Unit 13

AMINES

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1
Amines
Amines are essentially molecules of ammonia
One or more of the hydrogen atoms have been
replaced with an alkyl group.

H
N
H H
2
 Classification
Replacement of one hydrogen atom with an
alkyl group gives primary amine
Replacement of two hydrogen atoms with
alkyl groups gives secondary amine etc.
R R
R NH2 R
NH N R''
Primary amine R' R' R
Secondary amine
Tertiary amine Quater

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 Nomenclature
In IUPAC system, amines are named as
alkanamines, derived by replacement of ‘e’ of
alkane by the word amine.
CH3NH2 is methanamine.

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CH3.CH.(NH2)CH3 Propan-2-amine
CH3.NH.CH2.CH3 N-Methylethanamine
N(CH3)3 N,N-Dimethylmethanamine
N(CH3)2 (C2H5) N,N-Dimethylethanamine
 Aniline

 4-Bromoaniline

 2 Phenylethaneamine

(C2H5) 2N.CH2.CH2.CH2.CH3 N,N-Diethylbutan-1-amine

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Preparation of Amines
Reduction of nitro compounds
Nitro compounds are reduced to amines by passing
hydrogen gas in the presence of finely divided Ni, Pd
or Pt and also by reduction with metals in acidic
medium.

NO2 NH2
Sn / conc. HCl

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Ammonolysis of alkyl halides
-HX -
OH
+ - RNH2
RX + NH3 RNH3 X
The process of cleavage of C – X by ammonia
molecule is called ammonolysis.
The primary amine thus obtained behaves as a
nucleophile and can further react with alkyl halide to
form secondary and tertiary amines, and finally
quaternary ammonium salt.
RNH2--RX→R2NH --RX→R3N-- RX→R4N+X-

It gives mixture of primary, sec, tert amines. However

primary amine can be major product if ammonia is 7
 Reduction of nitriles
Nitriles on reduction with lithium aluminium hydride
(LiAlH4) or catalytic hydrogenation(H2/Ni) produce
primary amines. LiAlH
4
RCN RCH2NH2
dry ether

Reduction of amides
The amides on reduction with lithium
aluminium hydride yield amines.
O
LiAlH4
R C NH2 RCH2NH2
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Hoffmann bromamide degradation reaction
Primary amines are prepared by treating an amide with
bromine in an aqueous or ethanolic solution of
sodium/potassium hydroxide. The amine so formed contains
one carbon less than that present in the amide.

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Gabriel phthalimide synthesis

Aromatic primary amines

can not be repaired by this
process because ayl halide
do not undergo
nucleophilic substitution
with the anion formed by
phthalimide.

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 Physical Properties
 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.
 Boiling points of amines are lower than alcohols because weaker hydrogen bonding due to less
electonegativity of N as compared to O of alcohol.

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12
Chemical Reactions
Basic character of amines
Amines, being basic in nature, react with acids
to form salts.
R.NH2+HX→R.NH3+X-
NH2 + HCl NH3+Cl-

anilinium chloride

(CH3CH2)2NH + CH3COOH (CH3CH2)2NH2+, -OOCCH3

diethylammonium acetate

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Basic strength- aliphatic & aromatic
Aliphatic amines are stronger than ammonia
due to +I effect.

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Basicity of Pri,Sec, Tert Amines
1. Due to +I effect:
tertiary > secondary > primary.
2. Due to solvation:
primary > secondary > tertiary.
3. Steric factor:
primary > secondary > tertiary.

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The actual order
(C2H5)2NH> (C2H5)3N> (C2H5)NH2>NH3
20 > 30 > 10
(CH3)2NH > (CH3)NH2 > (CH3)3N > NH3
20 > 10 > 30
CH3 has less steric hinders

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*

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 Acylation
Aliphatic and aromatic primary and secondary
amines react with acid chlorides, anhydrides and
esters by nucleophilic substitution reaction
forming substituted amides. It is the
replacement of hydrogen atom of –NH 2 or >N–
H group by the acyl group.It is carried on in
strong basic medium to remove the acid formed
and shift reaction in forward direction.

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1

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Benzoylation
Amines react with benzoyl chloride .This is called
Benzoyation O O
H
RNH2 + C Cl C N R
O O
H
NH2 + C Cl C N

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Carbylamine reaction
Aliphatic and aromatic primary amines on
heating with chloroform and ethanolic
potassium hydroxide form isocyanides or
carbylamines which are foul smelling.
Secondary and tertiary amines do not show this
reaction.
R.NH2+CHCl3+3KOH→R.NC+3KCl+3H2O

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 Reaction with nitrous acid
Amines react with nitrous acid to form diazonium
salts.
Aliphatic diazonium salt being unstable forms
alcohol and liberate N2

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Alcohol / Water /
HBF4

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Electrophilic substitution
The -NH2 group is powerful activating group
and is ortho para directing.
Bromination
Aniline reacts with bromine water at room
temperature to give a white precipitate of 2,4,6-
tribromoaniline.
NH2 NH2
Br Br
+ Br2, aq. polyhalogenation!
Br
no catalyst needed
use polar solvent

Br Br Br
Br2,Fe HNO3 H2/Ni

H2SO4
NO2 NH2
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+ ortho-
If we have to prepare monosubstituted aniline
derivative, we have to protect the -NH2 group
by acetylation with acetic anhydride, then
carrying out the desired substitution followed
by hydrolysis of the substituted amide to the
substituted amine.

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Protection of –NH2 group by Acetylation

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 Nitration
Direct nitration of aniline yields three oxidation
products. In the strongly acidic medium, aniline is
protonated to form the anilinium ion which is meta
directing. That is why besides the ortho (2%) and para
(51%) derivatives, significant amount of meta (47%)
derivative is also formed.
However, by protecting the –NH2 group by acetylation
reaction with acetic anhydride, the nitration reaction
can be controlled and the p-nitro derivative can be
obtained as the major product.
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31
 Sulphonation
Aniline reacts with concentrated 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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NH2 NH3
NH2 NH3
+ H2SO4
+ H2SO4

SO3
SO3

cold H2SO4 cold H2SO4

453-473K
NH3 HSO4
NH3 HSO4

NH2
NH2 NH3
HNO3
TAR!
H2SO4 + H2SO4

(CH3CO)2O SO3

NH2
cold H2SO4 Zwitter ion
NHCOCH3 NHCOCH3
HNO3 H2O,OH-
SO 3H
H2SO4
NH3 HSO4

sulphanilic
NO NO
acid 2 2

+ ortho-
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Hinsberg Test
Benzene Sulphonyl Chloride

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