Kinetics and Mechanism of the Oxidation of Primary Alcohols by N-Bromoacetamide in Acid Medium

Article abstract of DOI:10.1021/jo00324a022

The kinetics of the oxidation of ten primary alcohols by N-bromoacetamide (NBA) has been studied in acid medium.The main product of the oxidation is the corresponding aldehyde.The reaction is first order in alcohol, NBA, and H(+).The oxidation of ethanol-1,1-d2 indicates no primary kinetic isotope effect.A solvent isotope effect, k(D2O)/k(H2O)= 1.16, was observed at 308 K.The rates were determined at four different temperatures and the activation parameters were evaluated.Addition of acetamide decreases the rate. (H2OBr)(+) has been postulated as the oxidizing species.A mechanism involving formation of a hypobromite ester in the rate-determining step has been proposed.The reaction constant, ρ^*, has a value of -1.53 at 303 K.