Mass spectrometry as a tool for characterization of N,N-dialkylaminoethane-2-thiols - precursors and degradation products of chemical warfare agents

N,N-dialkylaminoethane-2-thiols belong to the group of precursors and degradation products of chemical warfare agents (CWAs). These compounds were analyzed by means of electrospray ionization-multiple stage mass spectrometry (ion trap) and proposed fragments were confirmed by accurate mass measurement using a QqTOF system. The fragmentation pathways of studied compounds and the products of oxidation (formation of -S-S- linkage) were described. Some minor interesting processes, such as rearrangement of SH group, were observed and proved. A new mu LC/MS method, based on ion-pairing chromatography, was developed. Trifluoroacetic acid was employed as an ion-pairing agent to increase the low retention of compounds of interest in the reverse-phase system. The technique was compared with the UPLC/MS method, allowing fast analysis of all the studied thiols as well as an explorative control of originated disulfides. Copyright (C) 2009 John Wiley & Sons, Ltd.