Phenolysis of diaryl thiolcarbonates and thionocarbonates

Enrique A. Castro, Marjorie Cepeda, Paulina Paveza, José G. Santos

Resultado de la investigación: Contribución a una revistaArtículo

7 Citas (Scopus)

Resumen

The phenolysis of phenyl S-4-nitrophenyl thiolcarbonate (1), 4-chlorophenyl S-4-nitrophenyl thiolcarbonate (2), phenyl 4-nitrophenyl thionocarbonate (3), 3-chlorophenyl 4-nitrophenyl thionocarbonate (4) and 3-methoxyphenyl 4-nitrophenyl thionocarbonate (5) are studied kinetically in 44 wt% ethanol-water, at 25.0 °C, ionic strength 0.2 M. The Brøpnsted plots (log kN vs. PKa of phenols) for the reactions of 1 and 2 are linear and those of 3, 4 and 5 are curved. The Brønsted slopes for 1 and 2 are 0.64 and 0.60, respectively, which suggest a concerted mechanism for these reactions. The curved Brønsted plots for the reactions of 3, 4 and 5 show slope values of 1.0, 1.1 and 1.1, respectively, at low pKa and 0.39, 0.28 and 0.34, respectively, at high pK a. The shape and slope values of these Brønsted plots are in accordance with a stepwise mechanism. The reactivity towards phenoxides of the thiocarbonates increases with the increase in the Hammett σ value for the substituents in the non-leaving group. The fact that the phenolysis of 3 is stepwise, whereas that of phenyl 4-nitrophenyl carbonate is concerted can be attributed to the destabilization of the intermediate T-. A similar argument explains the stepwise phenolysis of 3, in contrast to the concerted phenolysis of 1, where there is an additional destabilization of T- caused by the change of the leaving group, from 4-nitrophenoxide in 3 to 4-nitrobenzenethiolate in 1. Thiolcarbonates 1 and 2 in 44 wt% ethanol-water are less reactive towards phenoxide anions (ca. 100-fold) than their corresponding oxycarbonates in water.

Idioma originalInglés
Páginas (desde-hasta)455-459
Número de páginas5
PublicaciónJournal of Physical Organic Chemistry
Volumen22
N.º5
DOI
EstadoPublicada - may 2009

Áreas temáticas de ASJC Scopus

  • Química física y teórica
  • Química orgánica

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