composition and method for the control of plant disease

专利摘要:
COMPOSITION AND METHOD FOR PLANT DISEASE CONTROL. The present invention relates to a composition for the control of plant diseases comprising a tetrazolinone compound indicated by formula (1): wherein n indicates an integer between 0 to 5; R1 indicates a halogen atom, and the like; R2 represents a C1-C3 alkyl group, and the like; R1 and R2 may independently have halogen atom (s) in an alkyl moiety; with the proviso that when n is an integer of 2 or more, two or more of R1 may be different from each other, and an azole compound, preferably the composition for the control of plant diseases, in which the ratio by weight of the tetrazolinone compound / the azole compound = 0.1 / 1 to 10/1, it shows an excellent efficacy of control over plant diseases.
公开号:BR112016001412B1
申请号:R112016001412-0
申请日:2014-07-15
公开日:2021-03-09
发明作者:Yuichi Matsuzaki
申请人:Sumitomo Chemical Company, Limited；
IPC主号:

专利说明:

TECHNICAL FIELD
[0001] This application claims priority for and benefit from Japanese Patent Application No. 2013-151418, filed on July 22, 2013, the entire of which is incorporated herein by reference.
[0002] The present invention relates to a plant disease control composition and its use. BACKGROUND TECHNIQUE
[0003] Until now, for the control of plant diseases, many compounds have been developed and used practically (see, Patent Literature 1 and 2). Citation List Patent Literature Patent Literature 1: WO brochure 99/05139 Patent Literature 2: WO brochure 2013/092224 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION
[0004] An object of the present invention is to provide a composition having an excellent efficacy to control plant diseases. METHODS FOR SOLVING PROBLEMS
[0005] The present inventors studied intensively to discover a composition having an excellent efficacy to control plant diseases. As a result, they found that a plant disease control composition comprising a tetrazolinone compound represented by the following formula (1) and one or more azole compounds selected from Group (A) below has excellent control effectiveness over plant diseases.
[0006] Specifically, the present invention includes the following: [1] A composition for the control of plant diseases comprising a tetrazolinone compound represented by the formula (1):
where n is an integer of 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 of 2 or more, two or more of R1 may be different from each other, and one or more azole compounds selected from Group (A): Group (A): a group that consists of propiconazole, protioconazole, triadimenol, prochloraz, penconazole, tebuconazole, flusilazole, diniconazole, bromuconazole, epoxiconazole, diphenoconazole, cyproconazole, metconazole, triflumizol, tetraconazol, hexagonal, fluorobenzol, trichlorazole himexazole, etridiazole, and flutriafol. [2] The composition for the control of plant diseases described in [1], in which a weight ratio of the tetrazolinone compound to the azole compound is that of the tetrazolinone compound / the azole compound = 0.1 / 1 to 10/1. [3] A method for the control of plant diseases that comprises applying each effective amount of a tetrazolinone compound represented by formula (1):
where n is an integer of 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 atom (s) in the alkyl portion; with the proviso that when n is an integer of 2 or more, two or more of R1 may be different from each other, and one or more azole compounds selected from Group (A): Group (A): a group that consists of propiconazole, protioconazole, triadimenol, prochloraz, penconazole, tebuconazole, flusilazole, diniconazole, bromuconazole, epoxiconazole, diphenoconazole, cyproconazole, metconazole, triflumizol, tetraconazol, hexagonal, fluorobenzol, trichlorazole himexazole, etridiazole, and flutriafol, to a plant or soil for growing the plant. [4] The method for controlling plant diseases described in [3], in which a weight ratio of the tetrazolinone compound to the azole compound is that of the tetrazolinone compound / the azole compound = 0.1 / 1 to 10/1. [5] The method for controlling plant diseases described in [3] or [4] where the plant or soil for growing the plant is wheat or the soil for growing wheat, respectively. MODE FOR CARRYING OUT THE INVENTION
[0007] A composition for the control of plant diseases (hereinafter, referred to as "composition of the present invention") comprises a tetrazolinone compound represented by formula (1):
[where n, R1 and R2 are as defined above, respectively.] (hereinafter referred to as "the present tetrazolinone compound") and one or more azole compounds selected from Group (A) (hereinafter referred to as " present azole compound ") Group (A): a group consisting of propiconazole, protioconazole, triadimenol, prochloraz, penconazole, tebuconazole, flusilazole, diniconazole, bromuconazole, epoxiconazole, diphenoconazole, cyproconazole, metconazol, tetronazole, triflum hexaconazole, fluquinconazole, triticonazole, bitercanol, imazalil, ipconazole, simeconazole, himexazole, etridiazole, and flutriafol.
[0008] The present tetrazolinone is explained.
[0009] The substituent (s) as described herein is / are described in detail as mentioned below.
[00010] The term "halogen atom" as used here includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
[00011] The term "C1-C6 alkyl group" as used herein represents a straight or branched chain 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.
[00012] The term "C1-C6 alkoxy group" as used herein 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 group , an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, a pentyloxy group, and a hexyloxy group.
[00013] The term "C1-C6 alkylthio group" as used herein 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 butylthio group , an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group, and a hexylthio group.
[00014] The term "C1-C3 alkyl group" as used herein includes a methyl group, an ethyl group, a propyl group, and an isopropyl group.
[00015] The term "C2-C3 alkenyl group" as used herein includes a vinyl group, a 1-propenyl group, and a 2-propenyl group.
[00016] The term "C2-C3 alkynyl group" as used herein includes an ethynyl group, a 1-propynyl group, and a 2-propynyl group.
[00017] The term "C3-C4 cycloalkyl group" as used herein includes a cyclopropyl group, and a cyclobutyl group.
[00018] The term "C1-C3 alkoxy group" as used herein includes a methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group.
[00019] The term "C1-C2 alkylthio group" as used herein includes a methylthio group, and an ethylthio group.
[00020] The phrase "may have halogen atom (s) in the alkyl portion" as used here means that in the definitions of R1 and R2, the C1-C6 alkyl group, C1-C3 alkyl group, C1-C6 alkoxy group, C1-C3 alkoxy group, C1-C6 alkylthio group, C1-C2 alkylthio group, and C3C4 cycloalkyl group can have halogen atom (s).
[00021] The C1-C6 alkyl group having halogen atom (s) as used herein includes, for example, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monochloromethyl group, a dichloromethyl group, a trichloromethyl group, a group dibromomethyl, 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 group 2,2-difluoropropyl, 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 4- group fluorobutyl, and a 5- fluorohexyl group.
[00022] The C1-C3 alkyl group having halogen atom (s) as used herein includes, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a group dibromomethyl, 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- dichloroethyl, a 2,2,2-trichloropropyl group, a pentafluoroethyl group, a 3-fluoropropyl group, a 3,3,3 -trifluoropropyl group, a heptafluoropropyl group, a heptafluoroisopropyl group, and a 1- (trifluoromethyl) group - 2,2,2-trifluoroethyl, and others.
[00023] The C1-C6 alkoxy group having halogen atom (s) as used herein includes, for example, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a chloromethoxy group, a dichloromethoxy group, a trichloromethoxy group, a group dibromomethoxy, 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 2,2 group -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-fluoroexyloxy group, and others.
[00024] 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-dichloroetoxy group, a 2,2-dichloroethoxy group, 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) -2,2,2 group -trifluoroethyloxy, and a 3-fluoropropyloxy group, and others.
[00025] 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-fluoroexylthio group, and others.
[00026] 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, and others.
[00027] 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, and others.
[00028] First, a process for the preparation of the present tetrazolinone compound is explained.
[00029] The present tetrazolinone compound can be prepared, for example, according to the processes mentioned below. (Case A)
[00030] The present tetrazolinone compound can be prepared by reacting a compound represented by formula (2) (hereinafter referred to as compound (2)) with a compound represented by formula (3) (hereinafter referred to as 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]
[00031] The reaction is usually carried out in a solvent.
[00032] 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.
[00033] 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 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.
[00034] In the reaction, the compound (3) is used generally within a range of 1 to 10 molar ratios, and the base is used generally within a range of 0.5 to 5 ratios (s) ) molar (s), when opposed to 1 mole of compound (2).
[00035] The reaction temperature is generally within the range of -20 to 150 ° C. The reaction time of the reaction is generally within a range of 0.1 to 24 hours.
[00036] If necessary, sodium iodide, tetrabutylammonium iodide, and others can be added to the reaction, and these compounds are used generally, within a range of 0.001 to 1.2 molar ratio (s) when in opposition to 1 mole of compound (2).
[00037] When the reaction is complete, the reaction mixtures are extracted with organic solvent (s), and the resulting organic layers are prepared (for example, drying and concentration) to isolate the present tetrazolinone compound. The isolated tetrazolinone compound can also be purified, for example, by chromatography and recrystallization. (Case B)
[00038] The present tetrazolinone compound can be prepared by reacting a compound represented by formula (4) (hereinafter referred to as compound (4)) with a compound represented by formula (5) (hereinafter referred to as compound (5) ) in the presence of a catalyst and a base.
[where, n, R1, R2 are as defined 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 toluenesulfonyloxy group, a B (OH) 2 group, an alkoxyboryl group, or a trifluoroborate (BF3-K +).]
[00039] The reaction is usually carried out in a solvent.
[00040] 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; acidic 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.
[00041] 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-chloroiodobenzene, 4-bromoiodobenzene, phenylboronic acid, 4-fluorophenylboronic acid, 4-chlorophenylboronic acid, 4-methylphenylboronic acid, and 4-methoxyphenylboronic acid.
[00042] Examples of the catalyst to be used in the reaction include copper (I) iodide, copper (II) acetate, palladium (II) acetate, dichlorobis (triphenylphosphine) palladium, tetracistriphenylphosphinapalladium (0), palladium (II) acetate / trisciclohexylphosphine, bis (diphenylphosphine ferrocenyl) dichloride palladium (II), 1,3-bis (2,6-diisopropylphenyl) imidazole-2-ylidene, aryl (chlorine) (1,4-naphthoquinone) dimer (1,3-dimesityl-1,3-dihydro-2H-imidazol-2-ylidene) palladium, or palladium (II) / dicyclohexyl (2 ', 4', 6'-triisopropylbiphenyl-2- il) phosphine, and tris (dibenzylidene acetone) dipaladium.
[00043] 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.
[00044] In the reaction, compound (5) is used generally within a range of 1 to 10 molar ratios, and the catalyst is used generally within a range of 0.001 to 5 molar ratio (s) (s), and the base is generally used within a range of 0.5 to 10 molar ratio (s), as opposed to 1 mole of compound (4).
[00045] If necessary, a binder, such as 1,10-phenanthroline, tetramethylenediamine, and others can be added to the reaction, and these compounds are used generally, within a range of 0.001 to 5 molar ratio (s) when in opposition to 1 mole of compound (4).
[00046] The reaction temperature is generally within the range of -20 to 150 ° C. The reaction time of the reaction is generally within a range of 0.1 to 24 hours.
[00047] When the reaction is complete, the reaction mixtures are extracted with organic solvent (s), and the resulting organic layers are prepared (for example, drying and concentration) to isolate the present tetrazolinone compound. The isolated tetrazolinone compound can also be purified, for example, by chromatography and recrystallization. Process C
[00048] The present tetrazolinone compound can be prepared by coupling a compound represented by formula (6) (hereinafter referred to as compound (6)) (which can be prepared according to the method similar to Process A) with a compound represented by formula (7) (hereinafter referred to as 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 B (OH) 2, an alkoxyboryl group , or trifluoroborate (BF3-K +).]
[00049] The reaction is usually carried out in a solvent.
[00050] 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; acidic 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.
[00051] 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, and 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 reacting the resulting mixtures with boronate esters to obtain boronate ester derivatives. In addition, the boronate ester derivatives obtained in the above-mentioned reaction can be hydrolyzed when necessary to the corresponding boronic acid derivatives. In addition, according to a method described in a review article by Molander et al., Acc. Chem. Res. 2007, 40, 275 and the like, the aforementioned boronate ester derivatives can be fluorinated with potassium bifluoride and the like to obtain the BF3-K + trifluoroborate salts.
[00052] 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 dimer, aryl (chlorine) (1,3-dimethyl-1,3-dihydro -2H-imidazol-2-ylidene) palladium or palladium (II) / dicyclohexyl (2 ', 4', 6'-triisopropylbiphenyl-2-yl) phosphine, and tris (dibenzylidene acetone) dipaladium, and others.
[00053] 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.
[00054] In the reaction, the compound (7) is used generally within a range of 1 to 10 molar ratios, and the base is used generally within a range of 1 to 10 molar ratios, and the catalyst is generally used within a range of 0.0001 to 1 molar ratio, as opposed to 1 mole of compound (6).
[00055] The reaction temperature is generally within the range of 0 to 150 ° C. The reaction time of the reaction is generally within a range of 0.1 to 24 hours.
[00056] When the reaction is complete, the reaction mixtures are extracted with organic solvent (s), and the resulting organic layers are prepared (for example, drying and concentration) to isolate the present tetrazolinone compound. The isolated tetrazolinone compound can also be purified, for example, by chromatography and recrystallization.
[00057] Next, a method for preparing a synthetic intermediate compound of the present tetrazolinone compound is explained in detail. Reference Process A
[00058] The compound represented by formula (9) (hereinafter referred to as compound (9)) can be prepared by reacting compound (2) with a compound represented by formula (8) (hereinafter referred to as 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 anacetyl group, a formyl group, a benzoyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group, and a group tert-butoxycarbonyl.]
[00059] The reaction can be carried out according to the above mentioned Process A. Reference Process B
[00060] The compound represented by formula (4) can be prepared by treating the compound (9) with a deprotecting agent.
[where, R2 and R3 are as defined above, respectively.]
[00061] The reaction is usually carried out in a solvent.
[00062] 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; acidic 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.
[00063] 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.
[00064] In the reaction, the deprotecting agent is generally used within a range of 1 to 100 molar ratios, as opposed to 1 mole of compound (9).
[00065] The reaction temperature is generally within the range of -20 to 150 ° C. The reaction time of the reaction is generally within a range of 0.1 to 24 hours.
[00066] When the reaction is complete, the reaction mixtures are extracted with organic solvent (s), and the resulting organic layers are prepared (for example, drying and concentration) to isolate the Compound (4). The isolated compound (4) can also be purified, for example, by distillation, chromatography and recrystallization. Reference Process C
[00067] The compound represented by formula (11) (hereinafter referred to as compound (11)) can be prepared by reacting a compound represented by formula (10) (hereinafter referred to as compound (10)) with an azidating agent .
[where, R2 is the same as defined above.]
[00068] The reaction is usually carried out in a solvent.
[00069] 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; acidic 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.
[00070] 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.
[00071] In the reaction, the azidation agent is used generally, within a range (s) of 1 to 10 molars when in opposition to 1 mole of compound (10).
[00072] The reaction temperature is generally within the range of -20 to 150 ° C. The reaction time of the reaction is generally within a range of 0.1 to 24 hours.
[00073] If necessary, a Lewis acid, such as aluminum chloride and zinc chloride, can be added to the reaction, and these compounds are used generally, within a range of 0.05 to 5 ratio (s) molar (ES), when opposed to 1 mole of compound (10).
[00074] When the reaction is complete, the reaction mixtures are extracted with organic solvent (s), and the resulting organic layers are prepared (for example, drying and concentration) to isolate the compound (11). The isolated compound (11) can also be purified, for example, by chromatography and recrystallization. Reference Process D
[00075] The compound represented by formula (13) (hereinafter referred to as compound (13)) can be prepared by reacting compound (11) with a compound represented by formula (12) (hereinafter referred to as compound (12) ) in the presence of a base.
[where R2 is the same as defined 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.]
[00076] The reaction is usually carried out in a solvent.
[00077] 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; acidic 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.
[00078] 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.
[00079] 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.
[00080] In the reaction, the compound (12) is used generally within a range of 1 to 10 molar ratios, and the base is used generally within a range of 0.5 to 10 ratios (ions ) molar (s), when opposed to 1 mole of compound (11).
[00081] The reaction temperature is generally within the range of -20 to 150 ° C. The reaction time of the reaction is generally within a range of 0.1 to 24 hours.
[00082] When the reaction is complete, the reaction mixtures are extracted with organic solvent (s), and the resulting organic layers are prepared (for example, drying and concentration) to isolate the compound (13). The isolated compound (13) can also be purified, for example, by chromatography and recrystallization. Reference Process E
[00083] The compound (2) can be prepared by reacting the compound (13) with a halogenating agent.
(13) [where, R2 and Z1 are as defined above, respectively.]
[00084] The reaction is usually carried out in a solvent.
[00085] 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-trifluorol, Α-trifluorol; 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.
[00086] Examples of the halogenating agent to be used in the reaction include a chlorinating agent, a bromination agent or an iodizing agent, such as chlorine, bromine, iodine, sulfuryl chloride, N-chlorosucinimide, N-bromosucinimide, 1, 3-dibromo-5,5-dimethylhydantoin, iodosuccinimide, tert-butyl hypochlorite, N-chloroglutarimide, N-bromoglutarimide, N-chloro-N-cyclohexyl-benzenesulfonamide, and N-bromophthalimide.
[00087] A radical initiator can be used in the reaction.
[00088] Examples of 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 ketone peroxide.
[00089] In the reaction, the halogenating agent is used generally within a range of 1 to 10 molar ratios, and the radical initiator is generally used within a range of 0.01 to 1 molar ratio , when opposed to 1 mole of compound (13).
[00090] The reaction temperature is generally within the range of -20 to 150 ° C. The reaction time of the reaction is generally within a range of 0.1 to 24 hours.
[00091] When the reaction is complete, the reaction mixtures are extracted with organic solvent (s), and the resulting organic layers are prepared (for example, drying and concentration) to isolate the compound (2). The isolated compound (2) can also be purified, for example, by chromatography and recrystallization. Reference Process F
[00092] A compound represented by formula (15) (hereinafter referred to as compound (15)) can be prepared by reacting a compound represented by formula (2-1) where R2 in a formula (2) represents Z1 (hereinafter hereinafter referred to as compound (2-1)) with a compound represented by formula (15) (hereinafter referred to as compound (15)).
[where, Z1 is the same as defined above, R4 represents a C1 C12 alkyl group or a phenyl group, and M represents sodium, potassium or lithium.]
[00093] The reaction is usually carried out in a solvent.
[00094] 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; acidic 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.
[00095] 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.
[00096] In the reaction, compound (14) is used generally within a range of 1 to 10 molar ratios when opposed to 1 mole of compound (2-1).
[00097] The reaction temperature is generally within the range of -20 to 150 ° C. The reaction time of the reaction is generally within a range of 0.1 to 24 hours.
[00098] When the reaction is complete, the reaction mixtures are extracted with organic solvent (s), and the resulting organic layers are prepared (for example, drying and concentration) to isolate the compound (15). The isolated compound (15) can also be purified, for example, by distillation, chromatography and recrystallization. Reference Process G
[00099] A compound represented by formula (16) (hereinafter referred to as compound (16)) can be prepared by reacting Compound (15) and Compound (7) in the presence of a base.
[where R2, R4, Z4 and Z1 are as defined above, respectively.] The reaction can be carried out according to the above mentioned Process C. Reference Process H
[000100] The compound (2) can also be prepared by reacting the compound (16) and a halogenating agent.
[where, R2, R4 and Z1 are as defined above, respectively.]
[000101] The reaction is usually carried out in a solvent.
[000102] Examples of the solvent to be used in the reaction include 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; 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.
[000103] Examples of the halogenating agent include hydrochloric acid, hydrobromic acid, and hydroiodic acid.
[000104] In the reaction, the halogenating agent is generally used within a range of 1 or more molar ratios when opposed to 1 mole of compound (16).
[000105] The reaction temperature is generally within the range of -20 to 150 ° C. The reaction time of the reaction is generally within a range of 0.1 to 24 hours.
[000106] When the reaction is complete, the reaction mixtures are extracted with organic solvent (s), and the resulting organic layers are prepared (for example, drying and concentration) to isolate the compound (2). The isolated compound (2) can also be purified, for example, by distillation, chromatography and recrystallization.
[000107] The present azole compounds are all known compounds, and they are described in "THE PESTICIDE MANUAL - 16th. Edition (published by BCPC) ISBN 9781901396867". These compounds can be obtained from commercially available formulations, or can be prepared according to known methods.
[000108] The present azole compounds are shown in [Table 1] below. Table 1


[000109] In the composition of the present invention, a weight ratio of the present tetrazolinone compound to the present azole compound includes, for example, the present tetrazolinone compound / the present azole compound = 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.
[000110] The composition of the present invention can be a mixture of the present tetrazolinone compound and the present azole compound, and is generally prepared by mixing the present tetrazolinone compound, the present azole compound and an inert carrier , optionally adding a surfactant and other formulation aids.
[000111] The composition of the present invention can be formulated in an oily solution, an emulsifiable concentrate, a flowable formulation, a wetting powder, a water-dispersible granule, a powder, or a granule. The formulations in this way can be used directly as a plant disease control agent, or used after the addition of other inert ingredients.
[000112] The total amount of the present tetrazolinone compound and the present azole compound in the composition of the present invention is generally within a range of 0.1% to 99% by weight, preferably 0.2% to 90% by weight, and more preferably, from 1% to 80% by weight.
[000113] 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, quartz powder, 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, acetate ethyl and butyl acetate), 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, trichloride ethylene and carbon tetrachloride), and others.
[000114] 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.
[000115] Examples of other auxiliary agents for 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 (acid isopropyl 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, and others.
[000116] The composition of the present invention can also be formulated by formulating each of the present tetrazolinone compound and the present azole compound, according to the aforementioned method and if necessary, diluting it with water to obtain a formulation containing the present tetrazolinone compound or diluted solutions containing it, or a formulation containing the present azole compound or diluted solutions containing it, respectively, followed by mixing the resulting formulations or diluted solutions together.
[000117] The composition of the present invention can be used to protect plants from plant diseases.
[000118] The control method of the present invention can control plant diseases by applying the composition of the present invention to plants or soil for plant cultivation, alternatively applying the present tetrazolinone compound or the present azole compound separately to plants or soil for cultivation of plants.
[000119] The method for applying the composition of the present invention is not particularly limited, in that the form of application is a way in which the present compound can be applied substantially, and includes, for example, an application to plants , such as a foliar application; an application to the area for growing plants such as a submerged treatment; and an application to the seed, such as disinfecting the seed.
[000120] The application dose of the composition of the present invention varies depending on climatic conditions, dosage forms, application times, application methods, areas to be applied, target diseases, target crops and others, and is in the range, generally, 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., is generally applied by diluting it with water. In this case, the concentration of the composition of the present invention after dilution is in the range, generally, from 0.0005 to 2% by weight, and preferably, 0.005 to 1% by weight, and the powder formulation or granular formulation, etc. , is generally applied in its natural state without diluting it. In application to seeds, the amount of the composition of the present invention is in the range, generally, from 0.001 to 100 g, and preferably, from 0.01 to 50 g per 1 kg of the seeds.
[000121] Examples of where plant diseases develop include rice paddies, fields, tea gardens, orchards, non-agricultural areas, houses, seed trays, seed boxes, seed soils and seed beds.
[000122] The composition of the present invention can be used as an agent for the control of plant disease in agricultural areas, such as fields, rice fields, lawns, and orchards. The composition of the present invention can control diseases occurring in agricultural or other areas to cultivate the following '' plants '', and others. Crops: corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybeans, peanuts, buckwheat, beets, canola, sunflowers, sugar cane, tobacco, and others; Vegetables: solanaceous vegetables (for example, eggplant, tomatoes, peppers, pepper and potatoes), cucurbits (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, crown daisy, artichoke and lettuce), lily vegetables (eg chives, onions, garlic and asparagus) ), starchy vegetables (for example, carrots, parsley, celery and parsnips), chenopodiate vegetables (for example, spinach and Swiss chard), lameaceous vegetables (for example, Perilla frutescens, mint and basil), strawberry, sweet potatoes, Dioscorea japonica , colocasia, and 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, and others; Non-fruit trees: tea, mulberry, angiospersms, 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); and others.
[000123] The aforementioned "plant" includes genetically modified crops.
[000124] Pests over 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 not 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 gibberellin (Fusarium gaminaarum, 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 rust (Ustilago tritici), saddlebag (Tilletia caries), ocellus (Pseudocercosporella herpotrichoides), speckled leaf spot (Mycosphaerella graminicola), glum stain (nodule glum ), 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), bare coal (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 héterostrophus), zoned spot (Gloeocercospora sorghi), polishing rust (Puccinia polisora), cercosporiosis (Cercospora zeae-maydis), and rhizoctonia (Rhizoctonia solani); Citrus diseases: melanosis (Diaporthe citri), warts (Elsinoe fawcetti), fruit rot (Penicillium digitatum, P. italicum); diseases caused by Phytophthora (Phytophthora parasitica, Phytophthora citroftora); Apple diseases: flowering rust (Monilinia mali), cancer (Waltz ceratosperma), powdery mildew (Podosphaera leucotricha), leaf spot caused by Alternaria (Alternaria alternata apple pathotype), wart (Venturia inaequalis), bitter rot (Colletotrichum acutatum), and crown rot (Phytophthora cactorum); Pear diseases: scabies (Venturia nashicola, V. pirina), black spot (pathogen of the Japanese pear Alternaria alternata), rust (Gymnosporangium haraeanum), and rot of the neck (Phytophthora 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), 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), wilt caused by fusarium (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), phytophora (phytophora) and phytophora (phytophora). wilting (Pythium sp.); Tomato diseases: black spot (Alternaria solani), cladosporium spot (Cladosporium fulvum), and late blight (Phytophthora infestans); Eggplant disease: 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); Galician onion 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), root and stem rot caused by phytophora (Phytophthoraoyae), soybean molasses (Rhizoctonia solani), target spot (Corynespora cassiicola), and stem rot caused by sclerotinia (Sclerotinia sclerotumum); 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 spot (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 spot caused by Cercospora (Cercospora beticola), leaf disease (Thanatephorus cucumeris), root rot (Thanatephorus cucumeris), and root rot caused by aphanomyces (Aphanomyces 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, and 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 stage of various plants caused by Aspergillus spp., Penicilliumspp., Fusariumspp., Gibberellaspp., Tricodermaspp., Thielaviopsisspp., Rhizopusspp., Mucorspp., Corticiumspp., Phomaspp., Rhizoctoniaspp. or Diplodiaspp .; and viral diseases of several plants mediated by Polimixa spp. or Olpidium spp .; and so on. EXAMPLES
[000125] Next, the following Process for the present tetrazolinone compound, and the Examples including Formulation Examples and Test Examples, serve to illustrate the present invention in greater detail, which should not be intended to limit the present invention.
[000126] First, Preparation Example for the present tetrazolinone compound is shown. Preparation Example 1
[000127] 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 being allowed to cool, water was added, and the mixtures were 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 provide 1- (2- {[1- (4-chlorophenyl) -1H-pyrazol-3-yl] oxymethyl} -3-chlorophenyl) -4-methyl- 1,4-dihydrotetrazol-5-one (hereinafter referred to as Present tetrazolinone compound 1) 0.61 g. Present tetrazolinone compound 1
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
[000128] 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 mixtures after allowing to cool, water was added and the mixtures were 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 provide 1- (2- {[1- (4-chlorophenyl) -1H-pyrazol-3-yl] oxymethyl} -3-bromophenyl) -4-methyl- 1,4-dihydrotetrazol-5-one (hereinafter referred to as Present tetrazolinone compound 2) 24.6 g. Present tetrazolinone compound 2
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
[000129] A mixture of the present tetrazolinone compound 2 (described in Preparation Example 2) 0.92 g, methyl boronic acid 0.18 g, tripotassium phosphate 1.27 g, water 0.11 ml, [1, 1'-bis (diphenylphosphino) ferrocene] -palladium (II) dichloromethane complex dichloride 0.16 g, and 7 mL dioxane was stirred with heating under reflux for one and a half hours. To the reaction solution after cooling, water was added, and the mixtures were 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 provide 1- (2 - {[1- (4-chlorophenyl) -1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) -4-methyl- 1,4-dihydrotetrazol-5-one (hereinafter referred to as Present tetrazolinone compound 3) 0.27 g. Present tetrazolinone compound 3
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
[000130] 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 mixtures after allowing to cool, water was added, and the mixtures were 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 provide 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 tetrazolinone compound 4) 0.28 g. Present tetrazolinone compound 4
1H-NMR (CDCl3) Δ (ppm): 7.57 (1H, d, J = 2.7 Hz), 7.49-7.44 (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
[000131] 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 mixtures after being allowed to cool, water was added and the mixtures were 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 provide 1- (2- {[1- (4-chlorophenyl) -1H-pyrazol-3-yl] oxymethyl} -3-methoxyphenyl) -4-methyl- 1,4-dihydrotetrazol-5-one (hereinafter referred to as Present tetrazolinone compound 5) 0.97 g. Present tetrazolinone compound 5
1H-NMR (CDCl3) Δ (ppm): 7.63 (1H, d, J = 2.7 Hz), 7.53-7.49 (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
[000132] A mixture of the present compound of 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, [1, 1'- bis (diphenylphosphino) ferrocene] -palladium (II) 0.16 g dichloride dichloride complex and 15 ml dioxane was stirred with heating under reflux for two hours. To the reaction solution after cooling, water was added, and the mixtures were 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 provide 1- (2- {[1- (4-chlorophenyl) -1H-pyrazol-3-yl] oxymethyl} -3-ethylpenyl) -4-methyl- 1,4-dihydroteterazol-5-one (hereinafter referred to as Present tetrazolinone compound 6) 0.24 g. Present compound of tetrazolinone 6
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
[000133] A mixture of the present tetrazolinone compound 2 (described in Preparation Example 2) 0.92 g, cyclopropyl boronic acid 0.26 g, tripotassium phosphate 1.27 g, water 0.11 ml, [1, 1'-bis (diphenylphosphino)] ferrocene] -palladium (II) dichloride dichloride complex 0.16 g, and 7 ml dioxane was stirred with heating under reflux for one and a half hours. To the reaction solution after cooling, water was added, and the mixtures were 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 provide 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. Present tetrazolinone compound 7
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
[000134] 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 10 ml acetonitrile was stirred with heating under reflux for four hours. To the reaction mixtures after being allowed to cool, water was added, and the mixtures were 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 provide 1- (2- {[1- (4-bromophenyl) -1H-pyrazol-3-yl] oxymethyl} -3-methylpheni) -4-methyl- 1,4-dihydrotetrazol-5-one (hereinafter referred to as Present tetrazolinone compound 8) 0.37 g. Present tetrazolinone compound 8
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
[000135] 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 mixtures after being allowed to cool, water was added, and the mixtures were 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 provide 1- (2- {[1- (4-chloro-3-fluorophenyl) -1H-pyrazol-3yl] oxymethyl} -3-methylphenyl) -4- methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 9) 0.12 g. Present compound of tetrazolinone 9
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
[000136] 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 mixtures after being allowed to cool, water was added, and the mixtures were 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 provide 1- (2 - {[1- (2-methoxyphenyl) -1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) -4-methyl- 1,4-dihydroteterazol-5-one (hereinafter referred to as Present tetrazolinone compound 10) 0.23 g. Present tetrazolinone compound 10
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
[000137] A mixture of 1- (2 - {[1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) - 4-methyl-1,4-dihydroteterazol-5-one (described in the Preparation Example Reference 14) 1.00 g, 4-chloro-2-methoxyphenyl boronic acid 0.78 g, copper (II) acetate 0.98 g, pyridine 0.59 mL, 4A molecular sieve 1.50 g, and acetonitrile 15 ml was stirred with heating under reflux for fifteen hours. To the reaction mixtures after being allowed to cool, water was added, and the mixtures were 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 provide 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. Present tetrazolinone compound 11
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).
[000138] Next, processes for the preparation of intermediates of the above-mentioned tetrazolinone compound are shown below as Reference Preparation Examples. Reference Preparation Example 1
[000139] Anhydrous aluminum chloride 21.9 g was added to N, N-dimethylformamide 250 ml under cooling, and the mixtures were stirred for fifteen minutes. To this was added 10.7 g sodium azide and the mixtures were stirred for fifteen minutes. To this was then added 1-chloro-3-isocyanate-2-methylbenzene 25.0 g, and the resulting mixtures were heated to 80 ° C for five hours. The reaction solutions after cooling were added to a mixture of sodium nitrite 35 g, water 2L and ice 500 g with stirring. The mixtures were acidified with 10% hydrochloric acid and 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 provide 1- (2-methyl-3-chlorophenyl) -1,4-dihydrotetrazole-5-one 17.0 g. 1- (2-methyl-3-chlorophenyl) -1,4-dihydrotetrazol-5-one
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
[000140] To a mixture of 1- (2-methyl-3-chlorophenyl) -1,4-dihydrotetrazol-5-one (described in Reference Preparation Example 1) 10.00g and N, N-dimethylformamide 100 mL 60% sodium hydride 2.30 g was added under cooling. The mixtures were raised to room temperature and were stirred for one hour. To the reaction mixtures, methyl iodide 3.2 ml was added under cooling. The mixtures were raised to room temperature and stirred for fourteen hours. To the reaction mixtures, water was added, and the mixtures were 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 provide 1- (2-methyl-3-chlorophenyl) -4-methyl-1,4-dihydrotetrazol-5-one 1.56 g. 1- (2-methyl-3-chlorophenyl) -4-methyl-1,4-dihydrotetrazol-5-one Cl
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
[000141] 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-bromosucinimide 1.42 g and chlorobenzene 30 ml was stirred with heating under reflux for five hours. To the reaction solutions after cooling, water was added, and the mixtures were 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 provide 1- (2-bromomethyl-3-chlorophenyl) -4-methyl-1,4-dihydrotetrazol-5-one 1.94 g. 1- (2-bromomethyl-3-chlorophenyl) -4-methyl-1,4-dihydrotetrazol-5-one
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
[000142] Anhydrous aluminum chloride 19.7 g was added to N, N-dimethylformamide 220 ml under cooling, and the mixture was stirred for fifteen minutes. To this was added sodium azide 9.6 g and the mixtures were stirred for fifteen minutes. To this was then added 1-bromo-3-isocyanate-2-methylbenzene 30.3 g and the resulting mixtures were heated to 80 ° C for five hours. The reaction solutions after cooling were added to a mixture of sodium nitrite 33 g, water 2 L and ice 500 g with stirring. The mixtures were acidified with 10% hydrochloric acid, and were 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 provide 1- (2-methyl-3-bromophenyl) -1,4-dihydrotetrazole- 5- one 31.4 g. 1- (2-methyl-3-bromophenyl) -1,4-dihydrotetrazol-5-one
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
[000143] 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 cooling. The reaction mixtures were raised to room temperature, and were stirred for one hour. To the reaction mixtures, methyl iodide 8.4 ml was added under cooling. The mixtures were raised to room temperature, and were stirred for fourteen hours. To the reaction mixtures, water was added and the mixtures were 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 residues were subjected to silica gel column chromatography to provide 1- (2-methyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one 8.47 g. 1- (2-methyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one
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
[000144] 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-bromosucinimide 6.44 g and chlorobenzene 125 ml was stirred with heating under reflux for five hours. To the reaction solutions after cooling, water was added and the resulting mixtures were 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 residues were subjected to silica gel column chromatography to provide 1- (2-bromomethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one 7.52 g. 1- (2-bromomethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazole-5-
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
[000145] Anhydrous aluminum chloride 16.0 g was added to N, N-dimethylformamide 180 ml under cooling, and the mixtures were stirred for fifteen minutes. To this was added sodium azide 7.8 g and the mixtures were stirred for fifteen minutes. To this was then added 1-methoxy-3-isocyanate-2-methylbenzene 17.0 g, and the resulting mixtures were heated to 80 ° C for four and a half hours. The reaction solutions after cooling were added to a mixture of 25 g sodium nitrite, 2 L water and 500 g ice with stirring. The mixtures were acidified with 10% hydrochloric acid and 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 provide 1- (2-methyl-3-methoxyphenyl) -1,4-dihydrotetrazole-5-one 16.2 g. 1- (2-methyl-3-methoxyphenyl) -1,4-dihydrotetrazol-5-one
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
[000146] 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 cooling. The reaction mixtures were raised to room temperature and were stirred for fourteen hours. To the reaction mixtures, methyl iodide 3.5 ml was added under cooling. The mixtures were raised to room temperature and were stirred for one hour. To the reaction mixtures, methyl iodide 3.5 ml was added under cooling. The mixtures were raised to room temperature and stirred for fourteen hours. To the reaction mixtures, water was added and the mixtures were 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 residues were subjected to silica gel column chromatography to provide 1- (2-methyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one 2.19 g. 1- (2-methyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one
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
[000147] 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-bromosucinimide 2.16 g and chlorobenzene 40 ml was stirred with heating under reflux for five hours. To the reaction solutions after cooling, water was added, and the resulting mixtures were 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 residues were subjected to silica gel column chromatography to provide 1- (2-bromomethyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one 2.36 g. 1- (2-bromomethyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazole-5-
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
[000148] 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 mixtures, saturated aqueous sodium bicarbonate solution was added, and the resulting mixtures were extracted with ethyl acetate. The organic layers were washed with saturated aqueous sodium bicarbonate solution, and then dried over anhydrous sodium sulfate. The mixtures were concentrated under reduced pressure to provide 1- (2-methoxymethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one 36.2 g. 1- (2-methoxymethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one
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
[000149] 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, [1,1'-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloride 10.6 g and dioxane 500 ml adduct was stirred at 90 ° C for five hours and a half. The reaction mixtures after cooling were filtered, and the filtrates were concentrated under reduced pressure. The resulting residues were subjected to silica gel column chromatography to provide 1- (2-methoxymethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one 25.6 g. 1- (2-methoxymethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one
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
[000150] 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 25% hydrogen bromide-acetic acid solution 50 ml was stirred at 65 ° C for one hour. To the reaction mixtures, saturated saline was added, and the mixtures were extracted with ethyl acetate. The organic layers were washed with saturated aqueous sodium bicarbonate solution and then dried over anhydrous sodium sulfate. The mixtures were concentrated under reduced pressure to provide 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one 27.9 g. 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one
Me 1H-NMR (CDCl3) Δ (ppm): 2.51 (3H, s), 3.75 (3H, s), 4.51 (2H, s), 7,227.24 (1H, m), 7, 36-7.39 (2H, m). Reference Preparation Example 13
[000151] 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 mixtures after being allowed to cool, water was added, and the resulting mixtures were 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 provide 1- (2- {[1-acetyl-1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) -4-methyl-1,4- dihydrotetrazol-5-one 0.58 g.
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
[000152] 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 mixtures were added to saturated aqueous sodium bicarbonate solution, and the resulting mixtures were 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 provide 1- (2- {[1H-pyrazol-3-yl] oxymethyl} -3-methylphenyl) -4-methyl-1,4-dihydrotetrazole- 5-one 2.5 g.
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).
[000153] The compounds selected from the present tetrazolinone compound 12 to the present tetrazolinone compound 81, which can be prepared according to the above mentioned Process A to Process C, are shown below.
[Table 2]

[Table 3]

[Table 4]


[000154] Examples of an embodiment of the present tetrazolinone compound include the compounds represented by formula (1) wherein the substituents represent the following: a tetrazolinone compound represented by formula (1) where n is an integer of any one of 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 of 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 of 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 of 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 of any number 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) wherein 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.
[000155] Examples of a form of the composition of the present invention include the following: a composition for the control of plant diseases comprising a tetrazolinone compound represented by formula (1) where n is an integer of 1 or 2, R1 represents a halogen atom or a C1-C6 alkoxy group, R2 represents a C1C3 alkyl group, 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 of 1 or 2, R1 represents a halogen atom or a C1-C3 alkoxy group, R2 represents a C1C3 alkyl group, 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 of 1 or 2, R1 represents a halogen atom or a C1-C6 alkoxy group, and R2 represents a C1C3 alkyl group, 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 of 1 or 2, R1 represents a halogen atom or a C1-C6 alkoxy group, and R2 represents a C1C3 alkyl group, 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 of 1 or 2, R1 represents a halogen atom or a C1-C6 alkoxy group, and R2 represents a C1C3 alkyl group, 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 of 1 or 2, R1 represents a halogen atom or a C1-C6 alkoxy group, and R2 represents a C1C3 alkyl group, 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 of 1 or 2, R1 represents a halogen atom or a C1-C6 alkoxy group, and R2 represents a C1C3 alkyl group, 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 of 1 or 2, R1 represents a halogen atom or a C1-C6 alkoxy group, and R2 represents a C1C3 alkyl group, 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 tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound I in the ratio of 0.1 / 1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound I at 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 I in the ratio 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 II in the ratio of 0.1 / 1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound II at 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 II in the 10/1 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 III in the ratio of 0.1 / 1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound III in the 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 III in the 10/1 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 IV in the ratio of 0.1 / 1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound IV at 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 IV in the 10/1 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 V in the ratio of 0.1 / 1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound V in the ratio of 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 V in the ratio 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 VI in the ratio of 0.1 / 1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound VI at 1/1 ratio; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound VI in the ratio of 10/1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound VII in the ratio 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 VII at 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 VII in the 10/1 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 0.1 / 1; a composition for the control of plant diseases, 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 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 the 10/1 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 IX in the ratio of 0.1 / 1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound IX at 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 IX in the 10/1 ratio; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound X in the ratio 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 at 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 X in the ratio 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 ratio of 0.1 / 1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound XI in the ratio of 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 the 10/1 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 XII in the ratio 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 at 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 XII in the 10/1 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 0.1 / 1; a composition for the control of plant diseases, 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 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 the 10/1 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 XIV in the ratio of 0.1 / 1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound XIV in the ratio of 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 the 10/1 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 XV in the ratio 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 at 1/1 ratio; 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 XV in the ratio 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 XVI in the ratio 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 XVI at 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 XVI in the 10/1 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 XVII in the ratio of 0.1 / 1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound XVII in the ratio of 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 the 10/1 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 XVIII in the ratio of 0.1 / 1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound XVIII in the ratio of 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 XVIII in the 10/1 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 XIX in the ratio 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 XIX at 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 XIX in the 10/1 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 XX in the ratio 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 XX at 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 XX in the ratio of 10/1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound XXI in the ratio 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 XXI in the 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 XXI in the 10/1 ratio; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound XXII in the ratio 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 XXII in the 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 XXII in the 10/1 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 XXIII in the ratio of 0.1 / 1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound XXIII in the ratio of 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 XXIII in the 10/1 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 XXIV in the ratio of 0.1 / 1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound XXIV in the 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 XXIV in the 10/1 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 XXV in the ratio 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 XXV in the ratio of 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 XXV in the 10/1 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 XXVI in the ratio of 0.1 / 1; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound XXVI in the ratio of 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 XXVI in the 10/1 ratio; a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound XXVII in the ratio 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 XXVII at 1/1 ratio; and a composition for the control of plant diseases, comprising any of the compounds selected from the present tetrazolinone compound 1 to the present tetrazolinone compound 81 and compound XXVII in the ratio of 10/1.
[000156] Next, the Formulation Examples are shown below. The term "part (s)" means "part (s) by weight". Formulation Example 1
[000157] Fifty (50) parts of any of the above mentioned compositions of the present invention, 3 parts of calcium lignosulfonate, 2 parts of magnesium lauryl sulfate and 45 parts of synthetic hydrated silicon dioxide are mixed well at the same time as grinding to obtain a formulation. Formulation Example 2
[000158] Twenty (20) parts of any of the above-mentioned compositions of the present invention, 1.5 parts of sorbitan trioleate are mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and the mixture is then finely ground by a wet grinding method. To this mixture are then added 40 parts of an aqueous solution containing 0.05 parts of xanthan gum and 0.1 parts of magnesium aluminum, silicate, and 10 parts of propylene glycol are also added thereto. The mixture is stirred to obtain a formulation. Formulation Example 3
[000159] Two (2) parts of any of the above mentioned compositions of the present invention, 88 parts of kaolin clay and 10 parts of talc are mixed - ground to obtain a formulation. Formulation Example 4
[000160] Five (5) parts of any of the aforementioned compositions of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzene sulfonate and 75 parts of xylene are mixed - ground to obtain a formulation. Formulation Example 5
[000161] Two (2) parts of any of the above mentioned compositions of the present invention, one part of synthetic hydrated silicon dioxide, 2 parts of calcium lignosulfonate, 30 parts of bentonite and 65 parts of kaolin clay are mixed - ground and water is added to them and the mixture is well kneaded and then granulated and dried to obtain a formulation. Formulation Example 6
[000162] Ten (10) parts of any of the above mentioned compositions of the present invention, 35 parts of white carbon containing 50 parts of ammonium polyoxyethylene alkyl ether sulfate, and 55 parts of water are mixed, and the mixture is then finely ground by a wet grinding method to obtain a formulation.
[000163] Next, test examples are used to show an effectiveness of the composition of the present invention in controlling plant diseases. The "Effectiveness" in each test means a value calculated by the following Equation 1, and it is classified depending on its numerical value shown in Table 5. "Equation 1" Effectiveness = 100 x (XY) / X where X: Degree of bacterial growth in untreated area Y: Degree of bacterial growth in treated area [Table 5]

Example Test 1: Control test against wheat leaf spot (Septoria tritici)
[000164] Each of the test compounds was diluted with dimethyl sulfoxide (DMSO) to the prescribed concentration, respectively, and each DMSO solution of the test compounds was dispensed on a title plate (with 96 wells) in the amount of 1 μL. This was subsequently dispensed with 150 μL of a potato dextrose broth in which wheat leaf rust fungus conidium was inoculated in advance. This plate was grown at 18 ° C for four days, thereby allowing wheat leaf rust fungus to proliferate, and the absorbance at 550 nm from each well of the title plate was then measured to determine a degree of growth of the fungus from the rust of wheat leaf. Efficacy 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 the following Table 6 to Table 16. [Table 6]

[Table 7]

[Table 8]
[Table 9]
[Table 10]
[Table 11]
[Table 12]
[Table 13]
[Table 14]
[Table 15]
[Table 16]
Industrial Applicability
[000165] The present invention can control plant diseases.

权利要求:
Claims (5)
[0001]
1. Composition for the control of plant diseases, characterized by the fact that it comprises a tetrazolinone compound represented by the formula (1):
[0002]
2. Plant disease control composition according to claim 1, characterized by the fact that the weight ratio of the tetrazolinone compound to the azole compound is that of the tetrazolinone compound / the azole compound = 0, 1/1 to 10/1.
[0003]
3. Method for the control of plant diseases, characterized by the fact that it comprises applying each effective amount of a tetrazolinone compound represented by formula (1):
[0004]
4. Method for the control of plant diseases according to claim 3, characterized by the fact that the weight ratio of the tetrazolinone compound to the azole compound is that of the tetrazolinone compound / the azole compound = 0, 1/1 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 the 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| Technical examination (opinion): publication of 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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2021-03-09| B16A| Patent or certificate of addition of invention granted|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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JP2013151418|2013-07-22|

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JP2013-151418|2013-07-22|

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PCT/JP2014/069267|WO2015012244A1|2013-07-22|2014-07-15|Plant disease control composition and application for same|

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