Beckmann Rearrangement

Beckmann Rearrangement

Session Objectives

By the end of this
session, students will be able to:

• Steps involved in Beckmann rearrangement

• Mechanism of Beckmann rearrangement

PREPARATION OF BENZANILIDE FROM BENZOPHENONE (BECKMANN
REARRANGEMENT)

Aldehydes and ketones react with hydroxyl amines in the
presence of sodium hydroxide to give an Oxime of low melting point (alpha or
syn aldoxime). 

• It rapidly rearranges to give an isomeric Oxime of higher
melting point by acids-(beta or anti aldoxime).

PREPARATION OF BENZANILIDE FROM BENZOPHENONE (BECKMANN REARRANGEMENT)

• Oximes of ketones undergo Beckmann rearrangement to
substituted amides under the influence of variety of acidic reagents e.g HCOOH,
PCl5, H2SO4, SOCl2, etc.

• In this rearrangement, the migrating group is always anti-
to –OH group and thus this reaction is stereo specific.

• Here benzophenone oxime in presence of PCl5 rearranges
to benzanilide.

Step involved in Beckmann Rearrangement

Reaction:
Step-I: Preparation of benzophenone oxime

Preparation of benzophenone oxime

Step-II:
Preparation of benzanilide from benzophenone oxime

Preparation of benzanilide from benzophenone oxime

Mechanism of Beckmann Rearrangement

MECHANISM: – Step-I: Preparation of benzophenone oxime

Preparation of benzophenone oxime

Step-II: Preparation
of benzanilide:

Preparation of benzanilide

Summary

• Aldehydes and ketones react with hydroxyl amines in the
presence of sodium hydroxide to give an Oxime of low melting point (alpha or
syn aldoxime). 

• This is stable in alkali but rapidly rearranges to give an
isomeric Oxime of higher melting point by acids-(beta or anti aldoxime).

• Oximes of ketones undergo Beckmann rearrangement to
substituted amides under the influence of variety of acidic reagents e.g HCOOH,
PCl5, H2SO4, SOCl2, etc.

• In this rearrangement, the migrating group is always anti-
to –OH group and thus this reaction is stereo specific.

• Here benzophenone oxime in presence of PCl5 rearranges to
benzanilide.

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