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Sodium perborate/NaNO2/KHSO4-triggered synthesis and kinetics of nitration of aromatic compounds

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Abstract

Sodium perborate (SPB) was used as efficient green catalyst for NaNO2/KHSO4-mediated nitration of aromatic compounds in aqueous acetonitrile medium. Synthesis of nitroaromatic compounds was achieved under both conventional and solvent-free microwave conditions. Reaction times were comparatively shorter in the microwave-assisted than conventional reaction. The reaction kinetics for nitration of phenols in aqueous bisulfate and acetonitrile medium indicated first-order dependence on [Phenol], [NaNO2], and [SPB]. Reaction rates accelerated with introduction of electron-donating groups but retarded with electron-withdrawing groups. Kinetic results did not fit well quantitatively with Hammett’s equation. Observed deviations from linearity were addressed in terms of exalted Hammett’s constants (\( \bar{\sigma } \) or σeff), para resonance interaction energy (ΔΔGp) parameter, and Yukawa–Tsuno parameter (r). This term provides a measure of the extent of resonance stabilization for a reactive structure that builds up charge (positive) in its transition state. The observed negative entropy of activation (−ΔS#) suggests greater solvation and/or cyclic transition state before yielding products.

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Authors and Affiliations

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

    K. C. Rajanna, Suresh Muppidi, Srinivas Pasnoori & P. K. Saiprakash

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  1. K. C. Rajanna
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  2. Suresh Muppidi
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  3. Srinivas Pasnoori
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  4. P. K. Saiprakash
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Correspondence to K. C. Rajanna.

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Rajanna, K.C., Muppidi, S., Pasnoori, S. et al. Sodium perborate/NaNO2/KHSO4-triggered synthesis and kinetics of nitration of aromatic compounds. Res Chem Intermed 44, 6023–6038 (2018). https://doi.org/10.1007/s11164-018-3473-2

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