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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Pyrolysis of Aryl Azides.X. Effects of Azide Concentration on Rate Constants and Product Yields

LK Dyall and PAS Smith

Australian Journal of Chemistry 43(6) 997 - 1007
Published: 1990

Abstract

First-order rate constants (k1) have been measured for pyrolysis of azidobenzenes in decalin solution, in the presence of a free-radical chain inhibitor to prevent any induced decomposition. The new values of k1 for the spontaneous unimolecular thermolysis are lower than previously reported ones, and require revision of published neighbouring group effects. Product yields ( azo compound and primary amine) vary with initial concentration of azide in ways which suggest the species responsible for induced decomposition is not triplet arylnitrene , but a solvent-derived free radical. There is no evidence for induced decomposition when nitrobenzene is the solvent.

For aryl azides with no neighbouring group effects operating in their pyrolysis, the Arrhenius parameters Eact and ΔSactobey a precise linear relationship.

https://doi.org/10.1071/CH9900997

© CSIRO 1990

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