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  • Articles  (3)
  • Physical Chemistry  (3)
  • 1995-1999  (3)
  • 1
    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
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  • 2
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The amide derivatives of t-butylsulfenic acid mentioned in the title have been thermolyzed in a stirred-flow reactor at temperatures of 273-390°C and pressures of 7-15 torr, using toluene as carrier gas, at residence times of 0.4-2 s. Isobutene formed in 95-99% yields, through order one reactions, following the Arrhenius equations: N, N-dimethyl t-butylsulfenamide: $$k(s^{-1})=10^{14.45\pm 0.46}\exp(-175\pm 5 {\rm kJ/mol}\,{\bf RT})$$ 2,6-dimethylpiperidyl t-butylsulfenamide: $$k(s^{-1})=10^{14.38\pm 0.26}\exp(-161\pm 3 {\rm kJ/mol}\,{\bf RT})$$ N-t-butyl t-butylsulfenamide: $$k(s^{-1})=10^{14.75\pm 0.37}\exp(-184\pm 7 {\rm kJ/mol}\,{\bf RT})$$These thermolyses are considered to take place through unimolecular, four-center cyclic transition-state reaction mechanisms, giving rise to isobutene plus the corresponding S-unsubstituted thiohydroxylamines. The latter decompose outside the reactor at temperatures above -78°C forming free sulfur and dimethylamine, 2,6-dimethylpiperidine, and t-butylamine, respectively. © 1996 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
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  • 3
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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=1015.10±0.74 exp(-238±11 kJ/mol·RT); CEPA: k=1015.61±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
    Additional Material: 1 Ill.
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