全 文 ：天然产物研究与开发 NatProdResDev2008, 20:630-632
文章编号:1001-6880(2008)04-0630-03
　
　
　ReceivedApril18, 2007;AcceptedSeptember11, 2007
＊CorespondingauthorTel:86-25-85322132;E-mail:chywc@yahoo.
com.cn
楮叶中香豆素和黄酮类化学成分研究
杜彰礼 1 ,殷志琦 1 ,王　磊 1 ,叶文才 1, 2＊ ,沈文斌 3 ,赵守训 1
1中国药科大学天然药化教研室 ,南京 210009;
2暨南大学中药及天然药物研究所 , 广州 510632;3中国药科大学分析测试中心 , 南京 210009
摘　要:本文对楮树(Broussonetiapapyrifera(L.)Vent.)叶中的香豆素和黄酮类成分进行研究 , 利用柱层析 、重
结晶 、色谱技术等分离手段 ,分离得到了 10个化合物 ,经理化性质和波谱数据分析鉴定为伞形花内酯(1)、七叶
内酯(2)、芹菜素(3)、木犀草素(4)、山柰酚(5)、牡荆素(6)、芹菜素-7-O-β-D-葡萄糖醛酸(7)、芫花素(8)、槲皮
素(9)、二氢槲皮素(10)。化合物 1 ～ 7均为首次从该植物中分离得到。
关键词:楮树;叶;香豆素;黄酮
中图分类号:R284.1;Q946 文献标识码:A
CoumarinsandFlavonoidsfromLeavesofBroussonetiapapyrifera
DUZhang-li1 , YINZhi-qi1 , WANGLei1 , YEWen-cai1, 2＊ , SHENWen-bin3 , ZHAOShou-xun1
1DepartmentofPhytochemistry, ChinaPharmaceuticalUniversity, Nanjing210009 , China;
2InstituteofTraditionalChineseMedicineandNaturalProducts, JinanUniversity, Guangzhou510632 , China
3CenterofInstrumentalAnalysis, ChinaPharmaceuticalUniversity, Nanjing210009 , China
Abstract:TostudytheantifungalconstituentsintheleavesofBrousonetiapapyrifera(L.)Vent., chromatographicand
NMRspectroscopictechniqueswereusedtoisolateandelucidatetheconstituents.Tencompoundswereisolatedandi-
dentifiedasumbelliferone(1), esculetin(2), apigenin(3), luteolin(4), kaempferol(5), vitexin(6), apigenin-7-O-β-D-
glucuronide(7), genkwanin(8), quercetin(9), anddihydroquercetin(10).Compounds1-7wereisolatedfromthisplant
forthefirsttime.
Keywords:Broussonetiapapyrifera;leave;coumarin;flavonoid
Introduction
Brousonetia(Moraceae)comprisesabout30 species
andisdistributedinAfrica, EastAsia, andNorthA-
merica.Onlythreespeciesofthisgenus, B.papyrifera,
B.kazinoki, andB.zeylanica, havebeenchemicaly
studied[ 1] .B.papyriferaisalsodistributedwidelyin
China[ 2] , andscientistshavealreadyisolatedseveral
kindsofcompoundsfromthisplantalovertheworld
includingdiphenylpropanes, flavonoidsandetc[ 1] .
Pharmacologicalresearchindicatesthattheextractof
B.papyriferapossessessomebioactivitiessuchasanti-
fungal, antiplatelet, antioxidant, antihepatotoxic, aro-
mataseinhibitoryandsoon[ 1] .Theethanolextractof
B.papyriferaleavesshowextremelyhighantifungalac-
tivities[ 3] .
Insearchfornaturalsubstancespossesingantifungalac-
tivityfromB.papyriferaleaves, wehavesystematicalyin-
vestigatedthechemicalconstituentsofB.papyriferaleav-
es.Twocoumarinsandeightflavonoidswereisolatedby
chemicalandchromatographicmethods.Theywereidenti-
fiedasumbeliferone(1), esculetin(2), apigenin(3),
luteolin(4), kaempferol(5), vitexin(6), apigenin-7-O-β-
D-glucuronide(7), genkwanin(8), quercetin(9), anddi-
hydroquercetin(10).Compounds1-7 wereisolatedfrom
thisplantforthefirsttime.
Experimental
Apparatusandmaterials
MeltingpointsweremeasuredonanX-4 meltingpoint
apparatusandareuncorected.NMRspectrawerere-
cordedonaBrukerAV300 andaBrukerAV 500
DOI :10.16333/j.1001-6880.2008.04.022
spectrometerandwithTMSasinternalstandard.Col-
umnchromatographywascariedoutonsilicagel(200-
300 mesh, QingdaoHaiyangChemicalGroupCo.of
China).SephadexLH-20 isproductofPharmaciaBio-
tech, Sweden.MacroporousresinsD101 isproductof
NankaiUniversity.Columnfractionsweremonitoredon
thin-layerchromatography(TLC)oversilicagel60H
(QingdaoHaiyangChemicalGroupCo.ofChina)pre-
coatedplates.
B.papyriferaleaveswerecolectedinAugust2005 at
NanjingBotanicalGardenMem.SunYat-Sen, Nanjing,
JiangsuProvinceofChina, andauthenticatedbyProf.
QinMin-jianofChinaPharmaceuticalUniversity.A
voucherspecimen(No.2005-08BP)wasdepositedin
theDepartmentofPhytochemistry, ChinaPharmaceuti-
calUniversity.
Extractionandisolation
TheleavesofB.papyrifera(20kg)wereextractedwith
80% EtOH(120L)for3 ×3 h.ThecombinedEtOH
extractwasevaporatedunderreducedpressuretoyield
adarkbrownresidue, whichwassuspendedindistiled
waterandthenextractedwithpetroleumether, EtOAc
andn-BuOHtogivefractionA(280.0 g), fractionB
(76.0 g)andfractionC(591.3g), respectively.
FractionBwasdividedintosixsubfractionsoversilica
gel(200-300 mesh)columngradientlyelutedwithpe-
troleumether-EtOAc(100∶15-100∶100).Subfraction
B-2 wassubjectedtosilicagelcolumnelutedwith
CHCl3-CH3OH(100∶0-100∶50)toyield1(67.3 mg)
and8(27.6mg).SubfractionB-3wasrepeatedlysepa-
ratedoversilicagelandSephadexLH-20columntoaf-
ford2(160.3mg), 3(988.2 mg), 5(25.1 mg)and9
(18.1 mg).SubfractionB-4wassubjectedtosilicagel
columnelutedwithCHCl3 -CH3OH(100∶10-100∶60)
toyield4(24.9 mg)and10(39.4 mg).FractionC
wasdividedintofoursubfractionsusingmacroporous
resinsD101 columnwithEtOH(15%, 35%, 50%,
75%)assolvents.SubfractionsC-1 andC-3 werere-
peatedlyseparatedoversilicagelandSephadexLH-20
columntoaford7(100.8 mg)and6(78.3 mg), re-
spectively.
Compoundidentification
Umbeliferone(1)　Whiteneedlecrystals(MeOH),
mp.221-223℃;1HNMR(500MHz, C5D5N)δ:12.86
(1H, s, 7-OH), 7.62(1H, d, J=9.4 Hz, H-4), 7.37
(1H, d, J=8.0Hz, H-5), 7.00(1H, dd, J=8.0, 2.2
Hz, H-6), 6.99(1H, d, J=2.2 Hz, H-8), 6.24(1H,
d, J=9.4 Hz, H-3);13CNMR(125 MHz, C5D5N)δ:
161.1(C-2), 112.1(C-3), 144.1(C-4), 129.9(C-
5), 114.0(C-6), 163.0(C-7), 103.3(C-8), 156.8
(C-9), 112.0(C-10).TheseNMRdatawereidentical
tothoseofumbeliferone[ 4] .
Esculetin(2)　Whiteneedles(MeOH), mp.278-280
℃;1HNMR(500 MHz, DMSO-d6)δ:9.70(2H, brs,
6-OH, 7-OH), 7.86(1H, d, J=9.4 Hz, H-4), 6.98
(1H, s, H-5), 6.74(1H, s, H-8), 6.16(1H, d, J=9.4
Hz, H-3);13CNMR(125 MHz, DMSO-d6)δ:160.8(C-
2), 111.5(C-3), 144.4(C-4), 112.3(C-5), 142.8
(C-6), 150.4(C-7), 102.6(C-8), 148.5(C-9),
110.7(C-10).TheseNMRdatawereidenticaltothose
ofesculetin[ 5] .
Apigenin(3)　Yelowamorphouspowder(MeOH),
mp.> 300 ℃;1H NMR(500 MHz, DMSO-d6 )δ:
12.95(1H, s, 5-OH), 10.79(1H, s, 7-OH), 10.31
(1H, s, 4′-OH), 7.92(2H, d, J=8.9 Hz, H-2′, 6′),
6.92(2H, d, J=8.9 Hz, H-3′, 5′), 6.77(1H, s, H-
3), 6.48(1H, d, J=2.1 Hz, H-8), 6.19(1H, d, J=
2.1 Hz, H-6);13 CNMR(125 MHz, DMSO-d6 )δ:
164.1(C-2), 102.8(C-3), 181.7(C-4), 157.3(C-
5), 98.8(C-6), 163.7(C-7), 93.9(C-8), 161.4(C-
9), 103.7(C-10), 121.1(C-1′), 128.4(C-2′, 6′),
115.9(C-3′, 5′), 161.1(C-4′).TheNMRdatawere
inaccordancewiththoseofapigenin[ 6] .
Luteolin(4)　Yelowamorphouspowder(MeOH),
mp.> 300 ℃;1HNMR(500 MHz, DMSO-d6 )δ:
12.97(1H, s, 5-OH), 10.80(1H, s, 7-OH), 9.89
(1H, s, 4′-OH), 9.38(1H, s, 3′-OH), 7.42(1H, dd, J
=8.3, 2.2 Hz, H-6′), 7.40(1H, d, J=2.2 Hz, H-
5′), 6.89(1H, d, J=8.3 Hz, H-2′), 6.67(1H, s, H-
3), 6.44(1H, d, J=2.1 Hz, H-8), 6.19(1H, d, J=
2.1 Hz, H-6);13 CNMR(125 MHz, DMSO-d6 )δ:
163.8(C-2), 102.8(C-3), 181.5(C-4), 157.2(C-
5), 98.7(C-6), 164.0(C-7), 93.7(C-8), 161.4(C-
9), 103.6(C-10), 118.9(C-1′), 113.3(C-2′), 145.7
(C-3′), 149.6(C-4′), 116.0(C-5′), 121.5(C-6′).
TheNMRdatawereidenticaltothoseofluteolin[ 7] .
Kaempferol(5 )　 Yelow amorphous powder
(MeOH), mp.274-276 ℃;1HNMR(300 MHz, DM-
631Vol.20 DUZhang-li, etal:CoumarinsandFlavonoidsfromLeavesofBrousonetiapapyrifera
SO-d6)δ:12.48(1H, s, 5-OH), 10.76(1H, s, 7-OH),
10.01(1H, s, 4′-OH), 9.37(1H, s, 3-OH), 8.05
(2H, d, J=7.0 Hz, H-2′, 6′), 6.93(2H, d, J=7.0
Hz, H-3′, 5′), 6.44(1H, d, J=2.0 Hz, H-8), 6.19
(1H, d, J=2.0 Hz, H-6);13CNMR(75 MHz, DMSO-
d6)δ:146.7(C-2), 135.0(C-3), 175.8(C-4), 156.1
(C-5), 98.1(C-6), 163.7(C-7), 93.3(C-8), 160.6
(C-9), 102.9(C-10), 121.5(C-1′), 129.3(C-2′,
6′), 115.3(C-3′, 5′), 159.0(C-4′).TheNMRdata
wereinaccordancewiththoseofkaempferol[ 8] .
Vitexin(6)　Yelowneedles(MeOH), mp.262-264
℃;1HNMR(500 MHz, DMSO-d6)δ:13.16(1H, s, 5-
OH), 10.76(1H, s, 7-OH), 10.31(1H, s, 4′-OH),
8.00(2H, d, J=8.6 Hz, H-2′, 6′), 6.89(2H, d, J=
8.6Hz, H-3′, 5′), 6.64(1H, s, H-6), 4.69(1H, d, J
=9.7 Hz, H-1″);13 CNMR(125 MHz, DMSO-d6)δ:
163.9(C-2), 102.4(C-3), 182.0(C-4), 160.3(C-
5), 98.1(C-6), 162.5(C-7), 104.6(C-8), 156.0(C-
9), 104.0(C-10), 121.6(C-1′), 128.9(C-2′, 6′),
115.7(C-3′, 5′), 161.1(C-4′), 78.6(C-1″), 73.3
(C-2″), 70.8(C-3″), 70.5(C-4″), 81.8(C-5″), 61.2
(C-6″).TheNMRdatawereidenticaltothoseofvitex-
in[ 9] .
Apigenin-7-O-β-D-glucuronide(7)　Brownamor-
phouspowder(MeOH), mp.>300 ℃;1HNMR(500
MHz, DMSO-d6)δ:12.95(1H, brs, 5-OH), 7.93
(2H, d, J=8.8 Hz, H-2′, 6′), 6.93(2H, d, J=8.8
Hz, H-3′, 5′), 6.83(1H, s, H-3), 6.81(1H, d, J=2.0
Hz, H-8), 6.43(1H, d, J=2.0 Hz, H-6), 5.12(1H,
d, J=7.2Hz, H-1″);13CNMR(125 MHz, DMSO-d6)
δ:164.2(C-2), 103.0(C-3), 181.9(C-4), 161.4(C-
5), 99.5(C-1″, C-6), 162.9(C-7), 94.6(C-8),
156.9(C-9), 104.0(C-10), 120.8(C-1′), 128.5(C-
2′, 6′), 115.9(C-3′, 5′), 161.0(C-4′), 72.9(C-2″),
74.3(C-3″), 71.8(C-4″), 76.2(C-5″), 172.0(C-
6″).TheNMRdatawereinaccordancewiththoseof
apigenin-7-O-β-D-glucuronide[ 10] .
Genkwanin(8 )　 Yelow amorphous powder
(MeOH), mp.283-285 ℃;1HNMR(500 MHz, DM-
SO-d6)δ:12.96(1H, s, 5-OH), 10.35(1H, s, 4′-
OH), 7.96(2H, d, J=6.8 Hz, H-2′, 6′), 6.94(2H,
d, J=6.8 Hz, H-3′, 5′), 6.84(1H, s, 3-OH), 6.77
(1H, d, J=2.3Hz, H-8), 6.38(1H, d, J=2.3Hz, H-
6), 3.87(3H, s, 7-OCH3);13CNMR(125 MHz, DM-
SO-d6)δ:164.0(C-2), 103.0(C-3), 181.9(C-4),
157.2(C-5), 97.9(C-6), 165.1(C-7), 92.6(C-8),
161.2(C-9), 104.0(C-10), 121.0(C-1′), 128.5(C-
2′, 6′), 115.9(C-3′, 5′), 161.1(C-4′), 56.0(7-
OCH3).TheNMRdatawereinaccordancewiththose
ofgenkwanin[ 11] .
Quercetin(9)　Yelowamorphouspower, mp.>300
℃.Itwasidentifiedasquercetinbycomparisonof
mixedmeltingpointandRfvaluewithanauthentic
sample.
Dihydroquercetin(10)　Yelowamorphouspower,
mp.210-212 ℃.[ α] 22D-21.9(c0.10 , EtOH).Itwasi-
dentifiedasdihudroquercetinbycomparisonofmixed
meltingpointandRfvaluewithanauthenticsample.
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