Kinetic study of the proton transfer reaction between 1-nitro-1-(4-nitrophenyl)alkanes and TBD and MTBD bases in acetonitrile solvent

Abstract

The rates of proton transfer reactions between C-acids of the series of nitroalkanes with increasing bulk of R = H, Me, Et, i-Pr substituent as: 4-nitrophenylnitromethane (0), 1-(4-nitrophenyl)-1-nitroethane (1), 1-(4-nitrophenyl)-1-nitropropane (2), 2-methyl-1-(4-nitrophenyl)-1-nitropropane (3) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) have been measured in acetonitrile at pseudo-first-order conditions. The product of the proton transfer reaction with MTBD in acetonitrile is dissociated into free ions while that of the TBD reaction is composed of a comparable amount of ions and ion pairs. The second-order rate constants (k2H) for these bases of almost equal strength in acetonitrile (pKa= 24.70, 24.97 for MTBD and TBD) and C-acids 1, 2, and 3 are: 317, 86, 7.6 dm3mol–1s–1; and 15 200, 5300, 1100 dm3mol–1s–1, respectively. The appropriate primary deuterium kinetic isotope effects (kH/kD) are 12.5, 10.8, 6.9; and 9.9, 11.2, 12.6. The influence of steric hindrance brought by reacting C-acids and bases is discussed. The different structure of the transition states and the products as mono- and double-hydrogen bonded complexes for these series of C-acids and MTBD and TBD bases is manifested by a distinct reaction mechanism which we attempt to explain.Key words: proton transfer, kinetic study, C-acids, organic bases, acetonitrile, kinetic isotope effects.