E.S.R. studies of the oxidative coupling of some bisphenols

Abstract

E.s.r. spectroscopy and the identification of products show that oxidation of 3,5,3?,5?-tetra-t-butyl-4,4?-dihydroxybenzophenone in neutral solution gives 3,5,3?,5?-tetra-t-butyldipheno-4,4?-quinone. If oxygen is present 2,6-di-t-butyl-p-benzoquinone is also formed. The evolution of carbon monoxide suggests that bis-spirodienones are intermediate in the formation of these products. E.s.r. spectra of radicals produced by oxidation of 3,5,3?,5?-tetra-t-butylbiphenyl-4,4?- dio and 2,6-di-t-butylhydro-quinone have been re-examined. In alkaline solution 3,5,3?,5?-tetra-t-butyl-4,4?-dihydroxybenzo-phenone is oxidized to a radical anion in which the unpaired electron is delocalized over both rings.     Attempts to detect unsymmetrical bisaryloxy radicals were unsuccessful, 3?,5?-di-t-butyl-4,4?-dihydroxy-3,5-dimethoxybenzophenone forming only the radical derived from the syringoyl portion, and 2,4?- oxydiphenol ether forming only the 4?-oxy radical. Comparison with the observation of both radicals when a mixture of guaiacol and p- methoxyphenol was oxidized suggests that C-O-C coupling in 2,4?- oxydiphenol proceeds by direct radical pairing.