REACTION OF CYCLOHEXANE AND CYCLOHEXYL RADICALS WITH ATOMIC AND MOLECULAR OXYGEN.

Article abstract of DOI:10.1021/ja00365a031

The reaction of oxygen atoms with cyclohexane in a fast-flow system was studied with a photoionization mass spectrometer. Cyclohexyl radicals formed by the initial hydrogen abstraction were detected directly. The subsequent reaction of the cyclohexyl radicals with atomic oxygen proceeds by both hydrogen abstraction (52%) and an oxygen atom addition reaction (48%). The product in the hydrogen abstraction reaction was cyclohexene. Most of the products in the oxygen atom addition reaction resulted from ring cleavage of the vibrationally hot cyclohexyloxy radicals. (The yield of cyclohexanone was just 3%). Competition experiments show that cyclohexyl radicals react (5. 0 plus or minus 1. 3) multiplied by 10** minus **2 times as fast with O//2 as with O(**3P). In the presence of an excess of O//2 both cyclohexene and cyclohexanone are observed but in decreased yields - cyclohexene (25%) and cyclohexanone (2%).