It was previously reported that the collision-induced dissociation of the Na+ adduct ions of pyrogallol tribenzyl ethers generated by electrospray mass spectrometry (ESI-CID) results in what is presumed to be the rapid loss of two of the adjacent benzyl groups to form the Na+ adduct ions of stable ortho-quinone structures.1,2 We recently described the synthesis of two isotopomeric derivatives of this triether, one with a d7-benzyl group at the 2-position and another with d7-benzyl groups at both the 1- and 3-positions. Mass spectrometric analysis showed that, surprisingly, loss of the central benzyl group is substantially favored. In order to learn more about the fragmentation patterns of these benzylated polyphenolic compounds, we prepared derivatives of 1,2,4-trihydroxybenzene with benzyl groups containing zero, two, and seven deuterium atoms and studied them using EI and ESI mass spectrometry. Differentially deuterated benzyl bromide could be selectively condensed at first with the 4- and then the 2-positions of 2,4-dihydroxyacetophenone using potassium carbonate in dry DMF at 100 �C. Subsequent Baeyer-Villiger rearrangement utilizing peracetic acid followed by hydrolysis was employed to convert the acetophenone derivative to the corresponding phenol, which was then benzylated at the 1-position. Complete characterization of all products using 1H and 13C NMR will be presented along with a discussion of the mass spectrometric results.1. D. Kuck, S. Heitkamp, M. C. Letzel, I. Ahmed, K. Krohn, 44th Annual Meeting of the German Mass Spectrometry Society (DGMS), Dortmund, Germany, 02/27�03/02, 2011.2. K. Krohn, I. Ahmed, M. John, M. C. Letzel, D. Kuck, Eur. J. Org. Chem. 2010 , 2544�2554.

Synthesis and mass spectrometric study of deuterium labeled 1,2,4-trihydroxybenzene tribenzyl ether

247th National Meeting (2014)

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