全 文 ：天然产物研究与开发 NatProdResDev2007, 19:430-432
文章编号:1001-6880(2007)03-0430-03
ReceivedApril18, 2006;AcceptedJune20, 2006
FoundationItem:ThisworkwassupportedbyNationalNaturalScience
Fund(29972017).
＊CorrespondingauthorTel:86-931-7650892;E-mail:jltycx@ 126.com
半卧狗娃花中的黄酮类化合物
杨彩霞 1＊ ,贾忠建 2
1西北师范大学化工学院 , 兰州 730070;2兰州大学化工学院 ,兰州 730000
摘 要:从半卧狗娃花(HeteropappussemiprostGriers)全草的乙醇提取物中分离并鉴定了 7个黄酮类化合物 , 通
过波谱分析及化学方法鉴定其结构为:3′, 4′, 5, 7-四羟基黄酮 (1), 3′-甲氧基槲皮素(2), 槲皮素-3-O-α-L-吡喃
鼠李糖甙 (3),槲皮素-3-O-β-D-吡喃半乳糖甙 (4),异鼠李亭-3-O-β-D-吡喃半乳糖甙(5), 槲皮素-3-O-α-L-吡喃
鼠李糖(1※ 6)-β-D-吡喃葡萄糖甙(6),异鼠李亭-3-O-α-L-吡喃鼠李糖(1※ 6)-β-D-吡喃葡萄糖甙(7),其中化合
物 1 ～ 5为首次从本属植物中分离得到。
关键词:半卧狗娃花;黄酮类化合物;槲皮素;异鼠李亭
中图分类号:R284.1;Q946.91 文献标识码:A
FlavonoidsfromHeteropappussemiprostGriers
YANGCai-xia1＊ , JIAZhong-jian2
1DepartmentofChemicalandEngineering, NorthwestNormalUniversity, Lanzhou730070 , China;
2DepartmentofChemicalandEngineering, LanzhouUniversity, Lanzhou730000 , China
Abstract:SevenflavonoidswereisolatedfromHeteropappussemiprostGriers, andidentifiedas3′, 4′, 5, 7-tetrahydroxyfla-
vone(1), 3′-methoxyquercetin(2), quercetin3-O-α-L-rhamnopyranoside(3), quercetin3-O-β-D-galactopyranoside(4),
isorhamnetin3-O-β-D-galactpyranoside(5), quercetin3-O-α-L-rhamnopyranoside(1※ 6)-β-D-glucopyranoside(6)and
isorhamnetin3-O-α-L-rhamnopyranoside(1※ 6)-β-D-glucopyranoside(7)onthebasisofspectralanalysisandchemical
methods.Amongthem, compounds1-5 wereobtainedfromthisplantforthefirsttime.
Keywords:HeteropappussemiprostGriers;flavonoids;quercetin;isorhamnetin
Introduction
ThegenusHeteropappus(Compositae)haslongbeen
usedasheat-clearinganddetoxificationdruginChina
andMongolia.Triterpeneglycosidesandflavonoidgly-
cosideshavebeenreportedasthemostwidespread
maincomponentsinthisgenus[ 1-3] .However, theplant
HeteropappussemiprostGriershasnotbeenstudiedup
todate.FromitsEtOHextract, sevenflavonoidswere
obtained, andidentifiedas3′, 4′, 5, 7-tetrahydroxyfla-
vone(1), 3′-methoxyquercetin(2), quercetin3-O-α-L-
rhamnopyranoside(3), quercetin3-O-β-D-galactopyr-
anoside(4), isorhamnetin3-O-β-D-galactopyranoside
(5), quercetin3-O-α-L-rhamnopyranoside(1※6)-β-
D-glucopyranoside(6)andisorhamnetin3-O-α-L-rham-
nopyranoside(1※ 6)-β-D-glucopyranoside(7)upon
spectralanalysisandchemicalmethods.Compounds1-
5wereobtainedfromthisplantforthefirsttime.
Experiment
Instrumentsandmaterials
MeltingpointsweredeterminedonaKeflermelting
pointapparatusuncorected.IRspectrawererecorded
onaNicoletNEXUS670 FT-IRspectrometer.FABMS
wereobtainedonaVG-ZAB-HSmassspectrometer.1H
NMR(300 MHz)and13CNMR(75 MHz)wererecor-
dedonaVarianMercuryPlus-300BBNMRspectrome-
terandchemicalshiftsarereportedinppmusingDM-
SO-d6 assolvent.Silicagel(200-300mesh)forcolumn
chromatographyandGF254(10-40μ)forTLCweresup-
pliedbytheQingdaoHaiyangChemicalCo., Ltd..
SpotsonTLCweredetectedunderUVlampandby
heatingafterspraying5% H2SO4 inC2H5OHor5%
FeCl3 inC2H5OH.ThewholeplantsofHeteropappus
DOI :10.16333/j .1001 -6880.2007.03.017
semiprostGrierswerecolectedinMaqu, GansuProv-
ince, China, inAugust2001.ItwasidentifiedbyProf.
Zhang Guo-liang, Colege ofBiologicalScience,
LanzhouUniversity.Avoucherspecimen(No.10821)
wasdepositedintheColegeofChemistryandChemi-
calEngineering, LanzhouUniversity.
Extractionandisolation
ThedriedandpoweredwholeplantsofH.semiprost
Griers(1.8 kg)weremaceratedthreetimeswith95%
EtOHatroomtemperature(eachtimefor7days), After
removingsolventsunderreducedpressure, theresulting
residue(130 g)wasseparatedonasilicagelcolumn
(6.0×150cm, 700g)elutedwithpetroleumether, pe-
troleum ether-Et2O(5∶1), CHCl3 , CHCl3-MeOH
(50∶1, 30∶1, 10∶1, 5∶1, 1∶1, 2000 mLeacheluent)to
afordeightfractions(Fr1 -Fr8)accordingtoTLCanaly-
sis.Fr4(CHCl3-MeOH50∶1, 2 g)wasseparatedona
silicagelcolumnelutedwithCHCl3-MeOHtogive1(9
mg, 10∶1)and2(7 mg, 3∶1).TheseparationofFr5
(CHCl3 -MeOH 30∶1, 389 mg)onsilicagelcolumn
andpolyamidecolumnelutingwithCHCl3-MeOHgave
3(9mg, 20∶1), 4(11 mg, 10∶1)and5(5 mg, 5∶1).
Fr6(CHCl3 -MeOH10∶1, 12g)wasseparatedonasili-
cagelcolumn(1.5×30 cm, 30 g)elutedwithCHCl3-
MeOH(50∶1-1∶1)toyield6(4 mg, 10∶1)and7(8
mg, 10∶1).
Identification
Fig.1 Chemicalstructuresofcompounds1-7
Compound1 Yelowneedlecrystals(MeOH), mp.
312-314℃;FABMSm/z:287 [ M+H] +;UVλMeOHmax
nm:212, 268(sh), 335;1HNMR(DMSO-d6)δ:12.48
(5-OH), 10.78(7-OH), 9.76(4′-OH), 9.36(3′-
OH), 7.65(1H, d, J=1.2 Hz, H-2′), 7.51(1H, d, J
=8.7 Hz, H-6′), 6.86(1H, d, J=8.7 Hz, H-5′),
6.39(1H, s, H-8), 6.17(1H, s, H-6), 6.00(1H, s, H-
3).Thesedatawereidenticalwith3′, 4′, 5 , 7 -tetra-
hydroxyflavone[ 4] .
Compound 2 Yelow powder, mp.302-305 ℃;
FABMSm/z:317 [ M+H] +;UVλMeOHmax nm:256, 265
(sh), 290(sh), 351;1HNMR(DMSO-d6)δ:12.46(5-
OH), 10.79(7-OH), 9.76(4′-OH), 9.45(3-OH),
3.85(3H, s, 3′-OCH3), 7.76(1H, s, H-2′), 7.69
(1H, d, J=8.1 Hz, H-6′), 6.95(1H, d, J=8.1 Hz,
H-5′), 6.49(1H, s, H-8), 6.21(1H, s, H-6).These
MSand1HNMRspectraldatawereidenticalwith3′-
methoxyquercetin[ 5].
Compound 3 Yelow powder, mp.165-167 ℃;
[ α] 20D +47°(c0.51, MeOH);FABMSm/z:471[ M+
Na] + , 455 [ M+Li] + , 302 [ aglycone] +;UVλMeOHmax
nm:257, 265, 355;1HNMR(DMSO-d6)δ:12.58(5-
OH), 10.82(7-OH), 9.66(4′-OH), 9.17(3′-OH),
7.53(1H, d, J=1.5 Hz, H-2′), 7.51(1H, d, J=8.0
Hz, H-6′), 6.81(1H, d, J=8.0 Hz, H-5′), 6.36(1H,
s, H-8), 6.17(1H, s, H-6), 5.31(1H, s, H-1″), (3H,
d, J=6.6 Hz, H-6″).Thespectraldatawereidentical
withquercetin3-O-α-L-rhamnopyranoside[ 4] .
Compound 4 Yelow powder, mp.230-231 ℃;
[ α] 20D-54°(c0.50, MeOH);FABMSm/z:487 [ M+
Na] + , 471 [ M+Li] +, 302 [ aglycone] +;UVλMeOHmax
nm:256, 266(sh), 357;1HNMR(DMSO-d6)δ:12.63
(5-OH), 10.83(7-OH), 9.78(4′-OH), 9.21(3′-
OH), 8.04(1H, s, H-2′), 7.68(1H, d, J=8.7 Hz, H-
6′), 6.84(1H, d, J=8.7 Hz, H-5′), 6.42(1H, s, H-
8), 6.22(1H, s, H-6), 5.39(1H, d, J=7.5 Hz, H-
1″).TheUV, MSand1HNMRdatawereidenticalwith
quercetin3-O-β-D-galactpyranoside[ 6].
Compound 5 Yelow powder, mp.186-188 ℃;
[ α] 20D -57°(c0.46, MeOH);FABMSm/z:501 [ M+
Na] + , 485[ M+Li] + , 316[ aglycone] +;UVλMeOHmax nm:
256, 266(sh), 354;1HNMR(DMSO-d6)δ:12.64(5-
OH), 10.84(7-OH), 9.80(4′-OH), 8.04(1H, s, H-
2′), 7.51(1H, d, J=8.1 Hz, H-6′), 6.91(1H, d, J=
8.7Hz, H-5′), 6.46(1H, s, H-8), 6.22(1H, s, H-6),
5.53(1H, d, J=7.5 Hz, H-1″), 3.86(3H, s, 3′-
OCH3);13CNMR(75 MHz, DMSO-d6)δ:157.0(C-
2), 133.8(C-3), 178.1(C-4), 161.9(C-5), 94.3(C-
6), 164.8(C-7), 99.4(C-8), 157.0(C-9), 104.7(C-
10), 121.7(C-1′), 114.2(C-2′), 150.0 (C-3′),
431Vol.19 YANGCai-xiaetal:FlavonoidsfromHeteropappussemiprostGriers
147.6(C-4′), 115.8(C-5′), 122.5(C-6′), 102.2(C-
1″), 71.9(C-2″), 73.7(C-3″), 68.6(C-4″), 76.6(C-
5″), 61.0(C-6″), 56.6(OCH3).Thesedatawerei-
denticalwithisorhamnetin3-O-β-D-galactpyranoside
[ 5, 7] .
Compound 6 Yelow powder, mp.190-192 ℃;
[ α] 20D -102.3°(c0.25, MeOH);FABMSm/z:611 [ M
+H] + , 302 [ aglycone] +;UVλMeOHmax nm:259, 266
(sh), 299(sh), 358;1HNMR(DMSO-d6)δ:12.58(5-
OH);10.85(7-OH), 9.67(4′-OH), 9.18(3′-OH),
7.53(1H, d, J=1.7Hz, H-2′), 7.51(1H, d, J=9.0
Hz, H-6′), 6.83(1H, d, J=9.0 Hz, H-5′), 6.39(1H,
d, J=1.8Hz, H-8), 6.19(1H, d, J=1.8 Hz, H-6);13C
NMR(75 MHz, DMSO-d6)δ:156.4(C-2), 133.3(C-
3), 177.4(C-4), 161.2(C-5), 98.7(C-6), 164.1(C-
7), 93.6(C-8), 156.6(C-9), 103.9(C-10), 121.2
(C-1′), 115.2(C-2′), 144.7(C-3′), 148.4(C-4′),
116.0(C-5′), 121.6(C-6′), 101.2(C-1″), 74.1(C-
2″), 76.5(C-3″), 70.6(C-4″), 75.9(C-5″), 67.0(C-
6″), 100.7(C-1 ), 70.3(C-2 ), 70.6(C-3 ), 71.9
(C-4 ), 68.2(C-5 ), 17.7(C-6 ).Theabove13C
NMRdatawereidenticalwithquercetin3-O-α-L-rham-
nopyranoside(1※6)-β-D-glucopyranoside[ 7].
Compound7 Yelowpowder, [ α] 20D-103.1°(c
0.21, MeOH);FABMSm/z:647 [ M+Na] +, 631[ M
+Li] + , 477[ M-rha-1] +, 316[ aglycone] +;UVλMeOHmax
nm:257, 266(sh), 352;1HNMR(DMSO-d6)δ:12.57
(5-OH), 10.88(7-OH), 9.79(4′-OH), 9.25(3′-
OH), 7.85(1H, d, J=1.8 Hz, H-2′), 7.50(1H, d, J
=8.1 Hz, H-6′), 6.90(1H, d, J=8.1 Hz, H-5′),
6.43(1H, d, J=2.4 Hz, H-8), 6.20(1H, d, J=2.4
Hz, H-6), 5.41(1H, d, J=7.5 Hz, H-1″), 5.15(1H,
s, H-1 ), 3.83(3H, s, 3′-OCH3), 0.98(3H, d, J=
1.8 Hz, 5 -H).Thesedatewereidenticalwithisorh-
amnetin3-O-α-L-rhamnopyranoside(1※6)-β-D-gluco-
pyranoside[ 8] .
Acknowledgement Thisworkwassupportedbythe
National Natural Science Foundation of China
(No.29972017).
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432 NatProdResDev Vol.19