全 文 :书广 西 植 物 Guihaia Mar.2014,34(2):143-147 http://journal.gxzw.gxib.cn
DOI:10.3969/j.issn.1000-3142.2014.02.001
黄永林,刘金磊,陈月圆,等.红背山麻杆叶的化学成分研究(Ⅱ)———黄酮和苯乙醇苷类化合物[J].广西植物,2014,34(2):143-147
Huang YL,Liu JL,Chen YY,et al.Chemical constituents from the leaves of Alchornea trewioides(2).Flavonoids and phenylethanoid glycosides[J].
Guihaia,2014,34(2):143-147
Chemical constituents from the leaves of Alchornea
trewioides(2).Flavonoids and phenylethanoid glycosides
HUANG Yong-Lin,LIU Jin-Lei,CHEN Yue-Yuan,
YANG Zi-Ming,YAN Xiao-Jie,LI Dian-Peng*
(Guangxi Key Laboratory of Functional Phytochemicals Research and Utilization,
Guangxi Institute of Botany,Guilin 541006,China)
Abstract:The 80%acetone extracts of the fresh leaves of Alchornea trewioides was successively separated by Sepha-
dex LH-20,MCI gel CHP 20P,ODS,and Toyopearl Butyl-650Ccolumn chromatography to yield seven flavonoids and
three phenylethanoid glycosides.Their structures were elucidated by spectroscopic analyses as:quercetin(1),querce-
tin-3-rhamnoside(2),quercetin-3-O-β-D-glucopyranoside(3),rutin(4),apigenin-6-C-β-D-glucopyranoside(5),apige-
nin-8-C-β-D-glucopyranoside(6),luteolin-7-O-a-L-rhamnopyranosyl(1→6)-β-D-glucopyranoside(7),2-phenylethylβ-
D-glucopyranoside(8),icariside D1(9),and 2-phenylethyl D-rutinoside(10).Compounds 1-3,5-6,8-10 were iso-
lated from the Alchorneafor the first time.
Key words:Alchornea trewioides;chemical constituents;flavonoid;phenylethanoid glycoside
CLC number:Q946.8 Document code:A Article ID:1000-3142(2014)02-0143-05*
红背山麻杆叶的化学成分研究(Ⅱ)
———黄酮和苯乙醇苷类化合物
黄永林,刘金磊,陈月圆,杨子明,颜小捷,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%丙酮提取物的水萃取部位,利用凝胶、MCI、反相碳18、及Toyopearl Butyl-650C柱色谱进
行分离纯化得到7个黄酮和3个苯乙醇苷类化合物。根据化合物的波谱数据分析鉴定为槲皮素(1)、槲皮苷
(2)、异懈皮苷(3)、芦丁(4)、异牡荆素(5)、牡荆素(6)、木犀草素-7-O-α-L-鼠李糖(1→6)-β-D-葡萄糖苷(7)、2-
phenethylβ-D-glucoside(8)、icariside D1(9)、2-苯乙基-D-芸香甙(10)。其中化合物1-3、5-6、8-10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;黄酮;苯乙醇苷
The genus Alchornea belongs to the family Eu-
phorbiaceae and contains approximately 70species.
Over 6species have been recorded in China(Editorial
Committee in Flora of China,1996),many of which
have been used for treating inflammation of the pros-
tate gland,hematuria,shigela,inflammation,lumbo-
* 收稿日期:2013-10-15 修回日期:2013-12-12
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(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。
crural pain and many other diseases(Jiangsu New Med-
ical Colege,1977).The A.trewioides belongs to the
family Alchornea,it was used as traditional medicines
to aleviate disease and discomfort.Previously,fla-
vonoid glycosides,phenolic acids and antioxidant activi-
ty have been reported from the species(Lu,2012;Qin,
2012;Lu,2011;Huang,2014).To further research for
the material basis of pharmacological efects from the
species A.trewioides,seven flavonoids and three phe-
nylethanoid glycosides were isolated from the 80%ac-
etone extracts of the fresh leaves of Alchornea
trewioides.Compounds 1-3,5-6,8-10 were isola-
ted from the Alchorneafor the first time.
1 Materials and methods
1 H-and 13C-NMR spectra were measured in CD3
OD or acetone-d6at 27℃using a Bruker Avance 500
spectrometer(500MHz for 1 H and 125MHz for 13C)
(Bruker Biospin AG,Faelanden,Switzerland)or a JE-
OL JNM-AL 400spectrometer(400MHz for 1 H and
100MHz for 13C)(JEOL Ltd.,Tokyo,Japan).Cou-
pling constants were expressed in Hz and chemical
shifts are given on aδ(ppm)scale.Column chromatog-
raphy was performed using MCI gel CHP 20P(75-150
μm;Mitsubishi Chemical,Tokyo,Japan),Sephadex
LH-20(25-100mm;GE Healthcare Bio-Science AB,
Uppsala,Sweden),Chromatorex ODS(100-200mesh,
Fuji Silysia Chemical Ltd.,kasugai,Japan),and Toyo-
pearl Butyl-650C(TOSOH Co.,Tokyo,Japan)col-
umns.TLC was performed on precoated Kieselgel 60
F254plates(0.2mm thick;Merck,Darmstadt,Germa-
ny)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 de-
tected by UV ilumination(254nm)and by spraying
with a 2%ethanolic FeCl3and 10%sulfuric acid rea-
gent,folowed by heating.
The leaves of A.trewioides were colected at
Guangxi Institute of Botany,Guangxi,China,in August
2011,and identified by Prof.Wei Fanan.The voucher
specimen(2011 0920N)was deposited in the Guangxi
key laboratory of functional phytochemicals research
and utilization,Guangxi Institute of Botany.
2 Extraction and separation
The fresh leaves of A.trewioides(5.35kg)were
cut into smal pieces and extracted with acetone-H2O(8
∶2,v/v)by maceration at room temperature.After
filtration,the plant debris remaining on the filter paper
was extracted with the same solvent a further two
times.The filtrate was combined and concentrated un-
der reduced pressure to give an aqueous solution with
dark green precipitates.The precipitant was mainly
composed of chlorophyls and waxes,and removed by
filtration.The extract(610g)was partitioned between
H2O(3L)and Et2O(1L)3times.The aqueous layer
was fractionated by Sephadex LH-20column chroma-
tography(10cm i.d.×40cm)with water containing
increasing proportions of MeOH(0-100%,10%step-
wise elution,each 2L)and finaly with 60%acetone,to
yield 9fractions(Fr.1-9).Fraction 1(18.7g)was
separated by a combination of column chromatography
over MCI gel CHP 20P(8cm i.d.×40cm)with 0-
100% MeOH(10%stepwise elution,each 1L),Toyo-
pearl 650C(2cm i.d.×30cm)with 0-100% MeOH
(10%stepwise elution,each 300mL),and Chromator-
ex ODS(2cm i.d.×30cm)with 0-100% MeOH
(10%stepwise elution,each 300mL),to aford 8(285
mg),9(23mg),10(91mg).Fraction 5(35.6g)was
separated by a combination of column chromatography
over MCI gel CHP 20P(8cm i.d.×40cm)with 0-
100% MeOH(10% stepwise elution,each 1L),and
Sephadex LH-20(2cm i.d.×30cm)with 0-100%
MeOH(10%stepwise elution,each 300mL),to aford 1
(275mg).Fraction 6(36.0g)was further fractionated
by MCI gel CHP 20Pcolumn chromatography(8cm i.
d.×40cm)with 0-100% MeOH(10%stepwise elu-
tion,each 1L)to give nine fractions:frs.6-1(6.30g),2
(1.02g),3(1.36g),4(2.45g),5(6.28g),6(6.10g),7
(4.12g),8(2.56g),9(1.25g).Fraction 6-3(1.36g)
was successively applied to a Sephadex LH-20column
chromatography(3cm i.d.×30cm)with 0-100%
MeOH (10%stepwise elution,each 200mL)to yield
2(20mg).Fraction 6-8was subjected to a Sephadex
441 广 西 植 物 34卷
Fig.1 Chemical structures of compounds 1-10
LH-20column chromatography(3cm i.d.×30cm)
with 0-100% MeOH(10%stepwise elution,each 200
mL)to yield 4(25mg),and 5(36mg).Fraction 6-9
was further fractionated by Sephadex LH-20column
chromatography(6cm i.d.×40cm)with 10-100%
MeOH(10%stepwise elution,each 200mL),and the
subfractions were purified by Toyopearl Butyl-650C(1
cm i.d.×30cm)with 0-100% MeOH(10%step-
wise elution,each 100mL)to get compound3(6mg),
6(10mg),and 7(648mg).
3 Results and analysis
Quercetin(1) Yelow amorphous powder,
C15H10O7.1 H-NMR(500MHz,CD3OD)δ:6.16(1H,
d,J=2.2Hz,H-6),6.36(1H,d,J=2.2Hz,H-8),
6.87(1H,d,J=8.5Hz,H-5′),7.61(1H,dd,J=2.2,
8.5Hz,H-6′),7.72(1H,d,J=2.2Hz,H-2′);13 C-
NMR(125MHz,CD3OD)δ:94.4(C-8),99.2(C-6),
104.5(C-10),116.0(C-2′),116.2(C-5′),121.7(C-
6′),124.1(C-1′),137.2(C-3),146.2(C-3′),147.3(C-
2),148.7(C-4′),158.2(C-5),162.5(C-9),165.5(C-
7),177.3(C-4)(Xiao,et al.,2006;Markhamet al.,
1976).
Quercetin-3-rhamnoside(2) Yelow amor-
phous powder,C21H20O11.1 H-NMR(400MHz,CD3
OD)δ:0.93(3H,d,J=5.9Hz,H-6″),3.34(1H,t,J=
5.8Hz,H-4″),3.40(1H,m,H-5″),3.73(1H,dd,J=
3.2,9.3Hz,H-3″),4.21(1H,br s,H-2″),5.34(1H,
br s,H-1″),6.18(1H,d,J=2.0Hz,H-6),6.36(1H,
J=2.0Hz,H-8),6.90(1H,d,J=8.3Hz,H-5′),7.
30(1H,dd,J=1.9,8.3Hz,H-6′),7.33(1H,J=1.9
Hz,H-2′);13 C-NMR(100MHz,CD3OD)δ:17.8(C-
6″),71.9(C-2″),72.1(C-5″),72.2(C-3″),73.3(C-4″),
94.7(C-8),99.8(C-6),103.5(C-1″),105.9(C-10),
116.4(C-5′),116.9(C-2′),122.9(C-6′),123.1(C-1′),
136.2(C-3),146.5(C-4′),149.8(C-3′),158.7(C-2),
159.5(C-9),163.3(C-5),165.9(C-7),179.7(C-4)
(Fossen et al.,1999).
Quercetin-3-O-β-D-glucopyranoside (3)
Yelow amorphous powder,C21H20O12.1 H-NMR(500
MHz,CD3OD)δ:3.21-3.83(6H,m,H-2,3,4,5,
6ax,6eq),5.10(1H,d,J=7.5Hz,H-1),6.18
(1H,d,J=2.0Hz,H-6),6.36(1H,d,J=2.0Hz,H-
8),6.88(1H,d,J=8.5Hz,H-5′),7.61(1H,dd,J=
2.5,8.5Hz,H-6′),7.68(1H,d,J=2.5Hz,H-2′);13
C-NMR(125MHz,CD3OD)δ:62.5(C-6),71.0(C-
4),75.6(C-2),78.2(C-3),78.4(C-5),95.2(C-
8),98.2(C-6),101.2(C-1),105.3(C-10),116.1(C-
2′),116.3(C-5′),123.2(C-1′),123.3(C-6′),135.9(C-
3),146.2(C-3′),150.1(C-4′),159.0(C-2),159.2(C-
9),163.1(C-5),166.4(C-7),179.4(C-4)(Liu et al.,
2010).
Rutin(4) Yelow amorphous powder,C27H30
O16.1 H-NMR(500MHz,CD3OD)δ:1.15(3H,d,J=
5.8Hz,H-6),3.27-3.54(10H,m,H-2″,3″,4″,5″,
6ax″,6eq″,2,3,4,5),5.18(1H,br s,H-1),5.13
(1H,d,J=8.0Hz,H-1″),6.22(1H,br s,H-6),6.41
(1H,br s,H-8),6.89(1H,d,J=8.5Hz,H-5′),7.65
(1H,dd,J=2.0,8.5Hz,H-6′),7.68(1H,d,J=2.0
Hz,H-2′);13C-NMR(125MHz,CD3OD)δ:16.5(C-
6),67.2(C-6″),68.3(C-5),70.0(C-3),70.7(C-
2),70.9(C-4″),72.6(C-4),74.3(C-2″),75.8(C-
5″),76.8(C-3″),93.5(C-8),98.6(C-6),101.0(C-1),
5412期 黄永林等:红背山麻杆叶的化学成分研究(Ⅱ)———黄酮和苯乙醇苷类化合物
103.3(C-1″),104.3(C-10),114.7(C-5′),116.3(C-
2′),121.8(C-6′),122.2(C-1′),134.2(C-3),144.4(C-
3′),148.4(C-4′),157.1(C-9),157.9(C-2),161.7(C-
5),164.6(C-7),178.0(C-4)(Sang et al.,2001).
Apigenin-6-C-β-D-glucopyranoside(5) Yelow
amorphous powder,C21H20O10.1 H-NMR(500MHz,
CD3OD)δ:3.45-3.52(3H,m,H-3″,4″,5″),3.78(1H,
dd,J=6.5,12.0Hz,H-6ax″),3.92(1H,d,J=12.0
Hz,H-6eq″),4.21(1H,t,J=9.8Hz,H-2″),4.61
(1H,d,J=9.8Hz,H-1″),6.42(1H,s,H-8),6.49
(1H,s,H-3),6.89(2H,d,J=8.0Hz,H-3′,5′),7.42
(2H,d,J=8.0Hz,H-2′,6′);13 C-NMR(125MHz,
CD3OD)δ:61.5(C-6″),70.4(C-2″),71.3(C-4″),73.9
(C-1″),78.7(C-3″),81.2(C-5″),93.9(C-8),102.4(C-
3),103.8(C-10),107.7(C-6),115.6(C-3′,5′),121.6
(C-1′),128.0(C-2′,6′),157.2(C-9),160.5(C-5),
161.3(C-4′),163.4(C-7),164.6(C-2),182.5(C-4)
(Talita et al.,2012;Maatooq et al.,1997).
Apigenin-8-C-β-D-glucopyranoside(6) Yelow
amorphous powder,C21H20O10.1 H-NMR(500MHz,
CD3OD)δ:3.46-3.52(3H,m,H-3″,4″,5″),3.78(1H,
dd,J=6.5,12.0Hz,H-6ax″),3.92(1H,d,J=12.0
Hz,H-6eq″),4.21(1H,t,J=9.8Hz,H-2″),4.61
(1H,d,J=9.8Hz,H-1″),6.21(1H,s,H-6),6.45
(1H,s,H-3),6.90(2H,d,J=8.0Hz,H-3′,5′),7.98
(2H,d,J=8.0Hz,H-2′,6′);13 C-NMR(125MHz,
CD3OD)δ:61.3(C-6″),70.6(C-2″),70.9(C-4″),73.4
(C-1″),78.7(C-3″),81.8(C-5″),98.2(C-6),102.5(C-
3),104.1(C-8),104.6(C-10),115.8(C-3′,5′),121.1
(C-1′),128.9(C-2′,6′),156.0(C-5),160.4(C-9),
161.1(C-4′),162.7(C-7),164.0(C-2),181.1(C-4)
(Talita et al.,2012).
Luteolin-7-O-α-L-rhamnopyranosyl(1→6)-β-
D-glucopyranoside(7) Yelow amorphous powder,
C27H30O15.1 H-NMR(500MHz,acetone-d6)δ:1.20
(3H,d,J=6.5Hz,H-6),3.43-3.48(10H,m,H-2″,
3″,4″,5″,6ax″,6eq″,2,3,4,5),4.80(1H,br s,H-
1),5.16(1H,d,J=7.5Hz,H-1″),6.53(1H,br s,H-
6),6.68(1H,br s,H-8),6.87(1H,br s,H-3),7.04
(1H,d,J=8.5Hz,H-5′),7.47(1H,dd,J=2.0,8.5
Hz,H-6′),7.50(1H,d,J=2.0Hz,H-2′);13 C-NMR
(125MHz,acetone-d6)δ:17.1(C-6),66.2(C-6″),68.
5(C-5),69.8(C-4″),70.6(C-3),71.2(C-2),72.5
(C-4),73.3(C-2″),75.7(C-5″),76.3(C-3″),95.2(C-
8),100.0(C-6),100.4(C-1),100.6(C-1″),103.3(C-
3),105.8(C-10),113.3(C-5′),116.0(C-2′),119.5(C-
6′),122.2(C-1′),145.6(C-3′),149.7(C-4′),157.4(C-
9),161.3(C-5),163.3(C-7),165.3(C-2),182.5(C-4)
(Petrovic et al.,1999).
2-Phenylethylβ-D-glucopyranoside(8) Amor-
phous powder,C14H20O6.1 H-NMR(400MHz,CD3
OD)δ:2.93(2H,t,J=7.8Hz,H2-β),3.20(1H,dd,J
=7.8,8.5Hz,H-2′),3.29-3.42(3H,m,H-3′,4′,
5′),3.67(1H,dd,J=5.1,11.7Hz,H-6ax′),3.72
(1H,m,H-αax),3.87(1H,dd,J=3.2,11.7Hz,H-
6eq′),4.09(1H,m,H-αeq),4.31(1H,d,J=7.8Hz,
H-1′),7.18(1H,s,H-4),7.25(4H,m,H-2,3,5,6);13
C-NMR(100MHz,CD3OD)δ:37.2(C-β),62.7(C-6′),
71.3(C-α),71.7(C-4′),75.0(C-2′),77.8(C-5′),78.0
(C-3′),104.6(C-1′),127.2(C-4),129.3(C-3,5),129.
9(C-2,6),140.0(C-1)(Miyase et al.,1988;Kaoru et
al.,1988).
Icariside D1(9) Colorless syrup,C19H28O10.1 H-
NMR(400MHz,CD3OD)δ:2.93(2H,t,J=6.9Hz,H2-β),
3.17(1H,dd,J=7.8,9.0Hz,H-2′),3.29-3.37(3H,m,H-
3′,4′,5′),3.32-3.36(2H,m,H-5ax″,5eq″),3.59(1H,dd,J
=6.1,11.2Hz,H-6ax′),3.74(1H,d,J=9.8Hz,H-4ax″),
3.75(1H,m,H-αax),3.89(1H,d,J=2.4Hz,H-2″),3.89
(1H,d,J=9.8Hz,H-4eq″),3.97(1H,dd,J=2.2,11.2
Hz,H-6eq′),4.04(1H,m,H-αeq),4.28(1H,d,J=7.8Hz,
H-1′),5.00(1H,d,J=2.4Hz,H-1″),7.16(1H,s,H-4),7.
25(4H,m,H-2,3,5,6);13C-NMR(100MHz,CD3OD)δ:37.
2(C-β),65.6(C-5″),68.7(C-6′),71.7(C-α),71.8(C-4′),75.
0(C-2′),75.1(C-4″),76.9(C-5′),78.0(C-3′),78.1(C-2″),
80.5(C-3″),104.4(C-1′),111.0(C-1″),127.2(C-4),129.3
(C-3,5),130.0(C-2,6),140.0(C-1)(Miyase et al.,1987).
2-Phenylethyl D-rutinoside(10) Colorless
syrup,C20H30O10.1 H-NMR(400MHz,CD3OD)δ:
1.20(3H,d,J=6.5Hz,H-6″),2.92(2H,t,J=7.0
Hz,H2-β),3.19(1H,dd,J=7.6,8.5Hz,H-2′),3.28
(1H,t,J=9.2Hz,H-4″),3.30-3.41(3H,m,H-3′,4′,
5′),3.61(1H,dd,J=5.5,11.2Hz,H-6ax′),3.67-3.
69(2H,m,H-3″,5″),3.72(1H,m,H-αax),3.82(1H,
dd,J=1.7,3.1Hz,H-2″),3.89(1H,dd,J=2.2,11.2
Hz,H-6eq′),4.04(1H,m,H-αeq),4.29(1H,d,J=7.
6Hz,H-1′),4.73(1H,d,J=1.7Hz,H-1″),7.17
641 广 西 植 物 34卷
(1H,s,H-4),7.25(4H,m,H-2,3,5,6);13 C-NMR
(100MHz,CD3OD)δ:18.0(C-6″),37.2(C-β),68.1(C-
6′),69.8(C-5″),71.6(C-α),71.8(C-4′),72.1(C-2″),
72.3(C-3″),74.0(C-4″),75.0(C-2′),76.7(C-5′),78.0
(C-3′),102.2(C-1″),104.4(C-1′),127.2(C-4),129.3
(C-3,5),130.0(C-2,6),140.0(C-1)(Kaoru et al.,
1988,Hase et al.,1995).
Acknowledgements The authors are grateful to
Mr.NING De-Sheng(Guangxi Key Laboratory of
Functional Phytochemicals Research and Utilization)
for NMR measurements.
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7412期 黄永林等:红背山麻杆叶的化学成分研究(Ⅱ)———黄酮和苯乙醇苷类化合物