Journal of the American Chemical Society 2005-06-29

Selective solvent interactions in a fluorous reaction system.

John T Gerig

Index: J. Am. Chem. Soc. 127(25) , 9277-84, (2005)

Full Text: HTML

Abstract

Mixtures of chloroform and perfluoro(methylcyclohexane) can be used as solvents for "fluorous" biphase reactions since they exist as two separate phases at low temperature but become a single phase at higher temperatures. Intermolecular nuclear Overhauser effects have been used to investigate the interactions of solvent components with the protons and fluorines of 3-heptafluorobutyrylcamphor in both phases of this biphasic system at 25 degrees C as well as the single phase at 54 degrees C. The results indicate that at 25 degrees C in the perfluorocarbon-rich phase, both solvent components interact with the solute selectively. There are no indications of unusual solute interactions of either solvent component in the chloroform-rich phase and only weak suggestions of selective interactions in the high-temperature phase. Various mechanisms for the enhancement of solute spin-solvent spin cross relaxation rates in the perfluoro(methylcyclohexane)-rich phase are considered. It is suggested that the solvation layer around the solute has a composition and possibly hydrodynamic properties different from those of the bulk solution in this phase. There are indications of appreciable regioselectivity of chloroform interactions with the hydrocarbon part of the solute in all phases.