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

Organic & Biomolecular Chemistry Pub Date: 2003-08-04 DOI: 10.1039/B305219M

Abstract

Enzymatic and chemical oxidation of 4-(4-N,N-dialkylaminobutyl)catechols leads to formation of 1,1-dialkylpyrrolidinium 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. The failure of the dialkylaminobutyl derivatives to cyclise to bicyclic betaines, in a manner analogous to lower homologues and monoalkylaminobutyl derivatives, is attributed to steric hindrance. This proposal is supported by evidence that the sterically hindered N-tert-butylaminobutyl derivative, in contrast to other secondary amines, does not cyclise but gives a para-quinomethane-derived product. Based on pulse radiolysis and spectrophotometric evidence, para-quinomethane formation appears to be much slower than cyclisation and only occurs when cyclisation is unfavourable. The ortho-quinones formed from 5-aminopentylcatechols neither cyclise nor tautomerise suggesting that the chain length in these derivatives is too long for both cyclisation and intramolecular deprotonation.

Graphical abstract: Formation of para-quinomethanes via 4-aminobutylcatechol oxidation and ortho-quinone tautomerism
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