Summary of the invention
Technical problem to be solved by this invention is: provide novel and contain 1,2, the pyridine derivatives of 3-thiadiazoles and synthetic method thereof, biological activity and the measuring method thereof of this compounds regulation and control agricultural, gardening and health and forestry plant insect and pathogen are provided, the application of these compounds in agriculture field, gardening field, field of forestry and health field is provided.
The present invention solves this technical problem the technical scheme that adopts: what have that agriculture field, gardening field, forestry and health field insecticidal activity, fungicidal activity, anti-phytoviral activity, inducing plant produce anti-disease activity, insect growth regulator activity contains 1, the chemical structure of general formula of the pyridine derivatives of 2,3-thiadiazoles is seen formula I:
General formula I:
Wherein, R
1Be selected from: replace saturated alkyl, replace unsaturated alkyl, substituted pyridinyl; R
1Preferably: methyl, dihydro substituted pyridinyl; R
2Be selected from: replace saturated alkyl, replace unsaturated alkyl, substituted pyridinyl; R
2Preferably: methyl, dihydro substituted pyridinyl; X is selected from: O, S; X is preferred: S.
The route that the pyridine derivatives I that contains 1,2,3-thiadiazoles of the present invention presses Scheme-1 synthesizes:
Wherein, R
1Be selected from: replace saturated alkyl, replace unsaturated alkyl, substituted pyridinyl; R
1Preferably: methyl, dihydro substituted pyridinyl; R
2Be selected from: replace saturated alkyl, replace unsaturated alkyl, substituted pyridinyl; R
2Preferably: methyl, dihydro substituted pyridinyl; X is selected from: O, S; X is preferred: S.
Scheme-1 contains the pyridine derivatives I synthetic route of 1,2,3-thiadiazoles
Specifically be divided into following steps:
A. contain the preparation of the pyridine compounds and their I of 1,2,3-thiadiazoles:
In 50 milliliters of round-bottomed flasks, add successively 3.90 mmole 4-and replace thiadiazoles-5-formaldehyde or 5-replacement thiadiazoles-4-formaldehyde, 7.80 mmole replaces methyl aceto acetate, 3.90 mmole ammonium acetate, 0.39 mmole aluminum trichloride (anhydrous), 10 milliliters of ethanol, reflux stirs, the TLC monitoring reaction, after question response is finished, underpressure distillation desolventizing ethanol, residuum volume ratio ethyl acetate: water=dissolving in 1: 1, organic layer is water successively, the saturated sodium bicarbonate washing, anhydrous sodium sulfate drying, column chromatography purification must contain 1,2, the pyridine compounds and their I of 3-thiadiazoles, the washing and dehydrating integrated machine volume ratio is 60~90 degrees centigrade of sherwood oils: ethyl acetate=5: 1, with gained sterling calculated yield; The amount of synthetic compound enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles; The described pyridine compounds and their I that contains 1,2,3-thiadiazoles is selected from: 2,6-dimethyl-4-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-Isosorbide-5-Nitrae-dihydropyridine-3,5-dicarboxylate; 2,6-dimethyl-4-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-Isosorbide-5-Nitrae-dihydropyridine-3, the 5-dicarboxylate.
B. the pyridine derivatives I of 1,2,3-thiadiazoles that contains of the present invention is to the mensuration of mythimna separata insecticidal activity:
Of the present inventionly contain 1,2, the pyridine derivatives I of 3-thiadiazoles adopts leaf dipping method to the screening of mythimna separata insecticidal activity: take by weighing 2 milligrams of medicine samples in 10 ml penicillin vials at analytical balance, add 10 milliliters of acetone, become the mother liquor of 200 mcg/ml, cover plug vibration dissolving, then liquid is become the working fluid of 5 mcg/ml with acetone diluted, with straight peen ophthalmology tweezers soaking maize blade, 2~3 seconds time, get rid of remaining liquid.Each 1, totally 8 in each sample; Be successively placed on the treatment paper by the sample flag sequence, after doing, liquid puts into the markd 10 centimetres culture dish of tool, with armyworm larvae at the beginning of elbow ophthalmology tweezers accesses 10 3 ages, to test to process places constant temperature standard insectary to cultivate check result after 24 hours or 48 hours, touch the larva body with little writing brush or tweezers, fully motionless as death standard take larva; With the positive contrast of cyanogen insect amide, the leaf of Semen Maydis of flooding with acetone soln is blank.
C. the pyridine derivatives I of 1,2,3-thiadiazoles that contains of the present invention is to the mensuration of pathogenic fungi fungicidal activity:
Of the present inventionly contain 1,2, the pyridine derivatives I sterilization of 3-thiadiazoles or bacteriostatic activity adopt thalli growth rate assay method, detailed process is: get 5 milligrams of sample dissolution at an amount of N, in the N dimethyl formamide, then with containing the medicament that a certain amount of polysorbas20 emulsifier aqueous solution is diluted to 500 mcg/ml, reagent agent is respectively drawn under aseptic condition in 1 milliliter of injection culture dish, add respectively again 9 milliliters of substratum, make 50 mcg/ml pastilles after shaking up dull and stereotyped, do blank with the flat board that adds 1 milliliter of aqua sterilisa, punch tool with 4 millimeters of diameters cuts the bacterium dish along the mycelia outer rim, move on the pastille flat board, being equilateral triangle puts, every processing repeats 3 times, culture dish is placed on cultivation in 24 ± 1 degrees centigrade of constant incubators, colony diameter to be contrasted expands to 2-3 centimetre of " Invest, Then Investigate " and respectively processes bacterium dish expansion diameter, average, relatively calculate relative bacteriostasis rate with blank, comprise the kind of multiple representative majority of plant pathogenic bacteria of the actual generation in field in China's agriculture production for the examination bacterial classification, its title and code name comprise AS: tomato early blight bacterium (AlternarI solani); BC: botrytis cinerea pers (Botrytis cinerea); CA: peanut Cercospora bacteria (Cercospora arachidicola); GZ: fusarium graminearum (Gibberella zeae); PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary); PP: Botryosphaeria berengeriana f. sp (Physalosporapiricola); PS: Rhizoctonia solani Kuhn (PellicularI sasakii); RC: Rhizoctonia cerealis (RhizoctonI cerealis); SS: Sclerotinia sclerotiorum (SclerotinI sclerotiorum).
D. the mensuration that contains the pyridine derivatives I inducing anti-disease activity of 1,2,3-thiadiazoles of the present invention:
The active screening method of pyridine derivatives I evoking tobacco resisting tobacco mosaic virus (TMV) that contains 1,2,3-thiadiazoles of the present invention is:
(1). the agent of standard activating plants: selecting tiadinil (TDL) (purity is greater than 99.5%) is the activating plants agent of standard;
(2). contain the screening method of the anti-TMV activity of pyridine derivatives I evoking tobacco of 1,2,3-thiadiazoles: the mensuration of the direct antiviral activity that exsomatizes adopts half leaf method to carry out; It is the common cigarette that seedling age is consistent that live body is induced, 3 basins are one group, cigarette seedling respectively at inoculation pre-treatment in front 7 days, processing mode comprises: spray test compound solution 2 to 3 times, each 10 milliliters, or soil treatment, each 10 milliliters, measuring concentration is 50 mcg/ml, the 7th day frictional inoculation TMV on the tobacco leaf that newly grows, with the cigarette seedling place cultivate 3 days under its growth optimal temperature and illumination after, check incidence, comprehensive scab number is calculated as follows out test compound to the inducing anti-disease toxic effect fruit of TMV, and 3 repetitions are established in each processing, and water and TDL are selected respectively in blank and the contrast of standard medicament:
Wherein, R is that new compound is to the effect of inducing of Resistance In Tobacco TMV, unit: %; CK is the average withered spot number of clear water contrast blade, unit: individual; I is for inducing the average withered spot number of processing rear blade, unit: individual through compound.
The invention has the beneficial effects as follows: the present invention is to containing 1,2, the pyridine derivatives I of 3-thiadiazoles has carried out the optimization of guide structure, and synthetic new compound carried out the mensuration of desinsection, antibacterial and inducing anti-disease activity, anti-phytoviral activity and mixed the research of using, this compounds can be used for disease, insect pest and the virus disease control in agriculture field, field of forestry, gardening field.
The present invention will by specific preparation and biological activity determination and with formulation that commercially available agricultural chemical is used in combination complete processing and selection be that embodiment more specifically describes and contains 1,2, synthetic and biological activity and the application thereof of the pyridine derivatives I of 3-thiadiazoles, but described embodiment only is used for specific description the present invention and unrestricted the present invention, especially its biological activity and complete processing only illustrate, and unrestricted this patent, embodiment is as follows:
Embodiment 1
2,6-dimethyl-4-replaces thiadiazolyl group-Isosorbide-5-Nitrae-dihydropyridine-3, and the 5-dicarboxylate is synthetic:
In 50 milliliters of round-bottomed flasks, add successively 3.90 mmole 4-and replace thiadiazoles-5-formaldehyde, 7.80 mmole replaces methyl aceto acetate, 3.90 mmole ammonium acetate, 0.39 mmole aluminum trichloride (anhydrous), 10 milliliters of ethanol, reflux stirs, the TLC monitoring reaction, after question response is finished, underpressure distillation desolventizing ethanol, residuum volume ratio ethyl acetate: water=dissolving in 1: 1, organic layer is water successively, the saturated sodium bicarbonate washing, anhydrous sodium sulfate drying, column chromatography purification, the washing and dehydrating integrated machine volume ratio is 60~90 degrees centigrade of sherwood oils: ethyl acetate=5: 1, yield 64.96%; The amount of synthetic compound enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles; 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-replaces thiadiazolyl group-Isosorbide-5-Nitrae-dihydropyridine-3, the 5-dicarboxylate is selected from 2,6-dimethyl-4-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1,4-dihydropyridine-3,5-dicarboxylate, 2,6-dimethyl-4-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-and Isosorbide-5-Nitrae-dihydropyridine-3, the 5-dicarboxylate.Wherein, 2,6-dimethyl-4-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-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-yl)-Isosorbide-5-Nitrae-dihydropyridine-3, the 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 sees Table 1.
Embodiment 2
Antibacterial or the fungicidal activity that contains 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 the field occurs in the agriculture production.Thalli growth rate method measurement result sees Table 2, and data show, when 50 mcg/ml, all compounds that the present invention synthesizes all have fungicidal activity in various degree, and Hxw002-12 is higher than 40% to the fungicidal activity of AS; Hxw002-12 is higher than 40% to the fungicidal activity of CA; Hxw002-12 is higher than 40% to the fungicidal activity of PP; Hxw002-12 is higher than 40% to the fungicidal activity of BC; Hxw002-12, Hxw002-13 are higher than 40% to the fungicidal activity of RC; Hxw002-12, Hxw002-13 are higher than 40% to the fungicidal activity of PS.Therefore, this compounds has shown preferably fungicidal activity
Embodiment 3
The insecticidal activity that contains the pyridine derivatives I of 1,2,3-thiadiazoles of the present invention
The pyridine derivatives I that contains 1,2,3-thiadiazoles of the present invention the results are shown in Table 3 to the insecticidal activity assay of small cabbage moth, data show when 200 mcg/ml, Hxw002-13 of the present invention is 65% to the insecticidal activity of mythimna separata, therefore, compound exhibits of the present invention insecticidal activity preferably.
Embodiment 4
The effect of the anti-Resistance In Tobacco tobacco mosaic virus (TMV) of the pyridine derivatives I that contains 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 of the present invention and Hxw002-13 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 is substantially suitable with virazole with contrast medicament Ningnanmycin, therefore, compound exhibits of the present invention preferably activity and the induced activity of anti-TMV.
Embodiment 5
Pyridine derivatives I and the application of insecticide composition in the control insect pest of the plant that contains 1,2,3-thiadiazoles of the present invention
Of the present invention all contain 1,2, the pyridine derivatives I of 3-thiadiazoles and existing sterilant: Chlorpyrifos 94, the inferior Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, efficient fenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, the Beta-cyfloxylate, cyfloxylate, the 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, young urea goes out, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, the pyridine worm is grand, lufenuron, the poisonous insect urea, penfluron, Noviflumuron is noviflumuron, and its CAS number is 121451-02-3, flucycloxuron, Novaluron is Rimon, fluorine pyridine urea, Bay sir 6874 i.e. { 1-[(3.5-two 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 is bistrifluron, furan tebufenozide, the 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, the desinsection list, disosultap, chlorantraniliprole, Flubendiamide, the fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, the young ketone of rattling away, Nylar, in the emaricin etc. any one or two kinds are used in combination for control agricultural and forestry and gardening plant insect pest; Of the present inventionly contain 1, the quality percentage composition of the pyridine derivatives I of 2,3-thiadiazoles in composition 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, the upper acceptable solvent of agricultural and emulsifying agent and solubility promoter and synergistic agent etc. are arranged in the preparation of composition, and the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine lacquer, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, plant the clothing agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, in the steam releasing agent any one; The insect pest that can prevent and treat mainly contains red spider, Asiatic migrotory locust, clouding car locust, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, the east mole cricket, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian manages 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, the flat angle of sugarcane 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, the 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, the 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), the 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, the straight burr rice hesperiidae, pelopidas mathias, the oranges and tangerines swallowtail butterfly, Common Mormon, small white, pyrameis indica, the yellow a kind of butterfly harmful to crop plants of ramie, the beans blister beetle, the 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, the 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, the yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm is hanged the cocoon ichneumon wasp, bollworm tooth lip ichneumon wasp, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, the melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, the black fly of diving of beans stalk, frit fly, plant fly, onion fly, the radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm lacks Agricultural pests such as must posting fly, forestry pest; Plant in control agricultural and forestry and the 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 has improved the defence capability of plant in desinsection, make plant produce defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 6
Pyridine derivatives I and the miticide that contains 1,2,3-thiadiazoles of the present invention is combined in the application that prevents and treats in the plant mites evil
Of the present inventionly contain 1, the pyridine derivatives I of 2,3-thiadiazoles and the upper acceptable auxiliary agent of agricultural 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, the Malathion, methacrifos, Phosalone, Volaton, methylpyrimidine sulphur phosphorus, Resitox, sulfotep, triazophos, vamidothion, isocarbophos, acephatemet, propetamphos, dialifos, R-1504, acrinathrin, bifenthrin, cyhalothrin, the 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, in the pyridaben any one or two kinds of medicament combinations are prepared into miticide and are used for control agricultural and forestry and gardening plant mite evil; Of the present inventionly contain 1, the total quality percentage composition of the pyridine derivatives I of 2,3-thiadiazoles in composition 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, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine lacquer, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, plant the clothing agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, in the steam releasing agent any one; Plant in composition for preventing and controlling agricultural and forestry and the gardening plant mite evil 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 applicable mite evil of composition is phytophagy evil mite, and it is that the harmful mite of Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae is that 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 that phytophagy evil mite is selected from tetranychid.
Embodiment 7
The pyridine derivatives I that contains 1,2,3-thiadiazoles of the present invention and sterilant are combined in the application in the controlling plant diseases
of the present invention own pyridine derivatives I and existing bactericide such as the diazosulfide that contains 1,2,3-thiadiazoles, tiadinil, be abbreviated as TDL, tisocromide, the first thiophene lures amine, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formate, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-Ethyl formate, the DL-beta-aminobutyric acid, isotianil, it is English general by name: isotInil, , 4-bis-chloroisothiazoles-5-formic acid, 3,4-, bis-chloroisothiazoles-5-sodium formate, 3,4-, bis-chloroisothiazoles-5-Ethyl formate, virazole, antofine, Ningnanmycin or salicylic acid, frost urea cyanogen, thiram, ziram, Mancozeb, aliette, thiophanate-methyl, Bravo, the enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, flumorph, dimethomorph, efficient metalaxyl, efficient M 9834, two chlorine zarilamids, flusulfamide, the first flusulfamide, thiophene fluorine bacterium amine, flutolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, the pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, iprodione, Fluoxastrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, pyraclostrobin, oxime bacterium ester, Enestroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, Cyproconazole, Difenoconazole, alkene azoles alcohol, efficient alkene azoles alcohol, epoxiconazole, RH-7592, Fluquinconazole, Flusilazole, Flutriafol, own azoles alcohol, glyoxalin, plant the bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Triadimenol, triticonazole, bitertanol, probenazole, furidazol, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid, Fenamidone, the Evil imidazoles, pefurazoate, famoxadone, SYP-Z048, hymexazo, the spirit of Evil frost, Guardian, Grandox fumigant, octhilinone, benthiozole, dodemorph, butadiene morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, Boscalid, fluopicolide, pyridine bacterium amine, cyprodinil, the fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, Fenarimol, nuarimol, chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, the benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, IBP, pyrazophos, tolelofos-methyl, blasticidin-S, kasugarnycin, polyoxin, Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, mebenil, carbendazim, benomyl, thiophanate-methyl, triazolone, bupirimate, dimethirimol, the phonetic phenol of second, difoltan, captan, folpet, vinclozolin, fluoromide, dimethachlon, Bravo, Isoprothiolane, kitazine, Yekuzuo, pentachloronitrobenzene, Propineb, phosethyl-Al, sulphur, Bordeaux mixture, copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone, Pencycuron, diclomezin, Rabcide, pyroquilon, volution bacterium amine, tricyclazole, triforine, the pyridine of many fruits, the hot salt of biguanides, iminoctadine, botran, the benzene flusulfamide, the toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane, metham-sodium, enemy's line ester, dazomet, nemamort, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, phonamiphos, dichlofenthion, isazofos, fosthietan, oxamyl, Aldicarb, carbofuran, vikane, dichloropropylene, dichloro-isonicotinic acid, other known any any one or two kinds that can be used as in bactericide such as allyl isothiazole are used in combination be used to preventing and treating agricultural and forestry and gardening plant disease, of the present inventionly contain 1, the total quality percentage composition of the pyridine derivatives I of 2,3-thiadiazoles in composition is 1%-90%, of the present inventionly contains 1, the pyridine derivatives I of 2,3-thiadiazoles and the ratio of aforementioned bactericide are mass percent 1%: 99% to 99%: 1%, the prevention effect of composition is good, and these compositions have certain synergistic effect and summation action, does not find to have the composition of antagonistic action, above-mentioned composition can be for the control of agricultural plant disease and gardening plant disease, controlling object comprises that more than 20 of the Achylas, Aphanomyces, pythium, Phytophthora, Sclerospora, Plasmopara, Pseudoperonospora, Peronospora of Oomycete etc. belong to the diseases that produce, as other diseases of plurality of cereals crop, industrial crops, gardening plant and the forestry plants 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 etc., the formulation of composition processing is selected from sustained release agent, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspension emulsion, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke agent, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, fine granule, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, liniment, the fritter poison bait, suspending agent, suspended emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in the steam releasing agent.These compositions are used for control agricultural and forestry and the applicable plant of gardening plant disease and comprise cereal: 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, contain various wild vegetable, bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, seedling and other garden crop garden crop such 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 has improved the defence capability of plant in sterilization, make plant produce defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 8
Pyridine derivatives I and the antiviral agent that contains 1,2,3-thiadiazoles of the present invention is combined in the application that prevents and treats in the 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, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, 3,4-two chloroisothiazoles-5-formic acid, 3,4-, two chloroisothiazoles-5-sodium formiate, 3,4-, two chloroisothiazoles-5-ethyl formate, the DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, the first thiophene lures amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, any 1 or 2 compound combinations are used for control agricultural and forestry and gardening plant virus disease in the jingganmycin; The disease of control agricultural and forestry and gardening plant virus disease is selected from tobacco mosaic virus disease, various melon virus diseases, various solanaceous vegetables virus diseases, the beans virus disease, the Cruciferae virus disease, the grain and oil crop virus disease, any in cotton virus disease and the 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, the fern leaf of tomato viral disease, pepper mosaic virus disease viral disease and tobacco veinal necrosis virus are sick, maize dwarf mosaic, cauliflower mosaic virus, the oranges and tangerines virus disease, cymbidium mosaic virus, any in the cybidium ring spot virus.The plant that these compositions are used for control agricultural and forestry and gardening plant virus disease 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, the agriculturals such as potted landscape, gardening, economical, the plants such as forestry; The use of these compositions has been induced the defence capability of plant generation to viral diseases of plants so that the immunizing power of crop self improves when producing the control of insect especially infection insect; Also can produce the direct prevention effect of virus disease; Therefore, these compositions can be used for preparation and the purposes of Antiphytoviral medicament and inducing plant Antiphytoviral medicament.Of the present inventionly contain 1, the total quality percentage composition of the pyridine derivatives I of 2,3-thiadiazoles in composition 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, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine lacquer, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, plant the clothing agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, in the steam releasing agent any one; All show addition or synergism between these compositions, when keeping insecticidal activity, the effect that its antiviral activity all uses separately greater than any one compound; Find no the composition of antagonistic action, the drug effect lasting period of composition is long.
Embodiment 9
Complete processing and the stability that contains pyridine derivatives I and the commercially available agricultural chemical compound preparation of 1,2,3-thiadiazoles of the present invention
Of the present inventionly contain 1,2, the pyridine derivatives I of 3-thiadiazoles and the mixture complete processing of commercially available agricultural chemical see Table 5, by as seen 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 the effect composition, the upper acceptable adjuvant component of other agriculturals such as tensio-active agent and filler, the cold storage test of process preparation, liquid preparation placed for 1 week without Precipitation at 0 ± 2 degree centigrade, solid preparation placed for 2 weeks at 54 ± 2 degrees centigrade, caking phenomenon does not appear in medicament, all preparations store the medicament drug effect of placement front and back without significant difference, the rate of decomposition of composition effective constituent in 5%, the composite preparation qualified stability.
Table 1 chemical structure and the physical and chemical parameter that contains the pyridine derivatives I of 1,2,3-thiadiazoles of the present invention
Table 2 contain the pyridine derivatives I of 1,2,3-thiadiazoles fungicidal activity (/ %)
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 contains pyridine derivatives I insecticidal activity (mythimna separata, the 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 contains the pyridine derivatives I of 1,2,3-thiadiazoles
The activity of resisting tobacco mosaic virus (inhibiting rate of 100 mcg/ml/%)
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 |
[0065]Table 5 contains the pyridine derivatives of 1,2,3-thiadiazoles
The working method that I and commercially available agricultural chemical are used with