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Kinetic and Mechanistic Investigation of the Aminolysis of 3-Methoxyphenyl 3-Nitrophenyl Thionocarbonate, 3-Chlorophenyl 3-Nitrophenyl Thionocarbonate, and Bis(3-nitrophenyl) Thionocarbonate
journal contribution
posted on 2002-05-09, 00:00 authored by Enrique A. Castro, Angelique Galvez, Leonardo Leandro, José G. SantosThe reactions of the title thionocarbonates (6, 7, and 8, respectively) with a series of secondary
alicyclic amines are subjected to a kinetic investigation in 44 wt % ethanol−water, 25.0 °C, ionic
strength 0.2 M (KCl). Under excess amine, pseudo-first-order rate coefficients (kobsd) are obtained
for all reactions. Reactions of substrates 6 and 7 with piperidine and of thionocarbonate 8 with the
same amine and piperazine, 1-(2-hydroxyethyl)piperazine, and morpholine show linear kobsd vs
[amine] plots, with slopes (k1) independent of pH. On the other hand, these plots are nonlinear
upward for the reactions of substrates 6 and 7 with all the amines, except piperidine, and also for
the reactions of compound 8 with 1-formylpiperazine and piperazinium ion. For all these reactions
a mechanistic scheme is proposed with the formation of a zwitterionic tetrahedral intermediate
(T±), which can transfer a proton to an amine to give an anionic intermediate (T-). Rate and
equilibrium microcoefficients of this scheme, k1, k-1, K1 (= k1/k-1), and k2, are obtained by fitting
the nonlinear plots through an equation derived from the scheme. The Brönsted-type plots for k1
are linear with slopes β1 = 0.19, 0.21, and 0.26 for the aminolysis of 6, 7, and 8, respectively. This
is consistent with the hypothesis that the formation of T± (k1 step) is the rate-determining step.
The k1 values for these reactions follow the sequence 8 > 7 > 6, consistent with the sequence of the
electron-withdrawing effects from the substituents on the “nonleaving” group of the substrates.
The k1 values for the aminolysis of 6, 7, and 8 are smaller than those for the same aminolysis of
3-methoxyphenyl, 3-chlorophenyl, and 4-cyanophenyl 4-nitrophenyl thionocarbonates (2, 3, and 4,
respectively). The k2 values (expulsion of the nucleofuge from T±) increase as the electron withdrawal
from the nonleaving group increases. These values are smaller for the aminolysis of 6, 7, and 8
compared to those for the same aminolysis of 2, 3, and 4, respectively.