WO2013084770A1 - Azole derivative, method for producing azole derivative, intermediate compound, drug for agricultural and horticultural applications, and industrial material protectant - Google Patents

Abstract

Provided is an azole derivative characterized by represented by general formula (I) or (Ia), for the purpose of providing a compound which has a high control effect on plant diseases and of which the toxic effect thereof can be reduced to a low level.

Description

Azole derivatives, methods for producing azole derivatives, intermediate compounds, agricultural and horticultural agents and industrial material protecting agents

The present invention relates to a novel azole derivative, a method for producing the azole derivative, and an intermediate compound. Moreover, it is related with the agricultural and horticultural chemical | medical agent and industrial material protecting agent which contain the said azole derivative as an active ingredient.

Conventionally, a large number of azolylmethylcyclopentanol derivatives have been developed as active ingredients of plant disease control agents. For example, 2- (halogenated hydrocarbon substitution) -5-benzyl-1-azolylmethylcyclopentanol Derivatives (for example, see Patent Document 1) and 5-mercapto- [1,2,4] triazolylmethyl-cyclopentanol derivatives (for example, see Patent Documents 2 to 5) have been developed.

International Publication WO2011 / 077071 (released on June 16, 2011) International Publication No. WO2010 / 122167 (released on October 28, 2010) International Publication No. WO2010 / 122169 (released on October 28, 2010) International Publication No. WO2010 / 122170 (October 28, 2010) International Publication WO2010 / 149414 (Released on December 29, 2010)

In addition to demands for safety and control effects, agricultural and horticultural drugs are also strongly desired to reduce phytotoxicity to plants.

Therefore, the present invention has been made in view of the above problems, and its purpose is to provide a high control effect against plant diseases, and as an active ingredient in agricultural and horticultural medicines with reduced phytotoxicity to plants. It is to provide an azole derivative to be contained.

As a result of intensive studies by the present inventors for solving the above-mentioned problems, the azole derivative represented by the following general formula (I) and the azole derivative represented by the following general formula (Ia) have excellent activity and phytotoxicity to plants. Has been found to be reduced, and the present invention has been completed.

That is, the present invention has been made on the basis of such novel findings, and includes the following inventions.

An azole derivative characterized by being represented by the following general formula (I) or (Ia).

(In the general formulas (I) and (Ia), Y ¹ represents a halogen atom,
R ¹ represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom,
Y ² represents a halogen atom, m represents 0, 1 or 2, and when m is 2, a plurality of Y ² may be different from each other;
A represents a nitrogen atom or a methine group.
In the general formula (I), X represents —SH, —SR ² , —SO—R ² , —SO ₂ —R ² or —SO ₃ H. R ² represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a haloalkenyl group having 2 to 6 carbon atoms, an aryl group, or an arylalkyl A group (the alkyl part has 1 to 4 carbon atoms), and in the aryl group and arylalkyl group in R ² , at least one hydrogen atom in the aromatic ring is a halogen atom, and an alkyl group having 1 to 4 carbon atoms (cyclohexane). An alkyl group), or a haloalkyl group having 1 to 4 carbon atoms. )
An intermediate compound used for producing the above azole derivative, which is represented by the following general formula (II) or (IIa).

(In the general formula (II) and ^{(IIa), R 1, Y} 2, m and A are the same as ^{R 1, Y} 2, m and A in each of the above general formula (I) and (Ia). General In the formula (II), X is the same as X in the general formula (I).)
A process for producing the above azole derivative, wherein an intermediate compound represented by the following general formula (II) or (IIa) is reacted with a halogen acid to produce an azole derivative represented by the above general formula (I) or (Ia) The manufacturing method of the azole derivative including the process of obtaining.

(In General Formulas (II) and (IIa), R ¹ , Y ² , m and A are the same as R ¹ , Y ² , m and A in General Formula (I), respectively. General Formula (II) In the formula, X is the same as X in the general formula (I).)
Moreover, this invention also includes the agricultural and horticultural chemical | medical agent or industrial material protecting agent characterized by containing the above-mentioned azole derivative as an active ingredient.

The azole derivative according to the present invention has an excellent bactericidal action against many bacteria that cause diseases on plants, and has low phytotoxicity on plants. Therefore, the chemical | medical agent which contains the azole derivative which concerns on this invention as an active ingredient has the effect which can suppress a chemical damage low while exhibiting the high control effect with respect to a wide range of plant diseases.

Hereinafter, the azole derivative according to the present invention will be described.

[Azole derivatives]
The azole derivative according to the present invention is an azole derivative represented by the following general formula (I) or (Ia). Hereinafter, the azole derivative represented by the general formula (I) is referred to as an azole derivative (I), and the azole derivative represented by the general formula (Ia) is referred to as an azole derivative (Ia).

(In the general formulas (I) and (Ia), Y ¹ represents a halogen atom,
R ¹ represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom,
Y ² represents a halogen atom, m represents 0, 1 or 2, and when m is 2, a plurality of Y ² may be different from each other;
A represents a nitrogen atom or a methine group.
In the general formula (I), X represents —SH, —SR ² , —SO—R ² , —SO ₂ —R ² or —SO ₃ H. R ² represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a haloalkenyl group having 2 to 6 carbon atoms, an aryl group, or an arylalkyl A group (the alkyl part has 1 to 4 carbon atoms), and in the aryl group and arylalkyl group in R ² , at least one hydrogen atom in the aromatic ring is a halogen atom, and an alkyl group having 1 to 4 carbon atoms (cyclohexane). An alkyl group), or a haloalkyl group having 1 to 4 carbon atoms. )
Y ¹ represents a halogen atom. Specific examples of the halogen atom for Y ¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a fluorine atom, a chlorine atom and a bromine atom are more preferred, and a chlorine atom and a bromine atom are more preferred. A chlorine atom is particularly preferred.

R ¹ represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and a 1-methylethyl group. Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, and a 1-methylethoxy group. Preferably, R ¹ is a hydrogen atom.

Y ² represents a halogen atom. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, among which a fluorine atom, a chlorine atom and a bromine atom are more preferable, and a fluorine atom and a chlorine atom are particularly preferable.

m represents 0, 1 or 2. When m is 1 or 2, the bonding position of Y ² is not particularly limited, but when m is 1, it is preferably a 4-substituted benzyl group. When m is 2, it is preferably a 2,4-substituted benzyl group. When m is 2, a plurality of Y ² may be different from each other, but more preferably the same as each other. Preferably m is 0 or 1.

A represents a nitrogen atom or a methine group. Preferably A is a nitrogen atom.

X represents —SH, —SR ² , —SO—R ² , —SO ₂ —R ² or —SO ₃ H. R ² represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a haloalkenyl group having 2 to 6 carbon atoms, an aryl group, or an arylalkyl group (Wherein the alkyl moiety has 1 to 4 carbon atoms).

Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, 1-methylethyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethyl group. Ethyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethyl Propyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1, 3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1, - trimethylpropyl group, 1,2,2-trimethyl propyl group, a 1-ethyl-1-methylpropyl group and 1-ethyl-2-methylpropyl group.

Examples of the alkenyl group having 2 to 6 carbon atoms include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-1- Propenyl group, 2-methyl-1-propenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-1-butenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 3-methyl-2 -Butenyl group, 1-methyl-3-butenyl group, 2-methyl-3-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1,2-dimethyl-1- Propeni Group, 1,2-dimethyl-2-propenyl group, 1-ethyl-1-propenyl group, 1-ethyl-2-propenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group 5-hexenyl group, 1-methyl-1-pentenyl group, 2-methyl-1-pentenyl group, 3-methyl-1-pentenyl group, 4-methyl-1-pentenyl group, 1-methyl-2-pentenyl group 2-methyl-2-pentenyl group, 3-methyl-2-pentenyl group, 4-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 2-methyl-3-pentenyl group, 3-methyl- 3-pentenyl group, 4-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 2-methyl-4-pentenyl group, 3-methyl-4-pentenyl group, 4-methyl-4-pentenyl group 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2- Dimethyl-3-butenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 2,2-dimethyl-3-butenyl group 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1 -Butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1 , 1,2-Trimethyl-2-propenyl group, 1-ethyl Examples include a 1-methyl-2-propenyl group, a 1-ethyl-2-methyl-1-propenyl group, and a 1-ethyl-2-methyl-2-propenyl group.

Examples of the haloalkyl group having 1 to 6 carbon atoms include chloromethyl group, bromomethyl group, dichloromethyl group, trichloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chlorofluoromethyl group, dichlorofluoromethyl group, chloro Difluoromethyl group, 1-chloroethyl group, 1-bromoethyl group, 1-fluoroethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2 -Fluoroethyl group, 2-chloro-2,2-difluoroethyl group, 2,2-dichloro-2-fluoroethyl group, 2,2,2-trichloroethyl group, pentafluoroethyl group and the like.

Examples of the haloalkenyl group having 2 to 6 carbon atoms include 2-chloroethenyl group, 2,2-dichloroethenyl group, 2-chloro-2-propenyl group, 3,3-dichloro-2-propenyl group, 2,3-dichloro -2-propenyl group, 3,3-dichloro-2-methyl-2-propenyl group, 3-chloro-2-butenyl group, 2-fluoroethenyl group, 2,2-difluoroethenyl group, 2-fluoro- 2-propenyl group, 3,3-difluoro-2-propenyl group, 2,3-difluoro-2-propenyl group, 3,3-difluoro-2-methyl-2-propenyl group, 3-fluoro-2-butenyl group 2-bromoethenyl group, 2,2-dibromoethenyl group, 2-bromo-2-propenyl group, 3,3-dibromo-2-propenyl group, 2,3-dibromo-2-propenyl group, 3 3-dibromo-2-methyl-2-propenyl group, 3-bromo-2-butenyl group, 2-iodoethenyl group, 2,2-diiodoethenyl group, 2-iodo-2-propenyl group, 3,3-diiodo-2 -Propenyl group, 2,3-diiodo-2-propenyl group and the like.

As the arylalkyl group (the alkyl part has 1 to 4 carbon atoms), phenylmethyl group, phenylnaphthyl group, 1-phenylethyl group, 2-phenylethyl group, 2-naphthylethyl group, 1-phenylpropyl group, 2 -Phenylpropyl group, 3-phenylpropyl group, 1-methyl-2-phenylethyl group, 1-methyl-1-phenylethyl group, 4-phenylbutyl group and the like can be mentioned.

Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group.

One, two or three of the hydrogen atoms in the aromatic ring of the aryl group and arylalkyl group for R ² are a halogen atom, an alkyl group having 1 to 4 carbon atoms (including a cycloalkyl group), or 1 to It may be substituted with 4 haloalkyl groups.

Examples of the halogen atom as a substituent in the aromatic ring of the aryl group and arylalkyl group in R ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Similarly, the alkyl group having 1 to 4 carbon atoms as a substituent includes a methyl group, an ethyl group, an n-propyl group, a 1-methylethyl group, an n-butyl group, a 1-methylpropyl group, and a 2-methylpropyl group. 1,1-dimethylethyl group, cyclopropylmethyl group and the like. Similarly, examples of the haloalkyl group having 1 to 4 carbon atoms as a substituent include a trifluoromethyl group, a pentafluoroethyl group, a chloromethyl group, a trichloromethyl group, and a bromomethyl group. More preferred are fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, trifluoromethyl group and chloromethyl group.

The azole derivative (Ia) is a tautomeric form (“thiono” form) of an azole derivative (“mercapto” form) represented by the following general formula (Ib) in which X in the general formula (I) is —SH. is there.

(In the general formula ^{(Ib), R 1, Y} 1, Y 2, m and A are each the same as ^{R 1, Y 1, Y 2} , m and A in the general formula (I).)
When the azole derivative (I) or (Ia) is used as an active ingredient of an agricultural or horticultural agent or an industrial material protecting agent, in a plant body or bacterial cell, a functional group -X or = S in the triazole ring or imidazole ring Is released, and its activity is expressed.

Specific examples of preferred azole derivatives according to the present invention include, but are not limited to, azole derivatives represented by the following general formula (Ic) or (Id).

(In the general formula (Ic) and ^{(Id), R 1, Y} 1, Y 2 and A are the same as ^{R 1, Y 1,} Y ² and A in each of the above general formula (I) and (Ia) In general formula (Ic), X is the same as X in general formula (I) above.)
Furthermore, specific examples of the azole derivative according to the present invention include azole derivatives represented by the following general formula (Ie).

(In the general formula (Ie), Y ³ represents a hydrogen atom, a fluorine atom or a chlorine atom.)
In the azole derivatives (I) and (Ia), there are stereoisomers based on the configuration of the organic group bonded to the cyclopentane ring, and optical isomers exist for each stereoisomer. Therefore, the azole derivatives (I) and (Ia) include both those containing these isomers alone and those containing each isomer in an arbitrary ratio. Among them, an azole derivative in which a hydroxy group bonded to a cyclopentane ring and a halomethyl group are in cis form is preferable, and a hydroxy group bonded to a cyclopentane ring and a halomethyl group and a substituted or unsubstituted benzyl group are in cis form. An azole derivative which is a type is more preferable.

[2. Method for producing azole derivative]
The production method of the azole derivatives (I) and (Ia) is not particularly limited. For example, an azole derivative represented by the following general formula (III) (hereinafter referred to as azole derivative (III)) is a starting material. Can be manufactured as. A method for producing the azole derivative (III) will be described later.

(In general formula (III), R ¹ , Y ² , m and A are the same as R ¹ , Y ² , m and A in general formula (I), respectively.)
Specifically, a method in which the azole derivative (III) is successively reacted with a strong base and sulfur in the presence of a diluent and then the product is hydrolyzed with water (reaction (a)), or the azole derivative (III) is used. Depending on the method of reacting in the presence of sulfur powder and dimethylformamide (reaction (b)), an azole derivative represented by the following general formula (IIa) (hereinafter referred to as azole derivative (IIa)), or the following general formula (IIb) Is obtained (hereinafter referred to as azole derivative (IIb)).

(In the general formulas (IIa) and (IIb), R ¹ , Y ² , m and A are the same as R ¹ , Y ² , m and A in the general formula (I), respectively.)
Next, by opening the oxetane ring of the obtained azole derivative (IIa) or azole derivative (IIb), the azole derivative (Ia) or an azole derivative represented by the above general formula (Ib) (hereinafter referred to as azole derivative ( Ib)) can be obtained.

In fact, in each step, the azole derivative (IIa) and the azole derivative (Ia) which are thiono forms are isolated. Therefore, in the following, as shown in Reaction Scheme 1, reaction (a) and reaction ( b) will be described as a method for producing the azole derivative (IIa), and the oxetane ring opening reaction will be described as a method for producing the azole derivative (Ia) from the azole derivative (IIa).

(Reaction (a))
In the reaction (a), the azole derivative (IIIa) is obtained by sequentially reacting the azole derivative (III) with a strong base and sulfur in the presence of a diluent, and then hydrolyzing the product with water.

Strong bases can include all strong alkali metal bases commonly used in similar reactions, such as n-butyllithium, lithium diisopropylamide, sodium hydride and sodium amide, and tetramethylethylenediamine ( Potassium t-butoxide as a mixture with TMEDA) can preferably be used.

Diluents can include all inert organic solvents commonly used in similar reactions, such as ethers such as tetrahydrofuran (THF), dioxane, diethyl ether and 1,2-dimethoxyethane, In addition, a strong polar solvent such as liquid ammonia or dimethyl sulfoxide can be preferably used.

The amount of sulfur used is, for example, 1 to 5 mol of sulfur, and preferably 1 to 1.5 mol of sulfur with respect to 1 mol of azole derivative (III). Sulfur is preferably used in a powder state.

Hydrolysis in reaction (a) may be carried out in the presence of an acid, which can include all inorganic or organic acids commonly used in similar reactions, such as acetic acid, Dilute sulfuric acid and dilute hydrochloric acid can be preferably used. However, the hydrolysis can also be carried out using an aqueous ammonium chloride solution.

The reaction temperature in the reaction (a) is, for example, −70 ° C. to 20 ° C., preferably −70 ° C. to 0 ° C.

The produced azole derivative (IIa) may be separated and purified by a conventional method such as recrystallization and chromatography.

(Reaction (b))
In the reaction (b), the azole derivative (IIa) is obtained by reacting the azole derivative (III) in the presence of sulfur powder and dimethylformamide.

When the azole derivative (IIa) is produced by the reaction (b), the azole derivative (III) can be diluted with a diluent. Any conventional aprotic polar organic solvent can be used as the diluent. Preferably, amides such as dimethylformamide; N-alkyl-pyrrolidones such as N-octyl-pyrrolidone and N-dodecyl-pyrrolidone; and N-alkyl-caprolactams such as N-methyl-caprolactam and N-octyl-caprolactam Kind.

The reaction temperature can be varied within a certain range, for example, a temperature of 140 ° C. to 200 ° C., preferably 150 ° C. to 160 ° C. The reaction can be carried out at atmospheric pressure or under pressure.

The amount of sulfur used is, for example, 6 to 15 mol of sulfur, and preferably 8 to 13 mol of sulfur with respect to 1 mol of azole derivative (III).

The azole derivative (IIa) produced may be separated and purified by a conventional method such as recrystallization and chromatography.

(Ring-opening reaction)
Next, by opening the oxetane ring of the azole derivative (IIa), the azole derivative (Ia) is obtained. As a method for opening the oxetane ring, a method in which an azole derivative (IIa) and a halogen acid are mixed in a solvent to generate a halogenated methyl group and a tertiary hydroxy group is preferably used.

Examples of the halogen acid include hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide. Of these, hydrogen chloride and hydrogen bromide are preferably used. The halogen acid may be introduced as a gas, or may be added after being dissolved in an organic solvent. By adding a halide salt (for example, lithium chloride and sodium chloride) and another acid (for example, Bronsted acid such as toluenesulfonic acid, methanesulfonic acid and sulfuric acid, or Lewis acid such as aluminum chloride). The azole derivative (Ia) may be obtained from the azole derivative (IIa) by generating a halogen acid in the system.

The solvent is not particularly limited, and examples thereof include amides such as N-methylpyrrolidone and N, N-dimethylformamide, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and dioxane, and water. Of these, dimethylformamide, methanol, water and dioxane are preferably used.

The amount of the halogen acid is, for example, 0.5 to 50 times mol, preferably 1 to 20 times mol with respect to the azole derivative (IIa).

The reaction temperature can be appropriately set depending on the solvent used and the like, and is, for example, −20 ° C. to 250 ° C., preferably −10 ° C. to 150 ° C., particularly 50 ° C. to 80 ° C. preferable. The reaction time can be appropriately set depending on the solvent used and the like. For example, the reaction time is 0.1 hour to several days, and preferably 1 hour to 48 hours.

When halogen acid is added to oxetane, the 1-position becomes a tertiary hydroxy group and the 2-position becomes a halogenated methyl group.

In addition, according to the manufacturing method of azole derivative (Ia) including this ring-opening reaction, only the geometric isomer in which the hydroxy group and halomethyl group which are couple | bonded with the cyclopentane ring can be obtained.

Regarding the azole derivative (I) other than the azole derivative (Ib), the following general formula (I) can be obtained from the azole derivative (IIa) or azole derivative (IIb) by the following reaction (c), (d) or (e). IIc) is synthesized (hereinafter referred to as azole derivative (IIc)), and the azole derivative (IIc) is reacted with a halogen acid to open the oxetane ring of the azole derivative (IIc). Other azole derivatives (I) other than the derivative (Ib) can be obtained.

(In the general formula ^{(IIc), R 1, Y} 2, m and A are each the same as ^{R 1, Y} 2, m and A in the general formula (I), ^{X 1} is ^-SR 2, -SO -R ² , -SO ₂ -R ² or -SO ₃ H is represented, and R ² is the same as R ² in the general formula (I).
Hereinafter, the reactions (c), (d), and (e) when the azole derivative (IIa) is used will be described. In addition, since the ring-opening reaction after reaction (c), (d) or (e) is the same as the ring-opening reaction at the time of obtaining azole derivative (Ia), description mentioned above can be used.

(Reaction (c))
In reaction (c), the azole derivative (IIa) is converted to a compound of the general formula (IV) in the presence of an acid binder and a diluent.
R ³ -L .. (IV)
(In the general formula (IV), R ³ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or a halo having 2 to 6 carbon atoms. An alkenyl group or an arylalkyl group (the alkyl moiety has 1 to 4 carbon atoms). L represents a halogen atom.)
X ¹ is —SR ² (wherein R ² is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 1 to 6 carbon atoms). An azole derivative (IIc) is obtained, which is a haloalkyl group, a haloalkenyl group having 2 to 6 carbon atoms, or an arylalkyl group (wherein the alkyl moiety has 1 to 4 carbon atoms).

R ³ alkyl group having 1 to 6 carbon atoms, alkenyl group having 2 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, haloalkenyl group having 2 to 6 carbon atoms, arylalkyl group (alkyl moiety) 1 to 4) has the same meaning as those of R ² .

L represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of acid binders include all commonly used inorganic bases and organic bases, such as alkali metal hydroxides or alkaline earth metal waters such as sodium hydroxide, calcium hydroxide and potassium hydroxide. Oxides; ammonium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate; alkali metal acetates or alkaline earth metal acetates such as sodium acetate, potassium acetate and calcium acetate; and Trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methyl-piperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) and diazabicycloun Decene (DB Tertiary amines such as U) can be suitably used.

Diluents can include all commonly used organic solvents such as diethyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, ethers such as tetrahydrofuran and dioxane, nitriles such as acetonitrile, and the like. A polar solvent such as dimethyl sulfoxide or dimethylformamide can be suitably used.

The reaction temperature is, for example, 0 ° C. to 120 ° C., preferably 20 ° C. to 100 ° C.

The amount of the halide represented by the general formula (IV) is, for example, 1 to 2 mol with respect to 1 mol of the azole derivative (IIa). As the acid binder, for example, an equivalent amount or an excess amount of the azole derivative (IIa) can be used.

(Reaction (d))
In the reaction (d), the azole derivative (IIa) obtained is sequentially converted into a strong base and a compound represented by the general formula (V)
R ⁴ —S—S—R ⁴ (V)
(In general formula (V), R ⁴ represents an aryl group.)
To obtain an azole derivative (IIc) in which X ¹ is —SR ² (where R ² represents an aryl group).

The aryl group in R ⁴ has the same meaning as the aryl group in R ² described above.

As the strong base and diluent, the strong base and diluent exemplified in the description of the reaction (a) can be used.

(Reaction (e))
In reaction (e), azole derivative (IIc) in which X ¹ is —SO ₃ H, —SO ₂ R ² or —SOR ² is obtained by reacting azole derivative (IIa) in the presence of an oxidizing agent and a diluent. Get. In the reaction (e), an azole derivative (IIc) in which X ¹ is —SR ² can be used instead of the azole derivative (IIa).

The oxidizing agent can include all substances commonly used for the oxidation of sulfur, such as hydrogen peroxide; peracids such as peracetic acid and metachloroperbenzoic acid; and inorganic salts such as potassium permanganate. Can be suitably used.

Diluents can include all solvents commonly used in similar reactions. For example, when hydrogen peroxide or peracid is used as the oxidizing agent, acetic acid or glacial acetic acid can be suitably used as the diluent. When potassium permanganate is used as the oxidizing agent, water or alcohol such as t-butanol can be preferably used.

The reaction temperature is, for example, 0 ° C. to 100 ° C., preferably 10 ° C. to 100 ° C.

When an SO compound is to be synthesized, the oxidant is preferably used in an equivalent amount relative to the azole derivative (IIc) in which X ¹ is —SR ² . On the other hand, when an SO ₂ compound is to be synthesized, the oxidant is preferably used in an excess amount relative to the azole derivative (IIc) in which X ¹ is —SR ² .

As mentioned above, although the method to manufacture azole derivative (I) other than azole derivative (Ib) from azole derivative (IIa) or azole derivative (IIb) was demonstrated, the manufacturing method of azole derivative (I) is limited to this. For example, by reacting the azole derivative (Ia) or the azole derivative (Ib) with the reaction similar to the above reaction (c), (d) or (e), other than the azole derivative (Ib) The azole derivative (I) may be produced.

As described above, the azole derivative (IIa) and the azole derivative (IIb) obtained by the reaction (a) or the reaction (b) and the azole derivative (IIc) obtained by the reaction (c), the reaction (d) or the reaction (e). ) Is suitably used for the production of the azole derivative (I) as an intermediate compound for producing the azole derivative (I). Therefore, the azole derivative (IIa) and the azole derivative (II) represented by the following general formula (II) are also included in the category of the present invention as suitable intermediate compounds for producing the azole derivative (I).

(In the general formula ^{(II), R 1, X} , Y 2, m and A are each the same as ^{R 1, X, Y 2,} m and A in the general formula (I).)
Similarly, a method for producing the azole derivative (I) including a step of obtaining the azole derivative (I) by reacting the azole derivative (II) with a halogen acid is also included in the scope of the present invention.

(Method for producing azole derivative (III))
Among the azole derivatives (III), the azole derivative (III) in which R ¹ is an alkyl group or a hydrogen atom may be a compound produced by a known method (for example, the method described in Patent Document 1).

Among the azole derivatives (III), an azole derivative in which R ¹ is an alkoxy group (hereinafter referred to as azole derivative (IIIa)) is represented by the following general formula (VII) by, for example, each step shown in Reaction Scheme 2. Azole derivative (hereinafter referred to as azole derivative (VII)). In addition, what is necessary is just to use the compound manufactured by a well-known method (for example, the method of patent document 1) as azole derivative (VII).

Hereinafter, each step shown in Reaction Scheme 2 will be described.

(Ring closure process)
In the ring closing step, the azole derivative (VII) is closed to obtain an azole derivative represented by the general formula (VI) (hereinafter referred to as azole derivative (VI)). A preferred method for synthesizing the azole derivative (VI) by ring closure includes a method of reacting the azole derivative (VII) in a solvent in the presence of a sulfonyl chloride and an excess amount of a base.

As the sulfonyl chlorides, p-toluenesulfonyl chloride, methanesulfonyl chloride and the like can be used. Of these, p-toluenesulfonyl chloride is preferably used.

The base is not particularly limited, and examples thereof include metal hydride compounds such as sodium hydride, and alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide and potassium t-butoxide. It can be used suitably. Among these, sodium hydride can be used more suitably.

The amount of sulfonyl chlorides is preferably 1 to 2 moles relative to the azole derivative (VII). The amount of the base is preferably 2.5 to 10-fold mol, more preferably 2.8 to 6-fold mol based on the azole derivative (VII).

The solvent is not particularly limited. For example, amides such as N-methylpyrrolidone and N, N-dimethylformamide, ethers such as tetrahydrofuran and dioxane, dimethyl sulfoxide, and a mixed solvent thereof can be used. . Among these, tetrahydrofuran can be preferably used.

The reaction temperature can be appropriately set depending on the type of solvent, azole derivative (VII), sulfonyl chlorides, base and the like used, but is preferably −100 ° C. to 200 ° C., more preferably −50 ° C. ~ 150 ° C. The reaction time can be appropriately set depending on the type of solvent, azole derivative (VII), sulfonyl chlorides, base and the like to be used, but is preferably 0.1 hour to several days, more preferably 0. 5 hours to 2 days.

(Alkylation process)
In the alkylation step, the azole derivative (IIIa) is obtained by alkylating the hydroxy group of the azole derivative (VI). In general formula (IIIa), R ⁵ is an alkyl group having 1 to 3 carbon atoms. The alkylation method is not particularly limited, but a metal alkoxide prepared from a hydroxy group of the azole derivative (VI) and an alkali metal base in a solvent is converted to an alkyl compound having 1 to 3 carbon atoms having a leaving group. The method of making it react at room temperature can be mentioned.

Solvents include ether solvents such as tetrahydrofuran, amide solvents such as N-methylpyrrolidone and N, N-dimethylformamide, aromatic solvents such as benzene and toluene, and halide solvents such as methylene chloride. Can be suitably used. Of these, tetrahydrofuran can be more preferably used.

Examples of the alkyl compound having 1 to 3 carbon atoms having a leaving group include alkyl halides such as alkyl iodide and alkyl bromide in which alkyl has 1 to 3 carbon atoms, and tosyl in which alkyl has 1 to 3 carbon atoms. Mention may be made of sulfonate esters such as oxyalkyl and mesyloxyalkyl. Of these, alkyl iodide can be preferably used. Furthermore, among alkyl iodides, it is more preferable to use methyl iodide.

Examples of the alkali metal base include sodium, sodium hydride, sodium hydroxide, and potassium hydroxide. Of these, sodium hydride is preferably used.

[3. (Agricultural and horticultural chemicals)
Since the azole derivatives (I) and (Ia) have a 1,2,4-triazolyl group or an imidazolyl group, they form acid addition salts of inorganic acids and organic acids, or metal complexes. Therefore, it can be used as an active ingredient such as agricultural and horticultural agents as part of acid addition salts and metal complexes.

(1) Plant disease control effect The azole derivatives (I) and (Ia) exhibit a control effect on a wide range of plant diseases. Examples of applicable diseases include: soybean rust (Phakopsora pachyrhizi, Phakopsora meibomiae), rice blast (Pyricularia grisea), rice sesame leaf (Cochliobolus miyabeanus), rice leaf blight (Xanthomonas oryzae), rice crest Blight (Rhizoctonia solani), rice small black rot (Helminthosporium sigmoideun), rice seedling disease (Gibberella fujikuroi), rice seedling blight (Pythium aphanidermatum), apple powdery mildew (Podosphaeraleucotricha), apple black infestation (Ventia qualia) ), Apple morinia disease (Moniliniamali), apple spotted leaf disease (Alternaria alternata), apple rot disease (Valsa mali),
Pear black spot disease (Alternaria kikuchiana), pear powdery mildew (Phyllactinia pyri), pear red star disease (Gymnosporangium asiaticum), pear black spot disease (Venturia nashicola), grape powdery mildew (Uncinula necator), grape mildew (Plasmopara viticola) ), Grape late rot (Glomerella cingulata), Barley powdery mildew (Erysiphe graminis f. Sp hordei), Barley black rust (Puccinia graminis), Barley yellow rust (Puccinia striiformis), Barley leaf rot (Pyrenophora graminea) , Barley cloud disease (Rhynchosporium secalis), wheat powdery mildew (Erysiphe graminis f. Sp tritici), wheat red rust (Puccinia recondita), wheat yellow rust (Puccinia striiformis), wheat eye spot (Pseudocercosporella herpotrichoides) Fungus (Fusarium graminearum, Microdochium nivale), wheat blight (Phaeosphaeria nodorum), wheat leaf blight (Septoria tritici), cucurbits This disease (Sphaerotheca fuliginea), cucumber anthracnose (Colletotrichum lagenarium), cucumber downy mildew (Pseudoperonospora cubensis), cucumber gray plague (Phytophthora capsici), tomato powdery mildew (Erysiphe cichoracearum), tomato ring rot disease (Alternaria solani) ), Eggplant powdery mildew (Erysiphe cichoracearum), strawberry powdery mildew (Sphaerotheca humuli), tobacco powdery mildew (Erysiphe cichoracearum), sugar beet brown spot (Cercospora beticola), corn smut (Ustilago maydis), fruit tree Monilinia fructicola, gray mold disease (Botrytis cinerea) that causes various crops, and sclerotia disease (Sclerotinia sclerotiorum). In addition, grape rust (Phakopsora ampelopsidis), watermelon vine (Fusarium oxysporumf.sp.niveum), cucumber vine (Fusarim oxysporumf.sp.cucumerinum), radish yellow (Fusarium oxysporumf.sp.raphani) ), Tobacco red streak (Alternaria longipes), potato summer rot (Alternaria solani), soybean brown spot (Septoria glycines), soybean purpura (Cercospora kikuchii), and the like.

Examples of applicable plants include wild plants, plant cultivars, plants and plant cultivars obtained by conventional biological breeding such as crossbreeding or protoplast fusion, and genetically modified plants and plant cultivars obtained by genetic manipulation. Is mentioned. Examples of genetically modified plants and plant cultivars include herbicide-tolerant crops, pest-tolerant crops incorporating insecticidal protein production genes, disease-resistant crops incorporating resistance-inducing substance production genes against diseases, food-enhancing crops, and yield improvement Examples include crops, crops with improved shelf life and crops with improved yield. Specific examples of genetically modified plant cultivars include those containing registered trademarks such as ROUNDUP READY, LIBERTY LINK, CLEARFIELD, YIELDGARD, HERCULEX, BOLLGARD and the like.

(2) Plant growth action In addition, the azole derivatives (I) and (Ia) have the effect of increasing the yield by adjusting the growth and the effect of improving the quality of a wide variety of crops and horticultural plants. . Examples of such crops include: wheat, barley, buckwheat and other wheat, rice, rapeseed, sugarcane, corn, maize, soybeans, peas, peanuts, sugar beet, cabbage, garlic, radish, carrots, apples, pears Citrus fruits such as oranges, oranges, lemons, peaches, cherry peaches, avocados, mangoes, papayas, peppers, cucumbers, melons, strawberries, tobacco, tomatoes, eggplants, grass, chrysanthemums, azaleas, and other ornamental plants.

(3) Industrial Material Protection Effect Furthermore, the azole derivatives (I) and (Ia) exhibit an excellent effect of protecting the material from a wide range of harmful microorganisms that invade the industrial material. Examples of such microorganisms include: Aspergillus sp., Trichoderma sp., Penicillium sp., Geotrichum sp., Which are paper and pulp-degrading microorganisms (including slime-forming bacteria). ), Ketomium (Caetomium sp.), Cadophora sp., Ceratostomella sp., Cladosporium sp., Corticium sp., Lentinus sp., Lenzites sp.), Forma sp., Polysticus sp., Pullularia sp., Stereum sp., Trichosporium sp., Aerobacter sp., Bacillus sp., Desulfovibrio sp., Pseudomonas sp., Flavobacterium ( Flavobacterium sp.) And fiber-degrading microorganisms such as Micrococcus sp., Aspergillus sp., Penicillium sp., Chaetomium sp., Myrothecium sp., Curvularia sp.), Gliomastix sp., Mennoniella sp., Sarcopodium sp., Stschybotrys sp., Stemphylium sp., Zygorhynchus sp .), Bacillus sp., And Staphylococcus sp., Wood-modifying fungi such as Tyromyces palustris, Coriolus versicolor, Aspergillus sp., Penicillium sp. ), Rhizopus sp., Aureobasidium sp., Aspergillus sp. And Penicillium sp., Skin-degrading microorganisms, such as Gliocladum sp., Cladosporium sp., Chaetomium sp., And Trichoderma sp. , Ketomium (Chaetomium sp.), Cladosporium (Cl.sporium sp.), Mucor (Mucor sp.), Paecilomyces sp., Pilobus (Pilobus sp.), Pullularia (Pullularia sp.), Trichosporon sp. ), And Aspergillus sp., Penicillium sp., Rhizopus sp., Trichoderma sp., Trichoderma sp., And Chaetomium sp, such as Tricothecium sp. .), Myrothecium sp., Streptomyces sp. Demonas (Pseudomonas sp.), Bacillus (Bacillus sp.), Micrococcus (Micrococcus sp.), Serratia (Serratia sp.), Margarinomyces sp., And Monascus sp. Microorganisms Aspergillus sp., Penicillium sp., Cladosporium sp., Aureobasidium sp., Gliocladium sp., Botryo diprodia (Botryodiplodia sp.), Macrosporium sp., Monilia sp., Forma (Phoma sp.), Pullularia sp., Sporotrichum sp., Trichoderma sp., Bacillus sp., Proteus sp., Pseudomonas sp., And Serratia sp.

(4) Formulation In order to apply the azole derivative (I) or (Ia) as an active ingredient of an agricultural or horticultural agent, it may be left as it is without adding any other components, but usually a solid carrier or a liquid carrier, a surfactant. And mixed with other formulation adjuvants, etc. to be used in various forms such as powders, wettable powders, granules and emulsions.

These preparations contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight, more preferably 2 to 80% by weight, of the azole derivative (I) or (Ia) as an active ingredient. To do.

Examples of solid carriers, liquid carriers (liquid diluents) and surfactants used as formulation adjuvants include talc, kaolin, bentonite, diatomaceous earth, white carbon, and clay as solid carriers. Examples of the liquid diluent include water, xylene, toluene, chlorobenzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethylformamide and alcohol. Surfactants should be properly used depending on their effects. Examples of emulsifiers include polyoxyethylene alkylaryl ether and polyoxyethylene sorbitan monolaurate. Dispersants include lignin sulfonate and dibutyl naphthalene. Examples of the wetting agent include alkyl sulfonates and alkyl phenyl sulfonates.

Some preparations are used as they are, while others are diluted to a predetermined concentration with a diluent such as water. The concentration of the azole derivative (I) when diluted is preferably in the range of 0.001 to 1.0%.

In addition, the amount of the azole derivatives (I) and (Ia) used is 20 to 5000 g, more preferably 50 to 2000 g per 1 ha of agricultural and horticultural lands such as fields, fields, orchards and greenhouses. Since these use concentrations and amounts vary depending on the dosage form, use time, use method, use place, target crop, etc., they can be increased or decreased without sticking to the above range.

Further, the azole derivatives (I) and (Ia) are combined with other active ingredients such as fungicides, insecticides, acaricides and herbicides as exemplified below to enhance performance as agricultural and horticultural agents. Can also be used.

<Antimicrobial substances>
Acibenzolar S-methyl, 2-phenylphenol (OPP), azaconazole, azoxystrobin, amisulbrom, bixaphene, benalaxyl, benomyl, bench avaricarb-isopropyl, bicarbonate, biphenyl, viteltanol, blasticidin-S, borax, bordeaux, boscalid, Bromuconazole, bronopol, bupirimate, secbutyramine, calcium polysulfide, captafor, captan, carbendazim, carboxin, carpropamide, quinomethionate, chloronebu, chloropicrin, chlorothalonil, clozolinate, cyazofamide, cyflufenamide, simoxanil, cyproconil, cyprodiazole Dazomet, debacarb, diclofuranide, diclocimet, dicro Gin, Dichlorane, Dietofencarb, Difenoconazole, Diflumethrin, Dimethomorph, Dimethoxystrobin, Diniconazole, Dinocup, Diphenylamine, Dithianon, Dodemorph, Dodine, Edifenfoss, Epoxyconazole, Etapoxam, Ethoxyquin, Etridiodone, Enestropheline, Namidon Fenarimol, fenbuconazole, fenflam, fenhexamide, phenoxanyl, fenpicuronyl, fenpropidin, fenpropimorph, fentin, felvam, ferrimzone, fluazinam, fludioxonil, flumorph, fluoromide, floxastrobin, fluquinconazole, flusilazole, fursulfamide , Flutolanil, flutriafol, Olpetet, Focetyl-aluminum, Fuberidazole, Furaxil, Furametopir, Fluopicolide, Fluopyram, Guazatine, Hexachlorobenzene, Hexaconazole, Himexazole, Imazalil, Imibenconazole, Iminotazine, Ipconazole, Iprobenfos, Iprodithiol , Kasugamycin, copper preparations such as copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper, crezooxime methyl, mancocapper, mancozeb, maneb, mandipropamide, mepanipyrim, mepronil, metalaxyl, metconazole , Methylam, metminosoutrobin, myrdiomycin, microbutanyl, nitrotal-isopropyl, nuari Mole, off-race, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxyl, oxytetracycline, pefrazoate, orisatrobin, penconazole, pencyclon, penthiopyrad, pyribencarb, fusalide, picoxystrobin, piperalin, polyoxin, probenazole, prochloraz, procymidone , Propamocarb, propiconazole, propinebole, proquinazide, prothioconazole, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroxylone, quinoxyphene, quintozen, silthiofam, cimeconazole, spiroxamine, sulfur and sulfur preparation, tebuconazole, teclophthalam, , Tetraconazole, thiabendazole, tifluzamide, thi Phanate-Methyl, Tyram, Thiazinyl, Torcrophos-Methyl, Tolylfluanid, Triadimefone, Triadimenol, Triazoxide, Tricyclazole, Tridemorph, Trifloxystrobin, Triflumizole, Triforin, Triticonazole, Validamycin, Vinclozoline, Zineb, ziram, zoxamide, amisulbrom, sedaxane, flutianil, varifenal, amethoctrazine, dimoxystrobin, metolaphenone, hydroxyisoxazole, floxapyroxad and metasulfocarb.

<Insecticide / acaricide / nematicide>
Abamectin, Acephate, Acrinathrin, Alanicarb, Aldicarb, Alletrin, Amitraz, Avermectin, Azadirachtin, Azamethifos, Azinphos-ethyl, Azinphos-methyl, Azocycline, Bacillus filmus, Bacillus subtilis, Bacillus thuringibulbbenthulbenbencarb , Benzoxymate, Bifenazite, Bifenthrin, Bioarethrin, Bioresmethrin, Bistriflurone, Buprofezin, Butocaboxin, Butoxycarboxyne, Kazusafos, Carbaryl, Carbofuran, Carbosulfan, Cartap, CGA50439, Chlordein, Chloretifol, Chlorfenapir Fenbinfoss, Chlorfluazuron Chlormefos, Chlorpyrifos, Chlorpyrifosmethyl, Chromaphenozide, Clofentedine, Clothianidin, Chloranthraliniprol, Counpafos, Cryolite, Cyanophos, Cycloproton, Cyfluthrin, Cyhalothrin, Cihexatin, Cipermethrin, Cifenotrin, Cyromazine, Ciazapyr, Sienopyrafen, DCIP, DDT, Deltamethrin, Demeton-S-methyl, Diafenthiuron, Diazinone, Dichlorophene, Dichloropropene, Dichlorvos, Dicofor, Dicrotophos, Dicyclanil, Diflubenzuron, Dimethoate, Dimethylvinphos, Franbutone, Dinobutone , Emamectin, endosulfan, EPN, esfenvalerate, etiophencarb, ethion, Tiprol, etofenprox, etoprofos, etoxazole, famflu, fenamifos, phenazaquin, fenbutatin oxide, fenitrothion, fenocarb, phenothiocarb, phenoxycarb, fenpropatrine, fenpyroximate, fenthionate, fenvalerate, fipronil, flunipyamide Ron, flucitrinate, fluphenoxuron, flumethrin, fulvalinate, flubendiamide, formethanate, fostiazate, halfenprox, furthiocarb, halohenozide, gamma-HCH, heptenofos, hexaflumuron, hexithiazox, hydramethylnon , Imidacloprid, imiprothrin, indoxacarb, isoprocar Bu, isoxathion, lufenuron, malathion, mecarbam, metham, methamidophos, methidathione, metiocarb, methomyl, methoprene, methosrine, methoxyphenozide, metorcarb, milbemectin, monocrotofos, nared, nicotine, nitenpyram, novalflumetron, oxyflumetron Tonmethyl, parathion, permethrin, phentoate, folate, fosaron, phosmet, phosphamidone, foxim, pirimicarb, pirimiphos methyl, profenofos, propoxur, prothiophos, pymetrozine, pyracrophos, pyrethrin, pyridaben, pyridalyl, pyrimidifene, pyriproxy Fen, Pyrifluquinazone, Pyriprole, Quinalfos, Shirafu Ofen, Spinosad, Spirodiclofen, Spiromethifene, Spirotetramat, Sulframide, Sulfotep, SZI-121, Tebufenozide, Tebufenpyrad, Tebupyrimfos, Teflubenzuron, Tefluthrin, Temefos, Terbufos, Tetrachlorbinfos, Thiacloprio, Thiamethioxam Fanox, thiometone, tolfenpyrad, tralomethrin, tralopyril, triazamate, triazophos, trichlorphone, triflumuron, bamidthione, varifenal, XMC, xylylcarb, imisiaphos and lepimectin.

<Plant growth regulator>
Ansimidol, 6-benzylaminopurine, paclobutrazole, diclobutrazole, uniconazole, methylcyclopropene, mepiquat chloride, ethephone, chlormequat chloride, inabenfide, prohexadione and salts thereof, and trinexa Pack ethyl etc. Also, jasmonic acid, brassinosteroid and gibberellin as plant hormones.

In order to apply the azole derivative (I) or (Ia) as an active ingredient of an industrial material protective agent, it may be used alone without adding other ingredients, but generally it can be dissolved in a suitable liquid carrier. Alternatively, it is dispersed or mixed with a solid carrier, and if necessary, an emulsifier, a dispersing agent, a spreading agent, a penetrating agent, a wetting agent, a stabilizer and the like are added, and a wettable powder, powder, granule, tablet It can be used as dosage forms such as pastes, suspensions and sprays. Moreover, you may mix | blend another fungicide, an insecticide, a degradation inhibitor, etc.

As the liquid carrier, any liquid may be used as long as it does not react with the active ingredient. For example, water, alcohols (for example, methyl alcohol, ethyl alcohol, ethylene glycol, and cellosolve), ketones (for example, acetone, and Methyl ethyl ketone, etc.), ethers (eg, dimethyl ether, diethyl ether, dioxane, and tetrahydrofuran), aromatic hydrocarbons (eg, benzene, toluene, xylene, and methylnaphthalene), aliphatic hydrocarbons (eg, gasoline, Kerosene, kerosene, machine oil, fuel oil, etc.), acid amides (eg, dimethylformamide, N-methylpyrrolidone, etc.), halogenated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), esters ( For example, acetate Glycol ester, and glycerine esters of fatty acids, etc.), nitriles (for example, using acetonitrile, etc.), as well as dimethyl sulfoxide and the like.

As the solid support, fine powders or granular materials such as kaolin clay, bentonite, acid clay, pyrophyllite, talc, diatomite, calcite, urea and ammonium sulfate can be used.

As emulsifiers and dispersants, surfactants such as soaps, alkylsulfonic acids, alkylarylsulfonic acids, dialkylsulfosuccinic acids, quaternary ammonium salts, oxyalkylamines, fatty acid esters, polyalkylene oxides and anhydrosorbitols Can be used.

When the azole derivative (I) or (Ia) is contained in the preparation as an active ingredient, the content ratio varies depending on the dosage form and the intended purpose, but in general, the concentration is 0.1 to 99.9% by weight. It is appropriate to add as follows. In actual use, the treatment concentration is usually adjusted to 0.005 to 5% by weight, preferably 0.01 to 1% by weight, by appropriately adding a solvent, a diluent, an extender and the like. It is preferable to do this.

As described above, the azole derivatives (I) and (Ia) exhibit an excellent bactericidal action against many fungi that cause plant diseases. In addition, the azole derivatives (I) and (Ia) have little phytotoxicity to plants. That is, by including the azole derivative (I) or (Ia) as an active ingredient, it is low in toxicity to human livestock, has excellent handling safety, exhibits a high control effect on a wide range of plant diseases, and has little phytotoxicity. A disease control agent can be realized.
(Additional notes)
As described above, the azole derivative according to the present invention is an azole derivative characterized by being represented by the following general formula (I) or (Ia).

(In the general formulas (I) and (Ia), Y ¹ represents a halogen atom,
R ¹ represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom,
Y ² represents a halogen atom, m represents 0, 1 or 2, and when m is 2, a plurality of Y ² may be different from each other;
A represents a nitrogen atom or a methine group.
In the general formula (I), X represents —SH, —SR ² , —SO—R ² , —SO ₂ —R ² or —SO ₃ H. R ² represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a haloalkenyl group having 2 to 6 carbon atoms, an aryl group, or an arylalkyl A group (the alkyl part has 1 to 4 carbon atoms), and in the aryl group and arylalkyl group in R ² , at least one hydrogen atom in the aromatic ring is a halogen atom, and an alkyl group having 1 to 4 carbon atoms (cyclohexane). An alkyl group), or a haloalkyl group having 1 to 4 carbon atoms. )
In the azole derivative according to the present invention, Y ¹ is preferably a chlorine atom.

The azole derivative according to the present invention may also be an azole derivative represented by the following general formula (Ic) or (Id).

(In the general formula (Ic) and ^{(Id), R 1, Y} 1, Y 2 and A are the same as ^{R 1, Y 1,} Y ² and A in each of the above general formula (I) and (Ia) In general formula (Ic), X is the same as X in general formula (I) above.)
In the azole derivative according to the present invention, A is preferably a nitrogen atom.

Further, the azole derivative according to the present invention is preferably an azole derivative represented by the following general formula (Ie).

(In the general formula (Ie), Y ³ represents a hydrogen atom, a fluorine atom or a chlorine atom.)
The intermediate compound according to the present invention is an intermediate compound used for producing the above-mentioned azole derivative, and is a compound represented by the following general formula (II) or (IIa).

(In the general formula (II) and ^{(IIa), R 1, Y} 2, m and A are the same as ^{R 1, Y} 2, m and A in each of the above general formula (I) and (Ia). General In the formula (II), X is the same as X in the general formula (I).)
In the intermediate compound according to the present invention, A is preferably a nitrogen atom.

The method for producing an azole derivative according to the present invention is a method for producing the above azole derivative,
The composition includes a step of reacting an intermediate compound represented by the following general formula (II) or (IIa) with a halogen acid to obtain an azole derivative represented by the above general formula (I) or (Ia).

(In General Formulas (II) and (IIa), R ¹ , Y ² , m and A are the same as R ¹ , Y ² , m and A in General Formula (I), respectively. General Formula (II) In the formula, X is the same as X in the general formula (I).)
Moreover, the manufacturing method of the azole derivative which concerns on this invention makes the compound shown by the following general formula (III) react with sulfur, the compound shown by the following general formula (IIa), or the compound shown by the following general formula (IIb) It is preferable to include the process of obtaining.

(In general formula (III), R ¹ , Y ² , m and A are the same as R ¹ , Y ² , m and A in general formula (I), respectively.)

(In the general formula (IIa), R ¹ , Y ² , m and A are the same as R ¹ , Y ² , m and A in the general formula (I), respectively.)

(In the general formula (IIb), R ¹ , Y ² , m and A are the same as R ¹ , Y ² , m and A in the general formula (I), respectively.)
Moreover, this invention also includes the agricultural and horticultural chemical | medical agent or industrial material protecting agent characterized by containing the above-mentioned azole derivative as an active ingredient.

Examples will be shown below, and the embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail. Further, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and the present invention is also applied to the embodiments obtained by appropriately combining the disclosed technical means. It is included in the technical scope of the invention. Moreover, all the literatures described in this specification are used as reference.

<Production Example: 2-[(5- (4-Chlorobenzyl) -2-chloromethyl-1-hydroxy-2-methylcyclopentyl) methyl] -2,4-dihydro-3H-1,2,4-triazole- Synthesis of 3-thione (compound (1))>

(1) 2-[(4- (4-Chlorobenzyl) -1-methyl-6-oxa-bicyclo [3.2.0] hept-5-yl) methyl] -2,4-dihydro-3H-1 , 2,4-Triazole-3-thione (Compound (2)) 1-[(4- (4-Chlorobenzyl) -1-methyl-6-oxa-bicyclo [3,2,0] hept-5 -Yl) methyl] -1H-1,2,4-triazole (compound (3)) 504.0 mg (1.59 mmol) was dissolved in 1 ml of dimethylformamide, where 506.2 mg (15.8 mmol) of powdered sulfur was dissolved; 10 eq.) Was added and heated to reflux for 6 hours. After cooling to room temperature, the reaction solution was filtered to remove insolubles, and the filtrate was dried under reduced pressure. Toluene and 10% aqueous sodium hydroxide solution were added to the residue, and the precipitated pink solid was filtered and washed with toluene. A 1M sulfuric acid aqueous solution and ethyl acetate were added to the solid, and the organic layer was separated. This organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Silicagel 60, 230-400 mesh, Merck, ethyl acetate / hexane = 1/1) to obtain 226 mg of compound (2) as a pale pink solid. (Yield 40.7%).
¹ H-NMR (CDCl ₃ )
1.24-1.38 (m, 1H), 1.38 (s, 3H), 1.60-1.87 (m, 3H), 1.97-2.05 (m, 1H), 2.48 (dd, 1H, J = 13.4, 10.6Hz), 2.54 ( dd, 1H, J = 13.4, 4.2Hz), 4.25 (d, 1H, J = 6.0Hz), 4.37 (dd, 1H, J = 5.9, 0.9Hz), 4.63 (dd, 2H, J = 16.2, 14.6Hz ), 7.10 (d, 2H, J = 8.4Hz), 7.16 (d, 2H, J = 8.4Hz), 7.81 (s, 1H), 12.13 (s, 1H).
(2) Synthesis of compound (1) 100.5 mg (0.287 mmol) of the obtained compound (2) was dissolved in 1 ml of dimethylformamide, 145.5 mg (3.43 mmol; 12 eq.) Of lithium chloride, and 65.9 mg (0.346 mmol; 1.2 eq.) of p-toluenesulfonic acid monohydrate was added, and the mixture was stirred at 80 ° C. for 3.5 hours. After cooling to room temperature, water and ethyl acetate were added, and the organic layer was separated. This organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Silicagel 60, 230-400 mesh, Merck, ethyl acetate / hexane = 2/1) to obtain 103.8 mg of compound (1) as a white solid. (Yield 93.5%). Melting point 170-171 ° C
¹ H-NMR (CDCl ₃ )
1.25 (s, 3H), 1.38-1.47 (m, 2H), 1.63-1.73 (m, 1H), 1.87-1.95 (m, 1H), 2.33-2.46 (m, 2H), 2.50-2.58 (m, 1H ), 3.65 (dd, 2H, J = 15.3, 10.7Hz), 4.00 (s, 1H), 4.54 (t, 2H, J = 15.1Hz), 7.11 (d, 2H, J = 8.4Hz), 7.21 (d , 2H, J = 8.4Hz), 7.84 (s, 1H), 11.9 (s, 1H).
LC-MS
(M + H ⁺ ) 386
<Reference Production Example: 1-[(4- (4-Chlorobenzyl) -1-methoxymethyl-6-oxa-bicyclo [3,2,0] hept-5-yl) methyl] -1H-1,2, Synthesis of 4-triazole (one embodiment of azole derivative (IIIa), hereinafter azole derivative (3a))>
(1) 1-[(4- (4-Chlorobenzyl) -1-hydroxymethyl-6-oxa-bicyclo [3,2,0] hept-5-yl) methyl] -1H-1,2,4- Synthesis of triazole (one embodiment of azole derivative (VI), hereinafter azole derivative (6)) 1-[(5- (4-chlorobenzyl) -1-hydroxy-2,2-bishydroxymethylcyclopentyl) methyl]- 30.0 mg (0.0853 mmol) of 1H-1,2,4-triazole (one embodiment of azole derivative (VII)) was dissolved in 0.9 ml of THF, and cooled to 0 ° C. in an ice bath. To this solution, 8.2 mg (0.205 mmol) of sodium hydride was added and stirred at 0 ° C. for 10 minutes. Further, 16.2 mg (0.0853 mmol) of p-toluenesulfonyl chloride was added and stirred for 2.5 hours while returning to room temperature. After completion of the reaction, water was added and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (chloroform / methanol = 30/1) to obtain an azole derivative (6).
Yield: 20.4 mg, Yield: 71.6%, Property: colorless liquid
¹ H-NMR (CDCl ₃ )
1.46-1.58 (m, 2H), 1.79-1.96 (m, 3H), 2.61 (dd, 1H, J = 13.7, 8.3Hz), 2.67 (dd, 1H, J = 13.7, 6.4Hz), 3.45 (dd, 1H, J = 12.9, 9.6Hz), 3.94 (dd, 1H, J = 12.9, 3.1Hz), 4.14 (d, 1H, J = 6.3Hz), 4.19 (d, 1H, J = 6.3Hz), 4.22 ( d, 1H, J = 15.0Hz), 4.57 (dd, 1H, J = 9.6, 3.1Hz), 4.68 (d, 1H, J = 15.0Hz), 7.01 (d, 2H, J = 8.4Hz), 7.25 ( d, 2H, J = 8.4Hz), 7.70 (s, 1H), 7.97 (s, 1H).
(2) Synthesis of azole derivative (3a) 50.0 mg of azole derivative (6) was dissolved in 1.5 ml of THF, 7.2 mg (0.180 mmol) of sodium hydride was added, and the mixture was stirred at room temperature for 15 minutes. To this was added 0.0112 ml (0.180 mmol) of iodomethane, and the mixture was stirred at room temperature for 1 hour and then stirred at 50 ° C. for 3 hours. Further, 0.0112 ml of iodomethane was added and stirred at the same temperature for 5 hours, 0.0112 ml of iodomethane and 7.2 mg of sodium hydride were added, and the mixture was stirred at room temperature for 15 hours, further stirred at 50 ° C. for 4 hours, and further, iodomethane was added in 0.1. 0112 ml and sodium hydride 7.2 mg were added and stirred for 1.5 hours. After completion of the reaction, water was added, extracted with ethyl acetate, and washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (ethyl acetate / hexane = 1/3) to obtain the azole derivative (3a).
Yield: 42.4 mg, Yield: 81.3%, Property: colorless viscous liquid
¹ H-NMR (CDCl ₃ )
1.45-1.53 (m, 1H), 1.57-1.64 (m, 1H), 1.68-1.76 (m, 1H), 1.81-1.94 (m, 2H), 2.33 (dd, 1H, J = 13.5, 4.0Hz), 2.45 (dd, 1H, J = 13.5, 9.6Hz), 3.34 (d, 1H, J = 10.1Hz), 3.38 (s, 3H), 3.39 (d, 1H, J = 10.1Hz), 4.14 (d, 1H , J = 6.1Hz), 4.48 (dd, 1H, J = 6.1, 1.3Hz), 4.53 (d, 1H, J = 14.8Hz), 4.73 (d, 1H, J = 14.8Hz), 7.05 (d, 2H , J = 8.4Hz), 7.21 (d, 2H, J = 8.4Hz), 7.96 (s, 1H), 8.16 (s, 1H).
<Formulation example>
Using the synthesized compound (1), wettable powder, powder, granule and emulsion were prepared.

(Wettable powder)
Compound (1) 50 parts lignin sulfonate 5 parts alkyl sulfonate 3 parts diatomaceous earth 42 parts were pulverized and mixed to obtain a wettable powder and diluted with water for use.

(Powder)
Compound (1) 3 parts Clay 40 parts Talc 57 parts were pulverized and mixed to prepare a powder used as dust.

(Granule)
Compound (1) 5 parts Bennite 43 parts Clay 45 parts Lignin sulfonate 7 parts were mixed uniformly, water was added and kneaded, and processed and dried into granules with an extrusion granulator to give granules.

(emulsion)
Compound (1) 20 parts polyoxyethylene alkyl aryl ether 10 parts polyoxyethylene sorbitan monolaurate 3 parts xylene 67 parts were mixed and dissolved uniformly to prepare an emulsion.

<Test Example 1: Cucumber gray mold control effect test by foliar spray treatment>
A hydrated form of compound (1) as shown in the above formulation example in a cotyledon stage cucumber (variety: SHARP1) cultivated using a square plastic pot (6 cm × 6 cm) with water at a predetermined concentration (100 mg / L) was diluted and suspended at a rate of 1,000 L / ha. The sprayed leaves were air-dried and then placed on a paper disk (diameter 8 mm) soaked with a spore solution of gray mold fungus and kept at 20 ° C. under high humidity. Five days after the inoculation, the morbidity of cucumber gray mold was investigated based on the survey criteria shown in Table 1, and the control value was calculated by the following formula.
Control value (%) = (1− (average morbidity in sprayed area / average illness in non-sprayed area)) × 100

As a result, the control value was 90% or more.

<Test Example 2: Wheat red rust control effect test by foliar spray treatment>
In a second leaf stage wheat (cultivar: Norin 61) grown using a square plastic pot (6 cm × 6 cm), a compound (1) in the form of a wettable powder as in Formulation Example 1 is washed with water. The suspension was diluted to a predetermined concentration (12.5 mg / L) and sprayed at a rate of 1,000 L / ha. The sprayed leaves were air-dried and then spray-inoculated with spores of wheat red rust fungus (adjusted to 200 cells / field of view, added with Grameen S to a final concentration of 60 ppm), and kept at 25 ° C. under high humidity for 48 hours. After that, it was managed in the greenhouse. On the 11th day after the inoculation, the morbidity of wheat rust was investigated based on the survey criteria shown in Table 2, and the control value was calculated by the following formula.
Control value (%) = (1− (average morbidity in sprayed area / average illness in non-sprayed area)) × 100

As a result, the control value was 90% or more.

<Test Example 3: Evaluation test for phytotoxicity of wheat growth suppression by seed treatment>
By pot test, the phytotoxicity of growth suppression by seed treatment was evaluated. After the compound (1) dissolved in DMSO so that the treatment amount is 20 or 200 g ai / 100 kg seeds is smeared on the wheat seeds (variety: Norin 61) in a vial, 8 wheat seeds in 80 cm ² pots Sowing. The lower water supply was controlled in a greenhouse, and the plant height of wheat was investigated 15 days after sowing. As a control, a test was conducted using the compound (9) represented by the following formula (IX) and metconazole instead of the compound (1) or without using any drug. The results are shown in Table 3.

Further, when the necrosis was observed, slight necrosis was observed in the plant body at any treatment amount when the compound (9) was used. In addition, when using metconazole at a treatment amount of 200 g ai / 100 kg seeds, slight necrosis was observed in the plant body, whereas when using compound (1), necrosis was observed at any treatment amount. Was not observed.

<Test Example 4: Test for evaluating phytotoxicity of growth inhibition for soybean>
The pot test evaluated the phytotoxicity of growth inhibition by foliar spray treatment. A soybean (cultivar: Enrei) cultivated using a square plastic pot (6 cm x 6 cm), a compound (1) in the form of a wettable powder as in Formulation Example 1, with water at a predetermined concentration (500 mg / L) Diluted and suspended at a rate of 1000 L / ha. The sprayed leaves were air-dried and managed in a greenhouse. The plant height of soybean was measured on the 13th day after the spraying of the drug. As a control, the test was performed using compound (9) instead of compound (1) or without using any drug. The results are shown in Table 4.

<Test Example 5: Evaluation of phytotoxicity for growth inhibition against cucumber>
The pot test evaluated the phytotoxicity of growth inhibition by foliar spray treatment. To a cucumber (variety: SHARP1) cultivated using a square plastic pot (6 cm × 6 cm), a compound (1) in the form of a wettable powder as in Formulation Example 1 was added with water at a predetermined concentration (1000 and 500 mg / day). L) was diluted and suspended and sprayed at a rate of 1000 L / ha. The sprayed leaves were air-dried and managed in a greenhouse. The second internode length of the cucumber was measured on the 11th day after the drug application. As a control, the test was conducted using compound (9) and metconazole instead of compound (1) or without using any drug. The results are shown in Table 5.

<Test Example 6: Antibacterial test against pathogenic bacteria>
In this test example, antibacterial properties against various phytopathogenic fungi were tested.

Compound (1) was dissolved in dimethyl sulfoxide and added to PDA medium (potato-dextrose-aggar medium) at around 60 ° C. After mixing well in an Erlenmeyer flask, it was poured into a petri dish and solidified to prepare a plate medium containing the compound (1) at a predetermined concentration (5 mg / L).

On the other hand, test bacteria (Pyrenophora graminea, Sclerotinia sclerotiorum, or Botrytis cinerea) previously cultured on a plate medium are punched out with a cork borer with a diameter of 4 mm. , Inoculated on the above-mentioned drug-containing plate medium. After inoculation, each fungus was cultured at an appropriate temperature for growth (for example, LIST OF CULTURES 1996 microorganisms 10th edition, refer to the literature of Foundation for Fermentation, etc.) for 1 to 14 days, and the growth of the fungus was measured by the fungus diameter. The growth degree of the bacteria obtained on the drug-containing plate medium was compared with the growth degree of the bacteria in the drug-free group, and the mycelial elongation suppression rate was determined by the following formula. In the following formula, R represents the hyphal elongation inhibition rate (%), dc represents the diameter of the fungus on the untreated plate, and dt represents the diameter of the fungus on the drug-treated plate.
R = 100 (dc−dt) / dc
As a result, the mycelial elongation suppression rate R was 80% or more for all the bacteria.

The present invention can be suitably used as an active ingredient of a control agent that can minimize plant phytotoxicity and can control plant diseases.

Claims (10)

1. An azole derivative represented by the following general formula (I) or (Ia):
   

   

   (In the general formulas (I) and (Ia), Y ¹ represents a halogen atom,
   R ¹ represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom,
   Y ² represents a halogen atom, m represents 0, 1 or 2, and when m is 2, a plurality of Y ² may be different from each other;
   A represents a nitrogen atom or a methine group.
   In the general formula (I), X represents —SH, —SR ² , —SO—R ² , —SO ₂ —R ² or —SO ₃ H. R ² represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a haloalkenyl group having 2 to 6 carbon atoms, an aryl group, or an arylalkyl A group (the alkyl part has 1 to 4 carbon atoms), and in the aryl group and arylalkyl group in R ² , at least one hydrogen atom in the aromatic ring is a halogen atom, and an alkyl group having 1 to 4 carbon atoms (cyclohexane). An alkyl group), or a haloalkyl group having 1 to 4 carbon atoms. )
2. The azole derivative according to claim 1, wherein Y ¹ is a chlorine atom.
3. The azole derivative according to claim 1 or 2, which is represented by the following general formula (Ic) or (Id).
   

   

   (In the general formula (Ic) and ^{(Id), R 1, Y} 1, Y 2 and A are the same as ^{R 1, Y 1,} Y ² and A in each of the above general formula (I) and (Ib) In general formula (Ic), X is the same as X in general formula (I) above.)
4. The azole derivative according to any one of claims 1 to 3, wherein A is a nitrogen atom.
5. The azole derivative according to any one of claims 1 to 4, which is represented by the following general formula (Ie):
   

   

   (In the general formula (Ic), Y ³ represents a hydrogen atom, a fluorine atom or a chlorine atom.)
6. An intermediate compound used for producing the azole derivative according to claim 1, wherein the intermediate compound is represented by the following general formula (II) or (IIa).
   

   

   (In the general formula (II) and ^{(IIa), R 1, Y} 2, m and A are the same as ^{R 1, Y} 2, m and A in each of the above general formula (I) and (Ia). General In the formula (II), X is the same as X in the general formula (I).)
7. The intermediate compound according to claim 6, wherein A is a nitrogen atom.
8. A process for producing the azole derivative according to any one of claims 1 to 5,
   An azole comprising a step of reacting an intermediate compound represented by the following general formula (II) or (IIa) with a halogen acid to obtain an azole derivative represented by the above general formula (I) or (Ia) A method for producing a derivative.
   

   

   (In General Formulas (II) and (IIa), R ¹ , Y ² , m and A are the same as R ¹ , Y ² , m and A in General Formula (I), respectively. General Formula (II) In the formula, X is the same as X in the general formula (I).)
9. 9. A step of reacting a compound represented by the following general formula (III) with sulfur to obtain a compound represented by the following general formula (IIa) or a compound represented by the following general formula (IIb). The manufacturing method as described in.
   

   

   (In general formula (III), R ¹ , Y ² , m and A are the same as R ¹ , Y ² , m and A in general formula (I), respectively.)
   

   

   (In the general formula (IIa), R ¹ , Y ² , m and A are the same as R ¹ , Y ² , m and A in the general formula (I), respectively.)
   

   

   (In the general formula (IIb), R ¹ , Y ² , m and A are the same as R ¹ , Y ² , m and A in the general formula (I), respectively.)
10. An agricultural or horticultural agent or an industrial material protective agent comprising the azole derivative according to any one of claims 1 to 5 as an active ingredient.