Abstract
We carried out an ab initio study on salicylaldehyde ando-hydroxyacetophenone with full optimization at the 3–21G level. The most stable conformation of the two compounds was that including an intramolecular hydrogen bond, the energy and structural effects of which were estimated. We also studied the stability of the respective tautomers arising from a proton transfer. Such tautomers are quinoid in nature, which implies the loss of the aromatic character of the benzene ring and hence leads to major destabilization. Thus, the tautomerization potential curve of salicylaldehyde featured an inverse barrier of only 2.1 kJ/mol; this barrier was not even present ino-hydroxyacetophenone owing to the effect of the methyl group, which thus overcome the low stability of the quinoid tautomer. In this tautomerization study some single-point calculations at the 6–31G** level were also carried out. In both compounds these calculations give rise to an increase of barriers.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Rowe, W. F.; Duerst, R. W.; Wilson, E. B.J. Am. Chem. Soc.,1976,98, 4021.
Baughcum, S. L.; Duerst, R. W.; Rowe, W. F.; Smith, Z.; Wilson, E. B.ibid.,1981,103, 6296.
Smith, Z.; Wilson, E. B.; Duerst, R. W.Spectrochim. Acta Part A,1984,39, 1117.
Baughcum, S. L.; Smith, Z.; Wilson, E. B.; Duerst, R. W.J. Am. Chem. Soc.,1984,106, 2260.
Turner, P.; Baughcum, S. L.; Coy, S. L.; Smith, Z.J. Am. Chem. Soc.,1984,106, 2265.
Brickmann, J.; Zimmerman, H.J. Phys. Chem.,1969,50, 1608.
Remko, M.; Polcin, J.Z. Phys. Chem. Leizpig,1977,258, 219.
Rajagopal, E.; Sivakumar, K. W.; Subrahmanyam, S. V.; Reddy, K. C.J. Chem. Soc. Faraday Trans. I, 1981,77, 2149.
Hirota, M.; Suzuki, T.; Abe, K. Bull.Chem. Soc. Jpn.,1977,50, 1129.
Schaefer, T.J. Phys. Chem.,1975,79, 1888.
Schuster, P.Chem. Phys. Lett.,1969,3, 433.
Dietrich, S.W.; Jorgensen, E. C.; Kollman, P. A.; Rothenberg, S.J. Am. Chem. Soc.,1976,98, 8310.
Emsley, J.J. Chem. Soc. Rev.,1980,9, 91.
Schaefer, T.; Sebastian, R.; Laatikainen, R.; Salman, S. R.Can. J. Chem.,1984,62, 326.
George, P.; Bock, C. W.; Trachtman, M.J. Mol. Struct. (Theochem.),1985,133, 11.
Butler, L. G.; Brown, T. L.J. Am. Chem. Soc.,1981,103, 6541.
Hunt, M. J.; Mackay, A. L.J. Magn. Reson.,1974,15, 402.
Jones, H.; Curl Jr, R. F.J. Mol. Spectrosc.,1972,42, 65.
Orttung, W. H.; Scott, G. W.; Vosooghi, D.J. Mol. Struct. (Theochem.),1984,109, 161.
Nishiya, T.; Yamauchi, S.; Hirota, N.; Fujiwara, Y.; Itoh, M.J. Am. Chem. Soc.,1984,108, 3880.
Nagaoka, S.; Hirota, N.; Sumitani, M.; Yoshihara, K.; Lipcznska-Kochany, E.; Iwamura, H.J. Am. Chem. Soc.,1984,106, 6913.
Konijnenberg, J.; Huizer, A. H.J. Chem. Soc. Faraday Trans. 2,1988,84, 363.
Gaussian 88, Frisch, M. J.; Head-Gordon, M.; Schlegel, H. B.; Raghavachari, K.; Binkley, J. S.; González, C.; Defrees, D. J.; Fox, D. J.; Whiteside, R. A.; Seeger, R.; Melius, C. F.; Baker, J.; Marting, R. L.; Kahn, L. R.; Steward, J. J. P.; Fluder, E. M.; Topiol, S.; Pople, J. A. Gaussian, Inc., Pittsburgh, PA, 1988.
Binkley, J. S.; Pople, J. A.; Hehre, W. J.J. Am. Chem. Soc.,1980,102, 939.
Hariharan, P. C.; Pople, J. A.Theor. Chim. Acta.,1973,28, 213.
Fluder, E. M.; De la Vega, J. R.J. Am. Chem. Soc.,1978,100, 5265.
Bicerano, J.; Schaefer, H. F. III; Miller, W. H.J. Am. Chem. Soc.,1983,105, 2550.
Data obtained by the authors.
Frisch, M. F.; Scheiner, A. C.; Schaefer III, H. F.; Brinkley, J. S.J. Chem. Phys.,1985,82, 4194.
Rios, M. A.; Rodriguez, J.J. Mol. Struct. (Theochem.),1990,204, 137.
Schiering, D. W.; Katon, J. E.Appl. Spectrosc.,1986,40, 1049.
Sánchez-Cabezudo, M.; De Paz, J. L. G.; Amat-Guerri, F.; Catalán, J.J. Mol. Struct. (Theochem.),1985,131, 277.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Graña, A.M., Ríos, M.A. & Rodríguez, J. Ab initio study of the structure and tautomerism of internally hydrogen-bonded aromatic carbonyls: Salicylaldehyde and o-hydroxyacetophenone. Struct Chem 2, 575–580 (1991). https://doi.org/10.1007/BF00673440
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00673440