Summary
The1H-NMR spectra of aryl-(hydroxynaphthyl)-methylpiperidines, which are model compounds for intramolecular hydrogen bonding, have been analyzed in order to investigate their conformations in solution. As dynamic phenomena can be assumed from line broadening, low temperature spectra have been measured to evaluate the coalescence temperatures and the energy barriers. The latter have been discussed with respect to the size and position of selected substituents. It can be shown that the molecules exist in one energetically favorable conformation with the aryl ring perpendicular to the plane of the naphthol ring system. The interaction between the naphthol ring and the aryl ring influences the conformation at the piperidine ring moiety. This effect leads to an increase of the inversion barrier of the piperidine residue.
Zusammenfassung
Die Konformation von Aryl-(hydroxynaphthyl)-methylpiperidinen wurde in Lösung mit Hilfe der1H-NMR-Spektroskopie untersucht, da diese Substanzen als Modellverbindungen für intramolekulare Wasserstoffbrückensysteme herangezogen werden. Zum Studium dynamischer Vorgänge wurden die Spektren bei verschiedenen Temperaturen vermessen und die entsprechenden Aktivierungsparameter bestimmt. Es konnte gezeigt werden, daß die erwähnten Moleküle in einer energetisch bevorzugten Konformation vorliegen, in der der Arylring senkrecht auf die Ebene des Naphtholringes steht. Die sterische Wechselwirkung zwischen Naphthol- und Arylring erhöht außerdem die Inversionsbarriere des Piperidinringes.
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Dedicated to Prof. Dr. K. Schlögl on the occasion of his 65th birthday
On Sabbatical Leave from Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan
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Ansari, S.M., Robien, W., Schlederer, M. et al. 1H-NMR investigations of the conformation of aryl-(hydroxynaphthyl)-methylpiperidines. Intramolecular interactions, IV. Monatsh Chem 120, 1003–1014 (1989). https://doi.org/10.1007/BF00808772
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DOI: https://doi.org/10.1007/BF00808772