Abstract
In a 1% dioxane–water solvent in the presence of Hg2+ ions thiocarbamates p-RC6H4NHC(S)OEt (R = MeO, Me, H, F) rapidly form complexes of 2 thiocarbamate: 1 Hg2+ stoichiometry. In the presence of an excess of Hg2+ ions partial conversion to the 2 : 2-complexes probably occurs which decompose to the corresponding carbamates (p-RC6H4NHCO2Et) and HgS. With R = NO2 the 2 : 2 complex is dominant even at low Hg2+ ion concentrations, and desulfurisation is then independent of [Hg2+]. Electron-withdrawal by R favours the 2 : 2 complex but decreases its rate of decomposition to products. The effects of changes in the hydrogen ion concentration suggest that ionisation of N-bound protons in the complexes favours reaction. A mechanism is suggested. The kinetic behaviour is somewhat similar to that found previously for thiobenzamides, but the new results suggest the mechanism previously proposed may need revision.
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Schedule a callMore From: Journal of the Chemical Society, Perkin Transactions 2
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