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Gas‐phase thermolysis of N ‐cyanomethyl‐ N ‐ethyl aniline, N ‐cyanomethyl‐ N ‐ethyl‐ p ‐anisidine, and N ‐cyanomethyl‐ N ‐ethyl‐ p ‐nitroaniline
Author(s) -
Martin Gonzalo,
Ascanio Julian,
Rodriguez Jesús
Publication year - 1998
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1998)30:6<451::aid-kin7>3.0.co;2-r
Subject(s) - chemistry , aniline , yield (engineering) , toluene , thermal decomposition , ketene , medicinal chemistry , thermochemistry , ethylene , arrhenius equation , activation energy , organic chemistry , catalysis , thermodynamics , physics
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 °C, pressures of 7–11 torr and residence times of 0.5–0.9 s, using toluene as carrier gas. N ‐cyanomethyl‐ N ‐ethyl‐ p ‐nitroaniline (ECNA) was thermolyzed at 640°C 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 =10 15.10±0.74 exp(−238±11 kJ/mol· RT ); CEPA: k =10 15.61±0.29 exp(−246±4 kJ/mol· RT ). The results 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. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 451–456, 1998