CN116143638A - Method for preparing nitrogen-containing aromatic compound by catalyzing lignin through Fe-terpyridine - Google Patents

Method for preparing nitrogen-containing aromatic compound by catalyzing lignin through Fe-terpyridine Download PDF

Info

Publication number
CN116143638A
CN116143638A CN202111401701.2A CN202111401701A CN116143638A CN 116143638 A CN116143638 A CN 116143638A CN 202111401701 A CN202111401701 A CN 202111401701A CN 116143638 A CN116143638 A CN 116143638A
Authority
CN
China
Prior art keywords
lignin
nitrogen
reaction
terpyridine
containing aromatic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111401701.2A
Other languages
Chinese (zh)
Inventor
李昌志
罗奇
安庆大
张涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Dalian Polytechnic University
Original Assignee
Dalian Institute of Chemical Physics of CAS
Dalian Polytechnic University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS, Dalian Polytechnic University filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN202111401701.2A priority Critical patent/CN116143638A/en
Publication of CN116143638A publication Critical patent/CN116143638A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/325—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups reduction by other means than indicated in C07C209/34 or C07C209/36
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a method for preparing a nitrogen-containing aromatic compound by catalyzing lignin with Fe-terpyridine, in particular to a novel method for converting lignin beta-O-4 model compounds or lignin raw materials into the nitrogen-containing aromatic compound by taking Fe-terpyridine as a catalyst, taking water as a solvent and a hydrogen source and taking nitrobenzene as a nitrogen source. The method realizes the reaction of lignin under mild conditions through a substrate and water under the condition of no external hydrogen source to prepare the nitrogen-containing aromatic compound. The yield is up to more than 70%. The invention uses renewable raw materials, and the raw materials are cheap and have wide sources; the reaction process does not need the use of an external hydrogenation source, and an ammonification reaction is realized by using lignin beta-O-4 model compound or lignin raw material and water; inorganic acid and alkali are not required for the reaction; the reaction condition is mild, the yield of the nitrogen-containing aromatic compound is high, and the catalyst has the advantages of longer service life, higher reaction activity and the like.

Description

Method for preparing nitrogen-containing aromatic compound by catalyzing lignin through Fe-terpyridine
Technical Field
The invention belongs to the field of lignin high-valued utilization, and particularly relates to a method for preparing a nitrogen-containing aromatic compound by catalyzing lignin model compounds or lignin raw materials through Fe-terpyridine.
Background
Aromatic amines and their derivatives play an important role as building blocks, functional bonds and key parts in polypeptides, polymers and pharmaceuticals, being important components of organic synthesis (chem. Oc. Rev.2014,43, 779-791). Has unique bioactivity and is widely applied to the aspects of contrast imaging chemicals, pharmacy, disinsection, dyes, ligands of transition metal catalysts and the like (Nature, 2008,451,46). Therefore, the development of low-toxicity, efficient, economical, simple and green aromatic amines and their derivatives has great significance in organic synthesis, and has become a research hotspot in the chemical industry.
Currently, there are many methods for preparing aromatic amine compounds, typically by alkylating an amine with a halide, however, such methods suffer from various problems such as excessive alkylation, toxicity of the halide and related alkylating agents, and the production of excessive amounts of by-products. In recent years, the preparation of nitrogen-containing aromatic amines and derivatives thereof by activating alcohols by means of a hydrogen strategy has become a focus of attention, namely: the alcohol is dehydrogenated under the action of catalyst to produce corresponding aldehyde or ketone, which is condensed with primary amine, dehydrated to produce imine, and then reduced by catalytic hydrogenation to produce corresponding secondary amine or tertiary amine (chem. Rev.2010,110, 1611-1641), and the method can realize the conversion of imine into aromatic amine and its derivative by catalytic external hydrogenation source. Nitrobenzene is a common nitrogen-containing compound, and aniline is produced by catalytic hydroconversion, which is carried out at relatively high pressure (10-15 MPa) and temperature (100-150 ℃) and has high requirements for equipment (applied chemical, 2017,46,784-793). By one-step synthesis of aromatic amines and their derivatives from nitrobenzene and alcohols by means of a hydrogen strategy, specific equipment, demanding reaction conditions and complicated operations are avoided (chem. Eur. J.2011,17, 2587-2591). The method takes fossil resources as raw materials to obtain the aromatic amine chemicals. With the increasing exhaustion of fossil resources, the renewable resources are utilized to develop a high-selection conversion technology to prepare the aromatic amine chemicals, so that the dependence on fossil energy sources can be reduced, the environmental pressure is lightened, and the method is particularly important for sustainable social development.
Lignin is the only renewable aromatic non-fossil resource in nature as an important component of biomass (chem. Rev.2015,115, 11559-11624). Lignin is a three-dimensional polymer with a complex structure, and is composed of different types of methoxyphenylpropyl monomers (the lignin monomer is shown as formula 1), the complex structure and the intractable chemical bonds limit the development and the utilization of lignin, only 5% of lignin is applied to low-value commercial application, the rest of lignin is used as fuel to provide heat energy, power and the like, and most lignin is still discharged as industrial pulping waste, so that serious environmental pollution is caused. Therefore, the development of the directional catalytic way for depolymerizing lignin to prepare the arylamine compound with high added value has the dual significance of effectively utilizing renewable resources and reducing environmental pollution. The preparation of aromatic amine compounds by amination reaction using renewable lignin as a raw material is regarded as a new way for using renewable resources, and has important theoretical and practical significance for reasonable development and utilization of lignin resources.
Figure BDA0003364761600000031
Disclosure of Invention
Based on the background art, the invention aims to provide a method for preparing nitrogen-containing aromatic compounds by catalyzing lignin with Fe-terpyridine. The lignin model compound or lignin is used as a raw material, and the lignin model compound or lignin raw material is used for realizing the novel method for preparing the aromatic amine compound, and the proportion of water, nitrobenzene and lignin model compound dimer is formulated according to the literature (Angew.chem.int.ed.2021, 60,20666).
In order to achieve the above purpose, the method provided by the invention is to prepare an arylamine compound by using Fe-terpyridine (the preparation method of the formula 2 is referred to by chemical journal, 2012,70,2306.) as a catalyst, water as a solvent, water and lignin as hydrogen sources, and nitrobenzene as a nitrogen source to dimer lignin model compounds or lignin raw materials.
Figure BDA0003364761600000032
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the lignin model compound or lignin raw material is used as a substrate, water is used as a reaction solvent, water and lignin are used as hydrogen sources, nitrobenzene is used as a nitrogen source, an Fe-terpyridine catalyst is added, and the reaction is carried out for 8-24 hours at 25-85 ℃ to prepare the amine compound shown in the formula 3:
Figure BDA0003364761600000041
based on the technical scheme, the dosage of the Fe-terpyridine catalyst is 0.1-10mol% of the lignin model compound dimer.
Based on the above technical scheme, preferably, the Fe-terpyridine is 4mol%.
Based on the above technical scheme, preferably, the reaction temperature is 65 ℃; the reaction time was 14h.
Based on the technical scheme, the mol ratio of the substrate to the catalyst is 1:0.04, the mol ratio of nitrobenzene to the substrate is 1:1, and the water is 1.5mL.
Based on the technical scheme, the lignin model compound is one or more of 2- (2-methoxyphenoxy) -1-phenylethanol, 2- (2-methoxyphenoxy) -1- (2-methoxy) phenylethanol and 2- (2-methoxyphenoxy) -1- (4-methoxy) phenylethanol, and the lignin model compound is shown in a formula 4.
Figure BDA0003364761600000042
Based on the technical scheme, the lignin raw material is as follows: one or more of organic lignin, calcium lignosulfonate, alkali lignin, wood grinding lignin, enzymolysis lignin and gas explosion lignin.
Based on the technical scheme, the aromatic amine compound is as follows: one or more of 1- (phenethyl) -aniline, 1- (2-methoxyphenyl) ethyl) aniline and 1- (4-methoxyphenyl) ethyl) aniline, wherein the aromatic amine compound is shown in formula 5 and the nuclear magnetic information is shown in formula 6.
Figure BDA0003364761600000051
Advantageous effects of the invention
(1) The invention uses the substrate and water as hydrogen sources to realize the reaction without additional hydrogen sources, and has novel route and strong innovation.
(2) The catalyst used in the invention has very long service life, and can still keep high activity after repeated recycling, thus greatly reducing the catalytic cost.
(3) The lignin used in the invention is a renewable raw material, the raw material is cheap and wide in source, an external hydrogenation source is not needed in the reaction process, and the whole process is realized by lignin substrate molecules and water to prepare the nitrogen-containing aromatic chemicals, so that the atomic economy is high, and the product yield is high.
(4) The invention has mild reaction condition and no need of higher pressure.
Drawings
FIG. 1 is a nuclear magnetic spectrum of guaiacol prepared in example 1;
FIG. 2 is a nuclear magnetic spectrum of the 1- (phenethyl) -aniline compound prepared in example 1;
FIG. 3 is a nuclear magnetic spectrum of a 1- (2-methoxyphenyl) ethyl) aniline compound prepared in example 19;
FIG. 4 is a nuclear magnetic spectrum of a 1- (4-methoxyphenyl) ethyl) aniline compound prepared in example 20.
Detailed Description
The present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples, wherein the amount of the solvent added is not limited, and the skilled person can adjust the amount of the lignin substrate molecule of the present invention to 0.1mmol, nitrobenzene of 0.1mmol, and solvent added to 1.5mL according to the actual situation.
The catalyst described in the examples was Fe-terpyridine, which was used in an amount of 4mol% based on the lignin model compound. The lignin model compounds 2-phenoxy-1-phenylethanol, 2- (2-methoxyphenoxy) -1-phenylethanol, 1- (4-methoxyphenyl) -2-phenoxyethanol were synthesized according to literature (j.am. Chem. Soc.2010,132, 12554); the organic lignin, lignosulfonate, alkali lignin, wood grinding lignin, enzymatic hydrolysis lignin and gas explosion lignin are synthesized according to the literature (Material 2013,6,359).
Example 1
0.1mmol of lignin model compound 2- (2-methoxyphenoxy) -1-phenylethanol, 4mol% of Fe-terpyridine catalyst and 1.5ml of water are added into a 35 ml pressure-resistant tube, 0.1mmol of nitrobenzene is replaced by argon gas for three times, and the temperature is raised to 65 ℃ for reaction for 14 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with ethyl acetate to obtain an organic phase of the product, which was subjected to chromatography with a conversion of 95.6% and a yield of guaiacol (shown in FIG. 1) of 86.4% and a yield of 1- (phenethyl) -aniline of 75.3%.
Examples 2 to 6
Other process conditions and experimental procedures were as in example 1, but different reaction temperatures were used, and the results are shown in Table 1.
Table 1. Experimental results of catalytic conversion of lignin model compounds by Fe-terpyridine at different reaction temperatures.
Figure BDA0003364761600000071
As shown in Table 1, the reaction temperature has a certain influence on the yield of the product, the temperature is 65 ℃, the yield of the product 1- (phenethyl) -aniline is 75.3%, and the yield of the product guaiacol can reach 86.4%.
Examples 9 to 13
Other process conditions and experimental procedures were as in example 1, but with different reaction times, the results are shown in Table 2.
Table 2 experimental results of Fe-terpyridine catalytic conversion lignin model compounds at different reaction times.
Figure BDA0003364761600000081
As shown in Table 2, the yield of 1- (phenethyl) -aniline increased with the increase of the reaction time, the conversion rate increased with the increase of the reaction time, the reaction time was 14 hours, the yield of the product 1- (phenethyl) -aniline was 75.3%, and the yield of the product guaiacol was 86.4%.
Examples 14 to 18
Other process conditions and experimental procedures were the same as in example 1, except that the amount of Fe-terpyridine used in the catalyst was varied, and the results are shown in Table 3.
Table 3 shows experimental results of catalytic conversion of lignin model compounds with different amounts of Fe-terpyridine.
Figure BDA0003364761600000082
Example 19
Other process conditions and experimental procedures were the same as in example 1, except that 2- (2-methoxyphenoxy) -1- (2-methoxy) phenylethanol was used as a substrate, the conversion was 92.4%, and the yield of the product 1- (2-methoxyphenyl) ethyl) aniline was 72.3% and the yield of guaiacol was 80.6%.
Example 20
Other process conditions and experimental procedures were the same as in example 1, except that 2- (2-methoxyphenoxy) -1- (4-methoxy) phenylethanol was used as a substrate, the conversion was 94.7%, and the yield of product 1- (4-methoxyphenyl) ethyl) anilinone was 74.6% and the yield of guaiacol was 87.3%.
Examples 21 to 25
Other process conditions and experimental procedures were as in example 1, but different lignin raw materials were used, and the results are shown in table 4.
Table 4. Experimental results for catalytic conversion of lignin raw materials by Fe-terpyridine.
Project Lignin Total yield of arylamine compound (%)
Example 21 Organic lignin 3.62
Example 22 Lignin calcium sulfonate 1.27
Example 23 Alkali lignin 3.31
Example 24 Wood grinding lignin 2.34
Example 25 Gas explosion lignin 5.25
As shown in Table 4, fe-terpyridine can effectively catalyze different lignin types to prepare aromatic amine compounds.
Examples 26 to 34
The catalyst is inspected to be recycled, and the specific operation is as follows: 0.1mmol of lignin model compound 2- (2-methoxyphenoxy) -1-phenylethanol, 4mol% of Fe-terpyridine catalyst and 1.5ml of water are added into a 35 ml pressure-resistant tube, 0.1mmol of nitrobenzene is replaced by argon gas for three times, and the temperature is raised to 65 ℃ for reaction for 14 hours. After the reaction is finished, cooling to room temperature, extracting with ethyl acetate, and performing chromatographic analysis on the obtained product organic phase; then, 0.1mmol of lignin substrate molecule 2- (2-methoxyphenoxy) -1-phenylethanol, 1.5ml of water and 0.1mmol of nitrobenzene were added, the temperature was raised to 65℃after three gas substitutions, and the reaction was continued for 14 hours, and the post-treatment was carried out in the same manner as above.
Table 5. Recycling results of Fe-terpyridine catalytic conversion lignin model compounds.
Figure BDA0003364761600000101
As shown in Table 5, the reactivity of Fe-terpyridine was maintained after 10 cycles.
Comparative examples 1 to 15
Other process conditions and experimental procedures were the same as in example 1, but using different catalysts, the catalysts obtained in comparative examples 2 to 14 were prepared according to the literature (angel. Chem. Int. Ed.2017,56,3050) to obtain a metal loading of 4mol% by impregnation-reduction, and the comparative results are shown in table 6.
Table 6. Experimental results of catalytic conversion of different lignin model compounds under different catalyst conditions.
Figure BDA0003364761600000102
/>
Figure BDA0003364761600000111
/>

Claims (8)

1. A method for preparing a nitrogen-containing aromatic compound by catalyzing lignin with Fe-terpyridine is characterized in that a lignin model compound or lignin raw material is used as a substrate, water is used as a reaction solvent, nitrobenzene is used as a nitrogen source, water and the lignin model compound or lignin raw material are used as a hydrogen source, and Fe-terpyridine is added as a catalyst to react to prepare the nitrogen-containing aromatic compound.
2. The method of claim 1, wherein the reaction temperature is 25 ℃ to 85 ℃; the reaction time is 8-24h.
3. The method of claim 1, wherein the reaction temperature is 65 ℃ and the reaction time is 14h.
4. The method of claim 1, wherein the molar ratio of substrate to catalyst is 1:0.04.
5. The method of claim 1, wherein the molar ratio of nitrogen source to lignin model compound is 1:1.
6. The method of claim 1, wherein the lignin model compound is one or more of 2- (2-methoxyphenoxy) -1 phenylethanol, 2- (2-methoxyphenoxy) -1- (2-methoxy) phenylethanol, and 2- (2-methoxyphenoxy) -1- (4-methoxy) phenylethanol.
7. The method according to claim 1, characterized in that the lignin raw material is: one or more of organic lignin, calcium lignosulfonate, alkali lignin, wood grinding lignin, enzymolysis lignin and gas explosion lignin.
8. The method of claim 1, wherein the nitrogen-containing aromatic compound is: one or more of 1- (phenethyl) -aniline, 1- (2-methoxyphenyl) ethyl) aniline, 1- (4-methoxyphenyl) ethyl) aniline.
CN202111401701.2A 2021-11-19 2021-11-19 Method for preparing nitrogen-containing aromatic compound by catalyzing lignin through Fe-terpyridine Pending CN116143638A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111401701.2A CN116143638A (en) 2021-11-19 2021-11-19 Method for preparing nitrogen-containing aromatic compound by catalyzing lignin through Fe-terpyridine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111401701.2A CN116143638A (en) 2021-11-19 2021-11-19 Method for preparing nitrogen-containing aromatic compound by catalyzing lignin through Fe-terpyridine

Publications (1)

Publication Number Publication Date
CN116143638A true CN116143638A (en) 2023-05-23

Family

ID=86360561

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111401701.2A Pending CN116143638A (en) 2021-11-19 2021-11-19 Method for preparing nitrogen-containing aromatic compound by catalyzing lignin through Fe-terpyridine

Country Status (1)

Country Link
CN (1) CN116143638A (en)

Similar Documents

Publication Publication Date Title
CN101475442B (en) Method for preparing ethylene glycol from oxalic ester
CN111217710B (en) Method for preparing 1, 5-pentanediamine by organic catalysis of L-lysine chemical decarboxylation
CN105693896A (en) Acenaphthenequinone-1,2-asymmetric diketinimatonickel complex catalyst, and preparation method and application thereof
CN109776628B (en) Mesoporous zirconium tannate catalyst and application thereof in catalyzing furfural hydrogenation
CN110878072A (en) Method for preparing 3-acetamido-5-acetylfuran from chitin monomer N-acetylglucosamine
CN103193623A (en) Method for catalytic preparation of acetylpropionic acid in one step by using waste residues obtained by producing xylose
CN102503774A (en) Method for synthesizing 1,2-cyclohexanediol by cyclohexene under selenium catalysis
CN112371150B (en) Nickel-aluminum bimetal nitrogen-carbon doped catalyst, preparation method thereof and application thereof in catalyzing levulinic acid hydrogenation to prepare gamma-valerolactone
CN116143638A (en) Method for preparing nitrogen-containing aromatic compound by catalyzing lignin through Fe-terpyridine
CN109704902B (en) Ionic liquid catalytic deoxidation method in lignin derivative hydrodeoxygenation process
CN116143631A (en) Pd/SnO 2 Method for preparing nitrogen-containing aromatic compound by catalyzing lignin
CN104817524A (en) Method for preparing 5-hydroxymethyl furoic acid through catalytic conversion on fructose
CN114436808B (en) CO based on cyclic conversion of imidazolecarboxylate and imidazolecarbonate 2 Method for preparing formic acid by hydrogenation
CN102416348A (en) Polymer supported imidazole ion catalyst as well as preparation method and application thereof
CN101429102A (en) Method for producing dimethyl ether with methanol dehydration
CN110590860B (en) Method for preparing lignin oligomer by selective reductive degradation
CN101531574B (en) Method for preparing 3,4,5-trimethoxy toluene
CN108707064B (en) Production method for co-producing dimethyl ether by using blast furnace gas
CN109438402B (en) Benzofuranone derivatives and synthesis method thereof
CN113416147A (en) Schiff base-metal organic complex and preparation method and application thereof
CN112142701A (en) Preparation of 3-acetamido-5-acetylfuran by catalyzing and degrading chitin monomer N-acetamido glucose with alcamines ionic liquid
CN112441888A (en) Pd-ReOx/CeO2Method for preparing nitrogen-containing aromatic compound by catalyzing lignin ammoniation reaction
US20210347750A1 (en) Rapid synthesis method for biomass-based amine
CN116023269B (en) Synthesis method of tetrabutylammonium bromide
CN110975939A (en) Ethylene carbonate hydrogenation heterogeneous catalyst, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination