全 文 ：晚香玉球茎中的一个新胆甾烷类配糖体
金建明 , 刘锡葵 , 杨崇仁
(中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室 , 云南 昆明　650204)
摘要:从晚香玉 (Polianthes tuberosa L.)球茎中分离到 3 个胆甾烷类配糖体。经波谱分析鉴
定 , 其中1 个为新的胆甾烷类配糖体 , 即 (22S)-胆甾烷-5-烯-1β , 3β , 16β , 22 , 25-五醇 1-O-β-
D-葡萄吡喃糖基-16-O-β-D-芹菜呋喃糖苷。
关键词:晚香玉;胆甾烷类配糖体;晚香玉甙A
中图分类号:Q 946　　文献标识码:A　　文章编号:0253-2700(2003)01-0107-04
A New Cholestane Glycoside from the Tubers of
Polianthes tuberosa
＊
JIN Jian-Ming , LIU Xi-Kui , YANG Chong-Ren＊＊
(State ! Key Laboratory of Phytochemistry and Plant Resources in West China , Kunming Institute of Botany ,
Chinese Academy of Sciences , Kunming 650204 , China)
Abstract:A new cholestane glycoside , (22S)-cholest-5-en-1β , 3β , 16β , 22 , 25-pentaol 1-O-β-D-
glucopyranosy l-16-O-β-D-apiofuranoside , together with two known cholestane gly cosides were isolated from
the tubers of Polianthes tuberosa .Their structures were elucidated on the basis of spectroscopic data.
Key words:Polianthes tuberosa;Cholestane glycosides;Tuberoside A
The genus Polianthes , comprising about 12 species , is native to Mexico.Polianthes tuberosa
L., a well-known ornamental plant , is widely cultivated in the south of China.Three steroidal sa-
pogenins were isolated from the tubers of P.tuberosa (Zhou et al , 1965).But there is no report about
steroidal glycosides in the tubers of P.tuberosa.During the investigation of steroidal constituents of
P.tuberosa , three cholestane glycosides including a new cholestane glycoside were isolated from the
tubers of P.tuberosa.Two known cholestane glycosides 1 and 2 were identified as(22S)-cholest-5-
en-1β , 3β , 16β , 22-tetraol 1-O-β-D-glucopyranosyl-16-O-β-D-apiofuranoside (1)(Mimaki et al ,
2000)and(22S)-cholest-5-en-1β , 3β , 16β , 22-tetraol 3 , 16-di-O-β-D-glucopyranoside (2)(Mi-
maki et al , 1995), respectively.
云 南 植 物 研 究　 2003 , 25 (1):107～ 110
Acta Botanica Yunnanica　　　　　　　　　　　　　　　　　　　　　　　　　　　

Author for correspondence
Received date:2002-06-19 , Accepted date:2002-07-16
作者简介:金建明 (1973-)男 , 浙江人 , 博士 , 主要从事植物化学的研究。
Foundation item:The project was f inancially supported by the National Natural Science Foundation of China (NSFC)
(39969005)
Results and Discussion
Compound 3 was obtained as an amorphous solid , [α] 20.1D -24.51°(c 0.1489 , pyridine).Its
molecular formula was deduced as C38H64O14 on the basis of
13C DEPT NMR and the negative ion FAB-
MS , which showed a quasi-molecular peak at m/z 743 [M-H] -.The negative ion FAB-MS of 3 ex-
hibited two fragment ion peaks at m/z 611 [M-H-132] - and 581 [M-H-162] - , except the molecular
ion peak at m/z 743 [M-H] -.Its 1H spectrum showed signals for three tertiary methyl groups atδH
0.96 , 1.27 and 1.41 , one secondary methyl groups atδH 1.02(3H , d , J=7.6Hz).In addition ,
two anomeric proton signals were observed atδH 4.97(1H , d , J=7.0 Hz)and 5.46(1H , br s).
Comparing the 13C NMR data of 3with those of 1(table 1), the signals of the two compounds in-
cluding the signals of sugar moieties were identical to each other , except for those of C-23 to C-27 ,
indicating that the β-D-glucopyranosyl unit should be attached to C-1 position of the aglycone and the
β-D-apiofuranosyl unit should be attached to C-16 position of the aglycone.DEPT spectrum of 3 indi-
cated that it afforded one more quaternary carbon signal atδC 70.1 , and lost one more carbon than
those of 1.By comparison of the chemical shifts of C-26 and C-27(δC 29.9 and 30.2)of 3 with
those of 1(δC 23.1 and 23.1), the downfield shifts(+6.8 and 7.1 ppm)of C-26 and C-27 sug-
gested the carbon signal atδC 70.1 should be assigned to C-25 of the aglycone.These results indicat-
ed that there was a hydroxyl group was attached to C-25 of 3.
Table 1　13C NMR data of compounds 1-3
Aglycone 　1 　2 　3 Sugar 　　　1 　 2 　 3
1 83.0(d) 83.0(d) 82.9(d) Glc1 1 　　101.3(d) 101.4(d) 101.4(d)
2 37.6(t) 37.6(t) 37.6(t) 2 　　75.5(d) 75.6(d) 75.5(d)
3 68.2(d) 68.2(d) 68.1(d) 3 　　78.7(d) 78.8(d) 78.7(d)
4 43.8(t) 43.8(t) 43.8(t) 4 　　72.5(d) 72.5(d) 72.5(d)
5 139.7(s) 139.6(s) 139.6(s) 5 　　78.2(d) 78.3(d) 78.4(d)
6 125.0(d) 125.1(d) 124.8(d) 6 　　63.7(t) 63.7(t) 63.7(t)
7 31.9(t) 32.0(t) 31.8(t) Api16 1 　　112.7(d) 112.9(d)
8 33.3(d) 33.3(d) 33.2(d) 2 　　78.2(d) 78.1(d)
9 50.4(d) 50.4(d) 50.3(d) 3 　　80.5(s) 80.2(s)
10 42.9(s) 43.0(s) 42.8(s) 4 　　66.2(t) 65.9(t)
11 24.0(t) 24.0(t) 23.9(t) 5 　　75.2(t) 75.1(t)
12 40.6(t) 40.7(t) 40.6(t) Glc16 1 107.1(d)
13 42.1(s) 42.3(s) 42.0(s) 2 75.8(d)
14 55.2(d) 55.3(d) 55.2(d) 3 78.9(d)
15 36.6(t) 37.4(t) 36.6(t) 4 71.8(d)
16 81.3(d) 82.9(d) 81.5(d) 5 78.3(d)
17 58.0(d) 58.3(d) 58.1(d) 6 63.0(t)
18 13.7(q) 14.4(q) 13.6(q)
19 14.9(q) 14.9(q) 14.8(q)
20 35.7(d) 36.1(d) 36.0(d)
21 12.0(q) 12.7(q) 12.1(q)
22 72.7(d) 72.5(d) 73.2(d)
23 34.5(t) 34.0(t) 35.8(t)
24 36.6(t) 36.9(t) 41.9(t)
25 28.9(d) 29.1(d) 70.1(s)
26 23.1(q) 23.2(q) 29.9(q)
27 23.1(q) 23.3(q) 30.2(q)
108　　　　　　 　　　　　　　　　云　南　植　物　研　究　　　　　 　　　　　　　　　25卷
　　In HMBC spectrum , methyl proton signal atδH 1.41(3H , s , H-26 and H-27)was correlated
with carbon signals atδC 29.9 (CH3 , C-26), 30.2 (CH3 , C-27), 41.9 (CH2 , C-24)and
70.1(C , C -25).In addition , Three-bond 1H-13C long-range correlations were observed that the
anomeric proton signals were correlated with the carbon signals atδH 4.97(H-Glc-1)andδC 82.9(C
-1 of aglycone), δH 5.46(H-Api-1)andδC 81.5(C-16 of aglycone)(Fig.1).Thus , the chem-
ical structure of 3 was determined as (22S)-cholest-5-en-1β , 3β , 16β , 22 , 25-pentaol 1-O-β-D-
glucopyranosyl-16-O-β-D-apiofuranoside , which was named as tuberoside A.
Fig.1　The key 1H-13C long-range correlations of 3 in the HMBC spectrum
Experimental Section
General　Optical rotations were measured with HORIBA SEPA-300 high-sensitive polarimeter.IR(KBr)spectra
were measured on Bio-Rad FTS-135 spectrophotometer.NMR spectra were recorded on a Bruker DRX-500 instrument at
25℃, using TMS as an internal standard.The negative ion and high-resolution FAB mass spectrawere recorded on a VG
AutoSpec-3000 mass spectrometer using glycerol as matrix.Precoated silica gel plates(Qingdao Haiyang Chemical Co.)
were used for TLC.Detection was done by spraying the plates with 5 % anisaldehyde-sulphric acid , followed by heating.
Plant material　The fresh tubers of P.tuberosa L.cv Double were collected from Kunming Qianhui Seed and
Seedling Limited Company at June 2001.
Extract and isolation　The fresh tubers of P.tuberosa (24 kg)were extracted with hot 80% ethanol three times
for 4 hours , the combined extract was concentrated under reduced pressure.Then concentrated extract was partitioned
between n-butanol and water.Half the n-butanol layer (450 g)was repeatedly chromatographed on silica gel with
CHCl3:MeOH:H2O and RP-8 with MeOH:H2O to give 1(345 mg), 2(2.2 g)and 3(50 mg).
Compound 1　A white amorphous powder:[ α] 17.1D -38.76°(c 0.0387 , pyridine).IRνKBrmax cm-1:3408(OH),
2944(CH), 1651 , 1464 , 1382 , 1159 , 1075 , 1015 , 988 , 835.Negative ion FAB-MS m/ z:727 [ M-H] -;1HNMR
(pyridine-d5 , 500MHz):δ3.92(1H , m , H-1), 3.82(1H , m , H-3), 5.55(1H , br d , J=4.7 Hz , H-6),
4.35(1H , m , H-16), 1.03(3H , s , H-18), 1.26(3H , s , H-19), 1.18(3H , d , J=5.7 Hz , H-21), 4.20
(1H , H-22), 0.87(3H×2 , d , J=5.5 Hz , H-26 and H-27), 4.95 (1H , d , J=7.0 Hz , H-Glc-1), 5.48
(1H , br s , H-Api-1);13C NMR data see table 1.
Compound 2　A white amorphous powder: [ α] 16.8D -14.43°(c 0.0537 , pyridine).IRνKBrmax cm-1:3369
(OH), 2951 (CH), 1699 , 1652 , 1382 , 1163 , 1071 , 1020 , 985 , 932 , 892 , 839;Negative ion FAB-MS m/z:757
[ M-H] - , 595 [ M-H-162] -;1H NMR(pyridine-d5 , 500MHz):δ3.93(1H , m , H-1), 3.82(1H , m , H-3),
1091 期　　　　　　　　金建明等:晚香玉球茎中的一个新胆甾烷类配糖体　　　　　　　　　　　
5.48(1H , br d , J=4.9 Hz , H-6), 4.31 (1H , m , H-16), 1.00(3H , s , H-18), 1.23 (3H , s , H-19),
1.15(3H , d , J=6.9 Hz , H-21), 4.20 (1H , H-22), 0.91 (6H , d , J=6.1 Hz , H-26 and H-27), 4.95
(1H , d , J=7.7 Hz , H-Glc1-1);4.73(1H , d , J=7.8 Hz , H-Glc16-1);13C NMR data see table 1.
Compound 3　A white amorphous powder: [ α] 20.1D -24.51°(c 0.1489 , pyridine).IRνKBrmax cm-1:3407
(OH), 2940 , 2881 , 1652 , 1465 , 1379 , 1267 , 1224 , 1158 , 1077 , 1053 , 990 , 955 , 909 , 835;Negative ion FAB-
MS m/ z:743 [ M-H] -, 611 [M-H-132] -, 581 [ M-H-162] -;HR FAB-MS m/ z:743.4177 [ M-H] -(calcd for
C38H63O14 , 743.4218);1H NMR(pyridine-d5 , 500MHz):δ3.94(1H , m , H-1), 3.82(1H , m , H-3), 5.55
(1H , br d , J=4.6 Hz , H-6), 4.34(1H , m , H-16), 0.96 (3H , s , H-18), 1.27(3H , s , H-19), 1.02
(3H , d , J=7.6 Hz , H-21), 1.41(6H , s , H-26 and H-27), 4.97(1H , d , J=7.0Hz , H-Glc-1), 5.46(1H ,
br s , H-Api-1);13C NMR data see table 1.
Acknowledgements:The authors are grateful to the members of the Analytical Group in State Key Laboratory of Phyto-
chemistry and Plant Resources inWest China , Kunming Institute of Botany , for measurements of all spectra.We are also
grateful to Professor Xingcong Li(University of Mississippi)for his help.
References:
Zhou J(周俊), Wu DG (吴大刚), Huang WG (黄伟光), 1965.Steroidal sapogenins from the plants in Yunnan province II.
Steroidal sapogenins from Dioscoreaceae and Agavaceae plants [ J] .Acta Pharm Sinica (药学学报), 1965 , 12 (6):392—
397
Mimaki Y , Kanmoto K , Kuroda M , et al , 1995.Steroidal saponins from the underground part s of Hosta longipes and their inhibitory on
tumor promoter-induced phospholipid metaboli sm [ J] .Chem Pharm Bull , 43 (7):1190—1196
Mimaki Y , Yokosuka A , Sashida Y , 2000.Steroidal glycosides from the aerial parts of Polianthes tuberosa [ J] .J Nat Prod , 63:
1519—1523
110　　　　　　 　　　　　　　　　云　南　植　物　研　究　　　　　 　　　　　　　　　25卷