BamfordDemjanov

Bamford–Demjanov rearrangement, often written BamfordDemjanov or Bamford–Demjanov reaction, is a named reaction in organic chemistry. It describes the rearrangement of hydroperoxides under acidic conditions to furnish carbonyl compounds, typically aldehydes or ketones, with concomitant migration of part of the carbon skeleton from the original molecule.

Substrates for the Bamford–Demjanov rearrangement are hydroperoxides derived from alcohols and related precursors. Under suitable acidic conditions, the hydroperoxide is activated and undergoes a rearrangement that leads to a carbonyl product. The exact distribution of products and the preferred migrating group depend on the structure of the starting material, with secondary and some tertiary hydroperoxides more commonly yielding ketones and, in appropriate cases, primary hydroperoxides yielding aldehydes.

Mechanistically, the reaction is thought to proceed through protonation of the hydroperoxide, formation of a cationic or partially cationic intermediate, and a 1,2-alkyl or aryl shift (a Wagner–Meerwein-type rearrangement) followed by capture and hydrolysis to the carbonyl compound. Conditions often require strong acid or irradiation, and reactions of sensitive peroxides demand careful handling.

History and significance: The rearrangement is named after chemists Bamford and Demjanov, who reported related transformations in the early to mid-20th century. Today, it is primarily of historical and methodological interest, cited in discussions of peroxide rearrangements and in some specialized synthetic contexts. Safety considerations are important due to the energetic and potentially explosive nature of hydroperoxides.