Gas-phase thermolysis of N-cyanomethyl-N-ethyl aniline, N-cyanomethyl-N-ethyl-p-anisidine, and N-cyanomethyl-N-ethyl-p-nitroaniline

✍ Scribed by Gonzalo Martin; Julian Ascanio; Jesús Rodriguez

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 153 KB
• Volume: 30
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/(sici)1097-4601(1998)30:6<451::aid-kin7>3.0.co;2-r

✦ Synopsis

N-cyanomethyl-N-ethyl aniline (CEAN) and N-cyanomethyl-N-ethyl-p-anisidine (CEPA) have been thermolyzed in a stirred-flow reactor, in the range of 510-560 ЊC, pressures of 7-11 torr and residence times of using toluene as carrier gas. N-cyanomethyl-N-0.5-0.9 s, ethyl-p-nitroaniline (ECNA) was thermolyzed at 640ЊC and 13% conversion. Ethylene and HCN formed in 43% yield each as products from all three starting materials. Phenyl methanaldimine and p-anisidyl methanaldimine were also products of CEAN and CEPA, respectively. The consumption of CEAN and CEPA showed first-order kinetics for a three-fold increase of reactant inflow and initial conversions of up to 40 percent. The following Arrhenius equations were obtained from the rate coefficients for the production of ethylene: CEAN: k ϭ CEPA:

The re-15.10Ϯ0.74 15.61Ϯ0.29 10 exp(Ϫ238 Ϯ 11 kJ/mol•RT); k ϭ 10 exp(Ϫ246 Ϯ 4 kJ/mol•RT). sults are explained by means of radical, nonchain thermolysis mechanisms. The thermochemistry of relevant reaction steps has been estimated from thermochemical parameters calculated by using the semiempirical AM1 method.