Abstract
The reactions of the title substrates (PTOC and NPTOC, respectively) with secondary alicyclic amines are subjected to a kinetic study in aqueous solution at 25.0 °C, ionic strength 0.2 M (KCl). Under amine excess, pseudo-first-order rate coefficients (kobsd) are found throughout. The order in amine is one for the reactions of piperidine but is of intermediate order between 1 and 2 for the reactions of the other amines. The kinetic results can be accommodated by a reaction scheme with two hypothetical tetrahedral intermediates: a zwitterionic (T±) and an anionic (T-) one, whereby amine catalysis (deprotonation of T± to give T-) is kinetically important. Both the pKa of T± and the rate coefficient for proton transfer (k3 ca. 1010 s-1 M-1) are estimated. The values of the other rate microcoefficients of the scheme are found by a nonlinear least-squares fitting, and these values are compared with those exhibited in the aminolysis of phenyl thionoacetate (PTOA), and S-phenyl and S-(4-nitrophenyl) O-ethyl dith...
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