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Kinetic and equilibrium studies of σ-adduct formation and nucleophilic substitution in the reactions of 2-chloro-3,5-dinitropyridine and 2-ethoxy-3,5-dinitropyridine with p-substituted anilines in DMSO

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Abstract

Rate and equilibrium results for the reactions of 2-chloro-3,5-dinitropyridine and 2-ethoxy-3,5-dinitropyridine with a series of p-substituted anilines in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) were studied in DMSO. The reactions yielded 2-anilino-3,5-dinitropyridine derivatives, and no accumulation of intermediates could be detected spectrophotometrically. The rates were compatible with a two-step mechanism involving initial nucleophilic attack followed by either base-catalysed or uncatalysed conversion to the product. The base-catalysed pathway was likely to involve rate-limiting proton transfer from the zwitterionic intermediate to the base to yield the anionic σ-adduct. Plots of log K 1 k DABCO against pK a values gave good straight lines at 25 °C, with slopes of 0.42 for 2-chloro- and 0.45 for 2-ethoxy-3,5-dinitropyridine. The results were compared with those for the reactions of 2-phenoxy-3,5-dinitropyridine with substituted anilines.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Applied Sciences, Umm Al-Qura University, P.O. Box: 9569, Makkah, Saudi Arabia

    Basim H. Asghar

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  1. Basim H. Asghar
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Correspondence to Basim H. Asghar.

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Asghar, B.H. Kinetic and equilibrium studies of σ-adduct formation and nucleophilic substitution in the reactions of 2-chloro-3,5-dinitropyridine and 2-ethoxy-3,5-dinitropyridine with p-substituted anilines in DMSO. Monatsh Chem 144, 301–306 (2013). https://doi.org/10.1007/s00706-012-0860-z

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  • DOI: https://doi.org/10.1007/s00706-012-0860-z

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