CHAPTER 8

Amines
OUTLINE
 Structure
 Classification
 Nomenclature
 Basicity
 Physical properties
Boiling point
 Reactions
 Uses
Introduction to Amines
 Amines are organic compounds and derivatives of ammonia
which have amino functional group.

 Like ammonia, amines contain a nitrogen atom with lone pair of

electron, making amines both weak bases and good
nucleophiles.
Classification of Amines
 There are 3 classes of amines which are primary (1°), secondary
(2°), and tertiary (3°). Their general structures are shown below:

R or R’ or R’’
represents carbon
chain

 Amine can also exist as quaternary (4°) ammonium ion in which

nitrogen atom is bonded to 4 alkyl or aryl groups and has a
positive charge
Naming of Amines
Primary aliphatic amines:

methanamine 2-aminoethanol

2-propanamine
1,4-butanediamine

3-amino-2-pentanone

cyclohexanamine
3-methyl-2-butanamine
Primary aromatic amines:

3-methylaniline
p-aminobenzoic acid

3-bromo-2-chloro-4-nitroaniline 1,4-benzenediamine
Secondary and Tertiary amines:

 Treat additional branches as a branch on the nitrogen

 Base name is based on longest chain that contains the amine

 Name other chain as alkyl substituent on the nitrogen

 Use N- at front of a branch name indicates that substituent is on

the nitrogen
Secondary amines (aliphatic and aromatic):

N-methylphenylamine @ N-methyl-1-propanamine
N-methylaniline

N-2-dimethyl-1-butanamine

4-methyl-N-propylaniline N-methyl-2-pentanamine
 Tertiary amines (aliphatic and aromatic):

N,N-dimethyl-2-pentamine
N,N-dimethylaniline

N-4-diethyl-N-methylaniline

N-ethyl-N-methyl-1-butanamine

N-ethyl-N-methylcyclohexanamine
Question
1. Draw structure for the following amines:
a) 1,3-propanediamine
b) m-aminobenzoic acid
c) 3-aminobutanal
d) N,N-dimethyl-1-pentanamine
e) 2-chloro-N-ethylaniline
f) Trimethylamine
2. Name the following amines using IUPAC nomenclature. For each
amine, state the class and whether they are aromatic or aliphatic:

1-butanamine

O-aminobenzoic acid N-ethylcyclopentaneamine

2-phenylpropanamine
N-methyl-2-propanamine
N-ethyl-N-propylaniline

N-methyl-N-propyl-2-hexanamine N,N-dimethyl-1-phenylmethanamine
Basicity of Amines
 Amines act as a base because of the presence of lone electron
pair on the nitrogen atom which can be donated to protons, H+
 Formula Name Kb/M
NH3 Ammonia 1.8 X 10-5
CH3NH2 Methanamine 4.4 X 10-4
(CH3)2NH N-methylmethanamine 5.9 X 10-4

 From NH3 to CH3NH2 to (CH3)2NH, the number of electron

donating groups increases, the lone electron pair on the
nitrogen atom is more available to be donated to acids H+

 So, basicity increases

 Formula Name Kb/M

CH3CH2NH2 Ethanamine 6.46 x 10-4

Phenylamine or aniline 4.27 X 10-10

• Phenylamine (aromatic amine) is less basic than ethanamine

(aliphatic amine)

• In phenylamine, the lone electron pair on the nitrogen atom is

delocalised into the benzene ring, thus it is less available to be
donated to acids, H+ ions
 Below is the resonance structures of phenylamine (aniline) in
which the lose electron pair on the nitrogen atom is delocalised
into the benzene ring.
Physical Properties of Amines
 Amines have fishy smell

 Amines are polar molecules

 Amines that have fewer than five carbons including (1°,2°,3°) are
soluble in water because they form hydrogen bond with water
Boiling point
 Amines have higher b.p. than alkanes , alkenes, haloalkanes, and
carbonyl compounds of similar relative molecular mass

 This is because amines can form stronger hydrogen bond

between molecules.

 Amines have lower b.p. than alcohols of similar relatives

molecular mass

 This is because of weaker hydrogen bond between molecules

due to nitrogen atom being less electronegative than oxygen
atom
 For isomeric amines, the order of b.p.is:
1°amine>2° amine> 3° amine

 This is due to the progressive decrease in intermolecular

hydrogen bonding.
Questions
1. Arrange the amines below according to increasing boiling
point. Explain.
• 1-propanamine
• N,N-dimethylmethanamine
• N-methylethanamine

2. Which is the stronger base, aniline or methylaniline? Explain.

Reactions of Amines and Phenylamines
1. Neutralisation (salt formation)
2. Reaction with nitrous acid
 Primary aliphatic amine
 Secondary amine
 Tertiary amine
3. Reactions of benzediazonium chloride (salts)
4. Amide formation (Acylation)
5. Reaction with acid anhydride
6. Reaction with esters
1. Neutralisation (salt formation)
 Amines react with acids to form salt by donating its lone pair on
the nitrogen atom and accepts a proton, H+ ion.
2. Reaction with nitrous acid
 Nitrous acid is generated from a reaction of sodium nitrite or
sodium nitrate (III), NaNO2 with hydrochloric acid, HCl or
sulphuric acid at 0-5 °C.

 This reaction can be used to differentiate primary aliphatic

amine, secondary amine, tertiary amine and primary aromatic
amine.
1) Primary aliphatic amine:

 With primary amines; N2, alcohol, alkene and haloalkene

is produces. Nitrogen gas is seen as effervescence or gas
bubble.
2) Secondary amine:
 Nitrous acid reacts with secondary amines (aliphatic and
aromatic) to form nitrosoamines which appear as
yellow oil.
3) Tertiary amine:
 Aliphatic tertiary amines react with nitrous acids at 0-5°C to
form mixture of salts which is soluble in water.

 Aromatic tertiary amines react with nitrous acid to

form a solid with nitroso group (-NO) is normally attached
to the para position of the benzene ring.
3. (Reactions of benzediazonium chloride
salts)

 Primary aromatic amines for example phenylamine reacts with

nitrous acid to form a stable benzenediazonium salt (less than
5°C).
4. Amide formation (Acylation)
 1° and 2° amines react with acyl chloride to form 2° amide and
3° amide

 3° amines do not react with acyl chloride because it does not

have hydrogen atom directly bonded to nitrogen atom
 Example:
5. Reaction with acid anhydride
 Primary amines react with acid anhydrides to form 2 ◦ amide
whereas secondary amines react to form 3◦ amide
6. Reaction with esters
Test for amines
1. Simple amines that dissolve in water, form solutions that smell
like ammonia and change litmus paper from red to blue

2. Phenylamine decolourise bromine water and form white

precipitate of 2,4,6-tribromophenylamine

3. Aliphatic amines do not show any reaction with bromine water

Question
1. Using a suitable chemical test, differentiate the following pairs:

a) Aniline and ethanamine

b) N,N-diethylaniline and aniline

c) Butanamine and N,N-dimethylethanamine

d) 2-methylbutanamine and 4-ethylaniline

Uses of Amine
 Amines are used in the synthesis of dyes and nylon

 Medical uses:

Depress central Stimulate central

nervous system nervous system
 Benzenediazonium salts are very useful in organic synthesis. The
diazonium group can substituted by a variety of nucleophiles