Abstract
A series of cyclic acetals, the 2-phenyl-l,3 dioxolanes, and their deuterated analogues were studied by electron ionization (EI), chemical ionization (CI), and fast-atom bombardment (FAB) mass spectrometry to gain insight into the primary ionization processes for these compounds in FAB/liquid secondary ion mass spectrometry. Comparison of EI and CI data with that of FAB led to the conclusion that the predominant [M - H]+ ion observed in FAB for the nondeuterated cyclic acetals cannot to a large extent be rationalized in thermodynamic terms by known gas-phase ion-molecule reactions. Instead, a condensed-phase model in which the multicharged transition state for hydride abstraction is better solvated than the transition state for proton transfer appears to be a plausible explanation for the FAB data obtained for the nonlabeled cyclic acetals; however, this explanation is not entirely sufficient to rationalize the FAB data for the deuterated cyclic acetals. For these compounds, a dramatic time dependence of protonation versus hydride abstraction is observed that suggests that beam-induced reactive species are responsible for hydride abstraction in the condensed phase. This time dependence can be interpreted in terms of a buildup of highly reactive beam-induced species in the bulk of solution. Comparison of the results obtained for deuterated acetals with different surface activities support this hypothesis. (J Am Sot Mass
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Barber, M.; Bordoli, R. S.; Sedgwick, R. D.; Tyler, A. N. J Chem. Soc. Chew. Commun. 1981, 325–327.
Barber, M.; Bordoli, R. S.; Elliot, G. I.; Sedgwick, R. D.; Tyler, A. N. Anal. Chem. 1982, 54, 645A-657A.
Wong, S. S.; Röllgen, F. W. Nucl. Instrurn. Methods 1986, B14, 436–447.
Sunner, J.; Ikonomou, M. G.; Kebarle, P. Int. J Mass Spectum. Ion Processes 1988, 82, 221–237.
Ligon, W. V.; Dorn, S. B. Int. 1. Mass Spectrom. Ion Processes 1986, 78, 99–113.
De Pauw, E. Adv. Mass Spectrom 1988, 12, 383–348.
Benninghoven, A. Int. I. Mass Spectrom. Ion Phys. 1983, 53, 85–99.
Todd, P. J. Org. Mass Spectrom. 1988, 23, 419–424.
Todd, P. J. J. Am. Soc. Mass Spectrom. 1991, 2, 33–44.
Barber, M.; Bordoli, R. S.; Sedgwick, R. D.; Tetler, L. W. Org. Mass Spectrom. 1981. 16, 256–260.
Cooks, R. G.; Busch, K. L. Int. l. Mass Spectrom. Ion Phys. 1983, 53, 11l-124.
Perreault, H.; Bertrand, M. J. Proceedings of the 36th ASMS Conference on Mass Spectrometry and Allied Topics; San Francisco, CA, 1988; p 61.
Sunner, J. A.; Kalutunga, R.; Kebarle, P. Anal. Chem. 1986, 58, 1312–1316.
Sunner, J.; Morales, A.; Kebarle, P. Anal. Chem. 1987, 59, 1378–1383.
Schroder, E.; Munster, H.; Budzikiewicz, H. Org. Mass Spectrom. 1986, 21, 707–715.
Munster, H.; Theobald, F.; Budzikiewicz, H.; Schroder, E. Int. J. Mass Spectrom. Ion Processes 1987, 79, 73–79.
Huang, Q.-W.; Wu, G.-L; Tang, H.-T, Int. J_ Mass Spectrom. Ion Processes 1986, 70, 145–152.
Banditelli, G.; Bandini, A. L.; Pacchioni, G.; Minghetti, G.; Seraglia, R.; Traldi, P. Org. Mass Spectrom. 1991, 26, 945–950.
Shiea, J.; Sunner, J. Int. J. Mass Spectrom. Ion Processes 1991, 109, 265–278.
Johnstone, R. A. W.; Lewis, I. A. S.; Rose, M. E. Tetrahedron 1983, 39, 1597–1603.
Bonas, G.; Bosso, C; Vignon, M. R. Rapid Commun. Mass Spectrom. 1988, 2, 88–89.
De Pauw, E. Anal. Chem. 1983, 55, 2195–2196.
Didonato, G. C.; Busch, K. L. Anal. Chim. Acta 1985, 171, 233–239.
Bartmess, J. E.; Phillips, L. R. Anal. Chem. 1987, 59, 20X-2014.
Caprioli, R. M. Anal. Chem. 1983, 55, 2387–2391.
Connolly, M. J.; Orth, R. G. Anal. Chem. 1987, 59, 903–908.
Sbiea, J.; Sunner, J. Org. Mass Spectrom. 1991, 26, 38–44.
Clayton, E.; Wakefield, A. J. C. J. Chem. Soc. Chem. Commun. 1984, 969–970.
Duffin, K. L.; Busch, K. L. Proceedings of the 36th ASMS Conference on Mass Spectrometry and Allied Topics; San Francisco, CA, 1988; p 765.
Takayama, M.; Fukai, T.; Nomura, T.; Nojima, K. Rapid Commun. Mass Spectrom. 1989, 3,4–66.
Rosen, R. T.: Hartman, T. G.; Rosen, J. D.; Ho, C.-T. Rapid Commun. Mass Spectvonr. 1988, 2,23–233.
Curcuruto, O.; Traldi, P.; Moneti, G.; Corda, L.; Podda, G. Org. Mass Spertrom. 1991, 26, 713–717.
Takayama, M.; Fukai, T.; Nomura, T.; Nojima, K. Int. J. Mass Spectrom. Ion Processes 1990, 96, 169–179.
Paul, G. J. C.; Bourg, S.; Bertrand, M. J. Rapid Commun. Mass Spectrom. 1992, 6, 85–88.
Zha, Q.; Bailey, M. D.; Bertrand, M. J. Can J. Appl. Spectros. 1990, 35, 141–148.
Kiremire, B. T.; Chiarello, D.; Traldi, P.; Bravo, P.; Resnati, G. Rapid Commun. Mass Specfvom. 1991, 5, 591–595.
Baldwin, M. A.; Welham, K. J.; Toth, I.; Gibbons, W. A. Org-Mass Spectrom. 1988, 23, 697–699.
Johnson, W. S.; Rogier, E. R.; Szmuszkovicz, J.; Hadler, H. I.; Ackerman, J.; Bhattacharyya, B. K.: Bloom, B. M.; Stalmann, L.; Clement, R. A.; Bannister, B.; Wynberg, H. J. Am. Chem. Soc. 1956, 78, 6289–6302.
Gross, M. L.; Chess, E. K.; Lyon, P. A.; Crow, F. W.; Evans, S.; Tudge, H. lnt. J. Mass Spectrom. Iot Phys. 1982, 42, 243–254.
Marshall, J. T. B.; Williams, D. H. Tetrahedron 1967, 23, 321–333.
Sanders, R. A. Anal. Chem. 1983, 55, 1194–1197.
Konopski, L.; Maslosz, J. Org. Mass Spectrom. 1988, 23, 692–696.
Pihlaja, K.; Kuosmanen, P.; Vainiotalo, P. Org. Mass Spectrom. 1988, 23, 70–776.
Bertrand, M.; Beynon, J. H.; Cooks, R. G. Int. J. Mass Spectrom. Ion Phys. 1972, 9, 346–350.
Harrison, A. G. Chemical Ionizatian Mass Spectromety, CRC Press: Boca Raton, FL, 1983.
Kralj, B.; Kramer, V.; Vrscaj, V. lnt. J. Mass Spectrom. Jon Phys. 1983, 46, 399–402.
Bojcsen, G.; Moller, J. Int. J. Mass Spectrom. Ion Processes 1986, 68, 239–248.
Renner, D.; Spitcller, G. Biomed. Mass Spectrom. 1986, 13, 401–404.
Dillow, G. W.; Kebarle, P. J. Am. Chem. Soc. 1988, 170, 4877–4882.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Paul, G.J.C., Bourg, S. & Bertrand, M.J. Fast-atom bombardment of the cyclic acetals: Evidence indicating the predominant involvement of condensed-phase processes in ionization. J Am Soc Mass Spectrom 4, 493–503 (1993). https://doi.org/10.1016/1044-0305(93)80007-L
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1016/1044-0305(93)80007-L