Photochemistry and Photophysics of Papaverine N-Oxide
F. A. Souto-Bachiller
Department of Chemistry, Faculty of Arts and Sciences, University of Puerto Rico, Mayagiiez, Puerto Rico
Search for more papers by this authorCorresponding Author
E. Perez-lnestrosa
Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Málaga, Málaga, Spain
*Departamento de Química Orginica, Facultad de Ciencias, Universidad de Málaga, E-29071, Málaga, Spain. Fax: (34) 952 13 19 41; e-mail:[email protected]Search for more papers by this authorR. Suau
Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Málaga, Málaga, Spain
Search for more papers by this authorR. Rico-Gómez
Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Málaga, Málaga, Spain
Search for more papers by this authorL. A. Rodríguez-Rodríguez
Department of Chemistry, Faculty of Arts and Sciences, University of Puerto Rico, Mayagiiez, Puerto Rico
Search for more papers by this authorM. E. Coronado-Pérez
Department of Chemistry, Faculty of Arts and Sciences, University of Puerto Rico, Mayagiiez, Puerto Rico
Search for more papers by this authorF. A. Souto-Bachiller
Department of Chemistry, Faculty of Arts and Sciences, University of Puerto Rico, Mayagiiez, Puerto Rico
Search for more papers by this authorCorresponding Author
E. Perez-lnestrosa
Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Málaga, Málaga, Spain
*Departamento de Química Orginica, Facultad de Ciencias, Universidad de Málaga, E-29071, Málaga, Spain. Fax: (34) 952 13 19 41; e-mail:[email protected]Search for more papers by this authorR. Suau
Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Málaga, Málaga, Spain
Search for more papers by this authorR. Rico-Gómez
Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Málaga, Málaga, Spain
Search for more papers by this authorL. A. Rodríguez-Rodríguez
Department of Chemistry, Faculty of Arts and Sciences, University of Puerto Rico, Mayagiiez, Puerto Rico
Search for more papers by this authorM. E. Coronado-Pérez
Department of Chemistry, Faculty of Arts and Sciences, University of Puerto Rico, Mayagiiez, Puerto Rico
Search for more papers by this authorAbstract
The photochemistry and photophysics of papaverine N-oxide in polar aprotic and protic solvents has been studied in detail. Complex energy and charge-transfer phenomena between chromophores occur in papaverine. New photochemistry for the papaverine N-oxide system is reported. Irradiation in protic media results in the formation of an emissive charge-transfer state with ensuing intramolecular hydroxylation in high isolated yields (75–80%).
References
- 1 Southon, I. W. and J. Buckingham (1989) In Dictionary of Alkaloids (Edited by G. A. Cordwell, M. Shamma, J. E. Saxton and G. F. Smith), p. 820. Chapman and Hall, London .
- 2 Bremner, J. B. and P. Wiriyachitra (1973) The photochemistry of papaverine N-oxide. Aust. J. Chem. 26, 437–442.
- 3 Albini, A. and M. Alpegiani (1984) The photochemistry of the N-oxide function. Chem. Rev. 84, 43–71.
- 4 Sammes, P. G., G. Serra-Errante and A. C. Tinker (1978) Intramolecular aromatic hydroxylation via irradiation of pyridine N-oxide derivatives. J. Chem. Soc. Perkin 1, pp. 853–863.
- 5 Streith, J., B. Danner and C. Sigwalt (1967) Photochemistry of pyridine oxides: atomic oxygen transfer in solution; a new synthesis of phenol. Chem. Commun., pp. 979–980.
- 6 Igeta, H., T. Tsuchiya, M. Yamada and H. Arai (1968) Synthesis of pyridazine derivatives. IX. Photo-induced oxygenation of hydrocarbons by pyridazine N-oxide. Chem. Pharm. Bull. 16, 767–769.
- 7
Jerina, D. M.,
D. R. Boyd and
J. W. Daly (1970) Photolysis of pyridine N-oxide: an oxygen atom transfer model for enzymatic oxygenation, arene oxide formation and the NIH shift.
Tetrahedron Lett., 11, 457–460.
10.1016/0040-4039(70)80074-0 Google Scholar
- 8
Tsuchiya, T.,
H. Arai and
H. Igeta (1969) Photo-induced oxygenation by pyridazine N-oxides. II. Formation of epoxides from ethylenic compounds.
Tetrahedron Lett., 10, 2747–2750; (1970), 2213.
10.1016/S0040-4039(01)88259-9 Google Scholar
- 9 Sako, M., K. Shimada, K. Hirota and Y. Maki (1985) Efficient oxygen-atom transfer agent; photochemical hydroxylation of benzene derivatives by pyrimido[5,4-g]pteridine N-oxide. Tetrahedron Lett., 26, 6493–6496.
- 10 Sako, M., K. Shimada, K. Hirota and Y. Maki (1986) Photochemical oxygen-atom transfer reaction by heterocycle N-oxides involving a single-electron transfer process: oxidative demeth-ylation of N, N-dimethylaniline. J. Am. Chem. Soc, 108, 6039–6041.
- 11 Suau, R., R. Rico-Gómez, F. A. Souto-Bachiller, L. A. Rodríguez-Rodríguez and M. L. Ruiz (1995) Efficient photoinduced electron-transfer in papaverine N-oxide. Regioselective intramolecular hydroxylation of papaverine as an alternative disconnection for the synthesis of cularine alkaloids. Tetrahedron Lett. 36, 2653–2656.
- 12 Hata, N., I. Ono and M. Kawasaki (1975) Photoinduced deox-ygenation reaction of heterocyclic N-oxides. Chem. Lett., pp. 25–28.
- 13 Fluorescence Spectroscopy Application Data Bulletin, Order No. FL-93 and ADS-134, Perkin-Elmer Co., Norwalk , CT 06856, USA.
- 14 Demas, J. N. and G. A. Crosby (1971) Measurement of photo-luminescence quantum yield. J. Phys. Chem. 71, 991–1024.
- 15 O'Connor, D. V. and D. Phillips (1984) Time Correlated Single Photon Counting, p. 31. Academic Press, Orlando , FL .
- 16 Maier, J. P., J. F. Muller, T. Kubota and M. Yamakawa (1975) Ionisation energies and the electronic structures of the N-oxides of azanaphthalenes and azaanthracenes. Helv. Chim. Acta 58, 1641–1648.
- 17 Weller, A. Z. Z. (1982) Photoinduced electron-transfer in solution. Exciplex and radical ion-pair formation free enthalpies and their solvent dependence. Physik. Chem. 133, 93–98.
- 18 Ochiai, E. (1967) Aromatic Amine Oxides, pp. 91–96. Elsevier, Amsterdam .
- 19 Warman, J. M., M. P. De Haas, M. N. Paddon-Row, E. Cotsaris, N. S. Hush, H. Oevering and J. W. Verhoeven (1986) Light-induced giant dipoles in simple-model compounds for photosynthesis. Nature 320, 615–616.
- 20 Stockburger, M., H. Gattermann and W. Klusmann (1975) Spectroscopic studies on naphthalene in the vapour phase. II. Fluorescence quantum yields from single vibronic levels in the first excited singlet state. Behavior of higher excited singlet states. J. Chem. Phys. 63, 4529–4540.
- 21 Hadley, S. G. (1971) Direct determination of singlet-rtriplet in-tersystem crossing quantum yield. Quinoline, isoquinoline and quinoxaline. J. Phys. Chem. 75, 2083–2086.
- 22 Kubota, T., M. Yamakawa and Y. Mizuno (1972) Singlet-triplet absorption spectra of heterocyclic amine N-oxides. I. Bull. Chem. Soc. Jpn. 45, 3282–3286.
- 23 Huber, J. R., M. Mahaney and J. V. Morris (1976) Temperature dependence of radiatioriless processes. Isoquinoline in solution. Chem. Phys. 16, 329–335.
- 24 Schuddeboom, W., T. Scherer, J. M. Warman and J. W. Ver-hoeven (1993) Formation of extended and folded charge separated states of donor-spacer-acceptor molecules with flexible and semirigid sigma-bond spacers. J. Phys. Chem. 97, 13092–13098.
