2034-60-8Relevant academic research and scientific papers
Formic-acid-induced depolymerization of oxidized lignin to aromatics
Rahimi, Alireza,Ulbrich, Arne,Coon, Joshua J.,Stahl, Shannon S.
, p. 249 - 252 (2014)
Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth and is one of the few renewable sources of aromatic chemicals. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin), lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10-20wt%). Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C-O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered.
Preparation and Reactivity of Biomass-Derived Dihydro-Dioxins
Montgomery, James R. D.,Kempf, Karl,Miles-Barrett, Daniel M.,Kempf, Oxana,Lebl, Tomas,Westwood, Nicholas J.
, p. 190 - 193 (2019)
The depolymerization of the biopolymer lignin can give pure aromatic monomers but selective catalytic approaches remain scarce. Here, an approach was rerouted to deliver an unusual phenolic monomer. This monomer's instability proved challenging, but a degradation study identified strategies to overcome this. Heterocycles and a useful synthetic intermediate were prepared. The range of aromatics available from the β-O-4 unit in lignin was extended.
SELECTIVE C-O BOND CLEAVAGE OF OXIDIZED LIGNIN AND LIGNIN-TYPE MATERIALS INTO SIMPLE AROMATIC COMPOUNDS
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Page/Page column 35, (2015/10/05)
A method to cleave C-C and C-0 bonds in β-Ο-4 linkages in lignin or lignin sub-units is described. The method includes oxidizing at least a portion of secondary benzylic alcohol groups in β-Ο-4 linkages in the lignin or lignin sub-unit to corresponding ketones and then leaving C-0 or C-C bonds in the oxidized lignin or lignin sub-unit by reacting it with an organic carboxylic acid, a salt of an organic carboxylic acids, and/or an ester of an organic carboxylic acids. The method may utilize a metal or metal-containing reagent or proceed without the metal or metal-containing reagent.
Selective oxidation of benzylic or allylic hydroxyl group of sec-1,2-diols
Peng, Kun,Chen, Fuxin,She, Xuegong,Yang, Chunhui,Cui, Yuxin,Pan, Xinfu
, p. 1217 - 1220 (2007/10/03)
A mild and efficient method to selectively oxidize chiral sec-1,2-diols has been developed, which demonstrates that 2,3-dichloro-5,6-dicyano-1,4- benzoquinone (DDQ) can selectively oxidize benzylic or allylic hydroxyl group of sec-1,2-diols under ultrasound wave promotion. The configuration of the adjacent chiral center is retained.
