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Gas phase thermolysis of cyanomethyl t-butyl sulfide and cyanomethyl t-butyl ether

✍ Scribed by Gonzalo Martin; Henry Martinez

Publisher
John Wiley and Sons
Year
1987
Tongue
English
Weight
453 KB
Volume
19
Category
Article
ISSN
0538-8066

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✦ Synopsis

The pyrolyses of cyanomethyl t-butyl sulfide and its oxygen homologue have been studied in a stirred-flow system over the temperature range 490440°C and pressures between 5 and 14 Tom. In both cases, isobutene is formed as product in over 97% yield. Hydrogen sulfide is obtained in about half the amount of isobutene in the pyrolysis of the sulfide. Hydrogen cyanide is formed in the pyrolysis of the ether. The first-order rate coefficients for the consumption of the reactants followed the Arrhenius equations Cyanomethyl t-butyl sulfide: k (s-l) = 1012.63=0.23 exp(-201.7 * 3.5) kJ/mol R T Cyanomethyl t-butyl ether: K ( ~-1 ) = 101127-tO.30 exp(-186 ? 5) kJ/mol R T A molecular mechanism involving polar four-centered cyclic transition states is proposed for both reactions, with the CN group stabilizing the partial negative charge developed at the S and 0 atoms.

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