全 文 ： 药学学报 Acta Pharmaceutica Sinica 2014, 49 (7): 1019−1021 · 1019 ·





A new iridoid derivative from the roots of
Scrophularia buergeriana
WU Xi-min1†, ZHANG Liu-qiang1†, CHEN Xiao-chong1, FENG Li1,
XING Wang-xing2*, LI Yi-ming1*
(1. School of Pharmacy, Shanghai University of Traditional Chinese Medicine, Shanghai 201203, China;
2. School of Medicine, Hangzhou Normal University, Hangzhou 310036, China)
Abstract: Phytochemical investigation of the roots of Scrophularia buergeriana Miq. (Scrophulariaceae),
resulted in the isolation of a new iridoid derivative named as buergerinin (1). Its structure was elucidated as
rel-(1R, 5R, 6R)-(2-oxa-bicyclo[3.3.0]oct-7-en-6, 7-diyl)dimethoxypropane based mainly on MS and 1D and 2D
NMR spectroscopic analyses.
Key words: Scrophularia buergeriana; iridoid derivative; buergerinin
CLC number: R284 Document code: A Article ID: 0513-4870 (2014) 07-1019-03
北玄参根中的一个新环烯醚萜衍生物
吴喜民 1†, 张刘强 1†, 陈小冲 1, 冯 丽 1, 邢旺兴 2*, 李医明 1*
(1. 上海中医药大学中药学院, 上海 201203; 2. 杭州师范大学医学院, 浙江 杭州 310036)

摘要: 从北玄参块根中发现了一个新的环烯醚萜衍生物, 命名为 buergerinin (1)。通过质谱和一、二维核磁
共振谱等分析, 鉴定了该新化合物结构, 并命名为 rel-(1R, 5R, 6R)-(2-oxa-bicyclo[3.3.0]oct-7-en-6, 7-diyl)dimethoxy
propane。
关键词: 北玄参; 环烯醚萜衍生物; buergerinin

The genus Scrophularia (Scrophulariaceae)
comprises about 200 species, about 36 species of
which occur in China. The root of Scrophularia
ningpoensis Hemsl. has been used as a traditional
Chinese medicine called “Xuan-Shen”, for the

Received 2014-01-14; Accepted 2014-02-19.
Project supported by Funding Scheme for Training Young Teachers in
Shanghai Colleges (ZZszy13057); Shanghai Municipal
Education Commission (2013JW11); the Program
for Professors of Special Appointment (Eastern
Scholar) in Shanghai Institutions of Higher Learning
(for Y M Li), the “XingLin” Scholars and Outstanding
Team Training Plan of SHUTCM and the National
Natural Science Foundation of China (81173518).
†Joint first authors.
*Corresponding author Tel / Fax: 86-21-51322191,
E-mail: ymlius@163.com;
Tel: 86-571-28865674, Fax: 86-571-51322191,
E-mail: xwx117@sina.com
treatment of fever, swelling, constipation, neuritis,
pharyngitis and laryngitis[1]. Scrophularia buergeriana
is a perennial plant native in northern China with an
important role in the traditional medicine of several
oriental cultures. In northern China, the root of
S. buergeriana was used as “Xuan-shen” in clinic
and called as “Bei Xuan-shen”. We have reported
on the isolation, structure elucidation[2, 3], as well as
antioxidation[4], anti-inflammation[5], and anti-platelet
aggregation[6] effects of iridoid and phenylpropanoid
glycosides from S. ningpoensis. We also reported nine
novel iridoid derivatives, two with new carbon skeleton
among them, from S. buergeriana[7]. In our continuous
chemical work on S. buergeriana, here we reported the
isolation and identification of a new iridoid derivative
from the titled plant.
DOI:10.16438/j.0513-4870.2014.07.004
· 1020 · 药学学报 Acta Pharmaceutica Sinica 2014, 49 (7): 1019−1021


Results and discussion
Compound 1 was obtained as light yellow oil.
HR-EI-MS exhibited the molecular-ion peak at m/z
[M]+ 210.125 5, corresponding to the molecular formula
C12H18O3 (calculated for 210.125 6). Its degree of
unsaturation was 4, the signals at δC 146.7 and 126.8 in
the 13C NMR spectrum (Table 1), as well as the signal
at δH 5.46 (1H, br s) in the 1H NMR spectrum (Table 1)
indicated that 1 contained only one double bond, which
was trisubstituted. In addition, 1 contained neither
sugar moieties, nor carbonyl and carboxyl groups. Thus,
there should be three rings in this structure. According
to its DEPT spectrum and chemical shifts, one CH-
group at δC 88.4 and three CH2-groups at δC 67.6, 62.4
and 60.6, should be associated with oxygen atoms. The
carbon at δC 102.1 indicated an aldehyde acetal existed
in its empirical formula, such as C-1 of harpagide.
Finally, two methyl groups at δH 1.32 (3H, s), 1.36 (3H,
s) and δC 24.5, 25.0 were observed in the NMR spectra.
Based on the above spectroscopic evidence,
the chemical shifts of 1 were the most plausible
according with ningpogenin, which was obtained from
S. ningpoensis[8], except for δC 24.5, 25.0 and 102.1,
which suggested that there was a more aldehyde
acetal group in 1. The above conclusion was further
elucidated by 2D NMR spectroscopy, including HMQC,
HMBC, 1H-1H COSY and NOESY.
In HMBC, there was a long-range coupling between
δH 1.32 (3H, s) and δC 25.0, between δH 1.36 (3H, s)
and δC 24.5, as well as between protons of two methyl
groups (δH 1.32, 1.36) and the carbon at δC 102.1, so the
connection of the two methyl groups to the carbon at
δC 102.1 was confirmed. In the meantime, there were
two long-range couplings between H-9, H-10 and the
carbon at δC 102.1, implicating that C-9 and C-10 were
each connected through the oxygen atom to the carbon
at δC 102.1, which formed the third ring together
with C-6, 7. Hence the structure of compounds 1 is
elucidated as rel-(1R, 5R, 6R)-(2-oxa-bicyclo[3.3.0]
oct-7-en-6, 7-diyl)dimethoxypropane (Figure 1), namely
buergerinin.


Figure 1 Structure of compound 1
Experimental
General experimental procedures Column
chromatography (CC): silica gel (SiO2, 200−300 mesh,
Qingdao Haiyang Co., China), Sephadex LH-20
(Pharmacia Biotech AB, Uppsala, Sweden). ODS
(Greenberbs Science & Technology Development Co.,
Ltd., Beijing, China). TLC: silica gel HSGF254 (Yantai
Jiangyou Guijiao Kaifa Co., China), Optical rotation:
Perkin-Elmer 341 polarimeter. NMR Spectra: Bruker
AV-400 instrument at 400 (1H) and 100 MHz (13C); in
CDCl3 soln.; δ in ppm rel. to Me4Si; J in Hz. EI-MS
and HR-EI-MS (70 eV) were carried out on a Finnigan
MAT 95 mass spectrometer.
Plant material The roots of S. buergeriana Miq.
were collected in Chang Bai Mountains, Jilin province,
China, and identified by Prof. Changheng Tan of
Shanghai Institutes of Materia Medica.
Extraction and isolation The air-dried roots (10
kg) of S. buergeriana were ground and extracted with
95% EtOH at r.t. The residue was taken up in H2O
and extracted with EtOAc and BuOH. After being
defatted with petroleum ether (PE), the EtOAc extract
was subjected to CC (SiO2; gradient of 100%, 50%,
20%, and 0 PE in EtOAc, then acetone): five fractions
(Fr. I−V). Fr. I was repeatedly purified by CC (SiO2;
gradient of 0, 5%, 10%, and 20% EtOAc in PE) to
furnish buergerinin (6.0 mg).
Buergerinin (1) Light yellow oil, [α] 22D = + 5.65
(c 0.064, CHCl3). EI-MS: m/z 210 [M]+ (100), 152
[M−CH3COCH3]+ (7), 134 (45), 122 (55), 94 (80), 59
[CH3COCH3+1]+ (60) (Figure 2). 1H and 13C NMR
(CDCI3) see Table 1.

Table 1 1H and 13C NMR (CDCl3) data of compound 1.
*Individual protons assigned by HMQC, HMBC and 1H-1H
COSY. ※C- the hemiacetal carbon atom. aOverlapped
No. δC DEPT δH* (J in Hz)
1 88.4 CH 5.06 (d, 7.2)
3 67.6 CH2 3.65-3.70a
4

27.6

CH2

1.78 (1H, m)
1.70 (1H, m)
5 42.2 CH 3.03 (m)
6 48.7 CH 2.92 (m)
7 146.7 C
8 126.8 CH 5.46 (br s)
9

62.4

CH2

3.72 (dd, 10.8, 4.7)
3.65 (dd, 10.8, 4.9)
10

60.6

CH2

4.14 (d, 13.1)
4.08 (d, 13.1)
※C 102.1 C
Me 24.5 CH3 1.32 (s)
Me 25.0 CH3 1.36 (s)
WU Xi-min, et al: A new iridoid derivative from the roots of Scrophularia buergeriana · 1021 ·




Figure 2 The proposed fragmentation pathways of compound 1
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