Chapter: Amines

Top concepts

1. Amines are regarded as derivatives of ammonia in which one, two or all

three hydrogen atoms are replaced by alkyl or aryl group

2. Classification of amines:

3. Preparation of amines:
(i)By reduction of nitro compounds:
Nitro compounds can be catalytically reduced by passing hydrogen gas in
presence of Raney Ni, finely divided Pt or Pd as catalyst at room
temperature.
Ni, Pt or Pd
R  NO2  3H2  R  NH2  2 H2O
Ni, Pt or Pd
Ar  NO2  3H2  Ar  NH2  2 H2O
Nitro compounds can also be reduced with active metals such as Fe, Sn, Zn
etc. with conc. HCl

Sn / HCl
R  NO2  3H2 
or Fe / HCl
 R  NH2  2H2O

Sn / HCl
Ar  NO2  3H2 
or Fe / HCl
 Ar  NH2  2H2O
(ii)By Hoffmann’s method (Ammonolysis of alkyl halides): Reaction of alkyl
halides with an ethanolic solution of ammonia in a sealed tube at 373 K
forms a mixture of primary, secondary and tertiary amine and finally
quarternary ammonium salt. Process of cleavage of C-X bond by ammonia is
called ammonolysis.

The free amine can be obtained from the ammonium salt by treatment with a
strong base:
  NaOH  
NH3  RX  RNH3 X  RNH2  H2O  Na X
o
(1 amin e)
  NaOH  
RNH2  RX  R 2NH2 X   R 2NH  H2O  Na X
o
(2 amin e)
  NaOH  
R2NH  RX  R 3NH X   R 3N  H2O  Na X
o
(3 amin e)

Order of reactivity of halides is: RI> RBr> RCl

Larger the size of halogen atom easier is the cleavage of R-X bond

Limitations of Hoffmann’s method:

Method gives mixture of amines which are difficult to separate in a laboratory

Methods to get only one product by Hoffmann’s method:

(i)When ammonia is taken in excess primary amine is formed as main
product
(ii)When alkyl halide is used in excess quarternary ammonium salt is formed
as main product

Important Note: Method is not suitable for preparation of aryl amines

because aryl amines are relatively less reactive than alkyl halides towards
nucleophilic substitution reactions

(iii) By reduction of nitriles: Nitriles can be reduced to amines using

H2 / Ni , LiAlH4 or Na(Hg ) / C2H5OH
(iii)By reduction of amides: Amides are reduced to corresponding amines by
LiAlH4

(iv) By Gabriel phthalimide synthesis: Gabriel synthesis is used for the

preparation of primary amines. Phthalimide on treatment with ethanolic
potassium hydroxide forms potassium salt of phthalimide which on heating
with alkyl halide followed by alkaline hydrolysis produces the corresponding
primary amine

Important Note: Aromatic primary amines cannot be prepared by this

method because aryl halides do not undergo nucleophilic substitution with
potassium phthalimide

(v) By Hoffmann bromamide degradation reaction: Primary amines can be

prepared from amides by treatment with Br2 and KOH. Amine contains one
carbon atom less than the parent amide
4. Physical properties of amines:

(i)Solubility: Lower aliphatic amine is soluble in water because they can form
hydrogen bonding with water. Solubility decreases with increases in molar
mass of amines due to increase in size of hydrophobic group

(ii)Boiling points: Among the isomeric amines primary and secondary amines
have high boiling point because they can form hydrogen bonding. Tertiary
amine cannot form hydrogen bonding due to the absence of hydrogen
atom available for hydrogen bond formation. Hence order of boiling of
isomeric amines is Primary>Secondary> Tertiary

5. Chemical properties of amines:

(a)Basic character of amines:
Amines have an unshared pair of electrons on nitrogen atom due to which
they behave as Lewis base. Basic character of amines can be better
understood in terms of their K b and pKb values

Greater K b value or smaller pKb indicates base is strong

(b)Comparison of basic strength of aliphatic amines and ammonia:
Aliphatic amines are stronger bases than ammonia due to +I effect of alkyl
groups leading to high electron density on the nitrogen atom
(c) Comparison of basic strength of primary, secondary and tertiary amines
(i)The order of basicity of amines in the gaseous phase follows the expected
order on the basis of +I effect: tertiary amine > secondary amine > primary
amine > NH3
(ii)In aqueous solution it is observed that tertiary amines are less basic than
either primary or secondary amines. This can be explained on basis of
following factors:

(a) Solvation effect: Greater is the stability of the substituted ammonium

cation formed, stronger is the corresponding amine as a base. Tertiary
ammonium ion is less hydrated than secondary ammonium ion which is less
hydrated than primary amine. Thus tertiary amines have fewer tendencies to
form ammonium ion and consequently are least basic.

On the basis of solvation effect order of basicity of aliphatic amines should be

primary amine>secondary amine>tertiary amine.

(b) Steric factor: As the crowding of alkyl group increases from primary to
tertiary amine hinderance to hydrogen bonding increases which eventually
decreases the basic strength. Thus there is a subtle interplay of the inductive
effect, solvation effect and steric hinderance of the alkyl group which decides
the basic strength of alkyl amines in the aqueous state.
When the alkyl group is small like CH3 there is no steric hindrance to
hydrogen bonding. In this case order of basicity in aqueous medium is

When alkyl group is ethyl group order of basicity in aqueous medium is

(c)Comparison of basic strength of aryl amines and alkanamines:

Generally aryl amines are considerably less basic than alkyl amines .Taking
an example of aniline and ethylamine it is observed that ethyl amine is more
basic than aniline. In aniline –NH2 group is directly attached to benzene
ring. Hence unshared pair of electron on nitrogen is less available for
protonation because of resonance. Below mentioned are resonating
structures of aniline.

In the above resonating structures there is a positive charge on nitrogen

atom making the lone pair less available for protonation. Hence aniline is less
basic than ethyl amine which has no resonating structures. Less basicity of
aniline can also be explained by comparing the relative stability of aniline and
anilinium ion obtained by accepting a proton. Greater the number of
resonating structures, greater is the stability of that species.

Aniline is resonance hybrid of five resonating structures whereas anilinium

ion has only two resonating structures.

Thus aniline has less tendency to accept a proton to form anilinium ion.
(d)Effect of substituent on basic character of amines:
Electron donating or electron releasing group/groups (EDG) increases basic
strength.
Electron withdrawing (EWG) decreases basic strength

6. Reactions of amines:
(a) Acylation Reaction: Aliphatic and aromatic primary and secondary amines
(which contain replaceable hydrogen atoms) react with acid chlorides,
anhydrides and esters to form substituted amide. Process of introducing an
acyl group (R-CO-) into the molecule is called acylation. The reaction is
carried out in the presence of a stronger base than the amine, like pyridine,
which removes HCl formed and shifts the equilibrium to the product side

Base
R  NH2  RCOCl   RNHCOR  HCl
Ac id Substituted
chloride amide

O O
|| ||
Base
R ' NH2  R C OC R   R 'NHCOR  RCOOH
Ac id Substituted
anhydride amide

Base
R 2NH  RCOCl   R 2NCOR  HCl

Important Note: Since tertiary amine do not contain replaceable hydrogen

atom they do not undergo acylation reaction
(b) Carbylamine reaction: Only aliphatic and aromatic primary amines on
heating with chloroform and ethanolic potassium hydroxide form isocyanides
or carbylamines

Important Note: Secondary and tertiary amines do not give the above test

(c)Reaction of primary amine with nitrous acid:

(i)Primary aliphatic amine on reaction with nitrous acid (HNO2) forms

aliphatic diazonium salt which being unstable decomposes to form alcohol
and evolve nitrogen

(ii)Primary aromatic amines on reaction with nitrous acid (HNO2) in cold

(273-278 K) forms diazonium salt

(d)Reaction with benzene sulphonyl chloride: Hinsberg’s reagent-

Benzenesulphonyl chloride (C 6H5SO2Cl) reacts with primary and secondary
amines to form sulphonamides

The hydrogen attached to nitrogen in sulphonamide formed by primary

amine is strongly acidic due to the presence of strong electron withdrawing
sulphonyl group. Hence, it is soluble in alkali.
Since sulphonamide formed by secondary amine does not contain any
hydrogen atom attached to nitrogen atom, so it is not acidic. Hence it is
insoluble in alkali.

7. Ring substitution in aromatic amine: Aniline is more reactive than benzene

and undergoes electrophilic substitution reaction preferably at ortho and para
position.
(i) Bromination: Aniline reacts with bromine water at room temperature to
give a white precipitate of 2, 4, 6-tribromoaniline

Important Note: In order to stop reaction at monosubstitution activating

effect of –NH2 group is reduced by acetylation. This prevents di and tri
substituted products. Acetyl group is removed by hydrolysis.

(ii) Nitration:
(a)Under strongly acidic medium aniline gets protonated to form anilinium
ion, which is deactivating group and is meta directing. Hence minitroaniline is
also formed in 47 % along with ortho and para products.
Important Note: Aromatic amines cannot be nitrated directly because
HNO3 being a strong oxidising agent oxidises it forming black mass

(b) Nitration by protecting the –NH2 group by acetylation reaction with acetic
anhydride:

(iii) Sulphonation: Aniline reacts with conc. H2SO4 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
8. Reactions of benzene diazonium chloride:
(a) Reactions involving displacement of nitrogen

(b) Reactions involving retention of diazo group, coupling reactions:

Diazonium ion acts as an electrophile because there is a positive charge on
terminal nitrogen. Therefore benzene diazonium chloride couples with
electron rich compounds like phenol and aniline to give azo compounds. Azo
compounds contain –N=N- bond and reaction is coupling reaction.