ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The title amines were pyrolyzed in a stirred-flow reactor at 380-510°C, pressures of 8-15 torr and residence times of 0.3-2.4 s, using toluene as carrier gas. The substrates with an allyl group yielded propene and iminonitriles as reaction products. HCN is formed by decomposition of the iminonitriles. The first-order rate coefficients for propene formation fit the Arrhenius equations Allyl cyanomethyl amine:\documentclass{article} \pagestyle{empty} \begin{document} $$ k({\rm s}^{ - {\rm 1}}) = 10^{13.29 \pm 0.35} {\rm exp(} - {\rm 189} \pm 5{\rm kJ/mol }RT{\rm)} $$ \end{document}Diallyl cyanomethyl amine:\documentclass{article} \pagestyle{empty} \begin{document} $$ k({\rm s}^{ - {\rm 1}}) = 10^{13.00 \pm 0.20} {\rm exp(} - {\rm 183} \pm 3{\rm kJ/mol }RT{\rm)} $$ \end{document} Diethyl cyanomethyl amine gave a 20:1 gas mixture of ehylene and ethane, plus HCN. The liquid product fraction contained mainly N-ethyl methanaldimine. The first-order rate coefficients for ethylene formation followed the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - {\rm 1}}) = 10^{15.30 \pm 0.24} {\rm exp(} - {\rm 226} \pm 3{\rm kJ/mol }RT{\rm)} $$\end{document} Diethyl propargyl amine decomposed cleanly into allene and N-ethyl ethanaldimine. The first-order rate coefficients for allene formation fit the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - {\rm 1}}) = 10^{12.84 \pm 0.30} {\rm exp(} - {\rm 168} \pm 4{\rm kJ/mol }RT{\rm)} $$\end{document} The results suggest that the above allyl and propargyl amines decompose unimolecularly by mechanisms involving six-center cyclic transition states. For diethyl cyanomethyl amine, a nonchain free radical mechanism is proposed. © 1995 John Wiley & Sons, Inc.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550270203
