WO2006125370A1 - Composes ether aromatiques, leur preparation et leur utilisation - Google Patents

Composes ether aromatiques, leur preparation et leur utilisation Download PDF

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Publication number
WO2006125370A1
WO2006125370A1 PCT/CN2006/000971 CN2006000971W WO2006125370A1 WO 2006125370 A1 WO2006125370 A1 WO 2006125370A1 CN 2006000971 W CN2006000971 W CN 2006000971W WO 2006125370 A1 WO2006125370 A1 WO 2006125370A1
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Prior art keywords
alkyl
group
substituted
compound
alkoxycarbonyl
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PCT/CN2006/000971
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English (en)
French (fr)
Inventor
Changling Liu
Miao Li
Zhinian Li
Liwen Geng
Hong Zhang
Defeng Zhou
Dongliang Cui
Yanmei Luo
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Sinochem Corporation
Shenyang Research Institute Of Chemical Industry
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Application filed by Sinochem Corporation, Shenyang Research Institute Of Chemical Industry filed Critical Sinochem Corporation
Priority to JP2008512671A priority Critical patent/JP4859919B2/ja
Priority to CN200680005095XA priority patent/CN101119972B/zh
Priority to EP06741861A priority patent/EP1884511B1/en
Priority to AT06741861T priority patent/ATE541834T1/de
Priority to US11/817,996 priority patent/US7786045B2/en
Priority to BRPI0609346A priority patent/BRPI0609346B1/pt
Publication of WO2006125370A1 publication Critical patent/WO2006125370A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N43/88—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 six-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with 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
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with 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
    • C07D261/12—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms 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
    • C07D417/02—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

Definitions

  • the invention belongs to the field of agricultural fungicides and insecticides. Specifically, it relates to an aryl ether compound and its preparation and application. Background technique
  • the natural product methoxy acrylate compound is a known biologically active compound.
  • a broad-spectrum bactericidal pyraclostrobin is disclosed in US Pat. No. 5,587, 517, US Pat. No. 6,045, 592, US Pat.
  • a bactericidal activity compound represented by the following formula is disclosed in the patent W09933812:
  • X! is selected from CH or N;
  • X 2 is selected from 0, S or NR 7;
  • R 7 is selected from hydrogen or (C r C 12 ) fluorenyl;
  • X 3 is selected from 0, S or NR S;
  • R 2 is independently selected from hydrogen, -C 12 fluorenyl or halogenated C r C 12 alkyl; selected from N and CR 9 ;
  • a 2 is selected from N and CR 10 ;
  • a 3 is selected from N and CR 11; when selected from N, A 2 is selected from CR 10 and
  • a 3 is selected from CR 11;
  • a 2 is selected from N, A!
  • R 3 is selected from hydrogen, a halogen atom, a C-Cu fluorenyl group, a halogenated dC 12 alkyl group or a dC 12 alkoxy group; and R 5 , R 6 , R 9 and R 10 , which may be the same or different and each selected from the group consisting of hydrogen, a halogen atom and a nitro group.
  • An object of the present invention is to provide an aryl ether compound which can control various pests and diseases at a small dose, and which can be applied to agriculture to control crop diseases and insect pests.
  • the present invention provides an aryl ether compound, as shown in Formula I:
  • X is selected from 0 S or NR 2
  • the 4-position of the pyrimidine is attached to the oxygen, and the 6-position oxygen is bonded to the benzene ring; from hydrogen, halogen, nitro, cyano, CONH 2 , CH 2 CONH 2 , CH 2 CN, CC 12 fluorenyl, halogenated C r C 12 alkyl, ⁇ alkoxy, halo-C 12 decyloxy, C r C 12 alkylthio, CC 12 alkanesulfonyl, dC 12 alkylcarbonyl , -Cu alkoxy dC 12 alkyl, C r C 12 alkoxycarbonyl, C r C 12 decyloxycarbonyl dC 12 fluorenyl, CC 12 halodecyloxy dC 12 fluorenyl, substituted or unsubstituted Amino-Cualkyl; selected from hydrogen, halogen, nitro, cyan
  • Preferred compounds in the present invention are:
  • X 2 is selected from CH 2
  • 3 ⁇ 4 is selected from 0 or N;
  • X 2 is selected from CH 2
  • Ri is selected from the group consisting of hydrogen, a halogen atom, a nitro group, a cyano group, a CONH 2 , a CH 2 CON 3 ⁇ 4, a CH 2 CN, a CC 6 alkyl group, a halogenated-C 6 alkyl group, a CC 6 alkoxy group, a halogenated group.
  • 3 ⁇ 4 is selected from the group consisting of hydrogen, CC 6 alkyl, halogenated dC 6 fluorenyl, CC 3 alkoxycarbonyl or QC 6 alkoxycarbonyl CC 3 ;
  • Xi is selected from 0 or NR 2 ;
  • X 2 is selected from C3 ⁇ 4
  • Ri is selected from the group consisting of hydrogen, chlorine, bromine, fluorine, nitro, cyano, CH 2 CN or CC 6 alkyl;
  • R 2 is selected from the group consisting of hydrogen, C r C 3 fluorenyl, halogenated CrC 3 alkyl, -C 3 alkoxycarbonyl or dC 3 alkoxycarbonyl CC 3
  • Ar when When Ar is selected from substituted or unsubstituted furan, thiophene or thiazole;
  • Ar is selected from substituted or unsubstituted phenyl, pyridyl, furan, thiophene or thiazole; the substituent is selected from a halogen atom, CN, nitro, CC 6 alkyl , -C 6 alkoxy, dC 6 alkylthio, CC 6 haloalkoxy, chlorophenyl or chlorophenoxy.
  • Still further preferred compounds are:
  • X 2 is selected from C3 ⁇ 4
  • the number of substituted amine substituent is C r C 3 alkyl, QC 3 alkoxy, halo-CrC 3 alkyl, haloalkyl CC 3 alkoxy, halogen, nitro, CN, or the like, the substituent may be It is 1 ⁇ 2.
  • the substituent in the substituted phenyl, benzyl, phenoxy, benzyloxy group is alkyl, alkoxy, haloalkyl, halomethoxy, halogen, nitro or CN, etc., the number of substituents may be 1 ⁇ 5.
  • Halogen refers to fluorine, chlorine, bromine or iodine.
  • Mercapto A straight or branched alkyl group such as methyl, ethyl, propyl, isopropyl or t-butyl.
  • Haloalkyl a linear or branched alkyl group in which a hydrogen atom may be partially or completely substituted by a halogen atom, for example, a halogenated fluorenyl group such as chloromethyl, dichloromethyl, trichloromethyl, Fluoromethyl, difluoromethyl or trifluoromethyl.
  • a halogenated fluorenyl group such as chloromethyl, dichloromethyl, trichloromethyl, Fluoromethyl, difluoromethyl or trifluoromethyl.
  • Alkoxy A linear or branched alkyl group bonded to a structure via an oxygen atom.
  • Haloalkoxy a linear or branched alkoxy group, and a hydrogen atom on these alkoxy groups may be partially or completely substituted by a halogen atom.
  • haloalkoxy such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy or trifluoroethoxy base.
  • Alkenyl straight or branched and may have a double bond at any position, such as a vinyl or allyl group.
  • Substituted alkenyl groups include optionally substituted aryl alkenyl groups.
  • Alkynyl straight or branched and may have a triple bond at any position, such as ethynyl or propargyl.
  • Substituted alkynyl groups include optionally substituted aralkynyl groups.
  • the aryl group in the aryl group as well as the aralkyl group, the arylalkenyl group, the aralkynyl group, the aryloxy group and the aryloxyalkyl group includes a phenyl group or a naphthyl group.
  • the heteroaryl group referred to in the present invention is a 5-membered ring or a 6-membered ring containing one or more, 0, S hetero atoms.
  • pyridine furan, pyrimidine, pyrazine, pyridazine, triazine, quinoline or benzofuran.
  • a stereoisomer can be formed due to a carbon-carbon double bond and a carbon-nitrogen double bond connecting different substituents (different configurations are represented by Z and E, respectively).
  • the present invention includes Z-isomers and E-isomers and mixtures thereof in any ratio.
  • the present invention can be illustrated by the compounds listed in Table 1 below, but does not limit the invention.
  • the invention also includes processes for the preparation of compounds of formula I.
  • the compound of the formula I and its stereoisomer are prepared by reacting a hydroxyl group-containing azole compound of the formula III with a benzyl halide of the formula IV under basic conditions:
  • R is a leaving group selected from chlorine or bromine; the other groups are as defined above.
  • Suitable solvents may be selected from, for example, tetrahydrofuran, acetonitrile, toluene, xylene, benzene, N,N-dimethylformamide, dimethyl sulfoxide, acetone or methyl ethyl ketone and the like.
  • Suitable bases may be selected from, for example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium t-butoxide or sodium t-butoxide.
  • a suitable temperature is from room temperature to the boiling point of the solvent, usually from 20 to 100 °C.
  • the reaction time is from 30 minutes to 20 hours, usually from 1 to 10 hours.
  • the intermediate III can be obtained by condensing the intermediate II with a (substituted) anthracene or a hydroxylamine according to a known method.
  • the intermediate II can be obtained by a known method or, for example, US3781438, CN1257490 and W09615115.
  • the compound of the formula IV can be obtained by known methods, as described in detail in US4723034 and US5554578.
  • the compound of the present invention has a broad spectrum of activity and can be used for controlling diseases caused by various pathogens such as Oomycetes, Basidiomycetes, Ascomycetes and Deuteromycetes on various crops, and since these compounds have high
  • the biological activity allows a very good effect to be obtained at very low doses.
  • These compounds have systemic activity and can be used as foliar and soil fungicides, and can be applied to the control of various crop diseases, such as: 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 disease, apple spotted leaf disease, rice sheath blight, rice blast, wheat rust , wheat leaf spot, wheat powdery mildew, rapeseed sclerotinia, corn leaf spot and other diseases have good control.
  • various crop diseases such as: 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 disease, apple spotted leaf disease, rice sheath blight, rice blast, wheat rust , wheat leaf spot, wheat powdery mildew,
  • Some of the compounds of the present invention also have excellent insecticidal and acaricidal activity and can be used for controlling pests and mites on various crops.
  • the present invention also provides an insecticidal, bactericidal composition
  • an insecticidal, bactericidal composition comprising a compound of formula I and an agriculturally acceptable carrier, the active ingredient being present in the composition in an amount of from 0.1 to 99% by weight.
  • the invention also provides a process for the preparation of a composition as defined above:
  • the compound of formula I is admixed with a carrier.
  • a composition may be a single compound or a mixture of several compounds of the invention.
  • the carrier in the composition of the present invention is a substance which, after being formulated with the active ingredient, is convenient for application to a site to be treated, for example, a plant, seed or soil; or is advantageous for storage, transportation or handling.
  • the carrier may be a solid or a liquid, and includes a material which is usually a gas but which has been compressed into a liquid, and a carrier which is usually used in the formulation of the insecticidal or bactericidal composition can be used. .
  • Suitable solid carriers include natural or synthetic clays or silicates such as diatomaceous earth, talc, attapulgite, aluminum silicate (kaolin), montmorillonite, mica; calcium carbonate; calcium sulfate; ammonium sulfate; Silica, synthetic calcium silicate or aluminum silicate; elements such as carbon, sulfur; natural or synthetic resins such as benzofuran resins, polyvinyl chloride, styrene polymers or copolymers; solid polychlorinated phenols; Such as beeswax, paraffin.
  • natural or synthetic clays or silicates such as diatomaceous earth, talc, attapulgite, aluminum silicate (kaolin), montmorillonite, mica; calcium carbonate; calcium sulfate; ammonium sulfate; Silica, synthetic calcium silicate or aluminum silicate; elements such as carbon, sulfur; natural or synthetic resins such as benzofuran resins, polyvinyl chloride, styrene poly
  • Suitable liquid carriers include water; alcohols such as isopropanol, ethanol; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexyl ketone; ethers; aromatic hydrocarbons such as benzene, toluene, xylene; petroleum fractions Such as kerosene, mineral oil; chlorinated hydrocarbons such as carbon tetrachloride, perchloroethylene, trichloroethylene. Usually, mixtures of these liquids are also suitable.
  • Insecticidal, bactericidal compositions are typically processed in the form of a concentrate and used for transport, which is diluted by the user prior to administration.
  • the presence of a small amount of surfactant carrier aids in the dilution process.
  • at least one of the carriers in accordance with the present invention is preferably a surfactant.
  • the composition may contain at least two carriers, at least one of which is a surfactant.
  • the surfactant may be an emulsifier, dispersant or wetting agent; it may be a nonionic or ionic surfactant.
  • suitable surfactants include sodium or calcium salts of polyacrylic acid pro-lignin sulfonic acid; condensation of fatty acids or fatty amines or amides having at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide Things.
  • composition of the present invention may be a wettable powder, a powder, a granule or a liquid, an emulsifiable concentrate, an emulsion, a suspension concentrate, an aerosol or an aerosol.
  • Wettable powders usually contain 25, 50 or 75% by weight of active ingredient, and usually contain 3-10% by weight of dispersing agent in addition to the solid inert carrier, and if necessary, can be added. 0-10% by weight of stability Agents and/or other additives such as penetrants or adhesives.
  • the powder may usually be formed into a powder concentrate having a composition similar to that of the wettable powder but without a dispersing agent, and further diluted with a solid carrier to obtain a composition usually containing 0.5 to 10% by weight of the active ingredient.
  • Granules are usually prepared to have from 10 to 100 mesh (1.676-0.152mm) size, and can be prepared by agglomeration or injection technique. Usually the granules comprise from 0.5 to 75% by weight of active ingredient and from 0 to 10% by weight of additives such as stabilizers, surfactants, slow release modifiers.
  • the so-called "flowable dry powder” consists of relatively small particles having a relatively high concentration of active ingredient.
  • Emulsifying concentrates in addition to solvents, usually contain a cosolvent, 1-50% W/V active ingredient, 2-20% W/V emulsifier and 0-20% W/V other additives such as stabilizers, infiltration when needed.
  • Agent and corrosion inhibitor Suspension concentrates typically contain from 10 to 75% by weight of active ingredient, from 0.5 to 15% by weight of dispersant, from 0.1 to 10% by weight of other additives such as antifoaming agents, corrosion inhibitors, stabilizers, penetrants or adhesives.
  • Aqueous dispersions and emulsions for example compositions obtained by diluting a wettable powder or concentrate according to the invention with water, are also within the scope of the invention.
  • the emulsion may be of two types, water-in-oil or oil-in-water.
  • bactericides By incorporating other one or more bactericides into the composition, it is more broadly active than the compound of formula I alone.
  • other fungicides may have a synergistic effect on the bactericidal activity of the compounds of formula I.
  • Compounds of formula I can also be combined with other insecticides or mixed with another fungicide and other insecticides. detailed description
  • Compound 8 The melting point was 98-100 °C. Sppm 2.47(3H, s), 3.73(3H, s), 3.75(3H, s), 3.81(3H, s), 5.18(2H, s), 5.83(1H, s), 7.24 (1H, m), 7.42 (3H, m), 7.65 (3H, m).
  • Compound 11 an oil. 5ppm 1.45(6H, s), 3.60(3H, s), 3.66(3H, s), 4.94(2H, s), 7.22(3 H, m), 7.30(3 H, m), 7.47(3H, m ).
  • Compound 12 an oil. 5ppm 3.73(3H, s), 3.75(3H, s), 3.81(3H, s), 3.82(3H, s), 5.18(2H s), 5.79(1H, s), 6.90(2H, m), 7.42 (3H, m), 7.61 (1H, m), 7.66 (2H, m).
  • Compound 17 an oil. Sppm 1.27(3H, t), 1.89(3H, s), 2.70(2H, q), 3.62(3 H, s), 3.78(6H : s) 5.32(2H, s), 7.22(2H, m), 7.28(2H, m), 7.40(3 H, m), 7.70(1H, m).
  • Compound 31 an oil. Sppm 3.73(3H, s), 3.76(3H, s), 3.82(3H, s), 5.18(2H, s), 5.78(1H, s), 7.01(1H, m), 7.20(1H, m), 7.24(1H, d), 7.42(3H, m), 7.60(1H, m).
  • Compound 64 an oil. Sppm 1.68(3H, s), 3.60(3H, s), 3.79(6H, s), 5.30(2H, s), 7.25(2H, d), 7.42(5H, m), 7.72(1 H, d) . .
  • Compound 78 an oil. Sppm 1.89 (31-1, s), 2.05 (3H, s), 3.61 (3H, s), 3.78 (6H, s), 5.31 (2H, s), 7.22 (2H, d), 7.29 (1H, d ), 7.38 (3H, m), 7.71 (1H, m).
  • Compound 107 an oil. ⁇ 2.39(3 ⁇ , s), 3.74(3H, s), 3.76(3H, s), 3.83(3H, s), 5.32(2H, s), 5.56(1H, s), 7.24 (2H, d), 7.42 (3H, m), 7.63 (3H, d).
  • Compound 204 an oil. 5ppm 3.62(3H, s), 3.78(6H, s), 6.43(2H, m), 7.19(1H, d), 7.38(4H, m), 7.48(1H, s), 8.08(1H, d), 8.50 (1H, s), 8.78 (1H, s).
  • Compound 418 Oil. ⁇ 2.89(3 ⁇ , d), 3.42(3 ⁇ , s), 3.94(3 ⁇ , s), 5.16(2 ⁇ , s), 6.43(1 ⁇ , m), 6.79(1 ⁇ , bs), 6 ⁇ 96(1 ⁇ , m ), 7.25(3 ⁇ , m), 7.46(3 ⁇ , m).
  • Compound 442 an oil. Sppm 3.63(3H, s), 3.73(3H, s), 3.85(3H 5 s), 3.92(3H, s), 4.05(3H, s), 5.00(2H, s), 5.67(1H, s), 6.79(2H, m), 6.92(2H, m), 7.25(1 H, m).
  • Example 5 35% emulsifiable concentrate
  • the phosphorous acid is dissolved in cyclohexanone: Compound 2 and ethoxylated triglyceride are then added to give a clear solution.
  • Example 6 60% wettable powder
  • Compound 64 sodium dodecylnaphthalene sulfonate, sodium lignosulfonate and kaolin (both solids) were mixed together and pulverized in a pulverizer until the granules reached the standard.
  • Example 7 30% aqueous suspension
  • Compound 121 was pulverized together with 80% of the water to be added and sodium dodecylnaphthalenesulfonate in a ball mill (1 mm beads). Hemicellulose and propylene oxide were dissolved in the remaining 20% of water, and then the above components were stirred.
  • Example 8 25% suspension of an emulsion concentrate
  • Epoxymethyl ethane propylene oxide copolymer 2.5%
  • Alkyl aryl fractions make up to 100%
  • Compound 11 is dissolved in 80% of the amount of solvent to be added (cyclohexanone and alkyl aryl fraction), followed by the addition of an emulsifier (dodecyl alcohol polyethylene glycol phosphate, ethoxy triglyceride and A calcium dodecylbenzenesulfonate) and a dispersing agent (2,5 parts of a copolymer of ethylene oxide propylene oxime) were thoroughly stirred. The mixture was comminuted in a ball mill (lmm beads) and then the remaining 20% solvent was added.
  • solvent to be added cyclohexanone and alkyl aryl fraction
  • Activity assays were carried out on various fungal diseases of plants using the compounds of the invention.
  • the test method is as follows: The potency assay and the therapeutic effect were determined by pot assay.
  • the test compound was dissolved in a small amount of acetone, and diluted to the desired concentration with water containing 0.1% Tween 80.
  • the protective action was first sprayed onto the plant sample and the disease was inoculated 24 hours later. After inoculation, the plants are placed in a constant temperature and humidity incubator to continue the infection, and the evaluation is conducted after the control is fully ill (usually one week).
  • the therapeutic effect was first inoculated with pathogenic bacteria, and spray treatment was carried out 4 days later, and the evaluation was conducted after the control was fully afflicted (3-4 days after the spray treatment).
  • test results were as follows - at a dose of 500 mg/L, compound 16 was 100% resistant to wheat powdery mildew (BLumeria gra z' ' ⁇ ) and more than 80% of compounds 1, 15, 26, 185, and 367.
  • compounds 1, 8, 15, 194, 367, and 415 were 100% resistant to cucumber downy mildew (Pseudoperonospora cubenis) and 90% to compounds 11, 391.
  • Compounds 15, 20, 63, and 78 were 100% resistant to cucumber downy mildew at 25 mg/L, and more than 95% resistant to wheat powdery mildew at 12.5 mg/L.
  • Compound 63 has a 100% control effect on cucumber anthracnose fCo / etot 'c1 ⁇ 2m !agma!'ium at a dose of 100 mg/L, and a 100% control effect at 1.56 mg/L.
  • Compound 63 except for rice blast disease oryzae), tomato late blight (Phytophthora infestans), cucumber downy mildew, wheat powdery mildew, cucumber anthracnose, Fuliginea) and rice sheath blight ⁇ Rhizoctonia solani) are effective for Custarsporium cucumerinum, apple rot Vaha malO, Sderotinia sclerotiorum, and tomato leaf mold iFulvia Fulva), Helminthosporium maydis, and Fusarium grammearum showed some activity.
  • insects and mites were tested for insecticidal activity using the compounds of the present invention.
  • the method of measurement is as follows: After the test compound is dissolved in a mixed solvent of acetone/methanol (1:1), it is diluted with water containing 0.1% Tween 80 to a desired concentration. '
  • the concentration of the drug solution was 600 mg/L
  • the mortality of compound 15, 20, 63, 64, etc. against armyworm, diamondback moth, peach aphid, and Culex pipiens pallens was more than 85%.
  • Compound 15 had a mortality rate of 90% for peach aphid at a dose of 200 mg/L and a mortality rate of 100% for Plutella xylostella at a dose of 200 mg/L.

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Description

技术领域
本发明属农用杀菌剂和杀虫剂领域。具体说涉及一种芳基醚类化合物及其制备与 应用。 背景技术
天然产物甲氧基丙烯酸酯化合物是已知的具有生物活性的化合物。 专利
US5869517、 US6054592、 CN1154692, CN1308065等中公开了广谱杀菌剂唑菌胺酯 (pyraclostrobin), 其化学结构如下：
Figure imgf000003_0001
唑菌胺酯 (pymclostrobin)
专利 DE19548786中公开了如下具有杀菌活性的化合物:
Figure imgf000003_0002
专利 W09933812中公开了如下通式所示的具有杀菌活性的化合物:
Figure imgf000003_0003
《农药学报》 （Nongyaoxue Xuebao, 2004, 6(1), 17-21 )报道如下通式所示的具 有杀菌活性的化合物：
Figure imgf000003_0004
在本发明之前， 我们曾递交了中国专利 ( CN1657524A ) 和 PCT 专利
(WO2005080344A) 申请， 涉及如下通式所示的取代唑类衍生物作为杀虫、 杀菌剂:
Figure imgf000004_0001
式中： X!选自 CH或 N; X2选自 0、 S或 NR7; R7选自氢或 (CrC12)垸基； X3选 自 0、 S或 NRS; 选自氢、 C C12烷基、卤代 C 2烷基、 -Cn烷氧基羰基、 Cj-Ciz 烷氧基羰基 C C12烷基； 、 R2分别选自氢、 -C12垸基或卤代 CrC12烷基； 选 自 N和 CR9; A2选自 N和 CR10; A3选自 N和 CR11; 当 选自 N时， A2选自 CR10， A3选自 CR11; 当 A2选自 N时， A!选自 CR9， A3选自 CRU; 当 A3选自 N时， A!选 自 CR9， A2选自 CRK); R3选自氢、 卤原子、 C-Cu垸基、 卤代 d-C12烷基或 d-C12 烷氧基； 、 R5、 R6、 R9、 R10, 可相同或不同， 分别选自氢、 卤原子、 硝基、 氰 基、 CONH2> C¾CO H2, Ci¾GN、 d-C12焼基、 代 d-Cn;^基、 d-C12;^氧基、 卤代 12烷氧基、 硫基、 d-c12烷磺酰基、 d-c12烷基羰基、 d-c12垸氧 基 CrC12烷基、 d-C12烷氧基羰基、 -C12烷氧基羰基 CrC12烷基、 C C12卤代烷氧 基 C C12烷基、任意取代胺基 CrCu烷基、任意取代的芳氧基、任意取代的芳 Q-C12 烷基氧基、 任意取代的芳基、 杂芳基、 任意取代的芳基 CrC12烷基、 杂芳基 -C12 烷基、 杂芳基 12烷氧基。
以上专利（申请）中所有公开的化合物虽与本发明化合物结构相似， 但存在显著 的不同。 发明内容
本发明的目的在于提供一种在很小剂量下就可以控制各种病虫害的芳基醚类化 合物， 它可应用于农业上以防治作物的病害和虫害。
本发明的技术方案如下：
本发明提供一种芳基醚类化合物， 如通式 I所示：
Figure imgf000004_0002
式中：
X〗选自 0 S或 NR2
Figure imgf000004_0003
当 ¾选自 z ^ 、0 时， 嘧啶的 4-位与氧相连， 6-位氧与苯环相连； 选自氢、 卤原子、 硝基、 氰基、 CONH2、 CH2CONH2、 CH2CN、 C C12垸基、 卤代 CrC12烷基、 ^烷氧基、 卤代 -C12垸氧基、 CrC12烷硫基、 C C12烷磺酰 基、 d-C12烷基羰基、 -Cu烷氧基 d-C12烷基、 CrC12烷氧基羰基、 CrC12垸氧基 羰基 d-C12垸基、 C C12卤代垸氧基 d-C12垸基、 取代或未取代的胺基 -Cu烷基； 选自氢、 C C12烷基、 卤代 12烷基、 d-C12垸氧基羰基或 12垸氧基羰 基 Ci-Ci2焼基；
Q选自如下所示的基团之一：
Figure imgf000005_0001
当 Q选自 Qi、 Q2、 Q3或 Q5， X2=CH2时， Ar选自取代或未取代的五元杂芳基; 当 Q=Q1 X2= 或当 Q=Q4， ¾=CH2时， Ax选自取代或未取代的芳基、 杂芳基； 取代基选自卤原子、 CN、 硝基、 CrC6烷基、 -¾烷氧基、 -¾垸硫基、 -C6烷磺酰基、 -Cs烷氧基羰基、 C C6卤代烷氧基、取代的芳基或取代的芳氧基; 及其立体异构体。
本发明中较为优选的化合物为： 通式 I 中
X！选自 0、 S或 NR2;
X2选自 CH2
Figure imgf000005_0002
选自氢、 卤原子、 硝基、 氰基、 CONH2、 CH2CON¾、 CH2CN、 C C6烷基、 卤代 d-C6烷基、 CrC6烷氧基、 卤代 CrC6垸氧基、 CrCe烷硫基、 C C6垸磺酰基、 CrC6烷基羰基、 CrC6烷氧基 -C6烷基、 d-C6烷氧基羰基、 CrC6垸氧基羰基 d-C6 烷基、 d-C6卤代烷氧基 C C6烷基、 取代或未取代的胺基 -C6烷基；
选自氢、 C C6烷基、 卤代 C C6烷基、 Q-C6烷氧基羰基或 d-C6烷氧基羰基 Ci-C6院基；
当 Q选自 Q!、 Q2、 Q3或 Q5， X2=CH2时， Ar选自取代或未取代的五元杂芳基； 当
Figure imgf000005_0003
时， Ar选自取代或未取代的芳基、 杂芳基； 取代基选自卤原子、 CN、 硝基、 CrC6烷基、 C C6垸氧基、 CrC6烷硫基、 - .烷磺酰基、 d-C6烷氧基羰基、 CrC6卤代垸氧基、取代的苯基或取代的苯氧基。 进一步优选的化合物为： 通式 I 中
¾选自 0或 N ;
X2选自 CH2
Figure imgf000006_0001
Ri选自氢、 卤原子、 硝基、 氰基、 CONH2、 CH2CON¾、 CH2CN、 C C6烷基、 卤代 -C6烷基、 C C6烷氧基、 卤代 -。6烷氧基、 d-C6烷硫基、 Q-C6烷磺酰基、 -C6垸基羰基、 C C6烷氧基 C C6垸基、 -C6烷氧基羰基、 -C6烷氧基羰基 d-C6 烷基、 C C6卤代垸氧基 C C6垸基、 取代或未取代的胺基 C C3烷基；
¾选自氢、 C C6烷基、 卤代 d-C6垸基、 C C3烷氧基羰基或 Q-C6烷氧基羰基 C C3院基；
当 Q选自 Qi、 Q2、 Q3或 Q5， X2=CH2时， Ar选自取代或未取代的呋喃、 噻吩或 噻唑； 当 Q=Qi，
Figure imgf000006_0002
时， Ax选自取代或未取代的 苯基、吡啶基、呋喃、噻吩或噻唑； 取代基选自卤原子、 CN、硝基、 CrC6烷基、 d-C6 烷氧基、 -C6垸硫基、 C C6烷磺酰基、 C C6卤代烷氧基、 取代的苯基或取代的苯 更进一步优选的化合物为： 通式 I 中
Xi选自 0或 NR2;
X2选自 C¾
Figure imgf000006_0003
Ri选自氢、 氯、 溴、 氟、 硝基、 氰基、 CH2CN或 C C6烷基；
R2选自氢、 CrC3垸基、 卤代 CrC3烷基、 -C3烷氧基羰基或 d-C3烷氧基羰基 C C3
当
Figure imgf000006_0004
时， Ar选自取代或未取代的呋喃、噻吩或噻唑；
当 Q=Qi，
Figure imgf000006_0005
或当 Q=Q4， X2=CH2时， Ar选自取代或未取代的苯基、 吡 啶基、 呋喃、 噻吩或噻唑； 取代基选自卤原子、 CN、 硝基、 C C6烷基、 -C6烷氧 基、 d-C6烷硫基、 C C6卤代烷氧基、 氯代苯基或氯代苯氧基。
再进一步优选的化合物为： 通式 I 中
选自 0或 NR2;
X2选自 C¾
Figure imgf000006_0006
选自氢或甲基；
选自氢、 甲基或异丙基; 当 Q=Qi、 Q2、 Q3或 Q5， X2=C¾时， Ar选自取代或未取代呋喃或噻吩；当 0=(^，
Figure imgf000007_0001
， ¾ ¾时， Ar选自取代或未取代的苯基、 吡啶基、 呋喃 或噻吩； 取代基选自卤原子、 d-C3烷基、 Q-C3烷氧基、 Q-C3烷硫基或 C C3卤代 烷氧基。 '
上面给出的通式 I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。
取代的胺基中取代基为 CrC3烷基、 Q-C3烷氧基、 卤代 CrC3烷基、 卤代 C C3 烷氧基、 卤素、 硝基或 CN等等， 取代基的数目可为 1~2。
取代的苯基、 苄基、 苯氧基、 苄氧基中取代基为烷基、 烷氧基、 卤代烷基、 卤代 垸氧基、 卤素、 硝基或 CN等等， 取代基的数目可为 1~5。
卤： 指氟、 氯、 溴或碘。
垸基： 直锋或支链烷基， 例如甲基、 乙基、 丙基、 异丙基或叔丁基。
卤代烷基：直链或支链烷基， 在这些垸基上的氢原子可部分或全部被卤原子所取 代， 例如， 卤代垸基诸如氯甲基、 二氯甲基、 三氯甲基、 氟甲基、 二氟甲基或三氟甲 基。
烷氧基： 直链或支链烷基， 经氧原子键连接到结构上。
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原 子所取代。 例如， 卤代烷氧基诸如氯甲氧基、 二氯甲氧基、 三氯甲氧基、 氟甲氧基、 二氟甲氧基、 三氟甲氧基、 氯氟甲氧基或三氟乙氧基。
链烯基： 直链或支链并可在任何位置上存在有双键， 例如乙烯基或烯丙基。取代 链烯基包括任意取代的芳基链烯基。
炔基： 直链或支链并可在任何位置上存在有三键， 例如乙炔基或炔丙基。取代炔 基包括任意取代的芳炔基。
芳基以及芳烷基、 芳基链烯基、芳炔基、 芳氧基和芳氧基烷基中的芳基部分包括 苯基或萘基。
本发明中所指杂芳基是含 1个或多个 、 0、 S杂原子的 5元环或 6元环。 例如 吡啶、 呋喃、 嘧啶、 吡嗪、 哒嗪、 三嗪、 喹啉或苯并呋喃。
在本发明的化合物中， 由于碳-碳双键和碳-氮双键连接不同的取代基而可以形成 立体异构体 (分别以 Z和 E来表示不同的构型)。本发明包括 Z型异构体和 E型异构体 及其任何比例的混合物。
可以用下面表 1中列出的化合物来说明本发明， 但并不限定本发明。
表 1
Figure imgf000007_0002
Figure imgf000008_0001
Figure imgf000009_0001
Figure imgf000010_0001
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
/ Ol900zAV.£G/:/>d6000900ZN
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
444 NCH3 CH2 H . 3,4-2CH3-C6H3 Q4
445 NCH3 CH2 H 2,5-2CH3-C6¾ Q4 ,
446 NCH3 CH2 H 2,6-2C¾-C6H3 Q4
447 NCH3 CH2 CH3 2'4-2CH3-C6H3 Q4
448 NCH3 CH2 CH3 3,4-2C¾-C6H3 Q4
449 NCH3 C¾ CH3 2,5-2CHrC6H3 Q4
450 NCH3 C¾ CH3 2,6-2CH3-C6H3 Q4 表中
Figure imgf000020_0001
本发明还包括通式 I化合物的制备方法。
通式 I化合物及其立体异构体由通式 III 所示的含羟基的唑类化合物与通式 IV 所示的苄卤在碱性条件下反应制得：
Figure imgf000020_0002
通式 IV 中， R是离去基团， 选自氯或溴； 其他各基团的定义同上。
适宜的溶剂可选自如四氢呋喃、 乙腈、 甲苯、 二甲苯、 苯、 N,N-二甲基甲酰胺、 二甲亚砜、 丙酮或丁酮等。
适宜的碱可选自如氢氧化钾、 氢氧化钠、 碳酸钠、 碳酸钾、 碳酸氢钠、 三乙胺、 吡啶、 甲醇钠、 乙醇钠、 氢化钠、 叔丁醇钾或叔丁醇钠等。
适当的温度指室温至溶剂沸点温度， 通常为 20~100°C。
反应时间为 30分钟至 20小时， 通常 1~10小时。
中间体 III可由中间体 II与 （取代的） 肼、 羟胺按照已知方法缩合得到， 中间 体 II可以购得或通过已知方法制得，具体参见 US3781438、 CN1257490和 W09615115 等。
通式 IV所示的化合物可以由已知方法制得，具体参见 US4723034和 US5554578
Figure imgf000020_0003
本发明的化合物具有广谱活性一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病菌引起的病害，而且由于这些化合物具有很高的生物活性 使得在很低的剂量下就可以获得很好的效果。该类化合物具有内吸活性并可用作叶面 和土壤杀菌剂，可应用在防治多种作物上的病害，例如：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、 苹果轮紋病、 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很好的防效。
本发明的部分化合物还具有很好的杀虫和杀螨活性，可用于防治多种作物上害虫 和螨。
本发明还提供了一种杀虫、 杀菌组合物， 该组合物中含有通式 I 的化合物和农 业上可接受的载体， 组合物中活性组分的重量百分含量为 0.1-99%。
本发明还提供了如上所定义的组合物的制备方法： 将通式 I 的化合物与载体混 合。 这种组合物可以为含本发明的单一化合物或几种化合物的混合物。
本发明组合物中的载体系满足下述条件的物质：它与活性成分配制后便于施用于 待处理的位点， 例如可以是植物、 种子或土壤； 或者有利于贮存、 运输或操作。 载体 可以是固体或液体， 包括通常为气体但已压缩成液体的物质， 通常在配制杀虫、 杀菌 组合物中所用的载体均可使用。 .
合适的固体载体包括天然或合成的粘土或硅酸盐， 例如硅藻土、 滑石、 硅镁土、 硅酸铝 （高岭土）、 蒙脱石、 云母; 碳酸钙； 硫酸钙； 硫酸铵； 合成的氧化硅、 合成 硅酸钙或硅酸铝； 元素如碳、 硫； 天然的或合成的树脂如苯并呋喃树脂， 聚氯乙烯、 苯乙烯聚合物或共聚物； 固体多氯苯酚； 沥青； 蜡如蜂蜡、 石蜡。
合适的液体载体包括水； 醇如异丙醇、 乙醇； 酮如丙酮、 甲基乙基酮、 甲基异丙 基酮、 环已基酮； 醚； 芳烃如苯、 甲苯、 二甲苯； 石油馏分如煤油、 矿物油； 氯代烃 如四氯化碳、 全氯乙烯、 三氯乙烯。 通常， 这些液体的混合物也是合适的。
杀虫、杀菌组合物通常加工成浓缩物的形式并以此用于运输， 在施用之前由使用 者将其稀释。少量的表面活性剂载体的存在有助于稀释过程。这样， 按照本发明的组 合物中至少有一种载体优选是表面活性剂。例如组合物可含有至少两种载体，其中至 少一种是表面活性剂。
表面活性剂可以是乳化剂、分散剂或润湿剂； 它可以是非离子的或离子的表面活 性剂。合适的表面活性剂的例子包括聚丙烯酸祖木质素磺酸的钠盐或钙盐； 分子中含 至少 12个碳原子的脂肪酸或脂肪胺或酰胺与环氧乙烷和 /或环氧丙烷的缩合物。甘醇、 山梨醇、 蔗糖或季戊四醇脂肪酸酯及这些酯与环氧乙烷和 /或环氧丙垸的缩合物 ； 脂 肪醇或烷基苯酚如对辛基苯酚或对辛基甲苯酚与环氧乙烷和 /或环氧丙烷的缩合物； 这些缩合产物的硫酸盐和磺酸盐； 在分子中至少含有 10个碳原子的硫酸或磺酸酯的 碱金属或碱土金属盐， 优选钠盐， 例如硫酸月桂酸酯钠， 硫酸仲烷基酯钠， 磺化蓖麻 油钠盐， 磺酸烷基芳基酯钠， 如十二烷基苯磺酸钠盐。
本发明的组合物的实例可以是可湿性粉剂、粉剂、颗粒剂或液剂， 可乳化的浓缩 剂.、 乳剂、 悬浮浓缩剂、 气雾剂或烟雾剂。 可湿性粉.剂通常含 25， 50或 75%重量活 性成分， 且通常除固体惰性载体之外， 还含有 3-10%重量的分散剂， 且若需要可加入. 0-10%重量的稳定剂和 /或其它添加剂如渗透剂或粘着剂。粉剂通常可成型为具有与可 湿性粉剂相似的组成但没有分散剂的粉剂浓缩剂， 再进一歩用固体载体稀释， 得到通 常含 0.5-10%重量活性组分的组合物。 粒剂通常制备成具有 10 至 100 目 (1.676-0.152mm)大小， 且可用成团或注入技术制备。 通常粒剂含 0.5-75%重量的活性 成分和 0-10%重量添加剂如稳定剂、 表面活性剂、 缓释改良剂。 所谓的"可流动干粉" 由具有相对高浓度活性成分的相对小的颗粒组成。可乳化浓缩剂除溶剂外， 当需要时 通常含有共溶剂， 1-50%W/V活性成分， 2-20%W/V乳化剂和 0-20%W/V其他添加剂 如稳定剂、 渗透剂和腐蚀抑制剂。 悬浮浓縮剂通常含有 10-75%重量的活性成分、 0.5-15%重量的分散剂、 0.1-10%重量的其它添加剂如消泡剂、 腐蚀抑制剂、 稳定剂、 渗透剂 或粘着剂。
水分散剂和乳剂，例如通过用水稀释按照本发明的可湿性粉剂或浓缩物得到的组 合物， 也列入本发明范围。 所说的乳剂可具有油包水或水包油两个类型。
通过在组合物中加入其他的一种或多种杀菌剂， 使其能比单独的通式 I 化合物 具有更广谱的活性。 此外， 其他杀菌剂可对通式 I化合物的杀菌活性具有增效作用。 也可将通式 I 化合物与其他杀虫剂混用， 或同时与另一种杀菌剂以及其他杀虫剂混 用。 具体实施方式
以下具体实施例来进一步说明本发明。
合成实施例
实例 1: 化合物 2的制备
Figure imgf000022_0001
ΠΙ-1 IV-1
将 2.12克对氯苯甲酰乙酸甲酯溶于 10毫升甲醇中， 加热回流。 滴加稍过量的甲 基肼， 回流 3 小时。 TLC监测反应完毕后， 浓缩， 冷却， 析出晶体。 过滤， 用少量 甲醇冲洗晶体。干燥，得 1.5克晶体 3-(4-氯苯基 )-1-甲基 -5-吡唑醇， 即化合物（111-1 )。
将上述晶体 0.5克溶于 5毫升 N,N-二甲基甲酰胺中， '加入氢化钠 0.17克， 搅拌 0.5小时。 加入化合物 （IV-1 ) 0.72克， 油浴 40°C， 搅拌 3小时。 TLC监测反应完毕 后，将反应液倒入 50毫升饱和食盐水中，用 60毫升乙酸乙酯分三次进行萃取，干燥。 脱溶后， 柱层析纯化得油状产品 0.56克， 即化合物 2。
核磁数据 (iHNMR, 300MHz, 内标 TMS, 溶剂 CDC13)如下：
δρριτι 3.75(6H5 s), 3.81(3H, s), 5.20(2H, s), 5.86(1H, s)， 7.35(2H, d), 7.44(31-1, m)， 7.54(1H, m), 7.69(2H, m)
实例 2: 化合物 21的制备
Figure imgf000023_0001
ΙΠ-2 IV-1
将 60%氢化钠 0.15克加入到反应瓶中， 用石油醚洗后， 加入 5毫升 N,N-二甲基 甲酰胺， 然后加入按照专利 CN1257490A方法制得的化合物 （ΠΙ-2) 1.0克， 室温搅 拌 2分钟后加入化合物 （IV-1 ) 1.40克， 60°C下搅拌反应 2小时。 TLC监测反应完 毕后， 将反应液倒入 50毫升饱和食盐水中， 用 100毫升乙酸乙酯分三次进行萃取， 干燥。 脱溶后， 柱层析纯化得油状产品 0.95克， 即化合物 21。
核磁数据 (^HNMR, 300MHz, 内标 TMS , 溶剂 CDC13)如下：
Sppm 3.75(3H, s), 3·76(3Η, s), 3.82(3Η, s), 5.21(2Η, s), 5.89(1Η, s), 7.33(1Η, d), 7.45(3Η, m), 7.58 (1Η, d), 8.06(1H, d), 8.68(1H, s)。
实例 3: 化合物 89的制备
Figure imgf000023_0002
参照专利 US3781438报道的方法，将 2克对甲基苯甲酰乙酸甲酯溶于甲醇中，并 加入稍过量的盐酸羟胺、 等摩尔量的氢氧化钠， 然后加热回流 3小时。 TLC监测反 应完毕后加水， 乙酸乙酯萃取， 干燥、 浓缩得固体 4-甲基苯基异恶唑 -5-醇， 即化合 物 （ΙΠ-3 )。
将 1克化合物（ΠΙ-3 )溶于 N,N-二甲基甲酰胺中， 加入氢化钠 0.45克， 搅拌 0.5 小时。 加入化合物 （IV-1 ) 1.7克， 油浴 50°C， 搅拌 6小时。 TLC监测反应完毕后， 将反应液倒入 50毫升饱和食盐水中， 用 100毫升乙酸乙酯分三次进行萃取， 干燥。 脱溶后， 柱层析纯化得油状产品 1.5克， 即化合物 89。
实例 4: 化合物 121的制备
Figure imgf000023_0003
III-1 IV-2
将化合物 (III- 1)1.0克、 化合物 （IV-2) (参照专利 WO 9807707， WO 9208703制 备） 1.7克及 2.1 克无水碳酸钾于 15 毫升 N,N-二甲基甲酰胺中的混合溶液加热到 70-80°C, 搅拌 7小时。 TLC监测反应完毕后， 将反应液倒入 100毫升饱和食盐水中， 用 100毫升乙酸乙酯分三次进行萃取，干燥。脱溶后，柱层析纯化得油状产品 1.1克， 即化合物 121。
其他化合物参照上述方法合成。
部分表 1中所示的通式 I化合物的理化性质和核磁数据 (^HNMR, 300MHz,内标 TMS, 溶齐 [J CDC13)如下：
化合物 1 : 油状物。 Sppm 3.75(6H, s), 3.81(3H, s), 5.19(2H, s), 5.86(1H, s)，
7.40(5H, m), 7.60(1H, m), 7.68(2H, d)。
化合物 8:熔点为 98-100°C。 Sppm 2.47(3H, s), 3.73(3H, s), 3.75(3H, s), 3.81(3H, s), 5.18(2H, s), 5.83(1H, s), 7.24 (1H, m), 7.42(3H, m), 7.65(3H, m)。
化合物 10：熔点为 89-91 °C。 6ppm3.75(6H, s), 3.79(3H, s), 5.20(2H, s), 6.07(1H, s), 7.24(2H, d), 7.42(4H, m), 7.58(1H, m), 7.75(1H, d)。
化合物 11： 油状物。 5ppm 1.45(6H, s), 3.60(3H, s), 3.66(3H, s), 4.94(2H, s), 7.22(3 H, m), 7.30(3 H, m), 7.47(3H, m)。
化合物 12：油状物。 5ppm 3.73(3H, s), 3.75(3H, s), 3.81(3H, s), 3.82(3H, s), 5.18(2H s), 5.79(1H, s), 6.90(2H, m), 7.42(3H, m), 7.61(1H, m), 7.66(2H, m)。
化合物 15:熔点为 90-92°C。 Sppm3.73(3H, s), 3.75(3H, s), 3.81(3H, s), 5.18(2H, s),
5.83(1H, s), 7.43 (3H, m), 7.47(1H， m), 7.50(1H, m), 7.60(3H, m)。
化合物 16:熔点为 93-95°C。 Sppm 2.36(3H, s), 3.74(3H, s), 3.76(3H， s)， 3.82(3H, s), 5.19(2H, s), 5.83(1H, s), 7.19 (2H, d), 7.42(3H, m), 7.63(3H, d)。
化合物 17:油状物。 Sppm 1.27(3H, t), 1.89(3H, s), 2.70(2H, q), 3.62(3 H, s), 3.78(6H: s) 5.32(2H, s), 7.22(2H, m), 7.28(2H, m), 7.40(3 H, m), 7.70(1H, m)。
化合物 20:油状物。 Sppm 3.57(6H, s), 3.79(6H, s), 5.26(2H, s), 5.73(1H, s), 7.37(6H: m), 7.50(1H, m), 7.69(1H, d)。
化合物 26: 熔点为 114-116°C。 δρρπι 3.75(6H, s), 3.81(3H, s), 4.79(2H, t), 5.21(2H, s), 5.83(1H, s), 7.44(3H, m), 7.58(1H, d), 8.06(1H, dd), 8.44(1H, s)。
化合物 28:油状物。 Sppm 3.72(3H, s), 3.75(3H, s), 3.82(3H, s), 5.17(2H, s), 5.78(1H, s), 6.43(1H, dd), 6.58(1H, m), 7.41(4H, m), 7.59(1H, m)。
化合物 29:油状物。 Sppm 3.69(3H, s), 3.74(3H, s), 3.81(3H, s), 5.16(2H, s), 5.70(1H: s), 6.82(1H, m), 6.98(1H, m), 7.42(3H, m), 7.56(1H, m)。
化合物 31 :油状物。 Sppm 3.73(3H, s), 3.76(3H， s), 3.82(3H, s), 5.18(2H, s), 5.78(1H, s)， 7.01(1H, m), 7.20(1H, m), 7.24(1H, d), 7.42(3H, m), 7.60(1H, m)。
化合物 63 :熔点为 66-68°C。 Sppm 1.90(3H, s)， 3.62(3H, s), 3.79(6H, s), 5.32(2H, s)， 7.30(2H, d), 7.42(6H, m), 7.72(1H, d), 7.60(3 H, m)。
化合物 64:油状物。 Sppm 1.68(3H, s), 3.60(3H, s), 3.79(6H, s), 5.30(2H, s), 7.25(2H, d), 7.42(5H, m), 7.72(1 H, d)。 .
化合物 74：油状物。 Sppm 1.88(31-1, s), 3.61(3H, s), 3.78(3H, s), 3.79(3 H, s), 3.86(3H, s), 5.32(2H, s), 6.99(2H, m), 7.22(2H, m)， 7.40(3 H, m), 7.69(11-1, m)。
化合物 78：油状物。 Sppm 1.89(31-1, s), 2.05(3H, s), 3.61(3H, s), 3.78(6H, s), 5.31(2H, s), 7.22(2H, d)， 7.29 (1H, d)， 7.38(3H, m), 7.71(1H, m)。 化合物 107:油状物。 δρρπι 2.39(3Η, s), 3.74(3H, s), 3.76(3H, s), 3.83(3H, s), 5.32(2H, s), 5.56(1H, s)， 7.24 (2H, d), 7.42(3H, m), 7.63(3H, d)。
化合物 185： 油状物。 5ppm 3.61(3H, s), 3.78(6H, s), 6.41 (2H, s), 7.20(1H, m), 7.35 (5H, m), 7.42(1H, m), 7.72(2H, d), 8.50(1H, s)。
化合物 194:油状物。 Sppm 1.50(6H, s), 3.61(3H, s), 3.77(6H, s), 6.32(1H, s), 7.40(1H, s), 7.20(1H, m), 7.34(6H, m), 7.48(1H, s), 7.74(2H, d), 8.50(1H, s)。
化合物 199：熔点为 142-144°Co 5ppm 2.37(3H, s), 3.61(3H, s), 3.77(6H, s), 6.39(2H, dd), 7.19(3H, d), 7.38(2H, m), 7.42(1H, m), 7.46(1H, s), 7.68(2H, d), 8.50(1H, s)。
化合物 204: 油状物。 5ppm 3.62(3H, s), 3.78(6H, s), 6.43(2H, m), 7.19(1H, d), 7.38(4H, m), 7.48(1H, s), 8.08(1H, d), 8.50(1H, s)， 8.78(1H, s)。
化合物 367:熔点为 130-132°C。5ppm 3.69(3H, s), 3.71(3H, s), 3.84(3H, s), 5.03(2H, s), 5.72(1H, s), 6.43(1H, dd), 6.61(1H, dd), 7.17(1H, m), 7·38(3Η, m), 7.48(1H, m), 7.61(lH, s)。
化合物 368:熔点为 92-94°Co5ppm 3.65(3H, s), 3.71(3H, s), 3.83(3H, s), 5.01(2H, s), 5.62(1H, s), 6.81(1H, d), 6.98(1H, d), 7.20(1H, m)， 7.37(2H, m), 7.48(1H, m), 7.60(1H, s)。
化合物 370:熔点为 96-98。C。 Sppm 3.69(3H, s), 3.71(3H, s), 3.84(3 H, s), 5.03(2H, s), 5.70(1H, s), 7.02(1H, m), 7.21(2H, m), 7.27(1H, m), 7.29(2H, m), 7.38(1H, m), 7.61(1H, s)。
化合物 391 : 熔点为 127-130°C。 Sppm 3.65(3H, s), 3.85(3H, s), 4.06(3H, s), 5.00(2H, s), 5.86(1H, s), 7.02(1H, m), 7.21 (3H, m)， 7.48(3H, m)。
化合物 392:油状物。 Sppm 3.72(3H, s), 3.84(3H, s), 4.04(3H, s), 5.02(2H, s), 5.60(1H, m), 6.94(1H, m), 7.21(1H, m), 7.46(4H, m)。
化合物 394:熔点为 88-90°C。 6ppm 3.68(3H, s), 3.85(3H, s), 4.06(3H, s), 5.01(2H, s), 5.73(1H, s), 6.42(1H, m), 6.62(2H, m), 7.25(1H, m), 7.41(2H, m), 7.46(1H, m)。
化合物 415:熔点为 139-141。C。Sppm 2.92(3H, d), 3.64(3H, s), 3.96(3H, s), 5.00(2H, s), 5.74(1H, s), 6.79(1H, bs), 7.02(1H, m), 7.22(3H, m), 7.45(2H, m), 7.49(1H, m)。
化合物 418： 油状物。 δρρπι 2.89(3Η, d), 3.42(3Η, s), 3.94(3Η, s), 5.16(2Η, s), 6.43(1Η, m), 6.79(1Η, bs), 6·96(1Η, m), 7.25(3 Η， m), 7.46(3Η, m)。
化合物 439:油状物。 Sppm 3.75(3H, s), 3.77(3H, s), 3.81(3H, s), 3.88(3H, s), 5.20(2H, s), 6.10(1H, s), 6.94(2H, m), 7.26(1H, m), 7.42(3H, m), 7.61 (1H, m), 7.87(1H, m)。
化合物 440:油状物。 Sppm 2.39(3H, s), 2.52(3H, s), 3.74(6H, s), 3.80(3H, s), 5.18(2H, s), 5.65(1H， s), 6.92(1H, s), 7.42(3H, m), 7.48(1H, m)。
化合物 441 : 油状物。 Sppm 2.39(3H, s), 2.51 (3 H, s), 3.66(3H, s), 3.69(3H, s), 3.81(3H, s), 5.00(21-1, s)， 6.56(1H, s), 6.86(1H, s)， 7.20(1H, m), 7.35(2H, m), 7.50(1H, m),
Figure imgf000025_0001
化合物 442: 油状物。 Sppm 3.63(3H, s), 3.73(3H, s), 3.85(3H5 s), 3.92(3H, s), 4.05(3H, s), 5.00(2H, s), 5.67(1H, s), 6.79(2H, m), 6.92(2H, m), 7.25(1 H, m)。
制剂实施例 （配方中活性组分的加入量为折百后计量加入，所有百分含量均为 重量百分含量）
实例 5 35 %乳油
化合物 2 (含量 97.2%) 35%
亚磷酸 ' 10%
乙氧基化甘油三酸酯 15%
环已酮' 补足至 100%
将亚磷酸溶解在环已酮中： 然后加入化合物 2和乙氧基化甘油三酸酯，得到透明 的溶液。
实例 6 60%可湿性粉剂
化合物 64 (含量 98.4% ) 60%
十二垸基萘磺酸钠 2%
木质素磺酸钠 9%
高岭土 . 补足至 100%
将化合物 64、 十二烷基萘磺酸钠、 木质素磺酸钠及高岭土 （均为固体）混合在 一起， 在粉碎机中粉碎， 直到颗粒达到标准。
实例 7 30%含水悬浮液
化合物 121 (含量 96.8%) 30%
十二烷基萘磺酸钠 4%
半纤维素 2%
环氧丙烷 8%
水 补足至 100%
将化合物 121与应加水量的 80%及十二垸基萘磺酸钠在球磨机中 （1mm珠） 中 一起粉碎。 半纤维素和环氧丙垸溶解在其余 20%的水中， 然后搅拌加入上述组分。
实例 8 25 %悬浮一乳剂浓缩物
化合物 11 (含量 96.2% ) 25%
环氧甲乙烷环氧丙垸共聚物 2.5%
十二烷基醇聚乙二 4%
乙氧基甘油三酸酯 2%
十二垸基苯磺酸钙 1.5%
环己酮 30%
烷基芳基馏分 补足至 100%
将化合物 11溶解在 80%的应加入溶剂量中（环己酮和烷基芳基馏分），然后加入 乳化剂（十二烷基醇聚乙二醇磷酸酯、 乙氧基甘油三酸酯及十二烷基苯磺酸钙）和分 散剂（2,5份环氧甲乙烷环氧丙垸共聚物），将混合物彻底搅抨。混合物在球磨机（lmm 珠） 中粉碎， 然后再加入其余 20%的溶剂。
生物活性测定
实例 9 杀菌活性测定
用本发明化合物对植物的多种真菌病害进行了活性测定。 试验方法如下： 保护作用和治疗作用测定采用盆栽测定法。待测化合物原药用少量丙酮溶解，用 含有 0.1%吐温 80的水稀释至所需的浓度。保护作用测定首先将药液喷雾处理到植物 试材上， 24 小时后进行病害接种。 接种后， 将植物放在恒温恒湿培养箱中， 使感染 继续， 待对照充分发病后（通常为一周时间）进行评估调查。 治疗作用则首先接种病 原菌， 4 天后进行喷雾处理，待对照充分发病后（喷雾处理后 3-4天）进行评估调査。
部分测试结果如下- 在 500 mg/L剂量下， 化合物 16等对小麦白粉病（ BLumeria gra z' '^)的防效为 100%, 化合物 1、 15、 26、 185、 367达到 80%以上。
在 500 mg/L 剂量下， 化合物 1、 8、 15、 194、 367、 415 等对黄瓜霜霉病 (Pseudoperonospora cubenis) 的防效为 100%， 化合物 11、 391为 90%。
在 500 mg/L剂量下， 化合物 21等对黄瓜灰霉病（ Botrytis d er )和小麦白粉病 的防效为 100%。
在 500 mg/L时， 化合物 10、 20、 63、 78等对黄瓜霜霉病和小麦白粉病的防效为 100%。
化合物 15、 20、 63、 78在 25 mg/L剂量下对黄瓜霜霉病的防效为 100%， 在 12.5 mg/L剂量下对小麦白粉病的防效达 95%以上。
化合物 63在 100 mg/L剂量下， 对黄瓜炭疽病 fCo /etot 'c½m !agma!'ium)具有 100%的防治效果， 1.56 mg/L时防效仍为 100%。
化合物 63除对稻瘟病 oryzae), 番茄晚疫病（ Phytophthora infestans), 黄瓜霜霉病、 小麦白粉病、 黄瓜炭疽病、
Figure imgf000027_0001
fuliginea) 和水稻 紋枯病 {Rhizoctonia solani) 有效夕卜， 对黄瓜黑星病 ( Cladosporium cucumerinum ) 、 苹果腐烂病 Vaha malO、油菜菌核病 Sderotinia sclerotiorum 也具有较好的活性， 对番茄叶霉病 iFulvia fulva) 、 玉米小斑病 Helminthosporium maydis) 、 小麦赤霉 病 ( Fusarium grammearum ) 表现出一定的活性。
化合物 63防治水稻纹枯病和小麦白粉病的试验结果见下表 2〜4。
表 2 化合物 63防治水稻紋枯病的试验结果
„ ^ , 1 天保护效果 （％)
药剂
lOOmg/ 50mg/L 25mg/L 12.5mg/ 6.25mg/L 3.125mg/L 1.5625mg/
63 100 100 80 75 65 60 55 甲基托布津 75 55 20 0 0 0 0
表 3 化合物 63防治小麦白粉病试验结果
1 天保护效果 （％)
药剂
25mg/L 12.5mg/L 6.25mg/L 3.125mg/L 1.56 mg/L 0.78mg/L 0.39mg/L 0.19 mg L
63 100 100 100 100 100 95 75 55 醚菌酯 100 100 98 70 40 15 0 - 表 4 化合物 63防治小麦白粉病试验结果 4天治疗效果 （％)
药剂 -
12.5mg/L 6.25mg/L 3.125 mg/L 1.56mg/L 0.78 mg/L 0.39rag/L
63 100 100 100 100 80 50 戊唑醇 85 70 45 15 0 0 唑菌胺酯 100 100 85 60 25 0 醚菌酯 100 20 15 10 0 0 实例 10 杀虫杀螨活性测定
用本发明化合物对几种昆虫和螨类进行了杀虫活性测定试验。 测定的方法如下： 待测化合物用丙酮 /甲醇（1 : 1 )的混合溶剂溶解后， 用含有 0.1%吐温 80的水稀 释至所需的浓度。 '
以粘虫 (·Lewcam'a separated、小菜蛾 ( ¾/ts//a x_y/ayte//a)禾口淡色库蚊 ( Q//ex pipiens pallens) 2龄幼虫、 桃蚜 (Myzus persicae ) 、 朱砂叶螨 ( Tetranychus cinnabarinus) 为靶标， 采用 airbrush喷雾法和浸液法（淡色库蚊幼虫）.进行杀虫活性测定， airbrush 喷雾处理的压力为 10 psi (约合 0.7 kg/cm2), 喷液量为 0.5 mL。 处理后 2天调查靶标 的死亡率。
部分测试结果如下：
药液浓度为 600 mg/L时， 化合物 15、 21、 63、 64等对粘虫、 小菜蛾、 桃蚜、 淡 色库蚊死亡率达 85%以上。
化合物 15在 200 mg/L剂量下对桃蚜死亡率为 90%，化合物 63在 200 mg/L剂量 下对小菜蛾死亡率为 100%。

Claims

1. 一种芳基醚类化合物， 如通式 Ϊ所示:
Figure imgf000029_0001
式中：
Xi选自 0、 S或 NR2;
权
X2选自 CH
当 ¾选自
Figure imgf000029_0002
时， 嘧啶的 4_位与氧相连， 6-位氧与苯环相连；
Ri选自氢、 卤原子、 硝基、 氰基、 CONH2、 CH2CO书¾、 CH2CN、 C C12烷基、 卤代 C C12烷基、 ^ ^烷氧基、 卤代 CrC12烷氧基、 d-C12烷硫基、 CrC12烷磺酰 基、 C C12烷基羰基、 -C12垸氧基 d-C12烷基、 d-C12烷氧基羰基、 CrC12烷氧基 羰基 CrC12烷基、 d-Cu卤代垸氧基 -C 垸基、 取代或未取代的胺基 垸基； R2选自氢、 C C12烷基、 卤代 C C12烷基、 -C12烷氧基羰基或 d-C12垸氧基羰 基 C!-C 烧基；
Q选自如下所示的基团之一：
Figure imgf000029_0003
当 Q选自 Qi、 Q2、 Q3或 Q5， X2=CH2时， Ar选自取代或未取代的五元杂芳基; 当 Q=Qi, 或当 Q=Q4, x2=CH2时， Ar选自取代或未取代的芳基、 杂芳基； 取代基选自卤原子、 CN、 硝基、 d-C6烷基、 d-C6烷氧基、 C 垸硫基、 C C6烷磺酰基、 CrC6垸氧基羰基、 C C6卤代垸氧基、取代的芳基或取代的芳氧基; 及其立体异构伴。 ,
根据权利要求 1所述的化合物， 其特征在于： 通式 I 中
Xi选自 0、 S或 NR2; X2选自 CH2
Figure imgf000030_0001
选自氢、 卤原子、 硝基、 氰基、 CONH2、 C¾CONH2、 CH2CN、 C C6烷基、 卤代 CrC6烷基、 d-C6垸氧基、 卤代 C C6垸氧基、 C C6烷硫基、 C C6烷磺酰基、 CrC6垸基羰基、 C C6烷氧基 C C6垸基、 C C6垸氧基羰基、 C C6烷氧基羰基 d- C6 烷基、 d-C6卤代烷氧基 -Cs烷基、 取代或未取代的胺基 d-C6垸基；
选自氢、 d-C6烷基、 卤代 C C6烷基、 C C6烷氧基羰基或 CrC6烷氧基羰基 Ci-C<s焼基；
当 Q选自 Qt、 Q2、 Q3或 Q5， X2=CH2时， Ar选自取代或未取代的五元杂芳基；
¾
Figure imgf000030_0002
Bi, Ar选自取代或未取代的芳基、 杂芳基； 取代基选自卤原子、 CN、 硝基、 C C6.烷基、 C C6烷氧基、 d-C6烷硫基、 C C6烷磺酰基、 d-C6烷氧基羰基、 CrC6卤代烷氧基、取代的苯基或取代的苯氧基。
3. 根据权利要求 2所述的化合物， 其特征在于： 通式 I 中
Xi选自 0或 NR2;
X2选自 CH2
Figure imgf000030_0003
选自氢、 卤原子、 硝基、 氰基、 CONH2、 CH2CONH2、 CH2CN、 C C6烷基、 卤代 C C6烷基、 C C6烷氧基、 卤代 C C6烷氧基、 d-C6烷硫基、 -C6烷磺酰基、 C C6烷基羰基、 C C6烷氧基 CrC6烷基、 Q-C6垸氧基羰基、 -C6烷氧基羰基 C C6 烷基、 C C6卤代垸氧基 C C6烷基、 取代或未取代的胺基 CrC3烷基；
选自氢、 Q-C6烷基、 卤代 -C6垸基、 d-C3烷氧基羰基或 C C6烷氧基羰基
C1-C3焼基；
当 Q选自 Qi、 Q2、 Q3或 Q5， X2=Ci¾时， Ar选自取代或未取代的呋喃、 噻吩或 噻唑； Q-Qi,
Figure imgf000030_0004
时， Ar选自取代或未取代的 苯基、吡啶基、呋喃、噻吩或噻唑；取代基选自卤原子、 CN、硝基、 烷基、 d-C6 烷氧基、 - 垸硫基、 C C6垸磺酰基、 -C6卤代烷氧基、 取代的苯基或取代的苯 氧基。
4. 根据权利要求 3所述的化合物， 其特征在于： 通式 I 中
选自 0或 NR2;
X2选自 C¾
Figure imgf000030_0005
选自氢、 氯、 溴、 氟、 硝基、 氰基、 CH2CN或 -C6垸基；
R2选自氢、 CrC3烷基、 卤代 C C3烷基、 CrC3烷氧基羰基或 d- 烷氧基羰基 C C3 ;1完基；
当 Q=Qi、 Q2、 Q3或 Qs， X2=CH2时， Ar选自取代或未取代的呋喃、噻吩或噻唑; 当 Q Q
Figure imgf000031_0001
时， Ar选自取代或未取代的苯基、 吡 啶基、 呋喃、 噻吩或噻唑； 取代基选自卤原子、 CN、 硝基、 -C6烷基、 C C6烷氧 基、 -¾烷硫基、 C C6卤代烷氧基、 氯代苯基或氯代苯氧基。
5. 根据权利要求 4所述的化合物， 其特征在于： 通式 I 中
Xi选自 0或 NR2;
X2选自 CH2
Figure imgf000031_0002
选自氢或曱基；
R2选自氢、 甲基或异丙基；
当 Q=Qi、 Q2、 Q3或 Q5， X2=CH2时， Ar选自取代或未取代呋喃或噻吩；当 Q=Q1 ;
X.
Figure imgf000031_0003
时， Ar选自取代或未取代的苯基、 吡啶基、 呋 喃或噻吩； 取代基选自 1-2个卤素、 d-Cs烷基、 d-C3烷氧基、 CrC3烷硫基或 C C3 卤代烷氧基。
6. 根据权利要求 1-5中任意一项所述的化合物， 其特征在于： 通式 I 的化合物 由式 III所示的含羟基的唑类化合物和式 IV所示的苄卤在碱性条件下反应制得：
Figure imgf000031_0004
ΙΠ IV
通式 IV中， R是离去基团， 选自氯或溴。
7. 一种权利要求 1所述的通式 I化合物在防治作物上害虫的应用。
8. 一种权利要求 1所述的通式 I化合物在防治作物上病菌的应用。
9. 一种杀虫、 杀菌组合物， 其特征在于含有如权利要求 1 所述的化合物和农业 上可接受的载体， 组合物中活性组分的重量百分含量为 1-99%。
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JP2008545664A (ja) 2008-12-18
EP1884511A1 (en) 2008-02-06
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JP4859919B2 (ja) 2012-01-25
CN100427481C (zh) 2008-10-22
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ATE541834T1 (de) 2012-02-15
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US20080275070A1 (en) 2008-11-06
CN1869034A (zh) 2006-11-29

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