Amination by reduction involves synthesis of amines

by reductive method
Amines may be defined as derivative of ammonia,
where one or more of the hydrogen are replaced by
alkyl, aryl, cycloalkyl or heterocyclic groups
Amines can be produced by reducing nitro, nitroso,
hydroxylamine, azoxy, azo compounds, as well as
oximes, amides, nitriles, and azides.
In each case a carbon to nitrogen bond already exists.

 Examples:

Amines are divided into three classes primary,

secondary, and tertiary-depending upon the number or
replaced hydrogen in the parent substance ammonia.
Primary amines contain two remaining hydrogen atoms
attached to ammonia
Secondary amines contain one
Tertiary amines have none remaining

Primary amines:
Primary amines are those amine in which
one hydrogen of ammonia is replaced by organic
group (aromatic or alkyl group(CH3)).

Methyl amine

Aniline

 SECONDARY AMINE

Secondary amines are those amine in which two

hydrogen of ammonia are replaced by organic
substituents (alkyl ,aryl or aromatic).

Di-phenylamine

 TERTIARY AMINE:

In tertiary amines, all three hydrogen atoms are replaced by

organic substituents.
Examples include:

Trimethylamie
Triphenyl amine

Amines occur as gases (methylamine)

Amines occur as liquids (aniline)
Amines occur as solids (1-nephthylamine)
Amines are basic (alkaline to litmus)
In general amines form crystalline water soluble salts

Rubber chemicals
Nylon
Pharmaceuticals
Gasoline
Surfactants
Textile auxiliaries
Photographic chemicals
Sweetening agent
Agriculture chemicals
Polyurethane
Ink
plastics

A great variety of reduction methods have been used for the

preparation of amines
Metal and acid

Iron and acid is the major example in this category , but other metals (tin and zinc
can also be employed. Generally hydrochloric acid is preferred , but sulfuric acid ,
acetic and formic acid can also be used.

Catalytic

Involve the use of hydrogen ( or hydrogen containing gases) and a catalyst sch as
nickel , copper , platinum , palladium or molybdinum sulfide

Sulfide

Used only for partial reduction of polynitro aromatic compounds.

Electrolytic
Metal and alkali

used mainly for production of azoxy , azo and hydrozo compounds

 Sodium hydrosulfide
Sulfite( piria method)

The reaction of sodium sulfite and bisulfite on an aromatic nitro

compound leads to a mixture of amine and acid

Metal hydrides
Strong caustic oxidation reduction
Hydrogenated quinolines and naphthalene

Metal and acid reductions are most vigorous and usually

yield amine as end products.

Chemical and physical factors

Amount of iron used

Physical condition of iron
Amount of water used
Amount of acid used
Effect of agitation
Reaction temperature
Yield of amine.


1.
2.
3.
4.

Considering iron and acid reduction, which is

mostly used.
Amount of iron used:
Use 2 mole of Fe per mole of nitro compound
Use iron in finely divided form
Any impurities are source of contamination
Some excess quantity of iron used say 2.5 to 5
moles per mole of reactant

1.
2.

1.
2.
3.

Physical condition of iron

Clean, finally divided, soft gray, cast iron yield best results
The rate of reduction depend on fineness and porosity of iron
particles.

Amount of water used

Normally 4-5 moles of water per mole of nitro compound is used

Slightly excess is better
Unnecessary dilution not recommended. because it reduce catalyst
concentration.

Amount of acid used:

1.
2.
3.

The acid usually employed in the reduction process are hydrochloric

acid and sulfuric acid
hydrochloric acid causes formation of small amount of chlorinated
amines
sulfuric acid causes formation of darker amines and lower yield

Effect of agitation:
1.
2.

Since reduction process is multiphase reaction, best results is obtained

with intimate contact
With slow mixing iron settle down therefore a double impeller type
stirrer is needed

Reaction temperature:
1.
2.
3.

Study shows the reduction process is exothermic.

It is necessary to remove surplus heat while maintaining the reduction
at the optimum reaction temperature.
To control temperature reflux condenser are used

Yield:
1.

Upto 85-90%

A standard reduction equipment a cast iron vessel

Some reducers are lined with acid resisting bricks
The vessel has outlet at bottom to remove iron sludge and
charge
Reducer is equipped with feeding device for iron and acid
A powerful agitator for keeping iron in suspension
Jacket for steam heating. live steam is also used for heating in
lined vessels

Carried out in batches or in continous process, in vapor phase or liquid

phase.
Advantageous for large volume production
Wide range of reaction conditions
temperature from 20 to 300O
Pressure from atmospheric to several thousand pounds
Catalyst included nickel, copper , cobalt , chromium , iron , tin , silver ,platinum ,
palladium , rhodium and many others.


1.
2.

Aniline is manufactured by two main processes

Iron acid reduction
Catalytic reduction

The reaction is carried out at very slight pressure over a reduced copper
carbonate catalyst at temperature ranging from about 200 at the entrance to
the catalytic chaber to 350 at the exit.
The process starts by vaporizing a descending film of nitro benzene in the
tubes of an evaporator by an ascending stream of preheated hydrogen.
From 500-600 kg/hr of nitrobenzene is vaporized into a circulating gas
stream of 6000 m3/hr.
Hydrogen and nitrobemzene vapor are passed over a catalyst contained in
two chambers in series .with fresh catalyst the reaction temperature is 170
on entering the first chamber. Gases leaving the second chamber will have
a temperature of 350-370 .
Reaction s strongly exothermic and temperature control is accomplished
by a relatively cool hydrogen.

It is necessary to reactivate the catalyst after 1200 tons of nitrobenzene has

been passed.
After passing through a heat exchanger , the reaction products are
separated from the circulating gas stream by two water cooled tubular
condensers followd by a separate cooler.
Aniline and water are separated in a separator.