Meisenheimer complexes bonded at carbon and at oxygen

Focus: McLafferty Rearrangement


The carbon-bonded gas-phase Meisenheimer complex of 2,4,6-trinitrotoluene (TNT) and the nitromethyl carbanion CH2NO2 (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 CH2NO2 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 CH2NO2 and the three dinitrobenzene isomers display distinctive fragmentations. The oxygen-bonded σ-complex of TNT with the deprotonated hemiacetal anion CH3OCH2 (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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© American Society for Mass Spectrometry 2004

Authors and Affiliations

  1. 1.Department of ChemistryPurdue UniversityWest LafayetteUSA

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