A DFT Study on the Mechanism of the Annulation Reaction of Trichloronitroethylene with Aniline in the Synthesis of Quinoxalinone-N-oxides


Ozpinar G. , ERDEM S., Meyer C., Kaufmann D. E.

JOURNAL OF ORGANIC CHEMISTRY, cilt.74, ss.4727-4739, 2009 (SCI İndekslerine Giren Dergi) identifier identifier identifier

  • Cilt numarası: 74 Konu: 13
  • Basım Tarihi: 2009
  • Doi Numarası: 10.1021/jo9003629
  • Dergi Adı: JOURNAL OF ORGANIC CHEMISTRY
  • Sayfa Sayıları: ss.4727-4739

Özet

The new annulation reaction of trichloronitroethylene with aniline results in the formation of a quinoxalinone-N-oxide derivative. The mechanism of this one-pot annulation reaction between trichloronitroethylene (TCNiE) and anilines has been extensively investigated with B3LYP/6-31+G** methodology. Five different paths (1-5) were proposed and modeled by using this method. These paths were compared in terms of the activation energies of their rate-determining steps and in regard to the experimental findings. Paths 3 and 5, proceeding via four-membered heterocyclic rings, were found to be the most plausible paths with activation energies of 32 and 29 kcal/mol for the rate-determining steps, respectively. The effects of substituent, solvent, temperature, and computational method on these steps were also investigated. The results showed that path 5 is the most plausible mechanism for the annulation reaction of trichloronitroethylene with aniline.