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DOI: 10.1039/A606098F (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1997, 547-552

Semi-empirical AM1 and PM3 molecular orbital calculations on the mechanism of the hydrolysis of unsaturated lactones: substituted (E[hair space])-5,5′-diphenylbifuranylidenediones and 3,7-diphenylpyrano[4,3-c]pyran-1,5-diones

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Keith Bowden, Walter M. F. Fabian[hair space] and Gert Kollenz

Abstract

Semi-empirical molecular orbital (AM1 and PM3) calculations including solvent effects by the SCRF model on the mechanism of the addition of nucleophiles to unsaturated five- and six-membered bislactones of the Pechmann dye type indicate a similar mechanism for both systems. The rate-determining step appears to be the addition of a second nucleophile to the enol of the ring-opened monolactone. The five-membered lactones are found to be more reactive than their six-membered analogues. Electron donor substituents ([hair space]p-Me, p-MeO) increase and acceptor substituents ([hair space]p-Cl, m-NO2) decrease the activation energy.

References

  1. G. Kollenz and W. Heilmayer, Trends Heterocycl. Chem., 1993, 3, 379 Search PubMed; C. Wentrup, W. Heilmayer and G. Kollenz, Synthesis, 1994,(Special issue), 1219 CrossRef CAS; Zs. Juhasz-Riedl, G. Hajos, G. Kollenz and A. Messmer, Chem. Ber., 1989, 122, 1935 CAS.
  2. E. Terpetschnig, G. Penn, G. Kollenz, K. Peters, E.-M. Peters and H. G. v. Schnering, Tetrahedron, 1991, 47, 3045 CrossRef CAS; G. Kollenz, H. Sterk and G. Hutter, J. Org. Chem., 1991, 56, 235 CrossRef CAS; C. O. Kappe, G. Kollenz, W. M. F. Fabian, C. Wentrup and G. Färber, J. Org. Chem., 1993, 58, 3361 CrossRef CAS.
  3. G. Kollenz, G. Penn, R. Theuer, W. M. F. Fabian, H. A. Abd El-Nabi, X. Zhang, K. Peters, E.-M. Peters and H. G. von Schnering, Tetrahedron, 1996, 52, 5427 CrossRef.
  4. K. Vyas and H. Manohar, J. Chem. Soc., Perkin Trans. 2, 1990, 1177 RSC; A. Pawlik, W. Grahn, A. Reisner, P. G. Jones and E. Ludger, Angew. Chem., Int. Ed. Engl., 1994, 33, 1958 CrossRef; M. T. Bogert and J. J. Ritter, J. Am. Chem. Soc., 1924, 46, 2871 CrossRef CAS; M. Irie and M. Kato, J. Am. Chem. Soc., 1985, 107, 1024 CrossRef CAS.
  5. G. Haucke and G. Graneβ, Angew. Chem., Int. Ed. Engl., 1995, 34, 67 CrossRef CAS.
  6. H. von Pechmann, Ber. Dtsch. Chem. Ges., 1882, 15, 881 Search PubMed; C. S. Fang and W. Bergmann, J. Org. Chem., 1951, 16, 1231 CrossRef CAS; E. Klingsberg, Chem. Rev., 1954, 54, 59 CrossRef CAS.
  7. K. Bowden and K. Bromley, J. Chem. Soc., Perkin Trans. 2, 1990, 2103, 2111 RSC; K. Bowden and F. P. Malik, J. Chem. Soc., Perkin Trans. 2, 1992, 5 RSC; K. Bowden and F. P. Malik, J. Chem. Soc., Perkin Trans. 2, 1993, 7, 635 RSC; K. Bowden and K. D. Williams, J. Chem. Soc., Perkin Trans. 2, 1994, 77 RSC.
  8. K. Bowden, R. Etemadi and R. J. Ranson, J. Chem. Soc., Perkin Trans. 2, 1991, 743 RSC.
  9. K. Bowden and R. J. Ranson, J. Phys. Org. Chem., submitted for publication Search PubMed.
  10. (a) K. B. Wilberg, K. M. Morgan and H. Maltz, J. Am. Chem. Soc., 1994, 116, 11 067 CrossRef; (b) O. N. Ventura, E. L. Coitiño, A. Lledos and J. Bertran, J. Comput. Chem., 1992, 13, 1037 CrossRef CAS; (c) M. D. Erion and M. R. Reddy, J. Comput. Chem., 1995, 16, 1513 CrossRef CAS; (d) I. H. Williams, D. Spangler, G. M. Maggiora and R. L. Schowen, J. Am. Chem. Soc., 1985, 107, 7717 CrossRef CAS; (e) I. H. Williams, J. Am Chem. Soc., 1987, 109, 6299 CrossRef CAS; (f) B. E. Thomas IV and P. A. Kollman, J. Org. Chem., 1995, 60, 8375 CrossRef; (g) K. B. Wiberg and R. F. Waldron, J. Am. Chem. Soc., 1991, 113, 7697 CrossRef CAS.
  11. (a) S. Hoz, K. Yang and S. Wolfe, J. Am. Chem. Soc., 1990, 112, 1319 CrossRef CAS; (b) S. Schröder, V. Daggett and P. Kollman, J. Am. Chem. Soc., 1991, 113, 8922 CrossRef; (c) V. Daggett, S. Schöder and P. Kollmann, J. Am. Chem. Soc., 1991, 113, 8926 CrossRef CAS; (d) T. Katagi, J. Comput. Chem., 1990, 11, 524; 1094; (e) L. M. Pratt and C. C. Chu, J. Comput. Chem., 1993, 14, 809 CrossRef CAS; (f) J. Frau, J. Donoso, F. Muñoz and F. G. Blanco, J. Comput. Chem., 1993, 14, 1545 CrossRef CAS.
  12. H. S. Rzepa and G. A. Suñer, J. Chem. Soc., Perkin Trans. 2, 1994, 1397 RSC.
  13. I. Rajyaguru and H. S. Rzepa, J. Chem. Soc., Perkin Trans. 2, 1987, 1819 RSC.
  14. M. J. S. Dewar, E. G. Zoebisch, E. F. Healy and J. J. P. Stewart, J. Am. Chem. Soc., 1985, 107, 3902 CrossRef.
  15. M. J. S. Dewar and D. M. Storch, J. Chem. Soc., Perkin Trans. 2, 1989, 877 RSC.
  16. J. J. P. Stewart, J. Comput. Chem., 1989, 10, 209; 221.
  17. K. Bowden, I. Prokes, A. Perjessy, P. Hrnciar and W. M. F. Fabian, unpublished results.
  18. R. Janoschek and W. M. F. Fabian, unpublished results.
  19. O. Tapia and O. Goscinski, Mol. Phys., 1975, 29, 1653 CAS.
  20. T. Clark, VAMP, Erlangen Vectorised Molecular Orbital Package, Version 4.40, Computer-Chemie-Centrum, University Erlangen-Nürnberg, Germany.
  21. SYBYL 6.2, Tripos Associates, St. Louis, MO, USA.
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