The oxidative coupling reaction of 2,6‐dimethylphenol and 2,6‐di‐tert‐butylphenol with molecular oxygen was performed by using a series of copper(II) chelate complexes as a catalyst, derived from copper(II), β‐diketone, and some Shiff bases. Under the applied reaction conditions, the reaction products of 2,6‐dimethylphenol were poly(2,6‐dimethyl‐1,4‐phenylene oxide) (CO coupling product) and 3,3′,5‐5′‐tetramethyl‐4,4′‐diphenoquinone (CC coupling product), and that of 2,6‐di‐tert‐butylphenol oxidation was only 3,3′,5‐5′‐tetra‐tert‐butyl‐4,4′‐diphenoquinone (CC coupling product). The catalytic activity has been shown to be dependent on the properties of the copper(II) chelates used as catalysts and the mole ratios of amine ligand to copper(II) chelate (ligand ratio). The basicity and the steric bulkiness of the amine used as a ligand for copper(II) β‐diketonato catalysts were found to be two of the main factors that govern the oxidative coupling mode (CO and/or CC coupling) of 2,6‐dimethylphenol. The oxidative coupling activity of 2,6‐dialkylphenol is discussed in terms of both the stabilities of the copper(II) chelates and of the copper(II) chelate‐amine adducts. The rate of oxygen absorption for 2,6‐dimethylphenol catalyzed by the copper(II) acetylacetonato‐piperidine system is first order in oxygen partial pressure and zero order in 2,6‐dimethylphenol concentration, respectively. A Cu(II)‐oxygen, as an intermediate is suggested on the basis of the results obtained.

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