CN111018816A - Choline chloride green catalysis chitin monomer N-acetylglucosamine degradation preparation 3-acetamido-5-acetylfuran - Google Patents
Choline chloride green catalysis chitin monomer N-acetylglucosamine degradation preparation 3-acetamido-5-acetylfuran Download PDFInfo
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- CN111018816A CN111018816A CN201911154155.XA CN201911154155A CN111018816A CN 111018816 A CN111018816 A CN 111018816A CN 201911154155 A CN201911154155 A CN 201911154155A CN 111018816 A CN111018816 A CN 111018816A
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- acetamido
- acetylfuran
- acetylglucosamine
- choline chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/66—Nitrogen atoms
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- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for catalyzing and degrading chitin monomer N-acetylglucosamine by choline chloride, which uses choline chloride as a catalyst and has the following operation method: under the temperature of 180 ℃ and 200 ℃, adding a small amount of chloride and boric acid as auxiliary catalysts, and refluxing for 10min at normal pressure by using N-methylpyrrolidone as a solvent to convert N-acetylglucosamine to obtain 3-acetamido-5-acetylfuran. The reaction system is simple, green and environment-friendly, the used raw materials are low in price, and the method solves the problem that the conventional ionic liquid synthesis operation is complex. The catalyst is easy to obtain and regenerate, and is proved to be a sustainable catalyst, and the use of the catalyst can greatly reduce the pollution to the environment and bring great economic and environmental benefits for chemical production business.
Description
Technical Field
The invention belongs to the field of renewable biomass catalytic conversion, and provides a nitrogen-containing platform compound 3-acetamido-5-acetylfuran prepared by using a monomer N-acetylglucosamine of biomass resource chitin as a raw material, using cheap and nontoxic quaternary ammonium salt choline chloride as a catalyst and organic solvents such as N-methylpyrrolidone as solvents in the presence of boric acid.
Background
At present, biomass utilization is mainly focused on woody biomass materials such as cellulose, lignin and the like, the research on cellulose and xylose biomass is relatively extensive, and the research on chitin biomass conversion is relatively lagged. Chitin biomass, the most common polysaccharide after cellulose, is usually obtained from industrial marine waste, and most importantly, it contains nitrogen itself, most of which is dumped into landfills and oceans, although it may be the only abundant renewable resource containing nitrogen chemicals and materials. Chitin contains nitrogen, and whether raw materials contain nitrogen or not has great influence, so that the development and utilization of chitin biomass have important significance.
The chitin biomass comprises chitin, chitosan and its corresponding monomer (N-acetylglucosamine) and its derivatives. Chitin biomass can be converted into various high value-added compound intermediates by catalytic conversion, such as nitrogen-containing compounds, 3-acetamido-5-acetylfuran, 3-acetamido-furan, acetaldehyde, pyrrole and the like, furan derivatives, 5-chloromethyl furfural, 5-hydroxymethyl furfural and the like, organic acids, levulinic acid, acetic acid and the like. The substances are important platform compounds, play important roles in a plurality of industries and have great application values. At present, more and more useful products from chitin continue to attract commercial development, so that chitin is not only an underutilized resource, but also a novel functional biological material with wide application prospect, and is a nitrogen source with huge potential.
In recent years, the synthesis and catalytic application of room temperature ionic liquids have attracted much attention because of their important attributes, such as wide range of liquid state, negligible vapor pressure, high catalytic activity, good chemical and thermal stability, potential recoverability, possibility of design, ease of separation from reactants, etc. However, most imidazoline ionic liquids are highly toxic, costly to prepare, and highly sensitive to water. The replacement of ionic liquids with an environmentally friendly alternative would be a huge sign, as it would provide a greener catalytic route. From the viewpoint, choline chloride has the characteristics of no toxicity, good water solubility, sustainability, reusability and the like, is a low-cost, biodegradable and safe quaternary ammonium salt, can be extracted from biomass, and can form a deep eutectic solvent system after being combined with hydrogen donors such as carboxylic acid, alcohol, hexose and the like. Choline chloride has been applied to catalytic conversion of cellulose so far, but studies on conversion of chitin biomass by choline chloride have not been utilized and reported.
In the invention, the monomer choline chloride is used as a catalyst for the first time, and the N-acetylglucosamine is catalytically degraded under the condition of oil bath to prepare the 3-acetamido-5-acetylfuran. The reaction time is short, the yield of the 3-acetamido-5-acetylfuran is high, the byproducts are few, the conversion rate of biomass is high, the operation is simple and convenient, great breakthrough is made in both yield and time, and the concept of sustainable development is reflected.
Disclosure of Invention
The invention mainly solves the technical problem of finding a low-cost, biodegradable and safe catalyst for catalyzing and degrading N-acetylglucosamine to obtain a nitrogen-containing platform compound 3-acetamido-5-acetylfuran with high added value. The invention is completed by the following modes:
the dosage ratio of the N-acetylglucosamine to the choline chloride catalyst is 1: 1, and the dosage of the raw materials is controlled to be 0.05-5 g. The reaction is carried out for 0.1-6h at the constant temperature of 100-200 ℃.
The additives under the above reaction conditions include: HCl, H3BO3、B2O3、AlCl3·6H2O、ZnCl2、MgCl2·6H2O、CrCl3·6H2O、NaCl、SnCl4·5H2O、CaCl2、CuCl2·H2O、FeCl3、FeCl2、BaCl2。
Taking a certain amount of chitin monomer N-acetylglucosamine, a certain amount of choline chloride catalyst and a cocatalyst into a round-bottom flask, adding a certain amount of organic solvent to dissolve the mixture into a homogeneous state, and reacting for a period of time at a constant temperature. Diluting the reactant with methanol to obtain diluted solution, and measuring the content of the 3-acetamido-5-acetylfuran produced by the reaction by using high performance liquid chromatography and a standard curve drawn by a standard substance. Extracting the reaction liquid with 20ml ethyl acetate, merging the extraction liquid after three times of extraction, and concentrating under reduced pressure to obtain a solid crude product containing 3-acetamido-5-acetylfuran.
The invention aims to provide a novel method for directly catalyzing and converting chitin monomer N-acetylglucosamine into 3-acetamido-5-acetylfuran in an organic solvent system by taking choline chloride as a catalyst. In the method, the product yield is high, the generated byproducts are less, great breakthrough is made in yield and time, and the concept of sustainable development is embodied.
Detailed Description
The following is a specific example for further illustrating the methods described herein, but the invention is not meant to be so limited.
Example 1 0.1g of H was added to a round bottom flask containing 0.1g N-acetylglucosamine and 0.05g of choline chloride3BO3As a cocatalyst, 10ml of N-methyl pyrrolidone is dissolved, heated and stirred in a constant temperature oil bath kettle at 180 ℃ and refluxed for 1 h. After the reaction is finished and the temperature is cooled to room temperature, the filtrate is decompressed and distilled to remove the solvent, 20ml of ethyl acetate is used for extraction, the extraction liquid is combined after three times of extraction, and the solid crude product containing the 3-acetamido-5-acetylfuran is obtained after decompression and concentration. The yield of 3-acetamido-5-acetylfuran can reach 55mol percent at most.
Example 2 0.1g N-acetylglucosamine, 0.05g choline chloride and 0.05g HCl were taken in a round-bottomed flask, and 0.1g H was added3BO3As the cocatalyst, 10ml of N-methyl pyrrolidone is taken to be dissolved, and heated, stirred and refluxed for 10min in a constant temperature oil bath kettle at 200 ℃. After the reaction is finished and the temperature is cooled to room temperature, the filtrate is decompressed and distilled to remove the solvent, 20ml of ethyl acetate is used for extraction, the extraction liquid is combined after three times of extraction, and the solid crude product containing the 3-acetamido-5-acetylfuran is obtained after decompression and concentration. The yield of 3-acetamido-5-acetylfuran can reach 65mol percent at most.
Example 30.1g N-acetylglucosamine, 0.15g choline chloride and 0.15g magnesium chloride were placed in a round bottom flask, and 0.1g H was added3BO3As a cocatalyst, 10ml of N-methyl pyrrolidone is dissolved, heated and stirred in a constant temperature oil bath kettle at 180 ℃ and refluxed for 1 h. After the reaction is finished and the temperature is cooled to room temperature, 1g of reaction solution is taken and added with 30ml of methanol for dilution, and the content of the 3-acetamido-5-acetylfuran is detected by a high performance liquid chromatography method. And distilling the filtrate under reduced pressure to remove the solvent, extracting with 20ml ethyl acetate for three times, combining the extract, and concentrating under reduced pressure to obtain a solid crude product containing the 3-acetamido-5-acetylfuran. The yield of the 3-acetamido-5-acetylfuran can reach 49mol percent at most.
Example 4 0.1g N-acetylglucosamine, 0.05g choline chloride and 0.05g AlCl were taken3To a round bottom flask, 0.1g H was added3BO3As a cocatalyst, 10ml of N-methyl pyrrolidone is dissolved, heated and stirred in a constant temperature oil bath kettle at 200 ℃ and refluxed for 1 h. After the reaction is finished and the temperature is cooled to room temperature, the filtrate is decompressed and distilled to remove the solvent, 20ml of ethyl acetate is used for extraction, the extraction liquid is combined after three times of extraction, and the solid crude product containing the 3-acetamido-5-acetylfuran is obtained after decompression and concentration. The yield of 3-acetamido-5-acetylfuran can reach 46mol percent at most.
Example 5 0.1g N-acetylglucosamine, 0.05g choline chloride and 0.05g NaCl were taken in a round-bottomed flask and 0.1g H was added3BO3As a cocatalyst, 10ml of N-methyl pyrrolidone is dissolved, heated and stirred in a constant temperature oil bath kettle at 200 ℃ and refluxed for 1 h. After the reaction is finished and the temperature is cooled to room temperature, the filtrate is decompressed and distilled to remove the solvent, 20ml of ethyl acetate is used for extraction, the extraction liquid is combined after three times of extraction, and the solid crude product containing the 3-acetamido-5-acetylfuran is obtained after decompression and concentration. The yield of 3-acetamido-5-acetylfuran can reach up to 40 mol%.
Example 6 0.1g N-acetylglucosamine, 0.05g choline chloride and 0.05g CaCl were taken2To a round bottom flask, 0.1g H was added3BO3As a cocatalyst, 10ml of dimethyl sulfoxide is taken to be dissolved, and heated, stirred and refluxed for 1h in a constant-temperature oil bath kettle at the temperature of 200 ℃. After the reaction was completed and cooled to room temperature, the solvent was removed from the filtrate by distillation under reduced pressure, and 20ml of ethyl acetate was usedExtracting with ethyl acetate, mixing extractive solutions, and concentrating under reduced pressure to obtain solid crude product containing 3-acetamido-5-acetylfuran. The yield of the 3-acetamido-5-acetylfuran can reach 53mol percent at most.
Claims (7)
1. A synthetic method for preparing 3-acetamido-5-acetylfuran by degrading chitin monomer N-acetamido glucose. The method is characterized in that choline chloride and hydrochloric acid are used as catalysts, boric acid is used as a cocatalyst, N-methyl pyrrolidone is used as a reaction solvent, reactants are mixed in a round bottom flask to be in a uniform reaction system, N-acetylglucosamine is degraded under the condition of oil bath, the N-acetylglucosamine is degraded under the condition of normal pressure and reflux for a period of time at a certain temperature, and insoluble impurities are removed by filtration after the reaction is stopped. And (3) carrying out rotary evaporation on the filtrate to remove the solvent, adding water to dissolve the residue, extracting by using ethyl acetate, and concentrating an ethyl acetate layer to obtain a crude product of the 3-acetamido-5-acetylfuran. The yield can reach 65mol percent at most.
2. The process for preparing 3-acetamido-5-acetylfuran by catalytic conversion of N-acetylglucosamine according to claim 1, further characterized in that: the solvent used includes methanol, ethanol, propanol, acetone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, etc.
3. The method of claim 1 for producing 3-acetamido-5-acetylfuran by catalytic conversion of N-acetylglucosamine, wherein the additive comprises: HCl and AlCl3·6H2O、ZnCl2、MgCl2·6H2O、CrCl3·6H2O、NaCl、SnCl4·5H2O、CaCl2、CuCl2·H2O、FeCl3、FeCl2、BaCl2。
4. The process for catalytically converting N-acetylglucosamine into 3-acetamido-5-acetylfuran of claim 1, further characterized in that: the reaction system is carried out under the conditions of oil bath heating and normal pressure reflux, the temperature is 140 ℃ and 200 ℃, and the reaction time is 0.1-5 h.
5. The process for preparing 3-acetamido-5-acetylfuran by catalytic conversion of N-acetylglucosamine according to claim 1, further characterized in that: the dosage of the substrate is 50mg-5g, and the molar weight of the added catalyst is 0.1-5 times of that of the substrate; the molar amount of the additive added is 0.1-5 times of that of the substrate. The amount of the solvent used is 0-100 mL.
6. The process for preparing 3-acetamido-5-acetylfuran by catalytic conversion of N-acetylglucosamine according to claim 1, further characterized in that: the reaction system is carried out in a 20-100ml round-bottom flask, the reaction temperature is 120-.
7. The process for preparing 3-acetamido-5-acetylfuran by catalytic conversion of N-acetylglucosamine according to claim 1, further characterized in that: the crude product content of the target product 3-acetamido-5-acetylfuran is extracted and concentrated, and the yield can reach 65mol percent at most.
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| CN201911154155.XA CN111018816A (en) | 2019-11-22 | 2019-11-22 | Choline chloride green catalysis chitin monomer N-acetylglucosamine degradation preparation 3-acetamido-5-acetylfuran |
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| CN201911154155.XA CN111018816A (en) | 2019-11-22 | 2019-11-22 | Choline chloride green catalysis chitin monomer N-acetylglucosamine degradation preparation 3-acetamido-5-acetylfuran |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024493A (en) * | 2021-03-25 | 2021-06-25 | 南京工业大学 | Method for preparing 3-acetamido-5-acetylfuran by catalyzing N-acetylglucosamine with ammonium chloride |
| CN114478446A (en) * | 2022-02-24 | 2022-05-13 | 中国科学院山西煤炭化学研究所 | Method for preparing chromogen III by converting D-acetylglucosamine |
| CN114507199A (en) * | 2022-02-16 | 2022-05-17 | 中国科学院山西煤炭化学研究所 | Method for preparing 3-acetamido-5-acetylfuran |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024493A (en) * | 2021-03-25 | 2021-06-25 | 南京工业大学 | Method for preparing 3-acetamido-5-acetylfuran by catalyzing N-acetylglucosamine with ammonium chloride |
| CN114507199A (en) * | 2022-02-16 | 2022-05-17 | 中国科学院山西煤炭化学研究所 | Method for preparing 3-acetamido-5-acetylfuran |
| CN114478446A (en) * | 2022-02-24 | 2022-05-13 | 中国科学院山西煤炭化学研究所 | Method for preparing chromogen III by converting D-acetylglucosamine |
| CN114478446B (en) * | 2022-02-24 | 2023-09-12 | 中国科学院山西煤炭化学研究所 | Method for preparing chromogen III by converting D-acetamido glucose |
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Application publication date: 20200417 |