Aryl Diazonium Salt

Intext Questions
13.4 Arrange the following in increasing order of their basic strength:

(i) C2H5NH2, C 6H 5NH2, NH3, C 6H 5CH 2NH 2 and (C2H 5) 2NH
(ii) C2H5NH2, (C2H5)2NH, (C2H5)3N, C6H5NH2
(iii) CH 3NH2, (CH3)2NH, (CH3)3N, C6H 5NH2, C6H 5CH2NH2.
13.5 Complete the following acid-base reactions and name the products:
(i) CH 3CH2CH2NH2 + HCl → (ii) (C2H5)3N + HCl →
13.6 Write reactions of the final alkylation product of aniline with excess of methyl
iodide in the presence of sodium carbonate solution.
13.7 Write chemical reaction of aniline with benzoyl chloride and write the name of
the product obtained.
13.8 Write structures of different isomers corresponding to the molecular formula,
C3H 9N. Write IUPAC names of the isomers which will liberate nitrogen gas on
treatment with nitrous acid.
II. DIAZONIUM SALTS

+ –
The diazonium salts have the general formula R N2 X where R stands
– – –
for an aryl group and X ion may be Cl Br, HSO−4 , BF4− , etc. They are
named by suffixing diazonium to the name of the parent hydrocarbon
from which they are formed, followed by the name of anion such as
+
chloride, hydrogensulphate, etc. The N2 group is called diazonium
+ –
group. For example, C 6 H 5 N 2 C l is named as benzenediazonium
+ –
chloride and C 6H 5N 2 HSO 4 is known as benzenediazonium
hydrogensulphate.
Primary aliphatic amines form highly unstable alkyldiazonium salts
(refer to Section 13.6). Primary aromatic amines form arenediazonium
salts which are stable for a short time in solution at low temperatures
(273-278 K). The stability of arenediazonium ion is explained on the
basis of resonance.
13.7 Method of Benzenediazonium chloride is prepared by the reaction of aniline with

nitrous acid at 273-278K. Nitrous acid is produced in the reaction
Preparation mixture by the reaction of sodium nitrite with hydrochloric acid. The
of Diazoniun conversion of primary aromatic amines into diazonium salts is known
Salts as diazotisation. Due to its instability, the diazonium salt is not
generally stored and is used immediately after its preparation.
+ –
273 −2 78K
C6 H 5NH 2 + NaNO 2 + 2HCl  → C6H 5 N2 Cl + NaCl + 2H 2O
Chemistry 396
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13.8 Physical Benzenediazonium chloride is a colourless crystalline solid. It is readily
soluble in water and is stable in cold but reacts with water when
Properties warmed. It decomposes easily in the dry state. Benzenediazonium
fluoroborate is water insoluble and stable at room temperature.
1 3 . 9 Chemical The reactions of diazonium salts can be broadly divided into two
categories, namely (A) reactions involving displacement of nitrogen and
Reactions (B) reactions involving retention of diazo group.
A. Reactions involving displacement of nitrogen
Diazonium group being a very good leaving group, is substituted
by other groups such as Cl –, Br–, I –, CN– and OH– which displace
nitrogen from the aromatic ring. The nitrogen formed escapes from
the reaction mixture as a gas.
– – –
1. Replacement by halide or cyanide ion: The Cl , Br and CN
nucleophiles can easily be introduced in the benzene ring in the
presence of Cu(I) ion. This reaction is called Sandmeyer reaction.
2 2
2 2
Alternatively, chlorine or bromine can also be introduced in the

benzene ring by treating the diazonium salt solution with corresponding
halogen acid in the presence of copper powder. This is referred as
Gatterman reaction.
The yield in Sandmeyer reaction is found to be better than

Gattermann reaction.
2. Replacement by iodide ion: Iodine is not easily introduced into
the benzene ring directly, but, when the diazonium salt solution
is treated with potassium iodide, iodobenzene is formed.
3. Replacement by fluoride ion: When arenediazonium chloride is

treated with fluoroboric acid, arene diazonium fluoroborate is
precipitated which on heating decomposes to yield aryl fluoride.
4. Replacement by H: Certain mild reducing agents like

hypophosphorous acid (phosphinic acid) or ethanol reduce
diazonium salts to arenes and themselves get oxidised to
phosphorous acid and ethanal, respectively.
397 Amines
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5. Replacement by hydroxyl group: If the temperature of the
diazonium salt solution is allowed to rise upto 283 K, the salt
gets hydrolysed to phenol.
6. Replacement by –NO2 group: When diazonium fluoroborate is

heated with aqueous sodium nitrite solution in the presence of
copper, the diazonium group is replaced by –NO2 group.
B. Reactions involving retention of diazo group

coupling reactions
The azo products obtained have an extended conjugate system having
both the aromatic rings joined through the –N=N– bond. These compounds
are often coloured and are used as dyes. Benzene diazonium chloride
reacts with phenol in which the phenol molecule at its para position is
coupled with the diazonium salt to form p-hydroxyazobenzene. This
type of reaction is known as coupling reaction. Similarly the reaction of
diazonium salt with aniline yields p-aminoazobenzene. This is an example
of electrophilic substitution reaction.
13.10 Importance From the above reactions, it is clear that the diazonium salts are very
good intermediates for the introduction of –F, –Cl, –Br, –I, –CN, –OH,
of Diazonium –NO2 groups into the aromatic ring.
Salts in Aryl fluorides and iodides cannot be prepared by direct halogenation.
Synthesis The cyano group cannot be introduced by nucleophilic substitution of
of Aromatic chlorine in chlorobenzene but cyanobenzene can be easily obtained
from diazonium salt.
Compounds
Thus, the replacement of diazo group by other groups is helpful in
Chemistry 398
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preparing those substituted aromatic compounds which cannot be
prepared by direct substitution in benzene or substituted benzene.
How will you convert 4-nitrotoluene to 2-bromobenzoic acid ? Example 13.5
Solution
Intext Question
13.9 Convert
(i) 3-Methylaniline into 3-nitrotoluene.
(ii) Aniline into 1,3,5 - tribromobenzene.
Summary
Amines can be considered as derivatives of ammonia obtained by replacement of
hydrogen atoms with alkyl or aryl groups. Replacement of one hydrogen atom of
ammonia gives rise to structure of the type R-NH2 , known as primary amine.
Secondary amines are characterised by the structure R2 NH or R-NHR′′ and tertiary
amines by R3 N, RNR ′R′′ ′′ or R2 NR′.
′. Secondary and tertiary amines are known as
simple amines if the alkyl or aryl groups are the same and mixed amines if the
groups are different. Like ammonia, all the three types of amines have one unshared
electron pair on nitrogen atom due to which they behave as Lewis bases.
Amines are usually formed from nitro compounds, halides, amides, imides, etc.
They exhibit hydrogen bonding which influence their physical properties. In
alkylamines, a combination of electron releasing, steric and H-bonding factors
influence the stability of the substituted ammonium cations in protic polar solvents
and thus affect the basic nature of amines. Alkyl amines are found to be stronger
bases than ammonia. In aromatic amines , electron releasing and withdrawing groups,
respectively increase and decrease their basic character. Aniline is a weaker base
399 Amines
2015-16

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Intext Questions

13.4 Arrange the following in increasing order of their basic strength:

II. DIAZONIUM SALTS

13.7 Method of Benzenediazonium chloride is prepared by the reaction of aniline with

Alternatively, chlorine or bromine can also be introduced in the

The yield in Sandmeyer reaction is found to be better than

3. Replacement by fluoride ion: When arenediazonium chloride is

4. Replacement by H: Certain mild reducing agents like

6. Replacement by –NO2 group: When diazonium fluoroborate is

B. Reactions involving retention of diazo group

How will you convert 4-nitrotoluene to 2-bromobenzoic acid ? Example 13.5

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