在一密闭的反应封管中加入0.2 mmol α-羰基二硫缩烯酮衍生物1、0.6 mmol碘化铵、二甲基亚砜0.9 mL、普通乙腈1.5 mL, 封管后反应混合物在135 ℃的温度下搅拌反应24 h.反应停止后, 反应液中加入10 mL水, 再用二氯甲烷(10 mL×3) 萃取, 有机相用无水Na2SO4干燥, 减压抽滤后脱去溶剂, 粗产品经柱层析提纯, 展开剂为石油醚和乙酸乙酯(V/V＝15/1).
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基苯乙酮(2a):黄色固体. m.p. 110~112 ℃; 1H NMR (CDCl3, 500 MHz) δ: 7.75~7.73 (m, 2H), 7.47~7.44 (m, 1H), 7.40~7.37 (m, 2H), 3.53 (dd, J＝7.25, 5.75 Hz, 2H), 3.46 (dd, J＝7.5, 5.5 Hz, 2H), 2.06 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 191.7, 175.6, 138.8, 130.8, 128.4, 127.5, 115.5, 40.6, 25.4, 18.7; HRMS calcd for C12H12OS3 268.0050, found 268.0056.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基邻甲氧基苯乙酮(2b): 黄色液体. 1H NMR (CDCl3, 500 MHz) δ: 7.40~7.37 (m, 1H), 7.28~7.26 (m, 1H), 6.98 (t, J＝7.25 Hz, 1H), 6.91 (d, J＝8.5, 1H), 3.82 (s, 3H), 3.60 (t, J＝6.5 Hz, 2H), 3.46 (t, J＝6.5 Hz, 2H), 2.07 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 192.6, 176.5, 156.5, 130.7, 130.5, 127.9, 120.2, 117.3, 110.6, 55.5, 40.9, 35.2, 18.4; HRMS calcd for C13H14O2S3 298.0156, found 298.0151.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基对甲氧基苯乙酮(2c): 黄色固体. m.p. 121~123 ℃; 1H NMR (CDCl3, 500 MHz) δ: 7.85~7.82 (m, 2H), 6.90~6.87 (m, 2H), 3.83 (s, 3H), 3.50 (dd, J＝7.5, 5.5 Hz, 2H), 3.37 (dd, J＝7.5, 5.5 Hz, 2H), 2.09 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 190.4, 172.4, 162.1, 131.2, 130.8, 115.8, 112.8, 55.2, 40.4, 35.5, 18.6; HRMS calcd for C13H14O2S3 298.0156, found 298.0152.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基间甲氧基苯乙酮(2d): 黄色液体; 1H NMR (CDCl3, 500 MHz) δ: 7.35~7.27 (m, 3H), 7.02~7.00 (m, 1H), 3.83 (s, 3H) 3.56 (dd, J＝7.25, 5.75 Hz, 2H), 3.38 (dd, J＝7.25, 5.75 Hz, 2H), 2.09 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 191.5, 175.8, 158.8, 140.2, 128.6, 121.0, 117.2, 115.6, 113.3, 55.3, 40.7, 35.4, 21.3, 18.8; HRMS calcd for C13H14O2S3 298.0156, found 298.0159.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基对甲基苯乙酮(2e): 黄色液体. H NMR (CDCl3, 500 MHz) δ: 7.70 (d, J＝7.5 Hz, 2H), 7.20 (d, J＝7.5 Hz, 3H), 3.53 (t, J＝6.25 Hz, 2H), 3.38 (t, J＝6.25 Hz, 2H), 2.39 (s, 3H), 2.09 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 191.6, 174.2, 141.6, 135.9, 128.8, 128.3, 115.8, 40.5, 35.5, 21.5, 18.7; HRMS calcd for C13H14OS3 282.0207, found 282.0212.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基间甲基苯乙酮(2f): 黄色液体; 1H NMR (CDCl3, 500 MHz) δ: 7.57~7.55 (m, 2H), 7.29~7.28 (m, 2H), 3.55 (dd, J＝7.5, 5.5 Hz, 2H), 3.40 (dd, J＝7.5, 5.5 Hz, 2H), 2.39 (s, 3H), 2.10 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 192.2, 175.0, 138.9, 137.3, 131.8, 129.1, 127.4, 125.7, 115.8, 40.6, 35.5, 21.3, 18.8; HRMS calcd for C13H14OS3 282.0207, found 282.0204.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基邻甲基苯乙酮(2g): 黄色固体. m.p. 120~122 ℃; 1H NMR (CDCl3, 500 MHz) δ: 7.30~7.27 (m, 1H), 7.25~7.24 (m, 1H), 7.20~7.17 (m, 2H), 3.58 (dd, J＝7.25, 5.75 Hz, 2H), 3.35 (dd, J＝7.25, 5.75 Hz, 2H), 2.30 (s, 3H), 2.04 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 194.2, 177.8, 140.4, 134.7, 129.9, 128.9, 126.2, 124.7, 116.1, 41.0, 35.1, 19.3, 18.5; HRMS calcd for C13H14OS3 282.0207, found 282.0201.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基-1-(3′, 4′-二氧亚甲基)苯乙酮(2h): 黄色固体. m.p. 115~117 ℃; 1H NMR (CDCl3, 500 MHz) δ: 7.42 (dd, J＝8, 1.5 Hz, 1H), 7.30 (d, J＝1.5 Hz, 1H), 6.80 (d, J＝8.5 Hz, 1H), 3.63 (d, J＝8.5 Hz, 1H), 6.00 (s, 2H), 3.50 (dd, J＝7.25, 5.25 Hz, 2H), 3.37 (dd, J＝7.5, 5.5 Hz, 2H), 2.10 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 190.2, 172.9, 150.4, 147.1, 132.6, 124.9, 115.7, 109.4, 107.5, 101.6, 40.5, 35.7, 18.8; HRMS calcd for C13H12O3S3 311.9949, found 311.9944.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基-1-对苯基苯乙酮(2i): 黄色液体; 1H NMR (DMSO-d6, 500 MHz) δ: 7.75~7.73 (m, 6H), 7.52~7.49 (m, 2H), 7.43~7.40 (m, 1H), 3.63 (dd, J＝7.5, 5.5 Hz, 2H), 3.49 (dd, J＝7.5, 5.5 Hz, 2H), 2.09 (s, 3H); 13C NMR (125 MHz, DMSO-d6) δ: 190.6, 176.0, 142.4, 139.2, 137.9, 129.0, 128.8, 128.0, 126.8, 126.0, 114.3, 40.6, 35.4, 18.4; HRMS calcd for C18H16OS3 344.0363, found 344.0369.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基对氯苯乙酮(2j):黄色液体; 1H NMR (CDCl3, 500 MHz) δ: 7.74~7.71 (m, 2H), 7.38~7.36 (m, 2H), 3.57 (dd, J＝7.5, 5.5 Hz, 2H), 3.40 (dd, J＝7.25, 5.75 Hz, 2H), 2.07 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 190.4, 177.1, 137.2, 137.1, 130.2, 127.8, 115.2, 40.8, 35.5, 18.8; HRMS calcd for C12H11ClOS3 301.9661, found 301.9667.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基邻氯苯乙酮(2k): 黄色固体. m.p. 176~178 ℃; 1H NMR (CDCl3, 500 MHz) δ: 7.38~7.37 (m, 1H), 7.34~7.30 (m, 1H), 7.29~7.26 (m, 2H), 3.63 (dd, J＝7.5, 6 Hz, 2H), 3.39 (dd, J＝7.5, 6 Hz, 2H), 2.09 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 191.0, 180.1, 140.3, 130.5, 129.9, 129.2, 127.5, 126.2, 115.5, 41.2, 35.2, 18.5; HRMS calcd for C12H11ClOS3 301.9661, found 301.9669.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基对溴苯乙酮(2l): 黄色固体. m.p. 139~141 ℃; 1H NMR (CDCl3, 500 MHz) δ: 7.66~7.63 (m, 2H), 7.54~7.51 (m, 2H), 3.56 (dd, J＝7.25, 5.75 Hz, 2H), 3.39 (dd, J＝7.5, 5.5 Hz, 2H), 2.06 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 190.5, 177.3, 137.6, 130.7, 130.2, 125.5, 115.0, 40.8, 35.4, 18.8; HRMS calcd for C12H11BrOS3 345.9155, found 345.9159.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基邻溴苯乙酮(2m): 黄色固体. m.p. 181~183 ℃; 1H NMR (CDCl3, 500 MHz) δ: 7.57 (d, J＝8 Hz, 1H), 7.36~7.33 (m, 1H), 7.28~7.24 (m, 2H), 3.65 (t, J＝6.5 Hz, 2H), 3.40 (t, J＝6.75 Hz, 2H), 2.11 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 191.9, 180.5, 142.6, 132.6, 130.3, 127.8, 127.0, 119.6, 115.5, 41.5, 35.5, 18.9; HRMS calcd for C12H11BrOS3 345.9155, found 345.9151.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基对碘苯乙酮(2n): 黄色固体. m.p. 158~160 ℃; 1H NMR (CDCl3, 500 MHz) δ: 7.76~7.74 (m, 2H), 7.51~7.48 (m, 2H), 3.56 (dd, J＝7.25, 5.75 Hz, 2H), 3.39 (dd, J＝7.25, 5.75 Hz, 2H), 2.07 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 190.7, 177.4, 138.2, 136.7, 130.2, 115.0, 98.0, 40.8, 35.4, 18.9; HRMS calcd for C12H11IOS3 393.9017, found 393.9021.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基邻碘苯乙酮(2o): 黄色固体. m.p. 180~182 ℃; 1H NMR (CDCl3, 500 MHz) δ: 7.83 (dd, J＝8, 1 Hz, 1H), 7.40~7.37 (m, 1H), 7.23 (dd, J＝7.5, 1.5 Hz, 1H), 7.11~7.08 (m, 1H), 3.66 (dd, J＝7.5, 6 Hz, 2H), 3.42 (dd, J＝7.5, 6 Hz, 2H), 2.11 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 193.1, 180.5, 146.1, 138.7, 130.0, 127.5, 127.1, 114.7, 92.8, 41.3, 35.3, 18.8; HRMS calcd for C12H11IOS3 393.9017, found 393.9023.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基对氟苯乙酮(2p):黄色固体. m.p. 101~103 ℃; 1H NMR (CDCl3, 500 MHz) δ: 7.84~7.80 (m, 2H), 7.10~7.05 (m, 2H), 3.56 (dd, J＝7.5, 5.5 Hz, 2H), 3.40 (dd, J＝7.5, 5.5 Hz, 2H), 2.08 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 190.3, 176.1, 164.3 (J＝251.3 Hz), 134.8 (J＝2.5 Hz), 131.2 (J＝8.8 Hz), 115.3, 114.6 (J＝21.3 Hz), 40.7, 35.5, 18.7; HRMS calcd for C12H11FOS3 285.9956, found 285.9951.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基-1-(3, 5-二溴)苯乙酮(2q): 黄色液体. H NMR (CDCl3, 500 MHz) δ: 7.79 (d, J＝1 Hz, 2H), 7.75 (s, 1H), 3.61 (t, J＝6.5 Hz, 2H), 3.42 (t, J＝6.5 Hz, 2H), 2.11 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 188.6, 180.0, 142.3, 135.9, 130.1, 122.2, 114.5, 41.0, 35.5, 19.0; HRMS calcd for C12H10Br2OS3 425.8240, found 425.8246.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基-1-(3, 4-二氯)苯基乙酮(2r): 黄色液体; 1H NMR (CDCl3, 500 MHz) δ: 7.82 (d, J＝2 Hz, 1H), 7.58 (dd, J1＝7.5 Hz, J2＝2 Hz, 1H), 7.44 (d, J＝8.5 Hz, 1H), 3.56 (dd, J＝7.5, 6 Hz, 2H), 3.38 (dd, J＝7.5, 5.5 Hz, 2H), 2.06 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 188.8, 179.0, 138.6, 134.8, 131.7, 130.4, 129.5, 127.8, 114.4, 40.8, 35.4, 18.8; HRMS calcd for C12H10Cl2OS3 335.9271, found 335.9267.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基-1-(3-氟-2, 6-二氯)苯乙酮(2s): 黄色液体. H NMR (CDCl3, 500 MHz) δ: 7.29~7.28 (m, 1H), 7.11 (t, J＝8.5 Hz, 1H), 3.70 (t, J＝5.75 Hz, 2H), 3.44 (t, J＝6 Hz, 2H), 2.21 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 187.0, 182.8, 156.8 (d, J＝248.8 Hz), 141.3, 128.6 (d, J＝7.5 Hz), 126.0 (d, J＝3.8 Hz), 119.0 (d, J＝20 Hz), 116.7 (d, J＝22.5 Hz), 114.3, 41.3, 35.3, 18.2; HRMS calcd for C12H9Cl2FOS3 353.9177, found 353.9183.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基-1-噻吩基乙酮(2t): 黄色液体; 1H NMR (CDCl3, 500 MHz) δ: 8.27 (d, J＝3 Hz, 1H), 7.59 (d, J＝4.5 Hz, 1H), 7.10 (t, J＝4 Hz, 1H), 3.55 (t, J＝6.25 Hz, 2H), 3.35 (t, J＝6.25 Hz, 2H), 2.29 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 180.3, 179.2, 141.6, 134.8, 133.9, 127.3, 114.3, 41.0, 34.9, 19.3; HRMS calcd for C18H16OS3 344.0363, found 344.0369.
2-(1, 3-二硫戊环-2-亚基)-2-硫甲基-1-(6-甲氧基)萘乙酮(2u): 黄色液体. H NMR (CDCl3, 500 MHz) δ: 8.32 (s, 1H), 7.85 (dd, J＝21.5, 8.5 Hz, 2H), 7.74 (d, J＝8.5 Hz, 1H), 7.18 (t, J＝7.8 Hz, 2H), 3.95 (s, 3H), 3.57 (t, J＝6.25 Hz, 2H), 3.43 (t, J＝6.25 Hz, 2H), 2.11 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 191.6, 174.0, 159.2, 136.3, 133.8, 130.8, 129.8, 127.6, 126.3, 126.0, 119.3, 116.1, 105.7, 55.4, 40.6, 35.6, 18.9; HRMS calcd for C17H16O2S3 348.0312, found 348.0316.
2-[(苯基)(硫甲基)甲叉基]-1, 3-二噻烷(4a):黄色液体; 1H NMR (CDCl3, 500 MHz) δ: 7.48~7.46 (m, 2H), 7.38~7.35 (m, 2H), 7.28~7.25 (m, 1H), 3.47~3.42 (m, 4H), 2.08 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 141.5, 139.7, 128.9, 128.2, 127.3, 118.8, 39.2, 37.6, 17.1; HRMS calcd for C11H12S3 240.0101, found 240.0106.
2-[(4-氟苯基)(硫甲基)甲叉基]-1, 3-二噻烷(4b):黄色液体; 1H NMR (CDCl3, 500 MHz) δ: 7.46~7.42 (m, 2H), 7.07~7.02 (m, 2H), 3.46~3.43 (m, 4H), 2.06 (s, 3H); 13C NMR (125 MHz, CDCl3) δ: 161.7 (J＝246.25 Hz), 137.5 (J＝3.75 Hz), 130.7 (J＝7.5 Hz), 117.6, 115.2 (J＝21.3 Hz), 39.2, 37.7, 17.1; HRMS calcd for C11H11FS3 258.0007, found 258.0001.
化学慧定制合成事业部摘录
