全 文 ： 2009 年 5 月 第 7 卷 第 3 期 Chin J Nat Med May 2009 Vol. 7 No. 3 187
Chinese Journal of Natural Medicines 7 (2009) 0187−0189
doi: 10.3724/SP.J.1009.2009.00187
Chinese
Journal of
Natural
Medicines
Megastigmane-type Compounds from Rotala rotundifolia
TAN Qin-Gang1,2, CAI Xiang-Hai1, FENG Tao1,2, LUO Xiao-Dong1*
1State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences,
Kunming 650204, China;
2Graduate School of the Chinese Academy of Sciences, Beijing 100039, China
Available online 20 May 2009
【ABSTRACT】 AIM: To investigate the chemical constituents of Rotala rotundifolia. METHOD: Silica gel column chromatography
was used to isolate the constituents. The structures were determined by extensive spectroscopic methods. RESULT: Two megastig-
mane-type compounds were obtained from the aerial parts of Rotala rotundifolia. CONCLUSION: Compound 1, named rotundifoline
A, is a new compound.
【KEY WORDS】 Rotundifoline A; Rotala rotundifolia; Lythraceae
【CLC Number】 R284.1 【Document code】 A 【Article ID】1672-3651(2009)03-0187-03
1 Introduction
Rotala rotundifolia, family Lythraceae, is widely distrib-
uted in Southern China, India, Malaysia, Sri Lanka and Ja-
pan[1]. In Yunnan province, China, Rotala rotundifolia has
been used for the treatment of carbuncle, furuncle, rheuma-
tism and arthralgia. Furthermore, recent investigation showed
its antibacterial activity against Staphylococcus aureus, Es-
cherichia coli and Bacillus diphtheriae[2]. In this paper, we
describe the isolation and structural elucidation of the new
compound rotundifoline A (1) and the known analogue
vomifoliol [3,4] (2) from the aerial parts of Rotala rotundifolia.
2 Results and Discussion
Compound 1 was obtained as colorless oil. Its molecular
formula was assigned to be C29H44O10 based on the negative
2 cle IDodeompound 1 is a new compound.e obtained from
the thods. nennHR-ESI-MS spectrum (m/z 575.283 3; Calcd.
575.283 2 for C29H44O10Na, [M + Na]+). The IR spectrum
exhibited bands at 3 426, 1 707 and 1 651 cm−1, attributable
to the presence of hydroxyl and conjugated carbonyl groups,
respectively. The 1H and 13C NMR spectra of 1 (see Table 1)
exhibited signals for six methyls without methoxyls, five
【Received on】 2008-02-25
【Foundation Item】 This project was supported by the National
Basic Research Program of China (973 Program 2009CB522300)
and the Chinese Academy of Sciences (XiBuZhiGuang Project)
【*Corresponding author】LUO Xiao-Dong, Prof., Tel: 86-871-
5223177, Fax: 86-871-5150227, E-mail: xdluo@mail.kib.ac.cn
methylenes including one terminal bond, eleven methines and
seven quaternary carbons. The presence of the -CH2-CO-
CH=C-CH3 group was indicated by the correlations of δH1.93
(3H, s, H-13) with δC 163.8 (s, C-1), 126.8 (d, C-2) and 79.3
(s, C-6), and the correlations of δH 2.16 (1H, d, J= 17.2 Hz,
H-4a) and 2.58 (1H, d, J= 17.2 Hz, H-4b) with δC197.6 (s,
C-3) in the HMBC spectrum of 1 (Fig.2). Furthermore, the
correlations of δH 1.05 (3H, s, H-12) and 1.03 (3H, s, H-11)
with δC79.3 (s, C-6), 50.3 (t, C-4) and 41.7 (s, C-5), and of
δH1.24 (3H, d, J= 6.3 Hz, H-10) with δC 133.2 (d, C-8) were
also observed. The presence of a trans-disubstituted double
bond was observed in the 1H NMR at δH5.99 (1H, d, J = 15.8
Hz, H-7), 5.79 (1H, dd, J = 15.8 Hz, 6.5 Hz, H-8) and sup-
ported by the correlations of δH 5.99 (1H, d, J = 15.8 Hz, H-7)
with δC133.2 (d, C-8). All these data suggested the existence
of carotenoid-like unit (megastigmane) in 1. By comparing
the data with those of vomifoliol[3,4], the chemical shift of δC
68.0 (d, C-9) in vomifoliol downfielded to 73.9 in 1. This
difference suggested another unit was connected with C-9 in
1. The signals of δH 3.25-3.42 (4H, m), 4.34 (1H, d, J = 7.8
Hz) in the 1H NMR spectrum and δC 101.1 (d, C-1) in the
13C-NMR spectrum suggested the presence of a sugar moiety.
The coupling constant (J = 7.8 Hz) of the anomeric proton
was compatible with the β-configuration for the sugar moiety.
The linkage position was unambiguously determined to be at
C-9 by the long-range correlation from δH 4.34 (1H, d, H-1)
of the sugar moiety to δC73.9 (d, C-9) of the megastigmane
unit in the HMBC spectrum of 1. Careful comparison of the
above NMR data with those of the known compound
(9R)-roseoside (δC-9 77.0)[5,6] and its diastereomer (9S)-roseo-
TAN Qin-Gang, et al. /Chinese Journal of Natural Medicines 2009, 7(3): 187−189
188 Chin J Nat Med May 2009 Vol. 7 No. 3 2009 年 5 月 第 7 卷 第 3 期
Table 1 1H NMR (400 MHz) and 13C NMR (125 MHz ) data of compound 1 in (CD3)2CO (δ, J in Hz)
Position δC (DEPT) δH Position δC (DEPT) δH
1 163.8 (s) C9-Glc 1 101.1 (d) 4.34 (1H, d, 7.8)
2 126.8 (d) 5.81 (1H, s) 2 74.6 (d) 3.25 (1H, m, 7.8, 9.1)
3 197.6 (s) 3 78.1 (d) 3.37 (1H, m, 9.1, 9.4)
4 50.3 (t) 2.16 (1H, d, 17.2) 2.58 (1H, d; 17.2) 4 71.4 (d) 3.35 (1H, dd, 9.4, 9.5)
5 41.7 (s) 5 74.9 (d) 3.42 (1H, ddd, 2.1, 6.0, 9.5)
6 79.3 (s) 6 64.6 (t) 4.19 (1H, dd, 11.8, 6.0) 4.48 (1H, dd, 11.8, 2.1)
7 132.9 (d) 5.99 (1H, d, 15.8) MTA 1 168.1 (s)
8 133.2 (d) 5.79 (1H, dd, 15.8, 6.5) 2 128.1 (s)
9 73.9 (d) 4.42 (1H, m) 3 143.5 (d) 6.81 (1H, tq, 6.9, 1.8)
10 22.3 (q) 1.24 (3H, d, 6.3) 4 24.1 (t) 2.21, 2.32 (2H, m)
11 24.6 (q) 1.03 (3H, s) 5 41.5 (t) 1.63 (2H, m)
12 23.3 (q) 1.05 (3H, s) 6 72.6 (s)
13 19.1 (q) 1.93 (3H, s) 7 146.3 (d) 5.95 (1H, dd, 17.3, 11.0)
8 111.7 (t) 5.02 (1H, dd, 17.3, 1.8) 5.27 (1H, dd, 11.0,1.8)
9 12.4 (q) 1.82 (3H, s)
10 28.4 (q) 1.28 (3H, s)
side (δC-974.0)[7-9], the absolute configuration of C-9 in com-
pound 1 (δC73.9) was in accordance with the latter one. The
presence of an α, β-unsaturated monoterpenoid carboxylic
acid was indicated by the correlations of δH1.82 (3H, s, H-9)
with δC 128.1 (s, C-2), 143.5 (d, C-3) and 168.0 (s, C-1),
of 6.81 (1H, tq, J = 6.9, 1.8 Hz, H-3) with δC24.1 (t, C-4),
41.5 (t, C-5) and 168.1 (s, C-1) in the HMBC spectrum of 1.
Furthermore, the correlation of a methyl (δH1.28, s, H-10)
with δC111.7 (t, C-8), 24.1(t, C-4), 41.5 (t, C-5) and 72.6
(s, C-6). These data were superimposable to those reported
of menthiafolic acid [10]. The attachment of this unit to C-6 of
the sugar moiety was established by its HMBC correlations
between δH4.19, 4.48 (2H, H-6) with δC168.1 (s, C-1). On
the basis of the evidence mentioned above, this new comp-
ound was characterized as rotundifoline A (1) shown in Fig. 1.
Fig. 1 Structures of compounds 1 and 2
Fig. 2 Key HMBC correlations for compound 1
3 Experimental
3.1 General
NMR spectra were recorded on Bruker AM-400 and
DRX-500 spectrometers with TMS as internal standard. Op-
tical rotation was measured with Horiba SEPA-300 po-
larimeter. IR spectrum was obtained on a Bruker Tensor-27
spectrometer with KBr pellets; Neg. ESI-MS spectra were
recorded on an API Qstar Pulsar I spectrometer. Column
chromatography was performed over silica gel (200-300
mesh, Qingdao Marine Chemical Inc., China), RP-18 silica
gel (40-65 μm, Merck Company,) and Sephadex LH-20
(40-70 μm, Pharmacia Fine Chemical Co., Ltd., Sweden),
respectively. TLC was carried on silica gel G plate and spots
were detected by 10% sulfuric acid reagents followed by
heating.
3.2 Plant material
The aerial parts of Rotala rotundifolia were collected in
Yunnan Province of China in April, 2007 and identified by
Mr. CUI Jing-Yun, Xishuangbanna Tropic Botanical Garden,
CAS. A voucher specimen (KUN 20070408) has been depos-
ited in the Herbarium of Kunming Institute of Botany, CAS.
TAN Qin-Gang, et al. /Chinese Journal of Natural Medicines 2009, 7(3): 187−189
2009 年 5 月 第 7 卷 第 3 期 Chin J Nat Med May 2009 Vol. 7 No. 3 189
3.3 Extraction and isolation
The dried and pulverized whole plant of Rotala rotundi-
folia (7.8 kg) was extracted with 95% EtOH (5 L × 3) at
room temperature (48 h × 3). After evaporation of the solvent
under reduced pressure, the viscous residue (300 g) was
re-dissolved in H2O, and then partitioned with EtOAc (1 L ×
3) to afford EtOAc and H2O layers. The EtOAc fraction (160
g) was subjected to silica gel column chromatography (9 ×
150 cm) and eluted with CHCl3-Me2CO (1∶0–1∶1, V/V) to
give seven fractions (I-VII). Fr. VII was submitted to RP-18
(30%-65%) to give three sub-fractions (A-C). Compound 1
(18 mg) was obtained from sub-fraction C by silica gel col-
umn chromatography (CHCl3-MeOH 12∶1) and Sephadex
LH-20 (eluted with MeOH).
Rotundifoline A, colorless oil, [α] 20D + 11.2° (c 2.40,
CHCl3). IR (KBr) vmax: 3 426 (OH), 1 707 (C=O), 1 651
(C=O) cm−1. Neg. HR-ESI-MS m/z 575.283 3 (Calcd. 575.
283 2 for C29H44O10Na [M + Na]+). 1H NMR and 13C NMR
data see Table 1.
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圆叶节节菜中 Megastigmane类型的化合物
谭钦刚 1,2, 蔡祥海 1, 冯 涛 1,2, 罗晓东 1,*
1中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室, 昆明 650204;
2中国科学院研究生院, 北京 100039
【摘 要】 目的：研究圆叶节节菜的化学成分。方法：运用硅胶柱色谱技术分离、光谱技术鉴定结构。结果：从其地上部
分分离得到两个 Megastigmane 类型化合物。结论：化合物 1(Rotundifoline A)是一个新化合物。
【关键词】 Rotundifoline A; 圆叶节节菜; 千屈菜科
【基金项目】 973 计划 (973 Program 2009CB522300)；中国科学院西部之光计划