三七中2 个微量人参皂苷的NMR信号全归属

波谱学杂志

三七中2 个微量人参皂苷的NMR信号全归属

黄桂坤1，邱莉1,2,3*，焦杨1，袁经权1,2,3，谢集照1，缪剑华2

1. 广西医科大学药学院，广西南宁 530021；2. 广西药用植物研究所，广西南宁 530023；
3. 暨南大学中药及天然药物研究所，广东广州 510632

收稿日期:2013-10-09 修回日期:2014-07-19 出版日期:2014-09-05 发布日期:2014-09-05
作者简介:黄桂坤(1987-)，女，硕士研究生，药物化学专业．*通讯联系人：邱莉，电话：13878897164，E-mail：qlydmyyq@163.com.
基金资助:
广西壮族自治区自然科学青年基金资助项目(2013GXNSFBB053001)，广西药用植物园青年科学基金资助项目(桂药基201101)．

NMR Assignments of Two Minor Ginsenosides Extratced from Panax notoginseng (Burk.) F. H. Chen

HUANG Gui-kun1，QIU Li1,2,3*，JIAO Yang1，YUAN Jing-quan1,2,3，XIE Ji-zhao1，MIAO Jian-hua2

1. College of Pharmacology, Guangxi Medical University, Nanning 530021, China;
2. Guangxi Institute of Medical Plant, Nanning 530023, China;
3. Institute of Traditional Chinese Medicine and Natural Products, Jinan University, Guangzhou 510632, China

Received:2013-10-09 Revised:2014-07-19 Online:2014-09-05 Published:2014-09-05
Supported by:
广西壮族自治区自然科学青年基金资助项目(2013GXNSFBB053001)，广西药用植物园青年科学基金资助项目(桂药基201101)．

摘要/Abstract

摘要：

从三七根的80%乙醇提取物中，分离并鉴定了2 个人参皂苷类化合物，分别为6-O-(β-D-glucopyranosyl)-20-O-(β-D-xylopyranosyl)-3β，6α，12β，20(S)-tetrahydroxydammar-24-ene（化合物1）和notoginsenoside U（化合物2）．应用1D 和2D NMR (¹H-¹H COSY、HSQC和HMBC)对这2 种化合物的结构进行解析，对化合物1 的¹³C NMR 文献报道数据进行了修正与讨论，并对化合物1 的¹H NMR 数据进行全归属．同时在2D NMR 的基础上对化合物2 在氘代吡啶溶液中的¹H NMR 和¹³C NMR 数据进行全归属．

关键词: 核磁共振(NMR), 人参皂苷, 三七, 归属

Abstract:

Two ginsenosides were isolated from the 80% ethanol extract of the root of Panax notoginseng, namely 6-O-(β-D-glucopyranosyl)-20-O-(β-D-xylopyranosyl)-3β，6α，12β，20(S)-tetrahydroxydammar-24-ene (compound 1) and notoginsenoside U (compound 2). Their structures were elucidated by one-imensional and two-dimensional NMR (i.e., ¹H-¹H COSY, HSQC and HMBC) experiments. The ¹³C NMR spectral data of compound 1 was compared with those reported in the previous references, and corrections were made for some previous assignments which were incorrect. The completed assignments of
compound 1 were obtained. The ¹H and ¹³C NMR signals of compound 2 in prydine-d₅ were assigned.

Key words: NMR, ginsenosides, Panax notoginseng, assignment

中图分类号:

O482.53

黄桂坤1，邱莉1,2,3*，焦杨1，袁经权1,2,3，谢集照1，缪剑华2. 三七中2 个微量人参皂苷的NMR信号全归属[J]. 波谱学杂志.

HUANG Gui-kun1，QIU Li1,2,3*，JIAO Yang1，YUAN Jing-quan1,2,3，XIE Ji-zhao1，MIAO Jian-hua2. NMR Assignments of Two Minor Ginsenosides Extratced from Panax notoginseng (Burk.) F. H. Chen[J]. Chinese Journal of Magnetic Resonance.

参考文献

[1] Zeng Jiang(曾江), Cui Xiu-ming(崔秀明), Zhou Jia-ming(周家明), et al. Studies on chemical constituents from rhizomes of Panax notoginseng(三七根茎的化学成分研究)[J]. Journal of Chinese Medicinal Materials(中药材), 2007, 30(11): 1 388－1 391.

[2] Ng T B. Pharmacological activity of sanchi ginseng (Panax notoginseng)[J]. J Pharm Pharmacol, 2006, 58: 1 007－1 019.

[3] Liu Li-min(刘利民)，Zhang Xiao-qi(张晓琦)，Wang Hao(汪豪), et al. Minor saponins constituents from Panax notoginseng tap root(三七主根的微量皂苷类成分研究)[J]. Journal of China Pharmaceutical University(中国药科大学学报), 2011,

42(2): 115－118.

[4] Sun H X, Ye Y P, Pan Y J. Immunological-adjuvant saponins from the roots of Panax notoginseng[J]. Chem Biodivers, 2005, 2: 510－515.

[5] Liang C, Zhang X D, Wei L P, et al. Investigation of the molecular ion structure for aldononitrile acetate derivatized muramic acid[J]. J Microbiol Meth, 2011, 86: 224－230.

[6] Tanaka O. Application of 13C-nuclear magnetic resonance spectrometry to structural studies on glycosides: saponins of Panax spp. and natural sweet glycosides[J]. Yakugaku Zasshi, 1985, 105, 323－351.

[7] Matsuura H, Kasai R, Tanaka O, et al. Further studies on dammarane-saponins of sanchi-ginseng[J]. Chem Pharm Bull, 1983, 31(7): 2 281－2 287.

[8] Teng Rong-wei(滕荣伟), Li Hai-zhou(李海舟), Wang De-zu(王德祖), et al. NMR complete assignments of three protopanaxadiol bisdesmosides(三七皂苷NMR 研究-3 个原人参二醇型双糖链配糖体的NMR 信号全归属)[J]. Chinese J Magn Reson(波谱学杂志), 2002, 19(1): 1－8.

[9] Wu Chun-hua(吴春华), Li Chun-mei(李春梅), Chen Feng(陈凤), et al. NMR characterization of two monoterpene glycosides isolated from Boshniakia rossica Fedtsh et Flerow(草苁蓉中2 个单萜苷类化合物的NMR 研究)[J]. Chinese J Magn Reson(波谱学杂志), 2013, 30(2): 247－255.

[10] Wu Li-jun(吴立军). Practical Spectral Analysis of Organic Compounds(实用有机化合物光谱解析)[M]. Beijing(北京): People's Health Publishing House(人民卫生出版社), 2009.

[11] Wang Jin-hui(王金辉). Studies on the chemical constitutions and bioactivities of leaves and stems of Panax quinquefolium L. (西洋参茎叶化学成分和生物活性的研究)[D]. Shenyang(沈阳): Shenyang Pharmaceutical University(沈阳药科大学), 1999.

[12] 上海吉友医药科技有限公司. 20-O-糖基及其原人参二醇类化合物及其制备方法: 中国, 200910201258.7. [P], 2010-07-21.

[13] Chen J, Zhao R, Zeng Y M, et al. Three new triterpenoid saponins from the leaves and stems of Panax quinquefolium[J]. J Asian Nat Prod Res, 2009, 11(3): 195－201.

[14] Liu Chang-da(刘昌达). Research on the chemieal constituents of flower buds of Panax quinquefolium L. (西洋参花蕾化学成分的研究)[D]. Shenyang(沈阳): Shenyang Pharmaceutical University(沈阳药科大学), 2008.

[15] Cui X M, Jiang Z Y, Zeng J, et al. Two new dammarane triterpene glycosides from the rhizomes of Panax notoginseng[J]. J Asian Nat Prod Res, 2008, 10(9): 845－849.

[16] Kun Zou, Shu Zhu, Meselhy R M, et al. Dammarane-type saponins from Panax japonicus and their neurite outgrowth activity in SK-N-SH Cells[J]. J Nat Prod, 2002, 65: 1 288－1 292.

[17] Yang T R, Kasai R, Zhou Jun, et al. Dammarane saponins of leaves and seeds of Panax notognseng[J]. Phytochenistry, 1983, 22(6): 1 473－1 478.

[18] 中国科学院大连化学物理研究所. 一种催化热解制备低极性人参皂苷及其苷元的方法: 中国, 1508147. [P], 2004-06-30.

[19] Nguyen M D, Kasai R, Ohtani K, et al. Saponins from vietnamese ginseng, Panax vietnamensis HA et Grushv. collected in central vietnam. II.[J]. Chem Pharm Bull, 1994, 42(1): 115－122.

[20] Song Jian-ping(宋建平), Zheng Jiang(曾江), Cui Xiu-ming(崔秀明), et al. Studies on chemical constituents from rhizomes of Panax notoginseng(Ⅱ)(三七根茎的化学成分研究(Ⅱ))[J]. Journal of Yunnan University(Natural sciences)[云南大学学报(自然科学版)], 2007, 29(3): 287－290.