Reactions of 1,2-dichlorotetrafluorocyclobut-1-ene and 1,2-dichlorohexafluorocyclopent-1-ene with 2-mercaptoethanol and ethanedithiol and of their products

Article abstract of DOI:10.1016/0022-1139(93)05006-M

1,2-Dichlorohexafluorocyclopent-1-ene and 1,2-dichlorotetrafluorocyclobut-1-ene in tetrahydrofuran solutions of 2-mercaptoethanol or 1,2-ethanedithiol and triethylamine give new mono- or di-substituted cycloolefins by displacement of one or two of the chlorine atoms at the double bond by -SCH2CH2OH or -SCH2CH2SH groups, respectively, as a function of the stoichiometry of the reactions.In several cases, the formation of spirocyclic compounds result via an intramolecular cyclization process with concomitant double-bond shift and loss of fluoride ion.Reactions of the spirocycles with nucleophiles, such as N-methylpiperazine, perfluoroglutaryl fluoride and phenylphosphonotionic chloride give rise to more highly substituted olefins and new macrofluoroheterocycles.