醇反应回顾与预览表15 columbia有机化学课件12 html.pptx

15.6

ReactionsofAlcohols:

AReviewandaPreview

Table15.2ReviewofReactionsofAlcoholsreactionwithhydrogenhalidesreactionwiththionylchloridereactionwithphosphoroustribromideacid-catalyzeddehydrationconversiontop-toluenesulfonateesters

NewReactionsofAlcoholsinThisChapterconversiontoethersesterificationestersofinorganicacidsoxidationcleavageofvicinaldiols

15.7

ConversionofAlcoholstoEthers

RCH2OHCH2ROHH+RCH2OCH2RHOH+ConversionofAlcoholstoEthersacid-catalyzedreferredtoasacondensationequilibrium;mostfavorableforprimaryalcohols

Example2CH3CH2CH2CH2OHH2SO4,130°CCH3CH2CH2CH2OCH2CH2CH2CH3(60%)

Figure15.2MechanismofFormationofDiethylEtherStep1:CH3CH2O???

?HHOSO2OHCH3CH2O?

?HOSO2OHH+–+

Figure15.2MechanismofFormationofDiethylEtherStep2:CH3CH2?

?HH+OCH3CH2O???

?H++CH3CH2CH3CH2O?

?H?

?HHO?

?

Figure15.2MechanismofFormationofDiethylEtherStep3:++CH3CH2CH3CH2O?

?HOSO2OH–???

???HOSO2OH????CH3CH2CH3CH2O?

???

reactionnormallyworkswell

onlyfor5-and6-membered

ringsIntramolecularAnalogHOCH2CH2CH2CH2CH2OHH2SO4130°O(76%)

IntramolecularAnalogHOCH2CH2CH2CH2CH2OHH2SO4130°O(76%)via:OH+OHH?

??

???

15.8

Esterification

condensationFischeresterificationacidcatalyzedreversibleEsterificationROHH2O+H++RCOHORCORO

ExampleofFischerEsterificationH2O+CH3OH+COHOCOCH3OH2SO40.1mol0.6mol70%yieldbasedonbenzoicacid

highyieldsnotreversiblewhencarriedout

inpresenceofpyridineReactionofAlcoholswithAcylChloridesROHHCl++RCClORCORO

pyridine+CClO2NOCH3CH2CH3OH(63%)NO2CH3CH2CH3OCOExample

analogoustoreactionwithacylchloridesReactionofAlcoholswithAcidAnhydridesROH++RCOROORCOCRORCOHO

pyridine(83%)+C6H5CH2CH2OHOF3CCOCCF3OC6H5CH2CH2OCCF3OExample

15.9

EstersofInorganicAcids

EstersofInorganicAcidsROH+HOEWGROEWG+H2OEWGisanelectron-withdrawinggroupHONO2(HO)2SO2(HO)3PO+–

EstersofInorganicAcidsROH+HOEWGROEWG+H2OEWGisanelectron-withdrawinggroupHONO2(HO)2SO2(HO)3PO+–CH3OH