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Kinetic and mechanistic study of micellar effects in ammonium metavanadate/NaNO2-triggered nitration of phenols in aqueous bisulfate and acetonitrile medium

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Abstract

Ammonium metavanadate (AMV)/NaNO2-triggered nitration of phenols (Ar–OH) in aqueous KHSO4-acetonitrile medium is too sluggish, even at elevated temperature. However, addition of surfactant [sodium dodecyl sulfate (SDS) or Triton X-100 (TX-100)] remarkably accelerates the nitration rate in a concentration-dependent fashion. The reaction kinetics are first order in [AMV], [Ar–OH], and [NaNO2]. Addition of acrylamide or acrylonitrile to the reaction mixture does not result in polymerization, indicating absence of free-radical intermediates. Ultraviolet–visible (UV–Vis) spectroscopic studies of AMV with SDS and TX-100 revealed binding interactions of AMV with micelles. Scanning electron microscopy studies revealed formation of nanostructured micelles with SDS as well as TX-100. On the basis of these observations, the rate acceleration in micellar media can be explained based on formation of more reactive micelle-bound AMV species that partake in the reaction by triggering nitration.

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Authors and Affiliations

  1. Department of Chemistry, Osmania University, Hyderabad, TS, 500 007, India

    N. Venkatesham, K. C. Rajanna, D. Keerthi Devi & P. Veerasomaiah

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  1. N. Venkatesham
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Venkatesham, N., Rajanna, K.C., Keerthi Devi, D. et al. Kinetic and mechanistic study of micellar effects in ammonium metavanadate/NaNO2-triggered nitration of phenols in aqueous bisulfate and acetonitrile medium. Res Chem Intermed 44, 3293–3312 (2018). https://doi.org/10.1007/s11164-018-3307-2

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