3-sulfur / selenium substituted phosphonimidate derivatives and methods of synthesis and use thereof

Abstract

The present application relates to the technical field of organic synthesis, in particular to a kind of 3-thio / seleno phosphorylated imidazole derivatives and synthesis method and application thereof, the structure general formula of the 3-thio / seleno phosphorylated imidazole derivative is, R 1 Be aryl or alkyl, X is sulfur element or selenium element, R 2 Be methyl or ethyl etc., R 3 Be ethyl or n-butyl etc.;The synthesis method is to use isothiocyanic acid ester or isoselenocyanate, isocyanate and phosphite as reaction raw material, synthesis by electrochemical oxidation reaction.The synthesis method provided by the present application adopts in the integrated cell without metal and chemical oxidant, constructs 3-thio / seleno phosphorylated imidazole derivative by one-pot three-component cross coupling cyclization, has the advantages of simple operation, raw material is cheap and easy to obtain, high synthesis efficiency, high atom economy, is conducive to large-scale preparation and production;3-thio / seleno phosphorylated imidazole derivative disclosed by the present application has excellent locust control activity and protective effect on wheat seedlings, and does not affect aquatic environment at low concentration, and has good biocompatibility, and can be used for preparing biological pesticide.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, specifically to a 3-thio / selenophosphorylated imidazole derivative and its synthesis method and application. Background Technology

[0002] The information disclosed in the background section of this invention is intended only to enhance the understanding of the overall background of the invention and is not necessarily to be regarded as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Imidazoles and their derivatives are an important class of organic heterocyclic compounds, ubiquitous in daily life, and commonly found in natural products, pharmaceuticals, functional materials, and organic ligands. The synthesis of 3-thio / selenophosphorylated imidazole derivatives is rarely studied. The first relevant report involved the C3-thiophosphorylation of imidazole[1,2-a]pyridine under heating conditions at 60°C, using imidazo[1,2-a]pyridine, phosphite, and S8 as starting materials, with tert-butyl hydroperoxide as the oxidant, and catalyzed by iodide. To date, there is no direct method for synthesizing 3-thio / selenophosphorylated imidazole derivatives. Summary of the Invention

[0004] To address the shortcomings and deficiencies of the prior art, the first objective of this invention is to provide a 3-thio / selenophosphorylated imidazole derivative.

[0005] The second objective of this invention is to provide a method for synthesizing the above-mentioned 3-thio / selenophosphorylated imidazole derivative, wherein the method can achieve one-pot three-component cross-coupling cyclization to construct the 3-thio / selenophosphorylated imidazole derivative under simple and mild electrochemical oxidation conditions.

[0006] A third objective of this invention is to provide the application of the above-mentioned 3-sulfo / selenophosphorylated imidazole derivative, which has excellent anti-locust activity and protective effect on wheat seedlings, does not affect the aquatic environment at low concentrations, and has good biocompatibility.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is shown in the following formula:

[0008] A 3-thio / selenophosphorylated imidazole derivative, the general structural formula of which is shown below:

[0009]

[0010] Among them, R 1 It is aryl or alkyl, etc.; X is sulfur or selenium; R 2 Methyl or ethyl, etc.; R3 It can be ethyl or n-butyl, etc.

[0011] The method for synthesizing the above-mentioned 3-thio / selenophosphorylated imidazole derivative involves using compounds represented by structural formula a, structural formula b, and structural formula c as reactants, and carrying out an electrochemical oxidation reaction under air conditions to obtain the 3-thio / selenophosphorylated imidazole derivative. The reaction formula is as follows:

[0012]

[0013] Furthermore, the compound represented by structural formula a is an isothiocyanate or isoselenic cyanate; the compound represented by structural formula b is an isocyanate; and the compound represented by structural formula c is a phosphite.

[0014] Further, the isothiocyanate is phenyl isothiocyanate, 4-methylphenyl isothiocyanate, 4-tert-butylphenyl isothiocyanate, 4-methoxyphenyl isothiocyanate, 4-bromophenyl isothiocyanate, 4-chlorophenyl isothiocyanate, 3-methylphenyl isothiocyanate, 3-chlorophenyl isothiocyanate, 3-trifluoromethylphenyl isothiocyanate, 3-fluorophenyl isothiocyanate, 2-bromophenyl isothiocyanate, 2-methylphenyl isothiocyanate, or 3,5-dimethylphenyl isothiocyanate; the isoselenate is 2-iodophenyl isothiocyanate, 3,4-(methylenedioxy)phenyl isothiocyanate, or 2-iodo-5-methylphenyl isothiocyanate.

[0015] The isocyanate is ethyl isocyanate or methyl isocyanate;

[0016] The phosphite is dimethyl phosphite, diethyl phosphite, dibutyl phosphite, or diphenyl phosphite.

[0017] Furthermore, the electrochemical oxidation reaction is carried out at room temperature, using carbon felt as the anode and platinum sheet as the cathode, and employing a constant current.

[0018] Furthermore, the current is 1.0 mA, and the electrochemical oxidation reaction time is 8 h.

[0019] Furthermore, the compounds represented by structural formula a and structural formula b are first reacted in an organic solvent under alkaline conditions for 1 hour, and then the compound represented by structural formula c and an acid are added to carry out an electrochemical oxidation reaction.

[0020] Furthermore, the molar ratio of the compound represented by structural formula a, the compound represented by structural formula b, the compound represented by structural formula c, the base, and the acid is 1:1:2:3:3.

[0021] Furthermore, the organic solvent is acetonitrile; the base is NaOH; and the acid is hydrochloric acid.

[0022] Furthermore, after the electrochemical oxidation reaction is completed, the reaction mixture needs to be washed, extracted, dried, concentrated, and separated.

[0023] Furthermore, the extraction is performed using dichloromethane; the drying is performed using anhydrous sodium sulfate.

[0024] Applications of the above-mentioned 3-thio / selenophosphorylated imidazole derivatives.

[0025] Furthermore, the application is for the preparation of pesticides.

[0026] Beneficial effects

[0027] The compounds synthesized in this invention have undergone a series of pesticide and bioactivity tests, demonstrating excellent anti-locust activity and protective effects on wheat seedlings. They do not affect the aquatic environment at low concentrations and exhibit good biocompatibility, providing a good model for pesticide screening. This invention utilizes readily available isothio / selenocyanide, isocyanate, and phosphite compounds as raw materials in a metal-free and chemically oxidizing integrated tank. First, a thiourea intermediate is generated under alkaline conditions, followed by electrochemical oxidation-induced one-pot three-component cross-coupling cyclization to construct a 3-thio / selenophosphorylated imidazole derivative. The synthesis method is mild, allowing for highly selective acquisition of the target product at room temperature and air using a small current. It offers advantages such as simple operation, readily available and inexpensive raw materials, broad substrate applicability, high synthesis efficiency, and high atom economy. The compounds synthesized in this invention exhibit excellent anti-locust activity and protective effects on wheat seedlings, do not affect the aquatic environment at low concentrations, and have good biocompatibility, making them suitable for pesticide preparation and showing promising application prospects. Attached Figure Description

[0028] Figure 1 This is a statistical graph showing the bioactivity results of the 3-thio / selenophosphorylated imidazole derivative prepared in Example 1 for 1 day. Figure 1 a is a phenotypic diagram of wheat resistance to locusts with ethanol; Figure 1 b is the phenotypic diagram of locust resistance in wheat at 1d; Figure 1 c is a statistical chart of the toxicity assessment results for day 1; Figure 1 d is a statistical graph of the cytotoxicity assessment results on day 1; Figure 1 e is a statistical graph showing the effect of 1d on the inflammatory factor IL-6; Figure 1 f is a statistical graph showing the effect of 1 day on the inflammatory factor THF-α. Detailed Implementation

[0029] The following description further sets forth specific details of the invention to provide a thorough understanding of it. The terminology used in this specification is for illustrative purposes only and is not intended to limit the scope of the invention.

[0030] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as understood by one of ordinary skill in the art. Unless otherwise specified, the pharmaceuticals or reagents used in this invention are used in accordance with the product instructions or conventional methods in the relevant field. The process of this invention is now further described with reference to the accompanying drawings and specific embodiments.

[0031] The electrolysis instrument used in the following examples is a dual-display potentiometer (DSS-292B or SS-L303SPD) (domestic).

[0032] Example 1

[0033]

[0034] In a dry, magnetically charged three-necked flask (25 mL), add phenyl isothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 1d, with a yield of 75%. The NMR characterization data are as follows:

[0035]

[0036] MRI: 1 H NMR (500MHz, CDCl3) δ = 7.82 (d, J = 1.7Hz, 1H), 7.52 (dd, J = 9.1, 6.1Hz, 3H), 7.47 (dd, J = 7.8, 1.5Hz, 2H), 4 .43(q,J=7.1Hz,2H),4.02–3.93(m,2H),3.88–3.79(m,2H),1.44(t,J=7.1Hz,3H),1.19(t,J=7.1Hz,6H). 13C NMR (126MHz, CDCl3) δ = 162.0 (d, J = 2.3Hz), 140.1 (d, J = 2.0Hz), 138.5 (d, J = 6.1Hz), 135.0, 129 .3(d,J=18.5Hz),127.4,120.5(d,J=8.7Hz),64.3(d,J=6.2Hz),60.9,15.8(d,J=7.4Hz),14.4.

[0037] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 16 H 21 N2O5PS:385.0982; found:385.0982

[0038] Example 2

[0039]

[0040] In a dry, magnetically fitted three-necked flask (25 mL), add phenyl 3-chloroisothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 2d, with a yield of 77%. The NMR characterization data are as follows:

[0041]

[0042] MRI: 1 H NMR (500MHz, CDCl3) δ = 7.75 (s, 1H), 7.49 (s, 1H), 7.44–7.39 (m, 2H), 7.31 (d, J = 7.5Hz, 1H), 4.36 (q ,J=7.1Hz,2H),4.02–3.92(m,2H),3.92–3.80(m,2H),1.36(t,J=7.1Hz,3H),1.16(t,J=7.1Hz,6H). 13C NMR (126MHz, CDCl3) δ = 161.8 (d, J = 2.2Hz), 140.0 (d, J = 1.9Hz), 138.7 (d, J = 6.3Hz), 135.9, 134.9, 130 .2,129.6,127.6,125.7,120.6(d,J=8.5Hz),76.8,64.5(d,J=6.5Hz),61.0,15.9(d,J=7.4Hz),14.3.

[0043] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 16 H 20 ClN2O5PS:419.0592; found:419.0592.

[0044] Example 3

[0045]

[0046] In a dry, magnetically fitted three-necked flask (25 mL), add phenyl 3-trifluoromethyl isothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 3d, with a yield of 75%. The NMR characterization data are as follows:

[0047]

[0048] MRI: 1 H NMR (500MHz, CDCl3) δ = 7.78 (d, J = 1.6Hz, 1H), 7.76 (s, 1H), 7.72 (dd, J = 4.4, 3.5Hz, 1H), 7.63 (d, J = 5.2Hz, 2H), 4 .37(q,J=7.1Hz,2H),3.99–3.90(m,2H),3.88–3.79(m,2H),1.37(t,J=7.1Hz,3H),1.14(td,J=7.0,0.6Hz,6H). 13C NMR (126MHz, CDCl3) δ = 161.7 (d, J = 2.4Hz), 140.4, 140.0 (d, J = 2.1Hz), 135. 3(d,J=32.0Hz),131.8(qd,J=33.3,5.5Hz),130.9(d,J=25.2Hz),130.0(d,J =10.3Hz), 126.3 (dq, J = 34.5, 7.1Hz), 124.5 (q, J = 3.7Hz), 123.2 (q, J = 273. 6Hz), 120.6 (d, J = 8.6Hz), 64.5 (d, J = 6.6Hz), 61.0, 15.7 (d, J = 7.3Hz), 14.3.

[0049] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 17 H 20 F3N2O5PS:453.0855; found:453.0857.

[0050] Example 4

[0051]

[0052] In a dry, magnetically charged three-necked flask (25 mL), add phenyl 2-methylisothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour over a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 4d, with a yield of 76%. The NMR characterization data are as follows:

[0053]

[0054] MRI: 1H NMR (500MHz, CDCl3) δ7.64=(d,J=1.7Hz,1H),7.37–7.31(m,2H),7.28(dd,J=14.7,7.1Hz,2H),4.37(q,J=7.1Hz,2H),3.99–3.91(m,1H),3 .90–3.83(m,1H),3.82–3.75(m,1H),3.71–3.64(m,1H),2.03(s,3H),1.38(t,J=7.1Hz,3H),1.16(t,J=7.0Hz,3H),1.09(t,J=7.0Hz,3H). 13 C NMR (126MHz, CDCl3) δ = 162.0 (d, J = 2.1Hz), 140.0 (d, J = 1.7Hz), 138.0 (d, J = 6.2Hz), 136.0, 133.9, 130 .9,129.9,129.3,126.5,121.2(d,J=8.6Hz),64.2(d,J=22.6Hz),60.9,17.7,15.8(d,J=14.4Hz),15.8 14.3.

[0055] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 17 H 23 N2O5PS:399.1138; found:399.1138.

[0056] Example 5

[0057]

[0058] In a dry, magnetically fitted three-necked flask (25 mL), add phenyl 4-chloroisothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour over a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 5d, with a yield of 51%. The NMR characterization data are as follows:

[0059]

[0060] MRI: 1 H NMR (500MHz, CDCl3) δ7.73(d,J=1.5Hz,1H),7.44(d,J=8.7Hz,2H),7.36(d,J=8.7Hz,2H),4.36(q,J= 7.1Hz,2H),4.00–3.91(m,2H),3.90–3.80(m,2H),1.37(t,J=7.1Hz,3H),1.16(td,J=7.1,0.7Hz,6H). 13 C NMR(126MHz, CDCl3)δ161.8(d,J=2.6Hz),140.0(d,J=1.6Hz),138.7,135.7,1 33.4,129.5,129.4,128.8,64.5(d,J=6.5Hz),61.0,15.9(d,J=7.4Hz),14.3.

[0061] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 16 H 20 ClN2O5PS:419.0592; found:419.0590.

[0062] Example 6

[0063]

[0064] In a dry, magnetically charged three-necked flask (25 mL), add phenyl 4-bromoisothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 6d, with a yield of 49%. The NMR characterization data are as follows:

[0065]

[0066] MRI: 1H NMR (500MHz, CDCl3) δ7.79 (s, 1H), 7.67 (d, J = 8.6Hz, 2H), 7.37 (d, J = 8.6Hz, 2H), 4.43 (q, J = 7. 1Hz, 2H), 4.07–3.98 (m, 2H), 3.97–3.88 (m, 2H), 1.44 (t, J = 7.1Hz, 3H), 1.23 (t, J = 7.1Hz, 6H). 13 C NMR (126MHz, CDCl3) δ161.8, 140.0, 138.7 (d, J = 5.8Hz), 133.9, 132.4, 129.1, 123.6, 120.5 (d, J = 8.7Hz), 64.5 (d, J = 6.4Hz), 61.0, 15.9 (d, J = 7.3Hz), 14.3.

[0067] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 16 H 20 BrN2O5PS:463.0087; found:463.0086.

[0068] Example 7

[0069]

[0070] In a dry, magnetically fitted three-necked flask (25 mL), add phenyl 3,5-dimethylisothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 7d, with a yield of 72%. The NMR characterization data are as follows:

[0071]

[0072] MRI: 1H NMR (500MHz, CDCl3) δ = 7.70 (d, J = 1.8Hz, 1H), 7.05 (s, 1H), 6.98 (s, 2H), 4.35 (q, J = 7.1Hz, 2H), 3 .98–3.86(m,2H),3.82–3.72(m,2H),2.31(s,6H),1.36(t,J=7.1Hz,3H),1.12(t,J=7.1Hz,6H). 13 C NMR (126MHz, CDCl3) δ = 162.0 (d, J = 2.3Hz), 140.1 (d, J = 2.1Hz), 139.1, 138.4 (d, J = 6.3Hz), 134.7, 130 .9,130.8,124.7,124.6,120.4(d,J=8.8Hz),64.1(d,J=6.1Hz),60.8,21.1,15.8(d,J=7.5Hz),14.3.

[0073] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 18 H 25 N2O5PS:413.1295; found:413.1295.

[0074] Example 8

[0075]

[0076] In a dry, magnetically charged three-necked flask (25 mL), add phenyl isothiocyanate (0.5 mmol), methyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 8d, with a yield of 73%. The NMR characterization data are as follows:

[0077]

[0078] MRI: 1H NMR (500MHz, CDCl3) δ = 7.82 (s, 1H), 7.52 (t, J = 7.2Hz, 3H), 7.49–7.44 (m, 2H), 3.95 (s, 3H), 3.90–3.79 (m, 2H), 1.19 (t, J = 7.1Hz, 6H). 13 C NMR (126MHz, CDCl3) δ=162.3, 149.0, 140.2, 134.9, 129.4, 129.2, 128.4 (d, J=8.2Hz), 127.4, 64.3 (d, J=6.3Hz), 51.9, 15.8 (d, J=7.3Hz). High resolution: HRMS (ESI) m / z: [M+H] + calcd for C 15 H 19 N₂O₅PS[M+H] + :371.0825; found:371.0826.

[0079] Example 9

[0080]

[0081] In a dry, magnetically charged three-necked flask (25 mL), phenyl isothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol) were added. Acetonitrile (8.0 mL) was slowly added to the reaction flask under air, and the mixture was stirred at room temperature for 1 hour. Dibutyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol) were then added, and the mixture was poured through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 9d, with a yield of 75%. The NMR characterization data are as follows:

[0082]

[0083] MRI: 1H NMR (500MHz, CDCl3) δ = 7.84 (s, 1H), 7.54–7.49 (m, 3H), 7.48–7.44 (m, 2H), 4.41 (q, J = 7.1Hz, 2H), 3.6 6–3.60(m,2H),3.53–3.46(m,2H),1.85–1.75(m,2H),1.42(t,J=7.1Hz,3H),0.82(d,J=6.7Hz,12H). 13 C NMR (126MHz, CDCl3) δ = 161.8, 140.1, 138.3 (d, J = 5.5Hz), 135.0 (d, J = 4.0Hz), 129.4, 129.2 ,127.5,120.7(d,J=5.6Hz),73.7(d,J=7.0Hz),60.9,28.8(d,J=7.4Hz),18.5,18.5,14.3.

[0084] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 20 H 29 N₂O₅PS[M+H] + :441.1608; found:441.1606.

[0085] Example 10

[0086]

[0087] In a dry, magnetically charged three-necked flask (25 mL), add phenyl 4-methylisothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 10d, with a yield of 64%. The NMR characterization data are as follows:

[0088]

[0089] MRI: 1H NMR(500MHz, CDCl3)δ7.79(d,J=1.5Hz,1H),7.34–7.30(m,4H),4.43(q,J=7.1Hz,2H),4.03 –3.95(m,2H),3.90–3.82(m,2H),2.43(s,3H),1.43(t,J=7.1Hz,3H),1.19(t,J=7.1Hz,6H). 13 C NMR (126MHz, CDCl3) δ162.0 (d, J = 2.4Hz), 140.2 (d, J = 2.0Hz), 139.6, 138.4 (d, J = 6.1Hz ),132.41,129.7,127.1,120.6,64.2(d,J=6.3Hz),60.9,21.1,15.8(d,J=7.5Hz),14.3.

[0090] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 17 H 23 N2O5PS:399.1138; found:399.1138.

[0091] Example 11

[0092]

[0093] In a dry, magnetically fitted three-necked flask (25 mL), add phenyl 3-fluoroisothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 11d, with a yield of 68%. The NMR characterization data are as follows:

[0094]

[0095] MRI: 1H NMR(500MHz, CDCl3)δ7.76(s,1H),7.44(dd,J=14.2,7.8Hz,1H),7.25–7.15(m,3H),4.36(q,J =7.1Hz,2H),4.02–3.92(m,2H),3.91–3.79(m,2H),1.38–1.34(m,3H),1.15(t,J=7.1Hz,6H). 13 C NMR (126MHz, CDCl3) δ162.4 (d, J = 250.1Hz), 161.8 (d, J = 2.3Hz), 140.0 (d, J = 2.1Hz), 138.7 (d, J = 6.2Hz), 136.1 (d, J = 10.0Hz), 130.5 (d, J = 8.9 Hz), 123.2 (d, J = 3.4Hz), 120.5 (d, J = 8.7Hz), 116.5 (d, J = 20.9Hz), 115.2 (d, J = 24.4Hz), 64.5 (d, J = 6.5Hz), 61.0, 15.8 (d, J = 7.3Hz), 14.3.

[0096] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 16 H 20 FN2O5PS:403.0887; found:403.0888.

[0097] Example 12

[0098]

[0099] In a dry, magnetically charged three-necked flask (25 mL), add phenyl 3-methylisothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 12d, with a yield of 71%. The NMR characterization data are as follows:

[0100]

[0101] MRI: 1 H NMR (500MHz, CDCl3) δ7.79(d,J=1.8Hz,1H),7.40(t,J=7.6Hz,1H),7.31(d,J=7.7Hz,1H),7.26(t,J=5.0Hz,2H),4.4 3(q,J=7.1Hz,2H),4.03–3.95(m,2H),3.89–3.80(m,2H),2.44(s,3H),1.44(t,J=7.1Hz,3H),1.19(t,J=7.1Hz,6H). 13 C NMR (126MHz, CDCl3) δ162.0 (d, J = 2.3Hz), 140.1 (d, J = 1.9Hz), 139.5, 138.5 (d, J = 6.1Hz), 134.9, 130 .0,129.0,127.8,124.3,120.5(d,J=8.7Hz),64.2(d,J=6.2Hz),60.9,21.2,15.9(d,J=7.5Hz),14.4.

[0102] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 17 H 23 N2O5PS:399.1138; found:399.1138.

[0103] Example 13

[0104]

[0105] In a dry, magnetically fitted three-necked flask (25 mL), add 0.5 mmol of 4-tert-butylisothiocyanate, 0.5 mmol of ethyl isocyanate, and 1.5 mmol of sodium hydroxide. Under air atmosphere, slowly add 8.0 mL of acetonitrile to the reaction flask, stir at room temperature for 1 hour, then add 1.0 mmol of diethyl phosphite and 1.5 mmol of hydrochloric acid (37%), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 13d, with a yield of 60%. The NMR characterization data are as follows:

[0106]

[0107] MRI: 1H NMR (500MHz, CDCl3) δ7.73 (s, 1H), 7.47 (d, J = 8.4Hz, 2H), 7.30 (d, J = 8.5Hz, 2H), 4.36 (dd, J = 14.0 ,7.0Hz,2H),3.92(m,2H),3.77(m,2H),1.37(t,J=7.1Hz,3H),1.29(s,9H),1.10(t,J=7.1Hz,6H). 13 C NMR (126MHz, CDCl3) δ162.0, 152.7, 140.2, 132.3, 126.9, 126.1, 120.6, 64.1 (d, J = 6.0Hz), 60.8, 34.8, 31.2, 15.8 (d, J = 7.5Hz), 14.3.

[0108] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 20 H 29 N2O5PS:441.1608; found:441.1607.

[0109] Example 14

[0110]

[0111] In a dry, magnetically charged three-necked flask (25 mL), add phenyl 2-bromoisothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 Electrolysis was performed at a constant current (1.0 mA) for 8 hours using a cathode. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain the 3-thiophosphorylated 3-thio / selenophosphorylated imidazole derivative in 70% yield. NMR characterization data are as follows:

[0112]

[0113] MRI: 1H NMR (500MHz, CDCl3) δ7.71–7.67(m,2H),7.60(dd,J=7.8,1.5Hz,1H),7.44(td,J=7.7,1.2Hz,1H),7.36(td,J=7.8,1.6Hz,1H),4 .38(q,J=7.1Hz,2H),4.17–4.01(m,2H),3.82–3.62(m,2H),1.39(t,J=7.1Hz,3H),1.24(t,J=7.0Hz,3H),1.09(t,J=7.1Hz,3H). 13 C NMR (126MHz, CDCl3) δ161.8(d,J=2.4Hz),139.9(d,J=2.2Hz),138.1(d,J=6.4Hz),134.1,133.2,131.3,131.2,128.0,1 22.8, 121.3 (d, J = 8.6Hz), 64.4 (d, J = 67.8Hz), 64.4 (d, J = 67.5Hz), 60.9, 15.9 (d, J = 16.0Hz), 15.8 (d, J = 15.6Hz), 14.3.

[0114] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 16 H 20 BrN2O5PS:463.0087; found:463.0087.

[0115] Example 15

[0116]

[0117] In a dry, magnetically charged three-necked flask (25 mL), add phenyl 2-iodo-5-methylisoselenocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 15d, with a yield of 60%. The NMR characterization data are as follows:

[0118]

[0119] MRI: 1 H NMR (500MHz, CDCl3) δ = 7.81 (d, J = 8.1Hz, 1H), 7.66 (s, 1H), 7.42 (s, 1H), 7.01 (d, J = 8.1Hz, 1H), 4.42 (q, J = 7.1Hz, 2H), 4 .20–4.07(m,2H),3.90–3.73(m,2H),2.38(s,3H),1.44(t,J=7.2Hz,3H),1.30(t,J=7.1Hz,3H),1.17(t,J=7.1Hz,3H). 13 C NMR=(126MHz, CDCl3)δ161.6,140.1,139.5(d,J=3.5Hz),139.0,138.3(d,J=13.5Hz),132.2(d,J=11.5Hz),13 1.2,130.7,130.3,94.3(d,J=49.2Hz),64.1(dd,J=63.3,6.0Hz),60.9,20.7,15.8(dd,J=17.9,7.4Hz),14.4.

[0120] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 17 H 22 IN₂O₅PSe[M+H] + :572.9549; found:572.9549.

[0121] Example 16

[0122]

[0123] In a dry, magnetically charged three-necked flask (25 mL), add phenyl 4-methoxyisothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 16d, with a yield of 55%. The NMR characterization data are as follows:

[0124]

[0125] MRI: 1 H NMR (500MHz, CDCl3) δ = 8.61 (s, 1H), 7.46 (d, J = 8.9Hz, 2H), 7.05 (d, J = 8.9Hz, 2H), 4.44 (q, J = 7.1Hz, 2 H),4.07–3.97(m,2H),3.97–3.89(m,2H),3.88(s,3H),1.41(t,J=7.1Hz,3H),1.23(t,J=7.1Hz,6H). 13 C NMR (126MHz, CDCl3) δ = 161.1, 158.4, 139.6 (d, J = 2.4Hz), 136.0, 132.3, 128.8, 1 15.2(d,J=3.1Hz),114.6,65.0(d,J=6.8Hz),62.3,55.7,15.8(d,J=7.4Hz),14.

[0126] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 17 H 23 N2O6PS:415.1087; found:415.1088.

[0127] Example 17

[0128]

[0129] In a dry, magnetically fitted three-necked flask (25 mL), add phenyl isothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add dimethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 17d, with a yield of 72%. The NMR characterization data are as follows:

[0130]

[0131] MRI: 1H NMR (500MHz, CDCl3) δ = 7.76 (s, 1H), 7.51–7.47 (m, 3H), 7.36 (d, J = 3.0Hz, 2H), 4.28 (q, J = 7.1Hz, 2H), 3.54 (s, 3H), 3.52 (s, 3H), 1.37 (t, J = 7.1Hz, 3H). 13 CNMR (126MHz, CDCl3) δ = 162.3, 140.2, 134.9, 129.4, 129.2, 128.4 (d, J = 8.0Hz), 127.4, 120.7 (d, J = 8.8Hz), 64.3 (d, J = 6.4Hz), 51.9, 15.8 (d, J = 7.5Hz).

[0132] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 14 H 17 N2O5PS:357.0669; found:357.0669.

[0133] Example 18

[0134]

[0135] In a dry, magnetically charged three-necked flask (25 mL), phenyl isothiocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol) were added. Acetonitrile (8.0 mL) was slowly added to the reaction flask under air atmosphere, and the mixture was stirred at room temperature for 1 hour. Then, diphenyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol) were added, and the mixture was poured through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 18d, with a yield of 56%. The NMR characterization data are as follows:

[0136]

[0137] MRI: 1H NMR(500MHz, CDCl3)δ=7.90(s,1H),7.42–7.37(m,3H),7.35–7.32(m,2H),7.30–7.27(m,4 H),7.23–7.17(m,3H),7.02(d,J=8.2Hz,3H),4.30(q,J=7.1Hz,2H),1.34(t,J=7.1Hz,3H). 13 C NMR (126MHz, CDCl3) δ = 160.9, 150.1 (d, J = 9.4Hz), 144.7, 140.8 (d, J = 1.6Hz), 134.5, 130. 4,129.7,129.4(d,J=2.4Hz),129.2,128.4,127.1,125.6,120.2(d,J=5.0Hz),61.1,14.2.

[0138] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 24 H 21 N2O5PS:481.0982; found:481.0982.

[0139] Example 19

[0140]

[0141] In a dry, magnetically charged three-necked flask (25 mL), add phenyl 2-iodoselenocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 19d, with a yield of 59%. The NMR characterization data are as follows:

[0142]

[0143] MRI: 1H NMR(500MHz, CDCl3)δ=7.98(d,J=7.9Hz,1H),7.77(d,J=1.4Hz,1H),7.75(s,1H),7.62(d,J=8.0Hz,1H),7.27–7.20(m,2H),4 .47–4.40(m,2H),4.20–4.08(m,2H),3.90–3.74(m,2H),1.45(t,J=7.1Hz,3H),1.30(t,J=7.1Hz,3H),1.17(t,J=7.1Hz,3H). 13 C NMR (126MHz, CDCl3) δ = 175.3, 140.4, 139.5, 138.5 (d, J = 10.7Hz), 131.4 (d, J = 9.8Hz), 130.7, 130.2 ,129.3,129.0,98.8(d,J=48.1Hz),64.3(dd,J=54.1,6.2Hz),61.1,15.9(dd,J=15.3,7.5Hz),14.4.

[0144] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 16 H 20 IN2O5PSe:558.9392; found:558.9393.

[0145] Example 20

[0146]

[0147] In a dry, magnetically charged three-necked flask (25 mL), add phenyl 3,4-(methylenedioxy)isoselenocyanate (0.5 mmol), ethyl isocyanate (0.5 mmol), and sodium hydroxide (1.5 mmol). Under air atmosphere, slowly add acetonitrile (8.0 mL) to the reaction flask, stir at room temperature for 1 hour, then add diethyl phosphite (1.0 mmol) and hydrochloric acid (37%, 1.5 mmol), and pour the mixture through a carbon felt (1.0 × 1.0 cm). 2 The anode is a platinum sheet (1.0 × 1.0 cm). 2 The cathode was used as a cathode, and electrolysis was performed at a constant current (1.0 mA) for 8 hours. After the reaction, the reaction mixture was washed with water and extracted with dichloromethane (10 mL × 3). The combined organic layers were dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain 20 d, with a yield of 59%. The NMR characterization data are as follows:

[0148]

[0149] MRI:1 H NMR (500MHz, CDCl3) δ = 7.78 (s, 1H), 6.94 (s, 1H), 6.88 (s, 2H), 6.06 (s, 2H), 4.40 (q, J = 7.1H z,2H),4.14–4.01(m,2H),4.00–3.91(m,2H),1.41(t,J=7.1Hz,3H),1.24(t,J=7.0Hz,6H). 13 C NMR(126MHz, CDCl3)δ=162.1,148.5,147.9,140.9,129.4,129.2,127.4,12 1.3,108.8,108.0,102.1,64.2(d,J=6.3Hz),60.9,15.8(d,J=7.5Hz),14.3.

[0150] High resolution: HRMS(ESI) m / z: [M+H] + calcd for C 17 H 21 N2O7PSe:477.0324; found:477.0324.

[0151] Performance testing

[0152] Furthermore, a series of bioactive applications have been carried out using the 3-thio / selenophosphorylated imidazole derivatives synthesized in this invention, with results as follows: Figure 1 As shown. First, using compound 1d prepared in Example 1 as a potential pesticide molecule, a wheat locust resistance experiment was conducted. Figure 1 The study showed that ethanol had no significant effect on wheat locusts. Figure 1 b shows that 0.5 mg / mL of compound 1 day can significantly reduce the number of wheat locusts, indicating that this type of molecule has good anti-locust activity against wheat. Subsequently, to assess the toxicity of such potential pesticide molecules to aquatic systems, a series of toxicity assessments were conducted using crucian carp fry as experimental subjects, and the results are as follows: Figure 1 As shown in c, when the concentration at 6 days was 5 mg / L, the mortality rate of crucian carp fry was 0. Furthermore, the effects of some compounds on the cytotoxicity of mouse RAW264.7 macrophages and the inflammatory factors IL-6 and THF-α were evaluated, and the results showed that these compounds had low cytotoxicity. Figure 1 d), and it will not significantly affect the inflammatory factor IL-6 ( Figure 1 e) and THF-α ( Figure 1 The level of f) indicates that the compounds synthesized in this invention have good biocompatibility.

[0153] In summary, the 3-thio / selenophosphorylated imidazole derivative synthesized in this invention can be used for locust control in wheat, exhibiting excellent pesticide activity and biocompatibility, and possessing great potential for pesticide application. Furthermore, when the concentration of the synthesized 3-thio / selenophosphorylated imidazole derivative is 5 mg / L, its toxicity to aquatic systems is zero. In addition, the 3-thio / selenophosphorylated imidazole derivative synthesized in this invention has low cytotoxicity and does not significantly affect the levels of cytotoxicity and inflammatory factors IL-6 and THF-α.

[0154] The above description merely illustrates several embodiments of the present invention and should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make modifications, substitutions, and improvements without departing from the concept and scope of the present invention, and these all fall within the protection scope of the present invention. Therefore, the patent protection scope of the present invention should be determined by the described claims.

Claims

1. A 3-thio / selenophosphorylated imidazole derivative, characterized in that, The general structural formula of the 3-thio / selenophosphorylated imidazole derivative is shown below: ； Among them, R 1 The following are possible values: phenyl, 3-chlorophenyl, 3-trifluoromethylphenyl, 2-methylphenyl, 4-chlorophenyl, 4-bromophenyl, 3,5-dimethylphenyl, 4-methylphenyl, 3-fluorophenyl, 3-methylphenyl, 4-tert-butylphenyl, or 2-bromophenyl; X is sulfur; R 2 It is methyl or ethyl; R 3 It is ethyl or n-butyl.

2. A method for synthesizing the 3-thio / selenophosphorylated imidazole derivative according to claim 1, characterized in that, The synthesis method involves using the compounds shown in structural formula a, structural formula b, and structural formula c as reactants, and carrying out an electrochemical oxidation reaction under air conditions to obtain the 3-thio / selenophosphorylated imidazole derivative. The reaction formula is as follows: The compounds represented by structural formula a and structural formula b are first reacted in an organic solvent under alkaline conditions for 1 hour, and then the compound represented by structural formula c and an acid are added to carry out an electrochemical oxidation reaction. The organic solvent is acetonitrile; the base is NaOH; and the acid is hydrochloric acid. Wherein, the compound represented by structural formula a is an isothiocyanate, the compound represented by structural formula b is an isocyanate, and the compound represented by structural formula c is a phosphite; The R 1 R 2 and R 3 Same as the definition in claim 1.

3. The synthesis method according to claim 2, characterized in that, The isothiocyanate is phenyl isothiocyanate, 4-methylphenyl isothiocyanate, 4-tert-butylphenyl isothiocyanate, 4-bromophenyl isothiocyanate, 4-chlorophenyl isothiocyanate, 3-methylphenyl isothiocyanate, 3-chlorophenyl isothiocyanate, 3-trifluoromethylphenyl isothiocyanate, 3-fluorophenyl isothiocyanate, 2-bromophenyl isothiocyanate, 2-methylphenyl isothiocyanate, or 3,5-dimethylphenyl isothiocyanate.

4. The synthesis method according to claim 2, characterized in that, The electrochemical oxidation reaction was carried out at room temperature, using a carbon felt as the anode and a platinum sheet as the cathode, with a constant current of 1.0 mA for 8 hours.

5. The synthesis method according to claim 2, characterized in that, The molar ratio of the compound represented by structural formula a, the compound represented by structural formula b, the compound represented by structural formula c, the base, and the acid is 1:1:2:3:

3.

6. The synthesis method according to claim 2, characterized in that, After the electrochemical oxidation reaction is completed, the reaction mixture needs to be washed, extracted, dried, concentrated and separated.

7. The synthesis method according to claim 6, characterized in that, The extraction was performed using dichloromethane; the drying was performed using anhydrous sodium sulfate.

8. The application of a 3-thio / selenophosphorylated imidazole derivative according to claim 1 and / or a 3-thio / selenophosphorylated imidazole derivative synthesized by the synthetic method according to any one of claims 2-7, characterized in that, The application is for preparing pesticides, which have locust-inhibiting activity.

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