Ion-molecule reactions of O,S-dimethyl methylphosphonothioate: evidence for intramolecular sulfur oxidation during VX perhydrolysis

The Journal of Organic Chemistry
Andrew Michael McAnoyStephen J Blanksby

Abstract

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 addition at phosphorus affording a reactive pentavalent intermediate that readily undergoes internal sulfur oxidation and concomitant elimination of CH(3)SOH to yield the methyl methylphosphonate anion. Consistent with previous solution phase observations of VX perhydrolysis, the toxic P-O cleavage product is not observed in this VX model system and theoretical calculations identify P-O cleavage to be energetically uncompetitive. Conversely, intramo...Continue Reading

References

Jun 12, 2002·Journal of the American Society for Mass Spectrometry·Jae C SchwartzJohn E P Syka
Aug 15, 2003·Organic Letters·Galina V KapustinFelicia A Etzkorn
Dec 31, 2005·Organic Letters·Yi Ren, Hiroshi Yamataka
Sep 30, 2006·Chemistry : a European Journal·Yi Ren, Hiroshi Yamataka
Jun 26, 2007·The Journal of Organic Chemistry·Yi Ren, Hiroshi Yamataka
Oct 19, 2007·Organic & Biomolecular Chemistry·David G Harman, Stephen J Blanksby
May 22, 2009·Journal of the American Chemical Society·Stephanie M VillanoVeronica M Bierbaum

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Citations

Dec 19, 2013·Journal of the American Society for Mass Spectrometry·Ditte L ThomsenVeronica M Bierbaum
Mar 12, 2015·Journal of Computational Chemistry·Wen-Yang ZhaoKai-Chung Lau
Jun 21, 2013·Journal of Computational Chemistry·Yi RenWai-Kee Li
Jul 27, 2012·The Journal of Physical Chemistry. a·Debasish MandalAbhijit K Das
Oct 23, 2012·The Journal of Organic Chemistry·Daniele MarcianoYossi Zafrani

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