Fractionation of woody biomass with boiling aqueous acetic acid containing a small amount of mineral acid at atmospheric pressure: Reactivity of arylglycerol-β-aryl ethers in lignins with aqueous acetic acid containing H2SO4

Abstract

To characterize the mechanism of the reaction of lignin with aqueous acetic acid (AW) containing a small amount of H2SO4, guaiacylglycerol-β-guaiacyl ether (GOG), and guaiacylglycerol-β-syringol ether (GOS) were refluxed in 90% AW with 0.28% H2SO4 for 0–120 min. Reaction products and their silylated derivatives were characterized by analytical methods such as gas chromatography-mass spectrometry and nuclear magnetic resonance. When the model compounds were allowed to react at boiling temperature for 0 min (heat-up time 30 min), most of their primary alcohol groups and some of their secondary alcohol groups were acetylated, but their phenolic groups were not. About 90% of GOG was degraded, polymerized, or both during boiling for at least 15 min, yielding guaiacol and isocoumaran compounds (GOG-e and GOG-f) in addition to homovanillin (II) as guaiacylvinyl alcohol (I) and other minor products. GOS yielded syringol, homovanillin (II), and a novel compound (V) together with unknown products but not the corresponding isocoumaran compounds.