Embodiment 1
2,6-dimethyl-4-replaces thiadiazolyl group-Isosorbide-5-Nitrae-dihydropyridine-3,5-dicarboxylic Lipase absobed:
In 50 milliliters of round-bottomed flasks, add 3.90 mmole 4-successively replace thiadiazoles-5-formaldehyde, 7.80 mmoles replace methyl aceto acetate, 3.90 mmole ammonium acetate, 0.39 mmole aluminum trichloride (anhydrous), 10 milliliters of ethanol, reflux stirs, TLC monitors reaction, after question response completes, underpressure distillation removing etoh solvent, residuum volume ratio ethyl acetate: water=1: 1 dissolves, organic layer uses water successively, saturated sodium bicarbonate washs, anhydrous sodium sulfate drying, column chromatography purification, washing and dehydrating integrated machine volume ratio is 60 ~ 90 degrees Celsius of sherwood oils: ethyl acetate=5: 1, yield 64.96%, the amount of synthetic compound expands by corresponding proportion or reduces, the volume scale of respective reaction container or reduce, utilizing 5-to replace thiadiazoles-4-formaldehyde replaces 4-replacement-5-thiadiazoles formaldehyde can prepare the new compound of substituting group position exchange, R
1be selected from: methyl, R
2be selected from: methyl.Described 2,6-dimethyl-4-replace thiadiazolyl group-Isosorbide-5-Nitrae-dihydropyridine-3,5-dicarboxylate is selected from 2,6-dimethyl-4-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-1,4-dihydropyridine-3,5-dicarboxylate, 2,6-dimethyl-4-(5-methyl isophthalic acids, 2,3-thiadiazoles-4-base)-Isosorbide-5-Nitrae-dihydropyridine-3,5-dicarboxylate.Wherein, 2,6-dimethyl-4-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-Isosorbide-5-Nitrae-dihydropyridine-3,5-dicarboxylate
1h-NMR (400MHz/CDCl
3) δ 6.13 (1H, s), 5.50 (1H, s), 4.13 (4H, q), 2.77 (3H, s), 2.35 (6H, s), 1.26 (6H, t); 2,6-dimethyl-4-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-base)-Isosorbide-5-Nitrae-dihydropyridine-3,5-dicarboxylate
1h-NMR (400MHz/CDCl
3) δ 5.27 (1H, s), 4.11 (4H, q, 2.77 (3H, s), 2.29 (6H, s), 1.23 (6H, t); The physical and chemical parameter of this compounds is in table 1.
Embodiment 2
Antibacterial or the fungicidal activity containing the pyridine derivatives I of 1,2,3-thiadiazoles of the present invention:
Title and the code name of the frequently seen plants pathogenic fungi of the present invention's test comprise AS: tomato early blight bacterium (AlternarIsolani); BC: botrytis cinerea pers (Botrytis cinerea); CA: peanut Cercospora bacteria (Cercospora arachidicola); GZ: fusarium graminearum (Gibberella zeae); PI: phytophthora infestans (Phytophthora infestans (Mont.) deBary); PP: Botryosphaeria berengeriana f. sp (Physalosporapiricola); PS: Rhizoctonia solani Kuhn (PellicularI sasakii); RC: Rhizoctonia cerealis (RhizoctonI cerealis); SS: Sclerotinia sclerotiorum (SclerotinI sclerotiorum), these bacterial classifications have good representativeness, can represent the kind of most of pathogenic bacteria that field occurs in agriculture production.Thalli growth rate method measurement result is in table 2, and data show, when 50 mcg/ml, all compounds of the present invention's synthesis all have fungicidal activity in various degree, Hxw002-12 to the fungicidal activity of AS higher than 40%; Hxw002-12 to the fungicidal activity of CA higher than 40%; Hxw002-12 to the fungicidal activity of PP higher than 40%; Hxw002-12 to the fungicidal activity of BC higher than 40%; Hxw002-12, Hxw002-13 to the fungicidal activity of RC higher than 40%; Hxw002-12, Hxw002-13 to the fungicidal activity of PS higher than 40%.Therefore, this compounds shows good fungicidal activity
Embodiment 3
The insecticidal activity containing the pyridine derivatives I of 1,2,3-thiadiazoles of the present invention
The insecticidal activity assay of pyridine derivatives I to small cabbage moth containing 1,2,3-thiadiazoles of the present invention the results are shown in Table 3, data show when 200 mcg/ml, Hxw002-13 of the present invention is 65% to the insecticidal activity of mythimna separata, and therefore, compound of the present invention shows good insecticidal activity.
Embodiment 4
The effect containing the anti-Resistance In Tobacco tobacco mosaic virus (TMV) of the pyridine derivatives I of 1,2,3-thiadiazoles of the present invention:
Anti-TMV determination of activity the results are shown in Table 4, and table 4 shows, commercial Genes For Plant Tolerance tobacco mosaic disease toxicant virazole has certain activity to TMV, and the therapeutic activity of Hxw002-12 and Hxw002-13 of the present invention is respectively 29.27 ± 4.88% and 41.05 ± 3.73%; The inactivate activity of Hxw002-13 is 44.45 ± 4.79%; Wherein, the therapeutic activity inactivate activity of Hxw002-13 is respectively 41.05 ± 3.73% and 44.45 ± 4.79%, and with to contrast medicament Ningnanmycin and virazole substantially suitable, therefore, compound of the present invention shows activity and the induced activity of good anti-TMV.
Embodiment 5
Of the present invention contain 1,2,3-thiadiazoles pyridine derivatives I and insecticide composition preventing and treating the application in insect pest of the plant
Of the present inventionly allly contain the pyridine derivatives I of 1,2,3-thiadiazoles and existing sterilant: Chlorpyrifos 94, the sub-Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, esfenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, Beta-cyfloxylate, cyfloxylate, Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, permethrin, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, d ichlorbenzuron, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, pyridine worm is grand, lufenuron, poisonous insect urea, penfluron, Noviflumuron and noviflumuron, its No. CAS is 121451-02-3, flucycloxuron, Novaluron and Rimon, chlorfluazuron, Bay sir 6874 i.e. { 1-[(3.5-bis-chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, Bay SIR-8514 i.e. [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, Bistrifluron and bistrifluron, furan tebufenozide, worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, Aphox, meta-tolyl-N-methylcarbamate (MTMC), isoprocarb, cartap, fenobucarb, leaf disperses, carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, benfuracarb, pymetrozine, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, ethiprole, Cupric sulfate, disosultap, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, to rattle away young ketone, Nylar, any one or two kinds in emaricins etc. combinationally use for preventing and treating agricultural and forestry and gardening plant insect pest, of the present inventionly contain 1, the pyridine derivatives I mass percentage in the composition of 2,3-thiadiazoles is 1%-90%, of the present inventionly contains 1, the pyridine derivatives I of 2,3-thiadiazoles and the ratio of above-mentioned sterilant are mass percent 1%: 99% to 99%: 1%, can directly be watered rear spraying, have agriculturally acceptable solvent and emulsifying agent and solubility promoter and synergistic agent etc. in the preparation of composition, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, with the seed of coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, the insect pest that can prevent and treat mainly contains red spider, Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), singly sting mole cricket, Oriental burmeister, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipe thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, sugarcane flat angle plant hopper, cotten aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, Nezara viridula smaragdula Fabricius., green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, cnidocampa flavescens walker, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, small cabbage moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, apple Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, Pyrausta nubilalis (Hubern)., yellow rice borer, Oeobia undalis, Cnaphalocrocis medinali(rice leaf roller), bar snout moth's larva, the wild snout moth's larva of lap leaf, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point diamond drill, black cutworm, large cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, Papilio xuthus, Common Mormon, small white, pyrameis indica, the yellow a kind of butterfly harmful to crop plants of ramie, beans blister beetle, Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, the little buprestid beetle of oranges and tangerines, gold edge buprestid beetle, tenebrio molitor, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, large daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, Phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm hangs cocoon ichneumon wasp, Campoletis chlorideae, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, Soybean stem borer, frit fly, plant fly, onion fly, radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm lacks must post the Agricultural pests such as fly, forestry pest, plant in control agricultural and forestry and gardening plant insect pest comprises paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape.Composition improves the defence capability of plant while desinsection, makes plant create defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 6
Of the present invention contain 1,2,3-thiadiazoles pyridine derivatives I and miticide be combined in the application prevented and treated in plant mites evil
The pyridine derivatives I containing 1,2,3-thiadiazoles of the present invention and agriculturally acceptable auxiliary agent and be selected from azocyclotin, cyhexatin, fenbutatin oxide, three phosphor tins, Zaprawa enolofos, dimethylvinphos, crotoxyphos, SD-1750, heptenopos, Phosdrin, monocrotophos, naled, Chlorpyrifos 94, Pyrimithate, imino-formyl chloride sulphur phosphorus, omethoate, dioxathion, Nialate, Malathion, methacrifos, Phosalone, Volaton, methylpyrimidine sulphur phosphorus, Resitox, sulfotep, triazophos, vamidothion, isocarbophos, acephatemet, propetamphos, dialifos, R-1504, acrinathrin, bifenthrin, cyhalothrin, essence lambda-cyhalothrin, Fenvalerate, flucythrinate, flumethrin, taufluvalinate, brofluthrinate, Bifenazate, fenothiocarb, aldicarb, butocarboxim, oxamyl, Talcord, thiofanox, F-1991, sok, carbofuran, carbosulfan, meta-tolyl-N-methylcarbamate (MTMC), promacyl, formetanate, single carbonamidine, medimeform, amitraz, chlordimeform, peruscabin, bromopropylate, cyflumetofen, acequinocyl, Nissol, flufenoxuron, macro tetrolide, piericidin, thuringiensin, tetranactin, macro tetrolide, Avrmectin, doractin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, nimbin, tubatoxin, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spiral shell mite ester, Fluacrypyrim, Ovotran, propargite, any one or two kinds of pharmaceutical agent combinations in pyridaben are prepared into miticide and do harm to for preventing and treating agricultural and forestry and gardening plant mite, of the present inventionly contain 1, pyridine derivatives I total mass percentage in the composition of 2,3-thiadiazoles is 1%-90%, of the present inventionly contains 1, the pyridine derivatives I of 2,3-thiadiazoles and the ratio of above-mentioned medicament are mass percent 1%: 99% to 99%: 1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, with the seed of coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, plant during composition for preventing and controlling agricultural and forestry and gardening plant mite do harm to is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape, the mite evil that composition is suitable for is phytophagy evil mite, phytophagy evil mite be selected from tetranychid and Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae harmful mite and Panonychus citri belongs to, tetranychus telarius belongs to and these global Agricultural Mites of itch mite of Eriophyidae, forestry harmful mites, the harmful mite of gardening and the harmful mite of health.
Embodiment 7
Pyridine derivatives I and the application of antimicrobial combination in controlling plant diseases containing 1,2,3-thiadiazoles of the present invention
Of the present invention all contain 1,2,3-thiadiazoles pyridine derivatives I and existing sterilant as diazosulfide, tiadinil, is abbreviated as TDL, tisocromide, first thiophene lures amine, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, DL-beta-aminobutyric acid, isotianil, it is English general by name: isotInil, , 4-bis-chloroisothiazole-5-formic acid, 3,4-bis-chloroisothiazole-5-sodium formiate, 3,4-bis-chloroisothiazole-5-ethyl formate, virazole, antofine, Ningnanmycin or Whitfield's ointment, frost urea cyanogen, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, flumorph, dimethomorph, mefenoxam, benalaxyl-M, two chlorine zarilamid, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, fultolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, RP-26019, Azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, Strobilurin, oxime bacterium ester, enostroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, SN-108266, difenoconazole, olefin conversion, efficient olefin conversion, epoxiconazole, RH-7592, fluquinconazole, fluzilazol, flutriafol, own azoles alcohol, imibenconazole, plant bacterium azoles, metconazole, nitrile bacterium azoles, Topaze, Wocosin 50TK, prothioconazoles, simeconazoles, tebuconazole, tertraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, fuberidazole, imazalil, efficient imazalil, prochloraz, fluorine bacterium azoles, cyazofamid, fenamidone, Evil imidazoles, pefurazoate, famoxadone, SYP-Z048, hymexazo, the spirit of Evil frost, Guardian, etridiazole, octhilinone, benthiozole, dodemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, boscalid amine, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, fenarimol, nuarimol, chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, iprobenfos, pyrazophos, tolclofosmethyl, miewensu, kasugamycin, polyoxin, Polyoxin, validamycin, jingganmycin, Streptomycin sulphate, metaxanin, furalaxyl, M 9834, ofurace, mebenil, derosal, F-1991, thiophanate_methyl, triazolone, bupirimate, dimethirimol, the phonetic phenol of second, Difolatan, Vancide 89, Phaltan, Vinclozoline, fluoromide, dimetachlone, m-tetrachlorophthalodinitrile, isoprothiolane, Kitazine, bismerthiazol, quintozene, zinc 1,2-propylene bisdithiocarbamate, fosetylaluminium, sulphur, Bordeaux mixture, copper sulfate, copper oxychloride, Red copper oxide, copper hydroxide, metrafenone, pencycuron, diclomezin, phthalide, pyroquilon, volution bacterium amine, tricyclazole, triforine, the pyridine of many fruits, the pungent salt of biguanides, iminoctadine, dicloran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, methyl iodide, metamsodium, enemy's line ester, dazomet, dichloroisopropyl ether, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, ethoprophos, dichlofenthion, isazofos, fosthietan, oxamyl, aldicarb, carbofuran, sulfuryl fluoride, dichloropropylene, dichloro-isonicotinic acid, other known any any one or two kinds that can be used as in sterilant such as allyl isothiazole combinationally use for preventing and treating agricultural and forestry and gardening plant disease, of the present inventionly contain 1, pyridine derivatives I total mass percentage in the composition of 2,3-thiadiazoles is 1%-90%, of the present inventionly contains 1, the pyridine derivatives I of 2,3-thiadiazoles and the ratio of aforementioned sterilant are mass percent 1%: 99% to 99%: 1%, the prevention effect of composition is good, and these compositions have certain synergism and summation action, does not find the composition with antagonistic action, above-mentioned composition may be used for the control of agricultural plants disease and gardening plant disease, the Achyla, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, Pseudoperonospora, Peronospora etc. more than 20 that controlling object comprises Oomycete belongs to the disease produced, as other diseases etc. of the plurality of cereals crops such as seedling blight of rice, tomato root maize ear rot, the late blight of potato, black shank, millet Powdery Mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose, cash crop, gardening plant and forestry plant, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, with the seed of coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent.These compositions comprise cereal for preventing and treating plant applicable in agricultural and forestry and gardening plant disease: paddy, wheat, barley, oat, corn, millet, Chinese sorghum; Tuber crops: sweet potato, potato, cassava; Beans: soybean, broad bean, pea, mung bean, red bean and fiber: cotton, crudefiber crop, silkworm and mulberry; Oil plant: peanut, rape, sesame, soybean, Sunflower Receptacle; Sugar material: beet, sugarcane; Beverage: tealeaves, coffee, cocoa; Hobby: tobacco leaf; Medicinal: ginseng, the bulb of fritillary; The torrid zone: rubber, coconut, oil palm, sisal hemp; Food crop and fruit, flowers, oil plant, sugar material and cotton, fiber crops, tea, tobacco, Chinese medicinal materials cash crop and plant melon, really, tea, silkworm and mulberry, vegetables, containing various wild vegetable, bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, seedling and other garden crop garden crops as tobacco: flue-cured tobacco, air-curing of tobacco leaves, suncured tabacco; Vegetables, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, melon: watermelon, muskmelon, hami melon, pawpaw; Beans: soybean, broad bean, pea-pods; Potato, wheat, corn, paddy rice, peanut, fruit tree: apple, banana, citrus, peach, papaya; Flowers: orchid; Potted landscape; Composition improves the defence capability of plant while sterilization, makes plant create defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 8
Of the present invention contain 1,2,3-thiadiazoles pyridine derivatives I and antiviral agent be combined in the application prevented and treated in viral diseases of plants
Of the present inventionly contain 1, 2, the pyridine derivatives I of 3-thiadiazoles and existing Antiphytoviral medicament diazosulfide, tiadinil, be abbreviated as TDL, isotianil, it is English general by name: isotInil, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-sodium formiate, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-ethyl formate, 3, 4-bis-chloroisothiazole-5-formic acid, 3, 4-bis-chloroisothiazole-5-sodium formiate, 3, 4-bis-chloroisothiazole-5-ethyl formate, DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lures amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, in jingganmycin, any 1 or 2 compound combinations are for preventing and treating agricultural and forestry and gardening plant virus disease, the disease of control agricultural and forestry and gardening plant virus disease is selected from tobacco mosaic virus disease, various melon virus disease, various solanaceous vegetables virus disease, beans virus disease, Cruciferae virus disease, grain and oil crop virus disease, any one in cotton virus disease and various fruit tree virus disease, wherein endanger serious being selected from: tobacco virus, peppery pimento virus disease, tomato virus disease, Chinese cabbage virus disease, Virus Diseases of Rice comprises rice dwarf virus disease, yellow dwart, stripe virus disease, fern leaf of tomato viral disease, pepper mosaic virus disease viral disease and tobacco veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, oranges and tangerines virus disease, cymbidium mosaic virus, any one in cybidium ring spot virus.These compositions are selected from paddy for the plant preventing and treating agricultural and forestry and gardening plant virus disease, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, the agriculturals such as potted landscape, gardening, economical, the plants such as forestry, the use of these compositions makes the immunizing power of crop self improve, while producing the control of insect especially infection insect, produce the defence capability to viral diseases of plants induction of plant, also can produce the direct prevention effect of virus disease, therefore, these compositions may be used for preparation and the purposes of Antiphytoviral medicament and inducing plant Antiphytoviral medicament.Of the present inventionly contain 1, pyridine derivatives I total mass percentage in the composition of 2,3-thiadiazoles is 1%-90%, of the present inventionly contains 1, the pyridine derivatives I of 2,3-thiadiazoles and the ratio of aforementioned Antiphytoviral medicament are mass percent 1%: 99% to 99%: 1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, with the seed of coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, all show addition or synergism between these compositions, while maintenance insecticidal activity, its antiviral activity is all greater than the effect that any one compound is used alone, find no the composition of antagonistic action, the drug effect lasting period of composition is long.
Embodiment 9
Of the present inventionly contain the pyridine derivatives I of 1,2,3-thiadiazoles and the complete processing of commercially available agricultural chemical compound preparation and stability
Of the present inventionly contain 1, 2, the pyridine derivatives I of 3-thiadiazoles and the mixture complete processing of commercially available agricultural chemical are in table 5, from table 5, most medicament all can be processed according to the method for statement, the main component of liquid preparation is effective constituent and solubility promoter and tensio-active agent, synergistic agent, antifreezing agent, stablizer, other the component etc. such as thickening material or permeate agent, the composition of solid preparation mainly includes effect composition, other agriculturally acceptable adjuvant components such as tensio-active agent and filler, the cold storage test of process preparation, liquid preparation places 1 week without Precipitation at 0 ± 2 degree Celsius, solid preparation is placed 2 weeks at 54 ± 2 degrees Celsius, there is not caking phenomenon in medicament, all formulation storage place the medicament drug effect of front and back without significant difference, the rate of decomposition of composition effective constituent is within 5%, composite preparation qualified stability.
Table 1 chemical structure and the physical and chemical parameter containing the pyridine derivatives I of 1,2,3-thiadiazoles of the present invention
Table 2 is containing the fungicidal activity (/ %) of the pyridine derivatives I of 1,2,3-thiadiazoles
Numbering |
Compound number |
AS |
CA |
GZ |
PP |
BC |
SS |
RC |
PS |
PI |
1 |
Hxw002-12 |
45.00 |
43.75 |
35.29 |
50.00 |
51.35 |
27.27 |
51.28 |
63.38 |
20.69 |
2 |
Hxw002-13 |
10.00 |
12.50 |
17.65 |
34.38 |
35.14 |
31.82 |
41.03 |
46.48 |
13.79 |
Data are the measurement result of 50 mcg/ml; AS: tomato early blight bacterium (AlternarI solani); BC: botrytis cinerea pers (Botrytiscinerea); CA: peanut Cercospora bacteria (Cercospora arachidicola); GZ: fusarium graminearum (Gibberella zeae); PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary); PP: Botryosphaeria berengeriana f. sp (Physalospora piricola); PS: Rhizoctonia solani Kuhn (PellicularI sasakii); RC: Rhizoctonia cerealis (RhizoctonI cerealis); SS: Sclerotinia sclerotiorum (SclerotinI sclerotiorum).
Table 3 is containing the pyridine derivatives I insecticidal activity (mythimna separata, 48h mortality ratio/%) of 1,2,3-thiadiazoles
Sequence number |
Compound |
200 mcg/ml |
1 |
Hxw002-12 |
25 |
2 |
Hxw002-13 |
65 |
3 |
Cyanogen insect amide |
100 |
4 |
Blank |
0 |
Table 4 is containing the pyridine derivatives I of 1,2,3-thiadiazoles
The activity (inhibiting rate/% of 100 mcg/ml) of resisting tobacco mosaic virus
Numbering |
Compound |
Therapeutic activity ± SD |
Inactivate activity ± SD |
Prolection ± SD |
Induced activity ± SD |
3 |
Hxw002-12 |
29.27±4.88 |
15.71±5.79 |
13.10±5.90 |
20.54±5.24 |
4 |
Hxw002-13 |
41.05±3.73 |
44.45±4.79 |
16.27±4.18 |
25.19±5.50 |
5 |
TDL |
22.36±5.50 |
32.57±5.18 |
30.55±2.99 |
52.32±4.19 |
6 |
Ningnanmycin |
49.59±1.86 |
48.66±4.03 |
48.81±3.57 |
39.53±4.19 |
7 |
Virazole |
42.27±4.28 |
48.66±5.78 |
44.45±4.18 |
39.15±2.92 |
Table 5 is containing the pyridine derivatives of 1,2,3-thiadiazoles
The working method that I is mixed with commercially available agricultural chemical