WO2001056979A1 - Substituted cyanoacetamide derivatives and herbicides - Google Patents

Substituted cyanoacetamide derivatives and herbicides Download PDF

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Publication number
WO2001056979A1
WO2001056979A1 PCT/JP2001/000603 JP0100603W WO0156979A1 WO 2001056979 A1 WO2001056979 A1 WO 2001056979A1 JP 0100603 W JP0100603 W JP 0100603W WO 0156979 A1 WO0156979 A1 WO 0156979A1
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group
alkoxy
alkyl
methyl
groups
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PCT/JP2001/000603
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French (fr)
Japanese (ja)
Inventor
Hiroyuki Yamanaka
Satoshi Kajita
Katsunori Tanaka
Masami Koguchi
Shigeo Yamada
Akihiro Takahashi
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Nippon Soda Co., Ltd.
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Priority to AU2001227114A priority Critical patent/AU2001227114A1/en
Publication of WO2001056979A1 publication Critical patent/WO2001056979A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • C07C317/46—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/04—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/32—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids

Definitions

  • the present invention relates to a substituted cyanoacetamide derivative in which a methylene moiety of a novel cyanoacetamide is substituted with a substituted benzoyl group, and a herbicide.
  • EP 0213892 describes a compound represented by the formula (A) having herbicidal activity and a method for producing the compound.
  • R 1 represents an alkyl group, a cycloalkyl group, and the like, and Q represents a heterocyclic group.
  • R 1 is bonded to a nitrogen atom as in the compound of the present invention. There is no description of the compound that is the group to be formed.
  • EP-A-625505 describes a compound represented by the following formula (C).
  • the compound represented by the formula (C) does not include a compound in which 1 to! ⁇ 5 is a heterocyclic group. Further, there is no description of a compound in which R 6 is an alkyl group or a cycloalkyl group and is a group formed by bonding to a nitrogen atom.
  • An object of the present invention is to provide a herbicide that can be synthesized industrially advantageously, is effective at a low dose, has high safety, and has good crop selectivity.
  • the present invention firstly provides a formula (1)
  • R 2 are each independently a hydrogen atom, a nitro group, Shiano group, a halogen atom, C 1-6 alkyl, C 1-6 alkoxy group, a haloalkyl group, C 1-6 Haroarukoki Represents a C 1-6 alkylthio group, an alkylsulfonyl group or a C 1-6 alkylsulfonyl group.
  • R 3 represents a nitro group, a cyano group, a halogen atom, an alkyl group, an alkoxy group, a C 6 haloalkyl group, a d- 6 haloalkoxy group, an alkylthio group, a C 1-6 alkylsulfenyl group or an alkylsulfonyl group.
  • n represents 0, 1 or 2.
  • R 4, R 5 are each independently a hydrogen atom, an alkyl group, C 2 - 6 alkenyl group, CI- 6 alkoxy group, C 1-6 haloalkyl group, C 1-6 hydroxycarboxylic alkyl group, Ji 6 Haroaru Kokishi group, C 3 - 8 cycloalkyl group, an alkoxy group, Haroaruko alkoxy C - 6 alkyl group, CI- 6 alkoxy C 1-6 alkoxy group, C 1-6 haloalkoxy CM ⁇ alkoxy group, alkylthio C - 6 Alkyl group, C 1-6 alkylthio C 1-6 alkoxy group, amino group, CM alkylamino group, dialkylamino group, alkylcarbonyl group, c1 -s alkoxycarbonyl group, haloalkylcarbonyl group, haloalkoxy carbonyl group, CM alkylsulfonyl group, the haloalky
  • R 4 and R 5 are joined together to form an alkylene chain having 2 to 5 carbon atoms, or R 4 and R 5 together with the bonded nitrogen atom are substituted with a C 1-6 alkyl group or the like. May form a 5- or 6-membered nitrogen-containing heterocyclic ring containing 2 to 4 oxygen or nitrogen atoms.
  • X represents an oxygen atom or a sulfur atom.
  • Z is a formyl group, di-d-6 alkoxymethyl group, C 2 _ 6 alkenyl, C 2-6 Arukini Le group, C 1-6 alkoxides Consequences amino methyl, C 1-6 halo alkoxides Consequences amino methyl group, C 2 _ 6 ⁇ Luque two Ruiminomechiru group, C 26 Haroaruke two Ruiminomechiru group, (halogen atom, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 haloalkyl group, Shiano group, such as nitro group)
  • the optionally substituted heterocyclic group in z of the compound represented by the formula (l) is preferably a kind of group selected from the group shown below.
  • R 6 and R 7 each independently represent a hydrogen atom, a halogen atom, a C 1-6 alkyl group, a haloalkyl group, or a C 1-6 alkoxy group.
  • the present invention provides a herbicide containing one or more of the compound represented by the formula (1) or a salt thereof as an active ingredient.
  • R i and R 2 are each independently a hydrogen atom, a nitro group, a cyano group,
  • Halogen atoms such as fluorine, chlorine, and bromine
  • a C 1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isoptyl, s-butyl, t-butyl, etc.
  • Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, t-butoxy,
  • 6- haloalkyl groups such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 1,1-difluoroethyl, 1,1,1-trifluoroethyl and pentafluoroethyl , C such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1-fluoroethoxy, 1,1-difluoroethoxy, 1,1,1-trifluoroethoxy, pentafluoroethoxy, etc. 1-6 noroanorecoxy group,
  • C w alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, and butylthio;
  • 6- alkyl sulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfenyl, isopropylsulfenyl, butylsulfenyl and t-butylsulfenyl;
  • Alkyl sulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, t-butylsulfonyl, etc.
  • R 3 is a nitro group, a cyano group
  • Halogen atoms such as fluorine, chlorine, and bromine
  • alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isoptyl, S-butyl, t-butyl, etc.
  • Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, t-butoxy,
  • haloalkyl groups chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1-fluoroethoxy, 1,1 difluoroethoxy, 1,1,1-trifluoroethoxy, pentafluoro Roethoxy etc.
  • CM alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, and t-butylthio;
  • a C 1-6 alkyl sulfonyl group such as methylsulfonyl, ethylsulfonyl, propylsulfenyl, isopropylsulfonyl, butylsulfonyl, t-butylsulfonyl, etc.
  • Alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and t-butylsulfonyl;
  • R 4 and R 5 are each independently a hydrogen atom
  • Ci-6 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isoptyl, s-butyl, t-butyl, etc.
  • CM alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, t-butoxy,
  • Haloalkyl groups such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 1,1-difluoroethyl, 1,1,1-trifluoroethyl and pentafluoroethyl; C such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1_fluoroethoxy, 1,1-difluoroethoxy, 1,1,11-trifluoroethoxy, pentafluoroethoxy, etc. 6 halo anolecoxy group,
  • C 3-8 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
  • haloalkoxy C 1-6 alkyl group such as trifluoromethyloxymethyl, trifluoromethylethyl, etc.
  • Alkoxy c 1-6 alkoxy groups such as methoxy methoxy, methoxy ethoxy, ethoxy methoxy, etc.
  • C i- 6 haloal such as trifluorometoxime toxic, trifluorometoxetoxy, etc.
  • C 1-6 alkylthio 6 alkyl groups such as methylthiomethyl, methylthioethyl, ethylthiomethyl,
  • C 1-6 alkylthioalkoxy groups such as methylthiomethoxy, methylthioethoxy, and ethylthiomethoxy;
  • Alkylamino groups such as methylamino, ethylamino, propylamino, isopropylamino, and butylamino;
  • Dialkylamino groups such as dimethylamino, getylamino, and ethylmethylamino
  • Alkylcarbonyl groups such as acetyl, propionyl, and petyryl
  • D- 6 alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl,
  • Haloalkylcarbonyl groups such as fluoroacetyl, chloroacetyl, trifluoroacetyl, trichloroacetyl,
  • R 4 and R 5 are joined together to form an alkylene chain having 2 to 5 carbon atoms of ethylene, trimethylene, tetramethylene, or pentamethylene, or R 4 and R 5 are a substituent together with a bonding nitrogen atom. May form a nitrogen-containing heterocycle containing 2 to 4 5- or 6-membered nitrogen or oxygen atoms.
  • Such heterocycles include morpholine 41-yl, piperazine 1-1-yl, 1,3,5-perhydrotriazine 1-yl, imidazole 11-yl, pyrazole 11-yl , 1, 2, 4-triazole-l-yl, oxazolidine-l-yl, tetrazol-l-yl and the like. These may be substituted with a C 1-6 alkyl group such as methyl and ethyl.
  • Z is a formyl group
  • Dialkoxymethyl groups such as dimethoxymethyl and diethoxymethyl
  • Echiniru 1 one propynyl, C 2 2-propynyl, and the like - 6 alkynyl group
  • Haloalkoxyminomethyl groups such as fluoromethinominomethyl, chloromethoxyminomethyl, trifinoleolomethoxyminomethyl, and trichloromethoxyminomethyl;
  • More preferred examples of the optionally substituted heterocyclic group for Z include the following groups.
  • R 6 and R 7 are each independently a hydrogen atom, a halogen atom such as fluorine, chlorine, or bromine; an alkyl group such as methyl or ethyl; a d- 6 haloalkyl group such as chloromethyl or trifluoromethyl; Represents a C 1-e alkoxy group such as methoxy and ethoxy.
  • X represents an oxygen atom or a sulfur atom.
  • Table 1 shows typical examples of the compound of the present invention.
  • the abbreviations of AZ1-Z30 used in column Z of this table and Table 2 have the following meanings.
  • the compound (2) and the compound represented by the formula: Ar COQ are reacted in the presence of a base in a solvent in an amount of 1 mol or an excess of each of them, whereby the compound represented by the formula (1) is obtained. Is obtained.
  • Solvents that can be used in this reaction include hydrocarbons such as benzene and toluene, ethers such as tetrahydrofuran (THF) and getyl ether, halogenated hydrocarbons such as methylene chloride and chloroform, and dimethylformamide. (DMF), dimethyl sulfoxide (DMSO), acetonitrile, water, or a mixed solvent thereof.
  • hydrocarbons such as benzene and toluene
  • ethers such as tetrahydrofuran (THF) and getyl ether
  • halogenated hydrocarbons such as methylene chloride and chloroform
  • dimethylformamide dimethylformamide
  • DMF dimethyl sulfoxide
  • acetonitrile water, or a mixed solvent thereof.
  • the base examples include aliphatic amines such as triethylamine and diisopropylethylamine; organic bases such as pyridine; alkali metal hydroxides such as KOH and NaOH; alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, alkaline earth metal carbonates such as calcium carbonate, alcoholates such as sodium methylate and magnesium ethylate, NaH, lithium Diisopropylamide (LDA) or the like can be used.
  • aliphatic amines such as triethylamine and diisopropylethylamine
  • organic bases such as pyridine
  • alkali metal hydroxides such as KOH and NaOH
  • alkali metal carbonates such as sodium carbonate and potassium carbonate
  • Alkali earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, alkaline earth metal carbonates such as calcium carbonate, alcoholates such as sodium methylate
  • the reaction proceeds smoothly from ⁇ 78 ° C. to the boiling point of the solvent used, preferably from ⁇ 10 ° C. to room temperature.
  • the present compound (1) is the compound (2) wherein: A r C0 2 H (.
  • a r is said to represent the same meaning) dicyclohexyl a compound represented by cyclohexyl Cal positive imide (DC It can also be obtained by reacting in the presence of a dehydrating condensing agent such as C).
  • Examples of the solvent used in this reaction include methylene chloride, chloroform, toluene, ethyl acetate, DMF, THF, 1,2-dimethyloxetane (DME), and acetate nitrile.
  • the reaction mixture is stirred at 110 ° C to 50 ° C until the reaction is completed, and processed by a conventional method.
  • Compound (2) can be obtained, for example, by an amidation reaction between a cyanoacetic acid ester and a corresponding amine, a reaction between a cyanoacetic acid and an amine using a dehydrating condensing agent such as DCC, It can be produced by a general synthetic chemistry technique such as a reaction between chloride and amines.
  • the compound (1) of the present invention contains a free hydroxyl group
  • the compound can be obtained by a known method from an enamine or an analog thereof, an acylate, a sulfonate, a sulfamate, an ether, a thioether, a sulfoxide or a sulfone derivative. And so on.
  • Said suitable enamines or analogs thereof are those in which the OH moieties are each of the formula: — NR e R f (wherein 16 and 1 are each independently hydrogen or a substitution of 1 to 6 carbon atoms. Represents an alkyl group or an aryl group which may be substituted.), Halogen, S (0) g Rh (where Rh is an alkyl group or an aryl group having 1 to 6 carbon atoms which may be substituted) And g represents 0, 1 or 2.).
  • the OH portion is represented by the following formula: —OCOR i, —OR j or OCONRkR l (wherein, R i and R j have the same meanings as the above Rh. And Rk and R 1 have the same meaning as the above-mentioned R e.).
  • the compound represented by the formula (1) can be derived into a salt thereof, particularly, an agriculturally / horticulturally acceptable salt.
  • agriculturally and horticulturally acceptable salts include alkali metal salts such as sodium and potassium, alkaline earth salts such as calcium and ammonium salts, and the like.
  • ammonium salts include those of the formula: N + R a Rb R c R d (where R a, Rb, R c and Rd are each independently substituted by hydrogen or a hydroxy group, etc. And a 10- alkyl group.
  • R a, Rb, R c and Rd are each independently substituted by hydrogen or a hydroxy group, etc.
  • a 10- alkyl group When any of Ra, Rb, Rc, and Rd is a substituted alkyl group, these preferably contain 1 to 4 carbon atoms.
  • the compound (1) of the present invention may have, for example, the following tautomers.
  • R 4 or R 5 is a hydrogen atom, the following tautomers may exist.
  • the compound of the present invention can be obtained by carrying out a usual post-treatment after completion of the reaction.
  • the structure of the compound of the present invention can be determined by measuring various spectra such as IR, NMR and MS.
  • the herbicide of the present invention contains one or more of the compounds of the present invention as an active ingredient.
  • the compound of the present invention can be used in a pure form without adding other components.
  • it can be used in the form of general pesticides that can be used for pesticides, for example, wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, flowables and the like.
  • mineral powder such as soy flour, flour, etc., vegetable powder, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay, etc.
  • Organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate can be used. .
  • oil fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethyls
  • a surfactant may be added, if desired, to obtain a uniform and stable form in these preparations.
  • the surfactant is not particularly limited, and examples thereof include an alkylphenyl ether to which polyoxetylene is added, an alkyl ether to which polyoxetylene is added, a higher fatty acid ester to which polyoxyethylene is added, and a polyoxyethylene.
  • Nonionic surfactants such as sorbitan higher fatty acid esters to which oxyethylene is added, tristyrylphenyl ether to which polyoxyethylene is added, sulfate salts of alkylphenyl ether to which polyoxyethylene is added, alkyl naphthalene sulfonates, Examples include polycarboxylates, ligninsulfonates, formaldehyde condensates of alkylnaphthalenesulfonates, and copolymers of isobutylene-maleic anhydride.
  • the concentration of the active ingredient in the herbicide of the present invention can be changed to various concentrations depending on the form of the preparation described above.
  • concentrations for example, in a wettable powder, 5 to 90% by weight (hereinafter simply referred to as%), preferably 10 to 85%, and in an emulsion, 3 to 70%, preferably 5 to 90%.
  • the concentration can be adjusted to about 60%, in the case of granules, from 0.01 to 50%, preferably from 0.05 to 40%.
  • the wettable powder or emulsion thus obtained is diluted with water to a predetermined concentration to form a suspension or an emulsion, and the granules are directly sprayed or dispersed on soil before or after germination of the weeds. It is mixed.
  • the actual application amount of the herbicide of the present invention is preferably 0.1 g or more of the active ingredient per hectare.
  • the herbicide of the present invention can be used in combination with known fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers, and the like.
  • the synergistic action of the mixed drug can be expected to have even higher effects.
  • a combination with a plurality of known herbicides is also possible.
  • agents suitable for use in combination with the herbicide of the present invention include the following. It is.
  • Anilide herbicides such as diflupanican and propanil; chloroacetamide herbicides such as arlacrol and pretilachlor; aryloxyalkanoic acid herbicides such as 2,4-D, 2,4-DB; diclohop- Aryloxy phenoxy alkanoic acid herbicides such as methyl and phenyl oxapropetyl; arylcarboxylic acid herbicides such as dicampa and pyrithiobac; imidazoline herbicides such as imazaquin and imazethapyr Urea herbicides such as diperon and isoprolon; carbamate herbicides such as chlorprofam and phenmedipham; thiobencalp, EPTC and other chitosan-bameto herbicides; trifluralin, dinitroa such as pendimethalin, etc.
  • Diphenyl herbicides diphenyl ethers such as acifluorene and homesaphene Herbicides; Sulfonyl-peryl herbicides such as benzulfuron monomethyl and nicosulfuron; Triazinone herbicides such as metripzine and metamethanone; Triazine herbicides such as atrazine and cyanazine; Triazopyrimidines such as flumellam Herbicides; Nitrile herbicides such as promoxinil and dikopenyl; Phosphoric acid herbicides such as glyphosate and glyphosinate; Quaternary ammonium salt herbicides such as paracoat and dibenzozot; Cyclic imidic herbicides such as fluthiacet-methyl; benzoylaminopropionic acid herbicides such as benzoylp mouthpethyl and flancropethyl; others, isoxaben, etofumesate, oxadiazone,
  • Additives such as vegetable oils and oil concentrates can also be added to compositions combining these.
  • the compound of the present invention shows a high herbicidal activity in soil treatment and foliage treatment under upland cropping conditions, is effective for various upland weeds such as meadowgrass, Aquinoenoko mouth, Ichibi, and Inubu, and is effective for corn, wheat, soybean, peta, etc. Some compounds are selective for crops.
  • the compound of the present invention Objects can also be applied to the control of weeds in orchards, lawns, track ends, vacant lots, etc.
  • the compounds of the present invention also include compounds that exhibit a plant growth regulating effect such as a growth inhibitory effect on useful plants such as crops, ornamental plants and fruit trees.
  • the compounds of the present invention include compounds that have excellent herbicidal activity against various paddy weeds such as nobie, tamagayari, omodaka, firefly, etc., and have selectivity to rice.
  • the compounds of the present invention also include those having a plant growth regulating activity, a bactericidal activity, an insecticidal and acaricidal activity.
  • Table 2 shows typical examples of the compounds of the present invention obtained as described above, including the above Examples.
  • NMR-4 2.74 (3H, s) 3,28 (3H, s) 3.37 (3H, s) 3.86 (3H, s) 7.85 (1H, d) 8.23 (1H, d)
  • NMR-5 2.36 ( 3H, s) 2.73 (3H, s) 3.32 (6H, s) 7.69 (1 H, d) 8.37 (1 H, d) 8.39 (1 H, s)
  • NMR-6 2.36 (3H, s) 2.83 (3H , s) 3.38 (3H, s) 3.85 (3H, s) 7.72 (1H, d) 8.29 (1H, d)
  • the above ingredients are uniformly mixed and finely pulverized to obtain a wettable powder containing 20% of the active ingredient.
  • the herbicidal effect was investigated according to the following criteria and expressed as a herbicidal index.
  • 1, 3, 5, 7, and 9 are intermediate values between 0 and 2, 2 and 4, 4 and 6, 6 and 8, and 8 and 10, respectively.
  • a 200 cm 2 pot was filled with soil, and seedlings of Meechishiba, Achinonokorogosa, Inubu, Ichibi and Maize were sown on the surface layer, lightly covered with soil, and grown in a greenhouse.
  • the aqueous dilution of the emulsion shown in Example 8 for each test compound is added to 50 liters / 10 liters so that the active ingredient has a predetermined dose.
  • a Sprayed to the foliage of weeds with a small sprayer in an amount equivalent to the spray amount.

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Abstract

Substituted cyanoacetamide derivatives of the general formula (1) and salts thereof, exhibiting excellent herbicidal activity; and preparations containing the derivatives or the salts and being useful as herbicides excellent in crop selectivity wherein R1 and R2 are each hydrogen, nitro, cyano, halogeno, C1-6 alkyl, C1-6 alkylsulfonyl, or the like; R3 is nitro, cyano, halogeno, C1-6 alkyl, or the like; n is 0, 1 or 2; R4 and R5 are each hydrogen, C1-6 alkyl, C1-6 alkoxy, or the like, or alternatively they may be united to form an alkylene chain, a heterocyclic group, or the like; X is oxygen or sulfur; and Z is formyl, di(C1-6 alkoxy)methyl, phenyl, a heterocyclic group, or the like.

Description

明 細 書  Specification
置換シァノアセトアミ ド誘導体及び除草剤 技術分野：  Substituted cyanoacetamide derivatives and herbicides
本発明は、 新規なシァノアセトアミ ドのメチレン部に置換ベンゾィル基が置換した 置換シァノアセトアミ ド誘導体及び除草剤に関する。 背景技術：  The present invention relates to a substituted cyanoacetamide derivative in which a methylene moiety of a novel cyanoacetamide is substituted with a substituted benzoyl group, and a herbicide. Background technology:
農園芸作物の栽培にあたり、 多大の労力を必要としてきた雑草防除に多くの除草剤 が使用されるようになってきた。 しかし作物に薬害を生じたり、 環境に残留したり、 汚染したりすることから、 より低薬量で効果が確実でしかも安全に使用できる薬剤 の開発が望まれている。  Many herbicides have come to be used for weed control, which has required a great deal of effort in cultivating agricultural and horticultural crops. However, there is a need for the development of drugs that can be used safely and safely at lower dosages because they cause phytotoxicity, remain in the environment, and pollute crops.
本発明化合物と関連した化合物を開示したものとしては、 以下のものがある。 The following are disclosures of compounds related to the compounds of the present invention.
(1) E P. 0213892号公報には、 除草活性を有する式 （A) で表される化 合物及び該化合物の製造法が記載されている。
Figure imgf000003_0001
(1) EP 0213892 describes a compound represented by the formula (A) having herbicidal activity and a method for producing the compound.
Figure imgf000003_0001
(式中、 Aは COR， 、 C02R， 、 CONR， R" を表し、 Bは CN基等を表し、 Vは水素原子等を表し、 Wは置換フ 二ル基等を表す。 ） (COR, wherein, A is, C0 2 R,, CONR, represent R ", B represents a CN group, V is a hydrogen atom, etc., W represents a substituent full sulfonyl group.)
しかしながら、 Wが本発明のような置換基を有するフ ニル基である化合物の記載 はない。  However, there is no description of a compound in which W is a phenyl group having a substituent as in the present invention.
(2) WO 96/26193号公報には、 式 （B) で表される化合物が除草活性を有 する旨及び該化合物の製造法が記載されている。
Figure imgf000004_0001
(2) WO 96/26193 describes that the compound represented by the formula (B) has herbicidal activity and a method for producing the compound.
Figure imgf000004_0001
(式中、 R1はアルキル基、 シクロアルキル基等を表し、 Qは複素環基を表す。 ） しかしながら、 上記式 （B) において、 本発明化合物のように R1が窒素原子と結合 して形成される基である化合物の記載はない。 (In the formula, R 1 represents an alkyl group, a cycloalkyl group, and the like, and Q represents a heterocyclic group.) However, in the above formula (B), R 1 is bonded to a nitrogen atom as in the compound of the present invention. There is no description of the compound that is the group to be formed.
(3) また E P. 625505号公報には、 下記式 （C) で表される化合物が記載 されている。  (3) Further, EP-A-625505 describes a compound represented by the following formula (C).
Figure imgf000004_0002
しかしながら、 この式 （C) で表される化合物には、 1〜!^5が複素環基である化 合物は含まれない。 また、 R6はアルキル基又はシクロアルキル基であり、 窒素原子 と結合して形成される基である化合物の記載はない。 発明の開示：
Figure imgf000004_0002
However, the compound represented by the formula (C) does not include a compound in which 1 to! ^ 5 is a heterocyclic group. Further, there is no description of a compound in which R 6 is an alkyl group or a cycloalkyl group and is a group formed by bonding to a nitrogen atom. DISCLOSURE OF THE INVENTION:
本発明の目的は、 工業的に有利に合成でき、 より低い薬量で効果の確実な安全性の 高い、 作物選択性の良い除草剤を提供することにある。  An object of the present invention is to provide a herbicide that can be synthesized industrially advantageously, is effective at a low dose, has high safety, and has good crop selectivity.
本発明は、 第 1に、 式 （1)  The present invention firstly provides a formula (1)
Figure imgf000004_0003
Figure imgf000004_0003
[式中、 R2は、 それぞれ独立して、 水素原子、 ニトロ基、 シァノ基、 ハロゲン 原子、 C1-6アルキル基、 C1-6アルコキシ基、 ハロアルキル基、 C1-6ハロアルコキ シ基、 c1-6アルキルチオ基、 アルキルスルフヱニル基又は c1-6アルキルスルホ二 ル基を表す。 Wherein, R 2 are each independently a hydrogen atom, a nitro group, Shiano group, a halogen atom, C 1-6 alkyl, C 1-6 alkoxy group, a haloalkyl group, C 1-6 Haroarukoki Represents a C 1-6 alkylthio group, an alkylsulfonyl group or a C 1-6 alkylsulfonyl group.
R3は、 ニトロ基、 シァノ基、 ハロゲン原子、 アルキル基、 アルコキシ基、 C 6ハロアルキル基、 d-6ハロアルコキシ基、 アルキルチオ基、 C1-6アルキルス ルフヱニル基又は アルキルスルホ二ル基を表す。 nは、 0、 1又は 2を表す。 R 3 represents a nitro group, a cyano group, a halogen atom, an alkyl group, an alkoxy group, a C 6 haloalkyl group, a d- 6 haloalkoxy group, an alkylthio group, a C 1-6 alkylsulfenyl group or an alkylsulfonyl group. n represents 0, 1 or 2.
R4， R5は、 それぞれ独立して、 水素原子、 アルキル基、 C2— 6アルケニル基、 Ci— 6アルコキシ基、 C1-6ハロアルキル基、 C1-6ヒ ドロキシアルキル基、 じ 6ハロアル コキシ基、 C3-8シクロアルキル基、 アルコキシ アルキル基、 ハロアルコ キシ C — 6アルキル基、 Ci— 6アルコキシ C1-6アルコキシ基、 C1-6ハロアルコキシ CMァ ルコキシ基、 アルキルチオ C — 6アルキル基、 C1-6アルキルチオ C1-6アルコキシ基、 アミノ基、 CMアルキルアミノ基、 ジじ アルキルアミノ基、 アルキルカルボ二 ル基、 c1-sアルコキシカルボニル基、 ハロアルキルカルボニル基、 ハロアル コキシカルボニル基、 CMアルキルスルホニル基、 ハロアルキルスルホ二ル基又 は、 （ハロゲン原子、 アルキル基、 C 6アルコキシ基又は ハロアルキル基等 で） 置換されていてもよいフヱニル基を表す。 また、 R4と R5は、 一緒になつて炭素 数 2 — 5のアルキレン鎖、 又は R4と R5は結合している窒素原子とともに、 C1-6アル キル基等で置換されていてもよい酸素原子又は窒素原子を 2— 4個含む 5員若しく は 6員の含窒素複素環を形成してもよい。 R 4, R 5 are each independently a hydrogen atom, an alkyl group, C 2 - 6 alkenyl group, CI- 6 alkoxy group, C 1-6 haloalkyl group, C 1-6 hydroxycarboxylic alkyl group, Ji 6 Haroaru Kokishi group, C 3 - 8 cycloalkyl group, an alkoxy group, Haroaruko alkoxy C - 6 alkyl group, CI- 6 alkoxy C 1-6 alkoxy group, C 1-6 haloalkoxy CM § alkoxy group, alkylthio C - 6 Alkyl group, C 1-6 alkylthio C 1-6 alkoxy group, amino group, CM alkylamino group, dialkylamino group, alkylcarbonyl group, c1 -s alkoxycarbonyl group, haloalkylcarbonyl group, haloalkoxy carbonyl group, CM alkylsulfonyl group, the haloalkylsulfonyl group or, (halogen atom, an alkyl group, C 6 alkoxy group or a haloalkyl group) is substituted Even if representing a good Fuweniru group. R 4 and R 5 are joined together to form an alkylene chain having 2 to 5 carbon atoms, or R 4 and R 5 together with the bonded nitrogen atom are substituted with a C 1-6 alkyl group or the like. May form a 5- or 6-membered nitrogen-containing heterocyclic ring containing 2 to 4 oxygen or nitrogen atoms.
Xは、 酸素原子、 硫黄原子を表す。  X represents an oxygen atom or a sulfur atom.
Zは、 ホルミル基、 ジ d— 6アルコキシメチル基、 C2_6アルケニル基、 C2-6アルキニ ル基、 C1-6アルコキシィミノメチル基、 C1-6ハロアルコキシィミノメチル基、 C2_6ァ ルケ二ルイミノメチル基、 C 26ハロアルケ二ルイミノメチル基、 （ハロゲン原子、 C1-6アルキル基、 C1-6アルコキシ基、 C1-6ハロアルキル基、 シァノ基、 ニトロ基等の） 置換基を有していてもよいフヱニル基又は （ハロゲン原子、 CMアルキル基、 C ァ ルコキシ基又は ハロアルキル基等で） 置換されていてもよい酸素原子、 窒素原 子もしく くは硫黄原子を 1〜4個含む 5員〜 6員の複素環基を表す。 ] で表される 化合物又はその塩を提供する。 前記式 （l ) で表される化合物の zにおける置換されていてもよい複素環基として は、 下記で表される群から選ばれた一種の基であるのが好ましい。Z is a formyl group, di-d-6 alkoxymethyl group, C 2 _ 6 alkenyl, C 2-6 Arukini Le group, C 1-6 alkoxides Consequences amino methyl, C 1-6 halo alkoxides Consequences amino methyl group, C 2 _ 6 § Luque two Ruiminomechiru group, C 26 Haroaruke two Ruiminomechiru group, (halogen atom, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 haloalkyl group, Shiano group, such as nitro group) An optionally substituted phenyl group or (optionally substituted with a halogen atom, a CM alkyl group, a C alkoxy group or a haloalkyl group) an oxygen atom, a nitrogen atom or a sulfur atom. Represents a 5- to 6-membered heterocyclic group containing up to 4 members. ] Or a salt thereof. The optionally substituted heterocyclic group in z of the compound represented by the formula (l) is preferably a kind of group selected from the group shown below.
R7
Figure imgf000006_0001
R 7
Figure imgf000006_0001
R7
Figure imgf000006_0002
'ヽ R 7
Figure imgf000006_0002
'ヽ
N 7 N 7
(式中、 R6及び R7は、 それぞれ独立して、 水素原子、 ハロゲン原子、 C 1-6アルキル 基、 ハロアルキル基又は C 1-6アルコキシ基を表す。 ） (In the formula, R 6 and R 7 each independently represent a hydrogen atom, a halogen atom, a C 1-6 alkyl group, a haloalkyl group, or a C 1-6 alkoxy group.)
本発明は、 第 2に、 前記式 （1 ) で表わされる化合物又はその塩の 1種若しくは 2 種以上を有効成分として含有する除草剤を提供する。  Secondly, the present invention provides a herbicide containing one or more of the compound represented by the formula (1) or a salt thereof as an active ingredient.
以下、 本発明を詳細に説明する。  Hereinafter, the present invention will be described in detail.
前記式 （1 ) において、 R i, R2はそれぞれ独立して、 水素原子、 ニトロ基、 シァ ノ基、 In the above formula (1), R i and R 2 are each independently a hydrogen atom, a nitro group, a cyano group,
フッ素、 塩素、 臭素等のハロゲン原子、  Halogen atoms such as fluorine, chlorine, and bromine,
メチル、 ェチル、 プロピル、 イソプロピル、 プチル、 イソプチル、 s —プチル、 t —プチル等の C 1-6アルキル基、 A C 1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isoptyl, s-butyl, t-butyl, etc.
メ トキシ、 エトキシ、 プロポキシ、 イソプロポキシ、 ブトキシ、 s —ブトキシ、 t —ブトキシ等の アルコキシ基、  Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, t-butoxy,
クロロメチル、 ジクロロメチル、 トリクロロメチル、 フルォロメチル、 ジフルォロ メチル、 トリフルォロメチル、 1—フルォロェチル、 1 , 1—ジフルォロェチル、 1， 1 ， 1—トリフルォロェチル、 ペンタフルォロェチル等の 6ハロアルキル基、 クロロメ トキシ、 ジクロロメ トキシ、 トリクロロメ トキシ、 フルォロメ トキシ、 ジ フルォロメ トキシ、 トリフルォロメ トキシ、 1—フルォロエトキシ、 1， 1—ジフ ルォロエトキシ、 1， 1 , 1一トリフルォロエトキシ、 ペンタフルォロエトキシ等 の C 1-6ノヽロアノレコキシ基、 6- haloalkyl groups such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 1,1-difluoroethyl, 1,1,1-trifluoroethyl and pentafluoroethyl , C such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1-fluoroethoxy, 1,1-difluoroethoxy, 1,1,1-trifluoroethoxy, pentafluoroethoxy, etc. 1-6 noroanorecoxy group,
メチルチオ、 ェチルチオ、 プロピルチオ、 イソプロピルチオ、 プチルチオ、 tーブ チルチオ等の C wアルキルチオ基、  C w alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, and butylthio;
メチルスルフヱニル、 ェチルスルフヱニル、 プロピルスルフヱニル、 イソプロピル スルフエニル、 ブチルスルフエニル、 t—プチルスルフエニル等の 6アルキルス ルフヱニル基、 6- alkyl sulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfenyl, isopropylsulfenyl, butylsulfenyl and t-butylsulfenyl;
メチルスルホニル、 ェチルスルホニル、 プロピルスルホニル、 イソプロピルスルホ ニル、 ブチルスルホニル、 tーブチルスルホニル等の アルキルスルホ二ル基を ^  Alkyl sulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, t-butylsulfonyl, etc.
R 3は、 二ト口基、 シァノ基、 R 3 is a nitro group, a cyano group,
フッ素、 塩素、 臭素等のハロゲン原子、  Halogen atoms such as fluorine, chlorine, and bromine,
メチル、 ェチル、 プロピル、 イソプロピル、 プチル、 イソプチル、 S—プチル、 t —プチル等の 6アルキル基、 6 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isoptyl, S-butyl, t-butyl, etc.
メ トキシ、 エトキシ、 プロポキシ、 イソプロポキシ、 ブトキシ、 s —ブトキシ、 t —ブトキシ等の アルコキシ基、  Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, t-butoxy,
クロロメチル、 ジクロロメチル、 トリクロロメチル、 フルォロメチル、 ジフルォロ メチル、 トリフルォロメチル、 1一フルォロェチル、 1， 1ージフルォロェチル、 1， 1， 1一 トリフルォロェチル、 ペンタフルォロェチル等の 0ト6ハロアルキル基、 クロロメ トキシ、 ジクロロメ トキシ、 トリクロロメ トキシ、 フルォロメ トキシ、 ジ フルォロメ トキシ、 トリフルォロメ トキシ、 1一フルォロエトキシ、 1 , 1ージフ ルォロエトキシ、 1， 1 , 1一トリフルォロエトキシ、 ペンタフルォロエトキシ等Chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 1,1 difluoroethyl, 1,1,1,1-trifluoroethyl, pentafluoroethyl, etc. 0 6 haloalkyl groups, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1-fluoroethoxy, 1,1 difluoroethoxy, 1,1,1-trifluoroethoxy, pentafluoro Roethoxy etc.
.の C 6ハ口アルコキシ基、 A C 6 haloalkoxy group,
メチルチオ、 ェチルチオ、 プロピルチオ、 イソプロピルチオ、 プチルチオ、 t —ブ チルチオ等の C Mアルキルチオ基、 メチルスルフヱニル、 ェチルスルフヱニル、 プロピルスルフエニル、 イソプロピル スルフヱニル、 プチルスルフヱニル、 t—ブチルスルフヱニル等の C 1-6アルキルス ルフヱニル基、 CM alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, and t-butylthio; A C 1-6 alkyl sulfonyl group such as methylsulfonyl, ethylsulfonyl, propylsulfenyl, isopropylsulfonyl, butylsulfonyl, t-butylsulfonyl, etc.
メチルスルホニル、 ェチルスルホニル、 プロピルスルホニル、 イソプロピルスルホ ニル、 プチルスルホニル、 t—ブチルスルホニル等の アルキルスルホ二ル基を Alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and t-butylsulfonyl;
¾す。 Pass
R 4， R 5は、 それぞれ独立して、 水素原子、 R 4 and R 5 are each independently a hydrogen atom,
メチル、 ェチル、 プロピル、 イソプロピル、 プチル、 イソプチル、 s—プチル、 t —プチル等の C i-6アルキル基、  Ci-6 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isoptyl, s-butyl, t-butyl, etc.
メ トキシ、 エトキシ、 プロポキシ、 イソプロボキシ、 ブトキシ、 s—ブトキシ、 t —ブトキシ等の C Mアルコキシ基、  CM alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, t-butoxy,
クロロメチル、 ジクロロメチル、 トリクロロメチル、 フルォロメチル、 ジフルォロ メチル、 トリフルォロメチル、 1—フルォロェチル、 1， 1—ジフルォロェチル、 1， 1 , 1一 トリフルォロェチル、 ペンタフルォロェチル等の ハロアルキル基、 クロロメ トキシ、 ジクロロメ トキシ、 トリクロロメ トキシ、 フルォロメ トキシ、 ジ フルォロメ トキシ、 トリフルォロメ トキシ、 1 _フルォロエトキシ、 1， 1—ジフ ルォロエトキシ、 1， 1 , 1一 トリフルォロエトキシ、 ペンタフルォロエトキシ等 の Cト6ハロアノレコキシ基、 Haloalkyl groups such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 1,1-difluoroethyl, 1,1,1-trifluoroethyl and pentafluoroethyl; C such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1_fluoroethoxy, 1,1-difluoroethoxy, 1,1,11-trifluoroethoxy, pentafluoroethoxy, etc. 6 halo anolecoxy group,
シクロプロピル、 シクロブチル、 シクロペンチル、 シクロへキシル等の C 3-8シクロ アルキル基、 C 3-8 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
メ トキシメチル、 メ トキシェチル、 エトキシメチル等の アルコキシじ 6ァルキ ル基、 Main Tokishimechiru, main Tokishechiru, alkoxy Ji 6 Aruki Le group such as ethoxymethyl,
トリフルォロメ トキシメチル、 トリフルォロメチルェチル等の 6ハロアルコキシ C 1-6アルキル基、 6 haloalkoxy C 1-6 alkyl group such as trifluoromethyloxymethyl, trifluoromethylethyl, etc.
メ トキシメ トキシ、 メ トキシェトキシ、 エトキシメ トキシ等の アルコキシ c 1-6 アルコキシ基、 Alkoxy c 1-6 alkoxy groups such as methoxy methoxy, methoxy ethoxy, ethoxy methoxy, etc.
トリフルォロメ トキシメ トキシ、 トリフルォロメ トキシェトキシ等の C i— 6ハロアル コキシ C 1-6アルコキシ基、 C i- 6 haloal such as trifluorometoxime toxic, trifluorometoxetoxy, etc. Coxy C 1-6 alkoxy group,
メチルチオメチル、メチルチオェチル、ェチルチオメチル等の C 1-6アルキルチオ 6 アルキル基、 C 1-6 alkylthio 6 alkyl groups such as methylthiomethyl, methylthioethyl, ethylthiomethyl,
メチルチオメ トキシ、 メチルチオエトキシ、 ェチルチオメ トキシ等の c 1-6アルキル チォ アルコキシ基、 C 1-6 alkylthioalkoxy groups such as methylthiomethoxy, methylthioethoxy, and ethylthiomethoxy;
アミノ基、  Amino group,
メチルァミ ノ、 ェチルァミノ、 プロピルァミノ、 イソプロピルァミノ、 プチルアミ ノ等の アルキルァミノ基、  Alkylamino groups such as methylamino, ethylamino, propylamino, isopropylamino, and butylamino;
ジメチルァミノ、 ジェチルァミノ、 ェチルメチルァミノ等のジじ^アルキルアミノ 基、  Dialkylamino groups such as dimethylamino, getylamino, and ethylmethylamino,
ァセチル、 プロピオニル、 プチリル等の アルキルカルボニル基、  Alkylcarbonyl groups such as acetyl, propionyl, and petyryl,
メ トキシカルボニル、 エトキシカルボニル、 プロポキシカルボニル、 イソプロポキ シカルボニル、 ブトキシカルボニル、 t—ブトキシカルボニル等の d-6アルコキシ カルボニル基、 D- 6 alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl,
フルォロアセチル、 クロロアセチル、 トリフルォロアセチル、 トリクロロアセチル 等の ハロアルキルカルボニル基、  Haloalkylcarbonyl groups such as fluoroacetyl, chloroacetyl, trifluoroacetyl, trichloroacetyl,
フルォロメ トキシカルボニル、 クロロメ トキシカルボニル、 トリフルォロメ トキシ カルボニル、 トリクロロメ トキシカルボニル等の C 1-6ハロアルコキシカルボニル基、 メチルスルホニル、 ェチルスルホニル、 プロピルスルホニル、 イソプロピルスルホ ニル、 プチルスルホニル、 tーブチルスルホニル等の アルキルスルホニル基、 フルォロメチルスルホニル、 クロロメチルスルホニル、 トリフルォロメチルスルホ ニル、 トリクロロメチルスルホニル等の c1-6ハロアルキルスルホニル基、 Furuorome butoxycarbonyl, chloromethane butoxycarbonyl, Torifuruorome butoxy carbonyl, C 1-6 haloalkoxycarbonyl group such as trichloroacetic main butoxycarbonyl, methylsulfonyl, Echirusuruhoniru, propylsulfonyl, isopropylsulfonyl, Puchirusuruhoniru, such as t-butylsulfonyl an alkylsulfonyl group, the full O b methylsulfonyl, chloromethylsulfonyl, triflumizole Ruo b methylsulfonyl, c 1-6 haloalkylsulfonyl groups such as trichloromethyl sulfonyl,
ベンゼン環の任意の位置に、 （フッ素、 塩素、 臭素等のハロゲン原子、 メチル、 ェ チル等の C Hアルキル基、 メ トキシ、 エトキシ等の C i— 6アルコキシ基又はクロロメチ ル、 ジクロロメチル、 トリクロロメチル、 フルォロメチル、 ジフルォロメチル、 ト リフルォロメチル等の C 1-6ハロアルキル基等） で置換されてもよいフヱ二ル基を表 す。 また、 R4と R5は一緒になつて、 エチレン、 トリメチレン、 テトラメチレン、 ペン タメチレンの炭素数 2〜 5のアルキレン鎖、 又は R4と R5は結合している窒素原子と ともに、 置換基を有してもよい 5員若しくは 6員の窒素原子又は酸素原子を 2—4 個含む含窒素複素環を形成してもよい。 At any position on the benzene ring, (halogen atoms such as fluorine, chlorine, and bromine, CH alkyl groups such as methyl and ethyl, Ci- 6 alkoxy groups such as methoxy and ethoxy, or chloromethyl, dichloromethyl, trichloromethyl Or a C 1-6 haloalkyl group such as fluoromethyl, difluoromethyl, trifluoromethyl, etc.). R 4 and R 5 are joined together to form an alkylene chain having 2 to 5 carbon atoms of ethylene, trimethylene, tetramethylene, or pentamethylene, or R 4 and R 5 are a substituent together with a bonding nitrogen atom. May form a nitrogen-containing heterocycle containing 2 to 4 5- or 6-membered nitrogen or oxygen atoms.
かかる複素環としては、 モルホリ ン一 4一ィル、 ピぺラジン一 1—ィル、 1， 3 , 5—ペルヒ ドロ トリアジン一 1—ィル、 イ ミダゾールー 1一ィル、 ピラゾール一 1 —ィル、 1 , 2 , 4一 トリァゾ一ルー 1一ィル、 ォキサゾリジン一 2—ィル、 テト ラゾールー 1 _ィル等を例示することができる。 また、 これらは、 メチル、 ェチル 等の C 1-6アルキル基等で置換されていてもよい。 Such heterocycles include morpholine 41-yl, piperazine 1-1-yl, 1,3,5-perhydrotriazine 1-yl, imidazole 11-yl, pyrazole 11-yl , 1, 2, 4-triazole-l-yl, oxazolidine-l-yl, tetrazol-l-yl and the like. These may be substituted with a C 1-6 alkyl group such as methyl and ethyl.
Zは、 ホルミル基、  Z is a formyl group,
ジメ トキシメチル、 ジエトキシメチル等のジじ^アルコキシメチル基、  Dialkoxymethyl groups such as dimethoxymethyl and diethoxymethyl,
ェテニル、 1一プロぺニル、 2—プロぺニル等の C 2— 6アルケニル基、 Eteniru, 1 one propenyl, and 2-propenyl C 2 - 6 alkenyl group,
ェチニル、 1一プロピニル、 2—プロピニル等の C 2— 6アルキニル基、 Echiniru, 1 one propynyl, C 2 2-propynyl, and the like - 6 alkynyl group,
メ トキシィ ミノメチル、 エトキシイ ミノメチル、 プロポキシイ ミノメチル、 ブトキ シィ ミノメチル等の C 1-6アルコキシィ ミノメチル基、 Main Tokishii Minomechiru, Etokishii Minomechiru, Puropokishii Minomechiru, C 1-6 Arukokishii Minomechiru groups such as butoxy Consequences Minomechiru,
フルォロメ トキシィ ミノメチル、 クロロメ トキシィミノメチル、 トリフノレオロメ ト キシィ ミノメチル、 トリクロロメ トキシィ ミノメチル等の ハロアルコキシィ ミ ノメチル基、  Haloalkoxyminomethyl groups such as fluoromethinominomethyl, chloromethoxyminomethyl, trifinoleolomethoxyminomethyl, and trichloromethoxyminomethyl;
ベンゼン環の任意の位置に、 （フッ素、 塩素、 臭素等のハロゲン原子、 メチル、 ェ チル等の C 1-6アルキル基、 メ トキシ、 エトキシ等のじ 6アルコキシ基又はクロロメチ ル、 ジクロロメチル、 トリクロロメチル、 フルォロメチル、 ジフルォロメチル、 ト リフルォロメチル等の C 1-6ハロアルキル基、 シァノ基、 ニトロ基等） で置換されて もよぃフヱニル基、 又は、 At any position of the benzene ring, (fluorine, chlorine, halogen atom such as bromine, methyl, C 1-6 alkyl group such as E chill, main butoxy, Flip of ethoxy 6 alkoxy group or Kuroromechi Le, dichloromethyl, trichloromethyl Methyl, fluoromethyl, difluoromethyl, trifluoromethyl, etc., C 1-6 haloalkyl group, cyano group, nitro group, etc.).
2—フリル、 3—フリル、 ォキサゾ一ルー 2 _ィル、 ォキサゾールー 4一ィル、 ォ キサゾ一ルー 5—ィル、 イソォキサゾールー 3 _ィル、 イソォキサゾールー 4ーィ ル、 イソォキサゾ一ルー 5—ィル、 1 , 2 , 4—ォキサジァゾ一ルー 3—ィル、 1， 2， 4—ォキサジァゾール _ 3—ィル、 1， 2 , 4—ォキサジァゾール一 5—ィル、 1， 3， 4—ォキサジァゾ一ルー 2 —ィル、 1 , 3 , 4 —ォキサジァゾール一 5— ィル、 チアゾール—2—ィル、 チアゾールー 4一ィル、 チアゾールー 5 —ィル、 ィ ソチアゾ一ル一 3—ィル、 イソチアゾール— 4一ィル、 イソチアゾールー 5—ィル、 1， 2 , 4—チアジアゾール— 3 —ィル、 1， 2， 4—チアジアゾ一ルー 5 —ィル、 1， 3， 4 —チアジアゾール— 2 —ィル、 1， 3， 4—チアジアゾール _ 5 —ィル、 イミダゾールー 2 —ィル、 イミダゾール— 4—ィル、 イミダゾールー 5 —ィル、 2 一チェニル、 3—チェニル、 ピラゾールー 3—ィル、 ピラゾールー 4一ィル、 ビラ ゾール—5—ィル、 1 , 2 , 4—トリァゾール— 3 —ィル、 1， 2 , 4 —トリァゾ —ルー 5—ィル、 テトラゾ一ル一 2—ィル、 4， 5 —ジヒドロイソォキサゾール一 3—ィル、 4， 5—ジヒドロイソォキサゾールー 4一ィル、 , 4 , 5—ジヒドロイソ ォキサゾールー 5 _ィル、 2—ピリジル、 3 _ピリジル、 4—ピリジル等の窒素原 子、 酸素原子、 硫黄原子を 1〜 4個含む 5員若しくは 6員の複素環基を表す。 2-furyl, 3-furyl, oxazolyl 2-yl, oxazol-41-yl, oxazolo-5-yl, isoxoxazole-3-yl, isoxazole-4-yl 1,2-, 4-oxazine-diyl 3-yl, 1,2,4-oxadiazole_3-yl, 1,2,4-oxadiazole-5-yl, 1,3,4-Oxaziazol-2-yl, 1,3,4—oxaziazol-1-yl, thiazole-2-yl, thiazol-41-yl, thiazol-5-yl, isotizazoyl 1,3-yl, isothiazole-41-yl, isothiazol-5-yl, 1,2,4-thiadiazole-3-yl, 1,2,4-thiadiazol-5-yl, 1,3 , 4 — thiadiazole — 2 — yl, 1, 3, 4- thiadiazole _ 5 — yl, imidazole -2- yl, imidazole -4- yl, imidazole -5 — yl, 2-thenyl, 3- phenyl, Pyrazole-3-yl, pyrazole-41-yl, virazol-5-yl, 1,2,4-triazole-3-yl, 1,2,4—triazo-lu-5-yl, tetrazole 1,2-yl, 4,5-dihydroisoxazole-13-yl, 5-dihydroisoxazole-4-yl,, 4,5-dihydroisoxazole-5-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl and other nitrogen, oxygen, and sulfur atoms Represents a 5- or 6-membered heterocyclic group containing four.
Zにおける置換されてもよい複素環基のより好ましい例としては、 次の各基を挙げ ることができる。  More preferred examples of the optionally substituted heterocyclic group for Z include the following groups.
Figure imgf000011_0001
Figure imgf000011_0001
Figure imgf000011_0002
Figure imgf000011_0002
式中、 R6, R7はそれぞれ独立して、 水素原子、 フッ素、 塩素、 臭素等のハロゲン 原子、 メチル、 ェチル等の アルキル基、 クロロメチル、 トリフルォロメチル等 の d-6ハロアルキル基又はメ トキシ、 エトキシ等の C 1-eアルコキシ基を表す。 Xは、 酸素原子、 硫黄原子を表す。 In the formula, R 6 and R 7 are each independently a hydrogen atom, a halogen atom such as fluorine, chlorine, or bromine; an alkyl group such as methyl or ethyl; a d- 6 haloalkyl group such as chloromethyl or trifluoromethyl; Represents a C 1-e alkoxy group such as methoxy and ethoxy. X represents an oxygen atom or a sulfur atom.
次に、 本発明化合物の代表例を第 1表に示す。 この表及び第 2表の Z欄において用 いた A Z 1— Z 3 0の略記号は以下の意味を表す。
Figure imgf000012_0001
H3 Next, Table 1 shows typical examples of the compound of the present invention. The abbreviations of AZ1-Z30 used in column Z of this table and Table 2 have the following meanings.
Figure imgf000012_0001
H 3
Z5: Z6: Z7: Z8: Z5: Z6: Z7: Z8:
Figure imgf000012_0002
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000012_0002
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000015_0001
C0900/T0df/X3d 6.69S/T0 OAV
Figure imgf000016_0001
9T C0900 / T0df / X3d 6.69S / T0 OAV
Figure imgf000016_0001
9T
Figure imgf000017_0001
/T0df/X3d 6.69S/T0 OAV 9T
Figure imgf000017_0001
/ T0df / X3d 6.69S / T0 OAV 9T
Figure imgf000018_0001
/T0df/X3d 6.69S/T0 OAV LI
Figure imgf000018_0001
/ T0df / X3d 6.69S / T0 OAV LI
Figure imgf000019_0001
/T0df/X3d 6.69S/T0 OAV -247 CI S02 e n=0 CH2CH2 O Z15-248 CI S02Me n=0 CH2CH2CH2 O Z15-249 CI S02Me n=0 CH2CH2CH2CH2 0 Z15-250 CI S02Me 5- Me Me Me 0 Z15-251 CI S02 e 5 - Me Me OMe 0 Z15-252 CI S02Me 5 - Me CH2CH2 0 Z15-253 Me S02Me n=0 Me Me 0 Z16-254 Me S02Me n=0 Me Et 0 Z16-255 Me S02Me n=0 Me OMe 0 Z16-256 Me S02Me n=0 CH2CH2 0 Z16-257 Me S02Me n=0 GH2GH2GH2 0 Z16-258 Me S02Me n=0 CH2CH2CH2CH2 0 Z16-259 Me S02Me 5- Me Me Me 0 Z16-260 Me S02Me 5-Me Me ' Et 0 Z16-261 Me S02Me 5- Me Me OMe 0 Z1 6-262 Me S02 e 5-Me CH2GH2 0 Z16-263 Me S02Me 5 - Me CH2CH2CH2 0 Z16-264 Me S02 e 5-Me CH2CH2CH2CH2 0 Z1 6-265 CI S02Me n=0 Me Me 0 Z16-266 CI S02Me n=0 Me OMe 0 Z16-267 CI S02Me n=0 CH2CH2 0 Z1 6-268 CI S02Me n=0 CH2CH2CH2 0 Z16-269 Gl S02Me n=0 0 Z16-270 CI S02Me 5-Me Me Me 0 Z16-271 CI S02Me 5-Me Me OMe 0 Z16-272 CI S02Me 5-Me CH2CH 0 Z16-273 Me S02Me n=0 Me Me 0 Z17-274 Me S02Me n=0 GHg 0 Z1 7-275 Me S02Me 5-Me Me Me 0 Z1 7-276 Me S02Me 5-Me CH2CH2 0 Z17-277 CI S02Me n=0 Me Me 0 Z1 7-278 CI S02Me n=0 CH2CH2 0 Z17-279 CI S02 e 5 - Me Me Me 0 Z1 7-280 CI S02Me 5-Me CH2CH2 0 Z1 7-281 Me S02Me n=0 Me Me 0 Z18-282 Me S02Me n=0 CH2CH 0 Z18 -283 Me S02Me 5-Me Me Me O Z18-284 Me S02 e 5-Me CH2CH2 O Z18-285 CI S02Me n=0 Me Me O Z18-286 CI S02Me n=0 CH2CH2 O Z18-287 CI S02Me 5-Me Me Me O Z18-288 CI S02 e 5-Me CH2CH2 O Z1.8-289 Me S02 e n=0 Me Me O Z19-290 Me S02Me n=0 Me Et 0 Z19-291 Me S02Me n=0 Me OMe O Z19-292 Me S02Me n=0 CH2CH2 O Z19-293 Me S02 e n=0 CH2CH2CH2 O Z19-294 Me S02Me n=0 CH2CH2CH2CH2 O Z19-295 Me S02 e 5-Me Me Me O Z19-296 CI S02Me n=0 Me Me O Z19-297 CI S02 e n=0 Me OMe O Z19-298 CI S02Me n=0 CH2CH2 O Z19-299 CI S02Me n=0 GH2GH2CH2 O Z19-300 CI S02Me n=0 CH2CH2CH2CH2 O Z19-301 CI S02Me 5-Me Me Me O Z19-302 Me S02Me n=0 Me Me O Z20-303 Me S02Me n=0 Me Et O Z20-304 Me S02Me n=0 Me OMe O Z20-305 Me S02Me n=0 CH2CH2 O Z20-306 Me S02Me n=0 CH2CH2CH2 0 Z20-307 Me S02Me n=0 CH2CH2CH2CH2 0 Z20-308 Me S02Me 5-Me Me Me 0 Z20-309 Me S02Me 5-Me Me Et 0 Z20-310 Me S02Me 5-Me Me OMe 0 Z20-311 Me S02Me 5-Me CH2CH2 0 Z20-312 Me S02 e 5-Me CH2CH2CH2 0 Z20-313 Me S02 e 5-Me CH2CH2CH2CH2 0 Z20-314 CI S02Me n=0 Me Me 0 Z20-315 CI S02Me n=0 Me OMe 0 - Z20-316 CI S02Me n=0 CH2CH2 0 Z20-317 CI S02 e n=0 GH2GH2CH2 0 Z20-318 CI S02Me n=0 CH2CH2CH2CH2 0 Z20 02
Figure imgf000019_0001
/ T0df / X3d 6.69S / T0 OAV -247 CI S0 2 en = 0 CH2CH2 O Z15-248 CI S0 2 Me n = 0 CH2CH2CH2 O Z15-249 CI S0 2 Me n = 0 CH2CH2CH2CH2 0 Z15-250 CI S0 2 Me 5- Me Me Me 0 Z15-251 CI S0 2 e 5-Me Me OMe 0 Z15-252 CI S0 2 Me 5-Me CH2CH2 0 Z15-253 Me S0 2 Me n = 0 Me Me 0 Z16-254 Me S0 2 Me n = 0 Me Et 0 Z16- 255 Me S0 2 Me n = 0 Me OMe 0 Z16-256 Me S0 2 Me n = 0 CH2CH2 0 Z16-257 Me S0 2 Me n = 0 GH 2 GH 2 GH 2 0 Z16-258 Me S0 2 Me n = 0 CH2CH2CH2CH2 0 Z16-259 Me S0 2 Me 5-Me Me Me 0 Z16-260 Me S0 2 Me 5-Me Me 'Et 0 Z16-261 Me S0 2 Me 5-Me Me OMe 0 Z1 6-262 Me S0 2 e 5-Me CH2GH2 0 Z16-263 Me S0 2 Me 5-Me CH2CH2CH2 0 Z16-264 Me S0 2 e 5-Me CH2CH2CH2CH2 0 Z1 6-265 CI S0 2 Me n = 0 Me Me 0 Z16-266 CI S0 2 Me n = 0 Me OMe 0 Z16-267 CI S0 2 Me n = 0 CH2CH2 0 Z1 6-268 CI S0 2 Me n = 0 CH2CH2CH2 0 Z16-269 Gl S0 2 Me n = 0 0 Z16-270 CI S0 2 Me 5 -Me Me Me 0 Z16-271 CI S0 2 Me 5-Me Me OMe 0 Z16-272 CI S0 2 Me 5-Me CH2CH 0 Z16-273 Me S0 2 Me n = 0 Me Me 0 Z17-274 Me S0 2 Me n = 0 GHg 0 Z1 7-275 Me S0 2 Me 5-Me Me Me 0 Z1 7-276 Me S0 2 Me 5-Me CH2CH2 0 Z17 -277 CI S0 2 Me n = 0 Me Me 0 Z1 7-278 CI S0 2 Me n = 0 CH2CH2 0 Z17-279 CI S0 2 e 5-Me Me Me 0 Z1 7-280 CI S0 2 Me 5-Me CH2CH2 0 Z1 7-281 Me S0 2 Me n = 0 Me Me 0 Z18-282 Me S0 2 Me n = 0 CH2CH 0 Z18 -283 Me S0 2 Me 5-Me Me Me O Z18 -284 Me S0 2 e 5-Me CH2CH2 O Z18-285 CI S0 2 Me n = 0 Me Me O Z18-286 CI S0 2 Me n = 0 CH2CH2 O Z18 -287 CI S0 2 Me 5-Me Me Me O Z18-288 CI S0 2 e 5-Me CH2CH2 O Z1.8-289 Me S0 2 en = 0 Me Me O Z19-290 Me S0 2 Me n = 0 Me Et 0 Z19-291 Me S0 2 Me n = 0 Me OMe O Z19-292 Me S0 2 Me n = 0 CH2CH2 O Z19-293 Me S0 2 en = 0 CH2CH2CH2 O Z19-294 Me S0 2 Me n = 0 CH2CH2CH2CH2 O Z19 -295 Me S0 2 e 5-Me Me Me O Z19-296 CI S0 2 Me n = 0 Me Me O Z19-297 CI S0 2 en = 0 Me OMe O Z19-298 CI S0 2 Me n = 0 CH2CH2 O Z19 -299 CI S0 2 Me n = 0 GH2GH2CH2 O Z19-300 CI S0 2 Me n = 0 CH2CH2CH2CH2 O Z19-301 CI S0 2 Me 5-Me Me Me O Z19 -302 Me S0 2 Me n = 0 Me Me O Z20 -303 Me S0 2 Me n = 0 Me Et O Z20-304 Me S0 2 Me n = 0 Me OMe O Z20-305 Me S0 2 Me n = 0 CH2CH2 O Z20-306 Me S0 2 Me n = 0 CH2CH2CH2 0 Z20 -307 Me S0 2 Me n = 0 CH2CH2CH2CH2 0 Z20-308 Me S0 2 Me 5-Me Me Me 0 Z20-309 Me S0 2 Me 5-Me Me Et 0 Z20-310 Me S0 2 Me 5-Me Me OMe 0 Z20-311 Me S0 2 Me 5-Me CH2CH2 0 Z20-312 Me S0 2 e 5-Me CH2CH2CH2 0 Z20-313 Me S0 2 e 5-Me CH2CH2CH2CH2 0 Z20-314 CI S0 2 Me n = 0 Me Me 0 Z20-315 CI S0 2 Me n = 0 Me OMe 0-Z20-316 CI S0 2 Me n = 0 CH2CH2 0 Z20-317 CI S0 2 en = 0 GH2GH2CH2 0 Z20-318 CI S0 2 Me n = 0 CH2CH2CH2CH2 0 Z20 02
Figure imgf000022_0001
/T0df/X3d 6.69S/T0 OAV -355 CI S02Me n=0 CH2CH2 O Z24-356 CI S02Me n=0 CH2CH2CH2 O Z24-357 CI S02Me n=0 CH2CH2CH2CH2 O Z24-358 Gl S02Me 5 - Me Me Me O Z24-359 Me S02Me n=0 Me Me O Z25-360 Me S02Me n=0 Me Et O Z25-361 Me S02Me n=0 Me OMe O Z25-362 Me S02Me n=0 CH2CH2 O Z25-363 Me S02Me n=0 CH2CH2CH2 O Z25-364 Me S02Me n=0 CH CH2CH2CH2 O Z25-365 Me S02Me 5 - Me Me Me O Z25-366 CI S02Me n=0 Me Me O Z25-367 CI S02Me n=0 Me OMe O Z25-368 CI S02Me n=0 CH GH2 O Z25-369 Gl S02 e n=0 CH2CH2CH2 O Z25-370 CI S02 e n=0 JH2CH2CH2GH2 O Z25-371 CI S02Me 5 - Me Me Me O Z25-372 Me S02Me n=0 Me Me O Z26-373 Me S02Me n=0 Me Et O Z26-374 Me S02Me n=0 Me OMe O Z26-375 Me S02Me n=0 CH2CH2 O Z26-376 Me S02Me n=0 CH2CH2CH2 O Z26-377 Me S02Me n=0 CH2CH2CH2CH2 O Z26-378 Me S02Me 5-Me Me Me O Z26-379 CI S02Me n=0 Me Me O Z26-380 CI S02Me n=0 Me OMe O Z26-381 CI S02Me n=0 CH2CH2 0 Z26-382 CI S02Me n=0 CH2CH2CH2 0 Z26-383 CI S02Me n=0 CH2CH2CH2CH2 0 Z26-384 CI S02Me 5 - Me Me Me 0 Z26-385 Me S02Me n=0 Me Me 0 Z27-386 Me S02Me n=0 Me Et 0 Z27-387 Me S02 e n=0 Me OMe 0 Z27-388 Me S02Me n=0 CH2CH2 0 Z27-389 Me S02Me n=0 CH2CH2CH2 0 Z27-390 Me S02Me n=0 ΟΗ2ΟΗ2ΟΗ2θΗ2 0 Z27 zz
Figure imgf000022_0001
/ T0df / X3d 6.69S / T0 OAV -355 CI S0 2 Me n = 0 CH2CH2 O Z24-356 CI S0 2 Me n = 0 CH2CH2CH2 O Z24-357 CI S0 2 Me n = 0 CH2CH2CH2CH2 O Z24-358 Gl S0 2 Me 5-Me Me Me O Z24- 359 Me S0 2 Me n = 0 Me Me O Z25-360 Me S0 2 Me n = 0 Me Et O Z25-361 Me S0 2 Me n = 0 Me OMe O Z25-362 Me S0 2 Me n = 0 CH2CH2 O Z25 -363 Me S0 2 Me n = 0 CH2CH2CH2 O Z25-364 Me S0 2 Me n = 0 CH CH2CH2CH2 O Z25-365 Me S0 2 Me 5-Me Me Me O Z25-366 CI S0 2 Me n = 0 Me Me O Z25-367 CI S0 2 Me n = 0 Me OMe O Z25-368 CI S0 2 Me n = 0 CH GH2 O Z25-369 Gl S0 2 en = 0 CH2CH2CH2 O Z25-370 CI S0 2 en = 0 JH2CH2CH2GH2 O Z25- 371 CI S0 2 Me 5 - Me Me Me O Z25-372 Me S0 2 Me n = 0 Me Me O Z26-373 Me S0 2 Me n = 0 Me Et O Z26-374 Me S0 2 Me n = 0 Me OMe O Z26-375 Me S0 2 Me n = 0 CH2CH2 O Z26-376 Me S0 2 Me n = 0 CH2CH2CH2 O Z26-377 Me S0 2 Me n = 0 CH2CH2CH2CH2 O Z26-378 Me S0 2 Me 5-Me Me Me O Z26 -379 CI S0 2 Me n = 0 Me Me O Z26-380 CI S0 2 Me n = 0 Me OMe O Z26-381 CI S0 2 Me n = 0 CH 2 CH 2 0 Z26-382 CI S0 2 Me n = 0 CH2CH2CH2 0 Z26-383 CI S0 2 Me n = 0 CH2CH2CH2CH2 0 Z26-384 CI S0 2 Me 5-Me Me Me 0 Z26-385 Me S0 2 Me n = 0 Me Me 0 Z27-386 Me S0 2 Me n = 0 Me Et 0 Z27-387 Me S0 2 en = 0 Me OMe 0 Z27-388 Me S0 2 Me n = 0 CH2CH2 0 Z27-389 Me S0 2 Me n = 0 CH2CH2CH2 0 Z27-390 Me S0 2 Me n = 0 ΟΗ 2 ΟΗ 2 ΟΗ2θΗ 2 0 Z27 zz
Figure imgf000024_0001
/T0df/X3d 6.69S/T0 OAV 82
Figure imgf000024_0001
/ T0df / X3d 6.69S / T0 OAV 82
Figure imgf000025_0001
/T0df/X3d 6.69S/T0 OAV -463 Me S02Me 5 - Me Me Me S Z24 -464 CI S02Me n=0 Me Me S Z24 -465 Me S02 e n=0 Me Me S Z25
Figure imgf000025_0001
/ T0df / X3d 6.69S / T0 OAV -463 Me S0 2 Me 5 - Me Me Me S Z24 -464 CI S0 2 Me n = 0 Me Me S Z24 -465 Me S0 2 en = 0 Me Me S Z25
1-466 Me S02Me n=0 Me OMe S Z251-466 Me S0 2 Me n = 0 Me OMe S Z25
1-467 Me S02 e 5-Me Me Me S Z251-467 Me S0 2 e 5-Me Me Me S Z25
1-468 CI S02 e n=0 Me Me S Z251-468 CI S0 2 en = 0 Me Me S Z25
1-469 Me S02Me n=0 Me Me S Z281-469 Me S0 2 Me n = 0 Me Me S Z28
1-470 Me S02Me n=0 Me OMe S Z281-470 Me S0 2 Me n = 0 Me OMe S Z28
1-471 Me S02Me 5 - Me Me Me S Z281-471 Me S0 2 Me 5-Me Me Me S Z28
1-472 CI S02Me n=0 Me Me S Z281-472 CI S0 2 Me n = 0 Me Me S Z28
1-473 Me S02Me n=0 Me Me S Z291-473 Me S0 2 Me n = 0 Me Me S Z29
1-474 Me S02Me n=0 Me OMe S Z291-474 Me S0 2 Me n = 0 Me OMe S Z29
1-475 Me S02Me 5-Me Me Me S Z291-475 Me S0 2 Me 5-Me Me Me S Z29
1-476 CI S02 e n=0 Me Me S Z291-476 CI S0 2 en = 0 Me Me S Z29
1-477 Me S02Me n=0 Me Me S Z301-477 Me S0 2 Me n = 0 Me Me S Z30
1-478 Me S02Me n=0 Me OMe S Z301-478 Me S0 2 Me n = 0 Me OMe S Z30
1-479 Me S02Me 5-Me Me Me S Z301-479 Me S0 2 Me 5-Me Me Me S Z30
1-480 Gl S02Me n=0 Me Me S Z30 本発明の化合物は次の方法によって製造することができる。 1-480 Gl S0 2 compounds of Me n = 0 Me Me S Z30 present invention can be prepared by the following method.
(製造法 1)  (Production method 1)
Figure imgf000026_0001
Figure imgf000026_0001
(式中、 1^〜15、 n及び Zは前記と同じ意味を表し、 Qはハロゲン原子、 またはィ ミダゾールー 1一ィルを表す。 ） (In the formula, 1 ^ to 15 , n and Z represent the same meaning as described above, and Q represents a halogen atom or imidazole-11-yl.)
すなわち、 化合物 （2) と式： A r COQで表される化合物の各々 1モルあるいは 一方の過剰量を、 溶媒中で塩基の存在下に反応させることによって、 式 （1) で表 される化合物を得ることができる。 That is, the compound (2) and the compound represented by the formula: Ar COQ are reacted in the presence of a base in a solvent in an amount of 1 mol or an excess of each of them, whereby the compound represented by the formula (1) is obtained. Is obtained.
この反応に用いることができる溶媒としては、 ベンゼン、 トルエン等の炭化水素類、 テトラヒドロフラン （THF) 、 ジェチルエーテル等のエーテル類、 塩化メチレン、 クロ口ホルム等のハロゲン化炭化水素類、 ジメチルホルムアミ ド （DMF) 、 ジメ チルスルホキシド （DM S O) 、 ァセトニトリル、 水又はこれらの混合溶媒等が挙 げられる。  Solvents that can be used in this reaction include hydrocarbons such as benzene and toluene, ethers such as tetrahydrofuran (THF) and getyl ether, halogenated hydrocarbons such as methylene chloride and chloroform, and dimethylformamide. (DMF), dimethyl sulfoxide (DMSO), acetonitrile, water, or a mixed solvent thereof.
また塩基としては、 トリェチルァミン、 ジイソプロピルェチルァミン等の脂肪族ァ ミン、 ピリジン等の有機塩基、 KOH、 N a OH等のアルカリ金属水酸化物、 炭酸 ナトリウム、 炭酸カリウム等のアルカリ金属炭酸塩、 水酸化カルシウム、 水酸化マ グネシゥム等のアル力リ土類金属水酸化物、 炭酸カルシウム等のアル力リ土類金属 炭酸塩、 ナトリウムメチラート、 マグネシウムェチラート等のアルコラート類、 N aH、 リチウムジイソプロピルアミ ド （LDA) 等を用いることができる。  Examples of the base include aliphatic amines such as triethylamine and diisopropylethylamine; organic bases such as pyridine; alkali metal hydroxides such as KOH and NaOH; alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, alkaline earth metal carbonates such as calcium carbonate, alcoholates such as sodium methylate and magnesium ethylate, NaH, lithium Diisopropylamide (LDA) or the like can be used.
反応は、 — 78°C〜用いられる溶媒の沸点温度、 好ましくは— 10°C〜室温で円滑 に進行する。  The reaction proceeds smoothly from −78 ° C. to the boiling point of the solvent used, preferably from −10 ° C. to room temperature.
(製造法 2)  (Production method 2)
また本発明化合物 （1) は、 化合物 （2) と式： A r C02H (A rは前記と同じ意 味を表す。 ） で表される化合物とをジシクロへキシルカルポジイミ ド （DC C) 等 の脱水縮合剤の存在下に反応させることによつても得ることができる。 The present compound (1) is the compound (2) wherein: A r C0 2 H (. A r is said to represent the same meaning) dicyclohexyl a compound represented by cyclohexyl Cal positive imide (DC It can also be obtained by reacting in the presence of a dehydrating condensing agent such as C).
この反応において用いられる溶媒としては、 塩化メチレン、 クロ口ホルム、 トルェ ン、 酢酸ェチル、 DMF、 THF、 1, 2—ジメ トキシェタン （DME) 、 ァセト 二トリル等が用いられる。 反応混合物は反応が完結するまで一 10°C〜50°Cで攪 拌され、 常法によって処理される。  Examples of the solvent used in this reaction include methylene chloride, chloroform, toluene, ethyl acetate, DMF, THF, 1,2-dimethyloxetane (DME), and acetate nitrile. The reaction mixture is stirred at 110 ° C to 50 ° C until the reaction is completed, and processed by a conventional method.
原料となる式： A r COQ (八1：及び(3は、 前記と同じ意味を表す。 ） 及び A r C 02H (A rは前記と同じ意味を表す。 ） で表される化合物は、 公知の方法に従って 製造することができる。 The compounds represented by the formulas: A r COQ (8: and (3 represents the same meaning as described above)) and A r C 0 2 H (A r represents the same meaning as described above) It can be produced according to a known method.
また化合物 （2) は、 例えばシァノ酢酸エステルと対応するアミン類とのアミ ド化 反応、 シァノ酢酸とァミン類との DC C等の脱水縮合剤を用いた反応、 シァノ酢酸 クロライドとアミン類との反応等の一般の合成化学的手法で製造することができる。 さらに本発明化合物 （1) が遊離のヒドロキシル基を含有している場合には、 公知 の方法により、 該化合物からェナミン又はその類似物、 ァシレート、 スルホネート、 力ルバメート、 エーテル、 チォエーテル、 スルホキシド又はスルホン誘導体等に誘 導することができる。 Compound (2) can be obtained, for example, by an amidation reaction between a cyanoacetic acid ester and a corresponding amine, a reaction between a cyanoacetic acid and an amine using a dehydrating condensing agent such as DCC, It can be produced by a general synthetic chemistry technique such as a reaction between chloride and amines. Furthermore, when the compound (1) of the present invention contains a free hydroxyl group, the compound can be obtained by a known method from an enamine or an analog thereof, an acylate, a sulfonate, a sulfamate, an ether, a thioether, a sulfoxide or a sulfone derivative. And so on.
前記適当なェナミン又はその類似物としては、 OH部分がそれぞれ、 式： — NR e R f (式中、 1 6及び1 は、 それぞれ独立して、 水素又は炭素数が 1〜 6個の置 換されていてもよいアルキル基又はァリール基を表す。 ） 、 ハロゲン、 S (0) g Rh (式中、 Rhは、 炭素数が 1~ 6個の置換されていてもよいアルキル基又はァ リール基を表し、 gは 0、 1又は 2を表す。 ） に転化されている化合物が挙げられ る。  Said suitable enamines or analogs thereof are those in which the OH moieties are each of the formula: — NR e R f (wherein 16 and 1 are each independently hydrogen or a substitution of 1 to 6 carbon atoms. Represents an alkyl group or an aryl group which may be substituted.), Halogen, S (0) g Rh (where Rh is an alkyl group or an aryl group having 1 to 6 carbon atoms which may be substituted) And g represents 0, 1 or 2.).
また、 前記適当なァシレート、 エーテル、 又は力ルバメート誘導体としては、 OH 部分がそれぞれ、 式： — OCOR i、 — OR j又は OCONRkR l (式中、 R i 及び R jは、 前記の Rhと同じ意味を表し、 Rk及び R 1は、 前記の R eと同じ意 味を表す。 ） に転化されている化合物が挙げられる。  Further, as the above-mentioned suitable acylate, ether, or olebamate derivative, the OH portion is represented by the following formula: —OCOR i, —OR j or OCONRkR l (wherein, R i and R j have the same meanings as the above Rh. And Rk and R 1 have the same meaning as the above-mentioned R e.).
これらの誘導体は、 通常の合成化学的手法で製造し得る。  These derivatives can be produced by ordinary synthetic chemistry techniques.
前記式 （1) で表される化合物は、 その塩、 特に農園芸的に許容される塩に誘導す ることができる。 かかる農園芸的に許容され得る塩としては、 ナトリウム、 力リウ ム等のアル力リ金属塩、 カルシウム等のアルカリ土類塩及びアンモニゥム塩等が挙 げられる。  The compound represented by the formula (1) can be derived into a salt thereof, particularly, an agriculturally / horticulturally acceptable salt. Examples of such agriculturally and horticulturally acceptable salts include alkali metal salts such as sodium and potassium, alkaline earth salts such as calcium and ammonium salts, and the like.
アンモニゥム塩の例としては、 式： N+R a Rb R c R d (式中、 R a、 Rb、 R c 及び Rdは、 各々独立して水素又はヒドロキシ基等により置換されていてもよい - 10アルキル基を表す。 ） のイオンとの塩が挙げられる。 Ra、 Rb、 R c、 及び R d はいずれかが置換されたアルキル基である場合には、 これらは 1〜4個の炭素原子 を含有していることが望ましい。 Examples of ammonium salts include those of the formula: N + R a Rb R c R d (where R a, Rb, R c and Rd are each independently substituted by hydrogen or a hydroxy group, etc. And a 10- alkyl group. When any of Ra, Rb, Rc, and Rd is a substituted alkyl group, these preferably contain 1 to 4 carbon atoms.
本発明化合物 （1) には、 例えば下記に示すような互変異性体が存在しうる。
Figure imgf000029_0001
また、 R4又は R5が水素原子である化合物の場合には、 下記に示す互変化異性体が存 在し得る。 The compound (1) of the present invention may have, for example, the following tautomers.
Figure imgf000029_0001
In the case where R 4 or R 5 is a hydrogen atom, the following tautomers may exist.
Figure imgf000029_0002
Figure imgf000029_0002
これらの化合物はすべて本発明の範囲に含まれる。 All of these compounds fall within the scope of the present invention.
本発明化合物は、 反応終了後、 通常の後処理を行うことにより得ることができる。 また、 本発明化合物の構造は、 I R、 N M R及び M S等の各種スペク トルを測定す ることにより決定することができる。  The compound of the present invention can be obtained by carrying out a usual post-treatment after completion of the reaction. The structure of the compound of the present invention can be determined by measuring various spectra such as IR, NMR and MS.
〔除草剤〕  (Herbicide)
本発明除草剤は、 本発明化合物の 1種又は 2種以上を有効成分として含有する。 本 発明化合物を実際に施用する際には他成分を加えず純粋な形で使用できる。 また農 薬として使用する目的で一般の農薬のとり得る形態、 例えば水和剤、 粒剤、 粉剤、 乳剤、 水溶剤、 懸濁剤、 フロアブル等の形態で使用することもできる。  The herbicide of the present invention contains one or more of the compounds of the present invention as an active ingredient. When the compound of the present invention is actually applied, it can be used in a pure form without adding other components. In addition, it can be used in the form of general pesticides that can be used for pesticides, for example, wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, flowables and the like.
添加剤及び担体としては、 固型剤を目的とする場合は、 大豆粉、 小麦粉等の植物性 粉末、 珪藻土、 燐灰石、 石こう、 タルク、 ベントナイ ト、 パイロフィライ ト、 クレ ィ等の鉱物性微粉末、 安息香酸ソーダ、 尿素、 芒硝等の有機及び無機化合物を使用 することができる。 .  As an additive and a carrier, when a solid agent is intended, mineral powder such as soy flour, flour, etc., vegetable powder, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay, etc. Organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate can be used. .
液体の剤型を目的とする場合は、 ケロシン、 キシレン及びソルベントナフサ等の石 油留分、 シクロへキサン、，シクロへキサノン、 ジメチルホルムアミ ド、 ジメチルス ルホキシド、 アルコール、 アセトン、 トリクロロエチレン、 メチルイソブチルケト ン、 鉱物油、 植物油、 水等を溶剤として使用する。 For liquid dosage form, use oil fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethyls Use rufoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water, etc. as solvents.
また、 これらの製剤において均一かつ安定な形態をとるために、 所望により界面活 性剤を添加することもできる。 界面活性剤としては、 特に限定はないが、 例えば、 ポリォキシェチレンが付加したアルキルフヱニルエーテル、 ポリォキシェチレンが 付加したアルキルエーテル、 ポリオキシエチレンが付加した高級脂肪酸エステル、 ポリオキシエチレンが付加したソルビタン高級脂肪酸エステル、 ポリオキシェチレ ンが付加したトリスチリルフヱニルエーテル等の非イオン性界面活性剤、 ポリオキ シェチレンが付加したアルキルフエニルエーテルの硫酸エステル塩、 アルキルナフ タレンスルホン酸塩、 ポリカルボン酸塩、 リグニンスルホン酸塩、 アルキルナフタ レンスルホン酸塩のホルムアルデヒド縮合物、 イソプチレン一無水マレイン酸の共 重合体等が挙げられる。  In addition, a surfactant may be added, if desired, to obtain a uniform and stable form in these preparations. The surfactant is not particularly limited, and examples thereof include an alkylphenyl ether to which polyoxetylene is added, an alkyl ether to which polyoxetylene is added, a higher fatty acid ester to which polyoxyethylene is added, and a polyoxyethylene. Nonionic surfactants such as sorbitan higher fatty acid esters to which oxyethylene is added, tristyrylphenyl ether to which polyoxyethylene is added, sulfate salts of alkylphenyl ether to which polyoxyethylene is added, alkyl naphthalene sulfonates, Examples include polycarboxylates, ligninsulfonates, formaldehyde condensates of alkylnaphthalenesulfonates, and copolymers of isobutylene-maleic anhydride.
本発明除草剤における有効成分の濃度は、 前述した製剤の形により種々の濃度に変 化させることができる。 例えば、 水和剤においては、 5〜9 0重量％ (以下、 単に％ と書く） 、 好ましくは 1 0〜8 5 %、 乳剤に於いては、 3〜7 0 %、 好ましくは 5 The concentration of the active ingredient in the herbicide of the present invention can be changed to various concentrations depending on the form of the preparation described above. For example, in a wettable powder, 5 to 90% by weight (hereinafter simply referred to as%), preferably 10 to 85%, and in an emulsion, 3 to 70%, preferably 5 to 90%.
〜6 0 %、 粒剤に於いては、 0 . 0 1〜 5 0 %、 好ましくは 0 . 0 5〜4 0 %の濃 度に調整することができる。 The concentration can be adjusted to about 60%, in the case of granules, from 0.01 to 50%, preferably from 0.05 to 40%.
このようにして得られた水和剤や乳剤は、 水で所定の濃度に希釈して懸濁液或 、は 乳濁液として、 粒剤はそのまま雑草の発芽前又は発芽後に土壌に散布処理もしくは 混和処理される。 実際の本発明除草剤の適用量は、 1ヘクタール当たり有効成分 0 . 1 g以上が好ましい。  The wettable powder or emulsion thus obtained is diluted with water to a predetermined concentration to form a suspension or an emulsion, and the granules are directly sprayed or dispersed on soil before or after germination of the weeds. It is mixed. The actual application amount of the herbicide of the present invention is preferably 0.1 g or more of the active ingredient per hectare.
本発明除草剤は、 公知の殺菌剤、 殺虫剤、 殺ダニ剤、 除草剤、 植物成長調整剤、 肥 料等と混合して使用することもできる。 特に、 除草剤と混合使用することにより、 使用薬量を減少させることが可能である。 また、 省力化をもたらすのみならず、 混 合薬剤の相乗作用により一層高い効果も期待できる。 その場合、 複数の公知除草剤 との組合せも可能である。  The herbicide of the present invention can be used in combination with known fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers, and the like. In particular, it is possible to reduce the amount of drug used by mixing and using herbicides. In addition to labor savings, the synergistic action of the mixed drug can be expected to have even higher effects. In that case, a combination with a plurality of known herbicides is also possible.
本発明除草剤と混合使用するにふさわしい薬剤としては、 例えば次のものが挙げら れる。 Examples of agents suitable for use in combination with the herbicide of the present invention include the following. It is.
ジフルフヱニカン、 プロパニル等のァニリ ド系除草剤 ； ァラクロール、 プレチラク ロール等のクロロアセトァ二リ ド系除草剤 ； 2 , 4— D、 2 , 4一 D B等のァリ一 ルォキシアルカン酸系除草剤； ジクロホップーメチル、 フヱノキサプロップーェチ ル等のァリールォキシフヱノキシアルカン酸系除草剤； ジカンパ、 ピリチォバック 等のァリ一ルカルボン酸系除草剤； イマザキン、 イマゼタピル等のィミダゾリ ン系 除草剤 ； ジゥロン、 イソプロッロン等のウレァ系除草剤 ； クロルプロファム、 フヱ ンメジファム等のカーバメ一ト系除草剤； チォベンカルプ、 E P T C等のチォ力一 バメ一ト系除草剤 ； トリフルラリン、 ペンジメタリ ン等のジニトロア二リ ン系除草 剤 ； アシフルオルフヱン、 ホメサフヱン等のジフヱニルエーテル系除草剤；ベンス ルフロン一メチル、 ニコスルフロン等のスルホニルゥレア系除草剤； メ トリプジン、 メタミ ト口ン等のトリアジノン系除草剤； アトラジン、 シァナジン等のトリアジン 系除草剤； フルメッラム等のトリアゾピリ ミ ジン系除草剤； プロモキシニル、 ジク 口べニル等のニトリル系除草剤 ； グリホサート、 グリホシネート等のリ ン酸系除草 剤 ；パラコー ト、 ジフヱンゾコ一ト等の第四アンモニゥム塩系除草剤； フルミロラ ック—ペンチル、 フルチアセッ ト一メチル等の環状イミ ド系除草剤；ベンゾィルプ 口ップェチル、 フランプロップェチル等のベンゾィルァミノプロピオン酸系除草剤 ； その他、 イソキサベン、 エトフメセート、 ォキサジァゾン、 ピぺロホス、 ダイムロ ン、 ベンタゾン、 ベンフルセート、 ダイフヱンゾコート、 ナプロァニリ ド、 トリア ゾフエナミ ド、 キンク口ラック、 クロマゾン、 スルコ トリオン、 ンメチリ ン、 ジ チォピル、 ピラゾレート、 ピリデート、 フルポキサム、 セトキシジム、 トラルコキ シジム等のシク口へキサンジオン系の除草剤等が挙げられる。  Anilide herbicides such as diflupanican and propanil; chloroacetamide herbicides such as arlacrol and pretilachlor; aryloxyalkanoic acid herbicides such as 2,4-D, 2,4-DB; diclohop- Aryloxy phenoxy alkanoic acid herbicides such as methyl and phenyl oxapropetyl; arylcarboxylic acid herbicides such as dicampa and pyrithiobac; imidazoline herbicides such as imazaquin and imazethapyr Urea herbicides such as diperon and isoprolon; carbamate herbicides such as chlorprofam and phenmedipham; thiobencalp, EPTC and other chitosan-bameto herbicides; trifluralin, dinitroa such as pendimethalin, etc. Diphenyl herbicides; diphenyl ethers such as acifluorene and homesaphene Herbicides; Sulfonyl-peryl herbicides such as benzulfuron monomethyl and nicosulfuron; Triazinone herbicides such as metripzine and metamethanone; Triazine herbicides such as atrazine and cyanazine; Triazopyrimidines such as flumellam Herbicides; Nitrile herbicides such as promoxinil and dikopenyl; Phosphoric acid herbicides such as glyphosate and glyphosinate; Quaternary ammonium salt herbicides such as paracoat and dibenzozot; Cyclic imidic herbicides such as fluthiacet-methyl; benzoylaminopropionic acid herbicides such as benzoylp mouthpethyl and flancropethyl; others, isoxaben, etofumesate, oxadiazone, pilophos, dimelone, bentazon, Ben Frussey , Difunzocote, naproanilide, triazofenamide, kink mouth lac, chromazone, sulcotrione, nmethyrine, dichopyr, pyrazolate, pyridate, flupoxam, sethoxydim, tralkoxydim, etc. Is mentioned.
また、 これらを組み合わせた組成物に植物油及び油濃縮物等の添加剤を添加するこ ともできる。  Additives such as vegetable oils and oil concentrates can also be added to compositions combining these.
本発明化合物は、 畑作条件で、 土壌処理及び茎葉処理で高い除草活性を示し、 メ ヒ シバ、 アキノエノコ口、 ィチビ、 ィヌビュ等の各種畑雑草に有効で、 トウモロコシ、 ムギ、 大豆、 ヮタ等の作物に選択性を示す化合物も含まれている。 また本発明化合 物は、 果樹園、 芝生、 線路端、 空き地等の雑草の防除にも適用することができる。 本発明化合物には、 作物、 観賞用植物、 果樹等の有用植物に対し、 生育抑制作用等 の植物成長調節作用を示す化合物も含まれている。 The compound of the present invention shows a high herbicidal activity in soil treatment and foliage treatment under upland cropping conditions, is effective for various upland weeds such as meadowgrass, Aquinoenoko mouth, Ichibi, and Inubu, and is effective for corn, wheat, soybean, peta, etc. Some compounds are selective for crops. The compound of the present invention Objects can also be applied to the control of weeds in orchards, lawns, track ends, vacant lots, etc. The compounds of the present invention also include compounds that exhibit a plant growth regulating effect such as a growth inhibitory effect on useful plants such as crops, ornamental plants and fruit trees.
本発明化合物には、 水田雑草のノビエ、 タマガヤッリ、 ォモダカ、 ホタルイ等の各 種水田雑草に対し、 優れた殺草効力を有し、 イネに選択性を示す化合物も含まれて いる。  The compounds of the present invention include compounds that have excellent herbicidal activity against various paddy weeds such as nobie, tamagayari, omodaka, firefly, etc., and have selectivity to rice.
また、 本発明化合物には植物成長調節作用、 殺菌活性、 殺虫，殺ダニ活性を有する ものも含まれる。 発明を実施するための最良の形態：  The compounds of the present invention also include those having a plant growth regulating activity, a bactericidal activity, an insecticidal and acaricidal activity. BEST MODE FOR CARRYING OUT THE INVENTION
次に実施例を挙げ、 本発明化合物をさらに具体的に説明する。  Next, the compound of the present invention will be described more specifically with reference to examples.
(実施例 1 )  (Example 1)
2—シァノ _N, N—ジメチルー 3— [2—メチル一 3—（3—メチルイソォキサ ゾール一 5—ィル）一 4一（メチルスルホニル）フエニル] ― 3—ォキソプロパンァミ ド （化合物 No.5) の製造  2-cyano _N, N-dimethyl-3- [2-methyl-3- (3-methylisoxazol-15-yl) -14- (methylsulfonyl) phenyl] -3-oxopropaneamide (Compound No. 5) manufacture
Me、 A"へ + Me to A "+
Μέ CN
Figure imgf000032_0001
 Μέ CN
Figure imgf000032_0001
N， N—ジメチルシアノアセトアミ ド 0. 96 gの THF 20m 1溶液に、 油性 N a H (純度約 60%) 0. 35 gを添加して室温で 30分撹拌した。 次いで、 反応 容器を氷浴に浸し液温を約 0°Cに冷却して、 2—メチルー 3—(3—メチルイソォキ サゾール— 5—ィル）ー 4—メチルスルホニルベンゾイルクロリ ド 1. 50 gを添加 し、 そのまま 30分撹拌した後、 室温でさらに一晩撹拌した。  To a solution of 0.96 g of N, N-dimethylcyanoacetamide in 20 ml of THF, 0.35 g of oily NaH (purity: about 60%) was added, followed by stirring at room temperature for 30 minutes. Next, the reaction vessel was immersed in an ice bath to cool the liquid temperature to about 0 ° C, and 1.50 g of 2-methyl-3- (3-methylisoxazole-5-yl) -4-methylsulfonylbenzoyl chloride was added. After the addition, the mixture was stirred as it was for 30 minutes, and further stirred at room temperature overnight.
反応液を氷浴下で希塩酸中へ注加し、 撹拌した後、 クロ口ホルムで分液抽出した。 有機層を飽和食塩水で洗浄後、 無水硫酸ナトリウムで乾燥し、 減圧濃縮レて黄土色 固体を得た。 クロ口ホルム一メタノールより再結晶を行い、 白色結晶として目的物 1. 48 gを得た。 （融点 212— 214°C) (実施例 2 ) The reaction solution was poured into dilute hydrochloric acid in an ice bath, stirred, and then separated and extracted with chloroform. The organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain an ocher solid. The crystals were recrystallized from chloroform-methanol to give 1.48 g of the desired product as white crystals. (Melting point 212-214 ° C) (Example 2)
2—シァノ一N—メチル一 3— [2—メチルー 3—（3—メチルイソォキサゾ一ル 一 5—ィル）一 4— (メチルスルホニル）フヱニル）  2-Cyano-1-N-methyl-3- (2-methyl-3- (3-methylisoxazol-15-yl) -14- (methylsulfonyl) phenyl)
] —3—ォキソプロパンアミ ド （化合物 No.1) の製造
Figure imgf000033_0001
] —Production of 3-oxopropane amide (Compound No.1)
Figure imgf000033_0001
N—メチルシアノアセトアミ ド 0. 94 gのトルエン 12m l溶液に、 油性 N a H (純度約 60%) 0. 23 gを添加し、 室温で 2時間撹拌した。 次いで、 反応液に 2—メチルー 3—（3—メチルイソォキサゾールー 5—ィル）一4ーメチルスルホニ ルペンゾイルクロリ ド 1. 00 gを添加して、 約 80°Cで 2. 5時間加熱した。 反 応混合物を室温に戻し、 酢酸水溶液を加えて酸性にした後、 クロ口ホルムで分液抽 出した。 有機層を飽和食塩水で洗浄後、 無水硫酸ナトリウムで乾燥し、 減圧濃縮し て得られた残渣をシリカゲルカラムクロマトグラフィーにて精製することにより、 淡黄色固体を得た。 クロ口ホルム一メタノールより再結晶行い、 淡黄色結晶として 目的物 0. 1 0 gを得た。 （融点 175— 180°C)  To a solution of 0.94 g of N-methylcyanoacetamide in 12 ml of toluene, 0.23 g of oily NaH (purity: about 60%) was added, and the mixture was stirred at room temperature for 2 hours. Then, add 1.00 g of 2-methyl-3- (3-methylisoxazole-5-yl) -1-methylsulfonyl benzoyl chloride to the reaction solution and heat at about 80 ° C for 2.5 hours did. The reaction mixture was returned to room temperature, and made acidic by adding an aqueous acetic acid solution. The organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give a pale yellow solid. The crystals were recrystallized from methanol-form-form to give 0.110 g of the desired product as pale yellow crystals. (Melting point 175-180 ° C)
(実施例 3 )  (Example 3)
3 - (ァゼチジン一 1—ィル） 一2— [2—メチル一3— (3—メチルイソォキサ ゾール一5—ィル） 一 4_ (メチルスルホニル） フエニル] —3—ォキソプロパン 二トリル （化合物 No.16) の製造
Figure imgf000033_0002
3- (Azetidine-1-yl) 1-2- [2-Methyl-3- (3-methylisoxazol-5-yl) -14- (methylsulfonyl) phenyl] -3-oxopropane nitrile (Compound No.16 ) Manufacturing of
Figure imgf000033_0002
N—（1—シァノ）ァセチルァゼチジン 0. 07 gの無水 TH F 2 m 1溶液に、 油性 N aH (純度約 60%) 0. 02 gを 0°Cで加え、 室温で 30分間攪拌した。 次いで、 反応液に 2—メチルー 3—(3—メチルイソォキサゾールー 5—ィル）ー4一メチル スルホニルベンゾイルクロリ ド 0. 19 gの無水 THF 2m 1溶液を 0°Cで滴下し、 室温で 2時間攪拌した。 反応混合物を希塩酸 5 m 1中に滴下し、 酢酸ェチルで抽出 した。 有機層を無水硫酸マグネシウムで乾燥、 濃縮して得られた残渣を、 シリカゲ ル薄層クロマトグラフィー（塩化メチレン： メタノール =40 ： 1)にて精製して、 赤色固体 0. 06 gを得た。 これをメタノール 1. 5m 1から再結晶することによ り、 橙色粉末として目的物を 0. 04 g得た（融点 158—163°C) To a solution of 0.07 g of N- (1-cyano) acetylazetidine in 2 ml of anhydrous THF, 0.02 g of oily NaH (about 60% purity) is added at 0 ° C, and then at room temperature for 30 minutes. Stirred. Next, a solution of 0.19 g of 2-methyl-3- (3-methylisoxazole-5-yl) -4-methylsulfonylbenzoyl chloride in anhydrous THF (2 ml) was added dropwise to the reaction mixture at 0 ° C. Stirred at room temperature for 2 hours. The reaction mixture was added dropwise to dilute hydrochloric acid (5 ml), and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated, and the resulting residue was purified by silica gel thin-layer chromatography (methylene chloride: methanol = 40: 1) to obtain 0.06 g of a red solid. This was recrystallized from 1.5 ml of methanol to obtain 0.04 g of the desired product as an orange powder (melting point: 158-163 ° C)
(実施例 4)  (Example 4)
2—シァノ一N—メ トキシー N—メチルー 3— [2—メチルー 3—（3—メチルイ ソォキサゾールー 5—ィル）一 4一（メチルスルホニル）フヱニル] ― 3—ォキソプロ パンアミ ド （化合物 No.9) の製造  2-cyano-N-methoxy N-methyl-3- [2-methyl-3- (3-methylisoxazol-5-yl) -1-41- (methylsulfonyl) phenyl] -3-oxopropanamide (Compound No. 9) Manufacturing of
+ MeO、+ MeO,
Figure imgf000034_0001
M Ye ： N
Figure imgf000034_0001
M Ye: N
、S02Me , S0 2 Me
1—シァノ一 N—メ トキシー N—メチルァセトアミ ド 0. 20 gの無水 THF 5 m 1溶液に、 油性 N a H (純度約 60%)0. 07 gを 0 °Cで加え、 室温で 30分間攪 拌した。 次いで、 反応液に 2—メチルー 3—（3—メチルイソォキサゾ一ルー 5—ィ ル）— 4ーメチルスルホニルベンゾイルクロリ ド 0. 49 gの無水 THF 3 m 1溶液 を 0°Cで滴下し、 室温で 2時間攪拌した。 反応混合物を希塩酸 10m 1中に滴下し、 酢酸ェチルで抽出した。 有機層を無水硫酸マグネシウムで乾燥、 濃縮して得られた 残渣を、 シリカゲル薄層クロマトグラフィー（塩化メチレン： メタノール =20 : 1) にて精製することにより、 茶色固体 0. 62 gを得た。 これをメタノール 3m lか ら再結晶し、 橙色粉末として目的物 0. 13 gを得た。 融点： 200— 206°C1-Cyanone N-methoxy N-methylacetamide To a solution of 0.20 g of anhydrous THF in 5 ml of THF, add 0.07 g of oily NaH (purity approx. 60%) at 0 ° C and at room temperature for 30 minutes Stirred. Then, a solution of 0.49 g of 2-methyl-3- (3-methylisoxazolyl 5-yl) -4-methylsulfonylbenzoyl chloride in anhydrous THF (3 ml) was added dropwise to the reaction mixture at 0 ° C. Then, the mixture was stirred at room temperature for 2 hours. The reaction mixture was added dropwise to 10 ml of diluted hydrochloric acid, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated, and the residue obtained was purified by silica gel thin-layer chromatography (methylene chloride: methanol = 20: 1) to obtain 0.62 g of a brown solid. This was recrystallized from 3 ml of methanol to obtain 0.13 g of the desired product as an orange powder. Melting point: 200-206 ° C
(実施例 5) (Example 5)
2—シァノ -N, N—ジメチルー 3—〔2—メチル一 3_(3—メチルー 4， 5—ジ ヒドロイソォキサゾ一ルー 5—ィル）一 4一（メチルスルホニル）フヱニル〕一 3—ォ キソプロパンアミ ド （化合物 No.51) の製造
Figure imgf000035_0001
2-Cyano-N, N-dimethyl-3- [2-methyl-3- (3-methyl-4,5-dihydroisoxazoyl-1-yl) -1-41- (methylsulfonyl) phenyl] -1- Production of oxopropane amide (Compound No. 51)
Figure imgf000035_0001
N， N—ジメチル一シァノアセトアミ ド 0. 49 g (4. 3 7mmo 1 ) とジェチ ルマグネシウム 0. 5 6 g (4. 7 1 mm 0 1 ) を無水トルエン 5 m 1に加え、 1 時間還流させた。 溶媒を留去して得られた残留物を無水 THF 8m 1に溶かし、 こ れに 2—メチル一 3— [3—メチル（4， 5—ジヒドロイソォキサゾ一ルー 5—ィ ル）] —4一（メチルスルホニル）ベンゾイルク口ライ ド 1. 0 3 g (3. 43 mm o 1 ) の無水 THF 2m 1溶液を 0°Cで加え、 室温で一晩攪拌した。 溶媒を留去して 得られた残留物にクロ口ホルム 50m 1を加え、 0. 1 N塩酸 20m 1で 2回、 次 いで飽和食塩水 2 0m 1で 1回洗浄した。 有機層を無水硫酸マグネシウムで乾燥、 濃縮して得られた残留物にメタノール 6m 1を加え攪拌すると白色粉末が析出した。 これをろ別、 減圧乾燥させて白色粉末結晶として目的物 0. 88 g (収率 6 5%) を得た。 融点： 1 62— 1 6 3°C 0.49 g (4.37 mmo 1) of N, N-dimethyl monocyanoacetamide and 0.56 g (4.71 mm 01) of methyl magnesium were added to 5 ml of anhydrous toluene and refluxed for 1 hour. Was. The residue obtained by distilling off the solvent was dissolved in 8 ml of anhydrous THF, and 2-methyl-1- [3-methyl (4,5-dihydroisoxazolyl-5-yl)] was added thereto. A solution of 1.03 g (3.43 mmol) of mono (methylsulfonyl) benzoyl chloride in 2 ml of anhydrous THF was added at 0 ° C, and the mixture was stirred at room temperature overnight. To the residue obtained by evaporating the solvent was added 50 ml of chloroform-form, and the mixture was washed twice with 20 ml of 0.1 N hydrochloric acid and then once with 20 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate and concentrated, and 6 ml of methanol was added to the resulting residue, followed by stirring to precipitate a white powder. This was filtered off and dried under reduced pressure to obtain 0.88 g (yield 65%) of the desired product as white powdery crystals. Melting point: 1 62—1 6 3 ° C
(実施例 6 )  (Example 6)
2—シァノ _N, N—ジメチル一 3—〔2—メチル一 3—（3—メチルー 4, 5—ジ ヒドロイソォキサゾール一 5—ィル）ー 4— (メチルスルホニル）フヱニル〕一 3—ォ キソプロパンアミ ドのナトリウム塩 （化合物 No.52) の製造  2-cyano _N, N-dimethyl-13- [2-methyl-13- (3-methyl-4,5-dihydroisoxazol-15-yl) -4- (methylsulfonyl) phenyl] -3- Production of sodium salt of oxopropane amide (Compound No. 52)
Figure imgf000035_0002
Figure imgf000035_0002
2—シァノー N, N_ジメチルー 3—〔2—メチル一 3—（3—メチル（4， 5—ジ ヒドロイソォキサゾ一ルー 5—ィル）ー 4— (メチルスルホニル）フヱニル）ォキソプ 口パンアミ ド 0. 13 g (0. 33mmo 1 ) をメタノール 1 m 1に懸濁させ、 2 8%ナトリウムメ トキシドメタノール溶液 0. 0666 g (0. 344mmo 1 ) を滴下した。 室温で 2時間攪拌後、 溶媒を留去することにより薄褐色の個体 0. 1 4 gを得た。 融点： 220— 230°C 2-cyano N, N_dimethyl-3- (2-methyl-1- (3-methyl (4,5-dihydroisosazozo-1-yl 5-yl) -4- (methylsulfonyl) phenyl) oxop 0.113 g (0.33 mmo 1) of the mouth panamide was suspended in 1 ml of methanol, and 0.0666 g (0.344 mmo 1) of a 28% sodium methoxide methanol solution was added dropwise. After stirring at room temperature for 2 hours, the solvent was distilled off to obtain 0.14 g of a light brown solid. Melting point: 220-230 ° C
(実施例 7) (Example 7)
2 _〔（ジメチルァミノ）チォキソメチル〕一 3— [2—メチル一 3—(3—メチルイ ソォキサゾ一ル一 5 _ィル）一4— (メチルスルホニル）フエニル） ] 一 3—ォキソプ 口パンニトリル （化合物 No.68) の製造 2 _ [(Dimethylamino) thioxomethyl] -13- [2-Methyl-13- (3-methylisoxazolyl-5_yl) -14- (methylsulfonyl) phenyl)] 13-Oxoppanpanitrile (compound No.68)
Me、、 Me,
M
Figure imgf000036_0001
M
Figure imgf000036_0001
N,N—ジメチルシアノチオアセトアミ ド 0. 15 gの THF 2. 5ml溶液に、 油 性 N a H (純度約 60%) 0. 05 gを添加して室温で 30分撹拌した。 次いで、 反応容器を氷浴に浸し液温を約 0°Cに冷却して、 2—メチル一 3—（3—メチルイソ ォキサゾール _ 5 _ィル）一 4一 （メチルスルホニル） ベンゾイルクロリ ド 0. 20 gを添加し、 そのまま 30分撹拌した後、 室温でさらに一晩撹拌した。 反応液を氷 浴下で希塩酸中へ注加し、 撹拌した後、 クロ口ホルムで分液抽出した。 有機層を飽 和食塩水で洗浄後、 無水硫酸ナトリウムで乾燥し、 減圧濃縮して黄土色固体を得た。 メタノールより再結晶を行い、 淡黄色結晶として目的物 0. 12 gを得た。 融点： 184-187 °C d e c.  To a solution of 0.15 g of N, N-dimethylcyanothioacetamide in 2.5 ml of THF was added 0.05 g of oily NaH (purity of about 60%), followed by stirring at room temperature for 30 minutes. Next, the reaction vessel was immersed in an ice bath to cool the solution temperature to about 0 ° C., and 2-methyl-1- (3-methylisoxazole_5-yl) -14- (methylsulfonyl) benzoyl chloride was added. 20 g was added, and the mixture was stirred as it was for 30 minutes, and further stirred at room temperature overnight. The reaction solution was poured into dilute hydrochloric acid under an ice bath, stirred, and then separated and extracted with chloroform. The organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain an ocher solid. The crystals were recrystallized from methanol to obtain 0.12 g of the desired product as pale yellow crystals. Melting point: 184-187 ° C de c.
(実施例 8) (Example 8)
2—シァノ一 N，N—ジメチルー 3 -〔2—メチルー 3—（ジメ トキシメチル）一 4— (メチルスルホニル）フヱニル〕— 3—ォキソプロパンアミ ド （化合物 No.86) の製 Preparation of 2-cyano-N, N-dimethyl-3- [2-methyl-3- (dimethoxymethyl) -14- (methylsulfonyl) phenyl] -3-oxopropanamide (Compound No.86)
Figure imgf000036_0002
N，N—ジメチルーシァノアセトアミ ド 1. 00 g (8. 91mmo l) を無水 TH F 15m lに溶かし、 0°Cで 60%水素化ナトリウム 0. 31 g (7. 7mmo 1 ) を加え 60分室温で攪拌した。 これとは別に 2—メチルー 3— (ジメ トキシメチル） — 4—メタンスルホニルベンゾイツクアシッ ド 1. 26 g (4. 37mmo l) を 無水 THF 8m 1に溶かし室温でカルボニルジイミダゾール 0. 85 g (5. 24 mmo 1) を加え 60分室温で攪拌した。 前者の反応液に後者の反応液を 0 °Cで素 早く加え 2時間分室温で攪拌した。 この反応液は THFを減圧留去後、 残さを水 3 0m 1に溶かしクロ口ホルム 10m lで 2回洗浄した。 水層を塩酸で酸性とし、 析 出した有機物をクロ口ホルム 3 Om lで抽出、 さらに飽和食塩水 1 Om lで洗浄、 硫酸マグネシウムで乾燥後溶媒を留去した。 残さにメタノール 12m 1を加え攪拌 すると標題の化合物を白色粉末結晶として 0. 92 g得た。 融点： 151— 154°C
Figure imgf000036_0002
Dissolve 1.00 g (8.91 mmol) of N, N-dimethyl-cyanoacetamide in 15 ml of anhydrous THF and dissolve 0.31 g (7.7 mmol) of 60% sodium hydride at 0 ° C. The mixture was stirred at room temperature for 60 minutes. Separately, 1.26 g (4.37 mmol) of 2-methyl-3- (dimethoxymethyl)-4-methanesulfonylbenzoic acid was dissolved in 8 ml of anhydrous THF, and 0.85 g of carbonyldiimidazole was added at room temperature. 24 mmo 1) was added and the mixture was stirred at room temperature for 60 minutes. The latter reaction solution was quickly added to the former reaction solution at 0 ° C., followed by stirring at room temperature for 2 hours. After THF was distilled off under reduced pressure, the residue was dissolved in 30 ml of water and washed twice with 10 ml of chloroform. The aqueous layer was acidified with hydrochloric acid, and the precipitated organic matter was extracted with 3 Oml of chloroform, washed with 1 Oml of saturated saline, dried over magnesium sulfate, and the solvent was distilled off. After adding 12 ml of methanol to the residue and stirring, 0.92 g of the title compound was obtained as white powder crystals. Melting point: 151-154 ° C
(参考例） ： (Reference example):
2—メチル _ 3— [3—メチル（4， 5—ジヒ ドロイソォキサゾールー 5—ィル）] — 4— (メチルスルホニル）ベンゾイツクァシッ ド （2) の製造 2-Methyl _ 3— [3-Methyl (4,5-dihydroisoxazole-5-yl)] — 4- (Methylsulfonyl) benzoic acid (2)
Figure imgf000038_0001
ァセトアルドキシム 2. 24 g (37. 9 mm o l) と N—クロロスクシイミ ド 4. 90 g (36. 6mmo 1) をクロ口ホルム 30m 1に溶かし、 ピリジン約 0. 0 6 gを滴下後 30分還流させた。 これに、 3—二トロー 2—メチルスチレン 4. 0 2 g (24. 6mmo 1) を加え、 反応液を 50〜60°Cに保ちながらトリェチル ァミン 3. 70 g (36. 5mmo 1 ) のクロ口ホルム 5 m 1溶液を滴下した。 さ らに 1時間還流させた後、 溶媒を留去して得られた残留物をシリカゲルカラムクロ マトグラフィー（クロ口ホルム：メタノール =40 ： 1)で精製して、 2—二トロー 6—（3—メチル一4, 5—ジヒドロイソォキサゾ一ル一5—ィル）トルエン （3) を 5. 57 g得た （収率 102%) 。
Figure imgf000038_0001
Dissolve 2.24 g (37.9 mmol) of acetoaldoxime and 4.90 g (36.6 mmo 1) of N-chlorosuccinimide in 30 ml of black-mouthed form, add about 0.06 g of pyridine and add 30 g Reflux for a minute. To this was added 4.02 g (24.6 mmo 1) of 3-nitro-2-methylstyrene, and 3.70 g (36.5 mmo 1) of triethylamine was added while maintaining the reaction solution at 50 to 60 ° C. A 5 ml solution of mouth form was added dropwise. After further refluxing for 1 hour, the solvent was distilled off, and the resulting residue was purified by silica gel column chromatography (form: methanol = 40: 1) to give 2-nitro-6- ( 5.57 g of 3-methyl-1,4-dihydroisoxazolyl-5-yl) toluene (3) was obtained (yield: 102%).
2—二トロ一 6—（3—メチル一4， 5—ジヒドロイソォキサゾールー 5—ィル）ト ルェン （.3) 5. 06 g (22. 9mmo 1 ) を酢酸ェチル 50 m 1に溶かし、 1 0%パラジウムカーボン（乾燥） 0. 20 gを添加した。 1気圧水素雰囲気下、 室温 で 12時間攪拌後、 不溶物をろ別し、 溶媒を留去することにより 2—メチルー 3— (3—メチル一4, 5—ジヒドロイソォキサゾール一 5—ィル） ァニリン （4) を 4. 39 g得た （収率 100%) 。 2-Nitro-6- (3-methyl-1,4,5-dihydroisoxazole-5-yl) toluene (.3) 5.06 g (22.9 mmo 1) in 50 ml of ethyl acetate After dissolution, 0.20 g of 10% palladium on carbon (dry) was added. 1 atm hydrogen atmosphere, room temperature After stirring for 12 hours, the insoluble material was filtered off, and the solvent was distilled off to give 2-methyl-3- (3-methyl-1,4,5-dihydroisoxazole-15-yl) aniline (4). 4. 39 g was obtained (100% yield).
2—メチルー 3— (3—メチルー 4， 5—ジヒドロイソォキサゾール一 5—ィル） ァニリン （4) 4. 62 g (24. 2mmo 1 ) とチオシアン酸ナトリウム 6. 0 6 g (74. 8mmo 1 ) とをメタノール 40 m 1に溶解させた。 これに飽和臭化 ナトリウムメタノール溶液 15m l と臭素 4. 5 gの混合物を一 10。Cで滴下し、 滴下終了後室温で 1時間さらに攪拌した。 溶媒を留去して得られた残留物に水 50 m 1を加え、 酢酸ェチル 100m lで 3回抽出した。 有機層をあわせて、 飽和食塩 水 50m lで洗浄し、 無水硫酸マグネシウムで乾燥、 濃縮して褐色オイル 5. 50 gを得た。 この褐色オイル 5. 50 gをエタノール 30m 1に溶かして得られた溶 液をナトリウムスルフィ ド · 9水和物 5. 87 g (24. 4 mm o l) の 30m l 水溶液へ 0°Cで滴下し、 室温で 1時間攪拌した。 反応混合物に、 ヨウ化メチル 3. 63 g (25. 5mmo 1 ) を室温で加え、 さらに 3時間攪拌した。 反応液から溶 媒を留去して得られた残留物に水 50m 1を加え、 生成物をクロ口ホルム 3 Om l で 2回抽出した。 有機層を合わせ、 飽和食塩水 2 Om 1で洗浄し、 無水硫酸マグネ シゥムで乾燥、 濃縮することにより褐色個体 3. 65 gを得た。 これをシリカゲル カラムクロマトグラフィー （クロ口ホルム ： メタノール =20 : 1) で精製して、 2—メチルー 3— （3—メチルー 4, 5—ジヒドロイソォキサゾール— 5—ィル） _4—メチルチオァニリン （5) を 2. 39 g得た （収率 45%) 。  2-Methyl-3- (3-methyl-4,5-dihydroisoxazole-5-yl) aniline (4) 4.62 g (24.2 mmo 1) and sodium thiocyanate 6.06 g (74. 8 mmo 1) was dissolved in 40 ml of methanol. A mixture of 15 ml of a saturated sodium bromide methanol solution and 4.5 g of bromine was added thereto. After dropwise addition, the mixture was further stirred at room temperature for 1 hour. 50 ml of water was added to the residue obtained by evaporating the solvent, and the mixture was extracted three times with 100 ml of ethyl acetate. The organic layers were combined, washed with 50 ml of a saturated saline solution, dried over anhydrous magnesium sulfate and concentrated to obtain 5.50 g of a brown oil. A solution obtained by dissolving 5.50 g of this brown oil in 30 ml of ethanol was dropped at 0 ° C into a 30 ml aqueous solution of 5.87 g (24.4 mmol) of sodium sulfide 9-hydrate. Then, the mixture was stirred at room temperature for 1 hour. To the reaction mixture, 3.63 g (25.5 mmo 1) of methyl iodide was added at room temperature, and the mixture was further stirred for 3 hours. The solvent was distilled off from the reaction solution, 50 ml of water was added to the residue obtained, and the product was extracted twice with 3 Oml of chloroform. The organic layers were combined, washed with saturated saline 2 Om1, dried over anhydrous magnesium sulfate, and concentrated to obtain 3.65 g of a brown solid. This was purified by silica gel column chromatography (form: methanol = 20: 1) to give 2-methyl-3- (3-methyl-4,5-dihydroisoxazole-5-yl) _4-methylthioa 2.39 g of nilin (5) was obtained (yield: 45%).
2—メチルー 3— (3—メチル一4, 5—ジヒドロイソォキサゾ一ルー 5—ィル） ー4ーメチルチオァニリン （5) 2. 39 g (1 0. 1 mmo 1 ) を濃塩酸 1 Om 1に溶解させ、 一 10°Cに冷却した。 次いで、 この溶液に亜硝酸ナトリウム 0. Ί 9 g (11. 4mmo 1 ) の水 3m 1溶液を滴下し、 一 10〜0°Cで 1時間熟成さ せてジァゾ二ゥム塩を調製した。 得られたジァゾ二ゥム塩をヨウ化カリウム 4. 3 3 g (26. Ommo 1 ) の水溶液 3m 1中へ 60〜80°Cで滴下し、 滴下後同温 にて 30分間熟成させた。 沈殿した褐色油状物をクロ口ホルム 5 Om lで 2回抽出 し、 有機層を 3%亜硫酸ナトリウム水 3 Om 1で 2回、 飽和食塩水 30 m 1でそれ ぞれ洗浄し、 無水硫酸マグネシウムで乾燥、 濃縮することにより褐色オイル 3. 02-Methyl-3- (3-Methyl-1,5-dihydroisoxazolyl-5-yl) -4-methylthioaniline (5) 2.39 g (10.1 mmo 1) of concentrated hydrochloric acid Dissolved in 1 Om 1 and cooled to 110 ° C. Then, to this solution was added dropwise a solution of 0.9 g (11.4 mmo 1) of sodium nitrite in 3 ml of water, and the mixture was aged at 110 to 0 ° C. for 1 hour to prepare a diazodium salt. The obtained diazodium salt was dropped into 60 ml of an aqueous solution of 4.33 g (26. Ommo 1) of potassium iodide at 60 to 80 ° C., and the mixture was aged at the same temperature for 30 minutes. The precipitated brown oil was extracted twice with 5 Oml of black-mouthed form. The organic layer was washed twice with 3% aqueous 3% sodium sulfite and with 30 ml of saturated saline, dried over anhydrous magnesium sulfate and concentrated to give a brown oil.
2 gを得た。 このものをシリカゲルカラムクロマトグラフィー （クロ口ホルム ： メ タノール =20 ： 1) で精製して、 2—ョ一ド一 5—メチルチオ一 6— （3—メチ ルー 4， 5—ジヒ ドロイソォキサゾ一ルー 5—ィル） トルエン （6) を 2. 81 得た （80%) 。 2 g were obtained. This was purified by silica gel column chromatography (chloroform: methanol = 20: 1) to give 2-hydroxy-5-methylthio-6- (3-methyl-4-, 5-dihydroisoxazolu-5-methyl). —Yl) 2.81 of toluene (6) were obtained (80%).
2—ョ一ドー 5—メチルチオ一 6— （3—メチル一4, 5—ジヒ ドロイソォキサゾ —ル一 5—ィル） トノレェン （6) 2. 81 g (8. 09mmo 1 ) 、 メタノール 5 m l、 THF 5m l、 トリー n—プチルァミ ン 2. 20 g (1 1. 8mmo l) 、 ， 及びビス （トリフエニルホスフィン） パラジウムジクロライ ド 0. 31 g (0. 4 4mmo l) を 50m lステンレス製ォートクレーブにそれぞれ加え、 75 k g * c m- 3の一酸化炭素加圧雰囲気下、 70〜80°Cで 10時間携拌した。 反応液を減圧 濃縮し、 得られた残留物にクロ口ホルム 6 Om 1を加え、 3%亜硫酸ナトリウム水 溶液 30 m 1、 2 %炭酸ナトリウム水溶液 30 m 1、 飽和食塩水 30m lでそれぞ れ洗浄し、 無水硫酸マグネシウムで乾燥、 濃縮して褐色オイル 6. 04 gを得 。 このものをシリ力ゲルカラムク口マトグラフィー （クロロホルム ： メタノ一ル = 2 0 : 1) で精製して、 メチル 2-hydroxy-5-methylthio-6- (3-methyl-1,5-dihydroisoxazozol-5-yl) tonolen (6) 2.81 g (8.09mmo1), methanol 5 ml, THF 5 ml, 2.20 g (11.8 mmol) of tree n-butylamine, 0.31 g (0.44 mmol) of bis (triphenylphosphine) palladium dichloride in a 50 ml stainless steel autoclave Each was added, and the mixture was stirred at 70 to 80 ° C. for 10 hours under a carbon monoxide pressurized atmosphere of 75 kg * cm- 3 . The reaction mixture was concentrated under reduced pressure.To the resulting residue was added 6 mL of formaldehyde, and 30 ml of a 3% aqueous sodium sulfite solution, 30 ml of a 2% aqueous sodium carbonate solution, and 30 ml of a saturated saline solution were added. The extract was washed, dried over anhydrous magnesium sulfate, and concentrated to give a brown oil (6.04 g). This product was purified by silica gel column chromatography (chloroform: methanol = 20: 1), and methyl
2—メチル一 3 - [3—メチル （4， 5—ジヒ ドロイソォキサゾールー 5—ィル） ] -4 - (メチルチオ） ベンゾェ一ト （7) を橙色液体として 2. 13 g得た （収率 93%) 。  2.13 g of 2-methyl-1- [3-methyl (4,5-dihydroisoxazole-5-yl)]-4- (methylthio) benzoate (7) was obtained as an orange liquid ( Yield 93%).
メチル 2—メチル _ 3— [3—メチル （4， 5—ジヒ ドロイソォキサゾールー 5 —ィル） ] —4— (メチルチオ） ベンゾェ一ト （7) 2. 13 g (7. 62mmo 1) をクロ口ホルム 4 Om 1に溶かし、 m—クロ口過安息香酸 （m— CP BA) 約 Methyl 2-methyl _ 3— [3-Methyl (4,5-dihydroisoxazole-5-yl)] —4- (Methylthio) benzoate (7) 2.13 g (7.62 mmo 1) Was dissolved in black mouth form 4 Om 1 and m-black mouth perbenzoic acid (m—CP BA)
3 gを添加した。 反応液の発熱が収まってから、 さらに m— C P B A約 1 gを追加 し 1 0時間室温で攪拌した。 析出した固体をろ別し、 ろ液を 5%チォ硫酸ナトリウ ム水溶液 20 m 1で 2回、 2 %炭酸ナトリウム水 30 m 1で 2回、 飽和食塩水 30 m 1でそれぞれ洗浄し、 無水硫酸マグネシウムで乾燥後濃縮すると淡橙色液体とし てメチル 3 g was added. After the heat generation of the reaction solution stopped, about 1 g of m-CPBA was further added, and the mixture was stirred at room temperature for 10 hours. The precipitated solid was filtered off, and the filtrate was washed twice with a 5% aqueous sodium thiosulfate solution (20 ml), twice with a 2% aqueous sodium carbonate solution (30 ml), and twice with a saturated saline solution (30 ml), and sulfuric anhydride was added. Concentrate after drying with magnesium to give a pale orange liquid Methyl
2—メチルー 3 - [3—メチル （4, 5—ジヒドロイソォキサゾールー 5—ィル） ] 一 4— (メチルスルホニル） ベンゾエート （8) を 2. 20 g得た （収率 92%) 。 メチル 2—メチル一 3— [3—メチル （4, 5—ジヒ ドロイソォキサゾ一ルー 5 —ィル） ] 一 4一 （メチルスルホニル） ベンゾェ一ト （8) 2. 20 g (7. 06 mmo 1) をメタノール 2 Om lに溶かし、 約 5%水酸化ナトリウム水溶液 2 Om 1を加え、 室温で 2日攪拌した。 反応液からメタノールを減圧下留去して得られた 残留物に水 2 Om 1を加え、 クロ口ホルム 1 Om 1で洗浄して水層中の不溶物をろ 過した。 得られた水層に濃塩酸をゆっく り滴下すると白色の固体が析出した。 これ をろ別、 減圧乾燥することにより、 白色粉末として 2—メチルー 3— [3—メチル 2.20 g of 2-methyl-3- [3-methyl (4,5-dihydroisoxazole-5-yl)]-1- (methylsulfonyl) benzoate (8) was obtained (yield 92%). . Methyl 2-methyl-3- (3-methyl (4,5-dihydroisoxazolyl-5-yl)) 1-41 (methylsulfonyl) benzoate (8) 2.20 g (7.06 mmo 1) Was dissolved in methanol (2 Oml), about 5% aqueous sodium hydroxide solution (2 Om1) was added, and the mixture was stirred at room temperature for 2 days. Methanol was distilled off from the reaction solution under reduced pressure, and 2 Om 1 of water was added to the obtained residue. The residue was washed with 1 Om 1 of chloroform and the insolubles in the aqueous layer were filtered off. When concentrated hydrochloric acid was slowly dropped into the obtained aqueous layer, a white solid was deposited. This is filtered off and dried under reduced pressure to give 2-methyl-3- [3-methyl
(4， 5—ジヒドロイソォキサゾール一 5—ィル） ] _4_ (メチルスルホニル) ベンゾイツクァシッ ド （2) を 1. 85 g得た （収率 88%) 。 融点： 167—1 74°C d e c. (4,5-dihydroisoxazol-1-yl)] _ 4_ (methylsulfonyl) benzoic acid (2) (1.85 g, yield 88%) was obtained. Melting point: 167-174 ° C de c.
上記実施例を含め、 以上のようにして得られる本発明化合物の代表例を第 2表に示 す。  Table 2 shows typical examples of the compounds of the present invention obtained as described above, including the above Examples.
第 2 表  Table 2
3
Figure imgf000041_0001
Three
Figure imgf000041_0001
No. , 2 R3n 4 R5 X Z 備考No., 2 R 3 n 4 R 5 XZ Remarks
1 Me S02Me n=0 H Me 0 Z3 175 - 1801 Me S0 2 Me n = 0 H Me 0 Z3 175-180
2 Me S02Me n=0 H iso-Pr 0 Z3 185 - 1882 Me S0 2 Me n = 0 H iso-Pr 0 Z3 185-188
3 Me S02Me n=0 H cycl-Pr 0 Z3 209 - 2103 Me S0 2 Me n = 0 H cycl-Pr 0 Z3 209-210
4 Me S02 e n=0 H 4-CI-Ph 0 Z3 237 - 2404 Me S0 2 en = 0 H 4-CI-Ph 0 Z3 237-240
5 Me S02Me n=0 Me Me 0 Z3 212 - 2145 Me S0 2 Me n = 0 Me Me 0 Z3 212-214
6 Me S02Me n=0 Et Et 0 Z3 151 - 1536 Me S0 2 Me n = 0 Et Et 0 Z3 151-153
7 Me S02Me n=0 Me iso-Pr 0 Z3 160 - 1627 Me S0 2 Me n = 0 Me iso-Pr 0 Z3 160-162
8 Me S02Me n=0 Me Et 0 Z3 203 - 2068 Me S0 2 Me n = 0 Me Et 0 Z3 203-206
9 Me S02 e n=0 Me OMe 0 Z3 200 - 206
Figure imgf000042_0001
9 Me S0 2 en = 0 Me OMe 0 Z3 200-206
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000043_0001
82 Me S02Me n=0 Me OMe 0 Z28 104-106 82 Me S0 2 Me n = 0 Me OMe 0 Z28 104-106
83 Me S02Me n=0 Me Me 0 Z29 169-17083 Me S0 2 Me n = 0 Me Me 0 Z29 169-170
84 Me S02Me n=0 Me Me 0 Z30 NMR-11 84 Me S0 2 Me n = 0 Me Me 0 Z30 NMR-11
85 Me S02 e n=0 Me Me 0 CHO 171-17385 Me S0 2 en = 0 Me Me 0 CHO 171-173
86 Me S02 e n=0 Me Me 0 CH(OMe)2 151-15486 Me S0 2 en = 0 Me Me 0 CH (OMe) 2 151-154
87 Me S02Me n=0 Me Me 0 CH=NOMe 151-15287 Me S0 2 Me n = 0 Me Me 0 CH = NOMe 151-152
88 Me S02Me n=0 Me Me 0 Z13 120-123 88 Me S0 2 Me n = 0 Me Me 0 Z13 120-123
'H- NMR(5、 ppm、 CDCI3 ) 'H-NMR (5, ppm, CDCI 3 )
NMR-1： 2.15(3H,s) 3.28(6H,s) 7.48(1 H,d) 7.53(1 H,d) 7.97(2H,s) NMR-1: 2.15 (3H, s) 3.28 (6H, s) 7.48 (1 H, d) 7.53 (1 H, d) 7.97 (2H, s)
NMR-2： 2.09(3H,s) 2,67(3H,s) 3.32(6H,s) 7.33(2H,m) 7.48(3H,m) 7.60(1 H,d) 8.20(1 H,d)  NMR-2: 2.09 (3H, s) 2,67 (3H, s) 3.32 (6H, s) 7.33 (2H, m) 7.48 (3H, m) 7.60 (1H, d) 8.20 (1H, d)
NMR-3： 2.08(3H,s) 2.65(3H,s) 3.36(3H,s) 3.85(3H,s) 7.33(2H,m) 7.48(3H,m) NMR-3: 2.08 (3H, s) 2.65 (3H, s) 3.36 (3H, s) 3.85 (3H, s) 7.33 (2H, m) 7.48 (3H, m)
7.62(1 H,d) 8.22(1 H,d) 7.62 (1 H, d) 8.22 (1 H, d)
NMR-4： 2.74(3H,s) 3,28(3H,s) 3.37(3H,s) 3.86(3H,s) 7.85(1 H,d) 8.23(1 H,d) NMR-5： 2.36(3H,s) 2.73(3H,s) 3.32(6H,s) 7.69(1 H,d) 8.37(1 H,d) 8.39(1 H,s) NMR-6： 2.36(3H,s) 2.83(3H,s) 3.38(3H,s) 3.85(3H,s) 7.72(1 H，d) 8.29(1 H,d) NMR-4: 2.74 (3H, s) 3,28 (3H, s) 3.37 (3H, s) 3.86 (3H, s) 7.85 (1H, d) 8.23 (1H, d) NMR-5: 2.36 ( 3H, s) 2.73 (3H, s) 3.32 (6H, s) 7.69 (1 H, d) 8.37 (1 H, d) 8.39 (1 H, s) NMR-6: 2.36 (3H, s) 2.83 (3H , s) 3.38 (3H, s) 3.85 (3H, s) 7.72 (1H, d) 8.29 (1H, d)
8.30(1 H,s) 8.30 (1 H, s)
NMR-7： 2.20(3H,s) 2.38(3H,s) 2.90(3H,s) 3,48— 3.53(2H,m) 3,69—3.73(2H,m) NMR-7: 2.20 (3H, s) 2.38 (3H, s) 2.90 (3H, s) 3,48- 3.53 (2H, m) 3,69-3.73 (2H, m)
6.38(1 H,s) 7.69(1 H,d) 8.12(1H,d) 6.38 (1 H, s) 7.69 (1 H, d) 8.12 (1H, d)
NMR-8： 2.26(3H,s) 2.45(3H,s) 2,96(3H,s) 3.70-3.82(4H,m) 6.44(1 H,s) 7.76 NMR-8: 2.26 (3H, s) 2.45 (3H, s) 2,96 (3H, s) 3.70-3.82 (4H, m) 6.44 (1H, s) 7.76
(1H,d) 8.21(1 H,d) (1H, d) 8.21 (1 H, d)
NMR-9： 1.57(6H,s) 2.41(3H,s) 3.18(2H,bs) 3.23(3H,s) 3,38(3H,s) 3.85(3H,s) NMR-9: 1.57 (6H, s) 2.41 (3H, s) 3.18 (2H, bs) 3.23 (3H, s) 3,38 (3H, s) 3.85 (3H, s)
7.67(1 H,d) 8.10(1H,d) 7.67 (1 H, d) 8.10 (1H, d)
NMR-10： 0.98(3H,d) 1.09(3H,d) 2.04(1 H,m) 2.37(3H,s) 3.20(3H，s) 3.00-3.40 NMR-10: 0.98 (3H, d) 1.09 (3H, d) 2.04 (1H, m) 2.37 (3H, s) 3.20 (3H, s) 3.00-3.40
(2H,m) 3.30(6H,s) 4.56(1 H,m) 7.77(1 H,d) 8.87(1 H,d) (2H, m) 3.30 (6H, s) 4.56 (1 H, m) 7.77 (1 H, d) 8.87 (1 H, d)
NMR-11 ： 1.06(3H,d) 1.38(3H,d) 2.41 (3H,s) 3.20(3H,bs) 3,28(6H，bs) 3.85(1 H,m) NMR-11: 1.06 (3H, d) 1.38 (3H, d) 2.41 (3H, s) 3.20 (3H, bs) 3,28 (6H, bs) 3.85 (1 H, m)
4.98(1 H,m) 7.63(1 H,d) 8.12(1H,d) 4.98 (1 H, m) 7.63 (1 H, d) 8.12 (1H, d)
〔除草剤〕 (Herbicide)
次に、 本発明除草剤に関する製剤例を若干示すが、 本発明においては、 有効成分化 合物、 添加物及び添加割合は本実施例にのみ限定されることなく、 広い範囲で変更 可能である。 製剤実施例中の部は重量部を示す。  Next, some formulation examples of the herbicide of the present invention are shown. In the present invention, the active ingredient compound, the additive, and the ratio of addition are not limited to the present example and can be changed in a wide range. . Parts in Formulation Examples are parts by weight.
(実施例' 9) 水和剤 本発明化合物 20部 (Example '9) wettable powder Compound of the present invention 20 parts
ホワイ トカ一ボン 20部  White Toka Bon 20 parts
ゲイソゥ土 52部  Geiseo soil 52 parts
アルキル硫酸ソーダ 8部  Sodium alkyl sulfate 8 parts
以上を均一に混合、 微細に粉砕して、 有効成分 20%の水和剤を得る。  The above ingredients are uniformly mixed and finely pulverized to obtain a wettable powder containing 20% of the active ingredient.
(実施例 10 ) 乳剤  (Example 10) Emulsion
本発明化合物 20部  Compound of the present invention 20 parts
キシレン 55部  Xylene 55 parts
ジメチルホルムァミ ド 15部  Dimethylformamide 15 parts
ポリオキシエチレンフヱニルエーテル 10部  Polyoxyethylene phenyl ether 10 parts
以上を混合、 溶解して有効成分 20%の乳剤を得る。  The above are mixed and dissolved to obtain an emulsion containing 20% of the active ingredient.
(実施例 1 1) 粒剤  (Example 11) Granules
本発明化合物 5部  5 parts of the compound of the present invention
タルク 40部  Talc 40 parts
クレー 38部  Clay 38 parts
ベントナイ ト 10部  Bentonite 10 parts
アルキル硫酸ソーダ 7部  Sodium alkyl sulfate 7 parts
以上を均一に混合して微細に粉砕後、 直径 0. 5 1. 0mmの粒状に造粒して有 効成分 5%の粒剤を得る。 産業上の利用可能性：  The above components are uniformly mixed and finely pulverized, and then granulated into particles having a diameter of 0.51.0 mm to obtain granules having an active ingredient of 5%. Industrial applicability:
次に本発明除草剤の効果に関する試験例を示す。  Next, test examples regarding the effect of the herbicide of the present invention will be described.
除草効果は下記の調査基準に従って調査し、 殺草指数で表した。  The herbicidal effect was investigated according to the following criteria and expressed as a herbicidal index.
調査基準  Survey criteria
殺 草 率 殺 草 指 数  Killing rate killing index
0 % 0  0% 0
20〜29% 2 40〜49% 4 20-29% 2 40-49% 4
60〜69% 6  60-69% 6
80〜89% 8  80-89% 8
100% 10  100% 10
また、 1、 3、 5、 7、 9の数値は、 各々 0と 2、 2と 4、 4と 6、 6と 8、 8と 10の中間の値を示す。  The values of 1, 3, 5, 7, and 9 are intermediate values between 0 and 2, 2 and 4, 4 and 6, 6 and 8, and 8 and 10, respectively.
(無処理区の地上部生草重一処理区の地上部生草重）  (Earth grass weight in untreated area)
殺草率 ） = X 100  Weed kill rate) = X 100
無処理区の地上部生草重  Aboveground raw grass weight in untreated area
(試験例 1 ) 畑作茎葉散布処理  (Test Example 1) Upland foliage spraying treatment
200 cm2のポッ トに土壌を充填し、 表層にメヒシバ、 アキノエノコログサ、 ィヌ ビュ、 ィチビ及びトウモロコシの各種子を播き、 軽く覆土後温室内で生育させた。 各雑草が 5〜10 cmの草丈に生育した時点で各供試化合物の実施例 8に示した乳 剤の水希釈液を、 有効成分が所定の薬量になるように、 50リツ トル /10 a散布 量相当量で小型噴霧器にて雑草の茎葉部に散布した。 3週間後に作物の薬害及び雑 草の除草効果を前記調査基準に従って調査し、 その結果を第 3表に示した。 A 200 cm 2 pot was filled with soil, and seedlings of Meechishiba, Achinonokorogosa, Inubu, Ichibi and Maize were sown on the surface layer, lightly covered with soil, and grown in a greenhouse. When each weed has grown to a plant height of 5 to 10 cm, the aqueous dilution of the emulsion shown in Example 8 for each test compound is added to 50 liters / 10 liters so that the active ingredient has a predetermined dose. a Sprayed to the foliage of weeds with a small sprayer in an amount equivalent to the spray amount. Three weeks later, the herbicidal effects of crops and the weeds of the weeds were investigated in accordance with the above-mentioned criteria, and the results are shown in Table 3.
ο衣 ο clothing
畑作茎葉処理  Upland field foliage treatment
化合物 薬量 (g/ha) ィチビ ィヌビュ アキノエノコ口 メヒシハ' トウモロコシ Compounds Dosage (g / ha)
No. 5 250 10 10 10 10 0 No. 5 250 10 10 10 10 0
No.10 250 10 8 10 10 0  No.10 250 10 8 10 10 0
No.11 250 9 8 10 8 0  No.11 250 9 8 10 8 0
No.14 250 9 10 10 10 0  No. 14 250 9 10 10 10 0
No.16 250 8 10 8 8 0  No. 16 250 8 10 8 8 0
No.19 250 9 10 10 10 0  No. 19 250 9 10 10 10 0
No.22 250 10 10 10 10 0  No. 22 250 10 10 10 10 0
No.48 250 9 10 10 10 0  No.48 250 9 10 10 10 0
No.66 250 10 10 10 10 2  No.66 250 10 10 10 10 2
No.68 250 10 10 10 10 0 No.79 250 10 9 10 10 0 No. 68 250 10 10 10 10 0 No. 79 250 10 9 10 10 0
(試験例 2) 畑作土壌処理 (Test Example 2) Upland soil treatment
表面積が 200 cm2のプラスチックポッ トに畑土壌を充填し、 メヒシバ、 アキノエ ノコログサ、 イチピ、 ィヌビュ及びトウモロコシの種子を播種し、 その上に 0. 5 cmの覆土をした。 翌日実施例 8に示した乳剤の希釈液を、 その有効成分が 10 a 当り、 200 gとなるように覆土上に均一に散布し、 処理後 20日後に作物の薬害 及び雑草の除草効果を、 前記調査基準に従って調査し、 その結果を第 4表に示した。 第 4表 Field soil was filled into a plastic pot with a surface area of 200 cm 2 , and seeds of Meechishiba, Aquino nokorogosa, Ichipi, Inuvu and corn were sown, and 0.5 cm of soil was covered on it. The next day, the diluted solution of the emulsion shown in Example 8 was evenly spread on the cover soil so that the active ingredient was 200 g per 10 a, and after 20 days from the treatment, the phytotoxicity of the crop and the herbicidal effect of weeds were evaluated. The survey was conducted according to the above-mentioned survey criteria, and the results are shown in Table 4. Table 4
畑作土壌処理  Upland soil treatment
薬量 (g/ha) ィチビ ィヌビュ アキノエノコ口 メヒシハ トウモロコシ Dosage (g / ha) Ichibi Inubu Akinoenoko Mezishiha Maize
No. 5 250 10 10 10 10 0 No. 5 250 10 10 10 10 0
No.10 250 10 10 10 10 0  No. 10 250 10 10 10 10 0
No.11 250 10 10 10 10 0  No.11 250 10 10 10 10 0
No.16 250 10 10 10 9 0  No. 16 250 10 10 10 9 0
No.21 250 10 10 10 10 0  No. 21 250 10 10 10 10 0
No.22 250 10 10 10 10 0  No. 22 250 10 10 10 10 0
No.28 250 10 10 10 10 0  No. 28 250 10 10 10 10 0
No.33 250 10 10 10 10 0  No.33 250 10 10 10 10 0
No.46 250 10 10 10 10  No. 46 250 10 10 10 10
No.48 250 10 10 10 10 0  No. 48 250 10 10 10 10 0
No.51 250 10 10 . 10 10 0  No.51 250 10 10 .10 10 0
No.52 250 10 10 10 10  No. 52 250 10 10 10 10
No.53 250 10 10 10 10 0  No.53 250 10 10 10 10 0
No.61 250 10 10 10 10  No.61 250 10 10 10 10
No.65 250 10 10 10 10  No. 65 250 10 10 10 10
No.66 250 10 10 10 10  No. 66 250 10 10 10 10
No.76 250 10 10 10 10  No. 76 250 10 10 10 10
No.77 250 10 10 10 10  No. 77 250 10 10 10 10
No.78 250 10 10 10 10  No.78 250 10 10 10 10
No.79 250 10 10 10 10  No. 79 250 10 10 10 10
No.80 250 10 10 10 10 ζ ΖNo. 80 250 10 10 10 10 ζ Ζ
Ο ο ρΟ ο ρ
00 00 0000 00 00
CO ND ro ) Ν5 ι J1 ο ο Ο CO ND ro) Ν5 ι J1 ο ο Ο
ο ο ο ο ο ο
ο ο ο ο ο ο
ο ο 。 ο ο.
ο ο ο ο ο ο

Claims

請 求 の 範 囲 The scope of the claims
式 （1)  Equation (1)
Figure imgf000049_0001
Figure imgf000049_0001
[式中、 Ri, R2は、 それぞれ独立して、 水素原子、 ニトロ基、 シァノ基、 ハロゲン 原子、 C1-6アルキル基、 じ 6アルコキシ基、 Ci-6ハロアルキル基、 C1-6ハロアルコキ シ基、 アルキルチオ基、 CMアルキルスルフヱニル基又は アルキルスルホ二 ル基を表す。 [Wherein Ri and R 2 each independently represent a hydrogen atom, a nitro group, a cyano group, a halogen atom, a C 1-6 alkyl group, a 6 alkoxy group, a Ci- 6 haloalkyl group, a C 1-6 haloalkoxy group. Represents a silyl group, an alkylthio group, a CM alkylsulfonyl group or an alkylsulfonyl group.
R3は、 ニトロ基、 シァノ基、 ハロゲン原子、 Ci-sアルキル基、 C1-6アルコキシ基、 ハロアルキル基、 C1-6ハロアルコキシ基、 Ci-6アルキルチオ基、 アルキルス ルフヱニル基又は アルキルスルホ二ル基を表す。 nは、 0、 1又は 2を表す。 R 3 is a nitro group, a cyano group, a halogen atom, a Ci-s alkyl group, a C 1-6 alkoxy group, a haloalkyl group, a C 1-6 haloalkoxy group, a Ci- 6 alkylthio group, an alkyl sulfonyl group or an alkyl sulfonyl group. Represents a hydroxyl group. n represents 0, 1 or 2.
R4, R5は、 それぞれ独立して、 水素原子、 CMアルキル基、 C2—6アルケニル基、 CMアルコキシ基、 C1-6ハロアルキル基、 C1-6ヒドロキシアルキル基、 ハロアル コキシ基、 C3_8シクロアルキル基、 Ci— 6アルコキシ C1-6アルキル基、 C1-6ハロアルコ キシ アルキル基、 C— 6アルコキシ C1-6アルコキシ基、 Ci-6ハロアルコキシ ァ ルコキシ基、 アルキルチオ C1-sアルキル基、 C1-6アルキルチオ C1-6アルコキシ基、 アミノ基、 アルキルアミノ基、 ジじ^アルキルアミノ基、 アルキルカルボ二 ル基、 アルコキシカルボニル基、 C1-6ハロアルキルカルボニル基、 ハロアル コキシカルボニル基、 アルキルスルホニル基、 CMハロアルキルスルホ二ル基又 は、 （ハロゲン原子、 アルキル基、 C1-6アルコキシ基又は Ci— 6ハロアルキル基で） 置換されていてもよいフヱニル基を表す。 また、 R4と R5は、 一緒になつて炭素数 2 一 5のアルキレン鎖、 又は R4と R5は結合している窒素原子とともに、 （： 6アルキル 基で置換されていてもよい酸素原子又は窒素原子を 2— 4個含む 5員若しくは 6員 の含窒素複素環を形成してもよい。 R 4, R 5 are each independently a hydrogen atom, CM alkyl groups, C 2 - 6 alkenyl, CM alkoxy, C 1-6 haloalkyl groups, C 1-6 hydroxyalkyl groups, Haroaru Kokishi groups, C 3 _ 8 cycloalkyl group, CI- 6 alkoxy C 1-6 alkyl group, C 1-6 Haroaruko alkoxyalkyl group, C-6 alkoxy C 1-6 alkoxy group, CI- 6 haloalkoxy § alkoxy group, an alkylthio C 1 -s alkyl group, C 1-6 alkylthio C 1-6 alkoxy group, an amino group, an alkylamino group, current events ^ alkylamino group, alkylcarbonyl two group, an alkoxycarbonyl group, C 1-6 haloalkylcarbonyl group, Haroaru Job aryloxycarbonyl group, an alkylsulfonyl group, also CM haloalkylsulfonyl groups, optionally substituted (halogen atom, an alkyl group, with a C 1-6 alkoxy group or CI- 6 haloalkyl group) Represents a phenyl group which may be substituted. R 4 and R 5 are joined together to form an alkylene chain having 215 carbon atoms, or R 4 and R 5 together with the nitrogen atom to which they are bonded together (: 6 oxygen which may be substituted by an alkyl group) It may form a 5- or 6-membered nitrogen-containing heterocyclic ring containing 2 to 4 atoms or nitrogen atoms.
Xは、 酸素原子、 硫黄原子を表す。  X represents an oxygen atom or a sulfur atom.
Zは、 ホルミル基、 ジ アルコキシメチル基、 C2_6アルケニル基、 C 2-6アルキニ ル基、 アルコキシィミノメチル基、 c1-6ハロアルコキシィミノメチル基、 c2— 6ァ ルケ二ルイミノメチル基、 C2-6ハロアルケ二ルイミノメチル基、 （ハロゲン原子、 アルキル基、 C -sアルコキシ基、 C1-6ハロアルキル基、 シァノ基、 ニトロ基で） 置換されていてもよいフヱニル基、 又は （ハロゲン原子、 C1-6アルキル基、 Ci— 6アル コキシ基又は ハロアルキル基で） 置換されていてもよい酸素原子、 窒素原子も しく くは硫黄原子を 1〜4個含む 5員〜 6員の複素環基を表す。 ] で表される化合 物又はその塩。 Z is a formyl group, di-alkoxymethyl group, C 2 _ 6 alkenyl, C 2 - 6 Arukini Group, alkoxides Consequences amino methyl, c 1-6 halo alkoxides Consequences amino methyl, c 2 - 6 § Luque two Ruiminomechiru groups, C 2 - 6 Haroaruke two Ruiminomechiru group, (halogen atom, alkyl group, C -s alkoxy Group, C 1-6 haloalkyl group, cyano group, nitro group) optionally substituted phenyl group, or (substituted with halogen atom, C 1-6 alkyl group, Ci- 6 alkoxy group or haloalkyl group) Represents a 5- to 6-membered heterocyclic group containing 1 to 4 oxygen atoms, nitrogen atoms or sulfur atoms which may be substituted. ] The compound represented by these, or its salt.
2. 前記 Zにおける置換されていてもよい複素環基が、 2. The optionally substituted heterocyclic group for Z is
Figure imgf000050_0001
Figure imgf000050_0001
Figure imgf000050_0002
Figure imgf000050_0002
(式中、 R6及び R7は、 それぞれ独立して、 水素原子、 ハロゲン原子、 CMアルキル 基、 6ハロアルキル基又は C1-6アルコキシ基を表す。 ） で表される群から選ばれた 一種の基である、 請求の範囲 1記載の式 （1) で表される化合物又はその塩。 (Wherein, R 6 and R 7 each independently represent a hydrogen atom, a halogen atom, a CM alkyl group, a 6 haloalkyl group, or a C 1-6 alkoxy group.) The compound represented by the formula (1) according to claim 1, which is a group of the following, or a salt thereof.
3. 前記式 （1) で表わされる化合物又はその塩の 1種若しくは 2種以上を有効成 分として含有する除草剤。 3. A herbicide containing one or more of the compound represented by the formula (1) or a salt thereof as an active ingredient.
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EP3382027A2 (en) 2011-09-13 2018-10-03 Monsanto Technology LLC Methods and compositions for weed control
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JP2007507444A (en) * 2003-09-29 2007-03-29 イサグロ リチェルカ ソシエタ ア レスポンサビリタ リミタータ Derivatives of 1,3-dione having herbicidal activity
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EP3296402A2 (en) 2011-09-13 2018-03-21 Monsanto Technology LLC Methods and compositions for weed control
WO2013040117A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control
WO2013040021A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and compositions for weed control
EP3382027A2 (en) 2011-09-13 2018-10-03 Monsanto Technology LLC Methods and compositions for weed control
EP3434779A1 (en) 2011-09-13 2019-01-30 Monsanto Technology LLC Methods and compositions for weed control
EP3434780A1 (en) 2011-09-13 2019-01-30 Monsanto Technology LLC Methods and compositions for weed control
WO2014151255A1 (en) 2013-03-15 2014-09-25 Monsanto Technology Llc Methods and compositions for weed control
CN104817511A (en) * 2015-04-27 2015-08-05 济南大学 Method for using maleic anhydride to prepare favipiravir key intermediate
CN107652217A (en) * 2017-10-24 2018-02-02 青岛清原化合物有限公司 Substituted benzoyl diketone nitrile compounds or its dynamic isomer, salt, preparation method, Herbicidal combinations and application

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