Conformational studies of ethylene glycol and its two methyl ether derivatives

Abstract

As a theoretical analysis of the conformational equilibria of ethylene glycol, methoxyethanol and dimethoxyethane, the energy of each stable conformational isomer (rotamer) of these molecules was calculated for various temperatures and solvent dielectric constants. Classical semi-empirical potential functions were used. Besides intrinsic potentials for rotation about single bonds, intramolecular dispersion and repulsive interaction, dipole-dipole interaction and hydrogen bonding energies were included. Interaction with the solvent was considered only in terms of a continuous dielectric medium interacting with the local dipoles and quadrupoles of the molecule. For each rotamer, the dihedral angles giving the lowest energy were determined. From the energies of each rotamer, Boltzmann distributions of populations were obtained, and total concentrations were calculated in various physically distinguishable states, e.g. those with and without internal hydrogen bonds, or those in which the central C-C bond takes a trans or a gauche conformation. It is shown that the equilibrium constants, K HB and K TG, for these two cases are not identical. While changes in the dielectric constant may alter strongly the geometries and energies of individual rotamers, their effect on the average geometries and on the two equilibrium constants is small. The same is true of temperature changes, and is due to the presence of several rotamers in each of the physical states considered. Thus the small temperature dependence of some observed physical properties is shown to be consistent with the distribution of molecules over several conformational states. In solution, the fraction of ethylene glycol molecules with two free OH groups (i.e. without an intramolecular hydrogen bond) is predicted to be at least 20 per cent. This shows that the presence of three-dimensional hydrogen-bonded structures in the liquid, which we propose, is possible in principle.