扁枝石松中石杉型三萜成分研究

1、扁枝石松中石杉型三萜成分研究【摘要】目的对扁枝石松全草80%乙醇提取物中的石杉型三萜类化学成分进展研究。方法利用正相和反相硅胶柱色谱方法进展别离纯化，通过S,1H-NR,13-NR波谱数据鉴定化合物构造。结果从扁枝石松共别离得到7个石杉型三萜类化合物，分别鉴定为serrat-14-en-3,21-dil；serrat-14-en-3,21-dil；3-hydrxy-21-aetxy-14-serraten；3,21-dihydrxy-14-serraten-24-iaid(lyernuiaidA,；14-serraten-3,21,24-tril(lylavanl,3,20,21-trihyd

2、rxy-14-serraten-24-iaid；21-episerratenedil-3-L-arabinpyranside(inundsideE,。结论化合物7为首次从该属植物中别离得到，化合物3为首次从该植物中分到。【关键词】扁枝石松；化学成分；石杉型三萜Abstrat：bjetiveTstudytheserratene-typetriterpenidsfrthe80%alhlextratfDiphasiastruplanatu.ethdsThepundsereislatedandpurifiedbysiliagel,18reverse-phasesiliagellunhratgraphi

3、ethds,andthEirstruturesereeluidatedbyspetralanalysis.ResultsSevenserratene-typetriterpenidserebtainedandidentifiedasserrat-14-en-3,21-dil(1),serrat-14-en-3,21-dil(2),3-hydrxy-21-aetxy-14-serraten(3),3,21-dihydrxy-14-serraten-24-iaid(lyernuiaidA,4),14-serraten-3,21,24-tril(lylavanl,5),3,20,21-trihydr

4、xy-14-serraten-24-iaid(6),21-episerratenedil-3-L-arabinpyranside(inundsideE,7).nlusinpund7asislatedfrDiphasiastruandpund3frtheplantfrthefirsttie.Keyrds：Diphasiastruplanatu;heialnstituents;Serratene-typetriterpenids扁枝石松DiphasiastruplanatuL.属石松科扁枝石松属植物，又名伸筋草、扁心草，具舒筋活血、祛风散寒、通经、消炎等作用，主治风湿骨痛，月经不调，跌打损伤，烧、

5、烫伤等1。石松科植物化学成分主要含有石松生物碱2和石杉型三萜。石杉型三萜是一类特殊的五环三萜，其中环为七元环，另外四个环为六元环，七个角甲基或其氧化形式，14-15位常有双键，3位和21位为氧接官能团。据报道该类化合物具有很强的抗肿瘤促进活性、肿瘤化学预防以及抑制白色念珠菌分泌型天冬氨酸蛋白酶活性35。因此我们对在贵州民间被广泛用于治疗风湿性关节炎、跌打损伤等疾病的扁枝石松进展三萜类化学成分的系统研究，从中别离得到7个石杉型三萜类化合物，化合物7为首次从该属植物中分得，化合物3为首次从该植物中分到。2方法与结果2.1提取别离15kg扁枝石松枯燥全草，粉碎，用80%乙醇料液比为15回流浸提4次，

6、提取时间分别为3h，3h，2h，2h，合并4次滤液，减压回收乙醇，得粗浸膏。浸膏加适量水混悬，依次以石油醚、氯仿、醋酸乙酯和正丁醇萃取，分别得石油醚、氯仿、醋酸乙酯和正丁醇萃取物210，150，380g和410g。石油醚萃取局部经硅胶柱层析，用石油醚-丙酮(10110)梯度洗脱，经TL检识，合并得5局部。其中Fr3局部经硅胶柱层析，用石油醚-丙酮(81)洗脱，得到化合物1(200g)和2(120g)；Fr4局部经硅胶柱层析，用石油醚-醋酸乙酯(101)洗脱，得到化合物3(300g)。氯仿萃取局部经硅胶柱层析，氯仿-甲醇(20111)梯度洗脱，经TL检识后合并得4局部，其中Fr3局部经硅胶柱层析

7、，石油醚-丙酮(8101)梯度洗脱，经TL检识后合并得Fr3-1，Fr3-2和Fr3-3三局部。Fr3-1经硅胶柱层析，氯仿-甲醇(201)洗脱得化合物4(120g)；Fr3-2局部经硅胶柱层析，氯仿-甲醇(151)洗脱得化合物5(70g)；Fr3-3局部经反相硅胶柱层析，30%、50%、70%、90%甲醇-水洗脱，经TL检识后合并得Fr3-3-1和Fr3-3-2两局部，经反复硅胶柱层析，氯仿-甲醇、石油醚-醋酸乙酯梯度洗脱后得白色粉末6(60g)和7(40g)。2.2构造鉴定2.2.1化合物1白色粉末，EI-S/z442+,427,409,391,234,220,207,189。1H-NR(

8、400Hz,Dl3-eD)：5.33(1H,brs,H-15),3.22(1H,dd,J=10.4,5.6Hz,H-21),3.17(1H,dd,J=10.4,6.4Hz,H-3),0.96,0.95,0.83,0.82,0.80,0.76,0.67(s,7H3)；13NR(100Hz,Dl3-eD)：38.3(-1),24.9(-2),78.1(-3),37.7(-4),55.4(-5),18.5(-6),44.8(-7),38.5(-8),56.8(-9),36.7(-10),26.6(-11),27.0(-12),62.5(-13),137.8(-14),121.8(-15),23.5(

9、-16),49.2(-17),38.4(-18),35.8(-19),26.8(-20),78.4(-21),36.8(-22),27.5(-23),15.0(-24),15.2(-25),19.3(-26),55.7(-27),12.9(-28),14.1(-29),26.8(-30)。其光谱数据与文献6报道的serrat-14-en-3,21-dil根本一致。2.2.2化合物2白色粉末，EI-S/z442+,427,409,302,284,269,255,234,220,207,189。1H-NR(400Hz,Dl3)：5.32(1H,brs,H-15),3.45(1H,brs,H-21)

10、,3.19(1H,dd,J=11.6,4.8Hz,H-3),0.97,0.93,0.89,0.83,0.80,0.77,0.69(s,7H3)。13-NR(400Hz,Dl3)：38.5(-1),25.2(-2),78.8(-3),38.1(-4),55.7(-5),18.9(-6),45.1(-7),38.9(-8),56.8(-9),35.9(-10),25.4(-11),27.1(-12),62.8(-13),138.5(-14),122.0(-15),24.0(-16),43.3(-17),37.1(-18),31.2(-19),27.5(-20),76.2(-21),37.4(-22

11、),28.1(-23),15.4(-24),15.7(-25),19.8(-26),56.2(-27),13.3(-28),21.8(-29),27.7(-30)。以上数据与文献6报道的serrat-14-en-3,21-dil一致。2.2.3化合物3白色晶体(氯仿-甲醇),EI-S/z484+,469,424,409,391,262,207,189。1H-NR(400Hz,Dl3)：5.32(1H,brs,H-15),4.50(1H,dd,J=11.2,4.4Hz,H-21),3.18(1H,dd,J=11.2,4.4Hz,H-3),2.06(3H,s,H3),0.97,0.90,0.84,

12、0.83,0.80,0.77,0.69(s,7H3)；13-NR(100Hz,Dl3)：38.6(-1),27.5(-2),78.8(-3),38.1(-4),55.7(-5),18.9(-6),45.1(-7),38.9(-8),62.8(-9),35.9(-10),25.3(-11),27.1(-12),57.0(-13),138.3(-14),121.9(-15),23.8(-16),49.6(-17),37.7(-18),36.7(-19),24.1(-20),81.1(-21),37.1(-22),28.1(-23),15.7(-24),15.4(-25),19.8(-26),56.

13、0(-27),13.4(-28),15.8(-29),27.5(-30),171.1(=),21.3(H3)。其光谱数据与文献7报道的3-hydrxy-21-aetxy-14-serraten一致。2.2.4化合物4白色粉末，EI-S/z472+,454,439,421,332,270,237,220,203,187。1H-NR(400Hz,5D5N)：5.46(1H,brs,H-15),3.65(1H,brs,H-21),3.36(1H,dd,J=12.0,4.0Hz,H-3),1.69,1.13,1.02,0.92,0.85,0.81(s,6H3)；13-NR(100Hz,5D5N)：39

14、.7(-1),29.4(-2),78.2(-3),49.4(-4),57.0(-5),21.3(-6),45.6(-7),37.3(-8),62.5(-9),38.9(-10),26.7(-11),27.7(-12),57.3(-13),139.0(-14),122.9(-15),24.6(-16),43.8(-17),36.4(-18),31.8(-19),25.7(-20),75.3(-21),38.0(-22),24.8(-23),180.9(-24),14.3(-25),19.8(-26),56.8(-27),13.9(-28),22.2(-29),28.7(-30)。其谱学数据与文献

15、5报道的3,21-dihydrxy-14-serraten-24-iaidlyernuiaidA根本一致。转贴于论文联盟.ll.2.2.5化合物5白色粉末，Ei-S/z458+,440,422,407,391,269,205,187,1H-NR(400Hz,5D5N)：5.44(1H,brs,H-15),4.44(1H,brs,H-3),4.10(1H,d,J=11.2Hz,H-24),3.86(1H,d,J=10.8Hz,H-24),3.66(1H,brs,H-21),1.59,1.15,0.93,0.89,0.83,0.80(s,6H3)。13-NR(100Hz,5D5N)：34.2(-1

16、),26.8(-2),70.0(-3),44.3(-4),50.3(-5),19.7(-6),46.0(-7),38.0(-8),63.1(-9),38.6(-10),25.5(-11),27.6(-12),57.4(-13),139.1(-14),122.7(-15),24.6(-16),43.8(-17),36.4(-18),31.9(-19),26.7(-20),75.3(-21),37.7(-22),23.7(-23),65.8(-24),16.6(-25),20.1(-26),56.8(-27),13.8(-28),22.2(-29),28.7(-30).其光谱数据与文献8报道的14

17、-serraten-3,21,24-tril(lylavanl)根本一致。2.2.6化合物6白色粉末，EI-S/z488+,470,452,437,408,372,250,237,219,201,187。1H-NR(400Hz,5D5N)：5.45(1H,brs,H-15),4.69(1H,brs,H-3),4.37(1H,d,J=10.4,H-20),3.82(1H,brs,H-21),1.75,1.19,1.12,0.95,0.92,0.84(s,6H3)。13-NR(100Hz,5D5N)：34.8(-1),27.9(-2),70.6(-3),48.6(-4),49.6(-5),21.2

18、(-6),45.7(-7),37.6(-8),62.6(-9),39.4(-10),25.8(-11),27.6(-12),57.6(-13),139.0(-14),122.8(-15),24.4(-16),41.3(-17),37.8(-18),43.3(-19),66.5(-20),79.6(-21),38.9(-22),25.5(-23),180.7(-24),14.1(-25),19.9(-26),56.9(-27),14.7(-28),21.7(-29),28.8(-30)。以上数据与文献8报道的3,20,21-trihydrxy-14-serraten-24-iaid一致。2.2.

19、7化合物7白色粉末，ESI-S/z573-H-,609+l-；EI-S/z488,470,455,439,277,259,205,187。1H-NR(400Hz,5D5N)：5.46(1H,brs,15-H),4.78(1H,d,J=6.8Hz,H-1),3.38(1H,dd,J=11.6,4.4Hz,H-21),1.28,1.15,0.97,0.93,0.80,0.79,0.77(s,7H3)；13-NR(100Hz,5D5N)：38.1(-1),26.6(-2),88.7(-3),39.8(-4),56.2(-5),19.1(-6),45.5(-7),38.0(-8),63.0(-9),3

20、8.9(-10),25.5(-11),27.5(-12),57.3(-13),139.0(-14),122.7(-15),24.6(-16),43.8(-17),36.4(-18),31.8(-19),27.0(-20),75.3(-21),37.4(-22),28.7(-23),16.1(-24),16.9(-25),20.1(-26),56.7(-27),13.8(-28),22.2(-29),28.3(-30),107.6(-1),73.0(-2),74.7(-3),69.6(-4),66.8(-5)。其光谱数据与文献9报道的21-episerratenedil-3-L-arabinpy

21、ranside(inundsideE)一致。3讨论石杉型三萜类化合物在氯仿、醋酸乙酯、甲醇、二甲亚砜以及水中的溶解性都比拟差，仅在吡啶中能充分溶解，因此给别离纯化及体外活性挑选工作带来很大的困难。鉴于石杉型三萜具有较强的细胞毒和抗肿瘤及抗真菌活性，为了进一步提醒该类化合物的生物活性，在其构造中引入糖基，从而进步该类化合物的水溶性是非常必要的。近几年来，未见有关石杉型三萜糖苷类化合物及其生物活性的研究报道，作者从扁枝石松中别离得到一个的石杉型三萜糖苷类化合物，并正在对其生物活性进展试验。继续深化的研究对石杉型三萜糖苷类化合物的发现及其生物活性的说明具有一定的科学意义。【参考文献】1何顺志,徐文芬.贵州中草药资源研究.贵阳：贵州科技出版社,2022：148.2a,XQ,GangDV.ThelypdiualkalidsJ.Nat.Prd.Rep,2022,21：752.3Tanak