• Conformation of hindered piperidines: Spectroscopic evidence for contribution of boat conformations

    • Fulltext

       

        Click here to view fulltext PDF


      Permanent link:
      https://www.ias.ac.in/article/fulltext/jcsc/122/04/0579-0586

    • Keywords

       

      NMR; 1H NMR; 13C NMR; conformational analysis; boat forms.

    • Abstract

       

      High resolution 1H and 13C NMR resonance assignments and conformational assignments were carried out for four $t(3)$-benzyl-$r$(2),𝑐(6)-bis(aryl)piperidin-4-ones 1-4 and their four 𝑁-nitroso-$t(3)$-benzyl-$r(2)$,$c(6)$-bis(aryl)piperidin-4-ones 5-8. In addition to conventional 1D NMR methods, 2D shiftcorrelated NMR techniques (1H-1H COSY and 1H-13C COSY) were used for signal assignments. At room temperature the $t(3)$-benzyl-$r(2)$,$c(6)$-bis(aryl)piperidin-4-ones 1-4 exist in only one isomeric form whereas their 𝑁-nitroso derivatives 5-8 exist in two isomeric forms. The preferred conformations of both the isomeric forms of nitrosamines were determined by comparison of the spectral data with those of the corresponding parent amines 1-4 and with the aid of substituent parameters. The results indicate the presence of an equilibrium mixture of boat forms B1 and B2 for Z isomers of 5-8. For the E isomers of 5-8, boat form B1 is predicted to be the major conformer. The piperidin-4-ones 1-4 exist in normal chair conformations with equatorial orientations of all the substituents.

    • Author Affiliations

       

      A Thangamani1 J Jayabharathi1 A Manimekalai1

      1. Department of Chemistry, Annamalai University, Annamalainagar 608 002
    • Dates

       
  • Journal of Chemical Sciences | News

© 2021-2022 Indian Academy of Sciences, Bengaluru.