Artículos de revistas
Cyclization Reactions Of Acylium And Thioacylium Ions With Isocyanates And Isothiocyanates: Gas Phase Synthesis Of 3,4-dihydro-2,4-dioxo-2h-1,3,5- Oxadiazinium Ions
Registro en:
Journal Of The American Society For Mass Spectrometry. , v. 16, n. 10, p. 1602 - 1607, 2005.
10440305
10.1016/j.jasms.2005.05.011
2-s2.0-25144431787
Autor
Meurer E.C.
Sparrapan R.
Tomazela D.M.
Eberlin M.N.
Augusti R.
Institución
Resumen
Gas-phase reactions of several acylium and thioacylium ions, that is H 2C=N-C+=O, H2C=N-C+=S, O=C=N-C +=O, S=C=N-C+=O, H3C-C+=O, and (CH3)2N-C+=O, with both a model isocyanate and isothiocyanate, that is, C2H5-N=C=O and C 2H5-N=C=S, were investigated using tandem-in-space pentaquadrupole mass spectrometry. In these reactions, the formation of mono- and double-addition products is observed concurrently with proton transfer products. The double-addition products are far more favored in reactions with ethyl isocyanate, whereas the reactions with ethyl isothiocyanate form, preferentially, either the mono-addition product or proton transfer products, or both. Retro-addition dominates the low-energy collision-induced dissociation of the mono- and double-addition products with reformation of the corresponding reactant ions. Ab initio calculations at Becke3LYP//6-311 + G(d,p) level indicate that cyclization is favored for the double-addition products and that products equivalent to those synthesized in solution, that is, of 3,4-dihydro-2,4-dioxo-2H-1,3,5-oxadiazinium ions and sulfur analogs, are formed. © 2005 American Society for Mass Spectrometry. 16 10 1602 1607 McLafferty, F.W., Tandem Mass Spectrometry - From Infancy to Maturity in 25 Years (1993) Org. Mass Spectrom, 28, pp. 1403-1406 Futrell, J.H., Development of Tandem Mass Spectrometry: One Perspective (2000) Int. J. Mass Spectrom, 200, pp. 495-508 Shukla, A.K., Futrell, J.H., Tandem Mass Spectrometry: Dissociation of Ions by Collisional Activation (2000) J. Mass Spectrom, 35, pp. 1069-1090 Stirk, K.M., Kiminkinen, L.K.M., Kenttamaa, H.I., Ion Molecule Reactions of Distonic Radical Cations (1992) Chem. Rev., 92, pp. 1649-1665 Brodbelt, J.S., Analytical Applications of Ion-Molecule Reactions (1997) Mass Spectrom. 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