Experimental and quantum-chemical study of the interaction of cyclohexanediones and their monoethylene ketals with hydrogen peroxide

The reactivity of cyclohexanediones and their monoethylene ketals with hydrogen peroxide was studied. It was established that 1,2- and 1,3-cyclohexanediones virtually do not react with H2O2, whereas 1,4-cyclohexanedione forms 1,4-dihydroxy-1,4-dihydroperoxycyclohexane. Monoethylene ketals of cyclohexanediones react with hydrogen peroxide to form the corresponding α-hydroxy-α-hydroperoxides. The stereoelectronic factors determining the difference in reactivity of the carbonyl fragment in cyclohexanone, 1,2-cyclohexanedione, and its monoethylene ketal were analyzed within the framework of the semiempirical quantum chemical method MNDO.