亞銅催化的分子內(nèi)羧酸氧烯基化和烷基胺氮烯基化反應(yīng)研究.pdf

1、同濟(jì)大學(xué)碩士學(xué)位論文亞銅催化的分子內(nèi)羧酸氧烯基化和烷基胺氮烯基化反應(yīng)研究姓名：孫長(zhǎng)輝申請(qǐng)學(xué)位級(jí)別：碩士專業(yè)：有機(jī)化學(xué)指導(dǎo)教師：李超忠20090301AbstractAbstractCoppercatalyzedGC，CX(X=N，O，Setc)bondformationhasbeenausefulandefficientmethodinorganicsynthesisInthisdissertation，onthebaseofourgr

2、oup’Sresearchaboutcoppercatalyzedintramolecularvinylation，weinvestigatedintramolecularOvinylationofcarboxylicacidsandNvinylationofaminesItcouldbedescribedasthefollowingtwoparts：1Synthesisoflactonesbycoppercatalyzedintram

3、olecularOvinylationofcarboxylicacidswasinvestigatedforthefirsttimeWeemployedvinylichalogensubstitutedcarboxylicacidsassubstrates，throughfurtheroptimization，weconcludedthattheoptimizedconditionsfor6exocyclizationreactionw

4、astouse10m01％CuI，20m01％Ⅳ，Ndimethylcyclohexane一1，2diamine，05eqK2C03andCH3CNThisconditionalsoallowed5exo、5endoand6endocyclizations，andfattycarboxylicacidandaromaticcarboxylicacidcouldalsobecardedoutFor4一exocyclizationreact

5、ion，throughexperimentswefoundthat4exocouldalsobecardedoutunderthisconditionBecauseoftheinstabilityofthefinalproduct，wecouldonlygetthedecomposedproductWealsotriedtocarryoutthecorresponding7endoand7exocyclizationreactions，

6、butwereunsuccessfulSOfarFurtherinvestigationwouldberequired2WehavecomprehensivelyinvestigatedtheNvinylationofaminesThroughourexperiments，wefoundthattheoptimizedconditionsforthisreactionwastouse10m01％CuI，20m01％110phenanth

7、roline，2eqCs2C03underrefluxinCH3CN，NvinylationreactionsofamidescouldbehighlyefficientandregioselectiveBycomparingdifferentsubstituentsattachedtothenitrogenatomofamides，weconcludedthatwiththeincreaseofthesubtituentselectr

8、onasborbingabilitythere酉onalselectivityofcyclizationwasgraduallyreducedFornonsubstitutedamines，withthe10mol％Culasthecatalyst，20mol％2isobutyrylcyclohexanoneastheligand，2eqCs2C03asthebaseandCH3CNasthesolvent，Nvinylationrea

9、ctionscouldalsobehighlyefficientandhighlyselectiveAccordingtocomparisonofdifferentcyclizationmodes，weuncoveredthatthezk巴功cyclizationwasfundamentallypreferredoverothermodesofcyclizationThisresultconfirmedthepriorityof4exo