Collect. Czech. Chem. Commun. 1981, 46, 1970-1975

Hydrolysis kinetics and mechanism of diaryldithiocarbamates in 20% aqueous dioxane

Jaromír Mindl, Jiří Sulzer and Miroslav Večeřa

Department of Organic Chemistry, Institute of Chemical Technology, 532 10 Pardubice


Nine diaryldithiocarbamates have been prepared. Kinetic study of their hydrolysis has revealed that this hydrolysis proceeds by E1cB mechanism in the pH range 2 to 12. Values of activation entropies, reaction constants, Broensted coefficient, and comparison with reactivity of the corresponding N-methyl analogue have been used as criteria for the suggested mechanism. In acid media pH 2 to 0.4 and H0 -0.6 the hydrolysis follows a mechanism analogous to AAc2. Results of hydrolyses of dithiocarbamates, thiocarbamates and carbamates are compared.