Diene thiazole derivatives, their synthesis methods and applications

Abstract

The present invention relates to the technical field of pharmaceutical synthesis, and specifically relates to diene thiazole derivatives and their synthesis methods and applications. The diene thiazole derivatives disclosed in the present invention are a series of brand-new compounds, which are proposed for the first time. The diene thiazole derivatives have the chemical structure shown in general formula (1). The synthesis method of the diene thiazole derivatives of the present invention uses 16-DPA as the basic raw material and obtains the diene thiazole derivatives of the present invention through a series of different reactions. The synthesis method has a high preparation yield, and the obtained product is easy to separate. It has been confirmed by biological assays that the diene thiazole derivatives exhibit good insecticidal activity against pests such as aphids, oriental armyworms, diamondback moths, and whiteflies, and can be used to prepare single-agent agricultural insecticides or mixed preparations containing the diene thiazole derivatives. #imgabs0#

Description

Technical Field

[0001] The present invention relates to the technical field of drug synthesis, and particularly relates to diene thiazole derivatives, their synthesis methods and applications. Background Art

[0002] Heterocyclic compounds are a class of compounds mainly composed of five-membered, six-membered ring systems or fused ring systems containing one or more heteroatoms (O, N or S). Since Anderson isolated pyrrole from bone tar in 1857, Scheele prepared furan in 1870, and Meyer discovered thiophene in 1882, it has been only over a century, and the number of heterocyclic compounds studied has developed to an astonishing figure. In the 1930s of this century, the number of heterocyclic compounds recorded in the Beilstein Handbook of Organic Chemistry accounted for about 1 / 3 of the then-known hundreds of thousands of organic compounds. Among these compounds, heterocyclic compounds containing nitrogen atoms are particularly important.

[0003] The thiazole heterocycle is an important five-membered aromatic heterocycle containing nitrogen and sulfur heteroatoms, with rich electrons, easy to form hydrogen bonds, coordinate with metal ions, and various non-covalent bond interactions such as Π-Π stacking, electrostatic and hydrophobic interactions. This structure endows thiazole compounds with many special properties. Especially with a series of thiazole compounds successfully used in clinical and agricultural production, the research and development of thiazole compounds has become one of the hot research fields in recent years and has extensive potential applications in many fields.

[0004] Piercing-sucking mouthpart pests are a relatively large group among garden plant pests. They are small in size, and the damage symptoms are often not obvious in the initial stage of occurrence, so they are easily ignored by people. However, they are extremely numerous and often inhabit tender branches, leaves, buds, flower buds, and fruits in groups, sucking the plant sap and robbing its nutrients, causing the branches, leaves and flowers to curl, and even the whole plant to wither or die. At the same time, it induces sooty mold, and sometimes the pests themselves are the vectors of virus diseases. These pests can damage most crops, causing serious losses to their yields and qualities. However, most of the currently effective control agents have developed serious resistance to piercing-sucking mouthpart pests after long-term use. Chewing mouthpart pests damage plants by causing various forms of mechanical damage. For example, feeding on leaves causes notches and holes. When it is serious, the mesophyll is eaten up, only the reticulate veins are left, and even all are eaten up. Therefore, it is urgent to screen out new control agents. Summary of the Invention

[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and provide diene thiazole derivatives, their synthesis methods and applications.

[0006] The purpose of the present invention is achieved by the following technical solutions: Diene thiazole derivatives have the chemical structure shown in general formula (1):

[0007]

[0008] Among them, R is any one of an alkyl group, a phenyl group or a substituted phenyl group, and the alkyl group is an aliphatic chain or a cycloalkane.

[0009] Furthermore, the alkyl group is (a) or (b):

[0010]

[0011] Furthermore, the phenyl group or the substituted phenyl group is any one of (c) to (i):

[0012]

[0013] Furthermore, the diene thiazole derivative has the following chemical structural formula:

[0014]

[0015] Synthesis method of the diene thiazole derivative, and the synthesis route is:

[0016]

[0017] Among them, the reaction conditions for step a are: 4-dimethylaminopyridine, triethylamine and acyl chlorides with various substituents are respectively added to dichloromethane dissolved with compound (2), and the reaction is carried out at room temperature for 5 to 7 h, preferably 6 h;

[0018] The reaction conditions for step b are: using tetrahydrofuran as the solvent, adding tetrabutylammonium fluoride trihydrate, and refluxing for 3 to 5 h, preferably 4 h.

[0019] Furthermore, the synthesis route of compound (2) is:

[0020]

[0021] Among them, the reaction conditions for step c are: adding bromoketone to the tetrahydrofuran solution of compound (4), and reacting at 63 to 68 °C for 6 to 10 h, preferably reacting at 65 °C for 8 h;

[0022] The reaction conditions for step d are: using ethanol as the solvent, adding thiourea, and reacting at 63 to 68 °C for 6 to 10 h, preferably reacting at 65 °C for 8 h;

[0023] The reaction conditions for step e are: using methanol as the solvent, adding Na2CO3, and reacting at 75 to 85 °C for 3 to 5 h, preferably reacting at 80 °C for 4 h;

[0024] The reaction conditions of step f are as follows: Compound (7) is dissolved in N,N-dimethylformamide, imidazole and tert-butyldimethylchlorosilane are added, and the reaction is carried out at room temperature for 10-14 h, preferably 12 h.

[0025] The above-mentioned dithiazole derivatives, the application of the dithiazole derivatives prepared by the above method in the control of plant pests.

[0026] Further, the plant pests are piercing-sucking and chewing mouthpart pests.

[0027] Further, the piercing-sucking and chewing mouthpart pests are aphids, oriental armyworms, diamondback moths and whiteflies.

[0028] An insecticide contains the above-mentioned dithiazole derivatives, the dithiazole derivatives prepared by the above method.

[0029] Further, the effective mass percentage content of the dithiazole derivatives is 0.01%-99.99%.

[0030] In order to apply the dithiazole derivatives in the fields of agriculture and plant protection, those skilled in the art can use one or several of the dithiazole derivatives as insecticidal active ingredients and combine them with a pesticidally acceptable carrier or other agricultural active ingredients to prepare a formulation convenient for application, such as water dispersible granules, wettable powders or dispersible oil suspensions and other dosage forms. When formulating the above different dosage forms, for those skilled in the art, in addition to using the selected bactericidal active ingredients, various auxiliaries also need to be selected, and different pesticide formulation auxiliary components (auxiliaries) can be selected according to needs. The auxiliary components can be one or several of a dispersion medium, a dispersant, an emulsifier, a wetting agent, a thickening agent, an antifoaming agent, an antifreezing agent, a disintegrant, a binder, a filler, etc. The present invention does not describe the preparation method of the single agent or composition preparation containing the dithiazole derivatives.

[0031] The present invention has the following advantages:

[0032] (1) The dithiazole derivatives disclosed in the present invention are a series of brand-new compounds, and the present invention is proposed for the first time. In addition, the present invention also provides a synthesis method of the dithiazole derivatives. Using 16-DPA as the basic raw material, the dithiazole derivatives of the present invention are obtained through a series of different reactions. The synthesis method has a high preparation yield, and the obtained product is easy to separate.

[0033] (2) It is confirmed by bioassay that the dithiazole derivatives show good insecticidal activity against pests such as aphids, oriental armyworms, diamondback moths and whiteflies, and can be used to prepare single agents for agricultural insecticides or mixed preparations containing the dithiazole derivatives. Brief Description of the Drawings

[0034] Figure 1 It is the single crystal diffraction pattern of the target compound (1)-9. Detailed Description of the Invention

[0035] The present invention will be further described below in conjunction with the drawings and embodiments. The protection scope of the present invention is not limited to the following:

[0036] Diene thiazole derivatives have the chemical structure described by the general formula (1):

[0037]

[0038] Among them, R is any one of alkyl, phenyl or substituted phenyl, and the alkyl is a fatty chain or a cycloalkane.

[0039] Synthesis method of diene thiazole derivatives, the synthesis route is:

[0040]

[0041] Among them, the synthesis route of compound (2) is:

[0042]

[0043] The reaction conditions for each step are:

[0044] Step a: R(C=O)Cl, Et3N, DMAP, rt;

[0045] Step b: TBAF, DMF, rt;

[0046] Step c: CuBr2, THF, reflux;

[0047] Step d: thiourea, EtOH, reflux;

[0048] Step e: Na2CO3, MeOH, 80 °C;

[0049] Step f: DMF, TBSCl, imidazole, rt.

[0050] The specific operation is as follows:

[0051] Synthesis and preparation of diene thiazole derivatives

[0052] (1) React pregnenolone acetate with ketone bromide to generate compound (5); then add thiourea with ethanol as the solvent to obtain compound (6), and then react with Na2CO3 using methanol as the solvent to remove the acetyl protection; finally, dissolve compound (7) in N,N-dimethylformamide and react with imidazole and tert-butyldimethylchlorosilane to obtain compound (2).

[0053] (2) Using compound (2) as the reaction raw material, with dichloromethane as the solvent, add 4-dimethylaminopyridine, triethylamine and acyl chloride containing various substituents to react to obtain compound (3), and then use tetrahydrofuran as the solvent and add tetrabutylammonium fluoride trihydrate to obtain compound (1).

[0054] Example 1: The synthesis steps of dithiazole derivatives are as follows:

[0055] Dissolve 3.57 g of pregnenolone acetate (10 mmol) in tetrahydrofuran (60 mL), add 4.50 g of CuBr2 (20 mmol), and react at 65 °C for 12 h. Concentrate under reduced pressure, extract with saturated NaCl aqueous solution and dichloromethane, dry the organic phase with anhydrous sodium sulfate, and concentrate under reduced pressure to obtain 4.00 g of white solid compound (5); then dissolve 3.48 g of compound (5) (8 mmol) in 70 mL of ethanol, and then add 0.92 g of thiourea (12 mmol) 2, and react at 80 °C for 8 h. Concentrate under reduced pressure, filter with dichloromethane to obtain a brownish-yellow liquid, dry with anhydrous sodium sulfate, and concentrate under reduced pressure to obtain 3.22 g of yellow solid compound (6); dissolve 2.06 g of compound (6) (5 mmol) in methanol (40 mL), and then add 0.80 g of sodium carbonate (7.5 mmol), and react at 70 °C for 5 h. Concentrate under reduced pressure, filter with ice water to obtain 1.78 g of light yellow solid compound (7); add 1.48 g of compound (7) (4 mmol) to the reaction flask, dissolve it in DCM (50 mL), add 603 mg of TBSCl (2.4 mmol) and 816 mg of imidazole (12 mmol). React at 0 °C for 8 h. After TLC detection shows the reaction is complete, add DCM and H2O for extraction, dry with anhydrous Na2SO4, and concentrate under reduced pressure to obtain 1.85 g of yellow solid compound (2).

[0056] Dissolve 121.2 mg of compound (2) (0.25 mmol) in dichloromethane, add 30 mg of DMAP (0.25 mmol), 150 mg of Et3N (1.5 mmol) and an acyl chloride with different substituents (1.0 mmol), react at room temperature for 4 h, then extract with water and dichloromethane. The organic phase is dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain compound (3); dissolve compound (3) (0.20 mmol) in anhydrous THF (5 mL), add 0.16 g of tetrabutylammonium fluoride trihydrate (0.6 mmol), stir at room temperature for 2 h, extract with diethyl ether and ethyl acetate, and concentrate under reduced pressure to obtain compound (1).

[0057] The dithiazole derivatives prepared by the above method are confirmed by 1 1H-NMR,[[]] 13 13C-NMR, and the structures of compounds (1)-9 are confirmed by single crystal diffraction method, as Figure 1 shown, and the specific results are as follows:

[0058] 1. Compound (1)-1

[0059]

[0060] 1 1H NMR (500 MHz, CDCl3) δ = 6.77 (s, 1H), 6.27 (s, 1H), 5.38 (s, 1H), 3.63–3.36 (m, 1H), 2.77–2.66 (m, 1H), 2.33 (dd, J = 13.1, 1.9 Hz, 1H), 2.26 (td, J = 6.7, 3.9 Hz, 3H), 2.24–2.21 (m, 1H), 2.10–1.97 (m, 2H), 1.86 (s, 3H), 1.85 (s, 1H), 1.80 (dd, J = 7.9, 6.0 Hz, 2H), 1.76 (d, J = 7.0 Hz, 2H), 1.75–1.68 (m, 3H), 1.68–1.54 (m, 6H), 1.55 (s, 2H), 1.52 (d, J = 8.0 Hz, 2H), 1.25 (d, J = 2.1 Hz, 1H), 1.07 (s, 4H), 1.04 (s, 3H).

[0061] 1313C NMR (125 MHz, CDCl3) δ = 174.30, 157.83, 148.56, 145.82, 141.15, 128.93, 121.39, 107.22, 71.74, 57.44, 50.52, 46.39, 45.43, 42.35, 37.20, 36.72, 35.67, 31.67, 31.58, 31.41, 30.33, 30.13, 26.04, 21.02, 19.36, 16.18.

[0062] 2. Compound (1)-2

[0063]

[0064] 1 1H NMR (500 MHz, CDCl3) δ = 10.63 (s, 1H), 6.77 (s, 1H), 6.28 (s, 1H), 5.38 (d, J = 5.0 Hz, 1H), 3.54 (tt, J = 10.9, 4.5 Hz, 1H), 2.68 (d, J = 8.0 Hz, 1H), 2.30 (s, 1H), 2.27 (d, J = 12.5 Hz, 1H), 2.23 (s, 1H), 2.23–2.19 (m, 1H), 2.07 (d, J = 5.4 Hz, 1H), 2.06–1.97 (m, 2H), 1.87 (s, 2H), 1.84 (s, 2H), 1.76 (s, 1H), 1.67 (d, J = 6.5 Hz, 3H), 1.57–1.49 (m, 4H), 1.07 (s, 3H), 1.03 (s, 3H).

[0065] 13 13C NMR (125 MHz, CDCl3) δ = 174.72, 158.42, 148.56, 145.70, 141.24, 129.11, 121.46, 107.27, 71.80, 57.58, 50.59, 46.43, 45.39, 42.40, 37.27, 36.80, 35.76, 31.72, 31.68, 31.51, 30.55, 30.38, 30.20, 26.17, 21.10, 19.46, 16.26.

[0066] 3. Compound (1)-3

[0067]

[0068] 11H NMR (500 MHz, CDCl3) δ = 8.08 (dd, J = 7.4, 2.0 Hz, 1H), 7.80 (dd, J = 7.4, 2.1 Hz, 1H), 7.70 (td, J = 7.5, 2.0 Hz, 1H), 7.62 (td, J = 7.5, 2.0 Hz, 1H), 7.32 (s, 1H), δ 7.26 (s, 1H), 5.65 (s, 1H), 5.39 (s, 1H), 3.97 (d, J = 5.1 Hz, 1H), 3.55 (d, J = 5.1 Hz, 1H), 2.30 (d, J = 15.7 Hz, 1H), 2.17 (dt, J = 13.0, 1.0 Hz, 1H), 2.10 (s, 1H), 2.05–1.98 (m, 1H), 1.92 (d, J = 13.0 Hz, 1H), 1.82–1.73 (m, 3H), 1.69 (s, 1H), 1.64–1.58 (m, 2H), 1.45–1.36 (m, 1H), 1.39–1.33 (m, 1H), 1.27 (s, 2H), 1.15 (s, 2H).

[0069] 13 13C NMR (125 MHz, CDCl3) δ = 169.31, 167.49, 147.56, 145.24, 143.97, 139.23, 134.97, 133.17, 133.11, 133.06, 128.19, 127.17, 125.60, 125.06, δ 71.74, 57.27, 56.32, 50.46, 46.42, 42.35, 37.21, 36.72, 35.62, 31.67, 31.56, 31.41, 30.35, 21.05, 19.38.

[0070] Compound (1)-4

[0071]

[0072] 1¹H NMR (500 MHz, MeOD) δ = 7.58 (d, J = 7.6 Hz, 1H), 7.54–7.46 (m, 2H), 7.42 (td, J = 7.3, 2.1 Hz, 1H), 6.99 (s, 1H), 6.26 (s, 1H), 5.37 (d, J = 5.0 Hz, 1H), 3.41 (tt, J = 10.6, 4.9 Hz, 1H), 2.34 (dt, J = 12.2, 3.6 Hz, 1H), 2.27 (d, J = 8.4 Hz, 1H), 2.24 (d, J = 5.6 Hz, 1H), 2.23–2.17 (m, 1H), 2.04 (d, J = 17.5 Hz, 2H), 2.01 (s, 1H), 2.00 (d, J = 5.9 Hz, 2H), 1.90–1.76 (m, 2H), 1.77 (s, 1H), 1.70 (d, J = 12.7 Hz, 2H), 1.70–1.64 (m, 2H), 1.54 (s, 1H), 1.51 (d, J = 5.9 Hz, 1H), 1.47 (s, 2H), 1.24 (t, J = 7.1 Hz, 1H), 1.08 (s, 3H), 1.04 (s, 3H).

[0073] 13 ¹³C NMR (125 MHz, MeOD) δ = 167.07, 158.32, 150.01, 147.98, 142.56, 135.63, 133.10, 132.45, 131.31, 130.42, 129.59, 128.26, 122.27, 108.80, 79.46, 58.68, 47.53, 43.05, 38.46, 37.86, 36.72, 32.67, 32.28, 32.23, 31.66, 22.13, 19.84, 16.58.

[0074] Compound (1)-5

[0075]

[0076] 1¹H NMR (500 MHz, MeOD) δ = 8.14 (d, J = 1.9 Hz, 1H), 7.94 (d, J = 7.7 Hz, 1H), 7.90 (d, J = 2.0 Hz, 1H), 7.74 (d, J = 30.6 Hz, 2H), 6.88 (s, 1H), 5.34 (d, J = 5.0 Hz, 1H), 3.41 (dq, J = 10.5, 5.5 Hz, 1H), 2.27 (q, J = 4.0, 2.8 Hz, 2H), 2.23 (s, 2H), 2.21 (dd, J = 6.2, 3.1 Hz, 1H), 2.17 (d, J = 6.2 Hz, 1H), 2.01 (s, 2H), 1.97–1.88 (m, 1H), 1.81 (ddd, J = 20.8, 11.3, 3.6 Hz, 3H), 1.66 (q, J = 6.1, 5.1 Hz, 2H), 1.51 (d, J = 6.2 Hz, 1H), 1.47 (d, J = 6.4 Hz, 1H), 1.45 (d, J = 6.1 Hz, 2H), 1.23 (t, J = 7.2 Hz, 1H), 1.05 (s, 3H), 1.01 (s, 3H).

[0077] 13 ¹³C NMR (125 MHz, MeOD) δ = 170.58, 165.86, 147.05, 142.24, 136.85, 136.62, 136.34, 135.70, 132.96, 131.31, 128.42, 127.46, 123.58, 72.10, 51.67, 48.49, 47.53, 47.29, 42.78, 38.19, 37.62, 36.48, 35.68, 32.43, 32.03, 31.34, 19.80, 16.60.

[0078] Compound (1)-6

[0079]

[0080] 11H NMR (500 MHz, CDCl3) δ = 7.68 (d, J = 7.0 Hz, 1H), 7.57 (d, J = 8.0 Hz, 1H), 7.52 (t, J = 5.8 Hz, 2H), 7.05 (s, 1H), 6.06 (s, 1H), 5.36 (d, J = 5.3 Hz, 1H), 3.53 (d, J = 12.5 Hz, 1H), 2.30 (q, J = 6.3, 5.6 Hz, 1H), 2.25 (d, J = 11.1 Hz, 1H), 2.19–2.12 (m, 1H), 2.04 (s, 1H), 1.96 (d, J = 13.8 Hz, 2H), 1.92 (s, 1H), 1.84 (d, J = 10.1 Hz, 2H), 1.71 (s, 1H), 1.63 (d, J = 17.4 Hz, 2H), 1.52–1.45 (m, 1H), 1.44 (s, 1H), 1.39–1.21 (m, 2H), 1.05 (s, 3H), 0.86 (s, 3H).

[0081] 13 13C NMR (125 MHz, CDCl3) δ = 168.24, 165.56, 149.83, 147.96, 141.24, 133.63, 132.03, 131.63, 131.13, 130.59, 129.82, 129.40, 127.82, 127.75, 121.47, 71.83, 57.12, 50.52, 46.59, 46.27, 42.38, 37.27, 36.79, 35.59, 35.06, 31.70, 31.61, 31.58, 30.38.

[0082] Compound (1)-7

[0083]

[0084] 11H NMR (500 MHz, CDCl3) δ = 7.75 (d, J = 5.1 Hz, 2H), 7.22–7.14 (m, 2H), 6.77 (s, 1H), 6.04 (s, 1H), 5.36 (s, 1H), 3.56 (td, J = 11.3, 6.5 Hz, 1H), 3.85 (s, 2H), 2.33 (d, J = 19.1 Hz, 1H), 2.28 (s, 1H), 2.25 (d, J = 12.6 Hz, 1H), 2.17 (d, J = 11.4 Hz, 1H), 2.01 (d, J = 28.5 Hz, 2H), 1.96–1.92 (m, 1H), 1.86 (d, J = 12.5 Hz, 3H), 1.70–1.65 (m, 1H), 1.61 (s, 1H), 1.55 (d, J = 13.2 Hz, 1H), 1.51 (s, 1H), 1.38 (t, J = 12.4 Hz, 1H), 1.29–1.20 (m, 1H), 1.08 (s, 1H), 1.05 (s, 3H), 0.98–0.94 (m, 3H).

[0085] 13 13C NMR (126 MHz, CDCl3) δ = 165.49, 158.72, 147.89, 146.02, 143.37, 141.10, 129.65, 129.53, 129.04, 127.82, 121.42, 107.10, 71.73, 56.75, 55.93, 50.63, 46.05, 42.33, 37.29, 36.69, 35.32, 31.64, 31.50, 31.24, 30.15, 21.73, 20.99, 19.35.

[0086] Compound (1)-8

[0087]

[0088] 11H NMR (500 MHz, CDCl3) δ = 7.84 (dd, J = 7.5, 2.0 Hz, 1H), 7.62 (t, J = 7.5 Hz, 1H), 7.39 (s, 1H), 7.20 (dd, J = 7.5, 2.0 Hz, 1H), 5.72 (s, 1H), 5.46 (s, 1H), 4.05 (d, J = 5.1 Hz, 1H), 3.56 (d, J = 4.9 Hz, 1H), 2.41–2.34 (m, 2H), 2.25 (t, J = 1.0 Hz, 1H), 2.17 (s, 1H), 2.09 (dt, J = 18.1, 1.0 Hz, 1H), 1.99 (d, J = 13.0 Hz, 1H), 1.89–1.80 (m, 3H), 1.77 (s, 1H), 1.72–1.65 (m, 2H), 1.52–1.44 (m, 2H), 1.08 (s, 3H), 1.04 (s, 3H).

[0089] 13 13C NMR (125 MHz, CDCl3) δ = 168.24, 165.56, 147.96, 147.40, 141.24, 141.20, 133.63, 131.63, 130.59, 127.82, 124.63, 121.47, 114.54, 71.83, 57.12, 50.52, 42.38, 37.27, 36.79, 31.70, 31.58, 30.38, 19.42, 15.92.

[0090] Compound (1)-9

[0091]

[0092] 11H NMR (500 MHz, CDCl3) δ = 7.47 (t, J = 5.6 Hz, 1H), 7.34 (s, 1H), 7.32–7.29 (m, 2H), 7.03 (dd, J = 8.2, 2.7 Hz, 1H), 5.99 (t, J = 2.6 Hz, 1H), 5.34 (s, 1H), 3.74 (s, 3H), 2.35–2.26 (m, 2H), 2.24 (d, J = 11.2 Hz, 1H), 2.22–2.15 (m, 1H), 2.16–2.08 (m, 1H), 2.08–1.94 (m, 2H), 1.94 (s, 1H), 1.84 (dt, J = 23.1, 13.0 Hz, 3H), 1.76–1.69 (m, 1H), 1.69–1.59 (m, 2H), 1.48 (s, 1H), 1.41 (dt, J = 10.8, 4.9 Hz, 1H), 1.26 (d, J = 6.5 Hz, 1H), 1.19 (dt, J = 12.2, 6.0 Hz, 1H), 1.05 (s, 3H), 0.99 (s, 4H).

[0093] 13 13C NMR (125 MHz, CDCl3) δ = 170.45, 165.19, 159.80, 146.11, 141.19, 135.06, 129.91, 129.81, 129.11, 128.82, 121.62, 119.62, 113.85, 110.67, 71.74, 57.03, 55.46, 50.49, 46.55, 46.25, 42.36, 37.27, 37.24, 36.73, 35.43, 34.80, 30.33, 19.40, 19.36.

[0094] Example 2:

[0095] The mortality rates of the dithiazole derivatives listed in Table 1 against Schizaphis graminum, Brevicoryne brassicae Linn, Aphis gossypii, Aphis citricola van der Goot, and Myzus persicae were determined by the slide dipping method. Specific method: Weigh a certain amount of the compound to be tested accurately, dissolve the compound with acetone as the solvent, and prepare a solution with a concentration of 100 μg / mL using a 0.1% Tween-80 aqueous solution. Let it stand at room temperature for half an hour, and store it for use after the sample is completely dissolved. Paste the aphids to be tested onto a glass slide with double-sided tape, then dip the slide with aphids into the prepared liquid medicine for 5 s and take it out, and blot the residual liquid medicine with absorbent paper. The positive control is acetamiprid, and the negative control is a 0.1% Tween-80 aqueous solution. Observe the mortality rate after moisturizing in a petri dish for 48 h, and the results are shown in Table 1.

[0096] Table 1 Mortality rates of the dithiazole derivatives of formula (1) of the present invention against five species of aphids

[0097]

[0098] — in the table represents inactivity

[0099] The indoor bioassay results in Table 1 show that the test compounds have good biological activities against Schizaphis graminum, Brevicoryne brassicae Linn, Aphis gossypii, Aphis citricola van der Goot, and Myzus persicae, and some compounds have similar insecticidal effects to flonicamid.

[0100] Example 3:

[0101] The mortality rates of the dithiazole derivatives listed in Table 2 against Mythimna separata and Plutella xylostella were determined by the leaf dipping method. Specific method: Weigh a certain amount of the compound to be tested accurately, dissolve the compound with acetone as the solvent, and prepare solutions with concentrations of 1000 μg / mL and 200 μg / mL using a 0.1% Tween-80 aqueous solution. Let it stand at room temperature for half an hour, and store it for use after the sample is completely dissolved. Cut fresh wheat leaves into pieces of 0.5×0.5 cm, put each leaf into the prepared solution for 3 - 5 s and take it out, and wait for the solution to dry; put the 3rd instar larvae of Mythimna separata into a 24-well plate, and feed them with the dried wheat leaves respectively; the positive controls are abamectin (with concentrations of 10 μg / mL and 2 μg / mL respectively), and the negative control is a 0.1% Tween-80 aqueous solution. Observe the mortality rate after 72 h, and the results are shown in Table 2.

[0102] Table 2 Mortality rates of the dithiazole derivatives of formula (1) of the present invention against Mythimna separata

[0103]

[0104] Note: The concentrations of chlorfenapyr were 50 μg / mL and 10 μg / mL respectively

[0105] Table 2 Indoor bioassay results showed that the test compounds had good bioactivity against Mythimna separata, and some compounds had similar insecticidal effects to abamectin

[0106] Example 4:

[0107] The toxicity of the dithiazole derivatives listed in Table 3 against Plutella xylostella was determined by the leaf-dipping method. The positive control was chlorfenapyr (concentrations were 1000 μg / mL and 200 μg / mL respectively), and the negative control was acetone. Observe the number of deaths after 72 h and calculate the corrected mortality rate. The results are shown in Table 3

[0108] Table 3 Mortality rates of the dithiazole derivatives of formula (1) of the present invention against Plutella xylostella

[0109]

[0110] Note: The concentrations of chlorfenapyr were 50 μg / mL and 10 μg / mL respectively

[0111] Table 3 Indoor bioassay results showed that the test compounds had good bioactivity against Plutella xylostella, and some compounds had similar insecticidal effects to chlorfenapyr

[0112] Example 5:

[0113] The toxicity of the dithiazole derivatives listed in Table 4 against whiteflies was determined by the foliar spraying method. Specific method: Accurately weigh a certain amount of the test compound, dissolve it with acetone, and prepare solutions with concentrations of 100 and 50 μg / mL with 0.1% Tween 80 aqueous solution for standby. Spray the liquid medicine on the back of cucumber leaves, and after it dries naturally, put the test whiteflies on the plant leaves. The positive control was thiamethoxam, and the negative control was acetone. Observe the number of deaths after 7 d and calculate the corrected mortality rate. The results are shown in Table 4

[0114] Table 4 Mortality rates of the dithiazole derivatives of formula (1) of the present invention against whiteflies

[0115]

[0116] Table 4 Indoor bioassay results showed that the test compounds had good bioactivity against whiteflies, and some compounds had similar insecticidal effects to thiamethoxam

[0117] The above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, making equivalent substitutions or changes, shall be covered by the protection scope of the present invention.

Claims

1. Diene thiazole derivatives, characterized in that, Having the chemical structure described by the general formula (1): Wherein, R is any one of alkyl, phenyl or substituted phenyl, and the alkyl is (a) or (b): The phenyl or substituted phenyl is any one of (c) to (i):

2. The dithiazole derivative according to claim 1, characterized in that, The dithienothiazole derivative has the following chemical structural formula:

3. The synthesis method of the dithiazole derivative according to claim 1, characterized in that, The synthetic route is as follows: Wherein, the reaction conditions of step a are: 4-dimethylaminopyridine, triethylamine and acyl chloride containing various substituents are respectively added to dichloromethane dissolving compound (2), and the reaction is carried out at room temperature for 5-7 h; The reaction conditions of step b are: using tetrahydrofuran as the solvent, adding tetrabutylammonium fluoride trihydrate, and refluxing for 3-5 h.

4. The synthesis method of the dithienothiazole derivative according to claim 3, characterized in that The synthetic route of compound (2) is as follows: Wherein, the reaction conditions of step c are: adding bromoketone to the tetrahydrofuran solution of compound (4), and reacting at 63-68 °C for 6-10 h; The reaction conditions of step d are: using ethanol as the solvent, adding thiourea, and reacting at 63-68 °C for 6-10 h; The reaction conditions of step e are: using methanol as the solvent, adding Na2CO3, and reacting at 75-85 °C for 3-5 h; The reaction conditions of step f are: dissolving compound (7) in N,N-dimethylformamide, adding imidazole and tert-butyldimethylchlorosilane, and reacting at room temperature for 10-14 h.

5. Use of the dithienothiazole derivative according to claim 1 or 2, or the dithienothiazole derivative prepared by the method according to claim 3 or 4 in the control of plant pests.

6. The application according to claim 5, wherein The plant pests are aphids, oriental armyworms, diamondback moths and whiteflies.

7. An insecticide, characterized in that, Containing the dithienothiazole derivative according to claim 1 or 2, or the dithienothiazole derivative prepared by the method according to claim 5 or 6.

8. An insecticide according to claim 7, characterized in that, The effective mass percentage content of the dithienothiazole derivative is 0.01%-99.99%.

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