- Experimental evidence for the formation of cationic intermediates during iodine(iii)-mediated oxidative dearomatization of phenols
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Iodine(iii)-based oxidants are commonly used reagents for the oxidative dearomatization of phenols. Having a better understanding of the mechanism through which these reactions proceed is important for designing new iodine(iii)-based reagents, catalysts, and reactions. We have performed a Hammett analysis of the oxidative dearomatization of substituted 4-phenylphenols. This study confirms that iodine(iii)-mediated oxidative dearomatizations likely proceed through cationic phenoxenium ions and not the direct addition of a nucleophile to an iodine-bound phenol intermediate.
- Tang, Ting,Harned, Andrew M.
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p. 6871 - 6874
(2018/10/02)
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- Structural and Solvent/Electrolyte Effects on the Selectivity and Efficiency of the Anodic Oxidation of Para-Substituted Aromatic Ethers. An Efficient Route to Quinol Ether Ketals and Quinol Ethers
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The anodic oxidations of the methyl ethers of p-arylphenols C6H4, o-C6H4, o-HO2CC6H4>, the 2-hydroxyethyl ethers of p-arylphenols , and the 2-hydroxyethyl ethers of p-alkylphenols and 4-methyl-1-naphthol were studied.The p-aryl aromatic ethers underwent anodic oxidation in good yield to give the corresponding p-quinol ether ketals.The ratio of nuclear to side-chain products from anodic oxidation of p-alkylanisole derivatives is dependent upon the electrolysis conditions.The 2-hydroxyethyl ether derivatives of p-alkylphenols markedly favor the formation of nuclear oxidation products - providing a useful route to the corresponding p-quinol ether ketals.In addition, methanolic potassium fluoride improves the efficiency of these anodic oxidation processes by about 400percent relative to methanolic potassium hydroxide.These reactions were performed at a constant current (1.0-2.0 A) in a single cell and serve as preparative routes to p-quinol ether ketals and quinol ethers via acid hydrolysis.
- Capparelli, Michael P.,DeSchepper, Richard E.,Swenton, John S.
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p. 4953 - 4961
(2007/10/02)
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- ANODIC OXIDATION STUDIES OF OXYGENATED BIPHENYLS. CONVENIENT SYNTHETIC ROUTES TO CERTAIN FUNCTIONALIZED BIPHENYLS
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The anodic oxidation of oxygenated biphenyls produces phenyl-substituted p-quinol ether ketals in good-to-excellent yield.These compounds are useful substrates for preparation of more highly functionalized biphenyls.
- DeSchepper, Richard E.,Swenton, John S.
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p. 4831 - 4834
(2007/10/02)
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