Correlations of the Specific Rates of Solvolysis of Aromatic Carbamoyl Chlorides, Chloroformates, Chlorothionoformates, and Chlorodithioformates Revisited

Additional specific rates of solvolysis are determined for phenyl chloroformate. These values are combined with literature values to give a total of 49 data points, which are used within simple and extended Grunwald-Winstein treatments. Literature values are also brought together to allow treatments in more solvents than previously for three N-aryl-N-methylcarbamoyl chlorides, phenyl chlorothionoformate, phenyl chlorodithioformate, and N,N-diphenylcarbamoyl chloride. For the last two listed, moderately strong evidence for a meaningful inclusion of a term governed by the aromatic ring parameter (I) was indicated. No evidence was found requiring inclusion of this parameter for ionization reactions with only one aromatic ring on the nitrogen of carbamoyl chlorides or for the solvolyses of the chloroformate or chlorothionoformate proceeding by an addition-elimination (association-dissociation) mechanism.