Gas phase thermolysis of allyl cyanomethyl amine, diallyl cyanomethyl amine, diethyl cyanomethyl amine, and diethyl propargyl amine

✍ Scribed by Gonzalo Martin; Julian Ascanio; Jesus Rodriguez

• Publisher: John Wiley and Sons
• Year: 1995
• Tongue: English
• Weight: 557 KB
• Volume: 27
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550270203

✦ Synopsis

The title amines were pyrolyzed in a stirred-flow reactor a t 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:

2920.35 exp(-189 2 5 kJ/mol RT) Diallyl cyanomethyl amine: k(s-') = 1013~00'0~20exp(-183 2 3 kJ/mol RT) Diethyl cyanomethyl amine gave a 20:l 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-l) = 1015.3020.24 exp(-226 2 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-l) = 1012.8420.30 exp(-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.