Ned Porter
Faculty Member
Last active: 5/29/2014

Structural analysis of diacyl peroxides by electrospray tandem mass spectrometry with ammonium acetate: bond homolysis of peroxide-ammonium and peroxide-proton adducts.

Yin H, Hachey DL, Porter NA
Rapid Commun Mass Spectrom. 2000 14 (14): 1248-54

PMID: 10918375 · DOI:10.1002/1097-0231(20000730)14:14<1248::AID-RCM18>3.0.CO;2-B

Organic peroxides have significant implications in organic chemistry and biological processes. The weak O-O bond makes them extremely difficult to characterize by conventional analytical methods. Diacyl peroxides are one of the major radical sources in polymerization and organic synthesis. It is well known that diacyl peroxides are thermal labile and thus are not amenable to study by gas chromatography/mass spectrometry (GC/MS). Electrospray tandem mass spectrometry (ESI-MS/MS) has been applied to the structural analysis of diacyl peroxides by formation of ammonium adducts. Collision induced dissociation (CID) studies of the ammonium adducts of the peroxide [M + NH(4)](+) give collision energy dependent fragments. For most diacyl peroxides, homolysis of the peroxy bond predominates the fragmentation pathways of the peroxide-ammonium adducts. Deuterated substrates have been employed to provide evidence for typical fragmentation pathways. The CID studies were also used to locate the O-18 in some O-18 specifically labeled diacyl peroxides. For branched alkyl or alkoxy substrates, McLafferty rearrangement and decarboxylation become a major pathway. By comparison with some anhydride analogues, ESI-MS/MS can also be used to study this class of compounds.

Copyright 2000 John Wiley & Sons, Ltd.

MeSH Terms (4)

Mass Spectrometry Peroxides Protons Quaternary Ammonium Compounds

Connections (2)

This publication is referenced by other Labnodes entities: