CHAPTER 21 Aromatie

Carboxylic
and Sulfonic Acids
2 ! 4

AROMATIC CARBOXYLIC ACIDS

A.
21A.1 INTRODUCTION
carboxylic group is attached directly to aromatic ring are known
The organic compounds whereBenzoica where
acid is a representative of this class. The compounds
s aromatic carborylic acids. acid and
present on the side chain of aromatic ring system as in phenyl acetic
carboxylic group is
behaviour as aliphatic carboxylic acids. In the aromatic carboxylic acids
cinnamic acid show similar hybridized carbon of the aromatic ring system while in
case
the carboxylic group is attached to sp
carboxylic group is directly attached to sp' hybridized carbon.
of aliphatic acids the

-H

carboxylic acid derivatives. However, the

acids are termed benzene
In IUPAC nomenclature, these more familiar and are also accepted
by IUPAC. A
acids are
common names of aromatic carboxylic
are as follows:
few selected examples of the family
697
898 Organic Chemis
COOI COOH COOH

Cl
Benzenecarborylic acd 4Chlorobenzoic aicd
2-Hydroxybenzoic acid
(Benroic acid) (Salicylic acid) (m-p. 243C)
(mp. 121'C) (m.p. 158'C)

CH=CHCOOH COOH
COOH

COOH

COOH
1.Phcny lpropcnoic acid Benzene-1L2dicarboxylic acid Benzene-1,4-dicarboxylhc acd
(Cinnamic acid) (Phthalic acid) erphthalc acid)
(Ter
(mp. 11C) (m.p. 208'C dec.) (mp. 308C sublime)

ÇOOH

COOH
Benzene- ,3-dicarbosylic acid
(sophthalic acid)
(m.p. 347°C)

Physical properties. The aromatic carboxylic acids exhibit polarity due to presence of polar
carbonyl and hydroxyl group. In general, carboxylic acids exist in the dimer form due to
intermolecular hydrogen bonding (as in case of aliphatic acids). The aromatic carboxylic acids are
generally crystalline solids with high melting point. However, the substituted carboxylic acids may
form intramolecular hydrogen bonding as in case of
2-hydroxybenzoic acid (salicylic acid).
Intramolecular
hydrogen
bonding

OH

Benzoc acid
Salicylic acd

21A.2 PREPARATION OF AROMATIC CARBOXYLIC ACIDS

Besides the preparative methods meant
meth d a s.uthar t th exclusivelv for aromatic carboxylic acids, some of the
o the sy athesi l al t:
 Aromatic Carborylie and Sulfonic Acids 699
also been given for the methods that have already been discussed in previous chapter. Various
methods for the preparation of aromatic carboxylic acids are as follows.

Oxidation reactions
Oxidation of alkyl or alkenyl benzenes. The oxidation of alkyl substituted benzene or
henzene with unsaturated carbon chain in the presence of strong oxidizing agent like acidified
potassium or sodium dichromate results in the formation of benzoic acid, irespective of the length
of carbon chain of the alkyl group (p. 291). The oxidation of xylenes results in the formation of
corespond1ng dicarboxyl1c acids in the following manner:
CH

Methylbenzene
(Toluenc)

CH,CH, COOH
Na,Cr,0,H*

Ethylbenzene Benzoic acid

HC=CH,

Ethenylbenzene
(Styrene) CH, COOH
Na,Cr,0,/H
~CH, cOOH
oXylene Phthalic acid

The oxidation cannot be carried out if groups like -OH and NH, are present on aromatic ring as
they are highly susceptible to oxidation.
2. Oxidation of primary aromatic alcohol. The oxidation of benzyl alcohol with acidified
sodium dichromale or potassium permanganate results in the formation of benzoic acid.

-CH,0H COOH
Na,Cr,0,/H
o KMaO,
Benzyl alcohol

3. Oxidation of aromatic carbonyl compounds. The afvmstic aldethy des or alkylaryl ketones on
ovdaton wnh scdificd dihromate or potass.um permanganie (Setin 18. 3.3) result in the
formation of aromatic carboxylic acid.
 B KMn)/ OH COOH

-CH,

Acetophenone

3) Hydrolysis reactions
1. lHvdrolysis of trihaloalkyl benzenes. The chlorination of toluene in the presence of ultraviolet
light results in the formation of trichloromethyl benzene. The alkaline hydrolysis of this product
gives benzotc acid.

OH
HO.
CH, CCl, wCOOH
ClJUV OH" H,0 OH H,0

Trichiorustnethylbenzene LRsable

2. Hydroly sis of aromatic nitriles: The hydrolyss of benzonitrile in acid1c or alh aline amed1um
Iesults in the formation of benzoic acid via formation of an amide. The mechunism s stmilar to that
discussed carlier in case of aliphatic carboxylic acids (refer Section 19.2.2: po, 624-26).

C=N -NH, -OH

H".H,0

Benzonitrile Benzamide Benzoic aciJ

CH,C=N CH,C-NH, CH,COOH

H, H,0

Phenylacetonitrile Pheuylacetamide Phenylacetic acid

3. Hsdrolysis of ester. The hydrolysis of alkyl or aryl benzoates yields aromatic carboxylic aci
and alcohol or phenol.
 Aromatic Carborylic and Sulfonie Acids 701

H'. H,0
-COOH + C,H,OH
Ethylbenzoate Benzoic acid Ethanol

H.H,0
-COOH + HO
Benzoic acid Phenol
Phenylbenzoate

mechanism has already been

The hydrolysis can occur in both acidic or alkaline media (the
discussed in Section 19.2.2: p. 626 with aliphatic carboxylic acids).

C)Other methods
1. Carboxylation of organometallic compounds. In organometallic compounds such as Grignard
adds carbon dioxide (a
reagent and phenyllithium, the aryl group behaves as a nucleophile. which
results in
weak nucleophile) to form carboxylate salts. The acidic hydrolysis of addition product
the formation of aromatic carboxylic acids.

H,on
Mg (=0
dry ether -MgBr dry cther
Phenylmagnesium
bromide

HO

Br
Bromobenzene

H,oH"
2Li
-LiBr dry ether -LiOH

Phenyllithium

2. Haloform reaction of acetophenone. The acetophenone is an aryl methyl ketone, which

reacts with halogen in the presence of sodium hydroxide to form haloform and sodium benzoate.

3NaOH
-CH, + 3X,

H,ONaOH + CHX,

Soxliun benaat: Haloform

708 Organic Chemistry

3. Preparation of hyd roxy benzole acids. Further, the carboxylic group may be introduc cd
phen ls bs using cathon duIde n th pescac ol sodium hydrox1de |Kolbe-Schmitt reaction
(p. S10)j and carbon tetrachlorde in the presence of sodium hydroxide (sim1lar to
Reimer-Tiemang
reaction (p. 511)) These methods are used for the preparation of hydroxy benzoic acids.

O Na OH OH
co N COOH
H.

Salicylic sd