AROMATIC CARBOXYLIC ACIDS
INTRODUCTION
• Are compounds in which one or more carboxyl
groups (-COOH) are attached directly to the
aromatic ring.
COOH COOH COOH
OH NH2
Benzoic acid Salicylic acid
o-hydroxy benzoic acid Anthranilic acid
COOH COOH
COOH
CH3 COOH
COOH
o-toluic acid m-nitro
Phthalic acid benzoic acid
SIDE CHAIN AROMATIC ACIDS
• The carboxylic group is attached directly to the
aromatic ring are called side chain aromatic
acids.
CH2COOH
Phenyl acetic acid
PREPARATION
1. By oxidation of alkyl benzenes with
acidic Na2Cr2O7
CH3 COOH CH2CH3
KMnO4 KMnO4
Toluene benzoic acid Ethyl benzene
2. By reaction of phenyl magnesium
bromide with CO2 followed by acid
hydrolysis of the addn product
MgBr COOMgBr COOH
CO2 H2O
Phenyl Benzoic acid
magnesium bromide
3. By acid hydrolysis of phenyl cyanide
CN COOH
CO2
Phenyl Benzoic acid
cyanide
4. By basic hydrolysis of
benzotrichloride
CCl3 COONa COOH
NaOH H2O
H2O
Benzo trichloride Benzoic acid
REACTIONS OF COOH GROUP
1. Salt formation
Benzoic acid reacts with NaOH/NaHCO3 to form
sodium benzoate.
COOH COONa
NaOH H2O
COOH COONa
NaHCO3 H2O CO2
2.Ester Formation
COOH COOC2H5
C2H5OH H2O
Ethyl benzoate
3.Acyl halide formation
COOH COCl
PC l 3 PO C l 3 HCl
COOH COCl
SO 2 HCl
SO C l2
4. Reduction to benzyl alcohol
COOH CH2OH
LiAlH4
5. Decarboxylation
COOH
CaO
CaCO3
REACTIONS OF BENZENE RING
• The benzene ring of benzoic acid undergoes
the usual electrophilic reaction.
• COOH group is meta directing and ring
deactivating.
COOH COOH
H2SO4
HNO3
NO2
m-nitro benzoic acid
ACIDITY OF BENZOIC ACID
• Resonance stabilization by the aromatic pi molecular
orbital would play a large role in the relative acidity of
benzoic acid. This is not so.
• Carboxylate ion with negative charge is shared by the two
carboxylate oxygen atoms but cannot be effectively
delocalized by the aromatic ring.
• The oxygen of the carboxylate anion are not directly
adjacent to the aromatic ring.
• Resonance structures cannot be drawn, because the
benzene ring does not participate in resonance
stabilization of the carboxylate group.
• Substituents on a benzene ring influence acidity primarily
by the inductive effect.
O
O
-
O H
OH
-
O
O
-- O
O
Resonance forms of carboxylate ion
ACIDITY CONSTANTS
OF BENZOIC ACID
Electron withdrawing substituents
• Regardless of the position of substitution an
electron withdrawing group usually increase
the acidity of a benzoic acid.
• This is because of an electronegative
substituent increases the acid strength are
again destabilization of the acid and
stabilization of the anion.
NO 2
O
NO 2 O
-
O H
OH
D e s ta b iliz e d b y e le c tr o n S ta b iliz e d b y e le c tr o n
w ith d r a w a l w ith d r a w a l
Electron releasing substituents
• Electron releasing alkyl substituent that is p
or m to the carboxyl group decreases the
acidity of benzoic acid.
O
CH3
OH
Ortho substituents
• Ortho (whether electron releasing or
electron withdrawing increase the acidity of
benzoic acid. Steric effect of two substituents
increase the acid strength.
COOH
X
Predicting acid strengths of substituted
benzoic acids
• The strength of the substituted benzoic acids is
determined largely by inductive effects because the
CO2 group does not enter into resonance with the
aromatic ring.
• Electron withdrawing substituents increase the
acidity of benzoic acid.
• Electron donating groups decrease the acidity of
benzoic acid.
• Substituents at the ortho position almost always
increase the acidity of a benzoic acid
