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Intramolecular Electrophilic Aromatic Substitution in Gas-phase Fragmentation of Protonated N-Benzylbenzaldimines

  • Research Article
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Journal of The American Society for Mass Spectrometry

Abstract

In this study, the gas-phase fragmentations of protonated N-benzylbenzaldimines were investigated by electrospray ionization tandem mass spectrometry (ESI-MSn). Upon collisional activation, several characteristic fragment ions are produced and their fragmentation mechanisms are rationalized by electrophilic aromatic substitution accompanied by benzyl cation transfer. (1) For N-(p-methoxybenzylidene)-1-phenylmethanimine, concomitant with a loss of HCN, a product ion at m/z 121 was observed. It is proposed to be generated from electrophilic substitution at the ipso-position by transferring benzyl cation rather than cleavage of the C-N double bond. (2) For N-(m-methoxybenzylidene)-1-phenylmethanimine, a product ion at m/z 209 was obtained, corresponding to the elimination of NH3 carrying two hydrogens from the two aromatic rings respectively. This process can be rationalized by two sequential electrophilic substitutions and cyclodeamination reaction based on the benzyl cation transfer. Deuterium-labeled experiments, density functional theory (DFT) calculation and substituent effect results also corroborate the proposed mechanism.

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Acknowledgments

The authors gratefully acknowledge financial support from the National Science Foundation of China (nos. 21025207 and 21372199).

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  1. Department of Chemistry, Zhejiang University, Hangzhou, 310027, China

    Shanshan Shen, Yunfeng Chai, Guofeng Weng & Yuanjiang Pan

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Correspondence to Yuanjiang Pan.

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Shen, S., Chai, Y., Weng, G. et al. Intramolecular Electrophilic Aromatic Substitution in Gas-phase Fragmentation of Protonated N-Benzylbenzaldimines. J. Am. Soc. Mass Spectrom. 25, 1662–1669 (2014). https://doi.org/10.1007/s13361-014-0935-7

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