An anomalous effect of methyl group on acidity of acylthioureas

Abstract
Dissociation constants and methanolysis rate constants have been measured of 1-acetyl- and 1-benzoylthioureas and their N-methyl derivatives. Replacement of hydrogen atom at N(1) (next to the acyl group) by methyl group increases the acidity of the benzoyl derivative by one order, that of the acetyl derivative by as much as two orders of magnitude. Replacement of both hydrogens at N(3) by methyl groups lowers the methanolysis rate constant by more than two orders, whereas the replacement of hydrogen atom at N(1) by methyl group increases the methanolysis rate by the factor of 30.

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