CARBOXYLIC ACID DERIVATIVES

 These are compounds that yield carboxylic acids upon reaction with
water.
 They are:
(i) Esters
(ii) Amide
(iii) Acid anhydrides
(iv) Acid halides
(v) nitriles.
 Esters of Carboxylic Acids
 The functional group of a carboxylic acid ester is an acyl group bonded to –OR or –OAr.

Nomenclature of Esters
 Naming of esters is derived from the corresponding carboxylic acid.
 esters are named by use of two words.
 The alkyl or aryl group bonded to oxygen is named first, followed by the name of the
carboxylic acid in which the suffix ‘-ic acid’ is replaced by the suffix –ate
O
O O
OCH2CH2CH3 O
O
Ethyl Ethanoate Propyl benzoate Phenyl propanoate
(Ethyl acetate)

O O O

O O O
Propyl ethanoate Ethyl butanoate Methyl propanoate
(Pears) (Pineapple)
 Preparation of Esters
 The reaction between a carboxylic acid with an alcohol in presence of a mineral acid and
heating leads to formation of an ester

 Acid (Acyl) halides react with alcohols to form the esters. The formed HX is normally
removed by adding some amount of tertiary amine like pyridine

O N O
OH
Cl + O
Butanoyl chloride 1-Butanol Butyl butanoate
 Another method of preparing ester is the reaction of salts of carboxylic acid with alkyl
halides O
CH2Cl + CH3CO2-Na+ + NaCl
O
Benzyl chloride Sodium chloride Benzyl acetate

Reactions of Esters
(a)Hydrolysis:
 Both acidic and basic hydrolysis of esters has been discussed earlier in the preparation of
carboxylic acid.
 Alkaline hydrolysis is also termed as saponification because soap formation involves the
method. In soap formation the carboxylic acid moiety has a long chained alkyl group.
(b) Reaction with Ammonia, 10 and 20 amines:
• Esters react with ammonia, primary and secondary amines to form corresponding amides.
• In all cases alcohols are formed as the other product.
O
NH3
Propanamide
Ammonia NH2
O O
CH3CH2NH2
O Ethanamine (1o) N N-Ethylpropanamide
Ethyl propanoate H

(CH3CH2)2NH O
N,N-Diethylpropanamide
Diethylamine (2o) N

(c) Reduction of Esters:

Esters react with lithium aluminum hydride (LiAlH4) to form two alcohols: the one derived
from the acyl group is primary alcohol and is usually the objective of the reduction.
 Amides
Introduction and nomenclature
 Amides are compounds with trivalent nitrogen bonded to a carbonyl group
 They are named by dropping the suffix -oic acid from name of parent carboxylic acid and
adding –amide
 If there is no substitution on the nitrogen, the amides are termed as primary (1o) amides.

O
O O
C NH2
H3C C NH2 H2N C CH CH CH
2 2 3
Ethanamide Butanamide Benzamide

 If the nitrogen atom of an amide is bonded to an alkyl or an aryl group, the group is named
and its location on nitrogen is indicated by N- and is termed as secondary (2o) amides.
 Two alkyl or aryl groups are attached to nitrogen are indicated by N,N-di and are termed as
tertiary (3o) amides
O O
H3C C NHCH3 C NHCH3
N-methylethanamide
N-Ethylbenzamide
(2o amide)
(2o amide)

O O CH2CH3
H3C C N(CH3)2 H3CH2CH2C C N
CH3
N,N-Dimethylethanamide
(3o amide) N-Ethyl-N-methylbutanamide
(3o amide)

 Amides are prepared from other derivatives of carboxylic acid (esters, acid halides and
acid anhydride) reacted with ammonia or amines.
(a) Amides from acid (acyl) halides
Acid halides react readily with ammonia, primary amine and secondary amines to form
primary, secondary and tertiary amides, respectively.
O O
H3C C Cl + 2 NH3 H3C C NH2 + NH4+Cl-

Ethanoyl chloride Ethanamide Ammonium

chloride
O O
+ 2 CH3NH2
C Cl C NHCH + CH3NH3+Cl-
3

Benzoyl chloride Methylamine N-methylbenzamide Methylammonium

chloride
O O
H3C C Cl + 2 (CH3CH2)2NH H3C C N(CH2CH3)2 + -
+ (CH3CH2)2NH2 Cl
Ethanoyl chloride Diethylamine N,N-Diethylethanamide Diethylammonium
chloride

Note: Two moles of ammonia or the amine are used; one to form the amide and the other to
neutralize the hydrogen halide formed.
(b) Amides from acid anhydrides
 Acid anhydrides react with ammonia, primary amines and secondary amines to form
primary, secondary and tertiary amides, respectively.
 As with acid halides, two moles are required: one to form the amide and the other to
neutralize the carboxylic acid formed as by-product.
O O O O
H3C C O C CH3 + 2 NH3 H3C C NH2 + H3C C O-NH4+
Acetic anhydride Ethanamide Ammonium
acetate
(c) Amides from esters
O O
R C OR' + NH3 R C NH2 + R'OH
Ester Amide Alcohol
 Reaction of amides
(a)Reduction reaction
 Amides are reduced by lithium aluminium hydride (LiAlH4) to for primary, secondary or
tertiary amines depending on the degree of substitution of the amide
 Like other carboxylic acid derivatives, amides are not reduced by the sodium borohydride
(NaBH4).
O
1. LiAlH4
H2N C CH2CH2CH3 +
CH3CH2CH2CH2NH2
2. H2O/H
Butanamide 1-butanamine

O
1. LiAlH4
H3C C N(CH3)2 CH3CH2N(CH3)2
2. H2O/H+
N,N-Dimethyl- N,N-Dimethyl-
ethanamide ethanamine
Acid halides
Introduction and Nomenclature
 Derivatives of carboxylic acids in which the hydroxyl group of the carboxylic acid is
replaced by a halogen
 The term acyl is used to represent a carbonyl group bonded to a hydrogen atom, an alkyl
group or an aryl group.
 Acid halides are named by changing the suffix –ic acid in the name of the parent carboxylic
acid to –yl halide.

O O O O O H H O
R C X H C Cl H3C C Br C Cl Cl C C C C Cl
H H
an acyl halide Methanoyl Ethanoyl Benzoyl Butanedioyl
(an acid halide) chloride bromide chloride chloride
Preparation of acid halides
 Reaction of carboxylic acids and thionyl chloride (SOCl2) or phosphorus trichloride (PCl3)
lead to formation of acid chlorides.
CH3CO2H + SOCl2 CH3COCl + SO2 + HCl
Ethanoic Ethanoyl
acid chloride

Reactions of acid halides

(a) Reaction with water
 Acyl halide, as mentioned earlier, reacts readily with water to form corresponding
carboxylic acid.
CH3COCl + H2O CH3CO2H + HCl
Ethanoyl Ethanoic
chloride acid
(b) Reaction with alcohols
Acid halides react with alcohols to form esters.
O O
R C Cl + R'OH R C OR' + HCl
an acid an alcohol an ester
halide
OH O
CH3CH2COCl + O C CH2CH3 + HCl
Propanoyl cyclohexanol Cyclohexyl
chloride propanoate

(c)Reaction with ammonia and amines

Acid halides react readily with ammonia and primary or secondary amines to form amides
O O
R C Cl + R'2NH R C NR'2 + HCl (R' = H or alkyl or
an acid ammonia or an amide aryl groups)
chloride o
1 amine or
2o amine
Acid anhydrides
Nomenclature of acid anhydrides
 Carboxylic acid anhydrides are organic compounds with two acyl groups bonded to an
oxygen atom.
 They are called acid anhydrides because they are formally derived from two molecules of
carboxylic acids losing a molecule of water.
 Acid anhydrides are named by replacing the word acid in the parent carboxylic acid by
the word anhydride.
O O O O O O
H3C C O C CH3 C O C H3C C O C

Ethanoic anhydride Benzoic anhydride Ethanoic benzoic anhydride

Reaction with water: Hydrolysis
 They react with water to form two molecules of carboxylic acid.
 If the acid anhydride is symmetrical two identical carboxylic acids are formed.
 If it is a mixed acid anhydride, two different acids are formed.

O O
H3C C O C CH3 + H2O 2 CH3CO2H
Ethanoic anhydride Ethanoic acid

O O
H C O C CH3 + H2O HCO2H + CH3CO2H
Ethanoic methanoic methanoic Ethanoic
anhydride acid acid
Reaction with alcohols
 Acid anhydrides react with alcohols to form one mole of ester and one mole of carboxylic
acid.
 The reaction is not reversible and does not require mineral acid catalyst.
 It is therefore a useful method for synthesis of esters.

Nitriles
Introduction and nomenclature
Nitriles are compounds with a cyano (C≡N) group bonded to a carbon or to alkyl group
IUPAC naming of the nitriles is by adding the suffix –nitrile to the parent alkane.
Reactions of Nitriles
Reaction with water (Hydrolysis)
 The cyano group is hydrolyzed in aqueous acid form a carboxyl group and ammonium ion.
 In aqueous base, the cyano group is hydrolyzed to carboxylic acid anion and ammonia.
Reduction reactions
 The cyano group reacts with lithium aluminium hydride (LiAlH4) to form primary amino
group.
 1. LiAlH4
H3C C N CH3CH2NH2
2. H2O
Ethanenitrile Ethanamine
(Acetonitrile) (Ethylamine)

C N CH2NH2
Br Br
1. LiAlH4
2. H2O

Br Br
2,4-Dibromobenzonitrile (2,4-Dibromophenyl)methanamine