化合物 5 白色針狀結晶(甲醇),mp 151~152 ℃,易溶於氯仿、丙酮、乙酸乙酯,微溶於石油醚、甲醇。紫外下有暗斑,香草醛濃硫酸顯紫紅色。1H,NMR(CDCl3, 300 MHz) δ:5.57(1H, br d, J=3.2 Hz, H,6), 5.38(1H, m, H,7), 5.20(2H, m, H,22, 23), 3.63(1H, m, H,3), 1.04(3H, d, J=6.6 Hz, H,21), 0.95(3H, s, H,19), 0.92(3H, d, J=6.8 Hz, H,28), 0.84(3H, d, J=4.5 Hz, H,26或27), 0.82(3H, d, J=4.5 Hz, H,26或 27), 0.63(3H, s, H,18);13C,NMR(CDCl3, 75 MHz)δ:141.3(C,8), 139.8(C,5), 135.6(C,22), 132.0(C,23), 119.6(C,6), 116.3(C,7), 70.5(C,3), 55.8(C,17), 54.5(C,14), 46.3(C,9), 42.8(C,13), 42.8(C,24), 40.8(C,4), 40.4(C,20), 39.1(C,12), 38.4(C,1), 37.0(C,10), 33.1(C,25), 32.0(C,2), 28.3(C,16), 23.0(C,15), 21.1(C,11), 21.1(C,21), 19.9(C,26), 19.6(C,27), 17.6(C,28), 16.3(C,19), 12.0(C,18)。以上數據與文獻[10]報道的數據一致,故化合物 5鑒定為麥角甾醇。
化合物 6 白色片狀結晶(石油醚),mp 181~182 ℃,易溶於石油醚、氯仿,難溶於甲醇、乙醇。香草醛,濃硫酸顯色,未加熱時顯粉紅色,加熱後顯紫紅色。1H,NMR(CDCl3, 300 MHz) δ:6.50(1H, d,J=8.5 Hz, H,7), 6.24(1H, d, J=8.5 Hz, H,6), 5.23(1H, dd, J=15.2, 8.1 Hz, H,23), 5.14(1H, dd, J=15.2, 7.5 Hz, H,22), 3.97(1H, m, H,3), 1.00(3H, d, J=6.5 Hz, H,21), 0.91(3H, d, J=6.6 Hz, H,28), 0.88(3H, br s, H,19), 0.83(3H, d, J=6.9 Hz, H,26), 0.82(3H, d, J=6.3 Hz, H,27), 0.81(3H, s, H,18);13C,NMR(CDCl3, 75 MHz) δ:135.4(C,6), 135.2(C,22), 132.3(C,23), 130.7(C,7), 82.1(C,5), 79.4(C,8), 66.4(C,3), 56.2(C,17), 51.7(C,14), 51.1(C,9), 44.5(C,13), 42.8(C,24), 39.7(C,20), 39.3(C,12), 36.9(C,4), 36.9(C,10), 34.7(C,1), 33.0(C,25), 30.1(C,2), 28.6(C,16), 23.4(C,11), 20.9(C,21), 20.6(C,15), 19.9(C,27), 19.6(C,26), 18.1(C,19), 17.5(C,28), 12.9(C,18)。以上數據與文獻[10]報道的數據一致,故化合物 6鑒定為麥角甾醇過氧化物。
化合物 7 白色針狀結晶(甲醇),mp 165~167 ℃,易溶於氯仿、丙酮,香草醛濃硫酸顯紫紅色。1H,NMR(CDCl3, 300 MHz) δ:6.59(1H, d, J=8.4 Hz, H,7), 6.28(1H, d, J=8.4 Hz, H,6), 5.43(1H, dd, J=5.9, 1.9 Hz, H,11), 5.25(1H, dd, J=15.2, 6.9 Hz, H,23), 5.16(1H, dd, J=15.2, 7.7 Hz, H,22), 4.01(1H, m, H,3), 1.09(3H,brs,H,19), 1.00(3H, d, J=6.6 Hz, H,21), 0.92(3H, d, J=6.8 Hz, H,28), 0.84(3H, d, J=4.8 Hz, H,27), 0.82(3H, d, J=4.8 Hz, H,26), 0.74(3H, s, H,18);13C,NMR(CDCl3, 75 MHz) δ:142.6(C,9), 135.5(C,6), 135.1(C,22), 132.4(C,23), 130.7(C,7), 119.7(C,11), 82.7(C,5), 78.3(C,8), 66.3(C,3), 55.9(C,17), 48.2(C,14), 43.6(C,13), 42.8(C,24), 41.2(C,12), 39.9(C,20), 38.0(C,10), 36.1(C,4), 33.1(C,25), 32.6(C,1), 30.6(C,2), 28.6(C,16), 25.5(C,19), 20.9(C,15), 20.7(C,21), 19.9(C,27), 19.6(C,26), 17.5(C,28), 13.0(C,18)。以上數據與文獻[13]報道的數據一致, 故化合物 7鑒定為(22E, 24R),5α, 8α,過氧化麥角甾,6, 9(11), 22,三烯,3β,醇。
化合物 8 白色針狀結晶(甲醇),易溶於石油醚、氯仿、丙酮,難溶於甲醇、乙醇,香草醛,濃硫酸顯紫紅色。1H,NMR(CDCl3, 500 MHz) δ:5.16(1H, m, H,7), 4.71(1H, s, H,28), 4.66(1H, d, J=1.2 Hz, H,28), 3.59(1H, m, H,3), 1.03(3H, d, J=2.6 Hz, H,27), 1.02(3H, d, J=2.7 Hz, H,26), 0.96(3H, d, J=6.6 Hz, H,21), 0.80(3H, s, H,19), 0.54(3H, s, H,18);13C,NMR(CDCl3, 125 MHz)δ:156.9(C,24), 139.6(C,8), 117.5(C,7), 106.0(C,28), 71.1(C,3), 56.1(C,17), 55.1(C,14), 49.5(C,9), 43.4(C,13), 40.3(C,5), 39.6(C,12), 38.0(C,4), 37.2(C,1), 36.2(C,20), 34.7(C,22), 34.2(C,10), 33.8(C,25), 31.5(C,2), 31.1(C,23), 29.7(C,6), 27.9(C,16), 23.0(C,15), 22.0(C,26), 21.9(C,27), 21.6(C,11), 18.9(C,21), 13.0(C,21), 11.9(C,18)。以上數據與文獻[14]報道的數據一致, 故化合物 8鑒定為麥角甾,7, 24(28),二烯,3β,醇。
化合物 9 白色粉末(丙酮),mp 228~230 ℃,易溶於氯仿,能溶於丙酮、乙酸乙酯、甲醇,濃硫酸香草醛反應呈鮮紅到紫紅色。1H,NMR(CDCl3, 300 MHz) δ:5.35(1H, d, J=5.3 Hz, H,7), 5.23(1H, dd, J=15.2, 7.1 Hz, H,23), 5.16(1H, dd, J=15.2, 7.7 Hz, H,22), 4.08(1H, m, H,3), 3.62(1H, d, J=5.1 Hz, H,6), 1.08(3H, br s, H,19), 1.03(3H, d, J=6.6 Hz, H,21), 0.92(3H, d, J=6.9 Hz, H,28), 0.84(3H, d, J=4.5 Hz, H,26), 0.82(3H, d, J=4.8 Hz, H,27), 0.60(3H, s, H,18);13C,NMR(CDCl3, 75 MHz)δ:144.0(C,8), 135.4(C,22), 132.2(C,23), 117.6(C,7), 77.2(C,5), 73.7(C,6), 67.8(C,3), 56.0(C,17), 54.8(C,14), 43.8(C,13), 43.5(C,24), 42.8(C,9), 40.4(C,20), 39.5(C,4), 39.2(C,12), 37.2(C,10), 33.1(C,25), 33.0(C,1), 30.9(C,2), 27.9(C,16), 22.9(C,15), 22.1(C,11), 21.1(C,21), 20.0(C,26), 19.7(C,27), 18.9(C,19), 17.6(C,28), 12.3(C,18)。以上數據與文獻[15,16]報道的數據一致, 故化合物 9鑒定為(22E, 24R),麥角甾,7, 22,二烯,3β, 5α, 6β,三醇。
化合物 10 白色粉末(甲醇),mp 156~158 ℃,易溶於氯仿、丙酮,能溶於石油醚、甲醇,香草醛濃硫酸顯紫紅色。ESI,MS m/z 255 [M-H]-。1H,NMR(CDCl3, 300 MHz) δ:5.27(2H, m, H,3, 7), 5.23(1H, m, H,22), 5.16(1H, m, H,23), 3.61(1H, br s, H,6), 1.10(3H, s, 19,Me), 1.03(3H, d, J=6.6 Hz, 21,Me), 0.92(3H, d, J=6.9 Hz, 28,Me), 0.91(3H, t, J=7.7 Hz, 16′,Me), 0.84(3H, d, J=4.7 Hz, 26,Me), 0.82(3H, d,J=4.7 Hz,27,Me), 0.60(3H, s, 18,Me);13C,NMR(CDCl3, 75 MHz) δ:173.4(C,1′), 144.0(C,8), 135.4(C,22), 132.2(C,23), 117.5(C,7), 75.7(C,5), 73.7(C,6), 70.7(C,3), 56.0(C,17), 54.7(C,14), 43.7(C,13), 43.2(C,24), 42.8(C,9), 40.4(C,20), 39.2(C,12), 37.2(C,10), 35.9(C,4), 34.7(C,1), 33.1(C,25), 32.7(C,2′), 31.9(C,14′), 29.7~29.1(C,4′~13′), 27.9(C,16), 27.0(C,2), 25.1(C,3′), 22.9(C,15), 22.7(C,15′), 21.9(C,11), 21.1(C,21), 19.9(C,26), 19.6(C,27), 18.6(C,19), 17.6(C,28), 14.1(C,16′), 12.3(C,18)。以上數據與文獻[15,17]報道的數據一致, 故化合物 10鑒定為(22E, 24R),麥角甾,7,22,二烯,3β, 5α, 6β,三醇,3,O,棕櫚酸酯。
化合物 11 白色粉末(甲醇),mp 157~159 ℃,易溶於氯仿、丙酮,能溶於石油醚、甲醇,香草醛濃硫酸顯紫紅色。1H,NMR(CDCl3, 500 MHz) δ:5.28(1H, d, J=5.4 Hz, H,7), 5.22(1H, dd, J=15.3, 7.3 Hz, H,23), 5.17(1H, dd, J=15.3, 7.9 Hz, H,22), 4.83(1H, d, J=5.2 Hz, H,6), 4.07(1H, m, H,3), 1.06(3H, s, H,19), 1.02(3H, d, J=6.7 Hz, H,21), 0.92(3H, d, J=6.9 Hz, H,28), 0.88(3H, t, J=6.8 Hz, H,16′), 0.84(3H, d, J=7.4 Hz, H,26), 0.82(3H, d, J=7.0 Hz, H,27), 0.58(3H, s, H,18);13C,NMR(CDCl3, 125 MHz) δ:173.1(C,1′), 145.6(C,8), 135.4(C,22), 132.2(C,23), 114.3(C,7), 75.3(C,5), 73.3(C,6), 67.4(C,3), 56.0(C,17), 54.9(C,14), 43.9(C,13), 43.4(C,9) ,42.9(C,24), 40.3(C,20), 39.3(C,12), 39.3(C,4), 37.3(C,10), 34.7(C,2′), 33.1(C,25), 32.5(C,1), 31.9(C,14′), 30.7(C,2), 29.7~29.1(C,4′~13′), 27.8(C,16), 25.0(C,3′), 22.9(C,15), 22.7(C,15′), 22.1(C,11), 21.1(C,21), 19.9(C,26), 19.6(C,27), 18.3(C,19), 17.6(C,28), 14.1(C,16′), 12.3(C,18)。以上數據與文獻[18]報道的數據一致, 故化合物 11鑒定為(22E, 24R),麥角甾,7,22,二烯,3β,5α,6β,三醇,6,O,棕櫚酸酯。