全 文 ： 2011 年 5 月 第 9 卷 第 3 期 Chin J Nat Med May 2011 Vol. 9 No. 3 191

Chinese Journal of Natural Medicines 2011, 9(3): 0190−0192
doi: 10.3724/SP.J.1009.2011.00190
Chinese
Journal of
Natural
Medicines







Triterpenes and Steroids from Semi-mangrove
Plant Hibiscus tiliaceus
WANG Zhong-Zhao1, LI Jun1, TANG Xv-Li2, LI Guo-Qiang1*
1School of Medicine and Pharmacy, Key Laboratory of Marine Drugs, Ministry of Education, Ocean University of China, Qingdao
266003, China;
2College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, China
Available online May 2011
[ABSTRACT] AIM: To study the chemical constituents of semi-mangrove plant Hibiscus tiliaceus. METHODS: The isolation and
purification of compounds were performed by silica gel, Sephadex LH-20 and HPLC, and their structures were determined by com-
parison of their physical and spectral data with the literatures. RESULTS: Ten compounds were isolated and identified as friedelin (1),
pachysandiol (2), glutinol (3), lupeol (4), germanicol (5), stigmast-4-en-3-one (6), stigmast-4, 22-dien-3-one (7), ergosta-4, 6, 8 (14),
22-tetraen-3-one (8), β-sitosterol (9), and stigmasterol (10). CONCLUSION: Compounds 3–5 and 8 were isolated from this plant for
the first time.
[KEY WORDS] Hibiscus tiliaceus; Triterpenes; Steroids
[CLC Number] R284.1 [Document code] A [Article ID] 1672-3651(2011)03-0191-03

1 Introduction
The semi-mangrove plant Hibiscus tiliaceus belonging
to the genus Hibiscus (family Malvaceae) is widely distribu-
ted in southeastern Asia, Philippines, Pacific Islands, the
South Sea Islands and India. As a Chinese medicine, it is
used as heat-clearing and detoxifying, stasis-dissipating and
detumescence agents in folk [1]. A survey of literatures re-
vealed that the constituents of the species H. tiliaceus were
studied rarely [2-4]. Our preliminary examination of the stem
and bark of H. tiliaceus collected from Hainan Island, South
China, resulted in the isolation and characterization of ten
compounds: friedelin (1), pachysandiol (2), glutinol (3), lu-
peol (4), germanicol (5), stigmast-4-en-3-one (6), stigmast-4,
22-dien-3-one (7), ergosta-4, 6, 8 (14), 22-tetraen-3-one (8),
β-sitosterol (9) and stigmasterol (10) (Fig.1). Compounds 3–5
and 8 were obtained from this plant for the first time.
2 Apparatus and Reagents
Melting points (mp) were determined on an X4 micro-
melting apparatus and uncorrected. ESI-MS spectra were

[Received on] 31-Dec.-2010
[Research Funding] This project was supported by State Bureau of
Oceanic Administration (No. 908-01-ST12)
[*Corresponding author] LI Guo-Qiang: Prof., Tel: 0532-82032323,
E-mail: liguoqiang@ouc.edu.cn
These authors have no any conflict of interest to declare.
recorded on a Waters Q-TOF LC-MS-MS mass spectrometer.
1H and 13C NMR spectra were recorded on a JEOL
JNM–ECP600 spectrometer with the residual CHCl3 (δH 7.26,
δC 77.0) as an internal standard. Reversed-phase HPLC
(Agilent 1100 series liquid chromatography equipped with a
VWD detector and a semi-preparative ODS [5 µm, 10 mm
(i.d.) × 25 cm] column), commercial Sigel (Qingdao Marine
Chemical Group Co., 200-300 and 400–600 mesh) and
Sephadex LH-20 (Pharmacia Biotech AB, Uppsala, Sweden)
were employed for separation and purifification.
3 Plant Material
The stems and barks of H. tiliaceus were collected in
Hainan Island, South China, in July, 2006. The plant material
was identified by Mr. ZHONG Cai-Rong, Administrative
Bureau of Dongzhai National Nature Conservation, Haikou,
Hainan province. A voucher specimen (060701) has been
deposited at School of Medicine and Pharmacy, Ocean Uni-
versity of China, Qingdao, China.
4 Extraction and Isolation
The air-dried and powdered stems and barks of H. tili-
aceus (11.0 kg) were extracted with industrial methanol three
times at room temperature. The extract was concentrated
under reduced pressure to generate a dark residue (336.0 g),
which was suspended in H2O and partitioned with petroleum
ether, ethyl acetate and n-butanol, yielding 83.0, 40.0 and
45.0 g of extraction fractions, respectively. Combined petro-
leum ether and ethyl acetate fraction based on TLC results.
WANG Zhong-Zhao, et al. /Chinese Journal of Natural Medicines 2011, 9(3): 191−193
192 Chin J Nat Med May 2011 Vol. 9 No. 3 2011 年 5 月 第 9 卷 第 3 期


Fig. 1 Structures of compounds 1-10
The petroleum ether and ethyl acetate fraction was subjected
to column chromatography on silica gel eluted with petro-
leum ether-acetone gradient (10 : 0-1 : 10) to give eight sub-
fractions Frs.1–8. Frs.1–3 were further purified by repeated
chromatographic techniques to yield compounds 1 (10 mg), 2
(50 mg), 3 (20 mg), 4 (6 mg), 5 (8.6 mg), 6 (10 mg), 7 (5 mg),
8 (6.7 mg), 9 (3.7 mg) and 10 (5.8 mg).
5 Identification
Compound 1 C30H50O, white needle, mp 261–263 °C.
1H NMR (600 MHz, CDCl3) δ: 2.39 (1H, ddd, J = 13.6, 5.1,
2.2 Hz, H-2a), 2.31 (1H, dd, J = 13.2, 7.3 Hz, H-2b), 2.25
(1H, q, J = 6.6 Hz, H-4), 1.97 (1H, m, H-1a), 1.75(1H, m,
H-6a), 1.68 (1H, m, H-1b), 1.18 (3H, s, H-28), 1.05 (3H, s,
H-27), 1.01 (3H, s, H-26), 1.00 (3H, s, H-29), 0.95 (3H, s,
H-30), 0.88 (3H, d, J = 6.6 Hz, H-23), 0.87 (3H, s, H -25),
0.72 (3H, s, H-24). 13C NMR (150 MHz, CDCl3) δ: 213.4
(C-3), 59.5 (C-10), 58.3 (C-4), 53.2 (C-8), 42.9 (C-18), 42.2
(C-5), 41.6 (C-2), 41.4 (C-6), 39.8 (C-13), 39.3 (C-22), 38.4
(C-14), 37.5 (C-9), 36.1 (C-16), 35.7 (C-11), 35.4 (C-19),
35.1 (C-30), 32.8 (C-15), 32.5 (C-21), 32.2 (C-28), 31.9
(C-29), 30.6 (C-12), 30.1 (C-17), 28.3 (C-20), 22.4 (C-1),
20.4 (C-26 ), 18.7 (C-27), 18.3(C-7), 18.0 (C-25), 14.7
(C-24), 6.9 (C-23). Compound 1 was identified as friedelin
by comparison of the physical and spectral data with the lit-
erature [5].
Compound 2 C30H52O2, white needle, mp 290–291 °C.
ESI-MS m/z 408 [M – 2H2O]+. 1H NMR (600 MHz, CDCl3)
δ:3.99 (1H, q, H-2), 3.54 (1H, t, H-3), 1.83 (1H, td, H-1b),
1.61 (1H, m, H-1a), 1.17 (3H, s, H-28), 1.01 (3H, s, H-26),
0.99 (6H, s, H-27, 29), 0.94 (3H, d, J = 7.2, H-23), 0.94 (3H,
s, H-24), 0.94 (3H, s, H-30), 0.85 (3H, s, H-25). Compound 2
was identified as pachysandiol by comparison of the physical
and spectral data with the literature [6].
Compound 3 C30H52O, white needle, mp 218–219 °C.
1H NMR (600 MHz, CDCl3) δ: 5.63 (1H, br d, J = 6.1 Hz,
H-6), 3.47 (1H, t, J = 2.8, H-3), 1.16 (3H, s, H-24), 1.14 (3H,
s, H-28), 1.09 (3H, s, H-23), 1.04 (3H, s, H-29), 1.00 (3H, s,
H-26), 0.99 (3H, s, H-27), 0.95 (3H, s, H-30), 0.85 (3H, s,
H-25). 13C NMR (150 MHz, CDCl3) δ: 141.7 (C-5), 122.2
(C-6), 76.4 (C-3), 49.8 (C-10), 47.5 (C-18), 43.1 (C-8), 40.9
(C-14), 39.4 (C-4), 39.0 (C-22), 37.9 (C-13), 36.1 (C-16),
35.2 (C-19), 34.9 (C-9), 34.7 (C-11), 34.6(C-29), 33.2 (C-21),
32.5 (C-28), 32.2 (C-15), 32.1 (C-30), 30.4 (C-12), 30.2
(C-17), 29.0 (C-23), 28.3 (C-20), 27.9 (C-7), 25.6 (C-24),
23.7 (C-1), 19.7 (C-27), 18.5 (C-26), 18.3 (C-2), 16.3(C-25).
Compound 3 was identified as glutinol by comparison of the
physical and spectral data with the literature [7].
Compound 4 C30H50O, white needle, mp 214.0–215.0
°C. ESI-MS m/z 408 [M – H2O]+. 1H NMR (600 MHz,
CDCl3) δ: 4.69 (1H, br s, H-29a), 4.57 (1H, br s, H-29b), 3.18
(1H, dd, J = 11.6, 5.0 Hz, H-3), 2.37 (1H, m, H-19), 1.68 (3H,
s, H-30), 1.03 (3H, s, H-26), 0.97 (3H, s, H-23), 0.94 (3H, s,
H-27), 0.83 (3H, s, H-25), 0.79 (3H, s, H-28), 0.76 (3H, s,
H-24). Compound 4 was identified as lupeol by comparison
of the physical and spectral data with the literature [8].
Compound 5 C30H50O, white crystal, mp 175–178 °C.
ESI-MS m/z 408 [M – H20]+. 1H NMR (600 MHz, CDCl3) δ:
4.86 (1H, s, H-19), 3.20 (1H, dd, J = 11.5, 6.2 Hz, H-3), 1.08
(3H, s, H-30), 1.02 (3H, s, H-29), 0.97 (3H, s, H-28), 0.94
(6H, s, H-26, 27), 0.88 (3H, s, H-24), 0.77 (3H, s, H-25), 0.75
(3H, s, H-23). 13C NMR (150 MHz, CDCl3) δ: 142.8 (C-18),
129.7 (C-19), 79.0 (C-3), 55.5 (C-5), 51.2 (C-9), 43.3 (C-14),
40.8 (C-8), 38.9 (C-4, 13), 38.4 (C-1), 37.7 (C-16), 37.3
(C-22), 37.2 (C-10), 34.6 (C-7), 34.4 (C-17), 33.3 (C-21),
32.3 (C-20), 31.3 (C-29), 29.2 (C-30), 28.0 (C-23), 27.5
(C-15), 27.4 (C-2), 26.2 (C-12), 25.3 (C-28), 21.1 (C-11),
18.3 (C-6), 16.7 (C-26), 16.1 (C-25), 15.4 (C-24), 14.6
(C-27). Compound 5 was identified as germanicol by com-
parison of the physical and spectral data with the literature [9].
Compound 6 C29H48O, white needle, mp 155.0–157.0
°C. ESI-MS m/z 412 [M]+. 1H NMR (600 MHz, CDCl3) δ:
5.72 (1H, s, H-4), 1.19 (3H, s, H-19), 0.92 (3H, d, J = 6.4 Hz,
H-21), 0.85 (3H, t, J = 8.1 Hz, H-29), 0.83 (3H, d, J = 7.2 Hz,
H-27), 0.81 (3H, d, J = 6.9 Hz, H-26), 0.71 (3H, s, H-18). 13C
NMR (150 MHz, CDCl3) δ: 199.7 (C-3), 171.7 (C-5), 123.7
(C-4), 56.0 (C-17), 55.9 (C-14), 53.8 (C-9), 45.8 (C-24), 42.4
(C-13), 39.6 (C-12), 38.6 (C-10), 36.1 (C-20), 35.7 (C-1),
WANG Zhong-Zhao, et al. /Chinese Journal of Natural Medicines 2011, 9(3): 191−193
2011 年 5 月 第 9 卷 第 3 期 Chin J Nat Med May 2011 Vol. 9 No. 3 193

35.6 (C-8), 34.0 (C-22), 33.9 (C-2), 32.9 (C-6), 32.0 (C-7),
29.1 (C-25), 28.1 (C-16), 26.1 (C-23), 24.1 (C-15), 23.0
(C-28), 21.0 (C-11), 19.8 (C-26), 19.0 (C-27), 18.8 (C-21),
17.4 (C-19), 11.9 (C-29), 11.9 (C-18). Compound 6 was
identified as stigmast-4-en-3-one by comparison of the
physical and spectral data with the literature [10].
Compound 7 C29H46O, white needle, mp 115–116 °C.
ESI-MS m/z 410 [M]+. 1H NMR (600 MHz, CDCl3) δ: 5. 72
(1H, s, H-4), 5.15 (1H, dd, J = 15.4, 8.3 Hz, H-22), 5.02 (1H,
dd, J = 15.4, 8.8 Hz, H-23), 1.18 (3H, s, H-19), 1.01 (3H, d, J
= 6.6 Hz, H-21), 0.85 (3H, d, J = 6.1 Hz, H-27), 0.80 (3H, t, J
= 7.7 Hz, H-29), 0.80 (3H, d, J = 6.1 Hz, H-26), 0.72 (3H, s,
H-18). Compound 7 was identified as stigmast-4, 22-dien-3-
one by comparison of the physical and spectral data with the
literature [11].
Compound 8 C28H40O, yellow needle, mp 110–113
°C. ESI-MS m/z 392 [M]+. 1H NMR (600 MHz, CDCl3) δ:
6.61 (1H, d, J = 9.5 Hz, H-7), 6.03 (1H, d, J = 9.5 Hz, H-6),
5.74 (1H, s, H-4), 5.24 (2H, m, H-22、23), 1.06 (3H, d, J =
6.7 Hz, H-21), 1.00 (3H, s, H-19), 0.96 (3H, s, H-18), 0.93
(3H, d, J = 6.8 Hz, H-28), 0.85 (3H, d, J = 8.0 Hz, H-27),
0.83 (3H, d, J = 7.1 Hz, H-26). Compound 8 was identified as
ergosta-4, 6, 8 (14), 22-tetraen-3-one by comparison of the
physical and spectral data with the literature [12].
Compound 9 C29H50O, white needle, mp 139–140 °C.
1H NMR (600 MHz, CDCl3) δ: 5.35 (1H, d, J = 4.9 Hz, H-6),
3.52 (1H, m, H-3), 1.01 (3H, s, H-19), 0.92 (3H, d, J = 6.6 Hz,
H-21), 0.85 (3H, t, J = 7.2 Hz, H-29), 0.83 (3H, d, J = 6.6 Hz,
H-27), 0.81(3H, d, J = 6.1 Hz, H-26), 0.68 (3H, s, H-18).
Compound 9 was identified as β-sitosterol by comparison of
the physical and spectral data with the literature [13].
Compound 10 C29H48O, white needle, mp 154–156 °C.
1H NMR (600 MHz, CDCl3) δ: 5.35 (1H, m, H-6), 5.16 (1H,
dd, J = 15.4, 8.3 Hz, H-22), 5.02 (1H, dd, J = 15.4, 8.8 Hz,
H-23), 3.52 (1H, m, H-3), 1.02 (3H, d, J = 6.6 Hz, H-21),
1.01 (3H, s, H-19), 0.85 (3H, d, J = 6.6 Hz, H-26), 0.80 (3H, t,
J = 7.7 Hz, H-29), 0.80 (3H, d, J = 6.6 Hz, H-27), 0.70 (3H, s,
H-18). Compound 10 was identified as stigmasterol by com-
parison of the physical and spectral data with the literature [14].
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半红树植物黄槿中的三萜和甾醇成分
王忠昭 1, 李 俊 1, 唐旭利 2, 李国强 1*
1中国海洋大学医药学院海洋药物教育部重点实验室, 青岛 266003;
2中国海洋大学化学化工学院, 青岛 266100
【摘 要】 目的：研究半红树植物黄槿(Hibiscus tiliaceus L.)的化学成分。方法：分离纯化采用硅胶色谱、Sephadex LH-20
凝胶色谱、高效液相色谱等方法。结构鉴定通过理化常数和波谱数据与文献对照确定。结果：从黄槿中共分离鉴定了 10 个化合
物, 分别为：木栓酮(1)、粉蕊黄杨二醇(2)、β-粘霉烯醇(3)、羽扇豆醇(4)、日耳曼醇(5)、豆甾-4-烯-3-酮(6)、豆甾-4, 22-二烯-3-
酮(7)、麦角甾-4, 6, 8 (14), 22-四烯-3-酮(8)、β-谷甾醇(9)和豆甾醇(10)。结论：化合物 3~5 和 8 为首次从该植物中分离得到。
【关键词】 黄槿; 三萜; 甾醇

【基金项目】 国家海洋局 908 专项项目(No. 908-01-ST12)