Abstract
The carbon-bonded gas-phase Meisenheimer complex of 2,4,6-trinitrotoluene (TNT) and the nitromethyl carbanion CH2NO −2 (m/z 60) is generated for the first time by chemical ionization using nitromethane as the reagent gas. Collision-induced dissociation (CID) of the Meisenheimer complex furnishes deprotonated TNT, a result of the higher gas-phase acidity of TNT than nitromethane. The formation of Meisenheimer complexes with CH2NO −2 in the gas phase is selective to highly electron-deficient compounds such as dinitrobenzene and trinitrobenzene and does not occur with organic molecules with lower electron-affinity such as methanol, methylamine, propionaldehyde, acetone, ethyl acetate, chloroform, toluene, m-methoxytoluene, and even nitrobenzene and p-fluoronitrobenzene. As such, the reaction allows selective detection of TNT in mixtures. Meisenheimer complexes between CH2NO −2 and the three dinitrobenzene isomers display distinctive fragmentations. The oxygen-bonded σ-complex of TNT with the deprotonated hemiacetal anion CH3OCH −2 (m/z 61), represents a different type of Meisenheimer complex. It displays characteristic fragmentation involving loss of HNO2 upon CID. The combination of a selective ion/molecule reaction (Meisenheimer complex formation) followed by a characteristic CID process provides a second novel and highly selective approach to the detection of TNT and closely related compounds in mixtures. The assay is readily implemented using neutral loss scans in a triple quadrupole mass spectrometer. Gas-phase reactions of denitrosylated TNT with benzaldehyde produce the corresponding dihydrofuran in an aldol condensation, a result that parallels the corresponding condensed-phase reaction.
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This article is dedicated with affection to Fred McLafferty in celebration of a life in mass spectrometry.
Published online June 8, 2004
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Chen, H., Chen, H. & Cooks, R.G. Meisenheimer complexes bonded at carbon and at oxygen. J Am Soc Mass Spectrom 15, 998–1004 (2004). https://doi.org/10.1016/j.jasms.2004.03.006
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DOI: https://doi.org/10.1016/j.jasms.2004.03.006