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Gas-phase thermolysis of N-methyl-N-phenyl-tert-butylsulfenamide and morpholinyl-tert-butylsulfenamide

✍ Scribed by Gonzalo Martin; Julian Ascanio; Jesus Rodriguez

Publisher
John Wiley and Sons
Year
1998
Tongue
English
Weight
78 KB
Volume
11
Category
Article
ISSN
0894-3230

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✦ Synopsis

N-Methyl-N-phenyl-tert-butylsulfenamide (MPSA) and morpholinyl-tert-butylsulfenamide (MOSA) were thermolyzed in a stirred-flow reactor at temperatures of 340-390 Β°C and pressures of 7-13 Torr, using toluene as carrier gas, at residence times of 0.3-1.3 s. Isobutene was formed in 99% yield through first-order reactions having the following Arrhenius parameters (A,s Γ€1 , E a , kJ mol Γ€1 ): MPSA, log A = 12.41 AE 0.02, E a = 158.8 AE 0.2; MOSA, log A = 12.91 AE 0.22, E a = 159 AE 3. It is proposed that the elimination of isobutene takes place by unimolecular reaction mechanisms involving polar, four-center cyclic transition states, forming S-unsubstituted thiohydroxylamines as coproducts. Thermochemical parameters, estimated by semiempirical AM1 calculations, are reported for the latter and for the parent molecules.

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