全 文 ：A Monoterpene Glycoside from Ehinacea purpurea
LI Ji-ren , BAI Yan-jing , WANG Bin , CHEN Gang , AI Tie-min , and ZHAO Yu-ying＊
(Department of Natural Medicines , School of Pharmaceutical Sciences ,
Peking University , Beijing 100083 , China)
Abstract:Aim　To separate and identify chemical constituents of Ehinacea purpurea.Methods　Five compounds
were isolated from the plant using chromatography.Their structures were elucidated by spectroscopy.Results　Five com-
pounds were isolated and their structures were identified as 2 , 6-dimethyl-7-octene-2 , 3 , 6-triol-2-O-β-D-glucopyranoside
(1), 7 , 8-furocoumarin(2), 6-methoxy-7-hydroxycoumarin(3), caffeic acid(4), methyl caffeate(5), and ethyl caffeate
(6).Conclusion　All these compounds were obtained from the plant for the first time.
Key words:Echinacea purpurea ;monoterpene glycoside;2 , 6-dimethyl-7-octene-2 , 3 , 6-triol-2-O-β-D-glucopyrano-
side
CLC number:R284.1;R284.2　　　Document code:A　　　Article ID:1003-1057(2003)04-181-03
Introduction
Echinacea purpurea (L.)Monech , which is native
in west and west-central America and has been cultivated
in many other places , has been widely used as anti-in-
flammatory and anti-infective agents.Its constituents and
bioactivities have been extensively studied especially in
Germany since 1980s.Previous chemical investigations
have shown that alkylamides
[ 1] , phenylpropanoids and
sesquiterpenoid have been isolated from Echinacea pur-
purea (L.)Monech[ 1 , 2] .This paper reports the isolation
and identification of 6 compounds from it.Their structures
were elucidated as 2 , 6-dimethyl-7-octene-2 , 3 , 6-triol-
2-O-β-D- glucopyranoside (1), 7 , 8-furocoumarin (2),
6-methoxy-7-hydroxycoumarin (3), caffeic acid (4),
methyl caffeate(5), and ethyl caffeate (6)by spectros-
copy.These compounds were obtained from the plant for
the first time.
Results and Discussion
Compound 1 was obtained as white powder.Acidic
hydrolysis on TLC gave glucose , which was identical with
authentic sample.The 1H NMR spectrum showed an ano-
meric proton atδ4.33(1H , d , J =8.0 Hz , glc 1-H)
Received date:2003-07-20.
＊Corresponding author:Tel 010-82801592 , Fax 010-82801592 ,
E-mail nmechem@bjmu.edu.cn
and other protons at δ2.9-3.6.13 C NMR showed a
group of signals attributable to glucose (Table 1).The
NMR data indicated that 1 was a glucoside and a β-con-
figuration for glucose was determined.1H NMR spectrum
also showed three methyl signals:δ1.05 , 1.10 , 1.14
(each 3H , s), three olefinic proton signals at δ4.91
(1H , dd , J =2.0 , 11.0 Hz), 5.09 (1H , dd , J =
2.0 , 17.5 Hz), and 5.85 (1H , t , J =11.0 , 17.5
Hz).In the 13C NMR spectrum of 1 ten signals for agly-
cone were observed.These results indicated that 1 is
monoterpene glycoside.
The numbers of all carbons from upfield to downfield
were assigned from a to p.The proton assignments were
based on HMQC and DEPT experiments(Table 1).The 1H-
1
H COSY spectrum correlated olefinic protons H2-o with H-
p , and methylene protons H2-e withH2-c(Figure 1).
Its HMBC spectrum showed the following
1
H
13
C
long-range correlations(Figure 1):(A)H3-d , H2-e and
OH with C-p(δ146.55);(B)from anomeric protonH-n
Figure 1　HMBC(→)and H-H COSY( )of A and B
181Journal of Chinese Pharmaceutical Sciences 2003 , 12(4)
Table 1　The data of NMR(DMSO-d6)
No. 13C NMR 1H NMR　　　　
1(b) 22.19　　CH3 1.05(3H , s)
2(m) 79.21　　C
3(j) 75.14　　CH 3.29(1H , s)
4(c) 25.32　　CH2 1.43 , 1.16(each 1H , m)
5(e) 39.61　　CH2 1.71(1H , dt , J =8.0 , 12.5 Hz)1.35(1H , br.t , J =12.5 Hz)
6(h) 71.41　　C
7(p) 146.55　　CH 5.85(1H , t , J=11.0 , 175 Hz)
8(o) 110.59　　CH2 5.09(dd , J=2.0 , 17.5 Hz , trans-7-H), 4.91(dt , J =2.0 , 11.0 Hz , cis-7-H)
2-CH3(a) 21.97　　CH3 1.10(3H , s)
6-CH3(d) 27.97　　CH3 1.14(3H , s)
glc-1((n) 96.10　　CH 4.33 , (1H , d , J=8.0 Hz)
2′(i) 73.66　　CH
3′(k) 76.53　　CH
4′(g) 70.14　　CH
5′(l) 76.77　　CH
6′(f) 61.04　　CH2
Figure 2　Structure and FAB-MS of 1
(δ4.33)with C-m(δ79.21);from H-j with methyl carbons
C-a , C-b and C-m , and led to establish the two partial
structures A and B (Figure 1).Connection between partial
structures A and B was confirmed by the correlation between
H2-e and C-j(Figure 1)in HMBC spectrum.
The structure of 1 was determined as 2 ,6-dimethyl-7-
octene-2 , 3 , 6-triol-2-O-β-D-glucopyranoside(Figure 2).
The FAB-MS m z (%)showed quasi molecular ion
peak at m z 351[M+1] + and fragment ions at 171 [M-
179] (6), 153 [M-179-H2O] (100), 163 [ glc] (5),
losing one glucose unit , followed by H2O;it supported
the structure of 1.The above data of NMR and MS were
in agreement with those of 6 ,7-dihydroxy- dihydrolinalool-
7-O-β-glucopyranoside[ 4] .
Experimental
General experimental procedures
Melting points were measured with an X4 micromelting
point apparatus and with an uncorrected thermometer.NMR
was recorded in DMSO-d6 with a BrukerAm-500 instrument.
MS spectrum was recorded on a Zabspece FAB-MS instru-
ment.For column chromatography , silica gel(Marine Chem-
ical Plant , Qingdao), Sephadex LH-20(Amersham Pharma-
cia Biotech AB , Sweden), and RP-18(The Great Eur-Asia
Sci.and Development Co.LTD)was used.
Plant material
The aerial parts of Echinacea purpurea(L.)Monech
were collected in Beijing and identified by Prof.Ai Tie-
min , School of Pharmaceutical Sciences , Peking Univer-
sity.A voucher specimen has been deposited in the her-
barium of the Department of Natural Medicines , School of
Pharmaceutical Sciences , Peking University.
Extraction and isolation
The powdered aerial parts of the plant (10.5 kg)
were extracted with 95%EtOH at room temperature.The
extract was concentrated under reduced pressure and di-
luted with H2O.The aqueous solution was extracted with
P.ether , EtOAc and n-BuOH , successively.The P.
ether extract was separated using silica gel column chrom-
atography (P.ether∶acetone=7∶3)to give 2.The EtO-
Ac extract was subjected to RA macroporous resin col-
umn , eluted with 95%EtOH , followed by repeated silica
gel column and PTLC [ P.ether-EtOAc(100∶0※80∶2),
CHCl3-MeOH(100∶0※90∶10)] to obtain 3-6.The n-
BuOH extract was chromatographed on D 101 macroporous
resin column , eluted with H2O , 30%, 50% and 70%
182 Journal of Chinese Pharmaceutical Sciences 2003 , 12(4)
EtOH , the H2O-eluted fractions(12 g)was subjected to
repeated chromatography on Rp-18 silica column eluted
with H2O , 20%MeOH and on Sephadex LH-20 column
eluted with 10%MeOH to give compound 1(30 mg).
Identification
Compound 1 was obtained as white powder , mp
94-96℃.Acidic hydrolysis on TLC gave glucose which
was identical with authentic sample.The data of 1H NMR
and
13
C NMR are shown in(Table 1).
Compound 2　White powder , 1H NMR(CDCl3):δ
7.79(1H , d , J =9.6 Hz , 4-H), 6.38(1H , d , J =
9.6 Hz , 3-H), 7.36(1H , d , J =8.7 Hz , 5-H), 7.42
(1H , d , J =8.7 Hz , 6-H), 7.68 (1H , d , J =2.1
Hz , a-H), 7.12(1H , d , J =2.1 Hz), b-H).All the
data are in agreement with 7 , 8-furocoumarin[ 4] .
Compound 3　White powder , 1H NMR(CDCl3):δ
6.2(1H , d , J =9.6 Hz , 3-H), 7.8 (1H , d , J =
9.6Hz , 4-H), 7.1(1H , s , 5-H), 6.7(1H , s , 8-H),
3.8 (3H , s , OCH3).13 C NMR (CDCl3):δC2-C10
164.1 , 112.4 , 147.1 , 112.4 , 146.1 , 153.1 , 103.9 ,
151.1 , 109.8.All the data are in agreement with 6-me-
thoxy , 7-hydroxycoumarin.
Compound 4　Caffeic acid , white powder , 1H NMR
(DMSO):δ6.1(1H , d , J =15.6 Hz), 7.3(1H , d ,
J =15.6 Hz), 6.7(1H , d , J =8.1 Hz), 6.8 (1H ,
d , J =8.1 Hz), 7.3(1H , d , J =1.8 Hz).IR(KBr)
cm
-1:1 712(COOH), 3 265(OH).
Compound 5　Methyl caffeate , white powder , 1H
NMR(CDCl3):δ3.8(3H , s , OCH3), 6.2(1H , d ,
J =15.6 Hz), 7.4(1H , d , J =15.6 Hz), 7.2(1H ,
d , J =1.8 Hz), 7.0(1H , dd , J =1.8 , 8.1Hz), 6.7
(1H , d , J =8.1 Hz).FAB-MS m z:194(M +), 179
(M +-CH3), 145(M +-CH3-2 OH).
Compound 6　Ethyl caffeate , white powder , 1H NMR
(CDCl3):δ1.3(3H , t , CH3), 4.2(2H , q , CH2), 6.3
(1H , d , J =15.9 Hz), 7.5(1H , d , J =15.9 Hz), 6.8
(1H , d , J =8.1 Hz), 7.0(1H , dd , J =2.1 , 8.1 Hz),
7.5 (1H , d , J =2.1 Hz).13 C NMR (CDCl3):δ14.2
(CH3), 60.6(CH2), 167.0 , 115.6 , 145.5 , 127.5 , 115.0 ,
146.2 , 148.7 , 116.2 , 122.4.
References
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from fresh aerial parts of Echinacea purpurea [ J] .Planta
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[ 3] Perry NB , Klink JW , Burgess EJ , et al.Alkamide levels in
Echinacea purpurea:a rapid analytical method revealing differ-
ences among roots , rhizomes , stems , leaves and flowers [ J] .
Planta Med , 1997 , 63:58-62.
[ 4] Kamel MS , Ohtani K , Hasanain HA , et al.Monoterpene and
pregnane glucosides from Solenostruma argel [ J] .Phytochem-
istry , 2000 , 53:937-940.
[ 5] Isihhi H , Nakamura M , Seo S , et al.Isolation , characteriza-
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紫花松果菊中的单萜苷
李继仁 , 白焱晶 , 王 , 陈 刚 , 艾铁民 , 赵玉英
(北京大学药学院天然药物学系 , 北京 100083)
摘要:目的　研究紫花松果菊中的化学成分。方法　用溶剂法和色谱方法分离紫花松果菊地上部分的化学成分 ,用波谱
技术对分离的化合物进行结构鉴定。结果　从紫花松果菊地上部分分离得到了 6个化合物。用波谱方法鉴定为2 , 6-二甲基-
7-辛烯-2 , 3 , 6-三醇-2-O -β-D- 葡萄糖苷(1), 7 , 8-呋喃香豆素(2), 6-甲氧基-7-羟基香豆素(3), 咖啡酸(4), 咖啡酸甲酯(5),
咖啡酸乙酯(6)。结论　6 个化合物均为首次从该植物中获得。
关键词:紫花松果菊;单萜苷;2 , 6-二甲基辛烯-7 , 3 , 6-三醇-2-O-β-D-葡萄糖苷
183Journal of Chinese Pharmaceutical Sciences 2003 , 12(4)