62842-25-5Relevant academic research and scientific papers
Gas Phase Thermolysis of Allyl Cyanomethyl Amine, Diallyl Cyanomethyl Amine, Diethyl Cyanomethyl Amine, and Diethyl Propargyl Amine
Martin, Gonzalo,Ascanio, Julian,Rodriguez, Jesus
, p. 99 - 108 (1995)
The title amines were pyrolyzed in a stirred-flow reactor at 380 - 510 deg 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: k(s-1) = 1013.29 +/- 0.35exp(-189 +/- 5 kJ/mol RT) Diallyl cyanomethyl amine: k(s-1) = 1013.00 +/- 0.20exp(-183 +/- 3 kJ/mol RT) Diethyl cyanomethyl amine gave a 20:1 gas mixture of ethylene 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 k(s-1) = 1015.30 +/- 0.24exp(-226 +/- 3 kJ/mol RT) Diethyl propargyl amine decomposed cleanly into allene and N-ethyl ethanaldimine.The first-order rate coefficients for allene formation fit the Arrhenius equation k(s-1) = 1012.84 +/- 0.30exp(-168 +/- 4 kJ/mol RT).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.
