石松生物碱和三萜成分的分离与鉴定

葛 越，孙琼会，吴继春，蒋金和，陈业高

（云南师范大学 化学化工学院，云南 昆明 650500）

石松生物碱和三萜成分的分离与鉴定

葛 越，孙琼会，吴继春，蒋金和，陈业高*

（云南师范大学 化学化工学院，云南 昆明 650500）

云南宣威产石松（Lycopodium japonicum）干燥全草用甲醇提取，利用硅胶柱层析和Sephadex LH-20柱层析进行化学成分分离纯化，从中分离得到12个生物碱和3个三萜化合物，根据现代波谱技术和理化性质对化合物结构进行鉴定，鉴定结构为：lycodoline(1),acetyllycoposerramine M (2),lycoposerramine-M(3),6α-hydroxylycopodine(4),12-epilycodoline(5),12β-hydroxy-acetylfawcettiine(6),lucidioline(7),α-obscurine(8),des-N-methyl-α-obscurine(9),lycopoclavamine-A(10),fawcettimine(11),lycoflexine N-oxide(12),α-onocerin(13),26-nor-8-oxo-α-onocerin(14)和diepiserratenediol (15).化合物4、5、12和15为首次从石松中分离得到.

石松；化学成分；结构鉴定

石松（Lycopodium japonicum Thunb）为石松科石松属植物,俗名过山龙、伸筋草，是一种多年生的草本药用植物，生长于海拔100～3000米的林下、灌丛中或草坡及岩石上，主要分布于全国除东北、华北以外的各个省区.石松全草具有祛风除湿、舒筋活络的等功效，在民间常被用于治疗风湿麻痹，跌打损伤及发热等症[1].上世纪八十年代，我国科学家从石松近缘植物蛇足石杉（Huperzia serrata）中分离得到了石杉碱甲（huperzine A）.该化合物不仅具有横纹肌松弛作用，而且其强效、高选择性、低毒的抗乙酰胆碱酯酶活性引起了世界药学界的广泛关注[2-5].因此，石松等近缘植物也被广泛的研究.石松的主要成分为生物碱和三萜化合物，伴有少量的黄酮及其它类型的化合物.为了寻找结构新颖、药理活性更强更好的生物碱，我们对云南宣威产石松的成分进行了分离鉴定.采用硅胶柱层析和Sephadex LH-20柱层析等分离方法，从中分离得到12个生物碱和3个三萜化合物，根据现代波谱技术和理化性质对化合物结构进行鉴定，鉴定结构为：lycodoline(1),acetyllycoposerramine M(2),lycoposerramine-M(3),6α-hydroxylycopodine(4),12-epilycodoline(5),12β-hydroxyacetylfawcettiine(6),lucidioline(7),α-obscurine(8), des-N-methyl-α-obscurine(9),lycopoclavamine-A (10),fawcettimine(11),lycoflexine N-oxide(12),α-on-

ocerin(13),26-nor-8-oxo-α-onocerin(14)和diepiserratenediol(15).化合物4、5、12和15为首次从石松中分离得到.

1 药材和仪器

1.1 仪器

Bruker DRX-500 MHz超导核磁共振仪（瑞士Bruker公司）；ZF-II型紫外分析仪（上海顾村中实仪器厂）；Sephadex LH-20:20-80μm（Pharmacia Fine Chemical Co.,Ltd.）；EYELA IV-1100型旋转蒸发仪（上海爱朗仪器有限公司）.

1.2 试剂

高效薄层层析硅胶板GF25（烟台化工研究院）；层析硅胶（青岛海洋化工厂）；显色剂为碘化铋钾溶液和10%浓硫酸-乙醇溶液；所用溶剂为工业纯，重蒸，其它试剂为化学纯或分析纯.

1.3 药材

石松全草采自云南省宣威市，由云南大学生命科学学院陆树刚教授鉴定为Lycopodium japonicum.

2 提取与分离

石松全草11 kg，粉碎后用工业甲醇浸提，浸出液减压浓缩得甲醇提取物.甲醇提取物先用1% H2SO4溶液调pH值1～2，然后用乙酸乙酯反复萃取；水层再用饱和Na2CO3溶液调pH值至10～11，然后用氯仿反复萃取，得到氯仿萃取物（40g）.将氯仿萃取物拌样后上柱，用氯仿-甲醇（50∶1→1∶1）梯度洗脱，经薄层层析检测，分为6部分：Fr-1(5.6g)、Fr-2(4.1g)、Fr-3(5.4g)、Fr-4(4.5g)、Fr-5(10.6g)、Fr-6(4.5g).将Fr-1-Fr-6部分分别经过硅胶层析和Sephadex LH-20柱层析反复分离纯化得到纯化合物.其中从Fr-1部分得到13(20 mg)，从Fr-2部分得到14(20 mg)和15(140 mg)，Fr-3部分得到8(50 mg),9(20 mg),10(5 mg)和12(20 mg)，Fr-4部分得到1(5 mg), 2(50 mg),4(10 mg)和5(13 mg)，Fr-5部分得到3(70 mg),7(6 mg)和11(107 mg)，Fr-6部分得到6(6 mg).

根据水利工程的功能，水利工程可分为防洪工程、农田水利工程、水力发电工程、巷道港口工程、城镇供排水工程、环境水利工程、渔业水利工程、海涂围垦工程等。对于大多数类型的水利工程，施工建设会对山体结构以及植被造成破坏，并不同程度地改变当地的地形，因而削弱了植物的光合作用以及保持水土、调节温度等功能，当地的温度、降雨量、地表蒸发量等气候条件都会出现一定的变化。

图1 化合物1～15的结构Fig.1 Structures of compounds 1～15

3 结构鉴定

化合物1:白色粉末.EI-MS m/z:264[M+H]+.1HNMR(CDCl3)δ:3.26(1H,m,H-9),2.96(1H,m,H-4), 2.07(1H,m,H-7),1.47(1H,m,H-15),0.94(3H,d, J=4.5 Hz,H-16);13C-NMR(CDCl3)δ:212.3(s,C-5), 69.4(s,C-12),61.4(s,C-13),46.1(t,C-9),46.1(t,C-1),44.2(t,C-6),43.1(d,C-4),40.6(d,C-7),36.0(t, C-14),35.6(t,C-8),30.1(t,C-11),24.1(d,C-15), 22.4(q,C-16),20.6(t,C-10),19.5(t,C-3),17.6(t,C-2).以上数据与文献[6]中的lycodoline一致，故鉴定化合物1为lycodoline.

化合物2：白色粉末.EI-MS m/z:306[M+H]+.1HNMR(CDCl3)δ:5.23(1H,s,H-11),3.24(1H,dd,J= 12.5,3.0 Hz,H-4),2.76(1H,dd,J=16.5,6.5 Hz,H-6),2.31(1H,s,H-7),2.21(1H,d,J=16.5 Hz,H-6), 2.08(3H,s,CH3CO),0.88(3H,d,J=6.5);13C-NMR (CDCl3)δ:214.1(s,C-5),170.0(s,C-OCCH3),72.1(d, C-11),58.8(s,C-13),47.0(t,C-1),46.7(d,C-12), 45.3(d,C-4),44.3(t,C-6),44.2(t,C-8),43.7(t,C-

14),41.9(t,C-9),35.0(d,C-7)31.0(t,C-10),25.3(d, C-15),22.5(q,C-16),21.7(q,CH3COO),19.9(t,C-3),19.3(t,C-2).以上数据与文献[7]中的acetyllycoposerramine M一致，故鉴定化合物2为acetyllycoposerramine M.

化合物3：白色粉末，1H-NMR(CDCl3)δ:3.92 (1H,ddd,J=2.8,2.8,2.8 Hz,H-11),3.58(1H,ddd, J=2.3,12.7,12.7 Hz,H-9α),3.02(1H,dt,J=12.7, 4.8 Hz,H-9β),0.85(1H,m,H-14),0.85(3H,d,J= 6.2 Hz,H-16);13C-NMR(CDCl3)δ:209.5(s,C-5), 66.7(d,C-11),64.5(s,C-13),47.0(t,C-12),46.6(d, C-1),45.4(d,C-4),44.2(t,C-6),42.8(t,C-8),42.6(t, C-14),39.3(t,C-9),35.4(d,C-7),31.5(t,C-10),25.7 (d,C-15),22.1(q,C-16),18.4(t,C-4),17.8(t,C-2).以上数据与文献[8]中的lycoposerramine-M一致，故鉴定化合物3为lycoposerramine-M.

化合物4：白色粉末，1H-NMR(CDCl3)δ:3.50 (1H,br.t,J=13.5 Hz,H-1α),2.90(1H,br.d,J=10.0 Hz,H-1β),2.10(1H,m,H-7),0.84(3H,d,J=5.0 Hz, H-16);13C-NMR(CDCl3)δ:213.5(s,C-5),78.1(d,C-6),60.6(s,C-13),47.7(t,C-9),46.7(t,C-1),44.6(d, C-12),42.9(t,C-14),42.4(d,C-7),39.8(t,C-8),39.3 (d,C-4),26.7(t,C-10),26.4(t,C-11),26.1(d,C-15), 23.1(q,C-16),19.4(t,C-3),18.6(t,C-2).以上数据与文献[9]中的6α-Hydroxylycopodine一致，故鉴定化合物4为6α-Hydroxylycopodine.

化合物5：白色粉末，1H-NMR(CD3OD)δ:3.91 (1H,m,H-9α),3.62(1H,m,H-9β),3.42(1H,m,H-3), 0.97(3H,d,J=6.0 Hz,H-16);13C-NMR(CD3OD)δ: 207.4(s,C-5),68.6(s,C-12),66.5(s,C-13),46.6(t, C-1),46.4(t,C-6),44.4(d,C-4),43.1(t,C-8),41.5 (d,C-7),34.8(t,C-14),32.8(t,C-11),27.7(t,C-9), 24.4(d,C-15),21.0(q,C-16),18.2(t,C-10),17.3(t, C-3),17.0(t,C-2).以上数据与文献[6]中的12-epilycodoline一致，故鉴定化合物5为12-epilycodoline.

化合物6：白色粉末，EI-MS m/z:366[M+H]+;1HNMR(CDCl3)δ:5.25(1H,dd,J=11.0,6.0 Hz,H-8), 5.15(1H,dd,J=6.0,0.5 Hz,H-5),3.25(1H,m,H-9), 3.25(1H,dd,J=12.5,3.0 Hz,H-4),2.77(1H,dd,J= 16.5,6.5 Hz,H-6),2.10(3H,s,5-CH3COO),2.00(3H, s,8-CH3COO)，1.00(3H，d,J=6.5 Hz，H-16);13CNMR(CDCl3)δ:170.4(s,8-CO),170.0(s,5-CO),77.7 (d,C-8),71.8(d,C-12),69.5(d,C-5),59.6(s,C-13), 47.0(t,C-1),45.7(t,C-9),42.5(d,C-7),34.9(t,C-14),32.6(d,C-4),30.2(t,C-10),28.3(d,C-15),26.3 (t,C-6),22.6(t,C-11),21.1(q,CH3COO),20.8(q, CH3COO),20.7(q,C-16),20.2(t,C-3),19.0(t,C-2).以上数据与文献[10]中的2β-hydroxy-acetylfawcettiine一致，故鉴定化合物6为2β-hydroxy-acetylfawcettiine.

化合物7：白色粉末，1H-NMR(C5D5N)δ:5.61 (1H,dd,J=4.5,3.0 Hz,H-11),4.42(1H,dd,J=5.5, 3.0 Hz,H-6),4.38(1H,d,J=5.5 Hz,H-7),0.92(3H, d,J=6.5 Hz,H-16);13C-NMR(C5D5N)δ:146.1(s,C-12),117.6(d,C-11),80.7(d,C-6),75.7(d,C-5),58.5 (s,C-13),50.3(d,C-7),49.7(t,C-1),46.9(t,C-9), 45.8(d,C-4),43.2(t,C-8),36.5(t,C-14),28.4(t,C-10),27.3(t,C-2),25.6(t,C-3),25.3(d,C-15),25.1 (q,C-16).以上数据与文献[11]中的lucidioline一致，故鉴定化合物7为lucidioline.

化合物8：白色粉末，EI-MS m/z:275[M+H]+;1HNMR(CDCl3)δ:2.78(2H,m,H-9),2.50(7H,m,H-2, 3,17),2.85(3H,d,J=6.5 Hz,N-CH3),0.93(3H,d, J=6.5 Hz,H-16);13C-NMR(CDCl3)δ:172.0(s,C-1), 130.6(s,C-5),114.1(s,C-4),58.9(s,C-13),51.4(t, C-9),43.5(t,C-14),42.8(t,C-8),36.0(q,C-17),35.4 (d,C-12),33.6(d,C-7),31.3(t,C-6),30.0(t,C-2), 27.1(d,C-15),26.5(t,C-11),22.3(q,C-16),19.4(t, C-3).以上数据与文献[12]中的α-obscurine一致，故鉴定化合物8为α-obscurine.

化合物9：白色粉末，1H-NMR(CDCl3)δ:2.81 (1H,m,H-7),2.50(1H,m,H-9α),2.49(1H,m,H-9β),1.43(1H,m,H-12),1.19(1H,m,H-15),0.87 (3H,d,J=6.0 Hz,H-16);13C-NMR(CDCl3)δ:171.7 (s,C-1),131.2(s,C-5),112.1(s,C-4),55.4(s,C-13), 46.2(t,C-9),44.6(d,C-12),43.5(t,C-14),42.7(t,C-8),33.5(d,C-7),31.2(t,C-6),30.0(t,C-2),27.4(t,C-10),26.5(d,C-15),26.0(t,C-11),22.0(q,C-16),18.8 (t,C-3).以上数据与文献[12]中的des-N-methyl-αobscurine一致，故鉴定化合物9为des-N-methyl-αobscurine.

化合物10：白色粉末，EI-MS m/z:262[M+H]+;1H-NMR(CDCl3)δ:6.95(1H,dd,J=8.0,2.5 Hz,H-3),3.75(1H,ddd,J=14.0,14.0,4.0 Hz,H-9),2.00 (1H,s,H-7),1.86(1H,d,J=17.5 Hz,H-6),1.50(2H, m,H-10,11),0.86(3H,d,J=6.5 Hz,H-16);13C-NMR (CDCl3)δ:206.9(s,C-5),141.7(s,C-4),136.1(d,C-3),87.6(s,C-13),54.4(s,C-12),46.7(t,C-1),45.5(t,

C-9),43.1(t,C-6),40.7(t,C-14),36.9(d,C-7),35.6 (t,C-8),30.3(t,C-11),30.2(t,C-2),26.7(d,C-15), 22.9(t,C-10),22.3(q,C-16).以上数据与文献[13]中的lycopoclavamine-A一致，故鉴定化合物10为lycopoclavamine-A.

化合物11：白色粉末，EI-MS m/z:264[M+H]+;1H-NMR(CDCl3)δ:11.0(1H,s,13-OH),6.64(1H,s, H-4),4.02(1H,ddd,J=4.0,8.5,13.5 Hz,H-9),0.99 (3H,d,J=6.5 Hz,H-16);13C-NMR(CDCl3)δ:216.2 (s,C-5),95.5(s,C-13),59.5(d,C-4),55.2(t,C-9), 50.7(t,C-1),47.4(s,C-12),43.4(d,C-7),41.4(t,C-14),40.1(t,C-6),33.4(t,C-3),31.4(t,C-8),26.9(t, C-11),24.4(t,C-2),23.9(d,C-15),21.4(q,C-16), 19.6(t,C-10).以上数据与文献[14]中的fawcettimine一致，故鉴定化合物11为fawcettimine.

化合物12：黄色粉末，EI-MS m/z:292[M+H]+;1H-NMR(CD3OD)δ:3.95(2H,m,H-9,17),3.83(1H, d,J=11.0 Hz,H-1),3.65(1H,m,H-9),2.20(1H,dd, J=8.55 Hz,H-17),1.07(3H,d,J=6.5 Hz,H-16);13C-NMR(CD3OD):215.0(s,C-5),213.6(s,C-13), 75.2(t,C-9),70.7(t,C-1),68.2(t,C-17),61.4(s,C-12),58.7(s,C-4),47.7(t,C-14),42.7(d,C-7),40.7(t, C-6),34.4(t,C-11),31.5(t,C-8),29.5(d,C-15),28.0 (t,C-10),22.8(t,C-2),22.1(q,C-16),22.0(t,C-3).以上数据与文献[7，13]中的lycoflexine N-oxide一致，故鉴定化合物12为lycoflexine N-oxide.

化合物13：无色粉末，1H-NMR(C5D5N)δ:5.28 (2H,s,H-26),5.09(2H,s,H-27),3.49(2H,dd,J= 10.2,5.0 Hz,H-3,21),2.50(2H,d,J=12.0 Hz,H-7, 15),2.12(2H,m,H-7,15),2.07(2H,dt,J=12.5,5.0 Hz,H-7,15),1.23(6H,s,H-23,29),1.03(6H,s,H-24,30),0.79(6H,s,H-25,28);13C-NMR(C5D5N)δ: 149.4(s,C-8,14),106.6(t,C-26,27),77.8(d,C-3, 21),57.7(d,C-9,13),54.8(d,C-5,17),39.5(s,C-4, 10,18,22),38.5(t,C-7,15),37.4(t,C-1,19),28.7(t, C-2,20),28.6(q,C-23,29),24.3(t,C-6,16),22.9(t, C-11,12),16.1(q,C-24,30),14.7(q,C-25,28).以上数据与文献[15]中的α-onocerin一致，故鉴定化合物13为α-onocerin.

化合物14：无色粉末，EI-MS m/z:467[M+Na]+;1H-NMR(C5D5N)δ:4.93(2H,s,H-27),3.37(1H,dd, J=11.6,4.0 Hz,H-3),3.26(1H,dd,J=11.2,4.5 Hz, H-21),2.40(2H,m,H-7),2.30(1H,m,H-15α),2.01 (1H,m,H-15β),1.08(3H,s,H-25),0.99(3H,s,H-28),0.83(3H,s,H-24),0.76(3H,s,H-30),0.66(3H, s,H-23),0.62(3H,s,H-29);13C-NMR(C5D5N)δ: 211.9(s,C-8),147.4(s,C-14),107.8(t,C-27),78.9 (d,C-21),78.6(d,C-3),64.7(d,C-9),57.2(d,C-13), 54.7(d,C-5),53.6(d,C-17),42.4(t,C-7),42.3(s,C-10),39.2(s,C-22),39.1(s,C-4),39.1(s,C-18),38.2 (t,C-15),37.2(t,C-1),36.9(t,C-19),29.7(q,C-29), 28.4(t,C-2),28.3(t,C-20),27.9(q,C-23),27.6(t,C-6),23.9(t,C-16),23.5(t,C-12),21.0(t,C-11),15.4 (q,C-24),15.3(q,C-30),14.8(q,C-28),14.5(q,C-25).以上数据与文献[15]中的26-nor-8-oxo-α-onocerin一致，故鉴定化合物14为26-nor-8-oxo-α-onocerin.

化合物15：无色粉末，1H-NMR(C5D5N)δ:3.66 (1H,br.s,H-3),5.44(1H,br.s,H-15),3.87(1H,m,H-21),0.83(3H,s,H-23),0.79(3H,s,H-24),0.83(3H, s,H-25),0.89(3H,s,H-26),0.92(3H,s,H-28),1.15 (3H,s,H-29),1.19(3H,s,H-30);13C-NMR(C5D5N)δ: 140.4(s,C-14),123.4(d,C-15),76.5(d,C-21),71.2 (d,C-12),67.0(t,C-24),64.3(d,C-3),62.9(d,C-9), 58.7(d,C-13),58.1(t,C-27),56.8(t,C-27),49.5(d, C-5),45.6(t,C-7),43.8(d,C-17),38.0(s,C-22), 39.5(s,C-4),39.3(s,C-10),38.2(s,C-8),37.5(s,C-18),34.1(t,C-1),31.9(t,C-19),28.8(t,C-2),28.8(q, C-30),27.6(t,C-12),26.7(t,C-20),25.5(t,C-11), 24.6(t,C-16),22.9(q,C-23),22.1(q,C-29),20.1(q, C-26),19.4(t,C-6),16.0(q,C-25),14.5(q,C-24), 13.8(q,C-28)23.以上数据与文献[16]中的diepiserratenediol一致，故鉴定化合物15为die

piserratenediol.

4 结论

从云南宣威产石松中分离得到12个生物碱和3个三萜化合物，根据现代波谱技术和理化性质对化合物结构进行鉴定，鉴定结构为：lycodoline(1),acetyllycoposerramine M(2),lycoposerramine-M(3),6α-hydroxylycopodine(4),12-epilycodoline(5),12β-hydroxy-acetylfawcettiine(6),lucidioline(7),α-obscurine(8),des-N-methyl-α-obscurine(9),lycopoclavamine-A(10),fawcettimine(11),lycoflexine N-oxide (12),α-onocerin(13),26-nor-8-oxo-α-onocerin(14)和diepiserratenediol(15).化合物4、5、12和15为首次从石松中分离得到.

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责任编辑：刘 红

Alkaloids and Triterpenoids from Lycopodium japonicum

GE Yue，SUN Qionghui，WU Jichun，JIANG Jinhe，CHEN Yegao*
（School of Chemistry and Chemical Engineering，Yunnan Normal University，Kunming 650500，China）

Fifteen compounds including twelve alkaloids,and three triterpenoids were isolated from the whole plants of Lycopodium japonicum Thunb,and their structures were elucidated as lycodoline(1),acetyllycoposerramine M(2),lycoposerramine-M(3),6α-hydroxylycopodine(4),12-epilycodoline(5),12β-hydroxy-acetylfawcettiine(6),lucidioline(7),α-obscurine(8),des-N-methyl-α-obscurine(9),lycopoclavamine-A(10),fawcettimine(11),lycoflexine N-oxide(12),α-onocerin (13),26-nor-8-oxo-α-onocerin(14)and diepiserratenediol(15)respectively.Compounds 4、5、12 and 15 were isolated from L.japonicum for the first time.

Lycopodium japonicum；Chemical constituents；Structure identification

R 248.1

A

1674-4942（2016）03-0277-05

2016-05-08

国家自然科学基金（21162045）

*通讯作者