Carboxylic acid B. Sc.

III semester

Carboxylic Acid
Organic compounds containing carboxyl (COOH) group are called carboxylic
acid. General formula is RCOOH or Carboxyl derivative of hydrocarbon
Example: HCOOH formic acid, CH3 COOH acetic acid.

Classification: Based on the number of COOH groups.

They are classified as mono, di and tri carboxylic acid
Mono carboxylic acid:- contains only one COOH group example HCOOHformic
acid.
Dicarboxylic acid:- Contains two COOH groups, example HOOC-COOH oxalic
acid
Tricarboxylic acid:- contains three COOH groups examplecitric acid

Nomenclature:- Common names are obtained from Latin words indicating the
source of the acid. IUPAC names of carboxylic acid is alkanoic acid is obtained
from alkane by replacing final ‘e’ by oic acid suffix

Examples:- Mono carboxylic acid (Alkanoic acid)

Formula Common name source IUPAC name

HCOOH Formic acid Latin Methanoic aid
Formica=ant
Latin
CH3COOH Acetic acid Acetum=Vinegar Ethanoic acid
protos,
CH3CH2COOH Propionic acid meaning "first", Propanoic acid
and pion,
meaning "fat";
(Greek)
CH3-(CH2)2COOH Butyric acid βούτῡρον, Butanoic acid
=better
CH3CH CH2COOH Chloro butyric - 3-chloro
Cl acid Butanoic acid

Dicarboxylic acid (Alkanedioic acid)

Formula Common name source IUPAC name

HOOC – COOH Oxalic acid wood- Ethanedioic acid
sorrel (Oxalis)
HOOCCH2CH2 COOH Succinic acid Latin succinum, Butane dioic acid
meaning amber

Tri calboxylic acid:- Alkane trioic acid

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Carboxylic acid B. Sc. III semester

Formula Common source IUPAC name

name
Citric acid Citrus fruits 3-Carboxyl-3-
hydroxy
pentane dioic
acid

Based on nature or structure acid are classified as aliphatic and aromatic

Examples
Aliphatic:- open chain structure
H COOH Formic acid CH3COOH acetic acid

Aromatic: Closed chain structure- examples

Formula Common name IUPAC name
Benzoic acid Benzene
carboxylic acid

Salicylic acid o -Hydroxy

benzoic acid

O OH Anthranilic (o-Amino benzoic

acid acid
NH 2

O OH
O
phthalic acid Benzene-1,2-
dicarboxylic acid
OH

Preparation:-

Arndt-Eistert reaction:- (Homologation)

1- Wolff rearrangement
N 2- Ag2O
O O CH2N2 N
SOCl2
R OH R O -HCl H2O
Cl O R

O
N2
R OH

Homologation of carboxylic acid takes place. First carboxylic acid is converted

to acid chloride on treating acid chloride with diazomethane and reacting the
resulting diazo with Ag2o and water give higher carboxylic acid. finally last
step is rearrangement, followed by hydrolysis.

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Carboxylic acid B. Sc. III semester

Synthesis of higher homolog of carboxylic acid from a lower member is called

as Arndt-Eistert synthesis.

Example

1- Wolff rearrangement
N 2- Ag2O
O O CH2N2 N
SOCl2 CH2
H3C OH H3C O -HCl H2O
Cl O CH3
Acetic acid

O
N2
H3C C OH
H2
Propanoic acud

Reactions:-
1) Formation of acid chloride:-

O
O
SOCl 2 SO 2 + HCl
R OH R Cl
thionyl
chloride

O O
PCl 3 H3PO 3
R OH R
Cl
Phosphorous acid

O O
PCl 5 POCl 3 HCl
R OH R Cl
Phosphorous
oxy chloride

Example

PCl 3
O or O
PCl 5
H3C OH H3C Acetyl chloride
or Cl
Acetic acid SOCl 2

2) Formation of amide:-

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Carboxylic acid B. Sc. III semester

O O O
NH 3
R OH R O Amide
NH 4 -H2O R NH 2

Ammonium
carboxylate
Example

O O O
NH 3
H3C OH H3C O Acetamide
NH 4 -H2O H3C NH 2
Acetic acid Ammonium
acetate

3) Formation of ester (Esterification):-formation of ester by combining acid

and alcohol in the presence of conc sulphuric acid.

O O
conc H2O
OH R OH R O
R H2SO 4 R
Carboxylic Alcohol Ester
acid

Example

O H3 O
C conc
HO CH 3 O H2O
H3C OH H3C
H2SO 4 C2H5
Ethyl alcohol
Acetic acid
Ethyl acetate

When alcohol reacts with carboxylic acid in presence of conc. H 2SO4 gives
ester and this reaction is called esterification

4). Formation of acid anhydride:- An acid anhydride is a compound that has

two acyl groups bonded to the same oxygen atom. Its general formula is
(RC(O))2O

It is obtained by the condensation of two molecules of acid with the elimination

of water molecule

Note: if R =CH3 it is acetic anhydride

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Acid Strength:- Strength of an acid or its acidity is proportional to the relative

ease with which it loses a proten (H+)
Carboxylic acid is a resonance hybrid of the following structure.

O O O

H O O
H Proton
R R R
O
H Carboxylate anion

Non equivalent

Internal energy is more

hence stability is less
Carboxylate anion also exhibit resonance

O O O

R O R O
R
O
Equivalent structures
Delocalized

Internal energy is less and

Hence stability is more.
This delocalization of the electron cloud means that both of the oxygen
atoms are less strongly negatively charged; the positive proton is therefore less
strongly attracted back to the carboxylate group once it has left; hence, the
carboxylate ion is more stable.
The acidity of carboxylic acid is due to the strong resonance stabilization
of its anion.Factors which stabilize the carboxylate anion more should
enhance the acidity and the factors which make the anion less stable should
decrease the acidity.

O O
<
<

D O W O

D = donating W = withdrawing group

Like CH3, OH, NH2 like NO2, CHO, CO
Destabilizes stabilizes
Acidity decreases Acidity increases

Electron donating or releasing groups intensify the negative charge on

carboxylate anion, destabilize it and decreases acidity. Therefore HCOOH
(formic acid) is stronger acid than CH3 COOH (acetic acid).

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Carboxylic acid B. Sc. III semester

Electron withdrawing or attracting groups disperse the negative charge on the

anion, stabilize it and increases the acidity of carboxylic acid

Example trichloro acetic acid Cl3CCOOH is stronger acid than dichloro acetic
acid Cl2 CH COOH.

Hydroxy acids:- Hydroxy derivative of carboxylic acid

Example:- CH3 – CH – COOH Lactic acid
OH (2-Hydroxy propanoic acid)

Effect of heat on alpha, beta and gamma hydroxy acids

In alpha hydroxy acid OH group is attached to alpha–Carbon atom

Alpha hydroxy acid on heating gives cyclic estersknown as lactide

H3C O
O
H3C
CH
CH C
HO Heat
OH O O

HO OH C CH

C CH CH 3
O
CH 3
O
Lactide
Lactic acid

Beta – hydroxy acid:- OH group attached to beta-Carbon atom

H
H3C C
CH Heat H
H3C C C COOH
HO H COOH H

2-Butenoic acid
3-Hydroxy
butanoic acid (Apha beta unsaturated acid)
crotonic acid

This acid on heating or treating with mineral acid (HCl) eliminates a water
molecule and converts into alpha beta unsaturated acid
Gamma- Hydroxy acid:- OH group attached to gamma - carbon atom
Gamma Hydroxy acid on heating undergoes intra molecular esterification to
form a five membered eyclic ester (internal ester)

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Carboxylic acid B. Sc. III semester

H2 H2C C
H2C C C COOH
Heat
H2
H2C O
HO -H2O
C
H2
Gamma hydroxy
butanoic acid Gamma butyro lactone

Questions

One mark
1. Define carboxylic acid
2. Give an example for dicarboxylic acid.
3. What is Arndt-Eistert reaction?
4. Which product is obtained when alpha hydroxyl acid is heated?

Two marks
1. Write any two reactions of carboxylic acid.
2. What is Arndt-Eistert reaction? Give
3. What happens when alpha and beta carboxylic acids are heated?

Three or four marks

1. How do you classify carboxylic acids?
2. Write a note on effect of heat on alpha, beta and gamma carboxylic acid.
3. Write a note on acidity of carboxylic acid.

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