A DFT study on secondary reaction pathways in the acid-catalysed Beckmann rearrangement of cyclohexanone oxime in aprotic solvent

In recent studies regarding acid-catalysed Beckmann rearrangement of cyclohexanone oxime in aprotic solvents it has been observed that a quite surprising hydrolysis of the starting material, i.e., cyclohexanone oxime, occurs even if the experimental conditions and the water concentration in the reaction mixture can not justify such a side-reaction. Being this apparent hydrolysis critical for catalyst selectivity and poisoning, a computational DFT study on a possible secondary reaction pathway, involving a bi-molecular reaction between two cyclohexanone oxime molecules in acid media as the primary step, is here reported to explain the experimental results.