Characterization and Differentiation of Heterocyclic Isomers. Tandem Mass Spectrometry and Molecular Orbital Calculations on 3-Methylisoxazolo- and 2-Methyloxazolopyridines

Metastable mass-analyzed ion kinetic energy (MIKE) and collision-induced dissociation MIKE spectrometries have been applied to the study of all members of two classes of heteroaromatic isomers: 3-methylisoxazolo-and 2-methyloxazolopyridines. The study revealed that tandem mass spectrometry can characterize and differentiate the isomeric ion structures produced by these heterocycles. In particular, the MIKE spectra of both the molecular ions and abundant fragments formed by CO and CH3CN losses show characteristic differences that allow distinction among the isomers dependent on the position of the nitrogen atom in the pyridine ring, and distinction of isoxazole derivatives from oxazoles. The results indicate that the isomerization of the isoxazole moiety to oxazole-proposed for other analogous compounds-does not occur in these heterocyclic systems. The experimental work is supported by molecular orbital calculations both on neutral molecules and on molecular and fragment ions. © 1995 American Society for Mass Spectrometry.