A theoretical study of the nitration of eugenol with the nitronium ion

Abstract

The nitration of eugenol was investigated by using density functional theory (DFT) calculations. Potential energy surface and molecular electrostatic potential of eugenol was constructed in order to find, respectively, the minimum energy conformers and the possible sites for electrophilic attack. Stationary points were located and characterized at the B3LYP/6-311++G(2d,2p) level of theory. A strongly bound π-complex was found, in which the distance between the nitrogen atom of the NO2 moiety and the C1 carbon atom of the aromatic ring is 2.15 Å in the gas phase and 2.06 Å in dichloromethane. The most favorable σ-complex or Wheland intermediate is the result from the interaction between the nitrogen and the C6 ring carbon atom. The transition state that connects both complexes is more resembling the σ-complex. The nitronium ion exothermically reacts with eugenol to give the π-complex without an energy barrier. The next stage of the reaction pathway, π-complex → σ-complex, is endothermic and involves a Gibbs energy of activation of 7.9–8.0 kcal mol–1 (gas phase) and 8.3–8.9 kcal mol–1 (CH2Cl2).