全 文 ：长序虎皮楠果实中的一个新的生物碱*
杨廷全1,2,邸迎彤1,何红平1,郝小江1**
(1中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室,
云南 昆明暋650204;2中国科学院研究生院,北京暋100049)
摘要:从长序虎皮楠 (Daphniphylumlongeracemosum )果实的甲醇提取物中分离得到一个新的虎皮楠生
物碱和三个已知的环烯醚萜苷型虎皮楠生物碱。通过现代波谱解析技术鉴定为daphlongeranineF (1),
caldaphnidineF(2),daphcalycinosidineB(3)anddaphcalycinosidineC(4)。其中,三个环烯醚萜苷虎皮楠
生物碱系首次从该种分离得到。
关键词:长序虎皮楠;虎皮楠生物碱;环烯醚萜苷型生物碱
中图分类号:Q946暋暋暋暋 暋暋文献标识码:A暋暋暋 暋暋暋暋文章编号:0253灢2700(2010)06灢561灢03
ANewAlkaloidfromtheFruitsofDaphniphylum
longeracemosum(Daphniphylaceae)
YANGTing灢Quan1,2,DIYing灢Tong1,HEHong灢Ping1,HAOXiao灢Jiang1**
(1StateKeyLaboratoryofPhytochemistryandPlantResourcesinWestChina,KunmingInstituteofBotany,
ChineseAcademicofSciences,Kunming650204,China;2GraduateUniversityofthe
ChineseAcademyofSciences,Beijing100049,China)
Abstract:Anew DaphniphylumalkaloiddaphlongeranineF (1)alongwiththreeknowniridoidalkaloids
wereisolatedfromthefruitsofDaphniphylumlongeracemosum .Theirstructuresweredeterminedbyspec灢
troscopicanalysisincludingmassspectrometryand2DNMR.Itmaybeworthytopointoutthatthethree
knowniridoidalkaloidscaldaphnidineF(2),daphcalycinosidineB(3)anddaphcalycinosidineC (4)which
wererarelydistributedinthisgenus,wereobtainedfromDaphniphylumlongeracemosumforthefirsttime.
Keywords:Daphniphylumlongeracemosum;Daphniphylumalkaloid;Iridoidalkaloid
暋 The Daphniphylum genusisremarkable
formetabolizingstructuralydiverse,complex
alkaloids with unique polycyclic skeletons
(KobayashiandMorita,2003).Daphniphylum
alkaloidshavebeenchalengingsubjectsinsyn灢
theticas wel asbiosyntheticresearchfields
(Kobayashiand Morita,2003).The Daph灢
niphylumlongeracemosumisanevergreentree
distributedin YunnanProvince,China (Liet
al灡,2006).Ourpreviousstudiesonthisplant
haveresultedintheisolationofaseriesofnovel
alkaloids.Asfurtherinvestigationonthefruits
of Daphniphylum longeracemosum,a new
DaphniphylumalkaloiddaphlongeranineF(1),
together with three known iridoid alkaloids
caldaphnidineF (2),daphcalycinosidineB (3)
anddaphcalycinosidineC (4),wereisolated.
Herein,wedescribetheisolationandstructure
elucidationofdaphlongeranineF(1)(Fig灡1).
云 南 植 物 研 究暋2010,32(6):561~563
ActaBotanicaYunnanica暋暋暋暋暋暋暋暋暋暋暋暋暋暋暋暋暋暋DOI:10灡3724/SP灡J灡1143灡2010灡10099
*
**
Foundationitem:TheSubjectofWesternDoctor(08065112W1)
Authorforcorrespondence;E灢mail:haoxj@mail灡kib灡ac灡cn;Tel:+86灢871灢5223263;Fax:+86灢871灢5219684
Receiveddate:2010灢05灢07,Accepteddate:2010灢09灢02
作者简介:杨廷全 (1985-)男,硕士研究生,研究方向为天然产物化学。E灢mail:ytq2005@163灡com
Fig灡1暋Thestructunesofcompounds1-4
ResultsandDiscussion
DaphlongeranineF (1)wasisolatedasan
opticalyactivecolorlesssolidanditsmolecular
formulawasestablishedasC24H35O4ontheba灢
sisofthepositiveHRESIMSatm/z402灡2641
[M+H]+ .TheUVabsorptionat296nm(log毰
=4灡12)andIRbandsat1692cm灢1,1650cm灢1
and1620cm灢1indicatedthepresenceofanester
C=OgroupconjugatedwithtwoC=Cbonds
(Chenetal灡,2005).TheNMRdataof1dis灢
playedthecharacteristicfeaturesofayuzurine灢
type Daphniphylum alkaloid,asjudgedfrom
thepresenceofanoxygenated methylene (毮C
63灡1,毮H3灡54,dd,J=12灡0,3灡1 Hzand毮H
4灡13,d,J=12灡0Hz),aN灢methyl(毮C46灡1,
毮H2灡13,br灡s)andaquaternarycarbon (毮C
100灡1).Extensive comparison of molecular
weightand13CNMRof1withthoseofdaphgra灢
ciline(Yamamuraetal灡,1980)revealedthat
theysharedhighlysimilarstructure,exceptfor
thedownfieldshiftofca.4ppmforthequater灢
naryhemiketalcarbon (毮C96灡0,C灢2).Itim灢
pliedthataMeO (毮H,3灡16)groupinsteadofa
OHgroupwaslinkedtoC灢2.Thestructureof1
wasfinalyestablished by detailed2D NMR
studies.The1H,1H灢COSYcorrelationsignals
disclosefoursubstructures:a(C灢19toC灢18),b
(C灢3toC灢4),c(C灢6toC灢7,C灢6toC灢12andC灢
11toC灢12)andd(C灢17toC灢16)asshownin
Fig灡2.TheHMBCcorrelationbetweentheme灢
thoxylprotons(毮H3灡16)andC灢2 (毮C100灡1)
furtherconfirmedtheabovespeculation.Thus,
italowedtheassignmentofcompound1toda灢
phlongeranineF,anewDaphniphylumalkaloid
oftheyuzurine灢type.
Fig灡2暋COSY(潵)andselectedHMBC(曻)
correlationsofDaphlongeranineF(1)
TheknownalkaloidscaldaphnidineF (2),
daphcalycinosidineB(3)anddaphcalycinosidine
C(4),therareiridoidalkaloids,wereidentified
onthebasisofreportedphysicalNMRandES灢
IMSdata.Thesethreeiridoidalkaloidswereob灢
tainedfromDaphniphylumlongeracemosumfor
thefirsttime,whichweredifferentfromonesi灢
solatedbyourgrouppreviously.
Experimental
GeneralExperimentalProcedures暋Opticalrotations
weremeasuredonaJASCODIP灢370digitalpolarimeter.
265暋暋暋暋暋暋暋暋暋暋暋暋 暋暋暋暋暋暋暋云暋南暋植暋物暋研暋究暋暋暋暋暋暋暋暋暋暋暋暋暋暋暋暋第32卷
IRspectrawasobtainedwithaTensor27FT灢IRspec灢
trometerwithKBrpelets.UVspectrawasmeasuredina
UV210Aspectrometer.NMRspectrawererecordedon
BrukerAM灢400andDRX灢500spectrometerswithTMSas
internalstandard.ESIMS wasrecordedonafinnigan
MAT90instrument,HRESIMSspectraonaVG Auto
Spec灢3000spectrometer.Columnchromatography was
performedonsilicagel(200-300mesh;QingdaoMarine
ChemicalInc.,Qingdao,People曚sRepublicofChina),
SephadexLH灢20(40-70毺m,AmershamPharmaciaBio灢
techAB,Uppsala,Sweden),andLichroprepRP灢18gel
(40-63毺m,MerckDarmstadt,Germany).Fractions
weremonitoredby TLCandspots werevisualizedby
Dragendorff曞sreagent.HPLC separations wereper灢
formedusinganAgilent1100seriespumpequippedwitha
UVdetectorandaZorbaxSB灢C18(10毺m,AgilentCo.
Ltd.Wilmington,DE)column(i.d.9灡4暳250mm)
PlantMaterial暋ThefruitsofDaphniphylumlonger灢
acemosumwerecolectedinHekouofYunnanProvince,
P.R.China,inOctober2008.Thematerialwasidenti灢
fiedbyProf.XunGong.
Extractionandisolation暋Theair灢driedandpowdered
fruitsofDaphniphylumlongeracemosum (13灡0kg)wereex灢
tractedwithCH3OH,andthecrudeextractwasadjustedto
pH3with2% HCl.Theacidicmixturewasdefattedwith
petroleumether,andthensubjectedtocationexchangresinto
givethecrudealkaloid(41灡0g).Thematerialwassubjected
toasilicagelCC(CHCl3/CH3OH,100暶0曻0暶1)toob灢
tainsixmajorfractions(Fr灡)A灢F.Fr灡B(2灡1g)wasfur灢
therchromatographedoverSigelCC (petroleumether/Et2
NH,100暶1曻40暶1,petroleumether/CH3COCH3,50暶
1曻 20暶1)folowedbySephadexLH灢20CCelutedwith
CH3OHtoaffordcompound1(6mg).Fr灡F(18灡0g)was
separatedonC18 silicagel,thenpurifiedbysemi灢HPLC
(MeOH/H2O20暶80)toget2(68mg),3(35mg).
Compounds4(3灡2g)wascrystalizedfromFr灡F.
DaphlongeranineF(1):C24H35O4,colorlesssolide;
[毩]23灡5D =-17灡7(c=0灡15,MeOH);UV毸max (log毰):
296(4灡12);IR毻KBrmaxcm灢1:2926,1692,1650,16201464,
1372,1210,1033;1Hand13CNMRdata,seeTable1;
PositiveESIMS m/z402 [M+H]+ ;HRESIMS m/z
402灡2641[M+H]+(calcd402灡2644).
Table1暋TheNMRdataofdaphlongeranineF(1)inCDCl3,毮inppm,JinHz
No. 毮C 毮H No. 毮C 毮H
1 62灡3t 2灡83(m) 13 42灡9t 2.61(m)
2灡32(d,11灡2) 1灡88(br灡d,14灡8)
2 100灡1s — 14 114灡8s —
3 23灡2t 1灡51(m) 15 168灡6s —
1灡27(m) 16 25灡7t 2灡66(m)
4 21灡4t 1灡97(m) 17 40灡1t 2灡71(m)
1灡62(m) 2灡81(m)
5 36灡4s — 18 27灡3t 2灡63(m)
6 30灡1d 1灡83(m) 1灡44(m)
7 56灡6t 2灡36(m) 19 8灡1q 0灡89(t,7灡0)
2灡40(m) 20 63灡1t 4灡13(d,12灡0)
8 46灡9s — 3灡54(dd,12灡0,3灡1)
9 149灡3s — 21 167灡7s —
10 152灡4s — 22 46灡1q 2灡13(br灡s,3H)
11 28灡5t 2灡56(m) 2灢OCH3 46灡7q 3灡16(s,3H)
1灡91(m) 21灢OCH3 51灡1q 3灡68(s,3H)
12 28灡1t 1灡71(m)
1灡54(m)
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3656期暋暋YANGTing灢Quanetal灡:ANewAlkaloidfromtheFruitsofDaphniphylumlongeracemosum ...暋暋暋