Fragmentation of 2-aroylbenzofuran derivatives by electrospray ionization tandem mass spectrometry

We investigated the gas-phase fragmentation reactions of a series of 2-aroylbenzofuran derivatives by electrospray ionization tandem mass spectrometry (ESI-MS/MS). The most intense fragment ions were the acylium ions m/z 105 and [M+H-C₆ H₆ ]⁺ , which originated directly from the precursor ion as a result of 2 competitive hydrogen rearrangements. Eliminations of CO and CO₂ from [M+H-C₆ H₆ ]⁺ were also common fragmentation processes to all the analyzed compounds. In addition, eliminations of the radicals •Br and •Cl were diagnostic for halogen atoms at aromatic ring A, whereas eliminations of •CH₃ and CH₂ O were useful to identify the methoxyl group attached to this same ring. We used thermochemical data, obtained at the B3LYP/6-31+G(d) level of theory, to rationalize the fragmentation pathways and to elucidate the formation of E, which involved simultaneous elimination of 2 CO molecules from B.