Amines

Structure, Classification and Nomenclature

Alkyl or aryl derivatives of ammonia are known as amines.

The nitrogen atom in amines is sp3 hybridised.

Due to the presence of an unshared pair of electrons, the C-N-H or C-N-C bond angle is
less than the normal tetrahedral bond angle of 109.5°.

The replacement of one atom, two and three hydrogen atoms of ammonia, with one, two
and three alkyl or aryl groups, yields primary, secondary and tertiary amines,
respectively.

Amines are called simple amines when all the alkyl or aryl groups are the same, and
mixed amines when they are different.

In the common system, an aliphatic amine is named by prefixing the alkyl group to the
amine.

In the IUPAC system, alkylamines are named alkanamines.

While naming arylamines according to the IUPAC system, the suffix ‘e’ of the arene is
replaced y ‘amine’.

Preparation

The reduction of nitro compounds can be carried out either by catalytic

reduction using H2/Ni/Pd/Pt, ...... or by using active metals such as
Fe/Sn/Zn/Conc.HCl.
Amines can also be prepared by the ammonolysis of alkyl or benzyl halides.
The process of cleavage of a carbon halogen bond by ammonia is called
ammonolysis.
The reduction of nitriles with lithium aluminium hydride or with hydrogen in
the presence of catalysts such as platinum, nickel or palladium yields
primary amines.
The reaction for the reduction of nitriles has synthetic importance as it is
used to step up the carbon chain.
The reduction of isonitriles or carbylamines yields secondary amines.
The Hoffman bromamide degradation reaction is used to step down the
carbon chain.

Chemical Reactions: Basic Character

Amines are basic in nature due to the presence of a lone pair of electrons on
nitrogen.
The relative basic strength of amines can be known from their Kb, the
stronger is the base.
The larger the value of Kb or smaller the value of p Kb, the stronger is the
base.
Aliphatic amines are stronger bases than ammonia, but aromatic amines are
weaker bases than ammonia.
The Kb or pKb values of amines are affected by: the inductive effect of the
groups present in amines, the ease of salvation of protonated amine and
steric hindrance.
In case of substituted aryl amines, electron-donating groups increase the
basic strength, whereas electron-withdrawing groups decrease it.

Diazonium Salts

Aryl diazonium salts are produced by reacting aniline with nitrous acid,
generated in situ, at 273-278 K. They must be prepared freshly before use.
In the Sandmeyer reactions, diazonium groups are replaced by chloride,
bromide or cyanide in the presence of copper (I) ions.
In the Gatterman reactions, diazonium groups are replaced with chlorine or
bromine by treating the diazonium salt solution with haloacid in the presence
of copper powder.
Diazinium group may be replaced by iodine by treatment with potassium
iodide. The Schiemann reaction is a method for the production of aryl
fluorides.
In reductive deamination, the diazonium group is replaced by hydrogen after
treatment with mild reducing agents such as hypophosphorous acid or
ethanol.
In nitration reaction, the diazonium group is replaced by an –NO2 group.
Phenols can be prepared from diazonium salts by hydrolysing with dilute
sulphuric acid and heating.
Azo coupling reactions occur when diazonium salts react with phenol or
aniline.