Cent. Eur. J. Chem. 11, 1711-1722 (2013)

DOI: 10.2478/s11532-013-0311-7

A theoretical study of the limits of the acidity of carbon acids in phase transfer catalysis in water and in liquid ammonia

The acidities of a large number of carbon acids have been theoretically calculated for the gas-phase and for DMSO solution. The gas-phase values, both ΔH and ΔG, are very well correlated with the available experimental data. From the calculated ΔG values in DMSO and the pKas in the same solvent, a homogeneous set of pKa (DMSO) values was devised that was used to generate pKa(water). These last pKas were used to establish the limits of the acidity of carbon acids for reactions under PTC conditions both alkylations and H/D exchange. A step further led to the pK as in liquid ammonia and from them to the virtual use of PTC using liquid ammonia instead of water.