METHOD FOR PREPARING CARBONYL SULFONE

Abstract

Disclosed is a method for preparing β-carbonyl sulfones. The method comprises: by taking an α-carbonyl diazo compound and sodium arylsulfinate as reaction substrates, cheap silver nitrate as an optimal catalyst, 1,10-phenanthroline as a ligand, and potassium persulfate as an oxidant, carrying out coupling reaction in a mixed solvent of acetonitrile and water to obtain a β-carbonyl sulfones compound. Compared with the prior art, the method has the following advantages: a wide range of reaction substrates, short reaction time, a relatively high reaction yield, a mild reaction condition, etc. In the present invention, non-toxic and harmless reagents are used as reaction raw materials, so that it has no harm to the environment and satisfies the requirements of contemporary green chemistry development. Post-reaction treatment is relatively simple, and is convenient for separation and purification. In addition, the reaction can achieve gram-scale synthesis, and lays a foundation for actual applications.

Claims

1. A method for preparing a β-carbonyl sulfone, comprising: reacting an α-carbonyldiazo compound with a sodium arylsulfinate, an N,N-bidentate compound as a ligand, a peroxide as an oxidant, in the presence of a metal compound as a catalyst, in a mixed solvent of an organic solvent and water, to obtain the β-carbonyl sulfone, wherein the α-carbonyldiazo compound has the following chemical formula: ##STR00021## R.sup.1 is selected from the group consisting of methyl, ethyl and hydrogen; R.sup.2 is alkoxy; the sodium arylsulfinate has the following chemical formula: ##STR00022## Ar is benzene or substituted benzene; and the β-carbonyl sulfone has the following chemical formula: ##STR00023##

2. The method according to claim 1, wherein the reaction is conducted at 40 to 90° C., for 4 to 12 hours.

3. The method according to claim 1, wherein the metal compound is a silver compound or a copper compound; the peroxide is potassium persulfate, sodium persulfate or ammonium persulfate, the N,N-bidentate compound is 1,10-phenanthroline, 2,2′-bipyridine, 4,7-dimethoxy-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, or 3,8-dibromo-1,10-phenanthroline.

4. The method according to claim 1, wherein a molar ratio of the catalyst to the sodium arylsulfinate is 1:10; a molar ratio of the oxidant to the sodium arylsulfinate is from 0.2:1 to 2:1; and a molar ratio of the ligand to the sodium arylsulfinate is 10:1; and a molar ratio of the α-carbonyldiazo compound to the sodium arylsulfinate is 2:1.

5. The method according to claim 1, wherein the reaction is conducted in the air.

6. The method according to claim 1, wherein the organic solvent is acetonitrile.

7. An application of a metal compound as a catalyst in the reaction of an α-carbonyldiazo compound and a sodium arylsulfinate to prepare a β-carbonyl sulfone, the metal compound is a silver compound or a copper compound.

8. The application according to claim 7, wherein the reaction is carried out in the presence of an N,N-bidentate compound and a peroxide, in a mixed solvent of an organic solvent and water; wherein a molar ratio of the metal compound is 10% of the sodium arylsulfinate; and a molar ratio of the α-carbonyldiazo compound to the sodium arylsulfinate is 2:1.

9. The application according to claim 8, wherein a molar ratio of the peroxide to the sodium arylsulfinate is from 0.2:1 to 2:1; and a molar ratio of the N,N-bidentate compound is 10% of the sodium arylsulfinate.

10. The β-carbonyl sulfone is prepared by the method according to claim 1.

Description

EXAMPLES OF THE INVENTION

[0023] The following further describes the present invention with reference to the examples: reacting an α-carbonyldiazo compound with a sodium arylsulfinate, an N,N-bidentate compound as a ligand, a peroxide as an oxidant, in the presence of a metal compound as a catalyst, in the mixed solvent of an organic solvent and water, to obtain the β-carbonyl sulfone.

[0024] The catalyst, the oxidant, ligands, sodium benzenesulfinate, sodium 4-methylbenzene sulfinate, sodium 4-fluorobenzene sulfinate, sodium 4-chlorobenzene sulfinate and the organic solvent of the present invention are all commercialized products and can be purchased directly. Diazo compounds are prepared with corresponding alcohols or amines as starting materials according to their different structures

Example 1

[0025] ##STR00004##

[0026] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2a (1.0 mmol, 114.1 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3aa, in a yield 80%. When the reaction was scaled up to 10 mmol (compound 1a), the yield of target product 3aa was still 74%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0027] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.97-7.95 (m, 2H), 7.72-7.68 (m, 1H), 7.61-7.57 (m, 2H), 4.17-4.12 (m, 4H), 1.19 (t, J=7.1 Hz, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 162.2, 138.7, 134.2, 129.2, 128.5, 62.3, 61.0, 13.8. HRMS (ESI-TOF): Anal. Calcd. For C.sub.10H.sub.12O.sub.4S+Na.sup.+: 251.0349, Found: 251.0353. IR (neat, cm.sup.−1): υ 3066, 2984, 2926, 2852, 1736, 1447, 1276, 1149.

Example 2

[0028] ##STR00005##

[0029] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2b (1.0 mmol, 128.1 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3ab, in a yield 76%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0030] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.97-7.94 (m, 2H), 7.71-7.67 ((m, 1H), 7.60-7.57 (m, 2H), 4.99-4.93 (m, 1H), 4.12 (s, 2H), 1.15 (d, J=6.3 Hz, 6H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 161.6, 138.6, 134.1, 129.0, 128.3, 70.2, 61.0, 21.2. HRMS (ESI-TOF): Anal. Calcd. For C.sub.11H.sub.14O.sub.4S+Na.sup.+: 265.0505, Found: 265.0511. IR (neat, cm.sup.−1): υ 3067, 2984, 2940, 2881, 1731, 1448, 1278, 1151.

Example 3

[0031] ##STR00006##

[0032] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2c (1.0 mmol, 142.2 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3ac, in a yield 70%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0033] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.96-7.94 (m, 2H), 7.71-7.67 ((m, 1H), 7.60-7.56 (m, 2H), 4.15 (s, 2H), 4.07 (t, J=6.7 Hz, 2H), 1.55-1.48 (m, 2H), 1.31-1.22 (m, 2H), 0.87 (t, J=7.4 Hz, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 162.2, 138.6, 134.1, 129.0, 128.2, 65.9, 60.7, 30.0, 18.6, 13.3. HRMS (ESI-TOF): Anal. Calcd. For C.sub.12H.sub.16O.sub.4S+Na.sup.+: 279.0662, Found: 279.0668. IR (neat, cm.sup.−1): υ 2960, 2937, 2875, 1736, 1448, 1279, 1150, 1083.

Example 4

[0034] ##STR00007##

[0035] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2d (1.0 mmol, 168.2 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3ad, in a yield 72%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0036] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.97-7.94 (m, 2H), 7.71-7.67 ((m, 1H), 7.60-7.56 (m, 2H), 4.76-4.57 (m, 1H), 4.12 (s, 2H), 1.77-1.64 (m, 4H), 1.53-1.48 (m, 1H), 1.37-1.18 (m, 5H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 161.7, 138.7, 134.1, 129.1, 128.4, 75.0, 61.1, 31.0, 25.0, 23.3. HRMS (ESI-TOF): Anal. Calcd. For C.sub.14H.sub.18O.sub.4S+Na.sup.+: 305.0818, Found: 305.0822. IR (neat, cm.sup.−1): υ 3065, 2937, 2860, 1731, 1448, 1281, 1150, 1083.

Example 5

[0037] ##STR00008##

[0038] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2e (1.0 mmol, 190.2 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3ae, in a yield 87%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0039] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.89-7.87 (m, 2H), 7.65-7.61 (m, 1H), 7.53-7.49 (m, 2H), 7.28-7.24 (m, 2H), 7.22-7.18 (m, 1H), 7.13-7.11 (m, 2H), 4.25 (t, J=7.1 Hz, 2H), 4.09 (s, 2H), 2.82 (t, J=7.1 Hz, 2H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 162.1, 138.4, 136.8, 134.1, 129.0, 128.6, 128.3, 128.2, 126.5, 66.4, 60.6, 34.3. HRMS (ESI-TOF): Anal. Calcd. For C.sub.16H.sub.16O.sub.4S+Na.sup.+: 327.0662, Found: 327.0652. IR (neat, cm.sup.−1): υ 3005, 2968, 2935, 1737, 1448, 1270, 1161, 1082.

Example 6

[0040] ##STR00009##

[0041] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.3 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2f (1.0 mmol, 240.3 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3af, in a yield 87%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0042] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.94 (d, J=8.0 Hz, 1H), 7.88-7.83 (m, 3H), 7.73 (d, J=8.0 Hz, 1H), 7.61-7.57 (m, 1H), 7.52-7.45 (m, 4H), 7.39-7.35 (m, 1H), 7.27-7.26 (m, 1H), 4.38 (t, J=7.3 Hz, 2H), 4.09 (s, 2H), 3.29 (t, J=7.3 Hz, 2H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 162.2, 138.5, 134.2, 133.7, 132.7, 131.7, 129.1, 128.8, 128.3, 127.5, 127.0, 126.2, 125.6, 125.4, 123.2, 66.0, 60.8, 31.6. HRMS (ESI-TOF): Anal. Calcd. For C.sub.20H.sub.18O.sub.4S+Na.sup.+: 377.0818, Found: 377.0817. IR (neat, cm.sup.−1): υ 3060, 3005, 2968, 2935, 1733, 1448, 1270, 1160.

Example 7

[0043] ##STR00010##

[0044] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2g (1.0 mmol, 186.3 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3ag, in a yield 72%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0045] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.97-7.94 (m, 2H), 7.69-7.67 ((m, 1H), 7.60-7.56 (m, 2H), 4.18-4.14 (m, 2H), 4.11 (s, 2H), 0.93-0.89 (m, 2H), 0.01 (s, 9H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 162.3, 138.7, 134.1, 129.1, 128.4, 64.7, 60.9, 17.0, −1.8. HRMS (ESI-TOF): Anal. Calcd. For C.sub.13H.sub.20O.sub.4SSi+Na.sup.+: 323.0744, Found: 323.0743. IR (neat, cm.sup.−1): ν 3066, 2954, 2899, 1736, 1448, 1274, 1150, 1084.

Example 8

[0046] ##STR00011##

[0047] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2h (1.0 mmol, 196.2 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3ah, in a yield 81%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0048] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.93-7.90 (m, 2H), 7.68-7.65 (m, 1H), 7.57-7.53 (m, 2H), 7.14-7.13 (m, 1H), 6.92-6.90 (m, 1H), 6.80-6.79 (m, 1H), 4.28 (t, J=6.8 Hz, 2H), 4.13 (s, 2H), 3.05 (t, J=6.8 Hz, 2H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 162.1, 138.8, 138.5, 134.2, 129.1, 128.3, 126.9, 125.6, 124.0, 66.1, 60.7, 28.6. HRMS (ESI-TOF): Anal. Calcd. For C.sub.14H.sub.14O.sub.4S.sub.2+Na.sup.+: 333.0226, Found: 333.0226. IR (neat, cm.sup.−1): υ 3104, 3006, 2962, 2853, 1736, 1449, 1270, 1160.

Example 9

[0049] ##STR00012##

[0050] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2i (1.0 mmol, 176.2 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3ai, in a yield 66%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0051] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.86-7.83 (m, 2H), 7.64-7.60 (m, 1H), 7.49-7.45 (m, 2H), 7.35-7.31 (m, 3H), 7.25-7.23 (m, 2H), 5.09 (s, 2H), 4.15 (s, 2H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 162.1, 138.4, 134.3, 134.1, 129.1, 128.54, 128.47, 128.4, 128.3, 67.8, 60.8. HRMS (ESI-TOF): Anal. Calcd. For C.sub.15H.sub.14O.sub.4S+Na.sup.+: 313.0505, Found: 313.0507. IR (neat, cm.sup.−1): υ 3065, 3006, 2943, 2849, 1737, 1448, 1273, 1148.

Example 10

[0052] ##STR00013##

[0053] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2j (1.0 mmol, 252.3 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3aj, in a yield 80%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0054] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.76-7.74 (m, 2H), 7.57-7.53 (m, 1H), 7.40-7.36 (m, 2H), 7.32-7.24 (m, 10H), 6.82 (s, 1H), 4.17 (s, 2H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 161.4, 138.7, 138.2, 134.1, 129.1, 128.4, 128.3, 128.1, 127.1, 78.9, 60.9. HRMS (ESI-TOF): Anal. Calcd. For C.sub.21H.sub.18O.sub.4S+Na.sup.+: 389.0818, Found: 389.0804. IR (neat, cm.sup.−1): ν 3063, 3007, 2929, 2853, 1738, 1448, 1265, 1149.

Example 11

[0055] ##STR00014##

[0056] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2k (1.0 mmol, 158.2 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3ak, in a yield 74%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0057] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.97-7.91 (m, 2H), 7.72-7.68 (m, 1H), 7.61-7.57 (m, 2H), 4.18 (t, J=6.5 Hz, 2H), 4.14 (s, 2H), 3.36 (t, J=6.5 Hz, 1H), 3.30 (s, 3H), 1.85-1.79 (m, 2H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 162.2, 138.6, 134.2, 129.1, 128.3, 68.4, 63.4, 60.8, 58.5, 28.4. HRMS (ESI-TOF): Anal. Calcd. For C.sub.12H.sub.16O.sub.5S+Na.sup.+: 295.0611, Found: 295.0619. IR (neat, cm.sup.−1): υ 3065, 2930, 2878, 1737, 1448, 1278, 1151, 1083.

Example 12

[0058] ##STR00015##

[0059] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2l (1.0 mmol, 128.2 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3a1, in a yield 71%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0060] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.91-7.88 (m, 2H), 7.71-7.67 ((m, 1H), 7.60-7.56 (m, 2H), 4.11 (dq, J=0.6, 7.2 Hz, 2H), 4.06 (q, J=7.2 Hz, 1H), 1.58 (d, J=7.2 Hz, 3H), 1.15 (t, J=7.2 Hz, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 166.1, 136.9, 134.1, 129.2, 128.9, 65.3, 62.1, 13.7, 11.6. HRMS (ESI-TOF): Anal. Calcd. For C.sub.11H.sub.14O.sub.4S+Na.sup.+: 265.0505, Found: 265.0509. IR (neat, cm.sup.−1): υ 3066, 2985, 2942, 1734, 1448, 1260, 1145, 1083.

Example 13

[0061] ##STR00016##

[0062] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2m (1.0 mmol, 142.2 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3am, in a yield 66%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0063] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.91-7.88 (m, 2H), 7.71-7.67 ((m, 1H), 7.60-7.56 (m, 2H), 4.11 (dq, J=0.6, 7.2 Hz, 2H), 4.06 (q, J=7.2 Hz, 1H), 1.58 (d, J=7.2 Hz, 3H), 1.15 (t, J=7.2 Hz, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 166.1, 136.9, 134.1, 129.2, 128.9, 65.3, 62.1, 13.7, 11.6. HRMS (ESI-TOF): Anal. Calcd. For C.sub.12H.sub.16O.sub.4S+Na.sup.+: 279.0662, Found: 279.0669. IR (neat, cm.sup.−1): υ 3069, 2979, 2852, 1731, 1451, 1187, 1162, 1079.

Example 14

[0064] ##STR00017##

[0065] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2n (1.0 mmol, 358.5 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3an, in a yield 61%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0066] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.96-7.94 (m, 2H), 7.71-7.68 (m, 1H), 7.60-7.57 (m, 2H), 4.71-4.65 (m, 1H), 4.09 (s, 2H), 2.47-2.40 (m, 1H), 2.11-2.01 (m, 1H), 1.92-1.91 (m, 1H), 1.77-1.13 (m, 16H), 0.98-0.94 (m, 1H), 0.85 (s, 3H), 0.82 (s, 3H), 0.71-0.68 (m, 1H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 221.0, 161.7, 138.6, 134.1, 129.0, 128.4, 75.8, 61.1, 54.0, 51.1, 47.6, 44.3, 36.3, 35.7, 35.4, 34.8, 33.3, 31.3, 30.5, 28.0, 26.8, 21.6, 20.3, 13.6, 12.0. HRMS (ESI-TOF): Anal. Calcd. For C.sub.27H.sub.36O.sub.5S+Na.sup.+: 495.2176, Found: 495.2160. IR (neat, cm.sup.−1): υ 3010, 2928, 2848, 1742, 1448, 1279, 1160, 1086.

Example 15

[0067] ##STR00018##

[0068] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1b (0.5 mmol, 89.1 mg), 2a (1.0 mmol, 114.1 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3ba, in a yield 63%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0069] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.82 (d, J=8.3 Hz, 2H), 7.37 (d, J=8.3 Hz, 2H), 4.15 (q, J=7.1 Hz, 2H), 4.10 (s, 2H), 2.46 (s, 3H), 1.20 (t, J=7.1 Hz, 3H). .sup.13C NMR (100 MHz, CDCl.sup.3) δ 162.4, 145.3, 135.7, 129.7, 128.5, 62.3, 61.0, 21.6, 13.8. HRMS (ESI-TOF): Anal. Calcd. For C11H14O4S+Na.sup.+: 265.0505, Found: 265.0515. IR (neat, cm.sup.−1): υ 2983, 2929, 2854, 1737, 1400, 1276, 1147, 1084.

Example 16

[0070] ##STR00019##

[0071] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1c (0.5 mmol, 91.1 mg), 2a (1.0 mmol, 114.1 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3ca, in a yield 62%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0072] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.01-7.96 (m, 2H), 7.30-7.24 (m, 2H), 4.18-4.13 (m, 4H), 1.21 (t, J=7.1 Hz, 3H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 166.0 (d, J=257.2 Hz), 162.2, 134.6 (d, J=3.2 Hz), 131.5 (d, J=9.8 Hz), 116.4 (d, J=22.8 Hz), 62.3, 60.9, 13.8. HRMS (ESI-TOF): Anal. Calcd. For C.sub.10H.sub.11FO.sub.4S+Na.sup.+: 269.0254, Found: 269.0258. IR (neat, cm.sup.−1): υ 3107, 3073, 2986, 2943, 1736, 1494, 1292, 1147.

Example 17

[0073] ##STR00020##

[0074] Compound AgNO.sub.3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K.sub.2S.sub.2O.sub.8 (0.25 mmol, 67.6 mg), 1d (0.5 mmol, 91.1 mg), 2a (1.0 mmol, 114.1 mg), MeCN/H.sub.2O=10:1 (2.0 mL). The reaction mixture was heated at 70° C. for 4 h, and the reaction was then quenched with saturated Na.sub.2SO.sub.3 solution and the mixture was extracted with ethyl acetate (20 mL×3). The organic layers were combined and dried with anhydrous Na.sub.2SO.sub.4. Removal of the organic solvent followed by flash column chromatographic purification using petroleum and ethyl acetate to obtain β-carbonyl sulfones 3da, in a yield 65%. The analytical data of the prepared product are as follows. The data of the actual synthetic products are consistent with the theoretical analysis.

[0075] .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.92-7.88 (m, 2H), 7.58-7.55 (m, 2H), 4.18-4.13 (m, 4H), 1.21 (t, J=7.1 Hz, 2H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 162.1, 140.9, 137.0, 130.0, 129.4, 62.4, 60.7, 13.7. HRMS (ESI-TOF): Anal. Calcd. For C.sub.10H.sub.11.sup.35ClO.sub.4S+Na.sup.+: 284.9959, Found: 284.9968; Anal. Calcd. For C.sub.10H.sub.11.sup.37ClO.sub.4S+Na.sup.+: 286.9929, Found: 286.9917. IR (neat, cm.sup.−1): υ 3093, 2985, 2941, 1736, 1475, 1277, 1151, 1084.