Diphenyl sulfone compounds and their preparation methods

Abstract

The present invention discloses a diaryl sulfone compound and a preparation method thereof, comprising the following steps: under an argon atmosphere, adding a tert-butyl 3-(phenylsulfinyl)propionate compound and a phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound into a Schlenk tube, successively adding cesium carbonate, potassium fluoride, 18-crown-6, and then adding the solvent DME, and reacting at room temperature for 4 hours; after the reaction is completed, performing extraction, chromatographic separation, and drying to obtain the target product. The reaction conditions are mild, the operation is simple, and the reaction does not require the use of expensive transition metal catalysts. Using inexpensive and readily available cesium carbonate as the base, potassium fluoride as the fluorine source, and ethylene glycol dimethyl ether as the reaction solvent, the arylation reaction of sulfite anions is realized. This method provides a new route for the preparation of various functionalized diaryl sulfones.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic compound synthesis and applications, and particularly relates to a diaryl sulfone compound and a preparation method thereof. Background Art

[0002] Sulfone motifs are widely present in various bioactive compounds, natural products, and some marketed drugs. For example, sulfone compounds such as dapsone and its derivatives are the main components of drugs used to treat leprosy on the market (Wiley-VCH Verlag: Weinheim, Germany, 2012.); amicarbazone, which is commonly used as a herbicide, also contains an aryl sulfone skeleton (J. Med. Chem. 2011, 54, 1587.). Given the important status and wide application of sulfone compounds, extensive research has been conducted on the synthesis of sulfones, especially those containing aryl structures.

[0003] There are many methods for the synthesis of sulfone compounds. The most common methods are to oxidize sulfur-containing compounds using strong oxidants (J. Chem. Rev. 2019, 1, 99.), and to obtain biaryl sulfones by using transition metal-catalyzed cross-coupling reactions of sulfinates with aryl boronic acids or aryl halides (ACS Catal. 2021, 11, 4169.). However, these synthesis strategies have serious defects. For example, (1) the use of strong oxidants limits the compatibility of substrate functional groups; (2) due to the incomplete oxidation of sulfides, sulfone by-products are usually generated; (3) expensive transition metal catalysts, relatively harsh reaction conditions, and higher reaction temperatures are required during the use of transition metal-catalyzed coupling. Therefore, although significant progress has been made in the synthesis of sulfone compounds, we still hope to develop a synthesis method for aryl sulfone compounds that is simple to operate, mild in conditions, and does not require the participation of transition metals. Summary of the Invention

[0004] The purpose of the present invention is to provide a synthesis and preparation method for diaryl sulfone compounds, which is simple and feasible, low in cost, and easy to purify. The present invention provides a method that uses inexpensive and readily available cesium carbonate as a base and potassium fluoride as a fluorine source to achieve the arylation reaction of sulfinate anions without a transition metal catalyst. The reaction conditions are mild, the operation is simple, and the reaction does not require the use of expensive transition metal catalysts. This method provides a new route for the preparation of various functionalized diaryl sulfones.

[0005] To achieve the above purpose, the present invention adopts the following technical solutions:

[0006] A diaryl sulfone compound, the general structural formula of which is:

[0007]

[0008] Wherein R1 is hydrogen, alkyl, alkoxy, halogen or trifluoromethyl; R2 is hydrogen, alkyl, alkoxy, halogen or trifluoromethyl.

[0009] The preparation method of the diaryl sulfone compound of the present invention comprises the following steps: Under an argon atmosphere, add the tert-butyl 3-(phenylsulfinyl)propionate compound and the phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound into a 10 mL Schlenk tube, successively add cesium carbonate, potassium fluoride, 18-crown-6, then add a solvent, and react at room temperature for 4 hours; After the reaction is completed, extract, chromatographically separate, and dry to obtain the target product. The reaction equation is as follows:

[0010]

[0011] The general formula of the tert-butyl 3-(phenylsulfinyl)propionate compound is:

[0012]

[0013] The structural general formula of the phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound is:

[0014]

[0015] Wherein R1 is hydrogen, alkyl, alkoxy, halogen or trifluoromethyl; R2 is hydrogen, alkyl, alkoxy, halogen or trifluoromethyl.

[0016] Furthermore, the molar ratio of the tert-butyl 3-(phenylsulfinyl)propionate compound to the phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound is 3:1.

[0017] Furthermore, the dosage of cesium carbonate is 12 times the molar amount of the phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound.

[0018] Furthermore, the dosage of potassium fluoride is 2 times the molar amount of the phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound.

[0019] Furthermore, the dosage of 18-crown-6 is 2 times the molar amount of the phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound.

[0020] Furthermore, the solvent is 1,2-dimethoxyethane. Based on the molar amount of 0.1 mmol of the phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound, the dosage of the solvent is 1 mL.

[0021] Furthermore, the extractant used for extraction is ethyl acetate.

[0022] Further, the eluent used in the chromatographic separation is ethyl acetate and petroleum ether with a volume ratio of 1:10.

[0023] Advantages of the present invention: The present invention provides a new approach for the preparation of various functionalized diaryl sulfones. This reaction uses inexpensive and readily available cesium carbonate as the base and potassium fluoride as the fluorine source to achieve the arylation reaction of sulfite anions without a transition metal catalyst. The reaction conditions are mild, without the need for high temperature and strong oxidants, the operation is simple, the method is efficient, the cost is low, and it is easy to purify, enriching the new process for constructing diaryl sulfone compounds under transition-metal-free catalysis, and is of great significance for the further research and application of aryl sulfone compounds. Detailed implementation manners

[0024] The following combines specific embodiments to further illustrate the present invention. It should be understood that the following embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. Those skilled in the art can make some non-essential improvements and adjustments based on the content of the above invention.

[0025] Example 1

[0026] The structural formula of the compound (4-tolyl)phenyl sulfone in this example is:

[0027]

[0028] The preparation method is as follows: Under an argon atmosphere, 80.4 mg (0.3 mmol) of tert-butyl 3-(p-tolylsulfinyl)propionate compound, 29.8 mg (0.1 mmol) of phenyl 2-(trimethylsilyl)trifluoromethanesulfonate, 391 mg (1.2 mmol) of cesium carbonate, 11.6 mg (0.2 mmol) of potassium fluoride, 53 mg (0.2 mmol) of 18-crown-6, and 1 mL of ethylene glycol dimethyl ether were successively added to a 10 mL Schlenk tube, and the reaction was carried out at room temperature for 4 hours; after the reaction was completed, it was extracted with ethyl acetate, concentrated under reduced pressure, and then chromatographically separated (silica gel 200-300 mesh, eluent: gradient elution with ethyl acetate / petroleum ether, ratio 1:10), dried to obtain a white solid with a yield of 82%; 1 H NMR (600 MHz, CDCl3) δ 7.95–7.91 (m, 2H), 7.83 (d, J = 8.3 Hz, 2H), 7.58–7.52 (m, 1H), 7.49 (dd, J = 8.3, 6.8 Hz, 2H), 7.32–7.28 (m, 2H), 2.39 (s, 3H) ppm. 13 C NMR (151 MHz, CDCl3) δ 144.2, 142.0, 138.7, 133.0, 129.9, 129.2, 127.7, 127.5, 21.6 ppm.

[0029] Example 2

[0030] The structural formula of the compound (2,4-dimethylphenyl)phenyl sulfone in this example is:

[0031]

[0032] The preparation method is as follows: Under an argon atmosphere, 84.6 mg (0.3 mmol) of tert-butyl 3-(2,4-dimethylbenzenesulfinyl)propionate compound, 29.8 mg (0.1 mmol) of phenyl 2-(trimethylsilyl)trifluoromethanesulfonate, 391 mg (1.2 mmol) of cesium carbonate, 11.6 mg (0.2 mmol) of potassium fluoride, 53 mg (0.2 mmol) of 18-crown-6, and 1 mL of ethylene glycol dimethyl ether were successively added to a 10 mL Schlenk tube and reacted at room temperature for 4 hours; after the reaction, extraction was carried out with ethyl acetate, and after concentration under reduced pressure, chromatographic separation was carried out (silica gel 200 - 300 mesh, eluent: gradient elution with ethyl acetate / petroleum ether, ratio 1:10), and drying gave a white solid with a yield of 73%; 1 H NMR(600MHz,CDCl3)δ8.10(d,J=8.1Hz,1H),7.85(d,J=7.0Hz,2H),7.55(t,J=7.4Hz,1H),7.48(t,J=7.8Hz,2H),7.19(d,J=8.2Hz,1H),7.03(s,1H),2.39(s,3H),2.36(s,3H)ppm. 13 C NMR(151MH z,CDCl3)δ144.5,141.7,137.8,136.0,133.4,132.8,129.7,129.0,127.5,127.1,21.3,20.1ppm.

[0033] Example 3

[0034] The structural formula of the compound (2,6-dimethylphenyl)phenyl sulfone in this example is:

[0035]

[0036] The preparation method is as follows: Under an argon atmosphere, 84.6 mg (0.3 mmol) of tert-butyl 3-(2,6-dimethylphenylsulfinyl)propionate compound, 29.8 mg (0.1 mmol) of phenyl 2-(trimethylsilyl)trifluoromethanesulfonate, 391 mg (1.2 mmol) of cesium carbonate, 11.6 mg (0.2 mmol) of potassium fluoride, 53 mg (0.2 mmol) of 18-crown-6, and 1 mL of 1,2-dimethoxyethane were successively added to a 10 mL Schlenk tube, and the reaction was carried out at room temperature for 4 hours; after the reaction was completed, extraction was carried out with ethyl acetate, and after concentration under reduced pressure, chromatographic separation was carried out (silica gel 200-300 mesh, eluent: gradient elution with ethyl acetate / petroleum ether, ratio 1:10), and drying gave a pale yellow solid with a yield of 70%; 1 1H NMR (600 MHz, CDCl3) δ 7.82–7.77 (m, 2H), 7.55 (t, J = 7.4 Hz, 1H), 7.48 (dd, J = 8.5, 7.1 Hz, 2H), 7.32 (t, J = 7.6 Hz, 1H), 7.13 (d, J = 7.6 Hz, 2H), 2.64 (s, 6H) ppm. 13 13C NMR (151 MHz, CDCl3) δ 143.3, 140.2, 136.8, 132.8, 132.7, 131.5, 128.9, 126.3, 22.9 ppm.

[0037] Example 4

[0038] The structural formula of the compound (4-ethylphenyl)phenyl sulfone in this example is:

[0039]

[0040] The preparation method is as follows: Under an argon atmosphere, 84.6 mg (0.3 mmol) of tert-butyl 3-(4-ethylphenylsulfinyl)propionate compound, 29.8 mg (0.1 mmol) of phenyl 2-(trimethylsilyl)trifluoromethanesulfonate, 391 mg (1.2 mmol) of cesium carbonate, 11.6 mg (0.2 mmol) of potassium fluoride, 53 mg (0.2 mmol) of 18-crown-6, and 1 mL of 1,2-dimethoxyethane were successively added to a 10 mL Schlenk tube, and the reaction was carried out at room temperature for 4 hours; after the reaction was completed, extraction was carried out with ethyl acetate, and after concentration under reduced pressure, chromatographic separation was carried out (silica gel 200-300 mesh, eluent: gradient elution with ethyl acetate / petroleum ether, ratio 1:10), and drying gave a white solid with a yield of 76%; 1H NMR (600MHz, CDCl3) δ7.94(d,J=7.1Hz,2H),7.85(d,J=8.4Hz,2H),7.54(t,J=7.4Hz,1H),7. 49(t,J=7.6Hz,2H),7.32(d,J=8.3Hz,2H),2.68(q,J=7.6Hz,2H),1.22(t,J=7.6Hz,3H)ppm. 13 C NMR (151MHz, CDCl3) δ150.3,142.0,138.9,133.0,129.2,128.8,127.8,127.5,28.8,15.0ppm.

[0041] Example 5

[0042] The structural formula of the compound (4-tert-butylphenyl)phenyl sulfone of the present embodiment is:

[0043]

[0044] The preparation method is as follows: under an argon atmosphere, 93.1 mg (0.3 mmol) of tert-butyl 3-(4-tert-butylphenylsulfinyl) propionate, 29.8 mg (0.1 mmol) of phenyl 2-(trimethylsilyl) trifluoromethanesulfonate, 391 mg (1.2 mmol) of cesium carbonate, 11.6 mg (0.2 mmol) of potassium fluoride, 53 mg (0.2 mmol) of 18-crown ether-6, and 1 mL of ethylene glycol dimethyl ether are added sequentially to a 10 mL Shrek tube, and the mixture is reacted at room temperature for 4 hours; after the reaction is completed, the mixture is extracted with ethyl acetate, concentrated under reduced pressure, and then chromatographed (silica gel 200-300 mesh, eluent: ethyl acetate / petroleum ether gradient elution, ratio 1:10), and dried to obtain a white solid with a yield of 82%; 1 H NMR (600MHz, CDCl3) δ7.95 (d, J = 7.7Hz, 2H), 7.86 (d, J = 8.5Hz, 2H), 7.52 (dd, J = 24.6, 7.7Hz, 5H), 1.31 (s, 9H) ppm. 13 C NMR (151MHz, CDCl3) δ157.1,142.0,138.6,133.0,129.2,127.6,127.5,126.3,35.2,31.0ppm.

[0045] Example 6

[0046] The structural formula of the compound (4-methoxyphenyl)phenyl sulfone of the present embodiment is:

[0047]

[0048] The preparation method is as follows: Under an argon atmosphere, 85.2 mg (0.3 mmol) of tert-butyl 3-(4-methoxyphenylsulfinyl)propionate compound, 29.8 mg (0.1 mmol) of phenyl 2-(trimethylsilyl)trifluoromethanesulfonate, 391 mg (1.2 mmol) of cesium carbonate, 11.6 mg (0.2 mmol) of potassium fluoride, 53 mg (0.2 mmol) of 18-crown-6, and 1 mL of 1,2-dimethoxyethane were successively added to a 10 mL Schlenk tube, and the reaction was carried out at room temperature for 4 hours; after the reaction was completed, extraction was carried out with ethyl acetate, and after concentration under reduced pressure, chromatographic separation was carried out (silica gel 200-300 mesh, eluent: gradient elution with ethyl acetate / petroleum ether, ratio 1:10), and drying gave a white solid with a yield of 65%; 1 1H NMR (600 MHz, CDCl3) δ 7.92 (d, J = 7.2 Hz, 2H), 7.88 (d, J = 8.9 Hz, 2H), 7.54 (t, J = 7.4 Hz, 1H), 7.48 (t, J = 7.4 Hz, 2H), 6.96 (d, J = 8.9 Hz, 2H), 3.84 (s, 3H) ppm. 13 13C NMR (151 MHz, CDCl3) δ 163.4, 142.4, 133.2, 132.8, 129.9, 129.2, 127.3, 114.5, 55.6 ppm.

[0049] Example 7

[0050] The structural formula of the compound (4-chlorophenyl)phenyl sulfone in this example is:

[0051]

[0052] The preparation method is as follows: Under an argon atmosphere, 86.4 mg (0.3 mmol) of tert-butyl 3-(4-chlorophenylsulfinyl)propionate compound, 29.8 mg (0.1 mmol) of phenyl 2-(trimethylsilyl)trifluoromethanesulfonate, 391 mg (1.2 mmol) of cesium carbonate, 11.6 mg (0.2 mmol) of potassium fluoride, 53 mg (0.2 mmol) of 18-crown-6, and 1 mL of 1,2-dimethoxyethane were successively added to a 10 mL Schlenk tube, and the reaction was carried out at room temperature for 4 hours; after the reaction was completed, extraction was carried out with ethyl acetate, and after concentration under reduced pressure, chromatographic separation was carried out (silica gel 200-300 mesh, eluent: gradient elution with ethyl acetate / petroleum ether, ratio 1:10), and drying gave a white solid with a yield of 67%; 11H NMR (600 MHz, CDCl3) δ 7.96–7.90 (m, 2H), 7.88 (d, J = 8.7 Hz, 2H), 7.58 (t, J = 7.4 Hz, 1H), 7.52 (t, J = 7.7 Hz, 2H), 7.49–7.46 (m, 2H) ppm. 13 13C NMR (151 MHz, CDCl3) δ 141.3, 140.2, 139.9, 133.4, 129.6, 129.4, 129.1, 127.7 ppm.

[0053] Example 8

[0054] The structural formula of the compound (4-bromophenyl)phenyl sulfone in this example is:

[0055]

[0056] The preparation method is as follows: Under an argon atmosphere, 99.6 mg (0.3 mmol) of tert-butyl 3-(4-bromobenzenesulfinyl)propionate compound, 29.8 mg (0.1 mmol) of phenyl 2-(trimethylsilyl)trifluoromethanesulfonate, 391 mg (1.2 mmol) of cesium carbonate, 11.6 mg (0.2 mmol) of potassium fluoride, 53 mg (0.2 mmol) of 18-crown-6, and 1 mL of ethylene glycol dimethyl ether were successively added to a 10 mL Schlenk tube and reacted at room temperature for 4 hours; after the reaction was completed, it was extracted with ethyl acetate, concentrated under reduced pressure, and then chromatographically separated (silica gel 200 - 300 mesh, eluent: gradient elution with ethyl acetate / petroleum ether, ratio 1:10), and dried to obtain a white solid with a yield of 57%; 1 1H NMR (600 MHz, CDCl3) δ 7.95–7.91 (m, 2H), 7.82–7.78 (m, 2H), 7.64 (d, J = 8.6 Hz, 2H), 7.58 (t, J = 7.4 Hz, 1H), 7.54–7.49 (m, 2H) ppm. 13 13C NMR (151 MHz, CDCl3) δ 141.2, 140.7, 133.5, 132.6, 129.4, 129.2, 128.5, 127.7 ppm.

[0057] Example 9

[0058] The structural formula of the compound (4-trifluoromethylphenyl)phenyl sulfone in this example is:

[0059]

[0060] The preparation method is as follows: Under an argon atmosphere, 99.6 mg (0.3 mmol) of tert-butyl 3-(4-trifluoromethylphenylsulfinyl)propionate compound, 29.8 mg (0.1 mmol) of phenyl(trimethylsilyl)trifluoromethanesulfonate, 391 mg (1.2 mmol) of cesium carbonate, 11.6 mg (0.2 mmol) of potassium fluoride, 53 mg (0.2 mmol) of 18-crown-6, and 1 mL of 1,2-dimethoxyethane were successively added to a 10 mL Schlenk tube, and the reaction was carried out at room temperature for 4 hours; after the reaction was completed, extraction was carried out with ethyl acetate, and after concentration under reduced pressure, chromatographic separation was carried out (silica gel 200 - 300 mesh, eluent: gradient elution with ethyl acetate / petroleum ether, ratio 1:10), and drying gave a white solid with a yield of 67%; 1 1H NMR (600 MHz, CDCl3) δ 8.08 (d, J = 8.2 Hz, 2H), 7.97 (d, J = 7.1 Hz, 2H), 7.77 (d, J = 8.2 Hz, 2H), 7.61 (t, J = 7.4 Hz, 1H), 7.54 (t, J = 7.8 Hz, 2H) ppm. 13 13C NMR (151 MHz, CDCl3) δ 145.3, 140.6, 134.9 (q, 2 J C-F = 33.2 Hz), 133.8, 129.5, 128.2, 127.9, 126.4, (q, 3 J C-F = 3.6 Hz) 123.1 (q, 1 J C-F = 273.3 Hz) ppm.

[0061] Example 10

[0062] The structural formula of the compound phenylnaphthyl sulfone in this example is as follows:

[0063]

[0064] The preparation method is as follows: Under an argon atmosphere, 91.2 mg (0.3 mmol) of tert-butyl 3-(naphthalenesulfinyl)propionate compound, 29.8 mg (0.1 mmol) of phenyl(trimethylsilyl)trifluoromethanesulfonate, 391 mg (1.2 mmol) of cesium carbonate, 11.6 mg (0.2 mmol) of potassium fluoride, 53 mg (0.2 mmol) of 18-crown-6, and 1 mL of 1,2-dimethoxyethane were successively added to a 10 mL Schlenk tube, and the reaction was carried out at room temperature for 4 hours; after the reaction was completed, extraction was carried out with ethyl acetate, and after concentration under reduced pressure, chromatographic separation was carried out (silica gel 200 - 300 mesh, eluent: gradient elution with ethyl acetate / petroleum ether, ratio 1:10), and drying gave a white solid with a yield of 68%; 11H NMR (600 MHz, CDCl3) δ 8.58 (d, J = 1.9 Hz, 1H), 8.03–7.96 (m, 3H), 7.93 (d, J = 8.7 Hz, 1H), 7.89–7.84 (m, 2H), 7.66–7.58 (m, 2H), 7.55 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.5 Hz, 2H) ppm. 13 13C NMR (151 MHz, CDCl3) δ 141.7, 138.5, 135.0, 133.2, 132.3, 129.7, 129.4, 129.3, 129.2, 129.1, 127.9, 127.7, 127.6, 122.7 ppm.

[0065] Example 11

[0066] The structural formula of the compound (3-methoxyphenyl)tolyl sulfone in this example is:

[0067]

[0068] The preparation method is as follows: Under an argon atmosphere, 80.4 mg (0.3 mmol) of tert-butyl 3-(p-tolylsulfinyl)propionate compound, 32.8 mg (0.1 mmol) of 6-methoxy-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 391 mg (1.2 mmol) of cesium carbonate, 11.6 mg (0.2 mmol) of potassium fluoride, 53 mg (0.2 mmol) of 18-crown-6, and 1 mL of 1,2-dimethoxyethane were successively added to a 10 mL Schlenk tube, and the reaction was carried out at room temperature for 4 hours; after the reaction was completed, extraction was carried out with ethyl acetate, and after concentration under reduced pressure, chromatography separation was carried out (silica gel 200 - 300 mesh, eluent: gradient elution with ethyl acetate / petroleum ether, ratio 1:10), and drying gave a white solid with a yield of 67%; 1 1H NMR (600 MHz, CDCl3) δ 7.82 (d, J = 8.3 Hz, 2H), 7.49 (d, J = 8.5 Hz, 1H), 7.44 (dd, J = 2.6, 1.6 Hz, 1H), 7.38 (t, J = 8.0 Hz, 1H), 7.29 (d, J = 8.0 Hz, 2H), 7.06 (dd, J = 8.3, 1.6 Hz, 1H), 3.83 (s, 3H), 2.40 (s, 3H) ppm. 13 13C NMR (151 MHz, CDCl3) δ 160.0, 144.2, 143.2, 138.7, 130.3, 129.9, 127.7, 119.8, 119.4, 112.1, 55.7, 21.5 ppm.

[0069] Example 12

[0070] The structural formula of the compound (3,4-dimethylphenyl)tolyl sulfone in this example is:

[0071]

[0072] The preparation method is as follows: Under an argon atmosphere, 80.4 mg (0.3 mmol) of tert-butyl 3-(p-tolylsulfinyl)propionate compound, 32.6 mg (0.1 mmol) of 4,5-dimethyl-2-(trimethylsilyl)phenyl trifluoromethanesulfonate, 391 mg (1.2 mmol) of cesium carbonate, 11.6 mg (0.2 mmol) of potassium fluoride, 53 mg (0.2 mmol) of 18-crown-6, and 1 mL of ethylene glycol dimethyl ether were successively added to a 10 mL Schlenk tube, and the reaction was carried out at room temperature for 4 hours; after the reaction was completed, extraction was carried out with ethyl acetate, and after concentration under reduced pressure, chromatographic separation was carried out (silica gel 200 - 300 mesh, eluent: gradient elution with ethyl acetate / petroleum ether, ratio 1:10), and drying gave a white solid with a yield of 70%; 1 H NMR (600 MHz, CDCl3) δ 7.81 (d, J = 8.3 Hz, 2H), 7.67 (s, 1H), 7.65 (d, J = 7.9 Hz, 1H), 7.28 (d, J = 8.0 Hz, 2H), 7.23 (d, J = 7.9 Hz, 1H), 2.38 (s, 3H), 2.29 (d, J = 3.5 Hz, 6H) ppm. 13 C NMR (151 MHz, CDCl3) δ 143.8, 142.6, 139.3, 139.2, 138.0, 130.4, 129.8, 128.3, 127.6, 125.1, 21.5, 19.9, 19.8 ppm.

[0073] Example 13

[0074] The structural formula of the compound tolylnaphthyl sulfone in this example is:

[0075]

[0076] The preparation method is as follows: Under an argon atmosphere, 80.4 mg (0.3 mmol) of tert-butyl 3-(p-tolylsulfinyl)propionate compound, 34.8 mg (0.1 mmol) of naphthalen-2-yl trifluoromethanesulfonate, 391 mg (1.2 mmol) of cesium carbonate, 11.6 mg (0.2 mmol) of potassium fluoride, 53 mg (0.2 mmol) of 18-crown-6, and 1 mL of 1,2-dimethoxyethane were successively added to a 10 mL Schlenk tube, and the reaction was carried out at room temperature for 4 hours; after the reaction was completed, extraction was carried out with ethyl acetate, and after concentration under reduced pressure, chromatographic separation was carried out (silica gel 200 - 300 mesh, eluent: gradient elution with ethyl acetate / petroleum ether, ratio 1:10), and drying gave a white solid with a yield of 48%; 1 1H NMR (600 MHz, CDCl3) δ 8.58–8.53 (m, 1H), 7.97 (d, J = 7.5 Hz, 1H), 7.94–7.82 (m, 5H), 7.65 - 7.65 (m, 2H), 7.29 (d, J = 8.1 Hz, 2H), 2.38 (s, 3H) ppm. 13 13C NMR (151 MHz, CDCl3) δ 144.2, 138.9, 138.8, 135.0, 132.3, 129.9, 129.6, 129.4, 129.0, 128.9, 127.9, 127.8, 127.6, 122.7, 21.6 ppm.

[0077] Example 14

[0078] The structural formula of the compound 5-(p-tolylsulfinyl)benzo[d][1,3]dioxole in this example is:

[0079]

[0080] The preparation method is as follows: Under an argon atmosphere, 80.4 mg (0.3 mmol) of 3-(trimethylsilyl)naphthalen-2-yl trifluoromethanesulfonate compound, 34.2 mg (0.1 mmol) of 6-(trimethylsilyl)benzo[1,3]dioxol-5-yl trifluoromethanesulfonate, 391 mg (1.2 mmol) of cesium carbonate, 11.6 mg (0.2 mmol) of potassium fluoride, 53 mg (0.2 mmol) of 18-crown-6, and 1 mL of 1,2-dimethoxyethane were successively added to a 10 mL Schlenk tube, and the reaction was carried out at room temperature for 4 hours; after the reaction was completed, extraction was carried out with ethyl acetate, and after concentration under reduced pressure, chromatographic separation was carried out (silica gel 200 - 300 mesh, eluent: gradient elution with ethyl acetate / petroleum ether, ratio 1:10), and drying gave a white solid with a yield of 68%; 11H NMR (600 MHz, CDCl3) δ 7.79 (d, J = 8.3 Hz, 2H), 7.52 (dd, J = 8.2, 1.8 Hz, 1H), 7.32–7.25 (m, 3H), 6.86 (d, J = 8.2 Hz, 1H), 6.03 (s, 2H), 2.39 (s, 3H) ppm. 13 13C NMR (151 MHz, CDCl3) δ 151.7, 148.3, 143.9, 139.1, 135.4, 129.9, 127.5, 123.4, 108.5, 107.8, 102.3, 21.5 ppm.

[0081] The foregoing has shown and described the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments, and what is described in the above embodiments and the specification is only to illustrate the principle of the present invention. Without departing from the spirit and scope of the present invention, the present invention will also have various changes and improvements, and these changes and improvements fall within the scope of the present invention claimed. The scope of protection claimed by the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing diaryl sulfone compounds, characterized in that It includes the following steps: Under an argon atmosphere, add the tert-butyl 3-(phenylsulfinyl)propionate compound and the phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound into a Schlenk tube, successively add cesium carbonate, potassium fluoride, 18-crown-6, and then add a solvent, and react at room temperature; after the reaction is completed, extract, chromatographically separate, and dry to obtain the target product. The reaction equation is as follows: ； The general formula of the tert-butyl 3-(phenylsulfinyl)propionate compound is: ； The structural general formula of the phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound is: ； wherein R1 is hydrogen, alkyl, alkoxy, halogen or trifluoromethyl; R2 is hydrogen, alkyl, alkoxy, halogen or trifluoromethyl; The molar ratio of the cesium carbonate to the phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound is 12:1; The molar ratio of the potassium fluoride to the phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound is 2:1; The molar ratio of the 18-crown-6 to the phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound is 2:1; The solvent is 1,2-dimethoxyethane.

2. The preparation method of the diaryl sulfone compound according to claim 1, wherein: The molar ratio of the tert-butyl 3-(phenylsulfinyl)propionate compound to the phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound is 3:

1.

3. The preparation method of the diaryl sulfone compound according to claim 1, characterized in that: Based on 0.1 mmol of the phenyl 2-(trimethylsilyl)trifluoromethanesulfonate compound, the amount of the solvent used is 1 mL.

4. The preparation method of the diaryl sulfone compound according to claim 1, characterized in that: The temperature of the reaction is room temperature, and the reaction time is 4 hours.

5. The preparation method of the diaryl sulfone compound according to claim 1, wherein: The extractant used for the extraction is ethyl acetate.

6. The preparation method of the diaryl sulfone compound according to claim 1, characterized in that: The eluent used for the chromatographic separation is ethyl acetate and petroleum ether with a volume ratio of 1:10.

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