WO2015050039A1 - Composition de lutte contre les maladies de plante et son utilisation - Google Patents

Composition de lutte contre les maladies de plante et son utilisation Download PDF

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WO2015050039A1
WO2015050039A1 PCT/JP2014/075543 JP2014075543W WO2015050039A1 WO 2015050039 A1 WO2015050039 A1 WO 2015050039A1 JP 2014075543 W JP2014075543 W JP 2014075543W WO 2015050039 A1 WO2015050039 A1 WO 2015050039A1
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compound
methyl
reaction
alkyl group
group
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PCT/JP2014/075543
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Japanese (ja)
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雄一 松崎
真 倉橋
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住友化学株式会社
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms

Definitions

  • the present invention relates to a plant disease control composition and its use.
  • Patent Documents 1 and 2 Conventionally, many compounds have been developed and put into practical use for controlling plant diseases (see, for example, Patent Documents 1 and 2).
  • An object of the present invention is to provide a composition having an excellent control effect against plant diseases.
  • R 1 represents a C1-C3 alkyl group which may have one or more halogen atoms or a halogen atom
  • R 2 represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group
  • R 3 represents a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a cyclopropyl group, or a C1-C3 alkoxy group optionally having one or more halogen atoms
  • Z 1 represents a C1-C3 alkyl group
  • Z 2 represents a hydrogen atom, a C1-C2 alkoxy group, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C2 alkylthio group, or a cyano group
  • Z 3 represents a hydrogen atom, a C1-C3 alkyl group which may have one or
  • R 1 represents a C1-C3 alkyl group which may have one or more halogen atoms or a halogen atom
  • R 2 represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group
  • R 3 represents a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a cyclopropyl group, or a C1-C3 alkoxy group optionally having one or more halogen atoms
  • Z 1 represents a C1-C3 alkyl group
  • Z 2 represents a hydrogen atom, a C1-C2 alkoxy group, a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom, a C1-C2 alkylthio group, or a cyano group
  • Z 3 represents a hydrogen atom, a C1-C3 alkyl group or a
  • the plant disease control method including the process of processing the effective amount of the tetrazolinone compound shown by 1 and the 1 or more types of QoI compound chosen from a group (A) to the soil which grows a plant or a plant.
  • the plant disease control composition of the present invention (hereinafter referred to as the present composition) is represented by the formula (1). [Wherein R 1 , R 2 , R 3 , Z 1 , Z 2 and Z 3 represent the same meaning as described above. ] And one or more QoI compounds selected from the group (A) (hereinafter referred to as the present QoI compound).
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the C1-C3 alkyl group represents a linear or branched alkyl group having 1-3 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • the C1-C3 alkyl group optionally having one or more halogen atoms represents a C1-C3 alkyl group in which one or more hydrogen atoms may be substituted with a halogen atom, such as a methyl group or an ethyl group , Propyl, isopropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, dibromomethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl Group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3-fluoropropyl group, 2,2-difluoropropyl group, 3,3, 3-trifluoropropyl group, heptafluoropropyl group, heptafluoroisopropyl
  • the C1-C3 alkoxy group represents a linear or branched alkoxy group having 1 to 3 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
  • the C1-C3 alkoxy group which may have one or more halogen atoms represents a C1-C3 alkoxy group in which one or more hydrogen atoms may be substituted with a halogen atom, such as a methoxy group, an ethoxy group, Propoxy group, isopropoxy group, fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, chloromethoxy group, dichloromethoxy group, trichloromethoxy group, dibromomethoxy group, chlorofluoromethoxy group, dichlorofluoromethoxy group, chlorodifluoromethoxy group 2-fluoroethoxy group, 2,2-difluoroethoxy group, 2,2,2-tri
  • Examples of the C1-C2 alkoxy group include a methoxy group and an ethoxy group.
  • Examples of the C1-C2 alkylthio group include a methylthio group and an ethylthio group.
  • the tetrazolinone compound can be synthesized, for example, by the following synthesis method.
  • the tetrazolinone compound comprises a compound represented by formula (A1) (hereinafter referred to as compound (A1)) and a compound represented by formula (A2) (hereinafter referred to as compound (A2)) in the presence of a base. It can manufacture by making it react.
  • A1 compound represented by formula (A1)
  • A2 compound represented by formula (A2)
  • R 1 , R 2 , R 3 , Z 1 , Z 2 and Z 3 represent the same meaning as described above, and Z 11 represents a leaving group such as a chlorine atom, a bromine atom or an iodine atom.
  • the reaction is usually performed in a solvent.
  • Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichlor
  • Examples of the base used in the reaction include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclononene and the like.
  • Alkali metal carbonates such as organic bases, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium hydroxide, hydroxide
  • Alkali metal hydroxides such as sodium, potassium hydroxide and cesium hydroxide
  • alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride
  • alkali metals such as lithium hydride, sodium hydride and potassium hydride Hydrogenation , Sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
  • the compound (A2) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 10 mol.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • sodium iodide, tetrabutylammonium iodide or the like may be added as necessary, and these compounds are usually in a ratio of 0.001 to 1.2 mol with respect to 1 mol of the compound (A1).
  • the tetrazolinone compound Used in After completion of the reaction, the tetrazolinone compound can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Alternatively, the tetrazolinone compound can be isolated by performing post-treatment operations such as filtration and concentration of the reaction mixture. The isolated tetrazolinone compound can be further purified by chromatography, recrystallization or the like.
  • the present tetrazolinone compound represented by the formula (1-B) in which Z 3 is R 100 (hereinafter referred to as the compound (1-B)) is represented by the formula (1-2). It can be produced by reacting a tetrazolinone compound (hereinafter referred to as compound (1-2)) with a halogenating agent.
  • a tetrazolinone compound hereinafter referred to as compound (1-2)
  • R 1 , R 2 , R 3 , Z 1 and Z 2 represent the same meaning as described above, and R 100 represents a halogen atom.
  • the reaction is usually performed in a solvent.
  • Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, nitriles such as acetonitrile and propionitrile, And mixtures thereof.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1
  • halogenating agent used in the reaction examples include N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, chlorine, bromine, iodine, and sulfuryl chloride.
  • the halogenating agent is usually used at a ratio of 1 to 10 mol per 1 mol of the compound (1-2).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (1-B) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated tetrazolinone compound can be further purified by chromatography, recrystallization or the like.
  • solvent used in the reaction examples include ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisole, methyl tert-butyl ether, diisopropyl ether, n-heptane, n -Hydrocarbons such as hexane, cyclohexane, n-pentane, toluene, xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, acetonitrile, propionitrile, etc.
  • ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisole, methyl tert-butyl ether, diiso
  • acid amides such as N-methylpyrrolidone
  • sulfoxides such as dimethyl sulfoxide
  • methanol, ethanol, propano Le alcohols and mixtures thereof, such as butanol.
  • cyanating agent used in the reaction include phosphorus oxychloride, phosphorus pentachloride, and phosphorus oxybromide.
  • a base may be used.
  • the base used examples include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicyclone. And organic bases such as decene and diazabicyclononene. These bases can also be used as a solvent.
  • the cyanating agent is usually used at a ratio of 1 to 20 moles and the base is usually used at a ratio of 1 to a large excess mole.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 72 hours.
  • the compound (1-C) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the compound (1-C) can be isolated by filtering the precipitate. Further, it may be purified by operations such as chromatography and recrystallization.
  • a compound represented by formula (11) (hereinafter referred to as compound (11)) is obtained by reacting a compound represented by formula (10) (hereinafter referred to as compound (10)) with an azidating agent. Can be synthesized. [Wherein R 3 represents the same meaning as described above. ]
  • the reaction is usually performed in a solvent.
  • the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, acetonitrile, nitriles and mixtures thereof, such as propionitrile and the like.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-d
  • the azidating agent used in the reaction examples include inorganic azides such as sodium azide, barium azide and lithium azide, and organic azides such as trimethylsilyl azide and diphenylphosphoryl azide.
  • the azidating agent is usually used at a ratio of 1 to 10 moles relative to 1 mole of the compound (10).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • a Lewis acid such as aluminum chloride or zinc chloride may be added as necessary, and these compounds are usually used at a ratio of 0.05 to 5 mol with respect to 1 mol of compound (10). It is done.
  • the compound (11) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (11) can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (13) (hereinafter referred to as the compound (13)) is obtained by mixing the compound (11) and the compound represented by the formula (12) (hereinafter referred to as the compound (12)) with the presence of a base. It can synthesize
  • R 3 represents the same meaning as described above, and Z 5 represents a leaving group such as a bromine atom, an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, and a p-toluenesulfonyloxy group.
  • the reaction is usually performed in a solvent.
  • Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichlor
  • alkyl halides such as methyl bromide and methyl iodide
  • dialkyl sulfates such as dimethyl sulfate
  • alkyl sulfates such as methyl p-toluenesulfonate and methyl methanesulfonate
  • aryl sulfates Can be mentioned.
  • Examples of the base used in the reaction include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclononene and the like.
  • Alkali metal carbonates such as organic bases, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium hydroxide, hydroxide
  • Alkali metal hydroxides such as sodium, potassium hydroxide and cesium hydroxide
  • alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride
  • alkali metals such as lithium hydride, sodium hydride and potassium hydride Hydrogenation , Lithium hydride, sodium hydride, an alkali metal hydride such as potassium hydride, sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
  • the compound (12) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 0.5 to 10 mol.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (13) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (13) can be further purified by chromatography, recrystallization and the like.
  • Compound (A1) can be synthesized by reacting compound (13) with a halogenating agent. [Wherein R 3 and Z 11 represent the same meaning as described above. ] The reaction is usually performed in a solvent.
  • the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • ethers such as methyl tert-butyl ether, diisopropyl ether, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, fluorobenzene, difluorobenzene, trifluorobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene , ⁇ , ⁇ , ⁇ -trifluorotoluene, halogenated hydrocarbons such as ⁇ , ⁇ , ⁇ -trichlorotoluene, esters such as ethyl acetate and methyl acetate, acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone, acetonitrile, nitriles and mixtures thereof, such as propionitrile and the like.
  • ethers such as methyl tert-butyl ether
  • halogenating agent examples include a chlorinating agent, a brominating agent, or an iodinating agent such as chlorine, bromine, iodine, sulfuryl chloride, N-chlorosuccinimide, N-bromosuccinimide, 1,3-dibromo. -5,5-dimethylhydantoin, iodosuccinimide, tert-butyl hypochlorite, N-chloroglutarimide, N-bromoglutarimide, N-chloro-N-cyclohexyl-benzenesulfonimide, N-bromophthalimide .
  • a radical initiator can also be used for this reaction.
  • the radical initiator used in the reaction examples include benzoyl peroxide, azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile and the like.
  • the halogenating agent is usually used in a proportion of 1 to 10 mol and the radical initiator is usually used in a proportion of 0.01 to 1 mol with respect to 1 mol of the compound (13).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (A1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (A1C) can be further purified by chromatography, recrystallization, and the like.
  • a compound represented by formula (15) is a compound represented by formula (A1-D) in which R 6 is Z 6 (hereinafter referred to as compound (15)).
  • A1-D)) and a compound represented by formula (14) (hereinafter referred to as compound (14)) can be produced.
  • Z 11 and Z 6 represent the same meaning as described above, R 4 represents a C1-C12 alkyl group or a phenyl group, and M represents sodium, potassium, or lithium.
  • the reaction is usually performed in a solvent.
  • solvent used in the reaction examples include ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisole, methyl tert-butyl ether, diisopropyl ether, n-heptane, n -Hydrocarbons such as hexane, cyclohexane, n-pentane, toluene, xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, acetonitrile, propionitrile, etc.
  • ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisole, methyl tert-butyl ether, diiso
  • Nitriles N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, Ketones such as Louis Seo ketone, methanol, ethanol, propanol, and mixtures thereof, such as butanol.
  • compound (14) sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium isopropoxide, sodium sec-butoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium Examples include butoxide, potassium isopropoxide, potassium sec-butoxide, potassium tert-butoxide, sodium phenoxide and the like.
  • compound (14) is usually used at a ratio of 1 to 10 mol with respect to 1 mol of compound (A1-D).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (15) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, purification may be performed by operations such as distillation, chromatography, recrystallization and the like.
  • the compound represented by formula (16) (hereinafter referred to as compound (16)) can be synthesized by coupling reaction of compound (15) and compound (7) in the presence of a base and a catalyst.
  • R 4 and Z 6 represent the same meaning as described above, R 3A represents a C1-C3 alkyl group or a cyclopropyl group, and Z 7 represents B (OH) 2 , an alkoxyboryl group, or a trifluoroborate salt. It represents a - (BF 3 K +).
  • the reaction is usually performed in a solvent.
  • Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, methanol, ethanol, propanol, alcohols such as butanol, water and mixtures thereof.
  • halogenated hydrocarbons such as carbon t
  • organic boron compound (7) used in the reaction a commercially available one is usually used, or N.I. Miyaura and A.M. Suzuki, Chem. Rev. , 1995, 95, 2457, etc., and those synthesized by known methods can also be used.
  • Organoboron compounds used in the reaction (7) for example, after the reaction of alkyl lithium such as butyl lithium and iodine compound of R 3A (R 3A -I) or bromo compound (R 3A -Br), boric Boronate ester derivatives can be synthesized by reacting with an acid ester. Further, a boronic acid derivative can be synthesized by hydrolyzing the boronic acid ester derivative obtained by the above-described reaction as necessary.
  • Catalysts used in the reaction include palladium (II) acetate, dichlorobis (triphenylphosphine) palladium, tetrakistriphenylphosphinepalladium (0), palladium (II) acetate / triscyclohexylphosphine, bis (diphenylphosphaneferrocenyl) ) Palladium (II) dichloride, 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene (1,4-naphthoquinone) palladium dimer, allyl (chloro) (1,3-dimesityl-1,3- Dihydro-2H-imidazol-2-ylidene) palladium or palladium (II) acetate / dicyclohexyl (2 ′, 4 ′, 6′-triisopropylbiphenyl-2-yl) phos
  • Examples of the base used in the reaction include organic bases such as triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene and diazabicyclononene.
  • organic bases such as triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene and diazabicyclononene.
  • Alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, etc., lithium hydroxide, sodium hydroxide, Alkali metal hydroxides such as potassium hydroxide and cesium hydroxide, alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride, alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride ,Rin Alkali metal phosphates such as tripotassium, sodium methoxide, sodium ethoxide, sodium tert- butoxide, alkali metal alkoxides such as potassium tert- butoxide.
  • the compound (7) is usually used in a proportion of 1 to 10 mol
  • the base is usually in a proportion of 1 to 10 mol
  • the catalyst is usually used in a proportion of 0.0001 to 1 mol. It is done.
  • the reaction temperature is usually in the range of 0 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (16) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. The isolated compound (16) can be further purified by chromatography, recrystallization and the like.
  • a compound represented by the formula (A1-F) (hereinafter referred to as compound (A1-F)) can be produced by reacting compound (16) with a halogenating agent.
  • a halogenating agent e.g., a halogenating agent for reacting compound (16) with a halogenating agent.
  • R 3A , R 4 and Z 6 represent the same meaning as described above.
  • the reaction is usually performed in a solvent.
  • the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane.
  • Halogenated hydrocarbons such as chlorobenzene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, organic acids such as formic acid, acetic acid and trifluoroacetic acid, water and mixtures thereof.
  • Examples of the halogenating agent used in the reaction include hydrochloric acid, hydrobromic acid, and hydriodic acid.
  • the halogenating agent is usually used at a ratio of 1 mol or more per 1 mol of the compound (16).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (A1-F) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, purification may be performed by operations such as distillation, chromatography, recrystallization and the like.
  • Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichlor
  • Examples of the base used in the reaction include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclononene and the like.
  • Alkali metal carbonates such as organic bases, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium hydroxide, hydroxide
  • Alkali metal hydroxides such as sodium, potassium hydroxide and cesium hydroxide
  • alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride
  • alkali metals such as lithium hydride, sodium hydride and potassium hydride Hydrogenation , Sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
  • the compound (XG1) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 10 mol.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • sodium iodide, tetrabutylammonium iodide or the like may be added as necessary, and these compounds are usually in a ratio of 0.001 to 1.2 mol with respect to 1 mol of the compound (A1).
  • the compound (XG2) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • compound (XG2) can be isolated by performing post-treatment operations such as filtration and concentration of the reaction mixture. Further, it can be purified by chromatography, recrystallization or the like.
  • Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichlor
  • Examples of the base used in the reaction include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclononene and the like.
  • Alkali metal carbonates such as organic bases, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium hydroxide, hydroxide
  • Alkali metal hydroxides such as sodium, potassium hydroxide and cesium hydroxide
  • alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride
  • alkali metals such as lithium hydride, sodium hydride and potassium hydride Hydrogenation , Sodium methoxide, sodium ethoxide, sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
  • the compound (XH1) is usually used at a ratio of 1 to 10 moles, and the base is usually used at a ratio of 1 to 10 moles.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • additives may be added as necessary, and examples of the additive include 18-crown-6 and dibenzo-18-crown-6. These additives are usually used in a proportion of 0.001 to 1.2 mol with respect to 1 mol of compound (XG2).
  • the compound (XH2) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, it can be purified by chromatography, recrystallization or the like.
  • a compound represented by the formula (XI1) (hereinafter referred to as compound (XI1)) can be produced by reacting compound (XH2) with hydrazines. [Wherein R 1 , R 2 , R 3 , R 92 and Z 3 represent the same meaning as described above. ] The reaction is usually performed in a solvent.
  • solvent used in the reaction examples include ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisole, methyl tert-butyl ether, diisopropyl ether, n-heptane, n -Hydrocarbons such as hexane, cyclohexane, n-pentane, toluene, xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, acetonitrile, propionitrile, etc.
  • ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisole, methyl tert-butyl ether, diiso
  • hydrazines used in the reaction include hydrazine monohydrate, hydrazine hydrochloride, hydrazine sulfate, and anhydrous hydrazine. In the reaction, hydrazines are usually used at a ratio of 1 to 100 mol with respect to 1 mol of compound (XH2).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (XI1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, it may be purified by operations such as chromatography and recrystallization.
  • Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichlor
  • a commercially available product can be used as the compound (XJ1) used in the reaction.
  • a commercially available product can be used.
  • a base may be used. Examples of the base used include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicyclone.
  • Organic bases such as decene and diazabicyclononene, alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and cesium hydrogen carbonate Salts, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, alkali metal halides such as sodium fluoride, potassium fluoride, cesium fluoride, lithium hydride, sodium hydride , Potassium hydride Alkali metal hydrides, lithium hydride, sodium hydride, an alkali metal hydride such as potassium hydride, sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
  • alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate
  • alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium
  • compound (XJ1) is usually used in a proportion of 1 to 10 mol
  • base is usually used in a proportion of 1 to 10 mol
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (XJ2) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound of the present invention can be further purified by chromatography, recrystallization and the like.
  • a compound represented by the formula (XK1) (hereinafter referred to as compound (XK1)) can be produced by reacting compound (XJ2) with a hydrolyzing agent.
  • a hydrolyzing agent e.g., water, alcohols such as methanol, ethanol, propanol, and butanol, hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, and diethyl ether.
  • the hydrolyzing agent used in the reaction examples include bases such as aqueous potassium hydroxide, sodium hydroxide and aqueous solutions, and acids such as hydrochloric acid and sulfuric acid.
  • the hydrolyzing agent is usually used at a ratio of 0.5 to 20 mol with respect to 1 mol of the compound (XJ2).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 72 hours.
  • the compound (XK1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (XK1) can be further purified by operations such as chromatography and recrystallization.
  • a compound represented by the formula (XL1) (hereinafter referred to as compound (XL1)) can be produced by reacting compound (XK1) with a halogenating agent.
  • a halogenating agent e.g., a halogenating agent for reacting compound (XK1) with a halogenating agent.
  • R 1 , R 2 , R 3 , R 100 , Z 1 and Z 3 represent the same meaning as described above.
  • the reaction is usually performed in a solvent.
  • the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether and diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane and chlorobenzene, esters such as ethyl acetate and methyl acetate , Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, and mixtures thereof.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane and chlorobenzene
  • esters such as ethyl acetate and methyl acetate
  • Ketones such as acetone, methyl eth
  • halogenating agent used in the reaction examples include phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus oxybromide, phosphorus tribromide, phosphorus pentabromide, phosphorus triiodide, and dichloride.
  • the halogenating agent is usually used at a ratio of 1 to 10 mol per 1 mol of the compound (XK1).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • a catalyst may be added, and N, N-dimethylformamide, triethylamine, diisopropylethylamine or the like is used, and the catalyst is used in a ratio of 0.001 to 1 mol with respect to 1 mol of compound (XK1).
  • the compound (XL1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the isolated compound (XL1) may be further purified by operations such as chromatography and recrystallization.
  • Compound (C1) can be produced by reacting compound (XL1) with an amidating agent.
  • R 1 , R 2 , R 3 , R 100 , Z 1 and Z 3 represent the same meaning as described above.
  • the solvent used in the reaction include ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, anisole, methyl tert-butyl ether, diisopropyl ether, n-heptane, n -Hydrocarbons such as hexane, cyclohexane, n-pentane, toluene, xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, acetonitrile, pro
  • the amidating agent used in the reaction include an aqueous ammonia solution, ammonia hydrochloride, ammonia sulfate, and ammonia gas.
  • An amidating agent can also be used as a solvent.
  • an amidating agent is usually used in a proportion of 1 mol to large excess with respect to 1 mol of compound (XL1).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 72 hours.
  • the compound (C1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the compound (C1) can be isolated by filtering the precipitate. Further, it may be purified by operations such as chromatography and recrystallization.
  • Compound (A2) can be produced by reacting a compound represented by the formula (YA1) (hereinafter referred to as compound (YA1)) with an acid.
  • YA1 a compound represented by the formula (YA1)
  • R 1 , R 2 , R 92 , Z 1 , Z 2 and Z 3 represent the same meaning as described above.
  • the reaction is usually performed in a solvent.
  • the solvent used in the reaction include alcohols such as methanol, ethanol, propanol, and butanol, water, acetic acid, and mixtures thereof.
  • the acid used in the reaction include acetic acid, hydrochloric acid, and hydrobromic acid, and these aqueous solutions can also be used as a solvent.
  • the reaction an acid is usually used in a large excess amount relative to 1 mol of the compound (YA1).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 100 hours.
  • the compound (A2) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the compound (A2) can be isolated by performing post-treatment operations such as concentration of the reaction mixture. Further, it can be purified by chromatography, recrystallization or the like.
  • Compound (YA1) can be produced by reacting a compound represented by formula (YB1) (hereinafter referred to as compound (YB1)) with compound (XJ1) in the presence of a base. [Wherein R 1 , R 2 , R 92 , Z 1 , Z 2 , Z 3 and Z 5 represent the same meaning as described above. ] This reaction can be carried out according to Reference Synthesis Method J.
  • a compound represented by formula (YC3) (hereinafter referred to as compound (YC3)) is a compound represented by formula (YC1) (hereinafter referred to as compound (YC1)) and a compound represented by formula (YC2) ( Hereinafter, it can be produced by reacting compound (YC2)) in the presence of a base.
  • YC3 a compound represented by formula (YC1)
  • YC2 a compound represented by formula (YC2)
  • R 1 , R 2 and Z 3 represent the same meaning as described above.
  • the reaction is usually performed in a solvent.
  • Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 Acid amides such as 1,3-dimethyl-2-imidazolidinone and N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, and nitriles such as acetonitrile and propionitrile. Beauty mixtures thereof.
  • Examples of the base used in the reaction include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclononene and the like.
  • Alkali metal carbonates such as organic bases, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium hydroxide, hydroxide
  • Alkali metal hydroxides such as sodium, potassium hydroxide and cesium hydroxide
  • alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride
  • alkali metals such as lithium hydride, sodium hydride and potassium hydride Hydrogenation , Sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
  • the compound (YC2) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 10 mol.
  • the reaction temperature of the reaction is usually in the range of ⁇ 78 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 72 hours.
  • the compound (YC3) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, it can be purified by chromatography, recrystallization or the like.
  • Compound (XG1) can be produced by reacting compound (YC3) in the presence of an acid.
  • R 1 , R 2 and Z 3 represent the same meaning as described above.
  • the reaction is usually performed in a solvent.
  • the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, nitromethane, acetonitrile, propionitrile, etc. Nitriles, and mixtures thereof.
  • the acid used in the reaction include aluminum trichloride, titanium tetrachloride, iron trichloride, hydrogen fluoride, hypochlorous acid, polyphosphoric acid, and the like.
  • an acid is usually used at a ratio of 1 to 10 mol per 1 mol of the compound (YC3).
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 72 hours.
  • the compound (XG1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, it can be purified by chromatography, recrystallization or the like.
  • a compound represented by formula (YE3) (hereinafter referred to as compound (YE3)) is a compound represented by formula (YE1) (hereinafter referred to as compound (YE1)) and a compound represented by formula (YE2). (Hereinafter referred to as compound (YE2)) in the presence of a base.
  • YE3 a compound represented by formula (YE1)
  • YE2 a compound represented by formula (YE2)
  • R 1 , R 2 , R 92 and Z 3 represent the same meaning as described above.
  • the reaction is usually performed in a solvent.
  • Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichlor
  • Examples of the base used in the reaction include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclononene and the like.
  • Alkali metal carbonates such as organic bases, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium hydroxide, hydroxide
  • Alkali metal hydroxides such as sodium, potassium hydroxide and cesium hydroxide
  • alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride
  • alkali metals such as lithium hydride, sodium hydride and potassium hydride Hydrogenation , Sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
  • the compound (YE2) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 10 mol.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • an additive may be added as necessary, and examples of the additive include 18-crown-6-ether and dibenzo-18-crown-6-ether. These additives are usually used in a proportion of 0.001 to 1.2 mol with respect to 1 mol of the compound (YE1).
  • the compound (YE3) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, it can be purified by chromatography, recrystallization or the like.
  • Compound (YB1) can be produced by reacting compound (YF2) with hydrazines. [Wherein R 1 , R 2 , R 92 , Z 2 and Z 3 represent the same meaning as described above. ] This reaction can be carried out according to Reference Synthesis Method I.
  • a compound represented by formula (YH3) (hereinafter referred to as compound (YH3)) is a compound represented by formula (YH1) (hereinafter referred to as compound (YH1)) and a compound represented by formula (YH2) ( Hereinafter, it can be produced by reacting with compound (YH2).
  • R 1 , R 2 , R 3 , R 92 , R 100 and Z 3 represent the same meaning as described above, Rf represents a C1-C3 perfluoroalkyl group, and n represents 0 or 1.
  • the reaction is usually carried out in a solvent.
  • Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, nitriles such as acetonitrile and propionitrile, Methanol, ethanol, alcohols such as isopropanol, water and mixtures thereof.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane
  • compound (YH2) is usually used at a ratio of 1 to 10 mol per 1 mol of compound (YH1).
  • the reaction temperature of the reaction is usually in the range of ⁇ 78 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 72 hours.
  • the compound (YH3) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, it can be purified by chromatography, recrystallization or the like.
  • a compound represented by the formula (YI1) (hereinafter referred to as compound (YI1)) can be produced by reacting compound (YH3) in the presence of an acid.
  • R 1 , R 2 , R 92 , Z 3 and Rf represent the same meaning as described above.
  • the reaction is usually performed in a solvent.
  • the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, nitriles such as acetonitrile and propionitrile, Methanol, ethanol, alcohols such as isopropanol, water and mixtures thereof.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane
  • Examples of the acid used in the reaction include acetic acid, hydrochloric acid, hydrobromic acid and the like, and these aqueous solutions can also be used as a solvent.
  • an acid is usually used at a ratio of 1 to 10 mol with respect to 1 mol of the compound (YH3).
  • the reaction temperature of the reaction is usually in the range of ⁇ 78 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 72 hours.
  • the compound (YI1) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer. Further, it can be purified by chromatography, recrystallization or the like.
  • the compound represented by the formula (YJ1) (hereinafter referred to as the compound (YJ1)) can be produced by reacting the compound (YE3) with the compound (YH2). [Wherein, n, R 1 , R 2 , R 92 , R 100 and Z 3 represent the same meaning as described above. ] The reaction is performed in a solvent or without a solvent.
  • Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, nitriles such as acetonitrile and propionitrile, And mixtures thereof.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1
  • An acid may be added to the reaction if necessary.
  • the acid used in the reaction include hydrochloric acid, sulfuric acid, acetic acid, hydrobromic acid, p-toluenesulfonic acid and the like.
  • the compound (YE3) is usually used in a proportion of 1 to 100 mol
  • the acid is usually used in a proportion of 1 to 100 mol.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture is concentrated under reduced pressure, extracted with an organic solvent, and the organic layer is dried, concentrated, filtered and post-treatment operations such as filtration can be performed to isolate the compound (YJ1).
  • the isolated compound of the present invention can be further purified by chromatography, recrystallization and the like.
  • the compound represented by the formula (YK1) (hereinafter referred to as the compound (YK1)) is the same as the compound represented by the formula (YJ1K) (hereinafter referred to as the compound (YJ1K)) and N, N-dimethylformamide and oxy. It can be produced by reacting with a formylating agent prepared from phosphorus chloride and then reacting with water. [Wherein, R 1 , R 2 and R 92 represent the same meaning as described above. ] The reaction is usually performed in a solvent.
  • solvent used in the reaction examples include hydrocarbons such as n-heptane, n-hexane, cyclohexane and n-pentane, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, methyl tert.
  • -Ethers such as butyl ether and diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1,3-dimethyl-2 Acid amides such as imidazolidinone and N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, acetonitrile Nitriles such as propionitrile and mixtures thereof.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenz
  • the formylating agent in the reaction is a mixture of 1 to 10 mol of N, N-dimethylformamide and 1 to 10 mol of phosphorus oxychloride with respect to 1 mol of compound (YJ1K), and water is compound (YJ1K). ) It is used at a ratio of 1 to 10 moles per mole.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (YK1) may be isolated by performing post-treatment operations such as adding usually 1 mol or more of water, extracting the reaction mixture with an organic solvent, and drying and concentrating the organic layer. it can.
  • the isolated compound of the present invention can be further purified by chromatography, recrystallization and the like.
  • Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichlor
  • Examples of the base used in the reaction include triethylamine, pyridine, N-methylmorpholine, N-methylpiperidine, 4-dimethylaminopyridine, diisopropylethylamine, lutidine, collidine, diazabicycloundecene, diazabicyclononene and the like.
  • Alkali metal carbonates such as organic bases, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium hydroxide, hydroxide
  • Alkali metal hydroxides such as sodium, potassium hydroxide and cesium hydroxide
  • alkali metal halides such as sodium fluoride, potassium fluoride and cesium fluoride
  • alkali metals such as lithium hydride, sodium hydride and potassium hydride Hydrogenation , Sodium tert- butoxide, and alkali metal alkoxides such as potassium tert- butoxide.
  • the compound (YL1) is usually used in a proportion of 1 to 10 mol, and the base is usually used in a proportion of 1 to 10 mol.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction is carried out by reacting the compound (YL1) with an alkali metal carbonate, alkali metal hydrogencarbonate, alkali metal hydroxide, alkali metal halide, alkali metal hydride or alkali metal alkoxide.
  • a salt can be prepared in advance and used in the reaction.
  • the metal salt of the compound (YL1) examples include sodium methoxide, sodium ethoxide, sodium propoxide, sodium isopropoxide, potassium methoxide, potassium ethoxide, sodium thiomethoxide, sodium thioethoxide. Is mentioned.
  • the metal salt of compound (YL1) is usually used at a ratio of 1 to 10 mol per 1 mol of compound (YK1).
  • the compound (YL2) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • the compound (YL2) can be isolated by performing post-treatment operations such as filtration and concentration of the reaction mixture. Further, it can be purified by chromatography, recrystallization or the like.
  • Examples of the solvent used in the reaction include hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • hydrocarbons such as n-heptane, n-hexane, cyclohexane, n-pentane, toluene, xylene, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether.
  • Ethers such as ter, anisole, methyl tert-butyl ether, diisopropyl ether, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, tetrachloroethane, chlorobenzene, N, N-dimethylformamide, 1 , 3-dimethyl-2-imidazolidinone, acid amides such as N-methylpyrrolidone, esters such as ethyl acetate and methyl acetate, sulfoxides such as dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketones such as down, nitriles such as acetonitrile and propionitrile, water and mixtures thereof.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichlor
  • Examples of the reducing agent used in the reaction include metal boronate compounds such as lithium borohydride, sodium borohydride and potassium borohydride, and trialkylsilane compounds such as triethylsilane.
  • Examples of the acid used in the reaction include boron trifluoride and trifluoroacetic acid.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 150 ° C.
  • the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound (YI2) can be isolated by performing post-treatment operations such as extraction of the reaction mixture with an organic solvent, and drying and concentration of the organic layer.
  • compound (YI2) can be isolated by performing post-treatment operations such as filtration and concentration of the reaction mixture. Further, it can be purified by chromatography, recrystallization or the like.
  • This QoI compound is a known compound, and is described, for example, in “THE PESTICIDE MANUAL-14th EDITION (BCPC) ISBN 190139396142”. These compounds can be obtained from commercial preparations or synthesized by known methods. Hereinafter, this QoI compound is shown in [Table 1].
  • the composition of the present invention may be a mixture of the tetrazolinone compound and the QoI compound itself, but the composition of the present invention is usually mixed with the tetrazolinone compound, the QoI compound and an inert carrier, and if necessary, surface active. And other preparation adjuvants.
  • the composition of the present invention may be formulated into oils, emulsions, flowables, wettable powders, granular wettable powders, powders, granules and the like. Such a preparation can be used as a plant disease control agent as it is or with addition of other inactive ingredients.
  • the present composition contains the present tetrazolinone compound and the present QoI compound in a total amount of usually 0.1 to 99% by weight, preferably 0.2 to 90% by weight, more preferably 1 to 80% by weight.
  • Examples of the solid carrier used in the formulation include clays (for example, kaolin, diatomaceous earth, synthetic hydrous silicon oxide, fubasamic clay, bentonite, acidic clay), talc, and other inorganic minerals (for example, sericite, Examples thereof include fine powders or granular materials such as quartz powder, sulfur powder, activated carbon, calcium carbonate, and hydrated silica).
  • Examples of the liquid carrier include water and alcohols (eg, methanol, ethanol).
  • Ketones for example, acetone, methyl ethyl ketone
  • aromatic hydrocarbons for example, benzene, toluene, xylene, ethylbenzene, methylnaphthalene
  • aliphatic hydrocarbons for example, n-hexane, cyclohexanone, kerosene
  • esters for example, ethyl acetate, butyl acetate
  • nitriles for example, acetonitrile, isobutyronitrate
  • d - ethers e.g., dioxane, diisopropyl d - ether
  • acid amides e.g., DMF, dimethylacetamide
  • halogenated hydrocarbons e.g., dichloroethane, trichlorethylene, carbon tetrachloride
  • surfactant examples include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylene compounds thereof, polyoxyethylene glycol ethers, polyvalent Examples include alcohol esters and sugar alcohol derivatives.
  • formulation adjuvants include, for example, fixing agents, dispersants, and stabilizers.
  • casein gelatin, polysaccharides (for example, starch, arabic gum, cellulose derivatives, alginic acid), lignin derivatives, Bentonite, sugars, synthetic water-soluble polymers (for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids), PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol) ), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, fatty acid or ester thereof, and the like.
  • polysaccharides for example, starch, arabic gum, cellulose derivatives, alginic acid
  • lignin derivatives Bentonite
  • sugars synthetic water-soluble polymers (for example, polyvinyl alcohol, polyvinyl pyrrol
  • composition of the present invention also contains a preparation containing the tetrazolinone compound and the QoI compound after the tetrazolinone compound and the QoI compound are formulated by the above-described methods, and diluted with water as necessary. It can also be prepared by mixing the preparations to be prepared or the dilutions thereof.
  • composition of the present invention can be used to protect plants from plant diseases.
  • the control method of the present invention comprises treating a plant disease by treating the composition of the present invention on a plant or soil on which the plant is cultivated, or treating the tetrazolinone compound and the QoI compound separately on the soil on which the plant or plant is cultivated.
  • the method of applying the composition of the present invention is not particularly limited as long as the composition of the present invention can be applied substantially, but for example, treatment of plants such as foliage spraying, plants such as soil treatment, etc. To seeds such as seed sterilization and so on.
  • the application amount of the composition of the present invention varies depending on weather conditions, formulation form, application time, application method, application location, target disease, target crop, etc., but is usually 1 to 500 g, preferably 2 to 200 g per 1000 m 2. is there.
  • Emulsions, wettable powders, suspensions and the like are usually diluted with water and applied.
  • the concentration of the composition of the present invention after dilution is usually 0.0005 to 2% by weight, preferably 0.005 to It is 1% by weight, and powders, granules and the like are usually applied as they are without dilution.
  • the amount of the composition of the present invention per 1 kg seed is usually applied in the range of 0.001 to 100 g, preferably 0.01 to 50 g.
  • habitats for plant diseases in the present invention include paddy fields, fields, tea gardens, orchards, non-agricultural lands, houses, seedling trays and seedling boxes, seedling culture soils and seedling mats.
  • composition of the present invention can be used as a plant disease control agent in agricultural land such as fields, paddy fields, lawns, orchards.
  • the composition of the present invention can control diseases of the cultivated land in cultivated lands where the following “plants” and the like are cultivated.
  • Agricultural crops corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybeans, peanuts, buckwheat, sugar beet, rapeseed, sunflower, sugarcane, tobacco, etc., vegetables; solanaceous vegetables (eggplants, tomatoes, peppers) , Pepper, potato, etc.), cucurbitaceae vegetables (cucumber, pumpkin, zucchini, watermelon, melon, etc.), cruciferous vegetables (radish, turnip, horseradish, cold rabi, Chinese cabbage, cabbage, mustard, broccoli, cauliflower -), Asteraceae vegetables (burdock, garlic, artichoke, lettuce, etc.), Liliaceae vegetables (leek, onion, garlic, asparagus), Aceraceae vegetables (carrots, parsley, celery, American redfish, etc.) , Red vegetables (spinach, chard, etc.), perilla vegetables (perilla, mint, basil) ), Strawberry, sweet potato, yam, taro, etc
  • Trees other than fruit trees tea, mulberry, flowering trees, street trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak, poplar, redwood, fu, sycamore, zelkova, black bean, peach tree, tsuga, rat, Pine, spruce, yew).
  • plants include genetically modified crops.
  • phytopathogenic fungi such as filamentous fungi, and the following can be mentioned in more detail, but are not limited thereto.
  • Rice diseases blast (Magnaporthe grisea), sesame leaf blight (Cochliobolus miyabeanus), blight (Rhizoctonia solani), idiotic seedling (Gibberella fujikuruoi).
  • Wheat diseases powdery mildew (Erysiphe graminis), red mold disease (Fusarium gramaminerum, F. avenacerum, F. culmorum, Microdochium nitrid, red rust (Puccinia isp.
  • Ustilago nuda Ustilago nuda
  • cloud disease Rhynchosporium secalis
  • reticular disease Pyrenophora teres
  • spot disease Cochliobolus sativus
  • leafy leaf disease Pyrenophora graminea
  • Rhizonia a Diseases of corn: smut (Ustilago maydis), sesame leaf blight (Cochliobolus heterostrohus), leprosy (Gloeocercospora sorgi), southern rust (Puccinia polysoria), gray leaf spot disease Rhizoctonia solani due to seedling.
  • pirina Black spot (Alternaria alternata Japan pearpathotype), Gimnosporangium haraeumto, disease Peach diseases: Monilinia fracticola, black scab (Cladosporium carpophilum), Phomopsis spoilage (Phomopsis sp.). Grape diseases: black scab (Elsinoe ampelina), late rot (Glomerella gingulata), powdery mildew (Uncinula adipelodia), black rot (Gikonivaladi) .
  • Oyster diseases Anthracnose (Gloeosporium kaki), deciduous leaf disease (Cercospora kaki, Mycosphaerella nawae). Diseases of cucurbits: Anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca furiginea), vine blight (Mycosphaerella meloniis), vine scab (Fusarium oxysporum), por disease (fusarium oxysporum) ), Seedling blight (Pythium sp.); Diseases of tomato: Alternaria solani, leaf mold (Cladosporium fulvum), plague (Phytophthora infestans).
  • Potato diseases Alternaria solani, Phytophthora infestans, Sputum rot septica, Spongosporia subteranean f.
  • Strawberry disease powdery mildew (Sphaerotheca humuli), anthracnose (Glomerella singulata).
  • Tea diseases net blast (Exobasidium reticulatum), white scab (Elsinoe leucospila), ring spot disease (Pestalotiosis sp.), Anthracnose (Colletotrichum theae-sinensis).
  • Tobacco disease Alternaria longipes, powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), epidemic (Phytophyti. Rapeseed diseases: Sclerotinia sclerotiorum, Rhizoctonia solani, and Rhizoctonia solani. Cotton disease; Rhizoctonia solani caused by Rhizoctonia spp. Diseases of sugar beet: brown spot disease (Cercospora beticola), leaf rot (Thanatephorus cucumeris), root rot (Thanatephorus cucumeris), black root disease (Aphanomyces cochlioides).
  • Rose diseases black spot (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa), downy mildew (Peronospora sparsa).
  • Diseases of chrysanthemum and asteraceae vegetables downy mildew (Bremia lactucae), brown spot disease (Septoria chrysanthemi-indici), white rust (Puccinia horiana).
  • Diseases of various crops Diseases caused by Pythium spp.
  • Aspergillus genus Penicillium genus, Fusarium genus, Gibberella genus, Tricoderder genus, Thielaviopsis genus, Rhizopus genus, Mucor genus, Corticium genus, Phoma genus, Rhizoctonia genus Disease. Viral diseases of various crops mediated by Polymixa genus or Olpidium genus.
  • Synthesis example 2 In Synthesis Example 1, 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 3 was used instead of 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one.
  • Synthesis example 3 In Synthesis Example 1, 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 10 was used instead of 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one.
  • Synthesis example 5 In Synthesis Example 1, 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 43 was used instead of 1- (2-bromomethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one.
  • Synthesis example 7 In Synthesis Example 1, instead of 4- (5-chloro-1,4-dimethyl-1H-pyrazol-3-yl) -2-methyl-phenol, 4- (1,4- The same reaction was carried out using dimethyl-5-methoxy-1H-pyrazol-3-yl) -2-methyl-phenol, and 1- ⁇ 3-methyl-2- [2-methyl-4- (1,4- Dimethyl-5-methoxy-1H-pyrazol-3-yl) -phenoxymethyl] -phenyl ⁇ -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 7) was obtained. .
  • Synthesis example 8 1- ⁇ 3-methyl-2- [2-methyl-4- (5-aminocarbonyl-1,4-dimethyl-1H-pyrazol-3-yl) -phenoxy described in Reference Synthesis Example 40 at 0 ° C. 0.26 g of phosphorus oxychloride was added to a mixture of 0.5 g of methyl] -phenyl ⁇ -4-methyl-1,4-dihydrotetrazol-5-one and 10 ml of pyridine. After stirring at room temperature for 3 hours, 30 ml of water was added.
  • the precipitate was collected by filtration, washed with 10 ml of water and 10 ml of hexane, dried under reduced pressure, and 1- ⁇ 3-methyl-2- [2-methyl-4- (5-cyano-1,4-dimethyl-1H-pyrazole). -3-yl) -phenoxymethyl] -phenyl ⁇ -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 8) (0.38 g) was obtained.
  • Synthesis Example 9 In Synthesis Example 1, instead of 4- (5-chloro-1,4-dimethyl-1H-pyrazol-3-yl) -2-methyl-phenol, 4- (1,4,4) described in Reference Synthesis Example 46 was used. The same reaction was carried out using 5-trimethyl-1H-pyrazol-3-yl) -2-methyl-phenol, and 1- ⁇ 3-methyl-2- [2-methyl-4- (1,4,5- Trimethyl-1H-pyrazol-3-yl) -phenoxymethyl] -phenyl ⁇ -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 9) was obtained.
  • Synthesis Example 10 In Synthesis Example 6, instead of 2-methyl-4- (1-methyl-5-trifluoromethyl-1H-pyrazol-3-yl) -phenol, 4- (1,4,4) described in Reference Synthesis Example 46 was used. The same reaction was carried out using 5-trimethyl-1H-pyrazol-3-yl) -2-methyl-phenol, and 1- ⁇ 3-ethyl-2- [2-methyl-4- (1,4,5- Trimethyl-1H-pyrazol-3-yl) -phenoxymethyl] -phenyl ⁇ -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 10) was obtained.
  • Synthesis Example 11 In Synthesis Example 5, instead of 4- (5-chloro-1,4-dimethyl-1H-pyrazol-3-yl) -2-methyl-phenol, 4- (1,4,4) described in Reference Synthesis Example 46 was used. A similar reaction is carried out using 5-trimethyl-1H-pyrazol-3-yl) -2-methyl-phenol, and 1- ⁇ 3-methoxy-2- [2-methyl-4- (1,4,5- Trimethyl-1H-pyrazol-3-yl) -phenoxymethyl] -phenyl ⁇ -4-methyl-1,4-dihydrotetrazol-5-one (hereinafter referred to as the present tetrazolinone compound 10) was obtained.
  • Reference synthesis example 1 21.9 g of anhydrous aluminum chloride was added to 250 mL of N, N-dimethylformamide under ice cooling, and the mixture was stirred for 15 minutes. To this was added 10.7 g of sodium azide and stirred for 15 minutes. Then, 25.0 g of 1-chloro-3-isocyanato-2-methylbenzene was added and heated at 80 ° C. for 5 hours. After cooling, the reaction solution was added to a mixture of 35 g of sodium nitrite, 2 L of water and 500 g of ice with stirring. The mixture was acidified with 10% hydrochloric acid and extracted with ethyl acetate.
  • Reference synthesis example 4 19.7 g of anhydrous aluminum chloride was added to 220 mL of N, N-dimethylformamide under ice cooling and stirred for 15 minutes. After adding 9.6 g of sodium azide and stirring for 15 minutes, 30.3 g of 1-bromo-3-isocyanato-2-methylbenzene described in Reference Synthesis Example 42 was added and heated at 80 ° C. for 5 hours. After cooling, the reaction solution was added to a mixture of 33 g of sodium nitrite, 2 L of water and 500 g of ice with stirring. The mixture was acidified with 10% hydrochloric acid and extracted with ethyl acetate.
  • Reference synthesis example 6 8.47 g of 1- (2-methyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 5, 1,1′-azobis (cyclohexane-1-carbohydrate (Nitrile) 1.54 g, N-bromosuccinimide 6.44 g and chlorobenzene 125 mL were stirred with heating under reflux for 5 hours. After cooling, water was poured into the reaction solution and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • Reference synthesis example 7 A mixture of 45.0 g of 1- (2-bromomethyl-3-bromophenyl) -4-methyl-1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 6, 37.4 g of sodium methoxide and 600 mL of tetrahydrofuran was obtained. Stir at room temperature for 3 hours. Saturated aqueous sodium hydrogen carbonate was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and dried over anhydrous sodium sulfate.
  • Reference synthesis example 9 25.6 g of 1- (2-methoxymethyl-3-methylphenyl) -4-methyl-1,4-dihydrotetrazol-5-one described in Reference Synthesis Example 8, 50 mL of acetic acid and 25% hydrogen bromide-acetic acid solution 50 mL of the mixture was stirred at 65 ° C. for 1 hour. Saturated brine was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate and dried over anhydrous sodium sulfate.
  • a mixture of 11.6 g of palladium and 500 mL of toluene was stirred with heating under reflux for 14 hours. After cooling, a saturated aqueous ammonium chloride solution was poured into the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • Reference Synthesis Example 12 At room temperature, a mixture of 11.2 g of 1- (4-methoxy-3-methyl) -ethanone described in Reference Synthesis Example 11 and 200 ml of tetrahydrofuran was mixed with 16.1 g of diethyl carbonate, 6.2 g of 55% sodium hydride, and dibenzo. 0.05 g of -18-crown-6 and 3 ml of ethanol were added, and the mixture was stirred with heating under reflux for 8 hours. Water was poured into the reaction mixture, the mixture was acidified with 10% aqueous hydrochloric acid, extracted with ethyl acetate, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • Reference synthesis example 15 At 0 ° C., 0.3 g of 5-chloro-4-formyl-3- (4-methoxy-3-methyl-phenyl) -1-methyl-1H-pyrazole described in Reference Synthesis Example 14 and 10 ml of trifluoroacetic acid To the mixture was added 0.27 g of triethylsilane. After stirring at room temperature for 3 hours, 5 ml of water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • Reference Synthesis Example 20 In Reference Synthesis Example 16, 3- (4-methoxy) described in Reference Synthesis Example 21 was used instead of 5-chloro-3- (4-methoxy-3-methyl-phenyl) -1,4-dimethyl-1H-pyrazole. Similar reaction was performed using -3-methyl-phenyl) -1,5-dimethyl-1H-pyrazole, and 2-methyl-4- (1,5-dimethyl-1H-pyrazol-3-yl) -phenol Got.
  • the precipitate was collected by filtration, washed with 30 ml of water and 30 ml of hexane, dried under reduced pressure, and 1- ⁇ 3-methyl-2- [2-methyl-4- (5-aminocarbonyl-1,4-dimethyl-1H- 2 g of pyrazol-3-yl) -phenoxymethyl] -phenyl ⁇ -4-methyl-1,4-dihydrotetrazol-5-one were obtained.
  • Reference synthesis example 43 1- (2-Bromomethyl-3-methoxyphenyl) -4-methyl-1,4-dihydrotetrazol-5-one was prepared by the following steps (1) to (4).
  • ⁇ Step (1)> A mixture of 15.0 g of 3-amino-1-methoxy-2-methylbenzene, 48.7 g of triphosgene and 350 ml of toluene was stirred with heating under reflux for 3 hours. The reaction mixture allowed to cool was concentrated under reduced pressure to obtain 17.0 g of 1-methoxy-3-isocyanato-2-methylbenzene.
  • Step (3)> To a mixture of 10.00 g of 1- (2-methyl-3-methoxyphenyl) -1,4-dihydrotetrazol-5-one and 100 mL of N, N-dimethylformamide was added 2.47 g of 55% sodium hydride under ice cooling. Was added. The mixture was warmed to room temperature and stirred for 1 hour. To the reaction mixture, 3.5 mL of methyl iodide was added under ice cooling. The mixture was warmed to room temperature and stirred for 14 hours. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate.
  • Reference Synthesis Example 44 A mixture of 5.9 g of 3- (4-methoxy-3-methyl-phenyl) -1,5-dimethyl-1H-pyrazole described in Reference Synthesis Example 19 at room temperature, 5.8 g of N-bromosuccinimide, and 100 ml of chloroform. After stirring for 17 hours, water was added and the mixture was extracted with chloroform. The organic layer was washed with water, dried over anhydrous magnesium, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 4.0 g of 3- (4-methoxy-3-methyl-phenyl) -4-bromo-1,5-dimethyl-1H-pyrazole.
  • Reference Synthesis Example 46 A mixture of 0.6 g of 3- (4-methoxy-3-methyl-phenyl) -1,4,5-trimethyl-1H-pyrazole described in Reference Synthesis Example 45, 5 ml of 47% hydrobromic acid, and 5 ml of acetic acid was used. The mixture was stirred for 13 hours under reflux. The solvent was distilled off, 30 ml of ethyl acetate was added to the residue, and the mixture was stirred at room temperature for 1 hour. The precipitate was filtered, washed with hexane, and then dried under reduced pressure to obtain 0.5 g of 4- (1,4,5-trimethyl-1H-pyrazol-3-yl) -2-methyl-phenol.
  • the present tetrazolinone compound 9 to the present tetrazolinone compound 55 that can be produced in accordance with the synthesis method C from the synthesis method A are shown below.
  • Me represents a methyl group
  • Et represents an ethyl group
  • OMe represents a methoxy group
  • OEt represents an ethoxy group
  • Br represents a bromine atom
  • Cl represents a chlorine atom
  • F represents a fluorine atom
  • CF3 represents a trifluoromethyl group
  • CN represents a cyano group
  • SMe represents a methylthio group
  • Cy represents a cyclopropyl group.
  • R 1 is a C1-C3 alkyl group or a halogen atom
  • R 2 is a hydrogen atom or a C1-C3 alkyl group
  • R 3 is a C1-C3 alkyl group, a C1-C3 alkoxy group, a halogen atom
  • Z 1 is a C1-C3 alkyl group
  • Z 2 is a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom or a cyano group
  • Z 3 A tetrazolinone compound in which is a hydrogen atom, a C1-C3 alkyl group or a halogen atom.
  • R 1 is a C1-C3 alkyl group or a halogen atom
  • R 2 is a hydrogen atom or a C1-C3 alkyl group
  • R 3 is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group.
  • Z 1 is a C1-C3 alkyl group
  • Z 2 is a C1-C3 alkyl group optionally having one or more halogen atoms, a halogen atom or a cyano group
  • Z 3 is a hydrogen atom, C1- A tetrazolinone compound which is a C3 alkyl group or a halogen atom
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom or a C1-C3 alkyl group
  • R 3 is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group
  • Z 1 is a C1-C3 alkyl group
  • Z 2 is 1 or more halogen atoms optionally C1-C3 may be alkyl groups having a halogen atom or a cyano group
  • Z 3 is a hydrogen atom, C1-C3 alkyl group Or a te
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group
  • Z 1 is a C1-C3 alkyl group
  • Z 3 is a C1-C3 alkyl group or a halogen atom.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group
  • Z 1 is a C1-C3 alkyl group
  • Z 2 is one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group
  • Z 3 is a C1-C3 alkyl group or a halogen atom.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a halogen atom
  • Z 1 is a C1-C3 alkyl group
  • Z 2 is 1 or more.
  • halogen atom optionally may C1-C3 alkyl group optionally having a halogen atom or a cyano group
  • tetrazolinone compound Z 3 is a C1-C3 alkyl group or a halogen atom.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a cyclopropyl group
  • Z 1 is a C1-C3 alkyl group
  • Z 2 is 1 or more.
  • halogen atoms optionally may C1-C3 alkyl group optionally having a halogen atom or a cyano group
  • tetrazolinone compound Z 3 is a C1-C3 alkyl group or a halogen atom.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 may have one or more halogen atoms, a C1-C3 alkyl group, a halogen atom, C1 -C3 alkoxy group or a cyclopropyl group
  • Z 1 is a C1-C3 alkyl group
  • Z 2 is C1-C2 alkoxy group
  • one or more halogen atoms include C1-C3 may be alkyl, halogen atom, a C1-C2 alkylthio group or a cyano group
  • Z 3 is a hydrogen atom
  • tetrazolinone compound is C1-C3 alkyl group or a halogen atom.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group
  • Z 1 is C1 an -C3 alkyl group
  • Z 2 is C1-C2 alkoxy group
  • one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group
  • Z 3 is a hydrogen atom, C1- A tetrazolinone compound which is a C3 alkyl group or a halogen atom;
  • composition of the present invention examples include the following.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group
  • Z 1 is a C1-C3 alkyl group
  • Z 3 is a C1-C3 alkyl group or a halogen atom
  • compounds I to VI A plant disease control composition containing any one of the above.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group
  • Z 1 is a C1-C3 alkyl group
  • Z 2 is 1 or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group
  • Z 3 is a C1-C3 alkyl group or a halogen atom, any compound 1 A plant disease control composition containing any one of these.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group
  • Z 1 is a C1-C3 alkyl group
  • Z 3 is a C1-C3 alkyl group or a halogen atom
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group
  • Z 1 is a C1-C3 alkyl group
  • Z 2 is 1 or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group
  • Z 3 is a C1-C3 alkyl group or a halogen atom, any of the compounds III A plant disease control composition containing any one of these.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group
  • Z 1 is a C1-C3 alkyl group
  • Z 2 is 1 or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group
  • Z 3 is a C1-C3 alkyl group or a halogen atom, any of the compounds IV A plant disease control composition containing any one of these.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group
  • Z 1 is a C1-C3 alkyl group
  • Z 2 is 1 or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group
  • Z 3 is a C1-C3 alkyl group or a halogen atom, any of the compounds V A plant disease control composition containing any one of these.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom or a cyclopropyl group
  • Z 1 is a C1-C3 alkyl group
  • Z 3 is a C1-C3 alkyl group or a halogen atom
  • a plant disease control composition containing any one of these.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group
  • Z 1 is C1 an -C3 alkyl group
  • Z 2 is C1-C2 alkoxy group
  • one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group
  • Z 3 is a hydrogen atom
  • C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom and any one of compounds I to VI.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group
  • Z 1 is C1 an -C3 alkyl group
  • Z 2 is C1-C2 alkoxy group
  • one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group
  • Z 3 is a hydrogen atom
  • C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom, and any one of compounds I.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group
  • Z 1 is C1 an -C3 alkyl group
  • Z 2 is C1-C2 alkoxy group
  • one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group
  • Z 3 is a hydrogen atom
  • C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom, and any one of compounds II.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group
  • Z 1 is C1 an -C3 alkyl group
  • Z 2 is C1-C2 alkoxy group
  • one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group
  • Z 3 is a hydrogen atom
  • C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom and any one of compounds III.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group
  • Z 1 is C1 an -C3 alkyl group
  • Z 2 is C1-C2 alkoxy group
  • one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group
  • Z 3 is a hydrogen atom
  • C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom and any one of compounds IV.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group
  • Z 1 is C1 an -C3 alkyl group
  • Z 2 is C1-C2 alkoxy group
  • one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group
  • Z 3 is a hydrogen atom
  • C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom, and any one of compounds V.
  • R 1 is a C1-C3 alkyl group
  • R 2 is a hydrogen atom
  • R 3 is a C1-C3 alkyl group, a halogen atom, or a C1-C3 alkoxy group
  • Z 1 is C1 an -C3 alkyl group
  • Z 2 is C1-C2 alkoxy group
  • one or more halogen atoms include C1-C3 may be alkyl group, a halogen atom or a cyano group
  • Z 3 is a hydrogen atom
  • C1- A plant disease control composition comprising a tetrazolinone compound which is a C3 alkyl group or a halogen atom and any one of compounds VI.
  • a plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 55 and compound I in a ratio of 0.1: 1;
  • a plant disease control composition comprising any one compound from the present tetrazolinone compound 1 to the present tetrazolinone compound 55 and compound I in a ratio of 1: 1;
  • a plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 55 and compound I in a ratio of 10: 1;
  • a plant disease control composition comprising any one compound from the present tetrazolinone compound 1 to the present tetrazolinone compound 55 and compound II in a ratio of 0.1: 1;
  • a plant disease control composition comprising any one compound of the present tetrazolinone compound 1 to the present tetrazolinone compound 55 and compound II in a ratio of 1: 1;
  • a plant disease control composition comprising any one compound of the
  • a part represents a weight part.
  • Formulation Example 1 A composition is obtained by thoroughly pulverizing and mixing 50 parts of any one of the compositions of the present invention, 3 parts of calcium lignin sulfonate, 2 parts of magnesium lauryl sulfate and 45 parts of synthetic silicon hydroxide.
  • Formulation Example 2 20 parts of any one of the compositions of the present invention and 1.5 parts of sorbitan trioleate were mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and pulverized by a wet pulverization method. Thereafter, 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate is added thereto, and further 10 parts of propylene glycol is added and stirred to obtain a preparation.
  • Formulation Example 3 A preparation is obtained by thoroughly pulverizing and mixing 2 parts of any one of the compositions of the present invention, 88 parts of kaolin clay and 10 parts of talc.
  • Formulation Example 4 A formulation is obtained by thoroughly mixing 5 parts of any one of the compositions of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene.
  • Formulation Example 5 Any one of the compositions of the present invention, 2 parts of composition, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are mixed and mixed well with water. The formulation is obtained by granulating and drying.
  • Formulation Example 6 10 parts of any one of the compositions of the present invention; 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt; and 55 parts of water are mixed and finely pulverized by a wet pulverization method. By doing so, a formulation is obtained.
  • Test Example 1 Control Trial against Wheat Leaf Blight Fungus (Septoria tritici) Each test compound diluted in DMSO (dimethyl sulfoxide) at a predetermined concentration was dispensed into a titer plate (96 well), and then the wheat leaf blight fungus was separated in advance. 150 ⁇ l of potato broth liquid medium (PDB medium) inoculated with live spores was dispensed. The plate was cultured at 18 ° C. for 4 days to grow wheat leaf blight fungi, and then the growth degree of wheat leaf blight fungi was measured by absorbance at 550 nm in each well of the titer plate. Based on the degree of growth, potency was calculated using “Formula 1” and ranked according to [Table 4]. The results are shown in [Table 5] to [Table 15].
  • Test example 2 A plastic pot is filled with soil, seeded with wheat (variety: Shirogane), and grown in a greenhouse for 14 days.
  • the test compound is made into a preparation according to the preparation example, then diluted with water to a predetermined concentration, and the diluted solution is sprayed so as to adhere sufficiently to the leaf surface of the wheat.
  • the plants are air-dried, and after 2 days, spray-inoculated with an aqueous suspension (about 1,000,000 cells / ml) of conidia of wheat leaf blight fungus (Mycosphaerella graminicola).
  • an aqueous suspension about 1,000,000 cells / ml
  • conidia of wheat leaf blight fungus Mycosphaerella graminicola
  • the lesion area of wheat leaf blight is investigated.
  • wheat is cultivated in the same manner as the treated area except that the diluted solution of the test compound is not sprayed on the foliage (this is referred to as an untreated area).
  • the lesion area of wheat leaf blight is investigated as in the treatment area.
  • a marked decrease in the lesion area of wheat treated with the disease control composition containing the present tetrazolinone compound and the present bactericidal active compound is recognized as compared with the lesion area in the untreated area.
  • Test example 3 The plastic pot is filled with soil, soybean (variety: Kurosengoku) is sown and grown in a greenhouse for 14 days.
  • the test compound is made into a preparation according to the preparation example, then diluted with water to a predetermined concentration, and the diluted solution is sprayed so as to sufficiently adhere to the leaves of the soybean.
  • the plants are air-dried, and after 2 days, spray-inoculated with an aqueous suspension (about 10,000 / ml) of a summer spore of soybean rust fungus (Phakopsora pachyrhizi).
  • an aqueous suspension about 10,000 / ml
  • aqueous suspension about 10,000 / ml
  • a summer spore of soybean rust fungus Puhakopsora pachyrhizi
  • soybeans are cultivated in the same manner as the treated group except that the diluted solution of the test compound is not sprayed on the foliage (this is referred to as the untreated group). Then, the lesion area of soybean rust is investigated as in the treatment area. As a result, the lesion area of soybean treated with the disease control composition containing the present tetrazolinone compound and the present bactericidal active compound is remarkably reduced as compared with the lesion area in the untreated area. According to the present invention, plant diseases can be controlled.
  • composition of the present invention exhibits an excellent control effect against plant diseases, it can be used as a plant disease control agent.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne une composition de lutte contre les maladies de plante, qui est efficace pour lutter contre les maladies de plante et contient un composé de tétrazolinone représenté dans la formule (1) (dans la formule, R1 représente un groupe alkyle C1-C3, etc., R2 représente un atome d'hydrogène, etc., R3 représente un groupe alkyle C1-C3, etc., Z1 représente un groupe alkyle C1-C3, Z2 représente un groupe alcoxy C1-C2, etc., et Z3 représente un groupe alkyle C1-C3, etc.) et un composé QoI et, idéalement, le rapport de poids entre le composé de tétrazolinone et le composé QoI est : composé de tétrazolinone/composé QoI = 0,1/1 à 10/1.
PCT/JP2014/075543 2013-10-02 2014-09-18 Composition de lutte contre les maladies de plante et son utilisation WO2015050039A1 (fr)

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WO2015147314A1 (fr) * 2014-03-28 2015-10-01 住友化学株式会社 Composés aromatiques et leurs utilisations
WO2015147337A1 (fr) * 2014-03-28 2015-10-01 住友化学株式会社 Composé tétrazolinone et application associée
WO2015147332A1 (fr) * 2014-03-28 2015-10-01 住友化学株式会社 Composé de tétrazolinone et son utilisation
EP3025586A4 (fr) * 2013-07-22 2017-01-04 Sumitomo Chemical Company Limited Composition de lutte contre les maladies des plantes et son application
US9907307B2 (en) 2014-03-28 2018-03-06 Sumitomo Chemical Company, Limited Aromatic compound and uses thereof
US10070646B2 (en) 2014-03-28 2018-09-11 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
CN109641879A (zh) * 2016-08-25 2019-04-16 住友化学株式会社 四唑啉酮化合物及其用途

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WO2013162072A1 (fr) * 2012-04-27 2013-10-31 Sumitomo Chemical Company, Limited Composés de tétrazolinone et leur utilisation en tant que pesticides
WO2014051161A1 (fr) * 2012-09-28 2014-04-03 Sumitomo Chemical Company, Limited Composés tétrazolinone et leur utilisation en tant que pesticide
WO2014051165A1 (fr) * 2012-09-28 2014-04-03 Sumitomo Chemical Company, Limited Composés de tétrazolinone et leur utilisation comme pesticides
JP2014097979A (ja) * 2013-10-17 2014-05-29 Sumitomo Chemical Co Ltd 有害生物防除組成物及びその用途

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WO2013162072A1 (fr) * 2012-04-27 2013-10-31 Sumitomo Chemical Company, Limited Composés de tétrazolinone et leur utilisation en tant que pesticides
WO2014051161A1 (fr) * 2012-09-28 2014-04-03 Sumitomo Chemical Company, Limited Composés tétrazolinone et leur utilisation en tant que pesticide
WO2014051165A1 (fr) * 2012-09-28 2014-04-03 Sumitomo Chemical Company, Limited Composés de tétrazolinone et leur utilisation comme pesticides
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Cited By (13)

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EP3025586A4 (fr) * 2013-07-22 2017-01-04 Sumitomo Chemical Company Limited Composition de lutte contre les maladies des plantes et son application
US9655364B2 (en) 2013-07-22 2017-05-23 Sumitomo Chemical Company, Limited Plant disease control composition and its use
US9822095B2 (en) 2014-03-28 2017-11-21 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
WO2015147332A1 (fr) * 2014-03-28 2015-10-01 住友化学株式会社 Composé de tétrazolinone et son utilisation
WO2015147337A1 (fr) * 2014-03-28 2015-10-01 住友化学株式会社 Composé tétrazolinone et application associée
US9788547B2 (en) 2014-03-28 2017-10-17 Sumitomo Chemical Company, Limited Aromatic compound and uses thereof
WO2015147314A1 (fr) * 2014-03-28 2015-10-01 住友化学株式会社 Composés aromatiques et leurs utilisations
US9826741B2 (en) 2014-03-28 2017-11-28 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
US9907307B2 (en) 2014-03-28 2018-03-06 Sumitomo Chemical Company, Limited Aromatic compound and uses thereof
US10070646B2 (en) 2014-03-28 2018-09-11 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
CN109641879A (zh) * 2016-08-25 2019-04-16 住友化学株式会社 四唑啉酮化合物及其用途
CN109641879B (zh) * 2016-08-25 2021-03-09 住友化学株式会社 四唑啉酮化合物及其用途
US11046673B1 (en) 2016-08-25 2021-06-29 Sumitomo Chemical Company, Limited Tetrazolinone compounds and its use

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