EPR and ENDOR studies of 6-substituted benzo[a]pyrene cation radicals

Sullivan, Paul D.; Ocasio, Ignacio; Chen, Xinhua.; Bannoura, Fouad

doi:10.1021/ja00262a012

Cited by 9 publications

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“…ESR studies of 9,10-diethylanthracene and 6-ethylbenzo[ a ]pyrene radical cations yield a hyperfine coupling constant indicative of a ca. 90° alignment of the ethyl group with respect to the aromatic plane, which would make deprotonation difficult in the presence of a compelling stereoelectronic effect. Indeed, we have discovered that 9,10-diethylanthracene undergoes inefficient side-chain oxidation with tris(phenanthroline)iron(III) in aqueous acetonitrile, a phenomenon we associated with steric inhibition of deprotonation …”

Section: Introductionmentioning

confidence: 99%

Chemistry of Arylalkyl Radical Cations: Deprotonation vs Nucleophilic Attack

Tolbert

Sirimanne

et al. 1997

J. Org. Chem.

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Radical-cation-mediated oxidation of 9-methylanthracene (9MA) by pyridine/iodine in chloroform produces mainly the product of nucleophilic attack at the open C-10 position. When methyl is replaced by ethyl as in 9-ethylanthracene (9EA), the nucleophilic product is the only one observed. Alternatively, aceanthrene (AA), the 1,9-ethano-bridged equivalent of 9EA, produces mainly the product of side-chain substitution. Stereoelectronic control in the deprotonation is proposed as the rationale for this difference in reactivity, as well as for other radical-cation-mediated oxidations.

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Section: Introductionmentioning

confidence: 99%