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Aliphatische azoverbindungen, 14. Eine kinetische analyse des thermischen zerfalls aliphatischer azonitrile

1983; Wiley; Volume: 184; Issue: 6 Linguagem: Inglês

10.1002/macp.1983.021840612

0025-116X

Werner Barbe, Christoph Rüchardt,

Chemical Reactions and Mechanisms

Abstract Ketenimines 4 are known to be formed in a side equilibrium during the thermal decomposition of azonitrile initiators 1 , as e.g. 2,2′‐azoisobutyronitrile (1a) . The concentration of 4 was monitored by IR during the decomposition reaction of 1 , and the final yield ratio of substituted succinonitrile 3 and nitrile 5 was determined by GC. Together with the rate constant k 1 of 1 , these data suffice for calculating k ‐3 , the rate of decomposition of 4 , and k 3 / k 2 the rate ratio of the two possible modes of dimerisation of α‐cyanoalkyl radicals 2 .