全 文 ：TwonewflavonesfromRubusbiflorusBuch
KANGShu-he1＊ , ZHENGShang-zhen2
(1.SchoolofChemicalEngineering, NorthwestMinoritiesUniversity, Lanzhou730030 , China;
2.SchoolofChemicalEngineering, NorthwestNormalUniversity, Lanzhou730060 , China)
Abstract:ThisprojectistostudychemicalconstituentsofRubusbiflorusBuch(Chinesename
“ Fenzhimei”), isolatedbysilicagelchromatographyandstructuredeterminedbyspectroscopic
techniques.Twoflavoneswereisolatedfrom RubusbiflorusBuchandidentifiedas8-methyl-6-(3″-
methylbut-2″-enyl)-5, 7-dihydroxy-5′-methoxy-3′, 4′-methylenedioxyflavone(A) and 8-methyl-5-
methoxy-6, 7-(2″, 2″-dimethylpyran)-3′, 4′-methylenedioxy-5′-(3 -methylbut-2 -enyl)flavone(B),
namedasfenzhiminesAandB, respectively.CompoundsAandBaretwonewflavonoids.
Keywords:flavone;RubusbiflorusBuch;RubusL;fenzhimine
CLCnumber:R284.1　　　Documentcode:A　　　ArticleID:0513-4870(2007)12-1288-04
Received2007-07-09.
＊Corespondingauthor　Tel:86-931-2927883,
Fax:86-931-2938253,
E-mail:kangshuhe@163.com
粉枝莓中的两种新黄酮成分
康淑荷1＊ , 郑尚珍 2
(1.西北民族大学 化工学院 , 甘肃 兰州 730030;2.西北师范大学 化工学院 , 甘肃 兰州 730060)
摘要:为研究粉枝莓(RubusbiflorusBuch)的化学成分 , 经柱色谱分离 ,从粉枝莓中分离得到 2个黄酮类化合物 ,
光谱分析鉴定其结构为:8-甲基-6-异戊烯基-5, 7-二羟基-5′-甲氧基-3′, 4′-二氧亚甲基黄酮(A), 和 8-甲基-5′-异戊烯
基-5-甲氧基-6, 7-(2″, 2″-二甲基吡喃)-3′, 4′-二氧亚甲基黄酮(B), 分别命名为粉枝莓素 A和粉枝莓素 B。化合物 A
和 B为新的黄酮类化合物。
关键词:黄酮;粉枝莓;悬钩子属;粉枝莓素
　　RubusbiflorusBuchisamedicinalplantofChina
used fortreating dysentery, improving eyesight,
tonifyingthekidney, etc.[ 1, 2] .Flavonoids, terpenoids,
sterolsandorganicacids, etc.havebeenfoundinthe
speciesofRubus[ 3] , butthechemicalconstituentsof
RubusbiflorusBuchhavenotbeenreported.This
paperdescribedtheisolationandstructuralelucidation
oftwoflavones, theirstructuresweredeterminedas
8-methyl-6-(3″-methylbut-2″-enyl)-5, 7-dihydroxy-
5′-methoxy-3′, 4′-methylenedioxyflavone(A)and8-
methyl-5′-(3 -methylbut-2 -enyl)-5-methoxy-6, 7-
(2″, 2″-dimethylpyran)-3′, 4′-methylenedioxyflavone
(B), namedasfenzhiminesAandB, respectively.
CompoundsAandBaretwonewflavonoids.
Resultsanddiscussion
CompoundA　wasisolatedasyelowneedles,
itsHRMSexhibitedm/z:410.189 3[ M] +, core-
spondingtothemolecularformulaC23H22O7.TheIR
spectrumexhibitedstrongabsorptionbandsat1 635
cm-1 (chelatedC=O) and 3 440 cm-1 (strong
H-bondingOH).Itwasidentifiedasflavonesmainly
viathecharacteristic13CNMR signalsofC-2 (δ
160.8), C-3(δ104.2), C-4(δ181.4), together
withitsUVspectraλMeOHmax nm:348 , 280, 245, 232
nm. Its yelow colordisappeared on zirconium
oxychloride-citricacid reaction, itsupported the
presenceofahydroxylgroup(δ12.88)atachedto
·1288· 药学学报 ActaPharmaceuticaSinica2007, 42(12):1288-1291
C-5.TheMSgavetheprominentfragmentsatm/z:
355[ M-55] +, 367[ M-43] +and354[ M-56] + ,
suggestedthepresenceofa3-methylbut-2-enyl(prenyl)
unit[ 4, 5] .Thissuggestionwasconfirmedbythe1HNMR
spectrumwhichshowedsignalsatδ3.26(d, 2H, CH2 ,J=7.2Hz), 5.16(t, 1H, CH, J=7.2 Hz), 1.70(s,
3H), and1.63(s, 3H)foraprenylgroup.1HNMR
spectraldatashowedaprotonsingletatδ6.55(s, 1H)
duetoH-3, andtwophenolichydroxylprotonsof
whichone(δ12.88, s, 1H, disappearedinD2O)
wasstronglyhydrogenbonded.A strongsingletat
δ6.07(s, 2H)wastypicalofamethylenedioxygroup.
InthelowfieldregionanABcouplingsystematδ7.24
(d, 1H, J=2.1 Hz)andδ7.30(d, 1H, J=2.1 Hz)
wereassignedtothe2′, 6′-unsubstitutedsysteminthe
B-ring.The1HNMR spectrum furthershowedthe
presenceofamethoxylsignal(δ3.94, s, 3H), andan
aromaticmethylsignal(δ2.36, s, 3H).HMBC
spectrum showedthatmethoxylprotons(δ3.94)
existedlong-rangeheteronuclearcorelationswithδ
147.6(C-5′), leadingtothelocationofmethoxyl
grouponC-5′.TheABcouplingsystemandfragment
ionatm/z176, producedbytheC-ringRDAfission,
indicatedthattheB-ringwassubstitutedatC-3′, C-4′
andC-5′positionswithamethylenedioxyandmethoxyl
group[ 6] .Theplacementofthemethylenedioxygroupδ
6.07(2H, s)atC-3′andC-4′wasalsoestablishedby
HMBCexperimentwhichshowedthecorelationsof
OCH2OprotonsandcarbonsatC-3′(δ142.8)and
C-4′(δ146.3).TheprenylunitwasasignedtoC-6
(δ110.2), becauseof13C-1Hlong-rangecorrelations
werededucedbetweenH-1″(δ3.26, d, 2H, J=7.2
Hz)andC-5(δ156.8)andC-7(δ155.3), andalso
betweenH-2″(δ5.16, t, 1H, J=7.2 Hz)andC-6(δ
110.2).Furthermore, theHMBCexperimentsindicated
the13C-1Hlong-rangecorelationsbetweenH(δ2.36)
ofaromaticmethylandC-7(δ155.3), C-8(δ105.7)
andC-9(δ151.3), andbetweenOH(δ10.32)and
C-7(δ155.3), andalsobetweenOH(δ12.88)and
C-5(δ156.8).Fromthesespectraldata, compoundA
wasidentifiedasthenovelflavone8-methyl-6-(3″-
methylbut-2″-enyl)-5, 7-dihydroxy-5′-methoxy-3′, 4′-
methylenedioxy flavone, named asfenzhimine A
(Figure1).
CompoundB　 analyzedbyHRMSform/z:
460.242 6[ M] +, indicatinganexperimentalformula
ofC28H28O6.IRspectrumofBshowedthepresenceof
carbonylgroup(1 645 cm-1 )andaromaticring
(1 590, 1 462 cm-1).The1HNMRspectrumofB
showedanaromaticmethylatδ2.34(s, 3H), a
methylenedioxygroupatδ6.02(s, 2H)similarto
thoseofA.Theprotonsignalsatδ6.55(s, 1H, -CH),
δ7.19(d, 1H, -CH, J=2.1 Hz)andδ7.28(d, 1H,
J=2.1 Hz)wereassignedtoH-3 andthe2′, 6′-
unsubstitutedsystemintheB-ring.Thedoubletsatδ
5.59 andδ6.68(1H, each, J=10.0 Hz)andthe
singletatδ1.45(s, 6H)werecharacteristicofthecis-
doublebondandgem-dimethylgroupofa2, 2-
dimethylchromenemoiety[ 7] .The13CNMRspectrum
andafragmentioninitsmassspectrumatm/z231
(C), atributedtoC-ringRDAfision, indicatedthat
the2, 2-dimethylpranringatC-6 andC-7 positionson
A-ring.ThiswassupportedbytheHMBCexperiment,
whichshowedcorelationsbetweenH-3″(δ5.59)and
C-6 (δ104.5), andbetweenH-4″(δ6.68)andC-5
(δ157.1), C-7(δ159.0), andC-2″(δ77.8).
Furthermore, 1HNMRspectrumrevealedresonances
foronemethoxylgroupatδ3.89(s, 3H)anda3-
methylbut-2-enylunit.However, inthiscase, 3-
methylbut-2-enylwasassignedtoC-5′, andmethoxyl
groupassignedtoC-5, becauseof13C-1Hlong-range
corelationsbetweenH-1 (δ3.21, d, 2H, J=7.2Hz)
andC-4′(δ145.2)andC-6′(δ118.6), andbetween
H-2 (δ5.22, t, 1H, J=7.2Hz)andC-5′(δ125.1),
andalsobetweenCH3O(δ3.89)andC-5(δ157.1).
Furthermore, acomparisonofthe13CNMRandDEPT
spectraofAandB, showedtheothermoietyofBwas
sameasthatofA.ThuscompoundBwasdeducedas
Figure1　StructuresofA, BandEI-MSfragmentionCofB
·1289·KANGShu-he, etal:TwonewflavonesfromRubusbiflorusBuch
8-methyl-5′-(3 -methylbut-2 -enyl)-5-methoxy-6, 7-
(2″, 2″-dimethylpyran)-3′, 4′-methylenedioxyflavone,
namedasfenzhimineB(Figure1).
Experimental
MeltingpointsweremeasuredonaChineseX-4
meltingpointapparatusanduncorrected.UVspectra
weremeationedonaShimadzuUV-250 spectrometerin
MeOH.IR spectrawereobtainedonPerkin-Elmer
599Bspectrometer, andmassspectrawereobtainedon
aMAT-112 masspectrometer.1HNMR, 13CNMR,
DEPTandHMBCwererecordedonaBrukerAM-400
spectrometer.
ThesamplesofRubusbiflorusBuchwerecolected
inSichuanProvince, China, onAugust2005, and
identifiedbyProfessionLIANYun-shan, Department
ofBiologyNorthwestNormalUniversity.
Theshade-driedandpowderedRubusbiflorus
Buch(3kg)wasextractedwith95% EtOHfourtimes
atroomtemperature(eachproceslasting7 days).
Afterremovalofthesolventbyevaporation, theEtOH
extracts(300g)wereextractedwithhexane, CH2Cl2 ,
EtOAcandMeOHunderreflux(threetimeseach).A
partoftheEtOAcextract(56 g)wassubjectedto
silicagelcolumnchromatographyandmixturesof
CH2Cl2 -EtOAcandEtOAc-MeOHofincreasingpolarity
wereusedaseluents, afording38 fractions.The
fractions20 waspurifiedbypreparativeTLC(GF254 ,
silicagel, Qindao, China)withCH2Cl2-EtOAc-MeOH
(3∶6.5 ∶0.5)aseluent, andafterrecrystalization
(CH2Cl2 -EtOAc)toyieldA(32 mg).TheCH2Cl2
extract(43 g)wassubjectedtosilicagelcolumn
chromatographyusingmixturesofhexane-CH2Cl2 and
CH2Cl2 -EtOAcofincreasingpolarityaseluentafording
36 fractions.Recolumnchromatographyoffractions
16-19withhexane-CH2Cl2-EtOAc(3∶5∶3)aseluent
gavecompoundB(41mg).
Identification
8-Methyl-6-(3″-methylbut-2″-enyl)-5 , 7-di-
hydroxy-5′-methoxy-3′, 4′-methylnedioxyflavone
(fenzhimineA)　 C23H22O7 , yelowneedles, mp
167-169℃.IR(KBr):3 440(OH), 2 965, 2 960,
1 635, 1 585, 1 465, 1 386, 1 280, 900-600cm-1.
UVshowedpeaksat348, 280, 245, 232 nm.MS
m/z:410 [ M] +(36), 395(58), 392(41), 367
(19), 355(100), 354(23), 340(7), 180(21),
176(16), 152(6).HREIMSm/z:found410.189 3,
calculatedforC23H22O7 , 410.189 8.1HNMR(400
MHz, CDCl3)δ:12.88(s, 1H, -OH), 10.32(s, 1H,
-OH), 7.30(d, 1H, CH, J=2.1 Hz, H-6′), 7.24(d,
1H, CH, J=2.1 Hz, H-2′), 6.52(s, 1H, CH, H-3),
6.07(s, 2H, OCH2O), 5.16(t, 1H, CH, J=7.2 Hz,
H-2″), 3.94(s, 3H, -OCH3), 3.26(d, 2H, CH2 , J=
7.2 Hz, H-1″), 2.36(s, 3H, -CH3), 1.70(s, 3H,
3″-CH3), 1.63(s, 3H, 3″-CH3).13CNMR(100 MHz,
CDCl3)δ:160.8(C-2), 104.2(C-3), 181.4(C-4),
156.8(C-5), 110.2(C-6), 155.3(C-7), 105.7
(C-8), 151.3(C-9), 104.6(C-10), 126.1(C-1′),
107.4(C-2′), 142.8(C-3′), 146.3(C-4′), 147.6
(C-5′), 104.5(C-6′), 21.1(C-1″), 121.6(C-2″),
130.2(C-3″), 8.8(-CH3), 100.8(-OCH2O-), 25.0(C-4″), 18.9(C-5″), 55.8(5′-OMe).
8-Methyl-5′-(3 -methylbut-2 -enyl)-5-methoxy-
6, 7-(2″, 2″-dimethylpyran)-3′, 4′-methylenedioxy
flavone(fenzhimineB)　C28H28O6 , yelowneedles,
mp178-180 ℃.IR(KBr):3 078, 2 964 , 2 875,
1 645, 1 590, 1 462, 1 383, 1 375 , 900-600cm-1.
UVshowedpeaksat256, 283, 307, 342 nm.MS
m/z:460 [ M] +(39), 445(100), 430(21), 417
(48), 401(23), 386(12), 224(8), 231(19), 148
(16).HREIMSm/z:found460.242 6, calculatedfor
C28H28O6 , 460.243 2.1HNMR(400 MHz, CDCl3)
δ:7.28(d, 1H, CH, J=2.1Hz, H-2′), 7.19(d, 1H,
CH, J=2.1 Hz, H-6′), 6.68(d, 1H, CH, J=10.0
Hz, H-4″), 6.55(s, 1H, CH, H-3), 6.02(s, 2H,
-OCH2O-), 5.59(d, 1H, CH, J=10.0 Hz, H-3″),
5.22(t, 1H, CH, J=7.2 Hz, H-2 ), 3.89(s, 3H,
-OCH3), 3.21(d, 2H, CH2 , J=7.2 Hz, H-1 ), 2.34
(s, 3H, -CH3), 1.64(s, 3H, 3 -CH3), 1.60(s, 3H,
3 -CH3), 1.45(s, 6H, CH3 , 2″-Me).13CNMR(100
MHz, CDCl3)δ:162.1(C-2), 104.9(C-3), 178.0
(C-4), 157.1(C-5), 104.5(C-6), 159.0(C-7),
106.2(C-8), 153.4(C-9), 105.3(C-10), 125.3
(C-1′), 106.9 (C-2′), 141.1 (C-3′), 145.2
(C-4′), 125.1(C-5′), 118.6(C-6′), 77.8(C-2″),
127.7(C-3″), 115.3(C-4″), 28.1(C-5″, C-6″),
27.4(C-1 ), 121.3(C-2 ), 130.0(C-3 ), 25.1
(C-4 ), 19.2(C-5 ), 8.6(8-Me), 59.8(5-OMe),
99.2(-OCH2O-).
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·1291·KANGShu-he, etal:TwonewflavonesfromRubusbiflorusBuch