Photochemical transformations. Part XXI. A comparison of the photolysis and pyrolysis of organic nitrites

Abstract

It has been confirmed that the pyrolysis of nitrites in the molten state does not lead to hydrogen-atom transfer reactions such as are well known in nitrite photolysis. An ionic mechanism has been advanced to explain the reactions of nitrites in the molten phase. Radicals are not involved in this scheme.

Vapour-phase pyrolysis of suitably constituted nitrites, on the other hand, has been shown to produce alkoxyradicals which rearrange by hydrogen-atom transfer in the manner expected. In the gas phase the ionic mechanism of decomposition is not available and the pyrolytic results can be reconciled with the extensive earlier kinetic studies.