全 文 ：书广 西 植 物 Guihaia Jan． 2014，34(1) :126－129 http:/ / journal． gxzw． gxib． cn
DOI:10． 3969 / j． issn． 1000-3142． 2014． 01． 024
黄永林，陈月圆，颜小捷，等． 红背山麻杆叶的化学成分研究(Ⅰ)———酚酸类及相关化合物［J］． 广西植物，2014，34(1) :126－129
Huang YL，Chen YY，Yan XJ，et al． Chemical constituents from the leaves of Alchornea trewioides(1)． Phenolic acids and related compounds［J］．
Guihaia，2014，34(1) :126－129
Chemical constituents from the leaves of Alchornea
trewioides(1)． Phenolic acids and related compounds
HUANG Yong-Lin，CHEN Yue-Yuan，YAN Xiao-Jie，
LIU Jin-Lei，YANG Zi-Ming，LI Dian-Peng*
(Guangxi Key Laboratory of Functional Phytochemicals Ｒesearch and Utilization，
Guangxi Institute of Botany，Guilin 541006，China )
Abstract:80% acetone extracts of the fresh leaves of Alchornea trewioides was successively separated by Sephadex LH-
20，MCI gel CHP 20P，and Toyopearl Butyl-650C column chromatography to yield ten phenolic acids and related com-
pounds． Their structures were elucidated by spectroscopic analyses as:salicylic acid(1) ，p-hydroxybenzoic acid(2) ，2
5-dihydroxybenzoic acid(3) ，3 4-dihydroxybenzoic acid(4) ，trans-p-coumaric acid(5) ，cis-p-coumaric acid(6) ，caffeic
acid(7) ，caffeic acid methyl ester(8) ，gallic acid(9) ，and methyl gallate(10)． Compounds 1－8，10 were isolated from
the Alchornea for the first time．
Key words:Alchornea trewioides;chemical constituents;phenolic acid
GLC Number:Q964． 81 Document Code:A Article ID:1000-3142(2014)01-0126-04
红背山麻杆叶的化学成分研究(Ⅰ)
———酚酸类及相关化合物
黄永林，陈月圆，颜小捷，刘金磊，杨子明，李典鹏*
(广西植物功能物质研究与利用重点实验室，广西植物研究所，广西 桂林 541006 )
摘 要:采用 80%丙酮提取石油醚萃取部位，利用凝胶、MCI及 Toyopearl Butyl-650C 柱色谱进行分离纯化得
到 10个酚酸类及相关化合物。根据化合物的波谱数据分析鉴定为水杨酸(1)、对羟基苯甲酸(2)、2，5-二羟基
苯甲酸(3)、3，4-二羟基苯甲酸(4)、反-对香豆酸(5)、顺-对香豆酸(6)、咖啡酸(7)、咖啡酸甲酯(8)、没食子酸
(9)、没食子酸甲酯(10)。其中化合物 1 ～ 8、10均为首次从本属植物中分离得到。
关键词:红背山麻杆;化学成分;酚酸
The genus Alchornea belongs to the family Euphor-
biaceae and contains approximately 70 species． Over 6
species have been recorded in China(Editorial Commit-
tee in Flora of China，1996) ，many of which have been
used for treating inflammation of the prostate gland，he-
maturia，shigella，inflammation，lumbocrural pain and
many other diseases(Jiangsu New Medical College，
1977)． The A． trewioides belongs to the family Alchor-
收稿日期:2013-10-15 修回日期:2013-11-25
基金项目:广西自然科学基金(2011GXNSFD018038);广西科技合作与交流计划项目(桂科合:1298014-10);广西植物研究所基本业务费项目(桂植
业 13002);广西植物功能物质研究与利用重点实验室开放基金(ZＲJJ2013-7)。
作者简介:黄永林(1974-)，男，广西桂林人，博士，研究员，主要从事天然产物物质基础、生物活性及开发利用研究，(E-mail)hyl@ gxib． cn。
* 通讯作者:李典鹏，博士，研究员，从事中药、天然药物和植物化学研究，(E-mail)ldp@ gxib． cn。
nea，it was used as traditional medicines to alleviate dis-
ease and discomfort． Previously，flavonoid glycosides，
phenolic acids and antioxidant activity have been repor-
ted from the species(Lu，2012;Qin，2012;Lu，2011)． To
further research for the material basis of pharmacological
effects from the species A． trewioides，ten phenolic acids
and related compounds were isolated from 80% acetone
extracts of the fresh leaves of A． trewioides． Compounds
1-8、10 were isolated from the Alchornea for the first
time．
1 Materials and methods
1H- and 13C-NMＲ spectra were measured in
CD3OD or acetone-d6 at 27 ℃ using a Bruker Avance
500 spectrometer(500 MHz for 1H and 125 MHz for
13C) (Bruker Biospin AG，Faellanden，Switzerland)or
a JEOL JNM-AL 400 spectrometer(400 MHz for 1H
and 100 MHz for 13C) (JEOL Ltd．，Tokyo，Japan)．
Coupling constants are expressed in Hz and chemical
shifts are given on a δ(mg /L)scale． Column chroma-
tography was performed using MCI gel CHP 20P(75－
150 μm;Mitsubishi Chemical，Tokyo，Japan) ，Sepha-
dex LH-20(25 －100 mm;GE Healthcare Bio-Science
AB，Uppsala，Sweden) ，and Toyopearl Butyl-650C
(TOSOH Co．，Tokyo，Japan)columns． TLC was per-
formed on precoated Kieselgel 60 F254 plates(0． 2 mm
thick;Merck，Darmstadt，Germany ) with CHCl3-
MeOH-H2O(9 ∶ 1 ∶ 0． 1，8 ∶ 2 ∶ 0． 2，or 7 ∶ 3 ∶ 0． 5，
v /v)and toluene-ethyl formate-formic acid(1 ∶ 7 ∶ 1，
v /v)as the solvent，and spots were detected by UV il-
lumination(254 nm)and by spraying with 2% ethanol-
ic FeCl3 and 10% sulfuric acid reagent，followed by
heating．
The leaves of A． trewioides were collected at
Guangxi Institute of Botany，Guangxi，China，in August
2011，and identified by Prof． WEI Fa-Nan． The
voucher specimen(20110920N)was deposited in the
Guangxi key laboratory of functional phytochemicals re-
search and utilization，Guangxi Institute of Botany．
2 Extraction and separation
The fresh leaves of A． trewioides(5． 35 kg)were cut
into small pieces and extracted with acetone-H2O(8 ∶
2，v /v)by maceration at room temperature． After filtra-
tion，the plant debris remaining on the filter paper was
extracted with the same solvent a further two times． The
filtrate was combined and concentrated under reduced
pressure to give an aqueous solution with dark green
precipitates． The precipitant was mainly composed of
chlorophylls and waxes，and removed by filtration． The
filtrate was defatted by partitioning with Et2O，to give an
Et2O fraction(Fr． E 5． 46 g)．
The Et2O fraction was subjected to Sephadex LH-
20 column chromatography with EtOH containing in-
creasing proportions of water(4 cm i． d． ×40 cm，0 －
50%，10% stepwise elution，each 400 mL)and finally
100% MeOH(500 mL)to give five fractions:frs． E-1
(2． 35 g) ，2(0． 15 g) ，3(0． 67 g) ，4(0． 53 g) ，5(1． 28
g)． Fraction E-1 was further fractionated by MCI gel
CHP 20P column chromatography(3 cm i． d． ×40 cm)
with 0－100% MeOH(10% stepwise elution，each 300
mL)and the subfractions were separated by column
chromatography using the Toyopearl Butyl-650C(2 cm
i． d． × 30 cm)with 0 － 100% MeOH(10% stepwise
elution，each 200 ml) to yield compounds 7 (4
mg) ，8(9 mg) ，9(937 mg) ，and 10(67 mg)． Fraction
E-3 was successively applied to a MCI gel CHP 20P
column chromatography(2 cm i． d． ×30 cm)with 0 －
100% MeOH(10% stepwise elution，each 100 mL)to
yield 3(7 mg)． Fraction E-4 was further fractionated by
MCI gel CHP 20P column chromatography(2 cm i． d． ×
40 cm)with 10% －100% MeOH(10% stepwise elu-
tion，each 100 ml)to yield compounds 1(17 mg) ，and 6
(6 mg)． Fraction E-5 was further fractionated by MCI
gel CHP 20P column chromatography(2 cm i． d． ×40
cm)with 10% －100% MeOH(10% stepwise elution，
each 150 mL) ，and the subfractions were purified by
Toyopearl Butyl-650C(1 cm i． d． × 30 cm)with 0 －
100% MeOH(10% stepwise elution，each 100 mL)to
get compounds 2(8 mg) ，4(17 mg) ，and 5(36 mg)．
3 Ｒesults and analysis
Salicylic acid (1) White amorphous powder，
C7H6O3．
1H-NMＲ(400 MHz，CD3OD)δ:6． 85(1H，dd，
J=1． 0，8． 3 Hz，H-3)，6． 88(1H，m，H-5)，7． 44(1H，m，H-
4)，7． 84(1H，dd，J=1． 7，8． 3 Hz，H-6);13C-NMＲ
7211期 黄永林:红背山麻杆叶的化学成分研究(Ⅰ)———酚酸类及相关化合物
Fig． 1 Chemical structures of compounds 1－10
(100 MHz，CD3OD)δ:114． 1(C-1) ，118． 1(C-3) ，
120． 0(C-5) ，131． 5(C-6) ，136． 5(C-4) ，163． 2(C-
2) ，173． 6(C-7) (Milena et al．，2004)．
p-Hydroxybenzoic acid(2) Brown amorphous
powder，C7H6O3 ．
1H-NMＲ (400 MHz，CD3OD )
δ:6． 90(2H，d，J = 8． 5 Hz，H-3，5) ，7． 77(2H，d，J
=8． 5 Hz，H-2，6) ;13C-NMＲ(100 MHz，CD3OD)δ:
116． 7(C-3，5) ，123． 6(C-1) ，133． 8(C-2，6) ，164． 2
(C-4) ，171． 3(C-7) (Penchom et al．，1998)．
2，5-Dihydroxybenzoic acid (3) Pale brown
amorphous powder，C7H6O4 ．
1H-NMＲ (400 MHz，
CD3OD)δ:6． 74(1H，d，J=8． 9 Hz，H-3) ，6． 91(1H，
dd，J=2． 2，8． 9 Hz，H-4) ，7． 25(1H，d，J=2． 2 Hz，H-
6) ;13C-NMＲ(100 MHz，CD3OD)δ:113． 6(C-1) ，
116． 2(C-6) ，118． 4(C-3) ，124． 2(C-4) ，150． 1(C-
5) ，156． 3(C-2) ，173． 1(C-7) (Akiyo et al．，1995)．
3，4-Dihydroxybenzoic acid(4) White amor-
phous powder，C7H6O4 ．
1H-NMＲ(400 MHz，CD3OD)
δ:6． 78(1H，d，J=8． 3 Hz，H-5) ，7． 41(1H，dd，J = 2．
2，8． 3 Hz，H-6) ，7． 42(1H，d，J = 2． 2 Hz，H-2) ;13C-
NMＲ(100 MHz，CD3OD)δ:116． 2(C-5) ，118． 2(C-
2) ，123． 6(C-6) ，124． 5(C-1) ，146． 6(C-3) ，151． 6
(C-4) ，170． 2(C-7) (Ban et al．，2007)．
Trans-p-coumaric acid(5) Pale brown amor-
phous powder，C9H8O3 ．
1H-NMＲ(400 MHz，CD3OD)
δ:6． 29(1H，d，J=15． 8 Hz，H-8) ，6． 80(2H，d，J = 8．
3 Hz，H-3，5) ，7． 41(2H，d，J = 8． 3 Hz，H-2，6) ，7． 58
(1H，d，J = 15． 8 Hz，H-7) ;13C-NMＲ(100 MHz，
CD3OD)δ:115． 1(C-8) ，116． 7(C-3，5) ，127． 2(C-
1) ，131． 1(C-2，6) ，146． 8(C-7) ，161． 3(C-4) ，171． 2
(C-9) (An et al．，2008)．
Cis-p-coumaric acid(6) Pale brown amorphous
powder，C9H8O3 ．
1H-NMＲ(400 MHz，CD3OD)δ:5．
67(1H，d，J = 12． 7 Hz，H-8) ，6． 64(2H，d，J = 8． 5
Hz，H-3，5) ，7． 70(1H，d，J = 12． 7 Hz，H-7) ，7． 50
(2H，d，J = 8． 5 Hz，H-2，6) ;13C-NMＲ(100 MHz，
CD3OD)δ:116． 5(C-3，5) ，126． 3(C-8) ，130． 1(C-
7) ，130． 2(C-2，6) ，131． 5(C-1) ，156． 6(C-4) ，171． 7
(C-8) (Kort et al．，1996)．
Caffeic acid (7 ) White amorphous pow-
der，C9H8O4 ．
1H-NMＲ(400 MHz，CD3OD)δ:6． 20
(1H，d，J = 15． 9 Hz，H-8) ，6． 77(1H，d，J = 8． 1 Hz，
H-5) ，6． 91(1H，dd，J = 2． 2，8． 1 Hz，H-6) ，7． 03
(1H，d，J = 2． 2 Hz，H-2) ，7． 52(1H，d，J = 15． 9 Hz，
H-7) ;13C-NMＲ(100 MHz，CD3OD)δ:115． 1(C-2) ，
115． 6(C-8) ，116． 5(C-5) ，122． 8(C-6) ，127． 8(C-
1) ，146． 7(C-3) ，147． 0(C-7) ，149． 4(C-4) ，171． 1
(C-9) (Fukuoka et al．，1982)．
Caffeic acid methyl ester(8) White amorphous
powder，C10H10O4 ．
1H-NMＲ(400 MHz，CD3OD)δ:3．
88(3H，s，OCH3) ，6． 30(1H，d，J =15． 9 Hz，H-8) ，6．
79(1H，d，J=8． 1 Hz，H-5) ，7． 05(1H，dd，J = 2． 2，8．
1 Hz，H-6) ，7． 15(1H，d，J=2． 2 Hz，H-2) ，7． 58(1H，
d，J = 15． 9 Hz，H-7) ;13C-NMＲ(100 MHz，CD3OD)
δ:56． 5(C-OCH3) ，111． 7(C-8) ，116． 0(C-2) ，116． 5
(C-5) ，124． 0(C-6) ，127． 8(C-1) ，146． 8(C-7) ，147．
3(C-3) ，150． 6(C-4) ，167． 9(C-9) (Shin et al．，
2004)．
Gallic acid (9 ) White amorphous pow-
der，C7H6O5 ．
1H-NMＲ(500 MHz，acetone-d6)δ:7．
821 广 西 植 物 34卷
14(2H，s，H-2，6) ;13C-NMＲ(125 MHz，acetone-d6)
δ:110． 1(C-2，6) ，121． 9(C-1) ，138． 7(C-4) ，146． 0
(C-3，5) ，168． 1(C-7) (Lu et al．，1999)．
Methyl gallate(10) White amorphous powder，
C8H8O5 ．
1H-NMＲ(400 MHz，acetone-d6) δ:3． 77
(3H，s，OCH3) ，7． 11(2H，s，H-2，6) ;
13C-NMＲ(100
MHz，acetone-d6)δ:51． 9(C-OCH3) ，109． 8(C-2，
6) ，121． 7(C-1) ，138． 7(C-4) ，145． 7(C-3，5) ，167． 2
(C-7) (Ma et al．，2005)．
Acknowledgements The authors are grateful to
Mr． NING De-Sheng(Guangxi Key Laboratory of Func-
tional Phytochemicals Ｒesearch and Utilization) for
NMＲ measurements．
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9211期 黄永林:红背山麻杆叶的化学成分研究(Ⅰ)———酚酸类及相关化合物