全 文 ： 2011 年 1 月 第 9 卷 第 1 期 Chin J Nat Med Jan. 2011 Vol. 9 No. 1 17

Chinese Journal of Natural Medicines 2011, 9(1): 0017−0021
doi: 10.3724/SP.J.1009.2011.00017
Chinese
Journal of
Natural
Medicines







·Original Papers·
A New Triterpenoid Saponin from the Leaves of Aralia elata
WANG Qiu-Hong1, ZHANG Jian 2, MA Xu3, YE Xu-Yan 1, YANG Bing-You 1,
XIA Yong-Gang 1, KUANG Hai-Xue1*
1Key Laboratory of Chinese Materia Medica (Heilongjiang University of Chinese Medicine), Ministry of Education, Harbin 150040,
China; 2Soochow University, Suzhou 215123, China; 3Patent Examination Cooperation Center, State Intellectual Property Office, Beijing
100083, China
Available online 20 Jan. 2011
[ABSTRACT] AIM: To study the chemical constituents of the leaves of Aralia elata (Miq.) Seem, and find new or effective compo-
nents. METHODS: Compounds were isolated by repeated silica gel, ODS and Sephadex LH-20 column chromatography. The struc-
tures were elucidated by NMR and HRESI-MS spectrometry. RESULTS: A triterpenoid saponin and two flavonoid glycosides were
isolated from the leaves of A. elata, and their structures were elucidated as echinocystic acid-3-O-β-D-glucopyranosyl-(1-3)-
β-D-glucuronopyranoside-6-O-butyl ester (1), 7-O-α-rhamnopyranosyl-(S)-quercetin-3-O-β-glucopyranosyl-(1→2)-α-rhamnopyrano-
side (2) and 7-O-α-rhamnopyranosyl-(S)-quercetin-3-O-β-6-caffeoyl-glucopyranosyl-(1→2)-α-rhamnopyranos-ide (3), respectively.
CONCLUSION: Compound 1 is a new triterpenoid saponin, which is the first one with a butyl group isolated from the genus Aralia,
while compounds 2 and 3 are reported from this species for the first time.
[KEY WORDS] Aralia elata; Triterpenoid saponin; Flavonoid glycosides
[CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2011)01-0017-05

1 Introduction
Aralia elata (Miq.) Seem is a small tree, which belongs
to the family Araliaceae with around 40 species occurring in
Asia and North America [1]. A. elata is widely distributed in
Heilongjiang, Liaoning and Jilin provinces of China and was
recorded in a Chinese ancient book, “Compendium of Mate-
ria Medica”. Its root bark was used as Chinese folk medicine
for the treatment of neurasthenia, arthritis and diabetes for a
long time [1]. In the past few years, a lot of triterpene saponins
have been isolated from the buds of A. elata [2-5]. However,
there are few studies on the constituents of the leaves of A.
elata. In continuation of our search for pharmacological and
structurally interesting substances from traditional Chinese
herbal drugs, we investigated the chemical constituents of the
leaves of A. elata by column chromatography and a triterpe-

[Received on] 30-Aug-2010
[Research Funding] This project was supported by International
Scientific and Technological Cooperation Program (No. 2007DFA
30930).
[*Corresponding author] KUANG Hai-Xue: Prof., Tel: 86-451-
82193001, Fax: 86- 451-82110803, E-mail:hxkuang@hotmail.com
These authors have no any conflict of interest to declare.
noid saponin and two flavonoid glycosides were obtained
(Fig. 1). The present paper deals with the experimental details
of separation and structural elucidation of these three com-
pounds on the basis of the spectroscopic analysis, including
2D-NMR techniques, HR-ESI-MS and the result of hydro-
lytic reaction.
2 Results and Discussion
Compound 1 was obtained as a white amorphous powder,
which was considered to be a triterpenoid glycoside due to
the positive results for the Liebermann-Burchard reaction
and Molish reagent. The IR spectrum of 1 indicated the pres-
ence of hydroxyl (3 421 cm-1), carboxyl (1 741 cm-1) and
carbonyl (1 698 cm-1) groups. Its molecular formula was
determined as C46H74O15 according to the positive
HRESI-MS from the [M + Na]+ signal at m/z 889.493 8
(Calcd. for C46H74NaO15, [M + Na]+, 889.492 5), indicating
ten degrees of unsaturation.
The 1H NMR spectrum (Table 1) displayed eight methyl
signals at δ 0.68 (3H, s), 0.76 (3H, s), 0.80 (3H, s), 0.86 (3H,
s), 0.90 (3H, s), 0.98 (3H, s), 1.31 (3H, s) and 0.87 (3H, t, J =
7.2 Hz), an oxygenated methine proton signal at δ 4.32 (1H,
br s), two anomeric sugar protons at δ 4.30 (1H, d, J = 7.2 Hz)
WANG Qiu-Hong, et al. /Chinese Journal of Natural Medicines 2011, 9(1): 17−21
18 Chin J Nat Med Jan. 2011 Vol. 9 No. 1 2011 年 1 月 第 9 卷 第 1 期

and 4.44 (1H, d, J = 8.0 Hz) and series of overlapped signals
suggesting an olean-type triterpene glycoside. A further fea-
ture of the 1H NMR spectrum was the signal at δ 5.19 (1H, br
s) typical of H-12 of ∆12 oleane skeleton, which was also
indicated by the signals at δ 121.0 and 144.0, due to C-12 and
C-13 in the 13C NMR spectrum. In the same spectrum the
presence of a carboxylic carbon at δ 178.8 and the carbon
resonances of rings D and E suggested no occurrence of a
glycosylated COOH group at C-28 [6-7]. The 13C NMR also
showed the presence of two anomeric carbon signals at
δ104.0 and 104.7, which correlated with the protons at δ 4.30
(1H, d, J = 7.2 Hz) and 4.44 (1H, d, J = 8.0 Hz) in the HSQC
spectrum. Besides, an oxygenated carbon signal at δ 72.9,
and one ester carbonyl carbon at δ 168.5 can be observed in

Fig. 1 Structures of compounds 1 – 3
Table 1 1H and 13C NMR data of 1 at 400 MHz for protons and 100 MHz for carbons (in DMSO-d6)
No. δC δH No. δC δH
1 38.0 1.51, 0.91 (m) GlcA 1 104.7 4.44 (d, J = 8.0 Hz)
2 25.5 1.65, 155 (m) 2 72.2 3.22 (m)
3 88.3 3.09 (m) 3 86.8 3.43 (m)
4 38.6 − 4 69.9 3.43 (m)
5 54.9 0.71 (m) 5 74.6 3.81 (m)
6 17.7 1.48 (m) 6 168.5 −
7 32.5 1.40, 1.22 (m) Glc 1 104.0 4.30 (d, J = 7.2 Hz)
8 38.8 − 2 73.7 3.05 (m)
9 46.0 1.54 (m) 3 76.8 3.18 (m)
10 36.2 − 4 70.0 3.02 (m)
11 22.7 1.78 (m) 5 75.9 3.15 (m)
12 121.0 5.19 (br s) 6 61.0 3.68 (dd, J = 12.6, 2.2 Hz), 3.37 (o)
13 144.0 − n-butyl 1 64.1 4.11 (m)
14 40.9 − 2 30.0 1.56 (m)
15 34.5 1.70, 1.21 (m) 3 18.3 1.31 (m)
16 72.9 4.32 (br s) 4 13.4 0.87 (t, J = 7.2 Hz)
17 47.2 −
18 39.8 2.90 (m)
19 46.4 2.20, 0.96 (m)
20 30.1 −
21 35.1 1.88, 1.05 (m)
22 31.2 1.74, 1.59 (m)
23 27.3 0.98 (s)
24 16.3 0.76 (s)
25 15.1 0.86 (s)
26 16.7 0.68 (s)
27 26.3 1.31 (s)
28 178.8 −
29 32.8 0.80 (s)
30 24.1 0.90 (s)

WANG Qiu-Hong, et al. /Chinese Journal of Natural Medicines 2011, 9(1): 17−21
2011 年 1 月 第 9 卷 第 1 期 Chin J Nat Med Jan. 2011 Vol. 9 No. 1 19

the 13C NMR spectrum. The above data suggest that 1 con-
tains two sugar moieties and a triterpenoid aglycone with the
skeleton of chinocystic acid [6-7].
Acidic hydrolysis of 1 gave D-glucose and D-glucuronic
acid, which was confirmed by TLC comparison with authen-
tic samples. 1H-1H COSY spectrum showed not only proton
correlation signals of echinocystic acid and two sugar moie-
ties, but also another three couples. They were δH 4.11 (2H,
m)/1.56 (2H, m), 1.56 (2H, m)/1.31 (2H, m), 1.31 (2H,
m)/0.87 (3H, t, J = 7.2 Hz). Meanwhile, HSQC spectrum
showed that proton signals at δH 4.11 (2H, m), 1.56 (2H, m),
1.31 (2H, m), 0.87 (3H, t, J = 7.2 Hz) attached to four carbon
signals at δC 64.1, 30.0, 18.3, 13.4, respectively. It suggested
that 1 contains a normal-butyl fragment. Their linkages could
be determined by the HMBC spectrum showing long-range
correlations between H-1 of GlcA (δ 4.44, 1H, d, J = 8.0 Hz)
and C-3 of the aglycone (δ 88.3), H-1 of Glc (δ 4.30, 1H, d,
J = 7.2 Hz) and C-3 of GlcA (δ 86.8), as well as H-1 of
butyl (δ 4.11) and C-6 of GlcA (δ 168.5) (Fig. 2). Based on
the above results, the structure of 1 could be deduced to be
echinocystic acid-3-O-β-D-glucopyranosyl-(1-3)-β-D-glucu-
ronopyranoside-6-O-butyl ester.

Fig. 2 Key 1H-1H COSY and HMBC correlations of 1
Compounds 2 and 3 were identified as 7-O-α-rhamno-
pyranosyl-quercetin-3-O-β-glucopyranosyl-(1→2)-α-rhamno-
pyranoside and 7-O-α-rhamnopyranosyl-quercetin-3-O-β-6-
caffeoyl-glucopyranosyl-(1→2)-α-rhamnopyranoside by de-
tailed 1D and 2D-NMR data.
However, in NOE difference spectrum of 2 (DIFNOE),
irradiation at H-2′ (δ 7.42) can enhance the signal intensities
of H-1′′ [δ 5.49 (1H, br s)] of the rhamnopyranosyl rather
than H-5′ (δ 6.91). Irradiation at H-6′ (δ 7.34) can enhance
the signal intensities of H-5′ (δ 6.91) rather than H-1′′.
Moreover, in phase sensitive NOESY (PSNOE), a notable
NOE correlation was observed between H-1′′ [δ 5.49 (1H, br.
s)] of the rhamnopyranosyl and H-2′ (δ 7.42). On the other
hand, no NOE correlation was observed between H-1′′ [δ
5.49 (1H, br s)] of the rhamnopyranosyl and H-6′ and H-5′,
respectively. Thus, the space distance between H-1′′ and H-2′
was quite close. However, the space position of H-1′′ was far
from H-5′ and H-6′. So we can conclude that the structure of
2 should be A rather than B (Fig. 3). Here, we named the B
ring with clockwise 3′, 4-substitution patterns as quercetin (R)
and B ring with counterclockwise 3′, 4-substitution patterns
as quercetin (S). In DIFNOE and PSNOE spectra of 3, there
was the same NOE effect as 2. On the basis of the above data,
2 and 3 were established as 7-O-α-rhamnopyranosyl-(S)-
quercetin-3-O-β-glucopyranosyl-(1→2)-α-rhamnopyranoside
and 7-O-α-rhamnopyranosyl-(S)-quercetin-3-O-β-6-caffeoyl-
glucopyranosyl-(1→2)-α-rhamnopyranoside, respectively.

Fig. 3 Two possible space orientations of 2
In conclusion, this is the first report of quercetin gly-
cosides with counterclockwise 3′, 4-substitution patterns of B
ring. It is well-known that the previous studies have isolated
many quercetin and kaempferol glycosides at C-3 with link-
ages of Glc-Rha from herb plants and it is very interesting to
find quercetin glycosides with linkages of Rha-Glc from this
plant.
3 Experimental
3.1 General experimental procedures
NMR spectra were recorded on JNM LA-500 (400 MHz
for 1H NMR and 100 MHz for 13C NMR), respectively.
Chemical shifts are given as δ values with reference to
tetramethylsilane (TMS) as internal standard, and coupling
constants are given as J in Hz. The UV and optical rotations
were recorded on Shimadzu UV-1601 and Perkin-Elmer 341
polarimeter, respectively. The HR-ESI-MS analyses were
conducted on IonSpec Ultima 7.0T FTICR. Analysis TLC
(Kieselgel 60 F254 and Rp-18) was from Merck, Germany.
3.2 Plant material
The leaves of A. elata were collected in July 1990 from
Taoshan Forestry Bureau of Heilongjiang Province, China
and identified by Prof. WANG Zhen-Yue of Heilongjiang
University of Chinese Medicine. The voucher specimen (No.
19900063) was deposited at Herbarium of Heilongjiang Uni-
versity of Chinese Medicine, Harbin, China.
3.3 Extraction and isolation
The dry leaves of A. elata (6.8 kg) were extracted under
reflux with 95% EtOH (25 L × 2 × 2 h each). The combined
95% EtOH extracts were evaporated to near dryness under
vacuum and the resulting mixture was suspended in H2O and
partitioned successively with petroleum ether (3 × 2 L),
CHCl3 (3 × 2.5 L) and n-BuOH (3 × 2.5 L) to afford petro-
leum ether extract (72 g), CHCl3 extract (60 g) and n-BuOH
extract (170 g). The n-BuOH fraction (98 g) was applied to a
silica-gel column chromatography with CHCl3/MeOH (30:1
→ 0:1, V/V) gradient to give fractions A1-A6. A4 (9.2 g) was
applied to ODS column chromatography with MeOH/H2O
(15:85 → 1:0, V/V) to yield four sub-fractions A4-1(1.1 g),
WANG Qiu-Hong, et al. /Chinese Journal of Natural Medicines 2011, 9(1): 17−21
20 Chin J Nat Med Jan. 2011 Vol. 9 No. 1 2011 年 1 月 第 9 卷 第 1 期

A4-2 (2.8 g), A4-3 (2.3 g) and A4-4 (1.2 g). A4-1 (1.1 g) was
applied to Sephadex LH-20 column chromatography with
MeOH/H2O (7:3, V/V) to yield compounds 3 (85 mg) and 2
(102 mg). A4-2 (1.2 g) was applied to ODS column chroma-
tography with MeOH/H2O (6:4, V/V) to yield compound 1
(120 mg).
Echinocystic acid-3-O-β-D-glucopyranosyl-(1-3)-β-D-
glucuronopyranoside-6-O-butyl ester (1, Fig. 1), C46H74O15,
white powder, [α]D25 −13.8° (c 0.15, MeOH); IR (KBr): 3 421,
2 947, 1 741, 1 698, 1 461, 1 383, 1 078; HR-ESI-MS m/z:
889.493 8 [M + Na]+ Calcd. for C46H74NaO15 889.492 5; 1H
and 13C NMR data see Table 1.
7-O-α-rhamnopyranosyl-(S)-quercetin-3-O-β-glucopyran
osyl-(1→2)-α-rhamnopyranoside (2, Fig. 1), C33H40O20, yel-
low amorphous powder; [α]D25 −6.8° (c 0.1, MeOH); UV
(MeOH): λmax: 258, 359 nm; HR-ESI-MS m/z: 779.202 4 [M
+ Na]+ Calcd. for C33H40O20Na 779.201 1; 1H and 13C NMR
data see Table 2.
Table 2 1H and 13C NMR data of 2 and 3 at 400 MHz for protons and 100 MHz for carbons (in DMSO-d6)
2 3
No.
δC δH δC δH
2 157.4 − 157.2 −
3 134.7 − 134.5 −
4 177.9 − 177.9 −
5 160.8 − 160.9 −
6 99.3 6.45 (1H, d, J = 2.1 Hz) 99.3 6.39 (1H, d, J = 2.1 Hz)
7 161.6 − 161.6 −
8 94.4 6.78 (1H, d, J = 2.1 Hz) 94.4 6.68 (1H, d, J = 2.1 Hz)
9 155.9 − 155.9 −
10 105.6 − 105.6 −
1 120.3 − 120.2 −
2 115.5 7.42 (1H, d, J = 2.0 Hz) 115.5 7.40 (1H, d, J = 2.1 Hz)
3 145.2 − 145.2 −
4 148.7 − 148.9 −
5 115.4 6.91 (1H, d, J = 8.2 Hz) 115.4 6.87 (1H, d, J = 8.2 Hz)
6 121.0 7.34 (1H, dd, J = 8.2, 2.0 Hz) 121.0 7.29 (1H, dd, J = 8.2, 2.1 Hz)
3-O-Rha 1 101.0 5.49 (1H, br s) 101.0 5.49 (1H, br s)
2 81.3 4.15 (1H, m) 81.6 4.16 (1H, m)
3 70.2 3.57 (1H, m) 70.0 3.59 (1H, m)
4 71.7 3.13 (1H, m) 71.7 3.13 (1H, m)
5 70.3 3.62 (1H, m) 70.2 3.64 (1H, m)
6 17.3 0.91 (1H, d, J = 6.3 Hz) 17.4 0.92 (1H, d, J = 6.3 Hz)
3-O-Glc 1 106.2 4.23 (1H, d, J = 7.7 Hz) 106.2 4.27 (1H, d, J = 7.9 Hz)
2 73.8 3.00 (1H, m) 73.7 3.05 (1H, m)
3 76.4 2.98 (1H, m) 75.9 2.97 (1H, m)
4 68.9 3.16 (1H, m) 69.2 3.16 (1H, m)
5 76.1 3.14 (1H, m) 73.6 3.12 (1H, m)
6 60.1 3.31 (1H, dd, J = 12.0, 4.8 Hz) 62.6 3.37 (1H, dd, J = 12.4, 5.0 Hz)
3.46 (1H, dd, J = 12.0, 2.2 Hz) 3.48 (1H, dd, J = 12.4, 2.1 Hz)
7-O-Rha 1 98.3 5.56 (1H, br s) 98.4 5.51 (1H, br s)
2 69.7 3.85 (1H, m) 69.8 3.82 (1H, m)
3 70.2 3.64 (1H, m) 70.4 3.61 (1H, m)
4 71.5 3.30 (1H, m) 71.6 3.28 (1H, m)
5 70.0 3.42 (1H, m) 69.8 3.40 (1H, m)
6 17.8 1.13 (1H, d, J = 6.6 Hz) 17.9 1.10 (1H, d, J = 6.1 Hz)
Caffeoyl 1 − 125.4 -
2 − 114.8 6.93(1H, d, J=2.1Hz)
3 − 145.5 −
4 − 148.3 −
5 − 115.5 6.66(1H, d, J=8.0Hz)
6 − 120.9 6.86(1H, dd, J=8.0, 2.1Hz)
7 − 145.1 7.37(1H, d, J=15.6Hz)
8 − 113.7 6.13(1H, d, J=15.6Hz)
9 − 166.3 −
WANG Qiu-Hong, et al. /Chinese Journal of Natural Medicines 2011, 9(1): 17−21
2011 年 1 月 第 9 卷 第 1 期 Chin J Nat Med Jan. 2011 Vol. 9 No. 1 21


7-O-α-rhamnopyranosyl-(S)-quercetin-3-O-β-6-caffeoyl-
glucopyranosyl-(1→2)-α-rhamnopyra-nside (3, Fig. 1),
C42H46O23, yellow amorphous powder; [α]D25 −17.3° (c 0.1,
MeOH); UV (MeOH): λmax: 266, 368 nm; HR-ESI-MS m/z:
941.231 6 [M + Na]+ Calcd. for C42H46O23Na 941.232 8; 1H
and 13C NMR data see Table 2.
References
[1] Chinese Academy of Sciences. Flora of China, Vol. 55 [M].
Chinese Science Press, 1979: 166.
[2] Ma ZQ, Zhang Y, Song SJ, et al. Two new glycosides from the
buds of Aralia e ata (Miq.) Seem [J]. Chin J Med Chem, 2008,
18(4): 300-301.
[3] Ma ZQ, Song SJ, Xu SX. Two new saponins from Aralia elata
(Miq.) Seem [J]. Chin J Med Chem, 2004, 14(1): 47-48.
[4] Li L, Song SJ, Liang ZX, et al. A new triterpene saponin from
the buds of Aralia elata (Miq.) Seem [J]. J Shenyang Pharm
Univ, 2006, 23(8): 499-500.
[5] Li L, Song SJ, Li LZ, et al. Chemical constituents of the buds
of Aralia elata (Miq.) Seem. (Ш) [J]. J Shenyang Pharm Univ,
2006, 23(8): 495-498.
[6] Xu LP, Wang H, Yuan Z. Triterpenoid saponins with
anti-inflammatory activity from Codonopsis ianceolata [J]. Lett
Planta Med, 2008, 74 (11): 1412-1415.
[7] Lee MK, Ha NR, Yang H, et al. Antiproliferative activity of
triterpenoids from Eclipta prostrata on hepatic stellate cells [J].
Phytomedicine, 2008, 15 (9): 775-780.

辽东楤木叶中一个新三萜皂苷
王秋红 1, 张 健 2, 马 旭 3, 叶旭炎 1, 杨炳友 1, 夏永刚 1, 匡海学 1*
1黑龙江中医药大学省部共建重点实验室, 哈尔滨 150040;
2苏州大学, 苏州 215123;
3国家知识产权局专利审查协作中心, 北京 100083
【摘 要】 目的：研究辽东　木叶的化学成分。方法：采用硅胶、ODS、Sephadex LH-20 等多种层析柱分离手段, 运用 NMR
和 HR-ESI-MS 等波谱技术鉴定化合物的结构。结果：从辽东　木叶分离并鉴定了 1 个三萜皂苷和 2 个黄酮苷类化合物：
3-O-β-D-glucopyranosyl(1-3)-β-D-glucuronopyranoside-6-O-butyl ester (1), 7-O-α-rhamnopyranosyl-(S)-quercetin-3-O-β-glucopyra-
nosyl-(1→2)-α-rhamnopyranoside (2) 和 7-O-α-rhamnopyranosyl-(S)-quercetin-3-O-β-6-caffeoyl-glucopyranosyl-(1→2)-α-rhamnopy-
ranoside (3)。结论：化合物 1 为新化合物, 也是从该属中分离出的第一个具有正丁基取代的三萜皂苷, 化合物 2 和 3 为首次从
该植物中分离得到。
【关键词】 辽东楤木叶; 三萜皂苷; 黄酮苷

【基金项目】国际科技合作计划 (No. 2007DFA 30930)

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