CN113024493A - Method for preparing 3-acetamido-5-acetylfuran by catalyzing N-acetylglucosamine with ammonium chloride - Google Patents
Method for preparing 3-acetamido-5-acetylfuran by catalyzing N-acetylglucosamine with ammonium chloride Download PDFInfo
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- chloride
- acetylglucosamine
- ammonium chloride
- acetylfuran
- acetamido
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 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 39
- 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 37
- 229950006780 n-acetylglucosamine Drugs 0.000 title claims abstract description 37
- 235000019270 ammonium chloride Nutrition 0.000 title claims abstract description 32
- 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 30
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 229920002101 Chitin Polymers 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229940052299 calcium chloride dihydrate Drugs 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims description 2
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 claims description 2
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 claims description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 16
- 239000002028 Biomass Substances 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 229910001514 alkali metal chloride Inorganic materials 0.000 abstract 1
- 150000002085 enols Chemical class 0.000 abstract 1
- 150000002576 ketones Chemical class 0.000 abstract 1
- 238000007142 ring opening reaction Methods 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- OVRNDRQMDRJTHS-RTRLPJTCSA-N N-acetyl-D-glucosamine Chemical compound CC(=O)N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-RTRLPJTCSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XUAXVBUVQVRIIQ-UHFFFAOYSA-N 1-butyl-2,3-dimethylimidazol-3-ium Chemical compound CCCCN1C=C[N+](C)=C1C XUAXVBUVQVRIIQ-UHFFFAOYSA-N 0.000 description 1
- HHHYPTORQNESCU-UHFFFAOYSA-M 1-butyl-2,3-dimethylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1C HHHYPTORQNESCU-UHFFFAOYSA-M 0.000 description 1
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- NMTRJAKSMWDJSY-UHFFFAOYSA-N Pyrrolosine Natural products C=1OC=2C(N)=NC=NC=2C=1C1OC(CO)C(O)C1O NMTRJAKSMWDJSY-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- LUNJGRUKBOURFM-UHFFFAOYSA-N methyl n-[5-[(5-carbamoylfuran-3-yl)carbamoyl]furan-3-yl]carbamate Chemical compound COC(=O)NC1=COC(C(=O)NC=2C=C(OC=2)C(N)=O)=C1 LUNJGRUKBOURFM-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- -1 nitrogenous sugars Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 108700039955 proximicin A Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
Images
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
Abstract
The invention discloses a method for preparing 3-acetamido-5-acetylfuran by catalyzing N-acetylglucosamine with ammonium chloride. N-acetylglucosamine (NAG) is used as a raw material, N, N-dimethylformamide is used as a solvent, and under the action of ammonium chloride serving as a catalyst and a small amount of alkali metal chloride serving as an additive, the raw material undergoes ring opening, ring closing and conversion between enol and ketone, and finally trimolecular water is removed to form 3A5 AF. The invention relates to a method for preparing 3-acetamido-5-acetylfuran by catalyzing N-acetylglucosamine with ammonium chloride, which prepares 3A5AF by using renewable biomass resource chitin monomer N-acetylglucosamine as a raw material, and is reasonable utilization of biomass resources; the ammonium chloride which is cheap and easy to obtain is used as the catalyst, the highest yield (41.46%) can be achieved within a short time (5 min) at a lower temperature (160 ℃), the production cost of 3A5AF is greatly reduced, and the industrial production of 3A5AF is facilitated.
Description
Technical Field
The invention belongs to the field of biomass conversion, and particularly relates to a method for preparing 3-acetamido-5-acetylfuran by catalyzing N-acetylglucosamine with ammonium chloride.
Background
With the gradual depletion of traditional fossil resources such as global oil and natural gas, people are striving to find new alternative energy. The biomass is a natural renewable resource, is huge in quantity and low in price, and abundant biomass resources are expected to become main sources for obtaining fuels and high-added-value chemicals in the future. Chitin is the second most abundant biomass resource on earth, except for cellulose, and the amount of globally produced chitin can reach about 100 million tons per year. Meanwhile, chitin molecules contain natural nitrogen elements, and the chitin molecules are excellent substrates for producing nitrogen-containing chemicals. Therefore, the research of converting chitin biomass into nitrogen-containing chemicals with high added value will become the key point of the development of chemical raw materials and energy industry in the future.
3-acetamido-5-acetylfuran (3A 5 AF) is an important nitrogen-containing platform compound, and contains a 3A5AF structure in a plurality of biomolecule intermediates, and the molecular structures of an anticancer agent Proximicin A, an alkaloid Hyrtioseramine A/B, Pyrrolosine and the like all contain a 3A5AF unit. The 3A5AF prepared by directly taking chitin as a raw material has the defects of low conversion rate and the like, so that the method has higher utilization value by fully utilizing nitrogen elements contained in chitin biomass and degrading chitin and N-acetylglucosamine monomer thereof to prepare 3A5 AF.
In 1984, the conversion of nitrogenous sugars to 3A5AF was reported, and FRANICH et al pyrolyzed GlcNAc at 400 ℃ by pyrolysis and found that 3A5AF was produced at 2% by mass by GC-MS detection. In another study, GlcNAc was mixed with anhydrous disodium hydrogen phosphate and quartz sand and reacted at 200 ℃ for 30 min to give 3A5AF, but only 0.04% yield. DROVER et al found that 1-butyl-3-methylimidazolium chloride salt [ alpha ], [ alphaBMIM]Cl and 1, 2-dimethyl-3-butylimidazolium chloride [ BMMIM ]]The Cl ionic liquid has good effect, and the yield of 3A5AF reaches 25.5 percent and 25.3 percent respectively. The chloride ion in the ionic liquid is crucial to the reaction, and only trace amount of 3A5AF can be obtained if the chloride ion is changed into bromide ion or acetate ion. Meanwhile, they have searched for a cocatalyst, and found that boric acid [ B (OH) ]3]Is good in cocatalyst effect, when B (OH)3When the using amount is 200% (mole fraction), NAG is heated to 180 ℃ by microwave for reaction for 3min, and the yield of 3A5AF is as high as 60.0%. OMARI and the like use dimethylacetamide as a solvent, NAG is heated by microwave under the condition of not adding other catalysts, and the yield of the generated 3A5AF reaches 31.3 percent. When the catalyst is screened, NaCl and B (OH)3 can obviously improve the yield of 3A5AF, and the yield can reach 58.0% under the optimal condition. However, in the reported research, ionic liquid is mostly used as a catalyst, which is expensive, and the reaction temperature is mostly between 180 ℃ and 220 ℃, which results in large energy consumption.
The literature 'research on preparing furan derivatives by catalytic conversion of chitin biomass [ D ]' and 'research on preparing high-added-value chemicals by degradation and conversion of chitin biomass [ D ]' both mention that the existence of Lewis acid has a great promoting effect on the conversion of chitin biomass resources to generate furan compounds, and meanwhile, the existence of chloride ions in the reports of the literature is the key point for preparing 3-acetamido-5-acetylfuran from chitin monomer N-acetylglucosamine. Ammonium chloride is a chemical having both lewis acid (ammonium ion) and chloride ion, and has a wide source and low cost. Therefore, the research on the production of 3-acetamido-5-acetylfuran by catalyzing N-acetylglucosamine by using ammonium chloride as a catalyst has certain industrial value.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing 3-acetamido-5-acetylfuran by catalyzing N-acetylglucosamine with ammonium chloride. The method takes natural renewable chitin biomass resource N-acetylglucosamine as a raw material, takes ammonium chloride with low price and wide sources as a catalyst, and can efficiently catalyze chitin monomer N-acetylglucosamine to be converted into a nitrogen-containing platform compound 3-acetamido-5-acetylfuran within a short time at a lower temperature. The reaction system is green and environment-friendly, and has good yield and simple operation.
A method for preparing 3-acetamido-5-acetylfuran by catalyzing N-acetylglucosamine with ammonium chloride comprises the following steps:
and 3, adding methanol with equal mass into the solid crude product containing 3A5AF for redissolution, dropwise adding into precooled deionized water for crystallization after redissolution, and filtering and drying to obtain a transparent needle-shaped 3A5AF crystal with the purity higher than 99.5%.
The improvement is that the solvent is one or the mixture of any two of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
The improvement is that the additive is any one or mixture of two of boric acid, sodium chloride, potassium chloride, lithium chloride, ammonium chloride, zinc chloride, aluminum chloride hexahydrate, cobalt chloride hexahydrate, magnesium chloride hexahydrate, anhydrous calcium chloride, calcium chloride dihydrate, barium chloride dihydrate, cobalt chloride hexahydrate, ferric chloride hexahydrate, manganese chloride, hydrogen chloride, or 1-butyl-3-methylimidazole chloride salt.
As a modification, the heating temperature in step 1 is 160 ℃.
As a modification, the reaction time in step 1 was 5 min.
Has the advantages that:
compared with the prior art, the method for preparing 3-acetamido-5-acetylfuran by catalyzing N-acetylglucosamine with ammonium chloride utilizes renewable biomass resource chitin monomer N-acetylglucosamine as a raw material to prepare 3A5AF, and is reasonable in utilization of biomass resources; the ammonium chloride which is cheap and easy to obtain is used as the catalyst, the highest yield (41.46%) can be achieved within a short time (5 min) at a lower temperature (160 ℃), 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 3-acetamido-5-acetylfuran (3A 5 AF) standard;
FIG. 2 is the liquid phase detection result of NAG after 5min reaction under the catalyst.
Detailed description of the preferred embodiments
The present invention is further described by the following examples, which are not intended to limit the scope of the present invention, and the experimental methods in the examples are conventional methods unless otherwise specified.
Example 1
100mg of N-acetylglucosamine NAG and 48mg of ammonium chloride (catalyst) are put into a pressure-resistant pipe, 5mL of N, N-dimethylformamide (solvent) is added at the same time, and the mixture is heated and stirred for 20min at 160 ℃ in a magnetic stirring heater under the pressure condition. Cooling to room temperature after the reaction is finished; adding pure water with the same volume to mix and dissolve, extracting for multiple times by using ethyl acetate, combining extract liquor, decoloring the collected extract liquor by using activated carbon, and recovering a solvent by using a rotary evaporator to obtain a solid crude product containing 3A5 AF; adding methanol with equal mass into a solid crude product containing 3A5AF for redissolving, dropwise adding into precooled deionized water for crystallization after redissolving, filtering and drying, measuring the content of 3-acetamido-5-acetylfuran by using high performance liquid chromatography, and calculating the yield of the 3-acetamido-5-acetylfuran according to a standard curve. Obtaining transparent needle-shaped 3A5AF crystal with purity as high as 99.5%. The molar conversion was calculated to be 28.16% based on the liquid phase results.
Example 2
100mg NAG and 48mg ammonium chloride (catalyst) are put into a pressure tube, 5mL dimethyl sulfoxide (solvent) is added at the same time, and the mixture is heated and stirred for 20min at 160 ℃ in a magnetic stirring heater under the pressure condition. Cooling to room temperature after the reaction is finished; adding pure water with the same volume to mix and dissolve, extracting for multiple times by using ethyl acetate, combining extract liquor, decoloring the collected extract liquor by using activated carbon, and recovering a solvent by using a rotary evaporator to obtain a solid crude product containing 3A5 AF; adding methanol with equal mass into a solid crude product containing 3A5AF for redissolving, dropwise adding into precooled deionized water for crystallization after redissolving, filtering and drying, measuring the content of 3-acetamido-5-acetylfuran by using high performance liquid chromatography, and calculating the yield of the 3-acetamido-5-acetylfuran according to a standard curve. Obtaining transparent needle-shaped 3A5AF crystal with purity as high as 99.5%. The molar conversion was calculated to be 0.47% based on the liquid phase results.
Example 3
100mg NAG and 48mg ammonium chloride (catalyst) are put into a pressure tube, 5mL of N-methylpyrrolidone (solvent) is added at the same time, and the mixture is heated and stirred for 20min at 160 ℃ in a magnetic stirring heater under the pressure condition. Cooling to room temperature after the reaction is finished; adding pure water with the same volume to mix and dissolve, extracting for multiple times by using ethyl acetate, combining extract liquor, decoloring the collected extract liquor by using activated carbon, and recovering a solvent by using a rotary evaporator to obtain a solid crude product containing 3A5 AF; adding methanol with equal mass into a solid crude product containing 3A5AF for redissolving, dropwise adding into precooled deionized water for crystallization after redissolving, filtering and drying, measuring the content of 3-acetamido-5-acetylfuran by using high performance liquid chromatography, and calculating the yield of the 3-acetamido-5-acetylfuran according to a standard curve. Obtaining transparent needle-shaped 3A5AF crystal with purity as high as 99.5%. The molar conversion was 21.61% calculated from the liquid phase results.
In examples 1 to 3, 3A5AF showed different molar conversions (N, N-dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone) in different solvents without adding any additive, and the molar conversion was 28.16% at the highest when N, N-dimethylformamide was used as the solvent, when the reaction time and the reaction temperature were the same.
Example 4
100mg of NAG, 48mg of ammonium chloride (catalyst) and 0.066g of calcium chloride dihydrate (additive) are put into a pressure-resistant pipe, 5mL of N, N-dimethylformamide (solvent) is added at the same time, and the mixture is heated and stirred for 20min at 160 ℃ in a magnetic stirring heater under the pressure condition. Cooling to room temperature after the reaction is finished; adding pure water with the same volume to mix and dissolve, extracting for multiple times by using ethyl acetate, combining extract liquor, decoloring the collected extract liquor by using activated carbon, and recovering a solvent by using a rotary evaporator to obtain a solid crude product containing 3A5 AF; adding methanol with equal mass into a solid crude product containing 3A5AF for redissolving, dropwise adding into precooled deionized water for crystallization after redissolving, filtering and drying, measuring the content of 3-acetamido-5-acetylfuran by using high performance liquid chromatography, and calculating the yield of the 3-acetamido-5-acetylfuran according to a standard curve. Obtaining transparent needle-shaped 3A5AF crystal with purity as high as 99.5%. The molar conversion was 36.89% based on the liquid phase results.
Example 5
100mg of NAG, 48mg of ammonium chloride (catalyst) and 0.101g of anhydrous calcium chloride (additive) are put into a pressure-resistant pipe, 5mL of N, N-dimethylformamide (solvent) is added at the same time, and the mixture is heated and stirred for 20min at 160 ℃ in a magnetic stirring heater under the pressure condition. Cooling to room temperature after the reaction is finished; adding pure water with the same volume to mix and dissolve, extracting for multiple times by using ethyl acetate, combining extract liquor, decoloring the collected extract liquor by using activated carbon, and recovering a solvent by using a rotary evaporator to obtain a solid crude product containing 3A5 AF; adding methanol with equal mass into a solid crude product containing 3A5AF for redissolving, dropwise adding into precooled deionized water for crystallization after redissolving, filtering and drying, measuring the content of 3-acetamido-5-acetylfuran by using high performance liquid chromatography, and calculating the yield of the 3-acetamido-5-acetylfuran according to a standard curve. Obtaining transparent needle-shaped 3A5AF crystal with purity as high as 99.5%. The molar conversion was 34.32% calculated from the liquid phase results.
Example 6
100mg of NAG, 48mg of ammonium chloride (catalyst) and 0.077g of anhydrous lithium chloride (additive) are put into a pressure-resistant pipe, 5mL of N, N-dimethylformamide (solvent) is added at the same time, and the mixture is heated and stirred for 20min at 160 ℃ in a magnetic stirring heater under the pressure condition. Cooling to room temperature after the reaction is finished; adding pure water with the same volume to mix and dissolve, extracting for multiple times by using ethyl acetate, combining extract liquor, decoloring the collected extract liquor by using activated carbon, and recovering a solvent by using a rotary evaporator to obtain a solid crude product containing 3A5 AF; adding methanol with equal mass into a solid crude product containing 3A5AF for redissolving, dropwise adding into precooled deionized water for crystallization after redissolving, filtering and drying, measuring the content of 3-acetamido-5-acetylfuran by using high performance liquid chromatography, and calculating the yield of the 3-acetamido-5-acetylfuran according to a standard curve. Obtaining transparent needle-shaped 3A5AF crystal with purity as high as 99.5%. The molar conversion was 38.24% based on the liquid phase results.
In examples 4 to 6, N-dimethylformamide was used as a solvent, and the reaction was carried out at 160 ℃ for 20min, and by adding various additives, the conversion was 38.24% at the highest level in the case of lithium chloride as an additive.
Example 7
The molar conversion was 41.46% as calculated from the liquid phase results in the same manner as in example 6 except that the reaction time was changed to 5 min.
Example 8
The molar conversion was 38.29% based on the liquid phase results, except that the reaction time was changed to 60min in the same manner as in example 6.
In examples 6-8, the reaction time was 5min, 20min, and 60min, and the 3A5AF molar conversion reached the highest value of 41.46% at 5 min. The results show that the reduction of the molar conversion of 3A5AF is not significant with the increase of the reaction time in this system, and the yield remains relatively stable over time.
The method takes chitin monomer N-acetylglucosamine as a raw material to prepare 3A5AF, which is a reasonable utilization of biomass resources; the ammonium chloride which is cheap and easy to obtain and is nontoxic to the environment is used as the catalyst, so that the production cost is greatly reduced.
Combining the above documents with the production process of patent report 3A5AF, the temperature is mostly concentrated between 180 ℃ and 220 ℃ and microwave heating is mostly used, which limits the large-scale application thereof to some extent. The method of the invention has simple heating device, can achieve higher yield (41.46%) only by reacting for 5min at lower reaction temperature (160 ℃), has simple subsequent separation and purification mode and high product purity, and is suitable for industrial production.
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-acetamido-5-acetylfuran by catalyzing N-acetylglucosamine with ammonium chloride is characterized by comprising the following steps:
step 1, taking 0.025g-0.25g 0.25g N-acetylglucosamine, ammonium chloride and an additive into a pressure-resistant pipe, adding 1-100mL of a solvent for dissolving, heating to 120-180 ℃, reacting for 5-120min, stopping the reaction, filtering and taking a filtrate for later use, wherein the adding amount of the ammonium chloride and the additive is 0.1-10 times of that of NAG;
step 2, adding water with the same volume to the filtrate for mixing, extracting with ethyl acetate for three times, combining the extract liquor after extraction, decoloring with active carbon, and concentrating under reduced pressure to obtain a solid crude product containing 3A5 AF;
and 3, adding methanol with equal mass into the solid crude product containing 3A5AF for redissolution, dropwise adding into precooled deionized water for crystallization after redissolution, 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 catalyzing N-acetylglucosamine with ammonium chloride according to claim 1, wherein the solvent is one or a mixture of any two of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
3. The method for preparing 3-acetamido-5-acetylfuran by catalyzing N-acetylglucosamine with ammonium chloride according to claim 1, wherein the additive is any one or two of boric acid, sodium chloride, potassium chloride, lithium chloride, ammonium chloride, zinc chloride, aluminum chloride hexahydrate, cobalt chloride hexahydrate, magnesium chloride hexahydrate, anhydrous calcium chloride, calcium chloride dihydrate, barium chloride dihydrate, cobalt chloride hexahydrate, ferric chloride hexahydrate, manganese chloride, hydrogen chloride, or 1-butyl-3-methylimidazolium chloride salt.
4. The method for preparing 3-acetamido-5-acetylfuran from chitin monomer N-acetylglucosamine by using ammonium chloride as claimed in claim 1, wherein the heating temperature in step 1 is 160 ℃.
5. The method for preparing 3-acetamido-5-acetylfuran by catalyzing chitin monomer N-acetylglucosamine with ammonium chloride according to claim 1, wherein the reaction time in step 1 is 5 min.
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| CN110878072A (en) * | 2019-11-22 | 2020-03-13 | 天津工业大学 | Method for preparing 3-acetamido-5-acetylfuran from chitin monomer N-acetylglucosamine |
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| CN111072602A (en) * | 2019-11-22 | 2020-04-28 | 天津工业大学 | Preparation of 3-acetamido-5-acetylfuran from chitin monomer N-acetylglucosamine catalyzed by amino acid ionic liquid |
| CN112522339A (en) * | 2020-12-18 | 2021-03-19 | 南京工业大学 | Method for preparing 3-acetamido-5-acetylfuran by degrading N-acetyl-D-glucosamine with chitin |
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