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

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。

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℃, C_(56)H_(78)O_(22), which gave an aglyconemacedonic acid (V′) and two molecules of glucuronic acid after hydrolysis with hydrochloric acid. The spectral analysis of ^(13)CNMR 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℃, C_(35)H_(50)O_7. 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℃, C_(30)H_(46)O_8, 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 ^(13)CNMR, ~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.