Amines

 Amines are alkyl derivatives of ammonia where hydrogen atom(s) is / are replaced by
alkyl group.
–H
NH3 R – NH2 Primary amine
+R

– 2H
NH3 R – NH – R Secondary amine
+ 2R

– 3H
NH3 R–N–R Tertiary amine
+ 3R R

Classification of Amines

1) Aliphatic Amines.
 Amines in which the nitrogen atom is directly linked to one or more alkyl group.

2) Aromatic Amines.
 Amines in which nitrogen atom is linked directly with aryl group.
Eg: NH2

Aniline / Phenyl amine

Nomenclature

 Functional group: Amino group (– NH2).

 Common name: Alkyl amine / aryl amine / amino alkane.
 IUPAC name: Alkanamine.
 Eg: CH3NH2 Methyl amine or amino methane (Common name)
Methanamine (IUPAC name)
C2H5NH2 Ethyl amine or amino ethane (Common name)

Ethanamine (IUPAC name)

NH2
Aniline or phenyl amine or amino benzene (Common name)
Benzenamine (IUPAC name)

Preparation of Amines

1) Methyl amine from methyl iodide (Hoffman’s ammonolysis of alkyl halides).

 Methyl iodide (CH3I) is heated with alcoholic ammonia solution in a sealed tube.
Alcoholic
CH3 I + H NH2 CH3NH2 + HI
Methyl Methyl
iodide amine

2) Ethylamine from alkyl cyanides (Ethane nitrile) (Mendius reaction).

LiAlH4 or Na / alcoholic
R–C N + 4H R – CH2NH2
H2 / Ni primary amine
(10 amine)
LiAlH4
CH3 – C N + 4H CH3CH2NH2
Ethane nitrile / Na / alc.
Methyl cyanide
 The reduction of nitrile with Na / C2H5OH is called Mendius reaction.

3) Aniline from nitrobenzene by reduction.

 When nitrobenzene is reduced with tin and HCl or hydrogen gas in presence of a
catalyst Ni or Pt, aniline is formed.
 NO2 NH2
Sn / HCl
+ 6[H] + 2H2O

Nitrobenzene Aniline

NO2 NH2
Ni / Pt
+ 6[H] + 2H2O

Aniline

Physical Properties

Methyl amine Ethyl amine Aniline

 Is a colourless gas  Is a colourless liquid  Is a colourless oily

with ammonical fishy with fishy ammonical liquid with faint
smell. smell. characteristic smell.
 It has boiling point  It has boiling point  It has boiling point
266 K / – 7 0C. 292 K / 19 0C. 457 K / 184 0C.
 It is highly soluble in  It is soluble in water  It is sparingly soluble
water due to H- due to H-bonding. in water but dissolves
bonding.  Burns in air with readily in alcohol,
 Burns in air with yellow flame. chloroform and ether.
yellow flame.  On exposure to air
and light, it rapidly
darkens (brown) due
to oxidation.
 It is toxic in nature.
 Chemical Properties

a) Basic nature.
 Ammonia and amines are bases due to presence of lone pairs of electron on nitrogen
atom.
 Primary amines (ethyl amine) are stronger bases than ammonia. This is because in
primary amines alkyl groups are electron releasing groups and have +I effect. Due to
+I effect of alkyl groups, electron density on nitrogen atom of amino group is
increased and lone pairs of electron are easily available. Thus primary amines are
stronger bases than ammonia.
 Secondary amines are stronger bases than tertiary amines although tertiary amines
have three or more alkyl groups and more +I effect than secondary amines. This is
because alkyl groups are larger or bulky in size and have hindrance on the nitrogen
atom to donate lone pair of electron.
NH2
R
R – NH – R > R – NH2 > R – N – R > NH3 >

Decreasing order of basicity

i) Reaction with water.

R – NH2 + H2O RNH3OH [RNH3] + + OH–
1) Methyl amine.
CH3NH2 + H2O CH3NH3OH
Methyl ammonium hydroxide
2) Ethyl amine.
C2H5NH2 + H2O C2H5NH3OH
Ethyl ammonium hydroxide
3) Aniline.
NH2 NH3OH

+ H2 O

Anilium hydroxide
 ii) Reaction with acids.
1) Methyl amine.
CH3NH2 + HCl CH3NH3+Cl–
Methyl ammonium chloride
CH3NH2 + HNO2 CH3OH + N2 + H2O
2) Ethyl amine.
C2H5NH2 + HCl C2H5NH3+Cl–
Ethyl ammonium chloride
C2H5NH2 + HNO2 C2H5OH + N2 + H2O
3) Aniline.
NH2 NH3+Cl–

+ HCl

Anilium chloride

NH2 N+ NCl–
273 – 278 K
+ HNO2
HCl
Benzene diazonium chloride
 The process of converting an aromatic 10 amine into a diazonium salt by
treating with cold solution of HNO2 is called diazotisation.

b) Reaction with haloalkanes.

RX RX RX R
R–N–H R–N–R R–N–R R – N+ – R X–
H –HX H – HX R R
10 20 30 quaternary salt

Eg: C2H5NH2 + C2H5I (C2H5)2NH + HI

 Ethyl amine (10) Ethyl iodide Diethyl amine (20)

NH2 NHCH3 N(CH3)2 N+(CH3)3I–

+CH3I +CH3I +CH3I

–HI –HI –HI

Aniline (10) Methyl Dimethyl Trimethyl

aniline (20) aniline (30) phenyl
ammonium
iodide
(quaternary salt)

Azo Dyes

 Dye: A natural or synthetic substance (solution) used to add a colour to or change the
colour of something.
 Azo: Compound containing azo group (– N N –).
 Azo dye: A class of synthetic dye whose molecules contain two adjacent nitrogen
atoms between carbon.

N N

 Synthesis: Azo dyes are obtained by treating benzene diazonium salt with phenol or
N, N – dimethyl aniline. This reaction is called coupling reaction.

pH- 9-10

N2 Cl + H OH N N OH + HCl
Benzene Phenol 273-278 K p–hydroxy azo benzene
diazonium (orange)
chloride
 CH3 H+ pH- 4-5 CH3
N2 Cl + H N N N N + HCl
CH3 273-278 K CH3
Benzene N, N – dimethyl p – Dimethylamine azo
diazonium aniline benzene (yellow)
chloride

 Uses:

1) Azo dye test – Used to distinguish between aniline (primary aromatic amine)
and ethyl amine (primary aliphatic amine).
2) Used as indicators in acid–base titration (Eg: MeOH).
3) Used in DVD and CD as the recording layers.