高等学校化学学报

高等学校化学学报 ›› 1993, Vol. 14 ›› Issue (9): 1293.

• 研究论文 • 上一篇    下一篇

2D-HOHAHA和ROESY方法归属复杂天然有机化合物的NMR谱线

杨延武1, 何炳林1, 许肖龙2, 裘鉴卿2, 王德华2, 钱保功2   

  1. 1. 南开大学高分子化学研究所, 天津 300071;
    2. 中国科学院武汉物理研究所波谱与原子分子物理国家重点实验室, 武汉
  • 收稿日期:1992-12-29 修回日期:1993-04-23 出版日期:1993-09-24 发布日期:1993-09-24
  • 通讯作者: 杨延武.
  • 作者简介:第一作者:男, 30岁, 讲师.
  • 基金资助:

    国家自然科学基金;中国科学院上海有机化学研究所生命有机化学国家重点实验室

Structural Elucidation and 1H Spectral Assignments of Complex Natural Organic Compounds by2D-HOHAHA and ROESY Methods

YANG Yan-Wu1, HE Bing-Lin1, XU Xiao-Long2, QIU Jian-Qing2, WANG De-Hua2, QIAN Bao-Gong2   

  1. 1. Institute of Polymer Chemistry, Nankai University, Tianjin, 300071;
    2. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics, Chinese Academy of Sciences, Wuhan, 430071
  • Received:1992-12-29 Revised:1993-04-23 Online:1993-09-24 Published:1993-09-24

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摘要： 用同核化学位移相关谱及旋转坐标系中的同核化学位移相关谱和旋转坐标系中的同核NOE实验等新的二维核磁共振方法对首次从西洋参叶中分离出的Ocotillol型皂甙(OTS)的1H化学位移进行了完全归属,为OTS分子溶液中的三维空间结构研究提供了可靠的结构参数.

关键词: 旋转坐标系中的同核化学位移相关谱, 同核NOE实验, 谱线归属, 西洋参皂甙

Abstract: Because of the serious spectral overlap in several regions of the 1Hspectrum, the 1Hchemical shifts of an ocotillol-type saponin, which was first isolated from the leaves of panax Quinquetolium L., are completely assigned by recently developed two dimensional homonuclear Hartmann-Hahn spectroscopy (2D-HOHAHa) and rotating frame nuclear Overhauser effect spectroscopy (ROESY).The 2D-HOHAHAexperiment is able to obtain the phase sensitive two dimensional spectrum with all peaks in the near absorption mode, and the cross peaks multiplets are nearly in-phase.So the high detection resolution and sensitivity of 2D-HOHAHAexperiment make it possible to observe the cross peaks overlapped such as H13-H17 and H23a-H23e, and that covered by diagonal peaks with high strength in COSYspectrum, such as H2a-H2e.On the other hand, during the spin locking period of 2D-HOHAHAexperiment, relayed magnetization transfer will occurs.For shorter mixing period (shorter than 20 ms) little RELAY signals can be observed, but for longer mixing times single-RELAY and multiple-RELAY effects become significant.Through the RELAY cross peaks appeared in 2D-HOHAHA spectrum of OTS, the accurate 1Hchemical shifts of some proton signals in severe spectral overlap regions are assigned, such as, the 1Hchemical shifts of H22a, H22e, Hla, H1e and H9 proton are 1.592, 1.857, 1.026, 1.640 and 1.586 ppm respectively.The spin-locking NOEexperiment is used to provide through-space connectivity between the various coupling networks of protons.The linking position of glucosyl with aglycone in OTSand the chemical shift assignments of methyl protons which are easily distinguished but difficultly assigned are determined by ROESYspectrum.

Key words: 2D-HOHAHA, ROESY, Spectral assignments, Ocotillol-type saponin

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