Formation of para-quinomethanes via 4-aminobutylcatechol oxidation and ortho-quinone tautomerism.

Enzymatic and chemical oxidation of 4-(4-N,N-dialkylaminobutyl)catechols leads to formation of 1,1-dialkyl-pyrrolidinium salts in good yield. It is proposed that these products are formed by tautomerism of the initially formed ortho-quinones to para-quinomethanes. The corresponding secondary amines do not form para-quinomethanes but cyclise giving tetrahydro-1H-benzo[b]azepine-7,8-diones.

Mechanistic studies of catechol generation from secondary quinone amines relevant to indole formation and tyrosinase activation.

The biological significance of the spontaneous cyclization and redox reactions of ortho-quinone amines is that these appear to be the mechanism of formation of the indolic components of melanin and are also involved in the autoactivation of tyrosinase. We have previously shown that activation of tyrosinase is prevented by the formation of a cyclic betaine from a tertiary amine analogue. Evidence is presented to show that cyclization of ortho-quinones by Michael addition also occurs in the oxidation of secondary catecholamines.