Analysis of oligomeric peroxides in synthetic triacetone triperoxide samples by tandem mass spectrometry

    Authors

    M. E. Sigman; C. D. Clark; K. Painter; C. Milton; E. Simatos; J. L. Frisch; M. McCormick;J. L. Bitter

    Comments

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    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 Cl 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(CH(3))(2)](n)OOH, 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 CH(3)C(O)[OOC(CH(3))(2)](x)OOH, 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 (C) 2009 John Wiley & Sons, Ltd.

    Journal Title

    Rapid Communications in Mass Spectrometry

    Volume

    23

    Issue/Number

    3

    Publication Date

    1-1-2009

    Document Type

    Article

    First Page

    349

    Last Page

    356

    WOS Identifier

    WOS:000262905800003

    ISSN

    0951-4198

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