CN113929697A

CN113929697A - 1,3, 4-oxadiazole psoralen derivatives and preparation method and application thereof

Info

Publication number: CN113929697A
Application number: CN202111351143.3A
Authority: CN
Inventors: 范志金; 董静月; 洪泽宇; 李坤; 高卫; 陈蕾; 唐良富
Original assignee: Nankai University
Current assignee: Nankai University
Priority date: 2021-11-16
Filing date: 2021-11-16
Publication date: 2022-01-14
Anticipated expiration: 2041-11-16

Abstract

The invention provides 1,3, 4-oxadiazole psoralen derivatives, a preparation method and application thereof, and particularly relates to the 1,3, 4-oxadiazole psoralen derivatives, wherein the general chemical structure formula of the derivatives is shown as formula I:

Description

1,3, 4-oxadiazole 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 1,3, 4-oxadiazole psoralen compounds and a preparation method and application thereof.

Background

As part of bio-rational pesticides, plant-derived pesticides, the development and research thereof have been the focus of new pesticide research. The plant source pesticide can be degraded in nature, and generally does not pollute the environment and agricultural products. The possibility of accumulating toxicity in the environment and human body is low, the pesticide composition is relatively safe to human and livestock, has the characteristics of low toxicity and low residue, and can maintain high quality of agricultural products (Lidaofie et al, southern agriculture, 2018, 72 (13): 40-42, 45.). Psoralen is an important botanical drug intermediate, and has wide application value in the fields of food, medicine, pesticide and the like. The agricultural bactericide prepared by using psoralen as an active ingredient has excellent bactericidal activity, can be applied to preventing and treating diseases of various crops, is particularly suitable for preventing and treating agricultural fungal diseases, such as sclerotinia rot of colza, rice sheath blight, wheat scab and the like, and is an ideal bactericide in agriculture.

The heterocyclic compound contains nitrogen, oxygen, sulfur and other atoms, has high-efficiency, low-toxicity and broad-spectrum biological activity, and plays an important role in the design and synthesis of novel green pesticides. The literature reports that five-membered heterocyclic compounds have various activities such as insect killing, bacteriostasis, weeding, plant growth regulation and the like (Chendanping and the like, modern pesticides, 2014, 14 (2): 5-10.); wherein, the 1,3, 4-oxadiazole is taken as a common nitrogen-containing five-membered heterocycle, has good biological activity and pharmacological activity, such as anti-tumor, anti-HIV, anti-convulsion, antivirus, insecticidal, weeding, sterilization and the like, and is widely applied to the fields of pesticide, medicine and the like (Yanzihui, Kunming academy of academic, 2017, 39 (6): 85-88.). For example, the herbicide oxadiazon can effectively prevent and kill various annual monocotyledon and dicotyledon weeds, and the pesticide oxadiazon has the contact poisoning or stomach poisoning effect on insects and can be used for preventing and controlling pests such as cockroaches, aphids, leafhoppers and the like. In addition, the organic electroluminescent material has excellent electron injection and transport functions and is widely applied to organic electroluminescent materials. And the parent nucleus structure has hydrogen bond acceptor characteristics and can effectively improve the lipophilicity and the pharmacokinetic characteristics of the drug, so that the 1,3, 4-oxadiazole structure is still often selected as an effective active group in the creation of new pesticides.

In order to search 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 a 1,3, 4-oxadiazole structure into the lead structure of psoralen, designs and synthesizes 1,3, 4-oxadiazole 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 1,3, 4-oxadiazole 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 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 1,3, 4-oxadiazole psoralen compound with insecticidal, acaricidal, bactericidal, anti-plant virus and induced 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; r²Selected from: 4-methylbenzyl, 4-fluorobenzyl, 3-methylbenzyl, 4-nitrobenzyl, o-methylbenzyl, 4-chlorobenzyl, propargyl, 4-iodobenzyl, n-propyl, 2-naphthylmethyl, allyl, 2, 4-dichlorobenzyl, 4-tert-butylbenzyl, cyclopropylmethyl, 4-chlorobenzoylmethyl, 2-cyano-5-picolyl, 3-bromobenzyl, (E) -2- (2-methoxy-1- (methoxyimino) -2-oxyethyl) benzyl, (E) -2- (1, 3-dimethoxy-3-oxoprop-1-en-2-yl) benzyl, 3-methylbenzylBut-2-enyl, benzoylmethyl, 4-trifluoromethoxybenzyl, 2- (4-chlorophenyl) ethyl.

The synthetic route of the 1,3, 4-oxadiazole psoralen derivative I and the intermediate thereof is as follows:

synthetic route to Compounds I

The synthesis method of the 1,3, 4-oxadiazole 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 anhydrous 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, and carrying out column chromatography purification to obtain a compound 7;

E. preparation of compound 8:

taking the compound 7, adding a proper amount of methanol into a reaction bottle, slowly dropwise adding 80% hydrazine hydrate 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 by using anhydrous sodium sulfate, carrying out suction filtration under reduced pressure, concentrating the filtrate to remove the solvent, and carrying out column chromatography purification to obtain a compound 8;

F. preparation of compound 9:

putting the compound 8 into a reaction bottle, adding a proper amount of absolute ethyl alcohol, adding potassium hydroxide under stirring, then slowly dropwise adding carbon disulfide, and heating and refluxing; after the reaction is finished, removing most of ethanol under reduced pressure, adding 1 mol/L hydrochloric acid solution into the residue to adjust the pH of the system to be 1-2, extracting with ethyl acetate, washing an organic phase with saturated sodium chloride solution, drying with anhydrous sodium sulfate, carrying out suction filtration under reduced pressure, concentrating the filtrate to remove the solvent, and purifying by column chromatography to obtain a compound 9;

G. preparation of Compound I-a:

taking the compound 9, adding a proper amount of N, N-dimethylformamide into a reaction bottle, sequentially adding potassium hydroxide, chlorohydrocarbon or bromohydrocarbon, and stirring at room temperature; after the reaction is finished, adding a proper amount of 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 the filtrate to remove the solvent, and carrying out column chromatography purification to obtain a compound I-a;

H. preparation of Compound I-b:

under the condition of low-temperature ice bath, taking the compound I-a, adding a proper amount of dichloromethane into a reaction bottle, then slowly dropwise adding a dichloromethane solution dissolved with m-chloroperoxybenzoic acid, and moving the system to room temperature for stirring; after the reaction is finished, removing most dichloromethane under reduced pressure, adding a proper amount of ethyl acetate into the residue, washing the residue with 0.25 mol/L disodium hydrogen phosphate solution and saturated sodium chloride solution in sequence, drying the solution with anhydrous sodium sulfate, carrying out suction filtration under reduced pressure, concentrating the filtrate to remove the solvent, and carrying out column chromatography purification to obtain a compound I-b;

I. preparation of Compounds I-c:

under the condition of low-temperature ice bath, taking the compound I-a, adding a proper amount of acetic acid into a reaction bottle, slowly dropwise adding a hydrogen peroxide solution dissolved with ammonium molybdate while stirring, and then transferring the system to room temperature for stirring; after the reaction is finished, adding water and ethyl acetate for extraction, washing the organic phase with a saturated sodium bisulfate solution and a saturated sodium chloride solution successively, drying with anhydrous sodium sulfate, carrying out suction filtration under reduced pressure, concentrating the filtrate to remove the solvent, and carrying out column chromatography purification to obtain a compound I-c;

as a preferred embodiment, the synthesis method of the 1,3, 4-oxadiazole psoralen derivative provided by the invention 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:

1 g of compound 6 and 30 ml of anhydrous methanol are added into a 100 ml round-bottom flask, 1.5 ml of 98% concentrated sulfuric acid is slowly dropped into the flask under stirring at room temperature, and the reaction system is heated and refluxed for 5 hours after the dropping is finished. Monitoring by TLC, after the reaction is finished, standing the system to cool to room temperature, removing most methanol under reduced pressure, adding 30 ml of water into the residue, extracting three times with ethyl acetate (15 ml. times.3), washing the organic phase with saturated sodium chloride solution for three times (15 ml. times.3), and drying the combined organic layers with 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 7; the amount of compound 7 produced and the volume of the reaction vessel are scaled up or down accordingly.

E. Preparation of compound 8:

a100 ml round-bottom flask was charged with 1 mmol of Compound 7 and 30 ml of methanol, and 4 mmol of 80% hydrazine hydrate was slowly added dropwise with stirring at room temperature, and the reaction system was heated under reflux for 8 hours after completion of the addition. Monitoring by TLC, after the reaction is finished, standing the system to cool to room temperature, removing most methanol under reduced pressure, adding 30 ml of water into the residue, extracting three times with ethyl acetate (15 ml. times.3), washing the organic phase with saturated sodium chloride solution for three times (15 ml. times.3), and drying the combined organic layers with anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying with dichloromethane/methanol (15: 1, volume/volume) eluent column chromatography to obtain compound 8; the amount of compound 8 produced and the volume of the reaction vessel are scaled up or down accordingly.

F. Preparation of compound 9:

a100 ml round-bottom flask was charged with 1 mmol of Compound 8 and 20 ml of anhydrous ethanol, 1.2 mmol of potassium hydroxide was added at room temperature with stirring, 3 mmol of carbon disulfide was slowly added after 5 minutes, and the reaction was heated to reflux for 6 hours. Monitoring by TLC, after the reaction is finished, standing the system, cooling to room temperature, removing most ethanol under reduced pressure, adding 15 ml of water into the residue, adjusting the pH of the system to 1-2 by using 1 mol/l hydrochloric acid solution, extracting three times (15 ml × 3) by using ethyl acetate, washing three times (15 ml × 3) by using saturated sodium chloride solution for an organic phase, and drying combined organic layers by using anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying with dichloromethane/methanol (17: 1, volume/volume) eluent column chromatography to obtain compound 9; the amount of compound 9 produced and the volume of the reaction vessel are scaled up or down accordingly.

G. Preparation of Compound I-a:

a100-ml round-bottom flask was charged with 1 mmol of compound 9 and 20 ml of N, N-dimethylformamide, and 2.3 mmol of potassium hydroxide and 1.2 mmol of bromohydrocarbon or chlorohydrocarbon were sequentially added thereto under stirring at room temperature, followed by stirring of the reaction system at room temperature for 8 hours. TLC, 15 ml of water was added after the reaction was complete, extracted three times with ethyl acetate (15 ml × 3), the organic phase was washed 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 dichloromethane/methanol (30: 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.

H. Preparation of Compound I-b:

1 mmol of the compound I-a and 20 ml of dichloromethane were added to a 100 ml round-bottomed flask under ice-bath at low temperature, 1.6 mmol of m-chloroperoxybenzoic acid was slowly added with stirring, and then the reaction system was moved to room temperature for 6 hours. TLC, after completion of the reaction most of the dichloromethane was removed under reduced pressure, extracted three times with ethyl acetate (15 ml × 3), the organic phase was washed three times with 0.25 mol/l disodium hydrogen phosphate solution (15 ml × 3) and saturated sodium chloride solution (15 ml × 3) in sequence, and the combined organic layers were dried over anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying with dichloromethane/methanol (40: 1, volume/volume) eluent column chromatography 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.

I. Preparation of Compounds I-c:

under the condition of low-temperature ice bath, 1 mmol of the compound I-a and 20 ml of anhydrous acetic acid are added into a 100 ml round-bottom flask, a 30% hydrogen peroxide solution containing 0.05 mmol of ammonium molybdate is slowly added dropwise with stirring to 6 mmol, and then the reaction system is moved to room temperature for reaction for 8 hours. TLC, 15 ml of water was added after the reaction was complete, extraction was performed three times with ethyl acetate (15 ml × 3), the organic phase was washed three times with saturated sodium hydrogen sulfate solution (15 ml × 3) and saturated sodium chloride solution (15 ml × 3) in sequence, 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-c; the amount of compound I-c prepared and the volume of the reaction vessel are scaled up or down accordingly.

Wherein R is¹Selected from: hydrogen, 4-fluoro; r²Selected from: 4-methylbenzyl, 4-fluorobenzyl, 3-methylbenzyl, 4-nitrobenzyl, o-methylbenzyl, 4-chlorobenzyl, propargyl, 4-iodobenzyl, n-propyl, 2-naphthylmethyl, allyl, 2, 4-dichlorobenzyl, 4-tert-butylbenzyl, cyclopropylmethyl, 4-chlorobenzoylmethyl, 2-cyano-5-picolyl, 3-bromobenzyl, (E) -2- (2-methoxy-1- (methoxyimino) -2-oxyethyl) benzyl, (E) -2- (1, 3-dimethoxy-3-oxoprop-1-en-2-yl) benzyl, 3-methylbut-2-enyl, m-ethylbenzyl, n-propylbenzyl, n-2-propylbenzyl, p-ethylbenzyl, p-2-ethylbut-2-enyl, p-methyl-benzyl, p-2-ethylbenzyl, p-butyl-2-ethyl, p-benzyl, p-butyl-2-benzyl, p-methyl-2-benzyl, p-methyl, p-2-o-benzyl, p-methyl-benzyl, p-2-p, Benzoylmethyl, 4-trifluoromethoxybenzyl, 2- (4-chlorophenyl) ethyl.

The invention provides application of the 1,3, 4-oxadiazole psoralen derivative I in preparation of fungicides.

The invention provides application of the 1,3, 4-oxadiazole psoralen derivative I in preparation of an anti-tobacco mosaic virus agent.

The invention provides application of the 1,3, 4-oxadiazol psoralen derivative I in preparing a plant activator for inducing tobacco to resist tobacco mosaic virus.

The invention provides application of the 1,3, 4-oxadiazole psoralen derivative I in preventing and treating agricultural and forestry and horticultural plant insect pests.

The 1,3, 4-oxadiazole psoralen derivative I is applied together with agricultural chemicals; the agrochemical is selected from: one or more of insecticide, bactericide, plant virus resisting agent and acaricide.

The 1,3, 4-oxadiazole psoralen derivative I and any one or two of the insecticides are combined to form an insecticidal composition for preventing and treating insect pests of agricultural and forestry and horticultural plants;

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 mass percentage of the 1,3, 4-oxadiazole psoralen derivative I in the insecticidal composition is 1% -90%; preferably, the mass percentage of the 1,3, 4-oxadiazole psoralen derivative I to the pesticide 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.

The 1,3, 4-oxadiazole psoralen derivative I and any one or two of the bactericides are combined to form a bactericidal composition for preventing and treating diseases of agricultural, forestry and horticultural plants;

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 1,3, 4-oxadiazole psoralen derivative I accounts for 1-90% of the total mass of the sterilization composition; the proportion of the 1,3, 4-oxadiazole psoralen derivative I to the bactericide is 1 to 99 to 1 mass percent;

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 1,3, 4-oxadiazole 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 and 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 1,3, 4-oxadiazole psoralen derivative I accounts for 1-90% of the total mass of the antiviral composition; preferably, the ratio of the 1,3, 4-oxadiazole psoralen derivative I to the anti-plant virus agent is 1% to 99% to 1% in percentage by mass;

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 1,3, 4-oxadiazole psoralen derivative I and any one or two of acaricides are combined to form an acaricide composition for preventing and controlling mite damage of agricultural and 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 1,3, 4-oxadiazole psoralen derivative I in the acaricidal composition is 1% -90%; the ratio of the 1,3, 4-oxadiazole 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 1,3, 4-oxadiazole psoralen derivative I is determined as follows:

the bactericidal activity of the 1,3, 4-oxadiazole psoralen derivative I of the invention is determined as follows:

the bactericidal or bacteriostatic activity of the invention containing 1,3, 4-oxadiazole psoralen I adopts a thallus growth rate determination method, which comprises the following specific steps: 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 1,3, 4-oxadiazole psoralen derivatives I are subjected to lead optimization, and the 1,3, 4-oxadiazole psoralen derivatives are subjected to antibacterial activity screening.

The synthesis, biological activity and application of 1,3, 4-oxadiazole 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 limiting the invention, in particular, the biological activity is only illustrated and not limiting the patent, and the specific implementation modes are as follows:

example 1: 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. TLC monitoring, after the reaction was complete 30 ml of anhydrous methanol was added and poured into ice water to yield a large amount of white solid, the solid obtained was filtered off with suction, the crude product was washed with diethyl ether and taken in with ethanol-waterRecrystallizing 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:

a100 ml round-bottom flask was charged with 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 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 acetonitrile under reduced pressure, adding 30 ml of water into the residue, extracting for 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; 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 65%; the nuclear magnetic data are as follows:¹h NMR (400MHz, DMSO) δ 8.12(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). 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:

adding 2 g of compound 5 and 30 ml of isopropanol into a 100 ml round-bottom flask, slowly dropwise adding 60 ml of 1 mol/L sodium hydroxide solution at room temperature under stirring, heating and refluxing the reaction system for 4 hours after dropwise adding. 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 thereof was found to be 61%; the nuclear magnetic data are as follows:¹h NMR (400MHz, DMSO). delta.12.29 (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). 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:

1 g of compound 6 and 30 ml of anhydrous methanol are added into a 100 ml round-bottom flask, 1.5 ml of 98% concentrated sulfuric acid is slowly dropped into the flask under stirring at room temperature, and the reaction system is heated and refluxed for 6 hours after the dropping is finished. TLC, after the reaction was complete, the system was allowed to stand to cool to room temperature, most of the methanol was removed under reduced pressure, 15 ml of water was added to the residue, extracted three times with ethyl acetate (15 ml × 3), the organic phase was washed 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 (3: 1, volume/volume) eluent column chromatography to obtain compound 7; the yield is 79 percent; the nuclear magnetic data are as follows:¹h NMR (400MHz, DMSO) δ 8.47(s, 1H), 8.17(s, 1H), 7.87(dd, J ═ 8.7, 5.5Hz, 2H), 7.80(s, 1H), 7.38(t, J ═ 8.8Hz, 2H), 3.75(s, 2H), 3.63(s, 3H), 2.55(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 8:

a100 ml round-bottom flask was charged with 1 mmol of Compound 7 and 30 ml of methanol, and stirred at room temperature4 millimole of 80% hydrazine hydrate is slowly added dropwise, and the reaction system is heated and refluxed for 6 hours after the addition is finished. TLC, after the reaction was complete, the system was allowed to stand to cool to room temperature, most of the methanol was removed under reduced pressure, 15 ml of water was added to the residue, extracted three times with ethyl acetate (15 ml × 3), the organic phase was washed 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 dichloromethane/methanol (15: 1, volume/volume) eluent column chromatography to obtain compound 8; the yield is 53 percent; the nuclear magnetic data are as follows:¹h NMR (400MHz, DMSO). delta.9.18 (s, 1H), 8.44(s, 1H), 8.09(s, 1H), 7.85(s, 2H), 7.73(s, 1H), 7.38(s, 2H), 4.30(s, 2H), 3.51(s, 2H), 3.41(s, 3H). The amount of compound 8 produced and the volume of the reaction vessel are scaled up or down accordingly.

Example 6: preparation of compound 9:

a100 ml round bottom flask was charged with 0.2 g of Compound 8 and 20 ml of absolute ethanol, 0.033 g of potassium hydroxide was added with stirring, after 5 minutes 0.11 g of carbon disulfide was added slowly, and the reaction was heated to reflux for 5 hours. Monitoring by TLC, after the reaction is finished, standing the system, cooling to room temperature, removing most ethanol under reduced pressure, adding 15 ml of water into the residue, adjusting the pH of the system to 1-2 by using 1 mol/l hydrochloric acid solution, extracting three times (15 ml × 3) by using ethyl acetate, washing three times (15 ml × 3) by using saturated sodium chloride solution for an organic phase, and drying combined organic layers by using anhydrous sodium sulfate; vacuum filtering, concentrating the filtrate to remove solvent, and purifying with dichloromethane/methanol (17: 1, volume/volume) eluent column chromatography to obtain compound 9; the yield is 77%; the nuclear magnetic data are as follows:¹h NMR (400MHz, DMSO) δ 14.40(s, 1H), 8.47(s, 1H), 8.18(s, 1H), 7.89-7.83(m, 2H), 7.80(s, 1H), 7.37(t, J ═ 8.6Hz, 2H), 4.15(s, 2H), 2.63(s, 3H). The amount of compound 9 produced and the volume of the reaction vessel are scaled up or down accordingly.

Example 7: preparation of Compound I-a:

a100 ml round-bottom flask was charged with 0.2 g of Compound 9 and 20 ml of N, N-dimethylformamide, and 0.063 g of potassium hydroxide and 0.175 g of 4-iodobenzyl bromide were successively added under stirring, followed by stirring the system at room temperature for 8 hours. TLC, 30 ml of water was added after the reaction was complete, extracted three times with ethyl acetate (15 ml × 3), the organic phase was washed 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 dichloromethane/methanol (30: 1, volume/volume) eluent column chromatography to obtain compound I-a; yield: 71-95 percent; when R is¹Is 4-fluorophenyl, R²For 4-iodobenzyl, the nuclear magnetic data for compound I-a-1 is as follows:¹h NMR (400MHz, DMSO) δ 8.40(s, 1H), 8.09(s, 1H), 7.84-7.77(m, 2H), 7.70(s, 1H), 7.55(d, J ═ 7.9Hz, 2H), 7.33(t, J ═ 8.6Hz, 2H), 7.15(d, J ═ 7.9Hz, 2H), 4.37(s, 2H), 4.22(s, 2H), 2.56(s, 3H). The preparation amount of the compound I-a-1 and the volume of a reaction vessel are enlarged or reduced according to corresponding proportion; the physicochemical and structural parameters of compound I-a are shown in Table 1.

Example 8: preparation of Compound I-b:

0.58 g of Compound I-a-1 and 20 ml of methylene chloride were placed in a 100 ml round-bottomed flask in a cold ice bath, 0.256 g of m-chloroperoxybenzoic acid was slowly added with stirring, and the reaction was allowed to stand at room temperature for 6 hours. TLC, after completion of the reaction most of the dichloromethane was removed under reduced pressure, extracted three times with ethyl acetate (15 ml × 3), the organic phase was washed three times with 0.25 mol/l disodium hydrogen phosphate solution (15 ml × 3) and saturated sodium chloride solution (15 ml × 3) in sequence, and the combined organic layers were dried over anhydrous sodium sulfate; reducingPerforming pressure suction filtration, concentrating the filtrate to remove the solvent, and performing column chromatography purification by using dichloromethane/methanol (40: 1, volume/volume) eluent to obtain a compound I-b; yield: 65-91%; when R1 is 4-fluorophenyl, R²For 4-iodobenzyl, the nuclear magnetic data for compound I-b-1 is as follows:¹h NMR (400MHz, DMSO) δ 8.45(s, 1H), 8.17(s, 1H), 7.84(dd, J ═ 8.2, 5.5Hz, 2H), 7.79(s, 1H), 7.63(d, J ═ 8.1Hz, 2H), 7.36(t, J ═ 8.7Hz, 2H), 7.01(d, J ═ 8.0Hz, 2H), 4.68(q, J ═ 12.7Hz, 2H), 4.39(s, 2H), 2.63(s, 3H). The preparation amount of the compound I-b-1 and the volume of a reaction vessel are enlarged or reduced according to corresponding proportion; the physicochemical and structural parameters of the compounds I-b are shown in Table 1.

Example 9: preparation of Compounds I-c:

under the condition of low-temperature ice bath, 0.1 g of compound I-a-2 and 15 ml of anhydrous acetic acid are added into a 100 ml round-bottom flask, 10.7 ml of 30% hydrogen peroxide solution dissolved with 2 mg of ammonium molybdate is slowly dropped into the flask under stirring, and then the reaction system is moved to room temperature for reaction for 8 hours. TLC, 15 ml of water was added after the reaction was complete, extraction was performed three times with ethyl acetate (15 ml × 3), the organic phase was washed three times with saturated sodium hydrogen sulfate solution (15 ml × 3) and saturated sodium chloride solution (15 ml × 3) in sequence, 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-c; yield: 93 percent; when R is¹Is phenyl, R²In the case of 4-trifluoromethoxybenzyl group, the nuclear magnetic data of compound I-c-1 are as follows:¹h NMR (400MHz, DMSO) δ 8.51(s, 1H), 8.27(s, 1H), 7.87-7.81(m, 3H), 7.55(t, J ═ 7.5Hz, 2H), 7.46-7.41(m, 3H), 7.31(d, J ═ 8.1Hz, 2H), 5.25(s, 2H), 4.41(s, 2H), 2.65(s, 3H). The preparation amount of the compound I-c-1 and the volume of a reaction vessel are enlarged or reduced according to corresponding proportion; the physicochemical and structural parameters of the compounds I-c are shown in Table 1.

Example 10: the antibacterial activity determination result of the 1,3, 4-oxadiazole psoralen derivative I provided by the invention is as follows:

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-2-105, DJY-2-160, DJY-2-173, DJY-2-180, DJY-2-192, DJY-2-194, DJY-2-176 and DJY-2-200 are more than 65 percent and are all higher than 2210 percent of the control medicine bone lipid and YZK-C; for botrytis cinerea, the inhibition rates of the compounds DJY-2-160, DJY-2-174, DJY-2-170, DJY-2-178, DJY-2-184, DJY-2-176, DJY-2-199 and DJY-2-200 are more than 75%, the inhibition rates are superior to the control drugs of the bone lipid supplement and YZK-C22, especially the bactericidal activities of the compounds DJY-2-174, DJY-2-170 and DJY-2-176 are higher than 95%, and are higher than the control drugs of the bone lipid supplement and YZK-C2220%; for peanut brown spot pathogen, the inhibition rate of the compounds DJY-2-106, DJY-2-160, DJY-2-174 and DJY-2-127 is more than 70%, and is equal to or higher than that of a control medicament such as the bone lipid supplement drug and YZK-C22, wherein the bactericidal activity of the compound DJY-2-160 is the highest and reaches 88%, and is more than 20% higher than that of the control medicament such as the bone lipid supplement drug; for Gibberella tritici, the inhibition rates of the compounds DJY-2-105, DJY-2-112, DJY-2-129, DJY-2-160, DJY-2-168, DJY-2-173, DJY-2-174, DJY-2-192 and DJY-2-200 are more than 60 percent, and are equal to or higher than that of the control drugs for supplementing the bone lipoid and YZYZK-C22, wherein the inhibition rates of the compounds DJY-2-105, DJY-2-160 and DJY-2-168 are higher than that of the control drugs for supplementing the bone lipoid by nearly 10 percent; for apple ring spot bacteria, the inhibition rates of the compounds DJY-2-117, DJY-2-160, DJY-2-169, DJY-2-173, DJY-2-171, DJY-2-174, DJY-2-180 and DJY-2-192 are all over 60 percent and are over 20 percent higher than that of the control drug for supplementing the osteoproliferatin; for rhizoctonia solani, the inhibition rate of the compounds DKY-2-160 and DKY-2-192 is more than 70 percent and is more than 20 percent higher than that of a control medicament for supplementing the osseointegration; for Sclerotinia sclerotiorum, the inhibition rates of the compounds DJY-2-160, DJY-2-174, DJY-2-192 and DJY-2-194 are more than 65% and are better than the inhibition rates of the control drug-containing osteoproliferation and YZK-C22, wherein the inhibition rates of the compounds DJY-2-174, DJY-2-192 and DJY-2-194 are all higher than the inhibition rates of the control drug-containing osteoproliferation by more than 10%.

Example 11: the application of the 1,3, 4-oxadiazole psoralen derivative I in preparing the pesticide composition comprises the following steps:

the 1,3, 4-oxadiazole psoralen derivative I is used for preparing a pesticide composition, the composition contains the 1,3, 4-oxadiazole psoralen derivative I and an intermediate thereof as active ingredients, and the active ingredients are 0.1 to 99.9 weight percent, 99.9 to 0.1 weight percent of solid or liquid auxiliary agents and optionally 0 to 50 weight percent of surfactant.

Example 12: the application of the 1,3, 4-oxadiazole psoralen derivative I in preparing the pesticide compound composition comprises the following steps:

the 1,3, 4-oxadiazol 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 1,3, 4-oxadiazol psoralen derivative I and the intermediate thereof and other commercial pesticides, namely insecticides, acaricides, bactericides, antiviral agents or plant activators, which are taken as active ingredients, the ratio of the 1,3, 4-oxadiazol psoralen derivative I and the intermediate thereof to other commercial pesticides, namely insecticides, acaricides, bactericides, antiviral agents or plant activators is 1 percent to 99 percent to 1 percent by mass, the content of the active ingredients is 0.1 to 99.9 percent by weight, and the solid or liquid auxiliary agents of 99.9 to 0.1 percent by weight, and optionally from 0 to 50% by weight of a surfactant.

Example 13: the application of the combination of the 1,3, 4-oxadiazole psoralen derivative I and the insecticide in preventing and treating agricultural, forestry and horticultural plant insect pests:

the 1,3, 4-oxadiazole 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 1,3, 4-oxadiazole psoralen derivative I in the insecticidal composition is 1-90%, and the mass percentage of the 1,3, 4-oxadiazole psoralen derivative I in the invention and the commercial insecticide is 1: 99-99: 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 14: the application of the combination of the 1,3, 4-oxadiazole psoralen derivative I and the bactericide in preventing and treating agricultural, forestry and horticultural plant diseases:

the 1,3, 4-oxadiazole psoralen derivative I and any one or two of commercial bactericides are combined to form a bactericidal composition for preventing and treating diseases of agricultural, forestry and horticultural plants, wherein the commercial bactericides are selected from the following group: 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 1,3, 4-oxadiazole psoralen derivative I in the sterilization composition is 1-90%, and the mass percentage of the 1,3, 4-oxadiazole psoralen derivative I in the sterilization composition to the commercial bactericide is 1: 99-99: 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 15-use of 1,3, 4-oxadiazolidvachellin derivatives I of the present invention in combination with an anti-plant virus agent for the control of viral diseases in agricultural and forestry and horticultural plants:

the 1,3, 4-oxadiazole psoralen derivative I and any one or two of commercial antiviral medicaments form an antiviral composition for preventing and treating viral diseases of agricultural, forestry and horticultural plants, wherein the commercial antiviral medicament is selected from the following components: 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 1,3, 4-oxadiazole psoralen derivative I accounts for 1-90% of the total mass of the antiviral composition, and the ratio of the 1,3, 4-oxadiazole psoralen derivative I to the commercial anti-plant virus agent accounts for 1-99-1% of the mass; 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 16: the application of the combination of the 1,3, 4-oxadiazole psoralen derivative I and the acaricide in preventing and controlling the mite damage of agricultural, forestry and horticultural plants is as follows:

the 1,3, 4-oxadiazole psoralen derivative I and any one or two of commercial acaricides form an acaricidal composition for preventing and controlling acarids of agricultural and 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 1,3, 4-oxadiazole psoralen derivative I in the acaricidal composition is 1-90%, and the mass percentage of the 1,3, 4-oxadiazole psoralen derivative I in the invention to the commercial acaricide is 1: 99-99: 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 1,3, 4-oxadiazole psoralen derivatives; 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 1,3, 4-oxadiazolpsoralen derivatives I of the present invention (inhibition rate 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-2-103	64	45	30	39	32	17	44
2	DJY-2-104	60	31	28	48	21	21	37
									3	DJY-2-105	78	42	17	75	15	28	33
4	DJY-2-106	63	29	72	29	5	36	61
									5	DJY-2-107	57	40	24	52	38	24	24
6	DJY-2-109	64	39	14	52	21	21	35
									7	DJY-2-111	63	47	37	45	38	15	43
8	DJY-2-112	58	49	31	70	25	25	57
									9	DJY-2-114	56	58	47	40	43	21	60
10	DJY-2-115	44	55	21	49	19	13	45
									11	DJY-2-117	47	42	48	46	76	17	35
12	DJY-2-123	34	34	29	56	28	18	46
									13	DJY-2-121	59	50	38	24	24	9	52
14	DJY-2-129	43	47	38	61	12	11	55
									15	DJY-2-120	65	41	21	29	32	26	47
16	DJY-2-116	38	73	19	34	11	22	39
									17	DJY-2-108	57	43	35	25	26	24	53
18	DJY-2-160	89	85	88	73	77	77	65
									19	DJY-2-168	65	58	59	72	53	38	55
20	DJY-2-169	63	42	64	52	63	53	59
									21	DJY-2-173	75	49	63	67	75	23	62
22	DJY-2-171	66	45	60	51	72	27	57
									23	DJY-2-174	60	99	72	61	64	43	70
24	DJY-2-170	64	100	62	53	58	36	61
									25	DJY-2-178	50	88	62	40	31	28	48
26	DJY-2-180	72	44	59	34	65	38	56
									27	DJY-2-179	35	36	56	46	43	21	25
28	DJY-2-181	37	48	55	39	38	23	53
									29	DJY-2-192	70	66	46	67	70	74	76
30	DJY-2-197	64	53	61	48	59	24	59
									31	DJY-2-194	75	61	59	52	58	23	73
32	DJY-2-184	61	87	64	56	61	26	37
									33	DJY-2-176	72	99	63	52	53	25	54
34	DJY-2-199	37	57	32	50	38	31	22
									35	DJY-2-200	79	84	61	62	61	48	42
36	DJY-2-127	65	34	74	58	62	59	32
									37	Psoralen	56	50	65	63	44	52	58
38	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

1. A1, 3, 4-oxadiazole psoralen derivative is characterized by simultaneously containing 1,3, 4-oxadiazole and psoralen structures and has a structural general formula shown in a formula I:

2. The specific synthetic route and method of the 1,3, 4-oxadiazole psoralen derivative I according to claim 1 are as follows:

A：

B：

C：

D：

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:

B. preparation of compound 5:

C. preparation of compound 6:

D. preparation of compound 7:

E. preparation of compound 8:

F. preparation of compound 9:

G. preparation of Compound I-a:

H. preparation of Compound I-b:

I. preparation of Compounds I-c:

under the condition of low-temperature ice bath, taking the compound I-a, adding a proper amount of acetic acid into a reaction bottle, slowly dropwise adding a hydrogen peroxide solution dissolved with ammonium molybdate while stirring, and then transferring the system to room temperature for stirring; after the reaction is finished, adding water and ethyl acetate for extraction, washing the organic phase with a saturated sodium bisulfate solution and a saturated sodium chloride solution successively, drying with anhydrous sodium sulfate, carrying out suction filtration under reduced pressure, concentrating the filtrate to remove the solvent, and carrying out column chromatography purification to obtain the compound I-c.

3. Use of the 1,3, 4-oxadiazolidvachalene derivative I as claimed in claim 1 for the preparation of agricultural fungicides.

4. An agricultural fungicidal composition comprising the 1,3, 4-oxadiazolidvachellinoid derivative I according to claim 1 and an intermediate, which can be prepared as an agricultural fungicidal composition comprising the 1,3, 4-oxadiazolidvachellinoid derivative I according to 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 1,3, 4-oxadiazole psoralen derivative I and other commercial bactericides as active ingredients, wherein the mass percentage of the 1,3, 4-oxadiazole psoralen derivative I to the other commercial bactericides is 1 percent to 99 percent to 1 percent, the content of the active ingredients is 1 to 99 percent by weight, and the content of the solid or liquid auxiliary agents is 99 to 1 percent by weight.

6. An agricultural insecticidal and acaricidal compound composition, which comprises 1,3, 4-oxadiazole psoralen derivative I and other commercial insecticidal and acaricidal agents as active ingredients, wherein the mass percentage of the 1,3, 4-oxadiazole psoralen derivative I to the other commercial insecticidal and acaricidal 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. An anti-plant virus agent compound composition, which comprises 1,3, 4-oxadiazole psoralen derivative I and other commercial anti-plant virus agents of claim 1 as active ingredients, wherein the mass percentage of the 1,3, 4-oxadiazole psoralen derivative I and the other commercial anti-plant virus agents is 1% to 99% to 1%, the content of the active ingredients is 1 to 99% by weight, and the weight of the active ingredients is 99 to 1% by weight of solid or liquid auxiliary agents.