Oxidative Detoxification of Sulfur-Containing Chemical Warfare Agents by Electrophilic Iodine

Boris Smolkin, Noam Levi, Naama Karton-Lifshin, Lea Yehezkel, Yossi Zafrani, Ishay Columbus

Research output: Contribution to journalArticlepeer-review

17 Scopus citations

Abstract

Mild oxidation of sulfur-containing chemical warfare agents was performed in organic medium by electrophilic iodine reagents. Kinetic experiments on sulfur mustard (HD) showed rapid (t1/2 < 3 min) and selective oxidation to the nonvesicant sulfoxide product (HD-SO) in acetonitrile or propylene carbonate solutions (9% water added) containing excess N-iodosuccinimide (NIS). Molecular iodine solutions in these solvents led to similar results as with NIS but at much slower rates (t1/2 ∼ 90 min). Higher donor number solvents, such as THF, DMF, or DMSO, showed slower rates with both iodine and NIS. The oxidation of the nerve agent O-ethyl-S-2-(N,N-diisopropylaminoethyl)methylphosphonothioate (VX) selectively to the nontoxic ethyl methylphosphonic acid product exhibited fast rates (t1/2 = 6 min) using NIS in DMSO solution. In all other solvents tested with VX, rates were slower (t1/2 ∼ 30-70 min). Oxidation experiments under the same conditions with chloroethyl ethyl sulfide (HD simulant) and O,S-diethyl methylphosphonothioate (VX simulant) led to much faster reaction rates. These transformations are believed to proceed through electrophilic iodine attack on the sulfur moiety and display solvent dependency based on the agents' structural and chemical properties.

Original languageEnglish
Pages (from-to)13949-13955
Number of pages7
JournalJournal of Organic Chemistry
Volume83
Issue number22
DOIs
StatePublished - 16 Nov 2018
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2018 American Chemical Society.

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