79999-59-0Relevant academic research and scientific papers
A formal sigmatropic reaction involving free radical intermadiates: a mechanistic investigation
Bates, Gordon S.,Ramaswamy, S.
, p. 745 - 754 (2007/10/02)
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 deg C.An investigation of generality and specific mechanism of this formal 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-1 mol-1), crossover and trapping experiments, and the lack of a solvent effect (decane vs.DMF), an intermolecular, free-radical chain pathway has been proposed for the isomerization.During the rearrangement of several of the compounds esr signals were observed that were consistent with the presence of the proposed free-radical intermediates.These esr signals have been computer simulated.
