WO2017024971A1 - 一种不饱和肟醚类化合物及其用途 - Google Patents

一种不饱和肟醚类化合物及其用途 Download PDF

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WO2017024971A1
WO2017024971A1 PCT/CN2016/093000 CN2016093000W WO2017024971A1 WO 2017024971 A1 WO2017024971 A1 WO 2017024971A1 CN 2016093000 W CN2016093000 W CN 2016093000W WO 2017024971 A1 WO2017024971 A1 WO 2017024971A1
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compound
formula
alkyl
group
halogenated
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French (fr)
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张立新
程学明
赵杰
张静
李志念
徐利保
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沈阳中化农药化工研发有限公司
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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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
    • C07C251/60—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by carboxyl groups

Definitions

  • the invention belongs to the field of agricultural fungicides.
  • it relates to an unsaturated oxime ether compound and its use.
  • Strobilurin fungicides are a class of high-efficiency, low-toxic, broad-spectrum fungicides that are structurally characterized by beta-methoxy acrylate structural units; these compounds have been developed in a number of commercial varieties.
  • the patent CN1191670A discloses the following compound CK1 which has bactericidal and insecticidal activity. This compound has been developed as a commercial fungicide, and the Chinese name is "enesporum ester" (English name: Enoxastrobin).
  • the following compounds CK2 (compound 1), CK3 (compound 2), CK4 (compound 3), and CK5 (compound 4) are disclosed in the patent CN1580041A, which have bactericidal and insecticidal activity. As shown in the patent CN1580041A, the compounds CK2 to CK5 are the four stereoisomers of the compound CK1 (enestrobin).
  • the disease may cause resistance to it, and thus it is necessary to continuously develop new and improved bactericidal compounds and compositions to meet agricultural and forestry applications.
  • the compound provided by the present invention is used as a bactericide in the fields of agriculture and forestry, and can effectively inhibit pathogens in agriculture and forestry.
  • R 1 is selected from unsubstituted or optionally substituted aryl or heteroaryl
  • R 2 is selected from a C 1 -C 6 alkyl group or a halogenated C 1 -C 6 alkyl group;
  • W is selected from CH or N;
  • Q is selected from NH or O
  • B1 and B2 represent double bonds
  • R 1 is selected from phenyl which is unsubstituted or further substituted by 1 to 5 identical or different R 3 ;
  • R 2 is selected from C 1 -C 6 alkyl or halogenated C 1 -C 3 alkyl
  • R 3 is selected from the group consisting of halogen, cyano, nitro, hydroxy, decyl, amino, CONH 2 , COOH, CHO, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 3 -C 6 naphthenic , C 1 -C 3 alkoxy, halo C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, halo C 1 -C 3 alkylthio, C 1 -C 3 alkylamino , C 1 -C 3 dialkylamino, C 3 -C 6 cycloalkylamino, C 1 -C 3 alkoxycarbonyl, C 1 -C 3 alkylsulfonyl, C 1 -C 3 alkylaminocarbonyl Or a C 1 -C 3 alkylaminosulfonyl group;
  • W is selected from CH or N;
  • Q is selected from NH or O
  • R 1 is selected from phenyl which is unsubstituted or further substituted with from 1 to 4 identical or different R 3 ;
  • R 2 is selected from C 1 -C 6 alkyl
  • R 3 is selected from the group consisting of halogen, cyano, nitro, hydroxy, decyl, amino, COOH, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 3 alkoxy, halogen C 1- C 3 alkoxy, C 1 -C 3 alkylthio, halogenated C 1 -C 3 alkylthio, C 1 -C 3 alkylamino, C 1 -C 3 dialkylamino, C 1 - C 3 alkoxycarbonyl or C 1 -C 3 alkylsulfonyl;
  • W is selected from CH or N;
  • Q is selected from NH or O
  • R 1 is selected from phenyl which is unsubstituted or further substituted by 1 to 3 identical or different R 3 ;
  • R 2 is selected from C 1 -C 3 alkyl
  • R 3 is selected from the group consisting of halogen, cyano, nitro, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 3 alkoxy, halogenated C 1 -C 3 alkoxy, a C 1 -C 3 alkylamino group, a C 1 -C 3 dialkylamino group or a C 1 -C 3 alkylsulfonyl group;
  • W is selected from N;
  • Q is selected from NH
  • R 1 is selected from phenyl which is unsubstituted or further substituted by 1 to 3 identical or different R 3 ;
  • R 2 is selected from a methyl group
  • R 3 is selected from the group consisting of halogen, cyano, nitro, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 3 alkoxy, halogenated C 1 -C 3 alkoxy, a C 1 -C 3 dialkylamino group or a C 1 -C 3 alkylsulfonyl group;
  • W is selected from N;
  • Q is selected from NH
  • R 1 is selected from phenyl substituted with 1-2 of the same or different R 3 ;
  • R 2 is selected from a methyl group
  • R 3 is selected from halogen, cyano or halogenated C 1 -C 4 alkyl
  • W is selected from N;
  • Q is selected from NH
  • R 1 is selected from phenyl substituted by 1 R 3 and R 3 is at the 4-position of the phenyl ring;
  • R 2 is selected from a methyl group
  • R 3 is selected from halogen
  • the double bond B1 is a stereoisomer of the formula E, and other stereoisomers.
  • R 1 is selected from phenyl substituted by 1 R 3 and R 3 is at the 4-position of the phenyl ring;
  • R 2 is selected from a methyl group
  • R 3 is selected from fluorine or chlorine
  • Double bond B1 is E; and/or
  • the double bond B2 is of the E type.
  • R 1 is selected from unsubstituted or optionally substituted aryl or heteroaryl
  • R 2 is selected from a C 1 -C 6 alkyl group or a halogenated C 1 -C 6 alkyl group;
  • B1 and B2 represent double bonds
  • Aryl includes phenyl and naphthyl.
  • Heteroaryl means a five-membered ring, six-membered ring or fused heterocyclic ring containing one or more N, O, S heteroatoms.
  • Alkyl straight or branched alkyl such as methyl, ethyl, n-propyl, isopropyl or a different butyl, pentyl or hexyl isomer.
  • Haloalkyl a linear or branched alkyl group in which a hydrogen atom may be partially or completely substituted by a halogen such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl or difluoromethyl. Base, trifluoromethyl, heptafluoroisopropyl, and the like.
  • Halogen refers to fluorine, chlorine, bromine or iodine.
  • Cycloalkyl a substituted or unsubstituted cyclic alkyl group such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group; a substituent such as a methyl group, a halogen or the like.
  • Alkoxy a linear or branched alkyl group bonded to a structure via an oxygen atom such as a methoxy group, an ethoxy group, a t-butoxy group or the like.
  • Haloalkoxy a linear or branched alkoxy group in which a hydrogen atom may be partially or completely substituted by a halogen such as chloromethoxy, dichloromethoxy, trichloromethoxy or fluoro Methoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, and the like.
  • Alkylthio a linear or branched alkyl group bonded to a structure via a sulfur atom, such as a methylthio group, an ethylthio group or the like.
  • Halogenated alkylthio a linear or branched alkylthio group, and a hydrogen atom on these alkylthio groups may be partially or completely substituted by a halogen such as a difluoromethylthio group, a trifluoroethylthio group or the like.
  • Alkylamino a linear or branched alkyl group bonded to the structure via a nitrogen atom, such as methylamino, ethylamino, n-propylamino, isopropylamino or isomeric butylamine.
  • Dialkylamino two identical or different straight or branched alkyl groups bonded to the structure via a nitrogen atom, such as dimethylamino, methylethylamino and the like.
  • Cycloalkylamino cycloalkyl-NH-, such as cyclopropylamino.
  • Alkoxycarbonyl alkyl -O-CO-, for example, CH 3 OCO-.
  • Alkylsulfonyl alkyl-S(O) 2- , such as methylsulfonyl.
  • Alkylaminocarbonyl group an alkyl group -NH-CO-, for example, CH 3 NHCO-.
  • Alkylaminosulfonyl alkyl-NH-S(O) 2 - such as CH 3 NHS(O) 2 -.
  • the compound of the formula I of the present invention is used in the field of agriculture and forestry, and has an efficient bactericidal effect. Further studies on the compound of the formula I have revealed that the compound of the formula I has various stereoisomers. structure.
  • the double bond B1 is E or Z
  • the double bond B2 is E or Z
  • the stereoisomer structures shown have good bactericidal effects.
  • the isomers of the formula I according to the invention include the E or Z isomers, as well as mixtures of these isomers.
  • the compounds of the formulae I and II may have one or more due to different substitution modes. Chiral centers where they exist as a mixture of enantiomers or diastereomers.
  • the invention provides the use of the pure enantiomers or diastereomers and mixtures thereof and the pure enantiomers or diastereomers of the compounds of the formulae I and II or mixtures thereof.
  • Suitable compounds of the formulae I and II also include all possible stereoisomers (Z-form/E-isomer) and mixtures thereof.
  • a method for preparing a part of the compound of the formula I (the compound of the formula I-1) comprises:
  • the intermediate compound of the formula II and the compound of the formula III are reacted in the presence of a base in a suitable solvent at a temperature from -10 ° C to the boiling point of the solvent.
  • a base in a suitable solvent at a temperature from -10 ° C to the boiling point of the solvent.
  • the compound of the formula I-1 is obtained in 0.5 to 48 hours.
  • Suitable bases may be sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide or triethylamine.
  • Suitable solvents may be dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, methanol, ethanol, ethyl acetate, acetonitrile, dioxane, THF, DMF or DMSO.
  • the compound of the formula IV is obtained by reacting a compound of the formula IV with a compound of the formula V in a suitable solvent in an acid-free or acid-free condition at a temperature of from -10 ° C to the boiling point of the solvent for 0.5 to 48 hours.
  • suitable solvents may be dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, methanol, ethanol, ethyl acetate, acetonitrile, dioxane, THF, DMF or DMSO.
  • Suitable acids can be sulfuric acid, hydrochloric acid or acetic acid.
  • a method for preparing a part of the compound of the formula I (the compound of the formula I-2) comprises:
  • the compound of the formula I-2 can be obtained by reacting a compound of the formula I-1 in a suitable solvent with aqueous methylamine or methylamine hydrochloride at a temperature of from -10 ° C to the boiling point of the solvent for from 0.5 to 48 hours.
  • suitable solvents can be dichloromethane, chloroform, tetrachloro Carbon, hexane, benzene, toluene, methanol, ethanol, ethyl acetate, acetonitrile, dioxane, THF, DMF or DMSO.
  • the compound of the formula II is reacted with a compound of the formula VI (wherein X is a leaving group such as a halogen, etc.) in the presence of a base in a suitable solvent at a temperature of from -10 ° C to the boiling point of the solvent of 0.5 -
  • Suitable bases may be sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide or triethylamine.
  • Suitable solvents may be dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, methanol, ethanol, ethyl acetate, acetonitrile, dioxane, THF, DMF or DMSO.
  • the preparation of the compounds of the general formula II of the invention comprises:
  • the compound of the formula VII is reacted with ethyl 3-ethoxy-2-butenoate in the presence of a base in a suitable solvent at a temperature of from -10 ° C to the boiling point of the solvent for 0.5 to 48 hours.
  • the compound of the formula IV is prepared by reacting the compound of the formula IV with hydroxylamine hydrochloride in the presence of a base in a suitable solvent at a temperature from -10 ° C to the boiling point of the solvent for 0.5 to 48 hours.
  • Suitable bases may be sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide or triethylamine.
  • Suitable solvents may be dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, methanol, ethanol, ethyl acetate, acetonitrile, dioxane, THF, DMF or DMSO.
  • the intermediates III, V and VI can be prepared by known methods, for example, by the methods reported in U.S. Patent 4,723,034, U.S. Patent 5,545, 078, WO 972, 686, U.S. Patent No. 5,194, 662, or Chinese Journal of Chemistry, 27 (10), 2055-2060, 2009, et al.
  • the starting compounds of the formula VII, ethyl 3-ethoxy-2-butenoate and other conventional starting materials and reagents are generally commercially available or can be prepared according to conventional methods.
  • Stereoisomerism may exist in the general compounds II, IV, I-1 and I-2 depending on the difference in the reaction conditions or the starting materials.
  • the B1 key is E type or Z type
  • the B2 key is E type or Z type.
  • R 1 R 2 B1 bond configuration B2 bond configuration 2.1 C 6 H 5 CH 3 E E 2.2 2-Cl-C 6 H 4 CH 3 2.3 3-Cl-C 6 H 4 CH 3 2.4 4-Cl-C 6 H 4 CH 3 E E 2.5 4-Cl-C 6 H 4 CH 3 E Z 2.6 2-FC 6 H 4 CH 3 2.7 3-FC 6 H 4 CH 3 2.8 4-FC 6 H 4 CH 3 E E 2.9 4-FC 6 H 4 CH 3 E Z 2.10 2-Br-C 6 H 4 CH 3 2.11 3-Br-C 6 H 4 CH 3 2.12 4-Br-C 6 H 4 CH 3 2.13 2-Me-C 6 H 4 CH 3 2.14 3-Me-C 6 H 4 CH 3 2.15 4-Me-C 6 H 4 CH 3 2.16 2-CF 3 -C 6 H 4 CH 3 2.17 3-CF 3 -C 6 H 4 CH 3 2.18 4-CF 3 -C 6 H 4 CH 3 2.19 2-MeO-C 6 H 4 CH 3 2.20 3-MeO-C 6 H 4 CH 3 2.21 4-
  • stereoisomer of the compound of the formula I and the compound of the formula I and the stereoisomer of the compound of the formula II and the compound of the formula II are selected by selecting an appropriate starting material or controlling the reaction.
  • the conditions are such that an isomer excess product or a single isomer is obtained; or a single isomer is obtained by subjecting the crude product to separation by conventional means, including column chromatography, recrystallization, and the like.
  • the structure of these isomers can be determined by a conventional method such as X-ray single crystal diffraction, nuclear magnetic resonance or the like.
  • a bactericidal composition comprising the compound of the formula I or a stereoisomer thereof as an active ingredient and a composition comprising an agriculturally acceptable carrier, wherein the active ingredient is present in the composition in an amount of from 1 to 99% by weight. %.
  • the use of the compound of the present invention for controlling plant diseases can be used for controlling diseases caused by various pathogens such as oomycetes, basidiomycetes, ascomycetes and deuteromycetes on various crops, for example, at lower doses.
  • 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 sclerotium, corn leaf spot and other diseases have good control effects.
  • the compound of the present invention has excellent systemic activity and can be used as a foliar and soil bactericide.
  • the present invention also provides a bactericidal composition
  • a bactericidal composition comprising the compound of the formula I or a stereoisomer thereof as an active ingredient and an agriculturally acceptable carrier, the weight percent of the active ingredient in the composition being 1-99%.
  • the invention also provides a process for the preparation of a composition as defined above, wherein the compound of formula I or a stereoisomer thereof is mixed with a carrier.
  • the carrier in the composition of the present invention is a substance which, after being formulated with the active ingredient, is applied 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, including those which are normally gaseous but which have been compressed into a liquid, and which are usually employed in the formulation of the insecticidal or bactericidal compositions.
  • 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; Silicon, synthetic calcium silicate or aluminum silicate; elements such as carbon, sulfur; natural or synthetic resins such as benzofuran resin, polyvinyl chloride, styrene polymers or copolymers; solid polychlorinated phenol; asphalt; 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; Silicon, synthetic calcium silicate or aluminum silicate; elements such as carbon, sulfur; natural or synthetic resins such as benzofuran resin, polyvinyl chloride, styrene polymers or copolymers
  • 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.
  • Figure 1 is a diagram showing the molecular structure of the compound 1.144 of the present invention.
  • the aqueous phase was acidified to pH 2 with hydrochloric acid, and the resulting yellow solid was collected by filtration and washed with water and petroleum ether, respectively. , the intermediate acid is obtained.
  • the intermediate acid was placed in a 100 ml reaction flask, 25 ml of 1 N hydrochloric acid was added, and the temperature was raised to 50 ° C to decarboxylate to no gas evolution. After the reaction was completed by TLC, the reaction mixture was cooled to room temperature, and the mixture was evaporated and evaporated. The yield was 68%.
  • the nuclear magnetic data is as follows:
  • the petroleum ether is washed to obtain an intermediate acid.
  • the intermediate acid was placed in a 100 ml reaction flask, 25 ml of 1 N hydrochloric acid was added, and the temperature was raised to 50 ° C to decarboxylate to no gas evolution. After the reaction was completed by TLC, the reaction mixture was cooled to room temperature, and the mixture was evaporated. The yield was 65%.
  • the nuclear magnetic data is as follows:
  • the oil A contained two compounds of the same molecular weight of 1.140 and 1.141 which were similar in molecular weight, with a ratio of 75:25. Further purification of oil A gave 0.30 g of compound 1.140 and 0.10 g of compound 1.141.
  • the nuclear magnetic data is as follows:
  • the oil B contained two compounds of the same molecular weight of 1.144 and 1.145, and the ratio was 67:33. Oil B was further purified to give 0.64 g of compound 1.144 (white solid) and 0.32 g of compound 1.145 (white solid).
  • the nuclear magnetic data is as follows:
  • the compound 1.144 (0.5 g) was added to ethyl acetate, completely dissolved, and then a small amount of petroleum ether was added, and allowed to stand at room temperature to slowly evaporate to obtain a colorless transparent plate crystal, and a size of 0.36 mm x 0.28 mm x 0.20 mm was selected as a single crystal.
  • Example 7 bactericidal protection activity test
  • Protective activity test method using a live pot assay method, that is, a sample of the test compound is used with a small amount of solvent (such as acetone, methanol, DMF, etc., and according to its ability to dissolve the sample, the amount of solvent and the volume of the spray volume The ratio is equal to or less than 0.05) dissolved, diluted with water containing 0.1% Tween 80, formulated into a desired concentration of the test solution, and a solvent clear water solution is additionally used as a blank control.
  • the test solution was sprayed onto the disease host plant (the host plant was a standard potted seedling cultured in a greenhouse), and the disease was inoculated 24 hours later.
  • the diseased plants that need to be temperature-controlled and moisturized are inoculated and placed in an artificial climate chamber. After the disease is completed, the plants are transferred to the greenhouse for cultivation; the diseased plants that do not need moisturizing culture are directly inoculated and cultivated in the greenhouse.
  • the compound disease prevention effect evaluation was performed after the control was sufficiently ill (usually one week).
  • test results of some compound protection activities are as follows:
  • the concentration of the drug solution is 3.125 mg / liter, the compound 1.140 and the compound 1.144 are not effective against cucumber anthracnose. Less than 98%.
  • the concentration of the drug solution is 1.5625 mg/L
  • the control effect of the compound 1.140 on wheat powdery mildew is 100%
  • the sample A compound 1.140 and the compound 1.141 containing the mass ratio of 3:1
  • the sample B the mass ratio is 2:1 compound 1.144 and compound 1.145
  • compound 1.144, compound 1.145 have no less than 98% control effect on wheat powdery mildew;
  • the concentration of the drug solution is 0.39 mg/L
  • the control effect of the compound 1.144 on wheat powdery mildew is not less than 98%.
  • Example 8 Bactericidal treatment activity test
  • Therapeutic activity test method a live potting method is adopted, that is, the disease host plant (the host plant is a standard potted seedling cultured in a greenhouse) is inoculated with a disease before the spray treatment, and cultured for 24 hours as a test host plant. Further, the sample of the test compound is dissolved with a small amount of solvent (the type of the solvent such as acetone, methanol, DMF, etc., and is selected according to the solvency of the sample, and the volume ratio of the amount of the solvent to the amount of the sprayed liquid is equal to or less than 0.05). 0.1% Tween 80 water was diluted to prepare the desired concentration of the test solution, and a solvent clear water solution was additionally used as a blank control. On the crop sprayer, the test solution is sprayed onto the above-mentioned host plants, and then transferred to a greenhouse for normal culture. The effect of compound treatment was evaluated after a sufficient onset of control (usually one week).
  • solvent the type of the solvent such as acetone, methanol
  • the therapeutic activity of the compound 1.144 against cucumber anthracnose was not less than 90%.
  • the concentration of the drug solution is 25 mg / liter, the therapeutic activity of the compound 1.144 against wheat powdery mildew is 100%;
  • the concentration of the drug solution is 6.25 mg / liter, the therapeutic activity of the compound 1.144 against wheat powdery mildew is 100%;
  • the concentration of the drug solution was 1.5625 mg/L
  • the therapeutic activity of the compound 1.144 against wheat powdery mildew was 100%.
  • Example 9 Comparative test of bactericidal systemic activity
  • Compound test method for controlling the systemic activity of cucumber anthracnose the sample of the test compound is used with a small amount of solvent (the kind of solvent such as acetone, methanol, DMF, etc., and the volume of the solvent and the volume of the sprayed liquid are selected according to the solvency of the sample.
  • the ratio is equal to or less than 0.05) dissolved, diluted with water containing 0.1% Tween 80, formulated into a desired concentration of the test solution, and a solvent clear water solution is additionally used as a blank control.
  • the greenhouse seedlings with uniform growth in the greenhouse were selected as the host, and the leaves were treated with fixed doses. After treatment, they were transplanted into the greenhouse for normal culture and inoculated 24 hours later (see the protective activity test method for other methods).
  • Test method for controlling the systemic activity of wheat powdery mildew by using compound the sample of the test compound is used with a small amount of solvent (the kind of solvent such as acetone, methanol, DMF, etc., and is selected according to the solvency of the sample, the volume of the solvent and the volume of the sprayed liquid) The ratio is equal to or less than 0.05) dissolved, diluted with water containing 0.1% Tween 80, formulated into a desired concentration of the test solution, and a solvent clear water solution is additionally used as a blank control. Select the potted wheat seedlings in the greenhouse as the host, carry out fixed-point drip treatment on the leaves, transfer to the greenhouse for normal culture, and inoculate 24 hours later (see the protective activity test method for other methods).
  • solvent the kind of solvent such as acetone, methanol, DMF, etc.
  • the compounds CK1 to CK9 disclosed in the prior art were used as a control compound, and some of the compounds of the present invention and their stereoisomers were selected for activity comparison, such as sample A, compound 1.140, sample B, and compound 1.144.
  • the compound CK1 is prepared and isolated according to the method described in Synthesis Example 2 of Patent CN1191670A; the compounds CK2 to CK5 are prepared and isolated according to the methods described in Synthesis Examples 1 and 2 of Patent CN1580041A; CK6 was prepared and isolated according to the method described in Synthesis Example 1 of Patent CN1309897A; the compounds CK7 to CK9 were prepared and isolated according to the method described in Synthesis Example 8 of Patent WO0212172A1.

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Abstract

提供了一种不饱和肟醚类化合物及其应用。所述化合物如通式I所示，通式I化合物具有优异的杀菌活性，尤其对黄瓜炭疽病和小麦白粉病在较低剂量下仍具有良好的防治效果，同时还具有优异的内吸活性。因此，通式I所示化合物在农业和其它领域中用作杀菌剂的用途。

Description

一种不饱和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。具体地涉及一种不饱和肟醚类化合物及其应用。
背景技术
Strobilurin类杀菌剂是一类高效、低毒、广谱型杀菌剂，其结构特点是含有β-甲氧基丙烯酸酯结构单元；该类化合物目前已被开发出多个商品化品种。
诸如，专利CN1191670A中公开了如下化合物CK1，其具有杀菌和杀虫活性。该化合物现已被开发为商品化杀菌剂，中文通用名为“烯肟菌酯”(英文通用名：Enoxastrobin)。
Figure PCTCN2016093000-appb-000001
CK1(烯肟菌酯)
专利CN1580041A中公开了如下化合物CK2(化合物1)、CK3(化合物2)、CK4(化合物3)、CK5(化合物4)，具有杀菌和杀虫活性。如专利CN1580041A所示，化合物CK2～CK5为化合物CK1(烯肟菌酯)的四种立体异构体。
专利CN1309897A中公开了如下化合物CK6，具有杀菌活性。该化合物现已被开发为商品化杀菌剂，中文通用名为“烯肟菌胺”(英文通用名：Fenaminstrobin)。
Figure PCTCN2016093000-appb-000002
CK6(烯肟菌胺)
专利WO0212172A1中公开了如下化合物CK7(化合物3.16A)、CK8(化合物3.16B)、CK9(化合物3.16)，具有杀菌活性。
杀菌剂长时间使用后，病害会对其产生抗性等问题，因此需要不断研发新型的和改进的具有杀菌活性的化合物和组合物以满足农业、林业的应用。
发明内容
本发明的目的是提供一种不饱和肟醚类化合物及其用途。本发明提供的化合物作为杀菌剂，用于农业和林业领域，可有效抑制农业和林业中的病菌。
为实现上述目的，本发明的技术方案如下：
一种不饱和肟醚类化合物，如通式I所示：
Figure PCTCN2016093000-appb-000003
式I
式中：
R1选自未取代的或任意取代的芳基或杂芳基；
R2选自C1-C6烷基或卤代C1-C6烷基；
W选自CH或N；
Q选自NH或O；
B1和B2代表双键；
或，通式I所示化合物的立体异构体。
优选通式I中，
R1选自未取代的或被1-5个相同或不同的R3进一步取代的苯基；
R2选自C1-C6烷基或卤代C1-C3烷基；
R3选自卤素、氰基、硝基、羟基、巯基、氨基、CONH2、COOH、CHO、C1-C4烷基、卤代C1-C4烷基、C3-C6环烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C1-C3烷硫基、卤代C1-C3烷硫基、C1-C3烷基氨基、C1-C3二烷基氨基、C3-C6环烷基氨基、C1-C3烷氧基羰基、C1-C3烷基磺酰基、C1-C3烷基氨基羰基或C1-C3烷基氨基磺酰基；
W选自CH或N；
Q选自NH或O；
或，通式I所示化合物的立体异构体。
进一步优选，通式I中，
R1选自未取代的或被1-4个相同或不同的R3进一步取代的苯基；
R2选自C1-C6烷基；
R3选自卤素、氰基、硝基、羟基、巯基、氨基、COOH、C1-C4烷基、卤代C1-C4烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C1-C3烷硫基、卤代C1-C3烷硫基、C1-C3烷基氨基、C1-C3二烷基氨基、C1-C3烷氧基羰基或C1-C3烷基磺酰基；
W选自CH或N；
Q选自NH或O；
或，通式I所示化合物的立体异构体。
再进一步优选，通式I中，
R1选自未取代的或被1-3个相同或不同的R3进一步取代的苯基；
R2选自C1-C3烷基；
R3选自卤素、氰基、硝基、C1-C4烷基、卤代C1-C4烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C1-C3烷基氨基、C1-C3二烷基氨基或C1-C3烷基磺酰基；
W选自N；
Q选自NH；
或，通式I所示化合物的立体异构体。
更优选，通式I中，
R1选自未取代的或被1-3个相同或不同的R3进一步取代的苯基；
R2选自甲基；
R3选自卤素、氰基、硝基、C1-C4烷基、卤代C1-C4烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C1-C3二烷基氨基或C1-C3烷基磺酰基；
W选自N；
Q选自NH；
或，通式I所示化合物的立体异构体。
更进一步优选，通式I中，
R1选自被1-2相同或不同的个R3取代的苯基；
R2选自甲基；
R3选自卤素、氰基或卤代C1-C4烷基；
W选自N；
Q选自NH；
或，通式I所示化合物的的Z或E式立体异构体。
更再进一步优选：通式I中
R1选自被1个R3取代的苯基，且R3在苯环的4位；
R2选自甲基；
R3选自卤素；
或，通式I所示化合物中双键B1为E式的立体异构体，其它立体异构体。
最优选：通式I中
R1选自被1个R3取代的苯基，且R3在苯环的4位；
R2选自甲基；
R3选自氟或氯；
双键B1为E式；和/或
双键B2为E式。
一种用于制备通式I化合物的中间体，中间体如通式II所示：
Figure PCTCN2016093000-appb-000004
式II
式中：
R1选自未取代的或任意取代的芳基或杂芳基；
R2选自C1-C6烷基或卤代C1-C6烷基；
B1和B2代表双键；
或，通式II所示化合物的Z或E式立体异构体。
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。
芳基：包括苯基和萘基。
杂芳基：指含一个或多个N、O、S杂原子的五元环、六元环或稠杂环。例如吡咯基、呋喃基、噻吩基、咪唑基、吡唑基、恶唑基、噻唑基、异恶唑基、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、苯并恶唑基、苯并噻吩基、苯并噻唑基、苯并异恶唑基、苯并异噻唑基、苯并咪唑基、苯并吡唑基、喹喔啉基等。
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。
卤素：指氟、氯、溴或碘。
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。
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。
烷氧基羰基：烷基-O-CO-，例如CH3OCO-。
烷基磺酰基：烷基-S(O)2-，例如甲基磺酰基。
烷基氨基羰基：烷基-NH-CO-，例如CH3NHCO-。
烷基氨基磺酰基：烷基-NH-S(O)2-，例如CH3NHS(O)2-。
本发明通式I所示的化合物应用在农业和林业领域中，具有高效的杀菌效用，进一步对通式I所示化合物进行研究发现：所述通式I所示化合物具有多种立体异构体结构。
可选地，通I中，双键B1为E式或Z式，或者双键B2为E式或Z式，所示立体异构体结构均具良好的杀菌效用。本发明通式I所示异构体包括E式或Z式异构体，以及这些异构体的混合物。
在本发明的化合物中，由于不同的取代方式，通式I和II化合物可以具有一个或多 个手性中心，此时它们以对映体或非对映体的混合物存在。本发明提供了纯对映体或非对映体及其混合物以及通式I和II化合物的纯对映体或非对映体或其混合物的用途。合适的通式I和II化合物还包括所有可能的立体异构体(Z式/E式异构)及其混合物。
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。
(1)当Q＝O时，通式I中部分化合物(通式I-1化合物)的制备方法包括：
方法一：
Figure PCTCN2016093000-appb-000005
中间体通式II化合物与通式III化合物(通式III中X为离去基团，如卤素等)在碱的存在下，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-1化合物。适宜的碱可为碳酸钠、碳酸钾、氢氧化钠、氢氧化钾、甲醇钠、乙醇钠、叔丁醇钠、叔丁醇钾或三乙胺等。适宜的溶剂可为二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、甲醇、乙醇、乙酸乙酯、乙腈、二氧六环、THF、DMF或DMSO等。
方法二：
Figure PCTCN2016093000-appb-000006
通式IV化合物与通式V化合物在适宜的溶剂中，在无酸或有酸条件下，在温度从-10℃到溶剂沸点下反应0.5-48小时制得通式I-1化合物。适宜的溶剂可为二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、甲醇、乙醇、乙酸乙酯、乙腈、二氧六环、THF、DMF或DMSO等。适宜的酸可为硫酸、盐酸或醋酸。
(2)当Q＝N时，通式I中部分化合物(通式I-2化合物)的制备方法包括：
方法一：
Figure PCTCN2016093000-appb-000007
由通式I-1化合物在适宜的溶剂中，与甲胺水溶液或甲胺盐酸盐，在温度-10℃到溶剂沸点下反应0.5-48小时制得通式I-2化合物。适宜的溶剂可为二氯甲烷、氯仿、四氯 化碳、己烷、苯、甲苯、甲醇、乙醇、乙酸乙酯、乙腈、二氧六环、THF、DMF或DMSO等。
方法二：
Figure PCTCN2016093000-appb-000008
通式II化合物与通式VI化合物(通式VI中X为离去基团，如卤素等)在碱的存在下，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-2化合物。适宜的碱可为碳酸钠、碳酸钾、氢氧化钠、氢氧化钾、甲醇钠、乙醇钠、叔丁醇钠、叔丁醇钾或三乙胺等。适宜的溶剂可为二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、甲醇、乙醇、乙酸乙酯、乙腈、二氧六环、THF、DMF或DMSO等。
本发明的通式II化合物的制备包括：
Figure PCTCN2016093000-appb-000009
其中，除另有注明外，式中各基团的定义同前。
通式VII化合物与3-乙氧基-2-丁烯酸乙酯在碱的存在下，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IV化合物。通式IV化合物再与羟胺盐酸盐在碱的存在下，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。适宜的碱可为碳酸钠、碳酸钾、氢氧化钠、氢氧化钾、甲醇钠、乙醇钠、叔丁醇钠、叔丁醇钾或三乙胺等。适宜的溶剂可为二氯甲烷、氯仿、四氯化碳、己烷、苯、甲苯、甲醇、乙醇、乙酸乙酯、乙腈、二氧六环、THF、DMF或DMSO等。
上述制备方法中所涉及的原料及中间体来源如下：
中间体III、V及VI可以按公知方法制备，例如参照US4723034、US5554578、WO9721686、US5194662或Chinese Journal of Chemistry,27(10),2055-2060，2009等报道的方法制得。
原料通式VII化合物、3-乙氧基-2-丁烯酸乙酯及其它常规原料和试剂通常有市售，也可按照常规方法自制。
根据反应条件的差异或起始原料的不同，通式化合物II、IV、I-1和I-2均有可能存在立体异构现象。例如B1键为E式或Z式，B2键为E式或Z式。
进而获得本发明优选的部分通式I化合物及通式I所示化合物的立体异构体如表1所示，以及优选部分通式II化合物及通式II所示化合物的立体异构体如表2所示，但本 发明绝非仅限于这些化合物。
表1
Figure PCTCN2016093000-appb-000010
Figure PCTCN2016093000-appb-000011
Figure PCTCN2016093000-appb-000012
Figure PCTCN2016093000-appb-000013
Figure PCTCN2016093000-appb-000014
Figure PCTCN2016093000-appb-000015
Figure PCTCN2016093000-appb-000016
Figure PCTCN2016093000-appb-000017
Figure PCTCN2016093000-appb-000018
表2
Figure PCTCN2016093000-appb-000019
编号 R1 R2 B1键构型 B2键构型
2.1 C6H5 CH3 E E
2.2 2-Cl-C6H4 CH3    
2.3 3-Cl-C6H4 CH3    
2.4 4-Cl-C6H4 CH3 E E
2.5 4-Cl-C6H4 CH3 E Z
2.6 2-F-C6H4 CH3    
2.7 3-F-C6H4 CH3    
2.8 4-F-C6H4 CH3 E E
2.9 4-F-C6H4 CH3 E Z
2.10 2-Br-C6H4 CH3    
2.11 3-Br-C6H4 CH3    
2.12 4-Br-C6H4 CH3    
2.13 2-Me-C6H4 CH3    
2.14 3-Me-C6H4 CH3    
2.15 4-Me-C6H4 CH3    
2.16 2-CF3-C6H4 CH3    
2.17 3-CF3-C6H4 CH3    
2.18 4-CF3-C6H4 CH3    
2.19 2-MeO-C6H4 CH3    
2.20 3-MeO-C6H4 CH3    
2.21 4-MeO-C6H4 CH3    
2.22 2-CF3O-C6H4 CH3    
2.23 3-CF3O-C6H4 CH3 E E
2.24 4-CF3O-C6H4 CH3    
2.25 2-CHF2O-C6H4 CH3    
2.26 3-CHF2O-C6H4 CH3    
2.27 4-CHF2O-C6H4 CH3    
2.28 2-NO2-C6H4 CH3    
2.29 3-NO2-C6H4 CH3    
2.30 4-NO2-C6H4 CH3    
2.31 2-CN-C6H4 CH3    
2.32 3-CN-C6H4 CH3    
2.33 4-CN-C6H4 CH3    
2.34 2-N(CH3)2-C6H4 CH3    
2.35 3-N(CH3)2-C6H4 CH3    
2.36 4-N(CH3)2-C6H4 CH3    
2.37 2-吡啶基 CH3    
2.38 3-吡啶基 CH3    
2.39 4-吡啶基 CH3    
2.40 2-呋喃基 CH3    
2.41 2-噻唑基 CH3    
2.42 3-Cl-2-吡啶基 CH3    
2.43 4-Cl-2-吡啶基 CH3    
2.44 5-Cl-2-吡啶基 CH3    
2.45 6-Cl-2-吡啶基 CH3    
2.46 5-Cl-3-吡啶基 CH3    
2.47 3-Cl-4-吡啶基 CH3    
2.48 1-萘基 CH3    
2.49 2,4-2Cl-C6H3 CH3    
2.50 2,6-2Cl-C6H3 CH3 E E
2.51 3,4-2Cl-C6H3 CH3    
2.52 2-Cl-6-F-C6H3 CH3 E E
2.53 2-Cl-4-Me-C6H3 CH3    
2.54 3-Cl-4-Me-C6H3 CH3    
2.55 4-Cl-3-Me-C6H3 CH3    
2.56 2-F-4-Me-C6H3 CH3    
2.57 3-F-4-Me-C6H3 CH3    
2.58 2,4-2Me-C6H3 CH3    
2.59 2,5-2Me-C6H3 CH3    
2.60 3,4-2Me-C6H3 CH3    
2.61 2,4-2(MeO)-C6H3 CH3    
2.62 3,4-2(MeO)-C6H3 CH3    
2.63 3,5-2(MeO)-C6H3 CH3    
2.64 3,5-2(CF3)-C6H3 CH3 E E
2.65 2,5-2Cl-4-F-C6H2 CH3    
2.66 2,4,5-3Cl-C6H2 CH3    
2.67 2,4,6-3Cl-C6H2 CH3 E E
2.68 2,4,6-3CH3-C6H2 CH3    
2.69 4-苯并噻唑基 CH3    
其中，本发明通式I化合物及通式I所示化合物的立体异构体以及通式II化合物及通式II所示化合物的立体异构体化合物中，通过选择适当的起始原料或控制反应条件，以得到一种异构体过量的产物或单一异构体；或通过对粗产物进行常规手段的分离，包括柱色谱、重结晶等方法，得到单一的异构体。这些异构体的结构可以通过X-射线单晶衍射、核磁共振等常规方法确定。
一种通式I化合物及通式I所示化合物的立体异构体在农业、林业或卫生领域中作为杀菌剂的用途。
一种杀菌组合物，以所述通式I化合物或其立体异构体作为活性组分再与农业上可接受的载体组成组合物，组合物中活性组分的重量百分含量为1-99％。
一种防治病菌的方法，向作物或作物的生长介质或地点上施用杀菌有效剂量的所述的杀菌组合物。
本发明的化合物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病菌引起的病害，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。同时本发明的化合物具有优异的内吸活性可用作叶面和土壤杀菌剂。
本发明还提供了一种杀菌组合物，该组合物以通式I化合物或其立体异构体作为的活性组分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％。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化合物或其立体异构体与载体混合。
本发明组合物中的载体系满足下述条件的物质：它与活性成分配置后便与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、环己基酮；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。
附图说明
图1为本发明中化合物1.144的分子结构图。
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2.4和2.5的制备
Figure PCTCN2016093000-appb-000020
(1)中间体4-(4-氯苯基)-戊-3-烯-2-酮(IV-1)的制备
在100毫升反应瓶中加入对氯苯乙酮(5.60克，36.20毫摩尔)、3-乙氧基-2-丁烯酸乙酯(6.30克，39.80毫摩尔)和50毫升无水DMF，室温搅拌下分批加入叔丁醇钾(4.47克，39.80毫摩尔)。反应8小时后将反应液倒入200毫升水中，用2×100毫升乙酸乙酯除去未反应的原料，水相用盐酸酸化至pH＝2，过滤收集生成的黄色固体，分别用水和石油醚洗涤，得到中间体酸。将中间体酸投入到100毫升反应瓶中，加入25毫升1N的盐酸，升温至50℃脱羧至无气体放出。TLC监测反应完毕后，将反应液冷却至室温，用3×50毫升乙酸乙酯萃取，有机相经水、饱和食盐水洗涤后，用无水硫酸镁干燥，浓缩后得到黄色油状物4.8克，产率68％。核磁数据如下：
1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):2.51(s,3H),2.60(s,3H),6.48(s,1H),7.34-7.36(t,2H),7.40-7.45(m,2H)。
(2)化合物2.4和2.5的制备
在50毫升反应瓶中加入4-(4-氯苯基)-戊-3-烯-2-酮(0.50克，2.60毫摩尔)、盐酸羟胺(0.20克，2.80毫摩尔)、氢氧化钠(0.12克，2.80毫摩尔)和30毫升甲醇，加热回流3个小时。TLC监测反应完毕后，将反应液倒入100毫升水中，用2×30毫升乙酸乙酯萃取，有机相用饱和食盐水洗涤，无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析纯化后分别得到0.32克化合物2.4和0.16克化合物2.5，总产率90％。核磁数据如下：
化合物2.4：1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):2.13(s,3H),2.28(s,3H),6.12(s,1H),7.29-7.33(m,2H)，7.35-7.41(m,2H)。
化合物2.5：1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):2.15(s,3H),2.18(s,3H),6.43(s,1H),7.29-7.32(m,2H)，7.35-7.42(m,2H)。
实施例2：化合物2.8和2.9的制备
Figure PCTCN2016093000-appb-000021
(1)中间体4-(4-氟苯基)-戊-3-烯-2-酮(IV-2)的制备
在100毫升的反应瓶中加入对氟苯乙酮(5.00克，36.20毫摩尔)、3-乙氧基-2-丁烯酸乙酯(6.30克，39.80毫摩尔)和50毫升无水DMF，室温搅拌下分批加入叔丁醇钾(4.47克，39.80毫摩尔)。反应8小时后将反应液倒入200毫升水中，用2×100毫升乙酸乙酯除去未反应的原料，水相用盐酸酸化至pH＝2，过滤收集生成的黄色固体，分别用水和 石油醚洗涤，得到中间体酸。将中间体酸投入到100毫升反应瓶中，加入25毫升1N的盐酸，升温至50℃脱羧至无气体放出。TLC监测反应完毕后，将反应液冷却至室温，用3×50毫升乙酸乙酯萃取，有机相经水、饱和食盐水洗涤后，用无水硫酸镁干燥，浓缩后得到黄色油状物4.2克，产率65％。核磁数据如下：
1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):2.26(s,3H),2.48(s,3H),6.45(s,1H),7.00-7.06(t,2H),7.42-7.47(m,2H)。
(2)化合物2.8和2.9的制备
在50毫升反应瓶中加入4-(4-氟苯基)-戊-3-烯-2-酮(0.46克，2.60毫摩尔)、盐酸羟胺(0.20克，2.80毫摩尔)、氢氧化钠(0.12克，2.80毫摩尔)和30毫升甲醇，加热回流3个小时。TLC监测反应完毕后，将反应液倒入100毫升水中，用2×30毫升乙酸乙酯萃取，有机相用饱和食盐水洗涤，无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析纯化后分别得到0.28克化合物2.8和0.15克化合物2.9，总产率86％。核磁数据如下：
化合物2.8：1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):2.09(s,3H),2.28(s,3H),6.10(s,1H),6.99-7.05(m,2H)，7.38-7.43(m,2H)。
化合物2.9：1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):2.11(s,3H),2.15(s,3H),6.41(s,1H),6.70-7.06(m,2H)，7.43-7.47(m,2H)。
实施例3：化合物1.71和1.72的制备
Figure PCTCN2016093000-appb-000022
在50毫升反应瓶中加入4-(4-氯苯基)-戊-3-烯-2-酮(0.50克，2.57毫摩尔)、中间体V-1(0.67克，2.83毫摩尔)、30毫升甲醇及1滴冰醋酸，室温搅拌过夜。TLC监测反应完毕后，将反应液倒入100毫升水中，用2×30毫升乙酸乙酯萃取，有机相用饱和食盐水洗涤，无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析纯化得油状物，经LC-MS分析含有两个极性相近分子量相同的化合物，比例为75:25。油状物进一步纯化得到0.52克化合物1.71(油状物)和0.17克化合物1.72，总产率79％。核磁数据如下：
化合物1.71：1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):1.99(s,3H),2.19(s,3H),3.83(s,3H),4.03(s,3H),5.06(s,2H),6.02(s,1H),7.17-7.52(m,8H)。
化合物1.72：1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):1.83(s,3H),2.07(s,3H),3.73(s,3H),3.98(s,3H),4.98(s,2H),6.43(s,1H),7.14-7.45(m,8H)。
实施例4：化合物1.75和1.76的制备
Figure PCTCN2016093000-appb-000023
在50毫升反应瓶中加入4-(4-氟苯基)-戊-3-烯-2-酮(0.50克，2.80毫摩尔)、中间体V-1(0.74克，3.00毫摩尔)、30毫升甲醇及1滴冰醋酸，室温搅拌过夜。TLC监测反应完毕后，将反应液倒入100毫升水中，用2×30毫升乙酸乙酯萃取，有机相用饱和食盐水洗涤，无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析纯化得油状物，经LC-MS分析含有两个极性相近分子量相同的化合物，比例为67:33。油状物进一步纯化得到0.41克化合物1.75(白色固体)和0.2克化合物1.76(白色固体)，总产率55％。核磁数据如下：
化合物1.75：1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):1.99(s,3H),2.19(s,3H),3.84(s,3H),4.04(s,3H),5.06(s,2H),5.99(s,1H),6.97-7.49(m,8H)。
化合物1.76：1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):1.82(s,3H),2.07(s,3H),3.72(s,3H),3.98(s,3H),4.98(s,2H),6.40(s,1H),6.99-7.45(m,8H)。
实施例5：化合物1.140和1.141的制备
方法一：
Figure PCTCN2016093000-appb-000024
在50毫升反应瓶中加入含有75％化合物1.71和25％化合物1.72的油状物(0.60克，1.44毫摩尔)、20毫升甲醇及2毫升甲胺水溶液(40％)，室温搅拌过夜。TLC监测反应完毕后，将反应液倒入100毫升水中，用2×50毫升乙酸乙酯萃取，有机相用饱和食盐水洗涤，无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析纯化后得到0.48克油状物A，经LC-MS分析油状物A含有两个极性相近分子量相同的化合物1.140和1.141，比例为75:25。油状物A进一步纯化得到0.30克化合物1.140和0.10克化合物1.141。核磁数据如下：
化合物1.140：1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):1.99(s,3H),2.18(d,3H),2.88(d,3H),3.94(s,3H),5.06(s,2H),6.04(s,1H),6.76(s,1H),7.04-7.52(m,8H)。
化合物1.141：1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):2.07(s,3H),2.10(s,3H),2.80(d,3H),3.91(s,3H),4.98(s,2H),6.43(s,1H),6.68(s,1H),7.16-7.46(m,8H)。
方法二：
Figure PCTCN2016093000-appb-000025
在50毫升反应瓶中加入化合物1.71(0.30克，0.72毫摩尔)、20毫升甲醇及1毫升甲胺水溶液(40％)，室温搅拌过夜。TLC监测反应完毕后，将反应液倒入100毫升水中，用2×50毫升乙酸乙酯萃取，有机相用饱和食盐水洗涤，无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析纯化后得到0.24克化合物1.140，产率80％。
LC-MS(m/z):435.9(M+23)。
方法三：
Figure PCTCN2016093000-appb-000026
在50毫升反应瓶中加入化合物2.4(0.50克，2.39毫摩尔)、中间体VI-1(0.68克，2.39毫摩尔)、叔丁醇钾(0.30克，2.67毫摩尔)及30毫升DMF，升温至80℃反应8小时。TLC监测反应完毕后，将反应液倒入100毫升水中，用2×30毫升乙酸乙酯萃取，有机相用饱和食盐水洗涤，无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析纯化后得到0.32克化合物1.140，产率32％。
LC-MS(m/z):435.9(M+23)。
方法四：
Figure PCTCN2016093000-appb-000027
在50毫升反应瓶中加入化合物1.72(0.15克，0.36毫摩尔)、20毫升甲醇及1毫升甲胺水溶液(40％)，室温搅拌过夜。TLC监测反应完毕后，将反应液倒入100毫升水中，用2×50毫升乙酸乙酯萃取，有机相用饱和食盐水洗涤，无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析纯化后得到0.11克化合物1.141，产率73％。
LC-MS(m/z):435.9(M+23)。
实施例6：化合物1.144和1.145的制备
方法一：
Figure PCTCN2016093000-appb-000028
在50毫升反应瓶中加入含有67％化合物1.75和33％化合物1.76的油状物(1.20克，3.00毫摩尔)、40毫升甲醇及4毫升甲胺水溶液(40％)，室温搅拌过夜。TLC监测反应完毕后，将反应液倒入200毫升水中，用2×100毫升乙酸乙酯萃取，有机相用饱和食盐水洗涤，无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析纯化后得到1.0克油状物B，经LC-MS分析油状物B含有两个极性相近分子量相同的化合物1.144和1.145，比例为67:33。油状物B进一步纯化得到0.64克化合物1.144(白色固体)和0.32克化合物1.145(白色固体)。核磁数据如下：
化合物1.144：1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):1.99(s,3H),2.18(d,3H),2.88(d,3H),3.96(s,3H),5.05(s,2H),6.00(s,1H),6.76(s,1H),6.98-7.48(m,8H)。
化合物1.145：1H NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):2.05(d,3H),2.10(d,3H),2.80(d,3H),3.91(s,3H),4.98(s,2H),6.39(s,1H),6.68(s,1H),7.02-7.46(m,8H)。
将化合物1.144(0.5克)加入到乙酸乙酯中，完全溶解，然后加入少量石油醚，放置室温缓慢挥发得到无色透明片状晶体，从中选取大小为0.36mm x 0.28mm x 0.20mm进单晶进行衍射实验，在BRUKER SMART衍射仪上，采用经石墨单色器单色画的MoK\a射线
Figure PCTCN2016093000-appb-000029
作为入射辐射，在2.01°≤θ≤25.03°范围内，以ω-2θ扫描方式，在296(2)K温度下共收集25544个衍射点，其中独立衍射点数为5029(Rint＝0.0554),5029个可观察衍射点(I>2σ(I))用于结构测定和修正。衍射强度数据经Lp因子和经验吸收校正。晶体结构以直接法解出，以差值傅立叶合成法定出非氢原子坐标，并以各向异性热参数用全矩阵最小二乘法对其进行修正。氢原子坐标有理论方法获得，并参与结构因子计算。最终偏离因子R＝0.0513，wR＝0.1306。所有的计算均用SHELXL-97程序完成。得到的分子结构见图1。
方法二：
Figure PCTCN2016093000-appb-000030
在50毫升反应瓶中加入化合物1.75(0.30克，0.75毫摩尔)、20毫升甲醇及1毫升甲胺水溶液(40％)，室温搅拌过夜。TLC监测反应完毕后，将反应液倒入100毫升水中，用2×50毫升乙酸乙酯萃取，有机相用饱和食盐水洗涤，无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析纯化后得到0.25克白色固体(化合物1.144)，产率85％。
LC-MS(m/z):419.9(M+23)。
方法三：
Figure PCTCN2016093000-appb-000031
在50毫升反应瓶中加入化合物2.8(0.50克，2.59毫摩尔)、中间体VI-1(0.74克，2.59毫摩尔)、叔丁醇钾(0.32克，2.85毫摩尔)及30毫升DMF，升温至80℃反应8小时。TLC监测反应完毕后，将反应液倒入100毫升水中，用2×30毫升乙酸乙酯萃取，有机相用饱和食盐水洗涤，无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析纯化后得到0.31克白色固体(化合物1.144)，产率30％。
方法四：
Figure PCTCN2016093000-appb-000032
在50毫升反应瓶中加入化合物1.76(0.2克，0.50毫摩尔)、20毫升甲醇及1毫升甲胺水溶液(40％)，室温搅拌过夜。TLC监测反应完毕后，将反应液倒入100毫升水中，用2×50毫升乙酸乙酯萃取，有机相用饱和食盐水洗涤，无水硫酸镁干燥、过滤、减压脱溶，残余物柱层析纯化后得到0.16克白色固体(化合物1.145)，产率80％。
生物活性测定
用本发明化合物对植物的多种菌病害进行了试验。
实施例7：杀菌保护活性测试
保护活性测试方法：采用活体盆栽测定方法，即将待测化合物样品用少量溶剂(溶剂的种类如丙酮、甲醇、DMF等，并且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％吐温80的水稀释，配制成所需浓度待测液，另设溶剂清水液作为空白对照。在作物喷雾机上，将待测液喷施于病害寄主植物上(寄主植物为在温室内培养的标准盆栽苗)，24小时后进行病害接种。依据病害特点，将需要控温保湿培养的病害植物接种后放在人工气候室中培养，待病害完成侵染后，移入温室培养；将不需要保湿培养的病害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)进行化合物防病效果评估。
部分化合物保护活性测试结果如下：
药液浓度为25毫克/升时，化合物1.140、化合物1.144对黄瓜炭疽病的防效为100％；
药液浓度为6.25毫克/升时，化合物1.140对黄瓜炭疽病的防效不低于98％，化合物1.144对黄瓜炭疽病的防效为100％；
药液浓度为3.125毫克/升时，化合物1.140、化合物1.144对黄瓜炭疽病的防效均不 低于98％。
药液浓度为6.25毫克/升时，化合物1.140、化合物1.144、化合物1.145对小麦白粉病的防效为100％；
药液浓度为1.5625毫克/升时，化合物1.140对小麦白粉病的防效为100％，试样A(含有质量比为3:1的化合物1.140和化合物1.141)、试样B(含有质量比为2:1的化合物1.144和化合物1.145)、化合物1.144、化合物1.145对小麦白粉病的防效不低于98％；
药液浓度为0.39毫克/升时，化合物1.144对小麦白粉病的防效不低于98％。
实施例8：杀菌治疗活性测试
治疗活性测试方法：采用活体盆栽测定方法，即将病害寄主植物(寄主植物为在温室内培养的标准盆栽苗)于喷雾处理前进行病害接种，培养24小时作为测试寄主植物。另将待测化合物样品用少量溶剂(溶剂的种类如丙酮、甲醇、DMF等，并且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％吐温80的水稀释，配制成所需浓度待测液，另设溶剂清水液作为空白对照。在作物喷雾机上，将待测液喷施于上述寄主植物上，然后移入温室正常培养。待对照充分发病后(通常为一周时间)进行化合物治疗效果评估。
部分化合物治疗活性测试结果如下：
药液浓度为12.5毫克/升时，化合物1.144对黄瓜炭疽病的治疗活性不低于90％。
药液浓度为25毫克/升时，化合物1.144对小麦白粉病的治疗活性为100％；
药液浓度为6.25毫克/升时，化合物1.144对小麦白粉病的治疗活性为100％；
药液浓度为1.5625毫克/升时，化合物1.144对小麦白粉病的治疗活性为100％。
实施例9：杀菌内吸活性对比试验
化合物防治黄瓜炭疽病内吸活性测试方法：将待测化合物样品用少量溶剂(溶剂的种类如丙酮、甲醇、DMF等，并且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％吐温80的水稀释，配制成所需浓度待测液，另设溶剂清水液作为空白对照。选择温室内生长整齐一致盆栽黄瓜幼苗作为寄主，在其叶片上进行定点滴药处理，处理后移入温室正常培养，24小时后接种(其它方法见保护活性测试方法)。
表3 防治黄瓜炭疽病内吸活性对比试验结果
Figure PCTCN2016093000-appb-000033
Figure PCTCN2016093000-appb-000034
化合物防治小麦白粉病内吸活性测试方法：将待测化合物样品用少量溶剂(溶剂的种类如丙酮、甲醇、DMF等，并且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％吐温80的水稀释，配制成所需浓度待测液，另设溶剂清水液作为空白对照。选择温室内生长整齐一致盆栽小麦苗作为寄主，在其叶片上进行定点滴药处理，处理后移入温室正常培养，24小时后接种(其它方法见保护活性测试方法)。
表4 防治小麦白粉病内吸活性对比试验结果
Figure PCTCN2016093000-appb-000035
本试验将现有技术中公开的化合物CK1～CK9作为对照化合物，选取本发明中部分化合物及其立体异构体进行活性比较，如试样A、化合物1.140、试样B、化合物1.144。化合物CK1为按照专利CN1191670A中合成实施例2所描述的方法进行制备和分离得到的；化合物CK2～CK5为按照专利CN1580041A中合成实施例1和例2所描述的方法进行制备和分离得到的；化合物CK6为按照专利CN1309897A中合成实施例1所描述的方法进行制备和分离得到的；化合物CK7～CK9为按照专利WO0212172A1中合成实施例8所描述的方法进行制备和分离得到的。
虽然本发明披露如上，但本发明并非限定于此。任何本领域技术人员，在不脱离本发明的精神和范围内，均可作各种更动与修改，因此本发明的保护范围应当以权利要求所限定的范围为准。

Claims (10)

  1. 一种不饱和肟醚类化合物，如通式I所示：
    Figure PCTCN2016093000-appb-100001
    式中：
    R1选自未取代的或任意取代的芳基或杂芳基；
    R2选自C1-C6烷基或卤代C1-C6烷基；
    W选自CH或N；
    Q选自NH或O；
    或，通式I所示化合物的立体异构体。
  2. 根据权利要求1所述的化合物，其特征在于，通式I中，
    R1选自未取代的或被1-5个相同或不同的R3取代的苯基；
    R2选自C1-C6烷基或卤代C1-C3烷基；
    R3选自卤素、氰基、硝基、羟基、巯基、氨基、CONH2、COOH、CHO、C1-C4烷基、卤代C1-C4烷基、C3-C6环烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C1-C3烷硫基、卤代C1-C3烷硫基、C1-C3烷基氨基、C1-C3二烷基氨基、C3-C6环烷基氨基、C1-C3烷氧基羰基、C1-C3烷基磺酰基、C1-C3烷基氨基羰基或C1-C3烷基氨基磺酰基。
  3. 根据权利要求2所述的化合物，其特征在于，通式I中，
    R1选自未取代的或被1-4个相同或不同的R3取代的苯基；
    R2选自C1-C6烷基；
    R3选自卤素、氰基、硝基、羟基、巯基、氨基、COOH、C1-C4烷基、卤代C1-C4烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C1-C3烷硫基、卤代C1-C3烷硫基、C1-C3烷基氨基、C1-C3二烷基氨基、C1-C3烷氧基羰基或C1-C3烷基磺酰基。
  4. 根据权利要求3所述的化合物，其特征在于，通式I中，
    R1选自未取代的或被1-3个相同或不同的R3取代的苯基；
    R2选自C1-C3烷基；
    R3选自卤素、氰基、硝基、C1-C4烷基、卤代C1-C4烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C1-C3烷基氨基、C1-C3二烷基氨基或C1-C3烷基磺酰基；
    W选自N；
    Q选自NH。
  5. 根据权利要求4所述的化合物，其特征在于，通式I中，
    R2选自甲基；
    R3选自卤素、氰基、硝基、C1-C4烷基、卤代C1-C4烷基、C1-C3烷氧基、卤代C1-C3烷氧基、C1-C3二烷基氨基或C1-C3烷基磺酰基。
  6. 根据权利要求5所述的化合物，其特征在于，通式I中，
    R1选自被1-2相同或不同的个R3取代的苯基；
    R3选自卤素、氰基或卤代C1-C4烷基。
  7. 一种用于制备通式I化合物的中间体，其特征在于：中间体如通式II所示：
    Figure PCTCN2016093000-appb-100002
    式中：
    R1选自未取代的或任意取代的芳基或杂芳基；
    R2选自C1-C6烷基或卤代C1-C6烷基；
    或，通式II所示化合物的Z或E式立体异构体。
  8. 一种按照权利要求1-6中任意一项所述的通式I化合物及通式I所示化合物的立体异构体在农业、林业或卫生领域中作为杀菌剂的用途。
  9. 一种杀菌组合物，其特征在于：以如权利要求1-6中任意一项中所述通式I化合物或其立体异构体作为活性组分再与农业上可接受的载体组成组合物，组合物中活性组分的重量百分含量为1-99％。
  10. 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9所述的杀菌组合物。
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