CN110590719B - Green method for preparing 2-furoic acid - Google Patents
Green method for preparing 2-furoic acid Download PDFInfo
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Abstract
The invention relates to a green method for preparing 2-furanone acid, which is characterized by comprising the following steps: 1. preparing 5-60% of dilute sulfuric acid and 10-70% of sodium nitrite solution; 2. adding the recycled low-salt water, the catalyst and the 2-acetylfuran into a reaction kettle, stirring and heating to 20-90 ℃, adding dilute sulfuric acid, then dripping a sodium nitrite solution, and preserving heat for 0.1-24 hours; 3. cooling and extracting for 2-5 times by using ethyl acetate; 4. adjusting the pH of the water phase to 0.8-1.2, extracting with ethyl acetate for 2-20 times, combining the organic phases, distilling under reduced pressure, adding dichloromethane, crystallizing at-40-0 ℃ for 4-72 hours, and filtering to obtain 2-ketofuranone acid; 5. adjusting the pH value of the water phase to be neutral, crystallizing for 1-72 h at the temperature of-20 ℃, filtering to obtain water-containing sodium sulfate, and treating clear liquid by a negative pressure concentrator to obtain recycled water and recycled low-salinity water. The invention has the advantages that: the process is simple and easy to implement; the reaction is stable and efficient, the side reaction is less, and the industrial amplification production is easy to realize; the low-salt wastewater can be recycled, and basically no wastewater is discharged.
Description
Technical Field
The invention belongs to the field of preparation of organic synthesis intermediates and fine chemical intermediates, relates to the field of preparation of 2-ketofuranone acid by taking 2-acetylfuran as a raw material through oximation, rearrangement and hydrolysis, and particularly relates to a green method for preparing the 2-ketofuranone acid.
Background
Cefuroxime belongs to the second generation product in cephalosporin antibiotics, and is characterized by wide antibacterial spectrum, lower nephrotoxicity, strong permeability, higher stability to beta-lactamase, definite curative effect in clinical treatment and convenient use, thereby being widely used for various infectious diseases caused by anti-sensitive bacteria. Therefore, the market demand for cefuroxime and its upstream raw material drug and intermediate is greatly increased, and the research on synthesizing 2-furanone acid as an intermediate for synthesizing cefuroxime side chains is receiving more and more attention.
The main synthetic route of the 2-furanone acid comprises (1) taking 2-furanone acetic acid as a raw material, and preparing the 2-furanone acid by chlorination, cyanation and hydrolysis; (2) oximation, rearrangement and hydrolysis of 2-acetylfuran are carried out to synthesize 2-furanone ketonic acid; (3) under the action of a phase transfer catalyst, 2-acetylfuran and benzaldehyde are subjected to aldol condensation to prepare 1- (2-furyl) -3-phenylacetone, and then oxidized to prepare 2-furanone acid; (4) furan is used as an initial raw material, and is subjected to Friedel-crafts acylation reaction with oxalyl chloride or oxalyl chloride ester to obtain 2-furanone acyl chloride or 2-furanone ketoester, and the 2-furanone ketoacid is hydrolyzed to obtain 2-furanone acid; (5) taking furfural as a starting material, and carrying out cyanidation and oxidation to obtain 2-furanone ketonic acid; (6) furfural and chloroform are used as starting materials, 2-furanhydroxyacetic acid is obtained through haloform reaction and hydrolysis reaction, and 2-furanketonic acid is obtained through reoxidation.
In comparison, the method (2) has the advantages of guaranteed raw material supply, low process conditions, proper total yield (50-70%), suitability for industrial production and the like, and is adopted by most domestic manufacturers. However, the process still has the common difficulty of reaction control in the actual production; the generation of NO and NOx is accompanied, so that the hidden danger of environmental pollution is great; the yield is not too high; the pollution of three wastes (mainly saline wastewater) is serious, and the like.
Disclosure of Invention
The invention aims to solve the problems of excessive acidity of reaction liquid, violent reaction of sodium nitrite and acid, more side reactions, large material consumption, unstable reaction, large production process danger, high salt content of reaction wastewater, serious excessive COD (chemical oxygen demand) and the like in the conventional process of synthesizing 2-ketofuranone by oximation, rearrangement and hydrolysis of 2-acetylfuran.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a green method for preparing 2-ketofuranonic acid is characterized by comprising the following steps:
(1) preparing dilute sulfuric acid with the concentration of 5-60% by using deionized water or recycled water, and preparing a sodium nitrite solution with the concentration of 10-70% by using deionized water or recycled low-salt water;
(2) respectively adding deionized water or recycled low-salt water, a catalyst and 2-acetylfuran into a reaction kettle, stirring and heating to 20-90 ℃, firstly dripping dilute sulfuric acid, later dripping a sodium nitrite solution, controlling the dripping speed of the two materials to be consistent, and then carrying out heat preservation for 0.1-24 hours, wherein the deionized water or the recycled low-salt water: catalyst: 2-acetylfuran: dilute sulfuric acid: the mass ratio of the sodium nitrite solution is 100-2000: 0.01-20: 100: 10-2000: 10 to 3000;
(3) and (3) cooling to room temperature after the reaction is finished, extracting the reaction solution (with the pH value of 3-6) for 2-5 times by using ethyl acetate (removing unreacted raw materials and impurities), and controlling the mass ratio of the reaction solution to the ethyl acetate to be 1: 0.1-10, obtaining a water phase (containing 2-furanone sodium acetate) and an organic phase (containing unreacted raw materials and impurities), wherein the organic phase is subjected to reduced pressure distillation to recover unreacted 2-acetylfuran, and the solvent is recovered or reused;
(4) adjusting the pH of the water phase to 0.8-1.2 by using dilute sulfuric acid with the concentration of 5-60%, extracting for 2-20 times by using ethyl acetate, and controlling the mass ratio of the water phase to the ethyl acetate to be 1: 0.1-10, combining organic phases (ethyl acetate phase containing 2-furanonic acid) and distilling under reduced pressure (10-600 min, 0.05-0.099 MPa), adding dichloromethane into the distilled concentrated solution, and controlling the mass ratio of the concentrated solution to the dichloromethane to be 1: crystallizing for 4-72 hours at the temperature of minus 40-0 ℃ for 0.1-5 ℃, and then performing suction filtration to obtain 2-furanone acid with the purity of 95-99%;
(5) adjusting the pH of the extracted water phase to be neutral by using a sodium hydroxide solution with the concentration of 1-40%, putting the water phase into a cooling tank for crystallization and precipitation, controlling the temperature to be-20 ℃ and the time to be 1-72 hours, filtering the water phase after crystallization and precipitation to obtain a reaction byproduct, namely aqueous sodium sulfate, wherein the clear liquid is low-salt water (the salt content is 0.1-20%), and the low-salt water is treated by a negative pressure concentrator (the pressure is-0.05-0.10 MPa) to obtain recycled water and recycled low-salt water (the salt content is 0.2-30%).
(6) The reuse water is used for preparing dilute sulfuric acid in the step (1), the reuse low-salt water is used for preparing sodium nitrite solution in the step (1) and feeding in the step (2), the insufficient part is supplemented by deionized water, and the supplement amount is not higher than 20% of the whole water consumption.
Furthermore, the concentration of the dilute sulfuric acid in the step (1) is preferably 15-40%, and the concentration of the sodium nitrite solution is preferably 25-50%.
Further, the catalyst in the step (2) is any one or more of copper sulfate, copper chloride, copper nitrate, tetrabutylammonium bromide, tetrabutylammonium chloride, sodium dodecylbenzene sulfonate, dodecyltrimethylammonium bromide and dodecyltrimethylammonium chloride.
Further, the step (2) recycles low-salt water: catalyst: 2-acetylfuran: dilute sulfuric acid: the mass ratio of the sodium nitrite solution is preferably 200-800: 0.5-6: 100: 100-800: 200 to 1000.
Further, the heating temperature in the step (2) is preferably 40-70 ℃, and the heat preservation time is preferably 0.4-4 h.
Further, the salt content of the low-salt water obtained in the step (5) is 0.5-10%, and the salt content of the recycled low-salt water is 1-15%.
Through the analysis of the prior art (2-furan glyoxylic acid is synthesized by oximation, rearrangement and hydrolysis of 2-acetylfuran): the pre-adding of acid in the reaction process of the prior art can cause the reaction system to have large acidity, the dropwise added sodium nitrite solution and acid preferentially have acid-base reaction, so that the consumption of sodium nitrite and acid is increased, and simultaneously, a large amount of NO and NOx are overflowed to pollute the environment; the excessive acidity of the system can cause unstable structures of raw materials of the acetylfuran and products, and side reactions occur to influence the yield; because the temperature rises suddenly and the materials are mixed together due to violent reaction when the sodium nitrite solution is dripped too fast, the production cannot be carried out stably, the production safety is seriously influenced, and the residual wastewater after the reaction generally contains sodium chloride, sodium nitrite, sodium nitrate, sodium sulfate or sodium phosphate (if sulfuric acid or phosphoric acid is added or used in a system) and a large amount of acetylfuran ring-opening or polymerization byproducts, so that the wastewater has high salt content (about 30 percent), the COD (chemical oxygen demand) is seriously exceeded, and the treatment is difficult. The method controls the acidity of the system and the reaction progress by adopting a method of simultaneously and continuously dropwise adding dilute sulfuric acid and sodium nitrite, collects reaction products by an ethyl acetate extraction method, recovers reaction by-product sodium sulfate from reaction wastewater by a freezing crystallization method, and completely recycles low-salt water after recovering the sodium sulfate after simple concentration, thereby realizing basically no wastewater discharge.
The invention has the advantages that: 1. the method has simple and easy process, stable and efficient reaction, less side reaction and easy industrial amplification production; 2. the problems of overlarge acidity of reaction liquid, violent reaction of sodium nitrite and acid and high danger in the production process are solved; 3. unreacted raw materials in the reaction stock solution are extracted by ethyl acetate, so that the utilization rate of the raw materials is improved; 4. the ethyl acetate is adopted for extracting and adjusting the acid, and then the reaction stock solution is used for collecting the product, so that the efficiency is better than that of other chlorinated hydrocarbon solvents, and the yield is improved; 5. sodium sulfate is separated from reaction waste liquid by a freezing crystallization precipitation method, and the obtained low-salt waste water can be recycled, so that the green production without waste liquid is basically achieved.
Drawings
FIG. 1 is a simplified diagram of a green process for the preparation of 2-ketofuranonic acid.
Detailed Description
The invention is further explained by combining fig. 1, and the green synthesis method of 2-furanone acid comprises the following specific implementation steps:
example 1
(1) Slowly adding 80mL of deionized water into 40 g of concentrated sulfuric acid to prepare a dilute sulfuric acid solution, weighing 80g of sodium nitrite, and adding 120mL of deionized water to prepare a sodium nitrite solution;
(2) adding 100mL of deionized water, 25g of acetylfuran, 0.5g of copper sulfate and 0.5g of tetrabutylammonium chloride into a 500mL reaction bottle (three-mouth bottle) provided with a stirring device, a thermometer and a double constant pressure dropping funnel, starting stirring, heating to 60 ℃, firstly dropwise adding 10mL of the dilute sulfuric acid solution prepared in the step 1), synchronously dropwise adding 160mL of the sodium nitrite solution prepared in the step 1) after 10 minutes, controlling the dropwise adding speed, finishing the dropwise adding of the two solutions simultaneously (4 hours), and carrying out heat preservation reaction at 55-65 ℃ for 1 hour;
(3) after the reaction is finished, cooling to 30 ℃, and extracting the reaction solution (with the pH value of 3.0-7.0) for 2 times by using ethyl acetate (50 mL) to obtain a water phase (2-furanone sodium acetate) and an ethyl acetate phase (unreacted raw materials and impurities);
(4) distilling the ethyl acetate phase under reduced pressure (30 min, pressure-0.095 MPa) to recover 2g of unreacted 2-acetylfuran; adjusting the pH value of the water phase to 1 by using a 30% dilute sulfuric acid solution, extracting for 4 times by using ethyl acetate (50 mL), combining organic phases (ethyl acetate phase), adding 10 g of anhydrous sodium sulfate into the organic phases, drying, concentrating to obtain a 2-ketofuranonic acid crude product, adding dichloromethane which is 2 times of the mass of the 2-ketofuranonic acid crude product into the 2-ketofuranonic acid crude product, and recrystallizing to obtain 25g of 2-ketofuranonic acid with the yield of 78%;
(5) and (4) adjusting the pH value of the residual water phase extracted in the step (4) to 6-7 by using a 20% sodium hydroxide solution to obtain 430 g of solution, then placing the solution in a refrigerator for 24 hours at-10 ℃, separating out a large amount of white crystals, performing suction filtration at low temperature (-10 ℃) to obtain 120 g of solid sodium sulfate and 310 g of low-salt water with the salt content of 3%, and continuously performing reduced pressure distillation on the low-salt water for 60 minutes (the pressure is-0.095 MPa) to obtain 80g of reuse water and about 200g of reuse low-salt water, wherein the salt content of the reuse low-salt water is 5%.
Example 2
As in example 1, using 1g of cupric chloride instead of copper sulfate and tetrabutylammonium chloride, 23g of 2-furanone acid was obtained with a yield of 72% under the same conditions.
Example 3
In the same manner as in example 1, 25g of 2-furanone acid was obtained in 78% yield under the same conditions except that dodecyltrimethylammonium chloride was used instead of tetrabutylammonium chloride.
Example 4
The same as the example 1, except that the recovered water is used for preparing dilute sulphuric acid, the recovered low-salt water is used for preparing sodium nitrite and reacting, and other conditions are the same, 26g of 2-furanone acid is obtained, and the yield is 82%; crystallizing to obtain 130 g of solid sodium sulfate and 320 g of low-salt water, wherein the salt content of the low-salt water is 4 percent, and the low-salt water is subjected to reduced pressure distillation (60 min, the pressure is-0.095 MPa) to recover 80g of reuse water and about 305g of reuse low-salt water, and the salt content of the reuse low-salt water is 6 percent.
Example 5
The same as the embodiment 2, except that the water recovered in the embodiment 4 is used for preparing dilute sulfuric acid, the low-salt water recovered is used for preparing sodium nitrite and reacting, and other conditions are the same, 25-27 g of 2-furanone acid is obtained, and the yield is 78-86%; crystallizing to obtain 125-135 g of solid sodium sulfate and 300-330 g of low-salt water with salt content of 3-5%, and performing reduced pressure distillation to recover 80g of reuse water and 290-320 g of reuse low-salt water with salt content of 4-7%.
Claims (4)
1. A green method for preparing 2-ketofuranonic acid is characterized by comprising the following steps:
(1) preparing dilute sulfuric acid with the concentration of 5-60% by using deionized water or recycled water, and preparing a sodium nitrite solution with the concentration of 10-70% by using deionized water or recycled low-salt water;
(2) respectively adding deionized water or recycled low-salt water, a catalyst and 2-acetylfuran into a reaction kettle, stirring and heating to 20-90 ℃, firstly dripping dilute sulfuric acid, later dripping a sodium nitrite solution, controlling the dripping speed of the two materials to be consistent, and then carrying out heat preservation for 0.1-24 hours, wherein the deionized water or the recycled low-salt water: catalyst: 2-acetylfuran: dilute sulfuric acid: the mass ratio of the sodium nitrite solution is 100-2000: 0.01-20: 100: 10-2000: 10 to 3000; wherein the catalyst is any one or more of copper sulfate, copper chloride, copper nitrate, tetrabutylammonium bromide, tetrabutylammonium chloride, sodium dodecyl benzene sulfonate, dodecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium chloride;
(3) and cooling to room temperature after the reaction is finished, extracting the reaction liquid for 2-5 times by using ethyl acetate, and controlling the mass ratio of the reaction liquid to the ethyl acetate to be 1: 0.1-10, obtaining a water phase and an organic phase, wherein the organic phase is subjected to reduced pressure distillation to recover unreacted 2-acetylfuran, and the solvent is recovered or reused;
(4) adjusting the pH value of the water phase to 0.8-1.2 by using dilute sulfuric acid with the concentration of 5-60%, extracting for 2-20 times by using ethyl acetate, and controlling the mass ratio of the water phase to the ethyl acetate to be 1: 0.1-10, combining organic phases, then carrying out reduced pressure distillation, adding dichloromethane into a concentrated solution after distillation, and controlling the mass ratio of the concentrated solution to the dichloromethane to be 1: crystallizing for 4-72 hours at the temperature of minus 40-0 ℃ for 0.1-5 ℃, and then performing suction filtration to obtain 2-furanone acid with the purity of 95-99%;
(5) adjusting the pH value of the extracted water phase to be neutral by using a sodium hydroxide solution with the concentration of 1-40%, putting the water phase into a cooling tank for crystallization and precipitation, controlling the temperature to be-20 ℃, and the time to be 1-72 hours, filtering the water phase after crystallization and precipitation to obtain a reaction byproduct aqueous sodium sulfate, wherein the clear liquid is low-salt water, the salt content of the low-salt water is 0.5-10%, the low-salt water is treated by a negative pressure concentrator to obtain recycled water and recycled low-salt water, and the salt content of the recycled low-salt water is 1-15%;
(6) the reuse water is used for preparing dilute sulfuric acid in the step (1), the reuse low-salt water is used for preparing sodium nitrite solution in the step (1) and feeding in the step (2), the insufficient part is supplemented by deionized water, and the supplement amount is not higher than 20% of the whole water consumption.
2. The green process for the preparation of 2-ketofuranoate acid as defined in claim 1, wherein: in the step (1), the concentration of the dilute sulfuric acid is 15% -40%, and the concentration of the sodium nitrite solution is 25% -50%.
3. The green process for the preparation of 2-ketofuranoate acid as defined in claim 1, wherein: recycling low-salt water in the step (2): catalyst: 2-acetylfuran: dilute sulfuric acid: the mass ratio of the sodium nitrite solution is 200-800: 0.5-6: 100: 100-800: 200 to 1000.
4. The green process for the preparation of 2-ketofuranoate acid as defined in claim 1, wherein: and (3) heating in the step (2) at 40-70 ℃ and keeping the temperature for 0.4-4 h.
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| CN112979590A (en) * | 2021-03-01 | 2021-06-18 | 安徽金轩科技有限公司 | Novel process for preparing 2-acetylfuran by using furan |
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