Reduction of o-iodosobenzoate ion by sulfides and its oxidative regeneration

✍ Scribed by Clifford A Bunton; Houshang J Foroudian; Nicholas D Gillitt

• Book ID: 101288253
• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 100 KB
• Volume: 12
• Category: Article
• ISSN: 0894-3230
• DOI: 10.1002/(sici)1099-1395(199910)12:10<758::aid-poc200>3.0.co;2-a

✦ Synopsis

o-Iodosobenzoate and o-iodoxybenzoate ion (IBA and IBX, respectively) are turnover catalysts of hydrolyses of phosphonofluoridates and non-toxic simulants. Reactions of IBA with phosphonothioates are stoichiometric because sulfides (e.g. 4-methoxybenzenethiol) reduce IBA to o-iodobenzoate ion. Oxidants, e.g. HSO À 5 , as OXONE, and magnesium peroxyphthalate, MPPA, regenerate IBA and gradually oxidize it to IBX, which eventually decomposes. The procedure was tested on hydrolyses of p-nitrophenyl diphenylphosphate (pNPDPP) and 4-nitrobenzenesulfonyl fluoride, 1, catalyzed by IBA, and the catalyzed hydrolysis of 1 was examined. Some of the oxidation products of 4-methoxybenzene thiol were identified by 1 H NMR spectroscopy and oxidative decomposition of IBX was monitored. Periodate ion slowly oxidized o-iodobenzoate ion to IBA and IBX.