Artículos de revistas
Structurally Diagnostic Ion-molecule Reactions: Acylium Ions With α-, β- And γ-hydroxy Ketones
Registro en:
Journal Of Mass Spectrometry. , v. 37, n. 2, p. 162 - 168, 2002.
10765174
10.1002/jms.270
2-s2.0-0036180844
Autor
Moraes L.A.B.
Eberlin M.N.
Institución
Resumen
Gas-phase reactions of four acylium ions and a thioacylium ion with three isomeric α-, β- and γ-hydroxy ketones are performed by pentaquadrupole mass spectrometric experiments. Novel structurally diagnostic reactions are observed, and found to correlate directly with interfunctional group separation. All five ions tested (CH3CO+, CH2=CHCO+, PhCO+, (CH3)2NCO+ and (CH3)2NCS+) react with the γ-hydroxy ketone (5-hydroxy-2-pentanone) to form nearly exclusively a cyclic oxonium ion of m/z 85 that formally arises from hydroxy anion abstraction. With the β-hydroxy ketone (4-hydroxy-2-pentanone), CH2=CHCO+, PhCO+ and (CH3)2NCO+ form adducts that undergo fast cyclization via intramolecular water displacement, yielding resonance-stabilized cyclic dioxinylium ions. With the α-hydroxy ketone (3-hydroxy-3-methyl-2-butanone), PhCO+, (CH3)2NCO+ and (CH3)2NCS+ form stable adducts. Evidence that these adducts display cyclic structures is provided by the triple-stage mass spectra of the (CH3)2NCS+ adduct; it dissociates to (CH3)2NCO+ via a characteristic reaction-dissociation pathway that promotes sulfur-by-oxygen replacement. If cyclizations are assumed to occur with intramolecular anchimeric assistance, relationships between structure and reactivity are easily recognized. Copyright © 2001 John Wiley & Sons, Ltd. 37 2 162 168 Kemp, W., (1970) Qualitative Organic Analysis, , McGraw-Hill: New York McLafferty, F.W., (1983) Tandem Mass Spectrometry, , (ed). Wiley: New York Busch, K.L., Glish, G.L., McLuckey, S.A., (1988) Mass Spectrometry/Mass Spectrometry: Techniques and Applications of Tandem Mass Spectrometry, , VCH: New York Farrar, J.M., Saunders W.H., Jr., (1988) Techniques for the Study of Ion/Molecule Reactions, , (eds). Wiley: New York Brodbelt, J.S., (1997) Mass Spectrom. Rev., 16, p. 91 Green, M.K., Lebrilla, C.B., (1997) Mass Spectrom. Rev., 16, p. 53 Eberlin, M.N., (1997) Mass Spectrom. Rev., 16, p. 113 Filippi, A., Giardini, A., Piccirillo, S., Speranza, M., (2000) Int. J. Mass Spectrom., 198, p. 137 Gronert, S., (2001) Chem. Rev., 101, p. 329 Olah, G.A., Gramain, A., White, A.M., (1976) Carbonium Ions, Olah GA, Schleyer PvR, , (eds). Wiley: New York Al-Talib, M., Tashtoush, H., (1990) Org. Prep. Proceed. Int., 22, p. 1 Eberlin, M.N., Cooks, R.G., (1993) J. Am. Chem. Soc., 115, p. 9226 Grandinetti, F., Pepi, F., Ricci, A., (1996) Chem. Eur. J., 2, p. 495 Moraes, L.A.B., Gozzo, F.C., Eberlin, M.N., Vainiotalo, P., (1997) J. Org. Chem., 62, p. 5096 Creaser, C.S., Williamson, B.L., (1998) Eur. Mass Spectrom., 4, p. 103 Sharifi, M., Einhorn, J., (1999) Int. J. Mass Spectrom., 190-191, p. 253 Grützmacher, H.F., Dohmeier-Fischer, S., (1998) Int. J. Mass Spectrom. Ion. Processes, 179-180, p. 207 Reid, G.E., Tichy, S.E., Pérez, J., O'Hair, R.A.J., Simpson, R.J., kenttämaa, H.I., (2001) J. Am. Chem. Soc., 123, p. 1184 Meurer, E.C., Eberlin, M.N., (2001) Int. J. Mass Spectrom., 210-211, p. 469 Juliano, V.F., Kascheres, C., Gozzo, F.C., Eberlin, M.N., Lago, C.L., (1996) Anal. Chem., 68, p. 1328 Eberlin, M.N., Majumdar, T.K., Cooks, R.G., (1992) J. Am. Chem. Soc., 114, p. 2884 Moraes, L.A.B., Pimpim, R.S., Eberlin, M.N., (1996) J. Org. Chem., 61, p. 8726 Tiernan, T.O., Futrell, J.H., (1968) J. Phys. Chem., 72, p. 3080 Schwartz, J.C., Wade, A.P., Enke, C.G., Cooks, R.G., (1990) Anal. Chem., 62, p. 1809 Kim, J.K., Findlay, M.C., Henderson, W.G., Caserio, M.C., (1973) J. Am. Chem. Soc., 95, p. 2184 Wysocki, V.H., Burinsky, D.J., Cooks, R.G., (1985) J. Org. Chem., 50, p. 1287 Eichmann, E.S., Brodbelt, J.S., (1993) Org. Mass Spectrom., 28, p. 665 Freitas, M.A., O'Hair, R.A.J., Willians, T.D., (1997) J. Org. Chem., 62, p. 6112 Heck, A.J.R., de Koning, L.J., Nibbering, N.M.M., (1993) Org. Mass Spectrom., 28, p. 245 O'Hair, R.A.J., Freitas, M.A., Gronet, S., Schmidt, J.A.R., Williams, T.D., (1995) J. Org. Chem., 60, p. 1990 Vais, V., Etinger, A., Mandelbaum, A., (1999) J. Mass Spectrom., 34, p. 755 O'Hair, R.A., Gronet, S., (1999) Int. J. Mass Spectrom., 11, p. 1275 Sparrapan, R., Mendes, M.A., Eberlin, M.N., (2000) J. Mass Spectrom., 35, p. 189 Meurer, E.C., Eberlin, M.N., J. Mass Spectrom., , in press Moraes, L.A.B., Eberlin, M.N., (2001) J. Am. Soc. Mass Spectrom., 12, p. 150 Moraes, L.A.B., Eberlin, M.N., (1997) J. Chem. Soc., Perkin Trans., 2, p. 2105