Study of electron ionization mass spectra of bis(trimethylsilyl) esters of alkylphosphonic and alkylthiophosphonic acids

Gas chromatography/mass spectrometric analysis of methyl esters of N,N‐dialkylaminoethane‐2‐sulfonic acids for verification of the Chemical Weapons Convention

“…The ion with m/z 123 [8] was unexceptionally present in all compounds and produced the ion with m/z 79 [9] by elimination of C 2 H 4 O (Scheme 1). The molecular ion also fragmented by elimination of the alkyl radical from nitrogen (presumably in a charge-site initiation reaction followed by rearrangement of hydrogen, rH) producing ions [10] and [11].…”

“…We have recently reported the GC/MS analysis of esters of alkylphosphonic acids. 9 Since the dialkylami-of DAESAs in a sample submitted for off-site analysis implies contamination with either VX type nerve agents (schedule 1.A.3) or N,N-dialkylaminoethane thiols (schedule 2.B.12). Particularly, if due to complete degradation, the nerve agents themselves are not detected, then detection of alkylphosphonic acids along with DAESAs could reveal the identity of the original contaminant (the VX type nerve agent), which is the ultimate goal of verification analysis of the CWC.…”

“…Since gas chromatography coupled with mass spectrometry (GC/ MS) is the widely used technique for identification of CWCrelated compounds, [17][18][19][20] a great deal of work is devoted to the development of a mass spectral database of these compounds. 8,9,[21][22][23][24] The chemicals relevant to the convention are enlisted in three schedules of an annex of the CWC. The categorization of chemicals in the three schedules is based on the toxicity, past use as CWAs, and commercial applicability of chemicals.…”

Gas chromatography/mass spectrometric analysis of N,N‐dialkylaminoethyl‐2‐chlorides and trimethylsilyl derivatives of N,N‐dialkylaminoethan‐2‐ols for verification of the Chemical Weapons Convention

“…The molecular ion fragmented by elimination of an alkyl radical (presumably in a charge-site initiation reaction followed by rearrangement of hydrogen, rH) producing ions [8] and [10], which then further fragmented to ions [9] and [11], respectively. These ions were indistinguishable from other ions for most of the compounds (Table 1, examples: entry 2 for ion m/z 92 [5] and [10], entry 3 for ion m/z 120 [3] and [5], entry 4 for ion m/z 92 [5] and [10] and entry 6 for ion m/z 106 [5] and [10]); hence, formation of these species cannot be confirmed in the EI-MS of these compounds.…”

“…Since gas chromatography coupled with mass spectrometry (GC/MS) is the most widely used technique for identification of CWC-related compounds (CRCs), [17][18][19][20] a great deal of work has been devoted to the development of a GC/MS database of these compounds. 8,9,[21][22][23][24] The chemicals of significance are listed in three schedules of an annex of the CWC. The categorization of the chemicals is based on their toxicity, past use as CWAs, and their commercial applicability.…”