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

Abstract

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.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [2]; ORCiD logo [2];  [3];  [1]
  1. Joint BioEnergy Institute, Emeryville, CA (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Joint BioEnergy Institute, Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
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 Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1349690
Alternate Identifier(s):
OSTI ID: 1468340
Report Number(s):
PNNL-SA-122183
Journal ID: ISSN 2168-0485
Grant/Contract Number:  
AC05-76RL01830; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 5; Journal Issue: 5; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; depolymerization; lignin; methylation; quinone methide; repolymerization

Citation Formats

Kim, Kwang Ho, Dutta, Tanmoy, Walter, Eric D., Isern, Nancy G., Cort, John R., Simmons, Blake A., and Singh, Seema. Chemoselective methylation of phenolic hydroxyl group prevents quinone methide formation and repolymerization during lignin depolymerization. United States: N. p., 2017. Web. https://doi.org/10.1021/acssuschemeng.6b03102.
Kim, Kwang Ho, Dutta, Tanmoy, Walter, Eric D., Isern, Nancy G., Cort, John R., Simmons, Blake A., & Singh, Seema. Chemoselective methylation of phenolic hydroxyl group prevents quinone methide formation and repolymerization during lignin depolymerization. United States. https://doi.org/10.1021/acssuschemeng.6b03102
Kim, Kwang Ho, Dutta, Tanmoy, Walter, Eric D., Isern, Nancy G., Cort, John R., Simmons, Blake A., and Singh, Seema. Wed . "Chemoselective methylation of phenolic hydroxyl group prevents quinone methide formation and repolymerization during lignin depolymerization". United States. https://doi.org/10.1021/acssuschemeng.6b03102. https://www.osti.gov/servlets/purl/1349690.
@article{osti_1349690,
title = {Chemoselective methylation of phenolic hydroxyl group prevents quinone methide formation and repolymerization during lignin depolymerization},
author = {Kim, Kwang Ho and Dutta, Tanmoy and Walter, Eric D. and Isern, Nancy G. and Cort, John R. and Simmons, Blake A. and Singh, Seema},
abstractNote = {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.},
doi = {10.1021/acssuschemeng.6b03102},
journal = {ACS Sustainable Chemistry & Engineering},
number = 5,
volume = 5,
place = {United States},
year = {2017},
month = {3}
}

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Works referenced in this record:

Phenols from Lignin
journal, May 2008

  • Kleinert, M.; Barth, T.
  • Chemical Engineering & Technology, Vol. 31, Issue 5, p. 736-745
  • DOI: 10.1002/ceat.200800073

Toward Thermoplastic Lignin Polymers. Part 1. Selective Masking of Phenolic Hydroxyl Groups in Kraft Lignins via Methylation and Oxypropylation Chemistries
journal, December 2012

  • Sadeghifar, Hasan; Cui, Chengzhong; Argyropoulos, Dimitris S.
  • Industrial & Engineering Chemistry Research, Vol. 51, Issue 51, p. 16713-16720
  • DOI: 10.1021/ie301848j

Lignin Valorization: Improving Lignin Processing in the Biorefinery
journal, May 2014

  • Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J.
  • Science, Vol. 344, Issue 6185, p. 1246843-1246843
  • DOI: 10.1126/science.1246843

Lignin depolymerization (LDP) in alcohol over nickel-based catalysts via a fragmentation–hydrogenolysis process
journal, January 2013

  • Song, Qi; Wang, Feng; Cai, Jiaying
  • Energy & Environmental Science, Vol. 6, Issue 3, p. 994-1007
  • DOI: 10.1039/c2ee23741e

Formic-acid-induced depolymerization of oxidized lignin to aromatics
journal, November 2014

  • Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J.
  • Nature, Vol. 515, Issue 7526, p. 249-252
  • DOI: 10.1038/nature13867

Solvent free depolymerization of Kraft lignin to alkyl-phenolics using supported NiMo and CoMo catalysts
journal, January 2015

  • Kumar, Chowdari Ramesh; Anand, Narani; Kloekhorst, Arjan
  • Green Chemistry, Vol. 17, Issue 11
  • DOI: 10.1039/C5GC01641J

Lignin fast pyrolysis: Results from an international collaboration
journal, May 2010

  • Nowakowski, D. J.; Bridgwater, A. V.; Elliott, D. C.
  • Journal of Analytical and Applied Pyrolysis, Vol. 88, Issue 1, p. 53-72
  • DOI: 10.1016/j.jaap.2010.02.009

The use of calcium hydroxide pretreatment to overcome agglomeration of technical lignin during fast pyrolysis
journal, January 2015

  • Zhou, Shuai; Brown, Robert C.; Bai, Xianglan
  • Green Chemistry, Vol. 17, Issue 10
  • DOI: 10.1039/C5GC01611H

Lignin Depolymerization and Conversion A Review of Thermochemical Methods
journal, November 2010

  • Pandey, M. P.; Kim, C. S.
  • Chemical Engineering & Technology, Vol. 34, Issue 1, p. 29-41
  • DOI: 10.1002/ceat.201000270

Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization
journal, October 2016

  • Shuai, Li; Amiri, Masoud Talebi; Questell-Santiago, Ydna M.
  • Science, Vol. 354, Issue 6310
  • DOI: 10.1126/science.aaf7810

Towards Quantitative Catalytic Lignin Depolymerization
journal, April 2011

  • Roberts, Virginia. M.; Stein, Valentin; Reiner, Thomas
  • Chemistry - A European Journal, Vol. 17, Issue 21, p. 5939-5948
  • DOI: 10.1002/chem.201002438

Nature and Kinetic Analysis of Carbon−Carbon Bond Fragmentation Reactions of Cation Radicals Derived from SET-Oxidation of Lignin Model Compounds
journal, October 2010

  • Cho, Dae Won; Parthasarathi, Ramakrishnan; Pimentel, Adam S.
  • The Journal of Organic Chemistry, Vol. 75, Issue 19
  • DOI: 10.1021/jo1012509

Preparation of Diastereomerically Pure Dilignol Model Compounds
journal, November 2011

  • Buendia, Julien; Mottweiler, Jakob; Bolm, Carsten
  • Chemistry - A European Journal, Vol. 17, Issue 49
  • DOI: 10.1002/chem.201101579

Regioselectivity of Enzymatic and Photochemical Single Electron Transfer Promoted Carbon−Carbon Bond Fragmentation Reactions of Tetrameric Lignin Model Compounds
journal, April 2011

  • Cho, Dae Won; Latham, John A.; Park, Hea Jung
  • The Journal of Organic Chemistry, Vol. 76, Issue 8
  • DOI: 10.1021/jo200253v

Catalytic Depolymerization of Lignin in Supercritical Ethanol
journal, May 2014

  • Huang, Xiaoming; Korányi, Tamás I.; Boot, Michael D.
  • ChemSusChem, Vol. 7, Issue 8
  • DOI: 10.1002/cssc.201402094

Condensation Reactions of Some Lignin Related Compounds at Relatively Low Pyrolysis Temperature
journal, August 2007

  • Nakamura, Takeshi; Kawamoto, Haruo; Saka, Shiro
  • Journal of Wood Chemistry and Technology, Vol. 27, Issue 2
  • DOI: 10.1080/02773810701515143

Formation of phenolic oligomers during fast pyrolysis of lignin
journal, July 2014


Lignin and Lignans
book, August 2010


Quantitative Investigation of Free Radicals in Bio-Oil and their Potential Role in Condensed-Phase Polymerization
journal, February 2015


Formation and stabilization of persistent free radicals
journal, January 2007

  • Dellinger, Barry; Lomnicki, Slawomir; Khachatryan, Lavrent
  • Proceedings of the Combustion Institute, Vol. 31, Issue 1
  • DOI: 10.1016/j.proci.2006.07.172

Pyrolytic cleavage mechanisms of lignin-ether linkages: A study on p-substituted dimers and trimers
journal, January 2008

  • Kawamoto, Haruo; Nakamura, Takeshi; Saka, Shiro
  • Holzforschung, Vol. 62, Issue 1
  • DOI: 10.1515/HF.2008.007

Pyrolytic reactivities of deuterated β-ether-type lignin model dimers
journal, March 2015

  • Watanabe, Toshihiro; Kawamoto, Haruo; Saka, Shiro
  • Journal of Analytical and Applied Pyrolysis, Vol. 112
  • DOI: 10.1016/j.jaap.2015.02.028

    Works referencing / citing this record:

    Lignin depolymerization to monophenolic compounds in a flow-through system
    journal, January 2017

    • Kumaniaev, Ivan; Subbotina, Elena; Sävmarker, Jonas
    • Green Chemistry, Vol. 19, Issue 24
    • DOI: 10.1039/c7gc02731a

    Solvation effect on binding modes of model lignin dimer compounds on MWW 2D-zeolite
    journal, September 2019

    • Jain, Varsha; Wilson, Woodrow N.; Rai, Neeraj
    • The Journal of Chemical Physics, Vol. 151, Issue 11
    • DOI: 10.1063/1.5112101

    Dimethyl carbonate: a versatile reagent for a sustainable valorization of renewables
    journal, January 2018

    • Fiorani, G.; Perosa, A.; Selva, M.
    • Green Chemistry, Vol. 20, Issue 2
    • DOI: 10.1039/c7gc02118f