全 文 ：匙叶八角中一个新的倍半木脂素*
来国防2,董旭俊1,杨剑坤3,罗怀容1,王易芬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云南省食品药品检验所,云南 昆明暋650011;3云南省环境科学研究院,云南 昆明暋650034)
摘要:从匙叶八角 (Iliciumspathulatum )果实中分离得到一个新的倍半新木脂素,通过现代波谱技术确
定其结构为7曚,8曚灢反式灢7曞,8曞灢顺式灢5,3曚,3曞灢三甲氧基倍半新木脂素。
关键词:匙叶八角;八角属;木脂素;新木脂素
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)03灢281灢04
OneNewSesqui灢lignanfromIliciumspathulatum (Iliciaceae)
LAIGuo灢Fang2,DONGXu灢Jun1,YANGJian灢Kun3,
LUOHuai灢Rong1,WANGYi灢Fen1**
(1StateKeyLaboratoryofPhytochemistryandPlantResourcesinWestChina,KunmingInstituteofBotany,
ChineseAcademyofSciences,Kunming650204,China;2YunnanInstituteofFoodandDrugControl,
Kunming650011,China;3YunnanInstituteofEnvironmentalSciences,Kunming650034,China)
Abstract:Onenewsesqui灢neolignan,namedspathulatol,wasisolatedfromthepericarpsofIliciumspathula灢
tum .Itsstructurewaselucidatedas7曚,8曚灢trans灢7曞,8曞灢cis灢5,3曚,3曞灢trimethoxylsesquineolignanonbasis
ofspectralevidence(MS,IR,1Dand2DNMR).
Keywords:Iliciumspathulatum;Ilicium;Lignan;Neolignan
暋 Iliciumspecies,whichbelongtotheonlyge灢
nusofthefamilyIliciaceae,aremainlydistributed
inEastAsiaandtheSoutheastofNorthAmerica
(Wu,1997).Twenty灢eightspecies(over70% of
thespecies)inIliciaceaearedistributedinSouthern
andEasternofChina(Liuetal灡,1996).Fifteen
speciesofIliciumL.areusedasmedicinalplants,
includingIlicium spathulatum Hook.f.(Lin,
2002).ButonlyI灡verumandI灡jiadifengpiarein灢
cludedinthePharmacopoeiaofthePeople曚sRepub灢
licofChina (PharmacopoeiaCommissionofthe
People曚sRepublicofChina,2005).ThegenusIli灢
ciumisarichsourceofprenylatedC6灢C3compounds
(Tangetal灡,2009),neolignans(Kounoetal灡,
1989;SyandBrown,1998)andsesquiterpenelac灢
tones (Huangetal灡,2004;Yokoyamaetal灡,
2002).I灡spathulatumisatoxicshrub,mainlydis灢
tributedinSouthernChinaandusedinfolkmedicine
fortreatingrheumatismandinjuries(Lin,2002).
Aspartofourextensivestudiesonactivecom灢
poundsinIliciumspecies(Dongetal灡,2006),a
newsesqui灢neolignanwasisolatedfromthepericarps
ofIliciumspathulatum.
TheChinesestaranisesofIliciumspathu灢
latum werecolectedfrom WenshanofYunnan
Province.Afterrepeatedcolumnchromatographic
云 南 植 物 研 究暋2010,32(3):281~284
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09236
*
**
Foundationitems:NaturalScienceFoundation(20872148)andStateKeyLaboratoryofPhytochemistryandPlantResourcesin
WestChinaFoundation(P2008灢ZZ12)
Authorforcorrespondence;E灢mail:wangyifen@mail灡kib灡ac灡cn;Tel:86灢871灢5223097;Fax:86灢871灢5223038
Receiveddate:2009灢11灢25,Accepteddate:2010灢02灢26
作者简介:来国防 (1972-)男,博士,主管药师,主要从事植物化学及药品质量标准研究。
purificationonsilicagel,theAcOEtfractionof
itsextractafforded one new neolignan (1,
Fig灡1).Compound1wasobtainedasawhitea灢
morphoussolidanditsIRspectrum displayed
absorptionsofhydroxy (3423cm灢1),aromatic
groups (1612,1516,1496,1463cm灢1).The
negative灢ionhigh灢resolution massspectrometry
(HR灢FAB灢MS)showed aquasimolecularion
peakatm/z537灡2115,whichindicatedamolec灢
ularformulaofC30H33O9 (calcdfor537灡2124,
[M灢H]+ )havingfourteendegreeofun灢satura灢
tion.The1H NMRand1H灢1H COSYspectra
indicatedtwoseparateABXsystemsspectralda灢
ta[毮H6灡52(1H,d,J=1灡8Hz,H灢2曞),6灡39
(1H,dd,J=8灡2,1灡8Hz,H灢6曞),6灡56(1H,
d,J=8灡2Hz,H灢5曞),6灡31(1H,d,J=1灡6
Hz,H灢2曚),6灡61(1H,dd,J=8灡0Hz,H灢5曚),
6灡58(1H,dd,J=8灡0,1灡6Hz,H灢6曚)]intwo
aromaticrings.Furthermore,1HNMRspectral
datadisplayedonearomaticprotonat毮H 6灡58
(s),threemethoxylprotonsat毮H3灡43,3灡73,
3灡86(each3H,s),oneoxymethineprotonatd
5灡43(1H,d,J=2灡2Hz,H灢7曞),fourmethine
protonsat毮1灡67 (1H,m),1灡89 (1H,m),
2灡61(1H,m),3灡98(1H,d,J=9灡0Hz),one
metheneprotonsat毮2灡76(2H,m)andthree
oxygenatedmethyleneat毮H3灡79(1H,dd,J=
10灡9,3灡9,H灢9a),3灡63(1H,m,H灢9b),3灡67
(1H,dd,J =10灡8,4灡5 Hz,H灢9曚a),3灡45
(1H,dd,J =10灡8,9灡4 Hz,H灢9曚b),3灡61
(1H,dd,J=10灡9,5灡4,H灢9曞a),3灡49 (1H,
dd,J=10灡9,3灡6Hz,H灢9曞b).The13CNMR
andDEPTspectradisplayed27resonancesand
threeadditionalmethoxys,suggesting1tobea
sesquineolignanpossessingthreeprenylatedC6灢
C3.Its1H灢1HCOSYspectraalsodisplayedthe
presence of a sequence of methine灢methine灢
methenyl[CH(Ph)灢CH(O)灢CH2(OH)]succes灢
sivelycoupledinthisorder [毮H 2灡61,3灡61,
3灡49and5灡43]andanothersequenceof(HO)
CH2CH (CH2)CH (CH)CH2 (OH)ac灢
cordingtothecorrelationsofH7/H8/H8曚/H7曚,
H8/H9,andH8曚/H9曚(seeFig灡1).Thecorre灢
lationsofthecarbonsat毮C137灡8(s,C灢1曚)with
毮H 3灡98 (H灢7曚),1灡67 (H灢8曚),6灡31 (H灢2曚),
6灡61(H灢5曚)and6灡58(H灢6曚)showedone1,2,
4灢trisubstitutedphenylmoietylocatedatH灢7曚in
theHMBCspectrum.Longrangecorrelations
through3JintheHMBCwereobservedbetween
eachofH灢7曞/C灢4,H灢7曞/C灢3,andH灢8曞/C灢3,H灢
8曞/C灢4,indicatingthatcompound1possessesa
dihydrobenzofuran灢like skeleton. Meanwhile,
theHMBCspectrum alsoshowedthecorrela灢
tionsofH灢7withC灢1,C灢2,C灢6,C灢8,C灢9,C灢
8曚,H灢7曚withC灢1,C灢2,C灢3,C灢1曚,C灢2曚,C灢6曚,
C灢8,C灢8曚,C灢9曚,H灢7曞withC灢3,C灢4,C灢5,C灢
1曞,C灢2曞,C灢6曞,C灢8曞,C灢9曞,andH灢8曞withC灢2,
C灢3,C灢4,C灢1曞,C灢7曞,C灢9曞(Fig灡2).Threeaddi灢
tionalmethoxylgroupswerelocatedatC灢5,C灢3曚,
C灢3曞basedonthecorrelationsofthecarbonsat毮
143灡9(C灢5),148灡7(C灢3曚),148灡5(C灢3曞)withthe
methoxyprotonsat毮3灡82,3灡41,3灡68(each3H,
s),respectively.Thus,theplanarstructureof
compound1wasestablished.
Fig灡1暋Thestructureofcompound1
Therelativeconfigurationof1wasestablished
onthebasisof1HNMRdataandaROSEYexperi灢
ment.ThesmalcouplingconstantJ 7曞,8曞 (2灡3
Hz)suggestedthatH灢7曞andH灢8曞wasarranged
cis(Lietal灡,1997).Thelargecouplingcon灢
stantJ7曚,8曚 (9灡0Hz)suggestedthatH灢7曚and
H灢8曚wasarrangedtrans.TheROSEYcorrela灢
tionsofH灢7曚/H灢8,H灢7曚/H灢8曞,H灢8曞/H灢7曞indi灢
cated毩灢orientationsofH灢7曚,H灢8,H灢8曞,oral
ofwhich were毬灢oriented.Thus,therelative
configurationof1 wasestablished.Therefore,
thestructureof1 wasidentifiedtobe7曚,8曚灢
282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
Fig灡2暋ThekeycorrelationsinHMBC,ROSEYandCOSYspectraofcompound1
trans灢7曞,8曞灢cis灢5,3曚,3曞灢trimethoxylsesquine灢
olignan(namedspathulatol).
Experimental
General暋Columnchromatography (CC):Qingdao
silicagel(200-300mesh)andSephadexLH灢20.TLC:
Qingdaoprecoatedplates;Opticalrotationvalues:Hori灢
baSEAP灢300sensitivepolarimeter;IRspectra:BIO灢rad
FTSspectrometer,incm灢1;NMRspectra:BrukerAM灢
400 or DRX灢500spectrometer;CDCl3 solns; dvalues
(withref.tothesignalofCDCl3 withMe4Siasinternal
standard);dinppm,JinHz,Ms:VG AutoSpec3000
spectrometers;inm/z(rel.%).
暋暋Plantmaterial暋TheripefruitsofIliciumspathula灢
tumC.Y.WuwerecolectedinWenshangtown,Yun灢
nan,People曚sRepublicofChina,inJuly2004andidenti灢
fiedbyProfessorXi灢WenLi,KunmingInstituteotBota灢
ny,ChineseAcademyofSciences(CAS).Thevoucher
specimen(No.LP灢2004018)hasbeendepositedatState
KeyLaboratoryofPhytochemistryandPlantResourcesin
WestChina,KunmingInstituteofBotany,CAS.
暋暋ExtractionandIsolation暋ThedriedpericarpsofIli灢
ciumspathulatum (2灡5kg)wereextractedwithMeOHat
roomtemperaturetogiveabrownextract,whichwasdi灢
videdintomethanol灢solubleand methanol灢insolublepor灢
tions.Themethanol灢solubleportion(76g)wasfractionated
bychromatographycolumnonsilicagel(1500g,200-300
mesh,MeOH/CHCl30暶100,5暶100,1暶50,1暶20,1暶
10)toaffordeightfractions.FractionDwasfirstsubjec灢
tedtosilicagelchromatographyeluting with MeOH/
CHCl3(1暶9)togivefractionsD1灢D7.FractionD4was
separatedbySephadexLH灢20eluting with MeOH and
thenpurifiedonsilicagel(MeOH/CHCl31暶9)togive
compound1(53mg).
Spathulatol(7曚,8曚灢trans灢7曞,8曞灢cis灢5,3曚,3曞灢trim灢
ethoxylsesquineolignan,1,Fig灡1),whitepowder;mp.
114-116曟;[毩]:-103 (c0灡7,MeOH),UV毸MeOHmax
nm:283;IR毻KBrmaxcm灢1:3423(OH),2935,2841,1612,
1516,1496,1463,1431,1271,1207,1123,1033;Neg灢
ativeFAB灢MS m/z(%):537 [M灢H]+ (100),EIMS
m/z(%):538 [M]+ .Negative HR灢FAB灢MS m/z:
537灡2115 ([M灢H]+ ,calcd537灡2124).1H灢and 13C灢
NMRspectraldatawereshowninTable1.
Table1暋1H灢and13C灢NMRspectraldataofcompound1inCDCl3.毮inppm,JinHz
Position 1H (毩,毬) 13C Position 1H (毩,毬) 13C
1 130灡1s 6曚 6灡58(1H,dd,8灡0,1灡6) 122灡6d
2 131灡5s 7曚 3灡98(1h,d,9灡0) 45灡4d
3 127灡9s 8曚 1灡67(1H,m) 49灡3d
4 147灡6s 9曚 3灡45
(1H,dd,10灡8,9灡4)
3灡67(1H,dd,10灡8,4灡5) 61灡5t
5 143灡9s OMe 3灡45(3H,s) 56灡0q
6 6灡58(1H,s) 113灡2d 1曞 134灡6s
7 2灡76(2H,m) 34灡4t 2曞 6灡52(1H,d,1灡8) 110灡0d
8 1灡89(1H,m) 39灡5d 3曞 148灡5s
9 3灡63
(1H,m)
3灡79(1H,dd,10灡9,3灡9) 65灡9t 4曞 146灡5s
OMe 3灡82(3H,s) 56灡5q 5曞 6灡56(1H,d,8灡2) 115灡3d
1曚 137灡8s 6曞 6灡39(1H,dd,8灡2,1灡8) 118灡7d
2曚 6灡31(1H,d,1灡6) 112灡4d 7曞 5灡43(1H,d,2灡2) 87灡4d
3曚 148灡7s 8曞 2灡61(1H,dt,10灡9,3灡1) 53灡9d
4曚 145灡4s 9曞 3灡49
(1H,dd,10灡9,3灡6)
3灡61(1H,dd,10灡9,5灡4) 63灡1t
5曚 6灡61(1H,d,8灡0) 115灡5d OMe 3灡68(3H,s) 56灡2q
3823期暋暋 暋暋暋LAIGuo灢Fangetal灡:OneNewSesqui灢lignanfromIliciumspathulatum (Iliciaceae)暋暋 暋暋暋
Acknowledgements:Theauthorsaregratefultotheanalyt灢
icalgroupoftheLaboratoryofPhytochemistry,Kunming
InstituteofBotany,Chinese AcademyofSciencesfor
measuringNMR,MSandIRdata.
References:
DongX,ZhuX,WangYetal灡,2006.SecoprezizaaneSesquiter灢
penelactonesfrom Ilicium micranthum [J].Helvetica
ChimicaActa,89:983—987
HuangJM,YangCS,ZhaoRetal灡,2004.SevenNovelseco灢
Prezizaane灢TypeSesquiterpenesfromthePericarpsofIlici灢
ummerrilianum [J].Chemical&PharmaceuticalBuletin,
52:104—107
KounoI,HashimotoA,KawanoNetal灡,1989.NewSesqui灢
neolignanfromthepericarpsofIlicium macranthum [J].
Chemical&PharmaceuticalBuletin,37:1291—1292
LiS,IliefskiT,LundquistKetal灡,1997.Reassignmentofrel灢
ativestereochemistryatC灢7andC灢8inarylcoumaranneolig灢
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Lin Q,2002.MedicinalplantresourcesofIlicium L [J].
Zhongcaoyao,33:654—657
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SciencesPress,30(1):228—231
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2005.PharmacopoeiaofthePeople曚sRepublicofChina(中
国药典)[M].Beijing:ChineseMedicalScientificandTech灢
nologicalPress,Vol灡1
SyLK,BrownGD,1998.NovelPhenylpropanoidsandLignans
fromIliciumverum [J].JournalofNaturalProducts,61:
987—992
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C3compoundsandahighlyoxygenatedseco灢Prezizaane灢Type
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WuC,1997.FloraofChina [M].Beijing:SciencesPress,
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Prezizaane灢TypeSesquiterpenes,Jiadifenin withneurotro灢
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difengpi[J].JournalofNaturalProducts,65:527—531
* * * * * * * * * * * * * * *
暡上接第210页暢
根据编委会提出的意见和建议,详细纪要如下:
1暋更改刊名的必要性及意义
随着形势的发展,《云南植物研究》更改刊名不仅可行而且是必须的,主办单位下决心组织实施很有必要。编委
们对刊名的选择发表了较多意见,主要意见是:刊名若以 《植物分类学报》来定,面太窄,不利于期刊今后更大的发
展。部分编委建议刊物内容中可加入农、林方面的部分内容,对期刊会有更大影响。在主编的提议下,一致同意刊名
更改为:植物分类与资源学报 (JournalofPlantDiversityandResources)。
更改后的刊名中包含了 植物资源,这对稿件的征稿预留了较大空间,它可囊括生物多样性的各个方面,对期
刊的发展较为有利,而且要与国家级学会共同主办,会更易提升期刊的知名度。编委对更改刊名后栏目的设置也发表
了较多意见,最后一致同意不再按学科分栏目,而是统一分为 “综述、研究论文、研究快报暠等,这样更利于吸收更
多、更好的稿件。对于改刊后的期刊定位,编委意见非常一致认为:更改刊名后的期刊一定要定位于:国内本学科最
优秀、国外本学科有重要影响的期刊。
2暋提高稿件质量的举措
对于提高期刊质量,编委们建议:(1)一方面可邀请一些学科大家当编委作为期刊的门面,另一方面也要重视邀
请一些乐于奉献的年轻科学家为期刊的发展做实事 (审稿,投稿);(2)为保证文章的质量,设立责任编委;(3)制
定可行的操作方案,如编委在有可能的情况下,若有各自研究领域的专题研讨会,可组织文章进行专刊出版;(4)可
请一些学科上有创建的人作编委,并将其研究方向作一简单说明,这将是期刊最简明扼要的 征稿说明,且有一定
的影响;(5)主办单位在政策上给予足够的支持,包括在内部的考核上作相应的倾斜; (6)加强期刊的及时上网工
作,提高期刊的影响力。
3暋对于创立新刊的意见
目前天然产物的研究有逐渐东移的趋势,中国人要提早掌握此学术阵地,昆明植物所有较好的植物化学研究背
景,目前又有国家重点实验室,在国际上,植物所的文章都占有不少的份量,因此有必要自己成立一个新刊,将 《云
南植物研究》中的植物化学部分拿出,由于它的学科特点,有很好的条件创办英文期刊,而且创办后也可吸引国外的
稿件,只是在决定刊名上要慎重。
最后编委们都认为,这次会议的召开,是 《云南植物研究》发展历程中一次重要的会议,通过期刊的更名和重新
定位,有可能在现有基础上,可以谋求更大的发展,再铸 《云南植物研究》的辉煌,为我国广大植物学工作者坚守一
个重要的学术阵地,并开辟一个面向世界的国际学术窗口。
《云南植物研究》编辑部
482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