TY - JOUR
T1 - Reversible intramolecular 1,3-chlorine migration in the triad 'carbon-carbon-sulfur'
AU - Popkova, Vera Ya
AU - Anisimov, Victor M.
AU - Dolenko, Georgii N.
AU - Semenenko, Mikhail N.
AU - Fedoseev, Vladimir M.
PY - 1995
Y1 - 1995
N2 - 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.
AB - 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.
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U2 - 10.1039/p29950001375
DO - 10.1039/p29950001375
M3 - Article
AN - SCOPUS:37049083004
SN - 1472-779X
SP - 1375
EP - 1379
JO - Journal of the Chemical Society, Perkin Transactions 2
JF - Journal of the Chemical Society, Perkin Transactions 2
IS - 7
ER -