Preparation:-

1). from alkyl halides:-

Alkyl halides or benzyl halides on reaction with ethanolic solution of ammonia in a sealed tube
at 373 K undergo of C – X bond and the halo group (- X) is replaced by amino group ( - NH2).
This cleavage of C – X bond with ammonia is known as ammonolysis.
This reaction is a typical example of nucleophilic substitution reaction. Here, the ammonia
molecules in the first step and amine molecules in the subsequent steps act as nucleophiles.

Hence, the primary amine formed in the first step further reacts with alkyl halide to form
secondary amine, tertiary amine and finally quaternary ammonium salt.

The composition of the final mixture depends upon the molar ratio of alkyl halide and ammonia
at the beginning of the reaction. If alkyl halide is in excess the major product is quaternary
ammonium salt whereas if ethanolic ammonia is in excess the major product is primary amine.
The reactivity of various halides in this reaction is:

2).Gabriel Phthalimide synthesis:-

Potassium phthalimide is a -NH2-synthon which allows the preparation of primary amines by
reaction with alkyl halides. After alkylation, the phthalimid is not nucleophile and does not react
anymore. Product is cleaved by reaction with base or hydrazine, which leads to a stable cyclic
product.

Mechanism of the Gabriel Synthesis:-

Cleavage:-
3).Hoffmann's Bromamide reaction:-
Acid amides on reaction with bromine in the presence of alkalis at about 343 K give primary
amines.

The amine formed by this method has one carbon atom less than the parent compound.
This reaction involves migration of alkyl group from carbonyl in the precursor to nitrogen with
the elimination of CO2.
Mechanism :-

Mechanism can be also write in this way:-

Reactions of amines:-

1).Hoffmann and Zaitsev (Saytzeff) elimination:-

2). Carbylamine test:-

The carbyl amines reaction also known as Hoffman's isocyanide test is a chemical test for
detection of primary amines. In this reaction, the analyte is heated with alcoholic potassium
hydroxide and chloroform. If a primary amine is present, the isocyanide (carbylamine) is formed
which are foul smelling substances.
For example, the reaction with ethylamine:

The reaction with aniline:

The carbylamine test does not give a positive reaction with secondary and tertiary
amines.
3).The Hinsberg Test: Reaction with benzenesulfonyl chloride:-
Another electrophilic reagent, benzenesulfonyl chloride, reacts with amines in a fashion that
provides a useful test for distinguishing primary, secondary and tertiary amines (the Hinsberg
test). As shown in the following equations, 1º and 2º-amines react to give sulfonamide
derivatives with loss of HCl, whereas 3º-amines do not give any isolable products other than the
starting amine. In the latter case a quaternary "onium" salt may be formed as an intermediate, but
this rapidly breaks down in water to liberate the original 3º-amine (lower right equation).

The Hinsberg test is conducted in aqueous base (NaOH or KOH), and the benzenesulfonyl
chloride reagent is present as an insoluble oil. Because of the heterogeneous nature of this
system, the rate at which the sulfonyl chloride reagent is hydrolyzed to its sulfonate salt in the
absence of amines is relatively slow. The amine dissolves in the reagent phase, and immediately
reacts (if it is 1º or 2º), with the resulting HCl being neutralized by the base. The sulfonamide
derivative from 2º-amines is usually an insoluble solid. However, the sulfonamide derivative
from 1º-amines is acidic and dissolves in the aqueous base. Acidification of this solution then
precipitates the sulfonamide of the 1º-amine.
4).Reaction of Amines with Nitrous Acid:-

Primary Amines:-

Secondary Amines:-

The distinct behavior of 1º, 2º & 3º-aliphatic amines is an instructive challenge to our
understanding of their chemistry, but is of little importance as a synthetic tool. The SN1 product
mixtures from 1º-amines are difficult to control, and rearrangement is common when branched
primary alkyl groups are involved. The N-nitrosamines formed from 2º-amines are carcinogenic,
and are not generally useful as intermediates for subsequent reactions.
Aryl Amines:-

Aqueous solutions of these diazonium ions have sufficient stability at 0º to 10 ºC that they may
be used as intermediates in a variety of nucleophilic substitution reactions. For example, if water
is the only nucleophile available for reaction, phenols are formed in good yield.

2º-Aryl Amines:-
2º-Aryl amines give N-nitrosamine derivatives on reaction with nitrous acid, and thus behave
identically to their aliphatic counterparts.
3º-Aryl Amines:-
Depending on ring substitution, 3º-Aryl amines may undergo aromatic ring nitrosation at sites
ortho or para to the amine substituent. The nitrosonium cation is not sufficiently electrophilic to
react with benzene itself, or even toluene, but highly activated aromatic rings such as amines and
phenols are capable of substitution. Of course, the rate of reaction of NO(+) directly at nitrogen is
greater than that of ring substitution, as shown in the previous example. Once nitrosated, the
activating character of the amine nitrogen is greatly diminished; and N-nitrosoaniline derivatives,
or indeed any amide derivatives, do not undergo ring nitrosation.

5).Schotten-Baumann Reaction:-

The use of added base to drive the equilibrium in the formation of amides from amines and acid
chlorides.
The acylation of amines with carboxylic acid chlorides leads to the production of one equivalent
acid, which will form a salt with unreacted amine and diminish the yield. The addition of an
additional equivalent of base to neutralise this acid is a way to optimise the conditions.
Normally, aqueous base is slowly added to the reaction mixture.
Mechanism of the Schotten-Baumann Reaction:-
6).Electrophilic Substitution Reaction of Anilines:-