Thermal decomposition and isomerization of furfural and 2-pyrone: a theoretical kinetic study

Abstract

We have studied the decomposition and isomerization of furfural in the gas phase using quantum chemical and statistical reaction rate theory techniques. This work uncovers a variety of new reaction channels in furfural pyrolysis that lead to formation of the experimentally observed products, including CO2, which was previously unexplained. In addition to the known mechanism for furan + CO production, furfural is shown to isomerize directly to 2-pyrone, with a barrier height of 69 kcal mol−1, from where it can decompose to vinylketene + CO (highest barrier of 65 kcal mol−1) or to CO2+ 1,3-cyclobutadiene (highest barrier of 66 kcal mol−1). Alternative pathways to vinylketene + CO and 4-pyrone ..