12. ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

4. Answer the following

i. Write a note on –
a. Cannizaro reaction
b. Stephen reaction.

Answer:- a) Cannizaro Reaction
  • This reaction is given only by aldehydes having no α-hydrogen atom.
  • Aldehydes undergo self -oxidation and reduction reaction on heating with concentrated alkali.
  • In Cannizzaro reaction, one molecule of an aldehyde is reduced to alcohol and at the same time the second molecule is oxidized to carboxylic acid salt. Thus, the reaction is an example of disproportionation reaction.
e.g. 1. \[\begin{array}{cc} \ce{O\phantom{……………………………}}\ce{O\phantom{………………}}\ce{H\phantom{}}\\ ||\phantom{……………………………}||\phantom{……………….}|\\ \ce{\underset{\text{Formaldehyde}}{2H – C – H} + \underset{\text{Sodium hydroxide (50%)}}{NaOH} ->[\triangle] \underset{\text{Sodium formate}}{H – C – O- Na+} + H – C – OH}\\\phantom{………………………………………………}|\\\ce{\phantom{………………………………………………}\underset{\text{Methanol}}{H}}\end{array}\]
2.
cannizarro reaction
b. Stephen reaction. Nitriles are reduced to imine hydrochloride by stannous chloride in presence of hydrochloric acid which on acid hydrolysis give corresponding aldehydes. This reaction is called Stephen reaction.
\[\ce{\underset{(Alkane nitrile)}{R – C ≡ N +}2[H] ->[SnCl2, HCl]\underset{(Imine hydrochloride)}{R – HC = NH.HCl}->[H3O+]\underset{(Aldehyde)}{R – CHO} + NH4Cl}\] e.g. \[\ce{\underset{(Ethanenitrile)}{H3C – C ≡ N}+2[H] ->[SnCl2, HCl][(reduction)]\underset{(Ethanimine hydrochloride)}{CH3 – HC = NH.HCl}->[H3O+]\underset{(Ethanal)}{CH3 – CHO} + NH4Cl}\]

12. ALDEHYDES, KETONES AND CARBOXYLIC ACIDS page 281