2 ,2’,7,7’-四碘-9,9’-螺二芴的简便合成方法

PHOTOGRAPHICSCIENCEANDPHOTOCHEMISTRYVol.19󰀁No.3Aug.,2001󰀁󰀁研究快讯

APRACTICALMETHODTOSYNTHESIZE2,2󰀁,7,7󰀁-TETRAIODO-9,9󰀁-SPIROBIFLUORENE

WUXiao-ming,CHENXiao-chuan,CAOXiao-ping,PANXin-fu

(DepartmentofChemistry,NationalLaboratoryofAppliedOrganicChemistry,

LanzhouUniversity,Lanzhou730000,P.R.China)

Abstract:2,2󰀁,7,7󰀁-tetraiodo-9,9󰀁-spirobifluorene(2)isthekeyintermediateof

holetransportmediaandconductingpolymers.Wedevelopedapracticalmethodbywhich2washighlyselectivesynthesizedingoodyield.

Keywords:2,2󰀁,7,7󰀁-tetraiodo-9,9󰀁-spirobifluorene;spraincompound;Sand-meyerreaction

ArticleID:1000-3231(2001)03-0161-04󰀁󰀁CLCnumber:O644󰀁󰀁Documentcode:A

Conductingorganicpolymersandmacroorganicmoleculehaveattractedmuchrecentscientificinterest,sincetheymayplayakeyroleintheconstructionofmodernelectronic

systems.2,2󰀁,7,7󰀁-tetrabromo-9,9󰀁-spirobifluorene(1)[4]and2,2󰀁,7,7󰀁-tetraiodo-9,9󰀁-spirobifluorene(2)arespraincompoundswithadefinedphysicalstructureforuseinsynthe-sizingholetransportmediaOMeTAD(3)andTAD(4)whichhaveachievedimpressivesolar-to-electricalenergyconversionefficiencies[5].AsolarcellbasedonOMeTADconvertspho-tonstoelectriccurrentwithaveryhighyieldof33%.Inourresearchofsynthesizing3and4,wefound1hasn󰀁tenoughreactiveness,andtheyieldofcouplingreactionbetween2anddiphenylamineor4,4󰀁-dimethoxydiphenylamineisverylow,soitisveryimportanttofindapracticalmethodtosynthesize2.

[1-3]

1R=Br,2R=I,3R=N(Ph)2,4R=N(p-PhOMe)2

MoleculeStructure

收稿日期:2001-03-13;修回日期:2001-05-16;通讯联系人:潘鑫复作者简介:吴晓明(1974-),男,硕士研究生.

161

󰀁󰀁162感󰀁光󰀁科󰀁学󰀁与󰀁光󰀁化󰀁学19卷󰀁

󰀁󰀁Compound1hasbeenhighlyselectivesynthesizedinnearquantitativeyieldthroughaddingBr2into9,9󰀁-spirobifluorenewithcatalyticFeCl3inCH2Cl2.Unfortunately,therearen󰀁topenlyreportsonhighlyselectivesynthesisof2,2󰀁7,7󰀁-tetraiodo-9,9󰀁-spirobifluo-rene.MaybeitisbecausetheBr2ismoreeasilypolarizingthanI2.

AsshowninScheme1,compound6waseasilysynthesizedthroughtheSandmeyerre-actionfrom2-aminebiphenyl(5)in90%yield,thenat-78󰀁LithiumRegentofcom-pound6waspreparedbyaddingn-BuLianddroppedinthesolutionof9-fluoroneinTHF,socompound7waspreparedin86%yield.Compound8wasreadilyavailableinnearquant-itativeyieldthroughthedehydrolysisofthe7inaceticacidwithcatalyticconcentratedHCl,andrefluxingthemixtureof8andIClinaceticacidcompound2wassynthesizedin75%yield.

Scheme1

[4]

ReagentsandConditions

a:concentratedHCl,NaNO2,freshCuCl;b:n-BuLi,-78󰀁,9-fluorone;c:aceticacid,concentratedHCl;d:ICl,aceticacid.Insummary,2,2󰀁,7,7󰀁-tetraiodo-9,9󰀁-spirobifluorenewassynthesizedundermildre-actionconditionsandfromcommercialavailablestartingmaterialsandreagents.ExperimentProcedure

MassspectrawererecordedonaZAB-HSspectrometerusingFABtechnique.IRspec-trawererecordedinaNicolet179SXFT-IRspectrophotometer.1H-NMRspectrawererecordedonBRUKERAM-200instruments.Standardflashchromatographywasemployedtopurifythereactiveresidue.ElementalanalyseswereperformedonaCarloerba1106in-strument.

2-Chloro-1-phenylbenzene6:Toasolutionof5(169mg,1.0mmol)inconcentratedHCl(0.25mL)andwater(10mL)at0󰀁,wasaddedsodiumnitrite(80mg,1.2mmol)inwater(3mL).Thetemperaturewasheldat0󰀁throughouttheaddition.Theresultingso-lutionwasstirredfor45minat0,andthendroppedintofreshCuCl(120mg,1.2mmol)inwater(10mL).Thesolutionwasstirredovernightandthenextractedwithether(4󰀁25

󰀁3期

WUXiao-mingetal:APracticalMethodtoSynthesize

2,2󰀁,7,7󰀁-Tetraiodo-9,9󰀁-Spirobifluorene

󰀁163󰀁

mL).Thecombinedorganiclayerswerewashedwith3mol/Lhydrochloricacid(3󰀁5mL)anddriedovermagnesiumsulfatetoafford170mgofthedesiredcompoundasayellowso-lid,yield90%.1H-NMR󰀁7.95(dd,J=8.1,1.2Hz,1H),7.34(m,7H),7.03(tt,J=7.3,1.9Hz,1H).EI-MS(m/z)188(56,M+),189(18),187(18),152(100),127(12);IR3055.7,1578.4,1460.0,1426.6,1016.7,1004.0,746.8cm-1.

9-(2󰀁-Biphenyl)-9󰀁-fluorenol7:Toasolutionof6(189mg,1.0mmol)inTHF(5mL)wasaddedat-78󰀁n-butyllithium(0.67mL,1.2mmol,1.5mol/Linpetroleumether)over30min.Theresultingslurrywasstirredat-78󰀁for1h,and9-fluorenone(216

mg,1.2mmol)wasaddedinTHF(5mL)over10min.Thesolutionwaswarmedtoroomtemperaturefor30minandpouredintowater.Theaqueouslayerwasextractedwithether(4󰀁25mL),andthecombinedorganiclayerswerewashedwithbrineanddriedovermag-nesiumsulfate.Thecrudeproductwasrecrystalliezedfromethanoltoafford287mgofthedesiredcompoundasawhitesolid,yield86%.1H-NMR󰀁8.45(d,J=8.0Hz,1H),7.51(t,J=7.4Hz,1.4Hz,1H),7.2-7.1(m,1H),6.88(dd,J=7.5Hz,1.4Hz,1H),6.80(d,J=7.5Hz,1H),6.58(t,J=7.9Hz,2H),5.98(dd,J=8.1Hz,1.1Hz,2H),2.2(s,1H);EI-MS(m/z)334(86,M+),302(10),289(10),265(4),239(4),181(100),152(72);IR(KBr)3590,3063,3023,1450,1344,1160cm

-1

.

9,9󰀁-Spirobifluorene8:Toasolutionof7(334mg,1.0mmol)inrefluxingaceticacid(10mL)wasaddedconcentratedhydrochloricacid(0.1mL)andthesolutionheatedtorefluxfor30min.Thesolutionwascooledtoroomtemperature,andwater(10mL)wasadded.theresultingwhitesolidwasfilteredandwashedwithwateranddriedinvacuo.Nofurtherpurificationwasrequiredtoafford310mgofthedesiredcompoundasawhitesolidyield98%.H-NMR󰀁7.82(d,J=7.7Hz,4H),7.34(t,J=7.5Hz,4H),7.08(t,J=7.5Hz,4H),6.71(d,J=7.6Hz,4H);EI-MS(m/z)316(100,M+),261(2),181(2),156(24),143(11);IR(KBr)3038.2,3011.0,1654.2,1560.0,1447.6,749.3cm-1.2,2󰀁,7,7󰀁-Tetraiodo-9,9󰀁-spirobifluorene2:Toasolutionof8(316mg,1.0mmol)inaceticacid(10mL)wasaddedIC1(780mg,4.8mmol)andheatedtorefluxunderargonfor8h.Thesolutionwascooledtoroomtemperatureandpouredintowater(20mL).Theresultingwhitesolidwasfilteredandwashedwithwateranddriedinvacuo.Nofurtherpu-rificationwasrequiredtoafford615mgofthedesiredcompoundasawhitesolid,yield75%.1H-NMR󰀁7.82(d,J=8.4Hz,4H),7.55(dd,J=8.2Hz,1.8Hz,4H),6.70(d,J=1.5Hz,4H);MS(FAB)819.8(M++1,16)(16);IR(KBr)3046.7,1591.1,1449.4,819.0,756,74,726.8cm-1.C25H12I4requiresC36.62H1.48foundC36.57H1.41.References:

[1]󰀁HagenJurgen,SchaffrathWinfried,OtschikPeter,etal.Lowmolecularorganicglassesforelectroluminescence[J].

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󰀁󰀁164感󰀁光󰀁科󰀁学󰀁与󰀁光󰀁化󰀁学19卷󰀁

Synth.Met.,1997,91,209-215.

[2]󰀁MagenJurgen,SchaffrathWinfried,OtschikPeter,etal.Novelhybridsolarcellsconsistingofinorganicnanopart-i

clesandanorganicholetransportmaterial[J].Synth.Met.,1997,89,215-220.

[3]󰀁WangY,LiuYG,ChenJG,etal.Organiccharge-transportingmaterials[J].PhotographicScienceandPhoto-chemistry,1999,17(1),73.

[4]󰀁TourJamesM,WuRL,SchumnJeffryS.Approachestoorthogonallyfusedconductingpolymersformolecularelec-tronics[J].J.Am.Chem.Soc.,1990,112,5662-5663.

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conversionefficiencies[J].Nature,1998,395,583.

2,2󰀁,7,7󰀁-四碘-9,9󰀁-螺二芴的简便合成方法

吴晓明,陈小川,曹小平,潘鑫复

(兰州大学化学系,兰州730000)

摘󰀁要:2,2󰀁,7,7󰀁-四碘-9,9󰀁-螺二芴具有特殊的螺形结构,它是合成空穴导电材料OMeTAD和TAD及其它一些导电高分子的关键中间体.我们发展了一种

条件温和简便的方法,高产率地合成了目标分子.

关键词:

2,2󰀁,7,7󰀁-四碘-9,9󰀁-螺二芴;扭转化合物;Sandmeyer合成

通讯联系人:潘鑫复