全 文 ：天然产物研究与开发 Nat Prod Res Dev 2006, 18:53-54
文章编号:1001-6880(2006)01-0053-02
Received April 25 ,2005;Accepted June 13 , 2005
Fundation Item:Supported by the financial support from the State Key Lab-
oratory of Phytochemistry and Plant Resources inWest China , Kunming In-
stitute of Botany , Chinese Academy of Sciences;supported by the Knowl-
edge Innovat ion Project from the Northwest Institute of Plateau Biology ,
Chinese Academy of Sciences(No.CXLY-2002-7)
＊Corresponding author Tel:86-971-614366;E-mai l:wanghuan@nwipb.
ac.cn
大果大戟中的一个对映-贝壳杉烷型二萜
王 环1 , 3＊ ,张晓峰1 ,罗晓东2
(1.中国科学院西北高原生物研究所 ,西宁 810001;2.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;3.中国科学院研究生院 ,北京 100049)
摘 要:从大果大戟的根部首次分离得到一个对映-贝壳杉烷型二萜 , 利用波谱方法鉴定为 ent-16α, 17-dihydrox-
ykauran-3-one(1)。首次对化合物 1 在甲醇中的碳谱和氢谱数据进行了全归属。
关键词:大果大戟;大戟科;贝壳杉烷型二萜
中图分类号:R284.1;Q946.91 文献标识码:A
An ent-Kaurane Diterpene from Euphorbia wallichii
WANG Huan1 , 3＊ ,ZHANG Xiao-feng1 ,LUO Xiao-dong2
(1.Northwest Institute of Plateau Biology , Chinese Academy of Sciences , Xining 810001 , China;2.State Key Laboratory of
Phytochemistry and Plant Resources in West China , Kunming Institute of Botany , Chinese Academy of Sciences , Kunming
650204 , China;3.Graduate School of the Chinese Academy of Sciences , Beijing 100049 , China)
Abstract:One known ent-kaurane diterpene , ent-16α, 17-dihydroxykauran-3-one , were isolated from the roots of Euphorbia wal-
lichii for the first time.Its structure was elucidated on the basis of spectral methods.And the NMR assignments of the compound
in CD3OD were given for the first time.
Key words:Euphorbia wallichii;Euphorbiaceae;kaurane diterpene
Euphorbia wallichii hook.f.is a traditional Tibetan
medicine used for curing furuncle , exanthema and cuta-
neous anthrax.Our previous investigation on the species
resulted in the isolation of 24 compounds
[ 1-3] .In our con-
tinuous study , an ent-kaurane diterpene , ent-16α,17-dihy-
droxykauran-3-one (1[ 4]),was obtained from the alcohol
extract of the roots of the plant.In this paper , we report
the isolation and structure elucidation of the compound.
Results and Discussion
Compound 1 has a molecular formula of C20H32O3 as de-
termined by EIMS and
13
C NMR spectra.The 1D NMR
spectra showed signals of three tertiary methyls , eight
methylenes , three methines , three quaternary carbons , a
carbonyl(δC 221.0), a primary (δC 70.5)and a tertiary(δC 80.6)hydroxyl groups.These features are similar to
those of ent-16α, 17-dihydroxyatisan-3-one[ 3] and ent-
16α, 17-dihydroxykauran-3-one[ 4] .Compound 1 was de-
tected in CD3OD ,while the latter two compounds were de-
tected in CD3Cl or C6D6 , so it is hard to confirm the
skeleton of compound 1.To determine its skeleton and
give the NMR assignments , HMQC , HMBC and ROESY
spectra of 1were tested.Correlations in HMBC (see table
1)f rom H-14 to C-7 ,C-8 ,C-9 ,C-12 ,C-13 ,C-15 and C-
16 ,H-15 to C-7 ,C-8 , C-9 ,C-13 , C-14 ,C-16 and C-17 ,
H-17 to C-13 ,C-15 and C-16 revealed that compound 1
isn t an ent-atisane diterpene but an ent-kaurane diter-
pene .The relative stereochemistry of the compound was fi-
nally determined by Roesy spectrum , in whose NOE inter-
action between H-9 with H-5 , and H-11β , H-20 with H-
1α,H-13 , H-14α, and H-17 were observed.Thus 1 was
elucidated to be ent-16α, 17-dihydroxykauran-3-one.In
comparison with the reported data of compound 1 in
C6D6
[ 4] , the 13 C NMR spectra in CD3OD provided in-
creased signal , especially C-3 , whose chemical shift was
bigger than that in C6D6(δC 215.6)by 5.4 ppm.
Table 1 1D NMR data and HMBC of compound 1a(CD3OD)
δH δC HMBC
1 1.93 , 1.35(m , each 1H) 40.4(t) C-2 ,C-3, C-5, C-6 , C-9 , C-10, C-20
2 2.39(m , 2H) 35.0(t) C-1 ,C-3, C-4
3 - 221.0(s) -
4 - 48.2(s) -
5 1.39(m , 1H) 55.5(d) C-1 ,C-4, C-6, C-7 , C-9 , C-10, C-18 , C-19, C-20
6 1.37(m , 2H) 22.3(t) C-4 ,C-5, C-7, C-9 , C-10
7 1.38(m , 2H) 42.0(t) C-5 ,C-6, C-9, C-14
8 - 44.6(s) -
9 1.12(brd, J =8.6 Hz , 1H) 57.2(d) C-8 ,C-10 , C-11 ,C-12 , C-14, C-15 , C-20
10 - 39.7(s) -
11 2.05(m , 1H), 1.49(d , J =6.3 Hz , 1H) 20.2(t) C-8 ,C-9, C-10 , C-12, C-13
12 1.44 , 1.74(m , each 1H) 27.7(t) C-9 ,C-11 , C-13 ,C-14 , C-16
13 1.96(m , 1H) 42.1(d) C-12 , C-14
14 1.01(m , 1H), 1.85(dd , J=1.9, 12.2 Hz , 1H) 38.8(t) C-7 ,C-8, C-9, C-12 ,C-13 , C-15 ,C-16
15 1.34 , 1.31(m , each 1H) 52.8(t) C-7 ,C-8, C-9, C-13 ,C-14 , C-16 ,C-17
16 - 80.6(s) -
17 3.31(d , J =11.2 Hz , 1H), 3.20(d, J=11.2 Hz ,1H) 70.5(t) C-13 , C-15 ,C-16
18 0.96(s, 3H) 27.7(q) C-3 ,C-4, C-5, C-19
19 0.92(s, 3H) 21.4(q) C-3 ,C-4, C-5, C-18
20 1.00(s, 3H) 18.2(q) C-1 ,C-5, C-9, C-10
a 1D NMR data were measured at 400 MHz , and 2D NMR data at 500MHz.
Experimental
Apparatus and plant materials (see previously de-
scribed
[ 1])
Extraction and isolation
The air-dried roots(10 kg)of Euphorbia wallichii were
extracted with EtOH(95%)four times at room tempera-
ture , and the combined extracts were evaporated in vacuo.
The residue was suspended in H2O and then extracted
with CHCl3 for three times.The CHCl3 layer was concen-
trated in vacuo to give 200 g of residue ,which was chro-
matographed over silica gel.The column was eluted with
petroleum ether-EtOAc (from petroleum ether to
petroleum-EtOAc 1:1).According to differences in com-
position monitored by TLC (GF254),17 fractions were ob-
tained.Fraction 11(6.8 g)was subjected to CC on silica
gel with petrol-Me2CO (from 17:3 to 7:3).Five subfrac-
tions(a-e)were collected.Fraction e (1.2 g)was sub-
jected to CC on silica gel with CHCl3-Me2CO(90:10)to
give three subfractions (Ⅰ-Ⅲ).Sediment from fraction
Ⅱ(140 mg)was washed intensively with petrol-acetone
(10:1)and recrystallized by MeOH , then it was washed
intensively again to afford 1(45 mg).
Identification
ent-16α, 17-dihydroxykauran-3-one (1) C20H32O3 ,
colorless needles;1H NMR and 13C NMR (CD3OD)see
table 1;EIMS m/z 320 [M] +(1), 302(3), 289(100),
271(47),259(11),253(4),247(25),229(13),216(9),
203(16),189(18),177(12),171(4),165(7),159(10),
151(13), 145(21), 137(15), 121(21), 107(28), 97
(11),91(32),81(29),67(29),55(53).
References
1 Wang H , Zhang XF , Pan L , et al.Chemical constituents from
Euphorbia wllichii.Natural Product Research and Development ,
2003 , 15:483-486.
2 Wang H , Zhang XF , Cai XH , et al.Three new diterpenoids
from Euphorbia wallichii.Chin J Chem , 2004 , 22:199-202.
3 Wang H , Zhang XF ,Ma YB , et al.Diterpenoids from Euphor-
bia wallichii.Chinese Traditional Herbal Drugs , 2004 , 35:611-
614.
4 Gustafson KR , Munro MHG , Blunt JW , et al.HIV inhibitory
natural products.3.Diterpenes from Homalanthus acuminatus
and Chrysobalanus icaco.Tetrahedron , 1991 , 47:4547-4554.
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