CN112358444A - Oxime ether heterocyclic formamide derivatives, and preparation method and application thereof - Google Patents

Oxime ether heterocyclic formamide derivatives, and preparation method and application thereof Download PDF

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CN112358444A
CN112358444A CN202011199891.XA CN202011199891A CN112358444A CN 112358444 A CN112358444 A CN 112358444A CN 202011199891 A CN202011199891 A CN 202011199891A CN 112358444 A CN112358444 A CN 112358444A
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oxime ether
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范志金
郝泽生
陈浩崟
吕游
齐欣
高卫
刘笑宇
李坤
张越
陈蕾
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Nankai University
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    • C07—ORGANIC CHEMISTRY
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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    • C07D—HETEROCYCLIC COMPOUNDS
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    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • 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

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  • Agronomy & Crop Science (AREA)
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Abstract

The invention provides oxime ether heterocyclic formamide derivatives, a preparation method and application thereof, and particularly relates to oxime ether heterocyclic formamide derivatives, wherein the chemical structure general formula of the oxime ether heterocyclic formamide derivatives is shown as formula I:

Description

Oxime ether heterocyclic formamide derivatives, and preparation method and application thereof
Technical Field
The technical scheme of the invention relates to an oxime ether heterocyclic carboxamide compound, in particular to a (Z) -N- (2- (1- ((benzyloxy) imino) ethyl) phenyl heterocyclic carboxamide derivative.
Background
The oxime ether derivatives not only have wide medical application, but also are important active compounds in pesticides (Liu' ei et al, university of Master China (Nature science edition), 2004, 38 (1): 66-68); strobilurin fungicides and acaricides such as represented by trifloxystrobin (trifloxystrobin) and fluacrypyrin (fluacryprin); pyrimidine ether herbicides represented by pyribenzoxim (pyribenzoxim). Because the compounds have good biological activities of insect killing, mite killing, sterilization, weeding, detoxification, synergy and the like, and most of the compounds have the advantages of high efficiency, low toxicity, low residue and the like, the oxime ether structure is still often selected as an effective active group in the creation of new pesticides.
Pesticides containing amide structures have been the focus of research and are widely used in the variety structures of herbicides, insecticides and fungicides. The amide herbicides are efficient and high-selectivity herbicides. The herbicide has the advantages of wide herbicidal spectrum, low price, convenient application and the like, and mainly comprises alachlor (alachlor), napropamide (napropamide), metolachlor (metolachlor) and the like (Wangcao, et al, food safety quality detection bulletin, 2019, 10 (17): 5590-5591). The ryanodine receptor inhibitor pesticide raises the development of a hot tide due to a unique action mechanism and ultrahigh insecticidal activity and safety. Mainly comprises chlorantraniliprole (chlorantraniliprole), cyantraniliprole (cyantraniliprole) and the like. The succinate dehydrogenase inhibitor bactericide has no cross resistance with the methoxyl acrylate bactericide due to the unique action site, and effectively solves the problem of resistance (enemy is the winner, etc., modern pesticides, 2014, 13 (6): 1-7).
The amide structure promotes the production of a batch of new pesticides, and forms a new pesticide series. Needless to say, there are also newer amide pesticides developed and marketed. In order to find and discover pesticide lead and candidate compounds which are more efficient, broad-spectrum, low-toxicity, low-ecological risk and free of cross resistance, the invention introduces the oxime ether into the lead structure of the difluoropyrazole formamide, designs and synthesizes oxime ether heterocyclic formamide derivatives, and screens and evaluates the biological activity of the system.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a synthesis method of a novel oxime ether heterocyclic formamide derivative, provides a method for regulating and controlling the biological activity of agricultural, horticultural and sanitary and forestry plant pests and plant pathogens by using the compound and a determination method thereof, and also provides application of the compound in the agricultural field, the horticultural field, the forestry field and the sanitary field.
The technical scheme adopted by the invention for solving the technical problem is as follows: the oxime ether heterocyclic carboxamide compound with insecticidal activity, acaricidal activity, bactericidal activity, plant virus resistance activity and plant disease resistance activity induced in the agricultural field, the horticultural field and the forestry field has a chemical structural general formula shown in I:
Figure BSA0000223369140000021
wherein A is selected from: 2-chloropyridyl, 2-difluoromethylpyridyl, 3, 4-dichloroisothiazolyl, 2-difluoromethyl-4-methylpyrazolyl; r1Selected from: hydrogen, 4-fluoro; r2Selected from: hydrogen, methyl; r3Selected from: hydrogen, 4-fluoro, 4-methyl, 4-trifluoromethyl, 2-chloro-4-fluoro.
The synthesis route of the oxime ether heterocyclic formamide derivative I and the intermediate thereof is as follows:
Figure BSA0000223369140000022
synthetic route to Compounds I
The synthesis method of the oxime ether heterocyclic formamide derivative I comprises the following steps:
A. preparation of compound 3:
and (3) taking substituted benzyl bromide to be placed in a reaction bottle, adding N-hydroxyphthalimide and N, N-dimethylformamide, adding NaOH under stirring, reacting at 80 ℃, and finishing the reaction. Cooling the reaction liquid, adding water, stirring for 10 minutes, and filtering; extracting solid dichloromethane and water, washing with saturated saline solution, drying with sodium sulfate, filtering, and concentrating under reduced pressure to obtain white solid 3;
B. preparation of compound 4:
and (3) putting the compound 3 into a reaction bottle, adding absolute ethyl alcohol, adding 80% hydrazine hydrate under stirring, and carrying out reflux reaction to finish the reaction. Filtering, and concentrating under reduced pressure to obtain yellowish oily liquid 4;
C. preparation of compound 6:
and putting the compound 4 into a reaction bottle, adding the compound 5 and absolute ethyl alcohol, adding 2-3 drops of concentrated hydrochloric acid, and carrying out reflux reaction. Finishing the reaction; distilling under reduced pressure to remove ethanol, extracting with dichloromethane and water, and mixing organic phases; washing with saturated saline solution, drying with sodium sulfate, filtering, and separating by column chromatography to obtain yellowish oily liquid compound 6;
D. preparation of compound I:
adding acid into dichloromethane, adding oxalyl chloride and 2 drops of N, N-dimethylformamide, reacting at room temperature for 2 hr, removing oxalyl chloride and CH2Cl2Standby; adding Compound 6 to CH2Cl2Adding triethylamine, dissolving the reserved acyl chloride in dichloromethane, slowly dropwise adding the mixture into the reaction solution, reacting at normal temperature, and finishing the reaction; adding water, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with sodium sulfate, filtering, concentrating the filtrate to remove the solvent, and purifying by column chromatography to obtain compound I;
as a preferred embodiment of the present invention, the synthesis procedure of the oxime ether containing heterocyclic carboxamide derivative is as follows:
taking 11.69 mmol of substituted benzyl bromide, adding 11.69 mmol of N-hydroxyphthalimide and 25ml of N, N-dimethylformamide into a reaction bottle, adding 11.69 mmol of NaOH while stirring, reacting at 80 ℃, and detecting by TLC to finish the reaction. After the reaction solution was cooled, 20 ml of water was added, stirred for 10 minutes, and filtered. CH for solid2Cl2∶H2Dissolving in 1: 1 solution of O, and dissolving in CH2Cl2Extracting for 3 times, washing with saturated saline solution, drying with sodium sulfate, filtering, and concentrating under reduced pressure to obtain white solid 2- (substituted benzyloxy) isoindoline-1, 3-dione.
Adding 7.11 mmol of 2- (substituted benzyloxy) isoindoline-1, 3-diketone into a reaction bottle, adding 15 ml of absolute ethyl alcohol, adding 10.66 mmol of 80% hydrazine hydrate while stirring, carrying out reflux reaction, and finishing TLC detection reaction; filtering, and concentrating under reduced pressure to obtain a light yellow oily liquid O-substituted benzylhydroxylamine.
Taking 1.96 mmol of substituted O-benzylhydroxylamine to be put into a reaction bottle, adding 1.96 mmol of substituted 2-aminoacetophenone and 15 ml of absolute ethyl alcohol, adding 2-3 drops of concentrated hydrochloric acid, and carrying out reflux reaction; the TLC detection shows that the reaction is finished. Distilling under reduced pressure to remove ethanol, adding CH2Cl2Water extraction and merging organic phases. Washing with saturated brine, drying with sodium sulfate, filtering, and making into column colorSpectrum separation to obtain light yellow oily liquid (E) -1- (2-aminophenyl) ethyl-1-ketone-O-substituted benzyl oxime.
0.51 mmol of 2-difluoromethylnicotinic acid was taken in a reaction flask, and 1.52 mmol of oxalyl chloride and 10 ml of CH were added2Cl2Adding 2 drops of N, N-dimethylformamide, reacting at normal temperature for 2h, removing oxalyl chloride and CH2Cl2Standby; 0.51 mmol of (E) -1- (2-aminophenyl) ethyl-1-one-O-substituted benzyl oxime was put in a reaction flask, and 10 ml of CH was added2Cl2And 1.52 mmol triethylamine, the acid chloride to be used was dissolved in CH2Cl2Slowly dripping the mixture into the reaction solution under the ice bath condition, reacting at normal temperature, and detecting by TLC to finish the reaction; adding water and CH2Cl2Extracting for 3 times, combining organic phases, washing with saturated brine, drying with sodium sulfate, filtering, and concentrating under reduced pressure to obtain light yellow solid (Z) -N- (2- (1- ((substituted benzyloxy) imino) ethyl) phenyl) -2- (difluoromethyl) nicotinamide.
Wherein A is selected from: 2-chloropyridyl, 2-difluoromethylpyridyl, 3, 4-dichloroisothiazolyl, 2-difluoromethyl-4-methylpyrazolyl; r1Selected from: hydrogen, 4-fluoro; r2Selected from: hydrogen, methyl; r3Selected from: hydrogen, 4-fluoro, 4-methyl, 4-trifluoromethyl, 2-chloro-4-fluoro.
The invention provides application of the oxime ether heterocyclic carboxamide derivative I in preparation of fungicides.
The invention provides application of the oxime ether heterocyclic carboxamide derivative I in preparation of an anti-tobacco mosaic virus agent.
The invention provides application of the oxime ether heterocyclic carboxamide derivative I in preparation of a plant activator for inducing tobacco to resist tobacco mosaic virus.
The invention provides application of the oxime ether heterocyclic carboxamide derivative I in preventing and treating agricultural and forestry and horticultural plant insect pests.
The oxime ether heterocyclic carboxamide derivative I is co-administered with an agrochemical; the agrochemical is selected from: one or more of insecticide, bactericide, plant virus resisting agent and acaricide.
The oxime ether heterocyclic carboxamide derivative I and any one or two of the insecticides are combined to form an insecticidal composition for preventing and treating agricultural and forestry and horticultural plant insect pests;
the insecticide is selected from: methoprene, diazinon, acetamiprid, emamectin benzoate, milbemectin, abamectin, pleocidin, metaflumethrin, meperfluthrin, cyfluthrin, beta-cypermethrin, lambda-cyhalothrin, permethrin, allethrin, bifenthrin, permethrin, flumethrin, cyfluthrin, imidacloprid, nitenpyram, imidaclothianidin, thiacloprid, thiamethoxam, clothianidin, dinotefuran, cotinine, dinotefuran, diflubenzuron, chlorbenzuron, tefluazuron, flufenoxuron, lufenuron, chlorflufenoxuron, fluazuron, diflubenzuron, fluazuron, tezine, fluazuron, tezine, teflufenozide, tebufenozide, tezine, flufenozide, tebufenozide, tezine, tebufenozide, methoxyfenozide, chromafenozide, dichlorvos, quinalphos, pyridaphenthion, cicada powder, carbaryl, pirimicarb, metolcarb, isoprocarb, cartap, fenobucarb, tetrafenozide, fenitrothion, hexythiazox, carbaryl, fenisobromolate, hexythiazox, pyridate, clofentezine, spirodiclofen, spirotetramat, azocyclobutazine, buprofezin, monosultap, dimehypo, chlorantraniliprole, tetrachlorantranilide, flubendiamide, cyantraniliprole, butenenitrile, tolfenpyrad, chlorfenapyr, pyrazofos, pyrazinone, etoxazole, tebufenpyrad, pyridaben, emamectin, and pentapyraflufen;
the mass percentage of the oxime ether heterocyclic formamide derivatives I in the insecticidal composition is 1% -90%; preferably, the ratio of the oxime ether heterocyclic formamide derivatives I to the pesticide is 1 percent to 99 percent to 1 percent in percentage by mass;
the insecticide composition is processed into a dosage form selected from the group consisting of: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents;
the plant insect pests controlled by the insecticidal composition are selected from: meadow spodoptera, red spider, east Asian migratory locust, spruce-bug, Chinese rice locust, japanese yellow-back locust, single-prick mole cricket, oriental mole cricket, rice thrips, thrips tabaci, green house thrips, rice straw thistle, wheat simple pipe thrips, green house whitefly, bemisia tabaci, black tail hopper, big leaf hopper, cotton leafhopper, lesser leafhopper, brown plant hopper, white back plant hopper, gray plant hopper, sugarcane flat leaf planthopper, cotton aphid, binary wheat aphid, wheat straw aphid, peach aphid, sorghum aphid, radish aphid, mealybug, lybug, stinkbug, arrowhead bug, round scale, white insect, red wax insect, red worm, mealybug, pear net, banana net bug, tiny flower bug, laceleaf fly, green fly, rice moth, black armyworm, black fly, black rice moth, black armyworm, black rice moth, black rice plant, pink bollworm, sweet potato wheat moth, diamond back moth, peach fruit borer, soybean pod borer, peach fruit borer, apple tip leaf roller moth, brown banded leaf roller moth, pardos leaf roller moth, striped rice borer, pod borer, corn borer, yellow rice borer, cabbage moth, rice leaf roller borer, striped rice borer, cotton leaf borer, peach borer, armyworm, prodenia litura, rice bollworm, cotton small bridgehead moth, beet armyworm, sesamia inferen, cotton bollworm, Dinodon diamond-back moth, agrotis, yellow cutworm, robber venom moth, gypsy moth, sweet potato hawkmoth, bean hawkmoth, straight grain rice skipper, cryptophyte butterfly, caeruleuca, caeruleuciscus nigra, yellow mealyratus caeruleucade, yellow meadowrue, yellow rice beetle, yellow tiger, red ramie yellow vanne, yellow rice borer, yellow rice, Tribolium castaneum, verdigris, black tortoise, branchia palustris, longicorn beetle, pink neck longicorn beetle, ape leaf worm, yellow melon, flea beetle, mung bean weevil, pea weevil, broad bean weevil, corn weevil, rice weevil, wheat leaf bee, pear fruit bee, yellow stripe wasp, armyworm white star ichneumonid, sandfly bractenoconid, cotton bollworm tooth-lipped ichneumonid, borer black spot wart, mosquito, fly, horsefly, red mud fly, yellow leaf sucking serous, rice gall mosquito fly, citrus fruit fly, melon fruit fly, wheat leaf gray fly, American fly, black stalk black fly, wheat stem fly, seed fly, onion fly, radish skirt, eupatorium, corn borer, and armyworm;
the plants controlled by the insecticidal composition are selected from the following plants: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
The oxime ether heterocyclic carboxamide derivative I and any one or two of the bactericides are combined to form a bactericidal composition for preventing and treating agricultural and forestry and horticultural plant diseases;
the bactericide is selected from: benzothiadiazole, tiadinil, thianamide, methicillin, 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid, 4-methyl-1, 2, 3-thiadiazole-5-sodium formate, 4-methyl-1, 2, 3-thiadiazole-5-ethyl formate, DL-beta-aminobutyric acid, isotianil, 3, 4-dichloroisothiazole-5-carboxylic acid, 3, 4-dichloroisothiazole-5-sodium formate, 3, 4-dichloroisothiazole-5-ethyl formate, ribavirin, antofine, ningnanmycin or salicylic acid, cyanamide, thiram, ziram, mancozeb, fosetyl, thiophanate-methyl, chlorothalonil, chlormadinone, procymidone, fenpropidium rust, Thiophanate methyl, thiophanate, metalaxyl-M, flumorph, dimethomorph, metalaxyl-M, benalaxyl-M, diclocyanamide, sulfentram, sulfsulfamide, thifluzamide, folpet, cyprodinil, cyhalodiamide, silthiopham, carboxin, oxim-methyl, mefuram, fenazamide, flutolanil, furametpyr, thifluzamide, boscalid, penthiopyrad, isopyrazamide, bixafen, fluopyram, fluxastrobin, fluxapyroxad, flufenapyr, benconazole, iprovalicarb, flutriafolan, flufenpyrazamide, flufenacetmid, fluoxastrobin, fenhexamid, iprodione, trifloxystrobin, kresoximtrobin, trifloxystrobin, fenstrobin, fenstrobilurin, fenpyraclostrobin, fluoxastrobin, fluoxastrobilurin, fluoxastrobil, Enestroburin, dimethomorph, difenoconazole, bromhexine, epoxiconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole, difenoconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, imazalil, prochloraz, triflumizole, cyazofamid, fenamidone, imidazole, pefurazoate, famoxadone, pyridinozole, prodiamine, ethaboxam, hymexazol, penoxsulam, fenthion, fenpropimorph, tridemorph, fenpyroxanil, fluazinam, fenpropiconazole, fenpyrazamide, fluazinam, cyprodinil, flufenamidone, fenpyrad, fenpyro, Mepanipyrim, pyrimethanil, fenarimol, fluoropyrimidinol, mefenamate, dithianon, ethoxyquin, hydroxyquinoline, propoxymine, phenoxyquinoline, diethofencarb, iprovalicarb, benthiavalicarb, propamocarb, sulbencarb, edifenphos, iprobenfos, pyrazofos, tolclofos-methyl, blasticidin, kasugamycin, polyoxin, validamycin, streptomycin, metalaxyl, furalaxyl, benomyl, thiophanate-methyl, triadimefon, bupirimate, dimethirimol, ethirimol, captan, folpet, vinclozolin, fluocinolone, dimethachlon, chlorothalonil, isoprothiolane, pefurazone, bismerzole, quintozene, propineb, fosetyl, sulfur, polidocusate, cuprous oxide, cupric chloride, cupric oxide, cupric hydroxide, Metrafenone, pencycuron, pyridaben, tetrachlorophthalide, pyroquilon, spiroxamine, tricyclazole, azinam, dodine, diguanidinium salt, diguanidinium, niclosamide, bentiamine, tolfenpyrad, indole ester, sodium disulfate, quinconazole, probenazole, bronopol, methyl iodide, metam, dichloline ester, dazomet, dichloroisopropyl ether, fosthiazate, fosfenthion, fenamiphos, thiothifenthion, methiocarb, sulfuryl fluoride, dichloropropylene, dichloroisonicotinic acid, allylisothiazole;
the oxime ether heterocyclic carboxamide derivative I accounts for 1 to 90 percent of the total mass of the sterilization composition; the ratio of the oxime ether heterocyclic formamide derivatives I to the bactericide is 1 to 99 to 1 percent by mass percent;
the bactericidal composition is processed into a dosage form selected from the group consisting of: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents;
the plant diseases controlled by the bactericidal composition are selected from: rice seedling blight, tomato root rot, potato late blight, tobacco black shank, millet powdery mildew, grape downy mildew, lettuce downy mildew, cucumber anthracnose;
the plants suitable for the bactericidal composition are selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
The oxime ether heterocyclic carboxamide derivative I and any one or two of the antiviral medicaments are combined to form an antiviral composition for preventing and treating virus diseases of agricultural, forestry and horticultural plants;
the antiviral agent is selected from: benzothiadiazole, tiadinil, isotianil, 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid, 4-methyl-1, 2, 3-thiadiazole-5-sodium formate, 4-methyl-1, 2, 3-thiadiazole-5-ethyl formate, 3, 4-dichloroisothiazole-5-carboxylic acid, 3, 4-dichloroisothiazole-5-sodium formate, 3, 4-dichloroisothiazole-5-ethyl formate, DL-beta-aminobutyric acid, 2, 6-dichloroisonicotinic acid, N-cyanomethyl-2-chloroisonicotinamide, probenazole, virazole, antofine, ningnanmycin, thiamide, methiothiamide or salicylic acid, pyriminomycin, Dichloroisonicotinic acid, probenazole, validamycin, moroxydine hydrochloride;
the oxime ether heterocyclic formamide derivative I accounts for 1-90% of the antiviral composition in percentage by mass; preferably, the ratio of the oxime ether heterocyclic carboxamide derivative I to the anti-plant virus agent is 1 percent to 99 percent to 1 percent by mass percent;
the antiviral composition is processed into a dosage form selected from: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents;
the antiviral composition can be used for preventing and treating viral diseases selected from: rice dwarf, yellow dwarf, stripe disease, tomato fern leaf virus, pepper mosaic virus, tobacco vein necrosis virus, maize dwarf mosaic, cauliflower mosaic, citrus virus, cymbidium mosaic, cymbidium ringspot virus;
the plants for preventing and treating the antiviral composition are selected from the following plants: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
The oxime ether heterocyclic carboxamide derivative I and any one or two of acaricides are combined to form an acaricide composition for preventing and controlling mite damage of agricultural, forestry and horticultural plants;
the acaricide is selected from: dichlorvos, heptenophos, metofos, monocrotophos, phosphorus dibromide, pyrimidophos, chloromethylthion, ethion, chlorfenvinphos, vofenthion, pirimiphos, phoxim, isocarbophos, amicarbazone, chlormephos, fluthrin, bifenthrin, cyhalothrin, lambda-cyhalothrin, fenpropathrin, flumethrin, fluvalinate, bifenthrin, bifenazate, fenobucarb, butoxycarb, carbofuran, monocarb, benomyl, cloxacarb, butathiocarb, lufenuron, benzyl benzoate, bromopropylate, cyflumetofen, dimethrin, flufenpyr, fluazuron, bleomycin, chlortetracycline, abamectin, avermectin, lium, lividin, doramectin, epothidin, ivermectin, simethiofen, dimethofos, dimethrin, dimethoxim, fosetyl, chlorfenapyr, isofos, chlorfenapyr, dimethoxim, fluazurin, Nicotine, matrine, azadirachtin, rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spirodiclofen, fluacrypyrim, propargite and pyridaben;
the oxime ether heterocyclic formamide derivative I accounts for 1-90% of the acaricidal composition in total mass percentage; the ratio of the oxime ether heterocyclic formamide derivatives I to the acaricide is 1 to 99 to 1 percent in percentage by mass;
the acaricidal composition is processed into a dosage form selected from the following: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents;
the mite damage controlled by the mite-killing composition is selected from the following groups: the mite is selected from spider mite family, furaciidae, gall mite family, Tetranychus genus, and pest mites of gall mite family, which are world agricultural pest mites, forestry pest mites, horticultural pest mites, and health pest mites;
the plant for controlling the acaricidal composition is selected from the following plants: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, 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 oxime ether heterocyclic formamide derivative I is measured as follows:
n. determination of bactericidal activity of oxime ether heterocyclic carboxamide derivative I of the present invention:
the bactericidal or bacteriostatic activity of the heterocyclic formamide I containing oxime ether adopts a thallus growth rate measuring method, and the specific steps are as follows: dissolving 1.8 mg of sample in 2 drops of N, N-dimethylformamide, diluting with a water solution containing a certain amount of Tween 20 emulsifier to 500 micrograms/ml of medicament, sucking 1 ml of the medicament to be tested in a culture dish under an aseptic condition, adding 9 ml of PDA culture medium, shaking uniformly to prepare a medicament-containing flat plate with the concentration of 50 micrograms/ml, taking the flat plate added with 1 ml of sterile water as a blank control, cutting a bacterial disc by a puncher with the diameter of 4 mm along the outer edge of hypha, moving the bacterial disc to the medicament-containing flat plate, placing the bacterial disc in an equilateral triangle, repeating the treatment for 3 times, placing the culture dish in a constant temperature incubator with the temperature of 24 +/-1 ℃ for culture, investigating the expansion diameter of each treated bacterial disc after the diameter of the control bacterial colony is expanded to 2-3 cm, calculating the relative bacteriostasis rate by comparing with the blank control, wherein the strain is the species of most typical plant pathogenic bacteria actually occurring in the agricultural production of China, the code numbers and names are as follows: AS: tomato early blight, its latin name is: alternaria solani, BC: the cucumber botrytis cinerea with the latin name as follows: botrytis cinerea, CA: peanut brown spot pathogen, its latin name is: cercospora arachidicola, GZ: wheat scab, its latin name is: gibberella zeae, PI: the late blight of potato, its latin name is: phytophthora infestans (Mont.) de Bary, PP: apple ring rot, its latin name is: physiosporia piricola, PS: rhizoctonia solani, the Latin name of which is: pellicularia sasakii, RC: rhizoctonia cerealis, with the latin name: rhizoctonia cerealis, SS: sclerotinia sclerotiorum, its latin name is: sclerotina sclerotiorum.
The invention has the beneficial effects that: the oxime ether heterocyclic formamide derivatives I are subjected to lead optimization, and the oxime ether heterocyclic formamide derivatives are subjected to antibacterial activity screening.
The synthesis, biological activity and application of oxime ether heterocyclic carboxamide derivative I are more specifically illustrated by specific preparation and biological activity determination examples, which are only used for specifically illustrating the invention and not limiting the invention, and especially, the biological activity is only illustrated and not limiting the patent, and the specific implementation modes are as follows:
example 1: preparation of compound 3:
Figure BSA0000223369140000091
taking 11.69 mmol of the compound 1, adding 11.69 mmol of N-hydroxyphthalimide and 25mL of N, N-dimethylformamide into a reaction bottle, adding 11.69 mmol of NaOH while stirring, reacting at 80 ℃, and detecting by TLC to finish the reaction. After the reaction solution was cooled, 20 ml of water was added, stirred for 10 minutes, and filtered. CH for solid2Cl2∶H2Dissolving in 1: 1 solution of O, and dissolving in CH2Cl2Extracting for 3 times, washing with saturated saline solution, drying with sodium sulfate, filtering, and concentrating under reduced pressure to obtain white solid 2- (benzyloxy) isoindoline-1, 3-dione; the yield was 74%.
Example 2: preparation of compound 4:
Figure BSA0000223369140000092
adding 7.11 mmol of 2- (benzyloxy) isoindoline-1, 3-diketone into a reaction bottle, adding 15 ml of absolute ethyl alcohol, adding 10.66 mmol of 80% hydrazine hydrate while stirring, carrying out reflux reaction, and detecting the completion of the reaction by TLC. Filtering, and concentrating under reduced pressure to obtain light yellow oily liquid O-benzylhydroxylamine, wherein the yield is as follows: 62 percent.
Example 3: preparation of compound 6:
Figure BSA0000223369140000101
taking 1.96 mmol of substituted O-benzylhydroxylamine to be put into a reaction bottle, adding 1.96 mmol of substituted 2-aminoacetophenone and 15 ml of absolute ethyl alcohol, adding 2-3 drops of concentrated hydrochloric acid, and carrying out reflux reaction; the TLC detection shows that the reaction is finished. Distilling under reduced pressure to remove ethanol, adding CH2Cl2Water extraction and merging organic phases. Washing with saturated brine, drying over sodium sulfate, filtering, and separating by column chromatography to obtain (E) -1- (2-aminophenyl) ethyl-1-one-O-benzyl oxime as a pale yellow oily liquid, with the yield: 60 percent.
Example 4: preparation of compound I:
Figure BSA0000223369140000102
0.51 mmol of 2-difluoromethylnicotinic acid was taken in a reaction flask, and 1.52 mmol of oxalyl chloride and 10 ml of CH were added2Cl2Adding 2 drops of N, N-dimethylformamide, reacting at room temperature for 2 hours, removing oxalyl chloride and CH2Cl2Standby; 0.51 mmol of (E) -1- (2-aminophenyl) ethyl-1-one-O-substituted benzyl oxime was put in a reaction flask, and 10 ml of CH was added2Cl2And 1.52 mmol triethylamine, the acid chloride to be used was dissolved in CH2Cl2Slowly dripping into the reaction solution under the ice bath condition, reacting at normal temperature, and detecting by TLC to finish the reaction. Adding water, CH2Cl2Extracting for 3 times, combining organic phases, washing with saturated brine, drying with sodium sulfate, filtering, and concentrating under reduced pressure to obtain a light yellow solid (Z) -N- (2- (1- ((substituted benzyloxy) imino) ethyl) phenyl) -2- (difluoromethyl) nicotinamide, wherein the yield is as follows: 40 percent.
Example 5: the result of the determination of the antibacterial activity of the oxime ether heterocyclic carboxamide derivative I comprises the following steps:
the codes and names of the common plant pathogenic fungi tested by the invention are as follows: a.s: tomato early blight, its latin name is: alternaria solani, b.c: the cucumber botrytis cinerea with the latin name as follows: botrytis cinerea, C.a: peanut brown spot pathogen, its latin name is: cercospora arachidicola, G.z: wheat scab, its latin name is: gibberella zeae, P.i: the late blight of potato, its latin name is: phytophthora infestans (Mont.) de barr, P.p: apple ring rot, its latin name is: physiosporia piricola, P.s: rhizoctonia solani, the Latin name of which is: pellicularia sasakii, R.c: rhizoctonia cerealis, with the latin name: rhizoctonia cere, S.s: sclerotinia sclerotiorum, its latin name is: the strains have good representativeness and can represent the species of most pathogenic bacteria in the field in agricultural production.
The results of the cell growth rate method are shown in Table 2, and Table 2 shows that all the compounds synthesized by the invention have bactericidal activity of different degrees at 50 micrograms/ml. For botrytis cinerea, the inhibition rate of the compounds HZS-1-12, HZS-1-91, HZS-1-61, HZS-C-12 and HZS-1-0 reaches more than 70 percent, and is obviously superior to that of the control thifluzamide; the activity on peanut brown spot pathogen shows that the inhibition rates of the compounds HZS-1-12, HZS-1-55, HZS-C-17, HZS-1-117 and HZS-1-118 are all over 60 percent, and are equivalent to the control drugs of fluxapyroxad and thifluzamide; the activity on the wheat scabies bacteria shows that the inhibition rates of the compounds HZS-1-11, HZS-1-24, HZS-1-54, HZS-1-73, HZS-1-75, HZS-C-16, HZS-C-17, HZS-1-58, HZS-1-59, HZS-1-57, HZS-1-55, HZS-1-39, HZS-1-35 and HZS-1-12 are all more than 50 percent, and the control medicaments fluxapyroxad and thifluzamide are obviously superior; for ring rot apple germs, the inhibition rate of the compounds HZS-1-11, HZS-1-12, HZS-1-38, HZS-1-55, HZS-1-57, HZS-C-17 and HZS-1-117 is more than 50 percent, which is superior to that of the control drugs fluxapyroxad and thifluzamide, and especially the bactericidal activity of the compound HZS-1-57 is the highest and reaches 65 percent; for sclerotinia sclerotiorum, the bactericidal activity of the compounds HZS-1-12, HZS-1-35, HZS-1-54, HZS-1-59, HZS-C-12 and HZS-C-16 is more than 80 percent, and is equivalent to that of the control drugs fluxapyroxad and thifluzamide, wherein the inhibition rate of the compounds HZS-1-12, HZS-1-35, HZS-1-54 and HZS-C-16 is more than 90 percent, which is superior to that of the control drugs fluxapyroxad and thifluzamide, particularly the bactericidal activity of the compound HZS-C-16 is 96 percent; for rhizoctonia cerealis, the bactericidal activity of the compounds HZS-11, HZS-1-12, HZS-1-24, HZS-1-35, HZS-1-54, HZS-1-57, HZS-C-16 and HZS-C-17 is more than 70 percent, which is more than 10 percent higher than that of fluxapyroxad and thifluzamide serving as control drugs, particularly the bactericidal activity of the compounds HZS-1-24 is up to 88 percent; the activity on rhizoctonia solani shows that the bactericidal activity of the compounds HZS-1-11, HZS-1-12, HZS-1-24, HZS-1-59, HZS-1-61, HZS-C-16 and HZS-C-17 is more than 30 percent and is superior to that of the control drugs fluxapyroxad and thifluzamide; for potato late blight bacteria, the bactericidal activity of the compounds HZS-C-16, HZS-C-17, HZS-C-12, HZS-1-11, HZS-1-12, HZS-1-39, HZS-1-57 and HZS-1-58 is more than 30%, and the bactericidal activity is superior to that of the control drugs fluxapyroxad and thifluzamide.
Example 6: the application of the oxime ether heterocyclic formamide derivatives I in preparing the pesticide composition comprises the following steps:
the oxime ether heterocyclic carboxamide derivative I is used for preparing a pesticide composition, the composition contains the oxime ether heterocyclic carboxamide derivative I and an intermediate thereof as active ingredients, the content of the active ingredients is 0.1 to 99.9 percent by weight, 99.9 to 0.1 percent by weight of solid or liquid auxiliary agents and optionally 0 to 50 percent by weight of surfactant.
Example 7: the application of the oxime ether heterocyclic formamide derivative I in preparing the pesticide compound composition comprises the following steps:
the oxime ether heterocyclic carboxamide derivative I and the intermediate thereof can be compounded with other commercial pesticides, namely insecticides, acaricides, bactericides, antiviral agents or plant activators to prepare a pesticide compound composition, the compound composition comprises the oxime ether heterocyclic carboxamide derivative I and the intermediate thereof and other commercial pesticides, namely insecticides, acaricides, bactericides, antiviral agents or plant activators, as active ingredients, the proportion of the oxime ether heterocyclic carboxamide derivative I and the intermediate thereof to other commercial pesticides, namely insecticides, acaricides, bactericides, antiviral agents or plant activators is 1 percent to 99 percent to 1 percent by mass, the content of the active ingredients is 0.1 to 99.9 percent by weight, 99.9 to 0.1 percent by weight of solid or liquid auxiliaries, and optionally 0 to 50 percent by weight of surfactant.
Example 8: the oxime ether heterocyclic carboxamide derivative I of the invention is combined with insecticide to be applied to preventing and treating agricultural, forestry and horticultural plant insect pests:
the oxime ether heterocyclic carboxamide derivative I and any one or two of commercial insecticides are combined to form an insecticidal composition for preventing and treating agricultural and forestry and horticultural plant insect pests, wherein the commercial insecticide is selected from the following: methoprene, diazinon, acetamiprid, emamectin benzoate, milbemectin, abamectin, pleocidin, metaflumethrin, meperfluthrin, cyfluthrin, beta-cypermethrin, lambda-cyhalothrin, permethrin, allethrin, bifenthrin, permethrin, flumethrin, cyfluthrin, imidacloprid, nitenpyram, imidaclothianidin, thiacloprid, thiamethoxam, clothianidin, dinotefuran, cotinine, dinotefuran, diflubenzuron, chlorbenzuron, tefluazuron, flufenoxuron, lufenuron, chlorflufenoxuron, fluazuron, diflubenzuron, fluazuron, tezine, fluazuron, tezine, teflufenozide, tebufenozide, tezine, flufenozide, tebufenozide, tezine, tebufenozide, methoxyfenozide, chromafenozide, dichlorvos, quinalphos, pyridaphenthion, cicada powder, carbaryl, pirimicarb, metolcarb, isoprocarb, cartap, fenobucarb, tetrafenozide, fenitrothion, hexythiazox, carbaryl, fenisobromolate, hexythiazox, pyridate, clofentezine, spirodiclofen, spirotetramat, azocyclobutazine, buprofezin, monosultap, dimehypo, chlorantraniliprole, tetrachlorantranilide, flubendiamide, cyantraniliprole, butenenitrile, tolfenpyrad, chlorfenapyr, pyrazofos, pyrazinone, etoxazole, tebufenpyrad, pyridaben, emamectin, and pentapyraflufen; the mass percentage of the oxime ether heterocyclic carboxamide derivative I in the insecticidal composition is 1% -90%, and the mass percentage of the oxime ether heterocyclic carboxamide derivative I and the commercial insecticide is 1% to 99% to 1%; the insecticide composition is processed into a dosage form selected from the group consisting of: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents; the plant insect pests controlled by the insecticidal composition are selected from: meadow spodoptera, red spider, east Asian migratory locust, spruce-bug, Chinese rice locust, japanese yellow-back locust, single-prick mole cricket, oriental mole cricket, rice thrips, thrips tabaci, green house thrips, rice straw thistle, wheat simple pipe thrips, green house whitefly, bemisia tabaci, black tail hopper, big leaf hopper, cotton leafhopper, lesser leafhopper, brown plant hopper, white back plant hopper, gray plant hopper, sugarcane flat leaf planthopper, cotton aphid, binary wheat aphid, wheat straw aphid, peach aphid, sorghum aphid, radish aphid, mealybug, lybug, stinkbug, arrowhead bug, round scale, white insect, red wax insect, red worm, mealybug, pear net, banana net bug, tiny flower bug, laceleaf fly, green fly, rice moth, black armyworm, black fly, black rice moth, black armyworm, black rice moth, black rice plant, pink bollworm, sweet potato wheat moth, diamond back moth, peach fruit borer, soybean pod borer, peach fruit borer, apple tip leaf roller moth, brown banded leaf roller moth, pardos leaf roller moth, striped rice borer, pod borer, corn borer, yellow rice borer, cabbage moth, rice leaf roller borer, striped rice borer, cotton leaf borer, peach borer, armyworm, prodenia litura, rice bollworm, cotton small bridgehead moth, beet armyworm, sesamia inferen, cotton bollworm, Dinodon diamond-back moth, agrotis, yellow cutworm, robber venom moth, gypsy moth, sweet potato hawkmoth, bean hawkmoth, straight grain rice skipper, cryptophyte butterfly, caeruleuca, caeruleuciscus nigra, yellow mealyratus caeruleucade, yellow meadowrue, yellow rice beetle, yellow tiger, red ramie yellow vanne, yellow rice borer, yellow rice, Tribolium castaneum, verdigris, black tortoise, branchia palustris, longicorn beetle, pink neck longicorn beetle, ape leaf worm, yellow melon, flea beetle, mung bean weevil, pea weevil, broad bean weevil, corn weevil, rice weevil, wheat leaf bee, pear fruit bee, yellow stripe wasp, armyworm white star ichneumonid, sandfly bractenoconid, cotton bollworm tooth-lipped ichneumonid, borer black spot wart, mosquito, fly, horsefly, red mud fly, yellow leaf sucking serous, rice gall mosquito fly, citrus fruit fly, melon fruit fly, wheat leaf gray fly, American fly, black stalk black fly, wheat stem fly, seed fly, onion fly, radish skirt, eupatorium, corn borer, and armyworm; the plants controlled by the insecticidal composition are selected from the following plants: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
Example 9: the oxime ether heterocyclic carboxamide derivative I and the bactericide are combined to be applied to preventing and treating agricultural, forestry and horticultural plant diseases:
the oxime ether heterocyclic carboxamide derivative I and any one or two of commercial bactericides are combined to form a bactericidal composition for preventing and treating agricultural, forestry and horticultural plant diseases, wherein the commercial bactericides are selected from: benzothiadiazole, tiadinil, thianamide, methicillin, 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid, 4-methyl-1, 2, 3-thiadiazole-5-sodium formate, 4-methyl-1, 2, 3-thiadiazole-5-ethyl formate, DL-beta-aminobutyric acid, isotianil, 3, 4-dichloroisothiazole-5-carboxylic acid, 3, 4-dichloroisothiazole-5-sodium formate, 3, 4-dichloroisothiazole-5-ethyl formate, ribavirin, antofine, ningnanmycin or salicylic acid, cyanamide, thiram, ziram, mancozeb, fosetyl, thiophanate-methyl, chlorothalonil, chlormadinone, procymidone, fenpropidium rust, Thiophanate methyl, thiophanate, metalaxyl-M, flumorph, dimethomorph, metalaxyl-M, benalaxyl-M, diclocyanamide, sulfentram, sulfsulfamide, thifluzamide, folpet, cyprodinil, cyhalodiamide, silthiopham, carboxin, oxim-methyl, mefuram, fenazamide, flutolanil, furametpyr, thifluzamide, boscalid, penthiopyrad, isopyrazamide, bixafen, fluopyram, fluxastrobin, fluxapyroxad, flufenapyr, benconazole, iprovalicarb, flutriafolan, flufenpyrazamide, flufenacetmid, fluoxastrobin, fenhexamid, iprodione, trifloxystrobin, kresoximtrobin, trifloxystrobin, fenstrobin, fenstrobilurin, fenpyraclostrobin, fluoxastrobin, fluoxastrobilurin, fluoxastrobil, Enestroburin, dimethomorph, difenoconazole, bromhexine, epoxiconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole, difenoconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, imazalil, prochloraz, triflumizole, cyazofamid, fenamidone, imidazole, pefurazoate, famoxadone, pyridinozole, prodiamine, ethaboxam, hymexazol, penoxsulam, fenthion, fenpropimorph, tridemorph, fenpyroxanil, fluazinam, fenpropiconazole, fenpyrazamide, fluazinam, cyprodinil, flufenamidone, fenpyrad, fenpyro, Mepanipyrim, pyrimethanil, fenarimol, fluoropyrimidinol, mefenamate, dithianon, ethoxyquin, hydroxyquinoline, propoxymine, phenoxyquinoline, diethofencarb, iprovalicarb, benthiavalicarb, propamocarb, sulbencarb, edifenphos, iprobenfos, pyrazofos, tolclofos-methyl, blasticidin, kasugamycin, polyoxin, validamycin, streptomycin, metalaxyl, furalaxyl, benomyl, thiophanate-methyl, triadimefon, bupirimate, dimethirimol, ethirimol, captan, folpet, vinclozolin, fluocinolone, dimethachlon, chlorothalonil, isoprothiolane, pefurazone, bismerzole, quintozene, propineb, fosetyl, sulfur, polidocusate, cuprous oxide, cupric chloride, cupric oxide, cupric hydroxide, Metrafenone, pencycuron, pyridaben, tetrachlorophthalide, pyroquilon, spiroxamine, tricyclazole, azinam, dodine, diguanidinium salt, diguanidinium, niclosamide, bentiamine, tolfenpyrad, indole ester, sodium disulfate, quinconazole, probenazole, bronopol, methyl iodide, metam, dichloline ester, dazomet, dichloroisopropyl ether, fosthiazate, fosfenthion, fenamiphos, thiothifenthion, methiocarb, sulfuryl fluoride, dichloropropylene, dichloroisonicotinic acid, allylisothiazole; the total mass percentage of the oxime ether heterocyclic carboxamide derivative I in the sterilization composition is 1% -90%, and the mass percentage of the oxime ether heterocyclic carboxamide derivative I and the commercial sterilization agent is 1% to 99% to 1%; the bactericidal composition is processed into a dosage form selected from the group consisting of: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents; the plant diseases controlled by the bactericidal composition are selected from: rice seedling blight, tomato root rot, potato late blight, tobacco black shank, millet powdery mildew, grape downy mildew, lettuce downy mildew, cucumber anthracnose; the plants suitable for the bactericidal composition are selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
Example 10: the oxime ether heterocyclic carboxamide derivative I and the plant virus resisting agent are combined to be applied to preventing and treating virus diseases of agricultural, forestry and horticultural plants:
the oxime ether heterocyclic carboxamide derivative I and any one or two of commercial antiviral medicaments form an antiviral composition for preventing and treating virus diseases of agricultural, forestry and horticultural plants, wherein the commercial antiviral medicaments are selected from: benzothiadiazole, tiadinil, isotianil, 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid, 4-methyl-1, 2, 3-thiadiazole-5-sodium formate, 4-methyl-1, 2, 3-thiadiazole-5-ethyl formate, 3, 4-dichloroisothiazole-5-carboxylic acid, 3, 4-dichloroisothiazole-5-sodium formate, 3, 4-dichloroisothiazole-5-ethyl formate, DL-beta-aminobutyric acid, ribavirin, antofine, ningnanmycin, thiaamide, mehtothiazolamide or salicylic acid, pyriminomycin, dichloroisonicotinic acid, probenazole, validamycin hydrochloride; the total mass percentage content of the oxime ether heterocyclic carboxamide derivative I in the antiviral composition is 1% -90%, and the mass percentage of the oxime ether heterocyclic carboxamide derivative I and the commercial anti-plant virus agent is 1% to 99% to 1%; the antiviral composition is processed into a dosage form selected from: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents; the antiviral composition can be used for preventing and treating viral diseases selected from: rice dwarf, yellow dwarf, stripe disease, tomato fern leaf virus, pepper mosaic virus, tobacco vein necrosis virus, maize dwarf mosaic, cauliflower mosaic, citrus virus, cymbidium mosaic, cymbidium ringspot virus; the plants for preventing and treating the antiviral composition are selected from the following plants: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
Example 11: the oxime ether heterocyclic carboxamide derivative I and the acaricide are combined to be applied to preventing and treating mite damage of agricultural, forestry and horticultural plants:
the oxime ether heterocyclic carboxamide derivative I and any one or two of commercial acaricides form an acaricidal composition for preventing and controlling acarid damages of agricultural, forestry and horticultural plants, wherein the commercial acaricides are selected from the following groups: dichlorvos, heptenophos, metofos, monocrotophos, phosphorus dibromide, pyrimidophos, chloromethylthion, ethion, chlorfenvinphos, vofenthion, pirimiphos, phoxim, isocarbophos, amicarbazone, chlormephos, fluthrin, bifenthrin, cyhalothrin, lambda-cyhalothrin, fenpropathrin, flumethrin, fluvalinate, bifenthrin, bifenazate, fenobucarb, butoxycarb, carbofuran, monocarb, benomyl, cloxacarb, butathiocarb, lufenuron, benzyl benzoate, bromopropylate, cyflumetofen, dimethrin, flufenpyr, fluazuron, bleomycin, chlortetracycline, abamectin, avermectin, lium, lividin, doramectin, epothidin, ivermectin, simethiofen, dimethofos, dimethrin, dimethoxim, fosetyl, chlorfenapyr, isofos, chlorfenapyr, dimethoxim, fluazurin, Nicotine, matrine, azadirachtin, rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spirodiclofen, fluacrypyrim, propargite and pyridaben; the oxime ether heterocyclic carboxamide derivative I of the invention accounts for 1 to 90 percent of the total mass of the acaricidal composition, and the ratio of the oxime ether heterocyclic carboxamide derivative I to the commercial acaricide accounts for 1 to 99 to 1 percent of the mass of the acaricidal composition; the acaricidal composition is processed into a dosage form selected from the following: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents; the mite damage controlled by the mite-killing composition is selected from the following groups: the mite is selected from spider mite family, furaciidae, goiter family, Tetranychus genus, and pest mites of the goiter family, which are world agricultural pest mites, forestry pest mites, horticultural pest mites, and health pest mites; the plant for controlling the acaricidal composition is selected from the following plants: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
Industrial applicability
The invention provides oxime ether heterocyclic formamide derivatives; the derivative can regulate and control the biological activity of agricultural, horticultural and sanitary pests and plant pathogens of forestry plants, can be used for killing insects, killing mites, sterilizing, resisting plant viruses and inducing plants to generate disease resistance in the agricultural field, the horticultural field and the forestry field, and has better economic value and application prospect.
Figure BSA0000223369140000181
Figure BSA0000223369140000191
Figure BSA0000223369140000201
Figure BSA0000223369140000211
TABLE 2 bacteriostatic activity of the oxime ether heterocyclic carboxamide derivatives I of the present invention (inhibition rate of 50. mu.g/ml/%)
Serial number Compound (I) A.s B.c C.a G.z P.i P.p P.s R.c S.s
1 HZS-1-11 43 39 47 62 37 59 34 79 59
2 HZS-1-12 36 76 60 58 32 58 31 72 93
3 HZS-1-24 31 42 39 63 23 40 39 88 32
4 HZS-1-91 1 67 8 33 16 26 18 12 48
5 HZS-1-35 25 13 38 52 29 33 28 78 90
6 HZS-1-34 13 40 29 26 22 40 18 18 53
7 HZS-1-37 5 39 10 20 20 7 20 0 5
8 HZS-1-36 6 31 8 39 16 23 7 27 64
9 HZS-1-39 18 33 22 51 32 22 25 65 50
10 HZS-1-38 16 35 30 43 30 63 26 54 68
11 HZS-1-54 30 40 43 61 27 33 16 77 90
12 HZS-1-55 36 56 61 59 28 54 11 69 63
13 HZS-1-57 29 58 28 55 33 65 23 78 57
14 HZS-1-56 17 58 19 31 18 26 20 34 33
15 HZS-1-59 20 24 26 57 31 10 34 65 86
16 HZS-1-58 18 39 35 50 36 33 21 55 63
17 HZS-1-61 18 79 21 34 26 11 39 53 30
18 HZS-1-60 27 3 35 23 23 38 24 53 27
19 HZS-C-10 3 46 14 24 16 6 20 0 29
20 HZS-C-11 3 13 4 33 18 6 10 12 20
21 HZS-C-12 12 69 21 39 35 43 18 39 84
22 HZS-C-13 20 50 23 42 21 36 34 41 33
23 HZS-C-14 6 38 13 38 21 19 26 8 45
24 HZS-C-15 10 24 11 31 17 20 22 0 62
25 HZS-C-16 36 44 48 61 38 47 39 83 96
26 HZS-C-17 41 52 61 63 36 57 34 82 63
27 HZS-1-117 47 41 70 31 26 53 21 17 52
28 HZS-1-118 31 32 60 38 20 42 18 13 50
29 HZS-1-74 2 38 13 13 5 26 13 12 5
30 HZS-1-76 1 54 55 46 15 14 27 11 20
31 HZS-C-21 1 41 6 13 10 17 10 18 14
32 HZS-1-93 6 58 17 32 16 21 10 33 9
33 HZS-1-104 1 / 15 21 5 14 12 2 28
34 HZS-1-0 16 70 22 30 14 36 24 0 34
35 HZS-1-75 26 55 54 63 21 41 29 24 17
36 Fluxapyroxad 74 100 86 41 13 48 15 41 83
37 Thifluzamide 65 59 82 35 13 39 15 56 88
/: not determined
A.s: tomato early blight, its latin name is: alternaria solani, b.c: the cucumber botrytis cinerea with the latin name as follows: botrytis cinerea, C.a: peanut brown spot pathogen, its latin name is: cercospora arachidicola, G.z: wheat scab, its latin name is: gibberella zeae, P.i: the late blight of potato, its latin name is: phytophthora infestans (Mont.) de barr, P.p: apple ring rot, its latin name is: physiosporia piricola, P.s: rhizoctonia solani, the Latin name of which is: pellicularia sasakii, R.c: rhizoctonia cerealis, with the latin name: rhizoctonia cere, S.s: sclerotinia sclerotiorum, its latin name is: sclerotina sclerotomalis.

Claims (7)

1. The oxime ether heterocyclic formamide derivatives are characterized by simultaneously containing oxime ether and heterocyclic formamide structures and have a structural general formula shown in a formula I:
Figure FSA0000223369130000011
wherein Het is selected from: 2-chloropyridyl, 2-difluoromethylpyridyl, 3, 4-dichloroisothiazolyl, 2-difluoromethyl-4-methylpyrazolyl; r1 is selected from: hydrogen, 4-fluoro; r2 is selected from: hydrogen, methyl; r3 is selected from: hydrogen, 4-fluoro, 4-methyl, 4-trifluoromethyl, 2-chloro-4-fluoro.
2. The specific synthetic route and method of oxime ether heterocyclic carboxamide derivative I according to claim 1 are:
Figure FSA0000223369130000012
the definition of the substituent is as defined in claim 1, and the specific synthetic method comprises the following steps:
A. preparation of oxime ether heterocyclic carboxamide derivative I:
i is prepared by reacting intermediate difluoropyrazolothiazoformic acid, benzotriazol-1-yl-oxy-tripyrrolidinophosphonium hexafluorophosphate and N, N-diisopropylethylamine with substituted amine R- (CH) in dichloromethane solvent2)n-NH2Stirring at room temperature for reaction; the substituents are as defined in claim 1;
A. preparation of compound 3:
taking substituted benzyl bromide to a reaction bottle, adding N-hydroxyphthalimide and N, N-dimethylformamide, adding NaOH under stirring, reacting at 80 ℃, and finishing the reaction; cooling the reaction liquid, adding water, stirring for 10 minutes, and filtering; extracting solid dichloromethane and water, washing with saturated saline solution, drying with sodium sulfate, filtering, and concentrating under reduced pressure to obtain white solid 3;
B. preparation of compound 4:
putting the compound 3 into a reaction bottle, adding absolute ethyl alcohol, adding 80% hydrazine hydrate while stirring, and carrying out reflux reaction until the reaction is finished; filtering, and concentrating under reduced pressure to obtain yellowish oily liquid 4;
C. preparation of compound 6:
putting the compound 4 into a reaction bottle, adding the compound 5 and absolute ethyl alcohol, adding 2-3 drops of concentrated hydrochloric acid, and carrying out reflux reaction; finishing the reaction; distilling under reduced pressure to remove ethanol, extracting with dichloromethane and water, and mixing organic phases; washing with saturated saline solution, drying with sodium sulfate, filtering, and separating by column chromatography to obtain yellowish oily liquid compound 6;
D. preparation of compound I:
adding acid into dichloromethane, adding oxalyl chloride and 2 drops of N, N-dimethylformamide, reacting at room temperature for 2 hr, removing oxalyl chloride and CH2Cl2Standby; adding Compound 6 to CH2Cl2Adding triethylamine, dissolving the acyl chloride in dichloromethane, and slowly addingSlowly dropwise adding the mixture into the reaction solution, reacting at normal temperature, and finishing the reaction; adding water, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with sodium sulfate, filtering, concentrating the filtrate to remove the solvent, and purifying by column chromatography to obtain compound I;
as a preferred embodiment of the present invention, the oxime ether containing heterocyclic carboxamide derivative is synthesized by the following steps:
taking 11.69 mmol of substituted benzyl bromide, adding 11.69 mmol of N-hydroxyphthalimide and 25ml of N, N-dimethylformamide into a reaction bottle, adding 11.69 mmol of NaOH while stirring, reacting at 80 ℃, and detecting by TLC to finish the reaction; after the reaction solution was cooled, 20 ml of water was added, stirred for 10 minutes, and filtered; CH for solid2Cl2∶H2Dissolving in 1: 1 solution of O, and dissolving in CH2Cl2Extracting for 3 times, washing with saturated saline solution, drying with sodium sulfate, filtering, and concentrating under reduced pressure to obtain white solid 2- (substituted benzyloxy) isoindoline-1, 3-dione;
adding 7.11 mmol of 2- (substituted benzyloxy) isoindoline-1, 3-diketone into a reaction bottle, adding 15 ml of absolute ethyl alcohol, adding 10.66 mmol of 80% hydrazine hydrate while stirring, carrying out reflux reaction, and finishing TLC detection reaction; filtering, and concentrating under reduced pressure to obtain yellowish oily liquid O-substituted benzylhydroxylamine;
taking 1.96 mmol of substituted O-benzylhydroxylamine to be put into a reaction bottle, adding 1.96 mmol of substituted 2-aminoacetophenone and 15 ml of absolute ethyl alcohol, adding 2-3 drops of concentrated hydrochloric acid, and carrying out reflux reaction; TLC detection reaction is finished; distilling under reduced pressure to remove ethanol, adding CH2Cl2Extracting with water, and mixing organic phases; washing with saturated saline solution, drying with sodium sulfate, filtering, and separating by column chromatography to obtain light yellow oily liquid (E) -1- (2-aminophenyl) ethyl-1-ketone-O-substituted benzyl oxime;
0.51 mmol of 2-difluoromethylnicotinic acid was taken in a reaction flask, and 1.52 mmol of oxalyl chloride and 10 ml of CH were added2Cl22 drops of N, N-dimethylformamide are reacted for 2 hours at normal temperature to remove oxalyl chloride and CH2Cl2Standby; 0.51 mmol of (E) -1- (2-aminophenyl) ethyl-1-one-O-substituted benzyl oxime was put in a reaction flask, and 10 ml of CH was added2Cl2And 1.52 mmol triethylamine, the acid chloride to be used was dissolved in CH2Cl2Slowly dripping the mixture into the reaction solution under the ice bath condition, reacting at normal temperature, and detecting by TLC to finish the reaction; adding water and CH2Cl2Extracting for 3 times, mixing organic phases, washing with saturated saline, drying with sodium sulfate, filtering, and concentrating under reduced pressure to obtain light yellow solid (Z) -N- (2- (1- ((substituted benzyloxy) imino) ethyl) phenyl) -2- (difluoromethyl) nicotinamide;
wherein A is selected from: 2-chloropyridyl, 2-difluoromethylpyridyl, 3, 4-dichloroisothiazolyl, 2-difluoromethyl-4-methylpyrazolyl; r1Selected from: hydrogen, 4-fluoro; r2Selected from: hydrogen, methyl; r3Selected from: hydrogen, 4-fluoro, 4-methyl, 4-trifluoromethyl, 2-chloro-4-fluoro.
3. Use of the oxime ether heterocyclic carboxamide derivative I as claimed in claim 1 for the preparation of agricultural fungicides.
4. An agricultural fungicidal composition comprising the oxime ether heterocyclic carboxamide derivative I as claimed in claim 1 and an intermediate, which can be prepared as an agricultural fungicidal composition comprising the oxime ether heterocyclic carboxamide derivative I as claimed in claim 1 as active ingredient in an amount of 0.1 to 99.9% by weight, 99.9 to 0.1% by weight of a solid or liquid adjuvant and optionally 0 to 25% by weight of a surfactant.
5. An agricultural sterilization compound composition, which comprises the oxime ether heterocyclic carboxamide derivative I as claimed in claim 1 and other commercial bactericides as active ingredients, wherein the mass percentage of the oxime ether heterocyclic carboxamide derivative I to the other commercial bactericides is 1 percent to 99 percent to 1 percent, the content of the active ingredients is 1 to 99 percent by weight, and the solid or liquid auxiliary agent is 99 to 1 percent by weight.
6. An agricultural insecticidal and acaricidal compound composition, which comprises the oxime ether heterocyclic carboxamide derivative I as claimed in claim 1 and other commercial insecticidal and acaricidal agents as active ingredients, wherein the proportion of the oxime ether heterocyclic carboxamide derivative I to the other commercial insecticidal and acaricidal agents is 1% to 99% to 1% by mass, the content of the active ingredients is 1 to 99% by weight, and 99 to 1% by weight of solid or liquid auxiliary agents.
7. A compound composition of anti-plant virus agents, which comprises the oxime ether heterocyclic carboxamide derivative I as claimed in claim 1 and other commercial anti-plant virus agents which are compounded to serve as active ingredients, wherein the ratio of the oxime ether heterocyclic carboxamide derivative I to the other commercial anti-plant virus agents is 1 percent to 99 percent to 1 percent by mass, the content of the active ingredients is 1 to 99 percent by weight, and the content of the solid or liquid auxiliary agents is 99 to 1 percent by weight.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997030047A1 (en) * 1996-02-17 1997-08-21 Agrevo Uk Limited Fungicidal 1,2,4-oxadiazoles and analogues
US5824705A (en) * 1992-01-29 1998-10-20 Basf Aktiengesellschaft Carbamates and crop protection agents containing them
CN109970653A (en) * 2019-05-17 2019-07-05 南开大学 Methoxy acrylate derivative and its preparation method and application of the one kind containing difluoromethyl pyrazole

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5824705A (en) * 1992-01-29 1998-10-20 Basf Aktiengesellschaft Carbamates and crop protection agents containing them
WO1997030047A1 (en) * 1996-02-17 1997-08-21 Agrevo Uk Limited Fungicidal 1,2,4-oxadiazoles and analogues
CN109970653A (en) * 2019-05-17 2019-07-05 南开大学 Methoxy acrylate derivative and its preparation method and application of the one kind containing difluoromethyl pyrazole

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