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The labile stereochemistry of conjugated systems

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Zusammenfassung

Die Faktoren, welche die labile Stereochemie von konjugierten Systemen beeinflussen, werden diskutiert. Das Studium der Elektronenspektren solcher Systeme zeigt, dass in vielen Fällen Moleküle, welche in vorwiegend unebenen (nichtplanaren) Grundzuständen existieren, in vorwiegend ebene (planare) erregte Zustände übergehen. Die Gleichgewichtskonstellationen werden abgeleitet für Biphenylderivate, Arylketone, Styrole, Arylamine, Cyclohexenderivate und cyclische und acyclische Diene.

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References

  1. 1

    J. Dhar, Proc. Nat. Inst. Sci. India15, 11 (1949).

  2. 2

    O. Bastiansen, Acta Chem. Scand.3, 408 (1949).

  3. 3

    SeeR. Adams andH. C. Yuan, Chem. Reviews12, 261 (1933).

  4. 1

    L. W. Pickett, G. F. Walter, andH. France, J. Amer. Chem. Soc.58, 2296 (1936).

  5. 1a

    SeeE. A. Braude andE. S. Waight in “Progress in Stereochemistry” (W. Klyne, Ed.), Vol. 1., Chapter 4 (Butterworths, London 1954), for a summary of data and literature references.

  6. 1b

    E. A. Braude, F. Sondheimer, andW. F. Forbes, Nature173, 117 (1954), and forthcoming papers in J. Chem. Soc.

  7. 1

    E. A. Braude, F. Sondheimer, andW. F. Forbes, Nature173, 117 (1954), and forthcoming papers in J. Chem. Soc.

  8. 1

    Unless otherwise stated, the data in this and the following tables are taken fromE. A. Braude andE. S. Waight, “Progress in Stereochemistry” (W. Klyne, Ed.), Vol. 1., Chapter 4 (Butterworths, London, 1954), andE. A. Braude, F. Sondheimer, andW. F. Forbes, Nature173, 117 (1954), and forthcoming papers in J. Chem. Soc.

  9. 1c

    E. A. Braude andE. S. Waight, “Progress in Stereochemistry” (W. Klyne, Ed.). Vol. 1., Chapter 4 (Butterworths, London 1954), andE. A. Braude, F. Sondheimer, andW. F. Forbes, Nature173, 117 (1954) used a cosΘ function. The cos2 Θ function is more satisfactory because it has the value 1 forΘ=0 and 180°, as well as from other theoretical considerations.

  10. 2

    G. H. Beaven, D. M. Hall, M. S. Lesslie, andE. E. Turner, J. Chem. Soc.1952, 854.

  11. 2a

    G. H. Beaven, D. M. Hall, M. S. Lesslie, E. E. Turner, andG. R. Bird, J. Chem. Soc.1954, 131.

  12. 2b

    D. M Hall, S. Ridgwell, andE. E. Turner, J. Chem. Soc.1954, 2498.

  13. 3

    E. A. Braude, F. Sondheimer, andW. F. Forbes, Nature173, 117 (1954), and forthcoming papers in J. Chem. Soc.

  14. 1

    M. T. O'Shaughnessy andW. H. Rodebush, J. Amer. Chem. Soc.62, 2906 (1940).

  15. 1a

    E. A. Braude, F. Sondheimer, andW. F. Forbes, Nature173, 117 (1954), and forthcoming papers in J. Chem. Soc.

  16. 2

    J. B. Bentley, K. B. Everard, R. J. B. Marsden, andL. E. Sutton, J. Chem. Soc.1949, 2957.

  17. 1

    E. A. Braude, J. S. Fawcett, andD. D. E. Newman, J. Chem. Soc.1950, 793.

  18. 2

    W. R. Remington, J. Amer. Chem. Soc.67, 1838 (1945).

  19. 2a

    H. B. Klevens andJ. R. Platt, J. Amer. Chem. Soc.71, 1714 (1949).

  20. 1

    V. Prelog andP. Wieland, Helv. Chim. Acta27, 1127 (1944).

  21. 2

    B. M. Wepster, Rec. Trav. Chim. Pays-Bas72, 662 (1953).

  22. 3

    E. A. Braude, E. R. H. Jones, H. P. Koch, R. W. Richardson, F. Sondheimer, andB. J. Toogood, J. Chem. Soc.1949, 1890.

  23. 4

    R. B. Turner andD. M. Voitle, J. Amer. Chem. Soc.73, 1403 (1951).

  24. 1

    E. A. Braude, E. R. H. Jones, H. P. Koch, R. W. Richardson, F. Sondheimer, andJ. B. Toogood, J. Chem. Soc.1949, 1890.

  25. 1a

    E. A. Braude andE. R. H. Jones, J. Amer. Chem. Soc.72, 1041 (1950).

  26. 1

    C. H. MacGillavry, A. Kreuger, andE. L. Eichhorn, Proc. Acad. Sci. Amst.B54, 449 (1951), and private communication from ProfessorMacGillavry.

  27. 2

    E. A. Braude et al., loc. cit.

  28. 3

    R. S. Mulliken, J. Chem. Physics7, 121 (1939).

  29. 4

    J. G. Aston, G. Szasz, H. W. Wooley, andF. G. Brickwedde, J. Chem. Physics14, 67 (1946).

  30. 5

    V. Schomaker andL. Pauling, J. Amer. Chem. Soc.61, 1769 (1939).

  31. 6

    K. Bradacs andL. Kahovec, Z. physikal. Chem.B48, 635 (1940).

  32. 7

    G. J. Szasz andN. Sheppard, Trans. Faraday Soc.49, 358 (1953).

  33. 1

    E. A. Braude, Chem. and Industry1954, 1557.

  34. 1a

    In a recent paper,A. T. Blomquist andA. Goldstein [J. Amer. Chem. Soc.77, 998 (1955)] have described thecis-cis-isomer ofcyclodeca-1:3-diene which showsno band in the 2150–2300 Å region, indicating that the diene system in this isomer is highly non-planar.

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Summary of a lecture delivered at the Eidgenössische Technische Hochschule, Zürich, on January 24, 1955.

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Braude, E.A. The labile stereochemistry of conjugated systems. Experientia 11, 457–464 (1955). https://doi.org/10.1007/BF02172561

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