CN102816135A - 5-methyl-1,2,3-thiadiazole-containing 1,3,4-thiadiazole derivatives and their preparation method and use - Google Patents
5-methyl-1,2,3-thiadiazole-containing 1,3,4-thiadiazole derivatives and their preparation method and use Download PDFInfo
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Abstract
The invention provides 5-methyl-1,2,3-thiadiazole-containing 1,3,4-thiadiazole derivatives and their preparation method and use. The 5-methyl-1,2,3-thiadiazole-containing 1,3,4-thiadiazole derivatives are 1,2,3-thiadiazole-containing heterocyclic compounds. Intermediates of the 5-methyl-1,2,3-thiadiazole-containing 1,3,4-thiadiazole derivatives and the 5-methyl-1,2,3-thiadiazole-containing 1,3,4-thiadiazole derivatives respectively have a general structural formula III and a general structural formula IV. The invention discloses the general structural formula and the preparation method of the 5-methyl-1,2,3-thiadiazole-containing 1,3,4-thiadiazole derivatives, and also discloses a use of the 5-methyl-1,2,3-thiadiazole-containing 1,3,4-thiadiazole derivatives as bactericides, plant virus resistance agents and plant activators. After being mixing with agriculture acceptable assistants or synergists, the 5-methyl-1,2,3-thiadiazole-containing 1,3,4-thiadiazole derivatives can be used for preparation of bactericides, plant virus resistance agents and plant activators. The invention also discloses a use of the 5-methyl-1,2,3-thiadiazole-containing 1,3,4-thiadiazole derivatives combined with commercial insecticides, bactericides, plant virus resistance agents and plant activators in prevention and treatment on agricultural, forest and gardening diseases, insect pests and viral diseases, and also discloses a preparation method thereof.
Description
Technical field
Technical scheme of the present invention relates to and contains the 1,2-diazole compound, is specifically related to the 5-methyl isophthalic acid, and 2, the 3-thiadiazoles joins 1, the 3-4-thiadiazoles derivative.
Background technology
1, the 3-4-thiadiazoles is because of contain N, S heteroatoms simultaneously in the heterocycle molecule; Can therefore show wide biological activity (Liu Hanwen, organic chemistry simultaneously as participating in vital movement for body and acceptor; 20012,32,1332.); Particularly at pesticide field, more for example 1, the 3-4-thiadiazole compound is showed desinsection, sterilization, weeding and plant growth regulating activity preferably.No matter bis-heterocyclic compounds also becomes an important research direction at field of medicaments or at pesticide field.In same molecule, introduce two or more heterocyclic actives center, can change the electronic structure characteristics of fractionated molecule more flexibly, improve the biological activity of molecule; Thereby it is better to obtain activity, the compound that using value is higher (Sun Yanrong, organic chemistry; 2008,28,151.).Two heterocyclic synthesis strategies mainly contain with two different heterocycle minor structure direct splicing together; On existing heterocyclic basis one by one, utilize cyclization to synthesize the another one heterocycle.Utilizing the cyclization under acidic conditions of aroyl lsothiocyanates is to synthesize 1, and the concrete method of the classical way of 3-4-thiadiazoles (Hassan, M.A.Arch.Pharm.Pharm.Med.Chem.1998 331,385.) has POCl
3System, H
2SO
4/ ethanol system, H
2SO
4Bodies etc. are compared H with other cyclisation system
2SO4/CH
3The OH system has advantages such as reaction conditions is gentle, simple to operate, productive rate is higher, purification of products is convenient.1,2, the 3-thiadiazole compound has wide biological activity equally, and relevant patent and document are summed up and seen Bakulev, et al.Newyork:John Wiley&Sons; Inc, 2004 monograph, the research of relevant thiadiazoles mainly concentrates on 1,3; 4-thiadiazoles derivative, 1,2,5-thiadiazoles derivative and 1,2; On the 4-thiadiazoles derivative, and for 1,2, the active research report of 3-thiadiazoles derivative is but less relatively.1,2,3-thiadiazoles derivative commercial kind in medicine and agricultural chemicals is few, and agriculture field is used has only cotton defoliant--the clever (N-phenyl-N '-1 of disleave; 2,3-thiadiazoles-5-urea, TDZ), plant activator--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 research and design in earlier stage is synthetic and found that the first thiophene lures the inducing anti-disease activity of amine, at present just in the industrialization development process.In order to seek 1,2 of more high biological activities, 3-thiadiazole new compound; The present invention is 1,2, and 3-thiadiazoles ring is introduced two keys outward; One type of 5-methyl isophthalic acid has been synthesized in design, and 2, the 3-thiadiazoles joins 1; The 3-4-thiadiazoles derivative, and carried out the bioactive screening of system, in the hope of the candidate compound being provided for novel pesticide initiative research.
Summary of the invention
Technical problem to be solved by this invention is: new 5-methyl isophthalic acid is provided; 2; The 3-thiadiazoles joins-1; The compound method of 3-4-thiadiazoles derivative IV and intermediate III thereof provides this compounds to suppress agricultural and gardening and forestry plant pathogen and antiviral biological activity and measuring method, and the middle application of these compounds in agriculture field and gardening field and field of forestry is provided simultaneously.
The present invention solves this technical problem the technical scheme that is adopted: the 5-methyl isophthalic acid with agriculture field, gardening field, field of forestry fungicidal activity, anti-phytoviral activity, inducing plant generation anti-disease activity; 2; The 3-thiadiazoles joins-1, and the chemical structure of general formula of 3-4-thiadiazoles derivative IV and intermediate III thereof sees that formula is following:
Wherein, Ar is for being selected from phenyl, 4-fluorophenyl, 3-fluorophenyl, 2-nitrophenyl, 4-nitrophenyl, 3-chloro-phenyl-, 4-chlorobenzene
The group of base, 4-aminomethyl phenyl, 3-aminomethyl phenyl, 3-p-methoxy-phenyl.
5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins-1, and the compound method of 3-4-thiadiazoles derivative IV and intermediate III thereof is following:
Wherein, Ar is the group that is selected from phenyl, 4-fluorophenyl, 3-fluorophenyl, 2-nitrophenyl, 4-nitrophenyl, 3-chloro-phenyl-, 4-chloro-phenyl-, 4-aminomethyl phenyl, 3-aminomethyl phenyl, 3-p-methoxy-phenyl.
Specifically be divided into following steps:
A. the preparation of intermediate N (2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-formohydrazide group) sulfo-acyl group) substituted benzamide III:
With the 5-methyl isophthalic acid of 3.33 mmoles, 2, the replacement isothiocyanic acid ester II of 3-thiadiazoles-4-formyl hydrazine I, 3.33 mmoles and 20 milliliters of DMF join in 50 milliliters of three mouthfuls of round-bottomed flasks room temperature; Stirred 6 hours.White solid occurs, filter gained solid ethyl alcohol recrystallization, yield 60%-90%, measure fusing point with
1H NMR, the amount of synthetic compound III enlarges by corresponding proportion or dwindles, and the volume of reaction vessel enlarges by corresponding proportion or dwindles; The chemical structure and the physical and chemical parameter of compound III are seen table 1.
B.5-methyl isophthalic acid, 2, the 3-thiadiazoles joins-1, the preparation of 3-4-thiadiazoles IV:
N-(2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-formohydrazide group) sulfo-acyl group) substituted benzamide III, 20 methyl alcohol, 0.1 milliliter of vitriol oil of in 50 milliliters of original place flasks, adding 3.0 mmoles, stirring and refluxing 6 hours.White solid occurs, filter gained solid ethyl alcohol recrystallization, yield 60%-90%, measure fusing point with
1HNMR, the amount of synthetic compound IV enlarges by corresponding proportion or dwindles, and the volume of reaction vessel enlarges by corresponding proportion or dwindles; The chemical structure and the physical and chemical parameter of compound IV are seen table 1.
C.5-methyl isophthalic acid, 2, the 3-thiadiazoles joins-1, and 3-4-thiadiazoles derivative IV and intermediate III thereof are to the mensuration of pathogenic fungi growth activity:
5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins-1; 3-4-thiadiazoles derivative IV and intermediate III sterilization thereof or bacteriostatic activity adopt thalli growth rate assay method, and detailed process is: get 5 milligrams of sample dissolution in an amount of N, then with containing the medicament that a certain amount of polysorbas20 emulsifier aqueous solution is diluted to 500 mcg/ml; To supply the reagent agent under aseptic condition, respectively to draw in 1 milliliter of injection petridish, and add 9 milliliters of substratum more respectively, it is dull and stereotyped to process 50 mcg/ml pastilles after shaking up; Flat board to add 1 milliliter of aqua sterilisa is done blank, cuts the bacterium dish with the punch tool of 4 millimeters of diameters along the mycelia outer rim, moves on the pastille flat board; Being equilateral triangle puts; Every processing repetition 3 times is placed on cultivation in 24 ± 1 degrees centigrade of constant incubators with petridish, and colony diameter to be contrasted expands to 2-3 centimetre of " Invest, Then Investigate " and respectively handles bacterium dish expansion diameter; Average; Relatively calculate relative bacteriostasis rate with blank, supply the examination bacterial classification to comprise the kind of most of phytopathogen of the actual generation in multiple representative field in China's agriculture prodn, 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: ring rot of apple bacterium (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: cereal rhizoctonia (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum).
D. 5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins-1, the mensuration of 3-4-thiadiazoles derivative IV and intermediate III inducing anti-disease activity thereof:
5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins-1, and 3-4-thiadiazoles derivative IV and the active screening method of intermediate III evoking tobacco resisting tobacco mosaic virus (TMV) thereof are following: the mensuration of the direct antiviral activity that exsomatizes adopts half page of method to carry out; It is the common cigarette that seedling age is consistent that live body is induced, and 3 basins are one group, respectively at the cigarette seedling of inoculation pre-treatment in preceding 7 days; Processing mode comprises: spray test compound solution 2 to 3 times, and each 10 milliliters, or soil treating; Each 10 milliliters, the 7th day frictional inoculation TMV on the tobacco leaf that newly grows places its growth optimal temperature and the following cultivation of illumination after 3 days the cigarette seedling; The inspection incidence; Comprehensive scab number is calculated as follows out the inducing anti-disease toxic effect fruit of test compound to TMV, and 3 repetitions are established in each processing, and contrast divides blank and standard chemicals treatment to contrast 2 kinds; Selecting tiadinil (TDL) (purity is greater than 99.5%) is the plant inducing anti-disease activator of standard:
Wherein, R is the induce effect of new compound to the anti-TMV of tobacco, 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 handling rear blade, unit: individual through compound;
The invention has the beneficial effects as follows: the present invention is to the 5-methyl isophthalic acid; 2; The 3-thiadiazoles joins-1; 3-4-thiadiazoles derivative IV and intermediate III thereof have been carried out guide's optimization, and the synthetic new compound has been carried out the screening of bacteriostatic activity and antiviral activity and mixed the research of using, and this compounds can be used to prevent and treat agriculture field and the Plant diseases in field of forestry and gardening field and the control of virus disease.
The present invention specifies the 5-methyl isophthalic acid more through specific preparation and biological activity determination embodiment; 2, the 3-thiadiazoles joins-1, synthetic and the biological activity and the application thereof of 3-4-thiadiazoles derivative IV and intermediate III thereof; Said embodiment only is used to specify the present invention and unrestricted the present invention; Especially its biological activity only illustrates, and unrestricted this patent, embodiment is following:
Embodiment 1
The preparation of intermediate N (2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-formohydrazide group) sulfo-acyl group) substituted benzamide III:
With the 5-methyl isophthalic acid of 3.33 mmoles, 2, the replacement isothiocyanic acid ester II of 3-thiadiazoles-4-formyl hydrazine I, 3.33 mmoles and 20 milliliters of DMF join in 50 milliliters of three mouthfuls of round-bottomed flasks room temperature; Stirred 6 hours.White solid occurs, filter gained solid ethyl alcohol recrystallization, yield 60%-90%, measure fusing point with
1H NMR, the chemical structure and the physical and chemical parameter of compound III are seen table 1.
Embodiment 2
The 5-methyl isophthalic acid, 2, the 3-thiadiazoles joins-1, the preparation of 3-4-thiadiazoles IV:
N-(2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-formohydrazide group) sulfo-acyl group) substituted benzamide III, 20 methyl alcohol, 0.1 milliliter of vitriol oil of in 50 milliliters of original place flasks, adding 3.0 mmoles, stirring and refluxing 6 hours.White solid occurs, filter gained solid ethyl alcohol recrystallization, yield 60%-90%, measure fusing point with
1H NMR, the chemical structure and the physical and chemical parameter of compound IV are seen table 1.
Embodiment 3
5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins-1, the antibacterial or fungicidal activity of 3-4-thiadiazoles derivative IV and intermediate III thereof:
The title and the code name of the frequently seen plants pathogenic fungi of the present invention's test 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: ring rot of apple bacterium (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: cereal rhizoctonia (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), these bacterial classifications have good representativeness, can represent the kind of most of pathogenic bacteria that the field takes place in the agriculture prodn.Thalli growth rate method is measured the result and is seen table 2, and table 2 shows that when 50 mcg/ml, all compounds of synthetic of the present invention all have fungicidal activity in various degree, and TN-TDZ9, TN-TDZ10 are higher than 40% to the fungicidal activity of AS; TN-TDZi1, TN-TDZi7, TN-TDZi9, TN-TDZ9 are higher than 40% to the fungicidal activity of CA; TN-TDZi3, TN-TDZ6, TN-TDZi9, TN-TDZi9 are higher than 40% to the fungicidal activity of GZ; TN-TDZi1, TN-TDZ1, TN-TDZi2, TN-TDZ2, TN-TDZ3, TN-TDZi4, TN-TDZ4, TN-TDZi5, TN-TDZ5, TN-TDZi6, TN-TDZi7, TN-TDZ7, TN-TDZi8, TN-TDZi9, TN-TDZ9, TN-TDZi10 are higher than 40% to the fungicidal activity of PP; TN-TDZi3, TN-TDZ6, TN-TDZi9, TN-TDZi9 are higher than 40% to the fungicidal activity of GZ; TN-TDZi1, TN-TDZi3, TN-TDZ3, TN-TDZ4, TN-TDZ5, TN-TDZi7, TN-TDZ9 are higher than 40% to the fungicidal activity of BC; TN-TD4, TN-TDZi6, TN-TDZ6, TN-TDZi9, TN-TDZ9, TN-TDZi10 are higher than 40% to the fungicidal activity of SS; TN-TDZ4, TN-TDZ5, TN-TDZ6, TN-TDZ10 are higher than 40% to the fungicidal activity of PI; TN-TD4, TN-TDZi6, TN-TDZ6, TN-TDZi9, TN-TDZ9, TN-TDZi10 are higher than 40% to the fungicidal activity of SS; Except individual compound TN-TDZi4, TN-TDZ8, majority of compounds to the fungicidal activity of RC all greater than 40%; Except individual compound TN-TDZi2, TN-TDZ4, TN-Tdi4 majority of compounds to the fungicidal activity of PS all greater than 40%.Therefore, this compounds has shown fungicidal activity preferably.
Embodiment 4
5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins-1, the effect of the anti-tobacco resisting tobacco mosaic virus of 3-4-thiadiazoles derivative IV and intermediate III thereof:
The active mensuration result of anti-TMV sees table 3; Table 3 shows; Commercial plant resisting tobacco mosaic virus medicament virazole has certain activity to TMV; Most of 5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins-1; 3-4-thiadiazoles derivative IV and intermediate III thereof have the activity of anti-TMV preferably, and TN-TDZi1, TN-TDZ1, TN-TDZi2, TN-TDZ6, TN-TDZi7, TN-TDZ8, TN-TDZ9, the passivation effect of TN-TDZi10 when 100 mcg/ml all are significantly higher than contrast medicament virazole and the result of treatment of Ningnanmycin under the same concentrations.TN-TDZi1, TN-TDZ1, TN-TDZi3, TN-TDZi5, the result of treatment of TN-TDZ8 when 100 mcg/ml all are significantly higher than contrast medicament virazole and the passivation effect of Ningnanmycin under the same concentrations.TN-TDZ1, TN-TDZ4, the TN-TDZ8 effect of inducing when 100 mcg/ml all is significantly higher than the effect of inducing of contrast medicament tiadinil TDL under the same concentrations.
Embodiment 5
5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins-1, the application in 3-4-thiadiazoles derivative IV and intermediate III thereof and sterilant combination control agricultural and forestry and the gardening plant insect pest
All 5-methyl isophthalic acids of the present invention; 2; The 3-thiadiazoles joins-1; 3-4-thiadiazoles derivative IV and intermediate III thereof and existing sterilant: Chlorpyrifos 94, inferior Nong, acetamiprid, Affirm (Merck Co.), more visit that rhzomorph, Avrmectin, pleocidin, fenvalerate, efficient fenvalerate, PP-383, beta_cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, Beta-FCR-1272, FCR-1272, Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, WL 43479, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiophene worm quinoline, thiophene worm piperazine, thiophene worm amine, MTI-446, clothianadin, Da Tenan, diflubenzuron, the young urea that goes out, Teflubenzuron, deinsectization are grand, fluorine bell urea, WL 115110, pyridine worm are grand, Acarus tritici urea, poisonous insect urea, penfluron, Noviflumuron are noviflumuron, its CAS number for 121451-02-3, flucycloxuron, Novaluron be Rimon, fluorine pyridine urea, Bay sir 6874 promptly { 1-[(3.5-two chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, Bay SIR-8514 promptly [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, promptly two three WL 115110s of Bistrifluron, furans worm hydrazides, worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, PP-062, MTMC, isoprocarb, cartap, fenobucarb, leaf disperse, carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, azoles mite ester, pyridaben, four mite piperazines, alkynes mite Te, butyl ether urea, benfuracarb, pyrrole aphid ketone, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, PP618, ethoprophos, fluorine worm nitrile, desinsection list, disosultap, chlorine insect amide, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, azoles insect amide, tebufenpyrad, bromothalonil, pyrazine ketone, second mite azoles, tebufenpyrad, the young ketone of rattling away., any one or two kinds of combination uses in the pyrrole propyl ether, emaricin etc.; 5-methyl isophthalic acid of the present invention; 2, the 3-thiadiazoles joins-1, and 3-4-thiadiazoles derivative IV and intermediate III thereof the quality percentage composition in compsn is 1%-90%; 5-methyl isophthalic acid of the present invention; 2, the 3-thiadiazoles joins-1, and the ratio of 3-4-thiadiazoles derivative IV and intermediate III thereof and commercially available agricultural chemical is mass percent 1%: 99% to 99%: 1%; Spray after can directly converting water; Comprise agricultural in its preparation and go up acceptable solvent and emulsifying agent and solubility promoter and synergistic agent etc., Gu the formulation of compsn processing be selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, big granula, granule, microemulsion, oil-suspending agent, finish, the seed with coated pesticidal, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule granula, capsule suspension, can disperse dense dose, pulvis, dry mixing kind pulvis, 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, seed treatment suspension agent, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, big granula, drift pulvis, granula, ointment, thermal fog, solid-liquid mix dress agent, liquid/liquid mix dress agent, cold mist agent, admittedly/mixing adorns agent, medicine lacquer, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, bold and vigorously waters in agent, stylus, the agent of kind clothing, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspension agent, tablet, tracking pulvis, ultra low volume liquids, steam releasing agent, water-dispersible granules, wettable powder, the wet-mixing kind water-dispersible powder 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, east mole cricket, 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, 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, the hard a red-spotted lizard of Korea's ball, pear lace bug, banana lace bug, thin corner piece stinkbug, little minute pirate bugs, 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, intends smaller apple leaf roller, 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 selects diamond drill, black cutworm, big cutworm, yellow cutworm, robber poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, oranges and tangerines swallowtail butterfly, 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, golden edge buprestid beetle, tenebrio molitor, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, black dull cockchafer, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, big 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, the outstanding cocoon ichneumon wasp of corn earworm, 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, melon trypetid, wheat leaf ash are dived fly, Americal rice leaf miner, the black fly of diving of beans stalk, frit fly, kind fly, onion fly, radish fly, full skirt chase after and post that fly, Pyrausta nubilalis (Hubern). are strictly posted fly, armyworm lacks Agricultural pests, forestry pest, gardening pest insect and sanitary insect pests such as must posting fly, and the controlling mode while also comprises double controlling; The control effect of compsn is good, and drug effect plays stably, and has certain synergism and summation action, finds to have the compsn of antagonistic action; The crop that these compsns are suitable for comprise paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, yam, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, genseng, 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, yam, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape.Compsn makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection in the parasiticidal defence capability that improves plant simultaneously.
Embodiment 6
5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins-1, the application in 3-4-thiadiazoles derivative IV and intermediate III thereof and sterilant combination control agricultural and forestry and the gardening plant disease
All the present invention is 5 - methyl-1, 2,3 - thiadiazole United -1,3-4 - thiadiazole derivatives and intermediates III and IV existing fungicides such as benzothiadiazole, amine acid bacteria thiophene, thiazole amide, amine induced a thiophene 4 - methyl-1, 2,3 - thiadiazole-5 - carboxylic acid 4 - methyl-1, 2,3 - thiadiazole-5 - Sodium 4 - methyl-1, 2,3 - thiadiazole-5 - carboxylic acid ethyl ester, DL-β-aminobutyric acid, Isotianil (isotianil), ribavirin, An Tuofen, or Ningnanmycin salicylic acid, Cymoxanil, thiram, ziram, mancozeb, fosetyl, thiophanate-methyl, chlorothalonil, the enemy can be loose, procymidone, Fenpropidine, thiophanate-methyl, thiophanate, metalaxyl, salicylic acid, flumorph, Dimethomorph, efficient metalaxyl, efficient Benalaxyl, double-cypermethrin bacteria amine, flusulfamide, A flusulfamide, thiophene amine fluoride bacteria , flutolanil, leaf blight phthalate, cyclopropane amino acid bacteria, cyflufenamid, cycloalkyl amine acid bacteria, cyano bacteria amine, amine silica thiabendazole, furosemide topiramate amine bacteria, penthiopyrad, diacetylene amine acid bacteria, benzene amine acid bacteria, ofurace, carboxin, B strains Lee, iprodione, azoxystrobin, Kresoxim amines, fluoxastrobin, kresoxim, phenoxy bacteria amines, amine oxime ether bacteria, aerobic bacteria pyridine esters, pyraclostrobin, trifloxystrobin, enestroburin, allyl amine oxime bacteria, oxygen propiconazole, bromuconazole, cyproconazole, difenoconazole azole, Diniconazole, efficient diniconazole, fluorine Propiconazole, fenbuconazole, fluoro quinazoline, flusilazole, flutriafol, hexaconazole, imines azole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, Prothioconazole azole, simeconazole, tebuconazole, PTFE ether, triazole alcohol, sterilization azole, Bitertanol, thiabendazole, fuberidazole, imazalil, efficient imazalil, prochloraz, triflumizole, Cyazofamid, imidazole cycloheximide, evil imidazole, pefurazoate, Famoxadone, pyridine bacteria oxazole, hymexazol oxadixyl, thiophene pyraclostrobin, earth benomyl, octyl thiophene ketones, benzene thiophene thiocyanate, dodecyl tridemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, piperidine oxime spots, fungus amine piperidine ring, boscalid, fluazinam acid bacteria amines, amine piperidine bacteria, cyprodinil, mepanipyrim fluorine, ferimzone, mepanipyrim, pyrimethanil, fenarimol, nuarimol, Chinomethionate, dithianon, ethoxyquin morpholine, hydroxy quinoline, quinoline propoxyphene, phenoxy quinoline, diethofencarb, isopropyl bacteria amines, benzene thiabendazole amines Propamocarb, sulfur bacteria Granville, edifenphos, iprobenfos, topiramate bacteria phosphorus , methyl Tolclofos, blasticidin, kasugamycin, polymyxin, Polyoxin, validamycin, Jinggangmycin, streptomycin, metalaxyl, furalaxyl, Benalaxyl, furosemide amide, mepronil, carbendazim, benomyl, thiophanate-methyl, triadimefon, ethirimol sulfonate, dimethyl ethyl phenol, ethirimol, captafol, captan, sterilization Dan, vinclozolin, chlorofluorocarbons sclerotia Lee, Dimetachlone, chlorothalonil, Isoprothiolane, kitazine, leaf blight, PCNB, mancozeb, Propineb, triacetate phosphonic acid aluminum, sulfur, Bordeaux mixture, copper sulfate, copper oxychloride, cuprous oxide, cupric hydroxide, benzene cycloheximide, pencycuron, pyridazine cycloheximide tetrachlorophthalide, pyroquilon, spiro amine mellea , Tricyclazole, triforine, more fruit pyridine, Iminoctadine salt Iminoctadine amine, Dicloran, flusulfamide benzene, toluene flusulfamide, indole ester Fenaminosulf, oxolinic acid, allyl benzene thiazole, bronopol, methyl iodide, metam sodium, the enemy lines esters, dazomet, dichloro-isopropyl ether, Fosthiazate, Cadusafos, fensulfothion, insects fenamiphos, fenamiphos, Ethoprophos, except Line phosphorus, chlorine triazophos, carbosulfan cyclophosphamide, oxamyl, aldicarb, carbofuran, sulfuryl fluoride, dichloropropene, dichloro-isonicotinic acid,? allyl isothiazolin any other known as fungicides in combination with any one or two; the present invention is 5 - methyl-1, 2,3 - thiadiazole United -1,3-4 - thiadiazole derivatives and intermediates III IV in the composition percentage of the total mass of 1% -90%, the present invention is 5 - methyl-1, 2,3 - thiadiazole United -1,3-4 - thiadiazole derivatives IV and the pesticide intermediates III with the product ratio of 1% weight percentage: 99% to 99%: 1%; composition control effect is good, these compositions have a synergistic effect and the additive effect, we have not found to have antagonistic effects composition; said composition can be used for agricultural and horticultural plant disease plant disease prevention, control objects include Oomycete the genus Achlya, Aphanomyces spp, Pythium, Phytophthora, referring Terrier spp, uniaxial spp, fake downy mildew genus Peronospora spp produced more than twenty genera diseases, such as cotton seedlings rot, root rot of tomato, potato late blight, tobacco black shank, millet powdery mildew, downy mildew of grape , lettuce downy mildew, cucumber downy mildew, cucumber anthracnose and other crops, crops, horticultural and forestry plants, other diseases, etc.; processing composition selected from a wettable powder formulations, release agent, powder, microcapsule suspensions, dispersible liquid formulations, dispersible solid preparation, seed treatment, emulsions, aqueous emulsion, large grain, granules, micro-emulsions, oil suspensions, oil, seed coated with a pesticide, suspension emulsion, water-soluble granules, soluble concentrate agent, water dispersible granules, poison Valley, aerosols, block bait, release block, concentrated bait, capsules granules, capsules, suspensions, dispersible concentrate, powder, dry seed powder , emulsifiable concentrates, electrostatic sprays, oil-in-water emulsion, seed treatment agent, water-in-oil emulsions, aerosol cans, fine granules, smoke candle, smoke cartridges, smoke stick, seed treatment suspending agents, smoke tablet, aerosol, smoke pellets , granular bait, gas evolution agents, large granules, drifting powders, granules, ointments, thermal fog, solid / liquid mixing device agent, liquid / liquid mixing device agents, fog agent, solid / solid mixing device agent, drug paint, seed processing liquid, particulate agents, suspending agents oil, oil, oil dispersible powders, creams, flaky baits, thick glue, sprinkling agents, stick agents, seed coating, bait, liniment, small bait, suspensions, emulsions suspensions, water-soluble granule, soluble concentrate agents, film oil, soluble powders, water soluble powder for seed treatment, ultra low volume suspension, tablet, tracking powder, ultra low volume liquid, steam release agents, water-dispersible granules, wettable powders, water dispersible powder wet dressing of any one.The crop that these compsns are suitable for comprise cereal (comprising paddy, wheat, barley, oat, corn, millet, Chinese sorghum etc.), tuber crops (comprising sweet potato, yam, cassava etc.), beans (comprising soybean, broad bean, pea, mung bean, red bean etc.) and fiber (cotton, crudefiber crop, silkworm and mulberry etc.), oil plant (peanut, rape, sesame, soybean, Sunflower Receptacle etc.), sugar material (beet, sugarcane etc.), beverage (tealeaves, coffee, cocoa etc.), hobby (tobacco leaf etc.), medicinal (genseng, the bulb of fritillary etc.), the torrid zone (rubber, coconut, oil palm, the sisal hemp etc.) food crop of etc.ing and fruit, flowers, oil plant, sugared expect and cash crop such as cotton, fiber crops, tea, tobacco, Chinese medicinal materials and plant melon, really, tea, silkworm and mulberry, vegetables (containing various wild vegetable etc.), bamboo shoots, flowers and garden crop such as tobacco (flue-cured tobaccos such as ornamental plant, hops, medicinal material, pepper, seedling and other garden crops; Air-curing of tobacco leaves, suncured tabacco), vegetables, (tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic etc.), melon (watermelon, muskmelon, hami melon, pawpaw etc.), beans (soybean, broad bean, pea-pods etc.), yam, wheat, corn, paddy rice, peanut, fruit tree, (apple, banana, citrus, peach, papaya), flowers (like orchid), potted landscape etc.Compsn makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection in the germ-resistant defence capability that improves plant simultaneously.
Embodiment 7
5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins-1, and 3-4-thiadiazoles derivative IV and intermediate III thereof and antiviral agent are combined in the application in control agricultural and forestry and the gardening plant virus disease
The 5-methyl isophthalic acid; 2, the 3-thiadiazoles joins-1,3-4-thiadiazoles derivative IV and intermediate III thereof and existing Antiphytoviral medicament diazosulfide, tiadinil (TDL), different metsulfovax (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, DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lure any 1 or 2 compounds combinations in amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, the jingganmycin; Be used to prevent and treat the agricultural plants virus disease; These virus diseases are selected from tobacco mosaic virus disease, various melon virus disease, various solanberry viroid disease, beans virus disease, Cruciferae virus disease, grain and oil crop virus disease, cotton virus disease and the various fruit tree virus disease any, wherein endanger serious being selected from: tobacco virus, peppery pimento virus disease, tomato virus disease, Chinese cabbage virus disease, paddy rice virus disease comprise in rice dwarf virus disease, BYDV, stripe virus disease, fern leaf of tomato viral disease, chilli pepper mosaic virus disease and tobacco veinal necrosis virus disease, corn short mosaic disease, cauliflower mosaic virus, oranges and tangerines virus disease, cymbidium mosaic virus, the cybidium ring spot virus any.The crop that these compsns are suitable for be selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, yam, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, genseng, 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, yam, paddy rice, pepper, apple, banana, citrus, plants such as agricultural, gardening, economy, forestry such as peach, papaya, orchid, potted landscape; The use of these compsns makes the immunizing power of crop self be improved, and when producing the control of insect especially infection insect, has induced plant to produce the control to viral diseases of plants; Also can produce the direct control effect of virus disease; Therefore, these compsns can be used for Antiphytoviral medicament and inducing plant Antiphytoviral preparation of medicaments and purposes.5-methyl isophthalic acid of the present invention; 2, the 3-thiadiazoles joins-1, and 3-4-thiadiazoles derivative IV and intermediate III thereof the total quality percentage composition in compsn is 1%-90%; 5-methyl isophthalic acid of the present invention; 2, the 3-thiadiazoles joins-1, and the ratio of 3-4-thiadiazoles derivative IV and intermediate III thereof and commercially available agricultural chemical is mass percent 1%: 99% to 99%: 1%; The formulation of compsn processing is selected from wettable powder; Sustained release dosage; Pulvis; Micro-capsule suspension; The dispersible body preparation; The dispersible solid preparation; Seed treatment emulsion; Aqueous emulsion; Big granula; Granule; Microemulsion; Oil-suspending agent; Finish; Seed with coated pesticidal; Suspended emulsion agent; Water-soluble granule; Soluble thick agent; Water-dispersible granules; Poison grain; Aerosol; Block poison bait; Sustained-release block; Dense poison bait; The capsule granula; Capsule suspension; Can disperse dense dose; Pulvis; Dry mixing kind pulvis; 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 seed treatment suspension agent; The smog sheet; Smoke substance; The smog ball; Granular poison bait; Foaming agent; Big granula; The drift pulvis; Granula; Ointment; Thermal fog; Solid-liquid mixes the dress agent; Liquid/liquid mixes the dress agent; Cold mist agent; Gu Gu/mix and adorn 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; Soluble powder; The seed treatment water solube powder; The ultra-low volume suspension agent; Tablet; Follow the trail of pulvis; Ultra low volume liquids; The steam releasing agent; Water-dispersible granules; Wettable powder; In the wet-mixing kind water-dispersible powder any one; All show addition or synergism between these compsns, when keeping insecticidal activity, the effect that its antiviral activity all uses separately greater than any one compound; Do not find to have the compsn of antagonistic action, the drug effect lasting period of compsn is long.
Can know 5-methyl isophthalic acid, 2 from the basic principles of chemistry; The 3-thiadiazoles joins-1, thereby 3-4-thiadiazoles derivative IV and intermediate III thereof can produce 5-methyl isophthalic acid, 2 from the carbonyl fracture in plant with after the water molecules effect; 3-thiadiazoles-4-formic acid confirms also that through relevant software prediction and test compound of the present invention can produce 5-methyl isophthalic acid, 2 in the degraded of plant materials intracellular metabolite; 3-thiadiazoles-4-formic acid, 5-methyl isophthalic acid, 2; 3-thiadiazoles-4-formic acid has inducing plant and produces the resistance to the phytopathy original, can be used in the control of Plant diseases and viral diseases of plants.Therefore, these compsns can be used in preparation Antiphytoviral medicament and inducing plant Antiphytoviral medicament.Compsn has improved the defence capability of plant in Antiphytoviral, make plant produce the defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 8
5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins-1, the complete processing and the stability of 3-4-thiadiazoles derivative IV and intermediate III thereof and commercially available agricultural chemical compound preparation
5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins-1; The mixture complete processing of 3-4-thiadiazoles derivative IV and intermediate III thereof and commercially available agricultural chemical is seen table 4; Visible by table 4, most medicament all can be processed according to the method for statement, and the main component of liquid preparation is other a component etc. of effective constituent and solubility promoter and tensio-active agent, synergistic agent, antifreezing agent, stablizer, thickening material or permeate agent etc.; The composition of solid preparation mainly includes imitates upward acceptable adjuvant component of other agriculturals such as composition, tensio-active agent and filler; The cold storage test of process preparation, liquid preparation are placed 1 week not have to precipitate at 0 ± 2 degree centigrade and are separated out, and solid preparation placed for 2 weeks at 54 ± 2 degrees centigrade; Caking phenomenon does not appear in medicament; The medicament drug effect that all preparations store before and after placing does not have significant difference, the rate of decomposition of compsn effective constituent in 5%, the composite preparation qualified stability.
Table 15-methyl isophthalic acid, 2, the 3-thiadiazoles joins-1, the chemical structure of 3-4-thiadiazoles derivative IV and intermediate III thereof and physical and chemical parameter
Table 1 5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins-1, the chemical structure of 3-4-thiadiazoles derivative IV and intermediate III thereof and physical and chemical parameter (continuing)
Table 25-methyl isophthalic acid, 2, the 3-thiadiazoles joins-1, the biological activity of 3-4-thiadiazoles derivative IV and intermediate III thereof (/ %)
Compound number | AS | CA | GZ | PP | BC | SS | RC | PS | PI |
TN-TDZi1 | 17.86 | 40.00 | 9.76 | 40.54 | 45.16 | 15.15 | 64.81 | 28.75 | 29.63 |
TN-TDZ1 | 14.29 | 35.00 | 12.20 | 67.57 | 12.90 | 18.18 | 44.44 | 15.00 | 33.33 |
TN-TDZi2 | 7.14 | 30.00 | 14.63 | 64.86 | 25.81 | 3.03 | 50.00 | 11.25 | 3.70 |
TN-TDZ2 | 14.29 | 30.00 | 17.07 | 59.46 | 25.81 | 15.15 | 44.44 | 15.00 | 11.11 |
TN-TDZi3 | 16.13 | 25.00 | 40.00 | 30.00 | 67.86 | 34.15 | 52.38 | 54.79 | 36.67 |
TN-TDZ3 | 16.13 | 31.25 | 15.00 | 66.67 | 67.86 | 31.71 | 52.38 | 63.01 | 36.67 |
TN-TDZi4 | - | - | - | - | - | - | - | - | - |
TN-TDZ4 | 25.81 | 12.50 | 17.50 | 60.00 | 46.43 | 43.90 | 57.14 | 75.34 | 43.33 |
TN-TDZi5 | 27.59 | 17.65 | 75.44 | 43.33 | 21.74 | 9.30 | 62.22 | 58.21 | 30.00 |
TN-TDZ5 | 19.35 | 18.75 | 25.00 | 40.00 | 67.86 | 34.15 | 64.29 | 69.86 | 66.67 |
TN-TDZi6 | 31.03 | 29.41 | 31.58 | 50.00 | 39.13 | 51.16 | 80.00 | 59.70 | 30.00 |
TN-TDZ6 | 37.93 | 23.53 | 50.88 | 30.00 | 26.09 | 53.49 | 57.78 | 49.25 | 40.00 |
TN-TDZi7 | 34.48 | 47.06 | 33.33 | 73.33 | 69.57 | 74.42 | 80.00 | 56.72 | 6.67 |
TN-TDZ7 | 16.13 | 12.50 | 22.50 | 43.33 | 42.86 | 58.54 | 50.00 | 54.79 | 33.33 |
TN-TDZi8 | 25.00 | 35.00 | 14.63 | 40.54 | 35.48 | 9.09 | 44.44 | 6.25 | 18.52 |
TN-TDZ8 | 17.86 | 15.00 | 19.51 | 27.03 | 12.90 | 24.24 | 31.48 | 12.50 | 3.70 |
TN-TDZi9 | 7.14 | 45.00 | 43.90 | 72.97 | 77.42 | 48.48 | 94.44 | 57.50 | 37.04 |
TN-TDZ9 | 41.38 | 41.18 | 40.35 | 50.00 | 13.04 | 60.47 | 51.11 | 55.22 | 23.33 |
TN-TDZi10 | 20.69 | 29.41 | 22.81 | 43.33 | 17.39 | 48.84 | 60.00 | 47.76 | 33.33 |
TN-TDZ10 | 48.28 | 11.76 | 28.07 | 33.33 | 21.74 | 41.86 | 62.22 | 53.73 | 40.00 |
Data are the mensuration result of 50 mcg/ml; 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: ring rot of apple bacterium (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: cereal rhizoctonia (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum); ND: undetermined.
Table 35-methyl isophthalic acid, 2, the 3-thiadiazoles joins-1, the activity of 3-4-thiadiazoles derivative IV and the anti-TMV of intermediate III thereof
Compound | Concentration/mg/L | Therapeutic activity | SD | Inactivate activity | SD | Protection is active | SD | Induced activity | SD |
TN-TDZi1 | 100 | 50.85 | 4.49 | 44.44 | 5.09 | 22.89 | 4.34 | 16.02 | 4.84 |
TN-TDZ1 | 100 | 52.54 | 4.49 | 50.56 | 4.19 | 46.59 | 3.04 | 53.21 | 2.94 |
TN-TDZi2 | 100 | 59.32 | 5.09 | 17.78 | 5.09 | 51.41 | 2.51 | 22.43 | 4.00 |
TN-TDZ2 | 100 | 29.38 | 5.95 | 32.22 | 5.09 | 26.91 | 2.51 | 37.82 | 4.84 |
TN-TDZi3 | 100 | 14.94 | 3.04 | 42.46 | 2.48 | 29.78 | 1.68 | 26.67 | 4.41 |
TN-TDZ3 | 100 | 11.11 | 1.75 | 33.33 | 3.57 | 14.67 | 4.16 | 39.44 | 3.47 |
TN-TDZi4 | 100 | - | - | - | - | - | - | - | - |
[0062]
TN-TDZ4 | 100 | 15.71 | 2.89 | 21.83 | 2.99 | 50.89 | 3.01 | 46.67 | 5.00 |
TN-TDZi5 | 100 | 19.21 | 5.18 | 42.22 | 5.09 | 40.56 | 4.87 | 10.90 | 4.00 |
TN-TDZ5 | 100 | 37.55 | 2.89 | 21.83 | 4.18 | 28.44 | 2.14 | 12.22 | 4.20 |
TN-TDZi6 | 100 | 29.38 | 5.95 | 36.11 | 5.85 | 15.26 | 3.03 | 15.38 | 1.93 |
TN-TDZ6 | 100 | 50.57 | 3.45 | 34.52 | 2.38 | 7.33 | 2.31 | 25.56 | 3.47 |
TN-TDZi7 | 100 | 52.54 | 6.11 | 22.22 | 8.39 | 44.98 | 4.23 | 32.05 | 2.94 |
TN-TDZ7 | 100 | 39.08 | 3.45 | 8.33 | 2.38 | 14.44 | 2.14 | 25.00 | 4.41 |
TN-TDZi8 | 100 | 28.81 | 4.48 | 18.89 | 5.09 | 33.33 | 2.5 | 28.85 | 3.85 |
TN-TDZ8 | 100 | 41.24 | 4.26 | 41.11 | 8.39 | 26.11 | 3.04 | 51.28 | 2.94 |
TN-TDZi9 | 100 | 16.95 | 5.09 | 7.78 | 5.09 | 15.26 | 3.03 | 14.74 | 4.84 |
TN-TDZ9 | 100 | 59.32 | 4.49 | 33.33 | 6.67 | 27.31 | 3.03 | 22.44 | 2.94 |
TN-TDZi10 | 100 | 59.89 | 5.95 | 39.44 | 8.22 | 14.46 | 3.19 | 10.90 | 4.00 |
TN-TDZ10 | 100 | 5.75 | 2.30 | 13.49 | 3.64 | 9.33 | 4.16 | 31.67 | 3.34 |
TDL | 100 | 19.44 | 1.39 | 31.86 | 1.70 | 22.92 | 2.95 | 49.15 | 1.96 |
Ningnanmycin | 100 | 45.83 | 2.78 | 48.04 | 0.85 | 32.29 | 5.31 | 30.34 | 2.66 |
Virazole | 100 | 37.96 | 2.12 | 40.69 | 0.85 | 42.71 | 8.96 | 26.50 | 1.96 |
-: undetermined
Table 45-methyl isophthalic acid, 2, the 3-thiadiazoles joins-1, the working method that 3-4-thiadiazoles derivative IV and intermediate III thereof and commercially available agricultural chemical are used with
Claims (8)
1. one type of 5-methyl isophthalic acid, 2, the 3-thiadiazoles joins 1, and the 3-4-thiadiazoles derivative is characterized in that itself and its midbody has suc as formula the chemical structure of general formula shown in IV and the III:
Wherein, Ar is the group that is selected from phenyl, 4-fluorophenyl, 3-fluorophenyl, 2-nitrophenyl, 4-nitrophenyl, 3-chloro-phenyl-, 4-chloro-phenyl-, 4-aminomethyl phenyl, 3-aminomethyl phenyl, 3-p-methoxy-phenyl.
2. the described 5-methyl isophthalic acid of claim 1,2, the 3-thiadiazoles joins 1, the compound method of 3-4-thiadiazoles derivative IV and intermediate III thereof, concrete synthetic route is following:
Wherein, Ar is the group that is selected from phenyl, 4-fluorophenyl, 3-fluorophenyl, 2-nitrophenyl, 4-nitrophenyl, 3-chloro-phenyl-, 4-chloro-phenyl-, 4-aminomethyl phenyl, 3-aminomethyl phenyl, 3-p-methoxy-phenyl;
Specifically be divided into following steps:
A. the preparation of intermediate N (2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-formohydrazide group) sulfo-acyl group) substituted benzamide III:
With the 5-methyl isophthalic acid of 3.33 mmoles, 2, the replacement isothiocyanic acid ester II of 3-thiadiazoles-4-formyl hydrazine I, 3.33 mmoles and 20 milliliters of DMF join in 50 milliliters of three mouthfuls of round-bottomed flasks room temperature; Stirred 6 hours; White solid occurs, filter gained solid ethyl alcohol recrystallization, yield 60%-90%, measure fusing point with
1HNMR, the amount of synthetic compound III enlarges by corresponding proportion or dwindles, and the volume of reaction vessel enlarges by corresponding proportion or dwindles; The chemical structure and the physical and chemical parameter of compound III are seen table 1; B.5-methyl isophthalic acid, 2, the 3-thiadiazoles joins 1, the preparation of 3-4-thiadiazoles derivative IV:
N-(2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-formohydrazide group) sulfo-acyl group) substituted benzamide III, 20 methyl alcohol, 0.1 milliliter of vitriol oil of in 50 milliliters of original place flasks, adding 3.0 mmoles, stirring and refluxing 6 hours; White solid occurs, filter gained solid ethyl alcohol recrystallization, yield 60%-90%, measure fusing point with
1H NMR, the amount of synthetic compound IV enlarges by corresponding proportion or dwindles, and the volume of reaction vessel enlarges by corresponding proportion or dwindles; The chemical structure and the physical and chemical parameter of compound IV are seen table 1;
C.5-methyl isophthalic acid, 2, the 3-thiadiazoles joins 1, and 3-4-thiadiazoles derivative IV and intermediate III thereof are to the mensuration of pathogenic fungi growth activity:
5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins 1; 3-4-thiadiazoles derivative IV and intermediate III sterilization thereof or bacteriostatic activity adopt thalli growth rate assay method, and detailed process is: get 5 milligrams of sample dissolution in an amount of N, then with containing the medicament that a certain amount of polysorbas20 emulsifier aqueous solution is diluted to 500 mcg/ml; To supply the reagent agent under aseptic condition, respectively to draw in 1 milliliter of injection petridish, and add 9 milliliters of substratum more respectively, it is dull and stereotyped to process 50 mcg/ml pastilles after shaking up; Flat board to add 1 milliliter of aqua sterilisa is done blank, cuts the bacterium dish with the punch tool of 4 millimeters of diameters along the mycelia outer rim, moves on the pastille flat board; Being equilateral triangle puts; Every processing repetition 3 times is placed on cultivation in 24 ± 1 degrees centigrade of constant incubators with petridish, and colony diameter to be contrasted expands to 2-3 centimetre of " Invest, Then Investigate " and respectively handles bacterium dish expansion diameter; Average; Relatively calculate relative bacteriostasis rate with blank, supply the examination bacterial classification to comprise the kind of most of phytopathogen of the actual generation in multiple representative field in China's agriculture prodn, 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: ring rot of apple bacterium (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: cereal rhizoctonia (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum);
D. 5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins 1, the mensuration of 3-4-thiadiazoles derivative IV and intermediate III inducing anti-disease activity thereof:
5-methyl isophthalic acid of the present invention, 2, the 3-thiadiazoles joins 1, and 3-4-thiadiazoles derivative IV and the active screening method of intermediate III evoking tobacco resisting tobacco mosaic virus (TMV) thereof are following: the mensuration of the direct antiviral activity that exsomatizes adopts half page of method to carry out; It is the common cigarette that seedling age is consistent that live body is induced, and 3 basins are one group, respectively at the cigarette seedling of inoculation pre-treatment in preceding 7 days; Processing mode comprises: spray test compound solution 2 to 3 times, and each 10 milliliters, or soil treating; Each 10 milliliters, the 7th day frictional inoculation TMV on the tobacco leaf that newly grows places its growth optimal temperature and the following cultivation of illumination after 3 days the cigarette seedling; The inspection incidence; Comprehensive scab number is calculated as follows out the inducing anti-disease toxic effect fruit of test compound to TMV, and 3 repetitions are established in each processing, and contrast divides blank and standard chemicals treatment to contrast 2 kinds; Selecting tiadinil (TDL) (purity is greater than 99.5%) is the plant inducing anti-disease activator of standard:
Wherein, R is the induce effect of new compound to the anti-TMV of tobacco, 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 handling rear blade, unit: individual through compound.
3. the described 5-methyl isophthalic acid of claim 1,2, the 3-thiadiazoles joins 1, and 3-4-thiadiazoles derivative IV and intermediate III thereof go up the purposes of acceptable assistant in preparing sterilant with agricultural.
4. the described 5-methyl isophthalic acid of claim 1,2, the 3-thiadiazoles joins 1, and 3-4-thiadiazoles derivative IV and intermediate III thereof go up the purposes of acceptable assistant in preparing anti-plant virus agent with agricultural.
5. the described 5-methyl isophthalic acid of claim 1,2, the 3-thiadiazoles joins 1, and 3-4-thiadiazoles derivative IV and intermediate III thereof go up the purposes of acceptable assistant in preparing the plant activator with agricultural.
6. the described 5-methyl isophthalic acid of claim 1; 2; The 3-thiadiazoles joins 1; 3-4-thiadiazoles derivative IV and intermediate III thereof and agricultural go up acceptable assistant and be selected from Chlorpyrifos 94, inferior Nong, acetamiprid, Affirm (Merck Co.), more visit that rhzomorph, Avrmectin, pleocidin, fenvalerate, efficient fenvalerate, PP-383, beta_cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, Beta-FCR-1272, FCR-1272, Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, WL 43479, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiophene worm quinoline, thiophene worm piperazine, thiophene worm amine, MTI-446, clothianadin, Da Tenan, diflubenzuron, the young urea that goes out, Teflubenzuron, deinsectization are grand, fluorine bell urea, WL 115110, pyridine worm are grand, Acarus tritici urea, poisonous insect urea, penfluron, Noviflumuron are noviflumuron, its CAS 121451-02-3, flucycloxuron, Novaluron be Rimon, fluorine pyridine urea, Bay sir 6874 promptly { 1-[(3.5-two chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, Bay SIR-8514 promptly [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, promptly two three WL 115110s of Bistrifluron, furans worm hydrazides, worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, PP-062, MTMC, isoprocarb, cartap, fenobucarb, leaf disperse, one or more medicaments in the carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, azoles mite ester, pyridaben, four mite piperazines, alkynes mite Te, butyl ether urea, benfuracarb, pyrrole aphid ketone, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, PP618, ethoprophos, fluorine worm nitrile, desinsection list, disosultap, chlorine insect amide, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, azoles insect amide, tebufenpyrad, bromothalonil, pyrazine ketone, second mite azoles, tebufenpyrad, the young ketone of rattling away, pyrrole propyl ether, emaricin mix the purposes of using in preparing sterilant; The described 5-methyl isophthalic acid of claim 1; 2, the 3-thiadiazoles joins 1, and 3-4-thiadiazoles derivative IV and intermediate III thereof the total quality percentage composition in compsn is 1%-90%; The described 5-methyl isophthalic acid of claim 1; 2, the 3-thiadiazoles joins 1, and the ratio of 3-4-thiadiazoles derivative IV and intermediate III thereof and said medicament is mass percent 1%: 99% to 99%: 1%; The formulation of compsn is selected from sustained release dosage; Pulvis; Micro-capsule suspension; The dispersible body preparation; The dispersible solid preparation; Seed treatment emulsion; Aqueous emulsion; Big granula; Microemulsion; Suspended emulsion agent; Water-soluble granule; Soluble thick agent; Water-dispersible granules; Poison grain; Aerosol; Block poison bait; Sustained-release block; Dense poison bait; The capsule granula; Capsule suspension; Dry mixing kind pulvis; Missible oil; The electrostatic spray agent; Water-in-oil emulsion; Oil-in-water emulsion; Smoke candle; Granula subtilis; Smoke candle; Smoke cartridge; The smog rod; The seed treatment suspension agent; The smog sheet; Smoke substance; The smog ball; Granular poison bait; Foaming agent; The drift pulvis; Ointment; Thermal fog; Solid-liquid mixes the dress agent; Liquid/liquid mixes the dress agent; Cold mist agent; Gu Gu/mix and adorn agent; The medicine lacquer; Microgranules; Oil suspending agent; 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 emulsion; The film forming finish; Soluble powder; The seed treatment water solube powder; The ultra-low volume suspension agent; Tablet; Follow the trail of pulvis; Ultra low volume liquids; The steam releasing agent; In the wet-mixing kind water-dispersible powder any one; The plant that compsn is suitable for is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, yam, cassava, soybean, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, genseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tea, bamboo shoots, hops, pepper.
Claimed in claim 1, wherein the 5 - methyl-1, 2,3 - thiadiazole 1,3 -4- associated thiadiazole derivatives and intermediates III and IV agriculturally acceptable additives and with selected benzothiadiazole, thiophene acid bacteria amine, methyl amine induced thiophene 4 - methyl-1, 2,3 - thiadiazole-5 - carboxylic acid 4 - methyl-1, 2,3 - thiadiazole -5 - Sodium 4 - methyl-1, 2,3 - thiadiazole-5 - Ethyl 4 - (bromomethyl) -1,2,3 - thiadiazole-5 - carboxylic acid ethyl ester, 4 - iodomethyl-1, 2,3 - thiadiazole-5 - Ethyl 4 - bromo-5 - methyl-1, 2,3 - thiadiazole-4 - iodo-5 - methyl-1, 2,3 - thiadiazole, 4,4 - dibromo-1 ,2,3 - thiadiazole-5 - carboxylic acid ethyl ester, DL-β-aminobutyric acid, ribavirin, An tolfenamic, Ningnanmycin or salicylic acid, Cytosinpeptidemycin, dichloro-isonicotinic acid, allyl isothiazole, Isotianil, Cymoxanil, thiram, ziram, mancozeb, fosetyl aluminum, thiophanate-methyl, chlorothalonil, the enemy can be loose, procymidone, Fenpropidine, thiophanate, thiophanate, metalaxyl, salicylic acid, flumorph, Dimethomorph, Efficient metalaxyl, benalaxyl efficient, bis cypermethrin bacteria amine, flusulfamide, flusulfamide methyl, thiophene amine fluoride bacteria, flutolanil, leaf blight phthalate, cyclopropane amino acid bacteria, cyflufenamid, cycloalkyl acyl bacteria amine, cyano bacteria amine, amine silica thiabendazole, furosemide topiramate amine bacteria, penthiopyrad, diacetylene amine acid bacteria, zoxamide, ofurace, carboxin, acetic bacteria Lee, iprodione, ethyl bacteria ester, ether amines bacteria, fluoxastrobin, kresoxim-methyl, phenoxy bacteria amine, oxime ether amines bacteria, picoxystrobin, pyraclostrobin, trifloxystrobin, enestroburin, alkylene amines trifloxystrobin, Oxygen propiconazole, bromuconazole, cyproconazole, difenoconazole azole, Diniconazole, efficient diniconazole, Epoxiconazole, fenbuconazole, fluorine quinazoline, Flusilazole, Flutriafol, Hexaconazole alcohol, imine yl, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, PTFE Difenoconazole, triadimenol, sterilization azole, Bitertanol, thiabendazole, fuberidazole, imazalil, efficient imazalil, prochloraz, triflumizole, Cyazofamid, imidazole cycloheximide, evil imidazole, pefurazoate, oxazole Cycloheximide, pyridine bacteria oxazole, hymexazol oxadixyl, thiophene pyraclostrobin, earth benomyl, Xin chlorthalidone, benzoth thiocyanate, twelve tridemorph, fenpropimorph, tridemorph, mix species slightly, fludioxonil, fluazinam, piperidine oxime spots, fungus amine piperidine ring, boscalid, fluorine boscalid, piperidine amine bacteria, cyprodinil, mepanipyrim fluorine, ferimzone, ethyl bacteria amine, pyrimethanil, fenarimol, nuarimol, Chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, quinoline propoxy, phenoxy quinoline, diethofencarb, iso C bacteria amines, benzene thiabendazole amines Propamocarb, sulfur bacteria Granville, edifenphos, iprobenfos, topiramate bacteria phosphorus, tolclofos, blasticidin, kasugamycin, polymyxin, and more Polyoxins, validamycin, Jinggangmycin, streptomycin, metalaxyl, furalaxyl, Benalaxyl, furosemide amide, mepronil, carbendazim, benomyl, thiophanate-methyl, three Trazodone, ethirimol sulfonate, dimethyl ethyl phenol, ethirimol, captafol, captan, folpet, vinclozolin, chlorofluorocarbons sclerotia Lee, Dimetachlone, chlorothalonil, Isoprothiolane, kitazine, leaf blight, PCNB, mancozeb, Propineb, fosetyl-aluminum, sulfur, Bordeaux mixture, copper sulfate, copper oxychloride, cuprous oxide, copper hydroxide, benzene cycloheximide, Pencycuron, da cycloheximide, tetrachlorophthalide, pyroquilon, Spiro bacteria amines, Tricyclazole, triforine, more fruit pyridine, Iminoctadine salt Iminoctadine amine, Dicloran, flusulfamide benzene, toluene, flusulfamide, indole ester, Fenaminosulf, oxolinic acid, allyl benzene, thiazole, bronopol, methyl iodide, metham, enemy lines esters, dazomet, two chloro-isopropyl ether, Fosthiazate, Cadusafos, fensulfothion, insects fenamiphos, fenamiphos, Ethoprophos, except line phosphorus, chlorine triazophos, carbosulfan cyclophosphamide, oxamyl, aldicarb, g Budweiser, sulfuryl fluoride, dichloropropene in any one or combination of the two agents for the preparation of fungicides and their use in the control of plant diseases; composition is suitable for a plant selected from rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, beans, beans, peas, green beans, red beans, cotton, sericulture, peanut, rapeseed, sesame, sunflower, sugar beet, sugar cane, coffee, cocoa, ginseng, Fritillaria, rubber, coconut, oil Brown, sisal, tobacco, tea, bamboo shoots, hops, pepper; compositions for diseases selected from solani, Botrytis cinerea fungus, peanut leaf spot fungus, Fusarium graminearum, Phytophthora infestans, Apple Physalospora germs, Rhizoctonia solani, Sclerotinia sclerotiorum, Rhizoctonia cereal plant diseases caused; claim 1 5 - methyl-1 ,2,3 - thiadiazole-linked 1,3 -4- thiadiazole derivatives and intermediates III IV in the composition ratio of 1% -90% weight percentage, selected from a sustained release dosage form of the composition, powder, microcapsule suspensions, dispersible liquid formulations can be distributed solid preparation, seed treatment, emulsions, aqueous emulsion, large granules, micro-emulsion, suspension emulsion, a water-soluble granule, soluble concentrate agent, water dispersible granules, poison Valley, aerosols, block bait, release block, concentrated bait, capsules granules, capsules suspensions, dry dressing powders, emulsifiable concentrates, electrostatic sprays, oil-in-water emulsions, water-in-oil emulsion, aerosol cans, fine granules, smoke candle, smoke cartridges, smoke stick, suspension for seed treatment agents, smoke tablets, aerosols, smoke pellets, granular baits, made gas agent, rafting powder, ointment, thermal fogging agent, solid / liquid mixing device agent, liquid / liquid mixing device agent, fog agent, solid / solid mixing loading dose, drug paint, particles, oils suspending agents, oil dispersible powders, creams, flaky baits, thick glue, sprinkling agents, stick agents, seed coating, bait, liniment, small baits, suspended emulsion , forming oil, soluble powders, water soluble powder for seed treatment, ultra low volume suspension, tablet, tracking powder, ultra low volume liquid, vapor release agents, water-dispersible powder wet dressing of any one.
8. the described 5-methyl isophthalic acid of claim 1,2, the 3-thiadiazoles joins 1; 3-4-thiadiazoles derivative IV and intermediate III thereof and agricultural go up acceptable assistant and be selected from diazosulfide, tiadinil, 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, 4-brooethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-iodomethyl-1; 2,3-thiadiazoles-5-ethyl formate, 4-brooethyl-5-methyl isophthalic acid, 2; 3-thiadiazoles, 4-iodomethyl-5-methyl isophthalic acid, 2,3-thiadiazoles, 4; 4-dibromo methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, first thiophene lure any one or the two kinds of medicament combined preparation in amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, the different metsulfovax to become anti-plant virus agent or plant activator and prevent and treat the purposes of phytopathy in poisoning at Antiphytoviral disease or inducing plant; The described 5-methyl isophthalic acid of claim 1; 2, the 3-thiadiazoles joins 1, and 3-4-thiadiazoles derivative IV and intermediate III thereof the total quality percentage composition in compsn is 1%-90%; The described 5-methyl isophthalic acid of claim 1; 2, the 3-thiadiazoles joins 1, and the ratio of 3-4-thiadiazoles derivative IV and intermediate III thereof and above-mentioned medicament is mass percent 1%: 99% to 99%: 1%; The formulation of compsn is selected from sustained release dosage; Pulvis; Micro-capsule suspension; The dispersible body preparation; The dispersible solid preparation; Seed treatment emulsion; Aqueous emulsion; Big granula; Microemulsion; Suspended emulsion agent; Water-soluble granule; Soluble thick agent; Water-dispersible granules; Poison grain; Aerosol; Block poison bait; Sustained-release block; Dense poison bait; The capsule granula; Capsule suspension; Dry mixing kind pulvis; Missible oil; The electrostatic spray agent; Water-in-oil emulsion; Oil-in-water emulsion; Smoke candle; Granula subtilis; Smoke candle; Smoke cartridge; The smog rod; The seed treatment suspension agent; The smog sheet; Smoke substance; The smog ball; Granular poison bait; Foaming agent; The drift pulvis; Ointment; Thermal fog; Solid-liquid mixes the dress agent; Liquid/liquid mixes the dress agent; Cold mist agent; Gu Gu/mix and adorn agent; The medicine lacquer; Microgranules; Oil suspending agent; 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 emulsion; The film forming finish; Soluble powder; The seed treatment water solube powder; The ultra-low volume suspension agent; Tablet; Follow the trail of pulvis; Ultra low volume liquids; The steam releasing agent; In the wet-mixing kind water-dispersible powder any one; The plant that compsn is suitable for is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, yam, cassava, soybean, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, genseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tea, bamboo shoots, hops, pepper; The phytopathy that compsn is suitable for is poisoned and is selected from tobacco mosaic virus disease and chilli pepper mosaic virus disease.
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CN103012392A (en) * | 2013-01-08 | 2013-04-03 | 南开大学 | Pyridine derivatives containing 1.2,3-thiadiazole, and preparation method and application thereof |
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CN107258137A (en) * | 2017-07-28 | 2017-10-20 | 成都优耕生态农业科技有限公司 | A kind of modification method of acid soil and the implantation methods of plant |
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Cited By (6)
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CN103012391A (en) * | 2013-01-05 | 2013-04-03 | 天津出入境检验检疫局动植物与食品检测中心 | Pyrimidine derivatives containing 1.2,3-thiadiazole, and preparation method and application thereof |
CN103012391B (en) * | 2013-01-05 | 2015-04-22 | 天津出入境检验检疫局动植物与食品检测中心 | Pyrimidine derivatives containing 1,2,3-thiadiazole, and preparation method and application thereof |
CN103012392A (en) * | 2013-01-08 | 2013-04-03 | 南开大学 | Pyridine derivatives containing 1.2,3-thiadiazole, and preparation method and application thereof |
CN103467462A (en) * | 2013-09-14 | 2013-12-25 | 湖南科技大学 | 3-(1,3,4- thiadiazole)-1,3-benzooxazine-2-acetone compounds and application thereof |
CN103467462B (en) * | 2013-09-14 | 2015-07-08 | 湖南科技大学 | 3-(1,3,4- thiadiazole)-1,3-benzooxazine-2-acetone compounds and application thereof |
CN107258137A (en) * | 2017-07-28 | 2017-10-20 | 成都优耕生态农业科技有限公司 | A kind of modification method of acid soil and the implantation methods of plant |
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