Reaction with hydroperoxide anion

The hydroperoxide radical reacts with another molecule of oxygen (Reaction 5) to give the hydroperoxide-peroxy radical. This radical in turn reacts with a molecule of dihydroanthracene (Reaction 6), to give the dihydroperoxide and generate a radical to propagate the chain. However, the hydroperoxide radical formed in Reaction 4 may be decomposed by a carbanion to the anthracene diradical (Reaction 7). [An example of the decomposition of an unstable hydroperoxide by reaction with an anion is found in the basic autoxidation of 2-nitropropane (3).]... 

The mechanism of the reaction is believed to be that shown in equation (9), this bong a specific example of equation (1), with hydroperoxide anion being the reactive species. Detailed study has led to the proposal of various transition states at different pH values.However, the reaction may be carried out satisfactorily over a wide range of concentrations of base and hydrogen peroxide providing that the reaction mixture is kept alkaline, as otherwise radical reactions may intervene with deleterious stereochemical consequences. 

R = H) is a potent dienophile/ Unlike open-chain a/3-unsaturated sul-phones, it does not form the corresponding epoxide when treated with hydroperoxide anion, but instead yields the ketone (254) 3-substituted benzothiophen dioxides (253 R = Me, Et, or Ph) give alcohols (255) in this reaction. ... 

FIGURE 11.57 Reaction of trialkylborane with hydroperoxide anion. 

Free radicals are produced by the reactions of HBr and the bromide anion with hydroperoxide [198] ... 

The mechanism by which the hydroperoxide intermediate, (42) (Scheme 29) is converted into the products of Scheme 28 is not clear. The follow-up reaction of (42) may be diverted by reaction with an enone that undergoes epoxidation in 85 to 90% yield. Scheme 29, [121]. The epoxidation reaction does not take place directly from O2 and 02 but requires the formation of an intermediate of type (42) derived either from the enone or from an external carbon acid as in Scheme 29. Yields are considerably improved using an external carbon acid since the Michael addition between the enone and its anion otherwise competes with the epoxidation. For... 

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