Fragmentation of protonated 2-(2-phenylethyl)chromones from agarwood: the diagnostic role of ion/neutral complexes as reactive intermediates

Yang D, Xia B, Jiang Y, Mei W, Kuck D (2015)
European Journal Of Mass Spectrometry 21(3): 609-621.

Journal Article | Published | English

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Abstract
A positive-ion electrospray ionisation collision-induced dissociation mass spectrometric study on the fragmentation of the [M + H](+) ions of 2-(2-phenylethyl)chromone and a set of nine hydroxyl- and/or methoxy-substituted derivatives has revealed a highly prominent fragmentation channel, the loss of benzoquinomethanes or a benzaldehyde, respectively, as a diagnostic feature for 2-(2-phenylethyl)chromones that bear a hydroxyl group at the para- (4'-), ortho-(2'-) and/or benzylic (alpha-) position of the phenylethyl residue. Derivatives that bear only a meta-(3'-) hydroxyl group do not undergo this elimination. The intermediacy of ion/neutral complexes (INCs) is invoked to explain this fragmentation, which involves the remarkable intra-complex proton or hydrogen atom transfer from the remote 4'-OH (or the 2'- or alpha-OH) functionalities. Density functional theory (B3LYP/6-31G(d)) calculations confirm the energetic preference for these elimination channels and agree with the limited thermochemical data known for para- and ortho-benzoquinomethanes. The INC-mediated losses of the benzaldehydes from the [M + H](+) ions of the alpha-hydroxy-substituted 2-(2-phenylethyl) chromones correspond to a particularly facile (vinylogous) Grob fragmentation. The study may be viewed as a telling example of the diagnostic role of ion/neutral complexes as intermediates for the structural assignment of constitutional isomers by mass spectrometry.
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Yang D, Xia B, Jiang Y, Mei W, Kuck D. Fragmentation of protonated 2-(2-phenylethyl)chromones from agarwood: the diagnostic role of ion/neutral complexes as reactive intermediates. European Journal Of Mass Spectrometry. 2015;21(3):609-621.
Yang, D., Xia, B., Jiang, Y., Mei, W., & Kuck, D. (2015). Fragmentation of protonated 2-(2-phenylethyl)chromones from agarwood: the diagnostic role of ion/neutral complexes as reactive intermediates. European Journal Of Mass Spectrometry, 21(3), 609-621.
Yang, D., Xia, B., Jiang, Y., Mei, W., and Kuck, D. (2015). Fragmentation of protonated 2-(2-phenylethyl)chromones from agarwood: the diagnostic role of ion/neutral complexes as reactive intermediates. European Journal Of Mass Spectrometry 21, 609-621.
Yang, D., et al., 2015. Fragmentation of protonated 2-(2-phenylethyl)chromones from agarwood: the diagnostic role of ion/neutral complexes as reactive intermediates. European Journal Of Mass Spectrometry, 21(3), p 609-621.
D. Yang, et al., “Fragmentation of protonated 2-(2-phenylethyl)chromones from agarwood: the diagnostic role of ion/neutral complexes as reactive intermediates”, European Journal Of Mass Spectrometry, vol. 21, 2015, pp. 609-621.
Yang, D., Xia, B., Jiang, Y., Mei, W., Kuck, D.: Fragmentation of protonated 2-(2-phenylethyl)chromones from agarwood: the diagnostic role of ion/neutral complexes as reactive intermediates. European Journal Of Mass Spectrometry. 21, 609-621 (2015).
Yang, Delan, Xia, Bing, Jiang, Yan, Mei, Wenli, and Kuck, Dietmar. “Fragmentation of protonated 2-(2-phenylethyl)chromones from agarwood: the diagnostic role of ion/neutral complexes as reactive intermediates”. European Journal Of Mass Spectrometry 21.3 (2015): 609-621.
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PMID: 26307740
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