Quantitative Difference in the Rates of the β-O-4 Bond Cleavage between Lignin Model Compounds with and without y-Hydroxymethyl Groups during the Alkaline Pulping Process

To examine the effect of the presence of y-hydroxymethyl groups on the rate of the β-O-4 bond cleavage during the alkaline pulping process, the rates of the β-O-4 bond cleavage of non-phenolic lignin model compounds without a y-hydroxymethyl group, 2-(2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl)ethanol (G’G) and 2-(2,6-dimethoxyphenoxy)-1-(3,4-dimethoxyphenyl)ethanol (G’S), were compared with those of analogous model compounds with a y-hydroxymethyl group, 2-(2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol (GG) and 2-(2,6-dimethoxyphenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol (GS), under alkaline pulping conditions. The disappearance of G’G or G’S was accompanied by the quantitative liberation of 2-methoxyphenol or 2,6-dimethoxyphenol, respectively, indicating that the disappearance resulted from the β-O-4 bond cleavage. The disappearance rate of G’G or G’S was in between those of the erythro and threo isomers of GG or GS, respectively. This result seems to be reasonably explained when the steric repulsions of the three staggered conformations are taken into consideration. The disappearance rate of G’G or G’S increased, but the increment became moderate with increasing hydroxide concentration.