8.4.2 Hydroperoxide Rearrangement

Tertiary hydroperoxide with acid undergoes rearrangement to give ketone and alcohol or phenol. The mechanism is similar to that of Baeyer-Villiger reaction. For example, cumene forms hydroperoxide by autoxidation which is with acid rearranges to give phenol and acetone.

8.4.2 Dakin Reaction

Benzaldehyde or acetophenone bearing hydroxyl substituent in the ortho or para position proceed rearrangement to give catechol or quinol , respectively. The reaction is performed in the presence of alkaline hydrogen peroxide and the mechanism is similar to that of Baeyer-Villiger reaction.

Proposed Mechanism

Examples: