Reactions of [NH 3 , H2O] with carbonyl compounds: A McLafferty rearrangement within a complex?

  • G. van der Rest
  • L. B. Jensen
  • S. Abdel Azeim
  • P. Mourgues
  • H. E. Audier
Focus: McLafferty Rearrangement

Abstract

The reactions of the water solvated ammonia radical cation [NH 3 ·+ , H2O] with a variety of aldehydes and ketones were investigated. The reactions observed differ from those of low energy aldehydes and ketones radical cations, although electron transfer from the keto compound to ionized ammonia is thermodynamically allowed within the terbody complexes initially formed. The main process yields an ammonia solvated enol with loss of water and an alkene. This process corresponds formally to a McLafferty fragmentation within a complex. With aldehydes, another reaction can take place, namely the transfer of the hydrogen from the CHO group to ammonia, leading to the proton bound dimer of ammonia and water, and to the NH 4 + cation. Comparison between the available experimental results leads to the conclusion that the McLafferty fragmentation occurs within the terbody complex initially formed, with no prior ligand exchange, the water molecule acting as a spectator partner.

Keywords

Enol Carbonyl Compound Isobutene Collision Induce Dissociation Neutral Reactant 
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.

References

  1. 1.
    van der Rest, G.; Mourgues, P.; Nedev, H.; Audier, H.E. J. Am. Soc. Mass Spectrom. 2000, 11, 705–710.CrossRefGoogle Scholar
  2. 2.(a)
    Terlouw, J. K.; Heerma, W.; Burgers, P. C.; Holmes, J. L. Can. J. Chem. 1984, 62, 289.CrossRefGoogle Scholar
  3. 2.(b)
    Postma, R.; van Helden, S. P.; van Lenthe, J. H.; Ruttink, P. J. A.; Terlouw, J. K.; Holmes, J. L. Org. Mass Spectrom. 1988, 23, 503.CrossRefGoogle Scholar
  4. 3.
    van der Rest, G.; Mourgues, P.; Nedev, H.; Audier, H. E. J. Am. Chem. Soc. 2002, 124, 5561–5569.CrossRefGoogle Scholar
  5. 4.
    Martrenchard, S.; Dedonder-Lardeux, C.; Jouvet, C.; Rockland, U.; Solgadi, D. J. Phys. Chem. 1995, 99, 13716.CrossRefGoogle Scholar
  6. 5.
    Freriks, I. L.; de Koning, L. J.; Nibbering, N. M. M. J. Org. Chem. 1992, 57, 5976.CrossRefGoogle Scholar
  7. 6.(a)
    Brutschy, B. J. Phys. Chem. 1990, 94, 8637.CrossRefGoogle Scholar
  8. 6.(b)
    Brutschy, B.; Eggert, J.; James, C.; Baumgärtel, H. J. Phys. Chem. 1991, 95, 5041,CrossRefGoogle Scholar
  9. 6.(c)
    Riehn, C.; Lahmann, C.; Brutschy, B. J. Phys. Chem. 1992, 96, 3626.CrossRefGoogle Scholar
  10. 7.
    Troude, V.; van der Rest, G.; Mourgues, P.; Audier, H. E. J. Am. Chem. Soc. 1997, 119, 9287.CrossRefGoogle Scholar
  11. 8.
    Tu, Y.; Holmes, J. L. J. Am. Chem. Soc. 2000, 122, 3695.CrossRefGoogle Scholar
  12. 9.
    de Visser, S. P.; de Koning, L. J.; Nibbering, N. M. M. J. Am. Chem. Soc. 1998, 120, 1517.CrossRefGoogle Scholar
  13. 10.
    van der Rest, G.; Jensen, L. B.; Mourgues, P.; Audier, H., unpublishedGoogle Scholar
  14. 11.
    Kofel, P.; Allemann, M.; Kellerhals, H. P.; Wanczek, K. P. Int. J. Mass Spectrom. Ion Processes 1985, 65, 97.CrossRefGoogle Scholar
  15. 12.
    Caravatti, P.; Allemann, M. Org. Mass Spectrom. 1991, 26, 514.CrossRefGoogle Scholar
  16. 13.
    Sievers, H. L.; Grützmacher, H. F.; Caravatti, P. Int. J. Mass Spectrom. Ion Processes 1996, 157/158, 283.CrossRefGoogle Scholar
  17. 14.
    Frisch, M. J.; Trucks, G. W.; Schegel, H. B.; Scuseria, G. E., et al. Gaussian 98, Revision A.6; Gaussian Inc.: Pittsburgh, PA, 1998.Google Scholar
  18. 15.
    Bouchoux, G.; Chamot-Rooke, J.; Leblanc, D.; Mourgues, P.; Sablier, M. ChemPhysChem. 2001, 4, 235–241CrossRefGoogle Scholar
  19. 16.
    Hunter, E.; Lias, S. G. J. Chem. Phys. Ref. Data 1998, 27, 413.CrossRefGoogle Scholar
  20. 17.
    Audier, H. E.; McMahon, T. B. J. Am. Chem. Soc. 1994, 116, 8294–8299.CrossRefGoogle Scholar
  21. 18.
    Bouchoux, G. Mass Spectrom Rev. 1988, 7; 1–39;CrossRefGoogle Scholar
  22. 18.(a)
    ibid 203–255.CrossRefGoogle Scholar
  23. 19.
    van der Rest, G.; Jensen, L. B.; Mourgues, P.; Audier, H. E., unpublishedGoogle Scholar
  24. 20.
    van der Rest, G.; Nedev, H.; Chamot-Rooke, J.; Mourgues, P.; McMahon, T. B.; Audier, H. E. Int. J. Mass Spectrom. 2000, 202, 161–174.CrossRefGoogle Scholar
  25. 21.
    McLafferty, F. W.; Turecek, F. Interpretation of Mass Spectra, 4th ed. University Science Books: Mill Valey, CA, 1993, pp 1–371.Google Scholar

Copyright information

© American Society for Mass Spectrometry 2004

Authors and Affiliations

  • G. van der Rest
    • 1
  • L. B. Jensen
    • 1
  • S. Abdel Azeim
    • 1
  • P. Mourgues
    • 1
  • H. E. Audier
    • 1
  1. 1.Laboratoire des Mécanismes Réactionnels, UMR 7651 CNRSEcole PolytechniquePalaiseau CedexFrance

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