A polar nature of benzoic acids extrusion from nitroalkyl benzoates: DFT mechanistic study

Using DFT calculations at various theory levels, quantum-chemical simulations of decomposition paths were performed for a series of nitroalkyl benzoates. It was discovered, that these reactions proceed via polar, but one-step mechanism. It turned out that depending on the nature of the substituent in the ester molecule and on medium polarity, the studied reactions may take place via transition states with varied synchronicity—from E1-like structures, to E1cb-like structures. A purely ionic, two-stage mechanism was not identified in any of the cases.