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Chinese Journal of Natural Medicines 2011, 9(3): 01900192

Chinese
Journal of
Natural
Medicines

doi: 10.3724/SP.J.1009.2011.00190

Triterpenes and Steroids from Semi-mangrove


Plant Hibiscus tiliaceus
WANG Zhong-Zhao1, LI Jun1, TANG Xv-Li2, LI Guo-Qiang1*
1

School of Medicine and Pharmacy, Key Laboratory of Marine Drugs, Ministry of Education, Ocean University of China, Qingdao
266003, China;
2
College 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 comparison 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), -sitosterol (9), and stigmasterol (10). CONCLUSION: Compounds 35 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

Introduction

The semi-mangrove plant Hibiscus tiliaceus belonging


to the genus Hibiscus (family Malvaceae) is widely distributed 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 revealed 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), 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),
-sitosterol (9) and stigmasterol (10) (Fig.1). Compounds 35
and 8 were obtained from this plant for the first time.

2 Apparatus and Reagents


Melting points (mp) were determined on an X4 micro[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.
Copyright 2011, China Pharmaceutical University.
Published by Elsevier B.V. All rights reserved.
2011 5

melting apparatus and uncorrected. ESI-MS spectra were


recorded on a Waters Q-TOF LC-MS-MS mass spectrometer.
1
H and 13C NMR spectra were recorded on a JEOL
JNMECP600 spectrometer with the residual CHCl3 (H 7.26,
C 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 m, 10 mm
(i.d.) 25 cm] column), commercial Sigel (Qingdao Marine
Chemical Group Co., 200-300 and 400600 mesh) and
Sephadex LH-20 (Pharmacia Biotech AB, Uppsala, Sweden)
were employed for separation and purifification.

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 University of China, Qingdao, China.

Extraction and Isolation

The air-dried and powdered stems and barks of H. tiliaceus (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 petroleum ether and ethyl acetate fraction based on TLC results.
Chin J Nat Med May 2011

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WANG Zhong-Zhao, et al. /Chinese Journal of Natural Medicines 2011, 9(3): 191193

Fig. 1 Structures of compounds 1-10

The petroleum ether and ethyl acetate fraction was subjected


to column chromatography on silica gel eluted with petroleum ether-acetone gradient (10 : 0-1 : 10) to give eight subfractions Frs.18. Frs.13 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).

Identification

Compound 1 C30H50O, white needle, mp 261263 C.


H NMR (600 MHz, CDCl3) : 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) : 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 literature [5].
Compound 2 C30H52O2, white needle, mp 290291 C.
ESI-MS m/z 408 [M 2H2O]+. 1H NMR (600 MHz, CDCl3)
: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 218219 C.
1
H NMR (600 MHz, CDCl3) : 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,
1

192 Chin J Nat Med May 2011 Vol. 9 No. 3

H-25). 13C NMR (150 MHz, CDCl3) : 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 214.0215.0
C. ESI-MS m/z 408 [M H2O]+. 1H NMR (600 MHz,
CDCl3) : 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 175178 C.
ESI-MS m/z 408 [M H20]+. 1H NMR (600 MHz, CDCl3) :
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) : 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 comparison of the physical and spectral data with the literature [9].
Compound 6 C29H48O, white needle, mp 155.0157.0
C. ESI-MS m/z 412 [M]+. 1H NMR (600 MHz, CDCl3) :
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) : 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),
2011 5 9 3

WANG Zhong-Zhao, et al. /Chinese Journal of Natural Medicines 2011, 9(3): 191193

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 115116 C.
ESI-MS m/z 410 [M]+. 1H NMR (600 MHz, CDCl3) : 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-3one by comparison of the physical and spectral data with the
literature [11].
Compound 8 C28H40O, yellow needle, mp 110113
C. ESI-MS m/z 392 [M]+. 1H NMR (600 MHz, CDCl3) :
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-2223), 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 139140 C.
1
H NMR (600 MHz, CDCl3) : 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 -sitosterol by comparison of
the physical and spectral data with the literature [13].
Compound 10 C29H48O, white needle, mp 154156 C.
1
H NMR (600 MHz, CDCl3) : 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 comparison of the physical and spectral data with the literature [14].

References
[1]

[2]

[3]

[4]
[5]
[6]

[7]

[8]

[9]

[10]

[11]

[12]

[13]
[14]

Lin P, Lin YM, Yang ZW, et al. Research status, civil utilization and prospect on marine mangrove drug in China-a review[J]. Chin J Mar Drugs, 2005, 29 (9): 76-79.
Li LY, Huang XS, Sattler I, et al. Structure elucidation of a
new friedelane triterpene from the mangrove plant Hibiscus
tiliaceus [J]. Magn Reson Chem, 2006, 44 (6): 624-628.
Chen JJ, Huang SY, Duh CY, et al. A new cytotoxic amide
from the stem wood of Hibiscus tiliaceus [J]. Planta Med, 2006,
72 (10): 935-938.
Feng C, Li XM, Ji NY, et al. Triterpenoids from the mangrove
plant Hibiscus tiliaceus [J]. Helv Chim Acta. 2008, 91 (5): 850-855.
Liu J, Xie T, Wei XL, et al. Chemical studies on Rabdosia
rubenscens [J]. Chin J Nat Med, 2004, 2 (5): 276-279.
Cristina M, Fatima J, Regina T, et al. Synthetic secofriedelane
and friedelane derivatives as inhibitors of human lymphocyte
proliferation and growth of human cancer cell lines in vitro [J].
J Nat Prod, 2001, 64 (10): 1273-1277
Li C, Yue DK, Fu PB, et al . Chemical constituents from roots
of Ardisia punctata [J]. China J Chin Mater Med, 2006, 31 (7):
562-565.
Li LY, Li X, Shi C, et al. Studies on chemical constituents of
semi-mangrove plant Pongamia pinnata [J]. Chin J Mar Drugs,
2008, 27 (1): 18-24.
Zhou SY, Li RT, Li HM. Study on chemical constituents of
Kadsura interior [J]. J Kunming Univ Sci Tech (Sci Technol),
2008, 33 (5): 81-85
Liu A, Tian JK, Zou ZM, et al. Studies on chemical constituents of Uvaria tonkinensis var. subglabra [J]. Chin Tradit Herb
Drugs, 2002, 33 (3): 205-206.
Zhang LL, Wang ZC, Chen JD, et al. Studies on chemical
constituents in ethanolic extract from Acanthus ilicifolius as a
pharmaceutic mangrove [J]. Chin J Mar Drugs, 2007, 12 (26): 5-9.
Cui Y, Zhang XM, Chen JJ, et al. Chemical constituents from
root of Actinidia chinensis [J]. China J Chin Mater Med, 2007,
32 (6): 1663-1665.
Zheng Z, Pei YH. Chemical constituents from Sonneratia
ovata [J]. J Shenyang Pharm Univ, 2008, 25 (1): 35-37.
Sun HY, Long LJ, Wu J. Chemical constituents of mangrove
plant Barringtonia racemosa [J]. J Chin Med Mater, 2006, 29
(7): 671-672.

1,

1, 2, 1*

, 266003;

, 266100

(Hibiscus tiliaceus L.)Sephadex LH-20


10
, (1)(2)-(3)(4)(5)-4--3-(6)-4, 22--3(7)-4, 6, 8 (14), 22--3-(8)-(9)(10) 3~5 8
; ;

908 (No. 908-01-ST12)


2011 5

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