Protonated benzene, C(6)H(7) (+), has been studied extensively to understand the structure and energy of a protonated organic molecule in the gas phase. The formation of C(6)H(7) (+) is either through direct protonation of benzene, i.e., chemical ionization, or through fragmentation of certain radical cations produced from electron ionization or photon ionization. We report a novel observation of C(6)H(7) (+) as a product ion formed in the collision-induced dissociation (CID) of protonated benzamide and related molecules produced via electrospray ionization (ESI). The formation of C(6)H(7) (+) from these even-electron precursor ions during the CID process, which has not been previously reported, is proposed to occur from the protonated molecules via a proton migration in a five-membered ring intermediate followed by the cleavage of the mono-substituent C--C bond and concurrent formation of an ion-molecule complex. This unique mechanism has been scrutinized by examining some deuterated molecules and a series of structurally related model compounds. This finding provides a convenient mean to generate C(6)H(7) (+), a reactive intermediate of considerable interest, for further physical or chemical investigation. Further studies indicate that the occurrence of C(6)H(7) (+) in liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) appears to be a rather common phenomenon for many compounds that contain 'benzoyl-type' moieties. Hence, the observation of the C(6)H(7) (+) ion in LC/ESI-MS/MS can be used as an informative fragmentation pathway which should facilitate the identification of a great number of compounds containing the 'benzoyl-type' and similar structural features. These compounds are frequently present in food and pharmaceutical products as leachable impurities that require strict control and rapid elucidation of their identities.
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