Reactions of Nitric Oxide and Nitrogen Dioxide with Functionalised Alkenes and Dienes

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Pure nitric oxide does not add to alkenes containing acceptor or donor substituents, or to conjugated dienes, to afford beta-nitrosoalkyl radicals. EPR spectra show that reactions are initiated by NO2 addition to carbon-carbon double bonds to produce beta-nitroalkyl radicals which combine with nitric oxide to yield beta-nitro-nitroso-compounds. The latter trap other radicals to afford mixtures of aminoxyl radicals and, where possible, the nitroso-compounds tautomerise to oximes which oxidise to iminoxyl radicals. EPR spectra obtained on reaction of NO-NO2 mixtures with 2,5-dimethylhexa-2,4-diene have shown the presence of a di-tert-alkylaminoxyl plus a tert,sec-dialkylaminoxyl, providing good support for this mechanism. Product analyses have established that 2-oxo-4-methylpent-3-ene and 1-acetylcyclohexene undergo extensive oxidative degradation. For enol ethers, reaction with NO-NO2 leads to hydrolysis giving the corresponding carbonyl compound and alcohol, followed by ketal and ester formation.

Original languageEnglish
Pages (from-to)2579-2583
Number of pages5
JournalJournal of Chemical Society, Perkin Transactions 2
Issue number12
Publication statusPublished - Dec 1997




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