REVERSIBLE INTRAMOLECULAR 1,3-CHLORINE MIGRATION IN THE TRIAD CARBON-CARBON-SULFUR

An intramolecular 1,3-chlorine migration in the triad 'carbon-carbon-s ulfur' with nucleophilic solvent or catalyst assistance is proposed as a mechanism for the perfluoro-2-methylpent-2-ene-3-sulfenyl chloride 1 reversible arrow 2-chloroperfluoro-2-methylpentane-3-thione 2 tautom erism. The data from radionuclidic investigations were used to elucida te the aforementioned mechanism. The results of MNDO calculations show ed that the solvation lowers the height of the reaction barriers of bo th direct and reverse reactions and brings about different reaction pa thways for these two processes, providing greater assistance to the 1- ->2 than to the 2-->1 reaction.