WO2017024971A1 - Composé d'oximino-éther insaturé et son utilisation - Google Patents

Composé d'oximino-éther insaturé et son utilisation 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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Chinese (zh)
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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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  • Environmental Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention porte sur un composé d'oximino-éther insaturé et sur son utilisation. Le composé est tel que représenté par la formule générale I, le composé de formule I présentant une excellente activité bactéricide et, en particulier encore, présentant un bon effet de commande sur le mildiou du concombre et l'oïdium du blé à une dose relativement faible tout en présentant également une excellente action systémique. Par conséquent, le composé tel que représenté par la formule générale I est utilisé en tant que bactéricide dans les champs agricoles et autres.
PCT/CN2016/093000 2015-08-12 2016-08-03 Composé d'oximino-éther insaturé et son utilisation WO2017024971A1 (fr)

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