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

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.

References

  1. 1.

    van der Rest, G.; Mourgues, P.; Nedev, H.; Audier, H.E. J. Am. Soc. Mass Spectrom. 2000, 11, 705–710.

    Article  Google Scholar 

  2. 2.(a)

    Terlouw, J. K.; Heerma, W.; Burgers, P. C.; Holmes, J. L. Can. J. Chem. 1984, 62, 289.

    Article  CAS  Google 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.

    Article  CAS  Google Scholar 

  4. 3.

    van der Rest, G.; Mourgues, P.; Nedev, H.; Audier, H. E. J. Am. Chem. Soc. 2002, 124, 5561–5569.

    Article  Google Scholar 

  5. 4.

    Martrenchard, S.; Dedonder-Lardeux, C.; Jouvet, C.; Rockland, U.; Solgadi, D. J. Phys. Chem. 1995, 99, 13716.

    Article  Google Scholar 

  6. 5.

    Freriks, I. L.; de Koning, L. J.; Nibbering, N. M. M. J. Org. Chem. 1992, 57, 5976.

    Article  CAS  Google Scholar 

  7. 6.(a)

    Brutschy, B. J. Phys. Chem. 1990, 94, 8637.

    Article  CAS  Google Scholar 

  8. 6.(b)

    Brutschy, B.; Eggert, J.; James, C.; Baumgärtel, H. J. Phys. Chem. 1991, 95, 5041,

    Article  CAS  Google Scholar 

  9. 6.(c)

    Riehn, C.; Lahmann, C.; Brutschy, B. J. Phys. Chem. 1992, 96, 3626.

    Article  CAS  Google Scholar 

  10. 7.

    Troude, V.; van der Rest, G.; Mourgues, P.; Audier, H. E. J. Am. Chem. Soc. 1997, 119, 9287.

    Article  CAS  Google Scholar 

  11. 8.

    Tu, Y.; Holmes, J. L. J. Am. Chem. Soc. 2000, 122, 3695.

    Article  CAS  Google Scholar 

  12. 9.

    de Visser, S. P.; de Koning, L. J.; Nibbering, N. M. M. J. Am. Chem. Soc. 1998, 120, 1517.

    Article  Google Scholar 

  13. 10.

    van der Rest, G.; Jensen, L. B.; Mourgues, P.; Audier, H., unpublished

  14. 11.

    Kofel, P.; Allemann, M.; Kellerhals, H. P.; Wanczek, K. P. Int. J. Mass Spectrom. Ion Processes 1985, 65, 97.

    Article  CAS  Google Scholar 

  15. 12.

    Caravatti, P.; Allemann, M. Org. Mass Spectrom. 1991, 26, 514.

    Article  CAS  Google Scholar 

  16. 13.

    Sievers, H. L.; Grützmacher, H. F.; Caravatti, P. Int. J. Mass Spectrom. Ion Processes 1996, 157/158, 283.

    Article  Google 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, 235–241

    Article  Google Scholar 

  19. 16.

    Hunter, E.; Lias, S. G. J. Chem. Phys. Ref. Data 1998, 27, 413.

    Article  CAS  Google Scholar 

  20. 17.

    Audier, H. E.; McMahon, T. B. J. Am. Chem. Soc. 1994, 116, 8294–8299.

    Article  CAS  Google Scholar 

  21. 18.

    Bouchoux, G. Mass Spectrom Rev. 1988, 7; 1–39;

    Article  CAS  Google Scholar 

  22. 18.(a)

    ibid 203–255.

    Article  CAS  Google Scholar 

  23. 19.

    van der Rest, G.; Jensen, L. B.; Mourgues, P.; Audier, H. E., unpublished

  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.

    Article  Google 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 

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Correspondence to G. van der Rest.

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This work is dedicated to Fred W. McLafferty, who brought to all of us so much in our field, and it is not over!

Published online June 15, 2004

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van der Rest, G., Jensen, L.B., Azeim, S.A. et al. Reactions of [NH 3 , H2O] with carbonyl compounds: A McLafferty rearrangement within a complex?. J Am Soc Mass Spectrom 15, 966–971 (2004). https://doi.org/10.1016/j.jasms.2004.05.001

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Keywords

  • Enol
  • Carbonyl Compound
  • Isobutene
  • Collision Induce Dissociation
  • Neutral Reactant