Title
Analysis Of Oligomeric Peroxides In Synthetic Triacetone Triperoxide Samples By Tandem Mass Spectrometry
Abstract
Oligomeric peroxides formed in the synthesis of triacetone triperoxide (TATP) have been analyzed by mass spectrometry utilizing both electrospray ionization (ESI) and chemical ionization (CI) to form sodiated adducts (by ESI) and ammonium adducts (by CI and ESI). Tandem mass spectrometry and deuterium isotopic labeling experiments have been used to elucidate the collision-induced dissociation (CID) mechanisms for the adducts. The CID mechanisms differ for the sodium and ammonium adducts and vary with the size of the oligoperoxide. The sodium adducts of the oligoperoxides, H[OOC(CH3)2] nOOH, do not cyclize under CID, whereas the ammonium adducts of the smaller oligoperoides (n<6) do form the cyclic peroxides under CID. Larger oligoperoxide adducts with both sodium and ammonium undergo dissociation through cleavage of the backbone under CID to form acyl- and hydroperoxy-terminated oligomers of the general form CH3C(O)[OOC(CH3) 2]xOOH, where x is an integer less than the original oligoperoxide degree of oligomerization. The oligoperoxide distribution is shown to vary batch-to-batch in the synthesis of TATP and the post-blast distribution differs slightly from the distribution in the uninitiated material. The oligoperoxides are shown to be decomposed under gentle heating. Copyright © 2009 John Wiley & Sons, Ltd.
Publication Date
2-15-2009
Publication Title
Rapid Communications in Mass Spectrometry
Volume
23
Issue
3
Number of Pages
349-356
Document Type
Article
Personal Identifier
scopus
DOI Link
https://doi.org/10.1002/rcm.3879
Copyright Status
Unknown
Socpus ID
60149083716 (Scopus)
Source API URL
https://api.elsevier.com/content/abstract/scopus_id/60149083716
STARS Citation
Sigman, Michael E.; Clark, C. Douglas; Painter, Kimberly; Milton, Chatham; and Simatos, Ekaterina, "Analysis Of Oligomeric Peroxides In Synthetic Triacetone Triperoxide Samples By Tandem Mass Spectrometry" (2009). Scopus Export 2000s. 12219.
https://stars.library.ucf.edu/scopus2000/12219