- REACTIONS OF TRANSIENT C-NITROSOCARBONYL COMPOUNDS WITH DIENES, MONOOLEFINS, AND NUCLEOPHILES
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Nitrosocarbonylbenzene and nitrosocarbonylmethane, formed as transient intermediates by oxidation of benzo- and aceto-hydroxamic acid, respectively, with tetraethylammonium periodate, are trapped by cyclopentadiene to give the corresponding cycloadducts (5).The adduct (5; R=Ph) dissociates in solution at 80 deg C to reform nitrosocarbonylbenzene, which reacts with thebaine (1) to give (4; R=Ph) and with triphenylphosphine to give phenyl isocyanate.Cycloadducts of nitrosocarbonylbenzene with cyclohexa-1,3-diene (6) and with cyclo-octatetraene (7) have also been prepared.The adduct (3; R=Ph) of nitrosocarbonylbenzene and 9,10-dimethylanthracene, when heated with 1-allyl-3,4-methylenedioxybenzene, oct-1-ene, or 2,5-dimethylhexa-2,4-diene, gives the corresponding 'ene' reaction products of the olefins and nitrosocarbonylbenzene.When heated alone, the adduct (3; R=Ph) gives 9,10-dimethylanthracene, benzoic anhydride, and nitrous oxide.Oxidation of 2,4,6-trimethylbenzohydroxamic acid in the presence of thebaine gives the adduct (4; R=2,4,6-trimethylphenyl).However, 2,4,6-trimethylnitrosocarbonylbenzene is insufficiently stable to be isolated; in the absence of a diene it decomposes to give 2,4,6-trimethylbenzoic anhydride as the major product.
- Corrie, John E.T.,Kirby, Gordon W.,Mackinnon, John W.M.
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p. 883 - 886
(2007/10/02)
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