CN109824629B - Method for preparing 3-amino-5- (alpha-aminoethyl) tetrahydrofuran by using N-acetylglucosamine - Google Patents
Method for preparing 3-amino-5- (alpha-aminoethyl) tetrahydrofuran by using N-acetylglucosamine Download PDFInfo
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- 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 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 30
- 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 title claims abstract description 28
- 229950006780 n-acetylglucosamine Drugs 0.000 title claims abstract description 28
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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 claims abstract description 20
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
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Images
Abstract
The invention discloses a method for preparing 3-amino-5 (alpha-aminoethyl) tetrahydrofuran by utilizing N-acetylglucosamine, which comprises the steps of firstly utilizing the action of a catalyst to enable GlcNAc to form 3-acetamido-5-acetylfuran with a furan ring structure; catalytically synthesizing 3-amino-5- (alpha-aminoethyl) furan in steps by using a biological enzyme method, namely transaminase and deacetylase; finally, the 3-amino-5- (alpha-aminoethyl) furan is hydrogenated to generate 3-amino-5- (alpha-aminoethyl) tetrahydrofuran. Chitin with abundant reserves in the nature is used as a raw material, so that the chitin can be effectively utilized, has wider application prospect, and can replace diamine from petroleum-based sources to synthesize polyamide materials. The method has great economic significance.
Description
Technical Field
The invention belongs to the field of biomass conversion, and particularly relates to a method for preparing 3-amino-5- (alpha-aminoethyl) tetrahydrofuran by using N-acetylglucosamine.
Background
The global production of Polyamide (PA) is around 600 million tons and increases at a rate of 5.4% per year, of which 38% is used for fiber synthesis and 60% is injection molded or extrusion molded and the deep processed product accounts for around 2%. Particularly, as the automobile industry develops, the demand for nylon products will further increase, and the market share of $ 167 billion is expected to reach by 2020, while the monomeric diamine currently used for producing polyamides is still obtained in a chemical way, and is a derivative of petroleum. With the increasing exhaustion of petroleum resources and the general enhancement of awareness of people about environmental protection, more attention is paid to bio-manufacturing materials using renewable biomass resources as raw materials, and thus, the use of bio-based polyamides to replace traditional nylons is a necessary trend.
Chitin (C8H 13O 5N) N, a polymer in which chitin or chitin is bound by GlcNAc via a glycoside bond, is a nitrogenous polysaccharide substance and is an important component of the crustacean such as shrimp, crab, and insect. It is very widely distributed in nature and has a content second to cellulose, and is the second natural renewable resource in the world. The chitin monomolecular GlcNAc contains natural N element, and the N-containing compound is reasonably utilized, so that more economic benefits can be brought to the society, and the chitin monomolecular GlcNAc has important significance for waste treatment and environmental protection.
The method can apply the natural N-containing diamine unit to the synthesis of polyurethane materials, and has important significance for reducing the utilization of non-renewable resources and protecting the emission of carbon dioxide in the earth atmosphere. At present, the thermal decomposition of N-acetylglucosamine at high temperature to obtain 3-acetamido-5-acetylfuran, and the conversion preparation of many important nitrogen-containing compounds by using 3-acetamido-5-acetylfuran as a platform has been reported.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing 3-amino-5- (alpha-aminoethyl) tetrahydrofuran by using N-acetylglucosamine, which synthesizes 3-acetyl-5- (alpha-aminoethyl) furan with more value by using a monomer prepared by catalyzing natural polymer chitin through combining chemical catalysis and biological enzyme methods.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a method for preparing 3-amino-5- (alpha-aminoethyl) tetrahydrofuran from N-acetylglucosamine, comprising the steps of:
step 1, catalyzing N-acetylglucosamine to prepare 3-acetamido-5-acetylfuran
Putting N-acetylglucosamine, a catalyst and a cocatalyst into a parallel reactor, adding no more than 200mL of solvent for dissolving, heating to 110-200 ℃, stopping the reaction after reacting for 20-120min, filtering to remove insoluble impurities, distilling the filtrate under reduced pressure to remove the solvent, and dissolving the solid substance with 10-50mL of water to obtain 3-acetamido-5-acetylfuran solution for later use; the mass ratio of the N-acetylglucosamine to the catalyst to the cocatalyst is 0.1-1:0.02-0.15:0.02-0.15;
step 2, catalytically reducing the 5-carbonyl group of 3-acetamido-5-acetylfuran to an amino group using transaminase to produce 3-acetamido-5 (. Alpha. -aminoethyl) furan
Mixing a 3-acetamido-5-acetylfuran solution, a transaminase crude enzyme solution and a transaminase amino donor 1mol/L isopropylamine hydrochloride solution according to a volume ratio of 1-8;
step 3, catalyzing 3-acetamido-5 (alpha-aminoethyl) -furan deacetylation group by using deacetylase to generate 3-amino-5 (alpha-aminoethyl) furan
Adjusting the pH of the reaction solution in the step 2 to 6.5-7.5 by using acid, adding crude enzyme liquid of the deacetylase, uniformly mixing, incubating at 25-40 ℃ for 0.5-8 h, after the reaction is finished, removing protein after boiling water bath for 2-5 min, centrifuging to remove precipitate, collecting supernatant, extracting for three times by using 10-100 mL of an extracting agent, combining extract liquor, and concentrating under reduced pressure to obtain a crude solid product of the 3-amino-5 (alpha-aminoethyl) -furan, wherein the volume ratio of the reaction solution to the crude enzyme liquid of the deacetylase is 1-10;
step 4, synthesizing the 3-amino-5 (alpha-aminoethyl) -tetrahydrofuran by a chemical method with a hydrogenation metal catalyst of 3-amino-5 (alpha-aminoethyl) -furan
Taking 0.5-10g of 3-amino-5 (alpha-aminoethyl) -furan solid crude product and metal catalyst, adding the crude product and the metal catalyst into a high-pressure reaction kettle, then introducing hydrogen gas, wherein the hydrogen gas flow rate is 0.20-0.48 m 3 The mass ratio of the hydrogen to the 3-amino-5 (alpha-aminoethyl) -furan is 10-20: 0.5-2, under the conditions of 1.0-6.0 MPa and 80-200 ℃,the catalytic reaction is carried out for 90 to 150 hours at the rotating speed of 50 to 500rpm.
The improvement is that the N-acetylglucosamine in the step 1 is obtained by hydrolyzing shrimp and crab shells or fungal mycelia with chitin, and the solvent is dimethylformamide, N-methylpyrrolidone, dimethylacetamide or dimethyl sulfoxide.
The improvement is that the transaminase in step 2 is one or more of aspartate transaminase, ornithine transaminase in omega-transaminase class or 4-amino butyrate transaminase.
As a modification, the deacetylase in the step 3 is derived from a fungal or bacterial deacetylase and can be overexpressed in a model organism escherichia coli; the pH of the reaction solution is adjusted by using hydrochloric acid, sulfuric acid, acetic acid, sodium phosphate buffer solution or citric acid buffer solution.
The improvement is that the hydrogenation metal catalyst in the step 4 is one of Pd, pt, ni, rh, ru, re, co, cu or Fe, and the ratio of the metal content in the hydrogenation metal catalyst to the content of the substance of 3-amino-5- (alpha-aminoethyl) furan is 10 -4 -10 -1 。
Has the advantages that:
1. the method is a new unreported way for catalyzing monomers prepared from natural polymer chitin to synthesize 3-amino-5- (alpha-aminoethyl) tetrahydrofuran with more value by combining chemical catalysis and biological enzyme method.
2. The invention can utilize the waste shrimp and crab shells containing chitin and the N-acetylglucosamine extracted by fungi as the starting substrate of the reaction, thereby widening the value of the utilization of the waste. Realizes the reutilization of shrimp and crab shell waste resources.
3. Simple operation, single structure of enzyme catalysis product and green and environment-friendly catalysis process.
Drawings
FIG. 1 is a scheme of the reaction scheme;
FIG. 2 is a mass spectrum of 3-acetamido-5-acetylfuran;
FIG. 3 is a mass spectrum of 3-acetamido-5- (. Alpha. -aminoethyl) furan;
FIG. 4 is a mass spectrum of 3-amino-5- (. Alpha. -aminoethyl) furan;
FIG. 5 is a mass spectrum of 3-amino-5- (. Alpha. -aminoethyl) tetrahydrofuran.
Detailed Description
The present invention will be described in further detail below with reference to specific examples.
Example 1
A method for preparing 3-amino-5- (alpha-aminoethyl) tetrahydrofuran from N-acetylglucosamine, comprising the steps of:
step 1, 0.1g of 98% pure N-acetylglucosamine, 0.05g of boron oxide, 0.40g of MgCl 2 ·6H 2 Adding 10 mLN-methyl pyrrolidone into a round-bottom flask for dissolving, heating at 150 ℃ in a constant-temperature oil bath, stirring and refluxing for 1h; after the reaction was completed, the reaction mixture was cooled to room temperature and then filtered. Sampling, adding methanol for dilution, and detecting the content of 3-acetamido-5-acetylfuran by using a high performance liquid phase; distilling the filtrate under reduced pressure to remove the solvent, and dissolving the residue with 20mL of water; the molar conversion was 10 mmols%.
And 2, taking 10mL of the solution containing the product 3-acetamido-5-acetylfuran in the step 1, adding prepared enzyme solution of which the 1 (V: V) transaminase ATA117 gene is expressed in escherichia coli, adding 10mL of 1mol/L isopropyl amine hydrochloride (pH value 7.0) of an amino donor substance required for transamination, incubating for 8 hours at 37 ℃, centrifuging, taking supernatant, performing mass spectrometry, determining the generation of the product 3-acetamido-5 (alpha-aminoethyl) furan, and determining the molecular weight. Centrifuging and taking supernatant to carry out the next reaction;
and 3, adjusting the pH of the reaction liquid in the step 2 to 7.0 by using dilute hydrochloric acid, mixing the reaction liquid with the crude enzyme liquid added with the deacetylase, incubating for 3h at the temperature of 37 ℃ in a ratio of 1 (V: V) to obtain a mixture, after the reaction is finished, carrying out boiling water bath for 2min, removing protein, centrifuging to remove precipitate, and collecting supernatant. Centrifuging, taking the supernatant, and performing mass spectrum detection to determine the generation of the product 3-acetamido-5 (alpha-aminoethyl) furan. Extracting with 50mL ethyl acetate, mixing the extracts after three times of extraction, and concentrating under reduced pressure to obtain a solid crude product containing 3-amino-5 (alpha-aminoethyl) furan;
and 4, taking 5g of the extracted crude product obtained in the step 3 and 3% of a catalyst Pt, adding the mixture into a high-pressure reaction kettle, controlling the pressure to be 3Mpa, the temperature to be 150 ℃, the hydrogen flow rate to be 0.48h < -1 >, the mass ratio of hydrogen to the 3-amino-5- (alpha-aminoethyl) tetrahydrofuran to be 10, carrying out a catalytic reaction for 90h, and carrying out the hydrogenation conversion rate to be 80 percent.
Example 2
A method for preparing 3-amino-5- (alpha-aminoethyl) tetrahydrofuran from N-acetylglucosamine, comprising the steps of:
step 1, preparing 0.1g of purified N-acetylglucosamine (> 98%) from chitin powder in an experiment room, adding 0.063g of boron oxide and 0.383g of 3-butyl benzimidazole chloride into a round-bottom flask, dissolving in 10 mLN-methyl pyrrolidone, and heating, stirring and refluxing for 80min at 180 ℃ in a constant-temperature oil bath. After the reaction was completed, the reaction mixture was cooled to room temperature and then filtered. Sampling, diluting with methanol, and detecting the content of the 3-acetamido-5-acetylfuran by using a high performance liquid phase. The filtrate was distilled under reduced pressure to remove the solvent, and the residue was dissolved in 20mL of water. The molar conversion rate of the 3-acetamido-5-acetylfuran can reach 50 percent; the rest is the same as example 1.
Example 3
A method for preparing 3-amino-5- (alpha-aminoethyl) tetrahydrofuran from N-acetylglucosamine, comprising the steps of:
step 1, purifying chitin in the shell of hydrolyzed crayfish prepared in laboratory to obtain N-acetylglucosamine (A)>98%) 0.1g, 0.05g boron oxide, 0.109g AlCl 3 ·6H 2 Adding 10 mLN-methyl pyrrolidone into a round-bottom flask for dissolving, heating and stirring at 180 ℃ in a constant-temperature oil bath kettle for refluxing for 80min. After the reaction was completed, the reaction mixture was cooled to room temperature and then filtered. Sampling, diluting with methanol, and detecting the content of 3-acetamido-5-acetylfuran by using a high performance liquid phase; the molar conversion was 23%. The rest is the same as example 1.
Example 4
A method for preparing 3-amino-5- (alpha-aminoethyl) tetrahydrofuran from N-acetylglucosamine, comprising the steps of:
the total content of N-acetylglucosamine of chitin hydrolysate prepared in a laboratory is 0.1g, powder obtained by drying in an oven, 0.063g of boron oxide and 0.070g of benzimidazole chloride are put in a round bottom flask, 10mL of dimethyl sulfoxide is added for dissolving, and the mixture is heated, stirred and refluxed for 80min at 180 ℃ in a constant-temperature oil bath. After the reaction was completed, the reaction mixture was cooled to room temperature and then filtered. Sampling, diluting with methanol, and detecting the content of 3-acetamido-5-acetylfuran by using a high performance liquid phase. The filtrate was distilled under reduced pressure to remove the solvent, and the residue was dissolved in 20mL of water. The yield of the 3-acetamido-5-acetylfuran reaches 20mol percent; the rest is the same as example 1.
Example 5
A method for preparing 3-amino-5- (alpha-aminoethyl) tetrahydrofuran from N-acetylglucosamine, comprising the steps of:
the material is prepared from chitin powder hydrolysate, oven drying to remove water, 0.5g, 0.05g boron oxide, and 0.109g AlCl 3 ·6H 2 Adding 10 mLN-methyl pyrrolidone into a round-bottom flask for dissolving, heating and stirring at 180 ℃ in a constant-temperature oil bath kettle for refluxing for 80min. After the reaction was completed, the reaction mixture was cooled to room temperature and then filtered. Sampling, diluting with methanol, and detecting the content of 3-acetamido-5-acetylfuran by using a high performance liquid phase. The filtrate was distilled under reduced pressure to remove the solvent, and the residue was dissolved in 20mL of water. The conversion rate can reach 35mol%.
The rest is the same as example 1.
Compared with the prior art, the method for preparing 3-amino-5- (alpha-aminoethyl) tetrahydrofuran by using N-acetylglucosamine is a novel method which is not reported. The method synthesizes 3-acetyl-5- (alpha-aminoethyl) furan with more value by utilizing a monomer prepared by catalyzing natural polymer chitin by combining chemical catalysis and biological enzyme method, is novel, simple to operate, green and environment-friendly in catalysis process, and can realize wider application of resources.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.
Claims (5)
1. A method for preparing 3-amino-5- (alpha-aminoethyl) tetrahydrofuran by using N-acetylglucosamine, which comprises the following steps:
step 1, catalyzing N-acetylglucosamine to prepare 3-acetamido-5-acetylfuran
Putting N-acetylglucosamine, a catalyst and a cocatalyst into a parallel reactor, adding no more than 200mL of solvent for dissolving, heating to 110-200 ℃, stopping the reaction after reacting for 20-120min, filtering to remove insoluble impurities, distilling the filtrate under reduced pressure to remove the solvent, and dissolving the solid substance with 10-50mL of water to obtain 3-acetamido-5-acetylfuran solution for later use; the mass ratio of the N-acetylglucosamine to the catalyst to the cocatalyst is 0.1-1:0.02-0.15:0.02-0.15;
step 2, using transaminase to catalyze and reduce the 5-carbonyl of 3-acetamido-5-acetylfuran into amino group to generate 3-acetamido-5 (alpha-aminoethyl) furan
Mixing a 3-acetamido-5-acetylfuran solution, a transaminase crude enzyme solution and a 1mol/L isopropylamine hydrochloride solution of a transaminase amino donor according to a volume ratio of 1 to 8, 1 to 10, putting the mixture into a 50-500mL triangular shake flask, adding coenzyme 5-pyridoxal phosphate with a reaction volume concentration of 0.05 to 1mM/L, mixing, incubating for 0.5 to 10 hours at 30-40 ℃, centrifuging, and taking a supernatant as a reaction solution for later use, wherein the pH of the isopropylamine hydrochloride is 6.0 to 9.0;
step 3, catalyzing 3-acetamido-5 (alpha-aminoethyl) -furan deacetylation group by using deacetylase to generate 3-amino-5 (alpha-aminoethyl) furan
Adjusting the pH of the reaction liquid in the step 2 to 6.5 to 7.5 by using acid, then adding crude deacetylase liquid, uniformly mixing, incubating at 25 to 40 ℃ for 0.5 to 8 hours, after the reaction is finished, removing protein after boiling water bath for 2 to 5 minutes, centrifuging to remove precipitates, collecting supernatant, extracting for three times by using 10 to 100mL of an extracting agent, combining the extracts, and concentrating under reduced pressure to obtain a 3-amino-5 (alpha-aminoethyl) -furan solid crude product, wherein the volume ratio of the reaction liquid to the crude deacetylase liquid is 1 to 10;
step 4, synthesizing 3-amino-5 (alpha-aminoethyl) -tetrahydrofuran by using a chemical method to hydrogenate the 3-amino-5 (alpha-aminoethyl) -furan with a metal catalyst
Taking 0.5 to 10g of 3-amino-5 (alpha-aminoethyl) -furan solid crude product and a metal catalyst, adding the crude product and the metal catalyst into a high-pressure reaction kettle, and then introducing hydrogen at the hydrogen flow rate of 0.20 to 0.48m 3 The mass ratio of hydrogen to 3-amino-5 (alpha-aminoethyl) -furan is 10 to 20: 0.5 to 2, the catalytic reaction is carried out for 90 to 150 hours under the conditions of 1.0 to 6.0MPa and 80 to 200 ℃, and the rotating speed is 50 to 500rpm.
2. The method for preparing 3-amino-5- (. Alpha. -aminoethyl) tetrahydrofuran according to claim 1, wherein the N-acetylglucosamine is obtained by hydrolyzing shrimp and crab shells or fungal mycelia with chitin in step 1, and the solvent is dimethylformamide, N-methylpyrrolidone, dimethylacetamide or dimethylsulfoxide.
3. The method of claim 1, wherein the transaminase in step 2 is aspartate transaminase, ornithine transaminase of the ω -transaminase class or 4-aminobutyrate transaminase in combination with one or more of the group consisting of N-acetylglucosamine.
4. The method for preparing 3-amino-5- (alpha-aminoethyl) tetrahydrofuran according to claim 1, wherein the deacetylase in step 3 is derived from a fungal or bacterial deacetylase and can be overexpressed in E.coli, a model organism; the pH of the reaction solution is adjusted by using hydrochloric acid, sulfuric acid, acetic acid, sodium phosphate buffer solution or citric acid buffer solution.
5. The method for preparing 3-amino-5- (. Alpha. -aminoethyl) tetrahydrofuran according to claim 1, wherein the hydrogenation metal catalyst in step 4 is one of Pd, pt, ni, rh, ru, re, co, cu or Fe, and the amount of the metal contained in the hydrogenation metal catalyst is equal to that of 3-amino-5- (alpha. -aminoethyl) tetrahydrofuranThe ratio of the amounts of substances of alpha-aminoethyl) furan is 10 -4 -10 -1 。
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| GB801169A (en) * | 1956-06-25 | 1958-09-10 | Olin Mathieson | Process for the preparation of 2 (alpha-aminoethyl)-furan and derivatives thereof |
| CN101772485A (en) * | 2007-06-06 | 2010-07-07 | 诺瓦提斯公司 | Anti -inflammatory substituted cyclobutenedione compounds |
| CN107759546A (en) * | 2017-11-13 | 2018-03-06 | 天津工业大学 | A kind of method that catalyzed conversion chitin and monomer N acetylglucosamine prepares the acetyl furan of 3 acetylamino 5 |
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| GB801169A (en) * | 1956-06-25 | 1958-09-10 | Olin Mathieson | Process for the preparation of 2 (alpha-aminoethyl)-furan and derivatives thereof |
| CN101772485A (en) * | 2007-06-06 | 2010-07-07 | 诺瓦提斯公司 | Anti -inflammatory substituted cyclobutenedione compounds |
| CN107759546A (en) * | 2017-11-13 | 2018-03-06 | 天津工业大学 | A kind of method that catalyzed conversion chitin and monomer N acetylglucosamine prepares the acetyl furan of 3 acetylamino 5 |
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