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- W2073610688 abstract "Das Radikal Ph2C. — tBu (1) dimerisiert reversibel zum chinoiden Derivat 3 und nicht zum ethan-artigen 2, wie in der Literature berichtet. Im Gleichgewicht liegt weniger Radikal 1 vor als im Fall von Triphenylmethyl, ΔHDiss = 18.5 ± 2 kcal/mol für 3. Sowohl das Radikal 1 wie sein Dimeres 3 werden durch Sauerstoff rasch oxidiert. 1 gibt das Dialkylperoxid 6, das schon bei 20°C fragmentiert, hauptsächlich zu Benzophenon und tBu., 3 führt zum Keton 7, wahrscheinlich über das Hydroperoxid 10. 3 lagert sich, sowohl säure- wie basenkatalysiert, unter 1,5-H-Verschiebung um in das benzoide Derivat 4. Einzelheiten zu den Darstellungen sowie zur ESR-Spektroskopie werden angegeben. Sterically Hindered Free Radicals, XII. The Radical tert-Butyldiphenylmethyl, Its Dimer, and Their Autoxidation. A Reinvestigation The radical Ph2C. — tBu (1) dimerizes giving reversibly the quinonoid derivative 3, and not the ethane-like 2 as reported in the literature. In equilibrium there are less radicals 1 than in the case of triphenylmethyl, ΔHdiss = 18.5 ± 2 kcal/mol for 3. Both the radical 1 and its dimer 3 are rapidly oxidized by oxygen. 1 gives the dialkyl peroxide 6 which fragmentates already at 20°C mainly to benzophenone and tBu., 3 leads to the ketone 7, probably via the hydroperoxide 10. 3 rearranges catalysed by acid and by base as well via a 1,5-hydrogen migration forming the benzenoid derivative 4. Preparative and ESR details are given." @default.
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- W2073610688 date "1985-02-01" @default.
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- W2073610688 title "Über sterisch gehinderte freie Radikale, XII. Das Radikaltert-Butyldiphenylmethyl, sein Dimeres sowie deren Autoxidation. Eine Neuuntersuchung" @default.
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- W2073610688 doi "https://doi.org/10.1002/cber.19851180206" @default.
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