Seyed Esmaeil Hosseini1,2, Hamid Saeidian3, Ali Amozadeh1, Mohammad Taghi Naseri2, Mehran Babri2. 1. Department of Chemistry, Semnan University, P.O. Box 35131, -19111, Semnan, Iran. 2. Defense Chemical Research Lab (DCRL), P.O. Box 31585, -1461, Karaj, Iran. 3. Department of Science, Payame Noor University (PNU), P.O. Box 19395, -4697, Tehran, Iran.
Abstract
RATIONALE: For unambiguous identification of Chemical Weapons Convention (CWC)-related chemicals in environmental samples, the availability of mass spectra, interpretation skills and rapid microsynthesis of suspected chemicals are essential requirements. For the first time, the electron ionization single quadrupole and electrospray ionization tandem mass spectra of a series of O-alkyl N-[bis(dimethylamino)methylidene]-P-methylphosphonamidates (Scheme 1, cpd 4) were studied for CWC verification purposes. METHODS: O-Alkyl N-[bis(dimethylamino)methylidene]-P-methylphosphonamidates were prepared through a microsynthetic method and were analyzed using electron ionization and electrospray ionization mass spectrometry with gas and liquid chromatography, respectively, as MS-inlet systems. General EI and ESI fragmentation pathways were proposed and discussed, and collision-induced dissociation studies of the protonated derivatives of these compounds were performed to confirm proposed fragment ion structures by analyzing mass spectra of deuterated analogs. RESULTS: Mass spectrometric studies revealed some interesting fragmentation pathways during the ionization process, such as McLafferty rearrangement, hydrogen rearrangement and a previously unknown intramolecular electrophilic aromatic substitution reaction. CONCLUSIONS: The EI and ESI fragmentation routes of the synthesized compounds 4 were investigated with the aim of detecting and identifying CWC-related chemicals during on-site inspection and/or off-site analysis and toxic chemical destruction monitoring.
RATIONALE: For unambiguous identification of Chemical Weapons Convention (CWC)-related chemicals in environmental samples, the availability of mass spectra, interpretation skills and rapid microsynthesis of suspected chemicals are essential requirements. For the first time, the electron ionization single quadrupole and electrospray ionization tandem mass spectra of a series of O-alkyl N-[bis(dimethylamino)methylidene]-P-methylphosphonamidates (Scheme 1, cpd 4) were studied for CWC verification purposes. METHODS:O-Alkyl N-[bis(dimethylamino)methylidene]-P-methylphosphonamidates were prepared through a microsynthetic method and were analyzed using electron ionization and electrospray ionization mass spectrometry with gas and liquid chromatography, respectively, as MS-inlet systems. General EI and ESI fragmentation pathways were proposed and discussed, and collision-induced dissociation studies of the protonated derivatives of these compounds were performed to confirm proposed fragment ion structures by analyzing mass spectra of deuterated analogs. RESULTS: Mass spectrometric studies revealed some interesting fragmentation pathways during the ionization process, such as McLafferty rearrangement, hydrogen rearrangement and a previously unknown intramolecular electrophilic aromatic substitution reaction. CONCLUSIONS: The EI and ESI fragmentation routes of the synthesized compounds 4 were investigated with the aim of detecting and identifying CWC-related chemicals during on-site inspection and/or off-site analysis and toxic chemical destruction monitoring.
Authors: Marcelo C Santos; Fernanda D Botelho; Arlan S Gonçalves; Daniel A S Kitagawa; Caio V N Borges; Taynara Carvalho-Silva; Leandro B Bernardo; Cíntia N Ferreira; Rafael B Rodrigues; Denise C Ferreira Neto; Eugenie Nepovimova; Kamil Kuča; Steven R LaPlante; Antonio L S Lima; Tanos C C França; Samir F A Cavalcante Journal: Arch Toxicol Date: 2022-06-06 Impact factor: 6.168
Authors: Tanos C C Franca; Daniel A S Kitagawa; Samir F de A Cavalcante; Jorge A V da Silva; Eugenie Nepovimova; Kamil Kuca Journal: Int J Mol Sci Date: 2019-03-11 Impact factor: 5.923