C‐Nitroso compounds: Part. XI. Trans‐azodioxycyclohexane (dimeric nitrosocyclohexane) by photochemical nitrosation of cyclohexane with alkyl nitrites

Publisher Website
Google Scholar
Abstract
The photonitrosation of cyclohexane by tertiary butyl nitrite has been studied as a model system for the photochemical reaction between alkyl nitrites and hydrocarbons. The products are trans‐azodioxycyclohexane (trans‐dimeric nitrosocyclohexane) and a minor amount of cyclohexanone oxime, together in 81 % yield.Most of the trans‐dimer is formed via the cis‐dimer, which can be isolated at low temperature. It is shown that optimal conditions for this reaction involve the use of a tertiary alkyl nitrite in low concentration, wavelengths around 400 nm and temperatures slightly below room temperature.The free radical mechanism of this reaction is supported by electron spin resonance spectroscopy.