Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics of Oxidation of Nitrotoluenes by Acidic Hexacyanoferrate (Ⅲ)

  • Bhattacharjee, A. K. (Department of Chemistry, North-Eastern Hill University) ;
  • Mahanti, M. K. (Department of Chemistry, North-Eastern Hill University)
  • Published : 1983.06.20
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Abstract

The reaction of hexacyanoferrate (Ⅲ) with nitrotoluenes in aqueous acetic acid containing perchloric acid(1.0 M) at $50^{\circ}C$ gave the corresponding aldehyde as the major product. The order with respect to each of the reactants ― substrate, oxidant and acid ― was found to be unity. The Hammett plot yielded a ${\sigma}^+$ value of -1.30, and the kinetic isotope effect gave a $k_H/k_D$ value of 6.2. The pathway for the conversion of the nitrotoluenes to the products has been mechanistically visualized as proceeding through the benzylic radical intermediate, formed in the rate determining step of the reaction.

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