Phase-transfer-catalyzed alkylation of phenylacetonitrile in supercritical ethane

The first example of a phase-transfer-catalyzed alkylation reaction under supercritical fluid conditions is reported. The reaction is that of phenylacetonitrile and ethyl bromide in the presence of tetrabutylammonium bromide and potassium carbonate in supercritical ethane at 45, 60, and 75 degreesC and 138 bar. Results show that the reaction will go to completion in less than 24 h in the presence of the catalyst but that only a few percent conversion is achieved without it during the same period of time. The effects of catalyst concentration, temperature, and cosolvents are investigated. Catalyst solubility estimates and kinetic analyses suggest that the reaction takes place on the surface of the potassium carbonate particles. When the same reaction is attempted in supercritical carbon dioxide, both carboxylation and alkylation are observed. Cycloalkylation reactions between phenylacetonitrile and dibromoalkanes are also discussed.