STUDIES ON LIGNIN AND RELATED COMPOUNDS: XVI. PHENOL LIGNIN FROM SPRUCE WOOD, FROM FREUDENBERG SPRUCE LIGNIN AND WILLSTÄTTER SPRUCE LIGNIN

The condensation of lignin with phenol by treatment of spruce wood meal with this solvent, using hydrogen chloride as catalyst, yields two chemically different phenol lignins, namely, an ether-insoluble and an ether-dioxane–soluble phenol lignin, in a ratio of approximately 3 to 1. Duplicate preparations gave the same yields of these two fractions, analyses of which gave concordant results, indicating homogeneity and constancy of composition.The analytical results of the ether-insoluble phenol lignin, and of its methylated and acetylated derivatives, can be interpreted on the basis of the Brauns–Hibbert formula for the "native" lignin unit. It is found, in this way, that the ether-insoluble phenol lignin contains three new free phenolic hydroxyl groups capable of methylation with diazomethane, while one phenol group has reacted with one hydroxyl group in the lignin unit with formation of a phenyl-oxygen ether linkage.The analytical results of the ether-dioxane–soluble phenol lignin indicate that a much larger quantity of phenol has condensed with the "native" lignin building unit than in the case of the ether-insoluble fraction. The exact number of phenol molecules reacting to form this condensation product has not been determined experimentally although calculations based on analytical data point to a number as large as 15 or 21.The phenol condensation products were obtained from Freudenberg and Willstätter lignins in nearly quantitative yield and found to differ from the directly extracted phenol lignin in that neither of them could be resolved into two fractions, thus indicating that some change had taken place in the native lignin during the isolation process. The Brauns-Hibbert formula can also be applied to interpret the experimental data in both cases. These lignins appear to contain the same fundamental building unit as the ether-insoluble phenol lignin fraction isolated directly from spruce wood, with the difference that the former probably have one additional hydroxyl group capable of acetylation and diazomethane-methylation.The correlation found to exist in the present investigation between the phenol condensation products from native spruce lignin, isolated Freudenberg lignin and Willstätter lignin is regarded as providing definite experimental evidence indicating the presence of a chemical unit common to various lignins. The phenol condensation products, it is considered, may serve as valuable reference compounds for proving the identity of lignins obtained from different sources and by use of different chemical reagents.