Pyrazole-4-oxadiazine ring compounds and plant disease control agents using the same

Abstract

To provide an excellent plant disease control agent for agricultural and horticultural use. 【Solution means】 General formula [I] TIFF2026079567000027.tif3158 [In the formula, A represents an oxygen atom or a sulfur atom, R 1 represents a C1-C6 alkyl group or the like, R 2 represents a C1-C6 alkyl group or the like, R 3 represents a hydrogen atom, a C1-C6 alkyl group or the like, R 4 represents a hydrogen atom, a C1-C6 alkyl group or the like, R 5 and R 5’ represent a hydrogen atom, a C1-C6 alkyl group or the like, R 6 and R 6’ represent a hydrogen atom, a C1-C6 alkyl group or the like, Q 1 represents a C6-C 12 aryl group or the like, Q 2 represents a C6-C 12 aryl group or the like], a pyrazole-4-oxadiazine ring compound represented thereby, an optical isomer thereof, or a salt thereof, and a plant disease control agent for agricultural and horticultural use containing the same as an active ingredient are provided.

Description

[Technical Field]

[0001] The present invention relates to a novel pyrazole-4-oxadiazine ring compound, its optical isomer, or a salt thereof, or to a plant disease control agent for agricultural and horticultural use containing a pyrazole-4-oxadiazine ring compound, its optical isomer, or a salt thereof as an active ingredient. [Background technology]

[0002] Patent Document 1 describes a pyridazine-4-heterocyclic compound having plant disease control activity.

[0003] Patent document 2 describes a pyridine compound having plant disease control activity.

[0004] Patent Document 3 describes pyrimidine compounds or triazine compounds having plant disease control activity.

[0005] Patent Document 4 describes a bisheteroaryl-thioether-oxadiazine compound having plant disease control activity.

[0006] Patent Document 5 describes pyrazole-5-carboxamide compounds and pyrazole-5-carbothioamide compounds having plant disease control activity.

[0007] Patent document 6 describes a dihydrooxadiadinyl-pyridazinone compound having plant disease control activity.

[0008] Patent document 7 describes a pyridazine-dihydrooxadiazine compound having plant disease control activity.

[0009] Patent document 8 describes a five-membered heteroaryl ring compound having plant disease control activity.

[0010] Patent document 9 describes a pyrazole-4-carboxamide compound having plant disease control activity.

[0011] The above-mentioned patent documents do not disclose any pyrazole-4-oxadiazine ring compounds, which are the subject of the present invention. [Prior art documents] [Patent Documents]

[0012] [Patent Document 1] International Publication No. 2020 / 127780 [Patent Document 2] International Publication No. 2021 / 245083 [Patent Document 3] International Publication No. 2021 / 245087 [Patent Document 4] International Publication No. 2023 / 099445 [Patent Document 5] International Publication No. 2023 / 243678 [Patent Document 6] International Publication No. 2024 / 132895 [Patent Document 7] International Publication No. 2024 / 132901 [Patent Document 8] International Publication No. 2024 / 143338 [Patent Document 9] International Publication No. 2024 / 162284 [Overview of the project] [Problems that the invention aims to solve]

[0013] In the cultivation of agricultural and horticultural crops, numerous plant disease control agents are used to combat plant diseases caused by pathogenic fungi. However, conventional plant disease control agents often have insufficient efficacy, their use is restricted by the emergence of pathogenic fungi that develop resistance to the agents, and the resulting plant diseases. Furthermore, they do not always meet expectations in terms of phytotoxicity or contamination of plants, toxicity to humans, livestock, and fish, and environmental impact. Therefore, there is a strong demand for the development of plant disease control agents that have fewer of these drawbacks and can be used safely. [Means for solving the problem]

[0014] As a result of diligent research, the inventors have discovered that a drug containing a pyrazole-4-oxadiazine ring compound represented by the following formula [I], its optical isomer, or its salt as an active ingredient has a high control effect against plant diseases caused by pathogenic fungi in the cultivation of useful crops, and have completed the present invention.

[0015] In other words, the gist of this invention is as follows: (1) A compound represented by general formula [I], its optical isomer, or a salt thereof.

[0016] [ka]

[0017] [In the formula, A represents an oxygen atom, a sulfur atom, S=O, or S(=O)2. R 1 C1-C6 alkyl groups, C1-C6 haloalkyl groups, C3-C8 cycloalkyl groups, C1-C6 alkoxy-C1-C6 alkyl groups, C1-C6 haloalkoxy-C1-C6 alkyl groups, cyano C1-C6 alkyl groups, C6-C 12 Aryl-C1~C6 alkyl groups, C1~C6 alkylcarbonyl groups, C1~C6 alkylsulfonyl groups, C6~C 12 Aryl group, or C6~C 12 Aryl-C1~C6 alkyl group (the aryl group is one or more R 10 (May be substituted with substituents selected from) R 2is a hydrogen atom, a hydroxy group, a halogen atom, a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C8 cycloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C1-C6 alkyl-C3-C8 cycloalkyl group, a hydroxy C1-C6 alkyl group, a C1-C6 alkoxy-C1-C6 alkyl group, a C3-C8 cycloalkyl-C1-C6 alkyl group, a C1-C6 alkylcarbonyl group, a C1-C6 alkoxycarbonyl group, an aminocarbonyl group, a C1-C6 alkylsulfanyl group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C6-C 12 aryl group (the aryl group may be substituted with one or more substituents selected from R 10 ), a 5- to 12-membered heteroaryl group (the heteroaryl group may be substituted with one or more substituents selected from R 10 ), an amino group, a C1-C6 alkylamino group (the amino group may be substituted with a substituent selected from R 9 ), a C1-C6 alkylcarbonylamino group (the amino group may be substituted with a substituent selected from R 9 ), or a -C(=NR 7 )R 8 group, and Q 1 is a C3-C8 cycloalkyl group, a C6-C 12 aryl group (the aryl group may be substituted with one or more substituents selected from R 10 ), or a 5- to 12-membered heteroaryl group (the heteroaryl group may be substituted with one or more substituents selected from R 10 ), and Q 2 is a C6-C<00ooo019>aryl group (the aryl group may be substituted with one or more substituents selected from R 10 ), or a 5- to 12-membered heteroaryl group (the heteroaryl group may be substituted with one or more substituents selected from R 10 ), and R 3 represents a hydrogen atom, a C1-C6 alkyl group, or a C1-C6 alkylcarbonyl group. R 4 This represents a hydrogen atom or a C1-C6 alkyl group. R 5 and R 5’ This represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group. R 6 and R 6’ This represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group. R 7 C1-C6 alkyl group, C1-C6 alkylaminocarbonyl group (the amino group is R 9 (may be substituted with substituents selected from) or a C1-C6 alkyl-C3-C8 cycloalkylcarbonylamino group (the amino group is R 9 (may be substituted with substituents selected from) R 8 This represents a hydrogen atom or a C1-C6 alkyl group. R 9 This represents a C1-C6 alkyl group. R 10 These are hydroxyl groups, halogen atoms, cyano groups, C1-C6 alkyl groups, C1-C6 haloalkyl groups, C1-C6 alkoxy-C1-C6 alkyl groups, C1-C6 alkoxy groups, and C6-C 12 Aryl-C1~C6 alkoxy group, C1~C6 alkoxy-C1~C6 alkoxy group, cyano-C1~C6 alkoxy group, C1~C6 alkylsulfanyl group, C1~C6 alkylsulfinyl group, C1~C6 alkylsulfonyl group, C1~C6 alkylcarbonylamino group (the amino group is R 9 (May be substituted with substituents selected from), C1-C6 alkylaminocarbonylamino group (the amino group is R 9 (May be substituted with substituents selected from), C6~C 12 Aryl group, C6~C 12 Aryloxy group, 5-12 member heteroarylcarbonylamino group, 5-12 member heteroaryloxy group, 5-12 member heteroaryl-C1-C6 alkoxy group, or -C(=NR) 7 )R 8 [Indicates the basis.] (2) A plant disease control agent for agricultural and horticultural use, characterized by containing the compound described in (1), its stereoisomer, or its salt as an active ingredient. (3) The plant disease control agent for agricultural and horticultural use described in (2), wherein the plant disease is derived from the pathogenic fungus. (4) A plant disease control agent for agricultural and horticultural use as described in (3), wherein the pathogenic fungi are classified into the Fungi kingdom (Basidiomycetes, Ascomycota, Mucormiformes, etc.), Stramenopyla (Oomycetes, etc.), Rhizaria kingdom (Cercozoa, etc.), and Bacteria. (5) A plant disease control composition for agricultural and horticultural use comprising the compound described in (1), a stereoisomer thereof, or a salt thereof, and an agriculturally acceptable carrier. (6) A method for controlling diseases of useful plants, comprising spraying an effective amount of the compound described in (1), its stereoisomer, or its salt onto a useful plant, a part of a useful plant, or the place where the useful plant is growing. (7) The method according to (6), wherein the plant disease is derived from a pathogenic fungus. (8) The method according to (7), wherein the pathogenic fungus is classified into the kingdom Fungi (Basidiomycetes, Ascomycetes, Mucormiformes, etc.), Stramenopyla (Oomycetes, etc.), Rhizaria (Cercozoa, etc.), and Bacteria. (9) Use of the compounds described in (1), their stereoisomers, or their salts as plant disease control agents for useful plants in agriculture and horticulture. [Effects of the Invention]

[0018] The compounds of the present invention are useful as active ingredients in pesticides such as plant disease control agents for agricultural and horticultural use.

[0019] The plant disease control agent for agricultural and horticultural use containing the compound of the present invention exhibits excellent control effects against a wide range of plant diseases caused by fungi (Basidiomycetes, Ascomycota, Mucormycetes, etc.), Stramenopyla (Oomycetes, etc.), Rhizaria (Cercozoa, etc.), and bacteria, and can also control fungi that have acquired drug resistance. [Modes for carrying out the invention]

[0020] This section explains the symbols and terms used in this specification.

[0021] In this invention, "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0022] In this invention, the notation "C1~C6" indicates that the number of carbon atoms in the substituent following it is 1 to 6 in this case.

[0023] In the present invention, "C1-C6 alkyl group" refers to a linear or branched alkyl group having 1 to 6 carbon atoms, unless otherwise specified. Examples include groups such as methyl, ethyl, isopropyl, tert-butyl, n-propyl, sec-butyl, isobutyl, n-butane, 2-methylbutan-1-yl, 2-ethylbutan-2-yl, 3-methylbutan-2-yl, n-pentane, 2-methylpentan-2-yl, pentan-3-yl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, or n-hexyl.

[0024] In the present invention, "C1-C6 haloalkyl group" refers to a linear or branched haloalkyl group having 1 to 6 carbon atoms, substituted with the same or different 1 to 13 halogen atoms, unless otherwise specified. Examples include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, iodomethyl, chlorodifluoromethyl, bromodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, pen Examples of such groups include tafluoroethyl, 1-chloroethyl, 2-chloroethyl, 1,1-dichloroethyl, 2,2-dichloroethyl, 2,2,2-trichloroethyl, 2-bromoethyl, 2-iodoethyl, 2-chloro-2,2-difluoroethyl, 2-methyl-3-fluoropropan-2-yl, 2-methyl-3,3-difluoropropan-2-yl, 2-methyl-3,3,3-trifluoropropan-2-yl, 2-methyl-4-fluorobutan-2-yl, 2-methyl-4,4-difluorobutan-2-yl, or 2-methyl-4,4,4-trifluorobutan-2-yl.

[0025] In the present invention, "C3-C8 cycloalkyl group" refers to a cycloalkyl group having 3 to 8 carbon atoms unless otherwise specified, and the ring may be optionally substituted with alkyl groups within a specified range of carbon atoms. Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl groups.

[0026] In the present invention, unless otherwise specified, "C1-C6 alkyl-C3-C8 cycloalkyl group" means the alkyl portion and the cycloalkyl portion as described above, and refers to a (C1-C6 alkyl)-(C3-C8 cycloalkyl)-group in which an alkyl group is substituted on the cycloalkyl portion. Examples of such groups include 1-methylcyclopropyl, 2-methylcyclopropyl, 2,2-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1-n-propylcyclopropyl, 1-isopropylcyclopropyl, 1-tert-butylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1-methylcyclobutyl, 1-ethylcyclobutyl, 1-isopropylcyclobutyl, 2-methylcyclobutyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 4-methylcyclohexyl, or 4,4-dimethylcyclohexyl.

[0027] In the present invention, unless otherwise specified, "hydroxy C1-C6 alkyl group" refers to a hydroxy-(C1-C6 alkyl)-group in which the alkyl portion has the meaning described above. Examples of such groups include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxypropan-2-yl, 3-hydroxy-2-methylpropan-2-yl, 4-hydroxy-2-methylbutan-2-yl, or 5-hydroxy-2-methylpentan-2-yl.

[0028] In the present invention, unless otherwise specified, "cyano C1-C6 alkyl group" refers to a (cyano)-(C1-C6 alkyl)-group in which the alkyl portion has the meaning described above. Examples of such groups include cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 1-cyanopropyl, 2-cyanopropyl, 3-cyanopropyl, 2-cyano-2-propyl, 1-cyanobutyl, 4-cyanobutyl, 5-cyanopentyl, or 6-cyanohexyl.

[0029] In the present invention, unless otherwise specified, "C3-C8 cycloalkyl-C1-C6 alkyl" refers to a (C3-C8 cycloalkyl)-(C1-C6 alkyl)-group in which the cycloalkyl portion and the alkyl portion have the meanings described above. Examples of such groups include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, 1-cyclopropylethyl, 2-cyclopropylethyl, 2-cyclopropylpropan-2-yl, 2-cyclobutylpropan-2-yl, 2-cyclopentylpropan-2-yl, or 1-cyclopropylpropyl.

[0030] In the present invention, unless otherwise specified, "C1-C6 alkylcarbonyl group" refers to a (C1-C6 alkyl)-C(=O)- group in which the alkyl portion has the meaning described above. Examples of such groups include methylcarbonyl, ethylcarbonyl, isopropylcarbonyl, tert-butylcarbonyl, n-propylcarbonyl, sec-butylcarbonyl, isobutylcarbonyl, n-butylcarbonyl, 2-methylbutan-1-ylcarbonyl, 3-methylbutan-2-ylcarbonyl, n-pentylcarbonyl, pentan-3-ylcarbonyl, isopentylcarbonyl, neopentylcarbonyl, sec-pentylcarbonyl, tert-pentylcarbonyl, or n-hexylcarbonyl.

[0031] In the present invention, unless otherwise specified, "C1-C6 alkyl sulfanyl group" refers to a (C1-C6 alkyl)-S- group in which the alkyl portion has the meaning described above. Examples include groups such as methyl sulfanyl, ethyl sulfanyl, n-propyl sulfanyl, isopropyl sulfanyl, n-butyl sulfanyl, isobutyl sulfanyl, sec-butyl sulfanyl, or tert-butyl sulfanyl.

[0032] In the present invention, unless otherwise specified, "C1-C6 alkyl sulfinyl group" refers to a (C1-C6 alkyl)-S(=O)- group in which the alkyl portion has the meaning described above. Examples of such groups include methyl sulfinyl, ethyl sulfinyl, n-propyl sulfinyl, isopropyl sulfinyl, n-butyl sulfinyl, isobutyl sulfinyl, sec-butyl sulfinyl, or tert-butyl sulfinyl.

[0033] In the present invention, unless otherwise specified, "C1-C6 alkylsulfonyl group" refers to a (C1-C6 alkyl)-S(=O)2- group in which the alkyl portion has the meaning described above. Examples of such groups include methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, or tert-butylsulfonyl.

[0034] In the present invention, unless otherwise specified, "C1-C6 alkoxy group" refers to a (C1-C6 alkyl)-O- group in which the alkyl portion has the meaning described above. Examples of such groups include methoxy, ethoxy, isopropoxy, tert-butythoxy, n-propoxy, sec-butoxy, isobutoxy, n-butoxy, 2-methylbutane-1-yloxy, 2-ethylbutane-2-yloxy, 3-methylbutane-2-yloxy, n-pentoxy, 2-methylpentane-2-yloxy, pentane-3-yloxy, isopentyloxy, neopentyloxy, sec-pentyloxy, tert-pentyloxy, or n-hexyloxy.

[0035] In the present invention, unless otherwise specified, "C1-C6 haloalkoxy group" refers to a (C1-C6 haloalkyl)-O- group in which the haloalkyl portion has the meaning described above. Examples of such groups include difluoromethoxy, dichloromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, pentafluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy, 2-chloro-1,1,2,2-tetrafluoroethoxy, or 1,1,2,3,3,3-hexafluoropropoxy.

[0036] In the present invention, unless otherwise specified, "C1-C6 alkoxy-C1-C6 alkyl group" refers to a (C1-C6 alkoxy)-(C1-C6 alkyl)-group where the alkoxy portion and the alkyl portion have the meanings described above. Examples include methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, tert-butoxymethyl, 1-methoxyethyl, 1-methoxy-1-methylethyl, 2-methoxyethyl, 1-ethoxyethyl, 2-ethoxyethyl, and 1-isopropoxyethyl. Examples of groups include ethyl, 1-methoxypropyl, 2-methoxypropyl, 1-ethoxypropyl, 1-methoxybutyl, 1-ethoxybutyl, 3-methoxypropan-2-yl, 3-ethoxypropan-2-yl, 3-methoxy-2-methylpropan-2-yl, 3-ethoxy-2-methylpropan-2-yl, 4-methoxybutan-2-yl, 4-ethoxybutan-2-yl, 4-methoxy-2-methylbutan-2-yl, or 4-ethoxy-2-methylbutan-2-yl.

[0037] In the present invention, unless otherwise specified, "C1-C6 haloalkoxy-C1-C6 alkyl group" refers to a (C1-C6 haloalkoxy)-(C1-C6 alkyl)-group where the haloalkoxy portion and the alkyl portion have the meanings described above. Examples include 2-(difluoromethoxy)ethyl, 2-(trifluoromethoxy)ethyl, 2-(2,2-difluoroethoxy)ethyl, 2-(2,2,2-trifluoroethoxy)ethyl, 2-(3,3-difluoropropiooxy)ethyl, 2 Examples of groups include -(3,3,3-trifluoropropioxy)ethyl, 3-(difluoromethoxy)propyl, 3-(trifluoromethoxy)propyl, 3-(2,2-difluoroethoxy)propyl, 3-(2,2,2-trifluoroethoxy)propyl, 3-(3,3-difluoropropoxy)propyl, 3-(3,3,3-trifluoropropioxy)propyl, 4-(trifluoromethoxy)butyl, or 5-(trifluoromethoxy)pentyl.

[0038] In the present invention, unless otherwise specified, the "C1-C6 alkoxy-C1-C6 alkoxy group" means that the alkoxy portion has the meaning described above, and represents a (C1-C6 alkoxy)-(C1-C6 alkoxy)-group. Examples of such groups include methoxymethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 2-(n-propoxy)ethoxy, 2-isopropoxyethoxy, 2-(n-butoxy)ethoxy, 2-(sec-butoxy)ethoxy, 2-isobutoxyethoxy, or 2-(tert-butoxy)ethoxy.

[0039] In the present invention, unless otherwise specified, "cyano C1-C6 alkoxy group" refers to a (cyano)-(C1-C6 alkoxy)- group in which the alkoxy portion has the meaning described above. Examples of such groups include cyanomethoxy, 1-cyanoethoxy, 2-cyanoethoxy, 1-cyanopropoxy, 2-cyanopropoxy, 3-cyanopropoxy, 2-cyano-2-propoxy, 1-cyanobutoxy, 4-cyanobutoxy, 5-cyanopentyloxy, or 6-cyanohexyloxy.

[0040] In the present invention, unless otherwise specified, "C1-C6 alkoxycarbonyl group" refers to a (C1-C6 alkoxy)-C(=O)- group where the alkoxy portion has the meaning described above. Examples of such groups include methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, tert-butytoxycarbonyl, n-propoxycarbonyl, sec-butoxycarbonyl, isobutoxycarbonyl, n-butoxycarbonyl, 2-methylbutan-1-yloxycarbonyl, 2-ethylbutan-2-yloxycarbonyl, 3-methylbutan-2-yloxycarbonyl, n-pentoxycarbonyl, 2-methylpentan-2-yloxycarbonyl, pentan-3-yloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, or n-hexycarbonyloxycarbonyl.

[0041] In the present invention, "C6~C 12 Unless otherwise specified, the term "aryl group" refers to an aryl group having 6 to 12 carbon atoms, such as phenyl, naphthalene-1-yl, or naphthalene-2-yl.

[0042] In the present invention, "C6~C 12 Unless otherwise specified, the aryl portion of an aryl oxy group has the meaning described above (C6~C 12 The group exhibits an aryl)-O- group, and examples include phenyloxy, naphthalene-1-yloxy, or naphthalene-1-yloxy.

[0043] In the present invention, "C6~C 12 Unless otherwise specified, "aryl-C1~C6 alkyl group" means that the aryl portion and the alkyl portion have the meanings described above (C6~C 12The group represents an aryl)-(C1-C6 alkyl)- group, and examples of such groups include benzyl, 2-phenylethane-1-yl, 2-phenylethane-2-yl, 2-phenylpropane-1-yl, 2-phenylbutan-1-yl, naphthalene-1-ylmethyl, or naphthalene-2-ylmethyl.

[0044] In the present invention, "C6~C 12 Unless otherwise specified, "aryl-C1~C6 alkoxy group" means that the aryl portion and the alkoxy portion have the meanings described above (C6~C 12 The group represents an aryl)-(C1-C6 alkoxy)- group, and examples of such groups include benzyloxy, 2-phenylethane-1-yloxy, 2-phenylethane-2-yloxy, 2-phenylpropane-1-yloxy, 2-phenylbutan-1-yloxy, naphthalene-1-ylmethyloxy, or naphthalene-2-ylmethyloxy.

[0045] In the present invention, unless otherwise specified, "5-12 membered heteroaryl group" refers to a 5-12 membered monocyclic or fused bicyclic aromatic heterocycle containing one or more heteroatoms selected from oxygen, nitrogen, and sulfur atoms in addition to carbon atoms. Examples of monocyclic aromatic heterocycles include pyridine-2-yl, pyridine-3-yl, pyridine-4-yl, pyridinon-1-yl, pyridinon-3-yl, pyridinon-4-yl, pyridinon-5-yl, pyridinon-6-yl, pyrimidine-2-yl, pyrimidine-4-yl, pyrimidine-5-yl, Pyrazine-2-yl, pyridazine-3-yl, pyridazine-4-yl, 1,2,3-triazine-4-yl, 1,2,3-triazine-5-yl, 1,2,4-triazine-3-yl, 1,2,4-triazine-5-yl, 1,2,4-triazine-6-yl, 1,3,5-triazine-2-yl, thiophene-2-yl, thiophene-3-yl, fran-2-yl, fran-3-yl, pyrazole-1-yl, pyrazole-3-yl, pyrazole-4-yl, pyrazole-5-yl, thiazole-2-yl, thiazole-4-yl, thiazo Lu-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, imidazole-2-yl, imidazole-4-yl, imidazole-5-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5-yl, 1,2,4-triazol-1-yl, 1,2,4-triazol -3-yl, 1,2,4-triazole-5-yl, 1,3,4-thiadiazole-2-yl, 1,2,3-thiadiazole-4-yl, 1,2,3-thiadiazole-5-yl, 1,2,4-thiadiazole-3-yl, 1,2,4-thiadiazole-5-yl, 1,2,5-thiadiazole-3-yl, 1,3,4-oxadiazole-2-yl, 1,2,3-oxadiazole-4-yl, 1,2,3-oxadiazole-5-yl, 1,2,4-oxadiazole-3-yl, 1,2,4-oxadiazole-5-yl, or 1,2,Examples of groups include 5-oxadiazole-3-yl, and as a condensed bicyclic heterocycle, one of the monocyclic groups and a phenyl ring, or any of the groups of the monocyclic aromatic heterocycle, C8~C, 10Condensed bicyclic moieties formed by condensation to form a bicyclic group, for example, indole-1-yl, indole-2-yl, indole-3-yl, indole-4-yl, indole-5-yl, indole-6-yl, indole-7-yl, 1,3-benzodioxol-4-yl, 1,3-benzodioxol-5-yl, 2,3-dihydrobenzofuran-4-yl, 2,3-dihydrobenzofuran-5-yl, 2,3-dihydrobenzofuran-6-yl, 2,3-dihydrobenzofuran-7-yl, 1,4-benzodioxan-5-yl, 1,4-benzodioxan-6-yl, croman-5-yl, croman-6-yl, croman-7-yl, croman-8-yl, benzimidazole-1-yl, benzimidazole-2-yl, benzimidazole-4-yl, benzimidazole-5-yl, benzimidazole-6-yl, benzimidazole-7-yl, indazole-1-yl, indazole-3-yl, indazole-4-yl, indazole-5-yl, indazole-6-yl, in Dazole-7-yl, benzotriazole-1-yl, benzotriazole-4-yl, benzotriazole-5-yl, benzotriazole-6-yl, benzotriazole-7-yl, isoquinoline-1-yl, isoquinoline-3-yl, isoquinoline-4-yl, isoquinoline-5-yl, isoquinoline-6-yl, isoquinoline-7-yl, isoquinoline-8-yl, quinoline-2-yl, quinoline-3-yl, quinoline-4-yl, quinoline-5-yl, Quinoline-6-yl, Quinoline-7-yl, Quinoline-8-yl, Benzothiazole-2-yl, Benzothiazole-4-yl, Benzothiazole-5-yl, Benzothiazole-6-yl, Benzothiazole-7-yl, Benzofuran-2-yl, Benzofuran-3-yl, Benzofuran-4-yl, Benzofuran-5-yl, Benzofuran-6-yl, Benzofuran-7-yl, Benzothiophene-2-yl, Benzothiophene-3-yl, Benzothiophene -4-yl, benzothiophen-5-yl, benzothiophen-6-yl, benzothiophen-7-yl, benzoxazole-2-yl, benzoxazole-4-yl, benzoxazole-5-yl, benzoxazole-6-yl, benzoxazole-7-yl, 1,2-benzisoxazole-3-yl, 1,2-benzisoxazole-4-yl, 1,2-benzisoxazole-5-yl, 1,2-benzisoxazole-6-yl, 1,Examples of groups include 2-benzisoxazole-7-yl, pyrazolopyridine-1-yl, pyrazolopyridine-3-yl, pyrazolopyridine-4-yl, pyrazolopyridine-5-yl, pyrazolopyridine-6-yl, quinazolin-2-yl, quinazolin-4-yl, quinazolin-5-yl, quinazolin-6-yl, quinazolin-7-yl, quinazolin-8-yl, quinoxalin-2-yl, quinoxalin-3-yl, quinoxalin-5-yl, quinoxalin-6-yl, quinoxalin-7-yl, quinoxalin-8-yl, cinnolin-3-yl, cinnolin-4-yl, cinnolin-5-yl, cinnolin-6-yl, cinnolin-7-yl, or cinnolin-8-yl.

[0046] In the present invention, unless otherwise specified, "5-12 member heteroaryloxy group" refers to a (5-12 member heteroaryl)-O- group in which the 5-12 member heteroaryl portion has the meaning described above. Examples of monocyclic aromatic heterocycles include pyridine-2-yloxy, pyridine-3-yloxy, pyridine-4-yloxy, pyridinone-1-yloxy, pyridinone-3-yloxy, pyridinone-4-yloxy, pyridinone-5-yloxy, pyridinone-6-yloxy, pyrimidine-2-yloxy, pyrimidine-4-yloxy, pyrimidine-5- Iloxy, pyrazine-2-yloxy, pyridazine-3-yloxy, pyridazine-4-yloxy, 1,2,3-triazine-4-yloxy, 1,2,3-triazine-5-yloxy, 1,2,4-triazine-3-yloxy, 1,2,4-triazine-5-yloxy, 1,2,4-triazine-6-yloxy, 1,3,5-triazine-2-yloxy, thiophene-2-yloxy, thiophene-3-yloxy, furan-2-yloxy, furan-3-yloxy, pyrazole-1-yloxy, pyrazole-3-yloxy, pyrazole Zol-4-yloxy, pyrazole-5-yloxy, thiazole-2-yloxy, thiazole-4-yloxy, thiazole-5-yloxy, isothiazole-3-yloxy, isothiazole-4-yloxy, isothiazole-5-yloxy, oxazole-2-yloxy, oxazole-4-yloxy, oxazole-5-yloxy, isoxazole-3-yloxy, isoxazole-4-yloxy, isoxazole-5-yloxy, imidazole-2-yloxy, imidazole-4-yloxy, imidazole -5-yloxy, 1,2,3-triazole-1-yloxy, 1,2,3-triazole-4-yloxy, 1,2,3-triazole-5-yloxy, 1,2,4-triazole-1-yloxy, 1,2,4-triazole-3-yloxy, 1,2,4-triazole-5-yloxy, 1,3,4-thiadiazole-2-yloxy, 1,2,3-thiadiazole-4-yloxy, 1,2,3-thiadiazole-5-yloxy, 1,2,4-thiadiazole-3-yloxy, 1,2,4-thiadiazole-5-yloxy, 1,2,Examples of groups include 5-thiadiazole-3-yloxy, 1,3,4-oxadiazole-2-yloxy, 1,2,3-oxadiazole-4-yloxy, 1,2,3-oxadiazole-5-yloxy, 1,2,4-oxadiazole-3-yloxy, 1,2,4-oxadiazole-5-yloxy, or 1,2,5-oxadiazole-3-yloxy. As a condensed bicyclic heterocycle, one of the monocyclic groups and a phenyl ring, or any of the groups of the monocyclic aromatic heterocycle, C8~C, 10Condensed bicyclic moieties formed by condensation to form a bicyclic group, for example, indole-1-yloxy, indole-2-yloxy, indole-3-yloxy, indole-4-yloxy, indole-5-yloxy, indole-6-yloxy, indole-7-yloxy, 1,3-benzodioxol-4-yloxy, 1,3-benzodioxol-5-yloxy, 2,3-dihydrobenzofuran-4-yloxy, 2,3-dihydrobenzofuran-5-yloxy, 2,3-dihydrobenzofuran-6-yloxy, 2,3-dihydrobenzofuran-7-yloxy, 1,4-benzodioxane-5-yloxy, 1,4-benzodioxan-6-yloxy, chroman-5-yloxy, chroman-6-yloxy, chroman-7-yloxy, chroman-8-yloxy, benzimidazole-1-yloxy, benzimidazole-2-yloxy, benzimidazole-4-yloxy, benzimidazole-5-yloxy, benzimidazole-6-yloxy, benzimidazole-7-yloxy, indazole-1-yloxy, indazole-3-yloxy, indazole-4-yloxy, indazole-5-yloxy, indazole-6-yloxy Isoquinoline-1-yloxy, benzotriazole-1-yloxy, benzotriazole-4-yloxy, benzotriazole-5-yloxy, benzotriazole-6-yloxy, benzotriazole-7-yloxy, isoquinoline-1-yloxy, isoquinoline-3-yloxy, isoquinoline-4-yloxy, isoquinoline-5-yloxy, isoquinoline-6-yloxy, isoquinoline-7-yloxy, isoquinoline-8-yloxy, quinoline-2-yloxy, quinoline-3-yloxy, quinoline-4-yloxy Iroxy, quinoline-5-yloxy, quinoline-6-yloxy, quinoline-7-yloxy, quinoline-8-yloxy, benzothiazole-2-yloxy, benzothiazole-4-yloxy, benzothiazole-5-yloxy, benzothiazole-6-yloxy, benzothiazole-7-yloxy, benzofuran-2-yloxy, benzofuran-3-yloxy, benzofuran-4-yloxy, benzofuran-5-yloxy, benzofuran-6-yloxy, benzofuran-7-yloxy, benzothiophene-2-yloxy, Benzothiophene-3-yloxy, benzothiophene-4-yloxy, benzothiophene-5-yloxy, benzothiophene-6-yloxy, benzothiophene-7-yloxy, benzoxazole-2-yloxy, benzoxazole-4-yloxy, benzoxazole-5-yloxy, benzoxazole-6-yloxy, benzoxazole-7-yloxy, 1,2-benzisoxazole-3-yloxy, 1,2-benzisoxazole-4-yloxy, 1,2-benzisoxazole-5-yloxy, 1,2-Benzisoxazole-6-yloxy, 1,2-Benzisoxazole-7-yloxy, Pyrazolopyridine-1-yloxy, Pyrazolopyridine-3-yloxy, Pyrazolopyridine-4-yloxy, Pyrazolopyridine-5-yloxy, Pyrazolopyridine-6-yloxy, Quinazolin-2-yloxy, Quinazolin-4-yloxy, Quinazolin-5-yloxy, Quinazolin-6-yloxy, Quinazolin-7-yloxy, Examples of such groups include nazoline-8-yloxy, quinoxaline-2-yloxy, quinoxaline-3-yloxy, quinoxaline-5-yloxy, quinoxaline-6-yloxy, quinoxaline-7-yloxy, quinoxaline-8-yloxy, cinnoline-3-yloxy, cinnoline-4-yloxy, cinnoline-5-yloxy, cinnoline-6-yloxy, cinnoline-7-yloxy, or cinnoline-8-yloxy.

[0047] In the present invention, "5-12 member heteroaryl-C1-C6 alkoxy group" refers to a (5-12 member heteroaryl)-(C1-C6 alkoxy)-group where the 5-12 member heteroaryl moiety and the alkoxy moiety have the meanings described above, unless otherwise specified. Examples include pyridine-2-ylmethoxy, pyridine-3-ylmethoxy, pyridine-4-ylmethoxy, pyridinone-1-ylmethoxy, pyridinone-3-ylmethoxy, pyridinone-4-ylmethoxy, pyridinone-5-ylmethoxy, pyridinone-6-ylmethoxy, and pyrimidine-2-ylmethoxy. Pyrimidine-4-ylmethoxy, pyrimidine-5-ylmethoxy, pyrazine-2-ylmethoxy, pyridazine-3-ylmethoxy, pyridazine-4-ylmethoxy, 1,2,3-triazine-4-ylmethoxy, 1,2,3-triazine-5-ylmethoxy, 1,2,4-triazine-3-ylmethoxy, 1,2,4-triazine-5-ylmethoxy, 1,2,4-triazine-6-ylmethoxy, 1,3,5-triazine-2-ylmethoxy, thiophene-2-ylmethoxy, thiophene-3-ylmethoxy, furan-2-ylmethoxy, fura I-3-ylmethoxy, pyrazole-1-ylmethoxy, pyrazole-3-ylmethoxy, pyrazole-4-ylmethoxy, pyrazole-5-ylmethoxy, thiazole-2-ylmethoxy, thiazole-4-ylmethoxy, thiazole-5-ylmethoxy, isothiazole-3-ylmethoxy, isothiazole-4-ylmethoxy, isothiazole-5-ylmethoxy, oxazole-2-ylmethoxy, oxazole-4-ylmethoxy, oxazole-5-ylmethoxy, isooxazole-3-ylmethoxy, isooxazole-4-ylmethoxy Methoxy, isoxazole-5-ylmethoxy, imidazole-1-ylmethoxy, imidazole-2-ylmethoxy, imidazole-4-ylmethoxy, imidazole-5-ylmethoxy, 1,2,3-triazole-1-ylmethoxy, 1,2,3-triazole-4-ylmethoxy, 1,2,3-triazole-5-ylmethoxy, 1,2,4-triazole-1-ylmethoxy, 1,2,4-triazole-3-ylmethoxy, 1,2,4-triazole-5-ylmethoxy, 1,3,4-thiadiazole-2-ylmethoxy, 1,2,Examples of such groups include 3-thiadiazole-4-ylmethoxy, 1,2,3-thiadiazole-5-ylmethoxy, 1,2,4-thiadiazole-3-ylmethoxy, 1,2,4-thiadiazole-5-ylmethoxy, 1,2,5-thiadiazole-3-ylmethoxy, 1,3,4-oxadiazole-2-ylmethoxy, 1,2,3-oxadiazole-4-ylmethoxy, 1,2,3-oxadiazole-5-ylmethoxy, 1,2,4-oxadiazole-3-ylmethoxy, 1,2,4-oxadiazole-5-ylmethoxy, or 1,2,5-oxadiazole-3-ylmethoxy. As a condensed bicyclic heterocycle, one of the monocyclic groups and a phenyl ring, or any of the groups of the monocyclic aromatic heterocycle, C8~C, 10Condensed bicyclic moieties formed by condensation to form a bicyclic group, for example, indole-1-ylmethoxy, indole-2-ylmethoxy, indole-3-ylmethoxy, indole-4-ylmethoxy, indole-5-ylmethoxy, indole-6-ylmethoxy, indole-7-ylmethoxy, 1,3-benzodioxol-4-ylmethoxy, 1,3-benzodioxol-5-ylmethoxy, 2,3-dihydrobenzofuran-4-ylmethoxy, 2,3-dihydrobenzofuran-5-ylmethoxy, 2,3-dihydrobenzofuran-6-ylmethoxy, 2,3-dihydrobenzofuran-7-ylmethoxy, 1,4-benzodioxane-5-ylmethoxy, 1,4-Benzodioxan-6-ylmethoxy, croman-5-ylmethoxy, croman-6-ylmethoxy, croman-7-ylmethoxy, croman-8-ylmethoxy, benzimidazole-1-ylmethoxy, benzimidazole-2-ylmethoxy, benzimidazole-4-ylmethoxy, benzimidazole-5-ylmethoxy, benzimidazole-6-ylmethoxy, benzimidazole-7-ylmethoxy, indazole-1-ylmethoxy, indazole-3-ylmethoxy, indazole-4-ylmethoxy, indazole-5-ylmethoxy Methoxy, indazole-6-ylmethoxy, indazole-7-ylmethoxy, 1H-benzotriazole-1-ylmethoxy, 1H-benzotriazole-4-ylmethoxy, 1H-benzotriazole-5-ylmethoxy, 1H-benzotriazole-6-ylmethoxy, 1H-benzotriazole-7-ylmethoxy, isoquinoline-1-ylmethoxy, isoquinoline-3-ylmethoxy, isoquinoline-4-ylmethoxy, isoquinoline-5-ylmethoxy, isoquinoline-6-ylmethoxy, isoquinoline-7-ylmethoxy, isoquinoline -8-ylmethoxy, quinoline-2-ylmethoxy, quinoline-3-ylmethoxy, quinoline-4-ylmethoxy, quinoline-5-ylmethoxy, quinoline-6-ylmethoxy, quinoline-7-ylmethoxy, quinoline-8-ylmethoxy, benzothiazole-2-ylmethoxy, benzothiazole-4-ylmethoxy, benzothiazole-5-ylmethoxy, benzothiazole-6-ylmethoxy, benzothiazole-7-ylmethoxy, benzofuran-2-ylmethoxy, benzofuran-3-ylmethoxy, benzofuran-4-ylmethoxy, benzo 1, 1,2-Benzisoxazole-3-ylmethoxy, 1,2-Benzisoxazole-4-ylmethoxy, 1,2-Benzisoxazole-5-ylmethoxy, 1,2-Benzisoxazole-6-ylmethoxy, 1,2-Benzisoxazole-7-ylmethoxy, Pyrazolopyridine-1-ylmethoxy, Pyrazolopyridine-3-ylmethoxy, Pyrazolopyridine-4-ylmethoxy, Pyrazolopyridine-5-ylmethoxy, Pyrazolopyridine-6-ylmethoxy, Quinazoline-2-ylmethoxy, Quinazoline-4-ylmethoxy, Quinazoline-5-ylmethoxy Examples of groups include quinoxaline-6-ylmethoxy, quinoxaline-7-ylmethoxy, quinoxaline-8-ylmethoxy, quinoxaline-2-ylmethoxy, quinoxaline-3-ylmethoxy, quinoxaline-5-ylmethoxy, quinoxaline-6-ylmethoxy, quinoxaline-7-ylmethoxy, quinoxaline-8-ylmethoxy, sinnoline-3-ylmethoxy, sinnoline-4-ylmethoxy, sinnoline-5-ylmethoxy, sinnoline-6-ylmethoxy, sinnoline-7-ylmethoxy, or sinnoline-8-ylmethoxy.

[0048] In the present invention, unless otherwise specified, "C1-C6 alkylamino group" refers to a (C1-C6 alkyl)-NH- group in which the alkyl portion has the meaning described above. Examples of such groups include methylamino, ethylamino, isopropylamino, tert-butylamino, n-propylamino, sec-butylamino, isobutylamino, n-butylamino, 2-methylbutan-1-ylamino, 2-ethylbutan-2-ylamino, 3-methylbutan-2-ylamino, n-pentylamino, 2-methylpentan-2-ylamino, pentan-3-ylamino, isopentylamino, neopentylamino, sec-pentylamino, tert-pentylamino, or n-hexylamino.

[0049] In this invention, "aminocarbonyl group" refers to an N2H-C(=O)- group.

[0050] In the present invention, unless otherwise specified, "C1-C6 alkylaminocarbonyl group" refers to a (C1-C6 alkyl)-NH-C(=O)- group where the alkyl portion has the meaning described above. Examples of such groups include methylaminocarbonyl, ethylaminocarbonyl, isopropylaminocarbonyl, tert-butylaminocarbonyl, n-propylaminocarbonyl, sec-butylaminocarbonyl, isobutylaminocarbonyl, n-butylaminocarbonyl, 2-methylbutan-1-ylaminocarbonyl, 2-ethylbutan-2-ylaminocarbonyl, 3-methylbutan-2-ylaminocarbonyl, n-pentylaminocarbonyl, 2-methylpentan-2-ylaminocarbonyl, pentan-3-ylaminocarbonyl, isopentylaminocarbonyl, neopentylaminocarbonyl, sec-pentylaminocarbonyl, tert-pentylaminocarbonyl, or n-hexylaminocarbonyl.

[0051] In the present invention, unless otherwise specified, "C1-C6 alkylcarbonylamino group" refers to a (C1-C6 alkyl)-C(=O)-NH- group where the alkyl portion has the meaning described above. Examples of such groups include methylcarbonylamino, ethylcarbonylamino, isopropylcarbonylamino, tert-butylcarbonylamino, n-propylcarbonylamino, sec-butylcarbonylamino, isobutylcarbonylamino, n-butylcarbonylamino, 2-methylbutan-1-ylcarbonylamino, 3-methylbutan-2-ylcarbonylamino, n-pentylcarbonylamino, pentan-3-ylcarbonylamino, isopentylcarbonylamino, neopentylcarbonylamino, sec-pentylcarbonylamino, tert-pentylcarbonylamino, or n-hexylcarbonylamino.

[0052] In the present invention, unless otherwise specified, "C1-C6 alkyl-C3-C8 cycloalkylcarbonylamino group" means the alkyl portion and cycloalkyl portion as described above, and refers to a (C1-C6 alkyl)-(C3-C8 cycloalkyl)-C(=O)-NH- group in which an alkyl group is substituted on the cycloalkyl portion. Examples of such groups include 1-methylcyclopropanecarbonylamino, 1-methylcyclobutanecarbonylamino, 1-methylcyclopentanecarbonylamino, or 1-methylcyclohexanecarbonylamino.

[0053] In the present invention, unless otherwise specified, "C1-C6 alkylaminocarbonylamino group" refers to a (C1-C6 alkyl)-NH-C(=O)-NH- group where the alkyl portion has the meaning described above, for example, methylaminocarbonylamino, ethylaminocarbonylamino, isopropylaminocarbonylamino, tert-butylaminocarbonylamino, n-propylaminocarbonylamino, sec-butylaminocarbonylamino, isobutylaminocarbonylamino, n-butylaminocarbonylamino, 2-methylbutane- Examples of groups include 1-ylaminocarbonylamino, 2-ethylbutan-2-ylaminocarbonylamino, 3-methylbutan-2-ylaminocarbonylamino, n-pentylaminocarbonylamino, 2-methylpentan-2-ylaminocarbonylamino, pentan-3-ylaminocarbonylamino, isopentylaminocarbonylamino, neopentylaminocarbonylamino, sec-pentylaminocarbonylamino, tert-pentylaminocarbonylamino, or n-hexylaminocarbonylamino.

[0054] In the present invention, unless otherwise specified, "5-12 member heteroarylcarbonylamino group" refers to a (5-12 member heteroaryl)-C(=O)-NH- group in which the 5-12 member heteroaryl portion has the above meaning, for example, pyridine-2-ylcarbonylamino, pyridine-3-ylcarbonylamino, pyridine-4-ylcarbonylamino, pyridinone-1-ylcarbonylamino, pyridinone-3-ylcarbonylamino, pyridinone-4-ylcarbonylamino, pyridinone-5-ylcarbonylamino, pyridinone-6-ylcarbonylamino Pyrimidine-2-ylcarbonylamino, pyrimidine-4-ylcarbonylamino, pyrimidine-5-ylcarbonylamino, pyrazine-2-ylcarbonylamino, pyridazine-3-ylcarbonylamino, pyridazine-4-ylcarbonylamino, 1,2,3-triazine-4-ylcarbonylamino, 1,2,3-triazine-5-ylcarbonylamino, 1,2,4-triazine-3-ylcarbonylamino, 1,2,4-triazine-5-ylcarbonylamino, 1,2,4-triazine-6-ylcarbonylamino, 1,3,5-tri Adin-2-ylcarbonylamino, thiophene-2-ylcarbonylamino, thiophene-3-ylcarbonylamino, furan-2-ylcarbonylamino, furan-3-ylcarbonylamino, pyrazole-1-ylcarbonylamino, pyrazole-3-ylcarbonylamino, pyrazole-4-ylcarbonylamino, pyrazole-5-ylcarbonylamino, thiazole-2-ylcarbonylamino, thiazole-4-ylcarbonylamino, thiazole-5-ylcarbonylamino, isothiazole-3-ylcarbonylamino, isothiazole Zol-4-ylcarbonylamino, isothiazole-5-ylcarbonylamino, oxazole-2-ylcarbonylamino, oxazole-4-ylcarbonylamino, oxazole-5-ylcarbonylamino, isoxazole-3-ylcarbonylamino, isoxazole-4-ylcarbonylamino, isoxazole-5-ylcarbonylamino, imidazole-1-ylcarbonylamino, imidazole-2-ylcarbonylamino, imidazole-4-ylcarbonylamino, imidazole-5-ylcarbonylamino, 1,2,3-Triazole-1-ylcarbonylamino, 1,2,3-Triazole-4-ylcarbonylamino, 1,2,3-Triazole-5-ylcarbonylamino, 1,2,4-Triazole-1-ylcarbonylamino, 1,2,4-Triazole-3-ylcarbonylamino, 1,2,4-Triazole-5-ylcarbonylamino, 1,3,4-Thiadianazole-2-ylcarbonylamino, 1,2,3-Thiadianazole-4-ylcarbonylamino, 1,2,3-Thiadianazole-5-ylcarbonylamino, 1,2,4-Thiadianazole-3-ylcarbonylamino, 1,2,4-Thiadianazole-5-yl Examples of such groups include carbonylamino, 1,2,5-thiadiazole-3-ylcarbonylamino, 1,3,4-oxadiazole-2-ylcarbonylamino, 1,2,3-oxadiazole-4-ylcarbonylamino, 1,2,3-oxadiazole-5-ylcarbonylamino, 1,2,4-oxadiazole-3-ylcarbonylamino, 1,2,4-oxadiazole-5-ylcarbonylamino, or 1,2,5-oxadiazole-3-ylcarbonylamino. As a condensed bicyclic heterocycle, one of the monocyclic groups and a phenyl ring, or any of the monocyclic aromatic heterocycle groups and C8~C, 10Condensed bicyclic moieties formed by condensation to form a bicyclic group, for example, indole-1-ylcarbonylamino, indole-2-ylcarbonylamino, indole-3-ylcarbonylamino, indole-4-ylcarbonylamino, indole-5-ylcarbonylamino, indole-6-ylcarbonylamino, indole-7-ylcarbonylamino, 1,3-benzodioxole-4-ylcarbonylamino, 1,3-benzodioxole-5-ylcarbonylamino, 2,3-dihydrobenzofuran-4-ylcarbonylamino Rubonylamino, 2,3-dihydrobenzofuran-5-ylcarbonylamino, 2,3-dihydrobenzofuran-6-ylcarbonylamino, 2,3-dihydrobenzofuran-7-ylcarbonylamino, 1,4-benzodioxane-5-ylcarbonylamino, 1,4-benzodioxane-6-ylcarbonylamino, chroman-5-ylcarbonylamino, chroman-6-ylcarbonylamino, chroman-7-ylcarbonylamino, chroman-8-ylcarbonylamino, benzimidazole-1-ylcarbonylamino, benzimidazole -2-Ilcarbonylamino, Benzimidazole-4-Ilcarbonylamino, Benzimidazole-5-Ilcarbonylamino, Benzimidazole-6-Ilcarbonylamino, Benzimidazole-7-Ilcarbonylamino, Indazole-1-Ilcarbonylamino, Indazole-3-Ilcarbonylamino, Indazole-4-Ilcarbonylamino, Indazole-5-Ilcarbonylamino, Indazole-6-Ilcarbonylamino, Indazole-7-Ilcarbonylamino, 1H-Benzotriazole-1-Ilcarbonyl Amino, 1H-benzotriazole-4-ylcarbonylamino, 1H-benzotriazole-5-ylcarbonylamino, 1H-benzotriazole-6-ylcarbonylamino, 1H-benzotriazole-7-ylcarbonylamino, isoquinoline-1-ylcarbonylamino, isoquinoline-3-ylcarbonylamino, isoquinoline-4-ylcarbonylamino, isoquinoline-5-ylcarbonylamino, isoquinoline-6-ylcarbonylamino, isoquinoline-7-ylcarbonylamino, isoquinoline-8-ylcarbonylamino,Quinoline-2-ylcarbonylamino, Quinoline-3-ylcarbonylamino, Quinoline-4-ylcarbonylamino, Quinoline-5-ylcarbonylamino, Quinoline-6-ylcarbonylamino, Quinoline-7-ylcarbonylamino, Quinoline-8-ylcarbonylamino, Benzothiazole-2-ylcarbonylamino, Benzothiazole-4-ylcarbonylamino, Benzothiazole-5-ylcarbonylamino, Benzothiazole-6-ylcarbonylamino, Benzothiazole-7-ylcarbonylamino, Benzofuran-2-ylcarbonylamino Rubonylamino, benzofuran-3-ylcarbonylamino, benzofuran-4-ylcarbonylamino, benzofuran-5-ylcarbonylamino, benzofuran-6-ylcarbonylamino, benzofuran-7-ylcarbonylamino, benzothiophene-2-ylcarbonylamino, benzothiophene-3-ylcarbonylamino, benzothiophene-4-ylcarbonylamino, benzothiophene-5-ylcarbonylamino, benzothiophene-6-ylcarbonylamino, benzothiophene-7-ylcarbonylamino, benzooxazo 2-ylcarbonylamino, benzoxazole-4-ylcarbonylamino, benzoxazole-5-ylcarbonylamino, benzoxazole-6-ylcarbonylamino, benzoxazole-7-ylcarbonylamino, 1,2-benzisoxazole-3-ylcarbonylamino, 1,2-benzisoxazole-4-ylcarbonylamino, 1,2-benzisoxazole-5-ylcarbonylamino, 1,2-benzisoxazole-6-ylcarbonylamino, 1,2-benzisoxazole-7-ylcarbonyl Amino, pyrazolopyridine-1-ylcarbonylamino, pyrazolopyridine-3-ylcarbonylamino, pyrazolopyridine-4-ylcarbonylamino, pyrazolopyridine-5-ylcarbonylamino, pyrazolopyridine-6-ylcarbonylamino, quinazolin-2-ylcarbonylamino, quinazolin-4-ylcarbonylamino, quinazolin-5-ylcarbonylamino, quinazolin-6-ylcarbonylamino, quinazolin-7-ylcarbonylamino, quinazolin-8-ylcarbonylamino, quinoxaline-2-ylcarbonylamino,Examples of such groups include quinoxaline-3-ylcarbonylamino, quinoxaline-5-ylcarbonylamino, quinoxaline-6-ylcarbonylamino, quinoxaline-7-ylcarbonylamino, quinoxaline-8-ylcarbonylamino, cinnoline-3-ylcarbonylamino, cinnoline-4-ylcarbonylamino, cinnoline-5-ylcarbonylamino, cinnoline-6-ylcarbonylamino, cinnoline-7-ylcarbonylamino, or cinnoline-8-ylcarbonylamino.

[0055] In this invention, "one or more R 10 "May be substituted with substituents selected from" means "one or two or more R 10 This means that substitution may be made by substituents selected from the following. 10 If replaced by R 10 Each of them may be the same or different, R 10 These are hydroxyl groups, halogen atoms, cyano groups, C1-C6 alkyl groups, C1-C6 haloalkyl groups, C1-C6 alkoxy-C1-C6 alkyl groups, C1-C6 alkoxy groups, and C6-C 12 Aryl-C1~C6 alkoxy group, C1~C6 alkoxy-C1~C6 alkoxy group, cyano-C1~C6 alkoxy group, C1~C6 alkylsulfanyl group, C1~C6 alkylsulfinyl group, C1~C6 alkylsulfonyl group, C1~C6 alkylcarbonylamino group (the amino group is R 9 (May be substituted with substituents selected from), C1-C6 alkylaminocarbonylamino group (the amino group is R 9 (May be substituted with substituents selected from), C6~C 12 Aryl group, C6~C 12 Aryloxy group, 5-12 member heteroarylcarbonylamino group, 5-12 member heteroaryloxy group, 5-12 member heteroaryl-C1-C6 alkoxy group, or -C(=NR) 7 )R 8 It indicates the basis.

[0056] In this invention, "one or more R 9"May be substituted with substituents selected from" means "one or two or more R 9 This means that substitution may be made by substituents selected from the following. 9 If replaced by R 9 Each of them may be the same or different, R 9 This represents a hydrogen atom or a C1-C6 alkyl group.

[0057] In the present invention, a salt is a salt of a metal or organic base, or a mineral acid or organic acid, when a nitrogen-containing heterocyclic group, hydroxyl group, carboxyl group, or amino group, etc., is present in the structure of the compound of the present invention represented by general formula [I]. Examples of metals include alkali metals such as sodium or potassium, or alkaline earth metals such as magnesium or calcium. Examples of organic bases include triethylamine or diisopropylamine. Examples of mineral acids include hydrochloric acid, hydrobromic acid, or sulfuric acid. Examples of organic acids include formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, 4-toluenesulfonic acid, or trifluoromethanesulfonic acid.

[0058] Next, Tables 1 to 10 show representative examples of compounds included in the pyrazole-4-oxadiazine ring compound of the present invention, represented by general formula [I]. However, the compounds included in the present invention are not limited to these. Also, the compound numbers in the tables will be referenced in the following description.

[0059] Furthermore, while compounds included in the pyrazole-4-oxadiazine ring compounds of the present invention may have optical isomers due to the presence of one or more chiral carbon atoms and chiral sulfur atoms, the present invention encompasses all optically active compounds, racemates, or diastereomers.

[0060] Furthermore, while compounds included in the pyrazole-4-oxadiazine ring compounds of the present invention may have tautomers depending on the type of substituent, the present invention includes mixtures containing these in any proportion. Also, the naming of the compounds is not limited to any tautomers, and examples include, but are not limited to, those listed below. [ka]

[0061] In the tables used herein, the following notations represent the respective groups, for example, as shown below. Me: methyl; Et: ethyl; Pr-n: n-propyl; Pr-i: Isopropyl; Bu-n: n-butyl; Bu-i: Isobutyl; Bu-s:sec-butyl; But-t: tert-butyl; Pen-n: n-pentyl; Pen-i: isopentyl; Pen-s :sec-pentyl; Pen-neo: Neo-Pentyl; pen-t :tert-amir; Hex-n: n-hexyl; CF2H: Difluoromethyl; CF3: Trifluoromethyl; CH2CF3:2,2,2-trifluoroethyl; Pr-c: Cyclopropyl; Pr-c(1-Me):1-methylcyclopropyl; Bu-c: Cyclobutyl; Pen-c: Cyclopentyl; Hex-c: Cyclohexyl; Ac:methylcarbonyl; C(=O)OMe: Methyl ester; pyridin-3-yl: pyridin-3-yl; Ph(2,4-Me2): 2,4-dimethylphenyl; pyridin-3-yl(5-Cl): 5-chloropyridine-3-yl; pyrazol(1-Me)-5-yl: 1-methylpyrazole-5-yl;

[0062] [Table 01]

[0063] [Table 02]

[0064] [Table 03]

[0065] [Table 04]

[0066] [Table 05]

[0067] [Table 06]

[0068] [Table 07]

[0069] [Table 08]

[0070] [Table 09]

[0071] [Table 10]

[0072] On the other hand, the compound of the present invention represented by general formula [I] can be produced according to the following manufacturing methods, but is not limited to these methods. Hereinafter, for example, "compound represented by general formula [I]" and "compound [I]" are considered synonymous.

[0073] <Manufacturing method 1> Among the compounds of the present invention, the compound represented by general formula [I] can be produced according to the following method.

[0074] [ka]

[0075] (In the formula, A, R 1 , R 2 , R 3 , R 4 , R 5 , R 5’ R 6 , R 6’ Q 1 , and Q 2 (This has the same meaning as above.)

[0076] That is, the compound represented by general formula [I] can be produced by reacting compound [V] with a suitable solvent in the presence of a reactant such as thionyl chloride, oxalyl chloride, phosphoryl chloride, isobutyl chlorocarbonate, methanesulfonyl chloride, trifluoromethanesulfonyl chloride, or p-toluenesulfonyl chloride.

[0077] The amount of reagent used in this reaction can be appropriately selected from the range of 1 to 5 moles per mole of compound [V], and preferably 3.0 to 4.0 moles.

[0078] Examples of solvents that can be used in this reaction include halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; nitriles such as acetonitrile and propionitrile; or mixed solvents thereof. The amount of solvent used is 0.1 to 100 liters per mole of compound [V], preferably 0.3 to 50 liters.

[0079] The reaction temperature for this reaction can be selected from any temperature range from -20°C to the reflux temperature of the reaction system, and is preferably carried out in the range of 0°C to 100°C. The reaction time for this reaction varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 1 minute to 96 hours.

[0080] After the reaction is complete, compound [I] can be isolated by adding a saturated sodium bicarbonate aqueous solution to the reaction mixture, extracting it with an organic solvent, and then concentrating the mixture. The isolated compound [I] can be further purified by column chromatography, recrystallization, or other methods as needed.

[0081] <Manufacturing method 2> Among the compounds of the present invention, the compound represented by general formula [V] can be produced according to the following method.

[0082] [ka]

[0083] (In the formula, A, R 1 , R 2 , R 3 , R 4 , R 5 , R 5’ R 6 , R 6’ Q 1 , and Q 2 (This has the same meaning as above.)

[0084] In other words, the compound represented by general formula [V] can be produced by reacting compound [IV] with a suitable solvent in the presence of a reactant such as hydrazine hydrate, sulfuric acid, hydrochloric acid, or acetic acid.

[0085] The amount of reagent used in this reaction can be appropriately selected from the range of 1 to 5 moles per mole of compound [IV], and preferably 2.0 to 3.0 moles.

[0086] Examples of solvents that can be used in this reaction include halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; or mixed solvents thereof. The amount of solvent used is 0.1 to 100 liters per mole of compound [IV], preferably 0.3 to 50 liters.

[0087] The reaction temperature for this reaction can be selected from any temperature range from -20°C to the reflux temperature of the reaction system, and is preferably carried out in the range of 0°C to 100°C. The reaction time for this reaction varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 1 minute to 96 hours.

[0088] After the reaction is complete, compound [V] can be isolated by adding water to the reaction mixture, extracting it with an organic solvent, and then filtering or concentrating the solid precipitated with an acid such as hydrochloric acid.

[0089] <Manufacturing method 3> Among the compounds of the present invention, the compound represented by general formula [IV] can be produced according to the following method.

[0090] [ka]

[0091] (In the formula, W1 represents a halogen atom or a trifluoroacetoxy group, U represents a halogen atom, A, R 1 , R 2 , R 3 , R 4 , R 5 , R 5’ R 6 , R 6’ , Q 1 , and Q 2 have the same meaning as described above.)

[0092] That is, the compound represented by the general formula [IV] can be produced by reacting the compound [II] in a suitable solvent with or without a suitable catalyst to obtain the compound [III] which is an active derivative such as an acid halide, and then (Step 3-2) reacting the compound [III] with the compound [X-1] or the compound [X-2] in a suitable solvent with or without a suitable base. Further, the compound represented by the general formula [IV] can also be produced by reacting the compound [II] with the compound [X-1] or the compound [X-2] in a suitable solvent with or without a suitable condensing agent, with or without a suitable additive, with or without a suitable catalyst, and with or without a suitable base.

[0093] (Step 3-1) Examples of the reagent for converting the compound [II] to the compound [III] used in this reaction include thionyl chloride, oxalyl chloride, phosphoryl chloride, isobutyl chloroformate, methanesulfonyl chloride, trifluoromethanesulfonyl chloride, or p-toluenesulfonyl chloride. The amount of the reagent used for the conversion to the compound [III] may be appropriately selected from the range of 1 to 5 moles per 1 mole of the compound [II], and preferably 1.0 to 3.0 moles.

[0094] Examples of the catalyst that can be used in this reaction include N,N-dimethylformamide. The amount of the catalyst used may be appropriately selected from the range of 0.01 to 1.0 mole per 1 mole of the compound [II], and preferably 0.01 to 0.1 mole.

[0095] Examples of solvents that can be used in this reaction include ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; nitriles such as acetonitrile and propionitrile; or mixed solvents thereof. The amount of solvent used is 0.1 to 100 liters per mole of compound [II], preferably 0.3 to 50 liters.

[0096] The reaction temperature for this reaction can be selected from any temperature range from -20°C to the reflux temperature of the reaction system, and is preferably carried out in the range of 0°C to 150°C. The reaction time for this reaction varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 1 minute to 96 hours.

[0097] After the reaction is complete, compound [III] can be isolated by performing operations such as concentration.

[0098] (Step 3-2) The amount of compound [X-1] or compound [X-2] used in this reaction can be appropriately selected from the range of 1 to 5 moles per mole of compound [III], and preferably 1.0 to 2.5 moles.

[0099] Examples of bases that can be used in this reaction include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; inorganic bases such as alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; alkali metal phosphates such as tripotassium phosphate; metal hydrides such as sodium hydride and potassium hydride; metal salts of alcohols such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; or organic bases such as triethylamine, N,N-dimethylaniline, pyridine, 4-methylmorpholine, N-ethyldiisopropylamine, 4-N,N-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, 2,6-lutidine, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and potassium bis(trimethylsilyl)amide. The amount of base used can be appropriately selected from the range of 1.0 to 5.0 moles per mole of compound [III], and preferably 1.0 to 3.5 moles.

[0100] Examples of solvents that can be used in this reaction include halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; nitriles such as acetonitrile and propionitrile; ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; or mixed solvents thereof. The amount of solvent used is 0.1 to 100 liters per mole of compound [III], preferably 0.3 to 50 liters.

[0101] The reaction temperature for this reaction can be selected from any temperature range from -20°C to the reflux temperature of the reaction system, and is preferably in the range of 0°C to 80°C. The reaction time for this reaction varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually from 1 minute to 96 hours.

[0102] After the reaction is complete, compound [IV] can be isolated by adding a saturated sodium bicarbonate aqueous solution to the reaction mixture, extracting it with an organic solvent, and then concentrating the mixture. The isolated compound [IV] can be further purified by column chromatography, recrystallization, etc., as needed.

[0103] (Step 3-3) The amount of compound [X-1] or compound [X-2] used in this reaction can be appropriately selected from the range of 1 to 3 moles per mole of compound [II], and preferably 1.0 to 1.5 moles.

[0104] Examples of condensing agents that can be used in this reaction include 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, N,N'-carbonyldiimidazole, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, and 1H- Examples of suitable condensing agents include nzotriazole-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate, ({[(1-cyano-2-ethoxy-2-oxoethylidene)amino]oxy}-4-morpholinomethylene)dimethylammonium hexafluorophosphate, O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, and propylphosphonic anhydride. The amount of condensing agent used should be appropriately selected from the range of 1.0 to 5.0 moles per mole of compound[II], and preferably 1.0 to 3.0 moles.

[0105] Examples of catalysts that can be used in this reaction include 4-N,N-dimethylaminopyridine. The amount of catalyst used can be appropriately selected from the range of 0.01 to 1.0 moles per mole of compound [II], and preferably 0.01 to 0.1 moles.

[0106] Examples of additives that can be used in this reaction include 1-hydroxybenzotriazole, N-hydroxysuccinimide, and 1-hydroxy-7-azabenzotriazole. The amount of additive used should be appropriately selected from 0.01 to 3.0 moles per mole of compound[II], and preferably 1.0 to 1.5 moles.

[0107] Examples of bases that can be used in this reaction include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; inorganic bases such as alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; alkali metal phosphates such as tripotassium phosphate; metal hydrides such as sodium hydride and potassium hydride; metal salts of alcohols such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; or organic bases such as triethylamine, N,N-dimethylaniline, pyridine, 4-methylmorpholine, N-ethyldiisopropylamine, 4-N,N-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, 2,6-lutidine, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and potassium bis(trimethylsilyl)amide. The amount of base used can be appropriately selected from the range of 1.0 to 10.0 moles per mole of compound [II], and preferably 0.1 to 5.0 moles.

[0108] The reaction temperature for this reaction can be selected from any temperature range from -20°C to the reflux temperature of the reaction system, and is preferably in the range of 0°C to 80°C. The reaction time for this reaction varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually from 1 minute to 96 hours.

[0109] After the reaction is complete, compound [IV] can be isolated by adding water to the reaction mixture and filtering out the precipitated solid, or by extracting it with an organic solvent and then concentrating it. The isolated compound [IV] can be further purified by column chromatography, recrystallization, etc., as needed.

[0110] Furthermore, the amine derivative [X-1] or amine derivative [X-2] used as a raw material can be obtained by known methods, such as those described in International Publication No. 2020 / 127780 and International Publication No. 2021 / 255071.

[0111] <Manufacturing method 4> Among the compounds of the present invention, the compound represented by general formula [VIII] can be produced according to the following method.

[0112] [ka]

[0113] (In the formula, R 1 , R 2 , and Q 1 (This has the same meaning as above.)

[0114] That is, the compound represented by general formula [VIII] can be produced by reacting the compound represented by general formula [VII] with a suitable oxidizing agent in a suitable solvent, with or without a catalyst.

[0115] Examples of oxidizing agents that can be used in this reaction include organic peroxides such as m-chloroperbenzoic acid, performic acid, peracetic acid, or trifluoroperacetic acid; inorganic peroxides such as hydrogen peroxide, potassium permanganate, Oxon® (trade name of I. DuPont, containing potassium peroxobisulfate), and tert-butylhydroperoxide; and halide salts such as sodium periodate, sodium chlorite, and sodium hypochlorite. The amount of oxidizing agent used should be appropriately selected from the range of 0.5 to 5.0 moles per mole of compound [VII], and preferably 0.9 to 3.0 moles.

[0116] Examples of catalysts that can be used in this reaction include 2-methyl-2-butene, sodium dihydrogen phosphate, ruthenium trichloride hydrate, and vanadium(IV) acetylacetone oxide. The amount of catalyst used can be appropriately selected from the range of 0.001 to 10.0 moles per mole of compound [VII], and preferably 0.01 to 0.1 moles.

[0117] Examples of solvents that can be used in this reaction include halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; esters such as ethyl acetate, butyl acetate, and ethyl propionate; nitriles such as acetonitrile and propionitrile; aprotic polar solvents such as acetone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and 1,3-dimethyl-2-imidazolidinone; ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; alcohols such as methanol, ethanol, 2-propanol, tert-butyl alcohol, and methyl cellosolve; water, or mixtures thereof. The amount of solvent used is 0.1 to 1000 liters per mole of compound [VII], preferably 0.2 to 100 liters.

[0118] The reaction temperature for this reaction can be selected from any temperature range from -78°C to the reflux temperature of the reaction system, and is preferably carried out in the range of -10°C to 100°C. The reaction time for this reaction varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually from 1 minute to 96 hours.

[0119] After the reaction is complete, compound [VIII] can be isolated by adding water to the reaction mixture, extracting it with an organic solvent, and then concentrating the mixture. The isolated compound [VIII] can be further purified by column chromatography, recrystallization, or other methods as needed.

[0120] <Manufacturing method 5> Among the compounds of the present invention, the compound represented by general formula [VII] can be produced according to the following method.

[0121] [ka]

[0122] (In the formula, W 2 R indicates a halogen atom. 1 , R 2 and Q 1 (This has the same meaning as above.)

[0123] That is, the compound represented by general formula [VII] can be produced by reacting the compound represented by general formula [VI] with the compound represented by general formula [VI] in a suitable solvent, in or without a suitable base.

[0124] The amount of compound [IX] used in this reaction can be appropriately selected from the range of 1 to 5 moles per mole of compound [VI], and preferably 1.0 to 3.0 moles.

[0125] Examples of bases that can be used in this reaction include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; inorganic bases such as alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; alkali metal phosphates such as tripotassium phosphate; metal hydrides such as sodium hydride and potassium hydride; metal salts of alcohols such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; or organic bases such as triethylamine, N,N-dimethylaniline, pyridine, 4-methylmorpholine, N-ethyldiisopropylamine, 4-N,N-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, 2,6-lutidine, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, and potassium bis(trimethylsilyl)amide. The amount of base used can be appropriately selected from the range of 1.0 to 10.0 moles per mole of compound [VI], and preferably 1.0 to 5.0 moles.

[0126] Examples of solvents that can be used in this reaction include halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; esters such as ethyl acetate, butyl acetate, and ethyl propionate; nitriles such as acetonitrile and propionitrile; aprotic polar solvents such as acetone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and 1,3-dimethyl-2-imidazolidinone; ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; alcohols such as methanol, ethanol, 2-propanol, tert-butyl alcohol, and methyl cellosolve; water, or mixtures thereof. The amount of solvent used is 0.1 to 100 liters per mole of compound [VI], preferably 0.3 to 50 liters.

[0127] The reaction temperature for this reaction can be selected from any temperature range from -20°C to the reflux temperature of the reaction system, and is preferably carried out in the range of 0°C to 150°C. The reaction time for this reaction varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually 1 minute to 96 hours.

[0128] After the reaction is complete, compound [VII] can be isolated by adding water to the reaction mixture, extracting it with an organic solvent, and then concentrating the mixture. The isolated compound [VII] can be further purified by column chromatography, recrystallization, or other methods as needed.

[0129] Furthermore, the raw material compound [VI] is commercially available or can be obtained by known methods, such as Organic Letter, 2015, 17, 932-935, U.S. Patent Application Publication No. 2008 / 0194617, U.S. Patent Application Publication No. 2014 / 0194452, etc.

[0130] The plant disease control agent for agricultural and horticultural use of the present invention is characterized by containing a pyrazole-4-oxadiazine ring compound represented by the general formula [I] of the present invention, an optical isomer thereof, or a salt thereof as an active ingredient.

[0131] The plant disease control agent for agricultural and horticultural use of the present invention may, if necessary, contain additive components (carriers) commonly used in pesticide formulations.

[0132] Examples of these additives include carriers such as solid or liquid carriers, surfactants, binders, tackifiers, thickeners, colorants, spreading agents, adhesives, antifreeze agents, anticaking agents, disintegrants, and decomposition inhibitors. Depending on the circumstances, preservatives and plant fragments may also be used as additives. Furthermore, these additives may be used individually or in combination of two or more.

[0133] The above-mentioned additive ingredients are explained below.

[0134] Examples of solid carriers include mineral carriers such as pyrophyllite clay, kaolin clay, silica clay, talc, diatomaceous earth, zeolite, bentonite, acid clay, activated clay, attapargas clay, vermiculite, perlite, pumice, white carbon (synthetic silicic acid, synthetic silicates, etc.), and titanium dioxide; plant-based carriers such as wood flour, corn stalks, walnut shells, fruit kernels, rice husks, sawdust, bran, soybean flour, powdered cellulose, starch, dextrin, and sugars; inorganic salt carriers such as calcium carbonate, ammonium sulfate, sodium sulfate, and potassium chloride; and polymer carriers such as polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, and urea-aldehyde resin.

[0135] Examples of liquid carriers include monohydric alcohols such as methanol, ethanol, propanol, 2-propanol, butanol, and cyclohexanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, and glycerin; polyhydric alcohol derivatives such as propylene glycol ethers; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and isophorone; ethers such as ethyl ether, 1,4-dioxane, cellosolve, dipropyl ether, and tetrahydrofuran; aliphatic hydrocarbons such as n-paraffin, naphthene, isoparaffin, kerosene, and mineral oil; and toluene and C9-C 10 Examples include aromatic hydrocarbons such as alkylbenzenes, xylenes, solvent naphthas, alkylnaphthalenes, and high-boiling aromatic hydrocarbons; halogenated hydrocarbons such as 1,2-dichloroethane, chloroform, and carbon tetrachloride; esters such as ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, and dimethyl adipate; lactones such as γ-butyrolactone; amides such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; nitriles such as acetonitrile; sulfur compounds such as dimethyl sulfoxide; vegetable oils such as soybean oil, rapeseed oil, cottonseed oil, coconut oil, and castor oil, and lower alkyl esters of fatty acids derived from the aforementioned vegetable oils; and water.

[0136] The surfactant is not particularly limited, but preferably one that gels in water or exhibits swelling properties, for example, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene fatty acid diester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene dialkylphenyl ether, polyoxyethylene alkylphenyl ether formalin condensate, polyoxyethylene polyoxypropylene block polymer, alkylpolyoxyethylene polypropylene block polymer ether, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, polyoxyethylene fatty acid bisphenyl ether, polyalkylene benzylphenyl ether, polyoxyalkylene styrylphenyl ether, acetylenediol, polyoxyalkylene-added acetylenediol, polyoxyethylene ether-type silicone, ester-type silicone, f Nonionic surfactants such as oxyethylene-based surfactants, polyoxyethylene castor oil, and polyoxyethylene hydrogenated castor oil; alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styrylphenyl ether sulfates, alkylbenzene sulfonates, lignin sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, alkylnaphthalene sulfonates, salts of formalin condensates of naphthalene sulfonic acid, salts of formalin condensates of alkylnaphthalene sulfonic acid, fatty acid salts, polycarboxylates, N-methyl fatty acid sarcosinates, resin salts, polyoxyethylene alkyl ether phosphates, and polyoxyethylene alkylphenyl ether phosphates; cationic surfactants such as alkylamine salts such as laurylamine hydrochloride, stearylamine hydrochloride, oleylamine hydrochloride, stearylamine acetate, stearylaminopropylamine acetate, alkyltrimethylammonium chloride, and alkyldimethylbenzalkonium chloride;Examples include amphoteric surfactants such as betaine-type surfactants like dialkyldiaminoethylbetaine and alkyldimethylbenzylbetaine, and amino acid-type surfactants like dialkylaminoethylglycine and alkyldimethylbenzylglycine.

[0137] Examples of binders and tackifiers include carboxymethylcellulose and its salts, dextrin, water-soluble starch, xanthan gum, guar gum, sucrose, polyvinylpyrrolidone, acacia gum, polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, polyethylene glycol with an average molecular weight of 6,000 to 20,000, polyethylene oxide with an average molecular weight of 100,000 to 5,000,000, and natural phospholipids (e.g., cephalin, lecithin, etc.).

[0138] Examples of thickening agents include water-soluble polymers such as xanthan gum, guar gum, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymers, acrylic polymers, starch derivatives, and polysaccharides; and inorganic fine powders such as high-purity bentonite and white carbon.

[0139] Examples of colorants include inorganic pigments such as iron oxide, titanium dioxide, and Prussian blue; and organic dyes such as alizarin dyes, azo dyes, and metal phthalocyanine dyes.

[0140] Examples of expanding agents include silicone-based surfactants, cellulose powder, dextrin, modified starch, polyaminocarboxylic acid chelate compounds, cross-linked polyvinylpyrrolidone, maleic acid / styrene copolymers, methacrylic acid copolymers, half-esters of polyhydric alcohol polymers and dicarboxylic acid anhydrides, water-soluble salts of polystyrene sulfonic acid, polyoxyethylene alkanediols, polyoxyethylene alkynediols, alkynediols, and the like.

[0141] Examples of spreading agents include various surfactants such as sodium dialkyl sulfosuccinate, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene fatty acid esters; paraffin, terpenes, polyamide resins, polyacrylates, polyoxyethylene, waxes, polyvinyl alkyl ethers, alkylphenol formalin condensates, and synthetic resin emulsions.

[0142] Examples of antifreeze agents include ethylene glycol, diethylene glycol, propylene glycol, polyhydric alcohols such as glycerin, and so on.

[0143] Examples of anti-caking agents include polysaccharides such as starch, alginic acid, mannose, and galactose; polyvinylpyrrolidone, white carbon, ester gum, and petroleum resin.

[0144] Examples of disintegrants include sodium tripolyphosphate, sodium hexametaphosphate, metal stearate, cellulose powder, dextrin, copolymers of methacrylate esters, polyvinylpyrrolidone, polyaminocarboxylic acid chelate compounds, sulfonated styrene-isobutylene-maleic anhydride copolymers, and starch-polyacrylonitrile graft copolymers.

[0145] Examples of decomposition inhibitors include desiccants such as zeolite, quicklime, and magnesium oxide; antioxidants such as phenolic, amine, sulfur, and phosphoric acid-based agents; and ultraviolet absorbers such as salicylic acid-based and benzophenone-based agents.

[0146] Examples of preservatives include potassium sorbate and 1,2-benzothiazole-3(2H)-one.

[0147] Examples of plant materials include sawdust, coconut husks, corn cobs, and tobacco stalks.

[0148] On the other hand, in the plant disease control agent for agricultural and horticultural use of the present invention, when the above-mentioned additive components are included, the content ratio is usually selected in the range of 5 to 95%, preferably 20 to 90%, for carriers such as solid carriers or liquid carriers, on a mass basis; usually selected in the range of 0.1 to 30%, preferably 0.5 to 10%, for surfactants; and 0.1 to 30%, preferably 0.5 to 10%, for other additives.

[0149] The plant disease control agent for agricultural and horticultural use of the present invention can be formulated and used in any dosage form such as powder, granules, granules, wettable powder, water-soluble powder, wettable granules, tablets, jumbo formulations, emulsions, oils, liquids, flowable formulations, oily suspensions, emulsions, microemulsions, sposomal emulsions, trace sprays, microcapsules, fumigants, aerosols, baits, pastes, etc.

[0150] These formulations can be used as is or diluted to a predetermined concentration with a diluent such as water. Various formulations containing the compound of the present invention or their dilutions can be applied by commonly used application methods, namely, spraying (e.g., spraying, misting, atomizing, powdering, granulation, surface application, box application, etc.), soil application (e.g., mixing, drenching, etc.), surface application (e.g., coating, powdering, covering, etc.), seed treatment (e.g., coating, powdering, etc.), immersion, poison bait, fumigation, etc. It is also possible to mix the active ingredient with feed and feed it to livestock to control the occurrence and growth of harmful insects, especially harmful insects, in their excrement.

[0151] The method for controlling plant diseases in agriculture and horticulture according to the present invention can be carried out by using the amount of the pyrazole-4-oxadiazine ring compound, its optical isomer, or its salt according to the present invention in the application method described above.

[0152] The proportion (mass%) of the active ingredient in the plant disease control agent for agricultural and horticultural use of the present invention can be appropriately selected as needed. For example, when using powders, granules, or fine granules, it is preferable to select from the range of 0.01 to 20%, preferably 0.05 to 10%. When using granules, it is preferable to select from the range of 0.1 to 30%, preferably 0.5 to 20%. When using wettable powders or granular wettable powders, it is preferable to select from the range of 1 to 70%, preferably 5 to 50%. When using water-soluble powders or liquids, it is preferable to select from the range of 1 to 95%, preferably 10 to 80%. When using emulsions, it is preferable to select from the range of 5 to 90%, preferably 10 to 80%. When using oils, it is preferable to select from the range of 1 to 50%, preferably 5 to 30%. When using a flowable formulation or oily suspension, it is preferable to appropriately select from the range of 5-60%, preferably 10-50%. When using an emulsion formulation, microemulsion formulation, or suspend emulsion formulation, it is preferable to appropriately select from the range of 5-70%, preferably 10-60%. When using tablets, bait formulations, paste formulations, etc., it is preferable to appropriately select from the range of 1-80%, preferably 5-50%. When using a fumigant formulation, it is preferable to appropriately select from the range of 0.1-50%, preferably 1-30%. When using an aerosol formulation, it is preferable to appropriately select from the range of 0.05-20%, preferably 0.1-10%.

[0153] These formulations should be diluted to an appropriate concentration and sprayed, or applied directly.

[0154] When the plant disease control agent for agricultural and horticultural use of the present invention is used after dilution with a diluent, the active ingredient concentration is generally 0.1 to 5000 ppm. When the formulation is used as is, the application rate per unit area is 0.1 to 5000 g of the active ingredient compound per hectare, but is not limited to these values.

[0155] Furthermore, while it goes without saying that the compound of the present invention is sufficiently effective as an active ingredient in the plant disease control agent for agricultural and horticultural use, it can also be mixed and used in combination with other fertilizers, pesticides, such as fungicides, antivirals, insecticides, acaricides, nematicides, synergists, attractants, herbicides, and plant growth regulators as needed, and in this case, it may exhibit even better effects.

[0156] Next, examples of known fungicides (fungicide-active ingredients) or disease control compounds that may be mixed or used in combination are listed below.

[0157] Bactericidal active ingredients or disease control compounds: Agrobacterium radiobacter, azaconazole, acibenzolar-S-methyl, azoxystrobin, anilazine, amisulbrom, aminopyrifen, ametoctradin, aldimorph, isotianil, isopyrazam, isofetamide, isoflucypram, isoprothiolane, Ipconazole, ipflufenoquin, ipfentrifluconazole, iprodione, iprovalicarb, iprobenfos, imazalil, iminoctadine-albesilate, iminoctadine-triacetate, imibenconazole, inpyrfluxam, imprimatin A A) Imprimatin B, edifenphos, etaconazole, etaboxam, ethirimol, ethoxyquin, etridiazole, enestroburin, enoxastrobin, epoxyconazole, organic oiloils), oxadixyl, oxazinylazole, oxathiapiprolin, oxycarboxin, oxine-copper, oxytetracycline, oxpoconazole-fumarate, oxolinic acid, copper dioctanoate, octhilinone, ofurace, orysastrobin, o-phenylphenol, kasugamycin, captafol, galquin, carpropamid, carbendazim, carboxin, carvone, Candida Candida oleophila, Candida saitoana, quinoxyfen, quinofumelin, chinomethionate, captan, quinconazole, quintozene, guazatine, cufraneb, coumethoxystrobin, coumoxystrobin, Gliocradium catenulatum, Cryptococcus albidus, kresoxim-methyl, clozylacon, Clonostachys rosea rosea), chlozolinate, chloroinconazide, chlorothalonil, chloroneb, ketomium cupreum (Chaetomium)Cupreum, Coniothyrium minitans, cyazofamid, diethofencarb, diclocymet, dichlofluanid, diclobentiazox, diclomezine, dichloran, dichlorophen, dithianon, diniconazole, diniconazole-M Zineb, Dinocap, Dipymetitrone, Diphenylamine, Difenoconazole, Cyflufenamid, Diflumetrim, Cyproconazole, Cyprodinil, Simeconazole, Dimethirimol, Dimethyl disulfide disulfide), dimethomorph, cymoxanil, dimoxystrobin, Pseudozyma flocculosa, Pseudomonas aureofaciens, Pseudomonas chlororaphis, Pseudomonas syringae, Pseudomonas flurorescens, Pseudomonas rhodesiae, ziram, silthiofam, Zucchini yellow mosaic virus (attenuated strain), streptomycin, Streptomyces griseobilidisgriseoviridis, Streptomyces lygicus, spiroxamine, sedaxane, seboctylamine, zoxamide, solatenol, dazomet, Talaromyces flavus flavus), thiadinil, thiabendazole, thiram, thiophanate, thiophanate-methyl, thifluzamide, thiram, tecnazene, tecloftalam, tetraconazole, debacarb, tebuconazole, tebufloquin, terbinafine, dodine, dodemorph, triadimenol, triadimefon, triazoxide, triclamide, triclopyricarb, Trichoderma aspereram Trichoderma asperellum), Trichoderma atroviride, Trichoderma gamsii, Trichoderma stromaticum, Trichoderma paecilomyces, Trichoderma harzianum, Trichoderma viride, Trichoderma virens, Trichoderma polysporum, Trichoderma harzianum rifai, TrichodermaLignoran (Trichoderma lignorum), tricyclazole, triticonazole, tridemorph, triflumizole, trifloxystrobin, triforine, tolylfluanid, tolclofos-methyl, tolnifanide, tolprocarb, nabam, natamycin, naftifine, nitrapyrin, nitrothal-isopropyl, nuarimol, copper nonylphenol sulfonate, Paenibacillus polymixa Polymyxa), Burkholderia cepacia, Bacillus amyloliquefaciens, Bacillus simplex, Bacillus subtilis, Bacillus pumilus, Bacillus mycoides, Bacillus licheniformis, harpin protein, Variovorax paradoxus, validamycin, valifenalate, Pantoea agglomerans agglomerans, picarbutrazox, bixafen, picoxystrobin, Pythium oliganglidrumoligandrum), pydiflumetofen, bitertanol, binapacryl, hinokitiol, non-pathogenic Erwinia carotovora, non-pathogenic Rhizobium vitis, biphenyl, bifemetstrobin, piperalin, hymexazol, pyraoxystrobin, pyraclostrobin, pyraziflumid, pyrazophos, pyrapropion opoyne, pyrametostrobin, pyriophenone, pyrisoxazole, pyridaclomethyl, pyrifenox, pyributicarb, pyribencarb, pyrimethanil, pyroquilon, vinclozolin, ferbam, famoxadone, phenazine oxide Fusarium oxide, fenamidone, fenaminstrobin, fenarimol, fenoxanil, fenopyramid, ferimzone, fenpiclonil, fenpicoxamid, fenpyrazamine, fenbuconazole, fenfuram, fenpropidin, fenpropimorph, fenhexamid, folpet, phthalide, Fusarium oxysporum oxysporum), bupirimate, fuberidazole, blasticidin-S, furametpyr, furalaxyl, furancarboxylic acid, fluazinam, fluindapyr, fluoxastrobin, fluoxapiprolin, fluoxytioconazole, fluopicolide, fluopimomide, fluopyram, fluoroimide,Fluxapyroxad, fluquinometoate, fluquinconazole, furconazole, furconazole-cis, fludioxonil, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, flufenoxadiazam, flufenoxystrobin, flubeneteram, flumetylsulforim, flumetover, flumorph, Phlebiopsis gigantea gigantea), proquinazid, prochloraz, procymidone, prothiocarb, prothioconazole, bronopol, propamocarb-hydrochloride, propiconazole, propineb, probenazole, bromuconazole, flometoquin, floryl picoxamide ( Florylpicoxamid), hexaconazole, benalaxyl, benalaxyl-M, benodanil, benomyl, pefurazoate, penconazole, pencycuron, benzovindiflupyr, benthiazole, benthiavalicarb-isopropyl, penthiopyrad,Penflufen, boscalid, fosetyl (containing salts of aluminum, calcium, sodium, etc.), polyoxin, polycarbamate, Bordeaux mixture, mancopper, mancozeb, mandipropamid, mandestrobin, maneb, myclobutanil, mineral oil oils), mildiomycin, methasulfocarb, metam, metalaxyl, metalaxyl-M, metarylpicoxamide, metiram, methyltetraprole, metconazole, metominostrobin, metrafenone, mepanipyrim, mefentrifluconazole, meptyldinocap, mepronil, iodocarb, laminarin, ledprona, phosphorous acid and salts, basic copper chloride oxychloride), silver, copper(II) sulfate, cuprous oxide, copper hydroxide, potassium bicarbonate, sodium bicarbonate, sulfur, oxyquinoline sulfate, copper sulfate, UK-2A (code number), bisethylenediamine copper complex [II] dodecylbenzenesulfonate (DBEDC), triphenyltin acetate (TPTA),Triphenyltine chloride (TPTC), triphenyltin hydroxide (TPTH), 6-chloro-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-3-[3-(trifluoromethyl)phenoxy]pyridazine-4-carboxamide (chemical name, CAS registry number: 2435594-93-5) (International Publication No. 2020 / 109391), Racemi-3-[6-chloro-3-[3-(trifluoromethyl)phenoxy]pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (rac-3-[6-chloro-3-[3-(trifluoromethyl)phenoxy]pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1,2 ,4-oxadiazine) (Chemical name, CAS registry number: 2446124-68-9) (International Publication No. 2020 / 127780), 6-chloro-N-[2-(2,4-dimethylphenyl)-2,2-difluoroethyl]-5-methyl-3-[3-(trifluoromethyl)phenoxy]pyridazine-4-carboxamide (6-chloro-N-[2-(2,4-dimethylphenyl)-2,2-difluoroethyl]-5-methyl-3-[3-(trifluoromethyl)phenoxy]p 6-chloro-N-[2-(2,4-dimethylphenyl)ethyl]-3-[3-(trifluoromethyl)phenoxy]pyridazine-4-carboxamide) (chemical name,CAS Registry Number: 2435600-09-0) (International Publication No. 2020 / 109391), 6-chloro-N-[2-(2,4-dimethylphenyl)ethyl]-5-methyl-3-[3-(trifluoromethyl)phenoxy]pyridazine-4-carboxamide (chemical name, CAS Registry Number: 2435603-15-7) (International Publication No. 2020 / 109391), racemic-3- [6-chloro-5-methyl-3-[3-(trifluoromethyl)phenoxy]pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (rac-3-[6-chloro-5-methyl-3-[3-(trifluoromethyl)phenoxy]pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine) (Chemical name, CAS registry number: 2446123-98-2) (International Publication No. 2020 / 127780).

[0158] Next, examples of known insecticides (insecticidal active ingredients), acaricides (acaricidal active ingredients), nematicides (nematicidal active ingredients), and synergistic compounds (synergistic active ingredients) that may be mixed or used in combination are given below.

[0159] Insecticidal active ingredients, acaricidal active ingredients, nematicidal active ingredients, synergistic active ingredients: Acrin, azadirachtin, azamethiphos, acynonapyr, azinphos-ethyl, azinphos-methyl, acequinocyl, acetamiprid, acetoprole, acephate, azocyclotin, Abamectin, afidopyropen, afoxolaner, amidoflumet, amitraz, alanycarb, aldicarb, aldoxycarb, allethrin [including d-cis-trans and d-trans forms], isazophos, isamidofos ), isocarbophos, isoxathion, isocycloseram, isofenphos-methyl, isoflualanam, isoprocarb, epsilon-metofluthrin, epsilon-momfluorothrin, ivermectin n) Imicyafos, imidacloprid, imiprothrin, indazapyroxamet, indoxacarb, umifoxolaner, esfenvalerate, ethiofencarb, ethion, ethiprole, ethylene dibromide, etoxazole, etofenprox,Ethoprophos, etrimfos, emamectin, emamectin benzoate, endosulfan, empenthrin, oxazosulfyl, oxamyl, oxydemeton-methyl, oxydeprofos, omethoate, Nuclear polyhedrosis virus, cadusafos, kappa-tefluthrin, kappa-bifenthrin, karanjin, galquin, cartap, Granulosis virus Entero virus), coumaphos, cryolite, clothianidin, clofentezine, chromafenozide, chlorantraniliprole, chlorethoxyfos, chlordane, chloropicrin, chlorpyrifos, chlorpyrifos-methyl, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroprallethrin,Entomopoxi virus, Irido virus, cyazypyr, cyanophos, diafenthiuron, diamidaphos, cyantraniliprole, cyetpyrafen, dienochlor, cyenopyrafen, dioxabenzofos, diofenolan, Sigma virus (virus), cyclaniliprole, cycloxaprid, dicrotophos, diclofenthion, cyclobutrifluram, cycloprothrin, dichlorvos, dichloromezotiaz, dicofol, dicyclanil, disulfoton, dinotefuran, dinobuton, cyhalodiamide, cyhalothrin [including gamma- and lambda- forms], cy Phenothrin (cyphenothrin) [including (1R)-trans-isomer], cyfluthrin (cyfluthrin) [including beta-isomer], diflubenzuron, cyflumetofen, diflovidazin, cyproflanilide, cyhexatin, cypermethrin [including alpha-isomer, beta-isomer, theta-isomer, zeta-isomer], cybenzoxasulfyl, dimpropyridaz, dimethyl-2,2,2-trichloro-1-hydroxyethylphosphonate (DEP), dimethylvinphos,Dimethoate, dimefluthrin, jasmone, cis-jasmone, jasmonic acid, methyl jasmonate, silafluofen, cyromazine, Steinernema carpocapsae, Steinernema kushidai, Steinernema glacerai glaseri), spidoxamat, spinetoram, spinosad, spirodiclofen, spirotetramat, spiropidion, spirobudifen, spiromesifen, sulcofuron-sodium, sulfiflumin, sulfluramid, sulfoxaflor, sulfoxamyl, sulfotep, diazinon, thiacloprid, thiapyrachlor (t iapyrachlor), thiamethoxam, tioxazafen, thiodicarb, thiocyclam, thiosultap, thionazin, thiofanox, thiometon, thiorantraniliprole, tyclopyrazoflor, tigolaner, tetrachlorantraniliprole, tetrachlorvinphos, tetradifon, tetraniliprole,Tetramethylfluthrin, tetramethrin, tebupirimfos, tebufenozide, tebufenpyrad, tefluthrin, teflubenzuron, demeton-S-methyl, temephos, deltamethrin, terbufos, tralomethrin, transfluthrin, triazamate, triazophos, trichlorfon, Trichoderma asperellum, Trichoderma paecilomyces, Trichoderma Trichoderma harzianum, triflumuron, trifluenfuronate, triflumezopyrim, trimethacarb, tolfenpyrad, naled, nicotine, nicofluprole, nitenpyram, nemadectin, Denso virus, novaluron, nobiflumuron, paecilomyces lilacinus, Burkholderia cepacia, Verticillium lecanii, hydroprene, Pasteuria nisizawai nishizawae), Pasteuria penetrans, Bacillus amyloliquefaciens,Bacillus firmus, Bacillus sphaericus, Bacillus subtillis, Bacillus thuringiensis, and Bacillus thuringiensis are produced. The insect toxins include Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Israelensis, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis, Bacillus popilliae, and Bacillus licheniformis. (licheniformis), vadescana, vamidothion, parathion, parathion-methyl, halfenprox, halofenozide, bioallethrin, bioallethrin S-cyclopentenyl S-cyclopentenyl), pioxaniliprole, bioresmethrin, bis-(2-chloro-1-methylethyl) ether (DCIP), bistrifluron, bisulflufen, hydramethylnon, bifenazate, bifenthrin, pyflubumide, piperflanilide, piperonyl butoxide (piperonyl(butoxide), pymetrozine, pyraclofos, pyrafluprole, pyridaphenthion, pyridaben, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, pirimicarb, pyrimidifen, pyriminostrobin, pirimiphos-methyl, pyrethrin (pyret hrine), famphur, fipronil, fenazaquin, fenamiphos, fenitrothion, fenoxycarb, fenothiocarb, phenothrin [including (1R)-trans-isomer], fenobucarb, fenthion, phenthoate, fenvalerate, fenpyroximate, fenbutatin oxide (oxide), fenpropathrin, fenmezoditiaz, fonofos, sulfuryl fluoride, butocarboxim, butoxycarboxim, buprofezin, furathiocarb, prallethrin, fluacrypyrim, fluazaindolizine, fluazuron, fluensulfone, fluopyram, sodium fluoroacetateFluoracetate), fluxametamide, fluchlordiniliprole, flucycloxuron, flucythrinate, fluthrin, fluvalinate [including tau-isomer], flupyradifurone, flupyrazofos, flupyrimin, flupyroxystrobin, flufiprole, flufenerim, flufenoxystrobin, flufenoxuron, fluhexafon, flubendiamide, flupentiophenox (f Lupentiofenox, Flumetnicum, Flumethrin, Fluralaner, Flurimfen, Prothiofos, Protrifenbute, Flonicamid, Propaphos, Propargite, Prohydrojasmon, Profenofos, Broflanilide, Profluthrin, Propetamphos, Propoxur, Flometoquin, Bromopropylate, Hexythiazox, Hexaflumuron, Pekylomyces Pacilimyces tenuipes, Paecilomyces fumosoroceus, Paecilomyces lyraquinasLilacinus), heptafluthrin, heptenophos, permethrin, benclothiaz, benzpyrimoxan, bensultap, benzoximate, bendiocarb, benfuracarb, bentiolumin, Pochonia chlamydosporia, Beauveria tenella, Beauveria bassiana, Beauveria bronchitis brongniartii), phoxim, phosalone, fosthiazate, fosthietan, phosphamidon, phosmet, polynactins, formetanate, phorate, machine oil, malathion, mivorilaner, milbemectin, mecarbam, mesulfenfos, methomyl, metaldehyde, metaflumizone, metamidophos, metam, methiocarb, methidathion, methyl isothiocyanate isothiocyanate), methyl bromide (methylbromide), methoxychlor, methoxyfenozide, methothrin, metofluthrin, methoprene, metolcarb, mevinphos, meperfluthrin, modoflaner, Monacrosporium phymatophagum, monocrotophos, momfluorothrin, Trichoderma harzianum, litlure-A, litlure-B, aluminum phosphide, zinc phosphide Phosphide, hydrogen phosphine, lufenuron, rescalure, resmethrin, lepimectin, rotenone, cytoplasmic polyhedrosis virus embedding, fenbutatin oxide, calcium cyanamidecyanide, organotins, nicotine sulfate, (Z)-11-tetradecenyl acetate, (Z)-11-hexadecenal, (Z)-11-hexadecenyl acetate, (Z)-9,12-tetradecadienyl acetate, (Z)-9-tetradecen-1-ol, (Z,E)-9,11-tetradecadienyl Setate, (Z,E)-9,12-tetradecadienyl acetate, 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT), 1,3-dichloropropene, 4,6-dinitro-o-cresol (DNOC), Bt protein (Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cr (y3Bb,Cry34 / 35Ab1), Methyl eugenol, 4-(p-acetooxyphenyl)-2-butanone, (Z)-10-tetradecenyl acetate, (E,Z)-4,10-tetradecadienyl acetate, (Z)-8-dodecenyl acetate, (Z)-13-icosen-10-one, 14-methyl-1-octadecene, AKD-1193 (code number), BCS-AA1014 7 (code number), CL900167 (code number), O,O-diethyl-O-[4-(dimethylsulfamoyl)phenyl]-phosphorothionate (DSP), O-ethyl-O-4-(nitrophenyl)phenylphosphonothioate (EPN), RU15525 (code number), XMC (XMC), Z-13-icosen-10-one, ZXI8901 (code number), F4260 (code number).

[0160] Next, examples of known herbicides, herbicidal active ingredients, or plant growth regulators that may be mixed or used in combination are given below, but are not limited to these examples.

[0161] Herbicide compounds or herbicidal active ingredients: Ioxynil (including salts with lithium salt, sodium salt, octanonic acid, etc.), acroniphen, acrolein, azaphenidin, acifluorfen (including salts with sodium, etc.), azimsulfuron, asulam, acetochlor, atrazine, anilofos, amicarbazone, amidosulfuron, amitrole, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, ametryn, Araujia Mosaic Virus, alachlor, Alternaria Alternaria destruens, alloxydim (including salts with sodium, etc.), ancymidol, icafolin-methyl, isouron, isoxachlortole, isoxaflutole, isoxaben, isodecyl alcohol ethoxylate, isoproturon, ipfenc Arbazone), iptriazopyrid, imazaquin, imazapic (including salts with amines, etc.), imazapyr (including salts with isopropylamine, etc.), imazamethabenz, imazamethabenz-methyl, imazamox, imazethapyr, imazosulfuron, indaziflam,Indanofan, indolauxipyr-cyanomethyl, eglinazine-ethyl, esprocarb, ethametsulfuron-methyl, ethalfluralin, ethidimuron, ethoxysulfuron, ethoxyfen, ethoxyfen-ethyl Ethoxyfen-ethyl, etofumesate, etobenzanid, epiriphenacil, endothal-disodium, oxadiazon, oxadiargyl, oxaziclomefone, oxasulfuron, oxyfluorfen, oryzalin, Obuda Pepper virus (Obuda Pepper Virus), orthosulfamuron, orbencarb, oleic acid, cafenstrole, caprylic acid, capric acid, carfentrazone-ethyl, carbutilate, carbetamide, quizalofop, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, Xanthomonas campustris Campestris, quinoclamine, quinclorac, quinmerac, citric acid, cumyluron, clacyfos,Glyphosate (containing salts of sodium, potassium, amine, propylamine, isopropylamine, ammonium, isopropylammonium, guanidine, monoethanolamine, choline, BAPMA (N,N-bis-(aminopropyl)methylamine), dimethylamine, or trimethium), glufosinate (containing salts of amine or sodium), glufosinate-P, glufosinate-P-sodium, clethodim, clodinafop, clodinafop-propargyl, clopyralid (containing monoethanolamine salt), clomazone, chlomethoxyfen, clomeprop (clom eprop), chloransulam-methyl, chloramben, chloridazon, chlorimuron, chlorimuron-ethyl, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, chlorphthalim, chlorflurenol-methyl, chlorpropham, chlorbromuron, chloroxuron, chlorotoluron, ketospiradox (containing salts of sodium, calcium, or ammonia, etc.), choletotrichum Colletotrichum orbiculare, Colletotrichum gloeosporioides, Colletotrichum truncatum, Chondrostercum purpureum,Saflufenacil, sarmentine, cyanazine, cyanamide, diuron, diethatyl-ethyl, dioxopyritrione, dicamba (containing amines, diethylamine, isopropylamine, diglycolamine, dimethylammonium, diolamine, isopropylammonium, auramine, potassium, trolamine, BAPMA (N,N-bis-(aminopropyl)methylamine), choline, sodium or lithium salts, or esters such as methyl esters), cycloate, cyclooxydim, diclos Diclosulam, cyclosulfamuron, cyclopyranil, cyclopyrimorate, diclobenil, diclofop, diclofop-P-methyl, diclofop-methyl, dichlorprop, dichlorprop-P (containing salts of dimethylammonium, potassium, sodium, choline, etc., or esters such as butotyl ester, 2-ethylhexyl ester, isoctyl ester, methyl ester, etc.), diquat, diquat dibromide Dibromide, dithiopyr, siduron, dinitramine, cinidon-ethyl, cinosulfuron, dinoseb (including acetate), dinoterb, cyhalofop, cyhalofop-butyl, cypyrafluone, diphenamid, difenzoquat, diflufenican,Diflufenzopyr, simazine, dimesulfazet, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, simetryn, dimepiperate, dimefuron, Pseudomonas fluorescein Fluorescens), cinflubrolin, cinmethylin, swep, sulcotrione, sulfentrazone, sulfosate, sulfosulfuron, sulfometuron-methyl, setoxydim, Sclerotinia minor, terbacil, daimuron, thaxtomin A, Tobacco Mild Green Mosaic Tobamovirus, Tobacco Rattle Virus Virus), dalapon, thiazopyr, tiafenacil, thiencarbazone (including sodium salt, methyl ester, etc.), tiocarbazil, thiobencarb, thidiazimin, thidiazuron, thifensulfuron, thifensulfuron-methyl, desmedipham, desmetryne, tetflupyrolimet, thenylchlor, tebutam, tebuthiuron,Tepraloxydim, tefuryltrione, terbuthylazine, terbutryn, terbumeton, tembotrione, topramezone, tralcoxidim (, tralkoxydim), triaziflam, triasulfuron, triafamone, tri-allate, trietazine, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tritosulfuron, tripyrasulfone, trifludimoxazine Zin, triflusulfuron-methyl, trifluralin, trifloxysulfuron (including salts with sodium, etc.), tribenuron-methyl, tolpyralate, naptalam (including salts with sodium, etc.), naproanilide, nappropamide, nappropamide-M, nicosulfuron, lactic acid acid), Neburon, Norflurazon, Vernolate, Paraquat, Paraquat Dichloride, Halauxifen, Halauxifen-Benzyl, Halauxifen-Methyl, Haloxyfop, Haloxyfop-P, Haloxyfop-Etotyl, Haloxyfop-P-Methyl, Halosafen, Halosulfuron-Methyl, Bixlozone, Pichloram (including salts with dichloroammonium, trolamine, etc.),picolinafen, bicyclopyrone, bispyribac-sodium, pinoxaden, bipyrazone, bifenox, piperophos, pyraclonil, pyrasulfotole, pyrazoxyfen, pyrazosulfuron-ethyl, pyrazolynate, bilanafos, pyraflufen, pyraful Pyraflufen-ethyl, pyraquinate, pyridafol, pyrithiobac-sodium, pyridate, pyriftalid, pyributicarb, pyriflubenzoxim, pyribenzoxim, pyrimisulfan, pyriminobac-methyl, pyroxasulfone, pyroxsulam, phytopsola Palmivora (Phytophthora palmivora), phenisopham, fenuron, fenoxasulfone, fenoxaprop (containing methyl, ethyl, and isopropyl esters), fenoxaprop-P (containing methyl, ethyl, and isopropyl esters), feproxydim, fenquinotrione, fenthiaprop-ethyl, fentrazamide, fenpyrazone, phenmedipham, Phoma chenopodicola,Phoma herbarum, Phoma macrostoma, butachlor, butafenacil, butamifos, butyrate, Puccinia canaliculata, Puccinia suraspeos Thlaspeos), butenachlor, butralin, butroxydim, flazasulfuron, flamprop (containing methyl, ethyl, and isopropyl esters), flamprop-M (containing methyl, ethyl, and isopropyl esters), primisulfuron, primisulfuron-methyl, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, fluazolate, fluometuron, fluoroglycof en-ethyl), flucarbazone-sodium, fluchloraminopyr, fluchloralin, flucetosulfuron, flusulfinam, fluthiacet-methyl, flupyrsulfuron-methyl (containing salts such as sodium, calcium or ammonia), flufenacet, flufenoximacil, flufenpyr-ethyl, flupropanate (containing sodium salt), flupoxame, flumioxazin,Flumiclorac-pentyl, flumetsulam, fluridone, flurtamone, fluroxypyr (containing esters of butomethyl, meptyl, etc., or salts of sodium, calcium, ammonia, etc.), flurochloridone, pretilachlor, procarbazone (containing salts with sodium, etc.), proclozo Broclozone, prodiamine, prosulfuron, prosulfocarb, propaquizafop, propachlor, propazine, propanil, propyzamide, propisochlor, propyrisulfuron, propham, profluazole (profluazol), prohexadione-calcium, propoxycarbazone, propoxycarbazone-sodium, profoxydim, bromacil, brompyrazon, prometryn, prometon, bromoxynil (butyric acid, octanoic acid or hep (Including esters of tannic acid, etc.), bromophenoxime, bromobutide, florasulam, florpyrauxifen, florpyrauxifen-benzyl, hexazinone, petoxamide, benazolin, benazolin-ethyl, penoxsulam,Pepino Mosaic Virus, heptamaloxyloglucan, beflubutamid, beflubutamid-M, pebulate, pelargonic acid (acid), bencarbazone, benquitrione, benzfendizone, bensulide, bensulfuron, bensulfuron-methyl, benzobicyclon, benzofenap, bentazone, pentanochlor, pendimethalin, pentoxazone, benfluralin, benfuresate, fosamine, fomesafen, foramsulfuron, forchlorfenuron, mecoprop (sodium) , potassium, isopropylamine, triethanolamine, dimethylamine, diolamine, trolamine, choline, etc. (including salts of these, or esters of ethadyl esters, 2-ethylhexyl ester, isoctyl ester, methyl ester, etc.), mecoprop-P-potassium salt, mesosulfuron (including esters of methyl, etc.), mesotrione, metazachlor, metazosulfuron, metabenzthiazuron, metamitron, metamifop, metam (including salts of sodium, etc.), disodium methanearsone (DSMA), methiozolin, methyldymuron, metoxuron,Metosulam, metosulfuron-methyl, metobromuron, metproxybicyclone, metobenzuron, metolachlor, metribuzin, mepiquat chloride, ide), mefenacet, monosulfuron (including methyl, ethyl, and isopropyl esters), monolinuron, molinate, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium (lfuron-sodium), lactofen, lancotrione, linuron, rimisoxafen, rimsulfuron, lenacil, 2,2,2-trichloroacetic acid (TCA) (containing salts such as sodium, calcium, or ammonia), 2,3,6-trichlorobenzoic acid (2,3,6-TBA), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) , 2,4-dichlorophenoxyacetic acid (2,4-D) (containing salts of amines, diethylamine, triethanolamine, isopropylamine, dimethylammonium, diolamine, dodecylammonium, heptylammonium, tetradecylammonium, triethylammonium, tris(2-hydroxypropyl)ammonium, trolamine, choline, sodium or lithium, or esters such as butotyl ester, 2-butoxypropyl ester, 2-ethylhexyl ester, methyl ester, ethyl ester, butyl ester, isobutyl ester, octyl ester, pentyl ester, propyl ester, isoctyl ester, isopropyl ester, meptyl ester, tefuryl ester, etc.), 2,4-dichlorophenoxybutyric acid (2,4-DB) (containing salts of amines, diethylamine, triethanolamine, isopropylamine, dimethylammonium, choline, sodium or lithium, or esters such as isoctyl ester), 2-amino-3-chloro-1,4-Naphthoquinone (ACN), 2-methyl-4-chlorophenoxyacetic acid (MCPA) (containing salts of sodium, dimethylammonium, choline, etc., or esters such as 2-ethylhexyl ester, isoctyl ester, ethyl ester, etc.), 2-methyl-4-chlorophenoxybutyric acid (MCPB) (containing sodium salt, ethyl ester, etc.), 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), 4,6-dinitro-O-cresol (DNOC) (containing salts of amine or sodium, etc.), N4-(2,6-difluoro N4-(2,6-difluorophenyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine (Chemical name, CAS registry number: 1606999-43-2) (International Publication No. 2014 / 064094, International Publication No. 2015 / 162164), 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidined-2 -one (4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one) (chemical name, CAS registry number: 1708087-22-2) (International Publication No. 2015 / 059262, International Publication No. 2018 / 015476), 6-(1-fluorocyclopentyl)-N4-(2,3,5,6-tetrafluorophenyl)-1,3,5-triazine-2,4-diamine (6-(1-fluorocyclopentyl)-N4-(2,3, 5,6-tetrafluorophenyl)-1,3,5-triazine-2,4-diamine) (Chemical name, CAS registry number: 1820807-75-7) (International Publication No. 2015 / 162164), 6-(1-fluoro-1-methylethyl)-N4-(2,3,5,6-tetrafluorophenyl)-1,3,5-triazine-2,4-diamine(6-(1-fluoro-1-methylethyl)-N4-(2,3,5,6-tetrafluorophenyl)-1,3,5-triazine-2,4-diamine) (Chemical name, CAS registry number: 1606999-21-6) (International Publication No. 2014 / 064094, International Publication No. 2015 / 162164), 6-(1-methylcyclobutyl)-N4-(2,3,5,6-tetrafluorophenyl)-1,3,5-triazine-2,4-diamine (6-(1-methylcyclobutyl)-N4-(2,3,5,6-tetrafluorophenyl)-1,3,5-triazine-2,4-diamine) (Chemical name, CAS registry number: 1 607001-97-7) (International Publication No. 2014 / 064094, International Publication No. 2015 / 162164), AE-F-150944 (code number), IR-6396 (code number), MCPA-thioethyl, SYP-298 (code number), SYP-300 (code number), S-ethyldipropylthiocarbamate (EPTC), S-metolachlor, S-9750 (code number), MSMA (monosodium methyl arsenate), HW-02 (code number).

[0162] Plant growth regulators: 1-naphthylacetamide, 1-methylcyclopropene, 1,3-diphenylurea, 2,3,5-triiodobenzoic acid 5-(trifluoromethyl)benzo[b]thiophen-2-carboxylate methyl (CPA), 2-(naphthalene-1-yl)acetamide, 2,6-diisopropylnaphthalene, 3-[(6-chloro-4-phenylquinazoline-2-yl)amino]propane-1-ol, 4-oxo-4-(2-phenylethyl)aminobutyric acid (chemical name, CAS registry number: 1083-55-2), 4-chlorophenoxyacetic acid (4-CPA), 5-aminolevulinic acid hydrochloride, 5-(trifluoromethyl)benzo[b]thiophen-2-carboxylate methyl (CPA) 5-(trifluoromethyl)benzo[b]thiofen-2-carboxylate), AVG (aminoethoxyvinylglycine), n-decyl alcohol, anisiflupurin, aviglycine, ancymidol, abscisic acid, isoprothiolane, inabenfide, indole acetic acid, indole butyric acid, uniconazole, uniconazole-P, Ecolyst, etychlozate, ethephon, epocholeone, calcium chloride, choline chlorideChloride, oxine sulfate, kinetin, calcium peroxide, carvone, calcium formate, cloxyfonac, cloxyfonac-potassium, cloprop, chlormequat, chlormequat-chloride, chlorpropham, choline, cytokinins, oxidized glutathione, cyanamide, sodium cyanate cyanate), cyclanilide, dichlorprop (containing salts of dimethylammonium, potassium, sodium, choline, etc., or esters such as butotyl ester, 2-ethylhexyl ester, isoctyl ester, methyl ester, etc.), dichlorprop-P (containing salts of sodium, potassium, dimethylammonium, etc., or 2-ethylhexyl ester), diquat, diquat dibromide, dikegulac, gibberellinic acid, gibberellin A4, gibberellin A7, dimethipin, sintofen, jasmone, cis-jasmone, jasmonic acid, methyl jasmonate Jasmonate, streptomycin, calcium polysulfide, daminozide, calcium carbonateCarbonate, thidiazuron, decan-1-ol, triacontanol, tripenthenol, trinexapac-ethyl, tribufos, paclobutrazol, paraffin, bispyribac-sodium, hymexazol, butralin, fluthiacet-methyl, pyraflufen-ethyl ethyl), flumetralin, flurprimidol, flurenol, pronitridine, prohydrojasmon, prohexadione-calcium, heptamaloxyloglucan, 6-benzylaminopurine, pendimethalin, forchlorfenuron, formononetin, maleic hydrazide, mepiquat chloride, mefluidide, lipochitooligosaccharides (e.g., lipochitooligosaccharides SP104), calcium sulfate.

[0163] Next, examples of known pharmacokinetic mitigation compounds that may be mixed or used in combination are listed below.

[0164] Compounds that reduce drug-induced harm: Isoxadifen, isoxadifen-ethyl, oxabetrinil, octane-1,8-diamine, cloquintocet, cloquintcet-mexyl, dietholate, cyometrinil, dichlormid, dicyclonone, cyprosulfamide, daimuron, 1,8-naphthalic anhydride Anhydride), fenchlorazole, fenchlorazole-O-ethyl, fenchlorim, furilazole, fluxofenim, flurazole, benoxacor, metcamifen, mephenate, mefenpyr, mefenpi Mefenpyr-ethyl, mefenpyr-diethyl, lower alkyl-substituted benzoic acid, 2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamide (PPG-1292), 2-dichloromethyl-2-methyl-1,3-dioxane (MG-191), 3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine (R-29148), 4-dichloroacetyl-1-oxa-4-azaspiro[4.5] Decane (AD-67), 4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid (CL-304415, code number), MON4660 (code number), N1,N2-diallyl-N2-dichloroacetylglycinamide (DKA-24, code number), 1-bromo-4-[(chloromethyl)sulfonyl]benzene (CSB), 2-propenyl 1-oxa-4-azaspiro[4,5]decane-4-carboditioate (MG-838, code number), 3-(dichloroacetyl)-2,2-dimethyl-1,3-oxazolidine (R-28725, code number), R-29148 (code number), 1-(dichloroacetyl)azepane (TI-35, code number).

[0165] Next, examples of known biopesticides that may be mixed or used in combination are given.

[0166] Biopesticides: Haplothrips brevitubus, Franklinothrips vespiformis, Diglyphus isaea, Encarsia formosa, Amblyseius cucumeris, Pseudaphycus malinus, Amblyseius womersleyi, Aphidius colemani, Eretmocerus eremicus, Aphidoletes aphidimyza, Amblyseius swirskii, Orius Phytoseiulus persimilis, Amblyseius degenerans, Phytoseiulus persimilis, Orius sauteri, Dacnusa sibirica, Amblyseius californicus, Chrysoperla nipponensis, Anicetus beneficus.

[0167] Next, examples of known agricultural materials that may be mixed or used in combination are given.

[0168] Agricultural supplies: Ethylene, hypochlorous acid water (limited to that obtained by electrolysis of hydrochloric acid or potassium chloride aqueous solution), baking soda, vinegar, humic substances, humic acid, fulvic acid, seaweed extract, polysaccharides, amino acids, microbial materials, functional components derived from plants and animals, microbial metabolites, microbial activators, soil spreading agents, soil permeability regulators, soil water retention materials, etc., and biostimulants.

[0169] Next, examples of known agricultural fertilizer components that may be mixed or used in combination are given.

[0170] Fertilizers include inorganic fertilizers and organic fertilizers, but examples include ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium dihydrogen phosphate, ammonium urea nitrate, urea, calcium cyanamide, potassium nitrate, superphosphate, double superphosphate, potassium dihydrogen phosphate, potassium chloride, potassium sulfate, potassium carbonate, potassium silicate, oil cake, fish meal, rice bran, bat guano, and fermented chicken manure.

[0171] Specific examples of plant diseases that can be controlled by the plant disease control agent and method for controlling plant diseases of the present invention are provided, but the invention is not limited to these examples.

[0172] Basidiomycota: Rice sheath blight (Thanatephorus cucumeris); wheat rust (Puccinia recondite, Puccinia graminis, Puccinia hordei, Puccinia striiformis), snow mold (Typhula incarnata, Typhula ishikariensis), smut (Ustilago tritici, Ustilago nuda), smut (Tilletia spp.); grape rust (Phakopsora meliosmae-myrianthae, Phakopsora montana, Physopella ampelopsidis); apple rust (Gymnosporangium yamadae); pear rust (Gymnosporangium asiaticum); seedling blight for cucurbits and tomatoes (Rhizoctonia solani); onion rust (Puccinia allii, Uromyces Allii-monanthi (Uromyces japonicus), black rot (Sclerotium cepivorum); soybean rust (Phakopsora pachyrhizim, Phakopsora meibomiae); potato black spot (Rhizoctonia sp., Thanatephorus cucumeris); tea leaf blight (Exobasidium reticulatum); chrysanthemum white rust (Puccinia horiana); grass leaf blight (Rhizoctonia solani), rust (Puccinia zoysiae), fairy ring (Marasmius oreades, etc.); sugar beet root rot (Thanatephorus cucumeris) Ascomycota: Rice blast (Pyricularia oryzae), Sesame leaf blight (Cochliobolus miyabeanus), Gibberella fujikuroi, Seedling damping off (Fusarium avenaceum, Fusarium proliferatum, Fusarium solani, Trichoderma viride), Rice mildew (Villosiclava virens); Wheat powdery mildew (Blumeria) graminis f. sp. Hordeii, Blumeria graminis f. sp. tritici), Pyrenophora graminea, Pyrenophora teres, Fusarium asiaticum, Fusarium avenaceum, Fusarium crookwellense, Fusarium culmorum, Gibberella zeae, Microdochium majus,Microdochium nivale), Myriosclerotinia borealis, Microdochium nivale, Oculimacula acuformis,Oculimacula yallundae, Rhynchosporium secalis f. sp. hordei, Zymoseptoria tritici, Phaeosphaeria nodorum); grape powdery mildew (Erysiphe necator var. necator), black rot (Elsinoe ampelina), late rot (Colletotrichum aenigma, Colletotrichum fioriniae, Colletotrichum fructicola, Colletotrichum gloeosporioides s. str.), black rot (Guignardia bidwellii), vine wilt (Phomopsis viticola), brown spot (Pseudocercospora vitis); apple powdery mildew (Podosphaera leucotricha), black spot (Venturia inaequalis), leaf spot (Alternaria mali), Monilinia (Monilinia mali), canker (Valsa ceratosperma), ring spot (Botryosphaeria kuwatsukai), gray mold (Monilinia fructicola, Monilinia fructigena), brown spot (Diplocarpon mali), anthracnose (Colletotrichum aenigma, Colletotrichum fioriniae, Colletotrichum fructicola, Colletotrichum godetiae), black spot (Mycosphaerella pomi), sooty mold (Gloeodes) pomigena), sooty spot (Zygophiala jamaicensis); pear black spot (Alternaria kikuchiana), black spot (Venturia nashicola), brown spot (Mycosphaerella pyri), canker (Phomopsis fukushii), anthracnose (Colletotrichum fioriniae, Glomerella cingulata); peach gray mold (Monilinia fructicola, Monilinia fructigena), black spot (Cladosporium carpophilum), Phomopsis rot (Phomopsis sp.); persimmon anthracnose (Colletotrichum horii), horn spot leaf spot (Cercospora kaki), round leaf spot leaf spot (Mycosphaerella nawae); citrus black spot (Diaporthe citri, Diaporthe spp.), scab (Elsinoe fawcettii), blue mold (Penicillium italicum), green mold (Penicillium digitatum); cucurbit powdery mildew (Golovinomyces cucurbitacearum, Leveillula taurica, Podosphaera xanthii), anthracnose (Colletotrichum orbiculare), vine blight (Didymella bryoniae), vine wilt (Fusarium oxysporum f. sp. cucumerinum), brown spot (Corynespora cassiicola), gray mold (Botrytis cinerea), Phomopsis root rot (Phomopsis sp.); tomato ring spot (Alternaria linariae, Alternaria solani), anthracnose (Colletotrichum acutatum, Colletotrichum gloeosporioides, Colletotrichum nigrum), leaf mold (Fulvia fulva), Verticillium dahliae, wilt (Fusarium oxysporum f. sp. lycopersici); eggplant powdery mildew (Erysiphe cichoracearum, Leveillula taurica, Podosphaera xanthii), black blight (Corynespora cassiicola), sooty mold (Mycovellosiella nattrassii); rapeseed sclerotinia rot (Sclerotinia sclerotiorum); cruciferous crop black spot (Alternaria brassicae), white spot (Pseudocercosporella capsellae, Cercosporella brassicae), soybean sclerotinia rot (Sclerotinia sclerotiorum), purple spot (Cercospora kikuchii), black rot (Elsinoe glycines), black spot (Diaporthe phaseolorum var.Sojae), brown ring spot disease (Corynespora cassiicola); kidney bean anthracnose (Colletotrichum lindemuthianum); peanut black spot disease (Mycosphaerella berkeleyi), brown spot disease (Mycosphaerella arachidis, Cercospora canescens); pea powdery mildew (Erysiphe pisi); potato summer blight (Alternaria solani); tea white spot disease (Elsinoe leucospila), anthracnose (Gloeosporium theae-sinensis), ring spot disease (Neopestalotiopsis spp., Pestalotiopsis longiseta, Pestalotiopsis theae); tobacco red-red rust disease (Alternaria alternata), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum gloeosporioides); sugar beet powdery mildew (Oidium sp.), brown spot disease (Cercospora beticola); rose black spot disease (Diplocarpon rosae), powdery mildew (Erysiphe simulans, Podosphaera pannosa); chrysanthemum brown spot disease (Septoria obesa); strawberry powdery mildew (Podosphaera aphanis var. aphanis), anthracnose (Colletotrichum gloeosporioides, Colletotrichum acutatum, Glomerella cingulata, Colletotrichum aenigma, Colletotrichum fioriniae, Colletotrichum fragariae, Colletotrichum fructicola, Colletotrichum nymphaeae, Colletotrichum siamense); banana black sigatoka disease (Mycosphaerella fijiensis), yellow sigatoka disease (Mycosphaerella musicola), Panama disease (Fusarium oxysporum, Fusarium oxysporum f. sp.)Cuban grass; gray mold (Botrytis cinerea) and sclerotinia sclerotiorum on cucumbers, tomatoes, green beans, strawberries, grapes, etc.; dollar spot disease on grasses (Clarireedia jacksonii, Clarireedia monteithiana), leaf blight on Curvularia (Curvularia geniculata), damping-off (Gaeumannomyces graminis), and anthracnose (Colletotrichum caudatum). Mucoromycotina: Rice seedling blight (Rhizopus chinensis, Rhizopus oryzae) Oomycota: Rice seedling blight (Pythium spp.); cereal brown snow mold (Pythium iwayamai, Pythium paddicum, Pythium horinouchiense, Pythium graminicola, Pythium okanoganense); grape downy mildew (Plasmopara viticola); citrus brown rot (Phytophthora citricola, Phytophthora citrophthora, Phytophthora nicotianae, Phytophthora palmivora, Phytophthora syringae); pear blight (Phytophthora cactorum, Phytophthora syringae); peach blight (Phytophthora sp.); cucumber downy mildew (Pseudoperonospora cubensis), blight (Phytophthora melonis, Phytophthora nicotianae), seedling blight (Pythium cucurbitacearum, Pythium debaryanum); late blight of tomatoes, eggplants, and potatoes (Phytophthora infestans), seedling blight (Pythium vexans), root rot (Pythium aphanidermatum, Pythium myriotylum, Pythium dissotocum); white blight of leeks (Phytophthora porri); stem blight of soybeans (Phytophthora sojae), downy mildew (Peronospora manshurica); downy mildew of peas (Peronospora pisi); downy mildew of sugar beets (Peronospora schachtii), black root rot (Aphanomyces cochlioides); late blight of strawberries (Phytophthora cactorum, Phytophthora fragariaefolia, Phytophthora nicotianae, Phytophthora sp.), fruit rot (Pythium ultimum var. Pythium ultimum; Pythium periplocum, Pythium graminicola, Pythium vanterpoolii (grass species) Bacteria: Rice seedling blight (Burkholderia plantarii), bacterial leaf blight (Xanthomonas oryzae pv. oryzae), bacterial grain blight (Burkholderia gladioli, Burkholderia glumae), brown stripe disease (Acidovorax avenae subsp. avenae), glume browning (Pantoea ananatis); peach bacterial spot (Brenneria nigrifluens, Pseudomonas syringae pv. syringae, Xanthomonas arboricola pv. pruni); citrus canker (Xanthomonas citri subsp. citri); cucurbit bacterial spot (Pseudomonas syringae pv. lachrymans); tomato canker (Clavibacter michiganensis subsp. michiganensis); potato scab (Streptomyces spp.); Tea red blight (Pseudomonas syringae pv. theae); Bacterial wilt of tomatoes, potatoes, etc. (Ralstonia solanacearum); Soft rot of Chinese cabbage, leeks, onions, etc. (Pectobacterium carotovorum) Cercozoa: Clubroot disease in cruciferous crops (Plasmodiophora brassicae), etc.

[0173] The plant disease control agent of the present invention exhibits control effects even against the plant diseases exemplified above that have acquired resistance to existing plant disease control agents for agricultural and horticultural use. Furthermore, the plant disease control agent of the present invention can also be used on plants that have acquired characteristics such as insect resistance, disease resistance, and herbicide resistance through genetic modification, artificial crossbreeding, etc.

[0174] The "plants conferred with resistance by breeding methods or genetic modification technology" of this invention include not only plants conferred with resistance by classical crossbreeding and genetic modification technology, but also plants conferred with resistance by new breeding techniques (New Plant Breeding Techniques, NBTs) that combine conventional crossbreeding techniques with molecular biological methods. New breeding techniques (NBTs) are described in the book "Understanding New Plant Breeding Techniques" (International Literature Co., Ltd., by Ryo Osawa and Hiroshi Emoto), the review article "Genome Editing Tools in Plants" (Genes 2017, 8, 399, by Tapan Kumar Mohanta, Tufail Bashir, Abeer Hashem, Elsayed Fathi Abd_Allah and Hanhong Bae), etc.

[0175] Next, the manufacturing method, formulation method, and uses of the compound of the present invention will be described in detail in the following examples, but the present invention is not limited in any way to these examples. The melting point, which is a physical property of the compound of the present invention, was measured using a Yanaco MP-500V micro-melting point analyzer. The refractive index was measured using an Atago Abbe refractometer. 1 The 1H-NMR spectrum was measured using a JEOL JNM-ECS300 (300MHz) with tetramethylsilane (TMS) as the internal standard.

[0176] Furthermore, a method for producing the compound of the present invention is described. [Examples]

[0177] [Example 1] (1) Preparation of 3-[3-(tert-butyl)-5-(3-chlorophenoxy)-1-methyl-1H-pyrazole-4-yl]-5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine (Invention Compound No.: C-0042)

[0178] 0.60 g (1.2 mmol) of N-[1-(aminooxy)-3-(2,4-dimethylphenyl)propan-2-yl]-3-(tert-butyl)-5-(3-chlorophenoxy)-1-methyl-1H-pyrazole-4-carboxamide was dissolved in 40 ml of acetonitrile, to which 0.57 g (3.7 mmol) of phosphorus oxychloride was added, and the mixture was stirred at 100°C for 3 hours. After the reaction was complete, saturated sodium bicarbonate aqueous solution and ethyl acetate were added to the reaction mixture, and the organic layer obtained by liquid-liquid extraction was washed with saturated sodium bicarbonate aqueous solution and saturated brine, and dried over anhydrous magnesium sulfate. After filtering off insoluble matter, the solvent was removed under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (developing solvent, n-hexane:ethyl acetate = 2:1) to obtain 0.38 g of the target product (yield 66%).

[0179] 1 H-NMR data (300MHz, CDCl3 / TMSδ(ppm)):7.23(1H,t),7.09(1H,d),6.86-7.04(5H,m),4.36(1H,br),3.70(1H,dd), 3.60(3H,s),3.49-3.59(1H,m),3.36(1H,dd),2.67(1H,dd),2.50(1H,dd),2.29(3H,s),2.21(3H,s),1.37(9H,s)

[0180] (2) Preparation of N-[1-(aminooxy)-3-(2,4-dimethylphenyl)propan-2-yl]-3-(tert-butyl)-5-(3-chlorophenoxy)-1-methyl-1H-pyrazole-4-carboxamide

[0181] 0.78 g (1.3 mmol) of 3-(tert-butyl)-5-(3-chlorophenoxy)-N-{1-(2,4-dimethylphenyl)-3-[(1,3-dioxoisoindolin-2-yl)oxy]propan-2-yl}-1-methyl-1H-pyrazole-4-carboxamide was dissolved in 10 ml of dichloromethane and 10 ml of methanol. 0.19 g (3.8 mmol) of hydrazine monohydrate was added, and the mixture was stirred overnight at room temperature. After the reaction was complete, water and ethyl acetate were added to the reaction mixture. The organic layer obtained by liquid-liquid extraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering off insoluble matter, the solvent was removed under reduced pressure to obtain 0.60 g (98% yield) of the target product.

[0182] 1 H-NMR data (300MHz, CDCl3 / TMSδ(ppm)):7.24(1H,t),7.10(1H,d),6.88-6.95(3H,m),6.82(1H,d),6.73(1H,d d),6.37(1H,d),5.32(2H,br),4.38(1H,m),3.57(3H,s),3.42(2H,m),2.58(2H,d),2.25(6H,s),1.42(9H,s)

[0183] (3) Preparation of 3-(tert-butyl)-5-(3-chlorophenoxy)-N-{1-(2,4-dimethylphenyl)-3-[(1,3-dioxoisoindorin-2-yl)oxy]propan-2-yl}-1-methyl-1H-pyrazole-4-carboxamide

[0184] A 30 ml solution of DMF containing 0.50 g (1.6 mmol) of 3-(tert-butyl)-5-(3-chlorophenoxy)-1-methyl-1H-pyrazole-4-carboxylic acid and 0.80 g (2.1 mmol) of O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate was prepared under ice cooling. Then, a 15 ml solution of DMF containing 0.63 g (4.9 mmol) of N-ethyl-N-isopropylpropan-2-amine and 0.92 g (2.1 mmol) of 2-[2-amino-3-(2,4-dimethylphenyl)propoxy]isoindorin-1,3-dione-2,2,2-trifluoroacetate was added, and the mixture was heated to room temperature and stirred overnight. Water and ethyl acetate were added to the reaction mixture, and the organic layer obtained by liquid-liquid extraction was washed with saturated sodium bicarbonate aqueous solution and saturated saline solution, and dried over anhydrous magnesium sulfate. After filtering off the insoluble matter, the solvent was removed under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (eluent, n-hexane:ethyl acetate = 3:1) to obtain 0.88 g of the target product (yield 88%).

[0185] 1 H-NMR data (300MHz, CDCl3 / TMSδ(ppm)):7.75-7.85(4H,m),6.77-7.23(8H,m),4.31(1H,m),4 .22(1H,dd),3.93(1H,dd),3.61(3H,s),2.74(2H,d),2.29(3H,s),2.25(3H,s),1.41(9H,s)

[0186] [Example 2] (1) Preparation of 3-{3-(tert-butyl)-5-[(3-chlorophenyl)thio]-1-methyl-1H-pyrazole-4-yl}-5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine (Invention Compound No.: D-0002)

[0187] 1.30 g (2.6 mmol) of N-[1-(aminooxy)-3-(2,4-dimethylphenyl)propan-2-yl]-3-(tert-butyl)-5-[(3-chlorophenyl)thio]-1-methyl-1H-pyrazole-4-carboxamide was dissolved in 60 ml of acetonitrile, to which 2.00 g (13.0 mmol) of phosphorus oxychloride was added, and the mixture was stirred at 100°C for 3 hours. After the reaction was complete, saturated sodium bicarbonate aqueous solution and ethyl acetate were added to the reaction mixture, and the organic layer obtained by liquid-liquid extraction was washed with saturated sodium bicarbonate aqueous solution and saturated brine, and dried over anhydrous magnesium sulfate. After filtering off insoluble matter, the solvent was removed under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (developing solvent, n-hexane:ethyl acetate = 2:1) to obtain 0.86 g (yield 69%) of the target product.

[0188] 1 H-NMR data (300MHz, CDCl3 / TMSδ(ppm)):7.10-7.17(3H,m),6.86-6.96(4H,m),4.27(1H,br),4.0 1(1H,d),3.69-3.76(5H,m),2.84(1H,dd),2.64(1H,dd),2.27(3H,s),2.24(3H,s),1.40(9H,s)

[0189] (2) Preparation of N-[1-(aminooxy)-3-(2,4-dimethylphenyl)propan-2-yl]-3-(tert-butyl)-5-[(3-chlorophenyl)thio]-1-methyl-1H-pyrazole-4-carboxamide

[0190] 1.70 g (2.7 mmol) of 3-(tert-butyl)-5-[(3-chlorophenyl)thio]-N-[1-(2,4-dimethylphenyl)-3-((1,3-dioxoisoindorin-2-yl)oxy)propan-2-yl]-1-methyl-1H-pyrazole-4-carboxamide was dissolved in 40 ml of dichloromethane and 40 ml of methanol. 0.40 g (8.1 mmol) of hydrazine hydrate was added, and the mixture was stirred overnight at room temperature. After the reaction was complete, water and ethyl acetate were added to the reaction mixture. The organic layer obtained by liquid-liquid extraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering off the insoluble matter, the solvent was removed under reduced pressure to obtain 1.37 g (100% yield) of the target product.

[0191] 1 H-NMR data (300MHz, CDCl3 / TMSδ(ppm)):7.15-7.23(2H,m),7.10(2H,d),6.93(1H,br),6.82-6.88(2H,m),6.35(1H,b r),4.45-4.54(1H,m),3.81(3H,s),3.61(1H,dd),3.52(1H,dd),2.75(2H,t),2.30(3H,s),2.25(3H,s),1.38(9H,s)

[0192] (3) Preparation of 3-(tert-butyl)-5-((3-chlorophenyl)thio)-N-(1-(2,4-dimethylphenyl)-3-((1,3-dioxoisoindorin-2-yl)oxy)propan-2-yl)-1-methyl-1H-pyrazole-4-carboxamide

[0193] 1.00 g (3.1 mmol) of 3-(tert-butyl)-5-[(3-chlorophenyl)thio]-1-methyl-1H-pyrazole-4-carboxylic acid, 1.52 g (4.0 mmol) of O-(7-azabenzotriazol-1-yl)-N,N,N’,N’-tetramethyluronium hexafluorophosphate in 50 ml of DMF was cooled in ice, and 1.19 g (9.2 mmol) of N-ethyl-N-isopropylpropan-2-amine and 1.75 g (4.0 mmol) of 2-[2-amino-3-(2,4-dimethylphenyl)propoxy]isoindoline-1,3-dione-2,2,2-trifluoroacetate were added. The temperature was raised to 60 °C and stirred for 7 hours. After completion of the reaction, water and ethyl acetate were added to the reaction solution, and the organic layer obtained by liquid separation was washed with saturated aqueous sodium bicarbonate solution, water, and saturated brine, and dried over anhydrous magnesium sulfate. After filtering off the insoluble matter, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (developing solvent, n-hexane:ethyl acetate = 3:1) to obtain 1.80 g (yield 93%) of the target product.

[0194] 1 H-NMR data (300 MHz, CDCl3 / TMS δ (ppm)): 7.75 - 7.84 (4H, m), 7.20 (1H, d), 7.15 (1H, d), 7.06 (2H, dd), 6.90 - 6.97 (3H, m), 6.87 (1H, d), 4.42 - 4.51 (1H, m), 4.35 (1H, dd), 4.01 (1H, dd), 3.81 (3H, s), 3.06 (1H, dd), 2.96 (1H, dd), 2.37 (3H, s), 2.27 (3H, s), 1.37 (9H, s)

[0195] (4) Production of 3-(tert-butyl)-5-[(3-chlorophenyl)thio]-1-methyl-1H-pyrazole-4-carboxylic acid

[0196] To a solution of 5.50 g (18.0 mmol) of 3-(tert-butyl)-5-[(3-chlorophenyl)thio]-1-methyl-1H-pyrazole-4-carbaldehyde in 80 ml of tert-butanol and 20 ml of water were added 11.0 g (0.2 mmol) of 2-methyl-2-butene, 13.0 g (0.1 mmol) of sodium dihydrogen phosphate, and 4.80 g (53.0 mmol) of sodium chlorite, and the mixture was stirred at room temperature overnight. After completion of the reaction, water and ethyl acetate were added to the reaction solution, and the organic layer obtained by liquid separation was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering off the insoluble matter, the solvent was distilled off under reduced pressure, and the obtained crude product was washed with a mixed solution of diisopropyl ether and n-hexane to obtain 3.97 g (yield 69%) of the target product.

[0197] 1 H-NMR data (300 MHz, DMSO-d6 / TMS δ (ppm)): 7.28 - 7.40 (2H, m), 7.16 (1H, s), 7.10 (1H, dd), 3.75 (3H, s), 1.36 (9H, s) [[ID=,7]]

[0198] (5) Preparation of 3-(tert-butyl)-5-[(3-chlorophenyl)thio]-1-methyl-1H-pyrazole-4-carbaldehyde

[0199] To a solution of 4.00 g (20.0 mmol) of 3-(tert-butyl)-5-chloro-1-methyl-1H-pyrazole-4-carbaldehyde and 8.50 g (59.0 mmol) of 3-chlorobenzenethiol in 80 ml of DMF was added 1.70 g (30.0 mmol) of potassium hydroxide, and the mixture was stirred at 120 °C for 2 hours. After completion of the reaction, water and ethyl acetate were added to the reaction solution, and the organic layer obtained by liquid separation was washed with water and saturated brine and dried over anhydrous magnesium sulfate. After filtering off the insoluble matter, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (developing solvent, n-hexane:ethyl acetate = 3:2) to obtain 5.50 g (yield 89%) of the target product.

[0200] 1H-NMR data (300MHz, CDCl3 / TMSδ(ppm)): 10.06(1H,s),7.20-7.23(2H,m),7.07(1H,s),6.90(1H,dd),3.83(3H,s),1.42(9H,s)

[0201] Physical properties (melting point, refractive index, and 1 The 1H-NMR spectral data, including the values ​​from the above examples, are shown in Tables 11 and 15 below. The compound numbers and symbols in the tables have the same meaning as described above.

[0202] [Table 11]

[0203] [Table 12]

[0204] [Table 13]

[0205] [Table 14]

[0206] [Table 15]

[0207] Next, specific examples of formulations of the plant disease control agent for agricultural and horticultural use of the present invention, using the pyrazole-4-oxadiazine ring compound, its optical isomer, or its salt, manufactured as described above, will be explained. However, the types of compounds and additives and their mixing ratios are not limited to these and can be changed within a wide range. Also, in the following explanation, "parts" means parts by mass.

[0208] [Formulation Example 1] Emulsion 10 parts of each compound described in Tables 1 to 15<00,00960>30 parts of cyclohexanone 11 parts of polyoxyethylene alkyl aryl ether 4 parts of calcium alkylbenzene sulfonate 45 parts of methylnaphthalene The above was uniformly dissolved to obtain an emulsion.

[0209] [Formulation Example 2] Wettable Powder 10 parts of each compound described in Tables 1 to 15 0.5 part of sodium naphthalenesulfonate formalin condensate 0.5 part of polyoxyethylene alkyl aryl ether 24 parts of diatomaceous earth 65 parts of clay The above was uniformly mixed and pulverized to obtain a wettable powder.

[0210] [Formulation Example 3] Dust 2 parts of each compound described in Tables 1 to 15 5 parts of diatomaceous earth 93 parts of clay The above was uniformly mixed and pulverized to obtain a dust.

[0211] [Formulation Example 4] Granule 5 parts of each compound described in Tables 1 to 15 2 parts of sodium lauryl alcohol sulfate 5 parts of sodium lignin sulfonate 2 parts of carboxymethyl cellulose 86 parts of clay The above was uniformly mixed and pulverized. An amount equivalent to 20 parts of water was added to this mixture, kneaded, processed into 14 - 32 mesh granules using an extrusion granulator, and then dried to obtain granules.

[0212] [Formulation Example 5] Flowable 20 parts of each compound described in Tables 1 to 15 4 parts of polyoxyethylene styrenated phenyl ether sulfate Ethylene glycol 7 parts Silicone AF-118N (manufactured by Asahi Kasei Corporation) 0.02 parts Wednesday 68.98 parts The above ingredients were mixed in a high-speed agitator for 30 minutes, and then pulverized in a wet pulverizer to obtain a flowable formulation.

[0213] [Formulation Example 6] Granular wettable powder Ten copies of each compound listed in Tables 1-15. Sodium lignin sulfonate 5 parts Polyoxyethylene alkylaryl ether (1 part) Sodium polycarboxylate 3 parts White carbon 5 parts Pregelatinized starch (part 1) Calcium carbonate 65 units 10 parts water The above ingredients were mixed, kneaded, and pressed into granules. The resulting granular material was dried in a fluidized bed dryer to obtain a wettable powder granule.

[0214] Next, the effects of the disease control agent of the present invention will be explained with reference to test examples.

[0215] [Example Test] Cucumber gray mold (Botrytis cinerea) prevention efficacy test 1 Cucumber seeds were sown in pots, and the grown cucumber seedlings were sprayed with a chemical solution adjusted to an active ingredient concentration of 500 ppm. Subsequently, filter paper soaked in Botrytis cinerea gray mold fungus spores suspended in a liquid medium containing 0.3% yeast extract and 2% glucose was placed on the surface of the cucumber cotyledons for inoculation, and the plants were then moved to a humid chamber for storage. After the untreated group had fully developed the disease, the degree of disease on the inoculated leaves was investigated using an index according to the criteria in Table 16 below. The disease severity was calculated using the formula shown as Equation 1, and the control value was calculated using the formula shown as Equation 2.

[0216] [Table 16]

[0217]

number

[0218] [In the formula, N represents the total number of leaves surveyed, n0 represents the number of leaves with a disease index of 0, n1 represents the number of leaves with a disease index of 1, n2 represents the number of leaves with a disease index of 2, n3 represents the number of leaves with a disease index of 3, and n4 represents the number of leaves with a disease index of 4.]

[0219]

number

[0220] The test results showed that A-0012, A-0015, A-0021, A-0030, A-0062, C-0056, C-0057, C-0058, and C-0060 had a control value of 75 or more but less than 100, while A-0013, A-0017, A-0019, A-0020, A-0022, A-0024, A-0026, A-0028, A-0032, A-0064, A-0067, C-0017, and C-001 8, C-0025, C-0026, C-0031, C-0032, C-0042, C-0044, C-0048, C-0049, C-0050, C-0051, C-0052, C-0053, C-0061, C-0062, C-0063, C-0064, C-0065, C-0068, C-0069, C-0076, C-0077, D-0002, and D-0012 had a control value of 100. [Industrial applicability]

[0221] This invention provides a plant disease control agent containing a novel pyrazole-4-oxadiazine ring compound as an active ingredient, which has high control efficacy. It is useful in the fields of pesticides and agriculture and has industrial applicability.

Claims

1. A compound represented by general formula [I], its optical isomer, or its salt. 【Chemistry 1】 [In the formula, A is an oxygen atom, a sulfur atom, S=O, or S(=O) ２ Show, R １ is a hydrogen atom, C １ to C ６ alkyl group, C １ to C ６ haloalkyl group, C ３ to C ８ cycloalkyl group, C １ to C ６ alkoxy-C １ to C ６ alkyl group, C １ to C ６ haloalkoxy-C １ to C ６ alkyl group, cyano C １ to C ６ alkyl group, C ６ to C １２ aryl-C １ to C ６ alkyl group, C １ to C ６ alkylcarbonyl group, C １ to C ６ alkylsulfonyl group, C ６ to C １２ aryl group, or C ６ to C １２ aryl-C １ to C ６ alkyl group (the aryl group may be substituted with one or more substituents selected from R １０ ), and R ２ C is a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, a nitro group, and １ ~C ６ Alkyl alkyl group, C １ ~C ６ Haloalkyl group, C ３ ~C ８ Cycloalkyl groups, C １ ~C ６ Alkoxy group, C １ ~C ６ Haloalkoxy group, C １ ~C ６ Alkyl-C ３ ~C ８ Cycloalkyl groups, hydroxy C １ ~C ６ Alkyl alkyl group, C １ ~C ６ Alkoxy-C １ ~C ６ Alkyl alkyl group, C ３ ~C ８ Cycloalkyl-C １ ~C ６ Alkyl alkyl group, C １ ~C ６ Alkylcarbonyl group, C １ ~C ６ Alkoxycarbonyl group, aminocarbonyl group, C １ ~C ６ Alkyl sulfanyl group, C １ ~C ６ Alkyl sulfinyl group, C １ ~C ６ Alkyl sulfonyl group, C ６ ~C １２ Aryl group (the aryl group has one or more R １０ (The heteroaryl group may be substituted with substituents selected from the above), a 5-12 member heteroaryl group (the heteroaryl group has one or more R １０ (may be substituted with substituents selected from) amino group, C １ ~C ６ Alkylamino group (the amino group is R ９ (May be substituted with substituents selected from) C １ ~C ６ Alkylcarbonylamino group (the amino group is R ９ (may be substituted with substituents selected from), or -C (=NR ７ ) R ８ Show the basis, Q １ C ３ ~C ８ Cycloalkyl groups, C ６ ~C １２ Aryl group (the aryl group has one or more R １０ (The group may be substituted with substituents selected from the following), or a 5-12 member heteroaryl group (the heteroaryl group may have one or more R １０ (May be substituted with substituents selected from) Q ２ represents C ６ to C １２ aryl group (the aryl group may be substituted with one or more substituents selected from R １０ ), or a 5- to 12-member heteroaryl group (the heteroaryl group may be substituted with one or more substituents selected from R １０ ), and R ３ represents a hydrogen atom, C １ to C ６ alkyl group, or C １ to C ６ alkylcarbonyl group, and R ４ is a hydrogen atom, or C １ ~C ６ It shows an alkyl group, R ５ and R ５’ is a hydrogen atom, a halogen atom, or C １ ~C ６ It shows an alkyl group, R ６ and R ６’ is a hydrogen atom, a halogen atom, or C １ ~C ６ It shows an alkyl group, R ７ is C １ ~C ６ Alkyl alkyl group, C １ ~C ６ Alkylaminocarbonyl group (the amino group is R ９ (may be substituted with substituents selected from, or C) １ ~C ６ Alkyl-C ３ ~C ８ Cycloalkylcarbonylamino group (the amino group is R ９ (May be substituted with substituents selected from) R ８ is a hydrogen atom, or C １ ~C ６ It shows an alkyl group, R ９ is C １ ~C ６ It shows an alkyl group, R １０ is a hydroxyl group, halogen atom, cyano group, C １ ~C ６ Alkyl alkyl group, C １ ~C ６ Haloalkyl group, C １ ~C ６ Alkoxy-C １ ~C ６ Alkyl alkyl group, C １ ~C ６ Alkoxy group, C ６ ~C １２ Aryl-C １ ~C ６ Alkoxy group, C １ ~C ６ Alkoxy-C １ ~C ６ Alkoxy group, cyano C １ ~C ６ Alkoxy group, C １ ~C ６ Alkyl sulfanyl group, C １ ~C ６ Alkyl sulfinyl group, C １ ~C ６ Alkyl sulfonyl group, C １ ~C ６ Alkylcarbonylamino group (the amino group is R ９ (May be substituted with substituents selected from) C １ ~C ６ Alkylaminocarbonylamino group (the amino group is R ９ (May be substituted with substituents selected from) C ６ ~C １２ Aryl group, C ６ ~C １２ Aryloxy group, 5-12 member heteroarylcarbonylamino group, 5-12 member heteroaryloxy group, 5-12 member heteroaryl-C １ ~C ６ Alkoxy group, or -C(=NR ７ ) R ８ [Indicating the basis] A compound represented by, or a salt thereof.

2. A plant disease control agent for agricultural and horticultural use, characterized by containing the compound described in claim 1, an optical isomer thereof, or a salt thereof as an active ingredient.

3. The plant disease control agent for agricultural and horticultural use according to claim 2, wherein the plant disease is derived from a pathogenic fungus.

4. The plant disease control agent for agricultural and horticultural use according to claim 3, wherein the pathogenic fungi are classified into the kingdoms of Fungi, Stramenopyla, Rhizaria, and Bacteria.

5. A plant disease control composition for agricultural and horticultural use comprising the compound described in claim 1, an optical isomer thereof, or a salt thereof, and an agriculturally acceptable carrier.

6. A method for controlling diseases of useful plants, comprising spraying an effective amount of the compound described in claim 1, an optical isomer thereof, or a salt thereof onto a useful plant, a part of a useful plant, or a place where the useful plant is growing.

7. The method according to claim 6, wherein the plant disease is derived from a pathogenic fungus.

8. The method according to claim 7, wherein the pathogenic fungus is classified into the kingdoms of Fungi, Stramenopyla, Rhizaria, and Bacteria.

9. Use of the compound described in claim 1, its optical isomer, or its salt as a plant disease control agent for useful plants in agriculture and horticulture.

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