全 文 ：AnewnorditerpenoidalkaloidfromAconitumtaipaicum
HEYang-qing1＊ , MAZhan-ying2 , YANGQian1 , YAOBing-hua1 , GAOLi-ming3
(1.DepartmentofAppliedChemistry, Xi anUniversityofTechnology, Xi an710054 , China;
2.DepartmentofChemistry, XianyangNormalUniversity, Xianyang712000 , China;
3.KeyLaboratoryofPolymerMaterialsofGansuProvince, NorthwestNormalUniversity, Lanzhou730070 , China)
Abstract:ToinvestigatethechemicalconstituentsoftherootsofAconitumtaipaicum, silicagel
columnchromatographywasusedfortheisolationandpurificationofcompounds.Anewnorditerpenoid
alkaloid, isodelelatine(1), alongwithfiveknownalkaloids, atisine(2), delfissinol(3), liangshanine
(4), hypaconitine(5)anddelelatine(6)wereisolatedandidentified.Thestructureofthenew
compoundwaselucidatedonthebasisofspectraldata.
Keywords:Aconitumtaipaicum;diterpenealkaloid;isodelelatine
CLCnumber:R284.1　　　Documentcode:A　　　ArticleID:0513-4870(2008)09-0934-04
Received2008-02-19.
Projectsupportedby2005 ProgramofScienceCreationofXi an
UniversityofTechnology(108-210511).
＊Corespondingauthor　Tel:86-29-82066360,
E-mail:hyq7978863@163.com
太白乌头中一新的去甲二萜生物碱
何仰清 1＊ , 马占营 2 , 杨　谦1 , 姚秉华 1 , 高黎明 3
(1.西安理工大学 应用化学系 , 陕西 西安 710054;2.咸阳师范学院 化学系 , 陕西 咸阳 712000;
3.西北师范大学 甘肃省高分子重点实验室 , 甘肃 兰州 730070)
摘要:为了研究太白乌头(Aconitumtaipaicum)根的化学成分 , 采用硅胶柱色谱进行分离纯化 ,根据其理化性质
和波谱数据确定化合物结构。从该植物的根中分离得到 1个新的去甲二萜生物碱 isodelelatine(1)和 5个已知生物
碱 , 分别为 atisine(2)、delfissinol(3)、 liangshanine(4)、 hypaconitine(5)和 delelatine(6)。化合物 2 ～ 6均为首次从
该植物中分离得到。
关键词:太白乌头;二萜生物碱;isodelelatine
　　Aconitum taipaicum Hand-Mazzisaperennial
herbdistributedaroundanaltitudeof2 600 -3 400
metersin theSouthern ShaanxiProvinceand in
WesternHenanProvinceinChina.Itsrootshavebeen
usedinChinesefolkmedicineasanti-inflammatoryand
analgesicdrugforalongperiodoftime[ 1] .Previous
worksontheconstituentsofthisplantincludedthe
isolationofyunaconitine, neoline, talatisamineand
chamanine[ 2] .Furtherinvestigationontheconstituents
ofthisspecieshasnowresultedintheisolationofone
new(1)(Figure1), andfiveknown(2 -6)
alkaloids.Thispaperdescribestheisolationand
structuralelucidationofthenewalkaloid.
Resultsanddiscussion
Compound1 wasobtainedasamorphouspowder,
[ α] 27D -16.1°(c0.5, CHCl3).TheHR-SIMS-MS
spectrum exhibiteda[ M+H] + ionpeakatm/z
436.551 7, corespondingtoamolecularformulaof
C24H37NO6(calcd.for436.554 0).ItsIRspectrum
showedabsorptionbandsforhydroxylgroups(3 473
cm-1)andsimpleetherbonds(1 090 cm-1).The
13CNMRandDEPTspectraof1 exhibited24 carbon
signals(4×CH3 , 7 ×CH2 , 9×CH, and4×C).In
conjunctionwithits1HNMRspectrumitwasobvious
thatcompound1 possessedonemethylgroup(δC 25.3
andδH 0.93), anN-ethylgroup[ δC 14.1 and50.7;
·934· 药学学报 ActaPharmaceuticaSinica2008, 43(9):934-937DOI :10.16438/j.0513-4870.2008.09.002
δH 1.07(3H, t, J=7.2Hz), 2.64(1H, m)and2.76
(1H, m)] , amethylenedioxygroup[ δC 93.2;δH
5.07(1H, s)and5.17(1H, s)] , twomethoxylgroups
(δC 56.5 and60.0;δH 3.35 and3.28), aswelastwohydroxymethinemoieties(δC 74.7 and78.9, δH
4.10 and4.19, separately).Comparisonofthe1H
and13CNMRspectrawiththoseofdelelatine[ 3] and
eladine[ 4] suggested thatcompound 1 isa C19-
norditerpenoidalkaloidofthelycoctoninetype.The1H
and13CNMRchemicalshiftsof1weresimilartothose
ofdelelatine[ 3] exceptthatthelocationofthehydroxyl
groupatC-15 incompound1andatC-6indelelatine.
ThepresenceofahydroxylgroupatC-14 was
confirmedbythesignalatδH 4.10(1H, t, J=4.5 Hz)
inits1HNMRspectrum(Table1), characteristicof
C-14-βHwithaα-OHonC-14[ 3] , andbythe1H-1H
COSY correlationsbetween H-14 /H-9 andH-14/
H-13.TheabsenceofachemicalshiftofC-15 atδC
36.1 ineladineandthepresenceofamethylene
carbonsignalatδC 32.0 forC-6 (comparedwith33.4
fortatsinine[ 5] )suggestedanotherhydroxylgroup
locatedatC-15.ThiswasdetectedbytheHMBC
spectrum whichshowedcorrelationsofH-15/C-7,
H-15 /C-8 andH-15/C-16, andbythe1H-1HCOSY
spectrumwhichshowedcorelationofH-15/H-16.A
methinesignalatδC 91.6 inthe13CNMRspectrumis
characteristicofthepresenceofahydroxylgroupinthe
α-configurationattheC-15positionwhenthemethoxyl
groupispresentatC-16 intheβ-configuration[ 6] .
Therefore, thestructureofcompound1 wasestablished
asshowninFigure1andnamedasisodelelatine.Other
connectionsandconfirmationswerealsoconfirmedby
1H-1H COSY, HMBCandHSQC spectraandthe
significantcorelationswerelistedinTable1.
Table1　1H(400 MHz)and13C(100 MHz)chemicalshiftsand2Dcorelationsofcompound1 (inCDCl3)
No. δH(J/Hz) δC 　　　1H-1HCOSY 　　HMBC(H※C)
1 3.04(β), dd(9.6, 7.6) 84.1 H-2α, β H-α, β, H-17
2 2.02(β), m 26.3 H-1, H-2α, H-3α, H-3β H-1, H-3β
2.13(α), m H-2β
3 1.20(β), m 36.9 H-3α, H-18, H-β
1.58(α), m H-2α, H-2β, H-3β
4 34.3 H-18, H-β
5 1.26(β), s 56.1 H-6α, β H-1, H-18, H-α, β, H-17
6 1.77(β), m 32.0 H-5, H-6α
1.81(α), m H-5, H-6β
7 94.1 H-15
8 84.8 H-6α, β, H-9, H-10, H-14, H-15
9 3.65(β), m 42.8 H-10, H-14 H-10, H-12α, H-13
10 1.95(β), m 47.7 H-1, H-9 H-1, H-6β, H-9
11 49.7 H-17
12 2.04(β), m 26.9 H-12α, H-9
2.51(α), dd(9.8, 8.4) H-12β, H-13
13 2.40(β), m 36.1 H-12β, H-14 H-9, H-15
14 4.10(β), t(4.5) 74.7 H-9, H-13
15 4.19(β), d(6.0) 78.9 H-16 H-9, H-13, H-16
16 3.45(α), dd(10.8, 6.0) 91.6 H-13, H-15 H-14, H-15, 16-OCH3
17 3.28, s 63.9 H-1, H-5, H-19β
18 0.93, s 25.0
19 2.28(β)m 57.5 H-19α H-5, H-17, H-18, N-CH2
2.69(α)m H-19β
-OCH2O- 5.07(β), s 93.2
5.17(α), s
N-CH2 2.64, m 50.7 N-CH2 , -CH3 -CH3
2.76, m N-CH2 , -CH3 -CH3
-CH3 1.03t(7.2) 14.1 N-CH2 N-CH2
1-OCH3 3.23, s 56.0 H-1
16-OCH3 3.35, s 56.5 H-16
·935·HEYang-qing, etal:AnewnorditerpenoidalkaloidfromAconitumtaipaicum
Figure1　Thestructuresofcompounds1-6
Experimental
Melting pointsweredetermined on akofler
micromeltingpointapparatusanduncorrected.Optical
rotation was measured on a Perkin-Elmer 241
polarimeter.1H, 13C and 2D NMR spectrawere
recordedonaBrukerAM 400 NMRspectrometerin
CDCl3 withTMSasinternalstandard.HR-SIMS-MS
and EI-MS spectra were obtained on Bruker
APEXIFT-MS and MAT-112 spectrometers,
respectively.IRspectrawererecordedonaNicolet
NEXUS670 FT-IRspectrometer, usingKBrwindows
withCHCl3 assolventagainstanairbackground.Silica
gel(200-300mesh)forCCandGF254 forTLCwere
obtainedfromtheQingdaoMarineChemicalFactory.
Plantmaterial　TherootsofAconitumtaipaicum
Hand-Mazzwerecolectedfrom QinlingMountain,
Shaanxi, Chinaintheautumnof2005 andidentified
byProfessorWANGYi-fengatDepartmentofBotany,
NorthwestNormalUniversity.Avoucherspecimenwas
depositedintheDepartmentofBotany, Northwest
NormalUniversity.
Extractionandisolation　Theair-driedground
rootsofAconitumtaipaicum(2.5 kg)wereextracted
with90% EtOH(10 L)atroomtemperaturefor7
days.TheEtOHextractwastreatedwith5% HCl,
thentheacidicsolutionwasbasifiedwith26% NH4OH
topH 11 andextractedwithCHCl3 togivecrude
alkaloids(150 g)afterremovingthesolvent.This
residuewasseparatedbysilicagel(100-200 mesh)
columnchromatography(CC)withgradientelutionof
petroleumether-Me2CO-Et2NH, giving, inorderofthe
increasingpolarity, 1(18 mg), 2 (76 mg), 3 (200
mg), 4 (50 mg), 5(40mg), and6 (35 mg).
Isodelelatine(1)　Amorphouspowder, [ α] 27D
-16.1°(c0.5, CHCl3).IR(KBr, cm-1):3 473,
2 928, 1 456, 1 193, 1 090, 961, 753.HR-SI-MS:
m/z436.551 7[ M+H] +, Calcd.forC24 H38 NO6:
436.554 0.EI-MS:434 [ M-H] +(5), 404 [ M-
OCH3 ] +(100), 91(11), 71(19), 43(18).For
NMRdataseeTable1.
In addition, five known compoundsatisine
(2)[ 7, 8] , delfissinol(3)[ 9] , liangshanine(4)[ 10] ,
hypaconitine(5)[ 11] , anddelelatine(6)[ 3] were
identifiedbycomparisonoftheir1Hand13CNMR, IR
andMSspectroscopicdatawiththosereportedin
literatures, separately.
Acknowledgements:TheauthorsaregratefultoDrJIA
Xiao-dong, Department ofChemistry, Northwest Normal
University, People sRepublicofChina, forhisvaluablehelp
withtheHRMSandEIMSdeterminations.
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·937·HEYang-qing, etal:AnewnorditerpenoidalkaloidfromAconitumtaipaicum