全 文 ：【Received date】　2004-12-07
【＊Corresponding author】　Tel/Fax:(021)-50806728;E-mail:dyzhu
@mai l.shcnc.ac.cn
Megastigmanes and Flavonoid Glycosides of Equisetum de-
bile
XU Xiao-Hong1 , 2 ,RUAN Bao-Qiang3 , JIANG Shan-Hao1 , ZHU Da-Yuan1＊
1StateKey Laboratory of Drug Research , Shanghai Instiute of Materia Medica , Shanghai Institut for Biological Science , Chinese Academy
of Sciences , Shanghai 201203 , China;
2Department of Applied Chemistry , East China Institute of Technology , Fuzhou 344100 , Jiangxi China;
3Fuzhou Institute of Drug Control , Fuzhou 350009 , Fujian China
【ABSTRACT】　AIM:To study the chemical constituents of Equisetum debile.METHODS:Compounds were isolated by
column chromatography on silica gel , sephadex LH-20 , ODS-18 and their structures were elucidated based on the spectroscop-
ic methods including 2D NMR(COSY , HMQC , HMBC).RESULTS:Four megastigmane type compounds were isolated ,
one aglycone and three glucosides , identified as blumenol A(1), corchoinoside C (2), sammangaoside A(3), and (3S ,
5R , 6R , 7E , 9S)-megastigmane-7-ene-3-hydroxy-5 , 6-epoxy-9-O-β-D- glucopyranoside(4).Four flavonoid glycosides ,
kaempferol-3 , 7-di-β-D-glucoside(5), camelliaside C (6), kaempferol 3-O-β-sophoroside(7), clematine(8)were also
obtained from this plant.CONCLUSION:All megasigmane compounds and compound 6 , 8 were obtained from Equisetaceae
family for the first time.
【KEY WORDS】　Equisetsaceae;Equisetum debile;Chemical constituents;Megastigmane;Flavonoid glycosides
【CLC Number】　R284.1　　【Document code】　A　　【Ariticle ID】　1672-3651(2005)02-0093-04
1　Introduction
Equisetum debile Roxb., belonging to Equise-
taceae family , is widely distributed in Fujian province.
It has been used in the treatment of diarrhea , acute
hepatitis and urethritis in Chinese folk medicine.This
plant has not systematically been reported on its chemi-
cal constituents.This paper mainly investigates the
megastigmane and flavonoid glucosides from it.The
megastigmane compounds are isolated from the whole
family for the first time.Considering the bioactivity of
their analogues [ 1 , 2] , they are probable active compo-
nents of Equisetum debile , which will be the work in our
future study.
2　Materials and apparatus
2.1　Plant Material
The plant (Biguancao)was collected from Xia-
men , Fujian province in China , and a voucher was de-
posited in the Laboratory of Drug Research , Shanghai
Institute of Materia Medica.
2.2　Apparatus and Material
Optical rotation were measured with an Perkin-
Elmer Polarimeter 341.IR spectra (tablet)were deter-
mined on a Nicolet Magna 750 FTIR(KBr)spectrome-
ter.NMR spectra were obtained on a Bruker AM 400
instrument with TMS as internal standard.EI-MS were
carried on FinniganMAT95 mass spectrometer.ESI-MS
spectrum were measured on a Bruker esquire 3000-Agi-
lent1100 instrument.
Silica gel (200-300 , 400 mesh)and pre-coated
中国天然药物　2005年 3月　第 3卷　第 2期 Chin J Nat Med　Mar.2005　Vol.3　No.2　93　
plates of silica gel (HSGF254)(Qingdao Haiyang Chem-
ical Group Co., Qingdao , China)were used for column
chromatography (CC)and TLC , respectively.
2.3　Extraction and Isolation
The dry whole plant of Equisetum debile (50 kg)
was extracted with CHCl3 , then the residue was extract-
ed with 70%EtOH/H2O.The EtOH extract was evapo-
rated to give as water-suspension , then partitioned with
EtOAc and n-BuOH successively.
The EtOAc extract part (20 g)gave compound 1 ,
2 after chromatographing with silica gel , Sephadex LH-
20 and ODS-18 repeatedly.The n-BuOH soluble part
(60 g)was subjected to silca gel , ODS-18 and
sephadex LH-20 to afford compound 3-8.
3　Structures Identification
Compound 1 (blumenol A)C13H20O3:was ob-
tained as amorphous solid (CHCl3).EI-MS:m/z 224
[M] +;1H NMR(300 MHz , CDCl3)δ:1.00(3H , s ,
C12-H), 1.07(3H , s , C11-H), 1.29(3H , d , J =
6.4 Hz , C10-H), 1.90(3H , d , J =1.3 Hz , C13-H),
2.09(1H , d , J =12.0Hz ,C2-Ha), 2.96(1H , d , J
=12.0 Hz , C2-Hb), 4.41 (m , 1H , C9-H), 5.81
(1H , dd , J =0.7 , 15.7 Hz , C7-H), 5.85(1H , dd ,
J =5.4 , 15.7Hz , C8-H), 5.90(1H , br , s , C4-H).
13
C NMR(100 MHz , CDCl3)spectral data(see Table
1).All these data were in accordance with those in lit-
erature[ 3] .
Compound 2(corchoinoside C)C19H30O8:viscous
solid(CH3OH).1H NMR (300 MHz , CD3OD)δ:
1.01(3H , s , C12-CH3), 1.06 (3H , s , C11-CH3),
1.28(3H , d , J =6.6 Hz , C10-CH3), 1.94(3H , d ,
J =1.4 Hz , C13-CH3), 2.17(1H , d , J =17.0 Hz ,
C2-Ha), 2.61 (1H , d , J =17.0 Hz , C2-Hb), 4.53
(m , 1H , C9-H), 5.87(1H , brs , C4-H), 5.97(1H ,
d , J =15.4 Hz , C7-H), 5.72 (1H , dd , J =7.2 ,
15.4Hz , C8-H);Glu:C1′-H 4.27(1H , d , J =7.7
Hz), C2′-H 3.19 (1H , m), C3′-H 3.25 (1H , m),
C4′-H 3.22(1H , m), C5′-H 3.15 (1H , m), C6′-Ha
3.85(1H , dd , J = 11.9 , 2.2 Hz), C6′-Hb 3.64
(1H , dd , J =11.9 ,6.0 Hz).13C NMR(100 MHz ,
CDCl3)spectral data (see Table 1).All these data
were in accordance with those in literature[ 4] .
Compound 3(sammangaoside A)C19H32O8:amor-
phous gel(CH3OH).1H NMR(400MHz , CD3OD)δ:
0.93(3H , s , C12-CH3), 1.08 (3H , s , C11-CH3),
1.27(3H , d , J =6.3 Hz , C10-CH3), 1.24(3H , d ,
J =1.4 Hz , C13-CH3), 1.28 (1H , t , J =11.0 Hz ,
C2-Ha), 1.56 (1H , br , d , J =10.7 Hz , C2-Hb),
4.52(m , 1H , C9-H), 1.61(1H , dd , J =14.2 , 9.3
Hz , C4-Ha), 2.28(1H , dd , J =14.2 , 1.7 Hz , C4-
He), 3.76(m , 1H , C3-H), 6.06(1H , d , J =15.6
Hz , C7-H), 5.57(1H , dd , J =7.2 , 15.6 Hz , C8-
H);Glu:C1′-H4.27 (1H , d , J =7.6 Hz), C2′-H
3.19(1H , m), C3′-H 3.25 (1H , m), C4′-H 3.22
(1H , m), C5′-H 3.15(1H , m), C6′-Ha 3.86(1H ,
dd , J =11.8 , 1.8 Hz), C6′-Hb 3.64(1H , dd , J =
11.8 , 6.0 Hz).13C NMR(100MHz , CDCl3)spectra
data (see Table 1).All these data were in accordance
with those in literature
[ 5] .
Compound 4 (3S , 5R , 6R , 7E , 9S)-Megatsig-
mane-7-ene-3-hydroxy-5 , 6-epoxy-9-O-β-D-glucopyra-
noside)C19H34O9:viscous solid(CH3OH).1H NMR
(300 MHz , CD3OD)δ:0.91(3H , s , C12-CH3), 1.11
(3H , s , C11-CH3), 1.34(3H , d , J =6.6 Hz , C10-
CH3), 1.24 (3H , d , J =1.4 Hz , C13-CH3), 1.46
(1H , ddd , J =12.2 , 4.0 , 1.5 Hz , C2-Heq), 1.66
(1H , t , J =12.2 Hz , C2-Hax), 4.56(m , 1H , C9-
H), 4.07(1H , m , C3-H), 6.19(1H , d , J =15.8
Hz , C7-H), 5.67(1H , dd , J =8.0 , 15.8 Hz , C8-
H);Glu:C1′-H 4.42(1H , d , J =7.8 Hz), C2′-H
3.19(1H , m), C3′-H 3.25 (1H , m), C4′-H 3.22
(1H , m), C5′-H 3.15(1H , m), C6′-Ha 3.88(1H ,
dd , J =12.0 , 2.2 Hz), C6′-Hb 3.68(1H , dd , J =
12.0 , 5.7Hz).13C NMR(100MHz , CDCl3)spectral
data (see Table 1).All these data were in accordance
in literature[ 6] .
Compound 5(kaempferol-3 , 7-di-β-D-glucoside)
C27H30O15 Yellow powder (CH3OH), 1H NMR (400
MHz , DMSO-d6).δ:8.07(2H , d , J =9.0 Hz , C2′,
C6′-H), 6.90 (2H , d , J =9.0 Hz , C3′, C5′-H),
6.80(1H , d , J =2.1 Hz , C6-H), 6.45(1H , d , J
=2.0 Hz , C8-H), 5.48 (1H , d , J =7.2 Hz ,
anomeric H), 5.08(1H , overlapped , anomeric H),
94　　Chin J Nat Med　Mar.2005　Vol.3　No.2 中国天然药物　2005年 3月　第 3卷　第 2期
3.2-3.8(12 H , m).13C NMR(100MHz , DMSO-d6)
see table 1.All the data were in consistent with those in
literature[ 7] .
Tab 1　13C-NMR data of compounds 1-8
1a 2b 3b 4b 5 6b 7c 8 5c 6b 7c 8c
1 41.2 42.9 36.3 41.2 1 Glu2-
2 49.7 51.2 42.0 46.8 2 156.0 158.9 156.3 78.4 1′′ 99.4 104.1
3 197.9 201.8 65.0 65.6 3 133.5 135.4 132.9 42.01 2′′ 73.1 74.4
4 126.9 127.6 48.3 45.9 4 177.7 180.2 177.5 197.0 3′′ 76.4 77.5
5 162.8 167.6 68.6 78.1 5 160.9 163.6 161.3 162.5 4′′ 69.6 69.7
6 79.0 80.5 71.7 79.6 6 99.7 100.5 97.9 96.44 5′′ 77.5 77.0
7 128.9 134.3 130.1 136.1 7 162.8 166.4 164.0 163.0 6′′ 60.6 60.8
8 135.7 134.2 136.5 133.4 8 94.5 95.2 93.6 95.6 Gal-
9 67.9 75.4 75.2 75.7 9 156.8 159.3 156.3 165.2 1′′ 105.1
10 24.0 22.7 22.9 22.8 10 105.7 106.3 104.2 103.4 2′′ 76.0
11 22.9 20.1 30.6 28.5 1′ 120.8 123.3 120.9 131.0 3′′ 78.4
12 23.8 24.0 25.5 26.8 2′ 131.0 132.8 131.0 117.9 4′′ 71.6
13 18.9 25.2 21.2 27.5 3′ 115.2 116.7 115.3 146.5 5′′ 78.4
Glc- 4′ 160.2 162.0 159.9 148.0 6′′ 63.1
1′ 101.7 101.8 100.9 5′ 115.2 116.7 115.3 112.2 Rha-
2′ 75.1 75.5 75.4 6′ 131.0 132.8 131.0 114.2 1′′ 100.6
3′ 78.7 78.7 78.7 OCH3 55.8 2′′ 708
4′ 72.2 72.2 72.0 Glu1- 3′′ 70.3
5′ 78.8 78.6 78.5 1′ 100.7 101.5 98.7 99.6 4′′ 72.1
6′ 63.3 63.3 63.1 2′ 74.2 82.9 82.4 73.0 5′′ 68.3
3′ 76.4 78.7 76.6 76.3 6′′ 17.8
4′ 69.9 71.8 69.7 69.7
5′ 77.2 78.7 76.6 75.6
6′ 60.6 62.9 60.5 66.1
a measured in CDCl3;b in CD3OD;c in DMSO-d6
　　Compound 6 (camelliaside C)C27H30O15 Yellow
amorphous solid (CH3 OH), mp 200 ～ 202 ℃.
1H NMR(300 MHz , CD3OD)δ:8.03(2H , d , J =
8.8 Hz , C2′, C6′-H), 6.90 (2H , d , J =8.8 Hz ,
C3′, C5′-H), 6.35(1H , d , J =1.5Hz , C8-H), 6.15
(1H , d , J =1.5Hz , C6-H), 5.40(1H , d , J =7.4
Hz , Glc C1-H), 4.78(1H , d , J =6.2 Hz , Gal C1-
H), 3.8-3.2(12H , m).13C NMR(100 MHz , CD3
OD)see table 1.All the data were in consistent with
those in literature[ 8] .
Compound 7 (kaempferol 3-O-β-sophoroside)
C27H30O15:Yellow needles (CH3OH), mp 194 ～ 200
℃.1H NMR(100 MHz , DMSO-d6):δ12.65(1H ,
s , OH), 10.82(1H , br s , OH), 10.15(1H , br s ,
OH), 8.08(2H , d , J =9.0 Hz , C2′, C6′-H), 6.92
(2H , d , J =9.0 Hz , C3′, C5′-H), 6.43(1H , d , J
=2.0 Hz , C8-H), 6.20 (1H , d , J =2.0 Hz , C6-
H), 5.68(1H , d , J =7.4 Hz , anomeric H), 4.60
(1H , d , J =7.4 Hz , anomeric H), 3.2-3.8 (12 H ,
m).All the data were in consistent with those in litera-
ture [ 7 , 9] .
Compound 8(clematine)C28H34O15:White powder
中国天然药物　2005年 3月　第 3卷　第 2期 Chin J Nat Med　Mar.2005　Vol.3　No.2　95　
(CH3OH), mp 263 ～ 265 ℃.1H NMR(400 MHz ,
DMSO-d6)δ:12.02(1H , s , C5-OH), 9.10(1H , s ,
C4′-OH), 6.90(1H , d , J =2.2 Hz , C2′-H), 6.92
(1H , d , J =9.0 Hz , C5′-H), 6.93 (1H , dd , J =
2.0 , 9.0Hz , C6′-H), 6.14(1H , d , J =2.0 Hz , C6-
H), 6.12(1H , d , J =2.0 Hz , C8-H), 5.51(1H ,
dd , J =12.0 , 2.6 Hz , C2-H), 4.97 (1H , d , J =
7.3 Hz , Glc C1-H), 4.50(1H , s , Rha C1-H), 3.77
(3H , s , C3′-OCH3), 3.32 (1H , overlapped , C3-
Hax), 2.76(1H , dd , J =3 , 17 Hz , C3-Heq), 1.08
(3H , d , J =6.4 Hz , Rha C6-H).13C NMR (100
MHz , DMSO-d6)see table 1.All the data were in con-
sistent with those in literature[ 10] .
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笔管草中Megastigmane及黄酮苷类化学成分
许小红1 , 2 ,阮宝强3 ,蒋山好1 ,朱大元1＊
1 中国科学院上海生命科学研究院 , 药物研究所 , 国家新药研究重点实验室 , 上海 201203;
2 东华理工学院应用化学系 ,江西 抚州 344100;
3 福建省福州市药检所 ,福建 福州 350009
【摘　要】　目的:研究木贼科植物笔管草(Equisetum debile)的化学成分。 方法:采用硅胶 、sephadex LH-20 凝胶柱色谱
进行分离纯化 , 通过理化方法和光谱分析鉴定化合物结构。结果:从笔管草全草乙酸乙酯和正丁醇提取物中分离得到 4
个 megastigmane 型化合物和 4个黄酮苷 , 分别鉴定为 blumenol A(1), corchoinoside C(2), sammangaoside A(3), (3S , 5R , 6R ,
7E , 9S)-megastigmane-7-ene-3-hydroxy-5 , 6-epoxy-9-O-β-D-glucopyranoside(4),山柰酚-3 , 7-双葡萄糖苷(5), camelliaside C(6),
山柰酚-3-槐糖苷(7)and clematine(8).化合物 1-4 , 6 , 8 均为从木贼科植物首次分得。
【关键词】　木贼科;笔管草;化学成分;megastigmane 类化合物;黄酮苷
96　　Chin J Nat Med　Mar.2005　Vol.3　No.2 中国天然药物　2005年 3月　第 3卷　第 2期