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

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. Finally, this approach could be directed toward alteration of natural lignification processes to produce biomass that is more amenable to chemical depolymerization.

View Accepted Manuscript (DOE)

Research Organization:: 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)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)

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

OSTI ID:: 1349690

Alternate ID(s):: OSTI ID: 1356483
OSTI ID: 1468340

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

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

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (23)

Phenols from Lignin Kleinert, M.; Barth, T. Chemical Engineering & Technology, Vol. 31, Issue 5, p. 736-745 https://doi.org/10.1002/ceat.200800073	journal	May 2008
Lignin Depolymerization and Conversion A Review of Thermochemical Methods Pandey, M. P.; Kim, C. S. Chemical Engineering & Technology, Vol. 34, Issue 1, p. 29-41 https://doi.org/10.1002/ceat.201000270	journal	November 2010
Towards Quantitative Catalytic Lignin Depolymerization Roberts, Virginia. M.; Stein, Valentin; Reiner, Thomas Chemistry - A European Journal, Vol. 17, Issue 21, p. 5939-5948 https://doi.org/10.1002/chem.201002438	journal	April 2011
Preparation of Diastereomerically Pure Dilignol Model Compounds Buendia, Julien; Mottweiler, Jakob; Bolm, Carsten Chemistry - A European Journal, Vol. 17, Issue 49 https://doi.org/10.1002/chem.201101579	journal	November 2011
Catalytic Depolymerization of Lignin in Supercritical Ethanol Huang, Xiaoming; Korányi, Tamás I.; Boot, Michael D. ChemSusChem, Vol. 7, Issue 8 https://doi.org/10.1002/cssc.201402094	journal	May 2014
Quantitative Investigation of Free Radicals in Bio-Oil and their Potential Role in Condensed-Phase Polymerization Kim, Kwang Ho; Bai, Xianglan; Cady, Sarah ChemSusChem, Vol. 8, Issue 5 https://doi.org/10.1002/cssc.201403275	journal	February 2015
Formation of phenolic oligomers during fast pyrolysis of lignin Bai, Xianglan; Kim, Kwang Ho; Brown, Robert C. Fuel, Vol. 128 https://doi.org/10.1016/j.fuel.2014.03.013	journal	July 2014
Lignin fast pyrolysis: Results from an international collaboration Nowakowski, D. J.; Bridgwater, A. V.; Elliott, D. C. Journal of Analytical and Applied Pyrolysis, Vol. 88, Issue 1, p. 53-72 https://doi.org/10.1016/j.jaap.2010.02.009	journal	May 2010
Pyrolytic reactivities of deuterated β-ether-type lignin model dimers Watanabe, Toshihiro; Kawamoto, Haruo; Saka, Shiro Journal of Analytical and Applied Pyrolysis, Vol. 112 https://doi.org/10.1016/j.jaap.2015.02.028	journal	March 2015
Formation and stabilization of persistent free radicals Dellinger, Barry; Lomnicki, Slawomir; Khachatryan, Lavrent Proceedings of the Combustion Institute, Vol. 31, Issue 1 https://doi.org/10.1016/j.proci.2006.07.172	journal	January 2007
Toward Thermoplastic Lignin Polymers. Part 1. Selective Masking of Phenolic Hydroxyl Groups in Kraft Lignins via Methylation and Oxypropylation Chemistries Sadeghifar, Hasan; Cui, Chengzhong; Argyropoulos, Dimitris S. Industrial & Engineering Chemistry Research, Vol. 51, Issue 51, p. 16713-16720 https://doi.org/10.1021/ie301848j	journal	December 2012
Nature and Kinetic Analysis of Carbon−Carbon Bond Fragmentation Reactions of Cation Radicals Derived from SET-Oxidation of Lignin Model Compounds Cho, Dae Won; Parthasarathi, Ramakrishnan; Pimentel, Adam S. The Journal of Organic Chemistry, Vol. 75, Issue 19 https://doi.org/10.1021/jo1012509	journal	October 2010
Regioselectivity of Enzymatic and Photochemical Single Electron Transfer Promoted Carbon−Carbon Bond Fragmentation Reactions of Tetrameric Lignin Model Compounds Cho, Dae Won; Latham, John A.; Park, Hea Jung The Journal of Organic Chemistry, Vol. 76, Issue 8 https://doi.org/10.1021/jo200253v	journal	April 2011
Formic-acid-induced depolymerization of oxidized lignin to aromatics Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J. Nature, Vol. 515, Issue 7526, p. 249-252 https://doi.org/10.1038/nature13867	journal	November 2014
The use of calcium hydroxide pretreatment to overcome agglomeration of technical lignin during fast pyrolysis Zhou, Shuai; Brown, Robert C.; Bai, Xianglan Green Chemistry, Vol. 17, Issue 10 https://doi.org/10.1039/C5GC01611H	journal	January 2015
Solvent free depolymerization of Kraft lignin to alkyl-phenolics using supported NiMo and CoMo catalysts Kumar, Chowdari Ramesh; Anand, Narani; Kloekhorst, Arjan Green Chemistry, Vol. 17, Issue 11 https://doi.org/10.1039/C5GC01641J	journal	January 2015
Lignin depolymerization (LDP) in alcohol over nickel-based catalysts via a fragmentation–hydrogenolysis process Song, Qi; Wang, Feng; Cai, Jiaying Energy & Environmental Science, Vol. 6, Issue 3, p. 994-1007 https://doi.org/10.1039/c2ee23741e	journal	January 2013
Towards effective lignin conversion: HZSM-5 catalyzed one-pot solvolytic depolymerization/hydrodeoxygenation of lignin into value added compounds Singh, Sunit K.; Ekhe, Jayant D. RSC Advances, Vol. 4, Issue 53 https://doi.org/10.1039/c4ra02968b	journal	January 2014
Condensation Reactions of Some Lignin Related Compounds at Relatively Low Pyrolysis Temperature Nakamura, Takeshi; Kawamoto, Haruo; Saka, Shiro Journal of Wood Chemistry and Technology, Vol. 27, Issue 2 https://doi.org/10.1080/02773810701515143	journal	August 2007
Lignin Valorization: Improving Lignin Processing in the Biorefinery Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J. Science, Vol. 344, Issue 6185, p. 1246843-1246843 https://doi.org/10.1126/science.1246843	journal	May 2014
Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization Shuai, Li; Amiri, Masoud Talebi; Questell-Santiago, Ydna M. Science, Vol. 354, Issue 6310 https://doi.org/10.1126/science.aaf7810	journal	October 2016
Lignin and Lignans Heitner, Cyril; Dimmel, Don; Schmidt, John https://doi.org/10.1201/EBK1574444865	book	August 2010
Pyrolytic cleavage mechanisms of lignin-ether linkages: A study on p-substituted dimers and trimers Kawamoto, Haruo; Nakamura, Takeshi; Saka, Shiro Holzforschung, Vol. 62, Issue 1 https://doi.org/10.1515/HF.2008.007	journal	January 2008

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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
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Chemoselective Methylation of Phenolic Hydroxyl Group Prevents Quinone Methide Formation and Repolymerization During Lignin Depolymerization

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Chemoselective methylation of phenolic hydroxyl group prevents quinone methide formation and repolymerization during lignin depolymerization

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