CN108675971B - Method for preparing 2, 5-furan dicarbaldehyde - Google Patents
Method for preparing 2, 5-furan dicarbaldehyde Download PDFInfo
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- CN108675971B CN108675971B CN201810308799.9A CN201810308799A CN108675971B CN 108675971 B CN108675971 B CN 108675971B CN 201810308799 A CN201810308799 A CN 201810308799A CN 108675971 B CN108675971 B CN 108675971B
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- 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
Abstract
The invention provides a method for preparing 2, 5-furan dicarbaldehyde, which comprises the following steps: fructose is used as a raw material, piperidine nitrogen oxide is used as a catalyst, acid and nitrite are used as cocatalyst, and the product 2, 5-furan dicarbaldehyde is obtained by reaction in the presence of an organic solvent and an oxygen source. The invention is a method for preparing 2, 5-furan dicarbaldehyde (2, 5-DFF) by fructose in one step, has mild reaction conditions, is a method for preparing the 2, 5-furan dicarbaldehyde with low price, environmental protection, high activity and high yield, and has wide industrial application prospect.
Description
Technical Field
The invention relates to a method for preparing 2, 5-furan dicarbaldehyde. In particular to a method for preparing 2, 5-furan dicarbaldehyde by taking fructose as a starting material.
Background
Petroleum is an important dependence on human development since the 20 th century, and with the reduction in petroleum reserves and the increase in demand for petroleum products, the search for renewable petroleum substitutes has received much attention in recent years. Biomass has received much attention as the only renewable organic carbon resource. 5-Hydroxymethylfurfural (HMF) is an important platform molecule that can be obtained from biomass and converted into a variety of liquid fuels and chemicals. Can be converted into 2, 5-furandicarboxylic acid (2, 5-FDCA), 2, 5-furandicarboxaldehyde (2, 5-DFF) and the like through oxidation, and the latter is a chemical intermediate with important potential application value and can be used in a plurality of fields such as medicines, high molecular monomers, adhesives and the like. However, due to the abundant functional groups of HMF, a series of side reactions such as peroxidation, ether formation and hydrolysis may occur, making high yield access of 2, 5-DFF challenging.
Early 2, 5-DFF was obtained by oxidizing 5-HMF using an equivalent amount of an oxidizing agent such as permanganate, chromium trioxide or sodium hypochlorite. However, the preparation method has high cost and serious environmental pollution.
Lilga et al in patent US 2008/0103318A1 used active gamma-MnO2The reaction was carried out under reflux for 8 hours in methylene chloride as a catalyst, whereby 80% of 2, 5-DFF yield was obtained. However, this process uses over 600 wt% active γ -MnO2As a catalyst, post-treatment is difficult; the reaction time is longer, and the activity is very low; the yield of the product is also low.
Liu' an et al in patent CN 106674162A using sodium nitrite as the oxidant and trifluoroacetic acid as the solvent gave 2, 5-DFF in 90% yield. The reaction system is simple and easy to purify. However, trifluoroacetic acid is used as a solvent, so that the requirement on equipment is high.
Wei Kanjun et al used Cu (NO) in patent CN 106008416A3)2·3H2O is used as an oxidant, and 2, 5-furan dicarbaldehyde with the yield of 99.5 percent is prepared in a water-acetonitrile/nonpolar solvent two-phase reaction system. But catalyst Cu (NO)3)2·3H2The dosage of O reaches 180 percent of that of 5-HMF.
Liuhai super et al in CN 102731448B and Yao et al in Green Chemistry14(2012) 2986-. The reaction condition of the process is mild, and the yield of the 2, 5-DFF reaches up to 99 percent. However, the solvent used in the reaction system is a high boiling point solvent, which makes the separation of the product in the system difficult.
In ChemCatChem, 2015, 7 (9): 1470-1477, polyaniline-VO (acac)2Using fructose as a starting material as a catalyst, 2, 5-DFF was obtained in tetrachlorotoluene at a yield of 86.2%. The system is complex, the solvent used is toxic, and the yield is low
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing 2, 5-furan dicarbaldehyde (2, 5-DFF) from fructose (one step) under mild reaction conditions, which is cheap, green and environment-friendly, has high activity and high yield.
To this end, the present invention provides the following aspects:
a method for preparing 2, 5-furandicarboxaldehyde, comprising the steps of:
fructose is used as a raw material, piperidine nitrogen oxide is used as a catalyst, acid and nitrite are used as cocatalyst, and the product 2, 5-furan dicarbaldehyde is obtained by reaction in the presence of an organic solvent and an oxygen source.
<2> the production method according to <1>, wherein the amount of the substance of the piperidine nitrogen oxide catalyst is 0.1% to 100% of the amount of the substance of fructose.
<3> the production method according to any one of the preceding claims, wherein the ratio of the fructose mass to the volume of the organic solvent is 1 to 1000 g/L.
The production method according to any one of the preceding claims, wherein the amount of substance of the acid is 0.1% to 100% of the amount of substance of the fructose, and the amount of substance of the salt is 0.1% to 100% of the amount of substance of the fructose.
The production method according to any one of the preceding claims, wherein the piperidine nitrogen oxide catalyst is at least one of the following structures
The production method according to any one of the preceding claims, wherein
The acid is selected from at least one of sulfuric acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, hydroiodic acid, perchloric acid, periodic acid, chlorine, bromine, nitric acid, phosphoric acid, glacial acetic acid, and formic acid.
The production method according to any one of the preceding claims, wherein the organic solvent is selected from at least one of dichloroethane, tetrachloroethane, monochloromethane, dichloromethane, trichloromethane, tetrachloromethane, ethyl acetate, toluene, dioxane, tetrahydrofuran and acetonitrile.
The production method according to any one of the preceding claims, wherein the salt is sodium nitrite or potassium nitrite.
The production method according to any one of the preceding claims, wherein the reaction is carried out at a temperature of 0 to 200 ℃ for 0.1 to 72 hours.
<10> a 2, 5-furandicarboxaldehyde prepared by the preparation method of any one of the foregoing.
Drawings
FIG. 1 shows the NMR spectrum of 2, 5-furandicarboxaldehyde obtained by the process of the present invention.
Detailed Description
The preparation method of the 2, 5-furan diformaldehyde is characterized in that the piperidine oxynitride is used as a catalyst for the first time to directly convert the fructose into the 2, 5-furan diformaldehyde.
The fructose to be used in the present invention may be commercially available or synthesized in the laboratory, and its isomer glucose may be used, but the use of the isomer glucose is not recommended from the viewpoint of the yield of 2, 5-DFF.
In one embodiment of the invention, fructose, piperidine nitrogen oxide catalyst, acid, salt and oxygen source are used as raw material groups, the fructose is added into an organic solvent, then the piperidine nitrogen oxide catalyst, acid and salt are added to form a raw material mixed solution, and molecular oxygen is used as an oxidizing agent at 0-200 ℃, preferably 10-50 ℃, and most preferably 20-30 ℃ to perform oxidation reaction on the fructose for 0.1-72h, preferably 0.5-12h, and most preferably 2-5h under the action of the piperidine nitrogen oxide, acid and salt, so as to obtain the product 2, 5-furandicarboxaldehyde. The oxygen source is air or oxygen.
The ratio of the mass of the fructose to the volume of the organic solvent is 20-300g/L, preferably 50-100g/L, and most preferably 50-80 g/L; the amount of material of the piperidine nitrogen oxide catalyst is 0.1 to 100%, preferably 1 to 20%, most preferably 1 to 5% of the amount (i.e., moles) of material of the fructose; the amount of said acid material is 0.1-100%, preferably 0.5-10%, most preferably 1-5% of the amount of said fructose material, and the amount of said salt material is 0.1-100%, preferably 0.1-5%, most preferably 0.5-2% of the amount of said fructose material.
The piperidine nitrogen oxide catalyst is one or more of the following structures
The acid is at least one of sulfuric acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, hydroiodic acid, perchloric acid, periodic acid, chlorine gas, bromine, nitric acid, phosphoric acid, glacial acetic acid, and formic acid, and hydrochloric acid, hydrobromic acid, or hydroiodic acid is particularly preferably used from the viewpoint of the yield of 2, 5-DFF.
The organic solvent is one or more selected from dichloroethane, tetrachloroethane, monochloromethane, dichloromethane, trichloromethane, tetrachloromethane, ethyl acetate, toluene, dioxane, tetrahydrofuran and acetonitrile, and dichloromethane is particularly preferably used as the solvent from the viewpoint of the yield of 2, 5-DFF.
The salt is sodium nitrite or potassium nitrite.
The obtained product after oxidation reaction is reaction mixed liquid, and the product 2, 5-furan dicarbaldehyde exists in the reaction mixed liquid and can be obtained by a proper separation mode. The solid phase in the reaction mixed liquid is sodium salt or potassium salt, and the liquid phase comprises the product 2, 5-DFF, unreacted raw material fructose, acid, organic solvent and piperidine nitrogen oxide catalyst. Therefore, in one separation example of the present invention, the reaction mixture is first subjected to solid-liquid separation by filtration to remove the solid phase; evaporating and concentrating the liquid phase, removing the organic solvent to obtain a concentrated solution, and cooling and crystallizing the concentrated solution to obtain the product 2, 5-DFF. FIG. 1 shows a hydrogen nuclear magnetic spectrum of 2, 5-DFF obtained by the method of the present invention.
As can be seen from the above-mentioned preparation process, the present invention provides a method for preparing 2, 5-furandicarboxaldehyde (2, 5-DFF) from fructose in a one-step process. The method has mild reaction conditions, is a method for preparing the 2, 5-furan dicarbaldehyde with low price, environmental protection, high activity and high yield, and has wide industrial application prospect.
Examples
Example 1
This example prepares 2, 5-furandicarboxaldehyde (2, 5-DFF) as follows:
90mg of fructose (Shanghai pottery Biotech Co., Ltd., product No. T2954) (0.5 mmol in total) was dissolved in 2mL of dichloroethane, and 2ul of HCl (0.025 mmol in total, 5% based on the amount of 5-HMF substance), 7.8mg of TEMPO (0.025 mmol in total, 5% based on the amount of 5-HMF substance), and 2.13mg of NaNO were added2(0.025 mol in total, accounting for 5% of the fructose substance) to obtain a raw material group mixed solution, and stirring and reacting for 4 hours in the air at room temperature and normal pressure to obtain a reaction mixture.
The reaction mixture employs LC as the detection means and biphenyl as the internal standard.
Example 2
The specific reaction procedure and detection method were the same as in example 1 except that fructose was changed to glucose, and as a result, 2, 5-DFF was obtained in a yield of 10.6%.
Example 3
The detailed procedure and examination were carried out in the same manner as in example 1 except that methylene chloride was changed to toluene, and as a result, 2, 5-DFF was obtained in a yield of 78.7%.
Example 4
The specific reaction procedure and detection method were the same as in example 1 except that dichloromethane was changed to dioxane, and as a result, 2, 5-DFF was obtained as a product with a yield of 70.8%.
Example 5
The specific reaction procedure and detection method were the same as in example 1 except that dichloromethane was changed to acetonitrile, and as a result, 2, 5-DFF was obtained in a yield of 92.5%.
Example 6
The specific reaction procedure and detection method were the same as in example 1 except that dichloromethane was changed to dioxane, and as a result, 2, 5-DFF was obtained as a product with a yield of 70.8%.
The structures of this examples 5 and 6 illustrate that dichloromethane can achieve particularly high yields of 2, 5-DFF for the preparation process of the present invention.
Example 7
The detailed procedure and examination were carried out in the same manner as in example 1 except that dichloroethane was changed to dichloromethane, whereby 2, 5-DFF was obtained as a result, and the yield was 89.2%.
Example 8
The detailed procedure and detection were the same as in example 1 except that ethyl acetate was used instead of methylene chloride, and as a result, 2, 5-DFF was obtained in a yield of 75.3%.
Example 9
The specific reaction procedure and detection method were the same as in example 5 except that hydrochloric acid was changed to sulfuric acid, and as a result, 2, 5-DFF was obtained in a yield of 86.3%.
Example 10
The specific reaction procedure and detection method were the same as in example 5 except that hydrochloric acid was changed to hydrobromic acid, and as a result, 2, 5-DFF was obtained as a product and the yield was 98.2%.
Example 11
The specific reaction procedure and detection method were the same as in example 5 except that hydrochloric acid was changed to hydrofluoric acid, and as a result, 2, 5-DFF was obtained in a yield of 78.4%.
Example 12
The specific reaction procedure and detection method were the same as in example 5 except that hydrochloric acid was changed to hydroiodic acid, and as a result, 2, 5-DFF was obtained in a yield of 94.3%.
Example 13
The specific reaction procedure and detection method were the same as in example 5 except that hydrochloric acid was changed to nitric acid, and as a result, 2, 5-DFF was obtained in a yield of 89.5%.
Example 14
The specific reaction procedure and detection method were the same as in example 5 except that hydrochloric acid was changed to phosphoric acid, and as a result, 2, 5-DFF was obtained in a yield of 64.8%.
Example 15
The specific reaction procedure and detection method were the same as in example 5 except that hydrochloric acid was changed to glacial acetic acid, and as a result, 2, 5-DFF was obtained in a yield of 80.7%.
Example 16
The specific reaction procedure and detection method were the same as in example 5 except that hydrochloric acid was changed to formic acid, and as a result, 2, 5-DFF was obtained in a yield of 80.2%.
Example 17
The specific reaction procedure and detection method were the same as in example 10 except that TEMPO was changed to piperidine nitroxide 2, and as a result, the product obtained was 2, 5-DFF, and the yield was 94.6%.
Example 18
The specific reaction procedure and detection method were the same as in example 10 except that TEMPO was changed to piperidine nitroxide 3, and as a result, the product obtained was 2, 5-DFF, and the yield was 92.8%.
Example 19
The specific reaction procedure and detection method were the same as in example 10 except that TEMPO was changed to piperidine nitroxide 3, and as a result, the product obtained was 2, 5-DFF with a yield of 93.7%.
Example 20
The specific reaction procedure and detection method were the same as in example 10 except that TEMPO was changed to piperidine nitroxide 4, and as a result, the product obtained was 2, 5-DFF with a yield of 90.9%.
Example 21
The specific reaction procedure and detection method were the same as in example 10 except that TEMPO was changed to piperidine nitroxide 5, and as a result, the product obtained was 2, 5-DFF, and the yield was 93.5%.
Example 22
The specific reaction procedure and detection method were the same as in example 10 except that TEMPO was changed to piperidine nitroxide 6, and as a result, the product obtained was 2, 5-DFF, and the yield was 91.8%.
Example 23
The specific reaction procedure and detection method were the same as in example 10 except that TEMPO was changed to piperidine nitroxide 7, and as a result, the product obtained was 2, 5-DFF, and the yield was 93.3%.
Example 24
The specific reaction procedure and detection method were the same as in example 10 except that TEMPO was changed to piperidine nitroxide 8, and as a result, the product obtained was 2, 5-DFF with a yield of 94.6%.
Example 24
The specific reaction procedure and detection method were the same as in example 10 except that TEMPO was changed to piperidine nitroxide 9, and as a result, the product obtained was 2, 5-DFF with a yield of 94.1%.
Example 25
The specific reaction procedure and detection method were the same as in example 1 except that the reaction time was changed to 2 hours, and as a result, the product obtained was 2, 5-DFF, and the yield was 60.1%.
Example 26
The specific reaction procedure and detection method were the same as in example 1 except that the reaction time was changed to 5 hours, and as a result, the product obtained was 2, 5-DFF, and the yield was 80.3%.
Example 27
The specific reaction process and detection method were the same as in example 1 except that the reaction temperature was changed to 50 deg.C, and as a result, the product was 2, 5-DFF, and the yield was 75.4%.
Example 28
The specific reaction procedure and detection method were the same as in example 1 except that the reaction temperature was changed to 80 ℃ to obtain 2, 5-DFF as a result, and the yield was 78.9%.
Example 29
The detailed procedure and examination were carried out in the same manner as in example 1 except that the amount of TEMPO used was changed to 11.7mg, as a result, the product obtained was 2, 5-DFF, and the yield was 79.6%.
Example 30
The detailed procedure and examination were carried out in the same manner as in example 1 except that the amount of TEMPO used was changed to 15.6mg, as a result, the obtained product was 2, 5-DFF, and the yield was 82.1%.
While the invention has been described with reference to specific preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A process for preparing 2, 5-furandicarboxaldehyde, comprising the steps of:
fructose is used as a raw material, piperidine nitrogen oxide is used as a catalyst, acid and nitrite are used as a cocatalyst, and the product 2, 5-furan dicarbaldehyde is obtained by one-pot reaction in the presence of an organic solvent and an oxygen source, wherein the piperidine nitrogen oxide catalyst is selected from at least one of the following structures:
2. the production method according to claim 1, wherein the amount of the substance of the piperidine nitrogen oxide catalyst is 0.1 to 100% of the amount of the substance of fructose.
3. The production method according to claim 1, wherein the ratio of the fructose mass to the organic solvent volume is 1 to 1000 g/L.
4. The production method according to claim 1, wherein the amount of the substance of the acid is 0.1-100% of the amount of the substance of the fructose, and the amount of the substance of the nitrite is 0.1-100% of the amount of the substance of the fructose.
5. The production method according to claim 1, wherein the acid is selected from at least one of sulfuric acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, hydroiodic acid, nitric acid, phosphoric acid, glacial acetic acid, and formic acid.
6. The production method according to claim 1, wherein the organic solvent is at least one selected from the group consisting of dichloroethane, tetrachloroethane, dichloromethane, trichloromethane, tetrachloromethane, ethyl acetate, toluene, dioxane, tetrahydrofuran and acetonitrile.
7. The production method according to claim 1, wherein the nitrite is sodium nitrite or potassium nitrite.
8. The production method according to claim 1, wherein the reaction is carried out at a temperature of 0-200 ℃ for 0.1-72 hours.
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| CN106674162A (en) * | 2016-12-07 | 2017-05-17 | 合肥学院 | Preparation method of 2,5-furan diformaldehyde |
Non-Patent Citations (3)
| Title |
|---|
| Cascade catalysis via dehydration and oxidation: one-pot synthesis of 2,5-diformylfuran from fructose using acid and V2O5/ceramic catalysts;Mei Cui,et al;《RSC Adv.》;20170123;第7卷;第7560–7566页 * |
| Polymers from biomass: one pot two-step synthesis of furilydenepropanenitrile derivatives with MIL-100(Fe) catalyst;Anastasia Rapeyko，et al;《Catal. Sci. Technol》;20170530;第7卷;第3008–3016卷 * |
| The "one-pot" synthesis of 2,5-diformylfuran, a promising synthon for organic materials in the conversion of biomass;Kashparova et al.;《Russian Chemical Bulletin, International Edition》;20150531;第64卷(第5期);第1069—1073页 * |
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