全 文 :·Original Papers·
C-glycosylflavones from Stellaria media
HU Yong-Mei1 , YE Wen-Cai1 , 2* , LI Qian1 , TIAN Hai-Yan1 ,WANG Hao1 ,DU Hong-Yu3
1Department of Phytochemistry , China Pharmaceutical University , Nanjing 210009;
2 Institute of Traditional Chinese Medicine and Natural Products , Jinan University , Guangzhou 510632 ;
3Zhe Jiang Apeloa Pharmaceutical Co.Ltd , Hengdian 3221184 , P.R.China
【ABSTRACT】 AIM:To isolate the chemical constituents from the aerial parts of Stellaria media(L.)Cyr..METH-
ODS:The compounds were isolated through column chromatography and recrystallization.The structures were elucidated by
means of physio-chemical data and spectroscopy.RESULT:Fourteen C-Glycosylflavones were isolated from this plant , and
their structures were elucidated as apigenin(1), vicenin(6 , 8-di-C-β-D-glucopyranosyl apigenin)(2), 8-C-β-D-galactopy-
ranosyl isovitexin(6-C-β-D-glucopyranosyl-8-C-β-D-galactopyranosyl apigenin)(3), 6-C-β-D-galactopyranosyl vitexin (6-
C-β-D-galactopyranosyl-8-C-β-D-glucopyranosyl apigenin)(4), 6 , 8-di-C-α-L-arabinopyranosyl apigenin (5), schaftoside
(6-C-β-D-glucopyranosyl-8-C-α-L-arabinosyl apigenin)(6), isoschaftoside (6-C-α-L -arabinosyl-8-C-β-D-glucopyranosyl
apigenin)(7), 6-C-β-D-galactopyranosyl-8-C-α-L-arabinosyl apigenin(8), 8-C-β-D-galactosy l apigenin(9), vitexin(8-
C-β-D-glucopy ranosy l apigenin)(10), isovitexin(6-C-β-D-glucopyranosy l apigenin)(11), tricetin 6 , 8-di-C-β-D-glucopy-
ranosyl(12), tricetin 6-C-α-L-arabinosyl-8-C-β-D-glucopyranosyl(13)and 7-O-β-D-glucopyranosyl-6-C-β-D-6″-acetyl-
glucopyranosyl apigenin(14).CONCLUSIONS:Compounds 3~ 8 and compounds 12 and 13 have been found in the plant for
the first time , and compound 14 is a new C-glycosylflavone.
【KEY WORDS】 C-glycosylflavones;Stellaria media(L.)Cyr.
【CLCNumber】 R284.1 【Document code】 A 【Ariticle ID】 1672-3651(2006)06-0420-05
【Received on】 2006-04-05
【* Corresponding author】 Ye Wen-Cai:Professor , Tel:(86)-25-
85322132 , E-mail:clcywc@yahoo.com.cn
1 Introduction
Stellaria media(L.)Cyr.is a Chinese material
medicine for folk use , which shows very effective anti-
inflammatory and antiviral activities[ 1] .Our chemical
researches about the plant provide a substantial base for
the studies of its activities.On the other hand , the
plant belongs to Caryophyllaceae , which is characteristic
in containing typical C-glycosylflavones.Our discovery
about 14 C-glycosylflavones from the plant further sup-
ported the viewpoint about the Plant Chemotaxonomy of
this distinct group of Caryophyllaceae
[ 2] .
2 Results and Discussion
The 95%ethanolic extract of the aerial parts of S .
media was partitioned successively with petroleum
ether , ethyl acetate , saturated aqueous n-butanol and
water.The EtOAc and BuOH soluble fractions were
subjected to repeated column chromatography to afford
fourteen compounds.
On the basis of spectroscopic and physio-chemical
data , compounds 1 ~ 13 were identified as apigenin[3 , 4]
(1), vicenin(6 , 8-di-C-β-D-glucopyranosyl apigenin)[ 5]
(2), 8-C-β-D-galactopyranosyl isovitexin(6-C-β-D-glu-
copyranosyl-8-C-β-D-galactopyranosyl apigenin)[6 , 7](3),
6-C-β-D-galactopyranosyl vitexin (6-C-β-D-galactopyra-
nosyl-8-C-β-D-glucopyranosyl apigenin)[ 7] (4), 6 ,8-di-
C-α-L-arabinopyranosyl apigenin[ 8 ,9](5), schaftoside (6-
C-β-D-glucopyranosyl-8-C-α-L-arabinosyl apigenin)[ 9-11]
(6), isoschaftoside(6-C-β-D-arabinosyl-8-C-β-D-glu-
copyranosyl apigenin)[ 10](7), 6-C-β-D-galactopyranosyl-
8-C-β-D-arabinosyl apigenin[12](8), 8-C-β-D-galactosyl
apigenin[ 13] (9), vitexin(8-C-β-D-glucopyranosyl api-
genin)[ 14](10), isovitexin (6-C-β-D-glucopyranosyl api-
genin)[ 15] (11), tricetin 6 , 8-di-C-β-D-glucopyra-
nosyl[16 ,17](12)and tricetin 6-C-arabinosyl-8-C-β-D-glu-
copyranosyl
[ 17](13).These glycosides except compounds
1 ,2 ,9 ,10 have not been reported previously from S.me-
dia.
Compound 14was obtained as pale amorphous yel-
420 Chin J Nat Med Nov.2006 Vol.4 No.6 2006年 11月 第 4卷 第 6期
low powders (EtOH).The chromatographic and UV
spectral data of compound 14 closely resemble those of
apigenin[ 3] .Assignment of the molecular formula
C29H32O16 was based on the
1H NMR , 13C NMR and
HRESIMS(m/z [ M +Na] + 656.122 5 , calcd.for
656.145 5) spectral data.The IR (KBr) spectrum
showed bands at 3 353 cm-1(hydroxyl), 1 657 and 1 575
cm-1.The 1H NMR spectra of aglycone moiety in com-
pound 14 were similar to those in compound 11with the
absence of H-6 signal , the presence of singlets at δ6.
79 (1H , s , H-3)and δ6.93 (1H , s , H-8), two
doublets at δ7.93 (H-2′, H-6′)and δ7.23(H-3′,
H-5′), suggesting a 6-C-glycosyl substituted apigenin
structure.The deduction was further supported by the
13
C NMR spectral data(Table 1)between δ182.1 and
94.2 , the carbon signals of C-6(δC 110.7)was down-
field shift +11.8 from C-glycosylation compared with
apigenin (δC 98.9).
The 13C NMR spectral data showed signals for one
C-glucosyl residue at δ73.4(1″), 69.9(2″), 77.6
(3″), 68.6(4″), 78.9(5″), 65.3(6″), which may be
substituted at C-6 position and for one O-glucosyl
residue atδ104.8 , 74.5 , 76.2 , 71.5 , 76.4 , 61.0.
The hydroxyl proton signals atδ13.77(1H , s , 5-OH)
and 9.03(1H , s , 4′-OH)and the down field shift
+2.5 of C-7(δC 163.8)compared with apigenin (δC
162.3)imply the O-glucosyl residue may be substituted
at the 7-hydroxyl group of isovitexin.
Two carbon signals were observed at δC 171.5 ,
22.3 , and the methyl proton signal at δH 1.80(3H , s ,
CH3) present one acetyl group.Furthermore , the
13C NMR spectral comparison of compound 14 with iso-
vitexin 11(Table 2)showed the acetyl group is specifi-
cally located at 6″-position of the glucose moiety.Thus ,
there is the expected downfield shift[ 18 , 19] of 4.8 of the
C-6″resonance in compound 14 compared with 11 , with
a concomitant upfield shift of 2.8 of the C-5″signal.
The complete assignment of the signal of compound
14 was based on 2D NMR and chemical experiments.
The HMBC correlation between H-6″(δH 3.62 , Glc″)
and C =O (δC 171.5 acetyl)further indicated the
acetyl group was substituted at C-6″(δC 65.3)of the
C-glucosyl group.Similarly , the correlation between H-
1 (δH 4.86)and C-7(δC 163.7)further confirmed an-
other glucose linked at 7-hydroxyl group of compound
14.Prolonged acid hydrolysis only produced the glucose
in water solution (TLC analysis), and the aglycone in
the n-BuOH extraction.The NMR spectra and R f val-
ues of aglycone resembled those of compound 11 , con-
firming one glucose moiety was substituted at C-6 ,
which was consistent with the correlations of H-1″
(δ3.65)to C-5(δ159.1)and C-6(δ110.7).Thus
compound 14 was elucidated as 7-O-β-D-gluco-pyra-
nosyl-6-C-β-D-6″-acetyl-glucopyranosyl apigenin ,which
is a new compound.
R1 R2 R3 R4
1 H H H H
2 Glc H Glc H
3 Glc H Gal H
4 Gal H Glc H
5 Ara H Ara H
6 Glc H Ara H
7 Ara H Glc H
8 Gal H Ara H
9 H H Gal H
10 H H Glc H
11 Glc H H H
12 Glc H Glc OH
13 Ara H Glc OH
14 Glc-6″acety l Glc H H
Fig 1 The structures of compounds 1-14
Fig 2 The key HMBC correlations of compound 14
3 Experimental
3.1 General Experimental Procedures
HP5989A instrument;Bruker ACF-300 and Bruk-
er ACF-400 instrument(TMS was used as an internal
standard);Shimadzu UV-2501 PC spectrophotometer;
X-4 micro-melting point apparatus (uncorrected);
TLC:Silica gel 60GF254 , made in Chemical Factory of
Yantai;LC:Silica gel 200 ~ 300 mesh and silica gel
400 ~ 500 mesh (Ocean Chemical Factory of Qing-
dao);RP-18 F254HPTLC and ODSwere made in Merck
company;Sephadex LH-20 Pharmacia company;All
reagents were of analytical pure grade.
3.2 Plant material
The herbal pieces were obtained from Nanjing in
November of 2004 , and authorized by Professor Chen
Chongming , Institute of Botany , Jiangsu Province , P.
R.China.
2006年 11月 第 4卷 第 6期 Chin J Nat Med Nov.2006 Vol.4 No.6 421
3.3 Extraction and Isolation
The air-dried plant material (2 kg)of Stellaria
media was extracted with 95%EtOH.The concentrated
solution was partitioned with petroleum ether , EtOAc
and n-BuOH , successively.The EtOAc soluble fraction
(20 g)was adsorbed on polyamide and applied in H2O
to a polymide column (5 cm ×60 cm).Elution was
carried out with H2O , followed by 30% MeOH and
MeOH.Pure compounds 1 (50 mg)was obtained by
column chromatography (Si gel), compound 9(8mg),
compounds 10(12 mg)and 11(6 mg)were obtained
by repeated , combined CC , PC and PLC methods.The
crystallization , with compound 1 was done from MeOH-
EtOAc and EtOH-H2O , respectively.Other individual
compounds from n-BuOH-soluble fraction (87 g)were
achieved by repeated silica gel , polymide , ODS
columns.Pure compound 2(10 mg), 3(8 mg), 4(5
mg)and 5(6 mg)were further obtained by preparative
HPLC methods (12 %CH3CN).Two isomers 6 (10
mg), 7(8 mg)and compound 8(4 mg)were obtained
from 10 %CH3CN fraction throughHPLC.Two isomers
12(8 mg)and 13 (4 mg)were also obtained by
preparative HPLC methods(8 %CH3CN).
Chromatography-CC:Cellulose microcrystalline for
CC , Merck (solvents:3% up to 20% HOAc),
Sephadex LH-20(solvent:20%MeOH , 60%MeOH ,
80%MeOH), Silica gel(CH3Cl-MeOH-H2O);TLC:
cellulose(3%up to 20%HOAc), silica gel(CH3Cl-
MeOH-H2O , BAW , TBA), Polymide (MeOH-H2O
10%~ 60%);PC:Whatman No.3 paper(H2O , 15%
HOAc , BAW).
3.4 Hydrolysis procedures
Acid hydrolysis:The pure compounds were treated
with 2 mol·L-1 HCl at 100 ℃ for 2 h.Hydrolysates
were extracted with EtOAc (aglycones), then n-BuOH
(C-glycoside).Sugars were identified with authentic
sugars in aqueous residue by CC.
3.5 Structure Elucidation
Compound 3 Light yellow needles(MeOH), C27
H30O15 , ESI-MS m/z 595.1 [M +H] + , mp 232 ~
234 ℃, UV (MeOH)λmax 270 , 331 nm.1H NMR
(400MHz , DMSO-d6):δ13.80(1H , s , 5-OH), 10.
34(1H , s , 7-OH), 9.18(1H , s , 4′-OH), 7.99
(2H , d , J =8.8 Hz , H-2′, 6′), 6.90(2H , d , J
=8.8 Hz H-3′, 5′), 6.78(1H , s H-3), 3.30 ~ 5.00
(22H , hexosyl residues).
Compound 4 Light yellow needles(MeOH), C27
H30O15 , ESI-MS m/z 595.1 [M+H] + , UV(MeOH)
λmax 270 , 331 nm.1H NMR(400 MHz , DMSO-d6):
δ13.80(1H , s , 5-OH), 10.34(1H , s , 7-OH), 9.
18(1H , s , 4′-OH), 7.99(2H , d , J =8.8 Hz , H-
2′, 6′), 6.90(2H , d , J =8.8Hz H-3′, 5′), 6.78
(1H , s H-3), 3.30 ~ 5.00(22H , hexosyl residues).
Compound 5 Light yellow needles(MeOH), C25
H26O13 , ESI-MS m/z 533.1 [ M-H] - , 1H NMR(400
MHz , DMSO-d6):δ13.70(1H , s , 5-OH), 10.30
(1H , s , 7-OH), 9.17(1H , s , 4′-OH), 7.99(2H ,
d , J = 8.8 Hz H-2′, 6′), 6.88 (2H , d , J =
8.8 Hz , H-3′, 5′), 6.76(1H , s H-3), 3.30 ~ 4.82
(18H , hexosyl residues).
Compound 6 Amorphous yellow powders
(MeOH), C26 H28 O14 , ESI-MS m/z 565.1 [ M +
H] + , UV (MeOH)λmax 271 , 332 nm.1H NMR(400
MHz , DMSO-d6):δ13.70(1H , s , 5-OH), 10.30
(1H , s , 7-OH), 9.17(1H , s , 4′-OH), 7.99(2H ,
d , J =8.8 Hz H-2′, 6′), 6.88 (2H , d , J =
8.8 Hz , H-3′, 5′), 6.76(1H , s H-3), 3.30 ~ 4.82
(18H , hexosyl residues).
Table 1 13C NMR data of aglycone moieties in compounds 1~ 13(DMSO-d6 , δ)
C 1 2 3 4 5 6 7 8 9 10 11 12 13
2 164.1 164.5 164.0 164.1 164.0 164.0 163.7 164.0 164.0 164.2 164.0 164.0 164.0
3 102.9 103.1 102.7 103.1 102.5 102.2 101.9 103.0 102.8 103.2 102.8 102.4 102.9
4 181.8 182.1 182.4 182.4 182.1 182.0 181.2 182.1 182.2 182.1 182.1 182.1 182.2
5 161.5 159.1 159.1 159.0 159.1 159.1 158.1 159.0 159.4 159.1 159.1 158.6 159.1
6 98.9 109.0 109.5 108.3 108.5 108.0 108.2 108.9 99.0 98.2 109.1 108.6 108.5
7 163.8 162.1 161.3 161.4 162.4 162.0 161.1 161.2 161.0 162.0 161.0 161.0 161.1
8 94.0 104.9 103.8 104.6 104.1 104.2 104.8 104.5 104.8 104.9 94.8 104.6 104.8
9 157.3 155.4 154.2 155.1 156.0 154.6 154.1 154.1 155.8 155.6 153.8 159.1 156.1
10 103.8 103.7 103.8 103.8 104.1 103.8 103.4 103.8 103.7 103.7 103.5 103.4 102.8
1′ 121.2 122.1 121.3 121.4 121.1 121.1 122.1 122.1 122.1 122.1 121.5 120.5 120.4
2′ 128.5 130.1 129.1 128.7 129.0 129.0 129.0 129.0 130.1 130.1 128.8 105.8 105.9
3′ 116.0 115.4 116.2 116.4 115.8 115.8 115.4 115.8 115.4 115.4 115.8 148.8 148.8
4′ 161.2 161.8 162.0 162.0 160.4 161.0 161.8 161.8 161.8 161.4 161.4 140.1 140.1
5′ 116.0 115.4 116.2 116.4 115.8 115.8 115.4 115.8 115.6 115.4 115.8 148.8 148.8
6′ 128.5 130.1 129.1 128.7 129.0 129.0 129.0 129.0 130.2 130.1 128.8 105.8 105.9
422 Chin J Nat Med Nov.2006 Vol.4 No.6 2006年 11月 第 4卷 第 6期
Table 2 13C NMR data of sugar residue of compounds 2 ~ 13(DMSO-d6 , δ)
C 2 3 4 5 6 7 8 9 10 11 12 13
C-6 glc glc gal arab glc arab gal glc glc arab
1 74.8 73.7 73.2 73.6 73.6 74.5 73.8 73.7 74.8 74.1
2 71.1 70.8 68.9 68.8 69.0 73.6 69.4 69.0 71.1 68.3
3 77.8 79.1 75.5 74.9 79.1 70.8 75.0 79.2 77.8 75.0
4 69.3 68.4 68.8 69.8 68.5 70.6 68.2 68.5 69.3 68.9
5 82.1 81.8 78.5 71.0 81.7 68.1 79.0 81.7 81.7 71.0
6 61.1 61.3 60.3 60.7 60.7 60.8 61.1
C-8 glc gal glc arab arab glc arab gal glc glc glc
1 73.5 74.5 73.3 73.6 73.9 73.2 73.9 74.7 73.6 73.5 73.8
2 70.9 70.7 70.2 68.4 68.1 69.7 68.1 69.0 69.2 70.9 69.1
3 78.1 73.2 78.5 74.4 74.6 79.0 74.6 73.6 79.8 78.1 79.0
4 69.1 69.7 69.3 70.8 69.1 68.4 69.1 68.5 68.4 69.1 68.7
5 81.9 79.0 81.6 72.7 71.0 81.8 71.0 79.1 81.6 81.9 81.2
6 61.1 60.8 60.9 60.8 60.7 60.7 61.1 61.7
Table 3 The full assignment of carbons and proton signals of
compound 14
Position δC δH(mult , J HZ) HMBC(H to C)
2 164.1
3 103.1 6.78(s) C-2 , 4, 10 ,1′
4 182.1
5 159.1
6 110.7
7 163.7
8 94.2 6.83(s) C-6 , 7, 9 , 10
9 156.5
10 103.2
1′ 120.9
2′ 128.5 7.93(d ,8.8) C-2′, 4′,3′, 5′, 6′
3′ 116.0 7.23(d ,8.8) C-1′, 4′,3′, 5′
4′ 161.4
5′ 116.0 7.23(d ,8.8) C-1′, 4′,3′, 5′
6′ 128.5 7.93(d ,8.8) C-2′, 4′,3′, 5′, 6′
Sugar
Glc″
1″ 73.4 3.63(d ,7.8) C-6 , 2″
2″ 69.9 3.20(t , 7.8) C-1″
3″ 77.6 3.50(m)
4″ 68.6 3.81(m)
5″ 78.9 4.66(m) C-6″
6″ 65.3 3.62(m) C=O ,C-5″
C=O 171.5
-CH3 22.3 1.80(s) C=O
Glc
1 104.8 4.86(d ,7.8) C-2
2 74.5 3.45(m) C-3
3 76.2 3.10(m) C-4
4 71.5 3.21(m) C-5
5 76.4 3.35(m)
6 61.0 3.18(m) C-5
*Measured in DMSO-d6.Assignments were established by DEPT , 1H-
1H COSY , HMQC and HMBC experiments.J values (in Hz) are in
parentheses.
Compound 7 Amorphous yellow powders
(MeOH-H2O), C26H28O14 , ESI-MS m/z 565.1 [M+
H] + , UV (MeOH)λmax 274 , 336 nm.1H NMR(400
MHz , DMSO-d6):δ13.70(1H , s , 5-OH), 10.30
(1H , s , 7-OH), 9.17(1H , s , 4′-OH), 7.99(2H ,
d , J =8.8 Hz , H-2′, 6′), 6.88(2H , d , J =8.8
Hz , H-3′, 5′), 6.76(1H , s H-3), 3.30 ~ 4.82(18
H , hexosyl residues).
Compound 8 Amorphous yellow powders(EtOH-
H2O), C26H28O14 , ESI-MS m/z 565.1 [M+H] + ,
UV(MeOH)λmax 274 , 282 , 332 nm.1H NMR(400
MHz , DMSO-d6):δ13.70(1H , s , 5-OH), 10.30
(1H , s , 7-OH), 9.17(1H , s , 4′-OH), 7.99(2H ,
d , J =8.8 Hz , H-2′, 6′), 6.88(2H , d , J =8.8
Hz , H-3′, 5′), 6.76(1H , s H-3), 3.30 ~ 4.82
(18H , hexosyl residues).
Compound 12 Amorphous yellow powders (E-
tOH), C27H30O17 , ESI-MS m/z 627.1 [M +H] + ,
UV(MeOH)λmax 275 , 360 nm.1H NMR:δ6.79
(1H , s , H-3), 7.01 (2H , ws , H-2′, 6′), 13.77
(1H , s , 5-OH), 10.2(1H , s , 7-OH), 9.03(1H , s ,
4′-OH), 8.21(2H , s , 3′, 5′-OH).
Compound 13 Amorphous yellow powders (E-
tOH), C26H28O16 , ESI-MS m/z 595 [M-H] - , UV
(MeOH)λmax 275 , 356 nm.1H NMR:δ6.78(1H ,
s , H-3), 7.03(2H , ws , H-2′, 6′), 13.77(1H , s ,
5-OH), 10.2(1H , s , 7-OH), 9.03(1H , s , 4′-OH)
and 8.21(2H , s , 3′, 5′-OH).
Compound 14 Amorphous yellow powders (E-
tOH-H2O);mp 283 ~ 285 ℃;UV(MeOH)λmax 271 ,
330 nm;+NaOAc 277 , 350;+ AlCl3 279 , 305 ,
348 , 381;+ AlCl3 +HCl 280 , 304 , 344 , 381;
HRESI MS(m/z [M +Na] + 656.122 5 , calcd.for
656.145 5), ESIMS m/z 605 [M-H] - , C28H30O15 ,
1H NMR:δ6.79(1H , s , H-3), 6.93 (1H , s , H-
8), 7.93(H-2′, H-6′), 7.23(H-3′, H-5′).
2006年 11月 第 4卷 第 6期 Chin J Nat Med Nov.2006 Vol.4 No.6 423
References
[ 1] Zhou RH , Duan JA.Plant chemotaxonomy[ M] .Sanghai:Sciences
and Technology Press , 2005 ,10:1.
[ 2] Pande A , Shukla YN , Tripathi AK , et al.Lipid constituents from
Stellaria media[ J] .Phytochemistry , 1995 , 39(3):709-711.
[ 3] Mabry TJ , Markham KR , ThomasMB.The systematic identification
of flavonoids [M] .New York , 1970.
[ 4] Lin L , Xie N , Cheng ZH.Flavonoids from Cajanus cajan L.[ J] .J
China PharmUniv , 1999 , 30(1):21-23.
[ 5] Zhang ML , Li ZP , Jia XM. Study on chemical constituents of
Urtica cannabina L.[ J] .Nat Prod Res Dev , 2005 , 17(2):175-
176.
[ 6] Chop J , Boui llant ML.Besson E.The flavonoids advances in
research[M] .Harborne JB and Mabry TJ , Chapman &Hall , Lon-
don , 1982:449.
[ 7] Dubois MA , Zoll A , Markham KR , et al.6-C-β-D-gluco-
pyranosyl-8-C-β-D-galactopyranosyla pigenin from Ceratium arvense
[ J] .Phytochemistry , 1984 , 23(3):706-707.
[ 8] Osterdahl BG.Ph D.thesis , Act.Univ.Upsaliensis , 1979:516.
[ 9] Renate T , Kenneth R.The structures of new flavone di-C-
glycosides from Apometzgeria pubesscens[ J] .Phytochemistry , 1981 ,
20(6):1457-1458.
[ 10] Besson E , Dombris A , Raynaud J , et al.Corymboside , nouvelle
di-C-glycosylflavone des Racines de carline corymbosa[ J] .Phyto-
chemistry , 1979, 18:1899-1900.
[ 11] Zhang YM , Xu XD , Hu BH , et al.Isof lavones from Glycyrrhiza
eurycarapu[ J] .Acta Pharm Sin , 1977 , 32(4):301-304.
[ 12] Chopin J , Dellamonica G , Besson E , et al.C-galactosylf lavones
from Polygonatum multiflorum [ J] .Phytochemistry , 1977 , 16:
1999-2001.
[ 13] Chari VM , Harborne JB , Williams CA.Identification of 6″-O-
acetyl-8-C-galactosylapigenin in Briza media[ J] .Phytochemistry ,
1980 , 19:983-984.
[ 14] Huang WZ , Li YH , Zhang WD , et al.Studies on chemical con-
stituents of Malachium aquaticum (L.)Fries[ J] .Res Pract Chin
Med , 2005, 19(5):27-28.
[ 15] Li W , Chen FK , Yi XW , et al.Chemical constituents of Folium
isatidis[ J] .J Shenyang Pharm Univ , 2005 , 22(1):15-17.
[ 16] Mues R , Zinsmeister HD.Flovonoids of Plagiochi la [ J] .Phyto-
chemistry , 1976, 15:1757-1760.
[ 17] Theodor R , Zinsmeister HD , Mues R , et al.Flavone C-glycosides
of Apometzgeria pubescens.[ J] .Phytochemistry , 1980 , 19:1695-
1700.
[ 18] Chari VM , Wagner H , Neszmelyi A.Flavonoids and bioflavonoids.
Akademiai Kiado , Budapest.1977.
[ 19] Markham KR , Ternai B , Stanley R , et al.Carbon-B NMR studies
of flavonids-Ⅲ.Tetrahedron , 1978 , 34:1389-1397.
繁缕中的黄酮碳苷类化合物
胡永美1 ,叶文才1 , 2* ,李 茜1 ,田海妍1 ,汪 豪1 ,杜红玉3
1中国药科大学天然药物化学教研室 ,南京 210009;
2暨南大学中药及天然药物研究所 ,广州 510632;
3浙江普洛康裕制药有限公司 ,浙江 横店 3221184
【摘 要】 目的:研究繁缕中的黄酮类化合物。方法:95%的乙醇提取物的水混悬液依次用石油醚 、乙酸乙酯和正丁
醇萃取 ,各种柱层析进行分离纯化 , UV , NMR 等波谱数据进行结构鉴定。结果:从中分离得到 14 个黄酮碳苷类化合物 , 其
结构鉴定为:芹菜素(apigenin)(1),芹菜素-6 , 8-二-C-β-D-吡喃葡萄糖苷(2), 即新西兰牡荆苷-2[ vicenin-Ⅱ (6 , 8-二-C-β-D-
glucopyranosyl apigenin)] , 芹菜素-6-C-β-D-葡萄糖-8-C-β-D-半乳糖苷(8-C-β-D-galactopy ranosy lisovitexin (6-C-β-D-glucopyra-
nosyl-8-C-β-D-galactopyranosyl apigenin)(3),芹菜素-6-C-β-D-半乳糖-8-C-β-D-葡萄糖苷(6-C-β-D-galactopyranosylvitexin 6-C-β-
D-galactopyranosyl-8-C-β-D-glucopyranosyl apigenin)(4), 芹菜素-6 , 8-二-C-α-L-阿拉伯糖苷(6 , 8-di-C-α-L-arabinopyranosyl api-
genin)(5),芹菜素-6-C-β-D-葡萄糖-8-C-α-L-阿拉伯糖苷[ schaftoside(6-C-β-D-glucopyranosyl-8-C-α-L-arabinosyl apigenin)](6),
芹菜素-6-C-α-L-阿拉伯糖-8-C-β-D-葡萄糖苷[ isoschaftoside(6-C-α-L-arabinosyl-8-C-β-D-glucopyranosyl apigenin)] (7),芹菜素-
6-C-β-D-半乳糖-8-C-α-L-阿拉伯糖苷(6-C-β-D-galactopyranosyl-8-C-α-L-arabinosyl apigenin)(8), 芹菜素-8-C-β-D-半乳糖(8-
C-β-D-galactosyl apigenin)(9),牡荆素[ vitexin(8-C-β-D-glucopyranosyl apigenin)] (10), 异牡荆素[ isovitexin(6-C-β-D-glucopyra-
nosyl apigenin)] (11),麦黄酮-6 , 8-二-C-β-D 葡萄糖苷(tricetin 6 , 8-di-C-β-D-glucopyranoside)(12),麦黄酮-6-C-α-L-阿拉伯糖-8-
C-β-D-葡萄糖苷[ tricetin 6-C-α-L-arabinosyl-8-C-β-D-galactopyranoside](13), 7-O-β-D-葡萄糖基-6-C-β-D-葡萄糖(6″-乙酰基)
芹菜素[ 7-O-β-D-glucopy ranosyl-6-C-β-D-6″-acetyl-glucopy ranosyl apigenin](14)。结论:9个化合物(3 ~ 8 及 12、13)为首次从该
植物中分离得到 ,化合物 14 为新化合物。
【关键词】 黄酮碳苷;繁缕
424 Chin J Nat Med Nov.2006 Vol.4 No.6 2006年 11月 第 4卷 第 6期