全 文 ：A New Diterpenoid from Aralia fargesii
ZHANG Yu_Mei＊ , YANG Jun_Shan
(Institute of Medicinal Plant Development , Chinese Academy of Medical Science and Peking Union Medical College , Beijing 100094, China)
Abstract:　Four diterpenoids , including a new ent_kaurane diterpene (1), were isolated from the rhizome of
Aralia fargesii Franch.On the basis of chemical and spectral evidence (IR , EI_MS , HREI_MS , 1H-NMR ,
13C_NMR and HMQC), the structure of compound 1 was established to be 17_acetoxy_16α_ent_kauran_19_oic
acid.The other three known compounds were identified as ent_pimara_8(14),15_dien_19_oic acid (2), 16α_
hydroxy_(-)_kauran_19_oic acid (3)and 16α_17_dihydroxy_ent_kauran_19_oic acid (4).The three known
diterpenoids were obtained from this plant for the first time.
Key words:　Aralia fargesii;diterpenoid;17_acetoxy_16α_ent_kauran_19_oic acid
　　The rhizome of Aralia fargesii was used in folk
medicine in China as an antirheumatic and analgesic
agent.It was mainly distributed in Sichuan and Yunnan
provinces
[ 1] .We reported the isolation and elucidation of
a new ent_kaurane derivative 16α_hydroxy_17_isovaleroy-
loxy_ent_kauran_19_oic acid from A.fargesii previous-
ly
[ 2] .In our continuing study , four diterpenoids were iso-
lated from the rhizome of A.fargesii.On the basis of
spectroscopic analysis and chemical methods , their struc-
tures were determined as 17_acetoxy_16α_ent_kauran_19_
oic acid (1), ent_pimara_8(14), 15_dien_19_oic acid(2), 16α_hydroxy_(-)_kauran_19_oic acid (3), 16α_
17_dihydroxy_ent_kauran_19_oic acid (4)(Fig.1).
Among them , 1 was a new compound , 2 , 3 and 4 were
isolated from this plant for the first time.
1　Results and Discussion
Compound 1was obtained as white powder , with mp
of 122-124 ℃, [ α] 20D -59°(c 0.051 0 , CHCl3).It
showed positive reactions both to Liebermann_Burchard
agent and 0.05%bromophenol blue solution , and had a
molecular formula as C22H34O4 (HREI_MS , Found.
362.244 7;Calcd.362.245 7).Its IR spectrum showed
strong absorptions at 1 739 cm
-1
and 1 699 cm
-1
owing
to the ester carbonyl and carboxyl groups , respectively.
The
1
H_NMR spectrum (Table 1)showed two angular
methyl signals atδ0.91 andδ1.21(each 3H , s)and
onemethyl group signal at δ2.02 (3H , s)due to the
acetoxy group.The 13C_NMR spectrum(Table 2)showed
the presence of 22 carbon atoms.Two tertiary methyl
groups atδ1.21 and δ0.91 in the 1H_NMR and the
carbon signals at δ182.0 (C_19), 28.9 (C_18)and
15.6(C_20)in 13C_NMR were typical of the axial C_20
and equatorial C_18 of diterpenoids with a C_19 axial car-
boxyl acid[ 3] .The 1H_NMR and 13C_NMR spectral data of
compound 1 were very similar to those of 17_hydroxy_16α_
ent_kauran_19_oic acid[ 4] , suggesting that compound 1
has the 17_hydroxy_16α_ent_kauran_19_oic acid skeleton.
Furthermore , the 1H and 13C_NMR spectral data of
C_17 and acetoxy group of compound 1 were coincident
with those of 17_acetoxy_18_isobutyryloxy_16_ent_kauran_
19_oic acid[ 5] , and the proton signals atδ3.83(2H , d ,
J =8.0 Hz)and carbon signal atδ68.7 were assignable
to the C_17 , suggesting that the OAc was attached to the
C_17.The structure of compound 1 was thus established
as 17_acetoxy_16α_ent_kauran_19_oic acid.
2　Experimental
2.1　General experimental procedures
Melting points were determined on X4 micro-melting
point apparatus uncorrected.IR spectra were measured on
Peking_Elmer 983G spectrometer.NMR spectrawere ob-
tained on Bruker AM_500 MHz spectrometer with TMS as
internal standard.HREI_MS and EI_MS were record on
KYKY_XSP_50 mass spectrometer.One hundred to two
hundred mesh silica gel and 10-40 μsilica gel H were
used for column chromatography.
2.2　Plant materials
Rhizomes of Aralia fargesii Franch.were collected
from Mount Emei , Sichuan Province , China , and identi-
fied by Professor ZHU Zhao_Yi.The specimen was de-
posited in the herbarium of Institute of Medicinal Plant
Development , Chinese Academy of Medical Science and
Peking Union Medical College.
2.3　Extraction and isolation
Rhizomes of Aralia fargesii(3.0 kg)were extracted
in Soxhlet extraction with petroleum ether for three times.
After removal of the solvent by evaporation , the residue(90 g)was subjected to column chromatography on silica
gel , eluted with gradient elution petroleum_EtOAc to give
20 fractions.Compound 1(3mg)was obtained from frac-
tions 4-9 by repeated chromatography on silica gel H.
Compounds 2(1.8 g), 3(7mg)and 4(4mg)were ob-
tained from fractions 3-9 and 10-14 by repeated chro-
matography on silica gel and silica gel H , respectively.
2.4　Identification
Compound 1 was obtained as white powder with mp
Received:2001-06-12　Accepted:2001-10-10
Supported by the National Natural Science Foundation of China(39740062).
＊Author for correspondence.
植　物　学　报　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　

Acta Botanica Sinica　2002 , 44(4):474-476
Fig.1.　Structures of diterpenoids 1-4.
Table 1　1H-NMR spectral data of compound 1(in CDCl3 , TMS as
internal standard , 500 MHz)
No. H No. H
1 0.79 1.87 13 2.04
2 1.42 1.85 14 2.13 2.15
3 1.83 1.84 15 0.93 1.58
5 1.04 16 2.05
6 1.76 1.78 17 3.83
7 1.49 1.50 18 1.21
9 0.99 20 0.91
11 1.51 1.60 2′ 2.02
12 1.40 1.53
Table 2　13C_NMR spectral data of compound 1 (in CDCl3 , 125
MHz)
No. C No. C No. C　
1 40.8 8 43.6 15 45.1
2 19.1 9 55.4 16 39.5
3 37.1 10 39.6 17 68.7
4 44.9 11 18.8 18 28.9
5 57.0 12 31.2 19 182.0
6 22.4 13 38.5 20 15.6
7 41.6 14 37.9 1′ 171.4
2′ 21.0
of 122-124 ℃, [ α] 20D -59°(c 0.051 0 , CHCl3),
Liebermann_Burchard test (+), C22H34O4.HREI_MS
(Found.362.244 7; Calcd. 362.245 7). IRνKBrmax
cm
-1:3 430 , 2 930 , 2 850 , 1 739 , 1 699 , 1 460 ,
1 360 , 1 239.EI_MS m/ z(%):362 (M+ , 2), 344
(M+-H2O , 28), 316 (90), 302 (36), 287 (21),
258(22), 243 (40).1H_NMR and 13C_NMR data are
shown in Table 1 and Table 2.
Compound 2was obtained as white needles , mp 141
-143 ℃, [ α] 20D -104°(c 0.117 8 , CHCl3), Lieber-
mann_Burchard test(+).IRνKBrmaxcm-1:3 430 , 3 080 ,
2 955 , 2 925 , 1 695 , 1 450 , 1 263 , 920.EI_MS m/ z
(%):302 , (M+ , 88), 287 (44), 269 (5), 257(32), 241(21), 220 (4), 201 (9), 187(15), 167(88), 187(15), 167(88), 148(43), 134(78), 123
(100), 107(73).1H_NMR(δ, CDCl3 , 500 MHz)and
13C_NMR(δ, CDCl3 , 125 MHz)data were in agreement
with those of reference [ 6] .
Compound 3 was obtained as white crystal , mp 215
-216 ℃, [ α] 20D -80°(c 0.125 5 , MeOH/CHCl3).
Liebermann_Burchard test (+).IR νKBrmax cm-1:3 450 ,
2 955 , 2 940 , 1 700 , 1 462 , 1 443 , 1 377 , 1 230 ,
915.EI_MS m/z (%):320 (M+ , 6),302(46), 287(28), 274(8), 262(35), 247(11), 217 (15), 187
(24), 159(21), 135(41).1H_NMR(δ, C5D5N , 500
MHz)and 13C_NMR(δ, C5D5N , 125 MHz)data were in
agreement with those of reference [ 7] .
Compound 4 was obtained as white crystal , mp 256
-258 ℃, [α] 20D -50°(c 0.03 , MeOH), Liebermann_
Burchard test (+).IR νKBrmax cm-1:3 430 , 3 240 ,
2 940 , 2 860 , 1 695 , 1 461 , 1 398 , 1 222 , 1 170 ,
1 160 , 1 025.EI_MS m/ z(%):336(M+ , 0.5), 318(5), 306(20), 305(100), 287(30), 260(19), 259
(55), 241 (12).1H_NMR(δ, C5D5N , 500 MHz)and
13
C_NMR(δ, C5D5N , 125MHz)data were in agreement
with those of references [ 8] and [ 9] .
References:
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药管理局).Chinese Medicinal Herbal Symposium.Shang-
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旭东).A new kaurane derivative from Aralia fargesii.
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[ 4] 　Xiong J , Ma Y , Xu Y.Diterpenoids from Siegesbeckia
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ZHANG Yu_Mei et al:A New Diterpenoid from Aralia fargesii 475　
ent_16β_17_dihydroxy_ent_kauran_19_oic acid as an anti_
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111.(in Chinese)
龙眼独活中的一个新二萜成分
张聿梅＊　杨峻山
(中国协和医科大学 、中国医学科学院药用植物研究所 , 北京 100094)
摘要:　从四川产 木属(Aralia)草本植物龙眼独活(Aralia fargesii Franch.)根茎的石油醚提取部分分离得到 4个二
萜化合物 ,根据理化性质测定和各种光谱(IR、EI_MS、HREI_MS 、1H-NMR、13C_NMR和 HMQC)数据分析 ,它们的结构分
别鉴定为17_acetoxy_16α_ent_kauran_19_oic acid(1), ent_pimara_8(14), 15_dien_19_oic acid (2), 16α_hydroxy_(-)_kauran_
19_oic acid(3)和 16α_17_dihydroxy_ent_kauran_19_oic acid(4)。化合物 1 为新化合物 , 3 为首次从该属植物中分离得
到 , 2～ 4为首次从龙眼独活中分离得到。
关键词:　龙眼独活;二萜;17_acetoxy_16α_ent_kauran_19_oic acid
中图分类号:R914　　　文献标识码:A　　　文章编号:0577-7496(2002)04-0474-03
收稿日期:2001-06-12　接收日期:2001-10-10
基金项目:国家自然科学基金(39740062)。
＊通讯作者。
(责任编辑:王　葳)
476　 植物学报　Acta Botanica Sinica　Vol.44　No.4　2002