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云南甘草次皂甙和云南甘草皂甙元的结构鉴定

GLYYUNNANPROSAPOGENIN AND GLYYUNNANSAPOGENIN FROM THE ROOTS OF GLYCYRRHIZA YUNNANENSIS

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【作者】 曾路张如意王动庞吉海张志亮高从元楼之岑

【Author】 L Zeng, RY Zhang, D Wang~*, JH Pang~*, ZL Zhang, CY Gao~* and ZC Lou (School of Pharmaceutical Sciences, ~* Analysis and Calculation Center, Beijing Medical University, Beijing 100083)

【机构】 北京医科大学药学院北京医科大学分析计算中心北京医科大学药学院 北京 100083北京 100083北京 100083

【摘要】 本文报告从云南甘草(Glycyrrhiza yunnanensis)中分离得到的另二个新三萜类成分,云南甘草次皂甙D(glyyunnanprosapogenin D)(Ⅴ)和云南甘草皂甙元F(glyyunnansapogenin F)(Ⅸ)的结构。经光谱分析和化学反应证明,云南甘草次皂甙D(Ⅴ)的结构为oleana-11,13(18)-dien-29-oic acid,3β,21α-di-(O-β-D-glucuronic acid)pyranoside;云南甘草皂甙元F(Ⅸ)的结构为3β,24-dihydroxy-16-oxo-oleana-11,13(18)-dien-30-oic acid。此外,本文还对云南甘草皂甙元C,E,F和马其顿酸等具齐墩果烷-11,13(18)-二烯类化合物的质谱裂解途径进行了探讨和分析。

【Abstract】 Two new triterpenoidal sapogenins of oleanane type, namely glyyunnanprosapogenin D(Ⅴ) and glyyunnansapogenin F(Ⅸ) were isolated from the roots of-Glycyrrhiza yunnanensis Cheng f. et L. K. Tai, family Leguminosae, collected from Yunnan Province, China. V was obtáined as hexaacetate and dimethyl ester form (Vc), mp 168~170℃, C56H78O22, which gave an aglyconemacedonic acid (V′) and two molecules of glucuronic acid after hydrolysis with hydrochloric acid. The spectral analysis of 13CNMR and 1HNMR showed that Vc had two glycoside residues attached to the aglycone, and therefore the structure of V was established as oleana-11, 13(18)-dien-29-oic acid, 3β, 21α-di-(O-β-D-glucuronic acid) pyranoside.Ⅸ was obtained as its diacetate and monomethyl ester form (Ⅸc), mp 188~190℃, C35H50O7. The IR, 1HNMR and UV spectra showed that the Ⅸc had a skeleton of oleanane type triterpenoid with heteroannular diene. Ⅸb, diacetate of Ⅸ, unpurifed, was converted to Ⅸf with chromium trioxide in glacial acetic acid. Ⅸf, mp 160~164℃, C30H46O8, was proved to be olean-12-en-11-oxo-3β, 24-diacetoxy-18β-hydroxy-30-oic acid, 30→18β lactone with another carbonyl group at C-15, 16, 21 or 22 by the analysis of 13CNMR, 1HNMR and MS spectra. Ⅸc exhibited a negative absorption in Cd spectrum at 298nm, in accord with C-16-oxo of oleana-11, 13(18)-diene compounds, thus the structure of Ⅸ is 3β, 24-dihydroxy-16-oxo-oleana-11, 13(18)-dien-30-oic acid and that of ixf is 3β, 24-diacetoxy-11, 16-dioxo-18β-hydroxy-olean-12-en-30-oicacid, 30→18β lactone.

  • 【文献出处】 药学学报 ,Acta Pharmaceutica Sinica , 编辑部邮箱 ,1990年10期
  • 【被引频次】19
  • 【下载频次】207
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