Unit 2C - Aromatic Acids

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Aromatic Acids
Aromatic Acids
• The organic compounds where a carboxylic group is attached directly to aromatic ring are
known as aromatic carboxylic acids.
• Benzoic acid is a representative of this class.
• In the aromatic carboxylic acids the carboxylic group is attached to sp2 hybridized carbon of
the aromatic ring system while in case of aliphatic acids the carboxylic group is directly
attached to sp3 hybridized carbon.
Dr. Deepak K. Lokwani, Assistant Professor, Department of Pharmaceutical Chemistry, R. C. Patel Institute of
Pharmaceutical Education and Research, Shirpur
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Aromatic Acids
• The compounds where carboxylic group is present on the side chain of aromatic ring
system as in phenyl acetic acid and cinnamic acid show similar behaviour as aliphatic
carboxylic acids.
Phenyl Acetic acid
Aromatic Acids
• In IUPAC nomenclature, these acids are termed benzene carboxylic acid derivatives.
• However, the common names of aromatic carboxylic acids are more familiar and are also
accepted by IUPAC
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Aromatic Acids
• 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
5
acid).
Acidic Character of Aromatic Carboxylic Acids
• The acidic strength of aromatic carboxylic acid is attributed to resonance stabilization of

carboxylate ion formed by the loss of proton.
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• The aromatic carboxylic acids have high acidic strength compared to aliphatic carboxylic acid.
• In aromatic carboxylic acids, -COOH group is attached to sp2 hybridized carbon of phenyl
ring, whereas in carboxylic acids the -COOH group is attached to sp3 hybridized carbon of
alkyl group.
• The sp2 -hybridized carbon is more electronegative compared to sp3 hybridized carbon.
• Thus, phenyl ring stabilizes the carboxylate ion more effectively compared to alkyl group
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Effect of substituents on acidic strength of Aromatic Carboxylic Acids

• The presence of electron withdrawing groups increases the acidic strength as these groups
delocalize the negative charge and stabilize the carboxylate ion.
• However, the electron releasing groups decrease the acidic strength by intensifying the negative
charge and thus, destabilizing the carboxylate ion.
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• The high acidic strength of p-nitrobenzoic acid is due to both -I and -R effects of nitro group
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• Comparison of acidic strength in isomeric substituted benzoic acids
• In case of aromatic carboxylic acids the acidic strength depends upon two factors:
i. Inductive effect which in turn depends upon the position of the substituent (lesser the distance
between the substituents, stronger is the inductive effect) and is experienced in the order ortho
> meta > para.
ii. Resonance effect of substituents, which is observed maximum at ortho and para positions
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• The order of acidic strength of ortho, meta, and para nitrobenzoic acid is as follows:
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• The order of acidic strength of ortho, meta, and para nitrobenzoic acid is as follows:
• The nitro group is electron withdrawing in nature and increases the acidic strength of
carboxylic acid through -I and -R effects.
• The resonance effect is operative more at ortho and para positions; thus ortho and para isomers
are more acidic compared to meta isomer.
• Among ortho and para, the ortho isomer is more acidic due to inductive (-I) effect which is
more operative for ortho isomer.
• Thus, the overall acidic strength in case of isomeric nitrobenzoic acids follows the order
ortho > para > meta. 14
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• The order of acidic strength of ortho, meta, and para chlorobenzoic acid
• Chlorine exhibits + R effect but at the same time it exhibits a strong -I effect. In this case
inductive effect is the only factor, which contributes towards acidic strength. The impact of
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inductive effect follows the order ortho > meta > para
• The order of acidic strength of ortho, meta, and para hydroxybenzoic acid is as follows:
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• The order of acidic strength of ortho, meta, and para hydroxybenzoic acid is as follows:
• The -OH group is electron withdrawing in nature due to inductive (-1) effect but at the same
time it exhibits a + R effect.
• Thus, the only factor contributing towards acidic strength in this case is inductive effect which
follows the order ortho > meta > para.
• Further, the relatively high acidic strength of ortho

isomer is the result of stabilization of carboxylate ion
through intramolecular hydrogen bonding
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PREPARATION OF AROMATIC CARBOXYLIC ACIDS
A. Oxidation reactions
1. Oxidation of Alkyl or alkenyl

benzenes:
• The oxidation of alkyl substituted benzene
or benzene with unsaturated carbon chain in
the presence of strong oxidizing agent like
acidified potassium or sodium dichromate
results in the formation of benzoic acid,
irrespective of the length of carbon chain of
the alkyl group.
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1. Oxidation of Alkyl or alkenyl benzenes: The of xylenes results in the formation of

corresponding dicarboxylic acid
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2. Oxidation of Primary Aromatic Alcohol: The oxidation of benzyl alcohol with acidified
sodium dichromate or potassium permanganate results in the formation of benzoic acid.
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2. Oxidation of Aromatic Carbonyl Compounds: The aromatic aldehydes or alkyl aryl ketones
on oxidation with acidified dichromate or potassium permanganate results in the formation of
aromatic carboxylic acid.
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B. Hydrolysis reactions
1. Hydrolysis 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 benzoic acid.
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2. Hydrolysis of aromatic nitriles. The hydrolysis of benzonitrile in acidic or alkaline medium

results in the formation of benzoic acid via formation of an amide.
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3. Hydrolysis of ester. The hydrolysis of alkyl or aryl benzoates yields aromatic carboxylic acid
and alcohol or phenol.
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C. Other methods
1. Carboxylation of organometallic compounds:

• In organometallic compounds
such as Grignard reagent and
phenyllithium, the aryl group
behaves as a nucleophile,
which adds carbon dioxide (a
weak nucleophile) to form
carboxylate salts. The acidic
hydrolysis of addition product
results in the formation of
aromatic carboxylic acids. 25
C. Other methods
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.
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C. Other methods
3. Preparation of hydroxy benzoic acids: The carboxylic group may be introduced to phenols
by using carbon dioxide in the presence of sodium hydroxide (Kolbe-Schmitt reaction). These
methods are used for the preparation of hydroxy benzoic acids.
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REACTIONS OF AROMATIC CARBOXYLIC ACIDS
• Aromatic acid undergo reactions by three different way:
1. Reactions involving acidic hydrogen: In these reactions, the

cleavage of oxygen-hydrogen bond takes place.
2. Reactions Involving -OH Group: Nucleophilic Acyl

Substitution
3. Reactions Involving -COOH Group
4. Reactions involving aromatic ring: These reactions involve the

electrophilic substitution reactions of benzene ring and COOH
group remains intact during these reactions.
5. Reduction Reaction 28
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1. Reactions involving acidic hydrogen: In these reactions, the cleavage of oxygen-hydrogen
bond takes place.
a) The aromatic carboxylic acids react with bases such as sodium hydroxide, sodium carbonate,
and sodium bicarbonate to form sodium carboxylate.
• The reaction with sodium

bicarbonate is used for
qualitative detection of
carboxylic acid functional
group since the reaction
occurs with evolution of
carbon dioxide in the form of
brisk effervescence.
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Sodium benzoate is used as a food preservative and is effective in acidic medium.

1. Reactions involving acidic hydrogen: In these reactions, the cleavage of oxygen-hydrogen
bond takes place.
b) Reaction with diazomethane (formation of methyl ester): The aromatic carboxylic acids on
reaction with diazomethane form methyl esters. For example, the reaction of benzoic acid with
diazomethane results in a high yield of methyl benzoate at room temperature.
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2. Reactions Involving -OH Group: Nucleophilic Acyl Substitution
• These are the nucleophilic substitution reactions of carboxylic acid, which occur through an
addition-elimination mechanism. The reactions may be acid or base catalysed.
• The general reaction may be written as follows:
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• Mechanism: Acid Catalysed Substitution:
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• Mechanism: Acid Catalysed Substitution:
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• Mechanism: Base Catalysed Substitution:
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2. Reactions Involving -OH
Group: Nucleophilic
Acyl Substitution
• The formation of acid
derivatives, namely acid
chlorides, acid anhydrides,
esters, and amides are the
examples of nucleophilic
substitution reactions
occurring through
addition-elimination
mechanism. 35

• These reactions are carried out as salts of carboxylic acids
a) Formation of hydrocarbons: Heating sodium salt of benzoic acid with soda lime results in
the formation of benzene.
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b) Hunsdiecker reaction: Silver salt of benzoic acid is heated with bromine to yield
bromobenzene with the evolution of carbon dioxide
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c) Formation of aromatic
carbonyl compounds.
Calcium salt of benzoic
acid, when heated forms
benzophenone while
heating calcium benzoate
with calcium formate or
calcium acetate results in
the formation of
benzaldehyde and
acetophenone respectively
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4. Reduction Reaction:
• The reduction of carboxylic acids is carried out in the presence of strong reducing agents like
lithium aluminium hydride. The reaction involves the hydride transfer and reduces the
carboxylic acid to alcohol
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5. Electrophilic Substitution Reactions:
• The carboxylic functional group attached directly to benzene ring behaves as an electron
withdrawing group through -R effect. Due to electron withdrawing character (-R effect), the
functional group behaves as a ring deactivator and makes the ortho and para positions electron
deficient.
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5. Electrophilic Substitution Reactions:
• Thus, the carboxylic acid

group behaves as a ring
deactivator and meta
director towards
electrophilic substitution
reactions such as
halogenation and nitration.
Aromatic carboxylic acids
do not undergo Friedel-
Crafts reaction
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Unit 2C - Aromatic Acids

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07-09-2019

• Benzoic acid is a representative of this class.

Phenyl Acetic acid

• However, the substituted

Acidic Character of Aromatic Carboxylic Acids

• The acidic strength of aromatic carboxylic acid is attributed to resonance stabilization of

Acidic Character of Aromatic Carboxylic Acids

• The acidic strength of aromatic carboxylic acid is attributed to resonance stabilization of

Acidic Character of Aromatic Carboxylic Acids

• The acidic strength of aromatic carboxylic acid is attributed to resonance stabilization of

Acidic Character of Aromatic Carboxylic Acids

Effect of substituents on acidic strength of Aromatic Carboxylic Acids

Effect of substituents on acidic strength of Aromatic Carboxylic Acids

Effect of substituents on acidic strength of Aromatic Carboxylic Acids

• Comparison of acidic strength in isomeric substituted benzoic acids

Effect of substituents on acidic strength of Aromatic Carboxylic Acids

• Comparison of acidic strength in isomeric substituted benzoic acids

Effect of substituents on acidic strength of Aromatic Carboxylic Acids

• Comparison of acidic strength in isomeric substituted benzoic acids

Effect of substituents on acidic strength of Aromatic Carboxylic Acids

• Comparison of acidic strength in isomeric substituted benzoic acids

Effect of substituents on acidic strength of Aromatic Carboxylic Acids

• Comparison of acidic strength in isomeric substituted benzoic acids

Effect of substituents on acidic strength of Aromatic Carboxylic Acids

• Comparison of acidic strength in isomeric substituted benzoic acids

• Further, the relatively high acidic strength of ortho

PREPARATION OF AROMATIC CARBOXYLIC ACIDS

1. Oxidation of Alkyl or alkenyl

PREPARATION OF AROMATIC CARBOXYLIC ACIDS

1. Oxidation of Alkyl or alkenyl benzenes: The of xylenes results in the formation of

PREPARATION OF AROMATIC CARBOXYLIC ACIDS

PREPARATION OF AROMATIC CARBOXYLIC ACIDS

PREPARATION OF AROMATIC CARBOXYLIC ACIDS

1. Hydrolysis of trihaloalkyl benzenes: The chlorination of toluene in the presence of

PREPARATION OF AROMATIC CARBOXYLIC ACIDS

2. Hydrolysis of aromatic nitriles. The hydrolysis of benzonitrile in acidic or alkaline medium

PREPARATION OF AROMATIC CARBOXYLIC ACIDS

PREPARATION OF AROMATIC CARBOXYLIC ACIDS

1. Carboxylation of organometallic compounds:

PREPARATION OF AROMATIC CARBOXYLIC ACIDS

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

PREPARATION OF AROMATIC CARBOXYLIC ACIDS

REACTIONS OF AROMATIC CARBOXYLIC ACIDS

• Aromatic acid undergo reactions by three different way:

1. Reactions involving acidic hydrogen: In these reactions, the

2. Reactions Involving -OH Group: Nucleophilic Acyl

3. Reactions Involving -COOH Group

4. Reactions involving aromatic ring: These reactions involve the

REACTIONS OF AROMATIC CARBOXYLIC ACIDS

• The reaction with sodium

REACTIONS OF AROMATIC CARBOXYLIC ACIDS

REACTIONS OF AROMATIC CARBOXYLIC ACIDS

REACTIONS OF AROMATIC CARBOXYLIC ACIDS

REACTIONS OF AROMATIC CARBOXYLIC ACIDS

REACTIONS OF AROMATIC CARBOXYLIC ACIDS

REACTIONS OF AROMATIC CARBOXYLIC ACIDS

REACTIONS OF AROMATIC CARBOXYLIC ACIDS

REACTIONS OF AROMATIC CARBOXYLIC ACIDS

REACTIONS OF AROMATIC CARBOXYLIC ACIDS

REACTIONS OF AROMATIC CARBOXYLIC ACIDS

REACTIONS OF AROMATIC CARBOXYLIC ACIDS

REACTIONS OF AROMATIC CARBOXYLIC ACIDS