Autoxidation of cycloalkanes(C5–C8) with molecular oxygen under catalyst-free and solvent-free conditions was conducted systematically for the first time, focusing on the autoxidation temperature and product distribution. The autoxidation of cyclopentane, cyclohexane, cycloheptane and cyclooctane occurs at 120 ℃,130 ℃, 120 ℃, and 105 ℃ respectively, with obvious oxidized products formation. At 140 ℃, 145 ℃, 130 ℃ and 125 ℃, acceptable yields of the oxidized products could be obtained for them, and the oxidized product distributions were investigated in detail. The autoxidation of cycloalkanes follows the pseudo-first-order kinetic model and the apparent activation energies(E_a) for the autoxidation of cyclopentane and cyclohexane are 159.76 kJ·mol^(-1) and 86.75 kJ·mol^(-1) respectively. This study can act as an important reference in screen of suitable reaction temperature and comparison of the performance of various catalysts in the catalytic oxidation of cycloalkanes in the attempt to enhance the oxidized product selectivity.
Haimin ShenYan WangJinhui DengLong ZhangYuanbin She
