Structural Chemistry

, Volume 3, Issue 6, pp 381–387 | Cite as

Ab initio study of the structure and tautomerism of internally hydrogen-bonded aromatic carbonyls: Salicylamide, salicylic Acid, and O-hydroxybenzoyl cyanide

  • Carlos M. Estévez
  • Miguel A. Ríos
  • Jesús Rodríguez
Article
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Abstract

We carried out an ab initio study at the 3–21 G level with full geometric optimization of three compounds with intramolecular hydrogen bonds in their most stable conformations, namely salicylamide, salicylic acid, ando-hydroxybenzoyl cyanide. The energy of the hydrogen bonds was estimated and their structural effects were analyzed. We also studied the stability of the tautomers resulting from a proton transfer between the oxygen atoms by analyzing the potential surfaces of the tautomerization process. The potential surfaces of salicylamide and salicylic acid showed a single minimum, while that of the cyanide showed a double minimum with a scarcely significant inverse barrier (3.01 kJ/mol). Single point calculations at the 6–31+G* level on salicylic acid showed a trend to appear a second minimum in the potential surface. Both the strength of the hydrogen bond and the occurrence of stable tautomers were found to be clearly correlated with the electron-releasing and electron-withdrawing ability of the organic functions present in each compound (-NH2,-OH and -CN, respectively).

Keywords

Cyanide Salicylic Acid Proton Transfer Potential Surface Intramolecular Hydrogen Bond 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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Copyright information

© Plenum Publishing Corporation 1992

Authors and Affiliations

  • Carlos M. Estévez
    • 1
  • Miguel A. Ríos
    • 1
  • Jesús Rodríguez
    • 1
  1. 1.Departamento de Química Física, Facultad de QuímicaUniversidad de Santiago de CompostelaSantiago de CompostelaSpain

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