JP2013100238A - Triazole derivative, intermediate compound, method for producing triazole derivative, agricultural and horticultural chemical, and industrial material protective agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound capable of showing high control effect to a plant disease and reducing phytotoxicity generated therefrom.SOLUTION: This triazole derivative is represented by general formula (I). (In the general formula (I), Rrepresents a 1-4C alkyl group, Rrepresents a hydrogen atom, a halogen atom, a 1-4C alkyl group, a 1-4C haloalkyl group, a 1-4C alkoxy group or a 1-4C haloalkoxy group, and L represents a halogen atom).

Description

  The present invention relates to a novel triazole derivative, an intermediate compound thereof, and a method for producing a triazole derivative. The present invention also relates to an agricultural and horticultural agent and an industrial material protective agent containing the triazole derivative as an active ingredient.

  Conventionally, many azolylmethylcyclopentanol derivatives have been developed as active ingredients of plant disease control agents, such as 2- (halogenated hydrocarbon substitution) -5-benzyl-1-azolylmethylcyclopentanol. Derivatives (for example, see Patent Document 1) and 2- (hydrocarbon-substituted) -5-benzylidene-1-azolylmethylcyclopentanol derivatives (for example, see Patent Document 2) have been developed.

International Publication WO2011 / 077071 (released on June 16, 2011) Japanese Patent Laid-Open No. 2-237979 (published on September 20, 1990)

  Conventionally, there has been a demand for a plant disease control agent that has low toxicity to human livestock, is excellent in handling safety, and exhibits a high control effect on a wide range of plant diseases. In addition, there is a need for a disease control agent that can minimize adverse effects on the healthy growth of plants, that is, has low phytotoxicity.

  Therefore, the present invention has been made in view of the above problems, and an object of the present invention is to provide a compound that meets the above-mentioned needs.

  As a result of intensive studies by the present inventors for solving the above-mentioned problems, the present inventors have found that the triazole derivative represented by the following general formula (I) has excellent activity and reduced phytotoxicity to plants. To complete.

  That is, this invention is made | formed based on the novel knowledge which concerns, and includes the following inventions.

  A triazole derivative represented by the following general formula (I).

(In General Formula (I), R ¹ represents an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. Haloalkyl group, an alkoxy group having 1 to 4 carbon atoms, or a haloalkoxy group having 1 to 4 carbon atoms, and L represents a halogen atom.)
In the triazole derivative according to the present invention, R ² is preferably a halogen atom, a haloalkyl group having 1 to 2 carbon atoms, or a haloalkoxy group having 1 to 2 carbon atoms.

In the triazole derivative according to the present invention, R ² is preferably a halogen atom.

  In the triazole derivative according to the present invention, L is preferably a chlorine atom or a bromine atom.

  Furthermore, the present invention also includes an intermediate compound of the above-described triazole derivative, which is an intermediate compound represented by the following general formula (II).

(In the formula (II), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (I), ^{R 3} is good number of carbon atoms 1 to be a hydrogen atom be substituted 3 represents an alkyl group, a phenyl group or a naphthyl group.)
The present invention also includes an intermediate compound of the above-described triazole derivative, which is an intermediate compound represented by the following general formula (III).

(In the above formula (III), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (I).)
The present invention also includes an intermediate compound of the above-described triazole derivative, which is an intermediate compound represented by the following general formula (IV).

(In the formula (IV), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the above formula (I), ^{R 4} represents an alkyl group having 1 to 4 carbon atoms. )
The present invention also includes an intermediate compound of the above-described triazole derivative, which is an intermediate compound represented by the following general formula (V).

(In the formula (V), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the above formula (I), ^{R 4} represents an alkyl group having 1 to 4 carbon atoms. )
The present invention also includes an intermediate compound of the above-described triazole derivative, which is an intermediate compound represented by the following general formula (VI).

(In the formula (VI), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the above formula (I), ^{R 4} represents an alkyl group having 1 to 4 carbon atoms. )
Furthermore, the present invention provides a method for producing the above triazole derivative, wherein the substituted sulfonyloxy group represented by —OSO ₂ R ³ in the intermediate compound represented by the following general formula (II) is substituted with a halogen atom. A method for producing a triazole derivative including a step of obtaining a triazole derivative represented by the general formula (I) is also included.

(In the formula (II), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (I), ^{R 3} is good number of carbon atoms 1 to be a hydrogen atom be substituted 3 represents an alkyl group, a phenyl group or a naphthyl group.)
The present invention also provides a method for producing the triazole derivative, wherein the intermediate compound represented by the following general formula (II) is obtained by sulfonylating the intermediate compound represented by the following general formula (III): The manufacturing method of the triazole derivative containing this is also included.

(In the above formula (III), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (I).)

(In the formula (II), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (I), ^{R 3} is good number of carbon atoms 1 to be a hydrogen atom be substituted 3 represents an alkyl group, a phenyl group or a naphthyl group.)
The present invention also provides a method for producing the above triazole derivative, comprising the step of obtaining an intermediate compound represented by the following general formula (III) by reducing an intermediate compound represented by the following general formula (IV): And a method for producing a triazole derivative.

(In the formula (IV), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the above formula (I), ^{R 4} represents an alkyl group having 1 to 4 carbon atoms. )

(In the above formula (III), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (I).)
The present invention also provides a method for producing the triazole derivative, wherein the intermediate compound represented by the following general formula (V) obtained by oxirane conversion of the intermediate compound represented by the following general formula (VI): A method for producing a triazole derivative including a step of obtaining an intermediate compound represented by the following general formula (IV) by reacting with a compound represented by the formula (IX) is also included.

(In the formula (VI), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the above formula (I), ^{R 4} represents an alkyl group having 1 to 4 carbon atoms. )

(In the formula (V), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the above formula (I), ^{R 4} is identical to ^{R 4} in the formula (VI). )

(In the above formula (IX), M represents a hydrogen atom or an alkali metal.)

(In the formula (IV), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the above formula (I), ^{R 4} is identical to ^{R 4} in the formula (VI). )
Moreover, this invention also includes the agricultural and horticultural chemical | medical agent or industrial material protecting agent characterized by containing the above-mentioned triazole derivative as an active ingredient.

  The azole derivative according to the present invention has an excellent bactericidal action against many fungi 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.

  One embodiment of the triazole derivative according to the present invention will be described.

[1. Triazole derivative)
The triazole derivative according to the present invention is a triazole derivative represented by the following general formula (I) (hereinafter referred to as triazole derivative (1)).

In general formula (I), R ¹ represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, 1-methylpropyl group, 2-methylpropyl group, n-butyl group, and 1,1- A dimethylethyl group etc. are mentioned. Of these, an alkyl group having 1 to 3 carbon atoms is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.

R ² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a haloalkoxy group having 1 to 4 carbon atoms. Represents. Among these, a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a haloalkoxy group having 1 to 3 carbon atoms. A halogen atom, a haloalkyl group having 1 to 2 carbon atoms, and a haloalkoxy group having 1 to 2 carbon atoms are more preferable, and a halogen atom is particularly preferable.

Examples of the alkyl group having 1 to 4 carbon atoms in R ² include the alkyl groups mentioned as examples of the organic group represented by R ¹ .

  Examples of the haloalkyl group having 1 to 4 carbon atoms include a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a 2-chloroethyl group, a 1-chloroethyl group, a 2,2-dichloroethyl group, and 1,2-dichloroethyl. Group, 2,2,2-trichloroethyl group, 3-chloropropyl group, 2,3-dichloropropyl group, 1-chloro-1-methylethyl group, 2-chloro-1-methylethyl group, 2-chloropropyl Group, 4-chlorobutyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, 1-fluoroethyl group, 2,2-difluoroethyl group, 1,2-difluoroethyl group, 2, 2,2-trifluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 3-fluoropropyl group, 2,3-difluoropropyl Pyl group, 1-fluoro-1-methylethyl group, 2-fluoro-1-methylethyl group, 2-fluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoro Propyl group, 2,2,3,3,3-pentafluoropropyl group, 4-fluorobutyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, 2-bromoethyl group, 1-bromoethyl group, 2,2- Dibromoethyl group, 1,2-dibromoethyl group, 2,2,2-tribromoethyl group, 3-bromopropyl group, 2,3-dibromopropyl group, 1-bromo-1-methylethyl group, 2-bromo -1-methylethyl group, 2-bromopropyl group, 4-bromobutyl group, iodomethyl group, diiodomethyl group, 2-iodoethyl group, 1-iodoethyl group, 2,2-di Dodoethyl group, 1,2-diiodoethyl group, 2,2,2-triiodoethyl group, 3-iodopropyl group, 2,3-diiodopropyl group, 1-iodo-1-methylethyl group, 2-iodo- Examples include 1-methylethyl group, 2-iodopropyl group, and 4-iodobutyl group. Of these, a haloalkyl group having 1 to 2 carbon atoms is preferable, and a trifluoromethyl group, 1,1,2,2,2-pentafluoroethyl group, a chloromethyl group, a trichloromethyl group, and a bromomethyl group are more preferable.

  Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, and an n-propoxy group.

  Examples of the haloalkoxy group having 1 to 4 carbon atoms include a trifluoromethoxy group, a difluoromethoxy group, a 1,1,2,2,2-pentafluoroethoxy group, and a 2,2,2-trifluoroethoxy group. Etc.

Examples of the halogen atom in R ² include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom and a chlorine atom are preferable, and a chlorine atom is particularly preferable.

Not particularly limited bonding position of R ^2, but is preferably bonded to 4-position of the benzyl group.

  L represents a halogen atom. Specific examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom, a chlorine atom and a bromine atom are more preferable, and a chlorine atom is particularly preferable.

  Examples of particularly preferred triazole derivatives (I) include triazole derivatives represented by the following formula (I-1).

  In general formula (I), the bond with the benzene ring indicated by the wavy line in the carbon atom having a double bond means that the E configuration and the Z configuration are not distinguished from each other with respect to the configuration in the double bond. Yes. That is, the triazole derivative (I) in the present embodiment may be any of E isomer and Z isomer, and may also be a mixture of E isomer and Z isomer.

  Further, the triazole derivative (I) includes geometric isomers in which a hydroxy group bonded to a cyclopentane ring and a methyl halide group bonded to a cyclopentane ring are cis-type and trans-type. Can exist. Therefore, the triazole derivative (I) in the present embodiment includes both those containing any one of such geometric isomers and those containing each geometric isomer in an arbitrary ratio.

  The triazole derivative (I) can be produced, for example, by the production method described below, but is not limited to the compound produced by this production method.

[2. Method for producing triazole derivative]
The triazole derivative (I) can be produced from a compound obtained by a known technique according to the following overall scheme.
(Overall scheme)

  Hereinafter, each step will be described.

(Step 1: Alkylation)
In Step 1, compound (VII) is obtained by alkylating compound (VIII) (see reaction formula (1)).
(Reaction Formula (1))

R ⁴ in the compound (VIII) represents an alkyl group having 1 to 4 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, 1-methylethyl group, n-butyl group, Examples include 2-methylpropyl group, 1-methylpropyl group, and 2,2-dimethylethyl group. Especially, a C1-C3 alkyl group is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is further more preferable.

R ¹ in the compound (VII) has the same meaning as R ¹ described above. More specifically, it is the same group as R ¹ in the triazole derivative (I).

Examples of the method of alkylating compound (VIII) include a method of reacting compound (VIII) with an alkyl halide represented by the general formula: R ¹ -L ′ in a solvent in the presence of a base. Here, L ′ represents a halogen atom, for example, a chlorine atom, a bromine atom or an iodine atom.

  Bases used in the reaction include alkali metal carbonates such as sodium carbonate and potassium carbonate, metal hydrides such as sodium hydride and potassium hydride, and alkali metals such as sodium methoxide, sodium ethoxide and potassium t-butoxide. The alkoxide of etc. can be mentioned.

  The solvent is not particularly limited as long as it is an aprotic solvent, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ethers such as diethyl ether, tetrahydrofuran and dioxane, and N, N-dimethylformamide, Examples include amides such as N, N-dimethylacetamide and N-methyl-2-pyrrolidinone.

  Examples of the alkyl halide include methyl iodide, methyl bromide, ethyl iodide, ethyl bromide and isopropyl iodide. Among them, methyl iodide and methyl bromide are preferable.

  The amount of the alkyl halide is, for example, 0.5 to 2.0 times mol, preferably 0.9 to 1.5 times mol for the compound (VIII).

  The reaction temperature and reaction time can be appropriately set depending on the type of solvent, alkyl halide and base. The reaction temperature is, for example, -20 ° C to 100 ° C, preferably 0 ° C to 50 ° C. The reaction time is, for example, 0.5 hours to several days, and preferably 1 hour to 24 hours.

  Compound (VIII) can be easily synthesized from adipic acid diesters using a known reaction, or commercially available 2-oxocyclopentanecarboxylic acid esters may be used.

(Process 2: benzylidene conversion)
In step 2, compound (VII) is benzylidene to obtain compound (VI) (see reaction formula (2)).
(Reaction Formula (2))

Examples of the method for benzylidation of compound (VII) include a method in which compound (VII) is reacted with a substituted or unsubstituted benzaldehyde in a solvent in the presence of basicity. In the compound (VI), R ² has the same meaning as R ² described above. More specifically, it is the same group as R ² in the triazole derivative (I).

  Examples of the substituted or unsubstituted benzaldehyde include chlorobenzaldehyde, fluorobenzaldehyde, bromobenzaldehyde, trifluoromethoxybenzaldehyde, trifluoromethylbenzaldehyde, and methylbenzaldehyde. Among them, p-chlorobenzaldehyde and p-fluorobenzaldehyde are included. preferable.

  Examples of the base used in the reaction include sodium methoxide, sodium ethoxide, alkali metal alkoxides such as sodium t-butoxide and potassium t-butoxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydride, hydrogen Examples thereof include metal hydrides such as potassium hydroxide, organic bases such as pyridine, triethylamine and 4-dimethylaminopyridine, and alkali metal hydroxides such as sodium hydroxide.

  The solvent used in the reaction is not particularly limited. For example, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ethers such as diethyl ether, tetrahydrofuran and dioxane, N, N-dimethylformamide, N, N- Examples thereof include amides such as dimethylacetamide and N-methyl-2-pyrrolidinone, and alcohols such as methanol, ethanol and isopropanol.

  The reaction temperature and reaction time can be appropriately set depending on the kind of the solvent, compound (VII) and base. The reaction temperature is, for example, -20 ° C to 200 ° C, preferably 0 ° C to 100 ° C. The reaction time is, for example, 0.5 hours to several days, and preferably 1 hour to 24 hours.

(Step 3: Oxiraneization)
In step 3, compound (VI) is oxiraneated to give compound (V) (see reaction formula (3)).
(Reaction Formula (3))

  Examples of the method for oxirane-izing compound (VI) include a method in which compound (VI) is reacted with a sulfur ylide such as dimethylsulfonium methylide in a solvent.

  The amount of the sulfonium methylide used in the reaction is, for example, 0.5 to 5 times mol, preferably 0.8 to 2 times mol for the compound (VI).

  The solvent used in the reaction is not particularly limited, and examples thereof include amides such as dimethyl sulfoxide, N-methylpyrrolidone and N, N-dimethylformamide, ethers such as tetrahydrofuran and dioxane, and mixed solvents thereof. it can.

  The reaction temperature and reaction time can be appropriately set depending on the type of the solvent, compound (VI), and sulfonium salt. The reaction temperature is, for example, −100 ° C. to 200 ° C., and preferably −50 ° C. to 150 ° C. The reaction time is, for example, 0.1 hour to several days, and preferably 0.5 hour to 2 days.

  The sulfonium methylides used in the reaction can be produced by reacting a sulfonium salt (for example, trimethylsulfonium iodide or trimethylsulfonium bromide) with a base in a solvent.

  The base used for the production of sulfonium methylides is not particularly limited, and examples thereof include metal hydride compounds such as sodium hydride and alkali metal such as sodium methoxide, sodium ethoxide, sodium t-butoxide and potassium t-butoxide. An alkoxide etc. can be mentioned.

(Step 4: Azolation)
In step 4, compound (IV) is obtained by reacting compound (V) with a 1,2,4-triazole compound (compound (IX)) (see reaction formula (4)).
(Reaction Formula (4))

  M in the compound (IX) represents a hydrogen atom or an alkali metal. As the alkali metal, sodium and potassium are preferable.

  Compound (IV) is obtained by mixing compound (V) and compound (IX) in a solvent, so that carbon between the carbon atom constituting the oxirane ring in compound (V) and the nitrogen atom of compound (IX) is carbon. -Manufactured by the formation of nitrogen bonds.

  The solvent is not particularly limited, and examples thereof include amides such as N, N-dimethylacetamide, N-methylpyrrolidone and N, N-dimethylformamide, and dimethyl sulfoxide.

  The usage-amount of compound (IX) with respect to compound (V) is 0.5-10 times mole, for example, and is 0.8-5 times mole suitably.

  Moreover, you may add a base if desired. Examples of the base include alkali alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide and potassium t-butoxide, and potassium carbonate.

  The usage-amount of the base with respect to compound (IX) is 0-5 times mole (however, 0 is excluded), for example, and it is more preferable that it is 0.5-2 times mole.

  The reaction temperature can be appropriately set depending on the solvent, base and the like. The reaction temperature is, for example, 0 ° C to 250 ° C, preferably 10 ° C to 150 ° C. Moreover, reaction time can be suitably set with a solvent, a base, etc. The reaction time is, for example, 0.1 hour to several days, preferably 0.5 hour to 2 days.

(Step 5: Reduction reaction)
In step 5, compound (III) is obtained by reducing compound (IV) (see reaction formula (5)).
(Reaction Formula (5))

  Examples of the reducing agent for reducing compound (IV) include a hydride-type reducing agent. Examples of the hydride-type reducing agent include sodium borohydride, calcium borohydride, lithium borohydride, lithium aluminum hydride, and the like. Of these, sodium borohydride and calcium borohydride are preferably used. In addition, the reducing agent can be prepared in the system as necessary.

  The amount of the reducing agent is, for example, 0.2 to 50 times mol, preferably 0.5 to 20 times mol with respect to compound (IV).

  Examples of the solvent include alcohols such as methanol, ethanol and isopropanol, ethers such as diethyl ether, tetrahydrofuran and dioxane, and a mixed solvent thereof. Of these, methanol, ethanol and tetrahydrofuran are preferably used.

  The reaction temperature and reaction time can be appropriately set depending on the solvent used, the type of reducing agent, the presence or absence of additives, and the like. For example, the reaction temperature when sodium borohydride is used as the reducing agent is preferably −30 ° C. to 70 ° C., and more preferably −20 ° C. to 50 ° C. The reaction time is preferably 0.5 hours to 24 hours, and more preferably 1 hour to 8 hours.

(Step 6: Sulfonylation)
In Step 6, compound (II) having a substituted sulfonyloxy group is obtained by reacting compound (III) with a substituted sulfonyl chloride represented by the general formula: R ³ SO ₂ Cl (compound (X)) ( Reaction formula (6) reference).
(Reaction Formula (6))

R ³ in the compound (X) represents an alkyl group having 1 to 3 carbon atoms, a phenyl group or a naphthyl group in which a hydrogen atom may be substituted. Examples of the alkyl group having 1 to 3 carbon atoms in which a hydrogen atom may be substituted include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a trifluoromethyl group. Examples of the phenyl group and naphthyl group in which a hydrogen atom may be substituted include a 4-methylphenyl group, a 2-nitrophenyl group, and a 5-dimethylaminonaphthyl group. Of these, methyl group and 4-methylphenyl group are more preferred as R ³ .

  The usage-amount of compound (X) with respect to compound (III) is 0.5-10 times mole, for example, Preferably it is 0.8-5 times mole.

  Although the reaction may proceed without adding a base, it is preferable to add a base in order to remove generated hydrogen chloride. In that case, the usage-amount of the base with respect to compound (III) is 0-5 times mole (however, 0 is excluded), for example, Preferably it is 0.5-3 times mole. The base is not particularly limited, and examples thereof include alkali metal hydrogen compounds such as sodium hydride, potassium hydride and lithium hydride, and organic amines such as triethylamine, pyridine, 4-dimethylaminopyridine and N, N-dimethylaniline. Etc.

  The solvent is not particularly limited, and for example, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as methylene chloride and chloroform, and ethers such as tetrahydrofuran and diethyl ether can be used.

  The reaction temperature can be appropriately set depending on the solvent and base used. The reaction temperature is, for example, −50 ° C. to 200 ° C., and preferably −20 ° C. to 150 ° C. Moreover, reaction time can be suitably set with the solvent, base, etc. which are used. The reaction time is, for example, 0.1 hour to several days, and preferably 0.5 hour to 1 day.

(Step 7: Halogenation)
In step 7, compound (I) (triazole derivative (I)) is obtained by substituting the substituted sulfonyloxy group in compound (II) with a halogen atom (see reaction formula (7)).
(Reaction Formula (7))

  Examples of the method for substituting the substituted sulfonyloxy group with a halogen atom include a method for substituting with a halogenated salt in a solvent. The reaction in this method is performed, for example, by mixing compound (II) and a halide salt in a solvent.

  Examples of the halogenated salt include potassium fluoride, cesium fluoride, lithium chloride, potassium chloride, lithium bromide, magnesium bromide and sodium iodide. Of these, lithium chloride and lithium bromide are preferable.

  The usage-amount of the halogenated salt with respect to compound (II) is 0.1-100 times mole, for example, Preferably it is 0.8-20 times mole. Moreover, as reaction temperature, it is 0-250 degreeC, for example, It is room temperature-200 degreeC suitably. The reaction time is, for example, 0.1 hour to several days, and preferably 0.2 hour to 2 days.

  In addition, the compound (VI), the compound (V), the compound (IV), the compound (III) and the compound (II) obtained in the above-mentioned steps 2, 3, 4, 5 and 6 are the triazole derivative (I). Since the intermediate compound is suitably used for the production of the triazole derivative (I), these intermediate compounds are also included in the category of the present invention.

  Furthermore, since the triazole derivative (I) can be suitably produced by including at least any one of the above-mentioned steps 3, 4, 5, 6, and 7, at least steps 3, 4, 5, 6, and 7 are included. A method for producing the triazole derivative (I) including any one step is also included in the category of the present invention.

[3. (Agricultural and horticultural chemicals)
Since triazole derivative (I) has 1,2,4-triazolyl, it forms an acid addition salt of an inorganic acid and an organic acid, or a metal complex. 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 triazole derivative (I) exhibits 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 black rot (Helminthosporium sigmoideun), rice seedling disease (Gibberella fujikuroi), rice seedling blight (Pythium aphanidermatum), apple powdery mildew (Podosphaera leucotricha), apple black astronomy inaequalis), apple morinia disease (Monilinia mali), 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 scab (Venturia nashicola), grape powdery mildew (Uncinula necator), grape downy 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 spot (Pyrenophora graminea), barley cloud sp ), Wheat powdery mildew (Erysiphe graminis f. Sp tritici), wheat red rust (Puccinia recondita), wheat yellow rust (Puccinia striiformis), wheat eye spot (Pseudocercosporella herpotrichoides), wheat red mold (Fusarium graminearum, Microdochium) nivale), wheat blight (Phaeosphaeria nodorum), wheat leaf blight (Septoria tritici), cucumber powdery mildew (Sphaerotheca fuliginea), cucumber anthracnose (Colletotrichum lagenarium), cucumber downy mildew (Pseudoperonospora cubensis), Cucumber gray plague (Phytophthora capsici), tomato powdery mildew (Erysiphe cichoracearum), tomato ring 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 (Ustillaga maydis), ash of fruit tree Star disease (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 oxysporum f.sp.niveum), cucumber vine (Fusarim oxysporum f.sp.cucumerinum), radish yellow (Fusarium oxysporum f. sp. raphani), tobacco red star disease (Alternaria longipes), potato summer blight (Alternaria solani), soybean brown spot disease (Septoria glycines), soybean purple spot disease (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 The triazole derivative (I) has an effect of increasing the yield by adjusting its growth and an effect of improving its quality, etc., for 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 triazole derivative (I) exhibits 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.), Micrococcus sp., And other fiber-degrading microorganisms such as Aspergillus sp., Penicillium (Penicillium sp.), Ketomium (Chaetomium sp.), Myrothecium sp., Curvularia sp. ), Gliomastix, (Gliomastix sp.), Mennoniella sp., Sarcopodium, Stschybotrys sp., Stemphylium sp., Zygorhynchus sp. , Bacillus sp., Staphylococcus sp., And other wood-modifying fungi Tyromyces palustris, Coriolus versicolor, Aspergillus sp., Penicillium sp. (Rhizopus sp.), Aureobasidium sp., Glyocladium Gliocladum sp.), Cladosporium sp., Ketomium (Chaetomium sp.), Trichoderma sp., Etc., Aspergillus sp., Penicillium sp. Chaetomium sp., Cladosporium sp., Mucor sp., Paecilomyces sp., Pilobus sp., Pullularia sp., Trichosporon sp., Trichosporon sp. (Tricothecium sp.), Etc. Aspergillus sp., Penicillium sp., Rhizopus sp., Trichoderma sp., Chaetomium sp., Milotesium (Myrothecium sp.), Streptomyces sp., Pseudomonas sp., Bacillus Bacillus sp.), Micrococcus sp., Serratia sp., Margarinomyces sp., Monascus sp., Etc., Aspergillus sp., Penicillium (Penicillium sp.), Cladosporium sp., Aureobasidium sp., Gliocladium sp., Botryodiplodia sp., Macrosporium sp.), Monilia sp., Forma (Phoma sp.), Pullularia (Pullularia sp.), Sporotrichum sp., Trichoderma sp., Bacillus (. bacillus sp.), Proteus ( Proteus sp.), Pseudomonas sp., And Serratia sp.

(4) Formulation In order to apply the triazole derivative (I) as an active ingredient of an agricultural and 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 other preparations. It is mixed with adjuvants and formulated into various forms such as powders, wettable powders, granules and emulsions.

  These preparations are formulated so that the triazole derivative (I) is contained as an active ingredient in an amount of 0.1 to 95% by weight, preferably 0.5 to 90% by weight, more preferably 2 to 80% by weight.

  For example, talc, kaolin, bennite, diatomaceous earth, white carbon, and clay are listed 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 triazole derivative (I) when used after dilution is preferably in the range of 0.001 to 1.0%.

  Moreover, the usage-amount of a triazole derivative (I) is 20-5000g per agricultural / horticultural land 1ha, such as a field, a field, an orchard, and a greenhouse, More preferably, it is 50-2000g. 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 triazole derivative (I) should be used in combination with other active ingredients such as fungicides, insecticides, acaricides and herbicides as exemplified below to enhance performance as agricultural and horticultural agents. You can also.

<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, flusulfamide , Flutolanil, flutriafol, Olpetet, Focetyl-aluminum, Fuberidazole, Furaxil, Frametopyr, Fluopicolide, Fluopyram, Guazatine, Hexachlorobenzene, Hexaconazole, Himexazole, Imazalil, Imibenconazole, Iminocazine, Ipconazole, Iprobenfos, Iprodithiol, Isoprovalil , Kasugamycin, copper preparations such as copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper, crezoxime methyl, manco kappa, 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, Torcrofos-Methyl, Tolylfluanid, Triadimefone, Triadimenol, Triazoxide, Tricyclazole, Tridemorph, Trifloxystrobin, Triflumizole, Trifolin, Triticonazole, Validamycin, Vinclozoline, Zineb, ziram, zoxamide, amisulbrom, sedaxane, flutianil, varifenal, amethoctrazine, dimoxystrobin, metolaphenone, hydroxyisoxazole and metasulfocarb.

<Insecticide / acaricide / nematicide>
Abamectin, Acephate, Acrinathrin, Alanicarb, Aldicarb, Alletrin, Amitraz, Avermectin, Azadirachtin, Azamethyphos, Azinphos-ethyl, Azinphos-methyl, Azocycline, Bacillus filmus, Bacillus subtilis, Bacillus thuringibulbbenthulbenbencarben , Benzoxymate, Bifenazite, Bifenthrin, Bioarethrin, Bioresmethrin, Bistriflurone, Buprofezin, Butocaboxin, Butoxycarboxyne, Kazusafos, Carbaryl, Carbofuran, Carbosulfan, Cartap, CGA50439, Chlordein, Chloretifol, Chlorfenapyr 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, Dicophor, Dicrotophos, Dicyclanil, Diflubenzuron, Dimethoate, Dimethylvinphos, Dinobutone, 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, flufenoxuron, flumethrin, fulvalinate, fulvendiamide, 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, phosfamidone, foxim, pirimicarb, pirimiphos methyl, profenofos, propoxur, prothiophos, pymetrozine, pyracrofos, pyrethrin, pyridaben, pyridalyl, pyrimidifene, pyriproxy Fen, Pyrifluquinazone, Pyriprole, Quinarfos, Shirafu Ofen, Spinosad, Spirodiclofen, Spiromesifen, Spirotetramat, Sulfamide, Sulfotep, SZI-121, Tebufenozide, Tebufenpyrad, Tebupyrimfos, Teflubenzuron, Tefluthrin, Temefos, Terbufos, Tetrachlorbinfos, Thiacloprio, Thiamethioxam Fanox, thiometon, tolfenpyrad, tralomethrin, tralopyril, triazamate, triazophos, trichlorphone, triflumuron, bamidithione, 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.

  The industrial material protective agent containing the triazole derivative (I) as an active ingredient may contain various components in addition to the triazole derivative (I). The industrial material protective agent containing the triazole derivative (I) as an active ingredient can be used by being dissolved or dispersed in a suitable liquid carrier, or mixed with a solid carrier. The industrial material protective agent containing the triazole derivative (I) as an active ingredient may further contain an emulsifier, a dispersant, a spreading agent, a penetrating agent, a wetting agent, a stabilizer and the like, if necessary. Examples of the dosage form of the industrial material protective agent containing the triazole derivative (I) as an active ingredient include wettable powders, powders, granules, tablets, pastes, suspensions and sprays. The industrial material protective agent containing the triazole derivative (I) as an active ingredient may contain other fungicides, insecticides, deterioration inhibitors and the like.

  The liquid carrier is not particularly limited as long as it does not react with the active ingredient. Examples of the liquid carrier include water, alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol and cellosolve), ketones (eg, acetone and methyl ethyl ketone), ethers (eg, dimethyl ether, diethyl ether, dioxane and tetrahydrofuran). Etc.), aromatic hydrocarbons (eg benzene, toluene, xylene and methylnaphthalene), aliphatic hydrocarbons (eg gasoline, kerosene, kerosene, machine oil and fuel oil), acid amides (eg dimethylformamide) And N-methylpyrrolidone) halogenated hydrocarbons (eg chloroform and carbon tetrachloride), esters (eg ethyl acetate and glycerin esters of fatty acids), nitriles (eg aceto Nitrile, 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, diatomaceous earth, 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 triazole derivative (I) is contained in the preparation as an active ingredient, the content ratio varies depending on the dosage form and purpose of use, but is 0.1 to 99.9% by weight with respect to the total amount of the preparation. Good. In actual use, the treatment concentration is adjusted by adding a solvent, a diluent, an extender, etc., as appropriate, for example, 0.005 to 5% by weight, preferably 0.01 to 1% by weight. It is preferable to do this.

  As described above, the triazole derivative (I) exhibits an excellent bactericidal action against many bacteria that cause plant diseases. That is, an agricultural and horticultural disease control agent containing the triazole derivative (I) as an active ingredient 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 horticultural disease control agent can be realized.

  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 1: Synthesis of methyl 1-methyl-2-oxo-cyclopentanecarboxylate]
51.83 g of anhydrous potassium carbonate was added to 170 ml of molecular sieve 4A dry acetone, and 35.54 g of 2-methoxycarbonylcyclopentanone and 39.0 g of methyl iodide were successively added with stirring. Since heat was generated during the reaction, the reaction solution was cooled with ice water. After the heat generation stopped, the temperature was returned to room temperature and stirred overnight. The reaction solution was filtered, and the residue was washed with acetone. The filtrate was concentrated under reduced pressure, and water and diethyl ether were added to the residue for partitioning. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, and dried over anhydrous sodium sulfate. The organic layer was filtered and washed, and then the solvent was distilled off under reduced pressure to give a crude reaction product of methyl 1-methyl-2-oxo-cyclopentanecarboxylate (hereinafter referred to as compound (7)) as a pale yellow liquid. As a result, 35.02 g (yield 89.7%) was obtained. This crude reaction product was purified by simple distillation to obtain 26.86 g of colorless liquid (yield 68.8%).
97-98 ° C / 1.4kPa
¹ H-NMR (400 MHz, CDCl ₃ , δ ppm):
1.32 (s, 3H), 1.83-2.11 (m, 3H), 2.27-2.56 (m, 3H), 3.71 (s, 3H)
[Production Example 2: Synthesis 1 of methyl 3- (4-chlorobenzylidene) -1-methyl-2-oxo-cyclopentanecarboxylate]
10.0 g of the compound (7) obtained in Production Example 1 and 9.9 g of p-chlorobenzaldehyde were dissolved in 100 ml of methanol, cooled to 0 ° C. with ice water, and 13.60 g of 28% sodium methoxide was added. After stirring at the same temperature for 45 minutes, a part of the reaction solution was distilled off under reduced pressure, and cold water was added to the residue, followed by extraction with ethyl acetate. The organic layer was washed successively with water and saturated brine, and then dried over anhydrous sodium sulfate. The organic layer was filtered and washed, and then the solvent was distilled off under reduced pressure to remove methyl 3- (4-chlorobenzylidene) -1-methyl-2-oxo-cyclopentanecarboxylate (hereinafter referred to as compound (6)). Was obtained as a yellow oil. The crude reaction product was purified by silica gel chromatography to obtain 11.50 g (yield 64.4%) of compound (6).
¹ H-NMR (400 MHz, CDCl ₃ , δ ppm):
1.43 (s, 3H), 1.87 (ddd, 1H, J = 7.6, 8.4, 13.1Hz), 2.65 (ddd, 1H, J = 4.7, 8.5, 13.2Hz), 2.89-3.08 (m, 2H), 3.72 ( s, 3H), 7.39 (dd, 2H, J = 8.6Hz), 7.42 (t-like, 1H, J = 2.7Hz), 7.48 (d, 2H, J = 8.5Hz)
[Production Example 3: Synthesis 2 of methyl 3- (4-chlorobenzylidene) -1-methyl-2-oxo-cyclopentanecarboxylate 2]
The same reaction as in Production Example 2 was performed using potassium carbonate instead of sodium methoxide to obtain compound (6). The yield is shown in Table 1.

[Production Example 4: Synthesis of methyl 3- (4-chlorobenzylidene) -2-hydroxy-1-methyl-2- [1,2,4] triazol-1-ylmethylcyclopentanecarboxylate]
(1) Synthesis of methyl 7- (4-chlorobenzylidene) -4-methyl-1-oxaspiro [2.4] cyclopentanecarboxylate 0.260 g of 60% sodium hydride was taken and washed once with hexane. To this, 5.0 ml of anhydrous DMSO was added, and the temperature was raised to 80 ° C., followed by stirring at 80 ° C. for 3 minutes. The temperature was returned to room temperature, 15 ml of anhydrous THF was added when the internal temperature was 70 ° C, and the mixture was cooled to -10 ° C using a dry ice-acetone solution. Next, 1.15 g of trimethylsulfonium iodide dissolved in 5 ml of anhydrous DMSO was added dropwise over 3 minutes, and the mixture was stirred at −10 ° C. for 15 minutes. To this solution, 1.40 g of the compound (6) obtained in Production Example 2 dissolved in 4 ml of anhydrous THF was added dropwise. After dropping, the mixture was stirred at room temperature for 3.5 hours. After THF was distilled off, water was added to the residue and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and then dried over anhydrous sodium sulfate. The organic layer was filtered and washed, and then the solvent was distilled off under reduced pressure to obtain methyl 7- (4-chlorobenzylidene) -4-methyl-1-oxaspiro [2.4] cyclopentanecarboxylate (hereinafter referred to as compound (5). )) Was obtained as an orange-colored product.

(2) Synthesis of methyl 3- (4-chlorobenzylidene) -2-hydroxy-1-methyl-2- [1,2,4] triazol-1-ylmethylcyclopentanecarboxylate Crude reaction product of compound (5) Was dissolved in 3 ml of DMF, and this was added to a solution of 6 ml of DMF to which 0.444 g of 1,2,4-triazole and 1.74 g of potassium carbonate were added. After the addition, the mixture was stirred at 90 ° C. for 2 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and methyl 3- (4-chlorobenzylidene) -2-hydroxy-1-methyl-2- [1,2,4] triazol-1-ylmethylcyclopentanecarboxylate (hereinafter referred to as compound) 0.881 g of the crude reaction product of (4) was obtained as a dark brown rod-like product. The crude reaction product was purified by silica gel chromatography to obtain 0.200 g of compound (4) as a mixture of two isomers (yield 11.0% from compound (6)).
Isomeric ratio: Isomer-I: Isomer-II = 81: 19
Furthermore, the reaction similar to the above was separately performed using 32.6 g of compound (6). As a result, a total of 4.2 g of the compound (4) was obtained together with the compound (4) obtained above. Ethyl acetate was added to the obtained compound (4) and heated to 70 ° C., and then the solid was dispersed and ground using an ultrasonic cleaner. Next, hexane was added, and the mixture was heated again to 70 ° C., and then left overnight at room temperature. The solid was filtered through a G4 glass filter, washed with a mixed solvent of ethyl acetate / hexane, and then dried with hot air at 50 ° C. to obtain 2.80 g of a white powder.
Melting point: 152.9 ° C
Isomer ratio Isomer-I: Isomer-II = 81.5: 18.5
Isomer-I:
¹ H-NMR (400 MHz, CDCl ₃ , δ ppm)
1.24 (s, 3H), 1.84-1.92 (m, 1H), 2.40-2.50 (m, 1H), 2.61-2.74 (m, 2H), 3.71 (s, 3H), 4.28 (d, 1H, J = 14.1 Hz), 4.33 (d, 1H, J = 14.3Hz), 5.89 (t-like, 1H, J = 2.5Hz), 7.11 (d, 2H, J = 8.6Hz), 7.26 (d, 2H, J = 8.6 Hz) 7.86 (s, 1H),
8.09 (s, 1H)
Isomer-II:
¹ H-NMR (400 MHz, CDCl ₃ , δ ppm)
1.42 (s, 3H), 1.78-1.92 (m, 1H), 2.40-2.50 (m, 1H), 2.61-2.74 (m, 2H), 3.63 or 3.70 (s, 3H), 4.33 (d, 1H, J = 14.1Hz), 4.49 (d, 1H, J = 14.0Hz), 6.00 (t-like, 1H, J = 2.5Hz), 7.14 (d, 2H, J = 8.8Hz), 7.26 (d, 2H, J = 8.8Hz) 7.81 (s, 1H), 8.29 (s, 1H)
[Production Example 5: Synthesis of 5- (4-chlorobenzylidene) -2-hydroxymethyl-2-methyl-1- [1,2,4] triazol-1-ylmethylcyclopentanol]
To 1.873 g of the compound (4) obtained in Production Example 4, 45 ml of THF and 9 ml of methanol were added and dissolved, followed by cooling with ice water. Subsequently, 719 mg of calcium chloride and 495 mg of sodium borohydride were sequentially added, and the mixture was stirred at 1.5 ° C. for 3 hours. Since compound (4) remained by TLC analysis, 701 mg of calcium chloride and 503 mg of sodium borohydride were further added. After stirring at the same temperature for 40 minutes, the mixture was returned to room temperature and stirred overnight. The reaction solution was poured into water and extracted with chloroform. The organic layer was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The organic layer was filtered and washed, and then the solvent was distilled off under reduced pressure to give 5- (4-chlorobenzylidene) -2-hydroxymethyl-2-methyl-1- [1,2,4] triazol-1-yl. 1.78 g of a crude reaction product of methylcyclopentanol (hereinafter referred to as compound (3)) was obtained as a white solid. To this solid, 15 ml of chloroform and 1.5 ml of ethyl acetate were added, dispersed using an ultrasonic cleaner, and cooled in a refrigerator for 1 hour. The solid was filtered through a G4 glass filter, washed with a mixed solvent of chloroform / ethyl acetate, and then dried with hot air at 50 ° C. to obtain 1.313 g of compound (3) as a white powder solid (yield 76). %).
Melting point: 194.9 ° C
Isomeric ratio: Isomer-I: Isomer-II = 93.8: 6.2 (based on methyl group ratio in NMR)
¹ H-NMR (400 MHz, CDCl ₃ , δ ppm):
1.05 (s, 3H), 1.60-1.65 (m, 1H), 1.77-1.86 (m, 1H), 2.17 (t, 1H, J = 5.1Hz), 2.66-2.72 (m, 2H), 3.60 (s, 1H), 3.77 (dd, 1H, J = 5.3, 10.9Hz), 3.85 (dd, 1H, J = 5.3, 10.9Hz), 4.40 (d, 1H, J = 14.1Hz), 4.57 (d, 1H, J = 14.1Hz), 5.65 (t, 1H, J = 2.6Hz), 7.07 (d, 2H, J = 8.5Hz), 7.24 (d, 2H, J = 8.6Hz) 7.86 (s, 1H), 8.13 (s , 1H)
[Production Example 6: Synthesis 1 of toluene-4-sulfonic acid 3- (4-chlorobenzylidene) -2-hydroxy-1-methyl-2- [1,2,4] triazol-1-ylmethylcyclopentylmethyl ester]
Under an argon stream, 60 mg of 60% sodium hydride was taken and washed once with hexane. To this, 2 ml of dehydrated THF was added and suspended. Next, at room temperature, 0.25 g of a compound (3) containing Isomer-I as a main component suspended in 4 ml of THF (hereinafter referred to as compound (3a)) was added while paying attention to foaming, followed by stirring for 30 minutes. This solution was cooled with ice water, 0.21 g of p-toluenesulfonyl chloride dissolved in 2 ml of THF was added, and the mixture was stirred at the same temperature for 5 minutes. The mixture was returned to room temperature and further stirred for 4 hours. The reaction solution was poured into water and partitioned by adding chloroform. The aqueous layer was further extracted with chloroform. The organic layer was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and toluene-4-sulfonic acid 3- (4-chlorobenzylidene) -2-hydroxy-1-methyl-2- [1,2,4] triazol-1-ylmethylcyclopentylmethyl ester 0.41 g of a crude reaction product (hereinafter referred to as compound (2a)) was obtained as a pale yellow viscous solid. The crude reaction product was purified using Waters Sep-Pak Vac 35 cc (SiO ₂ , 10 g), and the isomer toluene-4-sulfonic acid 3- (4-chlorobenzylidene) -2-hydroxy- derived from the compound (3a) 0.32 g (yield: 87.6%) of 1-methyl-2- [1,2,4] triazol-1-ylmethylcyclopentylmethyl ester (hereinafter referred to as compound (2a)) was obtained as a white solid. .

Separately, 60% sodium hydride was used in the same amount as the compound (3a), and the same reaction as described above was performed. As a result, 0.42 g of a crude reaction product of compound (2a) was obtained as a pale yellow viscous product. The crude reaction product was purified using Waters Sep-Pak Vac 35 cc (SiO ₂ , 10 g) to obtain 0.30 g (yield 82.1%) of compound (2a) as a white solid.

The white solids of the compound (2a) obtained by each reaction and purification described above were combined and used in the subsequent reaction.
Melting point: 54.7 ° C
¹ H-NMR (400 MHz, CDCl ₃ , δ ppm):
0.90 (s, 3H), 1.62-1.71 (m, 1H), 1.88-1.99 (m, 1H), 2.47 (s, 3H), 2.55-2.73 (m, 2H), 3.64 (s, 1H), 4.06 ( d, 1H, J = 10.1Hz), 4.13 (d, 1H, J = 10.1Hz), 4.28 (s, 2H), 5.61 (t-like, 1H), 7.03 (d, 2H, J = 8.5Hz), 7.38 (d, 2H, J = 8.5Hz), 7.38 (d, 2H, J = 8.0Hz), 7.82 (d, 2H, J = 8.3Hz) 7.86 (s, 1H), 8.04 (s, 1H)
In addition, the components eluted after the compound (2a) was eluted in silica gel chromatography in each of the above reactions were combined to obtain a total of 18 mg of components. By NMR, the main component (hereinafter referred to as “component A”) in the component was toluene-4-sulfonic acid 3- (4-) derived from Isomer-II of compound (3) (hereinafter referred to as compound (3b)). Chlorobenzylidene) -2-hydroxy-1-methyl-2- [1,2,4] triazol-1-ylmethylcyclopentylmethyl ester.
¹ H-NMR (400 MHz, CDCl ₃ , δ ppm):
1.13 (s, 3H), 1.53-1.64 (m, 1H), 2.03-2.11 (m, 1H), 2.39 (s, 3H), 2.32-2.50 (m, 2H), 3.88 (d, 1H, J = 10.2 Hz), 3.92 (d, 1H, J = 10.5Hz), 4.09 (s, 1H), 4.13 (d, 1H, J = 14.0Hz), 4.36 (d, 1H, J = 14.0Hz), 5.51 (t- like, 1H), 6.97 (d, 2H, J = 8.5Hz), 7.21 (d, 2H, J = 8.5Hz), 7.23 (d, 2H, J = 8.5Hz), 7.69 (d, 2H, J = 8.3 Hz) 7.91 (s, 1H), 8.00 (s, 1H)
[Production Example 7: Synthesis 2 of 3- (4-chlorobenzylidene) -2-hydroxy-1-methyl-2- [1,2,4] triazol-1-ylmethylcyclopentylmethyl ester of toluene-4-sulfonic acid]
Under an argon stream, 67.1 mg of 60% sodium hydride was taken and washed with hexane. To this, 2 ml of dehydrated THF was added and suspended. Next, 0.28 g of the compound (3b) suspended in 4 ml of THF was dropped into this solution over 3 minutes at room temperature, and the mixture was stirred at the same temperature for 30 minutes. This solution was cooled with ice water, and 0.240 g of p-toluenesulfonyl chloride dissolved in 2 ml of THF was added dropwise over 2 minutes. After stirring at the same temperature for 12 minutes, the mixture was returned to room temperature and stirred for 1.25 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. Under reduced pressure, the solvent was distilled off, and the isomeric toluene-4-sulfonic acid 3- (4-chlorobenzylidene) -2-hydroxy-1-methyl-2- [1,2,4] triazole derived from the compound (3b) 0.444 g of a crude reaction product of -1-ylmethylcyclopentylmethyl ester (hereinafter referred to as compound (2b)) was obtained as an orange bowl. The crude reaction product was purified using Waters Sep-Pak Vac 20 cc (SiO ₂ , 5 g) to obtain 0.327 g of compound (2b) as a pale yellowish white solid. (However, as a result of NMR analysis, the purity is 85% and the yield is 67.9%). As a result of NMR analysis, the obtained compound (2b) was in agreement with the component A obtained in Production Example 6.

[Production Example 8: Synthesis of 5- (4-chlorobenzylidene) -2-chloromethyl-2-methyl-1H- [1,2,4] triazol-1-ylmethylcyclopentanol]
0.33 g of the compound (2a) obtained in Production Example 6 was dissolved in 3.0 ml of DMF, and 0.340 g of lithium chloride and 0.156 g of p-toluenesulfonic acid hydrate were added thereto. It reacted for 2 hours in an oil bath. After cooling, the reaction solution was poured into water and extracted with chloroform. The organic layer was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and 5- (4-chlorobenzylidene) -2-chloromethyl-2-methyl-1H- [1,2,4] triazol-1-ylmethylcyclopentanol (hereinafter referred to as compound ( 0.27 g of the crude reaction product of 1) was obtained as an ocherous solid. The solid was purified using Waters Sep-Pak Vac 20 cc (SiO ₂ , 5 g) to obtain 0.203 g (yield: 85.2%) of compound (1) as a light ocher solid.

  Separately, 0.253 g of the compound (2a) was used, and the reaction was performed in the same manner except that the silica gel chromatography purification was omitted to obtain 0.16 g of a crude reaction product of the compound (1) as an ocher solid.

The compound (1) obtained above was combined and recrystallized with a mixed solvent of ethyl acetate / hexane to obtain 0.257 g of compound (1) as white flocculent crystals.
Melting point: 157.0 ° C.,
¹ H-NMR (400 MHz, CDCl ₃ , δ ppm):
1.11 (s, 3H), 1.77-1.93 (m, 2H), 2.63-2.72 (m, 2H), 3.19 (s, 1H), 3.70 (d, 1H, J = 11.3Hz), 3.79 (d, 1H, J = 11.3Hz), 4.36 (d, 1H, J = 14.0Hz), 4.47 (d, 1H, J = 14.0Hz), 5.69 (t-like, 1H, J = 2.6Hz), 7.07 (d, 2H, J = 8.5Hz), 7.24 (d, 2H, J = 8.5Hz), 7.86 (s, 1H), 8.13 (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: Evaluation test of phytotoxicity of wheat growth suppression by seed treatment>
By pot test, the phytotoxicity of growth suppression by seed treatment was evaluated. The compound (1) dissolved in DMSO was applied to the wheat seeds in a vial so that the treatment amount was 200 g ai / 100 kg seeds or 20 g ai / 100 kg seeds, and then 8 wheat seeds were seeded in 80 cm ² pots. . The lower water supply was controlled in a greenhouse, and the degree of wheat growth was investigated 27 days after sowing. The growth inhibition index was calculated from the criteria shown in Table 2. It shows that the smaller the growth inhibition index, the smaller the phytotoxicity of growth inhibition by chemical treatment. As a control, instead of compound (1), 5- (4-chlorobenzyl) -2-chloromethyl-2-methyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclo Pentanol (compound (11)) and 2- (4-chlorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol (Triticazole): compound (12 )). The results are shown in Table 3.

In addition, when using any amount of compound (1), necrosis was not observed in the plant body at the time point 19 days after sowing.
<Test Example 2: Control effect of wheat rust caused by seed treatment>
By pot test, the control effect of wheat red rust caused by seed treatment was evaluated. The compound (1) dissolved in DMSO was applied to the wheat seeds in a vial so that the treatment amount was 200 g ai / 100 kg seeds or 20 g ai / 100 kg seeds, and then 8 wheat seeds were seeded in 80 cm ² pots. . The lower water supply was controlled in a greenhouse, and 27 days after sowing, wheat red rust fungus was inoculated and stored in a wet box for 2 days. Thereafter, the lower water supply was managed again in the greenhouse, and on the 12th day after inoculation, the diseased area ratio was investigated, and the control value was calculated by the following formula.
Control value (%) = (1− (Affected area ratio of treated area / Affected area ratio of untreated area)) × 100
As a control, a test was conducted using compound (11) instead of compound (1). The results are shown in Table 4.

<Test Example 3: Cucumber gray mold control effect test by foliar spray treatment>
In a cotyledon 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 is added to water at a predetermined concentration (200 mg). / L) 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. On the fourth day after inoculation, the morbidity of cucumber gray mold was investigated, and the control value was calculated by the following formula.
Control value (%) = (1− (average morbidity of sprayed area / average morbidity of non-sprayed area)) × 100
As a result, the control value was 80% or more.
<Test Example 4: 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 60 ppm), and kept at 25 ° C. under high humidity for 48 hours. After that, it was managed in the greenhouse. On the 10th day after inoculation, the morbidity of wheat red rust was investigated, and the control value was calculated in the same manner as in Test Example 3. As a control, the test was conducted using compound (12) instead of compound (1). The results are shown in Table 5.

<Test Example 5: Antibacterial test 1 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 previously cultured on a plate medium (Phaeosphaeria nodorum), wheat eye spot fungus (Pseudocercoporella herpotrichoides), wheat red snow rot fungus (Microdochium nivale), wheat blight fungus (Gaeumannomyces graminis), Barley leaf mold (Pyrenophora graminea), wheat leaf mold (Fusarium graminearum), rice seedling fungus (Gibberella fujikuroi), mycorrhizal fungus (Sclerotinia sclerotiorum), gray mold fungus (Botrytis cinerea), anthracnose fungus (Glomerellacingur) Cucumber vines (Fusarium oxysporum), citrus blue mold (Penicillium Italicum), sugar beet brown fungus (Cercospora beticola), wheat leaf blight (Septoria tritici) or barley cloud fungus (Rhynchosporium secalis) And inoculated on the above-mentioned drug-containing plate medium. After inoculation, the cells were cultured for 1 to 14 days at a suitable temperature for growth of each fungus (for example, see LIST OF CULTURES 1996 microorganisms 10th edition, literature from the Institute for Fermentation, etc.), 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.

<Test Example 6: Antibacterial test 2 against pathogenic bacteria>
In this test example, a control using the compound (12) instead of the compound (1) was included as a comparative example to test antibacterial activity against various phytopathogenic fungi.

  In the same manner as in Test Example 5, a plate medium containing Compound (1) or Compound (12) at a predetermined concentration (1.25 to 5 mg / L) was prepared.

  On the other hand, a test bacterium previously cultured on a plate medium (wheat red snow rot fungus, rice seedling blight fungus, sugar beet brown blight fungus, barley cloud fungus, or wheat leaf blight fungus) was punched out with a cork borer having a diameter of 4 mm. Were inoculated on a drug-containing plate medium. After inoculation, the cells were cultured for 1 to 14 days at the appropriate growth temperature for each fungus. The growth of the fungus was measured by the fungus diameter, and the hyphal elongation inhibition rate was determined in the same manner as in Test Example 5. The results are shown in Tables 6-10.

  INDUSTRIAL APPLICABILITY The present invention can be suitably used as an active ingredient of a control agent that can suppress phytotoxicity to plants and can control plant diseases.

Claims (14)

A triazole derivative represented by the following general formula (I).

(In General Formula (I), R ¹ represents an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. Haloalkyl group, an alkoxy group having 1 to 4 carbon atoms, or a haloalkoxy group having 1 to 4 carbon atoms, and L represents a halogen atom.) The triazole derivative according to claim 1, wherein R ² is a halogen atom, a haloalkyl group having 1 to 2 carbon atoms, or a haloalkoxy group having 1 to 2 carbon atoms. The triazole derivative according to claim 1 or 2, wherein R ² is a halogen atom.   The triazole derivative according to any one of claims 1 to 3, wherein L is a chlorine atom or a bromine atom. An intermediate compound of the triazole derivative according to any one of claims 1 to 4,
An intermediate compound represented by the following general formula (II).

(In the formula (II), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (I), ^{R 3} is may carbon number 1 to be a hydrogen atom be substituted 3 represents an alkyl group, a phenyl group or a naphthyl group.) An intermediate compound of the triazole derivative according to any one of claims 1 to 4,
An intermediate compound represented by the following general formula (III).

(In the above formula (III), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (I).) An intermediate compound of the triazole derivative according to any one of claims 1 to 4,
An intermediate compound represented by the following general formula (IV).

(In the formula (IV), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the above formula (I), ^{R 4} represents an alkyl group having 1 to 4 carbon atoms. ) An intermediate compound of the triazole derivative according to any one of claims 1 to 4,
The intermediate compound shown by the following general formula (V).

(In the formula (V), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the above formula (I), ^{R 4} represents an alkyl group having 1 to 4 carbon atoms. ) An intermediate compound of the triazole derivative according to any one of claims 1 to 4,
An intermediate compound represented by the following general formula (VI).

(In the formula (VI), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the above formula (I), ^{R 4} represents an alkyl group having 1 to 4 carbon atoms. ) A method for producing a triazole derivative according to any one of claims 1 to 4,
The triazole comprising the step of obtaining the triazole derivative represented by the above general formula (I) by substituting the substituted sulfonyloxy group represented by -OSO ₂ R ³ with a halogen atom in the intermediate compound represented by the following general formula (II) A method for producing a derivative.

(In the formula (II), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (I), ^{R 3} is good number of carbon atoms 1 to be a hydrogen atom be substituted 3 represents an alkyl group, a phenyl group or a naphthyl group.) A method for producing a triazole derivative according to any one of claims 1 to 4,
The manufacturing method of a triazole derivative including the process of obtaining the intermediate compound shown by the following general formula (II) by sulfonylating the intermediate compound shown by the following general formula (III).

(In the above formula (III), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (I).)

(Wherein (II), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (I), ^{R 3} is good number of carbon atoms 1 to be a hydrogen atom be substituted 3 represents an alkyl group, a phenyl group or a naphthyl group.) A method for producing a triazole derivative according to any one of claims 1 to 4,
The manufacturing method of a triazole derivative including the process of obtaining the intermediate compound shown by the following general formula (III) by reducing the intermediate compound shown by the following general formula (IV).

(In the formula (IV), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the above formula (I), ^{R 4} represents an alkyl group having 1 to 4 carbon atoms. )

(In the above formula (III), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the formula (I).) A method for producing a triazole derivative according to any one of claims 1 to 4,
By reacting an intermediate compound represented by the following general formula (V) obtained by oxiranating an intermediate compound represented by the following general formula (VI) with a compound represented by the following general formula (IX), The manufacturing method of a triazole derivative including the process of obtaining the intermediate compound shown by general formula (IV).

(In the formula (VI), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the above formula (I), ^{R 4} represents an alkyl group having 1 to 4 carbon atoms. )

(In the formula (V), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the above formula (I), ^{R 4} is identical to ^{R 4} in the formula (VI). )

(In the above formula (IX), M represents a hydrogen atom or an alkali metal.)

(In the formula (IV), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} in the above formula (I), ^{R 4} is identical to ^{R 4} in the formula (VI). )   An agricultural or horticultural agent or an industrial material protective agent comprising the triazole derivative according to any one of claims 1 to 4 as an active ingredient.