全 文 ：朝鲜蓟叶中的酚性糖苷化合物
刘 荣1 , 2 , 蒋孟圆1 ,2 , 周忠玉1 , 2 , 刘吉开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 : 从朝鲜蓟 ( Cynara scolymus) 叶中分离得到 2 个酚性糖苷化合物 , 其中一个是新化合物 , 通过波谱学
方法确定其结构为 2-甲氧基-4 - (2 , 3-二羟基-丙酰基)-苯基-1- O -(6′- O-没食子酰基)-β-D-吡喃葡萄糖苷 (1)。
关键词 : 朝鲜蓟 ; 菊科 ; 酚性糖苷
中图分类号 : Q 946 文献标识码 : A 文章编号 : 0253 - 2700 (2009) 01 - 089 - 04
Phenolic Glucoside Gallates from the Leaves of
Cynara scolymus (Compositae)
LIU Rong
1 , 2
, J IANG Meng-Yuan
1 , 2
, ZHOU Zhong-Yu
1 , 2
, LIU Ji-Kai
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: A new phenolic glucoside gallate, named 2-methoxy-4 -( 2 , 3-dihydroxy-propionyl )-phenyl-1- O-( 6′-O-gal-
loyl)-β-D-glucopyranoside (1) , together with aknown phenolic glucosidegallate (2) , were isolatedfromthe leaves of Cy-
nara scolymus (Artichoke) . The structureof 1 was elucidated mainly by extensive spectral methods (MS, IR , 1D and2D
NMR techniques) .
Key words: Cynara scolymus; Compositae; Phenolic glycoside
Cynara scolymus L . ( Artichoke) is an ancient
herbaceous plant, belonging to the family Compositae
and originating from the Mediterranean area . Today,
artichoke is widely grown all over the world and its
sprout is eaten as a vegetable . The leaves of artichoke
havebeenused as acholeretic and diuretic in tradition-
al medicine since ancient times ( Kirchhoff et al. ,
1994) . Various chemical constituents ( Wang et al. ,
2003; Shimoda et al. , 2003; Zhu et al. , 2004;
Schütz et al. , 2004) fromartichoke includingpolyphe-
nols such as cynarin, caffeoylquinic acids and chloro-
genic acids, flavonoids, sesquiterpenes and sesquiter-
pene glycosides have been found and have shown some
pharmacological activities (Dranik et al. , 1996; Kraft,
1997; Brown et al. , 1998 ) such as antibacterial , an-
tioxidative, choleretic, bileexpelling and hepatoprotec-
tive activities . We have further carried out a chemical
investigation on the leaves of artichoke which is culti-
vated in Vietnamand isolated a new phenolic glucoside
gallate, 2-methoxy-4 - ( 2 , 3-dihydroxy-propionyl ) -
phenyl-1- O- (6′- O-galloyl ) -β-D-glucopyranoside (1) .
This paper reports the isolation and structural elucida-
tion of compound 1 .
Results and Discussion
Compound 1 was obtained as white amorphous
云 南 植 物 研 究 2009 , 31 (1) : 89～92
Acta Botanica Yunnanica DOI : 10 .3724?SP. J . 1143 .2009.08173
? ?Author for correspondence; E-mail : jkliu@ mail .kib. ac. cn; Tel : + 86 - 871 - 5216327
Received date: 2008 - 09 - 12 , Accepted date: 2008 - 11 - 10
作者简介 : 刘荣 ( 1980 - ) 男 , 在读博士研究生 , 主要从事高等真菌的化学研究。
power and showed a quasi-molecular ion peak at m?z
549 .1403 [ M + Na] + ( calcd for C23 H26 O14 Na
549 .1406 ) in its HRESIMS corresponding to the mo-
lecular formula C23 H26 O14 . The IR spectrum exhibited
absorption bands for hydroxyls ( 3 406 cm- 1 ) , carbon-
yls (1 720 and 1 705 cm- 1 ) and aromatic moieties
(1 612 , 1 516 , and 1 351 cm- 1 ) . The 1 H NMR data
suggested thepresenceof agalloyl groupδH 7.09 (2H,
s, H - 2″and H - 6″) , an ABX benzene ring with one
methoxy groupδH 3 .88 ( 3H, s, OMe) , 7 . 15 ( 1H,
d, J = 8 .8 Hz, H - 6) , 7 . 57 ( 1H, d, J = 1 .7 Hz,
H - 3) , 7 . 37 (1H, dd, J = 8 .8 , 1 .7 Hz, H - 5) , an
anomeric proton signalδH 5 .02 ( 1H, d, J = 7.7 Hz,
H - 1′) , and a glycol groupδH 5 .18 (1H , t, J = 4 .1
Hz, H - 8) , 3 . 91 (1H, m, H - 9) , 3 . 72 ( 1H, m, H
- 9 ) . The 13 C NMR spectrum and DEPT experiment
displayed twenty-three carbon signals: onemethyl , two
methylenes, eleven methines and nine quaternary car-
bons, of which the signals atδC 152 .5 ( s) , 150 .8
( s) , 112 .8 ( d) , 130 .5 ( s) , 124 .4 ( d) , 116 .2
( d) , and atδC 121 .5 (s) , 110 .4 ( d) , 146 .6 (s) ,
139 .9 (s) , 146.6 (s) , 110 .4 ( d) were attributed to
two benzene rings . In addition, 13 C NMR data gave
two carbonyl signals atδC 199 .7 ( ketone group) and
168 .0 ( galloyl group) , and one glucopyranose unit .
Acid hydrolysis of 1 afforded D-glucosewhichwas com-
pared with authentic samplesof D-glucoseby TLC . The
large3 JH1′, H2′ coupling constant ( J = 7 .7 Hz) deduced
theglucose possessed aβ- anomeric configuration . As
shown in theTable1 , the NMR spectral dataof 1 were
very similar to those of compound 2 ( Ishimaru et al. ,
1987; Saijo et al. , 1989) , which suggested that com-
pound 1 possessed theβ-D-glucopyranose unit . Simi-
larly, the same biogenetic point of view also suggested
that compound 1 and 2 had the sameβ-D-configuration
for the glucopyranose . In the HMBC spectrum
(Fig. 2 ) , the correlations between signals atδH 4 .61
( dd, J = 11 .8 , 2 .2 Hz, H - 6′) , δH 4 .36 ( dd, J =
11 .8 , 8 .0 Hz, H - 6′) andδC 168 .0 (s, C - 7″) , and
δH 5 .02 ( d, J = 7 .7 Hz, H - 1′) andδC 152 .5 (s, C
- 1) indicated that the aglycone was linked at theC -
1′position and thegalloyl group was linked at theC -
6′position of the glucose unit . The correlations be-
tween signals atδH 3 .88 (s, OMe) andδC 150 .8 (s,
C - 2) , δH 7 .09 (s, H - 2″and H - 6″) andδC 168 .0
(s, C - 7″) , δH 7 .57 ( d, J = 1 .7 Hz, H - 3 ) , δH
7 .37 ( dd, J = 8 .8 , 1 .7 Hz, H - 5 ) andδC 199 .7
(s, C - 7 ) , δH 5 .18 ( t, J = 4 .1 Hz, H - 8) andδC
199 .7 (s, C - 7) , δC 130 .5 (s, C - 4) , andδH 3 .91
( m, H - 9 ) , δH 3.72 (m, H - 9) andδC 199 .7 (s, C
- 7) , δC 75 .6 ( d, C - 8) revealed that the OMe, C -
1″, C - 4 , C - 7 and C - 8 were linked at the C - 2 , C
- 7″, C - 7 , C - 8 and C - 9 positions, respectively .
Moreover, theROESY correlationof H - 3 and H3 -OMe
supported the link order between methoxy group and
glucose unit with benzene moiety . Therefore, com-
pound 1 was elucidated as 2-methoxy-4 -( 2 , 3-di-
hydroxy-propionyl )-phenyl-1- O-( 6′- O-galloyl ) -β-D-
glucopyranoside .
Fig . 1 Structures of compounds 1 and 2
09 云 南 植 物 研 究 31 卷
Table 1 1 H and 13C NMR data ( 500 and 125 MHz, resp .) of 1 and 2 ( in CD3 OD; J values in Hz in parentheses)
No .
1 ?
δC δH
2 4
δC δH
1 ?152 4. 5 (s) 152 . 6 (s)
2 ?150 4. 8 (s) 103 .9 ( d) 6 }. 69 ( d, 2 . 8)
3 ?112 /. 8 ( d) 7 . 57 (d, 1 C. 7) 149 . 1 (s)
4 ?130 4. 5 (s) 143 . 0 (s)
5 ?124 /. 4 ( d) 7 . 37 (dd , 8 h. 8 , 1 ?. 7) 116 .0 ( d) 6 }. 61 ( d, 8 . 8)
6 ?116 /. 2 ( d) 7 . 15 (d, 8 C. 8) 110 .2 ( d) 6 }. 55 ( dd, 8 . 8 , 2 . 8)
7 ?199 4. 7 (s)
8 ?75 ?. 6 ( d) 5 . 18 (t, 4 3. 1)
9 ?66 %. 2 ( t) 3 . 91 (m) ; 3 . 72 ( m)
-OMe 56 ?. 7 ( q) 3 . 88 (s) 56 .3 (q) 3 }. 70 ( s)
Glucose
1 ?′ 101 /. 8 ( d) 5 . 02 (d, 7 C. 7) 103 .9 ( d) 4 }. 72 ( d, 7 . 7)
2 ?′ 74 ?. 7 ( d) 3 . 58 (m) 74 .9 (d) 3 }. 44 ( m)
3 ?′ 77 ?. 9 ( d) 3 . 52 (m) 77 .8 (d) 3 }. 46 ( m)
4 ?′ 72 ?. 0 ( d) 3 . 42 (m) 71 .7 (d) 3 }. 42 ( m)
5 ?′ 75 ?. 9 ( d) 3 . 81 (m) 75 .5 (d) 3 }. 71 ( m)
6 ?′ 64 %. 9 ( t) 4 . 61 (dd , 11 .8 , 2 @. 2 ) ; 64 .9 (t) 4 }. 58 ( dd, 11 ?. 6 , 2 . 2) ;
4 . 36 (dd , 11 ?. 8 , 8 @. 0 ) 4 }. 42 ( dd, 11 ?. 6 , 6 . 6)
1 ?″ 121 4. 5 (s) 121 . 3 (s)
2 ?″ 110 /. 4 ( d) 7 . 09 (s) 110 .2 ( d) 7 }. 09 ( s)
3 ?″ 146 4. 6 (s) 146 . 4 (s)
4 ?″ 139 4. 9 (s) 139 . 8 (s)
5 ?″ 146 4. 6 (s) 146 . 4 (s)
6 ?″ 110 /. 4 ( d) 7 . 09 (s) 110 .2 ( d) 7 }. 09 ( s)
7 ?″ 168 4. 0 (s) 168 . 2 (s)
Fig . 2 Key HMBC correlations of compound 1
The known compound 2 and the new compound 1
shared similar physical and spectroscopic data, except
that a 1 , 3 , 4-trisubstituted benzenemoiety instead of
a 1 , 2 , 4-trisubstituted one was located at the C - 1′
position in 2 . In addition, the 2 , 3-dihydroxy-propio-
nyl group linked at theC - 4 positionof 1 wassubstitut-
ed for the hydroxyl group of 2 . By detailed analysis of
theNMR spectroscopic dataand comparison with litera-
ture data, compound 2 was determined to be 4-
hydroxy-3-methoxy-phenyl-1- O -( 6′- O-galloyl ) -β-D-
glucopyranoside ( Ishimaru et al. , 1987; Saijo et al. ,
1989) .
Experimental
General experimental procedures TLC: visualization by
heating silica-gel platessprayed with10% H2 SO4 in EtOH . Sili-
ca gel ( 200 - 300 mesh, Qingdao Marine Chemical Inc ., Chi-
na) , Lichroprep RP-18 gel ( 40 - 63μm, Merck, Dramstadt,
Germany) and Sephadex LH-20 (Amersham Biosciences, Swe-
den) were used for column chromatography . Optical rotation was
measured on a Horbia SEPA-300 polarimeter . IR spectrumwas
obtained on a Bruker Tensor 27 instrument with KBr pellets . 1 H-
and
13
C- NMR spectra were recorded on Bruker AM-400 and
Bruker DRX-500 spectrometers in CD3 OD with TMS as an inter-
nal standard . FAB-MS was taken on a VG Auto Spec-3000 spec-
trometer, and HRESI-MS was recorded with an API QSTAR Pul-
sar 1 spectrometer .
Plant material The leaves of Cynara scolymus L . (Arti-
choke) were collected from Ho Chi Minh, Vietnam, in Februa-
ry , 2007 . The plant was identified by Hsiehs Biotech Co .,
191 期 LIU Rong et al . : Phenolic Glucoside Gallates from theLeaves of Cynara scolymus (Compositae)
Ltd . . The voucher specimen (20070208-Tony-01) was deposited
in the Herbariumof Kunming Instituteof Botany, ChineseAcad-
emy of Sciences (CAS) .
Extraction and isolation Thedried leaves of Cynara sco-
lymus L . ( Artichoke) ( 5 kg) were mashed and extracted with
75% ethanol at roomtemperature for 3×48 h . The extract was
combined and concentrated to dryness under reduced pressure .
The residue (380 g) was suspended in H2 O and partitioned, se-
quentially, with petroleumether, EtOAc, and n-BuOH . The n-
BuOH extract (60 g) was separated into nine fractions (F1 - F9 )
by column chromatography on silica gel using a CHCl3?MeOH
gradient . Thefraction F8 (6 . 1 g) eluted withCHCl3?MeOH (1∶
1 , v?v) , mainly containing the polyphenolic derivatives, were
further repeatedly separated by Sephadex LH-20 and RP-18 gel
column chromatography (MeOH?H2 O, 0∶100 - 80∶20) , afforded
thecompounds 1 (7 .0 mg) and 2 (7 .5 mg) .
Acid hydrolysis of 1 A solution of 6 mg of 1 in 0 .8 M
HCl ( 3 ml ) was heated at 90℃ for 3 h, andthereactionmixture
extracted three times with EtOAc . Afetr addition of H2 O, the
acidic solution was evaporated and then dried in vacuo to furnish
amonosaccharideresidue . Fromtheresidue, glucosewas detect-
ed by co-TLC with authentic sample .
2-methoxy-4 -( 2 , 3-dihydroxy-propionyl )-phenyl-1- O-
(6′- O-galloyl )-β-D-glucopyranoside ( 1 ) . C23 H26 O14 , white
amorphous power . [α]25D - 17°( c= 0.3 , MeOH) . IRνKBrmax cm- 1 :
3406 , 1720 , 1705 , 1612 , 1516 , 1351 . 1 H and 13 C NMR: see
Table 1 . Negative FABMS m?z 525 [M-H ] - ; HRESIMS m?z
549 .1403 [M + Na] + (calcd for C23 H26 O14 Na 549.1406) .
4-hydroxy-3-methoxy-phenyl-1- O -( 6′- O-galloyl )-β-D-
glucopyranoside ( 2 ) . C20 H22 O12 , white amorphous power .
[α]25D - 31 .3°( c= 0.5 , Me2 CO) . 1 H and13C NMR: sameas the
data reported in Ishimaru et al. (1987) and Saijo et al. (1989) .
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