1,3-diphenyl-1h-pyrazole derivatives, processes for their preparation and uses thereof

Abstract

This invention provides a class of 1,3-diphenyl-1H-pyrazole derivatives, their preparation methods, and uses. Specifically, it relates to a class of derivatives whose general chemical structural formula is shown in Formula I: I: This invention discloses the general structural formula of the above-mentioned compounds, their synthesis methods, and their uses as insecticides, acaricides, fungicides, antiviral agents for plants, and plant activators. It also discloses their uses and preparation methods in combination with agriculturally acceptable adjuvants or synergists, as well as in combination with commercial insecticides, acaricides, fungicides, antiviral agents for plants, and plant immune activators for the prevention and control of pests, mites, diseases, and viral diseases in agricultural, forestry, and horticultural plants.

Description

Technical Field

[0001] The technical solution of this invention belongs to the field of pesticides, and relates to 1,3-diphenyl-1H-pyrazole derivatives, their preparation methods and uses. Background Technology

[0002] Plant pathogens pose a severe threat to vegetable and grain production, becoming a major threat to global food security. Pathogens evolve rapidly, quickly overcoming crop resistance, leading to huge economic losses year after year from diseases such as potato late blight and wheat rust (Gao Fen, et al. Jiangsu Journal of Agricultural Sciences, 2014, 30(05): 1174-1179). Globalization and climate change have accelerated the transnational spread and northward expansion of new diseases, while fungal toxins produced by pathogens such as Fusarium further infiltrate agricultural products, threatening food safety (Zou Jingpei, et al. Journal of Pesticide Science, 2024, 26(04): 637-646).

[0003] Natural products are important sources of pesticide leads due to their structural diversity and good biocompatibility. The pyrazole ring, a five-membered nitrogen heterocycle, is widely used in pesticide molecule design. Its characteristics include a compact structure, numerous modifiable sites, and the ability to provide diverse hydrophobic, hydrogen bond, and π-π stacking interactions. In insecticides, herbicides, and fungicides, the pyrazole ring plays a crucial role as the core pharmacophore (Li Changxing. Guangzhou Chemical Industry, 2023, 51(05): 9-11+17; Luo Wei. Pesticides, 2019, 58(05): 327-331). Therefore, introducing this unique pyrazole ring skeleton into pesticide lead structures holds promise for discovering fungicide candidates with novel mechanisms of action and low resistance risk.

[0004] In order to find and discover more efficient, broad-spectrum, low-toxicity pesticide lead and candidate compounds without cross-resistance, this invention designed and synthesized a class of 1,3-diphenyl-1H-pyrazole derivatives, and found that they exhibited good fungicidal activity at low concentrations, and can be used as potential fungicide candidate compounds. Summary of the Invention

[0005] The technical problem to be solved by this invention is to provide a new method for synthesizing a class of compounds containing 1,3-diphenyl-1H-pyrazole derivatives, to provide methods for measuring the bioactivity of these compounds in regulating agricultural, horticultural, and forestry plant pests and pathogens, and to provide applications of these compounds in the fields of agriculture, horticulture, and forestry.

[0006] The technical solution adopted by this invention to solve this technical problem is: to synthesize a chemical structure containing a 1,3-diphenyl-1H-pyrazole derivative with insecticidal, acaricidal, fungicidal, antiviral, and plant disease-inducing activities in agriculture, horticulture, and forestry, as shown in Figure I:

[0007]

[0008] Wherein, R is selected from: aldehyde, ethyl alcohol, halogen; Rx1 is selected from: fluorine, chlorine, bromine, C1-C6 alkyl; Rx2 is selected from: fluorine, chlorine, bromine, C1-C6 alkyl.

[0009] The synthetic route of the present invention containing 1,3-diphenyl-1H-pyrazole derivative I and its intermediates is as follows:

[0010] Synthetic route of compound I

[0011] The method for synthesizing the 1,3-diphenyl-1H-pyrazole derivative I described in this invention comprises the following steps:

[0012] A. Preparation of compound 3:

[0013] Take a 100 mL round-bottom flask, add substituted acetophenone (10 mmol) and ethanol (200 mL), then add substituted phenylhydrazine hydrochloride (15 mmol). After stirring the reaction mixture for 18 hours, a solid precipitates. Remove the solvent under reduced pressure, add water (50 mL) to the resulting mixture, and extract with diethyl ether (3 × 50 mL). Combine the organic phases, dry to anhydrous sodium sulfate, and concentrate under reduced pressure. Purify the residue by silica gel column chromatography to give compound 3.

[0014] B. Preparation of compound 4:

[0015] Take a 100 mL round-bottom flask, add the substituted hydrazone (10 mmol) and N,N-dimethylformamide (30 mL), and slowly add phosphorus oxychloride (120 mmol) to the solution. Heat the reaction mixture at 80 °C for 10 hours. Cool the reaction to room temperature, pour the mixture into ice water, and alkalize with 30% sodium hydroxide solution to pH=8. Filter the solid, wash with water, and dry to obtain target compound 4.

[0016] C. Preparation of Compound I:

[0017] Take a 100 mL round-bottom flask, add the substituted aldehyde (5 mmol) and tetrahydrofuran (15 mL), add sodium borohydride (25 mmol) in portions to the solution under ice bath, stir at room temperature, and after the reaction is complete, extract with ethyl acetate (3 × 50 mL), wash with 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 1,3-diphenyl-1H-pyrazole derivative I.

[0018] D. Uses of 1,3-diphenyl-1H-pyrazole derivative I:

[0019] This invention provides the use of 1,3-diphenyl-1H-pyrazole derivative I in the preparation of insecticides.

[0020] This invention provides the use of 1,3-diphenyl-1H-pyrazole 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, scab of wheat, ring rot of apple, sheath blight of rice, and sclerotinia sclerotium of rapeseed.

[0021] This invention provides the use of 1,3-diphenyl-1H-pyrazole derivative I in the preparation of an anti-tobacco mosaic virus agent.

[0022] This invention provides the use of 1,3-diphenyl-1H-pyrazole 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 a pesticide composition containing 1,3-diphenyl-1H-pyrazole 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 1,3-diphenyl-1H-pyrazole derivative of claim 1 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 0% to 25% by weight of surfactants.

[0025] E. Compositions containing 1,3-diphenyl-1H-pyrazole derivative I and their uses:

[0026] An agricultural composition is formed by combining 1,3-diphenyl-1H-pyrazole derivative I with a commercial pesticide for application; the commercial pesticide is selected from one or more of insecticides, fungicides, antiviral agents for plants, acaricides, and plant immune activators. The composition contains 1,3-diphenyl-1H-pyrazole derivative I and other commercial insecticides, fungicides, antiviral agents for plants, acaricides, and plant immune activators as active ingredients; the content of the active ingredient in 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:

[0027] The 1,3-diphenyl-1H-pyrazole 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 mass percentage of the 1,3-diphenyl-1H-pyrazole derivative I in the insecticidal composition is 1%-90%; preferably, the ratio of the 1,3-diphenyl-1H-pyrazole 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 1,3-diphenyl-1H-pyrazole 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 1,3-diphenyl-1H-pyrazole derivative I in the bactericidal composition is 1%-90%; the ratio of the 1,3-diphenyl-1H-pyrazole 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 1,3-diphenyl-1H-pyrazole 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 1,3-diphenyl-1H-pyrazole derivative I in the antiviral composition is 1%-90%; preferably, the ratio of the 1,3-diphenyl-1H-pyrazole derivative I to the anti-plant virus 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 1,3-diphenyl-1H-pyrazole 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 1,3-diphenyl-1H-pyrazole derivative I in the acaricide composition is 1%-90%; the ratio of the 1,3-diphenyl-1H-pyrazole 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 1,3-diphenyl-1H-pyrazole derivative I described in this invention was determined as follows:

[0052] The bactericidal activity assay of the present invention containing 1,3-diphenyl-1H-pyrazole derivative I:

[0053] The bactericidal or bacteriostatic activity of the 1,3-diphenyl-1H-pyrazole 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, and 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 agent 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. A 4 mm diameter plate was used as the control. Mycelial discs were cut along the outer edge of the hyphae using a perforator 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 in each treatment was investigated, 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 agricultural production in my country. 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 achidicola, 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.

[0054] This invention provides more specific examples of the synthesis, bioactivity, and applications of 1,3-diphenyl-1H-pyrazole 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-1:

[0056] (1) Take a 100 mL round-bottom flask, add substituted acetophenone (10 mmol) and ethanol (200 mL), and then add substituted phenylhydrazine hydrochloride (15 mmol). After stirring the reaction mixture for 18 hours, a solid precipitates out. Remove the solvent under reduced pressure, add water (50 mL) to the resulting mixture, and extract with diethyl ether (3 × 50 mL). Combine the organic phases, dry to anhydrous sodium sulfate, and concentrate under reduced pressure. The residue is purified by silica gel column chromatography to give (E)-1-(4-fluorophenyl)-2-(1-(4-fluorophenyl)ethylene)hydrazine (white solid, 80% yield);

[0057] (2) Take a 100 mL round-bottom flask, add the substituted hydrazone (10 mmol) and N,N-dimethylformamide (30 mL), and slowly add phosphorus oxychloride (120 mmol) to the solution. Heat the reaction mixture at 80 °C for 10 hours. Cool the reaction to room temperature, pour the mixture into ice water, and alkalize it with 30% sodium hydroxide solution to pH=8. Filter the solid, wash it with water, and dry it to give 1,3-bis(4-fluorophenyl)-1H-pyrazole-4-carboxaldehyde (white solid, 85% yield);

[0058] (3) Take a 100 mL round-bottom flask, add the substituted aldehyde (5 mmol) and tetrahydrofuran (15 mL), add sodium borohydride (25 mmol) in portions to the solution under ice bath, stir at room temperature, and after the reaction is complete, extract with ethyl acetate (3 × 50 mL), wash with 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 (1,3-bis(4-fluorophenyl)-1H-pyrazole-4-yl)methanol (white solid, 75% yield).

[0059] Example 2: Results of antibacterial activity assay of the 1,3-diphenyl-1H-pyrazole 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; 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.

[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 bactericidal activity. The bioactivity of the new compounds was determined using different types of commercially available fungicides, such as fluopyram and the lead compound coelenterate, as positive controls. The results showed that the series of compounds exhibited moderate to good inhibitory effects against eight pathogens. Against *Bacillus thuringiensis*, compounds I-22, I-27, and I-32 showed inhibition rates of 81%, 80%, and 81%, respectively, comparable to fluopyram (77%), and 5.4, 5.3, and 5.4 times that of coelenterate. Against cucumber gray mold, compounds I-21, I-22, I-23, I-24, I-26, I-27, I-29, I-32, and I-34 showed inhibition rates of 91%, 100%, 87%, 86%, 87%, 80%, 87%, 86%, and 85%, respectively, which were more than 10% better than fluopyram (70%) and 3.8, 4.2, 3.6, 3.6, 3.6, 3.3, 3.6, 3.6, and 3.5 times that of coenzyme. Against peanut brown spot, compound I-22 showed an inhibition rate of 84%, comparable to fluopyram (84%) and 4 times that of coenzyme. Against *Fusarium graminearum*, compounds I-21–I-29, I-31, I-32, and I-34 showed inhibition rates ranging from 50% to 91%, superior to fluopyram (46%), and 1.6, 2.5, 1.4, 1.4, 1.9, 1.4, 2.1, 1.9, 2.1, 1.7, 2.2, and 1.4 times that of coenzyme. Against *Fusarium verticillatum*, compounds I-22 and I-27 showed inhibition rates of 84% and 73%, respectively, superior to fluopyram (67%) by approximately 10%, and 3.5 and 3.0 times that of coenzyme. Against *Rhizoctonia solani*, compounds I-21, I-22, I-24, I-27, I-29, and I-32 showed inhibition rates of 63%, 85%, 52%, 81%, 52%, and 80%, respectively, comparable to or better than fluopyram (52%), and 2.7, 3.7, 2.3, 3.5, 2.3, and 3.5 times that of coenzyme. Against *Rhizoctonia solani*, compound I-21 showed an inhibition rate of 88%, comparable to fluopyram (88%). I-22 and I-32 both showed inhibition rates of 100%, superior to fluopyram (88%), exceeding fluopyram by more than 10%, and 4.2, 4.8, and 4.8 times that of coenzyme. Against Sclerotinia sclerotinia, the inhibition rates of compounds I-21 and I-29 were 60% and 59%, respectively, comparable to fluopyram (57%), and 3.8 and 3.7 times that of coenzyme. The inhibition rates of I-22, I-27 and I-32 were 83%, 80% and 81%, respectively, superior to fluopyram (57%), and 5.2, 5.0 and 5.1 times that of coenzyme.

[0062] Example 3: Application of the present invention in combination with an insecticide containing 1,3-diphenyl-1H-pyrazole derivative I in the control of agricultural, forestry, and horticultural plant pests:

[0063] The present invention contains 1, 3-Diphenyl-1H-pyrazole derivative I, in combination with any one or two commercial insecticides, forms an insecticidal composition for the control of agricultural, forestry, and horticultural plant pests. The commercial insecticides are selected from: imidacloprid, difenoconazole, acetamiprid, emamectin, abamectin, spinosad, heptamethrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, deltamethrin, cypermethrin, β-cyhalothrin, λ-cyhalothrin, dichlorvos, permethrin, allethrin, bifenthrin, permethrin, fenpropathrin, flufenoxuron, flufenoxuron, imidacloprid, acetamiprid, chlorpyrifos, thiamethoxam, thiamethoxam, dinotefuran, diflubenzuron, diflubenzuron, diflubenzuron, flufenoxuron, flufenoxuron, and flufenoxuron. Urea, acetamiprid, lufenuron, fenfluramide, flufenoxuron, polyfluorourea, flufenoxuron, diphenylfluorourea, flufenoxuron, fenfluramide, fenfluramide, furazolidone, chlorfenapyr, methoxyfenozide, cyclophosphamide, dichlorvos, quinalphos, pyridaben, leafhopper spray, carbaryl, imidacloprid, isoprocarb, fenitrothion, methyl parathion, leaf spray, carbaryl, fenitrothion, bromopropylate, thiamethoxam, Azoxystrobin, pyridaben, tetradifon, propargite, difenoconazole, pymetrozine, spirodiclofen, spirotetramat, spirotetramat ethyl ester, triazophos, thiamethoxam, cartap, chlorantraniliprole, tetrachlorantraniliprole, flufenoxuron, flufenoxuron, cyantraniliprole, butenpyram, azoxystrobin, bromfenoxuron, pyrazinone, etoxazole, pyridaben, pyridaben, pyriproxyfen, emamectin, pendimethalin; the mass percentage of 1,3-diphenyl-1H-pyrazole derivative I in the insecticidal composition of the present invention is 1%-90%, the mass percentage of 1,3-diphenyl-1H-pyrazole derivative I in the insecticidal composition of the present invention is 1%, The ratio of 3-diphenyl-1H-pyrazole derivative I to the aforementioned commercial insecticide is 1% to 99% to 99% to 1% by mass; the formulation of the insecticide 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, 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.

[0064] Example 4: Application of the combination of the present invention containing 1,3-diphenyl-1H-pyrazole derivative I with a fungicide in the prevention and control of diseases in agricultural, forestry, and horticultural plants:

[0065] The present invention relates to a fungicidal composition comprising a 1,3-diphenyl-1H-pyrazole derivative I and 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, cyhalofop-p-ethyl, sulfadiazine, mesotrione, thiabendazole, chlorothalonil, propiconazole, cyclopropiconazole, cyclofluoroacetate, cyclopropiconazole, cyhalofop-p-ethyl, silthiamethoxam, carbendazim, oxychloride, and oxadixyl. Mefenoxam, sulfadiazine, fluopyram, furazolidone, thifluzamide, cyproconazole, pyraclostrobin, pyraclostrobin, bifenazate, fluopyram, fluoxastrobin, fluoxastrobin, fluoxastrobin aniline, benzyl-fluoroquinolones, isopyram, fluoxastrobin hydroxylamine, flufenoxuron, fluoxastrobin, diyrylamide, benzylamide, ethoxysulfuron, iprodione, pyraclostrobin Azoxystrobin, fluazolidone, azoxystrobin, fenoxystrobin, oxadiazon, azoxystrobin, pyraclostrobin, oxadiazon, tebuconazole, cyproconazole, difenoconazole, tebuconazole, high-efficiency tebuconazole, flutriafol, cyproconazole, fluquinazole, flusilazole, fenbendazole, hexaconazole, imidacloprid, tebuconazole, cyproconazole, propiconazole, tebuconazole Prothioconazole, silfluthazole, tebuconazole, tetraflufenazole, triazole, tebuconazole, bifenthrin, thiamethoxam, imazalil, pyraclostrobin, prochloraz, fluconazole, cyazofamid, imazalil, oxadiazon, isoprothiolane, oxadiazon, pyraclostrobin, oxadiazon, oxadiazon, thiamethoxam, terbufos, octothiamethoxam, benzylthiocyanate, dodecyl morpholine, butyl morpholine, trideclofenac Morpholine, Seed dressing, Fludioxonil, Fluazinam, Pyridabenoxime, Cyclopyralid, Fluazinam, Cyclopyralid, Azoxystrobin, Fluazinam, Thifluzamide, Azoxystrobin, Pyrimethanil, Chlorpyrimethanil, Fluazinam, Acaricide, Dicyandioxonone, Ethoxyquinoline, Hydroxyquinoline, Propoxyquinoline, Phenoxyquinoline, Ethiocarb, Isopropylamine, Benzylamine, Cymoxanil, Sulfocarb, Difenoconazole, 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, pyrazosulfuron, doxycycline, guanidine, biguanidine octyl salt, biguanidine octylamine, chlorothalonil, benzylsulfonamide, toluenesulfonamideIndole ester, sodium dichloroisocyanurate, quinacrine, allylbenzylthiazide, bromonitol, iodomethyl, methylparaben, dimethoate, dazomet, dichloroisopropyl ether, thiamethoxam, fenpropathrin, chlorpyrifos, fenpropathrin, thiophanate-methyl, chlorpyrifos, thiocarbamate, thiodimethylphosphonate, dichloropropene, dichloroisonicotinic acid, allylisothiazide; the total mass percentage of 1,3-diphenyl-1H-pyrazole derivative I in the bactericidal composition of the present invention is 1%-90%, the present invention contains 1, The percentage of 3-diphenyl-1H-pyrazole derivative I to the aforementioned commercial fungicide is 1% to 99% to 99% to 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 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, vaporizers, 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, vapor release agents; the fungicide The plant diseases for which the 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, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, peanut, rapeseed, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, pickled mustard greens, sugar 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 5: Application of the combination of the 1,3-diphenyl-1H-pyrazole derivative I of the present invention with an antiviral agent in the prevention and control of viral diseases in agricultural, forestry, and horticultural plants:

[0067] The present invention relates to an antiviral composition formed by combining 1,3-diphenyl-1H-pyrazole 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, antofenzyme, ningnanmycin, methyl thiamethoxam, or salicylic acid, pyrimethanil, dichloroisonicotinic acid, allylisothiazide, jinggangmycin, and morpholine guanidine hydrochloride. The total mass percentage of 1,3-diphenyl-1H-pyrazole derivative I in the antiviral composition of the present invention is 1%-90%. The ratio of 3-diphenyl-1H-pyrazole derivative I to the aforementioned commercial antiviral agent for plants is 1% to 99% to 1% by mass; the formulation 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, smoke candles, smoke tubes, smoke sticks, smoke sheets, smoke pellets, vaporizers, ointments, hot fogging agents, cold fogging agents, aerosols, solid / liquid mixtures, liquid / liquid mixtures, solid / solid mixtures, lacquer, microparticles, tracking powders, oil suspensions, oil-dispersible powders, concentrated gels, spraying agents, seed coating agents, coating agents, film-forming oils, ultra-low volume liquids, and vapor release agents; the antiviral composition controls the following viruses. The diseases selected are: rice dwarf virus, yellow dwarf virus, stripe leaf blight, tomato fern leaf virus, pepper mosaic virus, tobacco vein necrosis virus, corn dwarf mosaic virus, cauliflower mosaic virus, citrus virus, Cymbidium faberi leaf virus, and Cymbidium faberi ringspot virus; the plants used for the 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, 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.

[0068] Example 6: Application of the combination of the present invention containing 1,3-diphenyl-1H-pyrazole derivative I with an acaricide in the control of mite pests in agricultural, forestry, and horticultural plants:

[0069] The present invention relates to an acaricide composition comprising a 1,3-diphenyl-1H-pyrazole derivative I and any one or two commercial acaricides for the control of 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, chlorpyrifos, chlorpyrifos, fenpropathrin, bifenthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, flufenoxuron, deltamethrin, bromofenoxuron, bifenazate, benzyl methoxyfenozide, etc. Thiamethoxam, methyl ethyl methyl sulfide, methyl ethyl sulfide, carbaryl, chlorpyrifos, benomyl, chlorfenapyr, 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, dicofol, pyridaben; the total mass percentage of 1,3-diphenyl-1H-pyrazole derivative I in the acaricide composition of the present invention is 1%-90%, the present invention contains 1, The ratio of 3-diphenyl-1H-pyrazole 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, 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, liquid / liquid mixtures, solid / solid mixtures, medicated paints, microparticles, tracking powders, oil suspensions, oil-dispersible powders, concentrated gels, pouring agents, seed coating agents, smearing agents, film-forming oils, ultra-low volume liquids, vapor release agents; the acaricide composition The mites controlled by the compound are selected from the following mites: Tetranychidae, Trichoderma, Fusarium, Eriophyridae, Chlorella, and Chlorella species. These mites are global agricultural, forestry, horticultural, and sanitary pests. The plants used for control by the acaricide composition are selected from the following: 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.

[0070] Example 7: Application of the present invention containing 1,3-diphenyl-1H-pyrazole derivative I in the preparation of pesticide compositions:

[0071] The present invention relates to a pesticide composition containing 1,3-diphenyl-1H-pyrazole derivative I as an active ingredient, wherein the active ingredient comprises 0.1% to 99.9% by mass, a solid or liquid adjuvant comprises 99.9% to 0.1% by mass, and further comprises optionally 0% to 25% by mass of a surfactant.

[0072] Example 8: Application of the present invention containing 1,3-diphenyl-1H-pyrazole derivative I in the preparation of pesticide compound compositions:

[0073] The 1,3-diphenyl-1H-pyrazole 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 1,3-diphenyl-1H-pyrazole 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 1,3-diphenyl-1H-pyrazole 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.

[0074] Industrial applicability

[0075] This invention provides a class of 1,3-diphenyl-1H-pyrazole 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.

[0076] Table 1. Chemical structure and physicochemical parameters of the 1,3-diphenyl-1H-pyrazole derivatives of the present invention.

[0077]

[0078]

[0079]

[0080]

[0081] Table 2. Antibacterial activity of the present invention containing 1,3-diphenyl-1H-pyrazole derivative I (inhibition rate at 50 μg / mL / %)

Claims

1. A class of 1,3-diphenyl-1H-pyrazole derivatives having the general structural formula shown in Formula I: I: in, R is selected from: aldehyde, ethyl alcohol, halogen; R x 1 Selected from: fluorine, chlorine, bromine, C1-C6 alkyl; R x 2 Selected from: fluorine, chlorine, bromine, C1-C6 alkyl.

2. The specific synthetic route and method of the 1,3-diphenyl-1H-pyrazole derivative I according to claim 1 are as follows: The substituent is defined as described in claim 1, and the specific synthesis method comprises the following steps: A. Preparation of compound 3: Take a 100 mL round-bottom flask, add substituted acetophenone (10 mmol) and ethanol (200 mL), then add substituted phenylhydrazine hydrochloride (15 mmol). After stirring the reaction mixture for 18 hours, a solid precipitates. Remove the solvent under reduced pressure, add water (50 mL) to the resulting mixture, and extract with diethyl ether (3 × 50 mL). Combine the organic phases, dry to anhydrous sodium sulfate, and concentrate under reduced pressure. Purify the residue by silica gel column chromatography to give compound 3. B. Preparation of compound 4: Take a 100 mL round-bottom flask, add the substituted hydrazone (10 mmol) and DMF (30 mL), and slowly add phosphorus oxychloride (120 mmol) to the solution. Heat the reaction mixture at 80 °C for 10 hours. Cool the reaction to room temperature, pour the mixture into ice water, and alkalize it to pH 8 with 30% sodium hydroxide solution. Filter the solid, wash with water, and dry to obtain the target compound 4. C. Preparation of Compound I: Take a 100 mL round-bottom flask, add the substituted aldehyde (5 mmol) and tetrahydrofuran (15 mL), add sodium borohydride (25 mmol) in portions to the solution under ice bath, stir at room temperature, and after the reaction is complete, extract with ethyl acetate (3 × 50 mL), wash with 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 1,3-diphenyl-1H-pyrazole derivative I.

3. The use of the 1,3-diphenyl-1H-pyrazole 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, rice sheath blight, and sclerotinia sclerotium of rapeseed.

4. The use of the 1,3-diphenyl-1H-pyrazole derivative of claim 1 in the preparation of an agricultural plant immune activator, wherein the plant activator controls 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 claimed in claim 1, a 1,3-diphenyl-1H-pyrazole 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 1,3-diphenyl-1H-pyrazole derivative of claim 1 and other commercial fungicides; wherein the ratio of the 1,3-diphenyl-1H-pyrazole derivative to the other commercial fungicides 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 claimed in claim 1, a compound of 1,3-diphenyl-1H-pyrazole derivative and other commercial fungicides as active ingredients; wherein the ratio of 1,3-diphenyl-1H-pyrazole derivative to other commercial insecticides and acaricides 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 surfactants selected from 0 to 25% by weight.

8. A compound composition for resisting plant viruses, comprising, as an active ingredient, the 1,3-diphenyl-1H-pyrazole derivative of claim 1 and other commercial fungicides; wherein the ratio of the 1,3-diphenyl-1H-pyrazole 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 plant immune activators comprising, as an active ingredient, the 1,3-diphenyl-1H-pyrazole derivative of claim 1 and other commercial fungicides; wherein the ratio of the 1,3-diphenyl-1H-pyrazole derivative to the 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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