In situ nucleophilic substitution reaction of N,N-dialkylaminoethyl-2-chlorides monitored by gas chromatography/mass spectrometry

The detection and identification of degradation products of scheduled chemicals, which are characteristic markers of Chemical Warfare agents (CWAs), plays a key role in verification analysis. Identification of such non‐scheduled but specific markers of CWAs helps in deciphering the kind of agent that was present in the sample submitted for off‐site analysis. This paper describes the stability of N,N‐dialkylaminoethyl‐2‐chlorides, which are precursors for highly toxic chemicals like VX, in different solvents. These compounds are stable in chloroform, acetonitrile, hexane and dichloromethane but tend to undergo in situ nucleophilic substitution reaction in the presence of alcohols giving the corresponding alkyl ether. The study shows that N,N‐dialkylaminoethyl alkyl ethers can be used as markers of N,N‐dialkylaminoethyl‐2‐chlorides. A detailed degradation study of these compounds in the presence of alcohols was carried out and it was found that the reaction follows pseudo‐first order kinetics. Electron ionization mass spectral data for the methyl ethers of all the compounds are briefly discussed. Copyright © 2006 John Wiley & Sons, Ltd.