Relationships between the electrophilicity index and experimental rate coefficients for the aminolysis of thiolcarbonates and dithiocarbonates.

Quantitative relationships are reported between the global electrophilicity index and the experimental rate coefficients for the reactions of thiolcarbonates and dithiocarbonates with piperidine. The validated scale of electrophilicity is then used to rationalize the reaction mechanisms of these systems. This scale also makes it possible to predict both rate coefficients and Hammett substituent constants for a series of systems that have not been experimentally evaluated to date.