A class of 3,4-dihydro-5h-spiro[furan-2,3'-indolin]-2',5-dione derivatives, processes for their preparation and uses thereof

Abstract

The application provides a kind of 3, 4-dihydro-5H-spiro [furan-2, 3'-indoline]-2', 5-diketone derivatives and preparation method and purposes thereof, specifically relates to a kind of derivatives, and the chemical structure general formula is seen formula I: I: the structure general formula, synthesis method and purposes of the above compound are disclosed as insecticide, acaricide, fungicide, anti-plant virus agent, plant activator, which is combined with agriculturally 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 and preparation method.

Description

Technical Field

[0001] The technical solution of this invention belongs to the field of pesticides, and relates to 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivatives thereof, their preparation methods and uses. Background Technology

[0002] Fusarium fungi are a group of pathogenic fungi widely distributed in global agricultural ecosystems. They can infect crop roots, stems, and fruits, causing serious diseases such as wilting, root rot, and ear rot, posing a significant threat to various food and cash crops such as wheat, corn, and rice. These fungi not only directly cause crop yield reduction and quality decline, but some species can also produce fungal toxins, threatening human and animal health and further exacerbating agricultural losses (Xu Huaijian, et al. Acta Phytopathologica Sinica, 2025, 55(04):622-635). Currently, the control of Fusarium fungi still heavily relies on chemical fungicides, but long-term use has led to increasingly prominent problems of drug resistance. In addition, with increasingly stringent environmental protection policies, there is an urgent need to develop new fungicides with novel structures, unique mechanisms of action, and environmental friendliness (Wang Xia, et al. Henan Agricultural Sciences, 2007, 7: 57-60).

[0003] Spirocyclic structures have attracted much attention in medicinal chemistry and pesticide design due to their three-dimensional rigidity and unique spatial orientation. In the field of pesticides, the introduction of spirocyclic structures can optimize the physicochemical properties of molecules, enhance target binding specificity, and help overcome the resistance problem of existing agents (Yuan Ting, et al. Modern Pesticides, 2024, 23(01): 40-50). In order to find and discover more efficient, broad-spectrum, low-toxicity and non-cross-resistance pesticide lead and candidate compounds, this invention designed and synthesized a class of 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivatives, and found that they exhibited good fungicidal activity at low concentrations, and can be used as potential fungicide candidates. Summary of the Invention

[0004] The technical problem to be solved by this invention is to provide a new method for synthesizing a class of derivatives containing 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione, to provide methods for regulating the bioactivity of these compounds in agricultural, horticultural, and forestry plant pests and pathogens and their determination, and to provide applications of these compounds in the fields of agriculture, horticulture, and forestry.

[0005] The technical solution adopted by this invention to solve this technical problem is: The general chemical formula of a 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative with insecticidal, acaricidal, fungicidal, antiviral, and plant disease-inducing activities in agriculture, horticulture, and forestry is shown in Figure I.

[0006] I:

[0007] Wherein, R is selected from: phenyl, 1-5 R 1 Substituted phenyl, benzyl, 1-5 R 1 Substituted benzyl, acetophenone, 1-5 R 1 Substituted acetophenone group, 1-4 R 1 Substituted pyridinyl group, 1-3 R 1 Substituted pyrimidinyl, C1-C12 alkoxy; R 1 Selected from: fluorine, chlorine, bromine, C1-C6 alkyl.

[0008] The method for synthesizing the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I described in this invention comprises the following steps:

[0010] Synthetic route of compound I

[0011] A. Preparation of compound 2:

[0012] Compound 1 reacts with acrylic acid under acidic conditions to give compound 2;

[0013] Take a 100 mL round-bottom flask, add compound 1 (10.0 mmol), acrylic acid (10.0 mmol), acetic anhydride (1 mL), and acetic acid (10 mL), heat to 95 °C, and after the reaction is complete, adjust the pH to alkaline with 30% sodium hydroxide solution, extract three times with ethyl acetate (3 × 20 mL), discard the organic phase, adjust the pH to acidic with 1 mol / L hydrochloric acid, and a solid precipitates out. Filter to obtain compound 2.

[0014] B. Preparation of compound 3:

[0015] Compound 2 undergoes an oxidative cyclization reaction with sodium iodide and hydrogen peroxide to give compound 3;

[0016] Take a 100 mL round-bottom flask, add compound 2 (17.4 mmol), acetonitrile (100 mL), sodium iodide (1.7 mmol), and hydrogen peroxide (104.4 mmol), stir at room temperature, and after the reaction is complete, remove the acetonitrile under reduced pressure, extract with ethyl acetate (3 × 50 mL), wash successively with saturated sodium bicarbonate (3 × 50 mL) and saturated brine (50 mL), dry with anhydrous sodium sulfate, remove the organic solvent under reduced pressure, and purify the residue by silica gel column chromatography to obtain compound 3.

[0017] C. Preparation of Compound I:

[0018] Compound 3 reacts with a halogenated compound to give compound I;

[0019] Take a 100 mL round-bottom flask, add compound 3 (2.46 mmol), acetonitrile (15 mL), potassium carbonate (3.69 mmol), and substituted acetophenone / substituted benzyl bromide (2.46 mmol). Heat to 80 °C and stir until the reaction is complete. Remove acetonitrile under reduced pressure, extract with ethyl acetate (3 × 20 mL), wash successively with saturated sodium bicarbonate (3 × 20 mL) and saturated brine (20 mL), dry with anhydrous sodium sulfate, remove organic solvent under reduced pressure, and purify the residue by silica gel column chromatography to obtain derivative I containing 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione.

[0020] D. Uses of 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I:

[0021] This invention provides the use of 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I in the preparation of insecticides.

[0022] This invention provides the use of 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione 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, sheath blight of rice, and sclerotinia sclerotium of rapeseed.

[0023] This invention provides the use of 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I in the preparation of an anti-tobacco mosaic virus agent.

[0024] This invention provides the use of 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione 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.

[0025] 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.

[0026] This invention provides a 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione 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 pesticide composition includes agricultural fungicides, agricultural insecticides, agricultural antiviral compositions, and agricultural plant immune activators. The composition comprises the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative as described in claim 1 as the active ingredient. The composition contains 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 0% to 25% by weight of a surfactant.

[0027] E. Derivatives I containing 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione, compositions thereof, and their uses:

[0028] An agricultural composition is formed by combining 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I with a commercial pesticide for application. The commercial pesticide is selected from one or more of insecticides, fungicides, antiviral agents, acaricides, and plant immune activators. The composition contains 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I with other commercial insecticides, fungicides, antiviral agents, acaricides, and plant immune activators as active ingredients. The active ingredient content of the composition is 1%:99% to 99%:1% by weight. This compound composition contains 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. Specific combinations are as follows:

[0029] The 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I, combined with any one or two of the insecticides, forms an insecticidal composition for the control of agricultural, forestry, and horticultural plant pests.

[0030] 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;

[0031] The mass percentage of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I in the insecticidal composition is 1%-90%; preferably, the ratio of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I to the insecticide is 1%:99% to 99%:1% by mass percentage.

[0032] 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;

[0033] 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;

[0034] 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.

[0035] The 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione 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.

[0036] 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;

[0037] The total mass percentage of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I in the bactericidal composition is 1%-90%; the ratio of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I to the bactericide is 1%:99% to 99%:1% by mass percentage.

[0038] 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;

[0039] 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.

[0040] 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.

[0041] The 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione 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.

[0042] 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;

[0043] The total mass percentage of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I in the antiviral composition is 1%-90%; preferably, the ratio of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I to the antiviral agent is 1%:99% to 99%:1% by mass.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] The 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione 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.

[0048] 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;

[0049] The total mass percentage of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I in the acaricide composition is 1%-90%; the ratio of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I to the acaricide is 1%:99% to 99%:1% by mass percentage.

[0050] 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;

[0051] 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.

[0052] 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.

[0053] The bioactivity of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I described in this invention was determined as follows:

[0054] Determination of the bactericidal activity of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I of the present invention:

[0055] The bactericidal or bacteriostatic activity of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I of the present 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, and 1 mL of sterile water was added. For the blank control, agar plates were used. Mycelial discs were cut along the outer edge of the hyphae using a 4 mm diameter punch and transferred to the treated agar plates, arranged in an equilateral triangle. Each treatment was repeated three times. The petri dishes were incubated at 24±1°C. After the control colony diameter 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 this average value with the blank control. The tested fungal species represent most typical plant pathogens actually occurring in the field in my country's agricultural production. Their codes and names are as follows: As: *Alternaria alternata*, the Latin name of *Alternaria alternata*. solani, Bc: Botrytis cinerea, the causal agent of gray mold in cucumber; Ca: Cercospora arachidicola, the causal agent of brown spot in peanut; Fg: Fusarium graminearum, the causal agent of Fusarium graminearum; Fv: Fusarium verticillioides, the causal agent of Fusarium verticillioides; 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.

[0056] This invention provides more specific examples of the synthesis, bioactivity, and application of 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione 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:

[0057] Example 1: Preparation of compound I-1:

[0058] (1) Take a 100 mL round-bottom flask, add compound 1 (10.0 mmol), acrylic acid (10.0 mmol), acetic anhydride (1 mL), and acetic acid (10 mL), heat to 95°C, and after the reaction is complete, adjust the pH to alkaline with 30% sodium hydroxide solution, extract three times with ethyl acetate (3 × 20 mL), discard the organic phase, adjust the pH to acidic with 1 mol / L hydrochloric acid, and a solid precipitates out. Filter to obtain compound 2 (white solid, 80% yield);

[0059] (2) Take a 100 mL round-bottom flask, add compound 2 (1.7 mmol), acetonitrile (10 mL), sodium iodide (0.17 mmol), and hydrogen peroxide (10.4 mmol), stir at room temperature, and after the reaction is complete, remove acetonitrile under reduced pressure, extract with ethyl acetate (3 × 10 mL), wash successively with saturated sodium bicarbonate (3 × 10 mL) and saturated brine (10 mL), dry with anhydrous sodium sulfate, remove organic solvent under reduced pressure, and purify the residue by silica gel column chromatography to obtain compound 3 (white solid, 75% yield);

[0060] (3) Take a 100 mL round-bottom flask, add compound 3 (2.46 mmol), acetonitrile (15 mL), potassium carbonate (3.69 mmol), and benzyl bromide (2.46 mmol), heat to 80 °C and stir. After the reaction is complete, remove the acetonitrile under reduced pressure, extract with ethyl acetate (3 × 20 mL), wash successively with saturated sodium bicarbonate (3 × 20 mL) and saturated brine (20 mL), dry with anhydrous sodium sulfate, remove the organic solvent under reduced pressure, and purify the residue by silica gel column chromatography to obtain 1'-benzyl-3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione. (White solid, 76% yield);

[0061] Example 2: Results of antibacterial activity assay of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I of the present invention:

[0062] 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; Fv: *Fusarium verticillioides*, the Latin name for Fusarium verticillioides; 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.

[0063] 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. The bioactivity of the new compounds was determined using different types of commercially available fungicides, such as fluopyram, as positive controls. EC50 measurements showed that, against *Gyromyces cuspidatum*, compound I-19 (10.77 μg / mL) showed weaker activity than fluopyram (2.27 μg / mL). Against *Fusarium oxysporum*, all compounds exhibited superior antifungal activity compared to fluopyram (16.8 μg / mL). Among them, I-4 showed the best activity (0.88 μg / mL), with significantly better antifungal activity than fluopyram. The EC50 values ​​of the remaining compounds ranged from 2.17 to 12.80 μg / mL. Antimicrobial activity assessments against *Rhizoctonia solani* var. *mongolica* revealed that compounds I-4 and I-24 exhibited good activity, with EC50 values ​​of 3.50 and 12.73 μg / mL, respectively, showing superior antimicrobial activity compared to fluopyram (32.51 µg / mL). Antimicrobial activity tests against *Rhizoctonia solani* var. *mongolica* showed that compound I-12 had an EC50 value of 9.38 μg / mL, indicating weaker activity than fluopyram (0.01 μg / mL). Antimicrobial activity assays against *Sclerotinia sclerotinia* var. *rapeseed* showed that all compounds exhibited superior antimicrobial activity compared to fluopyram (27.4 μg / mL). Compound I-4 (1.79 μg / mL) showed the best antimicrobial activity. In addition, I-1 (8.95 μg / mL) and I-24 (6.52 μg / mL) also showed good antibacterial activity, while I-3 and I-23 had EC50 values ​​of 10.09 and 12.71 μg / mL, respectively, indicating moderate bactericidal activity.

[0064] Example 3: Application of the present invention, containing 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I in combination with an insecticide, in the control of agricultural, forestry, and horticultural plant pests:

[0065] The present invention relates to an insecticidal composition comprising a 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I, and any one or two commercial insecticides for the control of agricultural, forestry, and horticultural plant pests. The commercial insecticides are selected from: imidacloprid, difenoconazole, acetamiprid, emamectin, bamectin, spinosad, cypermethrin, deltamethrin, deltamethrin, cypermethrin, β-cypermethrin, λ-cypermethrin, dichlorvos, permethrin, allethrin, bifenthrin, permethrin, fenpropathrin, fenpropathrin, flufenoxuron, and cypermethrin. Cypermethrin, Imidacloprid, Acetaminophen, Chlorpyrifos, Thiamethoxam, Thiamethoxam, Dinotefuran, Conidine, Datnam, Diflubenzuron, Diflubenzuron, Flufenoxuron, Flufenoxuron, Acetaminophen, Lufenuron, Toluene, Flufenoxuron, Polyfluorourea, Flufenoxuron, Difenofos, Flufenoxuron, Azoxystrobin, Difenofos, Fenfenoxuron, Tebufenozide, Chlorfenapyr, Methoxyfenozide, Cyclofenozide, Dichlorvos, Quinalphos, Pyrazamthiophos, Leafhopper Spray, Sevin, Apiridoxam, Mefenoxuron, Isoprocarb, Pyrimethanil, Butyric acid, Leafhopper Spray, Carbaryl, Pyrimethanil, Bromopropylate, Thiamethoxam, Azoxystrobin, Pyridoxam, Tetramethrin, Propyrimethanil, Difenoconazole, Pymetrozine, Spirodiclofen, Spirodiclofen The insecticides include spirotetramat, triazophos, thiamethoxam, cartap, chlorantraniliprole, tetrachlorantraniliprole, flufenoxuron, flufenoxuron, cyantraniliprole, butenpyram, acetamiprid, bromfenoxuron, pyrazinone, etoxazole, pyridaben, pyriproxyfen, emamectin, pendimethalin; the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I of the present invention comprises 1%-90% by mass in the insecticidal composition, and the ratio of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I of the present invention to the aforementioned commercial insecticides is 1%:99% by mass. Up to 99%:1%; the formulation of the insecticidal composition is selected from: seed treatment emulsion, water emulsion, microemulsion, suspension emulsion, capsule suspension, water-soluble granules, fine granules, soluble concentrate, poison grain, block poison bait, granular poison bait, flake poison bait, concentrated poison bait, slow-release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke rod, smoke sheet, smoke pellet, gas generator, ointment, hot fog agent, cold fog agent, aerosol, solid / liquid mixture, liquid / liquid mixture, solid / solid mixture, medicated paint, microparticles, tracking powder, oil suspension, oil-dispersible powder, concentrated glue, pouring agent, seed coating agent, coating agent, film-forming oil, ultra-low volume liquid, vapor release agent;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.

[0066] Example 4: Application of the present invention, containing 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I, in combination with fungicides, in the prevention and control of diseases in agricultural, forestry, and horticultural plants:

[0067] The present invention relates to a fungicide composition formed by combining a 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I with any one or two commercial fungicides for the control of diseases in agricultural, forestry, and horticultural plants. The commercial fungicides are selected from: benzothiadiazole, thiamethoxam, methyl thiamethoxam, isothiazine, 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, diclofenac, sulfadiazine, mesotrione, thiabendazole, chlorothalonil, propiconazole, propiconazole, cyclopropiconazole, cyclofluoroacetate, cyclopyridamole. Cyazofamid, silthiamethoxam, carbendazim, oxycarbendazim, methyl methoxyfenozide, methyl methoxyfenozide, fluopyram, furazolidone, thifluzamide, cyproconazole, pyraclostrobin, pyraclostrobin, bifenazate, fluopyram, fluopyram, fluopyram, fluopyram, fluopyram, fluopyram aniline, benzyl-fluoroquinolone, isothiazamide, fluopyram hydroxylamine, fluopyram, fluopyram Bistyrax, benzoyl amide, ethoxysulfuron, iprodione, pyraclostrobin, azoxystrobin, fluopyram, azoxystrobin, fenoxystrobin, oxadiazon, azoxystrobin, pyraclostrobin, oxadiazon, tebuconazole, cyproconazole, difenoconazole, tebuconazole, tebuconazole, flutriafol, cyproconazole, fluquinazole, flusilazole, fenpyroxacin, hexaconazole, nitrile benzoyl benzoate Amiconazole, tebuconazole, fenbendazole, cyproconazole, tebuconazole, propiconazole, prothioconazole, silflubaconazole, tebuconazole, tetraflufenazole, triazole, tebuconazole, bifenthrin, thiamethoxam, imazalil, cypermethrin, prochloraz, fluopyram, cyazofamid, imazalil, oxadiazon, isoprothiolane, oxadiazon, pyraclostrobin, oxadiazon, oxadiazon, thiamethoxam, thiamethoxam, terbuconazole Octathione, benzothiazoline, dodecyl morpholine, butyl morpholine, tridemorpholine, seed dressing agent, fluazinam, fluazinam, pyridaben, cyclopyridamole, fluazinam, pyridaben, pyrimethanil, fluazinam, thifluzamide, pyrimethanil, chlorophenazine alcohol, fluphenazine alcohol, abamectin, dicyananthraquinone, ethoxyquinoline, hydroxyquinoline, propoxyquinoline, phenoxyquinoline, ethoxycarb. Isopropylamine, benomyl, cymoxanil, sulfadiazine, difenoconazole, isoprothiolane, pyraclostrobin, methyl thiophanate, cymoxanil, kasugamycin, polyoxin, polyoxin, methyl thiophanate, jinggangmycin, streptomycin, metalaxyl, furazolidone, benzalkonium chloride, furazolidone, carbendazim, benomyl, thiophanate-methyl, triadimefon, ethirimol sulfonate, dimethomorph, ethirimol, captan, captan, vinclozolin, fluchlorothalonil, 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, pyrazosulfuron, doxycycline, biguanide, octyl guanidineBiguanide octylamine, chlornitramine, benzylsulfamethoxam, toluenesulfonamide, indole ester, sodium dichloroisocyanurate, quinacrine, allylbenzylthiazide, bromonitol, iodomethane, methyl thiophanate, dimethomorph, dazomet, dichloroisopropyl ether, thiamethoxam, fenpropathrin, fenpropathrin, fenpropathrin, thiocarbamate, thiocarbamate, thiocarbamate, dichloropropene, dichloroisonicotinic acid, allylisothiazide; the total mass percentage of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I in the bactericidal composition of the present invention is 1%-90%, the present invention contains 3, The percentage of 4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I to the aforementioned commercial fungicide is 1%:99% to 99%:1%; the formulation of the fungicide 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, and vaporizers. The fungicidal compositions include: ointments, hot mist agents, cold mist 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, and vapor release agents; the plant diseases for which the fungicidal compositions are 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 compositions are applicable 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, scallion, garlic, watermelon, cantaloupe, honeydew melon, papaya, apple, citrus and peach trees, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.

[0068] Example 5: Application of the present invention, containing 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I and an antiviral agent, in the control of viral diseases in agricultural, forestry, and horticultural plants:

[0069] The present invention relates to an antiviral composition formed by combining the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I with any one or two commercial antiviral agents 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, antofenfen, ningnanmycin, methamidophos or salicylic acid, pyrimethanil, dichloroisonicotinic acid, allylisothiazide, jinggangmycin, and morpholine guanidine hydrochloride. The present invention also relates to the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative. The total mass percentage of substance I in the antiviral composition is 1%-90%. The ratio of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione 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 baits, granular poisoned baits, flake poisoned baits, concentrated poisoned baits, slow-release blocks, electrostatic sprays, oil-in-water emulsions, smoke cans, and smoke candles. Smoke tubes, smoke rods, 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 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, and cymbidium leaf virus. Orchid ringspot virus; the plants used for prevention and control of the antiviral 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, bonsai.

[0070] Example 6: Application of the present invention, containing 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I, in combination with an acaricide for the control of mites in agricultural, forestry, and horticultural plants:

[0071] The present invention relates to a combination of 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I with any one or two commercial acaricides to form 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, aphid, acephate, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, fenpropathrin, bifenthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, flufenoxuron, and bromophos. Pyrethroids, bifenazate, fenthiocarb, methyl ethyl ketone, chlorpyrifos, carbaryl, chlorfenapyr, benomyl, chlorfenapyr, thiamethoxam, tebufenozide, benzyl benzoate, bromopropylate, diflubenzuron, fenpyroximate, flufenoxuron, liuyangmycin, chlorfenapyr, thiophanate-methyl, liuyangmycin, abamectin, doramectin, epoxim, ivermectin, selamectin, moxibustion, pyrethroids, nicotine, matrine, azadirachtin, rotenone, pyridaben, pyridaben, azoxystrobin, tetradifon, propargite, thiamethoxam, spirodiclofen, pyrimethanil, dicofol, chlorfenapyr, pyridaben; the present invention contains 3,4-dihydro-5H- The total mass percentage of spiro[furan-2,3'-indoline]-2',5-dione derivative I in the acaricide composition is 1%-90%. The ratio of 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I to the commercial acaricide is 1%:99% to 99%:1% by mass. 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, poisoned grains, block poisoned baits, granular poisoned baits, flake poisoned baits, concentrated poisoned baits, slow-release blocks, and electrostatic sprays. The acaricide composition includes: sprays, oil-in-water emulsions, smoke cans, smoke candles, smoke tubes, smoke rods, smoke sheets, smoke pellets, vaporizers, ointments, hot sprays, cold sprays, aerosols, solid / liquid mixtures, liquid / liquid mixtures, solid / solid mixtures, medicated paints, microparticles, tracking powders, oil suspensions, oil-dispersible powders, concentrated adhesives, pouring agents, seed coating agents, smears, film-forming oils, ultra-low volume liquids, and vapor release agents; the acaricide composition controls mites selected from: mites from the Tetranychidae, Trichophyton, Fusarium, Eriophyidae, Chlorella, and Eriophyididae families, which are global agricultural, forestry, horticultural, and sanitary mites;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.

[0072] Example 7: Application of the present invention containing 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I in the preparation of pesticide compositions:

[0073] The present invention relates to a pesticide composition prepared by containing 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I, wherein the composition contains 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I as the active ingredient, the active ingredient having a mass percentage content of 0.1% to 99.9%, a solid or liquid adjuvant having a mass percentage content of 99.9% to 0.1%, and further contains optionally 0 to 25% by mass of a surfactant.

[0074] Example 8: Application of the present invention containing 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I in the preparation of pesticide compound compositions:

[0075] The 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I of the present invention can be compounded with other commercial pesticides, namely insecticides, acaricides, fungicides, antiviral agents, or plant immune activators, to prepare pesticide compound compositions. These compound compositions comprise the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I of the present invention and commercial pesticides, namely insecticides, acaricides, fungicides, antiviral agents, or plant immune activators. As the active ingredient, the present invention comprises a solid or liquid adjuvant containing 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I and other commercial pesticides, namely insecticides, acaricides, fungicides, antivirals or plant immune activators, in a mass percentage ratio of 1%:99% to 99%:1%, and an active ingredient mass percentage of 1%:99% to 99%:1%, and optionally a surfactant in a mass percentage of 0% to 25%.

[0076] Industrial applicability

[0077] This invention provides a class of derivatives containing 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione; 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.

[0078] Table 1. Chemical structure and physicochemical parameters of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivatives of the present invention.

[0079]

[0080]

[0081]

[0082]

[0083] Table 2. Antibacterial activity of the present invention containing 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I (inhibition rate / %) at 50 μg / mL

[0084] Table 3. Precision toxicity assay results of antibacterial activity of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I of the present invention (EC50) 50 (micrograms / ml)

Claims

1. A class of 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivatives having the general structural formula shown in Formula I: I: in, R is selected from: phenyl, 1-5 R 1 Substituted phenyl, benzyl, 1-5 R 1 Substituted benzyl, acetophenone, 1-5 R 1 Substituted acetophenone group, 1-4 R 1 Substituted pyridinyl group, 1-3 R 1 Substituted pyrimidinyl group, C1-C 12 Alkoxy; R 1 Selected from: fluorine, chlorine, bromine, C1-C6 alkyl.

2. The synthetic route and method for the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative I according to claim 1 are as follows: The substituent is defined as described in claim 1; the specific synthesis method comprises the following steps: Preparation of compound 2: Compound 1 reacts with acrylic acid under acidic conditions to give compound 2; Take a 100 mL round-bottom flask, add compound 1 (10.0 mmol), acrylic acid (10.0 mmol), acetic anhydride (1 mL) and acetic acid (10 mL), heat to 95 °C, and after the reaction is complete, adjust the pH to alkaline with 30% sodium hydroxide solution, extract three times with ethyl acetate (3 × 20 mL), discard the organic phase, adjust the pH to acidic with 1 mol / L hydrochloric acid, a solid precipitates out, filter to obtain compound 2; Preparation of compound 3: Compound 2 undergoes an oxidative cyclization reaction with sodium iodide and hydrogen peroxide to give compound 3; Take a 100 mL round-bottom flask, add compound 2 (17.4 mmol), acetonitrile (100 mL), sodium iodide (1.7 mmol), and hydrogen peroxide (104.4 mmol), stir at room temperature, and after the reaction is complete, remove acetonitrile under reduced pressure, extract with ethyl acetate (3 × 50 mL), wash successively with saturated sodium bicarbonate (3 × 50 mL) and saturated brine (50 mL), dry with anhydrous sodium sulfate, remove organic solvent under reduced pressure, and purify the residue by silica gel column chromatography to obtain compound 3; Preparation of compound I: Compound 3 reacts with a halogenated compound to give compound I; Take a 100 mL round-bottom flask, add compound 3 (2.46 mmol), acetonitrile (15 mL), potassium carbonate (3.69 mmol), substituted acetophenone / substituted benzyl bromide (2.46 mmol), heat to 80 °C and stir. After the reaction is complete, remove acetonitrile under reduced pressure, extract with ethyl acetate (3 × 20 mL), wash successively with saturated sodium bicarbonate (3 × 20 mL) and saturated brine (20 mL), dry with anhydrous sodium sulfate, remove organic solvent under reduced pressure, and purify the residue by silica gel column chromatography to obtain derivative I containing 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione.

3. The use of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative of claim 1 in the preparation of agricultural fungicides, wherein the fungicide controls the following fungi: early blight of tomato, gray mold of cucumber, brown spot of peanut, Fusarium graminearum, Fusarium verticillatum, ring spot of apple, sheath blight of rice, and sclerotinia sclerotium of rapeseed.

4. The use of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative of claim 1 in the preparation of agricultural plant immune activators, wherein the plant activator targets pathogens 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, as of claim 1, a 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative 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-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative of claim 1 and other commercial bactericides; wherein the ratio of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative to the 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 the active ingredient, the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative of claim 1 and other commercial fungicides; wherein the ratio of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative 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, as an active ingredient, the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative of claim 1 and other commercial fungicides; wherein the ratio of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative to the other commercial anti-plant virus agent 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 a plant immune activator, comprising, as an active ingredient, the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative of claim 1 and other commercial fungicides; wherein the ratio of the 3,4-dihydro-5H-spiro[furan-2,3'-indoline]-2',5-dione derivative to the other commercial plant immune activator 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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