Solvent Effects on Equilibria of Addition of Nucleophiles to Acetaldehyde and the Hydrophilic Character of Diols

Article abstract of DOI:10.1021/ja00343a044

Equilibria of addition of water, methanol, methanethiol, ammonia, methylamine, nitromethane, and ethylene glycol to acetaldehyde have been compared in water and in chloroform, and the partition coefficients of reactants and products between the two solvents have been estimated by direct and indirect methods.Single additions of oxygen nucleophiles were found to proceed equally favorably in either solvent, whereas single additions of sulfur, nitrogen, and carbon nucleophiles proceeded much further toward completion in water than in chloroform.Equilibria of acetal formation, involving methanol or ethylene glycol, were somewhat more favorable in chloroform than in water.Reexamination of the vapor pressures of ethylene glycol and related compounds over water indicated that their hydrophilic character was greater than had been supposed.