Chapter 23: Reactions of Nitrenes and Electron Deficient Oxygen

Practice Problems

1. (d) It is Hofmann Bromamide reaction, upto one mole of KOH, only one proton of amide will be
substitute by Br.

2. (b) It is Beckmann Rearrangement reaction, group anti to the OH group will migrate.

3. (d) Only primary amide undergo Hofmann Bromamide reaction.

4. (a) Correction!! Replace a,b,c,d with 1,2,3,4. In first reaction, first step is isocyanide test while the
second step is reduction. In second reaction, first step is Riemer Tiemann reaction while the second step
is reduction.

5. (b) It is Hoffman Bromamide reaction and the amine will add to the same side as amide.

6. (c) First, Hofmann Bromamide reaction will take place followed by substitution of Cl by amine through
SNAE (Substitution nucleophilic addition via elimination).

7. (a) It is Beckmann Rearrangement reaction, PCl5 will act as Lewis acid.

8. (b) It is Beckmann Rearrangement reaction, group anti to the OH group will migrate.

9. (a) Hoffman Bromamide reaction followed by acetylation of amine.

10. (d) It is Carbylamine test (Hofmann Isocyanide test).

11. (a) It is Beckmann Rearrangement reaction, group anti to the OH group will migrate.

12. (b) X is oxime formed by elimination of water molecule, Y is formed by Beckmann Rearrangement in
which amide is formed which then undergoes hydrolysis to form Carboxylic acid.

13. (b) It is Wolff rearrangement reaction.

14. (c) A is methyl amine formed by Hoffman Bromamide reaction while B is ethyl amine formed by
reduction.

15. (a) A is Salicylic acid formed by Kolbe Schmitt reaction which undergoes acetylation of OH group to
form 2-acetoxybenzoic acid or Aspirin.

16. (b) It is Wolff rearrangement reaction.

17. (b) It is Hofmann Broamide reaction.

Solution Manual for Solomons, Fryhle and Snyder Organic Chemistry For JEE (Main &
Advanced), Copyright©2017 Wiley India Pvt. Ltd. All rights reserved
18. (c) It is oxidation reaction, amine is oxidised to nitro.

19. (c) Methyl group will migrate in the Beckmann rearrangement reaction to form A (N-methyl
propanamide), which is then reduced by LAH from amide to amine.

20. (d) Isocyanide is also called carbylamine.

<H2> Linked Comprehension Type

1. (d) Br2 and KOH are required, the base will abstract proton from the amide, and the anion will then
attack bromine as nucleophile.

2. (d) Migration is the RDS in this reaction.

3. (b) Migration in Hofmann Bromamide is intramolecular only.

<H2> Matrix Match Type

a(p, r,s) ; b(q, r);c(p, r, s); d(p, r,s)

(a)- Hofmann Bromamide reaction, product A is Aniline. Since it is primary amine, hence it will give
isocyanide test.

(b)- Reduction reaction. Since it is primary amine, hence it will give isocyanide test.

(c)- Beckmann reaction, group anti to OH will migrate. Since primary amine is product, hence it wil give
isocyanide test.

(d)- Hofmann Bromamide reaction, product A is Aniline. Since it is primary amine, hence it will give
isocyanide test.

Solution Manual for Solomons, Fryhle and Snyder Organic Chemistry For JEE (Main &
Advanced), Copyright©2017 Wiley India Pvt. Ltd. All rights reserved