370104-79-3Relevant academic research and scientific papers
Kinetic study of the phenolysis of bis(4-nitrophenyl) carbonate, bis(4-nitrophenyl) thionocarbonate, and methyl 4-nitrophenyl thionocarbonate
Castro,Angel,Arellano,Santos
, p. 6571 - 6575 (2007/10/03)
The reactions of a homogeneous series of phenols with bis(4-nitrophenyl) carbonate (BNPC), bis-(4-nitrophenyl) thionocarbonate (BNPTOC), and methyl 4-nitrophenyl thionocarbonate (MNPTOC) are subjected to a kinetic investigation in water, at 25.0 °C and ionic strength of 0.2 M (KCl). Under excess of phenol over the substrate, all the reactions obey pseudo-first-order kinetics and are first order in phenoxide anion. The reactions of BNPC show a linear Broensted-type plot with slope β=0.66, consistent with a concerted mechanism (one step). In contrast, those of BNPTOC and MNPTOC show biphasic Broensted-type plots with slopes β=0.30 and 0.44, respectively, at high pKa, and β=1.25 and 1.60, respectively, at low pKa, consistent with stepwise mechanisms. For the reactions of both thionocarbonates, the pKa value at the center of the BrSnsted plot (pKa0) is 7.1, which corresponds to the pKa of 4-nitrophenol. This confirms that the phenolyses of the thionocarbonates are stepwise processes, with the formation of an anionic tetrahedral intermediate. By the comparison of the kinetics and mechanisms of the title reactions with similar reactions, the following conclusions can be drawn: (i) Substitution of S- by O- in an anionic tetrahedral intermediate (T-) destabilizes it. (ii) The change of MeO by 4-nitrophenoxy in T- results in an increase of both the rate constant and equilibrium constant, for the formation ofT-, and also in an enlargement of the rate coefficient for the expulsion of 4-nitrophenoxide from T-. (iii) Substitution of an amino group in a tetrahedral intermediate by ArO destabilizes it. (iv) Secondary alicyclic amines and other amines show greater reactivity toward MNPTOC than isobasic phenoxide anions.
Kinetics and mechanisms of the reactions of 3-methoxyphenyl, 3-chlorophenyl, and 4-cyanophenyl 4-nitrophenyl thionocarbonates with alicyclic amines
Castro,Leandro,Quesieh,Santos
, p. 6130 - 6135 (2007/10/03)
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 °C and an ionic strength of 0.2 M (KCl). Pseudo-first-order rate coefficients (kobsd) 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 kobsd 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 Broensted-type plots for k1 are linear with slopes of β1 = 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.
