Canadian journal of chemistry

A formal [1, 3] sigmatropic reaction involving free radical intermediates: a mechanistic investigation

GS Bates, S Ramaswamy

Index: Bates, Gordon S.; Ramaswamy, S. Canadian Journal of Chemistry, 1985 , vol. 63, p. 745 - 754

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Abstract

The quantitative isomerization of 2, 2-bis (ethylthio)-3, 3-dimethylpent-4-enal to 2, 2-bis (ethylthio)-5-methylhex-4-enal was studied over the temperature range 130-170° C. An investigation of the generality and specific mechanism of this formal [1, 3] sigmatropic shift was conducted with six related compounds. The rearrangements were found to obey first- order kinetics, and on the basis of significant positive entropies of activation (52-106 J deg ...