全 文 ：天然产物研究与开发 NatProdResDev2008, 20:770-772
文章编号:1001-6880(2008)05-0770-03
　
　
　ReceivedMarch31, 2008;AcceptedApril28, 2008
　FoundationItem:Thisresearchworkwasfinancialysupportedbythe
NationalKeyProjectforBasicResearch(2003CB114400)andNation-
alNaturalScienceFoundationofChina(30440046).
＊CorrespondingauthorTel:86-013159802118;E-mail:xiangwensheng@
yahoo.com.cn
垂子买麻藤中一个新的均二苯乙烯化合物
姜　冰 1 ,张　鑫 2 ,王相晶 1 ,郭锁莲 1 ,向文胜 1＊
1东北农业大学生命科学学院 , 哈尔滨 150030;2浙江海正药业股份有限公司 ,台州 318000
摘　要:从垂子买麻藤(Gnetumpendulum)茎中分离到四个双烯苯类化合物 , 经波谱学鉴定为 3, 5-二羟基-4-甲氧
基均二苯代乙烯(1)、银松素(2)、丹叶大黄素(3)、射干乙素(4)。其中化合物 1为新化合物。
关键词:买麻藤;垂子买麻藤;均二苯乙烯;3, 5-二羟基-4-甲氧基均二苯乙烯
中图分类号:R284.2;Q946.91 文献标识码:A
ANewStilbenefromtheLianasofGnetumpendulum
JIANGBing1 , ZHANGXin2 , WANGXiang-jing1 , GUOSuo-lian1 , XIANGWen-sheng1＊
1InstituteofLifeScience, NortheastAgriculturalUniversity, Harbin150030 , China;
2ZhejiangHisunPharmaceuticalCo., Ltd., Taizhou318000 , China
Abstract:Anewstilbene, 3, 5-dihydroxy-4-methoxystilbene(1), alongwithpinosylvin(2), rhapontigenin(3)andshe-
gansuB(4)wereisolatedfromthedriedstemsofGnetumpendulum.Thenewcompoundwasstructurallyelucidatedby
spectroscopicmethods.
Keywords:Gnetum;Gnetumpendulum;stilbenoid;3, 5-dihydroxy-4-methoxystilbene
Introduction
TheplantsofGnetumspecieshavebeenusedinthe
treatmentofbronchitisandarthritisinChinaasfolk
medicine[ 1] .Inrecentyears, varioustypesofstilbenes
showingpotentanti-inflammatoryactivitieshavebeen
foundfromthreeChineseGnetumspecies, G.parvifoli-
um, G.montanumandG.hainanense[ 2] .Tofurtherun-
derstandthebioactivesubstancesinG.pendulum, we
investigateditschemicalcomposition.Anewstilbene,
3, 5-dihydroxy-4-methoxystilbene(1), alongwiththree
knowncompounds, pinosylvin(2), rhapontigenin(3)
andshegansuB(4)(Fig.1 and2)wereisolatedfrom
thedriedstemsofG.pendulum.
Experimental
General
UVspectrawereobtainedonaVarianCARY300 BIO
spectrophotometer, IRspectraonaNicoletMagnaFT-
IR750 spectrometer(υmaxincm-1);1Hand13CNMR
spectrawererecordedonaBrukerDRX-400 (1H:400
MHz;13C:100MHz)spectrometer.Chemicalshiftsare
reportedonppm(δ), usingtheresidualCHCl3 (δH
7.28 ppm;δC 77.0)orCD3OD(δH 3.30;δC 49.0)as
internalstandard, couplingconstant(J)inHz.1Hand
13CNMRassignmentsweresupportedby1H-1HCO-
SY, HMQCandHMBCexperiments.TheESI-MSand
HRESI-MSspectraweretakenonaQ-TOFMicroLC-
MS-MS massspectrometer.The Sephadex LH-20
(Pharmacia)columnwaselutedwithMeOH.Sigel
(QingDaoHaiYangChemicalGroupCo., 100-200
and200-300 mesh)wasusedforcolumnchromatogra-
phy, precoatedSigelplates(YantaiZifuChemical
GroupCo., G60 F254)foranalyticalTLC.
Plantmaterial
PlantmaterialwascolectedinXishuangbannaofYun-
nanProvince, China, inJuly2003, andidentifiedas
GnetumpendulumC.Y.Cheng.byProf.Bao-zhongHu.
Thevoucherspecimen(200689)wasdepositedinthe
HerbariumofFacultyofScience, DepartmentofBota-
ny, NortheastAgriculturalUniversity.
Extractionandisolation
Thedriedgroundstems(4.0 kg)ofGnetumpendulum
werepercolatedwith95% ethanolextensivelyatroom
temperaturetogiveacrudeextract(170g).Thecrude
extractsuspendedinwater(1 L)waspartitionedwith
ethylacetatetooferethylacetatesolublefraction(30
g).Theethylacetatesolublefractionwassubjectedto
silicacolumnchromatographyelutedgradientlywith
petroleumether-acetonetoafordfractions1-10 onthe
basisofTLC.Fraction3(4.0 g)wasappliedtoasi-
licagelcolumnelutedwithpetroleumether-EtOAc(9∶1-
1∶1).ThefractionwithRf=0.5 (developingwithpe-
troleumether/acetone3∶2)wasthensubjectedtosili-
cagelcolumnchromatographyelutedwithpetroleume-
ther-acetone(9∶1-3∶2)togive1 (17 mg)and2(12
mg).Fraction6 (1.7g)wasseparatedoversilicagel
columnchromatographyelutedwithCHCl3-MeOH(99∶1-
17∶1).TheeluatewithRf=0.6 (developingwith
CHCl3-MeOH9∶1)wasthenseparatedoverSephadex
LH-20columnchromatography(100% MeOH)toyield
3(21mg)and4(11mg).
Identification
3, 5-Dihydroxy-4-methoxystilbene(1)　Whitea-
morphouspowder.UVλEtOHmax nm(ε):315(30250), 260
(6776);IRυKBrmaxcm-1:3506 (OH), 1586, 1522, 1446,
1330, 1273, 1199, 1047, 991 , 960, 816, 758, 694,
612;1HNMR(CDCl3)δ:7.47(2H, d, J=7.5Hz, H-
10, 14), 7.34 (2H, brt, J=7.5 Hz, H-11 , 13), 7.25
(1H, m, H-12), 6.98 (1H, d, J=16.3 Hz, H-7),
6.92 (1H, d, J=16.3 Hz, H-8), 6.69 (2H, s, H-2,
6), 5.48 (2H, brs, 3, 5-OH), 3.89 (3H, s, 4-
OCH3);13 CNMR(CDCl3)δ:148.9 (s, C-3, 5),
137.2 (s, C-9), 134.4 (s, C-1), 134.3 (s, C-4),
128.8 (d, C-8), 128.7 (d, C-11, 13), 128.0 (d, C-
7), 127.6 (d, C-12), 126.5 (d, C-10, 14), 106.4
(d, C-2, 6), 61.3 (q, 4-OCH3);ESI-MSm/z:241[ M-
H] -;HRESI-MSm/z:241.3296[ M-H] -(calcd.forC15
H14O3 , 241.3287).
Pinosylvin(2)　Whiteamorphouspowder.UVλEtOHmax
nm(ε):307 (29676), 211 (26510);IRυKBrmax cm-1:
3390 (OH), 1614, 1504 , 1470, 1250, 1148, 1007,
963, 840, 819, 747, 686;1HNMR(CDCl3 )δ:8.45
(2H, brs, 11, 13-OH), 7.57 (2H, d, J=7.8 Hz, H-
2, 6), 7.34 (2H, brt, J=7.8 Hz, H-3, 5), 7.25
(1H, m, H-4), 7.13 (1H, d, J=16.3Hz, H-8), 7.09
(1H, d, J=16.3Hz, H-7), 6.64 (2H, d, J=2.2 Hz,
H-10, 14), 6.37 (1H, t, J=2.2 Hz, H-12);ESI-MS
m/z:211[ M-H] -.
Rhapontigenin (3)　 White amorphous pow-
der.UVλEtOHmax nm(ε):326 (31050), 220 (24189);
IRυKBrmax cm-1:3378(OH), 1614, 1556 , 1504, 1454,
1025, 847;1HNMR(CDCl3)δ:8.61 (2H, brs, 11,
13-OH), 8.03 (1H, brs, 3-OH), 7.21 (1H, d, J=
1.8Hz, H-2, ), 7.04 (1H, d, J=16.3Hz, H-8), 7.01
(1H, dd, J=8.1, 1.8 Hz, H-6), 6.94 (1H, d, J=
16.3 Hz, H-7), 6.85 (1H, d, J=8.1 Hz, H-5), 6.60
(2H, d, J=2.2 Hz, H-10, 14), 6.33 (1H, t, J=2.2
Hz, H-12), 3.87 (3H, s, 4-OCH3);ESI-MSm/z:257
[ M-H] -.
ShegansuB(4)　Whiteamorphouspowder.[ α] 25D +
21.0 (c0.05, EtOH);UVλEtOHmax nm (ε):328
(29360), 285 (15170);IRυKBrmax cm-1:3426 (OH),
2845, 1722, 1543, 1340, 971, 846;1HNMR(CD3OD)
δ:7.07 (1H, s, H-2b), 6.95 (1H, d, J=16.2 Hz, H-
7b), 6.91 (1H, s, H-2a), 6.80 (1H, d, J=16.2 Hz,
H-8b), 6.78 (3H, s, H-5a, 6a, 6b), 6.43 (2H, s, H-
10b, 14b), 6.18 (1H, s, H-12a), 6.14 (1H, s, H-
12b), 6.13 (2H, s, H-10a, 14a), 5.40 (1H, d, J=
771Vol.20 　　　　　　JIANGBing, etal:ANewStilbenefromtheLianasofGnetumpendulum 　
8.8Hz, H-7a), 4.42(1H, d, J=8.8Hz, H-8a), 3.93
(3H, s, 3b-OCH3), 3.80(3H, s, 3a-OCH3);13CNMR
(CD3OD)δ:159.9 (s, C-11a, 13a), 159.6 (s, C-
11b, 13b), 149.4 (s, C-4b), 149.1 (s, C-3a), 147.8
(d, C-4a), 145.7(s, C-3b), 145.1 (s, C-9a), 141.1
(s, C-9b), 133.4 (s, C-1a), 133.2 (s, C-1b, 5b),
129.6 (d, C-7b), 127.9 (d, C-8b), 120.2 (d, C-
6a), 117.1 (d, C-6b), 116.2 (d, C-5a), 111.8 (d,
C-2b), 110.8 (d, C-2a), 107.8 (d, C-10a, 14a),
105.9 (d, C-10b, 14b), 102.8 (d, C-12b), 102.6
(d, C-12a), 95.5 (d, C-7a), 59.2 (d, C-8a), 56.8
(q, 3b-OCH3), 56.4 (q, 3a-OCH3);ESI-MSm/z:513
[ M-H] - , 515[ M+H] +.
ResultsandDiscussion
Compound1 wasobtainedasawhiteamorphouspow-
der.Themolecularformulaof1 wasdeterminedtobe
C15H14O3 onthebasisoftheESI-MSm/z241[ M-H] -
andHRESI-MSm/z:241.3296[ M-H] -(calcd.forC15
H13O3 , 241.3287).ItsIRspectrumshowedabroadab-
sorptionbandforthehydroxylgroup(3506cm-1).
The1HNMRspectrumof1 showedthesignalsofa
mono-substitutedphenylgroupatδ7.25 (1H, m),
7.34(2H, brt, J=7.5 Hz), 7.47 (2H, d, J=7.5
Hz), onetrans-doublebondatδ6.92and6.98 (each
1H, d, J=16.3 Hz), atetra-substitutedphenylgroup
atδ6.69 (2H, brs)andamethoxyatδ3.89 (3H,
s).The1H-1HCOSYexperimentalsosupportedthea-
bovepostulation.Inviewofits13CNMRdata, itcould
beconcludedthatthiscompoundwasastilbene.The
twohydroxyswerelocatedtoC-3andC-5, andtheme-
thoxytoC-4 onthebasisoftheHMBCcorelationsof
H-7/C-2 , C-6, andOMe/C-4(Fig.3).Thus, thestruc-
tureof1 waselucidatedtobe3, 5-dihydroxy-4-methox-
ystilbene.
Fig.3　ThekeyHMBCcorrelationsofcompound1
Thethreeknowncompoundswereidentifiedaspinosyl-
vin(2)[ 3, 4] , rhapontigenin(3)[ 5] andshegansuB(4)
[ 6] onthebasisofESI-MSandNMRdataandcompari-
sonofthemwiththosereported.
Acknowledgements　WewouldliketothankMr.
WangJi-dongforanalyzingtheNMRdata.
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