Preparation method of disulfonyl ethylene compound

Abstract

The invention relates to a preparation method of a disulfonyl olefin compound, which comprises the following steps: by taking aryl acetylene and a sodium benzenesulfinate compound as reaction substrates, adding a solvent, and carrying out blue light irradiation reaction for 6-12 hours in a buffer system of organic acid and alkali under the action of a photocatalyst to obtain the disulfonyl olefin compound. The method has the characteristics of wide substrate application range, easily available raw materials, simple operation and mild reaction conditions.

Description

Technical Field

[0001] This invention relates to the field of organic chemical synthesis, and more specifically to a method for preparing disulfone-ethylene compounds. Background Technology

[0002] Disulfone-based ethylene compounds, as an important class of sulfur-containing compounds, are a crucial skeletal structure in organic chemistry, serving as target molecules and general intermediates, and have wide applications in organic chemistry, agricultural chemistry, materials science, and medicinal chemistry. Their synthetic methods have always attracted considerable attention.

[0003] For decades, the direct functionalization of alkynes has been considered a powerful and practical method for assembling functionalized alkenes. Ortho-bifunctionalization of alkynes via radical relay has attracted considerable attention because this method can simultaneously form carbon-carbon and carbon-heterobonds within a carbon-carbon triple bond, providing a direct route for synthesizing complex molecules with excellent atom and step economy. Therefore, ortho-bifunctionalization of alkynes has become a simple and efficient route for synthesizing disulfonyl ethylene compounds. For example, Ning reported the copper-catalyzed disulfonation of terminal alkynes with sodium arylsulfonate in the presence of bromodifluoroacetate. Tang reported a similar reaction promoted by a high-valent iodine(III) reagent.

[0004] Despite significant progress in the synthesis of disulfone-based vinyl compounds, metal catalysts and high-valent iodine(III) reagents remain limiting factors in drug synthesis. Summary of the Invention

[0005] To address the shortcomings of current methods, this invention provides a method for preparing disulfone-based ethylene compounds. This method features a wide range of applicable substrates, readily available raw materials, simple operation, and high yield.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: a method for preparing disulfone-based ethylene compounds, the chemical reaction equation of which is as follows: ; The -Ar is one of the following: phenyl, 4-methylphenyl, 2-methylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-fluorophenyl, 2-fluorophenyl, 4-chlorophenyl, 3-bromophenyl, 4-trifluoromethylphenyl, and pyridine; The -R is one of phenyl, 4-fluorophenyl, 4-chlorophenyl, and 4-bromophenyl; The reaction includes the following steps: using arylacetylene and sodium benzenesulfonate as reaction substrates, adding solvent, and reacting under blue light irradiation for 6-12 hours in an organic acid and base buffer system under a nitrogen atmosphere and with the action of a photocatalyst. The solvent is one of toluene, ethylene glycol dimethyl ether, 1,4-dioxane, dichloroethane, and tetrahydrofuran; The alkali mentioned is one of cesium carbonate, potassium carbonate, and sodium carbonate; The organic acid mentioned is one of pentylene acid, trifluoroacetic acid, benzoic acid, and methanesulfonic acid.

[0007] The photocatalyst is one of tetrabromofluorescein, water-soluble eosin, and methylene blue.

[0008] The blue light intensity is in the range of 25-100W.

[0009] The amounts (molar parts) of each substance added are as follows: arylacetylene 1-2 parts; sodium benzenesulfonate 2-4 parts; photocatalyst 1-5 mol%; organic acid 1-3 parts; alkali 1-4 parts.

[0010] The preparation method further includes the following steps after the reaction: filtration using a filter funnel, rotary evaporation to remove solvent and obtain residue, column chromatography using a silica gel column, elution with eluent, collection of the eluent containing the target product, combining the eluents and removing solvent by vacuum concentration to obtain the target product. The beneficial effects of this invention are: the reaction involves various arylacetylenes and sodium benzenesulfinate compounds, wherein the arylacetylenes can be arylaceynes containing different substituents, including any one of pyridine heterocyclic alkynes; the sodium benzenesulfinate compounds can carry various electron-withdrawing groups, thus demonstrating the universality of its substrates.

[0011] The reaction mechanism is as follows: First, ground-state eosin Y (EY) is irradiated to generate excited-state eosin Y (EY*). Then, excited-state eosin Y (EY*) undergoes single-electron oxidation of the arylsulfinate anion, generating arylsulfonyl radical A. Aarylsulfonyl radical A undergoes radical addition to phenylacetylene 2a to generate intermediate B. Reduced-state eosin Y (EY-.) and intermediate B undergo single-electron reduction to generate intermediate C. Intermediate C is protonated to give monosubstituted product D. Finally, product D undergoes addition with arylsulfinate to give intermediate F. Intermediate F is reacted with alkaline conditions to give final product 3. .

[0012] In this invention, the entire reaction is carried out at room temperature and pressure, the reaction conditions are mild and easy to achieve, and the reaction time is short, resulting in low time cost.

[0013] The target product obtained by this invention is a disulfone ethylene compound, which is an attractive class of organosulfur compounds and an important skeletal structure in organic chemistry as a target molecule and a general intermediate. It has wide applications in organic chemistry, agrochemistry, materials science and medicinal chemistry. Detailed Implementation

[0014] Specific Example 1: Phenylacetylene (0.2 mmol), sodium p-toluenesulfinate (0.5 mmol), trifluoroacetic acid (0.4 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 57.7 mg of a white solid (E)-4,4'-(1-phenylethylene-1,2-disulfone)bis(toluene), with a yield of 70%. 1H NMR(400 MHz, CDCl3) δ 7.75 (s, 1H), 7.44 (d, J = 8.0 Hz, 2H), 7.39 – 7.32 (m,3H), 7.23 – 7.14 (m, 6H), 6.91 (d, J = 7.6 Hz, 2H), 2.40 (s, 3H), 2.39 (s,3H); 13C NMR (125 MHz, CDCl3) δ 152.9, 145.8, 145.5, 137.7, 136.4, 133.2,130.3, 130.3, 130.1, 129.9, 129.9, 129.8, 129.8, 129.3, 129.3, 128.3, 128.3,127.8, 127.8, 127.1, 21.8, 21.8. HRMS (ESI) m / z: [M + H]+ Calcd forC13H13F3NO2+: 272.0893; found: 272.0888.

[0015] Specific Example 2: p-tert-butylphenylacetylene (0.2 mmol), sodium p-toluenesulfinate (0.5 mmol), trifluoroacetic acid (0.4 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 58.9 mg of a white solid (E)-4,4'-(1-(4-(tert-butyl)phenyl)ethylene-1,2-disulfonyl)bis(toluene), with a yield of 63%. 1 H NMR (400 MHz, CDCl3) δ 7.74 (s, 1H), 7.39 – 7.33 (m, 4H), 7.19 –7.13 (m, 4H), 7.11 (d, J = 8.0 Hz, 2H), 6.79 (d, J = 8.4 Hz, 2H), 2.38 (s,3H), 2.37 (s, 3H), 1.29 (s, 9H); 13 C NMR (125 MHz, CDCl3) δ 153.5, 153.1,145.7, 145.1, 138.0, 136.3, 133.4, 130.0, 130.0, 129.7, 129.7, 129.7, 129.7,129.2, 129.2,128.3, 128.3, 124.8, 124.8, 123.9, 34.8, 31.3, 31.3, 31.3, 21.8,21.7.

[0016] Specific Example 3: 0.2 mmol of p-fluorophenylacetylene, 0.5 mmol of sodium p-toluenesulfinate, 0.4 mmol of trifluoroacetic acid, and 0.4 mmol of cesium carbonate were added to 2.0 mL of toluene. The mixture was stirred under a nitrogen atmosphere and irradiated with 100 W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluented with hexane using a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 51.6 mg of a white solid (E)-4,4'-(1-(4-fluorophenyl)ethylene-1,2-disulfonyl)bis(toluene), with a yield of 60%. 1 HNMR (400 MHz, CDCl3) δ 7.76 (s, 1H), 7.50 (d, J = 8.0 Hz, 2H), 7.40 (d, J =8.0 Hz, 2H), 7.28 – 7.20 (m, 4H), 7.00 – 6.89 (m, 4H), 2.44 (s, 3H), 2.42 (s, 3H); 13 C NMR (125 MHz, CDCl3) δ 163.9(d, 1 J C-F = 250.1 Hz), 151.8, 146.0, 145.8,138.1, 136.3, 133.1, 132.5(d, 3 J C-F =8.9 Hz,2C), 130.0, 130.0, 130.0, 130.0,129.2, 129.2, 128.3, 128.3, 123.0(d, 4 J C-F =3.5 Hz), 115.3(d, 2 J C-F =21.9 Hz, 2C), 21.8, 21.8; 19 F NMR (470 MHz, CDCl3) δ -109.39.

[0017] Specific Example 4: 0.2 mmol of p-chlorophenylacetylene, 0.5 mmol of sodium p-toluenesulfinate, 0.4 mmol of trifluoroacetic acid, and 0.4 mmol of cesium carbonate were added to 2.0 mL of toluene. The mixture was stirred under a nitrogen atmosphere and irradiated with 100 W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluented with hexane using a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 49.1 mg of a white solid (E)-4,4'-(1-(4-chlorophenyl)ethylene-1,2-disulfonyl)bis(toluene), with a yield of 55%. 1 H NMR (400 MHz, CDCl3) δ 7.78 (s, 1H), 7.53 (d, J = 8.0 Hz, 2H), 7.43 (d, J =8.0 Hz, 2H), 7.32 – 7.21 (m, 6H), 6.92 (d, J = 8.0 Hz, 2H), 2.47 (s, 3H), 2.45 (s, 3H); 13 C NMR (125 MHz, CDCl3) δ 151.6, 146.1, 145.9, 138.1, 136.7,136.2, 133.1, 131.6, 131.6, 130.1, 130.1, 130.0, 130.0, 129.3, 129.3, 128.3,128.3, 128.3, 128.3, 125.6, 21.9, 21.8.

[0018] Specific Example 5: Ethynylpyridine (0.2 mmol), sodium p-toluenesulfinate (0.5 mmol), trifluoroacetic acid (0.4 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 40.5 mg of a white solid (E)-3-(1,2-di-p-toluenesulfonylvinyl)pyridine, with a yield of 49%. 1H NMR (400MHz, CDCl3) δ 8.68 (s, 1H), 8.20 – 7.99 (m, 1H), 7.84 (s, 1H), 7.59 – 7.48(m, 3H), 7.42 (d, J = 8.0 Hz, 2H), 7.38 – 7.26 (m, 5H), 2.48 (s, 3H), 2.45(s, 3H). 13 C NMR (125 MHz, CDCl3) δ 149.9, 149.0, 148.8, 146.5, 146.2, 138.9,138.4, 135.9, 132.5, 130.3,130.3, 130.2, 130.2, 130.2, 129.1, 129.1, 128.2,128.2, 127.9, 21.8, 21.8. HRMS (ESI) m / z: [M + H] + Calcd for C 13 H 13 F3NO2 + :272.0893; found: 272.0888.

[0019] Specific Example 6: 3-Bromophenylacetylene (0.2 mmol), sodium p-toluenesulfinate (0.5 mmol), trifluoroacetic acid (0.4 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 51.8 mg of a white solid (E)-4,4'-(1-(3-bromophenyl)ethylene-1,2-disulfonyl)bis(toluene), with a yield of 53%. 1 H NMR (400 MHz, CDCl3) δ 7.75 (s, 1H), 7.49 – 7.35 (m, 5H), 7.25 – 7.17 (m,4H), 7.11 – 7.02 (m, 1H), 6.86 (s, 1H), 6.82 (d, J = 7.6 Hz, 1H), 2.43 (s, 3H), 2.41 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 151.3, 146.2, 145.9, 138.6,136.0, 133.1, 133.1, 132.8, 132.5, 130.0, 130.0, 130.0, 130.0, 129.4, 129.4,129.2, 129.0, 128.3,128.3, 121.9, 21.9, 21.9.

[0020] Specific Example 7: 2-Fluorophenylacetylene (0.2 mmol), sodium p-toluenesulfinate (0.5 mmol), trifluoroacetic acid (0.4 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 51.6 mg of a white solid (E)-4,4'-(1-(2-fluorophenyl)ethylene-1,2-disulfonyl)bis(toluene), with a yield of 60%. 1 HNMR (400 MHz, CDCl3) δ 7.78 (s, 1H), 7.41 (d, J = 8.4 Hz, 3H), 7.32 – 7.18(m, 5H), 7.15 – 7.05 (m, 2H), 6.96 – 6.82 (m, 1H), 2.46 (s, 3H), 2.43 (s,3H); 13 C NMR (125 MHz, CDCl3) δ 159.6(d, 1 J C-F =250.0 Hz), 146.5, 146.0, 145.8,138.4, 135.9, 132.9, 132.4(d, 3 J C-F =8.8 Hz), 131.4, 130.1, 130.1, 129.8,129.8, 129.3, 129.3, 128.4, 128.4, 123.7(d, 4 J C-F =3.8 Hz), 115.4 (d, 2J C-F =15.0Hz), 115.2(d, 2 J C-F =21.3 Hz), 21.8, 21.8; 19 F NMR (470 MHz, CDCl3) δ -110.94.

[0021] Specific Example 8: 2-Methylphenylacetylene (0.2 mmol), sodium p-toluenesulfinate (0.5 mmol), trifluoroacetic acid (0.4 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 44.5 mg of a white solid (E)-4,4'-(1-(o-tolyl)ethylene-1,2-disulfonyl)bis(toluene), with a yield of 54%. 1 H NMR (400 MHz, CDCl3) δ 7.70 (s, 1H), 7.40 (d, J = 8.4 Hz, 2H), 7.33 (d, J = 8.4 Hz, 2H), 7.22 – 7.13 (m, 5H), 7.03 – 6.91 (m, 2H), 6.56 (d, J = 7.2Hz, 1H), 2.37 (s, 6H), 1.70 (s, 3H); 13 C NMR (125 MHz, CDCl3) δ 152.7, 146.0,145.7, 138.7, 137.9, 137.9, 136.2, 133.2, 130.3, 130.2, 130.0, 130.0, 129.9,129.9, 129.7, 129.7, 128.4, 128.4, 126.5, 125.0, 21.9, 21.8, 19.5.

[0022] Specific Example 9: p-Methoxyphenylacetylene (0.2 mmol), sodium p-toluenesulfinate (0.5 mmol), trifluoroacetic acid (0.4 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 44.2 mg of a white solid (E)-4,4'-(1-(4-(p-methoxy)phenyl)ethylene-1,2-disulfonyl)bis(toluene), with a yield of 50%. 1 H NMR (400 MHz, CDCl3) δ 7.71 (s, 1H), 7.47 (d, J = 8.4 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.24 – 7.15 (m, 4H), 6.91 (d, J = 8.4 Hz, 2H), 6.72(d, J = 8.4 Hz, 2H), 3.80 (s, 3H), 2.41 (s, 3H), 2.38 (s, 3H); 13 C NMR (125MHz, CDCl3) δ 161.2, 152.8, 145.7, 145.4, 137.5, 136.5, 133.6, 131.9, 131.9,129.9, 129.9, 129.9, 129.9, 129.2, 129.2, 128.3, 128.3, 118.9, 113.4, 113.4,55.4, 21.8, 21.8.

[0023] Specific Example 10: 0.2 mmol of p-trifluoromethylphenylacetylene, 0.5 mmol of sodium p-toluenesulfinate, 0.4 mmol of trifluoroacetic acid, and 0.4 mmol of cesium carbonate were added to 2.0 mL of toluene. The mixture was stirred under a nitrogen atmosphere and irradiated with 100 W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane using a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The eluents were then dried under vacuum to obtain 59.5 mg of a white solid (E)-4,4'-(1-(4-(trifluoromethyl)phenyl)ethylene-1,2-disulfonyl)bis(toluene), with a yield of 62%. 1 H NMR (400 MHz, CDCl3) δ 7.78 (s, 1H), 7.47 – 7.42 (m, 3H), 7.38(d, J = 8.0 Hz, 2H), 7.24 – 7.18 (m, 5H), 7.03 (d, J = 8.0 Hz, 2H), 2.41 (s, 6H). 13 C NMR (125 MHz, CDCl3) δ 151.2, 146.3, 146.0, 138.6, 136.0, 133.0,132.5(t, 2 J C-F = 32.5 Hz), 130.6(t, 1 J C-F = 130.6 Hz), 130.7, 130.7, 130.1,130.1, 130.1, 130.1, 129.3, 129.3, 128.3, 128.3, 124.8(t, 3 J C-F = 3.8 Hz, 2C),, 122.7, 21.9, 21.8. 19 F NMR (470 MHz, CDCl3) δ -62.9.

[0024] Specific Example 11: 0.2 mmol of p-methylphenylacetylene, 0.5 mmol of sodium p-toluenesulfinate, 0.4 mmol of trifluoroacetic acid, and 0.4 mmol of cesium carbonate were added to 2.0 mL of toluene. The mixture was stirred under a nitrogen atmosphere and irradiated with 100 W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluented with hexane using a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 61.3 mg of a white solid (E)-4,4'-(1-(p-toluene)ethylene-1,2-disulfonyl)bis(toluene), with a yield of 72%. 1 H NMR (400 MHz, CDCl3) δ 7.71 (s, 1H), 7.47 (d, J = 8.0 Hz, 2H), 7.38 (d, J = 8.0 Hz, 2H), 7.23 – 7.17 (m, 4H), 7.01 (d, J = 8.0 Hz, 2H), 6.83 (d, J =8.0 Hz, 2H), 2.41 (s, 3H), 2.39 (s, 3H), 2.34 (s, 3H); 13 C NMR (125 MHz, CDCl3) δ 153.0, 145.7, 145.5, 140.5, 137.5, 136.5, 133.4, 130.2, 130.2,129.9, 129.9, 129.8, 129.8, 129.3, 129.3, 128.6, 128.6, 128.3, 128.3, 124.1,21.8, 21.8, 21.6.

[0025] Specific Example Twelve: Phenylacetylene (0.2 mmol), sodium benzenesulfinate (0.5 mmol), trifluoroacetic acid (0.4 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 30.7 mg of a white solid (E)-(1-phenylvinyl-1,2-disulfone)diphenyl, with a yield of 40%. 1 H NMR (400 MHz, CDCl3) δ 7.80 (s, 1H), 7.58 (d, J = 8.0 Hz, 4H), 7.50 (d, J = 8.0 Hz, 2H),7.44 – 7.33 (m, 5H), 7.21 – 7.14 (m, 2H), 6.89 (d, J = 7.6 Hz, 2H); 13 C NMR(125 MHz, CDCl3) δ 153.1, 139.3, 137.8, 136.2, 134.6, 134.3, 130.3, 130.2,130.2, 129.3, 129.3,129.3, 129.3, 129.2, 129.2, 128.3, 128.3, 128.0, 128.0,126.9. HRMS (ESI) m / z: [M + H] + Calcd for C 13 H 13 F3NO2 + : 272.0893; found:272.0888.

[0026] Specific Example 13: Phenylacetylene (0.2 mmol), sodium p-fluorobenzenesulfinate (0.5 mmol), trifluoroacetic acid (0.4 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 54.6 mg of a white solid (E)-4,4'-(1-phenylethylene-1,2-disulfone)bis(fluorobenzene), with a yield of 65%. 1 H NMR (400MHz, CDCl3) δ 7.85 (s, 1H), 7.66 – 7.50 (m, 4H), 7.48 – 7.39 (m, 1H), 7.36 –7.27 (m, 2H), 7.18 – 7.06 (m, 4H), 6.96 (d, J = 7.2 Hz, 2H); 13 C NMR (125 MHz, CDCl3) δ 166.4(d, 1 J C-F = 257.4 Hz), 166.2 (d, 1 J C-F = 256.6 Hz), 153.0, 138.0,135.2(d, 4 J C-F = 2.5 Hz), 132.2(d, 3 J C-F = 10.0 Hz, 2C), 132.1(d, 4 J C-F = 2.5 Hz), 131.3(d, 3 J C-F = 8.8 Hz,2C), 130.6, 130.3, 130.3, 128.2, 128.2, 126.8, 116.7(d, 2 J C-F = 23.8 Hz, 2C), 116.7(d, 2 J C-F= 22.5 Hz, 2C); 19 F NMR (470 MHz, CDCl3) δ -101.1, -101.8.

[0027] Specific Example 14: Phenylacetylene (0.2 mmol), sodium p-chlorobenzenesulfinate (0.5 mmol), trifluoroacetic acid (0.4 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 56.8 mg of a white solid (E)-4,4'-(1-phenylethylene-1,2-disulfone)bis(chlorobenzene), with a yield of 63%. 1 H NMR (400MHz, CDCl3) δ 7.79 (s, 1H), 7.47 – 7.33 (m, 9H), 7.25 – 7.18 (m, 2H), 6.93 –6.87 (m, 2H); 13 C NMR (125 MHz, CDCl3) δ 153.0, 141.7, 141.3, 138.0, 137.5,134.6, 130.7, 130.7, 130.6, 130.3, 130.3, 129.8, 129.8, 129.6, 129.6, 129.6,129.6, 128.2, 128.2, 126.6.

[0028] Specific Example 15: Phenylacetylene (0.2 mmol), sodium p-bromobenzenesulfinate (0.5 mmol), trifluoroacetic acid (0.4 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 53.9 mg of a white solid (E)-4,4'-(1-phenylethylene-1,2-disulfone)bis(bromobenzene), with a yield of 50%. 1H NMR (400MHz, CDCl3) δ 7.78 (s, 1H), 7.59 – 7.47 (m, 4H), 7.44 – 7.30 (m, 5H), 7.26 –7.18 (m, 2H), 6.90 (d, J = 7.6 Hz, 2H); 13 C NMR (125 MHz, CDCl3) δ 153.0,138.1, 138.0, 135.2, 132.6, 132.6, 132.6, 132.6, 130.7, 130.7, 130.6, 130.4,130.3, 130.3, 130.0, 129.8, 129.8, 128.2, 128.2, 126.6.

[0029] Specific Example 16: 1-Phenylacetylene (0.2 mmol), sodium p-toluenesulfinate (0.5 mmol), trifluoroacetic acid (0.4 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 25.6 mg of a white solid (E)-4,4'-(1-phenylprop-1-ene-1,2-disulfone)bis(toluene), with a yield of 30%. 1 H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 8.0 Hz, 2H), 7.33 – 7.26 (m, 3H), 7.17 (d, J = 8.0 Hz, 2H), 7.11 – 7.05 (m, 2H), 7.02 (d, J = 8.0 Hz, 2H), 6.96(d, J = 8.0 Hz, 2H), 2.40 (s, 3H), 2.33 (s, 3H), 2.13 (s, 3H); 13C NMR (125MHz, CDCl3) δ 151.3, 143.5, 141.4, 138.3, 137.9, 136.9, 136.8, 129.4, 129.4,129.3, 129.3, 128.6, 128.6, 128.5, 128.5, 128.4, 128.4, 128.3, 128.0, 128.0,21.7, 21.4, 18.3.

[0030] Specific Example 17: Phenylacetylene (0.2 mmol), sodium p-toluenesulfinate (0.5 mmol), trifluoroacetic acid (0.4 mmol), and potassium carbonate (0.8 mmol) were added to chlorobenzene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 28.8 mg of a white solid (E)-4,4'-(1-phenylethylene-1,2-disulfone)bis(toluene), with a yield of 35%. 1H NMR(400 MHz, CDCl3) δ 7.75 (s, 1H), 7.44 (d, J = 8.0 Hz, 2H), 7.39 – 7.32 (m,3H), 7.23 – 7.14 (m, 6H), 6.91 (d, J = 7.6 Hz, 2H), 2.40 (s, 3H), 2.39 (s,3H); 13C NMR (125 MHz, CDCl3) δ 152.9, 145.8, 145.5, 137.7, 136.4, 133.2,130.3, 130.3, 130.1, 129.9, 129.9, 129.8, 129.8, 129.3, 129.3, 128.3, 128.3,127.8, 127.8, 127.1, 21.8, 21.8. HRMS (ESI) m / z: [M + H]+ Calcd forC13H13F3NO2+: 272.0893; found: 272.0888.

[0031] Specific Example 18: Phenylacetylene (0.2 mmol), sodium p-toluenesulfinate (0.5 mmol), trifluoroacetic acid (0.4 mmol), and sodium carbonate (0.6 mmol) were added to iodobenzene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 456 nm 20 W blue light for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 14.1 mg of a white solid (E)-4,4'-(1-styryl-1,2-disulfone)bis(toluene), with a yield of 17%. 1H NMR(400 MHz, CDCl3) δ 7.75 (s, 1H), 7.44 (d, J = 8.0 Hz, 2H), 7.39 – 7.32 (m,3H), 7.23 – 7.14 (m, 6H), 6.91 (d, J = 7.6 Hz, 2H), 2.40 (s, 3H), 2.39 (s,3H); 13C NMR (125 MHz, CDCl3) δ 152.9, 145.8, 145.5, 137.7, 136.4, 133.2,130.3, 130.3, 130.1, 129.9, 129.9, 129.8, 129.8, 129.3, 129.3, 128.3, 128.3,127.8, 127.8, 127.1, 21.8, 21.8. HRMS (ESI) m / z: [M + H]+ Calcd forC13H13F3NO2+: 272.0893; found: 272.0888.

[0032] Specific Example 19: Phenylacetylene (0.2 mmol), sodium p-toluenesulfinate (0.5 mmol), pentylene acid (0.4 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 456 nm 25 W blue light for 8 hours under methylene blue catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 38.7 mg of a white solid (E)-4,4'-(1-phenylethylene-1,2-disulfonyl)bis(toluene), with a yield of 47%. 1H NMR(400 MHz, CDCl3) δ 7.75 (s, 1H), 7.44 (d, J = 8.0 Hz, 2H), 7.39 – 7.32 (m,3H), 7.23 – 7.14 (m, 6H), 6.91 (d, J = 7.6 Hz, 2H), 2.40 (s, 3H), 2.39 (s,3H); 13C NMR (125 MHz, CDCl3) δ 152.9, 145.8, 145.5, 137.7, 136.4, 133.2,130.3, 130.3, 130.1, 129.9, 129.9, 129.8, 129.8, 129.3, 129.3, 128.3, 128.3,127.8, 127.8, 127.1, 21.8, 21.8. HRMS (ESI) m / z: [M + H]+ Calcd forC13H13F3NO2+: 272.0893; found: 272.0888.

[0033] Specific Example 20: Phenylacetylene (0.2 mmol), sodium p-toluenesulfinate (0.5 mmol), methanesulfonic acid (0.6 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 456 nm 75 W blue light for 12 hours under the catalysis of water-soluble eosin. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 39.5 mg of a white solid (E)-4,4'-(1-phenylethylene-1,2-disulfone)bis(toluene), with a yield of 48%. 1H NMR(400 MHz, CDCl3) δ 7.75 (s, 1H), 7.44 (d, J = 8.0 Hz, 2H), 7.39 – 7.32 (m,3H), 7.23 – 7.14 (m, 6H), 6.91 (d, J = 7.6 Hz, 2H), 2.40 (s, 3H), 2.39 (s,3H); 13C NMR (125 MHz, CDCl3) δ 152.9, 145.8, 145.5, 137.7, 136.4, 133.2,130.3, 130.3, 130.1, 129.9, 129.9, 129.8, 129.8, 129.3, 129.3, 128.3, 128.3,127.8, 127.8, 127.1, 21.8, 21.8. HRMS (ESI) m / z: [M + H]+ Calcd forC13H13F3NO2+: 272.0893; found: 272.0888.

[0034] Specific Example 21: Phenylacetylene (0.2 mmol), sodium p-toluenesulfinate (0.5 mmol), benzoic acid (0.2 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 6 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 37.9 mg of a white solid (E)-4,4'-(1-phenylethylene-1,2-disulfonyl)bis(toluene), with a yield of 46%. 1H NMR(400 MHz, CDCl3) δ 7.75 (s, 1H), 7.44 (d, J = 8.0 Hz, 2H), 7.39 – 7.32 (m,3H), 7.23 – 7.14 (m, 6H), 6.91 (d, J = 7.6 Hz, 2H), 2.40 (s, 3H), 2.39 (s,3H); 13C NMR (125 MHz, CDCl3) δ 152.9, 145.8, 145.5, 137.7, 136.4, 133.2,130.3, 130.3, 130.1, 129.9, 129.9, 129.8, 129.8, 129.3, 129.3, 128.3, 128.3,127.8, 127.8, 127.1, 21.8, 21.8. HRMS (ESI) m / z: [M + H]+ Calcd forC13H13F3NO2+: 272.0893; found: 272.0888.

[0035] Specific Example 22: Phenylacetylene (0.2 mmol), sodium p-toluenesulfinate (0.8 mmol), trifluoroacetic acid (0.4 mmol), and cesium carbonate (0.4 mmol) were added to toluene (2.0 mL). The mixture was stirred under a nitrogen atmosphere and irradiated with 100W blue light at 456 nm for 8 hours under tetrabromofluorescein catalysis. The mixture was filtered through a funnel, and the solvent was removed by rotary evaporation to obtain the residue. The residue was eluted with hexane as the eluent through a silica gel column. The eluents were collected according to the actual gradient and analyzed by TLC. The eluents containing the target product were combined, and the solvent was removed by rotary evaporation. The combined eluents were dried under vacuum to obtain 61.8 mg of a white solid (E)-4,4'-(1-phenylethylene-1,2-disulfone)bis(toluene), with a yield of 75%. 1H NMR(400 MHz, CDCl3) δ 7.75 (s, 1H), 7.44 (d, J = 8.0 Hz, 2H), 7.39 – 7.32 (m,3H), 7.23 – 7.14 (m, 6H), 6.91 (d, J = 7.6 Hz, 2H), 2.40 (s, 3H), 2.39 (s,3H); 13C NMR (125 MHz, CDCl3) δ 152.9, 145.8, 145.5, 137.7, 136.4, 133.2,130.3, 130.3, 130.1, 129.9, 129.9, 129.8, 129.8, 129.3, 129.3, 128.3, 128.3,127.8, 127.8, 127.1, 21.8, 21.8. HRMS (ESI) m / z: [M + H]+ Calcd forC13H13F3NO2+: 272.0893; found: 272.0888.

[0036] Conclusion: The embodiments of this invention use arylacetylene and sodium benzenesulfinate as reaction substrates, tetrabromofluorescein as photocatalyst, cesium carbonate as base and trifluoroacetic acid as organic acid, and toluene as solvent as the basis. Examples 1 to 11 use the substitution of Ar in arylacetylene with different substituents as variables. The results show that Ar is well-suited to the method of this invention when substituted with different substituents (such as methyl, methoxy, trifluoromethyl, halogen). Notably, Ar is also well-suited to the method of this invention when substituted with heterocycles. Examples 12 to 15 use the substitution of R in sodium benzenesulfinate with different substituents as variables. The results show that R is well-suited to the method of this invention when substituted with different substituents (such as methyl hydrogen atom, halogen, etc.). Notably, Ar is also well-suited to the method of this invention when substituted with endyne, and all yield disulfone ethylene compounds.

[0037] The method of this invention can directly synthesize the target product without separating intermediate products. The target product can be obtained simply by stirring and irradiating the reaction under normal pressure, which greatly simplifies the process. Moreover, there is less waste solution and no other polluting gases or liquids are emitted during the reaction. Therefore, this invention reduces the discharge of waste solution and has the advantages of protecting the environment and ensuring the health of operators. The alkenyl sulfone products prepared by the method of this invention are easy to obtain and can be widely used in the fields of medicine, biochemistry, and organic synthesis.

[0038] The above description is merely a preferred embodiment of the present invention. The scope of protection of the present invention is not limited to the above embodiments. All technical solutions falling within the scope of the present invention's concept are within the scope of protection of the present invention. It should be noted that for those skilled in the art, any improvements and modifications made without departing from the principles of the present invention should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a disulfone-based ethylene compound, characterized in that: The reaction includes the following steps: using arylacetylene and sodium benzenesulfinate as reaction substrates, adding a solvent (any one of toluene, chlorobenzene, or iodobenzene), and reacting under a nitrogen atmosphere in an organic acid and base buffer system, with a photocatalyst and blue light irradiation for 6-12 hours. The chemical reaction formula is as follows:

2. The -Ar is one of the following: phenyl, 4-methylphenyl, 2-methylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-fluorophenyl, 2-fluorophenyl, 4-chlorophenyl, 3-bromophenyl, 4-trifluoromethylphenyl, and pyridine.

3. The -R is one of: phenyl, 4-fluorophenyl, 4-chlorophenyl, and 4-bromophenyl; in, The organic acid is any one of pentanoic acid, trifluoroacetic acid, benzoic acid, and methanesulfonic acid; the base is any one of cesium carbonate, potassium carbonate, and sodium carbonate; and the photocatalyst is any one of tetrabromofluorescein, water-soluble eosin, and methylene blue.

4. The method for preparing a disulfone-based ethylene compound according to claim 1, characterized in that: The blue light intensity is in the range of 25-100W.

5. The method for preparing a disulfone-based ethylene compound according to claim 1, characterized in that: The addition amounts (molar parts) of each substance are as follows: arylacetylene 1-2 parts; sodium benzenesulfonate 2-4 parts; photocatalyst 1-5 mol%; organic acid 1-3 parts; alkali 1-4 parts.

6. The method for preparing a disulfone-based ethylene compound according to claim 1, characterized in that: After the reaction was completed, the mixture was filtered using a filter funnel and then evaporated using a rotary evaporator to remove the solvent and obtain the residue. The residue was then separated by column chromatography using a silica gel column and eluted with eluent. The eluent containing the target product was collected, and the eluents were combined and concentrated under vacuum to remove the solvent and obtain the target product.

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