280

substituents.
Aidity incteases with increasingelectronegativity of

. F-(-(00HC-C-(00H
F
Tnßuoroaetic Tnchloroacetic

Adity increases with decreasing distance of halogen atom trom the carboxyi groun
CI
CHCHCH-C0OH> CHCH-CH-COOH>CI-CH,CH,CH-C00H
Electron donating groups (EDG)decrease the acidity by destabilising the conjugate
stronger acid than acetic acid.
Strength of aromatic carboxylic acids :
Electron withdrawing group attached to phenyl ring of aromatic carboxvic acid increases their cit
benzoic acid.
eg- p-nitrobenzoic acid is stronger acid than
Electron releasing group attached to phenyi ring decreases acidity, eg., p-methoxybenzoic
acid than benzoic acid.

Reactions Involving Cleavage of C-OH Bond

RCOOHH,S Pa, or PCi,
Anhvdride or P-0 or SOCI,in pyridine’RCOCI
Add choide
-H,0
ROHH R--OH
RCOOR'
Ester
-H,0 -H-0 ’RCONH,Amide

Mechanism of esterification : It is a nucleophilic acyl substitution.

(a) Protonation of carboxyl oxygen :

0-H
’R-OHOH
(b) Nucleophilic addition of alcohol:
Proton :ö-R
transfer
R-CO
OH
K-H --OH R-c-ÖH,
OH :OH
Terahedral intermediate
(c) Elimination of water molecule :
:ö-R O-R
-H,0
OH, R-C

OH -OH
Protonated ester
(d) Protonated ester loses a proton to give ester :
0-R'
R-C
+OH OR'
Reactions Involving - COOH Group Ester

RCH,0H -() LiAlH/ether

or B,H,ether
NaOH + CaO
(Reduction) () H,o" ’ RH+Na, CO%
R--0H NaOH, Electrolysis
(Decarboxylation)
>R-R+CO, + NaOH
(Kolbe electrolysis)