N-雜環(huán)硅烯鈀配合物的合成及其對Heck反應(yīng)的催化研究.pdf

1、江南大學(xué)碩士學(xué)位論文N雜環(huán)硅烯鈀配合物的合成及其對Heck反應(yīng)的催化研究姓名：張明申請學(xué)位級別：碩士專業(yè)：應(yīng)用化學(xué)指導(dǎo)教師：丁玉強(qiáng)20080601Abstract1rea扛11entofNheterocyclicsilylenesi[N(tBu)cH]2a11d[(礦c3H5)PdCl]2iIltolueneledto廿1efo衄ationofrnonomlclearcomplex(礦一c3H5)Pdsi【N(‘Bu)cH]2)c1，t

2、hesiliconanaloguetoNheterocycliccarbeneconlplex(礦c3H5)Pdc[N(‘Bu)cH]2)c1complex、Ⅳascllarac白erized謝tll1HNMR，1jCNMRandE1emen伽anmysesIIl仳sp印er，the證nportantdicmorideprecurSort0廿leNheterocyclicsilylene，SiCl2N【(2，6一iP曉C6H3]CH)2

3、、V鶴synthesized晰manewme廿10d謝tboutuSingHSiCl3Thediiminereacts、)l，imdilithjumm【phthmeneinTHFresultiI培i11themlitlliumderiVatiVe，wMchreactSwi吐1SiCl4to酉Vet11edicmorideprecursorT11eproductwasobtajnedi11eXcellemyield鋤dcharact麗ze

4、dbyIRand1HNMRspectnl加Nheterocyclicsilyleneisc峨nnya11areaofheavyresearchactivi夠111isp印erisfocus證培on也ecat2Llysisofpalladiun“Nheterocyclicsilylene)complexes，whichisa帥eofcatalySt謝t11potentialValueByusillgpalladi啪Nheterocycli

5、csilylenecomplexaStheprimaryc砌yst，styrelleandarylbromide嬲reactants，sodiunlacetate硒baSe，te砸bu巧laI】加10lliumbromideaspllase廿a11sferca：taly鞏reactinN，N—dimemylaceta】midehladditio瑪nlrou曲challgesomefactorssuCh嬲tenlperal=ure，rea

6、ctiontime，aIldreaCtaIlts，t11entestⅡleproductbyGCa11dGC—MSt0analysisnlecatal螄cbella、五ourof也epalladium一(N—heterocyclicsilylene)coInplexesFrom吐圮experimentald嘲瑚，nlee＆ctoftel珥煅a(bǔ)ture0nHeckreactionwaSiIlvestigatedbyuSillgpbromo

7、acetophenonea11d奶髑neasreaC僦at80a11d140oC，respectivelyRrevealsthatthePd(II)catalyst(礦c3H5)Pdsi時(shí)(‘Bu)cH]2)c1、機(jī)塢actiVatedillsitubyNaOAcinDMAat11ightenlperature(140oC)t0acllieveagoodyield，whereaSamoderateyieldofcouplingprodu

8、ctwasobtainedatalowertemperamre(80oC)foralonger婦nlee婦融ctofsubstitIle]ntsofarylbromidesonHeckreactionw嬲prelm血嘶1y協(xié)VeStigatedw砒l也ereactionofstyrene鋤dsomeSelectedarylbromidesp—bromoaCetopllenolle，pbromoallisoleandp—bromotolu

9、eIle，respectiVely，undermes鋤ereactionconditionsnreVealsnlattlletill∞forp_bromoacetopherlonewhjchbearsanelec廿0n晰t11draV眭ngsubstituentwaSshorcer(about4h)也a11tlloseofomerbromides，me觚、砌letlliscasegives也elligheStyield(abom99％)

10、111contrast，p—bromo撕solea11dpbr0Inotoluene、vhichconta誼elec仃Ion—donatingsubstituemsshowaloweryield(60％，48％，reSpectivel”iIla10nger缸eUnfbrtu】【la_tely，仃ea臼nemofpcllloroacetophenonea11dStyre船undershilarHeckreactioncollditions

11、ledto110fonnationof也eeXpectedproduCtAcomparisonoftllec砌”icacti訪夠oft11ecorrespondingpalladiunl—Nheterocycliccarbene)complexwasperformedConsideringoftllatthecoupliIlgreactionofg咿ene鋤dpbronloacetophenonecatalysedbycomplexga

12、VemehigheSt姐eld，acorrespondingreaCtionwasconductedforco瑚【plexul：1dertlles鋤econditionItwasfound曲眥mereaCtiongavetlleproductiIla姐eldofabout91％wKchw嬲littlelowermaIl也atofforcornplex(99％)Ho、№Ver，oncouplillgproductw2Lsfourldfor