title: Bis(dialkylamide)hydrogen dibromobromate precursors of hypobromite ion in reactions with nerve and blister agent simulants.
abstract: Hypobromite ion, BrO(-), is an effective alpha-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.
authors.affiliation: L.M. Litvinenko Institute of Physical Organic & Coal Chemistry, National Academy of Sciences of Ukraine, 83114 R. Luxemburg St., 70 Donetsk, Ukraine.
authors.forename: Yuri S
authors.initials: YS
authors.lastname: Simanenko
authors.forename: Vera A
authors.initials: VA
authors.lastname: Savelova
authors.forename: Tatyana M
authors.initials: TM
authors.lastname: Prokop'eva
authors.forename: Vasily A
authors.initials: VA
authors.lastname: Mikhailov
authors.forename: Marya K
authors.initials: MK
authors.lastname: Turovskaya
authors.forename: Eugen A
authors.initials: EA
authors.lastname: Karpichev
authors.forename: Anatolii F
authors.initials: AF
authors.lastname: Popov
authors.forename: Nicholas D
authors.initials: ND
authors.lastname: Gillitt
authors.forename: Clifford A
authors.initials: CA
authors.lastname: Bunton
mesh_terms: D001768:Blister / Q000139:chemically induced*; D017605:Bromine Compounds / Q000737:chemistry*; D002619:Chemical Warfare Agents / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration
chemical_list: D017605:Bromine Compounds; D002619:Chemical Warfare Agents