葛 越，孫瓊會，吳繼春，蔣金和，陳業(yè)高

（云南師范大學(xué) 化學(xué)化工學(xué)院，云南 昆明 650500）

石松生物堿和三萜成分的分離與鑒定

葛 越，孫瓊會，吳繼春，蔣金和，陳業(yè)高*

（云南師范大學(xué) 化學(xué)化工學(xué)院，云南 昆明 650500）

云南宣威產(chǎn)石松（Lycopodium japonicum）干燥全草用甲醇提取，利用硅膠柱層析和Sephadex LH-20柱層析進行化學(xué)成分分離純化，從中分離得到12個生物堿和3個三萜化合物，根據(jù)現(xiàn)代波譜技術(shù)和理化性質(zhì)對化合物結(jié)構(gòu)進行鑒定，鑒定結(jié)構(gòu)為：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為首次從石松中分離得到.

石松；化學(xué)成分；結(jié)構(gòu)鑒定

石松（Lycopodium japonicum Thunb）為石松科石松屬植物,俗名過山龍、伸筋草，是一種多年生的草本藥用植物，生長于海拔100～3000米的林下、灌叢中或草坡及巖石上，主要分布于全國除東北、華北以外的各個省區(qū).石松全草具有祛風(fēng)除濕、舒筋活絡(luò)的等功效，在民間常被用于治療風(fēng)濕麻痹，跌打損傷及發(fā)熱等癥[1].上世紀(jì)八十年代，我國科學(xué)家從石松近緣植物蛇足石杉（Huperzia serrata）中分離得到了石杉堿甲（huperzine A）.該化合物不僅具有橫紋肌松弛作用，而且其強效、高選擇性、低毒的抗乙酰膽堿酯酶活性引起了世界藥學(xué)界的廣泛關(guān)注[2-5].因此，石松等近緣植物也被廣泛的研究.石松的主要成分為生物堿和三萜化合物，伴有少量的黃酮及其它類型的化合物.為了尋找結(jié)構(gòu)新穎、藥理活性更強更好的生物堿，我們對云南宣威產(chǎn)石松的成分進行了分離鑒定.采用硅膠柱層析和Sephadex LH-20柱層析等分離方法，從中分離得到12個生物堿和3個三萜化合物，根據(jù)現(xiàn)代波譜技術(shù)和理化性質(zhì)對化合物結(jié)構(gòu)進行鑒定，鑒定結(jié)構(gòu)為：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為首次從石松中分離得到.

1 藥材和儀器

1.1 儀器

Bruker DRX-500 MHz超導(dǎo)核磁共振儀（瑞士Bruker公司）；ZF-II型紫外分析儀（上海顧村中實儀器廠）；Sephadex LH-20:20-80μm（Pharmacia Fine Chemical Co.,Ltd.）；EYELA IV-1100型旋轉(zhuǎn)蒸發(fā)儀（上海愛朗儀器有限公司）.

1.2 試劑

高效薄層層析硅膠板GF25（煙臺化工研究院）；層析硅膠（青島海洋化工廠）；顯色劑為碘化鉍鉀溶液和10%濃硫酸-乙醇溶液；所用溶劑為工業(yè)純，重蒸，其它試劑為化學(xué)純或分析純.

1.3 藥材

石松全草采自云南省宣威市，由云南大學(xué)生命科學(xué)學(xué)院陸樹剛教授鑒定為Lycopodium japonicum.

2 提取與分離

石松全草11 kg，粉碎后用工業(yè)甲醇浸提，浸出液減壓濃縮得甲醇提取物.甲醇提取物先用1% H2SO4溶液調(diào)pH值1～2，然后用乙酸乙酯反復(fù)萃?。凰畬釉儆蔑柡蚇a2CO3溶液調(diào)pH值至10～11，然后用氯仿反復(fù)萃取，得到氯仿萃取物（40g）.將氯仿萃取物拌樣后上柱，用氯仿-甲醇（50∶1→1∶1）梯度洗脫，經(jīng)薄層層析檢測，分為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).將Fr-1-Fr-6部分分別經(jīng)過硅膠層析和Sephadex LH-20柱層析反復(fù)分離純化得到純化合物.其中從Fr-1部分得到13(20 mg)，從Fr-2部分得到14(20 mg)和15(140 mg)，F(xiàn)r-3部分得到8(50 mg),9(20 mg),10(5 mg)和12(20 mg)，F(xiàn)r-4部分得到1(5 mg), 2(50 mg),4(10 mg)和5(13 mg)，F(xiàn)r-5部分得到3(70 mg),7(6 mg)和11(107 mg)，F(xiàn)r-6部分得到6(6 mg).

根據(jù)水利工程的功能，水利工程可分為防洪工程、農(nóng)田水利工程、水力發(fā)電工程、巷道港口工程、城鎮(zhèn)供排水工程、環(huán)境水利工程、漁業(yè)水利工程、海涂圍墾工程等。對于大多數(shù)類型的水利工程，施工建設(shè)會對山體結(jié)構(gòu)以及植被造成破壞，并不同程度地改變當(dāng)?shù)氐牡匦危蚨魅趿酥参锏墓夂献饔靡约氨３炙?、調(diào)節(jié)溫度等功能，當(dāng)?shù)氐臏囟?、降雨量、地表蒸發(fā)量等氣候條件都會出現(xiàn)一定的變化。

圖1 化合物1～15的結(jié)構(gòu)Fig.1 Structures of compounds 1～15

3 結(jié)構(gòu)鑒定

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).以上數(shù)據(jù)與文獻[6]中的lycodoline一致，故鑒定化合物1為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).以上數(shù)據(jù)與文獻[7]中的acetyllycoposerramine M一致，故鑒定化合物2為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).以上數(shù)據(jù)與文獻[8]中的lycoposerramine-M一致，故鑒定化合物3為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).以上數(shù)據(jù)與文獻[9]中的6α-Hydroxylycopodine一致，故鑒定化合物4為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).以上數(shù)據(jù)與文獻[6]中的12-epilycodoline一致，故鑒定化合物5為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).以上數(shù)據(jù)與文獻[10]中的2β-hydroxy-acetylfawcettiine一致，故鑒定化合物6為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).以上數(shù)據(jù)與文獻[11]中的lucidioline一致，故鑒定化合物7為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).以上數(shù)據(jù)與文獻[12]中的α-obscurine一致，故鑒定化合物8為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).以上數(shù)據(jù)與文獻[12]中的des-N-methyl-αobscurine一致，故鑒定化合物9為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).以上數(shù)據(jù)與文獻[13]中的lycopoclavamine-A一致，故鑒定化合物10為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).以上數(shù)據(jù)與文獻[14]中的fawcettimine一致，故鑒定化合物11為fawcettimine.

化合物12：黃色粉末，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).以上數(shù)據(jù)與文獻[7，13]中的lycoflexine N-oxide一致，故鑒定化合物12為lycoflexine N-oxide.

化合物13：無色粉末，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).以上數(shù)據(jù)與文獻[15]中的α-onocerin一致，故鑒定化合物13為α-onocerin.

化合物14：無色粉末，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).以上數(shù)據(jù)與文獻[15]中的26-nor-8-oxo-α-onocerin一致，故鑒定化合物14為26-nor-8-oxo-α-onocerin.

化合物15：無色粉末，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.以上數(shù)據(jù)與文獻[16]中的diepiserratenediol一致，故鑒定化合物15為die

piserratenediol.

4 結(jié)論

從云南宣威產(chǎn)石松中分離得到12個生物堿和3個三萜化合物，根據(jù)現(xiàn)代波譜技術(shù)和理化性質(zhì)對化合物結(jié)構(gòu)進行鑒定，鑒定結(jié)構(gòu)為：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為首次從石松中分離得到.

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責(zé)任編輯：劉 紅

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

國家自然科學(xué)基金（21162045）

*通訊作者