Lignocellulose-derived second-generation biofuels have promise for alternative energy but pose challenges for computational analysis; small monocyclic oxygenates are feasible targets for study and can serve as model compounds for larger lignocellulosic systems.   Effects of heteroatom substitution, ring size, functional group substitution, and alkyl substitution on carbon-hydrogen bond dissociation enthalpies (BDEs, ?H298) have been examined for several monocyclic oxygenates.  Using G3MP2B3 calculations, C-H BDEs were calculated for tetrahydrofuran, tetrahydropyran, cyclopentanone, and cyclohexanone, along with alkyl-substituted derivatives.  Initial results reveal that functionalization and ring size significantly affect BDE; for instance, C-H BDEs were calculated to be 415 kJ/mol, 382 kJ/mol, and 368 kJ/mol for cyclohexane, the 2-position of cyclohexanone, and the 2-position of 2-methyl cyclohexanone, respectively.   This project reports on an exhaustive examination of C-H BDE values for these monocyclic oxygenates, with the aim of better understanding initial reaction pathways in lignocellulosic biofuels.  Gaussian09 calculations were run via the Ohio Supercomputer Center.

Calculations of bond dissociation enthalpies in monocyclic oxygenates with implications for lignocellulosic biofuels

245th National Meeting (2013)

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