Abstraction and addition reactions of four γ‐lactones with H‐atoms and methyl radicals

Abstract

AbstractThe five‐membered cyclic esters, or γ‐lactones, are promising candidates as biofuel additives and green solvent components. A comprehensive study of thermochemical and kinetic properties of γ‐butyrolactone (GBL), γ‐valerolactone (GVL), γ‐caprolactone (GCL), and γ‐heptalactone (GHL) has been conducted. The entropy, , specific heat, , enthalpy function, , and the enthalphy of formation at 298.15 K, , as well as the adiabatic ionization potential and single bond dissociation energies are reported. Bimolecular rate constants for the abstraction of H‐atom by H• and CH are presented on a per abstractable hydrogen basis; abstraction at the tertiary carbon site is consistently favored, while abstraction by CH lags behind H•. Addition reactions of H• and CH have high barriers and favor addition to the C‐center.