Derivatives containing 3-(difluoromethyl)-1-methyl-1H-pyrazole as well as preparation method and application thereof

Abstract

The invention provides a derivative containing 3-(difluoromethyl)-1-methyl-1H-pyrazole as well as a preparation method and application thereof, and particularly relates to a derivative of which the chemical structural general formula is shown as a formula I: # imgabs0 #. The invention discloses the structural general formula and the synthesis method of the compound and application of the compound as an insecticide, an acaricide, a bactericide, a plant virus resisting agent and a plant activator. The invention relates to an application and a preparation method of the compound in preventing and treating insect pests, mite pests, diseases and virus diseases of agricultural, forestry and horticultural plants in combination with agriculturally acceptable auxiliaries or synergists and commercial insecticides, acaricides, bactericides, plant virus resisting agents and plant immune activators.

Description

Technical Field

[0001] The technical solution of the invention belongs to the field of pesticides, and specifically relates to 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives and preparation methods and uses thereof. Background Art

[0002] Plant pathogenic fungi have caused significant losses to global agricultural production, affecting a variety of crops such as cereals, fruits, vegetables and beans (Evidente, A. et al. Phytochem. Rev. 2019, 18, 843-870.). These fungi can cause diseases such as rust, smut, wilt and sheath blight, leading to reduced crop yields (Doehlemann, G. et al. Microbiol. Spectr. 2017, 701-726). Chemical fungicides remain the most widely used method for managing fungal diseases, although resistance to these chemicals is becoming increasingly worrying (Wang, Q. et al. J. Agric. Food Chem. 2022, 70, 7039-7048.). Rice is an important food and economic crop in the world. The main diseases of rice are rice blast and sheath blight, which seriously affect the yield and quality of rice. Creating new fungicides for rice disease control is an effective measure to reduce the application of pesticides in my country. With the increasing environmental requirements, the creation of green pesticides will be a new trend in the future development of pesticides.

[0003] Succinate dehydrogenase inhibitors are an important class of fungicides that target succinate dehydrogenase in the mitochondrial respiratory chain of fungi. Succinate dehydrogenase plays a key role in cellular energy production by promoting the conversion of succinate to fumarate. Succinate dehydrogenase inhibitors can disrupt fungal metabolism and cause cell death, and have a broad spectrum of fungicidal activity (Li, H. et al. J. Agric. Food Chem. 2020, 68, 14001-14008.). SDHI fungicides such as boscalid and penthiopyrad have been widely used to control ascomycete and basidiomycete pathogens. Long-term or excessive application of succinate dehydrogenase inhibitor fungicides has led to resistance of pathogens (Peng, JY et al. Phytopathology 2021, 111, 819-830). Therefore, creating a new succinate dehydrogenase inhibitor without cross-resistance is an effective means of plant protection.

[0004] In order to find and discover more efficient, broad-spectrum, low-toxic and non-cross-resistance pesticide lead and candidate compounds, the present invention designs and synthesizes a class of 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives, in the hope of designing and synthesizing SDHI fungicides with high fungicidal activity. The present invention develops a class of 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives and a preparation method thereof, and finds that they exhibit good fungicidal activity at lower concentrations, and can be used as potential fungicide candidate compounds. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a new synthesis method of 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives, provide biological activities of such compounds in regulating agricultural, horticultural, sanitary and forestry plant pests and plant pathogens and their determination methods, and provide applications of these compounds in the fields of agriculture, horticulture, forestry and sanitation. The technical solution adopted by the present invention to solve the technical problem is: the chemical structure of 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives having insecticidal, acaricidal, bactericidal, anti-plant virus activity and inducing plant disease resistance activity in the fields of agriculture, horticulture and forestry is shown in the general formula I:

[0006] I:

[0007] Among them, R 1 -R 5 Selected from: 2,6-dibromo-4-trifluoromethoxy, 2,6-dichloro-4-trifluoromethoxy, 2,4,6-trichloro, 3-tert-butyl, 3-isopropyl, [1,3]dioxane, 3-bromo-5-trifluoromethyl, 3-bromo-4-trifluoromethoxy, 3-trifluoromethyl-4-bromo, 3-bromo-5-methoxy, 3-bromo-4-methoxy, 2-bromo-4-trifluoromethyl, 3-phenoxy, 5,6, 7,8-Tetrahydronaphthalene, 2,3-dihydro-1H-indene, naphthalene, 2-bromo-trimethyl, 3-phenyl, 2-4'-chlorophenyl, 2-difluoromethoxy, 2-ethynyl, 2-tert-butyl, 2-cyano, 4-phenyl, 2-chloro-3-carbomethoxy, 2-isopropyl, 3-prop-1-en-2-yl, 3,5-ditrifluoromethyl, 2-chloro-6-fluoro, 2-4'-chlorophenoxy, 2-bromo-4-chloro-6-fluoro.

[0008] The synthetic route of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention is as follows:

[0009] Synthesis route of compound I

[0010] The synthesis method of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention is divided into the following steps:

[0011] A. Take a 100 ml round-bottom flask, add 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid (2.0 mmol), oxalyl chloride (4.0 mmol), anhydrous N,N-dimethylformamide (3 drops) and dichloromethane (10 ml) in sequence, stir at room temperature for 8 hours, and remove the solvent under reduced pressure for use; take a 100 ml round-bottom flask, add substituted amine (2.0 mmol), triethylamine (5.0 mmol) and dichloromethane (10 ml) in sequence, after the reaction is completed by thin layer chromatography, the solution is washed with dichloromethane (20 ml) and brine (20 ml), dried over anhydrous sodium sulfate and concentrated in vacuo, the solvent is removed under reduced pressure, and the residue is purified by 100-200 mesh silica gel column chromatography, the eluent is ethyl acetate / petroleum ether, to obtain 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I.

[0012] B. Uses of 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives I:

[0013] The present invention provides use of a 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I in preparing an insecticide.

[0014] The invention provides use of a 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I in preparing a fungicide. The fungi controlled by the fungicide are tomato early blight, cucumber gray mold, peanut brown spot, wheat fusarium, apple ring rot, rice sheath blight and rapeseed sclerotinia.

[0015] The present invention provides use of a 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I in preparing an anti-tobacco mosaic virus agent.

[0016] The invention provides the use of a 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I in preparing a plant immune activator for inducing tobacco resistance to tobacco mosaic virus and the use of a 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I in inducing Arabidopsis resistance to Arabidopsis downy mildew.

[0017] It should be noted that plant immune activators were also called plant activators or inducers in the past. They can induce host plants to produce broad-spectrum and long-lasting disease resistance.

[0018] The present invention provides a pesticide composition containing a 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I, which is suitable for preventing and controlling insect pests and pathogens of agricultural, forestry and horticultural plants and inducing plants to produce defense capabilities against plant pests and pathogens. The above-mentioned pesticide composition includes an agricultural fungicide composition, an agricultural insecticide composition, an agricultural anti-plant virus composition, and an agricultural plant immune activator composition. The composition contains the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative described in 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 a solid or liquid adjuvant, and 0 to 25% by weight of a surfactant selected from.

[0019] C. Compositions containing 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives I and uses thereof:

[0020] An agricultural composition is formed by applying 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I together with commercial pesticides; the commercial pesticides are selected from: one or more of insecticides, fungicides, anti-plant virus agents, acaricides, and plant immune activators. The composition contains 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I and other commercial insecticides, fungicides, anti-plant virus agents, 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, and the composite composition contains 1% to 99% by weight of active ingredients, 99% to 1% by weight of solid or liquid adjuvants, and 0 to 25% by weight of surfactants. The specific combination is as follows:

[0021] The 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I is combined with any one or two of the insecticides to form an insecticidal composition for controlling agricultural, forestry and horticultural plant pests;

[0022] The insecticide is selected from the group consisting of methoprene, dimethoate, acetamiprid, avermectin, mibemycin, avermectin, spinosad, tefluthrin, cypermethrin, cypermethrin, cypermethrin, deltamethrin, cypermethrin, β-cypermethrin, λ-cypermethrin, cypermethrin, allethrin, bifenthrin, permethrin, ether cypermethrin, flumethrin, cypermethrin, imidacloprid, nitenpyram, chlorthiazolin, thiacloprid, thiamethoxam, clothianidin, dinotefuran, clothianidin, datenam, diflubenzuron, diflubenzuron, flufenoxuron, acetamiprid, lufenuron, chlorpyrifos, flufenuron, polyflubenzuron, flufenuron , bisbenzenefluanid, chlorfluazuron, anthracene, bistrifluanid, furanfenozide, fenfenozide, chlorfenapyr, methoxyfenozide, chlorfenapyr, dichlorvos, quinalphos, pyridazine, leafhopper powder, carbaryl, pirimicarb, mefenamic acid, isoprocarb, cartap, fenbutyl, leaf flying powder, carbaryl, cartap, bromocriptine, hexythiazox, fenpyroximate, pyridabenzan, clofenazine, fenpyroximate, pyrimidine, pyridabenzan, clofenazine, fenpyroximate, pyrimidine, pyridabenzan, spirocyclon, spirocyclon, spirocyclon, triazotin, buprofezin, insecticide single, insecticide double, chlorantraniliprole, tetrachlorantraniliprole, flubendiamide, flucyram, cyanamide, butene flubendiamide, tolfenpyrad, bromofenapyr, pyrazinone, etoxazole, cypermethrin, pyridabenzan, pyriproxyfen, emamectin, pyrimidine;

[0023] The mass percentage of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I in the insecticide composition is 1%-90%; preferably, the mass percentage of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I to the insecticide is 1%:99% to 99%:1%;

[0024] The dosage form of the insecticide composition is selected from the group consisting of seed treatment emulsion, aqueous emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous grain, block poison bait, granular poison bait, sheet poison bait, concentrated poison bait, slow-release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gasifier, ointment, hot fog, cold fog, aerosol, solid / liquid mixed agent, liquid / liquid mixed agent, solid / solid mixed agent, lacquer, microgranule, tracking powder, oil suspension, oil dispersible powder, concentrated glue, pouring agent, seed coating agent, smear, film-forming oil agent, ultra-low volume liquid agent, steam release agent;

[0025] The plant pests controlled by the insecticide composition are selected from: fall armyworm, red spider, East Asian migratory locust, cloud-spotted locust, Chinese rice locust, Japanese yellow-spine locust, single-spined mole cricket, oriental mole cricket, rice thrips, tobacco thrips, greenhouse thrips, rice tube thrips, wheat tube thrips, greenhouse whitefly, Bemisia tabaci, black-tailed leafhopper, green leafhopper, cotton leafhopper, spotted wax cicada, brown planthopper, white-backed planthopper, gray planthopper, sugarcane flat-horned planthopper, cotton aphid, wheat aphid, wheat long-tube aphid, peach aphid, sorghum aphid, radish aphid, cotton scale, mulberry shield scale, arrow-pointed shield scale, pear round scale, white wax insect, red wax scale, Korean ball-hard scale , pear web bug, banana web bug, fine-horned flower bug, tiny flower bug, needle-edged bug, rice spider bug, rice brown bug, rice black bug, rice green bug, green stink bug, alfalfa stink bug, middle black stink bug, big lacewings, beautiful lacewings, Chinese lacewings, grain moth, clothes moth, yellow thorn moth, brown thorn moth, flat thorn moth, wheat moth, cotton pink bollworm, sweet potato wheat moth, diamondback moth, peach borer, soybean borer, peach borer, apple top leaf roller, brown-banded long leaf roller, quasi-small yellow leaf roller, striped stem borer, bean pod borer, corn borer, yellow stem borer, cabbage borer, rice leaf roller, striped stem borer, cotton leaf roller, peach borer, sticky insect, twill Noctuidae, rice borer, cotton bridgeworm, beet armyworm, stem borer, cotton bollworm, Dingdian diamond drill, small cutworm, large cutworm, yellow cutworm, thief moth, gypsy moth, sweet potato hawkmoth, bean hawkmoth, straight-striped rice hesperid, hidden grain hesperid, citrus swallowtail, jade-belt swallowtail, cabbage butterfly, ramie red admiral, ramie yellow admiral, bean sedge, Venus carabid, wrinkled sheath carabid, wheat ear carabid, ditch wireworm, fine-breasted wireworm, grain spot beetle, black skin beetle, citrus small borax, golden-margin borax, yellow mealworm, black mealworm, red flour beetle, mixed flour beetle, copper green exotic beetle, dark beetle, North China giant Black-gilled scarab beetle, mulberry longhorn beetle, star longhorn beetle, orange brown longhorn beetle, peach-necked longhorn beetle, big monkey leafworm, small monkey leafworm, yellow melon beetle, yellow-striped flea beetle, mung bean weevil, pea weevil, broad bean weevil, corn weevil, rice weevil, wheat sawfly, pear sawfly, yellow-banded ichneumon wasp, white-star ichneumon wasp of sticky insect, hanging cocoon ichneumon wasp of cotton bollworm, black-spotted warty ichneumon wasp of stem borer, mosquito, fly, horsefly, red wheat midge, yellow wheat midge, rice gall midge, citrus fruit fly, melon fruit fly, wheat leaf gray leafminer, American spotted leafminer, bean stalk black leafminer, wheat stalk fly, seed fly, onion fly, radish fly, skirt chasing fly, corn borer fly, and sticky insect;

[0026] The plants controlled by the insecticide composition are selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut, rapeseed, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard tuber, beet, rapeseed, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, and bonsai.

[0027] The 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I is combined with any one or two of the fungicides to form a fungicide composition for preventing and controlling agricultural, forestry and horticultural plant diseases;

[0028] The fungicide is selected from the group consisting of benzothiadiazole, thiazolamide, thiazolamide, DL-β-aminobutyric acid, isothiopyrad, viravirin, anthofen, ningnanmycin or salicylic acid, cymoxanil, thiram, zinc thiram, mancozeb, ethyl phosphine aluminum, methyl thiophanate, chlorothalonil, dichlorobenzene, procymidone, fenpropidin, methyl thiophanate, thiophanate, metalaxyl, flumorph, dimethomorph, high-efficiency metalaxyl, high-efficiency bensulfuron, dichlorocyanamide, sulfaquinoxaline, sulfaquinoxaline, thiofluanid, chlorothalonil, cyproconazole, cyprodinil, cyfluanid, cyprodinil, cyanamide, cyprodinil ... Azopyraclostrobin, Fluoxathiapiprolin, Fluoxathiapiprolin, Isopropyltrifloxacin, Fluoxathiapiprolin, Fluoxathiapiprolin, Fluoxathiapiprolin, Dimethomorph, Zoxystrobin, Ethioprolin, Iprodione, Azoxystrobin, Dimethomorph, Fluoxathiapiprolin, Dimethomorph, Ethiostrobin ... azole, cyproconazole, difenoconazole, diniconazole, high-efficiency diniconazole, fluepiconazole, nitrobenazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imidazole, cyproconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, silyfloxacin, tebuconazole, tetrafluconazole, triadimenol, trichlorfonazole, bifenthrin, thiabendazole, wheat spike, imazalil, high-efficiency imazalil, prochloraz, Flubaccon, cyazofamid, imidacloprid, oxacloprid, oxacloprid, oxacloprid, oxacloprid, oxacloprid, oxathiapiprolin, oxadixyl, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, oxathiapiprolin, Bensulfuron, furamide, carbendazim, benomyl, methyl thiophanate, triadimefon, ethiminol sulfonate, dimethoate, ethiminol, captan, foltan, vinyl sclerotin, fluchloric acid sclerotin, sclerotin, thiophanate-methyl, chlorothalonil, rice blast, rice blast, leaf chloranil, pentachloronitrobenzene, propineb, fosetyl-aluminum, sulfur, Bordeaux mixture, copper sulfate, copper oxychloride, cuprous oxide, copper hydroxide, bensulfuron, pencuron, pyraclostrobin, tetrachlorophthalide, pyroquilone, spiroxafil, tricyclazole, thiamethoxam, polypyrimidine, biguanide salt, biguanide octylamine, chloranil, benzylsulfuron, toluenesulfuron, indole ester, sodium sulfensulfuron, quinoline, allyl thiazole, bronopol, iodomethane, metamethylenetetramine, dazomethanil, dichloroisopropyl ether, thiathion, fensulfuron, chloranil,Oxamyl, sulfuryl fluoride, dichloropropylene, dichloroisonicotinic acid, allylisothiazole;

[0029] The total mass percentage of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I in the bactericidal composition is 1%-90%; the ratio of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I to the bactericide is 1%:99% to 99%:1% by mass percentage;

[0030] The dosage form of the bactericidal composition is selected from the group consisting of seed treatment emulsion, aqueous emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous grain, block poison bait, granular poison bait, sheet poison bait, concentrated poison bait, slow-release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gasifier, ointment, hot mist, cold mist, aerosol, solid / liquid mixed agent, liquid / liquid mixed agent, solid / solid mixed agent, lacquer, microgranule, tracking powder, oil suspension, oil dispersible powder, concentrated glue, pouring agent, seed coating agent, smear, film-forming oil agent, ultra-low volume liquid agent, steam release agent;

[0031] The plant diseases controlled by the bactericidal composition 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, cucumber anthracnose;

[0032] The plants suitable for the fungicidal composition are selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut, rapeseed, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard tuber, beet, rapeseed, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, and bonsai.

[0033] The 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I is combined with any one or two of the antiviral agents to form an antiviral composition for preventing and controlling viral diseases of agricultural, forestry and horticultural plants;

[0034] The antiviral agent is selected from: benzothiadiazole, thiazolamide, isothiazolamide DL-β-aminobutyric acid, 2,6-dichloroisonicotinic acid, N-cyanomethyl-2-chloroisonicotinamide, allylisothiazole, ribavirin, anthofin, ningnanmycin, methiothiazolamide or salicylic acid, pyrimidine, dichloroisonicotinic acid, allylisothiazole, Jinggangmycin, guanidine hydrochloride;

[0035] The total mass percentage of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I in the antiviral composition is 1%-90%; preferably, the ratio of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I to the anti-plant virus agent is 1%:99% to 99%:1% by mass percentage;

[0036] The dosage form of the antiviral composition is selected from the group consisting of seed treatment emulsion, aqueous emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous grain, block poison bait, granular poison bait, sheet poison bait, concentrated poison bait, slow-release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gasifier, ointment, hot mist, cold mist, aerosol, solid / liquid mixed agent, liquid / liquid mixed agent, solid / solid mixed agent, lacquer, microgranule, tracking powder, oil suspension, oil dispersible powder, concentrated glue, pouring agent, seed coating agent, smear, film-forming oil agent, ultra-low volume liquid agent, steam release agent;

[0037] The virus diseases controlled by the antiviral composition are selected from: rice dwarf disease, yellow dwarf disease, stripe leaf blight, tomato fern leaf virus disease, pepper mosaic virus disease, tobacco vein necrosis virus disease, corn dwarf mosaic virus, cauliflower mosaic virus, citrus virus disease, Jianlan orchid leaf virus, and Jianlan ringspot virus;

[0038] The plants for prevention and treatment of the antiviral composition are selected from the group consisting of rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut, rapeseed, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard tuber, beet, rapeseed, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, and bonsai.

[0039] The 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I is combined with any one or two of the acaricides to form an acaricidal composition for controlling acaricide damage in agriculture, forestry and horticultural plants;

[0040] The acaricide is selected from the group consisting of dichlorvos, heptylphos, cypermethrin, dibromophos, pyrimidophos, chlormethoxam, ethion, acaricide, phosalone, methyl pyrimidophos, quinalphos, aphidox, chlormethoxam, phosmet, flumethrin, bifenthrin, cyhalothrin, cyhalothrin, cyhalothrin, cyhalothrin, cyhalothrin, cyhalothrin, cyhalothrin, bifenthrin, fenthiocarb, butanone, oxamyl, cypermethrin, long-lasting cypermethrin, benomyl, chlormethrin ... Wei, butyralidone, cypermethrin, benzyl benzoate, bromocriptine, cyfluthrin, acequinoxaline, flumioxon, flufenoxuron, liuyangmycin, cypermethrin, thuringin, miticide, liuyangmycin, avermectin, doramectin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, azadirachtin, rotenone, cypermethrin, pyraclostrobin, cypermethrin ...

[0041] The total mass percentage of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I in the acaricide composition is 1%-90%; the ratio of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I to the acaricide is 1%:99% to 99%:1% by mass percentage;

[0042] The dosage form of the acaricide composition is selected from the group consisting of seed treatment emulsion, aqueous emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous grain, block poison bait, granular poison bait, sheet poison bait, concentrated poison bait, slow-release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gasifier, ointment, hot fog, cold fog, aerosol, solid / liquid mixed agent, liquid / liquid mixed agent, solid / solid mixed agent, lacquer, microgranule, tracking powder, oil suspension, oil dispersible powder, concentrated glue, pouring agent, seed coating agent, smear, film-forming oil agent, ultra-low volume liquid agent, steam release agent;

[0043] The mite pests controlled by the acaricidal composition are selected from the group consisting of pests of Tetranychus, Tenebriophyidae, Furonematodes, Cynocephalus, Tetranychus, and Cynocephalus, and the pests are global agricultural pests, forestry pests, gardening pests, and hygiene pests;

[0044] The plants for the control of the acaricide composition are selected from the group consisting of rice, wheat, barley, oats, corn, sorghum, sweet potatoes, potatoes, cassava, soybeans, snow peas, broad beans, peas, mung beans, adzuki beans, cotton, sericulture, peanuts, rapeseed, sesame, sunflowers, sugar beets, sugar cane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomatoes, peppers, radishes, cucumbers, cabbages, celery, mustard tubers, sugar beets, rapeseed, onions, garlic, watermelons, melons, cantaloupes, papayas, apples, citrus and peach trees, tea, wild vegetables, bamboo shoots, hops, peppers, bananas, papayas, orchids, and bonsai.

[0045] The biological activity of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I described in the present invention is determined as follows:

[0046] Determination of fungicidal activity of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention:

[0047] The bactericidal or antibacterial activity of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention is determined by a bacterial growth rate determination method, which specifically comprises the following steps: 1.8 mg of a sample is dissolved in 2 drops of dimethyl sulfoxide, and then diluted to 500 μg / ml of the drug with an aqueous solution containing a certain amount of Tween 20 emulsifier, 1 ml of each test drug is aseptically drawn into a culture dish, and then 9 ml of potato dextrose agar medium is added respectively, and after being shaken, a 50 μg / ml drug-containing plate is prepared, and a plate with 1 ml of sterilized water added is used as a blank control. , cut the bacterial disc along the outer edge of the hyphae with a 4 mm diameter puncher, move it to the drug-containing plate, and place it in an equilateral triangle. Repeat 3 times for each treatment, and place the culture dish in a constant temperature incubator at 24±1 degrees Celsius for culture. After the diameter of the control colony expands to 2-3 cm, investigate the expansion diameter of the bacterial disc of each treatment, calculate the average value, and calculate the relative inhibition rate by comparing with the blank control. The test strains are most of the typical plant pathogens that actually occur in the field in my country's agricultural production. Their codes and names are as follows: As: Tomato early blight pathogen, its Latin name is: Alternaria solani, Bc: Cucumber gray mold, its Latin name is: Botrytis cinerea, Ca: Peanut brown spot fungus, its Latin name is: Cercospora arachidicola, Fg: Grainaceous Fusarium, its Latin name is: Fusarium graminearum, Fv: Verticillium fusarium, its Latin name is: Fusarium verticillioides, Pp: Apple ring rot fungus, its Latin name is: Physalospora piricola, Rs: Rice sheath blight fungus, its Latin name is: Rhizoctonia solani, Ss: Rapeseed Sclerotinia, its Latin name is: Sclerotinia sclerotiorum.

[0048] The present invention further specifically illustrates the synthesis, biological activity and application of 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives I through specific preparation and biological activity determination examples. The examples are only used to specifically illustrate the present invention but not to limit the present invention. In particular, the biological activity is only an example and not to limit the present patent. The specific implementation methods are as follows:

[0049] Example 1: Preparation of Compound I-1:

[0050] In a 100 ml round-bottom flask, 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid (2.0 mmol), oxalyl chloride (4.0 mmol), anhydrous N,N-dimethylformamide (3 drops) and dichloromethane (10 ml) were added in sequence, and the mixture was stirred at room temperature for 8 hours, and the solvent was removed under reduced pressure for use; in a 100 ml round-bottom flask, substituted aniline (2.0 mmol), triethylamine (5.0 mmol) and dichloromethane (10 ml) were added in sequence. After the reaction was completed by thin layer chromatography, the solution was washed with dichloromethane (20 ml) and brine (20 ml), dried over anhydrous sodium sulfate and concentrated in vacuo, and the solvent was removed under reduced pressure. The residue was purified by 100-200 mesh silica gel column chromatography with ethyl acetate / petroleum ether as the eluent to obtain 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I. (white solid, 77% yield);

[0051] Example 2: Antibacterial activity test results of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention:

[0052] The codes and names of the common plant pathogenic fungi tested by the present invention are as follows: As: Alternaria solani, Bc: Botrytis cinerea, Ca: Cercospora arachidicola, Fg: Fusarium graminearum, Fv: Fusarium verticillioides, Pp: Physalospora piricola, Rs: Rhizoctonia solani, Ss: Sclerotinia sclerotiorum. These strains are very representative and can represent most of the species of pathogens occurring in the field during agricultural production.

[0053] The results of the bacterial growth rate method are shown in Table 2. Table 2 shows that all the compounds synthesized in the present invention have fungicidal activity to varying degrees. The present invention carried out the determination of the biological activity of the new compounds using different types of commercial fungicides such as fluopicolide as positive controls; the results showed that several compounds including compounds I-1, I-3 to I-5, I-7, I-8, I-10, I-13, I-15 and I-18 exhibited broad-spectrum fungicidal activity. It is worth noting that, except for I-9 and I-12, the inhibition rates of all the designed compounds on Rhizoctonia solani exceeded 70%. Further EC 50The measurements showed that these compounds had an EC 50 The values ​​ranged from 0.002 to 3.43 μg / mL, indicating that they had strong antifungal potential, among which compounds I-1, I-4, I-5, I-7, I-13, I-15, I-16, I-17, I-18, I-19, I-21, I-24, I-25, I-26, I-27, I-29, I-30, and I-31 were more active against Rhizoctonia solani than the positive control fluopicolide (EC 50 The activity of compounds I-2 and I-11 against Rhizoctonia solani was comparable to that of the positive control fluopicolide, highlighting their strong antifungal activity.

[0054] Example 3: Application of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention in combination with an insecticide in controlling insect pests in agriculture, forestry and horticultural plants:

[0055] The insecticide composition formed by the combination of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention and any one or two of the commercial insecticides is used for preventing and controlling agricultural, forestry and horticultural plant pests. The commercial insecticide is selected from the group consisting of methoprene, dimethoate, acetamiprid, avermectin, mibemycin, avermectin, spinosad, tefluthrin, cypermethrin, high-efficiency cypermethrin, high-efficiency cypermethrin, tri-cyhalothrin, deltamethrin, cypermethrin, β-cypermethrin, λ-cypermethrin, dichlorophenoxyacetate, permethrin, allethrin, bifenthrin, permethrin, ether cypermethrin, flumethrin, fluazifop, cypermethrin ... Pyrethroids, imidacloprid, nitenpyram, chlorthiophene, thiacloprid, thiamethoxam, clothianidin, dimethoate, clothianidin, dartenam, diflubenzuron, diflubenzuron, diflubenzuron, diflubenzuron, flufenoxuron, acetamiprid, lufenuron, chlorfenapyr, flufenoxuron, flufenoxuron, flufenoxuron, flufenoxuron, flufenoxuron, flufenoxuron, flufenoxuron, flufenoxuron, flufenoxuron, flufenoxuron, flufenoxuron, flufenoxuron, flufenoxuron, furanthinofen, fenfenoxadone, chlorfenoxadone, methoxyfenoxadone, chlor ... Ketone, spirodiclofen, spirothiocarb, spirothiocarb, triazotin, buprofezin, cypermethrin, chlorantraniliprole, tetrachlorvinphos, flubendiamide, flucythiocarb, cyantraniliprole, butene-fipronil, tolfenpyrad, chlorfenapyr, pyrazinone, etoxazole, cypermethrin, pyriproxyfen, pyriproxyfen, emamectin, and pyrimidine; the mass percentage of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I in the insecticide composition is 1%-90%, and the ratio of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I to the aforementioned commercial insecticide is 1%:99% to 99%:1% by mass; the The dosage form of the insecticide composition is selected from the group consisting of seed treatment emulsion, aqueous emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granule, fine granule, soluble concentrate, poisonous grain, block poison bait, granular poison bait, sheet poison bait, concentrated poison bait, slow-release block, electrostatic spray, oil-in-water emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gasifier, ointment, hot fog, cold fog, aerosol, solid / liquid mixed agent, liquid / liquid mixed agent, solid / solid mixed agent, lacquer, microgranule, tracking powder, oil suspension, oil dispersible powder, concentrated glue, pouring agent, seed coating agent, smear, film-forming oil agent, ultra-low volume liquid agent, steam release agent;The insecticide composition is applicable to plant pests selected from the group consisting of fall armyworm, red spider, East Asian migratory locust, cloud-spotted locust, Chinese rice locust, Japanese yellow-spine locust, single-spined mole cricket, oriental mole cricket, rice thrips, tobacco thrips, greenhouse thrips, rice tube thrips, wheat tube thrips, greenhouse whitefly, Bemisia tabaci, black-tailed leafhopper, green leafhopper, cotton leafhopper, spotted wax cicada, brown planthopper, white-backed Planthoppers, gray planthoppers, sugarcane flat-horned planthoppers, cotton aphids, wheat aphids, wheat long-tubed aphids, peach aphids, sorghum aphids, radish aphids, cotton scale, mulberry shield scale, arrow-pointed shield scale, pear round scale, white wax insect, red wax scale, Korean ball-hard scale, pear web bug, banana web bug, fine-horned flower bug, tiny flower bug, needle-edge bug, rice spider bug, rice brown bug, rice black bug, rice green bug, green blind bug, alfalfa blind bug, Middle black blind bug, large lacewings, beautiful lacewings, Chinese lacewings, grain moth, clothes moth, yellow thorn moth, brown thorn moth, flat thorn moth, wheat moth, cotton bollworm, sweet potato moth, diamondback moth, peach borer, soybean borer, peach borer, apple top leaf roller, brown-banded long leaf roller, quasi-small yellow leaf roller, striped stem borer, bean pod borer, corn borer, yellow stem borer, cabbage borer, rice leaf roller , striped borer, cotton leaf roller, peach borer, armyworm, armyworm, rice borer, cotton bridge worm, beet armyworm, greater stem borer, cotton bollworm, Dingdian diamond drill, small cutworm, large cutworm, yellow cutworm, thief moth, gypsy moth, sweet potato hawkmoth, bean hawkmoth, straight-striped rice hesperid, hidden grain hesperid, citrus swallowtail, jade-belt butterfly, cabbage butterfly, ramie red admiral, ramie yellow admiral Butterfly, bean lycopersicum, Venus carabiner, wrinkled carabiner, wheat ear carabiner, groove wireworm, fine-breasted wireworm, grain spot beetle, black skin beetle, citrus small jellyfish, golden edge jellyfish, yellow mealworm, black mealworm, red flour beetle, mixed flour beetle, copper green beetle, dark beetle, North China black gill beetle, mulberry longhorn beetle, star longhorn beetle, orange brown longhorn beetle, pink neck longhorn beetle, big monkey leaf beetle, small Ape leaf beetle, yellow melon beetle, yellow striped flea beetle, mung bean weevil, pea weevil, broad bean weevil, corn weevil, rice weevil, wheat sawfly, pear fruit bee, yellow-banded ichneumon wasp, white-star ichneumon wasp, hanging cocoon ichneumon wasp, cotton bollworm tooth-lipped ichneumon wasp, black-spotted warty ichneumon wasp, mosquito, fly, horsefly, red wheat midge, yellow wheat midge, rice gall midge, citrus fruit fly, melon fruit fly, wheat leaf ash leafminer, American spotted leafminer flies, bean stalk black miners, wheat stalk flies, seed flies, onion flies, radish flies, umbrella skirt chasing flies, corn borer flies, armyworms; the insecticide composition is applicable to plants selected from: rice, wheat, barley, oats, corn, sorghum, sweet potatoes, potatoes, cassava, soybeans, snow peas, broad beans, peas, mung beans, adzuki beans, cotton, sericulture, peanuts, rapeseed, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard tuber, beet, rapeseed, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach trees, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai. ;

[0056] Example 4: Application of the combination of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention and a fungicide in preventing and controlling agricultural, forestry and horticultural plant diseases:

[0057] The fungicide composition formed by the combination of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention and any one or two of the commercial fungicides is used for preventing and controlling agricultural, forestry and horticultural plant diseases. The commercial fungicides are selected from the group consisting of benzothiadiazole, thiazolamide, thiazolamide, isothiazolamide, viravir, anthofin, ningnanmycin or salicylic acid, cymoxanil, thiram, zinc thiram, mancozeb, fosetyl-aluminum, methyl thiophanate, chlorothalonil, dichlorvos, procymidone, fenpropidin, methyl thiophanate, thiophanate-methyl, metalaxyl, flumorph, dimethomorph, high-efficiency metalaxyl, high-efficiency bensulfuron, dichlorocyanamide, sulfaquinoxaline, sulfaquinoxaline, thiofluanid, chlorothalonil, cyproconazole, cyfluanid, cyclamoxadone, cyanamide, silthiophanate and carboxin. , oxycarboxin, oxamoxadone, furamide, oxamoxadone, flutolanil, furopyram, thiofuranil, boscalid, penthiopyrad, pyraclostrobin, bixafen, fluopyram, fluoxazolidinone, fluopyram, fluopyram, phenyltrichloroethane, isopyram, fluopyram hydroxylamide, fluphenazine, flutolanil, dimethomorph, flutolanil, oxazolidinone, flutolanil ... Propyl, Iprodione, Azoxystrobin, Dimethoate, Fluoxastrobin, Dimethoate, Benoxystrobin, Dimethoate, Picoxystrobin, Pyraclostrobin, Trifloxystrobin, Enstrobin, Enstrobin, Oxycyclazole, Furoconazole, Cyproconazole, Difenoconazole, Diniconazole, High-efficiency Diniconazole, Fluoxetine, Nibuconazole, Fluquinconazole, Flusilazole, Flutriafol, Hexaconazole, Imidazole, Imidazole, Meconazole, Methiconazole, Myclobutanil , penconazole, propiconazole, prothioconazole, silafluazole, tebuconazole, tetrafluconazole, triadimenol, chloranil, bifenthrin, thiabendazole, wheat spike, imazalil, high-efficiency imazalil, prochloraz, trifloxystrobin, cyazofamid, imidacloprid, oxamidazole, rice blast ester, oxadiazine, pyraclostrobin, oxadiazine, oxadiazine, trifloxystrobin, trifloxystrobin, thiabendazole, thiabendazole, thiabendazole, thiabendazole, thiabendazole, thiabendazole, octhiazol, thiocyanate, dodecacyclic phenoxyquin, fenpropimorph, tridemorph, fenthiocarb, fludioxonil, fluazinam, pyraclostrobin, cyclamox, fluopicolide, pyraclostrobin, cyprodinil, fluopicolide, thiofuran, pyraclostrobin, pyraclostrobin, chlorfenapyr, flufenapyr, miticide, dicyanoanthraquinone, ethoxyquinoline, hydroxyquinoline, propoxyquinoline, phenoxyquinoline, ethotripsy, isopropanil, benzathiapiprolin, cyproconazole, cyproconazole, Sulfonamide, dichlorvos, isothiocyanate, pyraclofos, methyl tolclofos, blasticide, kasugamycin, polyoxin, polyoxin, validamycin, Jinggangmycin, streptomycin, metalaxyl, furalaxyl, bensulfuron, furamide, carbendazim, benomyl, methyl thiophanate, triadimefon, pyrimidine sulfonate, dimethomorph, pyrimidine, captan, foltan, vinyl sclerotin, fluchloric acid sclerotin, sclerotin, thiophanate-methyl, chlorothalonil, pentachloronitrobenzene, propineb, fosetyl-aluminum, sulfur, Bordeaux mixture, copper sulfate, copper oxychloride, cuprous oxide, copper hydroxide, bensulfone, penthiopyralid, tetrachlorophthalide, pyroquinone, spiroxanil, tricyclazole, chloranil, polypyrrolidone, biguanide salt, biguanide amine, chlornitril, bensulfone,Tosulsulfuron, indole ester, sodium sulfone, quinclorac, allylbenzazole, bronopol, iodomethane, metamethylenetetracycline, dazomethan, dichloroisopropyl ether, thiathion, fenthiophos, cypermethrin, chloranil, butylthiophos, oxamyl, sulfuryl fluoride, dichloropropylene, dichloroisonicotinic acid, allylisothiazole; the total mass percentage of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I in the fungicide composition of the present invention is 1%-90%, and the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention is 1%-90%. The amount percentage of derivative I and the aforementioned commercial fungicide is 1%:99% to 99%:1%; the dosage form of the fungicide composition is selected from: seed treatment emulsion, aqueous emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granules, fine granules, soluble concentrate, poison valley, block poison bait, granular poison bait, sheet poison bait, concentrated poison bait, slow-release block, electrostatic spray, water-in-oil emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gasifier, ointment, hot fog agent, cold fog agent, aerosol, solid / liquid mixture The invention relates to a combination agent, a liquid / liquid mixed agent, a solid / solid mixed agent, a lacquer, a microgranule, a tracking powder, an oil suspension, an oil-dispersible powder, a concentrated gel, a pouring agent, a seed coating agent, a smear, a film-forming oil agent, an ultra-low volume liquid agent, and a steam release agent; the plant diseases applicable to the bactericidal composition 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 applicable to the bactericidal composition are selected from: rice, wheat, barley, Oats, corn, sorghum, sweet potatoes, potatoes, cassava, soybeans, snow peas, broad beans, peas, mung beans, adzuki beans, cotton, sericulture, peanuts, rapeseed, sesame, sunflowers, beets, sugar cane, coffee, cocoa, ginseng, Fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomatoes, peppers, radishes, cucumbers, cabbage, celery, mustard tubers, beets, rapeseed, onions, garlic, watermelons, melons, cantaloupes, papayas, apples, citrus and peaches, tea, wild vegetables, bamboo shoots, hops, peppers, bananas, papayas, orchids, bonsai.

[0058] Example 5: Application of the combination of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention and an anti-plant virus agent in preventing and controlling viral diseases of agricultural, forestry and horticultural plants:

[0059] The antiviral composition formed by combining the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention with any one or two of commercial antiviral agents is used for preventing and controlling viral diseases of agricultural, forestry and horticultural plants. The commercial antiviral agent is selected from: benzothiadiazole, thiazolamide, isothiazolamide, ribavirin, anthofin, ningnanmycin, methiophene or salicylic acid, pyrimidine, dichloroisonicotinic acid, allylisothiazole, jinggangmycin, and guanidine hydrochloride; the total mass of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I in the antiviral composition is 1.5-1.5wt%; The percentage content is 1%-90%, and the ratio of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention to the aforementioned commercial anti-plant virus agent is 1%:99% to 99%:1% by mass; the dosage form processed by the anti-virus composition is selected from: seed treatment emulsion, aqueous emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granules, fine granules, soluble concentrate, poison valley, block poison bait, granular poison bait, sheet poison bait, concentrated poison bait, slow-release block, electrostatic spray, water-in-oil emulsion, smoke canister, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gasifier , ointment, hot mist, cold mist, aerosol, solid / liquid mixed agent, liquid / liquid mixed agent, solid / solid mixed agent, lacquer, microgranules, tracking powder, oil suspension, oil dispersible powder, concentrated glue, pouring agent, seed dressing agent, smear, film-forming oil agent, ultra-low volume liquid agent, steam release agent; the virus diseases controlled by the antiviral composition are selected from: rice dwarf disease, yellow dwarf disease, stripe leaf blight, tomato fern leaf virus disease, pepper mosaic virus disease, tobacco vein necrosis virus disease, corn dwarf mosaic disease, cauliflower mosaic virus, citrus virus disease, Jianlan orchid leaf virus, Jianlan ringspot virus; the anti-disease The plants that the toxic composition is used to control are selected from: rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, sericulture, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard tuber, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.

[0060] Example 6: Application of the combination of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention and acaricide in preventing and controlling mite damage in agriculture, forestry and horticultural plants:

[0061] The miticide composition formed by the combination of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention and any one or two of the commercial miticides is used for preventing and controlling mite pests in agriculture, forestry and horticultural plants. The commercial miticide is selected from the group consisting of dichlorvos, heptylphos, cypermethrin, dibromophos, pyrifos, chlormethoxam, ethion, cypermethrin, phosalone, methyl pyrifos, quinalphos, aphidox, chlormethoxam, chlormethoxam, phosmet, flumethrin, acralthrin, bifenthrin, cyhalothrin, cyhalothrin, cyhalothrin, cyhalothrin, cyhalothrin, cyhalothrin, cyhalothrin, bifenthrin, fenthiocarb, butanone, oxamyl, cypermethrin, long-acting cypermethrin, benomyl, chlormethoxam, cypermethrin, benzyl benzoate, Bromocriptine, cyfluthrin, acequinoxaline, fluazifop, flufenoxuron, liuyangmycin, cypermethrin, thuringin, acaricide, liuyangmycin, avermectin, doramectin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, azadirachtin, rotenone, tebufenamide, pyridabenzamide, fenpyraclostrobin, clofenazine, fenpyraclostrobin, hexythiazox, spirocyclopentyl, pyrimidine, cypermethrin, propargite, and pyridabenzamide; the total mass percentage of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I in the acaricide composition is 1%-90%, and the ratio of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I to the commercial acaricide is 1%:99% to 99% by mass. :1%; the dosage form processed by the acaricidal composition is selected from: seed treatment emulsion, aqueous emulsion, microemulsion, suspoemulsion, capsule suspension, water-soluble granules, fine granules, soluble concentrate, poisonous valley, block poison bait, granular poison bait, sheet poison bait, concentrated poison bait, slow-release block, electrostatic spray, water-in-oil emulsion, smoke can, smoke candle, smoke tube, smoke stick, smoke sheet, smoke pill, gasifier, ointment, hot fog, cold fog, aerosol, solid / liquid mixed agent, liquid / liquid mixed agent, solid / solid mixed agent, lacquer, microgranule, tracking powder, oil suspension, oil dispersible powder, concentrated glue, pouring agent, seed coating agent, smear, film-forming oil, ultra-low volume liquid, steam release agent; the mite pests controlled by the acaricidal composition are selected from: mite pests selected from Tetranychus, fine palpable mites The invention relates to pests of the genus Tetranychus, the genus Anopheles, the genus Phylogenetica, the genus Phylogenetica, the genus Phylogenetica, and the genus Phylogenetica, which are worldwide agricultural pests, forestry pests, gardening pests, and sanitary pests; the plants for which the acaricidal composition is used to control are selected from the group consisting of rice, wheat, barley, oats, corn, sorghum, sweet potatoes, potatoes, cassava, soybeans, snow peas, broad beans, peas, mung beans, adzuki beans, cotton, sericulture, peanuts, rapeseed, sesame, sunflowers, beets, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomatoes, peppers, radishes, cucumbers, cabbages, celery, mustard tubers, beets, rapeseed, onions, garlic, watermelons, melons, cantaloupes, papayas, apples, citrus and peach trees, tea, wild vegetables, bamboo shoots, hops, peppers, bananas, papayas, orchids, and bonsai.

[0062] Example 7: Use of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention in the preparation of a pesticide composition:

[0063] The pesticide composition prepared by the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention contains the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention as an active ingredient, the mass percentage of the active ingredient is 0.1% to 99.9%, the mass percentage of a solid or liquid adjuvant is 99.9% to 0.1%, and the composition further contains an optional surfactant in an amount of 0 to 25% by mass.

[0064] Example 8: Use of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention in the preparation of a pesticide compound composition:

[0065] The 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention can be compounded with other commercial pesticides, namely insecticides, miticides, fungicides, antiviral agents or plant immune activators to prepare a pesticide compound composition. The compound composition comprises the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention and commercial pesticides, namely insecticides, miticides, fungicides, antiviral agents or plant immune activators as active ingredients. The ratio of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I of the present invention to the other commercial pesticides, namely insecticides, miticides, fungicides, antiviral agents or plant immune activators is 1%:99% to 99%:1% by mass, the mass percentage content of the active ingredient is 0.1% to 99.9%, a solid or liquid adjuvant with a mass percentage content of 99.9% to 0.1%, and a surfactant with a mass percentage content of 0 to 25% by mass.

[0066] Industrial Applicability

[0067] The present invention provides a class of 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives; the derivatives of the present invention can regulate the biological activities of agricultural, horticultural, sanitary and forestry plant pests and plant pathogens, can be used in the agricultural, horticultural and forestry fields to kill insects, mites, sterilize, resist plant viruses, and induce plants to produce disease resistance, and have good economic value and application prospects.

[0068] Table 1 Chemical structures and physicochemical parameters of 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives of the present invention

[0069]

[0070] Table 2 Antibacterial activity of 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives I of the present invention (inhibition rate at 50 μg / ml / %)

[0071]

[0072] As: Tomato early blight pathogen, its Latin name is: Alternaria solani, Bc: Cucumber gray mold pathogen, its Latin name is: Botrytis cinerea, Ca: Peanut brown spot pathogen, its Latin name is: Cercospora arachidicola, Fg: Grainaceous Fusarium graminearum, Fv: Verticillium fusarium, its Latin name is: Fusarium verticillioides, Pp: Apple ring rot pathogen, its Latin name is: Physalosporapiricola, Rs: Rice sheath blight pathogen, its Latin name is: Rhizoctonia solani, Ss: Rapeseed sclerotinia pathogen, its Latin name is: Sclerotinia sclerotiorum.

[0073] Table 3 Precision toxicity test results of the antibacterial activity of 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives I of the present invention (EC 50 :microgram / ml)

[0074]

[0075] As: Tomato early blight pathogen, its Latin name is: Alternaria solani, Bc: Cucumber gray mold pathogen, its Latin name is: Botrytis cinerea, Ca: Peanut brown spot pathogen, its Latin name is: Cercospora arachidicola, Fg: Grainaceous Fusarium graminearum, Fv: Verticillium fusarium, its Latin name is: Fusarium verticillioides, Pp: Apple ring rot pathogen, its Latin name is: Physalosporapiricola, Rs: Rice sheath blight pathogen, its Latin name is: Rhizoctonia solani, Ss: Rapeseed sclerotinia pathogen, its Latin name is: Sclerotinia sclerotiorum.

Claims

1. A class of 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives having the general structural formula shown in Formula I: I: in, R 1 -R 5 Selected from: 2,6-dibromo-4-trifluoromethoxy, 2,6-dichloro-4-trifluoromethoxy, 2,4,6-trichloro, 3-tert-butyl, 3-isopropyl, [1,3]dioxane, 3-bromo-5-trifluoromethyl, 3-bromo-4-trifluoromethoxy, 3-trifluoromethyl-4-bromo, 3-bromo-5-methoxy, 3-bromo-4-methoxy, 2-bromo-4-trifluoromethyl, 3-phenoxy, 5,6, 7,8-Tetrahydronaphthalene, 2,3-dihydro-1H-indene, naphthalene, 2-bromo-trimethyl, 3-phenyl, 2-4'-chlorophenyl, 2-difluoromethoxy, 2-ethynyl, 2-tert-butyl, 2-cyano, 4-phenyl, 2-chloro-3-carbomethoxy, 2-isopropyl, 3-prop-1-en-2-yl, 3,5-ditrifluoromethyl, 2-chloro-6-fluoro, 2-4'-chlorophenoxy, 2-bromo-4-chloro-6-fluoro.

2. The specific synthetic route and method of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I described in claim 1 are: In a 100 ml round-bottom flask, 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid (2.0 mmol), oxalyl chloride (4.0 mmol), anhydrous N,N-dimethylformamide (3 drops) and dichloromethane (10 ml) were added in sequence, and the mixture was stirred at room temperature for 8 hours, and the solvent was removed under reduced pressure for use; in a 100 ml round-bottom flask, substituted amine (2.0 mmol), triethylamine (5.0 mmol) and dichloromethane (10 ml) were added in sequence. After the reaction was completed by thin layer chromatography, the solution was washed with dichloromethane (20 ml) and brine (20 ml), dried over anhydrous sodium sulfate and concentrated in vacuo, and the solvent was removed under reduced pressure. The residue was purified by 100-200 mesh silica gel column chromatography with ethyl acetate / petroleum ether as the eluent to obtain 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative I.

3. Use of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative according to claim 1 in the preparation of an agricultural fungicide, wherein the fungi controlled by the fungicide are tomato early blight, cucumber gray mold, peanut brown spot, wheat fusarium, apple ring rot, rice sheath blight, and rapeseed sclerotinia.

4. Use of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative according to claim 1 in the preparation of an agricultural plant immune activator, wherein the plant immune activator is used to control Arabidopsis downy mildew.

5. An agricultural fungicidal composition, comprising the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative according to claim 1 as an active ingredient; the composition comprises 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.

6. An agricultural fungicide compound composition, comprising the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative according to claim 1 and other commercial fungicides as active ingredients; the ratio of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative to the other commercial fungicides is 1%:99% to 99%:1% by weight, and the compound composition contains 1% to 99% by weight of the active ingredient, 99% to 1% by weight of a solid or liquid adjuvant, and 0 to 25% by weight of a surfactant.

7. An agricultural insecticide and acaricide compound composition, comprising the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative according to claim 1 and other commercial fungicides as active ingredients; the ratio of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative to the other commercial insecticide and acaricide 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 a solid or liquid adjuvant, and 0 to 25% by weight of a surfactant selected from the group consisting of.

8. A composite composition of anti-plant virus agents, comprising the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives according to claim 1 and other commercial fungicides as active ingredients; the ratio of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivatives to the other commercial anti-plant virus agents is 1%:99% to 99%:1% by weight, and the composite composition comprises 1% to 99% by weight of the active ingredient, 99% to 1% by weight of a solid or liquid adjuvant, and 0 to 25% by weight of a surfactant selected from the group consisting of.

9. A plant immune activator compound composition, comprising the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative according to claim 1 and other commercial fungicides as active ingredients; the ratio of the 3-(difluoromethyl)-1-methyl-1H-pyrazole derivative and other commercial plant immune activators is 1%:99% to 99%:1% by weight, and the compound composition contains 1% to 99% by weight of the active ingredient, 99% to 1% by weight of a solid or liquid adjuvant, and 0 to 25% by weight of a surfactant selected from the group consisting of.

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