CN104496980B - Novel thiazole heterocyclic compounds and its preparation method and application - Google Patents

Abstract

The present invention relates to a thiazole heterocyclic compound and its preparation method and application. The invention discloses a thiazole heterocyclic compound represented by general formula III, whose general formula is: , wherein: X is selected from hydrogen, fluorine, chlorine, bromine, methyl, methoxy, cyano, isopropoxy and nitro; R is selected from hydrogen and methyl; the present invention is for thiazoles represented by general formula III Heterocyclic compounds were optimized first, and the antibacterial activity of the compound, the determination of the activity of inducing anti-plant virus, and the research of mixing with existing commercial preparations were carried out. Control of plant diseases and/or plant pests.

Description

A new type of thiazole heterocyclic compound and its preparation method and application

technical field

The present invention relates to a thiazole heterocyclic compound and its preparation method and application, in particular to a thiazole heterocyclic compound represented by the general formula III, its preparation method and application.

Background technique

Viruses, fungi and bacteria are one of the important factors affecting modern agricultural production. Various diseases caused by these pathogens seriously affect the yield and quality of agricultural products. Various chemical fungicides are one of the important means to reduce diseases and ensure the yield and quality of agricultural products. However, in recent years, the widespread and unscientific use of various fungicides has caused various pathogenic bacteria in my country's farmland to produce obvious resistance to existing traditional fungicides (Jia Junchao, Ma Lin, Fan Zhijin, etc. Journal of Pesticide Science, 2008 , 10(1): 19.). Methoxyacrylate fungicides were once one of the most widely used fungicides in China's farmland, and they have also produced obvious resistance in my country's farmland (Zhao Ping, Yan Qiuxu, Li Xin, etc. Pesticides, 2011, 50 (8 ): 547-542.). Therefore, it is imminent to develop fungicides with novel and simple structures and different modes of action. The trifluoromethyl dihydrothiazole compounds of the Japanese company have good bactericidal activity and certain insecticidal activity (JP2005330258).

Indole phytoalexins are a class of small molecular compounds with a wide range of biological activities. These small molecules all contain indole ring skeletons. For related patents and literature, see Jeandet P, Clément C, Courot E, etal.Modulation of phytoalexin biosynthesis in engineered plants for disease resistance. International journal of molecular sciences, 2013, 14(7): 14136-14170. Thiazole derivatives are also a class of hybrid compounds with a wide range of biological activities, with excellent bactericidal, insecticidal, antiviral and plant growth regulation, etc. Activity (Cui Shengfeng, Wang Yan, Lu Jingsong, DAMU GuriL.V., Zhou Chenghe, Science in China: Chemistry, Vol. 42 No. 8, 2012: 1105-1131)

Contents of the invention

The technical problem to be solved by the present invention is to provide a new type of fungicide with higher efficiency, broad spectrum, low toxicity, low ecological risk, and no cross-resistance with existing fungicides and higher biological Active 2-(5-substituted indol-2-yl)-4-(trifluoromethyl)thiazole heterocyclic compound and preparation method thereof, providing such compound to control plant pests in agriculture, horticulture, sanitation and forestry and biological activities of plant diseases and their determination methods, and at the same time provide applications of such compounds in the fields of agriculture, horticulture, forestry and health, in order to provide new candidate compounds and new ideas for the creation and research of new pesticides.

In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:

The present invention provides a thiazole heterocyclic compound represented by general formula III.

in:

X is selected from hydrogen, fluorine, chlorine, bromine, methyl, methoxy, cyano, isopropoxy and nitro;

R is selected from hydrogen and methyl.

The present invention also provides a method for preparing the compound represented by the above general formula III, comprising the following steps:

in:

X is selected from hydrogen, fluorine, chlorine, bromine, methyl, methoxy, cyano, isopropoxy and nitro;

R is selected from hydrogen and methyl.

A, the preparation of general formula II compound:

In the reaction vessel, add 80 ml of toluene, 100 mmol of compound I and 70 mmol of Lawson's reagent in sequence, stir and reflux for 3-6 hours, after the reaction is completed, the reaction solution is concentrated to remove toluene, and the residue is passed through a 200-300 mesh silica gel column layer Analysis and purification to obtain a light yellow solid, which is compound II, the eluent used is petroleum ether and ethyl acetate at 60-90 degrees Celsius, and the volume ratio of petroleum ether:ethyl acetate is 5:1-3:1 ;

B, the preparation of general formula IIIA compound:

In the reaction vessel, add 10 millimoles of compound II and 30 milliliters of absolute ethanol and stir, then add 10 millimoles of 3-bromo-1,1,1-trifluoroacetone, stir and reflux for 16 hours under nitrogen protection, after the reaction is completed, the reaction The liquid was concentrated to remove ethanol, and the residue was purified by 200-300 mesh silica gel column chromatography to obtain a white or light yellow solid, which was compound IIIA. The eluent used was petroleum ether and ethyl acetate at 60-90 degrees Celsius. The volume ratio of petroleum ether: ethyl acetate is 20:1-10:1;

C, the preparation of general formula IIIB compound:

In the reaction vessel, add 2.0 mmol of compound IIIA and 15 ml of anhydrous N,N-dimethylformamide and stir, cool to -5°C under nitrogen protection, add 3.0 mmol of sodium hydride, keep the temperature and stir for 15 Minutes, 3.0 mmoles of methyl iodide was added dropwise, and after the dropwise addition, the room temperature was gradually raised to room temperature and stirred for 16 hours; After washing and drying over anhydrous sodium sulfate, concentrate under reduced pressure to remove the solvent, and the residue is purified by 200-300 mesh silica gel column chromatography to obtain a white or light yellow solid, which is compound IIIB. The eluent used is 60-90 degrees Celsius Petroleum ether and ethyl acetate, the volume ratio of petroleum ether:ethyl acetate is 20:1-10:1.

The present invention includes pesticide acceptable salts of thiazole heterocyclic compounds represented by general formula III, such as salts formed with inorganic acids or organic acids, specifically, the inorganic acids are hydrochloric acid, hydrobromic acid, sulfuric acid or phosphoric acid, said organic acid including organic carboxylic acids such as citric acid (citric acid), lactic acid, malic acid, gluconic acid, tartaric acid, adipic acid, acetic acid, succinic acid, fumaric acid, ascorbic acid or itaconic acid, Or organic sulfonic acids such as methanesulfonic acid or benzenesulfonic acid.

The present invention also includes the pharmaceutically acceptable solvates of the thiazole heterocyclic compound represented by the general formula III including, without limitation, the thiazole heterocyclic compound represented by the general formula III and water, ethanol, isopropanol, ether, Solvates of acetone, etc.

The present invention also provides an insecticidal preparation comprising an effective amount of the compound represented by the general formula III or its agrochemically acceptable salt or its agrochemically acceptable solvate.

The pesticide preparation is an effective amount of the compound of general formula III or its pesticide acceptable salt or its pesticide acceptable solvate and one or both of the existing pesticides in a mass percentage of 1% : 99%-99%: 1% combined compound preparation.

The mass percent content of the effective amount of the compound of general formula III or its pesticide acceptable salt or its pesticide acceptable solvate in the insecticide preparation is 1%-90%.

The present invention also provides an antibacterial preparation comprising an effective amount of the compound of general formula III or its agrochemically acceptable salt or its agrochemically acceptable solvate.

The antibacterial preparation is an effective amount of the compound of general formula III or its pesticide acceptable salt or its pesticide acceptable solvate and one or both of the existing antibacterial agents in a mass percentage of 1%: 99 %-99%: 1% combined formulation.

The mass percent content of the effective amount of the compound of general formula III or its pesticide acceptable salt or its pesticide acceptable solvate in the antibacterial preparation is 1%-90%.

The present invention also provides an antiviral agent comprising an effective amount of the compound of general formula III or its agriculturally acceptable salt or its agriculturally acceptable solvate.

The antiviral agent is an effective amount of the compound of general formula III or its pesticide acceptable salt or its pesticide acceptable solvate and one or both of the existing antiviral agents in a mass percentage of 1 %: 99%-99%: 1% combined compound preparation.

The mass percent content of the effective amount of the compound of general formula III or its pesticide acceptable salt or its pesticide acceptable solvate in the antiviral agent is 1%-90%.

The present invention also relates to a compound of general formula III or its pesticide acceptable salt or its pesticide acceptable solvate for preventing and treating plant pathogenic fungus diseases and/or plant pests and diseases in the field of agriculture, forestry, gardening and hygiene. / or plant virus disease.

The present invention also relates to the application of the insecticide preparation in controlling agricultural, forestry, horticultural and/or hygienic pests.

The present invention also relates to the application of the antibacterial preparation in preventing and controlling agricultural, forestry and/or horticultural plant pathogenic fungus diseases.

The present invention also relates to the application of the antiviral agent in preventing and treating viral diseases of agricultural, forestry and/or horticultural plants.

The beneficial effect of the present invention is as follows: the present invention has carried out leading optimization to the compound of general formula III (IIIA and IIIB), and has carried out the antibacterial activity of this compound, the assay of inducing anti-plant virus activity and the research of mixed use with existing commercial preparations , this type of compound can be used for the prevention and treatment of plant diseases and/or plant pests in the fields of agriculture, forestry, horticulture and sanitation.

Description of drawings

Figure 1: Molecular structure diagram of compound mg001-1-1.

detailed description

In order to further clarify in more detail, the present invention will more specifically illustrate the synthesis, biological activity and application of the compound of general formula III through specific examples such as preparation and biological activity assay, and the described examples are only used to specifically illustrate the present invention. Non-limiting the present invention, especially its biological activity is only for illustration, but not limiting the patent, the specific implementation is as follows.

One, the preparation of the thiazole heterocyclic compound represented by general formula III

A, the preparation of general formula II compound:

Add 80 ml of toluene, 2.32 g (100 mmol) of compound I, and 2.83 g (70 mmol) of Lawson’s reagent to a 250 ml single-necked round-bottomed flask, and stir and reflux for 4 hours. After the reaction, the reaction solution is concentrated to remove toluene , the residue was purified by 200-300 mesh silica gel column chromatography to obtain a light yellow solid, namely compound II; wherein, the eluent used was petroleum ether and ethyl acetate at 60-90 degrees Celsius, and petroleum ether: ethyl acetate The volume ratio is 5:1;

The calculated pure product yield is 72-80%.

B, the preparation of general formula IIIA compound:

In a 50 ml three-neck round bottom flask, add 1.34 g (50 mmol) of compound II, 20 ml of ethanol, and 0.96 g (50 mmol) of 3-bromo-1,1,1-trifluoroacetone, and stir under nitrogen protection Reflux for 4 hours. After the reaction, the reaction solution was concentrated to remove ethanol, and the residue was purified by 200-300 mesh silica gel column chromatography to obtain a white solid, namely compound IIIA; wherein, the eluent used was petroleum ether at 60-90 degrees Celsius and Ethyl acetate, and the volume ratio of petroleum ether: ethyl acetate is 20:1;

The calculated pure product yield is 63-90%. The chemical structure and physical characterization data of the obtained compound of general formula IIIA are shown in Table 1.

C, the preparation of general formula IIIB compound:

In a 25 ml three-neck round bottom flask, add 0.62 g (2 mmol) of compound IIIA, 15 ml of anhydrous N, N-dimethylformamide, cool to -5 degrees Celsius under nitrogen protection, add 0.12 g of sodium hydride ( 3.0 mmol), kept the temperature and stirred for 15 minutes, added dropwise 0.43 g (3.0 mmol) of methyl iodide, gradually rose to room temperature and stirred for 16 hours after the dropwise addition, after the reaction ended, the reaction solution was poured into ice water, Extract with ethyl acetate, combine the organic phases, wash the organic phase with saturated brine and dry over anhydrous sodium sulfate, concentrate under reduced pressure to remove the solvent, and the residue is purified by 200-300 mesh silica gel column chromatography to obtain a white solid, which is compound IIIB ; The eluent used is petroleum ether and ethyl acetate at 60-90 degrees Celsius, and the volume ratio of petroleum ether:ethyl acetate is 20:1;

The calculated pure product yield is 59-72%. The chemical structure and physical parameters of the obtained compound of general formula IIIB are shown in Table 1.

Table 1 The chemical structure and physical parameter of general formula IIIA and IIIB compound of the present invention

D. Single crystal structure analysis of compound mg001-1-1

Put the ethyl acetate/petroleum ether (V:V=1:1) solution of the compound mg001-1-1 at room temperature, and let it stand for volatilization to obtain a colorless blocky crystal with a size of 0.20mm×0.18mm×0.12mm Single crystal of single crystal, collected single crystal diffraction data by φ-ω scanning at 113(2)K, 3222 independent diffraction data (Rint=0.1027) were used for crystal structure analysis, and all non-hydrogen atomic coordinates were determined by multiple rounds of Fourier synthesis , its atomic coordinates and anisotropy temperature factor are corrected by the full matrix least squares method, and its molecular structure is shown in Figure 1.

Two, the determination of the anti-phytopathogen activity of the thiazole heterocyclic compound represented by general formula IIIA and IIIB

In the present invention, the determination of the anti-phytopathogenic bacteria activity of the compounds of general formula IIIA and IIIB adopts the cell growth rate method, and the specific process is as follows: get 5 mg of compound IIIA or IIIB and dissolve them in an appropriate amount of dimethylformamide, and then use the compound containing Tween 20 Dilute the emulsifier aqueous solution to 500 micrograms/ml of the medicine, draw 1 milliliter of the medicine under aseptic conditions and inject it into a petri dish, then add 9 milliliters of culture medium, shake well and make a 50 micrograms per milliliter drug-containing plate. Use a plate with 1 ml of sterilized water as a blank control, use a puncher with a diameter of 4 mm to cut out the plate along the outer edge of the mycelium, move it to the plate containing the medicine, and place it in an equilateral triangle. Each treatment is repeated 3 times , place the petri dish in a constant temperature incubator at 24±1°C for cultivation. After the diameter of the control colony expands to 2-3 cm, record the expanded diameter of each treatment bacterial disc, calculate the average value, and compare it with the blank control to calculate the relative antibacterial rate;

Wherein, the contrast agent used is azoxystrobin, and its determination method is the same as above, and will not be repeated; the plant pathogenic bacteria include a variety of representative species of most of the plant pathogenic bacteria that actually occur in the field of agricultural production in my country, and their codes and names Including AS: Alternaria solani; BC: Botrytis cinerea; CA: Cercospora arachidicola; GZ: Gibberella zeae; PI: Potato late blight Phytophthora infestans (Mont.) de Bary); PP: Physalospora piricola; PS: Rice sheath blight (Pellicularia sasakii); RC: Rhizoctonia cerealis; SS: Rapeseed Sclerotinia sclerotiorum.

The measurement results are shown in Table 2.

Table 2 The antibacterial activity (concentration: 50 micrograms/ml, average bacteriostatic rate/%) of general formula IIIA and IIIB compound of the present invention

serial number compound AS CA GZ PP BC SS RC P.S. P.I. 1 mg001-1-1 24.32 35.66 40.13 36.6 37.76 70.11 72.02 53.5 25.83 2 mg001-1-2 29.72 38.91 36.54 60.19 72.76 31.21 38.64 37.64 22.29 3 mg001-1-3 23.78 29.18 46.97 63.54 87 87 89.16 83.06 57.96 4 mg001-1-4 23.78 9.73 18.26 50.16 47.08 35.66 47.55 36.6 26.75 5 mg001-1-5 19.45 29.72 26.75 8.44 75.53 49.81 92.6 42.23 25.83 6 mg001-1-6 21.4 23.78 62.41 42.8 53.5 47.08 76.43 38.02 17.84 7 mg001-1-7 47.14 59.45 44.59 32.1 56.65 10.7 39.24 25.34 0 8 mg001-1-8 28.54 59.45 53.5 35.66 84.97 4.28 67.7 70.4 22.29 9 mg001-1-9 23.78 38.21 25.18 27.62 36.79 38.64 37.04 91.71 19.45 10 mg001-1-10 19.45 11.89 26.75 19.71 81.82 68.26 78.2 18.31 33.2 11 mg001-1-11 0 0 40.13 17.84 53.5 27.82 52.41 25.34 8.91 12 mg001-1-12 23.78 7.64 12.58 34.52 33.44 14.86 20.58 87.89 34.05 13 mg001-1-13 29.72 30.57 9.44 27.62 36.79 23.78 12.35 61.14 29.18 14 mg001-1-14 24.32 35.66 40.13 36.6 37.76 70.11 72.02 53.5 25.83 15 mg001-1-15 29.18 35.66 24.08 0 44.06 57.19 76.13 54.91 22.14 16 mg001-1-16 41.61 30.57 3.15 13.8 86.94 80.25 45.27 78.33 19.45 17 mg001-1-17 17.47 8.68 22.71 47.21 32.47 74.05 65.39 41.73 18.32 18 mg001-1-18 34.36 30.21 29.15 20.47 27.11 37.34 51.49 51.25 48.28 32 Azoxystrobin 46.88 55.56 75 91.18 71.43 100 88.1 84.06 80.77

Table 2 shows that at 50 micrograms per milliliter, compounds IIIA and IIIB (Table 1) of the present invention all have different degrees of antibacterial activity, wherein the antibacterial activity of compounds mg001-1-7 and mg001-1-16 to AS is at 40% Above; compound mg001-1-7, mg001-1-8 antibacterial activity against CA is higher than 40%, activity is better than the contrast agent azoxystrobin; compound mg001-1-1, mg001-1-3, mg001-1- 6. The antibacterial activity of mg001-1-7, mg001-1-8, mg001-1-11, mg001-1-14 against GZ bacteria is above 40%; compounds mg001-1-2, mg001-1-3, mg001 -1-4, mg001-1-7, mg001-1-11, mg001-1-14 have higher than 40% antibacterial activity against PP, and higher than 40% antibacterial activity against PP; compounds mg001-1-2, mg001 -1-3, mg001-1-4, mg001-1-5, mg001-1-6, mg001-1-7, mg001-1-8, mg001-1-10, mg001-1-11, mg001-1 -14. The antibacterial activity of mg001-1-15 and mg001-1-16 against BC is higher than 40%, among which mg001-1-3, mg001-1-8, mg001-1-10 and mg001-1-16 are against BC The antibacterial activity of the drug is more than 80%, which is better than that of the contrast agent azoxystrobin; compounds mg001-1-1, mg001-1-3, mg001-1-5, mg001-1-6, mg001-1-10, mg001-1 -14, mg001-1-16, mg001-1-17 have antibacterial activity against SS higher than 40%; compounds mg001-1-1, mg001-1-3, mg001-1-5, mg001-1-6, mg001 -1-8, mg001-1-14, mg001-1-15, mg001-1-16 have an antibacterial activity against RC higher than 40%, and mg001-1-5 has an antibacterial activity against RC above 90%, which is better than Contrast drug azoxystrobin; compounds mg001-1-1, mg001-1-3, mg001-1-5, mg001-1-8, mg001-1-9, mg001-1-12, mg001-1-13, mg001 The antibacterial activity of -1-14, mg001-1-15, mg001-1-16, mg001-1-17, mg001-1-18 against PS was higher than 40%, and the antibacterial activity of mg001-1-9 against PS was More than 90%, better than the contrast drug azoxystrobin; the antibacterial activity of compounds mg001-1-3 and mg001-1-18 against PI is higher than 40%.

From the above results, it can be concluded that the thiazole heterocyclic compounds represented by the general formulas IIIA and IIIB exhibit excellent antibacterial activity and can be applied to prevent and control agricultural, forestry and/or horticultural plant fungal diseases.

Three, the determination of anti-tobacco mosaic virus (TMV) activity induced by thiazole heterocyclic compounds represented by general formula IIIA and IIIB

The assay method of general formula IIIA and IIIB compound inducing anti-TMV activity among the present invention adopts half-leaf method to carry out, and concrete steps are as follows:

A, standard plant activator: select tiiazil (TDL) (purity greater than 99.5%) as the standard plant activator;

B, the activity measurement of induction mode: with the common tobacco of consistent seedling age, 3 pots are a group, respectively inoculate the tobacco seedlings that have been processed before 7 days, and the processing method comprises: spraying test compound solution 2 to 3 times, each time 10 milliliter, or soil treatment, 10 milliliters each time, and the measured concentration was 50 micrograms per milliliter. On the 7th day, inoculate TMV on the newly grown tobacco leaves by rubbing. The incidence of disease, the number of comprehensive lesion according to the following formula to calculate the induced antiviral effect of the test compound to TMV, each treatment set 3 repetitions, blank control and standard drug control respectively select water and TDL;

C. Determination of therapeutic mode activity: Weigh the test compound according to the required concentration, add 5 drops of dimethylformamide (about 80 μL) to dissolve it, mix it with water containing a small amount of surfactant, and make a 50 μg/mL solution . Three pots of Shanxiyan tobacco at the age of 5 to 6 leaves were used as a group, and the test compound solution was sprayed 1 day after friction inoculation with TMV. After the seedlings were placed at 23±2°C and cultivated under light for 7 days, the disease incidence was checked. Grading criteria determine the disease grade and calculate the therapeutic activity of the compound.

D. Determination of protection mode activity: Weigh the test compound according to the required concentration, add 5 drops of dimethylformamide (about 80 μL) to dissolve it, mix it with water containing a small amount of surfactant, and make a 50 μg/mL solution . Select 5-6-leaf-aged Shanxiyan tobacco, 3 pots as a group, spray the test compound solution, rub inoculate TMV after 1 day, place the seedlings at 23±2°C and cultivate them under light for 7 days, and then check the disease. The disease grade was determined according to the grading standard, and the therapeutic activity of the compound was calculated.

E. Determination of passivation mode activity: the test is carried out at 23±2°C, accurately weigh the required agent, add 5 drops of dimethylformamide (about 80 μL) to dissolve it, and use 3.0x10-3mg/mL TMV solution Dilute to 0μg/mL, place passivation 1h. Afterwards, live friction inoculation was carried out on 5-6-leaf-age Shanxi tobacco plants. Using TMV solution containing 5 drops of dimethylformamide as a control, 5 leaves were inoculated for each treatment. After 3 days, the number of dead spots was investigated, and the inhibition rate was calculated. Each test was repeated 3 times.

in:

R is the induction effect of the test compound on TMV, unit: %;

CK is the average number of dead spots on the leaves of the blank control, unit: piece;

I is the average number of dead spots on the leaves after being induced by the test compound, unit: piece.

Wherein, the determination methods of ribavirin and ningnanmycin in different modes are the same as those described above, and will not be repeated here.

The determination results of the above-mentioned compounds of general formula IIIA and IIIB, ribavirin, ningnanmycin and TDL are shown in Table 3.

Table 3 The activity (concentration: 50 micrograms/ml, average inhibitory rate/%) of the compound of general formula IIIA and IIIB of the present invention against tobacco mosaic virus

serial number compound treat passivation Protect induce 1 mg001-1-1 10.65 40.23 29.25 27.99 2 mg001-1-2 27.69 37.93 56.46 25.67 3 mg001-1-3 12.91 27.78 15.59 27.13 4 mg001-1-4 22.5 68.97 40.14 59.45 5 mg001-1-5 17.99 29.63 21.51 24.71 6 mg001-1-6 15.74 63.79 28.57 47.12 7 mg001-1-7 15.04 14.35 40.16 65.73 8 mg001-1-8 31.71 43.05 25.3 41.03 9 mg001-1-9 21.76 44.25 57.14 29.23 10 mg001-1-10 13.25 37.96 54.22 25.64 11 mg001-1-11 29.54 58.04 12.24 39.36 12 mg001-1-12 22.65 46.76 32.13 30.43 13 mg001-1-13 25 65.52 18.37 25.29 14 mg001-1-14 19.66 29.17 11.25 29.06 15 mg001-1-15 18.06 50.58 19.05 16.39 16 mg001-1-16 19.72 26.43 52.38 42.55 17 mg001-1-17 10.83 43.11 22.45 11.87 18 mg001-1-18 18.47 21.3 44.74 28.31 19 Ribavirin 34.39 40.51 44.6 24.88 20 Ningnanmycin 54.93 55.78 53.35 28.58 twenty one TDL 7.94 23.57 40.84 59.25

Table 3 shows that at 50 micrograms per milliliter, compounds IIIA and IIIB (Table 1) of the present invention have different degrees of anti-TMV activity; in passivation mode, compounds mg001-1-1, mg001-1-4, mg001 -1-6, mg001-1-8, mg001-1-9, mg001-1-11, mg001-1-12, mg001-1-15, mg001-1-16, mg001-1-17 had inhibition rates greater than 40%, the activity was significantly better than that of the contrast drug ribavirin; in the protection mode, the compounds mg001-1-2, mg001-1-4, mg001-1-7, mg001-1-9, mg001-1-10, mg001- The inhibition rate of 1-16, mg001-1-18 is greater than 40%; in the induction mode, the inhibition rate of compound mg001-1-4, mg001-1-7, mg001-1-8, mg001-1-16 is greater than 40% %.

It can be seen that the compounds IIIA and IIIB of the present invention have good anti-TMV activity and can be applied to prevent and control agricultural, forestry and/or horticultural plant virus diseases.

4. Application of thiazole heterocyclic compounds represented by general formulas IIIA and IIIB alone or in combination with existing pesticides in the prevention and control of agricultural, forestry, horticultural and/or hygienic pests

When the thiazole heterocyclic compound represented by the general formula IIIA and IIIB is used alone as an insecticide to prevent and control agricultural, forestry, horticultural and/or hygienic pests, the thiazole heterocyclic compound represented by the general formula IIIA and IIIB includes not only the compound IIIA and IIIB also include the agrochemically acceptable salts of the compounds represented by the general formulas IIIA and IIIB or the agrochemically acceptable solvates thereof.

When the compound preparation of the thiazole heterocyclic compound represented by the general formula IIIA and IIIB combined with the existing insecticide is applied to the prevention and control of agricultural, forestry, horticultural and/or hygienic insect pests, the compound represented by the effective amount of IIIA and IIIB Its pesticide acceptable salt or its pesticide acceptable solvate is used in combination with one or two existing insecticides at a mass percentage of 1%:99%-99%:1%. Alternatively, the effective amount of the compound of general formula IIIA and IIIB or its pesticide acceptable salt or its pesticide acceptable solvate is 1%-90% by mass in the compound preparation.

Among them, the existing insecticides that can be used in combination with the compounds of the present invention include, but are not limited to: chlorpyrifos, diyron, acetamiprid, emamectin, mibamectin, abamectin, spinosa fenvalerate, beta-cyfluthrin, cypermethrin, beta-cypermethrin, cyhalothrin, deltamethrin, fenpropathrin, Beta-cyfluthrin, cyfluthrin, Lambda-cyhalothrin, dichlorophenyl ether permethrin, permethrin, allethrin, kungfu permethrin, bifenthrin, permethrin, ethofenproxil, bifenthrin, chlorofluvalinate fenvalerate, imidacloprid, acetamiprid, ene Acetamiprid, chlorothiaprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran, canidin, dartnam, diflubenzuron, diflubenzuron, chlorthiazuron, diflubenuron, difluben Urea, diflubenzuron, acetamiron, lufenuron, toxafluron, flufenuron, Noviflumuron is polyfluxuron, its CAS number is 121451-02-3, flufenuron, Novuron is diflufenuron, fluridine Urea, Bay sir 6874 ie {1-[(3.5-dichloro-4)4-nitrophenoxyphenyl 3-3-(2-chlorophenyl)-urea}, Bay SIR-8514 ie [1-( 4-trifluoromethoxyphenyl)-3-(2-chlorophenyl)-urea], chlorfenozuron, Bistrifluron i.e. bistriflubenzuron, furanozide, tebufenozide, chlorantraniliprozide, formazan Oxyfenozide, Cyclofenozide, Dimethoate, Omethoate, Dichlorvos, Acephate, Triazophos, Quetiafos, Pyridazinphos, Chlorazophos, Yechansan, Carbaryl, Anti- Pirimicarb, Meprocarb, Isoprocarb, Cartap, Zhongbucarb, Yefeisan, Carbaryl, Carbosulfan, Carbosulfan, Cartap, Bromofen, Hexythiazox, Fenpyroxifen, pyridaben, tetrafenazin, propargite, diafenthiuron, carbosulfan, pymetrozine, spirodiclofen, spirotetramat, spirotetramat, butene fipronil, three Azotin, buprofezin, fenmeth, fipronil, monosultap, dimehypo, chlorantraniliprole, flubendiamide, flucytraniliprole, cyantraniliprole, tolfenpyrad, tebufenpyrad, bromotraniliprole Nitrile, pyrazinone, etoxazole, tebufenpyrad, pyridoxone, pyriproxyfen, emamectin.

In addition, the dosage form that the compound preparation can be processed is selected from but not limited to wettable powder, sustained release agent, powder, microcapsule suspension, dispersible liquid preparation, dispersible solid preparation, seed treatment emulsion, water emulsion, large particle, Granules, microemulsions, oil suspensions, oils, seeds coated with pesticides, suspoemulsions, water-soluble granules, soluble concentrates, water-dispersible granules, poisonous grains, aerosols, block poison baits, slow Release blocks, concentrated poison baits, capsule granules, capsule suspensions, dispersible concentrates, powders, dry seed dressing powders, emulsifiable concentrates, electrostatic sprays, water-in-oil emulsions, seed treatment agents, oil-in-water emulsions, smoke tanks, powder Granules, smoke candles, smoke tubes, smoke sticks, seed treatment suspensions, smoke tablets, aerosols, smoke pills, granular poison baits, gas-generating agents, large granules, drifting powders, granules, ointments, thermal sprays, solids /liquid mixed agent, liquid/liquid mixed agent, cold mist, solid/solid mixed agent, medicinal paint, seed treatment liquid, microgranule, oil suspension, oil, oil dispersible powder, ointment, tablet Shaped poison baits, glue concentrates, pouring agents, rods, seed coating agents, poison baits, smears, small pieces of poison baits, suspensions, suspoemulsions, water-soluble granules, soluble concentrates, film-forming oils, soluble powders, Seed Treatment Water Soluble Powder, Ultra Low Volume Suspension Concentrate, Tablet, Tracking Powder, Ultra Low Volume Liquid, Vapor Release Agent, Water Dispersible Granule, Wettable Powder, Water Dispersible Powder for Wet Seed Dressing.

The pests that the compound preparation can control mainly include red spider mite, East Asian migratory locust, cloud-spotted car locust, Chinese rice locust, Japanese yellow-spine locust, single-spined mole cricket, oriental mole cricket, rice thrips, tabaci thrips, greenhouse thrips, Rice tube thrips, wheat tube thrips, greenhouse whitefly, whitefly, black-tailed leafhopper, leafhopper, cotton leafhopper, spotted waxhopper, brown planthopper, white-backed planthopper, brown planthopper, sugarcane Flat-horned planthopper, cotton aphid, wheat two-pronged aphid, wheat long tube aphid, peach aphid, sorghum aphid, radish aphid, cotton scale, mulberry shield scale, arrow point scale scale, pear round scale, white wax insect, red wax scale , Korean scorpion, pear net bug, banana net bug, slender horned bug, tiny flower bug, needle bug, rice spider bug, rice brown bug, rice black bug, rice green bug, green mirid bug, alfalfa blind Stinkbugs, Lygus midguts, Lacewings, Lacewings, Lacewings, Grain Moths, Clothes Moths, Yellow Lig Moths, Brown Lig Moths, Flat Lig Moths, Wheat Moths, Cotton Red Bollworms, Sweet Potato Wheat Moths, Diamondback Moths , Peach borer, soybean borer, peach borer, apple tip tip leaf roller, brown-banded leaf roller, pseudo yellow leaf roller, rice borer, bean pod borer, corn borer, rice borer, rice borer, rice leaf roller, strip Borer, cotton leaf roller, peach borer, armyworm, Spodoptera litura, rice borer, cotton small bridge builder, beet armyworm, large borer, cotton bollworm, tripod diamond, small cutworm, large cutworm, yellow cutworm Cutworm, poisonous moth, gypsy moth, sweet potato hornworm, bean hornworm, straight grain rice butterfly, hidden grain valley butterfly, citrus swallowtail, jade belt swallowtail, cabbage butterfly, ramie red nymph, ramie yellow nymph, Bean beetle, Venus beetle, wrinkled sheath beetle, wheat ear beetle, ditch needleworm, thin breast beetle, bark beetle, black beetle, citrus beetle, golden edge beetle, Tenebrio molitor, Tenebrio smut, red beetle, miscellaneous beetle, verdant beetle, dark beetle, North China giant beetle, mulberry beetle, star beetle, orange-brown beetle, pink-necked beetle, great ape leaf beetle , small ape leafworm, yellow shougua, yellow curly flea beetle, mung bean weevil, pea weevil, broad bean weevil, corn weevil, rice weevil, wheat sawfly, pear fruit bee, jaundice beetle, armyworm white star beetle, bollworm suspension Cocoon beetle, cotton bollworm toothed lip beetle, borer black spot wart bee, mosquito, fly, horsefly, wheat red midge, wheat yellow midge, rice gall midge, citrus fruit fly, melon fly, wheat leaf miner , Liriomyza americanum, Liriomyza bean stalk, wheat stalk fly, seed fly, onion fly, radish fly, umbrella skirt chasing fly, corn borer fly, armyworm lacking beard fly and other agricultural pests, forestry pests, Horticultural pests and sanitation pests; moreover, the compound preparation has good control effect, stable drug effect, certain synergistic and additive effects, and no antagonistic composition has been found.

The applicable crops of the compound preparation include rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, peanut, rape, sesame, sunflower, Beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, rapeseed, onion, garlic, watermelon, melon , cantaloupe, papaya, fruit, tea, wild vegetables, bamboo shoots, hops, potatoes, rice, pepper, apples, bananas, citrus, peach trees, papaya, orchids, bonsai. In addition, the compound preparation improves the defense ability of plants when killing insects, so that the plants have the defense ability against infection by pathogenic fungi, bacteria and viruses.

The use method of the compound preparation can adopt the method of directly watering and then spraying, and the compound preparation can also contain agriculturally acceptable solvents, emulsifiers, co-solvents and synergists.

5. Application of thiazole heterocyclic compounds represented by general formulas IIIA and IIIB alone or in combination with existing fungicides in the prevention and treatment of agricultural, forestry and/or horticultural plant fungal diseases

When the thiazole heterocyclic compounds represented by general formulas IIIA and IIIB are used alone as antibacterial agents for the prevention and treatment of agricultural, forestry and/or horticultural plant pathogens, the thiazole heterocyclic compounds represented by general formulas IIIA and IIIB include not only compounds IIIA and IIIB also includes the agrochemically acceptable salts of the compounds represented by the general formulas IIIA and IIIB or the agrochemically acceptable solvates thereof.

When the compound preparation of the thiazole heterocyclic compound represented by the general formula IIIA and IIIB combined with the existing insecticide is applied to the prevention and treatment of agricultural, forestry and/or horticultural plant fungus diseases, the effective amount of the compound represented by IIIA and IIIB Its pesticide acceptable salt or its pesticide acceptable solvate is used in combination with one or two existing pesticides at a mass percentage of 1%:99%-99%:1%; Alternatively, the effective amount of the compound of general formula IIIA and IIIB or its pesticide acceptable salt or its pesticide acceptable solvate is 1%-90% by mass in the compound preparation.

Among them, the existing fungicides that can be used in combination with the compounds of the present invention include, but are not limited to: benzothiadiazole, thiazilamide, thiamide, methiamide, 4-methyl-1,2,3- Thiadiazole-5-carboxylic acid, 4-methyl-1,2,3-thiadiazole-5-sodium carboxylate, 4-methyl-1,2,3-thiadiazole-5-carboxylic acid ethyl ester, DL- β-Aminobutyric acid, isotianil (isotianil), ribavirin, antorfin, ningnanmycin or salicylic acid, cymoxanil, thiram, thiram zinc, mancozeb, fosfosal, formazan Thiophanate, chlorothalonil, dicortisone, procymidone, fenpropidin, thiophanate-methyl, thiophanate, metalaxyl, salicylic acid, flumorph, dimethomorph, high-efficiency nail cream Ling, high-efficiency benalaxyl, diclofenamide, sulfanil, mesulfanil, thifluzamide, fluamide, yekuphthalein, cyproamid, cyclofluxamid, fenhexamid, Cyanoxanil, Sithiopylam, Fubifen, Penthiopyrad, Mandipyramide, Benzamid, Mefuramide, Wiltoxalin, Bactamil, Iprodione, Azoxystrobin, Kysoxystrobin, fluoxastrobin, kysstrobin, fenoxystrobin, oryzastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, enoxastrobin, enoxastrobin, oxycyclazole , Fuconazole, Cyproconazole, Difenoconazole, Diniconazole, Diniconazole, Econazole, Niconazole, Fluquinazole, Flusilazole, Fenconazole, Hexaconazole, Sub Amidazole, bacconazole, metconazole, mycloconazole, penconazole, propiconazole, prothioconazole, silicon fluconazole, tebuconazole, tetrafluconazole, triaconazole, fenconazole, Bentriconazole, Thiabendazole, Maisui Ning, Imazalil, Imazalil, Prochloraz, Flufenazole, Cyanazazole, Midazolone, Oximidazole, Rice Blastizolin, Oxafluconazole, Pyridoxazole, hymexazol, oxaxyl, ethaboxam, terrebendazim, octhinone, thiothiocyanate, dodecyclomorph, fenfenmorph, tridemorph, seed dressing, Fludioxonil, fluazinam, pyroxenil, fenfluxamid, boscalid, fludoxamid, boscalid, cyprodinil, fluoxanil, azoxychlor, hydrazone, Pyrimethanil, chlorpyrimidinol, fluoropyrimidinol, acetophenone, dicyanoanthraquinone, ethoxyquin, hydroxyquinoline, propoxyquinoline, phenoxyquinoline, Dimethocarb, Iprocarbamide , benthiacarb, propamocarb, sulfacarb, difenfo-fos, isofensin, pyrafos, tolclofos-methyl, blasticidin, kasugamycin, polyoxin, polyoxin , validamycin, Jinggangmycin, streptomycin, metalaxyl, furaxyl, benalaxyl, furamide, rustamine, carbendazim, benomyl, thiophanate-methyl, triadimefon, Ethyrimol sulfonate, pyrimol, pyrimethol, captafol, captan, folpet, vinclozolin, fluclochloride, sclerotin, chlorothalonil, rice blast , Dao blast net, Yekuzol, pentachloronitrobenzene, mancozeb, propineb, aluminum triethylphosphonate, sulfur, Bordeaux mixture, copper sulfate, copper oxychloride, cuprous oxide, copper hydroxide , metracyclone, pentocuron, pyridoxetone, tetrachlorophthalide, pyroquinone, spirulina, tricyclazole, azinamine, dorbutin, biguanide octyl salt, biguanidine octylamine, and chloramine . Metron, dichloroisopropyl ether, thiazolphos, fensofos, chrysanthemum, phenophos, phenophos, chlorazophos, fenthion, thiazolin, aldicarb, carbofuran, sulfur Acyl fluoride, dichloropropene, dichloroisonicotinic acid, allyl isothiazole.

In addition, the dosage form that the compound preparation can be processed is selected from but not limited to wettable powder, sustained release agent, powder, microcapsule suspension, dispersible liquid preparation, dispersible solid preparation, seed treatment emulsion, water emulsion, large particle, Granules, microemulsions, oil suspensions, oils, seeds coated with pesticides, suspoemulsions, water-soluble granules, soluble concentrates, water-dispersible granules, poisonous grains, aerosols, block poison baits, slow Release blocks, concentrated poison baits, capsule granules, capsule suspensions, dispersible concentrates, powders, dry seed dressing powders, emulsifiable concentrates, electrostatic sprays, water-in-oil emulsions, seed treatment agents, oil-in-water emulsions, smoke tanks, powder Granules, smoke candles, smoke tubes, smoke sticks, seed treatment suspensions, smoke tablets, aerosols, smoke pills, granular poison baits, gas-generating agents, large granules, drifting powders, granules, ointments, thermal sprays, solids /liquid mixed agent, liquid/liquid mixed agent, cold mist, solid/solid mixed agent, medicinal paint, seed treatment liquid, microgranule, oil suspension, oil, oil dispersible powder, ointment, tablet Shaped poison baits, glue concentrates, pouring agents, rods, seed coating agents, poison baits, smears, small pieces of poison baits, suspensions, suspoemulsions, water-soluble granules, soluble concentrates, film-forming oils, soluble powders, Seed Treatment Water Soluble Powder, Ultra Low Volume Suspension Concentrate, Tablet, Tracking Powder, Ultra Low Volume Liquid, Vapor Release Agent, Water Dispersible Granule, Wettable Powder, Water Dispersible Powder for Wet Seed Dressing.

The plant pathogenic diseases that can be prevented and controlled by the compound preparation include the genus Coccidiomyces, Aphanomyces, Pythium, Phytophthora, Dactylopsis, Plasmodium, Pseudomonas, and Peronospora of Oomycetes. Diseases caused by more than 20 genera, such as rice seedling rot, tomato root rot, potato late blight, tobacco black shank, millet powdery mildew, grape downy mildew, lettuce downy mildew, cucumber downy mildew, Cucumber anthracnose and other diseases of food crops, horticultural plants and forestry plants, etc.; and the compound preparation has a good control effect. These compositions have certain synergistic and additive effects, and no combination with antagonistic effects has been found. things. Wherein, the antibacterial activity determination method of the compound preparation can refer to the determination part of the antibacterial activity of compounds IIIA and IIIB, and will not be repeated here.

The crops suitable for the compound preparation include cereals (including rice, wheat, barley, oats, corn, millet, sorghum, etc.), potato crops (including sweet potatoes, potatoes, cassava, etc.), beans (including soybeans, broad beans, peas, mung bean, adzuki bean, etc.), fiber (cotton, hemp, sericulture, etc.), oil plant (peanut, rapeseed, sesame, soybean, sunflower, etc.), sugar material (beet, sugar cane, etc.), beverage (tea, coffee, cocoa, etc.), Hobbies (tobacco leaves, etc.), medicinal (ginseng, fritillary, etc.), tropical (rubber, coconut, oil palm, sisal, etc.) and other food crops and fruits, flowers, oil plants, sugar crops, cotton, hemp, tea, tobacco, traditional Chinese medicine Economic crops such as wood, melons, fruits, tea, sericulture, vegetables (including various wild vegetables, etc.), bamboo shoots, flowers and ornamental plants, hops, medicinal materials, pepper, seedlings and other horticultural crops, including tobacco (flue-cured tobacco, Tobacco, sun-dried tobacco), vegetables (tomatoes, peppers, radishes, cucumbers, cabbage, celery, mustard, beets, rapeseed, onions, garlic, etc.), melons (watermelon, melon, cantaloupe, papaya, etc.), beans (soybeans , broad beans, peas, etc.), potatoes, wheat, corn, rice, peanuts, fruit trees, (apple, banana, citrus, peach tree, papaya), flowers (such as orchids), bonsai, etc. The compound preparation improves the defense ability of the plant while sterilizing, so that the plant has the defense ability against the infection of pathogenic fungi, bacteria and viruses.

6. Application of thiazole heterocyclic compounds represented by general formulas IIIA and IIIB alone or in combination with existing antiviral agents in the prevention and treatment of agricultural, forestry and/or horticultural plant virus diseases

When the thiazole heterocyclic compound represented by the general formula IIIA and IIIB is used alone as an antiviral agent for the prevention and treatment of agricultural, forestry and/or horticultural plant pathogens, the thiazole heterocyclic compound represented by the general formula IIIA and IIIB includes not only the compound IIIA and IIIB also include the agrochemically acceptable salts of the compounds represented by the general formulas IIIA and IIIB or the agrochemically acceptable solvates thereof.

When the compound preparation of the thiazole heterocyclic compound represented by the general formula IIIA and IIIB combined with the existing antiviral agent is applied to the prevention and treatment of agricultural, forestry and/or horticultural plant pathogens, the effective amount of the compound represented by IIIA and IIIB Its pesticide acceptable salt or its pesticide acceptable solvate is used in combination with one or two of the existing antiviral agents at a mass percentage of 1%:99%-99%:1%; Alternatively, the effective amount of the compound of general formula IIIA and IIIB or its pesticide acceptable salt or its pesticide acceptable solvate is 1%-90% by mass in the compound preparation.

Among them, the existing antiviral agents that can be used in combination with the compounds of the present invention include, but are not limited to: benzothiadiazole, thiazilamide (TDL), isotianil, 4-methyl-1, 2,3-thiadiazole-5-carboxylic acid, 4-methyl-1,2,3-thiadiazole-5-sodium formate, 4-methyl-1,2,3-thiadiazole-5-carboxylic acid ethyl Esters, DL-β-aminobutyric acid, ribavirin, antorfin, Ningnanmycin, thiamide, methiamine or salicylic acid, pyrimenpeptidemycin, dichloroisonicotinic acid, allyl isothiazole, Jinggang hydroxylamine, Jinggangmycin.

The plant virus diseases that the antiviral agent can control include but are not limited to: tobacco mosaic virus disease, various melon virus diseases, various solanaceous fruit virus diseases, bean virus diseases, cruciferous virus diseases, grain and oil crop viruses Any one of cotton virus disease, cotton virus disease and various fruit tree virus diseases; wherein, the serious damage is selected from but not limited to: tobacco virus disease, spicy sweet pepper virus disease, tomato virus disease, Chinese cabbage virus disease, rice virus disease Including rice dwarf disease, yellow dwarf disease, stripe leaf blight, tomato fern virus disease, pepper mosaic virus disease and tobacco vein necrosis virus disease, corn dwarf mosaic disease, cauliflower mosaic virus disease, citrus virus disease, Jianlan Leaf virus, Jianlan ringspot virus in any one. The compositions of the antiviral preparation all show additive or synergistic effects, and while maintaining the insecticidal activity, its antiviral activity is greater than the effect of any one compound used alone; no antagonistic composition is found, the combination Drug effect duration is long. Wherein, the determination method of the antiviral activity of the composition, especially the determination method of the anti-tobacco virus disease, can refer to the determination of the anti-tobacco virus disease of compounds IIIA and IIIB, and will not be repeated.

The crops suitable for the compound preparation include rice, wheat, barley, oats, corn, sorghum, sweet potato, potato, cassava, soybean, snow pea, broad bean, pea, mung bean, adzuki bean, cotton, silkworm, peanut, rapeseed, sesame, sunflower, Beet, sugar cane, coffee, cocoa, ginseng, fritillary, rubber, coconut, oil palm, sisal, tobacco, tomato, pepper, radish, cucumber, cabbage, celery, mustard, beet, rapeseed, onion, garlic, watermelon, melon , cantaloupe, papaya, fruit, tea, wild vegetables, bamboo shoots, hops, potatoes, rice, pepper, apples, bananas, citrus, peach trees, papaya, orchids, bonsai and other agricultural, horticultural, economic and forestry plants. The use of the compound preparation improves the immunity of the crop itself, and induces plants to prevent and control plant virus diseases while producing pests, especially virus-transmitting insects; it can also produce direct control effects on virus diseases; therefore These compound preparations can be used for the preparation and application of anti-plant virus agents and anti-plant virus agents for inducing plants.

The dosage forms that can be processed by the compound preparation are selected from but not limited to: wettable powder, sustained release agent, powder, microcapsule suspension, dispersible liquid preparation, dispersible solid preparation, seed treatment emulsion, emulsion in water, macrogranule, granule Agents, microemulsions, oil suspensions, oils, seeds coated with pesticides, suspoemulsions, water-soluble granules, soluble concentrates, water-dispersible granules, poisonous grains, aerosols, block poisonous baits, sustained release Block, concentrated poison bait, capsule granule, capsule suspension, dispersible concentrate, powder, dry seed dressing powder, emulsifiable concentrate, electrostatic spray, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke tank, fine grain agent, smoke candle, smoke tube, smoke stick, seed treatment suspension, smoke sheet, aerosol, smoke pill, granular poison bait, gas-generating agent, large particle, drifting powder, granule, ointment, thermal spray, solid/ Liquid mixed agent, liquid/liquid mixed agent, cold mist agent, solid/solid mixed agent, medicinal paint, seed treatment liquid agent, microgranule, oil suspension, oil agent, oil dispersible powder, ointment, tablet Poison baits, glue concentrates, pouring agents, sticks, seed coatings, poison baits, smears, small pieces of poison baits, suspensions, suspoemulsions, water-soluble granules, soluble concentrates, film-forming oils, soluble powders, seeds Handle any one of water-soluble powder, ultra-low volume suspension concentrate, tablet, tracking powder, ultra-low volume liquid, steam release agent, water-dispersible granule, wettable powder, and wet seed dressing water-dispersible powder.

7. Processing technology and stability analysis of compound preparations of thiazole heterocyclic compounds represented by general formulas IIIA and IIIB and existing insecticides, fungicides and antiviral agents

Table 4 shows the processing methods of compound preparations of thiazole heterocyclic compounds represented by general formulas IIIA and IIIB and existing insecticides, bactericides and antiviral agents.

Table 4 The present invention comprises the processing method of the compound preparation of the thiazole heterocyclic compound represented by general formula IIIA and IIIB

Among them, commodity pesticides include existing insecticides, fungicides and antiviral agents.

As can be seen from Table 4, the compound preparation comprising the thiazole heterocyclic compound represented by general formula IIIA and IIIB can be processed according to the method described in Table 4, and the main components of the liquid preparation are active ingredients, cosolvents and surfactants, Other components such as synergists, antifreeze agents, stabilizers, thickeners or penetrating agents, etc. The composition of the solid preparation mainly includes active ingredients, surfactants, fillers and other agriculturally acceptable auxiliary components. Wherein, cosolvents, surfactants, antifreeze agents, synergists, other agriculturally acceptable additives such as stabilizers, thickeners or penetrants, etc., all belong to the prior art, and are no longer listed one by one. The purpose is to In order to show that the general formula IIIA of the present invention, the IIIB compound can be used with commercial pesticides and cosolvents in the prior art, surfactants, antifreeze agents, synergists, other agriculturally acceptable auxiliary agents such as stabilizers, thickeners Agents or penetrants, etc., are compounded according to the weight percentage content in Table 4 to make compound preparations, so as to be better used in the prevention and treatment of plant pathogenic fungus diseases and/or plant pests and / or plant virus disease, but not limited to the composition of the compound preparation containing thiazole heterocyclic compounds represented by general formulas IIIA and IIIB. Anyone who can be compounded with an effective amount of thiazole heterocyclic compounds represented by general formulas IIIA and IIIB is used to prevent and control plant fungal diseases and/or plant pests and/or plant virus diseases in the fields of agriculture, forestry, horticulture and hygiene, are within the protection scope of this patent.

In addition, a cold storage test was carried out on the compound preparation obtained above. The cold storage test of the compound preparation showed that the liquid preparation was placed at 0 ± 2 degrees Celsius for 1 week without precipitation, and the solid preparation was placed at 54 ± 2 degrees Celsius for 2 weeks. Agglomeration phenomenon; there is no significant difference in the drug efficacy of all preparations before and after storage, the decomposition rate of the active ingredients of the mixed preparation is within 5%, and the stability of the mixed preparation is qualified.

In summary, the claims and technical support of a class of novel thiazole heterocyclic compounds and their preparation methods and applications described in the present invention have been clarified, and any modifications and changes made based on the essence of the technical support of the present invention are still It belongs to the scope of technical support of the present invention.

Claims (10)

1. acceptable salt in a kind of thiazole heterocyclic compounds represented by below formula III or its Pesticide Science,

Wherein：

X is selected from hydrogen, fluorine, chlorine, bromine, methyl, methoxyl group, cyano group, isopropoxy and nitro；

R is selected from hydrogen and methyl.

2. acceptable salt in the Pesticide Science of general formula III compound according to claim 1, it is characterised in that：Including general formula III Compound with for hydrochloric acid, hydrobromic acid, sulfuric acid or phosphoric acid inorganic acid or be citric acid, lactic acid, malic acid, gluconic acid, wine The organic acid of stone acid, adipic acid, acetic acid, butanedioic acid, fumaric acid, ascorbic acid or itaconic acid or be methanesulfonic acid or benzene sulfonic acid Organic sulfonic acid formed salt.

3. a kind of method for preparing the compound that general formula III as claimed in claim 1 is represented, it is characterised in that including following step Suddenly：

Wherein：

X is selected from hydrogen, fluorine, chlorine, bromine, methyl, methoxyl group, cyano group, isopropoxy and nitro；

R is selected from hydrogen and methyl；

The preparation of A, Compounds of formula II：

In reaction vessel, 70 mMs of 80 milliliters of toluene, 100 mMs of chemical compounds I and lawesson reagent are sequentially added, stirred back Reaction solution concentration is removed toluene by stream 3-6 hours, reaction after terminating, and residue is obtained through the purifying of 200-300 mesh silica gel column chromatography Faint yellow solid, as compound II, the eluant, eluent for being used for 60-90 degrees Celsius of petroleum ether and ethyl acetate, the stone Oily ether：The volume ratio of ethyl acetate is 5：1-3：1；

The preparation of B, general formula III A compounds：

In reaction vessel, the 30 milliliters of stirrings of 10 mMs of compound ii and absolute ethyl alcohol are added, add 3- bromo- 1,1,1- tri- 10 mMs of fluorine acetone, stirred under nitrogen atmosphere is flowed back 16 hours, and reaction solution concentration is removed ethanol, residue by reaction after terminating Through 200-300 mesh silica gel column chromatography purifying obtain white or faint yellow solid, as compound IIIA, the eluant, eluent for being used for 60-90 degrees Celsius of petroleum ether and ethyl acetate, the petroleum ether：The volume ratio of ethyl acetate is 20：1-10：1；

The preparation of C, general formula III B compounds：

In reaction vessel, the 15 milliliters of stirrings of IIIA2.0 mMs of compound and anhydrous DMF, nitrogen are added - 5 degrees Celsius are cooled under protection, 3.0 mMs of sodium hydride is added, are kept for -5 degrees Celsius and stirred 15 minutes, iodomethane is added dropwise 3.0 mMs, room temperature is gradually increased to after dripping and is stirred 16 hours；After reaction terminates, reaction solution is poured into frozen water, acetic acid Ethyl ester is extracted, and merges organic phase, and organic phase is concentrated under reduced pressure after saturated common salt water washing and anhydrous sodium sulfate drying and removes solvent, Residue obtains white or faint yellow solid, as compound IIIB through the purifying of 200-300 mesh silica gel column chromatography, and what is used washes De- agent is 60-90 degrees Celsius of petroleum ether and ethyl acetate, the petroleum ether：The volume ratio of ethyl acetate is 20：1-10：1.

4. acceptable salt is in preventing and treating agricultural, woods on general formula III as claimed in claim 1 or 2 is represented compound or its Pesticide Science The application in terms of phytopathogen disease and/or viral diseases of plants in industry, gardening and health field.

5. a kind of antibiotic preparation, it is characterised in that：The compound of the general formula III as claimed in claim 1 or 2 comprising effective dose or Acceptable salt in its Pesticide Science.

6. antibiotic preparation according to claim 5, it is characterised in that：Being can in the general formula III compound or its Pesticide Science One or two of the salt of receiving and existing antiseptic are with mass percent 1%：99%-99%：The complex preparation of 1% combination.

7. antibiotic preparation according to claim 5, it is characterised in that：Can be connect in the general formula III compound or its Pesticide Science Weight/mass percentage composition of the salt received in the antibiotic preparation is 1%-90%.

8. a kind of antivirotic, it is characterised in that：The compound of the general formula III as claimed in claim 1 or 2 comprising effective dose or Acceptable salt in its Pesticide Science.

9. antivirotic according to claim 8, it is characterised in that：For can in the general formula III compound or its Pesticide Science One or two in the salt of receiving and existing antivirotic are with mass percent 1%：99%-99%：The complex preparation of 1% combination.

10. antivirotic according to claim 8, it is characterised in that：Can in the general formula III compound or its Pesticide Science Weight/mass percentage composition of the salt of receiving in the antivirotic is 1%-90%.