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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
Author(s) -
Egger Kurt W.,
Vitins Peter
Publication year - 1974
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19740570128
Subject(s) - chemistry , arrhenius equation , diluent , thermal decomposition , reaction rate constant , gas phase , decomposition , atmospheric temperature range , arrhenius plot , radical , kinetics , thermodynamics , homogeneous , activation energy , organic chemistry , physics , quantum mechanics
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.