全 文 ：旋花茄新鲜果实中的三个甾体皂苷
滕希峰1 , 2 , 张颖君1 * , 杨崇仁1
?
(1 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;
2 中国科学院研究生院 , 北京 100049 )
摘要 : 从茄科食用植物旋花茄 ( Solanumspirale) 的新鲜果实中分离得到 3 个化合物 , 其中一个为新成分 ,
经现代波谱学方法鉴定为 26- O-β-D-葡萄吡喃糖基-(25 R)-呋甾-3β, 22ξ, 26-三醇-5-烯-3-O-α-L-鼠李吡喃糖基
- (1-2)- [3- O-(3- O-乙酰基 )-α-L-鼠李吡喃糖基-(1-4) ]-β-D-葡萄吡喃糖苷 ( 1)。2 个已知化合物分别为 26- O-
β-D-葡萄吡喃糖基-(25 R)-呋甾-22ξ-甲氧基-3β, 26-二醇-5-烯-3- O-α-L-鼠李吡喃糖基- (1-2 )-β-D-葡萄吡喃糖苷
(2 ) 和 26- O-β-D-葡萄吡喃糖基- (25 R) -呋甾-3β, 22ξ, 26-三醇-5-烯-3-O-α-L-鼠李吡喃糖基-( 1-2 )-[α-L-鼠李
吡喃糖基-( 1-4) ]-β-D-葡萄吡喃糖苷 ( protodioscin) (3) , 均为首次从该植物中分离得到。
关键词 : 茄科 ; 旋花茄 ; 甾体皂苷
中图分类号 : Q 946 文献标识码 : A 文章编号 : 0253 - 2700 (2008) 02 - 239 - 04
Three Steroidal Glycosides from the Fresh Fruits
of Solanum spirale (Solanaceae)
TENG Xi-Feng
1 , 2
, ZHANG Ying-Jun
1 *
, YANG Chong-Ren
1 *
( 1 State Key Laboratory of Phytochemistry and Plant Resources in West China , Kunming Instituteof Botany,
Chinese Academy of Sciences, Kunming 650204 , China;
2 GraduateUniversity of Chinese Academy of Sciences, Beijing 100049 , China)
Abstract: One new steroidal glycoside, 26-O-β-D-glucopyranosyl - ( 25 R)-furost-3β, 22ξ, 26-triol-5- ene-3-α-L-rham-
nopyranosyl -(1-2) -[3 - O - (3- O-acetyl ) -α-L-rhamnopyranosyl -( 1-4 ) ] -β-D-glucopyranoside ( 1 ) were isolated from the
fresh fruits of the edible plant Solanumspirale Roxb ., together with two known ones, 26- O-β-D-glucopyranosyl - (25 R)-
furost-22ξ-methoxyl-3β, 26-diol-5-ene-3- O-α-L-rhamnopyranosyl - (1-2)-β-D-glucopyranoside ( 2) and26- O-β-D-glucopy-
ranosyl - (25 R )-furost-3β, 22ξ, 26-triol-5-ene-3- O-α-L-rhamnopyranosyl -( 1-2 )- [α-L-rhamnopyranosyl - ( 1-4 ) ]-β-D-
glucopyranoside ( protodioscin) (3) . Their structureswereelucidated by spectroscopic methods, especially 2D NMR . The
known compounds 2-3 were isolated from the title plant for the first time .
Key words: Solanaceae; Solanumspirale; Steriodal glycosides
Solanum spirale Roxb . is distributed mainly in
Yunnan, Guizhou, Guangxi , and Hunan provinces of
China, India, Bengal , Burma, Thailand, and Viet-
nam . In China, the tender leaves and fruits are edible
and have been used as a wild vegetable by Dai people
(Kunming Institute of Botany, Chinese Academy Sci-
ences, 1979) . The leaves are also reported to havethe
effects on killing intestinal worms and the roots are
used as anarcotic and diuretic in India . And theViet-
nameseuse the ripe fruits as vegetable and the leaves
as folk medicine against beriberi and swollen stomach
(Quyen et al. , 1987) .
Three compounds, tomatidenol , 15α-hydroxytoma-
tidenol and yamogenin, were isolated fromthe leaves of
云 南 植 物 研 究 2008 , 30 (2) : 239～242
Acta Botanica Yunnanica

? ?Author for correspondence; E-mail : zhangyj@ mail .kib. ac. cn, cryang@ mail . kib. ac. cn; Tel : + 86 - 871 - 5223235
Received date: 2007 - 08 - 27 , Accepted date: 2007 - 11 - 29
作者简介 : 滕希峰 (1977 - ) 男 , 在读博士研究生 , 主要从事中药资源与化学研究。
Fig . 1 Structures of compounds 1 - 3
S. spirale ( Quyen et al. , 1987 ) , while etioline, so-
laspiralidine and 3- O - (β-glucopyranosyl)-etiolinewere
reported from the roots ( Ripperger, 1996 ) . As a part
of our phytochemical investigation on edible plant in
West China, three steroidal glycosides ( 1 - 3 ) were
identified fromthe fresh fruits of this plant for the first
time (Fig . 1 ) . Of them, 1 is a new compound . Two
known compounds were determined to be 26- O-β-D-
glucopyranosyl -( 25R )-furost-22ξ-methoxyl-3β, 26-di-
ol-5-ene-3- O-α-L-rhamnopyranosyl -( 1-2 )-β-D-gluco-
pyranoside (2) (Silva et al. , 1998 ) , and 26- O-β-D-
glucopyranosyl -(25 R) -furost-3β, 22ξ, 26-triol-5-ene-
3- O-α-L-rhamnopyranosyl - (1-2) -[α-L-rhamnopyrano-
syl -( 1-4 ) ]-β-D-glucopyranoside ( protodioscin) ( 3 )
( Watanabe et al. , 1983) , respectively, bycomparison
of their NMR datawith the reported literaturevalues .
Compound 1 was obtained as white amorphous
powder and showed a positive reaction with the Ehrlich
reagent, suggesting that 1 was a furostanol glycoside .
Its molecular formula was assigned as C53 H86 O23 on the
basisof HRFABMS m?z1089 .5457 [M-H] - ( calcd .
for C53 H85 O23 : 1089 .5481 ) . The 1 H NMR spectrum
displayed four methyl signals of a typical steroidal skel-
eton at [δ0 .88 , 1 .04 ( each 3H , s) , 0 . 97 ( 3H, d,
J = 6 .2 Hz) , 1 . 32 (3H, d, J = 7 .1 Hz) ] as well as
four anomeric proton signals atδ 4 .80 ( 1H, d, J =
7 .6 Hz, GlcII H - 1) , 5 . 85 (1H, s, RhaII H - 1 ) ,
4 . 94 ( 1H, d, J = 7 .2 Hz, GlcI H - 1 ) , and 6 .39
(1H, br s, RhaI H - 1) ] . These NMR features were
closely related to those of protodioscin ( 3) , except for
the appearance of additional signals rising from an
acetyl group: an isolated methyl proton signals atδ
1 .94 ( 3H, s, OCO - 揽CH3 ) , a carbonyl carbon at δ
170 .8 , and a methyl carbon atδ20 .9 . Comparing to
those of 3 , the downfield shift of C - 3 of RhaII by 1 .4
ppmtogether with theupfield shift of C - 2 and C - 4 by
0 .8 and 1 .3 ppm, respectively, suggested that the
acetyl group was linked to C - 3 of RhaII in 1 . This
was further supported by the HMBC correlations of H -
3 (δ4 .82) of RhaII with the acetyl carbonyl carbon at
δ170 .8 . Other HMBC correlations (Fig . 2) confirmed
thestructureof 1 as 26- O-β-D-glucopyranosyl - (25 R) -
furost-3β, 22ξ, 26-triol-5-ene-3- O-α-L-rhamnopyrano-
syl -( 1-2 )-[ 3- O -( 3- O-acetyl )-α-L-rhamnopyranosyl -
(1-4) ]-β-D-glucopyranoside .
Experimental section
General Experimental Procedures Optical rotation was
measured on a HORIBA SEPA-3000 automatic digital polarime-
ter . The NMR spectrawererecorded in pyridine- d5 on aBrucker
AM-400 and DRX-500 instruments with TMS as internal stan-
dard . FABMS datawere recorded on a VG Auto Spec3000 spec-
trometer and the HRESIMS on API Qstar Pulsar spectrometer . Si
gel ( 200 - 300 mesh) for column chromatography ( CC ) and
GF254 for TLC were obtained fromthe Qingdao MarineChemical
Factory, Qingdao, People′s Republic of China . Rp-8 ( 40 - 63
μm) for CC was fromMerck Corporation .
Plant Material Thefresh fruits of S. spiralewere collected
042 云 南 植 物 研 究 30 卷
Fig . 2 Key HMBC correlations of 1
from Xishuangbanna, Yunnan, and identified by Prof . C . R .
Yang, Kunming Instituteof Botany, Chinese Academy of Sciences .
Extraction and Isolation The fresh fruits ( 540 g) of
S. spirale wereextracted with MeOH (800 ml×3 ) under reflux3
times . After removal of the solvent under reduced pressure, the
concentrate was suspended into H2 O and partioned successively
with petroleumether, AcOEt, and n-BuOH . The n-BuOH frac-
tion ( 25 g) was subjected to column chromatography on silica
gel , eluting with CHCl3 -MeOH-H2 O ( 7∶3∶0 .5 ) to give five
fractions (Fr . 1 - 5) , Fr . 3 wassubjected to reversephaseRP-8
column elutingwith MeOH-H2 O (7∶3) to afford 1 ( 35 mg) , 2
(60 mg) and 3 (12 mg) .
Table 1 13 C NMR spectral data of compounds 1 - 3
No . 1 ?2 ?3 sugar 1 H2 3
1 ?37 C. 6 37 .6 37 c. 5 GlcI-1 100 .5 100 <. 2 100 z. 4
2 ?30 C. 1 30 .0 30 c. 0 2 78 .0 79 <. 1 77 z. 9
3 ?78 C. 4 78 .7 78 c. 5 3 78 .0 78 <. 5 78 z. 0
4 ?39 C. 1 39 .0 39 c. 5 4 78 .3 71 <. 9 78 z. 2
5 ?141 C. 0 141 .0 140 c. 9 5 77 .0 78 <. 7 77 z. 0
6 ?121 C. 9 121 .9 121 c. 9 6 61 .4 63 <. 0 61 z. 6
7 ?32 C. 5 32 .5 32 c. 4 RhaI-1 102 .1 102 <. 1 102 z. 0
8 ?31 C. 8 31 .8 31 c. 8 2 72 .6 72 <. 4 72 z. 6
9 ?50 C. 5 50 .4 50 c. 5 3 72 .8 72 <. 8 72 z. 9
10 ?37 C. 2 37 .2 37 c. 2 4 74 .2 74 <. 2 74 z. 1
11 ?21 C. 2 21 .1 21 c. 1 5 69 .6 69 <. 5 69 z. 6
12 ?40 C. 0 39 .8 40 c. 0 6 18 .8 18 <. 7 18 z. 7
13 ?40 C. 9 40 .6 40 c. 9 RhaII-1 103 .0 102 z. 9
14 ?56 C. 7 56 .7 56 c. 2 2 71 .8 72 z. 6
15 ?32 C. 6 32 .5 32 c. 6 3 74 .2 72 z. 8
16 ?81 C. 2 81 .4 81 c. 3 3 f-O- - 蕿COCH3 170 .8
17 ?63 C. 9 64 .3 63 c. 8 3 R-O-CO - ?CH3 20 .9
18 ?16 C. 6 16 .4 16 c. 5 4 72 .6 73 z. 9
19 ?19 C. 5 19 .5 19 c. 5 5 70 .5 70 z. 5
20 ?40 C. 8 40 .9 40 c. 8 6 18 .6 18 z. 5
21 ?16 C. 5 16 .3 16 c. 4 GlcII-1 105 .0 105 <. 0 105 z. 0
22 ?110 C. 8 112 .7 110 c. 8 2 75 .2 75 <. 2 75 z. 3
23 ?37 C. 2 30 .9 37 c. 2 3 78 .7 78 <. 7 78 z. 6
24 ?28 C. 4 28 .3 28 c. 2 4 71 .9 71 <. 9 71 z. 8
25 ?34 C. 5 34 .3 34 c. 5 5 78 .5 78 <. 5 78 z. 5
26 ?75 C. 3 75 .2 75 c. 4 6 62 .8 63 <. 0 62 z. 9
27 ?17 C. 6 17 .2 17 c. 5
OMe 47 ?. 4
1422 期 TENG Xi-Feng et al .: Three Steroidal Glycosides fromthe Fresh Fruits of Solanumspirale (Solanaceae)
26- O-β-D-glucopyranosyl -( 25 R)-furost-3β, 22ξ, 26-triol-
5-ene-3- O-α-L-rhamnopyranosyl -( 1-2 )- [ 3- O- ( 3-O-acetyl )-α-
L-rhamnopyranosyl -( 1-4 ) ]-β-D-glucopyranoside ( 1 ) , C53 H86
O23 , Whiteamorphous powder , [α]22D - 51 .6 ( c 0 .18 , MeOH) .
FABMS ( negative ion mode) , m?z 1089 [M-H ] - , 943 [M-
146-H ] - , 901 [ M-146-42-H ] - , 739 [ M-146-42-162-H ] - ,
HRFABMS ( negative ion mode) : m?z 1089 .5457 [ M-H ] -
(calcd .C53 H85 O23 for 1089 .5481) ; 1 H NMR ( pyridine- d5 , 400
MHz) δ0 .88 (3H, s, H - 18) , 0. 97 ( 3H , d, J = 6 .2 Hz, H
- 27) , 1 . 04 (3H , s, H - 19) , 1 . 32 (3H, d, J = 7 .1 Hz, H -
21) , 1 . 61 (3H, d, J = 5 .5 Hz, RhaII H - 6 ) . 1. 75 (3H, d,
J = 5 .5 Hz, RhaI H - 6 ) , 1 . 94 ( 3H , s, RhaII 3-O-CO - ?CH3 ) ,
2 . 20 (1H, m, H - 20) , 2. 73 (1H, m, H - 4) , 4 . 80 (1H , d,
J = 7 .6 Hz, GlcII H - 1) , 4. 82 (1H, m, RhaII H - 3 ) , 4 . 94
(1H, d, J = 7 .2 Hz, GlcI H - 1 ) , 4 . 95 (1H, m, H - 16 ) ,
5 . 29 (1H, br s, H - 6) , 5 . 85 (1H, br s, RhaII H - 1 ) , 6 . 39
(1H , br s, RhaI H - 1) , 13 C-NMR ( pyridine- d5 , 100 MHz) :
see table1 .
26- O-β-D-glucopyranosyl - ( 25 R ) -furost-22ξ-methoxyl-3β,
26-diol-5-ene-3- O-α-L-rhamnopyranosyl - ( 1-2 )-β-D-glucopyrano-
side (2) , C46 H76 O18 , White amorphous powder, FAB-MS ( nega-
tive ion mode) m?z 915 [M-H ] - , 769 [M-146-H ] - ; 13 C
NMR ( pyridine- d5 , 100 MHz) : see table1 .
26- O-β-D-glucopyranosyl -( 25 R )-furost-3β, 22ξ, 26-triol-
5-ene-3- O-α-L-rhamnopyranosyl -( 1-2 )-[α-L-rhamnopyranosyl -
(1-4 ) ]-β-D-glucopyranoside ( protodioscin) ( 3 ) , C51 H84 O22 ,
White amorphous powder, FAB-MS ( negative ion mode) m?z
1047 [M-H ] - , 901 [M-146-H ] - , 755 [M-146-146-H ] - ,
593 [M-146-146-162-H] - , 431 [M-146-146-162-162-H] - ; 13 C
NMR ( pyridine- d5 , 100 MHz) : see table 1 .
Acknowledgment: The authors thank the staffs of the analytical
group at State Key Labrotory of Phytochemistry and Plant Re-
sources in West China, Kunming Institute of Botany, Chinese
Academy of Sciences, for measuring the spectral data .
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242 云 南 植 物 研 究 30 卷