A stereochemical test of similarly substituted tetramethylenediazene and cyclic azo decompositions in the gas phase at the same temperature

Abstract

Valid comparisons of stereochemical tests directed toward an understanding of the behavior of 1,4-diradicals (1) generated by very different methods have been complicated by the lack of examples in the literature where the type of substituents, degree of substitution, and reaction conditions have been the same. We report here the first comparison of the product compositions from similarly substituted tetramethylenediazene1 (2) and six-membered cyclic azo (3) thermal decompositions carried out in the gas phase at the same temperature (306° and 439°). This stereochemical test bears on the important question of whether one can generate the same reactive species (e.g., 1,4-diradicals) by the extrusion of nitrogen 'by two very different methods and hence from two different points on an energy surface.

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