Method for electrochemical synthesis of vinyl sulfonate compound

Abstract

The invention discloses a method for electrochemical synthesis of a vinyl sulfonate compound. According to the method, the reaction of olefin, sodium sulfinate and water is promoted by utilizing the mediation of halogen free radicals under an electrochemical condition, so that a series of polysubstituted vinyl sulphonate is directly synthesized. The method is simple and convenient in reaction operation, mild in reaction condition and high in regioselectivity, and does not need to use a transition metal catalyst.

Description

Technical Field

[0001] The invention relates to chemical synthesis technology, in particular to a method for electrochemically synthesizing vinyl sulfonate compounds. Background Art

[0002] Vinyl sulfonate compounds have shown important application value in many fields due to the unique properties of vinyl and sulfonate functional groups in their structures. These compounds have high chemical reactivity and can form a variety of polymers and functional materials through free radical polymerization, addition reaction, etc., and are widely used in materials science, pharmaceutical industry and electronics (Macromolecules, 2010, 43, 7021-7032, Journal of Membrane Science, 2016, 511, 119-129).

[0003] In emulsion polymerization, the addition of vinyl sulfonate as a functional monomer can significantly improve the stability and dispersibility of the emulsion. For example, its copolymers with styrene and acrylate can be used to prepare high-performance coatings, adhesives and emulsion stabilizers. This emulsion system exhibits excellent corrosion resistance and chemical resistance in industrial coatings (Molecules, 2022, 27, 6353–6364). On the other hand, in the field of electronic materials, homopolymers or copolymers of vinyl sulfonic acid are widely used in the manufacture of polymer electrolyte membranes and conductive polymer coatings for fuel cells due to their excellent conductivity and thermal stability (Journal of Petroleum Science and Engineerin, 2022, 213, 110331). Its application in semiconductor and display manufacturing has further improved the performance and reliability of modern electronic products (Chem. Sci., 2025, 16, 1250–1264).

[0004] In addition, vinyl sulfonate compounds also have certain potential in the pharmaceutical field. For example, they can be used as modified monomers of drug molecules to generate targeted and biocompatible drug delivery systems through chemical cross-linking or copolymerization. Related studies have shown that these compounds can improve the bioavailability of drugs by controlling the drug release rate, thereby reducing the side effects during treatment (ACS Appl. Mater. Interfaces., 2009, 15, 1002–1012).

[0005] Vinyl sulfonate compounds have broad application prospects in industry and scientific research due to their chemical diversity and functionality.

[0006] Vinyl sulfonate is an indispensable building block in organic synthesis, playing a key role in important reactions such as cross-coupling reactions, carbonylation reactions, and polymerization reactions. Although a variety of synthetic methods for vinyl sulfonate have been studied, these methods usually require multiple steps and intermediate purification as well as expensive metal catalysts. The problem of poor selectivity also makes the generation of cis / trans isomers and double bond isomers a challenge. So far, there have been few reports on the direct synthesis of vinyl sulfonate from styrene. Summary of the invention

[0007] The purpose of the present invention is to provide a method for electrochemically synthesizing vinyl sulfonate compounds in view of the shortcomings of the prior art. The method has simple reaction operation, mild reaction conditions, high regioselectivity, and does not require the use of transition metal catalysts.

[0008] The technical solution for achieving the purpose of the present invention is:

[0009] A method for electrochemically synthesizing vinyl sulfonate compounds, wherein the general synthesis formula of the synthesized vinyl sulfonate compounds is:

[0010] ,

[0011] Among them, R 1 , R 2 It is an aromatic group or an aliphatic group; the electrolyte is tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide or potassium iodide; the base is cesium carbonate, sodium carbonate or potassium carbonate; and the solvent is acetonitrile.

[0012] The synthesis process of the vinyl sulfonate compound is:

[0013] 1) 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of base and 0.04 mmol of electrolyte were added to a 10 ml three-necked bottle, 6 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode and a platinum sheet was used as a cathode, and the mixture was stirred and reacted at a constant current of 7-14 mA and 10-40 degrees Celsius for 2-4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with 3×5 ml of ethyl acetate;

[0014] 2) The organic layer of the mixture was dried over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:10-30) to obtain the target product. During the elution purification, silica gel, ethyl acetate / petroleum ether=1:10-30.

[0015] The technical solution utilizes halogen free radical mediation under electrochemical conditions to promote the reaction of olefins with sodium sulfinate and water, thereby directly synthesizing a series of multi-substituted vinyl sulfonates.

[0016] This method has simple reaction operation, mild reaction conditions, high regioselectivity, and does not require the use of transition metal catalysts. DETAILED DESCRIPTION

[0017] The present invention will be further described below with reference to the embodiments, but the present invention is not limited thereto.

[0018] Embodiment 1:

[0019] Preparation and characterization of 1-phenylvinyl-4-methylbenzenesulfonate (a):

[0020]

[0021] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of cesium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 7 mA constant current at 15 degrees Celsius for 3 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:30) to obtain the target product;

[0022] The product was characterized as: Light yellow liquid (23.0 mg, 84%). 1 H NMR (400 MHz, CDCl 3 )δ7.80(d,J=8.4Hz,2H),7.45–7.41(m,2H),7.30–7.26(m,5H),5.40(d,J=2.9Hz,1H),5.09(d,J=2.9Hz,1H),2.41(s,3H). 13 C NMR (100 MHz, CDCl 3 )δ152.9,145.3,133.5,133.1,129.7,129.4,128.5,128.4,125.5,103.1,21.8.HRMS(m / z)[ESI]:calculated for C 15 H 15 O 3 S + [M+H] + :275.0736,found 275.0738.

[0023] Embodiment 2:

[0024] Preparation and characterization of 1-(p-tolyl)vinyl-4-methylbenzenesulfonate (b):

[0025]

[0026] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of sodium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 10 mA constant current at 15 degrees Celsius for 3.5 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:30) to obtain the target product;

[0027] The product was characterized as: Light yellow liquid (23.0 mg, 80%). 1 H NMR (400 MHz, CDCl 3 )δ7.81(d,J=8.4Hz,2H),7.33(d,J=8.3Hz,2H),7.29(d,J=8.0Hz,2H),7.09(d,J=8 .0Hz,2H),5.33(d,J=2.8Hz,1H),5.00(d,J=2.8Hz,1H),2.42(s,3H),2.32(s,3H). 13 C NMR (100 MHz, CDCl 3 )δ153.0,145.2,139.5,133.2,130.7,129.7,129.1,128.5,125.4,102.1,21.8,21.38.HRMS(m / z)[ESI]:calculated for C 16 H 17 O 3 S + [M+H] + :289.0893,found 289.0891.

[0028] Embodiment 3:

[0029] Preparation and characterization of 1-(m-tolyl)vinyl-4-methylbenzenesulfonate (c):

[0030]

[0031] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of cesium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 14 mA constant current at 20 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:30) to obtain the target product;

[0032] The product was characterized as: Clear liquid (20.8, 72%). 1 H NMR (400 MHz, CDCl 3 )δ7.80(d,J=8.4Hz,2H),7.30–7.27(m,2H),7.23(d,J=7.8Hz,1H),7.20–7.19(m,1H),7.16(t,J=7.6H z,1H),7.10(d,J=7.5Hz,1H),5.37(d,J=2.8Hz,1H),5.05(d,J=2.8Hz,1H),2.42(s,3H),2.29(s,3H). 13 C NMR (100 MHz, CDCl 3 )δ153.1,145.2,138.0,133.3,133.2,130.1,129.7,128.5,128.3,126.2,122.7,103.0,21.8,21.4.HRMS(m / z)[ESI]:calculated forC 16 H 17 O 3 S + [M+H] + :289.0893,found 289.0892.

[0033] Embodiment 4:

[0034] Preparation and characterization of 1-(o-tolyl)vinyl-4-methylbenzenesulfonate (d):

[0035]

[0036] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of sodium carbonate, and 0.04 mmol of tetrabutylammonium iodide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 14 mA constant current at 40 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:30) to obtain the target product;

[0037] The product was characterized as: Clear liquid (18.5 mg, 64%). 1 H NMR (400 MHz, CDCl 3 )δ7.62(d,J=8.4Hz,2H),7.19(d,J=0.8Hz,1H),7.17(t,J=1.5Hz,1H),7.16(d,J=1.8Hz,1H),7.14(d,J =1.3Hz,1H),7.08–7.03(m,2H),5.29(d,J=2.2Hz,1H),5.00(d,J=2.2Hz,1H),2.39(s,3H),2.27(s,3H). 13 C NMR (100 MHz, CDCl 3 )δ153.5,144.9,136.4,133.8,133.3,130.4,129.6,129.5,129.3,128.3,125.5,107.7,21.7,20.3.HRMS(m / z)[ESI]:calculated forC 16 H 17 O 3 S + [M+H] + :289.0893,found 289.0895.

[0038] Embodiment 5:

[0039] Preparation and characterization of 1-(4-tert-butylphenyl)vinyl-4-methylbenzenesulfonate (e):

[0040]

[0041] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of cesium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 10 mA constant current at 30 degrees Celsius for 3 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:25) to obtain the target product;

[0042] The product was characterized as: Clear liquid (28.1 mg, 85%). 1 H NMR (400 MHz, CDCl 3 )δ7.82–7.77(m,2H),7.37–7.33(m,2H),7.28(d,J=6.4Hz,2H),7.27–7.24(m ,2H),5.34(d,J=2.8Hz,1H),5.02(d,J=2.8Hz,1H),2.41(s,3H),1.28(s,9H). 13 C NMR (100 MHz, CDCl 3 )δ153.0,152.6,145.1,133.2,130.6,129.7,128.5,125.4,125.3,102.4,34.7,31.3,21.7.HRMS(m / z)[ESI]:calculated for C 19 H 23 O 3 S + [M+H] + :331.1362, found 331.1358.

[0043] Embodiment 6:

[0044] Preparation and characterization of 1-(4-chloromethylphenyl)vinyl-4-methylbenzenesulfonate (f):

[0045]

[0046] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of sodium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 14 mA constant current at 30 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:15) to obtain the target product;

[0047] The product was characterized as: Clear liquid (24.5 mg, 76%). 1 H NMR (400 MHz, CDCl 3 )δ7.79(d,J=8.3Hz,2H),7.41(d,J=8.3Hz,2H),7.29(d,J=4.8Hz,2H),7.27(d,J=4 .8Hz,2H),5.41(d,J=2.9Hz,1H),5.10(d,J=2.9Hz,1H),4.54(s,2H),2.42(s,3H). 13 C NMR (100 MHz, CDCl 3 )δ152.4,145.4,138.6,133.6,133.0,129.8,128.7,128.5,125.9,103.8,45.7,21.8.HRMS(m / z)[ESI]:calculated for C 16 H 16 C1O 3 S + [M+H] + :323.0503, found 323.0503.

[0048] Embodiment 7:

[0049] Preparation and characterization of 1-(4-fluorophenyl)vinyl-4-methylbenzenesulfonate (g):

[0050]

[0051] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of cesium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 10 mA constant current at 15 degrees Celsius for 3 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:25) to obtain the target product;

[0052] The product was characterized as: Light yellow liquid (19.0 mg, 65%). 1 H NMR (400 MHz, CDCl 3 )δ7.79(d,J=8.4Hz,2H),7.41(dd,J=8.9,5.2Hz,2H),7.31–7.27(m,2H),6.9 6(t,J=8.7Hz,2H),5.32(d,J=2.9Hz,1H),5.05(d,J=2.9Hz,1H),2.42(s,3H). 13 C NMR (100 MHz, CDCl 3 )δ164.6,162.1,152.0,145.4,133.0,129.8,128.5,127.6,127.5,115.6,115.4,103.1,103.0,21.8. 19 F NMR (376 MHz, CDCl 3 )δ-111.53.HRMS(m / z)[ESI]:calculated forC 15 H 14 FO 3 S + [M+H] + :293.0642,found293.0636.

[0053] Embodiment 8:

[0054] Preparation and characterization of 1-(4-chlorophenyl)vinyl-4-methylbenzenesulfonate (h):

[0055]

[0056] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of potassium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, and 4 ml of acetonitrile solvent was added to dissolve. A carbon rod was used as an anode and a platinum sheet was used as a cathode. The mixture was stirred and reacted at 15 degrees Celsius for 3 hours at a constant current of 10 mA. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:25) to obtain the target product;

[0057] The product was characterized as: Light yellow liquid (22.2 mg, 72%). 1 H NMR (400 MHz, CDCl 3 )δ7.80(d,J=8.4Hz,2H),7.37(d,J=8.7Hz,2H),7.32–7.29(m,2H),7.25(d ,J=6.6Hz,2H),5.39(d,J=3.0Hz,1H),5.09(d,J=3.0Hz,1H),2.43(s,3H). 13 C NMR (100 MHz, CDCl 3 )δ151.8,145.4,135.3,132.8,131.9,129.7,128.6,128.4,126.7,103.6,21.7.HRMS(m / z)[ESI]:calculated for C 15 H 14 C1O 3 S + [M+H] + :309.0347, found 309.0341.

[0058] Embodiment 9:

[0059] Preparation and characterization of 1-(4-bromophenyl)vinyl-4-methylbenzenesulfonate (i):

[0060]

[0061] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of cesium carbonate, and 0.04 mmol of tetrabutylammonium iodide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 14 mA constant current at 40 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:25) to obtain the target product;

[0062] The product was characterized as: Light yellow liquid (24.0 mg, 68%). 1 H NMR (400 MHz, CDCl 3 )δ7.79(d,J=8.4Hz,2H),7.41(d,J=8.6Hz,2H),7.30(d,J=2.4Hz,2H),7.3 0–7.27(m,2H),5.39(d,J=3.1Hz,1H),5.10(d,J=3.1Hz,1H),2.43(s,3H). 13 C NMR (100 MHz, CDCl 3 )δ151.9,145.5,132.9,132.5,131.7,129.8,128.5,127.1,123.6,103.8,21.8.HRMS(m / z)[ESI]:calculated for C 15 H 14 B O 3 S + [M+H] + :352.9842, found 352.9840.

[0063] Embodiment 10:

[0064] Preparation and characterization of 1-(3-bromophenyl)vinyl-4-methylbenzenesulfonate (j):

[0065]

[0066] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of cesium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 14 mA constant current at 40 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:25) to obtain the target product;

[0067] The product was characterized as: Clear liquid (21.9 mg, 62%). 1 H NMR (400 MHz, CDCl 3 )δ7.78(d,J=8.4Hz,2H),7.46(t,J=1.9Hz,1H),7.40(dd,J=7.9,1.0Hz,1H),7.38–7.35(m,1H),7. 30–7.28(m,2H),7.15(t,J=7.9Hz,1H),5.41(d,J=3.0Hz,1H),5.15(d,J=3.0Hz,1H),2.42(s,3H). 13 C NMR (100 MHz, CDCl 3 )δ151.4,145.6,135.5,132.9,132.3,130.0,129.9,128.6,128.5,124.2,122.6,104.8,21.8.HRMS(m / z)[ESI]:calculated for C 15 H 14 B O 3 S + [M+H] + :352.9842,found352.9840.

[0068] Embodiment 11:

[0069] Preparation and characterization of 1-phenylvinylbenzenesulfonate (k):

[0070]

[0071] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of sodium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 7 mA constant current at 15 degrees Celsius for 3 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:30) to obtain the target product;

[0072] The product was characterized as: Clear liquid (20.3 mg, 78%). 1 H NMR (400 MHz, CDCl 3 )δ7.97–7.90(m,2H),7.64–7.59(m,1H),7.50(t,J=7.8Hz,2H),7.45–7.39(m,2H),7.2 9(d,J=1.8Hz,2H),7.27(d,J=2.9Hz,1H),5.42(d,J=2.9Hz,1H),5.12(d,J=3.0Hz,1H). 13 C NMR (100 MHz, CDCl 3 )δ152.9,136.2,134.1,133.3,129.4,129.1,128.5,125.5,103.4.HRMS(m / z)[ESI]:calculated for C 14 H 13 O 3 S + [M+H] + :261.0580,found 261.0580.

[0073] Embodiment 12:

[0074] Preparation and characterization of 1-phenylvinyl-4-methoxybenzenesulfonate (1):

[0075]

[0076] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of cesium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 10 mA constant current at 25 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:10) to obtain the target product;

[0077] The product was characterized as: Clear liquid (17.1 mg, 59%). 1 H NMR (400 MHz, CDCl 3 )δ7.85(d,J=9.0Hz,2H),7.44–7.41(m,2H),7.29(d,J=2.1Hz,2H),7.28(d,J=1.8Hz, 1H), 6.93 (d, J = 9.0Hz, 2H), 5.40 (d, J = 2.8Hz, 1H), 5.10 (d, J = 2.8Hz, 1H), 3.86 (s, 3H). 13 C NMR (100 MHz, CDCl 3 )δ164.1,130.8,129.4,128.5,125.5,114.3,103.2,55.8.HRMS(m / z)[ESI]:calculated for C 15 H 15 O 4 S + [M+H] + :291.0686,found 291.0690.

[0078] Embodiment 13:

[0079] Preparation and characterization of 1-phenylvinyl-4-fluorobenzenesulfonate (m):

[0080]

[0081] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of cesium carbonate, and 0.04 mmol of potassium iodide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 10 mA constant current at 30 degrees Celsius for 3 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:20) to obtain the target product;

[0082] The product was characterized as: Clear liquid (19.2 mg, 69%). 1 H NMR (400 MHz, CDCl 3 )δ7.92(dd,J=8.9,5.0Hz,2H),7.40(dd,J=7.7,2.0Hz,2H),7.28(d,J=7.4Hz, 2H), 7.15 (dd, J=8.9, 8.2Hz, 2H), 5.43 (d, J=2.9Hz, 1H), 5.13 (d, J=2.9Hz, 1H). 13 C NMR (100 MHz, CDCl 3 )δ152.9,133.2,131.4,131.3,129.6,128.5,125.5,116.6,116.4,103.7. 19 F NMR (376 MHz, CDCl 3 )δ-102.39.HRMS(m / z)[ESI]:calculated for C 14 H 12 FO 3 S + [M+H] + :279.0486,found 279.0489.

[0083] Embodiment 14:

[0084] Preparation and characterization of 1-phenylvinyl-4-chlorobenzenesulfonate (n):

[0085]

[0086] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of cesium carbonate, and 0.04 mmol of tetrabutylammonium iodide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 10 mA constant current at 25 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:20) to obtain the target product;

[0087] The product was characterized as: Clear liquid (18.6 mg, 63%). 1 H NMR (400 MHz, CDCl 3 )δ7.84(d,J=8.6Hz,2H),7.45(d,J=8.6Hz,2H),7.40(dd,J=7.7,1.9Hz,2H),7. 30(d,J=2.0Hz,2H),7.28(s,1H),5.43(d,J=3.0Hz,1H),5.12(d,J=2.9Hz,1H). 13 C NMR (100 MHz, CDCl 3 )δ152.9,140.9,134.6,133.1,129.9,129.6,129.5,128.5,125.5,103.7.HRMS(m / z)[ESI]:calculated for C 14 H 11 C1O 3 SNa + [M+Na] + :317.0010, found 317.0010.

[0088] Embodiment 15:

[0089] Preparation and characterization of 1-phenylvinyl-4-bromobenzenesulfonate (o):

[0090]

[0091] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of cesium carbonate, and 0.04 mmol of tetrabutylammonium iodide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 10 mA constant current at 25 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:20) to obtain the target product;

[0092] The product was characterized as: Light yellow liquid (24.4 mg, 72%). 1 H NMR (400 MHz, DMSO-d 6 )δ7.86(d,J=1.0Hz,3H),7.51–7.43(m,3H),7.38–7.34(m,3H),5.77(d,J=3.4Hz,1H),5.04(d,J=3.4Hz,1H). 13 C NMR (100 MHz, DMSO-d 6 )δ152.19,134.52,133.31,132.9,130.5,130.0,129.0,128.2,125.5,104.8.HRMS(m / z)[ESI]:calculated for C 14 H 12 B O 3 S + [M+H] + :338.9685, found 338.9678.

[0093] Embodiment 16:

[0094] Preparation and characterization of 1-phenylvinyl-4-m-toluenesulfonate (p):

[0095]

[0096] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of cesium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 10 mA constant current at 25 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:30) to obtain the target product;

[0097] The product was characterized as: Clear liquid (20.3 mg, 74%). 1 H NMR (400 MHz, CDCl 3 )δ7.74–7.69(m,2H),7.43–7.41(m,2H),7.39(s,1H),7.36(t,J=7.4Hz,1H),7.28(d,J=1. 9Hz,2H),7.27(d,J=1.9Hz,1H),5.41(d,J=2.9Hz,1H),5.10(d,J=2.9Hz,1H),2.38(s,3H). 13 C NMR (100 MHz, CDCl 3 )δ152.9,139.5,136.0,134.9,133.4,129.4,129.0,128.8,128.4,125.6,125.5,103.4,21.3.HRMS(m / z)[ESI]:calculated for C 15 H 15 O 3 S + [M+H] + :275.0736,found275.0741.

[0098] Embodiment 17:

[0099] Preparation and characterization of 1-phenylvinyl-4-o-toluenesulfonate (q):

[0100]

[0101] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of sodium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 14 mA constant current at 25 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:30) to obtain the target product;

[0102] The product was characterized as: Clear liquid (18.6 mg, 68%). 1 H NMR (400 MHz, CDCl 3 )δ7.95(dd,J=7.9,1.4Hz,1H),7.52(dd,J=7.5,1.4Hz,1H),7.49–7.46(m,2H),7.37–7.32(m,2H),7. 31(d,J=2.2Hz,2H),7.29(d,J=4.1Hz,1H),5.34(d,J=3.0Hz,1H),4.89(d,J=3.0Hz,1H),2.73(s,3H). 13 C NMR (100 MHz, CDCl 3 )δ153.0,138.6,134.1,133.6,132.7,130.4,129.5,128.5,126.2,125.6,102.8,20.7.HRMS(m / z)[ESI]:calculated for C 15 H 15 O 3 S + [M+H] + :275.0736,found 275.0734.

[0103] Embodiment 18:

[0104] Preparation and characterization of 1-phenylvinyl-2-naphthalenesulfonate (r):

[0105]

[0106] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of potassium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 14 mA constant current at 25 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:25) to obtain the target product;

[0107] The product was characterized as: Clear liquid (16.1 mg, 52%). 1 H NMR (500 MHz, DMSO-d 6 )δ8.69(s,1H),8.26–8.23(m,1H),8.19(d,J=8.8Hz,1H),8.09(d,J=8.8Hz,1H),7.94(d,J=6.7Hz,1H),7.78 (s,1H),7.71(d,J=1.3Hz,1H),7.53–7.50(m,2H),7.31(s,3H),5.73(d,J=3.3Hz,1H),5.00(d,J=3.3Hz,1H). 13 C NMR (126 MHz, DMSO-d 6 )152.3,135.5,133.1,132.3,131.9,130.7,130.4,130.1,129.9,129.0,128.5,128.4,125.5,123.0,104.4.HRMS(m / z)[ESI]:calculated for C 18 H 15 O 3 S + [M+H] + :311.0736, found 311.0728.

[0108] Embodiment 19:

[0109] Preparation and characterization of 1-phenylvinyl ethyl sulfonate (s):

[0110]

[0111] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of cesium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 14 mA constant current at 15 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:30) to obtain the target product;

[0112] The product was characterized as: Light yellow liquid (15.7 mg, 74%). 1 H NMR (400 MHz, CDCl 3 )δ7.60–7.55(m,2H),7.40(d,J=3.7Hz,1H),7.38(d,J=2.3Hz,2H),5.51(d,J=3 .1Hz,1H),5.36(d,J=3.0Hz,1H),3.27(q,J=7.4Hz,2H),1.49(t,J=7.4Hz,3H). 13 C NMR (100 MHz, CDCl 3 )δ152.2,133.6,129.7,128.7,125.6,103.0,46.0,8.4.HRMS(m / z)[ESI]:calculated forC 10 H 13 O 3 S + [M+H] + :213.0580,found 213.0565.

[0113] Example 20: Preparation and Characterization of 1-phenylvinyl cyclopropyl sulfonate (t):

[0114]

[0115] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of cesium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 14 mA constant current at 40 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:30) to obtain the target product;

[0116] The product was characterized as: Light yellow liquid (18.6 mg, 78%). 1 H NMR (400 MHz, CDCl 3 )δ7.49(d,J=8.0Hz,2H),7.18(d,J=7.9Hz,2H),5.46(d,J=2.0Hz,1H),5.33(d,J=2.8Hz,1H ), 2.53(td,J=8.0,5.6Hz,1H),2.36(s,3H),1.34–1.28(m,2H),1.02(dt,J=8.0,4.1Hz,2H). 13 C NMR (101 MHz, CDCl 3 )δ152.8,139.8,131.0,129.4,125.5,102.7,77.1,28.7,21.4,6.5.HRMS(m / z)[ESI]:calculated for C 12 H 16 O 3 S + [M+H] + :239.0736,found 239.0728.

[0117] Embodiment 21:

[0118] Preparation and characterization of ((1R,4R)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptane-1-yl)methanesulfonic acid 1-phenylvinyl ester (u):

[0119]

[0120] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of sodium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 14 mA constant current at 30 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:10) to obtain the target product;

[0121] The product was characterized as: light yellow liquid (20.7 mg, 62%). 1 H NMR (400 MHz, CDCl 3)δ7.62–7.57(m,2H),7.42–7.35(m,3H),5.51(d,J=3.1Hz,1H),5.41(d,J=3.1Hz,1H),3.81(d, J=14.9Hz,1H),3.17(d,J=14.9Hz,1H),2.52(ddd,J=14.8,11.7,3.9Hz,1H),2.40(dt,J=18.5,4 .1Hz,1H),2.12(t,J=4.6Hz,1H),2.06(ddt,J=12.0,8.0,4.6Hz,1H),1.96(d,J=18.5Hz,1H),1. 70(ddd,J=14.0,9.4,4.7Hz,1H),1.44(ddd,J=13.1,9.3,3.9Hz,1H),1.13(s,3H),0.88(s,3H). 13 C NMR (100 MHz, CDCl 3 )δ214.0,152.4,133.5,129.5,128.6,125.5,102.6,58.1,48.2,47.9,42.8,42.4,26.8,25.1,19.9,19.6.HRMS(m / z)[ESI]:calculated for C 18 H 23 O 4 S + [M+H] + :335.1312, found 335.1302.

[0122] Embodiment 22:

[0123] Preparation and characterization of 4-(1-(p-toluenesulfonyloxy)vinyl)benzyl 2-(4-isobutylphenyl)propionate (v):

[0124]

[0125] 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of cesium carbonate, and 0.04 mmol of tetrabutylammonium bromide were added to a 10 ml three-necked bottle, 4 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode, a platinum sheet was used as a cathode, and a stirring reaction was carried out at 14 mA constant current at 40 degrees Celsius for 4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with ethyl acetate (3×5 ml), the organic layer was dried over anhydrous sodium sulfate, the solvent was dried under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:10) to obtain the target product;

[0126] The product was characterized as: light yellow liquid (42.4 mg, 86%). 1 H NMR (400 MHz, CDCl 3 )δ7.79(d,J=8.3Hz,2H),7.37(d,J=8.4Hz,2H),7.30–7.26(m,2H),7.19(d ,J=8.1Hz,2H),7.11(dd,J=12.6,8.1Hz,4H),5.37(d,J=3.0Hz,1H),5.09–5 .03(m,3H),3.74(q,J=7.1Hz,1H),2.46(d,J=7.2Hz,2H),2.42(s,3H),1.8 5(dt,J=13.5,6.8Hz,1H),1.51(d,J=7.2Hz,3H),0.91(s,3H),0.90(s,3H). 13 C NMR (101 MHz, CDCl 3 )δ174.5,152.5,145.3,140.8,137.6,137.4,133.2,133.1,129.8,129.4,128.5,127.7,12 7.3,125.6,103.2,65.7,45.2,45.1,30.3,22.5,21.8,18.5.HRMS(m / z)[ESI]:calculated for C 29 H 32 O 5 SNa + [M+Na] + :515.1863, found 515.1865.

[0127] In summary, the strategy for halogen radical-mediated olefin functionalization provided by this method shows that more new technologies for high-value conversion of styrene are expected to be developed based on this method.

Claims

1. A method for electrochemically synthesizing vinyl sulfonate compounds, characterized in that: The synthetic general formula of the synthetic vinyl sulfonate compound is: ， Among them, R 1 , R 2 It is an aromatic group or an aliphatic group; the electrolyte is tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide or potassium iodide; the base is cesium carbonate, sodium carbonate or potassium carbonate; and the solvent is acetonitrile.

2. The method for electrochemically synthesizing vinyl sulfonate compounds according to claim 1, characterized in that: The synthesis process of the vinyl sulfonate compound is: 1) 0.1 mmol of olefin, 0.2 mmol of sodium sulfinate, 0.2 mmol of base and 0.04 mmol of electrolyte were added to a 10 ml three-necked bottle, 6 ml of acetonitrile solvent was added to dissolve, a carbon rod was used as an anode and a platinum sheet was used as a cathode, and the mixture was stirred and reacted at a constant current of 7-14 mA and 10-40 degrees Celsius for 2-4 hours. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the mixture was extracted with 3×5 ml of ethyl acetate; 2) The organic layer of the mixture was dried over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate / petroleum ether=1:10-30) to obtain the target product. During the elution purification, silica gel, ethyl acetate / petroleum ether=1:10-30.

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