Amines

hat the tormer is a weaker base than the

latter. In
n aniline, the N-atonm is attached H CH NH+OH
to the benzene ring and therefore the lone
CH-N1,
These O ions react with FeCl, as:
pair on N is delocalise the entire
over
As result, it cannot accept 2FeClh+ 6OH> 2Fe(OH)1 or Fe,O,.3H,O
benzee ing. a
hydrated ferric
a proton or any other electrophile.
oxide

mixture
(i) During nitration, the nitration
NH NH2 Used (conc. HNO, and conc. H,SO,)
protonates the NH, group
to produce
anilinium ion as

NH2
(1) (11) (I11) conc. HSO,
+conc. HNO,

Anilinium ion
NH2 NH2 Aniline
This anilinium ion acts as a deactivating
group and directs the incoming

nucleophile -

NO, to neta position

meta-isomer of nitroaniline 1s
and the
(V) (IV) obtained.
NH NH3 NH2
This is why it has a lower K, value (lower
basic strength) and high corresponding
pK, valuue.
In methylamine, CH,NH, the electron
is greater than that
O NH,OH

NO2
O NO2
m-Nitroaniline

density on nitrogen
in case of aniline. This is because -CH3 (v) During Friedel-Crafts reaction, anhydrou1s
virtue of its +I
AICl is used as a Lewis acid for
group in methylamine, by generation of the electrophile trom the
effect, increases electron density on N, electrophilic reagent.
which is more available for protonation.

(in) Any compound capable of forming CH:AIClh>H,+[AICL°

electrophile
hydrogen bonds withwater, dissolves in generated

it. Ethylamine is able to do the same and But when this reaction is carried out with
hence its solubility. aniline, no electrophile generation takes
N-... H place. The reason being the presence ot
aniline as a base.
HC2N H-0 H-N-C2H« Aniline is a Lewis base, reacts with

H H AICl and hence deactivates it. The

Lewis acid is theretore no more available
However, in aniline, the bulky for electrophile generation and hence
hydrocarbon part C,H, prevents the
-

reaction does not take place.

formation of effective hydrogen bonding
and therefore it is not soluble.
ferric oxide
NH NH2AICl
T h e formation of hydrated
into
may be understood by taking
Consideration the basic strength of +AICl3
Lewis
CH,NH2, water
CHNH2. In presence of Lewis base acid Deactivated AICl,
hydrolyses as
 (vi) Diazonium salts carry a N atom with a
is
positive charge. This positive charge
well dispersed in aromatic diazonium
salts through resonance as shown below:

N=N: N=N N=N

NEN

Such a charge delocalisation is not

possible in aliphatic amines and hence
they are less stable.
(vii) Gabriel phthalimide reaction gives
pure primary amines without any
contamination of secondary and tertiary
amines. Therefore, it is preferred for
synthesising primary amines.