DIAZONIUM SALTS (c) Benzenediazonium chloride when treated with

presence of CuBr gives bromobenzene. HBr

Compounds"containing NX as functional group are called
diazonium salts. They have general formula ArN,X where N,CI 3r
Ar arylgroup and X ion may be Cl, Br, HSO, BF4, etc.
+HBr CuBr
reparation of Benzenediazonium Chloride
Aniline when treated with sodium nitrite and hydrochloric acid Bromobenzene
at 273-278 K gives benzenediazonium chloride. This
reaction2. Gatterman reaction: The
replacement of N.CI grOUn
rOup of
is called diazotisation.
benzenediazonium chloride by CI or Br ion by the reacie
NH
NaNO, +HC N,CI with halogen acid in presence of copper powder is cale
273 -278 K
+NaCl+2H,O Gatterman reaction.

Properties of Benzenediazonium Chloride -Cl

Benzenediazonium chloride is a colourless crystalline solid.
It is readily soluble in water.
N.CHCI C +N, +CuCI
It is stable for a short time at low temperature (273-278 K).
Chlorobenzene
Therefore it is not stored and is used immediately after its
Br
preparation. +HBr +N +CuBr
Alkyl diazonium salts are highly unstable because
spC N bond of aliphatic amine is weaker and breaks The vield in Gatterman reaction is poor.
easily. 3. Action of KI : Benzenediazonium chloride when treated
with potassium iodide gives iodobenzene.
-CN=Ni >-C* +N, + CI
Arene diazonium salts are relatively more stable due to
partial double bond character ofsp+C- N bond in aromatic
N+KI
due to Benzenediazonium lodobenzene
compound arising resonan ce.
chloride

N-N N=N 4. Action of HBF, : Benzenediazonium ch loride when treated

with fluoroboric acid gives benzenediazonium fluoroborate
which on heating decomposes to yield aryl fluoride.

HBF HBF N,BF

-
NN
BF,

Chemical reactions of benzenediazonium chloride:

+ 5. Reduction: Benzenediazonium Fluorobenzene
chloride is reduced o
of
1. Sandmeyer reaction: The replacement of -N,CI group mild reducing agent like hypophosphorus acid or ethano
Br and
benzenediazonium chloride by the nucleophiles Cl , give benzene.
CN in the presence ofCu (I) ion as catalyst is called Sandmeyer
N,CI HP0 +
reaction.
Benzenediazonium chloride when treated with KCN
in H,PO, +N;* HCI
(a) Phosphorus
presence of CuCN gives cyanobenzene. Benzene acid

N.CI CN
CI CH,CH,OH +CH,CH0 +N, +HCl
CuCN Ethanal
+KCN N Benzenediazonium Benzene
Cyanobenzene chloride

Benzenediazonium chloride when

treated with HCI in
chloride solution undergo
(b) chlorobenzene.
6. Hydrolysis : Benzenediazonium

presence of
CuCl gives hydrolysis at 283 K to give phenol.
N,CI CI OH
-NCH,O N,+HC
+HCI +N, Phenol
Chlorobenzene
 itration: Benzenediazonium chloride when treated
ives
benzenediazon
fluoroborate. It is heated with
with
(11)Benzenediazonium chloride when treated with aniline gives
Bqueous sodium nitrite ution in the presence of Cu (1) ion p-amino azo benzene.
0 give nitrobenzene.

N,CI +H NH
NCI +HBF
HBF NBF NaNO
Cu, N=N->NH,
P-Aminoazobenzene
NO2 (Yellow dye)
Advantages of benzenediazonium chloride
+N+NaBF Aryl fluorides, aryl iodides and aryl cyanides can be
prepared
using benzenediazonium chloride which is not possible
Coupling reaction : Combination of benzenediazonium otherwise.
Ssaltswith other aromatic compounds is called
coupling reaction. POINTS TO BE
Benzenediazonium chloride reacts with
phenol to give NOTED
phydroxyazobenzene. Aliphatic diazonium salts are highly unstable whereas
arene diazonium salts are stable for a short time in
CIH OH> solution at lower temperature.
Benzenediazonium fluoroborate is water insoluble and
stableat room temperature
N=N -OH Aryl fluorides, aryl iodides and aryl cyanides cannot be
(Orange dye) prepared by direct halogenation. These are prepared by
P-Hydroxyazobenzene Sandmeyer reaction only

Saemanary
Amines are alkyl aryl derivatives of ammonia.
or
However boiling points of amines are lower than
e.g. R NH, Ph NH etc corresponding alcohols. The order of boiling points of
There are three types of isomeric amines are in the order primary > secondary >
amines
a) Primary amine contains NH, grou tertiary
R-
NH, Ar NH, Aliphatic amines are more basic than NH because electron
(0) Secondary amine
R- NH R or
contains NH group. releasing inductive effect (+I ctfect) of alkyl group
R NH R increaseselectron density on nitrogen atom.
C)lertiary amine containsNgroup. In gaseous state inductive effect only affects basicity of
amines. Hence basic strength of 3 amine 2°-amine
RN or R NR or R-NRR 1-amine ammonia
Dcondary and tertiary amines are classifiedas simple Inaqueous solution (polar protiesolvents)a combination
iines when all the alkyl or aryl groups are same and of electron releasing (+) inductive effect, steric and
mixed amines whe the alkyl orarylgroups are different. H-bonding influence the stability of substituted ammonium
mnes are also known as aliphatic and aromatic if they cations and affect the basic nature of amine.
Contain alkyl the order of basicity of methyl amines
Therefore
or (R) aryl (Ar)
group pair (Lone pair) on are in the order
All theamines have nshared electron (CH),NH> CHNH,(CH),N> NH, and basicity of
nitroge atom. Hend they behave as Lewis bases. other alkyl amines are in the order
Amines are preparedby
RNH RN> RNH, >NHj
4 Reduction of nitro compound. Aromatic amines are
weaker base than NH, because the
lone pair of electrons of nitrogen
Ammonolysis
c) Reduction of alkyl halide with the benzene ring.
is involved in
resonance
or alkaline degradation (Hoffmann's Electron releasing group attached
to benzene ring
omamide degradation reaction) of amides. increases whereas electron withdrawing
d) Reduction of imines. groups decreases their basic character
Amineemolecules undergo intermolecular association due
oe Carbylamine reaction Primary amines (aliphatic and
ydrogen have boiling points aromatic) react with CHCI, and KOH to give
higher than Dydrocarbons andamines
onding. Hence alkyl halides ofcomparable smelling isocyanide (carbylamine), This reactionpungent
is used
to identify 19-amines
olecular mass