Experimental and theoretical studies on the nucleofugality patterns in the aminolysis and phenolysis of S-Aryl O-Aryl thiocarbonates

Enrique A. Castro, Margarita Aliaga, Paola R. Campodónico, Marjorie Cepeda, Renato Contreras, José G. Santos

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(Chemical Equation Presented) The reactions of S-phenyl, S-(4-chlorophenyl), and S-(2,3,4,5,6-pentafluorophenyl) 4-nitrophenyl thiocarbonates (9, 11, and 16, respectively) with a series of secondary alicyclic (SA) amines and those of S-(4-methylphenyl) 4-nitrophenyl thiocarbonate (8) and compounds 9 and 11 with a series of phenols are subjected to a kinetic investigation in 44 wt % ethanol-water, at 25.0°C and an ionic strength of 0.2 M. The reactions were followed spectrophotometrically. Under nucleophile excess, pseudo-first-order rate coefficients (kobsd) were found. For all these reactions, plots of kobsd vs. free amine or phenoxide anion concentration at constant pH are linear, the slope (k N) being independent of pH. The Brønsted-type plots (log kN vs. pKa of the conjugate acids of the nucleophiles) for the aminolysis of 9, 11, and 16 are linear with slopes β = 0.85, 0.90, and 0.67, respectively. The two former slopes are consistent with a stepwise mechanism, through a zwitterionic tetrahedral intermediate, which breaking to products is rate determining. The latter β value is consistent with a concerted mechanism. The Brønsted-type plots for the phenolysis of thiocarbonates 8, 9, and 11 are linear with slopes β = 0.62, 0.70, and 0.69, respectively. These β values and the absence of curvature at pK a = 7.5 confirm a concerted mechanism. In all these reactions, except those of 16, the main nucleofuge is 4-nitrophenoxide, being the thio benzenethiolate the minor nucleofuge. For the reactions of thiocarbonate 16 the main nucleofuge is pentafluorobenzenethiolate whereas little 4-nitrophenoxide was found. The reactions of two SA amines with S-(3-chlorophenyl) 4-nitrophenyl thiocarbonate (10) were subjected to product analysis, showing 60% 4-nitrophenoxide and 40% 3-chlorobenzenethiolate. The study is completed with a theoretical analysis based on the group electrophilicity index, a reactivity descriptor that may be taken as a measure of the ability of a group or fragment to depart from a molecule with the bonding electron pair. The theoretical analysis is in accordance with the experimental results obtained and predicts relative nucleofugalities of O-aryl vs. S-aryl groups in a series of diaryl thiocarbonates not experimentally evaluated to date.

Original languageEnglish
Pages (from-to)9173-9179
Number of pages7
JournalJournal of Organic Chemistry
Issue number23
Publication statusPublished - 4 Dec 2009

ASJC Scopus subject areas

  • Organic Chemistry


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