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Bis(dialkylamide)hydrogen Dibromobromate Precursors of Hypobromite Ion in Reactions with Nerve and Blister Agent Simulants

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journal contribution
posted on 24.12.2004, 00:00 by Yuri S. Simanenko, Vera A. Savelova, Tatyana M. Prokop'eva, Vasily A. Mikhailov, Marya K. Turovskaya, Eugen A. Karpichev, Anatolii F. Popov, Nicholas D. Gillitt, Clifford A. Bunton
Hypobromite ion, BrO-, is an effective α-nucleophile that reacts rapidly with activated phosphorus(V) and sulfonate esters. The parent acid rapidly oxidizes organic sulfides and aryloxide ions. At pH 10−11 BrO- and HOBr coexist in water and are potentially useful as decontaminants of chlorosulfide blister agents and the phosphonyl nerve agents. Bis(dialkylamide)hydrogen dibromobromates are well characterized, stable, solids which rapidly form HOBr−BrO- in mildly alkaline water. Reactions of 4-nitrophenyl diethyl phosphate and phosphonate, which are simulants of the phosphonofluoridate nerve agents, and of 4-nitrophenyl tosylate, with BrO- are rapid (t1/2 = 60−700 s) with 0.1 M BrO-, under conditions in which oxidations of organic sulfides are too fast to be followed by conventional methods.