Solvation Properties of Aliphatic Alcohol–Water and Fluorinated Alcohol–Water Solutions for Amide Molecules Studied by IR and NMR Techniques

Abstract

Solvation properties of aliphatic alcohol–water and fluorinated alcohol–water solutions were probed by amide molecules as solutes using infrared (IR) and 1H and 13C NMR techniques. These include four alcohols: ethanol (EtOH), 2-propanol (2-PrOH), 2,2,2-trifluoroethanol (TFE), and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and three amides: N-methylformamide (NMF), N-methylacetamide (NMA) and N-methylpropionamide (NMP). The hydrogen bonds of the amide carbonyl oxygen with water are gradually weakened as the alcohol content increases. This decreases in the order of HFIP > TFE ≈ 2-PrOH > EtOH. In TFE– and HFIP–water solutions, the hydrogen bond between the amide amino hydrogen and water is also gradually broken with increasing xA. This trend is more notable in the order of NMP > NMA > NMF. The hydrophobic moieties of the amide methyl and ethyl groups are solvated by the fluoroalkyl groups of fluorinated alcohols due to the hydrophobic interaction among them. Thus, the steric hindrance generated by the solvated alkyl group of amides promotes the breaking of the hydrogen bonds between amide and water.