Method for degrading oxidation lignin into small molecular aromatic compound

A technology of aromatic compounds and lignin, which is applied in the field of small molecule aromatic compounds, can solve the problems of harsh catalytic process conditions, metal residues, and unsatisfactory effects, and achieve the effects of convenient operation, high conversion rate, and mild reaction conditions

Inactive Publication Date: 2017-07-07
JILIN UNIV
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AI Technical Summary

Problems solved by technology

Among them, the research on degrading lignin by breaking the C-C bond is mainly based on transition metal catalysts, and the effect is not very satisfactory.
In addition, the harsh conditions in the catalytic process of transition metal catalysts (inert atmosphere or high temperature and high pressure, etc.) and the problem of metal residues after the end of the reaction limit its industrial application to a certain extent.

Method used

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  • Method for degrading oxidation lignin into small molecular aromatic compound
  • Method for degrading oxidation lignin into small molecular aromatic compound
  • Method for degrading oxidation lignin into small molecular aromatic compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026]

[0027] (1) Add substrate oxidized lignin dimer 1 (1.211g, 1eq.), oxidant m-chloroperoxybenzoic acid (m-CPBA) (1.73g, 2eq.), and 150mL of methylene chloride to a 250mL round bottom flask. It was dissolved and stirred at room temperature for 12 hours. Column chromatography (petroleum ether) gave acetal 1a (1.12 g, 98% yield) as a colorless oil. NMR data:

[0028] 1 H NMR (500MHz, Chloroform-d) δ8.07 (dd, J = 8.3, 1.3 Hz, 2H), 7.58 (t, J = 7.3 Hz, 1H), 7.44 (t, J = 8.0 Hz, 2H), 7.35 –7.31(m,2H),7.12(d,J=8.5Hz,2H),7.07(t,J=7.3Hz,1H),6.03(s,2H); 13 C NMR(126MHz, CDCl 3 )δ165.6, 157.1, 133.6, 130.0, 129.8, 129.5, 128.6, 122.9, 116.3, 86.4.

[0029] (2) Add step (1) Oxidation product-acetal 1a (0.57g, 2.5mmol) in a 250mL round bottom flask and dissolve it in tetrahydrofuran solvent, add 1mol / L hydrochloric acid solution (0.5mL) as a catalyst, and stir at room temperature for 6 hour. Column chromatography (ethyl acetate: petroleum ether = 1:10, volume ratio) gave the product w...

Embodiment 2

[0033]

[0034] (1) Change the oxidant to hydrogen peroxide (H 2 O 2 ) (2eq.), and other conditions were the same as the step (1) of Example 1, to obtain a colorless oil 1a (1.10g, yield 96%).

[0035] NMR data: as in Example 1.

[0036] (2) Change the solvent to methanol, and other conditions are as in step (2) of Example 1, to obtain colorless liquid methyl benzoate (yield 98%) and colorless liquid phenol (yield 90%).

[0037] NMR data:

[0038] Methyl benzoate 1 H NMR(CDCl 3 ,400MHz): δ8.04(d,J=7.6Hz,2H),7.55(t,J=7.4Hz,1H),7.43(t,J=7.8Hz,2H),3.92(s,3H); 13 C NMR(CDCl 3 ,100MHz): δ167.1, 132.9, 130.1, 129.5, 128.3, 52.0.

[0039] Phenol is as in Example 1.

Embodiment 3

[0041]

[0042] (1) Change the substrate to 2 in the above formula, and other conditions are the same as step (1) of Example 1, to obtain a red oil 2a (yield 30%) and a white solid 2b (yield 65%).

[0043] NMR data:

[0044] 2a 1 H NMR(500MHz, CDCl 3 )δ7.70(dd,J=8.5,2.1Hz,1H),7.51(d,J=2.1Hz,1H),7.13-7.07(m,1H),7.03(td,J=7.8,1.6Hz,1H ), 6.88 (dd, J = 8.2, 1.5 Hz, 1H), 6.83 (dt, J = 9.2, 3.4 Hz, 2H), 6.59 (dd, J = 5.9, 4.1 Hz, 1H), 4.06 (dd, J = 11.9,5.9Hz,1H), 3.98(dd,J=11.9,4.2Hz,1H), 3.88(d,J=6.3Hz,6H), 3.80(s,3H), 3.48(s,1H); 13 C NMR(126MHz, CDCl 3 )δ165.07,153.43,150.77,148.62,145.23,124.72,124.13,121.61,121.04,120.08,112.28,112.11,110.28,97.32,63.17,55.96,55.94,55.77.

[0045] 2b 1 H NMR(500MHz, CDCl 3 )δ7.15–7.02(m,2H), 6.97–6.87(m,2H), 6.81(d,J=8.4Hz,1H), 6.67–6.60(m,2H), 4.90(t,J=4.3Hz ,1H), 4.20(d,J=4.4Hz,2H), 3.89–3.79(m,27H),3.61(s,1H); 13 C NMR(126MHz, CDCl 3 )δ168.64,150.60,149.40,147.08,146.78,143.92,124.04,121.16,118.82,112.66,112.46,111.17,105.53,80.71,63.26,56.17,5...

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Abstract

Belonging to the technical field of biomass degradation, the invention relates to a method for degrading oxidation lignin into a small molecular aromatic compound, and in particular relates to a method of breaking C-C bond by nontransition metal catalysis to degrade oxidation lignin into a small molecular aromatic compound. The method includes: firstly oxidizing oxidation lignin in an organic solvent with an oxidizing agent, then subjecting the obtained intermediate product to alcoholysis or hydrolysis under the action of a catalyst so as to obtain a small molecular aromatic compound, like methoxy substituted benzoic acid, methoxy substituted phenol, methoxy substituted benzoate and chain alcohol, etc. The method provided by the invention has the advantages of simple steps, mild reaction conditions, high conversion rate (up to 100%), no need for transition metals and the like, has effect on multiple connection modes of oxidation lignin, can reach the purpose of high selectivity and efficient degradation of lignin, and is conducive to large-scale industrial application.

Description

Technical field [0001] The invention belongs to the technical field of biomass degradation, and specifically relates to a method for breaking the C-C bond through an organic method catalyzed by a non-transition metal to degrade oxidized lignin into a small molecule aromatic compound. Background technique [0002] With the continuous advancement of my country's urbanization process, energy demand continues to grow, and the contradiction between energy supply and demand is becoming more and more prominent. The development of new energy and renewable energy is the proper meaning of sustainable energy development. Biomass resources are extremely rich, clean and renewable resources. Lignocellulose is transformed from green plants through photosynthesis. It has a wide source and low price. It is a non-food renewable biomass resource. The world produces about 17 billion tons of lignocellulose every year through photosynthesis, but its utilization is less than 1% of the total, which has...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/00C07C69/78C07C27/02C07C63/06C07C37/055C07C39/04C07C69/92C07C69/712C07C65/21C07C59/125C07C41/26C07C43/23C07C67/08C07C69/708
CPCY02P20/52C07C67/00C07C37/0555C07C41/26C07C51/09C07C67/08C07C69/78C07C69/92C07C69/712C07C63/06C07C65/21C07C59/125C07C39/04C07C43/23C07C69/708
Inventor 张越涛何江华王银玲
Owner JILIN UNIV
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