Oxidative phenolic coupling

Reaction that can be carried out by the oxidative coupling of radicals may also be initiated by irradiation with UV light. This procedure is especially useful if the educt contains oleflnic double bonds since they are vulnerable to the oxidants used in the usual phenol coupling reactions. Photochemically excited benzene derivatives may even attack ester carbon atoms which is generally not observed with phenol radicals (I. Ninoraiya, 1973 N.C. Yang, 1966). 

W. I. Taylor and A. R. Battersby, eds.. Oxidative Coupling of Phenols, Marcel Dekket, New York, 1967. 

Polymerization Mechanism. The mechanism that accounts for the experimental observations of oxidative coupling of 2,6-disubstituted phenols involves an initial formation of aryloxy radicals from oxidation of the phenol with the oxidized form of the copper—amine complex or other catalytic agent. The aryloxy radicals couple to form cyclohexadienones, which undergo enolization and redistribution steps (32). The initial steps of the polymerization scheme for 2,6-dimethylphenol are as in equation 6. 

Removal of tert-AW Groups, Alkyl groups on a phenol nucleus can be removed selectively to produce a desired synthetic result. The oxidative coupling of phenol offers a good example. 2,6-Di-/ f2 -butylphenol can be coupled under oxidative conditions to... 

Oxidative Reactions. The majority of pesticides, or pesticide products, are susceptible to some form of attack by oxidative enzymes. For more persistent pesticides, oxidation is frequently the primary mode of metaboHsm, although there are important exceptions, eg, DDT. For less persistent pesticides, oxidation may play a relatively minor role, or be the first reaction ia a metaboHc pathway. Oxidation generally results ia degradation of the parent molecule. However, attack by certain oxidative enzymes (phenol oxidases) can result ia the condensation or polymerization of the parent molecules this phenomenon is referred to as oxidative coupling (16). Examples of some important oxidative reactions are ether cleavage, alkyl-hydroxylation, aryl-hydroxylation, AJ-dealkylation, and sulfoxidation. 

When chloroform or methanol is used as the solvent for the oxidation of phenols, other products, originating from coupling of aryloxy radicals, e.g., polyphenylene ethers and/or diphenoquinones, are also formed. ... 

Various 2,6-di8ubstituted p-benzoquinones have been prepared by oxidation of the corresponding 2,6-disubstituted phenols with potassium nitrosodisulfonate or lead dioxide in formic acid. Oxidative coupling of 2,6-disubstituted phenols to poly-2,6-disubstituted phenylene ethers followed by treatment of the polymers in acetic acid with lead dioxide is reported to give low yields of the corresponding 2,6-disubstituted p-benzoquinones. 

Although this isoquinoline at first bears little structural resemblance to morphine (108), careful rearrangement of the structure (A) shows the narcotic to possess the benzylisoquinoline fragment within its framework. Indeed, research on the biogenesis of morphine has shown that the molecule is formed by oxidative coupling of a phenol closely related to papaverine. 

When oxidized by iron(III) ions 4-aminoantipyrine reacts with phenols to yield colored quinonoid derivatives (cf. 4-aminoantipyrine — potassium hexacyanoferrate(III) reagent in Volume 1 a). It is an oxidative coupling based on the Emerson reaction. 

Dec J, J-M Bollag, (1994) Dehalogenation of chlorinated phenols during oxidative coupling. Environ Sci Technol 28 484-490. 

High potential Oj reduction to H O coupled to oxidation of phenols... 

Chauhan, M. Dean, F. M. Hindley, K. Robinson, M. Phenoxylium ion from a-tocopherol spirodimer and its significance for the mechanism of oxidative coupling in phenols. Chem. Commun. 1971, 19, 1141-1143. 

The stoichiometric oxidative coupling of various phenols proceeds with moderate selectivity (76% ee) in the presence of (-)-sparteine CuCl2, Eq. 106 (127). As mentioned above, selectivity seems to be driven by solubility issues since isolation of the product from the precipitate or from solution results in different enantiose-lectivities. Indeed, this system performs far worse under catalytic conditions. The best result involves the use of silver chloride as reoxidant the heterooxidative coupling of two naphthols 182 and 183 affords the product 184 in 41% yield and 32% ee using 10 mol% catalyst, Eq. 107. 

We were interested in the behaviour of polymeric catalysts in order to confirm that typical polymer effects may occur. Oxidative coupling of 2,6-disubstituted phenols, as developped by Hay (7), was chosen as a model reaction and the catalytic activities of coordination complexes of copper with several polymeric tertiary amines were compared with the activities of their low molecular weight analogs. The overall reaction scheme is presented in scheme 1. 

Table I Kinetic results on oxidative coupling of 2,6-disubstituted phenols at 25°C in the solvent mixture 1,2-dichlorobenzene/methanol (13 2 v/v).

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