, Volume 20, Issue 10, pp 652–663 | Cite as

Mass spectra of pyrrolidides of oxy, hydroxy and trimethylsilyloxy octadecanoic acids

  • A. P. Tulloch


Pyrrolidides of 16 isomeric oxooctadecanoic acids and 17 isomeric hydroxyoctadecanoic acids and their trimethylsily (TMS) ethers have been prepared and their mass spectra measured. Comparison of spectra of all the isomers has shown the variation in amide- and substituent-directed fragmentation with position of the substitutent on the 18 carbon chain. Five diagnostic ions are present in spectra of most oxo pyrrolidides, and the most important one is formed by cleavage between the carbons α and β to the oxo group on the amide side. Mass spectra of hydroxy pyrrolidides have four diagnostic ions; the principal one in most spectra is formed by α-cleavage at the oxygenated carbon on the terminal methyl side. There are four characteristic ions in spectra of the trimethylsiloxy pyrrolidides, and the two formed by α-cleavage on one or the other side of the oxygenated carbon are the most important. Spectra of the 2-, 3- and 4-substituted isomers are considerably different from those of the other isomers. Mass spectra of pyrrolidides of three specifically deuterated oxo acids and of eight deuterated hydroxy acids and their trimethylsilyl ethers also were recorded and used to confirm the mode of formation of almost all the ions in the spectra. Two unusual hydrogen migrations, from the carbon α to the oxygenated carbon on the terminal methyl side, are involved in fragmentation of the trimethylsilyl ethers. Spectra have been compared with those of the corresponding oxygenated methyl esters.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Ryhage, R., and Stenhagen, E. (1960) Arkiv Kemi 15, 545–574.Google Scholar
  2. 2.
    Tulloch, A.P. (1980) Lipids 15, 881–888.Google Scholar
  3. 3.
    Tulloch, A.P., and Hoffman, L.L. (1973) Lipids 8, 617–622.CrossRefGoogle Scholar
  4. 4.
    Eglinton, G., Hunneman, D.H., and McCormick, A. (1968) Org. Mass Spec. 1, 593–611.CrossRefGoogle Scholar
  5. 5.
    Richter, W.J., and Burlingame, A.L. (1968) J. Chem. Soc. Chem. Commun. 1158–1160.Google Scholar
  6. 6.
    Leu, K., and Andersson, J. (1974) Lebensm.-Wiss. Technol. 7, 42–46.Google Scholar
  7. 7.
    Nicolaides, N., Soukup, V.G., and Ruth, E.C. (1983) Biomed. Mass. Spec. 10, 441–449.CrossRefGoogle Scholar
  8. 8.
    Vetter, W., Walther, W., and Vecchi, M. (1971) Helv. Chim. Acta 54, 1599–1605.CrossRefGoogle Scholar
  9. 9.
    Duffield, A.M., and Djerassi, C. (1965) J. Amer. Chem. Soc. 87, 4554–4559.CrossRefGoogle Scholar
  10. 10.
    Andersson, B.A., and Holman, R.T. (1974) Lipids 9, 185–190.PubMedGoogle Scholar
  11. 11.
    Andersson, B.A., Christie, W.W., and Holman, R.T. (1975) Lipids 10, 215–219.CrossRefGoogle Scholar
  12. 12.
    Valicenti, A.J., Heimermann, W.H., and Holman, R.T. (1979) J. Org. Chem. 44, 1068–1073.CrossRefGoogle Scholar
  13. 13.
    Andersson, B.A. (1978) Prog. Chem. Fats Other Lipids 16, 279–308.PubMedCrossRefGoogle Scholar
  14. 14.
    Andersson, B.A. (1979) in Advances in the Biochemistry and Physiology of Plant Lipids (Appelquist, L.-A., and Liljenberg, C., eds.) pp. 257–262, Elsevier/North Holland Amsterdam.Google Scholar
  15. 15.
    McLafferty, F.W. (1980) Interpretation of Mass Spectra, 3rd edn., pp. 19–21, 195–205, 223–224, University Science Books, California.Google Scholar
  16. 16.
    Eagles, J., Fenwick, G.R., and Self, R. (1979) Biomed. Mass Spec. 6, 462–464.CrossRefGoogle Scholar
  17. 17.
    Tulloch, A.P. (1964) J. Amer. Oil Chem. Soc. 41, 833–836.Google Scholar
  18. 18.
    Tulloch, A.P. (1977) Lipids 12, 92–98.PubMedCrossRefGoogle Scholar
  19. 19.
    Heinz, E., Tulloch, A.P., and Spencer, J.F.T. (1969) J. Biol. Chem. 244, 882–888.PubMedGoogle Scholar
  20. 20.
    Tulloch, A.P. (1978) Org. Mag. Reson. 11, 109–115.CrossRefGoogle Scholar
  21. 21.
    Tulloch, A.P., and Hoffman, L.L. (1976) Phytochemistry 15, 1145–1151.CrossRefGoogle Scholar
  22. 22.
    Ubik, K., Stransky, K., and Streibl, M. (1975) Coll. Czech. Chem. Commun. 40, 1718–1730.Google Scholar
  23. 23.
    Wolff, R.E., Greff, M., and McCloskey, J.A. (1968) Adv. Mass Spec. 4, 193–197.CrossRefGoogle Scholar
  24. 24.
    Diekman, J., Thomson, J.B., and Djerassi, C. (1967) J. Org. Chem. 32, 3904–3919.CrossRefGoogle Scholar
  25. 25.
    Tulloch, A.P. (1985) Chem. Phys. Lipids 37, 197–213.CrossRefGoogle Scholar
  26. 26.
    Andersson, B.A., and Holman, R.T. (1975) Lipids 10, 716–717.PubMedCrossRefGoogle Scholar

Copyright information

© American Oil Chemists’ Society 1985

Authors and Affiliations

  • A. P. Tulloch
    • 1
  1. 1.Plant Biotechnology InstituteNational Research Council of CanadaSaskatoonCanada

Personalised recommendations