CN101891710B - 4-halogenated methyl-1,2,3-thiadiazole compounds and preparation method and application thereof - Google Patents

Abstract

The invention provides a class of 4-halogenated methyl-1,2,3-thiadiazole compounds and a preparation method and application thereof, relating to heterocyclic compounds containing 1,2,3-thiadiazole, which have the following chemical general formula as shown in the specification of the invention. The invention discloses the general formula, the synthesis method of the compounds, application of the compounds used as insecticides, disinfectants, antiphytoviral agents and plant activators and the process for preparing insecticides, disinfectants, antiphytoviral agents and plant activators by mixing the compounds with agriculturally acceptable additives or synergists; the invention also discloses the application of combining the compounds with commercial insecticides, disinfectants, antiphytoviral agents and plant activators to prevent and treat diseases, pests, virus diseases in agriculture, forestry and horticulture, and the preparation method of the compounds.

Description

One type of 4-halogenated methyl-1,2, the 3-thiadiazole compound

Technical field

Technical scheme of the present invention relates to the heterogeneous ring compound that contains 1,2-diazole, is specifically related to 4-halogenated methyl-1,2,3-thiadiazole verivate.

Background technology

Heterogeneous ring compound has wide biological activity, all comprises heterogeneous ring compound, 1 in the patent of many biologically actives; 2, the biological activity of 3-thiadiazoles derivative is causing extensive concern, and contriver's early-stage Study is found; 1; 2,3-thiadiazole verivate has the activity of good inducing plant viral diseases and fungal disease, and the first thiophene lures amine just in industrialization process; The most successful plant activator of commercialized development diazosulfide (BTH) and tiadinil (TDL) also are 1,2, the verivate of 3-thiadiazoles; But commercial 1,2,3-thiadiazoles pesticide species is actually rare.Halogen is bioactive important activity group; In molecule, introduce halogen atom and become novel pesticide molecular designing synthetic main approaches and means; In the pesticide species of commercial halogen atom-containing, majority comprises the Cl atom, and Rynaxypyr is exactly good illustration; But the introducing of Br and I also can be played unexpected effect; Just comprise the I atom in the Ryanicide acceptor inhibitor Flubendiamide molecule of for example succeeding in developing recently; And the introducing of F atom often also can improve the biological activity of molecule, and the sterilant SYP-L190 replaces back initiative invention with the Cl atom in the HSDB 6915 molecule with the F atom.In order to seek highly active agricultural chemicals candidate compound simple in structure; The present invention designs and has synthesized one type of 4-halogenated methyl-1,2,3-thiadiazole compound; Simultaneously this compounds is carried out the comparatively bioactivity screening and the evaluation of system, obtained good biological activity.

Summary of the invention

Technical problem to be solved by this invention is: new 4-halogenated methyl-1 is provided; 2; The compound method of 3-thiadiazole verivate; 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, gardening field, field of forestry is provided simultaneously.

The present invention solves this technical problem the technical scheme that is adopted: the 4-halogenated methyl-1 with agriculture field, gardening field, field of forestry insecticidal activity, fungicidal activity, anti-phytoviral activity, inducing plant generation anti-disease activity, insect growth regulator activity; 2, the chemical structure of general formula of 3-thiadiazole verivate is suc as formula shown in the I:

Wherein: X is respectively the group that is selected from F, Cl, Br, I; R is the group that is selected from methyl, ethyl, cyclopropyl, phenyl, trifluoromethyl, methoxycarbonyl, ethoxycarbonyl, carbobenzoxy.

4-halogenated methyl-1 of the present invention; 2; Chlorinated compound in 3-thiadiazoles-5-ramification of carboxylic esters and bromo cpd can be through free radical reaction preparation, other 4-halogenated methyls-1,2; 3-thiadiazoles-5-ramification of carboxylic esters can utilize the bromo of free radical reaction preparation or the product of chloro further to prepare, and its synthetic reaction equation is following:

Wherein: CCl ₄It is solvent; NBS is the initiator of free radical reaction: the N-bromo-succinimide; NCS is the initiator of free radical reaction: the N-chlorosuccinimide; AIBN is a Diisopropyl azodicarboxylate; X is the group that is selected from F, Cl, Br, I; R ₁For being selected from the group of methyl, ethyl, cyclopropyl, trifluoromethyl, phenyl, methoxycarbonyl, ethoxycarbonyl, carbobenzoxy.

4-halogenated methyl-1,2 of the present invention, 3-thiadiazoles-5-substitutive derivative can utilize reduction reaction that 5-is replaced-1,2; 3-thiadiazoles-4-ethyl formate verivate is reduced to corresponding 4-hydroxymethyl-5-and replaces-1,2, and the 3-thiadiazoles derivative utilizes 4-hydroxymethyl-5-to replace-1 then; 2,3-thiadiazoles derivative and sulfur oxychloride prepared in reaction 4-chloromethyl-5-get-1,2, and the 3-thiadiazoles is for verivate; Other 4-halogenated methyl-5-replaces-1,2, and 3-thiadiazole verivate can utilize 4-chloromethyl-5-to replace-1; 2, the preparation of 3-thiadiazoles derivative, its synthetic reaction equation is following:

Wherein: X is the group that is selected from F, Cl, Br, I; R ₂For being selected from the group of methyl, ethyl, cyclopropyl, trifluoromethyl, phenyl, methoxycarbonyl, ethoxycarbonyl, carbobenzoxy.

4-fluoro methyl isophthalic acid, 2,3-thiadiazoles-5-substitutive derivative can adopt following prepared in reaction:

Embodiment

Enforcement of the present invention is specifically carried out according to the following steps:

A.4-chloromethyl-1,2, the preparation of 3-thiadiazoles-5-manthanoate:

In 50 milliliters of round-bottomed flasks, add 10 milliliters of tetracol phenixin, add the 4-methyl isophthalic acid again, 2,3-thiadiazoles-5-manthanoate 3.55 mmoles; The N-chlorosuccinimide, i.e. NCS, 4.04 mmoles, Diisopropyl azodicarboxylate; Be AIBN, 0.30 mmole feeds 4.04 mmole chlorine in batches, finishes after reaction system was under agitation refluxed 8 hours; Filtration product, solid merges organic phase with tetracol phenixin 10 milliliters * 3 washings; After removing solvent, the organic phase decompression gets 4-chloromethyl-1,2 with 200-300 order silica gel column chromatography, 3-thiadiazoles-5-manthanoate; Eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE, volume ratio are 40: 1, with the pure article calculated yield of gained; Its physical and chemical parameter and structural parameter are seen table 1; With the described method of C, with 4-brooethyl-1,2,3-thiadiazoles-5-manthanoate and Repone K prepared in reaction 4-chloromethyl-1,2,3-thiadiazoles-5-manthanoate has same effect; Synthetic 4-chloromethyl-1,2, the consumption of 3-thiadiazoles-5-manthanoate enlarges by corresponding proportion or dwindles; Said 4-methyl isophthalic acid, 2,3-thiadiazoles-5-manthanoate is selected from the 4-methyl isophthalic acid, and 2,3-thiadiazoles-5-methyl-formiate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-phenyl formate; Said 4-chloromethyl-1,2,3-thiadiazoles-5-manthanoate is selected from 4-chloromethyl-1,2,3-thiadiazoles-5-methyl-formiate, 4-chloromethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-chloromethyl-1,2,3-thiadiazoles-5-phenyl formate; Said 4-brooethyl-1,2,3-thiadiazoles-5-manthanoate is selected from 4-brooethyl-1,2,3-thiadiazoles-5-methyl-formiate, 4-brooethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-brooethyl-1,2,3-thiadiazoles-5-phenyl formate.

B.4-brooethyl-1,2, the preparation of 3-thiadiazoles-5-manthanoate:

In 50 milliliters of round-bottomed flasks, add 10 milliliters of tetracol phenixin, add the 4-methyl isophthalic acid again, 2,3-thiadiazoles-5-manthanoate (0.61 gram; 3.55 mmole, N-bromo-succinimide, i.e. NBS, 4.04 mmoles; Diisopropyl azodicarboxylate, i.e. AIBN, 3 mmoles drip 4 mmole bromines in batches; Reaction system finished after under agitation refluxing 8 hours, filtration product, and solid merges organic phase with tetracol phenixin 10 milliliters * 3 washings; Organic phase is with hypo solution washing 3 times, and anhydrous sodium sulfate drying behind the distilled water wash 3 times gets 4-brooethyl-1,2 with 200-300 order silica gel column chromatography after then solvent being removed in the organic phase decompression; 3-thiadiazoles-5-manthanoate, eluent are 60-90 degree centigrade sherwood oil: ETHYLE ACETATE, volume ratio are 40: 1, with the pure article calculated yield of gained; Its physical and chemical parameter and structural parameter are seen table 1; Synthetic 4-brooethyl-1,2, the consumption of 3-thiadiazoles-5-manthanoate enlarges by corresponding proportion or dwindles; Said 4-methyl isophthalic acid, 2,3-thiadiazoles-5-manthanoate is selected from the 4-methyl isophthalic acid, and 2,3-thiadiazoles-5-methyl-formiate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-phenyl formate; Said 4-brooethyl-1,2,3-thiadiazoles-5-manthanoate is selected from 4-brooethyl-1,2,3-thiadiazoles-5-methyl-formiate, 4-brooethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-brooethyl-1,2,3-thiadiazoles-5-phenyl formate.

C.4-iodomethyl-1,2, the preparation of 3-thiadiazoles-5-manthanoate:

Add 4-brooethyl-1,2,3-thiadiazoles-5-manthanoate 1.2 mmoles at the bottom of 50 milliliters of gardens in the flask; Add 15 milliliters of solvent acetone and potassiumiodide 1.8 mmoles, stirring at normal temperature 22 hours filters out the solid in the solution; Filtrate decompression gets 4-iodomethyl-1,2 with 200-300 order silica gel column chromatography after steaming solvent, 3-thiadiazoles-5-manthanoate; Eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE, volume ratio are 10: 1, with the pure article calculated yield of gained; Its physical and chemical parameter and structural parameter are seen table 1; Synthetic 4-iodomethyl-1,2, the consumption of 3-thiadiazoles-5-manthanoate enlarges by corresponding proportion or dwindles; Utilize 4-chloromethyl-1,2,3-thiadiazoles-5-manthanoate replaces 4-brooethyl-1,2, and 3-thiadiazoles-5-manthanoate prepares 4-iodomethyl-1,2, and 3-thiadiazoles-5-manthanoate carries out above-mentioned reaction and has effect same; Said 4-chloromethyl-1,2,3-thiadiazoles-5-manthanoate is selected from 4-chloromethyl-1,2,3-thiadiazoles-5-methyl-formiate, 4-chloromethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-chloromethyl-1,2,3-thiadiazoles-5-phenyl formate; Said 4-brooethyl-1,2,3-thiadiazoles-5-manthanoate is selected from 4-brooethyl-1,2,3-thiadiazoles-5-methyl-formiate, 4-brooethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-brooethyl-1,2,3-thiadiazoles-5-phenyl formate; Said 4-iodomethyl-1,2,3-thiadiazoles-5-manthanoate is selected from 4-iodomethyl-1,2,3-thiadiazoles-5-methyl-formiate, 4-iodomethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-iodomethyl-1,2,3-thiadiazoles-5-phenyl formate.

D.4-methyl fluoride-1,2, the preparation of 3-thiadiazoles-5-manthanoate:

Add 4-brooethyl-1,2 at the bottom of 50 milliliters of gardens in the flask, 3-thiadiazoles-5-manthanoate 1.2 mmoles adds 15 milliliters of solvent acetonitriles; Then add tetrabutyl ammonium fluoride 2.4 mmoles, reflux 4 hours filters out the solid in the solution; Filtrate decompression gets 4-methyl fluoride-1,2 with 200-300 order silica gel column chromatography after steaming solvent, 3-thiadiazoles-5-manthanoate; Eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE, volume ratio are 20: 1, with the pure article calculated yield of gained; Its physical and chemical parameter and structural parameter are seen table 1; Synthetic 4-methyl fluoride-1,2, the consumption of 3-thiadiazoles-5-manthanoate enlarges by corresponding proportion or dwindles; Said 4-brooethyl-1,2,3-thiadiazoles-5-manthanoate is selected from 4-brooethyl-1,2,3-thiadiazoles-5-methyl-formiate, 4-brooethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-brooethyl-1,2,3-thiadiazoles-5-phenyl formate; Said 4-methyl fluoride-1,2,3-thiadiazoles-5-manthanoate is selected from 4-methyl fluoride-1,2,3-thiadiazoles-5-methyl-formiate, 4-methyl fluoride-1,2,3-thiadiazoles-5-ethyl formate, 4-methyl fluoride-1,2,3-thiadiazoles-5-phenyl formate; With 4-chloromethyl-1,2,3-thiadiazoles-5-manthanoate replaces 4-brooethyl-1,2, and 3-thiadiazoles-5-manthanoate prepares 4-methyl fluoride-1,2, and 3-thiadiazoles-5-manthanoate also has same effect; Said 4-chloromethyl-1,2,3-thiadiazoles-5-manthanoate is selected from 4-chloromethyl-1,2,3-thiadiazoles-5-methyl-formiate, 4-chloromethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-chloromethyl-1,2,3-thiadiazoles-5-phenyl formate.

E.4-hydroxymethyl-5-replaces-1,2, the preparation of 3-thiadiazoles:

In 100 milliliters of round-bottomed flasks, add 5-methyl isophthalic acid, 2,3-thiadiazoles-4-ethyl formate 58 mmoles; 1000 milliliters of absolute ethyl alcohols, ice bath to 0 degree centigrade adds Peng Qinghuana 128 mmoles in batches under the induction stirring; Finish; Ice bath continues reaction 1 hour down, removes ice bath then, continues stirring reaction 6 hours under the room temperature; Stopped reaction, suction filtration is removed solid, and the mother liquor concentrating under reduced pressure is removed most of solvent, adds 50 ml waters then; Ethyl acetate extraction with 60 milliliters * 3 after the merging organic phase, is used anhydrous sodium sulfate drying, filters the back removal of solvent under reduced pressure; Get 4-hydroxymethyl-5-methyl isophthalic acid, 2,3-thiadiazoles with 200～300 order silica gel column chromatographies; Eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE, volume ratio are 3: 1, with the pure article calculated yield of gained; Its physical and chemical parameter and structural parameter are seen table 1; Synthetic 4-hydroxymethyl-5-methyl isophthalic acid, 2, the consumption of 3-thiadiazoles enlarges by corresponding proportion or dwindles; With 5-ethyl-1,2,3-thiadiazoles-4-ethyl formate, 5-cyclopropyl-1,2; 3-thiadiazoles-4-ethyl formate, 5-phenyl-1,2,3-thiadiazoles-4-ethyl formate, 5-Trifluoromethyl-1,2; 3-thiadiazoles-4-ethyl formate replaces the 5-methyl isophthalic acid, and 2,3-thiadiazoles-4-ethyl formate carries out above-mentioned prepared in reaction 4-hydroxymethyl-5-ethyl-1,2; 3-thiadiazoles, 4-hydroxymethyl-5-cyclopropyl-1,2,3-thiadiazoles, 4-hydroxymethyl-5-phenyl-1,2; 3-thiadiazoles, 4-hydroxymethyl-5-Trifluoromethyl-1,2, the 3-thiadiazoles has same effect.

F.4-methyl fluoride-5-replaces-1,2, the preparation of 3-thiadiazoles:

In 50 milliliters of round-bottomed flasks, add Et ₂NSF ₃9.5 5 milliliters of mmole and methylene dichloride are cooled to-15 degrees centigrade with acetone is on the rocks, adopt acetone to add liquid nitrogen and also can obtain same effect; With 4-hydroxymethyl-5-methyl isophthalic acid, 2,3-thiadiazoles 2.7 mmoles are dissolved in 15 milliliters of methylene chloride, slowly drip to reaction flask, drip off in about 20 minutes, slowly are warming up to room temperature then, continue reaction 1 hour; In 20 milliliters of frozen water of reaction solution impouring, tell organic phase after, water is with 20 milliliters * 2 dichloromethane extraction; Merge organic phase behind the separatory; Anhydrous sodium sulfate drying, decompression steam behind the solvent with 200-300 order silica gel column chromatography, and eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE; Volume ratio is 4: 1, with the pure article calculated yield of gained; Synthetic 4-methyl fluoride-5-methyl isophthalic acid, 2, the consumption of 3-thiadiazoles enlarges by corresponding proportion or dwindles; With 4-hydroxymethyl-5-ethyl-1,2,3-thiadiazoles, 4-hydroxymethyl-5-cyclopropyl-1,2; 3-thiadiazoles, 4-hydroxymethyl-5-phenyl-1,2,3-thiadiazoles, 4-hydroxymethyl-5-Trifluoromethyl-1,2; The 3-thiadiazoles replaces 4-hydroxymethyl-5-methyl isophthalic acid, and 2, the 3-thiadiazoles carries out above-mentioned prepared in reaction 4-methyl fluoride-5-ethyl-1,2; 3-thiadiazoles, 4-methyl fluoride-5-cyclopropyl-1,2,3-thiadiazoles, 4-methyl fluoride-5-phenyl-1,2; 3-thiadiazoles, 4-methyl fluoride-5-Trifluoromethyl-1,2, the 3-thiadiazoles has same effect.

G.4-chloromethyl-5-replaces-1,2, the preparation of 3-thiadiazoles:

In 50 milliliters of round-bottomed flasks, add 4-methylol-5-methyl isophthalic acid, 2,3-thiadiazoles 8.5 mmoles; 60 milliliters of methylene dichloride, ice bath to 0 degree centigrade is dissolved in sulfur oxychloride 15.4 mmoles in 10 milliliters of methylene dichloride; Slowly drip to reaction solution, drip and finish, ice bath continues reaction 0.5 hour down; Remove ice bath then, continued stirring reaction 4 hours under the room temperature; Behind the stopped reaction, reaction mixture is used 30 ml waters and 30 milliliters of saturated common salt water washings, separatory respectively; Organic phase is used anhydrous sodium sulfate drying; Filter the back removal of solvent under reduced pressure, use 200～300 order silica gel column chromatographies again, eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE; Volume ratio is 4: 1, with the pure article calculated yield of gained; Its physical and chemical parameter and structural parameter are seen table 1; Synthetic 4-chloromethyl-5-methyl isophthalic acid, 2, the consumption of 3-thiadiazoles enlarges by corresponding proportion or dwindles; Utilize 4-hydroxymethyl-5-ethyl-1,2,3-thiadiazoles, 4-hydroxymethyl-5-cyclopropyl-1,2; 3-thiadiazoles, 4-hydroxymethyl-5-phenyl-1,2,3-thiadiazoles, 4-hydroxymethyl-5-Trifluoromethyl-1,2; The 3-thiadiazoles replaces 4-hydroxymethyl-5-methyl isophthalic acid, and 2, the 3-thiadiazoles carries out above-mentioned prepared in reaction 4-chloromethyl-5-ethyl-1,2; 3-thiadiazoles, 4-chloromethyl-5-cyclopropyl-1,2,3-thiadiazoles, 4-chloromethyl-5-phenyl-1,2; 3-thiadiazoles, 4-chloromethyl-5-Trifluoromethyl-1,2, the 3-thiadiazoles has same effect.

H.4-brooethyl-5-replaces-1,2, the preparation of 3-thiadiazoles:

In 50 milliliters of round-bottomed flasks, add 4-chloromethyl-5-methyl isophthalic acid, 2,3-thiadiazoles 2.7 mmoles, Potassium Bromide 4 mmoles, 20 milliliters of Tetrabutyl amonium bromide 0.54 mmole and toluene, reflux is 20 hours under the induction stirring; Stopped reaction adds 20 ml waters, with 20 ml waters and 20 milliliters of saturated common salt water washings in reaction mixture; Separatory, organic phase is used anhydrous sodium sulfate drying, filters the back removal of solvent under reduced pressure and gets product 4-brooethyl-5-methyl isophthalic acid; 2, the 3-thiadiazoles is used 200～300 order silica gel column chromatographies again; Eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE, volume ratio are 30: 1, with the pure article calculated yield of gained; Its physical and chemical parameter and structural parameter are seen table 1; Synthetic 4-brooethyl-5-methyl isophthalic acid, 2, the consumption of 3-thiadiazoles enlarges by corresponding proportion or dwindles; With 4-chloromethyl-5-ethyl-1,2,3-thiadiazoles, 4-chloromethyl-5-cyclopropyl-1,2; 3-thiadiazoles, 4-chloromethyl-5-phenyl-1,2,3-thiadiazoles, 4-chloromethyl-5-Trifluoromethyl-1,2; The 3-thiadiazoles replaces 4-chloromethyl-5-methyl isophthalic acid, and 2, the 3-thiadiazoles carries out above-mentioned prepared in reaction 4-brooethyl-5-ethyl-1,2; 3-thiadiazoles, 4-brooethyl-5-cyclopropyl-1,2,3-thiadiazoles, 4-brooethyl-5-phenyl-1,2; 3-thiadiazoles, 4-brooethyl-5-Trifluoromethyl-1,2, the 3-thiadiazoles has same effect.

I.4-iodomethyl-5-replaces-1,2, the preparation of 3-thiadiazoles:

In 50 milliliters of round-bottomed flasks, add 4-chloromethyl-5-methyl isophthalic acid, 2,3-thiadiazoles 2.7 mmoles add 15 milliliters of solvent acetone; Then add potassiumiodide 4.0 mmoles, stirring at normal temperature is spent the night, and filters the back removal of solvent under reduced pressure; Get 4-iodomethyl-5-methyl isophthalic acid, 2,3-thiadiazoles with 200-300 order silica gel column chromatography; Eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE, volume ratio are 3: 1, with the pure article calculated yield of gained; Synthetic 4-iodomethyl-5-methyl isophthalic acid, 2, the consumption of 3-thiadiazoles enlarges by corresponding proportion or dwindles; With 4-chloromethyl-5-ethyl-1,2,3-thiadiazoles, 4-chloromethyl-5-cyclopropyl-1,2; 3-thiadiazoles, 4-chloromethyl-5-phenyl-1,2,3-thiadiazoles, 4-chloromethyl-5-Trifluoromethyl-1,2; The 3-thiadiazoles replaces 4-chloromethyl-5-methyl isophthalic acid, and 2, the 3-thiadiazoles carries out above-mentioned prepared in reaction 4-iodomethyl-5-ethyl-1,2; 3-thiadiazoles, 4-iodomethyl-5-cyclopropyl-1,2,3-thiadiazoles, 4-iodomethyl-5-phenyl-1,2; 3-thiadiazoles, 4-iodomethyl-5-Trifluoromethyl-1,2, the 3-thiadiazoles has same effect; Adopt aforesaid method, replace-1,2 with 4-brooethyl-5-, 3-thiadiazoles or 4-chloromethyl-5-replaces-1; 2, the 3-thiadiazoles replaces 4-chloromethyl-5-methyl isophthalic acid, 2; The 3-thiadiazoles carries out above-mentioned prepared in reaction 4-iodomethyl-5-and replaces-1,2, and the 3-thiadiazoles has same effect; Said 4-brooethyl-5-replaces-1,2, and the 3-thiadiazoles is selected from 4-brooethyl-5-methyl isophthalic acid, 2; 3-thiadiazoles, 4-brooethyl-5-ethyl-1,2,3-thiadiazoles, 4-brooethyl-5-cyclopropyl-1; 2,3-thiadiazoles, 4-brooethyl-5-phenyl-1,2; 3-thiadiazoles, 4-brooethyl-5-Trifluoromethyl-1,2, the 3-thiadiazoles; Said 4-chloromethyl-5-replaces-1,2, and the 3-thiadiazoles is selected from 4-chloromethyl-5-methyl isophthalic acid, 2; 3-thiadiazoles, 4-chloromethyl-5-ethyl-1,2,3-thiadiazoles, 4-chloromethyl-5-cyclopropyl-1; 2,3-thiadiazoles, 4-chloromethyl-5-phenyl-1,2; 3-thiadiazoles, 4-chloromethyl-5-Trifluoromethyl-1,2, the 3-thiadiazoles; Said 4-iodomethyl-5-replaces-1,2, and the 3-thiadiazoles is selected from 4-iodomethyl-5-methyl isophthalic acid, 2; 3-thiadiazoles, 4-iodomethyl-5-ethyl-1,2,3-thiadiazoles, 4-iodomethyl-5-cyclopropyl-1; 2,3-thiadiazoles, 4-iodomethyl-5-phenyl-1,2; 3-thiadiazoles, 4-iodomethyl-5-Trifluoromethyl-1,2, the 3-thiadiazoles.

J.4-halogenated methyl-1,2,3-thiadiazole compound are to the mensuration of pathogenic fungi growth activity influence:

4-halogenated methyl-1,2 of the present invention, the mensuration of 3-thiadiazole compound bacteriostatic activity adopt thalli growth rate assay method; Detailed process is: get 5 milligrams of sample dissolution in an amount of N, with containing the medicament that a certain amount of polysorbas20 emulsifier aqueous solution is diluted to 500 mcg/ml, will supply the reagent agent under aseptic condition, respectively to draw in 1 milliliter of injection petridish then; Add 9 milliliters of substratum more respectively, it is dull and stereotyped to process 50 mcg/ml pastilles after shaking up, and does 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, be equilateral triangle and put, every processing repetition 3 times; Petridish is placed on cultivation in 24 ± 1 degrees centigrade of constant incubators; Colony diameter to be contrasted expands to 2-3 centimetre of " Invest, Then Investigate " and respectively handles bacterium dish expansion diameter, averages, and relatively calculates relative bacteriostasis rate with blank; Supply the examination bacterial classification to comprise frequently seen plants pathogenic bacteria on the various agricultural, its title and code name comprise AS: tomato early blight bacterium (Alternaria solani); CA: peanut Cercospora bacteria (Cercospora arachidicola); PP: ring rot of apple bacterium (Physalospora piricola); BC: botrytis cinerea pers (Botrytis cinerea); P S: Rhizoctonia solani Kuhn (Pellicularia sasakii); GZ: fusarium graminearum (Gibberella zeae); PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum); RC: cereal rhizoctonia (Rhizoctonia cerealis), these pathogenic fungies can be represented the kind of most of pathogenic bacteria of the actual generation in field in China's agriculture prodn.

K. 4-halogenated methyl-1,2 of the present invention, the mensuration of 3-thiadiazole compound inducing anti-disease activity:

4-halogenated methyl-1,2 of the present invention, the active screening method of 3-thiadiazole compound evoking tobacco resisting tobacco mosaic virus (TMV) is following: the mensuration of the direct antiviral activity that exsomatizes adopts half leaf method to carry out; It is the common cigarette that seedling age is consistent that live body is induced, 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, simultaneously reference literature Fan Z.J.; Et al.J.Agric.Food Chem., 2010,58 (5): 2630-2636 and ZuoX.; Et al.J.Agric.Food Chem., 2010,58 (5): the method that 2755-2762 describes is carried out the biological activity of compound to protection, passivation, treatment and the withered spot of half leaf of tobacco mosaic virus(TMV).

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

Wherein, R is the 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 the average withered spot number of chemicals treatment rear blade, unit: individual;

The invention has the beneficial effects as follows: the present invention is to 4-halogenated methyl-1; 2; The 3-thiadiazole compound has carried out mensuration antibacterial and inducing anti-disease activity and anti-phytoviral activity (activity that comprises protection, passivation, treatment and the withered spot of half leaf); This compounds can be used for the control of disease, insect pest and the virus disease in agriculture field, field of forestry, gardening field; Promptly can be used to prepare sterilant, antiviral agent, plant activator, sterilant, also can comprise sterilant, sterilant, anti-plant virus agent, plant activator combination use with the agricultural chemicals of commodity.

The present invention will more specifically explain 4-halogenated methyl-1 through specific preparation and biological activity determination embodiment; 2; Synthetic and the biological activity and the application thereof of 3-thiadiazole compound, unrestricted the present invention, especially its biological activity only illustrate but said embodiment only is used to specify the present invention; And unrestricted this patent, embodiment is following:

Embodiment 1

The compound 4-chloro methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-5-ethyl formate (ZHH-15) and structure are identified

In 50 milliliters of round-bottomed flasks, add 10 milliliters of tetracol phenixin, add the 4-methyl isophthalic acid again, 2,3-thiadiazoles-5-ethyl formate (0.67 gram; 3.90 mmole), N-chlorosuccinimide (NCS) (0.80 gram, 5.99 mmoles), Diisopropyl azodicarboxylate (AIBN) (0.04 gram; 0.24 mmole), reaction system was under agitation refluxed 48 hours, after reaction finishes, filtration product; Solid merges organic phase with tetracol phenixin 10 milliliters * 3 washings, and with 200-300 order silica gel column chromatography, eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE behind the decompression removal solvent; Volume ratio is 40: 1, and with the pure article calculated yield of gained, yield 26% carries out ¹The mensuration of HNMR, ¹HNMR (solvent: CDCl ₃), chemical shift: 5.282 (s, 2H, CH ₂), 4.493-4.439 (q, 2H, J=7.2Hz, J=14.4Hz, CH ₂), 1.449-1.414 (t, 3H, J=7.2Hz, CH ₃), this compound ¹The HNMR data presentation is consistent with its chemical structure; Its physical and chemical parameter and structural parameter are seen table 1.With reference to embodiment 3, utilize 4-brooethyl-1,2,3-thiadiazoles-5-ethyl formate and Repone K prepared in reaction 4-chloromethyl-1,2,3-thiadiazoles-5-ethyl formate also has same effect, and its yield is greater than 50%.

Adopt aforesaid method, utilize the 4-methyl isophthalic acid, 2; 3-thiadiazoles-5-methyl-formiate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-phenyl formate replaces the 4-methyl isophthalic acid; 2,3-thiadiazoles-5-ethyl formate prepares 4-chloromethyl-1,2 respectively; 3-thiadiazoles-5-methyl-formiate, 4-chloromethyl-1,2,3-thiadiazoles-5-phenyl formate has same effect.

Embodiment 2

Compound 4-brooethyl-1,2, the preparation of 3-thiadiazoles-5-ethyl formate (ZHH-1) and structure are identified

In 50 milliliters of round-bottomed flasks, add 10 milliliters of tetracol phenixin, add the 4-methyl isophthalic acid again, 2,3-thiadiazoles-5-ethyl formate (0.61 gram; 3.55 mmole), N-bromo-succinimide (NBS) (0.72 gram, 4.04 mmoles), Diisopropyl azodicarboxylate (AIBN) (0.05 gram; 0.30 mmole), reaction system was under agitation refluxed 8 hours, after reaction finishes, filtration product; Solid merges organic phase with tetracol phenixin 10 milliliters * 3 washing, and organic phase is with hypo solution washing 3 times, anhydrous sodium sulfate drying behind the distilled water wash 3 times; Remove under reduced pressure then behind the solvent with 200-300 order silica gel column chromatography, eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE, volume ratio are 40: 1; With the pure article calculated yield of gained, productive rate 34% carries out ¹The mensuration of HNMR, ¹HNMR (solvent: CDCl ₃, chemical shift): 5.067 (s, 2H, CH ₂), 4.483-4.430 (q, 2H, J=7.2Hz, J=14.4Hz, CH ₂), 1.443-1.407 (t, 3H, J=7.2Hz, CH ₃), this compound ¹H NMR data presentation is consistent with its chemical structure; Its physical and chemical parameter and structural parameter are seen table 1.

Adopt aforesaid method, utilize the 4-methyl isophthalic acid, 2; 3-thiadiazoles-5-methyl-formiate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-phenyl formate replaces the 4-methyl isophthalic acid; 2,3-thiadiazoles-5-ethyl formate prepares 4-brooethyl-1,2 respectively; 3-thiadiazoles-5-methyl-formiate, 4-brooethyl-1,2,3-thiadiazoles-5-phenyl formate has effect same.

Embodiment 3

Compound 4-iodomethyl-1,2, the preparation of 3-thiadiazoles-5-ethyl formate (ZHH-13) and structure are identified

Add 4-brooethyl-1,2 at the bottom of 50 milliliters of gardens in the flask, 3-thiadiazoles-5-ethyl formate (0.30 gram; 1.2 mmole), add 15 milliliters of solvent acetone, then add potassiumiodide (0.30 gram; 1.8 mmole), stirring at normal temperature 22 hours filters out the solid in the solution; Filtrate decompression gets 4-iodomethyl-1,2 with 200-300 order silica gel column chromatography after steaming solvent, 3-thiadiazoles-5-ethyl formate; Eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE, volume ratio are 10: 1, with the pure article calculated yield of gained; Productive rate 64% carries out ¹The mensuration of HNMR, ¹HNMR (solvent: CDCl ₃), chemical shift: 5.119 (s, 2H, CH ₂), 4.488-4.435 (q, 2H, J=7.2Hz, J=14.4Hz, CH ₂), 1.454-1.419 (t, 3H, J=7.2Hz, CH ₃), this compound ¹H NMR data presentation is consistent with its chemical structure; Its physical and chemical parameter and structural parameter are seen table 1; Utilize 4-chloromethyl-1,2,3-thiadiazoles-5-ethyl formate replaces 4-brooethyl-1,2, and 3-thiadiazoles-5-ethyl formate carries out above-mentioned reaction and also has same effect, and its yield is greater than 50%.

Adopt aforesaid method, utilize 4-chloromethyl-1,2,3-thiadiazoles-5-manthanoate replaces 4-brooethyl-1,2, and 3-thiadiazoles-5-manthanoate prepares 4-iodomethyl-1,2, and 3-thiadiazoles-5-manthanoate carries out above-mentioned reaction and has effect same; Said 4-chloromethyl-1,2,3-thiadiazoles-5-manthanoate is selected from 4-chloromethyl-1,2,3-thiadiazoles-5-methyl-formiate, 4-chloromethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-chloromethyl-1,2,3-thiadiazoles-5-phenyl formate; Said 4-brooethyl-1,2,3-thiadiazoles-5-manthanoate is selected from 4-brooethyl-1,2,3-thiadiazoles-5-methyl-formiate, 4-brooethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-brooethyl-1,2,3-thiadiazoles-5-phenyl formate; Said 4-iodomethyl-1,2,3-thiadiazoles-5-manthanoate is selected from 4-iodomethyl-1,2,3-thiadiazoles-5-methyl-formiate, 4-iodomethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-iodomethyl-1,2,3-thiadiazoles-5-phenyl formate.

Embodiment 4

Compound 4-methyl fluoride-1,2, the preparation of 3-thiadiazoles-5-ethyl formate (ZHH-F1) and structure are identified

Add 4-brooethyl-1,2 at the bottom of 50 milliliters of gardens in the flask, 3-thiadiazoles-5-ethyl formate (0.30 gram, 1.2 mmoles); Add 15 milliliters of solvent acetonitriles, then add tetrabutyl ammonium fluoride (0.63 gram, 2.4 mmoles); Reflux 4 hours filters out the solid in the solution, and filtrate decompression steams behind the solvent with 200-300 order silica gel column chromatography; Eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE, volume ratio are 20: 1, with the pure article calculated yield of gained; Productive rate 80%, this compound ¹H NMR data presentation is consistent with its chemical structure; Utilize 4-chloromethyl-1,2,3-thiadiazoles-5-ethyl formate replaces 4-brooethyl-1,2, and 3-thiadiazoles-5-ethyl formate carries out above-mentioned reaction and also has same effect, and its yield is greater than 50%.

Adopt aforesaid method, with 4-brooethyl-1,2; 3-thiadiazoles-5-methyl-formiate, 4-brooethyl-1,2,3-thiadiazoles-5-phenyl formate replaces 4-brooethyl-1; 2,3-thiadiazoles-5-ethyl formate prepares 4-methyl fluoride-1,2; 3-thiadiazoles-5-methyl-formiate, 4-methyl fluoride-1,2,3-thiadiazoles-5-phenyl formate has same effect; With 4-chloromethyl-1,2,3-thiadiazoles-5-manthanoate replaces 4-brooethyl-1,2, and 3-thiadiazoles-5-manthanoate prepares 4-methyl fluoride-1,2, and 3-thiadiazoles-5-manthanoate also has same effect; Said 4-chloromethyl-1,2,3-thiadiazoles-5-manthanoate is selected from 4-chloromethyl-1,2,3-thiadiazoles-5-methyl-formiate, 4-chloromethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-chloromethyl-1,2,3-thiadiazoles-5-phenyl formate; Said 4-brooethyl-1,2,3-thiadiazoles-5-manthanoate is selected from 4-brooethyl-1,2,3-thiadiazoles-5-methyl-formiate, 4-brooethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-brooethyl-1,2,3-thiadiazoles-5-phenyl formate; Said 4-methyl fluoride-1,2,3-thiadiazoles-5-manthanoate is selected from 4-methyl fluoride-1,2,3-thiadiazoles-5-methyl-formiate, 4-methyl fluoride-1,2,3-thiadiazoles-5-ethyl formate, 4-methyl fluoride-1,2,3-thiadiazoles-5-phenyl formate.

Embodiment 5

Compound 4-hydroxy ylmethyl-5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles (ZZ4-27) and structure are identified

In 100 milliliters of round-bottomed flasks, add the 5-methyl isophthalic acid, 2,3-thiadiazoles-4-ethyl formate (10 grams; 58 mmoles), absolute ethyl alcohol (1000 milliliters), ice bath to 0 degree centigrade; Add Peng Qinghuana (4.8 grams, 128 mmoles) under the induction stirring in batches, finish; Ice bath continues reaction 1 hour down, removes ice bath then, continues stirring reaction 6 hours under the room temperature.Stopped reaction, suction filtration is removed solid, and mother liquor concentrates removes most of solvent; Add 50 ml waters then, with 60 milliliters * 3 ethyl acetate extractions, after the merging organic phase; Use anhydrous sodium sulfate drying, with 200～300 order silica gel column chromatographies, eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE after the removal of solvent under reduced pressure; Volume ratio is 3: 1, yield 90%.Carry out ¹The mensuration of HNMR, ¹HNMR (solvent: CDCl ₃), chemical shift: 2.651 (s, 3H, CH ₃), 3.713 (s, 1H, OH), 5.024 (s, 2H, CH ₂), this compound ¹The HNMR data presentation is consistent with its chemical structure; Its physical and chemical parameter and structural parameter are seen table 1.

Adopt aforesaid method, with 5-ethyl-1,2,3-thiadiazoles-4-ethyl formate, 5-cyclopropyl-1; 2,3-thiadiazoles-4-ethyl formate, 5-phenyl-1,2,3-thiadiazoles-4-ethyl formate, 5-Trifluoromethyl-1; 2,3-thiadiazoles-4-ethyl formate replaces the 5-methyl isophthalic acid, and 2,3-thiadiazoles-4-ethyl formate carries out above-mentioned prepared in reaction 4-hydroxymethyl-5-ethyl-1; 2,3-thiadiazoles, 4-hydroxymethyl-5-cyclopropyl-1,2,3-thiadiazoles, 4-hydroxymethyl-5-phenyl-1; 2,3-thiadiazoles, 4-hydroxymethyl-5-Trifluoromethyl-1,2, the 3-thiadiazoles has effect same.

Embodiment 6

Compound 4-methyl fluoride-5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles (ZHH-F2) and structure are identified

In 50 milliliters of round-bottomed flasks, add Et ₂NSF ₃9.5 5 milliliters of mmole and methylene dichloride are cooled to-15 degrees centigrade with acetone is on the rocks, adopt acetone to add liquid nitrogen and also can obtain same effect; With 4-hydroxymethyl-5-methyl isophthalic acid, 2,3-thiadiazoles 2.7 mmoles are dissolved in 15 milliliters of methylene chloride, slowly drip to reaction flask, drip off in about 20 minutes, slowly are warming up to room temperature then, continue reaction 1 hour; In 20 milliliters of frozen water of reaction solution impouring, tell organic phase after, water is with 20 milliliters * 2 dichloromethane extraction; Merge organic phase behind the separatory, anhydrous sodium sulfate drying, decompression steams behind the solvent with 200-300 order silica gel column chromatography; Eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE; Volume ratio is 4: 1, with the pure article calculated yield of gained, yield 40%.

Adopt aforesaid method, utilize 4-hydroxymethyl-5-ethyl-1,2,3-thiadiazoles, 4-hydroxymethyl-5-cyclopropyl-1; 2,3-thiadiazoles, 4-hydroxymethyl-5-phenyl-1,2,3-thiadiazoles, 4-hydroxymethyl-5-Trifluoromethyl-1; 2, the 3-thiadiazoles replaces 4-hydroxymethyl-5-methyl isophthalic acid, and 2, the 3-thiadiazoles prepares 4-methyl fluoride-5-ethyl-1; 2,3-thiadiazoles, 4-methyl fluoride-5-cyclopropyl-1,2,3-thiadiazoles, 4-methyl fluoride-5-phenyl-1; 2,3-thiadiazoles, 4-methyl fluoride-5-Trifluoromethyl-1,2, the 3-thiadiazoles has same effect.

Embodiment 7

Compound 4-chloro methyl-5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles (ZZ4-29) and structure are identified

In 250 milliliters of round-bottomed flasks, add 4-methylol-5-methyl isophthalic acid, 2,3-thiadiazoles (6.18 grams, 47 mmoles); Methylene dichloride (60 milliliters), ice bath to 0 degree centigrade is with sulfur oxychloride (11.3 grams; 94 mmoles) be dissolved in the methylene dichloride (20 milliliters), slowly drip to reaction solution, drip and finish; Ice bath continues reaction 0.5 hour down, removes ice bath then, continues stirring reaction 4 hours under the room temperature; Stopped reaction, reaction mixture are used 60 ml waters and 60 milliliters of saturated common salt water washings, separatory respectively; Organic phase is used anhydrous sodium sulfate drying, filters the back removal of solvent under reduced pressure, gets 4-chloromethyl-5-methyl isophthalic acid with 200～300 order silica gel column chromatographies again; 2,3-thiadiazoles, eluent are 60-90 degree centigrade sherwood oil: ETHYLE ACETATE; Volume ratio is 3: 1, yield 92%; Carry out ¹The mensuration of HNMR, ¹HNMR (solvent: CDCl ₃), chemical shift: 2.68 (s, 3H, CH ₃), 5.00 (s, 2H, CH ₂), this compound ¹The HNMR data presentation is consistent with its chemical structure; Its physical and chemical parameter and structural parameter are seen table 1.

Adopt aforesaid method, utilize 4-hydroxymethyl-5-ethyl-1,2,3-thiadiazoles, 4-hydroxymethyl-5-cyclopropyl-1; 2,3-thiadiazoles, 4-hydroxymethyl-5-phenyl-1,2,3-thiadiazoles, 4-hydroxymethyl-5-Trifluoromethyl-1; 2, the 3-thiadiazoles replaces 4-hydroxymethyl-5-methyl isophthalic acid, and 2, the 3-thiadiazoles prepares 4-chloromethyl-5-ethyl-1; 2,3-thiadiazoles, 4-chloromethyl-5-cyclopropyl-1,2,3-thiadiazoles, 4-chloromethyl-5-phenyl-1; 2,3-thiadiazoles, 4-chloromethyl-5-Trifluoromethyl-1,2, the 3-thiadiazoles has same effect.

Embodiment 8

Compound 4-brooethyl-5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles (WSX-295) and structure are identified

In 50 milliliters of round-bottomed flasks, add 4-chloromethyl-5-methyl isophthalic acid, 2,3-thiadiazoles (0.4 gram; 2.7 mmole), Potassium Bromide (0.48 gram, 4 mmoles); Reflux is 20 hours under Tetrabutyl amonium bromide (0.17 gram, 0.54 mmole) and toluene (20 milliliters) induction stirring; Stopped reaction adds 20 ml waters, with 20 ml waters and 20 milliliters of saturated common salt water washings in reaction mixture; Separatory, organic phase is used anhydrous sodium sulfate drying, filters the back removal of solvent under reduced pressure and gets product; Use 200～300 order silica gel column chromatographies again; Eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE, volume ratio are 30: 1, yield 70%; Carry out ¹The mensuration of HNMR, ¹HNMR (solvent: CDCl ₃), chemical shift: 2.642 (s, 3H, CH ₃), 4.845 (s, 2H, CH ₂), this compound ¹The HNMR data presentation is consistent with its chemical structure; Its physical and chemical parameter and structural parameter are seen table 1.

Adopt aforesaid method, utilize 4-chloromethyl-5-ethyl-1,2,3-thiadiazoles, 4-chloromethyl-5-cyclopropyl-1; 2,3-thiadiazoles, 4-chloromethyl-5-phenyl-1,2,3-thiadiazoles, 4-chloromethyl-5-Trifluoromethyl-1; 2, the 3-thiadiazoles replaces 4-chloromethyl-5-methyl isophthalic acid, and 2, the 3-thiadiazoles carries out above-mentioned prepared in reaction 4-brooethyl-5-ethyl-1; 2,3-thiadiazoles, 4-brooethyl-5-cyclopropyl-1,2,3-thiadiazoles, 4-brooethyl-5-phenyl-1; 2,3-thiadiazoles, 4-brooethyl-5-Trifluoromethyl-1,2, the 3-thiadiazoles has same effect.

Embodiment 9

Compound 4-iodomethyl-5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles (ZHH-20, same WSX-287) and structure are identified

In 50 milliliters of round-bottomed flasks, add 4-chloromethyl-5-methyl isophthalic acid, 2,3-thiadiazoles (0.40 gram, 2.7 mmoles); Add 15 milliliters of solvent acetone, then add potassiumiodide (0.67 gram, 4.0 mmoles), stirring at normal temperature is spent the night; Filter the back removal of solvent under reduced pressure, get 4-iodomethyl-5-methyl isophthalic acid, 2,3-thiadiazoles with 200-300 order silica gel column chromatography; Eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE, volume ratio are 3: 1, with the pure article calculated yield of gained; Productive rate 86% is red-purple liquid, carries out ¹The mensuration of HNMR, ¹HNMR (solvent: CDCl ₃), chemical shift: 4.735 (s, 2H, CH ₂), 2.547 (s, 3H, CH ₃), this compound ¹H NMR data presentation is consistent with its chemical structure; Its physical and chemical parameter and structural parameter are seen table 1.With 4-brooethyl-5-methyl isophthalic acid, 2, the 3-thiadiazoles replaces 4-chloromethyl-5-methyl isophthalic acid, and 2, the 3-thiadiazoles carries out above-mentioned prepared in reaction 4-iodomethyl-5-methyl isophthalic acid, and 2, the 3-thiadiazoles has same effect.

Adopt aforesaid method, replace-1,2 with 4-brooethyl-5-, 3-thiadiazoles or 4-chloromethyl-5-replaces-1; 2, the 3-thiadiazoles replaces 4-chloromethyl-5-methyl isophthalic acid, 2; The 3-thiadiazoles carries out above-mentioned prepared in reaction 4-iodomethyl-5-and replaces-1,2, and the 3-thiadiazoles has same effect; Said 4-brooethyl-5-replaces-1,2, and the 3-thiadiazoles is selected from 4-brooethyl-5-methyl isophthalic acid, 2; 3-thiadiazoles, 4-brooethyl-5-ethyl-1,2,3-thiadiazoles, 4-brooethyl-5-cyclopropyl-1; 2,3-thiadiazoles, 4-brooethyl-5-phenyl-1,2; 3-thiadiazoles, 4-brooethyl-5-Trifluoromethyl-1,2, the 3-thiadiazoles; Said 4-chloromethyl-5-replaces-1,2, and the 3-thiadiazoles is selected from 4-chloromethyl-5-methyl isophthalic acid, 2; 3-thiadiazoles, 4-chloromethyl-5-ethyl-1,2,3-thiadiazoles, 4-chloromethyl-5-cyclopropyl-1; 2,3-thiadiazoles, 4-chloromethyl-5-phenyl-1,2; 3-thiadiazoles, 4-chloromethyl-5-Trifluoromethyl-1,2, the 3-thiadiazoles; Said 4-iodomethyl-5-replaces-1,2, and the 3-thiadiazoles is selected from 4-iodomethyl-5-methyl isophthalic acid, 2; 3-thiadiazoles, 4-iodomethyl-5-ethyl-1,2,3-thiadiazoles, 4-iodomethyl-5-cyclopropyl-1; 2,3-thiadiazoles, 4-iodomethyl-5-phenyl-1,2; 3-thiadiazoles, 4-iodomethyl-5-Trifluoromethyl-1,2, the 3-thiadiazoles.

Embodiment 10

4-halogenated methyl-1,2 of the present invention, the bacteriostatic activity of 3-thiadiazole compound:

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); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum); RC: cereal rhizoctonia (Phizoctonia cerealis), 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; Table 2 shows; Synthetic compound of the present invention has good bacteriostatic action to the growth of most of pathogenic fungi of mensuration: when 50 mcg/ml; Compound ZHH-1 and ZHH-13 all have excellent bactericidal activity to all fungies of test, and ZHH-1 has reached 100% to the activity of GZ, PP, RC, PS and SS; ZHH-13 has reached 100% to the activity of PP, RC, PS and SS.ZHH-15 is to PS; ZZ4-27 to SS, ZZ4-29 to AS and CA; WSX295 is to CA, GZ, RC, SS and PI; WSX-287 all has excellent bactericidal activity to GZ, SS and PI, and its activity is all greater than 70%; And starting raw material E4MTCA only has excellent bactericidal activity to SS, has reached 100%, and is all not high to the activity of other pathogenic bacterias; TDL to the activity of RC and SS greater than beyond 80%, not high to activity of other test bacterium yet.Test result is visible, 1,2 of bromo and iodo, the 3-thiadiazoles derivative has the fungicidal activity of significant wide spectrum, and chloro 1,2,3-thiadiazoles derivative and the alcohol compound for preparing these halides have selective bactericidal activity efficiently.

Embodiment 11

4-halogenated methyl-1,2 of the present invention, the effect of 3-thiadiazole compound resisting tobacco mosaic virus or evoking tobacco resisting tobacco mosaic virus

The mensuration result of antiviral activity and induced activity sees table 3; Table 3 shows; The plant inducing anti-disease activator tiadinil of standard has the activity of good protection and passivation TMV; Well evoking tobacco produces the resistance to TMV, but the antiviral agent virazole has well directly antiviral activity, but does not almost have induced activity; 4-halogenated methyl-1 of the present invention; 2; The 3-thiadiazole compound partly has the activity of direct anti-TMV preferably, and ZHH-1 has the activity of significant passivation and the withered spot of half leaf, also has the activity of the anti-TMV of significant evoking tobacco; ZZ4-29 has the activity of the withered spot of good half leaf, and other compounds all have in various degree directly antiviral activity and induced activity; The induced activity of simultaneously corresponding ester is the induced activity of methyl greater than the corresponding position; And the intermediate E 4MTCA of synthetic these halogenated product also keeps good induced activity.Therefore, compound of the present invention has Antiphytoviral and inducing plant produce resistance to viral diseases of plants effect.

Embodiment 12

4-halogenated methyl-1,2 of the present invention, 3-thiadiazole compound and sterilant combined preparation desinsection, disease-resistant and desinsection, the application of plant activator in control agricultural, forestry, gardening plant disease, insect pest

4-halogenated methyl-1 of the present invention; 2, the total quality percentage composition of 3-thiadiazole compound in compsn is 1%-90%, 4-halogenated methyl-1 of the present invention; 2, the ratio of 3-thiadiazole compound 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., the formulation that compsn is processed is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, can disperse dense dose, seed treatment emulsion, aqueous emulsion, any one in granula, granule, microemulsion, oil-suspending agent, finish, the seed with coated pesticidal, suspended emulsion agent, water-soluble granule, soluble thick agent, the water-dispersible granules greatly; 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; 4-halogenated methyl-1 of the present invention; 2; The 3-thiadiazole compound can with the sterilant of following group in one or more mixes uses: 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 swell, fluorine bell urea, WL 115110, pyridine worm swell, Acarus tritici urea, poisonous insect urea, penfluron, Noviflumuron, flucycloxuron, Novaluron, fluorine pyridine urea, Bay sir 6874, piperazine worm urea, 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 spy, 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, Flubendiamide, chlorine insect amide or tebufenpyrad, bromothalonil, pyrazine ketone, second mite azoles, tebufenpyrad, the young ketone of rattling away, pyrrole propyl ether, emaricin etc.; The control effect of combination medicament is good, and drug effect is played stably; Because compound of the present invention has excellent bactericidal activity and the long-living activity to the pathogenic fungi resistance of inducing plant; Therefore; Combination medicament also has good preventive effect to Plant diseases in the control insect pest of the plant, can also improve the immunological competence of plant, therefore; This based composition not only has parasiticidal effect; Also have sterilization and improve via plant immunity to obtain the effect of disease resistance and virus disease, compsn can prepare sterilant, sterilant, antiviral agent and sterilant, plant activator, and its drug effect is played stably.

Embodiment 13

4-halogenated methyl-1,2 of the present invention, 3-thiadiazole compound and the sterilization of sterilant combined preparation, the application of plant activator in control agricultural, forestry, gardening plant virus disease

Bioassay results showed that all four of the present invention - halomethyl-1 ,2,3 - thiadiazole compounds with existing fungicides such as benzo-thiadiazole, thiazole acid bacteria amines, amides thiophene, methyl thiophene induced amine 4 - methyl-1, 2,3 - thiadiazole-5 - carboxylic acid 4 - methyl-1, 2,3 - thiadiazole-5 - Sodium 4 - methyl-1, 3 - thiadiazol-5 - carboxylic acid ethyl ester, 5 - bromo-1 ,2,3 - thiadiazol-4 - carboxylic acid ethyl ester, 5 - iodo-1 ,2,3 - thiadiazole - 4 - Ethyl 4 - methyl-5 - bromo-1 ,2,3 - thiadiazole-4 - methyl-5 - iodo-1 ,2,3 - thiadiazole, 5, 5 - dibromo-1 ,2,3 - thiadiazol-4 - carboxylic acid ethyl ester, 5 - methyl-1, 2,3 - thiadiazol-4 - carboxylic acid, 5 - methyl-1 ,2 3 - thiadiazol-4 - sodium 5 - methyl-1, 2,3 - thiadiazol-4 - carboxylic acid ethyl ester, DL-β-aminobutyric acid, ribavirin, An Tuofen, mildew Ningnan Su, thiophene amides, amines or acid methyl thiophene lure, Cymoxanil, thiram, ziram, mancozeb, fosetyl, thiophanate-methyl, chlorothalonil, the enemy can be loose, procymidone , Fenpropidine, thiophanate, thiophanate, metalaxyl, salicylic acid, flumorph, Dimethomorph, efficient metalaxyl, efficient Benalaxyl, double-cypermethrin bacteria amine, flusulfamide , a flusulfamide, thiophene amine fluoride bacteria, flutolanil, phthalocyanine leaf blight, bacterial cyclopropane amino acid, cyflufenamid, cycloalkyl amine acid bacteria, cyano bacteria amine, amine silica thiabendazole, furosemide bacteria topiramate amine, pyridine thiophene bacteria amines, amine diacetylene acid bacteria, zoxamide, ofurace, carboxin, B strains Lee, iprodione, azoxystrobin, Kresoxim amines, fluoxastrobin, kresoxim, phenoxy bacteria amines, amine oxime ether bacteria, picoxystrobin, pyraclostrobin, trifloxystrobin, enestroburin, alkenyl amines trifloxystrobin, oxygen Propiconazole, bromuconazole, cyproconazole, difenoconazole yl, Diniconazole, efficient diniconazole, Epoxiconazole, fenbuconazole, fluorine quinazoline, Flusilazole, Flutriafol, Hexaconazole, imines azole, Ipconazole, Metconazole, myclobutanil, amyl bacteria yl, propiconazole, prothioconazole, 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, thiazole bacteria amines, earth benomyl, octyl thiophene ketones, benzene thiophene thiocyanate, dodecyl tridemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, piperidine oxime spots, fungus piperidine ring amines, boscalid, fluorine boscalid, piperidine amine bacteria, cyprodinil, mepanipyrim fluorine, ferimzone, mepanipyrim, pyrimethanil, fenarimol, nuarimol, off mites fierce, Dithianon, ethoxyquin, hydroxyquinoline, quinoline propoxyphene, phenoxy quinoline, diethofencarb, isopropyl bacteria amines, benzene thiabendazole amines Propamocarb, sulfur bacteria Granville, the enemy plague phosphorus, iprobenfos, topiramate bacteria phosphorus, tolclofos, blasticidin, kasugamycin, polymyxin, Polyoxin, validamycin, Jinggangmycin, streptomycin, A Cream Spirit furalaxyl, Benalaxyl, furosemide amide, mepronil, carbendazim, benomyl, thiophanate-methyl, triadimefon, 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, cupric hydroxide, benzene, cycloheximide, pencycuron, pyridazine cycloheximide, carbon tetrachloride phthalide, pyroquilon, Spiro bacteria amines, Tricyclazole, triforine, more fruit pyridine, Iminoctadine salt Iminoctadine amine, Dicloran, flusulfamide benzene, toluene flusulfamide, indole esters, Fenaminosulf, oxolinic acid, allyl benzene, thiazole, bronopol, methyl iodide, metham, enemy lines esters, dazomet dichloride, isopropyl ether, Fosthiazate, Cadusafos, fensulfothion,-worm phosphorus, fenamiphos, Ethoprophos, in addition to line phosphorus, chlorine triazophos, carbosulfan cyclophosphamide, oxamyl, aldicarb, carbofuran, sulfuryl fluoride, dichloropropene, dichloro-isonicotinic acid, allyl C isothiazole any other known as a fungicide in combination with any one or more of; the present invention is 4 - halomethyl-1 ,2,3 - thiadiazole compounds in the composition of the total The weight percentage of 1% -90%, the present invention is 4 - halomethyl-1 ,2,3 - thiadiazole compounds of pesticides with the product ratio of 1% weight percentage: 99% to 99%: 1%; pharmaceutical control effect is good, these compositions have a synergistic effect and the additive effect, we have not found to have a composition antagonistic effect; said composition can be used for agricultural and horticultural plant disease prevention and control of plant diseases, including control object Oomycetes of Achlya genus Aphanomyces spp, Pythium, Phytophthora, referring Terrier spp, Plasmopara genus false 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 food crops, cash crops , horticultural and forestry plants, other diseases, etc.; the compound of the present invention have good fungicidal activity and induction of disease activity and therefore, such compositions while carrying disease control, can improve the immune system of plants, the plants pathogenic fungi produce systemic acquired resistance, such compositions may be prepared that plant activator; processing composition selected from a wettable powder formulations, release agent, powder, microcapsule suspensions, dispersible concentrate agents, seed Processing emulsions, water emulsions, large grain, granules, micro-emulsions, oil suspensions, oil, seed coated with a pesticide, suspension emulsion, a water-soluble granule, soluble concentrate agent, water dispersible granules in any one kind.

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.

Embodiment 14

4-halogenated methyl-1,2 of the present invention, 3-thiadiazole compound and antiviral agent combined preparation antiviral agent, the application of plant activator in control agricultural, forestry, gardening plant virus disease

4-halogenated methyl-1,2,3-thiadiazole compound and existing Antiphytoviral medicament 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, 5-methyl isophthalic acid, 2,3-thiadiazoles-4-formic acid, 5-methyl isophthalic acid, 2; 3-thiadiazoles-4-sodium formiate, 5-methyl isophthalic acid, 2,3-thiadiazoles-4-ethyl formate, 5-brooethyl-1,2; 3-thiadiazoles-4-ethyl formate, 5-iodomethyl-1,2,3-thiadiazoles-4-ethyl formate, 4-methyl-5-brooethyl-1,2; 3-thiadiazoles, 4-methyl-5-iodomethyl-1,2,3-thiadiazoles, 5; 5-dibromo methyl isophthalic acid, 2,3-thiadiazoles-4-ethyl formate, DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lure in amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, the allyl isothiazole any one or the combination of multiple compound; Can produce the resistance of viral diseases of plants and the resistance of fungal disease by inducing plant; Especially the anti-TMV of evoking tobacco or be used for directly preventing and treating the activity of TMV, these compsns are suitable for inductive plant staple crop and comprise: paddy, wheat, barley, oat, corn, millet, Chinese sorghum, sweet potato, yam, cassava, soybean, broad bean, pea, pea-pods, mung bean, red bean, cotton, crudefiber crop, silkworm and mulberry, peanut, rape, sesame, soybean, Sunflower Receptacle, beet, sugarcane, tealeaves, coffee, cocoa, tobacco leaf, tobacco, flue-cured tobacco, genseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, fruit, flowers, oil plant, sugar material, cotton, fiber crops, tea, Chinese medicinal materials, plantation melon, really, tea, silkworm and mulberry, vegetables, various wild vegetable, bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, seedling, garden crop, air-curing of tobacco leaves, suncured tabacco, vegetables, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, yam, paddy rice, peanut, fruit tree, apple, banana, citrus, peach, papaya, orchid, potted landscape etc.; Virus disease comprises 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 various fruit tree virus diseases etc., wherein endangers serious mainly containing: tobacco virus, peppery pimento virus disease, tomato virus disease, Chinese cabbage virus disease, paddy rice virus disease comprise 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, cybidium ring spot virus etc.; The use of these compsns makes the immunizing power of crop self be improved, and has induced plant to produce the control to viral diseases of plants; Also can produce the direct control effect of virus disease, be green eco-friendly novel pesticide formulation; Therefore, these compsns can be used for the Antiphytoviral medicament and inducing plant Antiphytoviral medicament is the preparation and the application of plant activator.4-halogenated methyl-1 of the present invention; 2, the total quality percentage composition of 3-thiadiazole compound in compsn is 1%-90%, 4-halogenated methyl-1 of the present invention; 2, the ratio of 3-thiadiazole compound 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, 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; All show addition or synergism between these compsns, when keeping fungicidal activity, the effect that the antiviral activity of its antiviral activity or inducing plant is all used 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.

Except 4-halogenated methyl-1,2, outside the induced activity of 3-thiadiazole compound excellence itself, can know from the basic principles of chemistry; 4-halogenated methyl-1,2,3-thiadiazole compound can be degraded and produce the 4-methyl isophthalic acid in plant with after the water molecules effect; 2,3-thiadiazoles-5-formic acid confirms also that through relevant software prediction and test compound of the present invention can produce the 4-methyl isophthalic acid in the degraded of plant materials intracellular metabolite; 2,3-thiadiazoles-5-formic acid, bibliographical information confirms: the 4-methyl isophthalic acid; 2,3-thiadiazoles-5-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 also be used to prepare the Antiphytoviral medicament and inducing plant Antiphytoviral medicament has rationale.

Embodiment 15

4-halogenated methyl-1,2 of the present invention, the complete processing and the stability of 3-thiadiazole compound and commercially available agricultural chemical compound preparation

4-halogenated methyl-1 of the present invention; 2, the mixed preparation complete processing of 3-thiadiazole compound and commercially available agricultural chemical is seen table 4, and table 4 is visible; Most medicament all can be processed according to the method for statement; The main component of liquid preparation is other a component etc. of effective constituent and solubility promoter and tensio-active agent and synergistic agent, antifreezing agent, stablizer, thickening material or permeate agent etc., and the composition of solid preparation mainly includes imitates other agriculturals such as composition, tensio-active agent and filler and go up acceptable adjuvant components, and the preparation of processing is carried out cold storage test; Liquid preparation is placed 1 week not have to precipitate at 0 ± 2 degree centigrade and is separated out; Solid preparation placed for 2 weeks at 54 ± 2 degrees centigrade, and caking phenomenon does not appear in medicament, and the medicament drug effect that all preparations store before and after placing does not have significant difference; The rate of decomposition of mixing effective constituent is explained the medicament qualified stability in 5%.

Embodiment 16

4-halogenated methyl-1,2 of the present invention, the insecticidal activity of 3-thiadiazole compound

4-halogenated methyl-1,2 of the present invention, the 3-thiadiazole compound also has active preferably to insect pest of the plant, the insect among the embodiment 12 is all had insecticidal activity in various degree.

Table 1 synthetic 4-of the present invention halogenated methyl-1,2, the chemical structure of 3-thiadiazole compound

Table 2 synthetic 4-of the present invention halogenated methyl-1,2, the fungicidal activity of 3-thiadiazole compound (%)

Compound	AS	CA	GZ	PP	BC	RC	PS	SS	PI
										ZHH-F1	?-	-	-	-	-	?-	-	-	-
ZHH-15	6.67	12.50	30.00	21.15	40	50.98	80.26	43.14	16.22
										ZHH-1	42.86	42.11	100	100	88.89	100	100	100	66.67
ZHH-13	72.22	43.75	82.05	100	76.19	100	100	100	70.83
										ZZ4-27	13.04	22.22	0	50.00	20.00	30.30	23.68	92.11	0
ZHH-F2	-	-	-	-	-	-	-	-	-
										ZZ4-29	82.61	77.78	4.00	42.00	33.33	51.52	50.00	0	20.83
WSX295	44.44	93.75	79.49	36.59	42.86	79.17	21.13	94.74	100
										WSX-287	5.56	43.75	87.18	31.71	23.81	54.17	30.99	94.74	83.33
E4MTCA	34.78	38.89	0	54.00	26.67	42.42	42.11	100	4.17
										TDL	30.00	30.00	37.50	67.31	52.50	80.39	32.89	84.31	27.03

Data are the mensuration result of 50 mcg/ml in the table; The EMTCA:4-methyl isophthalic acid, 2,3-thiadiazoles-5-manthanoate; WSX-287=ZHH-20.

Table 34-halogenated methyl-1,2, the activity (%) of anti-TMV of 3-thiadiazole compound or the anti-TMV of evoking tobacco

The E4MTCA:4-methyl isophthalic acid, 2,3-thiadiazoles-5-manthanoate; TDL: tiadinil; *: the mensuration concentration of induced activity is 50 mcg/ml;

*: the mensuration concentration of induced activity is 100 mcg/ml; WSX-287=ZHH-20.

Table 44-halogenated methyl-1,2, the 3-thiadiazole compound mixes the working method of using preparation with commercially available agricultural chemical

Claims (6)

1. 4-halogenated methyl-1,2, the 3-thiadiazole compound is characterized in that: have suc as formula the general structure shown in the I:

Wherein, X is respectively the group that is selected from F, I; R is the group that is selected from methyl, ethyl, methoxycarbonyl, ethoxycarbonyl.

2. the described 4-halogenated methyl-1,2 of claim 1, the compound method of 3-thiadiazole compound I, concrete synthetic route is following:

Wherein, X is respectively the group that is selected from F, I; R ₁For being selected from the group of methyl, ethyl, methoxycarbonyl, ethoxycarbonyl; R ₂For being selected from the group of methyl, ethyl, methoxycarbonyl, ethoxycarbonyl.

3. the described 4-halogenated methyl-1,2 of claim 1,3-thiadiazole compound I goes up the purposes of acceptable assistant in the preparation sterilant with agricultural.

4. the described 4-halogenated methyl-1,2 of claim 1,3-thiadiazole compound I goes up the purposes of acceptable assistant in preparation Antiphytoviral medicament with agricultural.

5. the described 4-halogenated methyl-1,2 of claim 1,3-thiadiazole compound I goes up acceptable assistant is used for controlling plant diseases at preparation plant activator purposes with agricultural.

6. the described 4-halogenated methyl-1,2 of claim 1,3-thiadiazole compound I goes up the purposes that acceptable assistant is used to prevent and treat viral diseases of plants at preparation plant activator with agricultural.