The Mechanism of Decomposition of Azo Compounds. II. Cage Effects in the Decomposition of α,α-Azoisobutyronitrile and Related Compounds

Abstract

The rate of formation of dimethyl-N-(2-cyano-2-propyl)-ketenimine (RR') from α, α'-azoisobutyronitrile (RN_2R) has been studied in carbon tetrachloride, benzene and styrene. A particularly detailed study was made in carbon tetrachloride solution at 62.5°. The yield of tetramethylsuccinonitrile (RR) from RN_2R in the presence of bromine has also been estimated. The results, coupled with other available information concerning the decomposition of RN_2R and RR', show that the ketenimine is produced by coupling of both primary and secondary decomposition fragments. Application of the theory of the cage effect as an important part of the mechanism of decomposition of azonitriles and ketenimines is justified.

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