Pyrolysis of Lignin in the Presence of Tetramethylammonium Hydroxide (TMAH): Products Stemming from β-5 Substructures

Lignin model compounds, synthetic lignins, and cedar wood have been analyzed by pyrolysis−gas chromatography(−mass spectrometry) in the presence of tetramethylammonium hydroxide (TMAH) to examine the behavior of β-5 substructures specifically under these conditions. Two model compounds contained a β-5 linkage and a γ-CH2OH group. The phenolic model compound produced stilbene products by way of a formaldehyde elimination of the γ-CH2OH. The nonphenolic model compound underwent dehydration to give arylbenzofuran products. Dehydrogenation polymers of coniferyl alcohol gave a large amount of stilbene products in TMAH/pyrolysis. TMAH/pyrolysis of a Japanese cedar (Cryptomeria japonica) wood yielded a very small amount of stilbene products. The results demonstrated that synthetic lignins are rich in terminal β-5 substructures, but cedar (a softwood) contains a paucity of the terminal β-5 substructures. Keywords: Lignin; β-5 substructures; pyrolysis−gas chromatography(−mass spectrometry); tetramethylammonium hyd...