Publication: A DFT Study on the Mechanism of the Annulation Reaction of Trichloronitroethylene with Aniline in the Synthesis of Quinoxalinone-N-oxides
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Date
2009
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AMER CHEMICAL SOC
Abstract
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.
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Keywords
DENSITY-FUNCTIONAL THERMOCHEMISTRY, TRANSITION-STATE GEOMETRIES, POLYHALOGENATED NITROBUTADIENES, ADJUSTABLE-PARAMETERS, ACTIVATION-ENERGIES, BIOLOGICAL-ACTIVITY, BARRIER HEIGHTS, EXACT-EXCHANGE, DERIVATIVES, CHEMISTRY