全 文 ：Received 24 Nov. 2003 Accepted 27 Feb. 2004
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Acta Botanica Sinica
植 物 学 报 2004, 46 (5): 621-624
Curculigoside C, a New Phenolic Glucoside from Rhizomes
of Curculigo orchioides
FU Da-Xu, LEI Guang-Qing, CHENG Xiao-Wei, CHEN Jia-Kuan, ZHOU Tong-Shui*
(Research Center of Natural Products, School of Life Sciences, Fudan University, Shanghai 200433, China)
Abstract: A new phenolic glucoside, curculigoside C (3 ), was isolated from the rhizomes of Curculigo
orchioides Gaertn., together with three known compounds, curculigoside (1 ), curculigoside B (2 ), and 2,6-
dimethoxyl benzoic acid (4 ). The structure of the new compound (3 ) was elucidated as 5-hydroxy-2-O-b-
D-glucopyranosyl benzyl-3-hydroxy-2, 6-dimethoxybenzoate by using spectroscopic methods.
Key words: Curculigo orchioides ; Hypoxidaceae; rhizomes; phenolic glucoside
Curculigo orchioides is a tiny herbal plant widely dis-
tributed in China, India, Malaya, Japan and Australia. Its
rhizomes having the properties of warming kidney, invigo-
rating yang, expelling cold and eliminating dampness are
used as traditional Chinese medicine “Xianmao” to cure
impotence, enuresis, cold sperm, cold pain of back and knee,
and numbness of the limb (Liu, 2001). In India, the tuber-
ous roots of this plant are considered to be tonic, alterative,
demulcent, diuretic, and restorative, and are used as a poul-
tice for itch and skin diseases (Shri et al., 1989). Previous
phytochemical investigations on the rhizomes of this spe-
cies revealed the presence of curculigoside (Li et al., 2003),
curculigoside B (Xu and Xu, 1992a), orcinol glycosides (Li
et al., 2003), 2,6-dimethoxyl benzoic acid (Chen et al., 1999),
curculigines A-C (Chen et al., 1999), curculigol (Triguna et
al., 1990), curculigosaponins A-M (Xu and Xu, 1992b), 2,3,
4,7-tetramethoxyxan thone, 1,3,7-t rimethy lxan th ine,
daucosterol (Li et al., 2003), and aliphatic long-chain ke-
tones (Triguna et al., 1984). In the current study, a new
phenolic glucoside, curculigoside C (3), together with three
known compounds, curculigoside (1), curculigoside B (2 )
and 2,6-dimethoxyl benzoic acid (4), was isolated. The struc-
ture of curculigoside C was elucidated on the basis of spec-
tral data.
1 Results and Discussion
Compound 3 , co lo rles s need les , had a molecu lar
formula of C22H26O12 as established by its ESI-MS and
NMR data. The IR spectrum resembled those of compounds
1 and 2, showing absorptions for hydroxyl groups, an es-
ter carbonyl group, and aromatic rings. The 1H-NMR spec-
trum s howed proton signals for two phenolic hydroxyl
groups at d 9.19 and 9.06 (each 1H, s, D2O-exchangeable),
an oxygenated methylene group at d 5.33 (2H, s), two
methoxyl groups at d 3.71 and 3.70 (each 3H, s), and an
anomeric proton of the glucose moiety at d 4.63 (1H, d, J =
6.6 Hz). The configuration at C-1¢¢ of the sugar moiety was
determined to be b-oriented as judged by the coupling con-
stant of H-1¢¢. Moreover, three aromatic proton signals at
d 6.99 (1H, d, J = 8.8 Hz), 6.82 (1H, d, J = 2.3 Hz), and 6.65 (1H,
dd, J = 2.3, 8.8 Hz) assignable to the A ring and two aromatic
doublets at d 6.88 (1H, d, J = 8.9 Hz) and 6.67 (1H, d, J = 8.9
Hz) attributable to the B ring were also observed. The 13C-
NMR spectrum resolved 22 carbon signals, corresponding
to a benzyl benzoate skeleton bearing two methoxyl groups
and the b-glucose moiety. By comparing the NMR spectral
data of compounds 1, 2 and 3 (Tables 1 and 2), it could be
inferred that compounds 1-3 had the s ame substitu tion
pattern in the A ring, and compound 3 attached one more
hydroxyl group at C-3¢ in the B ring than compound 1 (Fig.
1).
On the basis of HMQC, HMBC and NOESY s pect ral
analys is, the s t ructu re o f compound 3 was fu rther
determined, and all the p roton and carbon signals were
fully assigned. In the HMBC spectrum, the proton at d 4.63
(1H, d, J = 6.6 Hz, H-1¢¢) coupled with C-2 (d 147.6), and the
hydroxyl group at d 9.06 correlated with C-4 (d 114.9), C-5 (d
152.3), and C-6 (d 114.6), suggest ing that the b-g lucose
moiety and the hydroxyl group were located at C-2 and C-5,
respectively (Fig.2). The hydroxyl and methoxyl groups in
the B ring were also assigned by the HMBC correlations.
The linkage of two aromatic parts was verified by the HMBC
cross peaks of H2-7 at d 5.33 (2H, s) with C-2, C-6, and C-7¢
(d 165.3). The structure of compound 3 was also confirmed
by the NOESY experiment (Fig.3). Compound 3 was there-
fo re elucidated as 5-hydroxy-2-O-b-D-g lucopyranos yl

FU Da-Xu et al.: Curculigoside C, a New Phenolic Glucoside from Rhizomes of Curculigo orchioides 623
gel column developed with CH3Cl-MeOH (10:1, 9:1, 8:1, 7:1,
6:1, 5:1 and 4:1) to give seven fractions (G1-G7 ). Each
fraction was purified repeatedly by column chromatogra-
phy over Sephadex LH-20 eluted with aqueous MeOH to
afford compounds 1 (1.8 g), 2 (40 mg), 3 (20 mg) and 4 (800
mg).
2.4 Identification
Compound 1 Colorless needles (MeOH), C22H26O11 ,
mp 159-161 °C. IR (KBr) nmax cm-1: 3 370 (OH), 2 922, 1 724
(ester), 1 598 (aromatic ring). ESI-MS m/z: 484 [M+NH4]+,
489 [M+Na]+. See Tables 1 and 2 for 1 H-NMR and 13C-
NMR data.
Compound 2 Colorless needles (MeOH), C21H24O11 ,
mp 210-211 °C. IR (KBr) nmax cm-1: 3 375 (OH), 2 920, 1 724
(ester), 1 598 (aromatic ring). ESI-MS m/z: 470 [M+NH4]+,
Table 2 13C-NM R ass ignment s for compounds 1-3 (in
DM SO-d6)
Position 1 2 3
1 127.7 127.4 126.5
2 147.9* 148.0* 147.6
3 117.7 117.8 117.2
4 115.2 115.2 114.9
5 152.8* 152.7* 152.3
6 114.9 114.9 114.6
7 61.8 61.3 61.5
1 104.8 102.7 118.7
2 157.1 156.1 144.6
3 113..2 111.4 143.8
4 131.7 131.7 117.6
5 113.2 109.0 107.3
6 157.1 157.9 148.5
7 165.9 166.6 165.3
2¢ (OCH3) 56.3 60.5
6¢ (OCH3) 56.3 56.2 56.1
1 103.1 103.1 102.5
2 73.8 73.8 73.3
3 77.5 77.4 77.0
4 70.3 70.3 69.8
5 77.0 76.9 76.5
6 61.4 61.7 60.8
*, the assignments for the C-2 and C-5 of compounds 1 and 2 were
reversed in t he literature (Xu and Xu, 1992a; Li et al., 2003 ), and
were revised in this paper.
475 [M+Na]+. See Tab les 1 and 2 for 1H-NMR and 13C-
NMR data.
Compound 3 Colorless needles (MeOH), C22H26O12 ,
mp 107-108 °C. IR (KBr) nmax cm-1: 3 380 (OH), 2 923, 1 724
(ester), 1 598 (aromatic ring). ESI-MS m/z: 500 [M+NH4]+,
505 [M+Na]+. See Tab les 1 and 2 for 1H-NMR and 13C-
NMR data.
Compound 4 Colorless needles (MeOH), C9 H10O4 .
ESI-MS m/z: 183 [M+H]+. 1H-NMR d (in DMSO-d6): 3.75
(6H, s, 2×OCH3), 6.68 (2H, d, J = 8.4 Hz, H-3, 5), 7.30 (1H,
t, J = 8.4 Hz, H-4), 12.88 (1H, br s, COOH). 13C-NMR d (in
DMSO-d6): 116.9 (C-1), 156.9 (C-2, 6), 104.9 (C-3, 5), 131.2
(C-4), 168.7 (COOH), 56.5 (OCH3).
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(Managing editor: WANG Wei)