Advertisement

Chemistry of Heterocyclic Compounds

, Volume 33, Issue 12, pp 1405–1420 | Cite as

Porphyrins.

36.cis,trans-Isomerism and atropisomerism in molecules of ethylenebisporphyrins
  • G. V. Ponomarev
  • D. V. Yashunskii
  • V. V. Borovkov
  • E. Sakata
  • D. Arnold
Article
  • 79 Downloads

Abstract

The synthesis of octaalkyl esters of 1,2-(meso-coproporphyrin-I-yl)ethane has been carried out from the corresponding copper complexes ofmeso-hydroxymethyl- and the nickel complexes ofmeso-dimethylaminomethylporphyrins. Their conversion into the correspondingtrans- andcis-ethylenebisporphyrins has been investigated. On boiling in AcOH or xylene, ethylenebisporphyrins form an equilibrium mixture ofcis andtrans isomers. The cis and trans isomers of 1,2-di(octaethylporphyrin-I-yl)ethylene and the octaethyl ester of 1,2-di(coproporphyrin-I-yl)ethylene have been isolated and their interconversions investigated. It was demonstrated by PMR that thecis isomers of ethylenebisporphyrins have a rigid structure in which there is no free rotation of the porphyrin rings. The presence of two atropisomers is also a characteristic of thecis isomer of the coproporphyrin-I derivative. The formation of metal complexes in combination with the preparation of complexes with additional ligands enables control of the conformation of ethanebisporphyrins in solution. A mechanism has been proposed for the oxidation of ethanebisporphyrins totrans-ethylenebisporphyrins in acetic and other lower aliphatic acids.

Keywords

Copper Ethylene Ester Nickel Ethane 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    G. V. Ponomarev, D. V. Yashunskii, and A. S. Moskovkin, Khim. Geterotsikl. Soedin., No. 3, 324 (1997).Google Scholar
  2. 2.
    G. V. Ponomarev, V. V. Borovkov, K. Sugiura, Y. Sakata, and A. M. Shul'ga, Tetrahedron Lett.,34, 2153 (1993).Google Scholar
  3. 3.
    G. V. Ponomarev, V. V. Borovkov, A. M. Shul'ga, and Y. Sakata, J. Chem. Soc., Chem. Commun., No. 17, 1927 (1994).Google Scholar
  4. 4.
    T. Nagata, R. Marujama, and K. Toriumi, Angew. Chem.,103, 579 (1991).Google Scholar
  5. 5.
    M. R. Wasielewski, Chem. Rev.,92, 435 (1992).Google Scholar
  6. 6.
    G. V. Ponomarev, Dissertation for Doctor of Chemical Sciences, Moscow (1984).Google Scholar
  7. 7.
    G. V. Ponomarev and A. M. Shul'ga, Khim. Geterotsikl. Soedin., No. 2, 278 (1986).Google Scholar
  8. 8.
    A. M. Shul'ga and G. V. Ponomarev, Khim. Geterotsikl. Soedin., No. 3, 339 (1988).Google Scholar
  9. 9.
    V. V. Borovkov, G. V. Ponomarev, A. Ishida, T. Kaneda, and Y. Sakata, Chem. Lett., No. 8, 1409 (1993).Google Scholar
  10. 10.
    M. O. Senge, K. R. Gerzevske, M. G. H. Vicente, T. P. Forsyth, and K. M. Smith, Angew. Chem., Intern. Ed. Engl.,32, 750 (1993).Google Scholar
  11. 11.
    H. Higuchi, K. Shimizu, K.-I. Sugiura, and Y. Sakata, Tetrahedron Lett.,36, 5359 (1995).Google Scholar
  12. 12.
    D. V. Yashunsky, G. V. Ponomarev, and D. P. Arnold, Tetrahedron Lett.,36, 8485 (1995).Google Scholar
  13. 13.
    L. Jaqinod, D. J. Nurco, C. J. Medforth, R. K. Pandey, T. P. Forsyth, M. M. Olmstead, and K. M. Smith, Angew. Chem., Intern. Ed. Engl.,35, 1013 (1996).Google Scholar
  14. 14.
    G. V. Ponomarev and A. M. Shul'ga, Authors Certificate No. 1,172,922 SSSR; Byull. Izobret., No. 30, 99 (1985).Google Scholar
  15. 15.
    G. V. Ponomarev and A. M. Shul'ga, Authors Certificate No. 1,172,923 SSSR; Byull. Izobret., No. 30, 99 (1985).Google Scholar
  16. 16.
    G. V. Ponomarev, Khim. Geterotsikl. Soedin., No. 10, 1430 (1993).Google Scholar
  17. 17.
    G. V. Ponomarev, Khim. Geterotsikl. Soedin., No. 12, 1692 (1993).Google Scholar
  18. 18.
    D. V. Yashunsky, G. V. Ponomarev, and D. P. Arnold, Tetrahedron Lett.,37, 7147 (1996).Google Scholar
  19. 19.
    D. Arnold, A. W. Johnson, and M. Winter, J. Chem. Soc., Perkin Trans. I, No. 7, 1643 (1977).Google Scholar
  20. 20.
    K. M. Smith, G. M. F. Bisset, and M. J. Bushell, Bioorg. Chem.,9, 1 (1980).Google Scholar
  21. 21.
    D. V. Yashunskii, G. V. Ponomarev, and D. P. Arnold, Khim. Geterotsikl. Soedin., No. 11/12, 1659 (1996).Google Scholar
  22. 22.
    M. Chachisvilis, V. S. Chirvony, A. M. Shulga, B. Kallebring, B. Larsson, and V. Sundstrom, J. Phys. Chem.,100, 13857 (1996).Google Scholar
  23. 23.
    M. Chachisvilis, V. S. Chirvony, A. M. Shulga, B. Kallebring, B. Larsson, and V. Sundstrom, J. Phys. Chem.,100, 13867 (1996).Google Scholar
  24. 24.
    R. Kitagawa, Y. Kay, G. V. Ponomarev, K. Sugiura, V. V. Borovkov, and Y. Sakata, Chem. Lett., No. 6, 1071 (1993).Google Scholar
  25. 25.
    G. V. Ponomarev, Khim. Geterotsikl. Soedin., No. 7, 923 (1979).Google Scholar
  26. 26.
    K. Sugiura, Y. Sakata, G. V. Ponomarev, S. Okubo, A. Tajiri, A. Iwasaki, and S. Hino, Synth. Met.,71, 2095 (1995).Google Scholar
  27. 27.
    G. V. Ponomarev, Khim. Geterotsikl. Soedin., No. 10, 1339 (1993).Google Scholar
  28. 28.
    M. O. Senge, M. G. H. Vicente, K. R. Gerzevske, T. P. Forsyth, and K. M. Smith, Inorg. Chem.,33, 5625 (1994).Google Scholar
  29. 29.
    M. O. Senge, G. V. Ponomarev, T. P. Forsyth, and K. M. Smith, Z. Naturforsch. B,51, 1644 (1996).Google Scholar
  30. 30.
    P. B. Hitchcock, J. Chem. Soc., Dalton Trans., No. 9, 2127 (1983).Google Scholar
  31. 31.
    I. M. Karnaukh, A. S. Moskovkin, and G. V. Ponomarev, Khim. Geterotsikl. Soedin., No. 11, 1478 (1993).Google Scholar

Copyright information

© Plenum Publishing Corporation 1998

Authors and Affiliations

  • G. V. Ponomarev
  • D. V. Yashunskii
  • V. V. Borovkov
  • E. Sakata
  • D. Arnold

There are no affiliations available

Personalised recommendations