CN112592338A - 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivatives, and preparation method and application thereof - Google Patents
3, 4-dichloroisothiazole coumarin methoxyl acrylate derivatives, and preparation method and application thereof Download PDFInfo
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- CN112592338A CN112592338A CN202110006447.XA CN202110006447A CN112592338A CN 112592338 A CN112592338 A CN 112592338A CN 202110006447 A CN202110006447 A CN 202110006447A CN 112592338 A CN112592338 A CN 112592338A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
Abstract
The invention provides 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivatives, a preparation method and application thereof, wherein the chemical structure general formula is shown as formula I: i:
Description
Technical Field
The technical scheme of the invention relates to a 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative.
Background
The heterocyclic compound has high-efficiency, low-toxicity and broad-spectrum biological activity, and most of the biological active compounds reported in patent documents have heterocyclic structures; the literature reports that the five-membered heterocyclic compound has the activities of a plant activator, a bactericide, a plant growth regulator and an insecticide (Chendanping, modern pesticide, 2014, 14 (2): 5-10), wherein the coumarin compound has the physiological activities of cancer resistance, antibiosis, anti-inflammation, antioxidation and the like, and also has good agricultural activities of insecticide, sterilization and the like. Recent researches show that the coumarin compound has more outstanding acaricidal activity and unique action targets, and has the potential of developing novel acaricides (Liu loop forest, etc.. the agricultural and pharmaceutical science, 2019, 21 (5-6): 692-.
The strobilurin fungicide is a novel bionic fungicide with high efficiency, broad spectrum, safety and growth promotion, is a milestone type agricultural fungicide after triazole fungicides in the world pesticide field, and has great development potential and application prospect (Wuhaibo et al Henan agriculture 2020, 04: 22). The resistance problem caused by the use of a large amount of high-frequency high-intensity bactericide is very prominent due to the single action site of the Strobilurin bactericide (Fisher, N.Pest. Manage. Sci.2005, 61 (10): 973-; the plant activator has a broad-spectrum lasting system to obtain disease resistance, and acts on the plant itself without directly acting on pathogens, so that the risk of drug resistance is avoided, and the research on the preparation of the plant activator is urgent.
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 an N-containing S-containing isothiazole pharmacophore 3, 4-dichloroisothiazole ring and a natural active component coumarin structure into a lead structure of methoxyacrylate, designs and synthesizes a class of 3, 4-dichloroisothiazole coumarin methoxyacrylate derivatives, and carries out systematic screening and evaluation of biological activity so as to provide more candidate compounds with high activity and low resistance risk for the research of new pesticide creation.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a synthetic method of 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivatives, provides a method for regulating and controlling the biological activity of agricultural, horticultural and sanitary pests and plant pathogens of forestry plants by using the compounds and a determination method thereof, and simultaneously provides applications of the compounds 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 general chemical structure formula of the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivatives with insecticidal, acaricidal, bactericidal, plant virus resisting and plant disease resisting activities in the agricultural field, the horticultural field and the forestry field is shown as I:
I：
wherein R is1Selected from: hydrogen, methyl, chlorine; r2Selected from: hydrogen, methyl, ethyl, fluorine, chlorine.
The synthetic route of the 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I is as follows:
the synthesis method of the 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I comprises the following steps:
A. synthesis of 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I:
3, 4-dichloroisothiazole coumarin derivative 1(1.0 mmol) and compound 2(1.1 mmol) were dispersed in dry acetonitrile (5.0 ml) and dissolved with stirring at room temperature. Heating and refluxing for 12-24 hours. After the reaction was completed by thin layer chromatography, the reaction mixture was concentrated, ethyl acetate (10 ml) and water (10 ml) were added, the mixture was stirred and left to stand for separation, the aqueous phase was extracted with ethyl acetate (2 × 10 ml), the organic phases were combined, the organic phase was washed successively with saturated sodium bicarbonate solution, water and saturated brine, and dried by adding anhydrous sodium sulfate. Vacuum filtering, concentrating, and performing column chromatography (V)Petroleum ether∶VEthyl acetateAnd (2) purifying the obtained product by the ratio of 10: 1-3: 1) to obtain the 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I. The preparation amount of the compound I and the volume of a reaction vessel are enlarged or reduced according to corresponding proportion;
wherein, the substituent R1、R2As defined above; r1Selected from: hydrogen, methyl, chlorine. R2Selected from: hydrogen, methyl, ethyl, fluorine, chlorine.
The invention provides application of the 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I in preparation of fungicides.
The invention provides application of the 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I in preparation of a tobacco mosaic virus resistant agent.
The invention provides application of the 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I in preparing a plant activator for inducing tobacco to resist tobacco mosaic virus.
The invention provides application of the 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I in prevention and treatment of agricultural, forestry and horticultural plant insect pests.
Co-administering the 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I with an agrochemical; the agrochemical is selected from: one or more of insecticide, bactericide, plant virus resisting agent and acaricide.
The 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I and any one or two of the insecticides are combined to form an insecticidal composition for preventing and treating insect pests of agricultural and forestry and horticultural plants;
the insecticide is selected from: methoprene, diazinon, acetamiprid, emamectin benzoate, milbemectin, abamectin, pleocidin, metaflumethrin, cyhalothrin, lambda-cypermethrin, lambda-cyhalothrin, permethrin, allethrin, bifenthrin, permethrin, flumethrin, cyhalothrin, imidacloprid, nitenpyram, imidacloprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran, flufenoxuron, lufenuron, chlorfluazuron, fluazuron, diflubenzuron, fluazuron, teuron, novaluron, flufenoxuron, fluazuron, flufenoxuron, fluazuron, tezine, flufenozide, teflufenozide, tebufenozide, tezine, flufenozide, tebufenozide, flufenozide, flufeno, Chlorantraniliprole, methoxyfenozide, chromafenozide, dichlorvos, quinalphos, pyridaphenthion, cicada powder, carbaryl, pirimicarb, metolcarb, isoprocarb, cartap, fenobucarb, tetrafenozide, fenitrothion, chlorfenpyr, tetrafenozide, fenitrothion, hexythiazox, fenpyroximate, pyridaben, clofentezine, diafenthiuron, pymetrozine, spirodiclofen, spirotetramat, azocyclotin, buprofezin, monosultap, dimehypo, chlorantraniliprole, tetrachlorantranilide, flubendiamide, cyantraniliprole, crotafloxacin, tolfenpyrazamide, chlorfenapyr, imazemazone, imazalil, tebufenpyrad, pyridalyl, pyriproxyfen, emamectin, and guadipyridamole;
the 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I accounts for 1-90% of the insecticidal composition by mass; preferably, the ratio of the 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I to the pesticide is 1 to 99 to 1 percent by mass percent;
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 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I and any one or two of the bactericides are combined to form a bactericidal composition for preventing and treating diseases of agricultural, forestry and horticultural plants;
the bactericide is selected from: benzothiadiazole, tiadinil, thifluzamide, DL-beta-aminobutyric acid, isotianil, ribavirin, antofine, ningnanmycin or salicylic acid, cymoxanil, thiram, mancozeb, fosetyl-aluminium, thiophanate-methyl, chlorothalonil, dichlorvos, procymidone, fenpropidin, thiophanate-methyl, metalaxyl-M, flumorphine, dimethomorph, propamocarb, dichlormid, flusulfamide, sulfenamide, thifluvalicarb-isopropyl, cyprodinil, cyhalodiamide, silthiopham, carboxin, metalaxyl oxide, furamex, triflumimide, furametryn, thifluzamide, boscalid, penthiopyrad, pyrazopyram, bixafen, fluopyram, fluoxafen, epoxiconazole, fenpyraclostrobin, flutriafolan, flufenazamide, flufenapyr-methyl, flufenamate, flufenapyr, thiflufenamate, flufenamate, flufenapyr, thiflufenamate, benconazole, iprazole, flufenacet, fluxapyroxad, flufenacet, flufenamid, mandipropamid, zoxamide, ethirimide, iprodione, azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, enestroburin, alkene oxime amine, epoxiconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole, tebuconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, imazalil, prochloraz, cyazofamid, pyraclostrobin, famoxadone, isoprothiolane, imazalil, Pyrisoxazole, hymexazol, oxadixyl, ethaboxam, hymexazol, octreone, thiobencarb, dodemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, cyprodinil, fluopicolide, pyrimethanil, cyprodinil, mepanipyrim, pyrimethanil, fenamidol, fluoropyrimidinol, flufenamidol, fenamiphen, dithianon, ethoxyquinoline, hydroxyquinoline, propoxymine, phenoxyquinoline, diethofencarb, iprovalicarb, benthiavalicarb, propamocarb, edifenphos, iprobenfos, pyrazophos, tolon, tolfenclofos, kasugamycin, polyoxin, validamycin, jinggangmycin, streptomycin, metalaxyl, furalaxyl, benalaxyl, furalaxyl, carbendazim, benomyl, thiophanaton, thizalone, triadimefon, fenamidone, fenamidothiobac, pyrimethanil, Ethirimol, captafol, captan, folpet, vinclozolin, fluoxynil, dimethachlon, chlorothalonil, isoprothiolane, metconazole, quintozene, propineb, fosetyl-aluminum, sulfur, bordeaux, copper sulfate, copper oxychloride, cuprous oxide, copper hydroxide, metrafenone, pencycuron, pyridaben, tetrachlorophthalide, pyroquilon, spiroxamine, tricyclazole, fluazinam, dodine, iminoctadine, octylamine, clonidine, benthiamid, indoxyl, diuron, quinconazole, probenazole, bronopol, methyl iodide, metam, fenamate, dazomet, dichloroprofen, fosthiazate, foscarnet, fenamiphos, dichlofos, thiocarb, thioflonicamid, dichloropropylene, dichlorisoisothiazole;
the 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I accounts for 1-90% of the total mass of the bactericidal composition; the ratio of the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative 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 3, 4-dichloroisothiazole coumarin methoxyl acrylate 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 and forestry and horticultural plants;
the antiviral agent is selected from: benzothiadiazole, tiadinil, isotianil, DL-beta-aminobutyric acid, 2, 6-dichloroisonicotinic acid, N-cyanomethyl-2-chloroisonicotinamide, allylisothiazole, ribavirin, antofine, ningnanmycin, methicillin-induced amine or salicylic acid, pyriminomycin, dichloroisonicotinic acid, allylisothiazole, validamycin, moroxydine hydrochloride;
the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I accounts for 1-90% of the antiviral composition in percentage by mass; preferably, the ratio of the 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I to the anti-plant virus agent is 1 to 99 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 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I and any one or two of the acaricides are combined to form an acaricide composition for preventing and controlling acarid pests of agricultural and forestry and horticultural plants;
the acaricide is selected from: dichlorvos, heptenophos, metophos, dibromophos, pirimiphos-methyl, ethion, chlorfenvinphos, vofenphos, pirimiphos-methyl, quinalphos, aphidmethomyl, amicarbaz, chlorfenphos, phosmet, fluthrin, bifenthrin, cyhalothrin, lambda-cyhalothrin, fenpropathrin, bifenazate, fenobucarb, butoxycarb, oxamyl, carbofuran, monocarb, benomyl, cloxacarb, butathion, lufenuron, benzoate, bromopropylate, cyflumetofen, flufenpyr, flufenoxuron, chlorfenapyr, sumicin, miticide, ruscin, avermectin, doramectin, norubicin, eprinomectin, ivermectin, larmectin, moxidectin, chrysanthemin, nicotine, alkali, dimethomorphin, chlorfenapyr, Nimbin, rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spirodiclofen, fluacrypyrim, acaricide, propargite and pyridaben;
the 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I accounts for 1% -90% of the acaricidal composition in total mass percentage; the ratio of the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I to the acaricide is 1 to 99 to 1 percent by mass percent;
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 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I is determined as follows:
B. the bactericidal activity of the 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I is determined as follows:
the bactericidal or bacteriostatic activity of the 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I is measured by a thallus growth rate measuring method, and the method comprises the following specific steps: dissolving 1.8 mg of sample in 2 drops of dimethyl sulfoxide, diluting the sample to 500 micrograms/ml of medicament with aqueous solution containing a certain amount of Tween 20 emulsifier, sucking 1 ml of the reagent to be tested in a culture dish under an aseptic condition, adding 9 ml of PDA culture medium respectively, shaking uniformly to prepare a 50 micrograms/ml medicament-containing flat plate, 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 to be placed in an equilateral triangle, repeating the treatment for 3 times, placing the culture dish in a constant-temperature culture box at 24 +/-1 ℃ for culturing, 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 average value, comparing with the blank control to calculate the relative bacteriostasis rate, wherein the test bacterial strain is the species of most of typical plant pathogenic bacteria actually generated in the field in agricultural production in 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 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I is subjected to lead optimization, and the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I is subjected to antibacterial activity screening.
The synthesis, biological activity and application of the 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I are more specifically illustrated by specific preparation and biological activity determination examples, which are only used for specifically illustrating the invention and are not used for limiting the invention, and particularly, the biological activity is only illustrated and is not used for limiting the patent, and the specific implementation modes are as follows:
example 1: preparation of Compound I-1:
3, 4-dichloroisothiazole coumarin 1a (314 mg, 1.0 mmol) and compound 2(343 mg, 1.1 mmol) were dispersed in dry trifluoroacetic acid (5.0 ml) and dissolved with stirring at room temperature. The reaction was heated under reflux for 12 hours. After the reaction was completed by thin layer chromatography, the reaction mixture was concentrated, ethyl acetate (10 ml) and water (10 ml) were added, the mixture was stirred and left to stand for separation, the aqueous phase was extracted with ethyl acetate (2 × 10 ml), the organic phases were combined, the organic phase was washed successively with saturated sodium bicarbonate solution, water and saturated brine, and dried by adding anhydrous sodium sulfate. Vacuum filtering, concentrating, and performing column chromatography (V)Petroleum ether∶VEthyl acetate10: 1-3: 1) to obtain a 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I-1 with the yield of 98 percent; the nuclear magnetic data are as follows:1H NMR(400MHz，CDCl3) δ 7.57-7.35(m, 3H), 7.23-7.20(m, 2H), 6.91-6.80(m, 2H), 6.31(s, 1H), 5.04(s, 2H), 4.05(s, 3H), 3.87(s, 3H); the preparation amount of the compound I-1 and the volume of a reaction vessel are enlarged or reduced according to corresponding proportion;
the physicochemical and structural parameters of compound I are shown in Table 1.
Example 2: the determination result of the antibacterial activity of the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I comprises the following steps:
the codes and names of the common plant pathogenic fungi tested by the invention 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: 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 the rhizoctonia cerealis, the inhibition rates of the compounds LY02-20, LY02-27 and LY02-35 of the invention reach more than 60 percent, and are equivalent to the control drugs trifloxystrobin and kresoxim-methyl; for ring rot apple germs, the inhibition rates of compounds LY02-20 and LY02-27 are 55% and 58% respectively, and are equivalent to those of control drugs trifloxystrobin and kresoxim-methyl; for sclerotinia sclerotiorum, the inhibition rates of compounds LY02-21, LY02-27, LY02-29, LY02-31, LY02-33, LY02-35, LY02-37, LY02-49 LY02-45 and LY02-50 are all above 70 percent, and the inhibition rates are not good enough compared with control drugs pyraclostrobin, trifloxystrobin and kresoxim-methyl; the activity of the compound on the gibberella zeae shows that the compound is not good overall, but the inhibition rate of the compound LY02-35 is 56 percent, and is equivalent to the control drug trifloxystrobin; for botrytis cinerea, the inhibition rate of compound LY02-22 is 71%, but the inhibition rate is not good compared with that of a control drug; for potato late blight bacteria, the compound has poor overall performance; for peanut brown spot germs, the compound has poor overall performance; for tomato early blight bacteria, the compound has poor overall performance; the activity on rice sheath blight bacteria shows that the compound has poor overall performance; in conclusion, the compounds show good activity to sclerotinia sclerotiorum; wherein the compounds LY02-20 and LY02-27 show broad-spectrum bactericidal activity.
Example 3: the application of the 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I in the preparation of the pesticide composition comprises the following steps:
the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I is used for preparing a pesticide composition, the composition contains the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I and an intermediate thereof as active ingredients, and the active ingredients are 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 4: the application of the 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I in the preparation of the pesticide compound composition comprises the following steps:
the 3, 4-dichloroisothiazole coumarin methoxyacrylate 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 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I and the intermediate thereof and other commercial pesticides, namely insecticides, acaricides, bactericides, antiviral agents or plant activators, as active ingredients, the 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I and the intermediate thereof and other commercial pesticides, namely insecticides, acaricides, bactericides, antiviral agents or plant activators have the mass percent of 1 percent to 99 percent to 1 percent, and the content of the active ingredients is 0.1 to 99.9 percent, 99.9% to 0.1% by weight of a solid or liquid adjuvant, and optionally 0 to 50% by weight of a surfactant.
Example 5: the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I and the pesticide are combined to be applied to preventing and treating agricultural, forestry and horticultural plant insect pests:
the 3, 4-dichloroisothiazole coumarin methoxyl acrylate 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 insecticides are selected from the following components: methoprene, diazinon, acetamiprid, emamectin benzoate, milbemectin, abamectin, pleocidin, metaflumethrin, cyhalothrin, lambda-cypermethrin, lambda-cyhalothrin, permethrin, allethrin, bifenthrin, permethrin, flumethrin, cyhalothrin, imidacloprid, nitenpyram, imidacloprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran, flufenoxuron, lufenuron, chlorfluazuron, fluazuron, diflubenzuron, fluazuron, teuron, novaluron, flufenoxuron, fluazuron, flufenoxuron, fluazuron, tezine, flufenozide, teflufenozide, tebufenozide, tezine, flufenozide, tebufenozide, flufenozide, flufeno, Chlorantraniliprole, methoxyfenozide, chromafenozide, dichlorvos, quinalphos, pyridaphenthion, cicada powder, carbaryl, pirimicarb, metolcarb, isoprocarb, cartap, fenobucarb, tetrafenozide, fenitrothion, chlorfenpyr, tetrafenozide, fenitrothion, hexythiazox, fenpyroximate, pyridaben, clofentezine, diafenthiuron, pymetrozine, spirodiclofen, spirotetramat, azocyclotin, buprofezin, monosultap, dimehypo, chlorantraniliprole, tetrachlorantranilide, flubendiamide, cyantraniliprole, crotafloxacin, tolfenpyrazamide, chlorfenapyr, imazemazone, imazalil, tebufenpyrad, pyridalyl, pyriproxyfen, emamectin, and guadipyridamole; the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I accounts for 1-90% of the insecticidal composition by mass, and the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I and the commercial insecticide are in a ratio of 1% to 99% to 1% 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.
Example 6: the application of the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I and the bactericide composition in preventing and treating agricultural, forestry and horticultural plant diseases:
the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I and any one or two of commercial bactericides are combined to form a bactericidal composition for preventing and treating diseases of agricultural, forestry and horticultural plants, wherein the commercial bactericides are selected from the following group: benzothiadiazole, tiadinil, thifluzamide, DL-beta-aminobutyric acid, isotianil, ribavirin, antofine, ningnanmycin or salicylic acid, cymoxanil, thiram, mancozeb, fosetyl-aluminium, thiophanate-methyl, chlorothalonil, dichlorvos, procymidone, fenpropidin, thiophanate-methyl, metalaxyl-M, flumorphine, dimethomorph, propamocarb, dichlormid, flusulfamide, sulfenamide, thifluvalicarb-isopropyl, cyprodinil, cyhalodiamide, silthiopham, carboxin, metalaxyl oxide, furamex, triflumimide, furametryn, thifluzamide, boscalid, penthiopyrad, pyrazopyram, bixafen, fluopyram, fluoxafen, epoxiconazole, fenpyraclostrobin, flutriafolan, flufenazamide, flufenapyr-methyl, flufenamate, flufenapyr, thiflufenamate, flufenamate, flufenapyr, thiflufenamate, benconazole, iprazole, flufenacet, fluxapyroxad, flufenacet, flufenamid, mandipropamid, zoxamide, ethirimide, iprodione, azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, enestroburin, alkene oxime amine, epoxiconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole, tebuconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, imazalil, prochloraz, cyazofamid, pyraclostrobin, famoxadone, isoprothiolane, imazalil, Pyrisoxazole, hymexazol, oxadixyl, ethaboxam, hymexazol, octreone, thiobencarb, dodemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, cyprodinil, fluopicolide, pyrimethanil, cyprodinil, mepanipyrim, pyrimethanil, fenamidol, fluoropyrimidinol, flufenamidol, fenamiphen, dithianon, ethoxyquinoline, hydroxyquinoline, propoxymine, phenoxyquinoline, diethofencarb, iprovalicarb, benthiavalicarb, propamocarb, edifenphos, iprobenfos, pyrazophos, tolon, tolfenclofos, kasugamycin, polyoxin, validamycin, jinggangmycin, streptomycin, metalaxyl, furalaxyl, benalaxyl, furalaxyl, carbendazim, benomyl, thiophanaton, thizalone, triadimefon, fenamidone, fenamidothiobac, pyrimethanil, Ethirimol, captafol, captan, folpet, vinclozolin, fluoxynil, dimethachlon, chlorothalonil, isoprothiolane, metconazole, quintozene, propineb, fosetyl-aluminum, sulfur, bordeaux, copper sulfate, copper oxychloride, cuprous oxide, copper hydroxide, metrafenone, pencycuron, pyridaben, tetrachlorophthalide, pyroquilon, spiroxamine, tricyclazole, fluazinam, dodine, iminoctadine, octylamine, clonidine, benthiamid, indoxyl, diuron, quinconazole, probenazole, bronopol, methyl iodide, metam, fenamate, dazomet, dichloroprofen, fosthiazate, foscarnet, fenamiphos, dichlofos, thiocarb, thioflonicamid, dichloropropylene, dichlorisoisothiazole; the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I accounts for 1-90% of the total mass of the sterilization composition, and the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I accounts for 1% -99% of the mass of the commercial bactericide; 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 7: the 3, 4-dichloroisothiazole coumarin methoxyl acrylate 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 3, 4-dichloroisothiazole coumarin methoxyl acrylate 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: diazosulfide, tiadinil, isotianil, DL-beta-aminobutyric acid, ribavirin, antofine, ningnanmycin, methicillin or salicylic acid, pyriminomycin, dichloroisonicotinic acid, probenazole, validamycin, moroxydine hydrochloride; the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I accounts for 1-90% of the antiviral composition in total mass percent, and the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I and the commercial anti-plant virus agent are in a ratio of 1% to 99% to 1% in 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.
Example 8: the application of the combination of the 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I and the acaricide in preventing and controlling the mite damage of agricultural, forestry and horticultural plants is as follows:
the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I and any one or two of commercial acaricides form an acaricidal composition for controlling agricultural and forestry and horticultural plant acarids, wherein the commercial acaricides are selected from the following components: dichlorvos, heptenophos, metophos, dibromophos, pirimiphos-methyl, ethion, chlorfenvinphos, vofenphos, pirimiphos-methyl, quinalphos, aphidmethomyl, amicarbaz, chlorfenphos, phosmet, fluthrin, bifenthrin, cyhalothrin, lambda-cyhalothrin, fenpropathrin, bifenazate, fenobucarb, butoxycarb, oxamyl, carbofuran, monocarb, benomyl, cloxacarb, butathion, lufenuron, benzoate, bromopropylate, cyflumetofen, flufenpyr, flufenoxuron, chlorfenapyr, sumicin, miticide, ruscin, avermectin, doramectin, norubicin, eprinomectin, ivermectin, larmectin, moxidectin, chrysanthemin, nicotine, alkali, dimethomorphin, chlorfenapyr, Nimbin, rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spirodiclofen, fluacrypyrim, acaricide, propargite and pyridaben; the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I accounts for 1-90% of the acaricidal composition in total mass percent, and the 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative I and the commercial acaricide are in proportion of 1% to 99% to 1% in mass percent; 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 a 3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative. 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.
TABLE 23 bacteriostatic activity of 4-dichloroisothiazole coumarin methoxyacrylate derivative I (inhibition of 50. mu.g/ml/%)
| Serial number | Compound (I) | R.c | P.p | S.s | G.z | B.c | P.i | C.a | A.s | P.s |
| 1 | LY01-58 | 44 | 30 | 59 | 46 | 40 | 31 | 35 | 33 | 24 |
| 2 | LY02-20 | 60 | 55 | 68 | 45 | 42 | 36 | 41 | 30 | 37 |
| 3 | LY02-21 | 48 | 28 | 81 | 20 | 48 | 18 | 45 | 28 | 14 |
| 4 | LY02-22 | 54 | 25 | 66 | 47 | 71 | 46 | 51 | 30 | 45 |
| 5 | LY02-26 | 51 | 31 | 63 | 43 | 60 | 29 | 30 | 28 | 23 |
| 6 | LY02-27 | 61 | 58 | 75 | 32 | 34 | 18 | 46 | 33 | 24 |
| 7 | LY02-42 | 37 | 29 | 55 | 15 | 42 | 17 | 41 | 26 | 8 |
| 8 | LY02-29 | 56 | 36 | 82 | 45 | 34 | 44 | 35 | 31 | 45 |
| 9 | LY02-31 | 58 | 38 | 72 | 43 | 38 | 35 | 35 | 28 | 35 |
| 10 | LY02-32 | 46 | 25 | 66 | 32 | 26 | 28 | 41 | 28 | 24 |
| 11 | LY02-43 | 32 | 21 | 64 | 16 | 34 | 0 | 30 | 22 | 3 |
| 12 | LY02-33 | 48 | 4 | 82 | 42 | 56 | 46 | 41 | 28 | 45 |
| 13 | LY02-35 | 62 | 25 | 71 | 56 | 48 | 44 | 47 | 47 | 44 |
| 14 | LY02-36 | 49 | 39 | 53 | 32 | 45 | 38 | 40 | 29 | 34 |
| 15 | LY02-37 | 43 | 25 | 72 | 48 | 55 | 47 | 42 | 30 | 48 |
| 16 | LY02-49 | 57 | 28 | 74 | 31 | 60 | 27 | 33 | 30 | 25 |
| 17 | LY02-45 | 31 | 24 | 74 | 44 | 34 | 33 | 38 | 26 | 30 |
| 18 | LY02-50 | 59 | 42 | 76 | 42 | 50 | 46 | 33 | 27 | 44 |
| 19 | LY02-23 | 47 | 17 | 63 | 38 | 13 | 14 | 23 | 11 | 14 |
| 20 | LY02-44 | 16 | 0 | 63 | 0 | 38 | 8 | 8 | 1 | 3 |
| 21 | LY02-48 | 14 | 0 | 58 | 6 | 42 | 12 | 10 | 4 | 10 |
| 22 | Pyraclostrobin (Kresoxim-methyl) | 86 | 74 | 100 | 74 | 100 | 61 | 81 | 68 | 67 |
| 23 | Trifloxystrobin | 70 | 51 | 100 | 60 | 100 | 60 | 53 | 43 | 63 |
| 24 | Kresoxim-methyl | 71 | 62 | 92 | 71 | 100 | 66 | 54 | 46 | 68 |
| 25 | Isotianil | 4 | 19 | 8 | 5 | 74 | 7 | 13 | 7 | 14 |
R.c: rhizoctonia cerealis, with the latin name: rhizoctonia cere, P.p: apple ring rot, its latin name is: physiosporia piricola, S.s: sclerotinia sclerotiorum, its latin name is: sclerotina sclerotomalis, G.z: wheat scab, its latin name is: gibberella zeae, b.c: the cucumber botrytis cinerea with the latin name as follows: botrytis cinerea, P.i: the late blight of potato, its latin name is: phytophthora infestans (Mont.) de barr, C.a: peanut brown spot pathogen, its latin name is: cercospora arachidicola, A.s: tomato early blight, its latin name is: alternaria solani, P.s: rhizoctonia solani, the Latin name of which is: pellicularia sasakii.
Claims (7)
1. A3, 4-dichloroisothiazole coumarin methoxyl acrylate derivative has a structural general formula shown in formula I:
wherein R is1Selected from: hydrogen, methyl, chlorine; r2Selected from: hydrogen, methyl, ethyl, fluorine, chlorine.
2. The specific synthetic route and method of the 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I as claimed in claim 1 is as follows:
the definition of the substituent is as defined in claim 1, and the specific synthetic method comprises the following steps:
synthesis of 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I:
3, 4-dichloroisothiazole coumarin derivative 1(1.0 mmol) and compound 2(1.1 mmol) were dispersed in dry acetonitrile (5.0 ml) and dissolved with stirring at room temperature; heating and refluxing for reaction for 12-24 hours; after the detection reaction of the thin layer chromatography, concentrating the reaction solution, adding ethyl acetate (10 ml) and water (10 ml), stirring, standing, layering, extracting the water phase with ethyl acetate (2X 10 ml), combining the organic phases, washing the organic phases with saturated sodium bicarbonate solution, water and saturated salt solution in turn, and adding anhydrous sodium sulfate for drying; vacuum filtering, concentrating, and performing column chromatography (V)Petroleum ether∶VEthyl acetatePurifying the obtained product at a ratio of 10: 1-3: 1) to obtain a 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I; the preparation amount of the compound I and the volume of a reaction vessel are enlarged or reduced according to corresponding proportion;
wherein, the substituent R1、R2As defined above; r1Selected from: hydrogen, methyl, chlorine; r2Selected from: hydrogen, methyl, ethyl, fluorine, chlorine.
3. Use of the 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I as claimed in claim 1 for the preparation of agricultural fungicides.
4. An agricultural fungicidal composition comprising the 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I as described in claim 1 and an intermediate, which can be prepared as an agricultural fungicidal composition comprising the 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I as described in claim 1 as an 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 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I as claimed in claim 1 and other commercial bactericides as active ingredients, wherein the mass percentage of the 3, 4-dichloroisothiazole coumarin methoxy acrylate 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, and the weight of the active ingredients is 99 to 1 percent of solid or liquid auxiliary agents.
6. An agricultural insecticidal and acaricidal compound composition, which comprises the 3, 4-dichloroisothiazole coumarin methoxyacrylate derivative I as claimed in claim 1 and other commercial insecticidal and acaricidal agents as active ingredients, wherein the insecticidal and acaricidal ratio of the 3, 4-dichloroisothiazole coumarin methoxyacrylate 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 the content of the active ingredients is 99 to 1% by weight of solid or liquid auxiliaries.
7. A compound composition of an anti-plant virus agent, which comprises the 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I as claimed in claim 1 and other commercial anti-plant virus agents which are compounded to serve as active ingredients, wherein the mass percentage of the 3, 4-dichloroisothiazole coumarin methoxy acrylate derivative I to the other commercial anti-plant virus agents is 1% to 99% to 1%, the content of the active ingredients is 1 to 99% by weight, and the weight of the active ingredients is 99 to 1% by weight of solid or liquid auxiliaries.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107226812A (en) * | 2016-03-25 | 2017-10-03 | 南开大学 | One class piperidines thiazole oxime ether methoxy base acrylate derivative and its production and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107226812A (en) * | 2016-03-25 | 2017-10-03 | 南开大学 | One class piperidines thiazole oxime ether methoxy base acrylate derivative and its production and use |
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| LAI CHEN ET AL: ""Synthesis of Novel 3,4-Chloroisothiazole-Based Imidazoles as Fungicides and Evaluation of Their Mode of Action"", 《JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY》 * |
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