Direct assignment of positional isomers by mass spectrometry: ortho,meta and para acyl and amidyl anilines and phenols and derivatives |
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Authors: | Lilian Lúcia da Rocha Regina Sparrapan Rodinei Augusti Marcos N Eberlin |
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Institution: | 1. Institute of Chemistry, State University of Campinas—UNICAMP, CP 6154, 13083-970 Campinas, SP, Brazil;2. Department of Chemistry (ICEx), Federal University of Minas Gerais, 31270-901 Belo Horizonte, MG, Brazil |
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Abstract: | A direct MS/MS method for the ortho, meta or para configuration assignment of any single molecule that forms reference ions upon ionization and dissociation is demonstrated. Gas-phase structure diagnostic ion–molecule reactions with acetonitrile are shown to distinguish the isomeric 2-, 3- and 4-hydroxybenzoyl cations and the 2- from the 3- and 4-aminobenzoyl cations. These reference ions, which display indistinguishable 15 eV collision-induced dissociation product ion mass spectra, react with acetonitrile to yield characteristic ratios of product ions, most particularly for the 2-isomers. The reactivity of the 2-benzoyl cations is the most characteristic since the ortho configuration allows for 4+ + 2] polar cycloaddition that yields relatively stable heterocycles in N-protonated forms. Distinction of the reference isomeric 2-, 3- and 4-hydroxy- and aminobenzoyl cations permits, therefore, partially or completely, direct ‘MS-only’ positional assignment of either ortho, meta or para configuration for any single molecule that forms such reference ions upon ionization and dissociation. This “class-universal” method for direct MS assignment of a single positional isomer should therefore be applicable to many members of the homologous series of isomeric ortho, meta and para acyl and amidyl anilines and phenols and derivatives. Such molecules dissociate, or are likely to dissociate, after or during ionization processes to form the reference and structurally diagnostic ortho, meta or para hydroxy- or aminobenzoyl cations. Copyright © 2004 John Wiley & Sons, Ltd. |
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Keywords: | pentaquadrupole mass spectrometry acylium ions cyclization reactions isomer distinction ortho meta and para structural assignment |
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