53146-16-0Relevant academic research and scientific papers
Gas-phase thermolysis of N-substituted diallyl- and allylpropargylamines
Martin, Gonzalo,Ascanio, Julian,Rodriguez, Jesus
, p. 49 - 54 (2007/10/03)
Various diallyl- and allylpropargylamines were pyrolyzed in a stirred-flow reactor at temperatures in the range of 330-500 °C, pressures of 8-16 Torr and residence times of 0·4-2·4 s using toluene as carrier gas. The reaction products were propene, allene and aldimines. The allene to propene ratio changed considerably with the third substituent on the N atom. At conversions in the range 13-55%, the consumption of the amines showed first-order kinetics. The following Arrhenius parameters [A (s-1) and Ea (kj mol-1)] were obtained from the rate coefficients: diallyl-tert-butylamine, log A = 10·32±0·12, Ea = 139±2; diallylneopentylamine, log A = 12·87±0·26, Ea = 168±3; allylpropargyl-tert-butylamine, log A = 10·23±0·18, Ea = 126±2; allylpropargyltosylamine, log A = 13·05±0.36, Ea = 197±5; and allylpropargylphenylamine, log A = 12·10± 0·35, Ea = 162±4. Polar, six-center cyclic transition states are suggested for the elimination of propene and allene, via non-concerted bond breaking-bond forming mechanisms.
