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Chemical constituents from the leaves of Alchornea trewioides(4). Polyphenols

红背山麻杆叶的化学成分研究(Ⅳ)—多酚类化合物(英文)



全 文 :广 西 植 物 Guihaia Aug.2015,35(4):564-568           http://journal.gxzw.gxib.cn 
DOI:10.11931/guihaia.gxzw201312033
黄永林,李典鹏,杨子明.红背山麻杆叶的化学成分研究 (Ⅳ)———多酚类化合物[J].广西植物,2015,35(4):564-568
HuangYL,LiDP,YangZM.ChemicalconstituentsfromtheleavesofAlchorneatrewioides(4).Polyphenols[J].Guihaia,2015,35(4):564-568
Chemicalconstituentsfromtheleavesof
Alchorneatrewioides(4).Polyphenols
HUANGYongGLin∗,LIDianGPeng,YANGZiGMing
(GuangxiKeyLaboratoryofFunctionalPhytochemicalsResearchandUtilization,
GuangxiInstituteofBotany,Guilin541006,China)
Abstract:Alchorneatrewioides,asatraditionalChinesemedicine,wasusedtoaleviateilnessanddiscomfortinChiG
na,butthematerialbasisofpharmacodynamicwasunknown.InordertoresearchforthematerialbasisofpharmacoG
dynamicfromA.trewioidesleaves,thefreshleavesofA.trewioideswereextractedwith80%aqueousacetoneand
assignedbypetroleumetherandwater.ThepetroleumetherandwaterextractsweresubjectedtothecolumnchroG
matographybyMCIgelCHP20P,SephadexLHG20,andToyopearlButylG650C,respectively,toyieldninepolyG
phenols.Theirstructureswereidentifiedbymeansof1HNMR,13CNMR,DEPT,andcomparisonwithliterature
as:elagicacid(1),3GOGmethylelagicacid(2),decarboxyelagicacid(3),1GOGgaloylGβGDGglucose(4),1,6GdiGOG
galoylGβGDGglucose(5),corilagin(6),phylanthusinD(7),furosonin(8),andgeranin(9),respectively.Compounds
2G9wereobtainedfromA.trewioidesforthefirsttime.
Keywords:Alchorneatrewioides;chemicalconstituents;polyphenols;elagicacid;extractionandseparation
CLCnumber:Q946.91,R284.1  Documentcode:A  ArticleID:1000G3142(2015)04G0564G05
红背山麻杆叶的化学成分研究(Ⅳ)———多酚类化合物
黄永林∗,李典鹏,杨子明
(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:红背山麻杆(Alchorneatrewioides)为山麻杆属植物,作为传统的中药被用来减轻疾病和身体不适,
但它的药效物质基础尚未完全清楚.为了全面掌握红背山麻杆药效物质基础,采用80%丙酮对其新鲜叶进
行提取,并利用 MCIgelCHP20P、SephadexLHG20等色谱柱进行分离共得到9个化合物.这些化合物的结
构经氢谱与碳谱比较分析鉴定为鞣花酸(1)、3GOG甲基没食子酸(2)、decarboxyelagicacid(3)、1GOG没食子酰
基GβGDG葡萄糖(4)、1,6G二GOG没食子酰基GβGDG葡萄糖(5)、柯里拉京(6)、叶下珠鞣质D(7)、furosonin(8)、老鹳
草素(9).其中化合物2~9均为首次从该属植物中分离得到.
关键词:红背山麻杆;化学成分;多酚;鞣花酸;提取与分离
   Alchorneatrewioides,asatraditionalChinese
medicine,wasusedtoreduceilness,discomfort,and
treatedinflammationoftheprostategland,hematuria,
andotherdiseasesinChina(JiangsuNewMedicalColG
lege,1977).Inpreviously,thepolyphenols,suchas
flavonoids,quinicacids,phenylethanoids,andphenolG
收稿日期:2014G12G26  修回日期:2015G02G09
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1298014G10);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(ZRJJ2013G7).
作者简介:黄永林(1974G),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,(EGmail)hyl@gxib.cn.
∗通讯作者
icacidshavebeenreported(Lu,2012;Qin,2012,
Huang,2013,2014,2015).However,theothermain
componentsofpolyphenolshavenotbeenreported,
andthe materialbasisofpharmacodynamicisunG
known.InordertograspforthematerialbasisofA.
trewioides,80% acetoneextractsweresubjectedto
thecolumnchromatographybyMCIgelCHP20P,
SephadexLHG20,andToyopearlButylG650C,respecG
tively,toyieldninepolyphenols.Theirstructureswere
identifiedbymeansof1H NMR,13CNMR,DEPT
andcomparisonwithliterature.Compounds2G9were
obtainedfromtheA.trewioidesforthefirsttime.
1 MaterialsandMethods
1HGand13CGNMRspectraweremeasuredwitha
JEOLJNMGAL400spectrometer(Tokyo,Japan),
operatingat400MHzfor1H,and100MHzfor13C,
oraBrukerAvance500spectrometer(BrukerBiospin
AG,Faelanden,Switzerland),operatingat500MHz
for1H,and125MHzfor13C.Couplingconstantsand
chemicalshiftsweregiveninHzandonaδ(ppm)
scale,respectively.Columnchromatographywasused
onMCIgelCHP20P,SephadexLHG20andToyopearl
ButylG650C.TLCwascarriedoutonsilicagel60F254
(Merck),withformicacidGformateGtolueneGethyl(2∶
8∶2,or1∶7∶1v/v),andsportswerevisualized
witha2%ethanolicFeCl3.
TheleavesofAlchorneatrewioideswerecolected
intheGuilinBotanicalGarden,Guangxi,China,in
August2011.ThesampleplantwasidentifiedbyProf.
WEIFaGNanofGuangxiInstituteofBotany,anda
herbariumspecimen(20110920N)wasdepositedin
theGuangxiInstituteofBotany.
2 ExtractionandIsolation
Thesmalpieces,freshleavesof(5.35kg)were
extractedwith80%acetoneforthreetimes,atroom
temperature.ThefiltratewasevaporatedbyrotaryeG
vaporationtogiveanextract.Theextract(610g)was
assignedbetweenEt2O(1L)andH2O(3L)3times.
ThepartofEt2OGsolublefraction(Fr.E5.46g)was
dissolvedinEtOHandappliedtoaSephadexLHG20
column(3.5cmi.d.×45cm)with100%-0EtOH
(20% stepwiseelution,each300mL)togivefive
fractions.TheEG3(0.67g)wasappliedtoaMCIgel
CHP20Pcolumn(2.5cmi.d.×25cm)withMeOHG
H2O(0∶100-100∶0)toobtain3(70mg).Thepart
ofwaterGsolublefractionwasdissolvedinwaterand
appliedtoaSephadexLHG20column(10cmi.d.×40
cm),elutingsuccessivelywithH2O,20%,40%,
60%,80%,100% MeOHGH2Otoyield9fractions
(Fr.1G9).Thefraction3(6.51g)wasappliedbya
combinationofcolumnchromatographyoverSephadex
LHG20,MCIgelCHP20P,andToyopearlButylG650C
toobtain4(45mg)and5(28mg).Fraction6(36.0g)
wasseparatedbyMCIgelCHP20PcolumnchromaG
tographytogivesevenfractions.Fraction6G4(2.45g)
wasseparatedbyacolumnchromatographyoverSephG
adexLHG20column(4cmi.d.×35cm)withMeOHG
H2O(0∶100)toyield6(2.15g).Fraction7(43.0g)
wasappliedbya MCIgelCHP20Pcolumnwith
MeOHGH2O(0∶100)toafordfivefractions.FracG
tion7G1wasfurtherseparatedbyMCIgelCHP20P
andSephadexLHG20columntogive6(4.52g),8(116
mg).Separationoffraction7G2usingSephadexLHG20
(3cmi.d.×50cm)withMeOHGH2O(0∶100-100
∶0),andfinalywith60%acetonetoaford7(476
mg).Separationoffraction7G3usedSephadexLHG20,
ChromatorexODS,andToyopearlButylG650CtoafG
ford1(14mg),2(31mg),9(6.41g).
3 ResultsandAnalysis
Elagicacid (1) amorphouswhitepowder,
C14H6O8.1HGNMR(400MHz,DMSO)β:7.50(2H,
s,HG5,5′);13CGNMR(125MHz,DMSO)β:106.8
(CG1,1′),109.7(CG5,5′),112.6(CG6,6′),136.3(CG
2,2′),140.6(CG3,3′),148.1(CG4,4′),159.1(CG7,
7′)(Khacetal.,1990).
3GOGMethylelagicacid(2) amorphouswhite
powder,C15H8O8.1HGNMR(500MHz,DMSO)β:
4.03(3H,s,3GOMe),7.43(1H,s,HG5′),7.50(1H,
s,HG5,5′);13CGNMR(125MHz,DMSO)β:60.7(CG
OMe),107.1(CG6′),110.7(CG5′),111.6(CG5),111.9
5654期        黄永林等:红背山麻杆叶的化学成分研究(Ⅳ)———多酚类化合物
Fig.1 Chemicalstructuresofcompounds1-9
(CG1),112.5(CG6),113.1(CG1′),137.0(CG2′),
134.0(CG3′),141.6(CG3),140.9(CG2),148.1(CG
4′),152.2(CG4),158.6(CG7′),158.8(CG7)(Baiet
al.,2008).
Decarboxyelagicacid(3) amorphouswhite
powder,C13H8O7.1HGNMR(400MHz,CD3OD)
β:6.73(1H,d,J=8.1Hz,HG5′),7.41(1H,s,
HG5),8.42(1H,d,J=8.1Hz,HG6′);13CGNMR
(100MHz,CD3OD)β:108.1(CG5),112.1(CG6),
112.4(CG5′),112.8(CG1′),118.5(CG1),119.1(CG
6′),133.3(CG3′),141.1(CG3),141.8(CG2′),144.0
(CG2),146.4(CG4),146.8(CG4′),163.8(CG6)
(Pfundsteinetal.,2010).
1GOGGaloylGβGDGglucose (4)  amorphous
brownpowder,C13H16O10.1HGNMR(500MHz,
acetoneGd6)β:3.18(1H,t,J=8.8Hz,HG4),
665 广 西 植 物                  35卷
3.21G3.55(3H,m,HG2,3,5),3.46(1H,dd,J=
6.1,12.0Hz,HG6ax),3.64(1H,dd,J=3.9,
12.0Hz,HG6eq),5.53(1H,d,J=8.5Hz,HG1),
7.23(2H,s,HG2′,6′);13CGNMR(125MHz,aceG
toneGd6)β:60.3(CG6),69.6(CG4),72.3(CG2),
75.6(CG5),76.1(CG3),93.4(CG1),108.9(2C,CG
2′,6′),119.4(CG1′),137.0(CG4′),144.0(2C,CG
3′,5′),165.2(CG7′)(ElGEkkawyetal.,1995).
1,6GDiGOGgaloylGβGDGglucose(5) amorphous
brownpowder,C20H20O14.1HGNMR(500MHz,
acetoneGd6)β:3.21G3.75(4H,m,HG2,3,4,5),
4.42(1H,dd,J=6.5,12.0Hz,HG6ax),4.58
(1H,dd,J=2.7,12.0Hz,HG6eq),5.67(1H,d,
J=7.5Hz,HG1),7.08,7.15(each2H,s,HG2′,
6′and2″,6″);13CGNMR(125MHz,acetoneGd6)β:
63.3(CG6),70.3(CG4),73.6(CG2),75.1(CG5),
76.8(CG3),95.7(CG1),107.9,108.0(each2C,CG
2′,6′and2′,6″),119.3,119.4(CG1′,1″),136.9,
137.4(CG4′,4″),143.9,144.0(each2C,CG3′,5′
and3″,5″),165.1,165.1(CG7′,7″)(Yanetal.,
2007).
Corilagin(6) amorphousbrownpowder,
C27H22O18.1HGNMR(500 MHz,acetoneGd6)β:
4.08(1H,brs,HG2),4.13(1H,dd,J=8.5,11.0
Hz,HG6ax),4.46(1H,brs,HG4),4.52(1H,t,
J=8.5Hz,HG5),4.83(1H,brs,HG3),4.91
(1H,t,J=11.0Hz,HG6eq),6.38(1H,s,HG1),
6.70(1H,s,HGringBG5),6.84(1H,s,HGringCG
5),7.12(2H,s,HGringAG2,6);13CGNMR(125
MHz,acetoneGd6)β:61.3(CG4),63.5(CG6),68.1
(CG2),69.9(CG3),74.7(CG5),93.5(CG1),107.1
(CGringBG5),109.1(CGringCG5),109.8(2C,CG
ringAG2,6),115.1(CGringBG1),115.8(CGringCG
1),119.8(CGringAG1),124.7(CGringCG2),124.8
(CGringBG2),135.7(CGringCG3),136.3(CGringBG
3),138.5(CGringAG4),143.9(CGringCG4),144.0
(CGringBG4),144.1(CGringCG6),144.5(CGringBG
6),145.0(2C,CGringAG3,5),164.6(CGringAG
7),166.5(CGringCG6),167.9(CGringBG7)(Chung
etal.,2003;Thitilertdechaetal.,2010).
Phylanthusin D (7) amorphousbrown
powder,C44H32O27.1HGNMR(500MHz,acetoneG
d6)β:2.19(3H,s,HGringEG9′),2.98(1H,d,J
=15.5Hz,HGringEG7ax′),3.47(1H,d,J=15.5
Hz,HGringEG7eq′),4.40(1H,dd,J=7.5,10.0
Hz,HG6ax),4.78(1H,t,J=7.5Hz,HG6eq),
4.81(1H,t,J=7.5Hz,HG5),4.91(1H,brs,HG
ringEG1′),5.43(1H,brs,HG4),5.53(1H,brs,
HG3),5.56(1H,brs,HG2),6.30(1H,s,HGring
EG3′),6.57(1H,brs,HGglcG1),6.65(1H,s,HG
ringBG3),7.07(1H,s,HGringCG3),7.17(2H,s,
HGringAG2,6),7.23(1H,s,HGringDG3);13CG
NMR(125 MHz,acetoneGd6)β:31.0(CGringEG
9′),49.1(CGringEG7′),51.1(CGringEG1′),61.5
(CG3),63.0(CG6),65.8(CG4),69.5(CG2),72.3(CG
5),80.0(CGringEG5′),91.0(CG1),107.0(CGringCG
3),108.8(CGringEG6′),109.5(CGringBG3),109.8
(2C,CGringAG2,6),112.5(CGringDG3),114.5(CG
ringCG1),116.0(CGringDG1),116.4(CGringCG1),
119.3(CGringAG1),119.3(CGringDG2),123.5(CG
ringBG2),124.5(CGringCG2),126.0(CGringEG3),
135.6(CGringCG5),136.5(CGringDG5),136.9(CG
ringBG5),139.6(CGringAG4),143.8(CGringBG4),
144.1(CGringBG6),144.4(CGringCG6),144.6(CG
ringCG4),144.7(CGringEG2′),145.2(2C,CGring
AG3,5),146.1(CGringDG6),146.8(CGringDG4),
163.9(CGringEG10′),164.3(CGringDG7),164.6(CG
ringAG7),165.4(CGringBG7),167.7(CGringCG7),
196.8(CGringEG4′),205.3(CGringEG8′)(Fooet
al.,1992;Yoshindetal.,1992).
Furosonin(8) amorphousbrownpowder,
C46H36O31.1HGNMR(500 MHz,acetoneGd6)β:
1.63(1H,d,J=14.0Hz,HGringEG3ax),2.73
(1H,d,J=14.0Hz,HGringEG3eq),3.93(1H,
dd,J=2.5,9.5Hz,HGringFG1ax),4.09(1H,m,
HGringFG2),4.12(1H,dd,J=5.5,9.5Hz,HG
ringFG1eq),4.16(1H,d,J=1.5Hz,HGringFG
3),4.44(1H,t,J=10.0Hz,HG6ax),4.73(1H,
m,HG6eq),4.75(1H,s,HGringEG1),4.91(1H,
t,J=9.0Hz,HG5),5.05(1H,s,HGringFG5),
5.36(1H,brs,HG4),5.61(1H,brs,HG2),5.66
(1H,brs,HG3),6.53(1H,brs,HG1),6.64
(1H,s,HGringBG3),7.07(1H,s,HGringCG3),
7.21(2H,s,HGringAG2,6),7.33(1H,s,HGring
DG3);13CGNMR(125MHz,acetoneGd6)β:31.6(CG
ringEG3),51.2(CGringEG1),52.5(CGringEG2),
7654期        黄永林等:红背山麻杆叶的化学成分研究(Ⅳ)———多酚类化合物
62.1(CG3),63.2(CG6),65.4(CG4),69.7(CG2),
72.6(CG5),74.4(CGringFG1),76.4(CGringFG5),
76.5(CGringFG2),80.7(CGringFG3),90.9(CG1),
97.7(CGringEG4),98.1(CGringEG6),98.2(CGring
EG5),106.8(CGringCG3),108.9(CGringFG4),
109.6(CGringCG3),109.8(2C,CGringAG2,6),
110.6(CGringDG1),113.9(CGringDG3),114.8(CG
ringBG1),116.3(CGringCG1),118.3(CGringDG2),
119.0(CGringAG1),123.5(CGringBG2),124.6(CG
ringCG2),135.6(CGringBG5),137.1(CGringCG5),
138.1(CGringDG5),139.4(CGringAG4),144.0(CG
ringBG4),144.1(CGringCG4),144.4(CGringDG6),
144.5(CGringBG6),144.7(CGringCG6),145.1(CG
ringDG4),145.2(2C,CGringAG3,5),164.7(CG
ringBG7),165.1(CGringDG7),165.8(CGringAG7),
168.1(CGringCG7),169.9(CGringEG7)(Taniguchi
etal.,2012).
Geranin (9) amorphousbrownpowder,
C41H28O27.1HGNMR(500 MHz,acetoneGd6)β:
4.33[1H,dd,J=6.0,10.5Hz,H(a)G6ax],4.44
[1H,dd,J=8.0,10.5Hz,H(b)G6ax],4.76
[1H,d,J=1.6Hz,H(b)GringEG1′],4.80[1H,
m,H(a)G5],4.80[1H,m,H(b)G5],4.91[1H,
m,H(b)G6eq],4.94[1H,t,J=10.5Hz,H(a)G
6eq],5.19[1H,s,H(a)GringEG1′],5.54[1H,
brs,H(a)G4],5.44[1H,brs,H(b)G4],5.50
[1H,brs,H(a)G3],5.57[1H,brs,H(b)G3],
5.58[1H,brs,H(a)G2],5.58[1H,brs,H(b)G
2],6.27[1H,d,J=1.6Hz,H(b)GringEG3′],
6.54[1H,brs,H(b)G1],6.58[1H,s,H(a)G1],
6.58[1H,s,H(a)GringEG3′],6.67[1H,s,H
(b)GringCG3],6.68[1H,s,H(a)GringCG3],7.10
[1H,s,H(b)GringBG3],7.16[1H,s,H(a)Gring
BG3],7.21[2H,s,H(a)GringAG2,6],7.21[2H,
s,H(b)GringAG2,6],7.23[1H,s,H(a)GringDG
3],7.27[1H,s,H(b)GringDG3];13CGNMR(125
MHz,acetoneGd6)β:46.2[C(a)GringEG1′],52.0
[C(b)GringEG1′],62.5[C(b)G3],63.8[C(a)G6],
63.8[C(b)G6],63.9[C(a)G3],65.9[C(a)G4],
66.0[C(b)G4],70.2[C(a)G2],70.6[C(b)G2],
72.7[C(a)G5],73.3[C(b)G5],90.9[C(a)G1],
91.8[C(b)G1],91.9[C(b)GringEG5′],91.9[C
(b)GringEG6′],92.4[C(a)GringEG6′],96.3[C
(a)GringEG5′],107.9[C(b)GringCG3],108.0[C
(a)GringCG3],109.8[C(b)GringBG3],110.6[C
(a)GringBG3],110.7 [2C,C(b)GringAG2,6],
110.9[2C,C(a)GringAG2,6],113.4[C(b)Gring
DG3],113.5[C(a)GringDG3],115.2[C(b)GringCG
1],115.3[C(a)GringCG1],115.9[C(a)GringDG
1],117.0[C(b)GringBG1],117.1[C(b)GringDG
2],117.2[C(a)GringBG1],119.5[C(a)GringDG
2],120.1[C(b)GringAG1],120.2[C(b)GringDG
1],120.7[C(a)GringAG1],124.7[C(b)GringBG
2],124.8[C(a)GringBG2],125.1[C(b)GringEG
3′],125.5[C(b)GringCG2],125.7[C(a)GringCG
2],128.7[C(a)GringEG3′],136.4[C(b)GringCG
5],136.5[C(a)GringCG5],137.2[C(b)GringDG
5],137.7[C(b)GringBG5],137.8[C(a)GringBG
5],139.0[C(a)GringDG5],139.9[C(a)GringAG
4],140.0[C(b)GringAG4],143.5[C(a)GringDG
6],144.6[C(b)GringBG4],144.9[C(a)GringCG
6],144.9[C(b)GringBG6],145.0[C(a)GringBG
6],145.2[C(b)GringCG6],145.3[C(a)GringBG
4],145.4[C(b)GringCG4],145.5[C(a)GringCG
4],145.8[C(a)GringDG4],145.9[2C,C(a)Gring
AG3,5],145.9[2C,C(b)GringAG3,5],147.0[C
(b)GringDG6],147.6[C(b)GringDG4],149.3[C
(b)GringEG2′],154.7[C(a)GringEG2′],164.7[C
(a)GringAG7],164.9[C(b)GringAG7],165.4[C
(b)GringDG7],165.5[C(a)GringDG7],165.6[C
(a)GringEG7′],165.8[C(b)GringBG7],165.9[C
(b)GringEG7′],166.2[C(a)GringBG7],168.4[C
(b)GringCG7],168.5[C(a)GringCG7],194.6[C
(b)GringEG4′],191.9[C(a)GringEG4′](Yoshindet
al.,1992).
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