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DOI: 10.1039/A606399C (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1997, 997-1002

Reactions of carbonyl compounds in basic solutions. Part 26.1 The mechanisms of the base-catalysed cyclisation of 1,2-diacetylbenzene, 1,8-diacetylnaphthalene, 4,5-diacetylphenanthrene and 2,2′-diacetylbiphenyl

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Keith Bowden and Andrew Brownhill

Abstract

Rate coefficients have been measured for the base-catalysed cyclisation of 1,2-diacetylbenzene 1, 1,8-diacetylnaphthalene 2, 4,5-diacetylphenanthrene 3 and 2,2′-diacetylbiphenyl 4 in a range of aqueous dimethyl sulfoxide (DMSO) compositions at 30.0 °C, as well as at 45.0 and 60.0 °C at certain concentrations, containing tetramethylammonium hydroxide. For three of the substrates, 1, 2 and 4, the di-[2H3]acetyl compounds were also studied. Studies of the relative rates, activation parameters, kinetic isotope and solvent isotope effects and correlation of the rates with an acidity function were made to give detailed mechanistic pathways. Thus, 2, 3 and 4 react with rate-determining base-catalysed ionisation to give the enolate anion, followed by relatively rapid intramolecular nucleophilic attack and dehydration to give the corresponding cyclic enones; whereas, 1 reacts by the same pathway but with rate-determining intramolecular nucleophilic attack. An intermolecular base-catalysed aldol reaction was also detected for the product of the intramolecular reaction of 2 at high DMSO contents.

References

  1. Part 25. A. Al-Najjar, K. Bowden and M. V. Horri, J. Chem. Soc., Perkin Trans. 2, 1997, 993 Search PubMed.
  2. A. T. Neilson and W. J. Houlihan, Org. React., 1968, 16, 1.
  3. C. R. Hauser, F. W. Swamer and J. T. Adams, Org. React., 1954, 8, 59.
  4. K. Bowden and A. M. Last, J. Chem. Soc., Perkin Trans. 2, 1973, 351 RSC.
  5. K. Bowden and M. Chehel-Amiran, J. Chem. Soc., Perkin Trans. 2, 1986, 2035 RSC.
  6. R. W. Nagorski, T. Mizerski and J. P. Richard, J. Am. Chem. Soc., 1995, 117, 4718 CrossRef CAS.
  7. J. M. Desper and R. Breslow, J. Am. Chem. Soc., 1994, 116, 12 081 CrossRef CAS; R. Breslow, J. Desper and Y. Huang, Tetrahedron Lett., 1996, 37, 2541 CrossRef CAS.
  8. T. Koch, J.-L. Reymond and R. A. Lerner, J. Am. Chem. Soc., 1995, 117, 9383 CrossRef CAS.
  9. D. S. Noyce, W. A. Pryor and A. H. Bottini, J. Am. Chem. Soc., 1955, 77, 1402 CrossRef CAS.
  10. K. Bowden and D. C. Parkin, Can. J. Chem., 1969, 47, 185 CAS.
  11. R. P. Bell and B. G. Cox, J. Chem. Soc. (B), 1970, 194 RSC.
  12. V. J. Shiner, Jr., in Isotope Effects in Chemical Reactions, eds. C. J. Collins and N. S. Bowman, Van Nostrand Reinhold, New York, 1970 Search PubMed.
  13. B. M. Davis, P. H. Gore, K. A. K. Lott, E. L. Short and H. G. Shinouda, J. Chem. Soc., Perkin Trans. 2, 1981, 58 RSC.
  14. D. Dolman and R. Stewart, Can. J. Chem., 1967, 45, 911 CAS.
  15. D. S. Noyce and W. L. Reed, J. Am. Chem. Soc., 1959, 81, 625.
  16. F. G. Bordwell, Acc. Chem. Res., 1988, 21, 456 CrossRef CAS.
  17. J. Appleyard and M. J. C. Crabbe, Desktop Molecular Modeller (version 2.0), Oxford University Press, Oxford, 1991 Search PubMed.
  18. K. Bowden and A. M. Last, J. Chem. Soc., Perkin Trans. 2, 1973, 1144 RSC.
  19. P. Deslongchamps, in Stereoelectronic Effects in Organic Chemistry, Pergamon Press, Oxford, 1983 Search PubMed; H. B. Burgi, J. D. Dunitz and E. Shefter, J. Am. Chem. Soc., 1973, 95, 5065 Search PubMed.
  20. L. L. Ingraham, in Steric Effects in Organic Chemistry, ed. M. S. Newman, Wiley, New York, 1956, ch. 9 Search PubMed; M. R. Abbaszadeh and K. Bowden, J. Chem. Soc., Perkin Trans. 2, 1990, 2081 Search PubMed.
  21. K. Bowden, in Organic Reactivity: Physical and Biological Aspects, eds. B. T. Golding, R. J. Griffin and H. Maskill, Royal Society of Chemistry, Cambridge, 1995, p. 123 Search PubMed.
  22. S. Goldschmidt and A. Zoebden, Can. J. Chem., 1966, 44, 1323.
  23. W. Trapp and T. Zincke, Liebigs Ann. Chem., 1905, 362, 342 Search PubMed; W. Trapp and T. Zincke, Liebigs Ann. Chem., 1905, 363, 302 Search PubMed; S. Goldschmidt and A. Zoebden, Chem. Ber., 1961, 94, 169 CAS; R. Creigee, E. Hager, G. Huber, P. Kruck, F. Marktsheffel and H. Schevenberger, Liebigs Ann. Chem., 1956, 599, 81 Search PubMed.
  24. S. Toma, E. Solcaniova and D. G. Leppard, Acta Fac. Rerum. Nat. Univ. Comeniannae, Chim., 1982, 30, 7 (Chem. Abstr., 1983, 98, 160892u) Search PubMed.
  25. E. Laarge, F. Grimm and R. Stoermer, Chem. Ber., 1917, 50, 959 Search PubMed.
  26. R. Creigee and L. Kraft, Annalen, 1933, 507, 159 Search PubMed; D. M. Hall, J. E. Ladbury, M. S. Lesslie and E. E. Turner, J. Chem. Soc., 1956, 3474 Search PubMed; D. E. Cooke and J. Turner, J. Chem. Soc., 1937, 117 RSC.
  27. K. Bowden and M. J. Price, J. Chem. Soc. (B), 1971, 1748 Search PubMed; K. Bowden and R. S. Cook, J. Chem. Soc. (B), 1971, 1765; 1771 RSC.
  28. K. Bowden and A. M. Last, J. Chem. Soc., Perkin Trans. 2, 1973, 345 RSC.
  29. J. H. Espenson, Chemical Kinetics and Reaction Mechanisms, McGraw-Hill, New York, 2nd edn., 1991, ch. 2 Search PubMed.
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