全 文 ：天然产物研究与开发 NatProdResDev2009, 21:963-965
文章编号:1001-6880(2009)06-0963-03
　
　
　ReceivedAugust5, 2008;AcceptedOctober29, 2008
＊CorrespondingauthorTel:86-21-50806728;E-mail:dyzhu@mail.shc-
nc.ac.cn
醉魂藤的化学成分研究
庄鹏宇 1, 2 ,付文卫 1, 2 ,谭昌恒 1 ,杨淑敏 1 ,刘　菲 2 ,王喆星 2 ,朱大元 1＊
1中国科学院上海生命科学研究院上海药物研究所国家新药研究重点实验室 , 上海 201203
2沈阳药科大学中药学院 ,沈阳 110016
摘　要:运用多种色谱技术从云南产醉魂藤 Heterostemmaalatumwight中分离得到 10个化合物。通过理化鉴别
和波谱数据确定了他们的化合物结构分别为 β-谷甾醇(1)、 正二十四烷酸(2)、芹菜素(3)、胡萝卜苷(4)、芹菜
素-7-O-β-D-葡萄糖苷(5)、醉魂藤碱 A(6)、醉魂藤碱 B(7)、醉魂藤碱 C(8)、醉魂藤碱 D(9)和醉魂藤碱 F
(10)。这些化合物均为首次从该植物中分离得到。
关键词:醉魂藤;β-谷甾醇;胡萝卜苷;芹菜素;芹菜素-7-O-β-D-葡萄糖苷;醉魂藤碱
中图分类号:Q946.91;R285 文献标识码:A
StudyontheChemicalConstituentsofHeterostemmaalatumWight
ZHUANGPeng-yu1, 2 , FUWen-wei1, 2 , TANChang-heng1 ,
YANGShu-min1 , LIUFei2 , WANGZhe-xing2 , ZHUDa-yuan1＊
1StateKeyLaboratoryofDrugResearch, ShanghaiInstituteofMateriaMedica, Chinese
AcademyofSciences, Shanghai201203 , China;2CollegeofTraditionalChineseMateriaMedica,
ShenyangPharmaceuticalUniversity, Shenyang110016 , China
Abstract:TencompoundswereobtainedfromHeterostemmaalatumwight.Byspectralanalysis, theyweredeterminedas
β-sitosterol(1), (n)-tetracosanoicacid(2), Apigenin(3), daucosterol(4), apigenin-7-O-β-D-glucopyranoside(5),
heterominesA(6), B(7), C(8), D(9)andF(10).Theywereisolatedfromtheplantforthefirsttime.
Keywords:Heterostemmaalatum;steroids;flavonoids;Alkalolids
Introduction
HeterostemmaalatumwightisaChinesefolkmedicine,
usedasanexpelingdampnesanddetoxifyingagentin
southwestofchina[ 1] .Previouslystudiesreportedthei-
solationofsomepurinederivativesfromthisgenus,
whichshowedanti-tumoractivityinvitroandinvivo
[ 2-4] .Inthecourseofphytochemicalinvestigationonthe
plant, weobtained10 knowncompounds, includingtwo
steroids, β-sitosterol(1), daucosterol(4);twofla-
vonoids, apigenin(3), apigenin-7-O-β-D-glucopyrano-
side(5);fourpurinederivatives, heterominesA(6),
B(7), C(8), andD(9);apyrimidinederivative
HeteromineF(10);and(n)-tetracosanoicacid(2).
Theabovecompoundswereobtainedfrom thetitle
plantforthefirsttime.Here, wedescribetheisolation
andstructureelucidationofthesecompounds.
Experimental
General
AlmeltingpointsweredeterminedonaBǜ CHI510
meltingpointapparatusandareuncorected.Optical
rotationsweremeasuredusingaPerkin-Elmer341 po-
larimeter.IRspectrawererecordedonaNicoletMag-
na750 FTIR(KBr)spectrometer.EI-MSdatawereob-
tainedwithaMAT-95 massspectrometer.NMRspectra
wererecordedonaBrukerAvanceDRX-300 orVarian
MercuryVX 400 NMR spectrometers, thechemical
shiftvaluesarereportedinppm(δ)andcouplingcon-
stants(J)aregiveninHz.Silicagel(200-300, 400
mesh)andprecoatedplatesofsilicagel(HSGF-254)
(QingdaoHaiyangChemicalGroupCo., Qingdao)
wereusedforcolumnchromatography(CC)andTLC,
respectively.
DOI :10.16333/j.1001-6880.2009.06.037
Plantmaterial
TheaerialpartsofHeterostemmaalatumwight.were
colectedinXishuangbannaCounty, YunnanProvince,
China, inJuly2006.Theplantswereidentifiedby
Prof.Jing-YunCui, XishuangbannaTropicalBotanical
Garden, AcademicaSinica, China.Avoucherspecimen
(No.2006-64)wasdepositedinourlaboratory.
Extractionandisolation
TheaerialpartsofHeterostemmaalatumwight.(7.0
kg)wassoakedwith95% ethanol(60 L×3, each7
d)atroomtemperature.Thesolventswereevaporated
underreducedpressuretogive524gresidue.Thecon-
centratedextractwassuspendedinH2O(3L)andpar-
titionedsuccessivelywithpetroleumether(PE, 60-90
℃), CHCl3 , EtOAc.TheEtOAc-solublefraction(30
g)wassubjectedrepeatedlytoCConsilicageleluted
withCH2Cl2-MeOH, andfurtherpurifiedsuccessively
throughODS, andSephadexLH-20 columnstoyield
successivelycompounds1(4 mg), 2(4 mg), 3(17
mg), 4(26 mg), 5(23 mg), 6(102 mg), 7(47 mg),
and8(16 mg).TheH2O-solublefractionwasdivided
intoH2O, 30% , 60% and95 % EtOHsubfractions
throughamacroporeresinD1400 (YangzhouPharma-
ceuticalFactory, Yangzhou, China)column( 10×85
cm).The30%(55 g)and60%EtOH(4.4 g)subfrac-
tionswerefurtherpurifiedsuccessivelythroughsilica
gel, andSephadexLH-20 columnstoafordcompounds
5(53 mg), 6(5.3g), 7(0.6 g), 8(0.2g), 9(21mg)
and10(22 mg), respectively.
Identification
β-sitosterol(1)　C29H50O.Colorlessneedles(EtO-
Ac), mp.135-137 ℃.EI-MSm/z:414 [ M] +.1H
NMR(CDCl3 , 300 MHz)δ:0.68 (3H, s, H-18), 0.81
(3H, d, J=6.3 Hz, H-27), 0.83 (3H, d, J=6.3
Hz, H-26), 0.85(3H, t, J=7.2 Hz, H-29), 0.93
(3H, d, J=6.3Hz, H-21), 1.02(3H, s, H-19), 5.35
(1H, m, H-6), 3.51 (1H, m, H-3);13 CNMR(
CDCl3 , 100MHz)δ:37.2(C-1), 31.6(C-2), 71.8(C-
3), 42.3(C-4), 140.7(C-5), 121.7(C-6), 31.9(C-
7), 31.8(C-8), 50.1 (C-9), 36.5 (C-10), 21.1(C-
11), 39.7(C-12), 42.3(C-13), 56.7(C-14), 24.3
(C-15), 28.2(C-16), 56.0(C-17), 12.0(C-18),
19.4(C-19), 36.1 (C-20), 18.8(C-21), 33.9(C-
22), 26.0(C-23), 45.8(C-24), 29.1(C-25), 19.8
(C-26), 19.0(C-27), 23.0(C-28), 11.8(C-29).The
structurewasidentifiedasβ-sitosterolbycomparisonof
itsphysicalandspectraldatawiththosereportedinthe
literature[ 5] .
(n)-tetracosanoicacid(2)　C24H48O2.Whitepow-
der, mp.80-85 ℃.EI-MSm/z:368 [ M] +, 354, 340,
326, 312, 298, 284, 269, 255, 241, 99, 85, 71, 57, atan
intervalofCH2.1HNMR(CDCl3 , 400 MHz)δ:2.34 (
2H, t, J=7.5 Hz, CH2 COOH), 1.63, 1.30 (CH2),
0.88(3H, t, J=6.7 Hz);13 CNMR(CDCl3 , 100
MHz)δ:179.3, 33.9, 31.9, 29.7, 29.4, 29.4, 29.2,
29.0, 24.7, 22.7, 14.1.Thespectraldataarematched
withacharacteristic(n)-tetracosanoicacid, soitwas
identifiedas(n)-tetracosanoicacid[ 6] .
Apigenin(3)　C15H10O5.Yelowpowder.ESI-MSm/
z:269 [ M-H] - , 271 [ M+H] +.1HNMR(DMSO-d6 ,
300MHz)δ:7.89(2H, d, J=8.6 z, 2H, 2′, 6′-H),
6.90(2H, d, J=8.6Hz, 3′, 5′-H), 6.73(1H, s, 3-H),
6.46(1H, brs, 8-H), 6.17(1H, brs, 6-H).Spectral
datawereinagreementwiththereportedvalues[ 7] .
Daucosterol(4)　C35H60O6.Whitegrain.TheFAB-
MSandIRdatawereidenticalwiththoseofdaucoste-
rol[ 8] , andTLCbehaviorwasidenticalwiththoseofau-
thenticdaucosterol.
Apigenin-7-O-β-D-glucopyranoside(5)　C21H20O10
.Yelowamorphouspowder.ESI-MSm/z:431 [ M-
H] - , 433 [ M+H] +.1HNMR(DMSO-d6 300 Hz)δ:
8.07(2H, d, J=8.8 Hz, H-2′, 6′), 7.13 (2H, d, J
=8.8 Hz, H-3′, 5′), 6.69 (1H, s, H-3), 6.86 (1H,
d, J=2.2Hz), 6.46 (1H, d, J=2.2Hz), 5.08 (1H,
d, J=7.4Hz, H-1″);13CNMR(DMSO-d6 , 100MHz)
δ:182.0(C-4), 163.8 (C-2), 163.0 (C-7), 162.4
(C-5), 161.4(C-4′), 156.9 (C-9), 128.4 (C-2′,
6′), 120.7 (C-1′), 114.6 (C-3′, 5′), 105.4 (C-
10), 103.8(C-3), 99.5(C-6), 94.9(C-8), glc(C-
1– C-6):105.4, 99.9 , 73.1, 77.2 , 69.5, 76.4,
60.6.Thedataof1HNMRand13CNMRwereconsist-
entwiththoseofthereference[ 9] .
HeteromineA(6)　C10H16N5OCl, waspresumedto
beaquaternaryammoniumchloridebecauseitformed
aprecipitatewithAgNO3.Whitepowder.ESI-MSm/z:
222[ M] +.1H NMR(CD3OD, 300 MHz)δ:4.18
964 NatProdResDev　　　　　　　　　　　　　　　　　　　　 　Vol.21
(3H, s, O-CH3), 4.09(3H, s, 7-CH3), 3.87(3H, s, 9-
CH3), 3.26(6H, s, N-(CH3)2);13CNMR(CD3OD,
100MHz)δ:162.4(C-2), 160.1(C-6), 154.5 (C-
4), 141.2(C-8), 106.3 (C-5), 38.2(N-(CH3)2),
31.9(9-CH3), 37.2(7-CH3), 55.7 (O-CH3).The
dataof1HNMRand13CNMRwereinagreementwith
thoseofthereference[ 3].
HeteromineB(7)　C9H14N5OCl, wasaquaternary
ammoniumchlorideduetogivingAgClprecipitationas
reaction with AgNO3.White powder.ESI-MS m/z
208
[ M] +.1HNMR(CD3OD, 300 MHz)δ:4.13 (3H,
s, O-CH3), 4.08(3H, s, 7-CH3), 3.87(3H, s, 9-
CH3), 2.97(6H, s, N-CH3);13CNMR(CD3OD, 100
MHz)δ:163.6(C-2), 160.1(C-6), 154.3 (C-4),
140.1(C-8), 106.9 (C-5), 29.1(N-CH3), 32.0(9-
CH3), 37.2(7-CH3), 55.0 (O-CH3).Thedataof1H
NMRand13CNMRwereconsistentwiththoseofthe
reference[ 3] .
HeteromineC(8)　C8H12N5OCl, wasaquaternary
ammoniumchlorideduetogivingAgClprecipitationas
reactionwithAgNO3.Whitepowder.ESI-MSm/z:194
[ M] +.1HNMR(CD3OD, 300 MHz)δ:3.94 (3H, s,
O-CH3), 3.92 (3H, s, 7-CH3), 3.02 (3H, s, 9-
CH3);13CNMR(CD3OD, 100MHz)δ:162.6(C-2),
159.9(C-6), 151.9 (C-4), 140.1(C-8), 106.5 (C-
5), 31.6(9-CH3), 35.3(7-CH3), 55.2 (O-CH3)
.Thedataof1HNMRand13CNMRwereconsistent
withthoseofthereference[ 3] .
HeteromineD(9)　C9H14N5OCl, alsowasaquater-
naryammoniumchlorideduetogivingAgClprecipitati-
onasreactionwithAgNO3.Whitepowder.ESI-MSm/z
208 [ M] +.1HNMR(CD3OD, 300 MHz)δ:4.11
(3H, s, 7-CH3), 3.81(3H, s, 9-CH3), 3.21(6H, s, N-
(CH3)2), 8.98(H, s, 8-H);13CNMR(CD3OD, 100
MHz)δ:156.5(C-2), 156.3(C-6), 152.1 (C-4),
140.5(C-8), 108.5 (C-5), 38.9(N-(CH3)2), 32.1
(9-CH3), 36.6(7-CH3).Thedataof1HNMRand13C
NMRwereconsistentwiththoseofthereference[ 4] .
HeteromineF(10)　C10H16N5O.Whitepowder.ESI-
MSm/z:240[ M+H] +.1HNMR(CDCl3 , 300 MHz)
δ:7.89(1H, brs, CHO), 4.64(1H, brs, N-H), 3.86
(3H, s, O-CH3), 3.16(6H, s, N-(CH3)2), 2.98(3H,
s, 7-CH3), 2.96(3H, d, J=4.9 Hz, 9-CH3);13CNMR
(CDCl3 , 100 MHz)δ:166.0(C-8), 165.3 (C-6),
161.0 (C-4), 160.1(C-2), 94.0 (C-5), 36.8(N-
(CH3)2), 27.7(9-CH3), 31.7(7-CH3), 53.0 (O-
CH3).Thedataof1HNMRand13CNMRwerecon-
sistentwiththoseofthereference[ 4] .
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965Vol.21 　　　　　　ZHUANGPeng-yu, etal:StudyontheChemicalConstituentsofHeterostemmaalatumwight