Peroxidation of secondary carbon in alkanes and cycloalkanes

A method for the peroxidation of secondary carbon in hydrocarbons selected from the group consisting of alkanes and cycloalkanes to produce secondary hydroperoxides comprising:

• a. peroxidizing said hydrocarbon with molecular oxygen at a temperature of from 100.degree. to 200.degree. C. in the presence of a tertiary hydroperoxide initiator containing no more than 50 mole percent tertiary alcohol and the amount of tertiary hydroperoxide is from 0.5 to 10 mole percent of said hydrocarbon to produce a mixture of said secondary hydroperoxide, an unreacted quantity of said hydrocarbon, as unreacted quantity of said tertiary hydroperoxide and said tertiary alcohol;
• b. subjecting said mixture to azeotropic distillation whereby first a minimum boiling binary azeotrope of said tertiary alcohol and a portion of said unreacted hydrocarbon is removed from said mixture as overhead leaving a bottoms containing said secondary hydroperoxide, remaining unreacted hydrocarbon and said unreacted quantity of tertiary hydroperoxide;
• c. subjecting said bottoms to a further azeotropic distillation whereby a second minimum boiling binary azeotrope of said tertiary hydroperoxide and at least a portion of said remaining unreacted hydrocarbon is removed from said bottoms as an overhead and recycling said second minimum boiling azeotrope to said peroxidizing step.