Conformations and enthalpies of formation of methylenecyclohexane, 1,4‐dimethylenecyclohexane, cyclohexanone, 4‐methylenecyclohexanone, 1,4‐cyclohexanedione, and their mono‐ and dioxa derivatives by G3(MP2)//B3LYP calculations

Abstract

AbstractA computational study of the stable conformations and gas‐phase enthalpies of formation at 25 °C of the title compounds has been carried out by G3(MP2)//B3LYP calculations. The work stems from our early observations on the thermodynamic and NMR spectroscopic properties of 2‐methylenetetrahydropyran and related compounds suggesting a dominating chair conformation, with poor p–π overlap in the OCC moiety, for these compounds. Besides computational verification of the chair conformation of 2‐methylenetetrahydropyran, the work was extended to find out the stable conformations of a number of other related compounds and to evaluate the relative stabilities of the various conformers. Another important goal of the work was the estimation of the gas‐phase enthalpies of formation of the present compounds, for which such literature data are scarce. A significant error in the literature value of the enthalpy of formation of methylenecyclohexane was found. Finally, the relative enthalpy levels of the isomeric compounds of this work are discussed. The high thermodynamic stability of the compounds containing an ester functional group, OCO, relative to the stability of isomeric compounds with an OCC moiety in place of the ester function, is demonstrated. Copyright © 2009 John Wiley & Sons, Ltd.