WO2017129122A1 - Dérivés de strobilurine d'étheroxime d'isothiazole, leur procédé de préparation et leurs utilisations - Google Patents

Dérivés de strobilurine d'étheroxime d'isothiazole, leur procédé de préparation et leurs utilisations Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
agent
smoke
group
rice
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2017/072557
Other languages
English (en)
Chinese (zh)
Inventor
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nankai University
Original Assignee
Nankai University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201610185795.7A external-priority patent/CN106995417B/zh
Application filed by Nankai University filed Critical Nankai University
Priority to US16/073,089 priority Critical patent/US10906880B2/en
Publication of WO2017129122A1 publication Critical patent/WO2017129122A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C07D275/03—Heterocyclic 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.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne des dérivés de strobilurine d'étheroxime d'isothiazole, leur procédé de préparation et leurs utilisations. La présente invention concerne des dérivés de strobilurine d'étheroxime de 3,4-dichloroisothiazole de structure chimique générale présentée en IV. La présente invention concerne des composés de structure générale indiquée, leur procédé de synthèse et leurs utilisations comme pesticides, fongicides et agents antiviraux pour les plantes, leurs utilisations et un procédé de préparation des dérivés utilisés en association avec des excipients ou des synergistes acceptables sur le plan agricole et avec des pesticides, fongicides, agents antiviraux pour les plantes et acaricides commercialisés pour la prévention et le traitement des nuisibles, des maladies ou des virus touchant les végétaux du domaine agricole, forestier ou horticole.
PCT/CN2017/072557 2016-01-26 2017-01-25 Dérivés de strobilurine d'étheroxime d'isothiazole, leur procédé de préparation et leurs utilisations Ceased WO2017129122A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/073,089 US10906880B2 (en) 2016-01-26 2017-01-25 Kind of isothiazole oxime ether-containing strobilurin derivatives and its preparation methods and application

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201610058411.5 2016-01-26
CN201610058411 2016-01-26
CN201610185795.7A CN106995417B (zh) 2016-01-26 2016-03-25 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
CN201610185795.7 2016-03-25

Publications (1)

Publication Number Publication Date
WO2017129122A1 true WO2017129122A1 (fr) 2017-08-03

Family

ID=59397458

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/072557 Ceased WO2017129122A1 (fr) 2016-01-26 2017-01-25 Dérivés de strobilurine d'étheroxime d'isothiazole, leur procédé de préparation et leurs utilisations

Country Status (1)

Country Link
WO (1) WO2017129122A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113729074A (zh) * 2021-10-11 2021-12-03 安徽农业大学 一种用于防治梨炭疽病的保鲜剂及其应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1042900A (zh) * 1988-11-21 1990-06-13 帝国化学工业公司 杀真菌剂
CA2005345A1 (fr) * 1988-12-29 1990-06-29 Hans Peter Isenring Derives de l'acide acrylique
CN1065658A (zh) * 1991-01-30 1992-10-28 帝国化学工业公司 杀真菌剂
WO1992018487A1 (fr) * 1991-04-15 1992-10-29 Zeneca Limited 2-phenyl-3-methoxypropenoates substitues utilises comme fongicides
CN1191670A (zh) * 1998-02-10 1998-09-02 化工部沈阳化工研究院 不饱和肟醚类杀虫、杀真菌剂
CN1306506A (zh) * 1998-07-16 2001-08-01 诺瓦提斯公司 苯基－甲氧亚氨基－乙酸衍生物农药
WO2008104101A1 (fr) * 2007-02-28 2008-09-04 Sinochem Corporation Composés de 1-(3-méthyl-4-fluoro)phényl-1-méthylcyclopropane et leur utilisation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1042900A (zh) * 1988-11-21 1990-06-13 帝国化学工业公司 杀真菌剂
CA2005345A1 (fr) * 1988-12-29 1990-06-29 Hans Peter Isenring Derives de l'acide acrylique
CN1065658A (zh) * 1991-01-30 1992-10-28 帝国化学工业公司 杀真菌剂
WO1992018487A1 (fr) * 1991-04-15 1992-10-29 Zeneca Limited 2-phenyl-3-methoxypropenoates substitues utilises comme fongicides
CN1191670A (zh) * 1998-02-10 1998-09-02 化工部沈阳化工研究院 不饱和肟醚类杀虫、杀真菌剂
CN1306506A (zh) * 1998-07-16 2001-08-01 诺瓦提斯公司 苯基－甲氧亚氨基－乙酸衍生物农药
WO2008104101A1 (fr) * 2007-02-28 2008-09-04 Sinochem Corporation Composés de 1-(3-méthyl-4-fluoro)phényl-1-méthylcyclopropane et leur utilisation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113729074A (zh) * 2021-10-11 2021-12-03 安徽农业大学 一种用于防治梨炭疽病的保鲜剂及其应用

Similar Documents

Publication Publication Date Title
CN103172613B (zh) 一类含n-氰基砜(硫)亚胺的邻甲酰氨基苯甲酰胺衍生物及其制备方法和用途
CN103467463B (zh) 一类木脂素类衍生物及其制备方法和用途
CN103450154B (zh) 一类含硫醚、n-氰基硫(砜)亚胺结构的取代吡唑甲酰胺类双酰胺衍生物及其制备方法和用途
CN107619408B (zh) 一类氨基噻唑羧酸衍生物及其制备方法和用途
WO2017129113A1 (fr) Composés de bromohexahydroindanone, leur procédé de préparation et leurs utilisations
CN104650062B (zh) 一类含氮杂环的噻唑衍生物及其制备方法和用途
CN103172614B (zh) 一类含砜(硫)亚胺的邻甲酰氨基苯甲酰胺衍生物及其制备方法和用途
CN104650061B (zh) 一类噻唑醛肟醚类化合物及其制备方法和用途
CN109970650A (zh) 一类吡唑苯基甲酰胺类衍生物及其制备方法和用途
CN103483287B (zh) 一类含3,4-二氯异噻唑的双酰胺类化合物及其制备方法和用途
CN102382108B (zh) 一类含1,2,3-噻二唑亚甲基的四氮唑类化合物及其制备方法和用途
CN102417505B (zh) 含甲基-1，2，3-噻二唑的四氮唑类化合物及其制备方法和用途
WO2017129121A1 (fr) Dérivés de strobilurine d'étheroxime de thiadiazole, leur procédé de préparation et leur utilisation
CN104649996B (zh) 一类异噻唑肟醚衍生物及其制备方法和用途
CN103641795B (zh) 一类含1，2，3-噻二唑的苯乙酮衍生物及其制备方法和用途
CN102816135B (zh) 一类5-甲基-1，2，3-噻二唑联-1，3-4-噻二唑衍生物及其制备方法和用途
CN110041260A (zh) 一类多取代吡唑酰胺衍生物及其制备方法和用途
CN109970653A (zh) 一类含二氟甲基吡唑的甲氧基丙烯酸酯衍生物及其制备方法和用途
CN106995417A (zh) 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
CN104650059B (zh) 一类噻唑酮肟醚类衍生物及其制备方法和用途
CN103483288B (zh) 一类3，4-二氯异噻唑双酰肼类化合物及其制备方法和用途
CN107226812A (zh) 一类哌啶噻唑肟醚甲氧基丙烯酸酯衍生物及其制备方法和用途
CN107459509B (zh) 一类含氮含硫磺酰亚胺衍生物及其制备方法和用途
CN105503708B (zh) 一类含二氟乙基的杂环化合物及其制备方法和用途
CN103214476B (zh) 一类含4-甲基-1,2,3-噻二唑的甲脒衍生物及其制备方法和用途

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17743737

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17743737

Country of ref document: EP

Kind code of ref document: A1