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

• Authors: Ibon Alkorta , José Elguero , Roger Gallo
• Languages of publication: EN

Abstracts

EN

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 pK a (DMSO) values was devised that was used to generate pK a (water). These last pK as 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. [...]

Keywords

EN

PTC; Liquid ammonia; Carbon acids; pKa; DFT calculations

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2013
• Volume: 11
• Issue: 11
• Pages: 1711-1722

Dates

published

1 - 11 - 2013

online

25 - 8 - 2013

Contributors

author

Ibon Alkorta

• Institute of Medical Chemistry, CSIC, E-28006, Madrid, Spain

author

José Elguero

• Institute of Medical Chemistry, CSIC, E-28006, Madrid, Spain

author

Roger Gallo

• Institute of Medical Chemistry, CSIC, E-28006, Madrid, Spain

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Identifiers

DOI

10.2478/s11532-013-0311-7