Predominant formation of aromatic aldehyde and acid from a dimeric β-O-4-type lignin model compound under hydrogen peroxide bleaching conditions with high pH levels

Abstract

When a dimeric non-phenolic β-O-4-type lignin model compound, 2-(2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol (veratrylglycerol-β-guaiacyl ether (VG)), was treated under alkaline oxygen or hydrogen peroxide bleaching conditions (O2 or H2O2 system, respectively), 3,4-dimethoxybenzaldehyde (veratraldehyde) and 3,4-dimethoxybenzoic acid (veratric acid) formed with yields dependent on the system. The yield of veratraldehyde based on the mole amount of disappearing VG (VG disappearance) was about 30% in the O2 system at a high pH level. However, the total yield of veratraldehyde and veratric acid was 70–80% based on VG disappearance in the H2O2 system at high pH levels, where H2O2 was added stepwise. A prolonged reaction with the further stepwise addition of H2O2 at the high pHs would further increase the formations of veratraldehyde and veratric acid with maintaining the yields based on VG disappearance. The yields (70–80%) are higher than those reported in the previous study, which employed VG, oxygen, and 1,10-phenanthroline and copper (II) sulfate as the catalysts. The high yields in the H2O2 system with high pH levels can be explained by the reactivity of oxyl anion radical, which is the most responsible active oxygen species at these high pHs and preferably attacks the aliphatic side-chain of VG rather than the aromatic nucleus.