Consecutive loss of two benzyl radicals from the [M + Na]+ adduct ions of pyrogallol tribenzyl ether and its derivatives

• Published in: European journal of mass spectrometry (Chichester, England) Vol. 24; no. 1; pp. 23 - 32
• Main Authors: Kuck, Dietmar, Heitkamp, Sandra, Letzel, Matthias, Ahmed, Ishtiaq, Krohn, Karsten
• Format: Journal Article
• Language: English
• Published: London, England SAGE Publications 01-02-2018
• Subjects: homolytic cleavage; collision-induced dissociation; benzyl radicals; sodiated molecules; phenoxy radicals; benzyl aryl ethers; benzoquinones; Electrospray mass spectrometry
• ISSN: 1469-0667; 1751-6838
• DOI: 10.1177/1469066717729300

The electrospray ionization–collision-induced dissociation mass spectra of nine pyrogallol tribenzyl ethers, 2–10, and a catechol dibenzyl ether, 11, that bear various functional groups or larger structural extensions have been studied with respect to the occurrence of a highly characteristic consecutive loss of two benzyl radicals from the sodiated molecular ions, [M + Na]+. It is shown that this specific fragmentation reaction strongly dominates other fragmentation routes, such as loss of carbon monoxide, formaldehyde and water. In addition, elimination of benzaldehyde occurs as a minor fragmentation channel in most cases. In contrast to these aryl–benzyl ethers, the consecutive two-fold loss of C7H7• is suppressed in the [M + Na]+ ions of dibenzyl ethers derived from multiply benzylated gallocatechin and catechin, where the elimination of benzyl alcohol prevails the primary fragmentation almost completely. The secondary fragmentation of the [M + Na]+ ions, which also comprises the two-fold loss of C7H7•, as well as a remarkable primary fragmentation of a flavene-based congener leading to particularly stable sodium-free chromylium product ions is also presented.
†
Deceased.