Cyclohexene Epoxidation with Cyclohexyl Hydroperoxide: A Catalytic Route to Largely Increase Oxygenate Yield from Cyclohexane Oxidation

The industrially important deperoxidation reaction of cyclohexyl hydroperoxide was combined with the epoxidation of cyclohexene over a series of mesoporous titanium silicates. The process was found to proceed with high selectivity, forming cyclohexanol, cyclohexanone, and epoxy-cyclohexane. The deperoxidation and epoxidation reactions were found to compete. However, by changing the surface hydrophobicity of the catalysts or the applied olefin/peroxide ratio, the overall mechanism could be directed in favor of the epoxidation. In this way, the combined selectivity toward valuable alicyclic oxygenates from cyclohexane oxidation based on peroxide conversion could be increased up to 170%. The catalysts where found to be stable from recycling and filtration experiments.