Department of Chemical University of Engineering and Technology,

Engineering Lahore

Assignment on
Amination

Submitted to:
Sir Abdul Ghaffar

Submitted by:
2020-CH-18
Muhammad Rafe Amin

Section:
B
Muhammad Rafe Amin 2020-CH-18

Table of Contents
Definition ...................................................................................................................................................... 2
Example (Laboratory Scale) ................................................................................................................... 2
First Step ................................................................................................................................................ 2
Second Step ............................................................................................................................................ 2
Scope in Chemical Industry ........................................................................................................................ 3
Pharmaceutical Industry ....................................................................................................................... 3
Dyes Industry ......................................................................................................................................... 3
Most Common Amine ............................................................................................................................. 3
Production at Industrial Scale .................................................................................................................... 3
Example 1 ................................................................................................................................................. 3
Scope ...................................................................................................................................................... 3
Reactants Reaction Conditions .............................................................................................................. 4
Flow Sheet ............................................................................................................................................. 4
Explanation of Preparation ................................................................................................................... 4
Example 2 ................................................................................................................................................. 5
Hydrazine ............................................................................................................................................... 5
Scope of Hydrazine ................................................................................................................................ 5
Reactants and Reaction Conditions for Preparation of Hydrazine ....................................................... 5
Flow Sheet Diagram for Hydrazine Preparation .................................................................................. 6
Explanation of Preparation of Hydrazine ............................................................................................. 8
Applications in Pakistani Market............................................................................................................... 8

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Amination
Definition

It is defined as the process of introduction of an amino group ( ) into an organic molecule.

This reaction has significant importance due to the pervasive nature of the organo-nitrogen
compounds. If this reaction takes place in the presence of reducing agents which are usually or
a metal catalyst for the purpose of increase in the rate of reaction, then it is known as reductive
amination.

Example (Laboratory Scale)

The laboratory scale amination method which is commonly used is for the preparation of amino
acids. This reaction takes place in two different steps and α-ketonic acid is used as a starting
material.

First Step

In the first step, α-ketonic acid is reacted with ammonia to give intermediate product which is
imine. This step takes place in the presence of which acts as a catalyst.

Second Step
In this step, imine is reduced with in the presence of palladium catalyst to give amino acid.

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Scope in Chemical Industry

The most common method of amination which is being used at the industrial scale is for the
production of amines which is best known as reductive amination.
Pharmaceutical Industry
Reductive amination holds very key importance in the medical and pharmaceutical chemical
industries due to the advantages of its synthetic merits and the presence of amines in addition to
active biological compounds which are necessary for the preparation of a large number of
medicines including pain killers such as Morphine and Demerol.
Dyes Industry
Reductive amination process is used in the preparation of amines which acts as an intermediate
product for the preparation of dyes in the industry. The most common amines which are used as
an intermediate product are the aromatic amines which lead to the formation of azo dyes such as
methyl orange, sunset yellow and ponceau colours.
Most Common Amine
The most common type of amine which is used globally at a very large scale is ethanol amine. It
is also prepared by using the reaction of reductive amination in the presence of Ni or Al 2O3 as a
catalyst.

Production at Industrial Scale

Example 1

The most common compound which is mostly seen to be synthesized at industrial scale is of
isopropyl amine. Its structural formula is given as:

Scope

Isopropyl amine covers a wide range of applications. The main uses of this compound includes:
➢ For the purification of penicillin and streptomycin.
➢ Used as a dehairing agent.
➢ Used as an intermediate product for the production of insecticides, pharmaceuticals,
bactericides, dyes, herbicides and rubber accelerators.
➢ It is also used in the paints and in the varnishes industry.
➢ Its use in the production of the surface active agents is also very significant.

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Reactants Reaction Conditions

For the preparation of isopropyl amine, isopropanol is used as a starting material. It reacts with
ammonia in the presence of catalyst which may be copper, cobalt or nickel.
The reaction and reaction conditions are:

Flow Sheet

isopropanol ammonia

Pressurized Amination
Chamber
Steam inlet

Water outlet
H2O

Container for Storage of

Isopropanol

Explanation of Preparation

The preferred starting material for the preparation of isopropyl amine is the isopropanol. The
reaction takes place in the presence of Hydrogen and in the presence or absence of water
molecules. The catalysts used are a mixture of phosphoric acid or boric acid in addition to the
presence of cobalt, nickel and copper. The ideal temperature required for this reaction to complete
is 100-2500C while the pressure is also set at super-atmospheric pressure level which is ideally 20-
200atm for the effective completeness of this reaction.

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In the past, various methods were used for the preparation of isopropyl amine without the use of
catalysts and without defining the temperature limits. But, these methods have many flaws which
includes a large amount of piperazine was obtained in spite of giving very high temperature, a high
proportion of N-substituted amines were formed along with the formation of large amount of
piperazine and sometimes the reactions were incomplete and sometimes after-amination was also
required by using copper as a catalyst.

Example 2

Hydrazine
The most common compound which is produced at industrial scale as a result of amination is the
hydrazine. It is a colourless liquid whose odour is similar to that of ammonia. It is not able to
synthesize hydrazine in a single step, so a number of steps are followed till we reach the end
product.

Scope of Hydrazine

Hydrazine has a wide range of applications in various fields of life. Some of the important locations
where scope of hydrazine is found are:
➢ Used for the deoxygenation of boiled water.
➢ For the preparation of the chemical blowing agents.
➢ Also used as an intermediate product for the preparation of pharmaceutical and agricultural
chemicals.
➢ It is also used as a reducing agent for the formulations of metals and halogens.
➢ It is also used for the preparation of textile dyes.
➢ The most fundamental and advanced use of hydrazine is its use as the fuel of spacecraft and
the jet engines.

Reactants and Reaction Conditions for Preparation of Hydrazine

The starting material used for the preparation of hydrazine is acetone which reacts with ammonia
in the first step to form imine. For the preparation of hydrazine, amination step is done twice out
of series of steps.
The step-wise reactions followed for the preparation of hydrazine are:

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Flow Sheet Diagram for Hydrazine Preparation

Aqueous Ammonia First Amination Chamber

Acetone

H2O

Imine

H2O2 (Catalyst) Dehydration Chamber

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H2O

dimethyloxaziridine

Aqueous Ammonia Second Amination Chamber

H2O

Azine

Reaction with Acetone

H2O

Hydrazone

2H2O Hydrolysis of Hydrazone

Hydrazine Acetone

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Explanation of Preparation of Hydrazine

For the preparation of hydrazine, aqueous ammonia is treated with acetone in the first step resulting
in the formation of imine which is an intermediate product and elimination of a water molecule.
In the next step, imine is fed into a dehydration chamber in the presence of hydrogen peroxide
resulting in dimethyloxaziridine. Then, dimethyloxaziridine is again treated with aqueous
ammonia resulting in elimination of a molecule of water and production of azine.
Then, this azine is treated with acetone to form hydrazone which is last intermediate product for
the formation of hydrazine. In the final step, hydrolysis of hydrazone is done which results in the
formation of final product which is hydrazine and the recovery of acetone which is again used in
the reaction.

Applications in Pakistani Market

The reaction of amination finds its applications in various industries of Pakistan out of which some
of the following are:
Pharmaceutical Industries
There are currently 800 pharmaceutical units in Pakistan including 25 registered as multi-national
companies. The reaction of amination is carried out at a bulk scale in the pharmaceutical industries.
Some of the medicines which are produced by using amination are Citalopram, Eletriptan,
Oxyphenonium and Isoetharine. The Pakistani pharmaceutical market is fulfilling 70% needs of
the finished medicine in the country. The names of the a few important pharmaceutical
manufacturing companies in Pakistan include: Remington Pharmaceuticals (Lahore), Mkb
Pharmaceuticals (Peshawar) and Vega Pharmaceuticals (Lahore).
Dyes Manufacturing Industries
The leading dyes manufacturing company in Pakistan is Archroma, which is also known for the in
the field of textile, paper and construction industries. A dye which is being prepared on a large
scale is a fluorescent dye namely Lucifer Yellow which contains the amino group as a functional
group.