Reaction of Lewisite-1 with Alcohols, Diols, and Thiols in Water—A Simple Method of Derivatization of Thiodiglycol

Abstract

Reaction of 2-chlorovinyldichloroarsine (Lewisite-1) with alcohols, thiols, diols, and hydroxy thiols in water at 40°C has been examined. The expected derivatization products, dialkyl 2-chlorovinylarsonites or corresponding arsonodithiolites, were obtained with alcohols and thiols, whereas reactions with bifunctional diols and hydroxythiols produced analogous cyclic esters. All derivatives may be easily detected using gas chromatography. This reaction was found useful to easily transform bis(2-hydroxyethyl) sulfide (thiodiglycol), a sulfur mustard decomposition product, to a stable eight-membered cyclic arsonite derivative. After extraction with dichloromethane, the derivative may be easily and selectively detected using GC/MS at a 100 ppb level thiodiglycol content in water matrices, eliminating tedious evaporation of water and then silylation. This method may be applied to analyze Chemical Weapons Convention related environmental water samples.

Keywords:

• Alcohols
• derivatization
• diols
• gas chromatography
• lewisite
• thiodiglycol

Acknowledgments

We would like to thank Dr. Peter Siegenthaler for performing the NMR spectra.