CN113929694A - Sulfonyl hydrazide psoralen derivatives, and preparation method and application thereof - Google Patents
Sulfonyl hydrazide psoralen derivatives, and preparation method and application thereof Download PDFInfo
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- CN113929694A CN113929694A CN202111351113.2A CN202111351113A CN113929694A CN 113929694 A CN113929694 A CN 113929694A CN 202111351113 A CN202111351113 A CN 202111351113A CN 113929694 A CN113929694 A CN 113929694A
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- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
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Abstract
The invention provides a sulfonyl hydrazide psoralen derivative, a preparation method and application thereof, and particularly relates to a sulfonyl hydrazide psoralen derivative, wherein the chemical structure general formula of the sulfonyl hydrazide psoralen derivative is shown as formula I:
Description
Technical Field
The technical scheme of the invention belongs to the field of pesticides, and particularly relates to sulfonyl hydrazide psoralen compounds, and a preparation method and application thereof.
Background
The botanical fungicide utilizes certain antibacterial substances contained in some plants or induced plant defensins to kill or inhibit the growth of pathogenic bacteria, and has the advantages of high efficiency, low toxicity or no toxicity, easy degradation, high selectivity, difficult generation of drug resistance and the like (Yangjinmei, Fujian agricultural science, 2012, 27 (11): 1246-1249.). In recent years, botanical fungicides have received a great deal of attention as an important component of "environmentally-friendly pesticides" and "biologically-rational pesticides".
Psoralen is a furan type coumarin natural bioactive molecule derived from fructus psoraleae, has extremely strong photosensitization and physiological and pharmacological activities (Yuan sea dragon and other Chinese herbal medicines, 2021, 52 (01): 289 and 298), is an important plant source medicine intermediate, and has wide application value in the fields of food, medicine, pesticide and the like. With the use of a large amount of pesticides and the characteristics of easy generation of drug resistance and high iteration speed of pathogenic bacteria, the demand of antibacterial agents or antibacterial sources which have ideal antibacterial effects and can be widely applied is increasing, and natural antibacterial substances derived from plants are favored. The existing research shows that psoralen has inhibitory effect on pathogenic bacteria such as staphylococcus aureus, escherichia coli and the like; it also has inhibitory effect on pathogenic fungi such as Sclerotinia sclerotiorum and Rhizopus oryzae which cause crop yield reduction.
The sulfonyl hydrazide compounds are compounds containing nitrogen and sulfur atoms, are widely applied to the design and synthesis of pesticide molecules, and have a plurality of biological activities such as bacteriostasis, tumor resistance, HIV resistance, disinsection, anti-inflammation, antioxidation and the like (Chen ren hong et al. chemical research and application 2020, 32 (6): 1053-. The nitrogen atom is taken as an electron-rich group, can form hydrogen bonds with various enzymes in organisms, and is powerful for improving the biological activity of the compound.
In order to find and discover pesticide lead and candidate compounds which are more efficient, broad-spectrum, low-toxicity, low-ecological risk and free of cross resistance, the invention introduces sulfonyl hydrazide into the lead structure of psoralen, designs and synthesizes sulfonyl hydrazide psoralen derivatives, and screens and evaluates the biological activity of the system.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a synthesis method of a novel sulfonyl hydrazide psoralen derivative, provides a method for regulating and controlling the biological activity of agricultural, horticultural and sanitary and forestry plant pests and plant pathogens by using the compound and a determination method thereof, and also provides application of the compound in the agricultural field, the horticultural field, the forestry field and the sanitary field.
The technical scheme adopted by the invention for solving the technical problem is as follows: the chemical structural general formula of the sulfonyl hydrazide psoralen compound with insecticidal, acaricidal, bactericidal, anti-plant virus and plant disease-resistant activities in the agricultural field, the horticultural field and the forestry field is shown as I:
wherein R is1Selected from: hydrogen, 4-fluoro, 4-chloro; r2Selected from: hydrogen, methyl; r3Selected from: 4-methylphenyl, 4-chlorophenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-bromophenyl, phenyl, 4-trifluoromethylphenyl, 4-trifluoromethoxyphenyl, 5-chloro-2, 4-difluorophenyl, 4-tert-butylphenyl, 2, 4-dichlorophenyl, 3-fluorophenyl, 2-trifluoromethoxyphenyl, 3-methylphenyl, methyl, 3, 4-difluorophenyl, 4-iodophenyl, 2-naphthyl, trifluoromethyl, 4-cyanophenyl, 3-pyridyl, 4-ethylphenyl, cyclopropyl.
The synthesis route of the acyl sulfonyl hydrazide psoralen derivative I and the intermediate thereof is as follows:
the synthesis method of the sulfonyl hydrazide psoralen derivative I comprises the following steps:
A. preparation of compound 3:
putting the compound 1 into a reaction bottle, adding the compound 2, then slowly dropwise adding 98% concentrated sulfuric acid while stirring, and stirring at room temperature; after the reaction is finished, adding a proper amount of methanol, then pouring the methanol into ice water to generate a large amount of white solid, and performing suction filtration and drying to obtain a compound 3;
B. preparation of compound 5:
putting the compound 3 into a reaction bottle, adding a proper amount of anhydrous acetonitrile, then sequentially adding potassium carbonate, potassium iodide and the compound 4 while stirring, and heating and refluxing; after the reaction is finished, removing most of acetonitrile under reduced pressure, adding water and ethyl acetate for extraction, washing an organic phase by using a saturated sodium chloride solution, drying anhydrous sodium sulfate, carrying out suction filtration under reduced pressure, concentrating a filtrate to remove a solvent, and carrying out column chromatography purification to obtain a compound 5;
C. preparation of compound 6:
adding a compound 5 into a reaction bottle, adding a proper amount of isopropanol, slowly dropwise adding 1 mol/L sodium hydroxide solution while stirring, and heating and refluxing; after the reaction is finished, removing most of isopropanol under reduced pressure, adjusting the pH of the system to be 1-2 by using 1 mol/L hydrochloric acid solution, and performing suction filtration and drying on the generated solid to obtain a compound 6;
D. preparation of compound 7:
taking the compound 6, adding a proper amount of methanol into a reaction bottle, then slowly dropwise adding 98% concentrated sulfuric acid while stirring, and heating and refluxing; after the reaction is finished, removing most of methanol under reduced pressure, adding water and ethyl acetate into the residue for extraction, washing an organic phase by using a saturated sodium chloride solution, drying the organic phase by using anhydrous sodium sulfate, carrying out suction filtration under reduced pressure, concentrating the filtrate to remove the solvent, adding methanol into the residue, slowly dropwise adding 80% hydrazine hydrate under stirring at room temperature, and heating and refluxing; after the reaction is finished, removing most of solvent under reduced pressure, adding water and ethyl acetate for extraction, washing an organic phase by using a saturated sodium chloride solution, drying anhydrous sodium sulfate, carrying out suction filtration under reduced pressure, concentrating a filtrate to remove the solvent, and carrying out column chromatography purification to obtain a compound 7;
E. preparation of compound I:
taking the compound 7, adding a proper amount of anhydrous pyridine into a reaction bottle, then slowly adding substituted sulfonyl chloride while stirring, and stirring at room temperature; after the reaction is finished, adding water and ethyl acetate for extraction, washing an organic phase by using a 1 mol/L hydrochloric acid solution and a saturated sodium chloride solution in sequence, drying by using anhydrous sodium sulfate, carrying out vacuum filtration, concentrating a filtrate to remove a solvent, and carrying out column chromatography purification to obtain the compound I.
As a preferred embodiment, the synthesis method of the sulfonyl hydrazide psoralen derivative comprises the following steps:
A. preparation of compound 3:
a100 ml round-bottom flask was charged with 18.2 mmol of resorcinol and 18.2 mmol of dimethyl acetylsuccinate, followed by slowly dropping 2.73 ml of 98% concentrated sulfuric acid under stirring, and after the dropping was completed, the reaction system was stirred at room temperature overnight. Monitoring by TLC, adding 30 ml of anhydrous methanol after the reaction is finished, pouring the anhydrous methanol into ice water to generate a large amount of white solid, performing suction filtration on the obtained solid, washing the crude product with diethyl ether, and recrystallizing with ethanol-water to obtain a compound 3; the amount of compound 3 produced and the volume of the reaction vessel are scaled up or down accordingly.
B. Preparation of compound 5:
in a 100 ml round-bottom flask were charged 4.03 mmol of compound 3 and 30 ml of anhydrous acetonitrile, and 4.836 mmol of compound 4, 16.12 mmol of anhydrous potassium carbonate and 0.403 mmol of potassium iodide were sequentially added under stirring at room temperature, followed by heating and refluxing the reaction system for 5 hours. Monitoring by TLC, standing and cooling to room temperature after the reaction is finished, removing most of solvent under reduced pressure, adding 30 ml of water into the residue, extracting for three times (15 ml. times.3) by ethyl acetate, washing the organic phase for three times (15 ml. times.3) by saturated sodium chloride solution, and drying the combined organic layers by anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying with petroleum ether/ethyl acetate (3: 1, volume/volume) eluent column chromatography to obtain compound 5; the amount of compound 5 produced and the volume of the reaction vessel are scaled up or down accordingly.
C. Preparation of compound 6:
1 g of compound 5 and 30 ml of isopropanol are added into a 100 ml round-bottom flask, 30 ml of 1 mol/l sodium hydroxide solution is slowly added dropwise under stirring at room temperature, and the reaction system is heated and refluxed for 4 hours after the dropwise addition. Monitoring by TLC, standing the system after the reaction is finished, cooling to room temperature, removing most isopropanol under reduced pressure, adding 1 mol/L hydrochloric acid solution into the residue to adjust the pH of the system to 1, precipitating a large amount of solid, performing suction filtration, and drying to obtain a compound 6; the amount of compound 6 produced and the volume of the reaction vessel are scaled up or down accordingly.
D. Preparation of compound 7:
a100-ml round-bottom flask was charged with 1 g of Compound 6 and 30 ml of anhydrous methanol, and 1.5 ml of 98% concentrated sulfuric acid was slowly added dropwise with stirring, followed by heating the reaction system under reflux for 4 hours. Monitoring by TLC, after the reaction is finished, standing the system, cooling to room temperature, removing most of solvent under reduced pressure, adding 30 ml of water into the residue, extracting three times (15 ml. times.3) by using ethyl acetate, washing the organic phase for three times (15 ml. times.3) by using saturated sodium chloride solution, and drying the combined organic layers by using anhydrous sodium sulfate; suction filtration was carried out under reduced pressure, the filtrate was concentrated to remove the solvent, and the crude product was used in the next step without purification.
1 g of the crude product and 30 ml of anhydrous methanol were added to a 100 ml round-bottom flask, 10 ml of 80% hydrazine hydrate was slowly added dropwise with stirring at room temperature, and after completion of the addition, the system was heated under reflux for 5 hours. Monitoring by TLC, after the reaction is finished, standing the system, cooling to room temperature, removing most of solvent under reduced pressure, adding 30 ml of water into the residue, extracting for three times (15 ml. times.3) by using ethyl acetate, separating out an organic phase, washing for three times (15 ml. times.3) by using a saturated sodium chloride solution, and drying a combined organic layer by using anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying with dichloromethane/methanol (25: 1, volume/volume) eluent column chromatography to obtain compound 7; the amount of compound 7 produced and the volume of the reaction vessel are scaled up or down accordingly.
E. Preparation of compound I:
a100 ml round-bottom flask was charged with 1 mmol of Compound 7 and 5 ml of anhydrous pyridine, and 1 mmol of substituted sulfonyl chloride was slowly added with stirring, followed by stirring the reaction system at room temperature overnight. TLC, after the reaction was complete 30 ml of water was added, extracted three times with ethyl acetate (15 ml × 3), the organic phase was washed twice with 1 mol/l hydrochloric acid solution (15 ml × 2) and three times with saturated sodium chloride solution (15 ml × 3), and the combined organic layers were dried over anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying with petroleum ether/ethyl acetate (1: 1, volume/volume) eluent column chromatography to obtain compound I; the amount of compound I prepared and the volume of the reaction vessel are scaled up or down accordingly.
Wherein, the substituent R1、R2、R3As defined above; r1Selected from: hydrogen, 4-fluoro, 4-chloro; r2Selected from: hydrogen, methyl; r3Selected from: 4-methylphenyl, 4-chlorophenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-bromophenyl, phenyl, 4-trifluoromethylphenyl, 4-trifluoromethoxyphenyl, 5-chloro-2, 4-difluorophenyl, 4-tert-butylphenyl, 2, 4-dichlorophenyl, 3-fluorophenyl, 2-trifluoromethoxyphenyl, 3-methylphenyl, methyl, 3, 4-difluorophenyl, 4-iodophenyl, 2-naphthyl, trifluoromethyl, 4-cyanophenyl, 3-pyridyl, 4-ethylphenyl, cyclopropyl.
The invention provides application of the sulfonyl hydrazide psoralen derivative I in preparing a fungicide.
The invention provides application of the sulfonyl hydrazide psoralen derivative I in preparing an anti-tobacco mosaic virus agent.
The invention provides application of the sulfonyl hydrazide psoralen derivative I in preparing a plant activator for inducing tobacco to resist tobacco mosaic virus.
The invention provides application of the sulfonyl hydrazide psoralen derivative I in preventing and treating agricultural and forestry and horticultural plant insect pests.
Co-administering the sulfonyl hydrazide psoralen derivative I and an agricultural chemical; the agrochemical is selected from: one or more of insecticide, bactericide, plant virus resisting agent and acaricide.
The sulfonyl hydrazide psoralen derivative I and any one or two of the insecticides are combined to form an insecticidal composition for preventing and treating agricultural and forestry and horticultural plant insect pests;
the insecticide is selected from: methoprene, diazinon, acetamiprid, emamectin benzoate, milbemectin, abamectin, pleocidin, metaflumethrin, meperfluthrin, cyfluthrin, beta-cypermethrin, lambda-cyhalothrin, permethrin, allethrin, bifenthrin, permethrin, flumethrin, cyfluthrin, imidacloprid, nitenpyram, imidaclothianidin, thiacloprid, thiamethoxam, clothianidin, dinotefuran, cotinine, dinotefuran, diflubenzuron, chlorbenzuron, tefluazuron, flufenoxuron, lufenuron, chlorflufenoxuron, fluazuron, diflubenzuron, fluazuron, tezine, fluazuron, tezine, teflufenozide, tebufenozide, tezine, flufenozide, tebufenozide, tezine, tebufenozide, tezine, tebufenozide, tezine, tebufalin, tezine, tebenflumetsulbenflumetsulbens, tezine, tebenil, tezine, tebenil, tebenflumetsulbens, tebenil, tebens, tezine, tebens, and tebens, and the like, Methoxyfenozide, chromafenozide, dichlorvos, quinalphos, pyridaphenthion, cicada powder, carbaryl, pirimicarb, metolcarb, isoprocarb, cartap, fenobucarb, tetrafenozide, fenitrothion, hexythiazox, carbaryl, fenisobromolate, hexythiazox, pyridate, clofentezine, spirodiclofen, spirotetramat, azocyclobutazine, buprofezin, monosultap, dimehypo, chlorantraniliprole, tetrachlorantranilide, flubendiamide, cyantraniliprole, butenenitrile, tolfenpyrad, chlorfenapyr, pyrazofos, pyrazinone, etoxazole, tebufenpyrad, pyridaben, emamectin, and pentapyraflufen;
the content of the sulfohydrazide psoralen derivative I in the insecticidal composition is 1-90% by mass; preferably, the ratio of the sulfonyl hydrazide psoralen derivative I to the pesticide is 1 percent to 99 percent to 1 percent by mass percentage;
the insecticide composition is processed into a dosage form selected from the group consisting of: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents;
the plant insect pests controlled by the insecticidal composition are selected from: meadow spodoptera, red spider, east Asian migratory locust, spruce-bug, Chinese rice locust, japanese yellow-back locust, single-prick mole cricket, oriental mole cricket, rice thrips, thrips tabaci, green house thrips, rice straw thistle, wheat simple pipe thrips, green house whitefly, bemisia tabaci, black tail hopper, big leaf hopper, cotton leafhopper, lesser leafhopper, brown plant hopper, white back plant hopper, gray plant hopper, sugarcane flat leaf planthopper, cotton aphid, binary wheat aphid, wheat straw aphid, peach aphid, sorghum aphid, radish aphid, mealybug, lybug, stinkbug, arrowhead bug, round scale, white insect, red wax insect, red worm, mealybug, pear net, banana net bug, tiny flower bug, laceleaf fly, green fly, rice moth, black armyworm, black fly, black rice moth, black armyworm, black rice moth, black rice plant, black rice plant, black rice plant, green plant, rice plant, black rice plant, green plant, rice plant, green plant, rice plant, pink bollworm, sweet potato wheat moth, diamond back moth, peach fruit borer, soybean pod borer, peach fruit borer, apple tip leaf roller moth, brown banded leaf roller moth, pardos leaf roller moth, striped rice borer, pod borer, corn borer, yellow rice borer, cabbage moth, rice leaf roller borer, striped rice borer, cotton leaf borer, peach borer, armyworm, prodenia litura, rice bollworm, cotton small bridgehead moth, beet armyworm, sesamia inferen, cotton bollworm, Dinodon diamond-back moth, agrotis, yellow cutworm, robber venom moth, gypsy moth, sweet potato hawkmoth, bean hawkmoth, straight grain rice skipper, cryptophyte butterfly, caeruleuca, caeruleuciscus nigra, yellow mealyratus caeruleucade, yellow meadowrue, yellow rice beetle, yellow tiger, red ramie yellow vanne, yellow rice borer, yellow rice, yellow rice borer, yellow rice borer, yellow rice borer, yellow rice borer, yellow rice borer, yellow rice borer, yellow rice borer, yellow rice, yellow rice borer, yellow rice borer, yellow rice borer, yellow rice, yellow rice borer, yellow rice borer, yellow rice, yellow rice borer, yellow rice, Tribolium castaneum, verdigris, black tortoise, branchia palustris, longicorn beetle, pink neck longicorn beetle, ape leaf worm, yellow melon, flea beetle, mung bean weevil, pea weevil, broad bean weevil, corn weevil, rice weevil, wheat leaf bee, pear fruit bee, yellow stripe wasp, armyworm white star ichneumonid, sandfly bractenoconid, cotton bollworm tooth-lipped ichneumonid, borer black spot wart, mosquito, fly, horsefly, red mud fly, yellow leaf sucking serous, rice gall mosquito fly, citrus fruit fly, melon fruit fly, wheat leaf gray fly, American fly, black stalk black fly, wheat stem fly, seed fly, onion fly, radish skirt, eupatorium, corn borer, and armyworm;
the plants controlled by the insecticidal composition are selected from the following plants: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
The sulfonyl hydrazide psoralen derivative I and any one or two of the bactericides are combined to form a bactericidal composition for preventing and treating agricultural and forestry and horticultural plant diseases;
the bactericide is selected from: benzothiadiazole, tiadinil, thianamide, methicillin, 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid, 4-methyl-1, 2, 3-thiadiazole-5-sodium formate, 4-methyl-1, 2, 3-thiadiazole-5-ethyl formate, DL-beta-aminobutyric acid, isotianil, 3, 4-dichloroisothiazole-5-carboxylic acid, 3, 4-dichloroisothiazole-5-sodium formate, 3, 4-dichloroisothiazole-5-ethyl formate, ribavirin, antofine, ningnanmycin or salicylic acid, cyanamide, thiram, ziram, mancozeb, fosetyl, thiophanate-methyl, chlorothalonil, chlormadinone, procymidone, fenpropidium rust, Thiophanate methyl, thiophanate, metalaxyl-M, flumorph, dimethomorph, metalaxyl-M, benalaxyl-M, diclocyanamide, sulfentram, sulfsulfamide, thifluzamide, folpet, cyprodinil, cyhalodiamide, silthiopham, carboxin, oxim-methyl, mefuram, fenazamide, flutolanil, furametpyr, thifluzamide, boscalid, penthiopyrad, isopyrazamide, bixafen, fluopyram, fluxastrobin, fluxapyroxad, flufenapyr, benconazole, iprovalicarb, flutriafolan, flufenpyrazamide, flufenacetmid, fluoxastrobin, fenhexamid, iprodione, trifloxystrobin, kresoximtrobin, trifloxystrobin, fenstrobin, fenstrobilurin, fenpyraclostrobin, fluoxastrobin, fluoxastrobilurin, fluoxastrobin, fluoxastrobilurin, fluoxastrobin, fluoxastrobilurin, fluoxastrobin, fluoxastrobilurin, fluoxastrobin, fluoxastrobilurin, fluoxastrobin, fluopicolide, fluopicolinate, fluopicolide, fluopicolinate, fluopicolide, fluopicolinate, fluo, Enestroburin, dimethomorph, difenoconazole, bromhexine, epoxiconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole, difenoconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, imazalil, prochloraz, triflumizole, cyazofamid, fenamidone, imidazole, pefurazoate, famoxadone, pyridinozole, prodiamine, ethaboxam, hymexazol, penoxsulam, fenthion, fenpropimorph, tridemorph, fenpyroxanil, fluazinam, fenpropiconazole, fenpyrazamide, fluazinam, cyprodinil, flufenamidone, fenpyrad, fenpyroxim, fenpyroxapyroxapyroxad, fenpyroxad-methyl, fenpyroxad-a, Mepanipyrim, pyrimethanil, fenarimol, fluoropyrimidinol, mefenamate, dithianon, ethoxyquin, hydroxyquinoline, propoxymine, phenoxyquinoline, diethofencarb, iprovalicarb, benthiavalicarb, propamocarb, sulbencarb, edifenphos, iprobenfos, pyrazofos, tolclofos-methyl, blasticidin, kasugamycin, polyoxin, validamycin, streptomycin, metalaxyl, furalaxyl, benomyl, thiophanate-methyl, triadimefon, bupirimate, dimethirimol, ethirimol, captan, folpet, vinclozolin, fluocinolone, dimethachlon, chlorothalonil, isoprothiolane, pefurazone, bismerzole, quintozene, propineb, fosetyl, sulfur, polidocusate, cuprous oxide, cupric chloride, cupric oxide, cupric hydroxide, Metrafenone, pencycuron, pyridaben, tetrachlorophthalide, pyroquilon, spiroxamine, tricyclazole, azinam, dodine, diguanidinium salt, diguanidinium, niclosamide, bentiamine, tolfenpyrad, indole ester, sodium disulfate, quinconazole, probenazole, bronopol, methyl iodide, metam, dichloline ester, dazomet, dichloroisopropyl ether, fosthiazate, fosfenthion, fenamiphos, thiothifenthion, methiocarb, sulfuryl fluoride, dichloropropylene, dichloroisonicotinic acid, allylisothiazole;
the total mass percentage of the sulfonyl hydrazide psoralen derivative I in the bactericidal composition is 1-90%; the ratio of the sulfonyl hydrazide psoralen derivative I to the bactericide is 1 to 99 to 1 percent by mass;
the bactericidal composition is processed into a dosage form selected from the group consisting of: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents;
the plant diseases controlled by the bactericidal composition are selected from: rice seedling blight, tomato root rot, potato late blight, tobacco black shank, millet powdery mildew, grape downy mildew, lettuce downy mildew, cucumber anthracnose;
the plants suitable for the bactericidal composition are selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
The sulfonyl hydrazide psoralen derivative I and any one or two of the antiviral medicaments are combined to form an antiviral composition for preventing and treating virus diseases of agricultural, forestry and horticultural plants;
the antiviral agent is selected from: benzothiadiazole, tiadinil, isotianil, 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid, 4-methyl-1, 2, 3-thiadiazole-5-sodium formate, 4-methyl-1, 2, 3-thiadiazole-5-ethyl formate, 3, 4-dichloroisothiazole-5-carboxylic acid, 3, 4-dichloroisothiazole-5-sodium formate, 3, 4-dichloroisothiazole-5-ethyl formate, DL-beta-aminobutyric acid, 2, 6-dichloroisonicotinic acid, N-cyanomethyl-2-chloroisonicotinamide, probenazole, virazole, antofine, ningnanmycin, thiamide, methiothiamide or salicylic acid, pyriminomycin, Dichloroisonicotinic acid, probenazole, validamycin, moroxydine hydrochloride;
the total mass percentage of the sulfonyl hydrazide psoralen derivative I in the antiviral composition is 1-90%; preferably, the ratio of the sulfonyl hydrazide psoralen derivative I to the anti-plant virus agent is 1 percent to 99 percent to 1 percent by mass percentage;
the antiviral composition is processed into a dosage form selected from: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents;
the antiviral composition can be used for preventing and treating viral diseases selected from: rice dwarf, yellow dwarf, stripe disease, tomato fern leaf virus, pepper mosaic virus, tobacco vein necrosis virus, maize dwarf mosaic, cauliflower mosaic, citrus virus, cymbidium mosaic, cymbidium ringspot virus;
the plants for preventing and treating the antiviral composition are selected from the following plants: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
The sulfonyl hydrazide psoralen derivative I and any one or two of the acaricides are combined to form an acaricide composition for preventing and controlling acarid damage of agricultural, forestry and horticultural plants;
the acaricide is selected from: dichlorvos, heptenophos, metofos, monocrotophos, phosphorus dibromide, pyrimidophos, chloromethylthion, ethion, chlorfenvinphos, vofenthion, pirimiphos, phoxim, isocarbophos, amicarbazone, chlormephos, fluthrin, bifenthrin, cyhalothrin, lambda-cyhalothrin, fenpropathrin, flumethrin, fluvalinate, bifenthrin, bifenazate, fenobucarb, butoxycarb, carbofuran, monocarb, benomyl, cloxacarb, butathiocarb, lufenuron, benzyl benzoate, bromopropylate, cyflumetofen, dimethrin, flufenpyr, fluazuron, bleomycin, chlortetracycline, abamectin, avermectin, lium, lividin, doramectin, epothidin, ivermectin, simethiofen, dimethofos, dimethrin, dimethoxim, fosetyl, chlorfenapyr, isofos, chlorfenapyr, dimethoxim, fluazurin, isomycin, chlorfenacin, avermectin, chlorfenacin, chlorfenapyr, chlorpyrifos, chlorpyri, Nicotine, matrine, azadirachtin, rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spirodiclofen, fluacrypyrim, propargite and pyridaben;
the total mass percentage of the sulfonyl hydrazide psoralen derivative I in the acaricidal composition is 1-90%; the ratio of the sulfonyl hydrazide psoralen derivative I to the acaricide is 1 to 99 to 1 percent by mass percent;
the acaricidal composition is processed into a dosage form selected from the following: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents;
the mite damage controlled by the mite-killing composition is selected from the following groups: the mite is selected from spider mite family, furaciidae, gall mite family, Tetranychus genus, and pest mites of gall mite family, which are world agricultural pest mites, forestry pest mites, horticultural pest mites, and health pest mites;
the plant for controlling the acaricidal composition is selected from the following plants: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
The biological activity of the sulfonyl hydrazide psoralen derivative I is measured as follows:
F. the bactericidal activity of the sulfonyl hydrazide psoralen derivative I is determined as follows:
the bactericidal or bacteriostatic activity of the sulfonyl hydrazide psoralen I adopts a thallus growth rate measuring method, and the specific steps are as follows: dissolving 1.8 mg of sample in 2 drops of N, N-dimethylformamide, diluting with a water solution containing a certain amount of Tween 20 emulsifier to 500 micrograms/ml of medicament, sucking 1 ml of the medicament to be tested in a culture dish under an aseptic condition, adding 9 ml of PDA culture medium, shaking uniformly to prepare a medicament-containing flat plate with the concentration of 50 micrograms/ml, taking the flat plate added with 1 ml of sterile water as a blank control, cutting a bacterial disc by a puncher with the diameter of 4 mm along the outer edge of hypha, moving the bacterial disc to the medicament-containing flat plate, placing the bacterial disc in an equilateral triangle, repeating the treatment for 3 times, placing the culture dish in a constant temperature incubator with the temperature of 24 +/-1 ℃ for culture, investigating the expansion diameter of each treated bacterial disc after the diameter of the control bacterial colony is expanded to 2-3 cm, calculating the relative bacteriostasis rate by comparing with the blank control, wherein the strain is the species of most typical plant pathogenic bacteria actually occurring in the agricultural production of China, the code numbers and names are as follows: AS: tomato early blight, its latin name is: alternaria solani, BC: the cucumber botrytis cinerea with the latin name as follows: botrytis cinerea, CA: peanut brown spot pathogen, its latin name is: cercospora arachidicola, GZ: wheat scab, its latin name is: gibberella zeae, PP: apple ring rot, its latin name is: physiosporia piricola, PS: rhizoctonia solani, the Latin name of which is: pellicularia sasakii, SS: sclerotinia sclerotiorum, its latin name is: sclerotina sclerotiorum.
The invention has the beneficial effects that: the sulfonyl hydrazide psoralen derivatives I are subjected to lead optimization, and the sulfonyl hydrazide psoralen derivatives are subjected to antibacterial activity screening.
The synthesis, biological activity and application of the sulfonyl hydrazide psoralen derivatives I are more specifically illustrated by specific preparation and biological activity determination examples, which are only used for specifically illustrating the invention and not for limiting the invention, and particularly, the biological activity is only illustrated by way of example and not for limiting the patent, and the specific embodiments are as follows:
example 1: preparation of compound 3:
adding 18.2 mmol of resorcinol and 18.2 mmol of dimethyl acetyl succinate into a 100 ml round-bottom flask, then slowly dropwise adding 2.73 ml of 98% concentrated sulfuric acid under stirring, and stirring the reaction system at room temperature overnight after dropwise adding; monitoring by TLC, adding 30 ml of anhydrous methanol after the reaction is finished, pouring the anhydrous methanol into ice water to generate a large amount of white solid, performing suction filtration on the obtained solid, washing the crude product with diethyl ether, and recrystallizing with ethanol-water to obtain a compound 3; the yield is 81%; the nuclear magnetic data are as follows:1h NMR (400MHz, DMSO) δ 10.50(s, 1H), 7.59(d, J ═ 8.8Hz, 1H), 6.79(dd, J ═ 8.7, 2.1Hz, 1H), 6.69(d, J ═ 2.1Hz, 1H), 3.61(s, 2H), 3.57(s, 3H), 2.30(s, 3H). The amount of compound 3 produced and the volume of the reaction vessel are scaled up or down accordingly.
Example 2: preparation of compound 5:
in a 100 ml round-bottom flask were charged 4.03 mmol of compound 3 and 30 ml of anhydrous acetonitrile, and 4.836 mmol of compound 4, 16.12 mmol of anhydrous potassium carbonate and 0.403 mmol of potassium iodide were sequentially added under stirring at room temperature, followed by heating and refluxing the reaction system for 5 hours. Monitoring by TLC, standing and cooling to room temperature after the reaction is finished,most of the solvent was removed under reduced pressure, 30 ml of water was added to the residue, extracted three times with ethyl acetate (15 ml. times.3), the organic phase was washed three times with saturated sodium chloride solution (15 ml. times.3), and the combined organic layers were dried over anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying with petroleum ether/ethyl acetate (3: 1, volume/volume) eluent column chromatography to obtain compound 5; the yield is 62 percent; the nuclear magnetic data are as follows:1h NMR (400MHz, DMSO) δ 8.04(d, J ═ 7.2Hz, 2H), 7.78-7.68(m, 2H), 7.59(t, J ═ 7.7Hz, 2H), 7.11(d, J ═ 2.5Hz, 1H), 7.05(dd, J ═ 8.9, 2.6Hz, 1H), 5.76(s, 2H), 3.67(s, 2H), 3.62(s, 3H), 2.39(s, 3H). The amount of compound 5 produced and the volume of the reaction vessel are scaled up or down accordingly.
Example 3: preparation of compound 6:
1 g of compound 5 and 30 ml of isopropanol are added into a 100 ml round-bottom flask, 30 ml of 1 mol/l sodium hydroxide solution is slowly added dropwise under stirring at room temperature, and the reaction system is heated and refluxed for 4 hours after the dropwise addition. Monitoring by TLC, standing the system after the reaction is finished, cooling to room temperature, removing most isopropanol under reduced pressure, adding 1 mol/L hydrochloric acid solution into the residue to adjust the pH of the system to 1, precipitating a large amount of solid, performing suction filtration, and drying to obtain a compound 6; the yield is 54 percent; the nuclear magnetic data are as follows:1h NMR (400MHz, DMSO) δ 12.54(s, 1H), 8.49(s, 1H), 8.18(s, 1H), 7.84(d, J ═ 7.3Hz, 2H), 7.78(s, 1H), 7.58(t, J ═ 7.6Hz, 2H), 7.48(dd, J ═ 15.2, 7.8Hz, 1H), 3.68(s, 2H), 2.55(s, 3H). The amount of compound 6 produced and the volume of the reaction vessel are scaled up or down accordingly.
Example 4: preparation of compound 7:
a100-ml round-bottom flask was charged with 1 g of Compound 6 and 30 ml of anhydrous methanol, and 1.5 ml of 98% concentrated sulfuric acid was slowly added dropwise with stirring, followed by heating the reaction system under reflux for 4 hours. Monitoring by TLC, after the reaction is finished, standing the system, cooling to room temperature, removing most of solvent under reduced pressure, adding 30 ml of water into the residue, extracting three times (15 ml. times.3) by using ethyl acetate, washing the organic phase for three times (15 ml. times.3) by using saturated sodium chloride solution, and drying the combined organic layers by using anhydrous sodium sulfate; suction filtration was carried out under reduced pressure, the filtrate was concentrated to remove the solvent, and the crude product was used in the next step without purification.
1 g of the crude product and 30 ml of anhydrous methanol were added to a 100 ml round-bottom flask, 10 ml of 80% hydrazine hydrate was slowly added dropwise with stirring at room temperature, and after completion of the addition, the system was heated under reflux for 5 hours. Monitoring by TLC, after the reaction is finished, standing the system, cooling to room temperature, removing most of solvent under reduced pressure, adding 30 ml of water into the residue, extracting for three times (15 ml. times.3) by using ethyl acetate, separating out an organic phase, washing for three times (15 ml. times.3) by using a saturated sodium chloride solution, and drying a combined organic layer by using anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying with dichloromethane/methanol (25: 1, volume/volume) eluent column chromatography to obtain compound 7; the yield is 71%; the nuclear magnetic data are as follows:1h NMR (400MHz, DMSO) δ 9.15(s, 1H), 8.41(s, 1H), 8.08(s, 1H), 7.77(d, J ═ 7.5Hz, 2H), 7.69(s, 1H), 7.53(t, J ═ 7.5Hz, 2H), 7.42(t, J ═ 7.2Hz, 1H), 4.24(s, 2H), 3.48(s, 2H), 2.46(s, 3H). The amount of compound 7 produced and the volume of the reaction vessel are scaled up or down accordingly.
Example 5: preparation of compound I:
a100 ml round-bottom flask was charged with 1 mmol of Compound 7 and 5 ml of anhydrous pyridine, and 1 mmol of substituted sulfonyl chloride was slowly added with stirring, followed by stirring the reaction system at room temperature overnight. TLC was monitored, 30 ml of water were added after the reaction was complete, extraction was carried out three times with ethyl acetate (15 ml. times.3) and the organic phase was successively dissolved in 1 mol/l hydrochloric acidTwo washes (15 ml × 2) and three washes with saturated sodium chloride solution (15 ml × 3), and the combined organic layers were dried over anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying with petroleum ether/ethyl acetate (1: 1, volume/volume) eluent column chromatography to obtain compound I; yield: 52 to 92 percent; when R is1Is phenyl, R2For 4-methylphenyl, the nuclear magnetic data for compound I-1 is as follows:1h NMR (400MHz, DMSO) δ 10.24(d, J ═ 3.4Hz, 1H), 9.79(d, J ═ 3.4Hz, 1H), 8.47(s, 1H), 8.15(s, 1H), 7.84-7.79(m, 3H), 7.68(d, J ═ 8.2Hz, 2H), 7.55(t, J ═ 7.6Hz, 2H), 7.45(d, J ═ 7.4Hz, 1H), 7.27(d, J ═ 8.1Hz, 2H), 3.46(s, 2H), 2.36(s, 3H), 2.27(s, 3H). The preparation amount of the compound I-1 and the volume of a reaction vessel are enlarged or reduced according to corresponding proportion; the physicochemical and structural parameters of compound I are shown in Table 1.
Example 6: the determination result of the antibacterial activity of the sulfonyl hydrazide psoralen derivative I comprises the following steps:
the codes and names of the common plant pathogenic fungi tested by the invention are as follows: a.s: tomato early blight, its latin name is: alternaria solani, b.c: the cucumber botrytis cinerea with the latin name as follows: botrytis cinerea, C.a: peanut brown spot pathogen, its latin name is: cercospora arachidicola, G.z: wheat scab, its latin name is: gibberella zeae, P.p: apple ring rot, its latin name is: physiosporia piricola, P.s: rhizoctonia solani, the Latin name of which is: pellicularia sasakii, S.s: sclerotinia sclerotiorum, its latin name is: the strains have good representativeness and can represent the species of most pathogenic bacteria in the field in agricultural production.
The results of the cell growth rate method are shown in Table 2, and Table 2 shows that all the compounds synthesized by the invention have bactericidal activity of different degrees at 50 micrograms/ml. For tomato early blight bacteria, the inhibition rates of the compounds DJY-2-46, DJY-1-129, DJY-1-147, DJY-1-142, DJY-1-133, DJY-1-146, DJY-2-45, DJY-2-49 and DJY-1-151 are all more than 50%, and are equivalent to or higher than that of control medicaments such as bone lipid supplement and YZK-C22, wherein the inhibition rates of the compounds DJY-2-46, DJY-1-142 and DJY-2-49 are all more than 68%, and are all more than that of the control medicaments such as bone lipid supplement and YZK-C2210%; for botrytis cinerea, the inhibition rate of the compounds DKY-1-142, DKY-1-165 and DKY-3-21 is more than 60%, which is more than 10% higher than that of a control medicament for supplementing bone lipoprotein, and especially the bactericidal activity of the compound DKY-3-21 is the highest and reaches 78%; for peanut brown spot pathogen, the inhibition rate of the compounds DJY-1-165, DJY-1-164, DJY-1-133, DJY-1-154 and DJY-1-159 is more than 60 percent, and the inhibition rate is equivalent to or higher than that of control medicaments such as the bone lipid supplement and YZK-C22, particularly the compound DJY-1-164 has the highest bactericidal activity which is 77 percent and is more than 10 percent higher than that of the control medicaments such as the bone lipid supplement; for apple ring rot germ, the inhibition rate of the compounds DJY-1-165 and DJY-1-154 is more than 60 percent, which is higher than that of the control drug for supplementing the bone lipoprotein by about 20 percent.
Example 7: the application of the sulfonyl hydrazide psoralen derivative I in preparing the pesticide composition comprises the following steps:
the invention relates to a pesticide composition prepared from sulfonyl hydrazide psoralen derivatives I, which comprises 0.1 to 99.9 weight percent of sulfonyl hydrazide psoralen derivatives I and intermediates thereof as active ingredients, 99.9 to 0.1 weight percent of solid or liquid auxiliary agents and 0 to 50 weight percent of optional surfactant.
Example 8: the application of the sulfonyl hydrazide psoralen derivative I in preparing the pesticide compound composition comprises the following steps:
the sulfonyl hydrazide psoralen derivative I and the intermediate thereof can be compounded with other commercial pesticides, namely insecticides, acaricides, bactericides, antiviral agents or plant activators to prepare a pesticide compound composition, the compound composition comprises the sulfonyl hydrazide psoralen derivative I and the intermediate thereof and other commercial pesticides, namely insecticides, acaricides, bactericides, antiviral agents or plant activators, as active ingredients, the ratio of the sulfonyl hydrazide psoralen derivative I and the intermediate thereof to the other commercial pesticides, namely insecticides, acaricides, bactericides, antiviral agents or plant activators is 1 to 99 percent to 1 percent by mass, the content of the active ingredients is 0.1 to 99.9 percent by weight, 99.9 to 0.1 percent by weight of solid or liquid auxiliaries, and optionally 0 to 50 percent by weight of surfactant.
Example 9: the application of the combination of the sulfonyl hydrazide psoralen derivatives I and the pesticide in preventing and treating the insect pests of agricultural, forestry and horticultural plants is as follows:
the sulfonyl hydrazide psoralen derivative I and any one or two of commercial insecticides are combined to form an insecticidal composition for preventing and treating agricultural and forestry and horticultural plant insect pests, wherein the commercial insecticide is selected from the following components: methoprene, diazinon, acetamiprid, emamectin benzoate, milbemectin, abamectin, pleocidin, metaflumethrin, meperfluthrin, cyfluthrin, beta-cypermethrin, lambda-cyhalothrin, permethrin, allethrin, bifenthrin, permethrin, flumethrin, cyfluthrin, imidacloprid, nitenpyram, imidaclothianidin, thiacloprid, thiamethoxam, clothianidin, dinotefuran, cotinine, dinotefuran, diflubenzuron, chlorbenzuron, tefluazuron, flufenoxuron, lufenuron, chlorflufenoxuron, fluazuron, diflubenzuron, fluazuron, tezine, fluazuron, tezine, teflufenozide, tebufenozide, tezine, flufenozide, tebufenozide, tezine, tebufenozide, tezine, tebufenozide, tezine, tebufalin, tezine, tebenflumetsulbenflumetsulbens, tezine, tebenil, tezine, tebenil, tebenflumetsulbens, tebenil, tebens, tezine, tebens, and tebens, and the like, Methoxyfenozide, chromafenozide, dichlorvos, quinalphos, pyridaphenthion, cicada powder, carbaryl, pirimicarb, metolcarb, isoprocarb, cartap, fenobucarb, tetrafenozide, fenitrothion, hexythiazox, carbaryl, fenisobromolate, hexythiazox, pyridate, clofentezine, spirodiclofen, spirotetramat, azocyclobutazine, buprofezin, monosultap, dimehypo, chlorantraniliprole, tetrachlorantranilide, flubendiamide, cyantraniliprole, butenenitrile, tolfenpyrad, chlorfenapyr, pyrazofos, pyrazinone, etoxazole, tebufenpyrad, pyridaben, emamectin, and pentapyraflufen; the mass percentage of the sulfonyl hydrazide psoralen derivative I in the insecticidal composition is 1-90%, and the mass percentage of the sulfonyl hydrazide psoralen derivative I and the commercial insecticide is 1% to 99% to 1%; the insecticide composition is processed into a dosage form selected from the group consisting of: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents; the plant insect pests controlled by the insecticidal composition are selected from: meadow spodoptera, red spider, east Asian migratory locust, spruce-bug, Chinese rice locust, japanese yellow-back locust, single-prick mole cricket, oriental mole cricket, rice thrips, thrips tabaci, green house thrips, rice straw thistle, wheat simple pipe thrips, green house whitefly, bemisia tabaci, black tail hopper, big leaf hopper, cotton leafhopper, lesser leafhopper, brown plant hopper, white back plant hopper, gray plant hopper, sugarcane flat leaf planthopper, cotton aphid, binary wheat aphid, wheat straw aphid, peach aphid, sorghum aphid, radish aphid, mealybug, lybug, stinkbug, arrowhead bug, round scale, white insect, red wax insect, red worm, mealybug, pear net, banana net bug, tiny flower bug, laceleaf fly, green fly, rice moth, black armyworm, black fly, black rice moth, black armyworm, black rice moth, black rice plant, black rice plant, black rice plant, green plant, rice plant, black rice plant, green plant, rice plant, green plant, rice plant, pink bollworm, sweet potato wheat moth, diamond back moth, peach fruit borer, soybean pod borer, peach fruit borer, apple tip leaf roller moth, brown banded leaf roller moth, pardos leaf roller moth, striped rice borer, pod borer, corn borer, yellow rice borer, cabbage moth, rice leaf roller borer, striped rice borer, cotton leaf borer, peach borer, armyworm, prodenia litura, rice bollworm, cotton small bridgehead moth, beet armyworm, sesamia inferen, cotton bollworm, Dinodon diamond-back moth, agrotis, yellow cutworm, robber venom moth, gypsy moth, sweet potato hawkmoth, bean hawkmoth, straight grain rice skipper, cryptophyte butterfly, caeruleuca, caeruleuciscus nigra, yellow mealyratus caeruleucade, yellow meadowrue, yellow rice beetle, yellow tiger, red ramie yellow vanne, yellow rice borer, yellow rice, yellow rice borer, yellow rice borer, yellow rice borer, yellow rice borer, yellow rice borer, yellow rice borer, yellow rice borer, yellow rice, yellow rice borer, yellow rice borer, yellow rice borer, yellow rice, yellow rice borer, yellow rice borer, yellow rice, yellow rice borer, yellow rice, Tribolium castaneum, verdigris, black tortoise, branchia palustris, longicorn beetle, pink neck longicorn beetle, ape leaf worm, yellow melon, flea beetle, mung bean weevil, pea weevil, broad bean weevil, corn weevil, rice weevil, wheat leaf bee, pear fruit bee, yellow stripe wasp, armyworm white star ichneumonid, sandfly bractenoconid, cotton bollworm tooth-lipped ichneumonid, borer black spot wart, mosquito, fly, horsefly, red mud fly, yellow leaf sucking serous, rice gall mosquito fly, citrus fruit fly, melon fruit fly, wheat leaf gray fly, American fly, black stalk black fly, wheat stem fly, seed fly, onion fly, radish skirt, eupatorium, corn borer, and armyworm; the plants controlled by the insecticidal composition are selected from the following plants: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
Example 10: the application of the combination of the sulfonyl hydrazide psoralen derivatives I and the bactericide in preventing and treating agricultural, forestry and horticultural plant diseases:
the sulfonyl hydrazide psoralen derivative I and any one or two of commercial bactericides form a bactericidal composition for preventing and treating agricultural, forestry and horticultural plant diseases, and the commercial bactericides are selected from the following components: benzothiadiazole, tiadinil, thianamide, methicillin, 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid, 4-methyl-1, 2, 3-thiadiazole-5-sodium formate, 4-methyl-1, 2, 3-thiadiazole-5-ethyl formate, DL-beta-aminobutyric acid, isotianil, 3, 4-dichloroisothiazole-5-carboxylic acid, 3, 4-dichloroisothiazole-5-sodium formate, 3, 4-dichloroisothiazole-5-ethyl formate, ribavirin, antofine, ningnanmycin or salicylic acid, cyanamide, thiram, ziram, mancozeb, fosetyl, thiophanate-methyl, chlorothalonil, chlormadinone, procymidone, fenpropidium rust, Thiophanate methyl, thiophanate, metalaxyl-M, flumorph, dimethomorph, metalaxyl-M, benalaxyl-M, diclocyanamide, sulfentram, sulfsulfamide, thifluzamide, folpet, cyprodinil, cyhalodiamide, silthiopham, carboxin, oxim-methyl, mefuram, fenazamide, flutolanil, furametpyr, thifluzamide, boscalid, penthiopyrad, isopyrazamide, bixafen, fluopyram, fluxastrobin, fluxapyroxad, flufenapyr, benconazole, iprovalicarb, flutriafolan, flufenpyrazamide, flufenacetmid, fluoxastrobin, fenhexamid, iprodione, trifloxystrobin, kresoximtrobin, trifloxystrobin, fenstrobin, fenstrobilurin, fenpyraclostrobin, fluoxastrobin, fluoxastrobilurin, fluoxastrobin, fluoxastrobilurin, fluoxastrobin, fluoxastrobilurin, fluoxastrobin, fluoxastrobilurin, fluoxastrobin, fluoxastrobilurin, fluoxastrobin, fluopicolide, fluopicolinate, fluopicolide, fluopicolinate, fluopicolide, fluopicolinate, fluo, Enestroburin, dimethomorph, difenoconazole, bromhexine, epoxiconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole, difenoconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, imazalil, prochloraz, triflumizole, cyazofamid, fenamidone, imidazole, pefurazoate, famoxadone, pyridinozole, prodiamine, ethaboxam, hymexazol, penoxsulam, fenthion, fenpropimorph, tridemorph, fenpyroxanil, fluazinam, fenpropiconazole, fenpyrazamide, fluazinam, cyprodinil, flufenamidone, fenpyrad, fenpyroxim, fenpyroxapyroxapyroxad, fenpyroxad-methyl, fenpyroxad-a, Mepanipyrim, pyrimethanil, fenarimol, fluoropyrimidinol, mefenamate, dithianon, ethoxyquin, hydroxyquinoline, propoxymine, phenoxyquinoline, diethofencarb, iprovalicarb, benthiavalicarb, propamocarb, sulbencarb, edifenphos, iprobenfos, pyrazofos, tolclofos-methyl, blasticidin, kasugamycin, polyoxin, validamycin, streptomycin, metalaxyl, furalaxyl, benomyl, thiophanate-methyl, triadimefon, bupirimate, dimethirimol, ethirimol, captan, folpet, vinclozolin, fluocinolone, dimethachlon, chlorothalonil, isoprothiolane, pefurazone, bismerzole, quintozene, propineb, fosetyl, sulfur, polidocusate, cuprous oxide, cupric chloride, cupric oxide, cupric hydroxide, Metrafenone, pencycuron, pyridaben, tetrachlorophthalide, pyroquilon, spiroxamine, tricyclazole, azinam, dodine, diguanidinium salt, diguanidinium, niclosamide, bentiamine, tolfenpyrad, indole ester, sodium disulfate, quinconazole, probenazole, bronopol, methyl iodide, metam, dichloline ester, dazomet, dichloroisopropyl ether, fosthiazate, fosfenthion, fenamiphos, thiothifenthion, methiocarb, sulfuryl fluoride, dichloropropylene, dichloroisonicotinic acid, allylisothiazole; the total mass percentage of the sulfonyl hydrazide psoralen derivative I in the sterilization composition is 1-90%, and the mass percentage of the sulfonyl hydrazide psoralen derivative I and the commercial sterilization agent is 1% to 99% to 1%; the bactericidal composition is processed into a dosage form selected from the group consisting of: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents; the plant diseases controlled by the bactericidal composition are selected from: rice seedling blight, tomato root rot, potato late blight, tobacco black shank, millet powdery mildew, grape downy mildew, lettuce downy mildew, cucumber anthracnose; the plants suitable for the bactericidal composition are selected from the group consisting of: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
Example 11: the application of the combination of the sulfonyl hydrazide psoralen derivatives I and the plant virus resisting agent in preventing and treating virus diseases of agricultural, forestry and horticultural plants is as follows:
the sulfonyl hydrazide psoralen derivative I and any one or two of commercial antiviral medicaments form an antiviral composition for preventing and treating virus diseases of agricultural, forestry and horticultural plants, wherein the commercial antiviral medicaments are selected from: benzothiadiazole, tiadinil, isotianil, 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid, 4-methyl-1, 2, 3-thiadiazole-5-sodium formate, 4-methyl-1, 2, 3-thiadiazole-5-ethyl formate, 3, 4-dichloroisothiazole-5-carboxylic acid, 3, 4-dichloroisothiazole-5-sodium formate, 3, 4-dichloroisothiazole-5-ethyl formate, DL-beta-aminobutyric acid, ribavirin, antofine, ningnanmycin, thiaamide, mehtothiazolamide or salicylic acid, pyriminomycin, dichloroisonicotinic acid, probenazole, validamycin hydrochloride; the total mass percentage of the sulfonyl hydrazide psoralen derivative I in the antiviral composition is 1-90%, and the mass percentage of the sulfonyl hydrazide psoralen derivative I and the commercial anti-plant virus agent is 1-99-1%; the antiviral composition is processed into a dosage form selected from: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents; the antiviral composition can be used for preventing and treating viral diseases selected from: rice dwarf, yellow dwarf, stripe disease, tomato fern leaf virus, pepper mosaic virus, tobacco vein necrosis virus, maize dwarf mosaic, cauliflower mosaic, citrus virus, cymbidium mosaic, cymbidium ringspot virus; the plants for preventing and treating the antiviral composition are selected from the following plants: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
Example 12: the application of the combination of the sulfonyl hydrazide psoralen derivatives I and the acaricide in preventing and treating the mite damage of agricultural, forestry and horticultural plants is as follows:
the sulfonyl hydrazide psoralen derivative I and any one or two of commercial acaricides form an acaricidal composition for preventing and controlling acarid damages of agricultural, forestry and horticultural plants, wherein the commercial acaricides are selected from the following groups: dichlorvos, heptenophos, metofos, monocrotophos, phosphorus dibromide, pyrimidophos, chloromethylthion, ethion, chlorfenvinphos, vofenthion, pirimiphos, phoxim, isocarbophos, amicarbazone, chlormephos, fluthrin, bifenthrin, cyhalothrin, lambda-cyhalothrin, fenpropathrin, flumethrin, fluvalinate, bifenthrin, bifenazate, fenobucarb, butoxycarb, carbofuran, monocarb, benomyl, cloxacarb, butathiocarb, lufenuron, benzyl benzoate, bromopropylate, cyflumetofen, dimethrin, flufenpyr, fluazuron, bleomycin, chlortetracycline, abamectin, avermectin, lium, lividin, doramectin, epothidin, ivermectin, simethiofen, dimethofos, dimethrin, dimethoxim, fosetyl, chlorfenapyr, isofos, chlorfenapyr, dimethoxim, fluazurin, isomycin, chlorfenacin, avermectin, chlorfenacin, chlorfenapyr, chlorpyrifos, chlorpyri, Nicotine, matrine, azadirachtin, rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spirodiclofen, fluacrypyrim, propargite and pyridaben; the total mass percentage of the sulfonyl hydrazide psoralen derivative I in the acaricidal composition is 1-90%, and the ratio of the sulfonyl hydrazide psoralen derivative I to the commercial acaricide is 1-99% to 99-1%; the acaricidal composition is processed into a dosage form selected from the following: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water soluble granules, fine granules, soluble concentrates, venoms, block baits, granular baits, tablet baits, concentrated baits, sustained release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cartridges, aerosol sticks, aerosol tablets, aerosol pellets, gas generants, ointments, hot fogging formulations, cold fogging formulations, aerosols, solid/liquid mixtures, liquid/liquid mixtures, solid/solid mixtures, lacquers, microgranules, chasing powders, oil suspensions, oil dispersible powders, concentrated gels, pour-on formulations, seed coatings, paints, film-forming oils, ultra-low volume liquids, vapor release agents; the mite damage controlled by the mite-killing composition is selected from the following groups: the mite is selected from spider mite family, furaciidae, goiter family, Tetranychus genus, and pest mites of the goiter family, which are world agricultural pest mites, forestry pest mites, horticultural pest mites, and health pest mites; the plant for controlling the acaricidal composition is selected from the following plants: rice, wheat, barley, oats, corn, sorghum, sweet potato, cassava, soybean, sweet broad bean, pea, mung bean, small bean, cotton, silkworm, peanut, rape, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chili, radish, cucumber, cabbage, celery, tuber mustard, sugar beet, rape, shallot, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, bonsai.
Industrial applicability
The invention provides a sulfonyl hydrazide psoralen derivative; the derivative can regulate and control the biological activity of agricultural, horticultural and sanitary pests and plant pathogens of forestry plants, can be used for killing insects, killing mites, sterilizing, resisting plant viruses and inducing plants to generate disease resistance in the agricultural field, the horticultural field and the forestry field, and has better economic value and application prospect.
TABLE 2 antibacterial Activity of Sulfonylhydrazide psoralen derivatives I of the present invention (inhibition ratio of 50. mu.g/ml/%)
| Serial number | Compound (I) | A.s | B.c | C.a | G.z | P.p | P.s | S.s |
| 1 | DJY-1-109 | 42 | 43 | 43 | 40 | 31 | 14 | 29 |
| 2 | DJY-1-111 | 46 | 18 | 32 | 28 | 22 | 28 | 23 |
| 3 | DJY-1-121 | 28 | 39 | 42 | 27 | 25 | 15 | 24 |
| 4 | DJY-1-122 | 47 | 38 | 40 | 41 | 26 | 21 | 23 |
| 5 | DJY-1-126 | 35 | 24 | 29 | 21 | 21 | 24 | 23 |
| 6 | DJY-1-127 | 35 | 20 | 31 | 22 | 29 | 19 | 22 |
| 7 | DJY-1-128 | 36 | 41 | 42 | 27 | 25 | 22 | 18 |
| 8 | DJY-1-130 | 33 | 24 | 33 | 22 | 21 | 38 | 28 |
| 9 | DJY-1-132 | 38 | 23 | 32 | 23 | 16 | 39 | 29 |
| 10 | DJY-2-46 | 71 | 38 | 40 | 28 | 35 | 25 | 16 |
| 11 | DJY-1-129 | 60 | 26 | 27 | 22 | 16 | 19 | 27 |
| 12 | DJY-1-133 | 52 | 27 | 66 | 39 | 26 | 14 | 23 |
| 13 | DJY-1-140 | 39 | 31 | 39 | 30 | 22 | 44 | 23 |
| 14 | DJY-1-145 | 38 | 34 | 41 | 24 | 26 | 25 | 25 |
| 15 | DJY-1-146 | 51 | 34 | 39 | 25 | 21 | 13 | 18 |
| 16 | DJY-1-147 | 65 | 21 | 33 | 30 | 38 | 26 | 24 |
| 17 | DJY-1-150 | 33 | 29 | 39 | 23 | 22 | 30 | 24 |
| 18 | DJY-1-142 | 68 | 61 | 31 | 26 | 33 | 38 | 24 |
| 19 | DJY-1-148 | 38 | 24 | 44 | 23 | 20 | 23 | 25 |
| 20 | DJY-2-49 | 70 | 42 | 44 | 39 | 27 | 24 | 20 |
| 21 | DJY-1-164 | 27 | 31 | 77 | 23 | 26 | 18 | 27 |
| 22 | DJY-2-45 | 57 | 24 | 35 | 32 | 22 | 24 | 28 |
| 23 | DJY-1-155 | 32 | 24 | 14 | 23 | 24 | 23 | 23 |
| 24 | DJY-1-165 | 41 | 67 | 72 | 34 | 63 | 23 | 31 |
| 25 | DJY-1-162 | 39 | 24 | 32 | 19 | 23 | 23 | 28 |
| 26 | DJY-1-154 | 32 | 37 | 64 | 23 | 67 | 21 | 30 |
| 27 | DJY-1-159 | 37 | 26 | 63 | 29 | 18 | 27 | 28 |
| 28 | DJY-1-152 | 32 | 24 | 36 | 22 | 22 | 23 | 22 |
| 29 | DJY-1-151 | 62 | 25 | 42 | 24 | 31 | 23 | 25 |
| 30 | DJY-3-21 | 22 | 78 | 59 | 41 | 34 | 38 | 50 |
| 31 | DJY-3-16 | 9 | 33 | 25 | 32 | 5 | 4 | 19 |
| 32 | DJY-3-15 | 20 | 37 | 27 | 30 | 12 | 7 | 14 |
| 33 | Psoralen | 56 | 50 | 65 | 63 | 44 | 52 | 58 |
| 34 | YZK-C22 | 58 | 72 | 74 | 75 | 57 | 81 | 61 |
A.s: tomato early blight, its latin name is: alternaria solani, b.c: the cucumber botrytis cinerea with the latin name as follows: botrytis cinerea, C.a: peanut brown spot pathogen, its latin name is: cercospora arachidicola, G.z: wheat scab, its latin name is: gibberella zeae, P.p: apple ring rot, its latin name is: physiosporia piricola, P.s: rhizoctonia solani, the Latin name of which is: pellicularia sasakii, S.s: sclerotinia sclerotiorum, its latin name is: sclerotina sclerotomalis.
Claims (7)
1. A sulfonyl hydrazide psoralen derivative is characterized by simultaneously containing sulfonyl hydrazide and psoralen structures and has a structural general formula shown in a formula I:
wherein R is1Selected from: hydrogen, 4-fluoro, 4-chloro; r2Selected from: hydrogen, methyl; r3Selected from: 4-methylphenyl, 4-chlorophenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-bromophenyl, phenyl, 4-trifluoromethylphenyl, 4-trifluoromethoxyphenyl, 5-chloro-2, 4-difluorophenyl, 4-tert-butylphenyl, 2, 4-dichlorophenyl, 3-fluorophenyl, 2-trifluoromethoxyphenyl, 3-methylphenyl, methyl, 3, 4-difluorophenyl, 4-iodophenyl, 2-naphthyl, trifluoromethyl, 4-cyanophenyl, 3-pyridyl, 4-ethylphenyl, cyclopropyl.
2. The specific synthetic route and method of the sulfonyl hydrazide psoralen derivative I as claimed in claim 1 are as follows:
A：
B：
the definition of the substituent is as defined in claim 1, and the specific synthetic method comprises the following steps:
A. preparation of compound 3:
putting the compound 1 into a reaction bottle, adding the compound 2, then slowly dropwise adding 98% concentrated sulfuric acid while stirring, and stirring at room temperature; after the reaction is finished, adding a proper amount of methanol, then pouring the methanol into ice water to generate a large amount of white solid, and performing suction filtration and drying to obtain a compound 3;
B. preparation of compound 5:
putting the compound 3 into a reaction bottle, adding a proper amount of anhydrous acetonitrile, then sequentially adding potassium carbonate, potassium iodide and the compound 4 while stirring, and heating and refluxing; after the reaction is finished, removing most of acetonitrile under reduced pressure, adding water and ethyl acetate for extraction, washing an organic phase by using a saturated sodium chloride solution, drying anhydrous sodium sulfate, carrying out suction filtration under reduced pressure, concentrating a filtrate to remove a solvent, and carrying out column chromatography purification to obtain a compound 5;
C. preparation of compound 6:
adding a compound 5 into a reaction bottle, adding a proper amount of isopropanol, slowly dropwise adding 1 mol/L sodium hydroxide solution while stirring, and heating and refluxing; after the reaction is finished, removing most of isopropanol under reduced pressure, adjusting the pH of the system to be 1-2 by using 1 mol/L hydrochloric acid solution, and performing suction filtration and drying on the generated solid to obtain a compound 6;
D. preparation of compound 7:
taking the compound 6, adding a proper amount of methanol into a reaction bottle, then slowly dropwise adding 98% concentrated sulfuric acid while stirring, and heating and refluxing; after the reaction is finished, removing most of methanol under reduced pressure, adding water and ethyl acetate into the residue for extraction, washing an organic phase by using a saturated sodium chloride solution, drying the organic phase by using anhydrous sodium sulfate, carrying out suction filtration under reduced pressure, concentrating the filtrate to remove the solvent, adding methanol into the residue, slowly dropwise adding 80% hydrazine hydrate under stirring at room temperature, and heating and refluxing; after the reaction is finished, removing most of solvent under reduced pressure, adding water and ethyl acetate for extraction, washing an organic phase by using a saturated sodium chloride solution, drying anhydrous sodium sulfate, carrying out suction filtration under reduced pressure, concentrating a filtrate to remove the solvent, and carrying out column chromatography purification to obtain a compound 7;
E. preparation of compound I:
taking the compound 7, adding a proper amount of anhydrous pyridine into a reaction bottle, then slowly adding substituted sulfonyl chloride while stirring, and stirring at room temperature; after the reaction is finished, adding water and ethyl acetate for extraction, washing an organic phase by using a 1 mol/L hydrochloric acid solution and a saturated sodium chloride solution in sequence, drying by using anhydrous sodium sulfate, carrying out vacuum filtration, concentrating a filtrate to remove a solvent, and carrying out column chromatography purification to obtain the compound I.
3. Use of the sulfonylhydrazide psoralen derivative I as claimed in claim 1 for the preparation of an agricultural fungicide.
4. An agricultural fungicidal composition comprising the sulfonyl hydrazide psoralen derivative I as claimed in claim 1 and an intermediate, which can be prepared into an agricultural fungicidal composition comprising the sulfonyl hydrazide psoralen derivative I as claimed in claim 1 as an active ingredient in an amount of 0.1 to 99.9% by weight, 99.9 to 0.1% by weight of a solid or liquid adjuvant, and optionally 0 to 25% by weight of a surfactant.
5. An agricultural sterilization compound composition, which comprises the sulfonyl hydrazide psoralen derivative I as claimed in claim 1 and other commercial bactericides which are compounded to serve as active ingredients, wherein the ratio of the sulfonyl hydrazide psoralen derivative I to the other commercial bactericides is 1 percent to 99 percent to 1 percent by mass, the content of the active ingredients is 1 to 99 percent by weight, and the solid or liquid auxiliary agent accounts for 99 to 1 percent by weight.
6. An agricultural insecticidal and acaricidal compound composition, which comprises the sulfonyl hydrazide psoralen derivative I as claimed in claim 1 and other commercial insecticidal and acaricidal agents as active ingredients, wherein the insecticidal and acaricidal ratio of the sulfonyl hydrazide psoralen derivative I to the other commercial agents is 1% to 99% to 1%, the content of the active ingredients is 1 to 99% by weight, and the content of the solid or liquid auxiliary agents is 99 to 1% by weight.
7. A compound composition of an anti-plant virus agent comprises the sulfonyl hydrazide psoralen derivative I and other commercial anti-plant virus agents which are compounded as active ingredients in claim 1, wherein the ratio of the sulfonyl hydrazide psoralen derivative I to the other commercial anti-plant virus agents is 1 to 99 to 1 percent, the content of the active ingredients is 1 to 99 percent by weight, and 99 to 1 percent by weight of solid or liquid auxiliary agents.
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| US20030105339A1 (en) * | 1993-06-28 | 2003-06-05 | Cerus Corporation | Compounds for the photodecontamination of pathogens in blood |
| KR20100113862A (en) * | 2009-04-14 | 2010-10-22 | 한국화학연구원 | Composition for controlling plant diseases comprising psoralen corylifolia extract, and method for controlling plant diseases using the same |
| CN102067850A (en) * | 2011-03-02 | 2011-05-25 | 江苏省中国科学院植物研究所 | Application of psoralen as agricultural disinfectant or pesticide |
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- 2021-11-16 CN CN202111351113.2A patent/CN113929694A/en active Pending
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| US20030105339A1 (en) * | 1993-06-28 | 2003-06-05 | Cerus Corporation | Compounds for the photodecontamination of pathogens in blood |
| KR20100113862A (en) * | 2009-04-14 | 2010-10-22 | 한국화학연구원 | Composition for controlling plant diseases comprising psoralen corylifolia extract, and method for controlling plant diseases using the same |
| CN102067850A (en) * | 2011-03-02 | 2011-05-25 | 江苏省中国科学院植物研究所 | Application of psoralen as agricultural disinfectant or pesticide |
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