composition and method for the control of plant diseases

专利摘要:
COMPOSITION AND METHOD FOR PLANT DISEASE CONTROL. A plant disease control composition comprising a tetrazolinone compound represented by formula (1): where n is an integer equal to any one from 0 to 5; R1 represents a halogen atom and the like; R2 represents a C1-C3 alkyl group and the like; R1 or R2 can independently have halogen atom (s) in the alkyl portion; with the proviso that when n is an integer equal to 2 or more, two or more of R1 can be different from each other, and a carboxamide compound, preferably the composition for the control of plant diseases where the weight ratio of the compound tetrazolinone for the carboxamide compound it is that of the tetrazolinone compound / carboxamide compound 0.1 / 1 to 10/1, it shows an excellent control efficacy in plant diseases.
公开号:BR112016001401B1
申请号:R112016001401-4
申请日:2014-07-15
公开日:2021-03-16
发明作者:Yuichi Matsuzaki
申请人:Sumitomo Chemical Company, Limited；
IPC主号:

专利说明:

Technical Field
[001] This application claims priority and benefit from Japanese Patent Application No. 2013-151419, filed on July 22, 2013, the full text of which is incorporated herein by reference.
[002] The present invention relates to a composition for the control of plant diseases and its use. Prior Art
[003] So far, many compounds have been developed and used in practice to control plant diseases (see Patent Literature 1 and 2). Citation List Patent Literature
[004] Patent Literature 1: WO pamphlet 99/05139 Patent Literature 2: WO pamphlet 2013/092224 Summary of the Invention Problems to be solved by the Invention
[005] It is the objective of the present invention to offer a composition having an excellent control efficacy in plant diseases. Means to solve the Problems
[006] The present inventors studied intensively to find a composition having an excellent control efficacy in plant diseases. As a result, they found that a plant disease control composition comprising a tetrazolinone compound represented by the formula (1) below and one or more carboxamide compounds selected from Group (A) mentioned below has excellent control effectiveness in diseases of plants.
[007] Specifically, the present invention includes the following: [1] A composition for the control of plant diseases comprising a tetrazolinone compound represented by formula (1):
where n is an integer equal to any one from 0 to 5; R1 represents a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a nitro group or a cyano group; R2 represents a C1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogen atom, a C1-C3 alkoxy group, a C1-C2 alkylthio group, a C2-C3 alkenyl group, or a C2-C3 alkynyl group, R1 or R2 may independently have halogen atom (s) in the alkyl portion; with the proviso that when n is an integer equal to 2 or more, two or more of R1 can be different from each other, and one or more carboxamide compounds selected from Group (A): Group (A): a group consisting of bixafen, benzovindiflupir, fluxpyroxad, pentiopirad, N- (1,1,3-trimethylindan-4-yl) -1-methyl-3-difluoromethylpyrazole-4-carboxylic acid amide, a compound represented by the following formula (b):
isofetamid, isopirazam, boscalid, fluopyram, silkxane, penflufen, flutolanil, mepronil, carboxin, tifluzamide, and furametpir. [2] The composition for the control of plant diseases described in item [1] in which the weight ratio of the tetrazolinone compound to the carboxamide compound is that of the tetrazolinone compound / carboxamide compound = 0.1 / 1 to 10/1. [3] A method for the control of plant diseases that comprises applying an effective amount of a tetrazolinone compound represented by formula (1):
where n is an integer equal to any one from 0 to 5; R1 represents a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a nitro group or a cyano group; R2 represents a C1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogen atom, a C1-C3 alkoxy group, a C1-C2 alkylthio group, a C2-C3 alkenyl group, or a C2-C3 alkynyl group, R1 or R2 can independently have halogen atoms in the alkyl portion; with the proviso that when n is an integer equal to 2 or more, two or more of R1 can be different from each other, and one or more carboxamide compounds selected from Group (A): Group (A): a group consisting of bixafen, benzovindiflupir, fluxpyroxad, pentiopirad, N- (1,1,3-trimethylindan-4-yl) -1-methyl-3-difluoromethylpyrazole-4-carboxylic acid amide, a compound represented by the following formula (b):
isofetamid, isopirazam, boscalid, fluopyram, silkxane, penflufen, flutolanil, mepronil, carboxin, tifluzamide, and furametpir,
[008] to a plant or soil for growing the plant. [4] The method for the control of plant diseases described in item [3] where the weight ratio of the tetrazolinone compound to the carboxamide compound is that of the tetrazolinone compound / carboxamide compound = 0.1 / 1 to 10/1. [5] The method for controlling plant diseases described in item [3] or [4] where the plant or soil for growing the plant is wheat or soil for growing wheat, respectively. Mode for Carrying Out the Invention
[009] A composition for the control of plant diseases (hereinafter "the composition of the present invention") comprises a tetrazolinone compound represented by formula (1):
[where n, R1 and R2 have the same definitions given above, respectively.] (hereinafter "present tetrazolinone compound") and one or more carboxamide compounds selected from Group (A) (hereinafter "present carboxamide compound")
[0010] Group (A): a group consisting of bixafen, benzovindiflupir, fluxpyroxad, pentiopirad, N- (1,1,3-trimethylindan-4-yl) -1-methyl-3-difluoromethylpyrazol-4- acid amide carboxylic acid, a compound represented by the following formula (b):
isofetamid, isopirazam, boscalid, fluopyram, silkxane, penflufen, flutolanil, mepronil, carboxin, tifluzamide, and furametpir.
[0011] The present tetrazolinone is explained.
[0012] The substituent (s) described in this report are described in more detail below.
[0013] The term "halogen atom" as used in this report includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
[0014] The term "C1-C6 alkyl group" as used in this report represents a straight or branched hydrocarbon group having 1 to 6 carbon atoms, and includes, for example, a methyl group, an ethyl group, a propyl group , an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.
[0015] The term "C1-C6 alkoxy group" as used in this report can be a straight or branched chain group, and includes, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, a pentyloxy group, and a hexyloxy group.
[0016] The term "C1-C6 alkylthio group" as used in this report can be a straight or branched chain group, and includes, for example, a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a group butylthio, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group, and a hexylthio group.
[0017] The term "C1-C3 alkyl group" as used in this report includes a methyl group, an ethyl group, a propyl group, and an isopropyl group.
[0018] The term "C2-C3 alkenyl group" as used in this report includes a vinyl group, a 1-propenyl group, and a 2-propenyl group.
[0019] The term "C2-C3 alkynyl group" as used in this report includes an ethynyl group, a 1-propynyl group, and a 2-propynyl group.
[0020] The term "C3-C4 cycloalkyl group" as used in this report includes a cyclopropyl group, and a cyclobutyl group.
[0021] The term "C1-C3 alkoxy group" as used in this report includes a methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group.
[0022] The term "C1-C2 alkylthio group" as used in this report includes a methylthio group and an ethylthio group.
[0023] The expression "may have halogen atom (s) in the alkyl portion" as used in this report means that in the definitions of R1 and R2, the C1-C6 alkyl group, the C1-C3 alkyl group, the C1-C6 group alkoxy, C1-C3 alkoxy group, C1-C6 alkylthio group, C1-C2 alkylthio group, and C3-C4 cycloalkyl group can have halogen atom (s).
[0024] The C1-C6 alkyl group having halogen atom (s) as used in this report includes, for example, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monochloromethyl group, a dichloromethyl group, a trichloromethyl group, dibromomethyl group, a chlorofluoromethyl group, a dichlorofluoromethyl group, a chlorodifluoromethyl group, a 2-fluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a 3-fluoropropyl group, a 3 2,2-difluoropropyl group, a 3,3,3-trifluoropropyl group, a heptafluoropropyl group, a heptafluoroisopropyl group, a 1- (trifluoromethyl) -2,2,2-trifluoroethyl group, a 3-fluoropropyl group, a group 4 - fluorobutyl, and a 5-fluorohexyl group.
[0025] The C1-C3 alkyl group having halogen atom (s) as used in this report includes, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a dibromomethyl group, a chlorofluoromethyl group, a dichlorofluoromethyl group, a chlorodifluoromethyl group, a 2-fluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 2-chloroethyl group, a 2,2 group -dichloroethyl, a 2,2,2-trichloropropyl group, a pentafluoroethyl group, a 3-fluoropropyl group, a 3,3,3 group, -trifluoropropyl, a heptafluoropropyl group, a heptafluoroisopropyl group, and a 1- (trifluoromethyl) group -2,2,2-trifluoroethyl, among others.
[0026] The C1-C6 alkoxy group having halogen atom (s) as used in this report includes, for example, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a chloromethoxy group, a dichloromethoxy group, a trichloromethoxy group, dibromomethoxy group, a chlorofluoromethoxy group, a dichlorofluoromethoxy group, a chlorodifluoromethoxy group, a 2-fluoroethoxy group, a 2,2, -difluoroethoxy group, a 2,2,2-trifluoroethoxy group, a 2-chloroethoxy group, a group 2, 2-dichloroethoxy, a 2,2,2-trichloroethoxy group, a pentafluoroethoxy group, a 3-fluoropropyloxy group, a 3,3,3-trifluoropropyloxy group, a heptafluoropropyloxy group, a heptafluoroisopropyloxy group, a 1- (trifluoromethyl) group 2,2,2-trifluoroethyloxy, a 3-fluoropropyloxy group, a 4-fluorobutyloxy group, and a 5-fluorohexyloxy group, among others.
The C1-C3 alkoxy group having halogen atom (s) includes, for example, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a chloromethoxy group, a dichloromethoxy group, a trichloromethoxy group, a dibromomethoxy group, chlorofluoromethoxy group, a dichlorofluoromethoxy group, a chlorodifluoromethoxy group, a 2-fluoroethoxy group, a 2,2-difluoroethoxy group, a 2,2,2-trifluoroethoxy group, a 2-chloroethoxy group, a 2,2-dichloroethoxy group, a 2,2-dichloroethoxy group, 2,2,2-trichloroethoxy group, a pentafluoroethoxy group, a 3-fluoropropyloxy group, a 3,3,3-trifluoropropyloxy group, a heptafluoropropyloxy group, a heptafluoroisopropyloxy group, a 1- (trifluoromethyl) -2,2,2 group -trifluoroethyloxy, and a 3-fluoropropyloxy group, among others.
The C1-C6 alkylthio group having halogen atom (s) includes, for example, a monofluoromethylthio group, a difluoromethylthio group, a trifluoromethylthio group, a monochloromethylthio group, a dichloromethylthio group, a trichloromethylthio group, a dibromomethylthio group chlorofluoromethylthio group, a dichlorofluoromethylthio group, a chlorodifluoromethylthio group, a 2-fluoroethylthio group, a 2,2-difluoroethylthio group, a 2,2,2-trifluoroethylthio group, a pentafluoroethylthio group, a 3-fluoropropylthio group, a 2,2 group -difluoropropylthio, a 3,3,3-trifluoropropylthio group, a heptafluoropropylthio group, a heptafluoroisopropylthio group, a 1- (trifluoromethyl) -2,2,2-trifluoroethylthio group, a 3-fluoropropylthio group, a 4-fluorobutyl group, and a 5-fluorohexylthio group, among others.
The C1-C2 alkylthio group having halogen atom (s) includes, for example, a monofluoromethylthio group, a difluoromethylthio group, a trifluoromethylthio group, a monochloromethylthio group, a dichloromethylthio group, a trichloromethylthio group, a dibromomethylthio group chlorofluoromethylthio group, a dichlorofluoromethylthio group, a chlorodifluoromethylthio group, a 2-fluoroethylthio group, a 2,2-difluoroethylthio group, a 2,2,2-trifluoroethylthio group, and a pentafluoroethylthio group, among others.
The C3-C4 cycloalkyl group having halogen atom (s) includes, for example, a 2-fluorocyclopropyl group, a 2,2-difluorocyclopropyl group, a 2-chloro-2-fluorocyclopropyl group, a 2.2 group -dichlorocyclopropyl, a 2,2-dibromocyclopropyl group, and a 2,2,3,3-tetrafluorocyclobutyl group, among others.
[0031] First, a process for the preparation of the present tetrazolinone compound is explained.
[0032] The present tetrazolinone compound can be prepared, for example, according to the processes mentioned below. Process A
[0033] The present tetrazolinone compound can be prepared by reacting a compound represented by formula (2) (hereinafter called Compound (2)) with a compound represented by formula (3) (hereinafter called Compound (3)) in the presence of a base.
[where, n, R1 and R2 are as defined above, respectively, and Z1 represents a leaving group such as a chlorine atom, a bromine atom, or an iodine atom].
[0034] The reaction is usually carried out in a solvent.
[0035] Examples of the solvent to be used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, and xylene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisol, methyl tert-butyl ether, and diisopropyl ether; halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, and chlorobenzene; acid amides such as N, N-dimethylformamide, 1,3-dimethyl-2-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; nitriles such as acetonitrile, and propionitrile; Water; and mixed solvents thereof.
[0036] Examples of the base to be 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, and cesium carbonate; alkali metal bicarbonates such as lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, 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; and alkali metal alkoxides such as sodium tert-butoxide, and potassium tert-butoxide.
[0037] In the reaction, Compound (3) is normally used in a range of molar ratios from 1 to 10, and the base is normally used in a range of molar ratios from 0.5 to 5, in relation to 1 mol of Compound (2).
[0038] The reaction temperature normally ranges from -20 to 150 ° C. The reaction time usually ranges from 0.1 to 24 hours.
[0039] If necessary, sodium iodide, tetrabutylammonium iodide, among others can be added to the reaction, and these compounds are generally used in a range of molar ratios from 0.001 to 1.2 with respect to 1 mole of Compound (2) .
[0040] When the reaction is over, the reaction mixture is extracted with organic solvents, and the resulting organic layers are worked (for example, drying and concentration) to isolate the present tetrazolinone compound. The isolated tetrazolinone compound can be further purified, for example, by chromatography and recrystallization. Process B
[0041] The present tetrazolinone compound can be prepared by reacting a compound represented by formula (4) (hereinafter called Compound (4)) with a compound represented by formula (5) (hereinafter called Compound (5)) in the presence of a catalyst and a base.
[where, n, R1, R2 are defined as above, respectively, and Z2 represents a leaving group, such as a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, and a p-toluenesulfonyloxy group, a B (OH) 2, an alkoxyboryl group, or a trifluoroborate (BF3-K +).]
[0042] The reaction is usually carried out in a solvent.
[0043] Examples of the solvent to be used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, and xylene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisol, methyl tert-butyl ether, and diisopropyl ether; halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, and chlorobenzene; acid amides such as N, N-dimethylformamide, 1,3-dimethyl-2-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; nitriles such as acetonitrile, and propionitrile; and mixed solvents thereof.
[0044] The Compound (5) to be used in the reaction can generally be used as a commercially available product. Specific examples include chlorobenzene, bromobenzene, iodobenzene, paradichlorobenzene, 4-chlorobromobenzene, 4-chloriodobenzene, 4-bromoiodobenzene, phenylboronic acid, 4-fluorophenylboronic acid, 4-chlorophenylboronic acid, 4-methylphenylboronic acid, and 4-methoxyphenylboronic acid.
[0045] Examples of the catalyst to be used in the reaction include copper (I) iodide, copper (II) acetate, palladium (II) acetate, dichlorobis (triphenylphosphine) palladium, tetrakistriphenylphosphine palladium (0), palladium acetate (II ) / trisciclohexylphosphine, bis (diphenylphosphine ferrocenyl) dichloride palladium (II), 1,3-bis (2,6-diisopropylphenyl) imidazole-2-ylidene (1,4-naphthoquinone) palladium, aryl ( chlorine) (1,3-dimesityl-1,3-dihydro-2H-imidazol-2-ylidene) palladium, or palladium (II) acetate / dicyclohexyl (2 ', 4', 6'-tri- isopropylbiphenyl-2-yl) phosphine, and tris (dibenzylidene acetone) dipaladium.
[0046] Examples of the base to be 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, and cesium carbonate; alkali metal bicarbonates such as lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, 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; alkali metal phosphates such as tripotassium phosphate; and alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide.
[0047] In the reaction, Compound (5) is normally used in a range of molar ratios from 1 to 10, and the catalyst is normally used in a range of molar ratios from 0.001 to 5, and the base is normally used in a range of molar ratios from 0.5 to 10, in relation to 1 mol of Compound (4).
[0048] If necessary, a binder such as 1,10-phenanthroline, tetramethylenediamine, among others, can be added to the reaction, and these compounds are generally used in a range of molar ratios from 0.001 to 5 with respect to 1 mole of Compound ( 4).
[0049] The reaction temperature normally ranges from -20 to 150 ° C. The reaction time usually ranges from 0.1 to 24 hours.
[0050] When the reaction is over, the reaction mixture is extracted with organic solvents, and the resulting organic layers are worked (for example, drying and concentration) to isolate the present tetrazolinone compound. The isolated tetrazolinone compound can be further purified, for example, by chromatography and recrystallization. Process C
[0051] The present tetrazolinone compound can be prepared by coupling a compound represented by formula (6) (hereinafter called Compound (6)) (which can be prepared according to the invention a method similar to that of Process A) with a compound represented by formula (7) (hereinafter called Compound (7)) in the presence of a base and a catalyst.
[where n, R1 and R2 are as defined above, respectively, Z3 represents a chlorine atom, a bromine atom, an iodine atom, or a trifluoromethanesulfonyloxy group, and Z4 represents a B (OH) 2, an alkoxyboryl group , or a trifluoroborate (BF3-K +).]
[0052] The reaction is usually carried out in a solvent.
[0053] Examples of the solvent to be used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, and xylene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisol, methyl tert-butyl ether, and diisopropyl ether; halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, and chlorobenzene; acid amides such as N, N-dimethylformamide, 1,3-dimethyl-2-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; nitriles such as acetonitrile, and propionitrile; alcohols such as methanol, ethanol, propanol, and butanol; Water; and mixed solvents thereof.
[0054] The organoboro compound (7) to be used in the reaction can be used as a commercially available compound, or it can be prepared according to a method described in a review article by N. Miyaura and A. Suzuki, Chem. Rev. 1995, 95, 2457, among others. The organoboro compound (7) to be used in the reaction can be prepared, for example, by reacting an iodine compound for R2 (R2-I) or a bromine compound for R2 (R2-Br) with an alkyl lithium ( such as butyl lithium), followed by reaction of the resulting mixture with boronate esters to obtain boronate ester derivatives. Also, the boronate ester derivatives obtained in the reaction mentioned above can be hydrolyzed as needed to give the corresponding boronic acid type derivatives. In addition, according to a method described in a review article by Molander et al. Acc. Chem. Res. 2007, 40, 275, among others, the boronate ester derivatives mentioned above can be fluorinated with potassium bifluoride and the like to obtain the trifluoroborate salts BF3-K +.
[0055] Examples of the catalyst to be used in the reaction include palladium (II) acetate, dichlorobis (triphenylphosphine) palladium, tetracycliphenylphosphinapalladium (0), palladium (II) acetate / bis (diphenylphosphine) ferrocenyl (diphenylphosphine) ferrocenyl II), 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene (1,4-naphthoquinone) palladium, aryl (chlorine) (1,3-dimethyl-1,3-di- hydro-2H-imidazol-2-ylidene) palladium or palladium (II) / dicyclohexyl (2 ', 4', 6'-triisopropylbiphenyl-2-yl) phosphine, and tris (dibenzylidenoacetone) dipaladium, between others.
[0056] Examples of the base to be 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, and cesium carbonate; alkali metal bicarbonates such as lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, 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; alkali metal phosphates such as tripotassium phosphate; and alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide.
[0057] In the reaction, Compound (7) is normally used in a range of molar ratios from 1 to 10, and the base is normally used in a range of molar ratios from 1 to 10, and the catalyst is normally used in a molar ratio range from 0.0001 to 1, in relation to 1 mol of Compound (6).
[0058] The reaction temperature usually ranges from 0 to 150 ° C. The reaction time usually ranges from 0.1 to 24 hours.
[0059] When the reaction is over, the reaction mixture is extracted with organic solvents, and the resulting organic layers are worked (for example, drying and concentration) to isolate the present tetrazolinone compound. The isolated tetrazolinone compound can be further purified, for example, by chromatography and recrystallization.
[0060] In the following, a method for the preparation of a synthetic intermediate compound of the present compound tetrazolinone is explained in detail. Reference Process A
[0061] The compound represented by formula (9) (hereinafter called Compound (9)) can be prepared by reacting Compound (2) with a compound represented by formula (8) (hereinafter called Compound (8)) in the presence of a base.
[where R2 and Z1 are as defined above, respectively, and R3 represents a protecting group such as an acetyl group, a formyl group, a benzoyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group, and a tert group - butoxycarbonyl.]
[0062] The reaction can be carried out according to process A mentioned above. Reference Process B
[0063] The compound represented by formula (4) can be prepared by treating Compound (9) with a deprotecting agent.
[where, R2 and R3 are as defined above, respectively.]
[0064] The reaction is usually carried out in a solvent.
[0065] Examples of the solvent to be used in the reaction include ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisol, methyl tert-butyl ether, and diisopropyl ether; hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, and xylene; halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, and chlorobenzene; nitriles such as acetonitrile, and propionitrile; acid amides such as N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone; sulfoxides such as dimethyl sulfoxide; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohols such as methanol, ethanol, propanol, and butanol; Water; and mixed solvents thereof.
[0066] The deprotecting agent to be used in the reaction can be used as a base or an acid. Examples of the base include organic bases such as triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, and diazabicyclononene, piperidine; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide. Examples of the acid include trifluoroacetic acid, hydrochloric acid, and sulfuric acid.
[0067] In the reaction, the deprotecting agent is normally used in a range of molar ratios from 1 to 100 in relation to 1 mol of Compound (9).
[0068] The reaction temperature usually ranges from -20 to 150 ° C. The reaction time usually varies within a range of 0.1 to 24 hours.
[0069] When the reaction is over, the reaction mixture is extracted with organic solvents, and the resulting organic layers are worked (for example, drying and concentration) to isolate the Compound (4). Compound (4) alone can be further purified, for example, by distillation, chromatography and recrystallization. Reference Process C
[0070] The compound represented by formula (11) (hereinafter called compound (11)) can be prepared by reacting a compound represented by formula (10) (hereinafter called Compound (10)) with an azidating agent.
(10) (11) [where, R2 has the same definition given above.]
[0071] The reaction is usually carried out in a solvent.
[0072] Examples of the solvent to be used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, and xylene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisol, methyl tert-butyl ether, and diisopropyl ether; halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, and chlorobenzene; acid amides such as N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone; esters such as ethyl acetate, and methyl acetate; sulfoxides such as dimethyl sulfoxide; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; nitriles such as acetonitrile, and propionitrile; and mixed solvents thereof.
[0073] Examples of the azidation agent to be 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.
[0074] In the reaction, the azidation agent is normally used in a range of molar ratios from 1 to 10 in relation to 1 mol of Compound (10).
[0075] The reaction temperature usually ranges from -20 to 150 ° C. The reaction time usually ranges from 0.1 to 24 hours.
[0076] If necessary, a Lewis acid such as aluminum chloride and zinc chloride can be added to the reaction, and these compounds are generally used in a range of molar ratios from 0.05 to 5 with respect to 1 mole of Compound (10).
[0077] When the reaction is over, the reaction mixture is extracted with organic solvents, and the resulting organic layers are worked (for example, drying and concentration) to isolate the Compound (11). Compound (11) alone can be further purified, for example, by chromatography and recrystallization. Reference Process D
[0078] The compound represented by formula (13) (hereinafter called Compound (13)) can be prepared by reacting Compound (11) with a compound represented by formula (12) (hereinafter called Compound (12)) in the presence of a base.
[where, R2 has the same definition given above, and Z5 represents a leaving group, such as a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, and a p-toluenesulfonyloxy group.]
[0079] The reaction is usually carried out in a solvent.
[0080] Examples of the solvent to be used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, and xylene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisol, methyl tert-butyl ether, and diisopropyl ether; halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, and chlorobenzene; acid amides such as N, N-dimethylformamide, 1,3-dimethyl-2-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; nitriles such as acetonitrile, and propionitrile; Water; and mixed solvents thereof.
[0081] The Compound (12) to be used in the reaction can generally be used as a commercially available product. Specific examples include alkyl halides such as methyl bromide, and methyl iodide; dialkyl sulfates such as dimethyl sulfate; alkyl or aryl sulfates such as methyl p-toluenesulfonate, and methyl methanesulfonate.
Examples of the base to be used in the reaction include organic bases such as triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclone; alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; alkali metal bicarbonates such as lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, 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; and alkali metal alkoxides such as sodium tert-butoxide, and potassium tert-butoxide.
[0083] In the reaction, Compound (12) is normally used in a range of molar ratios from 1 to 10, and the base is normally used in a range of molar ratios from 0.5 to 10, in relation to 1 mol of Compound (11).
[0084] The reaction temperature usually ranges from -20 to 150 ° C. The reaction time usually ranges from 0.1 to 24 hours.
[0085] When the reaction is finished, the reaction mixture is extracted with organic solvents, and the resulting organic layers are worked (for example, drying and concentration) to isolate the Compound (13). Compound (13) alone can be further purified, for example, by chromatography and recrystallization. Reference Process E
[0086] Compound (2) can be prepared by reacting Compound (13) with a halogenating agent.
[where, R2 and Z1 are as defined above, respectively.]
[0087] The reaction is usually carried out in a solvent.
[0088] Examples of the solvent to be used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, and xylene; ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisol, methyl tert-butyl ether, and diisopropyl ether; halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, fluorobenzene, difluorobenzene, trifluorobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, α, α, α-trifluorotene; 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 mixed solvents thereof.
[0089] Examples of the halogenating agent to be used in the reaction include a chlorinating agent, a brooding agent or an iodizing 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-benzenesulfonamide, and N-bromophthalimide.
[0090] A radical initiator can be used in the reaction.
[0091] Examples of the radical initiator to be used in the reaction include benzoyl peroxide, azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile, diacylperoxide, dialkyl peroxydicarbonate, tert-alkyl peroxyester, monoperoxy carbonate, di (tert-alkyl peroxy and cetal peroxy) cetal peroxide and cetal peroxyethoxy and cetal peroxide). of ketone.
[0092] In the reaction, the halogenating agent is normally used in a range of molar ratios from 1 to 10, and the radical initiator is normally used in a range of molar ratios from 0.01 to 1, in relation to 1 mol of Compound (13).
[0093] The reaction temperature usually ranges from -20 to 150 ° C. The reaction time usually ranges from 0.1 to 24 hours.
[0094] When the reaction is over, the reaction mixture is extracted with organic solvents, and the resulting organic layers are worked (for example, drying and concentration) to isolate the Compound (2-1). Compound (2-1) alone can be further purified, for example, by chromatography and recrystallization. Reference Process F
[0095] A compound represented by formula (15) (hereinafter called Compound (15)) can be prepared by reacting a compound represented by formula (2-1) where R2 in formula (2) represents Z1 (hereinafter called Compound ( 2-1)) with a compound represented by the formula (15) (hereinafter called Compound (15)).
[where, Z1 has the same definition given above, R4 represents a C1-C12 alkyl group or a phenyl group, and M represents sodium, potassium or lithium.]
[0096] The reaction is usually carried out in a solvent.
[0097] Examples of the solvent to be used in the reaction include ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisol, methyl tert-butyl ether, and diisopropyl ether; hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, and xylene; halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, and chlorobenzene; nitriles such as acetonitrile, and propionitrile; acid amides such as N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone; sulfoxides such as dimethyl sulfoxide; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohols such as methanol, ethanol, propanol, and butanol; and mixed solvents thereof.
[0098] Examples of Compound (14) include sodium methoxide, sodium ethoxide, sodium n-propoxide, sodium n-butoxide, sodium isopropoxide, sodium sec-butoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium n-propoxide, potassium n-butoxide, potassium isopropoxide, potassium sec-butoxide, potassium tert-butoxide, potassium methoxide, and sodium phenoxide.
[0099] In the reaction, Compound (14) is normally used in a range of molar ratios from 1 to 10 in relation to 1 mol of Compound (2-2).
[00100] The reaction temperature normally ranges from -20 to 150 ° C. The reaction time usually ranges from 0.1 to 24 hours.
[00101] When the reaction is over, the reaction mixture is extracted with organic solvents, and the resulting organic layers are worked (for example, drying and concentration) to isolate the Compound (15). Compound (15) alone can be further purified, for example, by distillation, chromatography and recrystallization. Reference Process G
[00102] A compound represented by the formula (16) (hereinafter called Compound (16)) can be prepared by reacting Compound (15) and Compound (7) in the presence of a base.
R2, R4, Z4 and Z1 are as defined above, respectively.]
[00103] The reaction can be carried out according to Process C mentioned above. Reference Process H
[00104] Compound (2) can also be prepared by reacting Compound (16) and a halogenating agent.
R2, R4 and Z1 are as defined above, respectively.]
[00105] The reaction is usually carried out in a solvent.
[00106] Examples of the solvent to be used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, npentane, toluene, and xylene; halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, and 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 mixed solvents thereof.
[00107] Examples of the halogenating agent include hydrochloric acid, hydrobromic acid, and hydroiodic acid.
[00108] In the reaction, the halogenating agent is normally used in a range of molar ratios of 1 or more in relation to 1 mol of Compound (16).
[00109] The reaction temperature normally ranges from -20 to 150 ° C. The reaction time usually ranges from 0.1 to 24 hours.
[00110] When the reaction is over, the reaction mixture is extracted with organic solvents, and the resulting organic layers are worked (for example, drying and concentration) to isolate the Compound (2-1). Compound (2-1) alone can be further purified, for example, by distillation, chromatography and recrystallization.
[00111] The present carboxamide compounds are all known compounds, and they are described in "THE PESTICIDE MANUAL - 16th EDITION (published by BCPC) ISBN 9781901396867", and in documents WO 2011/162397, WO 2006/016708, or WO 2007 / 072999. These compounds can be obtained from commercially available formulations or can be prepared according to known methods.
[00112] Examples of an N- (1,1,3-trimethylindan-4-yl) -1-methyl-3-difluoromethylpyrazole-4-carboxylic acid amide embodiment described in this report include a compound represented by the formula (a1) :
, and / or a compound represented by the formula (a2):

[00113] The present carboxamide compounds are shown in [Table 1] below. Table 1

[00114] In the composition of the present invention, a weight ratio of the present tetrazolinone compound to the present carboxamide compound includes, for example, the present tetrazolinone compound / the present carboxamide compound type = 0.01 / 1 to 500/1, 0, 1/1 to 10/1, and 0.1 / 1 to 3/1, and preferably 0.3 / 1 to 3/1.
[00115] The composition of the present invention can be a mixture of the present tetrazolinone compound and the present carboxamide compound, and is generally prepared by mixing the present tetrazolinone compound, the present carboxamide compound and an inert carrier, optionally with the addition of a surfactant and other formulation aids.
[00116] The composition of the present invention can be formulated as an oily solution, an emulsifiable concentrate, a flowable formulation, a wetting powder, a water-dispersible granule, a powder, or a granule. The formulations thus obtained can be used directly as a plant disease control agent, or can be used after the addition of other inert ingredients.
[00117] The total amount of the present tetrazolinone compound and the present carboxamide compound in the composition of the present invention normally ranges from 0.1% to 99% by weight, preferably from 0.2% to 90% by weight, and more preferably from 1% to 80% by weight.
[00118] Examples of the solid carrier to be used in the formulation include clays (for example, kaolin, diatomaceous earth, synthetic hydrated silicon dioxide, Fubasami clay, bentonite and acid clay), talc or other inorganic minerals (for example, sericite, powder quartz, sulfur powder, activated charcoal, calcium carbonate and hydrated silica) in the form of fine or particulate powders, and examples of the liquid carrier include water, alcohols (for example, methanol and ethanol), ketones (for example, acetone and methyl ethyl ketone), aromatic hydrocarbons (for example, benzene, toluene, xylene, ethylbenzene and methyl naphthalene), aliphatic hydrocarbons (for example, n-hexane, cyclohexane and kerosene), esters (for example, ethyl acetate and butyl acetates), nitriles (for example, acetonitrile and isobutyronitrile), ethers (for example, dioxane and diisopropyl ether), acid amides (for example, DMF and dimethylacetamide), halogenated hydrocarbons (for example, dichloroethane, trichlorethylene and carbon tetrachloride), among others.
[00119] Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylene compounds thereof, polyethylene glycol ethers, polyol esters and sugar alcohol derivatives.
[00120] Examples of other auxiliary agents for the formulation include an adhesive, a dispersant and a stabilizer, and specific examples include casein, gelatin, polysaccharides (e.g., starch, gum arabic, cellulose derivatives and alginic acid), lignin derivatives , bentonite, sugars, water-soluble synthetic polymers (for example, polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylic acids), PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA ( a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, fatty acids or fatty acid esters thereof, among others.
[00121] The composition of the present invention can also be formulated by formulating each of the present tetrazolinone compound and the present carboxamide compound according to the method mentioned above and, if necessary, diluting it with water to obtain a formulation containing the the present tetrazolinone compound or diluted solutions containing the same, or a formulation containing the present carboxamide compound or diluted solutions containing the same, respectively, followed by mixing the resulting formulations or diluted solutions with one another.
[00122] The composition of the present invention can be used to protect plants against plant diseases.
[00123] The control method of the present invention can control plant diseases by applying the composition of the present invention to plants or soil for growing plants, alternatively by applying the present tetrazolinone compound or the present carboxamide compound separately to plants or to soil for growing plants.
[00124] The method for applying the composition of the present invention is not particularly limited, as long as the application form is a form by which the present compound can be applied in considerable quantity, and includes, for example, an application to plants such as a foliar application; an application to the area for the cultivation of plants such as a submerged treatment; and an application to seeds such as seed disinfection.
[00125] The application dose of the composition of the present invention varies depending on climatic conditions, dosage forms, application time, application methods, areas to be applied, target diseases, target cultures, among others, and generally varies in range from 1 to 500 g, and preferably from 2 to 200 g per 1,000 m2 of the area to be applied. Emulsifiable concentrate, wettable powder or suspension concentrate etc. it is usually applied by diluting it with water. In this case, the concentration of the composition of the present invention after dilution generally ranges from 0.0005 to 2% by weight, and preferably from 0.005 to 1% by weight, and the powder formulation or granular formulation etc. it is usually applied as is without being diluted. In seed application, the amount of the composition of the present invention generally ranges from 0.001 to 100 g, and preferably from 0.01 to 50 g per 1 kg of seed.
[00126] Examples of where plant diseases develop include rice paddies, fields, tea gardens, orchards, non-agricultural land, houses, seed trays, seed boxes, seed soils and seed beds.
[00127] The composition of the present invention can be used as an agent to control plant diseases in agricultural land such as fields, rice fields, lawns, and orchards. The composition of the present invention can control diseases occurring on agricultural land or other land for the cultivation of the following '' plants '', among others. Crops: corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybeans, peanuts, buckwheat, beets, canola, sunflowers, sugar cane, tobacco, among others; Vegetables: solanaceous vegetables (for example, eggplant, tomatoes, peppers, pepper and potatoes), cucurbitaceous vegetables (for example, cucumber, pumpkin, zucchini, watermelon and melon), cruciferous vegetables (for example, Japanese radish, white turnip, spicy horseradish , kohlrabi, chinese cabbage, cabbage, mustard leaf, broccoli, cauliflower), asteraceous vegetables (eg burdock, daisy, crown, artichoke and lettuce), lily vegetables (eg chives, onions, garlic and asparagus) , amiaceous vegetables (for example, carrots, parsley, celery and parsnips), chenopodiaceous vegetables (for example, spinach and Swiss chard), lameaceous vegetables (for example, Perilla frutescens, mint and basil), strawberry, sweet potatoes, Dioscorea japonica , colocasia, among others; Flowers: Ornamental foliage plants: Fruits: pomegranate fruits (for example, apple, pear, Japanese pear, Chinese quince and quince), stone fruits (for example, peach, plum, nectarine, umê, cherry, apricot and prune) , citrus fruits (for example, mikan, orange, lemon, lime and grapefruit), nuts (for example, chestnut, walnuts, hazelnuts, almonds, pistachios, cashews and macadamia nuts), soft fruits (for example, blueberry , cranberry, blackberry and raspberry), grapes, persimmon, olive, loquat, banana, coffee, date, coconut, among others; Non-fruit trees: tea, mulberry, angiosperms, roadside trees (eg ash, birch, dogwood, eucalyptus, ginkgo biloba, lilac, maple, oak, poplar, Judas tree, Liquidambar formosana, maple, zelkova, Japanese arborvitae, fir, hemlock, juniper, Pinus, Picea, and Taxus cuspidate); between others.
[00128] The "plant" mentioned above includes genetically modified crops.
[00129] The pests in which the composition of the present invention has a controlling efficacy include plant pathogens, such as filamentous fungus, and specifically include the following examples, but are limited to them. Rice diseases: blast (Magnaporthe grisea), brown spot (Cochliobolus miyabeanus), sheath burning (Rhizoctonia solani) and bakanae disease (Gibberella fujikuroi); Wheat diseases: powdery mildew (Erysiphe graminis), wheat gibberellas (Fusarium graminaarum, F. avenaceum, F. culmorum, Microdochium nivale), wheat leaf rust (Puccinia striiformis, P. graminis, P. recondita), snow pest (Micronectriella nivale), rust on typhula snow (Typhula sp.), Loose soot (Ustilago tritici), saddlebag (Tilletia caries), ocellus (Pseudocercosporella herpotrichoides), speckled leaf spot (Mycosphaerella graminicola), gluma patch ) and tan spot (Pyrenophora tritici-repentis); Barley diseases: powdery mildew (Erysiphe graminis), gibberellus caused by Fusarium (Fusarium gaminaarum, F. avenaceum, F. culmorum, Microdochium nivale), rust (Puccinia striiformis, P. graminis, P. hordei), bark (Ustilago nuda) , scalding (Rhynchosporium secalis), reticular spot (Pyrenophora teres), brown spot (Cochliobolus sativus), leaf stripe (Pyrenophora graminaa), and sowing rust caused by rhizoctonia (Rhizoctonia solani); Corn diseases: corn coal (Ustilago maydis), southern leaf rust (Cochliobolus heterostrophus), zoned spot (Gloeocercospora sorghi), polishing rust (Puccinia polysora), cercosporiosis (Cercospora zeae-maydis), and rust caused by rust rhizoctonia (Rhizoctonia solani); Citrus diseases: melanosis (Diaporthe citri), warts (Elsinoe fawcetti), fruit rot (Penicillium digitatum, P. italicum); diseases caused by Phytophthora (Phytophthora parasitica, Phytophthora citrophthora); Apple diseases: flowering rust (Monilinia mali), cancer (Waltz ceratosperma), powdery mildew (Podosphaera leucotricha), leaf blotch caused by Alternaria (Alternaria alternata apple pattern), wart (Venturia inaequalis), bitter rot (Colletotrichum acutatum) , and crown rot (Phytophtora cactorum); Pear diseases: scabies (Venturia nashicola, V. pirina), black spot (Alternaria alternata Japanese pear pattern), rust (Gymnosporangium haraeanum) and colon rot (Phytophtora cactorum); Peach diseases: brown rot (Monilinia fructicola), scabies (Cladosporium carpophilum) and Phomopsis rot (Phomopsis sp.); Grape diseases: anthracnose (Elsinoe ampelina), ripe grape rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black rot (Guignardia bidwellii), and downy mildew (Plasmopara viticola); Japanese persimmon diseases: anthracnose (Gloeosporium kaki), and leaf spot (Cercospora kaki, Mycosphaerella nawae); Diseases of the gourd family: anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea), bitter rot (Mycosphaerella melonis), withering caused by Fusarium (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), phytophora (phytophora), phytophora (phytophora). wilting (Pythium sp.); Tomato diseases: black spot (Alternaria solani), cladosporium spot (Cladosporium fulvum), and late blight (Phytophthora infestans); Eggplant diseases: dry branches (Phomopsis vexans), and powdery mildew (Erysiphe cichoracearum); Cruciferous vegetable diseases: alternate leaf spot (Alternaria japonica), white spot (Cercosporella brassicae), cruciferous hernia (Plasmodiophora brassicae), and downy mildew (Peronospora parasitica); Chives diseases: rust (Puccinia allii), and downy mildew (Peronospora destructor); Soy diseases: purple spot (Cercospora kikuchii), sphaceloma scab (Elsinoe glycines), pod and stem rust (Diaporthe phaseolorum var .oyae), brown spot caused by septoria (Septoria glycines), frog eye spot (Cercospora sojina), Asian rust (Phakopsora pachyrhizi), and stem and root rot caused by phytophora (Phytophthoraoyae), soybean molasses (Rhizoctonia solani), target spot (Corynespora cassiicola), and stem rot caused by sclerotinia (Sclerotinia scclerotinia ); Purple bean diseases: anthracnose (Colletotrichum lindemthianum); Peanut diseases: black spot (Cercospora personata), brown spot (Cercospora arachidicola) and Sclerotium wilt (Sclerotium rolfsii); Pea diseases: powdery mildew (Erysiphe pisi); Potato diseases: black spot (Alternaria solani), late blight (Phytophthora infestans), pink rot (Phytophthora Erythroseptica), and powdery mange (Spongospora subterranean f. Sp. Subterranea); Strawberry diseases: powdery mildew (Sphaerotheca humuli), and anthracnose (Glomerella cingulata); Tea diseases: tea rust (Exobasidium reticulatum), white mange (Elsinoe leucospila), gray rust (Pestalotiopsis sp.) And anthracnose (Colletotrichum theae-sinensis); Tobacco diseases: brown spots (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), and late blight (Phytophthora nicotianae); Canola diseases: rot caused by sclerotinia (Sclerotinia sclerotiorum), and root rot (Rhizoctonia solani); Cotton diseases: root rot (Rhizoctonia solani); Beet diseases: leaf spots caused by Cercospora (Cercospora beticola), leaf disease (Thanatephorus cucumeris), root rot (Thanatephorus cucumeris), and root rot caused by aphanomyces (Aphanidermatum cochlioides); Diseases of the rose: black spot (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa), and downy mildew (Peronospora sparsa); Chrysanthemum diseases: downy mildew (Bremia lactucae), leaf rust (Septoria chrysanthemi-indici), and white rust (Puccinia horiana); Various harvest diseases: diseases caused by Pythium spp. (Pythium aphanidermatum, Pythium debarianum, Pythium irregulare, Pythium ultimum), gray mold (Botrytis cinerea), and rot caused by sclerotinia (Sclerotinia sclerotiorum); Japanese radish diseases: leaf spot caused by Alternaria (Alternaria brassicicola); Lawn diseases: dollar-shaped spot (Sclerotinia homeocarpa), brown spot and large spot (Rhizoctonia solani); Banana diseases: Sigatoka disease (Mycosphaerella fijiensis, Mycosphaerella musicola); Seed diseases or diseases in the early growth stages of various plants caused by Aspergillus spp., Penicillium spp., Fusarium spp., Gibberella spp., Tricoderma spp., Thielaviopsis spp., Rhizopus spp., Mucor spp., Corticium spp. , Phoma spp., Rhizoctonia spp. or Diplodia spp .; and viral diseases of various plants mediated by Polymixa spp. or Olpidium spp .; and so on. EXAMPLES
[00130] Next, the following process for the present tetrazolinone compound, and the examples, including formulation examples and test examples, serve to illustrate the invention in more detail, which is not intended to limit the present invention.
[00131] First, Preparation Examples for the present tetrazolinone compound are shown. Preparation Example 1
[00132] A mixture of 1- (2-bromomethyl-3-chlorophenyl) -4-methyl-1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 3) 1.21 g, 1- (4-chlorophenyl) -1H-pyrazol-3-ol 0.78 g, potassium carbonate 0.66 g and acetonitrile 30 ml was stirred with heating under reflux for four hours. To the reaction mixture after resting to cool, water was added, and the mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2 - {[1- (4-chlorophenyl) -1H-pyrazol-3-yl] oxymethyl} -3-chlorophenyl) -4-methyl -1,4-dihydrotetrazol-5-one (hereinafter referred to as Present compound tetrazolinone 1) 0.61 g.
[00133] Present tetrazolinone compound 1

[00134] 1H-NMR (CDCl3) δ (ppm): 7.64 (1H, d, J = 2.7 Hz), 7.62 7.60 (1H, m), 7.53-7.49 ( 2H, m), 7.45 (1H, t, J = 8.0 Hz), 7.39-7.35 (3H, m), 5.80 (1H, d, J = 2.7 Hz), 5.54 (2H, s), 3.61 (3 H, s). Preparation Example 2
[00135] A mixture of 1- (2-bromomethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 6) 18.5 g, 1- (4-chlorophenyl) -1H-pyrazol-3-ol 10.4 g, potassium carbonate 8.8 g and acetonitrile 400 mL was stirred with heating under reflux for four hours. To the reaction mixture after resting to cool, water was added and the mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2 - {[1- (4-chlorophenyl) -1H-pyrazol-3-yl] oxymethyl} -3-bromophenyl) -4-methyl -1,4-dihydrotetrazol-5-one (hereinafter referred to as Present compound tetrazolinone 2) 24.6 g.
[00136] Present tetrazolinone compound 2

[00137] 1H-NMR (CDCl3) δ (ppm): 7.81-7.79 (1H, m), 7.65 (1H, d, J = 2.4 Hz), 7.54-7.50 (2H, m), 7.42-7.35 (4H, m), 5.81 (1H, d, J = 2.4 Hz), 5.53 (2H, s), 3.60 (3H, s). Preparation Example 3
[00138] A mixture of the present compound tetrazolinone 2 (described in Preparation Example 2) 0.92 g, methyl boronic acid 0.18 g, tripotassium phosphate 1.27 g, water 0.11 ml, dichloride complex of [1 , 1'-bis (diphenylphosphino) ferrocene] -paladium (II) dichloromethane 0.16 g, and 7 mL dioxane was stirred with heating under reflux for an hour and a half. To the reaction solution after cooling, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2 - {[1- (4-chlorophenyl) -1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) -4-methyl -1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 3) 0.27 g.
[00139] Present tetrazolinone compound 3

[00140] 1H-NMR (CDCl3) δ (ppm): 7.64 (1H, d, J = 2.7 Hz), 7.52 7.49 (2H, m), 7.42-7.35 ( 4H, m), 7.27-7.24 (1H, m), 5.82 (1H, d, J = 2.7 Hz), 5.33 (2H, s), 3.63 (3H, s ), 2.56 (3H, s). Preparation Example 4
[00141] A mixture of 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 12) 0.30 g, 1- (4-methoxyphenyl) -1H-pyrazol-3-ol 0.21 g, 0.19 g potassium carbonate and 10 ml acetonitrile was stirred with heating under reflux for two hours. To the reaction mixture after resting to cool, water was added, and the mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2 - {[1- (4-methoxyphenyl) -1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) -4-methyl -1,4-dihydrotetrazol-5-one (hereinafter referred to as the present compound tetrazolinone 4) 0.28 g.
[00142] Present tetrazolinone compound 4

[00143] 1H-NMR (CDCl3) δ (ppm): 7.57 (1H, d, J = 2.7 Hz), 7,497.44 (2H, m), 7.39-7.36 (2H, m ), 7.27-7.23 (1H, m), 6.96-6.91 (2H, m), 5.77 (1H, d, J = 2.7 Hz), 5.32 (2H, s), 3.83 (3H, s), 3.61 (3H, s), 2.56 (3H, s). Preparation Example 5
[00144] A mixture of 1- (2-bromomethyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 9) 1.20 g, 1- (4-chlorophenyl) -1H-pyrazol-3-ol 0.78 g, potassium carbonate 0.66 g, and acetonitrile 30 ml was stirred with heating under reflux for four hours. To the reaction mixture after resting to cool, water was added and the mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2 - {[1- (4-chlorophenyl) -1H-pyrazol-3-yl] oxymethyl} -3-methoxyphenyl) -4-methyl -1,4- dihydrotetrazol-5-one (hereinafter referred to as Present compound tetrazolinone 5) 0.97 g.
[00145] Present tetrazolinone compound 5

[00146] 1H-NMR (CDCl3) δ (ppm): 7.63 (1H, d, J = 2.7 Hz), 7,537.49 (2H, m), 7.46 (1H, dd, J = 8 , 5, 8.0 Hz), 7.38 - 7.34 (2H, m), 7.08 (1H, d, J = 8.5 Hz), 7.04 (1H, d, J = 8, 0 Hz), 5.80 (1H, d, J = 2.7 Hz), 5.43 (2H, s), 3.92 (3H, s), 3.57 (3H, s). Preparation Example 6
[00147] A mixture of the present compound tetrazolinone 2 (described in Preparation Example 2) 0.92 g, ethyl boronic acid 0.22 g, tripotassium phosphate 1.27 g, water 0.11 ml, dichloride complex of [1, 1'-bis (diphenylphosphino) ferrocene] -palladium (II) dichloromethane 0.16 g and dioxane 15 mL was stirred with heating under reflux for two hours. To the reaction solution after cooling, water was added, and the mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2 - {[1- (4-chlorophenyl) -1H-pyrazol-3-yl] oxymethyl} -3-ethylpenyl) -4-methyl -1,4-dihydroteterazol-5-one (hereinafter referred to as Present compound tetrazolinone 6) 0.24 g.
[00148] Present tetrazolinone compound 6

[00149] 1H-NMR (CDCl3) δ (ppm): 7.65 (1H, d, J = 2.7 Hz), 7.53 7.49 (2H, m), 7.47-7.42 ( 2H, m), 7.39-7.35 (2H, m), 7.27-7.24 (1H, m), 5.81 (1H, d, J = 2.7 Hz), 5.34 (2H, s), 3.61 (3H, s), 2.90 (2H, q, J = 7.6 Hz), 1.30 (3H, t, J = 7.6 Hz). Preparation Example 7
[00150] A mixture of the present compound tetrazolinone 2 (described in Preparation Example 2) 0.92 g, cyclopropyl boronic acid 0.26 g, tripotassium phosphate 1.27 g, water 0.11 ml, dichloride complex of [1, 1'-bis (diphenylphosphino)] ferrocene] -paladium (II) dichloromethane 0.16 g, and 7 mL dioxane was stirred with heating under reflux for an hour and a half. To the reaction solution after cooling, water was added, and the mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2 - {[1- (4-chlorophenyl) -1H-pyrazol-3-yl] oxymethyl} -3-cyclopropylphenyl) -4-methyl -1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 7) 0.35 g.
[00151] Present tetrazolinone compound 7

[00152] 1H-NMR (CDCl3) δ (ppm): 7.63 (1H, d, J = 2.7 Hz), 7.51 7.46 (2H, m), 7.41-7.37 ( 1H, m), 7.36-7.32 (2H, m), 7.24-7.21 (2H, m), 5.80 (1H, d, J = 2.7 Hz), 5.53 (2H, s), 3.58 (3H, s), 2.26-2.19 (1H, m), 1.03-0.99 (2H, m), 0.78-0.74 (2H , m). Preparation Example 8
[00153] A mixture of 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 12) 0.30 g, 1- (4-bromophenyl) -1H-pyrazol-3-ol 0.27 g, potassium carbonate 0.19 g, and acetonitrile 10 ml was stirred with heating under reflux for four hours. To the reaction mixture after resting to cool, water was added, and the mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2 - {[1- (4-bromophenyl) -1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) -4-methyl -1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 8) 0.37 g.
[00154] Present tetrazolinone compound 8

[00155] 1H-NMR (CDCl3) δ (ppm): 7.64 (1H, d, J = 2.4 Hz), 7.53- 7.49 (2H, m), 7.45-7.37 (4H, m), 7.27-7.24 (1H, m), 5.82 (1H, d, J = 2.4 Hz), 5.33 (2H, s), 3.62 (3H, s), 2.55 (3H, s). Preparation Example 9
[00156] A mixture of 1- (2 - {[1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) - 4-methyl-1,4-dihydrotetrazol-5-one (described in the Preparation Example Reference 14) 0.49 g, 4-chloro-3-fluorophenylboronic acid 0.33 g, copper (II) acetate 0.51 g, pyridine 0.28 g, molecular sieve 4A 1.00 g, and acetonitrile 10 mL was stirred with heating under reflux for forty-eight hours. To the reaction mixture after resting to cool, water was added, and the mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2 - {[1- (4-chloro-3-fluorophenyl) -1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 9) 0.12 g.
[00157] Present tetrazolinone compound 9

[00158] 1H-NMR (CDCl3) δ (ppm): 7.64 (1H, d, J = 2.7 Hz), 7.44- 7.38 (4H, m), 7.28-7.23 (2H, m), 5.84 (1H, d, J = 2.7 Hz), 5.33 (2H, s), 3.65 (3H, s), 2.56 (3H, s). Preparation Example 10
[00159] A mixture of 1- (2-bromomethyl-3-methylpenyl) -4-methyl-1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 12) 0.30 g, 1- (2-methoxyphenyl) -1H-pyrazol-3-ol 0.20 g, potassium carbonate 0.19 g and acetonitrile 10 mL was stirred with heating under reflux for four hours. To the reaction mixture after resting to cool, water was added, and the mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2- {[1- (2-methoxyphenyl) -1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) -4-methyl- 1,4-dihydroteterazol-5-one (hereinafter referred to as Present compound tetrazolinone 10) 0.23 g.
[00160] Present tetrazolinone compound 10

[00161] 1H-NMR (CDCl3) δ (ppm): 7.89 (1H, d, J = 2.5 Hz), 7.70 (1H, dd, J = 8.0, 1.6 Hz), 7.41-7.37 (2H, m), 7.26-7.18 (2H, m), 7.06-6.99 (2H, m), 5.76 (1H, d, J = 2 , 5 Hz), 5.32 (2H, s), 3.88 (3H, s), 3.61 (3H, s), 2.55 (3H, s). Preparation Example 11
[00162] A mixture of 1- (2 - {[1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) - 4-methyl-1,4-dihydroteterazol-5-one (described in the Example of Reference Preparation 14) 1.00 g, 4-chloro-2-methoxyphenyl boronic acid 0.78 g, copper (II) acetate 0.98 g, pyridine 0.59 mL, molecular sieve 4A 1.50 g, and 15 mL acetonitrile was stirred with heating under reflux for fifteen hours. To the reaction mixture after resting to cool, water was added, and the mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2 - {[1- (4-chloro-2-methoxyphenyl) -1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) -4-methyl-1,4-dihydroteterazol-5-one (hereinafter referred to as the present tetrazolinone compound 11) 0.15 g.
[00163] Present tetrazolinone compound 11

[00164] 1H-NMR (CDCl3) δ: 7.87 (1H, d, J = 2.5 Hz), 7.65 (1H, d, J = 8.5 Hz), 7.42-7.37 (2H, m), 7.26-7.24 (1H, m), 7.03 (1H, dd, J = 8.5, 2.3 Hz), 6.99 (1H, d, J = 2 , 3 Hz), 5.77 (1H, d, J = 2.5 Hz), 5.30 (2H, s), 3.89 (3H, s), 3.63 (3H, s), 2, 55 (3H, s).
[00165] In the following, processes for the preparation of intermediates of the Present tetrazolinone compound mentioned above are shown below as Reference Preparation Examples. Reference Preparation Example 1
[00166] Anhydrous aluminum chloride 21.9 g was added to N, N-dimethylformamide 250 ml under ice cooling, and the mixture was stirred for fifteen minutes. To this mixture was added sodium azide 10.7 g and the mixture was stirred for fifteen minutes. To this mixture was then added 1-chloro-3-isocyanate-2-methylbenzene 25.0 g, and the resulting mixture was heated at 80 ° C for five hours. The reaction solution after cooling was added to a mixture of sodium nitrite 35 g, water 2 L and ice 500 g with stirring. The mixture was acidified with 10% hydrochloric acid and was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to give 1- (2-methyl-3-chlorophenyl) -1,4-dihydrotetrazole- 5- on 17.0 g.
[00167] 1- (2-methyl-3-chlorophenyl) -1,4-dihydrotetrazol-5-one

[00168] 1H-NMR (CDCl3) δ (ppm): 2.32 (3H, s), 7.28-7.36 (2H, m), 7.57 (1H, dd, J = 6.8, 2.2 Hz), 13.08 (1H, s). Reference Preparation Example 2
[00169] To a mixture of 1- (2-methyl-3-chlorophenyl) -1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 1) 10.00 g and N, N-dimethylformamide 100 ml 60% sodium hydride 2.30 g was added under ice cooling. The mixture had the temperature raised to room temperature and was stirred for one hour. To the reaction mixture was added methyl iodide 3.2 ml under ice-cooling. The mixture had the temperature raised to room temperature and was stirred for fourteen hours. To the reaction mixture, water was added, and the mixture was extracted with ethyl acetate. The organic layers were washed with 10% hydrochloric acid, water and saturated saline, and were dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2-methyl-3-chlorophenyl) -4-methyl-1,4-dihydrotetrazol-5-one 1.56 g.
[00170] 1- (2-methyl-3-chlorophenyl) -4-methyl-1,4-dihydrotetrazol-5-one

[00171] 1H-NMR (CDCl3) 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 Preparation Example 3
[00172] A mixture of 1- (2-methyl-3-chlorophenyl) -4-methyl-1,4-dihydrotetrazol-5-one (described in Reference Example 2) 1.56 g, 1.1 ' - azobis (cyclohexane-1-carbonitrile) 0.34 g, N-bromosuccinimide 1.42 g and chlorobenzene 30 ml was stirred with heating under reflux for five hours. To the reaction solution after cooling, water was added, and the mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2-bromomethyl-3-chlorophenyl) -4-methyl-1,4-dihydrotetrazol-5-one 1.94 g.
[00173] 1- (2-bromomethyl-3-chlorophenyl) -4-methyl-1,4-dihydrotetrazol-5-one

[00174] 1H-NMR (CDCl3) 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 Preparation Example 4
[00175] Anhydrous aluminum chloride 19.7 g was added to N, N-dimethylformamide 220 ml under ice cooling, and the mixture was stirred for fifteen minutes. To this mixture was added sodium azide 9.6 g and the mixture was stirred for fifteen minutes. To this mixture was then added 1-bromo-3-isocyanate-2-methylbenzene 30.3 g and the resulting mixture was heated at 80 ° C for five hours. The reaction solution after cooling was added to a mixture of 33 g sodium nitrite, 2 L water and 500 g ice with stirring. The mixture was acidified with 10% hydrochloric acid, and was extracted with ethyl acetate. The organic layers were washed with water and saturated saline and then dried over anhydrous magnesium sulfate and were then concentrated under reduced pressure to give 1- (2-methyl-3-bromophenyl) -1,4-dihydrotetrazole- 5-one 31.4 g.
[00176] 1- (2-methyl-3-bromophenyl) -1,4-dihydrotetrazol-5-one

[00177] 1H-NMR (DMSO-d6) 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 Preparation Example 5
[00178] To a mixture of 1- (2-methyl-3-bromophenyl) -1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 4) 31.40 g and N, N-dimethylformamide 250 ml 60% sodium hydride 5.90 g was added under ice cooling. The reaction mixture had the temperature raised to room temperature, and was stirred for one hour. To the reaction mixture, methyl iodide 8.4 ml was added under ice cooling. The mixture had the temperature raised to room temperature, and was stirred for fourteen hours. To the reaction mixture, water was added and the mixture was extracted with ethyl acetate. The organic layers were washed with 10% hydrochloric acid, water and saturated saline, and dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2-methyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one 8.47 g.
[00179] 1- (2-methyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one

[00180] 1H-NMR (CDCl3) 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 Preparation Example 6
[00181] To a mixture of 1- (2-methyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 5) 8.47 g, 1 , 1'-azobis (cyclohexane-1-carbonitrile) 1.54 g, N-bromosuccinimide 6.44 g and chlorobenzene 125 ml was stirred with heating under reflux for five hours. To the reaction solution after cooling, water was added and the resulting mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, and dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2-bromomethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one 7.52 g.
[00182] 1- (2-bromomethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one

[00183] 1H-NMR (CDCl3) 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 Preparation Example 7
[00184] Anhydrous aluminum chloride 16.0 g was added to N, N-dimethylformamide 180 ml under cooling with ice, and the mixture was stirred for fifteen minutes. To this mixture was added sodium azide 7.8 g and the mixture was stirred for fifteen minutes. To this mixture was then added 1-methoxy-3-isocyanate-2-methylbenzene 17.0 g, and the resulting mixture was heated at 80 ° C for four and a half hours. The reaction solution after cooling was added to a mixture of 25 g sodium nitrite, 2 L water and 500 g ice with stirring. The mixture was acidified with 10% hydrochloric acid and was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to give 1- (2-methyl-3-methoxyphenyl) - 1,4-dihydrotetrazole-5- on 16.2 g.
[00185] 1- (2-methyl-3-methoxyphenyl) -1,4-dihydrotetrazol-5-one

[00186] 1H-NMR (DMSO-d6) δ (ppm): 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). Reference Preparation Example 8
[00187] To a mixture of 1- (2-methyl-3-methoxyphenyl) -1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 7) 10.00 g and N, N-dimethylformamide 100 ml 60% sodium hydride 2.47 g was added under ice cooling. The reaction mixture had the temperature raised to room temperature and was stirred for fourteen hours. To the reaction mixture, 3.5 ml methyl iodide was added under ice cooling. The mixture had the temperature raised to room temperature and was stirred for one hour. To the reaction mixture, 3.5 ml methyl iodide was added under ice cooling. The mixture had the temperature raised to room temperature and was stirred for fourteen hours. To the reaction mixture, water was added and the mixture was extracted with ethyl acetate. The organic layers were washed with 10% hydrochloric acid, water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to column chromatography on silica gel to give 1-9 (2.-methyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one 2.19 g.
[00188] 1- (2-methyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one

[00189] 1H-NMR (CDCl3) δ (ppm): 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) Reference Preparation Example 9
[00190] To a mixture of 1- (2-methyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 8) 2.19 g, 1 , 1'-azobis (cyclohexane-1-carbonitrile) 0.52 g, N-bromosuccinimide 2.16 g and chlorobenzene 40 ml was stirred with heating under reflux for five hours. To the reaction solution after cooling, water was added, and the resulting mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to column chromatography on silica gel to give 1- (2-bromomethyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one 2.36 g.
[00191] 1- (2-bromomethyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazole-5-

[00192] 1H-NMR (CDCl3) δ (ppm): 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 Preparation Example 10
[00193] A mixture of 1- (2-bromomethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 6) 45.0 g, methoxide sodium 37.4 g and tetrahydrofuran 600 mL was stirred at room temperature for three hours. To the reaction mixture, a saturated aqueous solution of sodium bicarbonate was added, and the resulting mixture was extracted with ethyl acetate. The organic layers were washed with a saturated aqueous solution of sodium bicarbonate, and then dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure to give 1- (2-methoxymethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one 36.2 g.
[00194] 1- (2-methoxymethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one

[00195] 1H-NMR (CDCl3) 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 Preparation Example 11
[00196] A mixture of 1- (2-methoxymethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 10) 36.2 g, methylboronic acid 23.2 g, cesium fluoride 66.7 g, adduct of [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride with dichloromethane 10.6 g and dioxane 500 mL was stirred at 90 ° C for five and a half hours. The reaction mixture after cooling was filtered, and the filtrates were concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2-methoxymethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one 25.6 g.
[00197] 1- (2-methoxymethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one

[00198] 1H-NMR (CDCl3) 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 Preparation Example 12
[00199] A mixture of 1- (2-methoxymethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 11) 25.6 g, acetic acid 50 mL and a 25% hydrogen bromide solution in 50 mL acetic acid was stirred at 65 ° C for one hour. To the reaction mixture, saturated saline was added, and the mixture was extracted with ethyl acetate. The organic layers were washed with a saturated aqueous solution of sodium bicarbonate and then dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure to give 1- (2-bromomethyl-3-methylphenyl) - 4-methyl-1,4-dihydrotetrazol-5-one 27.9 g.
[00200] 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazole-5-

[00201] 1H-NMR (CDCl3) 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 Preparation Example 13
[00202] A mixture of 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 12) 1.0 g, 1- acetyl-1H-pyrazol-3-ol 0.47 g, potassium carbonate 0.63 g and acetonitrile 20 ml was stirred with heating under reflux for two hours. To the reaction mixture after resting to cool, water was added, and the resulting mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2 - {[1-acetyl-1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) -4-methyl-1,4 -dihydrotetrazol-5-one 0.58 g.

[00203] 1H-NMR (CDCl3) δ (ppm): 8.01 (1H, d, J = 2.9 Hz), 7.43 7.38 (2H, m), 7.26 (1H, dd, J = 6.9, 2.1 Hz), 5.88 (1H, d, J = 2.9 Hz), 5.31 (2H, s), 3.69 (3H, s), 2.55 ( 3H, s), 2.54 (3H, s). Reference Preparation Example 14
[00204] A mixture of 1- (2 - {[1-acetyl-1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 13) 3.4 g, 0.59 sodium methoxide and 30 ml methanol were stirred at room temperature for two hours. The reaction mixture was added to a saturated aqueous solution of sodium bicarbonate, and the resulting mixture was extracted with ethyl acetate. The organic layers were washed with water and saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography to give 1- (2 - {[1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) -4-methyl-1,4-dihydrotetrazole -5-

[00205] 1H-NMR (CDCl3) δ (ppm): 9.61 (1H, s), 7.40-7.35 (2H, m), 7.27 (1H, d, J = 2.4 Hz ), 7.24 (1H, dd, J = 6.5, 2.8 Hz), 5.63 (1H, d, J = 2.4 Hz), 5.23 (2H, d, J = 11, 2 Hz), 3.66 (3H, s), 2.52 (3H, s).
[00206] The compounds selected from the present tetrazolinone compound to the present tetrazolinone compound 81, which can be prepared according to Process A to Process C mentioned above, are shown below.
Table 2
Table 3
Table 4


[00207] Examples of an embodiment of the present tetrazolinone compound include compounds represented by formula (1) in which the substituents represent the following. a tetrazolinone compound represented by formula (1) where n is an integer equal to any one from 0 to 2; R1 represents a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a nitro group or a cyano group; and R2 represents a methyl group, a cyclopropyl group, a chlorine atom, a bromine atom, an ethyl group, or a methoxy group; a tetrazolinone compound represented by formula (1) where n is an integer equal to any one from 0 to 2; R1 represents a halogen atom, a methyl group, an ethyl group, or a methoxy group; and R2 represents a C1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogen atom, a C2-C3 alkenyl group, a C1-C3 alkoxy group, a C1-C2 alkylthio group, or a C2-C3 alkynyl group ; a tetrazolinone compound represented by formula (1) where n is an integer equal to any one from 0 to 2; R1 represents a halogen atom, a methyl group, an ethyl group, or a methoxy group; and R2 represents a methyl group, a cyclopropyl group, a chlorine atom, a bromine atom, an ethyl group, or a methoxy group; a tetrazolinone compound represented by formula (1) where n is an integer equal to any one from 0 to 2; R1 represents a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 alkylthio group, a nitro group, or a cyano group, a tetrazolinone compound represented by formula (1) in which n is an integer equal to any one from 0 to 2; and R1 represents a halogen atom, a methyl group, an ethyl group, or a methoxy group; a tetrazolinone compound represented by formula (1) wherein R2 represents a C1-C3 alkyl group, a C3-C4 cycloalkyl group, a halogen atom, a C2-C3 alkenyl group, a C1-C3 alkoxy group, a C1- group C2 alkylthio, or a C2-C3 alkynyl group; a tetrazolinone compound represented by formula (1) wherein R2 represents a methyl group, a cyclopropyl group, a chlorine atom, a bromine atom, an ethyl group, or a methoxy group; a tetrazolinone compound represented by formula (1) wherein R2 represents a C1-C3 alkyl group; a tetrazolinone compound represented by formula (1) wherein R2 represents a methyl group; a tetrazolinone compound represented by formula (1) wherein R2 represents an ethyl group; a tetrazolinone compound represented by formula (1) wherein R2 represents a C3-C4 cycloalkyl group; a tetrazolinone compound represented by formula (1) wherein R2 represents a cyclopropyl group; a tetrazolinone compound represented by formula (1) in which R2 represents a halogen atom; a tetrazolinone compound represented by formula (1) wherein R2 represents a chlorine atom; a tetrazolinone compound represented by formula (1) wherein R2 represents a bromine atom; a tetrazolinone compound represented by formula (1) wherein R2 represents a C1-C3 alkoxy group; and a tetrazolinone compound represented by formula (1) wherein R2 represents a methoxy group.
[00208] Examples of a composition embodiment of the present invention include the following. a plant disease control composition comprising a tetrazolinone compound represented by formula (1) where n is an integer equal to 1 or 2, R1 represents a halogen atom or a C1-C6 alkoxy group, R2 represents a C1 group -C3 alkyl, a C3-C4 cycloalkyl group, a halogen atom, or a C1-C3 alkoxy group, and any of Compounds I to VI; a plant disease control composition comprising a tetrazolinone compound represented by formula (1) where n is an integer equal to 1 or 2, R1 represents a halogen atom or a C1-C3 alkoxy group, R2 represents a C1 group -C3 alkyl, a C3-C4 cycloalkyl group, a halogen atom or a C1-C3 alkoxy group, and any of Compounds I to VI; a plant disease control composition comprising a tetrazolinone compound represented by formula (1) where n is an integer equal to 1 or 2, R1 represents a halogen atom or a C1-C6 alkoxy group, and R2 represents a group C1-C3 alkyl, a C3-C4 cycloalkyl group, a halogen atom or a C1-C3 alkoxy group, and Compound I; a plant disease control composition comprising a tetrazolinone compound represented by formula (1) where n is an integer equal to 1 or 2, R1 represents a halogen atom or a C1-C6 alkoxy group, and R2 represents a group C1-C3 alkyl, a C3-C4 cycloalkyl group, a halogen atom or a C1-C3 alkoxy group, and Compound II; a plant disease control composition comprising a tetrazolinone compound represented by formula (1) where n is an integer equal to 1 or 2, R1 represents a halogen atom or a C1-C6 alkoxy group, and R2 represents a group C1-C3 alkyl, a C3-C4 cycloalkyl group, a halogen atom or a C1-C3 alkoxy group, and Compound III; a plant disease control composition comprising a tetrazolinone compound represented by formula (1) where n is an integer equal to 1 or 2, R1 represents a halogen atom or a C1-C6 alkoxy group, and R2 represents a group C1-C3 alkyl, a C3-C4 cycloalkyl group, a halogen atom or a C1-C3 alkoxy group, and Compound IV; a plant disease control composition comprising a tetrazolinone compound represented by formula (1) where n is an integer equal to 1 or 2, R1 represents a halogen atom or a C1-C6 alkoxy group, and R2 represents a group C1-C3 alkyl, a C3-C4 cycloalkyl group, a halogen atom or a C1-C3 alkoxy group, and Compound V; a plant disease control composition comprising a tetrazolinone compound represented by formula (1) where n is an integer equal to 1 or 2, R1 represents a halogen atom or a C1-C6 alkoxy group, and R2 represents a group C1-C3 alkyl, a C3-C4 cycloalkyl group, a halogen atom or a C1-C3 alkoxy group, and Compound VI; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound I in the proportion of 0.1 / 1; a plant disease control composition in which it comprises any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound I in 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound I in the ratio 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound II in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound II in a 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound II in the ratio of 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound III in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound III in a 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound III in the proportion of 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound IV in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound IV in a 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound IV in the ratio of 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 to the present compound tetrazolinone 81 and Compound V in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound V in a 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound V in the proportion of 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound VI in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound VI in a 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound VI in the ratio of 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound VII in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound VII in a 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound VII in the proportion of 10/1; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound VIII in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound VIII in a 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound VIII in the ratio of 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound IX in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound IX in a 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound IX in the proportion of 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 to the present compound tetrazolinone 81 and Compound X in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound X in a 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound X in the proportion of 10/1; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound XI in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound XI in a 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound XI in the ratio of 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound XII in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound XII in 1/1 proportion; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound XII in the ratio of 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 to the present compound tetrazolinone 81 and Compound XIII in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound XIII in a 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound XIII in the ratio of 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 to the present compound tetrazolinone 81 and Compound XIV in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound XIV in a 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 to the present compound tetrazolinone 81 and Compound XIV in the ratio of 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound XV in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound XV in 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound XV in the proportion of 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound XVI in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 for the present tetrazolinone compound 81 and Compound XVI in 1/1 proportion; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound XVI in the ratio of 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 to the present compound tetrazolinone 81 and Compound XVII in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and Compound XVII in a 1/1 ratio; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound XVII in the ratio of 10/1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 to the present compound tetrazolinone 81 and Compound XVIII in the proportion of 0.1 / 1; a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 to the present compound tetrazolinone 81 and Compound XVIII in a 1/1 ratio; and a plant disease control composition comprising any of the compounds selected from the present compound tetrazolinone 1 for the present compound tetrazolinone 81 and Compound XVIII in the proportion of 10/1.
[00209] Below, Formulation Examples are shown below. The term "part (s)" means "part (s) by weight". Formulation Example 1
[00210] Fifty (50) parts of any of the compositions of the present invention mentioned above, 3 parts of calcium lignosulfonate, 2 parts of magnesium lauryl sulfate and 45 parts of synthetic hydrated silicon dioxide were mixed well while being ground to obtain of a formulation. Formulation Example 2
[00211] Twenty (20) parts of any of the compositions of the present invention mentioned above, 1.5 part of sorbitan trioleate were mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and the mixture was then finely crushed by a wet grinding method. To this mixture were then added 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of mixed magnesium and aluminum silicate, and 10 parts of propylene glycol were further added to the mixture. The mixture was stirred to obtain a formulation. Formulation Example 3
[00212] Two (2) parts of any of the compositions of the present invention mentioned above, 88 parts of kaolin clay and 10 parts of talc were mixed together to obtain a formulation. Formulation Example 4
[00213] Five (5) parts of any of the compositions of the present invention mentioned above, 14 parts of polyoxyethylene styrene phenyl ether, 6 parts of calcium dodecylbenzene sulfonate and 75 parts of xylene were mixed together to obtain a formulation. Formulation Example 5
[00214] Two (2) parts of any of the compositions of the present invention mentioned above, one part of synthetic hydrated silicon dioxide, 2 parts of calcium lignosulfonate, 30 parts of bentonite and 65 parts of kaolin clay were ground and mixed together. To the mixture, water was added and the mixture was well kneaded and then granulated and dried to obtain a formulation. Formulation Example 6
[00215] Ten (10) parts of any of the compositions of the present invention mentioned above, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether ammonium sulfate, and 55 parts of water were mixed, and the mixture was then finely ground by a wet grinding method to obtain a formulation.
[00216] In the following, test examples are used to show the effectiveness of the composition of the present invention in controlling plant diseases.
[00217] Here the control effects were evaluated by visual observation of an area with lesion in the tested plants when examined and were followed by a comparison of the area with lesion of the plants treated with the composition of the present invention with an area with lesion of the plants not treated.
[00218] The "Effectiveness" in each test means a value calculated by "Equation 1" below, and is classified depending on its numerical value shown in Table 5. "Equation 1" Effectiveness = 100 x (X - Y) / X where X: Degree of fungal growth in the untreated area Y: Degree of fungal growth in the treated area [Table 5]

[00219] Test Example 1: Control test against wheat leaf spot (Septoria tritici)
[00220] Each of the test compounds was diluted as dimethyl sulfoxide (DMSO) to the prescribed concentration, respectively, and each solution of the test compounds in DMSO was dispensed on a titration plate (with 96 wells) in the amount of 1 μL . It was then dispensed with 150 μL of a potato dextrose broth to which conidia of the wheat leaf pustule fungus were previously inoculated. This plate was grown at 18 ° C for four days, thus allowing the fungus of the wheat leaf pustule to proliferate, and the absorbance at 550 nm of each well on the titration plate was then measured to determine the degree of growth of the fungus. of the wheat leaf pustule. The effectiveness was calculated from the degree of growth obtained by "Equation 1" mentioned above, and was then classified according to [Table 5]. The test results are shown in Table 6 to Table 16 below. Table 6
Table 7

Table 8

Table 9
Table 10

Table 11

Table 12
Table 13
Table 14

Table 15
Table 16
Industrial Applicability
[00221] The present invention can control plant diseases.

权利要求:
Claims (5)
[0001]
1. Composition for the control of plant diseases, characterized by comprising a tetrazolinone compound represented by the formula (1):
[0002]
2. Plant disease control composition according to claim 1, characterized in that the weight ratio of the tetrazolinone compound to the carboxamide compound is that of the tetrazolinone compound / carboxamide compound = 0.1 / 1 to 10/1.
[0003]
3. Method for the control of plant diseases, characterized by comprising applying each effective amount of a tetrazolinone compound represented by formula (1):
[0004]
4. Plant disease control method according to claim 3, characterized in that the weight ratio of the tetrazolinone compound to the carboxamide compound is that of the tetrazolinone compound / 0.1 / carboxamide compound 1 to 10/1.
[0005]
5. Method for the control of plant diseases according to claim 3 or 4, characterized by the fact that the plant or soil for growing the plant is wheat or soil for growing wheat, respectively.

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法律状态:
2019-05-21| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2020-08-18| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-01-12| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-16| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/07/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2013-151419|2013-07-22|

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JP2013151419|2013-07-22|

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PCT/JP2014/069266|WO2015012243A1|2013-07-22|2014-07-15|Plant disease control composition and application for same|

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