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大戟脂中三萜类化学成分的研究(二)

来源:时间:2025-04-21 09:08:00

因為C-3連接的大戟的研基團不同,所以A環和9,脂中 19-環丙基環上的H與C數據不一樣,而C環、萜类D環及21、化学23側鏈數據基本一致。成分通過1H-1H COSY和HSQC圖譜解析,大戟的研對化合物2的脂中NMR譜中氫及其直接相連的碳信號進行了確定。在化合物2中H1-3與A環上C-1、萜类C-2、化学C-3、成分C-4、大戟的研C-27和C-28以及H2-19與C-9、脂中C-10、萜类C-5、化学C-8、成分C-1在HMBC光譜中的程相關性所證實的。綜上所述,將化合物2鑒定為cycloartan-1,24-diene-3-ol,為新化合物。在ROESY譜中顯示H-5/H3-29、H-5/H-7α、H-7α/H3-30、H-8/H3-18、H-8/H-19β、H-19β/H3-28相關,證明 H-5、H3-29、H3-30為α構型,H-8、H3-18、H3-28為β構型;H-3/H-5相關,說明C-3位上的羥基為β構型。

化合物3無色膠狀固體,茴香醛-10%硫酸乙醇溶液顯色呈藍色。HR-ESI-MS m/z 441.37271 +,分子式為C30 H49 O2。1H-NMR(CDCl3, 400MHz)δH:3.24(1H, dd, J=10.6, 5.4Hz,CH-3),1.02(1H,m,CH-5),1.70(1H,m,CH-17),0.88(3H,s,CH3-18),1.20(3H,s, CH3-19),1.20(3H,s,CH3-19),0.83(3H, s, CH3-29),1.00(3H, s, CH3-30);13C-NMR(CDCl3,100MHz)δC:35.12(C-1),28.36(C-2),78.92(C-3),39.01(C-4),51.75(C-5),18.10(C-6),29.75(C-7),161.42(C-8),139.61(C-9),37.15(C-10),199.14(C-11),51.27(C-12),44.67(C-13),51.20(C-14),30.05(C-15),27.54(C-16),50.52(C-17),17.72(C-18),19.97(C-19),35.87(C-20),18.48(C-21),37.15(C-22),28.36(C-23),124.72(C-24),131.29(C-25),25.76(C-26),18.48(C-27),24.24(C-28),15.76(C-29),25.19(C-30)。以上波譜數據與文獻的數據基本一致,故鑒定該化合物為3β-hydroxy-lanosta-8,24-diene-11-one。

化合物4白色膠狀固體,茴香醛-10%硫酸乙醇溶液顯色呈紫紅色。1H-NMR(CDCl3,400MHz)δH: 0.88(3H,s, CH3-30), 0.73(3H, s, CH3-18), 1.05(3H, d,J=6.6Hz, CH3-21), 0.94(3H, s, CH3-19), 3.23(1H, dd, J=11.5,4.5Hz,CH-3),0.80(3H,s,CH3-29); 13C-NMR (CDCl3,100MHz)δC:35.08(C-1),27.54(C-2),78.84(C-3),38.86(C-4),50.83(C-5),18.80(C-6),27.27(C-7),133.03(C-8),134.25(C-9),37.22(C-10),21.22(C-11),29.94(C-12),44.21(C-13),49.64(C-14),29.65(C-15),27.98(C-16),50.15(C-17),15.98(C-18),20.09(C-19),40.99(C-20),20.19(C-21),165.19(C-22),130.69(C-23),194.45(C-24),27.81(C-28),15.48(C-29),24.23(C-30)。以上波譜數據與文獻的數據基本一致,故鑒定該化合物為lnonotusane C。

化合物5淡黃色膠狀固體,茴香醛-10%硫酸乙醇溶液顯色呈藍色。ESI-MS m/z 455+,分子式為C30H46O3。1H-NMR(CDCl3, 400MHz)δH: 1.10(3H,s,CH3-30), 0.82(3H, s, CH3-18), 0.91(3H, d, J=6.4Hz,CH3-21), 1.32(3H,s, CH3-19), 1.04(3H, s, CH3-28), 1.62(3H, s, CH3-27), 3.32(1H, dd, J=12.0, 4.8Hz, CH-3),5.08(1H, t, J=7.1Hz, CH-24);13C-NMR(CDCl3,100MHz)δC:33.82(C-1),27.52(C-2),78.86(C-3),39.49(C-4),48.37(C-5),35.69(C-6),199.86(C-7),149.73(C-8),154.66(C-9),37.94(C-10),202.02(C-11),51.44(C-12),44.99(C-13),47.8(C-14), 31.68(C-15),28.10(C-16),49.27(C-17),18.34(C-18),19.67(C-19),35.04(C-20),18.40(C-21),35.63(C-22),25.04(C-23),124.48(C-24),131.34(C-25),25.68(C-26),17.63(C-27),27.52(C-28),14.99(C-29),23.95(C-30)。以上波譜數據與文獻的數據基本一致,故鑒定該化合物為eupha-8,24-diene-3β-ol-7,11-dione。

化合物6白色針狀結晶,茴香醛-10%硫酸乙醇溶液顯色呈紫紅色。1H-NMR(CDCl3,400MHz)δH:1.08(3H, s, CH3-30), 0.92(3H, s, CH3-18), 0.89(3H, d,J= 6.6 Hz,CH3-21), 1.31(3H, s, CH3-19), 3.30(1H, dd, J=10.4, 5.9Hz,CH-3), 0.90(3H,s,CH3-29);13C-NMR (CDCl3,150MHz)δC:34.04(C-1),27.73(C-2),78.09(C-3),38.72(C-4),48.61(C-5),35.90(C-6),200.07(C-7),149.92(C-8),154.96(C-9),38.19(C-10),202.17(C-11),51.58(C-12),45.28(C-13),47.89(C-14), 31.98(C-15),28.06(C-16),49.44(C-17),18.46(C-18),17.90(C-19),36.27(C-20),18.41(C-21),34.70(C-22),31.38(C-23),156.58(C-24),33.94(C-25),22.13(C-26),22.99(C-27),27.73(C-28),15.19(C-29),24.11(C-30),106.37(C-31)。以上波譜數據與文獻的數據基本一致,故鑒定該化合物為eupha-24-methylene-8-ene-3β-ol-7,11-dione。

化合物7白色膠狀固體,茴香醛-10%硫酸乙醇溶液顯色呈紫紅色。ESI-MS m/z457 +,分子式為C30H49O3。1H-NMR(CDCl3,400MHz)δH:3.34(1H,dd,J=9.4,6.5 Hz,CH-3),1.66(1H,m,CH-5),1.59(1H,m,CH-17),0.73(3H,s,CH3-18),1.28(3H,s,CH3-19),1.48(1H,m,CH-20),0.89(3H,d,J=6.5Hz,CH3-21),1.71(3H,s,CH3-26),1.63(3H,s,CH3-27),1.01(3H,s,CH3-28),0.93(3H,s,CH3-29),1.16(3H,s,CH3-30);13C-NMR(CDCl3,100MHz)δC:33.70(C-1),27.41(C-2),78.30(C-3),39.12(C-4),48.26(C-5),35.90(C-6),200.20(C-7),140.48(C-8),161.26(C-9),39.62(C-10),68.22(C-11),42.88(C-12),46.21(C-13),48.06(C-14),31.84(C-15),27.91(C-16),48.70(C-17),16.28(C-18),19.74(C-19),35.70(C-20),18.84(C-21),35.70(C-22),24.86(C-23),124.93(C-24),131.23(C-25),25.83(C-26),17.79(C-27),27.65(C-28),15.27(C-29),25.77(C-30)。以上波譜數據與文獻的數據基本一致,故鑒定該化合物為eupha-8,24-diene-3β,11β-diol-7-one。

4 討論

大戟脂中含三萜化合物主要的類型為甘遂烷型、大戟烷型及相應的降三萜。本實驗對大戟脂中的三萜類化合物進行研究,從中分離得到了2個新的三萜化合物,2個化合物皆為環阿爾廷烷型。環阿爾廷烷基本骨架與羊毛脂烷很相似,差別僅在於環阿爾廷烷C-10位相連的甲基與C-9位脫氫形成三元碳環,C-3位羥基大多與乙酸形成乙酸酯,C-17位的取代側鏈由於雙鍵位置和羥基取代位置的變化而使結構變得更為複雜。國內外學者對此類型的某些三萜的抗病毒、抗菌抗炎、抗腫瘤、免疫調節、肝損傷保護和心血管係統等方麵的生物活性給予了很大的關注。因此,希望從大戟脂中分離出多樣性成分,尤其是具有多樣性骨架類型的三萜類成分,以期能夠從中發現具有新穎骨架從而為新藥研發提供新的結構基礎。

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相關鏈接:化合物乙醇光譜