CN101845054A - Bis-triazolothiadiazole compounds containing 1,2,3-thiadiazole and preparation method and application thereof - Google Patents

Abstract

The invention provides bis-triazolothiadiazole derivatives containing 1,2,3-thiadiazole and a preparation method and application thereof. The invention relates to heterocyclic compounds containing 1,2-diazole, which have the following chemical structure general formula shown as the specification. The invention discloses a chemical structure and a synthesis method of the compounds with the general formula, a using method and application of the compounds for resisting TMV virus, and a using method and application of the compounds for inducing tobacco anti-TMV viruses. The invention further discloses a using method and application of the compounds with the general formula in inhibiting the growth of plant pathogenic fungi. The invention further discloses application of the compounds with the general formula in controlling agricultural, forest and garden plant diseases and plant virus diseases through the combination use with the traditional antivirus agents and bactericides.

Description

Contain 1,2, two s-triazolothiadiazole compounds of 3-thiadiazoles and its production and use

Technical field

Technical scheme of the present invention relates to the heterogeneous ring compound that contains 1,2-diazole, is specifically related to two triazolothiadiazole derivatives.

Background technology

1,2, the 3-thiadiazoles derivative has wide biological activity, but commercial medical kind and pesticide species are all rare, contriver's early-stage Study finds that this analog derivative has the activity of good inducing plant viral diseases and fungal disease, wherein, the first thiophene lures amine to belong to low toxicity compounds, just in the industrialization development process; Diazosulfide (BTH) and tiadinil (TDL) are the most successful plant activator of commercialized development, also are 1,2, the derivative of 3-thiadiazoles.1,2, the 4-triazole derivative also had suitable wide biological activity, and this two classes active group is connected to the compound s-triazolo-thiadiazoles that forms in a part promptly synthetic and bibliographical information (Shafiee, A. in 1977; Lalezari, I.; Mirrashed, M.; Nercesian, D.1,2,3-Selenadiazolyl-1,3,4-oxadiazole, 1,2,3-thiadiazolyl-1,3,4-oxadiazole and 5-(1,2,3-thiadiazolyl)-and s-triazolo[3,4-b]-1,3,4-thiadiazole.J.Heterocyclic.Chem.1977,14,567-571), thereafter, bibliographical information contain s-triazolo-thiadiazoles derivative and anti-microbial activity (Zhang Ziyi, the Chen Xin of pyridine group, fused heterocyclic compound research-I.3-(4 '-pyridyl)-the 6-aryl-all-triazolo [3,4-b]-1,3, synthetic and the anti-microbial property of 4-thiadiazoles, the chemistry journal, 1991,49 (5): 513-520); The s-triazolo-thiadiazoles derivative that the part aryl replaces has certain biological activity (Zhang Ziyi, Li Ming, Zhao Lan, Li Zhengming, Liao Renan, the research of fused heterocyclic compound (X)-3-aryl-6-benzamido s-triazolo-[3,4-b]-1,3, the synthetic and biological activity of 4-thiadiazole compound. SCI, 1994,15 (2): 220-223; Tensiometry, Zhang An incites somebody to action, Zhou Guangqiang, Zhang Ziyi .3-aryl-6-trichloromethyl-1,2,4-triazolo [3,4-b]-1,3, the synthetic and spectroscopic characterization of 4-thiadiazoles. organic chemistry, 2002,22 (9): 663-666); The s-triazolo-thiadiazoles derivative and the biological activity thereof that contain Glucopyranose (contain glucose substituting group s-triazolo-[3,4-b]-1,3, the synthetic and bioactivity research of 4-thiadiazoles fused heterocyclic compound. Beijing Institute of Technology's journal, 2002,22 (6): 761-764).Contriver's research and design has in earlier stage been synthesized a class and has been contained 1,2, the triazolo thiadiazoles derivative (200810054334.1) of 3-thiadiazoles, and its chemical structure is as follows:

Bioactivity screening finds that this compounds has excellent bactericidal activity.In order to seek the more compound of high biological activity, the present invention designs and has synthesized a class and contain 1,2, and two s-triazolothiadiazole compounds of 3-thiadiazoles carry out bioactive screening and evaluation simultaneously, for the initiative research of novel pesticide provides the candidate compound.

Summary of the invention

Technical problem to be solved by this invention is: provide new and contain 1,2, the synthetic method of two triazolo thiadiazoles derivatives of 3-thiadiazoles, provide this compounds to suppress biological activity and the measuring method thereof of agricultural and gardening and forestry plant pathogen and plant virus, 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: have two [3-(4-methyl isophthalic acids that agricultural, gardening and forestry fungicidal activity or antiviral activity or inducing plant produce antiviral activity, 2,3-thiadiazoles-5-yl) s-triazolo-thiadiazoles] chemical structure of general formula of derivative is as follows:

Wherein: X is 0 or is selected from ethylene, trimethylene, tetramethylene, 1,5-pentylidene, hexamethylene, 1, the inferior heptyl, 1 of 7-, 2-phenylene, 1,3-phenylene 1,4-phenylene, 2,5-furylidene, 2, the inferior thienyl, 2 of 5-, 6-pyridylidene, suitable-1, the 2-vinylidene, anti--vinylene, 2,2 '-Ya biphenylyl, 1,1-cyclobutyl, 1,1-Dimethylenecyclohexacompound, 3, the group of the inferior imidazolyl of 5-.

The synthetic method of two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo-thiadiazoles] derivatives of the present invention is as follows:

Wherein: X is 0 or is selected from ethylene, trimethylene, tetramethylene, 1,5-pentylidene, hexamethylene, 1, the inferior heptyl, 1 of 7-, 2-phenylene, 1,3-phenylene 1,4-phenylene, 2,5-furylidene, 2, the inferior thienyl, 2 of 5-, 6-pyridylidene, suitable-1, the 2-vinylidene, anti--vinylene, 2,2 '-Ya biphenylyl, 1,1-cyclobutyl, 1,1-Dimethylenecyclohexacompound, 3, the group of the inferior imidazolyl of 5-.

Embodiment

Enforcement of the present invention specifically is divided into following steps:

A.3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-4-amino-5-sulfydryl-1,2, the preparation of 4-triazole:

3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-4-amino-5-sulfydryl-1,2, the preparation of 4-triazole is carried out with reference to the method for Chinese patent 200810054334.1.

B. the preparation of two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo-thiadiazoles] derivatives:

With 1-2.2 mmole 3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-4-amino-5-sulfydryl-1,2, the dicarboxylic acid of 4-triazole, 0.5-1.1 mmole and 0.25-0.5 mmole Tetrabutyl amonium bromide add 50 milliliters of round-bottomed flasks, add 15 milliliters of POCl again ₃, under the induction stirring, oil bath is heated to 60 degrees centigrade, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, dry crude product, according to the pure product calculated yield of gained, measure fusing point and ¹HNMR, the consumption of synthetic compound can or dwindle by corresponding proportion expansion; The chemical structure of compound sees Table 1;

C. contain 1,2, the mensuration that two triazolothiadiazole derivatives of 3-thiadiazoles influence the pathogenic fungi growth activity:

Of the present inventionly contain 1,2, the two triazolo thiadiazoles derivative sterilization of 3-thiadiazoles or the measuring method of bacteriostatic activity are as follows:

Adopt thalli growth rate assay method, detailed process is, get 5 milligrams of sample dissolution in an amount of dimethyl formamide, then with containing the medicament that a certain amount of polysorbas20 emulsifier aqueous solution is diluted to 500 mcg/ml, reagent agent is respectively drawn under aseptic condition in 1 milliliter of injection culture dish, add 9 milliliters of substratum more respectively, make 50 mcg/ml pastille flat boards after shaking up, do blank with the flat board that adds 1 milliliter of aqua sterilisa, punch tool with 4 millimeters of diameters cuts the bacterium dish along the mycelia outer rim, move on the pastille flat board, being equilateral triangle puts, every processing repeats 3 times, and culture dish is placed on 24 ± 1 degrees centigrade interior cultivation of constant incubator, 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, comprise frequently seen plants pathogenic bacteria on 9 kinds of agriculturals for the examination bacterial classification, as: F: tomato early blight bacterium (Alternaria solani); D: peanut Cercospora bacteria (Cercospora arachidicola); I: ring rot of apple bacterium (Physalospora piricola); L: botrytis cinerea pers (Botrytis cinerea); T: Rhizoctonia solani Kuhn (Pellicularia sasakii); G: fusarium graminearum (Gibberella zeae); AK: phytophthora infestans (Phytophthorainfestans (Mont.) de Bary); N: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum); RC: cereal rhizoctonia (Rhizoctonia cerealis);

D. of the present inventionly contain 1,2, the mensuration of the derivative induced anti-disease activity of two triazolothiadiazoles of 3-thiadiazoles:

Of the present inventionly contain 1,2, the active screening method of the derivative induced tobacco resisting tobacco mosaic virus of two triazolothiadiazoles of 3-thiadiazoles (TMV) is as follows: the mensuration of the direct antiviral activity that exsomatizes adopts half page of method to carry out; It is common cigarette with the seedling age unanimity that live body is induced, 3 basins are one group, cigarette seedling respectively at inoculation pre-treatment in preceding 7 days, processing mode comprises: spray test compound solution 2 to 3 times, each 10 milliliters, or soil treatment, each 10 milliliters, the 7th day frictional inoculation TMV on the tobacco leaf that newly grows, the cigarette seedling is placed its growth optimal temperature and illumination, and cultivation is after 3 days down, and inspection incidence, comprehensive scab number are calculated as follows out the inducing anti-disease toxic effect fruit of test compound to TMV, 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:

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

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 containing 1; 2; two triazolo thiadiazoles of 3-thiadiazoles have carried out the optimization of first guide structure; and the synthetic new compound carried out the screening of bacteriostatic activity, this compounds can be used for the plant protection that agriculture field and field of forestry and gardening field disease carry out.

The present invention will more specifically describe by specific preparation and biological activity determination embodiment and contain 1,2, synthetic and the biological activity and the application thereof of two triazolo thiadiazoles derivatives of 3-thiadiazoles, but described 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 as follows:

Embodiment 1

Compound 3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-4-amino-5-sulfydryl-1,2, the preparation of 4-triazole and structure are identified

6.25 grams, 80% hydrazine hydrate is joined in 50 milliliters of dehydrated alcohols, stir down, slowly drip 17.2 gram 4-methyl isophthalic acids, 2,3-thiadiazoles-5-ethyl formate drips complete vigorous stirring, about 15 minutes, moment was separated out a large amount of solids, and suction filtration is also washed with dehydrated alcohol, be spin-dried for filtrate, obtain yellow solid, sherwood oil is washed, combining solid, infrared lamp are dry down, obtain orange-yellow 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl hydrazine 14.9 grams, productive rate 94.2%; With 11.6 gram 4-methyl isophthalic acids, 2,3-thiadiazoles-5-formyl hydrazine joins in 150 milliliters of ethanol solutions that are dissolved with 7.5 gram 82%KOH, stirs and makes it dissolving, drips CS again ₂8.36 gram has orange/yellow solid to separate out, stirring at room 4 hours gradually; Leave standstill, suction filtration obtains orange-yellow 4-methyl isophthalic acid, and 2,3-thiadiazoles-5-formohydrazide group dithio formic acid sylvite 19.57 grams, productive rate 98% is directly used in next step reaction; With 19 gram 4-methyl isophthalic acids, 2,3-thiadiazoles-5-formohydrazide group dithio formic acid sylvite joins in 120 milliliters of dehydrated alcohols, stirring is yellow emulsion, adds 8.6 grams, 80% hydrazine hydrate again, reflux 6 hours, cooling adds 100 ml waters, obtain yellow-green soln, concentrated hydrochloric acid is acidified to pH=2-3, and a large amount of white solids are separated out, standing over night, suction filtration also washes with water to neutrality, dry 3-(4-methyl isophthalic acid, 2 of getting under the infrared lamp, the 3-thiadiazolyl group)-4-amino-5-sulfydryl-1,2,4-triazole 10.4 grams, productive rate 70%; ¹H NMR (δ, DMSO-d ₆): 14.338 (s, H, NH), 6.805 (s, 2H, N-NH ₂), 2.948 (s, 3H, thiadiazolyl-CH ₃).

Embodiment 2

Compound WSX-8:1, the synthetic and structure of 6-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] hexane is identified

With 2.2 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 1 mmole suberic acid and 0.5 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 15 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 90% is used DMF-C ₂H ₅The OH recrystallization gets white crystal; Fusing point is greater than 250 degrees centigrade, ¹HNMR (δ, DMSO-d ₆): 1.496-1.859 (m, 8H, 4CH ₂), 3.137-3.173 (t, 4H, 2CH ₂), 3.064 (s, 6H, 2thiadiazolyl-CH ₃).

Embodiment 3

Compound WSX-11:1, the synthetic and structure of 1-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-methylene radical] hexanaphthene is identified

With 1.1 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.5 mmole 1,1-cyclohexanediacetic acid and 0.25 mmole Tetrabutyl amonium bromide join in 25 milliliters of round-bottomed flasks, add 8 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 76% is used DMF-C ₂H ₅The OH recrystallization gets white crystal; Fusing point: the 247-248 degree, ¹HNMR (δ, DMSO-d ₆) 1.605-1.710 (m, 10H, cyclohexyl-H), 3.115-3.139 (t, 4H, 2CH ₂), 3.083 (s, 6H, 2thiadiazolyl-CH ₃).

Embodiment 4

Compound WSX-12:1, the synthetic and structure of 1-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] tetramethylene is identified

With 1.1 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.5 mmole 1,1-cyclobutyl dioctyl phthalate and 0.25 mmole Tetrabutyl amonium bromide join in 25 milliliters of round-bottomed flasks, add 8 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 89% is used DMF-C ₂H ₅The OH recrystallization gets the yellowish brown crystal; Fusing point is greater than 250 degrees centigrade.

Embodiment 5

Compound WSX-16:2, the synthetic and structure of 6-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] pyridine is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole, 2,6 dinicotinic acids and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 90% is used DMF-C ₂H ₅The OH recrystallization gets pale yellow crystals; Fusing point is greater than 250 degrees centigrade.

Embodiment 6

Compound WSX-17:1, the synthetic and structure of 2-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] ethane is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole Succinic Acid and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 79% is used DMF-C ₂H ₅The OH recrystallization gets white crystal; Fusing point is greater than 250 degrees centigrade, ¹HNMR (δ, DMSO-d ₆): 3.764 (s, 4H, 2CH ₂), 3.023 (s, 6H, 2thiadiazolyl-CH ₃).

Embodiment 7

Compound WSX-18: the synthetic and structure of di-[3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles] is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole oxalic acid and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 55% is used DMF-C ₂H ₅The OH recrystallization gets the yellowish brown crystal; Fusing point is greater than 250 degrees centigrade, ¹HNMR (δ, DMSO-d ₆): 3.023 (s, 6H, 2thiadiazolyl-CH ₃).

Embodiment 8

Compound WSX-19: suitable-1, the synthetic and structure of 2-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] ethene is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole maleic acid and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃Wash with water again behind the solution washing to neutrality, the dry crude product that gets, productive rate 45% is used DMF-C ₂H ₅The OH recrystallization gets yellow crystals; Fusing point is greater than 250 degrees centigrade, ¹HNMR (δ, DMSO-d ₆): 8.180 (s, 2H, CH=CH), 3.102 (s, 6H, 2thiadiazolyl-CH ₃).

Embodiment 9

Compound WSX-20: anti--1, the synthetic and structure of 2-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] ethene is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole FUMARIC ACID TECH GRADE and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 61% is used DMF-C ₂H ₅The OH recrystallization gets pale yellow crystals; Fusing point is greater than 250 degrees centigrade.

Embodiment 10

Compound WSX-22:1, the synthetic and structure of 3-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] benzene is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole m-phthalic acid and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 88% is used DMF-C ₂H ₅The OH recrystallization gets white needle-like crystals; Fusing point is greater than 250 degrees centigrade.Results of elemental analyses: calculated value (%), C ₁₈H ₁₀N ₁₂S ₄: C, 41.37; H, 1.93; N, 32.16. measured value of experiment: C, 41.09; H, 1.96; N, 31.48.

Embodiment 11

Compound WSX-25:1, the synthetic and structure of 4-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] benzene is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole terephthalic acid and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 91% is used DMF-C ₂H ₅The OH recrystallization gets white crystal; Fusing point is greater than 250 degrees centigrade.Results of elemental analyses: calculated value (%), C ₁₈H ₁₀N ₁₂S ₄: C, 41.37; H, 1.93; N, 32.16. measured value of experiment: C, 41.05; H, 1.96; N, 30.31.

Embodiment 12

Compound WSX-26:2, the synthetic and structure of 5-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] thiophene is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole 2,5-thiophene dioctyl phthalate and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃Wash with water behind the solution washing to neutrality again and get crude product, productive rate 90% is used DMF-C ₂H ₅The OH recrystallization gets yellow crystals; Fusing point is greater than 250 degrees centigrade, ¹HNMR (δ, DMSO-d ₆): 7.953 (s, 2H, thienyl-H), 3.107 (s, 6H, 2thiadiazolyl-CH ₃).

Embodiment 13

Compound WSX-28:2, the synthetic and structure of 5-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] furans is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole, 2,5 furans dioctyl phthalate and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃Wash with water behind the solution washing to neutrality again and get crude product, productive rate 70% is used DMF-C ₂H ₅The OH recrystallization gets yellow crystals; Fusing point is greater than 250 degrees centigrade, ¹HNMR (δ, DMSO-d ₆): 8.011 (s, 2H, furyl-H), 3.116 (s, 6H, 2thiadiazolyl-CH ₃).

Embodiment 14

Compound WSX-29:2, the synthetic and structure of 2 '-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] diphenyl is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole, 2,2 ' biphenyl dicarboxylic acid and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 67% is used DMF-C ₂H ₅The OH recrystallization gets pale yellow crystals; Fusing point is greater than 250 degrees centigrade, ¹HNMR (δ, DMSO-d ₆): 7.714-7.947 (m, 8H, ArH), 2.906 (s, 6H, 2thiadiazolyl-CH ₃).

Embodiment 15

Compound WSX-30:1, the synthetic and structure of 7-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] heptane is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole nonane diacid and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 92% is used DMF-C ₂H ₅The OH recrystallization gets white crystal; Fusing point is greater than 250 degrees centigrade, ¹HNMR (δ, DMSO-d ₆): 1.429-1.804 (m, 10H, 5CH ₂), 3.127-3.163 (t, 4H, 2CH ₂), 3.055 (s, 6H, 2thiadiazolyl-CH ₃).

Embodiment 16

Compound WSX-32:1, the synthetic and structure of 3-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] propane is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole pentanedioic acid and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 85% is used DMF-C ₂H ₅The OH recrystallization gets the grey needle-like crystal; Fusing point is greater than 250 degrees centigrade.Results of elemental analyses: calculated value (%), C ₁₅H ₁₂N ₁₂S ₄: C, 36.87; H, 2.48; N, 34.40. measured value of experiment: C, 36.51; H, 2.73; N, 33.17.

Embodiment 17

Compound WSX-33:1, the synthetic and structure of 5-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] pentane is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole pimelic acid and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 78% is used DMF-C ₂H ₅The OH recrystallization gets pale yellow crystals; Fusing point: the 229-231 degree, ¹HNMR (δ, DMSO-d ₆): 1.550-1.910 (m, 6H, 3CH ₂), 3.155-3.190 (t, 4H, 2CH ₂), 3.060 (s, 6H, 2thiadiazolyl-CH ₃).

Embodiment 18

Compound WSX-35:3, the synthetic and structure of 5-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] pyrazoles is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole 3,5-pyrazoles diacid and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 78% is used DMF-C ₂H ₅The OH recrystallization gets white crystal; Fusing point is greater than 250 degrees centigrade, ¹HNMR (δ, DMSO-d ₆): 7.952 (s, 1H, pyrazolyl-NH), 3.110 (s, 1H, pyrazolyl-CH), 2.730 (s, 3H, thiadiazolyl-CH ₃), 2.890 (s, 3H, thiadiazolyl-CH ₃).

Embodiment 19

Compound WSX-39:1, the synthetic and structure of 2-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] benzene is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole phthalic acid and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 45% is used DMF-C ₂H ₅The OH recrystallization gets the yellowish brown crystal; Fusing point is greater than 250 degrees centigrade.

Embodiment 20

Compound WSX-73:1, the synthetic and structure of 4-two [3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl) s-triazolo--[3,4-b]-1,3,4-thiadiazoles-6-yl] butane is identified

With 1.5 mmole 3-phenyl-4-amino-5-sulfydryl-1,2,4-triazole, 0.7 mmole hexanodioic acid and 0.35 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 10 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, the dry crude product that gets, and productive rate 91% is used DMF-C ₂H ₅The OH recrystallization gets white crystal; Fusing point is greater than 250 degrees centigrade.

Embodiment 21

Of the present inventionly contain 1,2, the bacteriostatic activity of two triazolo thiadiazoles derivatives of 3-thiadiazoles:

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 (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: ring rot of apple bacterium (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum); RC: cereal rhizoctonia (Rhizoctonia cerealis), these bacterial classifications have good representativeness, can represent the kind of most of pathogenic bacteria that the field takes place in the agriculture production.Thalli growth rate method measurement result sees Table 2, table 2 shows, synthetic part of compounds of the present invention has bacteriostatic action in various degree to the growth of the part pathogenic fungi of mensuration: when 50 mcg/ml, active best control compounds YZK-C-22 better active to most of pathogenic bacteria of test under equal conditions in the patent document 200810054334.1 that the contriver has applied for, but relatively poor to the restraining effect of GZ, BC, SS and four kinds of pathogenic fungies of RC of test; And WSX-26 is 35.29%% to the restraining effect of GZ, is higher than control compounds YZK-C-22 far away; WSX-12, WSX-16, WSX-33 and WSX-35 are respectively the restraining effect of BC: 34.38%, 43.75%, 68.75% and 43.75%, also be higher than control compounds YZK-C-22 far away; WSX-8, WSX-18, WSX-26, WSX-30 and WSX-35 and WSX-73 are respectively the inhibiting rate of SS: 41.67%, 33.33%, 69.44%, 88.89% and 61.11% and 38.89%, also be higher than control compounds YZK-C-22 far away; Other compounds are all not remarkable to the restraining effect of other pathogenic fungies.Above result shows, contains 1,2, and two triazolo thiadiazoles derivatives of 3-thiadiazoles have been because the introducing of close ester spacer group has changed the close ester of target molecule, thereby makes the biological activity of compound be significantly improved.

Embodiment 22

Of the present inventionly contain 1,2, the effect of the anti-tobacco resisting tobacco mosaic virus of two triazolo thiadiazoles derivatives of 3-thiadiazoles:

The active measurement result of anti-TMV sees Table 3, table 3 shows, commercial plant resisting tobacco mosaic virus medicament virazole has certain activity to TMV, the two triazolo thiadiazoles derivatives of major part of the present invention have the activity of direct anti-TMV preferably, WSX-8, WSX-18, WSX-20, WSX-25, WSX-26 and the WSX-32 part of compounds antiviral effect when 500 mcg/ml and 100 mcg/ml is all more than 40%, these compounds all are higher than the measurement result of similar medicament TDL far away in the activity of 500 mcg/ml, and measurement result almost is the twice of TDL; The measurement result that also is higher than the best Ningnanmycin of widely used conventional antiviral agent virazole and antiviral effect.And the antiviral effect of these medicaments also is significantly higher than three of mensuration contrast medicament TDL and virazole and Ningnanmycin when 100 mcg/ml.Therefore, above-claimed cpd can be prepared into antiviral agent with acceptable assistant on the agricultural, is used for the control of the viroses of plant.Select the good compound of antiviral activity to carry out the mensuration of induced activity, found that, the induced activity height of control compounds YZK-C-22 in the patent document 200810054334.1 that above-mentioned WSX-8, WSX-18, WSX-20, WSX-25, WSX-26 and the WSX-32 induced activity under same concentrations has all been applied for than the contriver, also be higher than contrast medicament TDL and induce effect under same concentrations, induced activity and the TDK of YZK-C-22 are suitable; Therefore, above-claimed cpd can be prepared into the plant activator with acceptable assistant on the agricultural, is used for the control of the viroses of plant.In process of the test, find that these compounds show in various degree poisoning to tobacco, therefore, this compounds may show certain weeding activity.The specific activity of compound WSX-8 of the present invention, WSX-18, WSX-20, WSX-25, WSX-26 and the anti-TMV of WSX-32 evoking tobacco has only a unitary chemical combination object height of triazolo thiadiazoles active structure, maximum exceeds more than 20%, these compounds have the advantage of the comparison induced activity more outstanding than compound YZK-C-22, its reason is to contain 1,2, two triazolo thiadiazoles derivatives of 3-thiadiazoles have been because the introducing of close ester spacer group has changed the close ester of target molecule, thereby make the biological activity of compound be significantly improved.

Embodiment 23

Of the present inventionly contain 1,2, two triazolo thiadiazoles derivatives of 3-thiadiazoles and antiviral agent are combined in the application in control agricultural and forestry and the gardening plant virus disease:

The result of preliminary biological assay test shows, of the present invention all contain 1,2, two triazolo thiadiazoles derivatives of 3-thiadiazoles and existing Antiphytoviral medicament diazosulfide (BTH), tiadinil (TDL), the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid (TDLA), the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate (TDLS), the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate (ETDLA), DL-beta-aminobutyric acid (BABA), virazole, antofine, Ningnanmycin and tisocromide, the first thiophene lures that any 1 or the combination of 2 compounds can be used for the anti-TMV of evoking tobacco or be used for directly preventing and treating TMV in amine and the Whitfield's ointment, all show summation action or synergism between these compositions, the effect that the effect of its antiviral activity is all used separately greater than any one compound; There is not antagonistic action.The reason that produces these effects is that the compound of compound of the present invention and its combination is complementary on mechanism of action, and the existing compound that directly acts on TMV also acts on plant itself, improves the compound of plant self-defense ability.

The staple crop that these compositions are suitable for comprises that cereal crop (comprise paddy, wheat, barley, oat, corn, millet, Chinese sorghum etc.), tuber crops (comprise sweet potato, potato, cassava etc.), legume crop (comprises soybean, broad bean, pea, mung bean, red bean etc.) and fibre crops (cotton, crudefiber crop, silkworm and mulberry etc.), oil crops (peanut, rape, sesame, soybean, Sunflower Receptacle etc.), sugar crop (beet, sugarcane etc.), beverage crops (tealeaves, coffee, cocoa etc.), hobby crop (tobacco leaf etc.), medicinal crop (genseng, the bulb of fritillary etc.), tropical crops (rubber, coconut, oil palm, sisal hemp etc.) food crop and fruit such as, flowers, oil plant, sugar material and cotton, fiber crops, tea, tobacco, cash crop and plantation melons such as Chinese medicinal materials, really, tea, silkworm and mulberry, vegetables (containing various wild vegetable etc.), bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, garden crop such as tobacco (flue-cured tobaccos such as 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.), potato, wheat, corn, paddy rice, peanut, fruit tree, (apple, banana, citrus, peach, papaya), flowers (as orchid), potted landscape etc.; Virus disease comprises tobacco mosaic virus disease, various melon virus diseases, various solanberry viroid diseases, the beans virus disease, the Cruciferae virus disease, the grain and oil crop virus disease, cotton virus disease and various fruit tree virus diseases etc. wherein endanger serious mainly containing: tobacco virus, pepper virus disease, the pimento virus disease, tomato virus disease, Chinese cabbage virus disease, the paddy rice virus disease comprises rice dwarf virus disease, yellow dwart, stripe virus disease, the fern leaf of tomato viral disease, sick and the tobacco veinal necrosis virus disease of chilli pepper mosaic virus, the corn short mosaic disease, cauliflower mosaic virus, the oranges and tangerines virus disease, cymbidium mosaic virus, cybidium ring spot virus etc.These medicaments are combined in the major reason why control of carrying out above-mentioned virus disease on the above-mentioned crop have a unusual effect, and compound of the present invention has good induced activity, and induced activity has wide spectrum and hold the characteristics of effect.

Embodiment 24

Of the present inventionly contain 1,2, the application in two triazolo thiadiazoles derivatives of 3-thiadiazoles and sterilant combination control agricultural and forestry and the gardening plant disease:

The result of preliminary biological assay test shows, of the present invention all contain 1,2, two triazolo thiadiazoles derivatives of 3-thiadiazoles and existing sterilant such as white urea cyanogen, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, the enemy can be loose, derosal, procymidone, RP-26019, Vancide 89, the mould prestige of second, ester bacterium urea, fultolanil, F-1991, cyproconazole, methasulfocarb, fenpropidin Evil acid amides, triazolone, thiophanate methyl, metaxanin, Metalaxyl-M, M 9834, hymexazol, dimethomorph, flumorph, tridemorph, fluzilazol, alkene azoles alcohol, tebuconazole hymexazo Difenoconazole, mepanipyrim, Azoxystrobin, Wocosin 50TK, diazosulfide, Whitfield's ointment, tiadinil, tisocromide, the first thiophene lures other known any any one or two kinds that can be used as in the sterilant such as amine to be used in combination the control that can be used for agricultural plants disease and gardening plant disease, controlling object comprises the Achyla of Oomycete, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, false Peronospora, a disease that genus produces surplus the Peronospora etc. 20, as seedling blight of rice, the tomato root rot, the late blight of potato, black shank, the millet Powdery Mildew, downy mildew of garpe, downy mildew of lettuce, other diseases of plurality of cereals crops such as cucumber downy mildew and cash crop etc., the formulation of using can be a wettable powder, sustained release dosage, pulvis, micro-capsule suspension, can disperse dense dose, seed treatment emulsion, aqueous emulsion, big granula, granule, microemulsion, finish, seed with coated pesticidal, suspension agent, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules or the like, of the present inventionly contain 1,2, the ratio of two triazolo thiadiazoles derivatives in composition of 3-thiadiazoles is between 1%-90%, the prevention effect of medicament is good, these compositions have synergism and summation action, do not have antagonistic action.

Utilize similar method can determine that combination between compound of the present invention and the above-mentioned commercial sterilant can be used to the disease of inducing anti-plant pathogenetic bacteria of agricultural crops and forestry plant and gardening plant and plant pathogenic fungi to cause.These crops comprise: cereal crop (comprise paddy, wheat, barley, oat, corn, millet, Chinese sorghum etc.), tuber crops (comprise sweet potato, potato, cassava etc.), legume crop (comprises soybean, broad bean, pea, mung bean, red bean etc.) fibre crops (cotton, crudefiber crop, silkworm and mulberry etc.), oil crops (peanut, rape, sesame, soybean, Sunflower Receptacle etc.), sugar crop (beet, sugarcane etc.), beverage crops (tealeaves, coffee, cocoa etc.), hobby crop (tobacco leaf etc.), medicinal crop (genseng, the bulb of fritillary, safflower, schizonepeta, Hindu Datura Flower Hairy Datura Flower, monkshood and Root of Indigowoad etc.), tropical crops (rubber, coconut, oil palm, sisal hemp etc.) food crop and fruit such as, flowers, oil plant, sugar material and cotton, fiber crops, tea, tobacco, cash crop and plantation melons such as Chinese medicinal materials, really, tea, silkworm and mulberry, vegetables (containing various wild vegetable etc.), bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, garden crops such as seedling and other garden crops.

These medicaments are combined in the major reason why control of carrying out above-mentioned disease on the above-mentioned crop have a unusual effect, and compound of the present invention has good induced activity, and induced activity has wide spectrum and hold the characteristics of effect.

The chemical structure characteristic of the two triazolothiadiazole derivatives of table 1 synthetic part of the present invention

The chemical structure characteristic (continuing) of the two triazolothiadiazole derivatives of table 1 synthetic part of the present invention

The fungicidal activity of the compound among table 2 the present invention (/ %)

Compound	??AS	??CA	??GZ	??PP	??BC	??SS	??RC	??PS	??PI
										??WSX-8	??11.11	??21.43	??5.88	??22.58	??25.00	??41.67	??3.85	??7.14	??22.73
??WSX-11	??16.67	??14.29	??14.71	??19.35	??28.13	??13.89	??0	??7.14	??22.73
										??WSX-12	??5.56	??14.29	??0	??22.58	??34.38	??22.22	??3.85	??14.29	??13.64
??WSX-16	??0	??0	??20.59	??29.03	??43.75	??8.33	??7.69	??5.36	??18.18
										??WSX-17	??27.78	??28.57	??2.94	??22.58	??28.13	??16.67	??0	??75.00	??18.18
??WSX-18	??11.11	??21.43	??2.94	??22.58	??18.75	??33.33	??3.85	??71.43	??9.09
										??WSX-19	??33.33	??28.57	??26.47	??25.81	??25.00	??11.11	??7.69	??5.36	??18.18
??WSX-20	??11.11	??14.29	??17.65	??35.48	??37.50	??22.22	??23.08	??5.36	??27.27
										??WSX-22	??0	??21.43	??14.71	??19.35	??34.38	??22.22	??11.54	??44.64	??36.36
??WSX-25	??22.22	??7.14	??17.65	??32.26	??18.75	??0	??11.54	??62.50	??22.73
										??WSX-26	??16.67	??0	??35.29	??74.19	??25.00	??69.44	??11.54	??80.36	??18.18
??WSX-28	??5.56	??21.43	??2.94	??32.26	??28.13	??33.33	??7.69	??7.14	??22.73
										??WSX-29	??11.11	??28.57	??11.76	??35.48	??28.13	??19.44	??7.69	??7.14	??9.09
??WSX-30	??0	??28.57	??32.35	??29.03	??31.25	??88.89	??7.69	??71.43	??18.18
										??WSX-32	??11.11	??21.43	??14.71	??35.48	??37.50	??27.78	??15.38	??7.14	??22.73
??WSX-33	??27.78	??7.14	??11.76	??35.48	??68.75	??19.44	??7.69	??8.93	??13.64
										??WSX-35	??11.11	??14.29	??17.65	??45.16	??43.75	??61.11	??7.69	??17.86	??36.36
??WSX-39	??9.09	??16.67	??30.00	??5.26	??41.18	??77.59	??57.69	??28.95	??31.03
										??WSX-73	??16.67	??0	??8.82	??38.71	??25.00	??38.89	??15.38	??14.29	??22.73
??YZK-C-22	??69.44	??68.75	??8.82	??88.89	??7.14	??11.11	??15.38	??88.89	??74.19

Data are the measurement result of 50 mcg/ml in the table; ND: undetermined

The activity of the compound evoking tobacco resisting tobacco mosaic virus among table 3 the present invention

Compound	Concentration (mcg/ml)	Average inhibiting rate ± SD (%)	Concentration (mcg/ml)	Average inhibiting rate ± SD (%)
					??WSX-8	??500	??56.40±3.53	??100	??45.13±2.87
??WSX-23	??500	??19.93±2.82	??100	??43.15±2.74
					??WSX-11	??500	??43.22±15.90	??100	??22.99±4.67
??WSX-16	??500	??28.70±8.36	??100	??43.01±0.95
					??WSX-17	??500	??33.53±7.55	??100	??35.95±4.53
??WSX-18	??500	??48.50±6.75	??100	??51.08±7.29
					??WSX-19	??500	??19.29±8.78	??100	??21.77±1.59
??WSX-20	??500	??48.50±6.75	??100	??41.90±23.81
					??WSX-22	??500	??30.44±13.05	??100	??60.54±4.49
??WSX-25	??500	??57.09±2.56	??100	??43.31±10.73
					??WSX-26	??500	??60.78±4.11	??100	??42.90±13.52
??WSX-28	??500	??37.43±1.89	??100	??36.21±2.62
					??WSX-29	??500	??38.21±0.95	??100	??32.46±5.43
??WSX-30	??500	??39.35±4.98	??100	??29.98±5.81
					??WSX-32	??500	??53.82±5.95	??100	??40.85±4.65
??WSX-33	??500	??37.29±3.09	??100	??32.65±2.75
					??WSX-35	??500	??27.55±4.62	??100	??21.77±1.59
??WSX-39	??500	??25.03±2.91	??100	??18.07±3.73
					??WSX-73	??500	??21.08±6.12	??100	??33.74±11.98
??YZK-C-22	??500	??33.05±5.37	??100	??38.99±3.52
					??TDL	??500	??32.09±2.97	??100	??37.00±2.08
Ningnanmycin	??500	??48.07±4.22	??100	??38.99±5.74
					Virazole	??500	??39.15±4.17	??100	??35.51±1.90

Claims (8)

1. one kind contains 2, and two triazolo thiadiazoles derivatives of 3-thiadiazoles is characterized in that having following chemical structure of general formula:

Wherein: X is O or is selected from ethylene, trimethylene, tetramethylene, 1,5-pentylidene, hexamethylene, 1, the inferior heptyl, 1 of 7-, 2-phenylene, 1,3-phenylene 1,4-phenylene, 2,5-furylidene, 2, the inferior thienyl, 2 of 5-, 6-pyridylidene, suitable-1, the 2-vinylidene, anti--vinylene, 2,2 '-Ya biphenylyl, 1,1-cyclobutyl, 1,1-Dimethylenecyclohexacompound, 3, the group of the inferior imidazolyl of 5-.

2. claim 1 is described contains 1,2, and the synthetic method of the two triazolo thiadiazoles derivatives of 3-thiadiazoles is specially:

With 2.2 mmole 3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-4-amino-5-sulfydryl-1,2,4-triazole, 1.1 mmole dicarboxylic acid and 0.5 mmole Tetrabutyl amonium bromide join in 50 milliliters of round-bottomed flasks, add 15 milliliters of POCl again ₃, under the induction stirring, the oil bath heating keeps 60 degrees centigrade of temperature, is incubated 4 hours, is warming up to 120 degrees centigrade then and refluxes 10 hours down, and reaction is finished, and the ice-water bath cooling slowly drips frozen water down, separates out a large amount of solids, standing over night, suction filtration is used saturated NaHCO ₃The solution washing product washes with water to neutrality again, dry crude product, according to the pure product calculated yield of gained, measure fusing point and ¹H NMR, the consumption of synthetic compound enlarges by corresponding proportion or dwindles.

3. antiviral agent, it is characterized in that: claim 1 is described to contain 1,2, and two triazolo thiadiazoles derivatives of 3-thiadiazoles are gone up the purposes of acceptable assistant in the preparation antiviral agent with agricultural.

4. a kind of plant activator, it is characterized in that: claim 1 is described to contain 1,2, and two triazolo thiadiazoles derivatives of 3-thiadiazoles are gone up the purposes of acceptable assistant in preparation plant activator with agricultural.

5. sterilant, it is characterized in that: claim 1 is described to contain 1,2, and two triazolo thiadiazoles derivatives of 3-thiadiazoles are gone up the purposes of acceptable assistant in the preparation sterilant with agricultural.

6. the composition of an Antiphytoviral, it is characterized in that: claim 1 is described to contain 1,2, two triazolo thiadiazoles derivatives of 3-thiadiazoles and agricultural go up acceptable assistant and be selected from diazosulfide, tiadinil, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, the DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, the first thiophene lures any one or the two kinds of combined preparation in amine or the Whitfield's ointment to become anti-plant virus agent and the purposes in the control viral diseases of plants thereof; Claim 1 is described to contain 1,2, the ratio of two triazolo thiadiazoles derivatives in composition of 3-thiadiazoles is 1%-90%, the processing formulation be selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, can disperse dense dose, seed treatment emulsion, aqueous emulsion, in the big granula, granule, microemulsion, oil-suspending agent, finish, seed, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules any one with coated pesticidal; Wherein said plant be selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, 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, melon, really, tea, wild vegetable, bamboo shoots, hops, pepper; Described viral diseases of plants is selected from tobacco mosaic virus disease, pepper virus disease, pimento virus disease, tomato virus disease, Chinese cabbage virus disease, rice dwarf virus disease, yellow dwart, 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, cybidium ring spot virus.

7. fungicidal composition, it is characterized in that: claim 1 is described to contain 1,2, two triazolo thiadiazoles derivatives of 3-thiadiazoles and agricultural go up acceptable assistant and be selected from white urea cyanogen, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, the enemy can be loose, derosal, procymidone, RP-26019, Vancide 89, the mould prestige of second, ester bacterium urea, fultolanil, F-1991, cyproconazole, methasulfocarb, fenpropidin Evil acid amides, triazolone, thiophanate methyl, metaxanin, Metalaxyl-M, M 9834, hymexazol, dimethomorph, flumorph, tridemorph, fluzilazol, alkene azoles alcohol, tebuconazole hymexazo Difenoconazole, mepanipyrim, Azoxystrobin, Wocosin 50TK, diazosulfide, Whitfield's ointment, tiadinil, tisocromide, the first thiophene lures any one or the combination of two kinds of sterilant in the amine to be used for preparing sterilant and they purposes in controlling plant diseases; Wherein said plant be selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, 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, melon, really, tea, wild vegetable, bamboo shoots, hops, pepper; Described disease is selected from seedling blight of rice, tomato root rot, the late blight of potato, black shank, the downy mildew of millet, downy mildew of garpe, downy mildew of lettuce, botrytis cinerea pers; Claim 1 is described to contain 1,2, the ratio of two triazolo thiadiazoles derivatives in composition of 3-thiadiazoles is 1%-90%, and the formulation of wherein said sterilant is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, can disperse in dense dose, 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 any one.

8. claim 1 is described contains 1,2, the complete processing that two triazolo thiadiazoles derivatives of 3-thiadiazoles and commercially available agricultural chemical are combined to form preparation.