Tetrahedron

3d-orbital resonance in divalent sulphide—X: The effects of α-aryl and α-alkylmercapto groups on the rate of decarboxylation of α-substituted carboxylic acids

S Oae, W Tagaki, K Uneyama, I Minamida

Index: Oae,S. et al. Tetrahedron, 1968 , vol. 24, p. 5283 - 5291

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Citation Number: 12

Abstract

Several α-mercaptoacetic and related acids were synthesized and the rates of the amine- catalysed decarboxylation were measured. In the carbanion-forming reaction, the α- mercapto group exhibits a dramatic rate-enhancement, due to the 3d-orbital resonance effect of the divalent sulphide group. For example, the rate of the decarboxylation of diphenylmercaptoacetic acid was 8· 8× 103 fold greater than that of the oxygen analog, ...