全 文 ：Received 15 Jul. 2003 Accepted 17 Feb. 2004
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Acta Botanica Sinica
植 物 学 报 2004, 46 (5): 618-620
Chemical Constituents of Smilax perfoliata
CHENG Yu-Biao, ZHANG Dong-Ming*, YU Shi-Shan
(Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, China)
Abstract : One new compound named smilglaside F (1 ) and five known ones (2-6 ) were isolated from
the EtOAc portion of the 95% ethanolic extract of Smilax perfoliata Lour. by silica gel and ODS column
chromatography. On the basis of chemical and spectral methods, they were identified as 1, 6-O-diferuloyl-
(3-O-p-coumaroyl)-b-D-fructofuranosyl-(2→1)-2-O-acetyl-a-D-glucopyranoside (1 ), rutin (2 ), narcissin (3 ),
cassiamin A (4 ), cassiamin B (5 ) and 1, 2, 3-trimethoxy-5-hydroxyphenol-1-O-b-D-glucopyranoside (6 ) ,
respectivety. Compounds 1 , 3-6 were obtained from the genus Smilax for the first time.
Key words: Liliaceae; Smilax perfoliata ; smilglaside F
Smilax perfoliata is distributed in provinces of Taiwan,
Guangdong, Guangxi, Yunnan and Hainan. Its rhizoma plays
a role in strengthening functions of spleen, stomach, muscle
and bone, and also used to cure rheumatism and lumbago
(China Herb Company, 1994). From the EtOAc port ion of
the 95% ethanolic extracts of the rhizoma of this plant, six
compounds, smilglaside F (1), rutin (2) (Ernest and Hugo,
1977), narcissin (3) (Markham et al., 1978), cassiamin A (4)
(Koyama et al., 2001), cassiamin B (5) (Koyama et al., 2001),
and 1,2,3-t rimethoxy-5-hydroxyphenol-1-O-b-D -
glucopyranoside (6) (Shimomura et al., 1988; Saijo et al.,
1989) were isolated. Among them, 1 was determined to be a
new compound, namely smilglaside F. Their structures were
elucidated by spectroscopic methods including HRFAB-
MS and 2D-NMR and chemical experiments.
1 Results and Discussion
Compound 1 exhibited a [M+Na]+ peak at m/z 905 and a
[M-(glu+Ac)]+ peak at m/z 661 in its positive FAB-MS
(Fig.1). The formula of 1 was established as C43H46O20 by
the positive HR-FAB-MS ([M+Na]+ found m/z 905.245 1,
calcd. for C43H46O20, 905.248 0). The UV spectrum showed
absorption bands ascribable to cinnamoyl residues at 204,
323 nm. The IR spectrum showed the presence of hydroxyl
group (3 408 cm-1) and carbonyl (1 711 cm-1). Analysis of
the 1H-NMR spectrum of 1, combined with the 1H-1 H
COSY, indicated the presence of two (E)-feruloyls, one (E)-
p-coumaroyl and one sucrose. The 13C-NMR spectrum con-
firmed the above mentioned deductions, suggesting that 1
was likely a phenylpropanoid glycoside. On acid hydrolysis,
it afforded glucose and fructose, while on alkaline hydroly-
sis it gave (E)-p -coumaric acid and (E)-ferulic acid. Their
connect locat ions were determined by means o f the
heteronuclear multiple bond coherence (HMBC). In HMBC
spectrum of 1 (Fig.2), long-range correlations (3JHCOC) were
obs erved between the carbonyl carbons signals at d
167.36, 166.59 (C-g of each feruloyl) and the proton signals
at d 4.14, 4.51 due to the H-1 and H-6 of fructose,
res pect ively , between the carbonyl carbon signal at
d 166.55 (C-g of p-coumaroyl) and the proton signal at d 5.59
due to the H-3 of fructose, between the carbon signal at d
171.05 (carbonyl carbon of acetyl) and the proton signal at
d 4.62 due to the H-2 of glucose. Based on the above data,
the structure of 1 was elucidated as 1,6-O-diferuloyl-(3-O-
p-coumaroyl)-b-D-fructofuranosyl-(2→1)-2-O-acetyl-a-D-
glucopyranoside, namely smilglaside F.
2 Experimental
2.1 General experimental procedures
Melting point was meas ured with XT4-100X, and the
temperature was uncorrected. 1H-NMR, 13C-NMR, 1H-1H
COSY and HMBC were recorded at INOVA-500 spectrom-
eter using TMS as internal standard. FAB-MS and HRFAB-
MS were measured by Zabspec Tofspec Platform-ESI mass
spectrometer.
2.2 Plant material
Smilax perfo l ia ta Lour. was co llected from
Xishuangbanna of Yunnan Province, China，and identi-
fied by CUI Jing-Yun of Kunming Institute of Botany,
The Chinese Academy of Sciences.
2.3 Extraction and isolation
Rhizoma (13 kg) of S. perfoliata was powdered，and
extracted with 95% EtOH for 3× 2 h. The ext ract was
evaporated in vacuum. The residue was part itioned in

Acta Botanica Sinica 植物学报 Vol.46 No.5 2004620
Compound 2 Ligh t yellow powder. Formula:
C27H30O16. FAB-MS m/z: 611 [M+H]+. 13C-NMR (125 MHz,
CD3OD) δ:158.56 (C-2), 135.63(C-3), 179.44 (C-4), 163.03
(C-5), 99.98 (C-6), 166.15 (C-7), 94.89 (C-8), 159.36 (C-9),
105.63 (C-10), 123.14 (C-1), 116.07 (C-2), 145.87 (C-3),
149.84 (C-4), 117.69 (C-5), 123.6 (C-6), Glu:104.71 (C-1),
75.74 (C-2), 78.20 (C-3), 72.11 (C-4), 77.25 (C-5), 68.55
(C-6). Rham: 102.44 (C-1), 72.26 (C-2), 71.41 (C-3), 73.94
(C-4), 69.72 (C-5), 17.87 (C-6).
Compound 3 Light yellow powder. Formula:
C28H32O16 . FAB-MS m/z: 625 [M+H]+. 13 C-NMR (125
MHz, CD3OD)δ：158.43 (C-2), 135.44 (C-3), 179.28 (C-4),
162.95 (C-5),99.94 (C-6), 166.00 (C-7), 94.91 (C-8), 158.81 (C-
9), 105.65 (C-10), 122.93 (C-1), 114.49 (C-2), 150.80 (C-3),
148.25 (C-4), 116.06 (C-5), 123.94 (C-6), 56.72 (3-OCH3).
Glu : 104.43 (C-1), 75.89 (C-2), 78.12 (C-3), 72.04 (C-4),
77.31 (C-5), 68.48 (C-6). Rham: 102.50 (C-1), 72.23 (C-2),
71.57 (C-3), 73.81 (C-4), 69.76 (C-5), 17.88 (C-6).
Compound 4 Orange p late crys tal. Mp>300 oC.
Formula: C30H18O9. FAB-MS: 523 [M+H]+. [a] D20 -193° (c
0.145, pyridine). 1H-NMR (500 MHz, DMSO)δ：2.15 (6H,
s, 3-CH3, 3-CH3), 6.61 (1H, d, J=2.4 Hz, H-7), 7.16 (1H, d,
J=2.4 Hz, H-5), 7.38 (1H, d, J=8.1 Hz, H-7), 7.72-7.84 (4H, m,
H-4, H-4, H-5, H-6); 11.43 (1H, 6-OH), 11.86 (1H, 8-OH),
12.01 (1H, 8-OH), 12.19 (1H, 1-OH), 12.37 (1H, 1-OH). 13C-
NMR (125 MHz, DMSO) δ:158.97 (C-1), 130.16 (C-2),
147.67 (C-3), 120.86 (C-4), 109.05 (C-5), 146.53 (C-6), 107.99
(C-7), 165.79 (C-8), 189.81 (C-9), 181.33 (C-10), 113.65 (C-1a),
132.48 (C-4a), 108.99 (C-5a), 135.19 (C-8a), 158.86 (C-1),
130.16 (C-2), 146.74 (C-3), 120.86 (C-4), 137.47 (C-5), 119.41
(C-6), 124.48 (C-7), 161.33 (C-8), 191.87 (C-9), 181.33 (C-
10), 113.95 (C-1a), 132.40 (C-4a), 133.34 (C-5a), 115.94 (C-
8a), 20.01 (3-CH3, 3-CH3).
Compound 5 Orange plate crystal. Mp>300 oC. Formula:
C30H18O10. [a] D20 -18.5° (c 0.054, pyridine). FAB-MS: 539
[M+H]+ . 1H-NMR (500 MHz，DMSO) δ: 2.24 (6H, s, 3-
CH3, 3-CH3), 6.61 (2H, d, J=2.4 Hz, H-7, H-7)，7.16 (2H, d,
J =2.4 Hz, H-5, H-5), 7.72 (2H, s, H-4, H-4). 13C-NMR (125
MHz, DMSO) δ：158.56 (C-1, C-1)，130.16 (C-2, C-2),
149.52 (C-3, C-3), 120.76 (C-4, C-4), 108.99 (C-5, C-5), 146.64
(C-6, C-6), 107.99 (C-7, C-7), 165.83 (C-8, C-8), 189.70 (C-9,
C-9), 181.34 (C-10, C-10), 113.65 (C-1a, C-1a), 132.38 (C-4a,
C-4a), 135.21 (C-8a, C-8a), 108.99 (C-5a, C-5a), 19.96 (3-
CH3, 3-CH3).
Compound 6 White plate crystal. Formula: C15H22O9.
Mp 212-214 oC. [a] D20 –50.8° (c 0.295, MeOH). FAB-MS
m/z: 347 [M+H]+. 13 C-NMR (125 MHz, DMSO)δ: 153.95
(C-2), 153.08 (C-1, C-3), 132.43 (C-5), 94.38 (C-4, C-6), 101.00
(C-1), 77.24 (C-5), 76.72 (C-3), 73.16 (C-2), 70.03 (C-4),
60.82 (C-6), 60.07 (2-OCH3), 55.72 (1-OCH3, 3-OCH3).
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(Managing editor: WANG Wei)