The thermodynamic properties of delta-lactones

Abstract

The enthalpies of formation of δ-hexanolactone and δ-nonanolactone were determined by combustion calorimetry. Conformational analysis and quantum-chemical calculations of equilibrium structures, fundamental vibrations, moments of inertia, and total energies were performed for δ-pentanolactone (I), δ-hexanolactone (II), and δ-nonanolactone (III) by the B3LYP/6-311G(d,p), B3LYP/6-311++G(d,p), and G3MP2 methods. The experimental IR spectra and calculated vibrational frequencies were used to suggest the assignment of vibrational frequencies of stable conformations. The thermodynamic properties of I–III in the ideal gas state were determined over the temperature range 0–1500 K. A thermodynamic analysis of mutual isomerization in the gas and liquid phases over the temperature range 298.15–900 K and liquid-phase polymerization of γ- and δ-pentanolactones and 4-pentenoic acid over the temperature range 298.15–500 K was performed.