Mechanism of reactions of α- diazosulfones. Part V. Substituent effects in the acid-catalysed hydrolysis of arenesulfonyldiazomethanes †

The synthesis of the α-diazosulfones m-XC6H4SO2CHN2 (X = CH3O, CH3, Cl, CF3 and NO2) by the method of van Leusen and Strating is described. The pseudo first order rate constants for the acid-catalysed hydrolysis of these a-diazosulfones and those of p-XC6H4SO2CHN2 (X = CH3O, CH3, H, Cl, NO2) in 40% (v/v) dioxane-water at 25° have been correlated by the Hammettqσ equation. The deviation found for the p-CH3O-derivative is discussed. A linear correlation has been found between the logarithm of the rate constants and the frequencies of the infrared absorption of the diazo group at about 2100 cm−1. This relationship between rate data and infrared frequencies can be extended to the acid-catalysed solvolysis of other types of aliphatic diazo compounds.