全 文 ：Study on Chemical Constituents from Breynia fruticosa
FU Guang-Miao ,YU Bo-Yang ,ZHU Dan-Ni
(Department of Complex Recipe of CMM , China Pharmaceutical University , Nanjing 210038 , China)
【ABSTRACT】　AIM:To investigate the chemical constituents from the aerial parts of Breynia fruticosa..METHOD:Various
chromatographic techniques were employed for isolation and purification of the constituents.The structures were elucidated by
chemical evidence and spectral methods.RESULT:Eight compounds were obtained and identified by spectroscopic methods
and compared with authentic samples as n-butyl-β-D-fructopyranoside , ethyl-β-D-fructopyranoside , tetracosylferulate , β-sitos-
terol , n-dotriacontanol , daucosterol , arbutin and (-)-epicatechin.CONCLUSION:All compounds were firstly isolated from
Breynia fruticosa(L.)Hook.f.
【KEY WORDS】　Breynia fruticosa ;Euphorbiaceae;Chemical constituent;Isolation;Identification
【CLC Number】　R284.2　　【Document code】　A　　【Article ID】　1000-5048(2004)02-0114-03
　　Breynia fruticosa(L.)Hook.f.is found abun-
dantly in the south of China and has been used as a tra-
ditional Chinese medicine for the treatment of chronic
bronchitis and inflammation , and also as a folk
medicine[ 1] .Breynia fruticosa belongs to the genus
Breynia of the family Euphorbiaceae.Previous chemical
investigations of Breynia genus were very little.To the
best of our knowledge there is no phytochemical and
pharmaceutical data on Breynia fruticosa.In the course
of our study , eight compounds have been isolated from
the chloroform fraction and n-butanol fraction of the
ethanol extracts.This paper deals with the isolation and
structure elucidation of these compounds , n-butyl-β-D-
fructopyranoside(Ⅰ), Ethyl-β-D-fructopyranoside(Ⅱ),
tetracosylferulate(Ⅲ), β-sitosterol(Ⅳ), n-dotriacon-
tanol(Ⅴ), daucosterol(Ⅵ ), arbutin(Ⅶ )and (-)-epi-
catechin(Ⅷ),which has been isolated for the first time
from this plant.
1　Apparatus and reagents
All melting points were determined on a X-4 micro
melting point apparatus and are uncorrected.The
1HNMR and 13CNMR spectra were recorded on Brucker
ACF-300 instrument , and the chemical shifts were ex-
pressed in δrelative to tetramenthysilane.Optical rota-
tions were measured using a JASCO DIP-180 digital
spectropolarimeter.UV spectra were measured in MeOH
on a Beckman DU 640 spectrophotometer.The IR spec-
tra were recorded on a Nicolet Compact 40 spectrometer.
MS were recorded with a JMS D300 mass spectrometer.
Sephadex LH-20 was used for open column chromatogra-
phy.TLC was performed using silica gel 60 G plates.
The aerial parts of Breynia fruticosa were collected
in September 2001 from the area of Sanya ,Hainan ,Chi-
na.The plant material was identified by XU Zeng-Lai , a
Ph.D.candidate in the school of Chinese MateriaMed-
ica of China Pharmaceutical University.A voucher spec-
imen is deposited in the herbarium of Jiangsu Botanical
Institute of Chinese Academy of Sciences.
2　Extraction and isolation
Dried and powdered aerial parts of Breynia fruti-
cosa(4.75 kg)were extracted with 95% ethanol(3×40
L)at 85 ℃ for 2 h and the solvent was evaporated off
under reduced pressure.The 95% ethanol extract(276
g)was suspended in water and the aqueous suspension
was extracted with CHCl3 and n-BuOH successively.
The CHCl3 extract(88 g)and the n-BuOH extract
(126 g)was subjected to column chromatography on sil-
ica gel and eluted with Petrol-EtOAc and CHCl3-MeOH
114
【Received date】　2003-09-11　　【＊Corresponding author】　Tel:025-85391042　E-mai l:boyangyu@hotmail.com
中国药科大学 学 报
Journal of China Pharmaceutical University　2004 ,35(2):114 ～ 116
gradually increasing polarity respectively.The elutes
were collected in 500 ml portions , monitored by TLC.
Fractions eluted with Petrol-EtOAc gave compound Ⅲ(8
mg), Ⅳ(66 mg), and Ⅴ(34 mg).The n-BuOH extract
(126 g)was separated into seven fractions , fr.Ⅰ-Ⅶ .
Fractions Ⅲ was crystallized from CHCl3-MeOH giving
compound Ⅵ(30 mg).Fractions Ⅳ～ Ⅶ were further
subject to column chromatography on Sephadex LH-20
with MeOH gave compound Ⅰ(125 mg), Ⅱ(86 mg),
Ⅶ (18 mg)and Ⅷ(42 mg)respectively.
3　Structrue elucidation
Compound Ⅰ 　Colorless needle crystals(Me2CO), mp 152
～ 154 ℃;It was soluble in MeOH and slightly soluble in CHCl3
and EtOAc , IR(KBr)νmax:3520-3120 , 2950 , 1401 , 1118 , 1062 ,
912 , 890 , 864 , 780 , 649 cm-1;1HNMR(500 MHz , CD3OD)δ:
3.90(1H , d , J=10.0 Hz ,H-3′), 3.83(1H ,m ,H-5′), 3.77(1H ,
dd , J =1.8 Hz , 10.0 Hz ,H-4′), 3.76(1H , dd , J =1.9 Hz , 12.0
Hz ,H-6′), 3.73(1H , d , J =11.3 Hz , H-1′), 3.69(1H , d , J =
11.3 Hz ,H-1′), 3.65(1H , dd , J=1.9 Hz , 12.0 Hz ,H-6′), 3.51
(2H ,m ,H-1), 1.56(2H ,m ,H-2), 1.40(2H , m ,H-3), 0.93(3H ,
t , J=7.3 Hz ,H-4);13CNMR(125 MHz , CD3OD)δ:99.9(C-2′),
69.9(C-4′), 69.4(C-5′), 69.1(C-3′), 63.5(C-6′), 61.8(C-1′),
59.9(C-1), 31.6(C-2), 18.8(C-3), 12.6(C-4).EIMS m/ z 236
[ M] +, 205 , 163 , 149 , 145 , 127 , 103 , 77 , 73 , 57;Compound I
yielded fructose on hydrochloric acid hydrolysis.Compound Ⅰ
was identified as n-butyl-β-D-fructopy ranoside by comparison of
the physical and spectrum data with the reported data[ 2] .
Compound Ⅱ　Colorless needle crystals(Me2CO), mp 157
～ 158 ℃;It was dissolved easily in MeOH and dissolved little in
CHCl3 and EtOAc, 1HNMR(500 MHz , CD3OD)δ:3.85(1H , d , J
=9.6 Hz ,H-3′), 3.83(1H ,m ,H-5′), 3.78(1H , dd , J=1.8 Hz ,
9.6 Hz ,H-4′), 3.76(1H , dd , J =1.8 Hz , 12.0 Hz ,H-6′), 3.73
(1H , d , J =11.3 Hz ,H-1′), 3.69(1H , d , J =11.3 Hz ,H-1′),
3.66(1H , dd , J=1.8 Hz , 12.0 Hz ,H-6′), 3.58(2H , q , J =7.0
Hz ,H-1), 1.18(3H , t , J=7.0 Hz ,H-2);13CNMR(500MHz , CD3
OD)δ:101.7(C-2′), 71.6(C-4′), 71.1(C-5′), 70.8(C-3′),
65.2(C-6′), 63.7(C-1′), 57.4(C-1), 15.8(C-2);ESI-MS m/ z
439[ 2M+Na] +, 231[ M+Na] +;Compound Ⅱ yielded fructose
on hydrochloric acid hydrolysis.Based on the inspection of the
physical date , Compound Ⅱ was identified as ethyl-β-D-fructopy-
ranoside by comparison of the 1HNMR and 13CNMR spectrum with
the reported data[ 3] .
Compound Ⅲ 　Colorless amorphous powder(MeOH),mp 71
～ 72 ℃;UV(MeOH)λmax324 , 298 nm;IR(KBr)νmax:3410 , 2912 ,
1724(CO), 1640 , 1608 , 1270 , 1170 , 708 cm-1;1HNMR(300
MHz , CDCl3)δ:7.61(1H , d , J=16.0 Hz ,H-2′), 7.08(1H , dd , J
=8.0 , 1.6 Hz ,H-6), 7.03(1H , d , J =1.6 Hz ,H-2), 6.91(1H ,
d , J =8.0 Hz , H-5), 6.29(1H , d , J =16.0 Hz , H-1′), 4.19
(2H , t , J=6.8 Hz ,H-1′′), 3.93(3H , s , OCH3), 1.69(2H ,m , H-
2′′), 1.64(2H ,m ,H-3′′), 1.25(40H , m , (CH2)20), 0.87(3H , t ,
J=6.8 Hz , CH3-24′′);13CNMR(75 MHz , CDCl3)δ:167.1(C-
3′), 147.6(C-4), 146.5(C-3), 144.3(C-1′), 126.8(C-1), 122.7
(C-6), 115.5(C-2′), 114.4(C-5), 109.1(C-2), 64.3(C-1′′),
55.7(OCH3), 31.7(C-2′′), 29.4 , 29.3 , 29.0(lots of , C-4′′～ C-
21′′), 28.5(C-22′′), 25.7(C-3′′), 22.4(C-23′′), 13.8(C-
24′′);ESI-MS m/ z 529([ M-H] +).Compound Ⅲ was identified
as tetracosyl ferulate by comparison of the physical and spectrum
data with the reported data[ 4] .
Compound Ⅴ　Colorless amorphous solid(CHCl3);mp 88～
90 ℃;1HNMR(300 MHz , CDCl3)δ:3.64(2H ,m , J=6.8 Hz , H-
1), 0.88(3H , t , J =6.8 Hz ,H-32);13CNMR(75 MHz , CDCl3)δ:
63.1(C-1), 31.9(C-2), 29.7 , 29.6 , 29.5 , 29.4(lots of , C-4 ～ C-
30), 25.7(C-3), 22.7(C-31), 14.1(C-32);EI-MS m/ z 448(M-
H2O), 434 , 420 , 406 , 392 , 378 , 364 , series of CnH2n+.and Cn
H2n-1+.alkyl ion with descending fourteen.Compound Ⅴ was i-
dentified as n-dotriacontanol by comparison of the phy sical and
spectrum data with the reported data.
Compound Ⅶ 　Colorless amorphous powder(CHCl3);mp
198～ 200 ℃;IR(KBr)νmax 3384 , 2910 , 1513 , 1442 , 1401 , 1212 ,
1065 , 1014 , 833 cm-1;1HNMR(300 MHz , CDCl3)δ:6.76(2H ,
d , J=6.9 Hz ,H-3 ,H-5), 6.58(2H , d , J=6.9 Hz ,H-2 ,H-6),
4.62(1H , d , J =6.1 Hz , H-1′), 3.70(1H , dd , J =11.7 Hz , 3
Hz ,H-6′), 3.60(1H , 1H , dd , J =11.7 Hz , 4.8 Hz , H-6′),
3.22-3.50(4H , m , H-2′, H-3′, H-4′, H-5′);13CNMR(75 MHz ,
CDCl3)δ:151.8(C-4), 149.8(C-1), 117.5(C-3 , C-5), 115.0(C-
2 , C-6), 101.4(C-1′), 76.1(C-3′), 75.5(C-5′), 72.7(C-2′),
69.7(C-4′), 61.1(C-6′).Compound Ⅶ was identified as arbutin
by comparison of the physical and spectrum data with the reported
data[ 5] .
Compound Ⅷ 　yellow amorphous powder(CHCl3-MeOH);
mp 215～ 219 ℃;[α] 20D-21°(c 0.5 ,MeOH);IR(KBr)νmax:3379 ,
1628 , 1520 , 1460 , 1375 , 1286 , 1146 , 1030 , 875 , 760 cm-1;
1HNMR(300 MHz , CD3OD)δ:6.96(1H , d , J=1.8 Hz , H-2′),
6.79(1H , dd , J =1.8 Hz , 8.1 Hz ,H-6′), 6.74(1H , d , J =8.1
Hz ,H-5′), 5.94(1H , d , J =2.4 Hz ,H-8), 5.90(1H , d , J=2.4
Hz ,H-6), 4.80(1H , br ,H-2), 4.16(1H , br , H-3), 2.85(1H , dd ,
J=16.8 Hz , 4.5 Hz ,H-4), 2.72(1H , dd , J=16.8 Hz , 3.0 Hz ,
H-4);13CNMR(75 MHz , CD3OD)δ:158.0(C-5), 157.7(C-7),
157.4(C-9), 146.0(C-4′), 145.8(C-3′), 132.3(C-1′), 119.5
115　No.2 FU Guang-Miao , et al:Study on chemical constituents from Breynia fruticosa
(C-6′), 116.5(C-2′), 115.5(C-5′), 100.2(C-10), 96.6(C-6),
96.0(C-8), 79.9(C-2), 67.5(C-3), 29.2(C-4).Compound Ⅷ
was identified as (-)-epicatechin by comparison of the physical
and spectrum data with the reported data[ 6] .
Compound Ⅳ and Ⅵ were identified as β-sitosterol and
doucosterol respectively.
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黑面神化学成分的研究
浮光苗 ,余伯阳 ,朱丹妮
(中国药科大学中药复方研究室 , 南京 210038)
【摘　要】　目的:研究中草药黑面神的化学成分。方法:黑面神嫩枝和叶子用 95%乙醇回流提取 ,提取物分别用氯仿 、
正丁醇萃取 ,将氯仿部位和正丁醇部位分别进行硅胶柱层析 ,其中正丁醇部位的化合物采用重结晶 、Sephadex LH-20 柱层析
方法进行纯化;通过 IR、UV、MS、1HNMR和13CNMR等波谱解析方法以及和化合物标准品对比的方法进行结构鉴定。结果:
从黑面神氯仿部位分离得到了 8个化合物 ,分别鉴定为正丁基-β-D-吡喃果糖苷(n-butyl-β-D-fructopyranoside , Ⅰ)、乙基-β-D-
吡喃果糖苷(ethyl-β-D-fructopyranoside , Ⅱ)、阿魏酸二十四烷醇酯(tetracosylferulate , Ⅲ)、β-谷甾醇(β-sitosterol , Ⅳ)、正三十二烷
醇(n-dotriacontanol , Ⅴ)、胡萝卜苷(daucosterol , Ⅵ)、熊果苷(arbutin , Ⅶ )和(-)-表儿茶素((-)-epicatechin , Ⅷ)。结论:8 个化合物
均为首次从该植物中分离得到。
【关键词】　黑面神;大戟科;化学成分;分离;鉴定
116 中 国 药 科 大 学 学 报 　 J China Pharm Univ Vol.35