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Gas‐phase thermolysis of sulfur compounds. Part VIII. Chloromethyl allyl, cyanomethyl allyl, 1‐cyanoethyl allyl and neopentyl allyl sulfides
Author(s) -
Martin Gonzalo,
Martinez Henry,
Suhr Harald,
Suhr Ursula
Publication year - 1986
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/kin.550180308
Subject(s) - chemistry , alkyl , medicinal chemistry , sulfide , propene , thermal decomposition , moiety , sulfur , arrhenius equation , reactivity (psychology) , organic chemistry , catalysis , activation energy , medicine , alternative medicine , pathology
Abstract The pyrolyses of four alkyl allyl sulfides with substituents on the αC atom of the alkyl moiety have been studied in a stirred‐flow system over the temperature range 340‐400°C and pressures between 2 and 12 torr. The only products formed are propene and thioaldehydes. The reactions showed first‐order kinetics with the rate coefficients following the Arrhenius equations: Chloromethyl allyl sulfide:\documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{{\rm - 1}}) = 10^{10.74 \pm 0.23} \exp ( - 144 \pm 3){\rm kJ/mol}RT $$\end{document}Cyanomethyl allyl sulfide:\documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{{\rm - 1}}) = 10^{10.20 \pm 0.19} \exp ( - 129 \pm 2){\rm kJ/mol}RT $$\end{document}1‐cyanoethyl allyl sulfide:\documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{{\rm - 1}}) = 10^{11.09 \pm 0.18} \exp ( - 141.5 \pm 2.2){\rm kJ/mol}RT $$\end{document}Neopentyl allyl sulfide:\documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{{\rm - 1}}) = 10^{10.54 \pm 0.24} \exp ( - 144 \pm 3){\rm kJ/mol}RT $$\end{document}The effects of these and other substituents on the reactivity is discussed in relation with the stabilization of a polar six‐centered transition state. The results support a non‐concerted mechanism where the 1–5 αH atom shift is assisted by its acidic character.