This communication describes the synthesis and gas chromatography/mass spectrometric (GC/MS) analysis of N,N-dialkylphosphoramidic dihalides and alkylphosphonic difluorides, which are synthones of nerve agents. The study was undertaken with a view to developing a spectral database of these compounds for verification purposes of the Chemical Weapons Convention (CWC). The modified synthetic approach reported here has advantages over traditional syntheses in terms of time and yield. GC/MS analysis of these synthones yielded electron ionization (EI) mass spectra and, based on these spectra, generalized fragmentation routes are proposed that rationalize most of the characteristic ions.