Practical benzylation of N,N-substituted ethanolamines related to chemical warfare agents for analysis and detection by electron ionization gas chromatography–mass spectrometry

The benzylation of three low molecular weight N,N-disubstituted ethanolamines related to chemical warfare agents (CWAs) to furnish derivatives with improved gas chromatography-mass spectrometry (GC-MS) profiles is described. Due to their low molecular weight and polar nature, N,N-disubstituted ethanolamines are notoriously difficult to detect by routine GC-MS analyses during Organisation for the Prohibition of Chemical Weapons (OPCW) proficiency tests (PTs), particularly in scenarios when they are present at low levels (~1–10 ppm) amidst more abundant interferences. Our studies revealed that the optimal derivatization conditions involved the treatment of the ethanolamine with benzyl bromide in the presence of an inorganic base (e.g., Na₂CO₃) in dichloromethane at 55°C for 2 h. This optimized set of conditions was then successfully applied to the derivatization of N,N-dimethylethanolamine, N,N-diethylethanolamine and N,N-diisopropylethanolamine present separately at 1 and 10 μg/mL concentrations in a glycerol-rich matrix sample featured in the 48th OPCW PT. The benzylated derivatives of the three ethanolamines possessed retention times long enough to clear the massive glycerol-containing matrix interferences. The protocol herein is introduced as an alternative method for derivatization of these CWA and pharmaceutically important species and should find broad applicability in laboratories where routine forensic analysis is carried out.     

The Syrian chemical weapons disarmament process in context: narratives of coercion,consent, and everything in between

This article explores the successful Syrian chemical weapons disarmament process (2013–2014) within the context of post-Cold War coercive arms control policy and scholarship, particularly related to the Middle East. Based on extensive interviews with individuals involved in the process, we explore the coexistence of two rival, apparently contradictory narratives: one (backed by Western states) claimed coercion was the main contributor to disarmament, while the other (defended by Syrian authorities and Russia) insisted on the process’s consensual features. Our study suggests that the hybrid disarmament framework, embodied in a unique joint mission between the United Nations and the Organisation for the Prohibition of Chemical Weapons, conveniently accommodated both narratives, which in turn contributed to the mission’s success. We then ask whether, with the apparent US retreat in the Middle East, the Syrian case (as well as the 2015 Iran nuclear deal) signals a possible turn in international non-conventional arms control processes that would leave more room for consent and diplomacy.