20 .1 Preparation of Aryl Amines 20 .

4 Illustrative Examples

20 .2 Properties of Aryl Amines EXERCISES

20 .3 Preparation and Reactions of Diazonium Salts SOLUTIONS

When 1°, 2°, or 3° amino group is directly attached to benzene nucleus, compunds are known as aromatic
amines or aryl amines

NH2 NHR NRR′

(R and R′ may be any alkyl or aryl (group)

Aniline, 1° N-Alkylaniline N, N-Dialkylaniline

(Aminobenzene) (2° amine) (3° amine)

One should note that when amino group is indirectly attached to benzene ring, the compound is called as aryl
substituted aliphatic amine. In such compounds, —NH2 group behaves as that of aliphatic amines.

NH2 NH2 CH2NH2 CH2NHCH3

CH3 NH2

o-Toluidine o-Phenylenediamine Benzylamine (1°) N-Methylbenzylamine (2°)

(o -Methylaniline)

Aromatic amines Aryl substituted aliphatic amine

 EBD_7091
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20.1 Preparation of Aryl Amines

Most of the methods used for preparing aromatic amines are very similar to that used for aliphatic amines.

1. Reduction of nitro compounds. The most widely used method for preparing aromatic amines is the reduction of
the nitro group to the amino group. This reduction can be achieved by catalytic hydrogenation, or most frequently
with an acid and a metal (Fe, Zn, Sn) or a metal salt like SnCl2.
H 2 , Catalyst
C6H5NO2  → C6H5NH2
or (i) Fe, HCl, (ii) OH −

Nitrobenzene Aniline

+
NO2 NH3 NH2

–
Fe, Hcl OH
  → →

CH3 CH3 CH3

p-Nitrotoluene p-Toluidine

COCH3 COCH3
(i) Sn, HCl

– →
(ii ) OH
NO2 NH2
m-Nitroacetophenone m-Aminoacetophenone

Remember that LiAlH4 does not reduce PhNO2 to PhNH2.

Since nitro compounds are readily prepared by direct nitration, the primary aromatic amines obtained by the
reduction of these nitro compounds are readily converted into diazonium salts ; the diazonium group, in turn, can be
replaced by a large number of other groups. This route gives a common and most useful method for introducing different
groups in benzene nucleus.
Ar—H → Ar—NO2 → Ar—NH2 → Ar—N2+ → Other compounds.

1. Give steps involved in the following conversions.

(a) Toluene to p-toluidine (b) o-Isopropylaniline from benzene
(c) m-Aminoacetophenone from benzene (d) 4-Isopropyl-1, 3-benzenediamine from benzene.
(e) Toluene to p-aminobenzoic acid.

Selective reduction of one nitro group of a dinitro compound can often be achieved by NH 4HS or through the use
of carefully measured amount of hydrogen sulphide in aqueous (or alcoholic) ammonia

NO2 NH2
NH HS or
   4   →
H2S, NH3, C2H5OH
NO2 NO2
m-Dinitrobenzene m-Nitroaniline
 961
Remember that

(i) use of an excess amount of H2S may result in the reduction of more than one nitro group.
(ii) it is always not possible to predict which —NO2 group will be reduced, e.g.
CH3 CH3
NO2 NO2
2H S, NH
  3→

NO2 NH2

NH2 NH2
NO2 NO2
H S, NH
 2  3→

NO2 NH2

2. Hofmann degradation.
Br2/NaOH
C 6 H 5 CONH2 ¾¾¾® C6 H5 NH2
Benzamide Aniline

3. Curtius reaction
N 3H, conc. H 2SO 4
C6H5COOH ¾¾¾¾¾¾® C6H5NH2 + CO2 + N2
heat

H3O+
4. By acidic hydrolysis of isocyanides. C6H5NC ¾¾® C6H5NH2 + HCOOH
5. By reduction of azobenzene.
H2, Ni H2, Ni
N= N under
NH—NH under
2 NH2
pressure pressure
Azobenzene Hydrazobenzene Aniline

Sn, NaOH (i) SnCl 2 , H 3 O + , (ii) OH -

ArN = NAr → ArNH—NHAr ¾¾¾¾¾¾¾¾¾¾¾¾® 2ArNH2
(mild reduction) (vigorous reduction)

6. Hofmann Martius rearrangement. When a 3° or 2° aromatic amine hydrochloride is heated, it is converted into
primary amine hydrochloride.

N(CH3)2HCl NH(CH3).HCl NH2HCl NH2

CH3 – CH3
heat heat OH

N, N-Dimethylaniline
hydrochloride CH3 CH3 CH3

7. Commercially, aniline is prepared by passing ammonia over chlorobenzene in presence of Cu2O as catalyst and
under pressure and at 200°C.
Cu 2 O
C6H5Cl + NH3 ¾¾¾¾¾¾¾¾® C6H5NH2
pressure, 200° C

Like aliphatic secondary amines, aromatic secondary amines can be prepared by reducing the corresponding
isocyanide. C6H5NC → C6H5NHCH3.
 EBD_7091
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20.2 Properties of Aryl Amines

Aryl amines give most of properties of aliphatic amines in exactly similar fashion, viz. solubility, basicity,
alkylation, acetylation, benzoylation, carbylamine reaction, condensation with aldehydes to form Schiff base, oxidation
etc. Two properties deserve special attention, viz. reaction with nitrous acid and electrophilic substitution.
1. Reaction with nitrous acid. As is aliphatic amines, each class of aromatic amine yields a different kind of
product when treated with nitrous acid, HONO. Primary aromatic amines react with nitrous acid to yield arene
diazonium salts.
cold
ArNH2 + NaNO2 + 2HX ¾¾® Ar—N ≡ N+X– + NaX + 2H2O
1° Aromatic amine Arenediazonium salt
Although arenediazonium salts are far more stable than aliphatic diazonium salts, especially at low temperatures
(0–5°C), they slowly decompose even at low temperature, hence always used immediately after preparation.
Why arenediazonium ions are more stable than alkyldiazonium ions ? This is due to two factors.
(a) Electron-release from the ortho and para positions of the ring stabilizes the arenediazonium ions.

+ + – + –

:
:
N≡ N: N≡ N ; + N≡N:
+

(b) The arene cation, Ar+, is very difficult to be formed as compared to R+ from RN+ ≡ N.
Secondary amines, both aliphatic and aromatic, react with nitrous to form N-nitrosamines which shown
Libermann’s nitroso reaction
C6H5NHCH3 + NaNO2 + HCl → C6H5N(NO)CH3
N-Methylaniline N-Nitroso-N-methylaniline
Tertiary aromatic amines undergo ring substitution discussed in electrophilic substitution.

2. Electrophilic Substitution. Arylamines contain two functional groups, the amino group and the aromatic ring.
The reactivity of the amino group is affected by its aryl substituent, and the reactivity of the ring is affected by its
amino group. The same electron delocalization that reduces the basicity and the nucleophilicity of an arylamine
nitrogen increases the electron density in the aromatic ring and thus makes arylamines extremely reactive
towards electrophilic aromatic substitution. + +
NH2 NH2
We know that the —NH2, —NHR, and —NR2 groups are ortho, para-
H
directing and exceedingly powerful activating groups in
electrophilic aromatic substitution. These effects are due to the Y
formation of the especially stable intermediate carbocations I and II, in
which every atom (except hydrogen) has a complete octet of electrons. H Y
Thus the chief problem encountered in electrophilic substitution with aromaticI amines is that they II
are hightly reactive. For example,
(a) In halogenation substitution tends to occur at every available ortho and para position and thus monohalogenated
product can’t be prepared

NH2 NH2
Br Br
+ Br2 (aq.)

Br
Aniline 2, 4, 6-Tribromoaniline

NH2 NH2
Br2 ( aq.) Br Br

CH3 CH3
 963
(b) Nitric acid not only nitrates, but also oxidizes the highly reactive ring as well, with loss of much material as
dark-coloured tar. Furthermore, in the strongly acidic nitration medium, the amine is converted into anilinium
ion (—NH3+) ; substitution is thus controlled not by the —NH2 group but by the —NH3+ group which, because
of its positive charge, directs the entering group to the meta- position instead of ortho, and para-.
+
: NH2 NH3

Conc. HNO3,
Conc. H2SO4,
+
—NH2 gp. o , p -director —NH3 gp. m -director
However, all these difficulties are overcome by protecting the amino group by acetylation, with either acetyl
chloride or acetic anhydride. Acetylation (—NH2 → NHCOCH3) converts —NH2 group to acetamido (—NHCOCH3)
group which is o, p-directing but lesser activating toward electrophilic aromatic substitution than the parent —NH2 group.
H H
+
: NH2 O
:N N
C—CH3 C—CH3
CH3 CCl 
O O–
Aniline Acetanilide Resonance in acetanilid due to amide group
(electron pair can delocalize (note that electron pair on N can also delocalize to
only to benzene ring making amide group, hence —NHCOCH3 gp. becomes
o, p-positions highly reactive) weak activator than the —NH2 group)

Thus protection of the amino group of an arylamine moderates the reactivity of the —NH2 group and permits
nitration (or halogenation) of the ring to be achieved in the required o, p-positions. Another important feature of the N-
acetyl protecting group is that after it has served its purpose, it may be removed by hydrolysis (acidic or basic) liberating
the parent amino group (deprotection).
Bromination
NH2 NHCOCH3 NHCOCH3 NHCOCH3
Br
(CH3CO)2O Br2 / CH3COOH
  →   → +
(protection step) (bromination step)

Aniline
Br
NH2 NH2
+ – Br
(i) H2O, H ; (ii) OH
      → +
(deprotection step)

Br
o-Bromoaniline p-Bromoaniline
Nitration
NH2 NHCOCH3 NHCOCH3 NHCOCH3
NO2
(CH 3CO)2O HNO3, H2SO4, 15°C
+

NO2
NH2 NH2
+ NO2
(i) H2O, H , heat
+
–
(ii ) OH

NO2
o-Nitroaniline p-Nitroaniline
 EBD_7091
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Sulphonation
Aniline is usually sulphonated by “baking” the salt, anilinium hydrogen sulphate at 180–200°C ; the main
product is the para isomer-
+ – +
NH2 NH3 HSO4 NHSO3H NH3

H2SO4 180–200°C 180–200°C

(—H 2O) 3 hours

–
SO3
Anilinium Sulphamic Sulphanilic
Aniline
hydrogen sulphate acid acid
It is believed that sulphonation of amines proceeds by a mechanism that is entirely different from ordinary
aromatic substitution.
Sulphanilic acid (p-Aminobenzenesulphonic acid) is a salt of special type, called a dipolar ion* (sometimes called
a Zwitterion). It is formed by the reaction of on acidic group (—SO2OH) and a basic group (—NH2) that are part of the
same molecule, hence it is also called inner salt. It is interesting to note that its properties are different from that of a typical
amine and a sulphonic acid. Such properties are (a) high melting point, (b) insolubility in water and organic solvents, (c)
solubility in aqueous NaOH, and (d) insolubility in aqueous HCl. These properties can be explained on the basis of its
structure.
(a) High melting point is due to its ionic nature.
(b) Insolubility in organic solvents is also due to its ionic nature. Its insolubility in water is typical of dipolar salts.
Not all salts dissolve in water.
(c) Its solubility in aq. NaOH is because of transference of H + from the weakly acidic —NH3+ group to strongly
basic OH– ion to form p-aminobenzene sulphonate ion (II), which, like most sodium salts, is soluble in water.

+
NH3 NH2
–
HCl OH
No reaction ←  →

– –
SO3 SO3
I (Insoluble in water) II (Soluble in water)

(d) Its insolubility in aq. HCl is due to the fact that the —SO3– ion is too weak base to accept H+ from strong acids
(recall that sulphonic acids are strong acids, hence their anions are very weak bases).

1. Account for the fact that p-aminobenzoic acid, p-NH2C6H4COOH, does not exist as a dipolar ion, although 2-aminoethanoic acid
(glycine) exists as a dipolar ion.

Friedel-Crafts reactions are normally not successful to unprotected anilines.

NHCOCH3 NHCOCH3
CH2CH3 CH2CH3
CH3COCl
AlCl 3

COCH3
2-Ethylacetanilide 4-Acetamido-3-ethylacetophenone

* A dipolar ion is formed only when a molecule contains both an amino as well as an acidic group, and the amine is more basic than the
anion of the acid.
 965
Coupling reaction. Aniline having a strongly activating (—NH2) group undergoes coupling reaction with
benzenediazonium salt (a weak electrophile).
+
+ H
ArN2 + NH2 Ar—N = N NH2

A weak electrophile A strongly p-Aminoazobenzene

activated ring

Nitrosation. In an electrophilic aromatic nitrosation, the attacking reagent is nitrosonium ion. The nitrosonium
ion is a very weak electrophile and hence nitrosation can take place only in rings bearing powerfully activating
dialkylamino (—NR 2) or hydroxy (—OH) group, i.e., in tert-amines and phenols.

N(CH3)2 N(CH3)2
+
NO
 →

NO
N, N-Dimethylaniline p-Nitroso–N, N– dimethylaniline

1. Complete the following reaction by supplying structure to the bracketed compounds.

NH2 NH2
1 mol of
(a) + Glyoxal [E] (b)   → [F]
HONO, 5°C
NH2 NH2

C H CHO
6 5 HNO 3 H3 O+
(c) Aniline → [G] → [H] + [I] → [J] + [K] + [L]
2. Arrange the following amines in their decreasing basic character.

NH2 NH2 CH2NH2 NH2

(a) , and (b) and

N N
H

20.3 Preparation and Reactions of Diazonium Salts

When a primary aromatic amine dissolved or suspended in cold aqeuous mineral acid, is treated with sodium
nitrite, arenediazonium salts are formed.
0 − 5 °C
Ar—NH2 + NaNO2 + 2HX → Ar—N ≡ N+X– + NaX + 2H2O
1° Aromatic amine A diazonium salt
As described earlier, aryl diazonium ions are substantially more stable than alkyl diazonium ions, and are of
enormous synthetic value. The important synthetic reactions of diazonium salts may be divided into two classes. (a)
replacement reactions, in which nitrogen is lost as N2 and its place is taken by some other atom or group, and (b) coupling
reactions, in which the nitrogen is retained in the product.
1. Reactions involving replacement of —N+ ≡ N. Diazonium group can be replaced easily be any one of a number
of groups or atoms like —F, —Cl, —Br, —I, —CN, —OH, —H, and —NO2. Most of these replacement reactions do
not require any special and drastic condition ; simply the requisite reagent is added to the solution of diazonium
salt which is then gently warmed. The required substituted compound is formed along with the evolution of
nitrogen.
Ar—N+ ≡ N + : Z → Ar—Z + N2
 EBD_7091
966
(a) Replacement of the —N2+ group by —Cl, —Br, or —CN (the Sandmeyer reaction). Arenediazonium salts react with
cuprous chloride, cuprous bromide, and cuprous cyanide to give products in which diazonium group has been
replaced by —Cl, —Br, and —CN respectively. These reactions are known as Sandmeyer reactions.
CuX
Ar—N2+X– ¾¾® Ar—X + N2 (X = —Cl, —Br, —or—CN)
Sometimes the synthesis is carried out by a modification known as the Gattermann reaction, in which copper
powder and hydrogen halide (HCl or HBr) are used in place of cuprous halide.
(b) Replacement by —NO2 group
NaHCO3
Ar—N+2Cl– + NaNO2 ¾¾¾¾¾¾¾® Ar—NO2 + N2
Cu2 + or Cu 2O

(c) Replacement by —I. This can simply be achieved by mixing the diazonium salt with potassium iodide at room
temperature.
Ar—N2+X– + I– → Ar—I + N2 + X–
(d) Replacement by —F. The diazonium group can be replaced by fluorine by treating the diazonium salt with
fluoroboric acid (HBF 4). The precipitated diazonium fluoroborate is isolated, dried and heated until
decomposition occurs to yield the aryl fluoride. This reaction is known as Balz-Schiemann reaction.

HBF4 heat
Ar—N2+X– ¾¾® Ar—N2+BF4–↓ ¾¾® Ar—F + BF3 + N2
(e) Replacement by —OH. Diazonium salts react with water, of course slowly at low temperature, even ice cold, and
vigorously at room or high temperature to yield phenols and this is the reason why these salts are used immediately
after preparation.
heat
Ar—N2+X– + H2O ¾¾® Ar—OH + N2 + H+
This is the most general method for the preparation of phenols. Sulphuric acid is normally used instead of
hydrochloric acid in the diazotization steps so as to minimise the competition with water for capture of the
cationic intermediate ; HSO4– is less nucleophilic than Cl–.
As we shall see later, the phenol so formed may undergo coupling reaction with the unreacted diazonium salt.
Since this coupling takes place easily in alkaline medium, we can minimize this further by making the solution
more acidic ; for which diazonium solution is added slowly to a large volume of boiling dil. H2SO4.
Diazonium group can be replaced by —OH group also by adding cuprous oxide to a dilute solution of the
diazonium salt containing a large excess of cupric nitrate.

Cu 2 O
Ar—N2+ HSO4– ¾¾¾¾¾¾¾® Ar—OH
Cu2 + , H 2 O

This variation of Sandmeyer reaction is a much simpler and safer procedure than the above older method for
preparing phenol.
(f) Replacement by hydrogen (deamination via diazotization). This can be brought about by a number of reducing
agents, e.g., H3PO2, C2H5OH, NaBH4, or Na2SO3; most useful of these is hypophosphorous acid, H3PO2.
Ar—N2+X– + H3PO2 + H2O → Ar—H + H3PO3 + HX
Aniline can directly be converted to benzene by carrying out its diazotization in presence of hypophosphorous
acid for which amine is dissolved in hypophosphorous acid and sodium nitrite is added (diazonium salt is
reduced as fast as it is formed).

3 2 2 H PO , NaNO
Ar—NH2 ¾¾¾¾¾¾® Ar—H + N2 + H2O
Replacement of —NH2 group via the diazonium group by hydrogen is very useful reaction because introduction
of —NH2 group (precursor of —N2X) can be used to introduce the new group in a p-position which is sometimes
not possible by direct reaction as illustrated in the following preparation.
(g) Replacement by phenyl group (Gattermann reaction) :

+ – Cu bronze
H3 C N 2 Cl powder, heat H3C CH 3
 967
Preparation of m-bromotoluene : Here the two o, p-directing groups are situated meta for each other, hence
neither bromination of toluene nor methylation of bromobenzne would yield the required m-bromotoluene.

CH3 CH3

bromination methylation

Br
(Not formed) Br

However, this can be prepared from toluene in the following way.

CH3 CH3 CH3

CH3
+
HNO3 Fe, H (CH 3CO)2O
H2SO4 (to reduce the activating
effect of —NH 2)

NO2 NH2 NHCOCH3

Toluene p-Nitrotoluene p-Toluidine (—NHCOCH3 is much stronger
(separated from o-isomer) o, p-director than —CH3)

CH3 CH3 CH3 CH3

– NaNO2 H3PO2
Br2 OH , H2O
HCl Br Br
Br Br
+ –
NHCOCH3 NH2 N2 Cl
m-Bromotoluene

1. In diazotisation of arylamines, excess of mineral acid is used. Explain.

2. Complete the following by supplying structures to the bracketed compounds.

NO2

NaNO4, HBF4 NaNO2 NH4HS heat

(a) [A] [B] [C] [D]
5°C Cu2O
heat
NH2

NH2

H 2SO 4 NaNO 2 , HCl N, N-Dimethylaniline

(b) →
heat
[A] →
5°C
[B] → [C]

3. Give intermediate steps to carry out the following transformations.

(a) Toluene to p-toluic acid (b) Nitrobenzene to m-bromophenol
(c) p-Nitroaniline to 1, 2, 3-tribromobenzene (d) Benzene to 1, 3, 5-tribromobenzene
(e) Benzene to m-bromochlorobenzene (f) Aniline to p-dinitrobenzene
(g) C6H5NH 2 to C6H5D.
4. Direct bromination of toluene gives a mixture of o- and p-bromotoluenes which are very difficult to separate, so devise a scheme
that can be used for converting toluene to o- and p-bromotoluenes.
 EBD_7091
968
2. Coupling reactions of diazonium salts. Like nitrosonium ion (+NO), arenediazonium ions (ArN2+) are weak
electrophiles, and are thus capable of attacking only very reactive rings. Hence the aromatic ring undergoing
attack by the diazonium ion must contain a powerfully electron-releasing group, generally —OH, —NR 2, —
NHR, —or NH2. Substitution mainly occurs para to the activating group.

+
N≡N + ← G → N=N G
–
X
G = —NH2, —NHR, An azo compound
—NR2, or —OH

(a) Couplings between arenediazonium cation, and phenols take place most rapidly in slighlty alkaline solution.
In alkaline medium, an appreciable amount of phenol is present as a phenoxide ion which is more reactive
toward electrophilic substitution than the parent phenol.
+ – 0°C, NaOH
N ≡ N Cl + OH      → N=N OH
H2O

p-Hydroxyazobenzene
However, the solution should not be too alkaline because in strongly alkaline medium the arenediazonium ion
exists in equilibrium with an un-ionized diazohydroxide and diazotate ; neither of these couple.

NaOH NaOH
¾¾¾® Ar—N = N—O– Na+
¾¾¾® Ar—N = N—OH ¬¾¾¾
Ar—N ≡ N+ OH– ¬¾¾¾
H+ H+

Arenediazonium ion Diazohydroxide Diazotate ion

(couples) (does not couple) (does not couple)
(b) Couplings between arenediazonium cation and amines take place mostly in slightly acidic solutions (pH 5–7).

+ – 0°C,
N ≡ N Cl + N(CH3)2  → N=N N(CH3)2
CH3COONa, H2O

– + –
O3S N≡ N + N(CH3)2 O3S N=N N(CH3)2

Methyl orange

The higher acidity increases the amount of protonated amine which is unreactive toward electrophilic substitution

HA +
NR2 →
 → N R2
H
Amine Aminium salt
(couples) (does not couple)

Azo compounds are usually intensely coloured because the azo linkage (—N = N—) brings the two aromatic
rings into conjugation. This gives an extended system of delocalized π electrons and allows absorption of light
in the visible region. Because of their intense colours, many azo compounds are extensively used as dyes. Azo
compounds undergo reduction in the following manner.

Sn, NaOH H H
(i) Ar—N = N—Ar′ ¾¾¾¾¾¾¾® Ar— N — N —Ar
(mild reduction) A hydrazo compound

(i) SnCl 2 , H + ; (ii) OH -

(ii) Ar—N = N—Ar′ ¾¾¾¾¾¾¾¾¾® ArNH2 + H2NAr′
(vigorous reduction)

Azo compounds can exist in cis and trans forms ; the former being less stable due to steric strain.

Ar Ar
Ar
:

N=N N= N
:
:
:

cis-Azobenzene Ar
trans-Azobenzene
 969
3. Reduction. Arenediazonium salts are reduced to phenylhydrazine hydrochloride by means of SnCl2 and HCl or
with sodium sulphite.

SnCl 2 , HCl
C6H5—N ≡ N+ Cl– ¾¾¾¾¾® C6H5NHNH2 . HCl
or Na 2 SO 3
Benzenediazonium chloride Phenylhydrazine hydrochloride

20.4 Illustrative Examples

Example 1 :
Supply the structure of bracketed compounds in each of the following conversions.

[B] / Conc. H 2 SO 4 NaNO 2 , HCl CuCl

(a) [A] Acid ¾¾¾¾¾¾® [C] ¾¾¾¾¾® [D] ¾¾® p-Nitrochlorobenzene
5°C

C2 H 5 Br HNO 3 NBS excess

(b) C6H6 ¾¾¾® [A] ¾¾¾® [B] ¾¾® [C] ¾¾¾® [D]
AlCl 3 H 2 SO 4 NH3

(i) H +O
(CH 3 CO)2 O ClSO 2 OH NH 3 3
(c) C6H5NH2 ¾¾¾¾® [A] ¾¾¾¾® [B] ¾¾® [C] ¾¾¾¾®
– [D]
(ii) OH

C6 H 5N 2+ Cl - 6 5 2C H N + Cl -
(d) [B] ¬¾¾¾¾¾ HO NH2 ¾¾¾¾® [A]
H+ OH –

C2H5
NHCOCH3
HNO 3 OH – Cl 2
(e) ¾¾¾¾® [A] ¾¾® [B] ¾¾® [C]
H 2SO 4

Solution :
(a) Proceed backward with the structure of the knwon compound, p-nitrochlorobenzene and the knwon reagent.

+ –
Cl N2 Cl NH2 COOH

CuCl NaNO [B] is N3H / conc. H2SO4

←     ←   2 ←        →
Sandmeyer HCl, 5° (Curtius reaction)
reaction

NO2 NO2 Cl Cl

[D] [C] [A]

CH2CH3 CH2CH3 CH(Br)CH3 CH(NH2 )CH3

(b) ; ; ;

NO2 NO2 NO2

[A] [B] [C] [D]
 EBD_7091
970

NHCOCH3 NHCOCH3 NHCOCH3 NH2

(c) ; ; ;

SO2Cl SO2NH2 SO2NH2

(d) HO NH2 HO NH2

N = NC6H5 N = NC6 H5
[A] [B]
C2H5 C2H5 C2 H5
NHCOCH3 NH2 NH2

(e)
O2N O2N O2N Cl
[A] [B] [C]

Example 2 :
Give steps involved in the following conversions.
(a) C6H5NH2 to C6H5D (b) C6H6 to optically active sec-butylbenzene
(c) Aniline to benzoic acid.
NH2 C2H5 C2H5
NH2 Cl
(d) (e)
O2N Cl Cl
CH2 NH2

(f) Benzene to ethyl m-fluorophenyl ketone (g)   →

NO2
Solution :
2 NaNO DPH 2 PO 2
(a) C6H5NH2 → C6H5N2+Cl– → C6H5D
HCl, 5° C
CH3 CH3
CH CH
C2H5 C2H5
CH3 AlCl 3 (i) HNO3, H2SO4
(b) + ClCH  →
(ii ) Sn, HCl
CH2CH3 (iii) OH
–

sec-Butyl chloride racemate

NH2
reacemate
CH3 CH3
CH CH
C2H5 C2H5
resolve with (i) HONO, 5°C
 →
(+)- or (–)- (ii ) H3PO2
tartaric acid

NH2
separated enantiomers separated
sec-Butylbenzenes
 971

+
NH2 N2 CN COOH

HONO CuCN hydrolysis

(c) 5°C

Aniline Benzoic acid

NO2 NHCOCH3 NHCOCH3

HNO (i) Sn, HCl HNO

(d)  3→ →   3→
H2SO4 (ii) (CH3 CO)2 O H2SO4

Benzene
NO2

NH2 NH2 CN CH2NH2

–
OH (i) Sn, HCl (i) HONO, 5°C LiAlH
→   – →   4→
(ii ) OH ( ii) CuCN

NO2 NH2 CN CH2NH2

C2H5 C2H5 C2H5 C2H5

NH2 Cl – Cl Cl
(i) HONO, 5°C (i) Sn, HCl ; OH H3PO2
(e)
(ii ) CuCl (ii ) HNO2, 5°C
– +
O2N Cl O2N Cl ClN2 Cl Cl

COCH2CH3 COCH2CH3

CH3CH2COCl (i) HNO3, H2 SO4

(f) –
AlCl3 (ii) Fe, HCl ; OH
NH2
Benzene

COCH2CH3 COCH2 CH3

HONO, 5°C ( i) HBF4

+ – ( ii) heat
N2 Cl F
Ethyl m-fluorophenyl ketone

(i) HNO3, H2SO4 CH3COCl

(g) –
(ii) Fe, HCl ; OH

Isopropylbenzene
(Cumene) NH2 NHCOCH3

(I) HNO3 , H2 SO4 HONO, 5°C H3PO2

–
(ii ) OH
NO2 NO2 NO2
+
NH2 N2
m-Isopropylnitrobenzene
 EBD_7091
972

Example 3 :
An unknown compound X containing nitrogen and chlorine is readily soluble in water to give a solution that
turns blue litmus red. Titration of X with standard sodium hydroxide gives a neutralization equivalent of 129.
When compound X is treated with [Link], a liquid containing nitrogen but no chlorine separates out. Liquid
Y gives a red precipitate on treatment with nitrous acid and -naphthol under suitable conditions. Assign structure
to X and Y.
Solution :
Solubility of the compound X in water, and its reaction with NaOH to form Y with the loss of chlorine indicates that
X is the hydrochloric acid salt. Further compound Y (not having chlorine) seems to be 1° primary aromatic amine
due to its reaction with HCl (diazotisation) and β-naphthol (coupling) to form red precipitate. The 1° aromatic
amine hydrochloride should be C6H5NH3+Cl–, indicated by its N.E. 129.
C6H5NH3+Cl– + H2O → C6H5NH2 + H2O + HCl
(X) NE = 129 (Y)
C6H5NH3+Cl– + NaOH → C6H5NH2 + H2O + NaCl
(X) (Y)

Example 4 :
Deduce structure of the compound (A) of the formula C7H7NO2 which is insoluble in dil. acid and base. On vigorous
oxidation, it gives compound (B), C 7H5NO4 which is soluble in dil. aqueous NaHCO3 and gives two isomeric
monochloro substitution products.
Solution :
Since the compound (A), C7H7NO2 is insoluble in dil. acid and base, and its nitrogen is not removed on oxidation,
so it should contian —NO2 group as one of the substitutents which is present as such in B. Hence the other
substituent in B (C7H5NO4) should be —COOH as indicated by its solubility in aq. NaHCO3. So, the compound B,
C7H5NO4 is C6H4(NO2)COOH. The two substituents must be present in para to each other so as to explain the
formation of two isomeric monochloro substitution products. Thus (A) should be p-nitrotoluene

COOH R CH3

vigorous
Two ← or
possible oxidation
sites
NO2 NO2 NO2
(B) (A)

Example 5 :
Deduce a possible structure for the compund (A) of the formula C8H9NO which is insoluble in dil. acid and base. On
treatment with KMnO4 in H2SO4 , it gives compound B, which is free of nitrogen, soluble in aqueous NaHCO3 and
gives only one mononitro substitution product.
Solution :

KMnO 4 nitration
[A] → [B] ¾¾¾¾® One mononitro derivative
H 2 SO 4

C8H9NO (soluble in aq. NaHCO3)

 973
Students are advised to start the problem from any knwon reaction fact or strucutre given in the problem. For example,
in the present question it is given that compound [B] is soluble in aq. NaHCO3, so it must contain —COOH group.
Further it is given that (B) forms only one mononitro derivative which indicates that it should contian two —COOH
groups and that too in para to each other.
COOH COOH
X
Substitution
     →

COOH COOH
(B) All four positions
are equivalent
Now since compound B is obtained by acidic –KMnO4 oxidation of A, A should have two substituents and one
substituent must contain nitrogen in such form which is insoluble in acids and bases and is liable to be converted to
—COOH group by KMnO4 + H2SO4.
The nitrogen containing group which coincides with all the given* characteristics is —CONH2. Hence the other
substituent in A (C8H9NO) should be —CH3 and that too in para position to explain the formation of B.
CH3 COOH

KMnO
  4 →
H2SO4

CONH2 COOH
(A) C8H9NO (B)

Example 6 :
An azo compound (X) is cleaved by stannous chloride to form two amines, namely 2-methyl-4-aminophenol (A) and
3-bromo-4-aminotoluene (B). Deduce the structure of the azo compound. Can both of the amines (A and B) be used
for preparing the parent azo compound by coupling reaction, if so give the synthesis of the azo compound.
Solution :
In such questions, first draw structures of both of amines in such a way that their amino groups face each other. Now
replace the two amino groups by azo linkage, —N = N—.

CH3 Br CH3 Br
SnCl2
HO NH2+ H2N CH3 ←   HO N=N CH3

(A) (B) (X)

The two possible pairs that can be used for preparing the azo compound X by coupling are

CH3 Br CH3 Br
+ –
HO N2 Cl + CH3 or HO + ClN2 CH3

(From amine A) (From amine B)

However, the first combination is not feasible because the benzene ring does not bear reactive —OH or —NH 2
group, i.e., it is not sufficiently reactive to be attacked by the electrophilic diazonium cation.

* Other important N containing groups are —NO2 (not removed by KMnO4 + H2SO 4), —NH2, —NHCOCH3, etc. (liable to destroy the
benzene ring).
 EBD_7091
974

Example 7 :
A nitrobenzene derivative (A) of the formula C8H9NO2 when treated with metallic tin and NaOH, it forms compound
(B). Compound B rearranges to an aromatic diamine (C) on treatment with strong mineral acid. Compound (C) is
treated first with nitrous acid at low temperature and then heated with ethanol to give 3, 3 -diethyldiphenyl. Deduce
the structure of the compound (A) and write the reactions involved.
Solution :
C 2H 5 C 2H 5
Sn HCl (i) HNO 2 , 5°C
C8H9NO2 → [B] ¾¾® [C] ¾¾¾¾¾¾¾®
NaOH (ii) C2 H 5 OH, heat

[A] C6H5NO2.C2H4
The above series of reactions lead to following points.
(i) Compound (C) is a diamine and is formed by treating [B] with strong HCl, involving rearrangement, [C] must
have two —NH2 groups in para positions.
C2H5
C2H5 C2H5 C2H5
HCl
H2N NH2 NHNH

[C] [B]
Thus the compound [B] must be a substituted hydrazobenzene with undergoes rearrangement (benzidine
rearrangement) on treatment with strong mineral acid.
(ii) Formation of hydrazobenzene by the reduction of compound A with Sn and OH– indicates that A must be
2-ethylnitrobenzene.
C2H5 C2H5
C2H5
Sn
2 NO2  →
– NHNH
OH

[A] [B]

Example 8 :
Pyridine undergoes electrophilic substitution at position 3 rather than at 2 or 4. Explain.
Solution :
Due to the presence of N in ring, pyridine behaves like a strongly deactivated benzene (e.g. nitrobenzene), thus positions
2 and 4 are deactivated towards electrophiles. This is evident by the fact that Friedel–Crafts reactions fail while other
electrophilic substitutions require unusually strong conditions. Thus formation of 3-substituted product (the relatively
less deactivated position) can be explained by higher stability of the corresponding intermediate.
Attack at 3-position :
+
H H H
NO2 NO2 NO2
+ +
N N N
Attack at 2-position :

+ +
H H H
N NO2 N N
+ NO2 NO2
No octet on N (Unfavourable)
Thus the intermediate corresponding to 2- (as well as 4-) substituted product is less stable than the 3-substituted
intermediate.
 975

Example 9 :
2-Chloropyridine when treated with sodium methoxide gives 2-methoxypyridine, while no such reaction occurs
with 3-chloropyridine. Explain.
Solution :
This is an example of nucleophilic substitution, recall that pyridine is deactivated toward attack by electrophiles, it is
activated toward attack by nucleophiles. Thus if a good leaving group is present either at 2 or 4 position, a nucleophile
can attack and displace the leaving group. The intermediate due to attack at 2 or 4 position is stabilized by delocalization
of the negative charge, since this stabilization is not possible if attack occurs at the 3-position, 3-chloropyridine is not
converted to 3-methoxypyridine.
Nucleophilic attack at C-2

–
OCH 3– – : –
: –Cl
OCH3 NH2 OCH3
..
N Cl N
. .– Cl N
.. OCH3 .N. Cl N OCH3
N has octet, II III
–ve charge on N
(especially stable)
I

Similar situation arises in case of 4-chloropyridine.

Nucleophilic attack at C-3 (not observed)

Cl . –. OCH3 OCH3 OCH3

OCH3–
Cl –: Cl Cl
N N N N
–:

None of the structure has –ve charge on N (hence unfavouable situation)

Example 10 :
Propose mechanism for the following reaction.

H2 , Pt

O CN N
H
You may use an acid or a base, wherever you require.
Solution :

+
H2 H2 H
Pt Pt .. + ..
.O. NH2 O:
O C≡N O C = NH + O:
NH2 NH2
H H H ..

+
base H
+ ..
N N N
OH H : OH
.. H + OH
.. 2 H
H

–H2O H2, Pt
base
.. +
+ N N N N
H H ..
H
 EBD_7091
976

Example 11 :
Draw all the resonating structures of the 2-substituted intermediate obtained by treating pyrrole in acetic anhydride
(CH3CO+ is the electrophile). Is there any difference in the relative stability of these structures?
Solution :

+
H H H
+ +
N COCH3 N COCH3 N COCH3
H H H
Every atom has a full octet
(especially stable)

Example 12 :
An optically active naturally occurring toxic liquid C8H17N (X), in hemlock that was said to cause Socrates death
dissolves in aq. HCl and gives no gas will nitrous acid. It gives a precipitate with benzenesulphonyl chloride in
presence of NaOH. when treated with excess of methyl iodide, then with moist oxide and finally heated, it gives a
compound (Y) C10H21N. Compound (Y) is treated similarly as (X) and finally gives 1, 4-octadiene and 1, 5-octadiene.
Suggest structure to (X) and )(Y) and explain all the reactions. Is there any possible structural isomer of (X); if so give
the complete set of reaction with this?
Solution :
(i) The given reactions (solubility in aq. HCl, no gas with HONO and a precipitate with C6H5CO2Cl / NaOH)
indicate that the given compound is a secondary amine.
(ii) Since the given compound eliminates nitrogen by two sequence of Hofmann degradation, N must be present in
the ring.
(iii) Formation of two unbranched alkenes as the final products indicates that the alkyl group or groups consisting
of 3-C must be present on the a-carbons and it must be unbranched. Two possibilities arise : (a) one CH3 and one
C2H5 groups are present on the two a-carbons, (b) one n-C3H7 group is present on one of the a-carbons. However,

(I) 2CH3 I β (i) CH3I

(ii) Ag2 O, heat (ii) Ag 2 O, heat +
N CH2CH2CH3 N β 1, 4-octadiene 1, 5-octadiene
H
H3C CH3
2- n -Propylpiperidine, [Y]
Coniine [X]

(i) 2CH3I (i) CH3I

+
(ii) Ag2O, Δ (ii) Ag2O, heat
N N
H H3C CH3 1, 6-Octadiene 1, 5-Octadiene
2-Ethyl-6-methyl
piperidine, isomer of (X)
 977

EXERCISE 20.1 (MCQ - ONE option correct)

1. Which of the following is not a property of sulphanilic acid ? (a) C6H5CH 2NH2 (b) C6H5COOH
(a) It is soluble in [Link] (c) C6H5NHCH3 (d) C6H5 NH2 .
(b) It is soluble in aq. HCl 7. How many diazo group will be introduced when resorcinol is
(c) It is insoluble in organic solvents treated with excess of benzenediazonium chloride in alkaline
(d) It does not melt but decomposes. medium ?
(a) 1 (b) 2
2. H 3C N=N NMe2 can be produced (c) 3 (d) Nil.

by coupling reaction of which of the following pair? NH2

Conc. HNO 3
(a) H 3C NH 2 + NMe2 8. → X. Here X is mainly
Conc. H 2SO 4

(a) o-Nitroaniline
(b) H 3C + H2N NMe2 (b) p-Nitroaniline
(c) a mixture of (a) and (b)
(c) Both (a) and (b)
(d) m-Nitroaniline.
(d) Neither of the two.
9. What should be the final product in the following reaction ?
3. Arrange the following compounds in decreasing order of coupling
with benzenediazonium chloride.
O2 N NH 2 + 2ICl   → Main product
– +
OH O NH3 NH2
NH2 NH2
Cl Cl I I
(a) (b)
(I) (II) (III) (IV)
(a) IV > I > II > III
(b) II > I > IV > III NO2 NO2
(c) II > IV > I > III
(d) II > III > IV > I. NH2
4. Arrange the following diazonium cation in decreasing order of I Cl
coupling with phenol. (c) (d) No reaction.
+ + + +
N2 N2 N2 N2
NO2 NO2
10. Which of the following has lowest pK b value ?
(a) Benzylamine (b) Aniline
(c) Acetanilide (d) p-Nitroaniline
CH3 NO2 NO2 11. Which of the following is stronger than aniline ?
(I) (II) (III) (IV) NH2
(a) I > II > III > IV NHCOCH3
(b) IV > III > II > I
(c) IV > III > I > II (a) (b)
(d) II > I > III > IV.
5. Predict the nature of P in the following reaction. COCH3
NH2 NO2 NH2
CH3
+ → P (c) (d) None.

12. The increasing order of pKb values for the three anilines (I, II and
CH3
III) is
NO2 NH2 NH2 NH2

(a) O O (b) HN CH3

NO2
(c) H 2N CHO (d) H2 N COOH
NO2
6. Predict the product [B] in the following series of reactions. I II III
3 CHCl H 3 O+ (a) I < II < III (b) III < II < I
C6H5NH2 → [A] → [B] (c) I < III < II (d) II < I < III.
KOH
 EBD_7091
978
13. Arrange the following amines according to their decreasing Kb 21. Which of the following statement is not correct regarding aniline?
values. (a) It is less basic than ethylamine
(b) It can be steam distilled
NH2 NH2 NH2 NH2 (c) It reacts with sodium to give hydrogen
(d) It is soluble in water
22. Benzenediazonium chloride on reaction with phenol in weakly
basic medium gives
(a) diphenyl ether (b) p-hydroxyazobenzene
(c) chlorobenzene (d) benzene
CH3 OCH3 CF3 NO2 23. The correct stability order of the following resonance structures is
I II III IV + – + –
(a) I > II > III > IV H2C = N = N H2C – N = N
(b) IV > III > II > I (I) (II)
(c) II > I > III > IV – + – +
(d) II > I > IV > III. H 2C – N = N H2C – N = N
14. Of the four orders given below for the basic character of the four (III) (IV)
compounds, which one is correct order ?
(a) I > II > IV > III (b) I > III > II > IV
CH3 NH2 NH2 (c) II > I > III > IV (d) III > I > IV > II
24. Which of the following gives paracetamol on acylation?
OH OH
NH2
N N N (a) (b)
I II III IV NH2
(a) IV > III > II > I
OH
(b) IV > I > II > III
(c) IV > II > I > III NH2
(d) I > II > IV > III.
15. The correct order for decreasing basic character of the four amines (c) (d)
I to IV is
NH2
NH2 25. Which of the following is strongly basic :
NH2
CH3NH2 NH2
NH
N
(a) (b)
I II III H IV
(a) I > II > III > IV (b) I > IV > III > II CH2
(c) I > II > IV > III (d) IV > I > III > II. NH2 NH2
16. Which of the following is most basic, and which one is least ?
O O (c) (d)

– –
NH NK N N 26. Which of the following statements is not correct?
(a) Aliphatic amines are stronger bases than ammonia
(b) Aromatic amines are stronger bases than ammonia
O (c) The alkyl group in alkyl ammonium ion stabilizes the ion
I II III IV more relative to the amine
(a) II and IV respectively (b) II and I respectively (d) The aryl group in aryl ammonium ion stabilizes the ion less
(c) I and II respectively (d) IV and I respectively. relative to the amine
17. When a 2°aromatic amine hydrochloride is heated, it leads to the Cl Cl
formation of 1° amine hydrochloride, the reaction is known as
(a) Hofmann degradation
(b) Fries migration 27. Δ
(c) Hofmann Martius rearrangement X+Y
(d) None of the three.
Regarding X and Y which of the following statement is/are correct?
18. Fluorobenzene can be prepared from aniline via diazotisation,
I. Both X and Y are aromatic
the reaction is known as
II. One of them is anti-aromatic
(a) Sandmeyer reaction (b) Gattermann reaction III. All the carbon in X and Y are sp2 hybridized
(c) Schiemann reaction (d) Modified Sandmeyer reaction IV. One of the above species can give addition reaction with
19. Benzenediazonium chloride on reaction with phenol in weakly
basic medium gives Cl
(a) diphenyl ether (b) p-hydroxyazobenzene pyrrole and can produce as a major product.
(c) chlorobenzene (d) benzene. N
20. A positive carbylamine test is given by (a) I, III (b) I, III, IV
(a) N, N-dimethylaniline (c) III, IV (d) II, IV
(b) 2,4-dimethylaniline 28. Benzenediazonium chloride forms coloured compound when
(c) N-methyl-o-methylaniline treated with :
(d) p-methylbenzyl amine (a) Phenol (b) Cresol
(c) Resorcinol (d) All of the above
 979
29. Which of the following statements is correct? 32. Electrophilic aromatic substitution of pyridine resembles with
(a) Reaction of stereoisomeric alcohol with SOCl2 in presence (a) benzene (b) aniline
of pyridine gives the product with retention of configuration (c) nitrobenzene (d) none of these
(b) Solvolysis of secondary substrate is found to depend upon 33. For the diazonium ions, the order of reactivity towards diazo-
only the nucleophilic power of solvent not upon the coupling with phenol in the presence of [Link] is
ionization power of solvent.
+ + +
(c) p-Aminobenzoic acid exists as Zwitterion in aqueous solvent +
N2 N2 N2 N2
(d) Coupling of diazonium salt with phenol is carried out in
mildly alkaline solution and with amines in mildly acidic
solution I II III IV
30. Which of the following substances represent a colourless
substance? NO2 N(CH3)2
CH3 OCH3
N C6H5
(a) I < IV < II < III (b) IV < II < I < III
H5C6 N (c) I < II < IV < III (d) III < IV < II < I
(a) 34. When aniline is treated with acetyl chloride in presence of
O anhydrous aluminium chloride, the main product is
N (a) o - aminoacetophenone(b) p-aminoacetophenone
C6H5
(b) (c) both (a) and (b) (d) m-aminoacetophenone
H5C 6 N 35. Benzenediazonium chloride when treated with phenols gives azo
NH C6H5 dyes, to get best result the pH of the medium should be
(c) (a) around 4 (b) around 8
H5C6 NH (c) around 10 (d) 12
(d) None of the above 36. Amongst the compounds given, the one that would form a brilliant
31. Pyrrole and pyridine both are basic and form salts with acids? colored dye on treatment with NaNO 2 in dil. HCl followed by
+ addition to an alkaline solution of β-naphthol is
+
H
.. + .. H
+
N N N N
H H2 H
I II (a) (b)
III IV
Which of the following statement is true regarding the aromatic
character of the four species?
(a) All the four are aromatic
(b) I, III and IV are aromatic (c) (d)
(c) I, II and III are aromatic
(d) I and III are aromatic

EXERCISE20.2
3. Which of the following can exist as inner salt ?
DIRECTIONS for Q. 1 to Q. 15 : Multiple choice questions with (a) p-Aminobenzenesulphonic acid
one or more than one correct option(s). (b) p-Aminobenzoic acid
(c) Aminoacetic acid
1. Which of the following reaction can be used for preparing ani-
(d) Alanine
line ?
4. Which of the following pairs show coupling reaction ?
N 3 H, conc. H 2 SO 4
(a) C6H5COOH → + –
N2 Cl OCH3
H3 O+
(b) C6H5NC →
LiAlH 4 (a) +
(c) C6H5NC →
Br2/NaOH
(d) C6H5CONH2 → + –
2. Examine the following two structures for the anilinium ion, pre- N2 Cl
dict which of the following statement is FALSE regarding the NO2 OCH3
two canonical structures for anilinium ion ? (b) +
+
N H3 NH3

⊕ NO2
← →
+ –
N2 Cl CH3
(I) (II)
O2N NO2
(a) II is not an acceptable canonical structure because
carbocations are less stable than ammonium ions. (c) +
(b) II is not acceptable canonical structure because nitrogen
has 10 valence electrons. H3C CH3
(c) II is not acceptable canonical structure because it is non- NO2
aromatic.
(d) II is acceptable structure. (d) Diazotised sulphanilic acid + Dimethylaniline
 EBD_7091
980
5. Which of the following statement is false regarding following 13. The correct orders are :
reaction ? COOH COOH
Cl CH3
1 NO2 (a) > ......acid strength
6 2 heat
+ NH3 →
5 3 pressure
4 COOH COOH
CH3
Cl
(a) No reaction is possible because —Cl is present on benzene (b) > ..... rate of decarboxylation
ring. by soda lime
(b) A nucleophilic substitution will take place in which both NH2 NH2
—Cl will be replaced by two —NH2 groups.
(c) A nucleophilic substitution will take place in which only C2H5
—Cl attached on C1 will be replaced by —NH2. (c) > ..... basic strength
(d) A nucleophilic substitution will take place in which only
—Cl attached on C4 will be replaced by —NH2. Me Me
6. Libermann’s nitroso reaction is used for testing
(a) 1° amine (b) 2° amine N NH2
(c) phenol (d) 3° amine. Me Me Me Me
(d)
7. Which of the following statement is true regarding reaction of p- >
aminophenol with arenediazonium chloride?
3 2 .... basic strength
–
HO NH2 + ArN2 Cl
+
 → 14. The feasible reactions are :
O O
5 6
(a) Reaction takes place at position 2 in presence of HCl. C CH2NH2
(b) Reaction takes place at position 3 in presence of NaOH. (a) NaBH 4
NH2  →
(c) No reaction occurs.
(d) Four azo groups can be introduced in the molecule.
8. p-Chloraniline and aniline hydrochloride can't be distinguished by OH ONa
(a) Sandmeyer reaction (b) NaHCO3 O2N NO2 O2N NO2
(c) AgNO3 (d) Carbylamine test. NaHCO3
9. Oxidation of A gives p-benzoquinone. A can be : (b) 
→
OH
NH2 NO2 NO2
+CO 2 ↑ +H 2 O
(a) (b)

OH ⊕ –
(c) HCl
OH OH ..  → N
..
N
Cl
N
..
N
H H
(c) (d) H
CH 3 CH 3 CH 3
10. Among the following statements on the nitration of aromatic | | |
compounds, the correct ones are (d) Na/ether
CH 3 − C − Br  → CH 3 − C = CH 2 + CH 3 − C − H
(a) the rate of nitration of benzene is almost the same as that of | |
hexadeutrobenzene. CH 3 CH 3
(b) the rate of nitration of toluene is greater than that of benzene.
(c) the rate of nitration of benzene is greater than that of 15. In which reaction, major product formed is correct
hexadeutrobenzene O
(d) nitration is an electrophilic substitution reaction. NH2
11. When nitrobenzene is treated with Br 2 in presence of FeBr3, the NH2 Br2/ NaOH
major product formed is m-bromonitrobenzene. Statements which (a) + CHBr3 + CO2
are related to obtain the m-isomer are
(a) The electron density on meta carbon is more than that on –
COO
ortho and para positions O
(b) The intermediate carbonium ion formed after initial attack OH OH
of Br+ at the meta position is least destabilised
(c) Loss of aromaticity when Br+ attacks at the ortho and para CHO
CHBr3 + NaOH
positions and not at meta position (b)
(d) Easier loss of H+ to regain aromaticity from the meta
position than from ortho and para positions. →
NH2 N= C
.x. .y. .z.
12. N=N NH2 .....(P) CH3 CH3
CH2 – NH2
The correct statements about the compound (P) is/are : (c) HNO2
O
(a) Nitrogen (x) is most basic in nautre OH
(b) The lone pair of electrons of nitrogen (z) is delocalized in
the aromatic ring HNO
(d) 2 → R − C − OH
R − C − NH 2 
(c) All the nitrogen atoms x, y and z are sp2 hybridized P P
(d) The compound ‘P’ has stereoisomers O O
 981
H O
INSTRUCTION for Q. 16 to 26 : Read the passages given below and 20. → C6 H 5 N 2 X − 2 → C 6 H 5 OH + N 2 + H +
C6 H 5 NH 2 
answer the questions that follow. In the preparation of the above diazonium salt, use of H2SO4 is
preferred to HCl because
PASSAGE 1 (a) sulphuric acid is a stronger acid
2-Chloropyridine when treated with sodium methoxide gives
(b) HSO −4 is less nucleophilic than Cl –
2-methoxypyridine. The intermediate is stabilized by delocalization of
the negative charge; since this type of stabilization is not possible if (c) sulphuric acid absorbs water
attack occurs at the 3-position, hence 3-chloropyridine is not converted (d) None of the three
into 3-methoxypyridine.
21. Coupling reaction is not in feasible in
–
OCH3 + –
OCH3 (a) N2 Cl + OH
..
N Cl N
.. Cl
–
I
+ –
(b) N2 Cl + NO2
–
– :
: –Cl
–
Cl OCH3
N N N + –
.. OCH3 .. Cl OCH3 (c) HO3 S N2 Cl + NMe 2
II III
(d) All are feasible
16. Which of the three resonating structures is especially stable? 22. Which of the following statement is false?
(a) I (b) II (a) Coupling between arenediazonium cation and amines take
(c) III (d) none
place in strongly acidic conditions
17. The unstability of the corresponding intermediate from
3-chloropyridine is because of the fact that (b) Coupling between arenediazonium cation and phenols takes
(a) the intermediate has lesser number of canonical structures place in slightly alkaline medium
(b) none of the canonical structure has negative charge on N (c) Both are correct
(c) both of the above reasons (d) Neither is correct
(d) none of the two
23. In strongly alkaline medium, the arenediazonium cation exists in
18. What would happen if 2-chloropyridine is replaced by 4-
chloropyridine? the following equilibrium
(a) 2-Methylpyridine will be formed NaOH NaOH
+ – – +
(b) 3-Methoxypyridine will be formed Ar – N = N OH Ar – N = N – OH Ar – N = N – ONa
+ +
(c) 4-Methoxypyridine will be formed H H
I II III
(d) No reaction
Which of the above can undergo coupling reaction?
PASSAGE 2 (a) I (b) II
Primary ar omatic a mines react with nitrous acid to yield (c) III (d) II and III
arenediazonium salts.
cold
ArNH 2 + NaNO 2 → Ar − N ≡ N + X − + NaX + 2H 2 O
+ 2HX  PASSAGE 3
1° aromatic Arenediazonium
aniline salt p-Amino-N, N-dimethylaniline is added to a strongly acidic solution
of X. The resulting solution is treated with a few drops of aqueous
Although arenediazonium salts are far more stable than aliphatic
solution of Y to yield blue coloration due to the formation of methylene
diazonium salts, especially at low temperature (0 - 5°), they slowly
decompose even at low temperature, hence always used immediately blue. Treatment of the aqueous solution of Y with the reagent potassium
after preparation. hexacyanoferrate(II) leads to the formation of an intense blue
Secondary amines, both aliphatic and aromatic, react with nitrous to precipitate. The precipitate dissolves on excess addition of the reagent.
form N-nitrosoamines which show Libermann’s nitroso reaction Similarly, treatment of the solution of Y with the solution of potassium
C6 H 5 NHCH 3 + NaNO 2 + HCl 
→ C6 H 5 N(NO)CH 3 hexacyanoferrate (III) leads to a brown coloration due to the formation
N − Methylaniline of Z.
Aryldiazonium ions are substantially more stable than alkyldiazonium
ions, and are of enormous synthetic value. The important synthetic 24. The compound X is
reactions of diazonium salts may be divided into two classes. (a) (a) NaNO3 (b) NaCl
replacement reaction, in which nitrogen is lost as N2 and its place is (c) Na 2 SO 4 (d) Na 2S
taken by some other atom or group, and (b) coupling reactions, in
which the nitrogen is retained in the product. 25. The compound Y is
(a) MgCl2 (b) FeCl2
19. Arenediazonium ions are more stable than alkyldiazonium ions (c) FeCl3 (d) ZnCl2
because 26. The compound Z is
(a) resonance stabilization of the corresponding cation (a) Mg2[Fe(CN)6] (b) Fe[Fe(CN)6]
(b) thearene cation, Ar+ is very difficult to be formecd
(c) both the above factors (c) Fe4[Fe(CN) 6] 3 (d) K2Zn3[Fe(CN) 6] 2
(d) none of the two
 EBD_7091
982
33. STATEMENT - 1 : Aniline on reaction with NaNO 2 / HCl at
Instructions for Q. 27 to 29 : Following questions are Multiple 0oC followed by coupling with β-naphthol gives a dark blue
Matching type Questions : precipitate.
STATEMENT - 2 : The colour of the compound formed in the
27. Column - I Column - II reaction of aniline with NaNO2/HCl at 0oC followed by coupling
Basic compound pKa of ammonium ions with β-naphthol is due to the extended conjugation.
34. Statement 1 : pKb for aniline is more than that of methylamine.
(A) NH2 (a) 0.4 Statement 2 : Higher pKb means less basic.
35. Statement 1 : Amino group is o- and p-directing in aromatic
(B) NH3 (b) 4.63 electrophilic substitution reactions, aniline on nitration gives a
substantial amount of m-nitroaniline.
(C) NH (c) 5.25 Statement 2 : Direct nitration of aniline gives a substantial
amount of p-nitroaniline
36. Statement 1 : Diazonium salts of aromatic amines are more
(D) NH (d) 9.26 stable than those of aliphatic amines.
Statement 2 : Diazonium ion shows resonance.
37. Statement 1 : Ethylamine is soluble in water, whereas aniline is
not.
(E) N (e) 11.27 Statement 2 : Ethylamine forms hydrogen bonds with water
molecules.
28. Column - I Column - II
38. Statement 1 : Aniline undergo Friedel-Crafts reaction.
(A) Aldehyde + Zn(Hg) (a) distinguish between Statement 2 : Aniline forms salt with aluminium chloride (a
+ conc. HCl primary and lewis acid) which is used as a catalyst.
other amines 39. Statement 1 : Gabriel phthalimide synthesis is preferred for
(B) Carbylamine (b) White precipitate synthesising aliphatic primary amines.
reaction Statement 2 : Aryl halides undergo nucleophilic substitution
(C) Schiff bases (c) Hydrocarbon with the anion formed by phthalimide.
(D) 2, 4, 6-tri bromo- (d) Antioxidation ⊕
aniline 40. Statement 1 : Toluene undergoes diazo coupling with Ph N 2
29. Column - I Column - II
COOH NH2 and O2N N N.

Conc. H2SO 4 NO2

(A) + HN3 (a) pH 5 - 7
⊕
Statement 2 : Ar N 2 is a weak electrophile and undergoes
Cl Cl diazo coupling only with highly activated ring.
41. Statement 1 : In strongly acidic medium aniline becomes less
+
NH2 + C6H5N2 reactive towards electrophilic reagent.
(B) (b) Curtius reaction
Statement 2 : NH2 group is ortho and para directing.
42. Statement - 1 : In strongly acidic solutions, aniline becomes
Azo dye.
more reactive towards electrophilic reagents.
+
Statement-2 : The amino group being completely protonated
(C) OH + C6H 5N2 (c) Sulphanilic acid in strongly acidic solution, the lone pair of electrons on the
nitrogen is no longer available for resonance.
Azo dye.
(D) Methyl orange (d) pH 9 - 10
Instructions for Q. 43 to 45 : Following questions are Integer Type
Questions :
Instructions for Q. 30 to 42 : Following questions are Assertion and
Reasoning Type Questions : NO2
Note : Each question contains STATEMENT-1 (Assertion) and
STATEMENT-2 (Reason). Each question has 5 choices (a), (b), (c), NH SH Br /H O NaNO CuBr − HBr
(d) and (e) out of which ONLY ONE is correct. 43. 
4 → 
2 2 → 
2 → →
excess HCl
(a) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1.
(b) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a NO2
correct explanation for Statement-1. Sn /HCl Br2 /H 2 O
→  → major end product.
(c) Statement -1 is True, Statement-2 is False. Find the total number of halogen atoms present in the major end
(d) Statement -1 is False, Statement-2 is True. product.
(e) Statement -1 is False, Statement-2 is False. 44.
NaNO /HCl
2
Ph − NH 2  2
→  →(X)
Ph − NH
0 − 5° C dil. HCl
30. Statement-1 : Benzene diazonium chloride does not give tests Find the sum of number of nitrogen atoms present in (X) and the
for nitrogen. total number of stereoisomers of (X) formed.
(+)
Statement-2 : Loss of N2 gas takes place during heating. Ph 2 / Δ
H / HO dil. H2SO4
31. Statement-1 : Anilinium chloride is more acidic than ammonium 45. N A B+ C
chloride. H OH
Statement-2 : Anilinium ion is resonance-stabilized. H2O
32. Statement-1 : p-O2 N—C2H 5COCH 3 is prepared by Friedel
Craft's acylation of nitrobenzene. 1. NaNO2/ H
+
Br2
Statement-2 : Nitrobenzene easily undergoes electrophilic E D Bis insoluble layer
2. Cu / HBr
substitution reaction. E has how many halogens ?
 983

EXERCISE 20.3 (Subjective Problems)

1. Write down structures of the following compounds. (c) m-Nitro–N–methylaniline + HONO
(a) p-Toluidine (b) Anilinium chloride (d) m-Toluidine + aq. Br2 (excess)
(c) N, N-Diethylaniline (d) 2, 4-Dimethylaniline (e) p-Toluidine + aq. Br2 (excess)
(e) Benzylamine (f) Diphenylamine (f) p-CH3C6H4NHCOCH3 + HNO3 + H2SO 4
(g) p, p′-Diaminodiphenyl (h) N-n-Propylaniline. (g) Benzanilide + Br2 + Fe.
2. Compare the behaviour of aniline, N-methylaniline and N, 5. Complete the following.
N-dimethylaniline toward each of the following reagents.
(a) Dil. HCl (b) excess of CH3I PCl 5 3 2 5 NH PO H+ , heat
(a) C6H5COOH → [A] → [B] → [C] → [D]
(c) C6H5COCl + pyridine (d) C6H5SO 2Cl + aq. KOH
(b) C6H5NH 2 + [E] + [F] → C 6H5NHCONHC6H5
(e) Bromine water.
3. Give structures and names of the principal organic products NaNO , HCl
2 anisole
(c) 2, 4-Dinitroaniline → [G] → [H]
expected from the action of sodium nitrite and hydrochloric 5° C
acid on each of the following compound.
(a) o-Toluidine (b) N-Methylaniline Br water
2 2(i) NaNO , HCl, 5 °C
(d) Aniline → [I] → [J]
(c) N, N-Dimethylaniline (d) 4, 4′-Diaminodiphenyl (ii) C 2H 5 OH
(e) Benzylamine (f) Sulphanilic acid.
Br , Fe
4. Write balanced equations for the following reactions. (e) 2
CH3CONHC6H5 → [K] + [L].
(a) Benzanilide + aq. NaOH (boiling)
(b) Methyl formate + aniline