CN112522339A - Method for preparing 3-acetamido-5-acetylfuran by degrading N-acetyl-D-glucosamine with chitin - Google Patents

Method for preparing 3-acetamido-5-acetylfuran by degrading N-acetyl-D-glucosamine with chitin Download PDF

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CN112522339A
CN112522339A CN202011503133.2A CN202011503133A CN112522339A CN 112522339 A CN112522339 A CN 112522339A CN 202011503133 A CN202011503133 A CN 202011503133A CN 112522339 A CN112522339 A CN 112522339A
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chitin
3a5af
nag
chloride
glucosamine
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CN112522339B (en
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陈可泉
吴超强
张阿磊
王成勇
曹飞
欧阳平凯
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Nanjing Tech University
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    • C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
    • C12P17/02—Oxygen as only ring hetero atoms
    • C12P17/04—Oxygen as only ring hetero atoms containing a five-membered hetero ring, e.g. griseofulvin, vitamin C
    • 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
    • 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
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    • 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 relates to preparation of chemicals, in particular to a method for preparing 3-acetamido-5-acetylfuran by degrading N-acetyl-D-glucosamine by using chitin, which is a nitrogen-containing platform compound with high added value, can be used for various nitrogen-containing fine chemical synthesis and has great application value. The method comprises the steps of firstly degrading chitin by using chitinase to serve as a monomer N-acetyl-D-glucosamine, then using the chitin as a starting substrate, using N, N-dimethylacetamide as a reaction solvent, and carrying out cyclodehydration to form 3A5AF under the action of catalysts such as ammonium thiocyanate and structural analogues thereof and a small amount of metal salt serving as auxiliary catalysts. The method has the advantages of simple reaction steps, low catalyst cost, convenient operation, high product yield and better industrialization prospect.

Description

Method for preparing 3-acetamido-5-acetylfuran by degrading N-acetyl-D-glucosamine with chitin
Technical Field
The invention belongs to the field of biomass conversion, and particularly relates to a method for preparing 3-acetamido-5-acetylfuran by degrading N-acetyl-D-glucosamine with chitin.
Background
The nitrogen-containing compound is an important chemical, has important application value in the fields of chemical industry, medicine and materials, is generally synthesized from nonrenewable fossil resources such as coal, petroleum and the like, needs an additional amino donor, and has high energy consumption, low conversion rate and poor economic benefit.
Chitin (C)8H13O5N)nThe polymer, also called chitin, formed by bonding NAG through beta-1, 4 glycosidic bonds, is widely distributed in nature, mainly exists in exoskeletons of shrimps, crabs, insects and the like, has the content second to cellulose, and is the second most renewable resource in the world. The chitin structure contains nitrogen element, and is an excellent substrate for synthesizing nitrogen-containing chemicals. Therefore, the chitin is directly converted into the nitrogen-containing compound with high added value, which not only brings great economic benefits to the modern society, but also has important significance for waste treatment and environmental protection.
3-acetamido-5-acetylfuran (3A5AF) is a nitrogen-containing platform compound with high added value, which can be obtained from chitin, and has great application prospect and research value in the field of synthesis of nitrogen-containing fine chemicals. For example, 3A5AF is an important component of several bioactive macromolecular compounds, including the anticancer agent, proximicin a, the alkaloids, hyposeragine a and B, and pyrrolosine, among others. In addition, the method can also be used for synthesizing furan diamine chemicals.
At present, the synthesis of 3A5AF by using chitin and its monomer NAG as substrates has been reported. For example, Yan et al prepared 3A5AF with chitin as the substrate in 7.5% yield. However, the yield of 3A5AF was low with chitin as substrate, a maximum of 18%. The yield can be effectively improved by taking the degradation product NAG of the chitin as a substrate. FRANICH et al reported pyrolysis of NAG at high temperature to give the nitrogen-containing compound 3A5 AF. Drover et al reported that boric acid was added at 180 deg.C[B(OH)3]In the presence of ionic liquid NAG was converted to 3A5AF in 60% yield. Omari et al 220 ℃ in B (OH)3And NaCl in the presence of conversion of NAG to 3A5AF with microwave irradiation in 58% yield. However, in the reported research, ionic liquid is mostly used as a catalyst, the price is expensive, and the production cost is high due to the substrate.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing 3-acetamido-5-acetylfuran (3A5AF) by degrading N-acetyl-D-glucosamine (NAG) with chitin, the method utilizes a green biological enzyme method to degrade renewable biomass chitin into N-acetyl-D-glucosamine by chitinase, and further utilizes a chemical catalysis method to synthesize NAG into 3A5AF with high added value under the conditions that N, N-dimethylacetamide is used as a solvent, ammonium thiocyanate and structural analogues thereof are used as catalysts, and metal salt is added as a cocatalyst.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing 3-acetamido-5-acetylfuran by degrading N-acetyl-D-glucosamine with chitin comprises the following steps:
step 1, adding chitinase, phosphate buffer solution and metal ions into chitin, carrying out enzymolysis for 24-120 h at the temperature of 30-50 ℃ and the pH value of 6-8, separating supernatant after the enzymolysis is finished, and then carrying out adsorption, vacuum concentration and freeze drying on the supernatant to obtain NAG crystals;
and 2, adding 5mL of solvent into NAG, a catalyst and a metal salt cocatalyst into a pressure-resistant tube for dissolving, heating for reacting for 5-240 min, filtering, taking filtrate, adding water with the same volume into the filtrate for mixing, extracting with ethyl acetate for three times, combining extract liquor after extracting for three times, concentrating under reduced pressure to obtain a solid crude product containing 3A5AF, adding 1mL of methanol for redissolving, dropwise adding into precooled deionized water for crystallization, filtering and drying to obtain a transparent needle-shaped 3A5AF crystal with the purity higher than 99.5%.
The improvement is that the chitinase is one or a mixture of two of chitinase endoenzyme, chitinase exoenzyme or N-acetamidohexosidase.
The improvement is that the dosage of the chitin is 0.025g-1g, the dosage of the NAG is 0.025g-1g, the mass of the catalyst is 0.1-5 times of that of the NAG substrate, and the mass of the cocatalyst is 0.1-5 times of that of the NAG substrate.
The improvement is that the catalyst is one or the mixture of any two of ammonium thiocyanate, thiourea, potassium thiocyanate, thiobenzamide, thioacetamide or thiosemicarbazide.
The improvement is that the solvent in the step 2 is one or a mixture of any two of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and ethanol, and the dosage of the solvent is 1-100 mL.
The improvement is that the cocatalyst is one or the mixture of any two of boric acid, sodium chloride, potassium chloride, lithium chloride, ammonium chloride, zinc chloride, aluminum chloride hexahydrate, cobalt chloride hexahydrate, magnesium chloride hexahydrate, calcium chloride dihydrate, barium chloride dihydrate, ferric chloride hexahydrate, manganese chloride, hydrogen chloride and 1-butyl-3-methylimidazolium chloride salt.
As a modification, the reaction temperature in step 2 is 120-200 ℃.
Has the advantages that:
compared with the prior art, the method for preparing 3-acetamido-5-acetylfuran by degrading N-acetyl-D-glucosamine by using chitin utilizes the renewable biomass resource chitin monomer NAG as a raw material to prepare 3A5AF, thereby widening the research on effective utilization of biomass; the cheap and easily obtained ammonium thiocyanate is used as the catalyst, so that the production cost of 3A5AF is greatly reduced, and the industrial production of 3A5AF is facilitated.
Drawings
FIG. 1 shows the results of liquid phase detection of 3A5 AF;
FIG. 2 is a liquid phase detection result of NAG after 45min reaction under a catalyst.
Detailed Description
The following examples are provided to aid in a further understanding of the invention.
Example 1
Converting chitin with chitinase in 200mL reaction system (chitin powder 40 g/L, chitinase 1.3U/mL, N-acetylhexosaminidase 1.35U/mL, CaCl2 15 mM, phosphate buffer solution with pH 8), reacting at 37 ℃ and 200rpm for 36 h under stirring, separating supernatant after the reaction is finished, adsorbing by ion exchange resin, concentrating in vacuum, and freeze-drying to obtain NAG crystal.
Then 100mg NAG and 50mg ammonium thiocyanate (catalyst) are put into a 50mL pressure resistant tube, 5mL N, N-dimethylacetamide (solvent) is added, and the mixture is heated and stirred for 45min at 180 ℃ in a magnetic stirring heater under the pressure condition. After the reaction is finished and cooled to room temperature, adding pure water with the same volume as the reaction product, dissolving the mixture in water, extracting the mixture for multiple times by using ethyl acetate, concentrating the mixture under reduced pressure to obtain a solid crude product containing 3A5AF, adding 1mL of methanol to redissolve the solid crude product, dropwise adding the solid crude product into precooled deionized water to crystallize, filtering and drying the crystals to obtain the high-purity (99.5%) transparent needle-shaped 3A5AF crystal. The liquid phase found that the concentration of 3A5AF in the reaction mixture was 4.43g/L and the molar conversion was 29.31%.
Example 2
Converting chitin with chitinase, wherein the reaction system (chitin powder particle 40 g/L, chitinase 1.3U/mL, N-acetylhexosaminidase 1.35U/mL, CaCl2 15 mM, pH 8 phosphate buffer) at 37 ℃ under 200rpm for 36 h, separating the supernatant after the reaction is finished, adsorbing by ion exchange resin, concentrating in vacuum, and freeze-drying to obtain NAG crystal.
Then 100mg NAG and 50mg ammonium thiocyanate are put into a 50mL pressure resistant tube, 5mL dimethyl sulfoxide (solvent) is added, and the mixture is heated and stirred for 45min at 180 ℃ in a magnetic stirring heater under the condition of pressurization. After the reaction is finished and cooled to room temperature, adding pure water with the same volume as the reaction product, dissolving the mixture in water, extracting the mixture for multiple times by using ethyl acetate, concentrating the mixture under reduced pressure to obtain a solid crude product containing 3A5AF, adding 1mL of methanol to redissolve the solid crude product, dropwise adding the solid crude product into precooled deionized water to crystallize, filtering and drying the crystals to obtain the high-purity (99.5%) transparent needle-shaped 3A5AF crystal. The liquid phase measurement shows that the concentration of 3A5AF in the reaction solution is 0.15g/L, and the molar conversion rate is 0.99%.
Example 3
Converting chitin with chitinase, wherein the reaction system (chitin powder particle 40 g/L, chitinase 1.3U/mL, N-acetylhexosaminidase 1.35U/mL, CaCl2 15 mM, pH 8 phosphate buffer) at 37 ℃ under 200rpm for 36 h, separating the supernatant after the reaction is finished, adsorbing by ion exchange resin, concentrating in vacuum, and freeze-drying to obtain NAG crystal.
Then 100mg NAG and 50mg ammonium thiocyanate are put into a 50mL pressure resistant tube, 5mL N-methyl pyrrolidone (solvent) is added, and the mixture is heated and stirred for 45min at 180 ℃ in a magnetic stirring heater under the pressure condition. After the reaction is finished and cooled to room temperature, adding pure water with the same volume as the reaction product, dissolving the mixture in water, extracting the mixture for multiple times by using ethyl acetate, concentrating the mixture under reduced pressure to obtain a solid crude product containing 3A5AF, adding 1mL of methanol to redissolve the solid crude product, dropwise adding the solid crude product into precooled deionized water to crystallize, filtering and drying the crystals to obtain the high-purity (99.5%) transparent needle-shaped 3A5AF crystal. The liquid phase measurement shows that the concentration of 3A5AF in the reaction solution is 1.00g/L, and the molar conversion rate is 6.60%.
Example 4
Converting chitin with chitinase, wherein the reaction system (chitin powder particle 40 g/L, chitinase 1.3U/mL, N-acetylhexosaminidase 1.35U/mL, CaCl2 15 mM, pH 8 phosphate buffer) at 37 ℃ under 200rpm for 36 h, separating the supernatant after the reaction is finished, adsorbing by ion exchange resin, concentrating in vacuum, and freeze-drying to obtain NAG crystal.
Then 100mg NAG, 50mg ammonium thiocyanate and 0.0132g sodium chloride are taken, 5mL of N, N-dimethylacetamide is added into a 50mL pressure resistant tube, and the mixture is heated and stirred for 45min at 180 ℃ in a magnetic stirring heater under the pressure condition. After the reaction is finished and cooled to room temperature, adding pure water with the same volume as the reaction product, dissolving the mixture in water, extracting the mixture for multiple times by using ethyl acetate, concentrating the mixture under reduced pressure to obtain a solid crude product containing 3A5AF, adding 1mL of methanol to redissolve the solid crude product, dropwise adding the solid crude product into precooled deionized water to crystallize, filtering and drying the crystals to obtain the high-purity (99.5%) transparent needle-shaped 3A5AF crystal. The liquid phase measurement shows that the concentration of 3A5AF in the reaction solution is 5.66g/L, and the molar conversion rate is 37.43%.
Example 5
Converting chitin with chitinase, wherein the reaction system (chitin powder particle 40 g/L, chitinase 1.3U/mL, N-acetylhexosaminidase 1.35U/mL, CaCl2 15 mM, pH 8 phosphate buffer) at 37 ℃ under 200rpm for 36 h, separating the supernatant after the reaction is finished, adsorbing by ion exchange resin, concentrating in vacuum, and freeze-drying to obtain NAG crystal.
Then 100mg NAG, 50mg ammonium thiocyanate and 0.067g calcium chloride dihydrate are taken, 5mL of N, N-dimethylacetamide is added into a 50mL pressure resistant tube, and the mixture is heated and stirred for 45min at 180 ℃ in a magnetic stirring heater under the pressure condition. After the reaction is finished and cooled to room temperature, adding pure water with the same volume as the reaction product, dissolving the mixture in water, extracting the mixture for multiple times by using ethyl acetate, concentrating the mixture under reduced pressure to obtain a solid crude product containing 3A5AF, adding 1mL of methanol to redissolve the solid crude product, dropwise adding the solid crude product into precooled deionized water to crystallize, filtering and drying the crystals to obtain the high-purity (99.5%) transparent needle-shaped 3A5AF crystal. The liquid phase showed that the 3A5AF concentration in the reaction mixture was 6.53g/L, the molar conversion was 43.24%.
Example 6
Converting chitin with chitinase, wherein the reaction system (chitin powder particle 40 g/L, chitinase 1.3U/mL, N-acetylhexosaminidase 1.35U/mL, CaCl2 15 mM, pH 8 phosphate buffer) at 37 ℃ under 200rpm for 36 h, separating the supernatant after the reaction is finished, adsorbing by ion exchange resin, concentrating in vacuum, and freeze-drying to obtain NAG crystal.
Then 100mg NAG, 50mg ammonium thiocyanate and 0.034 potassium chloride are taken, 5mL of N, N-dimethylacetamide is added into a 50mL pressure resistant tube, and the mixture is heated and stirred for 45min at 180 ℃ in a magnetic stirring heater under the pressure condition. After the reaction is finished and cooled to room temperature, adding pure water with the same volume as the reaction product, dissolving the mixture in water, extracting the mixture for multiple times by using ethyl acetate, concentrating the mixture under reduced pressure to obtain a solid crude product containing 3A5AF, adding 1mL of methanol to redissolve the solid crude product, dropwise adding the solid crude product into precooled deionized water to crystallize, filtering and drying the crystals to obtain the high-purity (99.5%) transparent needle-shaped 3A5AF crystal. The liquid phase measurement shows that the concentration of 3A5AF in the reaction solution is 5.38g/L, and the molar conversion rate is 35.58%.
Example 7
Using chitinaseConverting chitin, wherein the reaction system (chitin powder 40 g/L, chitinase 1.3U/mL, N-acetylhexosaminidase 1.35U/mL, CaCl2 15 mM, pH 8 phosphate buffer) at 37 ℃ under 200rpm for 36 h, separating the supernatant after the reaction is finished, adsorbing by ion exchange resin, concentrating in vacuum, and freeze-drying to obtain NAG crystal.
Then 100mg NAG, 50mg ammonium thiocyanate and 0.067g calcium chloride dihydrate are taken, 5mL of N, N-dimethylacetamide is added into a 50mL pressure resistant tube, and the mixture is heated and stirred for 5min at 180 ℃ in a magnetic stirring heater under the pressure condition. After the reaction is finished and cooled to room temperature, adding pure water with the same volume as the reaction product, dissolving the mixture in water, extracting the mixture for multiple times by using ethyl acetate, concentrating the mixture under reduced pressure to obtain a solid crude product containing 3A5AF, adding 1mL of methanol to redissolve the solid crude product, dropwise adding the solid crude product into precooled deionized water to crystallize, filtering and drying the crystals to obtain the high-purity (99.5%) transparent needle-shaped 3A5AF crystal. The liquid phase found that the concentration of 3A5AF in the reaction mixture was 7.28g/L and the molar conversion was 48.14%.
Example 8
Converting chitin with chitinase, wherein the reaction system (chitin powder particle 40 g/L, chitinase 1.3U/mL, N-acetylhexosaminidase 1.35U/mL, CaCl2 15 mM, pH 8 phosphate buffer) at 37 ℃ under 200rpm for 36 h, separating the supernatant after the reaction is finished, adsorbing by ion exchange resin, concentrating in vacuum, and freeze-drying to obtain NAG crystal.
Then 100mg NAG, 50mg ammonium thiocyanate and 0.067g calcium chloride dihydrate are taken, 5mL of N, N-dimethylacetamide is added into a 50mL pressure resistant tube, and the mixture is heated and stirred for 30min at 180 ℃ in a magnetic stirring heater under the pressure condition. After the reaction is finished and cooled to room temperature, adding pure water with the same volume as the reaction product, dissolving the mixture in water, extracting the mixture for multiple times by using ethyl acetate, concentrating the mixture under reduced pressure to obtain a solid crude product containing 3A5AF, adding 1mL of methanol to redissolve the solid crude product, dropwise adding the solid crude product into precooled deionized water to crystallize, filtering and drying the crystals to obtain the high-purity (99.5%) transparent needle-shaped 3A5AF crystal. The liquid phase measurement shows that the concentration of 3A5AF in the reaction solution is 7.45g/L, and the molar conversion rate is 49.30%.
Example 9
Converting chitin with chitinase, wherein the reactantThe system (chitin powder particle 40 g/L, chitin incision enzyme 1.3U/mL, N-acetaminohexosidase 1.35U/mL, CaCl2 15 mM, pH 8 phosphate buffer) at 37 ℃ under 200rpm for 36 h, separating the supernatant after the reaction is finished, adsorbing by ion exchange resin, concentrating in vacuum, and freeze-drying to obtain NAG crystal.
Then 100mg NAG, 50mg ammonium thiocyanate and 0.067g calcium chloride dihydrate are taken, 5mL of N, N-dimethylacetamide is added into a 50mL pressure resistant tube, and the mixture is heated and stirred for 120min at 180 ℃ in a magnetic stirring heater under the pressure condition. After the reaction is finished and cooled to room temperature, adding pure water with the same volume as the reaction product, dissolving the mixture in water, extracting the mixture for multiple times by using ethyl acetate, concentrating the mixture under reduced pressure to obtain a solid crude product containing 3A5AF, adding 1mL of methanol to redissolve the solid crude product, dropwise adding the solid crude product into precooled deionized water to crystallize, filtering and drying the crystals to obtain the high-purity (99.5%) transparent needle-shaped 3A5AF crystal. The liquid phase found that the concentration of 3A5AF in the reaction mixture was 6.76g/L and the molar conversion was 44.71%.
Example 10
Converting chitin with chitinase, wherein the reaction system (chitin powder particle 40 g/L, chitinase 1.3U/mL, N-acetylhexosaminidase 1.35U/mL, CaCl2 15 mM, pH 8 phosphate buffer) at 37 ℃ under 200rpm for 36 h, separating the supernatant after the reaction is finished, adsorbing by ion exchange resin, concentrating in vacuum, and freeze-drying to obtain NAG crystal.
Then 150mg NAG, 50mg ammonium thiocyanate and 0.075g calcium chloride dihydrate are added into a 50mL pressure resistant tube with 10mL N, N-dimethylacetamide, and heated and stirred in a magnetic stirring heater at 180 ℃ for 25min under the pressure condition. After the reaction is finished and cooled to room temperature, adding pure water with the same volume as the reaction product, dissolving the mixture in water, extracting the mixture for multiple times by using ethyl acetate, concentrating the mixture under reduced pressure to obtain a solid crude product containing 3A5AF, adding 1mL of methanol to redissolve the solid crude product, dropwise adding the solid crude product into precooled deionized water to crystallize, filtering and drying the crystals to obtain the high-purity (99.5%) transparent needle-shaped 3A5AF crystal. The liquid phase found that the concentration of 3A5AF in the reaction mixture was 8.56g/L and the molar conversion was 56.66%.
Example 11
The same procedure as in example 1 was repeated except that the NAG reaction temperature was changed to 160 ℃, and the 3A5AF concentration in the reaction mixture was 1.20g/L and the molar conversion was 7.92% as measured in the liquid phase.
Example 12
In the same manner as in example 1 except that the NAG reaction temperature was changed to 170 ℃, the concentration of 3A5AF in the reaction solution was 3.12g/L and the molar conversion was 20.67% as measured in the liquid phase.
Example 13
In the same manner as in example 1 except that the NAG reaction temperature was changed to 190 ℃, the concentration of 3A5AF in the reaction solution was 4.20g/L and the molar conversion was 27.81% as measured in the liquid phase.
Example 14
The same as in example 1 except that the NAG reaction catalyst was changed to thiourea, the concentration of 3A5AF in the reaction solution was 4.18g/L and the molar conversion was 27.69%, as measured in the liquid phase.
Comparative example 1
In patent CN111072602A, amino acid ionic liquid is used as a catalyst to catalyze N-acetylglucosamine to be 3-acetamido-5-acetylfuran, which has the advantages that the catalyst raw material is cheap and easy to obtain, the highest conversion rate can reach 52.61%, but the reaction temperature reaches 200 ℃, and only a 3A5AF crude product is finally obtained. The method adopts ammonium thiocyanate as a catalyst, the optimal yield can reach 56.66% at 180 ℃, the cost of the catalyst ammonium thiocyanate is lower than that of amino acid ionic liquid, the process of preparing the ionic liquid is avoided, and the reaction process is simplified. Meanwhile, the patent provides a crystallization method for obtaining high-purity 3A5AF crystal, which is beneficial to obtaining high-purity 3A5AF product.
The invention directly starts from chitin, firstly, the chitin is degraded into NAG by a green biological enzyme method, and on the basis, low-price ammonium thiocyanate and structural analogues thereof are used as catalysts, so that the chitin can be finally efficiently converted into a platform chemical 3A5AF for chemical production.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only illustrative of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A method for preparing 3-acetamido-5-acetylfuran by degrading N-acetyl-D-glucosamine with chitin is characterized by comprising the following steps:
step 1, adding chitinase, phosphate buffer solution and metal ions into chitin, carrying out enzymolysis for 24-120 h at the temperature of 30-50 ℃ and the pH value of 6-8, separating supernatant after the enzymolysis is finished, and then carrying out adsorption, vacuum concentration and freeze drying on the supernatant to obtain NAG crystals;
and 2, adding a solvent to dissolve NAG, a catalyst and a metal salt cocatalyst into a pressure-resistant tube, reacting at a set temperature, filtering after the reaction is finished, taking a filtrate, adding water with the same volume into the filtrate for mixing, extracting with ethyl acetate for three times, combining extract liquor after extracting for three times, concentrating under reduced pressure to obtain a solid crude product containing 3A5AF, adding 1mL of methanol for redissolving, dropwise adding into precooled deionized water for crystallization, filtering and drying to obtain a transparent needle-shaped 3A5AF crystal with the purity higher than 99.5%, adding 1mL of methanol for redissolving, dropwise adding into precooled deionized water for crystallization, and filtering and drying to obtain a transparent needle-shaped 3A5AF crystal with the purity higher than 99.5%.
2. The method for preparing 3-acetamido-5-acetylfuran by degrading N-acetyl-D-glucosamine with chitin according to claim 1, wherein the chitinase is one or two of endo-chitinase, exo-chitinase and N-acetylhexosaminidase.
3. The method of claim 1, wherein the chitin is used in an amount of 0.025g to 1g, the NAG is used in an amount of 0.025g to 1g, the catalyst is used in an amount of 0.1 to 5 times the molar mass of the NAG substrate, and the promoter is used in an amount of 0.1 to 5 times the molar mass of the NAG substrate.
4. The method for preparing 3-acetamido-5-acetylfuran by degrading N-acetyl-D-glucosamine with chitin according to claim 1, wherein the catalyst is one or a mixture of any two of ammonium thiocyanate, thiourea, potassium thiocyanate, thiobenzamide, thioacetamide or thiosemicarbazide, and the molar mass of the catalyst is 0.1-5 times that of NAG substrate.
5. The method for preparing 3-acetamido-5-acetylfuran by degrading N-acetyl-D-glucosamine with chitin according to claim 1, wherein the solvent in step 2 is one or a mixture of any two of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and ethanol, and the amount of the solvent is 1-100 mL.
6. The method for preparing 3-acetamido-5-acetylfuran by degrading N-acetyl-D-glucosamine with chitin according to claim 1, wherein the promoter is one or a mixture of any two of boric acid, sodium chloride, potassium chloride, lithium chloride, ammonium chloride, zinc chloride, aluminum chloride hexahydrate, cobalt chloride hexahydrate, magnesium calcium chloride hexahydrate, calcium chloride dihydrate, barium chloride dihydrate, ferric chloride hexahydrate, manganese chloride, hydrogen chloride, and 1-butyl-3-methylimidazolium chloride.
7. The method of claim 1, wherein the reaction temperature in step 2 is 120 ℃ to 200 ℃.
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CN112876438A (en) * 2021-01-20 2021-06-01 南京工业大学 Separation and purification method of high-purity 3-acetamido-5-acetylfuran
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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
CN113528490A (en) * 2021-06-07 2021-10-22 昆明理工大学 Chitinase, coding gene and application thereof

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