CN103012391B - Pyrimidine derivatives containing 1,2,3-thiadiazole, and preparation method and application thereof - Google Patents

Abstract

The invention provides pyrimidine derivatives containing 1.2,3-thiadiazole, and a preparation method and application thereof. The invention relates to heterocyclic compounds containing 1.2,3-thiadiazole, which have the chemical structure general formula disclosed as I. The invention discloses a structural general formula of the compounds, a synthesis method, application to insecticides, bactericides, plant-virus resisting agents and plant activators, and a processing technique for preparing insecticides, bactericides, plant-virus resisting agents and plant activators by mixing the compounds with agriculturally acceptable assistants or synergists. The invention also discloses application of the compounds in combination with commercial pesticides, bactericides, plant-virus resisting agents and plant activators in preventing and treating diseases, insect pests and virus diseases in agriculture, forestry and horticulture, and a preparation method thereof.

Description

One class contains pyridine derivatives of 1,2,3-thiadiazoles and its production and use

Technical field

Technical scheme of the present invention relates to 1,2,3-thiadiazole compound, is specially and contains the pyridine derivatives of 1,2,3-thiadiazoles.

Background technology

Dihydropyrimidinonesand (DHPMs) and derivative thereof have biological activity widely due to it, have caused people in recent years and have paid close attention to greatly.3,4-dihydropyrimidinones is as heterocycle compound, play a very important role at medicinal chemistry art tool, there is shown the effects such as well antiviral, antitumor, anti-oxidant, sterilization, anti-inflammatory, simultaneously, dihydropyrimidinones also has biological activity widely, as α _1aadrenergic receptor antagonist, hypotensor, calcium ion channel blockor, mitotic kinesins Eg5 protein inhibitor etc., the compound of some natural selectivity AntiHIV1 RT activity is also found to have dihydropyrimidinonesand class formation (Medicinal Cgemistry Research (2012), 21 (12), 4506-4511).

1, 2, 3-thiadiazole compound has biological activity (Bakulev widely equally, et al.Newyork:John Wiley & Sons, Inc, 2004), about the research of thiadiazoles mainly concentrates on 1, 3, 4-thiadiazoles derivative, 1, 2, 5-thiadiazoles derivative and 1, 2, on 4-thiadiazoles derivative, and 1, 2, the research report of 3-thiadiazoles derivative activity is relatively less, medicine and agricultural chemicals in commercial kind few, what agriculture field was applied has cotton defoliant, disleave spirit (N-phenyl-N '-1, 2, 3-thiadiazoles-5-urea, TDZ), activating plants agent-Acibenzolar (phendioxin, 2,3-thiadiazoles-7-thiocarboxylic acid methyl esters, BTH), rice field sterilant-tiadinil (3 '-chloro-4,4 '-dimethyl-1,2,3-thiadiazoles-5-formylaniline, TDL).Contriver's design and synthesis in early stage has also found that first thiophene lures the inducing anti-disease activity of amine, at present just in industrialization development process.In order to find 1 of more high biological activity, 2,3-thiadiazole new compound, for New pesticides discovery research provides candidate compounds, the present invention is by 1,2,3-Thiadiazole is introduced in pyrimidines molecules, and design and synthesis one class is containing 1,2, the pyridine derivatives of 3-thiadiazoles, and the bioactive screening having carried out system.

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, this kind of compound modulates agricultural, the biological activity of gardening and health and forestry plant insect and pathogen and measuring method thereof are provided, the application of these compounds in agriculture field, horticultural field, field of forestry and health field is provided.

The present invention solves this technical problem adopted technical scheme: there is agriculture field, horticultural field, forestry and health field insecticidal activity, fungicidal activity, anti-phytoviral activity, inducing plant produce anti-disease activity, insect growth regulator activity containing 1, the chemical structure of general formula of the pyridine derivatives of 2,3-thiadiazoles is shown in formula I:

General formula I:

Wherein, R ¹be selected from: replace saturated alkyl, replace unsaturated alkyl, substituted pyrimidyl; R ¹preferred: methyl, tetrahydrochysene substituted pyrimidyl; R ²be selected from: replace saturated alkyl, replace unsaturated alkyl, substituted pyrimidyl; R ²preferred: methyl, tetrahydrochysene substituted pyrimidyl; X is selected from: O, S; X is preferred: S.

The pyridine derivatives I containing 1,2,3-thiadiazoles of the present invention presses the route synthesis of Scheme-1:

Wherein: R ¹be selected from: replace saturated alkyl, replace unsaturated alkyl, substituted pyrimidyl; R ¹preferred: methyl, tetrahydrochysene substituted pyrimidyl; R ²be selected from: replace saturated alkyl, replace unsaturated alkyl, substituted pyrimidyl; R ²preferred: methyl, tetrahydrochysene substituted pyrimidyl; X is selected from: O, S; X is preferred: S.

Scheme-1 is containing the pyridine derivatives I synthetic route of 1,2,3-thiadiazoles

Specifically be divided into following steps:

A. containing the preparation of the pyrimidines I of 1,2,3-thiadiazoles:

In 50 milliliters of round-bottomed flasks, add 3.9 mmole 4-successively replace that thiadiazoles-5-formaldehyde or 5-replace thiadiazoles-4-formaldehyde, 3.9 mmoles replace methyl aceto acetates, 5.86 mmole thiocarbamides, 0.07 gram of tosic acid, 5 milliliters of ethanol, stirring reaction 10 minutes under 80 degrees Celsius of microwave conditions, TLC controls reaction to carry out, underpressure distillation removing etoh solvent after completion of the reaction, residuum ethyl acetate: water=1: 1 dissolves, separate organic layer, use saturated NaHCO successively ₃, saturated common salt water washing, anhydrous sodium sulfate drying, column chromatography purification must containing the pyrimidines I of 1,2,3-thiadiazoles, and eluent volume ratio used 60 ~ 90 degrees Celsius of sherwood oils: ethyl acetate=3: 1, by gained sterling calculated yield; The amount of synthetic compound expands by corresponding proportion or reduces; The volume scale of respective reaction container or reduce; The described pyrimidines I containing 1,2,3-thiadiazoles is selected from: 2-sulfo--1,2,3,4-tetrahydrochysene-6-methyl-4-(4-methyl isophthalic acid, 2,3 ,-thiadiazoles-5-bases) pyrimidine-5-ethyl formate; 2-sulfo--1,2,3,4-tetrahydrochysene-6-methyl-4-(5-methyl isophthalic acid, 2,3 ,-thiadiazoles-4-bases) pyrimidine-5-ethyl formate.

B. the pyridine derivatives I containing 1,2,3-thiadiazoles 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: on analytical balance, take 2 milligrams of medicine samples in 10 ml penicillin vials, add 10 milliliters of acetone, become the mother liquor of 200 mcg/ml, cover plug vibration and dissolve, then liquid acetone diluted is become the working fluid of 5 mcg/ml, with straight peen ophthalmology tweezers soaking maize blade, 2 ~ 3 seconds time, get rid of remaining liquid.Each 1, totally 8, each sample; Be successively placed in treatment paper by sample flag sequence, the culture dish of markd 10 centimetres of tool is put into after liquid is done, armyworm larvae at the beginning of 10 3 ages is accessed with elbow ophthalmology tweezers, test process is placed in constant temperature standard insectary and cultivates check result after 24 hours or 48 hours, larva body is touched with little writing brush or tweezers, completely motionless for death standard with larva; Taking cyanogen insect amide as positive control, is blank by the leaf of Semen Maydis of acetone soln dipping.

C. the pyridine derivatives I containing 1,2,3-thiadiazoles 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 appropriate N, in N-dimethylformamide, then with the medicament being diluted to 500 mcg/ml containing a certain amount of polysorbas20 emulsifier aqueous solution, reagent agent is aseptically respectively drawn in 1 milliliter of injection culture dish, add 9 milliliters of substratum more respectively, 50 mcg/ml pastilles are made dull and stereotyped after shaking up, blank is done with the flat board adding 1 milliliter of aqua sterilisa, bacterium dish is cut along mycelia outer rim with the punch tool of diameter 4 millimeters, move on pastille flat board, put in equilateral triangle, often process repetition 3 times, culture dish is placed in 24 ± 1 degrees Celsius of constant incubators and cultivates, treat that contrast colony diameter expands to 2-3 centimetre of " Invest, Then Investigate " and respectively processes bacterium dish expansion diameter, average, compare with blank and calculate relative bacteriostasis rate, the kind of the majority of plant pathogenic bacteria of the actual generation in multiple representative field in China's agriculture production is comprised for examination bacterial classification, its title and code name comprise AS: tomato early blight bacterium (Alternaria 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 (pellicularia sasakii), RC: Rhizoctonia cerealis (Rhizoctonia cerealis), SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum).

D. the mensuration containing the pyridine derivatives I inducing anti-disease activity of 1,2,3-thiadiazoles of the present invention:

The screening method containing pyridine derivatives I evoking tobacco resisting tobacco mosaic virus (TMV) activity of 1,2,3-thiadiazoles of the present invention is:

(1). standard plant activator: select the activating plants agent that tiadinil (TDL) (purity is greater than 99.5%) is standard;

(2). the screening method containing the anti-TMV activity of pyridine derivatives I evoking tobacco of 1,2,3-thiadiazoles: the mensuration of in vitro directly antiviral activity adopts half leaf method to carry out, live body induction is by common cigarette consistent for seedling age, 3 basins are one group, respectively at the cigarette seedling of inoculation pre-treatment in first 7 days, processing mode comprises: spray test compounds solution 2 to 3 times, each 10 milliliters, or soil treatment, each 10 milliliters, measuring concentration is 50 mcg/ml, 7th day frictional inoculation TMV on the tobacco leaf newly grown, cultivate under cigarette seedling being placed in its growth optimal temperature and illumination after 3 days, check incidence, comprehensive scab number is calculated as follows out the inducing anti-disease toxic effect fruit of test compound to TMV, 3 repetitions are established in each process, blank and standard agent contrast select water and TDL respectively:

$R=\frac{\mathrm{CK}-I}{\mathrm{CK}}\×100$

Wherein, R is the inducing effect of new compound to Resistance In Tobacco TMV, unit: %; CK is the average withered spot number of clear water contrast blade, unit: individual; I is the average withered spot number through compound induction process rear blade, unit: individual.

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 desinsection, antibacterial and inducing anti-disease activity, the mensuration of anti-phytoviral activity and research used in combination have been carried out to the new compound of synthesis, this compounds can be used for agriculture field, field of forestry, the disease of horticultural field, insect pest and virus disease control.

The present invention will be that embodiment more specifically describes containing 1 by specific preparation and biological activity determination and with the formulation that commercially available agricultural chemical combinationally uses complete processing and selection, 2, the synthesis of the pyridine derivatives I of 3-thiadiazoles and biological activity and application thereof, but described embodiment is unrestricted the present invention for specific description the present invention only, especially its biological activity and complete processing only illustrate, and unrestricted this patent, embodiment is as follows:

Embodiment 1

2-replaces the preparation that-4-replaces thiadiazolyl group-1,2,3,4-tetrahydrochysene-6-methylpyrimidine-5-ethyl formate I

In 50 milliliters of round-bottomed flasks, add 3.9 mmole 4-successively replace-5-thiadiazoles aldehyde, 3.9 mmoles replacement methyl aceto acetates, 5.86 mmole thiocarbamides, 0.07 gram of tosic acid, 5 milliliters of ethanol, stirring reaction 10 minutes under 80 degrees Celsius of microwave conditions, TLC controls reaction to carry out, underpressure distillation removing etoh solvent after completion of the reaction, residuum ethyl acetate: water=1: 1 dissolves, separate organic layer, use saturated NaHCO successively ₃, saturated common salt water washing, anhydrous sodium sulfate drying, column chromatography purification obtain 2-replace-4-replace thiadiazolyl group-1,2,3,4-tetrahydrochysene-6-methylpyrimidine-5-ethyl formate I, eluent volume ratio used 60 ~ 90 degrees Celsius of sherwood oils: ethyl acetate=3: 1, yield 13%; The amount of synthetic compound expands by corresponding proportion or reduces; The volume scale of respective reaction container or reduce; The 2-utilizing 5-replacement thiadiazoles-4-formaldehyde to replace 4-replacement-5-thiadiazoles formaldehyde can prepare substituting group position exchange replaces-4-replacement thiadiazolyl group-1,2,3,4-tetrahydrochysene-6-methylpyrimidine-5-ethyl formate I; Described 2-replaces-4-and replaces thiadiazolyl group-1,2,3,4-tetrahydrochysene-6-methylpyrimidine-5-ethyl formate is selected from 2-sulfo--4-(4-methyl isophthalic acid, 2,3,-thiadiazoles-5-base)-1,2,3,4-tetrahydrochysene-6-methylpyrimidine-5-ethyl formate, 2-sulfo--4-(5-methyl isophthalic acid, 2,3,-thiadiazoles-4-base)-1,2,3,4-tetrahydrochysene-6-methylpyrimidine-5-ethyl formate.Wherein, 2-sulfo--4-(4-methyl isophthalic acid, 2,3 ,-thiadiazoles-5-bases)-1,2,3,4-tetrahydrochysene-6-methylpyrimidine-5-ethyl formate ¹h-NMR (400MHz/CDCl ₃) δ 5.65 (1H, s), 4.21 (2H, q), 2.75 (3H, s), 2.48 (3H, s), 1.29 (4H, t); 2-sulfo--4-(5-methyl isophthalic acid, 2,3 ,-thiadiazoles-4-bases)-1,2,3,4-tetrahydrochysene-6-methylpyrimidine-5-ethyl formate ¹h-NMR (400MHz/CDCl ₃) δ 7.53 (1H, s), 4.46 (2H, q), 2.74 (3H, s), 2.48 (3H, s), 1.37 (4H, 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 (Alternariasolani); 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 (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: Rhizoctonia cerealis (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia 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 table 2 shows, when 50 mcg/ml, all compounds of the present invention's synthesis all have fungicidal activity in various degree, Hxw001-30 to the fungicidal activity of AS higher than 40%; Hxw001-30 to the fungicidal activity of CA higher than 40%; Hxw001-29, Hxw001-30 to the fungicidal activity of GZ higher than 40%; Hxw001-29, Hxw001-30 to the fungicidal activity of PP higher than 40%, wherein Hxw001-30 to the fungicidal activity of PP bacterium higher than 90%; Hxw001-30 to the fungicidal activity of BC higher than 40%; Hxw001-29, Hxw001-30 to the fungicidal activity of SS higher than 40%; Hxw001-29, Hxw001-30 to the fungicidal activity of RC higher than 40%, wherein Hxw001-30 to the fungicidal activity of RC higher than 80%; Hxw001-30 to the fungicidal activity of PS higher than 40%, wherein Hxw001-30 to the fungicidal activity of PS higher than 80%.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, Hxw001-29 of the present invention is 40% to the insecticidal activity of mythimna separata, 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 inactivate activity of Hxw001-30 of the present invention is 32.57 ± 5.18%; The induced activity of Hxw001-29 and Hxw001-30 is respectively 37.21 ± 6.98% and 30.62 ± 4.40%; 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, benzene sulphur becomes, aldicarb, butocarboxim, oxamyl, Talcord, thiofanox, F-1991, sok, grams hundred one-tenth, 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: isotianil, , 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: isotianil, 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	Hxw001-29	16.13	24.00	55.32	41.82	32.56	46.15	61.54	29.17	22.73
2	Hxw001-30	54.84	76.00	57.45	94.55	72.09	57.69	88.46	83.33	27.27

Data are the measurement result of 50 mcg/ml; AS: tomato early blight bacterium (Alternaria 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 (Pellicularia sasakii); RC: Rhizoctonia cerealis (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia 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	Hxw001-29	40
2	Hxw001-30	20
			5	Cyanogen insect amide	100
6	Blank	0

Table 4 is containing the activity (inhibiting rate/% of 100 mcg/ml) of the pyridine derivatives I resisting tobacco mosaic virus of 1,2,3-thiadiazoles

Numbering	Compound	Therapeutic activity ± SD	Inactivate activity ± SD	Prolection ± SD	Induced activity ± SD
						1	Hxw001-29	12.60±4.28	17.24±4.60	20.24±5.45	37.21±6.98
2	Hxw001-30	21.54±6.14	32.57±5.18	5.95±3.57	30.62±4.40
						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 I of 1,2, the 3-thiadiazoles working method mixed with commercially available agricultural chemical

Claims (8)

1. a class is containing the pyridine derivatives of 2,3-thiadiazoles, it is characterized in that having the chemical structure of general formula such as formula shown in I:

2. a class according to claim 1 is containing the synthetic method of the pyridine derivatives I of 1,2,3-thiadiazoles, and concrete synthetic route is as follows:

Concrete steps are as follows:

In 50 milliliters of round-bottomed flasks, add 3.9 mmole 4-successively replace that thiadiazoles-5-formaldehyde or 5-replace thiadiazoles-4-formaldehyde, 3.9 mmoles replace methyl aceto acetates, 5.86 mmole thiocarbamides, 0.07 gram of tosic acid, 5 milliliters of ethanol, stirring reaction 10 minutes under 80 degrees Celsius of microwave conditions, TLC controls reaction to carry out, underpressure distillation removing etoh solvent after completion of the reaction, residuum ethyl acetate: water=1: 1 dissolves, separate organic layer, use saturated NaHCO successively ₃, saturated common salt water washing, anhydrous sodium sulfate drying, column chromatography purification must containing the pyrimidines I of 1,2,3-thiadiazoles, and eluent volume ratio used 60 ~ 90 degrees Celsius of sherwood oils: ethyl acetate=3: 1, by gained sterling calculated yield; The described pyrimidines I containing 1,2,3-thiadiazoles is selected from: 2-sulfo--1,2,3,4-tetrahydrochysene-6-methyl-4-(4-methyl isophthalic acid, 2,3 ,-thiadiazoles-5-bases) pyrimidine-5-ethyl formate; 2-sulfo--1,2,3,4-tetrahydrochysene-6-methyl-4-(5-methyl isophthalic acid, 2,3 ,-thiadiazoles-4-bases) pyrimidine-5-ethyl formate.

3. the purposes in sterilant prepared by the pyridine derivatives I containing 1,2,3-thiadiazoles according to claim 1 and agriculturally acceptable auxiliary agent.

4. the purposes in sterilant prepared by the pyridine derivatives I containing 1,2,3-thiadiazoles according to claim 1 and agriculturally acceptable auxiliary agent.

5. the purposes in resisting tobacco mosaic virus agent prepared by the pyridine derivatives I containing 1,2,3-thiadiazoles according to claim 1 and agriculturally acceptable auxiliary agent.

6. according to claim 1 contain 1,2,3-thiadiazoles pyridine derivatives I and insecticide composition preventing and treating the application in agricultural and forestry and gardening plant insect pest:

According to claim 1ly 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, Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, bifenthrin, permethrin, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, 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 }, BaySIR-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, 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, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, to rattle away young ketone, Nylar, any one or two kinds in emaricin combinationally use for preventing and treating agricultural and forestry and gardening plant insect pest, according to claim 1ly contain 1, the pyridine derivatives I mass percentage in the composition of 2,3-thiadiazoles is 1%-90%, according to claim 1ly contains 1, the pyridine derivatives I of 2,3-thiadiazoles and the ratio of foregoing pesticidal agent are mass percent 1%: 99% to 99%: 1%, the formulation of composition processing is selected from seed treatment emulsion, aqueous emulsion, microemulsion, suspended emulsion agent, water-soluble granule, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, electrostatic spray agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, 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, microgranules, oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle and water agent, seed coat agent, basting agent, film forming finish, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, the insect pest of control is selected from 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, greenhouse is from aleyrodid, 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, bean 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, the plant of these composition for preventing and controlling 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, apple, citrus and peach, tea, wild vegetable, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape.

7. the pyridine derivatives I containing 1,2,3-thiadiazoles according to claim 1 is preventing and treating agricultural and forestry with antimicrobial combination respectively

And the application in gardening plant disease:

According to claim 1ly allly contain the pyridine derivatives I of 1,2,3-thiadiazoles and existing sterilant: 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: isotianil, 3,4-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, any one or two kinds in allyl isothiazole combinationally use for preventing and treating agricultural and forestry and gardening plant disease, according to claim 1ly contain 1, pyridine derivatives I total mass percentage in the composition of 2,3-thiadiazoles is 1%-90%, according to claim 1ly 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 object of above-mentioned composition control is selected from 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, the formulation of composition processing is selected from seed treatment emulsion, aqueous emulsion, microemulsion, suspended emulsion agent, water-soluble granule, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, electrostatic spray agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, 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, microgranules, oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle and water agent, seed coat agent, basting agent, film forming finish, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, the plant that these compositions are suitable for 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, apple, citrus and peach, tea, wild vegetable, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape.

8. the pyridine derivatives I containing 1,2,3-thiadiazoles according to claim 1 combines the application prevented and treated in agricultural and forestry and gardening plant virus disease respectively with anti-plant virus agent:

According to claim 1ly contain 1, 2, the pyridine derivatives I of 3-thiadiazoles and existing antiviral agent diazosulfide, tiadinil, be abbreviated as TDL, isotianil, it is English general by name: isotianil, 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, disease for preventing and treating agricultural and forestry and gardening plant virus disease is selected from any one in 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, cybidium ring spot virus, these compositions are selected from paddy for the plant prevented and treated, 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, apple, citrus and peach, tea, wild vegetable, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape, according to claim 1ly contain 1,2, pyridine derivatives I total mass percentage in the composition of 3-thiadiazoles is 1%-90%, according to claim 1ly contain 1, the pyridine derivatives I of 2,3-thiadiazoles and the ratio of aforementioned anti-plant virus agent are mass percent 1%: 99% to 99%: 1%, the formulation of composition processing is selected from seed treatment emulsion, aqueous emulsion, microemulsion, suspended emulsion agent, water-soluble granule, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, electrostatic spray agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, 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, microgranules, oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle and water agent, seed coat agent, basting agent, film forming finish, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent.