Correlation of the rates of solvolysis of phenyl chlorothionoformate and phenyl chlorodithioformate

The specific rates of solvolysis of phenyl chlorothionoformate (PhOCSCl) ar e remarkably similar to those previously reported for phenyl chlorothioform ate (PhSCOCl). When analyzed using the extended Grunwald-Winstein equation over the usual range of solvent types, these solvolyses show essentially id entical divisions into the solvents favoring the addition-elimination chann el and those favoring the ionization channel. The introduction of one sulfu r caused a partial shift away from the addition-elimination pathway, which was dominant over the full range of solvents for phenyl chloroformate (PhOC OCl). Consistent with these results, introduction of the second sulfur with in phenyl chlorodithioformate (PhSCSCl) leads to a completion of this shift , such that an extended Grunwald-Winstein treatment of the specific rates o f solvolysis now shows the ionization pathway to be dominant over the full range of solvents.