Esterification and ester hydrolysis:

Alkyl-oxygen
bond- AL
O
R C O R

Acyl-oxygen
bond- AC

Alcohols react with carboxylic acids in acidic medium to form esters. The reaction is
reversible and as a result, under suitable conditions, esters can be hydrolysed back to carboxylic acids and
alcohols. Although esters cant be formed in basic medium, they can be hydrolysed in basic medium which
is called saponification.
Mechanism in acidic medium:
I. AAC2 (Acidic medium, acyl-oxygen cleavage, bimolecular)
Carboxylic acids/esters, which do not have any special structural features, undergo this type of
esterification/ester hydrolysis.

Esterification:
O O
H+
R-C-OH + R'H R-C-OR' + H2O
+ rds +
O OH OH OH OH OH O
H+ K2
+
R-C-OH R-C-OH R-C-OH R-C-OH R-C-OH2 R-C-OR' R-C-OR' + H+
Keq R'OH
R'OH R'O R'O
+
+
OH
Rate = k2
R-C-OH

= k2 keq [RCOOH] [H+] [R'OH]

= k' [RCOOH] where k' = k2 keq [H+] [R'OH]

During esterification, alcohol is taken as a solvent to drive the equilibrium in the forward direction.
As solvent is generally taken in excess, its concentration hardly changes. The role of acid in esterification is
catalyst. Its concentration does not change too. As a result, acid catalysed esterification is a pseudo-first
order reaction.

Ester Hydrolysis (AAC2):

O O
H+
R-C-OR' + H2O R-C-OH + R'OH
+ +
O OH OH OH OH OH O
H+ rds
+
R-C-OR' R-C-OR' R-C-OR' R-C-OR' R-C-OH-R' R-C-OH R-C-OH + H+
HOH
+ R'OH
HOH OH OH
+
+
OH
Rate = k
R-C-OR'

= k keq [RCOOR'] [H+] [H2O]

= k' [RCOOR'] where k' = k keq [H+] [H2O]

During ester hydrolysis, water is taken as a solvent to drive the equilibrium in the forward direction.
As solvent is generally taken in excess, its concentration hardly changes. The role of acid in ester
hydrolysis is catalyst. Its concentration does not change too. As a result, acid catalysed ester hydrolysis is
a pseudo-first order reaction.
 Transesterification (AAC2):
O O
H+
R-C-OR + R'OH R-C-OR' + ROH
Mechanism of transesterification in normal esters is similar to that of esterification (AAC2) or ester
hydrolysis (AAC2). Transesterification will be of any practical use only when the equilibrium can be shifted in
the forward direction either by taking any of the reactants in excess or by removing any of the products time
to time.

Hydroxy esters undergo different reactions in acidic medium depending upon the
position of hydroxyl group, i.e. , , etc.
O
OH O Intra molecular esterification is difficult
H+ O because of the ring strain. Dehydration
CH3-CH-C-OH
O is difficult because the carbocation
-hydroxy ester at position is unstable.
O

O O
Intra molecular esterification is difficult
OH
H+ because of the ring strain. Dehydration
CH3-CH-CH2-C-OH CH3-CH=CH-C-OH is favorable because of the stability of
the alkene.
-hydroxy ester
OH O
H+ O O Intra molecular esterification is favourable.
CH3-CH-CH2-CH2-C-OH
Cyclic esters are called lactones.
-hydroxy ester
a lactone

II. AAL1 (Acidic medium, alkyl-oxygen bond cleavage, uni-molecular)

O CH3 H+
CH3-C-O-C CH3 CH3COOH + (CH3)3COH
H2O
CH3
CH2=C(CH3)2
Mechanism:
+ - H+
O CH3 OH CH3
H+ rds
CH3-C-O-C CH3 CH3-C-O-C CH3 CH3COOH + (CH3)3C+
H2O
CH3 CH3 H2O

(CH3)3COH + H+
Transesterification (AAL1):
Transesterification under AAL1 conditions is not possible because it gives ether instead.
O CH3 H+
CH3-C-O-C CH3 CH3COOH + (CH3)3COCH3
CH3OH
CH3
CH2=C(CH3)2
Mechanism:
+ - H+
O CH3 OH CH3
H+ rds
CH3-C-O-C CH3 CH3-C-O-C CH3 CH3COOH + (CH3)3C+

CH3 CH3 CH3OH

(CH3)3COCH3 + H+
III. AAC1 (Acidic medium, acyl-oxygen bond cleavage, uni-molecular):

CH3 O CH3 O
H+
CH3-C C-OCH3 CH3-C C-OH + CH3OH
H2O
CH3 CH3

(CH3)3COH + H+
H2O
- H+
CH2=C(CH3)2 (CH3)3C+ + CO
Mechanism:

CH3 O CH3 O CH3 O

H+ + rds
CH3-C C-OCH3 CH3-C C-OCH3 CH3-C C+ + CH3OH
H2O H
CH3 CH3 CH3

H2O

CH3 O
+
CH3-C C-OH + H
CH3
The following ester too undergoes similar mechanism (AAC1) but gives an unexpected product.
O O
C-O-Me
Ph Ph Ph
H+

H2O

Ph Ph
The unexpected product is obtained as a result of the attack of acylium carbocation on one of the
benzene rings (ArSE) intra-molecularly.

Polyester fibre manufacture

Esterification reaction is used to make the polyester fibres that are used for textile production. Terylene, or Dacron,
for example, is a polyester of the dicarboxylic acid terephthalic acid and the diol ethylene glycol.
O

COOH O O *
O
OH H+ O
+ HO
* O O
ethylene glycol n
COOH O
terephthalic
a polyester fibre
acid
 Mechanism in basic medium:
O O
R'OH R'OH
R-C-OH R-C-O- No reaction
NaOH or even R'O-
Partial positive charge on the carbonyl carbon in carboxylate ion is too small to
react even with alkoxide ion. As a result, one can't prepare ester in basic medium.
But ester can be hydrolysed in basic medium which is called as saponification.
Saponification
The preparation of soaps begin by boiling triglycerides (nothing but esters) with sodium hydroxide. The reaction that
takes place is nothing but the ester hydrolysis.

O CH2-O-C-R
CH2-OH
3 NaOH
R-C-O-CH
saponification CHOH + 3 RCOONa

CH2-O-C-R Sodium soaps

CH2-OH
O
glycerol
a triglyceride

Mechanism of ester hydrolysis in basic medium, saponification.

I. BAC2 (Basic medium, acyl-oxygen bond cleavage, bi-molecular):
Normal esters undergo hydrolysis in basic medium according to the following mechanism.
O O- O O
OH-
R-C-OR' R-C-OR' R-C-OH + R'- R-C-O- + R'H

OH acid base reaction

first step is rds. which is highly favourable

Rate = k [RCOOR'] [NaOH]

II. BAL2 (Basic medium, alkyl-oxygen bond cleavage, bi-molecular):
Esters with bulky carboxylate alkyl group undergo this mechanism.
CH3 O CH3 O
OH-
CH3-C C-OCH3 CH3-C C-O- + CH3OH
H2O
CH3 CH3

Mechanism:

CH3 O CH3 O CH3 O

OH-
CH3-C C-O-CH3 CH3-C C-OH + CH3O- CH3-C C-O- + CH3OH
CH3 CH3 CH3
rds