title: Fragmentation pathways of O-alkyl methylphosphonothionocyanidates in the gas phase: toward unambiguous structural characterization of chemicals in the Chemical Weapons Convention framework.
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.
authors.affiliation: Department of Science, Payame Noor University (PNU), P.O. Box: 19395-4697, Tehran, Iran. h_porkaleh@yahoo.com
authors.forename: Hamid
authors.initials: H
authors.lastname: Saeidian
authors.forename: Mehran
authors.initials: M
authors.lastname: Babri
authors.forename: Davood
authors.initials: D
authors.lastname: Ashrafi
authors.forename: Mansour
authors.initials: M
authors.lastname: Sarabadani
authors.forename: Mohammad Taghi
authors.initials: MT
authors.lastname: Naseri
mesh_terms: D002619:Chemical Warfare Agents / Q000032:analysis* / Q000737:chemistry*; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D005740:Gases / Q000032:analysis* / Q000737:chemistry*; D009498:Neurotoxins / Q000032:analysis* / Q000737:chemistry*; D044367:Phase Transition
chemical_list: D002619:Chemical Warfare Agents; D005740:Gases; D009498:Neurotoxins