Advertisement

Experientia

, Volume 10, Issue 3, pp 81–90 | Cite as

The constitutions of cevine and some related alkaloids

  • D. H. R. Barton
  • O. Jeger
  • V. Prelog
  • R. B. Woodward
Article

Keywords

Alkaloid Related Alkaloid Cevadin 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Zusammenfassung

Die sauerstoffreichen Veratrum-Alkaloide gewinnen in letzter Zeit als blutdrucksenkende Arzneimittel immer mehr an Bedeutung. Darüber hinaus erwecken sie ein grosses Interesse vom Standpunkt des organischen Chemikers, da sie zu den kompliziertest gebauten niedrig molekularen Naturstoffen gehören.

Bei der Konstitutionsaufklärung des Alkamins Cevin (XXXII), das eine Schlüsselstellung in dieser Reihe einnimmt, wurden unter anderem die folgenden neuen Ergebnisse erhalten:
  1. a)

    Die Konstitution zweier Abbauprodukte des Cevins — der Decevinsäure (XIII) und der « Hexan-tetracarbonsäure » (XVIII) — konnte bestimmt werden.

     
  2. b)

    Das sogenannte Anhydrocevin wurde als ein Orthoazetat XLII erkannt.

     
  3. c)

    Das Cevadin [XLI,R=CH3CH=C(CH3)CO], aus dem das Cevin durch alkalische Hydrolyse entsteht, gab bei milder Oxydation mit Chromsäure durch spontane Zyklisation des entstandenen Zwischenproduktes XLVII ein 7-Oxy-hydrindanon-(1)-Derivat (XLVI).

     

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

Literatur

  1. 4.
    T. A. Henry,The Plant Alkaloids, 4th ed. (J. & A. Churchill, London, 1949), p.700.Google Scholar
  2. 4a.
    L. F. Fieser andM. Fieser,Natural Products Related to Phenanthrene, 3rd ed. (Reinhold Publishing Corp., New York, 1949), p. 600.Google Scholar
  3. 4b.
    V. Prelog andO. Jeger,Solanum and Veratrum Alkaloids in “The Alkaloids, Chemistry and Physiology”, edited byR. H. F. Manske andH. L. Holmes, Vol. III (Academic Press Inc., New York, 1953), p. 270.Google Scholar
  4. 4c.
    J. McKenna, Quart. Rev.7, 231 (1953).CrossRefGoogle Scholar
  5. 1(a).
    W. A. Jacobs andS. W. Pelletier, J. Org. Chem.18, 765 (1953).CrossRefGoogle Scholar
  6. 2.
    T. A. Henry,The Plant Alkaloids, 4th ed. (J. & A. Churchill, London, 1949), p. 700.Google Scholar
  7. 2a.
    L. F. Fieser andM. Fieser,Natural Products Related to Phenanthrene, 3rd ed. (Reinhold Publishing Corp., New York, 1949), p. 600.Google Scholar
  8. 2b.
    V. Prelog andO. Jeger,Solanum and Veratrum Alkaloids in “The Alkaloids Chemistry and Physiology”, edited byR. H. F. Manske andH. L. Holmes, Vol. III (Academic Press Inc., New York, 1953), p. 270.Google Scholar
  9. 2c.
    J. McKenna, Quart. Rev.7, 231 (1953).CrossRefGoogle Scholar
  10. 3.
    S. M. Kupchan, D. Lavie, C. V. Deliwala, andB. Y. A. Andoh, J. Amer. Chem. Soc.75, 5519 (1953).CrossRefGoogle Scholar
  11. 1.
    L. C. Craig andW. A. Jacobs, J. Amer. Chem. Soc.61, 2252 (1939); J. Biol. Chem.134, 123 (1940);141, 253 (1941).CrossRefGoogle Scholar
  12. 2a).
    L. C. Craig andW. A. Jacobs, J. Biol. Chem.141, 253 (1941).Google Scholar
  13. 1.
    N. Bland andJ. F. Thorpe, J. Chem. Soc.101, 856 (1912).Google Scholar
  14. 1a.
    Cf. alsoH. Schmid andW. Bencze, Helv. chim. Acta36, 1468 (1953).CrossRefGoogle Scholar
  15. 1.
    F. Gautschi, O. Jeger, V. Prelog, andR. B. Woodward, Helv. chim. Acta37 (1954), in preparation. — In this chart the stereochemistry of the compounds concerned is not indicated.Google Scholar
  16. 1.
    F. Gautschi, O. Jeger, V. Prelog, andR. B. Woodward, Helv. chim. Acta37 (1954), in preparation.Google Scholar
  17. 2b).
    L. C. Craig andW. A. Jacobs, J. Biol. Chem.141, 253 (1941).Google Scholar
  18. 3.
    C. F. Huebner andW. A. Jacohs, J. Biol. Chem.170, 181 (1947).Google Scholar
  19. 3a.
    L. F. Fikser andM. Fieser,Natural Products Related to Phenanthrene, 3rd ed. (Reinhold Publishing Corp., New York, 1949), p. 606.Google Scholar
  20. 3b.
    W. Y. Huang, H. L. Holmes, andL. F. Fieser, J. Amer. Chem. Soc.74, 5920 (1952).CrossRefGoogle Scholar
  21. 4.
    Cf. N. Elming, Ch. Vogel, O. Jeger, andV. Prelog, Helv. chim. Acta35, 2541 (1952);36, 2022 (1953).CrossRefGoogle Scholar
  22. 1.
    O. Jeger, R. Mirza V. Prelog, Ch. Vogel, andR. B. Woodward, Helv. chim. Acta37 (1954), in preparation.Google Scholar
  23. 3.
    Cf. G. Stork undW. Burgsthaler, J. Amer. Chem. Soc.75, 3544 (1951) and alsoJ. Kalvoda, D. Arigoni, andO. Jeger, Helv. chim. Acta37 (1954), in preparation.CrossRefGoogle Scholar
  24. 4.
    D. K. Banerjee, J. Ind. Chem. Soc.17, 424 (1940).Google Scholar
  25. 1(b).
    W. A. Jacobs andS. W. Pelletier, J. Org. Chem.18, 765 (1953).CrossRefGoogle Scholar
  26. 1.
    D. H. R. Barton andJ. F. Eastham, J. Chem. Soc.1953, 424.Google Scholar
  27. 2.
    D. H. R. Barton andC. J. W. Brooks, Chem. Ind.1953, 1366.Google Scholar
  28. 2a.
    D. H. R. Barton, C. J. W. Brooks, andJ. S. Fawcett, J. Chem. Soc.1954, in press.Google Scholar
  29. 3.
    Cf. N. J. Leonard andM. A. Rebenstorf, J. Amer. Chem. Soc.67, 49 (1945).CrossRefGoogle Scholar
  30. 4.
    D. H. R. Barton, C. J. W. Brooks, andJ. S. Fawcett, J. Chem. Soc.1954, in press.Google Scholar
  31. 4a.
    V. Prelog andA. Kathriner, Helv. chim. Acta31, 505 (1948).CrossRefGoogle Scholar
  32. 1.
    D. H. R. Barton, C. J. W. Brooks, andJ. S. Fawcett, J. Chem. Soc.1954, in press.Google Scholar
  33. 2.
    D. H. R. Barton, C. J. W. Brooks, andP. de Mayo, J. Chem. Soc., in preparation.Google Scholar
  34. 3.
    W. A. Jacobs andL. C. Craig, J. Biol. Chem.120, 447 (1937).Google Scholar
  35. 1(c).
    W. A. Jacobs, L. C. Craig, andG. I. Lavin, J. Biol. Chem.141, 51 (1941).Google Scholar
  36. 3.
    Cf. O. Wintersteiner andM. Moore, J. Amer. Chem. Soc.72, 1923 (1950). It is further worthy of note, in connection with the very ready cleavage of the C.12–C.14 glycol system, thatcis cyclopentane-1,2-diol is cleaved by lead tetraacetate more then 8000 times as fast ascis cyclohexane-1,2 diol [R. Criegee, L. Kraft, andB. Rank, Lieb. Ann.507, 159 (1933), andR. Criegee, E. Büchner, andW. Walter, Ber.73, 571 (1940)].CrossRefGoogle Scholar
  37. 4.
    D. H. R. Barton andJ. F. Eastham, J. Chem. Soc.1953, 424.Google Scholar
  38. 1.
    S. M. Kupchan, D. Lavie, C. V. Deliwala, andB.Y.A. Andoh, J. Amer. Chem. Soc.75, 5519 (1953).CrossRefGoogle Scholar
  39. 2a).
    T. A. Henry,The Plant Alkaloids, 4th ed. (J. & A. Churchill, London, 1949), p. 700.Google Scholar
  40. 2b).
    L. F. Fieser andM. Fieser,Natural Products Related to Phenanthrene, 3rd ed. (Reinhold Publishing Corp., New York, 1949), p. 600.Google Scholar
  41. 2b).
    V. Prelog andO. Jeger,Solanum and Veratrum Alkaloids in “The Alkaloids, Chemistry and Physiology”, edited byR. H. F. Manske andH. L. Holmes, Vol. III (Academic Press Inc., New York, 1953), p. 270.Google Scholar
  42. 2d).
    J. McKenna, Quart. Rev.7, 231 (1953).CrossRefGoogle Scholar
  43. 3a.
    S. M. Kupchan, D. Lavie, C. V. Deliwala, andB. Y. A. Andoh, J. Amer. Chem. Soc.75, 5519 (1953).CrossRefGoogle Scholar
  44. 3a.
    S. W. Pelletier andW. A. Jacobs, J. Amer. Chem. Soc.75, 3248 (1953).CrossRefGoogle Scholar
  45. 4.
    A. Stoll andE. Seebeck, Helv. chim. Acta35, 1270 (1952)CrossRefGoogle Scholar
  46. 2.
    D. H. R. Barton andC. J. W. Brooks, Chem. Ind.1953, 1366.Google Scholar
  47. 2a.
    D. H. R. Barton, C. J. W. Brooks, andJ. S. Fawcett, J. Chem. Soc.1954, in press.Google Scholar
  48. 1.
    H. Auterhoff, Arch. Pharm.286, 319 (1953).Google Scholar
  49. 1a.
    E. Sundt, O. Jeger, andV. Prelog, Chem. Ind.1953, 1365.Google Scholar
  50. 1b.
    A. Stoll, D. Stauffacher, andE. Seebeck, Helv. chim. Acta36, 2027 (1953).CrossRefGoogle Scholar
  51. 2.
    S. M. Kupchan andD. Lavie, J. Amer. Chem. Soc.76, 314 (1954).CrossRefGoogle Scholar
  52. 3.
    D. H. R. Barton andJ. F. Eastham, J. Chem. Soc.1953, 424,Google Scholar
  53. 4.
    D. H. R. Barton, C. J. W. Brooks, andP. de Mayo, J. Chem. Soc., in preparation.Google Scholar
  54. 5.
    A. Stoll andE. Seebeck, Helv. chim. Acta35, 1270 (1952);36, 189 (1953).CrossRefGoogle Scholar
  55. 6.
    A. Stoll andE. Seebeck, Helv. chim. Acta35, 1943 (1952).Google Scholar
  56. 7.
    D. H. R. Barton, C. J. W. Brooks, andJ. S. Fawcett, J. Chem. Soc.1954, in press.Google Scholar
  57. 7a.
    D. H. R. Barton, C. J. W. Brooks, andP. de Mayo, J. Chem. Soc.1954, in preparation.Google Scholar
  58. 2.
    D. H. R. Barton, C. J. W. Brooks, andP. de Mayo, J. Chem. Soc., in preparation.Google Scholar
  59. 3.
    M. V. Mijović, E. Sundt, E. Kyburz, O. Jeger, andV. Prelog, Helv. chim. Acta37 (1954), in preparation.Google Scholar
  60. 1.
    Cf. W. Kuhn andH. Schinz, Helv. chim. Acta36, 161 (1953).CrossRefGoogle Scholar
  61. 2c).
    L. C. Craig andW. A. Jacobs, J. Biol. Chem.139, 263 (1941).Google Scholar
  62. 3.
    T. A. Henry,The Plant Alkaloids, 4th ed. (J. & A. Churchill, London, 1949), p. 700.Google Scholar
  63. 3a.
    L. F. Fieser andM. Fieser,Natural Products Related to Phenanthrene, 3rd ed. (Reinhold Publishing Corp., New York, 1949), p. 600.Google Scholar
  64. 3b.
    V. Prelog andO. Jeger,Solanum and Veratrum Alkaloids in “The Alkaloids, Chemistry and Physiology” edited byR. H. F. Manske andH. L. Holmes, Vol. III (Academic Press Inc., New York, 1953), p. 270.Google Scholar
  65. 3c.
    J. McKenna, Quart. Rev.7, 231 (1953).CrossRefGoogle Scholar
  66. 4.
    S. M. Kupchan, M. Fieser, C. R. Narayanan, L. F. Fieser, andJ. Fried, J. Amer. Chem. Soc.76 (1954), in press.Google Scholar
  67. 1.
    S. M. Kupchan, M. Fieser, C. R. Narayanan, L. F. Fieser, andJ. Fried, J. Amer. Chem. Soc.76 (1954), in press.Google Scholar
  68. 2d).
    L. C. Craig andW. A. Jacobs, J. Biol. Chem.148, 57 (1943).Google Scholar
  69. 3.
    Cf. the differential ease of elimination of glycolic acid from strychninolic and dihydrostrychninonic acids:H. L. Holmes inThe Alkaloids, Chemistry and Physiology, edited byR. H. F. Manske andH. L. Holmes, Vol. II (Academic Press Inc., New York, 1952), p. 517.Google Scholar
  70. 4.
    T. A. Henry,The Plant Alkaloids, 4th ed. (J. & A. Churchill, London, 1949), p. 709.Google Scholar
  71. 4a.
    L. F. Fieser andM. Fieser,Natural Products Related to Phenanthrene, 3rd ed. (Reinhold Publishing Corp., New York, 1949), p. 607.Google Scholar
  72. 4(b).
    V. Prelog andO. Jeger,Solanum and Veratrum Alkaloids in “The Alkaloids, Chemistry and Physiology”, edited byR. H. F. Manske andH. L. Holmes, Vol. III (Academic Press Inc., New York, 1953), p. 308.Google Scholar
  73. 4e).
    J. McKenna, Quart. Rev.7, 231 (1953).CrossRefGoogle Scholar

Copyright information

© Verlag Birkhäuser AG 1954

Authors and Affiliations

  • D. H. R. Barton
    • 1
  • O. Jeger
    • 2
  • V. Prelog
    • 2
  • R. B. Woodward
    • 3
  1. 1.Birkbeck CollegeUniversity of LondonUK
  2. 2.Organisch-chemisches LaboratoriumEidg. Technische HochschuleZürich
  3. 3.Converse Memorial LaboratoryHarvard UniversityCambridgeU.S.A.

Personalised recommendations