Electron ionization mass spectral study of oxo- and thio derivatives of minor tobacco alkaloids

The electron-ionization mass spectra (EI-MS) of oxo- and thio-derivatives of minor tobacco alkaloids and structurally similar piperidine alkaloids, i.e. thiocotinine (1), 2'-oxo-N-methylanabasine (2), 2'-thio-N- methylanabasine (3), 2'-oxoanabasamine (4) and 2'-thioanabasamine (5) are discussed and general fragmentation routes of their molecular cations are proposed. Comparison of the data obtained for 1 with the EI-MS data of metameric metabolites of nicotine: 3'-hydroxycotinine, (A) and 5'-hydroxycotinine, (B) allows a differentiation between these metamers. The data will be useful for the identification of metabolites of alkaloids of these types in biological matrices.