46271-32-3Relevant academic research and scientific papers
A classical but new kinetic equation for hydride transfer reactions
Zhu, Xiao-Qing,Deng, Fei-Huang,Yang, Jin-Dong,Li, Xiu-Tao,Chen, Qiang,Lei, Nan-Ping,Meng, Fan-Kun,Zhao, Xiao-Peng,Han, Su-Hui,Hao, Er-Jun,Mu, Yuan-Yuan
, p. 6071 - 6089 (2013/09/12)
A classical but new kinetic equation to estimate activation energies of various hydride transfer reactions was developed according to transition state theory using the Morse-type free energy curves of hydride donors to release a hydride anion and hydride acceptors to capture a hydride anion and by which the activation energies of 187 typical hydride self-exchange reactions and more than thirty thousand hydride cross transfer reactions in acetonitrile were safely estimated in this work. Since the development of the kinetic equation is only on the basis of the related chemical bond changes of the hydride transfer reactants, the kinetic equation should be also suitable for proton transfer reactions, hydrogen atom transfer reactions and all the other chemical reactions involved with breaking and formation of chemical bonds. One of the most important contributions of this work is to have achieved the perfect unity of the kinetic equation and thermodynamic equation for hydride transfer reactions. The Royal Society of Chemistry.
A RATE AND EQUILIBRIUM STUDY OF THE ADDITION OF ACETONE ENOLATE ION TO THE 2-METHYL-5-NITROISOQUINOLINIUM CATION IN AQUEOUS SOLUTION
Bunting, John W.,Tam, James W.
, p. 973 - 979 (2007/10/02)
Rate and equilibrium constants for the reaction between acetone and the 2-methyl-5-nitroisoquinolinium cation to give 1-acetonyl-1,2-dihydro-2-methyl-5-nitroisoquinoline (2) have been evaluated over the pH range 10.0-11.3 in aqueous solutions at 25 deg C.This reaction is shown to occur under much milder conditions (temperature, pH) and in much shorter reaction times than previously used for the synthesis of this adduct.Analogous data for the reaction of hexadeuteroacetone with this heterocyclic cation are also presented.The formation of 2 is shown to be first order in each of acetone, isoquinolinium cation, and hydroxide ion, and is not catalyzed by carbonate buffer species.These data are consistent with the rate-determining attack of the acetone enolate anion upon the isoquinolinium cation.The microscopic reverse of this reaction is the uncatalyzed decomposition of 2, which is consistent with the observed pH independence of the first-order rate constant for this process.Quantitative comparisons of rates and equilibria for the addition of hydroxide ion and acetone enolate ion to this isoquinolinium cation and to substituted benzaldehydes are now available.
