CN113845499A - Method for synthesizing 2, 5-furandicarboxylic acid by using N-heterocyclic carbene to catalyze carbon dioxide - Google Patents
Method for synthesizing 2, 5-furandicarboxylic acid by using N-heterocyclic carbene to catalyze carbon dioxide Download PDFInfo
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- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 112
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 22
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 7
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000012044 organic layer Substances 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HDJLSECJEQSPKW-UHFFFAOYSA-N Methyl 2-Furancarboxylate Chemical compound COC(=O)C1=CC=CO1 HDJLSECJEQSPKW-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- HSCVIIISAAEVQT-UHFFFAOYSA-N Propyl 2-furoate Chemical compound CCCOC(=O)C1=CC=CO1 HSCVIIISAAEVQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
- NHXSTXWKZVAVOQ-UHFFFAOYSA-N Ethyl furoate Chemical compound CCOC(=O)C1=CC=CO1 NHXSTXWKZVAVOQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- HDKCVDHYIIKWFM-UHFFFAOYSA-K octanoate;rhodium(3+) Chemical compound [Rh+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HDKCVDHYIIKWFM-UHFFFAOYSA-K 0.000 claims description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 230000020477 pH reduction Effects 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009825 accumulation Methods 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 5
- AETGYSUEDWYSME-UHFFFAOYSA-N 5-methoxycarbonylfuran-2-carboxylic acid Chemical compound COC(=O)C1=CC=C(C(O)=O)O1 AETGYSUEDWYSME-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- -1 furoate ester Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- SMMNUDQGZVFDTO-UHFFFAOYSA-N 5-ethoxycarbonylfuran-2-carboxylic acid Chemical compound CCOC(=O)C1=CC=C(C(O)=O)O1 SMMNUDQGZVFDTO-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- FUIBMNRLZXTCML-UHFFFAOYSA-N CC(C)OC(=O)c1ccc(o1)C(O)=O Chemical compound CC(C)OC(=O)c1ccc(o1)C(O)=O FUIBMNRLZXTCML-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
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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
- C07D307/56—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
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 2, 5-furandicarboxylic acid by using nitrogen heterocyclic carbene to catalyze carbon dioxide, which comprises the following steps: (1) dissolving furoate, N-heterocyclic carbene NHC and metal compound catalyst in a first solvent, and introducing CO2Reacting to obtain 2, 5-furandicarboxylic acid 2-formic ether; (2) dissolving 2, 5-furandicarboxylic acid 2-formic ether and alkali in a second solvent for reaction to obtain 2, 5-furandicarboxylic acid salt; (3) dissolving 2, 5-furandicarboxylic acid salt in deionized water, and acidifying with acid to obtain 2, 5-furandicarboxylic acid; compared with the prior art, the invention has simple reaction system, no accumulation of intermediate oxidation products, high yield and high industrial application potential of FDCA; with CO2Is also a carbon resource with abundant reserves, low price and easy obtaining, and converts CO by catalysis2Efficiently converting into products with high economic added value2And (4) discharging.
Description
Technical Field
The invention belongs to the technical field of 2, 5-furandicarboxylic acid synthesis, and particularly relates to a method for synthesizing 2, 5-furandicarboxylic acid by catalyzing carbon dioxide with azacyclo-carbene.
Background
2, 5-furandicarboxylic acid is a bio-based aromatic monomer, can be used for synthesizing high-performance polyesters, polyamides and epoxy resins, is determined by the U.S. department of energy as one of the 12 most potential bio-based platform compounds, and is also considered as "sleeping giant". At present, 2, 5-furandicarboxylic acid is mainly prepared by chemically catalyzing 5-hydroxymethylfurfural, the 2, 5-furandicarboxylic acid is synthesized by catalyzing furoate ester at the starting stage, and CO is not used in the existing reports2Catalyzing to generate 2, 5-furandicarboxylic acid.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a method for synthesizing 2, 5-furandicarboxylic acid by using nitrogen heterocyclic carbene to catalyze carbon dioxide.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing 2, 5-furandicarboxylic acid by using nitrogen heterocyclic carbene to catalyze carbon dioxide comprises the following steps:
(1) dissolving furoate, N-heterocyclic carbene NHC and metal compound catalyst in a first solvent, and introducing CO2Reacting to obtain 2, 5-furandicarboxylic acid 2-formic ether;
(2) dissolving 2, 5-furandicarboxylic acid 2-formic ether and alkali in a second solvent for reaction to obtain 2, 5-furandicarboxylic acid salt;
(3) dissolving 2, 5-furandicarboxylic acid salt in deionized water, and acidifying with acid to obtain 2, 5-furandicarboxylic acid;
wherein R is selected from C1-C5 alkyl.
Preferably, the method comprises the following steps:
in the step (1), the N-heterocyclic carbene is selected from imidazole N-heterocyclic carbenes.
In the step (1), the N-heterocyclic carbene is selected from the following structures:
in the step (1), the furoate ester is any one of methyl furoate, ethyl furoate, propyl furoate and the like; the metal compound catalyst is any one of rhodium chloride, rhodium acetate, rhodium nitrate, rhodium octanoate and the like; the first solvent is N, N-dimethylformamide; the molar ratio of the furoate to the azacyclo-carbene to the metal compound catalyst to the first solvent is 1:
(0.008-0.013)：(0.015-0.025)：100。
in the step (1), the reaction is carried out in CO2Reacting in the atmosphere, wherein the reaction time is 36-48h, and the temperature is 130-150 ℃.
In step (1), after the reaction is finished, the solvent is removed from the reaction mixture in vacuum, and column chromatography (SiO) is carried out2Dichloromethane/methanol, 30: 1) 2, 5-Furan dicarboxylic acid 2-carboxylate was obtained as a white solid.
In the step (2), the alkali is any one of sodium hydroxide and potassium hydroxide; the second solvent is methanol, ethanol, 2-formic ether of 2, 5-furandicarboxylic acid and alkali in a molar ratio of 1: (1-1.1); the dosage of the second solvent is 8-10 times of the total mass of the 2-formic ether of 2, 5-furandicarboxylic acid and the alkali;
in the step (2), the reaction temperature is 60-75 ℃; the reaction time is 12-16 h.
In the step (3), the acid is strong acid without oxidation, preferably concentrated hydrochloric acid.
In the step (3), acidifying to obtain a 2, 5-furandicarboxylate crude product, removing the solvent in vacuum, adding a proper amount of deionized water, and extracting with dichloromethane (preferably three times); the organic layer was acidified with concentrated hydrochloric acid until pH 2; the heterogeneous solution was extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate and the solvent was removed in vacuo to give 2, 5-furandicarboxylic acid
Has the advantages that: compared with the prior art, the invention has simple reaction system, no accumulation of intermediate oxidation products, high yield and high industrial application potential of FDCA; with CO2Is also oneThe carbon resource with abundant reserves, low price and easy obtaining is used for catalyzing and converting CO2Efficiently converting into products with high economic added value2And (4) discharging.
Drawings
FIG. 1 is a hydrogen spectrum of N-heterocyclic carbene in step 1 of the example.
FIG. 2 is a hydrogen spectrum of the product of step 1 in example 1.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The azaheterocyclic carbenes used in the following examples are selected from the following structures:
example 1:
the method comprises the following steps: 1.26g of methyl furoate, 0.118g of azacyclocarbene and 44.2mg of rhodium acetate dimer are added to a dry flask, 30ml of DMF is added, vacuum is applied and CO is introduced2Reaction at 150 deg.c for 48 hr to obtain crude methyl 2, 5-furandicarboxylate product, which is subjected to column chromatography to obtain 1.47g of 2, 5-furandicarboxylate methyl 2-carboxylate in 86.41% yield.
Step two: 1.47g of 2, 5-furandicarboxylic acid methyl 2-carboxylate and sodium hydroxide were dissolved in methanol and reacted at 60 ℃ for 14 hours to obtain 1.45g of crude 2, 5-furandicarboxylic acid salt with a yield of 100%.
Step three: removing the solvent from 1.45g of 2, 5-furandicarboxylate crude product in vacuum, adding a proper amount of deionized water, and extracting with a proper amount of dichloromethane for three times; acidifying the organic layer with concentrated hydrochloric acid until the pH is 2; the heterogeneous solution was extracted with 250mL of ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and the solvent was removed in vacuo to give 1.07g of 2, 5-furandicarboxylic acid as a white powder in 99% yield.
Example 2:
the method comprises the following steps: 1.40g of furoic acid ethyl esterEster, 0.118g azacyclocarbene and 44.2mg rhodium acetate dimer were added to a dry flask, 30ml DMF was added, vacuum was applied and CO was passed through2Reaction at 150 deg.c for 48 hr to obtain crude ethyl 2, 5-furandicarboxylate product, which is subjected to column chromatography to obtain 1.53g of 2, 5-furandicarboxylate ethyl 2-carboxylate, yield 83.08%.
Step two: 1.53g of 2, 5-furandicarboxylic acid ethyl 2-carboxylate and sodium hydroxide were dissolved in methanol and reacted at 60 ℃ for 14 hours to obtain 1.396g of crude 2, 5-furandicarboxylic acid salt with a yield of 100%.
Step three: removing the solvent from 1.396g of 2, 5-furandicarboxylate crude product in vacuum, adding a proper amount of deionized water, and extracting with a proper amount of dichloromethane for three times; acidifying the organic layer with concentrated hydrochloric acid until the pH is 2; the heterogeneous solution was extracted with 250mL of ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and the solvent was removed in vacuo to give 1.031g of 2, 5-furandicarboxylic acid as a white powder in 99% yield.
Example 3:
the method comprises the following steps: 1.54g of propyl furoate, 0.118g of azacyclocarbene and 44.2mg of rhodium acetate dimer were added to a dry flask, 30ml of DMF was added, and the flask was evacuated and charged with CO2Reaction at 150 deg.c for 48 hr to obtain 2-propyl 2, 5-furandicarboxylate, which was purified by column chromatography to obtain 2, 5-furandicarboxylate, 2-propyl 2-carboxylate, 1.47g, in 74.18% yield.
Step two: 1.47g of 2, 5-furandicarboxylic acid propyl 2-carboxylate and sodium hydroxide were dissolved in methanol and reacted at 60 ℃ for 14 hours to obtain 1.247g of crude 2, 5-furandicarboxylic acid salt with a yield of 100%.
Step three: removing the solvent from 1.247g of 2, 5-furandicarboxylate crude product in vacuum, adding a proper amount of deionized water, and extracting with a proper amount of dichloromethane for three times; acidifying the organic layer with concentrated hydrochloric acid until the pH is 2; the heterogeneous solution was extracted with 250mL of ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and the solvent was removed in vacuo to give 0.921g of 2, 5-furandicarboxylic acid as a white powder in 99% yield.
Example 4:
the method comprises the following steps: 1.26g of methyl furoate, 0.118g of azacyclocarbene and 44.2mg of rhodium acetate dimer were charged to a dry flaskAdding 30ml of DMMF, vacuumizing and introducing CO2Reaction at 130 deg.c for 42 hr to obtain crude methyl 2, 5-furandicarboxylate product, which is subjected to column chromatography to obtain 1.40g of 2, 5-furandicarboxylate methyl 2-carboxylate in 82.29% yield.
Step two: 1.40g of 2, 5-furandicarboxylic acid methyl 2-carboxylate and sodium hydroxide were dissolved in methanol and reacted at 60 ℃ for 14 hours to obtain 1.38g of crude 2, 5-furandicarboxylic acid salt with a yield of 100%.
Step three: removing the solvent from 1.38g of 2, 5-furandicarboxylate crude product in vacuum, adding a proper amount of deionized water, and extracting with a proper amount of dichloromethane for three times; acidifying the organic layer with concentrated hydrochloric acid until the pH is 2; the heterogeneous solution was extracted with 250mL of ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and the solvent was removed in vacuo to give 1.026g2, 5-furandicarboxylic acid as a white powder in 99% yield.
Example 5:
the method comprises the following steps: 1.26g of methyl furoate, 0.118g of azacyclocarbene and 44.2mg of rhodium acetate dimer are added to a dry flask, 30ml of DMF is added, vacuum is applied and CO is introduced2Reaction at 150 deg.c for 36 hr to obtain crude methyl 2, 5-furandicarboxylate product, which is subjected to column chromatography to obtain 1.38g of 2, 5-furandicarboxylate methyl 2-carboxylate in 81.12% yield.
Step two: 1.38g of 2, 5-furandicarboxylic acid methyl 2-carboxylate and sodium hydroxide were dissolved in methanol and reacted at 60 ℃ for 14 hours to obtain 1.36g of crude 2, 5-furandicarboxylic acid salt with a yield of 100%.
Step three: removing the solvent from 1.45g of 2, 5-furandicarboxylate crude product in vacuum, adding a proper amount of deionized water, and extracting with a proper amount of dichloromethane for three times; acidifying the organic layer with concentrated hydrochloric acid until the pH is 2; the heterogeneous solution was extracted with 250mL of ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and the solvent was removed in vacuo to give 1.00g of 2, 5-furandicarboxylic acid as a white powder in 99% yield. .
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for synthesizing 2, 5-furandicarboxylic acid by using nitrogen heterocyclic carbene to catalyze carbon dioxide is characterized by comprising the following steps:
(1) dissolving furoate, N-heterocyclic carbene NHC and metal compound catalyst in a first solvent, and introducing CO2Reacting to obtain 2, 5-furandicarboxylic acid 2-formic ether;
(2) dissolving 2, 5-furandicarboxylic acid 2-formic ether and alkali in a second solvent for reaction to obtain 2, 5-furandicarboxylic acid salt;
(3) dissolving 2, 5-furandicarboxylic acid salt in deionized water, and acidifying with acid to obtain 2, 5-furandicarboxylic acid;
wherein R is selected from C1-C5 alkyl.
2. The method for synthesizing 2, 5-furandicarboxylic acid by using N-heterocyclic carbene to catalyze carbon dioxide according to claim 1, wherein in the step (1), the N-heterocyclic carbene is selected from imidazole N-heterocyclic carbenes.
3. The method for synthesizing 2, 5-furandicarboxylic acid by using azacyclo-carbene to catalyze carbon dioxide as claimed in claim 1, wherein in step (1), the azacyclo-carbene is selected from the following structures:
4. the method for synthesizing 2, 5-furandicarboxylic acid by using N-heterocyclic carbene as a catalyst, according to claim 1, wherein in the step (1), the furoate is any one of methyl furoate, ethyl furoate and propyl furoate; the metal compound catalyst is any one of rhodium chloride, rhodium acetate, rhodium nitrate and rhodium octanoate; the first solvent is N, N-dimethylformamide; the molar ratio of the furoate to the azacyclo-carbene to the metal compound catalyst to the first solvent is 1: (0.008-0.013): (0.015-0.025): 100.
5. the method for synthesizing 2, 5-furandicarboxylic acid by using N-heterocyclic carbene to catalyze carbon dioxide according to claim 1, wherein in the step (1), the reaction is carried out in CO2Reacting in the atmosphere, wherein the reaction time is 36-48h, and the temperature is 130-150 ℃.
6. The method for synthesizing 2, 5-furandicarboxylic acid by using N-heterocyclic carbene as a catalyst according to claim 1, wherein in the step (1), after the reaction is finished, the solvent is removed from the reaction mixture in vacuum, and the reaction mixture is subjected to column chromatography to obtain white solid 2, 5-furandicarboxylic acid 2-formate.
7. The method for synthesizing 2, 5-furandicarboxylic acid by using N-heterocyclic carbene to catalyze carbon dioxide according to claim 1, wherein in the step (2), the base is any one of sodium hydroxide and potassium hydroxide; the second solvent is methanol, ethanol, 2-formic ether of 2, 5-furandicarboxylic acid and alkali in a molar ratio of 1: (1-1.1); the dosage of the second solvent is 8-10 times of the total mass of the 2-formic ether of 2, 5-furandicarboxylic acid and the alkali.
8. The method for synthesizing 2, 5-furandicarboxylic acid by using N-heterocyclic carbene to catalyze carbon dioxide according to claim 1, wherein in the step (2), the reaction temperature is 60-75 ℃; the reaction time is 12-16 h.
9. The method for synthesizing 2, 5-furandicarboxylic acid by using N-heterocyclic carbene to catalyze carbon dioxide according to claim 1, wherein in the step (3), the acid is strong non-oxidizing acid, preferably concentrated hydrochloric acid.
10. The method for synthesizing 2, 5-furandicarboxylic acid by using N-heterocyclic carbene to catalyze carbon dioxide according to claim 1, wherein in the step (3), a crude product of 2, 5-furandicarboxylic acid salt is obtained after acidification, the solvent is removed in vacuum, a proper amount of deionized water is added, and dichloromethane is used for extraction; the organic layer was acidified with concentrated hydrochloric acid until pH 2; the heterogeneous solution was extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed in vacuo to give 2, 5-furandicarboxylic acid.
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| CN108299353A (en) * | 2017-01-12 | 2018-07-20 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of 5- formic acid ester group furan compound |
| CN108299355A (en) * | 2017-01-12 | 2018-07-20 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the disubstituted furan compounds of 2,5- |
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| CN108299353A (en) * | 2017-01-12 | 2018-07-20 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of 5- formic acid ester group furan compound |
| CN108299355A (en) * | 2017-01-12 | 2018-07-20 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the disubstituted furan compounds of 2,5- |
Non-Patent Citations (1)
| Title |
|---|
| SCHMALZBAUER, M: "Redox-neutral Photocatalytic CH Carboxylation of Arenes and Styrenes with CO2", CHEM, 31 October 2020 (2020-10-31) * |
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| CN115260390A (en) * | 2022-07-26 | 2022-11-01 | 合肥工业大学 | Preparation of novel polymerized N-heterocyclic carbene catalyst and application of catalyst in furoic acid synthesis process |
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