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Answer the following · Q1

Q.Write a note on --
a. Cannizzaro reaction
b. Stephen reaction.

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✓ Free question

Step 1. Cannizzaro reaction (section 12.8.2h). Given ONLY by aldehydes with no alpha-hydrogen atom (so a normal aldol condensation is not available as a competing pathway). On heating with concentrated alkali, the aldehyde undergoes a disproportionation (self-oxidation-and-reduction): one molecule is reduced to the alcohol, a second is simultaneously oxidised to the carboxylate salt. Worked example: 2 H-CHO + NaOH (50%), heat, gives sodium formate (H-COONa) + methanol. A cross Cannizzaro reaction, between formaldehyde and a different non-enolisable aldehyde, always oxidises the formaldehyde to formic acid while reducing the other aldehyde to its alcohol -- e.g. formaldehyde + benzaldehyde, conc.NaOH then H3O+, gives phenylmethanol (benzyl alcohol) + formic acid.

Step 2. Stephen reaction (section 12.4.2b). A route from a nitrile to an ALDEHYDE (not directly obtainable by simple hydrolysis, which instead gives an acid, as in section 12.5.1). The nitrile is first reduced with stannous chloride and HCl to an imine hydrochloride: R-C#N + 2[H], SnCl2/HCl, gives R-CH=NH.HCl. This imine hydrochloride is then acid-hydrolysed (H3O+) to the aldehyde: R-CH=NH.HCl + H3O+ gives R-CHO + NH4Cl. Worked examples: ethanenitrile gives ethanal; benzonitrile gives benzaldehyde.

✓Final answer

Cannizzaro reaction converts a no-alpha-H aldehyde, with conc. alkali, into an alcohol + a carboxylate salt (disproportionation); Stephen reaction converts a nitrile, via SnCl2/HCl then H3O+, into the corresponding aldehyde.

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