ORGANIC COMPOUNDS CONTAINING NITROGENT

2020
1. How do you convert the following? 1+1+1=3
(i) Benzene to phenol
(ii) Nitroethane to dimethylamine
(iii) Aniline to phenylisocyanide

Ans. (i)
SO3H OH

Oleum
i. NaOH
ii. H+

(ii)
CHCl3 , alc.KOH Na/C2H5OH
CH3NO2 Sn / HCl
CH3NH2 CH3NC CH3NHCH3
(reduction)

Nitromethane

NH2 N C

+ CHCl3 + 3KOH
(iii)
Carbyamine reaction
Aniline Phenylisocyanide

2. An organic compound ‘A’ on treatment with aqueous ammonia and heating forms
compound ‘B’ which on heating with Br2 and KOH forms compound ‘C’ of molecular
formula C6H7N. Write the structures and IUPAC names of compound A, B, and C. 3
Ans. Since the compound ‘C’ with M.F C6H7N is formed from compound ‘B’ on treatment with
Br2 + KOH (Hofmann bromamide reaction), therefore, compound ‘B’ must be an amide
and ‘C’ must be an amine. The only amine with M.F C6H7N is aniline (C6H5NH2).
Since ‘C’ is aniline, therefore, the amide from which it is formed must be benzamide
(C6H5CONH2).
CONH2
NH2

Br2/KOH
Hofmann bromamide
Benzamide (B) reaction Benzamine (aniline)
(M.F= C7H7O) (C)
( M.F= C6H7N )
 Since the compound ‘B’ is formed from compound ‘A’ with aqueous ammonia
and heating, therefore compound ‘A’ must be benzoic acid.

COOH CONH2

aq.NH3

Benzoic acid Benzamide (B)

(A) (M.F= C7H7O)

2019
1. Aniline does not undergo Friedel-craft reaction. Why? 2
Ans. Aniline does not undergo Friedel-craft reaction due to salt formation with aluminium
chloride, the Lewis acid which is used as a catalyst. Due to this, nitrogen atom of aniline
acquires a positive charge and hence act as a strong deactivating group for further
reaction.

NH2 NH2AlCl3
AlCl3

Aniline
2. How you will convert aniline to chlorobenzene? 1

NH2 N2Cl Cl

NaNO2/HCl Cu/HCl
273-278k
Aniline Benzenediazonium chloride Chlorobenzene

3. Give a chemical test to distinguish the following pairs of compounds: 1 ⁄ +1 ⁄ =3

(i) Methylamine and dimethylamine
(ii) Aniline and benzylamine
 (i) By carbylamine test

CH3NH2 + CHCl3 + 3KOH CH3NC + 3KCl + 3H2O

Methylamine

CH3NHCH3 + 3KOH + CHCl3 No reaction

dimethylamine

(ii) By Nitrous acid test: Benzyl amine reacts with nitrous acid to form diazonium salt which
is being unstable decomposes to evolve N2 gas.

NaNO2/HCl decomposes
C6H5CH2NH2 [C6H5CH2 N NCl ]

Benzylamine 273-278k (Unstable)

C6H5OH + N2 + HCl
Aniline on the other hand react with nitrous acid at 273-278k to form
benzenediazoniumchloride which is stable and does not decomposes to evolve N2 gas.
NH2
N NCl
NaNO2/HCl
273-278k
Aniline Benzenediazoniumchloride
2. Account for the following: 2x1.5=3
(i) Ethylamine is soluble in water but aniline is not.
(ii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric chloride
Ans. (i) Ethylamine is soluble in water due to formation intermolecular hydrogen bonds

H H

H N H O H N H O

C2H5 H C2H5 H
However, in aniline, due to large hydrocarbon part the extent of H-bonding decreases and
Hence aniline is not soluble in water.
(ii) Methylamine is being more basic than water accept a proton from water liberating OH-
ions. These OH- ions combine with Fe+3 ions present in water to form brown ppt. of
hydrated ferric oxide.
 CH3NH2 + H OH CH3NH3 + OH-

FeCl3 Fe+3 + 3Cl-

Fe+3 + 3OH- Fe(OH)3 or Fe2O3.3H2O

Hydrated ferric oxide (Brown ppt.)

2018
1. Arrange the following compounds in the increasing order of their basic strength in aqueous
Solution: 1
.
NH3 , C2H5NH2 , (C2H5)2NH , (C2H5)3N
Ans.
NH3 C2H5NH2 (C2H5)3N (C2H5)2NH
.
2. Answer the following; 1X3=3
(i) Give a chemical test for primary amines
(ii) What happens when aniline is reacts with bromine water at room temperature?
(iii) Write the diazotization reaction of aniline
Ans.
(i) Primary amines can be distinguish from secondary and tertiary amines by carbylamines or
Isocyanide test

R NH2 + CHCl3 + 3KOH Heat

R NC + 3KCl + 3H2O
(ii) When aniline reacts with bromine water it forms 2, 4, 6-tribromoaniline

NH2 NH2
Br2-H2O Br Br

Aniline Br
2,4,6-tribromoaniline
(iii) Diazotization reaction of aniline
C6H5NH2 + NaNO2 + 2HCl 273-278k C6H5N2Cl + NaCl + 2H2O
 2017
1. Give the IUPAC name the following compound: 1

COOH

NH2

2. Identify the organic product in the following reaction. Give its IUPAC name. 1

NaNO2 + HCl
C6H5NH2 ?
3. Name the following reactions: 2

CuCl/HCl
(i) C6H5N2+Cl- C6H5 Cl + N2

Cu/HCl
(ii) C6H5N2+Cl- C6H5 Cl + N2 + CuCl

2016
1. How do you convert aniline into phenol? Give necessary chemical equation. 2
2015
1. Give the formula of A, B, C and D in the following reactions- 2

ethanolic NaCN H2/Ni

(i) CH3CH2 Cl A B

(ii) C6H5NO2 Fe/HCl NaNO2/HCl

C D
273-278k
2. Answer the followings: 2
(a) Arrange in increasing order of basic strength:

CH3NH2 , (CH3)2NH , (CH3)3N (in aqueous solution)

(b) Kb of aniline is less than that of methylamine, why?

2014
1. An aromatic compound (A) on treatment with aqueous ammonia and heating forms a
Compound (B). Which on heating with Br2 and KOH forms a compound (C) of molecular
Formula C6H7N. Write the structure and the IUPAC names of the compounds A,B and C. 2
2. Methanamine can be prepared by using Gabriel phthalimide synthesis. Write chemical
equation for the synthesis 2
3. How can you convert aniline to p-nitroaniline? Give chemical equation only. 2

2013
1. Identify A, B, C and D: 2

KCN LiAlH4
(i) CH3CH3Br A B
Fe + HCl NaNO2
(ii) C6H5NO2 C
HCl
00C
2. Write one chemical test to distinguish between ethylamine and aniline. 1

EXTRA QUESTIONS
1. Account for the following:
(a) Although amino group is o/p-directing in aromatic substitution reactions,
Aniline on nitration gives a substantial amount of m-nitroaniline.
(b) Pkb of aniline is more than that of methylamine.
(c) Aromatic amine cannot be prepared by Gabriel phthalimide synthesis.
(d) Aliphatic amines are stronger base than aromatic amines.
(e) Primary amines have stronger boiling point than tertiary amines.
2. Give a chemical test to distinguish between the following pairs of
compounds:
(i) Methylamine and dimethylamine
(ii) Secondary amine and tertiary amine
(iii) Ethylamine and aniline
(iv) Aniline and benzylamine
(v) Aniline and N-methylaniline
3. How you will convert
(a) Ethanoic acid to methamine
(b) Methanamine into ethanamine
(c) Nitromethane into dimethylamine
(d) Aniline to benzyl alcohol
(e) Aniline to p-bromoaniline
 (f) Benzamide to toluene
(g) 4-nitrotoluene into 2-bromobenzoic acid
(h) Benzene into aniline
(i) Benzene into N, N-dimethylaniline
4. Write short notes on the following:
(i) Carbylamine reaction
(ii) Diazotization
(iii) Hofmann bromamide reaction
(iv) Gabriel phthalimide synthesis
(v) Ammonolysis
(vi) Coupling reaction
5. Arrange the following in increasing order of their basic strength:

(i) C2H5NH2 , C6H5NH2 , NH3 , C6H5CH2NH2 , and (C2H5)2NH

(ii) C2H5NH2 , (C2H5)2NH , (C2H5)3N , C6H5NH2

(iii) CH3NH2 , (CH3)2NH , (CH3)3N , C6H5NH2 , C6H5CH2NH2

6. Arrange the following:
6. Write A , B and C in the following reactions:

7. Complete the following reactions: