CHAPTER 3

Carboxylic Acids
• Carboxyl group, -COOH consist of a carbon
atom joined to an oxygen atom by a
double bond and to a hydroxyl group, OH,
by a single bond.

O
R C OH

• General formula: CnH2nCOOH

 Naming of Carboxylic Acids

• Find the longest continuous carbon

chain containing the carboxyl group.

• Start numbering from the one that

closest to the carboxyl group, COOH.

• The ‘–e’ ending of the parent alkane is

replaced with ‘–oic acid’.
Example 1:

O
CH3CHCH2 C OH
CH3

3-methyl-butanoic acid
Example 2:

Cl O
CH3 C C OH
CH3

2-chloro-2-methyl-propanoic acid
Example 3:

O
CH3 C OH

4-methylcyclohexanoic acid
Example 4:

O
C OH

benzoic acid
 Preparation of Carboxylic Acids

• Carboxylic acids come from alkenes by

the process called hydration.

• In between the conversion of alkenes to

carboxylic acids, alcohol and aldehydes
are formed by oxidation process.
Example:

H OH
CH2 CH2 H2 O/H+ KMnO4/H+
CH2 CH2
ethene heat
ethanol

H O O
H
KMnO 4/H + CH2 C OH
CH2 C H
heat ethanoic acid
ethanal
 Preparation of Benzoic Acid by
Oxidation of Alkyl Benzene

CH3 CH2OH COOH

[O] [O]
 Preparation of Carboxylic Acid by
Hydrolisis of Nitriles

R CH2 Cl + NaCN ethanol

reflux

R CH2 CN
nitrile

H2O/H+

R CH2 COOH
Carboxylation of Grignard Reagents

O
[1] CO2
R MgX + R C OH
[2] H3O

• Grignard reagents react with CO2 to give

carboxylic acids after protonation with
aqueous acid.
 Grignard Synthesis

(CH3CH2)2O
R X + Mg R Mg X
Grignard reagents

(CH3CH2)2O
H3C Br + Mg H3C Mg Br
Methylmagnesium
bromide
Example:

Cl MgCl COOH

Mg CO2/H3O+
[1] [2]

phenylmagnesium
chloride

1) Formation of Grignard Reagent

2) Reaction with CO2
Reactions of
Carboxylic
Acids
 Formation of Salt

• Carboxylic acids are weak acids. They turn

blue litmus to red.

• They undergo neutralization reactions

with base to form salts of carboxylic acid
and water.
Example:

RCOOH + NaOH RCOO- Na+ + H2O

carboxylic acid sodium sodium carboxylate
hydroxide

CH3COOH + NaOH CH3COO- Na+ + H2O

ethanoic acid sodium ethanoate
 Reduction to Alcohols

• Carboxylic acids are reduced to primary

alcohols when it is reacts with lithium
aluminum hydride (LiAlH4) in dry ether.

• The reaction doesn’t work with other

reducing agent.
General reaction:

O H
R C OH LiAlH 4 in ether
R C OH
carboxylic acid
H
primary alcohol
Example:

O H
CH3 C OH LiAlH 4 in ether CH3 C OH
ethanoic acid
H
ethanol
 Formation of Acyl Chlorides
• Carboxylic acids canNOT be converted to
acid chlorides by using Cl- as a nucleophile
because Cl- is a weaker base than the
departing leaving group –OH.

• Carboxylic acids react with thionyl chloride,

SOCl2 at room temperature to form acyl
chlorides.
General reaction:

O
room temp.
R C OH + SOCl2
carboxylic acid
O

R C Cl
acyl chloride
 Formation of Esters

• Carboxylic acids is heated with alcohols

in the presence of acid catalyst to form
an ester.

• This reaction is called Fisher

esterification.
General reaction:

O
conc. H2SO4
R C OH + HO R'
heat
carboxylic acid alcohol

O
R C O R' + H2O
ester
Example of Esterification

O
conc. H2SO4
CH3 C OH + HO CH2CH3 heat
ethanoic acid ethanol

O
CH3 C O CH2CH3 + H2O
ethylethanoate
 Formation of Amides
• Two-step of reactions. Step 1: The
preparation of ammonium salt. Carboxylic
acid reacts with ammonia to produce an
ammonium salt of carboxylic acid.

• Step 2: Formation of amide. The

ammonium salts of carboxylic acid is
heated to form amide.
General reaction:

O NH3
O

R C OH
(ammonia)
R C O- NH4+
carboxylic acid ammonium salt

heat

O
R C NH2 + H2O
amide
Example:

O
C - +
CH3 O NH4 heat
ammonium ethanoate

O
CH3 C NH2 + H2O
ethanamide
 Formation of Acid Anhydrides

• Acid anhydride is prepared in the

laboratory from reaction of carboxylic
acid with acyl chloride in the presence of
pyridine.
General reaction:

N
O O
R C OH + Cl C R' pyridine
carboxylic acid acyl chloride

O O
R C O C R' + HCl
acid anhydride
Example:

N
O O
pyridine
CH3 C OH + Cl C CH3
ethanoic acid ethanoyl chloride

O O

CH3 C O C CH3 + HCl

ethanoic anhydride