The influence of the size and structure of a spectator alkyl group on the relative rates of alkyl radical elimination from ionised tertiary amines

European Journal of Mass Spectrometry

Volumn 5, Issue 5, 1999, Pages 339-351

  Mandeville, Simon J ^a   Bowen, Richard D ^a   Trikoupis, Moschoula A ^b   Terlouw, Johan K ^b  

^a UNIVERSITY OF BRADFORD   (United Kingdom)

^b MCMASTER UNIVERSITY   (Canada)

Author keywords

Alkyl radical loss; Competing processes; Ionised alkylamines; Metastable ions; cleavage

Indexed keywords

EID: 0008100534     PISSN: 14690667     EISSN: None     Source Type: Journal    
DOI: 10.1255/ejms.294     Document Type: Article

References (38)

1. For a modern text, see: F.W. McLafferty and F. Turecek, Interpretation of Mass Spectra, 4th Edn. University Science Books, Mill Valley, California (1993).
2. J.J. Zwinselmann, N.M.M. Nibbering, N.E. Middlemiss, J.H. Vajda and A.G. Harrison, Int. J. Mass Spectroni. Ion Phys. 38, 163 (1981).
3. S. Hammerum and P.J. Derrick, J. Chem. Soc., Chem Commun. 996 (1985).
4. R.D. Bowen and A.D. Wright, J. Chem. Soc., Chem. Commun. 1055 (1991); R.D. Bowen and A.D. Wright, J. Chem. Soc., Chem. Commun. 96 (1992); A.D. Wright and R.D. Bowen, Can. J. Chem. 71, 1073 (1993).
5. R.D. Bowen and A.D. Wright, J. Chem. Soc., Chem. Commun. 1055 (1991); R.D. Bowen and A.D. Wright, J. Chem. Soc., Chem. Commun. 96 (1992); A.D. Wright and R.D. Bowen, Can. J. Chem. 71, 1073 (1993).
6. R.D. Bowen and A.D. Wright, J. Chem. Soc., Chem. Commun. 1055 (1991); R.D. Bowen and A.D. Wright, J. Chem. Soc., Chem. Commun. 96 (1992); A.D. Wright and R.D. Bowen, Can. J. Chem. 71, 1073 (1993).
7. H.M. Rosenstock, K. Draxl, B.W. Steiner and J.T. Herron, J. Phys Chem. Ref. Data 6, Suppl. 1 (1977); S.G. Lias, J.F. Liebman and R.D. Levin, J. Phys Chem. Ref. Data 13, 695 (1984).
8. H.M. Rosenstock, K. Draxl, B.W. Steiner and J.T. Herron, J. Phys Chem. Ref. Data 6, Suppl. 1 (1977); S.G. Lias, J.F. Liebman and R.D. Levin, J. Phys Chem. Ref. Data 13, 695 (1984).
9. R.G. Cooks, J.H. Beynon, R.M. Caprioli and G.R. Lester, Metastable Ions. Elsevier, Amsterdam (1973).
10. For reviews on the applications of metastable ions in mechanistic organic chemistry, see: D.H. Williams, Acc. Chem. Res. 10, 280 (1977); D.H. Williams, Philos. Trans. R. Soc. London Ser. A 293, 117 (1977); R.D. Bowen, D.H. Williams and H. Schwarz, Angew. Chem. Int. Edn. Eng. 18, 451 (1979); R.D. Bowen and D.H. Williams, in Rearrangements in Ground and Excited States, Ed by P. DeMayo, Vol. 1. Academic Press, New York, Chap. 2 (1980).
11. For reviews on the applications of metastable ions in mechanistic organic chemistry, see: D.H. Williams, Acc. Chem. Res. 10, 280 (1977); D.H. Williams, Philos. Trans. R. Soc. London Ser. A 293, 117 (1977); R.D. Bowen, D.H. Williams and H. Schwarz, Angew. Chem. Int. Edn. Eng. 18, 451 (1979); R.D. Bowen and D.H. Williams, in Rearrangements in Ground and Excited States, Ed by P. DeMayo, Vol. 1. Academic Press, New York, Chap. 2 (1980).
12. For reviews on the applications of metastable ions in mechanistic organic chemistry, see: D.H. Williams, Acc. Chem. Res. 10, 280 (1977); D.H. Williams, Philos. Trans. R. Soc. London Ser. A 293, 117 (1977); R.D. Bowen, D.H. Williams and H. Schwarz, Angew. Chem. Int. Edn. Eng. 18, 451 (1979); R.D. Bowen and D.H. Williams, in Rearrangements in Ground and Excited States, Ed by P. DeMayo, Vol. 1. Academic Press, New York, Chap. 2 (1980).
13. For reviews on the applications of metastable ions in mechanistic organic chemistry, see: D.H. Williams, Acc. Chem. Res. 10, 280 (1977); D.H. Williams, Philos. Trans. R. Soc. London Ser. A 293, 117 (1977); R.D. Bowen, D.H. Williams and H. Schwarz, Angew. Chem. Int. Edn. Eng. 18, 451 (1979); R.D. Bowen and D.H. Williams, in Rearrangements in Ground and Excited States, Ed by P. DeMayo, Vol. 1. Academic Press, New York, Chap. 2 (1980).
14. S. Hammerum, unpublished work.
15. For a recent review of the chemistry of ionised amines, see: R.D. Bowen, in The Chemistry of Functional Groups, Supplement F2: The Chemistry of Amino, Nitro and Nitroso and Related Groups, Ed by S. Patai and Z. Rappoport. Wiley. Chapter 5, pp. 205-248 (1996).
16. T. Weiske and H. Schwarz, Chem. Ber. 116, 323 (1983); T. Weiske, H. Halim and H. Schwarz, Chem. Ber. 118, 495 (1985); T. Weiske and H. Schwarz, Tetrahedron 42, 6245 (1986).
17. T. Weiske and H. Schwarz, Chem. Ber. 116, 323 (1983); T. Weiske, H. Halim and H. Schwarz, Chem. Ber. 118, 495 (1985); T. Weiske and H. Schwarz, Tetrahedron 42, 6245 (1986).
18. T. Weiske and H. Schwarz, Chem. Ber. 116, 323 (1983); T. Weiske, H. Halim and H. Schwarz, Chem. Ber. 118, 495 (1985); T. Weiske and H. Schwarz, Tetrahedron 42, 6245 (1986).
19. R.D. Bowen, P. Clifford, J.T. Francis and J.K. Terlouw, Int. J. Mass Spectrom. Ion Processes 165/166, 155 (1997).
20. K. Fukui, Acc. Chem. Res. 4, 57 (1971).
21. I. Fleming, Frontier Orbitals and Organic Chemical Reactions. Wiley, London (1976).
22. For reviews on INCs, see: T.H. Morton, Tetrahedron 38, 3195 (1982); D.J. McAdoo, Mass Spectrom. Rev. 7, 363 (1988); S. Meyerson, Org. Mass Spectrom. 24, 267 (1989); S. Hammerum, in Fundamentals of Gas-Phase Ion Chemistry, Ed by K.R. Jennings. Kluwer, Dordrecht, p. 379 (1990); R.D. Bowen, Acc. Chem. Res. 24, 364 (1991); P. Longevialle, Mass Spectrom. Rev. 11, 157 (1992); D.J. McAdoo and T.H. Morton, Acc. Chem. Res. 26, 295 (1993).
23. For reviews on INCs, see: T.H. Morton, Tetrahedron 38, 3195 (1982); D.J. McAdoo, Mass Spectrom. Rev. 7, 363 (1988); S. Meyerson, Org. Mass Spectrom. 24, 267 (1989); S. Hammerum, in Fundamentals of Gas-Phase Ion Chemistry, Ed by K.R. Jennings. Kluwer, Dordrecht, p. 379 (1990); R.D. Bowen, Acc. Chem. Res. 24, 364 (1991); P. Longevialle, Mass Spectrom. Rev. 11, 157 (1992); D.J. McAdoo and T.H. Morton, Acc. Chem. Res. 26, 295 (1993).
24. For reviews on INCs, see: T.H. Morton, Tetrahedron 38, 3195 (1982); D.J. McAdoo, Mass Spectrom. Rev. 7, 363 (1988); S. Meyerson, Org. Mass Spectrom. 24, 267 (1989); S. Hammerum, in Fundamentals of Gas-Phase Ion Chemistry, Ed by K.R. Jennings. Kluwer, Dordrecht, p. 379 (1990); R.D. Bowen, Acc. Chem. Res. 24, 364 (1991); P. Longevialle, Mass Spectrom. Rev. 11, 157 (1992); D.J. McAdoo and T.H. Morton, Acc. Chem. Res. 26, 295 (1993).
25. For reviews on INCs, see: T.H. Morton, Tetrahedron 38, 3195 (1982); D.J. McAdoo, Mass Spectrom. Rev. 7, 363 (1988); S. Meyerson, Org. Mass Spectrom. 24, 267 (1989); S. Hammerum, in Fundamentals of Gas-Phase Ion Chemistry, Ed by K.R. Jennings. Kluwer, Dordrecht, p. 379 (1990); R.D. Bowen, Acc. Chem. Res. 24, 364 (1991); P. Longevialle, Mass Spectrom. Rev. 11, 157 (1992); D.J. McAdoo and T.H. Morton, Acc. Chem. Res. 26, 295 (1993).
26. For reviews on INCs, see: T.H. Morton, Tetrahedron 38, 3195 (1982); D.J. McAdoo, Mass Spectrom. Rev. 7, 363 (1988); S. Meyerson, Org. Mass Spectrom. 24, 267 (1989); S. Hammerum, in Fundamentals of Gas-Phase Ion Chemistry, Ed by K.R. Jennings. Kluwer, Dordrecht, p. 379 (1990); R.D. Bowen, Acc. Chem. Res. 24, 364 (1991); P. Longevialle, Mass Spectrom. Rev. 11, 157 (1992); D.J. McAdoo and T.H. Morton, Acc. Chem. Res. 26, 295 (1993).
27. For reviews on INCs, see: T.H. Morton, Tetrahedron 38, 3195 (1982); D.J. McAdoo, Mass Spectrom. Rev. 7, 363 (1988); S. Meyerson, Org. Mass Spectrom. 24, 267 (1989); S. Hammerum, in Fundamentals of Gas-Phase Ion Chemistry, Ed by K.R. Jennings. Kluwer, Dordrecht, p. 379 (1990); R.D. Bowen, Acc. Chem. Res. 24, 364 (1991); P. Longevialle, Mass Spectrom. Rev. 11, 157 (1992); D.J. McAdoo and T.H. Morton, Acc. Chem. Res. 26, 295 (1993).
28. For reviews on INCs, see: T.H. Morton, Tetrahedron 38, 3195 (1982); D.J. McAdoo, Mass Spectrom. Rev. 7, 363 (1988); S. Meyerson, Org. Mass Spectrom. 24, 267 (1989); S. Hammerum, in Fundamentals of Gas-Phase Ion Chemistry, Ed by K.R. Jennings. Kluwer, Dordrecht, p. 379 (1990); R.D. Bowen, Acc. Chem. Res. 24, 364 (1991); P. Longevialle, Mass Spectrom. Rev. 11, 157 (1992); D.J. McAdoo and T.H. Morton, Acc. Chem. Res. 26, 295 (1993).
29. The expression "critical energy" corresponds conceptually to the term "activation energy", A. Maccoll, Org. Mass Spectrom. 15, 225 (1980).
30. B.F. Yates, W.J. Bouma and L. Radom, J. Am. Chem. Soc. 106, 5805 (1984).
31. For a review of distonic ions, see: S. Hammerum, Mass Spectrom. Rev. 7, 123 (1988).
32. S. Ingemann, S. Hammerum and P.J. Derrick, J. Am. Chem. Soc. 110, 3869 (1988); S. Ingemann, S. Hammerum, P.J. Derrick, R, H. Fokkens and N.M.M. Nibbering, Org Mass Spectrom. 24, 885 (1989); S. Ingemann, E. Kluft, N.M.M. Nibbering, C.E. Alison, P.J. Derrick, and S. Hammerum, Org Mass Spectrom. 26, 875 (1991).
33. S. Ingemann, S. Hammerum and P.J. Derrick, J. Am. Chem. Soc. 110, 3869 (1988); S. Ingemann, S. Hammerum, P.J. Derrick, R, H. Fokkens and N.M.M. Nibbering, Org Mass Spectrom. 24, 885 (1989); S. Ingemann, E. Kluft, N.M.M. Nibbering, C.E. Alison, P.J. Derrick, and S. Hammerum, Org Mass Spectrom. 26, 875 (1991).
34. S. Ingemann, S. Hammerum and P.J. Derrick, J. Am. Chem. Soc. 110, 3869 (1988); S. Ingemann, S. Hammerum, P.J. Derrick, R, H. Fokkens and N.M.M. Nibbering, Org Mass Spectrom. 24, 885 (1989); S. Ingemann, E. Kluft, N.M.M. Nibbering, C.E. Alison, P.J. Derrick, and S. Hammerum, Org Mass Spectrom. 26, 875 (1991).
35. H.F. Garderen, P.J.A. Ruttink, P.C. Burgers, G.A. McGibbon and J.K. Terlouw, Int. J. Mass Spectrom. Ion Processes 121, 159 (1992).
36. K. Levsen, Fundamental Aspects of Organic Mass Spectrometry. Verlag-Chemie, Weinheim (1978).
37. M.A. Baldwin, R.P. Morgan and P.J. Derrick, Org. Mass Spectrom. 11, 440 (1976).
38. G.W. Kabalka, M. Varma, R.S. Varma, P.C. Srivastava and F.F. Knapp, J. Org. Chem. 51, 2386 (1986).