Electron Transfer Reactions in Pulping Systems (II): Electrochemistry of Anthraquinone/Lignin Model Quinonemethides

Abstract

Abstract Electron transfer reactions have been observed during the electrolyses of solutions containing anthraquinone and 8-aryl ether lignin model quinonemethides. In dry acetonitrile at a reduction potential of -0.9V (vs. Ag/AgCl) electrons are transferred from the electrode to anthraquinone (AQ) to form stable anthrahydroquinone radical anions (AHQ−). The lignin model quinonemethides are not reduced directly at the electrode at this potential but are reduced by AHQ− to give quinonemethide radical anions (QM−) and AQ. The QM− species rapidly fragment at their β-aryl ether bond to give phenolate ions and radicals; the latter further reduces to another phenolate ion. For example, the β-methyl lignin model QM 1 gives guaiacol and isoeugenol upon electrolysis at -0.9V in the presence of AQ. In wet acetonitrile, reduction of AQ at -0.9V leads to both anthrahydroquinone radical anion and dianion; the dianion is formed by direct electrolysis of the radical anion and by disproportlonation of the radical anion. ...