Structural Chemistry

, Volume 11, Issue 6, pp 335–340 | Cite as

Basicity and Proton Transfer in Proton Sponges and Related Compounds: An Ab Initio Study

  • Ibon Alkorta
  • José Elguero


Theoretical calculations at the B3LYP/6-31G* level were carried out on a family of 1,8-diR-naphthalenes, which include the proton sponge (1,8-bisdimethylaminonaphthalene, R = NMe2) and other substituents (R = NH2, R = OH, R = CH3, R = F). Their basicity was compared with that of the corresponding monosubstituted benzenes. The dianion of 1,8-dihydroxynaphthalene should be a compound of extraordinary high basicity. The barriers to proton transfer, geometry, and density at the bond critical point of the hydrogen bond have been calculated and compared with experimental data when available.

Proton sponges proton transfer basicity monosubstituted benzenes LBHB 


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  1. 1.
    Alder, R. W.; Bowman, P. S.; Streele, W. R. S.; Winterman, D. R. J. Chem. Soc. Chem. Commun. 1968, 723–724.Google Scholar
  2. 3.
    Staab, H. A.; Kriger, C.; Hieber, G.; Oberdorf, K. Angew. Chem. Int. Ed. Engl. 1997, 36, 1884–1886.Google Scholar
  3. 4.
    Staab, H. A.; Kirsch, A.; Barth, T.; Krieger, C.; Neugebauer, F. A. Eur. J. Org. Chem. 2000, 1617–1622.Google Scholar
  4. 5.
    Pozharskii, A. F. Russ. Chem. Rev. 1998, 67, 1–24.Google Scholar
  5. 6.
    Pozharskii, A. F.; Ozeryanskii, V. A. Russ. Chem. Bull. 1998, 47, 66–73.Google Scholar
  6. 7.
    Pozharskii, A. F.; Tregub, N. G.; Vistorobskii, N. V.; Romanova, E. Yu.; Starikova, Z. A.; Yanovsky, A. I. Russ. Chem. Bull. 1999, 48, 1299–1309.Google Scholar
  7. 8.
    Platts, J. A.; Howard, S. T.; Wozniak, K. J. Org. Chem. 1994, 59, 4647–4651.Google Scholar
  8. 9.
    Platts, J. A.; Howard, S. T. J. Org. Chem. 1996, 61, 4480–4482.Google Scholar
  9. 10.
    Howard, S. T.; Platts, J. A. J. Org. Chem. 1998, 63, 3568–3571.Google Scholar
  10. 11.
    M. Peräkylä, J. Org. Chem. 1996, 61, 7420–7425.Google Scholar
  11. 12.
    Szemik-Hojniak, A.; Zwier, J. M.; Buma, W. J.; Bursi, R.; van der Waals, J. H. J. Amer. Chem. Soc. 1998, 120, 4840–4844.Google Scholar
  12. 13.
    Wozniak, K.; He, H.; Klinowski, J.; Barr, T. L.; Milart, P. J. Phys. Chem. 1996, 100, 11420–11426.Google Scholar
  13. 14.
    Wozniak, K.; Wilson, C. C.; Knight, K. S.; Jones, W.; Grech, E. Acta Crystallogr. Ser. B 1996, 52, 691–696.Google Scholar
  14. 15.
    Mallinson, P. R.; Wozniak, K.; Wilson, C. C.; McCormack, K. L.; Yufit, D. S. J. Amer. Chem. Soc. 1999, 21, 4640–4646.Google Scholar
  15. 16.
    Wozniak, K.; Raczynska, E. D.; Korybut-Daszkiewicz, B. Israel J. Chem. 1999, 39, 245–252.Google Scholar
  16. 17.
    Llamas-Saiz, A.; Foces-Foces, C.; Elguero, J. J. Mol. Struct. 1994, 328, 297–323.Google Scholar
  17. 18.
    Llamas-Saiz, A.; Foces-Foces, C.; Martínez, A.; Elguero, J. J. Chem. Soc. Perkin Trans. 2 1995, 923–927.Google Scholar
  18. 19.
    López, C.; Claramunt, R. M.; Llamas-Saiz, A. L.; Foces-Foces, C.; Elguero, J.; Sobrados, I.; Aguilar-Parrilla, F.; Limbach, H.-H. New J. Chem. 1996, 20, 523–536.Google Scholar
  19. 20.
    López, C.; Llorente, P.; Claramunt, R. M.; Marín, J., Foces-Foces, C.; Llamas-Saiz, A. L.; Elguero, J.: Limbach, H.-H. Ber. Bunsenges. Phys. Chem. 1998, 102, 414–418.Google Scholar
  20. 21.
    Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andrés, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, Gaussian 94, Revision B.3, Gaussian, Pittsburgh, Pennsylvania, 1995.Google Scholar
  21. 22.
    6-31G*: Krishnam, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. J. Chem. Phys. 1984, 80, 650–654.Google Scholar
  22. 23.
    Becke, A. D. J. Chem. Phys. 1993, 98, 5648–5652.Google Scholar
  23. 24.
    Bader, R. F. W. Atoms in Molecules. A Quantum Theory, Oxford University Press, New York, 1990.Google Scholar
  24. 25.
    Bieger-Konig, F. W.; Bader, R. F. W.; Tang, T. H. J. Comp. Chem. 1982, 3, 317–328.Google Scholar
  25. 26.
    Lau, Y. K.; Saluja, P. P. S.; Kebarle, P.; Alder, R. W. J. Amer. Chem. Soc. 1978, 100, 7328–7333.Google Scholar
  26. 27.
    Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. J. Phys. Chem. Ref. Data 1988, 17(S1), 1–861.Google Scholar
  27. 28.
    DeTuri, V. F.; Ervin, K. M. Int. J. Mass Spectrum. Ion Proc. 1998, 175, 123–132.Google Scholar
  28. 29.
    Moore, L.; Lubinski, R.; Baschky, M. C.; Dahlke, G. D., Hare, M.; Arrowood, T.; Glasovac, Z.; Eckert-Maksic, M.; Kass, S. R. J. Org. Chem. 1997, 62, 7390–7396.Google Scholar
  29. 30.
    Wiberg, K. B.; Rablen, P. R. I. J. Org. Chem. 1998, 63, 3722–3730.Google Scholar
  30. 31.
    Suárez, D.; Menéndez, J. A.; Fuente, E.; Montes-Morán, M. A. Angew. Chem. Int. Ed. Engl. 2000, 39, 1320–1323.Google Scholar
  31. 32.
    March, J. Advanced Organic Chemistry, 4th Ed., Wiley, New York, 1992, 255.Google Scholar
  32. 33.
    Alkorta, I.; Elguero, J. Tetrahedron 1997, 53, 9741–9748.Google Scholar

Copyright information

© Plenum Publishing Corporation 2000

Authors and Affiliations

  • Ibon Alkorta
    • 1
  • José Elguero
    • 2
  1. 1.Instituto Química Médica, CSICMadridSpain
  2. 2.Instituto Química Médica, CSICMadridSpain

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