The thermodynamic properties of alkylated γ-lactones
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The enthalpies of formation of γ-pentanolactone (I), γ-hexanolactone (II), and γ-nonanolactone (III) were determined by combustion calorimetry. The enthalpies of vaporization of these lactones were measured by the transfer method. Conformational analysis was performed and equilibrium structures, sets of fundamental vibrations, moments of inertia, and total energies of the stablest conformers of I, II, and III were calculated by the B3LYP/6-311G(d,p), G3MP2, and CBS-QB3 methods. The experimental IR spectra and calculated vibrational frequencies were used to obtain sets of fundamental vibrations of the stablest conformations. The thermodynamic properties of I–III in the ideal gas state were determined over the temperature range 0–1500 K. Additive and quantum-chemical methods were applied to estimate the Δf H o(g) values of a number of γ-lactones. Composite quantum-chemical methods were used to obtain the energies of monomethyl γ-butyrolactones and estimate their relative stability depending on the position of the methyl substituent in the ring.
KeywordsLactone Standard Enthalpy Conformational Analysis Fundamental Vibration Combustion Calorimetry
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