CN109705067B - Preparation method of 2, 5-diformylfuran - Google Patents
Preparation method of 2, 5-diformylfuran Download PDFInfo
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Abstract
A preparation method of 2, 5-diformylfuran, relating to 2, 5-diformylfuran. Mixing reaction raw materials with a composite catalyst consisting of a main catalyst iron-based compound and a cocatalyst, an oxidant, an oxidation promoter and a reaction solvent, heating the mixture in a reactor for reaction, and cooling the mixture to room temperature to obtain a reaction solution of 2, 5-diformylfuran; cooling the reaction liquid of the 2, 5-diformylfuran to room temperature, filtering to remove the catalyst, carrying out reduced pressure distillation to recover the reaction solvent to obtain light yellow powder, dissolving the light yellow powder in dichloromethane, washing the dichloromethane solution by using a saturated sodium chloride solution, carrying out reduced pressure distillation to recover the dichloromethane to obtain light yellow powder, and drying to obtain the 2, 5-diformylfuran, wherein the obtained 2, 5-diformylfuran is light yellow. The adopted oxidant is easy to obtain, the catalyst is cheap, the dosage is less, the product yield is high, the reaction condition is mild, the product is easy to separate, and the preparation method is green and economic and has potential industrial value.
Description
Technical Field
The invention relates to 2, 5-diformylfuran, in particular to a preparation method of 2, 5-diformylfuran by using air or oxygen as an oxidant and efficiently catalyzing and oxidizing 5-hydroxymethylfurfural or 5-formyloxymethylfurfural under mild conditions in a composite catalyst system.
Background
Nowadays, with increasingly outstanding environmental problems, fossil energy is exhausted, green, environment-friendly and renewable biomass resources with abundant reserves are developed, the environment-friendly biomass resources are based on the starting point of environmental protection, the shortage of petroleum resources is replaced or supplemented, and the economic and environment-friendly energy development road of sustainable development is taken, so that the environment-friendly biomass resources are deeply concerned and valued at home and abroad. 5-hydroxymethylfurfural and 5-formyloxymethylfurfural are important platform compounds for biomass conversion and are readily prepared by dehydration of sugar compounds under acidic conditions (Acs Catalysis 5.11(2015): 150916132449005; Chemical Reviews,2013,113(3): 1499-572; Carbohyd-rate Polymers,2015,130: 420-428; Green Chemistry,2014,16(2): 548-572). The oxidized derivative of 5-hydroxymethylfurfural, namely 2, 5-diformylfuran, is one of important downstream products converted from biomass, is an important intermediate for synthesizing various fine chemical products and furan-based polymers, and has potential application value in the aspect of synthesizing fibers and polyesters. (A chem.,2014,388, 123-132; Top, Catal.,2004,27, 11-30; Greenchem.,2011,13, 754-793; ChemSuschem,2011,4, 51-54. Adv; Synth. Catal.,2001,343, 102-111.) however, due to the special molecular structure, aldehyde groups are easily oxidized into carboxyl groups, and furan rings are easily hydrolyzed to open rings to generate intermolecular polymerization. Therefore, the difficulty in oxidizing 5-hydroxymethylfurfural or 5-formyloxymethylfurfural to 2, 5-diformylfuran is high selectivity and high efficiency. Manganese dioxide, chromium trioxide and sodium hypochlorite are reported to be used as oxidants, and the methods have great environmental pollution and do not meet the requirements of modern green development; at present, molecular oxygen is used as an oxidant, so that the requirement on reaction equipment is high, the conversion efficiency is low, and industrialization is difficult to realize; therefore, the development of an oxidation route with high yield, easy product separation, low cost and low pollution has important application value in industry.
Disclosure of Invention
The invention aims to provide a preparation method of 2, 5-diformylfuran by using air or oxygen as an oxidant and efficiently catalyzing and oxidizing 5-hydroxymethylfurfural or 5-formyloxymethylfurfural under mild conditions in a composite catalyst system.
The invention comprises the following steps:
1) mixing reaction raw materials with a composite catalyst consisting of a main catalyst iron-based compound and a cocatalyst, an oxidant, an oxidation promoter and a reaction solvent, sealing in a reactor for heating reaction, and then cooling to room temperature to obtain a reaction solution of 2, 5-diformylfuran;
2) cooling the reaction liquid of the 2, 5-diformylfuran obtained in the step 1) to room temperature, filtering to remove the catalyst, and carrying out reduced pressure distillation to recover the reaction solvent to obtain light yellow powder;
3) dissolving the light yellow powder obtained in the step 2) in dichloromethane, washing the dichloromethane solution by using a saturated sodium chloride solution, carrying out reduced pressure distillation to recover dichloromethane to obtain light yellow powder, and drying to obtain 2, 5-diformylfuran, wherein the obtained 2, 5-diformylfuran is light yellow.
The reaction raw material can be at least one of 5-hydroxymethylfurfural or 5-formyloxymethylfurfural, and the mass concentration of the reaction raw material can be 0.001-1 g/m L, preferably 0.021 g/ml.
The main catalyst iron-based compound can be at least one selected from ferric nitrate, ferric oxide, ferric trichloride, ferric sulfate, ferric phosphate and the like, and the dosage of the main catalyst iron-based compound can be 0.1-40% of the mass percentage of the reaction raw materials, preferably 5%; the cocatalyst can be at least one selected from sodium nitrate, sodium nitrite, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium nitrate, potassium nitrite, potassium hydrogen phosphate, potassium dihydrogen phosphate, calcium nitrate, magnesium sulfate, magnesium phosphate, magnesium hydrogen phosphate, zinc chloride, zinc nitrate, copper chloride, copper bromide, copper oxide, copper nitrate, copper sulfate and the like, and the amount of the cocatalyst can be 0-50% of the mass percentage of the reaction raw materials. When the amount of the main catalyst or the co-catalyst is increased, the time for complete conversion of the reaction raw material is shortened, but the selectivity is decreased.
The oxidant can be at least one of air or oxygen, the dosage pressure of the oxidant can be 0.01-5 MPa, the air pressure is 0.1MPa as the best pressure, and the oxygen pressure is 0.01MPa as the best pressure; the oxidation accelerator can be at least one selected from potassium persulfate, potassium hydrogen persulfate, sodium hydrogen persulfate and the like, and the molar amount of the oxidation accelerator and the reaction raw materials can be (0.01-2): 1, and is preferably 10 mol%.
The reaction solvent may be at least one selected from acetonitrile, dioxane, acetone, butyronitrile, benzonitrile, toluene, n-hexane, ethyl acetate, dichloromethane, dichloroethane, etc., preferably acetonitrile.
The temperature of the heating reaction can be 25-110 ℃, and preferably 80 ℃; the heating reaction time can be 0.17-20 h, preferably 1.5 h.
The outstanding technical effects of the invention are as follows:
1) the method has the advantages of easily obtained oxidant, cheap catalyst, low consumption, high product yield, mild reaction conditions, easy product separation, green and economic preparation method and potential industrial value.
2) The product yield can reach 99%, the purified and separated product has high quality, and the separated product has purity over 99% through gas chromatography quantitative analysis, nuclear magnetic resonance instrument spectrum and other tests.
Drawings
FIG. 1 shows the isolation of 2, 5-diformylfuran from example 21H NMR(DMSO-d6) A nuclear magnetic resonance image;
FIG. 2 shows the isolation of 2, 5-diformylfuran from example 213C NMR (DMSO-d6) nuclear magnetic resonance image.
Detailed Description
The invention is further illustrated by the following examples and figures.
Example of 5-formyloxymethylfurfural preparation of 2, 5-diformylfuran:
example 1: 0.5mmol of 5-formyloxymethylfurfural, 5 wt% of Fe (NO)3)35 wt% of Cu (NO)3)2Adding 0.05mmol of potassium hydrogen persulfate into a stainless steel homogeneous phase tank of the polyfluortetraethylene endosulfan, adding 5ml of acetonitrile, and then carrying out temperature programming to 80 ℃ and keeping for 3 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 99 percent, and the selectivity is more than 99 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on the organic layer under reduced pressure to obtain a yellowish solid, and performing freeze drying to obtain a yellowish powdered solid.
Example 2: magnification experiment 10 times: 5mmol of 5-formyloxymethylfurfural and 5 wt% of Fe (NO)3)3、5wt％Cu(NO3)2Adding 0.5mmol of potassium hydrogen persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 50ml of acetonitrile, and then carrying out temperature programming to 80 ℃ and keeping for 3 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 98 percent, and the selectivity is more than 97 percent; centrifugally removing solid salt, recovering solvent, rotary evaporating, and addingMixing with sodium chloride solution and dichloromethane, shaking, separating, evaporating organic layer to obtain yellowish solid, and freeze drying to obtain yellowish powdered solid.
EXAMPLE 2 isolation of the product 2, 5-Dimethylofuran1H NMR(DMSO-d6) NMR chart referring to FIG. 1, example 2 isolated product 2, 5-diformylfuran13The C NMR (DMSO-d6) NMR chart is shown in FIG. 2.
Example 3: 0.5mmol of 5-formyloxymethylfurfural, 10 wt% of Fe (NO)3)3Adding 0.05mmol of sodium hydrogen persulfate into a stainless steel homogeneous tank of polyfluortetraethylene endosulfan, adding 5ml of dioxane, and then carrying out temperature programming to 80 ℃ and keeping for 3.5 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 46.8 percent, and the selectivity is more than 96 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 4: 0.5mmol of 5-formyloxymethylfurfural, 10 wt% of Fe (NO)3)310 wt% of CuSO4Adding 0.05mmol of potassium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of acetonitrile, and then programming to 90 ℃ and keeping for 9 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 99 percent, and the selectivity is more than 73 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 5: 0.5mmol of 5-formyloxymethylfurfural and 20 wt% of FeCl320 wt% Cu (NO)3)2Adding 1mmol of potassium hydrogen persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of acetonitrile, and then programming to 90 ℃ and keeping for 5 hours;after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 99 percent, and the selectivity is more than 49 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 6: 0.5mmol of 5-formyloxymethylfurfural and 10 wt% of FeCl 310 wt% of NaNO3Adding 0.05mmol of potassium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of acetonitrile, and then programming to 100 ℃ and keeping for 10 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 99 percent, and the selectivity is more than 37 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 7: 0.5mmol of 5-formyloxymethylfurfural and 10 wt% of Fe2O310 wt% of CuCl2Adding 0.5mmol of potassium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of acetonitrile, and then programming to 50 ℃ and keeping for 6 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 88 percent, and the selectivity is more than 97 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 8: 0.5mmol of 5-formyloxymethylfurfural, 10 wt% of Fe (NO)3)310 wt% Mg (NO)3)2Adding 0.5mmol sodium persulfate into stainless steel homogeneous tank of polyfluortetraethylene endosulfan, adding 5ml butyronitrile, heating to 90 deg.C, and maintaining11 h; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 91 percent, and the selectivity is more than 54 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 9: 0.5mmol of 5-formyloxymethylfurfural, 5 wt% of Fe (NO)3)35 wt% of CuSO4Adding 0.5mmol of sodium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of acetonitrile, and then programming to 70 ℃ and keeping for 2 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 79 percent, and the selectivity is more than 97 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 10: 0.5mmol of 5-formyloxymethylfurfural, 15 wt% of Fe (NO)3)215 wt% of CuBr2Adding 0.5mmol of potassium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of acetonitrile, and then programming to 70 ℃ and keeping for 2 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 99 percent, and the selectivity is more than 33 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 11: 0.5mmol of 5-formyloxymethylfurfural, 10 wt% of Fe (NO)3)310 wt% Ca (NO)3)2And 0.5mmol of sodium hydrogen persulfate were charged into a stainless steel homogeneous pot of polyfluortetraethylene endosulfan, 5ml of benzonitrile was further added, and then the procedure was followedHeating to 100 ℃, and keeping for 3 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 97 percent, and the selectivity is more than 53 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 12: 0.5mmol of 5-formyloxymethylfurfural, 10 wt% of Fe (NO)3)310 wt% of Na2HPO4Adding 0.5mmol of potassium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of dichloroethane, and then raising the temperature to 30 ℃ by program and keeping the temperature for 9 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 79 percent, and the selectivity is more than 83 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 13: 0.5mmol of 5-formyloxymethylfurfural, 10 wt% of Fe (NO)3)310 wt% ZnCl2Adding 0.25mmol of potassium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of toluene, and then programming to 110 ℃ and keeping for 1 h; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 94 percent, and the selectivity is more than 40 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 14: 0.5mmol of 5-formyloxymethylfurfural, 10 wt% of Fe (NO)3)310 wt% of CuSO4Adding 0.5mmol potassium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, and adding5ml of acetonitrile is added, then the temperature is programmed to 70 ℃, and the temperature is kept for 2 h; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 50 percent, and the selectivity is more than 93 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 15: 0.5mmol of 5-formyloxymethylfurfural, 10 wt% of Fe (NO)3)3Adding 10 wt% of CuO and 0.5mmol of potassium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of acetonitrile, and then carrying out temperature programming to 80 ℃ and keeping for 9 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 93 percent, and the selectivity is more than 86 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 16: 0.5mmol of 5-formyloxymethylfurfural, 10 wt% of Fe (NO)3)3Adding 0.5mmol of potassium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of acetonitrile, and then programming to 90 ℃ and keeping for 4 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 99 percent, and the selectivity is more than 43 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 17: 0.5mmol of 5-formyloxymethylfurfural and 10 wt% of CuSO4Adding 0.05mmol of potassium hydrogen persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of dioxane, and then carrying out temperature programming to 90 ℃ and keeping for 5 hours; reaction ofAfter the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 19 percent, and the selectivity is more than 59 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 18: 0.5mmol of 5-formyloxymethylfurfural and 10 wt% of Fe2(SO4)3Adding 0.05mmol of potassium hydrogen persulfate into a stainless steel homogeneous phase tank of the polyfluortetraethylene endosulfan, adding 5ml of acetonitrile, and then carrying out temperature programming to 90 ℃ and keeping for 4 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 14.42 percent, and the selectivity is more than 99 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example of 5-hydroxymethylfurfural production of 2, 5-diformylfuran:
example 19: mixing 0.5mmol of 5-hydroxymethylfurfural and 5 wt% of Fe (NO)3)35 wt% of Cu (NO)3)2Adding 0.5mmol of potassium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of acetonitrile, and then programming to 90 ℃ and keeping for 3 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 99 percent, and the selectivity is more than 99 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on the organic layer under reduced pressure to obtain a yellowish solid, and performing freeze drying to obtain a yellowish powdered solid.
Example 20: 0.5mmol of 5-hydroxymethylfurfural and 10 wt% of Fe (NO)3)3And 0.05mmol of potassium hydrogen persulfate are added into a stainless steel homogeneous phase tank of the polyfluortetraethylene endosulfan, and then the potassium hydrogen persulfate is added5ml of dioxane, then the temperature is programmed to 70 ℃, and the temperature is kept for 3.5 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 30.4 percent, and the selectivity is more than 97 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 21: 0.5mmol of 5-hydroxymethylfurfural and 10 wt% of Fe (NO)3)310 wt% of CuSO4Adding 0.5mmol of potassium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of acetonitrile, and then programming to 30 ℃ and keeping for 9 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 49 percent, and the selectivity is more than 83 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 22: 0.5mmol of 5-hydroxymethylfurfural and 10 wt% of Fe (NO)3)310 wt% Cu (NO)3)2Adding 0.5mmol of potassium persulfate into a 20ml reaction kettle, adding 5ml of acetonitrile, finally filling 1MPa of oxygen, then carrying out temperature programming to 80 ℃, and keeping for 3 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 31.54 percent, and the selectivity is more than 22 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 23: 0.5mmol of 5-hydroxymethylfurfural and 10wt percent of FeCl 310 wt% of NaNO3And 0.5mmol of potassium persulfate were added to a stainless steel homogeneous tank containing polyfluortetraethylene endosulfan, and 5ml of the mixture was addedAcetonitrile, then temperature programming to 100 ℃, and keeping for 10 h; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 99 percent, and the selectivity is more than 37 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 24: 0.5mmol of 5-hydroxymethylfurfural and 10 wt% of Fe2O310 wt% of CuCl2Adding 0.5mmol of potassium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of acetonitrile, and then programming to 50 ℃ and keeping for 6 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 68 percent, and the selectivity is more than 67 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 25: 0.5mmol of 5-hydroxymethylfurfural and 10 wt% of Fe (NO)3)310 wt% Mg (NO)3)2Adding 0.5mmol of sodium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of butyronitrile, and then carrying out temperature programming to 90 ℃ and keeping for 11 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 81 percent, and the selectivity is more than 64 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 26: 0.5mmol of 5-hydroxymethylfurfural and 10 wt% of Fe (NO)3)310 wt% of Na2HPO4Adding 0.5mmol potassium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, and addingAdding 5ml of dichloroethane, then raising the temperature to 30 ℃ by program, and keeping the temperature for 9 hours; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 79 percent, and the selectivity is more than 83 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 27: 0.5mmol of 5-hydroxymethylfurfural and 10 wt% of Fe (NO)3)310 wt% ZnCl2Adding 0.5mmol of potassium persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of toluene, and then programming to 110 ℃ and keeping for 1 h; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 89%, and the selectivity is more than 36%; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Example 28: 0.5mmol of 5-hydroxymethylfurfural and 10 wt% of Fe (NO)3)310 wt% of CuSO4Adding 0.5mmol of sodium hydrogen persulfate into a stainless steel homogeneous phase tank of polyfluortetraethylene endosulfan, adding 5ml of acetonitrile, and then carrying out temperature programming to 70 ℃ and keeping for 2 h; after the reaction is finished, quickly cooling the mixture in the reaction system to room temperature, sampling and carrying out gas chromatography quantitative analysis, wherein the conversion rate of the raw material is more than 43 percent, and the selectivity is more than 68 percent; centrifuging to remove solid salt, recycling, performing rotary evaporation to recover the solvent, adding saturated sodium chloride solution and dichloromethane, sufficiently shaking, separating liquid, performing rotary evaporation on an organic layer to obtain a light yellow solid, and performing freeze drying to obtain a light yellow powdery solid.
Claims (7)
1. A preparation method of 2, 5-diformylfuran is characterized by comprising the following steps:
1) mixing reaction raw materials with a composite catalyst consisting of a main catalyst iron-based compound and a cocatalyst, an oxidant, an oxidation promoter and a reaction solvent, sealing in a reactor for heating reaction, and then cooling to room temperature to obtain a reaction solution of 2, 5-diformylfuran; the main catalyst iron-based compound is selected from at least one of ferric nitrate, ferric oxide, ferric trichloride, ferric sulfate and ferric phosphate, and the dosage of the main catalyst iron-based compound is 0.1-40% of the mass percentage of the reaction raw materials; the cocatalyst is selected from at least one of sodium nitrate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium nitrate, potassium hydrogen phosphate, potassium dihydrogen phosphate, calcium nitrate, magnesium sulfate, magnesium phosphate, magnesium hydrogen phosphate, zinc chloride, zinc nitrate, copper chloride, copper bromide, copper oxide, copper nitrate and copper sulfate, and the amount of the cocatalyst is 0-50% of the mass percentage of the reaction raw materials; the oxidant is selected from at least one of air or oxygen, and the dosage pressure of the oxidant is 0.01-5 MPa; the oxidation accelerator is at least one of potassium persulfate, potassium hydrogen persulfate, sodium persulfate and sodium hydrogen persulfate, and the molar amount of the oxidation accelerator and the reaction raw materials is (0.01-2): 1;
the reaction raw material is at least one of 5-hydroxymethylfurfural or 5-formyloxymethylfurfural, and the mass concentration of the reaction raw material is 0.001-1 g/m L;
the reaction solvent is at least one selected from acetonitrile, dioxane, acetone, butyronitrile, benzonitrile, toluene, n-hexane, ethyl acetate, dichloromethane and dichloroethane;
2) cooling the reaction liquid of the 2, 5-diformylfuran obtained in the step 1) to room temperature, filtering to remove the catalyst, and carrying out reduced pressure distillation to recover the reaction solvent to obtain light yellow powder;
3) dissolving the light yellow powder obtained in the step 2) in dichloromethane, washing the dichloromethane solution by using a saturated sodium chloride solution, carrying out reduced pressure distillation to recover dichloromethane to obtain light yellow powder, and drying to obtain 2, 5-diformylfuran;
2. the process according to claim 1, wherein the reaction raw material has a mass concentration of 0.021 g/ml.
3. The method according to claim 1, wherein the amount of the iron-based compound as the main catalyst is 5% by mass of the reaction raw materials.
4. The process for producing 2, 5-diformylfuran according to claim 1, wherein the molar amount of the oxidation promoter to the reaction raw material is 10 mol%.
5. The process according to claim 1, wherein the reaction solvent is acetonitrile.
6. The method according to claim 1, wherein the heating reaction is carried out at a temperature of 25 to 110 ℃; the heating reaction time is 0.17-20 h.
7. The process for producing 2, 5-diformylfuran according to claim 6, wherein the temperature of the heating reaction is 80 ℃; the heating time for the reaction was 1.5 h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101987839A (en) * | 2009-07-31 | 2011-03-23 | 中国科学院大连化学物理研究所 | Method for preparing 2,5-diformylfuran by oxidizing 5-hydroxymethylfurfural |
| CN104478835A (en) * | 2014-12-26 | 2015-04-01 | 合肥利夫生物科技有限公司 | Method for preparing 2,5-diformylfuran |
| CN108863998A (en) * | 2018-06-22 | 2018-11-23 | 厦门大学 | A kind of method that manganese bimetallic catalyst oxidation 5 hydroxymethyl furfural prepares 2,5- diformyl furans |
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| WO2008054804A2 (en) * | 2006-10-31 | 2008-05-08 | Battelle Memorial Institute | Hydroxymethyl furfural oxidation methods |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101987839A (en) * | 2009-07-31 | 2011-03-23 | 中国科学院大连化学物理研究所 | Method for preparing 2,5-diformylfuran by oxidizing 5-hydroxymethylfurfural |
| CN104478835A (en) * | 2014-12-26 | 2015-04-01 | 合肥利夫生物科技有限公司 | Method for preparing 2,5-diformylfuran |
| CN108863998A (en) * | 2018-06-22 | 2018-11-23 | 厦门大学 | A kind of method that manganese bimetallic catalyst oxidation 5 hydroxymethyl furfural prepares 2,5- diformyl furans |
Non-Patent Citations (1)
| Title |
|---|
| Selective oxidation of 5-hydroxymethyl furfural over non-precious metal heterogeneous catalysts;Florentina Neatu et al.;《Applied Catalysis B: Environmental》;20150728;第180卷;第751-757页 * |
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