CN101921244B - Derivative of 4-methyl-1,2,3-thiadiazole containing 4-(1,1,2,2-tetrafluoroethoxy)-3,5-dichlorobenzene amino and synthesis method and application thereof - Google Patents

Abstract

The invention provides a derivative of 4-methyl-1,2,3-thiadiazole containing 4-(1,1,2,2-tetrafluoroethoxy)-3,5-dichlorobenzene amino and a synthesis method and application thereof. The invention relates to heterocyclic compounds containing 1,2-diazole, in particular to 4-methyl-1,2,3-thiadiazole containing 1,1,2,2-tetrafluoroethoxy, which has the chemical structural general formula shown in the specification. The invention discloses a structural general formula and a synthesis method of the compounds, discloses an application of the compounds used as insecticide, bactericide, anti-plant virus agent and plant activator, discloses a process for mixing the compounds with agriculturally acceptable assistants or synergists to prepare the insecticide, the bactericide, the anti-plant virus agent and the plant activator, discloses an application of the combination of the compounds and commercial insecticide, bactericide, anti-plant virus agent or plant activator for preventing and treating diseases, insect pests and virus diseases in agriculture, forestry and horticulture, and discloses a preparation method of the compounds.

Description

Contain 4-(1,1,2,2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the verivate of 3-thiadiazoles and preparation method and use thereof

Technical field

Technical scheme of the present invention relates to the heterogeneous ring compound that contains 1,2-diazole, is specifically related to contain 4-(1,1,2,2-tetrafluoro oxyethyl group)-3,1,2 of 5-dichlorobenzene amido, 3-thiadiazoles derivative.

Background technology

Heterogeneous ring compound is the important source with lead compound of physiologically active, 1,2; The 3-thiadiazoles is the heterogeneous ring compound with wide biological activity, and wherein, tiadinil (TDL) and diazosulfide (BTH) all are commercial 1; 2,3-thiadiazole plant activator, plant activator are " environment friendly agriculturals " truly; Contriver's early-stage Study finds that N-(5-methyl-1,3-thiazole-2-yl)-4-methyl-1,2,3-thiadiazole has good induced activity (ZL 200610013185.5), at present just in industrialization process.

Polycomponent Ugi reaction is a kind of by the four component condensation reactions of the orientation between aldehyde, amine, acid and the isonitrile; In combinatorial chemistry, be widely used; Good stereoselectivity is arranged, based on the appropriate design of reactive component functional group, solid state reaction and complete synthesis in be widely used, this reaction has good Atom economy; Belong to the Green Chemistry reaction, significant in discovery of guide structure formerly and the optimization.Our early-stage Study is utilized Ugi reaction having carried out exploratory study; Synthesized the part new compound; Part of compounds has certain induced activity, and part of compounds has certain fungicidal activity, considers physico-chemical property that the F atom is special and to bioactive contribution.Early-stage Study is also found 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3, the 5-dichlorphenamide bulk powder is introduced the new compound (201010198522.9) of having found to have the high reactivity insecticidal activity equally in the lead compound, in order to widen the scope of guide's composition optimizes; The present invention has carried out deep structure to this compounds and has derived under the subsidy of state natural sciences fund (20872071 and 20911120069) and Tianjin natural science fund (10JCZDJC17500); From the principle of active substructure splicing, (4-(1,1 in target molecule, to introduce the F atom; 2;-3,5-dichlorphenamide bulk powder), and carried out the mensuration of desinsection, sterilization and antiviral and induced activity 2-tetrafluoro oxyethyl group).

Summary of the invention

Technical problem to be solved by this invention is: the new various 4-of containing (1 are provided; 1; 2,2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido; 2; The compound method of 3-thiadiazoles Hete rocyclic derivatives, provide the active of activity, the activity that suppresses pathogenic fungi and inducing anti-disease that this compounds suppresses insect growth and directly anti-phytoviral activity provide these compounds to carry out the application of plant protection in agriculture field, field of forestry, health field and gardening field as agrochemicals simultaneously like active and the protection activity and the therapeutic activity of the withered spot method of half leaf.

The present invention solves this technical problem the technical scheme that is adopted: have insecticidal activity, fungicidal activity and directly antiviral activity and induced activity contain 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3; The 4-methyl isophthalic acid of 5-dichlorobenzene amido; 2, the chemical structure of general formula of 3-thiadiazoles Hete rocyclic derivatives is suc as formula I, and the chemical structure of particular compound is seen table 1:

Wherein: R ₁Be 4-(1,1,2,2-tetrafluoro oxyethyl group)-3,5-dichlorphenamide bulk powder, R ₃During for cyclohexyl, R ₂For be selected from phenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, adjacent fluorophenyl, a fluorophenyl, to the group of fluorophenyl, o-trifluoromethyl phenyl, m-trifluoromethylphenyl, p-trifluoromethyl phenyl, ortho-nitrophenyl base, m-nitro base, p-nitrophenyl, o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, a hydroxy phenyl, p-hydroxybenzene, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl;

R ₁Be 4-(1,1,2,2-tetrafluoro oxyethyl group)-3,5-dichlorphenamide bulk powder, R ₃During for sec.-propyl, R ₂For be selected from phenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, adjacent fluorophenyl, a fluorophenyl, to the group of fluorophenyl, o-trifluoromethyl phenyl, m-trifluoromethylphenyl, p-trifluoromethyl phenyl, ortho-nitrophenyl base, m-nitro base, p-nitrophenyl, o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, a hydroxy phenyl, p-hydroxybenzene, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl;

The 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of the present invention, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the compound method of 3-thiadiazoles Hete rocyclic derivatives is following:

Wherein: R ₁Be 4-(1,1,2,2-tetrafluoro oxyethyl group)-3,5-dichlorophenyl; R ₂For be selected from phenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, adjacent fluorophenyl, a fluorophenyl, to the group of fluorophenyl, o-trifluoromethyl phenyl, m-trifluoromethylphenyl, p-trifluoromethyl phenyl, ortho-nitrophenyl base, m-nitro base, p-nitrophenyl, o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, a hydroxy phenyl, p-hydroxybenzene, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl; R ₃For being selected from the group of cyclohexyl, sec.-propyl.

Specifically be divided into following steps:

A. contain 4-(1,1,2,2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the preparation of 3-thiadiazoles Hete rocyclic derivatives:

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid again, 2,3-thiadiazoles-5-formic acid II, aminated compounds R ₁NH ₂III and aldehyde compound R ₂CHO VI and isonitrile compounds R ₃Each 2 mmole of NC V, with reaction system stirring reaction static placement after 0.5 hour at room temperature, the TCL monitoring reaction is after reaction in two days finishes; Reaction is if there is solid to generate, then filter solid phase prod, solid phase prod is used methanol wash; Perhaps use 200～300 order silica gel column chromatographies, eluent is 60～90 degrees centigrade a sherwood oil: ETHYLE ACETATE, according to the difference of product; Volume ratio is between 8: 1～1: 5, with the pure article calculated yield of gained, measure fusing point, carry out MS and ¹The mensuration of H NMR is synthesized and is contained 4-(1,1,2,2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, and 2, the amount of 3-thiadiazoles Hete rocyclic derivatives enlarges by corresponding proportion or dwindles;

B. contain 4-(1,1,2,2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the mensuration that 3-thiadiazoles Hete rocyclic derivatives influences the pathogenic fungi growth activity:

The 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of the present invention, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the measuring method of 3-thiadiazoles Hete rocyclic derivatives fungicidal activity or bacteriostatic activity is following:

Adopt thalli growth rate assay method, detailed process is: get 5 milligrams of sample dissolution in an amount of N, then with containing the medicament that a certain amount of polysorbas20 emulsifier aqueous solution is diluted to 500 mcg/ml; To supply the reagent agent under aseptic condition, respectively to draw in 1 milliliter of injection petridish, and add 9 milliliters of substratum more respectively, it is dull and stereotyped to process 50 mcg/ml pastilles after shaking up; Flat board to add 1 milliliter of aqua sterilisa is done blank, cuts the bacterium dish with the punch tool of 4 millimeters of diameters along the mycelia outer rim, moves on the pastille flat board; Being equilateral triangle puts; Every processing repetition 3 times is placed on cultivation in 24 ± 1 degrees centigrade of constant incubators with petridish, and colony diameter to be contrasted expands to 2-3 centimetre of " Invest, Then Investigate " and respectively handles bacterium dish expansion diameter; Average; Relatively calculate relative bacteriostasis rate with blank, supply the examination bacterial classification to comprise 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 (Cercosporaarachidicola); PP: ring rot of apple bacterium (Physalospora piricola); BC: botrytis cinerea pers (Botrytiscinerea); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); GZ: fusarium graminearum (Gibberella zeae); PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary); SS: Sclerotinia sclerotiorum (Sclerotiniasclerotiorum); 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.

C. the 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of the present invention, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the mensuration of 3-thiadiazoles Hete rocyclic derivatives inducing anti-disease activity:

The 4-(1,1,2 that contains of the present invention; 2-tetrafluoro oxyethyl group)-3; The 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the active screening method of 3-thiadiazoles Hete rocyclic derivatives 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; The direct antiviral activity of live body is measured and is comprised that protection mensuration active and therapeutic activity adopts frictional inoculation method to carry out; The activity of evoking tobacco resisting tobacco mosaic virus adopts live body to induce the method for frictional inoculation 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 Zuo X.; 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):

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;

D. the 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of the present invention, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2,3-thiadiazoles Hete rocyclic derivatives I is to the mensuration of small cabbage moth insecticidal activity:

The 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of the present invention, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, I is following to the screening method of the insecticidal activity of small cabbage moth for 3-thiadiazoles Hete rocyclic derivatives: adopt the blade medicine embrane method; Sample carries out active primary dcreening operation with 200 mg/litre earlier; Former medicine is earlier with the small amount of acetone dissolving, and then with 0.5 ‰ Triton-100 dilution, 0.5 ‰ Triton-100 water are contrast, and each concentration repeats for 4 times, and about 10 of each re-treatments try worm; Get fresh free of contamination cabbage leaves, in the soup of series concentration gradient, soaked 10 seconds, in indoor dry about 2 hours after, put into the petridish of 9 centimetres of diameters, insert 2 initial stage in age of the small cabbage moth larva of big or small basically identical respectively; Tighten with bungee and to be placed in the small cabbage moth constant temperature insectary check result and calculation correction mortality ratio after 96 hours or 120 hours; Touching polypide with little writing brush or tweezers, can not coordinated movement be dead; With the positive contrast of young urea of going out.

E. the 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of the present invention, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2,3-thiadiazoles Hete rocyclic derivatives I is to the mensuration of mosquito larvae insecticidal activity:

The 4-(1,1,2 that contains of the present invention; 2-tetrafluoro oxyethyl group)-3; The 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, I is following to the screening method of the insecticidal activity of mosquito larvae for 3-thiadiazoles Hete rocyclic derivatives: culex pipiens pallens; Its latin name is: Culex pipienspallens, the normal population of indoor feeding; Take by weighing 2.0 milligrams of test compounds in the Synnematin B medicine bottle, add 10 milliliters of acetone, vibration dissolving sample is mixed with the mother liquor of 200 mcg/ml; Pipette 1 milliliter of mother liquor in 150 ml beakers that fill 89 ml waters, choose mosquito larvae at the beginning of 10 4 ages, pour in the lump in the beaker together with 10 milliliters of feeding liquids, its liquor strength is 2 mcg/ml.It is 25 degrees centigrade of cultivations that the solution of handling well is put into the indoor maintenance temperature of standard treated together with the beaker of mosquito larvae; Begin check result after 24 hours; Add a small amount of mosquito feed and sucking-off tumbler every day, replenish in the beaker 5 milliliters/day of moisture evaporated, all dead or pupate up to mosquito larvae; Most larvas pupated in 8 days; With the aqueous solution that contains 1 milliliter of acetone is blank; With the positive contrast of fluorine bell urea.

The invention has the beneficial effects as follows: the present invention lures amine-one 1 to the plant activator first thiophene with independent intellectual property right; 2; The verivate of 3-thiadiazoles-the carried out optimization of the first guide structure of system; Utilize the principle design of active substructure splicing to synthesize serial new compound and the synthetic new compound has been carried out wide biological activity mensuration; Measure the mensuration that activity comprises bacteriostatic activity and inducing anti-disease activity, anti-phytoviral activity (activity that comprises protection, passivation, treatment and the withered spot of half leaf) and insecticidal activity; This compounds can be used for the control of disease, insect pest and the virus disease of agriculture field, field of forestry, gardening field and health field; Promptly can be used for preparing sterilant, antiviral agent, plant activator, sterilant and hygienic insecticide, also can comprise sterilant, hygienic insecticide, sterilant, anti-plant virus agent, plant activator combination use with the agricultural chemicals of commodity.

The present invention will more specifically explain through specific preparation and biological activity determination embodiment and contain 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2; Synthetic and the biological activity and the purposes of 3-thiadiazoles Hete rocyclic derivatives, unrestricted the present invention, especially its bioactive research only illustrate but said embodiment only is used for bright specifically the present invention; Rather than the restriction this patent, concrete embodiment is following:

Embodiment 1: the synthetic and structure of compound WH-C1 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and phenyl aldehyde, cyclohexyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, and hold over night afterreaction system has solid to separate out, and filters and gets thick product with the methanol wash solid; Mother liquor is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 10: 3: 2; Yield: 40%, fusing point: 178-181 degree centigrade, HR MS (m/z): 619.0955 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.38-7.05 (m, 7H), 6.18 (s, 1H), 6.12-5.85 (t, 1H), 5.372 (d, 1H), 3.87-3.85 (m, 1H), 2.88 (s, 3H), 2.02-1.04 (m, 10H), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 2: the synthetic and structure of compound WH-C2 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2; 3-thiadiazoles-5-formic acid, 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and 4-chloro-benzaldehyde, cyclohexyl isonitrile 1.9 mmoles at room temperature stirred reaction system 8 hours; It is muddy that hold over night afterreaction system becomes, and has a small amount of white solid to separate out, and filters and get thick product with the methanol wash solid; Yield: 30%, fusing point: 187-189 degree centigrade, HR MS (m/z): 653.0565 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.38-7.05 (m, 6H), 6.09 (s, 1H), 6.13-5.87 (t, 1H), 5.38 (d, 1H), 3.85-3.83 (m, 1H), 2.87 (s, 3H), 2.01-1.08 (m, 10H), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 3: the synthetic and structure of compound WH-C3 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and PARA HYDROXY BENZALDEHYDE, cyclohexyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, and hold over night, reaction system do not have solid and separate out; Reaction mixture concentrates the back and obtains the thick product of white with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 3: 2: 1; Yield: 24%, fusing point: 123-125 degree centigrade, HR MS (m/z): 635.0904 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.41 (s, 1H), 6.97 (d, 2H), 6.73 (d, 2H), 6.09 (s, 1H), 6.13-5.87 (t, 1H), 5.63 (s, 1H), 5.43 (d, 1H), 3.85-3.83 (m, 1H), 2.87 (s, 3H), 1.99-1.25 (m, 10H), this compound ¹HNMR is consistent with its chemical structure with the MS data presentation.

Embodiment 4: the synthetic and structure of compound WH-C4 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and o-chlorobenzaldehyde, cyclohexyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Mother liquor is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 6: 2: 1; Yield: 62%, fusing point: 163-166 degree centigrade, HR MS (m/z): 653.0570 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.43-7.02 (m, 6H), 6.56 (s, 1H), 6.10-5.84 (t, 1H), 5.52 (d, 1H), 3.91-3.87 (m, 1H), 2.87 (s, 3H), 2.06-1.09 (m, 10H), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 5: the synthetic and structure of compound WH-C5 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and m chlorobenzaldehyde, cyclohexyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Mother liquor is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 6: 1: 1; Yield: 40%, fusing point: 119-123 degree centigrade, HRMS (m/z): 655.0539 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.72-7.00 (m, 6H), 6.09 (s, 1H), 6.13-5.87 (t, 1H), 5.43 (d, 1H), 3.89-3.83 (m, 1H), 2.88 (s, 3H), 2.02-1.12 (m, 10H), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 6: the synthetic and structure of compound WH-C6 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and Ortho Nitro Benzaldehyde, cyclohexyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 7: 1: 6; Yield: 25%, fusing point: 189-191 degree centigrade, HR MS (m/z): 664.0806 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.97-7.28 (m, 6H), 6.57 (s, 1H), 6.10-5.84 (t, 1H), 5.61 (d, 1H), 3.87-3.84 (m, 1H), 2.88 (s, 3H), 2.05-1.09 (m, 10H), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 7: the synthetic and structure of compound WH-C7 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and m-nitrobenzaldehyde, cyclohexyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, the solid of a small amount of white is arranged, filter and use the methanol wash solid; Mother liquor is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 4: 1: 2; Yield: 40%, fusing point: 214-216 degree centigrade, HR MS (m/z): 664.0812 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 8.19 (d, 1H), 8.14 (d, 1H), 7.67-7.31 (m, 4H), 6.19 (s, 1H), 6.12-5.86 (t, 1H), 5.54 (d, 1H), 3.91-3.81 (m, 1H), 2.90 (s, 3H), 2.04-1.26 (m, 10H), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 8: the synthetic and structure of compound WH-C8 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and paranitrobenzaldehyde, cyclohexyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 6: 2: 3; Yield: 34%, fusing point: 179-181 degree centigrade, HR MS (m/z): 664.0818 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 8.17 (d, 2H), 7.43 (d, 2H), 7.35 (br, 1H), 7.12 (br, 1H), 6.15 (s, 1H), 6.12-5.86 (t, 1H), 5.49 (d, 1H), 3.88-3.86 (m, 1H), 2.89 (s, 3H), 2.03-1.05 (m, 10H), this compound ¹HNMR is consistent with its chemical structure with the MS data presentation.

Embodiment 9: the synthetic and structure of compound WH-C9 is identified

In 50 milliliters of round-bottomed flasks, add 10ml methyl alcohol, add the 4-methyl isophthalic acid then, 2; 3-thiadiazoles-5-formic acid, 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and o-methyl-benzene formaldehyde, cyclohexyl isonitrile 1.9 mmoles are with reaction system stirring reaction 8 hours at room temperature; Stopped reaction also gets product with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 6: 1: 3.

Embodiment 10: the synthetic and structure of compound WH-C10 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2; 3-thiadiazoles-5-formic acid, 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3, each 2 mmole of a 5-dichlorphenamide bulk powder and a tolyl aldehyde, cyclohexyl isonitrile 1.9 mmoles at room temperature stirred reaction system 8 hours; There is a small amount of white solid to separate out in the hold over night afterreaction system, filters and get thick product, yield: 24% with the methanol wash solid; Fusing point: 138-140 degree centigrade, HR MS (m/z): 633.1112 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.52-6.88 (m, 6H), 6.14 (s, 1H), 6.12-5.86 (t, 1H), 5.36 (d, 1H), 3.87-3.85 (m, 1H), 2.89 (s, 3H), 2.25 (s, 3H), 2.01-1.10 (m, 10H), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 11: the synthetic and structure of compound WH-C11 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and p-tolyl aldehyde, cyclohexyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 16: 1: 4; Yield: 38%, fusing point: 125-127 degree centigrade, HRMS (m/z): 633.1118 (M+H) ^{+ 1}HNMR (solvent: CDCl ₃, chemical shift): δ 7.52-6.97 (m, 6H), 6.13 (s, 1H), 6.12-5.86 (t, 1H), 5.36 (d, 1H), 3.87-3.83 (m, 1H), 2.88 (s, 3H), 2.30 (s, 3H), 2.00-1.00 (m, 10H), this compound ¹HNMR is consistent with its chemical structure with the MS data presentation.

Embodiment 12: the synthetic and structure of compound WH-C12 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and adjacent fluorobenzaldehyde, cyclohexyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 18: 3: 5; Yield: 36%, product is a weak yellow liquid, HR MS (m/z): 637.0861 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.31 (d, 1H), 7.08-7.00 (m, 3H), 6.64 (s, 2H), 6.42 (s, 1H), 6.15-5.85 (t, 1H), 5.54 (d, 1H), 3.88-3.87 (m, 1H), 2.88 (s, 3H), 2.04-1.18 (m, 10H), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 13: the synthetic and structure of compound WH-C13 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of a 5-dichlorphenamide bulk powder and a fluorobenzaldehyde, cyclohexyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 18: 3: 5; Yield: 36%, fusing point: 162-164 degree centigrade, HR MS (m/z): 637.0862 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.52-6.92 (m, 3H), 6.10 (s, 1H), 6.13-5.87 (t, 1H), 5.42 (d, 1H), 3.88-3.84 (m, 1H), 2.89 (s, 3H), 2.02-1.040 (m, 10H), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 14: the synthetic and structure of compound WH-C14 is identified

In 50 milliliters of round-bottomed flasks, add 10ml methyl alcohol, add the 4-methyl isophthalic acid then, 2; 3-thiadiazoles-5-formic acid, 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and p-Fluorobenzenecarboxaldehyde, cyclohexyl isonitrile 1.9 mmoles are with reaction system stirring reaction 8 hours at room temperature; Stopped reaction also gets product with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 2: 1: 1.

Embodiment 15: the synthetic and structure of compound WH-C15 is identified

In 50 milliliters of round-bottomed flasks, add 10ml methyl alcohol, add the 4-methyl isophthalic acid then, 2; 3-thiadiazoles-5-formic acid, 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and 2-(Trifluoromethyl) benzaldehyde, cyclohexyl isonitrile 1.9 mmoles are with reaction system stirring reaction 8 hours at room temperature; Stopped reaction also gets product with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 3: 1: 2.

Embodiment 16: the synthetic and structure of compound WH-C16 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and m-trifluoromethyl phenyl aldehyde, cyclohexyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE=5: 1; Yield: 36%, fusing point: 164-166 degree centigrade, HR MS (m/z): 687.0829 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.60-7.26 (m, 6H), 6.20 (s, 1H), 6.12-5.86 (t, 1H), 5.46 (d, 1H), 3.89-3.87 (m, 1H), 2.90 (s, 3H), 2.04-1.04 (m, 10H), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 17: the synthetic and structure of compound WH-C17 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3,5-dichlorphenamide bulk powder and to each 2 mmole of trifluoromethylated benzaldehyde, cyclohexyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE=6: 1; Yield: 60%, fusing point: 176-178 degree centigrade, HR MS (m/z): 687.0828 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.57-6.96 (m, 6H), 6.15 (s, 1H), 6.12-5.86 (t, 1H), 5.42 (d, 1H), 3.88-3.85 (m, 1H), 2.89 (s, 3H), 2.03-1.12 (m, 10H), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 18: the synthetic and structure of compound WH-C18 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and m-hydroxybenzaldehyde, cyclohexyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 12: 2: 5; Yield: 39%, fusing point: 191-194 degree centigrade, HR MS (m/z): 635.0904 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.52-6.65 (m, 6H), 6.07 (s, 1H), 6.13-5.87 (t, 1H), 5.47 (d, 1H), 5.28 (d, 1H), 3.85-3.83 (m, 1H), 2.87 (s, 3H), 2.002-1.10 (m, 10H), this compound ¹HNMR is consistent with its chemical structure with the MS data presentation.

Embodiment 19: the synthetic and structure of compound WH-C19 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2; 3-thiadiazoles-5-formic acid, 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and O-methoxy phenyl aldehyde, cyclohexyl isonitrile 1.9 mmoles at room temperature stirred reaction system 8 hours; There is a small amount of white solid to separate out in the hold over night afterreaction system, filters and get thick product, yield: 33% with the methanol wash solid; Fusing point: 144-145 degree centigrade, HR MS (m/z): 649.1061 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.30-6.79 (m, 6H), 6.43 (s, 1H), 6.11-5.84 (t, 1H), 5.38 (d, 1H), 3.89-3.87 (m, 1H), 2.80 (s, 3H), 2.88 (s, 3H), 2.01-1.02 (m, 10H), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 20: the synthetic and structure of compound WH-C20 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and NSC 43794, cyclohexyl isonitrile 1.9 mmoles; Filter also and use methanol wash, reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filtration also gets thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE=5: 1; Yield: 27%, fusing point: 116-118 degree centigrade, HRMS (m/z): 649.1063 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.52-6.61 (m, 6H), 6.13 (s, 1H), 6.13-5.86 (t, 1H), 5.44 (d, 1H), 3.89-3.85 (m, 1H), 3.69 (s, 3H), 2.88 (s, 3H), 2.01-1.33 (m, 10H), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 21: the synthetic and structure of compound WH-C21 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and aubepine, cyclohexyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 5: 1: 1; Yield: 74%, fusing point: 152-155 degree centigrade, HR MS (m/z): 649.1060 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.52-6.77 (m, 6H), 6.13 (s, 1H), 6.13-5.87 (t, 1H), 5.38 (d, 1H), 3.86-3.83 (m, 1H), 3.77 (s, 3H), 2.88 (s, 3H), 2.01-1.07 (m, 10H), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 22: the synthetic and structure of compound WH-E1 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and paranitrobenzaldehyde, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 5: 1: 1; Yield: 34%, fusing point: 153-155 degree centigrade, HR MS (m/z): 646.0312 (M+Na) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 8.17 (d, 2H, J=8.4Hz), 7.43 (d, 2H, J=8.4Hz), 6.13 (s, 1H); 6.00-5.46 (t, 1H), 5.45 (d, 1H, J=7.6Hz), 4.23-4.15 (m, 1H), 2.90 (s; 3H), 1.24 (d, 2H, J=6.4Hz), 1.14 (d, 2H, J=6.4Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 23: the synthetic and structure of compound WH-E2 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2; 3-thiadiazoles-5-formic acid, 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and o-methyl-benzene formaldehyde, sec.-propyl isonitrile 1.9 mmoles at room temperature stirred reaction system 8 hours; There is a small amount of white solid to separate out in the hold over night afterreaction system, filters and get thick product, yield: 23% with the methanol wash solid; Fusing point: 185-187 degree centigrade, HRMS (m/z): 593.0799 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.52-6.77 (m, 6H), 6.50 (s, 1H), 6.11-5.85 (t, 1H), 5.31 (d; 1H, J=7.6Hz), 4.23-4.18 (m, 1H), 2.89 (s, 3H), 2.44 (s, 3H); 1.22 (d, 3H, J=6.4Hz), 1.35 (d, 3H, J=6.8Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 24: the synthetic and structure of compound WH-E3 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of a 5-dichlorphenamide bulk powder and a tolyl aldehyde, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 4: 1: 2; Yield: 34%, fusing point: 136-139 degree centigrade, HR MS (m/z): 593.0807 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.52-6.88 (m, 6H), 6.13 (s, 1H), 6.13-5.86 (t, 1H), 5.33 (d; 1H, J=7.6Hz), 4.20-4.15 (m, 1H), 2.89 (s, 3H), 2.45 (s, 3H); 1.21 (d, 3H, J=6.4Hz), 1.114 (d, 3H, J=6.8Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 25: the synthetic and structure of compound WH-E4 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2; 3-thiadiazoles-5-formic acid, 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and p-tolyl aldehyde, sec.-propyl isonitrile 1.9 mmoles at room temperature stirred reaction system 8 hours; There is a small amount of white solid to separate out in the hold over night afterreaction system, filters and get thick product, yield: 42% with the methanol wash solid; Fusing point: 160-163 degree centigrade, HR MS (m/z): 593.0808 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.52-6.97 (m, 6H), 6.13 (s, 1H), 6.12-5.87 (t, 1H), 5.35 (d; 1H, J=7.6Hz), 4.19-4.14 (m, 1H), 2.88 (s, 3H), 2.30 (s, 3H); 1.20 (d, 3H, J=6.4Hz), 1.113 (d, 3H, J=6.4Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 26: the synthetic and structure of compound WH-E5 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and phenyl aldehyde, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 4: 1: 1; Yield: 31%, fusing point: 144-146 degree centigrade, HR MS (m/z): 579.0642 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.52-6.88 (m, 7H), 6.13 (s, 1H), 6.13-5.86 (t, 1H), 5.33 (d, 1H, J=7.6Hz), 4.20-4.15 (m, 1H), 2.89 (s, 3H), 1.21 (d, 3H, J=6.4Hz), 1.114 (d, 3H, J=6.4Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 27: the synthetic and structure of compound WH-E6 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and Ortho Nitro Benzaldehyde, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 4: 1: 2; Yield: 25%, fusing point: 103-105 degree centigrade, HRMS (m/z): 624.0493 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.96-7.26 (m, 6H), 6.56 (s, 1H), 6.10-5.84 (t, 1H), 5.63 (d, 1H, J=7.6Hz), 4.19-4.14 (m, 1H), 2.88 (s, 3H), 1.24 (d, 3H, J=6.8Hz) 1.12 (d, 3H, J=6.4Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 28: the synthetic and structure of compound WH-E7 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and m-nitrobenzaldehyde, sec.-propyl isonitrile 1.9 mmoles; Begin most to have small amount of crystal to produce, after reaction system was at room temperature stirred, crystal disappeared; Reaction system was at room temperature continued to stir 8 hours, and the adularescent solid is separated out in the hold over night afterreaction system, filters and gets thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 3: 1: 2; Yield: 31%, fusing point: 127-130 degree centigrade, HR MS (m/z): 624.0485 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 8.20-7.00 (m, 6H), 6.17 (s, 1H), 6.13-5.86 (t, 1H), 5.48 (d, 1H, J=7.6Hz), 4.21-4.16 (m, 1H), 2.91 (s, 3H), 1.25 (d, 3H, J=6.8Hz), 1.14 (d, 3H, J=6.4Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 29: the synthetic and structure of compound WH-E8 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and adjacent fluorobenzaldehyde, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 8: 1: 2; Yield: 31%, fusing point: 145-148 degree centigrade, HR MS (m/z): 597.0548 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.32-7.00 (m, 6H), 6.40 (s, 1H), 6.11-5.84 (t, 1H), 5.48 (d, 1H, J=7.6Hz), 4.21-4.17 (m, 1H), 2.88 (s, 3H), 1.24 (d, 3H, J=6.8Hz), 1.151 (d, 3H, J=6.8Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 30: the synthetic and structure of compound WH-E9 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of a 5-dichlorphenamide bulk powder and a fluorobenzaldehyde, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 8: 1: 2; Yield: 39%, fusing point: 121-123 degree centigrade, HRMS (m/z): 597.0552 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.30-6.92 (m, 6H), 6.08 (s, 1H), 6.13-5.87 (t, 1H), 5.38 (d, 1H, J=7.6Hz), 4.20-4.14 (m, 1H), 2.89 (s, 3H), 1.22 (d, 3H, J=6.8Hz), 1.13 (d, 3H, J=6.8Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 31: the synthetic and structure of compound WH-E10 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and p-Fluorobenzenecarboxaldehyde, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 8: 1: 2; Yield: 45%, fusing point: 153-155 degree centigrade, HR MS (m/z): 597.0546 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.30-6.97 (m, 6H), 6.11 (s, 1H), 6.11-5.86 (t, 1H), 5.35 (d, 1H, J=7.6Hz), 4.19-4.13 (m, 1H), 2.88 (s, 3H), 1.22 (d, 3H, J=6.8Hz), 1.12 (d, 3H, J=6.4Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 32: the synthetic and structure of compound WH-E11 is identified

In 50 milliliters of round-bottomed flasks, add 10ml methyl alcohol, add the 4-methyl isophthalic acid then, 2; 3-thiadiazoles-5-formic acid, 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and 2-(Trifluoromethyl) benzaldehyde, sec.-propyl isonitrile 1.9 mmoles are with reaction system stirring reaction 8 hours at room temperature; Stopped reaction also gets product with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE: methylene dichloride is 6: 2: 3.

Embodiment 33: the synthetic and structure of compound WH-E12 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and m-trifluoromethyl phenyl aldehyde, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE=6: 1; Yield: 53%, fusing point: 134-135 degree centigrade, HR MS (m/z): 669.0335 (M+Na) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.30-6.92 (m, 6H), 6.08 (s, 1H), 6.13-5.87 (t, 1H), 5.38 (d, 1H, J=7.6Hz), 4.20-4.14 (m, 1H), 2.89 (s, 3H), 1.22 (d, 3H, J=6.4Hz), 1.13 (d, 3H, J=6.8Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 34: the synthetic and structure of compound WH-E13 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3,5-dichlorphenamide bulk powder and to each 2 mmole of trifluoromethylated benzaldehyde, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE=6: 1; Yield: 48%, fusing point: 126-128 degree centigrade, HR MS (m/z): 669.0335 (M+Na) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.56 (d, 2H, J=8.4Hz), 7.31 (d, 2H, J=8.0Hz), 6.13 (s, 1H); 6.00-5.86 (t, 1H), 5.39 (d, 1H, J=7.6Hz), 4.22-4.16 (m, 1H), 2.90 (s; 3H), 1.23 (d, 3H, J=6.8Hz), 1.134 (d, 3H, J=6.4Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 35: the synthetic and structure of compound WH-E14 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of a 5-dichlorphenamide bulk powder and a hydroxyl formaldehyde, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE=4: 1; Yield: 54%, fusing point: 140-142 degree centigrade, HR MS (m/z): 617.0411 (M+Na) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.15 (t, 3H), 6.79 (m, 1H), 6.67 (m, 2H); 6.13-5.87 (t, 1H), 6.04 (s, 1H), 5.45 (d, 1H, J=7.6Hz); 4.22-4.13 (m, 1H), 2.99 (s, 1H), 2.87 (s, 1H), 1.20 (d; 3H, J=6.4Hz), 1.11 (d, 3H, J=6.4Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 36: the synthetic and structure of compound WH-E15 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and PARA HYDROXY BENZALDEHYDE, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE=3: 1; Yield: 43%, fusing point: 106-108 degree centigrade, HR MS (m/z): 617.0411 (M+Na) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 6.97 (d, 2H, J=8.4Hz), 6.73 (d, 2H, J=8.4Hz); 6.13-5.87 (t, 1H), 6.08 (s, 1H), 5.38 (d, 1H, J=7.6Hz); 5.36 (s, 1H), 4.18-4.13 (m, and 1H) 2.88 (s, 3H), 1.20 (d; 3H, J=6.4Hz), 1.11 (d, 3H, J=6.4Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 37: the synthetic and structure of compound WH-E16 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and o-chlorobenzaldehyde, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE=10: 1; Yield: 17%, fusing point: 163-165 degree centigrade, HR MS (m/z): 613.0249 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.30-6.92 (m, 6H), 6.08 (s, 1H), 6.13-5.87 (t, 1H), 5.38 (d, 1H, J=7.6Hz), 4.20-4.14 (m, 1H), 2.89 (s, 3H), 1.22 (d, 3H, J=6.8Hz) 1.13 (d, 3H, J=6.8Hz), this compound ¹HNMR is consistent with its chemical structure with the MS data presentation.

Embodiment 38: the synthetic and structure of compound WH-E17 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and m chlorobenzaldehyde, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE=10: 1; Yield: 17%, fusing point: 128-130 degree centigrade, HR MS (m/z): 635.0072 (M+Na) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.31 (d, 2H, J=8Hz), 7.22 (t, 2H), 7.00 (d; 2H, J=7.6Hz), 6.14-5.86 (t, 1H), 6.07 (s, 1H), 5.39 (d; 2H, J=7.6Hz), 4.19-4.14 (m, and 1H) 2.89 (s, 3H), 1.22 (d; 3H, J=6.8Hz), 1.13 (d, 3H, J=6.8Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 39: the synthetic and structure of compound WH-E18 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and 4-chloro-benzaldehyde, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE=3: 1; Yield: 21%, fusing point: 177-179 degree centigrade, HR MS (m/z): 613.0252 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.30-6.92 (m, 6H), 6.08 (s, 1H), 6.13-5.87 (t, 1H), 5.38 (d, 1H, J=7.6Hz), 4.20-4.14 (m, 1H), 2.89 (s, 3H), 1.22 (d, 3H, J=6.4Hz), 1.13 (d, 3H, J=6.4Hz), this compound ¹HNMR is consistent with its chemical structure with the MS data presentation.

Embodiment 40: the synthetic and structure of compound WH-E19 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and O-methoxy formaldehyde, sec.-propyl isonitrile 1.9 mmoles; Reaction system was at room temperature stirred 8 hours, have a small amount of white solid to separate out in the hold over night afterreaction system, filter and get thick product with the methanol wash solid; Filtrating is with 200～300 order silica gel column chromatographies, and eluent is a volume ratio, 60～90 degrees centigrade sherwood oil: ETHYLE ACETATE=3: 1; Yield: 42%, fusing point: 184-185 degree centigrade, HR MS (m/z): 609.0748 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.30-6.79 (m, 6H), 6.41 (s, 1H), 6.10-5.84 (t, 1H), 5.35 (d; 1H, J=7.6Hz), 4.23-4.14 (m, 1H), 3.79 (s, 3H), 2.88 (s, 3H); 1.20 (d, 3H, J=6.4Hz), 1.12 (d, 3H, J=6.4Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 41: the synthetic and structure of compound WH-E20 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2,3-thiadiazoles-5-formic acid, 4-(1; 1,2,2-tetrafluoro oxyethyl group)-3, each 2 mmole of 5-dichlorphenamide bulk powder and meta-methoxy formaldehyde, sec.-propyl isonitrile 1.9 mmoles; After reaction system at room temperature stirred 8 hours, leave standstill and separate out solid, filter and get product with methanol wash; Yield: 22%, fusing point: 121-122 degree centigrade, HR MS (m/z): 609.0748 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.21 (t, 3H), 6.84 (m, 1H), 6.71 (d.1H, J=7.6Hz); 6.61 (s, 1H), 6.14-5.86 (t, 1H), 5.36 (d, 1H, J=7.6Hz); 4.20-4.14 (m, 1H), 3.69 (s, 3H), 2.89 (s, 3H), 1.21 (d; 3H, J=6.8Hz), 1.12 (d, 3H, J=6.4Hz), this compound ¹HNMR is consistent with its chemical structure with the MS data presentation.

Embodiment 42: the synthetic and structure of compound WH-E21 is identified

In 50 milliliters of round-bottomed flasks, add 10 ml methanol, add the 4-methyl isophthalic acid then, 2; 3-thiadiazoles-5-formic acid, 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3,5-dichlorphenamide bulk powder and to each 2 mmole of methoxyl group formaldehyde, sec.-propyl isonitrile 1.9 mmoles at room temperature stirred reaction system 8 hours; There is a small amount of white solid to separate out in the hold over night afterreaction system, filters and get thick product, yield: 22% with the methanol wash solid; Fusing point: 141-143 degree centigrade, HR MS (m/z): 609.0750 (M+H) ^{+ 1}H NMR (solvent: CDCl ₃, chemical shift): δ 7.30-6.78 (m, 6H), 6.11 (s, 1H), 6.13-5.87 (t, 1H), 5.36 (d; 1H, J=7.6Hz), 4.19-4.13 (m, 1H), 3.77 (s, 3H), 2.88 (s, 3H); 1.20 (d, 3H, J=6.4Hz), 1.114 (d, 3H, J=6.4Hz), this compound ¹H NMR is consistent with its chemical structure with the MS data presentation.

Embodiment 43: 4-(1,1,2,2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the antibacterial or fungicidal activity of 3-thiadiazoles Hete rocyclic derivatives I of containing of the present invention

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 prodn.Thalli growth rate method is measured the result and is seen table 2; Table 2 shows; When 50 mcg/ml; Synthetic majority of compounds of the present invention all has fungicidal activity in various degree, and the similar positive control medicament young urea that goes out does not almost have fungicidal activity, and especially outstanding is the fungicidal activity of synthetic compound WH-C12 of the present invention to AS; WH-C15 is to the fungicidal activity of BC; WH-C1, WH-C5, WH-C11, WH-C12 are to the fungicidal activity of PP; WH-C15 is to the fungicidal activity of PS; WH-C2, WH-C6, WH-C14, WH-C17, WH-E1, WH-E3, WH-E12, WH-E13, WH-C15, WH-E16, WH-E18, WH-E19 are to the fungicidal activity of SS; WH-C12, WH-C14, WH-C15, WH-E15 all are higher than 60% to the fungicidal activity of RC; Also be higher than under the same terms the positive control medicament activity of young urea of going out to corresponding pathogenic fungi; Therefore; This compounds has shown fungicidal activity preferably, explains that this compounds also has the better prevention effect to disease in pest control.

Embodiment 44: 4-(1,1,2,2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the antiviral activity of 3-thiadiazoles Hete rocyclic derivatives I of containing of the present invention

Because the quantity of compound is many, the mensuration of antiviral activity is carried out at twice, and twice mensuration result shows; Synthetic of the present invention contains 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2; 3-thiadiazoles Hete rocyclic derivatives has the anti-phytoviral activity and the activity of inducing plant Antiphytoviral preferably preferably, and the antiviral activity of C series and the mensuration result of induced activity see table 3, and 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; The 4-(1,1,2 that contains of the present invention; 2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2; 3-thiadiazoles Hete rocyclic derivatives partly has the activity of direct anti-TMV preferably; WH-C16 and WH-C20 have good protection activity, and WH-C1, WH-C2, WH-C5, WH-C6, WH-C8, WH-C20 have significant inactivate activity, and WH-C1, WH-C2, WH-C3, WH-C8, WH-C10, WH-C12, WH-C14, WH-C16, WH-C17 have good therapeutic activity; WH-C1, WH-C4, WH-C10, WH-C13, WH-C17, WH-C18, WH-C19, WH-C21 have good induced activity; It is active that WH-C3, WH-C5, WH-C7, WH-C10, WH-C12, WH-C13, WH-C17, WH-C18 and WH-C19 have the withered spot of good half leaf, with contrast medicament virazole quite or be higher than the activity of virazole.The antiviral activity of E series is seen table 4 with the mensuration result of induced activity, and table 4 shows, the protection of WH-E5 and WH-E8 is active and contrast medicament quite or be higher than the contrast medicament; The inactivate activity of WH-E1, WH-E5, WH-E6, WH-E7, WH-E8, WH-E12, WH-E14, WH-E18 and WH-E20 and contrast medicament are quite or be higher than the contrast medicament; The therapeutic activity of WH-E12, WH-E13 and WH-E18 and contrast medicament are quite or be higher than the contrast medicament; The induced activity of WH-E10 and WH-E19 and contrast medicament are quite or be higher than the contrast medicament; It is active that WH-E3, WH-E4, WH-E6, WH-E7 and WH-E10 have the withered spot of good half leaf, with contrast medicament virazole quite or be higher than the activity of virazole.Twice measurement result finds that other compounds all have in various degree directly antiviral activity and induced activity.The half leaf method determination of activity is the result show, the antiviral activity of C of the present invention series and E series compound under 500 μ g/mL all with virazole quite or be higher than virazole.Above-mentioned activity good or active fine be meant its activity greater than or be far longer than the activity of positive control medicament commercially available medicine agent TDL, virazole or Ningnanmycin; Therefore, part of compounds of the present invention has significant Antiphytoviral and inducing plant and produces the effect that viral diseases of plants is produced resistance.

Can know from the basic principles of chemistry, contain 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2; Thereby 3-thiadiazoles Hete rocyclic derivatives can produce 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid from the carbonyl fracture in plant with after the water molecules effect; Confirm also that through relevant software prediction and test compound of the present invention can produce 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid in the degraded of plant materials intracellular metabolite; Bibliographical information confirms the 4-methyl isophthalic acid, 2, and 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, compound of the present invention can be used in Antiphytoviral medicament or inducing plant Antiphytoviral preparation of medicaments.

Embodiment 45: 4-(1,1,2,2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the insecticidal activity of 3-thiadiazoles Hete rocyclic derivatives I of containing of the present invention

Synthetic new compound WH-C3 of the present invention, WH-C15, WH-C20 have extraordinary desinsection to mosquito larvae and live, and its activity insecticidal activity with positive control medicament fluorine bell urea under 2 μ g/mL concentration is suitable, has all reached 100% (table 5); Reduce the active test well afoot of concentration.Synthetic new compound of the present invention all has insecticidal activity in various degree to small cabbage moth under 200 μ g/mL concentration, WH-C2, WH-C3, WH-C5, WH-C7, WH-C8, WH-C12, WH-C17 and WH-C18 and WH-E5, WH-E8, WH-E9 and WH-E10 to the activity of small cabbage moth and positive control medicament go out young urea insecticidal activity quite or be higher than the go out insecticidal activity (table 5) of young urea of positive control medicament;

Embodiment 46: the 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of the present invention, and the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2,3-thiadiazoles Hete rocyclic derivatives I and antiviral agent are combined in the application in control agricultural and forestry and the gardening plant virus disease

Contain 4-(1,1,2,2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido; 2,3-thiadiazoles Hete rocyclic derivatives I 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-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, 4-brooethyl-1,2,3-thiadiazoles-5-ethyl formate, 4-iodomethyl-1,2; 3-thiadiazoles-5-ethyl formate, 4-brooethyl-5-methyl isophthalic acid, 2,3-thiadiazoles, 4-iodomethyl-5-methyl isophthalic acid, 2; 3-thiadiazoles, 4,4-dibromo methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lure any 1 or 2 compounds combinations in amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, the allyl isothiazole; Be used to prevent and treat Agricultural pests such as Asiatic migrotory locust; Clouding car locust; Chinese rice grasshopper; Patanga japonica (l.Bol.); Single thorn mole cricket; The east mole cricket; Rice thrips; Onion thrips; Greenhouse thrips; Haplothrips aculeatus; Mai Jian manages thrips; Trialeurodes vaporariorum Westwood; Bemisia tabaci; Rice green leafhopper; Green leaf hopper; Chlorita biguttula; Spot clothing plant hopper; Brown paddy plant hopper; White backed planthopper; Small brown rice planthopper; The flat angle of sugarcane plant hopper; Cotten aphid; Green bugs; Grain aphid; Black peach aphid; Kaoliang aphid; Radish aphid; Icerya purchasi; Pseudaulacaspis pentagona; Unaspis shield kuwana; San jose scale; Wax insect; Ceroplastes rubens; The hard a red-spotted lizard of Korea's ball; Pear lace bug; The 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; The apple Spilonota lechriaspis; Brown belt length leaf roller; Intend smaller apple leaf roller; Striped rice borer; Bean-pod borer; Pyrausta nubilalis (Hubern).; Yellow rice borer; Oeobia undalis; Cnaphalocrocis medinali(rice leaf roller); The bar snout moth's larva; The wild snout moth's larva of lap leaf; Dichocrocis punctiferalis; Armyworm; Prodenia litura; Rice green caterpillar; Anomis flava; Beet armyworm; Pink rice borer; Bollworm; Ancient cooking vessel point diamond drill; Black cutworm; Big cutworm; Yellow cutworm; Steal poison moth; Gypsymoth; Palaearctic sweet potato; Greenish brown hawk moth; The straight burr rice hesperiidae; Pelopidas mathias; The oranges and tangerines swallowtail butterfly; Common Mormon; Small white; Pyrameis indica; The yellow a kind of butterfly harmful to crop plants of ramie; The beans blister beetle; The Venus ground beetle; Wrinkle sheath ground beetle; Wheat head ground beetle; Pleonomus canaliculatus; Agriotes subrittatus Motschulsky; Khapra beetle; Attagenus piceus; The little buprestid beetle of oranges and tangerines; Gold edge buprestid beetle; Tenebrio molitor; Dark mealworm; Red flour beetle; Confused flour beetle; The verdigris different beetle; 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; The yellowish leukorrhea ichneumon wasp; Armyworm white star ichneumon wasp; Corn earworm is hanged the cocoon ichneumon wasp; Bollworm tooth lip ichneumon wasp; Snout moth's larva stain wart ichneumon wasp; Mosquito; Fly; Horsefly; Wheat midge; Contarinia tritici; Pachydiplosis oryzae; Citrus fruit fly; The melon trypetid; The latent fly of wheat leaf ash; Americal rice leaf miner; The black fly of diving of beans stalk; Frit fly; Plant fly; Onion fly; The radish fly; Full skirt chases after posts fly; Pyrausta nubilalis (Hubern). is strict posts fly; Armyworm lacks the harm that must post insect pests such as fly; Can also produce resistance or inducing plant to viral diseases of plants and produce resistance virus disease and fungal disease; Especially the anti-TMV of evoking tobacco or be used for directly preventing and treating the activity of TMV, be used for the inductive plant comprise paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, yam, cassava, soybean, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, genseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, melon, really, plants such as agricultural, gardening, economy, forestry such as tea, wild vegetable, bamboo shoots, hops, pepper; The use of these compsns makes the immunizing power of crop self be improved, and when producing the control of insect especially infection insect, has induced plant to produce the control to viral diseases of plants; Also can produce the direct control effect of virus disease; Therefore, these compsns can be used for Antiphytoviral medicament and inducing plant Antiphytoviral preparation of medicaments and purposes.The 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of the present invention; The 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the total quality percentage composition of 3-thiadiazoles Hete rocyclic derivatives I in compsn is 1%-90%, the 4-(1 that contains of the present invention; 1,2,2-tetrafluoro oxyethyl group)-3; The 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the ratio of 3-thiadiazoles Hete rocyclic derivatives I 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 insecticidal activity, the effect that its antiviral activity all uses separately greater than any one compound; Do not find to have the compsn of antagonistic action, the drug effect lasting period of compsn is long.

Can know from the basic principles of chemistry, contain 4-(1,1,2; 2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, thus 3-thiadiazoles Hete rocyclic derivatives I can produce the 4-methyl isophthalic acid from the carbonyl fracture 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 Antiphytoviral medicament and inducing plant Antiphytoviral medicament.

The staple crop that these compsns are suitable for comprise cereal crop (comprising paddy, wheat, barley, oat, corn, millet, Chinese sorghum etc.), tuber crops (comprising sweet potato, yam, cassava etc.), legume crop (comprising 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, 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.; 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.Embodiment 47: the 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of the present invention, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the application in 3-thiadiazoles Hete rocyclic derivatives I and sterilant combination control agricultural and forestry and the gardening plant disease

Bioassay results showed that all of the present invention containing 4 - (1,1,2,2 - tetrafluoro-ethoxy) -3,5 - dichlorobenzene amino-4 - methyl-1, 2,3 - thiadiazole heterocyclic derivatives I and azole fungicides such existing 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, 2,3 - thiadiazole-5 - carboxylic acid ethyl ester, 5 - bromo-1 ,2 3 - thiadiazol-4 - carboxylic acid ethyl ester, 5 - iodo-1 ,2,3 - thiadiazol-4 - carboxylic acid ethyl ester 4 - methyl-5 - bromomethyl-1, 3 - thiadiazole-4 - methyl-5 - iodo-1 ,2,3 - thiadiazole, 5,5 - dibromo-1 ,2,3 - thiadiazol-4 - carboxylic acid ethyl ester, 4 - (bromomethyl) -1,2,3 - thiadiazole-5 - Ethyl 4 - iodo-methyl-1, 2,3 - thiadiazole-5 - Ethyl 4 - bromo-methyl -5 - methyl-1, 2,3 - thiadiazole-4 - iodo-5 - methyl-1, 2,3 - thiadiazole, 4,4 - dibromo-1 ,2 3 - thiadiazol-5 - carboxylic acid ethyl ester, DL-β-aminobutyric acid, ribavirin, An Tuofen, Ningnanmycin, thiophene amide, amine or acid induced a thiophene, cymoxanil, Fumei double, ziram, mancozeb, fosetyl, thiophanate-methyl, chlorothalonil, the enemy can be loose, procymidone, Fenpropidine, thiophanate, thiophanate, metalaxyl, water salicylic acid, flumorph, Dimethomorph, efficient metalaxyl, efficient Benalaxyl, double cypermethrin bacteria amine, flusulfamide, A flusulfamide, thiophene bacteria amine fluoride, fluorine amide, leaf blight phthalocyanine ring propionyl bacteria amine, cyflufenamid, cycloalkyl amine acid bacteria, cyano bacteria amine, amine silica thiabendazole, furosemide topiramate amine bacteria, penthiopyrad, diacetylene amine acid bacteria, zoxamide, ofurace, wilt rust Spirit B strains Lee, iprodione, azoxystrobin, Kresoxim amines, fluoxastrobin, kresoxim, phenoxy bacteria amines, amine oxime ether bacteria, picoxystrobin, pyraclostrobin, trifloxystrobin esters, enestroburin, allyl amine oxime bacteria, oxygen propiconazole, bromuconazole, cyproconazole, difenoconazole azole, Diniconazole, efficient diniconazole, Epoxiconazole, fenbuconazole, mefloquine azole, Flusilazole, Flutriafol, Hexaconazole, imines azole, Ipconazole, Metconazole, myclobutanil, penconazole, 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, thiophene pyraclostrobin, earth benomyl, Xin chlorthalidone, benzoth thiocyanate, twelve morpholine ring , fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, piperidine oxime plaque, bacteria amine piperidine ring, boscalid, fluorine boscalid, piperidine amine bacteria, azoxystrobin ring amines, amine fluoxastrobin, ferimzone, mepanipyrim, pyrimethanil, fenarimol, nuarimol, Chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, propoxy quinoline morpholine, phenoxy quinoline, diethofencarb, isopropyl bacteria amines, benzene thiabendazole amines Propamocarb, sulfur bacteria Granville, edifenphos, iprobenfos, topiramate bacteria phosphorus, tolclofos, blast off Su, kasugamycin, polymyxin, Polyoxin, validamycin, Jinggangmycin, streptomycin, metalaxyl, furalaxyl, Benalaxyl, furosemide amide, mepronil, carbendazim , benomyl, thiophanate-methyl, triadimefon, ethirimol sulfonate, dimethyl ethyl phenol, ethirimol, captafol, captan, folpet, vinclozolin, chlorofluorocarbons sclerotia Lee, Dimetachlone, chlorothalonil, Isoprothiolane, kitazine, leaf blight, PCNB, mancozeb, Propineb, fosetyl-aluminum, sulfur, Bordeaux mixture, copper sulfate, copper oxychloride, cuprous oxide, copper hydroxide, benzene cycloheximide, Pencycuron, da cycloheximide, tetrachlorophthalide, pyroquilon, Spiro bacteria amines, Tricyclazole, triforine, more fruit piperidine, Iminoctadine salts, biguanides octylamine, Dicloran, benzene, flusulfamide, toluene flusulfamide, indole ester, Fenaminosulf, oxolinic acid, allyl benzene, thiazole, bronopol, methyl iodide, metam sodium, the enemy lines esters, dazomet, dichloro-isopropyl ether, Fosthiazate, Cadusafos, fensulfothion, insects fenamiphos, fenamiphos, Ethoprophos, except line phosphorus, chlorine triazophos, carbosulfan cyclophosphamide, oxamyl, aldicarb, carbofuran, sulfuryl fluoride, dichloropropene, dichloro-isonicotinic acid, allyl isothiazolin any other known as a fungicide in any one or two used in combination; the present invention containing 4 - (1,1,2,2 - tetrafluoro-ethoxy) -3,5 - dichlorobenzene amino-4 - methyl-1, 2,3 - thiadiazole heterocycle derivative (I) in the composition in mass percent of the total content of 1% -90%, of the present invention containing 4 - (1,1,2,2 - tetrafluoro-ethoxy) -3,5 - dichloroaniline group 4 - methyl-1, 2,3 - thiadiazole heterocyclic derivative (I) with the product ratio of weight percentage of pesticide 1%: 99% to 99%: 1%; pharmaceutical control effect is good, these compositions has a certain synergy and additive effect is not found to have antagonistic effects composition; said composition can be used for agricultural and horticultural plant disease plant disease prevention and control, prevention and treatment of objects including Oomycetes genus Achlya, 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 other plant diseases, etc.; combination processed material is selected from a wettable powder formulations, release agent, powder, microcapsule suspensions, dispersible concentrate agent, seed treatment, emulsions, aqueous emulsion, large grain, granules, micro-emulsions, oil suspensions, oil with pesticide coated seeds, suspension emulsion, a water-soluble granule, soluble concentrate agent, water dispersible granules in any one.

The crop that these compsns are suitable for comprise cereal (comprising paddy, wheat, barley, oat, corn, millet, Chinese sorghum etc.), tuber crops (comprising sweet potato, yam, cassava etc.), beans (comprising soybean, broad bean, pea, mung bean, red bean etc.) and fiber (cotton, crudefiber crop, silkworm and mulberry etc.), oil plant (peanut, rape, sesame, soybean, Sunflower Receptacle etc.), sugar material (beet, sugarcane etc.), beverage (tealeaves, coffee, cocoa etc.), hobby (tobacco leaf etc.), medicinal (genseng, the bulb of fritillary etc.), the torrid zone (rubber, coconut, oil palm, the sisal hemp etc.) food crop of etc.ing and fruit, flowers, oil plant, sugared expect and cash crop such as cotton, fiber crops, tea, tobacco, Chinese medicinal materials and plant melon, really, tea, silkworm and mulberry, vegetables (containing various wild vegetable etc.), bamboo shoots, flowers and garden crop such as tobacco (flue-cured tobaccos such as ornamental plant, hops, medicinal material, pepper, seedling and other garden crops; Air-curing of tobacco leaves, suncured tabacco), vegetables, (tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic etc.), melon (watermelon, muskmelon, hami melon, pawpaw etc.), beans (soybean, broad bean, pea-pods etc.), yam, wheat, corn, paddy rice, peanut, fruit tree, (apple, banana, citrus, peach, papaya), flowers (like orchid), potted landscape etc.

Embodiment 48: the 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of the present invention, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the application in 3-thiadiazoles Hete rocyclic derivatives I and sterilant combination control agricultural and forestry and the gardening plant insect pest

The 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of the present invention; The 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the total quality percentage composition of 3-thiadiazoles Hete rocyclic derivatives I in compsn is 1%-90%, the 4-(1 that contains of the present invention; 1,2,2-tetrafluoro oxyethyl group)-3; The 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the ratio of 3-thiadiazoles Hete rocyclic derivatives I 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; The 4-(1 that contains of the present invention; 1; 2; 2-tetrafluoro oxyethyl group)-3; The 4-methyl isophthalic acid of 5-dichlorobenzene amido; 2; 3-thiadiazoles Hete rocyclic derivatives 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 combination medicament preventive effect is good, efficacy stability.

Embodiment 49: 4-(1,1,2,2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the complete processing and the stability of 3-thiadiazoles Hete rocyclic derivatives I and commercially available agricultural chemical compound preparation of containing of the present invention

The 4-(1,1,2 that contains of the present invention; 2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2; The mixed preparation complete processing of 3-thiadiazoles Hete rocyclic derivatives I and commercially available agricultural chemical is seen table 6, and table 6 is visible, and 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, 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, the cold storage test of process preparation; 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 compsn effective constituent is less than 5%, qualified stability.

The chemical structure of table 1 synthetic new compound of the present invention

Table 2 synthetic of the present invention contains the 4-methyl isophthalic acid, and 2, the bacteriostatic activity of 3-thiadiazoles derivative (/ %) (concentration is 50 mcg/ml)

Compound	F	L	D	G	AK	I	T	N	RC
											AS	BC	CA	GZ	PI	PP	PS	SS	RC
WH-C1	33.33	18.18	14.29	0	0	64.10	14.08	45.45	41.94
										WH-C2	4.76	18.18	21.43	0	23.81	46.15	14.08	72.73	41.94
WH-C3	14.29	0	0	0	0	33.33	7.04	18.18	48.39
										WH-C4	9.52	0	0	0	0	33.33	14.08	54.55	32.26
WH-C5	33.33	27.27	0	0	14.29	71.79	14.08	36.36	48.39
										WH-C6	4.76	4.55	0	0	0	20.51	42.25	72.73	0
WH-C7	33.33	36.36	0	0	0	20.51	42.25	54.55	22.58
										WH-C8	33.33	27.27	14.29	0	0	38.46	4.23	45.45	32.26
WH-C9	20.00	38.46	26.32	21.88	7.41	40.00	3.95	58.06	45.00
										WH-C10	0	0	14.29	0	19.05	38.46	42.25	36.36	22.58
WH-C11	47.62	0	21.43	23.81	23.81	61.54	14.08	45.45	9.68
										WH-C12	61.90	27.27	42.86	0	23.81	71.79	21.13	0	64.52
WH-C13	47.62	27.27	0	0	9.52	28.21	0	45.45	41.94
										WH-C14	33.33	59.09	0	0	0	20.51	42.25	63.64	70.97
WH-C15	45.00	73.08	47.37	40.63	33.33	47.50	63.16	70.97	100.00
										WH-C16	14.29	4.55	0	0	0	53.85	14.08	36.36	29.03
WH-C17	33.33	4.55	0	0	0	33.33	42.25	63.64	32.26
										WH-C18	0	4.55	0	0	0	7.69	14.08	27.27	16.13
WH-C19	42.86	4.55	21.43	0	0	58.97	42.25	54.55	0
										WH-C20	23.81	13.64	0	0	23.81	28.21	0	27.27	16.13
WH-C21	33.33	0	0	0	0	33.33	0	27.27	22.58
										WH-E1	0	55.17	0	7.69	14.81	21.05	8.45	65.12	31.58
WH-E2	5.26	17.24	0	0	3.70	18.42	4.23	37.21	23.68
										WH-E3	5.26	41.38	0	0	14.81	18.42	0	60.47	31.58
WH-E4	5.26	44.83	0	0	11.11	31.58	4.23	20.93	18.42
										WH-E5	5.26	37.93	0	0	3.70	18.42	0	39.53	18.42
WH-E6	5.26	37.93	0	0	33.33	23.68	4.23	48.84	31.58
										WH-E7	15.79	34.48	0	11.54	11.11	0	4.23	32.56	5.26
WH-E8	21.05	17.24	0	7.69	3.70	15.79	4.23	39.53	26.32
										WH-E9	5.26	31.03	0	0	29.63	31.58	0	16.28	26.32
WH-E10	5.26	27.59	0	0	3.70	5.26	4.23	27.91	18.42
										WH-E11	ND	ND	ND	ND	ND	ND	ND	ND	ND
WH-E12	9.09	21.88	0	0	17.24	38.46	32.35	66.67	21.62
										WH-E13	15.79	34.48	0	19.23	22.22	2.63	4.23	60.47	21.05
WH-E14	5.26	55.17	21.43	0	22.22	18.42	35.21	55.81	57.89
										WH-E15	5.26	55.17	14.29	0	3.70	31.58	0	53.49	73.68
WH-E16	26.32	44.83	0	7.69	11.11	10.53	4.23	62.79	15.79
										WH-E17	5.26	44.83	0	19.23	3.70	31.58	14.08	27.91	26.32
WH-E18	26.32	10.34	0	7.69	3.70	18.42	0	44.19	15.79
										WH-E19	26.32	51.72	0	0	33.33	18.42	4.23	65.12	23.68
WH-E20	4.55	28.13	5.56	3.03	24.14	38.46	5.88	66.67	43.24
										WH-E21	5.26	31.03	0	0	11.11	21.05	0	0	18.42
Young urea goes out	5.26	21.88	0	4.00	3.45	21.05	14.08	18.42	3.70

Table 3 synthetic of the present invention contains the 4-methyl isophthalic acid, and 2, (data are inhibiting rate/%) to the antiviral activity of 3-thiadiazoles derivative C series

*: what concentration 500 mcg/ml of induced activity were corresponding is 100 mcg/ml; What 100 mcg/ml were corresponding is 50 mcg/ml

Table 4 synthetic of the present invention contains the 4-methyl isophthalic acid, and 2, (data are inhibiting rate/%) to the antiviral activity of 3-thiadiazoles derivative E series

*: what concentration 500 mcg/ml of induced activity were corresponding is 100 mcg/ml; What 100 mcg/ml were corresponding is 50 mcg/ml

Table 5 synthetic of the present invention contains the 4-methyl isophthalic acid, and 2, the insecticidal activity of 3-thiadiazoles derivative (/ %)

Compound	Concentration (mg/L)	Mosquito larvae mortality ratio (%)	Concentration (mg/L)	Small cabbage moth mortality ratio (%)
					WH-C1	2	20	200	7.89
WH-C2	2	20	200	22.86
					WH-C3	2	100	200	21.62
WH-C4	2	40	200	7.69
					WH-C5	2	20	200	17.50
WH-C6	2	0	200	5.41
					WH-C7	2	10	200	21.05
WH-C8	2	0	200	23.68
					WH-C9	2	10	200	ND
WH-C10	2	10	200	5.26
					WH-C11	2	0	200	7.89
WH-C12	2	20	200	15.00
					WH-C13	2	30	200	ND
WH-C14	2	10	200	ND
					WH-C15	2	100	200	ND
WH-C16	2	20	200	2.63
					WH-C17	2	20	200	15.79
WH-C18	2	40	200	22.92
					WH-C19			200	10.81
WH-C20	2	100	200	7.90
					WH-C21	2	20	200	20
WH-E1	2	30	200	ND
					WH-E2	ND	ND	200	0
WH-E3	2	10	200	5.71
					WH-E4	2	10	200	10.53
WH-E5	2	20	200	20.59
					WH-E6	2	10	200	10.53
WH-E7	2	0	200	10.53
					WH-E8	2	20	200	12.82
WH-E9	2	10	200	12.82
					WH-E10	2	20	200	17.50
WH-E11	2	ND	200	ND
					WH-E12	2	30	200	ND
WH-E13	2	20	200	9.09
					WH-E14	2	10	200	ND
WH-E15	2	30	200	ND
					WH-E16	2	30	200	8.11
WH-E17	2	20	200	ND
					WH-E18	2	0	200	10.53
WH-E19	2	10	200	10.53
					WH-E20	2	30	200	ND
WH-E21	2	10	200	ND
					Fluorine bell urea	2	100	-	-
Young urea goes out	2	40	200	12.50

Table 6 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of the present invention, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2,3-thiadiazoles Hete rocyclic derivatives I mixes the preparation processing method of using with commercially available agricultural chemical

Claims (6)

1. one kind contains 4-(1,1,2,2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, and 2,3-thiadiazoles Hete rocyclic derivatives is characterized in that: have suc as formula the general structure shown in the I:

Wherein: R ₁Be 4-(1,1,2,2-tetrafluoro oxyethyl group)-3,5-dichlorophenyl; R ₂For be selected from phenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, adjacent fluorophenyl, a fluorophenyl, to the group of fluorophenyl, o-trifluoromethyl phenyl, m-trifluoromethylphenyl, p-trifluoromethyl phenyl, ortho-nitrophenyl base, m-nitro base, p-nitrophenyl, o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, a hydroxy phenyl, p-hydroxybenzene, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl; R ₃For being selected from the group of cyclohexyl, sec.-propyl.

2. the described 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of claim 1, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2, the compound method of 3-thiadiazoles Hete rocyclic derivatives I, concrete synthetic route is following:

Wherein: R ₁Be 4-(1,1,2,2-tetrafluoro oxyethyl group)-3,5-dichlorophenyl; R ₂For be selected from phenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, adjacent fluorophenyl, a fluorophenyl, to the group of fluorophenyl, o-trifluoromethyl phenyl, m-trifluoromethylphenyl, p-trifluoromethyl phenyl, ortho-nitrophenyl base, m-nitro base, p-nitrophenyl, o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, a hydroxy phenyl, p-hydroxybenzene, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl; R ₃For being selected from the group of cyclohexyl, sec.-propyl.

3. the described 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of claim 1, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2,3-thiadiazoles Hete rocyclic derivatives I goes up the purposes of acceptable assistant in the preparation sterilant with agricultural, and said worm is selected from mosquito larvae and small cabbage moth.

4. the described 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of claim 1, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2,3-thiadiazoles Hete rocyclic derivatives I goes up the purposes of acceptable assistant in the preparation sterilant with agricultural.

5. the described 4-(1,1,2 that contains of claim 1; 2-tetrafluoro oxyethyl group)-3, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2; 3-thiadiazoles Hete rocyclic derivatives I goes up the purposes of acceptable assistant in preparation Antiphytoviral medicament with agricultural, and said plant virus is a tobacco mosaic virus(TMV).

6. the described 4-(1,1,2,2-tetrafluoro oxyethyl group)-3 that contains of claim 1, the 4-methyl isophthalic acid of 5-dichlorobenzene amido, 2,3-thiadiazoles Hete rocyclic derivatives I goes up acceptable assistant is used for the plant activator of viral diseases of plants in preparation purposes with agricultural.