全 文 ：　　　　 天然产物研究与开发　 　　　　　
2004　Vol.16　No.3 NATU RAL PRODUCT RESEARCH AND DEVELOPMENT　 　　　　　　　　　　
　
　
　
　
　　Received 11 November 2003;Accepted 9 December 2003
Foundation Item:Science Foundation of Guangxi University
(DD040003)
　 ＊Corresponding author Tel:86-771-3233718;E-mail:w xwei@
gxu.edu.cn
THE STRUCTURES IN CRYSTAL AND IN
SOLUTION OF FRIEDELIN ISOLATED
FROM PHYLLANTHUS NIRURI LINN
WEI Wan-xing1＊ ,PAN Yuan-jiang2 ,ZHANG Hong3 ,CHEN Yao-zu2
(1.Department of Chemistry , Guangxi Univesity , Nanning 530004 , China;
2.Department of Chemistry , Zhejiang University ,Hangzhou 310027 , China)
Abstract　Friedelin w as first isolated from Phyllanthus niruri linn.Its structure w as determined by means of spec-
troscopy methods and X-ray crystallography.Chemical shifts of all carbons and pro tons were assigned based on the
2D NMR methods.The structure elucidated by means o f NMR coincided w ith the structure got from X-ray diffrac-
tion method.It means that structure of friedelin in cry stal an in solution have a same configura tion.This compound
crystallized in the or thorhombic space group P2(1)2(1)2(1)with a= 6.361(2) , b=13.933(3) , c=28.440
(6) , α=90°, β=90°, γ=90°, V=2520.6(11) 3 , Z=4.A slightlyintermolecular contact C-H.....O=C was ob-
served firstly in this crystal.This contact w as supposed to be the determinative facto r of formation of the crystal.
Key words　crystal structure;Phy llanthus niruri Linn;Friedelin;NM R assignment
从珠子草中分离得到的化合物:软木三萜酮
在溶液和晶体中的结构
韦万兴1＊　潘远江2 　张　虹2 　陈耀祖2
(1.广西大学化学系　南宁　530004;2.浙江大学化学系　杭州　310027)
摘　要　首次从大戟科植物珠子草中分离得到软木三萜酮。利用晶体 X-射线法与一维和二维核磁共振法
测定了该化合物的结构 , 指认了核磁共振信号的归属。晶体衍射结果表明 ,化合物是以斜方晶体空间群形成
晶体 , 晶体数据维 P2(1)2(1)2(1)with a=6.361(2) , b=13.933(3) , c=28.440(6) , α=90°, β=90°, γ
=90°, V=2520.6(11) 3 , Z=4.在晶体中存在一个微弱的分子间的作用力 C-H.....O=C ,此作用力被认为
是晶体形成的重要因素。 NMR方法确定化合物的结构相同 , 表明了软木三萜酮在晶体和溶液具有相同的构
型。
关键词　珠子草;软木三萜酮;晶体结构;核磁共振
Introduction
Phyllanthus niruri Linn was a well-known medicinal
plant , and was used for treatment of hepatitis disease in
India[ 1 , 2] .Many works had been done on the chemical
components of this plant[ 3 , 4 , 5] .The interesting biological
activities of this plant prompted us to work on this
specie.Many compounds were obtained from this plant in
our previous works[ 6 , 7].In our present work friedelin was
firstly isolated f rom this species.Although f riedelin have
been investigated in previous reports , and chemical shif t
reagents were used to assign carbon sequence of this com-
pound
[ 8 , 9] , its NMR signals have not been assigned com-
pletely by means of 1D and 2D NMR.In this work ,we t ry
to report the complete NMR assignments of f riedelin.The
structure of this compound based on the NM R assign-
ments was coincided with the crystal structure.
Experimental Details
General methods　1H NMR (500 MHz)and 13C NMR
201
(125 MHz)were recorded on a Bruker AM-500 spec-
trometer.Sample dissolved in CDCl3 for NMR stud-
ies.Chemical shifts were reported in ppm.EIMS spect rum
was recorded using HP5989B mass spect rome-
ter.Elementary analysis was performed on a PE2400
CHN elemental analyzer.
Plant material 　The plant material was collected from
Longan county ,Guangxi province at August 2001 and was
identified as Phllanthus niruri L.A voucher specimen
was kept in the biological Department of Zhejiang Univer-
sity.
Isolation and purification　The air-dried P.nirur i (3.5
kg)was ext racted with ethanol , under constant mechani-
cal stirring , and this procedure w as repeated until no fur-
ther ext ract bud was obtained.The combined ex tracts
were filtered w hile warm through glass wool , and then
concent rated.The residue(120 g)was ext racted succes-
sively with pet roleum ether and ethyl acetate.The mixture
of petroleum ether ext racts and ethyl acetate ext racts was
centrifuged , and concentrated to dryness and got 15 g
residue.Chromatography of the 15 g residue was applied
in silica gel(40 ～ 60μm)column using the solvent system
petroleum ether to ethyl acetate (v/v)as eluent.After
repetition of chromatography on silica gel column the pure
compound 1 was obtained.
Fig.1　Structure of the title compound(1)
Fig.2　Principal NOYSY correlations of the title compound
As mostly perfect in shape , a single crystal obtained from
the solution of compound 1 in methanol w as mounted on
the diffractometer for X-ray data collection.The structure
was solved by SHELXS-97[ 10] , and expanded using
Fourier techniques.The non-hydrogen atoms were refined
anisot ropy.The hydrogen atoms involved in hydrogen
bonding of CHO were deduced f rom different Fourier
maps , their position and Ueq were involved in the refine-
ment procedure;while the others were placed in calculated
positions , their Ueq are 20% larger than that of parent
atoms.
The weighting scheme used at the final stage was W =
[ α2C(F20)+(0.0477P)2] -1 , where P =(F20 +2F2C)/3.
Atomic scattering facts used were taken from international
Table for X-ray crystallography[ 11] .
Results and Discussions
Compound 1 , a colorless crystal ,molecular formula C30H50
O.EI-MS showed molecular weight 426.70.Elementary
analysis gave the result C 84.4%,H 11.8%,O 3.8%.
Table 1　Crystal data and structure refinement
Empirical formula C 30 H50O
Formula w eight 426.70
Temperature 295(2)K
Wavelength 0.71073
Crystal system Orthorhombic
Space group P2(1)2(1)2(1)
Unit cell dimensions a=6.361(2) 　　alpha = 90°
b = 13.933(3) 　　beta=90°
c=28.440(6) 　　gamma=90°
Volume ,Z 2520.6(11) 3 , 4
Density (calculated) 1.124 g/ cm3
Absorption coeff icient 0.065 mm-1
F(000) 952
Crystal size 0.50×0.40 × 0.12 mm
T heta range for data collec-
ti on
1.63 to 26.00 deg.
Limit ing indices 0≤h≤7 , 0≤k≤17 ,-1≤l≤35
Reflections collected 3095
Independent ref lect ions 2933[ R(int)=0.0105]
Absorption correction None
Refinement method Full-matrix least-squares on F2
Data/ rest raints/ parameters 2933/ 0/ 289
Goodness-of-f it on F2 0.815
Final R indices[ I >2sigma
(I)] R1 = 0.0483 ,WR2 = 0.0809
R indices(all data) R1 = 0.1165 ,WR2 = 0.0974
Absolute st ructu re parameter -5(4)
Ext inction coeff icient 0.0060(5)
Larges t dif f.peak and hole 0.145 and-0.173 e.A -3
H-bonds:
C1 H 1B O 0.97 2.57 3.415(5) 145.8 4-556
C24 H 24B O 0.96 2.65 3.613(5) 176.1 4-556
Most crystal data of the t itle compound coincided
w ith previous repo rt
[ 12] .Investigation of Rogers had
no t give format ion of cause of this cry stal.In this
compound , there are not any hydroxy l g roups and
other atoms that form normal hydrogen bonds.Con-
fo rmation of this cry stal is depended on non-bond in-
teraction among molecules.Tw o abno rmal hydrogen
bonds exited in the crystal , that 3.613(5) is for
bond of C24-H24B...O and 3.415(5) fo r C1-
H1B...O just showed in Fig.3.These intermolecular
contacts are slight.The C-H bond lengths in the C-
H...O are not vary to other C-H bonds.Because of no
any no rmal hydrogen bond in the crystal , the main
factor of formation of the crystal was supposed to be
due to the abnormal hydrogen bonds and other Van
Der Waals bonds.The structure of compound show ed
in Fig.1 revealed that ring 1 , 2 and 3 w ere in chair
conformation and ring 4 and 5 in boat conforma-
tion.Chemical shif ts of protons and carbons were as-
signed based on NMR methods included 1D 1H
NMR , 13C NMR , DEPT (90°and 135°)and 1H-1H
202　　　　　　　　　 天然产物研究与开发 2004　Vol.16　No.3
COSY , 13 C-1H COSY , HMBC , and NOESY.The
structure elucidated by NMR was showed in Fig.2.It
showed three chair ring s and tw o boat ring s in the
molecule in solution stage.There are no t differences
between molecular st ructures of f riedelin in solution
state and in cry stal state.
Table 2　NMR data of the title compound(in CDCl3)
Atoms
No. C(δ) H(δ) Multiplicity
1H-1H
COSY
HMBC NOESY
1 22.54 1.96 ,1.68 CH 2 2 , 10 3 , 5 , 9
2 41.79 2.40 ,2.30 CH 2 1 3 , 10 4 ,6
3 213.50 CO
4 58.49 2.26 CH 23 3 ,5 10
5 42.40 C
6 41.56 1.74 ,1.30 CH 2 7 5 ,8 ,10 4
7 18.50 1.52 ,1.45 CH 2 6 ,8 5 , 8 , 9
8 43.06 1.58 CH 7 , 6 ,9 ,14 ,
9 37.71 C
10 59.74 1.55 CH 1 5 , 2 , 9 11
11 35.60 1.45 CH 2 12 9 , 13
12 32.68 1.22 CH 2 11 , 9 , 13
13 38.56 C
14 39.96 C
15 33.04 1.20 CH 2 16 14 ,17 18
16 35.89 1.34 CH 2 15 17 ,14 , 18 15
17 30.25 C
18 53.37 1.39 CH 19 13 ,17 , 20 12
19 36.27 1.27 CH 2 18 13 ,20 , 29 22
20 28.43 C
21 30.76 1.38 CH 2 22 20 ,17
22 39.51 1.51 CH 2 21 17 ,18 , 28 16 ,30
23 7.07 0.87 CH 3 4 3 ,5
24 14.91 0.73 CH 3 5 ,4 ,10
25 18.20 0.88 CH 3 9 ,10 , 11
26 32.04 1.01 CH 3 14 , 13 ,15 , 8
27 18.91 1.05 CH 3 13 ,12 , 18
28 32.35 1.18 CH 3 17 ,18
29 35.27 0.95 CH 3 20 ,30
30 20.51 1.00 CH 3 20 ,29
Fig.3　A stereoscopic illustration of the unit cell packing
of the title compound
Conclusion
The cry stal st ructure of this compound showed a
slight contact C-H.....O=C between molecules.
Those intermolecular contacts were supposed to be the
main cause of the formation of the cry stal.The com-
plete NMR signal assignment of friedelin was done
and , a st ructure w as elucidated by spect roscopy.The
results show ed the structure of f riedelin in solut ion
coincided w ith the st ructure in crystal.In solution the
molecule of f riedelin , tw o boat rings and three chair
rings consisted the molecule.
Fig.4 　View of the title compound showing the atomic
numbering scheme
Acknowledgements The autho rs are thankful to the
Science Foundation of Guangxi University(No.DD040003)for the financial supports of this re-
search.
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2032004　Vol.16　No.3 韦万兴等:从珠子草中分离得到的化合物:软木三萜酮在溶液和晶体中的结构