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Fragmentation pathways of O-alkyl methylphosphonothionocyanidates in the gas phase: Toward unambiguous structural characterization of chemicals in the Chemical Weapons Convention framework

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Abstract

The electron-impact (EI) mass spectra of a series of O-alkyl methylphosphonothionocyanidates were studied for Chemical Weapons Convention (CWC) purposes. General EI fragmentation pathways were constructed and discussed, and collision-induced dissociation studies of the major EI ions were performed to confirm proposed fragment structures by analyzing fragment ions of deuterated analogs and by use of density functional theory (DFT) calculations. Thiono–thiolo rearrangement, McLafferty-type rearrangement, and a previously unknown intramolecular electrophilic aromatic substitution reaction were observed and confirmed. The study also focused on differentiation of isomeric compounds. Retention indices for all compounds, and an electrophilicity index for several compounds, are reported and interpreted.

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Authors and Affiliations

  1. Department of Science, Payame Noor University (PNU), P.O. Box: 19395–4697, Tehran, Iran

    Hamid Saeidian

  2. Defense Chemical Research Lab (DCRL), P.O. Box 31585–1461, Karaj, Iran

    Mehran Babri, Davood Ashrafi, Mansour Sarabadani & Mohammad Taghi Naseri

Authors
  1. Hamid Saeidian
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  2. Mehran Babri
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  3. Davood Ashrafi
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  4. Mansour Sarabadani
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  5. Mohammad Taghi Naseri
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Corresponding author

Correspondence to Hamid Saeidian.

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Dedicated to the late Professor Ali Massoumi on his 80th birthday.

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Saeidian, H., Babri, M., Ashrafi, D. et al. Fragmentation pathways of O-alkyl methylphosphonothionocyanidates in the gas phase: Toward unambiguous structural characterization of chemicals in the Chemical Weapons Convention framework. Anal Bioanal Chem 405, 6749–6759 (2013). https://doi.org/10.1007/s00216-013-7094-8

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  • DOI: https://doi.org/10.1007/s00216-013-7094-8

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