Copper(II)-catalyzed reactions of activated aromatics

The catalytic reaction of cis-bisglycinato copper(II) monohydrate in the presence of hydrogen peroxide leads to hydroxylation of phenol to give catechol and hydroquinone (1:1.2 ratio) in good yield. 2,6-Dimethylphenol can be hydroxylated by hydrogen peroxide and a catalytic amount of cis-bisglycinato copper(II) monohydrate to give an aggregate of 1,4-dihydroxy-2,6-dimethylbenzene and 2,6-dimethylphenol. A similar reaction of o-cresol gives 2,5-dihydroxytoluene. The reactivity of cis-bisglycinato copper(II) monohydrate in hydrogen peroxide with o-cresol is 4.5 times faster than that of a similar reaction by trans-bisglycinato copper(II) monohydrate. A catalytic reaction of cis-bisglycinato copper(II) monohydrate with aniline in aqueous hydrogen peroxide gives polyanilines in the form of pernigraniline with different amounts of Cu(OH)2 attached to them. The two major components of polyanilines obtained have Mn values of 1040 and 1500, respectively. Resistance of films of these polyanilines increases with temperatures from 40 degrees C to a maximum value at 103 degrees C and then decreases in the region of 103-150 degrees C, showing the property of a thermolectric switch. The aggregate prepared from hydroxylation of 2,6-dimethylphenol shows a similar property in the region of 30-180 degrees C.