α-Substituted β-diketones: effect of the α substituent on the complexation and selectivity for lanthanides

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Quyen T. H. Le, Shigeo Umetani, Mitsuko Suzuki and Masakazu Matsui


Abstract

Some β-diketones having a substituent at the α position have been prepared and their keto–enol tautomerism, acid dissociation reaction and complexation with lanthanides have been studied. The tautomerism was examined by 1H NMR spectroscopy, revealing that substitution of a methyl and bromo group at the α position of PhC(O)CH2C(O)Ph or PhC(O)CH2C(O)CF3 decreases the percentage of the enol form drastically, whereas the parent diketones exist quantitatively in the enol form in CDCl3. The pKa value of PhC(O)CHMeC(O)CF3 determined in 75% (v/v) 1,4-dioxane–water containing 0.1 mol dm-3 NMe4ClO4 at 25 °C was 10.36, being much larger than that of PhC(O)CH2C(O)CF3 (8.10). This weak acidity could be attributed to the strong intramolecular hydrogen bond which results upon decreasing the separation between the two donating oxygens through the steric repulsion between the α-methyl substituent and the terminal phenyl and trifluoromethyl groups. The diketone structures and the intramolecular hydrogen bond were evaluated using semiempirical molecular orbital calculations (MNDO/H), taking into account the hydrogen bond. The complexation with lanthanides has been examined via the solvent-extraction method. The lanthanides were extracted from a lower pH region with PhC(O)CH2C(O)CF3 than with PhC(O)CHMeC(O)CF3 owing to its higher acidity. On the contrary, the separation with the latter was found to be better than that with the former. The separability is discussed with regard to the structures of the diketones.


References

  1. Principles and Practices of Solvent Extraction, eds. J. Rydberg, C. Musikas and G. R. Choppin, Marcel Dekker, New York, 1992 Search PubMed.
  2. T. Sekine and Y. Hasegawa, in Solvent Extraction Chemistry, Marcel Dekker, New York, 1977 Search PubMed.
  3. J. Emsley, Struct. Bonding (Berlin), 1984, 57, 147 CAS.
  4. G. Gilli, F. Bellucci, V. Ferretti and V. Bertolasi, J. Am. Chem. Soc., 1989, 111, 1023 CrossRef CAS.
  5. A. Roy and K. Nag, J. Inorg. Nucl. Chem., 1978, 40, 331 CrossRef CAS.
  6. S. Umetani and M. Matsui, Bull. Chem. Soc. Jpn., 1983, 56, 3426 CAS.
  7. S. Umetani and H. Freiser, Inorg. Chem., 1987, 26, 3179 CrossRef CAS.
  8. Q. T. H. Le, S. Umetani, H. Takahara and M. Matsui, Anal. Chim. Acta, 1993, 272, 293 CrossRef CAS.
  9. S. Umetani, Y. Kawase, H. Takahara, Q. T. H. Le and M. Matsui, J. Chem. Soc., Chem. Commun., 1993, 78 RSC.
  10. R. W. Kluibert, J. Am. Chem. Soc., 1960, 82, 4839 CrossRef.
  11. L. B. Barkley and R. Levine, J. Am. Chem. Soc., 1953, 75, 2059 CrossRef CAS.
  12. M. J. Frisch, G. W. Trucks, M. Head-Gordon, P. M. W. Gill, M. W. Wong, J. B. Foresman, B. G. Johnson, H. B. Schlegel, M. A. Robb, E. S. Replogle, R. Gomperts, J. L. Andres, K. Raghavachari, J. S. Binkley, C. Gonzalez, R. L. Martin, D. J. Fox, D. J. Defress, J. Baker, J. J. P. Stewart and J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1992.
  13. L. G. Van Uitert and C. G. Hass, J. Am. Chem. Soc., 1953, 75, 451 CrossRef CAS.
  14. H. M. N. H. Irving and U. S. Mannot, J. Inorg. Nucl. Chem., 1968, 30, 1215 CrossRef CAS.
  15. K. Y. Burstein and A. N. Isaev, Theor. Chim. Acta, 1984, 64, 397 CrossRef CAS.
  16. M. J. S. Dewar, E. G. Zeobisch, E. F. Healy and J. J. P. Stewart, J. Am. Chem. Soc., 1985, 107, 3902 CrossRef.
  17. J. J. P. Stewart, J. Comput. Chem., 1989, 10, 209 CrossRef CAS.
  18. A. Camerman, D. Mastropaolo and N. Camerman, J. Am. Chem. Soc., 1983, 105, 1584 CrossRef CAS.
  19. A. L. Andreassen and S. H. Bauer, J. Mol. Struct., 1972, 12, 381 CrossRef CAS.
  20. K. Iijima, A. Ogoshi and S. Shibata, J. Mol. Struct., 1987, 156, 111 CrossRef CAS.
  21. T. S. Kopleva and D. N. Shigorin, Russ. J. Phys. Chem., 1974, 48, 312 Search PubMed.
  22. E. E. Ernstbrunner, J. Chem. Soc. A, 1970, 1558 RSC.
  23. R. M. Silverstein, G. C. Bassler and T. C. Morrill, in Spectrometric Identification of Organic Compounds, Wiley, New York, 1981 Search PubMed.
  24. D. C. Nonhebel, Tetrahedron, 1968, 24, 1896 CrossRef.
  25. H. Freiser, in Concepts & Calculations in Analytical Chemistry, CRC Press, Boca Raton, FL 1992 Search PubMed.
  26. J. Stary, in The Solvent Extraction of Metal Chelates, Pergamon, London, 1964 Search PubMed.
  27. E. C. Lingafelter and R. L. Braun, J. Am. Chem. Soc., 1966, 88, 2951 CrossRef CAS.
  28. C. S. Erasmus and J. C. A. Boeyens, J. Cryst. Mol. Struct., 1971, 1, 83 Search PubMed.
  29. J. G. White, Inorg. Chim. Acta, 1976, 16, 159 CrossRef CAS.
  30. G. J. McDougall and R. D. Hancock, J. Chem. Soc., Dalton Trans., 1980, 654 RSC.
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