Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Die Photoenolisierung, Autoxidation und Dimerisation von 2-Isobutyliden-1,3-indandion

Organic Lewis acids, 351. Photoenolisation, autoxidation, and dimerisation of 2-isobutyliden-1,3-indandione

Zur Kenntnis organischer Lewis-Säuren, 35

  • 49 Accesses

  • 4 Citations


The title compound,1, slowly decomposes in solution by autodixation, especially in daylight. The chemism of this photoinduced autoxidation has been investigated.

Upon irradiation1 passes to the brick red isolable dienol2. The quantum yield is 0.3 at 313 nm in methanol. In solution an equilibrium is set up within several minutes between2 and the colorless deconjugated3. Unpolar or moderately polar solvents shift the equilibrium completely to3, whereas in highly polar solvents2 and3 coexist. In the dark the equilibrium12 (ca. 50∶1 in methanol) is established very slowly.3 upon irradiation reacts further to dimer8.

2 instantaneously reacts with oxygen. With high oxygen concentrations, hydroperoxide9 is formed, with lower ones dehydrodimer10, inter alia.9 and10 may further form12, 14, and15. These reactions, together with ESR spectroscopy, point to a central role of the free radical13 both in the autoxidation and in the reaction1014.

Basic catalysis sets up an equilibrium between1 and its dimer,17. The photoreaction12 has been investigated by sensitizing and quenching experiments.

This is a preview of subscription content, log in to check access.


  1. 2

    A. Sevin, B. Bigot undM. Pfau, Helv. Chim. Acta62, 699 (1979), und dort zitierte Literatur; Übersichten:P. G. Sammes, Tetrahedron32, 405 (1976);N. C. Yang in: Reactivity of the Photoexcited Organic Molecules, S. 145 ff. New York: Interscience. 1967.

  2. 3

    R. Noyori, H. Inoue undM. Kato, J. Amer. Chem. Soc.92, 6699 (1970).

  3. 4

    N. C. Yang undM. J. Jorgenson, Tetrahedron Lett.1964, 1203;N. C. Yang undC. Rivas, J. Amer. Chem. Soc.83, 2213 (1961);M. Pfau, N. D. Heindel undT. F. Lemke, C. R. Acad. Sci.261, 1017 (1965).

  4. 5

    Analoge Reaktionen:H. Peham, O. E. Polansky undF. Wessely, Mh. Chem.98, 1665 (1967);F. P. Schmook undO. E. Polansky, Mh. Chem.100, 1631 (1969).

  5. 6

    C. M. Harris, J. J. Cleary undT. M. Harris, J. Org. Chem.39, 72 (1974).

  6. 7

    J. Rigaudy undP. Derible, Bull. Soc. Chim. Fr.1965, 3047, 3055, 3061.

  7. 8

    A. Hantzsch, Liebigs Ann. Chem.392, 286 (1912);A. Hantzsch undF. Gajewski, ebenda Liebigs Ann. Chem.392, 302 (1912).

  8. 9

    J. Lindberg, O. Neiland, A. Veis undG. Vanag, Dokl. Akad. Nauk SSSR, Ser. Khim.154, 1385 (1964).

  9. 10

    E. S. Gould, Mechanismus und Struktur in der Organischen Chemie, S. 231–233. Weinheim/Bergstr.: Verlag Chemie. 1962.

  10. 11

    J. Leitich, H. Partale undO. E. Polansky, Chem. Ber.112, 3293 (1979).

  11. 12

    W. G. Herkstroeter undG. S. Hammond, J. Amer. Chem. Soc.88, 4769 (1966).

  12. 13

    S. L. Murov, Handbook of Photochemistry, S. 1 ff. New York: M. Dekker. 1973.

  13. 14

    I. V. Khudyakov, A. I. Yasmenko undV. A. Kuzmin, Int. J. Chem. Kinet.11, 621 (1979);A. B. Gagarina, L. M. Pisarenko, L. I. Murza undN. M. Emanuel, Dokl. Akad. Nauk SSSR, Ser. Khim.215, 894 (1974); Übersicht:V. V. Moiseev undI. T. Poluktov, Russian Chemical Reviews42, 214 (1973).

  14. 15

    F. J. Kunz undO. E. Polansky, Mh. Chem.100, 95 (1969).

  15. 16

    J. B. Stothers, Carbon-13 NMR Spectroscopy. New York: Academic Press. 1972.

  16. 17

    H. Görner undD. Schulte-Frohlinde, J. Phys. Chem.82, 2653 (1978).

Download references

Author information

Additional information

34. Mitteilung:J. Bitter, J. Leitich, H. Partale, O. E. Polansky, W. Riemer, U, Ritter-Thomas, B. Schlamann undB. Stilkerieg, Chem. Ber., im Druck.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Görner, H., Leitich, J., Polansky, O.E. et al. Die Photoenolisierung, Autoxidation und Dimerisation von 2-Isobutyliden-1,3-indandion. Monatshefte für Chemie 111, 309–329 (1980). https://doi.org/10.1007/BF00938736

Download citation


  • 2-Alkylidene-1,3-indandiones
  • Autoxidation
  • 1-Hydroxy-2-vinylinden-3-ones
  • Photoenolisation
  • 2-Vinyl-1,3-indandion-2-yl radicals