Mass spectrometric study on O(S)-alkyl N,N-dimethylamino alkylphosphonates (alkylphosphonothiolates) for Chemical Weapons Convention verification purposes

Mass spectral characterization of the CWC‐related isomeric dialkyl alkylphosphonothiolates/alkylphosphonothionates under gas chromatography/mass spectrometry conditions

“…The spectra of P‐methyl‐group‐containing compounds include the [M – CH 3 ] + ion, but there are other possible routes for the loss of methyl radical from the alkyl groups attached to O/S. The P‐C 3 H 7 ‐alkyl‐group‐containing compounds show a [M–C 3 H 6 ] +• ion at m/z 140 that is formed by a [1,4] C–P hydrogen shift (propyl) or a [1,3] C–P hydrogen shift (isopropyl) . The [M–C 3 H 5 ] + ion (McLafferty + 1 rearrangement), which is characteristically observed in O/S‐C 3 H 7 ‐group‐containing compounds, is absent in the P‐C 3 H 7 compounds; however, these compounds show a low‐abundance [M–C 3 H 7 ] + ion at m/z 139 formed through α‐cleavage (Supplementary Fig.…”

“…The typical EI‐induced gas phase 'thiono‐thiolo rearrangement', i.e., conversion of > P(S)‐O‐R into > P(O)‐S‐R, has been observed in many classes of phosphorus‐containing compounds such as phosphines, phosphates, phosphonates and phosphoramidates, etc . Cooks et al .…”

“…The P-C 3 H 7 -alkyl-group-containing compounds show a [M-C 3 H 6 ] + • ion at m/z 140 that is formed by a [1,4] C-P hydrogen shift (propyl) or a [1,3] C-P hydrogen shift (isopropyl). [37] The [M-C 3 H 5 ] + ion (McLafferty + 1 rearrangement), which is characteristically observed in O/S-C 3 H 7 -group-containing compounds, is absent in the P-C 3 H 7 compounds; however, these compounds show a low-abundance [M-C 3 H 7 ] + ion at m/z 139 formed through a-cleavage ( Supplementary Fig. S1, Supporting Information).…”

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

“…For unequivocal identification of CWC-related chemicals in real samples or PTs, the availability of mass spectra and interpretation skills are essential requirements. Despite global efforts, due to the extreme toxicity of the CWC-related chemicals, there are a limited number of research reports available for such chemicals [7][8][9][10][11][12][13]. Toxic chemical destruction can be defined as a method involving the conversion of toxic chemicals into harmless and non-toxic products by suitable chemical reaction [14,15].…”

Gas Chromatography-Mass Spectrometric Studies of O-Alkyl O-2-(N,N-Dialkylamino) Ethyl Alkylphosphonites(Phosphonates) for Chemical Weapons Convention Verification

“…[1][2][3] This convention, which prohibits development, production, stockpiling and use of chemical weapons, was available for signature on January 13, 1993 and came into force on April 29, 1997. For CWC implementation, toxic chemicals, precursors and most related chemicals are listed in three distinct CWC schedules contained in the annex on chemicals.…”