Gas-phase reactions for selective detection of the explosives TNT and RDX.
Highly selective gas-phase reactions with ethyl vinyl ether (EVE) of major electron (EI) and chemical ionization (CI) fragment ions of the explosives TNT and RDX have been uncovered. The fragment ion of m/z 210 from TNT undergoes [4(+)+ 2] cycloaddition with EVE to form an oxo-iminium ion of m/z 282, which dissociates by acetaldehyde loss after a [1,5-H] shift to form a quinolynium ion of m/z 238. The fragment ion of m/z 149 from RDX reacts with EVE by a formal vinylation reaction, that is, the elusive cyclic adduct loses ethanol to yield a nitro-iminium ion of m/z 175, which reacts further with EVE to form a second cyclic product ion of m/z 247. Calculations and MS/MS experiments support the proposed structures. These highly characteristic reactions of diagnostic EI and CI fragment ions improve selectivity for TNT and RDX detection.
Meurer
Eduardo C
EC
Institute of Chemistry, State University of Campinas, UNICAMP, SP, Brazil.
Chen
Hao
H
Riter
Leah
L
Cotte-Rodriguez
Ismael
I
Eberlin
Marcos N
MN
Cooks
R Graham
RG