Reactions of 2-Butanol with Hydroperoxyl and 2-Hydroxy-2-Butyl Peroxy Radicals

Abstract

Using density functional theory with the hybrid functional B3LYP in the 6-311++G(d, p) basis set, the Fukui functions were calculated for hydrogen atoms of CH bonds of 2-butanol in the cases of electrophilic and nucleophilic attacks, transition states were located, and the activation energies and enthalpies were computed for elementary reactions of the electrophilic hydroperoxyl radical (HOO•) and 2-hydroxy-2-butyl peroxy radical ((CH3)(C2H5)C(OH)OO•) with CH bonds of all types in 2-butanol. It was shown that the target of the attack of the peroxy radicals on CH bonds of 2-butanol is controlled by the ratio between the electron-donating and electron-accepting abilities of hydrogen atoms of CH bonds of the alcohol. The relationship between the activation energy, the length of the CH bond being cleaved in the transition state, and the nucleophilicity of the formed carbon-centered radical was determined.