The most ubiquitous chemical reaction that can affect the environmental fate of chemicals is hydrolysis, so it represents the baseline against which the significance of all other processes must be considered. The OH- anion is thought to react with nitroatromatic compounds by several different mechanisms, including Meisenheimer complex formation, direct nitro substitution, and alkyl and arene proton abstractions.  Because these are energetic compounds, other atypical reactions may also be possible, such nitrate abstraction, and ether hydrolysis in nitro anisoles.   The talk will present results for solution phase reaction energies and activation barriers for the candidate mechanisms using electronic structure calculations with implicit solvent models and AIMD/MM free energy calculations.  These types of calculations have shown that there is a large diversity in mechanisms and kinetics of hydrolysis of the various nitroaromatic compounds and that simple QSAR models may not be predictive.  The talk will also discuss the computational challenges in determining accurate activation barriers, and our experiences with using different free energy methods.

Quantifying the many possible hydrolysis reactions of nitroaromatic compounds using computational methods

246th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.