AMINES

Amines are the derivatives of ammonia in

which one, two or all the three hydrogen
atoms are replaced by alkyl and/or aryl
groups.
Nitrogen of all amines are sp3 hybridised and
Structure of amines

the geometry of amines is pyramidal.

The bond angle decreases from the
tetrahedral angle of 109.5º to 107º in primary
(1º) and secondary (2º) amines and ammonia.

 In case of tertiary (3º) amines, the bond angle

may increase from 107º due to steric hindrance
between the three bulky alky groups
For example, it is 108º in case of trimethylamine as
shown in following figure.
Nomenclature
Aliphatic amines are commonly named by
naming alkyl groups attached to the
nitrogen atom followed by the suffix-amine.
The names are written in one word.
In IUPAC system, amines are named as
alkanamines.
(ii) When more than one amino group is
present at different positions in the parent
chain, their positions are specified as
follows:
 In case of aromatic amines (arylamines),
group is directly attached to the benzene
ring. In IUPAC nomenclature, suffix ‘e’ of
arene is replaced by ‘amine’. For example,
(aniline) is named as benzenamine.

 In case of complex amine, only IUPAC

nomenclature is used in which amino group
is considered as a substituent and its
position on the chain is indicated by the
lowest possible number.
Q2.(i) Write structures of different isomeric amines
corresponding to the molecular
formula, C4H11N.
(ii) Write IUPAC names of all the isomers.
(iii) What type of isomerism is exhibited by different
pairs of amines?
preparation
(i) Reduction of nitro compounds
Reduction with Fe/HCl is preferred
because FeCl2 formed during reaction
gets hydrolysed to HCl which can be
used for further reaction. .
(ii) Reduction of nitriles
(iii) Reduction of amides:
CONVERTION
1.CH3COOH CH3CH2NH2

2.CH3Cl CH3CH2NH2
CONVERTION(ans)
1.CH3COOH---NH3-- CH3CONH2
---LiAlH4CH3CH2NH2

2.CH3Cl ---KCNCH3CN---H2/PtCH3CH2NH2
(iv) Ammonolysis of alkyl halides:
If alkyl halide is in excess, the amine formed further
reacts with akyl halide to form 2º, 3º amines and finally
quaternary ammonium salts.
Disadvantages
1. a mixture of primary, secondary and tertiary amines
and also a quaternary ammonium salt is
obtained .Hence separation is difficult.
However, primary amine is obtained as a major
product by taking large excess of ammonia.
2.Aromatic amines cannot be prepared.
Ques
Write chemical equations for the following reactions:
(i) Reaction of ethanolic NH3 with C2H5Cl.
(ii) Ammonolysis of benzyl chloride and reaction of
amine so formed with two moles of CH3Cl.
(v) By Hoffmann bromamide degradation
reaction
When an amide is treated with Br2 and NaOH or
KOH , a 10 amine is formed which contains one carbon
less than the parent amide.
(vi) Gabriel phthalimide synthesis
Gabriel synthesis is used for the
preparation of primary amines.
Phthalimide on treatment with
ethanolic KOH forms potassium salt of
phthalimide which on heating with
alkyl halide followed by alkaline
hydrolysis produces the corresponding
primary amine.
Gabriel phthalimide synthesis
LIMITATION
Aromatic amines cannot be prepared by this method
because aryl halides do not undergo nucleophilic
substitution with the anion formed by phthalimide.
(vii) Preparation of Aniline
From nitrobenzene
QUES
Physical Properties of Amines

(i) The lower amines are gases (or low-boiling liquids)

with ammonia-like smell (fishy odour). Primary
amines with more than two carbon atoms are liquid
and still higher ones are solid. Aniline and other
aromatic amines are usually colourless but get
coloured on oxidation.
(ii) Solubility
A)Amines are soluble in water because they form
hydrogen bonds in water. However, solubility
decreases in higher amines due to increase in size of
the hydrophobic alkyl group. Amines are also soluble
in organic solvents like alcohol, ether and benzene.
B)For amines with same molar mass, the
order of solubility is 10> 20> 30. It is due to
decrease in extent of H bonding from
primary to tertiary because of the decrease
in the no. of H atom.
C) Alcohols are more soluble than amine
because alcohols form strong H bonding
with water due to greater electronegativity
of oxygen. [alcohols are more polar than
amines.]
(iii) BP
In general, amines have higher boiling points than non-
polar compounds of similar molecular weights. This is
because amines are polar compounds and form
intermolecular hydrogen bonds.
Order of BP is 10> 20> 30.
Primary and secondary amines form intermolecular
hydrogen bonding but this intermolecular association
is more in primary amines than in secondary amines
as there are more hydrogen atoms.
Tertiary amines do not have intermolecular association
due to the absence of hydrogen atom available for
hydrogen bond formation. Hence least BP.
CHEMICAL
PROPERTIES
1.Basicity of amines
Amines are basic in nature because they have lone pair
of electrons on nitrogen atom. Basic strength of
amines can be compared using Kb and PKb
 Kb α basicity

PKb α 1
basicity
Larger the value of
stronger is the base.
Comparison of Basicity
1.Aliphatic amines are more basic than ammonia.
The alkyl groups of amines show +I effect and thus
they release electrons towards the nitrogen atom. Due
to this, the electron density around nitrogen atom
increases which increases the availability of lone pair
of electrons.
(b) Aryl amines are less basic than
ammonia
It is because in aniline or other aryl amines,
the -NH2 group is attached directly to the
benzene ring. So the unshared electron pair
on nitrogen atom is in conjugation with the
Л es of benzene ring, hence due to
resonance ,electron density in N decreases
and are less basic.
3.Comparison of Basicity of Aliphatic
amines
In gas phase the order is 30 >20 >10
The greater the number of electron-releasing [+I
effect] alkyl groups (R), greater the availability of lone
pair of electrons on nitrogen and stronger the base.
(Fig)
In aqueous soln,
The basisity of amines in aq.soln depends on
i)+I effect of R groups
ii)extend of H bonding with water [solvation]
iii)sterric effect
Hence the order is
20 >10 >30[R = -CH3]
20 >30 >10[R = -C2H5]
The less basicity of trimethyl amine is due to steric
crowding of three methyl groups and less solvation due to
less extent of H bonding
Effect of substituents on basisity
In case of substituted aniline, electron releasing
groups like –OCH3, –CH3 increases basic strength
whereas electron withdrawing groups like –NO2, –
SO3,–COOH, –X decreases it.
(2) Alkylation
(3) Acylation
Aliphatic and aromatic primary and
secondary amines react with acid
chlorides, anhydrides and esters by
nucleophilic substitution reaction.
This reaction is known as acylation.
(4)Reaction with chloroform (carbylamine
reaction)
Aliphatic and aromatic 10 amines on
heating with chloroform and alc. KOH form
isocyanides or carbylamines which are foul
smelling substances. 20and 30 amines do not
show this reaction. This reaction is known
as carbylamine reaction or isocyanide test
and is used as a test for primary amines.
(5) Reaction with nitrous acid
(a)Reaction with nitrous acid helps in distinguishing
between three classes of aliphatic amines.
Primary amines react with nitrous acid to form
alcohols.
20 Amines react with nitrous acid to form a yellow
green oily layer of N-nitrosoamines. N-Nitroamines on
warming with a crystal of phenol and a few drops of
conc. H2SO4 form green solution which when treated
with aqueous NaOH, turns deep blue and then red on
dilution. This reaction is called Liberman’s nitroso
reaction.
ter-Amines readily dissolve in
nitrous acid forming crystalline
trialkyl ammonium nitrite.
(b) Diazotisation:
Aromatic amines react with nitrous acid at low
temperatures (273-278 K) to form diazonium salts
(6) Reaction with Benzenesulphonyl
chloride (C6H5SO2Cl)- Hinsberg’s reagent
 Hinsberg’s reagent reacts with primary and secondary
amines to form sulphonamides.
(a) The reaction of benzenesulphonyl chloride with
primary amine yields N-alkylbenzenesulphonyl amide
which is soluble in alkali.
(b) In the reaction with secondary
amine, N,N-diethyl- benzene
sulphonamide is formed which is
insoluble in alkali.
(c) Tertiary amines do not react with
benzenesulphonyl chloride. These days
benzenesulphonyl chloride is replaced by p-
toluenesulphonyl chloride.
(7) Electrophilic substitution reaction:
Due to resonance electron density increases at ortho
and para positions as compared to meta positions.
Therefore group directs the incoming group to ortho
and para positions.
A. Bromination:
B. Nitration
In strongly acidic medium significant amount of para
isomer is obtained. This is due to the formation of
anilinium ion which is para directing.
C. 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.
C. Sulphonation
D. Friedel-Craft reaction:
Aniline does not undergo Friedel-Crafts reaction
(alkylation and acetylation) due to salt formation with
AlCl3, the Lewis acid, which is used as a catalyst. Due
to this, nitrogen of aniline acquires positive charge and
hence acts as a strong deactivating group for further
reaction.
D. Friedel-Craft reaction: