Kinetics of hydrolysis of aromatic bicycling disulfonyl dichlorides

Abstract

Hydrolysis of 16 compounds ClO2S—Ar—B—Ar—SO2Cl (B, bridge) in 20% H2O, 80% v/v CH3CO2H, 0.5 mol dm−3 CH3CO2Na at 298.15 K has been investigated by a polarographic method. From plots of the hydrolysis, pseudo-first-order rate constants for two consecutive reactions [Formula: see text] have been computed and the influence of -SO2Cl groups, bridges B, and SO3− groups on the reactivity of -SO2Cl groups has been discussed. The ratio of rate constants k2/k1 ranges from 0.45 to 30, depending on the structure. Log (k1/(2kH)) correlated linearly with [Formula: see text] and log (k2/k1) correlated linearly with ΔpK for the analogous diamine series H2N—Ar—B—Ar—NH2.