title: Kinetics and mechanisms of the reactions of 3-methoxyphenyl, 3-chlorophenyl, and 4-cyanophenyl 4-nitrophenyl thionocarbonates with alicyclic amines.
abstract: The reactions of 3-methoxyphenyl, 3-chlorophenyl, and 4-cyanophenyl 4-nitrophenyl thionocarbonates (1, 2, and 3, respectively) with a series of secondary alicyclic amines are studied kinetically in 44 wt % ethanol-water at 25.0 degrees C and an ionic strength of 0.2 M (KCl). Pseudo-first-order rate coefficients (k(obsd)) are obtained for all reactions (amine excess was used). The reactions of compound 1 with piperidine, piperazine, and 1-(2-hydroxyethyl)piperazine and of compounds 2 and 3 with these amines and morpholine exhibit linear k(obsd) versus amine concentration plots with slopes (k1) independent of pH. In contrast, the plots are nonlinear upward for the reactions of substrate 1 with morpholine, 1-formylpiperazine, and piperazinium ion and of substrates 2 and 3 with the two latter amines. For all these reactions, a reaction scheme is proposed with a zwitterionic tetrahedral intermediate (T+/-), which can be deprotonated by an amine to yield an anionic intermediate (T-). When the nonlinear plots are fit through an equation derived from the scheme, rate and equilibrium microcoefficients are obtained. The Brönsted-type plots for k1 are linear with slopes of beta1 = 0.22, 0.20, and 0.24 for the aminolysis of 1, 2, and 3, respectively, indicating that the formation of T+/- (k1 step) is rate-determining. The k1 values for these reactions follow the sequence 3 > 2 > 1, which can be explained by the sequence of the electron-withdrawing effects from the substituents on the nonleaving group of the substrates.
authors.affiliation: Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago 22, Chile. ecastro@puc.cl
authors.forename: E A
authors.initials: EA
authors.lastname: Castro
authors.forename: L
authors.initials: L
authors.lastname: Leandro
authors.forename: N
authors.initials: N
authors.lastname: Quesieh
authors.forename: J G
authors.initials: JG
authors.lastname: Santos