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The Thermochemical Kinetics of Retro “-Ene” Reactions of Molecules with the General Structure (Allyl)XYH in the Gas Phase. 8.. The Thermal Decomposition of Methylallylaniline in the Gas Phase

✍ Scribed by Kurt W. Egger; Peter Vitins

Publisher
John Wiley and Sons
Year
1974
Tongue
German
Weight
568 KB
Volume
57
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

The thermal decomposition of N‐methyl‐N‐allylaniline in the gas phase over the temperature range 575 to 665 K appears to be a homogeneous radical chain reaction yielding allyl and C~6~H~5~NCH~3~ radicals in the primary step as is indicated by the numerous chain‐terminating radical recombination products and the effect of diluents on the rate constants. From experiments carried out with excess of diluent, first order rate constants which can be identified with the rate determining chain initiating step, were calculated using the internal standard technique and found to fit the Arrhenius relationship \documentclass{article}\pagestyle{empty}\begin{document}$\ log({\rm k}/{\rm s}^{ - 1}) = 13.75 \pm 0.43 - (48.50 \pm 1.23,{\rm kcal mol}^{{\rm - 1}})/2.303,{\rm RT} $\end{document}. Although the Arrhenius parameters are slightly low, which is attributed to some loss of substrate by secondary reactions, they are in general agreement with prediction. The relevance of these results to the thermal behavior of allylamines and the nature of six‐center transition states is discussed.

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