AbstractThe gas phase thermal decomposition of triallylamine was studied in the temperature range 531 to 620 K. The major products observed in the reaction were propylene and 3‐picoline. The first order rate constants for depletion of triallylamine, obtained using the internal standard technique, are found to be independent of pressure and conversion, and fit theArrheniusrelationship\documentclass{article}\pagestyle{empty}\begin{document}$$ \log ({\rm k}/{\rm s}^{ - 1}) = 11.74 \pm 0.07 - (38.27 \pm 0.19)/\theta \,\,{\rm where}\,\theta = 2.303\,{\rm RT}\,{\rm kcal/mol} $$\end{document}The reaction appears to be homogeneous, as a 15‐fold change in thc surface‐to‐volume ratio of the vessel left the rate constants unchanged. The Arrhenius parameters are consistent with a molecular elimination reaction involving a six‐center transition state, yielding propylene and N‐allyl‐prop‐2‐enaldimine. It is proposed that the latter product undergoes a 1,5‐hydrogen transfer, followed by a ring closure reaction to yield dihydropicoline, which in turn reacts forming 3‐picoline via a self‐initiated