Stabilization of even-electron ions by cyclization of substituents on 3N- and 4N-nitrogens in 4N-substituted cytosines

Electron impact mass spectra of 4N-substituted derivatives of cytosine are reported. The strong influence of 4N-substituents on the mode of mass fragmentation occurring upon electron impact ionization was proved. The presence of α-carbon in the 4N-substituent extends the possibilities of fragmentation via rearrangement leading to formation of even-electron bicyclic ions containing quaternary 3N-nitrogen. When β-carbon was present in the 4N-substituent, the decomposition based on elimination of alkenes was detected as well as the rearrangement leading to formation of bicyclic even-electron ions containing quaternary 3N- or 4N-nitrogen.