正文 茯苓的化學成分研究(2 / 3)

化合物4 無定形粉末,HREI-MS m/z 443[M-H]-。1H-NMR(pyridine-d5,300 MHz) δ:5.94(1H,s,H-7),5.25(1H,dd,J=7.5,10.5 Hz,H-23),5.21(1H,dd,J=7.5,10.5 Hz,H-22),4.93(1H,m,H-3),1.15(3H,s,H-19),1.02(3H,d,J=6.6 Hz,H-28),0.96(3H,d,J=6.5 Hz,H-21),0.86~0.84(6H,d,J=6.0 Hz,H-26,27),0.63(3H,s,H-18);13C-NMR(pyridine-d5,150 MHz) δ:199.1(C-6),164.1(C-7),135.2(C-22),132.4 (C-23),120.3(C-8),79.8 (C-5),75.0(C-9),66.8(C-3),56.1(C-17),56.0 (C-14),45.3(C-13),43.1(C-24),42.2(C-10),40.6(C-20),40.6(C-12),38.2(C-4),33.3(C-25),31.5(C-2),28.9 (C-11),28.3(C-16),26.4(C-1),22.7(C-15),21.3 (C-21),20.4(C-27),20.1(C-19),19.8 (C-26),17.9(C-28),12.4(C-18)。參考文獻[5-6]中的數據,化合物4鑒定為3β,5α,9α-三羥基麥角甾-7,22-二烯-6-酮。

化合物5 白色針狀晶體(甲醇),ESI-(-)-MS m/z 395[M-H]-。1H-NMR(pyridine-d5,300 MHz) δ:5.16(1H,s,H-7),5.25~5.21 (2H,t,J=12.0 Hz,H-22,23),1.26(3H,s,H-19),1.06(3H,d,J=6.6 Hz,H-21),0.96(3H,d,J=6.6 Hz,H-28),0.86(3H,d, J=6.6 Hz,H-27),0.84(3H,d,J=6.6 Hz,H-26),0.60(3H,s,H-18);13C-NMR(pyridine-d5,125 MHz) δ:210.2(C-3),139.6 (C-8),136.2(C-22),132.1 (C-23),117.5(C-7),56.1(C-17),52.2(C-14),49.0 (C-9),44.4(C-4),43.5 (C-13),43.1(C-24),43.0 (C-2),40.8(C-20),39.5(C-12),38.8 (C-5),38.3(C-1),34.6(C-10),33.4(C-25),30.0(C-6),28.5(C-16),22.9(C-15),21.9 (C-11),21.4(C-26),20.2(C-27),19.8 (C-21),17.8(C-28),12.3 (C-19),12.3(C-18)。參考文獻[7]中的數據,化合物5鑒定為麥角甾-7,22-二烯-3-酮。

化合物6 白色針狀晶體,ESI-(+)-MS m/z 413[M+H]+。1H-NMR(pyridine-d5,300 MHz) δ:5.74 (1H,br s,H-7),5.29~5.22(2H,m,H-22,23),4.32(1H,s,H-3),3.03(1H,d,J=12.3 Hz,H-6),1.69(3H,s,H-19),1.08(3H,d,J=6.0 Hz,H-21),0.96(3H,d, J=3.3 Hz,H-28),0.91-0.80(6H,m,H-26,27),0.67(3H,s,H-18);13C-NMR (pyridine-d5,125 MHz) δ:141.5(C-8),136.2 (C-22),132.1 (C-23),120.5(C-7),76.1(C-9),74.2(C-6),67.6(C-3),56.1(C-17),52.2 (C-14),43.8(C-13),43.7 (C-10),43.1(C-24),42.0(C-20),40.9(C-12),39.9(C-4),38.0(C-5),33.8(C-25),33.3(C-1),32.6(C-2),28.5(C-16),23.5(C-11),22.4 (C-15),21.4 (C-21),20.1 (C-26),19.8(C-27),18.8(C-19),17.8(C-28),12.5(C-18)。 參考文獻[8]中的數據,化合物6鑒定為6,9-環氧麥角甾-7,22-二烯-3β-醇。

化合物7 白色針狀晶體(甲醇),ESI-(-)-MS m/z 395[M-H]-。1H-NMR (pyridine-d5,300 MHz) δ:5.72(1H,br s,H-4),5.29~5.22(2H,m,H-22,23),1.21(3H,s,H-19),1.02(3H,d,J=6.6 Hz,H-21),0.92(3H,d,J=6.6 Hz,H-28),0.84(3H,d,J=6.6 Hz,H-26),0.86(3H,d,J=6.6 Hz,H-27),0.70(3H,s,H-18);13C-NMR (pyridine-d5,125 MHz) δ:199.7 (C-3),171.8(C-5),138.1 (C-22),129.4 (C-23),123.7(C-4),56.0(C-14),55.9(C-17),53.8(C-9),43.1 (C-20),42.4 (C-13),41.9(C-24),39.6(C-12),36.3(C-1),35.6(C-8),34.6(C-10),34.0 (C-2),32.9(C-6),32.7(C-7),31.5(C-25),28.1(C-16),24.2(C-15),21.0(C-11),20.5(C-27),19.4(C-26),18.8 (C-21),17.6(C-28),17.4 (C-19),11.9(C-18)。參考文獻[4]中的數據,化合物7鑒定為麥角甾-4,22-二烯-3-酮。

化合物8 白色針狀晶體(甲醇),ESI-(+)-MS m/z 453[M+Na]+。1H-NMR (pyridine-d5,400 MHz) δ:5.76(1H,dd,J=4.8,2.4 Hz,H-7),5.27(1H,dd,J=15.2,7.6 Hz,H-23),5.19(1H,dd,J=15.2,7.6 Hz,H-22) ,4.83(1H,m,H-3),4.32(1H,br s,H-6),0.67(3H,s,H-18),1.52(3H,s,H-19),1.04(3H,d,J=6.4 Hz,H-21),0.97(3H,d,J=6.8 Hz,H-28),0.88(3H,d, J=6.8 Hz,H-27),0.87(3H,d, J=6.8 Hz,H-26);13C-NMR(pyridine-d5,125 MHz) δ:33.6(C-1),32.4(C-2),67.4(C-3),40.1 (C-4),75.9(C-5),74.1(C-6),120.3(C-7),141.3(C-8),43.5(C-9),37.8(C-10),22.2 (C-11),39.7(C-12),42.8(C-13),55.0(C-14),23.3(C-15),28.3(C-16),55.9(C-17),12.3 (C-18),18.6(C-19),40.7(C-20),21.2(C-21),136.0 (C-22),131.9(C-23),43.1(C-24),33.1 (C-25),19.9(C-26),19.6(C-27),17.6 (C-28)。參考文獻[5-6]中的數據,化合物8鑒定為麥角甾-7,22-二烯-3β,5α,6β-三醇。

化合物9 白色粉末,mp 229~231 ℃。ESI-(+)-MS m/z 413[M+H]+。1H-NMR(pyridine-d5,500 MHz) δ:5.21~5.17(3H,m,H-7,22,23),4.32(1H,m,H-3),3.05(1H,t,J=12.5 Hz,H-6),0.65(3H,s,H-18),1.05(3H,s,H-19),0.95(3H,d,J=5.0 Hz,H-21),0.85(3H,d,J=5.0 Hz,H-28),0.82(3H,d,J=5.0 Hz,H-27),0.79(3H,d,J=5.0 Hz,H-26);13C-NMR(pyridine-d5,125 MHz) δ:32.6(C-1),30.6(C-2),67.6(C-3),39.9 (C-4),76.1(C-5),74.2(C-6),120.5(C-7),141.5(C-8),43.7(C-9),38.0(C-10),22.4(C-11),40.9(C-12),43.0(C-13),55.2(C-14),23.4(C-15),28.5 (C-16),56.1(C-17),12.5(C-18),18.8(C-19),40.0(C-20),21.4(C-21),136.2(C-22),132.1 (C-23),41.9 (C-24),33.3(C-25),20.1(C-26),19.8 (C-27),17.8(C-28)。參考文獻[9]中的數據,化合物9鑒定為麥角甾-7,22-二烯-5,6-環氧-3-醇。