Electron ionization mass spectral studies of phenoxide derivatives of mustards: Implications for analysis to support chemical weapons convention

• EI-MS of phenoxide derivatives of sulfur and nitrogen mustards was investigated.
• Fragmentation routes were investigated via analysis of fragments of deuterated analogs.
• A previously unknown intramolecular Claisen-type rearrangement was observed in EI-MS.

Mass spectrometric (MS) analytical features of phenoxide derivatives of sulfur and nitrogen mustards were described. Electron ionization (EI) mass spectra of title chemicals with possible fragmentation routes were investigated via analysis of fragment ions of deuterated analogs, MS–MS experiments and density functional theory calculations. EI-MS and EI-MS/MS analysis revealed phenoxide, ethane, CO, CS and H2S exclusions, α-cleavages, retro Diels–Alder cycloaddition, hydrogen rearrangements and a previously unknown intramolecular Claisen-type rearrangement. The results would be valuable during toxic chemical destruction monitoring in support of chemical weapons convention (CWC) and for the verification of state-parties activities, based on CWC context.

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