3,4-dichloroisothiazole benzamide derivatives, processes for their preparation and uses thereof

Abstract

The application provides a kind of 3, 4-dichloroisothiazole benzamide derivatives and preparation method and purposes thereof, specifically relates to a kind of derivatives, and the chemical structure general formula is seen formula I: the application discloses the general formula of the structure of the above compound, synthesis method and as insecticide, acaricide, fungicide, anti-plant virus agent, plant activator purposes, it is combined with agricultural acceptable adjuvant or synergist and with commercial insecticide, acaricide, fungicide, anti-plant virus agent, plant immune activator in the prevention and treatment of agricultural, forestry, horticultural plant pest, mite damage, disease, viral disease purposes and preparation method.

Description

Technical Field

[0001] The technical solution of this invention belongs to the field of pesticides, and relates to a class of 3,4-dichloroisothiazol benzamide derivatives, their preparation methods and uses. Background Technology

[0002] Plant diseases are a significant factor affecting crop yield and quality. Pathogens such as fungi, bacteria, and viruses can infect leaves, stems, flowers, and fruits, causing yield reduction, quality degradation, and post-harvest rot. Currently, plant disease control still relies heavily on chemical agents, but long-term use can lead to increased pathogen resistance and may result in pesticide residues and environmental safety issues. Therefore, developing plant disease control agents with novel mechanisms of action and good environmental compatibility is of great importance.

[0003] Plant immune activators can activate the plant's own defense response and enhance its resistance to pathogen infection. They typically do not directly kill pathogens, thus exhibiting low resistance risk and strong complementarity with traditional fungicides, making them promising for disease control in green agriculture (Nomoto, M. et al. Cell Rep. 2021, 37, 110125). However, existing plant immune activators still suffer from limited structural types and insufficient activity stability, necessitating the development of novel and highly efficient plant immune activators.

[0004] The 3,4-dichloroisothiazolium structural unit has significant value in pesticide development (Lv, Y. et al. J. Agric. Food Chem. 2021, 69, 4567−4576), and the benzamide skeleton has a stable structure and a large space for modification. This invention combines the 3,4-dichloroisothiazolium fragment with the benzamide skeleton to design and synthesize a class of 3,4-dichloroisothiazolium benzamide derivatives. These derivatives exhibit good induction of disease resistance against plant diseases and can be used as potential plant immune activators for plant disease control. Summary of the Invention

[0005] The technical problem to be solved by this invention is to provide a new method for synthesizing 3,4-dichloroisothiazol benzamide derivatives, and to provide applications of these compounds in agriculture, horticulture and forestry.

[0006] The technical solution adopted by this invention to solve this technical problem is: to synthesize 3,4-dichloroisothiazolium benzamide derivatives with insecticidal, acaricidal, fungicidal, antiviral, and plant disease-inducing activities in agriculture, horticulture, and forestry, and their general chemical structural formula is shown in Figure I:

[0007]

[0008] Wherein, R is selected from: any substituted phenyl, any substituted benzyl, any substituted phenethyl, preferably from 4-chlorophenyl, 2-chlorophenyl, 2-methoxyphenyl, 4-fluorophenyl, 3-bromophenyl, 3-bromo-4-methoxyphenyl, 3-bromo-5-methoxyphenyl, 2-(3-fluorophenyl)ethyl, 2-(2-fluorophenyl)ethyl, 2-isopropenylphenyl, indanyl or 3-tert-butylphenyl; n is 0, 1, 2 or 3; preferably, n is 0 or 1.

[0009] The synthetic route and method for the above-mentioned 3,4-dichloroisothiazol benzamide derivative I are as follows:

[0010]

[0011] The specific synthesis method consists of the following steps:

[0012] A. Preparation of compound 2:

[0013] Compound 1 (15.0 mmol) and tetrahydrofuran (20.0 mL) were added to a 100 mL round-bottom flask and stirred until dissolved. Potassium carbonate (45.0 mmol) and potassium iodide (15.0 mmol) were added sequentially. After stirring at room temperature for 1 hour, methyl benzoate of o-hydroxy substituted form (25.0 mmol) was slowly added dropwise. After the addition was complete, the mixture was heated to 80 °C and refluxed for 8 hours. After the reaction was complete, the mixture was cooled to room temperature and the reaction was terminated by adding water. The mixture was extracted three times with ethyl acetate, 25 mL each time. The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography to obtain compound 2.

[0014] B. Preparation of compound 3:

[0015] Take a 250 mL round-bottom flask, add compound 2 (12.0 mmol), and a mixed solution of lithium hydroxide aqueous solution / anhydrous ethanol, wherein the volume ratio of lithium hydroxide aqueous solution to anhydrous ethanol is 4:1. Heat to 80 degrees Celsius with stirring and react for 6 hours. After the reaction is complete, cool to room temperature. Adjust the pH of the reaction solution to 2 to 3 with 1 mol / L dilute hydrochloric acid. A white solid precipitates out. Collect by suction filtration, wash with water and dry to obtain compound 3.

[0016] C. Preparation of Compound I:

[0017] Take a 100 mL round-bottom flask, add compound 3 (3.0 mmol) and dichloromethane (20.0 mL), stir to dissolve, and slowly add triethylamine (3.6 mmol), followed by the addition of the substituted amine R-NH2 (3.6 mmol), then successively add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (3.6 mmol) and 1-hydroxybenzotriazole (3.0 mmol). Stir the reaction overnight at room temperature. After the reaction is complete, add water to terminate the reaction. Extract three times with dichloromethane, 25 mL each time. Combine the organic phases, dry with anhydrous sodium sulfate, remove the solvent under reduced pressure, and purify the residue by column chromatography to obtain 3,4-dichloroisothiazol benzamide derivative I.

[0018] Uses of 3,4-dichloroisothiazol benzamide derivative I:

[0019] This invention provides the use of 3,4-dichloroisothiazol benzamide derivative I in the preparation of insecticides.

[0020] This invention provides the use of 3,4-dichloroisothiazol benzamide derivative I in the preparation of fungicides, wherein the fungicides control fungi such as early blight of tomato, gray mold of cucumber, brown spot of peanut, Fusarium graminearum, Fusarium verticillatum, ring spot of apple, rice sheath blight, and sclerotinia sclerotium of rapeseed.

[0021] This invention provides the use of 3,4-dichloroisothiazol benzamide derivative I in the preparation of an anti-tobacco mosaic virus agent.

[0022] This invention provides the use of 3,4-dichloroisothiazol benzamide derivative I in the preparation of plant immune activators for inducing tobacco resistance to tobacco mosaic virus and for inducing Arabidopsis resistance to Arabidopsis downy mildew.

[0023] It should be noted that plant immune activators were formerly called plant activators or resistance inducers. They can induce host plants to produce broad-spectrum and long-lasting disease resistance.

[0024] This invention provides 3,4-dichloroisothiazol benzamide derivative I suitable for controlling pests and pathogens in agricultural, forestry, and horticultural plants, and for inducing plants to develop defense capabilities against plant pests and pathogens. The above-mentioned pesticide composition includes agricultural fungicides, agricultural insecticides, agricultural antiviral compositions, and agricultural plant immune activators. The composition contains the above-mentioned 3,4-dichloroisothiazol benzamide derivative I as an active ingredient. The composition contains 0.1% to 99.9% by weight of the active ingredient, 99.9% to 0.1% by weight of solid or liquid adjuvants, and surfactants selected from 0 to 25% by weight.

[0025] 3,4-Dichloroisothiazol benzamide derivative I and its composition and uses:

[0026] 3,4-Dichloroisothiazolium benzamide derivative I is combined with a commercial pesticide to form an agricultural composition for application; the commercial pesticide is selected from one or more of insecticides, fungicides, antiviral agents for plants, acaricides, and plant immune activators. This composition, 3,4-dichloroisothiazolium benzamide derivative I, is compounded with other commercial insecticides, fungicides, antiviral agents for plants, acaricides, and plant immune activators as active ingredients; the content of the active ingredient in this composition is 1%:99% to 99%:1% by weight, and the compounded composition contains 1% to 99% by weight of the active ingredient, 99% to 1% by weight of a solid or liquid adjuvant, and a surfactant selected from 0 to 25% by weight. Specific combinations are as follows:

[0027] The 3,4-dichloroisothiazol benzamide derivative I, combined with any one or two of the insecticides, forms an insecticidal composition for the prevention and control of pests in agricultural, forestry, and horticultural plants.

[0028] The insecticides mentioned are selected from: imidacloprid, difenoconazole, acetamiprid, emamectin benzoate, abamectin, spinosad, heptamethrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, deltamethrin, cypermethrin, β-cyhalothrin, λ-cyhalothrin, dichlorvos, permethrin, allethrin, bifenthrin, permethrin, fenpropathrin, flufenoxuron, cyhalothrin, imidacloprid, acetamiprid, chlorpyrifos, thiamethoxam, thiamethoxam, dinotefuran, fenpropathrin, fenpropathrin, difenoconazole, fenpropathrin, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole, difenoconazole , bis(phenylfluorouron), flufenoxuron, fenflurfen, bis(triflufenoxuron), furazolidone, chlorfenapyr, methoxyfenozide, cyclone dichlorvos, dichlorvos, quinalphos, pyridazin, leafhopper powder, carbaryl, pirimicarb, methamidophos, isoprocarb, pyridaben, methyl parathion, methyl parathion, bromopropylate, thiamethoxam, azoxystrobin, pyridaben, tetradifon, propargite, bufenozide, pymetrozine, spirodiclofen, spirotetramat, triazophos, thiamethoxam, chlorfenapyr, tetrachlorfenapyr, flufenoxuron, flufenoxuron, cyanfenoxuron, butenylflufenoxuron, azoxystrobin, bromopropylate, pyrazinazole, etoxazole, pyridaben, pyridaben, pyriproxyfen, emamectin, pendimethalin;

[0029] The 3,4-dichloroisothiazol benzamide derivative I is present in the insecticidal composition at a mass percentage of 1%-90%; preferably, the ratio of the 3,4-dichloroisothiazol benzamide derivative I to the insecticide is 1%:99% to 99%:1% by mass.

[0030] The formulation of the insecticidal composition is selected from: seed treatment emulsions, water-in-oil emulsions, microemulsions, suspensions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, poison grains, block poison baits, granular poison baits, flake poison baits, concentrated poison baits, slow-release blocks, electrostatic sprays, oil-in-water emulsions, smoke cans, smoke candles, smoke tubes, smoke sticks, smoke sheets, smoke pellets, gas generators, ointments, hot fogging agents, cold fogging agents, aerosols, solid / liquid mixtures, liquid / liquid mixtures, solid / solid mixtures, medicated paints, microparticles, tracking powders, oil suspensions, oil-dispersible powders, concentrated gels, pouring agents, seed coating agents, coating agents, film-forming oils, ultra-low volume liquids, and vapor release agents;

[0031] The plant pests controlled by the insecticidal composition are selected from: fall armyworm, spider mite, Oriental migratory locust, spotted locust, Chinese rice locust, Japanese yellow-spined locust, single-spined mole cricket, oriental mole cricket, rice thrips, tobacco thrips, greenhouse thrips, rice tube thrips, wheat tube thrips, greenhouse whitefly, tobacco whitefly, black-tailed leafhopper, large green leafhopper, cotton leafhopper, spotted lanternfly, brown planthopper, white-backed planthopper, gray planthopper, sugarcane flat-horned planthopper, cotton aphid, wheat two-forked aphid, wheat long-tubed aphid, peach aphid, sorghum aphid, radish aphid, cottony cushion scale, mulberry shield scale, arrowhead shield scale, pear round scale, white wax insect, red wax scale, Korean ball scale. Pear lace bug, banana lace bug, slender horned flower bug, miniature flower bug, needle-edged bug, rice spider-web bug, rice brown bug, rice black bug, rice green bug, green mirid bug, alfalfa mirid bug, medium black mirid bug, large lacewing, beautiful lacewing, Chinese lacewing, grain moth, clothes moth, yellow tussock moth, brown tussock moth, flat tussock moth, wheat moth, cotton bollworm, sweet potato wheat moth, diamondback moth, peach fruit moth, soybean fruit moth, peach fruit moth, apple top leafroller, brown-banded long leafroller, false yellow leafroller, rice stem borer, bean pod borer, corn borer, three-spined rice stem borer, cabbage stem borer, rice leaf roller, striped stem borer, cotton leafroller, peach borer, armyworm, sedge beetle. Noctuid moth, rice stem borer, cotton budworm, beet armyworm, large stem borer, cotton bollworm, *Diamond borer*, small cutworm, large cutworm, yellow cutworm, tussock moth, gypsy moth, sweet potato hawk moth, bean hawk moth, straight-striped rice skipper, hidden-striped rice skipper, citrus swallowtail butterfly, white-banded swallowtail butterfly, cabbage white butterfly, ramie red nymph, ramie yellow nymph, bean blister beetle, golden ground beetle, wrinkled sheath beetle, wheat ear beetle, wireworm, fine-breasted wireworm, grain bark beetle, black bark beetle, citrus small jewel beetle, golden-edged jewel beetle, yellow mealworm, black mealworm, red flour beetle, mixed flour beetle, green-green scarab beetle, dark scarab beetle, North China large Black-breasted beetle, mulberry longhorn beetle, star longhorn beetle, orange brown longhorn beetle, peach red-necked longhorn beetle, large ape leaf beetle, small ape leaf beetle, yellow cucumber beetle, yellow striped flea beetle, green bean weevil, pea weevil, broad bean weevil, corn weevil, rice weevil, wheat leaf beetle, pear fruit wasp, yellow-banded ichthys wasp, armyworm white-spotted ichthys wasp, moth larvae hanging cocoon ichthys wasp, cotton bollworm toothed ichthys wasp, moth black-spotted wart ichthys wasp, mosquito, fly, horsefly, wheat red midge, wheat yellow midge, rice gall midge, citrus fruit fly, melon fruit fly, wheat leaf gray leafminer, American serpentine leafminer, bean stalk black leafminer, wheat straw fly, seed fly, onion fly, turnip fly, umbrella-skirted parasitic fly, corn borer parasitic fly, armyworm;

[0032] The insecticidal composition controls plants selected from: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, peanut, rapeseed, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili pepper, radish, cucumber, cabbage, celery, pickled mustard greens, beet, rapeseed, onion, garlic, watermelon, cantaloupe, honeydew melon, papaya, apple, citrus and peach trees, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, and bonsai.

[0033] The 3,4-dichloroisothiazol benzamide derivative I, combined with any one or two of the fungicides, forms a fungicidal composition for the prevention and control of diseases in agricultural, forestry, and horticultural plants.

[0034] The fungicides are selected from: benzothiadiazole, thiamethoxam, methyl thiamethoxam, DL-β-aminobutyric acid, isothiazamide, ribavirin, antofenfen, ningnanmycin or salicylic acid, cymoxanil, thiram, zinc thiram, mancozeb, aluminum fosetyl-aluminum, thiophanate-methyl, chlorothalonil, dichlorvos, iprodione, benzyl benzoate, thiophanate-methyl, thiophanate-methyl, metalaxyl, flumorph, dimethomorph, high-efficiency metalaxyl, high-efficiency benzyl benzoate, diclofenac, sulfadiazine, mesotrione, thiabendazole, chlorothalonil, propiconazole, cyclopropiconazole, cyclofluoroacetate, cyclopropiconazole, cyproconazole, silthiamethoxam, carbendazim, oxidized carbendazim, carbendazim, mefenoxam, chlorpyrifos, fluopyram, furazolidone, thiabendazole, cyproconazole, pyraclostrobin, pyraclostrobin, bifenazate, fluopyram, fluorinated parabens. Azoxystrobin, fluopyram, fluopyram aniline, benzyl-fluoroquinolones, isothiazamide, fluopyram hydroxylamine, flufenoxuron, fluopyram, diyrylamide, benzylamide, ethoxysulfuron, iprodione, pyraclostrobin, azoxystrobin, fluopyram, azoxystrobin, fenoxystrobin, oxadiazon, azoxystrobin, oxadiazon, oxadiazon, oxadiazon, oxadiazon, oxadiazon, oxadiazon, oxadiazon, oxadiazon, oxadiazon, oxadiazon, fenoxystrobin Azoxystrobin, propiconazole, difenoconazole, tebuconazole, high-efficiency tebuconazole, flutriafol, cyproconazole, fluquinazole, flusilazole, fenbendazole, hexaconazole, imidacloprid, tebuconazole, propiconazole, thiophanate-methyl, siloxyfenozide, tebuconazole, tetrafluoroether, triazole, tebuconazole, bifenthrin, thiamethoxam, cyproconazole, imazalil, high-efficiency imazalil, prochloraz. Fluopyram, Cyazofamid, Imidacloprid, Oxalide, Isoprothiolane, Oxalide, Pyrimethanil, Oxafloxacin, Oxafloxacin, Thiazolamide, Tebuconazole, Benzylthiocyanate, Dodecylmorpholine, Butylmorpholine, Tridemorpholine, Seed dressing, Fludioxonil, Fluazinam, Pyridabenoxac, Cyclopyridamole, Fluazinam, Pyrimethanil, Azoxystrobin, Fluazinam, Thifluzamide, Azoxystrobin, Pyrimethanil, Chlorpyrimethanil, Fluazinam, Acaricide, Dicyandioxonone, Ethoxyquinoline, Hydroxyquinoline, Propoxyquinoline, Phenoxyquinoline, Ethiocarb, Isopropamidone, Benzylthiamethoxam, Cymoxanil, Sulfocarb, Difenoconazole, Isoprothiolane, Pyridaben, Methyl thiophanate, Pyrimethanil, Kasugamycin, Polyoxin, Polyoxin, Activiamycin, Jinggangmycin, Streptomycin, Metalaxyl, Furazolidone Benzoyl, furazolidone, carbendazim, benomyl, thiophanate-methyl, triadimefon, ethirimol sulfonate, dimethomorph, ethirimol, captan, captan, thiophanate-methyl, chlorothalonil, fluchlorothalonil, chlorothalonil, isoprothiolane, isoprothiolane, tebuconazole, pentachloronitrobenzene, propineb, aluminum tris(ethylphosphonate), sulfur, Bordeaux mixture, copper sulfate, copper oxychloride, cuprous oxide, copper hydroxide, benomyl, pendimethalin, pyridaben, tetrachlorophthalide, quinclorac, spirocycline, tricyclazole, pyrazosulfuron, doxycycline, biguanide octyl salt, biguanide octylamine, chlorothalonil, benzylsulfonamide, toluenesulfonamide, indole ester, sodium dichloroisocyanurate, quinclorac, allylbenzylthiazide, bromonitol, iodomethyl, methyl methoxide, dimethoate, dazomet, dichloroisopropyl ether, thiamethoxam, fensodium, fenoxam, fenpyroxim, fenpyroximKiller carbendazim, thiocyanate, dichloropropene, dichloroisocyanuric acid, allylisothiazol;

[0035] The total mass percentage of the 3,4-dichloroisothiazolium benzamide derivative I in the bactericidal composition is 1%-90%; the ratio of the 3,4-dichloroisothiazolium benzamide derivative I to the bactericide is 1%:99% to 99%:1% by mass.

[0036] The formulation of the bactericidal composition is selected from: seed treatment emulsions, water-in-oil emulsions, microemulsions, suspensions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, poison grains, block poison baits, granular poison baits, flake poison baits, concentrated poison baits, slow-release blocks, electrostatic sprays, oil-in-water emulsions, smoke cans, smoke candles, smoke tubes, smoke sticks, smoke sheets, smoke pellets, gas generators, ointments, hot fogging agents, cold fogging agents, aerosols, solid / liquid mixtures, liquid / liquid mixtures, solid / solid mixtures, medicated paints, microparticles, tracking powders, oil suspensions, oil-dispersible powders, concentrated gels, pouring agents, seed coating agents, coating agents, film-forming oils, ultra-low volume liquids, and vapor release agents;

[0037] The plant diseases controlled by the bactericidal composition are selected from: rice seedling cottony rot, tomato root rot, potato late blight, tobacco black shank, millet powdery mildew, grape downy mildew, lettuce downy mildew, cucumber downy mildew, and cucumber anthracnose.

[0038] The plants suitable for use in the bactericidal composition are selected from: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, peanut, rapeseed, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili pepper, radish, cucumber, cabbage, celery, pickled mustard greens, beet, rapeseed, onion, garlic, watermelon, cantaloupe, honeydew melon, papaya, apple, citrus and peach trees, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, and bonsai.

[0039] The 3,4-dichloroisothiazol benzamide derivative I, combined with any one or two of the antiviral agents, forms an antiviral composition for the prevention and control of viral diseases in agricultural, forestry, and horticultural plants.

[0040] The antiviral agents are selected from: benzothiadiazole, thiamethoxam, isothiazine DL-β-aminobutyric acid, 2,6-dichloroisonicotinic acid, N-cyanomethyl-2-chloroisonicotinamide, allylisothiazide, ribavirin, antofen, ningnanmycin, methiazolinone or salicylic acid, pyrimethanil, dichloroisonicotinic acid, allylisothiazide, jinggangmycin, and morpholine guanidine hydrochloride;

[0041] The total mass percentage of the 3,4-dichloroisothiazolium benzamide derivative I in the antiviral composition is 1%-90%; preferably, the ratio of the 3,4-dichloroisothiazolium benzamide derivative I to the antiviral agent is 1%:99% to 99%:1% by mass.

[0042] The dosage forms of the antiviral composition are selected from: seed treatment emulsions, water-in-oil emulsions, microemulsions, suspensions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, poison grains, block poison baits, granular poison baits, flake poison baits, concentrated poison baits, slow-release blocks, electrostatic sprays, oil-in-water emulsions, smoke cans, smoke candles, smoke tubes, smoke sticks, smoke sheets, smoke pellets, gas generators, ointments, hot fogging agents, cold fogging agents, aerosols, solid / liquid mixtures, liquid / liquid mixtures, solid / solid mixtures, medicated paints, microparticles, tracking powders, oil suspensions, oil-dispersible powders, concentrated gels, pouring agents, seed coating agents, coating agents, film-forming oils, ultra-low volume liquids, and vapor release agents.

[0043] The antiviral composition controls viral diseases selected from: rice dwarf virus, yellow dwarf virus, stripe leaf blight, tomato fern leaf virus, pepper mosaic virus, tobacco vein necrosis virus, maize dwarf mosaic virus, cauliflower mosaic virus, citrus virus, Cymbidium faberi leaf virus, and Cymbidium faberi ringspot virus.

[0044] The antiviral composition is used to prevent and control diseases from plants selected from: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, peanut, rapeseed, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili pepper, radish, cucumber, cabbage, celery, pickled mustard greens, beet, rapeseed, onion, garlic, watermelon, cantaloupe, honeydew melon, papaya, apple, citrus and peach trees, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, and bonsai.

[0045] The 3,4-dichloroisothiazol benzamide derivative I, combined with any one or two of the acaricides, forms an acaricide composition for the prevention and control of mite infestations in agricultural, forestry, and horticultural plants.

[0046] The acaricides are selected from: dichlorvos, heptamethrin, methamidophos, dibromophos, pyrimiphos, chlorpyrifos, ethion, chlorfenapyr, fenpropathrin, methyl pyrimiphos, quinalphos, abamectin, acephate, chlorpyrifos, fenpropathrin, bifenthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, flufenoxuron, deltamethrin, bifenazate, benzalkonium chloride, methyl ethyl methyl methoxide, chlorpyrifos, chlorfenapyr, chlorpyrifos, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr. Carbendazim, thiamethoxam, tebufenozide, benzyl benzoate, bromopropylate, diflubenzuron, fenpyroximate, flufenoxuron, liuyangmycin, chlorfenapyr, thiophanate-methyl, acaricide, liuyangmycin, avermectin, doramectin, epoxim, ivermectin, selamectin, moxibustion, pyrethroid, nicotine, matrine, azadirachtin, rotenone, pyridaben, pyridaben, azoxystrobin, tetradifon, propargite, thiamethoxam, spirodiclofen, pyrimethanil, dicofol, dicofol, pyridaben;

[0047] The total mass percentage of the 3,4-dichloroisothiazolium benzamide derivative I in the acaricide composition is 1%-90%; the ratio of the 3,4-dichloroisothiazolium benzamide derivative I to the acaricide is 1%:99% to 99%:1% by mass.

[0048] The formulation of the acaricide composition is selected from: seed treatment emulsions, water-in-oil emulsions, microemulsions, suspensions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, poison grains, block poison baits, granular poison baits, flake poison baits, concentrated poison baits, slow-release blocks, electrostatic sprays, oil-in-water emulsions, smoke cans, smoke candles, smoke tubes, smoke sticks, smoke sheets, smoke pellets, gas generators, ointments, hot fogging agents, cold fogging agents, aerosols, solid / liquid mixtures, liquid / liquid mixtures, solid / solid mixtures, medicated paints, microparticles, tracking powders, oil suspensions, oil-dispersible powders, concentrated gels, pouring agents, seed coating agents, coating agents, film-forming oils, ultra-low volume liquids, and vapor release agents;

[0049] The mites controlled by the acaricide composition are selected from the following: the mites are selected from the Tetranychidae, Tetranychidae, Fusarium, Eriophyridae, Chlorella, and Eriophyridae families, and the mites are global agricultural mites, forestry mites, horticultural mites and sanitary mites.

[0050] The acaricide composition is used to control plants selected from: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, peanut, rapeseed, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili pepper, radish, cucumber, cabbage, celery, pickled mustard greens, beet, rapeseed, onion, garlic, watermelon, cantaloupe, honeydew melon, papaya, apple, citrus and peach trees, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, and bonsai.

[0051] The bioactivity of the 3,4-dichloroisothiazol benzamide derivative I described in this invention was determined as follows:

[0052] Determination of the bactericidal activity of the 3,4-dichloroisothiazol benzamide derivative I of the present invention:

[0053] The bactericidal or bacteriostatic activity of the 3,4-dichloroisothiazol benzamide derivative I of this invention was determined by the cell growth rate assay. The specific steps are as follows: 1.8 mg of sample was dissolved in 2 drops of dimethyl sulfoxide, then diluted to 500 μg / mL with an aqueous solution containing a certain amount of Tween 20 emulsifier. Under aseptic conditions, 1 mL of the test reagent was placed in each petri dish, and 9 mL of potato dextrose agar medium was added. After shaking well, a 50 μg / mL drug-containing plate was prepared. A plate with 1 mL of sterile water added was used as a blank control. The reaction was carried out using a direct... Using a 4 mm diameter punch, mycelial discs were cut along the outer edge of the hyphae and transferred to drug-containing plates, arranged in an equilateral triangle. Each treatment was repeated three times. The petri dishes were incubated in a constant temperature incubator at 24 ± 1 degrees Celsius. After the diameter of the control colonies expanded to 2-3 cm, the diameter of the expanded mycelial discs for each treatment was measured, and the average value was calculated. The relative inhibition rate was calculated by comparing the average value with the blank control. The tested fungal species are most of the typical plant pathogens that actually occur in the field in my country's agricultural production. Their codes and names are as follows: As: Tomato early blight pathogen, its Latin name is Alternaria. solani, Bc: Botrytis cinerea, the causal agent of gray mold in cucumber; Ca: Cercospora aracidola, the causal agent of brown spot in peanut; Fg: Fusarium graminearum, the causal agent of Fusarium graminearum; Pp: Physalospora piricola, the causal agent of ring rot in apple; Rs: Rhizoctonia solani, the causal agent of sheath blight in rice; Ss: Sclerotinia sclerotiorum, the causal agent of sclerotinia in rapeseed.

[0054] This invention provides more specific examples of the synthesis, bioactivity, and application of 3,4-dichloroisothiazolium benzamide derivative I through specific preparation and bioactivity assays. These examples are for illustrative purposes only and are not intended to limit the invention. In particular, the bioactivity is merely illustrative and not intended to limit this patent. Specific implementation methods are as follows:

[0055] Example 1: Preparation of compound I-17:

[0056] (1) Take 100 mL of round bottom flask, add compound 1 (15.0 mmol) and tetrahydrofuran (20.0 mL), stir to dissolve, then add potassium carbonate (45.0 mmol) and potassium iodide (15.0 mmol) in sequence, stir at room temperature for 1 hour, then slowly add methyl 2-hydroxybenzoate (25.0 mmol) dropwise. After the addition is complete, heat to 80 degrees Celsius and reflux for 8 hours. After the reaction is complete, cool to room temperature, add water to stop the reaction, extract with ethyl acetate three times, 25 mL each time, combine the organic phases, dry with anhydrous sodium sulfate, remove the solvent under reduced pressure, and purify the residue by column chromatography to obtain compound 2;

[0057] (2) Take a 250 mL round-bottom flask, add compound 2 (12.0 mmol) and a mixed solution of lithium hydroxide aqueous solution / anhydrous ethanol, wherein the volume ratio of lithium hydroxide aqueous solution to anhydrous ethanol is 4:1. Heat to 80 degrees Celsius with stirring and react for 6 hours. After the reaction is complete, cool to room temperature. Adjust the pH of the reaction solution to 2 to 3 with 1 mol / L dilute hydrochloric acid. A white solid precipitates out. Collect by suction filtration, wash with water and dry to obtain compound 3.

[0058] (3) Take a 100 mL round-bottom flask, add compound 3 (3.0 mmol) and dichloromethane (20.0 mL), stir to dissolve, and slowly add triethylamine (3.6 mmol), followed by 3-bromoaniline (3.6 mmol), then add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (3.6 mmol) and 1-hydroxybenzotriazole (3.0 mmol) in sequence. Stir the reaction at room temperature overnight. After the reaction is complete, add water to terminate the reaction. Extract three times with dichloromethane, 25 mL each time. Combine the organic phases, dry with anhydrous sodium sulfate, remove the solvent under reduced pressure, and purify the residue by column chromatography to obtain 3,4-dichloroisothiazol benzamide derivative I-17.

[0059] Example 2: Results of antibacterial activity assay of the 3,4-dichloroisothiazol benzamide derivative I of the present invention:

[0060] The common plant pathogenic fungi tested in this invention are coded and named as follows: As: *Alternaria solani*, the Latin name for early blight of tomato; Bc: *Botrytis cinerea*, the Latin name for gray mold of cucumber; Ca: *Cercospora arachidicola*, the Latin name for brown spot of peanut; Fg: *Fusarium graminearum*, the Latin name for Fusarium graminearum; Pp: *Physalospora piricola*, the Latin name for ring rot of apple; Rs: *Rhizoctonia solani*, the Latin name for sheath blight of rice; Ss: *Sclerotinia sclerotiorum*, the Latin name for sclerotinia sclerotiorum, the Latin name for sclerotinia sclerotiorum. These species are highly representative and can represent most of the pathogenic fungi occurring in the field during agricultural production.

[0061] The results of the cell growth rate assay are shown in Table 2. Table 2 shows that all compounds synthesized in this invention have varying degrees of fungicidal activity. Using commercially available plant immune activators benzothiadiazole (BTH) and isothiazamine (ISO) as positive controls, the results showed that at a concentration of 50 μg / mL, compounds I-5 and I-6 exhibited relatively good antibacterial activity against *Rhizoctonia solani*, with inhibition rates of 50.1% and 49.1%, respectively; compounds I-5 and I-14 showed good activity against *Early Blight* causal agent of tomato, with inhibition rates of 52.2% and 51.7%, respectively; compound I-6 showed superior activity against *Gyromitra esculenta* causal agent of cucumber, with an inhibition rate of 68.0%; and compounds I-9 and I-12 showed good activity against *Brachys thunbergii* causal agent of peanut brown spot, with inhibition rates of 51.2% and 49.2%, respectively.

[0062] The results of the induction of disease resistance are shown in Table 3. Table 3 shows that the 3,4-dichloroisothiazol benzamide derivatives I synthesized in this invention all exhibited different degrees of induction of disease resistance activity. Using commercially available plant immune activators benzothiadiazole (BTH) and isothiazamine (ISO) as positive controls, the results showed that at a concentration of 50 μmol / L, compound I-17 exhibited the best induction of disease resistance activity, with an inhibition rate of 93.4%, superior to the positive controls BTH (90.5%) and ISO (52.2%). Compound I-10 also showed strong induction of disease resistance activity, with an inhibition rate of 86.1%. Furthermore, compounds I-9, I-13, I-14, and I-15 also showed good induction of disease resistance effects, with inhibition rates of 71.9%, 76.3%, 71.3%, and 73.3%, respectively.

[0063] Example 3: Application of the 3,4-dichloroisothiazol benzamide derivative I of the present invention in combination with insecticides for the control of agricultural, forestry, and horticultural plant pests:

[0064] The 3,4-dichloroisothiazol benzamide derivative I of the present invention, in combination with any one or two commercial insecticides, forms an insecticidal composition for controlling pests in agricultural, forestry, and horticultural plants. The commercial insecticides are selected from: imidacloprid, difenoconazole, acetamiprid, emamectin, mibamectin, abamectin, spinosad, cypermethrin, cypermethrin, deltamethrin, deltamethrin, cypermethrin, β-cypermethrin, λ-cypermethrin, dichlorvos, permethrin, allethrin, bifenthrin, permethrin, fenpropathrin, flufenoxuron, and deltamethrin. Imidacloprid, acetamiprid, chlorpyrifos, thiamethoxam, thiamethoxam, dinotefuran, conidine, datnam, diflubenzuron, diflubenzuron, flufenoxuron, flufenoxuron, acetamiprid, lufenuron, fenflurfen, flufenoxuron, polyfluorourea, flufenoxuron, difenourea, flufenoxuron, fenflurfen, difenourea, fenflurfen, chlorfenapyr, methoxyfenozide, cyclophosphamide, dichlorvos, quinalphos, pyridazin, leafhopper spray, carbaryl, imidacloprid, fenpropathrin, isoprocarb, fenitrothion, sec-butylcarbide, leaf spray, carbaryl, fenitrothion, bromopropylate, thiamethoxam, azoxystrobin, pyridaben, tetradifon, propargite, buprofen The insecticide composition contains pymetrozine, spirodiclofen, spirotetramat, spirotetramat ethyl ester, triazophos, thiamethoxam, cartap, chlorantraniliprole, tetrachlorantraniliprole, flufenoxuron, flufenoxuron, cyanantraniliprole, butenpyram, acetamiprid, bromfenoxuron, pyrazinone, etoxazole, pyridoxamine, pyridoxine, pyriproxyfen, emamectin, pendimethalin; the 3,4-dichloroisothiazolium benzamide derivative I of the present invention has a mass percentage content of 1%-90% in the insecticidal composition, and the ratio of the 3,4-dichloroisothiazolium benzamide derivative I of the present invention to the aforementioned commercial insecticides is 1%:99% to 99%:1% by mass percentage; the insecticidal composition The formulations processed include: seed treatment emulsions, water-in-oil emulsions, microemulsions, suspensions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, poisoned grains, block poisoned baits, granular poisoned baits, flake poisoned baits, concentrated poisoned baits, slow-release blocks, electrostatic sprays, oil-in-water emulsions, smoke cans, smoke candles, smoke tubes, smoke sticks, smoke sheets, smoke pellets, gas generators, ointments, hot fogging agents, cold fogging agents, aerosols, solid / liquid mixtures, liquid / liquid mixtures, solid / solid mixtures, medicated paints, microparticles, tracking powders, oil suspensions, oil-dispersible powders, concentrated gels, pouring agents, seed coating agents, coating agents, film-forming oils, ultra-low volume liquids, and vapor release agents.The insecticidal composition is suitable for the following plant pests: fall armyworm, spider mite, Oriental migratory locust, spotted locust, Chinese rice locust, Japanese yellow-spined locust, single-spined mole cricket, oriental mole cricket, rice thrips, tobacco thrips, greenhouse thrips, rice tube thrips, wheat tube thrips, greenhouse whitefly, tobacco whitefly, black-tailed leafhopper, large green leafhopper, cotton leafhopper, spotted lanternfly, brown planthopper, white-backed leafhopper. Planthoppers, gray planthoppers, sugarcane flat-horned planthoppers, cotton aphids, wheat two-pronged aphids, wheat long-tubed aphids, peach aphids, sorghum aphids, radish aphids, cottony cushion scale, mulberry shield scale, arrowhead shield scale, pear round scale, white wax insect, red wax scale, Korean ball scale, pear lace bug, banana lace bug, slender flower bug, tiny flower bug, needle-edged bug, rice spider-edged bug, rice brown bug, rice black bug, rice green bug, green mirid bug, alfalfa mirid bug, Black mirid bug, large lacewing, beautiful lacewing, Chinese lacewing, grain moth, clothes moth, yellow tussock moth, brown tussock moth, flat tussock moth, wheat moth, cotton bollworm, sweet potato wheat moth, diamondback moth, peach fruit moth, soybean fruit moth, peach fruit moth, apple top leafroller, brown-banded long leafroller, false yellow leafroller, rice stem borer, bean pod borer, corn borer, three-spined rice stem borer, cabbage stem borer, rice leaf roller, rice leaf roller The following are listed: Rice leaf roller, cotton leaf roller, peach borer, armyworm, beet armyworm, rice stem borer, cotton bollworm, beet armyworm, large stem borer, cotton bollworm, *Gnaphalium affine*, cutworm, large cutworm, yellow cutworm, tussock moth, gypsy moth, sweet potato hawk moth, bean hawk moth, straight-striped rice skipper, hidden-striped rice skipper, citrus swallowtail butterfly, white-banded swallowtail butterfly, cabbage white butterfly, ramie red ramie butterfly, ramie yellow ramie butterfly. Butterfly, Bean Fern, Golden Ground Beetle, Wrinkled-Sheath Ground Beetle, Wheat Ear Ground Beetle, Threadworm, Fine-breasted Threadworm, Grain-spotted Ground Beetle, Black Ground Beetle, Citrus Small Jewel Beetle, Golden-edged Jewel Beetle, Yellow Mealworm, Black Mealworm, Red Flour Beetle, Mixed Flour Beetle, Green-green Scarab Beetle, Dark Scarab Beetle, North China Large Black-gilled Scarab Beetle, Mulberry Longhorn Beetle, Star Longhorn Beetle, Orange Brown Longhorn Beetle, Peach Red-necked Longhorn Beetle, Large Ape Leaf Beetle, Small Leaf beetle, cucumber beetle, yellow-striped flea beetle, bean weevil, pea weevil, broad bean weevil, corn weevil, rice weevil, wheat leaf beetle, pear fruit wasp, yellow-banded ichneumon wasp, armyworm white-spotted ichneumon wasp, larval ichneumon wasp, cotton bollworm toothed ichneumon wasp, larval black-spotted wart ichneumon wasp, mosquito, fly, horsefly, wheat red midge, wheat yellow midge, rice gall midge, citrus fruit fly, melon fruit fly, wheat leaf miner, American serpentine leafminer Flies, including black leafminer flies, wheat stem flies, seed flies, onion flies, turnip flies, umbrella-shaped leafminer flies, corn borers, and armyworms; the insecticidal composition is suitable for plants selected from: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, peanut, rapeseed, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili pepper, radish, cucumber, cabbage, celery, pickled mustard greens, beet, rapeseed, onion, garlic, watermelon, cantaloupe, honeydew melon, papaya, apple, citrus and peach trees, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, and bonsai.

[0065] Example 4: Application of the combination of the 3,4-dichloroisothiazol benzamide derivative I of the present invention with a fungicide in the prevention and control of diseases in agricultural, forestry, and horticultural plants:

[0066] The 3,4-dichloroisothiazol benzamide derivative I of the present invention, in combination with any one or two commercial fungicides, forms a fungicidal composition for the control of diseases in agricultural, forestry, and horticultural plants. The commercial fungicides are selected from: benzothiadiazole, thiamethoxam, methyl thiamethoxam, isothiazamide, ribavirin, anthraquinone, ningnanmycin or salicylic acid, cymoxanil, thiram, thiram, mancozeb, fosetyl-aluminum, thiophanate-methyl, chlorothalonil, dichlorvos, iprodione, benzyl benzoate, thiophanate-methyl, thiophanate-methyl, metalaxyl, flumorph, dimethomorph, high-efficiency metalaxyl, high-efficiency benzyl benzoate, dichloroisothiazide, sulfadiazine, mesotrione, thiabendazole, chlorothalonil, propiconazole, cyclopropiconazole, cyclofluoroacetate, cyclopropiconazole, cyproconazole, silthiamethoxam, carbendazim, oxychloride, and wheat bran. Rust-killing agent, methomyl, rust-killing agent, fluopyram, furazolidone, thifluzamide, cyproconazole, pyraclostrobin, pyraclostrobin, bifenthiophanate-methyl, fluopyram, fluoxastrobin, fluoxastrobin, fluoxastrobin aniline, benzyl-fluoroquinolone, isothiazamide, fluoxastrobin hydroxylamine, flufenoxuron, fluoxastrobin, diyrylamide, benzyl-fluoroquinolone, ethoxysulfuron, iprodione, pyrimethanil Ester, azoxystrobin, fluopyram, azoxystrobin, fenoxystrobin, oxadiazon, azoxystrobin, pyraclostrobin, oxadiazon, tebuconazole, oxadiazon ... Prothioconazole, silfluzazole, tebuconazole, tetraflufenazole, triazole, tebuconazole, bifenthrin, thiabendazole, imazalil, pyraclostrobin, imazalil, prochloraz, fluconazole, cyazofamid, imazalil, oxadiazon, isoprothiolane, oxadiazon, pyraclostrobin, oxadiazon, oxadiazon, thiabendazole, terbufos, octothiazoline, benzylthiazoline, dodecyl morpholine, butyl morpholine, trideclofenac Morpholine, Seed dressing, Fludioxonil, Fluazinam, Pyridabenoxime, Cyclopyralid, Fluazinam, Cyclopyralid, Azoxystrobin, Fluazinam, Thifluzamide, Azoxystrobin, Pyrimethanil, Chlorpheniramine, Flupheniramine, Acaricide, Dicyandioxonone, Ethoxyquinoline, Hydroxyquinoline, Propoxyquinoline, Phenoxyquinoline, Ethiocarb, Isopropylamine, Benzylamine, Cymoxanil, Sulfocarb, Dichlorvos, Isopropylamine Isoprothiolane, pyraclostrobin, methyl thiophanate, cymoxanil, kasugamycin, polyoxin, polyoxin, effectivemycin, jinggangmycin, streptomycin, metalaxyl, furazolidone, benzalkonium chloride, furazolidone, carbendazim, benomyl, thiophanate-methyl, triadimefon, ethirimol sulfonate, dimethomorph, ethirimol, captan, captan, vinclozolin, chlorothalonil, isoprothiolane, isoprothiolane, tebuconazole, pentachloronitrobenzene, propineb, aluminum triethylphosphonate, sulfur, Bordeaux mixture, copper sulfate, copper oxychloride, cuprous oxide, copper hydroxide, benomyl, pendimethalin, pyridaben, tetrachlorophthalide, quinolones, spirocycline, tricyclazole, azithromycin, doxycycline, biguanide octyl salt, biguanide octylamine, chlorothalonil, benzylsulfonamide, toluenesulfonamide, indole esterSodium dichloroisothiazide, quinacrine, allylbenzyl thiamethoxam, bromonitol, iodomethane, methyl thiophanate, dimethoate, dazomet, dichloroisopropyl ether, thiamethoxam, fenpropathrin, chlorpyrifos, fenpropathrin, thiamethoxam, chlorpyrifos, thiocarbamate, thiodimethyl fluoride, dichloropropene, dichloroisonicotinic acid, allylisothiazide; the total mass percentage of the 3,4-dichloroisothiazide benzamide derivative I of the present invention in the bactericidal composition is 1%-90%, and the mass percentage of the 3,4-dichloroisothiazide benzamide derivative I of the present invention to the aforementioned commercial bactericides is [missing information]. 1%:99% to 99%:1%; the formulation of the bactericidal composition is selected from: seed treatment emulsions, water-in-oil emulsions, microemulsions, suspensions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, poisoned grains, block poisoned bait, granular poisoned bait, flake poisoned bait, concentrated poisoned bait, slow-release blocks, electrostatic sprays, oil-in-water emulsions, smoke cans, smoke candles, smoke tubes, smoke sticks, smoke sheets, smoke pellets, vaporizers, ointments, hot fogging agents, cold fogging agents, aerosols, solid / liquid mixtures, and liquid / liquid mixtures. Solid / solid mixtures, medicated paints, microparticles, tracking powders, oil suspensions, oil-dispersible powders, concentrated colloids, pour-over agents, seed coating agents, coating agents, film-forming oils, ultra-low volume liquids, and vapor release agents; the plant diseases for which the fungicidal composition is applicable are selected from: rice seedling rot, tomato root rot, potato late blight, tobacco black shank, millet powdery mildew, grape downy mildew, lettuce downy mildew, cucumber downy mildew, and cucumber anthracnose; the plants for which the fungicidal composition is applicable are selected from: rice, wheat, barley, oats, and corn. Sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, peanut, rapeseed, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili pepper, radish, cucumber, cabbage, celery, pickled mustard greens, beet, rapeseed, scallion, garlic, watermelon, cantaloupe, honeydew melon, papaya, apple, citrus and peach trees, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.

[0067] Example 5: Application of the combination of the 3,4-dichloroisothiazol benzamide derivative I of the present invention and an antiviral agent in the prevention and control of viral diseases in agricultural, forestry, and horticultural plants:

[0068] The 3,4-dichloroisothiazolium benzamide derivative I of the present invention, in combination with any one or two commercial antiviral agents, forms an antiviral composition for the prevention and control of viral diseases in agricultural, forestry, and horticultural plants. The commercial antiviral agents are selected from: benzothiadiazole, thiamethoxam, isothiazamide, ribavirin, antofenzyme, ningnanmycin, methamidophos, or salicylic acid, pyrimethanil, dichloroisonicotinic acid, allylisothiazol, jinggangmycin, and morpholine guanidine hydrochloride. The total mass percentage of the 3,4-dichloroisothiazolium benzamide derivative I in the antiviral composition is 1%-9%. 0%, the ratio of the 3,4-dichloroisothiazolium benzamide derivative I of the present invention to the aforementioned commercial antiviral agent is 1%:99% to 99%:1% by mass; the dosage form of the antiviral composition is selected from: seed treatment emulsions, water-in-oil emulsions, microemulsions, suspensions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, poisoned grains, block poisoned bait, granular poisoned bait, flake poisoned bait, concentrated poisoned bait, slow-release blocks, electrostatic sprays, oil-in-water emulsions, smoke cans, smoke candles, smoke tubes, smoke sticks, smoke sheets, smoke pellets, vaporizers, ointments, hot foggers, and cold foggers. Agents, aerosols, solid / liquid mixtures, liquid / liquid mixtures, solid / solid mixtures, medicated paints, microparticles, tracking powders, oil suspensions, oil-dispersible powders, concentrated colloids, pouring agents, seed coating agents, coating agents, film-forming oils, ultra-low volume liquids, vapor release agents; the viral diseases controlled by the antiviral composition are selected from: rice dwarf virus, yellow dwarf virus, stripe leaf blight, tomato fern leaf virus, pepper mosaic virus, tobacco vein necrosis virus, maize dwarf mosaic virus, cauliflower mosaic virus, citrus virus, Cymbidium faberi leaf virus, Cymbidium ringspot virus; the antiviral composition is used for The plants selected for prevention and control include: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, peanut, rapeseed, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili pepper, radish, cucumber, cabbage, celery, pickled mustard greens, beet, rapeseed, scallion, garlic, watermelon, cantaloupe, honeydew melon, papaya, apple, citrus and peach trees, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, and bonsai.

[0069] Example 6: Application of the combination of the 3,4-dichloroisothiazol benzamide derivative I of the present invention with an acaricide in the control of mite pests in agricultural, forestry, and horticultural plants:

[0070] The 3,4-dichloroisothiazol benzamide derivative I of the present invention, in combination with any one or two commercial acaricides, forms an acaricide composition for controlling mite pests in agricultural, forestry, and horticultural plants. The commercial acaricides are selected from: dichlorvos, heptamethrin, methamidophos, dibromophos, pyrimiphos, chlorpyrifos, ethion, chlorfenapyr, fenpropathrin, methyl pyrimiphos, quinalphos, abamectin, acephate, chlorpyrifos, chlorpyrifos, chlorfenapyr, bifenthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, flufenoxuron, deltamethrin, bromoflufenoxuron, bifenazate, fenthiocarb, methyl ketone carbendazim, nematicide, chlorpyrifos, chlorfenapyr, chlorpyrifos ... Ester, dicofol, dicofol, flufenoxuron, flufenoxuron, liuyangmycin, chlorfenapyr, thuringin, dicofol, liuyangmycin, avermectin, doramectin, epoximectin, ivermectin, selamectin, moxibustion, pyrethroid, nicotine, matrine, azadirachtin, rotenone, pyridaben, pyridaben, azoxystrobin, tetradifon, propargite, thiamethoxam, spirodiclofen, pyrimethanil, dicofol, clodinafop-methyl, pyridaben; the total mass percentage of the 3,4-dichloroisothiazol benzamide derivative I of the present invention in the acaricide composition is 1%-90%, and the ratio of the 3,4-dichloroisothiazol benzamide derivative I of the present invention to the commercial acaricide is 1%:99% to 99%:1% by mass percentage; the acaricide composition The formulations used in the processing of the acaricides are selected from: seed treatment emulsions, water-in-oil emulsions, microemulsions, suspensions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, poisoned grains, block poisoned baits, granular poisoned baits, flake poisoned baits, concentrated poisoned baits, slow-release blocks, electrostatic sprays, oil-in-water emulsions, smoke cans, smoke candles, smoke tubes, smoke sticks, smoke sheets, smoke pellets, gas generators, ointments, hot fogging agents, cold fogging agents, aerosols, solid / liquid mixtures, liquid / liquid mixtures, solid / solid mixtures, medicated paints, microparticles, tracking powders, oil suspensions, oil-dispersible powders, concentrated gels, spraying agents, seed coating agents, smearing agents, film-forming oils, ultra-low volume liquids, and vapor release agents; the acaricide composition controls acaricides from the following mites: Tetranychidae, Trichophyton, and Fusarium mites. The mite-killing composition is formulated to control harmful mites belonging to the families Erythropodidae, Chlorophytum, and Chlorophytum. These mites are global agricultural, forestry, horticultural, and sanitary pests. The plants used in the mite-killing composition are selected from: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, peanut, rapeseed, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili pepper, radish, cucumber, cabbage, celery, pickled mustard greens, beet, rapeseed, onion, garlic, watermelon, cantaloupe, honeydew melon, papaya, apple, citrus and peach trees, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, and bonsai.

[0071] Example 7: Application of the 3,4-dichloroisothiazol benzamide derivative I of the present invention in the preparation of pesticide compositions:

[0072] The present invention provides a pesticide composition for preparing a pesticide composition containing the 3,4-dichloroisothiazol benzamide derivative I of the present invention as an active ingredient, wherein the active ingredient has a mass percentage content of 0.1% to 99.9%, a solid or liquid adjuvant has a mass percentage content of 99.9% to 0.1%, and further contains optionally a surfactant with a mass percentage content of 0 to 25%.

[0073] Example 8: Application of the 3,4-dichloroisothiazol benzamide derivative I of the present invention in the preparation of pesticide compound compositions:

[0074] The 3,4-dichloroisothiazol benzamide derivative I of the present invention can be compounded with other commercial pesticides, namely insecticides, acaricides, fungicides, antivirals, or plant immune activators, to prepare pesticide compound compositions. These compound compositions contain the 3,4-dichloroisothiazol benzamide derivative I of the present invention and the commercial pesticides, namely insecticides, acaricides, fungicides, antivirals, or plant immune activators, as active ingredients. The ratio of the 3,4-dichloroisothiazol benzamide derivative I of the present invention to other commercial pesticides, namely insecticides, acaricides, fungicides, antivirals, or plant immune activators, is 1%:99% to 99%:1% by mass. The active ingredient has a mass percentage content of 0.1% to 99.9%, a solid or liquid adjuvant content of 99.9% to 0.1% by mass, and optionally a surfactant content of 0% to 25% by mass.

[0075] Industrial applicability

[0076] This invention provides a class of 3,4-dichloroisothiazol benzamide derivatives; the derivatives of this invention can regulate the biological activity of agricultural, horticultural, sanitary, and forestry plant pests and plant pathogens, and can be used in the fields of agriculture, horticulture, and forestry for insecticidal, acaricidal, bactericidal, antiviral, and inducing plant disease resistance, and have good economic value and application prospects.

[0077] Table 1. Chemical structure and physicochemical parameters of 3,4-dichloroisothiazol benzamide derivative I of the present invention.

[0078]

[0079]

[0080] Table 2. Antibacterial activity of the 3,4-dichloroisothiazol benzamide derivative I of the present invention (inhibition rate at 50 μg / mL / %)

[0081] Table 3. Results of the phytoimmunological activity assay of the 3,4-dichloroisothiazol benzamide derivative I in Arabidopsis thaliana using the method for determining spores of *Arabidopsis thaliana*.

Claims

1. A class of 3,4-dichloroisothiazolium benzamide derivatives having the general structural formula shown in Formula I: in, R is selected from: any substituted phenyl, any substituted benzyl, any substituted phenethyl, preferably from 4-chlorophenyl, 2-chlorophenyl, 2-methoxyphenyl, 4-fluorophenyl, 3-bromophenyl, 3-bromo-4-methoxyphenyl, 3-bromo-5-methoxyphenyl, 2-(3-fluorophenyl)ethyl, 2-(2-fluorophenyl)ethyl, 2-isopropenylphenyl, indenyl or 3-tert-butylphenyl; n is 0, 1, 2 or 3; preferably, n is 0 or 1.

2. The synthetic route and method for the 3,4-dichloroisothiazolium benzamide derivative I according to claim 1 are as follows: The definitions of substituents R and n are as described in claim 1, and the specific synthesis method comprises the following steps: Preparation of compound 2: Compound 1 (15.0 mmol) and tetrahydrofuran (20.0 mL) were added to a 100 mL round-bottom flask and stirred until dissolved. Potassium carbonate (45.0 mmol) and potassium iodide (15.0 mmol) were added sequentially. After stirring at room temperature for 1 hour, methyl benzoate of o-hydroxy substituted form (25.0 mmol) was slowly added dropwise. After the addition was complete, the mixture was heated to 80 °C and refluxed for 8 hours. After the reaction was complete, the mixture was cooled to room temperature and the reaction was terminated by adding water. The mixture was extracted three times with ethyl acetate, 25 mL each time. The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography to obtain compound 2. Preparation of compound 3: Take a 250 mL round-bottom flask, add compound 2 (12.0 mmol), and a mixed solution of lithium hydroxide aqueous solution / anhydrous ethanol, wherein the volume ratio of lithium hydroxide aqueous solution to anhydrous ethanol is 4:

1. Heat to 80 degrees Celsius with stirring and react for 6 hours. After the reaction is complete, cool to room temperature. Adjust the pH of the reaction solution to 2 to 3 with 1 mol / L dilute hydrochloric acid. A white solid precipitates out. Collect by suction filtration, wash with water and dry to obtain compound 3. Preparation of compound I: Take a 100 mL round-bottom flask, add compound 3 (3.0 mmol) and dichloromethane (20.0 mL), stir to dissolve, and slowly add triethylamine (3.6 mmol), followed by the addition of the substituted amine R-NH2 (3.6 mmol), then successively add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (3.6 mmol) and 1-hydroxybenzotriazole (3.0 mmol). Stir the reaction overnight at room temperature. After the reaction is complete, add water to terminate the reaction. Extract three times with dichloromethane, 25 mL each time. Combine the organic phases, dry with anhydrous sodium sulfate, remove the solvent under reduced pressure, and purify the residue by column chromatography to obtain 3,4-dichloroisothiazol benzamide derivative I.

3. The use of the 3,4-dichloroisothiazol benzamide derivative I according to claim 1 in the preparation of agricultural fungicides, wherein the fungicides control the following fungi: early blight of tomato, gray mold of cucumber, brown spot of peanut, Fusarium graminearum, Fusarium verticillatum, ring spot of apple, rice sheath blight, and sclerotinia sclerotium.

4. The use of the 3,4-dichloroisothiazol benzamide derivative I according to claim 1 in the preparation of an agricultural plant immune activator, wherein the target pathogens controlled by the plant activator are selected from: early blight of tomato, gray mold of cucumber, brown spot of peanut, Fusarium graminearum, Fusarium verticillatum, ring spot of apple, sheath blight of rice, sclerotinia sclerotium of rapeseed, and plant viral diseases.

5. An agricultural bactericidal composition comprising the 3,4-dichloroisothiazol benzamide derivative I of claim 1 as an active ingredient; the composition comprising 0.1% to 99.9% by weight of the active ingredient, 99.9% to 0.1% by weight of a solid or liquid adjuvant, and a surfactant selected from 0 to 25% by weight.

6. An agricultural bactericidal compound composition comprising, as an active ingredient, the 3,4-dichloroisothiazol benzamide derivative I of claim 1 and other commercial bactericides; wherein the ratio of 3,4-dichloroisothiazol benzamide derivative I to other commercial bactericides is 1%:99% to 99%:1% by weight, the compound composition comprising 1% to 99% by weight of the active ingredient, 99% to 1% by weight of solid or liquid adjuvants, and a surfactant selected from 0 to 25% by weight.

7. An agricultural insecticide and acaricide compound composition comprising, as an active ingredient, the 3,4-dichloroisothiazol benzamide derivative I of claim 1 and other commercial fungicides; wherein the ratio of 3,4-dichloroisothiazol benzamide derivative I to other commercial insecticides and acaricides is 1%:99% to 99%:1% by weight, and the compound composition comprises 1% to 99% by weight of the active ingredient, 99% to 1% by weight of solid or liquid adjuvants, and surfactants selected from 0 to 25% by weight.

8. A compound composition for resisting plant viruses, comprising the 3,4-dichloroisothiazolium benzamide derivative I of claim 1 and other commercial fungicides as active ingredients; wherein the ratio of 3,4-dichloroisothiazolium benzamide derivative I to other commercial anti-plant virus agents is 1%:99% to 99%:1% by weight, the compound composition comprising 1% to 99% by weight of the active ingredient, 99% to 1% by weight of solid or liquid adjuvants, and a surfactant selected from 0 to 25% by weight.

9. A compound composition of plant immune activators comprising, as an active ingredient, the 3,4-dichloroisothiazol benzamide derivative I of claim 1 and other commercial fungicides; wherein the ratio of 3,4-dichloroisothiazol benzamide derivative I to other commercial plant immune activators is 1%:99% to 99%:1% by weight, the compound composition comprising 1% to 99% by weight of the active ingredient, 99% to 1% by weight of solid or liquid adjuvants, and a surfactant selected from 0 to 25% by weight.

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