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      Permanent link:
      https://www.ias.ac.in/article/fulltext/jcsc/115/02/0129-0134

    • Keywords

       

      Substituted benzylamines; cetyltrimethylammonium permanganate; hydride-ion transfer

    • Abstract

       

      Oxidation of meta- and para-substituted benzylamines by cetyltrimethylammonium permanganate (CTAP) to the corresponding aldimines is first order with respect to both the amine and CTAP. Oxidation of deuteriated benzylamine (PhCD2NH2) exhibited the presence of a substantial kinetic isotope effect (kH/kD = 5.60 at 293 K). This confirmed the cleavage of an α-C-H bond in the rate-determining step. Correlation analyses of the rates of oxidation of 19 monosubstituted benzylamines were performed with various single and multiparametric equations. The rates of the oxidation showed excellent correlations in terms of Yukawa—Tsuno and Brown’s equations. The polar reaction constants are negative. The oxidation exhibited an extensive cross-conjugation, in the transition state, between the electron-donating substituents and the reaction centre. A mechanism involving a hydride-ion transfer from the amine to CTAP in the rate-determining step has been proposed.

    • Author Affiliations

       

      Raghvendra Shukla1 Pradeep K Sharma1 László Kótai2 Kalyan K Banerji1

      1. Department of Chemistry, JNV University, Jodhpur - 342 005, India
      2. Institute of Chemistry, Chemical Research Center, Hungarian Academy of Sciences, Pusztaseri u. 59-67, Budapest - H-1025, Hungary
    • Dates

       
  • Journal of Chemical Sciences | News

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