Abstract
The ion-molecule reactions of ions from acetone, dimethyl ether, 2-methoxyethanol, and vinyl methyl ether with vincamine were investigated. Reactions with dimethyl ether result in [M+13]+ and [M+45]+ products, reactions with 2-methoxyethanol produce [M+13]+ and [M+89]+ ions, and reactions with acetone or vinyl methyl ether ions generate predominantly [M+43]+ ions. Collision-activated dissociation and deuterium labeling experiments allowed speculation about the product structures and mechanisms of dissociation. The methylene substitution process was shown to occur at the hydroxyl oxygen and the phenyl ring of vincamine for dimethyl ether reactions, but the methylene substitution process was not favored at the hydroxyl oxygen for the 2-methoxyethanol reactions, instead favored at the 12 phenyl position. The reaction site is likely different for the 2-methoxyethanol ion due to its capability for secondary hydrogen-bonding interactions. For the [M+45]+ and [M+89]+ ions, evidence suggests that charge-remote fragmentation processes occur from these products. In general, the use of dimethyl ether ions or 2-methoxyethanol ions for ionmolecule reactions prove highly diagnostic for the characterization of vincamine; both molecular weight and structural information are obtained. Limits of detection for vincamine with dimethyl ether chemical ionization via this technique on a benchtop ion trap gas chromatography-tandem mass spectrometer are in the upper parts per trillion range.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Lounasmaa, M.; Tolvanen, A. In The Alkaloids, Vol. 42; Cordell, G. A., Ed.; Academic Press: New York, 1992; pp 1–116.
Dubruc, C.; Caqueret, H.; Bianchetti, G. J. Chromatogr. 1981, 204, 335–339.
Szepesi, G.; Gazdag, M. J. Chromatogr. 1981, 204, 341–348.
Pietta, P.; Rava, A.; Catenacci, E. J. Chromatogr. 1981, 210, 149–153.
Perera, P.; Van Beek T. A.; Verpoorte, R. J. Chromatogr. 1984, 285, 214–220.
Van Der Heijden, R.; Lamping, P. J.; Out, P. P.; Wijnsma, R.; Verpoorte, R. J. Chromatogr. 1987, 396, 287–295.
Bo, L. D.; Ceriani, G.; Broccali, F. J. Chromatogr. Biomed. Appl. 1992, 573, 158–162.
Hill, D. W.; Kind, A. J. J. Liquid Chromatogr. 1993, 16, 3941–3964.
Smyth, M. R. Analyst 1986, 111, 851–852.
Auriola, S.; Naaranlahti, T.; Kostiainen, R.; Lapinjoki, S. P. Biomed. and Environ. Mass Spectrom. 1990, 19, 609–612.
Bressolle, F.; Bres, J.; Brun, S. J. Chromatogr. 1979, 174, 421–433.
Lee, Y.-W.; Voyksner, R. D.; Fang, Q.-C.; Cook, C.-E.; Ito, C. E. J. Liquid Chromatogr. 1988, 11, 153–171.
Hoppen, H.-O.; Heuer, R.; Seidel, G. Biomed. Mass Spectrom. 1978, 5, 133–135.
Gazdag, M.; Mihályfi, K.; Szepesi, G. Fresenius’ Z. Anal. Chem. 1981, 309, 105–108.
Kinsun, H.; Moulin, M. A. J. Chromatogr. 1977, 144, 123–126.
Michotte, Y.; Massart, D. L. J. Chromatogr., Biomed. Appl. 1985, 344, 367–371.
Budzikiewicz, H.; Djerassi, C.; Williams, D. H. Structure Elucidation of Natural Products by Mass Spectrometry, Vol. 1: The Alkaloids; Holden-Day: San Francisco, CA 1964; pp 60–76.
Czira, G.; Tamás, J.; Kalaus, G. Org. Mass Spectrom. 1984, 19, 555–562.
Kovácik, V.; Kompis, I. Collect. Czech. Chem. Commun. 1969, 34, 2809–2818.
Vairamani, M.; Mirza, U. A.; Srinivas, R. Mass Spectrom. Rev. 1990, 9, 235–258.
Alvarez, E. J.; Brodbelt, J. S. J. Mass Spectrom. 1995, 30, 625–631.
Wang, S.; Sah, Y.; Xu, S.; Pan, J. Anal. Chem. 1985, 57, 2283–2286.
Eberlin, M. N.; Majumdar, T. K.; Cooks, R. G. J. Am. Chem. Soc. 1992, 114, 2884–2896.
van Doorn, R.; Nibbering, N. M. M. Org. Mass Spectrom. 1978, 13, 527–534.
Brodbelt, J.; Liou, C.-C Donovan, T. Anal. Chem. 1991, 63, 1205–1209.
Donovan, T.; Liou, C.-C.; Brodbelt, J. J. Am. Soc. Mass Spectrom. 1992, 3, 39–46.
Keough, T. Anal. Chem. 1982, 54, 2540–25467.
Ferrer-Correia, A. J. V.; Jennings, K. R.; Sen Sharma, D. K. Org. Mass Spectrom. 1976, 11, 867–872.
Chai, R.; Harrison, A. G. Anal. Chem. 1981, 53, 34–37.
Ghaderi, S.; Kilkarni, P. S.; Ledford, E. B., Jr.; Wilkins, C. L.; Gross, M. L. Anal. Chem. 1981, 53, 428–437.
Eichmann, E. S.; Brodbelt, J. S. J. Am. Soc. Mass Spectrom. 1993, 4, 230–241.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Bauerle, G.F., Hall, B.J., Tran, N.V. et al. Ion-molecule reactions of oxygenated chemical ionization reagents with vincamine. J Am Soc Mass Spectrom 7, 250–260 (1996). https://doi.org/10.1016/1044-0305(95)00650-8
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1016/1044-0305(95)00650-8