Detection of Explosives via Photolytic Cleavage of Nitroesters and Nitramines
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74230 with supporting info.pdf
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6.86 MB
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Adobe PDF
Checksum (MD5)
9c8a053ea0cab87d8955bc8c15880a64
Author(s)
Swager, Timothy Manning
Andrew, Trisha Lionel
Date Issued
March 2011
Journal
Journal of Organic Chemistry
Publisher
American Chemical Society (ACS)
Citation
Andrew, Trisha L., and Timothy M. Swager. “Detection of Explosives via Photolytic Cleavage of Nitroesters and Nitramines.” The Journal of Organic Chemistry 76.9 (2011): 2976–2993.
Version
Author's final manuscript
Abstract
The nitramine-containing explosive RDX and the nitroester-containing explosive PETN are shown to be susceptible to photofragmentation upon exposure to sunlight. Model compounds containing nitroester and nitramine moieties are also shown to fragment upon exposure to UV irradiation. The products of this photofragmentation are reactive, electrophilic NO[subscript x] species, such as nitrous and nitric acid, nitric oxide, and nitrogen dioxide. N,N-Dimethylaniline is capable of being nitrated by the reactive, electrophilic NO[subscript x] photofragmentation products of RDX and PETN. A series of 9,9-disubstituted 9,10-dihydroacridines (DHAs) are synthesized from either N-phenylanthranilic acid methyl ester or a diphenylamine derivative and are similarly shown to be rapidly nitrated by the photofragmentation products of RDX and PETN. A new (turn-on) emission signal at 550 nm is observed upon nitration of DHAs due to the generation of fluorescent donor−acceptor chromophores. Using fluorescence spectroscopy, the presence of ca. 1.2 ng of RDX and 320 pg of PETN can be detected by DHA indicators in the solid state upon exposure to sunlight. The nitration of aromatic amines by the photofragmentation products of RDX and PETN is presented as a unique, highly selective detection mechanism for nitroester- and nitramine-containing explosives and DHAs are presented as inexpensive and impermanent fluorogenic indicators for the selective, standoff/remote identification of RDX and PETN.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/jo200280c
