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Electron ionization-induced fragmentation of N- and O-alkoxymethylated carbostyril and phenanthridinone
Szmigielski, Rafal,Danikiewicz, Witold
, p. 781 - 790 (2004)
Unimolecular fragmentation patterns of N-alkoxymethylated carbostyril and phenanthridinone and their O-alkoxymethyl isomers were studied. The main fragmentation reaction observed for the studied compounds is the elimination of an aldehyde molecule. The main products of this reaction are the appropriate N-methyl derivatives, but ions with other structures are also formed. This reaction is supposed to proceed via 1,3-H shift in the alkoxymethyl group in the case of the N-alkoxymethyl derivatives and by a multi-step mechanism for O-alkoxymethylated compounds. Another important fragmentation common for all studied compounds is the loss of an alkyl radical from N- and O-alkoxymethyl groups, yielding the appropriate stable isomeric cations, which, according to the results of the further fragmentation, undergo fast equilibration reaction via an ion-neutral complex. This process is accompanied by the unusually high kinetic energy release value. Copyright
