Fragmentation reactions of N-benzyltetrahydroquinolines in electrospray ionization mass spectrometry: the roles of ion/neutral complex intermediates.

RATIONALE

Electrospray ionization mass spectrometry (ESI-MS) combined with the collision-induced dissociation (CID) technique has assumed increasing importance as an invaluable tool for the structural analysis of organic and biological molecules. However, general rules for elucidating the fragmentation behaviors of charged molecules in the gas phase are still lacking. Therefore, explorations on the mechanistic information are desirable at all times.

METHODS

CID experiments of protonated N-benzyltetrahydroquinolines were carried out on ESI ion trap mass spectrometer and accurate mass measurements were performed on a high-resolution ESI quadrupole time-of-flight (Q-TOF) mass spectrometer in positive ion mode.

RESULTS

An ion/neutral complex, [RC6H4CH2(+)/tetrahydroquinoline], resulting from cleavage of the C-N bond induced by the positive charge brought in by protonation, was proposed to be the intermediate to elucidate the fragmentation reactions. For all the compounds investigated, benzyl cation transfer, electron transfer and hydride transfer reactions mediated by the complex were observed. Moreover, for the compound substituted by a methyl group at the para-position of the benzylic phenyl ring, proton transfer reaction via the complex also occurs.

CONCLUSIONS

This study is a case for better understanding the intriguing roles of ion/neutral complexes in gas-phase fragmentation reactions and enriching the knowledge about the gas-phase chemistry of the benzyl cation. In addition, it provides useful information for researchers working on analysis or structural elucidation of complicated compounds which contain the N-benzyltetrahydroquinoline substructure.