WO2017129122A1 - Isothiazole oxime ether strobilurin derivatives, preparation method for same, and uses thereof - Google Patents

Isothiazole oxime ether strobilurin derivatives, preparation method for same, and uses thereof Download PDF

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WO2017129122A1
WO2017129122A1 PCT/CN2017/072557 CN2017072557W WO2017129122A1 WO 2017129122 A1 WO2017129122 A1 WO 2017129122A1 CN 2017072557 W CN2017072557 W CN 2017072557W WO 2017129122 A1 WO2017129122 A1 WO 2017129122A1
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agent
smoke
group
rice
compound
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PCT/CN2017/072557
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French (fr)
Chinese (zh)
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范志金
陈来
郭晓凤
朱玉洁
钱晓琳
马刘勇
张乃楼
王海霞
张秩鸣
徐京华
宋胤奇
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南开大学
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Priority claimed from CN201610185795.7A external-priority patent/CN106995417B/en
Application filed by 南开大学 filed Critical 南开大学
Priority to US16/073,089 priority Critical patent/US10906880B2/en
Publication of WO2017129122A1 publication Critical patent/WO2017129122A1/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72Biocides, 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
    • A01N43/80Biocides, 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D275/00Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C07D275/03Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings 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

Definitions

  • the technical scheme of the present invention relates to an N-containing S-containing isothiazolyl ether methoxy acrylate compound, in particular to a compound of 3,4-dichloroisothiazolium ether, namely 3,4-dichloroisothiazolium ether A methoxy acrylate derivative.
  • Heterocyclic compounds are high-efficiency, low-toxic, broad-spectrum biologically active lead compounds. Most of the active molecules reported in the patent literature have heterocyclic structures. The five-membered heterocyclic compounds have been reported in the literature as plant activators, fungicides, plant growth regulators, and Insecticide activity (Chen Danping. Modern Pesticide, 2014, 14(2): 5-10), wherein isothiazole is an important five-membered nitrogen-containing sulfur-containing heterocyclic compound. Mel'nikov found the plant growth regulating activity of the isothiazole compound (Mel'nikov N.N., Zhurnal Vseoyuznogo Khimic heskogo Obshchestva im. D. I. Mendeleeva. 1988, 33(6), 602-609).
  • the methoxy acrylate fungicide has a broad spectrum of bactericidal activity and is very active against almost all fungi (Ascomycetes, Basidiomycetes, Oomycetes and Deuteromycetes) diseases, such as wheat. Powdery mildew, leaf blight, red spot disease, net blotch, black shank, rice blast, sheath blight and downy mildew and disease (Guan Aiying. Fine and Specialty Chemicals, 2012, 20(4) :24-28). These agents have many advantages such as high efficiency, broad spectrum, low toxicity, systemic absorption and easy degradation. They have become the most important agricultural fungicides in the world (Yuan Xiaoyong. 2014, 34: 170-177).
  • azoxystrobin kresoxim-methyl, pyraclostrobin, and trifloxystrobin.
  • fluoxastrobin picoxystrobin, metaminostrobin, dimoxystrobin, oressastrobin, enestrobin, azole Pyraoxystrobin, enestrobin (SYP-1620), and the like.
  • Strobilurin fungicides Due to the single action site of Strobilurin fungicides, the resistance problem caused by a large number of high frequency and high intensity applications is very prominent (Fisher, N. Pest. Manage. Sci. 2005, 61 (10): 973-978); plant activators A system with a broad spectrum and long-lasting disease is resistant to disease and does not directly act on the pathogen and acts on the plant itself. Therefore, the risk of drug resistance is imperative.
  • the present invention will contain N-containing S-isothiazole pharmacophore 3,4-dichloro
  • the isothiazole ring was introduced into the lead structure of methoxy acrylate, and a class of isothiazolyl ether methoxy acrylate derivatives was designed and synthesized.
  • the biological activity of the system was screened and evaluated, in order to provide new pesticide creation research. More candidate compounds with high activity and low resistance risk.
  • the technical problem to be solved by the present invention is to provide a novel method for synthesizing a novel isothiazolyl ether methoxy acrylate derivative and its biological activity for regulating plant pests, plant pathogens in agriculture, horticulture, sanitary and forestry, and its determination
  • the method provides both the application of these compounds in the agricultural, horticultural, forestry, and health fields.
  • the technical solution adopted by the invention to solve the technical problem is: having an agricultural field, a horticultural field, a forestry field, an insecticidal activity, acaricidal activity, a bactericidal activity, an anti-plant virus activity, and an isothiazolyl ether methoxy group which induces a plant to produce disease resistance activity.
  • the chemical structure of the acrylates is shown in Formula IV:
  • R 1 is selected from the group consisting of methyl, hydrogen, and amine; and R 2 is selected from the group consisting of: 1,2-difluoroethyl, propargyl, cyclopropyl, methyl, 1-methylthio-2-methyl Prop-2-yl, (R)-1-methylthiopropan-2-yl;
  • Z is selected from the group consisting of carbon and nitrogen.
  • R 1 is selected from the group consisting of methyl, hydrogen, and amine; and R 2 is selected from the group consisting of: 1,2-difluoroethyl, propargyl, cyclopropyl, methyl, 1-methylthio-2-methyl Prop-2-yl, (R)-1-methylthiopropan-2-yl;
  • Z is selected from the group consisting of carbon and nitrogen.
  • the method for synthesizing the thiadiazolone methoxy acrylate derivative is divided into the following steps:
  • 3,4-dichloroisothiazol-5-substituted carbonyl compound is selected from the group consisting of: 3,4-dichloroisothiazol-5-formaldehyde, 3,4 -dichloroisothiazol-5-ethanone, 4-(3,4-dichloroisothiazol-5-yl)-but-3-en-2-one;
  • the compound I, 3,4-dichloroisothiazol-5-cyanamide and thioglycolic acid are separately added to the ethanol solution, and reacted at room temperature. After the reaction is completed, the reaction solution is concentrated, and the residue is purified to obtain the compound II. ;
  • the compound II and sodium hydroxide are added to the methanol solution, and then the reaction is carried out by heating under reflux. After the reaction is completed, the reaction liquid is concentrated, and the residue is diluted with ethyl acetate, then the residue is dissolved by water, the aqueous layer is separated, and then the aqueous layer is separated. The pH was adjusted to 3 with hydrochloric acid, then extracted with EtOAc. EtOAc (EtOAc)EtOAc. , that is, compound III;
  • the synthesis method of the isothiazolyl ether methoxy acrylate derivative of the present invention is divided into the following steps:
  • thiazole-5-substituted carbonyl compound is selected from the group consisting of 3,4-dichloroisothiazol-5-carbaldehyde, 3,4-dichloroisothiazol-5-ethanone, 4-(3,4-dichloroisothiazol-5 -Based on -but-3-en-2-one, finally adding two drops of 2 mol/L hydrochloric acid dropwise to the reaction system, stirring at room temperature for 12 hours, after completion of the reaction, the solvent was removed under reduced pressure, and the residue was passed through 200-300 mesh.
  • the eluent is petroleum ether: ethyl acetate of 60-90 degrees Celsius, according to the product, the volume ratio is 9:1-2:1, the yield is 70-80%; compound II
  • the amount prepared and the volume of the reaction vessel are enlarged or reduced in proportions.
  • the reaction solution was washed twice with 15 ml of water, the organic layer was separated, and the organic layer was washed with saturated sodium hydrogen carbonate and saturated sodium chloride. Once again, dried over anhydrous sodium sulfate, suction filtered, and the solvent was evaporated under reduced pressure.
  • the residue was purified by silica gel column chromatography from 200 to 300 mesh to afford white solid, eluent: petroleum ether: ethyl acetate, volume ratio of 60-90 ° C It is 4:1, the yield is 30-95%; the amount of the preparation of the compound IV and the volume of the reaction vessel are expanded or reduced in a corresponding ratio.
  • the invention also provides the use of the isothiazolidine methoxy acrylate derivative IV in the preparation of a bactericide, a tobacco mosaic virus agent or a plant activator.
  • the invention also provides the use of the isothiazolium ether methoxy acrylate derivative IV and an agriculturally acceptable adjuvant in the preparation of a bactericide, a tobacco mosaic virus agent or a plant activator.
  • the invention also provides the use of the isothiazolidine methoxy acrylate derivative IV for controlling agricultural and forestry and horticultural plant pests.
  • the isothiazolyl ether methoxy acrylate derivative IV is co-administered with an agricultural chemical; preferably, the agricultural chemical is selected from the group consisting of: an insecticide, a bactericide, an anti-plant virus agent, an acaricide One or several of them.
  • the isothiazolyl ether methoxy acrylate derivative IV is combined with any one or both of the insecticides to form an insecticidal composition for controlling agricultural and forestry and horticultural plant pests;
  • the insecticide is selected from the group consisting of: chlorpyrifos, scorpion guanidine, acetamiprid, emamectin, imipenem, avermectin, spinosyn, fenvalerate, high-efficiency acetonide Pyrethroid, cypermethrin, beta-cypermethrin, cyhalothrin, deltamethrin, fenpropathrin, Beta-cyfluthrin, Lambda-cyhalothrin, permethrin, permethrin, methrin, hydrazine Pyrethrin, permethrin, fenthrin, flumethrin, flufenacetate, imidacloprid, nitenpyram, chlorothiazide, thiacloprid, thiamethoxam, clothianidin, fur Nicotinamide, cotinine, Dartnam, diflubenz
  • the isothiazolium ether methoxy acrylate derivative IV is present in the pesticidal composition in an amount of from 1% to 90% by mass;
  • the ratio of the isothiazolyl ether methoxy acrylate derivative IV to the insecticide is mass% Ratio 1%: 99% to 99%: 1%;
  • the dosage form processed by the pesticidal composition is selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous valley, lumps Bait, granular bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, Hot mist, cold spray, aerosol, solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microparticle, trace powder, oil suspension, oil dispersible powder , thickener, pouring agent, seed coating agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam release agent;
  • the plant pests controlled by the insecticidal composition are selected from the group consisting of: red spider, oriental planthopper, cloud locust, Chinese rice blast, Japanese yellow ridge, single locust, oriental carp, rice locust, and tobacco Horse, greenhouse thrips, rice tube thrips, wheat tube horses, greenhouse whitefly, whitefly, black-tailed leafhopper, big green leafhopper, cotton leafhopper, spotted waxhopper, brown planthopper, white-backed planthopper , Laodelphax striatellus, sugarcane, flat-horned corn fly, cotton aphid, wheat bifurcation, wheat long tube, peach aphid, sorghum, radish, blown, sang shield, yam shield, pear round, White wax insects, red wax mites, Korean ball glutinous rice, pear net mites, banana net mites, fine-horned flower buds, tiny flower buds, needle-edge mites, rice spider mites, rice brown mites, rice black
  • the plant controlled by the pesticidal composition is selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, tapioca, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut , rapeseed, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, rape, Onions, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
  • the isothiazolyl ether methoxy acrylate derivative IV is combined with any one or both of the bactericides to form a bactericidal composition for controlling agricultural and forestry and horticultural plant diseases,
  • the bactericide is selected from the group consisting of: benzothiadiazole, thiazide, abbreviated as TDL, thiazamide, methyl thiazide, 4-methyl-1,2,3-thiadiazole-5- Formic acid, sodium 4-methyl-1,2,3-thiadiazol-5-carboxylate, ethyl 4-methyl-1,2,3-thiadiazol-5-carboxylate, DL- ⁇ -aminobutyric acid, Isotianil, its common name in English is: isotianil, 3,4-dichloroisothiazol-5-carboxylic acid, 3,4-dichloroisothiazol-5-formate, 3,4-dichloroisothiazol-5- Ethyl formate, ribavirin, antofin, nymidine or salicylic acid, cymoxanil, thiram, thiram, mancozeb, ethylphosphoric acid, thiophan
  • the total mass percentage of the isothiazolyl ether methoxy acrylate derivative IV in the germicidal composition is from 1% to 90%,
  • the ratio of the isothiazolyl ether methoxy acrylate derivative IV to the bactericide is 1% by mass: 99% to 99%: 1% by mass;
  • the bactericidal composition is processed in a dosage form selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous valley, block bait , granular bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, heat Spray, cold spray, aerosol, solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microparticle, trace powder, oil suspension, oil dispersible powder, Thickener, pouring agent, seed coating agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam release agent;
  • the plant disease controlled by the bactericidal composition is selected from the group consisting of: rice seedling cotton rot, tomato root rot, potato late blight, tobacco black shank, millet powdery mildew, grape downy mildew, lettuce downy mildew, cucumber Downy mildew, cucumber anthracnose;
  • the bactericidal composition is suitable for plants selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut, Rape, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, rape, onion , garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
  • the isothiazolyl ether methoxy acrylate derivative IV is combined with any one or both of the antiviral agents to form an antiviral composition for controlling agricultural and forestry and horticultural plant virus diseases;
  • the antiviral agent is selected from the group consisting of: benzothiadiazole, thiazide, abbreviated as TDL, isotianil, and its common name in English is: isotianil, 4-methyl-1,2,3- Thiadiazole-5-carboxylic acid, sodium 4-methyl-1,2,3-thiadiazole-5-carboxylate, ethyl 4-methyl-1,2,3-thiadiazole-5-carboxylate, 3, 4-Dichloroisothiazol-5-carboxylic acid, 3,4-dichloroisothiazol-5-formate, 3,4-dichloroisothiazol-5-carboxylic acid ethyl ester, DL- ⁇ -aminobutyric acid, ribavirin, Antofin, ningnanmycin, thiazamide, methyl thiazide or salicylic acid, glutathione, dichloroisonicotinic acid, allylisothiazole,
  • the total mass percentage of the isothiazolyl ether methoxy acrylate derivative IV in the antiviral composition is from 1% to 90%,
  • the ratio of the isothiazolyl ether methoxy acrylate derivative IV to the anti-plant virus agent is 1% by mass: 99% to 99%: 1% by mass;
  • the antiviral composition is processed in a dosage form selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous valley, lumps Bait, granular bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, Hot mist, cold spray, aerosol, solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microparticle, trace powder, oil suspension, oil dispersible powder , thick glue, splash Pouring agent, seed coating agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam release agent;
  • a dosage form selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension
  • the viral disease controlled by the antiviral composition is selected from the group consisting of rice dwarf disease, yellow dwarf disease, stripe leaf blight, tomato fern leaf virus disease, pepper mosaic virus disease, tobacco vein necrosis virus disease, corn dwarf Mosaic disease, cauliflower mosaic virus, citrus virus disease, broccoli virus, Jianlan ring spot virus;
  • the plant for controlling the antiviral composition is selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, tapioca, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture , peanuts, rapeseed, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, Rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
  • the isothiazolyl ether methoxy acrylate derivative IV is combined with any one or both of the acaricides to form a acaricidal composition for controlling agricultural and forestry and horticultural plant damage;
  • the acaricide is selected from the group consisting of: triazole tin, tricyclotin, phenbutyltin, triphosphorus, chlorpyrifos, methyl chlorpyrifos, phytophos, dichlorvos, heptene phosphorus, quick-killing phosphorus, long time Phosphorus, dibromophosphorus, chlorpyrifos, pyrimidine, chloromethylimine, omethoate, chlorpyrifos, ethion, malathion, worm, phoxim, phoxim, Pyrithione, quetiapine, strontium phosphate, triazophos, quenching, acesulfame, methamidophos, acesulfame, chloroimidate, imipenem, flumethrin, Bifenthrin, cyhalothrin, cyhalothrin, fenpropathrin, fluvalerate, fluorate,
  • the total mass percentage of the isothiazolyl ether methoxy acrylate derivative IV in the acaricidal composition is from 1% to 90%,
  • the ratio of the isothiazolyl ether methoxy acrylate derivative IV to the acaricide is 1% by mass: 99% to 99%: 1% by mass;
  • the dosage form processed by the acaricidal composition is selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous valley, block Bait, granular bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, Hot mist, cold spray, aerosol, solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microparticle, trace powder, oil suspension, oil dispersible powder , thickener, pouring agent, seed coat Agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam release agent;
  • the cockroach damage controlled by the acaricidal composition is selected from the group consisting of: the mites are selected from the group consisting of the genus Aphididae, the genus Diptera, the eucalyptus, the genus Eucalyptus, the genus Eucalyptus, and the mites. World agricultural pests, forest pests, horticultural pests and health hazards;
  • the plant for controlling the acaricidal composition is selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture , peanuts, rapeseed, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, Rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
  • the biological activity of the isothiazolyl ether methoxy acrylate derivative IV of the present invention is determined as follows:
  • the bactericidal or bacteriostatic activity of the isothiazolyl ether methoxy acrylate IV of the present invention is determined by a cell growth rate method, and the specific steps are as follows: a 1.8 mg sample is dissolved in 2 drops of N,N-dimethylformamide, Then dilute to 500 ⁇ g / ml of the drug with an aqueous solution containing a certain amount of Tween 20 emulsifier, and take 1 ml of the test agent under sterile conditions into the culture dish, then add 9 ml of PDA medium separately, shake well Then make a 50 ⁇ g/ml drug-containing plate, add a 1 ml sterilized water plate as a blank control, use a 4 mm diameter puncher to cut the fungus disc along the outer edge of the hyphae, and transfer it to the drug-containing plate.
  • the triangles were placed and the treatment was repeated 3 times.
  • the culture dishes were placed in a constant temperature incubator at 24 ⁇ 1 ° C. After the diameter of the control colonies was extended to 2-3 cm, the expanded diameter of each treated disk was investigated and averaged. The relative inhibition rate was calculated by blank control.
  • the tested strains were the species of most typical plant pathogens actually occurring in the field of agricultural production in China.
  • the codes and names are as follows: AS: tomato early blight, its Latin name: Alternaria Solani, BC: Cucumber gray mold, its Latin name: Botrytis cinerea, CA: peanut brown spot disease, its Latin name: Cercospora arachidicola, GZ: Fusarium graminearum, its Latin name: Gibberella zeae, PI: Phytophthora infestans, Its Latin name is: Phytophthora infestans (Mont.) de Bary, PP: Apple ring rot, its Latin name: Physalospora piricola, PS: Rhizoctonia solani, its Latin name: Pellicularia sasakii, RC: cereal Nuclear bacteria, its Latin name: Rhizoctonia cerealis, SS: Sclerotinia sclerotiorum, its Latin name: Sclerotinia sclerotiorum.
  • the screening method for the activity of the isothiazolyl ether methoxy acrylate derivative IV is as follows.
  • the tobacco mosaic virus is abbreviated as TMV:
  • Positive control plant activator select a plant activator with a purity purity greater than 99.5% of thiazide as a positive control; thiazide is abbreviated as TDL;
  • the beneficial effects of the present invention are: lead optimization of the isothiazolyl ether methoxy acrylate derivative IV, and screening of the isothiazolyl ether methoxy acrylate derivative for bacteriostatic activity.
  • the present invention more specifically illustrates the synthesis and biological activity and use of the isothiazolium ether methoxy acrylate derivative IV by specific preparation and biological activity assay examples, which are intended to specifically illustrate the invention and not to limit the invention.
  • the biological activity is merely illustrative and not limiting, and the specific embodiments are as follows:
  • thiazole-5-substituted carbonyl compound is selected from the group consisting of 3,4-dichloroisothiazol-5-carbaldehyde, 3,4-dichloroisothiazol-5-ethanone, 4-(3,4-dichloroisothiazol-5 -butyl-3-butan-2-one, two drops of 2 mol/L hydrochloric acid were added dropwise in the final reaction system, and stirred at room temperature for 12 hours.
  • the present invention synthesizes the compound CL05-00 reported in the literature, and the specific synthesis steps are as follows:
  • Example 7 Determination of the antibacterial activity of the isothiazolyl ether methoxy acrylate derivative IV of the present invention:
  • the code and name of the common phytopathogenic fungi tested in the present invention are as follows: AS: tomato Phytophthora infestans, Latin name: Alternaria solani, BC: Botrytis cinerea, Latin name: Botrytis cinerea, CA: Peanut brown spot disease Its Latin name: Cercospora arachidicola, GZ: Fusarium graminearum, its Latin name: Gibberella zeae, PI: Phytophthora infestans, Latin name: Phytophthora infestans (Mont.) de Bary, PP: Apple wheel The pathogen, its Latin name: Physalospora piricola, PS: Rhizoctonia solani, its Latin name: Pellicularia sasakii, RC: Rhizoctonia cereal, its Latin name: Rhizoctonia cerealis, SS: Sclerotinia sclerotiorum, its The Latin name is: Sclerotinia sclerotiorum, which is
  • the compound CL04-00 in the present invention is a known compound whose chemical structure is reported closest to the target compound of the present invention as reported in the patent WO 2000003974 A1.
  • the present invention synthesizes The known compound CL04-00 having the structure closest to the target compound of the present invention is used as a control compound and compared with the activity of the target compound of the present invention.
  • Table 2 shows that at 50 ⁇ g/ml, all of the compounds of the isothiazolyl ether methoxy acrylate synthesized by the present invention have different degrees of bactericidal activity.
  • the inhibition rates of CL04-22D, CL04-25C, CL04-17, CL04-32A, CL04-32B, CL04-32C and CL04-32D are all above 30%.
  • the bactericidal activity of the above compounds is higher than that reported in the literature.
  • the bactericidal activity of the compound with the closest chemical structure of the target compound CL04-00 is more than 10%, in addition to the compounds CL03-50, CL04-03, CL04-04, CL04-06, CL04-15B, CL04-15C and CL04-32D.
  • the bactericidal activity was higher than that reported in the literature, and the bactericidal activity of the compound CL05-00 which is the closest to the chemical structure of the target compound of the present invention was more than 10%, and the inhibition rate of the compound CL04-04 and CL04-15B was above 80%.
  • the compound CL04-15B has the highest bactericidal activity, up to 100%;
  • the inhibition rates of CL04-22C, CL04-22D, CL04-22E, CL04-25C, CL04-17, CL04-32A, CL04-32B, CL04-32C and CL04-32D are all above 30%, and the antibacterial activity of the above compounds
  • the antibacterial activity of the compound CL04-00 which is the closest to the chemical structure of the target compound of the present invention is more than 10%, and the compounds CL04-04, CL04-04, CL04-15B, CL04-15C, CL04-
  • the inhibition rates of 22D and CL04-32D were all above 75%, which were higher than the bactericidal activity of the compound CL
  • the antibacterial activity of the compound CL04-00 and the control drug enestrobin which are the closest to the chemical structure of the target compound of the present invention are more than 10%, wherein the compounds CL04-03, CL04-04, CL04-04, CL04-06, CL04-15B, CL04-15C, CL04-22A, CL04-22B, CL04-22C, CL04-22D, CL04-25B, CL04-25C, CL04-17, CL04-32B, CL04
  • the antibacterial activity of -32C and CL04-32F is higher than that of the compound CL05-00 which is the closest to the chemical structure of the target compound of the present invention, which is more than 10%, among which the compounds CL04-15C, CL04-22B, CL04-22D, CL04-
  • the inhibition rates of 25C, CL04-32B and CL04-32D were all above 80%, which were more than 10% higher than the control azoxystrobin, especially the sterilization of compounds CL04-22B, CL04-22D, CL04-25C and CL04-
  • the chemical structure of the closest compound CL04-00 has more than 10% antibacterial activity, among which compounds CL03-49, CL03-50, CL04-03, CL04-04, CL04-06, CL04-15C, CL04-22D, CL04-
  • the inhibition rate of 32C was above 70%, which was higher than the compound CL05-00 and the control drug enestrobin which are the closest to the chemical structure of the target compound of the present invention, and the compound CL04-03 had the highest bactericidal activity of 86.96%.
  • the antibacterial activity of the above compounds was higher than that of the compound CL04-00 which is the closest to the chemical structure of the target compound of the present invention, and the antibacterial activity was more than 10%.
  • the bactericidal activity of -25C, CL04-17, CL04-32B, CL04-32C and CL04-32D was higher than that of the control drug enestrobin more than 10%, and the compounds CL04-03, CL04-04, CL04-06, CL04 -15A, CL04-15B, CL
  • the inhibition rates of 04-15C, CL04-22B and CL04-22D were all higher than 90%, which were higher than the antibacterial activity of the compound CL05-00 which is the closest to the chemical structure of the target compound of the present invention, which
  • the control azoxystrobin especially the compounds CL04-03, CL04-06, CL04-15A, CL04-22B, CL04-22D, has the highest inhibition rate of 100%; for Rhizoctonia cerealis, compound CL03-49 , CL03-50, CL04-03, CL04-04, CL04-04, CL04-06, CL04-15A, CL04-15B, CL04-15C, CL04-22A, CL04-22B, CL04-22C, CL04-22D , CL04-22E, CL04-22F, CL04-24, CL04-25A, CL04-25B, CL04-25C, CL04-25E, CL04-17, CL04-32A, CL04-32B, CL04-32C, CL04-32D and CL04
  • the inhibition rate of -32F is above 50%, and the antibacterial activity of the above compound is higher than the antibacterial activity of the compound CL04-00 which is the closest to the chemical structure of the target compound of the present invention, which is more than 40%, wherein the compound CL03-49 The inhibition rates of
  • the antibacterial activity of the closest compound CL05-00 is more than 10% and both higher than the control azoxystrobin by more than 10% and the enestrobin ester by more than 20%, and the compounds CL03-49, CL03-50, CL04-03, CL04-04 and CL04-06 have the highest inhibition rate of 100%; for rice sheath blight, compounds CL03-49, CL03-50, CL04-03, CL04-04, CL04-04, CL04 -06, CL04-15A, CL04-15B, CL04-15C, CL04-22B, CL04-22C, CL04-22B, CL04-25A, CL04-25C, CL04-17, CL04-32A, CL04-32B, CL04-32C And the inhibition rate of CL04-32D is more than 35%.
  • the antibacterial activity of the above compound is higher than the antibacterial activity of the compound CL04-00 which is the closest to the chemical structure of the target compound of the present invention, which is more than 10%, wherein the compound CL04
  • the antibacterial activities of -06, CL04-15A, CL04-15B, CL04-15C, CL04-22B, CL04-22D, CL04-25C, CL04-32B, CL04-32C and CL04-32D were higher than those reported in the literature.
  • the bacteriostatic activity of the compound with the closest chemical structure of the target compound CL05-00 is more than 10% and both are higher than the control drug enestrobin by more than 10%, and the compounds CL04-22D, CL04-25C and CL04-32D
  • the rate is above 80%, which is higher than the control azoxystrobin; the activity against Phytophthora infestans shows that the compounds CL03-49, CL03-50, CL04-03, CL04-04, CL04-04, CL04 -06, CL04-15A, CL04-15B, CL04-15C, CL04-22A, CL04-22B, CL04-22C, CL04-22D, CL04-25A, CL04-25C, CL04-17, CL04-32A, CL04-32B , CL04-32C and CL04-32D suppression
  • the bacteriostatic activity of the above compounds is higher than the antibacterial activity of the compound CL04-00 and the control drug enestrobin which are the closest to the chemical structure of the target compound of the present invention,
  • the compound CL05-00 has a bacteriostatic activity of more than 10%, and the compounds CL04-22C, CL04-22D, CL04-25A, CL04-25C, CL04-32B, CL04-32C and CL04-32D have the highest inhibition rate of 100%; In summary, the compounds CL04-03, CL04-15B, CL04-15C, CL04-22D have a broad spectrum of bactericidal activity.
  • Example 8 Field trial results of the isothiazolyl ether methoxy acrylate derivative IV of the present invention for controlling cucumber powdery mildew:
  • the invention carries out a field efficacy test on a highly active compound, and the name and code of the selected control object are as follows: powdery mildew (Sphaerotheca fuliginea); the selected test crop variety is "Jinyou 40" cucumber.
  • Table 3 shows that the average control effect of 9.60% CL04-22D emulsifiable concentrate on cucumber powdery mildew is 78.62%; and the average control of 250g/L azoxystrobin SC (produced by British Syngenta Co., Ltd.) The effect is 70.19%, the activity of the compound of the present invention is higher than that of the control agent by nearly 10%; the average control effect of 50% of sputum ester (FLINT) WG (manufactured by Bayer CropScience Co., Germany) is 68.02%, and the chemical structure of trifloxystrobin The structure of the compound of the present invention is closest to that of the compound of the present invention, and the activity of the compound of the present invention is higher than that of the control agent by more than 10%.
  • Example 9 Field test results of the isothiazolyl ether methoxy acrylate derivative IV of the present invention for controlling cucumber downy mildew:
  • the invention carries out a field efficacy test on a highly active compound, and the name and code of the selected control object are as follows: cucumber downy mildew (Pseudoperponspora cubensis); the selected test crop variety "Jinlu No. 3" cucumber.
  • Application method and water consumption (liters/ha): In the early stage of cucumber downy mildew, spray application. The plants were evenly sprayed with a dose of 675 L/hm 2 , and the blank control was sprayed with equal amount of water. The experimental results are shown in Table 4.
  • Table 4 shows that the average control effect of 9.60% CL04-22D emulsifiable concentrate on cucumber downy mildew is 79.18%; and the control agent 50% sputum ester (FLINT) WG (produced by Bayer CropScience Co., Germany)
  • the average control effect is 72.02%, and the activity of the compound of the present invention is higher than 5% of the control agent; the average control effect of 250 g/L pyraclostrobin EC (produced by BASF Plant Protection (Jiangsu) Co., Ltd.) is 77.52%,
  • the activity of the compounds of the invention is comparable to the control agent.
  • TMV Tobacco mosaic virus
  • Table 5 shows that most of the compounds of the present invention have better anti-TMV activity; at 100 ⁇ g/ml, all compounds synthesized by the present invention have different degrees of anti-TMV activity. .
  • the compounds CL03-49, CL04-50, CL04-03, CL04-25A, CL04-25D, CL04-17, CL04-32B and CL04-32F were all resistant to tobacco mosaic virus activity above 30%.
  • the anti-tobacco mosaic virus activities of the compounds CL03-49, CL04-50, CL04-03, CL04-25A, CL04-32B and CL04-32F were higher than those reported in the literature as the closest compound to the chemical structure of the target compound of the present invention.
  • the anti-tobacco mosaic virus activity of the above compounds is higher than the reported compounds CL04-00, CL05-00 and Isobacteria which are closest to the chemical structure of the target compound of the present invention.
  • the amine has more than 10%, wherein the protective activities of the compounds CL03-50, CL04-04, CL04-06, CL04-22B, CL04-25C and CL04-32F are all above 50%; in the induction mode, the compound CL03-49, CL03-50, CL04-03, CL04-04, CL04-04, CL04-06, CL04-15A, CL04-15B, CL04-15C, CL04-22A, CL04-22B, CL04-22C, CL04-22D, The induction effects of CL04-22F, CL04-24, CL04-25A, CL04-25C, CL04-17, CL04-32A, CL04-32B, CL04-32D and CL04-32F are all above 30%.
  • Leaf virus activity More than 10% of the compounds CL04-00 and CL05-00 closest to the chemical structure of the target compound of the present invention are reported in the literature, among which compounds CL03-49, CL03-50, CL04-03, CL04-04 on CL04-06, CL04
  • the induction activity of -22C reached 80%, which was higher than the control drugs TDL, BTH, SZG-7 and isotianil; in the induction mode, the above compounds showed good induction activity. It can be seen that the compound CL04-04 and CL04-32B have good inhibitory activity against TMV. Most of the compounds of the invention have excellent anti-TMV activity.
  • the isothiazolyl ether methoxy acrylate derivative IV of the present invention is also resistant to rice dwarf disease, yellow dwarf disease, stripe leaf blight, tomato fern leaf virus disease, pepper mosaic virus disease, tobacco vein necrosis virus, corn Dwarf mosaic disease, cauliflower mosaic virus, Citrus virus disease, orchid flower virus disease, agriculture and forestry of Jianlan ring spot virus, and horticultural plant virus disease have good antiviral activity.
  • Example 11 Application of the combination of isothiazolium ether methoxy acrylate derivative IV of the present invention and insecticide in controlling agricultural and forestry and horticultural plant pests:
  • insectsticides are selected from the group consisting of: chlorpyrifos, dexamethasone, acetamiprid, emamectin, milavirin, avermectin, spinosyn, fenvalerate, high-grade fenvalerate, cypermethrin, and high efficiency Cypermethrin, cyhalothrin, deltamethrin, fenpropathrin, Beta-cyfluthrin, Lambda-cyhalothrin, permethrin, permethrin, methrin, bifenthrin, permethrin Ester, fenthrin, flumethrin, flufenacetate, imidaclopri
  • Example 12 Application of the combination of the isothiazolium ether methoxy acrylate derivative IV of the present invention and a bactericide in the control of agricultural and forestry and horticultural plant diseases:
  • All of the isothiazolium ether methoxy acrylate derivative IV of the present invention is combined with any one or two of the commercial bactericides to form a bactericidal composition for controlling agricultural and forestry and horticultural plant diseases.
  • the bactericidal composition processed dosage form is selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble thickener , poisonous valley, block bait, granular bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, hair Air agent, ointment, hot mist, cold spray, aerosol, solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microparticle, tracking powder, oil suspension Agent, oil dispersible powder, thickener, pouring agent, seed coating agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam releasing agent; the plant disease controlled by the bactericidal composition is selected from: rice Miao cotton rot, tomato root rot, potato
  • Example 13 Application of the combination of the isothiazolium ether methoxy acrylate derivative IV of the present invention and an anti-plant virus agent in controlling agricultural and forestry and horticultural plant virus diseases:
  • All of the isothiazolyl ether methoxy acrylate derivative IV of the present invention is combined with any one or both of the commercial antiviral agents to form an antiviral composition for controlling agricultural and forestry and horticultural plant virus diseases, the commodity Antiviral
  • the agent is selected from the group consisting of: benzothiadiazole, thiazide, abbreviated as TDL, isothiazide, and its common name in English is: isotianil, 4-methyl-1,2,3-thiadiazol-5-carboxylic acid , 4-methyl-1,2,3-thiadiazol-5-formate, 4-methyl-1,2,3-thiadiazole-5-carboxylic acid ethyl ester, 3,4-dichloroisothiazole- 5-carboxylic acid, sodium 3,4-dichloroisothiazol-5-carboxylate, ethyl 3,4-dichloroisothiazol-5-carboxylate, DL- ⁇ -aminobutyric acid
  • the antiviral composition processed dosage form is selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule , soluble concentrate, poisonous valley, block bait, granular poison Bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, hot aerosol ,cold spray, aerosol, solid/liquid mixture, liquid/liquid mixture, solid/solid mixture, lacquer, granule, trace powder, oil suspension, oil dispersible powder, thick rubber Agent, splashing agent, seed coating agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam release agent; the virus disease controlled by the antiviral composition is selected from the group consisting of rice dwarf disease, yellow dwarf disease, Stripe leaf
  • Example 14 Application of the combination of isothiazolyl ether methoxy acrylate derivative IV of the present invention and acaricide in controlling agricultural and forestry and horticultural plant damage:
  • All of the isothiazolium ether methoxy acrylate derivative IV of the present invention is combined with any one or both of the commercial acaricides to form a miticide composition for controlling agricultural and forestry and horticultural plant mites.
  • Acaricides are selected from the group consisting of: triazolyl tin, tricyclotin, phenbutyltin, triphosphorus, chlorpyrifos, methyl chlorpyrifos, phytophos, dichlorvos, heptene phosphorus, fast-acting phosphorus, monocrotophos, dibromo Phosphorus, chlorpyrifos, pyrimidine phosphorus, chloromethionine, omethoate, chlorpyrifos, ethion, malathion, chlorpyrifos, sulforaphane, phoxim, methyl pyrithione, Quetiapine, guanidine, triazophos, quenching, acesulfame,
  • the invention provides a class of isothiazolium ether methoxy acrylate derivatives, a preparation method thereof and use thereof.
  • the compound provided by the invention can regulate the biological activity of plant pests and plant pathogens in agriculture, horticulture, sanitary and forestry, and can be used in agriculture, horticulture, forestry, insecticide, acaricidal, bactericidal, anti-plant virus, induced plant production Disease resistance, with good economic value and application prospects.

Abstract

Provided in the present invention are isothiazole oxime ether strobilurin derivatives, a preparation method for same, and uses thereof. The present invention relates to 3,4-dichloroisothiazole oxime ether strobilurin derivatives, which have a chemical structural formula as represented by IV. Disclosed are the structural formula of the compounds, a synthesis method for same, and uses thereof as pesticides, fungicides, and antiviral agents for plants, uses of and a preparation method for the derivatives being used in conjunction with agriculturally acceptable excipients or synergists and with commercialized pesticides, fungicides, antiviral agents for plants, and acaricides in prevention and treatment of pests, diseases, viral diseases of plants in agriculture, forestry, and gardening.

Description

一类异噻唑肟醚甲氧基丙烯酸酯衍生物及其制备方法和用途Isothiazolyl ether methoxy acrylate derivative, preparation method and use thereof 技术领域Technical field
本发明的技术方案涉及含N含S的异噻唑肟醚甲氧基丙烯酸酯类化合物,具体涉及3,4-二氯异噻唑肟醚类的化合物,即3,4-二氯异噻唑肟醚甲氧基丙烯酸酯衍生物。The technical scheme of the present invention relates to an N-containing S-containing isothiazolyl ether methoxy acrylate compound, in particular to a compound of 3,4-dichloroisothiazolium ether, namely 3,4-dichloroisothiazolium ether A methoxy acrylate derivative.
背景技术Background technique
杂环化合物是高效、低毒、广谱的生物活性先导化合物,专利文献报道的活性分子大部分具有杂环结构;文献报道五元杂环化合物具有植物激活剂、杀菌剂、植物生长调节剂和杀虫剂的活性(陈丹萍.现代农药,2014,14(2):5-10),其中,异噻唑是重要的五元含氮含硫杂环化合物。Mel′nikov发现异噻唑化合物的植物生长调节活性(Mel′nikov N.N.,Zhurnal Vseoyuznogo Khimic heskogo Obshchestva im.D.I.Mendeleeva.1988,33(6),602-609)。Heterocyclic compounds are high-efficiency, low-toxic, broad-spectrum biologically active lead compounds. Most of the active molecules reported in the patent literature have heterocyclic structures. The five-membered heterocyclic compounds have been reported in the literature as plant activators, fungicides, plant growth regulators, and Insecticide activity (Chen Danping. Modern Pesticide, 2014, 14(2): 5-10), wherein isothiazole is an important five-membered nitrogen-containing sulfur-containing heterocyclic compound. Mel'nikov found the plant growth regulating activity of the isothiazole compound (Mel'nikov N.N., Zhurnal Vseoyuznogo Khimic heskogo Obshchestva im. D. I. Mendeleeva. 1988, 33(6), 602-609).
甲氧基丙烯酸酯类杀菌剂具有广谱的杀菌活性,对几乎所有真菌类(子囊菌纲、担子菌纲、卵菌纲和半知菌类)病害都有很好的活性,如麦类的白粉病、叶枯病、赤斑病、网斑病、黑腥病、水稻的稻瘟病、纹枯病及霜霉病和疫病等(关爱莹.精细与专用化学品,2012,20(4):24-28)。该类药剂具备高效、广谱、低毒、内吸和易降解等多种优点,现已成为全球最主要的农用杀菌剂(袁小勇.2014,34:170-177)。已成功商品化的甲氧基丙烯酸酯类杀菌剂中重要的品种主要有:嘧菌酯(azoxystrobin)、醚菌酯(kresoxim-methyl)、吡唑醚菌酯(pyraclostrobin)、肟菌酯(trifloxystrobin)、氟嘧菌酯(fluoxastrobin)、啶氧菌酯(picoxystrobin)、苯氧菌胺(metaminostrobin)、醚菌胺(dimoxystrobin)、肟醚菌胺(orysastrobin)、烯肟菌酯(enestrobin)、唑菌酯(pyraoxystrobin)、烯肟菌胺(SYP-1620)等。由于Strobilurin类杀菌剂作用位点单一,大量高频高强度使用带来的抗性问题十分突出(Fisher,N.Pest.Manage.Sci.2005,61(10):973-978);植物激活剂具有广谱持久的***获得抗病性,不直接作用于病原物而作用于植物本身,因此,无抗药性的风险,其创制研究迫在眉睫。The methoxy acrylate fungicide has a broad spectrum of bactericidal activity and is very active against almost all fungi (Ascomycetes, Basidiomycetes, Oomycetes and Deuteromycetes) diseases, such as wheat. Powdery mildew, leaf blight, red spot disease, net blotch, black shank, rice blast, sheath blight and downy mildew and disease (Guan Aiying. Fine and Specialty Chemicals, 2012, 20(4) :24-28). These agents have many advantages such as high efficiency, broad spectrum, low toxicity, systemic absorption and easy degradation. They have become the most important agricultural fungicides in the world (Yuan Xiaoyong. 2014, 34: 170-177). The most important varieties of methoxy acrylate fungicides that have been successfully commercialized are: azoxystrobin, kresoxim-methyl, pyraclostrobin, and trifloxystrobin. ), fluoxastrobin, picoxystrobin, metaminostrobin, dimoxystrobin, oressastrobin, enestrobin, azole Pyraoxystrobin, enestrobin (SYP-1620), and the like. Due to the single action site of Strobilurin fungicides, the resistance problem caused by a large number of high frequency and high intensity applications is very prominent (Fisher, N. Pest. Manage. Sci. 2005, 61 (10): 973-978); plant activators A system with a broad spectrum and long-lasting disease is resistant to disease and does not directly act on the pathogen and acts on the plant itself. Therefore, the risk of drug resistance is imperative.
为寻找和发现更加高效、广谱、低毒、低生态风险并与现有杀菌剂无交互抗性的农药先导化合物,本发明将含N含S的异噻唑药效团3,4-二氯异噻唑环引入甲氧基丙烯酸酯的先导结构中,设计合成了一类异噻唑肟醚甲氧基丙烯酸酯衍生物,同时进行了***的生物活性的筛选和评价,以期为新农药创制研究提供更多的高活性低抗性风险的侯选化合物。In order to find and discover pesticide lead compounds which are more efficient, broad spectrum, low toxicity, low ecological risk and have no cross-resistance with existing fungicides, the present invention will contain N-containing S-isothiazole pharmacophore 3,4-dichloro The isothiazole ring was introduced into the lead structure of methoxy acrylate, and a class of isothiazolyl ether methoxy acrylate derivatives was designed and synthesized. At the same time, the biological activity of the system was screened and evaluated, in order to provide new pesticide creation research. More candidate compounds with high activity and low resistance risk.
发明内容Summary of the invention
本发明所要解决的技术问题是:提供一类新的异噻唑肟醚甲氧基丙烯酸酯衍生物的合成方法及其调控农业、园艺、卫生和林业植物害虫、植物病原物的生物活性及其测定方法,同时提供这些化合物在农业领域、园艺领域、林业领域以及卫生领域中的应用。 The technical problem to be solved by the present invention is to provide a novel method for synthesizing a novel isothiazolyl ether methoxy acrylate derivative and its biological activity for regulating plant pests, plant pathogens in agriculture, horticulture, sanitary and forestry, and its determination The method provides both the application of these compounds in the agricultural, horticultural, forestry, and health fields.
本发明解决该技术问题所采用的技术方案是:具有农业领域、园艺领域、林业领域杀虫、杀螨活性、杀菌活性、抗植物病毒活性、诱导植物产生抗病活性的异噻唑肟醚甲氧基丙烯酸酯类化合物的化学结构通式见式Ⅳ:The technical solution adopted by the invention to solve the technical problem is: having an agricultural field, a horticultural field, a forestry field, an insecticidal activity, acaricidal activity, a bactericidal activity, an anti-plant virus activity, and an isothiazolyl ether methoxy group which induces a plant to produce disease resistance activity. The chemical structure of the acrylates is shown in Formula IV:
Ⅳ:
Figure PCTCN2017072557-appb-000001
IV:
Figure PCTCN2017072557-appb-000001
其中,R1选自:甲基、氢、胺基;R2选自:1,2-二氟乙基、炔丙基、环丙基、甲基、1-甲硫基-2-甲基丙-2-基、(R)-1-甲硫基丙-2-基;X选自:氧、氮,n=1,2;Y选自:CHOH-CH2,CHO-CH2,(CH=CH)m,m=0,1;Z选自:碳、氮。Wherein R 1 is selected from the group consisting of methyl, hydrogen, and amine; and R 2 is selected from the group consisting of: 1,2-difluoroethyl, propargyl, cyclopropyl, methyl, 1-methylthio-2-methyl Prop-2-yl, (R)-1-methylthiopropan-2-yl; X is selected from the group consisting of: oxygen, nitrogen, n = 1, 2; Y is selected from: CHOH-CH 2 , CHO-CH 2 , ( CH=CH) m , m=0,1; Z is selected from the group consisting of carbon and nitrogen.
本发明的3,4-二氯异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ的合成方法如下:The synthesis method of the 3,4-dichloroisothiazolyl ether methoxy acrylate derivative IV of the present invention is as follows:
Figure PCTCN2017072557-appb-000002
Figure PCTCN2017072557-appb-000002
其中,R1选自:甲基、氢、胺基;R2选自:1,2-二氟乙基、炔丙基、环丙基、甲基、1-甲硫基-2-甲基丙-2-基、(R)-1-甲硫基丙-2-基;X选自:氧、氮,n=1,2;Y选自:CHOH-CH2,CHO-CH2,(CH=CH)m,m=0,1;Z选自:碳、氮。Wherein R 1 is selected from the group consisting of methyl, hydrogen, and amine; and R 2 is selected from the group consisting of: 1,2-difluoroethyl, propargyl, cyclopropyl, methyl, 1-methylthio-2-methyl Prop-2-yl, (R)-1-methylthiopropan-2-yl; X is selected from the group consisting of: oxygen, nitrogen, n = 1, 2; Y is selected from: CHOH-CH 2 , CHO-CH 2 , ( CH=CH) m , m=0,1; Z is selected from the group consisting of carbon and nitrogen.
优选地,所述的噻二唑肟醚甲氧基丙烯酸酯衍生物的合成方法分为以下步骤:Preferably, the method for synthesizing the thiadiazolone methoxy acrylate derivative is divided into the following steps:
A.化合物Ⅱ的制备:A. Preparation of Compound II:
在25毫升单口圆底烧瓶中加入1.10毫摩尔将化合物I、3,4-二氯异噻唑-5-取代羰基化合物和盐酸分别加入乙醇溶液中,在室温下反应,反应完全后减压除去溶剂,将残余物纯化,即得所述化合物II;其中,所述3,4-二氯异噻唑-5-取代羰基化合物选自:3,4-二氯异噻唑-5-甲醛、3,4-二氯异噻唑-5-乙酮、4-(3,4-二氯异噻唑-5-基)-丁-3-烯-2-酮;Add 1.10 mmol of the compound I, 3,4-dichloroisothiazol-5-substituted carbonyl compound and hydrochloric acid to a solution of ethanol in a 25 ml single-neck round bottom flask, react at room temperature, and remove the solvent under reduced pressure after completion of the reaction. Purifying the residue to obtain the compound II; wherein the 3,4-dichloroisothiazol-5-substituted carbonyl compound is selected from the group consisting of: 3,4-dichloroisothiazol-5-formaldehyde, 3,4 -dichloroisothiazol-5-ethanone, 4-(3,4-dichloroisothiazol-5-yl)-but-3-en-2-one;
或B.化合物Ⅱ的制备:Or B. Preparation of Compound II:
将化合物I、3,4-二氯异噻唑-5-甲氰与巯基乙酸分别加入乙醇溶液中,在室温下反应,反应完全后将反应液浓缩,将残余物纯化,即得所述化合物II;The compound I, 3,4-dichloroisothiazol-5-cyanamide and thioglycolic acid are separately added to the ethanol solution, and reacted at room temperature. After the reaction is completed, the reaction solution is concentrated, and the residue is purified to obtain the compound II. ;
C.化合物Ⅲ的制备方法:C. Preparation method of compound III:
将化合物Ⅱ与氢氧化钠加入甲醇溶液中,然后加热回流进行反应,反应完全后将反应液浓缩,残余物用乙酸乙酯稀释,然后加入水将残余物溶解,分离出水层,然后将水层用盐酸调节pH至3,然后用乙酸乙酯萃取,水层用乙酸乙酯反萃一遍,合并有机层,有机层用饱和氯化钠洗,无水硫酸钠干燥,抽滤,减压除去溶剂,即得化合物Ⅲ; The compound II and sodium hydroxide are added to the methanol solution, and then the reaction is carried out by heating under reflux. After the reaction is completed, the reaction liquid is concentrated, and the residue is diluted with ethyl acetate, then the residue is dissolved by water, the aqueous layer is separated, and then the aqueous layer is separated. The pH was adjusted to 3 with hydrochloric acid, then extracted with EtOAc. EtOAc (EtOAc)EtOAc. , that is, compound III;
D.化合物Ⅳ的制备方法:D. Preparation of Compound IV:
将化合物Ⅲ、EDCI与HOBT加入至二氯甲烷中,在室温反应,然后向反应体系中加入R2-XHn,n=1,2,室温下继续反应,反应完全后,反应液用水洗两遍,分离出有机层,有机层分别用饱和碳酸氢钠和饱和氯化钠洗,无水硫酸钠干燥,抽滤,减压除去溶剂,将残余物纯化,即得到所述化合物Ⅳ。Adding compound III, EDCI and HOBT to dichloromethane, reacting at room temperature, then adding R 2 -XH n , n=1,2 to the reaction system, and continuing the reaction at room temperature. After the reaction is completed, the reaction solution is washed with water. The organic layer was separated, and the organic layer was washed with saturated sodium hydrogen sulfate and saturated sodium chloride, dried over anhydrous sodium sulfate, filtered,
作为一个优选的实施方案,本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物的合成方法分为以下步骤:As a preferred embodiment, the synthesis method of the isothiazolyl ether methoxy acrylate derivative of the present invention is divided into the following steps:
A.化合物Ⅱ的制备方法一:A. Preparation method of compound II:
在25毫升单口圆底烧瓶中加入1.10毫摩尔化合物I,用15毫升乙醇溶解,再加入1.00毫摩尔3,4-二氯异噻唑-5-取代羰基化合物,所述3,4-二氯异噻唑-5-取代羰基化合物选自:3,4-二氯异噻唑-5-甲醛、3,4-二氯异噻唑-5-乙酮、4-(3,4-二氯异噻唑-5-基)-丁-3-烯-2-酮,最后向反应体系中滴加两滴2摩尔/升的盐酸,室温搅拌12小时,反应完全后减压除去溶剂,残余物经200~300目硅胶柱层析纯化得化合物Ⅱ,洗脱剂为60~90摄氏度的石油醚:乙酸乙酯,根据产物的不同,体积比为9:1-2:1,收率70-80%;化合物Ⅱ制备的量和反应容器的体积按相应比例扩大或缩小。Into a 25 ml single-neck round bottom flask was added 1.10 mmol of Compound I, dissolved in 15 mL of ethanol, and then 1.00 mmol of 3,4-dichloroisothiazol-5-substituted carbonyl compound, 3,4-dichloro The thiazole-5-substituted carbonyl compound is selected from the group consisting of 3,4-dichloroisothiazol-5-carbaldehyde, 3,4-dichloroisothiazol-5-ethanone, 4-(3,4-dichloroisothiazol-5 -Based on -but-3-en-2-one, finally adding two drops of 2 mol/L hydrochloric acid dropwise to the reaction system, stirring at room temperature for 12 hours, after completion of the reaction, the solvent was removed under reduced pressure, and the residue was passed through 200-300 mesh. Purified by silica gel column chromatography to obtain compound II, the eluent is petroleum ether: ethyl acetate of 60-90 degrees Celsius, according to the product, the volume ratio is 9:1-2:1, the yield is 70-80%; compound II The amount prepared and the volume of the reaction vessel are enlarged or reduced in proportions.
B.化合物Ⅱ的制备方法二:B. Preparation method II of compound II:
在50毫升单口圆底烧瓶中加入1.43毫摩尔化合物I,加入20毫升的乙醇,再向反应体系中加入0.20克,即1.10毫摩尔的3,4-二氯异噻唑-5-甲氰,然后加入0.10克的巯基乙酸,室温搅拌过夜,反应结束后将反应液浓缩,残余物经200~300目硅胶柱层析纯化得到白色固体,洗脱剂为60~90摄氏度的石油醚:乙酸乙酯,体积比为10:1,收率97%;化合物Ⅱ制备的量和反应容器的体积按相应比例扩大或缩小。Into a 50 ml single-neck round bottom flask, 1.43 mmol of Compound I was added, 20 ml of ethanol was added, and 0.20 g, ie, 1.10 mmol of 3,4-dichloroisothiazol-5-cyanide was added to the reaction system, and then Add 0.10 g of thioglycolic acid, and stir at room temperature overnight. After the reaction is completed, the reaction mixture is concentrated. The residue is purified by silica gel column chromatography from 200 to 300 mesh to afford white solid. The volume ratio is 10:1, and the yield is 97%; the amount of the compound II prepared and the volume of the reaction vessel are expanded or reduced in a corresponding ratio.
C.化合物III的制备:C. Preparation of Compound III:
在25毫升单口圆底烧瓶中加入0.24毫摩尔化合物Ⅱ,用15毫升甲醇溶解,向反应中加入0.03克,即0.72毫摩尔氢氧化钠,然后加热回流30分钟,反应结束后将反应液浓缩,残余物用10毫升乙酸乙酯稀释,加入10毫升的水将固体全部溶解,分离出水层,水层用2摩尔/升的盐酸调节pH至3,然后用乙酸乙酯萃取,水层用乙酸乙酯反萃一遍,合并有机层,有机层用饱和氯化钠洗一遍,无水硫酸钠干燥,抽滤,减压除去溶剂,得化合物Ⅲ;收率95-100%;化合物Ⅲ制备的量和反应容器的体积按相应比例扩大或缩小。To a 25 ml single-necked round bottom flask was added 0.24 mmol of Compound II, dissolved in 15 ml of methanol, and 0.03 g of 0.72 mmol of sodium hydroxide was added to the reaction, followed by heating under reflux for 30 minutes. After the reaction was completed, the reaction mixture was concentrated. The residue was diluted with 10 ml of ethyl acetate. The solid was completely dissolved by adding 10 ml of water. The aqueous layer was separated. The aqueous layer was adjusted to pH 3 with 2 mol/L hydrochloric acid, and then extracted with ethyl acetate. The ester was back-extracted, and the organic layer was combined. The organic layer was washed with saturated sodium chloride and dried over anhydrous sodium sulfate, filtered, and then evaporated to remove solvent to afford compound III; yield 95-100%; The volume of the reaction vessel is enlarged or reduced in proportion to the corresponding ratio.
D.化合物Ⅳ的制备:D. Preparation of Compound IV:
在25毫升单口圆底烧瓶中加入0.30毫摩尔化合物Ⅲ,用15毫升干燥的二氯甲烷溶解,向反应中加入0.69克,即0.36毫摩尔EDCI,即1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐和0.43克,即0.32毫摩尔的HOBT,即1-羟基苯并三氮唑,加完之后室温搅拌30分钟,然后向反应体系中加入0.32毫摩尔的R2-XHn,n=1,2,室温搅拌2小时,反应结束后,反应 液用15毫升的水洗两遍,分离出有机层,有机层用饱和碳酸氢钠和饱和氯化钠各洗一遍,无水硫酸钠干燥,抽滤,减压除去溶剂,残余物经200~300目硅胶柱层析纯化得到白色固体,洗脱剂为60~90摄氏度的石油醚:乙酸乙酯,体积比为4:1,收率30-95%;化合物Ⅳ制备的量和反应容器的体积按相应比例扩大或缩小。0.35 mmol of compound III was added to a 25 ml single-neck round bottom flask, dissolved in 15 ml of dry dichloromethane, and 0.69 g, 0.36 mmol of EDCI, ie 1-ethyl-(3-dimethyl), was added to the reaction. Aminopropyl)carbodiimide hydrochloride and 0.43 g, ie 0.32 mmol of HOBT, ie 1-hydroxybenzotriazole, were stirred at room temperature for 30 minutes after addition, and then 0.32 mmol was added to the reaction system. R 2 -XH n , n = 1, 2, stirred at room temperature for 2 hours. After the reaction was completed, the reaction solution was washed twice with 15 ml of water, the organic layer was separated, and the organic layer was washed with saturated sodium hydrogen carbonate and saturated sodium chloride. Once again, dried over anhydrous sodium sulfate, suction filtered, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography from 200 to 300 mesh to afford white solid, eluent: petroleum ether: ethyl acetate, volume ratio of 60-90 ° C It is 4:1, the yield is 30-95%; the amount of the preparation of the compound IV and the volume of the reaction vessel are expanded or reduced in a corresponding ratio.
本发明还提供了所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在制备杀菌剂、抗烟草花叶病毒剂或植物激活剂中的用途。The invention also provides the use of the isothiazolidine methoxy acrylate derivative IV in the preparation of a bactericide, a tobacco mosaic virus agent or a plant activator.
本发明还提供了所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与农业上可接受的助剂在制备杀菌剂、抗烟草花叶病毒剂或植物激活剂中的用途。The invention also provides the use of the isothiazolium ether methoxy acrylate derivative IV and an agriculturally acceptable adjuvant in the preparation of a bactericide, a tobacco mosaic virus agent or a plant activator.
本发明还提供了所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在防治农业和林业以及园艺植物虫害中的用途。The invention also provides the use of the isothiazolidine methoxy acrylate derivative IV for controlling agricultural and forestry and horticultural plant pests.
优选地,所述异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与农业化学品共同施用;优选地,所述农业化学品选自:杀虫剂、杀菌剂、抗植物病毒剂、杀螨剂中的一种或几种。Preferably, the isothiazolyl ether methoxy acrylate derivative IV is co-administered with an agricultural chemical; preferably, the agricultural chemical is selected from the group consisting of: an insecticide, a bactericide, an anti-plant virus agent, an acaricide One or several of them.
优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述杀虫剂中的任意一种或两种组合形成杀虫组合物用于防治农业和林业以及园艺植物虫害;Preferably, the isothiazolyl ether methoxy acrylate derivative IV is combined with any one or both of the insecticides to form an insecticidal composition for controlling agricultural and forestry and horticultural plant pests;
优选地,所述杀虫剂选自:毒死蜱、地亚哝、啶虫脒、甲氨基阿维菌素、弥拜菌素、阿维菌素、多杀菌素、氰戊菊酯、高效氰戊菊酯、氯氰菊酯、高效氯氰菊酯、三氟氯氰菊酯、溴氰菊酯、甲氰菊酯、Beta-氟氯氰菊酯、Lambda-三氟氯氰菊酯、二氯苯醚菊酯、苄氯菊酯、丙烯菊酯、联苯菊酯、氯菊酯、醚菊酯、氟氯苯菊酯、氯氟胺氰戊菊酯、吡虫啉、烯啶虫胺、氯噻啉、噻虫啉、噻虫嗪、噻虫胺、呋虫胺、可尼丁、达特南、除虫脲、灭幼脲、伏虫隆、除虫隆、氟铃脲、氟虫脲、啶虫隆、虱螨脲、毒虫脲、氟幼脲、Noviflumuron即多氟脲,其CAS号为121451-02-3、氟螨脲、Novaluron即双苯氟脲、氟啶脲、Bay sir 6874即1-[(3.5-二氯-4)4-硝基苯氧基苯基3-3-(2-氯苯)-脲、Bay SIR-8514即1-(4-三氟甲氧基苯基)-3-(2-氯苯)-脲、嗪虫脲、Bistrifluron即双三氟虫脲、呋喃虫酰肼、虫酰肼、氯虫酰肼、甲氧虫酰肼、环虫酰肼、乐果、氧化乐果、敌敌畏、乙酰甲胺磷、***磷、喹硫磷、哒嗪硫磷、氯唑磷、叶蝉散、西维因、抗蚜威、速灭威、异丙威、杀螟丹、仲丁威、叶飞散、甲萘威、丙硫克百威、丁硫克百威、杀螟丹、溴螨酯、噻螨酮、唑螨酯、哒螨酮、四螨嗪、炔螨特、丁醚脲、吡蚜酮、螺螨酯、螺虫酯、螺虫乙酯、丁烯氟虫腈、***锡、噻嗪酮、灭线磷、氟虫腈、杀虫单、杀虫双、氯虫酰胺、氟虫酰胺、氟氰虫酰胺、氰虫酰胺、唑虫酰胺、溴虫腈、吡嗪酮、乙螨唑、吡螨胺、哒幼酮、吡丙醚、埃玛菌素;Preferably, the insecticide is selected from the group consisting of: chlorpyrifos, scorpion guanidine, acetamiprid, emamectin, imipenem, avermectin, spinosyn, fenvalerate, high-efficiency acetonide Pyrethroid, cypermethrin, beta-cypermethrin, cyhalothrin, deltamethrin, fenpropathrin, Beta-cyfluthrin, Lambda-cyhalothrin, permethrin, permethrin, methrin, hydrazine Pyrethrin, permethrin, fenthrin, flumethrin, flufenacetate, imidacloprid, nitenpyram, chlorothiazide, thiacloprid, thiamethoxam, clothianidin, fur Nicotinamide, cotinine, Dartnam, diflubenzuron, chlorbenzuron, flubenzuron, chlorfenapyr, hexaflumuron, flubenzuron, acetamiprid, guanidine, chlorpyrifos, flubenzuron, Noviflumuron is a polyfluorourea with a CAS number of 121451-02-3, fluoroquinone urea, Novaluron, ie, diphenylfluorourea, chlorfluazuron, and Bay sir 6874, 1-[(3.5-dichloro-4)4-nitro Phenoxyphenyl 3-3-(2-chlorophenyl)-urea, Bay SIR-8514, 1-(4-trifluoromethoxyphenyl)-3-(2-chlorophenyl)-urea, oxazide Urea, Bistrifluron, bis-trifluoroidazolium, furanyl hydrazide, tebufenozide, Tebufenozide, methoxyfenhydrazide, chlorfenapyr, dimethoate, omethoate, dichlorvos, acephate, triazophos, quetiapine, pyridazin, chlorpyrifos, arsenic, Xiweiyin, Kangwei, Kuweiwei, Weiweiwei, Zhidan, Zhongdingwei, Yefeisan, carbaryl, propylthiocarbamate, butyl thiocarb, chlorpyrifos, bromo oxime ester , thiazolone, oxazolidine, anthrone, tetrazine, alkyne, dibutyl ether urea, pymetrozine, spirodecyl ester, spirotetramat, spirotetramat, butene fipronil, triazole Tin, buprofezin, chlorpyrifos, fipronil, insecticidal, insecticidal, chlorantranil, flubendiamide, flufenamide, cyanamide, azole, chlorfenapyr, pyrazinone , etoxazole, pyridoxamine, ketone, pyriproxyfen, emamectin;
优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在所述杀虫组合物中的质量百分含量是1%-90%;Preferably, the isothiazolium ether methoxy acrylate derivative IV is present in the pesticidal composition in an amount of from 1% to 90% by mass;
优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述杀虫剂的比例为质量百分 比1%∶99%到99%∶1%;Preferably, the ratio of the isothiazolyl ether methoxy acrylate derivative IV to the insecticide is mass% Ratio 1%: 99% to 99%: 1%;
优选地,所述杀虫组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;Preferably, the dosage form processed by the pesticidal composition is selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous valley, lumps Bait, granular bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, Hot mist, cold spray, aerosol, solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microparticle, trace powder, oil suspension, oil dispersible powder , thickener, pouring agent, seed coating agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam release agent;
优选地,所述杀虫组合物防治的植物虫害选自:红蜘蛛、东亚飞蝗、云斑车蝗、中华稻蝗、日本黄脊蝗、单刺蝼蛄、东方蝼蛄、稻蓟马、烟蓟马、温室蓟马、稻管蓟马、麦简管蓟马、温室白粉虱、烟粉虱、黑尾叶蝉、大青叶蝉、棉叶蝉、斑衣蜡蝉、褐飞虱、白背飞虱、灰飞虱、甘蔗扁角飞虱、棉蚜、麦二叉蚜、麦长管蚜、桃蚜、高粱蚜、萝卜蚜、吹绵蚧、桑盾蚧、矢尖盾蚧、梨圆蚧、白蜡虫、红蜡蚧、朝鲜球坚蚧、梨网蝽、香蕉网蝽、细角花蝽、微小花蝽、针缘蝽、稻蛛缘蝽、稻褐蝽、稻黑蝽、稻绿蝽、绿盲蝽、苜蓿盲蝽、中黑盲蝽、大草蛉、丽草蛉、中华草蛉、谷蛾、衣蛾、黄刺蛾、褐刺蛾、扁刺蛾、麦蛾、棉红铃虫、甘薯麦蛾、小菜蛾、桃小食心虫、大豆食心虫、桃小食心虫、苹果顶梢卷叶蛾、褐带长卷叶蛾、拟小黄卷叶蛾、二化螟、豆荚螟、玉米螟、三化螟、菜螟、稻纵卷叶螟、条螟、棉卷叶野螟、桃蛀螟、黏虫、斜纹夜蛾、稻螟蛉、棉小造桥虫、甜菜夜蛾、大螟、棉铃虫、鼎点金刚钻、小地老虎、大地老虎、黄地老虎、盗毒蛾、舞毒蛾、甘薯天蛾、豆天蛾、直纹稻弄蝶、隐纹谷弄蝶、柑橘凤蝶、玉带凤蝶、菜粉蝶、苎麻赤蛱蝶、苎麻黄蛱蝶、豆芫菁、金星步甲、皱鞘步甲、麦穗步甲、沟金针虫、细胸金针虫、谷斑皮蠹、黑皮蠹、柑橘小吉丁虫、金缘吉丁虫、黄粉虫、黑粉虫、赤拟谷盗、杂拟谷盗、铜绿异丽金龟、暗黑金龟、华北大黑鳃金龟、桑天牛、星天牛、橘褐天牛、桃红颈天牛、大猿叶虫、小猿叶虫、黄守瓜、黄曲条跳甲、绿豆象、豌豆象、蚕豆象、玉米象、米象、小麦叶蜂、梨实蜂、黄带姬蜂、黏虫白星姬蜂、螟蛉悬茧姬蜂、棉铃虫齿唇姬蜂、螟黑点疣姬蜂、蚊、蝇、虻、麦红吸浆虫、麦黄吸浆虫、稻瘿蚊、柑橘大实蝇、瓜实蝇、麦叶灰潜蝇、美洲斑潜蝇、豆秆黑潜蝇、麦秆蝇、种蝇、葱蝇、萝卜蝇、伞裙追寄蝇、玉米螟厉寄蝇、黏虫;Preferably, the plant pests controlled by the insecticidal composition are selected from the group consisting of: red spider, oriental planthopper, cloud locust, Chinese rice blast, Japanese yellow ridge, single locust, oriental carp, rice locust, and tobacco Horse, greenhouse thrips, rice tube thrips, wheat tube horses, greenhouse whitefly, whitefly, black-tailed leafhopper, big green leafhopper, cotton leafhopper, spotted waxhopper, brown planthopper, white-backed planthopper , Laodelphax striatellus, sugarcane, flat-horned corn fly, cotton aphid, wheat bifurcation, wheat long tube, peach aphid, sorghum, radish, blown, sang shield, yam shield, pear round, White wax insects, red wax mites, Korean ball glutinous rice, pear net mites, banana net mites, fine-horned flower buds, tiny flower buds, needle-edge mites, rice spider mites, rice brown mites, rice black mites, rice green mites, Green-spotted scorpion, scorpion scorpion, black-spotted scorpion, large grass scorpion, cypress, Chinese grass scorpion, valley moth, clothing moth, yellow thorn moth, brown thorn moth, spur moth, wheat moth, cotton bollworm, Sweet potato moth, diamondback moth, peach small heartworm, soybean heartworm, peach small heartworm, apple tip leaf moth, brown leaf moth, pseudo-small leaf moth, stem borer, bean pod Corn borer, stem borer, rapeseed meal, rice leaf roller, barley, cotton leaf bark, peach aphid, armyworm, Spodoptera litura, rice bran, cotton small bridgeworm, beet armyworm, giant salamander , cotton bollworm, Ding Ding diamond, small tiger, earth tiger, yellow tiger, poisonous moth, gypsy moth, sweet potato hawk moth, bean hawk moth, straight grain rice butterfly, cryptic valley butterfly, citrus swallow butterfly, jade belt Swallowtail butterfly, cabbage butterfly, ramie red butterfly, ramie butterfly, bean phthalocyanine, Venus carapace, wrinkle sheath, armor, wheat burdock, echinoderma, scutellaria, variegata, black skin蠹, citrus small jiding insects, Jinyuan jiding insects, yellow mealworms, black mealworms, red worms, miscellaneous pirates, patina, golden tortoises, dark golden tortoises, North China black scorpion, sangtian cattle, star days Cow, Orange Brown Beech, Peach Red-necked Beef, Big Leafhopper, Small Leafhopper, Yellow Cucumber, Yellow-curved Flea, Green Bean, Pea, Broad Bean, Corn, Rice, Wheat Leaf, Pear Real bees, yellow-banded bees, sticky insects, white-spotted bee, stag beetle, cotton bollworm, beetle, bee, black-spotted bee, mosquito, fly, dragonfly Wheat red worm, wheat yellow worm, rice blast, citrus fruit fly, melon flies, larvae, larvae, stalk snail, stalk fly, fly, onion fly, radish fly , umbrella skirts to catch flies, corn scorpion flies, sticky insects;
优选地,所述杀虫组合物防治的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。 Preferably, the plant controlled by the pesticidal composition is selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, tapioca, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut , rapeseed, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, rape, Onions, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述杀菌剂中的任意一种或两种组合形成杀菌组合物用于防治农业和林业以及园艺植物病害,Preferably, the isothiazolyl ether methoxy acrylate derivative IV is combined with any one or both of the bactericides to form a bactericidal composition for controlling agricultural and forestry and horticultural plant diseases,
优选地,所述杀菌剂选自:苯并噻二唑、噻酰菌胺,简写为TDL、噻酰胺、甲噻诱胺、4-甲基-1,2,3-噻二唑-5-甲酸、4-甲基-1,2,3-噻二唑-5-甲酸钠、4-甲基-1,2,3-噻二唑-5-甲酸乙酯、DL-β-氨基丁酸、异噻菌胺,其英文通用名为:isotianil、3,4-二氯异噻唑-5-甲酸、3,4-二氯异噻唑-5-甲酸钠、3,4-二氯异噻唑-5-甲酸乙酯、病毒唑、安托芬、宁南霉素或水杨酸、霜脲氰、福美双、福美锌、代森锰锌、乙磷铝、甲基硫菌灵、百菌清、敌可松、腐霉利、苯锈啶、甲基托布津、托布津、精甲霜灵、氟吗啉、烯酰吗啉、高效甲霜灵、高效苯霜灵、双氯氰菌胺、磺菌胺、甲磺菌胺、噻氟菌胺、氟酰胺、叶枯酞、环丙酰菌胺、环氟菌胺、环酰菌胺、氰菌胺、硅噻菌胺、呋吡菌胺、吡噻菌胺、双炔酰菌胺、苯酰菌胺、甲呋酰胺、萎锈灵、乙菌利、异菌脲、嘧菌酯、醚菌胺、氟嘧菌酯、醚菌酯、苯氧菌胺、肟醚菌胺、啶氧菌酯、唑菌胺酯、肟菌酯、烯肟菌酯、烯肟菌胺、氧环唑、糠菌唑、环丙唑醇、苯醚甲环唑、烯唑醇、高效烯唑醇、氟环唑、腈苯唑、氟喹唑、氟硅唑、粉唑醇、己唑醇、亚胺唑、种菌唑、叶菌唑、腈菌唑、戊菌唑、丙环唑、丙硫菌唑、硅氟唑、戊唑醇、四氟醚唑、***醇、灭菌唑、联苯***醇、噻菌灵、麦穗宁、抑霉唑、高效抑霉唑、咪鲜胺、氟菌唑、氰霜唑、咪唑菌酮、噁咪唑、稻瘟酯、噁唑菌酮、啶菌噁唑、噁霉灵、噁霜灵、噻唑菌胺、土菌灵、辛噻酮、苯噻硫氰、十二环吗啉、丁苯吗啉、十三吗啉、拌种咯、咯菌腈、氟啶胺、啶斑肟、环啶菌胺、啶酰菌胺、氟啶酰菌胺、啶菌胺、嘧菌环胺、氟嘧菌胺、嘧菌腙、嘧菌胺、嘧霉胺、氯苯嘧啶醇、氟苯嘧啶醇、灭螨猛、二氰蒽醌、乙氧喹啉、羟基喹啉、丙氧喹啉、苯氧喹啉、乙霉威、异丙菌胺、苯噻菌胺、霜霉威、磺菌威、敌瘟磷、异稻瘟净、吡菌磷、甲基立枯磷、灭瘟素、春雷霉素、多抗霉素、多氧霉素、有效霉素、井冈霉素、链霉素、甲霜灵、呋霜灵、苯霜灵、呋酰胺、灭锈胺、多菌灵、苯菌灵、甲基硫菌灵、***酮、乙嘧酚磺酸酯、二甲嘧酚、乙嘧酚、敌菌丹、克菌丹、灭菌丹、乙烯菌核利、氟氯菌核利、菌核净、百菌清、稻瘟灵、稻瘟净、叶枯唑、五氯硝基苯、丙森锌、三乙膦酸铝、硫磺、波尔多液、硫酸铜、氧氯化铜、氧化亚铜、氢氧化铜、苯菌酮、戊菌隆、哒菌酮、四氯苯酞、咯喹酮、螺环菌胺、三环唑、嗪胺灵、多果啶、双胍辛盐、双胍辛胺、氯硝胺、苯磺菌胺、甲苯磺菌胺、吲哚酯、敌磺钠、喹菌酮、烯丙苯噻唑、溴硝醇、碘甲烷、威百亩、敌线酯、棉隆、二氯异丙醚、噻唑磷、硫线磷、丰索磷、虫线磷、苯线磷、灭线磷、除线磷、氯唑磷、丁硫环磷、杀线威、涕灭威、克百威、硫酰氟、二氯丙烯、二氯异烟酸、烯丙异噻唑;Preferably, the bactericide is selected from the group consisting of: benzothiadiazole, thiazide, abbreviated as TDL, thiazamide, methyl thiazide, 4-methyl-1,2,3-thiadiazole-5- Formic acid, sodium 4-methyl-1,2,3-thiadiazol-5-carboxylate, ethyl 4-methyl-1,2,3-thiadiazol-5-carboxylate, DL-β-aminobutyric acid, Isotianil, its common name in English is: isotianil, 3,4-dichloroisothiazol-5-carboxylic acid, 3,4-dichloroisothiazol-5-formate, 3,4-dichloroisothiazol-5- Ethyl formate, ribavirin, antofin, nymidine or salicylic acid, cymoxanil, thiram, thiram, mancozeb, ethylphosphoric acid, thiophanate, chlorothalonil, enemy Cortisone, procymidone, benzopyridin, methyl thiophanate, thiophanate, refined metalaxyl, flumorph, enoylmorpholine, high-performance metalaxyl, high-efficiency benzoxanthin, chloramphenicol, sulfonate Bismuthamide, mesalamide, thifluzamide, fluamide, leaf cumin, cyclopropionamide, cycloflufenamide, fenhexamid, cyanamide, thiastrobin, flufenamide, Pentimidamide, dipropiylamide, benzilamide, mefenamide, wilting, etoxin, iprodione, azoxystrobin, fenfluramine, fluoxastrobin Epoxystrobin, phenoxystrobin, difloxacin, picoxystrobin, pyraclostrobin, trifloxystrobin, enestrobin, enestrobin, oxycyclazole, carbendazole, cyproconazole , difenoconazole, diniconazole, high-efficiency diniconazole, epoxiconazole, nitrile azole, fluoroquinazole, flusilazole, fluconazole, hexaconazole, imidazole, inocastazole, leaf fungus Azole, myclobutanil, penconazole, propiconazole, prothioconazole, silicon fluoride, tebuconazole, tetrafluoroetherazole, triazole alcohol, sterilized azole, biphenyl triazole alcohol, thiabendazole, Maisuining, imazalil, high-efficiency imazalil, prochloraz, fluconazole, cyanoxazole, imidazolone, moxalimid, rice sterol ester, famoxadone, pyridine oxazole, carbendazim, Ointment, ethaboxam, carbendazim, octyl ketone, thiothiazide, dodecaline morpholine, butyl morpholine, thirteen morpholine, seed dressing, fludioxonil, fluazinam, pyridine Cantharidin, Cycloheximide, boscalid, fluaziram, azoxystrobin, cyprodinil, fluzalazine, azoxystrobin, azoxystrobin, pyrimethanil, chlorpyrimidine, Fluoropyrimidin, chlorpyrifos, dicyanoquinone, ethoxyquin, quinolin, C Quinoline, phenoxyquinoline, carbendazim, isopropylidene, phenothiamine, propamocarb, sulfavir, enemies, diarrhea, pyridoxine, methyl chlorpyrifos, chlorpyrifos Alizarin, Chunleimycin, Polymycin, Polyoxomycin, Adamycin, Jinggangmycin, Streptomycin, Metalaxyl, Furosemide, Benzocycline, Furfuramide, Detergent, Polysaccharide Ling, benomyl, thiophanate-methyl, triadimefon, acetaminophen sulfonate, dipyridamole, acetem, chlorpyrifos, captan, sterilized dan, vinyl nucleus, fluoride Chlorella, sclerotium, chlorothalonil, indigo, rice bran, leaf azole, pentachloronitrobenzene, zinc propyl, aluminum triethylphosphonate, sulfur, Bordeaux, copper sulfate, oxygen Copper chloride, cuprous oxide, copper hydroxide, benomyl, pentosan, chlorhexidine, tetrachlorophenyl hydrazine, praziquantel, spiroxylamine, tricyclazole, pyridazin, polyglycine, Bismuth octyl salt, bis-octylamine, chloramine, sulfonamide, toluidine, oxime ester, sodium sulfonate, quinocodone, allyl benzothiazole, bronopol, methyl iodide, Weibaimu, Enemy ester, cotton, dichloroisopropyl ether, thiazolyl, Sulfur, phosphorus, phenophos, insect phosphorus, benzene phosphorus, phosphine, phosphatidylcholine, chlorpyrifos, sulphur cyclophosphine, chlorpyrifos, aldicarb, carbofuran, sulfuryl fluoride, two Chloropropene, dichloroisonicotinic acid, allyl isothiazole;
优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在所述杀菌组合物中的总的质量百分含量是1%-90%, Preferably, the total mass percentage of the isothiazolyl ether methoxy acrylate derivative IV in the germicidal composition is from 1% to 90%,
优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述杀菌剂的比例为质量百分比1%∶99%到99%∶1%;Preferably, the ratio of the isothiazolyl ether methoxy acrylate derivative IV to the bactericide is 1% by mass: 99% to 99%: 1% by mass;
优选地,所述杀菌组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;Preferably, the bactericidal composition is processed in a dosage form selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous valley, block bait , granular bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, heat Spray, cold spray, aerosol, solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microparticle, trace powder, oil suspension, oil dispersible powder, Thickener, pouring agent, seed coating agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam release agent;
优选地,所述杀菌组合物防治的植物病害选自:稻苗绵腐病、番茄根腐病、马铃薯晚疫病、烟草黑胫病、谷子白粉病、葡萄霜霉病、莴苣霜霉病、黄瓜霜霉病、黄瓜炭疽病;Preferably, the plant disease controlled by the bactericidal composition is selected from the group consisting of: rice seedling cotton rot, tomato root rot, potato late blight, tobacco black shank, millet powdery mildew, grape downy mildew, lettuce downy mildew, cucumber Downy mildew, cucumber anthracnose;
优选地,所述杀菌组合物适用的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。Preferably, the bactericidal composition is suitable for plants selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut, Rape, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, rape, onion , garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述抗病毒药剂中的任意一种或两种组合形成抗病毒组合物用于防治农业和林业以及园艺植物病毒病害;Preferably, the isothiazolyl ether methoxy acrylate derivative IV is combined with any one or both of the antiviral agents to form an antiviral composition for controlling agricultural and forestry and horticultural plant virus diseases;
优选地,所述抗病毒药剂选自:苯并噻二唑、噻酰菌胺,简写为TDL、异噻菌胺,其英文通用名为:isotianil、4-甲基-1,2,3-噻二唑-5-甲酸、4-甲基-1,2,3-噻二唑-5-甲酸钠、4-甲基-1,2,3-噻二唑-5-甲酸乙酯、3,4-二氯异噻唑-5-甲酸、3,4-二氯异噻唑-5-甲酸钠、3,4-二氯异噻唑-5-甲酸乙酯、DL-β-氨基丁酸、病毒唑、安托芬、宁南霉素、噻酰胺、甲噻诱胺或水杨酸、嘧肽霉素、二氯异烟酸、烯丙异噻唑、井冈羟胺、井冈霉素;Preferably, the antiviral agent is selected from the group consisting of: benzothiadiazole, thiazide, abbreviated as TDL, isotianil, and its common name in English is: isotianil, 4-methyl-1,2,3- Thiadiazole-5-carboxylic acid, sodium 4-methyl-1,2,3-thiadiazole-5-carboxylate, ethyl 4-methyl-1,2,3-thiadiazole-5-carboxylate, 3, 4-Dichloroisothiazol-5-carboxylic acid, 3,4-dichloroisothiazol-5-formate, 3,4-dichloroisothiazol-5-carboxylic acid ethyl ester, DL-β-aminobutyric acid, ribavirin, Antofin, ningnanmycin, thiazamide, methyl thiazide or salicylic acid, glutathione, dichloroisonicotinic acid, allylisothiazole, Jinggang hydroxylamine, Jinggangmycin;
优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在所述抗病毒组合物中的总的质量百分含量是1%-90%,Preferably, the total mass percentage of the isothiazolyl ether methoxy acrylate derivative IV in the antiviral composition is from 1% to 90%,
优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述抗植物病毒剂的比例为质量百分比1%∶99%到99%∶1%;Preferably, the ratio of the isothiazolyl ether methoxy acrylate derivative IV to the anti-plant virus agent is 1% by mass: 99% to 99%: 1% by mass;
优选地,所述抗病毒组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼 浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;Preferably, the antiviral composition is processed in a dosage form selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous valley, lumps Bait, granular bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, Hot mist, cold spray, aerosol, solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microparticle, trace powder, oil suspension, oil dispersible powder , thick glue, splash Pouring agent, seed coating agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam release agent;
优选地,所述抗病毒组合物防治的病毒病害选自:水稻矮缩病、黄矮病、条纹叶枯病、番茄蕨叶病毒病、辣椒花叶病毒病、烟草脉坏死病毒病、玉米矮花叶病、花椰菜花叶病毒、柑橘病毒病、建兰花叶病毒、建兰环斑病毒;Preferably, the viral disease controlled by the antiviral composition is selected from the group consisting of rice dwarf disease, yellow dwarf disease, stripe leaf blight, tomato fern leaf virus disease, pepper mosaic virus disease, tobacco vein necrosis virus disease, corn dwarf Mosaic disease, cauliflower mosaic virus, citrus virus disease, broccoli virus, Jianlan ring spot virus;
优选地,所述抗病毒组合物用于防治的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。Preferably, the plant for controlling the antiviral composition is selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, tapioca, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture , peanuts, rapeseed, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, Rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述杀螨剂中的任意一种或两种组合形成杀螨组合物用于防治农业和林业以及园艺植物螨害;Preferably, the isothiazolyl ether methoxy acrylate derivative IV is combined with any one or both of the acaricides to form a acaricidal composition for controlling agricultural and forestry and horticultural plant damage;
优选地,所述杀螨剂选自:***锡、三环锡、苯丁锡、三磷锡、毒虫畏、甲基毒虫畏、巴毒磷、敌敌畏、庚烯磷、速灭磷、久效磷、二溴磷、毒死蜱、嘧啶磷、氯甲亚胺硫磷、氧乐果、敌杀磷、乙硫磷、马拉硫磷、虫螨畏、伏杀硫磷、辛硫磷、甲基嘧啶硫磷、喹硫磷、治螟磷、***磷、蚜灭多、水胺硫磷、甲胺磷、胺丙畏、氯亚胺硫磷、亚胺硫磷、氟丙菊酯、联苯菊酯、氯氟氰菊酯、精高效氯氟氰菊酯、甲氰菊酯、氟氰戊菊酯、氟氯苯菊酯、氟胺氰菊酯、溴氟菊酯、联苯肼酯、苯硫威、涕灭威、丁酮威、杀线威、抗虫威、久效威、苯菌灵、氯灭杀威、克百威、丁硫克百威、速灭威、蜱虱威、伐虫脒、单甲脒、杀螨脒、双甲脒、杀虫脒、苯甲酸苄酯、溴螨酯、丁氟螨酯、灭螨醌、氟蚜螨、氟虫脲、浏阳霉素、虫螨霉素、苏云金素、杀螨素、浏阳霉素、阿维菌素、多拉菌素、埃普利诺菌素、伊维菌素、赛拉菌素、莫西菌素、除虫菊素、烟碱、苦参碱、印楝素、鱼藤酮、吡螨胺、哒螨酮、唑螨酯、四螨嗪、炔螨特、噻螨酮、螺螨酯、嘧螨酯、杀螨酯、克螨特、哒螨灵;Preferably, the acaricide is selected from the group consisting of: triazole tin, tricyclotin, phenbutyltin, triphosphorus, chlorpyrifos, methyl chlorpyrifos, phytophos, dichlorvos, heptene phosphorus, quick-killing phosphorus, long time Phosphorus, dibromophosphorus, chlorpyrifos, pyrimidine, chloromethylimine, omethoate, chlorpyrifos, ethion, malathion, worm, phoxim, phoxim, Pyrithione, quetiapine, strontium phosphate, triazophos, quenching, acesulfame, methamidophos, acesulfame, chloroimidate, imipenem, flumethrin, Bifenthrin, cyhalothrin, cyhalothrin, fenpropathrin, fluvalerate, flumethrin, fluvalinate, bifenthrin, biphenyl hydrazine Ester, phenylthiocarb, aldicarb, butanone, chlorpyrifos, anti-insect, long-acting, benomyl, chlorhexidine, carbofuran, butyl thiocarb, fast-acting, 蜱Converse, worm, monomethyl hydrazine, acaricidal, amitraz, chlorpyrifos, benzyl benzoate, bromo oxime ester, butyl fluoro ester, guanidine, fluoranthene, flubenzuron, Liuyang Neomycin, echinomycin, sulphate, acaricidin, liuyangmycin Avermectin, doramectin, eplenomycin, ivermectin, serramycin, moxidectin, pyrethrin, nicotine, matrine, azadirachtin, rotenone, pyridoxine Amine, anthrone, oxazolidine, tetrazine, alkyne , thiazolone , spirodecyl ester, pyridoxine , acaricidal ester , ketone, hydrazine ;
优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在所述杀螨组合物中的总的质量百分含量是1%-90%,Preferably, the total mass percentage of the isothiazolyl ether methoxy acrylate derivative IV in the acaricidal composition is from 1% to 90%,
优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述杀螨剂的比例为质量百分比1%∶99%到99%∶1%;Preferably, the ratio of the isothiazolyl ether methoxy acrylate derivative IV to the acaricide is 1% by mass: 99% to 99%: 1% by mass;
优选地,所述杀螨组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣 剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;Preferably, the dosage form processed by the acaricidal composition is selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous valley, block Bait, granular bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, Hot mist, cold spray, aerosol, solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microparticle, trace powder, oil suspension, oil dispersible powder , thickener, pouring agent, seed coat Agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam release agent;
优选地,所述杀螨组合物防治的螨害选自:螨害选自叶螨科、细须螨科、呋线螨、瘿螨科、红叶螨属、瘿螨科的害螨,这些害螨是世界性农业害螨、林业害螨、园艺害螨和卫生害螨;Preferably, the cockroach damage controlled by the acaricidal composition is selected from the group consisting of: the mites are selected from the group consisting of the genus Aphididae, the genus Diptera, the eucalyptus, the genus Eucalyptus, the genus Eucalyptus, and the mites. World agricultural pests, forest pests, horticultural pests and health hazards;
优选地,所述杀螨组合物用于防治的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。Preferably, the plant for controlling the acaricidal composition is selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture , peanuts, rapeseed, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, Rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
本发明所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ的生物活性测定如下:The biological activity of the isothiazolyl ether methoxy acrylate derivative IV of the present invention is determined as follows:
E.本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ的杀菌活性测定:E. Determination of bactericidal activity of the isothiazolyl ether methoxy acrylate derivative IV of the present invention:
本发明的异噻唑肟醚甲氧基丙烯酸酯Ⅳ的杀菌或抑菌活性采用菌体生长率测定法,具体步骤为:取1.8毫克样品溶解在2滴N,N-二甲基甲酰胺中,然后用含有一定量吐温20乳化剂的水溶液稀释至500微克/毫升的药剂,将供试药剂在无菌条件下各吸取1毫升于培养皿内,再分别加入9毫升PDA培养基,摇匀后制成50微克/毫升含药平板,以添加1毫升灭菌水的平板做空白对照,用直径4毫米的打孔器沿菌丝外缘切取菌盘,移至含药平板上,呈等边三角形摆放,每处理重复3次,将培养皿放在24±1摄氏度恒温培养箱内培养,待对照菌落直径扩展到2-3厘米后调查各处理菌盘扩展直径,求平均值,与空白对照比较计算相对抑菌率,供试菌种为我国农业生产中田间实际发生的大部分典型植物病原菌的种属,其代号和名称如下:AS:番茄早疫病菌,其拉丁名为:Alternaria solani、BC:黄瓜灰霉病菌,其拉丁名为:Botrytis cinerea、CA:花生褐斑病菌,其拉丁名为:Cercospora arachidicola、GZ:小麦赤霉病菌,其拉丁名为:Gibberella zeae、PI:马铃薯晚疫病菌,其拉丁名为:Phytophthora infestans(Mont.)de Bary、PP:苹果轮纹病菌,其拉丁名为:Physalospora piricola、PS:水稻纹枯病菌,其拉丁名为:Pellicularia sasakii、RC:禾谷丝核菌,其拉丁名为:Rhizoctonia cerealis、SS:油菜菌核病菌,其拉丁名为:Sclerotinia sclerotiorum。The bactericidal or bacteriostatic activity of the isothiazolyl ether methoxy acrylate IV of the present invention is determined by a cell growth rate method, and the specific steps are as follows: a 1.8 mg sample is dissolved in 2 drops of N,N-dimethylformamide, Then dilute to 500 μg / ml of the drug with an aqueous solution containing a certain amount of Tween 20 emulsifier, and take 1 ml of the test agent under sterile conditions into the culture dish, then add 9 ml of PDA medium separately, shake well Then make a 50 μg/ml drug-containing plate, add a 1 ml sterilized water plate as a blank control, use a 4 mm diameter puncher to cut the fungus disc along the outer edge of the hyphae, and transfer it to the drug-containing plate. The triangles were placed and the treatment was repeated 3 times. The culture dishes were placed in a constant temperature incubator at 24 ± 1 ° C. After the diameter of the control colonies was extended to 2-3 cm, the expanded diameter of each treated disk was investigated and averaged. The relative inhibition rate was calculated by blank control. The tested strains were the species of most typical plant pathogens actually occurring in the field of agricultural production in China. The codes and names are as follows: AS: tomato early blight, its Latin name: Alternaria Solani, BC: Cucumber gray mold, its Latin name: Botrytis cinerea, CA: peanut brown spot disease, its Latin name: Cercospora arachidicola, GZ: Fusarium graminearum, its Latin name: Gibberella zeae, PI: Phytophthora infestans, Its Latin name is: Phytophthora infestans (Mont.) de Bary, PP: Apple ring rot, its Latin name: Physalospora piricola, PS: Rhizoctonia solani, its Latin name: Pellicularia sasakii, RC: cereal Nuclear bacteria, its Latin name: Rhizoctonia cerealis, SS: Sclerotinia sclerotiorum, its Latin name: Sclerotinia sclerotiorum.
F.本发明的3,4-二氯异噻唑肟醚甲氧基丙烯酸酯衍生物诱导抗病活性的测定:F. Determination of the inducing activity of the 3,4-dichloroisothiazolyl ether methoxy acrylate derivative of the present invention:
异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ的活性筛选方法如下,烟草花叶病毒简写为TMV:The screening method for the activity of the isothiazolyl ether methoxy acrylate derivative IV is as follows. The tobacco mosaic virus is abbreviated as TMV:
(1).阳性对照植物激活剂:选择质量纯度纯度大于99.5%的噻酰菌胺为阳性对照的植物激活剂;噻酰菌胺简写为TDL;(1). Positive control plant activator: select a plant activator with a purity purity greater than 99.5% of thiazide as a positive control; thiazide is abbreviated as TDL;
(2).异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ的诱导烟草抗TMV活性的筛选方法:离体直接抗病毒活性的测定采用半叶法进行;活体诱导是将苗龄一致的普通烟,3盆为一组,分别 于接种前7天前处理过的烟苗,处理方式包括:喷施供试化合物溶液2到3次,每次10毫升,或土壤处理,每次10毫升,测定浓度为100微克/毫升,第7天于新长出的烟叶上摩擦接种TMV,将烟苗置于其生长适宜温度及光照下培养3天后,检查发病情况,综合病斑数目按下式计算出供试化合物对TMV的诱导抗病毒效果,每一处理设3次重复,空白对照和标准药剂对照分别选择水和TDL:(2) Screening method for inducing tobacco anti-TMV activity of isothiazolyl ether methoxy acrylate derivative IV: The determination of direct antiviral activity in vitro is carried out by the half-leaf method; the living body induction is a common cigarette with uniform seedling age. , 3 pots are a group, respectively The tobacco seedlings treated before 7 days before inoculation include: spraying the test compound solution 2 to 3 times, each time 10 ml, or soil treatment, 10 ml each time, the concentration is determined to be 100 μg/ml, On the 7th day, the TMV was rubbed on the newly grown tobacco leaves, and the seedlings were placed in the growth temperature and light for 3 days. The disease was examined. The number of lesions was calculated according to the following formula. The virus effect was set to 3 replicates per treatment, and the blank and standard drug controls were selected for water and TDL, respectively:
Figure PCTCN2017072557-appb-000003
Figure PCTCN2017072557-appb-000003
其中,R为供试化合物对烟草抗TMV的诱导效果,单位:%;CK为清水对照叶片的平均枯斑数,单位:个;I为经供试化合物诱导处理后叶片的平均枯斑数,单位:个。Wherein, R is the inducing effect of the test compound on tobacco anti-TMV, unit: %; CK is the average number of dead spots of the control leaves of clear water, unit: one; I is the average number of leaves of the leaves after induction treatment by the test compound, unit: PCS.
本发明的有益效是:对异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ进行了先导优化,并对异噻唑肟醚甲氧基丙烯酸酯衍生物进行了抑菌活性的筛选。The beneficial effects of the present invention are: lead optimization of the isothiazolyl ether methoxy acrylate derivative IV, and screening of the isothiazolyl ether methoxy acrylate derivative for bacteriostatic activity.
本发明通过特定制备和生物活性测定实施例更加具体说明异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ的合成与生物活性及应用,所述实施例仅用于具体说明本发明而非限制本发明,尤其是生物活性仅是举例说明,而非限制本专利,具体实施方式如下:The present invention more specifically illustrates the synthesis and biological activity and use of the isothiazolium ether methoxy acrylate derivative IV by specific preparation and biological activity assay examples, which are intended to specifically illustrate the invention and not to limit the invention. In particular, the biological activity is merely illustrative and not limiting, and the specific embodiments are as follows:
实施例1:化合物Ⅱ的制备方法一:Example 1: Preparation of Compound II Method 1:
在25毫升单口圆底烧瓶中加入1.10毫摩尔化合物I,用15毫升乙醇溶解,再加入1.00毫摩尔3,4-二氯异噻唑-5-取代羰基化合物,所述3,4-二氯异噻唑-5-取代羰基化合物选自:3,4-二氯异噻唑-5-甲醛、3,4-二氯异噻唑-5-乙酮、4-(3,4-二氯异噻唑-5-基)-丁-3-烯-2-酮,最后反应体系中滴加两滴2摩尔/升的盐酸,室温搅拌12小时,反应完全后减压除去溶剂,残余物经200~300目硅胶柱层析纯化得化合物Ⅱ,洗脱剂为60~90摄氏度的石油醚:乙酸乙酯,体积比为9:1,收率70-80%;当R1为甲基,Y为(CH=CH)m,m=0,Z为氮时,核磁数据如下:1HNMR(CDCl3)δ7.51(s,1H,Ph-H),7.47-7.43(m,2H,Ph-H),7.24-7.20(m,1H,Ph-H),5.23(s,2H,Ph-CH2),4.06(s,3H,O-CH3),3.83(s,3H,O-CH3),2.52(s,3H,N=C-CH3)。化合物Ⅱ制备的量和反应容器的体积按相应比例扩大或缩小。化合物Ⅱ的理化参数和结构参数见表1。Into a 25 ml single-neck round bottom flask was added 1.10 mmol of Compound I, dissolved in 15 mL of ethanol, and then 1.00 mmol of 3,4-dichloroisothiazol-5-substituted carbonyl compound, 3,4-dichloro The thiazole-5-substituted carbonyl compound is selected from the group consisting of 3,4-dichloroisothiazol-5-carbaldehyde, 3,4-dichloroisothiazol-5-ethanone, 4-(3,4-dichloroisothiazol-5 -butyl-3-butan-2-one, two drops of 2 mol/L hydrochloric acid were added dropwise in the final reaction system, and stirred at room temperature for 12 hours. After the reaction was completed, the solvent was removed under reduced pressure, and the residue was subjected to silica gel from 200 to 300 mesh. Column chromatography to obtain compound II, the eluent is 60-90 degrees Celsius petroleum ether: ethyl acetate, the volume ratio is 9:1, the yield is 70-80%; when R 1 is methyl, Y is (CH = CH) m , m = 0, when Z is nitrogen, the nuclear magnetic data are as follows: 1 H NMR (CDCl 3 ) δ 7.51 (s, 1H, Ph-H), 7.47-7.43 (m, 2H, Ph-H), 7.24 -7.20 (m, 1H, Ph-H), 5.23 (s, 2H, Ph-CH 2 ), 4.06 (s, 3H, O-CH 3 ), 3.83 (s, 3H, O-CH 3 ), 2.52 ( s, 3H, N = C-CH 3 ). The amount of the compound II prepared and the volume of the reaction vessel are enlarged or reduced in a corresponding ratio. The physical and chemical parameters and structural parameters of Compound II are shown in Table 1.
实施例2:化合物Ⅱ的制备方法二:Example 2: Preparation of Compound II Method 2:
在25毫升单口圆底烧瓶中加入1.10毫摩尔化合物I,用15毫升乙醇溶解,再加入1.00毫摩尔3,4-二氯异噻唑-5-甲氰,最后反应体系中滴加0.10克巯基乙酸,室温搅拌12小时,反应完全后减压除去溶剂,残余物经200~300目硅胶柱层析纯化得化合物Ⅱ,洗脱剂为60~90摄氏度的石油醚:乙酸乙酯,根据产物的不同,体积比为10:1,收率80-97%;当R1氨基,Y为(CH=CH)m,m=0,Z为氮时,核磁数据如下:1HNMR(CDCl3)δ7.40-7.30(m,3H,Ph-H),7.13(d,J=6.4Hz,1H,Ph-H),5.18(s,2H,NH2),4.91(s,2H,Ph-CH2),3.97(s,3H,O-CH3),3.79(s,3H,O-CH3)。化合物Ⅱ制备的量和反应容器的体积按相应比例扩大或缩小。化合物Ⅱ的理化参数和结构 参数见表1。Into a 25 ml single-neck round bottom flask, 1.10 mmol of Compound I was added, dissolved in 15 ml of ethanol, and then 1.00 mmol of 3,4-dichloroisothiazol-5-cyanide was added. Finally, 0.10 g of thioglycolic acid was added dropwise to the reaction system. After stirring at room temperature for 12 hours, the solvent is removed under reduced pressure. The residue is purified by silica gel column chromatography from 200 to 300 mesh to afford compound II, eluent: petroleum ether: ethyl acetate, 60-90 ° C, depending on product The volume ratio is 10:1, the yield is 80-97%; when R 1 amino group, Y is (CH=CH) m , m=0, Z is nitrogen, the nuclear magnetic data is as follows: 1 HNMR(CDCl 3 ) δ7. 40-7.30 (m, 3H, Ph-H), 7.13 (d, J = 6.4 Hz, 1H, Ph-H), 5.18 (s, 2H, NH 2 ), 4.91 (s, 2H, Ph-CH 2 ) , 3.97 (s, 3H, O-CH 3 ), 3.79 (s, 3H, O-CH 3 ). The amount of the compound II prepared and the volume of the reaction vessel are enlarged or reduced in a corresponding ratio. The physical and chemical parameters and structural parameters of Compound II are shown in Table 1.
实施例3:化合物III的制备方法:Example 3: Preparation of Compound III:
在25毫升单口圆底烧瓶中加入0.24毫摩尔化合物Ⅱ,用15毫升甲醇溶解,向反应中加入0.03克,即0.72毫摩尔氢氧化钠,然后加热回流30分钟,反应结束后将反应液浓缩,残余物用10毫升乙酸乙酯稀释,加入10毫升的水将固体全部溶解,分离出水层,水层用2摩尔/升的盐酸调节pH至3,然后用乙酸乙酯萃取,水层用乙酸乙酯反萃一遍,合并有机层,有机层用饱和氯化钠洗一遍,无水硫酸钠干燥,抽滤,减压除去溶剂,得白色固体III;收率95%。化合物III制备的量和反应容器的体积按相应比例扩大或缩小。化合物III的理化参数和结构参数见表1。To a 25 ml single-necked round bottom flask was added 0.24 mmol of Compound II, dissolved in 15 ml of methanol, and 0.03 g of 0.72 mmol of sodium hydroxide was added to the reaction, followed by heating under reflux for 30 minutes. After the reaction was completed, the reaction mixture was concentrated. The residue was diluted with 10 ml of ethyl acetate. The solid was completely dissolved by adding 10 ml of water. The aqueous layer was separated. The aqueous layer was adjusted to pH 3 with 2 mol/L hydrochloric acid, and then extracted with ethyl acetate. The ester was back-extracted and the organic layer was combined. The organic layer was washed with saturated sodium chloride, dried over anhydrous sodium sulfate, filtered and evaporated The amount of Compound III prepared and the volume of the reaction vessel are expanded or reduced in proportions. The physical and chemical parameters and structural parameters of Compound III are shown in Table 1.
实施例4:化合物Ⅳ的制备方法:Example 4: Preparation of Compound IV:
在25毫升单口圆底烧瓶中加入0.30毫摩尔化合物III,用15毫升干燥的二氯甲烷溶解,向反应中加入0.69克,即0.36毫摩尔EDCI和0.43克,即0.32毫摩尔的HOBT,加完之后室温搅拌30分钟,然后向反应体系中加入0.32毫摩尔的1,2-二氟乙胺,室温搅拌2小时,反应结束后,反应液用15毫升的水洗两遍,分离出有机层,有机层分别用饱和碳酸氢钠和饱和氯化钠各洗一遍,再无水硫酸钠干燥,抽滤,减压除去溶剂,残余物经200~300目硅胶柱层析纯化得到白色固体Ⅳ,洗脱剂为60~90摄氏度的石油醚:乙酸乙酯,体积比为4:1,收率95%;当R1为甲基,R2为1,2-二氟乙基,X为氮,Y为(CH=CH)m,m=0,Z为氮时,该化合物的核磁数据如下:1HNMR(CDCl3)δ7.57-7.39(m,3H,Ph-H),7.22(dd,J=6.7,1.9Hz,1H,Ph-H),7.11(s,1H,Ph-H),5.91(tdd,J=55.9,8.6,4.3Hz,1H,CHF2),5.18(d,J=38.8Hz,2H,Ph-CH2),4.00(d,J=13.8Hz,3H,O-CH3),3.83-3.65(m,2H,N-CH2),2.42(d,J=72.2Hz,3H,N=C-CH3)。化合物Ⅳ制备的量和反应容器的体积按相应比例扩大或缩小。化合物Ⅳ的理化参数和结构参数见表1。0.35 mmol of Compound III was added to a 25 ml single-neck round bottom flask, dissolved in 15 ml of dry dichloromethane, and 0.69 g, 0.36 mmol EDCI and 0.43 g, 0.32 mmol of HOBT was added to the reaction. After stirring at room temperature for 30 minutes, 0.32 mmol of 1,2-difluoroethylamine was added to the reaction system, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, the reaction solution was washed twice with 15 ml of water to separate an organic layer. The layers were washed with saturated sodium bicarbonate and saturated sodium chloride and dried over anhydrous sodium sulfate. The agent is 60-90 degrees Celsius petroleum ether: ethyl acetate, the volume ratio is 4:1, the yield is 95%; when R 1 is methyl, R 2 is 1,2-difluoroethyl, X is nitrogen, Y When (CH=CH) m , m=0, and Z is nitrogen, the nuclear magnetic data of the compound are as follows: 1 H NMR (CDCl 3 ) δ 7.57-7.39 (m, 3H, Ph-H), 7.22 (dd, J =6.7, 1.9 Hz, 1H, Ph-H), 7.11 (s, 1H, Ph-H), 5.91 (tdd, J = 55.9, 8.6, 4.3 Hz, 1H, CHF 2 ), 5.18 (d, J = 38.8) Hz, 2H, Ph-CH 2 ), 4.00 (d, J = 13.8 Hz, 3H, O-CH 3 ), 3.83 - 3.65 (m , 2H, N-CH 2 ), 2.42 (d, J = 72.2 Hz, 3H, N = C-CH 3 ). The amount of Compound IV prepared and the volume of the reaction vessel are enlarged or reduced in corresponding proportions. The physical and chemical parameters and structural parameters of compound IV are shown in Table 1.
实施例5:化合物CL04-00的制备方法:Example 5: Preparation of Compound CL04-00:
Figure PCTCN2017072557-appb-000004
Figure PCTCN2017072557-appb-000004
在25毫升单口圆底烧瓶中加入1.10毫摩尔化合物b,用15毫升乙醇溶解,再加入1.00毫摩尔3-氯异噻唑-5-乙酮,最后反应体系中滴加两滴2摩尔/升的盐酸,室温搅拌12小时,反应完全后减压除去溶剂,残余物经200~300目硅胶柱层析纯化得化合物CL04-00,洗脱剂为60~90摄氏度的石油醚:乙酸乙酯,体积比为4:1,收率68.22%。In a 25 ml single-neck round bottom flask, 1.10 mmol of compound b was added, dissolved in 15 ml of ethanol, and then 1.00 mmol of 3-chloroisothiazol-5-ethanone was added. Finally, two drops of 2 mol/L were added to the reaction system. Hydrochloric acid, stirred at room temperature for 12 hours, the reaction was completed, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography from 200 to 300 mesh to obtain compound CL04-00, eluent: petroleum ether: ethyl acetate, 60-90 ° C, volume The ratio was 4:1 and the yield was 68.22%.
实施例6:化合物CL05-00的制备方法: Example 6: Preparation of Compound CL05-00:
Figure PCTCN2017072557-appb-000005
Figure PCTCN2017072557-appb-000005
为了比较结构与本发明中的化合物结构最接近的化合物之间的活性差异,本发明合成了文献报道的化合物CL05-00,具体合成步骤如下:In order to compare the difference in activity between the compounds whose structure is closest to the structure of the compound in the present invention, the present invention synthesizes the compound CL05-00 reported in the literature, and the specific synthesis steps are as follows:
在25毫升单口圆底烧瓶中加入1.00毫摩尔化合物A,用15毫升DMF溶解,再加入1.50毫摩尔碳酸铯,最后反应体系中加入1.5毫摩尔的化合物B,室温搅拌12小时,反应完全后减压除去溶剂,残余物经200~300目硅胶柱层析纯化得化合物CL05-00,洗脱剂为60~90摄氏度的石油醚:乙酸乙酯,体积比为8:1,收率55.57%。Into a 25 ml single-neck round bottom flask, 1.00 mmol of Compound A was added, dissolved in 15 ml of DMF, and then 1.50 mmol of cesium carbonate was added. Finally, 1.5 mmol of Compound B was added to the reaction system, and the mixture was stirred at room temperature for 12 hours. The solvent was removed by pressure, and the residue was purified by silica gel column chromatography from 200 to 300 mesh to afford compound CL05-00. The eluent was petroleum ether: ethyl acetate of 60 to 90 degrees Celsius. The volume ratio was 8:1 and the yield was 55.57%.
实施例7:本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ的抑菌活性测定结果:Example 7: Determination of the antibacterial activity of the isothiazolyl ether methoxy acrylate derivative IV of the present invention:
本发明测试的常见植物病原真菌的代号和名称如下:AS:番茄早疫病菌,其拉丁名为:Alternaria solani、BC:黄瓜灰霉病菌,其拉丁名为:Botrytis cinerea、CA:花生褐斑病菌,其拉丁名为:Cercospora arachidicola、GZ:小麦赤霉病菌,其拉丁名为:Gibberella zeae、PI:马铃薯晚疫病菌,其拉丁名为:Phytophthora infestans(Mont.)de Bary、PP:苹果轮纹病菌,其拉丁名为:Physalospora piricola、PS:水稻纹枯病菌,其拉丁名为:Pellicularia sasakii、RC:禾谷丝核菌,其拉丁名为:Rhizoctonia cerealis、SS:油菜菌核病菌,其拉丁名为:Sclerotinia sclerotiorum,这些菌种具有很好的代表性,能够代表农业生产中田间发生的大部分病原菌的种属。The code and name of the common phytopathogenic fungi tested in the present invention are as follows: AS: tomato Phytophthora infestans, Latin name: Alternaria solani, BC: Botrytis cinerea, Latin name: Botrytis cinerea, CA: Peanut brown spot disease Its Latin name: Cercospora arachidicola, GZ: Fusarium graminearum, its Latin name: Gibberella zeae, PI: Phytophthora infestans, Latin name: Phytophthora infestans (Mont.) de Bary, PP: Apple wheel The pathogen, its Latin name: Physalospora piricola, PS: Rhizoctonia solani, its Latin name: Pellicularia sasakii, RC: Rhizoctonia cereal, its Latin name: Rhizoctonia cerealis, SS: Sclerotinia sclerotiorum, its The Latin name is: Sclerotinia sclerotiorum, which is well-represented and represents the species of most pathogens that occur in the field of agricultural production.
值得注意的是本发明中化合物CL04-00为专利WO 2000003974 A1中报道过的化学结构与本发明目标化合物最接近的已知化合物,为了比较本发明合成的新化合物的生物活性,本发明合成了结构最接近本发明目标化合物的已知化合物CL04-00作为对照化合物,并与本发明目标化合物进行活性比较。It is to be noted that the compound CL04-00 in the present invention is a known compound whose chemical structure is reported closest to the target compound of the present invention as reported in the patent WO 2000003974 A1. In order to compare the biological activities of the novel compound synthesized by the present invention, the present invention synthesizes The known compound CL04-00 having the structure closest to the target compound of the present invention is used as a control compound and compared with the activity of the target compound of the present invention.
菌体生长率法测定结果见表2,表2表明,在50微克/毫升时,本发明合成的异噻唑肟醚甲氧基丙烯酸酯所有化合物均有不同程度的杀菌活性。对番茄早疫病菌而言,化合物CL03-49、CL03-50、CL04-03、CL04-04上、CL04-04下、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22A、CL04-22D、CL04-25C、CL04-17、CL04-32A、CL04-32B、CL04-32C和CL04-32D的抑制率均在30%以上,上述化合物的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL04-00的杀菌活性10%以上,此外化合物CL03-50、CL04-03、CL04-04上、CL04-06、CL04-15B、CL04-15C和CL04-32D的杀菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00的杀菌活性10%以上,其中化合物CL04-04上、CL04-15B的抑菌率均在80%以上,均高出对照药嘧菌酯10%以上和对照药烯肟菌酯30%以上,尤其是化合物CL04-15B杀菌活性最高,达100%;化合物对花 生褐斑菌而言,化合物CL03-49、CL03-50、CL04-04上、CL04-04下、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22A、CL04-22B、CL04-22C、CL04-22D、CL04-22E、CL04-25C、CL04-17、CL04-32A、CL04-32B、CL04-32C和CL04-32D的抑制率均在30%以上,上述化合物的抑菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL04-00的抑菌活性10%以上,此外化合物CL04-04上、CL04-04下、CL04-15B、CL04-15C、CL04-22D和CL04-32D的抑制率均在75%以上,均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00的杀菌活性10%以上,均高出对照药嘧菌酯和烯肟菌酯20%以上,且化合物CL04-03和CL04-15B的抑制率分别达到了100%和91.67%;对小麦赤霉病菌而言,化合物CL03-49、CL03-50、CL04-03、CL04-04上、CL04-04下、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22A、CL04-22B、CL04-22C、CL04-22D、CL04-22E、CL04-22F、CL04-24、CL04-25A、CL04-25B、CL04-25C、CL04-25E、CL04-17、CL04-32A、CL04-32B、CL04-32C、CL04-32D和CL04-32F的抑制率均在30%以上,上述化合物的抑菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL04-00和对照药烯肟菌酯的抑菌活性10%以上,其中化合物CL04-03、CL04-04上、CL04-04下、CL04-06、CL04-15B、CL04-15C、CL04-22A、CL04-22B、CL04-22C、CL04-22D、CL04-25B、CL04-25C、CL04-17、CL04-32B、CL04-32C和CL04-32F的抑菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00 10%以上,其中化合物CL04-15C、CL04-22B、CL04-22D、CL04-25C、CL04-32B和CL04-32D的抑制率均在80%以上,均比对照药嘧菌酯高出10%以上,尤其化合物CL04-22B、CL04-22D、CL04-25C和CL04-32D的杀菌最高,达100%;对苹果轮纹病菌而言,CL03-49、CL03-50、CL04-03、CL04-04上、CL04-04下、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22B、CL04-22C、CL04-22D、CL04-17、CL04-32B、CL04-32C和CL04-32D的抑菌活性均在45%以上,上述化合物的抑菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL04-00的抑菌活性10%以上,其中化合物CL03-49、CL03-50、CL04-03、CL04-04上、CL04-06、CL04-15C、CL04-22D、CL04-32C的抑制率均在70%以上,均高出与本发明目标化合物化学结构最接近的化合物CL05-00和对照药烯肟菌酯10%以上,且化合物CL04-03杀菌活性最高,达86.96%;对黄瓜灰霉病菌的活性测试表明,CL03-49、CL03-50、CL04-03、CL04-04上、CL04-04下、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22A、CL04-22B、CL04-22C、CL04-22D、CL04-22E、CL04-22F、CL04-25C、CL04-17、CL04-32A、CL04-32B、CL04-32C和CL04-32D的杀菌活性均在45%以上,上述化合物的抑菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL04-00的抑菌活性10%以上,其中化合物CL03-49、CL03-50、CL04-03、CL04-04上、CL04-04下、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22D和CL04-22E的杀菌活性均高出对照药烯肟菌酯10%以上,且化合物CL03-49、CL03-50、CL04-03、CL04-04上、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22D和CL04-17抑制率达到了100%, 均高于文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00的抑菌活性25%以上且高于对照药嘧菌酯的杀菌活性;对油菜菌核病菌的活性测试表明,化合物CL03-49、CL03-50、CL04-03、CL04-04上、CL04-04下、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22A、CL04-22B、CL04-22C、CL04-22D、CL04-22F、CL04-25A、CL04-25B、CL04-25C、CL04-25D、CL04-25E、CL04-17、CL04-32A、CL04-32B、CL04-32C、CL04-32D和CL04-32F的抑制率均在40%以上,上述化合物的抑菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL04-00的抑菌活性10%以上,化合物CL03-49、CL03-50、CL04-03、CL04-04上、CL04-04下、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22A、CL04-22B、CL04-22C、CL04-22D、CL04-25C、CL04-17、CL04-32B、CL04-32C和CL04-32D的杀菌活性均高出对照药烯肟菌酯10%以上,且化合物CL04-03、CL04-04上、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22B、CL04-22D的抑制率均高于90%,均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00的抑菌活性20%以上且高于对照药嘧菌酯,尤其是化合物CL04-03、CL04-06、CL04-15A、CL04-22B、CL04-22D的抑制率最高,达100%;对禾谷丝核菌而言,化合物CL03-49、CL03-50、CL04-03、CL04-04上、CL04-04下、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22A、CL04-22B、CL04-22C、CL04-22D、CL04-22E、CL04-22F、CL04-24、CL04-25A、CL04-25B、CL04-25C、CL04-25E、CL04-17、CL04-32A、CL04-32B、CL04-32C、CL04-32D和CL04-32F的抑制率均在50%以上,上述化合物的抑菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL04-00的抑菌活性40%以上,其中化合物CL03-49、CL03-50、CL04-03、CL04-04上、CL04-06、CL04-15B、CL04-22D、CL04-25C和CL04-32B的抑制率均达90%以上,均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00的抑菌活性10%以上且均高出对照药嘧菌酯10%以上和烯肟菌酯20%以上,且化合物CL03-49、CL03-50、CL04-03、CL04-04上和CL04-06的抑制率最高,达100%;对水稻纹枯病菌而言,化合物CL03-49、CL03-50、CL04-03、CL04-04上、CL04-04下、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22B、CL04-22C、CL04-22B、CL04-25A、CL04-25C、CL04-17、CL04-32A、CL04-32B、CL04-32C和CL04-32D的抑制率均在35%以上,上述化合物的抑菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL04-00的抑菌活性10%以上,其中化合物CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22B、CL04-22D、CL04-25C、CL04-32B、CL04-32C和CL04-32D的抑菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00的抑菌活性10%以上且均高出对照药烯肟菌酯10%以上,且化合物CL04-22D、CL04-25C和CL04-32D的抑制率均在80%以上,均高于对照药嘧菌酯;对于马铃薯晚疫病菌的活性表明,化合物CL03-49、CL03-50、CL04-03、CL04-04上、CL04-04下、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22A、CL04-22B、CL04-22C、CL04-22D、CL04-25A、CL04-25C、CL04-17、CL04-32A、CL04-32B、CL04-32C和CL04-32D的抑制 率均在40%以上,上述化合物的抑菌活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL04-00和对照药烯肟菌酯的抑菌活性10%以上,其中化合物CL04-03、CL04-04下、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22A、CL04-22B、CL04-22C、CL04-22D、CL04-25A、CL04-25C、CL04-32A、CL04-32B、CL04-32C和CL04-32D的抑制率均在55%以上,均高出对照药嘧菌酯10%以上,其中化合物CL04-15B、CL04-15C、CL04-22C、CL04-22D、CL04-25A、CL04-25C、CL04-32A、CL04-32B、CL04-32C和CL04-32D的抑制活性均在86%以上,均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL05-00的抑菌活性10%以上,且化合物CL04-22C、CL04-22D、CL04-25A、CL04-25C、CL04-32B、CL04-32C和CL04-32D抑制率最高,达100%;综上可见,化合物CL04-03、CL04-15B、CL04-15C、CL04-22D具有广谱的杀菌活性。The results of the cell growth rate measurement are shown in Table 2. Table 2 shows that at 50 μg/ml, all of the compounds of the isothiazolyl ether methoxy acrylate synthesized by the present invention have different degrees of bactericidal activity. For tomato early blight, compounds CL03-49, CL03-50, CL04-03, CL04-04, CL04-04, CL04-06, CL04-15A, CL04-15B, CL04-15C, CL04-22A The inhibition rates of CL04-22D, CL04-25C, CL04-17, CL04-32A, CL04-32B, CL04-32C and CL04-32D are all above 30%. The bactericidal activity of the above compounds is higher than that reported in the literature. The bactericidal activity of the compound with the closest chemical structure of the target compound CL04-00 is more than 10%, in addition to the compounds CL03-50, CL04-03, CL04-04, CL04-06, CL04-15B, CL04-15C and CL04-32D. The bactericidal activity was higher than that reported in the literature, and the bactericidal activity of the compound CL05-00 which is the closest to the chemical structure of the target compound of the present invention was more than 10%, and the inhibition rate of the compound CL04-04 and CL04-15B was above 80%. More than 10% of the control azoxystrobin and more than 30% of the control drug enestrobin, especially the compound CL04-15B has the highest bactericidal activity, up to 100%; For the brown spot, the compounds CL03-49, CL03-50, CL04-04, CL04-04, CL04-06, CL04-15A, CL04-15B, CL04-15C, CL04-22A, CL04-22B, The inhibition rates of CL04-22C, CL04-22D, CL04-22E, CL04-25C, CL04-17, CL04-32A, CL04-32B, CL04-32C and CL04-32D are all above 30%, and the antibacterial activity of the above compounds The antibacterial activity of the compound CL04-00 which is the closest to the chemical structure of the target compound of the present invention is more than 10%, and the compounds CL04-04, CL04-04, CL04-15B, CL04-15C, CL04- The inhibition rates of 22D and CL04-32D were all above 75%, which were higher than the bactericidal activity of the compound CL05-00 which is the closest to the chemical structure of the target compound of the present invention, which was higher than 10%, both higher than the control azoxystrobin and More than 20% of enestrobin, and the inhibition rates of compounds CL04-03 and CL04-15B reached 100% and 91.67%, respectively; for wheat scab, compounds CL03-49, CL03-50, CL04-03, CL04-04, CL04-04, CL04-06, CL04-15A, CL04-15B, CL04-15C, CL04-22A, CL04-22B, CL04-22C, CL04-22D, CL04-22E, CL04-22F, CL04-24, C The inhibition rates of L04-25A, CL04-25B, CL04-25C, CL04-25E, CL04-17, CL04-32A, CL04-32B, CL04-32C, CL04-32D and CL04-32F are all above 30%. The antibacterial activity of the compound CL04-00 and the control drug enestrobin which are the closest to the chemical structure of the target compound of the present invention are more than 10%, wherein the compounds CL04-03, CL04-04, CL04-04, CL04-06, CL04-15B, CL04-15C, CL04-22A, CL04-22B, CL04-22C, CL04-22D, CL04-25B, CL04-25C, CL04-17, CL04-32B, CL04 The antibacterial activity of -32C and CL04-32F is higher than that of the compound CL05-00 which is the closest to the chemical structure of the target compound of the present invention, which is more than 10%, among which the compounds CL04-15C, CL04-22B, CL04-22D, CL04- The inhibition rates of 25C, CL04-32B and CL04-32D were all above 80%, which were more than 10% higher than the control azoxystrobin, especially the sterilization of compounds CL04-22B, CL04-22D, CL04-25C and CL04-32D. The highest, up to 100%; for apple ringworm, CL03-49, CL03-50, CL04-03, CL04-04, CL04-04, CL04-06, CL04-15A, CL04-15B, CL04- 15C, CL04-22B The antibacterial activities of CL04-22C, CL04-22D, CL04-17, CL04-32B, CL04-32C and CL04-32D are all above 45%. The antibacterial activity of the above compounds is higher than that reported in the literature and the target compound of the present invention. The chemical structure of the closest compound CL04-00 has more than 10% antibacterial activity, among which compounds CL03-49, CL03-50, CL04-03, CL04-04, CL04-06, CL04-15C, CL04-22D, CL04- The inhibition rate of 32C was above 70%, which was higher than the compound CL05-00 and the control drug enestrobin which are the closest to the chemical structure of the target compound of the present invention, and the compound CL04-03 had the highest bactericidal activity of 86.96%. Activity tests on Botrytis cinerea showed CL03-49, CL03-50, CL04-03, CL04-04, CL04-04, CL04-06, CL04-15A, CL04-15B, CL04-15C, CL04 Bactericidal activity of -22A, CL04-22B, CL04-22C, CL04-22D, CL04-22E, CL04-22F, CL04-25C, CL04-17, CL04-32A, CL04-32B, CL04-32C and CL04-32D Above 45%, the antibacterial activity of the above compound is higher than the antibacterial activity of the compound CL04-00 which is the closest to the chemical structure of the target compound of the present invention, which is reported in the literature, is 10%. , in which compounds CL03-49, CL03-50, CL04-03, CL04-04, CL04-04, CL04-06, CL04-15A, CL04-15B, CL04-15C, CL04-22D and CL04-22E sterilization The activity is higher than the control drug enestrobin ester by more than 10%, and the compounds CL03-49, CL03-50, CL04-03, CL04-04, CL04-06, CL04-15A, CL04-15B, CL04-15C, CL04 -22D and CL04-17 inhibition rate reached 100%, The antibacterial activity of the compound CL05-00 which is the closest to the chemical structure of the target compound of the present invention is more than 25% higher than that of the control azoxystrobin; the activity test on Sclerotinia sclerotiorum shows that the compound CL03-49, CL03-50, CL04-03, CL04-04, CL04-04, CL04-06, CL04-15A, CL04-15B, CL04-15C, CL04-22A, CL04-22B, CL04-22C, CL04-22D, CL04-22F, CL04-25A, CL04-25B, CL04-25C, CL04-25D, CL04-25E, CL04-17, CL04-32A, CL04-32B, CL04-32C, CL04-32D and CL04- The inhibition rate of 32F was above 40%. The antibacterial activity of the above compounds was higher than that of the compound CL04-00 which is the closest to the chemical structure of the target compound of the present invention, and the antibacterial activity was more than 10%. Compounds CL03-49, CL03 -50, CL04-03, CL04-04, CL04-04, CL04-06, CL04-15A, CL04-15B, CL04-15C, CL04-22A, CL04-22B, CL04-22C, CL04-22D, CL04 The bactericidal activity of -25C, CL04-17, CL04-32B, CL04-32C and CL04-32D was higher than that of the control drug enestrobin more than 10%, and the compounds CL04-03, CL04-04, CL04-06, CL04 -15A, CL04-15B, CL The inhibition rates of 04-15C, CL04-22B and CL04-22D were all higher than 90%, which were higher than the antibacterial activity of the compound CL05-00 which is the closest to the chemical structure of the target compound of the present invention, which was more than 20% higher than the above. The control azoxystrobin, especially the compounds CL04-03, CL04-06, CL04-15A, CL04-22B, CL04-22D, has the highest inhibition rate of 100%; for Rhizoctonia cerealis, compound CL03-49 , CL03-50, CL04-03, CL04-04, CL04-04, CL04-06, CL04-15A, CL04-15B, CL04-15C, CL04-22A, CL04-22B, CL04-22C, CL04-22D , CL04-22E, CL04-22F, CL04-24, CL04-25A, CL04-25B, CL04-25C, CL04-25E, CL04-17, CL04-32A, CL04-32B, CL04-32C, CL04-32D and CL04 The inhibition rate of -32F is above 50%, and the antibacterial activity of the above compound is higher than the antibacterial activity of the compound CL04-00 which is the closest to the chemical structure of the target compound of the present invention, which is more than 40%, wherein the compound CL03-49 The inhibition rates of CL03-50, CL04-03, CL04-04, CL04-06, CL04-15B, CL04-22D, CL04-25C and CL04-32B were all above 90%, both higher than those reported in the literature. Target compounding The antibacterial activity of the closest compound CL05-00 is more than 10% and both higher than the control azoxystrobin by more than 10% and the enestrobin ester by more than 20%, and the compounds CL03-49, CL03-50, CL04-03, CL04-04 and CL04-06 have the highest inhibition rate of 100%; for rice sheath blight, compounds CL03-49, CL03-50, CL04-03, CL04-04, CL04-04, CL04 -06, CL04-15A, CL04-15B, CL04-15C, CL04-22B, CL04-22C, CL04-22B, CL04-25A, CL04-25C, CL04-17, CL04-32A, CL04-32B, CL04-32C And the inhibition rate of CL04-32D is more than 35%. The antibacterial activity of the above compound is higher than the antibacterial activity of the compound CL04-00 which is the closest to the chemical structure of the target compound of the present invention, which is more than 10%, wherein the compound CL04 The antibacterial activities of -06, CL04-15A, CL04-15B, CL04-15C, CL04-22B, CL04-22D, CL04-25C, CL04-32B, CL04-32C and CL04-32D were higher than those reported in the literature. The bacteriostatic activity of the compound with the closest chemical structure of the target compound CL05-00 is more than 10% and both are higher than the control drug enestrobin by more than 10%, and the compounds CL04-22D, CL04-25C and CL04-32D The rate is above 80%, which is higher than the control azoxystrobin; the activity against Phytophthora infestans shows that the compounds CL03-49, CL03-50, CL04-03, CL04-04, CL04-04, CL04 -06, CL04-15A, CL04-15B, CL04-15C, CL04-22A, CL04-22B, CL04-22C, CL04-22D, CL04-25A, CL04-25C, CL04-17, CL04-32A, CL04-32B , CL04-32C and CL04-32D suppression The bacteriostatic activity of the above compounds is higher than the antibacterial activity of the compound CL04-00 and the control drug enestrobin which are the closest to the chemical structure of the target compound of the present invention, and the compound has a bacteriostatic activity of more than 10%. CL04-03, CL04-04, CL04-06, CL04-15A, CL04-15B, CL04-15C, CL04-22A, CL04-22B, CL04-22C, CL04-22D, CL04-25A, CL04-25C, CL04 The inhibition rates of -32A, CL04-32B, CL04-32C and CL04-32D were all above 55%, both higher than the control azoxystrobin by more than 10%, among which compounds CL04-15B, CL04-15C, CL04-22C, CL04 The inhibitory activities of -22D, CL04-25A, CL04-25C, CL04-32A, CL04-32B, CL04-32C and CL04-32D were all above 86%, which were higher than the reported chemical structure of the target compound of the present invention. The compound CL05-00 has a bacteriostatic activity of more than 10%, and the compounds CL04-22C, CL04-22D, CL04-25A, CL04-25C, CL04-32B, CL04-32C and CL04-32D have the highest inhibition rate of 100%; In summary, the compounds CL04-03, CL04-15B, CL04-15C, CL04-22D have a broad spectrum of bactericidal activity.
实施例8:本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ防治黄瓜白粉病的田间试验结果:Example 8: Field trial results of the isothiazolyl ether methoxy acrylate derivative IV of the present invention for controlling cucumber powdery mildew:
本发明对高活性化合物开展了田间药效试验,选择的防治对象的名称及代号如下:白粉病(Sphaerotheca fuliginea);选择的试验作物品种为“津优40”的黄瓜。施药方法及用水量(升/公顷):在发病前或者发病初期,采用喷雾法施药。以675L/hm2的药液量对植株均匀喷雾,空白对照喷等量清水。实验结果见表3,表3表明,9.60%CL04-22D乳油对黄瓜白粉病的平均防效为78.62%;而对照药剂250g/L嘧菌酯SC(英国先正达有限公司生产)的平均防效为70.19%,本发明的化合物的活性高出对照药剂将近10%;50%肟菌酯(FLINT)WG(德国拜耳作物科学公司生产)的平均防效为68.02%,肟菌酯的化学结构与本发明专利化合物结构最接近,本发明化合物的活性高出该对照药剂10%以上。经方差分析和多重比较,9.60%CL04-22D乳油37.5克/公顷的防效显著高于两对照药剂250g/L嘧菌酯SC和50%肟菌酯(FLINT)WG的防效。试验期间观察,9.60%CL04-22D乳油各处理对黄瓜植株无药害等不良影响。综上所述:9.60%CL04-22D乳油对黄瓜白粉病有较好的防治效果。The invention carries out a field efficacy test on a highly active compound, and the name and code of the selected control object are as follows: powdery mildew (Sphaerotheca fuliginea); the selected test crop variety is "Jinyou 40" cucumber. Application method and water consumption (liters/ha): Spraying before or after the onset of the disease. The plants were evenly sprayed with a dose of 675 L/hm 2 , and the blank control was sprayed with equal amount of water. The experimental results are shown in Table 3. Table 3 shows that the average control effect of 9.60% CL04-22D emulsifiable concentrate on cucumber powdery mildew is 78.62%; and the average control of 250g/L azoxystrobin SC (produced by British Syngenta Co., Ltd.) The effect is 70.19%, the activity of the compound of the present invention is higher than that of the control agent by nearly 10%; the average control effect of 50% of sputum ester (FLINT) WG (manufactured by Bayer CropScience Co., Germany) is 68.02%, and the chemical structure of trifloxystrobin The structure of the compound of the present invention is closest to that of the compound of the present invention, and the activity of the compound of the present invention is higher than that of the control agent by more than 10%. After analysis of variance and multiple comparisons, the control effect of 9.60% CL04-22D emulsifiable concentrate 37.5 g/ha was significantly higher than that of the two control agents 250 g/L azoxystrobin SC and 50% fentanyl ester (FLINT) WG. During the experiment, it was observed that 9.60% of CL04-22D emulsifiable concentrate had no adverse effects on cucumber plants. In summary: 9.60% CL04-22D EC has a good control effect on cucumber powdery mildew.
实施例9:本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ防治黄瓜霜霉病的田间试验结果:Example 9: Field test results of the isothiazolyl ether methoxy acrylate derivative IV of the present invention for controlling cucumber downy mildew:
本发明对高活性化合物开展了田间药效试验,选择防治对象的名称及代号如下:黄瓜霜霉病(Pseudoperponspora cubensis);选择的试验作物品种“津绿3号”的黄瓜。施药方法及用水量(升/公顷):在黄瓜霜霉病发病初期,采用喷雾法施药。以675L/hm2的药液量对植株均匀喷雾,空白对照喷等量清水。实验结果见表4,表4表明,9.60%CL04-22D乳油对黄瓜霜霉病的平均防效为79.18%;而对照药剂50%肟菌酯(FLINT)WG(德国拜耳作物科学公司生产)的平均防效为72.02%,本发明的化合物的活性高出对照药剂5%以上;250g/L吡唑醚菌酯EC(巴斯夫植物保护(江苏)有限公司生产)的平均防效为77.52%,本发明的化合物的活性与该对照药剂相当。经方差分析和多重比较,9.60%CL04-22D乳油75克/公顷的防效与对照药剂250g/L吡唑醚菌酯EC的防效相当,无显著差异;但显著高于化学结构与本发明专利化合物最接近的对照药剂50%肟菌酯WG的平均防效。试验期间观察,9.60%CL04-22D乳油对黄瓜植株无药害等不良影响。综上所述:9.60%CL04-22D乳油对黄瓜霜霉病有较好的防 治效果。The invention carries out a field efficacy test on a highly active compound, and the name and code of the selected control object are as follows: cucumber downy mildew (Pseudoperponspora cubensis); the selected test crop variety "Jinlu No. 3" cucumber. Application method and water consumption (liters/ha): In the early stage of cucumber downy mildew, spray application. The plants were evenly sprayed with a dose of 675 L/hm 2 , and the blank control was sprayed with equal amount of water. The experimental results are shown in Table 4. Table 4 shows that the average control effect of 9.60% CL04-22D emulsifiable concentrate on cucumber downy mildew is 79.18%; and the control agent 50% sputum ester (FLINT) WG (produced by Bayer CropScience Co., Germany) The average control effect is 72.02%, and the activity of the compound of the present invention is higher than 5% of the control agent; the average control effect of 250 g/L pyraclostrobin EC (produced by BASF Plant Protection (Jiangsu) Co., Ltd.) is 77.52%, The activity of the compounds of the invention is comparable to the control agent. After analysis of variance and multiple comparisons, the control effect of 9.60% CL04-22D EC 75 g/ha was comparable to that of the control agent 250 g/L pyraclostrobin EC, no significant difference; but significantly higher than the chemical structure and the present invention. The average control effect of the patented compound closest to the control agent 50% trifloxystrobin WG. During the experiment, 9.60% of CL04-22D emulsifiable concentrate had no adverse effects on cucumber plants. In summary: 9.60% CL04-22D emulsifiable concentrate has a good anti-treatment effect on cucumber downy mildew.
实施例10:本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ的抗烟草花叶病毒(简称TMV)活性:Example 10: Tobacco mosaic virus (TMV) activity of the isothiazolyl ether methoxy acrylate derivative IV of the present invention:
抗TMV活性的测定结果见表5,表5表明,本发明的大部分化合物具有较好的抗TMV的活性;在100微克/毫升时,本发明合成的所有化合物均有不同程度的抗TMV活性。在治疗模式下,化合物CL03-49、CL04-50、CL04-03、CL04-25A、CL04-25D、CL04-17、CL04-32B和CL04-32F抗烟草花叶病毒活性均在30%以上,其中化合物CL03-49、CL04-50、CL04-03、CL04-25A、CL04-32B和CL04-32F的抗烟草花叶病毒活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL04-00、CL05-00和异噻菌胺10%以上,且化合物CL04-32F的抗烟草花叶病毒活性在60%以上,尤其是化合物CL04-25A和CL04-32B抗烟草花叶病毒活性高于对照药宁南霉素;在钝化模式下,化合物CL03-49、CL03-50、CL04-03、CL04-04上、CL04-04下、CL04-15A、CL04-15B、CL04-15C、CL04-22A、CL04-22B、CL04-22E、CL04-17、CL04-32A、CL04-32B、CL04-32C和CL04-32D抗烟草花叶病毒活性均在30%以上,上述化合物的抗烟草花叶病毒活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL04-00、CL05-00和异噻菌胺10%以上,其中化合物CL03-50、CL04-04上和CL04-32B的钝化抑制率均在70%以上,与对照药病毒唑的钝化抑制率相当,且化合物CL04-03的钝化抑制率最高,达80%以上;在保护模式下,化合物CL03-50、CL04-04上、CL04-04下、CL04-06、CL04-15A、CL04-22B、CL04-22D、CL04-25A、CL04-25C、CL04-32A、CL04-32E和CL04-32F的保护效果均在40%,上述化合物的抗烟草花叶病毒活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL04-00、CL05-00和异噻菌胺10%以上,其中化合物CL03-50、CL04-04上、CL04-06、CL04-22B、CL04-25C和CL04-32F的保护活性均在50%以上;在诱导模式下,化合物CL03-49、CL03-50、CL04-03、CL04-04上、CL04-04下、CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22A、CL04-22B、CL04-22C、CL04-22D、CL04-22F、CL04-24、CL04-25A、CL04-25C、CL04-17、CL04-32A、CL04-32B、CL04-32D和CL04-32F的诱导效果均在30%以上,上述化合物的抗烟草花叶病毒活性均高出文献报道的与本发明目标化合物化学结构最接近的化合物CL04-00和CL05-00 10%以上,其中化合物CL03-49、CL03-50、CL04-03、CL04-04上CL04-06、CL04-15A、CL04-15B、CL04-15C、CL04-22C、CL04-22D、CL04-25A、CL04-32B、CL04-32E的诱导活性在70%以上,尤其是化合物CL03-50、CL04-15C、CL04-22C的诱导活性达到了80%,高于对照药TDL、BTH、SZG-7和异噻菌胺;在诱导模式下,上述的化合物表现了良好的诱导活性。可见,化合物CL04-04上和CL04-32B对TMV具有良好的抑制活性。本发明的大部分化合物具有很好的抗TMV的活性。The results of the determination of anti-TMV activity are shown in Table 5. Table 5 shows that most of the compounds of the present invention have better anti-TMV activity; at 100 μg/ml, all compounds synthesized by the present invention have different degrees of anti-TMV activity. . In the treatment mode, the compounds CL03-49, CL04-50, CL04-03, CL04-25A, CL04-25D, CL04-17, CL04-32B and CL04-32F were all resistant to tobacco mosaic virus activity above 30%. The anti-tobacco mosaic virus activities of the compounds CL03-49, CL04-50, CL04-03, CL04-25A, CL04-32B and CL04-32F were higher than those reported in the literature as the closest compound to the chemical structure of the target compound of the present invention. 00, CL05-00 and Isotianil 10% or more, and the activity of compound CL04-32F against tobacco mosaic virus is above 60%, especially the activity of compounds CL04-25A and CL04-32B against tobacco mosaic virus is higher than that of the control. Ningnanmycin; in passivation mode, compounds CL03-49, CL03-50, CL04-03, CL04-04, CL04-04, CL04-15A, CL04-15B, CL04-15C, CL04-22A The anti-tobacco mosaic virus activities of CL04-22B, CL04-22E, CL04-17, CL04-32A, CL04-32B, CL04-32C and CL04-32D were all above 30%, and the anti-tobacco mosaic virus activities of the above compounds were all More than 10% of the compounds CL04-00, CL05-00 and isotianil, which are the closest to the chemical structure of the target compound of the present invention, the compound CL03-5 0, CL04-04 and CL04-32B passivation inhibition rate are above 70%, and the control drug ribavirin passivation inhibition rate is equivalent, and compound CL04-03 passivation inhibition rate is the highest, up to 80%; In protected mode, compounds CL03-50, CL04-04, CL04-04, CL04-06, CL04-15A, CL04-22B, CL04-22D, CL04-25A, CL04-25C, CL04-32A, CL04- Both 32E and CL04-32F have a protective effect of 40%. The anti-tobacco mosaic virus activity of the above compounds is higher than the reported compounds CL04-00, CL05-00 and Isobacteria which are closest to the chemical structure of the target compound of the present invention. The amine has more than 10%, wherein the protective activities of the compounds CL03-50, CL04-04, CL04-06, CL04-22B, CL04-25C and CL04-32F are all above 50%; in the induction mode, the compound CL03-49, CL03-50, CL04-03, CL04-04, CL04-04, CL04-06, CL04-15A, CL04-15B, CL04-15C, CL04-22A, CL04-22B, CL04-22C, CL04-22D, The induction effects of CL04-22F, CL04-24, CL04-25A, CL04-25C, CL04-17, CL04-32A, CL04-32B, CL04-32D and CL04-32F are all above 30%. Leaf virus activity More than 10% of the compounds CL04-00 and CL05-00 closest to the chemical structure of the target compound of the present invention are reported in the literature, among which compounds CL03-49, CL03-50, CL04-03, CL04-04 on CL04-06, CL04 The induction activities of -15A, CL04-15B, CL04-15C, CL04-22C, CL04-22D, CL04-25A, CL04-32B, CL04-32E are above 70%, especially the compounds CL03-50, CL04-15C, CL04 The induction activity of -22C reached 80%, which was higher than the control drugs TDL, BTH, SZG-7 and isotianil; in the induction mode, the above compounds showed good induction activity. It can be seen that the compound CL04-04 and CL04-32B have good inhibitory activity against TMV. Most of the compounds of the invention have excellent anti-TMV activity.
本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ还对水稻矮缩病、黄矮病、条纹叶枯病、番茄蕨叶病毒病、辣椒花叶病毒病、烟草脉坏死病毒病、玉米矮花叶病、花椰菜花叶病毒、 柑橘病毒病、建兰花叶病毒病、建兰环斑病毒的农业和林业以及园艺植物病毒病害具有很好的抗病毒活性。The isothiazolyl ether methoxy acrylate derivative IV of the present invention is also resistant to rice dwarf disease, yellow dwarf disease, stripe leaf blight, tomato fern leaf virus disease, pepper mosaic virus disease, tobacco vein necrosis virus, corn Dwarf mosaic disease, cauliflower mosaic virus, Citrus virus disease, orchid flower virus disease, agriculture and forestry of Jianlan ring spot virus, and horticultural plant virus disease have good antiviral activity.
实施例11:本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与杀虫剂组合在防治农业和林业以及园艺植物虫害中的应用:Example 11: Application of the combination of isothiazolium ether methoxy acrylate derivative IV of the present invention and insecticide in controlling agricultural and forestry and horticultural plant pests:
本发明的所有异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与商品杀虫剂中的任意一种或两种组合形成杀虫组合物用于防治农业和林业以及园艺植物虫害,所述商品杀虫剂选自:毒死蜱、地亚哝、啶虫脒、甲氨基阿维菌素、弥拜菌素、阿维菌素、多杀菌素、氰戊菊酯、高效氰戊菊酯、氯氰菊酯、高效氯氰菊酯、三氟氯氰菊酯、溴氰菊酯、甲氰菊酯、Beta-氟氯氰菊酯、Lambda-三氟氯氰菊酯、二氯苯醚菊酯、苄氯菊酯、丙烯菊酯、联苯菊酯、氯菊酯、醚菊酯、氟氯苯菊酯、氯氟胺氰戊菊酯、吡虫啉、烯啶虫胺、氯噻啉、噻虫啉、噻虫嗪、噻虫胺、呋虫胺、可尼丁、达特南、除虫脲、灭幼脲、伏虫隆、除虫隆、氟铃脲、氟虫脲、啶虫隆、虱螨脲、毒虫脲、氟幼脲、Noviflumuron即多氟脲,其CAS号为121451-02-3、氟螨脲、Novaluron即双苯氟脲、氟啶脲、Bay sir 6874即{1-[(3.5-二氯-4)4-硝基苯氧基苯基3-3-(2-氯苯)-脲}、Bay SIR-8514即[1-(4-三氟甲氧基苯基)-3-(2-氯苯)-脲]、嗪虫脲、Bistrifluron即双三氟虫脲、呋喃虫酰肼、虫酰肼、氯虫酰肼、甲氧虫酰肼、环虫酰肼、乐果、氧化乐果、敌敌畏、乙酰甲胺磷、***磷、喹硫磷、哒嗪硫磷、氯唑磷、叶蝉散、西维因、抗蚜威、速灭威、异丙威、杀螟丹、仲丁威、叶飞散、甲萘威、丙硫克百威、丁硫克百威、杀螟丹、溴螨酯、噻螨酮、唑螨酯、哒螨酮、四螨嗪、炔螨特、丁醚脲、吡蚜酮、螺螨酯、螺虫酯、螺虫乙酯、丁烯氟虫腈、***锡、噻嗪酮、灭线磷、氟虫腈、杀虫单、杀虫双、氯虫酰胺、氟虫酰胺、氟氰虫酰胺、氰虫酰胺、唑虫酰胺、溴虫腈、吡嗪酮、乙螨唑、吡螨胺、哒幼酮、吡丙醚、埃玛菌素;本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在所述杀虫组合物中的质量百分含量是1%-90%,本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与前述商品杀虫剂的比例为质量百分比1%∶99%到99%∶1%;所述杀虫组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;所述杀虫组合物防治的植物虫害选自:红蜘蛛、东亚飞蝗、云斑车蝗、中华稻蝗、日本黄脊蝗、单刺蝼蛄、东方蝼蛄、稻蓟马、烟蓟马、温室蓟马、稻管蓟马、麦简管蓟马、温室白粉虱、烟粉虱、黑尾叶蝉、大青叶蝉、棉叶蝉、斑衣蜡蝉、褐飞虱、白背飞虱、灰飞虱、甘蔗扁角飞虱、棉蚜、麦二叉蚜、麦长管蚜、桃蚜、高粱蚜、萝卜蚜、吹绵蚧、桑盾蚧、矢尖盾蚧、梨圆蚧、白蜡虫、红蜡蚧、朝鲜球坚蚧、梨网蝽、香蕉网蝽、细角花蝽、微小花蝽、针缘蝽、稻蛛缘蝽、稻褐蝽、稻黑蝽、稻绿蝽、绿盲蝽、苜蓿盲蝽、中黑盲蝽、 大草蛉、丽草蛉、中华草蛉、谷蛾、衣蛾、黄刺蛾、褐刺蛾、扁刺蛾、麦蛾、棉红铃虫、甘薯麦蛾、小菜蛾、桃小食心虫、大豆食心虫、桃小食心虫、苹果顶梢卷叶蛾、褐带长卷叶蛾、拟小黄卷叶蛾、二化螟、豆荚螟、玉米螟、三化螟、菜螟、稻纵卷叶螟、条螟、棉卷叶野螟、桃蛀螟、黏虫、斜纹夜蛾、稻螟蛉、棉小造桥虫、甜菜夜蛾、大螟、棉铃虫、鼎点金刚钻、小地老虎、大地老虎、黄地老虎、盗毒蛾、舞毒蛾、甘薯天蛾、豆天蛾、直纹稻弄蝶、隐纹谷弄蝶、柑橘凤蝶、玉带凤蝶、菜粉蝶、苎麻赤蛱蝶、苎麻黄蛱蝶、豆芫菁、金星步甲、皱鞘步甲、麦穗步甲、沟金针虫、细胸金针虫、谷斑皮蠹、黑皮蠹、柑橘小吉丁虫、金缘吉丁虫、黄粉虫、黑粉虫、赤拟谷盗、杂拟谷盗、铜绿异丽金龟、暗黑金龟、华北大黑鳃金龟、桑天牛、星天牛、橘褐天牛、桃红颈天牛、大猿叶虫、小猿叶虫、黄守瓜、黄曲条跳甲、绿豆象、豌豆象、蚕豆象、玉米象、米象、小麦叶蜂、梨实蜂、黄带姬蜂、黏虫白星姬蜂、螟蛉悬茧姬蜂、棉铃虫齿唇姬蜂、螟黑点疣姬蜂、蚊、蝇、虻、麦红吸浆虫、麦黄吸浆虫、稻瘿蚊、柑橘大实蝇、瓜实蝇、麦叶灰潜蝇、美洲斑潜蝇、豆秆黑潜蝇、麦秆蝇、种蝇、葱蝇、萝卜蝇、伞裙追寄蝇、玉米螟厉寄蝇、黏虫;所述杀虫组合物防治的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。All of the isothiazolium ether methoxy acrylate derivative IV of the present invention is combined with any one or two of the commercial insecticides to form an insecticidal composition for controlling agricultural and forestry and horticultural plant pests. Insecticides are selected from the group consisting of: chlorpyrifos, dexamethasone, acetamiprid, emamectin, milavirin, avermectin, spinosyn, fenvalerate, high-grade fenvalerate, cypermethrin, and high efficiency Cypermethrin, cyhalothrin, deltamethrin, fenpropathrin, Beta-cyfluthrin, Lambda-cyhalothrin, permethrin, permethrin, methrin, bifenthrin, permethrin Ester, fenthrin, flumethrin, flufenacetate, imidacloprid, nitenpyram, chlorothiazol, thiacloprid, thiamethoxam, clothianidin, dinotefuran, cotinine , Dartnam, diflubenzuron, chlorbenzuron, flubenzuron, chlorfenapyr, hexaflumuron, flubendiamide, acetamiprid, guanidine urea, chlorfenapyr, fluorolactam, Noviflumuron, polyfluorourea, Its CAS number is 121451-02-3, fluorofurazone, Novaluron, ie, diphenylfluorourea, chlorfluazuron, Bay sir 6874, ie {1-[(3.5-dichloro) -4) 4-nitrophenoxyphenyl 3-3-(2-chlorophenyl)-urea}, Bay SIR-8514 is [1-(4-trifluoromethoxyphenyl)-3-(2 -Chlorobenzene)-urea], oxazide urea, Bistrifluron, bistrifluridine, furanyl hydrazide, tebufenozide, chlorfenapyr, methoxyfenozide, chlorfenapyr, dimethoate, oxidized music Fruit, dichlorvos, acephate, triazophos, quetiapine, pyridazin, chlorpyrifos, scutellaria, carbaryl, carbaryl, acesulfame, isoprocarb, chlorpyrifos, Zhong Dingwei, Ye Feisan, Carbaryl, Propionine, Binger, Bupidin, Bromoxyl, Thiazolone, Azathioprine, Anthrone, Tetramethylazine, Alkyne , dibutyl ether urea, pyridoxine, spirodecyl ester, spirotetramat, spirotetramat, butene fipronil, triazole tin, buprofezin, phosphazone, fipronil, insecticidal, insecticidal Bis, chlorantraniliprole, flubendiamide, flufenamide, cyanamide, oxazolamide, chlorfenapyr, pyrazinone, etoxazole, pyridoxamine, ketone, pyriproxyfen, emam The mass percentage of the isothiazolyl ether methoxy acrylate derivative IV of the present invention in the insecticidal composition is 1 -90%, the ratio of the isothiazolyl ether methoxy acrylate derivative IV of the present invention to the aforementioned commercial insecticide is 1% by mass: 99% to 99%: 1% by mass; the insecticidal composition is processed The dosage form is selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble thickener, poisonous valley, block bait, granular bait, flaky bait, concentrated bait , slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, hot spray, cold spray, aerosol , solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microgranule, trace powder, oil suspension, oil dispersible powder, thick glue, pouring agent, seed coat Agent, smear agent, film-forming oil agent, ultra-low-volume liquid agent, steam release agent; the plant pests controlled by the insecticidal composition are selected from the group consisting of: red spider, East Asian locust, cloud locust, Chinese rice blast, Japan Yellow ridge, single locust, oriental carp, rice locust, smoky horse, greenhouse hummer, rice Hummer, Maijianguan Hummer, Greenhouse Whitefly, Bemisia tabaci, Black-tailed Leafhopper, Daqingye, Cotton Leafhopper, Spotted Wax, Brown Planthopper, White-backed Flycatcher, Mad Planthopper, Sugarcane Fly mites, cotton aphid, wheat bifurcation, wheat long tube stalk, peach sorghum, sorghum, radish scorpion, blown sorghum, sang shield, yam shield, pear round scorpion, white wax insect, red wax scorpion, North Korea Ball scorpion, pear net, banana net, fine-horned flower bud, tiny flower bud, needle rim, rice spider mites, rice brown carp, rice black carp, rice green carp, green blind owl, 苜蓿 blind 蝽, Black blind, Dacao, Licao, Chinese grass, moth, moth, yellow moth, brown moth, flat moth, wheat moth, cotton bollworm, sweet potato moth, diamondback moth, peach small heartworm, soybean borer , peach small heartworm, apple top-rolled leaf moth, brown-striped leaf moth, pseudo-small leaf moth, stem borer, bean pod, corn borer, stem borer, rapeseed meal, rice leaf roller, bark, cotton leaf bark , peach aphid, sticky insect, Spodoptera litura, rice blast, cotton small bridge worm, beet armyworm, big cockroach, cotton bollworm, tripod diamond, small tiger, earth tiger, yellow tiger, poisonous moth, dance Toxic moth, sweet potato hawk moth, bean hawk moth, straight grain rice butterfly, cryptic valley butterfly, citrus phoenix butterfly, jade phoenix butterfly, cabbage butterfly, ramie red butterfly, ramie butterfly, bean phthalocyanine, Venus , wrinkle sheath, armor, wheat stalk, sphaerocephala, scutellaria, scutellaria, black scorpion, citrus small gibber, sylvestre, yellow mealworm, black mealworm, red valley Pirates, miscellaneous pirates, patina, golden tortoises, dark golden tortoises, North China Black Turtles, Sang Tianniu, Xingtianiu, Orange Day , pink neck beetle, big leafhopper, small leafhopper, yellow squash, yellow scalloped, green bean, pea, broad bean, corn, rice, wheat leaf bee, pear bee, yellow belt Bee, worm, white star worm, cockroach cockroach, cotton bollworm, larvae, cockroach, cockroach, cockroach, cockroach, cockroach, cockroach, larvae, larvae, citrus , melon flies, larvae, larvae, larvae, stalks, stalks, stalks, stalks, stalks, stalks, stalks, snails, snails, snails The plant controlled by the pesticidal composition is selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut, rapeseed, Sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, rape, onion, garlic , watermelon, melon, cantaloupe, papaya, apple, mandarin And peach, tea, mountain vegetables, bamboo shoots, hops, pepper, banana, papaya, orchids, bonsai.
实施例12:本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与杀菌剂组合在防治农业和林业以及园艺植物病害中的应用:Example 12: Application of the combination of the isothiazolium ether methoxy acrylate derivative IV of the present invention and a bactericide in the control of agricultural and forestry and horticultural plant diseases:
本发明的所有异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与商品杀菌剂中的任意一种或两种组合形成杀菌组合物用于防治农业和林业以及园艺植物病害,所述商品杀菌剂选自:苯并噻二唑、噻酰菌胺,简写为TDL、噻酰胺、甲噻诱胺、4-甲基-1,2,3-噻二唑-5-甲酸、4-甲基-1,2,3-噻二唑-5-甲酸钠、4-甲基-1,2,3-噻二唑-5-甲酸乙酯、DL-β-氨基丁酸、异噻菌胺,其英文通用名为:isotianil、3,4-二氯异噻唑-5-甲酸、3,4-二氯异噻唑-5-甲酸钠、3,4-二氯异噻唑-5-甲酸乙酯、病毒唑、安托芬、宁南霉素或水杨酸、霜脲氰、福美双、福美锌、代森锰锌、乙磷铝、甲基硫菌灵、百菌清、敌可松、腐霉利、苯锈啶、甲基托布津、托布津、精甲霜灵、氟吗啉、烯酰吗啉、高效甲霜灵、高效苯霜灵、双氯氰菌胺、磺菌胺、甲磺菌胺、噻氟菌胺、氟酰胺、叶枯酞、环丙酰菌胺、环氟菌胺、环酰菌胺、氰菌胺、硅噻菌胺、呋吡菌胺、吡噻菌胺、双炔酰菌胺、苯酰菌胺、甲呋酰胺、萎锈灵、乙菌利、异菌脲、嘧菌酯、醚菌胺、氟嘧菌酯、醚菌酯、苯氧菌胺、肟醚菌胺、啶氧菌酯、唑菌胺酯、肟菌酯、烯肟菌酯、烯肟菌胺、氧环唑、糠菌唑、环丙唑醇、苯醚甲环唑、烯唑醇、高效烯唑醇、氟环唑、腈苯唑、氟喹唑、氟硅唑、粉唑醇、己唑醇、亚胺唑、种菌唑、叶菌唑、腈菌唑、戊菌唑、丙环唑、丙硫菌唑、硅氟唑、戊唑醇、四氟醚唑、***醇、灭菌唑、联苯***醇、 噻菌灵、麦穗宁、抑霉唑、高效抑霉唑、咪鲜胺、氟菌唑、氰霜唑、咪唑菌酮、噁咪唑、稻瘟酯、噁唑菌酮、啶菌噁唑、噁霉灵、噁霜灵、噻唑菌胺、土菌灵、辛噻酮、苯噻硫氰、十二环吗啉、丁苯吗啉、十三吗啉、拌种咯、咯菌腈、氟啶胺、啶斑肟、环啶菌胺、啶酰菌胺、氟啶酰菌胺、啶菌胺、嘧菌环胺、氟嘧菌胺、嘧菌腙、嘧菌胺、嘧霉胺、氯苯嘧啶醇、氟苯嘧啶醇、灭螨猛、二氰蒽醌、乙氧喹啉、羟基喹啉、丙氧喹啉、苯氧喹啉、乙霉威、异丙菌胺、苯噻菌胺、霜霉威、磺菌威、敌瘟磷、异稻瘟净、吡菌磷、甲基立枯磷、灭瘟素、春雷霉素、多抗霉素、多氧霉素、有效霉素、井冈霉素、链霉素、甲霜灵、呋霜灵、苯霜灵、呋酰胺、灭锈胺、多菌灵、苯菌灵、甲基硫菌灵、***酮、乙嘧酚磺酸酯、二甲嘧酚、乙嘧酚、敌菌丹、克菌丹、灭菌丹、乙烯菌核利、氟氯菌核利、菌核净、百菌清、稻瘟灵、稻瘟净、叶枯唑、五氯硝基苯、丙森锌、三乙膦酸铝、硫磺、波尔多液、硫酸铜、氧氯化铜、氧化亚铜、氢氧化铜、苯菌酮、戊菌隆、哒菌酮、四氯苯酞、咯喹酮、螺环菌胺、三环唑、嗪胺灵、多果啶、双胍辛盐、双胍辛胺、氯硝胺、苯磺菌胺、甲苯磺菌胺、吲哚酯、敌磺钠、喹菌酮、烯丙苯噻唑、溴硝醇、碘甲烷、威百亩、敌线酯、棉隆、二氯异丙醚、噻唑磷、硫线磷、丰索磷、虫线磷、苯线磷、灭线磷、除线磷、氯唑磷、丁硫环磷、杀线威、涕灭威、克百威、硫酰氟、二氯丙烯、二氯异烟酸、烯丙异噻唑;本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在所述杀菌组合物中的总的质量百分含量是1%-90%,本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与前述商品杀菌剂的比例为质量百分比1%∶99%到99%∶1%;所述杀菌组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;所述杀菌组合物防治的植物病害选自:稻苗绵腐病、番茄根腐病、马铃薯晚疫病、烟草黑胫病、谷子白粉病、葡萄霜霉病、莴苣霜霉病、黄瓜霜霉病、黄瓜炭疽病;所述杀菌组合物适用的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。All of the isothiazolium ether methoxy acrylate derivative IV of the present invention is combined with any one or two of the commercial bactericides to form a bactericidal composition for controlling agricultural and forestry and horticultural plant diseases. From: benzothiadiazole, thiazide, abbreviated as TDL, thiazamide, methyl thiazide, 4-methyl-1,2,3-thiadiazole-5-carboxylic acid, 4-methyl-1 , 2,3-thiadiazol-5-formate, 4-methyl-1,2,3-thiadiazole-5-carboxylic acid ethyl ester, DL-β-aminobutyric acid, isotianil, common in English Named: isotianil, 3,4-dichloroisothiazol-5-carboxylic acid, 3,4-dichloroisothiazol-5-formate, 3,4-dichloroisothiazol-5-carboxylic acid ethyl ester, ribavirin, An Tofin, nymidine or salicylic acid, cymoxanil, thiram, thiram, mancozeb, ethylphosphonium, thiophanate, chlorothalonil, diclofenac, procymidone, benzene Rustidine, methyl thiophanate, thiophanate, refined metalaxyl, flumorph, enoylmorpholine, high-performance metalaxyl, high-efficiency benzoxanthin, chloramphenicol, sulfamethoxazole, mesalamide, Thiofuramide, fluoroamide, leaf sputum, cyclopropionamide, cycloflufenamide, cyclyl Amine, cyanamide, thiastrobin, flufenamide, penthiopyram, dipropionamide, fenhexamide, mefenamide, rust, acetophene, iprodiurea, azoxystrobin Ester, leptin, fluoxastrobin, ether oxystrobin, phenoxystrobin, anthracycline, picoxystrobin, pyraclostrobin, trifloxystrobin, enestrobin, enestrobin, oxygen Cyclosazole, carbendazole, cyproconazole, difenoconazole, diniconazole, high-efficiency diniconazole, epoxiconazole, nitrile azole, fluoroquinazole, flusilazole, fluconazole, hexaconazole , imidazole, inocastazole, cytosine, myclobutanil, penconazole, propiconazole, prothioconazole, flufenazole, tebuconazole, tetrafluoroetherazole, triazole alcohol, azole , biphenyl triazole alcohol, Thiabendazole, Maishenning, imazalil, high-efficiency imazalil, prochloraz, fluconazole, cyanoxazole, imidazolone, moxalimid, rice blast, famoxadone, pyridine oxazole, Moxacillin, oxacillin, ethaboxam, carbendazim, thiazepine, thiothiazide, dodecaline morpholine, butyl morpholine, thirteen morpholine, seed dressing, flavonoids, fluoride Acridine, aglycone, cycloheximide, boscalid, flufenamide, acridine, cyprodinil, fluzalazine, azoxystrobin, azoxystrobin, pyrimethanil, chlorine Pyrimidyl alcohol, fluoropyrimidine alcohol, chlorpyrifos, dicyanoquinone, ethoxyquin, quinolin, propoxyquinoline, phenoxyquinoline, carbendazim, isopropyl amide, phenothimethamine , downy mildew, sulfavir, enemies, diarrhea, pyridoxine, methyl chlorpyrifos, quercetin, geranol, polymycin, polyoxymycin, tyrosin, Jinggangmycin, streptomycin, metalaxyl, furosemide, benzathine, furfuramide, rust-killing amine, carbendazim, benomyl, thiophanate-methyl, triazolone, acetaminophenone Ester, dipyridamole, acetem, captan, captan, sterilized Dan Ethylene nucleus, chlorofluorobacteria, sclerotium, chlorothalonil, indole, rice blast, leaf azole, pentachloronitrobenzene, zinc propyl, triethylphosphonate, sulphur, Bordeaux Liquid, copper sulfate, copper oxychloride, cuprous oxide, copper hydroxide, benomyl, pentosan, chlorfenapyr, tetrachlorophenyl hydrazine, praziquantel, spiroxylamine, tricyclazole, azine Ling, polypyridinium, biguanide salt, bis-octylamine, chloramine, sulfonamide, toluidine, oxime ester, sodium sulfonate, quinoflazer, allyl benzothiazole, bronopol, iodine Methane, Weibaimu, enemy ester, cotton, dichloroisopropyl ether, thiazophos, sulphur, phosphorus, sulphate, phenylphosphorus, phosphine, phosphazone, phosphazene, Butylthiophosphorus, chlorpyrifos, aldicarb, carbofuran, sulfuryl fluoride, dichloropropene, dichloroisonicotinic acid, allylisothiazole; isothiazolyl ether methoxy acrylate derivatives of the invention The total mass percentage of IV in the germicidal composition is from 1% to 90%, and the ratio of the isothiazolyl ether methoxyacrylate derivative IV of the present invention to the commercial fungicide is 1% by mass. 99% to 99%: 1%; the bactericidal composition processed dosage form is selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble thickener , poisonous valley, block bait, granular bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, hair Air agent, ointment, hot mist, cold spray, aerosol, solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microparticle, tracking powder, oil suspension Agent, oil dispersible powder, thickener, pouring agent, seed coating agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam releasing agent; the plant disease controlled by the bactericidal composition is selected from: rice Miao cotton rot, tomato root rot, potato late blight, tobacco black shank, millet powdery mildew, grape downy mildew, lettuce downy mildew, cucumber downy mildew, cucumber anthracnose; plants suitable for the bactericidal composition From: rice, wheat, barley, oats, corn, sorghum, sweet potatoes, Potato, cassava, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut, rape, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sword Hemp, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops , pepper, banana, papaya, orchid, bonsai.
实施例13:本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与抗植物病毒剂组合在防治农业和林业以及园艺植物病毒病害中的应用:Example 13: Application of the combination of the isothiazolium ether methoxy acrylate derivative IV of the present invention and an anti-plant virus agent in controlling agricultural and forestry and horticultural plant virus diseases:
本发明的所有异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与商品抗病毒药剂中的任意一种或两种组合形成抗病毒组合物用于防治农业和林业以及园艺植物病毒病害,所述商品抗病毒 药剂选自:苯并噻二唑、噻酰菌胺,简写为TDL、异噻菌胺,其英文通用名为:isotianil、4-甲基-1,2,3-噻二唑-5-甲酸、4-甲基-1,2,3-噻二唑-5-甲酸钠、4-甲基-1,2,3-噻二唑-5-甲酸乙酯、3,4-二氯异噻唑-5-甲酸、3,4-二氯异噻唑-5-甲酸钠、3,4-二氯异噻唑-5-甲酸乙酯、DL-β-氨基丁酸、病毒唑、安托芬、宁南霉素、噻酰胺、甲噻诱胺或水杨酸、嘧肽霉素、二氯异烟酸、烯丙异噻唑、井冈羟胺、井冈霉素;本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在所述抗病毒组合物中的总的质量百分含量是1%-90%,本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与前述商品抗植物病毒剂的比例为质量百分比1%∶99%到99%∶1%;所述抗病毒组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;所述抗病毒组合物防治的病毒病害选自:水稻矮缩病、黄矮病、条纹叶枯病、番茄蕨叶病毒病、辣椒花叶病毒病、烟草脉坏死病毒病、玉米矮花叶病、花椰菜花叶病毒、柑橘病毒病、建兰花叶病毒、建兰环斑病毒;所述抗病毒组合物用于防治的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。All of the isothiazolyl ether methoxy acrylate derivative IV of the present invention is combined with any one or both of the commercial antiviral agents to form an antiviral composition for controlling agricultural and forestry and horticultural plant virus diseases, the commodity Antiviral The agent is selected from the group consisting of: benzothiadiazole, thiazide, abbreviated as TDL, isothiazide, and its common name in English is: isotianil, 4-methyl-1,2,3-thiadiazol-5-carboxylic acid , 4-methyl-1,2,3-thiadiazol-5-formate, 4-methyl-1,2,3-thiadiazole-5-carboxylic acid ethyl ester, 3,4-dichloroisothiazole- 5-carboxylic acid, sodium 3,4-dichloroisothiazol-5-carboxylate, ethyl 3,4-dichloroisothiazol-5-carboxylate, DL-β-aminobutyric acid, ribavirin, antofin, southern nanmycin Or thiazamide, methyl thiazide or salicylic acid, glutathione, dichloroisonicotinic acid, allylisothiazole, Jinggang hydroxylamine, Jinggangmycin; derivative of isothiazolyl ether methoxy acrylate of the present invention The total mass percentage of the substance IV in the antiviral composition is from 1% to 90%, and the ratio of the isothiazolyl ether methoxy acrylate derivative IV of the present invention to the commercial anti-plant virus agent is quality. Percentage 1%: 99% to 99%: 1%; the antiviral composition processed dosage form is selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule , soluble concentrate, poisonous valley, block bait, granular poison Bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, hot aerosol ,cold spray, aerosol, solid/liquid mixture, liquid/liquid mixture, solid/solid mixture, lacquer, granule, trace powder, oil suspension, oil dispersible powder, thick rubber Agent, splashing agent, seed coating agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam release agent; the virus disease controlled by the antiviral composition is selected from the group consisting of rice dwarf disease, yellow dwarf disease, Stripe leaf blight, tomato fern leaf virus disease, pepper mosaic virus disease, tobacco vein necrosis virus disease, corn dwarf mosaic disease, cauliflower mosaic virus, citrus virus disease, Jianlan leaf virus, Jianlan ring spot virus; Antiviral composition The plant used for control is selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut, rapeseed, Sesame, sunflower, beet, sugar cane, Brown, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya , apples, citrus and peach trees, tea, wild vegetables, bamboo shoots, hops, pepper, bananas, papaya, orchids, bonsai.
实施例14:本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与杀螨剂组合在防治农业和林业以及园艺植物螨害中的应用:Example 14: Application of the combination of isothiazolyl ether methoxy acrylate derivative IV of the present invention and acaricide in controlling agricultural and forestry and horticultural plant damage:
本发明的所有异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与商品杀螨剂中的任意一种或两种组合形成杀螨组合物用于防治农业和林业以及园艺植物螨害,所述商品杀螨剂选自:***锡、三环锡、苯丁锡、三磷锡、毒虫畏、甲基毒虫畏、巴毒磷、敌敌畏、庚烯磷、速灭磷、久效磷、二溴磷、毒死蜱、嘧啶磷、氯甲亚胺硫磷、氧乐果、敌杀磷、乙硫磷、马拉硫磷、虫螨畏、伏杀硫磷、辛硫磷、甲基嘧啶硫磷、喹硫磷、治螟磷、***磷、蚜灭多、水胺硫磷、甲胺磷、胺丙畏、氯亚胺硫磷、亚胺硫磷、氟丙菊酯、联苯菊酯、氯氟氰菊酯、精高效氯氟氰菊酯、甲氰菊酯、氟氰戊菊酯、氟氯苯菊酯、氟胺氰菊酯、溴氟菊酯、联苯肼酯、苯硫威、涕灭威、丁酮威、杀线威、抗虫威、久效威、苯菌灵、氯灭杀威、克百威、丁硫克百威、速灭威、蜱虱威、伐虫脒、单甲脒、杀螨脒、双甲脒、杀虫脒、苯甲酸苄酯、溴螨酯、丁氟螨酯、灭螨醌、氟蚜螨、氟虫脲、浏阳霉素、虫螨霉素、苏云金素、杀螨素、浏阳霉素、阿维菌素、多拉菌素、埃普利诺菌素、伊维菌素、赛拉菌素、莫西菌素、除虫菊素、烟碱、苦参碱、印楝素、鱼藤酮、吡螨胺、哒螨酮、唑螨酯、四螨嗪、炔螨特、噻 螨酮、螺螨酯、嘧螨酯、杀螨酯、克螨特、哒螨灵;本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在所述杀螨组合物中的总的质量百分含量是1%-90%,本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述商品杀螨剂的比例为质量百分比1%∶99%到99%∶1%;所述杀螨组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;所述杀螨组合物防治的螨害选自:螨害选自叶螨科、细须螨科、呋线螨、瘿螨科、红叶螨属、瘿螨科的害螨,这些害螨是世界性农业害螨、林业害螨、园艺害螨和卫生害螨;所述杀螨组合物用于防治的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。 All of the isothiazolium ether methoxy acrylate derivative IV of the present invention is combined with any one or both of the commercial acaricides to form a miticide composition for controlling agricultural and forestry and horticultural plant mites. Acaricides are selected from the group consisting of: triazolyl tin, tricyclotin, phenbutyltin, triphosphorus, chlorpyrifos, methyl chlorpyrifos, phytophos, dichlorvos, heptene phosphorus, fast-acting phosphorus, monocrotophos, dibromo Phosphorus, chlorpyrifos, pyrimidine phosphorus, chloromethionine, omethoate, chlorpyrifos, ethion, malathion, chlorpyrifos, sulforaphane, phoxim, methyl pyrithione, Quetiapine, guanidine, triazophos, quenching, acesulfame, methamidophos, acesulfame, chloroimidate, imipenem, flumethrin, bifenthrin, Cyhalothrin, cyhalothrin, fenvalerate, fluvalerate, flumethrin, fluvalinate, bifenthrin, bifenyl ester, phenylthiocarbamate , aldicarb, butanone, chlorpyrifos, anti-insect, long-acting, benomyl, chlorhexidine, carbofuran, butyl thiocarb, chlorpyrifos, converse, worm脒, monomethyl 脒,螨脒, amitraz, chlorpyrifos, benzyl benzoate, bromo oxime ester, butyl fluoro ester, guanidine, fluoroquinone, flufenacetil, liuyangmycin, echinomycin, sulphate, kill Alizarin, liuyangmycin, avermectin, doramectin, eplenomycin, ivermectin, serramycin, moxidectin, pyrethrin, nicotine, matrine, imprint Alizarin, rotenone, pyridoxamine, anthrone, oxazolidine, tetrazine, alkyne , thiazolone , spirodecyl ester, pyridoxine , acaricidal ester , ketone, hydrazine ; The total mass percentage of the isothiazolyl ether methoxy acrylate derivative IV of the invention in the acaricidal composition is from 1% to 90%, the isothiazolyl ether methoxy acrylate derivative of the invention The ratio of IV to the commercial acaricide is 1% by mass: 99% to 99%: 1% by mass; the dosage form processed by the acaricidal composition is selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, Capsule suspension, water-soluble granules, fine granules, soluble concentrate, poisonous valley, block bait, granular bait, flake bait, concentrated bait, slow release block, static electricity Spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, hot spray, cold spray, aerosol, solid/liquid mixture Agent, liquid/liquid mixed agent, solid/solid mixed agent, lacquer, granule, trace powder, oil suspension, oil dispersible powder, thickener, pouring agent, seed coating agent, smear agent, Membrane oil agent, ultra low volume liquid agent, steam release agent; the cockroach damage controlled by the acaricidal composition is selected from the group consisting of: the cockroach damage is selected from the group consisting of the genus Aphididae, the genus Euphorbiaceae, the eucalyptus, the genus Amaranthus, the genus Amaranthus, The pests of the family are the world's agricultural pests, forest pests, horticultural pests and health hazards; the plants used for the control of the acaricidal composition are selected from the group consisting of: rice, wheat, barley, oats , corn, sorghum, sweet potato, potato, cassava, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut, rape, sesame, sunflower, sugar beet, sugar cane, coffee, cocoa, ginseng, fritillaria, rubber, Coconut, oil palm, sisal, tobacco, tomato, pepper, radish, Melon, cabbage, celery, mustard, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, Bonsai.
表1本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ的化学结构和理化参数Table 1 Chemical structure and physical and chemical parameters of the isothiazolyl ether methoxy acrylate derivative IV of the present invention
Figure PCTCN2017072557-appb-000006
Figure PCTCN2017072557-appb-000006
Figure PCTCN2017072557-appb-000007
Figure PCTCN2017072557-appb-000007
Figure PCTCN2017072557-appb-000008
Figure PCTCN2017072557-appb-000008
表2本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ的抑菌活性(50微克/毫升的抑制率/%)Table 2 Antibacterial activity of the isothiazolyl ether methoxy acrylate derivative IV of the present invention (inhibition rate/% of 50 μg/ml)
序号Serial number 化合物Compound ASAS CACA GZGZ PPPP BCBC SSSS RCRC PSPS PIPI
11 CL03-49CL03-49 42.8642.86 66.6766.67 52.1752.17 78.2678.26 100100 80.0080.00 100100 64.7164.71 52.6352.63
22 CL03-50CL03-50 57.1457.14 66.6766.67 73.9173.91 78.2678.26 100100 53.3353.33 100100 64.7164.71 57.8957.89
33 CL04-03CL04-03 57.1457.14 100100 60.8760.87 86.9686.96 100100 100100 100100 58.8258.82 47.3747.37
44 CL04-04上On CL04-04 85.7185.71 75.0075.00 60.8760.87 73.9173.91 100100 90.0090.00 100100 52.9452.94 42.1142.11
55 CL04-04下Under CL04-04 50.0050.00 75.0075.00 73.9173.91 60.8760.87 58.3358.33 76.6776.67 92.5992.59 64.7164.71 52.6352.63
66 CL04-06CL04-06 57.1457.14 50.0050.00 73.9173.91 73.9173.91 100100 100100 100100 70.5970.59 78.9578.95
77 CL04-15ACL04-15A 47.0647.06 50.0050.00 41.1841.18 53.0353.03 100100 100100 85.4585.45 76.9276.92 78.9578.95
88 CL04-15BCL04-15B 100100 91.6791.67 70.5970.59 62.1262.12 100100 90.0090.00 98.1898.18 69.2369.23 94.7494.74
99 CL04-15CCL04-15C 52.9452.94 75.0075.00 94.4494.44 71.2171.21 100100 98.0098.00 89.0989.09 76.9276.92 89.4789.47
1010 CL04-22ACL04-22A 37.1437.14 42.8642.86 78.9578.95 40.3540.35 53.8553.85 84.0084.00 87.7087.70 20.0020.00 80.0080.00
1111 CL04-22BCL04-22B 28.5728.57 35.7135.71 100100 49.1249.12 51.9251.92 100100 86.8986.89 73.3373.33 80.0080.00
1212 CL04-22CCL04-22C 27.8727.87 44.0044.00 63.6463.64 61.4061.40 47.3747.37 80.0080.00 60.9860.98 56.7656.76 100100
1313 CL04-22DCL04-22D 47.5447.54 87.5087.50 100100 80.7780.77 100100 100100 100100 89.1989.19 100100
1414 CL04-22ECL04-22E 27.2727.27 45.8345.83 51.5251.52 42.8642.86 62.5062.50 29.4129.41 76.0076.00 21.2121.21 28.5728.57
1515 CL04-22FCL04-22F 16.3616.36 12.5012.50 33.3333.33 32.7732.77 45.5445.54 52.9452.94 76.0076.00 15.1515.15 17.1417.14
1616 CL04-24CL04-24 12.7312.73 16.6716.67 33.3333.33 39.5039.50 37.5037.50 52.9452.94 62.0062.00 24.2424.24 22.8622.86
1717 CL04-25ACL04-25A 8.208.20 20.0020.00 54.5554.55 19.3019.30 42.1142.11 46.6746.67 65.8565.85 45.9545.95 100100
1818 CL04-25BCL04-25B 21.3121.31 28.0028.00 63.6463.64 22.8122.81 36.8436.84 73.3373.33 85.3785.37 18.9218.92 33.3333.33
1919 CL04-25CCL04-25C 34.4334.43 44.0044.00 100100 40.3540.35 57.8957.89 66.6766.67 100100 83.7883.78 100100
2020 CL04-25DCL04-25D 16.3616.36 12.5012.50 21.2121.21 27.7327.73 39.2939.29 52.9452.94 62.0062.00 15.1515.15 17.1417.14
21twenty one CL04-25ECL04-25E 9.099.09 16.6716.67 45.4545.45 10.9210.92 35.7135.71 52.9452.94 54.0054.00 21.2121.21 11.4311.43
22twenty two CL04-17CL04-17 35.7135.71 50.0050.00 60.8760.87 47.8347.83 100100 86.6786.67 81.4881.48 58.8258.82 47.3747.37
23twenty three CL04-32ACL04-32A 34.4334.43 36.0036.00 45.4545.45 29.8229.82 52.6352.63 53.3353.33 85.3785.37 35.1435.14 90.4890.48
24twenty four CL04-32BCL04-32B 40.9840.98 52.0052.00 81.8281.82 64.9164.91 47.3747.37 80.0080.00 100100 78.3878.38 100100
2525 CL04-32CCL04-32C 47.5447.54 60.0060.00 63.6463.64 71.9371.93 57.8957.89 73.3373.33 70.7370.73 67.5767.57 100100
2626 CL04-32DCL04-32D 54.1054.10 84.0084.00 100100 64.9164.91 84.2184.21 73.3373.33 85.3785.37 89.1989.19 100100
2727 CL04-32ECL04-32E 5.455.45 12.5012.50 24.2424.24 39.5039.50 32.1432.14 41.1841.18 58.0058.00 15.1515.15 11.4311.43
2828 CL04-32FCL04-32F 12.7312.73 12.5012.50 60.6160.61 57.9857.98 42.8642.86 52.9452.94 62.0062.00 21.2121.21 20.0020.00
2929 CL04-00CL04-00 21.5421.54 22.6022.60 29.6329.63 36.9736.97 32.4432.44 22.6422.64 12.0312.03 21.2821.28 32.0232.02
3030 CL05-00CL05-00 44.4444.44 65.0065.00 50.0050.00 61.2161.21 75.0075.00 66.6766.67 85.7185.71 53.9153.91 76.3676.36
3131 嘧菌酯Azoxystrobin 75.0075.00 55.5655.56 71.4371.43 100100 91.1891.18 88.1088.10 84.0684.06 80.7780.77 46.8846.88
3232 烯肟菌酯Enoxacin 50.0050.00 55.2255.22 21.5421.54 59.0959.09 48.5748.57 44.0044.00 73.9773.97 57.5057.50 32.9732.97
表3本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ防治黄瓜白粉病的活性Table 3 Activity of the isothiazolyl ether methoxy acrylate derivative IV of the present invention for controlling cucumber powdery mildew
Figure PCTCN2017072557-appb-000009
Figure PCTCN2017072557-appb-000009
表4本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ防治黄瓜霜霉病的活性Table 4 Activity of the isothiazolyl ether methoxy acrylate derivative IV of the present invention for controlling cucumber downy mildew
Figure PCTCN2017072557-appb-000010
Figure PCTCN2017072557-appb-000010
表5本发明的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ的抗烟草花叶病毒的活性(100微克/毫升的抑制率/%)Table 5 Activity of the anti-tobacco mosaic virus of the isothiazolyl ether methoxy acrylate derivative IV of the present invention (100 μg/ml inhibition rate/%)
序号Serial number 化合物Compound 治疗模式Treatment mode 钝化模式Passivation mode 保护模式Protection mode 诱导模式Induction mode
11 CL03-49CL03-49 39.41±2.9939.41±2.99 52.48±0.6452.48±0.64 35.90±0.6335.90±0.63 75.90±0.8375.90±0.83
22 CL03-50CL03-50 48.32±5.8848.32±5.88 70.19±0.4170.19±0.41 54.02±0.5154.02±0.51 84.02±5.5184.02±5.51
33 CL04-03CL04-03 45.04±4.1545.04±4.15 81.75±2.8381.75±2.83 35.13±0.3935.13±0.39 75.13±0.6975.13±0.69
44 CL04-04上On CL04-04 19.10±2.1319.10±2.13 75.46±7.9175.46±7.91 61.60±1.2561.60±1.25 71.60±1.5571.60±1.55
55 CL04-04下Under CL04-04 19.10±2.0019.10±2.00 65.46±7.4665.46±7.46 45.46±3.7045.46±3.70 55.46±6.7055.46±6.70
66 CL04-06CL04-06 22.43±6.8522.43±6.85 22.22±5.9022.22±5.90 54.08±3.8154.08±3.81 74.08±5.8174.08±5.81
77 CL04-15ACL04-15A 1.52±0.621.52±0.62 54.76±1.2654.76±1.26 40.53±0.8440.53±0.84 70.53±0.8470.53±0.84
88 CL04-15BCL04-15B 27.00±4.1327.00±4.13 52.13±6.4852.13±6.48 14.74±2.7314.74±2.73 74.74±2.7374.74±2.73
99 CL04-15CCL04-15C 1.52±0.621.52±0.62 59.94±2.7659.94±2.76 25.08±4.3325.08±4.33 85.08±5.3385.08±5.33
1010 CL04-22ACL04-22A 23.44±5.5823.44±5.58 49.90±3.6349.90±3.63 30.71±2.0630.71±2.06 60.71±2.2660.71±2.26
1111 CL04-22BCL04-22B 1.52±0.621.52±0.62 36.70±4.9836.70±4.98 53.10±0.7553.10±0.75 53.10±0.7553.10±0.75
1212 CL04-22CCL04-22C 4.62±0.554.62±0.55 4.44±0.854.44±0.85 23.57±0.5723.57±0.57 83.57±0.0783.57±0.07
1313 CL04-22DCL04-22D 32.78±3.3632.78±3.36 4.44±0.854.44±0.85 49.05±2.7749.05±2.77 79.05±7.7779.05±7.77
1414 CL04-22ECL04-22E 20.25±5.5820.25±5.58 45.40±2.2045.40±2.20 22.71±2.0522.71±2.05 12.71±6.0512.71±6.05
1515 CL04-22FCL04-22F 1.52±0.621.52±0.62 00 23.76±3.4223.76±3.42 63.76±3.5263.76±3.52
1616 CL04-24CL04-24 14.96±3.0814.96±3.08 27.30±6.5627.30±6.56 36.78±5.5036.78±5.50 46.78±7.7046.78±7.70
1717 CL04-25ACL04-25A 82.36±5.0282.36±5.02 00 40.74±2.5140.74±2.51 70.74±2.8170.74±2.81
1818 CL04-25BCL04-25B 20.51±1.8420.51±1.84 00 19.56±3.3619.56±3.36 18.56±3.7618.56±3.76
1919 CL04-25CCL04-25C 14.68±4.8414.68±4.84 00 59.82±4.2359.82±4.23 69.82±5.2769.82±5.27
2020 CL04-25DCL04-25D 35.93±1.6335.93±1.63 00 21.15±1.6921.15±1.69 21.15±3.6921.15±3.69
21twenty one CL04-25ECL04-25E 19.12±6.5619.12±6.56 00 26.00±4.7126.00±4.71 16.00±7.7116.00±7.71
22twenty two CL04-17CL04-17 31.56±3.9531.56±3.95 35.93±1.5335.93±1.53 29.27±1.3129.27±1.31 39.27±1.4139.27±1.41
23twenty three CL04-32ACL04-32A 1.52±0.621.52±0.62 37.75±6.6237.75±6.62 45.32±2.0045.32±2.00 45.32±2.0045.32±2.00
24twenty four CL04-32BCL04-32B 81.33±5.4981.33±5.49 72.13±5.5972.13±5.59 23.43±1.0223.43±1.02 73.43±4.0973.43±4.09
2525 CL04-32CCL04-32C 31.56±3.9131.56±3.91 41.40±0.9241.40±0.92 19.00±0.7219.00±0.72 16.00±7.7116.00±7.71
2626 CL04-32DCL04-32D 1.52±0.621.52±0.62 69.27±1.0269.27±1.02 39.07±2.7339.07±2.73 39.07±2.7339.07±2.73
2727 CL04-32ECL04-32E 1.52±0.621.52±0.62 13.65±0.5513.65±0.55 40.79±0.7740.79±0.77 70.79±3.7770.79±3.77
2828 CL04-32FCL04-32F 63.67±5.6663.67±5.66 7.71±1.427.71±1.42 53.40±4.7353.40±4.73 63.40±6.7363.40±6.73
2929 CL04-00CL04-00 27.32±1.2427.32±1.24 20.68±2.1020.68±2.10 26.30±2.4726.30±2.47 20.34±2.1620.34±2.16
3030 CL05-00CL05-00 26.39±1.2226.39±1.22 19.68±1.1019.68±1.10 25.30±1.4725.30±1.47 19.34±1.1419.34±1.14
3131 宁南霉素Ningnanmycin 74.10±2.0474.10±2.04 -- -- --
3232 TDLTDL -- -- -- 65.00±2.0065.00±2.00
3333 BTHBTH -- -- 78.10±0.5478.10±0.54 78.00±1.3478.00±1.34
3434 SZG-7SZG-7 -- -- -- 79.00±2.2779.00±2.27
3535 病毒唑Ribavirin -- 78.00±1.0078.00±1.00 -- --
3636 异噻菌胺Isotianil 27.31±2.1227.31±2.12 20.77±7.3020.77±7.30 24.80±5.8524.80±5.85 44.44±5.1844.44±5.18
工业实用性Industrial applicability
本发明提供了一类异噻唑肟醚甲氧基丙烯酸酯衍生物及其制备方法和用途。本发明提供给的化合物能够调控农业、园艺、卫生和林业植物害虫、植物病原物的生物活性,可用于农业领域、园艺领域、林业领域杀虫、杀螨、杀菌、抗植物病毒、诱导植物产生抗病性,具有较好的经济价值和应用前景。 The invention provides a class of isothiazolium ether methoxy acrylate derivatives, a preparation method thereof and use thereof. The compound provided by the invention can regulate the biological activity of plant pests and plant pathogens in agriculture, horticulture, sanitary and forestry, and can be used in agriculture, horticulture, forestry, insecticide, acaricidal, bactericidal, anti-plant virus, induced plant production Disease resistance, with good economic value and application prospects.

Claims (11)

  1. 一类异噻唑肟醚甲氧基丙烯酸酯衍生物,其特征在于具有如式Ⅳ所示的化学结构通式:A class of isothiazolyl ether methoxy acrylate derivatives characterized by having the chemical structural formula shown in Formula IV:
    Figure PCTCN2017072557-appb-100001
    Figure PCTCN2017072557-appb-100001
    其中,R1选自:甲基、氢、胺基;R2选自:1,2-二氟乙基、炔丙基、环丙基、甲基、1-甲硫基-2-甲基丙-2-基、(R)-1-甲硫基丙-2-基;X选自:氧、氮,n=1,2;Y选自:CHOH-CH2,CHO-CH2,(CH=CH)m,m=0,1;Z选自:碳、氮。Wherein R 1 is selected from the group consisting of methyl, hydrogen, and amine; and R 2 is selected from the group consisting of: 1,2-difluoroethyl, propargyl, cyclopropyl, methyl, 1-methylthio-2-methyl Prop-2-yl, (R)-1-methylthiopropan-2-yl; X is selected from the group consisting of: oxygen, nitrogen, n = 1, 2; Y is selected from: CHOH-CH 2 , CHO-CH 2 , ( CH=CH) m , m=0,1; Z is selected from the group consisting of carbon and nitrogen.
  2. 权利要求1所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ的合成方法,具体合成路线如下:The method for synthesizing the isothiazolium ether methoxy acrylate derivative IV according to claim 1, wherein the specific synthetic route is as follows:
    Figure PCTCN2017072557-appb-100002
    Figure PCTCN2017072557-appb-100002
    其中,R1选自:甲基、氢、胺基;R2选自:1,2-二氟乙基、炔丙基、环丙基、甲基、1-甲硫基-2-甲基丙-2-基、(R)-1-甲硫基丙-2-基;X选自:氧、氮,n=1,2;Y选自:CHOH-CH2,CHO-CH2,(CH=CH)m,m=0,1;Z选自:碳、氮。Wherein R 1 is selected from the group consisting of methyl, hydrogen, and amine; and R 2 is selected from the group consisting of: 1,2-difluoroethyl, propargyl, cyclopropyl, methyl, 1-methylthio-2-methyl Prop-2-yl, (R)-1-methylthiopropan-2-yl; X is selected from the group consisting of: oxygen, nitrogen, n = 1, 2; Y is selected from: CHOH-CH 2 , CHO-CH 2 , ( CH=CH) m , m=0,1; Z is selected from the group consisting of carbon and nitrogen.
  3. 根据权利要求2所述的合成方法,其特征在于,所述的噻二唑肟醚甲氧基丙烯酸酯衍生物的合成方法分为以下步骤:The method according to claim 2, wherein the method for synthesizing the thiadiazolone methoxy acrylate derivative is divided into the following steps:
    A.化合物Ⅱ的制备:A. Preparation of Compound II:
    在25毫升单口圆底烧瓶中加入1.10毫摩尔将化合物I、3,4-二氯异噻唑-5-取代羰基化合物和盐酸分别加入乙醇溶液中,在室温下反应,反应完全后减压除去溶剂,将残余物纯化,即得所述化合物II;其中,所述3,4-二氯异噻唑-5-取代羰基化合物选自:3,4-二氯异噻唑-5-甲醛、3,4-二氯异噻唑-5-乙酮、4-(3,4-二氯异噻唑-5-基)-丁-3-烯-2-酮;Add 1.10 mmol of the compound I, 3,4-dichloroisothiazol-5-substituted carbonyl compound and hydrochloric acid to a solution of ethanol in a 25 ml single-neck round bottom flask, react at room temperature, and remove the solvent under reduced pressure after completion of the reaction. Purifying the residue to obtain the compound II; wherein the 3,4-dichloroisothiazol-5-substituted carbonyl compound is selected from the group consisting of: 3,4-dichloroisothiazol-5-formaldehyde, 3,4 -dichloroisothiazol-5-ethanone, 4-(3,4-dichloroisothiazol-5-yl)-but-3-en-2-one;
    或B.化合物Ⅱ的制备:Or B. Preparation of Compound II:
    将化合物I、3,4-二氯异噻唑-5-甲氰与巯基乙酸分别加入乙醇溶液中,在室温下反应,反应完全后将反应液浓缩,将残余物纯化,即得所述化合物II;The compound I, 3,4-dichloroisothiazol-5-cyanamide and thioglycolic acid are separately added to the ethanol solution, and reacted at room temperature. After the reaction is completed, the reaction solution is concentrated, and the residue is purified to obtain the compound II. ;
    C.化合物Ⅲ的制备方法:C. Preparation method of compound III:
    将化合物Ⅱ与氢氧化钠加入甲醇溶液中,然后加热回流进行反应,反应完全后将反应液浓缩,残余物用乙酸乙酯稀释,然后加入水将残余物溶解,分离出水层,然后 将水层用盐酸调节pH至3,然后用乙酸乙酯萃取,水层用乙酸乙酯反萃一遍,合并有机层,有机层用饱和氯化钠洗,无水硫酸钠干燥,抽滤,减压除去溶剂,即得化合物Ⅲ;The compound II and sodium hydroxide are added to the methanol solution, and then the reaction is carried out by heating under reflux. After the reaction is completed, the reaction solution is concentrated, the residue is diluted with ethyl acetate, then the residue is dissolved by water, and the aqueous layer is separated, and then The aqueous layer was adjusted to pH 3 with hydrochloric acid, and then extracted with ethyl acetate. The aqueous layer was extracted with ethyl acetate. The organic layer was combined and washed with saturated sodium chloride and dried over anhydrous sodium sulfate Pressing the solvent to obtain the compound III;
    D.化合物Ⅳ的制备方法:D. Preparation of Compound IV:
    将化合物Ⅲ、EDCI与HOBT加入至二氯甲烷中,在室温反应,然后向反应体系中加入R2-XHn,n=1,2,室温下继续反应,反应完全后,反应液用水洗两遍,分离出有机层,有机层分别用饱和碳酸氢钠和饱和氯化钠洗,无水硫酸钠干燥,抽滤,减压除去溶剂,将残余物纯化,即得到所述化合物Ⅳ。Adding compound III, EDCI and HOBT to dichloromethane, reacting at room temperature, then adding R 2 -XH n , n=1,2 to the reaction system, and continuing the reaction at room temperature. After the reaction is completed, the reaction solution is washed with water. The organic layer was separated, and the organic layer was washed with saturated sodium hydrogen sulfate and saturated sodium chloride, dried over anhydrous sodium sulfate, filtered,
  4. 权利要求1所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在制备杀菌剂、抗烟草花叶病毒剂或植物激活剂中的用途。Use of the isothiazolyl ether methoxy acrylate derivative IV according to claim 1 for the preparation of a bactericide, a tobacco mosaic virus agent or a plant activator.
  5. 权利要求1所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与农业上可接受的助剂在制备杀菌剂、抗烟草花叶病毒剂或植物激活剂中的用途。Use of the isothiazolyl ether methoxy acrylate derivative IV according to claim 1 and an agriculturally acceptable adjuvant for the preparation of a bactericide, a tobacco mosaic virus agent or a plant activator.
  6. 权利要求1所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在防治农业和林业以及园艺植物虫害中的用途。Use of the isothiazolyl ether methoxy acrylate derivative IV according to claim 1 for controlling agricultural and forestry and horticultural plant pests.
  7. 根据权利要求6所述的用途,其特征在于,所述异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与农业化学品共同施用;优选地,所述农业化学品选自:杀虫剂、杀菌剂、抗植物病毒剂、杀螨剂中的一种或几种。The use according to claim 6, characterized in that the isothiazolyl ether methoxy acrylate derivative IV is co-administered with an agricultural chemical; preferably, the agricultural chemical is selected from the group consisting of insecticides, sterilization One or more of an agent, an anti-plant virus agent, and an acaricide.
  8. 根据权利要求6或7所述的用途,其特征在于,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述杀虫剂中的任意一种或两种组合形成杀虫组合物用于防治农业和林业以及园艺植物虫害;The use according to claim 6 or 7, wherein the isothiazolyl ether methoxy acrylate derivative IV is combined with any one or both of the insecticides to form an insecticidal composition. Used to control agricultural and forestry and horticultural plant pests;
    优选地,所述杀虫剂选自:毒死蜱、地亚哝、啶虫脒、甲氨基阿维菌素、弥拜菌素、阿维菌素、多杀菌素、氰戊菊酯、高效氰戊菊酯、氯氰菊酯、高效氯氰菊酯、三氟氯氰菊酯、溴氰菊酯、甲氰菊酯、Beta-氟氯氰菊酯、Lambda-三氟氯氰菊酯、二氯苯醚菊酯、苄氯菊酯、丙烯菊酯、联苯菊酯、氯菊酯、醚菊酯、氟氯苯菊酯、氯氟胺氰戊菊酯、吡虫啉、烯啶虫胺、氯噻啉、噻虫啉、噻虫嗪、噻虫胺、呋虫胺、可尼丁、达特南、除虫脲、灭幼脲、伏虫隆、除虫隆、氟铃脲、氟虫脲、啶虫隆、虱螨脲、毒虫脲、氟幼脲、Noviflumuron即多氟脲,其CAS号为121451-02-3、氟螨脲、Novaluron即双苯氟脲、氟啶脲、Bay sir6874即1-[(3.5-二氯-4)4-硝基苯氧基苯基3-3-(2-氯苯)-脲、Bay SIR-8514即1-(4-三氟甲氧基苯基)-3-(2-氯苯)-脲、嗪虫脲、Bistrifluron即双三氟虫脲、呋喃虫酰肼、虫酰肼、氯虫酰肼、甲氧虫酰肼、环虫酰肼、乐果、氧化乐果、敌敌畏、乙酰甲胺磷、***磷、喹硫磷、哒嗪硫磷、氯唑磷、叶 蝉散、西维因、抗蚜威、速灭威、异丙威、杀螟丹、仲丁威、叶飞散、甲萘威、丙硫克百威、丁硫克百威、杀螟丹、溴螨酯、噻螨酮、唑螨酯、哒螨酮、四螨嗪、炔螨特、丁醚脲、吡蚜酮、螺螨酯、螺虫酯、螺虫乙酯、丁烯氟虫腈、***锡、噻嗪酮、灭线磷、氟虫腈、杀虫单、杀虫双、氯虫酰胺、氟虫酰胺、氟氰虫酰胺、氰虫酰胺、唑虫酰胺、溴虫腈、吡嗪酮、乙螨唑、吡螨胺、哒幼酮、吡丙醚、埃玛菌素;Preferably, the insecticide is selected from the group consisting of: chlorpyrifos, scorpion guanidine, acetamiprid, emamectin, imipenem, avermectin, spinosyn, fenvalerate, high-efficiency acetonide Pyrethroid, cypermethrin, beta-cypermethrin, cyhalothrin, deltamethrin, fenpropathrin, Beta-cyfluthrin, Lambda-cyhalothrin, permethrin, permethrin, methrin, hydrazine Pyrethrin, permethrin, fenthrin, flumethrin, flufenacetate, imidacloprid, nitenpyram, chlorothiazide, thiacloprid, thiamethoxam, clothianidin, fur Nicotinamide, cotinine, Dartnam, diflubenzuron, chlorbenzuron, flubenzuron, chlorfenapyr, hexaflumuron, flubenzuron, acetamiprid, guanidine, chlorpyrifos, flubenzuron, Noviflumuron is a polyfluorourea with a CAS number of 121451-02-3, fluoroquinone urea, Novaluron, ie, diphenylfluorourea, chlorfluazuron, and Bay sir6874, 1-[(3.5-dichloro-4)4-nitrobenzene. Oxyphenyl-3-3(2-chlorophenyl)-urea, Bay SIR-8514, 1-(4-trifluoromethoxyphenyl)-3-(2-chlorophenyl)-urea, oxazide , Bistrifluron, bistriazole, furanyl hydrazide, tebufenozide, chlorine Hydrazide, methoxyfenozide, tebufenozide ring, dimethoate, omethoate, dichlorvos, acephate, triazophos, quinalphos, pyridaphenthion, cloxacillin phosphorus, leaves 蝉散, 西维因,抗蚜威,速灭威,Isowei, 杀螟丹,仲丁威, 叶飞散,甲奈威,丙thiocarbany, butyl thiocarb, chlorpyrifos, Bromobromide, thiazolone, oxazolidine, anthrone, tetrazine, alkyne, dibutyl ether urea, pymetrozine, spirodecyl ester, spirotetramat, spirotetramat, butene fipronil , triazolyl tin, buprofezin, chlorpyrifos, fipronil, insecticidal, insecticidal, chlorantraniliprole, flubendiamide, flufenamide, cyanamide, oxazolamide, chlorfenapyr, Pyrazinone, etoxazole, pyridoxamine, ketone, pyriproxyfen, emamectin;
    优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在所述杀虫组合物中的质量百分含量是1%-90%;Preferably, the isothiazolium ether methoxy acrylate derivative IV is present in the pesticidal composition in an amount of from 1% to 90% by mass;
    优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述杀虫剂的比例为质量百分比1%∶99%到99%∶1%;Preferably, the ratio of the isothiazolyl ether methoxy acrylate derivative IV to the insecticide is 1% by mass: 99% to 99%: 1% by mass;
    优选地,所述杀虫组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;Preferably, the dosage form processed by the pesticidal composition is selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous valley, lumps Bait, granular bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, Hot mist, cold spray, aerosol, solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microparticle, trace powder, oil suspension, oil dispersible powder , thickener, pouring agent, seed coating agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam release agent;
    优选地,所述杀虫组合物防治的植物虫害选自:红蜘蛛、东亚飞蝗、云斑车蝗、中华稻蝗、日本黄脊蝗、单刺蝼蛄、东方蝼蛄、稻蓟马、烟蓟马、温室蓟马、稻管蓟马、麦简管蓟马、温室白粉虱、烟粉虱、黑尾叶蝉、大青叶蝉、棉叶蝉、斑衣蜡蝉、褐飞虱、白背飞虱、灰飞虱、甘蔗扁角飞虱、棉蚜、麦二叉蚜、麦长管蚜、桃蚜、高粱蚜、萝卜蚜、吹绵蚧、桑盾蚧、矢尖盾蚧、梨圆蚧、白蜡虫、红蜡蚧、朝鲜球坚蚧、梨网蝽、香蕉网蝽、细角花蝽、微小花蝽、针缘蝽、稻蛛缘蝽、稻褐蝽、稻黑蝽、稻绿蝽、绿盲蝽、苜蓿盲蝽、中黑盲蝽、大草蛉、丽草蛉、中华草蛉、谷蛾、衣蛾、黄刺蛾、褐刺蛾、扁刺蛾、麦蛾、棉红铃虫、甘薯麦蛾、小菜蛾、桃小食心虫、大豆食心虫、桃小食心虫、苹果顶梢卷叶蛾、褐带长卷叶蛾、拟小黄卷叶蛾、二化螟、豆荚螟、玉米螟、三化螟、菜螟、稻纵卷叶螟、条螟、棉卷叶野螟、桃蛀螟、黏虫、斜纹夜蛾、稻螟蛉、棉小造桥虫、甜菜夜蛾、大螟、棉铃虫、鼎点金刚钻、小地老虎、大地老虎、黄地老虎、盗毒蛾、舞毒蛾、甘薯天蛾、豆天蛾、直纹稻弄蝶、隐纹谷弄蝶、柑橘凤蝶、玉带凤蝶、菜粉蝶、苎麻赤蛱蝶、苎麻黄蛱蝶、豆芫菁、金星步甲、皱鞘步甲、麦穗步甲、沟金针虫、细胸金针虫、谷斑皮蠹、 黑皮蠹、柑橘小吉丁虫、金缘吉丁虫、黄粉虫、黑粉虫、赤拟谷盗、杂拟谷盗、铜绿异丽金龟、暗黑金龟、华北大黑鳃金龟、桑天牛、星天牛、橘褐天牛、桃红颈天牛、大猿叶虫、小猿叶虫、黄守瓜、黄曲条跳甲、绿豆象、豌豆象、蚕豆象、玉米象、米象、小麦叶蜂、梨实蜂、黄带姬蜂、黏虫白星姬蜂、螟蛉悬茧姬蜂、棉铃虫齿唇姬蜂、螟黑点疣姬蜂、蚊、蝇、虻、麦红吸浆虫、麦黄吸浆虫、稻瘿蚊、柑橘大实蝇、瓜实蝇、麦叶灰潜蝇、美洲斑潜蝇、豆秆黑潜蝇、麦秆蝇、种蝇、葱蝇、萝卜蝇、伞裙追寄蝇、玉米螟厉寄蝇、黏虫;Preferably, the plant pests controlled by the insecticidal composition are selected from the group consisting of: red spider, oriental planthopper, cloud locust, Chinese rice blast, Japanese yellow ridge, single locust, oriental carp, rice locust, and tobacco Horse, greenhouse thrips, rice tube thrips, wheat tube horses, greenhouse whitefly, whitefly, black-tailed leafhopper, big green leafhopper, cotton leafhopper, spotted waxhopper, brown planthopper, white-backed planthopper , Laodelphax striatellus, sugarcane, flat-horned corn fly, cotton aphid, wheat bifurcation, wheat long tube, peach aphid, sorghum, radish, blown, sang shield, yam shield, pear round, White wax insects, red wax mites, Korean ball glutinous rice, pear net mites, banana net mites, fine-horned flower buds, tiny flower buds, needle-edge mites, rice spider mites, rice brown mites, rice black mites, rice green mites, Green-spotted scorpion, scorpion scorpion, black-spotted scorpion, large grass scorpion, cypress, Chinese grass scorpion, valley moth, clothing moth, yellow thorn moth, brown thorn moth, spur moth, wheat moth, cotton bollworm, Sweet potato moth, diamondback moth, peach small heartworm, soybean heartworm, peach small heartworm, apple tip leaf moth, brown leaf moth, pseudo-small leaf moth, stem borer, bean pod Corn borer, stem borer, rapeseed meal, rice leaf roller, barley, cotton leaf bark, peach aphid, armyworm, Spodoptera litura, rice bran, cotton small bridgeworm, beet armyworm, giant salamander , cotton bollworm, Ding Ding diamond, small tiger, earth tiger, yellow tiger, poisonous moth, gypsy moth, sweet potato hawk moth, bean hawk moth, straight grain rice butterfly, cryptic valley butterfly, citrus swallow butterfly, jade belt Swallowtail butterfly, cabbage butterfly, ramie red butterfly, ramie butterfly, bean phthalocyanine, Venus carapace, wrinkle sheath, armor, wheat burdock, sphaerocephala, scutellaria, scutellaria, Black scorpion scorpion, citrus small jiding insect, Jinyuan jiding insect, yellow mealworm, black mealworm, red worm, worm, glutinous glutinous, turmeric, black turkey, turkey, turkey Star beetle, orange brown beetle, pink neck beetle, big leafhopper, small leafhopper, yellow squash, yellow stalked beetle, mung bean, pea, broad bean, corn, rice, wheat leaf bee , pear real bee, yellow belt wasp, sticky insect white star wasp, cockroach cockroach cockroach, cotton bollworm, larvae, cockroach, cockroach, cockroach, cockroach, cockroach, cockroach, larvae, larvae, Rice blast, citrus fruit fly, cucurbit fly, larvae, larvae, stalk, black stalk, stalk, fly, onion, radish, umbrella, chasing fly, corn Severely flies, sticky insects;
    优选地,所述杀虫组合物防治的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。Preferably, the plant controlled by the pesticidal composition is selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, tapioca, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut , rapeseed, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, rape, Onions, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
  9. 根据权利要求6或7所述的用途,其特征在于,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述杀菌剂中的任意一种或两种组合形成杀菌组合物用于防治农业和林业以及园艺植物病害,The use according to claim 6 or 7, wherein the isothiazolyl ether methoxy acrylate derivative IV is combined with any one or both of the bactericides to form a bactericidal composition for Control of agricultural and forestry and horticultural plant diseases,
    优选地,所述杀菌剂选自:苯并噻二唑、噻酰菌胺,简写为TDL、噻酰胺、甲噻诱胺、4-甲基-1,2,3-噻二唑-5-甲酸、4-甲基-1,2,3-噻二唑-5-甲酸钠、4-甲基-1,2,3-噻二唑-5-甲酸乙酯、DL-β-氨基丁酸、异噻菌胺,其英文通用名为:isotianil、3,4-二氯异噻唑-5-甲酸、3,4-二氯异噻唑-5-甲酸钠、3,4-二氯异噻唑-5-甲酸乙酯、病毒唑、安托芬、宁南霉素或水杨酸、霜脲氰、福美双、福美锌、代森锰锌、乙磷铝、甲基硫菌灵、百菌清、敌可松、腐霉利、苯锈啶、甲基托布津、托布津、精甲霜灵、氟吗啉、烯酰吗啉、高效甲霜灵、高效苯霜灵、双氯氰菌胺、磺菌胺、甲磺菌胺、噻氟菌胺、氟酰胺、叶枯酞、环丙酰菌胺、环氟菌胺、环酰菌胺、氰菌胺、硅噻菌胺、呋吡菌胺、吡噻菌胺、双炔酰菌胺、苯酰菌胺、甲呋酰胺、萎锈灵、乙菌利、异菌脲、嘧菌酯、醚菌胺、氟嘧菌酯、醚菌酯、苯氧菌胺、肟醚菌胺、啶氧菌酯、唑菌胺酯、肟菌酯、烯肟菌酯、烯肟菌胺、氧环唑、糠菌唑、环丙唑醇、苯醚甲环唑、烯唑醇、高效烯唑醇、氟环唑、腈苯唑、氟喹唑、氟硅唑、粉唑醇、己唑醇、亚胺唑、种菌唑、叶菌唑、腈菌唑、戊菌唑、丙环唑、丙硫菌唑、硅氟唑、戊唑醇、四氟醚唑、***醇、灭菌唑、联苯***醇、噻菌灵、麦穗宁、抑霉唑、高效抑霉唑、 咪鲜胺、氟菌唑、氰霜唑、咪唑菌酮、噁咪唑、稻瘟酯、噁唑菌酮、啶菌噁唑、噁霉灵、噁霜灵、噻唑菌胺、土菌灵、辛噻酮、苯噻硫氰、十二环吗啉、丁苯吗啉、十三吗啉、拌种咯、咯菌腈、氟啶胺、啶斑肟、环啶菌胺、啶酰菌胺、氟啶酰菌胺、啶菌胺、嘧菌环胺、氟嘧菌胺、嘧菌腙、嘧菌胺、嘧霉胺、氯苯嘧啶醇、氟苯嘧啶醇、灭螨猛、二氰蒽醌、乙氧喹啉、羟基喹啉、丙氧喹啉、苯氧喹啉、乙霉威、异丙菌胺、苯噻菌胺、霜霉威、磺菌威、敌瘟磷、异稻瘟净、吡菌磷、甲基立枯磷、灭瘟素、春雷霉素、多抗霉素、多氧霉素、有效霉素、井冈霉素、链霉素、甲霜灵、呋霜灵、苯霜灵、呋酰胺、灭锈胺、多菌灵、苯菌灵、甲基硫菌灵、***酮、乙嘧酚磺酸酯、二甲嘧酚、乙嘧酚、敌菌丹、克菌丹、灭菌丹、乙烯菌核利、氟氯菌核利、菌核净、百菌清、稻瘟灵、稻瘟净、叶枯唑、五氯硝基苯、丙森锌、三乙膦酸铝、硫磺、波尔多液、硫酸铜、氧氯化铜、氧化亚铜、氢氧化铜、苯菌酮、戊菌隆、哒菌酮、四氯苯酞、咯喹酮、螺环菌胺、三环唑、嗪胺灵、多果啶、双胍辛盐、双胍辛胺、氯硝胺、苯磺菌胺、甲苯磺菌胺、吲哚酯、敌磺钠、喹菌酮、烯丙苯噻唑、溴硝醇、碘甲烷、威百亩、敌线酯、棉隆、二氯异丙醚、噻唑磷、硫线磷、丰索磷、虫线磷、苯线磷、灭线磷、除线磷、氯唑磷、丁硫环磷、杀线威、涕灭威、克百威、硫酰氟、二氯丙烯、二氯异烟酸、烯丙异噻唑;Preferably, the bactericide is selected from the group consisting of: benzothiadiazole, thiazide, abbreviated as TDL, thiazamide, methyl thiazide, 4-methyl-1,2,3-thiadiazole-5- Formic acid, sodium 4-methyl-1,2,3-thiadiazol-5-carboxylate, ethyl 4-methyl-1,2,3-thiadiazol-5-carboxylate, DL-β-aminobutyric acid, Isotianil, its common name in English is: isotianil, 3,4-dichloroisothiazol-5-carboxylic acid, 3,4-dichloroisothiazol-5-formate, 3,4-dichloroisothiazol-5- Ethyl formate, ribavirin, antofin, nymidine or salicylic acid, cymoxanil, thiram, thiram, mancozeb, ethylphosphoric acid, thiophanate, chlorothalonil, enemy Cortisone, procymidone, benzopyridin, methyl thiophanate, thiophanate, refined metalaxyl, flumorph, enoylmorpholine, high-performance metalaxyl, high-efficiency benzoxanthin, chloramphenicol, sulfonate Bismuthamide, mesalamide, thifluzamide, fluamide, leaf cumin, cyclopropionamide, cycloflufenamide, fenhexamid, cyanamide, thiastrobin, flufenamide, Pentimidamide, dipropiylamide, benzilamide, mefenamide, wilting, etoxin, iprodione, azoxystrobin, fenfluramine, fluoxastrobin Epoxystrobin, phenoxystrobin, difloxacin, picoxystrobin, pyraclostrobin, trifloxystrobin, enestrobin, enestrobin, oxycyclazole, carbendazole, cyproconazole , difenoconazole, diniconazole, high-efficiency diniconazole, epoxiconazole, nitrile azole, fluoroquinazole, flusilazole, fluconazole, hexaconazole, imidazole, inocastazole, leaf fungus Azole, myclobutanil, penconazole, propiconazole, prothioconazole, silicon fluoride, tebuconazole, tetrafluoroetherazole, triazole alcohol, sterilized azole, biphenyl triazole alcohol, thiabendazole, Maisuining, imazalil, high-efficiency imazalil, Prochloraz, fluconazole, cyanoxazole, imidacloprid, meemazole, rice oxime ester, famoxadone, pyridine oxazole, carbendazim, oxacillin, ethaboxam, carbendazim, sim Thiolone, phenothithiocyanate, dodecamorpholine, butylmorpholine, tridemorpholine, seed dressing, fludioxonil, fluazinam, pyridoxine, cyclosporine, boscalid, Fluazimidamide, acridine, cyprodinil, fluzalazine, azoxystrobin, azoxystrobin, pyrimethanil, chlorpyrimidine, fluoropyrimidinol, chlorpyrifos, dicyandiamide , ethoxyquinoline, hydroxyquinoline, propoxyquinoline, phenoxyquinoline, carbendazim, isopropylidene, phenothimethamine, propamocarb, sulfavir, enemies, and glutinous rice , pyridoxine, methyl chlorpyrifos, quercetin, chun ergmycin, polymycin, polyoxomycin, tyrosin, jinggangmycin, streptomycin, metalaxyl, furosemide, benzene Creaming, furamide, rust-eliminating amine, carbendazim, benomyl, thiophanate-methyl, triadimefon, acetaminophen sulfonate, dipyridamole, pyrethenol, dipyridamole, gram fungus Dan, sterilized Dan, vinyl nucleus, chlorofluorobacteria, sclerotium net, hundred Qing, Dao Lingling, Daojingjing, Yezosin, Pentachloronitrobenzene, Propylene Zinc, Aluminum Triethylphosphinate, Sulfur, Bordeaux Liquid, Copper Sulfate, Copper Oxide, Cuprous Oxide, Copper Hydroxide , benomyl, pentosan, chlorfenapyr, tetrachlorophenyl hydrazine, praziquantel, spirocyclammine, tricyclazole, pyrazinamide, polyglycosidine, biguanide salt, bis-octylamine, chloramine , sulfonamide, toluidine, oxime ester, sodium sulfonate, quinocodone, allyl benzothiazole, bronopol, iodomethane, Weibaimu, enemy ester, cotton, dichloroisopropyl Ether, thiazolyl, thiophosphorus, folsop, phosphorus, benzene, phosphorus, phosphide, phosphatidylcholine, butyl thiophosphorus, chlorpyrifos, aldicarb, carbofuran, Sulfuryl fluoride, dichloropropene, dichloroisonicotinic acid, allylic isothiazole;
    优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在所述杀菌组合物中的总的质量百分含量是1%-90%,Preferably, the total mass percentage of the isothiazolyl ether methoxy acrylate derivative IV in the germicidal composition is from 1% to 90%,
    优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述杀菌剂的比例为质量百分比1%∶99%到99%∶1%;Preferably, the ratio of the isothiazolyl ether methoxy acrylate derivative IV to the bactericide is 1% by mass: 99% to 99%: 1% by mass;
    优选地,所述杀菌组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;Preferably, the bactericidal composition is processed in a dosage form selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous valley, block bait , granular bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, heat Spray, cold spray, aerosol, solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microparticle, trace powder, oil suspension, oil dispersible powder, Thickener, pouring agent, seed coating agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam release agent;
    优选地,所述杀菌组合物防治的植物病害选自:稻苗绵腐病、番茄根腐病、马铃薯晚疫病、烟草黑胫病、谷子白粉病、葡萄霜霉病、莴苣霜霉病、黄瓜霜霉病、黄瓜炭疽病; Preferably, the plant disease controlled by the bactericidal composition is selected from the group consisting of: rice seedling cotton rot, tomato root rot, potato late blight, tobacco black shank, millet powdery mildew, grape downy mildew, lettuce downy mildew, cucumber Downy mildew, cucumber anthracnose;
    优选地,所述杀菌组合物适用的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。Preferably, the bactericidal composition is suitable for plants selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut, Rape, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, rape, onion , garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
  10. 根据权利要求6或7所述的用途,其特征在于,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述抗病毒药剂中的任意一种或两种组合形成抗病毒组合物用于防治农业和林业以及园艺植物病毒病害;The use according to claim 6 or 7, wherein the isothiazolyl ether methoxy acrylate derivative IV is combined with any one or both of the antiviral agents to form an antiviral composition. Used to control agricultural and forestry and horticultural plant virus diseases;
    优选地,所述抗病毒药剂选自:苯并噻二唑、噻酰菌胺,简写为TDL、异噻菌胺,其英文通用名为:isotianil、4-甲基-1,2,3-噻二唑-5-甲酸、4-甲基-1,2,3-噻二唑-5-甲酸钠、4-甲基-1,2,3-噻二唑-5-甲酸乙酯、3,4-二氯异噻唑-5-甲酸、3,4-二氯异噻唑-5-甲酸钠、3,4-二氯异噻唑-5-甲酸乙酯、DL-β-氨基丁酸、病毒唑、安托芬、宁南霉素、噻酰胺、甲噻诱胺或水杨酸、嘧肽霉素、二氯异烟酸、烯丙异噻唑、井冈羟胺、井冈霉素;Preferably, the antiviral agent is selected from the group consisting of: benzothiadiazole, thiazide, abbreviated as TDL, isotianil, and its common name in English is: isotianil, 4-methyl-1,2,3- Thiadiazole-5-carboxylic acid, sodium 4-methyl-1,2,3-thiadiazole-5-carboxylate, ethyl 4-methyl-1,2,3-thiadiazole-5-carboxylate, 3, 4-Dichloroisothiazol-5-carboxylic acid, 3,4-dichloroisothiazol-5-formate, 3,4-dichloroisothiazol-5-carboxylic acid ethyl ester, DL-β-aminobutyric acid, ribavirin, Antofin, ningnanmycin, thiazamide, methyl thiazide or salicylic acid, glutathione, dichloroisonicotinic acid, allylisothiazole, Jinggang hydroxylamine, Jinggangmycin;
    优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在所述抗病毒组合物中的总的质量百分含量是1%-90%,Preferably, the total mass percentage of the isothiazolyl ether methoxy acrylate derivative IV in the antiviral composition is from 1% to 90%,
    优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述抗植物病毒剂的比例为质量百分比1%∶99%到99%∶1%;Preferably, the ratio of the isothiazolyl ether methoxy acrylate derivative IV to the anti-plant virus agent is 1% by mass: 99% to 99%: 1% by mass;
    优选地,所述抗病毒组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸汽释放剂;Preferably, the antiviral composition is processed in a dosage form selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous valley, lumps Bait, granular bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, Hot mist, cold spray, aerosol, solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microparticle, trace powder, oil suspension, oil dispersible powder , thickener, pouring agent, seed coating agent, smear agent, film forming oil agent, ultra low volume liquid agent, steam release agent;
    优选地,所述抗病毒组合物防治的病毒病害选自:水稻矮缩病、黄矮病、条纹叶枯病、番茄蕨叶病毒病、辣椒花叶病毒病、烟草脉坏死病毒病、玉米矮花叶病、花椰菜花叶病毒、柑橘病毒病、建兰花叶病毒、建兰环斑病毒;Preferably, the viral disease controlled by the antiviral composition is selected from the group consisting of rice dwarf disease, yellow dwarf disease, stripe leaf blight, tomato fern leaf virus disease, pepper mosaic virus disease, tobacco vein necrosis virus disease, corn dwarf Mosaic disease, cauliflower mosaic virus, citrus virus disease, broccoli virus, Jianlan ring spot virus;
    优选地,所述抗病毒组合物用于防治的植物选自:稻谷、小麦、大麦、燕麦、 玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。Preferably, the plant for controlling the antiviral composition is selected from the group consisting of: rice, wheat, barley, oats, Corn, sorghum, sweet potato, potato, cassava, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut, rape, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillaria, rubber, coconut , oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, mountain Wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
  11. 根据权利要求6或7所述的用途,其特征在于,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述杀螨剂中的任意一种或两种组合形成杀螨组合物用于防治农业和林业以及园艺植物螨害;The use according to claim 6 or 7, wherein the isothiazolyl ether methoxy acrylate derivative IV is combined with any one or both of the acaricides to form a miticide composition Used to control agricultural and forestry and horticultural plant damage;
    优选地,所述杀螨剂选自:***锡、三环锡、苯丁锡、三磷锡、毒虫畏、甲基毒虫畏、巴毒磷、敌敌畏、庚烯磷、速灭磷、久效磷、二溴磷、毒死蜱、嘧啶磷、氯甲亚胺硫磷、氧乐果、敌杀磷、乙硫磷、马拉硫磷、虫螨畏、伏杀硫磷、辛硫磷、甲基嘧啶硫磷、喹硫磷、治螟磷、***磷、蚜灭多、水胺硫磷、甲胺磷、胺丙畏、氯亚胺硫磷、亚胺硫磷、氟丙菊酯、联苯菊酯、氯氟氰菊酯、精高效氯氟氰菊酯、甲氰菊酯、氟氰戊菊酯、氟氯苯菊酯、氟胺氰菊酯、溴氟菊酯、联苯肼酯、苯硫威、涕灭威、丁酮威、杀线威、抗虫威、久效威、苯菌灵、氯灭杀威、克百威、丁硫克百威、速灭威、蜱虱威、伐虫脒、单甲脒、杀螨脒、双甲脒、杀虫脒、苯甲酸苄酯、溴螨酯、丁氟螨酯、灭螨醌、氟蚜螨、氟虫脲、浏阳霉素、虫螨霉素、苏云金素、杀螨素、浏阳霉素、阿维菌素、多拉菌素、埃普利诺菌素、伊维菌素、赛拉菌素、莫西菌素、除虫菊素、烟碱、苦参碱、印楝素、鱼藤酮、吡螨胺、哒螨酮、唑螨酯、四螨嗪、炔螨特、噻螨酮、螺螨酯、嘧螨酯、杀螨酯、克螨特、哒螨灵;Preferably, the acaricide is selected from the group consisting of: triazole tin, tricyclotin, phenbutyltin, triphosphorus, chlorpyrifos, methyl chlorpyrifos, phytophos, dichlorvos, heptene phosphorus, quick-killing phosphorus, long time Phosphorus, dibromophosphorus, chlorpyrifos, pyrimidine, chloromethylimine, omethoate, chlorpyrifos, ethion, malathion, worm, phoxim, phoxim, Pyrithione, quetiapine, strontium phosphate, triazophos, quenching, acesulfame, methamidophos, acesulfame, chloroimidate, imipenem, flumethrin, Bifenthrin, cyhalothrin, cyhalothrin, fenpropathrin, fluvalerate, flumethrin, fluvalinate, bifenthrin, biphenyl hydrazine Ester, phenylthiocarb, aldicarb, butanone, chlorpyrifos, anti-insect, long-acting, benomyl, chlorhexidine, carbofuran, butyl thiocarb, fast-acting, 蜱Converse, worm, monomethyl hydrazine, acaricidal, amitraz, chlorpyrifos, benzyl benzoate, bromo oxime ester, butyl fluoro ester, guanidine, fluoranthene, flubenzuron, Liuyang Neomycin, echinomycin, sulphate, acaricidin, liuyangmycin Avermectin, doramectin, eplenomycin, ivermectin, serramycin, moxidectin, pyrethrin, nicotine, matrine, azadirachtin, rotenone, pyridoxine Amine, anthrone, oxazolidine, tetrazine, alkyne, thiazolone, spirodecyl ester, pyridoxine, acaricidal ester, ketone, hydrazine;
    优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ在所述杀螨组合物中的总的质量百分含量是1%-90%,Preferably, the total mass percentage of the isothiazolyl ether methoxy acrylate derivative IV in the acaricidal composition is from 1% to 90%,
    优选地,所述的异噻唑肟醚甲氧基丙烯酸酯衍生物Ⅳ与所述杀螨剂的比例为质量百分比1%∶99%到99%∶1%;Preferably, the ratio of the isothiazolyl ether methoxy acrylate derivative IV to the acaricide is 1% by mass: 99% to 99%: 1% by mass;
    优选地,所述杀螨组合物加工的剂型选自:种子处理乳剂、水乳剂、微乳剂、悬乳剂、胶囊悬浮剂、水溶性粒剂、细粒剂、可溶性浓剂、毒谷、块状毒饵、粒状毒饵、片状毒饵、浓毒饵、缓释块、静电喷雾剂、水包油乳剂、烟雾罐、烟雾烛、烟雾筒、烟雾棒、烟雾片、烟雾丸、发气剂、油膏、热雾剂、冷雾剂、气雾剂、固/液混合装剂、液/液混合装剂、固/固混合装剂、药漆、微粒剂、追踪粉剂、油悬剂、油分散性粉剂、浓胶剂、泼浇剂、种衣剂、涂抹剂、成膜油剂、超低容量液剂、蒸 汽释放剂;Preferably, the dosage form processed by the acaricidal composition is selected from the group consisting of: seed treatment emulsion, water emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous valley, block Bait, granular bait, flake bait, concentrated bait, slow release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gas generator, ointment, Hot mist, cold spray, aerosol, solid/liquid mixed charge, liquid/liquid mixed charge, solid/solid mixed charge, lacquer, microparticle, trace powder, oil suspension, oil dispersible powder , thickener, pouring agent, seed coating agent, smear agent, film forming oil agent, ultra low volume liquid agent, steaming Vapor release agent;
    优选地,所述杀螨组合物防治的螨害选自:螨害选自叶螨科、细须螨科、呋线螨、瘿螨科、红叶螨属、瘿螨科的害螨,这些害螨是世界性农业害螨、林业害螨、园艺害螨和卫生害螨;Preferably, the cockroach damage controlled by the acaricidal composition is selected from the group consisting of: the mites are selected from the group consisting of the genus Aphididae, the genus Diptera, the eucalyptus, the genus Eucalyptus, the genus Eucalyptus, and the mites. World agricultural pests, forest pests, horticultural pests and health hazards;
    优选地,所述杀螨组合物用于防治的植物选自:稻谷、小麦、大麦、燕麦、玉米、高粱、甘薯、马铃薯、木薯、大豆、荷兰豆、蚕豆、豌豆、绿豆、小豆、棉花、蚕桑、花生、油菜、芝麻、向日葵、甜菜、甘蔗、咖啡、可可、人参、贝母、橡胶、椰子、油棕、剑麻、烟草、番茄、辣椒、萝卜、黄瓜、白菜、芹菜、榨菜、甜菜、油菜、葱、大蒜、西瓜、甜瓜、哈密瓜、木瓜、苹果、柑桔和桃树、茶、山野菜、竹笋、啤酒花、胡椒、香蕉、番木瓜、兰花、盆景。 Preferably, the plant for controlling the acaricidal composition is selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture , peanuts, rapeseed, sesame, sunflower, beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, Rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
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