全 文 ：中华青荚叶的一个新果糖酯
?
来国防1 ,2 , 赵沛基1 , 倪志伟1 , 许云龙1 ,
王 梅2 , 罗士德1 , 王易芬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 云南省食品药品检验所 , 云南 昆明 650011 )
摘要 : 从山茱萸科中华青荚叶 ( Helwingia chinensis) 的乙醇提取物中分离得到一个新果糖酯和十个已知化
合物。通过现代波谱技术分别鉴定为 : 2- O -( E) -咖啡酰-3- O -( 3 , 5-二甲氧基香豆酰) -α-D-呋喃果糖甙
( 1) , 2- O-β-D-呋喃果糖基α-D-异吡喃糖酯 (2 ) , 甘草甜素 (3) , 4′-羟基-7- O-葡萄糖-2 , 3-二羟黄酮甙 (4) ,
黄豆甙 (5) , 5-葡萄糖芹菜甙 (6) , 7- O-葡萄糖芹菜甙 (7) , 4- O-葡萄糖香豆酸 (8) , 葡萄糖咖啡酸 (9 ) ,
3β-赤杨醇 (10) , 薯蓣皂甙 3- O -{α-L-鼠李糖吡喃糖基 (1→2 ) -[α-L-阿拉伯呋喃糖基 (1→3 ) ]-β-D-葡萄糖
吡喃糖} (11)。
关键词 : 中华青荚叶 ; 山茱萸科 ; 呋喃果糖 ; 黄酮甙 ; 抗细菌活性
中图分类号 : Q 946 文献标识码 : A 文章编号 : 0253 - 2700 (2008) 01 - 115 - 06
A New Fructofuranoside from Helwingia chinensis (Cornaceae)
LAI Guo-Fang1 , 2 , ZHAO Pei-Ji1 , NI Zhi-Wei1 , XU Yun-Long1 ,
WANG Mei
2
, LUO Shi-De
1
, WANG Yi-Fen
1 **
( 1 State Key Laboratory of Phytochemistry and Plant Resources in West China , Kunming Instituteof Botany,
Chinese Academy of Sciences, Kunming 650204 , China;
2 Yunnan Institute for Food and Drug Control , Kunming 650011 , China)
Abstract : A newfructofuranoside, togetherwith ten knowncompoundswere isolated fromtheEtOH extractionof theaerial
part of Helwingia chinensis . Their structureswereelucidated to be 2 - O- ( E)-caffeoyl-3- O -(3 , 5-dimethoxylcoumaroyl )-
α-D-fructofuranose (1) , 2- O-β-D-fructofuranosyl-α-D-allopyranose (2 ) , liquiritigenin ( 3) , 4′-hydroxy-2 , 3-dihydro-fla-
vonone-7- O-β-D-glucoside ( 4) , daidzin ( 5) , apigenin5- O-glucopyranoside (6) , apigenin-7- O-β-D-glucoside (7) , cou-
maric acid4- O-β-D-glucopyranoside (8) , glucopyranosylcaffeic acid (9) , 3β-hydroxyglutin-5-ene (10 ) , diosgenin3- O-α-
L-rhamnopyranosyl ( 1 → 2 ) -[α-L-arabinofuranosyl ( 1→ 3 ) ] -β-D-glucopyranoside ( 11 ) by intensive interpretation of
spectral data .
Key words: Helwingia chinensis; Cornaceae; Fructofuranose; Flavonoids; Antibacterial activity
Helwingia chinensis Batal ( Cornaceae) is distrib-
uted in thewestern and southern regions of China, for
example, Gansu, Guizhou, Hubei , Hunan, Shanxi ,
Sichuan, Tibet and Yunnan (Song et al. , 1990 ) . Its
flowers and leaves were edible, and a decoction of the
leaves and the bark are ingested for treating skin in-
flammations ( Zhonghua Bencao Bianweihui , 1999 ) .
The aerial part of this plant has longbeen used to treat
dysentery, hematochezia, swelling, etc (How, 1997) .
Our previous investigation of the plant reported the iso-
云 南 植 物 研 究 2008 , 30 (1) : 115～120
Acta Botanica Yunnanica

?
?? ?Author for correspondence
Received date: 2007 - 08 - 09 , Accepted date: 2007 - 11 - 02
作者简介 : 来国防 (1972 - ) 男 , 博士 , 主管药师 , 主要从事植物化学及药品质量标准的研究。 ?
Foundation item: This work was financially supported by Yunnan Natural Science Foundation (2006C0045Q)
lation and characterization of three new triterpenoids
(Lai et al. , 2003) and secoiridoid glycosides ( Lai et
al. , 2006 ) . In continuation of our work on this genus,
a new fructofuranose and ten known compounds were
isolated from the EtOH extraction of the aerial part of
Helwingia chinensis . Their structures were elucidated
by intensive interpretation of spectral data .
Results and Discussion
Compound 1 was isolated as an amorphous pow-
der, showed the molecular formula C26 H28 O13 based on
the [M-H] + ion peak at m?z 547 in thenegative FAB
mass spectrum (MS) and NMR spectral data, which
was confirmed by negative high resolution (HR )-FAB
mass experiment at m?z547 .1438 ( [M-H] + , C26 H27
O13 , cald . 547.1643) . 13 unsatuated degrees and its
13 C-NMR data showed the presence of two phenyl
groups in the structure of 1 . The 13 C-NMR and DEPT
experiments indicated the presence of two methoxyls,
two methylenes, twelve methines and ten quaternary
carbons . In the
1
H-NMR spectrum (seeTable 1) of 1 ,
a typical ABX aromatic proton systematδH 7 .14 (1H,
d, J = 8 .4 Hz) , 7. 23 ( 1H, dd, J = 8.4 , 1 .4 Hz)
and 7 .43 ( 1H, d, J = 1 .4 Hz) and one trans-α, β-
unsaturated olefin atδH 6 .87 , 8 .01 ( each 1H , d, J
= 15.9 Hz) were observed, which suggested the pres-
ence of a ( E )-caffeoyl moiety . This was confirmed by
the HMBC experiments basedon the correlations of be-
tween atδH 8 .01 andδC 123 .6 ( s, C - 1′) , 111 .4
(d, C - 2′) , 115 .4 ( d, C - 8′) , 167 .9 (s, C = O)
(see Figure . 2 ) . Moreover, its 1 H-NMR spectrum
contained another set of signals of a trans-α, β-unsat-
urated olefin atδH 6 .71 , 8 .12 (each 1H, d, J = 15 .8
Hz) and two aromatic proton signals atδH 7.13 ( 2H,
s) . The carbon signals atδC 166.9 (s) , 149.3 ( ×2 ,
s) , 146 .7 (d) , 140 .6 (s) , 125 .2 (s) , 115 .3 ( d) ,
107.0 (×2, d) , 56 .5 (×2 , q) showed the presence
of 3 , 5-dimethoxylcoumaroyl group . This was confirmed
Fig . 1 The structures of compounds 1 - 11
611 云 南 植 物 研 究 30 卷
Fig . 2 Key HMBC Correlations of compound 1
by the HMQC and HMBC experiments based on the
correlations atδH 3 .86 (6H, s) withδC 149 .3 ( ×2 ,
s) , δH 6 .71 withδC 125 .2 (s) ( see Figure) . Except
the abovementioned evidences, sixcarbon signalswere
present atδC 105 .0 (s) , 84 .9 ( d) , 79 .6 ( d) , 74 .2
( d) , 65.9 ( t) , 63.5 ( t) . The presenceofα-D-fruct-
ofuranose was identified by compared themwith that of
literature ( Leslie et al. , 1980) .
Long-rang correlations through 3 J in the HMBC
spectrum (See Figure 2) atδH 6 .50 (1H , d, J = 7 .7
Hz, H - 3) withδC 166 .9 (s, C = O) indicated that
3 , 5-dimethoxylcoumaroyl group located at C - 3 . The
weak correlations between atδH 6 .87 ( 1H, d, J =
15 .9 Hz) withδC 105.0 (s) showed that ( E )-caffeoyl
moiety was located at C - 2 . Basedon abovementioned
evidence, the structureof 1 was identified to be 2- O -
( E )-caffeoyl-3- O -( 3″, 5″-dimethoxyl )-( E )-cou-
maroyl-α-D-fructofuranose .
Compounds 2 - 11 were elucidated to be 2- O-β-D-
fructofuranosyl-α-D-allopyranose ( 2 ) ( Hongh et al. ,
1986) , liquiritigenin (3) (Tsutomu et al. , 1985) , 4′-
hydroxy-2, 3-dihydro-flavonone 7- O-β-D-glucopyrano-
side (4) (Shul′ts et al. , 2000 ) , daidzin (5) (Park et
al. , 1992 ) , apigenin 5- O-β-D-glucopyranoside ( 6 )
(Martin et al. , 1991) , apigenin-7- O-β-D-glucopyrano-
side (7) ( Wang et al. , 1990 ) , coumaric acid 4- O-β-
D-glucopyranoside (8 ) ( Cui et al. , 1992 ) , glucopyr-
anosylcaffeic acid (9) (Cui et al. , 1992) , 3β-hydrox-
yglutin-5-ene (10 ) (Antonio et al. , 1987 ) , diosgenin
3-O-α-L-rhamnopyranosyl ( 1 → 2 ) -[α-L-arabino-
furanosyl (1→3 ) ]-β-D-glucopyranoside ( 11) ( Xu et
al. , 1988 ) by NMR spectra data and compared with
the report in the literatures . By the paper diffusion
method ( 5 mm diameter) to assay their activities of
against Shigella flexneri , S. dysenteriae, S. sonnei ,
Mycobacteriumtuberculosis, α-Hemolytic sterepteococcus
and Streptococcus pneumoniae, compounds 1 and 6
showed weak activities against S. flexneri and M. tub-
erculosis in agar diffusion assay, respectively . In this
paper, wedescribe the structures elucidationbyvarious
NMR spectra analysis .
Experimental
General experimental procedures Optical rotation was
taken ona SEPA-300 polarimeter . FABMSdata wereobtainedon
a VG AutoSpec-3000 spectrometer . 1 H- , 13 C- , and 2D-NMR
spectra wererecordedon aBruker AM 400 NMR and aDRX-500
spectrometer withTMS asinternal standard . Silicagel (200 - 300
mesh, or silica gel H , 10 - 40μm) for column chromatography
(CC) and silicagel plate (GF254) for thin-layer chromatography
(TLC) were obainedfromthe QingdaoMarineChemical Factory,
Qingdao, Shandong Province China .
Plant material The aerial parts of Helwingia chinensis
were collected in Xishuangbanna, Yunnan, P . R . China in July
2002 (Lai et al. , 2003) .
Extraction and Isolation The air-dried aerial parts ( 40
kg) were extracted twice with 95% EtOH at r . t . and the frac-
tionswere described as in the literature (Lai et al. , 2006) . The
fraction B was rechromatographed over silica gel ( 200 - 300
mesh) , eluting with CHCl3∶MeOH ( 99∶1 to 10∶1 ) to afford
compound10 (32 mg) . The fraction D ( 3. 1 g) was purified by
repeatedCC on silica gel (CHCl3∶MeOH 50∶1 , 30∶1 , 20∶1 ,
10∶1) and then Sephadex LH-20 eluted by MeOH to give 1 ( 12
mg) , 3 (16 mg) and 5 (24 mg) . The fraction E ( 1 . 9 g) was
purified byCC on silica gel ; CHCl3∶MeOH 20∶1 to 4∶1 ) and
then Sephadex LH-20 (MeOH) to give 4 ( 28 mg) , 6 ( 38 mg)
and 7 (57 mg) . TheBuOH extract (15 g) was fractionated byCC
on silica gel (200 - 300 mesh) , CHCl3∶MeOH from20∶1 to2∶1)
and then RP-18 (MeOH-H2 O 6∶4 to8∶2) to afford thecompounds
2 (1 .2 g) , 8 (19 mg) , 9 (325 mg) and 11 (14 mg) .
Antimicrobial activity assay Inhibitory activities of com-
pounds 1 - 11 against Shigella flexneri , S. dysenteriae, S. s-
onnei , Mycobacterium tuberculosis, α-Hemolytic sterepteococcus
and Streptococcus pneumoniaewere determined by the paper disk
diffusion assay on agar plates as described ( Wang et al. ,
2003) . Only compounds 1 and 6 showed weak activities (6 mm?
disk) against S. flexneri and M. tuberculosis, respectively .
7111 期 LAI Guo-Fang et al. : A New Fructofuranosidefrom Helwingia chinensis ( Cornaceae)
Table 1 The 1 H- , 13C-NMR and 2D NMR spectral data of 1 in C5 D5 N (500 MHz and 125 MHz, δ in ppm)
No . δH ( Multiplicity, J in Hz) δC HMBC (H→C)
1 y4 ?. 32 (2H , s) 65 .9 t C - 2 3, 3
2 y105 ?. 0 s
3 y6 ?. 50 (1H , d, 7 . 7 ) 79 .6 d C - 1 3, 2 , 4 , 9″
4 y5 ?. 46 (1H , t, 7 . 5 ) 74 .2 d C - 2 3, 3 , 5 , 6
5 y4 ?. 78 (1H , m) 84 .9 d C - 4 3, 6
6 y4 ?. 57 ( 1H , dd, 11 . 8 , 3 .9)
4 ?. 64 ( 1H , dd, 11 . 8 , 4 .8) 63 ?. 5 t
C - 4 3, 5
C - 4 , 5
1 l′ 123 ?. 6 s
2 l′ 7 ?. 43 (1H , s) 111 .4 d C - 1 3′, 3′, 4′, 6′, 7′
3 l′ 149 ?. 0 s
4 l′ 151 ?. 1 s
5 l′ 7 ?. 14 (1H , d, 8 . 4 ) 106 .8 d C - 1 3′, 3′, 4′
6 l′ 7 ?. 23 (1H , d, 8 . 4 ) 116 .7 d C - 1 3′, 2′, 4′, 5′, 7′
7 l′ 8 ?. 01 (1H , d, 15 . 9) 145 .8 d C - 1 3′, 2′, 6′, 8′, 9′
8 l′ 6 ?. 87 (1H , d, 15 . 9) 115 .4 d C - 2 3, 1′, 7′, 9′
9 l′ 167 ?. 9 s
1 l″ 125 ?. 2 s
2 *″, 6″ 7 ?. 13 (2H , s) 107 .0 d C - 1 3″, 6″( 2″) , 3″, 4″, 5″, 7″
3 *″, 5″ 149 ?. 3 s
4 l″ 140 ?. 6 s
7 l″ 8 ?. 12 (1H , d, 15 . 8) 146 .7 d C - 1 3″, 2″, 6″, 8″, 9″
8 l″ 6 ?. 71 (1H , d, 15 . 8) 115 .3 d C - 1 3″, 7″, 9″
9 l″ 166 ?. 9 s
OMe 3 ?. 86 (6H , s) 56 .5 q C - 3 3″, 5″
Chinenicside B (1 ) : white powder, C26 H28 O13 , negative
FAB-MS m?z ( % ) : 547 [ M-H ] - ( 100 ) , 532 [ M-16 ] +
(23) , 255 (46) , 223 ( 18) , 177 ( 17) ; negative HR-FAB-MS
m?z: 547 .1438 ( [M-H ] - , C26 H27 O13 , cald . 547 .1643) ; 1 H-
NMR and 13 C-NMR (see table 1) .
2- O-β-D-fructofuranosyl-α-D-allopyranose ( 2 ) : white
powder, C12 H22 O11 , negative FAB-MS m?z ( % ) : 341 [ M-
H] - (100) , 293 ( 7 ) , 127 ( 12 ) ; 1 H-NMR ( CD3 OD, 400
MHz)δ: 5 . 20 (1H , d, J = 10 .6 Hz, H - 1′) , 5. 07 (1H, d,
J = 10 .6 Hz, H - 1′) , 5 . 15 ( 1H , d, J = 3 .7 Hz, H - 1 ) ,
4 . 81 (1H, dd, J = 5 .3 , 11 .9 Hz, H - 6 ) , 4 . 42 ( 1H , dd, J
= 2 .0 , 11 .9 Hz, H - 6 ) , 4 .77 (1H, d, J = 10 .2 Hz, H - 6′) ,
4 . 52 (1H, d, J = 10 .2 Hz, H - 6′) ; 13 C-NMR ( CD3 OD, 100
MHz)δ: 62 .1 ( t, C - 1′) , 104 .1 (s, C - 2′) , 77.0 ( d, C -
3′) , 74 .3 ( d, C - 4′) , 82 .6 ( d, C - 5′) , 62 .2 ( t, C - 6′) ,
91 .8 ( d, C - 1) , 71 .7 ( d, C - 2) , 72 .9 (×2 , d, C - 3 , 5 ) ,
69 .8 ( d, C - 4) , 60.5 (t, C - 6) .
Liquiritigenin ( 3) : yellow powder , C15 H12 O4 , EI-MS m?
z ( % ) : 256 [M] + ( 100 ) , 239 (7) , 228 (12 ) , 163 (17 ) ,
145 (22) , 137 (73 ) , 121 ( 95 ) , 110 ( 41 ) , 101 (55 ) , 85
(40) , 55 (70 ) ; 1 H-NMR (400 MHz, CD3 OD) δ: 2. 75 (1H,
dd, J = 2 .8 , 16 .9 Hz, H - 3β) , 3. 25 (1H , dd, J = 13 .6 ,
16 .5 Hz, H - 3α) , 5 . 55 (1H, dd, J = 2.8 , 13 .0 Hz, H - 2β) ,
6 . 80 (1H, d, J = 2 .0 Hz, H - 8) , 6. 88 ( 1H , dd, J = 2 .0 ,
8 .8 Hz, H - 6) , 7. 21 ( 2H , br . d, J = 8 .6 Hz, H - 3′, 5′) ,
7 . 53 (2H, br . d, J = 8 .7 Hz, H - 2′, 6′) , 8 . 16 ( 1H , d, J
= 8 .8 Hz, H - 5 ) ; 13 C-NMR (100 MHz, CD3 OD) δ: 190 .4
(s, C - 4) , 166 .5 (s, C - 7) , 164 .5 (s, C - 9 ) , 159 .3 (s, C
- 4′) , 130 .2 (s, C - 1′) , 129 .5 ( d, C - 5 ) , 128.7 (×2 , d,
C- 2′, 6′) , 116.5 (×2 , d, C - 3′, 5′) , 114 .9 (s, C - 10 ) ,
111 .5 (d, C - 6) , 103 .7 ( d, C - 8 ) , 80 .3 ( d, C - 2 ) , 44 .4
(t, C - 3 ) .
4′-Hydroxy-2, 3-dihydroflavonone 7- O-β-D-glucoside (4) :
yellow powder , C21 H22 O9 , negative FAB-MS m?z ( % ) : 417
[M-H ] - (64 ) , 403 ( 16 ) , 385 ( 5 ) , 357 (8 ) , 325 (100 ) ,
311 978) , 293 (12) , 265 (17) , 156 ( 4) , 80 ( 14 ) ; 1 H-NMR
(400 MHz, C5 D5 N) δ ppm: 5 . 54 ( 1H, dd, J = 2 .8 , 12 .9
Hz, H - 2) , 2 . 94 (1H, dd, J = 2 .8 , 16 .6 Hz, H - 3β) , 3 . 22
(1H, dd, J = 13 .0 , 16 .6 Hz, H - 3α) , 8 . 20 (1H, d, J = 8 .7
Hz, H - 5 ) , 6. 94 ( 1H , dd, J = 2 .0 , 8 .7 Hz, H - 6) , 6 . 85
(1H, d, J = 2 .2 Hz, H - 8) , 7 . 52 (2H, d, J = 8 .7 Hz, H -
2′, 6′) , 7 . 40 (2H, d, J = 8 .7 Hz, H - 3′, 5′) , 5 . 70 (1H,
d, J = 7 .4 Hz, H - 1″) , 4. 58 (1H, J = 11 .8 Hz, H - 6″) ,
4 . 34 - 4 .44 ( 4H , m) ; 13 C-NMR (100 MHz, C5 D5 N) δppm:
190 .2 (s, C - 4) , 166.7 (s, C - 7) , 164.5 (s, C - 9) , 158 .9
(s, C - 4′) , 133.4 (s, C - 1′) , 129 .5 ( d, C - 5 ) , 128.3 (×
811 云 南 植 物 研 究 30 卷
2 , d, C - 2′, 6′) , 117 .5 (×2 , d, C - 3′, 5′) , 114 .5 (s, C
- 10) , 111 .8 ( d, C - 6) , 80.2 ( d, C - 2) , 44 .8 (t, C - 3 ) ,
102 .2 ( d, C - 1″) , 78.9 (d, C - 3″) , 78 .6 ( d, C - 5″) , 74 .9
(d, C - 2″) , 71 .5 ( d, C - 4″) , 62 .5 (t, C - 6″) .
Daidzin (5) : white powder, C21 H20 O9 , negative FAB-MS
m?z ( % ) : 569 [M+ 154] - (100) , 415 [M-H ] - (15) , 253
[M-162 ] - ( 45 ) ; 1 H-NMR ( 500 MHz, CD3 OD) δ: 8 . 36
(1H , dd, J = 3 .1 , 8 .2 Hz, H - 3′, 5′) , 8 . 14 (1H, dd, J =
3 .1 , 8 .2 Hz, H - 2′, 6′) , 7 . 78 ( 1H , dd, J = 2 .9 , 8 .1 Hz,
H - 5) , 7 . 43 (1H, s, H - 2 ) , 7. 29 ( 1H , dd, J = 2 .6 , 8 .2
Hz, H - 6) , 5 .82 ( 1H , d, J = 7 .2 Hz, H - 1′) , 4 . 62 (2H,
d, J = 11 .9 Hz, H - 6′) , 4 . 27 - 4.45 (3H, m) , 4 . 26 ( 1H , br
s) ; 13 C-NMR (125 MHz, CD3 OD)δ: 175 .8 (s, C - 4) , 162 .4
(s, C - 7) , 159 .2 (s, C - 9) , 157 .9 (s, C - 4′) , 153 .0 ( d, C
- 2) , 131 .1 (d, C - 2′, 6′) , 127 .9 ( d, C - 5) , 125 .2 (s, C
- 1′) , 119 .3 (s, C - 10) , 116 .4 ( d, C - 3′, 5′) , 116 .1 ( d, C
- 6) , 104 .3 (d, C - 8) , 101 .9 (d, C - 1″) , 79 .3 ( d, C - 3″) ,
78 .5 ( d, C - 5″) , 74 .9 ( d, C - 2″) , 71 .3 ( d, C - 4″) , 62 .5
(t, C - 6″) .
Apigenin 5- O-β-D-glucopyranoside ( 6 ) : white powder,
C21 H20 O10 , negative FAB-MS m?z ( % ) : 431 [ M-H ] -
(100) , 405 ( 8) , 282 ( 13) , 215 (17 ) , 145 ( 24 ) ; 1 H-NMR
(500 MHz, CD3 OD)δppm: 7 . 88 ( 1H, d, J = 8 .6 Hz, H -
2′, 6′) , 7 . 20 ( 1H , d, J = 6.1 Hz, H - 3′, 5′) , 7 . 11 (1H,
d, J = 1 .2 Hz, H - 8 ) , 6 .91 (1H, s, H - 3) , 6 . 86 (1H , d, J
= 1 .5 Hz, H - 6) , 5 . 86 (1H, d, J = 7 .4 Hz, H - 1′) , 4 . 58
(2H , d, J = 10 .6 Hz, H - 6′) , 4 .44 - 4 .34 ( 3H , m, ) , 4 . 23
(1H , br s) ; 13 C-NMR ( 125 MHz, CD3 OD) δppm: 182 .9 (s,
C - 4) , 165 .0 (s, C - 5) , 164 .1 (s, C - 7 ) , 162 .9 (s, C - 9) ,
162 .6 (s, C - 2) , 157 .9 (s, C - 4′) , 129 .0 ( d, C - 3′, 5′) ,
122 .1 (s, C - 1′) , 116 .9 (d, C - 2′, 6′) , 106 .6 (s, C - 10) ,
104 .1 ( d, C - 3) , 100 .7 ( d, C - 6) , 95 .4 ( d, C - 8) , 101 .8
(1d, C - 1″) , 79 .3 ( d, C - 3″) , 78.5 ( d, C - 5″) , 74 .9 (d, C
- 2″) , 71 .2 ( d, C - 4″) , 62 .4 (t, C - 6″) .
Apigenin-7- O-β-D-glucoside (7 ) : white powder, C21 H20
O10 , negative FAB-MS m?z ( % ) : 431 [M-H ] - ( 100 ) , 415
(11 ) , 269 [M-162 ] - ( 70) ; 1 H-NMR ( 400 MHz, CD3 OD) δ:
8 . 11 (1H, s, H - 2) , 7 .70 (2H, d, J = 8 .5 Hz, H - 3′, 5′) ,
7 . 28 (2H, d, J = 8 .5 Hz, H - 2′, 6′) , 6 . 94 (1H, d, J = 2 .7
Hz, H - 8) , 6. 86 (1H, d, J = 2 .7 Hz, H - 6) , 5 . 81 (1H, d,
J = 7 .3 Hz, H - 1′) , 4. 57 (2H, d, J = 11 .8 Hz, H - 6′) ,
4 . 44 - 4 .34 (3H , m) , 4 . 20 (1H , br s) ; 13 C-NMR (100 MHz,
CD3 OD)δ: 181 .4 (s, C - 4) , 164 .4 (s, C - 7) , 159 .4 (s, C
- 5) , 158 .1 (s, C - 4′) , 163.0 (s, C - 9) , 153 .9 (s, C - 2) ,
131 .0 ( d, C - 2′, 6′) , 122 .1 (s, C - 1′) , 116.4 ( d, C - 3′,
5′) , 107 .3 (s, C - 10) , 100 .7 ( d, C - 6 ) , 95 .2 ( d, C - 8 ) ,
100 .7 ( d, C - 6 ) , 101 .7 ( d, C - 1″) , 79 .3 ( d, C - 3″) , 78 .5
(d, C - 5″) , 74 .8 ( d, C - 2″) , 71 .2 ( d, C - 4″) , 62 .4 (t, C
- 6″) .
Coumaric acid-4- O-β-D-glucopyranoside ( 8 ) : white
powder, C15 H18 O8 , negative FAB-MS m?z ( % ) : 325 [M-H] -
(100) , 163 (27) ; 1 H-NMR (400 MHz, C5 D5 N)δ: 7 . 30 (2H,
d, J = 8.6 Hz, H - 2 , 6) , 6 . 71 (2H, d, J = 8 .6 Hz, H - 3 ,
5) , 7 . 75 (1H, d, J = 15 .9 Hz, H -α) , 6 . 30 (1H, d, J =
15 .9 Hz, H -β) , 5 . 64 ( 1H , d, J = 7 .8 Hz, H - 1′) , 4 . 54
(1H , d, J = 10 .5 Hz, H - 6′) , 4. 42 - 4 .26 (4H, m) ; 13 C-
NMR (100 MHz, C5 D5 N) δ: 170 .5 ( s, CO) , 159 .7 (s, C -
4) , 143 .2 ( d, C -α) , 130 .5 (×2 , d, C - 2 , 6) , 127.5 (s, C
- 1 ) , 117 .8 ( d, C -β) , 116 .5 (×2 , d, C - 3 , 5) , 103 .6
(d, C - 1′) , 79 .2 ( d, C - 3′) , 78 .4 ( d, C - 5′) , 74 .9 (d, C
- 2′) , 71 .1 ( d, C - 4′) , 62 .2 (t, C - 6′) .
Glucopyranosylcaffeic acid ( 9 ) : white powder, C15 H18
O9 , negative FAB-MS m?z ( % ) : 341 [M-H ] - ( 100 ) , 324
(11 ) , 179 ( 26 ) ; 1 H-NMR (400 MHz, C5 D5 N)δ: 8 . 04 (1H,
d, J = 15 .9 Hz, H -α) , 7. 62 (1H, d, J = 1 .7 Hz, H - 2 ) ,
7 . 53 (1H, d, J = 8 .3 Hz, H - 5) , 7. 11 ( 1H , dd, J = 1 .6 ,
8 .3 Hz, H - 6 ) , 6. 87 (1H, d, J = 15 .9 Hz, H -β) , 5 . 62
(1H , d, J = 7 .7 Hz, H - 1′) , 4 . 52 (1H, d, J = 10.2 Hz, H
- 6′) , 4 . 42 - 4 .26 (4H, m) ; 13 C-NMR (100 MHz, C5 D5 N) δ:
169 .7 (s, CO) , 149 .9 ( s, C - 3) , 148 .6 (s, C - 4 ) , 144 .4
(d, C -α) , 130 .9 (s, C - 1) , 120 .9 (d, C - 2) , 118 .9 ( d, C
- 5) , 116.5 ( d, C -β) , 103 .6 (d, C - 1′) , 79 .2 ( d, C - 3′) ,
78 .4 ( d, C - 5′) , 74 .9 ( d, C - 2′) , 71 .1 ( d, C - 4′) , 62 .2
(t, C - 6′) .
3β-Hydroxyglutin-5-ene ( 10) : white powder, C30 H50 O,
EI-MS m?z ( % ) : 426 [M] + (18) , 408 (21) , 393 (5) , 274
(100) , 259 (57) , 245 (9) , 205 (28) , 173 (23) , 119 (43) ,
109 (54) , 95 (72) , 69 ( 84) , 55 (75) ; 1 H-NMR ( 400 MHz,
CDCl3 ) δ: 1 . 07 , 1 .04 , 1 .00 , 0 .95 , 0.91 , 0.90 , 0.86 ,
0 .82 , 0 .81 , 0 .76 (each, 3H, s) , 3 . 37 ( 1H , br s, H - 3 ) ,
5 . 52 (1H, d, J = 4 .8 Hz, H - 5 ) ; 13 C-NMR (100MHz, CDC-
l3 ) δ: 18 .1 ( t, C - 1 ) , 27 .7 ( t, C - 2) , 76 .1 ( d, C - 3 ) ,
40 .5 (s, C - 4 ) , 141 .6 (s, C - 5 ) , 121 .6 ( d, C - 6) , 23 .4
(t, C - 7 ) , 47 .3 ( d, C - 8) , 34 .6 (s, C - 9) , 49.6 ( d, C -
10) , 32 .9 (t, C - 11) , 30.2 ( C - 12) , 37 .7 (s, C - 13 ) , 39 .1
(s, C - 14 ) , 34 .5 ( t, C - 15) , 34 .9 ( t, C - 16) , 29 .9 (s, C
- 17) , 42 .9 ( d, C - 18) , 34 .9 (t, C - 19) , 28 .1 (s, C - 20) ,
31 .9 (t, C - 21) , 39 .1 ( t, C - 22 ) , 28 .8 ( q, C - 23) , 25 .2
(q, C - 24) , 16 .0 ( q, C - 25) , 18 .1 (q, C - 26) , 18 .2 ( q, C
- 27) , 32 .2 (q, C - 28) , 31 .9 ( q, C - 29) , 34 .3 ( q, C -
30) .
Diosgenin 3- O-α-L-rhamnopyranosyl (1→2)-[α-L-ara-
binofueranosyl ( 1 → 3 ) ] -β-D-glucopyranoside ( 11 ) : white
powder, C44 H70 O16 , negative FAB-MS m?z ( % ) : 853 [ M-
9111 期 LAI Guo-Fang et al. : A New Fructofuranosidefrom Helwingia chinensis ( Cornaceae)
H] - (100) , 721 (14) , 691 ( 18) , 479 (11) , 447 (24) , 411
(39 ) ; 1 H-NMR (400 MHz, C5 D5 N) δ: 6 . 30 ( 1H , br s, H -
1″) , 5 . 31 (1H, d, J = 4 .7 Hz, H - 6) , 4 . 98 (1H, d, J = 3 .7
Hz, H - 1?) , 4 . 96 (1H, d, J = 5 .7 Hz, H - 1′) , 3 . 59 (1H,
br d, J = 10 .7 Hz, H - 26α) , 3 .51 (1H , dd, J = 10 .7 , 10 .8
Hz, H - 26β) , 4 . 63 (1H, dd, J = 3 .3 , 9 .3 Hz, H - 3) , 1 . 78
(3H, d, J = 6.3 Hz, H - 6″) , 1. 14 (1H, d, J = 6 .9 Hz, H -
21) , 1. 05 ( 3H , s, H - 19) , 0 .83 ( 3H , s, H - 18 ) , 0 . 70
(3H, d, J = 5.0 Hz, H - 27) ; 13 C-NMR (100 MHz, C5 D5 N)
δ: 37 .6 ( t, C - 1) , 31.9 ( t, C - 2 ) , 77 .8 ( d, C - 3) , 39 .9
(t, C - 4) , 140 .8 (s, C - 5) , 121 .9 ( d, C - 6) , 32 .3 (t, C -
7) , 31 .7 (d, C - 8) , 50.3 ( d, C - 9) , 37 .2 (s, C - 10) , 21 .2
(t, C - 11) , 39 .0 (t, C - 12) , 40 .5 (s, C - 13) , 56 .7 ( d, C
- 14) , 30 .2 (t, C - 15) , 81 .2 ( d, C - 16) , 62 .9 (d, C - 17) ,
19 .5 ( q, C - 18) , 16 .4 ( q, C - 19) , 42 .0 ( d, C - 20) , 15 .1
(q, C - 21) , 109 .3 (s, C - 22) , 32 .4 (t, C - 23) , 29 .3 (t, C
- 24) , 30.7 ( d, C - 25 ) , 66 .9 (t, C - 26 ) , 17.4 ( q, C -
27) , Glc: 100 .2 ( C - 1′) , 78 .1 (C - 2′) , 77 .9 ( C - 3′) , 76 .8
(C - 4′) , 77 .0 ( C - 5′) , 62 .6 ( C - 6′) , Rha: 102 .0 (C - 1″) ,
72 .6 (C - 2″) , 72 .9 (C - 3″) , 74 .2 (C - 4″) , 69 .6 ( C - 5″) ,
18 .7 (C - 6″) , Ara: 109.7 (C - 1?) , 82.8 ( C - 2?) , 77 .5 ( C
- 3?) , 86 .7 ( C - 4?) , 61 .4 ( C - 5?) .
Acknowledgement: The authors are grateful to the analytical
group of the Laboratory of Phytochemistry, Kunming Institute of
Botany, Chinese Academy of Sciences for measuring NMR and
MS data .
References:
Anto ?nio GG, Esteban EF , Angel GR , 1987 . Triterpenes from Maytenus
horrida [ J ] . Phytochemistry, 26 : 2785—2788
Cui ?CB , Tezuka Y , Kikuchi T et al. , 1992 . Constituents of a fern,
Davallia mariesii moore . IV . Isolation and structures of anovel nor-
carotane sesuiterpene glycoside, a chromone glucuronide, and two
epicatechin glycosides [ J ] . ChemPharmBull , 40 (8 ) : 2035—2040
Houg .h L , O′Brien E, 1986 . Synthesisof 3-deoxy- and 3-deoxy-3-fluoro-
sucrose, andα-D-allopyranosylβ-D-fructofuranoside [ J ] . Carbohydr
Res, 147 ( 1) : 149—154
How ?FC, 1997 , A Dictionary of Traditional Chinese Drug [ M ] . Shang-
hai : Shanghai Science and Technology Press, 646
Lai ?GF , Wang YF , Lu CH et al. , 2003 . Three novel triterpenoids from
the aerial part of Helwingia chinensis [ J ] . Helv Chim Acta, 86 :
2136—2141
Lai ?GF (来 国防 ) , Wang Y F ( 王易 芬 ) , Wang M ( 王 梅 ) et al. ,
2006 . A new secoiridoid glycoside from Helwingia chinensis ( Cor-
naceae) [ J ] . Acta Bot Yunnan (云南植物研究 ) , 28 : 676—678
Lesl ?ie H , Eugene O, 1980 .α-D-Allopyranosylβ-D-fructofuranoside ( al-
lo-sucrose) and its derivatives [ J ] . Carbohydrate Res, 84 : 95—102
Mart ?in G, Walter F , 1991 . Flavonoid 5-glucosides from Prunus cerasus
bark and their characteristic weak glycosidic bonding [ J ] . Phyto-
chemistry, 30 : 1519—1521
Park ?HH , HaramatsukaT, Noguchi H et al. , 1992 . Isoflavoneglycosides
exist as their 6″- O-malonyl esters in Pueraria lobata and its cell sus-
pension cultures [ J ] . Chem Pharm Bull , 40 : 1978—1980
Shul ?′ts EE, Petrova TN , Shakirov MM et al. , 2000 . Flavonoids of roots
of Glycyrrhiza uralensis growing in Siberia [ J ] . ChemNat Compd,
36 : 362—368
Song ?ZP (宋滋圃 ) , HuWG (胡文光 ) , 1990 . Floraof China (中国植
物志 ) [B] . 56 : 20—35
Tsen ?g CF , Iwakami S, Mikajiri A et al. , 1992 . Inhibition of in vitro
prostaglandin and leukotriene biosyntheses by cinnamoyl-b-phenethyl-
amine and N-acyldopamine derivatives [ J ] . Chem Pharm Bull , 40 :
396—400
Tsut ?omu Nakanishi , Akira Inada, Kazuko Kambayashi et al. , 1985 . Fla-
vonoid glycosides of the roots of Glycyrrhiza uralensis [ J ] . Phyto-
chemistry, 24 (2 ) : 339—341
Wang ?JX ( 王军宪 ) , Hou GN ( 侯桂宁 ) , 1990 . Chemical study on the
flower of Ligust rumlucidumait [ J ] . Zhongguo Zhongyao Zazhi
( 中国中药杂志 ) , 3 : 168—170
WangYF , Lai GF , Lu CH et al. , 2003 . A new indolizinonefrom Polyg-
onatum kingianum [ J ] . Planta Med, 69 : 1066—1068
XuXM (徐 学民 ) , Zhong ZC ( 钟 炽昌 ) , 1988 . Chemical study on
Paris polyphylla var . chinensis [ J ] . Zhongcaoyao ( 中草药 ) , 19 :
194—198
Zhon ?ghua Bencao Bianweihui ( 中 华本 草 编 委会 ) , 1999 . Zhonghua
Bencao ( 中华本草 ) [ M ] , Vol . 15 . Shanghai : Shanghai Science
and Technology Press, 746—747
021 云 南 植 物 研 究 30 卷