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WHAT ARE AMINES ?

Amines can be considered derivatives of ammonia , obtained by

replacement of one , two or all three hydrogen atoms by alkyl and/or
aryl groups

Examples of this are:  CH₃NH₂ and C₆H₅NH₂

Further, like ammonia, nitrogen atom of amines is trivalent and carries

an unshared pair of electrons. Nitrogen atoms in amines are therefore
sp3 hybridised and geometry of amines is pyramidal . Each of the three
sp3 hybridised orbital of nitrogen overlap with orbitals of hydrogen or
carbon depending upon the composition of amine. The fourth orbital of
nitrogen in all amines contains an unshared pair of electrons. Due to
the presence of unshared pair of electron the angle C-N-E ,where e is
carbon or hydrogen, is less than 109.5 degrees

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 CLASSIFICATION OF AMINES

Further, amines can be classified on the basis of the number of

hydrogen atoms replaced by alkyl or aryl group in ammonia molecule
as:

i. Primary amine

If one hydrogen atom is replaced by R(alkyl) or Ar(aryl), we get a

primary amine

ii. Secondary amine

If two hydrogen atom is replaced by R or Ar ,we get a secondary amine

iii. Tertiary amine

If three hydrogen atom is replaced by R or Ar ,we get a tertiary amine

For example:

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 NOMENCLATURE OF AMINES

Common System: In this system an alphabetic amine is named by

prefixing alkyl group to amine ,that is alkylamine as one word. In
secondary and tertiary amines , when two or more groups are the same
,the prefix di or tri is attached before the name of alkyl group

For Example:  Ethylamine( C2H5NH2)

o-Toluidine

IUPAC System: In this system amines are named as alkanamines ,

derived by the replacement of ‘e’ of alkane by the word amine. In case,
more than one amino group is present at different position in the
parent chain, their positions are specified by giving number to the
carbon atoms bearing –NH 2 groups and suitable prefix such as di, tri,
etc.

For Example: Ethanamine( C2H5NH2)

2-Aminotoluene

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 Physical properties of amines

Primary amines with three or more carbon atoms are liquid and still
higher ones are solid. Aniline and other arylamines are usually clourless
but get coloured on storage due to atmospheric oxidation.

Solubility:

Lower aliphatic amines are soluble in water because they can form
hydrogen bonds with water molecules. However , solubility decreases
with increase in molar mass of amines due to increase in size of
hydrophobic alkyl part.

Amines are soluble in organic solvents like alcohol, ether and benzene

Boiling Point:

Primary and secondary amines are often engaged in the intermolecular

association as a result of hydrogen bonding between nitrogen of one
and hydrogen of the other molecule. The intermolecular association is
more prominent in case of primary amines as compared to secondary
due to the availability of two hydrogen atoms. In tertiary amines, there
is no intermolecular association due to the absence of free hydrogen
atom for bonding. The order of boiling point of amines is as follows:
Primary > Secondary > Tertiary.

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 PREPARATION OF AMINES

Amines can be prepared by various processes. Here are few of those

processes:

Reduction of Nitro Compounds:

Nitro compounds are reduced to amines by passing hydrogen gas in the

presence of finely divided nickel, palladium or platinum and also by
reduction with metals in acidic medium. Nitroalkanes can also be
similarly reduced to the corresponding alkanamines

Reduction of nitrites:

Nitrites on reduction with lithium aluminium hydride or catalytic

hydrogenation produce primary amine.

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Gabriel phthalimide synthesis:

It is used for the preparation of primary amine. Phthalimide on

treatment with ethanolic potassium hydrxide forms potassium salt of
phthalimide which on heating with alkyl halide followed by alkaine
hydrolysis produces corresponding primary amine

Aromatic primary amines cannot be prepared by this method because

aryl halides do not undergo nucleophilic substitution with the anion
formed by phthalimide

Hoffmann bromamide degradation reaction:

Hoffmann developed a method for preparation of primary amines by

treating an amide with bromine in an aqueous or ehanoic solution of
sodium hydroxide. In this degradation reaction, migration of an alkyl or
aryl group takes place from carbonyl carbon of the amide to the
nitrogen atom. The amine so formed contains one carbon less than that
present in the amide.

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 Chemical properties and reactions of amines

Basic character of amines:

Amines, being basic in nature , react with acids to form salts.

Amines salts are soluble in water but insoluble in organic solvents like
ether

Acylation:

Aliphatic and aromatic primary and secondary amines react with acidic
chlorides, anhydrides and esters by nucleophilic substitution reaction.
This reaction is known as acylation.

Carbylamine reaction:
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Aliphatic and aromatic primary amines on heating with chloroform and
ethanoic potassium hydroxide from isocyanides or carbylamines which
are foul smelling substances . This reaction is known as a test for
primary amine.

Electrophilic substitution reactions:

1.Bromination

Aniline reacts with bromine water at room temperature to give a white

precipitate of 2,4,6-tribromoaniline

2.Sulphonification

Aniline reacts with Conc. Sulphuric acid to form anilinium

hydrogensulphate which on heating with sulphuric acid at 453-473K
produces p-aminobenzene sulphonic acid, commonly known as
sulphanilic acid, as the major product

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3.Nitration

Direct nitration of aniline yields tarry oxidation products in addition to

the nitro derivatives. Moreover, in the strongly acidic medium, aniline is
protonated to form the anilinium ion which is meta directing .

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 DIAZONIUM SALTS

Diazonium compounds or diazonium salts are a group of organic

compounds sharing a common functional group R−N+2X− where R can
be any organic group, such as an alkyl or an aryl, and X is an inorganic
or organic anion, such as a halogen.

PROPERTIES:

According to X-ray crystallography the C–N≡N linkage is linear in typical

diazonium salts. The N-N bond distance in benzenediazonium
tetrafluoroborate is 1.083(3) Å, which is almost identical to that for
dinitrogen molecule (N2).
The linear free energy constants σm and σp indicate that the diazonium
group is strongly electron-withdrawing. Thus, the diazonio-substituted
phenols and benzoic acids have greatly reduced pKa values compared to
their unsubstituted counterparts. The phenolic proton of 4-
hydroxybenzenediazonium is 3.4, vs 9.9 for phenol itself. In other
words, the diazonium group lowers the pKa (enhances the acidity) by a
million-fold.
The stability of arenediazonium salts is highly sensitive to the
counterion. Phenyldiazonium chloride is dangerously explosive,
but phenyldiazonium tetrafluoroborate is easily handled on the bench.
SN1 and SN2 reactions do not occur.

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IMPORTANT REACTIONS:

Sandmeyer reaction
Benzenediazonium chloride heated with cuprous chloride or cuprous
bromide respectively dissolved in HCl or HBr
yield chlorobenzene or bromobenzene, respectively.

C6H5N+2 + CuCl → C6H5Cl + N2 + Cu+

Gattermann reaction
In the Gattermann reaction, benzenediazonium chloride is warmed
with copper powder and HCl or HBr to produce chlorobenzene and
bromobenzene respectively. It is named after the German
chemist Ludwig Gattermann.

2 Cu + 2 C6H5N+2 → 2 Cu+ + (C6H5)2 + 2 N2 (initiation)

C6H5N+2 + HX → C6H5X + N2 + H+ (Cu+ catalysis)

Replacement by iodide
Arenediazonium cations react with potassium iodide to give the aryl
iodide:

C6H5N+2 + KI → C6H5I + K+ + N2

Replacement by fluoride
Fluorobenzene is produced by thermal decomposition
of benzenediazonium fluoroborate. The conversion is called the Balz-
Schiemann reaction.
[C6H5N+2]BF−4 → C6H5F + BF3 + N2
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The traditional Balz–Schiemann reaction has been the subject of many
motivations, e.g. using hexafluorophosphates (PF−6) and
hexafluoroantimonate (SbF−6) in place of tetrafluoroborates. The
diazotization can be effected with nitrosonium salts such as [NO]SbF6

Replacement by hydrogen
Arenediazonium cations reduced by hypophosphorous acid,
 ethanol, sodium stannite or alkaline sodium thiosulphate gives
benzene:

[C6H5N+2]Cl− + H3PO2 + H2O → C6H6 + N2 + H3PO3 + HCl

[C6H5N+2]Cl− + CH3CH2OH → C6H6 + N2 + CH3CHO + HCl
Replacement by a hydroxyl group
Phenols are produced by heating aqueous solutions of arenediazonium
salts:

C6H5N+2 + H2O → C6H5OH + N2 + H+

This reaction goes by the German name Phenolverkochung ("cooking

down to yield phenols"). The phenol formed may react with the
diazonium salt and hence the reaction is carried in the presence of an
acid which suppresses this further reaction. A Sandmeyer-type
hydroxylation is also possible using Cu2O and Cu2+ in water.
Replacement by a nitro group
Nitrobenzene can be obtained by treating benzenediazonium
fluoroborate with sodium nitrite in presence of copper. Alternatively,
the diazotisation of the aniline can be conducted in presence of
cuprous oxide, which generates cuprous nitrite in situ:
C6H5N+2 + CuNO2 → C6H5NO2 + N2 + Cu+
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 APPLICATION AND USES OF AMINES

Amines are largely used in pharmaceutical industry. Morphine and

Demerol are used as analgesics that are pain killers.
Amines are used in making azo-dyes and nylon apart from medicines
and drugs. They are widely used in developing chemicals for crop
protection, medication and water purification.

They also find use in products of personal care.Ethanol amines are the
most common type of amine used in the global market.

The reaction between amines and carboxylic acids to form amides is

biologically important. It is through this reaction that amino acids link
together in a polymer to form proteins.

Amines participate in important metabolic and physiological functions

in living organisms. Polyamines are essential for cell proliferation,
growth, renewal, and metabolism. They are involved in nearly every
step of DNA, RNA, and protein synthesis, and regulate the permeability
and stability of cellular membranes.

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 CONCLUSION

At the end of the day amines are chemical compounds or substances

which help us in our day to day life directly or maybe indirectly. We use
it to make drugs and medicines, they are inside our bodies participating
in various chemical reactions to keep us healthy and alive. These
substances help us achieve remarkable feats and we should respect
that we have the knowledge to make these things happen.

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 BIBLIOGRAPHY

i. Chemistry book, NCERT

ii. The internet

AMINES

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