WO2015050040A1

WO2015050040A1 - Plant disease control composition and use thereof

Info

Publication number: WO2015050040A1
Application number: PCT/JP2014/075544
Authority: WO
Inventors: 雄一松崎; 真倉橋
Original assignee: 住友化学株式会社
Priority date: 2013-10-02
Filing date: 2014-09-18
Publication date: 2015-04-09

Abstract

This plant disease control composition is effective in controlling plant diseases, and contains a tetrazolinone compound represented in formula (1) (in the formula, R¹ represents a C1-C3 alkyl group, etc., R² represents a hydrogen atom, etc., R³ represents a C1-C3 alkyl group, etc., Z¹ represents a C1-C3 alkyl group, Z² represents a C1-C2 alkoxy group, etc., and Z³ represents a C1-C3 alkyl group, etc.) and a bactericidally active compound, and ideally, the weight ratio between the tetrazolinone compound and the bactericidally active compound is tetrazolinone compound / bactericidally active compound = 0.1/1 to 10/1.

Description

Plant disease control composition and use thereof

The present invention relates to a plant disease control composition and its use.

Conventionally, many compounds have been developed and put into practical use for controlling plant diseases (see, for example, Patent Documents 1 and 2).

International Publication No. 99/05139 International Publication No. 2013/092224

An object of the present invention is to provide a composition having an excellent control effect against plant diseases.

As a result of studying to find a composition having an excellent control effect against plant diseases, the present inventor has found that a tetrazolinone compound represented by the following formula (1) and one or more bactericidal active compounds selected from the following group A: It has been found that a plant disease control composition containing an excellent control effect against plant diseases.
That is, the present invention is as follows: [1] Formula (1)

[Where,
R ¹ represents a C1-C3 alkyl group which may have one or more halogen atoms or a halogen atom,
R ² represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group,
R ³ represents a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a cyclopropyl group, or a C1-C3 alkoxy group optionally having one or more halogen atoms;
Z ¹ represents a C1-C3 alkyl group,
Z ² represents a hydrogen atom, a C1-C2 alkoxy group, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C2 alkylthio group, or a cyano group,
Z ³ represents a hydrogen atom, a C1-C3 alkyl group or a halogen atom. ]
A tetrazolinone compound represented by:
A plant disease control composition comprising one or more fungicidal active compounds selected from the group (A).
Group (A):
Propiconazole, Prothioconazole, Triadimenol, Prochloraz, Penconazole, Dibuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole bromconazole, epoxiconazole, difenoconazole, cyproconazole, metconazole, triflumizole, triflumizole aconazole, microbutanil, fenbuconazole, hexaconazole, fluquinconazole, triticonazole, tertanol, tertanol. ipconazole), simeconazole, hymexazole, etridiazole, flutriafol, bixafen, benzobindiflufirfulx Xapyroxad), penthiopyrad (penthiopyrad), N- (1,1,3- trimethyl indane-4-yl) -1-methyl-3-difluoromethyl-4-carboxylic acid amide,
A compound represented by the following formula (b):

Isofetamid, isopyrazam, boscalid, fluopyram, sedaxane, penflufen, fluthranil, flutronil, mepronil And furametopyr.
[2] The plant disease control composition according to [1], wherein the weight ratio of the tetrazolinone compound to the bactericidal active compound is tetrazolinone compound / bactericidal active compound = 0.1 / 1 to 10/1.

[3] Formula (1)

[Where,
R ¹ represents a C1-C3 alkyl group which may have one or more halogen atoms or a halogen atom,
R ² represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group,
R ³ represents a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a cyclopropyl group, or a C1-C3 alkoxy group optionally having one or more halogen atoms;
Z ¹ represents a C1-C3 alkyl group,
Z ² represents a hydrogen atom, a C1-C2 alkoxy group, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C2 alkylthio group, or a cyano group,
Z ³ represents a hydrogen atom, a C1-C3 alkyl group or a halogen atom. ]
The plant disease control method including the process of processing the effective amount of the tetrazolinone compound shown by 1 and the 1 or more types of fungicidal active compound chosen from a group (A) to the soil which grows a plant or a plant.
Group (A):
Propiconazole, Prothioconazole, Triadimenol, Prochloraz, Penconazole, Dibuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole bromconazole, epoxiconazole, difenoconazole, cyproconazole, metconazole, triflumizole, triflumizole aconazole, microbutanil, fenbuconazole, hexaconazole, fluquinconazole, triticonazole, tertanol, tertanol. ipconazole), simeconazole, hymexazole, etridiazole, flutriafol, bixafen, benzobindiflufirfulx Xapyroxad), penthiopyrad (penthiopyrad), N- (1,1,3- trimethyl indane-4-yl) -1-methyl-3-difluoromethyl-4-carboxylic acid amide,
A compound represented by the following formula (b):

Isofetamid, isopyrazam, boscalid, fluopyram, sedaxane, penflufen, fluthranil, flutronil, mepronil And furametopyr.
[4] The plant disease control method according to [3], wherein the weight ratio of the tetrazolinone compound to the bactericidal active compound is tetrazolinone compound / bactericidal active compound = 0.1 / 1 to 10/1.
[5] The plant disease control method according to [3] or [4], wherein the plant or the soil in which the plant is cultivated is wheat or soil in which the wheat is cultivated.

The plant disease control composition of the present invention (hereinafter referred to as the present composition) is represented by the formula (1).

[Wherein R ¹ , R ² , R ³ , Z ¹ , Z ² and Z ³ represent the same meaning as described above. ]
And a one or more bactericidal active compounds (hereinafter referred to as the present bactericidal active compound) selected from the group (A).

First, the tetrazolinone compound will be described.

The substituents in the present specification are described in detail below.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The C1-C3 alkyl group represents a linear or branched alkyl group having 1-3 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
The C1-C3 alkyl group optionally having one or more halogen atoms represents a C1-C3 alkyl group in which one or more hydrogen atoms may be substituted with a halogen atom, such as a methyl group or an ethyl group , Propyl, isopropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, dibromomethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl Group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,2-difluoropropyl group, 3,3, 3-trifluoropropyl group, heptafluoropropyl group, heptafluoroisopropyl 1- (trifluoromethyl) -2,2,2-trifluoroethyl group and a 3-fluoropropyl group.

The C1-C3 alkoxy group represents a linear or branched alkoxy group having 1 to 3 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
The C1-C3 alkoxy group which may have one or more halogen atoms represents a C1-C3 alkoxy group in which one or more hydrogen atoms may be substituted with a halogen atom, such as a methoxy group, an ethoxy group, Propoxy group, isopropoxy group, fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, chloromethoxy group, dichloromethoxy group, trichloromethoxy group, dibromomethoxy group, chlorofluoromethoxy group, dichlorofluoromethoxy group, chlorodifluoromethoxy group 2-fluoroethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 2-chloroethoxy group, 2,2-dichloroethoxy group, 2,2,2-trichloroethoxy group, Pentafluoroethoxy group, 3-fluoropropoxy group, 3 3,3-trifluoro-propoxy group, heptafluoropropoxy group, heptafluoro isopropoxy Po carboxymethyl group, 1- (trifluoromethyl) -2,2,2-trifluoroethoxy group and a 3-fluoropropoxy group.

Examples of the C1-C2 alkoxy group include a methoxy group and an ethoxy group.

Examples of the C1-C2 alkylthio group include a methylthio group and an ethylthio group.

First, a method for synthesizing the tetrazolinone compound will be described.

The tetrazolinone compound can be synthesized, for example, by the following synthesis method.

(Synthesis method A)
The tetrazolinone compound comprises a compound represented by formula (A1) (hereinafter referred to as compound (A1)) and a compound represented by formula (A2) (hereinafter referred to as compound (A2)) in the presence of a base. It can manufacture by making it react.

[Wherein R ¹ , R ² , R ³ , Z ¹ , Z ² and Z ³ represent the same meaning as described above, and Z ¹¹ represents a leaving group such as a chlorine atom, a bromine atom or an iodine atom. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
Examples of the base used in the reaction include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclononene and the like. Alkali metal carbonates such as organic bases, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium hydroxide, hydroxide Alkali metal hydroxides such as sodium, potassium hydroxide and cesium hydroxide, alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride, alkali metals such as lithium hydride, sodium hydride and potassium hydride Hydrogenation , Sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
In the reaction, with respect to 1 mol of the compound (A1), the compound (A2) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 10 mol.
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
In the reaction, sodium iodide, tetrabutylammonium iodide or the like may be added as necessary, and these compounds are usually in a ratio of 0.001 to 1.2 mol with respect to 1 mol of the compound (A1). Used in
After completion of the reaction, the tetrazolinone compound can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Alternatively, the tetrazolinone compound can be isolated by performing post-treatment operations such as filtration and concentration of the reaction mixture. The isolated tetrazolinone compound can be further purified by chromatography, recrystallization or the like.

(Synthesis method B)
Among the tetrazolinone compounds, the present tetrazolinone compound represented by the formula (1-B) in which Z ³ is R ¹⁰⁰ (hereinafter referred to as the compound (1-B)) is represented by the formula (1-2). It can be produced by reacting a tetrazolinone compound (hereinafter referred to as compound (1-2)) with a halogenating agent.

[Wherein, R ¹ , R ² , R ³ , Z ¹ and Z ² represent the same meaning as described above, and R ¹⁰⁰ represents a halogen atom. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, nitriles such as acetonitrile and propionitrile, And mixtures thereof.
Examples of the halogenating agent used in the reaction include N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, chlorine, bromine, iodine, and sulfuryl chloride.
In the reaction, the halogenating agent is usually used at a ratio of 1 to 10 mol per 1 mol of the compound (1-2).
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (1-B) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated tetrazolinone compound can be further purified by chromatography, recrystallization or the like.

(Synthesis Method C)
Among the tetrazolinone compounds, a compound represented by the formula (1-C) in which Z ² is a cyano group (hereinafter referred to as compound (1-C)) is a compound represented by the formula (C1) (hereinafter referred to as compound). (C1).) And a cyanating agent can be reacted.

[Wherein, R ¹ , R ² , R ³ , Z ¹ and Z ³ represent the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisole, methyl tert-butyl ether, diisopropyl ether, n-heptane, n -Hydrocarbons such as hexane, cyclohexane, n-pentane, toluene, xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, acetonitrile, propionitrile, etc. Nitriles, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, sulfoxides such as dimethyl sulfoxide, methanol, ethanol, propano Le, alcohols and mixtures thereof, such as butanol.
Examples of the cyanating agent used in the reaction include phosphorus oxychloride, phosphorus pentachloride, and phosphorus oxybromide.
In the reaction, a base may be used. Examples of the base used include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicyclone. And organic bases such as decene and diazabicyclononene. These bases can also be used as a solvent.
In the reaction, with respect to 1 mole of the compound (C1), the cyanating agent is usually used at a ratio of 1 to 20 moles and the base is usually used at a ratio of 1 to a large excess mole.
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 72 hours.
After completion of the reaction, the compound (1-C) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. In addition, when a precipitate is generated, the compound (1-C) can be isolated by filtering the precipitate. Further, it may be purified by operations such as chromatography and recrystallization.

(Reference Synthesis Method A)
A compound represented by formula (11) (hereinafter referred to as compound (11)) is obtained by reacting a compound represented by formula (10) (hereinafter referred to as compound (10)) with an azidating agent. Can be synthesized.

[Wherein R ³ represents the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, acetonitrile, nitriles and mixtures thereof, such as propionitrile and the like.
Examples of the azidating agent used in the reaction include inorganic azides such as sodium azide, barium azide and lithium azide, and organic azides such as trimethylsilyl azide and diphenylphosphoryl azide.
In the reaction, the azidating agent is usually used at a ratio of 1 to 10 moles relative to 1 mole of the compound (10).
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
In this reaction, a Lewis acid such as aluminum chloride or zinc chloride may be added as necessary, and these compounds are usually used at a ratio of 0.05 to 5 mol with respect to 1 mol of compound (10). It is done.
After completion of the reaction, the compound (11) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (11) can be further purified by chromatography, recrystallization and the like.

(Reference Synthesis Method B)
The compound represented by the formula (13) (hereinafter referred to as the compound (13)) is obtained by mixing the compound (11) and the compound represented by the formula (12) (hereinafter referred to as the compound (12)) with the presence of a base. It can synthesize | combine by making it react.

[Wherein R ³ represents the same meaning as described above, and Z ⁵ represents a leaving group such as a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, and a p-toluenesulfonyloxy group. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
As the compound (12) used in the reaction, a commercially available product can be used. Specifically, alkyl halides such as methyl bromide and methyl iodide, dialkyl sulfates such as dimethyl sulfate, alkyl sulfates such as methyl p-toluenesulfonate and methyl methanesulfonate, or aryl sulfates Can be mentioned.
Examples of the base used in the reaction include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclononene and the like. Alkali metal carbonates such as organic bases, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium hydroxide, hydroxide Alkali metal hydroxides such as sodium, potassium hydroxide and cesium hydroxide, alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride, alkali metals such as lithium hydride, sodium hydride and potassium hydride Hydrogenation , Lithium hydride, sodium hydride, an alkali metal hydride such as potassium hydride, sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
In the reaction, with respect to 1 mol of the compound (11), the compound (12) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 0.5 to 10 mol.
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (13) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (13) can be further purified by chromatography, recrystallization and the like.

(Reference Synthesis Method C)
Compound (A1) can be synthesized by reacting compound (13) with a halogenating agent.

[Wherein R ³ and Z ¹¹ represent the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ters, anisole, ethers such as methyl tert-butyl ether, diisopropyl ether, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, fluorobenzene, difluorobenzene, trifluorobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene , Α, α, α-trifluorotoluene, halogenated hydrocarbons such as α, α, α-trichlorotoluene, esters such as ethyl acetate and methyl acetate, acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone, acetonitrile, nitriles and mixtures thereof, such as propionitrile and the like.
Examples of the halogenating agent that can be used in the reaction include a chlorinating agent, a brominating agent, or an iodinating agent such as chlorine, bromine, iodine, sulfuryl chloride, N-chlorosuccinimide, N-bromosuccinimide, 1,3-dibromo. -5,5-dimethylhydantoin, iodosuccinimide, tert-butyl hypochlorite, N-chloroglutarimide, N-bromoglutarimide, N-chloro-N-cyclohexyl-benzenesulfonimide, N-bromophthalimide .
A radical initiator can also be used for this reaction.
Examples of the radical initiator used in the reaction include benzoyl peroxide, azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile and the like.
In the reaction, the halogenating agent is usually used in a proportion of 1 to 10 mol and the radical initiator is usually used in a proportion of 0.01 to 1 mol with respect to 1 mol of the compound (13).
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (A1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (A1C) can be further purified by chromatography, recrystallization, and the like.

(Reference Synthesis Method D)
A compound represented by formula (15) (hereinafter referred to as compound (15)) is a compound represented by formula (A1-D) in which R ⁶ is Z ⁶ (hereinafter referred to as compound (15)). A1-D)) and a compound represented by formula (14) (hereinafter referred to as compound (14)) can be produced.

[Wherein, Z ¹¹ and Z ⁶ represent the same meaning as described above, R ⁴ represents a C1-C12 alkyl group or a phenyl group, and M represents sodium, potassium, or lithium. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisole, methyl tert-butyl ether, diisopropyl ether, n-heptane, n -Hydrocarbons such as hexane, cyclohexane, n-pentane, toluene, xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, acetonitrile, propionitrile, etc. Nitriles, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, Ketones such as Louis Seo ketone, methanol, ethanol, propanol, and mixtures thereof, such as butanol.
As the compound (14), sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium isopropoxide, sodium sec-butoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium Examples include butoxide, potassium isopropoxide, potassium sec-butoxide, potassium tert-butoxide, sodium phenoxide and the like.
In the reaction, compound (14) is usually used at a ratio of 1 to 10 mol with respect to 1 mol of compound (A1-D).
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (15) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, purification may be performed by operations such as distillation, chromatography, recrystallization and the like.

(Reference Synthesis Method E)
The compound represented by formula (16) (hereinafter referred to as compound (16)) can be synthesized by coupling reaction of compound (15) and compound (7) in the presence of a base and a catalyst.

[Wherein R ⁴ and Z ⁶ represent the same meaning as described above, R ^3A represents a C1-C3 alkyl group or a cyclopropyl group, and Z ⁷ represents B (OH) ₂ , an alkoxyboryl group, or a trifluoroborate salt. It represents a - _(BF ³ ^{K +).} ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, methanol, ethanol, propanol, alcohols such as butanol, water and mixtures thereof.
As the organic boron compound (7) used in the reaction, a commercially available one is usually used, or N.I. Miyaura and A.M. Suzuki, Chem. Rev. , 1995, 95, 2457, etc., and those synthesized by known methods can also be used. Organoboron compounds used in the reaction (7), for ^example, after the reaction of alkyllithium and butyl Do lithium iodide compound of ^{R 3A} ^(R 3A -I) or bromo compound ^(R 3A -Br), Boronic ester derivatives can be synthesized by reacting with borate esters. Further, a boronic acid derivative can be synthesized by hydrolyzing the boronic acid ester derivative obtained by the above-described reaction as necessary. In addition, Molander et al. Acc. Chem. Res. , According to known methods described in the review of such 2007,40,275, by fluorinating with hydrogen fluoride potassium the boronic acid ester, trifluoroborate salt _BF ³ - it can be obtained ^{K +.}
Catalysts used in the reaction include palladium (II) acetate, dichlorobis (triphenylphosphine) palladium, tetrakistriphenylphosphinepalladium (0), palladium (II) acetate / triscyclohexylphosphine, bis (diphenylphosphaneferrocenyl) ) Palladium (II) dichloride, 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene (1,4-naphthoquinone) palladium dimer, allyl (chloro) (1,3-dimesityl-1,3- Dihydro-2H-imidazol-2-ylidene) palladium or palladium (II) acetate / dicyclohexyl (2 ′, 4 ′, 6′-triisopropylbiphenyl-2-yl) phosphine, tris (dibenzylideneacetone) dipalladium And the like.
Examples of the base used in the reaction include organic bases such as triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene and diazabicyclononene. Alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, etc., lithium hydroxide, sodium hydroxide, Alkali metal hydroxides such as potassium hydroxide and cesium hydroxide, alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride, alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride ,Rin Alkali metal phosphates such as tripotassium, sodium methoxide, sodium ethoxide, sodium tert- butoxide, alkali metal alkoxides such as potassium tert- butoxide.
In the reaction, with respect to 1 mol of the compound (15), the compound (7) is usually used in a proportion of 1 to 10 mol, the base is usually in a proportion of 1 to 10 mol, and the catalyst is usually used in a proportion of 0.0001 to 1 mol. It is done.
The reaction temperature is usually in the range of 0 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (16) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (16) can be further purified by chromatography, recrystallization and the like.

(Reference Synthesis Method F)
A compound represented by the formula (A1-F) (hereinafter referred to as compound (A1-F)) can be produced by reacting compound (16) with a halogenating agent.

[Wherein, R ^3A , R ⁴ and Z ⁶ represent the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane. Halogenated hydrocarbons such as chlorobenzene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, organic acids such as formic acid, acetic acid and trifluoroacetic acid, water and mixtures thereof. Can be mentioned.
Examples of the halogenating agent used in the reaction include hydrochloric acid, hydrobromic acid, and hydriodic acid.
In the reaction, the halogenating agent is usually used at a ratio of 1 mol or more per 1 mol of the compound (16).
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (A1-F) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, purification may be performed by operations such as distillation, chromatography, recrystallization and the like.

(Reference Synthesis Method G)
In the compound represented by the formula (XG2) (hereinafter referred to as the compound (XG2)), the compound (A1) and the compound represented by the formula (XG1) (hereinafter referred to as the compound (XG1)) are present in the presence of a base. It can manufacture by making it react under.

[Wherein R ¹ , R ² , R ³ , Z ³ and Z ¹¹ represent the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
Examples of the base used in the reaction include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclononene and the like. Alkali metal carbonates such as organic bases, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium hydroxide, hydroxide Alkali metal hydroxides such as sodium, potassium hydroxide and cesium hydroxide, alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride, alkali metals such as lithium hydride, sodium hydride and potassium hydride Hydrogenation , Sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
In the reaction, with respect to 1 mol of the compound (A1), the compound (XG1) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 10 mol.
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
In the reaction, sodium iodide or tetrabutylammonium iodide may be added as necessary. These compounds are usually added in an amount of 0.001 to 1.2 mol per 1 mol of the compound (A1). Used in proportions.
After completion of the reaction, the compound (XG2) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Alternatively, compound (XG2) can be isolated by performing post-treatment operations such as filtration and concentration of the reaction mixture. Further, it can be purified by chromatography, recrystallization or the like.

(Reference Synthesis Method H)
A compound represented by formula (XH2) (hereinafter referred to as compound (XH2)) is obtained by reacting compound (XG2) with a compound represented by formula (XH1) (hereinafter referred to as compound (XH1)) in the presence of a base. Can be manufactured.

[Wherein, R ¹ , R ² , R ³ and Z ³ represent the same meaning as described above, R ⁹² represents a C1-C3 alkyl group, and Z ¹²⁰ represents a C1-C3 alkoxy group or a halogen atom. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
Examples of the base used in the reaction include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclononene and the like. Alkali metal carbonates such as organic bases, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium hydroxide, hydroxide Alkali metal hydroxides such as sodium, potassium hydroxide and cesium hydroxide, alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride, alkali metals such as lithium hydride, sodium hydride and potassium hydride Hydrogenation , Sodium methoxide, sodium ethoxide, sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
In the reaction, with respect to 1 mole of the compound (XG2), the compound (XH1) is usually used at a ratio of 1 to 10 moles, and the base is usually used at a ratio of 1 to 10 moles.
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
In the reaction, additives may be added as necessary, and examples of the additive include 18-crown-6 and dibenzo-18-crown-6. These additives are usually used in a proportion of 0.001 to 1.2 mol with respect to 1 mol of compound (XG2).
After completion of the reaction, the compound (XH2) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, it can be purified by chromatography, recrystallization or the like.

(Reference Synthesis Method I)
A compound represented by the formula (XI1) (hereinafter referred to as compound (XI1)) can be produced by reacting compound (XH2) with hydrazines.

[Wherein R ¹ , R ² , R ³ , R ⁹² and Z ³ represent the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisole, methyl tert-butyl ether, diisopropyl ether, n-heptane, n -Hydrocarbons such as hexane, cyclohexane, n-pentane, toluene, xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, acetonitrile, propionitrile, etc. Nitriles, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, sulfoxides such as dimethyl sulfoxide, methanol, ethanol, propano Le, alcohols such as butanol, water and mixtures thereof.
Examples of hydrazines used in the reaction include hydrazine monohydrate, hydrazine hydrochloride, hydrazine sulfate, and anhydrous hydrazine.
In the reaction, hydrazines are usually used at a ratio of 1 to 100 mol with respect to 1 mol of compound (XH2).
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (XI1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, it may be purified by operations such as chromatography and recrystallization.

(Reference Synthesis Method J)
A compound represented by formula (XJ2) (hereinafter referred to as compound (XJ2)) is reacted with compound (XI1) and a compound represented by formula (XJ1) (hereinafter referred to as compound (XJ1)). Can be manufactured.

[Wherein R ¹ , R ² , R ³ , R ⁹² , Z ³ and Z ⁵ represent the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
As the compound (XJ1) used in the reaction, a commercially available product can be used. For example, chlorodifluoromethane, methyl bromide, ethyl bromide, n-propyl bromide, n-butyl bromide, n-pentyl bromide, n-hexyl bromide, methyl iodide, ethyl iodide, propyl iodide, Isopropyl iodide, isobutyl iodide, isoamyl iodide, 2-propynyl iodide, 2-butynyl iodide, allyl bromide, cyclopropyl bromide, 2-propynyl bromide, 2-butynyl bromide, cyclopropylmethyl bromide, Alkyl halides such as 1,1-difluoro-2-iodoethane and 1,1,1-trifluoro-2-iodoethane, dimethyl sulfate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, p-toluenesulfone Alkyl such as propyl acid, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, etc. Is an aryl sulfates, acyl halide of acetyl chloride, methanesulfonyl chloride, ethanesulfonyl chloride, isopropylsulfonyl chloride, cyclopropyl chloride, N, a sulfonic acid halide such as N- dimethyl chloride.
In the reaction, a base may be used. Examples of the base used include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicyclone. Organic bases such as decene and diazabicyclononene, alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and cesium hydrogen carbonate Salts, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, alkali metal halides such as sodium fluoride, potassium fluoride, cesium fluoride, lithium hydride, sodium hydride , Potassium hydride Alkali metal hydrides, lithium hydride, sodium hydride, an alkali metal hydride such as potassium hydride, sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
In the reaction, with respect to 1 mol of compound (XI1), compound (XJ1) is usually used in a proportion of 1 to 10 mol, and base is usually used in a proportion of 1 to 10 mol.
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (XJ2) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound of the present invention can be further purified by chromatography, recrystallization and the like.

(Reference Synthesis Method K)
A compound represented by the formula (XK1) (hereinafter referred to as compound (XK1)) can be produced by reacting compound (XJ2) with a hydrolyzing agent.

[Wherein, R ¹ , R ² , R ³ , R ⁹² , Z ¹ and Z ³ represent the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include water, alcohols such as methanol, ethanol, propanol, and butanol, hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, and diethyl ether. , Tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisole, methyl tert-butyl ether, diisopropyl ether and other ethers, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, etc. Mention may be made of halogenated hydrocarbons, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof.
Examples of the hydrolyzing agent used in the reaction include bases such as potassium hydroxide aqueous solution and sodium hydroxide aqueous solution, and acids such as hydrochloric acid and sulfuric acid.
In the reaction, the hydrolyzing agent is usually used at a ratio of 0.5 to 20 mol with respect to 1 mol of the compound (XJ2).
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 72 hours.
After completion of the reaction, the compound (XK1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (XK1) can be further purified by operations such as chromatography and recrystallization.

(Reference Synthesis Method L)
A compound represented by the formula (XL1) (hereinafter referred to as compound (XL1)) can be produced by reacting compound (XK1) with a halogenating agent.

[Wherein, R ¹ , R ² , R ³ , R ¹⁰⁰ , Z ¹ and Z ³ represent the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether and diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane and chlorobenzene, esters such as ethyl acetate and methyl acetate , Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, and mixtures thereof.
Examples of the halogenating agent used in the reaction include phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus oxybromide, phosphorus tribromide, phosphorus pentabromide, phosphorus triiodide, and dichloride. Oxalyl, oxalyl dibromide, triphosgene, diphosgene, phosgene and sulfuryl chloride.
In the reaction, the halogenating agent is usually used at a ratio of 1 to 10 mol per 1 mol of the compound (XK1).
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
In the reaction, a catalyst may be added, and N, N-dimethylformamide, triethylamine, diisopropylethylamine or the like is used, and the catalyst is used in a ratio of 0.001 to 1 mol with respect to 1 mol of compound (XK1).
After completion of the reaction, the compound (XL1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (XL1) may be further purified by operations such as chromatography and recrystallization.

(Reference Synthesis Method M)
Compound (C1) can be produced by reacting compound (XL1) with an amidating agent.

[Wherein, R ¹ , R ² , R ³ , R ¹⁰⁰ , Z ¹ and Z ³ represent the same meaning as described above. ]
Examples of the solvent used in the reaction include diethyl ether, tetrahydrofuran, 1,4-dioxane, ethers such as ethylene glycol-lucmethyl ether, anisole, methyl tert-butyl ether, diisopropyl ether, n-heptane, n -Hydrocarbons such as hexane, cyclohexane, n-pentane, toluene, xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, acetonitrile, propionitrile, etc. Nitriles, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, sulfoxides such as dimethyl sulfoxide, methanol, ethanol, propano Le, alcohols such as butanol, water and mixtures thereof.
Examples of the amidating agent used in the reaction include an aqueous ammonia solution, ammonia hydrochloride, ammonia sulfate, and ammonia gas. An amidating agent can also be used as a solvent. In the reaction, an amidating agent is usually used in a proportion of 1 mol to large excess with respect to 1 mol of compound (XL1).
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 72 hours.
After completion of the reaction, the compound (C1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. In addition, when a precipitate is generated, the compound (C1) can be isolated by filtering the precipitate. Further, it may be purified by operations such as chromatography and recrystallization.

(Reference Synthesis Method AA)
Compound (A2) can be produced by reacting a compound represented by the formula (YA1) (hereinafter referred to as compound (YA1)) with an acid.

[Wherein R ¹ , R ² , R ⁹² , Z ¹ , Z ² and Z ³ represent the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include alcohols such as methanol, ethanol, propanol, and butanol, water, acetic acid, and mixtures thereof.
Examples of the acid used in the reaction include acetic acid, hydrochloric acid, and hydrobromic acid, and these aqueous solutions can also be used as a solvent.
In the reaction, an acid is usually used in a large excess amount relative to 1 mol of the compound (YA1).
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 100 hours.
After completion of the reaction, the compound (A2) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Alternatively, the compound (A2) can be isolated by performing post-treatment operations such as concentration of the reaction mixture. Further, it can be purified by chromatography, recrystallization or the like.

(Reference Synthesis Method AB)
Compound (YA1) can be produced by reacting a compound represented by formula (YB1) (hereinafter referred to as compound (YB1)) with compound (XJ1) in the presence of a base.

[Wherein R ¹ , R ² , R ⁹² , Z ¹ , Z ² , Z ³ and Z ⁵ represent the same meaning as described above. ]
This reaction can be carried out according to Reference Synthesis Method J.

(Reference synthesis method AC)
A compound represented by formula (YC3) (hereinafter referred to as compound (YC3)) is a compound represented by formula (YC1) (hereinafter referred to as compound (YC1)) and a compound represented by formula (YC2) ( Hereinafter, it can be produced by reacting compound (YC2)) in the presence of a base.

[Wherein, R ¹ , R ² and Z ³ represent the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 Acid amides such as 1,3-dimethyl-2-imidazolidinone and N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, nitriles such as acetonitrile and propionitrile Beauty mixtures thereof.
Examples of the base used in the reaction include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclononene and the like. Alkali metal carbonates such as organic bases, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium hydroxide, hydroxide Alkali metal hydroxides such as sodium, potassium hydroxide and cesium hydroxide, alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride, alkali metals such as lithium hydride, sodium hydride and potassium hydride Hydrogenation , Sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
In the reaction, with respect to 1 mol of the compound (YC1), the compound (YC2) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 10 mol.
The reaction temperature of the reaction is usually in the range of −78 to 150 ° C. The reaction time is usually in the range of 0.1 to 72 hours.
After completion of the reaction, the compound (YC3) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, it can be purified by chromatography, recrystallization or the like.

(Reference synthesis method AD)
Compound (XG1) can be produced by reacting compound (YC3) in the presence of an acid.

[Wherein, R ¹ , R ² and Z ³ represent the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, nitromethane, acetonitrile, propionitrile, etc. Nitriles, and mixtures thereof.
Examples of the acid used in the reaction include aluminum trichloride, titanium tetrachloride, iron trichloride, hydrogen fluoride, hypochlorous acid, polyphosphoric acid, and the like.
In the reaction, an acid is usually used at a ratio of 1 to 10 mol per 1 mol of the compound (YC3).
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 72 hours.
After completion of the reaction, the compound (XG1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, it can be purified by chromatography, recrystallization or the like.

(Reference production method AE)
A compound represented by formula (YE3) (hereinafter referred to as compound (YE3)) is a compound represented by formula (YE1) (hereinafter referred to as compound (YE1)) and a compound represented by formula (YE2). (Hereinafter referred to as compound (YE2)) in the presence of a base.

[Wherein R ¹ , R ² , R ⁹² and Z ³ represent the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
Examples of the base used in the reaction include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclononene and the like. Alkali metal carbonates such as organic bases, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium hydroxide, hydroxide Alkali metal hydroxides such as sodium, potassium hydroxide and cesium hydroxide, alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride, alkali metals such as lithium hydride, sodium hydride and potassium hydride Hydrogenation , Sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
In the reaction, with respect to 1 mol of the compound (YE1), the compound (YE2) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 10 mol.
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
In the reaction, an additive may be added as necessary, and examples of the additive include 18-crown-6-ether and dibenzo-18-crown-6-ether. These additives are usually used in a proportion of 0.001 to 1.2 mol with respect to 1 mol of the compound (YE1).
After completion of the reaction, the compound (YE3) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, it can be purified by chromatography, recrystallization or the like.

(Reference production method AF)
In the compound represented by the formula (YF2) (hereinafter referred to as the compound (YF2)), the compound (YE1) and the compound represented by the formula (YF1) (hereinafter referred to as the compound (YF1)) are present in the presence of a base. It can manufacture by making it react.

[Wherein, R ¹ , R ² , Z ² , Z ³ , R ⁹² , and Z ¹²⁰ represent the same meaning as described above. ]
This reaction can be carried out according to Reference Synthesis Method H.

(Reference production method AG)
Compound (YB1) can be produced by reacting compound (YF2) with hydrazines.

[Wherein R ¹ , R ² , R ⁹² , Z ² and Z ³ represent the same meaning as described above. ]
This reaction can be carried out according to Reference Synthesis Method I.

(Reference synthesis method AH)
A compound represented by formula (YH3) (hereinafter referred to as compound (YH3)) is a compound represented by formula (YH1) (hereinafter referred to as compound (YH1)) and a compound represented by formula (YH2) ( Hereinafter, it can be produced by reacting with compound (YH2).

[Wherein R ¹ , R ² , R ³ , R ⁹² , R ¹⁰⁰ and Z ³ represent the same meaning as described above, Rf represents a C1-C3 perfluoroalkyl group, and n represents 0 or 1. ]
The reaction is usually carried out in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, nitriles such as acetonitrile and propionitrile, Methanol, ethanol, alcohols such as isopropanol, water and mixtures thereof.
In the reaction, compound (YH2) is usually used at a ratio of 1 to 10 mol per 1 mol of compound (YH1).
The reaction temperature of the reaction is usually in the range of −78 to 150 ° C. The reaction time is usually in the range of 0.1 to 72 hours.
After completion of the reaction, the compound (YH3) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, it can be purified by chromatography, recrystallization or the like.

(Reference Synthesis Method AI)
A compound represented by the formula (YI1) (hereinafter referred to as compound (YI1)) can be produced by reacting compound (YH3) in the presence of an acid.

[Wherein R ¹ , R ² , R ⁹² , Z ³ and Rf represent the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, nitriles such as acetonitrile and propionitrile, Methanol, ethanol, alcohols such as isopropanol, water and mixtures thereof.
Examples of the acid used in the reaction include acetic acid, hydrochloric acid, hydrobromic acid and the like, and these aqueous solutions can also be used as a solvent.
In the reaction, an acid is usually used at a ratio of 1 to 10 mol with respect to 1 mol of the compound (YH3).
The reaction temperature of the reaction is usually in the range of −78 to 150 ° C. The reaction time is usually in the range of 0.1 to 72 hours.
After completion of the reaction, the compound (YI1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, it can be purified by chromatography, recrystallization or the like.

(Reference production method AJ)
The compound represented by the formula (YJ1) (hereinafter referred to as the compound (YJ1)) can be produced by reacting the compound (YE3) with the compound (YH2).

[Wherein, n, R ¹ , R ² , R ⁹² , R ¹⁰⁰ and Z ³ represent the same meaning as described above. ]
The reaction is performed in a solvent or without a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, nitriles such as acetonitrile and propionitrile, And mixtures thereof. An acid may be added to the reaction if necessary. Examples of the acid used in the reaction include hydrochloric acid, sulfuric acid, acetic acid, hydrobromic acid, p-toluenesulfonic acid and the like. In the reaction, with respect to 1 mol of the compound (YE3), the compound (YH2) is usually used in a proportion of 1 to 100 mol, and the acid is usually used in a proportion of 1 to 100 mol.
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the reaction mixture is concentrated under reduced pressure, extracted with an organic solvent, and the organic layer is dried, concentrated, filtered and post-treatment operations such as filtration can be performed to isolate the compound (YJ1). The isolated compound of the present invention can be further purified by chromatography, recrystallization and the like.

(Reference synthesis method AK)
The compound represented by the formula (YK1) (hereinafter referred to as the compound (YK1)) is the same as the compound represented by the formula (YJ1K) (hereinafter referred to as the compound (YJ1K)) and N, N-dimethylformamide and oxy. It can be produced by reacting with a formylating agent prepared from phosphorus chloride and then reacting with water.

[Wherein, R ¹ , R ² and R ⁹² represent the same meaning as described above. ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane and n-pentane, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, methyl tert. -Ethers such as butyl ether and diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1,3-dimethyl-2 Acid amides such as imidazolidinone and N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, acetonitrile Nitriles such as propionitrile and mixtures thereof.
The formylating agent in the reaction is a mixture of 1 to 10 mol of N, N-dimethylformamide and 1 to 10 mol of phosphorus oxychloride with respect to 1 mol of compound (YJ1K), and water is compound (YJ1K). ) It is used at a ratio of 1 to 10 moles per mole.
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (YK1) may be isolated by performing post-treatment operations such as adding usually 1 mol or more of water, extracting the reaction mixture with an organic solvent, and drying and concentrating the organic layer. it can. The isolated compound of the present invention can be further purified by chromatography, recrystallization and the like.

(Reference synthesis method AL)
In the compound represented by the formula (YL2) (hereinafter referred to as the compound (YL2)), the compound (YK1) and the compound represented by the formula (YL1) (hereinafter referred to as the compound (YL1)) are present in the base. It can manufacture by making it react under.

[Wherein R ¹ , R ² and R ⁹² represent the same meaning as described above, R ⁵² represents a C1-C2 alkyl group, and Z ^2H represents OR ⁵² or SR ⁵² . ]
The reaction is usually performed in a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
Examples of the base used in the reaction include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclononene and the like. Alkali metal carbonates such as organic bases, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium hydroxide, hydroxide Alkali metal hydroxides such as sodium, potassium hydroxide and cesium hydroxide, alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride, alkali metals such as lithium hydride, sodium hydride and potassium hydride Hydrogenation , Sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
In the reaction, with respect to 1 mol of the compound (YK1), the compound (YL1) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 10 mol.
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
The reaction is carried out by reacting the compound (YL1) with an alkali metal carbonate, alkali metal hydrogencarbonate, alkali metal hydroxide, alkali metal halide, alkali metal hydride or alkali metal alkoxide. A salt can be prepared in advance and used in the reaction. Examples of the metal salt of the compound (YL1) that can be used include sodium methoxide, sodium ethoxide, sodium propoxide, sodium isopropoxide, potassium methoxide, potassium ethoxide, sodium thiomethoxide, sodium thioethoxide. Is mentioned.
In the reaction, the metal salt of compound (YL1) is usually used at a ratio of 1 to 10 mol per 1 mol of compound (YK1).
After completion of the reaction, the compound (YL2) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Alternatively, the compound (YL2) can be isolated by performing post-treatment operations such as filtration and concentration of the reaction mixture. Further, it can be purified by chromatography, recrystallization or the like.

(Reference synthesis method AM)
The compound represented by the formula (YI2) (hereinafter referred to as the compound (YI2)) is reacted with the compound represented by the formula (YM1) (hereinafter referred to as the compound (YM1)) with a reducing agent in the presence of an acid. Can be manufactured.

[Wherein R ¹ , R ² and R ⁹² represent the same meaning as described above, and Z ^2A represents Z ^2H and a chlorine atom. ]
The reaction is performed in a solvent or without a solvent.
Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether. Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
Examples of the reducing agent used in the reaction include metal boronate compounds such as lithium borohydride, sodium borohydride and potassium borohydride, and trialkylsilane compounds such as triethylsilane.
Examples of the acid used in the reaction include boron trifluoride and trifluoroacetic acid.
In the reaction, with respect to 1 mol of the compound (YM1), the reducing agent is usually used in a proportion of 1 to 10 mol, and the acid is usually used in a proportion of 1 to 10 mol or a large excess.
The reaction temperature of the reaction is usually in the range of −20 to 150 ° C. The reaction time is usually in the range of 0.1 to 24 hours.
After completion of the reaction, the compound (YI2) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Alternatively, compound (YI2) can be isolated by performing post-treatment operations such as filtration and concentration of the reaction mixture. Further, it can be purified by chromatography, recrystallization or the like.

Each of the present bactericidal active compounds has an action mechanism different from that of the present tetrazolinone compound, and is classified into the following groups (A1) and (A2).
Group (A1): azole compound propiconazole, prothioconazole, triazimenol, prochloraz, penconazole, tebuconazole, flusilazole, diniconazole, bromconazole, epoxiconazole, difenoconazole, cyproconazole, metconazole, triflumizole, tetra A group consisting of conazole, microbutanyl, fenbuconazole, hexaconazole, fluquinconazole, triticonazole, viteltanol, imazalyl, ipconazole, cimeconazole, himexazole, etridazole and flutriahol.
Group (A2): carboxamide compounds bixafen, benzobindiflupyr, floxapyroxide, penthiopyrad, N- (1,1,3-trimethylindan-4-yl) -1-methyl-3-difluoromethylpyrazole-4- Carboxylic acid amide,
A compound represented by the following formula (b):

The group consisting of isofetamide, isopyrazam, boscalid, fluopyram, sedaxane, penflufen, flutolanil, mepronil, carboxin, tifluzamide and flametopyr.
These bactericidal active compounds are all known compounds, and are described in, for example, “THE PESTICIDE MANUAL-14th EDITION (BCPC) ISBN 190139396142”, International Publication No. 2011/162397, or International Publication No. 2007/072999. ing. These compounds can be obtained from commercial preparations or synthesized by known methods. As an aspect of N- (1,1,3-trimethylindan-4-yl) -1-methyl-3-difluoromethylpyrazole-4-carboxylic acid amide in the present invention, a compound represented by the formula (a1)

And / or formula (a2)

The compound represented by these is mention | raise | lifted.
The bactericidal active compounds are shown in [Table 1] and [Table 2].

The weight ratio of the present tetrazolinone compound and the present bactericidal active compound in the composition of the present invention is, for example, the present tetrazolinone compound / the present bactericidal active compound = 0.01 / 1 to 500/1, 0.1 / 1 to 10/1. And 0.1 / 1 to 3/1, and 0.3 / 1 to 3/1 is particularly preferable.

The composition of the present invention may be a mixture of the tetrazolinone compound and the bactericidal active compound itself, but the composition of the present invention is usually mixed with the tetrazolinone compound, the bactericidal active compound and an inert carrier, if necessary. A surfactant and other formulation adjuvants are added.
The composition of the present invention may be formulated into oils, emulsions, flowables, wettable powders, granular wettable powders, powders, granules and the like. Such a preparation can be used as a plant disease control agent as it is or with addition of other inactive ingredients.
The composition of the present invention contains the present tetrazolinone compound and the present bactericidal active compound in a total amount of usually 0.1 to 99% by weight, preferably 0.2 to 90% by weight, more preferably 1 to 80% by weight.

Examples of the solid carrier used in the formulation include clays (for example, kaolin, diatomaceous earth, synthetic hydrous silicon oxide, fubasamic clay, bentonite, acidic clay), talc, and other inorganic minerals (for example, sericite, Examples thereof include fine powders or granular materials such as quartz powder, sulfur powder, activated carbon, calcium carbonate, and hydrated silica). Examples of the liquid carrier include water and alcohols (eg, methanol, ethanol). , Ketones (for example, acetone, methyl ethyl ketone), aromatic hydrocarbons (for example, benzene, toluene, xylene, ethylbenzene, methylnaphthalene), aliphatic hydrocarbons (for example, n-hexane, cyclohexanone, kerosene), esters (For example, ethyl acetate, butyl acetate), nitriles (for example, acetonitrile, isobutyronitrate) Le), ethers (e.g., dioxane, diisopropyl d - ether), acid amides (e.g., DMF, dimethylacetamide), halogenated hydrocarbons (e.g., dichloroethane, trichlorethylene, carbon tetrachloride) and the like.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylene compounds thereof, polyoxyethylene glycol ethers, polyvalent Examples include alcohol esters and sugar alcohol derivatives.

Examples of other formulation adjuvants include, for example, fixing agents, dispersants, and stabilizers. Specifically, casein, gelatin, polysaccharides (for example, starch, arabic gum, cellulose derivatives, alginic acid), lignin derivatives, Bentonite, sugars, synthetic water-soluble polymers (for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids), PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol) ), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, fatty acid or ester thereof, and the like.

The composition of the present invention is also prepared by formulating the tetrazolinone compound and the bactericidal active compound by the above-described methods, and then diluting with water as necessary to prepare the tetrazolinone compound and the bactericidal active compound. Can also be prepared by mixing the preparations containing these or their dilutions.

The composition of the present invention can be used to protect plants from plant diseases.

The control method of the present invention comprises treating a plant or soil for cultivating the plant with the present composition, or treating the tetrazolinone compound and the bactericidal active compound separately on the soil for cultivating the plant or plant, Can control disease

The method of applying the composition of the present invention is not particularly limited as long as the composition of the present invention can be applied substantially, but for example, treatment of plants such as foliage spraying, plants such as soil treatment, etc. To seeds such as seed sterilization and so on.

The application amount of the composition of the present invention varies depending on weather conditions, formulation form, application time, application method, application location, target disease, target crop, etc., but is usually 1 to 500 g, preferably 2 to 200 g per 1000 m ^2. is there. Emulsions, wettable powders, suspensions and the like are usually diluted with water and applied. In this case, the concentration of the composition of the present invention after dilution is usually 0.0005 to 2% by weight, preferably 0.005 to It is 1% by weight, and powders, granules and the like are usually applied as they are without dilution. In the treatment for seeds, the amount of the composition of the present invention per 1 kg seed is usually applied in the range of 0.001 to 100 g, preferably 0.01 to 50 g.

Examples of habitats for plant diseases in the present invention include paddy fields, fields, tea gardens, orchards, non-agricultural lands, houses, seedling trays and seedling boxes, seedling culture soils and seedling mats.

The composition of the present invention can be used as a plant disease control agent in agricultural land such as fields, paddy fields, lawns, orchards. The composition of the present invention can control diseases of the cultivated land in cultivated lands where the following “plants” and the like are cultivated.

Agricultural crops: corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybeans, peanuts, buckwheat, sugar beet, rapeseed, sunflower, sugarcane, tobacco, etc., vegetables; solanaceous vegetables (eggplants, tomatoes, peppers) , Pepper, potato, etc.), cucurbitaceae vegetables (cucumber, pumpkin, zucchini, watermelon, melon, etc.), cruciferous vegetables (radish, turnip, horseradish, cold rabi, Chinese cabbage, cabbage, mustard, broccoli, cauliflower -), Asteraceae vegetables (burdock, garlic, artichoke, lettuce, etc.), Liliaceae vegetables (leek, onion, garlic, asparagus), Aceraceae vegetables (carrots, parsley, celery, American redfish, etc.) , Red vegetables (spinach, chard, etc.), perilla vegetables (perilla, mint, basil) ), Strawberry, sweet potato, yam, taro, etc.,
Bridegroom,
Foliage plant,
Fruit trees; pears (apples, pears, Japanese pears, quince, quince, etc.), nuclear fruits (peaches, plums, nectarines, ume, sweet cherry, apricots, prune, etc.), citrus fruits (Satsuma mandarin, orange, lemon, lime) , Grapefruit, etc.), nuts (chestnut, walnut, hazel, almond, pistachio, cashew nut, macadamia nut, etc.), berries (blueberry, cranberry, blackberry, raspberry) -Grapes, oysters, olives, loquat, bananas, coffee, dates, coconuts, etc.
Trees other than fruit trees; tea, mulberry, flowering trees, street trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak, poplar, redwood, fu, sycamore, zelkova, black bean, peach tree, tsuga, rat, Pine, spruce, yew).

The above “plants” include genetically modified crops.

Examples of plant diseases that can be controlled by the composition of the present invention include phytopathogenic fungi such as filamentous fungi, and the following can be mentioned in more detail, but are not limited thereto.

Rice diseases: blast (Magnaporthe grisea), sesame leaf blight (Cochliobolus miyabeanus), blight (Rhizoctonia solani), idiotic seedling (Gibberella fujikuruoi).
Wheat diseases: powdery mildew (Erysiphe graminis), red mold disease (Fusarium gramaminerum, F. avenacerum, F. culmorum, Microdochium nitrid, red rust (Puccinia isp. (Microlectriella nivale), Snow rot microspora nuclear disease (Typhula sp.), Bare smut (Ustylago tritici), Tuna scab (Tilleletia carripe), Pseucercosporella morposis (Pseudocercosporella herposis) Blight (Stagonospo) a nodorum), Kimadarabyo (Pyrenophora tritici-repentis).
Diseases of barley: powdery mildew (Erysiphe graminis), red mold disease (Fusarium gramaminerum, F. avenacerum, F. culmorum, Microdochium nitrifle, black punishment) Ustilago nuda), cloud disease (Rhynchosporium secalis), reticular disease (Pyrenophora teres), spot disease (Cochliobolus sativus), leafy leaf disease (Pyrenophora graminea), and Rhizonia a.
Diseases of corn: smut (Ustilago maydis), sesame leaf blight (Cochliobolus heterostrohus), leprosy (Gloeocercospora sorgi), southern rust (Puccinia polysoria), gray leaf spot disease Rhizoctonia solani due to seedling.

Diseases of citrus: Black spot disease (Diaporthe citri), common scab (Elsinoe fawceti), fruit rot (Penicillium digitatum, P. italicum), Phytophthora paraphysitic or Phytophthora or Phytophthora parathitosis.
Diseases of apples: Monilia mary, rot (Valsa ceratosperma), powdery mildew (Podospataera leucotrica), spotted leaf disease (Alternaria altertaenta black) , Phytophactora catorum.
Pear diseases: Venturia nashicola, V. pirina, Black spot (Alternaria alternata Japan pearpathotype), Gimnosporangium haraeumto, disease
Peach diseases: Monilinia fracticola, black scab (Cladosporium carpophilum), Phomopsis spoilage (Phomopsis sp.).
Grape diseases: black scab (Elsinoe ampelina), late rot (Glomerella gingulata), powdery mildew (Uncinula adipelodia), black rot (Gikonivaladi) .
Oyster diseases: Anthracnose (Gloeosporium kaki), deciduous leaf disease (Cercospora kaki, Mycosphaerella nawae).
Diseases of cucurbits: Anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca furiginea), vine blight (Mycosphaerella meloniis), vine scab (Fusarium oxysporum), por disease (fusarium oxysporum) ), Seedling blight (Pythium sp.);
Diseases of tomato: Alternaria solani, leaf mold (Cladosporium fulvum), plague (Phytophthora infestans).
Diseases of eggplant: brown spot disease (Phomopsis vexans), powdery mildew (Erysiphe cichoacearum).
Diseases of cruciferous vegetables: black spot disease (Alternaria japonica), white spot disease (Cercosporella brassicae), clubroot (Plasmodiophora brassicae), downy mildew (Peronospora parasitica).
Diseases of leek: rust (Puccinia allii), downy mildew (Peronospora destructor).

Diseases of soybean: Purcosis (Cercospora kikuchii), black scab (Elsinoe glycines), black spot (Diaporthe phaseolum var. Phytophthora sojae, Rhizoctonia solani, Corynespora casiicola, Sclerotinia sclerotiorum.
Kidney disease: Anthracnose (Colletotrichum lindemthianum).
Peanut disease: black astringency (Cercospora personata), brown spot (Cercospora arachidicola), white silkworm (Sclerotium rolfsii).
Pea disease: powdery mildew (Erysiphe pisi).
Potato diseases: Alternaria solani, Phytophthora infestans, Sputum rot septica, Spongosporia subteranean f.
Strawberry disease: powdery mildew (Sphaerotheca humuli), anthracnose (Glomerella singulata).
Tea diseases: net blast (Exobasidium reticulatum), white scab (Elsinoe leucospila), ring spot disease (Pestalotiosis sp.), Anthracnose (Colletotrichum theae-sinensis).
Tobacco disease: Alternaria longipes, powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), epidemic (Phytophyti.
Rapeseed diseases: Sclerotinia sclerotiorum, Rhizoctonia solani, and Rhizoctonia solani.
Cotton disease; Rhizoctonia solani caused by Rhizoctonia spp.
Diseases of sugar beet: brown spot disease (Cercospora beticola), leaf rot (Thanatephorus cucumeris), root rot (Thanatephorus cucumeris), black root disease (Aphanomyces cochlioides).
Rose diseases: black spot (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa), downy mildew (Peronospora sparsa).
Diseases of chrysanthemum and asteraceae vegetables: downy mildew (Bremia lactucae), brown spot disease (Septoria chrysanthemi-indici), white rust (Puccinia horiana).
Diseases of various crops: Diseases caused by Pythium spp. (Phythium aphanidermatum, Pythium debarianum, Pythium graminicola, Pythium irregulare, Pythium ultimatum), Gray mold disease (Botritris rot)
Radish disease: Alternaria brassicicola.
Diseases of buckwheat: Dollar spot disease (Sclerotinia homeocarpa), Brown patch disease and Large patch disease (Rhizotonia solani).
Banana disease: Sigatoka disease (Mycosphaerella fijiensis, Mycosphaerella musicola).
Sunflower disease: downy mildew (Plasmopara halstedii).
Aspergillus genus, Penicillium genus, Fusarium genus, Gibberella genus, Tricoderder genus, Thielaviopsis genus, Rhizopus genus, Mucor genus, Corticium genus, Phoma genus, Rhizoctonia genus Disease.
Viral diseases of various crops mediated by Polymixa genus or Olpidium genus.

Next, the method for synthesizing the present tetrazolinone compound and the formulation examples and test examples of the composition of the present invention will be described more specifically, but the present invention is not limited to these examples.
First, a synthesis example of the tetrazolinone compound is shown.

Synthesis example 1
3.1 g of 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 9 and 4- (5- A mixture of chloro-1,4-dimethyl-1H-pyrazol-3-yl) -2-methyl-phenol 2.7 g, potassium carbonate 1.95 g and acetonitrile 70 mL was stirred with heating under reflux for 4 hours. Cool to room temperature, filter the reaction mixture and concentrate the filtrate. The obtained residue was subjected to silica gel column chromatography to give 1- {3-methyl-2- [2-methyl-4- (5-chloro-1,4-dimethyl-1H-pyrazol-3-yl) -phenoxy. 3.0 g of methyl] -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 1) was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.45-7.39 (3H, m), 7.37 (1H, dd, J = 8.5, 2.1 Hz), 7.28 (1H, dd, J = 7.0, 2.4 Hz), 6.88 (1H, d, J = 8.5 Hz), 5.06 (2H, s), 3.85 (3H, s), 3.62 (3H, s), 2.51 (3H, s), 2.15 (3H, s), 2.13 (3H, s).

Synthesis example 2
In Synthesis Example 1, 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 3 was used instead of 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one. The same reaction was carried out using 3-chlorophenyl) -4-methyl-1,4-dihydrotetrazol-5-one, and 1- {3-chloro-2- [2-methyl-4- (5-chloro-1) , 4-Dimethyl-1H-pyrazol-3-yl) -phenoxymethyl] -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 2).

¹ H-NMR (CDCl ₃ ) δ: 7.62 (1H, dd, J = 8.0, 1.4 Hz), 7.47 (1H, t, J = 8.0 Hz), 7.41-7. 39 (2H, m), 7.36 (1H, dd, J = 8.4, 2.2 Hz), 6.89 (1H, d, J = 8.5 Hz), 5.35 (2H, s), 3.85 (3H, s), 3.60 (3H, s), 2.14 (3H, s), 2.06 (3H, s).

Synthesis example 3
In Synthesis Example 1, 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 10 was used instead of 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one. The same reaction was carried out using 3-ethylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one, and 1- {3-ethyl-2- [2-methyl-4- (5-chloro- 1,4-Dimethyl-1H-pyrazol-3-yl) -phenoxymethyl] -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 3) was obtained. .

¹ H-NMR (CDCl ₃ ) δ: 7.50-7.44 (2H, m), 7.40 (1H, d, J = 1.6 Hz), 7.39-7.36 (1H, m) , 7.28 (1H, dd, J = 7.1, 2.1 Hz), 6.89 (1H, d, J = 8.2 Hz), 5.08 (2H, s), 3.85 (3H, s), 3.59 (3H, s), 2.85 (2H, q, J = 7.6 Hz), 2.15 (3H, s), 2.11 (3H, s), 1.28 (3H) , T, J = 7.7 Hz).

Synthesis example 4
1- {3-Methyl-2- [2-methyl-4- (1,5-dimethyl-1H-pyrazol-3-yl) -phenoxymethyl] -phenyl} -4 described in Reference Synthesis Example 41 at room temperature A mixture of 0.47 g of methyl-1,4-dihydrotetrazol-5-one, 0.17 g of N-chlorosuccinimide and 10 ml of chloroform was stirred for 12 hours. The mixture was extracted with chloroform, washed with a saturated aqueous sodium chloride solution, the organic layer was dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel chromatography to give 1- {3-methyl-2- [2-methyl-4- (4-chloro-1,5-dimethyl-1H-pyrazol-3-yl) -phenoxymethyl. ] 0.34 g of -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 4) was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.66 (1H, dd, J = 8.4, 2.2 Hz), 7.61-7.60 (1H, m), 7.44-7.39 ( 2H, m), 7.29-7.27 (1H, m), 6.89 (1H, d, J = 8.5 Hz), 5.06 (2H, s), 3.82 (3H, s) 3.62 (3H, s), 2.51 (3H, s), 2.28 (3H, s), 2.13 (3H, s).

Synthesis example 5
In Synthesis Example 1, 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 43 was used instead of 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one. The same reaction is carried out using 3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one to give 1- {3-methoxy-2- [2-methyl-4- (5-chloro- 1,4-Dimethyl-1H-pyrazol-3-yl) -phenoxymethyl] -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 5) was obtained. .

¹ H-NMR (CDCl ₃ ) δ: 7.49 (1H, t, J = 8.2 Hz), 7.40-7.39 (1H, m), 7.37 (1H, dd, J = 8. 5, 2.3 Hz), 7.13-7.09 (2H, m), 6.94 (1H, d, J = 8.5 Hz), 5.32 (2H, s), 3.96 (3H, s), 3.87 (3H, s), 3.62 (3H, s), 2.17 (3H, s), 2.06 (3H, s).

Synthesis Example 6
1- (2-Bromomethyl-3-ethylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one 0.3 g described in Reference Synthesis Example 10 and 2-methyl-4 described in Reference Synthesis Example 24 A mixture of 0.27 g of (1-methyl-5-trifluoromethyl-1H-pyrazol-3-yl) -phenol, 0.15 g of potassium carbonate and 10 mL of acetonitrile was stirred with heating under reflux for 4 hours. Cool to room temperature, filter the reaction mixture and concentrate the filtrate. The obtained residue was subjected to silica gel column chromatography to give 1- {3-ethyl-2- [2-methyl-4- (1-methyl-5-trifluoromethyl-1H-pyrazol-3-yl) -phenoxy. 0.3 g of methyl] phenyl} -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 6) was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.53-7.50 (2H, m), 7.48-7.43 (2H, m), 7.28 (1H, dd, J = 7.1) 2.1 Hz), 6.88 (1H, d, J = 8.2 Hz), 6.80 (1H, s), 5.09 (2H, s), 4.01 (3H, s), 3.58 (3H, s), 2.85 (2H, q, J = 7.6 Hz), 2.11 (3H, s), 1.28 (3H, t, J = 7.6 Hz).

Synthesis example 7
In Synthesis Example 1, instead of 4- (5-chloro-1,4-dimethyl-1H-pyrazol-3-yl) -2-methyl-phenol, 4- (1,4- The same reaction was carried out using dimethyl-5-methoxy-1H-pyrazol-3-yl) -2-methyl-phenol, and 1- {3-methyl-2- [2-methyl-4- (1,4- Dimethyl-5-methoxy-1H-pyrazol-3-yl) -phenoxymethyl] -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 7) was obtained. .

¹ H-NMR (CDCl ₃ ) δ: 7.44-7.39 (3H, m), 7.36 (1H, dd, J = 8.5, 2.2 Hz), 7.29-7.26 ( 1H, m), 6.87 (1H, d, J = 8.5 Hz), 5.06 (2H, s), 3.94 (3H, s), 3.71 (3H, s), 3.62 (3H, s), 2.51 (3H, s), 2.13 (3H, s), 2.12 (3H, s).

Synthesis example 8
1- {3-methyl-2- [2-methyl-4- (5-aminocarbonyl-1,4-dimethyl-1H-pyrazol-3-yl) -phenoxy described in Reference Synthesis Example 40 at 0 ° C. 0.26 g of phosphorus oxychloride was added to a mixture of 0.5 g of methyl] -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one and 10 ml of pyridine. After stirring at room temperature for 3 hours, 30 ml of water was added. The precipitate was collected by filtration, washed with 10 ml of water and 10 ml of hexane, dried under reduced pressure, and 1- {3-methyl-2- [2-methyl-4- (5-cyano-1,4-dimethyl-1H-pyrazole). -3-yl) -phenoxymethyl] -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 8) (0.38 g) was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.46-7.40 (3H, m), 7.37 (1H, dd, J = 8.4, 1.8 Hz), 7.28 (1H, dd, J = 6.9, 2.2 Hz), 6.90 (1H, d, J = 8.4 Hz), 5.07 (2H, s), 4.03 (3H, s), 3.64 (3H, s), 2.51 (3H, s), 2.33 (3H, s), 2.13 (3H, s).

Synthesis Example 9
In Synthesis Example 1, instead of 4- (5-chloro-1,4-dimethyl-1H-pyrazol-3-yl) -2-methyl-phenol, 4- (1,4,4) described in Reference Synthesis Example 46 was used. The same reaction was carried out using 5-trimethyl-1H-pyrazol-3-yl) -2-methyl-phenol, and 1- {3-methyl-2- [2-methyl-4- (1,4,5- Trimethyl-1H-pyrazol-3-yl) -phenoxymethyl] -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 9) was obtained.

¹ H-NMR (CDCl ₃ ) δ: 8.48-8.44 (3H, m), 8.41 (1H, dd, J = 8.2, 2.3 Hz), 8.31 (1H, dd, J = 7.0, 2.9 Hz), 7.91 (1H, d, J = 8.5 Hz), 6.10 (2H, s), 4.83 (3H, s), 4.66 (3H, s), 3.55 (3H, s), 3.24 (3H, s), 3.16 (3H, s), 3.14 (3H, s).

Synthesis Example 10
In Synthesis Example 6, instead of 2-methyl-4- (1-methyl-5-trifluoromethyl-1H-pyrazol-3-yl) -phenol, 4- (1,4,4) described in Reference Synthesis Example 46 was used. The same reaction was carried out using 5-trimethyl-1H-pyrazol-3-yl) -2-methyl-phenol, and 1- {3-ethyl-2- [2-methyl-4- (1,4,5- Trimethyl-1H-pyrazol-3-yl) -phenoxymethyl] -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 10) was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.49-7.43 (2H, m), 7.41-7.40 (1H, m), 7.37 (1H, dd, J = 8.4, 2.2 Hz), 7.28 (1 H, dd, J = 7.0, 2.2 Hz), 6.88 (1 H, d, J = 8.5 Hz), 5.08 (2 H, s), 3. 80 (3H, s), 3.58 (3H, s), 2.85 (2H, q, J = 7.6 Hz), 2.21 (3H, s), 2.11 (6H, s), 1 .27 (3H, q, J = 7.7 Hz).

Synthesis Example 11
In Synthesis Example 5, instead of 4- (5-chloro-1,4-dimethyl-1H-pyrazol-3-yl) -2-methyl-phenol, 4- (1,4,4) described in Reference Synthesis Example 46 was used. A similar reaction is carried out using 5-trimethyl-1H-pyrazol-3-yl) -2-methyl-phenol, and 1- {3-methoxy-2- [2-methyl-4- (1,4,5- Trimethyl-1H-pyrazol-3-yl) -phenoxymethyl] -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 10) was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.46 (1H, t, J = 8.2 Hz), 7.37 (1H, d, J = 1.6 Hz), 7.33 (1H, dd, J = 8.2, 2.3 Hz), 7.09 (1H, d, J = 3.2 Hz), 7.07 (1H, d, J = 2.5 Hz), 6.90 (1H, d, J = 8) .2 Hz), 5.28 (2H, s), 3.92 (3H, s), 3.79 (3H, s), 3.58 (3H, s), 2.20 (3H, s), 2 .09 (3H, s), 2.03 (3H, s).

Next, a reference synthesis example is shown for the synthesis of the synthesis intermediate of the tetrazolinone compound.

Reference synthesis example 1
21.9 g of anhydrous aluminum chloride was added to 250 mL of N, N-dimethylformamide under ice cooling, and the mixture was stirred for 15 minutes. To this was added 10.7 g of sodium azide and stirred for 15 minutes. Then, 25.0 g of 1-chloro-3-isocyanato-2-methylbenzene was added and heated at 80 ° C. for 5 hours. After cooling, the reaction solution was added to a mixture of 35 g of sodium nitrite, 2 L of water and 500 g of ice with stirring. The mixture was acidified with 10% hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and 1- (2-methyl-3-chlorophenyl) -1,4-dihydrotetrazol-5-one. 0 g was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 2.32 (3H, s), 7.28-7.36 (2H, m), 7.57 (1H, dd, J = 6.8, 2 .2 Hz), 13.08 (1 H, s).

Reference synthesis example 2
To a mixture of 10.00 g of 1- (2-methyl-3-chlorophenyl) -1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 1 and 100 mL of N, N-dimethylformamide was added 60% under ice cooling. 2.30 g of sodium hydride was added. The mixture was warmed to room temperature and stirred for 1 hour. To the reaction mixture, 3.2 mL of methyl iodide was added under ice cooling. The mixture was warmed to room temperature and stirred for 14 hours. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with 10% hydrochloric acid, water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 1.56 g of 1- (2-methyl-3-chlorophenyl) -4-methyl-1,4-dihydrotetrazol-5-one.

¹ H-NMR (CDCl ₃ ) δ (ppm): 2.30 (3H, s), 3.73 (3H, s), 7.27 (1H, d, J = 2.7 Hz), 7.28 ( 1H, d, J = 7.1 Hz), 7.52 (1H, dd, J = 2.7, 6.8 Hz).

Reference synthesis example 3
1- (2-Methyl-3-chlorophenyl) -4-methyl-1,4-dihydrotetrazol-5-one 1.56 g, 1,1′-azobis (cyclohexane-1-carbonitrile described in Reference Synthesis Example 2 ) A mixture of 0.34 g, 1.42 g of N-bromosuccinimide and 30 mL of chlorobenzene was stirred with heating under reflux for 5 hours. After cooling, water was poured into the reaction solution and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 1.94 g of 1- (2-bromomethyl-3-chlorophenyl) -4-methyl-1,4-dihydrotetrazol-5-one.

¹ H-NMR (CDCl ₃ ) δ (ppm): 3.76 (3H, s), 4.69 (2H, s), 7.35 (1H, dd, J = 1.2, 8.1 Hz), 7.43 (1H, t, J = 8.1 Hz), 7.58 (1H, dd, J = 1.2, 8.1 Hz).

Reference synthesis example 4
19.7 g of anhydrous aluminum chloride was added to 220 mL of N, N-dimethylformamide under ice cooling and stirred for 15 minutes. After adding 9.6 g of sodium azide and stirring for 15 minutes, 30.3 g of 1-bromo-3-isocyanato-2-methylbenzene described in Reference Synthesis Example 42 was added and heated at 80 ° C. for 5 hours. After cooling, the reaction solution was added to a mixture of 33 g of sodium nitrite, 2 L of water and 500 g of ice with stirring. The mixture was acidified with 10% hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and 1- (2-methyl-3-bromophenyl) -1,4-dihydrotetrazol-5-one 31. .4 g was obtained.

¹ H-NMR (DMSO-D ₆ ) δ (ppm): 2.22 (3H, s), 7.34 (1H, t, J = 7.2 Hz), 7.49 (1H, dd, J = 8) .2, 1.1 Hz), 7.82 (1H, dd, J = 8.0, 1.0 Hz), 14.72 (1H, s).

Reference synthesis example 5
To a mixture of 31.40 g of 1- (2-methyl-3-bromophenyl) -1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 4 and 250 mL of N, N-dimethylformamide was added 60 mL under ice-cooling. 5.90 g of% sodium hydride was added. The mixture was warmed to room temperature and stirred for 1 hour. To the reaction mixture, 8.4 mL of methyl iodide was added under water cooling. The mixture was warmed to room temperature and stirred for 14 hours. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with 10% hydrochloric acid, water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 8.47 g of 1- (2-methyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one.

¹ H-NMR (CDCl ₃ ) δ (ppm): 2.33 (3H, s), 3.73 (3H, s), 7.21 (1H, dt, J = 0.5, 7.8 Hz), 7.30 (1H, dd, J = 1.0, 8.0 Hz), 7.71 (1H, dd, J = 1.2, 8.3 Hz).

Reference synthesis example 6
8.47 g of 1- (2-methyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 5, 1,1′-azobis (cyclohexane-1-carbohydrate (Nitrile) 1.54 g, N-bromosuccinimide 6.44 g and chlorobenzene 125 mL were stirred with heating under reflux for 5 hours. After cooling, water was poured into the reaction solution and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 7.52 g of 1- (2-bromomethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one.

¹ H-NMR (CDCl ₃ ) δ (ppm): 3.76 (3H, s), 4.71 (2H, s), 7.34 (1H, t, J = 7.8 Hz), 7.38 ( 1H, dd, J = 8.0, 1.7 Hz), 7.77 (1H, dd, J = 7.8, 1.7 Hz).

Reference synthesis example 7
A mixture of 45.0 g of 1- (2-bromomethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 6, 37.4 g of sodium methoxide and 600 mL of tetrahydrofuran was obtained. Stir at room temperature for 3 hours. Saturated aqueous sodium hydrogen carbonate was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and dried over anhydrous sodium sulfate. After concentration under reduced pressure, 36.2 g of 1- (2-methoxymethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 3.23 (3H, s), 3.72 (3H, s), 4.67 (2H, s), 7.33 (1H, t, J = 7.8 Hz), 7.38 (1H, dd, J = 1.2, 8.1 Hz), 7.76 (1H, dd, J = 1.5, 7.8 Hz).

Reference synthesis example 8
1- (2-methoxymethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one 36.2 g described in Reference Synthesis Example 7, 23.2 g of methyl boronic acid, cesium fluoride 66. A mixture of 7 g, [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct 10.6 g and dioxane 500 ml was stirred at 90 ° C. for 5.5 hours. After cooling, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 25.6 g of 1- (2-methoxymethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one.

¹ H-NMR (CDCl ₃ ) δ (ppm): 2.48 (3H, s), 3.23 (3H, s), 3.72 (3H, s), 4.42 (2H, s), 7 .21 (1H, t, J = 5.1 Hz), 7.35 (2H, d, J = 4.8 Hz).

Reference synthesis example 9
25.6 g of 1- (2-methoxymethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 8, 50 mL of acetic acid and 25% hydrogen bromide-acetic acid solution 50 mL of the mixture was stirred at 65 ° C. for 1 hour. Saturated brine was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and dried over anhydrous sodium sulfate. After concentration under reduced pressure, 27.9 g of 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 2.51 (3H, s), 3.75 (3H, s), 4.51 (2H, s), 7.22-7.24 (1H, m), 7.36-7.39 (2H, m).

Reference synthesis example 10
1- (2-methoxymethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one 29.8 g described in Reference Synthesis Example 7, 35.2 g tributylvinyltin, tetrakistriphenylphosphine A mixture of 11.6 g of palladium and 500 mL of toluene was stirred with heating under reflux for 14 hours. After cooling, a saturated aqueous ammonium chloride solution was poured into the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 19.7 g of 1- (2-methoxymethyl-3-ethenylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.67 (1H, dd, J = 7.8, 1.3 Hz), 7.44 (1H, t, J = 7.8 Hz), 7.29 (1H, dd, J = 7.8, 1.3 Hz), 7.11 (1H, dd, J = 17.4, 11.1 Hz), 5.72 (1H, dd, J = 17.4, 1 .3 Hz), 5.44 (1H, dd, J = 11.1, 1.3 Hz), 4.45 (2H, s), 3.72 (3H, s), 3.23 (3H, s).
A mixture of 19.7 g of the obtained 1- (2-methoxymethyl-3-ethenylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one, 3.02 g of palladium-fibroin complex and 1 L of methanol was obtained. The mixture was stirred at room temperature for 11 hours under a hydrogen atmosphere. The reaction mixture was filtered and the filtrate was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 19.3 g of 1- (2-methoxymethyl-3-ethylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.42-7.38 (2H, m), 7.23-7.20 (1H, m), 4.44 (2H, s), 3. 72 (3H, s), 3.22 (3H, s), 2.82 (2H, q, J = 7.6 Hz), 1.27 (3H, t, J = 7.6 Hz).
A mixture of 19.3 g of the obtained 1- (2-methoxymethyl-3-ethylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one, 40 mL of acetic acid and 40 mL of 25% hydrogen bromide-acetic acid solution was added. The mixture was stirred at 65 ° C. for 1.5 hours. Saturated brine was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and dried over anhydrous sodium sulfate. After concentration under reduced pressure, 23.3 g of 1- (2-bromomethyl-3-ethylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.44-7.37 (2H, m), 7.23 (1H, dd, J = 7.1, 2.0 Hz), 4.56 (2H , S), 3.75 (3H, s), 2.85 (2H, q, J = 7.6 Hz), 1.33 (3H, t, J = 7.6 Hz).

Reference Synthesis Example 11
A mixture of 1- (4-hydroxy-3-methyl) -ethanone (5.0 g), methyl iodide (5.70 g), potassium carbonate (20.0 g) and acetone (200 ml) was stirred with heating under reflux for 6 hours. The reaction mixture was filtered, extracted with ethyl acetate, the organic layer was washed with water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and 1- (4-methoxy-3-methyl-phenyl) -ethanone. 3 g was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.82 (1H, dd, J = 8.5, 1.7 Hz), 7.79-7.76 (1H, m), 6.85 (1H, d, J = 8.5 Hz), 3.90 (3H, s), 2.55 (3H, s), 2.25 (3H, s).

Reference Synthesis Example 12
A mixture of 11.2 g of 1- (4-methoxy-3-methyl-phenyl) -ethanone described in Reference Synthesis Example 11 and 200 ml of tetrahydrofuran was added to 16.1 g of diethyl carbonate and 6.2 g of 55% sodium hydride at room temperature. Then, 0.05 g of dibenzo-18-crown-6 and 3 ml of ethanol were added, and the mixture was stirred with heating under reflux for 8 hours. Water was poured into the reaction mixture, the mixture was acidified with 10% aqueous hydrochloric acid, extracted with ethyl acetate, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 14.8 g of 3- (4-methoxy-3-methyl-phenyl) -3-oxo-propionic acid ethyl ester.

¹ H-NMR (CDCl ₃ ) δ: 7.81 (1H, dd, J = 8.5, 2.4 Hz), 7.76-7.76 (1H, m), 6.86 (1H, d, J = 8.5 Hz), 4.21 (2H, q, J = 7.1 Hz), 3.93 (2H, s), 3.90 (3H, s), 2.24 (3H, s), 1 .26 (3H, t, J = 7.1 Hz).

Reference Synthesis Example 13
At room temperature, 29 g of N-methylhydrazine was added to a mixture of 14.8 g of 3- (4-methoxy-3-methyl-phenyl) -3-oxo-propionic acid ethyl ester described in Reference Synthesis Example 12 and 100 ml of toluene. Stir for 12 hours. Toluene was distilled off under reduced pressure. At room temperature, 100 ml of water was poured into the reaction mixture, and the mixture was acidified with 10% aqueous hydrochloric acid and stirred for 3 hours. The precipitate was filtered, washed with 400 ml of water and 500 ml of ethyl acetate, and then dried under reduced pressure to obtain 9.3 g of 5-hydroxy-3- (4-methoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole. Obtained.

¹ H-NMR (DMSO-D ₆ ) δ: 7.58-7.56 (2H, m), 6.97 (1H, d, J = 8.9 Hz), 5.90 (1H, s), 3 .81 (3H, s), 3.60 (3H, s), 2.18 (3H, s).

Reference synthesis example 14
At 0 ° C., 4.0 g of N, N-dimethylformamide was added to 56 g of phosphorus oxychloride, and the mixture was stirred for 0.5 hour. Then, 5-hydroxy-3- (4-methoxy-3-methyl- described in Reference Synthesis Example 13 was used. 9.3 g of phenyl) -1-methyl-1H-pyrazole was added. After stirring at 100 ° C. for 7 hours, the reaction solvent was distilled off under reduced pressure. 100 ml of ice water was added to the reaction mixture, followed by extraction with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 6.3 g of 5-chloro-4-formyl-3- (4-methoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 9.93 (1H, s), 7.55 (1H, dd, J = 8.5, 2.2 Hz), 7.51 (1H, s), 6.90 (1H, d, J = 8.5 Hz), 3.92 (3H, s), 3.88 (3H, s), 2.27 (3H, s).

Reference synthesis example 15
At 0 ° C., 0.3 g of 5-chloro-4-formyl-3- (4-methoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole described in Reference Synthesis Example 14 and 10 ml of trifluoroacetic acid To the mixture was added 0.27 g of triethylsilane. After stirring at room temperature for 3 hours, 5 ml of water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 0.28 g of 5-chloro-3- (4-methoxy-3-methyl-phenyl) -1,4-dimethyl-1H-pyrazole.

¹ H-NMR (DMSO-D ₆ ) δ: 7.42-7.40 (2H, m), 6.98 (1H, d, J = 9.2 Hz), 3.81 (3H, s), 3 .80 (3H, s), 2.19 (3H, s), 2.11 (3H, s).

Reference Synthesis Example 16
0.4 g of 5-chloro-3- (4-methoxy-3-methyl-phenyl) -1,4-dimethyl-1H-pyrazole described in Reference Synthesis Example 15, 3 ml of 47% hydrobromic acid, and 3 ml of acetic acid The mixture was stirred for 15 hours under heating to reflux. The solvent was distilled off, 20 ml of ethyl acetate was added to the residue, and the mixture was stirred at room temperature for 1 hour. The precipitate was filtered, washed with hexane, and then dried under reduced pressure to obtain 0.3 g of 4- (5-chloro-1,4-dimethyl-1H-pyrazol-3-yl) -2-methyl-phenol.

¹ H-NMR (DMSO-D ₆ ) δ: 7.33 (1H, s), 7.24 (1H, d, J = 8.2 Hz), 6.83 (1H, d, J = 8.2 Hz) , 3.78 (3H, s), 2.15 (3H, s), 2.09 (3H, s).

Reference Synthesis Example 17
At room temperature, 3.07 g of 55% sodium hydride and 5.90 g of ethyl acetate were added to 50 ml of tetrahydrofuran, and the mixture was stirred for 0.5 hours. Next, 5.50 g of 1- (4-methoxy-3-methyl-phenyl) -ethanone, 0.024 g of dibenzo-18-crown-6, and 1 ml of ethanol were added, and the mixture was stirred with heating under reflux for 6 hours. Water was poured into the reaction mixture, acidified with a 10% aqueous hydrochloric acid solution, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 6.50 g of 1- (4-methoxy-3-methyl-phenyl) -butane-1,3-dione.

¹ H-NMR (CDCl ₃ : 23 ° C.) δ: 7.76 (1H, dd, J = 8.6, 2.3 Hz), 7.69 (1H, d, J = 1.4 Hz), 6.85 (1H, d, J = 8.5 Hz), 6.12 (1H, s), 3.89 (3H, s), 2.25 (3H, s), 2.17 (3H, s).

Reference Synthesis Example 18
At room temperature, hydrazine monohydrate was added to a mixture of 8.7 g of 1- (4-methoxy-3-methyl-phenyl) -butane-1,3-dione described in Reference Synthesis Example 17 and 100 ml of ethanol. 3 g was added and stirred for 12 hours. The reaction mixture was concentrated under reduced pressure until the amount of ethanol reached about 10 ml, and the resulting residue was subjected to silica gel column chromatography to give 3- (4-methoxy-3-methyl-phenyl) -5-methyl-1H-pyrazole. 8.6 g was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.49-7.46 (2H, m), 6.83-6.80 (1H, m), 6.26 (1H, s), 3.84 (3H , S), 2.31 (3H, s), 2.23 (3H, s).

Reference Synthesis Example 19
At 0 ° C., 55% of a mixture of 8.6 g of 3- (4-methoxy-3-methyl-phenyl) -5-methyl-1H-pyrazole described in Reference Synthesis Example 18 and 200 ml of N, N-dimethylformamide was added. 2.2 g of sodium hydride was added and stirred for 0.5 hour, and 59.0 g of methyl iodide was added. After stirring for 12 hours, water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 5.9 g of 3- (4-methoxy-3-methyl-phenyl) -1,5-dimethyl-1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 7.56-7.55 (1H, m), 7.53-7.50 (1H, m), 6.82 (1H, d, J = 8.5 Hz) 6.24 (1H, d, J = 0.7 Hz), 3.84 (3H, s), 3.80 (3H, s), 2.29 (3H, s), 2.25 (3H, s) ).

Reference Synthesis Example 20
In Reference Synthesis Example 16, 3- (4-methoxy) described in Reference Synthesis Example 21 was used instead of 5-chloro-3- (4-methoxy-3-methyl-phenyl) -1,4-dimethyl-1H-pyrazole. Similar reaction was performed using -3-methyl-phenyl) -1,5-dimethyl-1H-pyrazole, and 2-methyl-4- (1,5-dimethyl-1H-pyrazol-3-yl) -phenol Got.

¹ H-NMR (DMSO-D ₆ ) δ: 9.31 (1H, br s), 7.43 (1H, d, J = 1.7 Hz), 7.33 (1H, dd, J = 8.2) 2.2 Hz), 6.75 (1 H, d, J = 8.2 Hz), 6.29 (1 H, s), 3.71 (3 H, s), 2.24 (3 H, s), 2. 13 (3H, s).

Reference Synthesis Example 21
At room temperature, 1.9 g of 1- (4-methoxy-3-methyl-phenyl) -ethanone described in Reference Synthesis Example 11 and 200 ml of tetrahydrofuran were mixed with 11.9 g of trifluoroacetic acid ethyl ester and 20% -sodium. 28.5 g of ethoxide ethanol solution was added. After stirring for 6 hours under heating and refluxing, the reaction mixture was acidified by adding 100 ml of water and an aqueous 6N-hydrochloric acid solution. The mixture was extracted with ethyl acetate, and the organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 10 g of 4,4,4-trifluoro-1- (4-methoxy-3-methyl-phenyl) -butane-1,3-dione.

¹ H-NMR (CDCl ₃ : 23 ° C.) δ: 7.84 (1H, dd, J = 8.7, 2.4 Hz), 7.75 (1H, dd, J = 1.7, 0.7 Hz) 6.90 (1H, d, J = 8.7 Hz), 6.51 (1H, s), 3.93 (3H, s), 2.27 (3H, s).

Reference Synthesis Example 22
A mixture of 6.8 g of 4,4,4-trifluoro-1- (4-methoxy-3-methyl-phenyl) -butane-1,3-dione described in Reference Synthesis Example 21 and 100 ml of ethanol at 0 ° C. To the solution, 1.7 g of methyl hydrazine was added, and the mixture was warmed to room temperature and stirred for 1 hour. The mixture was concentrated under reduced pressure, and the resulting residue was subjected to silica gel column chromatography to give 5- (4-methoxy-3-methyl-phenyl) -2-methyl-3-trifluoromethyl-3,4-dihydro-2H. -3.2 g of pyrazol-3-ol was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.44-7.44 (1H, m), 7.33 (1H, dd, J = 8.5, 2.4 Hz), 6.79 (1H, d, J = 8.5 Hz), 3.85 (3H, s), 3.50 (1 H, d, J = 17.6 Hz), 3.24 (1 H, d, J = 17.6 Hz), 3.06 ( 3H, s), 2.87 (1H, s), 2.22 (3H, s).

Reference Synthesis Example 23
5- (4-Methoxy-3-methyl-phenyl) -2-methyl-3-trifluoromethyl-3,4-dihydro-2H-pyrazol-3-ol 2.3 g described in Reference Synthesis Example 22, 6N- A mixture of 4 ml of hydrochloric acid aqueous solution and 30 ml of tetrahydrofuran was stirred for 2 hours while heating under reflux. The mixture was extracted with ethyl acetate, the organic layer was washed with a saturated aqueous sodium carbonate solution and a saturated aqueous sodium chloride solution, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 2.2 g of 3- (4-methoxy-3-methyl-phenyl) -1-methyl-5-trifluoromethyl-1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 7.56-7.53 (2H, m), 6.85 (1H, d, J = 8.2 Hz), 6.81 (1H, s), 4.01 (3H, s), 3.86 (3H, s), 2.26 (3H, s).

Reference Synthesis Example 24
Of 2.2 g of 3- (4-methoxy-3-methyl-phenyl) -1-methyl-5-trifluoromethyl-1H-pyrazole described in Reference Synthesis Example 23, 24 ml of 47% hydrobromic acid, and 24 ml of acetic acid The mixture was stirred for 12 hours under heating to reflux. The solvent was distilled off, 70 ml of ice water was added, the precipitate was filtered, washed with 70 ml of ice water, dried under reduced pressure, and 2-methyl-4- (1-methyl-5-trifluoromethyl-1H-pyrazole-3- Yl) -phenol 2 g was obtained.

¹ H-NMR (DMSO-D ₆ ) δ: 9.52 (1H, s), 7.57 (1H, s), 7.47 (1H, d, J = 8.2 Hz), 7.22 (1H , S), 6.80 (1H, d, J = 8.5 Hz), 3.96 (3H, s), 2.15 (3H, s).

Reference Synthesis Example 25
A mixture of 10 g of 1- (4-hydroxy-3-methyl-phenyl) -ethanone, 13.6 g of izopropyl iodide, 18.4 g of potassium carbonate, and 250 ml of acetone was stirred with heating under reflux for 12 hours. After filtering the reaction mixture, the filtrate was concentrated under reduced pressure, and the resulting residue was subjected to silica gel column chromatography to obtain 9.5 g of 1- (4-isopropoxy-3-methyl-phenyl) -ethanone.

¹ H-NMR (CDCl ₃ ) δ: 7.80-7.78 (2H, m), 6.84 (1H, d, J = 8.2 Hz), 4.69-4.60 (1H, m) , 2.54 (3H, s), 2.23 (3H, s), 1.37 (6H, d, J = 6.0 Hz).

Reference Synthesis Example 26
At room temperature, 11.6 g of diethyl carbonate and 55% sodium hydride were added to a mixture of 9.4 g of 1- (4-isopropoxy-3-methyl-phenyl) -ethanone described in Reference Synthesis Example 25 and 150 ml of tetrahydrofuran. 5 g, 0.04 g of dibenzo-18-crown-6, and 3 ml of ethanol were added, and the mixture was stirred for 9 hours with heating under reflux. Water was poured into the reaction mixture, acidified with 10% aqueous hydrochloric acid, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 12.1 g of 3- (4-isopropoxy-3-methyl-phenyl) -3-oxo-propionic acid ethyl ester.

¹ H-NMR (CDCl ₃ ) δ: 7.79-7.76 (2H, m), 6.85-6.83 (1H, m), 4.68-4.62 (1H, m), 4 .21 (2H, q, J = 7.2 Hz), 3.93 (2H, s), 2.22 (3H, s), 1.37 (6H, d, J = 6.0 Hz), 1.26 (3H, t, J = 7.1 Hz).

Reference Synthesis Example 27
At room temperature, 21 g of N-methylhydrazine was added to a mixture of 12.1 g of 3- (4-isopropoxy-3-methyl-phenyl) -3-oxo-propionic acid ethyl ester described in Reference Synthesis Example 26 and 100 ml of toluene. The mixture was stirred for 12 hours. After toluene was distilled off under reduced pressure, 100 ml of water was poured into the reaction mixture at room temperature, and the mixture was acidified with 10% aqueous hydrochloric acid and stirred for 3 hours. The precipitate was filtered, washed with 400 ml of water and 500 ml of ethyl acetate, dried under reduced pressure, and 9.5 g of 5-hydroxy-3- (4-isopropoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole. Got.

¹ H-NMR (DMSO-D ₆ ) δ: 7.58-7.54 (2H, m), 7.01-6.98 (1H, m), 5.95 (1H, s), 4.66 -4.60 (1H, m), 3.62 (3H, s), 2.16 (3H, s), 1.28 (6H, d, J = 5.1 Hz).

Reference Synthesis Example 28
After adding 10.9 g of N, N-dimethylformamide to 150 g of phosphorus oxychloride at 0 ° C. and stirring for 0.5 hour, 5-hydroxy-3- (4-isopropoxy-3- 28 g of methyl-phenyl) -1-methyl-1H-pyrazole were added. After stirring at 100 ° C. for 10 hours, the reaction solvent was distilled off under reduced pressure. 100 ml of ice water was added to the reaction mixture and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 21 g of 5-chloro-4-formyl-3- (4-isopropoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 9.93 (1H, s), 7.52-7.50 (2H, m), 6.91-6.89 (1H, m), 4.63-4 .54 (1H, m), 3.92 (3H, s), 2.25 (3H, s), 1.36 (6H, d, J = 6.0 Hz).

Reference Synthesis Example 29
At room temperature, to a mixture of 4.8 g of 5-chloro-4-formyl-3- (4-isopropoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole described in Reference Synthesis Example 28 and 100 ml of tetrahydrofuran , 0.6 g of methanol, and 0.8 g of 55% sodium hydride were added and stirred for 3 hours. 50 ml of water was added to the reaction mixture, followed by extraction with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 4.5 g of 4-formyl-3- (4-isopropoxy-3-methyl-phenyl) -5-methoxy-1-methyl-1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 9.75 (1H, s), 7.39 (1H, d, J = 1.9 Hz), 7.35 (1H, dd, J = 8.3, 2. 3 Hz), 6.90 (1 H, d, J = 8.5 Hz), 4.63-4.54 (1 H, m), 4.30 (3 H, s), 3.71 (3 H, s), 2 .24 (3H, s), 1.36 (6H, d, J = 6.0 Hz).

Reference Synthesis Example 30
At 0 ° C., 4.2 g of 4-formyl-3- (4-isopropoxy-3-methyl-phenyl) -5-methoxy-1-methyl-1H-pyrazole described in Reference Synthesis Example 29, and 20 ml of trifluoroacetic acid To this mixture, 4.2 g of triethylsilane was added. After stirring at room temperature for 6 hours, the solvent was distilled off under reduced pressure, 10 ml of water was added, the mixture was extracted with ethyl acetate, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 3.8 g of 1,4-dimethyl-3- (4-isopropoxy-3-methyl-phenyl) -5-methoxy-1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 7.43 (1H, dd, J = 2.1, 0.7 Hz), 7.37-7.34 (1H, m), 6.86 (1H, d, J = 8.5 Hz), 4.57-4.51 (1H, m), 3.93 (3H, s), 3.71 (3H, s), 2.24 (3H, s), 2.14 (3H, s), 1.35 (6H, d, J = 6.0 Hz).

Reference Synthesis Example 31
A mixture of 7.4 g of 1,4-dimethyl-3- (4-isopropoxy-3-methyl-phenyl) -5-methoxy-1H-pyrazole described in Reference Synthesis Example 30 and 100 ml of 30% aqueous sulfuric acid solution was heated to reflux. Stir for 15 hours. The following post-processing was performed.
The resulting precipitate was filtered and washed with cold water to obtain a solid.
The filtrate was again concentrated under reduced pressure to about half, cooled to 0 ° C., and the generated precipitate was filtered and washed with cold water to obtain a solid.
This post-treatment operation was performed 4 times, and all the obtained solids were dried under reduced pressure to give 6.4 g of 4- (1,4-dimethyl-5-methoxy-1H-pyrazol-3-yl) -2-methyl-phenol. Got.

¹ H-NMR (DMSO-D ₆ ) δ: 9.33 (1H, s), 7.29 (1H, s), 7.20 (1H, d, J = 8.2 Hz), 6.79 (1H , D, J = 8.2 Hz), 3.87 (3H, s), 3.60 (3H, s), 2.14 (3H, s), 2.04 (3H, s).

Reference Synthesis Example 32
At 0 ° C., 10 g of propionyl chloride and 28 g of triethylamine were added to a mixture of 10 g of o-cresol and 100 ml of chloroform, and then the mixture was warmed to room temperature and stirred for 2 hours. Thereafter, the mixture was extracted with chloroform, and the organic layer was washed with water, dried over anhydrous magnesium, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 14 g of propionic acid-o-toluyl ester.

¹ H-NMR (CDCl ₃ ) δ: 7.24-7.18 (2H, m), 7.15-7.11 (1H, m), 7.01-6.99 (1H, m), 2 .61 (2H, q, J = 7.6 Hz), 2.17 (3H, s), 1.29 (3H, t, J = 7.6 Hz).

Reference Synthesis Example 33
Under 0 ° C., 30 g of aluminum trichloride was added to a mixture of 150 ml of nitromethane and 14 g of propionic acid-o-toluyl ester described in Reference Synthesis Example 32, and then the temperature was raised to 50 ° C. and stirred for 12 hours. To the mixture, 200 ml of ice water was poured and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 8.8 g of 1- (4-hydroxy-3-methyl-phenyl) -propan-1-one.

¹ H-NMR (CDCl ₃ ) δ: 7.80 (1H, d, J = 1.9 Hz), 7.75 (1H, dd, J = 8.5, 2.2 Hz), 6.86 (1H, d, J = 8.5 Hz), 6.65 (1H, s), 2.96 (2H, q, J = 7.2 Hz), 2.30 (3H, s), 1.22 (3H, td, J = 7.3, 1.3 Hz).

Reference Synthesis Example 34
In Synthesis Example 1, instead of 4- (5-chloro-1,4-dimethyl-1H-pyrazol-3-yl) -2-methyl-phenol, 1- (4-hydroxy-) described in Reference Synthesis Example 33 was used. The same reaction is carried out using 3-methyl-phenyl) -propan-1-one and 1- [2- (2-methyl-4-propionyl-phenoxymethyl) -3-methyl-phenyl] -4-methyl. -1,4-Dihydro-tetrazol-5-one was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.80 (1H, d, J = 8.47 Hz), 7.77-7.74 (1H, m), 7.47-7.39 (2H, m) 7.29 (1H, dJ = 7.33 Hz), 6.86 (1H, d, J = 8.47 Hz), 5.11 (2H, s), 3.62 (3H, s), 2. 94 (2H, q, J = 7.33 Hz), 2.50 (3H, s), 2.12 (3H, s), 1.20 (3H, t, J = 7.33 Hz).

Reference Synthesis Example 35
1- [2- (2-Methyl-4-propionyl-phenoxymethyl) -3-methyl-phenyl] -4-methyl-1,4-dihydro-tetrazol-5-one 6 described in Synthesis Example 34 at room temperature To a mixture of 0.1 g, diethyl oxalate 4.8 g, and N, N-dimethylformamide 100 ml, potassium tert-butoxide 3.7 g was added and stirred for 12 hours. After adding 70 ml of water, the mixture was acidified with 10% aqueous hydrochloric acid, extracted with ethyl acetate, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. 3-methyl-4- {3-methyl-4- [2-methyl-6- (4-methyl-5-oxo-4,5-dihydro-tetrazol-1-yl) -benzyloxy]- Obtained 3.8 g of phenyl} -2,4-dioxo-butyric acid ethyl ester.

¹ H-NMR (CDCl ₃ ) δ: 7.84 (1H, dd, J = 8.4, 2.3 Hz), 7.77 (1H, d, J = 1.6 Hz), 7.48-7. 41 (2H, m), 7.30 (1H, dd, J = 7.2, 1.8 Hz), 6.92 (1H, d, J = 8.6 Hz), 5.13 (2H, s), 5.01 (1H, q, J = 7.1 Hz), 4.27 (2H, q, J = 7.2 Hz), 3.65 (3H, s), 2.51 (3H, s), 2. 14 (3H, s), 1.44 (3H, d, J = 7.2 Hz), 1.30 (3H, t, J = 7.1 Hz).

Reference Synthesis Example 36
3-Methyl-4- {3-methyl-4- [2-methyl-6- (4-methyl-5-oxo-4,5-dihydro-tetrazol-1-yl) described in Reference Synthesis Example 35 at room temperature ) -Benzyloxy] -phenyl} -2,4-dioxo-butyric acid ethyl ester (3.8 g) and tetrahydrofuran (70 ml) were added with hydrazine monohydrate (0.39 g), and the mixture was stirred for 9 hours. The solvent was distilled off under reduced pressure, 100 ml of water was added, and the mixture was stirred for 0.5 hour. The precipitate was collected by filtration, washed with 50 ml of water and 50 ml of hexane, and dried under reduced pressure to give 1- {3-methyl-2- [2-methyl-4- (5-ethoxycarbonyl-4-methyl-1H-pyrazole). There was obtained 3.7 g of -3-yl) -phenoxymethyl] -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one.

¹ H-NMR (CDCl ₃ ) δ: 7.46-7.40 (2H, m), 7.33-7.31 (2H, m), 7.28 (1H, dd, J = 6.9, 2.4 Hz), 6.93-6.90 (1 H, m), 5.08 (2 H, s), 4.41 (2 H, q, J = 7.2 Hz), 3.64 (3 H, s) , 2.52 (3H, s), 2.41 (3H, s), 2.14 (3H, s), 1.42 (3H, t, J = 7.2 Hz).

Synthesis Example 37
1- {3-Methyl-2- [2-methyl-4- (5-ethoxycarbonyl-4-methyl-1H-pyrazol-3-yl) -phenoxymethyl]-described in Reference Synthesis Example 36 at 0 ° C. Phenyl} -4-methyl-1,4-dihydrotetrazol-5-one (0.5 g) and N, N-dimethylformamide (10 ml) were added with 55% sodium hydride (0.056 g) and stirred for 1 hour. 50.13 ml of methyl iodide were added. After stirring at room temperature for 12 hours, 5 ml of water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 1- {3-methyl-2- [2-methyl-4- (5-ethoxycarbonyl-1,4-dimethyl-1H-pyrazol-3-yl)- 0.19 g of phenoxymethyl] -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.45-7.40 (2H, m), 7.36-7.35 (1H, m), 7.32 (1H, dd, J = 8.3) 1.9 Hz), 7.28 (1 H, dd, J = 6.9, 2.4 Hz), 6.90 (1 H, d, J = 8.4 Hz), 5.07 (2 H, s), 4. 40 (2H, q, J = 7.1 Hz), 4.17 (3H, s), 3.64 (3H, s), 2.52 (3H, s), 2.36 (3H, s), 2 .13 (3H, s), 1.42 (3H, t, J = 7.1 Hz).

Reference synthesis example 38
1- {3-Methyl-2- [2-methyl-4- (5-ethoxycarbonyl-1,4-dimethyl-1H-pyrazol-3-yl) -phenoxymethyl] described in Synthesis Example 37 at room temperature To a mixture of -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one 2.1 g, tetrahydrofuran 30 ml, methanol 10 ml, and water 5 ml was added 0.3 g of lithium hydroxide and stirred for 12 hours. The solvent was removed under reduced pressure. 30 ml of 10% hydrochloric acid aqueous solution was added, the precipitate was collected by filtration, washed with water and hexane, dried under reduced pressure, and 2,4-dimethyl-5- {3-methyl-4- [2-methyl-6- ( 1.6 g of 4-methyl-5-oxo-4,5-dihydro-tetrazol-1-yl) -benzyloxy] -phenyl} -2H-pyrazole-3-carboxylic acid was obtained.

¹ H-NMR (DMSO-D ₆ ) δ: 7.54-7.51 (2H, m), 7.39-7.36 (1H, m), 7.34-7.32 (2H, m) 7.03 (1H, d, J = 9.2 Hz), 5.05 (2H, s), 4.05 (3H, s), 3.55 (3H, s), 2.50 (3H, s) ), 2.31 (3H, s), 2.05 (3H, s).

Reference Synthesis Example 39
2,4-Dimethyl-5- {3-methyl-4- [2-methyl-6- (4-methyl-5-oxo-4,5-dihydro-tetrazole-) described in Reference Synthesis Example 38 at room temperature To a mixture of 2.1 g of 1-yl) -benzyloxy] -phenyl} -2H-pyrazole-3-carboxylic acid and 25 ml of tetrahydrofuran was added 0.89 g of oxalyl dichloride and 0.1 ml of N, N-dimethylformamide. . After stirring for 3 hours, the solvent was distilled off under reduced pressure, and 2,4-dimethyl-5- {3-methyl-4- [2-methyl-6- (4-methyl-5-oxo-4,5-dihydro-) was obtained. 2.1 g of tetrazol-1-yl) -benzyloxy] -phenyl} -2H-pyrazole-3-carbonyl chloride were obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.46-7.41 (2H, m), 7.31-7.28 (3H, m), 6.92 (1H, d, J = 9.1 Hz) , 5.08 (2H, s), 4.16 (3H, s), 3.64 (3H, s), 2.52 (3H, s), 2.48 (3H, s), 2.14 ( 3H, s).

Reference Synthesis Example 40
2,4-Dimethyl-5- {3-methyl-4- [2-methyl-6- (4-methyl-5-oxo-4,5-dihydro-tetrazol-1-yl) described in Reference Synthesis Example 39 -Benzyloxy] -phenyl} -2H-pyrazole-3-carbonyl chloride 2.1 g was dissolved in 30 ml of tetrahydrofuran. At room temperature, 30 ml of the above tetrahydrofuran solution was added dropwise to 70 ml of 28-30% aqueous ammonia solution with stirring, and the mixture was further stirred for 2 hours. The precipitate was collected by filtration, washed with 30 ml of water and 30 ml of hexane, dried under reduced pressure, and 1- {3-methyl-2- [2-methyl-4- (5-aminocarbonyl-1,4-dimethyl-1H- 2 g of pyrazol-3-yl) -phenoxymethyl] -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one were obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.45-7.40 (2H, m), 7.34-7.31 (2H, m), 7.30-7.27 (1H, m), 6 .90 (1H, d, J = 8.4 Hz), 5.75 (2H, br s), 5.07 (2H, s), 4.13 (3H, s), 3.64 (3H, s) , 2.52 (3H, s), 2.36 (3H, s), 2.13 (3H, s).

Reference Synthesis Example 41
In Synthesis Example 1, instead of 4- (5-chloro-1,4-dimethyl-1H-pyrazol-3-yl) -2-methyl-phenol, 2-methyl-4- ( 1,5-Dimethyl-1H-pyrazol-3-yl) -phenol is used to carry out a similar reaction to give 1- {3-methyl-2- [2-methyl-4- (1,5-dimethyl-1H) -Pyrazol-3-yl) -phenoxymethyl] -phenyl} -4-methyl-1,4-dihydrotetrazol-5-one was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.54-7.52 (1H, m), 7.48 (1H, dd, J = 8.3, 2.3 Hz), 7.44-7.38 ( 2H, m), 7.30-7.26 (1H, m), 6.84 (1H, d, J = 8.5 Hz), 6.23 (1H, s), 5.05 (2H, s) , 3.80 (3H, s), 3.61 (3H, s), 2.51 (3H, s), 2.29 (3H, s), 2.11 (3H, s).

Reference synthesis example 42
A mixture of 25.0 g of 1-bromo-2-methyl-3-aminobenzene, 60.0 g of triphosgene and 400 ml of toluene was stirred with heating under reflux for 3 hours. The reaction mixture allowed to cool was concentrated under reduced pressure to obtain 30.3 g of 1-bromo-3-isocyanato-2-methylbenzene.

¹ H-NMR (CDCl ₃ ) δ: 2.42 (3H, s), 7.00 (1H, dt, J = 0.5, 8.0 Hz), 7.05 (1H, dd, J = 1. 7, 8.0 Hz), 7.39 (1H, dd, 1.5, 7.7 Hz).

Reference synthesis example 43
1- (2-Bromomethyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one was prepared by the following steps (1) to (4).
<Step (1)>
A mixture of 15.0 g of 3-amino-1-methoxy-2-methylbenzene, 48.7 g of triphosgene and 350 ml of toluene was stirred with heating under reflux for 3 hours. The reaction mixture allowed to cool was concentrated under reduced pressure to obtain 17.0 g of 1-methoxy-3-isocyanato-2-methylbenzene.

¹ H-NMR (CDCl ₃ ) δ: 2.19 (3H, s), 3.82 (3H, s), 6.69 (1H, d, J = 8.2 Hz), 6.72 (1H, dd , J = 0.5, 8.0 Hz), 7.09 (1H, t, J = 8.2 Hz).

<Step (2)>
16.0 g of anhydrous aluminum trichloride was added to 180 mL of N, N-dimethylformamide under ice cooling, and the mixture was stirred for 15 minutes. Sodium azide 7.8g was added here, and after stirring for 15 minutes, 17.0 g of 1-methoxy-3-isocyanato-2-methylbenzene was added, and it heated at 80 degreeC for 4.5 hours. After cooling, the reaction solution was added to a mixture of 25 g of sodium nitrite, 2 L of water and 500 g of ice with stirring. The mixture was acidified with 10% hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and 1- (2-methyl-3-methoxyphenyl) -1,4-dihydrotetrazol-5-one 16 0.2 g was obtained.

¹ H-NMR (DMSO-D ₆ ) δ: 1.99 (3H, s), 3.87 (3H, s), 7.01 (1H, d, J = 8.1 Hz), 7.17 (1H , D, J = 8.1 Hz). 7.36 (1H, t, J = 8.3 Hz), 14.63 (1H, s).

<Step (3)>
To a mixture of 10.00 g of 1- (2-methyl-3-methoxyphenyl) -1,4-dihydrotetrazol-3-one and 100 ml of N, N-dimethylformamide was added 2.47 g of 55% sodium hydride under ice cooling. Was added. The mixture was warmed to room temperature and stirred for 1 hour. To the reaction mixture, 3.5 ml of methyl iodide was added under ice cooling. The mixture was warmed to room temperature and stirred for 14 hours. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with 10% hydrochloric acid, water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 2.19 g of 1- (2-methyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-3-one.

¹ H-NMR (CDCl ₃ ) δ: 2.11 (3H, s), 3, 72 (3H, s), 3.88 (3H, s), 6.95 (1H, d, J = 8.2 Hz) ), 6.98 (1H, d, J = 8.5 Hz), 7.29 (1H, t, J = 8.2 Hz)

<Process (4)>
1- (2-Methyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one 2.19 g, 1,1′-azobis (cyclohexane-1-carbonitrile) 0.52 g, N -A mixture of 2.16 g of bromosuccinimide and 40 mL of chlorobenzene was stirred with heating under reflux for 5 hours. After cooling, water was poured into the reaction solution and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 2.36 g of 1- (2-bromomethyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one.

¹ H-NMR (CDCl ₃ ) δ: 3.74 (3H, s), 3.96 (3H, s), 4.93 (2H, s), 7.02 (1H, dd, J = 1.0) , 8.5 Hz), 7.04 (1H, d, J = 9.0 Hz), 7.43 (1H, t, J = 8.1 Hz).

Reference Synthesis Example 44
A mixture of 5.9 g of 3- (4-methoxy-3-methyl-phenyl) -1,5-dimethyl-1H-pyrazole described in Reference Synthesis Example 19 at room temperature, 5.8 g of N-bromosuccinimide, and 100 ml of chloroform. After stirring for 17 hours, water was added and the mixture was extracted with chloroform. The organic layer was washed with water, dried over anhydrous magnesium, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 4.0 g of 3- (4-methoxy-3-methyl-phenyl) -4-bromo-1,5-dimethyl-1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 7.67 (1H, dd, J = 8.5, 2.2 Hz), 7.62 (1H, d, J = 1.9 Hz), 6.87 (1H, d, J = 8.5 Hz), 3.86 (3H, s), 3.84 (3H, s), 2.31 (3H, s), 2.26 (3H, s).

Reference Synthesis Example 45
3- (4-Methoxy-3-methyl-phenyl) -4-bromo-1,5-dimethyl-1H-pyrazole 1.3 g described in Reference Synthesis Example 44, 1,4-dioxane 30 ml, water 5 ml, methylboronic acid A mixture of 1.0 g, [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct 0.4 g and potassium (III) phosphate 3.7 g was stirred with heating under reflux for 9 hours. . The reaction mixture was extracted with ethyl acetate, and the organic layer was washed with water, dried over anhydrous magnesium, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 0.6 g of 3- (4-methoxy-3-methyl-phenyl) -1,4,5-trimethyl-1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 7.43 (1H, s), 7.40 (1H, dd, J = 8.2, 2.2 Hz), 6.86 (1H, d, J = 8. 5 Hz), 3.85 (3H, s), 3.80 (3H, s), 2.25 (3H, s), 2.21 (3H, s), 2.11 (3H, s).

Reference Synthesis Example 46
A mixture of 0.6 g of 3- (4-methoxy-3-methyl-phenyl) -1,4,5-trimethyl-1H-pyrazole described in Reference Synthesis Example 45, 5 ml of 47% hydrobromic acid, and 5 ml of acetic acid was used. The mixture was stirred for 13 hours under reflux. The solvent was distilled off, 30 ml of ethyl acetate was added to the residue, and the mixture was stirred at room temperature for 1 hour. The precipitate was filtered, washed with hexane, and then dried under reduced pressure to obtain 0.5 g of 4- (1,4,5-trimethyl-1H-pyrazol-3-yl) -2-methyl-phenol.

¹ H-NMR (DMSO-D ₆ ) δ: 7.33 (1H, d, J = 2.2 Hz), 7.26 (1H, dd, J = 8.2, 2.2 Hz), 6.88 ( 1H, d, J = 8.2 Hz), 3.82 (3H, s), 2.26 (3H, s), 2.17 (3H, s), 2.08 (3H, s).

Reference Synthesis Example 47
5-chloro-4-formyl-3- (4-isopropoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole 2.0 g described in Reference Synthesis Example 28, potassium fluoride 2.0 g, sulfolane 11 ml , And 30 ml of toluene were heated to 170 ° C., and toluene was distilled off, followed by stirring at 220 ° C. for 4 hours. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 1.0 g of 5-fluoro-4-formyl-3- (4-isopropoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 9.85 (1H, s), 7.52-7.50 (2H, m), 6.91-6.89 (1H, m), 4.60-4 .58 (1H, m), 3.81 (3H, s), 2.25 (3H, s), 1.37 (6H, d, J = 6.0 Hz).

Reference synthesis example 48
Under 0 ° C., 1.0 g of 5-fluoro-4-formyl-3- (4-isopropoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole described in Reference Synthesis Example 47 and 18 ml of trifluoroacetic acid To the mixture, 1.4 ml of triethylsilane was added. After stirring at room temperature for 15 hours, 5 ml of water was added, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 0.75 g of 5-fluoro-3- (4-isopropoxy-3-methyl-phenyl) -1,4-dimethyl-1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 7.43 (1H, s), 7.37 (1H, dd, J = 8.4, 1.8 Hz), 6.87 (1H, d, J = 8. 6Hz), 4.58-4.52 (1H, m), 3.74 (3H, s), 2.24 (3H, s), 2.09 (3H, s), 1.35 (6H, d) , J = 6.1 Hz).

Reference Synthesis Example 49
A mixture of 0.75 g of 5-fluoro-3- (4-isopropoxy-3-methyl-phenyl) -1,4-dimethyl-1H-pyrazole described in Reference Synthesis Example 48 and 6 ml of 20% aqueous sulfuric acid was heated to reflux. The mixture was stirred at room temperature for 5 hours and then at room temperature for 12 hours. Water was added to the reaction mixture, neutralized with an aqueous sodium carbonate solution, and the solvent was distilled off. The obtained residue was subjected to silica gel column chromatography to obtain 0.54 g of 4- (5-fluoro-1,4-dimethyl-1H-pyrazol-3-yl) -2-methyl-phenol.

¹ H-NMR (CDCl ₃ ) δ: 7.42 (1H, s), 7.32 (1H, dd, J = 8.2, 2.3 Hz), 6.80 (1H, d, J = 8. 2 Hz), 4.99 (1H, s), 3.75 (3H, s), 2.28 (3H, s), 2.09 (3H, s).

Reference production example 50
A mixture of 5.76 g of 1- (4-methoxy-3-methyl-phenyl) -ethanone described in Reference Synthesis Example 11 and 7.46 ml of N, N-dimethylformamide diethyl acetal was stirred with heating under reflux for 24 hours. Concentration under reduced pressure gave 4.78 g of 3-dimethylamino-1- (4-methoxy-3-methyl-phenyl) -propenone.

¹ H-NMR (DMSO-D ₆ ) δ: 7.76 (1H, dd, J = 8.5, 2.2 Hz), 7.72 (1H, s), 7.64 (1H, d, J = 12.4 Hz), 6.95 (1H, d, J = 8.5 Hz), 5.80 (1H, d, J = 12.4 Hz), 3.83 (3H, s), 3.11 (3H, br s), 2.90 (3H, br s), 2.18 (3H, s).

Reference Production Example 51
In Reference Production Example 50, the same reaction was performed using 1- (3-chloro-4-methoxy-phenyl) -ethanone instead of 1- (4-methoxy-3-methyl-phenyl) -ethanone. 3-Dimethylamino-1- (3-chloro-4-methoxy-phenyl) -propenone was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.95 (1H, d, J = 2.2 Hz), 7.84 (1H, dd, J = 8.7, 2.2 Hz), 7.80 (1H, d, J = 12.3 Hz), 6.94 (1H, d, J = 8.7 Hz), 5.65 (1H, d, J = 12.3 Hz), 3.95 (3H, s), 3. 14 (3H, s), 2.95 (3H, s).

Reference Production Example 52
In Reference Production Example 18, instead of 1- (4-methoxy-3-methyl-phenyl) -butane-1,3-dione, 3-dimethylamino-1- (3-chloro- The same reaction was performed using 4-methoxy-phenyl) -propenone to give 3- (3-chloro-4-methoxy-phenyl) -1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 7.78 (1H, d, J = 1.9 Hz), 7.61-7.59 (2H, m), 6.92 (1H, d, J = 8. 7 Hz), 6.54 (1 H, dd, J = 2.2, 0.7 Hz), 3.92 (3 H, s).

Reference Production Example 53
In Reference Production Example 19, instead of 3- (4-methoxy-3-methyl-phenyl) -5-methyl-1H-pyrazole, 3- (3-chloro-4-methoxy-phenyl described in Reference Production Example 52 was used. ) -1H-pyrazole was used to carry out the same reaction to obtain 3- (3-chloro-4-methoxy-phenyl) -1-methyl-1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 7.81 (1H, d, J = 2.2 Hz), 7.64 (1H, dd, J = 8.6, 2.1 Hz), 7.36 (1H, d, J = 2.2 Hz), 6.95 (1H, d, J = 8.5 Hz), 6.45 (1H, d, J = 2.2 Hz), 3.94 (3H, s), 3. 93 (3H, s)

Reference production example 54
In Reference Preparation Example 44, instead of 3- (4-methoxy-3-methyl-phenyl) -1,5-dimethyl-1H-pyrazole, 3- (3-chloro-4-methoxy described in Reference Preparation Example 53 was used. -Phenyl) -1-methyl-1H-pyrazole was used for the same reaction to obtain 3- (4-methoxy-3-chloro-phenyl) -4-bromo-1-methyl-1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 7.92-7.91 (1H, m), 7.79-7.76 (1H, m), 7.44 (1H, s), 6.98 (1H , D, J = 8.5 Hz), 3.94 (3H, s), 3.92 (3H, s).

Reference Production Example 55
In Reference Production Example 45, 3- (4-methoxy) described in Reference Production Example 54 was used instead of 3- (4-methoxy-3-methyl-phenyl) -4-bromo-1,5-dimethyl-1H-pyrazole. Similar reaction was performed using -3-chloro-phenyl) -4-bromo-1-methyl-1H-pyrazole, and 3- (4-methoxy-3-chloro-phenyl) -1,4-dimethyl-1H- Pyrazole was obtained.

¹ H-NMR (CDCl ₃ ) δ: 7.70 (1H, d, J = 2.2 Hz), 7.53 (1H, dd, J = 8.5, 2.2 Hz), 7.18 (1H, s), 6.97 (1H, d, J = 8.5 Hz), 3.93 (3H, s), 3.88 (3H, s), 2.20 (3H, s).

Reference production example 56
A mixture of 9.5 g of 5-hydroxy-3- (4-isopropoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole described in Reference Production Example 27 and 70 ml of N, N-dimethylformamide at room temperature To the mixture, 2.5 g of 55% sodium hydride was added and stirred for 1 hour. To the reaction mixture, 9.7 g of dimethyl sulfate was added and stirred at 100 ° C. for 12 hours. 100 ml of water was added to the reaction mixture, followed by extraction with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 5.8 g of 5-methoxy-3- (4-isopropoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 7.55 (1H, dd, J = 2.3, 0.7 Hz), 7.49-7.47 (1H, m), 6.84 (1H, d, J = 8.5 Hz), 5.75 (1H, s), 4.56-4.50 (1H, m), 3.92 (3H, s), 3.66 (3H, s), 2.23 (3H, s), 1.35 (3H, s), 1.33 (3H, s).

Reference Production Example 37
At room temperature, 5.8 g of 5-methoxy-3- (4-isopropoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole described in Reference Production Example 56, 70 ml of chloroform, and N-chlorosuccinimide 3 g of the reaction mixture was stirred for 11 hours. 100 ml of water was added to the reaction mixture, followed by extraction with chloroform. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 5.6 g of 4-chloro-5-methoxy-3- (4-isopropoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole.

¹ H-NMR (CDCl ₃ ) δ: 7.62-7.59 (2H, m), 6.87 (1H, d, J = 9.1 Hz), 4.59-4.53 (1H, m) , 4.11 (3H, s), 3.70 (3H, s), 2.24 (3H, s), 1.36 (3H, s), 1.34 (3H, s).

Reference Production Example 58
A mixture of 5.6 g of 4-chloro-5-methoxy-3- (4-isopropoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole described in Reference Production Example 57 and 120 ml of 30% aqueous sulfuric acid was heated. The mixture was stirred for 20 hours under reflux. 100 ml of water was added to the reaction mixture, followed by extraction with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 1.2 g of 2-methyl-4- (4-chloro-5-methoxy-1-methyl-1H-pyrazol-3-yl) -phenol.

¹ H-NMR (CDCl ₃ ) δ: 7.59 (1H, d, J = 2.0 Hz), 7.55 (1H, dd, J = 8.4, 2.0 Hz), 6.80 (1H, d, J = 8.5 Hz), 5.06 (1H, s), 4.11 (3H, s), 3.70 (3H, s), 2.28 (3H, s).

The tetrazolinone compound 65 to the present tetrazolinone compound 12 that can be produced according to the synthesis method C from the synthesis method A are shown below.
In the table, Me represents a methyl group, Et represents an ethyl group, OMe represents a methoxy group, OEt represents an ethoxy group, Br represents a bromine atom, Cl represents a chlorine atom, and F represents a fluorine atom. CF3 represents a trifluoromethyl group, CN represents a cyano group, SMe represents a methylthio group, and Cy represents a cyclopropyl group.

The physical property data of the present tetrazolinone compounds 12 to 65 are shown below. ([] Represents the tetrazolinone compound number.)
[12] ¹ H-NMR (CDCl ₃ ) δ: 7.80 (1H, dd, J = 8.0, 1.4 Hz), 7.44 (1H, dd, J = 8.0, 1.4 Hz) 7.40-7.38 (2H, m), 7.36 (1H, dd, J = 8.1, 2.4 Hz), 6.87 (1H, d, J = 8.2 Hz), 5. 33 (2H, s), 3.79 (3H, s), 3.59 (3H, s), 2.20 (3H, s), 2.10 (3H, s), 2.07 (3H, s) ). [13] ¹ H-NMR (CDCl ₃ ) δ: 7.61 (1H, dd, J = 8.0, 1.4 Hz), 7.46 (1H, t, J = 8.0 Hz), 7.41 −7.39 (2H, m), 7.35 (1H, dd, J = 8.2, 2.3 Hz), 6.88 (1H, d, J = 8.2 Hz), 5.34 (2H, s), 3.79 (3H, s), 3.59 (3H, s), 2.20 (3H, s), 2.10 (3H, s), 2.05 (3H, s). [14] ¹ H-NMR (CDCl ₃ ) δ: 7.50 (1H, td, J = 8.2, 5.8 Hz), 7.38 (1H, s), 7.37-7.31 (2H , M), 7.29-7.27 (1H, m), 6.89 (1H, d, J = 8.2 Hz), 5.30 (2H, s), 3.79 (3H, s), 3.59 (3H, s), 2.20 (3H, s), 2.09 (3H, s), 2.02 (3H, s). [15] ¹ H-NMR (CDCl ₃ ) δ: 7.66 (1H, dd, J = 8.2, 2.2 Hz), 7.61 (1H, s), 7.49-7.43 (2H M), 7.28 (1H, dd, J = 7.1, 2.1 Hz), 6.90 (1H, d, J = 8.5 Hz), 5.08 (2H, s), 3.82. (3H, s), 3.58 (3H, s), 2.85 (2H, q, J = 7.6 Hz), 2.28 (3H, s), 2.11 (3H, s), 1. 28 (3H, t, J = 7.6 Hz) [16] ¹ H-NMR (CDCl ₃ ) δ: 7.63 (1H, dd, J = 8.4, 2.2 Hz), 7.57-7. 56 (1H, m), 7.46 (1 H, t, J = 8.2 Hz), 7.09-7.06 (2H, m), 6.92 (1H, d, J = 8.7 Hz), 5.29 (2H, s), 3. 3 (3H, s), 3.81 (3H, s), 3.58 (3H, s), 2.28 (3H, s), 2.03 (3H, s) [17] 1 H-NMR ( CDCl ₃ ) δ: 7.65 (1H, dd, J = 8.5, 2.3 Hz), 7.58 (1H, dd, J = 1.6, 0.7 Hz), 7.53-7.48 (1H, m), 7.30 (2H, dd, J = 17.1, 7.9 Hz), 6.90 (1H, d, J = 8.5 Hz), 5.31 (2H, s), 3 .81 (3H, s), 3.59 (3H, s), 2.28 (3H, s), 2.03 (3H, s). [18] ¹ H-NMR (CDCl ₃ ) δ: 7.54-7.52 (1H, m), 7.48 (1H, dd, J = 8.3, 2.3 Hz), 7.44-7 .38 (2H, m), 7.30-7.26 (1H, m), 6.84 (1H, d, J = 8.5 Hz), 6.23 (1H, s), 5.05 (2H) , S), 3.80 (3H, s), 3.61 (3H, s), 2.51 (3H, s), 2.29 (3H, s), 2.11 (3H, s). [19] ¹ H-NMR (CDCl ₃ ) δ: 7.54-7.52 (1H, m), 7.51-7.43 (3H, m), 7.29-7.26 (1H, m ), 6.85 (1H, d, J = 8.5 Hz), 6.23 (1H, s), 5.07 (2H, s), 3.80 (3H, s), 3.57 (3H, s), 2.89-2.81 (2H, m), 2.29 (3H, s), 2.10 (3H, s), 1.28 (3H, t, J = 7.6 Hz). [20] ¹ H-NMR (CDCl ₃ ) δ: 7.49-7.43 (3H, m), 7.07 (2H, dd, J = 8.2, 4.3 Hz), 6.87 (1H , D, J = 8.2 Hz), 6.21 (1H, s), 5.27 (2H, s), 3.92 (3H, s), 3.79 (3H, s), 3.56 ( 3H, s), 2.28 (3H, s), 2.02 (3H, s). [21] ¹ H-NMR (CDCl ₃ ) δ: 7.61 (1H, dd, J = 8.0, 1.1 Hz), 7.52 to 7.51 (1H, m), 7.49-7 .44 (2H, m), 7.40 (1H, dd, J = 8.0, 1.4 Hz), 6.85 (1H, d, J = 8.5 Hz), 6.23 (1H, d, J = 0.7 Hz), 5.33 (2H, s), 3.80 (3H, s), 3.57 (3H, s), 2.28 (3H, d, J = 2.5 Hz), 2 .05 (3H, s). [22] ¹ H-NMR (CDCl ₃ ) δ: 7.49 (1H, t, J = 8.2 Hz), 7.40-7.39 (1H, m), 7.37 (1H, dd, J = 8.5, 2.3 Hz), 7.13-7.09 (2H, m), 6.94 (1H, d, J = 8.5 Hz), 5.32 (2H, s), 3.96. (3H, s), 3.87 (3H, s), 3.62 (3H, s), 2.17 (3H, s), 2.06 (3H, s). [23] ¹ H-NMR (CDCl ₃ ) δ: 7.80 (1H, dd, J = 7.9, 1.5 Hz), 7.45-7.35 (4H, m), 6.88 (1H , D, J = 8.5 Hz), 5.33 (2H, s), 3.85 (3H, s), 3.60 (3H, s), 2.14 (3H, s), 2.07 ( 3H, s). [24] ¹ H-NMR (CDCl ₃ ) δ: 7.54-7.48 (1H, m), 7.38-7.27 (4H, m), 6.90 (1H, d, J = 8) .5Hz), 5.30 (2H, d, J = 0.7 Hz), 3.85 (3H, s), 3.60 (3H, s), 2.14 (3H, s), 2.03 ( 3H, s). [25] ¹ H-NMR (CDCl ₃ ) δ: 7.92 (1H, dd, J = 7.0, 2.2 Hz), 7.71-7.66 (2H, m), 7.40-7 .35 (2H, m), 6.88-6.86 (1H, m), 5.33 (2H, s), 3.85 (3H, s), 3.53 (3H, s), 2. 15 (3H, s), 2.05 (3H, s). [26] ¹ H-NMR (CDCl ₃ ) δ: 7.54-7.54 (1H, m), 7.51 (1H, dd, J = 8.4, 2.2 Hz), 7.45-7 .40 (2H, m), 7.28 (1H, dd, J = 7.0, 2.4 Hz), 6.87 (1H, d, J = 8.2 Hz), 6.80 (1H, s) , 5.07 (2H, s), 4.01 (3H, s), 3.62 (3H, s), 2.51 (3H, s), 2.13 (3H, s). [27] ¹ H-NMR (CDCl ₃ ) δ: 7.49 (2H, s), 7.47 (1H, s), 7.10-7.06 (2H, m), 6.90 (1H, d, J = 8.0 Hz), 6.78 (1H, d, J = 0.5 Hz), 5.29 (2H, s), 4.00 (3H, s), 3.93 (3H, s) , 3.58 (3H, s), 2.03 (3H, s). [28] ¹ H-NMR (CDCl ₃ ) δ: 7.81 (1H, dd, J = 7.8, 1.4 Hz), 7.52-7.49 (2H, m), 7.46-7 .38 (2H, m), 6.87 (1H, d, J = 8.2 Hz), 6.80 (1H, s), 5.33 (2H, s), 4.01 (3H, s), 3.59 (3H, s), 2.08 (3H, s). [29] ¹ H-NMR (CDCl ₃ ) δ: 7.62 (1H, dd, J = 8.0, 1.4 Hz), 7.52-7.49 (2H, m), 7.47 (1H , T, J = 8.0 Hz), 7.40 (1H, dd, J = 8.0, 1.4 Hz), 6.87 (1H, d, J = 8.5 Hz), 6.80 (1H, d, J = 0.5 Hz), 5.34 (2H, s), 4.00 (3H, s), 3.59 (3H, s), 2.06 (3H, s). [30] ¹ H-NMR (CDCl ₃ ) δ: 7.49-7.43 (2H, m), 7.41-7.40 (1H, m), 7.36 (1H, d, J = 8) .5 Hz), 7.28 (1H, dd, J = 7.0, 2.2 Hz), 6.88 (1H, d, J = 8.5 Hz), 5.08 (2H, s), 3.94 (3H, s), 3.71 (3H, s), 3.59 (3H, s), 2.85 (2H, q, J = 7.6 Hz), 2.13 (3H, s), 2. 11 (3H, s), 1.27 (3H, q, J = 7.6 Hz). [31] ¹ H-NMR (CDCl ₃ ) δ: 7.45 (1H, s), 7.34 (1H, s), 7.31 (1H, dd, J = 8.4, 2.2 Hz), 7.07 (1H, d, J = 4.4 Hz), 7.05 (1H, d, J = 3.9 Hz), 6.89 (1H, d, J = 8.2 Hz), 5.26 (2H) , S), 3.91 (3H, s), 3.90 (3H, s), 3.68 (3H, s), 3.56 (3H, s), 2.10 (3H, s), 2 .01 (3H, s). [32] ¹ H-NMR (CDCl ₃ ) δ: 7.80 (1H, dd, J = 8.0, 1.0 Hz), 7.45-7.33 (4H, m), 6.87 (1H , D, J = 8.2 Hz), 5.33 (2H, s), 3.93 (3H, d, J = 0.5 Hz), 3.70 (3H, s), 3.59 (3H, s) ), 2.13 (3H, s), 2.07 (3H, s). [33] ¹ H-NMR (CDCl ₃ ) δ: 7.61 (1H, dd, J = 8.0, 1.2 Hz), 7.46 (1H, t, J = 8.0 Hz), 7.41 −7.39 (2H, m), 7.34 (1H, dd, J = 8.5, 1.9 Hz), 6.87 (1H, d, J = 8.5 Hz), 5.34 (2H, s), 3.93 (3H, s), 3.70 (3H, s), 3.59 (3H, s), 2.12 (3H, s), 2.06 (3H, s). [34] ¹ H-NMR (CDCl ₃ ) δ: 7.52 (1H, td, J = 8.2, 5.9 Hz), 7.39 (1H, d, J = 1.4 Hz), 7.37 −7.28 (3H, m) 6.90 (1H, d, J = 8.5 Hz), 5.31 (2H, d, J = 0.9 Hz), 3.94 (3H, s), 3. 71 (3H, s), 3.61 (3H, s), 2.14 (3H, s), 2.03 (3H, s). [35] ¹ H-NMR (CDCl ₃ ) δ: 7.44-7.39 (3H, m), 7.37 (1H, dd, J = 8.3, 2.3 Hz), 7.29-7 .27 (1H, m), 6.87 (1H, d, J = 8.5 Hz), 5.06 (2H, s), 4.17-4.12 (2H, m), 3.71 (3H , S), 3.62 (3H, s), 2.51 (3H, s), 2.12 (3H, s), 2.11 (3H, s), 1.41 (3H, t, J = 7.0 Hz). [36] ¹ H-NMR (CDCl ₃ ) δ: 7.49-7.43 (2H, m), 7.41-7.41 (1H, m), 7.38-7.35 (1H, m ), 7.28 (1H, dd, J = 7.0, 2.2 Hz), 6.88 (1H, d, J = 8.2 Hz), 5.07 (2H, s), 4.14 (2H) , Q, J = 7.1 Hz), 3.70 (3H, s), 3.58 (3H, s), 2.85 (2H, q, J = 7.6 Hz), 2.11 (3H, s) ), 2.10 (3H, s), 1.41 (3H, t, J = 7.1 Hz), 1.28 (3H, t, J = 7.7 Hz). [37] ¹ H-NMR (CDCl ₃ ) δ: 7.46 (1H, t, J = 8.2 Hz), 7.37 (1H, s), 7.33 (1H, dd, J = 8.2) , 2.3 Hz), 7.08 (2H, dd, J = 8.1, 3.8 Hz), 6.90 (1H, d, J = 8.5 Hz), 5.28 (2H, s), 4 .16-4.09 (2H, m), 3.92 (3H, s), 3.70 (3H, s), 3.58 (3H, s), 2.10 (3H, s), 2. 02 (3H, s), 1.40 (3H, t, J = 7.1 Hz). [38] ¹ H-NMR (CDCl ₃ ) δ: 7.80 (1H, dd, J = 7.8, 1.4 Hz), 7.45-7.34 (4H, m), 6.87 (1H , D, J = 8.5 Hz), 5.33 (2H, s), 4.14 (2H, q, J = 7.1 Hz), 3.70 (3H, s), 3.59 (3H, s) ), 2.10 (3H, s), 2.0
6 (3H, s), 1.41 (3H, t, J = 7.1 Hz). [39] ¹ H-NMR (CDCl ₃ ) δ: 7.61 (1H, dd, J = 8.0, 1.4 Hz), 7.46 (1H, t, J = 8.0 Hz), 7.41 -7.39 (2H, m), 7.36-7.34 (1H, m), 6.87 (1H, d, J = 8.5Hz), 5.34 (2H, s), 4.14 (2H, q, J = 7.0 Hz), 3.70 (3H, s), 3.59 (3H, s), 2.10 (3H, s), 2.05 (3H, s), 1. 41 (3H, t, J = 7.1 Hz). [40] ¹ H-NMR (CDCl ₃ ) δ: 7.53-7.47 (1H, m), 7.39 (1H, d, J = 1.6 Hz), 7.36-7.26 (3H M), 6.88 (1H, d, J = 8.5 Hz), 5.29 (2H, s), 4.14 (2H, q, J = 7.1 Hz), 3.70 (3H, s). ), 3.59 (3H, s), 2.10 (3H, s), 2.02 (3H, s), 1.40 (3H, t, J = 7.1 Hz). [41] ¹ H-NMR (CDCl ₃ ) δ: 7.51-7.44 (2H, m), 7.40-7.36 (2H, m), 7.29 (1H, dd, J = 7) .1, 2.1 Hz), 6.91 (1H, d, J = 8.5 Hz), 5.09 (2H, s), 4.03 (3H, s), 3.60 (3H, s), 2.85 (2H, q, J = 7.6 Hz), 2.34 (3H, s), 2.12 (3H, s), 1.29 (3H, t, J = 7.6 Hz). [42] ¹ H-NMR (CDCl ₃ ) δ: 7.65 (1H, dd, J = 8.4, 2.3 Hz), 7.58 (1H, d, J = 2.0 Hz), 7.44 -7.39 (2H, m), 7.28-7.26 (1H, m), 6.89 (1H, d, J = 8.6 Hz), 5.06 (2H, s), 3.84 (3H, s), 3.62 (3H, s), 2.51 (3H, s), 2.30 (3H, s), 2.12 (3H, s). [43] ¹ H-NMR (CDCl ₃ ) δ: 7.44-7.38 (4H, m), 7.29-7.26 (1H, m), 6.88 (1H, d, J = 8) .5 Hz), 5.06 (2H, s), 3.98 (3H, s), 3.62 (3H, s), 2.51 (3H, s), 2.26 (6H, s), 2 .13 (3H, s). [44] ¹ H-NMR (CDCl ₃ ) δ: 7.49-7.42 (3H, m), 7.40 (1H, dd, J = 8.5, 2.2 Hz), 7.28 (1H , Dd, J = 7.0, 2.0 Hz), 6.89 (1H, d, J = 8.4 Hz), 5.08 (2H, s), 3.98 (3H, s), 3.59 (3H, s), 2.85 (2H, q, J = 7.6 Hz), 2.26 (6H, s), 2.11 (3H, s), 1.28 (3H, t, J = 7) .6 Hz). [45] ¹ H-NMR (CDCl ₃ ) δ: 7.46 (1H, t, J = 8.2 Hz), 7.39-7.38 (1H, m), 7.36 (1H, dd, J = 8.3, 2.2 Hz), 7.09-7.06 (2H, m), 6.91 (1H, d, J = 8.4 Hz), 5.28 (2H, s), 3.97. (3H, s), 3.92 (3H, s), 3.58 (3H, s), 2.25 (3H, s), 2.25 (3H, s), 2.03 (3H, s) . [46] ¹ H-NMR (CDCl ₃ ) δ: 7.62 (1H, t, J = 4.0 Hz), 7.50-7.37 (4H, m), 6.89 (1H, d, J = 8.5 Hz), 5.35 (2H, s), 3.98 (3H, s), 3.59 (3H, s), 2.26 (6H, s), 2.06 (3H, s) . [47] ¹ H-NMR (CDCl ₃ ) δ: 7.53-7.47 (1H, m), 7.41-7.40 (1H, m), 7.38 (1H, dd, J = 8) .5, 1.9 Hz), 7.33-7.26 (2 H, m), 6.89 (1 H, d, J = 8.4 Hz), 5.30 (2 H, s), 3.98 (3 H) , S), 3.59 (3H, s), 2.26 (3H, s), 2.25 (3H, s), 2.02 (3H, s). [48] MS: 439 (M + 1). [49] ¹ H-NMR (CDCl ₃ ) δ: 7.43 (1H, t, J = 7.9 Hz), 7.40 (1H, d, J = 1.8 Hz), 7.38 (1H, dd , J = 8.4, 2.2 Hz), 7.28 (2H, s), 6.93 (1H, d, J = 8.2 Hz), 5.29 (2H, s), 3.85 (3H) , S), 3.61 (3H, s), 2.15 (3H, s), 2.14-2.12 (4H, m), 1.01-0.97 (2H, m),. 78-0.74 (2H, m). [50] ¹ H-NMR (CDCl ₃ ) δ: 7.44 (1H, t, J = 7.8 Hz), 7.40-7.36 (2H, m), 7.28 (2H, d, J = 7.9 Hz), 6.94 (1H, d, J = 8.4 Hz), 5.29 (2H, s), 4.03 (3H, s), 3.62 (3H, s), 2. 34 (3H, s), 2.16-2.09 (4H, m), 1.02-0.97 (2H, m), 0.79-0.75 (2H, m). [51] ¹ H-NMR (CDCl ₃ ) δ: 7.64-7.61 (1H, m), 7.58-7.57 (1H, m), 7.44 (1 H, t, J = 7) .8 Hz), 7.30-7.27 (2 H, m), 6.94 (1 H, d, J = 8.5 Hz), 5.30 (2 H, s), 4.12 (3 H, s), 3.71 (3H, s), 3.61 (3H, s), 2.14-2.11 (4H, m), 1.01-0.97 (2H, m), 0.79-0. 76 (2H, m). [52] ¹ H-NMR (CDCl ₃ ) δ: 7.44 (1H, t, J = 7.9 Hz), 7.41 (1H, d, J = 1.4 Hz), 7.37 (1H, dd , J = 8.2, 2.1 Hz), 7.28 (2H, d, J = 8.0 Hz), 6.93 (1H, d, J = 8.5 Hz), 5.30 (2H, s) , 3.95 (3H, s), 3.72 (3H, s), 3.62 (3H, s), 2.16-2.13 (4H, m), 2.12 (3H, s), 1.03-0.98 (2H, m), 0.79-0.75 (2H, m). [53] ¹ H-NMR (CDCl ₃ ) δ: 7.45-7.41 (2H, m), 7.37 (1H, dd, J = 8.5, 2.3 Hz), 7.27-7 .26 (2H, m), 6.91 (1H, d, J = 8.5 Hz), 5.28 (2H, s), 4.17-4.12 (2H, m), 3.70 (3H) , S), 3.60 (3H, s), 2.14-2.10 (7H, m), 1.41 (3H, t, J = 7.1 Hz), 1.00-0.96 (2H) , M), 0.78-0.75 (2H, m). [54] ¹ H-NMR (CDCl ₃ ) δ: 7.45-7.40 (2H, m), 7.37 (1H, dd, J = 8.4, 1.7 Hz), 7.28-7 .26 (2H, m), 6.92 (1H, d, J = 8.5 Hz), 5.28 (2H, s), 3.80 (3H, s), 3.60 (3H, s), 2.21 (3H, s), 2.16-2.11 (4H, m), 2.10 (3H, s), 1.01-0.96 (2H, m), 0.78-0. 74 (2H, m). [55] ¹ H-NMR (CDCl ₃ ) δ: 7.45-7.39 (3H, m), 7.28-7.26 (2H, m), 6.93 (1H, d, J = 8) .5Hz), 5.29 (2H, s), 3.99 (3H, s), 3.61 (3H, s), 2.27 (6H, s), 2.16-2.10 (4H, m), 1.00-0.97 (2H, m), 0.78-0.76 (2H, m). [56] ¹ H-NMR (CDCl ₃ ) δ: 7.45-7.37 (3H, m), 7.29-7.27 (2H, m), 6.92 (1H, d, J = 8) .4 Hz), 5.28 (2H, s), 3.74 (3H, s), 3.61 (3H, s), 2.16-2.13 (1H, m), 2.11 (3H, s), 2.09 (3H, s), 1.02-0.97 (2H, m), 0.78-0.74 (2H, m). [57] ¹ H-NMR (CDCl ₃ ) δ: 7.43-7.36 (4H, m), 7.29-7.27 (1H, m), 6.88 (1H, d, J = 8) .4 Hz), 5.06 (2H, s), 3.74 (3H, s), 3.63 (3H, s), 2.51 (3H, s), 2.12 (3H, s), 2 .09 (3H, s). [58] ¹ H-NMR (CDCl ₃ ) δ: 7.50-7.36 (4H, m), 7.29-7.27 (1 H, m), 6.89 (1 H, d, J = 8) .6 Hz), 5.08 (2H, s), 3.74 (3H, s), 3.59 (3H, s), 2.85 (2H, q, J = 7.6 Hz), 2.11 ( 3H, s), 2.09 (3H, s), 1.28 (3H, t, J = 7.6 Hz). [59] ¹ H-NMR (CDCl ₃ ) δ: 7.47 (1H, t, J = 8.3 Hz), 7.37 (1H, s), 7.35-7.33 (1H, m), 7.09-7.07 (2H, m), 6.91 (1H, d, J = 8.4 Hz), 5.29 (2H, s), 3.93 (3H, s), 3.73 ( 3H, s), 3.59 (3H, s), 2.08 (3H, s), 2.03 (3H, s). [60] ¹ H-NMR (CDCl ₃ ) δ: 7.61 (1H, d, J = 2.2 Hz), 7.47-7.42 (2H, m), 7.16 (1H, s), 7.11 (1H, d, J = 8.2 Hz), 7.06 (1H, d, J = 8.5 Hz), 6.96 (1H, d, J = 8.5 Hz), 5.44 (2H , S), 3.94 (3H, s), 3.86 (3H, s), 3.63 (3H, s), 2.17 (3H, d, J = 0.7 Hz). [61] ¹ H-NMR (CDCl ₃ ) δ: 7.66 (1H, d, J = 2.2 Hz), 7.47 (1H, dd, J = 8.5, 2.2 Hz), 7.42 (1H, d, J = 7.8 Hz), 7.29 (2H, t, J = 8.1 Hz), 7.17 (1H, s), 6.97 (1H, d, J = 8.7 Hz) , 5.43 (2H, s), 3.87 (3H, s), 3.65 (3H, s), 2.19-2.15 (4H, m), 1.04-0.99 (2H) , M), 0.78-0.74 (2H, m). [62] ¹ H-NMR (CDCl ₃ ) δ: 7.62 (1H, dd, J = 8.4, 2.3 Hz), 7.57 (1H, dd, J = 2.0, 0.7 Hz) 7.45-7.39 (2H, m), 7.29-7.27 (1 H, m), 6.89 (1 H, d, J = 8.4 Hz), 5.07 (2H, s) , 4.11 (3H, s), 3.70 (3H, s), 3.62 (3H, s), 2.51 (3H, s), 2.12 (3H, s). [63] ¹ H-NMR (CDCl ₃ ) δ: 7.62 (1H, d, J = 8.5 Hz), 7.57 (1H, s), 7.49-7.43 (2H, m), 7.29-7.27 (1H, m), 6.89 (1H, d, J = 8.5 Hz), 5.08 (2H, s), 4.11 (3H, s), 3.70 ( 3H, s), 3.58 (3H, s), 2.84 (2H, q, J = 7.5 Hz), 2.11 (3H, s), 1.27 (3H, t, J = 7. 5 Hz). [64] ¹ H-NMR (CDCl ₃ ) δ: 7.58 (1H, dd, J = 8.5, 2.3 Hz), 7.53 (1H, d, J = 1.6 Hz), 7.46 (1H, t, J = 8.1 Hz), 7.09-7.06 (2H, m), 6.91 (1H, d, J = 8.7 Hz), 5.29 (2H, s), 4 .10 (3H, s), 3.92 (3H, s), 3.69 (3H, s), 3.58 (3H, s), 2.03 (3H, s). [65] ¹ H-NMR (CDCl ₃ ) δ: 7.63-7.59 (2H, m), 7.56 (1H, dd, J = 2.2, 0.6 Hz), 7.47 (1H , T, J = 8.0 Hz), 7.40 (1H, dd, J = 8.0, 1.4 Hz), 6.89 (1H, d, J = 8.5H), 5.35 (2H, s), 4.11 (3H, s), 3.70 (3H, s), 3.59 (3H, s), 2.06 (3H, s).

As an aspect of this tetrazolinone compound in this invention composition, the following are mentioned, for example.
In Formula (1), R ¹ is a C1-C3 alkyl group or a halogen atom, R ² is a hydrogen atom or a C1-C3 alkyl group, R ³ is a C1-C3 alkyl group, a C1-C3 alkoxy group, a halogen atom An atom or a cyclopropyl group, Z ¹ is a C1-C3 alkyl group, Z ² is a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom or a cyano group, and Z ³ A tetrazolinone compound in which is a hydrogen atom, a C1-C3 alkyl group or a halogen atom.
In formula (1), R ¹ is a C1-C3 alkyl group or a halogen atom, R ² is a hydrogen atom or a C1-C3 alkyl group, R ³ is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group. And Z ¹ is a C1-C3 alkyl group, Z ² is a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom or a cyano group, Z ³ is a hydrogen atom, C1- A tetrazolinone compound which is a C3 alkyl group or a halogen atom;
In formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom or a C1-C3 alkyl group, R ³ is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group, and Z ¹ is a C1-C3 alkyl group, ^{Z 2} is 1 or more halogen atoms optionally C1-C3 may be alkyl groups having a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1-C3 alkyl group Or a tetrazolinone compound which is a halogen atom.
In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group, and Z ¹ is a C1-C3 alkyl group A tetrazolinone compound in which Z ² is a C1-C3 alkyl group, a halogen atom or a cyano group optionally having one or more halogen atoms, and Z ³ is a C1-C3 alkyl group or a halogen atom.
In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, Z ¹ is a C1-C3 alkyl group, and Z ² is one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, tetrazolinone compound Z ³ is a C1-C3 alkyl group or a halogen atom.
In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a halogen atom, Z ¹ is a C1-C3 alkyl group, and Z ² is 1 or more. halogen atom optionally may C1-C3 alkyl group optionally having a halogen atom or a cyano group, tetrazolinone compound Z ³ is a C1-C3 alkyl group or a halogen atom.
In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a cyclopropyl group, Z ¹ is a C1-C3 alkyl group, and Z ² is 1 or more. halogen atoms optionally may C1-C3 alkyl group optionally having a halogen atom or a cyano group, tetrazolinone compound Z ³ is a C1-C3 alkyl group or a halogen atom.
In formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, and R ³ may have one or more halogen atoms, a C1-C3 alkyl group, a halogen atom, C1 -C3 alkoxy group or a cyclopropyl group, ^{Z 1} is a C1-C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl, halogen atom, a C1-C2 alkylthio group or a cyano group, ^{Z 3} is a hydrogen atom, tetrazolinone compound is C1-C3 alkyl group or a halogen atom.
In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A tetrazolinone compound which is a C3 alkyl group or a halogen atom;

Examples of the composition of the present invention include the following.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group, and Z ¹ is a C1-C3 alkyl group a group, Z ² is 1 or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, a tetrazolinone compound Z ³ is a C1-C3 alkyl group or a halogen atom, A plant disease control composition comprising any one of compounds I to VI.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group, and Z ¹ is a C1-C3 alkyl group a group, Z ² is 1 or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, a tetrazolinone compound Z ³ is a C1-C3 alkyl group or a halogen atom, A plant disease control composition containing any one of compounds I.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group, and Z ¹ is a C1-C3 alkyl group a group, Z ² is 1 or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, a tetrazolinone compound Z ³ is a C1-C3 alkyl group or a halogen atom, A plant disease control composition containing any one of compounds II.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group, and Z ¹ is a C1-C3 alkyl group a group, Z ² is 1 or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, a tetrazolinone compound Z ³ is a C1-C3 alkyl group or a halogen atom, A plant disease control composition containing any one of compounds III.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group, and Z ¹ is a C1-C3 alkyl group a group, Z ² is 1 or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, a tetrazolinone compound Z ³ is a C1-C3 alkyl group or a halogen atom, A plant disease control composition containing any one of compounds IV.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group, and Z ¹ is a C1-C3 alkyl group a group, Z ² is 1 or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, a tetrazolinone compound Z ³ is a C1-C3 alkyl group or a halogen atom, A plant disease control composition containing any one of the compounds V.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group, and Z ¹ is a C1-C3 alkyl group a group, Z ² is 1 or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, a tetrazolinone compound Z ³ is a C1-C3 alkyl group or a halogen atom, A plant disease control composition containing any one of the compounds VI.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom and any one of compounds I to VI.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom, and any one of compounds I.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom, and any one of compounds II.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom and any one of compounds III.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom and any one of compounds IV.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom, and any one of compounds V.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom and any one of compounds VI.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom and any one of compounds XXVIII to XXXIII.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom, and a compound XXVIII.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom and a compound XXIX.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom and a compound XXX.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom and a compound XXXI.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom and a compound XXXII.

In Formula (1), R ¹ is a C1-C3 alkyl group, R ² is a hydrogen atom, R ³ is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group, and Z ¹ is C1 an -C3 alkyl group, ^{Z 2} is C1-C2 alkoxy group, one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group, ^{Z 3} is a hydrogen atom, C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom and a compound XXXIII.

A plant disease control composition containing any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound I in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound I in a ratio of 1: 1;
A plant disease control composition comprising any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound I in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound II in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound II in a ratio of 1: 1;
A plant disease control composition comprising any one compound from the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound II in a ratio of 10: 1;
A plant disease control composition containing any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound III in a ratio of 0.1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound III in a ratio of 1: 1;
A plant disease control composition containing any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound III in a ratio of 10: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound IV in a ratio of 0.1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound IV in a ratio of 1: 1;
A plant disease control composition comprising any one compound from the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound IV in a ratio of 10: 1;
A plant disease control composition containing any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound V in a ratio of 0.1: 1;
A plant disease control composition containing any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound V in a ratio of 1: 1;
A plant disease control composition containing any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound V in a ratio of 10: 1;
A plant disease control composition containing any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound VI in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound VI in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound VI in a ratio of 10: 1;
A plant disease control composition containing any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound VII in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound VII in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound VII in a ratio of 10: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound VIII in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound VIII in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound VIII in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound IX in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound IX in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound IX in a ratio of 10: 1;
A plant disease control composition containing any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound X in a ratio of 0.1: 1;
A plant disease control composition containing any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound X in a ratio of 1: 1;
A plant disease control composition containing any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound X in a ratio of 10: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XI in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XI in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XI in a ratio of 10: 1;
A plant disease control composition comprising any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound XII in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XII in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XII in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XIII in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XIII in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XIII in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XIV in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XIV in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XIV in a ratio of 10: 1;
A plant disease control composition containing any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound XV in a ratio of 0.1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XV in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XV in a ratio of 10: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XVI in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XVI in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XVI in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XVII in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XVII in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XVII in a ratio of 10: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XVIII in a ratio of 0.1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XVIII in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XVIII in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XIX in a ratio of 0.1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XIX in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XIX in a ratio of 10: 1;
A plant disease control composition containing any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XX in a ratio of 0.1: 1;
A plant disease control composition containing any one compound from the tetrazolinone compound 1 to the tetrazolinone compound 65 and the compound XX in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XX in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXI in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXI in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXI in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXII in a ratio of 0.1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXII in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXII in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and XXIII in a ratio of 0.1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXIII in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXIII in a ratio of 10: 1;
Plant disease control composition containing any one compound from the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and XXIV in a ratio of 0.1: 1 Any one compound from the present tetrazolinone compound 1 to the present tetrazolinone compound 65 And a compound XXIV in a ratio of 1: 1 plant disease control composition;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXIV in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXV in a ratio of 0.1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXV in a ratio of 1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXV in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXVI in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXVI in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXVI in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXVII in a ratio of 0.1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXVII in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXVII in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXVIII in a ratio of 0.1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXVIII in a ratio of 1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXVIII in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXIX in a ratio of 0.1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXIX in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXIX in a ratio of 10: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXX in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXX in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXX in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXI in a ratio of 0.1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXI in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXI in a ratio of 10: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXII in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXII in a ratio of 1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXII in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXIII in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXIII in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXIII in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXIV in a ratio of 0.1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXIV in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXIV in a ratio of 10: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXV in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXV in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXV in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXVI in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXVI in a ratio of 1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXVI in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXVII in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXVII in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXVII in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXVIII in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXVIII in a ratio of 1: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXVIII in a ratio of 10: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXIX in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXIX in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXIX in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXX in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXX in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXX in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXXI in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXXI in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXXI in a ratio of 10: 1;
A plant disease control composition comprising any one of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXXII in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXXII in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXXII in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXXIII in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXXIII in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXXIII in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXXIV in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound from the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and the compound XXXXIV in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXXIV in a ratio of 10: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXXV in a ratio of 0.1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXXV in a ratio of 1: 1;
A plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 65 and compound XXXXV in a ratio of 10: 1;

Next, formulation examples are shown. In addition, a part represents a weight part.

Formulation Example 1
A composition is obtained by thoroughly pulverizing and mixing 50 parts of any one of the compositions of the present invention, 3 parts of calcium lignin sulfonate, 2 parts of magnesium lauryl sulfate and 45 parts of synthetic silicon hydroxide.

Formulation Example 2
20 parts of any one of the compositions of the present invention and 1.5 parts of sorbitan trioleate were mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and pulverized by a wet pulverization method. Thereafter, 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate is added thereto, and further 10 parts of propylene glycol is added and stirred to obtain a preparation.

Formulation Example 3
A preparation is obtained by thoroughly pulverizing and mixing 2 parts of any one of the compositions of the present invention, 88 parts of kaolin clay and 10 parts of talc.

Formulation Example 4
A formulation is obtained by thoroughly mixing 5 parts of any one of the compositions of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene.

Formulation Example 5
Any one of the compositions of the present invention, 2 parts of composition, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are mixed and mixed well with water. The formulation is obtained by granulating and drying.

Formulation Example 6
10 parts of any one of the compositions of the present invention; 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt; and 55 parts of water are mixed and finely pulverized by a wet pulverization method. By doing so, a formulation is obtained.

Next, test examples show that the composition of the present invention is useful for controlling plant diseases. “Efficacy” in each test means a value represented by the following formula 1, and is ranked as shown in [Table 5] according to the numerical value.
"Formula 1"
Efficacy = 100 × (XY) / X
X: Growth rate of untreated bacteria Y: Growth of treated bacteria

Test Example 1 Control Trial against Wheat Leaf Blight Fungus (Septoria tritici) Each test compound diluted in DMSO (dimethyl sulfoxide) at a predetermined concentration was dispensed into a titer plate (96 well), and then the wheat leaf blight fungus was separated in advance. 150 μl of potato broth liquid medium (PDB medium) inoculated with live spores was dispensed. The plate was cultured at 18 ° C. for 4 days to grow wheat leaf blight fungi, and then the growth degree of wheat leaf blight fungi was measured by absorbance at 550 nm in each well of the titer plate. Based on the degree of growth, the efficacy was calculated using “Formula 1” and ranked according to [Table 5].
The results are shown in [Table 6] to [Table 27].

Test example 2
A plastic pot is filled with soil, seeded with wheat (variety: Shirogane), and grown in a greenhouse for 14 days. The test compound is made into a preparation according to the preparation example, then diluted with water to a predetermined concentration, and the diluted solution is sprayed so as to adhere sufficiently to the leaf surface of the wheat. After spraying, the plants are air-dried, and after 2 days, spray-inoculated with an aqueous suspension (about 1,000,000 cells / ml) of conidia of wheat leaf blight fungus (Mycosphaerella graminicola). At first, after inoculation, place under high humidity at 18 ° C. for 3 days, take out from high humidity and cultivate in a constant temperature room at 18 ° C. for 14 days. Then, the lesion area of wheat leaf blight is investigated.
On the other hand, wheat is cultivated in the same manner as the treated area except that the diluted solution of the test compound is not sprayed on the foliage (this is referred to as an untreated area). After that, the lesion area of wheat leaf blight is investigated as in the treatment area.
As a result, a marked decrease in the lesion area of wheat treated with the disease control composition containing the present tetrazolinone compound and the present bactericidal active compound is recognized as compared with the lesion area in the untreated area.
Test example 3
The plastic pot is filled with soil, soybean (variety: Kurosengoku) is sown and grown in a greenhouse for 14 days. The test compound is made into a preparation according to the preparation example, then diluted with water to a predetermined concentration, and the diluted solution is sprayed so as to sufficiently adhere to the leaf surface of the die. After spraying, the plants are air-dried, and after 2 days, spray-inoculated with an aqueous suspension (about 10,000 / ml) of a summer spore of soybean rust fungus (Phakopsora pachyrhizi). First, after inoculation, place under high humidity at 23 ° C. for 1 day, take out from high humidity and cultivate in a 23 ° C. greenhouse for 10 days (this will be treated). Thereafter, the lesion area of soybean rust is investigated.
On the other hand, soybeans are cultivated in the same manner as the treated group except that the diluted solution of the test compound is not sprayed on the foliage (this is referred to as the untreated group). Then, the lesion area of soybean rust is investigated as in the treatment area.
As a result, the lesion area of soybean treated with the disease control composition containing the present tetrazolinone compound and the present bactericidal active compound is remarkably reduced as compared with the lesion area in the untreated area.
According to the present invention, plant diseases can be controlled.

Since the composition of the present invention exhibits an excellent control effect against plant diseases, it can be used as a plant disease control agent. .

Claims

Formula (1)

[Where,
R 1 represents a C1-C3 alkyl group which may have one or more halogen atoms or a halogen atom,
R 2 represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group,
R 3 represents a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a cyclopropyl group, or a C1-C3 alkoxy group optionally having one or more halogen atoms;
Z 1 represents a C1-C3 alkyl group,
Z 2 represents a hydrogen atom, a C1-C2 alkoxy group, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C2 alkylthio group, or a cyano group,
Z 3 represents a hydrogen atom, a C1-C3 alkyl group or a halogen atom. ]
A tetrazolinone compound represented by:
A plant disease control composition comprising one or more fungicidal active compounds selected from the group (A).
Group (A):
Propiconazole, Prothioconazole, Triadimenol, Prochloraz, Penconazole, Dibuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole bromconazole, epoxiconazole, difenoconazole, cyproconazole, metconazole, triflumizole, triflumizole aconazole, microbutanil, fenbuconazole, hexaconazole, fluquinconazole, triticonazole, tertanol, tertanol. ipconazole), simeconazole, hymexazole, etridiazole, flutriafol, bixafen, benzobindiflufirfulx Xapyroxad), penthiopyrad (penthiopyrad), N- (1,1,3- trimethyl indane-4-yl) -1-methyl-3-difluoromethyl-4-carboxylic acid amide,
A compound represented by the following formula (b):

Isofetamid, isopyrazam, boscalid, fluopyram, sedaxane, penflufen, fluthranil, flutronil, mepronil And furametopyr.
The plant disease control composition according to claim 1, wherein the weight ratio of the tetrazolinone compound to the bactericidal active compound is tetrazolinone compound / bactericidal active compound = 0.1 / 1 to 10/1.
Formula (1)

[Where,
R 1 represents a C1-C3 alkyl group which may have one or more halogen atoms or a halogen atom,
R 2 represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group,
R 3 represents a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a cyclopropyl group, or a C1-C3 alkoxy group optionally having one or more halogen atoms;
Z 1 represents a C1-C3 alkyl group,
Z 2 represents a hydrogen atom, a C1-C2 alkoxy group, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C2 alkylthio group, or a cyano group,
Z 3 represents a hydrogen atom, a C1-C3 alkyl group or a halogen atom. ]
The plant disease control method including the process of processing the effective amount of the tetrazolinone compound shown by 1 and the 1 or more types of fungicidal active compound chosen from a group (A) to the soil which grows a plant or a plant.
Group (A):
Propiconazole, Prothioconazole, Triadimenol, Prochloraz, Penconazole, Dibuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole, Tebuconazole bromconazole, epoxiconazole, difenoconazole, cyproconazole, metconazole, triflumizole, triflumizole aconazole, microbutanil, fenbuconazole, hexaconazole, fluquinconazole, triticonazole, tertanol, tertanol. ipconazole), simeconazole, hymexazole, etridiazole, flutriafol, bixafen, benzobindiflufirfulx Xapyroxad), penthiopyrad (penthiopyrad), N- (1,1,3- trimethyl indane-4-yl) -1-methyl-3-difluoromethyl-4-carboxylic acid amide,
A compound represented by the following formula (b):

Isofetamid, isopyrazam, boscalid, fluopyram, sedaxane, penflufen, fluthranil, flutronil, mepronil And furametopyr.
The method for controlling plant diseases according to claim 3, wherein the weight ratio of the tetrazolinone compound to the bactericidal active compound is tetrazolinone compound / bactericidal active compound = 0.1 / 1 to 10/1.
The plant disease control method according to claim 3, wherein the plant or the soil in which the plant is cultivated is wheat or soil in which the wheat is cultivated.
The plant disease control method according to claim 4, wherein the plant or the soil in which the plant is cultivated is wheat or soil in which the wheat is cultivated.