A New Approach Towards the Yellowing Inhibition of Mechanical Pulps. Part I: Selective Removal of α-Hydroxyl and α-Carbonyl Groups in Lignin Model Compounds

Holzforschung ◽  
1999 ◽  
Vol 53 (1) ◽  
pp. 43-48 ◽  
Author(s):  
T. Q. Hu ◽  
G. Leary ◽  
D. Wong
Keyword(s):  
Carbonyl Group ◽  
Trifluoroacetic Acid ◽  
Selective Removal ◽  
Hydroxyl Group ◽  
Carbonyl Groups ◽  
Model Compounds ◽  
Ether Linkage ◽  
Lignin Model Compounds ◽  
Lignin Model ◽  
Mechanical Pulps

Summary The α-hydroxyl group in lignin model compounds 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)-1,3-propanediol (1) and 1-(4-hydroxy-3-methoxyphenyl)ethanol (3), and the α-carbonyl group in 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)ethan-1-one (5) are removed by treatment of the model compounds with trifluoroacetic acid (CF3CO OH) and triethylsilane (Et3sih) in methylene chloride. The reaction is highly chemoselective and it tolerates the lignin γ-hydroxyl group, phenol and β-O-4-aryl ether linkage. The α-hydroxyl group in 1 has also been removed with triethylsilane in aqueous trifluoroacetic acid (CF3CO OH : H2o = 75 : 25). The combination of trifluoroacetic acid and sodium borohydride, or sodium triacetoxyborohydride, is also effective in removing the α-carbonyl group in 5 and the α-hydroxyl group in lignin model compound 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)ethanol (7) and in milled wood lignin. The selective removal of the lignin α-hydroxyl and α-carbonyl groups may potentially be used, in conjunction with the protection of the lignin phenol, to inhibit the light and/or heat-induced yellowing of mechanical pulps.

scholarly journals Study of the Reactivity of Lignin Model Compounds to Fluorobenzylation Using 13C and 19F NMR: Application to Lignin Phenolic Hydroxyl Group Quantification by 19F NMR

Molecules ◽  
2020 ◽  
Vol 25 (14) ◽  
pp. 3211
Author(s):  
Esakkiammal Sudha Esakkimuthu ◽  
Nathalie Marlin ◽  
Marie-Christine Brochier-Salon ◽  
Gérard Mortha
Keyword(s):  
Reaction Medium ◽  
19F Nmr ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Nmr Analysis ◽  
Model Compounds ◽  
Lignin Model Compounds ◽  
Wide Range ◽  
Lignin Model ◽  
13C And 19F Nmr

Lignin is an aromatic biopolymer derived from lignocellulosic biomass. Providing a comprehensive structural analysis of lignin is the primary motivation for the quantification of various functional groups, with a view to valorizing lignin in a wide range of applications. This study investigated the lignin fluorobenzylation reaction and performed a subsequent 19F-NMR analysis to quantify hydroxyl groups, based on a work developed two decades ago by Barrelle et al. The objectives were to check the assignments proposed in this previous study and to examine the reactivity of various types of lignin hydroxyls with the derivatization agent. Selected lignin model compounds containing phenolic and aliphatic hydroxyls were subjected to the fluorobenzylation reaction, and the obtained reaction medium was analyzed by 13C and 19F NMR spectroscopy. The model compound results showed that phenolic hydroxyls were totally derivatized, whereas aliphatic hydroxyls underwent minimal conversion. They also confirmed that 19F NMR chemical shifts from −115 ppm to −117.3 ppm corresponded to phenolic groups. Then, a 19F NMR analysis was successfully applied to Organosolv commercial lignin after fluorobenzylation in order to quantify its phenolic group content; the values were found to be in the range of the reported values using other analytical techniques after lignin acetylation.

Polyoxometalate (POM) oxidation of lignin model compounds

Holzforschung ◽  
2008 ◽  
Vol 62 (1) ◽  
pp. 38-49 ◽  
Author(s):  
Yong Sik Kim ◽  
Hou-min Chang ◽  
John F. Kadla
Keyword(s):  
Reaction Rate ◽  
Model Compound ◽  
Reaction Rates ◽  
Hydroxyl Group ◽  
Model Compounds ◽  
Lignin Model Compounds ◽  
Lignin Model Compound ◽  
First Order ◽  
Resonance Stabilization ◽  
Lignin Model

Abstract Various lignin model compounds were oxidized with polyoxometalate (POM), K5[SiVW11O40]·12 H2O, in sodium acetate buffer (I=0.2 M, pH 5.0) and the reaction kinetics were investigated. The reactions were found to have second order reaction rates, first order with regards to both lignin model compound and POM. A dramatic increase in reactivity was observed upon addition of methoxyl groups in ortho-positions to the phenolic hydroxyl group. Syringyl units reacted faster than guaiacyl units. Reaction rates of para-substituted guaiacyl and syringyl model compounds showed a strong dependency on the nature of the substituents. The reaction rate of a 5-5′ dimer lignin model compound was extremely fast. The addition of the ortho-phenol substituent not only increased the electron density of the aromatic ring, but also helped stabilize the intermediate phenoxy radical through resonance stabilization and delocalization.

Lignin to Value-Added Chemical Synthesis

2020 ◽  
Vol 16 ◽  
Author(s):  
Mahdieh Sharifi ◽  
Ramyakrishna Pothu ◽  
Rajender Boddula ◽  
Inamuddin
Keyword(s):  
Ionic Liquids ◽  
Lignocellulosic Biomass ◽  
Academic Research ◽  
Power Saving ◽  
Value Added ◽  
Glycerol Ether ◽  
Model Compounds ◽  
Lignin Model Compounds ◽  
Biomass Activity ◽  
Lignin Model

Background: There is a developing demand for innovation in petroleum systems replacements. Towards this aim, lignocellulosic biomass suggested as a possible sustainable source for the manufacturing of fuels and produced chemicals. The aims of this paper are to investigate different kinds of β-O-4 lignin model compounds for the production of value-added chemicals in presence of ionic liquids. Especially, a cheap β-O-4 lignin model Guaiacol glycerol ether (GGE) (Guaifenesin) is introduced to produce valuable chemicals and novel products. Methods: Research related to chemical depolymerization of lignocellulosic biomass activity is reviewed, the notes from different methods such as thermal and microwave collected during at least 10 years. So, this collection provides a good source for academic research and it gives an efficient strategy for the manufacturing of novel value-added chemicals at an industrial scale. Results: This research presented that ionic liquid microwave-assisted is a power saving, cost efficient, fast reaction, and clean way with high selectively and purity for production of high value chemicals rather that conversional heating. Guaiacol and catechol are some of these valuable chemicals that is produced from β-O-4 lignin model compounds with high word demands that are capable to produce in industry scale. Conclusion: The β-O-4 lignin model compounds such as Guaiacol glycerol ether (GGE) (Guaifenesin) are good platform for developing food materials, perfumery, biorefinery, and pharmaceutical industry by ionic liquids-assisted lignin depolymerization method.

Insights into the electrochemical degradation of phenolic lignin model compounds in protic ionic liquid-water system

2021 ◽  
Author(s):  
Guangyong Liu ◽  
Qian Wang ◽  
Dongxia Yan ◽  
Yaqin Zhang ◽  
Chenlu Wang ◽  
...  
Keyword(s):  
Water System ◽  
Value Added ◽  
Electrochemical Degradation ◽  
Aryl Ether ◽  
Model Compounds ◽  
Protic Ionic Liquid ◽  
Lignin Model Compounds ◽  
Mild Conditions ◽  
System P ◽  
Lignin Model

Cleavage of aryl ether (Caryl-O) bonds is crucial for conversion and value-added utilization of lignin and its derivatives, but remains extremely challenging under mild conditions due to strong Caryl-O linkages....

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