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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 more amenable to chemical depolymerization.

Authors:
ORCiD logo; ORCiD logo; ; ; ORCiD logo; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1356483
Report Number(s):
PNNL-SA-122183
Journal ID: ISSN 2168-0485; 48827; KP1704020
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
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:
Environmental Molecular Sciences Laboratory

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. doi: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. 2017. "Chemoselective Methylation of Phenolic Hydroxyl Group Prevents Quinone Methide Formation and Repolymerization During Lignin Depolymerization". United States. https://doi.org/10.1021/acssuschemeng.6b03102.
@article{osti_1356483,
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 more amenable to chemical depolymerization.},
doi = {10.1021/acssuschemeng.6b03102},
url = {https://www.osti.gov/biblio/1356483}, journal = {ACS Sustainable Chemistry & Engineering},
issn = {2168-0485},
number = 5,
volume = 5,
place = {United States},
year = {Thu Mar 30 00:00:00 EDT 2017},
month = {Thu Mar 30 00:00:00 EDT 2017}
}

Works referenced in this record:

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Works referencing / citing this record:

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


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


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