Sulfonium Chlorides Derived from 1-Chloroethyl Sulfides. 2. Effects of Solvent and Substrate Concentration

摘要

The hydrolysis reaction products of mustard (2,2'-dichlorodiethyl sulfide or H) and two monofunctional simulants (2-chloroethyl methyl sulfide (CEMS) and 2-chloroethyl ethyl sulfide (CEES)) are measured by 13C and/or 1H NMR with temperature at 20 C. The substrate concentration varies from 0.001 to 0.2 M, and the solvent systems include pure water, acetone water mixtures, a carbonate buffer at pH 10, and a carbonated microemulsion at pH 10. In the pH 10 solutions, the corresponding 2-hydroxyethyl sulfides are the initial products. However, dimeric sulfonium ions start to form as stable products subsequently. In the neutral solvent systems, two types of dimeric sulfonium chlorides (Compound I, (RSCH2CH2)S+(R) (CH2CH2OH) and Compound II, (RSCH2CH2)S+(R) (CH2CH2C1) are produced from 0.1 to 0.20 M substrates; only small amounts of the corresponding 2 hydroxyethyl sulfides are formed from hydrolysis. Keywords: Sulfonium chlorides, Mustard gas, Ethyl radicals, Chloroethyl sulfides, Acetone water, Nucleophilic attack, Hydroxyethyl sulfide, Sulfides. (MJM)