An intramolecular 1,3-chlorine migration in the triad 'carbon-carbon- sulfur' with nucleophilic solvent or catalyst assistance is proposed as a mechanism for the perfluoro-2-methylpent-2-ene-3-sulfenyl chloride 1 ⇌ 2-chloroperfluoro-2-methylpentane-3-thione 2 tautomerism. The data from radionuclidic investigations were used to elucidate the aforementioned mechanism. The results of MNDO calculations showed that the solvation lowers the height of the reaction barriers of both direct and reverse reactions and brings about different reaction pathways for these two processes, providing greater assistance to the 1 → 2 than to the 2 → 1 reaction.
|Original language||English (US)|
|Number of pages||5|
|Journal||Journal of the Chemical Society, Perkin Transactions 2|
|State||Published - 1995|
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