Chemoselective methylation of phenolic hydroxyl group prevents quinone methide formation and repolymerization during lignin depolymerization

Kim, Kwang Ho; Dutta, Tanmoy; Walter, Eric D.; Isern, Nancy G.; Cort, John R.; Simmons, Blake A.; Singh, Seema

doi:10.1021/acssuschemeng.6b03102

Title: Chemoselective methylation of phenolic hydroxyl group prevents quinone methide formation and repolymerization during lignin depolymerization

Journal Article · Wed Mar 22 00:00:00 EDT 2017 · ACS Sustainable Chemistry & Engineering

DOI:https://doi.org/10.1021/acssuschemeng.6b03102· OSTI ID:1349690

^[1];

^[1]; Walter, Eric D. ^[2]; Isern, Nancy G. ^[2];

^[2]; Simmons, Blake A. ^[3]; Singh, Seema ^[1]

Joint BioEnergy Institute, Emeryville, CA (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Joint BioEnergy Institute, Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Chemoselective blocking of the phenolic hydroxyl (Ar-OH) group by methylation was found to suppress secondary repolymerization and charring during lignin depolymerization. Methylation of Ar-OH prevents formation of reactive quinone methide intermediates, which are partly responsible for undesirable secondary repolymerization reactions. Instead, this structurally modified lignin produces more relatively low molecular weight products from lignin depolymerization compared to unmodified lignin. This result demonstrates that structural modification of lignin is desirable for production of low molecular weight phenolic products. This approach could be directed toward alteration of natural lignification processes to produce biomass that is more amenable to chemical depolymerization.

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Research Organization:: Sandia National Lab. (SNL-CA), Livermore, CA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Joint BioEnergy Institute (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830; AC02-05CH11231

OSTI ID:: 1349690

Alternate ID(s):: OSTI ID: 1468340

Report Number(s):: PNNL-SA-122183

Journal Information:: ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 5; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 43 works

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Cited By (2)

Solvation effect on binding modes of model lignin dimer compounds on MWW 2D-zeolite Jain, Varsha; Wilson, Woodrow N.; Rai, Neeraj The Journal of Chemical Physics, Vol. 151, Issue 11 https://doi.org/10.1063/1.5112101	journal	September 2019
Recent Efforts to Prevent Undesirable Reactions From Fractionation to Depolymerization of Lignin: Toward Maximizing the Value From Lignin Kim, Kwang Ho; Kim, Chang Soo Frontiers in Energy Research, Vol. 6 https://doi.org/10.3389/fenrg.2018.00092	journal	September 2018

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
depolymerization
lignin
methylation
quinone methide
repolymerization

Title: Chemoselective methylation of phenolic hydroxyl group prevents quinone methide formation and repolymerization during lignin depolymerization

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