The effect of substituting a hydrogen atom in the C-(2) of the ring of 5-acetoxymethyl-5-ethyl-1,3-dioxacyclohexane by a phenyl group on the dynamics of the resulting compound, 2-phenyl-5-acetoxymethyl-5-ethyl-1,3-dioxacyclohexane (HEDPA), is studied. Taking the ester residue and the phenyl group to define the configuration, the H-1 NMR spectrum of this compound shows that the mole ratio of cis/trans isomers is 0.70/0.30. Molecular dynamics calculations show that at room temperature the 1,3-dioxacyclohexane ring remains in the conformation used as a starting point of the MD trajectory during all the simulation. Calculations performed at higher temperatures (i.e., from 800 to 1200 K) allows the evaluation of lifetimes, population fractions, and interconversion energy barriers for the four conformations allowed for the cyclohexane ring. Extrapolation of both equilibrium and dynamic results to room temperature provides consistent values and allows the evaluation of the mean-squared dipole moment whose comparison with the experimental value, [mu(2)] = 7.9 D-2, provides a mole ratio 68/32 for the cis/trans configuration, in excellent agreement with the spectroscopic results.