Organic Chemistry Fourth Edition - Philadelphia …(PPT-31).ppt

19.14Mechanism of Acid-Catalyzed Esterification Acid-catalyzed Esterification Important fact: the oxygen of the alcohol isincorporated into the ester as shown. Mechanism of Fischer Esterification The mechanism involves two stages: 1) formation of tetrahedral intermediate (3 steps) 2) dissociation of tetrahedral intermediate  (3 steps) Mechanism of Fischer Esterification The mechanism involves two stages: 1) formation of tetrahedral intermediate (3 steps) 2) dissociation of tetrahedral intermediate  (3 steps) First stage: formation of tetrahedral intermediate methanol adds to the carbonyl group of the carboxylic acid the tetrahedral intermediate is analogous to a hemiacetal Second stage: conversion of tetrahedralintermediate to ester this stage corresponds to an acid-catalyzed dehydration Mechanism of formationoftetrahedral intermediate Step 1 Step 1 Step 1 carbonyl oxygen is protonated because cation produced is stabilized by electron delocalization (resonance) Step 2 Step 2 Step 3 Step 3 Tetrahedral intermediatetoester stage Step 4 Step 4 Step 4 Step 5 Step 5 Step 5 Step 6 Key Features of Mechanism Activation of carbonyl group by protonation of carbonyl oxygen Nucleophilic addition of alcohol to carbonyl groupforms tetrahedral intermediate Elimination of water from tetrahedral intermediate restores carbonyl group 19.15Intramolecular Ester Formation:Lactones Lactones Lactones are cyclic esters Formed by intramolecular esterification in acompound that contains a hydroxyl group anda carboxylic acid function Examples IUPAC nomenclature: replace the -oic acid ending of the carboxylic acid by -olide identify the oxygenated carbon by number Examples Common names Ring size is designated by Greek letter corresponding to oxygenated carbon A g lactone has a five-membered ring A d lactone has a six-membered ring Lactones Reactions designed to give hydroxy acids often yield the corresponding lactone, especially if theresulting ring is 5-