Monatshefte für Chemie / Chemical Monthly

, Volume 124, Issue 2, pp 209–215 | Cite as

Direct photolysis and electron transfer photooxygenation of enol acetates of 3-phenylpropiophenones

  • Felipe Algarra
  • María V. Baldoví
  • Hermenegildo García
  • Miguel A. Miranda
  • Jaime Primo
Organische Chemie Und Biochemie


Direct photolysis of enol acetates of 3-phenylpropiophenones1a–c gives rise to the parent propiophenones2a–c and the 1,3-acyl shift products3a–c. By contrast, 2,4,6-triphenylpyrylium tetrafluoroborate sensitized photolysis of substrates1a–c affords the α-acetyloxypropiophenones7a–c as the most general products. These results have been rationalized according to the generation of radical pairs in the direct photolysis and radical cations in the photoinduced electron transfer processes.


Enol acetates of 3-phenylpropiophenones 1,3-Acyl migration Photoinduced electron transfer 2,4,6-Triphenylpyrylium tetrafluoroborate 

Direkte Photolyse und Flektron-Transfer-Photooxygenierung von Enolacetaten von 3-Phenylpropiophenonen


Die direkte Photolyse von Enolacetaten der 3-Phenylpropiophenone1a–c ergab die zugrundeliegenden Propiophenone2a–c und die 1,3-acyl-verschobenen Produkte3a–c. Im Gegensatz dazu ergab die 2,4,6-Triphenylpyrylium-tetrafluorborat-sensitivierte Photolyse der Substrate1a–c die α-Acetyloxypropiophenone7a–c als generelle Produkte. Diese Ergebnisse sind mit der Erzeugung von Radikalpaaren bei der direkten Photolyse und der Bildung von Radikalkationen beim photoinduzierten Elektronen-Transfer-Prozess zu erklären.


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References and Notes

  1. [1]
    Miranda M. A., García H. (1992) Carboxylic Acid and Derivatives, The Chemistry of Functional Groups, Suppl. B, Ch. 26. Wiley, Patai, p. 1271Google Scholar
  2. [2]
    Climent M. J., García H., Iborra S., Miranda M. A., Primo J. (1991) Tetrahedron47: 9289Google Scholar
  3. [3]
    For references dealing with the use of TPT as PET sensitizer see: a) Mattes S. L., Farid S. (1983) Org. Photochem.6: 233;Google Scholar
  4. [3] b)
    Kavarnos G. J., Turro N. J. (1986) Chem. Rev.86: 401;Google Scholar
  5. [3] c)
    Mattay J. (1987) Angew. Chem., Int. Ed. Engl.26: 825Google Scholar
  6. [4]
    Lowe J. U. Jr., Ferguson L. N. (1965) J. Org. Chem.30, 3000Google Scholar
  7. [6]
    Alvaro M., Baldoví V., García H., Miranda M. A., Primo J. (1987) Tetrahedron Lett.28: 3613Google Scholar
  8. [7]
    Marquet J., Moreno-Mañas M., Pacheco P., Prat M., Katritzky A. R., Brycki B. (1990) Tetrahedron46: 5333Google Scholar
  9. [8]
    Murov S. L. (1973) Handbook of Photochemistry, Dekker, New York, p. 97Google Scholar
  10. [9]
    Shono T. (1984) Electroorganic chemistry as a New Tool in Organic Synthesis, springer, New York Berlin Heidelberg, pp. 21–23Google Scholar
  11. [10]
    Baldoví M. V., García H., Miranda M. A., Primo J. (1990) Monatsh. Chem.121: 371Google Scholar
  12. [11]
    Climent M. J., García H., Iborra S., Miranda M. A., Primo J. (1989) Heterocycles29: 115Google Scholar
  13. [13]
    Marquet J., Moreno-Mañas M., Pacheco P., Vallribera A. (1988) Tetrahedron Lett.29: 1469Google Scholar
  14. [14]
    Ohta H., lkemoto M., li H., Okamoto Y., Tsuchihashi G.-i. (1986) Chem. Lett. 1169Google Scholar
  15. [15]
    Ota H., Dobashi G. Japan Kokai Tokkyo Koho JP 62,208.298 (12 Sep. 1987); cf. C.A. (1988)108: 148914vGoogle Scholar

Copyright information

© Springer-Verlag 1993

Authors and Affiliations

  • Felipe Algarra
    • 1
  • María V. Baldoví
    • 1
  • Hermenegildo García
    • 1
  • Miguel A. Miranda
    • 1
  • Jaime Primo
    • 1
  1. 1.Instituto de Tecnología Química CSIC-UPV y Departamento de QuímicaUniversidad Politécnica de ValenciaValenciaSpain

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