Chemical ionization induced competing and consecutive heterolytic ring cleavages in the mass spectra of substituted tetrahydro-1,3,2-oxazaphosphorin-2-oxides

The chemical ionization mass spectra of some substituted heterocyclic systems, viz. tetrahydro-1,3,2-oxazaphosphorin-2-oxides, reveal polar cycloreversion reactions. The zwitterion intermediate formed by the heterolysis of the C? O bond undergoes stepwise clean heterolysis further resulting in the expulsion of the potential nucleophilic and electrophilic groups. The competitive and consecutive heterolysis of the ring bonds leads to the formation of the protonated phenylimine ions. Competing with heterolysis, elimination reactions involving hydrogen transfer leading to the formation of α-phenylethyl ions are also observed. The chemical ionization mass spectrometry of the heterocyclic system shows many features of the Grob type of fragmentation mechanism.