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

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Abstract
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 Hammett qσ 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.