全 文 ：Isodaphnoretin B , a New Bicoumarin from
Stellera chamaejasme
YANG Guo-Hong , CHEN Dao-Feng＊
Department of Pharmacognosy , Fudan University , Shanghai 200032 , P.R.China
【ABSTRACT】　AIM:To study the chemical constituents of the root of Stellera chamaejasme.METHODS:Silica gel col-
umn chromatogramphy was used to isolate the compounds , and spectroscopic techniques(NMR , UV , IR , MS and optical ro-
tations)were used for the structural elucidation.RESULTS:Two bicoumarins:7-hydroxy-5 , 6-dimethoxy-3-[ (2-oxo-2H-1-
benzopyran-7-yl)oxy] -2H-1-benzopyran-2-one , named isodaphnoretin B(1)and daphnoretin(2)were obtained from the root
of Stellera chamaejasme.CONCLUSION:Compound 1 is a new bicoumarin.
【KEY WORDS】Stellera chamaejasme;Bicoumarin;Isodaphnoretin B;Daphnoretin;Thymelaeaceae
【CLCNumber】　R284.1　　【Document code】　A　　【Ariticle ID】　1672-3651(2006)06-0425-03
【Received on】　2006-09-04
【Foundation Item】　This investigation was supported by Fudan Univer-
sity Graduate Innovation Foundation(CQF301804)awarded to Guohong
Yang.
【＊Corresponding author】　Chen Dao-Feng , Professor of Pharm-acog-
nosy , Tel:(86)-21-54237453 , Fax:(86)-21-64170921, E-mail:
dfchen@shmu.edu.cn.
　 　 The root of Stellera chamaejasme L.
(Thymelaeaceae), a toxic plant widely distributed in the
north and southwest of China , is used as “Langdu” in
traditional Chinese medicine.It has long been used for
the treatment of scabies , tinea , stubborn skin ulcers ,
chronic tracheitis , and tuberculosis in China[ 1] .In re-
cent years , “ Langdu” is also used for the treatment of
intestinal , gastric and pulmonary cancers[ 2 , 3] .S .
chamaejasme contains flavonoids , biflavonoids and bi-
coumarins , which show various bioactivities including
antibacterial , immunomodulating and anti-HIV activi-
ties[ 1 , 4-8] .In our previous study , some antimitotic and
antifungal biflavonoids have been isolated from this
plant[ 9] .Further investigation on the chemical con-
stituents of the title plant led to the isolation and char-
acterization of one new bicoumarin , isodaphnoretin B
(1), together with a known daphnoretin(2).This pa-
per reports the structural elucidation of the new com-
pound.
1　Results and Discussion
Compound 2 was identified as daphnoretin (see
Figure 1) by comparing its spectroscopic data
(1H NMR , 13C NMR , EIMS , UV , IR and optical rota-
tions)with those of reported[ 7] .
Fig 1　The structures of 1 and 2
Isodaphnoretin B(1), obtained as white amorphous
powder , showed strong blue fluorescence under UV , indi-
cating that 1 is a coumarin.It showed a [M-H] - peak at
m/z 381.061 0(calcd.for C20H13O8:381.061 0)in the
negative HR-ESI-MS , corresponding to a molecular for-
mula of C20H14O8.Its UV spectrum showed two strong
absorptions at 208(logε4.45)nm and 338(logε4.55)
nm , which are characteristic of a 7-hydroxyl or 7-oxy
coumarin[ 7] .The IR spectrum showed the presence of a
hydroxyl group(3 340 cm-1), lactone carbonyl group(1
730 cm-1), and aromatic ring(1 600 , 1 580 , 1 510 and
1 474cm-1).
The signals of a set of AB-type protons [ δ6.37
(1H , d , J =9.6 Hz), 8.03(1H , d , J =9.6 Hz)] ,
three coupling protons [ δ7.70(1H , d , J =8.5 Hz),
7.12(1H , dd , J =8.5 , 1.7Hz), δ7.17(1H , d , J
=1.7Hz)] , two single protons[ δ7.84(1H , s), δ
6.68(1H , s)] in the 1H NMR(see Table 1)were sim-
ilar to the known bicoumarin daphnoretin(2), indicat-
ing that 1 was also a bicoumarin.Comparison of the
1H NMR spectral data of 1 with those of 2 revealed that
the chemical shift values and splitting patterns of 1 a-
greed well with those of 2 , except that 1 was one
methoxyl group (δ3.93 , 3H , s)more than 2 , which
was confirmed by the
13
C NMR data (δc61.7).The
　2006年 11月　第 4卷　第 6期 Chin J Nat Med　Nov.2006　Vol.4　No.6　425　
HMBC(see Figure 2)correlations of the proton [ δ6.68
(1H , s)] with δc148.7(C-9), δc105.3(C-10), δc
137.7(C-6)and δc154.6(C-7)indicated that the pro-
ton signal at δ6.68 was 5-H or 8-H.According to the
literature , the chemical shift values for 5-H of coumarin
were about 7.30 , and those of 8-H were around 6.
70[ 10] , which indicated that the proton signal at δ6.68
was due to the 8-H.The HMBC correlations of one
methoxyl group[ δ3.79(3H , s)] with δc137.7(C-6)
and another methoxyl group [ δ3.93(3H , s)] with δc
149.0(C-5)indicated that these two methoxyl groups
were at C-5 and C-6 positions.The two coumarin units
of 1 were linked at C-3 and C-7′, which was deduced
by the HMBC correlations of δ7.84(4-H)with δc156.
7(C-7′)and δ7.12(6′-H)/ δ7.17(8′-H)with δc
135.2(C-3).The structure of 1was thus established to
be 7-hydroxy-5 , 6-dimethoxy-3-[(2-oxo-2H-1-benzopy-
ran-7-yl)oxy]-2H-1-benzopyran-2-one , and named iso-
daphnoretin B.
Table 1　1H NMR(400 MHz)and 13C NMR(100 MHz)data
of 1(DMSO-d6)
Position
1
H(δ) 13C(δ) Position 1H(δ) 13C(δ)
2 159.9, s 2′ 159.8 , s
3 135.2, s 3′ 6.37 , 1H , d , J=9.6Hz113.8 , d
4 7.84 ,1H , s 126.4, d 4′ 8.03 , 1H , d , J=9.6Hz144.0 , d
5 149.0, s 5′ 7.70 , 1H , d , J=8.5Hz129.8 , d
6 137.7, s 6′ 7.12 ,1H , dd ,
J =8.5, 1.7Hz 113.2 , d
7 154.6, s 7′ 156.7 , s
8 6.68 ,1H , s 98.7, d 8′ 7.17 ,1H , d, J=1.7Hz 103.7 , d
9 148.7, s 9′ 154.9 , s
10 105.3, s 10′ 114.2 , s
5-OMe 3.93, 3H , s 61.7, q
6-OMe 3.79, 3H , s 60.5, q
Fig 2　Key HMBC correlations of 1
2　Experimental
2.1　General
Optical rotations were measured on a P-1020 po-
larimeter (JASCO , Japan).UV spectra were obtained
with a UV-260 spectrophotometer (Shimadzu , Japan).
IR spectroscopic data were recorded on a Avatar 360 E.
S.R.FT-IR spectroscopy (Thermo Nicolet , U.S.A.)
with KBr pellets.NMR spectra were obtained on a
Bruker DRX-400 NMR;chemical shifts were reported
with respect to TMS.EI-MS were recorded on an Agi-
lent 5973N mass spectrometer.HR-ESI-MS data were
obtained on a Q-Tof Micro spectrometer (Micro Mass ,
England).Column chromatography was performed with
silica gel(200 ～ 300 mesh , Yantai , China), silica gel
H(10 ～ 40μm , Yantai , China).TLC analysis was run
on GF254 precoated silica gel plates(10 ～ 40 μm , Yan-
tai , China).
2.2　Plant Material
The roots of Stellera chamaejasme L.were collect-
ed in Ganzi , Sichuan Province , P.R.China , in
September of 2003.The identity of the plant material
was verified by one of authors Daofeng Chen , and a
voucher specimen (DFC-RXLD0309)is deposited in
the Herbarium of Materia Medica , Department of Phar-
macognosy , School of Pharmacy , Fudan University ,
Shanghai , China.
2.3　Extraction and Isolation
The roots (10 kg)of S.chamaejasme were air-
dried , ground , and extracted with 95%EtOH at room
temperature.The EtOH extract was evaporated in vacuo
to yield a semisolid (1 500 g), 1 490 g of which was
suspended in H2O (5 000 mL)and partitioned succes-
sively with petroleum ether , CHCl3 , EtOAc , n-BuOH
to yield 120 , 30 , 430 and 125 g , respectively.300 g
of the EtOAc extract was subjected to column chro-
matography on silica gel eluted with CHCl3-MeOH (99
∶1 , 49∶1 , 19∶1 , 9∶1 , 4∶1 , 1∶1)and MeOH
to yield fractions 1 ～ 10.Fraction 3(1.77 g)was chro-
matographed over silica gel(petroleum ether-EtOAc , 6.
5∶3.5)to give fractions 3a ～ 3e.Fraction 3b was pu-
rified by column chromatography over Si gel (petroleum
ether-EtOAc , 6∶4)to afford 1(12.5 mg).Fraction 3c
was chromatographed over silica gel eluting with
petroleum ether-acetone (6.5 ∶3.5)to provide 2
(10 mg).
3　Identification
Isodaphnoretin B (7-hydroxy-5 , 6-dimethoxy-3-
[(2-oxo-2H-1-benzopyran-7-yl ) oxy ] -2H-1-benzo-
pyran-2-one)(1)
C20H13O8 , white amorphous powder;[α] D22+62.5°
(c 0.1 , MeOH);UV (MeOH)λmax nm (log ε)208
(4.45), 338(4.55);IR(KBr)cm-1:3 340 , 1 730 , 1
610 , 1 580 , 1 510 , 1 474 , 1 428 , 1 272 , 1 236 , 1 124 ,
1 150 , 1 075 , 987 , 845;1H and 13C NMR data , see
Table 1;EI-MS m/z 382 ([M] +), 367 , 339 , 324 ,
426　　Chin J Nat Med　Nov.2006　Vol.4　No.6 　2006年 11月　第 4卷　第 6期
179 , 151 , 146 , 123 , 118 , 90 , 89 , 69 , 63 , 44 , 43 and
57;Negative HR-ESI-MS m/z 381.061 0 [M-H] -(cal-
cd.for C20H13O8:381.061 0).
References
[ 1] 　Xu ZH , Qin GW , Li XY , et al.New biflavanones and bioactive
compounds f rom Stellera chamaejasme L.[ J] .Acta Pharm Sin ,
2001 , 369(9):668-671.
[ 2] 　Feng WJ , Ikekawa T , Yoshida M.The antitumor activities of gnidi-
macrin isolated f rom Stellera chamadjasme L.[ J] .Chin J Oncol ,
1995 , 17(1):24-26.
[ 3] 　Fan JJ , Jia ZP , Xie JW.Antitumor activity of Chinese Stellera
(Stellera chamadjasme L.)[ J] .J Pharm Pract , 1996 , 14(1):9-
11.
[ 4] 　Liu GQ , Tatematsu H , Kurokawa M , et al.Novel C-3/C-3″-bifla-
vanones from Stellera chamaejasme L.[ J] .Chem Pharm Bull ,
1984 , 32(1):362-365.
[ 5] 　Niwa M , Tatematsu H , Liu GQ , et al.Isolation and structures of
two new C-3/ C-3″-biflavanones , neochamaejasmin A and
neochamaejasmin B [ J] .Chem Lett , 1984:539-542.
[ 6] 　Niwa M , Jiang PF , Hirata Y.Two new C-3/C-3″-bif lavanones from
Wikstroemia sikokiana [ J] .Chem Pharm Bull , 1986, 34 (9):
3631-3634.
[ 7] 　Liu GL , Wang J , Fu YQ , et al.Chemical constituents of S tellera
chamaejasme [ J] .J Chin Pharm Sci , 1997 , 6(3):125-128.
[ 8] 　Ikegawa T , Ikegawa A.Component having antiviral act iveity con-
tained in roudokou (rhizome of Alocasia odora)[ P] .Japanese
Patent:08311056 , 1996-11-26.
[ 9] 　Yang GH , Liao ZX , Xu ZY , et al.Antimitotic and antifungal C-3/
C-3″-biflavanones from Stellera chamaejasme [ J] .Chem Pharm
Bull , 2005, 53:776.
[ 10] Yao XS.Chemistry of natural drugs(the 3rd Edition)[M] .Bei-
jing:The Peoples Health Press , 2001:117-118.
瑞香狼毒中的一个新双香豆素———异西瑞香素 B
杨国红 ,陈道峰＊
复旦大学生药学教研室 ,上海 200032
【摘　要】　目的:研究瑞香狼毒的化学成分。方法:采用硅胶柱层析的方法分离和纯化化合物 , 根据理化性质和波谱方法
鉴定化合物结构。结果:从瑞香狼毒中分离得到两个双香豆素类化合物:7-羟基-5 , 6-二甲氧基-3-[ (2-羰基-2H-1-苯骈吡喃-
7)氧取代] -2H-1-苯骈吡喃-2-酮 , 命名为异西瑞香素 B(1)和西瑞香素(2)。结论:化合物 1为新化合物。
【关键词】　瑞香狼毒;双香豆素;异西瑞香素 B;西瑞香素;瑞香科
【基金项目】　复旦大学研究生创新基金(CQF301804)
·信　　息·
《中国天然药物》2005年影响因子为 0.624
根据《中国学术期刊综合评价数据库(CAJCED)》 2005 年 6 182 种统计刊源析出的 214 万条中国期刊引文数据及
CNKI“中国期刊网”中心网站 2005年 1 ～ 12 月全文下载记录(1.5 亿篇次)的大样本数据统计分析 , 《中国天然药物》
2005年影响因子为 0.624 , 即年指标 0.043 ,他引总引比 0.86 ,被引期刊数 71 , 被引半衰期 2.0 , 基金论文比 0.56 ,Web
即年下载率 29.2 , 说明《中国天然药物》的学术影响力不断扩大 , 呈现良好的发展趋势。
在“十一五”期间 ,《中国天然药物》将继续发扬勤奋踏实 、勇于创新的精神 ,努力突出刊物的专业特色 ,进一步提
高期刊的核心竞争力 ,为早日成为具有较高国际影响力的学术期刊而努力。
　2006年 11月　第 4卷　第 6期 Chin J Nat Med　Nov.2006　Vol.4　No.6　427