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SynthesisofEsters Chapter15:Alcohols,DiolsandThiols

SynthesisofEsters

Reactiontype:NucleophilicAcylSubstitution

Summary

ThisreactionisalsoknownastheFischeresterification.
Estersareobtainedbyrefluxingtheparentcarboxylicacidwiththeappropriatealcoholwithan
acidcatalyst.
Theequilibriumcanbedriventocompletionbyusinganexcessofeitherthealcoholorthe
carboxylicacid,orbyremovingthewaterasitforms.
Alcoholreactivityorder:CH3OH>1o>2o>3o(stericeffects)
Esterscanalsobemadefromothercarboxylicacidderivatives,especiallyacylhalidesand
anhydrides,byreactingthemwiththeappropriatealcoholinthepresenceofaweakbase(see
chapter20)

StudyTip:
Thecarboxylicacidandalcoholcombinationusedtoprepareanesterarereflectedbythenameof
theester,
e.g.ethylacetate(orethylethanoate),CH3CO2CH2CH3canbemadefromCH3CO2H,aceticacid(or
ethanoicacid)andHOCH2CH3(ethanol).
Thisgeneral"disconnection"isshownbelow:

MECHANISMFORREACTIONFORACID
catalyzedESTERIFICATION
Step1:
Anacid/basereaction.Protonationofthe
carbonylmakesitmoreelectrophilic.
Step2:
ThealcoholOfunctionsasthenucleophile
attackingtheelectrophilicCintheC=O,with
theelectronsmovingtowardstheoxonium
ion.
Step3:
Anacid/basereaction.Deprotonatethe
alcoholicoxygen.
Step4:
Anacid/basereaction.Needtomakethe
OHleave,soconvertitintoagoodleaving
groupbyprotonation.

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Step5:
Usetheelectronsofanadjacentoxygento
help"pushout"theleavinggroup,awater
molecule.
Step6:
Anacid/basereaction.Deprotonationofthe
oxoniumionrevealsthecarbonylintheester
product.

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