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

• Published in: Journal of organic chemistry 2004-12, Vol.69 (26), p.9238-9240
• Main Authors: Simanenko, Yuri S, Savelova, Vera A, Prokop'eva, Tatyana M, Mikhailov, Vasily A, Turovskaya, Marya K, Karpichev, Eugen A, Popov, Anatolii F, Gillitt, Nicholas D, Bunton, Clifford A
• Format: Article
• Language: English
• Subjects: Biological and medical sciences; Blister - chemically induced; Bromine Compounds - chemistry; Chemical and industrial products toxicology. Toxic occupational diseases; Chemical Warfare Agents - chemistry; Chemistry; Exact sciences and technology; Gas, fumes; Heterocyclic compounds; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Hydrogen-Ion Concentration; Kinetics and mechanisms; Medical sciences; Organic chemistry; Preparations and properties; Reactivity and mechanisms; Toxicology
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo0402430

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 (t 1/2 = 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.