Hydrolysis and Oxidation Products of the Chemical Warfare Agents 1,2-Bis[(2-chloroethyl)thio]ethane Q and 2,2′-Bis(2-chloroethylthio)diethyl Ether T

Syntheses of diols of structure [HOCH2CH2S]2(CH2)n in 86–95% yield from the sodium salt of 2-mercaptoethanol and Br(CH2)nBr (n = 1 to 5) or in 60–90% yield from 2-chloroethanol and NaS(CH2)nSNa (n = 2 to 5) are described. The diol [HOCH2CH2SCH2CH2]2O was prepared in 82% yield from the sodium salt of 2-mercaptoethanol and [ClCH2CH2]2O, and in 88% yield from 2-chloroethanol and [HSCH2CH2]2O. Mono- and bis-sulfoxides and bis-sulfones of these species were prepared in generally high yield by treatment with an equivalent of KIO4 in aqueous methanol, two equivalents of NaIO4 in aqueous methanol, or four equivalents of H2O2 in trifluoroacetic acid respectively. The compounds are important analytical standards for investigating the fate of the chemical warfare agents sesquimustard Q and oxygen mustard T in environmental samples.