全 文 ：　　　　 天然产物研究与开发　 　　　　　
2003　Vo1.15　No.1 NATU RAL PRODUCT RESEARCH AND DEVELOPMENT　 　　　　　　　　　　
　
　
　
　
　　收稿日期:2002-11-22　　　修回日期:2002-12-06
　　＊Corresponding author:Tel.021-64311833×349;Emai l:yw guo
@mail.shcnc.ac.cn
　　This research is supported by Nat ional Science Foundation for Out-
standing You th(30125044)and the “Foundation for S cholars Come Back
f rom Abroad” provided by Minist ry of Education , Minist ry of Personnel ,
and Chinese Academy of S ciences.
CRYSTAL STRUCTURE STUDY OF
(-)SYRINGARENOL ,A LIGNAN ISOLATED
FROM DIPLOCLISIA GLAUCESCENS
HUANG Xiao-chun1 　GUO Yue-wei1＊　LV Yang2 　WANG Cheng2 　ZHENG Qi-tai2
(1.State Key Laboratory of Drug Research , Institute of Materia Medica , Shanghai Institutes for
Biological Sciences , Chinese Academy of Sciences , Shanghai　200031 , China;
2.I nstitute of Material Medica , Chinese Academy of Medical Sciences , Beijing　100050 , China)
Abstract　The cry stal structure of the title compound was determined by single-cry stal X-ray diffraction anal-
ysis.The crystal belongs to o rtho rhombic sy stem , space g roup P212121 with unit cell parameters of a=8.6010
(3), b=13.0830(9), c=18.1130(11) , V=2038.20(20) 3 , Z=4 , Mr=418.49 , Dx =1.369 g/cm3 , λ
(MoKα)=0.71073 , μ(MoKα)=1.12 cm-1 , F(000)=888.The structure was solved by direct method
and refined by full matrix least-squares method.The final discrepancy facto r Rf=0.062 , Rw=0.055 fo r 1963
unique observed reflections[ Ⅰ ≥8σ(Ⅰ)] .
Key words　D .glaucescens;lignan;(-)sy ringarenol;crystal structure
1　INTRODUCTION
Lignans , a g roup of naturally occurring phenylpropane
dimers w hich are linked through the beta-carbon
atoms of the side chains , are long known natural prod-
ucts w idely spread in the plant kingdom.It has been
shown that lignans exhibit interesting biological and
pharmacological ef fects in many bioassays aimed at
screening agents w ith antitumor , antiviral , antimi totic
activi ties and being probable inhibitor of c-AMP phos-
phodieterase[ 1-3] .In the course of our w ork aimed at
searching for novel bioactive compounds f rom Chinese
medicinal plants , a plant D .glaucescens was collect-
ed , which has been used as tradi tional Chinese
medicine , especially as a treatment for biliousness and
venereal diseases[ 4] .Chemical investigation of the
stems of this plant led to the isolation of three lig-
nans , (-)Sy ringarenol(1)[ 5] , 5 , 5 -Dimethoxy lari-
ciresinol[ 6] and Dihydrodehydrodiconiferol[ 5] , of
w hich structures w ere elucidated by spectroscopic
analysis and comparison w ith model compounds in lit-
eratures , as w ell as X-ray dif fraction analy sis.In the
present paper we repo rt the single-crystal X-ray study
of compound 1.
Fig.1a　Structure of the title compound
2　EXPERIMENTAL
2.1　General
X-ray measurements w as performed on a MAC DIP-
2030K Image Plate Diff ractometer;The IR spect rum
1
were recorded on a Nicolet M agna FT-IR750 spec-
trometer , and UV spect ra w ere obtained on a Varian
CARY 300 BIO spect ropho tometers;1H and 13 C-
NMR spectra were measured on a 400 MHz Bruker
DRX400 spectrometer.Chemical shif ts were given in
ppm referenced to TMS as int.standard.1H and 13C-
NMR assignments w ere supported by 1H-1H COSY ,
HMQC and HMBC experiments;EIMS , ESIMS and
HREIM S spect ra were obtained on a Finnig an-MAT-
95 mass inst rument;Optical rotation w as measured on
a Perkin-Elmer 241MC Polarimeter in CHCl3;open
column chromatography , silica gel H(200-300 mesh);
TLC , silica gel GF 254(T LC plate).
2.2　Extraction and Isolation
The stems of D .glaucescens , collected in Guangxi
Province ,China in 1996 , were exhaust ively ext racted
w ith 95%EtOH.The CHCl3 soluble f ract ion from the
EtOH extract was f ractionated by silica gel column
chromatography(CC)[ gradient f rom light petroleum
ether(PE)-CHCl3 to CHCl3-MeOH] .The fractions e-
luted w ith PE-CHCl3(4∶6)were further purified by
silica gel CC(gradient f rom C6H6 to M e2CO)to af ford
pure compound 1(41.6 mg).
Compound 1 was isolated and cry stallized as optically
active colorless crystals{[ α] 20D =-12.1°,(c=0.21 ,
CHCl3)}.The negative opt ical rotation value of 1 sug-
gests that it has the same stereost ructure as that of
(-)Sy ringarenol[ 5] {[ α] 20D = -36.2 , (c =1.03 ,
CHCl3)}.The molecular fo rmula , C22H 26O8 , was es-
tablished by HREIMS(m / z 418.1628 , Δ=-0.1
mmu of that caculated);IRυmax(KBr):3440 , 2941 ,
1612 ,1519 , 1456 , 1425 , 1324 , 1203 , 1112 , 987 , 731
cm-1;UV λmax(CHCl3)nm(log ε):271(3.36);1H
NMR(400 MHz ,CDCl3):δ3.10(2 H , m ,H-6 A , H-
3 A),3.91(12 H , s ,OCH3), 3.92(2 H ,m , H-3ax , H-
6ax),4.29(2 H ,m ,H-3eq ,H-6eq),4.74(2 H , d , J =
4.3 Hz ,H-1 ,H-4),5.54(2 H ,brs OH), 6.59(4 H , s ,
Ar-H);13C NMR(100 MHz ,CDCl3):δ54.3(C-1 ,C-
3A),56.3(C-20 ,C-23 ,C-25 ,C-28),71.7(C-3 ,C-6),
86.0(C-1 , C-4), 102.6(C-8 , C-12 , C-14 , C-18),
132.0(C-7 , C-13), 134.2(C-10 ,C-17), 147.1(C-9 ,
C-11 , C-15 , C-17);EIMS:m/ z 418(M+ , 100%);
HREIM S:m/ z 418.1628.
2.3　X-ray Analysis
Single crystals sui table for X-ray analysis were ob-
tained by recry stallization f rom EtOAc/CHCl3(1∶1).
A colorless crystal of dimensions 0.05×0.10×0.20
mm was selected and used for X-ray dif f raction analy-
sis.The determination of unit cell and the data collec-
tion were performed on the MAC DIP-2030K dif frac-
tometer w ith MoKα(λ=0.71073 )and graphite
monochromator.The crystal belongs to o rthorhombic
system , space group P212121 ,unit cell parameters a=
8.6010(3), b =13.0830(9), c =18.1130(11) , V
=2038.20(20) 3 , Z =4 , μ=1.12 cm-1 , F(000)=
888.A total of 1988 independent reflections w ere col-
lected in the 2θrange of 0-50°by ωscan technique , in
w hich 1963 reflection wi th Ⅰ≥8σ(Ⅰ)were consid-
ered observed and used in the refinements.The struc-
ture was solved by direct method.Most of the non-
hydrogen atoms w ere located from E-map.The o thers
were determined with difference Fourier synthesis.
The hydrogen atoms w ere identified by a combinat ion
of geometric calculation and dif ference Fourier syn-
thesis , all of w hich were refined w ith fixed posit ion
parameters and thermal factors.The final refinement
by full matrix least-squares method w ith anisostropic
thermal parameters fo r non-hydrogen atoms w ere
converged with R f , Rw of 0.062 and 0.055[ ω=1/σ
[ F 2)] .The highest peak on the final dif ference
Fourier map had a height of 0.330e/ 3 , Δ/ρ=
0.091 ,S=3.747.All calculations were performed on
a SGI w ork station , PC using DENZO , SCALE-
PACK ,HKL ,SHELXS-86 Prog ram sy stem.
Fig.1b　Structure of the title compound(perspective view)
2　　　　　　　　　 天然产物研究与开发 2003　Vo1.15　No.1
Fig.2　Molecular packing in unit cell
3　RESULTS AND DISCUSSION
The fractional coordinates of non-hydrogen atoms and
equivalent iso tropic thermal parameters are given in
Table 1.Selected bond lengths and bond angles are
listed in Table 2 and 3 , respectively.Figure 1 is a per-
spective view of the title compound show ing the
atomic numbering scheme.Figure 2 show s the pack-
ing diagram of the tit le compound in a unit cell look-
ing down along a axis.
The molecular backbone of the tit le compound is
characterized by a tetracyclic system , including a 2 ,5-
dioxybicy clo[ 3 , 3 , 0] octane moiety and two trisubsi-
tuted phenyl rings.The central eight-membered 2 , 5-
dioxybicy clo[ 3 , 3 , 0] octane moiety is composed of
two tet rahydrofuran ring s w hich adopt envelop-like
conformation and are cis-fused to each other by C-
3A ,C-6A bridge atoms.The dihedral angle between
the tw o phenyl rings is 62.88°.There are two inter-
molecular H bonds O26...O2(1/2-x ,-y , 1/2+z)and
O21...O5(1/2-x ,-y , -1/2 +z)w ith bond leng ths
2.849 and 2.891 , respectively.
Table 1　Atomic Parameters and Biso( 2)
Atom x y z Bi so Atom x y z Bi so
C(1) -0.2880(9) 0.1870(4) -0.1970(3) 4.2(3) C(14) -0.3150(8) 0.4039(4) 0.0675(3) 4.0(3)
O(2) -0.2166(6) 0.2744(3) -0.2283(2) 4.6(2) C(15) -0.3236(8) 0.4909(4) 0.1120(3) 3.9(3)
C(3) -0.2243(10) 0.3545(4) -0.1732(3) 5.0(3) C(16) -0.3895(8) 0.5810(4) 0.0855(3) 3.6(3)
C(3A) -0.2262(8) 0.3007(4) -0.0994(3) 4.4(3) C(17) -0.4482(8) 0.5830(4) 0.0141(3) 3.8(3)
C(4) -0.3745(8) 0.3135(4) -0.0531(3) 4.2(3) C(18) -0.4462(8) 0.4949(5) -0.0287(3) 4.2(3)
O(5) -0.3875(5) 0.2207(3) -0.0109(2) 4.1(3) O(19) -0.0698(6) -0.0056(3) -0.4122(3) 4.5(2)
C(6) -0.3442(10) 0.1383(4) -0.0600(3) 5.1(4) C(20) 0.0363(8) 0.0747(5) -0.4312(3) 4.6(3)
C(6A) -0.2331(9) 0.1846(4) -0.1182(3) 4.6(3) O(21) -0.2117(6) -0.1754(3) -0.3645(2) 5.0(3)
C(7) -0.2560(8) 0.0914(4) -0.2417(3) 3.7(3) O(22) -0.3762(6) -0.1808(3) -0.2423(3) 5.6(3)
C(8) -0.1668(8) 0.0934(4) -0.3060(3) 3.8(3) C(23) -0.4494(11)-0.1898(5) -0.1712(4) 6.4(4)
C(9) -0.1512(7) 0.0032(4) -0.3468(3) 3.4(3) O(24) -0.2678(8) 0.4975(3) 0.1822(3) 6.3(3)
C(10) -0.2244(8) -0.0867(4) -0.3251(3) 3.7(3) C(25) -0.2477(10) 0.4037(5) 0.2231(3) 5.2(3)
C(11) -0.3113(8) -0.0876(4) -0.2601(3) 4.0(3) O(26) -0.3988(6) 0.6684(3) 0.1275(2) 4.7(2)
C(12) -0.3293(8) 0.0020(4) -0.2196(3) 4.0(3) O(27) -0.5071(6) 0.6740(3) -0.0137(3) 5.3(2)
C(13) -0.3797(8) 0.4057(4) -0.0033(3) 3.7(3) C(28) -0.6613(10) 0.6869(6) -0.0097(6) 8.7(6)
Biso=-2 π2(h2a＊2u11+k2b＊2u22+l2c＊2u33+2hka＊b＊u12+2hla＊c ＊u13+2klb＊c＊u23)
Table 2　Selected Bond Lengths( )
Bond Dist. Bond Dist.
C(1)-O(2) 1.461(7) C(7)-C(12) 1.387(8)
C(1)-C(6A) 1.505(8) C(8)-C(9) 1.399(8)
C(1)-C(7) 1.514(8) C(9)-C(10) 1.390(8)
O(2)-C(3) 1.449(7) C(10)-C(11) 1.394(8)
C(3)-C(3A) 1.512(8) C(11)-C(12) 1.392(8)
C(3A)-C(4) 1.535(9) C(13)-C(14) 1.399(8)
C(3A)-C(6A) 1.558(8) C(13)-C(18) 1.379(8)
C(4)-O(5) 1.438(7) C(14)-C(15) 1.398(8)
C(4)-C(13) 1.507(9) C(15)-C(16) 1.393(8)
O(5)-C(6) 1.446(7) C(16)-C(17) 1.388(8)
C(6)-C(6A) 1.546(10) C(17)-C(18) 1.390(8)
C(7)-C(8) 1.396(8)
Table 3　Selected Bond Angles(°)
Angle (°) Angle (°)
O(2)-C(1)-C(6A) 105.1(5) C(1)-C(7)-C(8) 122.0(5)
O(2)-C(1)-C(7) 112.0(5) C(1)-C(7)-C(12) 117.3(5)
C(6A)-C(1)-C(7) 115.6(5) C(8)-C(7)-C(12) 120.5(5)
C(1)=O(2)-C(3) 106.8(4) C(7)-C(8)-C(9) 118.5(5)
O(2)-C(3)-C(3A) 105.8(4) C(8)-C(9)-C(10) 121.4(5)
C(3)-C(3A)-C(4) 116.3(6) C(9)-C(10)-C(11) 119.3(5)
C(3)-C(3A)-C(6A) 105.1(5) C(10)-C(11)-C(12) 119.8(5)
C(4)-C(3A)-C(6A) 101.2(5) C(7)-C(12)-C(11) 120.5(5)
C(3A)-C(4)-O(5) 105.2(5) C(4)-C(13)-C(14) 121.5(5)
C(3A)-C(4)-C(13) 116.0(5) C(4)-C(13)-C(18) 119.4(5)
O(5)-C(4)-C(13) 110.9(4) C(14)-C(13)-C(18) 119.0(5)
C(4)-O(5)-C(6) 106.5(4) C(13)-C(14)-C(15) 119.6(5)
O(5)-C(6)-C(6A) 106.6(4) C(14)-(15)-(16) 20.8(5)
C(1)-C(6A)-C(3A) 101.5(5) C(15)-C(16)-C(17) 119.0(5)
C(1)-C(6A)-C(6) 117.5(6) C(16)-C(17)-C(18) 120.5(5)
C(3A)-C(6A)-C(6) 104.9(5) C(13)-C(18)-C(17) 124.4(5)
32003　Vo1.15　No.1　黄孝春等:苍白秤钩风(Diploclisia Glaucescens)中的木脂素———左旋丁香脂素的晶体结构研究　　　　　　　　　
Compound 1 is a common lignan which w as found in
many plants[ 7-10] .However , 1 was for the first time
isolated f rom the genus Diploclisia , and this is also
first report of the crystal st ructure of 1.Interest ingly ,
(-)sy ringarenol(1)was recently repo rted to be a new
type of DNA strand-scission agent[ 11] .In our bioas-
say , compounds 1 enhanced the proliferation capacity
of T and B cells.Other pharmacological studies fo r
compounds 1 and further chemical investigation of D .
glaucescens are currently in progress.
ACKNOWLEDGEMENT
The authors are g rateful to Professor Z.-T .Wang ,
China Pharmaceutical University , for collection and i-
dentification of the plant material.The NMR and the
mass spectra w ere obtained from the “SIMM-NMR ,
MS Services” .The stuff of both services is g ratefully
acknow ledged.Thanks are also due to Prof.J.-P .Zuo
and M r.W.-L.Zhou fo r biological test.
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苍白秤钩风(Diploclisia Glaucescens)中的木脂素
———左旋丁香脂素的晶体结构研究
黄孝春1　郭跃伟1＊　吕　扬2　王　诚2　郑启泰2
(1.中国科学院上海生命科学院药物研究所新药研究国家重点实验室　上海　200031;
2.中国医学科学院药物研究所　北京　100050)
摘　要　通过 X-射线单晶衍射法测定了标题化合物的晶体结构。 结果表明:晶体属正交晶系 , P212121
空间群 , a=8.6010(3), b=13.0830(9), c=18.1130(11) , V =2038.20(20) 3 , Z =4 , Mr=418.49 ,
Dx=1.369 g/ cm3 , λ(MoKα)=0.71073 , μ(MoKα)=1.12 cm-1 , F(000)=888。在 0<2θ<50°范围内
共收集了 1988 个独立衍射点 , 其中可观测衍射点 1963 个[ Ⅰ ≥8 σ(Ⅰ)] 。晶体结构用直接法解出 ,经全
矩阵最小二乘法修正 ,最终偏离因子 R f=0.062 , Rw=0.055。
关键词　晶体结构;左旋丁香脂素;木脂素;苍白秤钩风
4　　　　　　　　　 天然产物研究与开发 2003　Vo1.15　No.1