Such as fenvalerate, permethrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, θ-saidingin ( Theta-cypermethrin), beta-cypermethrin, deltamethrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin ), tefluthrin, kappa-tefluthrin, ethofenprox, flufenprox, cyfluthrin, beta-cyfluthrin (beta-) Cyfluthrin), fenpropathrin, flucythrinate, fluvalinate, cycloprothrin, pyrethrins, fenvalerate Esfenvalerate), tetramethrin, resmethrin, protrifenbute, bifenthrin, kappa-bifenthrin, acrinathrin, acridine Allethrin, tau-fluvalinate, tralmethrin, fenfluthrin (profluthrin), metofluthrin, epsilon-metofluthrin, heptafluthrin, phenothrin, flumethrin Pyrethroid-free compound of momfluorothrin, epsilon-momfluorothrin, silafluofen, chloroprallethrin ;
Such as diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, lufenuron, novaluron, triflumuron, Hexaflumuron, bistrifluron, noviflumuron, fluzuron benzamidine-based compounds;
Juvenile hormone compounds such as methoprene, pyriproxyfen, fenoxycarb, and diofenolan;
a pyridazinone compound such as pyridaben;
Such as fenpyroximate, fipronil, ethiprole, acetoprole, pyrafluprole, pyriprole, cyenopyrafen a pyrazole-based compound of flufiprole;
Such as flufluridum pyflubumide, tebufenpyrad, tolfenpyrad pyrazole carboamide compound;
Such as chlorantraniliprole, cyantraniliprole, cyclaniliprole, tetraniliprole, tyclopyrazoflor pyridylpyrazole compound;
Such as imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, nidinotefuran ), new nicotine compounds of dinotefuran, nithiazine;
Such as tebufenozide, methoxyfenozide, chromafenozide, halofenozide lanthanide compounds;
a pyridine compound such as pyridalyl or flonicamid;
Such as spirodiclofen, spiromesifen tetronic acid compound;
Such as spirotetramat, spiropidion pyrrolic acid (tetramic acid) compounds;
Such as fluacrypyrim, pyrimilastin strobilurin compound;
Such as flufenerim (flufenerim), pyrididin (pyrimidifen) pyridinamine compound;
Organic sulfur compounds such as malathion;
a urea compound such as flufenoxuron;
Such as triazine compounds of cyromazine;
Such as hydramethylnon lanthanide compounds;
Such as flubendiamide, broflanilide, cyhalodiamide diamine compound;
Such as diafenthiuron (diafenthiuron), chloromethiuron thiourea compound;
Such as amitraz, chlordimeform, chloromebuform, a methacrylate compound;
Such as pyridoxine (pymetrozine), pyrifluquinazone pyridine azomethine (Azomethine) compounds;
Such as afoxolaner, fluraraner, flumametamide, and isolazoline-based compounds;
Also, as other compounds, such as buprofezin, hexythiazox, triazamate, chlorfenapyr, indoxacarb, acequinocyl, Etoxazole, 1,3-dichloropropene, benclothiaz, bifenazate, propargite, clofentezine, cyanide Metaflumizone, cyflumetofen, fenazaquin, amidoflumet, sulfluramid, hydramethylnon, metaldehyde, Sulfoxaflor, fluensulfone, verbutin, dicloromeoziaz, triflumezopyrim, fluhexafon, tiooxafen, diclofenac Afidopyropen, flometoquin, flupyradifurone, flurazaindolizine, acynonapyr, benzpyrimoxan, flupyrimin, oxazosulfyl compounds, and the like.
Further, the compound of the present invention can be administered in combination with the following compounds.
For example, Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis israelensis, Bacillus thuringiensis japonensis, Bacillus thuringiensis tenebrionis or Bacillus thuringiensis crystal protein toxin, entomopathogenic virus agent, entomopathogenic filamentous fungus, nematode pathogenic filamentous fungus, etc. Microbial pesticides;
Such as abamectin, emamectin benzoate, ivermectin, milbemectin, milbemycin oxime, lepimectin, sinister ( Spinosad), spinetaram antibiotic and semi-synthetic antibiotics;
Such as azadirachtin, rotenone, ryanodine natural products;
Such as the repellent of deet;
Such as paraffin oil, mineral oil, physical control agent.

The desired aspect of the invention is as follows. However, the invention is not limited thereto.
[1] A compound represented by the formula (1) or a salt thereof.
The compound or a salt thereof according to the above [1], wherein B is selected from the group consisting of the formula (B-1) to the formula (B-18) and the formula (B-101) to the formula (B-128). A heterocyclic group in the group formed by the group.
The compound or a salt thereof according to the above [1], wherein B is a heterocyclic group selected from the group consisting of the groups represented by the formulae (B-1) to (B-4).
[4] The compound according to the above [1], wherein B is a group represented by the formula (B-1) or the formula (B-2), or a salt thereof.
[5] The compound according to the above [1] to [4], wherein R ^B is a hydroxyl group, an alkoxy group, a haloalkoxy group, a cycloalkyl alkoxy group, an alkoxy alkoxy group, or a salt thereof. Alkenyloxy, cycloalkyloxy, alkylcarbonyloxy, alkoxycarbonyloxy, alkylthio, amine, alkylamino, dialkylamino; R ^B' is a halogen atom or an alkane base.
[6] The compound according to the above [4], wherein R ^B1 is -L ^B -Y ^B , R ^B2 is an alkyl group, a haloalkyl group or a cycloalkyl group, and R ^B3 is a halogen atom.
The compound or a salt thereof according to the above [4], wherein R ^B1 is a hydroxyl group, an alkoxy group, a haloalkoxy group, a cycloalkyl alkoxy group, an alkoxy alkoxy group, or an alkenyloxy group. And a cycloalkyloxy group, an alkylcarbonyloxy group, an alkoxycarbonyloxy group, an alkylthio group, an amine group, an alkylamino group, a dialkylamino group; R ^B2 is an alkyl group, and R ^B3 is a halogen atom.
[8] The compound according to the above [1] to [7] or a salt thereof, wherein A is a phenyl group substituted with R ^A .
[9] The compound according to the above [1] to [7] or a salt thereof, wherein A is a phenyl group substituted by the same or different 2 to 3 R ^A groups.
[10] The compound according to the above [1] to [7] or a salt thereof, wherein A is a phenyl group in which at least one of the 2 and 4 positions is substituted with R ^A .
[11] The compound according to the above [1] to [7] or a salt thereof, wherein A is a benzodioxocyclopentyl group which is formed by bonding two R ^A and which may be substituted with Z ¹ .
[12] The compound according to the above [1] to [9], wherein R ^A is a halogen atom, an alkyl group, a haloalkyl group or a -L ^A -Y ^A group, or a salt thereof.
[13] The compound according to the above [1] to [12] wherein R ^A is the same or different is a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cyclic group, a nitro group, a cyano group, or a salt thereof. The group or -L ^A -Y ^A , or a bond of 2 R ^A , forms a ring which can be substituted by Z ¹ and Z ¹ is a halogen atom.

[14] A bactericidal agent for agricultural and horticultural use, which comprises the compound according to the above [1] to [13] or a salt thereof as an active ingredient.
[15] A method for controlling a plant disease, which comprises applying the compound according to the above [1] to [13] or a salt thereof to a plant or soil.

[Examples]

Next, although the examples of the invention are described, the invention is not limited thereto.

Synthesis Example 1: N-(1-(3,4-dichlorophenyl)-2-methyl-1-oxopropan-2-yl)-N-methoxy-1-methyl-3- ( Synthesis of methylthio)-1H-pyrazole-4-carboxyguanamine (Compound No. 310)
(1) Synthesis of 1-(3,4-dichlorophenyl)-2-methyl-2-nitropropan-1-ol in 3,4-dichlorobenzaldehyde (5g) and 2-nitro A mixture of propane (10.26 ml) was added with 1,5,7-triazabicyclo[4.4.0]non-5-ene (TBD, 1.19 g), and stirred at room temperature. After 24 hours, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate and filtered and evaporated. The residue was purified by column chromatography (yield: ethyl acetate /hexane) toield
¹ H NMR (CDCl _{3 /} 500 MHz): δ (ppm) = 7.50 (d, J = 2.0 Hz, 1H), 7.45 (d, J = 8.0 Hz, 1H), 7.21 (dd, J = 8.0, 2.0 Hz, 1H), 5.28 (s, 1H), 2.73 (brs, 1H), 1.57 (s, 3H), 1.46 (s, 3H).

(2) Synthesis of 1-(3,4-dichlorophenyl)-2-methyl-2-nitropropan-1-one in 1-(3,4-dichlorophenyl)-2-methyl A solution of 2-nitropropan-1-ol (0.97 g) in methylene chloride (20 mL) was then evaporated. The reaction mixture was poured into water, neutralized with an aqueous sodium hydrogencarbonate solution, and the insoluble material was filtered. The filtrate was extracted with ethyl acetate and the organic layer was washed with water. After drying over anhydrous magnesium sulfate and filtration, it was concentrated under reduced pressure. The residue was purified by column chromatography (yield: ethyl acetate /hexane) toield
¹ H NMR (CDCl _{3 /} 500 MHz): δ (ppm) = 7.90 (d, J = 1.5 Hz, 1H), 7.53-7.49 (m, 2H), 1.92 (s, 6H).

(3) Synthesis of 1-(3,4-dichlorophenyl)-2-(hydroxyamino)-2-methylpropan-1-one in 1-(3,4-dichlorophenyl)-2 a mixed solution of methyl-2-nitropropan-1-one (0.76g) with ammonium chloride (1.55g) in tetrahydrofuran (10mL), water (5mL), ethanol (5mL), and zinc under ice water ( 0.95 g) was added and stirred. After 15 minutes, the reaction mixture was filtered using celite, and the obtained filtrate was poured into water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate and filtered and evaporated. The residue was purified by column chromatography (EtOAc:EtOAc)

(4) Synthesis of 1-methyl-3-(methylthio)-1H-pyrazole-4-carboxylic acid 1-methyl-3-(methylthio)-1H synthesized according to U.S. Patent No. 5,223,526 Ethyl pyrazole-4-carboxylate (2.67 g) was suspended in ethanol (8.46 g), and a solution of sodium hydroxide (1.12 g) in water (13.4 g) was added and stirred at room temperature for 13 hours. After the reaction was completed, concentrated hydrochloric acid was added under ice to precipitate a solid. The precipitated solid was filtered and dried to give a solid object (yield: 2.15 g).
¹ H NMR (CDCl _{3 /300} MHz): δ (ppm) = 7.88 (s, 1H), 3.89 (s, 3H), 2.55 (s, 3H).

(5) N-(1-(3,4-Dichlorophenyl)-2-methyl-1-oxopropan-2-yl)-N-hydroxy-1-methyl-3-(methylthio) Synthesis of -1H-pyrazole-4-carboxyguanamine in 1-methyl-3-(methylthio)-1H-pyrazole-4-carboxylic acid (0.42 g) with N,N-dimethylmethyl A solution of decylamine (0.02 g) in tetrahydrofuran (4.45 g) was added to EtOAc (0.34 g) and stirred at room temperature for one hour to give 1-methyl-3-(methylthio)-1H-pyrazole- 4-carboxyindole chloride. The obtained carboxyindole chloride was dissolved in tetrahydrofuran (2.22 g) to prepare a tetrahydrofuran solution. Furthermore, tetrahydrofuran of 1-(3,4-dichlorophenyl)-2-(hydroxyamino)-2-methylpropan-1-one (0.25 g) and triethylamine (TEA, 0.58 g) A solution (4.43 g) was added to a stirred solution of carboxy chlorobenzene in tetrahydrofuran and stirred at room temperature for 2 hr. After completion of the reaction, water was added to extract with ethyl acetate, and the organic layer was concentrated under reduced pressure. The obtained residue was washed with ethanol to give a solid N-(1-(3,4-dichlorophenyl)-2-methyl-1-oxopropan-2-yl)-1-methyl- N-((1-methyl-3-(methylthio)-1H-pyrazole-4-carbonyl)oxy)-3-(methylthio)-1H-pyrazole-4-carboxamide (0.30 g). This was suspended in ethanol (7.12 g), and a solution of sodium hydroxide (0.11 g) in water (4.62 g) was added, and the mixture was stirred at 40 ° C for 11 hours. After the reaction was completed, water was added and extracted with ethyl acetate. The organic layer was concentrated under reduced pressure to give the title compound (0.17 g).
¹ H NMR (CDCl _{3 /} 300 MHz): δ (ppm) = 8.18 (d, J = 2.1 Hz, 1H), 7.93 (dd, J = 8.7, 2.1 Hz, 1H), 7.79 (s, 1H), 7.43 ( d, J=8.4 Hz, 1H), 7.18 (s, 1H), 3.84 (s, 3H), 2.56 (s, 3H), 1.65 (s, 6H).

(6) N-(1-(3,4-Dichlorophenyl)-2-methyl-1-oxopropan-2-yl)-N-methoxy-1-methyl-3-(A) Synthesis of thio)-1H-pyrazole-4-carboxyguanamine (Compound No. 310) to N-(1-(3,4-dichlorophenyl)-2-methyl-1-oxopropane- 2-, N-hydroxy-1-methyl-3-(methylthio)-1H-pyrazole-4-carboxamide (0.17 g) of N,N-dimethylformamide (1.28 g) The solution was added to sodium hydride (0.03 g, 60%) under ice and stirred. After 5 minutes, a solution of methyl iodide (0.14 g) in N,N-dimethylformamide (0.34 g) was added at the same temperature and stirred at room temperature for 1.5 hours. After completion of the reaction, water was added to extract with ethyl acetate, and the organic layer was concentrated under reduced pressure. The obtained residue was washed with a mixed solution of heptane: ethyl acetate = 1:1 to obtain a solid object (0.16 g, melting point: 199 to 201 ° C).
¹ H NMR (CDCl _{3 /} 300 MHz): δ (ppm) = 8.14 (d, J = 2.1 Hz, 1H), 7.90-7.86 (m, 2H), 7.41 (d, J = 8.4 Hz, 1H), 3.93 ( s, 3H), 3.89 (s, 3H), 2.42 (s, 3H), 1.68 (brs, 6H).

Synthesis Example 2: N-(1-(4-isopropoxy-2-methylphenyl)-2-methyl-1-oxopropan-2-yl)-N,3-dimethoxy- Synthesis of 1-methyl-1H-pyrazole-4-carboxyguanamine (Compound No. 259)
(1) Synthesis of 2-bromo-1-(4-isopropoxy-2-methylphenyl)-2-methylpropan-1-one as synthesized according to Japanese Laid-Open Patent Publication No. 2016-108332 A solution of 4-isopropoxy-2-methylphenyl)-2-methylpropan-1-one (14.41 g) in tetrahydrofuran (100 mL) was added trimethylphenylammonium bromide (28.87 g). Stir at room temperature for 5 hours. After completion of the reaction, the reaction mixture was filtered, and the obtained filtrate was concentrated under reduced pressure. The obtained residue was purified by column chromatography (yield: ethyl acetate /hexane) to afford (20.4 g).

(2) Synthesis of 1-(4-isopropoxy-2-methylphenyl)-2-methyl-2-nitropropan-1-one in 2-bromo-1-(4-isopropyloxy) a solution of benzyl-2-methylphenyl)-2-methylpropan-1-one (20.4 g) in dimethyl hydrazine (100 mL), sodium nitrite (7.6 g), and stirred at room temperature for 4 hours. Its reaction. Dimethylhydrazine (40 mL) was added and stirred at 40 ° C for 2 hours to cause a reaction. After completion of the reaction, water was added to room temperature, and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate and evaporated. The residue was purified by column chromatography (heptane:EtOAc)
¹ H NMR (CDCl _{3 /} 300 MHz): δ (ppm) = 7.31 (d, J = 8.7 Hz, 1H), 6.76 (d, J = 2.4 Hz, 1H), 6.64 (dd, J = 9.0, 2.7 Hz, 1H), 4.63-4.55 (m, 1H), 2.45 (s, 3H), 1.92 (s, 6H), 1.34 (d, J=6.0 Hz, 6H).

(3) Synthesis of 2-(hydroxyamino)-1-(4-isopropoxy-2-methylphenyl)-2-methylpropan-1-one in the same manner as in Synthesis Example 1 (3) Method, the object compound (0.5 g) was obtained from 1-(4-isopropoxy-2-methylphenyl)-2-methyl-2-nitropropan-1-one (1.0 g).
¹ H NMR (CDCl _{3 /} 300 MHz): δ (ppm) = 7.35 (d, J = 8.4 Hz, 1H), 6.73 (d, J = 2.4 Hz, 1H), 6.67 (dd, J = 8.7, 2.7 Hz, 1H), 4.60-4.52 (m, 1H), 2.38 (s, 3H), 1.36 (s, 6H), 1.32 (d, J=6.0 Hz, 6H).

(4) Synthesis of ethyl 3-methoxy-1-methyl-1H-pyrazole-4-carboxylate 3-hydroxy-1-methylpyrazole-4 synthesized according to JP-A-2002-348280 A solution of ethyl carboxylate (10.0 g) in N,N-dimethylformamide (150 mL). After 15 minutes, methane iodide (16.68 g) was added at the same temperature and stirred. After 4 hours and 30 minutes, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate and filtered and evaporated. The residue was purified by column chromatography (liluent: ethyl acetate /hexane) to
¹ H NMR (CDCl _{3 /} 300MHz): δ (ppm) = 7.66 (s, 1H), 4.27 (q, J = 7.2 Hz, 2H), 3.98 (s, 3H), 3.76 (s, 3H), 1.32 ( t, J = 7.2 Hz, 3H).

(5) Synthesis of 3-methoxy-1-methyl-1H-pyrazole-4-carboxylic acid in ethyl 3-methoxy-1-methyl-1H-pyrazole-4-carboxylate (10.2 g) A mixed solution of sodium hydroxide (2.21 g) in ethanol (20 mL) and water (250 mL) was added and stirred at 50 ° C for 2 hours and 45 minutes. Sodium hydroxide (0.5 g) was added, and the mixture was further stirred at the same temperature for 2 hours. After completion of the reaction, the mixture was cooled to room temperature and washed with ethyl acetate.
Hydrochloric acid was added to the aqueous layer, and the crystals which precipitated were collected by filtration and dried to give the object (5.88 g).
^{1 H NMR (DMSO-d6 /} 300MHz): δ (ppm) = 11.93 (brs, 1H), 8.00 (s, 1H), 3.80 (s, 3H), 3.69 (s, 3H).

(6) N-Hydroxy-N-(1-(4-isopropoxy-2-methylphenyl)-2-methyl-1-oxopropan-2-yl)-3-methoxy- Synthesis of 1-methyl-1H-pyrazole-4-carboxamide in a solution of 3-methoxy-1-methyl-1H-pyrazole-4-carboxylic acid (0.72 g) in toluene (10 mL). Grass chloroform (1.39 g) and N,N-dimethylformamide (0.01 g) were stirred at 90 ° C for 1 hour. The reaction mixture solution was concentrated under reduced pressure to give 3-methoxy-1-methyl-1H-pyrazole-4-carboxyindole chloride. The obtained carboxyindole chloride was dissolved in tetrahydrofuran (10 mL) to prepare a tetrahydrofuran solution. Furthermore, a solution of 2-(hydroxyamino)-1-(4-isopropoxy-2-methylphenyl)-2-methylpropan-1-one (0.55 g) in tetrahydrofuran (20 mL) was added in three Ethylamine (5.8 g) was added to a stirred solution of ruthenium chloride in tetrahydrofuran. Stir at room temperature for 2 hours and 30 minutes. After the reaction was completed, water was added and the mixture was extracted with ethyl acetate. After washing with saturated brine, the organic layer was dried over sodium sulfate and evaporated. The obtained residue was dissolved in ethanol (30 mL), and then, the mixture was stirred and evaporated. After the reaction was completed, water was added and the mixture was extracted with ethyl acetate. After washing with saturated brine, the organic layer was dried over sodium sulfate and evaporated. The residue was purified by column chromatography (heptane:EtOAc)
¹ H NMR (CDCl _{3 /300} MHz): δ (ppm) = 7.84 (s, 1H), 7.80 (d, J = 8.7 Hz, 1H), 7.54 (s, 1H), 6.71 (d, J = 2.4 Hz, 1H), 6.57 (dd, J=8.7, 2.4 Hz, 1H), 4.60-4.52 (m, 1H), 3.98 (s, 3H), 3.65 (s, 3H), 2.46 (s, 3H), 1.67 (s , 6H), 1.31 (d, J=6.0 Hz, 6H).

(7) N-(1-(4-Isopropoxy-2-methylphenyl)-2-methyl-1-oxopropan-2-yl)-N,3-dimethoxy-1 Synthesis of methyl-1H-pyrazole-4-carboxyguanamine (Compound No. 259) to N-hydroxy-N-(1-(4-isopropoxy-2-methylphenyl)-2- Methyl-1-oxopropan-2-yl)-3-methoxy-1-methyl-1H-pyrazole-4-carboxamide (0.15 g) of N,N-dimethylformamide (10 mL) solution, after adding sodium hydride (0.02 g, 60%), methane iodide (0.1 g) was added. The mixture was stirred at room temperature for 30 minutes to cause a reaction. After the reaction was completed, water was added and the mixture was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate and evaporated.
The residue obtained was purified by column chromatography (heptane: ethyl acetate) to give a mixture. The obtained mixture was purified by column chromatography (heptane: ethyl acetate) using ethylamine.
¹ H NMR (CDCl _{3 /} 300 MHz): δ (ppm) = 7.77 (d, J = 8.7 Hz, 1H), 7.63 (s, 1H), 6.67 (d, J = 2.4 Hz, 1H), 6.57 (dd, J=8.7, 2.4 Hz, 1H), 4.58-4.50 (m, 1H), 3.91 (s, 3H), 3.76 (s, 3H), 3.72 (s, 3H), 2.39 (s, 3H), 1.69 (brm , 6H), 1.29 (d, J=6.0 Hz, 6H).

Next, a representative example of the compound of the present invention is specifically listed in the first table. These compounds can be synthesized according to known methods in the above production method, the above-mentioned synthesis examples, and the technical field.
In the table, No. indicates a compound No.. The numerical value described in the physical property column of the first table is the melting point (°C), and the compound described as NMR indicates the ¹ H-NMR spectrum data in the second table. The abbreviations used in column B of the first table respectively indicate the following substituents. Further, Me represents a methyl group, Et represents an ethyl group, Pr represents an n-propyl group, iPr represents an isopropyl group, tBu represents a third butyl group, Ac represents an ethyl fluorenyl group, nBu represents an n-butyl group, and sBu represents a second butyl group. base.

Test Example 1: Bactericidal effect against wheat leaf blight Test YBG (yeast extract, Bacto Peptone, glycerol) medium containing the compound of the present invention dissolved in dimethyl hydrazine, inoculated with wheat leaf blight (Septoria) The cell suspension of tritici) was cultured at room temperature for 7 days to investigate the degree of growth.
Compound No. 4, 7, 11, 16, 19, 33, 37, 55, 57, 89, 96, 98, 100, 106, 113, 123, 136, 144, 156, 159, 169, 172, 178, 179, 182, 211, 233, 237, 243, 245, 253-255, 259, 267, 279, 282, 286, 288, 291, 306, 310, 314, 321, 332, 345, 351, 360, 365, 370-372, 379, 387, 397, 400, 429, 432, 435, 453-459, 461-472, 475-481, 484-486, 493, 495, 496, 498-508, 511, 514, 518, 520-535, 539, 541-550, 552-564, 566, 567, 569, 570, 572-579, 581-589, 596-611, 613, 620, 625-629, 631, 632, 636-645, 649, 650, 665, 666, 675, 690, 696-698, 702, 703, 717, 741, 748-752, 755-758, 764, 766, 768, 769, 774, 775, 781-795, 806~ 809, 811 to 820, and 823 inhibited the growth of wheat leaf blight by more than 70% at 30 ppm.

Test Example 2: Bactericidal effect against wheat scab is tested on YBA (yeast extract, protein) containing the compound of the present invention dissolved in dimethyl sulfoxide (Bacto Peptone), sodium acetate) medium, inoculated with a suspension of Fusarium graminearum, and cultured at room temperature for 3 days to investigate the degree of growth.
Compound No. 4, 11, 16, 19, 33, 37, 55, 57, 89, 96, 98, 100, 106, 113, 123, 136, 144, 156, 159, 169, 172, 178, 179, 182, 211, 224, 233, 237, 243, 245, 253-255, 259, 267, 279, 282, 286, 288, 291, 306, 310, 314, 332, 345, 351, 360, 365, 370~ 372, 379, 387, 394, 397, 400, 429, 432, 435, 453-458, 461-466, 468-472, 475-481, 484-486, 493-496, 498-508, 518, 520~ 540, 543-564, 566-570, 572-580, 582-589, 596-610, 620, 625-629, 631, 632, 636-645, 649, 650, 665, 666, 687-691, 696~ 698, 702, 703, 717, 719, 741, 742, 744, 748-752, 755-758, 764, 766, 768, 769, 773-775, 781-795, 806-809, 811-820 will be 30 ppm The growth inhibition of Fusarium graminearum is more than 70%.

Test Example 3: Effect test on wheat powdery mildew Wheat was cultivated in a vinyl pot having a diameter of 6 cm, and when the 1.5 to 2.0 leaf stage was reached, 10 ml of the compound of the present invention was prepared to be dispersed in a spray gun. After the liquid medicine was dried (on the day of treatment), the meristematic cells of Erysiphe graminis were sprinkled and inoculated, and kept in a constant temperature room at 20 °C. The control rate was investigated from the area of cell formation 7 days after the inoculation.
Compound No. 4, 11, 37, 98, 100, 106, 113, 123, 136, 144, 159, 172, 243, 253, 254, 259, 267, 279, 282, 345, 351, 365, 387, 397, 421, 454-456, 461, 462, 466-468, 474, 477, 481, 484, 493, 494, 497, 499, 503, 504, 529, 531, 570, 571, 573, 597, 598, 600, 602 to 604, 606, 607, 611, 637, 638, 643, 675, 741, 756 to 758, and 769 inhibited the onset of wheat powdery mildew by 90% or more at 100 ppm.

Test Example 4: Effect on mung bean gray mold The mung bean was cultivated with a 15 cm diameter polydip. When the leaf was fully developed, 5 mL of the compound of the present invention was prepared to be dispersed in a spray gun. After drying the liquid (on the day of the treatment or the next day), inoculate a paper disc of 8 mm in diameter containing a coniferous suspension of Botrytis cinerea prepared with PS (potato, sucrose) medium, under humid conditions. Keep in a constant temperature room at 20 °C. The rate of control was investigated from the length of the lesion 3 days after the inoculation.
Compound No. 19, 33, 55, 57, 89, 98, 113, 211, 233, 237, 243, 254, 259, 282, 286, 372, 429, 454, 462, 466, 471, 472, 476, 481, 503, 505, 506, 508, 528, 533, 561-564, 577, 583-589, 602, 637, 638, 675, 696, 750-752, 769, 783, 787, 788, 806-808, 811, 813, and 816 inhibited the onset of mung bean gray mold by more than 90% at 25 ppm.

Test Example 5: Effect on Mung Bean Sclerotium Disease Mung Bean was cultivated with a 15 cm diameter polydip. When the leaf was fully developed, 5 mL of the compound of the present invention was prepared to be dispersed in a spray gun. After drying the drug solution (on the day of the treatment or the next day), the flora surface of the sclerotium disk (4 mm in diameter) of the sclerotinia sclerotiorum cultured in PSA (potato, sucrose, and amaranth) medium is inoculated from above. , kept in a constant temperature room at 20 ° C under humid conditions. The rate of control was investigated from the length of the lesion 3 days after the inoculation.
Compound No. 16, 19, 33, 37, 55, 57, 89, 98, 113, 136, 144, 156, 172, 211, 237, 243, 253, 254, 259, 279, 282, 286, 291, 321, 360, 365, 371, 372, 379, 387, 397, 429, 432, 454, 457, 458, 463, 464, 466-472, 475-481, 485, 496, 498-500, 503, 505~ 508, 514, 525, 527, 528, 533, 556, 558, 561-564, 569, 570, 577, 578, 583-589, 599, 602, 603, 606-609, 629, 637, 638, 665, 666, 675, 690, 696-698, 702, 719, 749-752, 755-758, 766, 768, 769, 781-788, 791-794, 806-809, 811-813, 816, 818, 819 25 ppm inhibited the onset of mung bean disease by more than 90%.

Next, although the preparation examples of the composition of the present invention are described, the blending ratio, the dosage form, and the like are not limited to the description examples.
Formulation Example 1
(1) 20 parts by weight of the compound of the formula (1)
(2) 72 parts by weight of clay
(3) 8 parts by weight of ligninsulfonic acid soda is uniformly mixed as a wettable powder.
Formulation Example 2
(1) 5 parts by weight of the compound of the formula (1)
(2) 95 parts by weight of talc is uniformly mixed as a powder.
Formulation Example 3
(1) 20 parts by weight of the compound of the formula (1)
(2) 20 parts by weight of N,N'-dimethylacetamide
(3) 10 parts by weight of polyoxyethylene alkylphenyl ether
(4) 50 parts by weight of xylene is uniformly mixed or more as an emulsion.

Formulation Example 4
(1) 68 parts by weight of clay
(2) 2 parts by weight of lignin sulfonate soda
(3) 5 parts by weight of polyoxyethylene alkyl aryl sulfate
(4) 25 parts by weight of fine powder of cerium oxide A mixture of the above components and a compound of the formula (1) are mixed in a weight ratio of 4:1 to obtain a wettable powder.
Formulation Example 5
(1) 50 parts by weight of the compound of the formula (1)
(2) Oxylated polyalkylphenyl phosphate
- triethanolamine 2 parts by weight
(3) Polyoxyl 0.2 parts by weight
(4) 47.8 parts by weight of water, which are uniformly mixed or more, and further added to the pulverized stock solution to be uniformly mixed.
(5) 5 parts by weight of sodium polycarboxylate
(6) 42.8 parts by weight of anhydrous sodium sulfate was granulated and dried to obtain a granule wettable powder.
Formulation Example 6
(1) 5 parts by weight of the compound of the formula (1)
(2) 1 part by weight of polyoxyethylene octylphenyl ether
(3) 0.1 parts by weight of polyoxyethylene phthalate
(4) 93.9 parts by weight of granular calcium carbonate was mixed in advance (1) to (3), diluted with an appropriate amount of acetone, and then blown to (4) to remove acetone as a granule.

Formulation Example 7
(1) 2.5 parts by weight of the compound of the formula (1)
(2) N-methyl-2-pyrrolidone 2.5 parts by weight
(3) 95.0 parts by weight of soybean oil was dissolved in a uniform mixture or more as an ultra low volume formulation.
Formulation Example 8
(1) 20 parts by weight of the compound of the formula (1)
(2) Oxylated polyalkylphenol phosphate
- triethanolamine 2 parts by weight
(3) Polyoxyl 0.2 parts by weight
(4) 0.1 parts by weight of Sanxianjiao
(5) 5 parts by weight of ethylene glycol
(6) 72.7 parts by weight of water were uniformly mixed or pulverized as an aqueous suspension.

The specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. Hei.

Claims (11)

a compound represented by the formula (1) or a salt thereof, [Wherein, A is the substituted phenyl is substituted with the R ^A or R ^A pyridyl group, B is R ^B is substituted with the heterocyclic group (the heterocyclic group to be further substituted by 1 to 3 R ^{B 'substituent)} And R ^A may be the same or different in a halogen atom, an alkyl group which may be substituted by G ¹ , an alkenyl group, an alkynyl group which may be substituted by G ² , a cyclic group, a nitro group, a cyano group or a -L ^A -Y ^{A group} , Or may bond 2 R ^A to form a ring which may be substituted by Z ¹ , R ^B is -L ^B -Y ^B , R ^{B '} is a halogen atom, an alkyl group, a haloalkyl group, an alkoxyalkyl group, a cycloalkane Base or cyano group, L ^A is O, S, C(=O), C(=O)O, C(=O)N(R ¹ ), OC(=O), N(R ¹ ), N( R ¹ )C(=O), N(R ¹ )C(=O)O, C(=NR ² ), SO, SO ₂ or SO ₂ N(R ¹ ), Y ^A is a hydrogen atom, which can be Z ^a substituted alkyl group, an alkenyl group or a cyclic group which may be substituted by Z ³ , and L ^B is O, S, C(=O), C(=O)O, C(=O)N(R ³ ), OC(=O), OC(=O)O, N(R ³ ), N(R ³ )C(=O), N(R ³ )C(=O)O, C(=NR ⁴ ), SO , SO ₂ or SO ₂ N(R ³ ), Y ^B is a hydrogen atom, an alkyl group which may be substituted by Z ⁴ , an alkenyl group, a cycloalkyl group, a phenyl group which may be substituted by Z ⁵ or a impurity which may be substituted by Z ⁵ cycloalkyl group, R ¹ is a hydrogen atom or an alkyl group, R ² is a hydrogen atom, an alkyl or alkoxy Group, R ³ is a hydrogen atom or an alkyl group, R ⁴ is a hydrogen atom, an alkyl group or an alkoxy group, G ¹ is a halogen atom or an alkoxy group, G ² is a halogen atom or a cycloalkyl group, Z ¹ is a halogen atom, An alkyl group, an alkoxy group or a cycloalkyl group, Z ² is a halogen atom, a cyano group, a cycloalkyl group or an alkoxy group, Z ³ is a halogen atom or a halogen alkyl group, and Z ⁴ is a halogen atom, a cycloalkyl group or an alkoxy group. The group, Z ⁵ is a halogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group or an alkoxy group]. The compound of claim 1, wherein B is a 5-membered heterocyclic group represented by formula (B-1) to formula (B-18), and formula (B-101) to formula (B-128), or a salt thereof. a heterocyclic group represented by a group of 6-membered heterocyclic groups, [In the formula, any one of R ^B1 to R ^B3 , any one of R ^B4 to R ^B6 , any one of R ^B7 to R ^B9 , any one of R ^B10 to R ^B12 , and R ^B13 to R ^B15 Any one of R ^B16 to R ^B18 and any one of R ^B19 to R ^B20 is -L ^B -Y ^B , and the residue is a halogen atom, an alkyl group, a haloalkyl group, an alkoxyalkyl group, or a ring. Alkyl or cyano, L ^B and Y ^B are as defined in claim 1, * represents bond position] [In the formula, any one of R ^B101 to R ^B104 , any one of R ^B105 to R ^B108 , any one of R ^B109 to R ^B111 , and any one of R ^B112 to R ^B114 is -L ^B -Y ^B The residue is a halogen atom, an alkyl group, a haloalkyl group, an alkoxyalkyl group, a cycloalkyl group or a cyano group, and L ^B and Y ^B are as defined in the claim 1, and * represents a bonding position]. The compound of claim 2 or a salt thereof, wherein B is a heterocyclic group selected from the group consisting of heterocyclic groups represented by the following formulas (B-1) to (B-4), . The compound of claim 2, wherein B is a heterocyclic group represented by the following formula (B-1) or formula (B-2), or a salt thereof; . The compound of claim 4 or a salt thereof, wherein R ^B1 is -L ^B -Y ^B , R ^B2 is an alkyl group, a haloalkyl group or a cycloalkyl group, and R ^B3 is a halogen atom. The compound of claim 1, or a salt thereof, wherein A is a phenyl group substituted with R ^A . The compound of claim 1 or a salt thereof, wherein A is a phenyl group in which at least one of the 2 and 4 positions is substituted with R ^A . The compound of claim 1 or a salt thereof, wherein A is benzodioxolanyl which may be substituted by Z ¹ . The compound of claim 1, or a salt thereof, wherein R ^A is a halogen atom, an alkyl group, a haloalkyl group or -L ^A -Y ^A . A horticultural fungicide for agricultural and horticultural, which comprises the compound of claim 1 or a salt thereof as an active ingredient. A method for controlling plant diseases, which comprises applying the compound of claim 1 or a salt thereof to a plant or soil.