65448-74-0Relevant articles and documents
Kinetic study of the reactions of methyl 2,4,6-trinitrophenyl carbonate with anilines
Castro, Enrique A.,Aliaga, Margarita E.,Santos, Jose G.
experimental part, p. 23 - 30 (2011/05/15)
The title reactions in water are subjected to a kinetic investigation. Under excess amine, pseudo-first-order rate coefficients (kobsd) are obtained. Plots of kobsd against aniline concentration are linear, with kN as the slope. The Bronsted-type plot (log kN vs anilinium pK a) is linear with slope 0.7, consistent with a concerted mechanism. By comparison of these reactions with others, it is concluded that anilines destabilize the tetrahedral intermediate relative to isobasic pyridines. The change of 2,4-dinitrophenoxide by 2,4,6-trinitrophenoxide as the leaving group of the carbonate destabilizes the tetrahedral intermediate and makes possible a change in mechanism. ARKAT-USA, Inc.
