64037-64-5Relevant academic research and scientific papers
Gas-phase thermolysis of t-butylsulf enamides: N, N-dimethyl t-butylsulfenamide, 2,6-dimethylpiperidinyl t-butylsulfenamide, and N-t-butyl t-butylsulfenamide
Martin, Gonzalo,Ascanio, Julian,Rodriguez, Jesus
, p. 353 - 359 (2007/10/03)
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) = 1014.45±0.46exp(-175 ± 5 kJ/mol RT) 2,6-dimethylpiperidyl t-butylsulfenamide: k(s-1) = 1014.38±0.26exp(-161 ± 3 kJ/mol RT) N-t-butyl t-butylsulfenamide: k(s-1) = 1014.75±0.37exp(-184 ± 7 kJ/mol 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.
