Effect of substitution of oxygen by sulfur in the nonleaving group of a carbonate: kinetics of the phenolysis and benzenethiolysis of S‐methyl aryl thiocarbonates |
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| Authors: | Enrique A Castro Margarita Aliaga José G Santos |
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| Institution: | 1. Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago 6094411, Chile;2. Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago 6094411, ChileFacultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago 6094411, Chile.=== |
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| Abstract: | The phenolysis and benzenethiolysis of S‐methyl 4‐nitrophenyl thiocarbonate ( 1 ) and S‐methyl 2,4‐dinitrophenyl thiocarbonate ( 2 ) in water are studied kinetically. The Brønsted plots (log k N versus nucleophile basicity) are linear for all reactions. The Brønsted slopes for 1 and 2 are, 0.51 and 0.66 (phenolysis) and 0.55 and 0.70 (benzenethiolysis), respectively. These values suggest a concerted mechanism for these reactions, as found in the corresponding carbonates. Namely, substitution of OMe by SMe in the nonleaving group does not change the mechanism. Copyright © 2007 John Wiley & Sons, Ltd. |
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| Keywords: | phenolysis benzenethiolysis kinetics thiocarbonates |
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