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Chemical Structure| 14059-92-8

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Product Citations

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Deroma, Matteo ; Lauwaert, Jeroen ; Thybaut, Joris W ; De Clercq, Jeriffa ; Verberckmoes, An ;

Abstract: The valorization of lignin via mild reductive depolymerization has gained increasing interest, but various knowledge gaps regarding the underlying reaction mechanism continue to hinder the rational optimization of the process conditions. In order to fill these gaps, this work investigates both solvolytic and catalytic mild reductive depolymerization of a hydrolysis lignin at different reaction times (15 min – 10 h) and temperatures (150 °C – 200 °C). Novel insights into the depolymerization of (technical) lignins were achieved by investigating the modification of native end groups (NEGs), defined as para-substituted side chains attached to the end of the lignin polymers before depolymerization such as formyl and 3-oxo-1-propenyl. These were found to be stable in solvolysis but highly reactive in catalysis with Pd/γ-Al2O3. Furthermore, this work introduces a new catalytic reaction mechanism, whereby β-O-4-derived propanol side chains are converted into ethyl side chains at elevated temperatures. At 150 °C, these propanol groups remained largely intact, whereas at 200 °C, up to 40 % were transformed into ethyl chains. The findings further highlight distinctive depolymerization pathways for solvolysis and catalysis. Solvolysis proceeds via a “peeling-off” mechanism, while catalysis involves random cleavage of β-O-4 linkages. This results in a higher degree of depolymerization and monomer yield under catalytic conditions (up to 9 wt% compared to approximately 3 wt% for solvolysis). In both cases, the majority of depolymerization occurs within the first 3 h of reaction. Finally, it was proven that the Pd catalyst plays a primordial role in the modification of β-β and β-5 linkages, which remain stable under solvolytic conditions.

Keywords: Lignin ; Mild reductive depolymerization ; Heterogeneous catalysis ; Reaction mechanisms ; Bio-aromatics

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Product Details of [ 14059-92-8 ]

CAS No. :14059-92-8
Formula : C10H14O3
M.W : 182.22
SMILES Code : OC1=C(OC)C=C(CC)C=C1OC
MDL No. :MFCD01366571
InChI Key :PJWDIHUFLXQRFF-UHFFFAOYSA-N
Pubchem ID :61712

Safety of [ 14059-92-8 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H312-H315-H319-H335
Precautionary Statements:P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P305+P351+P338-P330-P332+P313-P337+P313-P362-P403+P233-P405-P501

Application In Synthesis of [ 14059-92-8 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 14059-92-8 ]

[ 14059-92-8 ] Synthesis Path-Downstream   1~6

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  • forest plant material [ No CAS ]
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  • wood [ No CAS ]
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YieldReaction ConditionsOperation in experiment
With water;HUSY (Si/Al=15); at 250℃; under 5250.53 Torr; for 2h;Inert atmosphere;Product distribution / selectivity; In an autoclave (batch reactor) lignin (0.5 g), HUSY (Si/Al=15) (0.5 g) and mixture of water and organic solvent (30 g) were charged. After flushing the reactor with nitrogen gas for 3 times, nitrogen (7 bar) was charged. Reactor was heated up to 230° C. under the stirring (100 rpm). After attaining the desired temperature of 230° C. stirring was increased up to 500 rpm. Reaction was stopped after 30 minutes. Analysis of reaction mixture was done by GC, GC-MS. The lignin used in these examples were organosolv or dealkaline.Yield: >25percentMass balance: >90percent.The effect of reaction temperature and reaction time on depolymerization reaction is demonstrated by the results presented in Table 8 using SiO2-Al2O3 as catalyst*. TABLE 8 Exp. Time Lignin Product yield, Mass balance, No. (min.) conversion percentpercentNo. percent 1. 30 85 26 80 2. 60 85 41 86 3. 90 92 50 84 4. 120 95 70 85 Lignin, 0.5 g; HUSY (Si/Al = 15), 0.5 g; N2 Pressure, 7 bar (at)RT; Temperature, 250° C.No.Monomer and dimer products soluble in water/organic solvents.
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  • lignin, softwood Kraft black liquor [ No CAS ]
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  • [ 498-02-2 ]
  • [ 108-95-2 ]
  • 6
  • [ 14059-92-8 ]
  • [ 2478-38-8 ]
 

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