Solution

AMINE

Class 12 - Chemistry
Section A

1. a.

b.

alc. KOH
c. C 6 H5 NH 2 + CHCl 3 −−−−−→ C6 H5 N
+
≡ C
−

Aniline Chloroform Phenyl isocyanide

2. Conversion from Benzene to p-nitroaniline involves the following steps:

3. a. A = CH3CH2CN
B = CH3CH2CONH2
C = CH3CH2NH2

b. A =

B=

C=

4. i. In aqueous solution, basic strength decreases in the order. (C2H5)NH > (C2H5)3N > C2H5NH2
ii. In increasing order of solubility in water:
nh

(C2H5)NH2> (C2H5)2NH> C6H5NH2

iii. In decreasing order of their pKb values:
NH3 > C2H5NH2 > C6H5NH2
5. Structure of A, B and C

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 6.

7. a. In case of chlorobenzene, the C-CI bond is quite difficult to break as it acquires a partial double bond character due to
conjugation. So, under the normal conditions, ammonolysis of chIorobenzene does not yield aniline.
b. Primary and secondary amines are engaged in intermolecular association due to hydrogen bonding between nitrogen of one
molecule and hydrogen of another molecule. Due to the presence of three hydrogen atoms, the intermolecular association is
more in primary amines than in secondary amines as there are two hydrogen atoms available for hydrogen bond formation in
it.
c. During the acylation of aniline, stronger base pyridine is added. This is done in order to remove the HCI so formed during the
reaction and to shift the equilibrium to the right hand side.
8. i. Acetylation:

ii. Gabriel phthalimide reaction:

9. i.

ii.

10. i. Aniline, N-ethylethanamine, Ethanamine

ii. Ethanamine, ethanol, ethanoic acid
iii. N, N dimethylmethanamine, methanamine, N-methylmethanamine
11.

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12.

In non-polar solvent (such as CS2) the activating effect of -NH2 group is reduced (due to resonance) and hence, mono substitution
occurs only at o- and p-positions while para is a minor product and ortho is a major product.
13. i. Conversion of CH3–CH2–Cl into CH3–CH2–CH2–NH2 involve the following steps:

ii. Conversion of C6H5–CH2–Cl into C6H5–CH2–CH2–NH2 involve the following steps:

14. It is because Ammonolysis yield a mixture of primary, secondary, tertiary amines and also a quaternary ammonium salt.
15. i. Conversion of Toluene into p-Toluidine involved the following steps:

ii. Conversion of p-Toluidine diazonium chloride into p-Toluic acid involved the following steps:

H2 /P d

16. R − NH 2
+ CHCl 3
+ 3 KOH → R− NC −−−−−−−→ R− NH − C H 3
o o
1 A min e Alkyl isocyanide (Re duction) 1 A min e

Carbylamine reaction is shown by 1o amine only which results in the replacement of two hydrogen atoms attached to N atom of -
NH2 group by one carbon atom in heating with choloform to form isocyanide or carbylamine. On catalytic reduction, the
isocyanide will give a secondary amine with one methyl group.
KCN LiAlH4

17. CH Br −−−→ CH CN −−−−→ CH CH NH

3 3 3 2 2

18. Conversion of p-Nitroaniline to 3,4,5-Tribromonitrobenzene involves the following steps:

19. Aniline forms anilinium chloride salt with aq. HCl which is soluble in water.

Heat

20. i. R-NH2 + CHCl3 + 3KOH −−−→ R-NC+ 3KCl + 3H2O

O

||

ii. R − C − NH 2 + Br2 + 4NaOH → R − NH 2 + Na 2 CO3 + 2NaBr + 2H2 O

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21. Following reaction involved in the conversion of 4-nitrotoluene to 2- Bromo benzoic acid:
i. Nitro compounds are reduced to an amine by Sn/HCl.
ii. Aliphatic amine reacts with nitrous acid to form an aliphatic diazonium salt.
iii. Mild reducing agents like hypophosphorous acid to reduce diazonium salts.

22. a. Sandmeyer's reaction

X = Cl, Br, CN
b. Combination of inductive effect and solvation effect/Due to greater H-bonding with water molecules, (CH3)2NH shows more
hydration or solvation effect.
23. a. Due to resonance stabilisation of arene diazonium ion /

b. Methyl amine being basic, gains a proton from water and releases hydroxyl ions which precipitate hydrated ferric oxide. It can
be shown in the form of chemical reaction as:
H2 O

CH3 NH2 −−→ CH3NH3+ + OH-

−
3OH

FeCl3 −−−→ Fe(OH)3 ↓ + 3Cl-

24. C H N H < (C H ) N H < C H N H
6 5 2 2 5 2 2 5 2

25. C H C H C ON H + Br + K OH → C H
3 2 2 2 3 C H2 N H2
(A) (B)

C H3 C H2 N H2 + C HC l3 + K OH → C H 3 C H2 N C
(B) (C)

A = Propanaimde
B = Ethyl amine (1o amine)
C = Ethyl isocyanide
D = N-ethyl benzene sulphonamide
26. i. Acetylation of anilline:

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 ii. Coupling reaction:

iii. Carbylamine reaction:

Heat

R-NH2 + CHCl3 + 3KOH −−−→ R-NC + 3KCl + 3H2O

27. C 6 H5 N H2 < C6 H5 N (C H3 )2 < C H3 N H2 < (C2 H5 )2 N H

28.

29. a. Aniline is acetylated, before nitration reaction in order to avoid formation of tarry oxidation products and protecting the amino
group, so that p-nitro derivative can be obtained as major product.
b. PKb of aniline is lower than the m-nitroaniline. The basic strength of aniline is more that m-nitroaniline. The pkb value is
inversely proportional to the basic strength. The presence of electron withdrawing group decreases basic strength.
c. Due to the presence of acidic hydrogen in the N-alkylbenzenesulphonamide formed by the treatment of primary amines.
d. Aniline does not react with methyl chloride in the presence of AlCl3 catalyst, because aniline is a base and AlCl3 is lewis acid
which lead to the formation of salt. (any three)
30. Conversion

i.

NH 3 Br2 /KOH

ii. CH 3 COOH −−→ CH3 CONH2 −−−−−→ CH3 NH 2

△
LiAlH 4

iii. CH 3 CH2 CH2 CN −−−−→ CH3 CH2 CH2 CH2 NH 2

Section B
31. i. AgCl forms a complex with methylamine
.AgC l + 2C H N H → [Ag(C H N H
3 2 3 2 )2
+ −
Cl
So lub le

ii. Tertiary amines do not undergo acylation because they do not have hydrogen attached to nitrogen.
iii. In aniline, -NH2 group is electron releasing, therefore, it increases electron density at o- and p-positions. Therefore, it forms 2,
4, 6- tribromoaniline.
32. An aromatic compound ‘A’ on heating with Br2 and KOH forms a compound.

where R = C6H6 .
Here, IUPAC name of A is Benzamide and its structure is

Molecular formula of B is C6H7N. Here, IUPAC name of B is Aniline and its structure is

5 / 17
 B on reacting with CHCl3 and alcoholic KOH produces a foul-smelling compound ‘C’. The reaction is,
alc.KOH

RN H2 + C HC l3 −−−−−→ R − NC

where R = C6H6 . Here, IUPAC name of C is Phenyl isocyanide and structure is

33. i.

ii.

iii.

34. i. Ethylamine forms strong hydrogen bonds with water molecules whereas in aniline due to the large hydrocarbon part, the
extent of H-bonding decreases.
ii. Because of protonation of aniline / formation of anilinium ion which deactivates the ring.
iii. Amines behaves as nucleophiles due to the presence of a lone pair of electrons on the nitrogen atom.
35. This reaction is an example of electrophilic aromatic substitution(atom attach to aromatic is replaced by an electrophile). In an
alkaline medium, phenol forms phenoxide ion which is more electron-rich than phenol and hence more reactive for the
electrophilic attack. The electrophile in this reaction is aryl diazonium cation a p-Nitrophenyldiazonium cation (O2N-C6H4-N=N)
is a stronger electrophile than p-toluene diazonium cation. Therefore, it couples preferentially with phenol.

36. a.

b.

37. a. It is a because-NH2 group is electron releasing group which increases electron density on a benzene ring and there is more
electron density at o- and p- position in resonating structures of aniline. Thus, it activates the benzene ring for electrophilic
substitution.
b. i. It is used for the manufacture of dyes.
ii. It is used for the manufacture of drugs.
38. i. C6H5NH2 < (CH2)2NH < CH3NH2

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 ii. (CH3)2NH > CH3NH2 > (CH3)3N
iii. (C2H5)3N < (C2H5)2NH < C2H5NH2
N H3 N aOBr

39. i. C H 3 C OOH −
− −
→ C H3 C ON H2 −−−−→ C H3 N H2
Δ
Fe/HCl N aN O2 +HCl

ii. C 6 H5 N O2 −−−−→ C6 H5 N H2 −−−−−−−−→ C6 H5 N2 C l

o o
0 −5 C
+
CuCN H2 O/H

iii. C 6 H5 N2
+ −
Cl −−−−→ C6 H5 C N −−−−−→ C6 H5 OH
Δ
Base

40. i. C2H5NH2 + CH3COCL −−−→ C2H5NHCOCH3 + HCL

ii.

iii.

41. The Primary, secondary and tertiary amines can be distinguished by Hinsberg test. The given amine is shaken with benzene
sulphonyl chloride.
i. Primary amine forms sulphonamide which is soluble in alkali.

ii. Secondary amine forms sulphonamide which is insoluble in alkali.

iii. Tertiary amine will not react with Hinsberg's reagent because there is no hydrogen present on nitrogen.

42. i.

Br2 /KOH

ii. CH 3 CONH2 −−−−−→ CH3 NH 2

LiAlH4

iii. CH 3 CN −−−−→ CH3 CH2 NH 2

43. i.

ii.

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 O

||

iii. CH − C − NH + Br + 4 KOH → CH NH + K CO + 2 KBr + 2H O

3 2 2 3 2 2 3 2
Ethylamide Methyla min e

44. p-aminodiazobenzene can be obtained from nitrobenzene as under:

p-Aminoazobenzene

45.

Since the compound (A) on hydrolysis in presence of an alkali gives an acid (B) and ammonia gas, it is a nitrile. The compound
(C) is a primary amine as it reacts with HN O and forms an alcohol (D).
2

A =CH3CH2CN
B = ​CH3CH2COOH,
C = ​CH3CH2CH2NH2
D = ​CH3CH2CH2OH
Equations are-

46. i. Propanamine contains three carbons. Hence, the amide molecule must contain four carbon atoms. Structure and IUPAC name
of the starting amide with four carbon atoms is as follows:
C H3 C H2 − C H2 − C − N H2

||
O

Butanamide

ii. Benzamide is an aromatic amide containing seven carbon atoms. Hence, the amine formed from benzamide is aromatic
primary amine containing six carbon atoms.

47. Based on the observations, structures of A, B and C are deduced as under:

Fe/HCl N aN O2 /HCl Na

C H3 C H2 C H2 N O2 −−−−→ C H3 C H2 C H2 N H2 −−−−−−−→ C H3 C H2 C H2 OH −
−→ C H3 C H2 C H2 ON a + H2
′ ′ ′ ′ ′ ′
A B C Sodium propoxide

1−N itropropane 1−Pr opana min e Pr opan−1−ol

(Mol. Formula = C3 H7 O2 N ) (Mol. Formula = C3 H4 N ) (Mol. Formula = C3 H8 O)

CrO3

C H3 C H2 C H2 OH −−−→ C H3 C H2 C HO
1−Pr opanol Pr opanal

LiAH4

48. i. C H 3 C H2 C H2 N O2 −−−−→ C H3 C H2 C H2 N H2 + 2H2 O

+
H

ii. C2 H5 N ≡ C + 2H2 O −→
− C2 H5 N H2 + HC OOH

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 iii.

49. i. The increasing order of basic strength in aqueous solution of the following amines is (CH3)3N < CH3NH2 < (CH3)2NH (Due
to steric hindrance and +I effect of alky groups).
ii. Hinsberg reagent is also known as benzene sulphonyl chloride (C6H6SO2Cl). When it reacts with primary and secondary
amines, it produces sulphonamides.
iii. Pyridine is used in the acylation of amines because it acts as a strong base which helps in removing the side product HCl from
the reaction mixture. Therefore, it acts as an acceptor for the acid by-product formed during the reaction.
50. Aniline reacts with methyl iodide to produce N, N-dimethylaniline.

With excess methyl iodide, in the presence of Na2CO3 solution, N, N-dimethylaniline produces N, N, N-trimethylanilinium
carbonate.

51. The aromatic compound A is benzoic acid C6H5COOH.

On treatment with aqueous ammonia and heating forms compound B, which is benzamide C6H5CONH2.
Benzamide on heating with bromine and KOH forms a compound C of molecular formula C6H7N, which is aniline C6H5NH2.
The reaction is called Hoffmann bromamide degradation.

52. It is given that compound 'C' having the molecular formula, C6H7N, and formed by the reaction of compound 'B' with Br2 and
KOH. This is a Hoffmann bromamide degradation reaction. Therefore, compound 'B' is an amide, and compound 'C' is an amine.
The only amine having the molecular formula C6H7N is aniline, (C6H5NH2).

Compound 'B' (from which 'C' is formed) must be benzamide, ​(C6H5CONH2).

Further, benzamide is formed by heating compound 'A' with aqueous ammonia. Therefore, compound 'A' must be benzoic acid.

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 The given reactions can be explained with the help of the following equations:

53. Primary, secondary and tertiary amines can be identified by Hinsberg's reagent (Benzenesulphonyl chloride C6H5SO2Cl). Primary
amines react with Hinsberg's reagent to form sulphonamides soluble in alkali whereas secondary amines form sulphonamides
insoluble in alkali. Tertiary amines do not react with Hinsberg's reagent.

KOH
C H SO Cl + R NH → C H SO NR
6 5 2 2 6 5 2 2
−−→ Insoluble
54. Reactions:

55. i. C6H5NH2<NH3<C6H5CH2NH2<C2H5NH2<(C2H5)2NH
ii. C6H5NH2<C2H5NH2<(C2H5)3N<(C2H5)2NH
iii. C6H5NH2<C6H5CH2NH2<(CH3)3N<CH3NH2<(CH3)2NH
Section C
56. i. Aniline is a Lewis base and it reacts with AlCl3 to form a salt / N of aniline acquires positive charge with AlCl3 and hence is a
deactivating group.
(CH3)3N < (CH3)3N < NH3 < C6H5NH2 / C2H5 NH2 < (CH3)3N < NH3 < C6H5NH2
ii. (As no medium (aqueous /gaseous) or phase is given both answers to be considered).
iii. Add Hinsberg reagent (benzene sulphonyl chloride) to both the compounds. CH3CH2NH2 gives ppt. that is soluble in alkali
while the ppt. formed by (CH3CH2)2 NH is insoluble in alkali.
OR

I.

II.

57. i. C6H5NH2 < NH3 < C6H5CH2NH2 < C2H5NH2 < (C2H5)2NH

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 ii. dimethylamine < methylamine < N-methylaniline < aniline.
iii. p-nitroaniline < aniline < p-toluidine < N, N-dimethyl-p-toluidine.
OR
Due to delocalization of the lone pair of electrons of the N-atom of aniline over the benzene ring, aniline is more acidic than
ammonia.
58. i. Hoffmann bromamide degradation is used for the preparation of primary amine.
ii. Formation of (iv)
The rate determining step is probably loss of Br- to form isocyanate as this is the slowest step.

iii.

OR

59. i. Benzene ring in aniline is highly activated. This is due to the sharing of lone pair of nitrogen with the ring which results in
increase in the electron density on the ring and hence facilitates the electrophilic attack.
ii. In aniline, the electron density is more at ortho and para positions than meta position, so, the substitution mainly takes place at
ortho and para positions.

iii.

OR
The amino group is an activating group and activate the ring at o- and p- positions. In benzene no group is present, so it does
not respond to the electrophilic substitution reaction readily.
Section D
O

||

60. i. A:- C H 3 C H2 C N , B:- C H 3 − C − N H2 , C:- C H3 N H2

P ropane nitrile Ethanamide Methanamine

ii. A:- C H 3 C H5 C N , B:- C 6 H5 C OOH , C:- C 6 H5 C ON H2

Cyano benzene Benzoic acid Benzamide

iii. A:- C H 3 C H2 C N , B:- C H 3 C H2 C H2 N H2 , C:- C H 3 C H2 OH

P ropane nitrile P ropanamine Ethanol

iv. A:- C 6 H5 N H2 , B:- C6 H5 N

2
+ −
Cl , C:- C 6 H5 OH
Aniline Benzene diazonium chloride P henol

v. A:- C H 3
C ON H2 , B:- C H3 N H2 , C:- C H 3
OH
Ethanamide Methanamine Methanol

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61. i. Aniline being a Lewis base reacts with Lewis acid (AlCl3) to form a salt.
+
−
C6 H5 NH 2 + AlCl3 ⟶ C6 H5 N H2 AlC l
3

As a result, N acquires a positive charge so, it acts as a strong deactivating group for electrophilic substitution reaction. Thus,
aniline does not undergo Friedel-Crafts reaction.
ii. Primary aromatic amines cannot be prepared by Gabriel phthalimide synthesis because aryl halides do not undergo
nucleophilic substitution with the anion formed by phthalimide. Gabriel phthalimide synthesis is used for the preparation of
primary amines.
iii. Aliphatic amines are stronger bases than the ammonia because the alkyl group in aliphatic amines has +I effect. So the alkyl
group tends to increase the electron density on the nitrogen atom whereas the electron releasing tendency of amines becomes
more than that of ammonia.
62. I. i. Aniline gets protonated and is deactivated/Aniline on protonation forms anilinium ion which is meta-directing therefore it
give good amount of m-nitroaniline.
ii. Due to combination of inductive effect and solvation effect.
iii. Ammonolysis of alkyl halide is not a good method to prepare pure primary amine because it forms a mixture of amines
that is difficult to separate.
II. i. R - NH2 + CHCl3 + NaOH → RNC + 3NaCl + H2O
ii.

63. i. Aniline is a Lewis base and forms a salt with Lewis acid.
Aniline being a Lewis base reacts with Lewis acid (AlCl3)to form a salt.
+
−
C6 H5 NH 2 + AlCl3 ⟶ C6 H5 N H2 AlC l
3

As a result, N acquires a positive charge so, it acts as a strong deactivating group for electrophilic substitution reaction. Thus,
aniline does not undergo Friedel-Crafts reaction.
ii. In aqueous solution, basic nature depends on + I-effect, H-bonding, and steric-effect.
The combined effect shows that (CH3)2·NH is more basic than (CH3)3·N as H-bonding is more in case of (CH3)2·NH than in
(CH3)3N, which predominates over the stability due to +I- effect of three -CH3 groups.
iii. Large pKb value means a weak base
In aniline, the lone pair of electrons on N-atom is delocalized over the benzene ring. As a result, electron density on the
nitrogen decreases and electrons are not available for donation. In contrast, in CH3-NH2, +I effect of -CH3 group increases the
electron density on the N-atom. Therefore, aniline is a weaker base than methylamine and hence, its pKb value is higher than
that of methylamine.
64. i. The structure of A and B on following reaction is:
a.

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 b.

ii. The chemical reaction of methyl amine with benzoyl chloride and IUPAC name of the product form is as follows:

iii. Increasing order of pKb values

⋅⋅ ⋅⋅ ⋅⋅

(C2 H5 )2 N H < C2 H5 N H2 < N H3 < C6 H5 N H2

65. I. Steps involved in the conversion are given below:

II. a.

b.

c.

66. a. i. Due to the electron-withdrawing effect of the acetyl group, the lone pair of electrons on N-atom is attracted by the acetyl
group. As a result, the lone pair of electrons on N-atom is not exclusively available for donation to the benzene ring and
hence, activating the effect of the - NH2 group is reduced.

ii. In aromatic amines, the lone pair of electrons present on nitrogen takes part in resonance and hence, not available for
donation. Alsoaniline is more stable than anilinium ion. Hence aniline has a very little tendency to accept a proton to form

13 / 17
 anilinium ion. However, in aliphatic amines, the lone pair is easily available for donation. That's why aliphatic amines are
more basic than aromatic amines.
iii. Nitration is usually carried out with a mixture of conc. HNO3 and cone. H2SO4. So in the presence of these acids, aniline
gets protonated to form anilinium ion. Therefore, the reaction mixture consists of aniline + and anilinium ion. -NH2 group
in aniline is o,p-directing and activating, whereas the +

NH 3
group in anilinium ism-directing and deactivating. Now, nitration
of aniline mainly gives p-nitroaniline due to steric hindrance at a-position and the nitration of anilinium ion gives m-
nitroaniline.

b. i. Gabriel phthalimide reaction Phthalimide on treatment with ethanolic KOHgives potassium phthalimide which on heating
with a suitable alkyl halide gives N-substituted phthalimide, which upon subsequent hydrolysis with alkali gives primary
amines.

This reaction is called Gabriel phthalimide reaction.

ii. Coupling reaction Arenediazonium salts react with highly reactive (i.e. electron-rich) aromatic compounds such as aniline,
phenols to form brightly coloured azo compounds, Ar-N = N-Ar. This reaction is called a coupling reaction. e.g. Benzene
diazonium chloride reacts with aniline in faintly acidic medium (pH 4- 5) at 273·278K, in which the molecule at its para-
position is coupled with the diazonium salt to form p-aminoazobenzene.
This is an example of a coupling reaction.

67. i. Aniline is typical of aromatic primary amines - where the -NH2 group is attached directly to a benzene ring. These are very
much weaker bases than ammonia.
Aniline is more basic than ethylamine because of resonance. When aniline loses a proton the resulting ion is more stable than
that of ethylamine and hence, aniline is more basic than ethylamine. Hence, aniline looses proton more readily than
ethylamine.
ii. Aniline being a Lewis base reacts with Lewis acid (AlCl3) to form a salt.
+
−
C6 H5 NH 2 + AlCl3 ⟶ C6 H5 N H2 AlC l
3

As a result, N acquires a positive charge so, it acts as a strong deactivating group for electrophilic substitution reaction. Thus,
aniline does not undergo Friedel-Crafts reaction.
iii. Gabriel phthalimide synthesis is a very convenient method for the preparation of pure aliphatic amines
Step 1: Phthalimide is treated with KOH to form potassium phthalimide

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 Step 2: Potassium phthalimide is treated with a suitable alkyl halide to form N-substituted phthalimides.

Step 3: N-substituted phthalimides undergoes hydrolysis in the presence of dil. HCl or with alkali(NaOH) to give primary
amines.

Overall reaction:

Gabriel phthalimide synthesis results in the formation of primary(1° amine) only. Secondary or tertiary amines are not formed
through this synthesis. Hence, Gabriel phthalimide synthesis preferred for the formation of primary amines only.

68. i. a.

b.

ii. a.

KCN LiAlH4 273K

CH3 CN CH3 CH2 NH2 CH3 CH2 OH
b. CH3Cl −−−→ −−−−→ −−−−→ + N2↑ + H2O
(A) (B) HN O2 (C )

69. Primary, secondary and tertiary amines can be identified and distinguished by Hinsberg's test. In this test, the amines are allowed
to react with Hinsberg's reagent (benzene sulphonyl chloride C6H5SO2Cl).
i. Primary amines react with benzenesulphonyl chloride to form N-alkyl benzenesulphonamide which is soluble in alkali.

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 ii. Secondary amines react with Hinsberg's reagent to form N, N-dialkyl benzene sulphonamide which is insoluble in alkali.

iii. Tertiary amines do not react with Hinsberg's reagent.

70. i. a.

b.

c.

ii. Increasing order of boiling point (CH3)3N < C2H5NH2 < C2H5OH Alcohols have a higher boiling point as compared to that of
amines because oxygen being more electronegative forms stronger hydrogen bond as compared to that of nitrogen. In tertiary
amine, there is no hydrogen bond formation due to the absence of H-atoms and hence, has the lowest boiling point.
iii. (CH3)2NH and (CH3)3N are secondary and tertiary amines respectively. These are distinguished by Hinsberg's reagent which
gives sulphonamide with secondary amines and no reaction with tertiary amines. (CH3)2NH reacts with benzene sulphonyl
chloride to give N, N-dimethyl benzene sulphonamide, which is insoluble in alkali. The reaction is as follows:

71. i. Hofmann bromamide degradation reaction It is a method for the preparation of primary amines by treating an amide with
bromine in an aqueous or ethanolic solution of sodium hydroxide. The amines so formed contain one carbon less than that
present in the parent amide.
ii. Gattermann reaction When benzene diazonium chloride is treated with Cu/HCl Cu/HBr, chlorobenzene or bromobenzene is
obtained. This reaction is known as Gattermann reaction
iii. Coupllng reaction Arenediazonium salts react with highly reactive (i.e. electron rich) aromatic compounds such as aniline,
phenols to form brightly coloured azo compounds, Ar-N =N-Ar. This reaction is called coupling reaction. e.g. Benzene
diazonium chloride reacts with aniline in faintly acidic medium (pH 4- 5) at 273·278K, in which the molecule at its para-
position is coupled with the diazonium salt to form p-aminoazobenzene. This is an example of coupling reaction.

72. i. Carbylamine reaction, i.e. conversion of -NH2 group in -NC group.

Δ CH3 CH2 − N =⃗ C
CH3 CH2 NH 2 + CHCl 3 + 3KOH(alc. ) −
→ + 3KCl + 3H2O
Ethyl isocyanide

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 ii. Benzene diazonium chloride form phenol with the reaction of water molecules and N2 is liberated.
H2 O

C6 H5 N
+

2
Cl
−
−−−→ C6 H5 OH + N2↑ + HCl
298K P henol

iii. Dlazonium salts form alcohol with boiling water and acidic medium.

Sn/HCl

73. i. C6H5-NO2 −−−−→ C6H5.NH2 (Aniline)

ii.

Br2 /KOH

iii. CH3CONH2 −−−−−−−−−−−−−−−−−−−→ CH3NH2+ K2CO3 + 2KBr + 2H2O

Hof mann bromamide degradation

74. i. These can be distinguished by the carbylamine test.

Δ

C H3 N H2 + C HC l3 + 3K OH −
→ C H3 N C + 3K C l + 3H2 O
Methyla min e (alc) Methylisocyanide
0
(1 A min e)
(of f ensive smell)

CHC l3 /KOH(alc)

C H3 N H −−−−−−−−−−→ N o reaction ​
Dimethyla min e
0
(2 ) a min e)

ii. Secondary and tertiary amines can be distinguished by Libermann nitrosoamine test. 2° amines react with nitrous acid to form
N-nitrosamines while 3° do not.
(C H3 C H2 ) N H + HO − N = 0 → (C H3 C H2 )2 N − N = O + H2 O
2
Diethyla min e N −N itrosodiethyla min e

(Y ellow colour)

iii. Azo dye test: Aniline and ethylamine can be distinguished by azo dye test. It involves the reaction of aniline with HNO2 at
273-278 K followed by treatment with an alkaline solution of β-naphthol, which gives a brilliant yellow, orange or red
coloured dye. Ethylamine under these condition gives a brisk evolution of N2 gas with the formation of primary alcohol.
iv. Nitrous acid test: Benzylamine reacts with nitrous acid to form a diazonium salt which being unstable even at low
temperature, decomposes with evolution of N2 gas.
Aniline, on the other hand, reacts with nitrous acid to form benzene diazonium chloride which is stable at 273 - 278 K and
hence does not decompose to evolve N2 gas.
v. Carbylamine test: Aniline being a primary amine gives carbylamine test whereas N-methylamine being a secondary amine
does not give this test. when aniline is heated with an alcoholic solution of KOH and CHCl3, it gives the offensive smell of
phenyl isocyanide.

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