Gas Chromatography—Electron Ionization—Mass Spectrometry Analysis of O,O′-Dialkyl Methylphosphonites for Verification Analysis of the Chemical Weapons Convention

Abstract

Gas chromatography–mass spectrometry (GC-MS) analysis of O,O′-dialkyl methylphosphonites (DAMPs) was carried out with a view to developing a database and understanding the mechanism of fragmentation. DAMPs are included in the list of schedule 2B4 chemicals of the Chemical Weapons Convention. GC-MS analysis of DAMPs and their deuterated analogs revealed that their fragmentations were dominated by α-cleavages, alkenyl radical loss and hydrogen rearrangements. Based on fragment ions of deuterated analogs and density functional theory calculations, the fragmentation routes were rationalized.