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Ion-Molecule Reactions Of O,S-Dimethyl Methylphosphonothioate: Evidence For Intramolecular Sulfur Oxidation During Vx Perhydrolysis, Jilliarne Williams, Martin Paine, Stephen J. Blanksby, Michael L. Rogers, Andrew M. Mcanoy
Ion-Molecule Reactions Of O,S-Dimethyl Methylphosphonothioate: Evidence For Intramolecular Sulfur Oxidation During Vx Perhydrolysis, Jilliarne Williams, Martin Paine, Stephen J. Blanksby, Michael L. Rogers, Andrew M. Mcanoy
Stephen Blanksby
The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO- with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic …