On the Origin of Alkali-Catalyzed Aromatization of Phenols

To gain an insight of the chemistry in the alkali-promoted aromatization of oxygen-containing heavily aromatic polymers or biomass; thermal degradations of sodium phenolates with different substituents have been investigated. The -ONa group strongly destabilizes the phenolates. The thermal stability of phenolates is largely in parallel with bond strengths of Ar substituents. De-substituents and the removal of aromatic hydrogens are dominant reactions in the main degradation step. CO is formed only at a very late stage. This degradation pattern is completely different from that of phenol. To account for this distinctive decomposition; a mechanism involving an unprecedented formation of an aromatic carbon radical anion generated from the homolytic cleavage of Ar substituent (or Ar–H) in keto forms has been proposed. The homolytic cleavage of Ar substituent (or Ar–H) is facilitated by the strong electron-donating ability of the oxygen anion. A set of free-radical reactions involved in the alkali-catalyzed aromatization have been established.