Abstract
N,N'-Dialkylimidazolium-based ionic liquids are capable of completely dissolving lignocellulosic biomass at elevated temperatures and are considered as promising green solvents for future biorefining technologies. However, the obtained ionic liquid lignin preparations may contain up to several percent nitrogen. This indicates strong interactions between the biopolymer and the IL cation, the nature of which has not yet been clarified. The present study investigates mechanisms and pathways of the formation of nitrogen-containing lignin compounds. To achieve this goal, eight monomeric lignin-related phenols bearing different functional groups (ketone, aldehyde, hydroxyl, carbon-carbon double bonds) were treated with 1-butyl-3-methylimidazolium acetate (BmimOAc) under typical conditions of IL-assisted lignocellulose fractionation (80-150 °C). A number of the resulting products were tentatively identified, for all the studied model compounds, by two-dimensional NMR spectroscopy and high-performance liquid chromatography-high-resolution mass spectrometry. They all possess covalently bonded Bmim residues and occur through the nucleophilic addition of an N-heterocyclic carbene (deprotonated Bmim cation) to electron-deficient groups. The reactivity of lignin functional groups in their interaction with Bmim is greatly affected by the temperature and dissolved oxygen. IL's thermal degradation products act as additional reactive species toward lignin, further complicating the range of products formed. The obtained results made it possible to answer the question posed in this article's title and to assert that N,N'-dialkylimidazolium-based ILs act as active reagents with respect to lignin during the dissolution of lignocellulose.