WO2021088756A1 - 一种肟醚类化合物及其用途 - Google Patents

一种肟醚类化合物及其用途 Download PDF

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WO2021088756A1
WO2021088756A1 PCT/CN2020/125780 CN2020125780W WO2021088756A1 WO 2021088756 A1 WO2021088756 A1 WO 2021088756A1 CN 2020125780 W CN2020125780 W CN 2020125780W WO 2021088756 A1 WO2021088756 A1 WO 2021088756A1
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alkyl
hydrogen
haloalkyl
following groups
cycloalkyl
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PCT/CN2020/125780
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English (en)
French (fr)
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程学明
于海波
陈亮
吴鸿飞
孙庚�
郭春晓
徐利保
徐靖博
孙宁宁
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沈阳中化农药化工研发有限公司
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Priority to EP20883937.3A priority Critical patent/EP4056554A4/en
Priority to US17/755,625 priority patent/US20220400678A1/en
Priority to BR112022008654A priority patent/BR112022008654A2/pt
Publication of WO2021088756A1 publication Critical patent/WO2021088756A1/zh

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • 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
    • C07D263/34—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 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
    • C07D263/48—Nitrogen atoms not forming part of a nitro radical
    • 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
    • C07D277/32—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 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
    • C07D277/38—Nitrogen atoms
    • C07D277/40—Unsubstituted amino or imino radicals
    • 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
    • C07D277/32—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 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
    • C07D277/38—Nitrogen atoms
    • C07D277/44—Acylated amino or imino radicals
    • C07D277/46—Acylated amino or imino radicals by carboxylic acids, or sulfur or nitrogen analogues thereof
    • 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
    • C07D277/32—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 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
    • C07D277/38—Nitrogen atoms
    • C07D277/50—Nitrogen atoms bound to hetero atoms
    • 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
    • C07D277/32—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 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
    • C07D277/38—Nitrogen atoms
    • C07D277/50—Nitrogen atoms bound to hetero atoms
    • C07D277/52—Nitrogen atoms bound to hetero atoms to sulfur atoms, e.g. sulfonamides
    • 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
    • C07D277/32—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 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
    • C07D277/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • the invention belongs to the field of agricultural fungicides. Specifically, it relates to an oxime ether compound and its use.
  • Oxime ether derivatives are a class of compounds with broad-spectrum biological activity, which are widely used in pesticides, herbicides and fungicides. Since the first commercial oxime ether fungicide Cymoxan developed by DuPont in the United States in 1974, new commercial varieties have appeared continuously.
  • Patent CN106916084A discloses the following compounds CK1, CK2 and CK3 (respectively compound numbers in CN106916084A Table 1: 107, 115 and 116), which have good activity against bacterial diseases and fungal diseases.
  • the purpose of the present invention is to provide an oxime ether compound with a novel structure, which can be used to prepare medicines for preventing and controlling pathogens in agriculture and other fields.
  • X is selected from sulfur or oxygen
  • Z is selected from hydrogen, unsubstituted or substituted C 1 -C 6 linear or branched alkyl groups: halogen, cyano, trifluoromethyl, trifluoromethoxy, hydroxyl, nitro Group, amino;
  • R 1 is selected from C 1 -C 8 alkyl
  • R 2 is selected from hydrogen or C 1 -C 8 alkyl
  • W connected by Q, N and N forms a 3-6 membered saturated or unsaturated ring
  • the saturated or unsaturated ring contains 0-2 NR 10 , O, S or oxidized S
  • the ring can also be R 11 is substituted or forms a fused ring with a benzene ring
  • R 3 is selected from hydrogen, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 haloalkenyl, C 2 -C 8 alkynyl, C 2 -C 8 haloalkynyl, C 1 -C 8 alkoxy C 1 -C 8 alkyl, N(R 12 )R 13 , optionally substituted aryl or optionally substituted Heteroaryl
  • R 4 is selected from hydrogen, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 5 is selected from C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkyl substituted phenyl or N(R 12 )R 13 ;
  • R 6 is selected from hydrogen or C 1 -C 8 alkyl
  • R 7 is selected from hydrogen or C 1 -C 8 alkyl
  • R 8 is selected from hydrogen, C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, unsubstituted or optionally substituted phenyl with the following groups, wherein the following groups are hydrogen, halogen, cyano , Nitro, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;
  • R 9 is selected from C 1 -C 8 alkyl, C 1 -C 8 haloalkyl, unsubstituted or optionally substituted phenyl with the following groups, wherein the following groups are hydrogen, halogen, cyano, nitro Group, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl;
  • R 10 is hydrogen, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkylcarbonyl or C 1 -C 2 alkoxycarbonyl;
  • R 11 is H, halogen, CN, NO 2 , C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 2 haloalkoxy, optionally substituted aryl ⁇ or S(O)nR 14 , where n is 0, 1 or 2;
  • R 12 is selected from C 1 -C 8 alkyl
  • R 13 is selected from C 1 -C 8 alkyl
  • R 14 is hydrogen, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 3 -C 6 cycloalkyl or C 1 -C 4 alkoxy;
  • X is selected from sulfur or oxygen
  • Z is selected from hydrogen, unsubstituted or C 1 -C 3 linear or branched alkyl groups substituted by any of the following groups: halogen, cyano, trifluoromethyl, trifluoromethoxy, hydroxyl, nitro Group, amino;
  • R 1 is selected from C 1 -C 4 alkyl
  • R 2 is selected from hydrogen or C 1 -C 4 alkyl
  • W connected by Q, N and N forms a 3-6 membered saturated or unsaturated ring
  • the saturated or unsaturated ring contains 0-2 NR 10 , O, S or oxidized S
  • the ring can also be R 11 is substituted or forms a fused ring with a benzene ring
  • R 4 is selected from hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl;
  • R 5 is selected from C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkyl substituted phenyl or N(R 12 )R 13 ;
  • R 6 is selected from hydrogen or C 1 -C 4 alkyl
  • R 7 is selected from hydrogen or C 1 -C 4 alkyl
  • R 8 is selected from hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, unsubstituted or optionally substituted phenyl with the following groups, wherein the following groups are hydrogen, halogen, cyano , Nitro;
  • R 9 is selected from C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, unsubstituted or optionally substituted phenyl with the following groups, wherein the following groups are hydrogen, halogen, cyano, nitro base;
  • R 10 is hydrogen, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkylcarbonyl or C 1 -C 2 alkoxycarbonyl;
  • R 11 is H, halogen, CN, NO 2 , C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 2 haloalkoxy, optionally substituted aryl ⁇ or S(O)nR 14 , where n is 0, 1 or 2;
  • R 12 is selected from C 1 -C 4 alkyl
  • R 13 is selected from C 1 -C 4 alkyl
  • R 14 is hydrogen, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 3 -C 6 cycloalkyl or C 1 -C 4 alkoxy;
  • X is selected from oxygen or sulfur
  • Z is selected from hydrogen, methyl or ethyl
  • R 1 is selected from methyl or ethyl
  • R 2 is selected from hydrogen, methyl or ethyl
  • W connected by Q, N and N forms a 3-6 membered saturated or unsaturated ring, said saturated or unsaturated ring contains 0-2 NR 10 , O, S or oxidized S, and the ring can also be combined with The benzene ring forms a fused ring;
  • R 4 is selected from hydrogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl
  • R 5 is selected from C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, methyl substituted phenyl or N(R 11 )R 12 ;
  • R 6 is selected from hydrogen, methyl or ethyl
  • R 7 is selected from hydrogen, methyl or ethyl
  • R 8 is selected from methyl, ethyl, trifluoromethyl, unsubstituted or optionally substituted phenyl with the following groups: the following groups are hydrogen, halogen, cyano, nitro;
  • R 9 is selected from methyl, ethyl, trifluoromethyl, unsubstituted or optionally substituted phenyl with the following groups: the following groups are hydrogen, halogen, cyano, nitro;
  • R 12 is selected from methyl or ethyl
  • R 13 is selected from methyl or ethyl.
  • X is selected from oxygen or sulfur
  • Z is selected from hydrogen
  • R 1 is selected from methyl or ethyl
  • R 3 is selected from C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, N(R 12 )R 13 , unsubstituted or optionally substituted benzene with the following groups Group, pyridyl, pyrazolyl, thiazolyl, isothiazolyl or thiadiazolyl: the following groups are hydrogen, halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkane Group, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio or C 1 -C 4 haloalkylthio;
  • R 5 is selected from C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, p-methylphenyl or N(R 12 )R 13 ;
  • R 6 is selected from hydrogen, methyl or ethyl
  • R 7 is selected from hydrogen, methyl or ethyl
  • R 8 is selected from methyl, ethyl, trifluoromethyl, unsubstituted or optionally substituted phenyl with the following groups: the following groups are hydrogen, halogen, cyano, nitro;
  • R 9 is selected from methyl, ethyl, trifluoromethyl, unsubstituted or optionally substituted phenyl with the following groups: the following groups are hydrogen, halogen, cyano, nitro;
  • R 12 is selected from methyl or ethyl
  • R 13 is selected from methyl or ethyl
  • a further optional compound in the present invention is: in general formula I
  • X is selected from sulfur
  • Z is selected from hydrogen
  • R 3 is selected from C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, unsubstituted or optionally substituted phenyl, pyridyl, pyrazolyl , Thiazolyl, isothiazolyl or thiadiazolyl: the following groups are hydrogen, halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkane Oxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio or C 1 -C 4 haloalkylthio;
  • R 8 is selected from methyl, ethyl, trifluoromethyl, unsubstituted or optionally substituted phenyl with the following groups: the following groups are hydrogen, halogen, cyano, nitro;
  • R 9 is selected from methyl, ethyl, trifluoromethyl, unsubstituted or optionally substituted phenyl with the following groups: the following groups are hydrogen, halogen, cyano, nitro;
  • a further optional compound in the present invention is: in general formula I
  • X is selected from sulfur
  • Z is selected from hydrogen
  • R 3 is selected from C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, any one of the groups represented by K 1 -K 10 , unsubstituted or any of the following groups
  • Substituted phenyl or pyridyl the following groups are halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio or C 1 -C 4 haloalkylthio;
  • K 1 -K 10 are expressed as follows:
  • Halogen refers to fluorine, chlorine, bromine or iodine.
  • Alkyl straight or branched chain alkyl, such as methyl, ethyl, n-propyl, isopropyl or different butyl, pentyl or hexyl isomers.
  • Halogenated alkyl groups straight or branched chain alkyl groups, the hydrogen atoms on these alkyl groups can be partially or completely replaced by halogens, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl Group, trifluoromethyl, heptafluoroisopropyl, etc.
  • Cycloalkyl substituted or unsubstituted cyclic alkyl, such as cyclopropyl, cyclopentyl or cyclohexyl; substituents such as methyl, halogen and the like.
  • Alkenyl includes linear or branched alkenes, such as vinyl, 1-propenyl, 2-propenyl and different butenyl, pentenyl and hexenyl isomers; alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
  • Haloalkenyl an alkenyl group in which at least one or more hydrogen atoms can be substituted by halogen atoms.
  • Alkynyl includes straight-chain or branched alkynes, such as ethynyl, 1-propynyl and different butynyl, pentynyl and hexynyl isomers; alkynyl also includes groups composed of multiple triple bonds Groups, such as 2,5-hexadiynyl.
  • Halogenated alkynyl an alkynyl group in which at least one or more hydrogen atoms can be substituted by halogen atoms.
  • Alkoxy straight or branched chain alkyl, connected to the structure via an oxygen atom bond, such as methoxy, ethoxy, tert-butoxy, etc.
  • Halogenated alkoxy groups straight or branched chain alkoxy groups, the hydrogen atoms on these alkoxy groups can be partially or completely replaced by halogen, such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluorine Methoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy and the like.
  • Alkylthio straight or branched chain alkyl, connected to the structure via a sulfur atom bond, such as methylthio, ethylthio and the like.
  • Halogenated alkylthio linear or branched alkylthio.
  • the hydrogen atoms on these alkylthio groups can be partially or completely replaced by halogens, such as difluoromethylthio, trifluoroethylthio and the like.
  • Alkylamino straight or branched chain alkyl, connected to the structure via a nitrogen atom bond, such as methylamino, ethylamino, n-propylamino, isopropylamino or isomeric butylamine.
  • Dialkylamino Two identical or different linear or branched alkyl groups are connected to the structure via a nitrogen atom bond, such as dimethylamino, methylethylamino, etc.
  • Cycloalkylamino cycloalkyl-NH-, such as cyclopropylamino.
  • Alkylaminocarbonyl alkyl-NH-CO-, for example CH 3 NHCO-.
  • Alkylaminosulfonyl alkyl -NH-S(O) 2 -, for example CH 3 NH S(O) 2 -.
  • Alkoxyalkyl alkyl-O-alkyl-, for example CH 3 OCH 2 -.
  • Halogenated alkoxyalkyl linear or branched alkoxyalkyl, the hydrogen atoms on these alkoxyalkyls can be partially or completely replaced by halogens, such as chloromethoxymethyl, dichloromethoxy Methyl, trichloromethoxymethyl, fluoromethoxymethyl, difluoromethoxymethyl, trifluoromethoxymethyl, chlorofluoromethoxymethyl, trifluoroethoxymethyl, etc. .
  • Alkoxyalkoxy alkyl-O-alkyl-O-, for example CH 3 OCH 2 O-.
  • Alkylsulfonyl alkyl-S(O) 2 -, such as methylsulfonyl.
  • Aryl a monocyclic or polycyclic aromatic group with 6-20 carbon atoms, such as phenyl and naphthyl.
  • Heteroaryl a monocyclic or polycyclic heteroaromatic group with 1-20 carbon atoms, 1-4 selected from N, S, O heteroatoms, such as pyrrolyl, furyl, thienyl, imidazolyl, Pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyridazinone, indolyl, benzofuranyl, benzoxazolyl, Benzothiophene, benzothiazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, benzopyrazolyl, quinoxalinyl and the like.
  • C 1 -C 4 alkyl substituted phenyl refers to the phenyl group can be substituted by 1-5 different or the same C 1 -C 4 alkyl group, such as 4-methylphenyl, 2-methyl-3ethyl Phenyl.
  • Arbitrarily substituted aryl any position of the aryl group can be substituted by any number of substituents.
  • the compound of general formula I of the present invention can be prepared according to the following method, unless otherwise noted, the definition of each group in the formula is the same as before.
  • the compound of general formula II and the compound of general formula III are reacted in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to prepare a compound of general formula I.
  • the compound of formula IV containing amino group is reacted with W and Q in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to prepare a compound of formula II.
  • the reaction can be carried out in the presence or absence of a base.
  • the compound of general formula IV and the compound of general formula III are reacted in a suitable solvent at a temperature from -10°C to the boiling point of the solvent for 0.5-48 hours to prepare a compound of general formula V.
  • LG represents a leaving group
  • a suitable leaving group can be selected from halogen or other conventional nucleating groups, such as methanesulfonic acid group or toluenesulfonic acid group.
  • M represents a cation, such as Na + , K + , CS + , Ag + or NH 4 + and the like.
  • Suitable solvents can be aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; halogenated aromatic hydrocarbons such as chloroform and dichloromethane; and esters such as methyl acetate and ethyl acetate.
  • Ethers such as tetrahydrofuran, dioxane, diethyl ether, 1,2-dimethoxyethane, water, acetonitrile, N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, etc.
  • Organic bases such as triethylamine, pyridine, DBU, DMAP, alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, Alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate, and metal alkoxides such as sodium methoxide and potassium ethoxide.
  • alkali metal hydrides such as sodium hydride and potassium hydride
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • Alkaline earth metal hydroxides such as calcium hydroxide
  • alkali metal carbonates such as sodium carbonate and potassium carbonate
  • alkali metal bicarbonates such as sodium bicarbonate
  • metal alkoxides such as sodium methoxide and potassium ethoxide.
  • Compounds of general formula III can be purchased or prepared according to known methods (for example: CN103804321, WO2008139481, US20130096098 or Journal of the Chemical Society of Pakistan, 33(3), 324-332, 2011, etc.).
  • the compound of general formula IV can be purchased or prepared according to a known method (for example: CN 101885708A or Journal of Medicinal Chemistry, 59(21), 9686-9720; 2016).
  • the compound of the present invention or its salt is used to control plant diseases, and can be used to prevent and control diseases caused by various fungi such as Oomycetes, Basidiomycetes, Ascomycetes and Deuteromycetes on a variety of crops.
  • Low doses of cucumber downy mildew, cucumber gray mold, cucumber anthracnose, cucumber powdery mildew, tomato early blight, tomato late blight, pepper blight, grape downy mildew, grape white rot, apple ring pattern, apple spot Diseases such as leaf fall disease, rice sheath blight, rice blast, wheat rust, wheat leaf spot, wheat powdery mildew, rape sclerotium, and corn spot disease are all well controlled.
  • the compound of the present invention also has good bactericidal activity, and can be used to prevent and treat a variety of plant bacterial diseases, such as bacterial wilt, bacterial blight, ulcer, soft rot, bacterial angular leaf spot, bacterial streak, Leaf blight, wildfire and bacterial scab disease, etc., including rice bacterial leaf streak, rice bacterial leaf blight, rice basal rot, rice bacterial brown streak, rice bacterial brown spot, potato bacterial wilt Disease, potato soft rot, potato black shank, potato ring rot, citrus canker, pear root cancer, pear fire blight, peach bacterial perforation, kiwi canker, walnut black spot, fruit tree bacterial root cancer Diseases, watermelon bacterial wilt, watermelon bacterial fruit rot, solanaceae vegetable bacterial wilt, cucumber bacterial angular leaf spot, melon bacterial angular leaf spot, cruciferous vegetable soft rot, bacterial black rot ,
  • the present invention also provides a bactericidal composition, which contains the compound of general formula I or its salt and an agriculturally acceptable carrier, and the compound of general formula I or its salt is used as the active component.
  • the weight percentage of the active component is 0.1-99%.
  • Example 8 Determination of the control effect on plant bacterial diseases
  • the compound of the present invention has been used for the prevention and control of a variety of plant bacterial diseases.
  • the test procedure is as follows:
  • melon fruit spot disease For melon fruit spot disease, dissolve the test compound with a small amount of N,N dimethylformamide and dilute with water to the required concentration. The pathogenic bacteria cultivated to the stable growth period are mixed with the quantitative compound solution, and the melon seeds that have been germinated are soaked in the mixture of the bacterial solution and the compound for half an hour, and then the seeds are sown in the earthworm soil culture cup and placed in the greenhouse Medium moisturizing culture, generally cultured for two weeks, after the control has fully developed the disease, the control effect will be investigated.
  • the type of solvent is acetone, methanol, DMF, etc., depending on its ability to dissolve the sample, and the volume ratio of solvent volume to spray volume is equal to or less than 0.05.
  • the compound of the present invention is used for foliar spray treatment according to the designed concentration.
  • a blank control sprayed with clean water was set up, repeated 3 times, and the disease was inoculated on the second day after treatment.
  • the plants were placed in an artificial climate room for moisturizing culture (temperature: day 25 °C, night 20 °C, relative humidity 95-99% ). After the test materials were cultivated for 24 hours, they were transferred to the greenhouse for cultivation, and plants that did not need to be moisturized for cultivation were directly inoculated and cultivated in the greenhouse. After the control is fully onset (usually within a week), the compound's control effect will be evaluated. The result of the investigation is referred to the "A Manual of Assessment Keys for Plant Diseases" compiled by the American Society of Phytopathology, which is represented by 100-0 and represented by "100" No disease and "0" grade represent the most severe disease severity.
  • the following compounds at a concentration of 400ppm such as compounds 10, 16, 19, 20, 22, 23, 34, 36, 47, 57, 65, 86, 87, 95, 98, 100, 117, 179, 363, 364, and 365 have good control effects on soybean rust, and the control effect is ⁇ 80%.
  • the following compounds at a concentration of 400ppm such as compounds 10, 16, 19, 20, 22, 23, 36, 45, 47, 57, 65, 86, 87, 95, 97, 98, 100, 117, 123, 134, 179, and 365 have good control effect on cucumber downy mildew, and the control effect is ⁇ 80%,
  • Example 10 Field trial of bacterial angular leaf spot of cucumber
  • the compound 47 and 97 were selected from the above-mentioned compounds for field verification test.
  • the control object is cucumber bacterial angular spot disease (Pseudomonas syringae pv.lachrymans).
  • the treatment dose of the test agent is 400 mg/L
  • the treatment dose of the control agent CK2 is 700 mg/L.
  • the test agent and the control agent are arranged in random blocks, the area of the block: 15m 2 , 3 repeats.
  • the spraying method of the whole plant is the spraying of the whole plant, with a total of three sprays, 7 days apart, and the control effect investigation is carried out 7 days after the last spray. During the investigation, samples were taken at 5 points in each plot, all leaves were investigated, and the diseased spot area of each leaf was classified according to the percentage of the entire leaf area, and the disease index and control effect were calculated. The results are shown in Table 5

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Abstract

本发明公开了一种结构新颖的肟醚类化合物，结构如通式(I)所示，式中各取代基的定义见说明书。通式(I)化合物具有优异的杀菌活性，对植物细菌病害和真菌病害具有良好的防治效果，本发明包括通式(I)化合物在农业和其它领域中用作杀菌剂的用途。

Description

一种肟醚类化合物及其用途 技术领域
本发明属农用杀菌剂领域。具体地涉及一种肟醚类化合物及其用途。
背景技术
肟醚衍生物是一类具有广谱生物活性的化合物，在农药中被广泛应用于杀虫剂、除草剂及杀菌剂。自从1974年美国杜邦公司开发的第一个商品化肟醚杀菌剂霜脲氰(Cymoxan)问世以来，不断有新的商品化品种出现。
专利CN106916084A公开了如下化合物CK1、CK2和CK3(分别为CN106916084A表1中化合物编号：107、115和116)，该类化合物对细菌病害和真菌病害有良好的活性。
Figure PCTCN2020125780-appb-000001
现有技术中，如本发明所示的肟醚类化合物及其杀菌活性未见报道。
发明内容
本发明的目的是提供一种结构新颖肟醚类化合物，它可用于制备农业和其它领域中防治病菌的药物。
为实现上述目的，本发明的技术方案如下：
一种肟醚类化合物，其特征在于：化合物如通式I所示：
Figure PCTCN2020125780-appb-000002
式中：
X选自硫或氧；
Z选自氢、未取代或被任意个下述基团取代的C 1-C 6的直链或支链烷基：卤素、氰基、三氟甲基、三氟甲氧基、羟基、硝基、氨基；
A选自CN、(C＝O)OR 1、(C＝O)NHR 2或(C＝O)NHNH 2；
R 1选自C 1-C 8烷基；
R 2选自氢或C 1-C 8烷基；
W选自氢、乙腈、C 1-C 8烷基、C 1-C 8卤代烷基、C 3-C 6环烷基、C 2-C 8烯基、C 2-C 8卤代烯基、C 2-C 8炔基、C 2-C 8卤代炔基、C 1-C 8烷氧基C 1-C 8烷基、C(＝O)R 3、C(＝O)CH 2R 3、C(＝O)CH 2OR 3、NO 2、OR 4、S(O) 2R 5、N(R 6)R 7或N＝C(R 8)R 9；
Q选自氢、乙腈、C 1-C 8烷基、C 1-C 8卤代烷基、C 3-C 6环烷基、C 2-C 8烯基、C 2-C 8卤代烯基、C 2-C 8炔基、C 2-C 8卤代炔基、C 1-C 8烷氧基C 1-C 8烷基或C(＝O)R 3；
或，Q、N和N相连的W形成3-6元饱和或不饱和环，所述饱和或不饱和环含有0-2个N-R 10、O、S或氧化的S，同时该环还可被R 11取代或与苯环形成并环；
R 3选自氢、C 1-C 8烷基、C 1-C 8卤代烷基、C 3-C 6环烷基、C 2-C 8烯基、C 2-C 8卤代烯基、C 2-C 8炔基、C 2-C 8卤代炔基、C 1-C 8烷氧基C 1-C 8烷基、N(R 12)R 13、任意取代的芳基或任意取代的杂芳基；
R 4选自氢、C 1-C 8烷基、C 1-C 8卤代烷基或C 3-C 6环烷基；
R 5选自C 1-C 2烷基、C 1-C 2卤代烷基、C 3-C 6环烷基、C 1-C 4烷氧基、C 1-C 4烷基取代的苯基或N(R 12)R 13；
R 6选自氢或C 1-C 8烷基；
R 7选自氢或C 1-C 8烷基；
R 8选自氢、C 1-C 8烷基、C 1-C 8卤代烷基、未取代的或被下述基团任意取代的苯基，其中，下述基团为氢、卤素、氰基、硝基、C 1-C 4烷基或C 1-C 4卤代烷基；
R 9选自C 1-C 8烷基、C 1-C 8卤代烷基、未取代的或被下述基团任意取代的苯基，其中，下述基团为氢、卤素、氰基、硝基、C 1-C 4烷基或C 1-C 4卤代烷基；
R 10为氢、C 1-C 2烷基、C 1-C 2卤代烷基、C 1-C 2烷基羰基或C 1-C 2烷氧基羰基；
R 11为H、卤素、CN、NO 2、C 1-C 2烷基、C 1-C 2卤代烷基、C 1-C 4烷氧基、C 1-C 2卤代烷氧基、任意取代的芳基或S(O)nR 14，其中n为0、1或2；
R 12选自C 1-C 8烷基；
R 13选自C 1-C 8烷基；
R 14为氢、C 1-C 2烷基、C 1-C 2卤代烷基、C 3-C 6环烷基或C 1-C 4烷氧基；
或通式I化合物的盐。
本发明中较可选的化合物为：通式I中
X选自硫或氧；
Z选自氢、未取代或被任意个下述基团取代的C 1-C 3的直链或支链烷基：卤素、氰基、三氟甲基、三氟甲氧基、羟基、硝基、氨基；
A选自CN、(C＝O)OR 1、(C＝O)NHR 2或(C＝O)NHNH 2；
R 1选自C 1-C 4烷基；
R 2选自氢或C 1-C 4烷基；
W选自氢、乙腈、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、C 2-C 4烯基、C 2-C 4卤代烯基、C 2-C 4炔基、C 2-C 4卤代炔基、C 1-C 4烷氧基C 1-C 4烷基、C(＝O)R 3、C(＝O)CH 2R 3、C(＝O)CH 2OR 3、NO 2、OR 4、S(O) 2R 5、N(R 6)R 7或N＝C(R 8)R 9；
Q选自氢、乙腈、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、C 2-C 4烯基、C 2-C 4卤代烯基、C 2-C 4炔基、C 2-C 4卤代炔基、C 1-C 4烷氧基C 1-C 4烷基或C(＝O)R 3；
或，Q、N和N相连的W形成3-6元饱和或不饱和环，所述饱和或不饱和环含有0-2个N-R 10、O、S或氧化的S，同时该环还可被R 11取代或与苯环形成并环；
R 3选自氢、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、C 2-C 4烯基、C 2-C 4卤代烯基、C 2-C 4炔基、C 2-C 4卤代炔基、C 1-C 4烷氧基C 1-C 4烷基、N(R 12)R 13或选自未取代的或被下述基团任意取代的苯基、吡啶基、吡唑基、噻唑基、异噻唑基或噻二唑基，其中，下述基团为氢、卤素、氰基、硝基、羟基、巯基、氨基、醛基、C(＝O)NH 2、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、C 1-C 3烷氧基、C 1-C 3卤代烷氧基、C 1-C 3烷硫基、C 1-C 3卤代烷硫基、C 1-C 3烷基氨基、C 1-C 3二烷基氨基、C 3-C 6环烷基氨基、C 1-C 3烷氧基羰基、C 1-C 3烷基磺酰基、C 1-C 3烷基氨基羰基、C 1-C 3烷基氨基磺酰基、未取代或被下述基团任意取代的苯基或吡啶基，下述基团为氢、卤素、氰基、硝基、C 1-C 4烷基或C 1-C 4卤代烷基；
R 4选自氢、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基；
R 5选自C 1-C 2烷基、C 1-C 2卤代烷基、C 3-C 6环烷基、C 1-C 4烷氧基、C 1-C 4烷基取代的苯基或N(R 12)R 13；
R 6选自氢或C 1-C 4烷基；
R 7选自氢或C 1-C 4烷基；
R 8选自氢、C 1-C 4烷基、C 1-C 4卤代烷基、未取代的或被下述基团任意取代的苯基，其中，下述基团为氢、卤素、氰基、硝基；
R 9选自C 1-C 4烷基、C 1-C 4卤代烷基、未取代的或被下述基团任意取代的苯基，其中，下述基团为氢、卤素、氰基、硝基；
R 10为氢、C 1-C 2烷基、C 1-C 2卤代烷基、C 1-C 2烷基羰基或C 1-C 2烷氧基羰基；
R 11为H、卤素、CN、NO 2、C 1-C 2烷基、C 1-C 2卤代烷基、C 1-C 4烷氧基、C 1-C 2卤代烷氧基、任意取代的芳基或S(O)nR 14，其中n为0、1或2；
R 12选自C 1-C 4烷基；
R 13选自C 1-C 4烷基；
R 14为氢、C 1-C 2烷基、C 1-C 2卤代烷基、C 3-C 6环烷基或C 1-C 4烷氧基；
或通式I化合物的盐。
本发明中进一步可选的化合物为：通式I中
X选自氧或硫；
Z选自氢、甲基或乙基；
A选自CN、(C＝O)OR 1、(C＝O)NHR 2或(C＝O)NHNH 2；
R 1选自甲基或乙基；
R 2选自氢、甲基或乙基；
W选自氢、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、C(＝O)R 3、OR 4、S(O) 2R 5、N(R 6)R 7或N＝C(R 8)R 9；
Q选自氢、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基或C(＝O)R 3；
或，Q、N和N相连的W形成3-6元饱和或不饱和环，所述饱和或不饱和环含有0-2个N-R 10、O、S或氧化的S，同时该环还可与苯环形成并环；
R 3选自C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、N(R 12)R 13、未取代的或被下述基团任意取代的苯基、吡啶基、吡唑基、噻唑基、异噻唑基或噻二唑基：下述基团为氢、卤素、氰基、硝基、C(＝O)NH 2、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、C 1-C 3烷氧基、C 1-C 3卤代烷氧基、C 1-C 3烷硫基、C 1-C 3卤代烷硫基、C 1-C 3烷基氨基、C 1-C 3二烷基氨基、C 3-C 6环烷基氨基、C 1-C 3烷氧基羰基、C 1-C 3烷基磺酰基、C 1-C 3烷基氨基羰基、C 1-C 3烷基氨基磺酰基、未取代或被以下基团任意取代的苯基、吡啶基：以下基团为氢、卤素、氰基、硝基、C 1-C 4烷基或C 1-C 4卤代烷基；
R 4选自氢、C 1-C 4烷基或C 1-C 4卤代烷基；
R 5选自C 1-C 2烷基、C 1-C 2卤代烷基、甲基取代的苯基或N(R 11)R 12；
R 6选自氢、甲基或乙基；
R 7选自氢、甲基或乙基；
R 8选自甲基、乙基、三氟甲基、未取代或被下述基团任意取代的苯基：下述基团为氢、卤素、氰基、硝基；
R 9选自甲基、乙基、三氟甲基、未取代或被下述基团任意取代的苯基：下述基团为氢、卤素、氰基、硝基；
R 12选自甲基或乙基；
R 13选自甲基或乙基。
或通式I化合物的盐。
本发明中进一步可选的化合物为：通式I中
X选自氧或硫；
Z选自氢；
A选自CN、(C＝O)OR 1或(C＝O)NH 2；
R 1选自甲基或乙基；
W选自氢、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、C(＝O)R 3、S(O) 2R 5、N(R 6)R 7或N＝C(R 8)R 9；
Q选自氢、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基或C(＝O)R 3；
R 3选自C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、N(R 12)R 13、未取代的或被下述基团任意取代的苯基、吡啶基、吡唑基、噻唑基、异噻唑基或噻二唑基：下述基团为氢、 卤素、氰基、硝基、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4烷氧基、C 1-C 4卤代烷氧基、C 1-C 4烷硫基或C 1-C 4卤代烷硫基；
R 5选自C 1-C 2烷基、C 1-C 2卤代烷基、对甲基苯基或N(R 12)R 13；
R 6选自氢、甲基或乙基；
R 7选自氢、甲基或乙基；
R 8选自甲基、乙基、三氟甲基、未取代或被下述基团任意取代的苯基：下述基团为氢、卤素、氰基、硝基；
R 9选自甲基、乙基、三氟甲基、未取代或被下述基团任意取代的苯基：下述基团为氢、卤素、氰基、硝基；
R 12选自甲基或乙基；
R 13选自甲基或乙基；
或通式I化合物的盐。
本发明中更进一步可选的化合物为：通式I中
X选自硫；
Z选自氢；
A选自CN或(C＝O)NH 2；
W选自氢、C 1-C 4烷基、C 3-C 6环烷基、C(＝O)R 3或N＝C(R 8)R 9；
Q选自氢、C 1-C 4烷基、C 3-C 6环烷基或C(＝O)R 3；
R 3选自C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、未取代的或被下述基团任意取代的苯基、吡啶基、吡唑基、噻唑基、异噻唑基或噻二唑基：下述基团为氢、卤素、氰基、硝基、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4烷氧基、C 1-C 4卤代烷氧基、C 1-C 4烷硫基或C 1-C 4卤代烷硫基；
R 8选自甲基、乙基、三氟甲基、未取代或被下述基团任意取代的苯基：下述基团为氢、卤素、氰基、硝基；
R 9选自甲基、乙基、三氟甲基、未取代或被下述基团任意取代的苯基：下述基团为氢、卤素、氰基、硝基；
或通式I化合物的盐。
本发明中再进一步可选的化合物为：通式I中
X选自硫；
Z选自氢；
A选自CN或(C＝O)NH 2；
W选自氢、C 1-C 4烷基或C(＝O)R 3；
Q选自氢、C 1-C 4烷基或C(＝O)R 3；
R 3选自C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、K 1-K 10所示任意一个基团、未取代或被下述基团任意取代的苯基或吡啶基：下述基团为卤素、氰基、硝基、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4烷氧基、C 1-C 4卤代烷氧基、C 1-C 4烷硫基或C 1-C 4卤代烷硫基；
K 1-K 10表示如下：
Figure PCTCN2020125780-appb-000003
或通式I化合物与盐酸、氢溴酸、硫酸、磷酸、甲酸、乙酸、丙酸、丁酸、戊酸、三氟乙酸、草酸、丙二酸、甲磺酸、4-甲苯磺酸、苹果酸、富马酸、乳酸、马来酸、水杨酸、酒石酸或柠檬酸形成的盐。
上面给出的通式化合物的定义中，汇集所用术语一般代表如下取代基：
未取代表示所有取代基都为氢。
卤素：指氟、氯、溴或碘。
烷基：直链或支链烷基，例如甲基、乙基、正丙基、异丙基或不同的丁基、戊基或己基异构体。
卤代烷基：直链或支链烷基，在这些烷基上的氢原子可部分或全部被卤素所取代，例如氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基、七氟异丙基等。
环烷基：取代或未取代的环状烷基，例如环丙基、环戊基或环己基；取代基如甲基、卤素等。
烯基：包括直链或支链烯类，例如乙烯基、1-丙烯基、2-丙烯基和不同的丁烯基、戊烯基和己烯基异构体；烯基还包括多烯类如1,2-丙二烯基和2,4-己二烯基。
卤代烯基：可被卤原子取代至少一个或多个氢原子的烯基。
炔基：包括直链或支链炔类，如乙炔基、1-丙炔基和不同的丁炔基、戊炔基和己炔基异构体；炔基还包括由多个三键组成的基团，例如2,5-己二炔基。
卤代炔基：可被卤原子取代至少一个或多个氢原子的炔基。
烷氧基：直链或支链烷基，经氧原子键连接到结构上，例如甲氧基、乙氧基、叔丁氧基等。
卤代烷氧基：直链或支链烷氧基，在这些烷氧基上的氢原子可部分或全部被卤素所取代，例如氯甲氧基、二氯甲氧基、三氯甲氧基、氟甲氧基、二氟甲氧基、三氟甲氧基、氯氟甲氧基、三氟乙氧基等。
烷硫基：直链或支链烷基，经硫原子键连接到结构上，例如甲硫基、乙硫基等。
卤代烷硫基：直链或支链烷硫基，在这些烷硫基上的氢原子可部分或全部被卤素所 取代，例如二氟甲硫基、三氟乙硫基等。
烷基氨基：直链或支链烷基，经氮原子键连接到结构上，例如甲基氨基、乙基氨基、正丙基氨基、异丙基氨基或同分异构的丁基胺。
二烷基氨基：两个相同或不同的直链或支链烷基，经氮原子键连接到结构上，例如二甲基氨基、甲基乙基氨基等。
环烷基氨基：环烷基-NH-，例如环丙氨基。
烷基氨基羰基：烷基-NH-CO-，例如CH 3NHCO-。
烷基氨基磺酰基：烷基-NH-S(O) 2-，例如CH 3NH S(O) 2-。
烷氧基烷基：烷基-O-烷基-，例如CH 3OCH 2-。
卤代烷氧基烷基：直链或支链烷氧基烷基，在这些烷氧基烷基上的氢原子可部分或全部被卤素所取代，例如氯甲氧基甲基、二氯甲氧基甲基、三氯甲氧基甲基、氟甲氧基甲基、二氟甲氧基甲基、三氟甲氧基甲基、氯氟甲氧基甲基、三氟乙氧基甲基等。
烷氧基烷氧基：烷基-O-烷基-O-，例如CH 3OCH 2O-。
烷氧基羰基：烷基-O-(C＝O)-，例如CH 3O(C＝O)-。
烷基磺酰基：烷基-S(O) 2-，例如甲基磺酰基。
芳基：具有6-20个碳原子的单环或多环芳族基团，例如苯基、萘基。
杂芳基：具有1-20个碳原子、1-4个选自N、S、O杂原子的单环或多环杂芳族基团，例如吡咯基、呋喃基、噻吩基、咪唑基、吡唑基、噁唑基、噻唑基、异噁唑基、异噻唑基、吡啶基、嘧啶基、哒嗪基、哒嗪酮基、吲哚基、苯并呋喃基、苯并噁唑基、苯并噻吩基、苯并噻唑基、苯并异噁唑基、苯并异噻唑基、苯并咪唑基、苯并吡唑基、喹喔啉基等。
C 1-C 4烷基取代的苯基：指苯基可被1-5个不同或相同的C 1-C 4烷基取代，例如4-甲基苯基、2-甲基-3乙基苯基。
任意取代的芳基：芳基任意位上可由任意个取代基取代。
被任意取代的C 1-C 6的直链或支链烷基：C 1-C 6的直链或支链烷基上各个C原子可由任意个取代基进行取代。
本发明部分通式I化合物如表1所示，但本发明绝非仅限于这些化合物。
表1
Figure PCTCN2020125780-appb-000004
Figure PCTCN2020125780-appb-000005
Figure PCTCN2020125780-appb-000006
Figure PCTCN2020125780-appb-000007
Figure PCTCN2020125780-appb-000008
Figure PCTCN2020125780-appb-000009
Figure PCTCN2020125780-appb-000010
Figure PCTCN2020125780-appb-000011
Figure PCTCN2020125780-appb-000012
Figure PCTCN2020125780-appb-000013
Figure PCTCN2020125780-appb-000014
Figure PCTCN2020125780-appb-000015
Figure PCTCN2020125780-appb-000016
Figure PCTCN2020125780-appb-000017
部分化合物的 1H NMR及物化性质如下：
表2
Figure PCTCN2020125780-appb-000018
Figure PCTCN2020125780-appb-000019
本发明的通式I化合物可按照以下方法制备，除另有注明外，式中各基团的定义同前。
方法一:
Figure PCTCN2020125780-appb-000020
通式II化合物与通式III化合物在适宜的溶剂中，在温度从-10℃到溶剂沸点下反应0.5-48小时制得通式I化合物。
Figure PCTCN2020125780-appb-000021
含有氨基的通式IV化合物与W和Q在适宜的溶剂中，在温度从-10℃到溶剂沸点下反应0.5-48小时制得通式II化合物，反应可在碱存在或非存在下进行。
方法二:
Figure PCTCN2020125780-appb-000022
含有氨基通式化合物V与W和Q在适宜的溶剂中，在温度从-10℃到溶剂沸点下反应0.5-48小时制得通式I化合物，反应可在碱存在或非存在下进行。
Figure PCTCN2020125780-appb-000023
通式IV化合物与通式III化合物在适宜的溶剂中，在温度从-10℃到溶剂沸点下反应0.5-48小时制得通式V化合物。
上述制备方法中：LG表示离去基团，合适的离去基团可选自卤素或其它常规的离核基团，例如甲磺酸基或甲苯磺酸基等。M表示阳离子，例如Na +、K +、CS +、Ag +或NH 4 +等。适宜的溶剂可可为苯、甲苯、二甲苯等芳烃类，丙酮、甲乙酮、甲基异丁酮等酮类，氯仿、二氯甲烷等卤代芳烃类，乙酸甲酯、乙酸乙酯等酯类，四氢呋喃、二噁烷、二乙醚、1，2-二甲氧基乙烷等醚类，水、乙腈、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二甲基亚砜等极性溶剂或上述溶剂的混合溶剂；碱可为三乙胺、吡啶、DBU、DMAP等有机碱，氢化钠、氢化钾等碱金属氢化物，氢氧化钠、氢氧化钾等碱金属氢氧化物，氢氧化钙等碱土类金属氢氧化合物，碳酸钠、碳酸钾等碱金属碳酸盐，碳酸氢钠等碱金属碳酸氢盐，甲醇钠、乙醇钾等金属醇盐。
通式III化合物可以购买或按公知方法(例如：CN103804321、WO2008139481、US20130096098或Journal of the Chemical Society of Pakistan,33(3),324-332,2011等)制 备。
通式IV化合物可以通过购买或按公知的方法(例如：CN 101885708A或Journal of Medicinal Chemistry,59(21),9686-9720；2016)制备。
本发明的化合物或其盐用于控制植物病害的用途，可用于防治在多种作物上由卵菌纲、担子菌纲、子囊菌和半知菌类等多种真菌引起的病害，例如在较低剂量下对黄瓜霜霉病、黄瓜灰霉病、黄瓜炭疽病、黄瓜白粉病、番茄早疫病、番茄晚疫病、辣椒疫病、葡萄霜霉病、葡萄白腐病、苹果轮纹病、苹果斑点落叶病、水稻纹枯病、水稻稻瘟病、小麦锈病、小麦叶斑病、小麦白粉病、油菜菌核病、玉米小斑病等病害都有着很好的防效。
本发明化合物还具有很好的杀细菌活性，可用于防治多种植物细菌性病害，例如青枯病、细菌性疫病、溃疡病、软腐病、细菌性角斑病、细菌性条斑病、叶枯病、野火病和细菌性疮痂病等，具体包括水稻细菌性条斑病、水稻白叶枯病、水稻基腐病、水稻细菌性褐条病、水稻细菌性褐斑病、马铃薯青枯病、马铃薯软腐病、马铃薯黑胫病、马铃薯环腐病、柑桔溃疡病、梨根癌病、梨火疫病、桃细菌性穿孔病、猕猴桃溃疡病、核桃黑斑病、果树细菌性根癌病、西瓜细菌性青枯病、西瓜细菌性果腐病、茄科蔬菜青枯病、黄瓜细菌性角斑病、甜瓜细菌性角斑病、十字花科蔬菜软腐病、细菌性黑腐病、细菌性黑斑病、花卉类细菌性病害等。
本发明还提供了一种杀菌组合物，该组合物中含有通式I的化合物或其盐和农业上可接受的载体，以通式I所示化合物或其盐为活性组分，组合物中活性组分的重量百分含量为0.1-99％。
具体实施方式
以下具体实施例用来进一步说明本发明，但不意味着限制本发明。
合成实施例
实施例1：化合物34的制备
Figure PCTCN2020125780-appb-000024
在50毫升反应瓶中加入((2-氨基噻唑-4-基)甲氧基)亚氨基酰亚胺二氰化物(0.5克，2.41毫摩尔)、三乙胺(0.37克，3.66毫摩尔)、DMAP(0.3克，2.46毫摩尔)和20毫升二氯甲烷，然后开动搅拌，然后将2.4-二氯苯甲酰氯(0.5克，2.39毫摩尔)溶于10毫升二氯甲烷中，冰浴条件下，向反应瓶中滴加酰氯溶液，滴毕继续室温搅拌反应，TLC(乙酸乙酯:石油醚＝1:5)监测，待反应完成后，减压蒸除溶剂，残余物柱色谱(乙酸乙酯:石油醚＝1:5作洗脱剂，青岛海洋生物化工厂分厂生产的100-140目硅胶)纯化得黄色固体0.42克，产率46％。
实施例2：化合物47的制备
中间体4-(氯甲基)噻唑-2-氨基盐酸盐的制备
Figure PCTCN2020125780-appb-000025
在100毫升反应瓶中加入硫脲(6.49克，85.26毫摩尔)和甲醇40毫升，然后将1，3-二氯丙酮(10.83克，85.26毫摩尔)溶于30毫升丙酮中，冰浴条件下将1，3-二氯丙酮溶液缓慢滴加到硫脲溶液中，滴毕撤去冰浴继续搅拌，室温搅拌过夜，旋干除去溶剂，然后将20毫升丙酮加入到残余物中，剧烈搅拌直至固体析出，然后抽滤晾干得白色固体13.5克，产率86％。
Figure PCTCN2020125780-appb-000026
在50毫升反应瓶中加入4-(氯甲基)噻唑-2-氨基盐酸盐(0.5克，2.7毫摩尔)、丙二腈肟醚钠盐(0.32克，2.7毫摩尔)、三乙胺(0.28克，2.77毫摩尔)和15毫升乙腈，升温至60℃搅拌反应，TLC(乙酸乙酯:石油醚＝1﹕1)监测，待反应完成后，减压蒸除溶剂，残余物柱色谱(乙酸乙酯:石油醚＝1:2作洗脱剂，青岛海洋生物化工厂分厂生产的100-140目硅胶)纯化得黄色固体0.21克，产率37％。
实施例3：化合物97的制备
Figure PCTCN2020125780-appb-000027
在50毫升反应瓶中加入((2-氨基噻唑-4-基)甲氧基)亚氨基酰亚胺二氰化物(0.27克，1.30毫摩尔)、三乙胺(0.19克，1.88毫摩尔)、DMAP(0.16克，1.31毫摩尔)和20毫升二氯甲烷，然后开动搅拌，然后将4-叔丁基苯甲酰氯(0.25克，1.27毫摩尔)溶于10毫升二氯甲烷中，冰浴条件下，向反应瓶中滴加酰氯溶液，滴毕继续室温搅拌反应，TLC(乙酸乙酯:石油醚＝1:5)监测，待反应完成后，减压蒸除溶剂，残余物柱色谱(乙酸乙酯:石油醚＝1:5作洗脱剂，青岛海洋生物化工厂分厂生产的100-140目硅胶)纯化得黑色油状物0.22克，产率47％。
实施例4：化合物179的制备
Figure PCTCN2020125780-appb-000028
在50毫升反应瓶中加入4-(氯甲基)噻唑-2-氨基盐酸盐(0.45克，2.43毫摩尔)、氰基乙酰胺肟醚(0.28克，2.48毫摩尔)、碳酸钾(1.01克，7.29毫摩尔)和25毫升乙腈，65℃搅拌反应8个小时，待反应液冷却后用硅藻土过滤得到澄清溶液，然后减压除去溶剂,残余物经过二氯甲烷洗涤得到黄色固体0.22克，产率40％。
实施例5：化合物361的制备
Figure PCTCN2020125780-appb-000029
在50毫升反应瓶中加入4-氟苯乙酮(2克，14.48毫摩尔)、氨基硫脲(1.32克，14.48毫摩尔)、醋酸0.2毫升和35毫升乙醇，加热回流反应8个小时，待反应液冷却后有白色固体析出，然后过滤得到目标物2.2克，产率72％。
Figure PCTCN2020125780-appb-000030
将上一步得到缩合产物(1.2克，5.68毫摩尔)、1，3-二氯丙酮(0.72克，5.68毫摩尔)加入单口瓶中，然后加入50毫升乙醇，加热至60度反应8个小时，TLC(乙酸乙酯:石油醚＝1:5)监测，待反应完成后，减压蒸除溶剂，残余物柱色谱(乙酸乙酯:石油醚＝1:5作洗脱剂，青岛海洋生物化工厂分厂生产的100-140目硅胶)纯化得黑色油状物0.66克，产率41％。
Figure PCTCN2020125780-appb-000031
在50毫升反应瓶中加入上一步得到的氯化物(0.4克，1.41毫摩尔)、丙二腈肟醚钠盐(0.17克，1.41毫摩尔)和15毫升乙腈，升温至60℃搅拌反应，TLC(乙酸乙酯:石油醚＝1﹕3)监测，待反应完成后，减压蒸除溶剂，残余物柱色谱(乙酸乙酯:石油醚＝1:3作洗脱剂，青岛海洋生物化工厂分厂生产的100-140目硅胶)纯化得黑色油状物0.18克，产率37％。
实施例6：化合物363的制备
Figure PCTCN2020125780-appb-000032
在50毫升反应瓶中加入((2-氨基噻唑-4-基)甲氧基)亚氨基酰亚胺二氰化物(0.21克，1.01毫摩尔)、三乙胺(0.16克，1.58毫摩尔)、DMAP(0.13克，1.06毫摩尔)和20毫升二氯甲烷，然后开动搅拌，然后将4-甲酸甲酯苯甲酰氯(0.20克，1.01毫摩尔)溶于10毫升二氯甲烷中，冰浴条件下，向反应瓶中滴加酰氯溶液，滴毕继续室温搅拌反应，TLC(乙酸乙酯:石油醚＝1:5)监测，待反应完成后，减压蒸除溶剂，残余物柱色谱(乙酸乙酯:石油醚＝1:5作洗脱剂，青岛海洋生物化工厂分厂生产的100-140目硅胶)纯化得黄色固体0.18克，产率48％。
实施例7：化合物364的制备
Figure PCTCN2020125780-appb-000033
在50毫升反应瓶中加入4-(氯甲基)噻唑-2-氨基盐酸盐(0.4克，2.16毫摩尔)、三乙胺(0.54克，5.34毫摩尔)、DMAP(0.26克，2.13毫摩尔)和20毫升二氯甲烷，然后开动搅拌。将邻乙氧基苯甲酰氯(0.39克，2.11毫摩尔)溶于10毫升二氯甲烷，然后冰浴条件下，向反应瓶中滴加酰氯，滴加完毕继续室温搅拌反应，TLC(乙酸乙酯:石油醚＝1:5)监测，待反应完成后，减压除去溶剂，残余物柱色谱(乙酸乙酯:石油醚＝1:5作洗脱剂，青岛海洋生物化工厂分厂生产的100-140目硅胶)纯化得白色固体0.46克，产率73％。
Figure PCTCN2020125780-appb-000034
在50毫升反应瓶中加入N-(4-(氯甲基)噻唑-2-基)-2-乙氧基苯甲酰胺(0.45克，1.52毫摩尔)、丙二腈肟醚钠盐(0.18克，1.54毫摩尔)和15毫升乙腈，升温至60℃搅拌反应，TLC(乙酸乙酯:石油醚＝1:3)监测，待反应完成后，减压蒸除乙腈，残余物柱色谱(乙酸乙酯:石油醚＝1:3作洗脱剂，青岛海洋生物化工厂分厂生产的100-140目硅胶)纯化得黄色固体0.25克，产率46％。
按照上述实施例的记载以及发明内容中通式I的合成路线，将原料进行替换即可获得通式I所示的其它化合物。
生物活性测定
实施例8：对植物细菌病害防治效果的测定
用本发明的化合物对多种植物细菌性病害进行了防效测定，针对不同的细菌性病害，试验程序如下：
甜瓜果斑病，将待测化合物用少量N，N二甲基甲酰胺溶解，用水稀释至所需要的浓度。将培养至稳定生长期的病原细菌与定量化合物溶液混合均匀，将经过催芽的甜瓜种子放入菌液与化合物的混合液中浸泡半小时，再将种子播种于蚯蚓土培养杯中，放入温室中保湿培养，一般培养两周时间，待对照充分发病后进行防效调查。
大白菜软腐病，切取2厘米见方的白菜叶片，放入垫有双层滤纸的玻璃培养皿中。将用N，N二甲基甲酰胺溶解，并用水稀释至所需浓度的化合物喷雾于白菜叶片表面，于通风橱内晾干白菜叶片表面药液后，使用接种针在白菜叶片表面针刺造成伤口，将培养至稳定生长期的大白菜软腐病菌取5微升加入伤口内，进行接种。最后将试材放入培养箱中避光培养48小时，待对照充分发病后进行防效调查。
测试结果如下：
400mg/L时，如化合物4、5、6、20、22、23、34、36、45、47、65、74、86、87、95、97、99、104、117、118、119、123、134、179、228、253、361、366、367对大白菜软腐病防效为100％。
400mg/L时，如化合物4、5、6、20、22、23、34、36、45、47、65、74、86、87、95、97、99、104、117、118、119、123、134、179、228、253、361、366、367对甜瓜 果斑病防效为100％。
实施例9：对植物真菌病害防治效果的测定
采用活体盆栽测定方法即将带测的化合物样品用少量溶剂(溶剂的种类如丙酮、甲醇、DMF等，依据其对样品的溶解能力而选择，溶剂量与喷液量的体积比等于或小于0.05。)溶解，用含有0.1％的吐温80的水稀释，配制成所需浓度的待测液。用本发明化合物按照设计浓度进行叶面喷雾处理。另设喷清水的空白对照，3次重复，处理后第二天进行病害接种，接种后将植物放在人工气候室中保湿培养(温度：昼25℃、夜20℃，相对湿度95-99％)。试验材料培养24小时后，移置温室培养，将不需要保湿培养的植物直接在温室内接种并培养。待对照充分发病后(通常为一周时间)进行化合物防治效果评估，结果调查参照美国植病学会编写的《A Manual of Assessment Keys for Plant Diseases》，用100-0来表示，用“100”级代表无病和“0”级代表最严重的发病程度。
对大豆锈病防效：
部分供试的化合物，下列化合物在浓度为400ppm时，如化合物10、16、19、20、22、23、34、36、47、57、65、86、87、95、98、100、117、179、363、364、365对大豆锈病防治效果较好，防效≥80％。
按照以上方法，选取化合物10、23、47、179和365与已知化合物CK1进行防治大豆锈病平行比较，试验结果见表3
表3
Figure PCTCN2020125780-appb-000035
对黄瓜霜霉病防效：
部分供试的化合物，下列化合物在浓度为400ppm时，如化合物10、16、19、20、22、23、36、45、47、57、65、86、87、95、97、98、100、117、123、134、179、365对黄瓜霜霉病防治效果较好，防效≥80％，
按照以上方法，选取化合物20、45、97和117与已知化合物CK1、CK2及CK3进行防治黄瓜霜霉病平行比较，试验结果见表4
表4
Figure PCTCN2020125780-appb-000036
实施例10：黄瓜细菌性角斑病田间试验
从上述化合物中选择化合物47和97进行田间验证试验，防治对象为黄瓜细菌性角斑病(Pseudomonas syringae pv.lachrymans)，供试药剂处理剂量为400mg/L，对照药剂CK2处理剂量为700mg/L，试验药剂和对照药剂采用随机区组排列，小区面积：15m 2，3次重复。施药方式为全株喷雾处理，共施药三次，间隔7天，最后一次施药后7天进行防效调查。调查时，每小区5点取样，调查全部叶片，以每叶片病斑面积占整个叶面积百分率分级，计算病情指数和防效。结果见表5
表5
Figure PCTCN2020125780-appb-000037

Claims (9)

  1. 一种肟醚类化合物，其特征在于：化合物如通式I所示：
    Figure PCTCN2020125780-appb-100001
    式中：
    X选自硫或氧；
    Z选自氢、未取代或被任意个下述基团取代的C 1-C 6的直链或支链烷基：卤素、氰基、三氟甲基、三氟甲氧基、羟基、硝基、氨基；
    A选自CN、(C＝O)OR 1、(C＝O)NHR 2或(C＝O)NHNH 2；
    R 1选自C 1-C 8烷基；
    R 2选自氢或C 1-C 8烷基；
    W选自氢、乙腈、C 1-C 8烷基、C 1-C 8卤代烷基、C 3-C 6环烷基、C 2-C 8烯基、C 2-C 8卤代烯基、C 2-C 8炔基、C 2-C 8卤代炔基、C 1-C 8烷氧基C 1-C 8烷基、C(＝O)R 3、C(＝O)CH 2R 3、C(＝O)CH 2OR 3、NO 2、OR 4、S(O) 2R 5、N(R 6)R 7或N＝C(R 8)R 9；
    Q选自氢、乙腈、C 1-C 8烷基、C 1-C 8卤代烷基、C 3-C 6环烷基、C 2-C 8烯基、C 2-C 8卤代烯基、C 2-C 8炔基、C 2-C 8卤代炔基、C 1-C 8烷氧基C 1-C 8烷基或C(＝O)R 3；
    或，Q、N和N相连的W形成3-6元饱和或不饱和环，所述饱和或不饱和环含有0-2个N-R 10、O、S或氧化的S，同时该环还可被R 11取代或与苯环形成并环；
    R 3选自氢、C 1-C 8烷基、C 1-C 8卤代烷基、C 3-C 6环烷基、C 2-C 8烯基、C 2-C 8卤代烯基、C 2-C 8炔基、C 2-C 8卤代炔基、C 1-C 8烷氧基C 1-C 8烷基、N(R 12)R 13、任意取代的芳基或任意取代的杂芳基；
    R 4选自氢、C 1-C 8烷基、C 1-C 8卤代烷基或C 3-C 6环烷基；
    R 5选自C 1-C 2烷基、C 1-C 2卤代烷基、C 3-C 6环烷基、C 1-C 4烷氧基、C 1-C 4烷基取代的苯基或N(R 12)R 13；
    R 6选自氢或C 1-C 8烷基；
    R 7选自氢或C 1-C 8烷基；
    R 8选自氢、C 1-C 8烷基、C 1-C 8卤代烷基、未取代的或被下述基团任意取代的苯基，其中，下述基团为氢、卤素、氰基、硝基、C 1-C 4烷基或C 1-C 4卤代烷基；
    R 9选自C 1-C 8烷基、C 1-C 8卤代烷基、未取代的或被下述基团任意取代的苯基，其中，下述基团为氢、卤素、氰基、硝基、C 1-C 4烷基或C 1-C 4卤代烷基；
    R 10为氢、C 1-C 2烷基、C 1-C 2卤代烷基、C 1-C 2烷基羰基或C 1-C 2烷氧基羰基；
    R 11为H、卤素、CN、NO 2、C 1-C 2烷基、C 1-C 2卤代烷基、C 1-C 4烷氧基、C 1-C 2卤代烷氧基、任意取代的芳基或S(O)nR 14，其中n为0、1或2；
    R 12选自C 1-C 8烷基；
    R 13选自C 1-C 8烷基；
    R 14为氢、C 1-C 2烷基、C 1-C 2卤代烷基、C 3-C 6环烷基或C 1-C 4烷氧基；
    或通式I化合物的盐。
  2. 根据权利要求1所述的化合物，其特征在于，通式I中，
    X选自硫或氧；
    Z选自氢、未取代或被任意个下述基团取代的C 1-C 3的直链或支链烷基：卤素、氰基、三氟甲基、三氟甲氧基、羟基、硝基、氨基；
    A选自CN、(C＝O)OR 1、(C＝O)NHR 2或(C＝O)NHNH 2；
    R 1选自C 1-C 4烷基；
    R 2选自氢或C 1-C 4烷基；
    W选自氢、乙腈、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、C 2-C 4烯基、C 2-C 4卤代烯基、C 2-C 4炔基、C 2-C 4卤代炔基、C 1-C 4烷氧基C 1-C 4烷基、C(＝O)R 3、C(＝O)CH 2R 3、C(＝O)CH 2OR 3、NO 2、OR 4、S(O) 2R 5、N(R 6)R 7或N＝C(R 8)R 9；
    Q选自氢、乙腈、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、C 2-C 4烯基、C 2-C 4卤代烯基、C 2-C 4炔基、C 2-C 4卤代炔基、C 1-C 4烷氧基C 1-C 4烷基或C(＝O)R 3；
    或，Q、N和N相连的W形成3-6元饱和或不饱和环，所述饱和或不饱和环含有0-2个N-R 10、O、S或氧化的S，同时该环还可被R 11取代或与苯环形成并环；
    R 3选自氢、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、C 2-C 4烯基、C 2-C 4卤代烯基、C 2-C 4炔基、C 2-C 4卤代炔基、C 1-C 4烷氧基C 1-C 4烷基、N(R 12)R 13或选自未取代的或被下述基团任意取代的苯基、吡啶基、吡唑基、噻唑基、异噻唑基或噻二唑基，其中，下述基团为氢、卤素、氰基、硝基、羟基、巯基、氨基、醛基、C(＝O)NH 2、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、C 1-C 3烷氧基、C 1-C 3卤代烷氧基、C 1-C 3烷硫基、C 1-C 3卤代烷硫基、C 1-C 3烷基氨基、C 1-C 3二烷基氨基、C 3-C 6环烷基氨基、C 1-C 3烷氧基羰基、C 1-C 3烷基磺酰基、C 1-C 3烷基氨基羰基、C 1-C 3烷基氨基磺酰基、未取代或被下述基团任意取代的苯基或吡啶基，下述基团为氢、卤素、氰基、硝基、C 1-C 4烷基或C 1-C 4卤代烷基；
    R 4选自氢、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基；
    R 5选自C 1-C 2烷基、C 1-C 2卤代烷基、C 3-C 6环烷基、C 1-C 4烷氧基、C 1-C 4烷基取代的苯基或N(R 12)R 13；
    R 6选自氢或C 1-C 4烷基；
    R 7选自氢或C 1-C 4烷基；
    R 8选自氢、C 1-C 4烷基、C 1-C 4卤代烷基、未取代的或被下述基团任意取代的苯基，其中，下述基团为氢、卤素、氰基、硝基；
    R 9选自C 1-C 4烷基、C 1-C 4卤代烷基、未取代的或被下述基团任意取代的苯基，其中，下述基团为氢、卤素、氰基、硝基；
    R 10为氢、C 1-C 2烷基、C 1-C 2卤代烷基、C 1-C 2烷基羰基或C 1-C 2烷氧基羰基；
    R 11为H、卤素、CN、NO 2、C 1-C 2烷基、C 1-C 2卤代烷基、C 1-C 4烷氧基、C 1-C 2卤代烷氧基、任意取代的芳基或S(O)nR 14，其中n为0、1或2；
    R 12选自C 1-C 4烷基；
    R 13选自C 1-C 4烷基；
    R 14为氢、C 1-C 2烷基、C 1-C 2卤代烷基、C 3-C 6环烷基或C 1-C 4烷氧基；
    或通式I化合物的盐。
  3. 根据权利要求2所述的化合物，其特征在于，通式I中，
    X选自氧或硫；
    Z选自氢、甲基或乙基；
    A选自CN、(C＝O)OR 1、(C＝O)NHR 2或(C＝O)NHNH 2；
    R 1选自甲基或乙基；
    R 2选自氢、甲基或乙基；
    W选自氢、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、C(＝O)R 3、OR 4、S(O) 2R 5、N(R 6)R 7或N＝C(R 8)R 9；
    Q选自氢、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基或C(＝O)R 3；
    或，Q、N和N相连的W形成3-6元饱和或不饱和环，所述饱和或不饱和环含有0-2个N-R 10、O、S或氧化的S，同时该环还可与苯环形成并环；
    R 3选自C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、N(R 12)R 13、未取代的或被下述基团任意取代的苯基、吡啶基、吡唑基、噻唑基、异噻唑基或噻二唑基：下述基团为氢、卤素、氰基、硝基、C(＝O)NH 2、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、C 1-C 3烷氧基、C 1-C 3卤代烷氧基、C 1-C 3烷硫基、C 1-C 3卤代烷硫基、C 1-C 3烷基氨基、C 1-C 3二烷基氨基、C 3-C 6环烷基氨基、C 1-C 3烷氧基羰基、C 1-C 3烷基磺酰基、C 1-C 3烷基氨基羰基、C 1-C 3烷基氨基磺酰基、未取代或被以下基团任意取代的苯基、吡啶基：以下基团为氢、卤素、氰基、硝基、C 1-C 4烷基或C 1-C 4卤代烷基；
    R 4选自氢、C 1-C 4烷基或C 1-C 4卤代烷基；
    R 5选自C 1-C 2烷基、C 1-C 2卤代烷基、甲基取代的苯基或N(R 11)R 12；
    R 6选自氢、甲基或乙基；
    R 7选自氢、甲基或乙基；
    R 8选自甲基、乙基、三氟甲基、未取代或被下述基团任意取代的苯基：下述基团为氢、卤素、氰基、硝基；
    R 9选自甲基、乙基、三氟甲基、未取代或被下述基团任意取代的苯基：下述基团为氢、卤素、氰基、硝基；
    R 12选自甲基或乙基；
    R 13选自甲基或乙基。
    或通式I化合物的盐。
  4. 根据权利要求3所述的化合物，其特征在于，通式I中，
    X选自氧或硫；
    Z选自氢；
    A选自CN、(C＝O)OR 1或(C＝O)NH 2；
    R 1选自甲基或乙基；
    W选自氢、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、C(＝O)R 3、S(O) 2R 5、N(R 6)R 7或N＝C(R 8)R 9；
    Q选自氢、C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基或C(＝O)R 3；
    R 3选自C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、N(R 12)R 13、未取代的或被下述基团任意取代的苯基、吡啶基、吡唑基、噻唑基、异噻唑基或噻二唑基：下述基团为氢、卤素、氰基、硝基、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4烷氧基、C 1-C 4卤代烷氧基、C 1-C 4烷硫基或C 1-C 4卤代烷硫基；
    R 5选自C 1-C 2烷基、C 1-C 2卤代烷基、对甲基苯基或N(R 12)R 13；
    R 6选自氢、甲基或乙基；
    R 7选自氢、甲基或乙基；
    R 8选自甲基、乙基、三氟甲基、未取代或被下述基团任意取代的苯基：下述基团为氢、卤素、氰基、硝基；
    R 9选自甲基、乙基、三氟甲基、未取代或被下述基团任意取代的苯基：下述基团为氢、卤素、氰基、硝基；
    R 12选自甲基或乙基；
    R 13选自甲基或乙基；
    或通式I化合物的盐。
  5. 根据权利要求4所述的化合物，其特征在于，通式I中，
    X选自硫；
    Z选自氢；
    A选自CN或(C＝O)NH 2；
    W选自氢、C 1-C 4烷基、C 3-C 6环烷基、C(＝O)R 3或N＝C(R 8)R 9；
    Q选自氢、C 1-C 4烷基、C 3-C 6环烷基或C(＝O)R 3；
    R 3选自C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、未取代的或被下述基团任意取代的苯基、吡啶基、吡唑基、噻唑基、异噻唑基或噻二唑基：下述基团为氢、卤素、氰 基、硝基、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4烷氧基、C 1-C 4卤代烷氧基、C 1-C 4烷硫基或C 1-C 4卤代烷硫基；
    R 8选自甲基、乙基、三氟甲基、未取代或被下述基团任意取代的苯基：下述基团为氢、卤素、氰基、硝基；
    R 9选自甲基、乙基、三氟甲基、未取代或被下述基团任意取代的苯基：下述基团为氢、卤素、氰基、硝基；
    或通式I化合物的盐。
  6. 根据权利要求5所述的化合物，其特征在于，通式I中，
    X选自硫；
    Z选自氢；
    A选自CN或(C＝O)NH 2；
    W选自氢、C 1-C 4烷基或C(＝O)R 3；
    Q选自氢、C 1-C 4烷基或C(＝O)R 3；
    R 3选自C 1-C 4烷基、C 1-C 4卤代烷基、C 3-C 6环烷基、K 1-K 10所示任意一个基团、未取代或被下述基团任意取代的苯基或吡啶基：下述基团为卤素、氰基、硝基、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4烷氧基、C 1-C 4卤代烷氧基、C 1-C 4烷硫基或C 1-C 4卤代烷硫基；
    K 1-K 10表示如下：
    Figure PCTCN2020125780-appb-100002
    或通式I化合物与盐酸、氢溴酸、硫酸、磷酸、甲酸、乙酸、丙酸、丁酸、戊酸、三氟乙酸、草酸、丙二酸、甲磺酸、4-甲苯磺酸、苹果酸、富马酸、乳酸、马来酸、水杨酸、酒石酸或柠檬酸形成的盐。
  7. 一种按照权利要求1所述的肟醚类化合物或其盐在农业、林业或卫生领域中用作杀菌剂的用途。
  8. 一种杀菌组合物，其特征在于：组合物中以权利要求1所示的肟醚类化合物或其盐为活性组份，所述组合物中活性组分的重量百分含量为0.1-99％。
  9. 一种防治病菌的方法，其特征在于：向作物或作物的生长介质或地点上施用杀菌有效剂量的如权利要求8所述的杀菌组合物。
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