E. Castro, R. Acevedo, José G. Santos
Jul 1, 2011
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Influential Citations
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Journal
Journal of Physical Organic Chemistry
Abstract
The reactions of bis(4-nitrophenyl), 3-chlorophenyl 4-nitrophenyl, and 3-methoxyphenyl 4-nitrophenyl thionocarbonates (1, 2, and 3, respectively) with a series of anilines are subjected to a kinetic investigation in 44 wt.% ethanol–water, at 25.0 °C and an ionic strength of 0.2 M. Under aniline excess, pseudo-first-order rate coefficients (kobs) are found. Plots of kobs versus aniline concentration are linear, with the slopes (kN) pH independent, kN being the rate coefficient for the anilinolysis of the thionocarbonates. The Bronsted plot (log kN vs. pKa of anilinium ions) for thionocarbonate 1 is linear, with slope (β) 0.62, which is consistent with a concerted mechanism. The Bronsted plots for thionocarbonates 2 and 3 are curved, with slopes 0.1 at high pKa for both reaction series and slopes 0.84 and 0.79 at low pKa for the reactions of 2 and 3, respectively. The latter plots are in accordance to stepwise mechanisms, through a zwitterionic tetrahedral intermediate (T±) and its anionic analogue (T−), the latter being formed by deprotonation of T± by the basic form of the buffer (HPO). The Bronsted curves are explained by a change in the rate-limiting step, from deprotonation of T± at low pKa, to its formation at high pKa. The influence of the amine nature and the non-leaving and electrophilic groups of the substrate on the kinetics and mechanism is also discussed. Copyright © 2010 John Wiley & Sons, Ltd.