CN111559994A - Method for preparing 2, 5-furan dicarbaldehyde from fructose - Google Patents
Method for preparing 2, 5-furan dicarbaldehyde from fructose Download PDFInfo
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- CN111559994A CN111559994A CN202010406882.7A CN202010406882A CN111559994A CN 111559994 A CN111559994 A CN 111559994A CN 202010406882 A CN202010406882 A CN 202010406882A CN 111559994 A CN111559994 A CN 111559994A
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- furandicarboxaldehyde
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- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 title claims abstract description 36
- 229930091371 Fructose Natural products 0.000 title claims abstract description 36
- 239000005715 Fructose Substances 0.000 title claims abstract description 36
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- -1 piperidine nitroxide Chemical class 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 8
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- CSGAUKGQUCHWDP-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1O CSGAUKGQUCHWDP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 3
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 3
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical compound CC(C)(C)ON=O IOGXOCVLYRDXLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012414 tert-butyl nitrite Substances 0.000 claims description 3
- RVWUHFFPEOKYLB-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1(C)CCCC(C)(C)[NH+]1[O-] RVWUHFFPEOKYLB-UHFFFAOYSA-N 0.000 claims description 2
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 claims description 2
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- NSGAOVRUPINXOM-UHFFFAOYSA-N [N]=O.N1CCCCC1 Chemical compound [N]=O.N1CCCCC1 NSGAOVRUPINXOM-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/006—Catalysts comprising hydrides, coordination complexes or organic compounds comprising organic radicals, e.g. TEMPO
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Furan Compounds (AREA)
Abstract
The invention provides a method for preparing 2, 5-furan dicarbaldehyde from fructose, which is characterized in that the fructose is used as a raw material, DFF is obtained by one-pot dehydration and oxidation under mild conditions, the difficulty in separating HMF is avoided, piperidine nitroxide free radicals are used on a catalyst, any metal ion can be avoided in the reaction process, the economic advantage of the whole synthesis process is obvious, and the synthesis process is more in line with the green chemical target.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for preparing 2, 5-furan dicarbaldehyde from fructose.
Background
2, 5-furan Dicarbaldehyde (DFF) is an important organic platform compound, and has good application prospect in a plurality of fields such as medicines, polymers, adhesives and the like because active groups contained in the molecular structure of the DFF can perform chemical reactions such as hydrogenation, oxidation, polymerization, hydrolysis and the like. Currently, the method for synthesizing DFF mainly uses 5-Hydroxymethylfurfural (HMF) obtained from biomass as a raw material and prepares the DFF through oxidation reaction, but HMF is difficult to separate and expensive, so the production cost is too high and industrialization is difficult to realize. The DFF is directly prepared by taking carbohydrate as a raw material, so that the expensive separation step of HMF can be avoided, and the method is more economic and environment-friendly.
Chinese patent CN101768142A proposes a two-step method for synthesizing DFF from carbohydrate as raw material, vanadium salt as catalyst and sodium bromide as additive, wherein the catalyst and additive can be separated by simple centrifugation, but the reaction selectivity and yield are low.
Chinese patent CN108675971A proposes a method for converting fructose into 2, 5-furandicarboxaldehyde using piperidine nitrogen oxide as catalyst and sodium nitrite or potassium nitrite as cocatalyst, although the reaction yield is still acceptable, the use of metal nitrite will cause electrochemical corrosion of reaction equipment in long-term large-scale practical production, and is not economical from the atom economy point of view.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides a method for preparing 2, 5-furan dicarbaldehyde from fructose, DFF is obtained by one-pot dehydration and oxidation under mild conditions by using the fructose as a raw material, the difficulty in separating HMF is avoided, piperidine nitroxide free radicals and nitroxide compounds without metal ions are used in a catalyst and a cocatalyst, the economic advantage of the whole synthesis process is obvious, and the synthesis process meets the green chemical target.
The invention provides a method for preparing 2, 5-furan dicarbaldehyde from fructose, which comprises the following steps: under the condition that piperidine nitroxide free radical is used as a catalyst and nitroxide compound and protonic acid is used as a cocatalyst, performing dehydration oxidation reaction on fructose and an oxidant to obtain 2, 5-furan dicarbaldehyde;
wherein the oxynitride is one or more of nitric oxide, nitrogen dioxide, nitric acid, methyl nitrite, ethyl nitrite, tert-butyl nitrite and isoamyl nitrite.
Preferably, the piperidine nitroxide radical is 2, 2, 6, 6-tetramethylpiperidine oxide or 4-hydroxy-2, 2, 6, 6-tetramethylpiperidine oxide.
Preferably, the amount of the piperidine nitroxide radical is 0.1-10% of the molar amount of fructose.
Preferably, the protic acid is hydrochloric acid.
Preferably, the protonic acid is used in an amount of 1 to 20% by mole based on the fructose.
Preferably, the oxidant is oxygen.
Preferably, the nitrogen oxide is used in an amount of 1 to 10% by mole based on the fructose.
Preferably, the solvent for the reaction is one or a combination of more of dichloromethane, 1, 2-dichloroethane, chloroform, chlorobenzene.
Preferably, the reaction temperature of the dehydration oxidation reaction is 0 to 120 ℃.
Preferably, the reaction time of the dehydration oxidation reaction is 1-24 h.
The invention uses piperidine nitroxide free radical as catalyst, nitrogen oxide compound and protonic acid as cocatalyst, and converts fructose into DFF in the presence of organic solvent and oxidant. The existing synthesis method and process are an improvement, and the synthesis process of the method avoids the defects of the existing method and is completely suitable for industrial production.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 2, 5-furandicarboxaldehyde obtained in example 1.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A method for preparing 2, 5-furan dicarbaldehyde from fructose specifically comprises the following steps:
fructose (1mol, 180.2g), 36% hydrochloric acid (0.1mol, 10.13g), 2, 6, 6-tetramethylpiperidine oxide (0.1mol, 15.6g) and chlorobenzene (500mL) are added into a 1L high-pressure reaction kettle, after uniform stirring, oxygen (4MPa) and nitric oxide (0.1mol, 0.27MPa) are introduced into the kettle to react for 5 hours at 120 ℃, gas in the kettle is introduced into an alkali solution absorption pool after the reaction is finished, a mixture in the kettle is kept stand for layering, solvent phase is subjected to pressure concentration to obtain a product 2, 5-furandicarbaldehyde, and the yield is 95.9%. Wherein, the hydrogen spectrum of 2, 5-furan dicarbaldehyde is shown in figure 1.
Example 2
A method for preparing 2, 5-furan dicarbaldehyde from fructose specifically comprises the following steps:
fructose (1mol, 180.2g), 36% hydrochloric acid (0.2mol, 20.3g), 4-hydroxy-2, 2, 6, 6-tetramethylpiperidine oxide (0.05mol, 8.6g) and 1, 2-dichloroethane (500mL) are added into a 1L high-pressure reaction kettle, after uniform stirring, oxygen (5MPa) and nitrogen dioxide (0.05mol, 0.16MPa) are introduced into the kettle and react for 1 hour at 50 ℃, gas in the kettle is introduced into an alkali solution absorption pool after the reaction is finished, a mixture in the kettle is kept stand for layering, and the solvent phase is subjected to pressure concentration to obtain a product 2, 5-furandicarbaldehyde with the yield of 93.2%.
Example 3
A method for preparing 2, 5-furan dicarbaldehyde from fructose specifically comprises the following steps:
fructose (1mol, 180.2g), 36% hydrochloric acid (0.01mol, 1.0g), 2, 6, 6-tetramethylpiperidine oxide (0.001mol, 0.156g), 98% nitric acid (0.01mol, 0.64 g) and dichloromethane (500mL) are added into a 1L high-pressure reaction kettle, after uniform stirring, oxygen (4MPa) is introduced into the kettle, the reaction is carried out for 18 hours at 30 ℃, gas in the kettle is introduced into an alkali solution absorption pool after the reaction is finished, a mixture in the kettle is kept stand for layering, solvent phase is subjected to pressure concentration, dichloroethane is recrystallized to obtain a product 2, 5-furandicarbaldehyde, and the yield is 88.5%.
Example 4
Fructose (1mol, 180.2g), 36% hydrochloric acid (0.1mol, l0.13g), 4-hydroxy-2, 2, 6, 6-tetramethylpiperidine oxide (0.1mol, 17.2g), isoamyl nitrite (0.1mol, 11.7g) and dichloromethane (500mL) are added into a 1L high-pressure reaction kettle, after uniform stirring, oxygen (3MPa) is introduced into the kettle, the reaction is carried out for 8 hours at 80 ℃, gas in the kettle is introduced into an alkali solution absorption pool after the reaction is finished, a mixture in the kettle is kept stand for layering, and the solvent phase is subjected to pressure concentration to obtain a product 2, 5-furandicarbaldehyde with the yield of 96.6%.
Example 5
A method for preparing 2, 5-furan dicarbaldehyde from fructose specifically comprises the following steps:
fructose (1mol, 180.2g), 36% hydrochloric acid (0.01mol, 1.0g), 4-hydroxy-2, 2, 6, 6-tetramethylpiperidine oxide (0.05mol, 8.6g), tert-butyl nitrite (0.05mol, 5.2g) and dichloromethane (500mL) are added into a 1L high-pressure reaction kettle, after uniform stirring, oxygen (4MPa) is introduced into the kettle, the reaction is carried out for 24 hours at 0 ℃, gas in the kettle is introduced into an alkali solution absorption cell after the reaction is finished, the mixture in the kettle is kept stand for layering, the solvent phase is subjected to pressure concentration, and the product 2, 5-furandicarbaldehyde is obtained, wherein the yield is 89.2%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical scope of the present invention, and equivalents and modifications thereof should be included in the technical scope of the present invention.
Claims (10)
1. A method for preparing 2, 5-furan dicarbaldehyde from fructose, which is characterized by comprising the following steps: under the condition that piperidine nitroxide free radical is used as a catalyst and nitroxide compound and protonic acid is used as a cocatalyst, performing dehydration oxidation reaction on fructose and an oxidant to obtain 2, 5-furan dicarbaldehyde;
wherein the oxynitride is one or more of nitric oxide, nitrogen dioxide, nitric acid, methyl nitrite, ethyl nitrite, tert-butyl nitrite and isoamyl nitrite.
2. The method of claim 1, wherein the piperidine nitroxide radical is 2, 2, 6, 6-tetramethylpiperidine oxide or 4-hydroxy-2, 2, 6, 6-tetramethylpiperidine oxide.
3. The method for preparing 2, 5-furandicarboxaldehyde from fructose according to claim 1 or 2, wherein the piperidine nitroxide radical is used in an amount of 0.1 to 10% by mole based on fructose.
4. The method for preparing 2, 5-furandicarboxaldehyde from fructose according to any one of claims 1 to 3, wherein the protonic acid is one or a combination of hydrochloric acid, sulfuric acid, nitric acid, sodium bisulfate, potassium bisulfate.
5. The process for preparing 2, 5-furandicarboxaldehyde from fructose according to any one of claims 1 to 4, wherein the protic acid is used in an amount of 1 to 20% by mole based on fructose.
6. The process for preparing 2, 5-furandicarboxaldehyde from fructose according to any one of claims 1 to 5, wherein the oxidizing agent is oxygen.
7. The process for preparing 2, 5-furandicarboxaldehyde from fructose as claimed in any one of claims 1 to 6, wherein the nitroxide is used in an amount of 1 to 10% by mole based on fructose.
8. The method for preparing 2, 5-furandicarboxaldehyde from fructose according to any one of claims 1 to 7, wherein the solvent for the reaction is one or more of dichloromethane, 1, 2-dichloroethane, chloroform, chlorobenzene or their combination.
9. The process for preparing 2, 5-furandicarboxaldehyde from fructose according to any one of claims 1 to 8, wherein the reaction temperature of the dehydration oxidation reaction is 0 to 120 ℃.
10. The process for preparing 2, 5-furandicarboxaldehyde from fructose according to any one of claims 1 to 9, wherein the reaction time of the dehydration oxidation reaction is 1 to 24 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112778231A (en) * | 2021-01-29 | 2021-05-11 | 杭州凯方科技有限公司 | Novel synthesis method of 4-methylthiazole-5-formaldehyde |
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|---|---|---|---|---|
| CN101565344A (en) * | 2008-04-25 | 2009-10-28 | 中国科学院大连化学物理研究所 | Method for preparing aldehyde or alkone by oxygen catalysis and alcohol oxidation under mild condition |
| CN102307839A (en) * | 2009-02-06 | 2012-01-04 | 赢创德固赛有限责任公司 | Method for producing aldehydes and ketones from primary and secondary alcohols |
| CN108675971A (en) * | 2018-04-04 | 2018-10-19 | 中国科学技术大学 | A method of preparing 2,5- furans dicarbaldehydes |
| CN110437190A (en) * | 2019-07-29 | 2019-11-12 | 中国科学技术大学 | The method that 2,5- furandicarboxylic acid is prepared by 5 hydroxymethyl furfural |
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