WO1998043949A1 - Composes d'ether d'oxime, leur utilisation et intermediaires pour leur preparation - Google Patents

Composes d'ether d'oxime, leur utilisation et intermediaires pour leur preparation Download PDF

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Publication number
WO1998043949A1
WO1998043949A1 PCT/JP1998/001408 JP9801408W WO9843949A1 WO 1998043949 A1 WO1998043949 A1 WO 1998043949A1 JP 9801408 W JP9801408 W JP 9801408W WO 9843949 A1 WO9843949 A1 WO 9843949A1
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group
alkyl
methyl
mmol
compound according
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PCT/JP1998/001408
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English (en)
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Taro Hirose
Norio Kimura
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Sumitomo Chemical Company, Limited
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Priority to AU65193/98A priority Critical patent/AU6519398A/en
Priority to EP98911069A priority patent/EP0975587A1/fr
Priority to BR9809746-6A priority patent/BR9809746A/pt
Publication of WO1998043949A1 publication Critical patent/WO1998043949A1/fr

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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
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    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/48—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a six-membered aromatic ring
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    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
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    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
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    • C07C255/00—Carboxylic acid nitriles
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    • C07C255/64—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to oxygen atoms
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    • C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
    • C07C259/06—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to hydrogen atoms or to acyclic carbon atoms
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    • C07C259/12—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. N-hydroxyamidines
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    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/63—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
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    • C07C327/00—Thiocarboxylic acids
    • C07C327/58—Derivatives of thiocarboxylic acids, the doubly-bound oxygen atoms being replaced by nitrogen atoms, e.g. imino-thio ethers
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    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C07C69/736—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D307/12—Radicals substituted by oxygen atoms

Definitions

  • the present invention relates to oxime ether compounds, their use and intermediates for preparation of the same . More particularly, the present invention provides compounds having excellent antifungal effects for agriculture and/or horticulture, and excellent insecticidal and/or acaricidal effects .
  • present invention provides oxime ether compounds (hereinafter referred to as present compound) represented by the general formula 4 :
  • R 1 represents hydrogen atom, alkyl group, cycloalkyl group, alkoxyalkyl group, haloalkyl group, cyano group, nitro group or alkoxycarbonyl group
  • one of T, U and V represents CR 2 group, the other one represents CH group or nitrogen atom and the rest one represents CR 3 group or nitrogen atom
  • W represents CR 33 group or nitrogen atom
  • R 2 , R 3 and R 33 are the same or different and represent hydrogen atom, halogen atom, alkyl group, alkoxy group, haloalkyl group, haloalkoxy group, cyano group, nitro group, alkoxycarbonyl group, alkylthio group or haloalkylthio group
  • R 4 represents hydrogen atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group or heterocyclic group, wherein the alkyl group, the alkenyl group, the alkynyl group, the cycloalkyl group, the cycloalkenyl group, the aryl group or the heterocyclic group may have one or more substituents,
  • X represents NR 7 group, oxygen atom or sulfur atom
  • R 7 represents alkyl group optionally having one or more substituents
  • Y represents CH group or nitrogen group
  • Z represents oxygen atom or NH group, provided that when
  • Y is CH group, then Z is oxygen atom, as well as antifungal agents for agriculture and/or horticulture, and insecticidal and/or acaricidal agents containing the same as an active ingredient.
  • the present invention further provides compounds represented by the general formula 5 : [compound 5]
  • R 1 , R 4 , R 6 , T, U, V, W and X are as defined above, compounds represented by the general formula 7 :
  • R 1 , R 5 , R 6 , T, U, V, W, X and Z are as defined above, and compounds represented by the general formula 8 :
  • examples of the alkyl group representedby R 1 include C1-C10 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, decyl group and the like.
  • examples of the cycloalkyl group represented by R 1 include C3-C10 cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclodecyl group and the like.
  • alkoxyalkyl group represented by R 1 examples include C2-C10 alkoxyalkyl group such as methoxymethyl group, 2-ethoxyethyl group, 4-methoxybutyl group, 5-pentyloxypentyl group and the like.
  • Examples of the haloalkyl group represented by R 1 include C1-C5 haloalkyl group such as trifluoromethyl group, chloromethyl group, 2-fluoroethyl group and the like.
  • Examples of the alkoxycarbonyl group represented by R 1 include C2-C5 alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n- butoxycarbony1 group, i-propoxycarbonyl group, i- butoxycarbonyl group, t-butoxycarbonyl group and the like.
  • Examples of the halogen atom represented by R 2 , R 3 or R 33 include chlorine atom, bromine atom, fluorine atom and the like.
  • Examples of the alkoxy group represented by R 2 , R 3 or R 33 include C1-C5 alkoxy group such as methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, pentyloxy group and the like.
  • Examples of the haloalkyl group represented by R 2 , R 3 or R 33 include C1-C5 haloalkyl group such as trifluoromethyl group and the like.
  • haloalkoxy group represented by R 2 , R 3 or R 33 examples include C1-C5 haloalkoxy group such as trifluoromethoxy group, difluoromethoxy group, bromodifluoromethoxy group, chlorodifluoromethoxy group, 1, 1, 2 , 2 , -tetrafluoroethoxy group, 2, 2, 2-trifluoroethoxy group and the like.
  • alkoxycarbonyl group represented by R 2 , R 3 or R 33 examples include C2-C5 alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, n- propoxycarbonyl group, n-butoxycarbonyl group, i- propoxycarbonyl group, i-butoxycarbonyl group, t- butoxycarbonyl group and the like.
  • alkylthio group represented by R 2 , R 3 or R 33 examples include C1-C5 alkylthio group such as methylthio group, ethylthio group, n-propylthio group, n-butylthio group, n- pentylthio group, i-propylthio group, i-butylthio group, t- butylthio group and the like.
  • Examples of the alkyl group represented by R 4 include C1-C10 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 1- methylpropyl group, pentyl group, 1-methylbutyl group, 1- ethylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 2 , 2-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1- dimethylpropyl group, hexyl group, 1-methylpentyl group, 1- ethylpentyl group, 3 , 3-dimethylbutyl group, heptyl group, 3 , 7-dimethyloctyl group and the like.
  • C1-C10 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 1- methylpropyl
  • alkenyl group represented by R 4 examples include
  • C3-C10 alkenyl group such as allyl group, l-methyl-2-propenyl group, 2-methyl-2-propenyl group, 3-methyl-2-propenyl group,
  • alkynyl group represented by R 4 examples include C3-C10 alkynyl group such as propargyl group, 1-methyl-2- propynyl, 3-methyl-2-propynyl group and the like.
  • Examples of the cycloalkyl group representedby R 4 include C5-C10 cycloalkyl group such as cyclopentyl group, cyclohexyl group and the like.
  • Examples of the cycloalkenyl group represented by R 4 include C5-C10 cycloalkenyl group such as cyclopentenyl group, cyclohexenyl group and the like.
  • Examples of the aryl group represented by R 4 include phenyl group, a -naphthyl group, ⁇ -naphthyl group and the like.
  • Examples of the heterocyclic group represented by R 4 include 2-pyridyl group, 4-pyridyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 3-pyrazolyl group, 2-thiazolyl group, 2-imidazolyl group, 3- (1, 2 , 4-triazolyl group) and the like.
  • Examples of the substituent ofthe alkyl group, the alkenyl group, the alkynyl group, the cycloalkyl group, the cycloalkenyl group, the aryl group and the heterocyclic group as R 4 include :
  • halogen atom chlorine atom, bromine atom, fluorine atom and the like
  • R 8 represents hydrogen atom, C1-C10 alkyl group [such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group and the like] , C1-C5 haloalkyl group
  • C3-C6 cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group an the like]
  • C2-C10 alkoxyalkyl group such as 2- methoxyethyl group and the like
  • C1-C10 acyl group such as formyl group, acetyl group, propanoyl group, pivaloyl group, C1-C10 alkanoyl group optionally substituted with halogen atom (chlorine atom, bromine atom, fluorine atom and the like) such as chloroacetyl group and the like, benzoyl group and the like]
  • C2-C11 alkoxycarbonyl group such as trifluoromethyl group, difluoromethyl group, bromodifluoromethyl group, 1, 1, 2, 2 , -tetrafluoroethyl group, 2, 2, 2 -trifluoroethyl group and the like
  • phenyl, a -naphthyl or ⁇ -naphthyl) sulfonyl group [such as p-toluenesulfonyl group and the like] , C1-C5 haloalkylsulfonyl group and the like [such as trifluoromethanesulfonyl group, trichloromethanesulfonyl group, 2,2,2, -trifluoroethanesulfonyl group and the like], C1-C5 alkylsulfinyl group [such as methylsulfinyl group and the like] or C1-C5 haloalkylsulfinyl group [such as trifluoromethanesulfinyl group and the like] , or phenyl group [the phenyl group may be substituted with halogen atom (ex.
  • R 9 and R 10 are taken together to represent tetramethylene group, pentamethylene group or 3- oxapentamethylene group ⁇ ;
  • R 13 and R 14 are the same or different and represent hydrogen atom, C1-C10 alkyl group [such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group and the like] , C3-C6 cycloalkyl group
  • phenyl group [such as cyclopropyl group, cyclopentyl group and cyclohexyl group] , or phenyl group [the phenyl group may be substituted with halogen atom (ex. chlorine atom, bromine atom, fluorine atom and the like) , C1-C5 alkyl group (such as methyl group, ethyl group, tert-butyl group and the like) , trifluoromethyl group, cyano group or nitro group; such as 4-chlorophenyl group, 4-trifluoromethylphenyl group, 4-ethylphenyl group, 3,4- dichlorophenyl group, 3 , 5-dichlorophenyl group, 2-chloro-6- fluorophenyl group, 4-fluorophenyl group, 4-cyanophenyl group, 4-nitrophenyl group and the like] ⁇ :
  • C1-C5 alkylthio group [such as methylthio group, ethylthio group, propylthio group, isopropylthio group, pentylthio group and the like] ;
  • C1-C5 haloalkylthio group [such as 2,2,2- trifluoroethylthio group, 4-chlorobutylthio group and the like] ;
  • C1-C10 acyl group [such as C1-C10 alkanoyl group (ex. formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, isobutanoyl group and the like) optionally substituted with halogen atom (ex.
  • C2-C11 alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group and the like;
  • N-(C1-C10 alkyl) carbamoyl group [such as N- methylcarbamoyl group, N-ethylcarbamoyl group and the like] ;
  • N,N-di(Cl-C10 alkyl ) carbamoyl group [such as N,N-dimethylcarbamoyl group, N,N-diethylcarbamoyl group and the like] ;
  • aryl group such as phenyl group, a -naphthyl group, ⁇ -naphthyl group and the like ; the aryl group may be substituted with halogen atom [such as chlorine atom, bromine atom, fluorine atom and the like] , C1-C10 alkyl group [such as methyl group, ethyl group, tert-butyl group and the like] , C3-C10 cycloalkyl group [such as cyclopropyl group, cyclopentyl group, cyclohexyl group and the like] , C1-C5 haloalkyl group [such as trifluoromethyl group and the like] , hydroxy group, C1-C10 alkoxy group [such as methoxy group, ethoxy group, propyloxy group, isopropyloxy group and the like] , C1-C5 haloalkoxy group [such as trifluoro
  • heterocyclic group such as 2-pyridyl group, 3- pyridyl group, 4-pyridyl group, 2-pyrimidinyl group, 4- pyrimidinyl group, 5-pyrimidinyl group, 1-pyrazolyl group, 3-pyrazolyl group, 4-pyrazolyl group, 5-pyrazolyl group, 2- thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 4- isoxazolyl group, 1- (1, 2, 4-triazolyl) group, 3-(l,2,4- triazolyl) group, 3-oxolanyl, succinimid-1-yl group, maleinimid-1-yl group, phthalimid-1-yl group and the like; the heterocyclic group may be substituted with one or more halogen atom [ex.
  • C1-C10 alkyl group such as methyl group, ethyl group, tert-butyl group and the like]
  • C3-C10 cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group and the like]
  • C1-C5 haloalkyl group such as trifluoromethyl group and the like]
  • hydroxy group, C1-C10 alkoxy group such as methoxy group, ethoxy group and the like]
  • amino group or C1-C10 alkylthio group such as methylthio group, ethylthio group and the like] ⁇ .
  • Examples of the alkyl group represented by R 5 or R 6 include C1-C5 alkyl group such as methyl group, ethyl group, propyl group and the like. Inter alia, methyl group is preferable from a viewpoint of antifungal effect for agriculture and horticulture.
  • Examples of the alkyl group represented by R 7 include C1-C5 alkyl group such as methyl group, ethyl group, propyl group and the like.
  • Examples of the substituent of R7 are halogen atom [such as chlorine atom, bromine atom, fluorine atom and the like] , C1-C5 alkoxy group [such as methoxy group, ethoxy group and the like] , C2-C5 alkoxycarbonyl group [such as methoxycarbonyl group, ethoxycarbonyl group and the like] , N-(C1-C5 alkyl) carbamoyl group [such as N-methylcarbamoyl group, N-ethylcarbamoyl group and the like], N,N-di(Cl-C5 alkyl) carbamoyl group [such as N,N-dimethylcarbamoyl group) , N,N-diethylcarbamoyl group and the like] , cyano group and the like.
  • halogen atom such as chlorine atom, bromine atom, fluorine atom and the like
  • 6-membered cyclic aromatic ring containing T, U, V and W examples include benzene ring, pyridine ring, pyrimidine ring and the like.
  • the present compounds wherein RI is methyl group, T is C-CH 3 , U is CH, V is CH, W is CH, R5 is methyl group, R6 is methyl group, X is oxygen atom, Y is CH and Z is oxygen atom are preferred.
  • Examples of the preferred compound include methyl 2- ⁇ 5- (1-benzyloxyiminoethyl) -2- methylphenoxy ⁇ -3-methoxyacrylate, methyl 3- [5- ⁇ l- (2 , 4- dichlorobenzyloxyimino) ethyl ⁇ -2-methylphenoxy] -3- methoxyacrylate, methyl 2- ⁇ 5- (1-propargyloxyiminoethyl) -2- methylphenoxy ⁇ -3-methoxyacrylate, methyl 2- ⁇ 5-(l-n- propyloxyiminoethyl) -2-methylphenoxy ⁇ -3-methoxyacrylate, and the like.
  • R 44 represents R 4 except for hydrogen, R 1 , R 5 , R 6 , T, U, V, W, X, Y and Z are as defined above, and L 1 represents a leaving group such as halogen atom (such as chlorine atom, bromine atom, iodine atom and the like) , sulfonate ester group (such as mesyloxy group, tosyloxy group and the like) , sulfate ester group (methoxysulfonyloxy group, ethoxysulfonyloxy group and the like) .
  • halogen atom such as chlorine atom, bromine atom, iodine atom and the like
  • sulfonate ester group such as mesyloxy group, tosyloxy group and the like
  • sulfate ester group methoxysulfonyloxy group, ethoxysulfonyloxy group and the like
  • R 1 , R 4 , R 5 , R 6 , T, U, V, , X, Y and L 1 are as defined above
  • L 2 is alkoxy group (ex. C1-C5 alkoxy group such as methoxy group, ethoxy group and the like) , aryloxy group (phenoxy group and the like) or acyloxy group (ex. C1-C5 acyloxy group such as acetoxy group and the like) when Y is CH group
  • L 2 is alkoxy group (ex. C1-C5 alkoxy group such as methoxy, group, ethoxy group, isoamyloxy group, butoxy group, tert- butoxy group and the like) or chlorine atom when Y is nitrogen.
  • R 1 , R 5 , R 6 , T, U, V, W, X, Y, L 1 and L 2 are as defined above, and R 11 represents alkyl group (ex. C1-C5 alkyl group such as methyl group, ethyl group, propyl group, butyl group and the like) or two R 11 ' s are taken together to represent alkylene group (ex. C2-C5 alkylene group such as ethylene group, 1, 2-dimethylethylene group, propylene group and the like).
  • a raw material compound 6 in the above Scheme 8 and a raw material compound [X] in the above Scheme 11 can be prepared, for example, according to the following Scheme 12
  • Process 12c L 11 — CH 2 C0 2 R 6
  • Process 12 b L 11 — CH 2 C0 2 R 6
  • L 1 represents halogen atom (such as chlorine atom, bromine atom, iodine atom and the like) or sulfonate ester group (such as mesyloxy group, tosyloxy group and the like) .
  • R 11 represents cyano group, alkoxycarbonyl group or nitro group
  • R 44 , L 1 , L 2 , X, T, U, V and W are as defined above
  • X' represents a group which can be synthetic-chemically derived into X-H group in process 13c
  • when X represents oxygen atom then X' represents an oxygen ether group such as benzyloxy group, methoxymethyloxy group, methylthiomethyloxy group, benzyloxymethyloxy group, tetrahydropyran-2-yloxy group and the like
  • when X represents sulfur atom then X' represents sulfur ether group such as methoxymethylthio group, isobutoxymethylthio group, tetrahydropyran-2-ylmethylthio group and the like
  • X' represents nitro group or N(R 7 )R 20 group (wherein R 7 is as defined above and R 20 represents acyl
  • a reaction temperature is usually in a range of 0 to 150 2 C
  • a reaction time is usually in a range of 1 to 24 hours
  • a molar ratio of the hydroxylamine derivative relative to the carbonyl compound is usually in a range of 1 to 5.
  • Hydroxylamine derivative may be used as a salt with an acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like.
  • an acid catalyst or base catalyst may be used in the reaction.
  • a molar ratio of the catalyst relative to the hydroxylamine derivative is usually in a range of 0.01 to 100.
  • the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, polyphosphoric acid and the like, carboxylic acids such as acetic acid, trifluoroacetic acid, oxalic acid, benzoic acid and the like, sulfonic acids such as p-toluenesulfonic acid, camphorsulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like, Lewis acids such as zinc chloride, boron trifluoride diethyl ether complex, trimethylsilyl chloride and the like and a mixture thereof .
  • the acid catalyst may form a salt with alkali metals such as sodium, potassium and the like, organic bases such as pyridine, triethylamine, N,N-dimethylaniline and the like. Examples thereof are pyridinium p-toluenesulfonate and the like.
  • the base catalyst examples include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, potassium carbonate and the like, alkali metal alkoxides such as sodium methoxide, sodium ethoxide and the like, alkaline earth metal alkoxides such as magnesium ethoxide and the like, organic bases such as pyridine, 2- picoline, 4-picoline, 4-dimethylaminopyridine, quinoline, triethylamine, ethyldiisopropylamine, N,N-dimethylaniline, N, -diethylaniline and the like and a mixture thereof .
  • inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, potassium carbonate and the like
  • alkali metal alkoxides such as sodium methoxide, sodium e
  • the base catalyst may form a salt with mineral acids such as hydrochloric acid, sulfuric acid and the like, carboxylic acids such as acetic acid, benzoic acid and the like, Lewis acids such as zinc chloride and the like. Examples thereof include sodium acetate and the like. If necessary, a solvent may be used in the reaction.
  • mineral acids such as hydrochloric acid, sulfuric acid and the like, carboxylic acids such as acetic acid, benzoic acid and the like, Lewis acids such as zinc chloride and the like. Examples thereof include sodium acetate and the like.
  • a solvent may be used in the reaction.
  • the solvent examples include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether and the like, aromatic hydrocarbon solvents such as toluene, xylene and the like, halogenated hydrocarbon solvents such as chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene and the like, organic base solvents such as pyridine, triethylamine, N-methylaniline, N,N- dimethylaniline, N,N-diethylaniline and the like, organic acid solvents such as acetic acid and the like, ester solvent
  • reaction solution can be subjected to conventional post-treatment such as extraction with organic solvents, concentration and the like and, if necessary, further purified by recrystallization, distillation, chromatography or the like to isolate the desired compound.
  • a reaction temperature is in a range of 0 to 150 a C
  • a reaction time is usually in a range of 1 to 24 hours
  • the reaction is usually carried out in the presence of a base, and a molar ratio of the base relative to the electrophilic reagent is usually in a range of 1 to 10.
  • the base include inorganic salts such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, potassium carbonate, sodium hydride, potassium hydride, silver oxide and the like, alkali metal alkoxides such as potassium-tert-butoxide, sodium methoxide, sodium ethoxide, and the like, alkaline earth metal alkoxides such as magnesium ethoxide and the like, organic bases such as pyridine, 2- picoline, 4-picoline, 4-dimethylaminopyridine, quinoline, triethylamine, ethyldiisopropylamine, N,N-dimethylaniline, N, N-diethylaniline, and the line and a mixture thereof.
  • a solvent may be used in the reaction.
  • the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether and the like, aromatic hydrocarbon solvents such as toluene, xylene and the like, halogenated hydrocarbon solvents such as chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene and the like, organic base solvents such as pyridine, triethylamine, N-methylaniline, N,N- dimethylaniline, N, N-diethylaniline and the like, ester solvents
  • reaction solution can be subjected to conventional post-treatment such as extraction with organic solvents, concentration and the like and, if necessary, further purified by recrystallization, distillation, chromatography or the like to isolate the desired compound.
  • a reaction temperature is usually in a range of 0 to 150 a C
  • a reaction time is usually in a range of 1 to 24 hours.
  • a reaction reagent used for acetalizing carbonyl compound [X] is an alcohol compound represented by R 11 OH, which is usually used at two or more moles excessive amount relative to carbonyl compound [X] .
  • the alcohol compound may be used also as a reaction solvent.
  • reaction reagent used for acetalizing carbonyl compound [X] is an alkylenediol compound which is corresponding to an acetal moiety, which is usually used at one mole or more excessive amount relative to carbonyl compound [X] .
  • the reaction is usually carried out in the presence of an acid catalyst and a molar ratio of the acid catalyst relative to carbonyl compound [X] is usually in a range of 0.01 to 100.
  • the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, polyphosphoric acid and the like, carboxylic acids such as acetic acid, trifluoroacetic acid, oxalic acid, benzoic acid and the like, sulfonic acids such as p- toluenesulfonic acid, camphorsulfonic acid, methanesulfonic acid, trifluoromethane sulfonic acid and the like, Lewis acids such as zinc chloride, boron trifluoride diethyl ether complex, trimethylsilyl chloride and the like, and a mixture thereof.
  • the acid catalyst may form a salt with alkali metals such as sodium, potassium and the like, organic bases such as pyridine, triethylamine, N,N-dimethylaniline and the like. Examples thereof are pyridinium p-toluenesulfonate and the like.
  • Orthoesters as a reaction reagent can be further added to the reaction to accelerate the reaction and a molar ratio of the orthoesters to be used relative to carbonyl compound [X] is in a range of 1 to an amount useable as a solvent.
  • the orthoesters include methyl orthoformate, ethyl orthoformate and the like.
  • reaction solution can be subjected to conventional post-treatment such as extraction with organic solvents, concentration and the like and, if necessary, further purified by recrystallization, distillation, chromatography or the like to isolate the desired compound.
  • a reaction temperature is usually in a range of 0 to 150 a C
  • a reaction time is usually in a range of 1 to 24 hours
  • the reaction is usually carried out in the presence of a base.
  • a base examples include inorganic bases such as sodium hydride, potassium hydride and the like, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium-tert-butoxide and the like, alkaline earth metal alkoxides such as magnesium ethoxide and the like, and alkali metal amides such as sodium amide, lithium amide, lithium diisopropylamide, sodium hexamethyldisilazide, lithium hexamethyldisilazide and the like and a mixture thereof.
  • a solvent may be used in the reaction.
  • reaction solution can be treated with an aqueous acidic solution such as dilute hydrochloric acid, subjected to conventional post-treatment such as extraction with organic solvents, concentration and the like and, if necessary, further purified by recrystallization, chromatography or the like to isolate the desired compound.
  • aqueous acidic solution such as dilute hydrochloric acid
  • a reaction temperature is usually in a range of 0 to 150 2 C
  • a reaction time is usually in a range of 1 to 24 hours
  • a solvent may be used in the reaction.
  • the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether and the like, aromatic hydrocarbon solvents such as toluene, xylene and the like, halogenated hydrocarbon solvents such as dichloroethane, carbon tetrachloride, monochlorobenzene and the like, nitro compound solvents such as nitroethane, nitrobenzene and the like, nitrile solvents such as acetonitrile, isobutyronitrile and the like, N,N- dimethyl
  • reaction solution can be subjected to conventional post-treatment such as extraction with organic solvents, concentration and the like and, if necessary, further purified by recrystallization, chromatography or the like to isolate the desired compound.
  • a reaction temperature is usually in a range of 0 to 150 a C
  • a reaction time is usually in a range of 1 to 24 hours.
  • a molar ratio of 2-chloro-2- (hydroxyimino) acetate ester to be used for the reaction relative to compound [II] or [VII] is usually in a range of 1 to 10.
  • a method of preparing 2-chloro-2- (hydroxyimino) acetate ester is described, for example, in U.S. P. No. 3584032.
  • the reaction is usually carried out in the presence of a base and a molar ratio of the base relative to compound [II] or [VII] is usually in a range of 1 to 100.
  • the base include inorganic beses such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, calcium carbonate and the like, organic bases such as pyridine, 2-picoline, 4-picoline, 4- dimethylaminopyridine , quinoline, triethylamine, ethyldiisopropylamine, N,N-dimethylaniline, N,N- diethylaniline and the like, and a mixture thereof.
  • a solvent may be used in the reaction.
  • the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether and the like, aromatic hydrocarbon solvents such as toluene, xylene and the like, halogenated hydrocarbon solvents such as chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene and the like, organic base solvents such as pyridine, triethylamine, N-methylaniline, N,N- dimethylaniline, N,N-diethylaniline and the like, organic acid solvents, organic
  • reaction solution can be subjected to conventional post-treatment such as extraction with organic solvents, concentration and the like and, if necessary, further purified by recrystallization, chromatography or the like to isolate the desired compound.
  • Examples of the acid to be used in the reaction include carboxylic acids such as acetic acid, propionic acid, butyric acid, trifluoroacetic acid, pentafluoropropionic acid, benzoic acid and the like, sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid and the like, mineral acids such as sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, perchloric acid and the like, Lewis acids such as zinc chloride, aluminium chloride, boron trifluoride diethyl ether complex, trimethylsilyl chloride, trimethylsilyl iodide and the like, and a mixture thereof.
  • carboxylic acids such as acetic acid, propionic acid, butyric acid, trifluoroacetic acid, pentafluoropropionic acid, benzoic acid and the like
  • a solvent may be used in the reaction.
  • the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether and the like, aromatic hydrocarbon solvents such as toluene, xylene and the like, halogenated hydrocarbon solvents such as chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene and the like, ester solvents such as ethyl formate, butyl acetate, ethyl acetate, diethyl carbonate and the like, nitro compound solvents such as nitroe
  • reaction solution can be subjected to conventional post-treatment such as extraction with organic solvents, concentration and the like and, if necessary, further purified by recrystallization, chromatography or the like to isolate the desired compound.
  • process 13c comprises a process represented by the following Scheme 14:
  • R 11 , R 44 , R 7 , T, U, V, W and L 1 are as defined above, and R 21 represents hydrogen atom, alkyl group such as methyl group, or haloalkyl group such as chloromethyl group, trichloromethyl group and trifluoromethyl group.
  • Process 14a is a reducing reaction carried out using zinc , iron, tin or tin (II) chloride usually in the presence of an acid.
  • a reaction temperature is usually in a range of 0 to 150 a C, and a reaction time is usually in a range of 1 to 100 hours.
  • a molar ratio of the acid relative to compound [XVII] is usually in a range of 1 to an amount useable as a solvent.
  • Examples of the acid to be used in the reaction include carboxylic acids such as acetic acid, propionic acid, butyric acid, trifluoroacetic acid, pentafluoropropionic acid and the like, sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid and the like, mineral acids such as sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid and the like, and a mixture thereof .
  • carboxylic acids such as acetic acid, propionic acid, butyric acid, trifluoroacetic acid, pentafluoropropionic acid and the like
  • sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid and the like
  • mineral acids such as sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid and the like, and a mixture thereof .
  • a solvent may be used in the reaction.
  • the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether and the like, aromatic hydrocarbon solvents such as toluene, xylene and the like, organic acid solvents such as acetic acid and the like, ester solvents such as ethyl formate, butyl acetate, ethyl acetate, diethyl carbonate and the like, and a mixture thereof.
  • alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like
  • reaction solution can be subjected to conventional post-treatment such as extraction with organic solvents, concentration and the like and, if necessary, further purified by recrystallization, chromatography or the like to isolate the desired compound.
  • An acylation reaction represented by process 14b is carried out using an acylating reagent such as R 21 COOH itself, or ester, acid halide or anhydride thereof.
  • a molar ratio of the acylating reagent relative to compound [XVIII] is usually in a range of 1 to an amount useable as a solvent.
  • a reaction temperature is usually in a range of 0 to 200 a C, and a reaction time is usually in a range of 1 to 200 hours.
  • the reaction may be carried out in the presence of an acid or base catalyst as necessary.
  • a molar ratio of the catalyst relative to raw material compound [XVIII] is in a range of 0.0001 to 100.
  • the base catalyst examples include inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, barium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, calcium carbonate and the like, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium-tert-butoxide and the like, alkaline earth metal alkoxides such as magnesium ethoxide and the like, alkali metal amides such as sodium amide, lithium amide, lithium diisopropylamide, sodium hexamethyldisilazide, lithium hexamethyldisilazide and the like, organic bases such as pyridine, 2-picoline, 4-picoline, 4-dimethylaminopyridine, quinoline, triethylamine, ethyldiisopropylamine, N,N-dimethylaniline, N,N- diethylaniline and the like, and
  • reaction solution can be subjected to conventional post-treatment such as extraction with organic solvents, concentration and the like and, if necessary, further purified by recrystallization, distillation, chromatography or the like to isolate the desired compound.
  • a reaction temperature is usually in a range of 0 to 150 a C
  • a reaction time is usually in a range of 1 to 24 hours.
  • a molar ratio of compound R 7 -L 1 relative to compound [XIX] is usually in a range of 1 to 10.
  • the reaction is usually carried out in the presence of a base and a molar.ratio of the base relative to compound R 7 -L 1 is usually in a range of 1 to 10.
  • the base include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, calcium carbonate, sodium hydride, potassium hydride, silver oxide and the like, alkali metal alkoxides such as potassium-tert-butoxide, sodium methoxide, sodium ethoxide and the like, alkaline earth metal alkoxides such as magnesium ethoxide and the like, organic bases such as pyridine, 2-picoline, 4-picoline, 4- dimethylaminopyridine, quinoline, triethylamine, ethyldiisopropylamine, N,N-dimethylaniline, N,N- diethylaniline and the like, and a mixture thereof.
  • a solvent may be used in the reaction.
  • the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether and the like, aromatic hydrocarbon solvents such as toluene, xylene and the like, halogenated hydrocarbon solvents such as chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene and the like, organic base solvents such as pyridine, triethylamine, N-methylaniline, N,N- di ethylaniline, N, N-diethylaniline and the like,
  • reaction solution can be subjected to conventional post-treatment such as extraction with organic solvents, concentration and the like and, if necessary, further purified by recrystallization, chromatography or the like to isolate the desired compound.
  • a reaction temperature is usually in a range of 0 to 150 a C
  • a reaction time is usually in a range of 1 to 24 hours.
  • the reaction is carried out usually in the presence of a base or an acid and a molar ratio of the base or the acid relative to compound [XX] is usually in a range of 0.001 to 1000.
  • the base examples include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, calcium carbonate and the like, alkali metal alkoxides such as potassium-t-butoxide, sodium methoxide, sodium ethoxide and the like, alkaline earth metal alkoxides such as magnesium ethoxide and the like, and a mixture thereof.
  • inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, calcium carbonate and the like
  • alkali metal alkoxides such as potassium-t-butoxide, sodium methoxide, sodium ethoxide and the like
  • alkaline earth metal alkoxides such as magnesium ethoxide and the like
  • the acid examples include mineral acids such as hydrochloric acid, perchloric acid, hydrobromic acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, polyphosphoric acid and the like, sulfonic acids such as p-toluenesulfonic acid, camphorsulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like, Lewis acids such as zinc chloride, boron trifluoride diethyl ether complex, trimethylsilyl chloride and the like, and a mixture thereof.
  • mineral acids such as hydrochloric acid, perchloric acid, hydrobromic acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, polyphosphoric acid and the like
  • sulfonic acids such as p-toluenesulfonic acid, camphorsulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like
  • Lewis acids
  • the acid may form a salt with alkali metals such as sodium, potassium and the like, organic bases such as pyridine, triethylamine, N,N-dimethylaniline and the like. Examples thereof are pyridinium p-toluenesulfonate and the like.
  • a solvent may be used in the reaction.
  • the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether and the like, aromatic hydrocarbon solvents such as toluene, xylene and the like, halogenated hydrocarbon solvents such as chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene and the like, organic base solvents such as pyridine, triethylamine, N-methylaniline, N,N- dimethylaniline, N,N-diethylaniline and the like, nitro compound solvent
  • reaction solution can be subjected to conventional post-treatment such as extraction with organic solvents, concentration and the like and, if necessary, further purified by recrystallization, chromatography or the like to isolate the desired compound.
  • compound [X] when X represents sulfur atom, compound [X] can be also prepared, for example, by reacting diazonium compound [XXII] and thiolate salt [XXIII] according to the following Scheme 15. Diazonium salt [XXII] can be prepared by the known methods .
  • R 1 , R 6 , T, U, V and W are as defined above, and L " represents halogen ion such as chlorine ion, bromine ion, or monoanion of strong acid such as sulfuric acid ion, nitric acid ion and the like.
  • L " represents halogen ion such as chlorine ion, bromine ion, or monoanion of strong acid such as sulfuric acid ion, nitric acid ion and the like.
  • the present compound is usually used by formulating into emulsifiable concentrate, water dispersible powder, suspension, dust or granule by mixing with solid carrier, liquid carrier, surfactant or other adjuvants for formulation although it may be used as it is without addition of any other ingredients.
  • These formulations contain as an active ingredient the present compound usually at a weight ratio of 0.1 to 99.9%, preferably 1 to 90%.
  • Examples of the solid carrier used for such formulation include fine powders or granules of caolin clay, attapulgite, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, maize rachis powder, walnut shell powder, urea, ammonium sulfate, synthetic hydrated silicon oxide and the like, and examples of the liquid carrier include aromatic hydrocarbons such as xylene, methylnaphthalene and the like, alcohols such as isopropanol, ethylene glycol, cellosolve and the like, ketones such as acetone, cyclohexanone, isophorone and the like, vegetable oils such as soybean oil, cotton seed oil and the like, dimethyl sulfoxide, acetonitrile, water and the like.
  • aromatic hydrocarbons such as xylene, methylnaphthalene and the like
  • alcohols such as isopropanol, ethylene glycol, cellosolve and the like
  • surfactant examples include anionic surfactants such as alkylsulfate salt, alkyl (aryl) sulfonate salt, dialkylsulfosuccinate salt, polyoxyethylene alkyl aryl ether phosphate salt, naphthalenesulfonate formalin condensate and the like, nonionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene alkyl polyoxypropylene block copolymer, sorbi an fatty acid ester and the like.
  • anionic surfactants such as alkylsulfate salt, alkyl (aryl) sulfonate salt, dialkylsulfosuccinate salt, polyoxyethylene alkyl aryl ether phosphate salt, naphthalenesulfonate formalin condensate and the like
  • nonionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene alkyl polyoxypropylene block copolymer, sorbi an
  • the adjuvant for formulation examples include lignin sulfonate salt, alginate salt, polyvinyl alcohol, gum arabic, CMC (carboxylmethyl cellulose) , PAP (isopropyl acid phosphate) and the like.
  • the present compound is applied by, for example, foliage application, soil treatment, seed disinfection although they can be usually used by any application method known to those skilled in the art.
  • an amount of the present compound to be applied may vary depending upon kind of subject plant (crop and the like) , kind of subject disease, occurrence degree of disease, formulation form, application method, application time, weather conditions and may be usually 0.01 to 50 g/are, preferably 0.05 to 10 g/are.
  • the application concentration of the present compound is usually 0.0001 to 0.5%, preferably 0.0005 to 0.2%, and dust, granule or the like is applied as it is without any dilution.
  • the present compound may be used as an agricultural and/or horticultural antifungal agent for farmland, paddy field, orchard, tea plantation, pasture, lawn area and potentiated antifungal effect can be expected by using by mixing with other agricultural and/or horticultural antifungal agent.
  • Example of the other agricultural and horticultural antifungal agent include azole antifungal compound such as propiconazole, triadimenol, prochloraz, penconazole, tebuconazole, flusilazole, diniconazole, bromoconazole, epoxyconazole, difenoconazole, cyproconazole, metconazole, triflumizole, tetraconazole, myclobutanil, fenbuconazole, hexaconazole, fluquinconazole, triticonazole (RPA 400727), bitertanol, imazalil, flutriafol and the like, cyclic amine antifungal compound such as fenpropimorph, tridemorph, fenpropidin and the like, benzimidazole antifungal compounds such as carbendazim, benomyl, thiabendazole, thiophanate-methyl and the like, proc
  • the present compounds may be used by mixing with or in combination with insecticide, acaricide, nematicide, herbicide, plant growth regulator, fertilizer or the like.
  • examples of the vegetable disease which can be controlled by the present compound are as follows: blast (Pyricularia orvzae) , leaf spot (Cochliobolus miyabeanus) and sheath blight (Rhizoctonia solani) of rice plant, powdery mildew (Ervsiphe ⁇ raminis) , scab (Gibberella zeae) , rust (Puccinia striiformis, P. ⁇ raminis, P. recondita. P.
  • powdery mildew (Sphaerotheca fuli ⁇ inea) , gummy stem blight (Mvcosphaerella elonis) , stem rot (Fusarium oxysporum) , downy mildew ( Pseudoperonospora cubensis) , late blight (Phvtophthora sp. ) and da ping-off (Pvthium SP.
  • the present compound When used as an active ingredient for insecticidal and/or acaricidal agent, they may be used as such without addition of any other ingredients. However, it is usually used by formulating into oil solution, emulsifiable concentrate, water dispersible powder, flowable agent, granule, dust, aerosol, fumigant (fogging agent or the like) , poisonbait or the like, by mixing with solid carrier, liquid carrier, gaseous carrier, bait or the like and, if necessary, adding surfactant, or other auxiliaries for formulation.
  • These preparations contain the present compound as an active ingredient, usually, in a ratio by weight of 0.01% to 95%.
  • the solid carrier used for such formulation are fine powders or granules of clay (such as caolin clay, diatomaceous earth, synthetic hydrated silicon oxide, bentonite, Fubasami clay, acid clay and the like) , talcs, ceramic, other inorganic minerals (such as cericite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica and the like) , chemical fertilizer (such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride and the like) .
  • clay such as caolin clay, diatomaceous earth, synthetic hydrated silicon oxide, bentonite, Fubasami clay, acid clay and the like
  • talcs ceramic
  • other inorganic minerals such as cericite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica and the like
  • liquid carrier examples include water, alcohols (such as methanol, ethanol and the like) , ketones (such as acetone, methyl ethyl ketone and the like) , aromatic hydrocarbons (such as benzene, toluene, xylene, ethylbenzene, methylnaphthalene and the like) , aliphatic hydrocarbons (such as hexane, cyclohexane, kerosine, light oil and the like) , esters (such as ethyl acetate, butyl acetate and the like) , nitriles (such as acetonitrile, isobutyronitrile and the like) , ethers (such as diisopropyl ether, dioxane and the like) , acid amides (such as N,N-dimethylformamide, N,N-dimethylacetamide and the like) , halogenated hydrocarbons (such as
  • surfactant examples include alkylsulfate salt, alkylsulfonate salt, alkylarylsulfonate salt, alkyl aryl ether and its polyoxyethylene compound, polyethylene glycol ether, polyhydric alcohol ester, sugar alcohol derivative and the like.
  • auxiliary for formulation such as adhesive agent and dispersing agent
  • polysaccharides such as starch powder, gum arabic, cellulose derivative, alginic acid and the like
  • lignin derivatives such as starch powder, gum arabic, cellulose derivative, alginic acid and the like
  • bentonite such as lignin derivatives
  • sugars such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid and the like
  • synthetic water-soluble polymer such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid and the like
  • the stabilizing agent examples include PAP (acid isopropyl phosphate), BHT (2, 6-di-tert-butyl-4- ethylphenol) , BHA (mixture of 2-tert-butyl-4-methoxyphenol and3-tert-butyl-4-methoxyphenol) , vegetable oil, mineral oil, surfactant, and fatty acid or ester thereof and the like.
  • PAP acid isopropyl phosphate
  • BHT 2, 6-di-tert-butyl-4- ethylphenol
  • BHA mixture of 2-tert-butyl-4-methoxyphenol and3-tert-butyl-4-methoxyphenol
  • vegetable oil mineral oil
  • surfactant and fatty acid or ester thereof and the like.
  • Examples of the base material for poison bait are components for bait such as cereal powder, vegetable oil, sugar, crystalline cellulose and the like, antioxidant such as dibutylhydroxytoluene, nordihydroguaiaretic acid and the like, preservative such as dehydroacetic acid and the like, substance for preventing erroneous eating such as red pepper powder, attractant flavor such as cheese flavor, onion flavor and the like.
  • the preparations thus prepared are used as they are or after diluted with water or the like.
  • the preparations may be used by mixing with or in combination with other insecticide, nematicide, acaricide, antifungal agent, herbicide, plant growth regulator, synergist, fertilizer, soil conditioner, animal feed, and the like.
  • the insecticide and/or nematocide and/or acaricide may include, for example, organophosphorus compounds such as
  • the application dosage is usually 0.1 g to 100 g/10 are.
  • the application concentration is usually 0.1 ppm to 5000 ppm.
  • Granule, dust and the like are applied as preparations themselves without any dilution.
  • emulsifiable concentrate, water dispersible powder, flowable agent and the like are usually applied after diluted with water to 0.1 ppm to 5000 ppm, and oil solution, aerosol, fumigant, poison bait and the like are applied as such.
  • application dosage and application concentration may vary depending upon kind of preparations, application timing, application place, application method, kind of insect pest, degree of damage and the like and they may be increased or decreased beyond the above range.
  • the harmful insects and harmful ticks and mites , against which the present compounds exhibit controlling activity may include, for example, the following: Hemiptera:
  • Planthoppers such as small brown planthopper (Laodelphax striatellus) , brown rice planthopper
  • Leafhoppers such as green rice leafhopper (Nephotettix cincticeos) and green rice leafhopper (Nephotettix virescense) ; aphids (Aphididae) , stink bugs (Pentatomidae) , whiteflies (Aleyrodidae) , scales
  • Pyralid moths such as rice stem borer (Chilo suppressalis) , rice leafroller (Cnaphalocrocis medinalis) and Indian meal moth (Plodia interpunctella) ; owlet moths (Noctuidae) such as common cutworm (Soodoptera litura) , rice armyworm (Pseudaletia separata) and cabbage armyworm (Mamestra brassicae) , white and sulfer butterflies (Pieridae) such as common cabbageworm (Pieris rapae crucivora) , tortricid moths
  • Trotricidae such as Adoxophyes spp . ; Carposinidae; lyonetiid moths (Lyonetiidae) ; tussock moth (Lymantriidae) ; Plusiae;
  • Agrothis spp. such as cutworm (A ⁇ rothis se ⁇ etum) and black cutworm (A ⁇ rothis ipsilon) : Heliothis spp.; diamondblack
  • Mosquitos (Calicidae) such as common mosquito (Culex pipiens pallens) and Culex tritaeniorhvnchus; Aedes spp. such as Aedes ae ⁇ vpti and Aedes albopictus; Anopheles spp. such as
  • Corn rootworm such as western corn rootworm (Diabrotica vir ⁇ ifora) and southern corn root worm (Diabrotica undecimpunctata) ; scarabs (Scarabaeidae) such as cupreous chafer (Anomala cuprea) and soybean beetle (Anomala rufocuprea) ; weevils (Cureulionidae) such as maize weevil (Sitophilus zeamalis) , rice water weevil (Lissorhoptrus orvzophilus) and adzuki bean weevil (Callosobruchys chineneis) ; darkling beetles (Tenebrionidae) such as yellow mealworm (Tenebrio moliter) and red flour beetles (Tribolium astaneum) ; leaf beetles (Chrysomelidae) such as striped flea beetles (Phyllotrata stroilata) and cucurbit leaf beet
  • German cockroach (Blattella ⁇ ermanica) , smokybrown cockroach (Periplaneta fuli ⁇ inosa) , American cockroch (Periolaneta americana) , brown cockroach (Periplaneta brunnea) and oriental cockroach (Blatta orientalis) Thysanoptera:
  • Thrips palmi and flower thrips (Thrips hawaiiensis) Hymenoptera:
  • Ants Formidae
  • Vespidae Vespidae
  • Bethylidae sawflies
  • Enthredinidae such as cabbage sawfly
  • cabbage sawfly Athalia rosae -iaponensis
  • Mole crickets (Gryllotalpidae; grasshoppers (Acrididae) Aphaniptera : Purex irritans Anoplura :
  • Phthirus pubis Isoptera Phthirus pubis Isoptera
  • Reticulitermes speratus Reticulitermes speratus .
  • Formosan subterrauean termite (Coptotermes formosanus) Acarina plant parasitic mites such as Tetranvchus urticae. Panonvchus citri, Tetranvchus cinnabarinus and Panonvchus ulmi . animal parasitic Ixodes such as Boophilus microphus . and house dust mites
  • the present compound is also effective for the control of insect pests with resistance to conventional insecticides or acaricides.
  • the organic layer was washed with dilute hydrochloric acid once and extracted twice with 300 ml of an aqueous solution of sodium carbonate.
  • the resulting sodium carbonate solution was made weakly acidic with concentrated hydrochloric acid to precipitate the desired material as crystals.
  • This mixture was extracted twice with 500 ml of ethyl acetate to obtain the organic layer, which was washed once with water, dried with magnesium sulfate and concentrated to obtain 1.1 g (3.7 mmol) of the desired methyl 3-hydroxy-2- (N-methyl-3-acetylanilino) acrylate.
  • N,N-dimethylformamide was stirred at room temperature overnight.
  • the resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate.
  • the organic layer was washed once with dilute hydrochloric acid and extracted twice with an aqueous solution of sodium carbonate.
  • the resulting aqueous alkaline layer was adjusted to around pH
  • the organic layer was dried with magnesium sulfate and concentrated to obtain the residue, and to this were added 0.20 liter of methanol and 0.30 g (1.6 mmol) of p-toluenesulfonic acid monohydrate, followed by heating to reflux for 3 hours. The mixture was allowed to cool to room temperature, and 1 ml (7.2 mmol) of triethylamine was added thereto, followed by concentration. The residue was partitioned between ethyl acetate and water and the organic layer was dried with magnesium sulfate and concentrated to obtain 3.5 g (19 mmol) of the desired N-methyl-3- (dimethoxymethyl) aniline .
  • the aqueous layer was made acidic by the addition of concentrated hydrochloric acid and the precipitates were extracted twice with ethyl acetate.
  • the organic layer was washed with water, dried with magnesium sulfate and concentrated to obtain 1.8 g (7.2 mmol) of the desired methyl 2- (3-acetylphenylthio) -3 -hydroxyacrylate .
  • reaction solution was poured into dilute hydrochloric acid, extracted with 20ml of ethyl acetate, and the organic layer was washed successively with dilute hydrochloric acid and an aqueous solution of sodiumbicarbonate, dried with magnesium sulfate and concentrated to obtain 593 mg (2.08 mmol) of the desired 2- ⁇ 3-(N- methyltrifluoroacetoamino) phenyl ⁇ -2- methoxyiminoacetonitrile .
  • the resulting reaction solution was poured into dilute hydrochloric acid, extracted with 20 ml of ethyl acetate, and the organic layer was washed successively with dilute hydrochloric acid and an aqueous solution of sodiumbicarbonate, dried with magnesium sulfate and concentrated to obtain the residue, which was subjected to silica gel column chromatography to obtain 192 mg (0.736 mmol) of the desired 2- ⁇ 3- (N-methyl-N-methoxycarbonylmethylamino) phenyl ⁇ -2- methoxyiminoacetonitrile (intermediate for preparing present compound) .
  • the organic layer was washed once with dilute hydrochloric acid, extracted twice with an aqueous solution of sodium carbonate, the combined aqueous sodium carbonate layers were made weakly acidic with concentrated hydrochloric acid, the precipitates were extracted with 20 ml of ethyl acetate, and the organic layer was washed once with water, dried with magnesium sulfate and concentrated to obtain 119 mg (0.412 mmol) of the desired 2- [3- ⁇ N-methyl-N- (methyl 3-hydroxyacrylate-2- y1) amino ⁇ phenyl] -2-methoxyiminoacetonitrile (intermediate for preparing present compound) .
  • the resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate .
  • the organic layer was washed once with dilute hydrochloric acid and extracted twice with an aqueous solution of sodium carbonate.
  • the resulting aqueous alkaline layer was adjusted to around pH 6 using concentrated hydrochloric acid, and the precipitates were extracted with ethyl acetate.
  • the organic layer was washed with water, dried with magnesium sulfate and concentrated to obtain 0.40 g (about 1.6 mol) of the crude product of the desired methyl 2- (5- acetyl-2-methylphenoxy) -3-hydroxyacrylate.
  • the aqueous layer was made acidic by the addition of concentrated hydrochloric acid, and the precipitates were extracted twice with ethyl acetate.
  • the ethyl acetate layers were combined, washed with water, dried with magnesium sulfate and concentrated to obtain 450 mg (1.69 mmol) of the desired methyl 2- (5-acetyl-2-methyl- phenylthio) -3-hydroxyacrylate .
  • the residue (17.90 g) obtained by concentration was dissolved in 50 ml of 95% ethanol, and to this was added 17.5 g of potassium hydroxide in portions at a bath temperature of 100 °C, followed by heating to reflux for 5 hours and 30 minutes. After ethanol was distilled off from the reaction mixture, water and diethyl ether were added to the residue, the layers were separated, and the aqueous layer was washed with diethyl ether three times.
  • Me represents methyl group
  • Et represents ethyl group
  • n-Pr represents propyl group
  • i-Pr represents isopropyl group
  • n-Bu represents butyl group
  • t- Bu represents tert-butyl group
  • Am represents amyl group
  • Bz represents benzyl group
  • F 5 BZ represents 2,3,4,5,6- pentafluorobenzyl group
  • Ph represents phenyl group
  • 4-CF 3 - PhCH(CH 3 ) represents 1- (4-trifluoromethylphenyl) ethyl group
  • Py represents pyridyl group
  • c represents cyclo
  • sec represents secondary
  • SUIM represents succinimid-1-yl group
  • (A) represents 3-Cl-5-CF 3 -Py-2-yl group
  • (B) represents 5- CF 3 -Py-2-yl group, respectively.
  • Each 2 parts of the present compounds 1-493 and 1001- 1078, 88 parts of caolin clay and 10 parts of talc are sufficiently ground and mixed to obtain each dust.
  • Formulation Example 4 Each 20 parts of the present compounds 1-493 and 1001-1078 , 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecyl benzenesulfonate and 60 parts of xylene are sufficiently mixed to obtain each emulsifiable concentrate.
  • Each 0.2 part of the present compounds 1-493 and 1001-1078 , 0.2 part of d-allethrin, 0.2 part of d-phenothrin, 5 parts of xylene, 3.4 parts of deodorized kerosine and 1 part of an emulsifier ⁇ ATMOS 300 (registered trade name by Atlas Chemical Co.) ⁇ is mixed to dissolve, and this solution and 50 parts of pure water are filled into an aerosol container, a valve part is attached thereto, and 40 parts of a propellant (liquefied petroleum gas) is filled under pressure through the valve part to obtain each aqueous aerosol .
  • a propellant liquefied petroleum gas
  • 0.3 g of d-allethrin is added to each 0.3 g of the present compounds 1-493 and 1001-1078, the mixture is dissolved in 20 ml of acetone, mixed with 99.4 g of a carrier for a mosquito coil (prepared by mixing Tabu powder, pyrethrum marc powder and wood flour in the ratio of 4:3:3) uniformly by stirring, 120 ml of water is added and sufficiently kneaded, molded and dried to obtain each mosquito coil.
  • Formulation Example 11 Acetone is added to each 0.4 g of the present compounds 1-493 and 1001-1078 , 0.4 g of d-allethrin and 0.4 g of piperonyl butoxide to dissolve to a total volume of 10 ml.
  • Each 10 mg of the present compounds 1-493 and 1001-1078 is dissolved in 0.5 ml of acetone, this solution is added to 5 g of solid bait powder for animals (Breeding Solid Feed CE-2; trade name by Japan Clea Co. , Ltd. ) and mixed uniformly. Then, acetone is removed by air-drying to obtain each 0.5% poison bait.
  • Test Examples indicate that the present compounds are useful as a microbicidal agent for agriculture and/or horticulture, and an insecticidal and/or acaricidal agent.
  • the present compounds are indicated by referring to chemical Nos . in Table 1 and Table 2.
  • Test Example 4 The efficacy of the invented compounds against brown leaf rust of wheat (preventive effect)
  • the plants were air-dried and spores of brown leaf rust of wheat were inoculated on the wheats . After inoculation, the plants were first placed at 23 °C in the darkness under high humidity for one day and further under illumination for 6 days, and the efficacy of the tested compound was assessed. As a result, all the compounds inhibited development of brown leaf rust of wheat. The rate of desease area on the treated plants was less than 30 %.
  • Test Example 5 Efficacy of the invented compounds against leaf blight of wheat (preventive effect)
  • Test Example 6 The efficacy of the invented compound against glume blotch of wheat (preventive effect)
  • Test Example 8 The efficacy of the invented compounds on downy mildew of cucumber (preventive effect)
  • Nos. 1, 2, 4, 115, 116, 163, 174, 215, 216, 217, 252, 272 was prepared into water dispersible powder according to the procedures of Formulation Example 1, diluted with water to a predetermined concentration (500 ppm) , and these were sprayed onto foliage of cucumbers sufficiently. After the treatment, the plants were air-dried and spores of downy mildew of cucumber were inoculated on the cucumbers. After inoculation, the plants were first placed at 23 °C under high humidity for 1 day and further in a greenhouse for 10 days, and the efficacy of the tested compound was assessed. As a result, all the compounds inhibited development of downy mildew of cucumber.
  • the plants were air-dried and spores of powdery mildew of cucumber were inoculated on the cucumbers . After inoculation, the plants were placed at 23 °C for 12 days, and the efficacy of the tested compound was assessed. As a result, all the compounds inhibited development of powdery mildew of cucumber. The rate of disease area on the treated plant was less than 30%.
  • the plants were air-dried and zoosporangia of downy mildew of grape were inoculated on the grapes . After inoculation, the plants were placed first at 23 °C under high humidity for 1 day and further in a greenhouse for 6 days, and the efficacy of the tested compound was assessed. As a result, all the compounds inhibited development of powdery mildew of grape. The rate of disease area on the treated plant was less than 30%.
  • Test Example 12 Insecticidal test against larva of common cutworm (Spodoptera litura) Each of the compounds Nos. 4, 9 and 13 was prepared into emulsifiable concentrate according to the procedures of Formulation Example 4, diluted with water to a predetermined concentration (500 ppm) to obtain 2 ml of a diluted solution, which was soaked into 13 g of an artificial feed for Spodoptera litura which had been prepared in a polyethylene cup having the diameter of 11 cm. 5 larvae of 4 week-age Spodoptera litura were released in the cup and, after 6 days, the death or survival thereof was investigated to obtain mortality. As a result, all the test compounds showed mortality of 80%. Test Example 13 : Insecticidal test against larva of brown planthopper (Nilaparvata lugens)
  • Nilaparvata lugens were released thereon. After release of larvas, the plants were left in a greenhouse for 6 days, the death or survival thereof was investigated to obtain mortality.
  • Test Example 14 Insecticidal test against larva of southern corn root worm (Diabrotica undecimpunctata)
  • Each of the compounds Nos. 2 and 4-10 was prepared into emulsifiable concentrate according to the procedures in Formulation Example 4 and diluted with water to a predetermined concentration (50 ppm) to obtain 1 ml of the diluted solution, whichwas added dropwise on the filter. About 30 eggs of southern corn root worm were placed on the filter, and one budding of corn was placed thereon as a feed. After 8 days, the death or survival of hatched larvae was investigated to obtain mortality. As a result, all the compounds showed mortality of 80% or more.
  • Test Example 15 Application test against cotton aphid (Aphid gossypii)
  • each of the present compounds 5, 6, 8 and 10 was prepared into emulsifiable concentrate according to the procedures of Formulation Example 4, diluted with water to a predetermined concentration (500 ppm) to obtain the diluted solution, which was sprayed at an amount of 20 ml/pot. 6 days after drug solution spray, the controlling value was obtained according to the following equation. As a result, the above compounds showed the controlling effect of 90% or more, respectively.
  • Controlling value ⁇ 1- (Cb»Tai) / (Tb»Cai) ⁇ x 100
  • Cb Number of worms in non-treated plot before treatment
  • Cai Number of worms in non-treated plot at observation
  • Tb Number of worms in test plot before treatment
  • Tai number of worms in test plot at observation
  • Example 16 Spraying test against Tetranychus urticae Bush bean (Phaseolus vulgaris L.var. humilis Alef.) (primordial leaf stage) planted in a polyethylene cup was made parasitic with 20 female adults of Tetranychus urticae per leaf and was placed in a constant temperature room.
  • each of the present compounds 5 , 6, 7, 8, 9, 10 and 13 was prepared into emulsifiable concentrate according to the procedures in Formulation Example 4, diluted with water to a predetermined concentration (500 ppm) to obtain the diluted solution, which was sprayed to the pot at an amount of 20 ml/pot. 8 days after the spray, degree of damage by Tetranychus urticae was investigated. As a result, in plots treated with the above test compounds, damage was hardly observed.
  • Test Example 17 Insecticidal test against house-fly (Musca domestica) The bottom of a polyethylene cup having a diameter of 5.5 cm was covered with a filter paper having the same diameter of that of the bottom. Each of the present compounds 1, 2, 4, 5, 7, 8, 9, 10 and 13 was prepared into emulsifiable concentrate, diluted with water to a predetermined concentration (500 ppm) to obtain 0.7 ml of diluted solution, which was added dropwise on the filter, and 30 mg of sucrose as a feed was placed uniformly in the cup. 10 female adults of Musca domestica were released in the cup, the cup was capped and, after 24 hours, the survival or death thereof was investigated to obtain mortality. As a result, the above test compounds showedmortality of 80% or more, respectively.
  • Test Example 18 Insecticidal test against common mosquito (Culex pipens pallens)
  • Each of the present compounds 1, 4, 6, 8, 10, 12 and 13 was prepared into emulsifiable concentrate according to the procedures of Formulation Example 4, diluted with water to a predetermined concentration (500 ppm) to obtain 0.7ml of a diluted solution, which was added to 100 ml of ion-exchanged water (concentration of an active ingredient: 3.5 ppm). 20 larvae of one week-age Culex pipens pallens were released therein and, 8 days after treatment, adult eclosion inhibiting rate was investigated. As a result, the above test compounds showed adult eclosion inhibiting rate of 80% or more, respectively.
  • the present compounds have excellent antifungal effect for agriculture and/or horticulture as well as excellent insecticidal and/or acaricidal effect.

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Abstract

La présente invention concerne des composés d'éther d'oxime représentés par la formule (I). Ces composés présentent un effet antifongique excellent pour l'agriculture et/ou l'horticulture ainsi qu'un effet insecticide et/ou acaricide excellent.
PCT/JP1998/001408 1997-04-01 1998-03-27 Composes d'ether d'oxime, leur utilisation et intermediaires pour leur preparation WO1998043949A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU65193/98A AU6519398A (en) 1997-04-01 1998-03-27 Oxime ether compounds, their use and intermediates for preparations of the same
EP98911069A EP0975587A1 (fr) 1997-04-01 1998-03-27 Composes d'ether d'oxime, leur utilisation et intermediaires pour leur preparation
BR9809746-6A BR9809746A (pt) 1997-04-01 1998-03-27 Compostos de éteres oxìmicos, seu uso e intermediários para preparações dos mesmos.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP8290097 1997-04-01
JP9/82900 1997-04-01
JP9/318031 1997-11-19
JP31803197 1997-11-19
JP2607498 1998-02-06
JP10/26074 1998-02-06

Publications (1)

Publication Number Publication Date
WO1998043949A1 true WO1998043949A1 (fr) 1998-10-08

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EP (1) EP0975587A1 (fr)
KR (1) KR20000075703A (fr)
CN (1) CN1251575A (fr)
AU (1) AU6519398A (fr)
BR (1) BR9809746A (fr)
WO (1) WO1998043949A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999067209A1 (fr) * 1998-06-20 1999-12-29 Hoechst Schering Agrevo Gmbh Derives d'acide hydroximique, procede et intermediaires pour leur preparation
WO2000003975A2 (fr) * 1998-07-16 2000-01-27 Aventis Agriculture Ltd. Derives d'arylvinylether et leur utilisation comme herbicides
WO2000018727A1 (fr) * 1998-09-30 2000-04-06 Sumitomo Chemical Company, Limited Intermediaires dans la production de composes d'oxime-ether
WO2012038521A1 (fr) * 2010-09-23 2012-03-29 Syngenta Participations Ag Microbiocides inédits
WO2020027214A1 (fr) 2018-07-31 2020-02-06 住友化学株式会社 PROCÉDÉ DE LUTTE CONTRE LA ROUILLE DU SOJA RÉSISTANT AUX INHIBITEURS DE Qo
WO2022181793A1 (fr) 2021-02-26 2022-09-01 住友化学株式会社 Dérivé d'acide phénylacétique, utilisation associée et intermédiaire de production associé

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102690246B (zh) * 2012-05-30 2014-06-04 华中农业大学 肟醚胺类化合物或其盐、包含肟醚胺类化合物或其盐的组合物及应用
CN102850246B (zh) * 2012-07-10 2015-04-22 江西理工大学 一种苯胺类衍生物引入巯基的方法

Citations (1)

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EP0464381A2 (fr) * 1990-06-16 1992-01-08 Bayer Ag Esters d'acides 2-méthoxyiminocarboxyliques

Patent Citations (1)

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EP0464381A2 (fr) * 1990-06-16 1992-01-08 Bayer Ag Esters d'acides 2-méthoxyiminocarboxyliques

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J.K. FAULKNER ET AL.: "Some derivatives of isovanillin", JOURNAL OF THE CHEMICAL SOCIETY, 1962, LETCHWORTH GB, pages 4737 - 4738, XP002073073 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999067209A1 (fr) * 1998-06-20 1999-12-29 Hoechst Schering Agrevo Gmbh Derives d'acide hydroximique, procede et intermediaires pour leur preparation
WO2000003975A2 (fr) * 1998-07-16 2000-01-27 Aventis Agriculture Ltd. Derives d'arylvinylether et leur utilisation comme herbicides
WO2000003975A3 (fr) * 1998-07-16 2000-08-03 Rhone Poulenc Agriculture Derives d'arylvinylether et leur utilisation comme herbicides
WO2000018727A1 (fr) * 1998-09-30 2000-04-06 Sumitomo Chemical Company, Limited Intermediaires dans la production de composes d'oxime-ether
WO2012038521A1 (fr) * 2010-09-23 2012-03-29 Syngenta Participations Ag Microbiocides inédits
WO2020027214A1 (fr) 2018-07-31 2020-02-06 住友化学株式会社 PROCÉDÉ DE LUTTE CONTRE LA ROUILLE DU SOJA RÉSISTANT AUX INHIBITEURS DE Qo
WO2022181793A1 (fr) 2021-02-26 2022-09-01 住友化学株式会社 Dérivé d'acide phénylacétique, utilisation associée et intermédiaire de production associé

Also Published As

Publication number Publication date
AU6519398A (en) 1998-10-22
BR9809746A (pt) 2000-06-20
CN1251575A (zh) 2000-04-26
EP0975587A1 (fr) 2000-02-02
KR20000075703A (ko) 2000-12-26

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