CN113929695B - Sulfimide psoralen derivatives, and preparation method and application thereof - Google Patents

Sulfimide psoralen derivatives, and preparation method and application thereof Download PDF

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CN113929695B
CN113929695B CN202111351115.1A CN202111351115A CN113929695B CN 113929695 B CN113929695 B CN 113929695B CN 202111351115 A CN202111351115 A CN 202111351115A CN 113929695 B CN113929695 B CN 113929695B
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CN113929695A (en
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范志金
董静月
洪泽宇
李坤
陈蕾
高卫
唐良富
王志宏
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Nankai University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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 sulfimide psoralen derivatives, a preparation method and application thereof, and in particular relates to sulfimide psoralen derivatives, the chemical structural general formula of which is shown in formula I:

Description

Sulfimide psoralen derivatives, and preparation method and application thereof
Technical Field
The technical scheme of the invention belongs to the field of pesticides, and particularly relates to a sulfimide psoralen compound, a preparation method and application thereof.
Background
Psoralen is furan coumarin compound derived from fructus Psoraleae, widely existing in radix Glehniae, radix Saposhnikoviae, radix Angelicae Pubescentis, etc., and has various physiological and pharmacological activities such as relaxing tracheal smooth muscle, preventing and treating osteoporosis, stopping bleeding, inhibiting bacteria, killing parasite, resisting cancer, resisting HIV, resisting inflammation, resisting oxidation, etc. (Yuan Hailong, etc.. Chinese herbal medicine, 2021, 52 (01): 289-298). The psoralen is used as a bactericide in agriculture, has wide bacteriostasis spectrum and long lasting period, and is an ideal bactericide in agriculture. Compared with the conventional pesticide, the psoralen has the effects of contact killing and stomach poisoning on pests, and has remarkable effect; psoralen is also an important plant source medicine intermediate, has the characteristics of low toxicity, no residue, no pollution and no public hazard for various commercial crops such as grains, melons, fruits, vegetables and the like, and is more beneficial to environmental protection.
The sulfimide compound is a hexavalent sulfur compound containing one oxygen atom, one nitrogen atom and two carbon substituents, and is a molecular fragment with biological activity and widely existing in biological active molecules such as pesticides, medicines and the like. Sulfinylimides are a very potent bioisostere in pharmaceutical chemistry, and the stereochemistry of sulfur atoms has a great impact on the biological activity of the compounds. Sulfinimides are used as isosteres of sulfones, nitrogen atoms provide modifiable sites, and are also important points of drug development, and the structural fragments are introduced into drug molecules, so that the water solubility of the drugs can be improved, and the physicochemical properties of the compounds are improved, thereby improving the activity of the compounds. Sulfinimides can also be used as chiral prosthetic groups, asymmetrically catalyzed ligands and as directing groups for hydrocarbon activation (Zhang Hongbin et al, university of Yunnan nationality, nature science edition, 2016, 25 (6): 491-498.).
In order to find and discover pesticide lead and candidate compounds which are more efficient, broad-spectrum, low in toxicity and ecological risk and have no interactive resistance, the invention introduces a sulfimide structure into a lead structure of the psoralen, designs and synthesizes a sulfimide psoralen derivative, and screens and evaluates the biological activity of the system.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: provides a novel synthesis method of sulfinimine psoralen derivatives, provides biological activities of the compounds for regulating and controlling plant pests and plant pathogens in agriculture, gardening, sanitation and forestry and a determination method thereof, and simultaneously provides application of the compounds in the fields of agriculture, gardening, forestry and sanitation.
The technical scheme adopted by the invention for solving the technical problems is as follows: the chemical structural general formula of the sulfimide psoralen compound with insecticidal, acaricidal, bactericidal, anti-plant virus and induced plant disease resistance activity in the agricultural field, the gardening field and the forestry field is shown as I:
Wherein R 1 is selected from: hydrogen, 4-fluoro, 4-chloro; r 2 is selected from: cyclopropanesulfonyl, 4-trifluoromethoxybenzenesulfonyl, 4-nitrobenzenesulfonyl, 4-methylbenzenesulfonyl, 2, 4-dichlorobenzenesulfonyl, 4-methoxybenzenesulfonyl, 4-fluorobenzenesulfonyl, 4-chlorobenzenesulfonyl, benzenesulfonyl, 4-tert-butylbenzenesulfonyl, methanesulfonyl, trifluoromethanesulfonyl, 4-iodobenzenesulfonyl, 4-bromobenzenesulfonyl, 4-ethylbenzenesulfonyl, 3, 4-difluorobenzenesulfonyl, 2-naphthalenesulfonyl, 4-tert-butylbenzoyl, hydrogen, 4-trifluoromethylbenzoyl, 3-bromobenzoyl, 3-trifluoromethoxybenzoyl, 4-methylbenzoyl, 4-fluorobenzoyl, acetyl, 1-naphthoyl, (3, 5-dichlorophenyl) carbamoyl, (4-trifluoromethoxyphenyl) carbamoyl, (4-fluorophenyl) carbamoyl, (3-methylphenyl) carbamoyl, 3-dichlorophenyl), 3, 4-dichloro-5-thiazole, 2-dimethylpentane, 2-fluoro-2-chlorobenzoyl, 2-fluoro-1-dimethylpentane, 2-fluoro-2-benzoyl.
The synthesis route of the sulfinimine psoralen derivative I and the intermediate thereof is as follows:
the synthesis method of the sulfimide psoralen derivative I comprises the following steps:
A. preparation of compound 3:
adding the compound 1 into a reaction bottle, adding the compound 2, then slowly dropwise adding 98% concentrated sulfuric acid under 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 carrying out suction filtration and drying to obtain a compound 3;
B. Preparation of compound 5:
Taking a compound 3, adding a proper amount of anhydrous acetonitrile into a reaction bottle, then sequentially adding potassium carbonate, potassium iodide and a compound 4 under stirring, and heating and refluxing; after the reaction is finished, removing most acetonitrile under reduced pressure, adding water and ethyl acetate for extraction, washing an organic phase with saturated sodium chloride solution, drying with anhydrous sodium sulfate, carrying out vacuum filtration, concentrating filtrate to remove solvent, and purifying by column chromatography to obtain a compound 5;
C. Preparation of Compound 6:
adding a proper amount of isopropanol into a reaction bottle, slowly dropwise adding 1 mol/L sodium hydroxide solution under stirring, and heating for reflux; after the reaction is finished, removing most of isopropanol under reduced pressure, regulating the pH value of a system to be 1-2 by using 1 mol/L hydrochloric acid solution, and carrying out suction filtration and drying on the generated solid to obtain a compound 6;
D. Preparation of compound 7:
Adding a proper amount of N, N-dimethylformamide into a reaction bottle, sequentially adding 1H-benzotriazole-1-yl oxygen tripyrrolidine hexafluorophosphate, N-diisopropylethylamine and 4-amino anisole sulfide under 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 saturated sodium chloride solution, drying by using anhydrous sodium sulfate, carrying out vacuum filtration, concentrating filtrate to remove a solvent, and purifying by column chromatography to obtain a compound 7;
E. Preparation of Compound I-a:
Adding a proper amount of absolute methanol into a reaction bottle, sequentially adding iodobenzene diacetic acid and ammonium carbonate under stirring, and stirring at room temperature; after the reaction is finished, removing most of methanol under reduced pressure, adding water and ethyl acetate for extraction, washing an organic phase with saturated sodium chloride solution, drying with anhydrous sodium sulfate, carrying out vacuum filtration, concentrating filtrate to remove solvent, and purifying by column chromatography to obtain a compound I-a;
F. preparation of Compound I-b:
Taking a compound I-a, adding a proper amount of anhydrous pyridine into a reaction bottle, then adding substituted sulfonyl chloride, and stirring at room temperature; after the reaction is finished, adding water and ethyl acetate for extraction, washing an organic phase by using a1 mol/L hydrochloric acid solution and a saturated sodium chloride solution in sequence, drying by using anhydrous sodium sulfate, carrying out vacuum filtration, concentrating filtrate to remove a solvent, and purifying by column chromatography to obtain a compound I-b;
G. preparation of Compounds I-c:
Adding a proper amount of anhydrous pyridine into a reaction bottle, then adding substituted acyl chloride, and stirring at room temperature; after the reaction is finished, adding water and ethyl acetate for extraction, washing an organic phase by using 1mol/L hydrochloric acid solution, saturated sodium bicarbonate solution and saturated sodium chloride solution in sequence, drying by using anhydrous sodium sulfate, carrying out vacuum filtration, concentrating filtrate to remove a solvent, and purifying by column chromatography to obtain a compound I-c;
H. preparation of Compounds I-d:
adding a proper amount of N, N-dimethylformamide into a reaction bottle, sequentially adding cuprous chloride and substituted isocyanate, and stirring at room temperature; after the reaction, water and ethyl acetate are added for extraction, an organic phase is washed by saturated sodium chloride solution, dried by anhydrous sodium sulfate, reduced pressure and suction filtration are carried out, the filtrate is concentrated to remove the solvent, and the compound I-d is obtained by column chromatography purification.
As a preferred embodiment, the synthesis method of the sulfinimine psoralen derivatives comprises the following steps:
A. preparation of compound 3:
Into a 100ml round bottom flask were added 18.2 mmol resorcinol and 18.2 mmol dimethyl acetylsuccinate followed by slowly dropwise adding 2.73 ml 98% concentrated sulfuric acid with stirring, after which the reaction was stirred at room temperature overnight. Monitoring TLC, adding 30 ml of absolute methanol after the reaction is finished, pouring the absolute methanol into ice water to generate a large amount of white solid, filtering the solid, washing a crude product with diethyl ether, and recrystallizing the crude product with ethanol-water to obtain a compound 3; the amount of compound 3 prepared and the volume of the reaction vessel are scaled up or down accordingly.
B. Preparation of compound 5:
To a 100 ml round bottom flask were added 4.03 mmol of compound 3 and 30 ml of anhydrous acetonitrile, 4.836 mmol of compound 4, 16.12 mmol of anhydrous potassium carbonate and 0.403 mmol of potassium iodide in this order with stirring at room temperature, and then the reaction system was heated to reflux for 5 hours. TLC monitoring, standing and cooling to room temperature after the reaction is finished, decompressing and removing most of the solvent, adding 30 ml of water into the residue, extracting with ethyl acetate three times (15 ml multiplied by 3), washing the organic phase with saturated sodium chloride solution three times (15 ml multiplied by 3), and combining the organic layers and drying with anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying with petroleum ether/ethyl acetate (3:1, v/v) eluent column chromatography to obtain compound 5; the amount of compound 5 prepared and the volume of the reaction vessel are scaled up or down accordingly.
C. Preparation of Compound 6:
Into a 100 ml round bottom flask were added 1g of compound 5 and 30 ml of isopropanol, 30 ml of 1 mol/l sodium hydroxide solution was slowly added dropwise with stirring at room temperature, and the reaction system was heated under reflux for 4 hours after the addition. Monitoring by TLC, standing the system after the reaction is finished, cooling to room temperature, decompressing and removing most of isopropanol, adding 1 mol/L hydrochloric acid solution into the remainder to adjust the pH value of the system to be 1, precipitating a large amount of solids, carrying out suction filtration and drying to obtain a compound 6; the amount of compound 6 prepared and the volume of the reaction vessel are scaled up or down accordingly.
D. Preparation of compound 7:
To a 100 ml round bottom flask were added 1 mmol of compound 6 and 15 ml of N, N-dimethylformamide, followed by stirring, 1.1 mmol of 1H-benzotriazol-1-yloxytripyrrolidinyl hexafluorophosphate, 2.5 mmol of N, N-diisopropylethylamine and 1.1 mmol of 4-aminoanisole, and stirring was carried out at room temperature for 6 hours. After completion of the reaction, 30ml of water was added and extracted three times with ethyl acetate (15 ml. Times.3), the organic phase was separated and 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, v/v) eluent column chromatography to obtain compound 7; the amount of compound 7 prepared and the volume of the reaction vessel are scaled up or down accordingly.
E. Preparation of Compound I-a:
To a 100 ml round bottom flask were added 1 mmole of compound 7 and 30 ml of anhydrous methanol, 2.3 mmole of iodobenzene diacetic acid and 1.5 mmole of ammonium carbonate in sequence with stirring, and stirring was carried out at room temperature for 8 hours. After completion of the reaction, most of methanol was removed under reduced pressure by TLC, 30 ml of water was added to the residue, extraction was performed three times with ethyl acetate (15 ml. Times.3), the organic phase was separated and 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 dichloromethane/methanol (20:1, volume/volume) eluent column chromatography to obtain compound I-a; the amount of compound I-a prepared and the volume of the reaction vessel are scaled up or down accordingly.
F. preparation of Compound I-b:
Into a 100 ml round bottom flask were added 1mmol of compound I-a and 15 ml of anhydrous pyridine, 1mmol of substituted sulfonyl chloride was added with stirring, and stirring was carried out at room temperature for 8 hours. After completion of the reaction, 30 ml of water was added and extracted three times with ethyl acetate (15 ml×3), and the organic phase was separated and washed three times with 1 mol/l hydrochloric acid solution (15 ml×3) and saturated sodium chloride solution in this order (15 ml×3), and the combined organic layers were dried over anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying by column chromatography with dichloromethane/methanol (100:1, volume/volume) eluent to obtain compound I-b; the amount of compound I-b prepared and the volume of the reaction vessel are scaled up or down accordingly.
G. preparation of Compounds I-c:
Into a 100 ml round bottom flask were added 1 mmol of compound I-a and 15 ml of anhydrous pyridine, 1 mmol of substituted acid chloride was added with stirring, and stirring was carried out at room temperature for 8 hours. After completion of the reaction, 30ml of water was added, extracted three times with ethyl acetate (15 ml×3), the organic phase was separated and washed three times with 1 mol/l hydrochloric acid solution (15 ml×3), saturated sodium bicarbonate solution (15 ml×3), saturated sodium chloride solution (15 ml×3) in this order, and the combined organic layers were dried over anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying by column chromatography with dichloromethane/methanol (100:1, volume/volume) eluent to obtain compound I-c; the amount of compound I-c prepared and the volume of the reaction vessel are scaled up or down accordingly.
H. preparation of Compounds I-d:
Into a 100 ml round bottom flask were added 1mmol of compound I-a and 30 ml of N, N-dimethylformamide, 0.1 mmol of cuprous chloride and 1mmol of substituted isocyanate in sequence with stirring, and stirring was carried out at room temperature for 8 hours. After completion of the reaction, 30 ml of water was added and extracted three times with ethyl acetate (15 ml. Times.3), the organic phase was separated and 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 by column chromatography with dichloromethane/methanol (100:1, volume/volume) eluent to obtain compound I-d; the amount of compound I-d prepared and the volume of the reaction vessel are scaled up or down accordingly.
Wherein the substituents R 1、R2 are as defined above; r 1 is selected from: hydrogen, 4-fluoro, 4-chloro; r 2 is selected from: cyclopropanesulfonyl, 4-trifluoromethoxybenzenesulfonyl, 4-nitrobenzenesulfonyl, 4-methylbenzenesulfonyl, 2, 4-dichlorobenzenesulfonyl, 4-methoxybenzenesulfonyl, 4-fluorobenzenesulfonyl, 4-chlorobenzenesulfonyl, benzenesulfonyl, 4-tert-butylbenzenesulfonyl, methanesulfonyl, trifluoromethanesulfonyl, 4-iodobenzenesulfonyl, 4-bromobenzenesulfonyl, 4-ethylbenzenesulfonyl, 3, 4-difluorobenzenesulfonyl, 2-naphthalenesulfonyl, 4-tert-butylbenzoyl, hydrogen, 4-trifluoromethylbenzoyl, 3-bromobenzoyl, 3-trifluoromethoxybenzoyl, 4-methylbenzoyl, 4-fluorobenzoyl, acetyl, 1-naphthoyl, (3, 5-dichlorophenyl) carbamoyl, (4-trifluoromethoxyphenyl) carbamoyl, (4-fluorophenyl) carbamoyl, (3-methylphenyl) carbamoyl, 3-dichlorophenyl), 3, 4-dichloro-5-thiazole, 2-dimethylpentane, 2-fluoro-2-chlorobenzoyl, 2-fluoro-1-dimethylpentane, 2-fluoro-2-benzoyl.
The invention provides application of the sulfinimine psoralen derivative I in preparing fungicides.
The invention provides application of a sulfimide psoralen derivative I in preparation of a tobacco mosaic virus resisting agent.
The invention provides application of a sulfimide psoralen derivative I in preparing a plant activator for inducing tobacco to resist tobacco mosaic virus.
The invention provides application of the sulfimide psoralen derivative I in preventing and controlling insect pests of agricultural and forestry and horticultural plants.
The sulfinimine psoralen derivative I is applied together with agricultural chemicals; the agricultural chemical is selected from: one or more of insecticide, bactericide, plant virus resisting agent and acaricide.
The sulfimide psoralen derivative I and any one or two of the pesticides are combined to form an insecticidal composition which is used for preventing and controlling insect pests of agricultural and forestry and horticultural plants;
The insecticide is selected from: bifenthrin, permethrin, ethofenprox, flumethrin, fluramid, imidacloprid nitenpyram, imidaclothiz, thiacloprid, thiamethoxam, clothianidin, dinotefuran, collidine bifenthrin, permethrin, ethofenprox, flumethrin, fluramid, imidacloprid, nitenpyram, imidaclothiz, thiacloprid, thiamethoxam, clothianidin, dinotefuran, collidine, tolfenpyrad daphne, chlorfluazuron, polyfluorourea, flufenuron, bisfenuron fluazuron, oxazine, bistrifluron, furtebufenozide, tebufenozide, chlorfenozide, methomyl, chromafenozide, dichlorvos, quetiapine, pyridaphethione, leafhopper powder, carbaryl, pirimicarb, carbofuran, isoprocarb, cartap, fenoxacarb, fenoxaprop-p-ethyl, pyridalyl, clomazone, clofentezine, propargite, diafenthiuron, pymetrozine, spirodiclofen, spirotetramat, azocyclotin, buprofezin, monosultap, chlorfenapyr, tetrachlorethamide, flufenamid, cyanogen, butene fipronil, tolfenpyrad, chlorfenapyr, pyrazinone, etoxazole, tebufenpyrad, pyridaben, pyrifos, tebufenozide;
the mass percentage of the sulfimide psoralen derivative I in the insecticidal composition is 1% -90%; preferably, the mass percentage of the sulfimide psoralen derivative I to the pesticide is 1 percent to 99 percent;
The formulation of the insecticidal composition is selected from the group consisting of: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, cereals, blocky baits, granular baits, sheeted baits, concentrated baits, slow release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cans, aerosol sticks, aerosol flakes, aerosol pellets, aerosols, ointments, hot aerosols, cold aerosols, solid/liquid mixed packages, liquid/liquid mixed packages, solid/solid mixed packages, paint, microgranules, tracing powders, oil suspensions, oil dispersible powders, concentrated gels, sprinkles, seed coatings, spreads, film forming oils, ultra low volume liquids, vapor release agents;
The plant insect pest controlled by the insecticidal composition is selected from the group consisting of: spodoptera frugiperda, red spider, migratory locust, fomes officinalis, chinese rice locust, japanese Huang Jihuang, mole cricket, thrips oryzae, thrips tabaci, thrips pratensis, thrips oryzae, thrips katzenii, thrips mairei, white fly, bemisia tabaci, black tail leafhopper, green leaf hopper, cotton leafhopper, cerclage, brown planthopper, white-back planthopper, white planthopper, sugarcane horn planthopper, cotton aphid, wheat binary aphid, wheat long tube aphid, peach aphid sorghum aphid, radish aphid, mealy bugs, sang Dun scale, sagittaria verrucosa, piricosa, meadow wax beetles, korean ball mealy bugs, pear net bugs, banana net bugs, lygus lucorum, small flower bugs, needle-border bugs, rice spider border bugs, brown bugs, rice black bugs, green bugs, alfalfa bugs, medium black bugs, chrysopa, lilaces, chinese chrysopa, moth, clothes moths, yellow thorns, brown moths, flat moths moths, pink bollworms, sweet potato moths, plutella xylostellas, peach fruit borers, soybean fruit borers, apple leaf roller, brown leaf roller, yellow leaf roller, chilo suppressalis, pod borers, and corn borer, rice borer, cabbage borer, rice leaf roller, striped borer, cotton leaf roller She Yeming, peach borer, armyworm, prodenia litura, rice borer fly, cotton budworm, beet armyworm, borer, cotton bollworm, ding point diamond-back, cotton bollworm, cotton boll moth, cotton bollworm, cotton boll moth, tiger, cutworm, yellow cutworm, pirate, gypsy, sweet potato astromoth, bean astromoth, straight line rice butterfly, hidden line valley butterfly, citrus phoenix butterfly, yu bel phoenix butterfly, cabbage butterfly, ramie red vanity butterfly, ramie yellow vanity butterfly, bean genkwa, jin Xingbu nail, cuckoo-bark beetle, ear beetle, ditch needle worm, chest needle worm, valley bark beetle, black bark beetle, citrus gill worm, jin Yuanji budworm, yellow meal worm, black meal worm, red-yellow larch, hybrid-yellow larch, copper green-yellow larch, dark-black tortoise, giant-black gill-white tortoise, mulberry longhorn, star longhorn, orange-brown longhorn, peach-red longhorn, great ape leaf worm, small ape leaf worm, yellow-head melon, yellow-curved striped flea, green bean image, pea image, broad bean image, corn image, rice image, wheat leaf bee, pear-fruit bee, yellow-banded cornflower, armyworm white star-cornflower, boll fly-hanging cornflower, cotton bollworm tooth-lip cornflower, borer black spot wart, mosquito, fly, horsefly, wheat red-sucking maggot, wheat Huang Xi thick beetle, rice gall midge, citrus fruit fly, melon fruit fly, wheat She Hui fly, american leaf fly, bean stalk black fly, wheat fly, seed fly, onion fly, radish fly, umbrella-skirt, corn borer, myalid fly, and insect;
The plants controlled by the insecticidal composition are selected from the group consisting of: rice, wheat, barley, oat, corn, sorghum, sweet potato, tapioca, soybean, netherlands, broad bean, pea, mung bean, cotton, mulberry, peanut, canola, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chilli, radish, cucumber, cabbage, celery, mustard, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild herbs, bamboo shoots, hops, peppers, banana, papaya, orchid, bonsai.
The sulfimide psoralen derivative I and any one or two of the bactericides are combined to form a bactericidal composition for preventing and controlling diseases of agricultural and forestry and horticultural plants;
The bactericide is selected from the group consisting of: benzothiadiazole, tiadinil, thiamide, methidathiamine, 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid, sodium 4-methyl-1, 2, 3-thiadiazole-5-carboxylate, ethyl 4-methyl-1, 2, 3-thiadiazole-5-carboxylate, DL-beta-aminobutyric acid, isothiamine, 3, 4-dichloroisothiazole-5-carboxylic acid, sodium 3, 4-dichloroisothiazole-5-carboxylate, ethyl 3, 4-dichloroisothiazole-5-carboxylate, ribavirin, antofen, ningnanmycin or salicylic acid, cymoxanil, thiram, ziram, zineb, fosetyl, thiophanate-methyl, chlorothalonil, The composition comprises the following components of cortisone, procymidone, fenpropidin, thiophanate methyl, mefenoxam, flumorph, dimethomorph, high-efficiency metalaxyl, high-efficiency benalaxyl, dichlorvos, sulfenamid, thiaflufenamid, folpet, ciprofloxacin, cyflufenamid, fenhexamid, silthiopham, carboxin, mefenoxam, mefenamid, flufenamid, furamemid, thifluzamide, boscalid, pyripyroxad, isopyrazamide, bixafen, fluoxastrobin, fluxapyroxad, penflufen, penflufenpyr, ipratropium, fluxapyroxad, fluxad, flufenamid, Fluofenamide, mandipropamid, zoxamide, etoxazole, iprodione, azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, zoxamide, picoxystrobin, pyraclostrobin, trifloxystrobin, enestrobin, enestroburin, epoxiconazole, furazoles, cyproconazole, difenoconazole, diniconazole, high-efficiency diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriazole, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triticonazole, bitriazole, thiabendazole, metin, imazalil, high-efficiency imazalil, Prochloraz, triflumizole, cyazofamid, imidazolone, oxaimidazole, fenoxanil, famoxadone, pyribenzoxazole, hymexazol, oxadixyl, ethaboxam, hymexazol, xin Sai one, benthiavalicarb-isopropyl, dodine, fenpropimorph, tridemorph, fenpiclonil, fluazinam, pyripyroxime, cyprodinil, fluopicolide, pyrimethanil, cyprodinil, azoxystrobin, azohydrazone, pyrimethanil, pyriminobac-methyl, pyribenzoxim, flubenomyl, fenamidone, dithianon, ethoxyquinoline, hydroxyquinoline, propiquin, benomyl, diethofencarb, iprovalicarb, benthiavalicarb, propamocarb, sulfenphos, iprobenfos, Pirfenphos, tolclofos, blasticidin, kasugamycin, polyoxin, validamycin, streptomycin, metalaxyl, furalaxyl, benalaxyl, furalamide, carbendazim, benomyl, thiophanate-methyl, triadimefon, bupirimate, pyriminol, ethirimol, captan, folpet, ethephon, flucloride, dimethachlon, chlorothalonil, isoprothiolane, pyrifos, metrafenoxine, metconazole, pentachloronitrobenzene, propineb, fosetyl-aluminum, sulfur, bordeaux, copper sulfate, copper oxychloride, copper hydroxide, benomyl, pencycuron, pyridalyl, fludioxonil, Spiroxamine, tricyclazole, zinyl, dodine, guanosine, chloronitenpyram, benomyl, sulfenpyrad, indolyl, sodium disultone, quizalofop, probenazole, bronopol, methyl iodide, carb mu, dixyl, dazomet, diisopropyl ether, fosthiazate, fenitrothion, benfophos, triazophos, carbosulfan, triadimefon, sulfuryl fluoride, dichloropropene, dichloroisonicotinic acid, and allylisothiazole;
the total mass percentage of the sulfimide psoralen derivative I in the bactericidal composition is 1-90%; the mass percentage of the sulfimide psoralen derivative I to the bactericide is 1 percent to 99 percent to 1 percent;
The dosage form of the bactericidal composition is selected from the group consisting of: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, cereals, blocky baits, granular baits, sheeted baits, concentrated baits, slow release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cans, aerosol sticks, aerosol flakes, aerosol pellets, aerosols, ointments, hot aerosols, cold aerosols, solid/liquid mixed packages, liquid/liquid mixed packages, solid/solid mixed packages, paint, microgranules, tracing powders, oil suspensions, oil dispersible powders, concentrated gels, sprinkles, seed coatings, spreads, film forming oils, ultra low volume liquids, vapor release agents;
The plant diseases controlled by the bactericidal composition are selected from the group consisting of: seedling blight, tomato root rot, potato late blight, tobacco black shank, millet powdery mildew, grape downy mildew, lettuce downy mildew, cucumber anthracnose;
Plants for which the fungicidal composition is suitable are selected from: rice, wheat, barley, oat, corn, sorghum, sweet potato, tapioca, soybean, netherlands, broad bean, pea, mung bean, cotton, mulberry, peanut, canola, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chilli, radish, cucumber, cabbage, celery, mustard, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild herbs, bamboo shoots, hops, peppers, banana, papaya, orchid, bonsai.
Any one or two of the sulfimide psoralen derivatives I and the antiviral agents are combined to form an antiviral composition which is used for preventing and treating viral diseases of agricultural and forestry plants and horticultural plants;
The antiviral agent is selected from: benzothiadiazole, tiadinil, isotiadinil, 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid, sodium 4-methyl-1, 2, 3-thiadiazole-5-carboxylate, ethyl 4-methyl-1, 2, 3-thiadiazole-5-carboxylate, 3, 4-dichloroisothiazole-5-carboxylic acid, sodium 3, 4-dichloroisothiazole-5-carboxylate, ethyl 3, 4-dichloroisothiazole-5-carboxylate, DL-beta-aminobutyric acid, 2, 6-dichloroisonicotinic acid, N-cyanomethyl-2-chloroisonicotinamide, allylisothiazole, ribavirin, antofine, ningnanmycin, thiamide, methiadipamide or salicylic acid, pyrimidone, dichloroisonicotinic acid, allylisothiazole, validoxylamine, validamycin, moroxydine hydrochloride;
The total mass percentage of the sulfinimine psoralen derivative I in the antiviral composition is 1% -90%; preferably, the mass percentage of the sulfimide psoralen derivative I to the plant virus resisting agent is 1 to 99 to 1 percent;
The antiviral composition is formulated in 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, cereals, blocky baits, granular baits, sheeted baits, concentrated baits, slow release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cans, aerosol sticks, aerosol flakes, aerosol pellets, aerosols, ointments, hot aerosols, cold aerosols, solid/liquid mixed packages, liquid/liquid mixed packages, solid/solid mixed packages, paint, microgranules, tracing powders, oil suspensions, oil dispersible powders, concentrated gels, sprinkles, seed coatings, spreads, film forming oils, ultra low volume liquids, vapor release agents;
The virus diseases prevented and treated by the antiviral composition are selected from the following: rice dwarf, yellow dwarf, stripe disease, tomato fern leaf virus, pepper mosaic virus, tobacco vein necrosis virus, maize dwarf mosaic, cauliflower mosaic virus, citrus virus, cymbidium mosaic virus, cymbidium ringspot virus;
the plants for which the antiviral composition is used for control are selected from: rice, wheat, barley, oat, corn, sorghum, sweet potato, tapioca, soybean, netherlands, broad bean, pea, mung bean, cotton, mulberry, peanut, canola, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chilli, radish, cucumber, cabbage, celery, mustard, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild herbs, bamboo shoots, hops, peppers, banana, papaya, orchid, bonsai.
The sulfimide psoralen derivative I and any one or two of the acaricides are combined to form an acaricidal composition which is used for preventing and controlling mites of agricultural and forestry and horticultural plants;
the acaricide is selected from the group consisting of: dichlorvos, heptylphosphines, acephate, dibromophosphorus, pyrimidine phosphorus, chlormethiphos, ethion, chlorfenphos, vos methyl pyrifos, quetiapine, aphid, amifos, chlorimfos, iminofos, flumethrin, bifenthrin cyhalothrin, lambda-cyhalothrin, fenpropathrin, flumetofen, fenhexamid, fenfluramine, bifenthrin, benfuracarb, carbofuran, fenoxacarb, benomyl, clomazone, ding Liusu methomyl, fenbucarb, fenbucin acarb, benzyl benzoate, bromopropylate, cyflumetofen, chloranil, flumetofen, flufenoxuron, liuyangmycin, chongmycin, thuringiensis, acaricide, liuyangmycin, avermectin, doramectin, eprinomectin, ivermectin, siramectin, moxidectin, pyrethrin, nicotine, matrine, azadirachtin, rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spirodiclofen, azoxystrobin, acaricide, clofentezine;
The total mass percentage of the sulfinimine psoralen derivative I in the acaricidal composition is 1% -90%; the mass percentage of the sulfimide psoralen derivative I to the acaricide is 1 percent to 99 percent to 1 percent;
The formulation of the acaricidal composition is selected from the group consisting of: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, cereals, blocky baits, granular baits, sheeted baits, concentrated baits, slow release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cans, aerosol sticks, aerosol flakes, aerosol pellets, aerosols, ointments, hot aerosols, cold aerosols, solid/liquid mixed packages, liquid/liquid mixed packages, solid/solid mixed packages, paint, microgranules, tracing powders, oil suspensions, oil dispersible powders, concentrated gels, sprinkles, seed coatings, spreads, film forming oils, ultra low volume liquids, vapor release agents;
The mite injury prevented and controlled by the mite-killing composition is selected from the following components: the mites are selected from the group consisting of spider mites, tetranychidae, furwire mites, goiter mites, red spider mites, goiter mites, said mites being world-wide agricultural, forestry, horticultural and hygiene mites;
The plants for which the acaricidal composition is used for control are selected from the group consisting of: rice, wheat, barley, oat, corn, sorghum, sweet potato, tapioca, soybean, netherlands, broad bean, pea, mung bean, cotton, mulberry, peanut, canola, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chilli, radish, cucumber, cabbage, celery, mustard, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild herbs, bamboo shoots, hops, peppers, banana, papaya, orchid, bonsai.
The biological activity of the sulfimide psoralen derivative I is determined as follows:
I. the bactericidal activity of the sulfinimine psoralen derivative I is measured:
The sterilization or bacteriostasis activity of the psoralen derivative I containing sulfimide adopts a thallus growth rate measuring method, and the specific steps are as follows: 1.8 mg of sample is dissolved in 2 drops of N, N-dimethylformamide, then the sample is diluted to 500 micrograms/ml of medicament by using an aqueous solution containing a certain amount of Tween 20 emulsifier, 1 ml of medicament to be tested is respectively sucked into a culture dish under the aseptic condition, 9 ml of PDA culture medium is respectively added, the culture dish is uniformly shaken to prepare 50 micrograms/ml of medicament-containing flat plates, 1 ml of sterilized water is added to serve as blank control, a puncher with the diameter of 4mm is used for cutting a fungus disk along the outer edge of hypha, the fungus disk is moved onto the medicament-containing flat plates to be placed in an equilateral triangle shape, each treatment is repeated for 3 times, the culture dish is placed into a constant temperature incubator with the temperature of 24+/-1 ℃ for culture, the expansion diameter of each treatment fungus disk is investigated after the diameter of a control colony is expanded to be 2-3 cm, the average value is calculated, and compared with the blank control, and the sample strain is the species of most typical plant pathogenic bacteria actually generated in the agricultural production in China, and the code and name are as follows: AS: the Latin name of the early blight bacteria of tomato is: ALTERNARIA SOLANI, BC: the Latin name of the Botrytis cinerea is: botrytis cinerea, CA: peanut brown spot germ, its latin name is: cercospora arachidicola, GZ: the gibberella wheat germ has the Latin name: gibberella zeae, PP: apple ring rot germ, its latin name is: physalospora piricola, PS: rhizoctonia solani, its Latin name is: pellicularia sasakii, SS: sclerotinia sclerotiorum, the Latin name of which is: sclerotinia sclerotiorum.
The beneficial effects of the invention are as follows: the sulfinimine psoralen derivative I is optimized in advance, and the sulfinimine psoralen derivative is screened for antibacterial activity.
The synthesis and biological activity and application of the sulfinimide psoralen derivatives I are more specifically described by specific preparation and biological activity measurement examples, which are only used for specifically describing the invention and are not limiting the invention, and particularly, the biological activity is only used for illustrating but not limiting the patent, and the specific embodiments are as follows:
Example 1: preparation of compound 3:
into a 100ml round bottom flask were added 18.2 mmol resorcinol and 18.2 mmol dimethyl acetylsuccinate followed by slowly dropwise adding 2.73 ml 98% concentrated sulfuric acid with stirring, after which the reaction was stirred at room temperature overnight. Monitoring TLC, adding 30 ml of absolute methanol after the reaction is finished, pouring the absolute methanol into ice water to generate a large amount of white solid, filtering the solid, washing a crude product with diethyl ether, and recrystallizing the crude product with ethanol-water to obtain a compound 3; yield 81%; the nuclear magnetic data were obtained by scaling up or down the volume of the reaction vessel and the amount of compound 3 prepared as follows ：1H NMR(400MHz,DMSO)δ10.50(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)..
Example 2: preparation of compound 5:
To a 100ml round bottom flask were added 1 mmol of compound 3 and 30 ml of anhydrous acetonitrile, and 1.2 mmol of compound 4, 4 mmol of anhydrous potassium carbonate and 0.1 mmol of potassium iodide were sequentially added with stirring at room temperature, followed by heating and refluxing the reaction system for 5 hours. TLC monitoring, standing and cooling to room temperature after the reaction is finished, decompressing and removing most of acetonitrile, adding 30 ml of water into the residue, extracting with ethyl acetate three times (15 ml multiplied by 3), washing an organic phase three times (15 ml multiplied by 3) with saturated sodium chloride solution, and combining organic layers and drying with anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying with petroleum ether/ethyl acetate (3:1, v/v) eluent column chromatography to obtain compound 5; the yield thereof was found to be 65%; the nuclear magnetic data were obtained by scaling up or down the volume of the reaction vessel and the amount of compound 5 prepared as follows ：1H NMR(400MHz,DMSO)δ8.12(s,2H),7.74(d,J＝8.8Hz,1H),7.42(t,J＝8.5Hz,2H),7.10(s,1H),7.04(d,J＝8.7Hz,1H),5.73(s,2H),3.67(s,2H),3.62(s,3H),2.38(s,3H)..
Example 3: preparation of Compound 6:
Into a 100 ml round bottom flask, 2g of compound 5 and 30ml of isopropyl alcohol were charged, 60 ml of 1 mol/l sodium hydroxide solution was slowly added dropwise with stirring at room temperature, and the reaction system was heated under reflux for 4 hours after the addition. Monitoring by TLC, standing the system after the reaction is finished, cooling to room temperature, decompressing and removing most of isopropanol, adding 1 mol/L hydrochloric acid solution into the remainder to adjust the pH value of the system to be 1, precipitating a large amount of solids, carrying out suction filtration and drying to obtain a compound 6; yield 61%; the nuclear magnetic data were obtained by scaling up or down the volume of the reaction vessel and the amount of compound 6 prepared as follows ：1H NMR(400MHz,DMSO)δ12.29(s,1H),8.30(s,1H),7.98(s,1H),7.70(s,1H),7.61(s,1H),7.22(s,2H),3.49(s,2H),2.36(s,3H)..
Example 4: preparation of compound 7:
A100 ml round bottom flask was charged with 0.3 g of Compound 6 and 15ml of N, N-dimethylformamide, followed by 0.49 g of 1H-benzotriazol-1-yloxytripyrrolidinyl hexafluorophosphate, 0.275 g of N, N-diisopropylethylamine and 0.13 g of 4-aminoanisole with stirring, and stirring was carried out at room temperature for 6 hours. After completion of the reaction, 30 ml of water was added and extracted three times with ethyl acetate (15 ml. Times.3), the organic phase was separated and 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, v/v) eluent column chromatography to obtain compound 7; the yield thereof was found to be 82%; the nuclear magnetic data were obtained by scaling up or down the volume of the reaction vessel and the amount of compound 7 prepared as follows ：1H NMR(400MHz,DMSO)δ10.24(s,1H),8.41(s,1H),8.09(s,1H),7.84(s,2H),7.70(s,1H),7.61(d,J＝7.6Hz,2H),7.37(t,J＝7.9Hz,2H),7.24(d,J＝7.5Hz,2H),3.82(s,2H),2.55(s,3H),2.45(s,3H)..
Example 5: preparation of Compound I-a:
Into a 100 ml round bottom flask was added 0.15 g of Compound 7 and 10 ml of absolute methanol, followed by 0.235 g of iodobenzene diacetic acid and 0.046 g of ammonium carbonate with stirring, and stirring was carried out at room temperature for 8 hours. After completion of the reaction, most of methanol was removed under reduced pressure by TLC, 30 ml of water was added to the residue, extraction was performed three times with ethyl acetate (15 ml. Times.3), the organic phase was separated and 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 dichloromethane/methanol (20:1, volume/volume) eluent column chromatography to obtain compound I-a; yield 74-83%; when R 1 is 4-fluorophenyl and R 2 is hydrogen, the nuclear magnetic data of compound I-a-1 are as follows: the nuclear magnetic data is that the amount of the compound I-a-1 prepared as follows ：1H NMR(400MHz,DMSO)δ10.56(s,1H),8.46(s,1H),8.18(s,1H),7.89-7.84(m,4H),7.79(d,J＝8.2Hz,3H),7.37(t,J＝8.7Hz,2H),4.07(s,1H),3.85(s,2H),3.02(s,3H),2.58(s,3H). and the volume of the reaction vessel are enlarged or reduced according to the corresponding proportion; the physicochemical and structural parameters of compound I-a are shown in Table 1.
Example 6: preparation of Compound I-b:
Into a 100 ml round bottom flask were added 0.1 g of Compound I-a-1 and 5ml of anhydrous pyridine, and 0.04 g of p-toluenesulfonyl chloride was added with stirring, and stirred at room temperature for 8 hours. After completion of the reaction, 30 ml of water was added and extracted three times with ethyl acetate (15 ml×3), and the organic phase was separated and washed three times with 1 mol/l hydrochloric acid solution (15 ml×3) and saturated sodium chloride solution in this order (15 ml×3), and the combined organic layers were dried over anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying by column chromatography with dichloromethane/methanol (100:1, volume/volume) eluent to obtain compound I-b; the yield is 64-94%; when R 1 is 4-fluorophenyl and R 2 is 4-methylbenzenesulfonyl, the nuclear magnetic data of the compound I-b-1 are expanded or contracted according to the corresponding proportion by the following ：1H NMR(400MHz,DMSO)δ10.73(s,1H),8.48(s,1H),8.21(s,1H),7.91-7.81(m,7H),7.61(d,J＝8.1Hz,2H),7.39(t,J＝8.8Hz,2H),7.29(d,J＝8.1Hz,2H),3.88(s,2H),3.55(s,3H),2.60(s,3H),2.35(s,3H). preparation amount of the compound I-b-1 and the volume of the reaction vessel; the physicochemical and structural parameters of compound I-b are shown in Table 1.
Example 7: preparation of Compounds I-c:
Into a 100 ml round bottom flask was added 0.05 g of Compound I-a-1 and 15 ml of anhydrous pyridine, 0.01 g of acetyl chloride was added with stirring, and stirring was performed at room temperature for 8 hours. After completion of the reaction, 30 ml of water was added, extracted three times with ethyl acetate (15 ml×3), the organic phase was separated and washed three times with 1 mol/l hydrochloric acid solution (15 ml×3), saturated sodium bicarbonate solution (15 ml×3), saturated sodium chloride solution (15 ml×3) in this order, and the combined organic layers were dried over anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying by column chromatography with dichloromethane/methanol (100:1, volume/volume) eluent to obtain compound I-c; the yield is 67-94%; when R 1 is 4-fluorophenyl and R 2 is acetyl, the nuclear magnetic data of the compound I-c-1 is that the prepared amount of the compound I-c-1 and the volume of the reaction vessel are enlarged or reduced according to corresponding proportions as follows ：1H NMR(400MHz,DMSO)δ10.66(s,1H),8.47(s,1H),8.20(s,1H),7.90-7.81(m,7H),7.38(t,J＝8.7Hz,2H),3.87(s,2H),3.39(s,3H),2.59(s,3H),1.97(s,3H).; the physicochemical and structural parameters of compounds I-c are shown in Table 1.
Example 8: preparation of Compounds I-d:
Into a 100 ml round bottom flask were added 0.1 g of compound I-a-1 and 20ml of N, N-dimethylformamide, followed by 0.004 cuprous chloride and 0.027 g of p-fluorophenyl isocyanate with stirring, and stirring at room temperature for 8 hours. After completion of the reaction, 30 ml of water was added and extracted three times with ethyl acetate (15 ml. Times.3), the organic phase was separated and 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 by column chromatography with dichloromethane/methanol (100:1, volume/volume) eluent to obtain compound I-d; yield 72-91%; when R 1 is 4-fluorophenyl and R 2 is (4-fluorophenyl) carbamoyl, the nuclear magnetic data of the compound I-d-1 is as follows ：1H NMR(400MHz,DMSO)δ10.66(s,1H),9.39(s,1H),8.47(s,1H),8.20(s,1H),8.06(d,J＝8.1Hz,1H),7.93(d,J＝8.3Hz,2H),7.87(s,3H),7.82(s,1H),7.51(d,J＝4.8Hz,2H),7.38(t,J＝8.3Hz,2H),7.03(t,J＝8.5Hz,2H),3.87(s,2H),3.45(s,3H),2.59(s,3H). the amount of the compound I-d-1 prepared and the volume of the reaction vessel are enlarged or reduced in corresponding proportion; the physicochemical and structural parameters of compounds I-d are shown in Table 1.
Example 9: the bacteriostasis activity measurement result of the sulfinimine psoralen derivative I:
The codes and names of the common plant pathogenic fungi tested by the invention are as follows: a.s: the Latin name of the early blight bacteria of tomato is: ALTERNARIA SOLANI, b.c: the Latin name of the Botrytis cinerea is: botrytis cinerea, C.a: peanut brown spot germ, its latin name is: cercospora arachidicola, G.z: the gibberella wheat germ has the Latin name: gibberella zeae, P.p: apple ring rot germ, its latin name is: physalospora piricola, P.s: rhizoctonia solani, its Latin name is: pellicularia sasakii, S.s: sclerotinia sclerotiorum, the Latin name of which is: sclerotinia sclerotiorumalis these species are well representative and can represent the species of most pathogenic bacteria occurring in the field in agricultural production.
The results of the cell growth rate assay are shown in Table 2, and Table 2 shows that all the compounds synthesized in the present invention have different degrees of bactericidal activity at 50. Mu.g/ml. For tomato early blight bacteria, the inhibition rate of the compound DJY-1-189、DJY-2-1、DJY-2-11、DJY-1-198、DJY-2-30、DJY-2-50、DJY-1-168、DJY-2-74、DJY-2-24、DJY-1-191、DJY-1-179、DJY-2-189、DJY-2-187、DJY-2-201、DJY-1-196、DJY-2-60-2、DJY-3-2、DJY-2-77 of the invention is above 50%, which is equal to or higher than that of the control drugs psoralen and YZK-C22, wherein the inhibition rate of the compounds DJY-2-1, DJY-2-11, DJY-1-191 and DJY-2-189 is above 65%, which is higher than that of the control drugs psoralen and YZK-C22 by nearly 10%; for gray mold bacteria of cucumber, the inhibition rate of the compounds DJY-2-44, DJY-2-74, DJY-1-191, DJY-2-61, DJY-2-186, DJY-2-187, DJY-1-196 and DJY-3-2 is above 60 percent, which is above 10 percent higher than that of the reference drug psoralen, wherein the inhibition rate of the compounds DJY-2-186 and DJY-3-2 is above 90 percent, which is above 2220 percent higher than that of the reference drug YZK-C, especially the sterilization activity of the compounds DJY-2-186 is highest, which is up to 93 percent; for brown spot germ of peanut, the inhibition rate of the compounds DJY-2-1, DJY-2-13, DJY-2-66 and DJY-2-24 is above 65%, which is equal to or higher than that of the control drugs psoralen and YZK-C22, wherein the sterilization activity of the compound DJY-2-13 is highest and is up to 88%, which is higher than that of the control drugs psoralen by above 20%; for apple ring rot fungi, the inhibition rate of the compounds DJY-1-192, DJY-2-29 and DJY-2-186 is above 60 percent, which is higher than that of the reference medicine psoralen by nearly 20 percent, wherein the sterilization activity of the compound DJY-2-186 is the highest and reaches 72 percent; for Rhizoctonia solani, the inhibition rate of the compounds DJY-2-66, DJY-2-67 and DJY-2-24 is above 70%, which is approximately 20% higher than that of the reference medicine psoralen; for Sclerotinia sclerotiorum, the inhibition rate of the compounds DJY-2-66, DJY-2-24, DJY-1-191, DJY-2-189, DJY-2-186, DJY-2-187, DJY-2-201 and DJY-3-2 is more than 50 percent, which is equal to or higher than that of the contrast drugs psoralen and YZK-C22, wherein the inhibition rate of the compounds DJY-2-24 and DJY-1-191 is more than 90 percent, which is higher than that of the contrast drugs psoralen and YZK-C22 by more than 30 percent, especially the sterilization activity of the compounds DJY-1-191 is up to 96 percent.
Example 10: the application of the sulfinimine psoralen derivative I in preparing pesticide compositions comprises the following steps:
The sulfilimine psoralen derivative I of the invention prepares a pesticide composition, and the composition contains the sulfilimine psoralen derivative I of the invention and an intermediate thereof as active ingredients, wherein 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 auxiliary agent, and optionally 0 to 50 percent by weight of surfactant.
Example 11: the application of the sulfimide psoralen derivative I in preparing a pesticide compound composition comprises the following steps:
The sulfimide psoralen derivative I and the intermediate thereof can be compounded with other commodity pesticides, namely, insecticides, acaricides, bactericides, antiviral agents or plant activators to prepare pesticide compound compositions, the compound compositions comprise the sulfimide psoralen derivative I and the intermediate thereof and other commodity pesticides, namely, insecticides, acaricides, bactericides, antiviral agents or plant activators as active ingredients, and the weight percentage of the sulfimide psoralen derivative I and the intermediate thereof and other commodity pesticides, namely, the insecticides, acaricides, bactericides, antiviral agents or plant activators is 1 percent to 99 percent to 1 percent, the content of the active ingredients is 0.1 to 99.9 percent, 99.9 to 0.1 percent of solid or liquid auxiliary agents, and optionally 0 to 50 percent of surfactants.
Example 12: the application of the sulfimide psoralen derivative I and the pesticide combination in preventing and controlling agricultural and forestry plant insect pests:
The sulfimide psoralen derivative I is combined with any one or two of commercial pesticides to form an insecticidal composition which is used for preventing and controlling insect pests of agricultural, forestry and horticultural plants, wherein the commercial pesticides are selected from the group consisting of: tefluthrin, bifenthrin high-efficiency cypermethrin tefluthrin, bifenthrin, beta-cypermethrin beta-cypermethrin, cyhalothrin, beta-cypermethrin deltamethrin, fenpropathrin, beta-cyhalothrin, lambda-cyhalothrin, permethrin, allethrin, bifenthrin, permethrin, ethofenprox, flumethrin, Diflubenzuron, hexaflumuron, flufenoxuron chlorazuron, lufenuron, chlorfluazuron chlorazuron, hexaflumuron, chlorfluazuron, lufenuron, chlorfluazuron flufenoxuron, polyfluoflufenoxuron, flucycloxuron, diphenflufenoxuron, fluazinuron, chlorfluazuron, fluazuron, bistriflumuron, carbofenozide, tebufenozide, chlorfenozide, methoxyfenozide, chromafenozide, dichlorvos, quetiaphos, pyridaphethione, leafhopper powder, carbaryl, triazamate, isoprocarb, cartap, fenobucarb, she Feisan, carbaryl, cartap, fenitrothion, fenpyroximate, hexythiazox, pyridaben, chlorpyrifos, pyridaben, Clofentezine, propargite, diafenthiuron, pymetrozine, spirodiclofen, spirotetramat, azocyclotin, buprofezin, monosultap, dimehypo, chlorantraniliprole, tetrachlorethamide, flubendiamide, cyantraniliprole, butene fipronil, tolfenpyrad, chlorfenapyr, pyrazinone, etoxazole, tebufenpyrad, pyridaben, pyriproxyfen, emamectin, tebufenozide; the mass percentage of the sulfimide psoralen derivative I in the insecticidal composition is 1% -90%, and the mass percentage of the sulfimide psoralen derivative I to the commercial insecticide is 1% -99% -1%; the formulation of the insecticidal composition is selected from the group consisting of: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, cereals, blocky baits, granular baits, sheetlike baits, concentrated baits, slow-release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cans, aerosol sticks, aerosol flakes, aerosol pellets, aerosols, ointments, hot aerosols, cold aerosols, solid/liquid mixed packages, liquid/liquid mixed packages, solid/solid mixed packages, paints, microgranules, tracing powders, oil suspensions, oil dispersible powders, concentrates, sprinkles, seed coatings, spreads, film-forming oils, formulations for the treatment of various diseases, and methods of making the same, Ultra low volume liquid and vapor release agents; the plant insect pest controlled by the insecticidal composition is selected from the group consisting of: spodoptera frugiperda, red spider, migratory locust, fomes yunnanensis, chinese rice locust, japanese Huang Jihuang, mole cricket, rice thrips, thrips tabaci, thrips green house, thrips oryzae, jian Guan thrips, white fly, bemisia tabaci, black tail leafhopper, dyer woad, cotton leafhopper, leaf spot wax cicada, brown planthopper, white back planthopper, white planthopper, sugar cane planthopper, cotton aphid, wheat aphid, long tube aphid, peach aphid, sorghum aphid, radish aphid, meadow, sang Dun scale, sagittaria, meadow beetle, pear round scale, white wax beetle, red wax scale, meadow beetle, banana net bug, fine horn bugs, small flower bugs, Stinking bug, spider bug, brown bug, black bug, green bug, alfalfa bug, middle black bug, bollworm, listblower, chinese sand fly, moth, brown moth, flat moth, pink bollworm, sweet potato moth, plutella xylostella, peach fruit borer, soybean borer, peach fruit borer the apple leaf roller, brown leaf roller, yellow leaf roller, chilo suppressalis, pod borer, corn borer, tryporyza incertulas, cabbage borer, cnaphalocrocis medinalis, rice leaf roller, striped borer cotton roll She Yeming, carpopodium borer, armyworm, prodenia litura, rice bollworm, cotton bridgeworm beet armyworm, borer, cotton bollworm, dingdian diamond, cutworm, cotton bollworm, cotton boll cotton bollworm, cotton, Tiger, yellow tiger, pirate moth, gypsymoth, sweet potato astromoth, bean astromoth, straight line rice butterfly, black stripe butterfly, citrus butterfly, belated butterfly, cabbage butterfly, red vanthopa, ramie yellow vanthopa, bean lilac, jin Xingbu a, cuckoo beetle, ear beetle, cabbage caterpillar, yellow needle worm, yellow meal beetle, black beetle, citrus budworm, jin Yuanji butea, yellow meal worm, black meal worm, red corkton, hybrid corkton, copper green tortoise, dark tortoise, north China holly beetle, mulberry longicorn, star beetle, orange brown longicorn, peach neck longicorn, great ape beetle, small ape leaf worm, yellow melon, yellow leaf beetle, green bean weeping, red beetle, Broad bean, corn, rice, wheat leaf bees, pear bees, yellow belt cornfish, mythistle bees, bollworm hanging coco cornutus, cotton bollworm tooth cornutus, black spot wart cornutus, mosquitoes, flies, tabanus, wheat red aspen, wheat Huang Xi aspen, gall midge, citrus fruit flies, melon flies, wheat She Hui liriomyza sativae, wheat straw flies, seed flies, shallot flies, radish flies, umbrella-like maize borer, and myza sativae; the plants controlled by the insecticidal composition are selected from the group consisting of: rice, wheat, barley, oat, corn, sorghum, sweet potato, tapioca, soybean, netherlands, broad bean, pea, mung bean, cotton, mulberry, peanut, canola, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chilli, radish, cucumber, cabbage, celery, mustard, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild herbs, bamboo shoots, hops, peppers, banana, papaya, orchid, bonsai.
Example 13: the application of the sulfimide psoralen derivative I and the bactericide combination in preventing and controlling agricultural and forestry and gardening plant diseases:
The sulfimide psoralen derivative I is combined with any one or two of commercial bactericides to form a bactericidal composition for preventing and controlling diseases of agricultural, forestry and horticultural plants, wherein the commercial bactericides are selected from the group consisting of: benzothiadiazole, tiadinil, thiamide, methiadinamide, 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid, sodium 4-methyl-1, 2, 3-thiadiazole-5-carboxylate, ethyl 4-methyl-1, 2, 3-thiadiazole-5-carboxylate, DL-beta-aminobutyric acid, isothiamine, 3, 4-dichloroisothiazole-5-carboxylic acid, sodium 3, 4-dichloroisothiazole-5-carboxylate, 3, 4-dichloroisothiazole-5-carboxylic acid ethyl ester, ribavirin, antofine, ningnanmycin or salicylic acid, cymoxanil, thiram, ziram, mancozeb, fosetyl-aluminum, thiophanate-methyl, chlorothalonil, prednisone, procymidone, fenpropidin, thiophanate-methyl, metalaxyl-M, flumorph, dimethomorph, high-efficiency metalaxyl high-efficiency benalaxyl, dicyclopentadienyl cyhalofop-butyl, sulfenamid, thiabendazole leaf-drying phthalide, cyclopropylamide, cyflufenamid, cymoxanil, fenhexamid silthiopham, carboxin oxide, mefenamid, flufenamid, furamemid, thifluzamide, boscalid, Penoxsulam, isopyrazam, bixafen, fluopicolide, epoxiconamide, fluxapyroxad, penflufen, iprovalicarb, fluxapyroxad, pencycuron, zoxamide, ethaboxirizine, iprodione, azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, zoxamide, picoxystrobin, pyraclostrobin, trifloxystrobin, enoxystrobin, enoximide, epoxiconamine, furfurazoles, cyproconazole, difenoconazole, diniconazole, high-efficiency diniconazole, epoxiconazole, fluquinconazole, flusilazole, flutriazole, hexaconazole, imibenconazole, ipconazole, penconazole, trifloxystrobin, Metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, mequindox, imazalil, high-efficiency imazalil, prochloraz, triflumizole, cyazofamid, imidazolone, imidazole, fenoxanil, famoxadone, hymexazol, oxadixyl, xin Sai one, benthiavalicarb-isopropyl, dodine, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyripyroxim, cyprodinil, fluazinam, boscalid, cyprodinil, pyriminostrobin, pyriminox, pyriminol, chlorpyriminol, Fluopyrimol, fenamic, dithianon, ethoxyquinoline, hydroxyquinoline, propioquinoline, phenoxyquinoline, diethofencarb, iprovalicarb, benthiavalicarb Sulfofacil, fenofos, iprobenfos, piroxicam, tolclofos-methyl, blasticidin, kasugamycin, polyoxin, validamycin, validomycin, streptomycin, metalaxyl, furalaxyl, benalaxyl, furalamide, carbendazim, benomyl, thiophanate-methyl, triazolone, bupirimate, pyrimethanil ethirimol, captan, folpet, captan, ethephon, flucycloril, chlorfluazuron sclerostin, chlorothalonil, isoprothiolane, metconazole, and, Pentachloronitrobenzene, propineb, fosetyl-aluminum, sulfur, bordeaux mixture, copper sulfate, copper oxychloride, cuprous oxide, copper hydroxide, metrafenone, pencycuron, pyridalyl, tetrachlorophthalide, fluquindox, spiroxamine, tricyclazole, zindoline, docusal, guanamine, chloronitenpyram, bensulfenamide, tosulfamide, indolyl ester, sodium disultone, quinocetone, probenazole, bronitol, methyl iodide, wilmu, diwire ester, dazomet, diisopropyl ether, fosthiazate, fenphos, tebufos, triazophos, carbosulfan, sulfuryl fluoride, dichloropropene, dichloroisonicotinic acid, allylisothiazole; the total mass percentage of the sulfimide psoralen derivative I in the sterilization composition is 1% -90%, and the mass percentage of the sulfimide psoralen derivative I and the commercial sterilization agent is 1% -99% -1%; the dosage form of the bactericidal composition is selected from the group consisting of: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, cereals, blocky baits, granular baits, sheetlike baits, concentrated baits, slow-release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cans, aerosol sticks, aerosol flakes, aerosol pellets, aerosols, ointments, hot aerosols, cold aerosols, solid/liquid mixed packages, liquid/liquid mixed packages, solid/solid mixed packages, paints, microgranules, tracing powders, oil suspensions, oil dispersible powders, concentrates, sprinkles, seed coatings, spreads, film-forming oils, formulations for the treatment of various diseases, and methods of making the same, Ultra low volume liquid and vapor release agents; the plant diseases controlled by the bactericidal composition are selected from the group consisting of: seedling blight, tomato root rot, potato late blight, tobacco black shank, millet powdery mildew, grape downy mildew, lettuce downy mildew, cucumber anthracnose; plants for which the fungicidal composition is suitable are selected from: rice, wheat, barley, oat, corn, sorghum, sweet potato, tapioca, soybean, netherlands, broad bean, pea, mung bean, cotton, mulberry, peanut, canola, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chilli, radish, cucumber, cabbage, celery, mustard, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild herbs, bamboo shoots, hops, peppers, banana, papaya, orchid, bonsai.
Example 14: the application of the sulfimide psoralen derivative I and the anti-plant virus agent in preventing and controlling the virus diseases of agriculture and forestry and gardening plants:
The sulfimide psoralen derivative I is combined with any one or two of commercial antiviral agents to form an antiviral composition for preventing and treating viral diseases of agriculture, forestry and horticultural plants, wherein the commercial antiviral agents are selected from the group consisting of: benzothiadiazole, tiadinil, isotiadinil, 4-methyl-1, 2, 3-thiadiazole-5-carboxylic acid, sodium 4-methyl-1, 2, 3-thiadiazole-5-carboxylate, ethyl 4-methyl-1, 2, 3-thiadiazole-5-carboxylate, 3, 4-dichloroisothiazole-5-carboxylic acid, sodium 3, 4-dichloroisothiazole-5-carboxylate, ethyl 3, 4-dichloroisothiazole-5-carboxylate, DL-beta-aminobutyric acid, ribavirin, antofine, ningnanmycin, thiamide, mefenamide or salicylic acid, pyrimidomycin, dichloroisonicotinic acid, allylisothiazole, validoxylamine, validamycin, moroxydine hydrochloride; the total mass percentage of the sulfimide psoralen derivative I in the antiviral composition is 1% -90%, and the mass percentage of the sulfimide psoralen derivative I to the commercial plant virus resisting agent is 1% -99% -1%; the antiviral composition is formulated in 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, cereals, blocky baits, granular baits, sheeted baits, concentrated baits, slow release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cans, aerosol sticks, aerosol flakes, aerosol pellets, aerosols, ointments, hot aerosols, cold aerosols, solid/liquid mixed packages, liquid/liquid mixed packages, solid/solid mixed packages, paint, microgranules, tracing powders, oil suspensions, oil dispersible powders, concentrated gels, sprinkles, seed coatings, spreads, film forming oils, ultra low volume liquids, vapor release agents; the virus diseases prevented and treated by the antiviral composition are selected from the following: rice dwarf, yellow dwarf, stripe disease, tomato fern leaf virus, pepper mosaic virus, tobacco vein necrosis virus, maize dwarf mosaic, cauliflower mosaic virus, citrus virus, cymbidium mosaic virus, cymbidium ringspot virus; the plants for which the antiviral composition is used for control are selected from: rice, wheat, barley, oat, corn, sorghum, sweet potato, tapioca, soybean, netherlands, broad bean, pea, mung bean, cotton, mulberry, peanut, canola, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chilli, radish, cucumber, cabbage, celery, mustard, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild herbs, bamboo shoots, hops, peppers, banana, papaya, orchid, bonsai.
Example 15: the application of the sulfimide psoralen derivative I and the acaricide in controlling the mites of agricultural and forestry and gardening plants is that:
The sulfimide psoralen derivative I and any one or two of commercial acaricides are combined to form an acaricide composition which is used for preventing and controlling agricultural, forestry and horticultural plant mites, and the commercial acaricide is selected from the group consisting of: dichlorvos, heptylphosphines, acephate, dibromophosphorus, pyrimidine phosphorus, chlormethiphos, ethion, chlorfenphos, vos methyl pyrifos, quetiapine, aphid, amifos, chlorimfos, iminofos, flumethrin, bifenthrin cyhalothrin, lambda-cyhalothrin, fenpropathrin, flumetofen, fenhexamid, fenfluramine, bifenthrin, benfuracarb, carbofuran, fenoxacarb, benomyl, clomazone, ding Liusu methomyl, fenbucarb, fenbucin acarb, benzyl benzoate, bromopropylate, cyflumetofen, chloranil, flumetofen, flufenoxuron, liuyangmycin, chongmycin, thuringiensis, acaricide, liuyangmycin, avermectin, doramectin, eprinomectin, ivermectin, siramectin, moxidectin, pyrethrin, nicotine, matrine, azadirachtin, rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spirodiclofen, azoxystrobin, acaricide, clofentezine; the total mass percentage of the sulfimide psoralen derivative I in the acaricidal composition is 1% -90%, and the mass percentage of the sulfimide psoralen derivative I to the commercial acaricide is 1% -99% -1%; the formulation of the acaricidal composition is selected from the group consisting of: seed treatment emulsions, aqueous emulsions, microemulsions, suspoemulsions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, cereals, blocky baits, granular baits, sheeted baits, concentrated baits, slow release blocks, electrostatic sprays, oil-in-water emulsions, aerosol cans, aerosol candles, aerosol cans, aerosol sticks, aerosol flakes, aerosol pellets, aerosols, ointments, hot aerosols, cold aerosols, solid/liquid mixed packages, liquid/liquid mixed packages, solid/solid mixed packages, paint, microgranules, tracing powders, oil suspensions, oil dispersible powders, concentrated gels, sprinkles, seed coatings, spreads, film forming oils, ultra low volume liquids, vapor release agents; the mite injury prevented and controlled by the mite-killing composition is selected from the following components: the mites are selected from the group consisting of Tetranychidae, phyllophaceae, fusarium, goiter, tetranychus, and goiter, and are world agricultural, forestry, horticultural, and hygiene mites; the plants for which the acaricidal composition is used for control are selected from the group consisting of: rice, wheat, barley, oat, corn, sorghum, sweet potato, tapioca, soybean, netherlands, broad bean, pea, mung bean, cotton, mulberry, peanut, canola, sesame, sunflower, sugar beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal, tobacco, tomato, chilli, radish, cucumber, cabbage, celery, mustard, beet, rape, onion, garlic, watermelon, melon, cantaloupe, papaya, apple, citrus and peach, tea, wild herbs, bamboo shoots, hops, peppers, banana, papaya, orchid, bonsai.
Industrial applicability
The invention provides sulfimide psoralen derivatives; the derivative can regulate and control the biological activity of plant pests and plant pathogens in agriculture, gardening and sanitation and forestry, can be used for killing insects, mites, bacteria and plant viruses in the agricultural field, the gardening field and the forestry field, induces plants to generate disease resistance, and has good economic value and application prospect.
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TABLE 2 bacteriostatic Activity of the sulfilimine-type psoralen derivatives I (inhibition rate of 50. Mu.g/ml/%)
Sequence number Compounds of formula (I) A.s B.c C.a G.z P.p P.s S.s
1 DJY-1-200 39 33 29 18 20 15 8
2 DJY-1-199 49 29 37 14 33 26 17
3 DJY-1-189 55 24 38 14 20 19 11
4 DJY-1-183 40 33 46 13 17 15 24
5 DJY-2-1 70 40 66 19 50 25 33
6 DJY-2-5 46 24 37 9 15 24 14
7 DJY-2-11 67 48 48 15 39 14 25
8 DJY-2-13 49 30 88 19 14 25 13
9 DJY-2-10 36 36 31 18 32 11 10
10 DJY-1-192 38 29 53 11 64 12 42
11 DJY-1-188 23 31 27 35 27 18 26
12 DJY-1-198 63 42 37 11 17 18 13
13 DJY-2-20 39 34 41 14 33 35 19
14 DJY-2-23 43 30 40 11 29 16 18
15 DJY-2-29 28 51 54 16 63 22 25
16 DJY-2-30 63 26 38 20 38 19 9
17 DJY-2-44 42 68 40 16 17 11 13
18 DJY-2-50 53 39 38 11 14 24 16
19 DJY-2-47 43 28 28 42 20 9 8
20 DJY-2-66 41 46 67 40 44 73 62
21 DJY-2-42 37 41 36 13 26 23 19
22 DJY-1-170 47 38 43 17 29 21 22
23 DJY-1-168 65 43 50 20 33 27 14
24 DJY-2-67 27 44 61 32 42 70 38
25 DJY-2-74 57 63 27 29 28 38 25
26 DJY-2-72 46 39 32 22 29 44 21
27 DJY-2-24 61 34 65 32 34 73 92
28 DJY-1-191 67 78 32 13 9 22 96
29 DJY-1-179 51 57 32 24 14 19 26
30 DJY-2-61 38 72 59 18 40 56 35
31 DJY-2-189 70 32 53 24 34 37 54
32 DJY-2-186 23 93 64 37 72 39 55
33 DJY-2-187 57 76 55 43 52 21 56
34 DJY-2-201 58 44 52 21 33 53 53
35 DJY-1-196 56 61 41 20 27 26 16
36 DJY-2-60-2 55 20 47 29 25 23 33
37 DJY-3-2 53 92 61 38 23 51 58
38 DJY-2-58 39 38 39 22 21 18 24
39 DJY-2-77 52 58 38 25 20 41 19
40 DJY-2-70 35 20 31 20 23 34 24
41 Psoralen 56 50 65 63 44 52 58
42 YZK-C22 58 72 74 75 57 81 61
A.s: the Latin name of the early blight bacteria of tomato is: ALTERNARIA SOLANI, b.c: the Latin name of the Botrytis cinerea is: botrytis cinerea, C.a: peanut brown spot germ, its latin name is: cercospora arachidicola, G.z: the gibberella wheat germ has the Latin name: gibberella zeae, P.p: apple ring rot germ, its latin name is: physalospora piricola, P.s: rhizoctonia solani, its Latin name is: pellicularia sasakii, S.s: sclerotinia sclerotiorum, the Latin name of which is: sclerotinia sclerotiorumalis.

Claims (5)

1. The sulfimide psoralen derivative is characterized by comprising sulfimide and psoralen structures, and has a structural general formula shown in a formula I:
Wherein R 1 is selected from: hydrogen, 4-fluoro, 4-chloro; r 2 is selected from: 2, 4-dichlorobenzenesulfonyl, 4-fluorobenzenesulfonyl, 4-tert-butylbenzenesulfonyl, 4-ethylbenzenesulfonyl, 4-nitrobenzenesulfonyl, 4-tert-butylbenzoyl, 4-trifluoromethylbenzoyl, 3-bromobenzoyl, 4-methylbenzoyl, 4-fluorobenzoyl, 1-naphthoyl, (4-trifluoromethoxyphenyl) carbamoyl, (4-fluorophenyl) carbamoyl, 3, 4-dichloroisothiazole-5-formyl.
2. The specific synthetic route and method of the sulfinimine derivatives according to claim 1 are as follows:
Wherein R 1 is selected from: hydrogen, 4-fluoro, 4-chloro; r 2 is selected from: 2, 4-dichlorobenzenesulfonyl, 4-fluorobenzenesulfonyl, 4-tert-butylbenzenesulfonyl, 4-ethylbenzenesulfonyl, 4-nitrobenzenesulfonyl, 4-tert-butylbenzoyl, 4-trifluoromethylbenzoyl, 3-bromobenzoyl, 4-methylbenzoyl, 4-fluorobenzoyl, 1-naphthoyl, (4-trifluoromethoxyphenyl) carbamoyl, (4-fluorophenyl) carbamoyl, 3, 4-dichloroisothiazole-5-formyl;
The specific synthesis method comprises the following steps:
A. preparation of compound 3:
adding the compound 1 into a reaction bottle, adding the compound 2, then slowly dropwise adding 98% concentrated sulfuric acid under 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 carrying out suction filtration and drying to obtain a compound 3;
B. Preparation of compound 5:
Taking a compound 3, adding a proper amount of anhydrous acetonitrile into a reaction bottle, then sequentially adding potassium carbonate, potassium iodide and a compound 4 under stirring, and heating and refluxing; after the reaction is finished, removing most acetonitrile under reduced pressure, adding water and ethyl acetate for extraction, washing an organic phase with saturated sodium chloride solution, drying with anhydrous sodium sulfate, carrying out vacuum filtration, concentrating filtrate to remove solvent, and purifying by column chromatography to obtain a compound 5;
C. Preparation of Compound 6:
adding a proper amount of isopropanol into a reaction bottle, slowly dropwise adding 1 mol/L sodium hydroxide solution under stirring, and heating for reflux; after the reaction is finished, removing most of isopropanol under reduced pressure, regulating the pH value of a system to be 1-2 by using 1 mol/L hydrochloric acid solution, and carrying out suction filtration and drying on the generated solid to obtain a compound 6;
D. Preparation of compound 7:
Adding a proper amount of N, N-dimethylformamide into a reaction bottle, sequentially adding 1H-benzotriazole-1-yl oxygen tripyrrolidine hexafluorophosphate, abbreviated as PyBOP, N-diisopropylethylamine and abbreviated as DIPEA and 4-amino anisole sulfide under 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 saturated sodium chloride solution, drying by using anhydrous sodium sulfate, carrying out vacuum filtration, concentrating filtrate to remove a solvent, and purifying by column chromatography to obtain a compound 7;
E. Preparation of Compound I-a:
Adding a proper amount of absolute methanol into a reaction bottle, sequentially adding iodobenzene diacetic acid (abbreviated as PhI (OAc) 2 and ammonium carbonate under stirring, and stirring at room temperature; after the reaction is finished, removing most of methanol under reduced pressure, adding water and ethyl acetate for extraction, washing an organic phase with saturated sodium chloride solution, drying with anhydrous sodium sulfate, carrying out vacuum filtration, concentrating filtrate to remove solvent, and purifying by column chromatography to obtain a compound I-a;
F. preparation of Compound I-b:
Adding a proper amount of anhydrous pyridine into a reaction bottle, then adding R 2 SO2Cl, and stirring at room temperature; after the reaction is finished, adding water and ethyl acetate for extraction, washing an organic phase by using a1 mol/L hydrochloric acid solution and a saturated sodium chloride solution in sequence, drying by using anhydrous sodium sulfate, carrying out vacuum filtration, concentrating filtrate to remove a solvent, and purifying by column chromatography to obtain a compound I-b;
G. preparation of Compounds I-c:
Adding a proper amount of anhydrous pyridine into a reaction bottle, then adding R 2 COCl, and stirring at room temperature; after the reaction is finished, adding water and ethyl acetate for extraction, washing an organic phase by using 1 mol/L hydrochloric acid solution, saturated sodium bicarbonate solution and saturated sodium chloride solution in sequence, drying by using anhydrous sodium sulfate, carrying out vacuum filtration, concentrating filtrate to remove a solvent, and purifying by column chromatography to obtain a compound I-c;
H. preparation of Compounds I-d:
Adding a proper amount of N, N-dimethylformamide into a reaction bottle, sequentially adding cuprous chloride and R 2 -N=C=O, and stirring at room temperature; after the reaction, water and ethyl acetate are added for extraction, an organic phase is washed by saturated sodium chloride solution, dried by anhydrous sodium sulfate, reduced pressure and suction filtration are carried out, the filtrate is concentrated to remove the solvent, and the compound I-d is obtained by column chromatography purification.
3. Use of a sulfilimine psoralen derivative according to claim 1 for the preparation of an agricultural fungicide; the fungi controlled by the agricultural fungicide are selected from: tomato early blight germ, cucumber gray mold germ, apple ring rot germ, rice sheath blight germ and sclerotinia rot germ.
4. An agricultural bactericidal composition comprising the sulfinimine-based derivative of claim 1 as an active ingredient; the composition comprises from 0.1% to 99.9% by weight of an active ingredient, from 99.9% to 0.1% by weight of a solid or liquid adjuvant, and from 0 to 25% by weight of a surfactant.
5. An agricultural bactericidal compound composition comprising the sulfinimine psoralen derivative of claim 1 and other commercial bactericides as active ingredients; the mass percentage of the sulfimide psoralen derivative and other commercial bactericides is 1 percent to 99 percent to 1 percent, and the compound composition comprises 1 percent to 99 percent of active ingredient and 99 percent to 1 percent of solid or liquid auxiliary agent.
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