CN112142701A - Preparation of 3-acetamido-5-acetylfuran by catalyzing and degrading chitin monomer N-acetamido glucose with alcamines ionic liquid - Google Patents
Preparation of 3-acetamido-5-acetylfuran by catalyzing and degrading chitin monomer N-acetamido glucose with alcamines ionic liquid Download PDFInfo
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- acetamido
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- GPLHPEIJJXDRBA-UHFFFAOYSA-N n-(5-acetylfuran-3-yl)acetamide Chemical compound CC(=O)NC1=COC(C(C)=O)=C1 GPLHPEIJJXDRBA-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 37
- 229920002101 Chitin Polymers 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 title claims abstract description 8
- 230000000593 degrading effect Effects 0.000 title claims abstract description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims description 3
- 239000008103 glucose Substances 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 3
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 claims abstract description 28
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 claims abstract description 28
- MBLBDJOUHNCFQT-LXGUWJNJSA-N N-acetylglucosamine Natural products CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 claims abstract description 28
- 229950006780 n-acetylglucosamine Drugs 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 alcohol amine Chemical class 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004327 boric acid Substances 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- 239000012043 crude product Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 15
- GJMPSRSMBJLKKB-UHFFFAOYSA-N 3-methylphenylacetic acid Chemical compound CC1=CC=CC(CC(O)=O)=C1 GJMPSRSMBJLKKB-UHFFFAOYSA-N 0.000 claims description 12
- 229940117957 triethanolamine hydrochloride Drugs 0.000 claims description 12
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 2
- 229940106681 chloroacetic acid Drugs 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 238000002390 rotary evaporation Methods 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000012824 chemical production Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 28
- 239000007787 solid Substances 0.000 description 13
- 239000002028 Biomass Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 230000006837 decompression Effects 0.000 description 8
- 239000000284 extract Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- MKIHPYJPBNFAMQ-UHFFFAOYSA-N 2-chloroacetate;tris(2-hydroxyethyl)azanium Chemical compound [O-]C(=O)CCl.OCC[NH+](CCO)CCO MKIHPYJPBNFAMQ-UHFFFAOYSA-N 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VEARVAHDXMYVRO-UHFFFAOYSA-N 1,1-dichloroethane;ethanol Chemical compound CCO.CC(Cl)Cl VEARVAHDXMYVRO-UHFFFAOYSA-N 0.000 description 1
- KAZRCBVXUOCTIO-UHFFFAOYSA-N 5-(chloromethyl)furan-2-carbaldehyde Chemical compound ClCC1=CC=C(C=O)O1 KAZRCBVXUOCTIO-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MSUYGSATOVDCFI-UHFFFAOYSA-N n-(furan-3-yl)acetamide Chemical compound CC(=O)NC=1C=COC=1 MSUYGSATOVDCFI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Saccharide Compounds (AREA)
Abstract
3-acetamido-5-acetylfuran is an important platform compound. The invention discloses a method for degrading chitin monomer N-acetylglucosamine by using an alcohol amine ionic liquid, which takes the alcohol amine ionic liquid as a catalyst and has the following operation method: at the temperature of 180 ℃ and 200 ℃, adding boric acid as a cocatalyst, taking N, N-dimethylacetamide as a solvent, refluxing for 20min under normal pressure, and converting N-acetylglucosamine to obtain 3-acetamido-5-acetylfuran. The reaction system is simple in method, green and environment-friendly, the used alcohol amine ionic liquid is simple in synthesis method, the raw materials are cheap and easy to obtain, and the alcohol amine ionic liquid can be repeatedly used as a catalyst, so that great economic benefits and environmental benefits are brought to chemical production business.
Description
Technical Field
The invention belongs to the field of renewable biomass catalytic conversion, and provides a method for preparing a nitrogen-containing platform compound 3-acetamido-5-acetylfuran in the presence of boric acid by using a monomer N-acetylglucosamine of biomass resource chitin as a raw material, using a cheap and green alcohol amine ionic liquid as a catalyst, and using organic solvents such as N, N-dimethylacetamide as a solvent.
Background
In recent years, with the increasing problems of exhaustion of fossil resources, environmental pollution and the like, the search for new green resources that can replace fossil resources is becoming an urgent issue to be solved at present. The biomass attracts the attention of scientists due to the advantages of renewability, easy degradation, no toxicity, no harm and the like, and becomes a research hotspot gradually.
Chitin biomass is the second most abundant biomass resource on earth, except for cellulose, and the amount of chitin produced in industrial waste from fisheries and marine industries worldwide can reach approximately 100 million tons per year. Therefore, the research of converting chitin biomass into high value-added chemicals becomes the key point of the development of chemical raw materials and energy industry in the future, and has important significance for the resource utilization of biomass, the alleviation of resource shortage and the solution of increasingly severe environmental problems.
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 catalysis, 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.
The ionic liquid is an emerging green solvent which is completely composed of anions and cations and is liquid at or near room temperature. Ionic liquids have received a great deal of attention due to their unique properties, such as wide range of liquid states, 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 and costly to prepare. Therefore, the ionic liquid which is green, environment-friendly, cheap and easy to obtain is found to have important value and significance. The alcamines ionic liquid has the characteristics of simple synthesis method, cheap and easily available raw materials, environmental protection and the like, and meets the requirement of green chemistry. However, no relevant report exists about the application of the alcohol amine ionic liquid in the aspect of chitin biomass at present.
In the invention, the alcohol amine ionic liquid is used as a catalyst, and the 3-acetamido-5-acetylfuran is prepared by directly catalyzing and degrading the N-acetylglucosamine under the condition of oil bath. 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, simple-preparation-method and reusable green catalyst for catalyzing and degrading N-acetylglucosamine to obtain a high-added-value nitrogen-containing platform compound 3-acetamido-5-acetylfuran. The invention is completed by the following modes:
1. the synthesis of the alcohol amine ionic liquid comprises the following steps: the synthesis of triethanolamine hydrochloride ionic liquid is exemplified. A certain amount of ethanolamine was weighed into a round bottom flask and added to the dichloroethane-ethanol solution. A small excess of organic or inorganic acid is weighed and slowly dropped into the round-bottom flask while stirring. Stirring at room temperature under reflux for 2 h. After the reaction was completed, the reaction mixture was washed with ethyl acetate several times for extraction, and rotary-evaporated. Then drying the mixture in vacuum at 50 ℃ for 24h to obtain the alcohol amine ionic liquid.
2. And (2) taking 100mg of N-acetylglucosamine, a certain amount of the synthesized alcohol amine ionic liquid catalyst and 100mg of cocatalyst into a round-bottom flask, adding 10mL of solvent for dissolving, heating to a set temperature, and stopping reaction after reacting for a certain time. Filtering to remove insoluble impurities, taking 0.5mL of filtrate, adding 15mL of methanol for dilution, and detecting the content of the 3-acetamido-5-acetylfuran by using high performance liquid chromatography. And distilling the filtrate under reduced pressure to remove the solvent, dissolving the residue in 20mL of water, extracting with 20mL of ethyl acetate, combining the extracts after three times of extraction, concentrating under reduced pressure to obtain a solid crude product containing 3-acetamido-5-acetylfuran, and recycling the alcohol amine ionic liquid.
The product is measured by high performance liquid chromatography to determine the content of 3-acetamido-5-acetylfuran, and the yield of 3-acetamido-5-acetylfuran is calculated according to a standard curve.
The ethanolamine in the method comprises monoethanolamine, diethanolamine and triethanolamine.
The organic or inorganic acid in the method includes hydrochloric acid, sulfuric acid, chloroacetic acid and the like.
In the method, the solvent is N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, water and the like.
The reaction for catalytically converting the N-acetylglucosamine into the 3-acetamido-5-acetylfuran is carried out in a 50mL round-bottom flask under the condition of normal pressure reflux, the reaction temperature is 150 ℃ and 210 ℃, and the reaction time is 10min-120 min.
The molar mass of the ionic liquid catalyst in the method is 1-7 times of that of the substrate.
The catalyst promoter in the method comprises boric acid, boron oxide, calcium chloride and the like.
The invention aims to provide a novel method for directly catalytically converting chitin monomer N-acetylglucosamine into 3-acetamido-5-acetylfuran in an organic solvent system with an alcohol amine ionic liquid 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 N-acetylglucosamine and 0.4g triethanolamine hydrochloride ionic liquid were placed in a round bottom flask and 0.1g H was added3BO3As a cocatalyst, 10ml of N, N-dimethylacetamide is taken to be dissolved, and heated, stirred and refluxed for 60min in a constant-temperature oil bath pan at 180 ℃. 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 the 3-acetamido-5-acetylfuran can reach 62mol percent.
EXAMPLE 2 0.1g N-acetylGlucosamine, 0.2g triethanolamine hydrochloride ionic liquid in round bottom flask, 0.1g H added3BO3As a cocatalyst, 10ml of N, N-dimethylacetamide is taken to be dissolved, and heated, stirred and refluxed for 60min in a constant-temperature oil bath pan at 180 ℃. 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 52 mol%.
Example 3 0.1g N-acetylglucosamine and 0.2g triethanolamine hydrochloride ionic liquid were placed in a round bottom flask and 0.1g H was added3BO3As a cocatalyst, 10ml of N-methyl pyrrolidone is dissolved, heated, stirred and refluxed in a constant temperature oil bath kettle at 180 ℃ for 60 min. And after the reaction is finished and the reaction product is cooled to room temperature, the filtrate is subjected to reduced pressure distillation to remove the solvent, the solvent is extracted by using 20mL of ethyl acetate, the extract liquor is combined after three times of extraction, and the solid crude product containing the 3-acetamido-5-acetylfuran is obtained through reduced pressure concentration. The yield of 3-acetamido-5-acetylfuran can reach 46mol percent at most.
Example 4 0.1g N-acetylglucosamine and 0.2g triethanolamine chloroacetate ionic liquid were placed in a round bottom flask, and 0.1g H was added3BO3As a cocatalyst, 10ml of N-methyl pyrrolidone is taken to be dissolved, and heated, stirred and refluxed for 60min in a constant-temperature oil bath pan at 180 ℃. And after the reaction is finished and the reaction product is cooled to room temperature, the filtrate is subjected to reduced pressure distillation to remove the solvent, the solvent is extracted by using 20mL of ethyl acetate, the extract liquor is combined after three times of extraction, and the solid crude product containing the 3-acetamido-5-acetylfuran is obtained through reduced pressure concentration. The yield of 3-acetamido-5-acetylfuran can reach up to 45 mol%.
Example 5A round-bottomed flask was charged with 0.1g B g of 0.1g N-acetylglucosamine and 0.2g of triethanolamine hydrochloride ionic liquid2O3As a cocatalyst, 10ml of N, N-dimethylacetamide is taken to be dissolved, and heated, stirred and refluxed for 60min in a constant-temperature oil bath pan at 180 ℃. Cooling to room temperature after the reaction, distilling the filtrate under reduced pressure to remove the solvent, extracting with 20ml ethyl acetate for three times, mixing the extractive solutions, and concentrating under reduced pressure to obtain the final product containing 3-acetamido-5-acetylA solid crude product of furan. The yield of 3-acetamido-5-acetylfuran can reach up to 50 mol%.
EXAMPLE 6 0.1g N-acetylglucosamine and 0.3g triethanolamine hydrochloride ionic liquid were placed in a round bottom flask and 0.1g H was added3BO3As a cocatalyst, 10ml of N, N-dimethylacetamide is taken to be dissolved, and heated, stirred and refluxed for 60min in a constant-temperature oil bath pan at 180 ℃. 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 the 3-acetamido-5-acetylfuran can reach 58mol percent at most.
Example 7A round-bottomed flask was charged with 0.1g H g of 0.1g N-acetylglucosamine and 0.5g of triethanolamine hydrochloride ionic liquid3BO3As a cocatalyst, 10ml of N, N-dimethylacetamide is taken to be dissolved, and heated, stirred and refluxed for 60min in a constant-temperature oil bath pan at 180 ℃. 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 62mol percent at most.
Example 8A round-bottomed flask was charged with 0.1g H g of 0.1g N-acetylglucosamine and 0.7g of triethanolamine hydrochloride ionic liquid3BO3As a cocatalyst, 10ml of N, N-dimethylacetamide is taken to be dissolved, and heated, stirred and refluxed for 60min in a constant-temperature oil bath pan at 180 ℃. 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 the 3-acetamido-5-acetylfuran can reach 63mol percent.
Example 9A round-bottomed flask was charged with 0.1g H g of 0.1g N-acetylglucosamine and 0.4g of triethanolamine hydrochloride ionic liquid3BO3As the cocatalyst, 10ml of N, N-dimethylacetamide is taken to be dissolved, and heated, stirred and refluxed for 60min in a constant-temperature oil bath pan at 160 ℃. Cooling to the end of the reactionAnd (3) distilling the filtrate at room temperature under reduced pressure to remove the solvent, extracting with 20ml of 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 3-acetamido-5-acetylfuran can reach up to 52 mol%.
Example 10A round-bottomed flask was charged with 0.1g H g of 0.1g N-acetylglucosamine and 0.4g of triethanolamine hydrochloride ionic liquid3BO3As the cocatalyst, 10ml of N, N-dimethylacetamide was dissolved, and heated, stirred and refluxed for 60min in a constant temperature oil bath 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 the 3-acetamido-5-acetylfuran can reach 63mol percent at most.
EXAMPLE 11A round-bottomed flask was charged with 0.1g H g of 0.1g N-acetylglucosamine and 0.4g of triethanolamine hydrochloride ionic liquid3BO3As the cocatalyst, 10ml of N, N-dimethylacetamide is taken to be dissolved, and heated, stirred and refluxed for 90min in a constant temperature oil bath kettle at 170 ℃. 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 the 3-acetamido-5-acetylfuran can reach 53mol percent at most.
EXAMPLE 12 0.1g N-acetylglucosamine and 0.4g triethanolamine chloroacetate Ionic liquid were put in a round-bottomed flask, and 0.1g H was added3BO3As the cocatalyst, 10ml of N, N-dimethylacetamide is taken to be dissolved, and heated, stirred and refluxed for 60min in a constant temperature oil bath kettle at 170 ℃. 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 the 3-acetamido-5-acetylfuran can reach 51mol percent at most.
Claims (8)
1. A synthetic method for preparing 3-acetamido-5-acetylfuran by degrading chitin monomer N-acetamido glucose. The method is characterized in that triethanolamine hydrochloride ionic liquid is used as a catalyst, boric acid is used as a cocatalyst, N, N-dimethylacetamide is used as a reaction solvent, reactants are mixed in a round bottom flask 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 at a certain temperature for a period of time, 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 62mol percent at most.
2. The method for preparing 3-acetamido-5-acetylfuran by using the alcamines ionic liquid to catalyze the degradation of chitin and monomers thereof according to claim 1, which is characterized in that the method for synthesizing the alcamines ionic liquid comprises the following steps: the monoethanolamine, the diethanolamine and the triethanolamine are respectively mixed with different inorganic acids and organic acids, such as: hydrochloric acid, sulfuric acid, chloroacetic acid and the like react to generate a series of alcohol amine ionic liquids.
3. 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 N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, water and the like.
4. The method of claim 1, wherein the promoter comprises: boric acid, boron oxide, calcium chloride, and the like.
5. 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 150 ℃ and 210 ℃, and the reaction time is 10-120 min.
6. 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 1-7 times of that of the substrate; the molar amount of the additive added is 1-5 times of that of the substrate. The amount of the solvent is 0-100 ml.
7. 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 150-210 ℃, and the reaction time is 10-120 min.
8. 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 62mol percent at most.
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