Iwona Binkowska

Kinetic and equilibrium study of the deprotonation of 4-nitrophenyl[bis(ethylsulphonyl)]methane by organic bases in acetonitrile in the presence of common cation BH+ and tetrabutylammonium perchlorate

The results of kinetic and equilibrium experiments with the set of reaction of proton abstraction from 4-nitrophenyl[bis(ethylsulphonyl)]methane in acetonitrile are reported. Two strong organic bases are used: 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD).The rates of proton transfer reaction have been measured by T-jump method in the presence of perchlorate of the appropriate base as a common cation BH+ and supporting electrolyte-tetrabutylammonium perchlorate (TBAP) in the temperature range between 20–40°C are: kH=1.32×107−2.00×107 and 2.82×107−4.84×107 dm 3mol−1s−1 for MTBD and TBD respectively. The enthalpies of activation ΔHMTBD≠=13.5 and ΔHTBD≠=18.1 kJmol−1. The entropies of activation are negative: ΔSMTBD≠=−62.3 and ΔSTBD≠=−40.3 Jmol−1K−1.The change of the absorbance of the anion of 4-nitrophenyl[bis9ethylsulphonyl)]methane at the temperature 25°C in the presence of common cation BH+ gives the equilibrium constants K=705 and 906 M−1 for MTBD and TBD respectively.Kinetic and equilibrium results are discussed. The possible mechanism of proton transfer reaction between 4-nitrophenyl[bis(ethylsulphonyl)]methane and cyclic organic bases: MTBD and TBD in acetonitrile is proposed.

Equilibrium and kinetic study of the proton transfer reactions between nitroalkanes and strong organic bases — phosphazenes in tetrahydrofuran solvent

AbstractProton transfer reactions rates between carbon acids 1-nitro-1-(4-nitrophenyl)ethane (NPNE), 2-methyl-1-nitro-1-(4-nitrophenyl)propane (MNPNP)) and phosphazenes (BEMP, BTPP, P1-t-Oct) in tetrahydrofuran have been measured, and the activation parameters were determined. The results are compared with those previously obtained for P1-t-Bu phosphazene, guanidines and amidines.