- Hydrolysis of sesquimustards
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The hydrolysis of the sesquimustards 1,2-bis(2-chloroethylthio)ethane (QN2) and 1,3-bis(2-chloroethylthio) propane (QN3) has been studied by 1H and 13C nuclear magnetic resonance spectroscopy. For both sesquimustards, stable cyclic sulfonium ions were observed in hydrolysis experiments in a 1 : 1 mixture of [D6]acetone and D2O. The cyclic sulfonium ions, which persist in the aqueous solution for up to a week, are likely to retain some toxicity and could possibly be used as markers for sesquimustards in the analysis of mustard-contaminated soil for chemical weapons treaty verification. The formation of a macrocyclic oxadithiaether was also demonstrated for QN2 but not QN3.
- St Quintin, Timothy D.,Ralph Leslie,Grant Collins
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- Unexpected Reaction Pathways Leading to Thiodiglycol during the Degradation of Long-Chain Sulfur Mustards
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Degradation of long-chain sulfur mustards with various commercial decontaminants unexpectedly forms thiodiglycol (TDG) through unreported reaction pathways. Chemical warfare agents (CWAs) degradation products have to be unambiguously related to their reference compounds in order to fulfill international verification protocols. Thus, the formation of TDG using water-based decontaminants introduces an uncertainty in the origin of this chemical that has been systematically used to unambiguously demonstrate the presence of yperite in environmental and biomedical samples. Therefore, these novel and unprecedented degradation pathways will result either in modifications of the international verification protocols for forensic purposes or in the exclusion of TDG as an exclusive marker of yperite.
- Gómez-Caballero, Esther,Martínez-álvarez, Roberto,Sierra, Miguel A.
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p. 12432 - 12439
(2018/10/15)
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- Mass spectral studies on vinylic degradation products of sulfur mustards under gas chromatography/mass spectrometry conditions
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Sulfur mustards are a class of vesicant chemical warfare agents that rapidly degrade in environmental samples. The most feasible degradation products of sulfur mustards are chloroethyl vinylic compounds and divinylic compounds, which are formed by the elimination of one and two HCl molecules from sulfur mustards, respectively. The detection and characterization of these degradation products in environmental samples are an important proof for the verifcation of sulfur mustard usage. In this study, we synthesized a set of sulfur mustard degradation products, i.e., divinylic compounds (1-7) and chloroethyl vinylic compounds (8-14), and characterized using gas chromatography/mass spectrometry (GC/MS) under electron ionization (EI) and chemical ionization (CI) (methane) conditions. The EI mass spectra of the studied compounds mainly included the fragment ions that resulted from homolytic cleavages with or without hydrogen migrations. The divinylic compounds (1-7) showed [M - SH]+ ions, whereas the chloroethylvinyl compounds (8-14) showed [M - Cl]+ and [M - CH2CH2Cl]+ ions. Methane/CI mass spectra showed [M + H]+ ions and provided molecular weight information. The GC retention index (RI) values were also calculated for the studied compounds. The EI and CI mass spectral data together with RI values are extremely useful for off-site analysis for the verifcation of the chemical weapons convention and also to participate in offcial Organization for the Prohibition of Chemical Weapons profciency tests.
- Sai Sachin,Karthikraj,Kalyan Kumar,Sony,Prasada Raju,Prabhakar
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p. 791 - 800
(2016/04/01)
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