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Journal of Chinese Pharmaceutical Sciences 2001, 10 (3) 113

Triterpenes and Other Constituents from Rhaponticum uniflorum

Zhang Yonghong1, Wang Wen2, Wang Tao1 and Wang Hanqing1*

1. Institute of Lanzhou Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000;
2. School of Pharmaceutical Sciences,Peking University, Beijing 100083

Received May 17, 2001; Accepted June 31, 2001

Abstract From the roots of Rhaponticum uniflorum a new triterpene was isolated together with
ursolic acid(2), 3-oxo-19a-hydroxyurs-12-en-28-oic acid (3), pomolic acid (4),
2a,3a,19a-trihydroxyurs-12-en-28-oic acid (5), arctic acid (6), catechin (7) and b-sitosterol (8). The structure
of the new compound was elucidated as 2a,3a,19a,25-tetrahydroxyurs-12-en-23,28-dioic acid (1) on the
basis of spectral and chemical methods.

Key words Rhaponticum uniflorum; Compositae; Ttriterpene

Introduction

Rhaponticum uniflorum (L.) DC. (Compositae) is
distributed in northern China. Its root has been used
as a Traditional Chinese Medicine for the treatment
of fever and intoxications[1]. Phytochemical studies
of R. uniflorum were reported previously[2~4]. This
paper describes the isolation and identification of a
new triterpene (1) along with other compounds.

Results and Discussion

Compound 1 was isolated as an amorphous pow-
der, mp 293~295oC, [a] 20D +43.6 (c 0.21, pyridine). It
gave a positive coloration with the Liebermann-Bur-
chard test for triterpenoids. The IR spectrum showed
the absorption for hydroxyl groups (3412 cm-1) and
carboxylic group (1689 cm-1). The 13C NMR and
DEPT spectral data indicated that 1 possessed five
methyl, nine methylene, seven methine and nine
quaternary carbons, from which the formula was
determined as C30H46O8. Furthermore, the EI mass
spectrum exhibited significant fragements at m/z 264,
246, 201, 187, 146, which indicated the presence of a
tertiary hydroxyl function on C-19 in the
urs-12-en-28-oic acid skeleton in accord with its 13C
NMR spectrum[5]. The 1H NMR spectrum of 1
showed signals for two protons on C-1 (d 1.47, 2.28,
m, 2H) and two geminal protons on C-25 (d 4.17,
4.22, dd, J=13.8, 1.5 Hz, 2H)[6]. Since the signal of
C-4 was shifted to lower field (d 54.70) than that of 5
(d 38.67) and that 1 differed from 5 by the
replacement of a methyl group with acrboxyl group,
which was assiged to C-23 on the basis of HMBC
and NOESY difference spectra. Thus, 1 was
elucidated as
2a,3a,19a,25-tetrahydroxyurs-12-en-23, 28-dioic
acid.










Fig. 1. Selected HMBC correlations of compound 1.

Experimental

Plant material
The roots of Rhaponticum uniflorum (L.) DC.
were purchased from the company of Chinese me-
dicinal materials in Gansu Province and were identi-
fied by Prof. Zhou Yinshou, Lanzhou Medical Col-
lege. A voucher specimen (98001) was deposited in
the Herbarium of the Pharmacy Department, Lan-
zhou Medical College.

Extraction and isolation
Dried and powdered roots of R. uniflorum (3 kg)
were exhaustively extracted with MeOH at room
temperature, and the combined extract was concen-
trated under reduced pressure. The residue was sus-
pended in water and subjected to sequential extrac-
tion with petrol, EtOAc and n-BuOH, successively.
The EtOAc extract (40 g) was chromatographed over
a silica gel column (200~300 mesh, 500 g) and gradi-
ently eluted with Petrol containing increasing
amounts of EtOAc. The fractions were combined by
TLC monitors. The fractions were submitted to silica
gel column to afford compounds 1 (46 mg), 2 (10
mg), 3 (14 mg), 4 (56 mg), 5 (41 mg), 6 (25 mg), 7
(45 mg) and 8 (18 mg).
*To whom correspondence should be addressed.
HOOC
HO
HO
HOH2C
HO
COOH





Journal of Chinese Pharmaceutical Sciences 2001, 10 (3) 114
Identification
Compound 1 Amorphous powder
(CHCl3-MeOH), mp 293~295
oC. IR (KBr) cm-1:
3412, 1689, 1605, 1558, 1461, 1398, 1051. FABMS
m/z 534[M]+, 517[M+H-H2O]
+. EIMS m/z 517, 264,
246, 201, 187, 146. 1H and 13C NMR data: see Table
1.
Ursolic acid 2 White needle, mp 284~286 oC.
EIMS m/z 456[M]+, 438, 423, 410, 395, 248, 208,
189, 135. Identified by co-IR spectra with an
authentic sample.
3-oxo-19a-hydroxyurs-12-en-28-oic acid 3
Amorphous powder, mp 196~197 oC. EIMS m/z
470[M]+, 452, 424, 409, 352, 264, 246, 206, 205, 146.
Spectral data as reported[7].
Pomolic acid 4 Crystalline powder, mp 272~
274 oC. EIMS m/z 472[M]+, 454, 439, 426, 408, 393,
354, 264, 246, 208, 207, 146. Spectral data as
reported[7].
2a,3a,19a-trihydroxyurs-12-en-28-oic acid 5
Crystalline powder, mp 270~271 oC. EIMS m/z
488[M]+, 470, 442, 424, 409, 264, 224, 223, 218, 146.
Spectral data as reported[7].
Arctic acid 6 Orange yellow needle, mp 215~
217 oC. EIMS m/z 248[M]+, 231, 203, 171, 159, 115.
Spectral data as reported[8].
Catechin 7 Platelets, mp 161~162 oC. EIMS
m/z 290[M]+, 152, 139, 123. Spectral data as re-
ported[6].

Table 1. NMR assignment of compound 1 (in pyridine-
d5)
13C 1H* 13C 1H
1 48.26 t 1.47 m,
2.28 m
16 26.96 t 2.02 m,
3.10 m
2 68.69 d 4.23 m 17 48.07 s
3 81.24 d 4.62 d
(8.4)
18 54.70 d 3.02 brs
4 54.70 s 19 72.70 s
5 52.34 d 2.23 m 20 42.31 d 1.30 m
6 21.37 t 21 26.40 t 1.40 m
7 33.31 t 22 38.54 t 2.04 m
8 40.44 s 23 181.05 s
9 48.07 d 24 13.73 q 1.68 s
10 38.54 s 25 64.79 t 4.17, 4.22 dd
(13.8, 1.5)
11 24.10 t 1.30 m,
2.09 m
26 17.31 q 1.06 s
12 127.63 d 5.54 m 27 24.61 q 1.62 s
13 140.08 s 28 181.05 s
14 42.09 s 29 27.08 q 1.39 s
15 29.25 t 1.16m,
2.21 m
30 16.74 q 1.08 d (6.6)
*J (Hz) in parentheses.

References

[1] Jiangsu New Medical College, The Encyclopaedia of Traditional Chinese Medicine [M]. Shanghai Science and Technology Press,
Shanghai, 1985: 2348
[2] Guo DA, Lou ZC, Gao CY, Qiao L and Peng JR. [J] Acta Pharm Sin, 1991, 26: 442
[3] Jiang XF and Li X. [J] Chin Tradi Herb Drugs, 1997, 28: 262
[4] Li XQ, Wang JH, Wang SX and Li X. [J] J Shengyang Pharm Univ, 2000, 17: 260
[5] Budzikiewicz H, Wilson JM and Djerassi C. [J] J Am Chem Soc, 1963, 85: 3688
[6] Jia ZJ, Liu XQ and Liu ZM. [J] Phytochemistry, 1993, 32: 155
[7] Cheng DL and Cao XP. [J] Phytochemistry, 1992, 31: 1317
[8] Wei HX, Gao WY, Tian YJ, Guan YK, Huang MH and Cheng DL. [J] Pharmazie, 1997, 52: 245


祁州漏芦中三萜及其他类化合物

张永红 1 王 文 2 汪 涛 1 汪汉卿 1

1. 中国科学院兰州化学物理研究所 OSSO国家重点实验室，兰州 730000；
2. 北京大学医学部天然药物及仿生药物国家重点实验室，北京 100083

摘 要 从中药祁州漏芦中分离得到一个新的三萜类化合物，根据波谱分析，理化常数测定确定其结构为
2a,3a,19a,25-四羟基乌苏-12-烯-23,28-二酸，同时还分到乌苏酸，3-氧-19a-羟基乌苏-12-烯-28-酸，坡模提酸，
2a,3a,19a-三羟基乌苏-12-烯-28-酸，牛蒡子酸，儿茶精和b-谷甾醇。

关键词 祁州漏芦；菊科；三萜