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.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
G. V. Ponomarev, D. V. Yashunskii, and A. S. Moskovkin, Khim. Geterotsikl. Soedin., No. 3, 324 (1997).
G. V. Ponomarev, V. V. Borovkov, K. Sugiura, Y. Sakata, and A. M. Shul'ga, Tetrahedron Lett.,34, 2153 (1993).
G. V. Ponomarev, V. V. Borovkov, A. M. Shul'ga, and Y. Sakata, J. Chem. Soc., Chem. Commun., No. 17, 1927 (1994).
T. Nagata, R. Marujama, and K. Toriumi, Angew. Chem.,103, 579 (1991).
M. R. Wasielewski, Chem. Rev.,92, 435 (1992).
G. V. Ponomarev, Dissertation for Doctor of Chemical Sciences, Moscow (1984).
G. V. Ponomarev and A. M. Shul'ga, Khim. Geterotsikl. Soedin., No. 2, 278 (1986).
A. M. Shul'ga and G. V. Ponomarev, Khim. Geterotsikl. Soedin., No. 3, 339 (1988).
V. V. Borovkov, G. V. Ponomarev, A. Ishida, T. Kaneda, and Y. Sakata, Chem. Lett., No. 8, 1409 (1993).
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).
H. Higuchi, K. Shimizu, K.-I. Sugiura, and Y. Sakata, Tetrahedron Lett.,36, 5359 (1995).
D. V. Yashunsky, G. V. Ponomarev, and D. P. Arnold, Tetrahedron Lett.,36, 8485 (1995).
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).
G. V. Ponomarev and A. M. Shul'ga, Authors Certificate No. 1,172,922 SSSR; Byull. Izobret., No. 30, 99 (1985).
G. V. Ponomarev and A. M. Shul'ga, Authors Certificate No. 1,172,923 SSSR; Byull. Izobret., No. 30, 99 (1985).
G. V. Ponomarev, Khim. Geterotsikl. Soedin., No. 10, 1430 (1993).
G. V. Ponomarev, Khim. Geterotsikl. Soedin., No. 12, 1692 (1993).
D. V. Yashunsky, G. V. Ponomarev, and D. P. Arnold, Tetrahedron Lett.,37, 7147 (1996).
D. Arnold, A. W. Johnson, and M. Winter, J. Chem. Soc., Perkin Trans. I, No. 7, 1643 (1977).
K. M. Smith, G. M. F. Bisset, and M. J. Bushell, Bioorg. Chem.,9, 1 (1980).
D. V. Yashunskii, G. V. Ponomarev, and D. P. Arnold, Khim. Geterotsikl. Soedin., No. 11/12, 1659 (1996).
M. Chachisvilis, V. S. Chirvony, A. M. Shulga, B. Kallebring, B. Larsson, and V. Sundstrom, J. Phys. Chem.,100, 13857 (1996).
M. Chachisvilis, V. S. Chirvony, A. M. Shulga, B. Kallebring, B. Larsson, and V. Sundstrom, J. Phys. Chem.,100, 13867 (1996).
R. Kitagawa, Y. Kay, G. V. Ponomarev, K. Sugiura, V. V. Borovkov, and Y. Sakata, Chem. Lett., No. 6, 1071 (1993).
G. V. Ponomarev, Khim. Geterotsikl. Soedin., No. 7, 923 (1979).
K. Sugiura, Y. Sakata, G. V. Ponomarev, S. Okubo, A. Tajiri, A. Iwasaki, and S. Hino, Synth. Met.,71, 2095 (1995).
G. V. Ponomarev, Khim. Geterotsikl. Soedin., No. 10, 1339 (1993).
M. O. Senge, M. G. H. Vicente, K. R. Gerzevske, T. P. Forsyth, and K. M. Smith, Inorg. Chem.,33, 5625 (1994).
M. O. Senge, G. V. Ponomarev, T. P. Forsyth, and K. M. Smith, Z. Naturforsch. B,51, 1644 (1996).
P. B. Hitchcock, J. Chem. Soc., Dalton Trans., No. 9, 2127 (1983).
I. M. Karnaukh, A. S. Moskovkin, and G. V. Ponomarev, Khim. Geterotsikl. Soedin., No. 11, 1478 (1993).
Additional information
For part 35 see [1]: for preliminary communications see [2, 3].
Institute of Biomedicinal Chemistry, Russian Academy of Medical Sciences, Moscow 119832.
Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki-shi, Osaka, 567, Japan. Queensland University of Technology. GPO Box 2434, Brisbane 4001, Australia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1627–1645, December, 1997.