Conformations of 1,2-dimethoxypropane and 5-methoxy-1,3-dioxane: Are ab initio quantum chemistry predictions accurate?

Abstract

High-level ab initio quantum chemistry calculations are shown to predict conformer populations of 1,2-dimethoxypropane and 5-methoxy-1,3-dioxane that are consistent with gas-phase NMR vicinal coupling constant measurements. The conformational energies of the cyclic ether 5-methoxy-1,3-dioxane are found to be consistent with those predicted by a rotational isomeric state (RIS) model based upon the acyclic analog 1,2-dimethoxypropane. The quantum chemistry and RIS calculations indicate the presence of strong attractive 1,5 C(H3)⋯O electrostatic interactions in these molecules, similar to those found in 1,2-dimethoxyethane.