CN110746385B - Method for preparing 2,5-dimethoxy-2,5-dihydrofuran by photocatalytic biomass furan - Google Patents
Method for preparing 2,5-dimethoxy-2,5-dihydrofuran by photocatalytic biomass furan Download PDFInfo
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- CN110746385B CN110746385B CN201911239487.8A CN201911239487A CN110746385B CN 110746385 B CN110746385 B CN 110746385B CN 201911239487 A CN201911239487 A CN 201911239487A CN 110746385 B CN110746385 B CN 110746385B
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Abstract
The invention discloses a method for preparing 2,5-dimethoxy-2,5-dihydrofuran by photocatalysis of biomass furan. The existing traditional synthesis methods comprise two methods, one is a chemical synthesis method, and is realized by the halogenation reaction of furan and elemental bromine, and the method has high production cost in the reaction process, has serious environmental pollution and is gradually eliminated; the other method is an electrolytic method, and the furan is prepared by electrolytic oxidation in a methanol solution, and the method also has the defects of high production cost, complex electrolyte treatment and the like. The invention takes biomass furan and methanol as raw materials, and synthesizes 2,5-dimethoxy-2,5-dihydrofuran under the irradiation of visible light and in the air atmosphere of room temperature and normal pressure through the action of a photocatalyst. The method disclosed by the invention is simple to operate, greatly reduces the production cost, avoids environmental pollution, and is a high-efficiency and environment-friendly synthesis method with industrial development value.
Description
Technical Field
The invention relates to the field of organic chemical synthesis, in particular to a method for preparing 2,5-dimethoxy-2,5-dihydrofuran by photocatalysis of biomass furan.
Background
2,5-Dimethoxy-2,5-dihydrofuran (2,5-dimetoxy-2,5-dihydrofuran, DHF) is a C4 synthetic block which is very useful in organic synthesis reaction, is an intermediate for synthesizing anticholine drug atropine sulfate and anisodamine hydrobromide, and is hydrolyzed by hydrochloric acid to generate 2-hydroxy-1,4-succinaldehyde; hydrogenation and hydrolysis to obtain succinaldehyde.
At present, the synthesis of 2,5-dimethoxy-2,5-dihydrofuran has two common methods, namely chemical synthesis and electrolysis. (1) chemical synthesis: the method is realized by the halogenation reaction of furan and elemental bromine, and 1.6kg of elemental bromine is consumed for producing 1kg of products. The method needs to be carried out at low temperature, reaction equipment needs to be corrosion-resistant, the consumption of bromine is high, the used liquid bromine is very easy to volatilize to form toxic and corrosive gas, a large amount of three wastes are generated in the whole reaction process, the production cost is high, the environmental pollution is serious, and the method is not adopted at present. (2) electrolytic method: the method is realized by using furan indirect oxidation, using methanol as electrolyte and halide as supporting electrolyte to directly generate a product on an anode, and is a main method for synthesizing 2,5-dimethoxy-2,5-dihydrofuran at present. Although the electrolytic method reduces the consumption of bromine and the discharge of three wastes, the electrolytic method still has the defects of electrolyte waste, complex electrolyte post-treatment, low production efficiency of the traditional electrochemical reactor caused by low electrolyte conductivity, need of developing a special reactor and the like.
Chinese patent application with the application number of 201610774331.X and the application date of 2016, 8, 31 discloses a method for preparing 2,5-dimethoxy-2,5-dihydrofuran, which has the technical scheme that methanol and furan are used as raw materials, chlorine replaces bromine under the condition of adding a catalyst, sodium methoxide is added as alkali to neutralize acid generated by reaction, and the reaction temperature is kept between 25 and 50 ℃; the catalyst is one or more of sodium bromide, zinc bromide and potassium bromide. Although the by-product is sodium chloride, the technical scheme is simple in treatment, but still has the following major defects: (1) Chlorine gas is a toxic and harmful gas, and the risk of escaping or leaking can exist in the experimental process; (2) Because chlorine gas is introduced to generate acid, in order to avoid the influence of acidity on the reaction in the reaction process, sodium methoxide solution is used as an acid-binding agent, so that the production cost is increased; (3) The amount of chlorine as gas is not easy to control, a sealing device is needed, the whole reaction temperature needs to be controlled at 25-50 ℃, the production control link is increased, and the requirement of the reaction environment is improved; (4) The catalyst is one or more of sodium bromide, zinc bromide and potassium bromide containing bromine, and toxic and harmful pollution is possible. In conclusion, the technical scheme also has the safety defect, and does not achieve the technical aims of strict environmental protection, high efficiency and saving.
Disclosure of Invention
The invention aims to provide a method for preparing 2,5-dimethoxy-2,5-dihydrofuran by photocatalytic biomass furan, which further reduces the production cost, improves the resource utilization rate, realizes the efficient synthesis of 2,5-dimethoxy-2,5-dihydrofuran, effectively reduces or avoids the use and generation of environmental poisons and pollutants in the synthesis process, and solves the defect problems of the prior art in scientific research and actual production.
In order to achieve the purpose, the invention provides a method for preparing 2,5-dimethoxy-2,5-dihydrofuran by photocatalysis of biomass furan, under the irradiation of visible light, biomass furan and methanol are synthesized into 2,5-dimethoxy-2,5-dihydrofuran under the action of a photocatalyst at room temperature and normal pressure in an air atmosphere, the catalyst is removed by filtration after the reaction is finished, and the filtrate is separated by reduced pressure distillation, wherein the reaction formula is as follows:
preferably, in the above reaction, biomass furan, methanol, catalyst are added to a three-necked round bottom flask equipped with a stirrer.
Preferably, in the above reaction, the catalyst is a photocatalyst comprising one or more of an organic ruthenium (ii) complex, an organic iridium (iii) complex, eosin Y, rose bengal.
Preferably, the biomass furan and methanol are used in a molar ratio of 1:2-1.
Preferably, the reaction conditions are visible light, room temperature, normal pressure and air.
Preferably, the wavelength range of the visible light is 380 to 780nm.
Compared with the prior art, the invention has the beneficial results that:
1. the reaction raw materials and the external energy source are green and renewable, the production cost can be further reduced, the resource utilization rate is improved, and the aim of efficiently synthesizing 2,5-dimethoxy-2,5-dihydrofuran in a saving way is fulfilled.
2. The reaction process is green and pollution-free, and the use and generation of environmental poisons and pollutants in the synthesis process are effectively reduced or avoided, so that the technical purposes of safety, environmental protection and no pollution are achieved.
3. The reaction condition is mild and easy to realize, the reaction device has no special requirement on corrosion resistance, the production condition limitation is further reduced, and the method is economical and practical and has industrial development value.
Drawings
FIG. 1 is a NMR spectrum of 2,5-dimethoxy-2,5-dihydrofuran;
FIG. 2 shows the NMR spectrum of 2,5-dimethoxy-2,5-dihydrofuran 1 H (protium) position diagram.
Detailed Description
The present invention will now be described more fully hereinafter with reference to the accompanying examples, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding biomass furan and methanol into a three-neck round-bottom flask with a stirrer according to a molar ratio of 1:4, and adding Ru (bpy) with the mass of 0.3wt% of furan 3 Cl 2 The ruthenium photocatalyst is placed under visible light to react in the air atmosphere at room temperature and normal pressure, the reaction process is monitored by adopting a thin-layer chromatography plate, the catalyst is removed by filtration after the reaction is finished, and the filtrate is subjected to reduced pressure distillation to separate 2,5-dimethoxy-2,5-dihydrofuran, wherein the yield is 82%.
Example 2
Adding biomass furan and methanol into a three-neck round-bottom flask with a stirrer according to a molar ratio of 1:4, and adding Ru (bpy) with the mass of 0.3wt% of furan 3 Cl 2 The ruthenium photocatalyst is placed under visible light to react in the air atmosphere at room temperature and normal pressure, the reaction process is monitored by adopting a thin-layer chromatography plate, the catalyst is removed by filtration after the reaction is finished, and the filtrate is subjected to reduced pressure distillation to separate 2,5-dimethoxy-2,5-dihydrofuran, wherein the yield is 80%.
Example 3
The biomass furan and the methanol are mixed according to the molar ratio of1:4 to a three neck round bottom flask equipped with a stirrer, ru (bpy) was added in an amount of 0.3wt% based on the weight of furan 3 Cl 2 The ruthenium photocatalyst is placed under visible light to react in argon atmosphere at room temperature and normal pressure, the reaction process is monitored by adopting a thin-layer chromatography plate, the catalyst is removed by filtration after the reaction is finished, and 2,5-dimethoxy-2,5-dihydrofuran is separated from filtrate by reduced pressure distillation, wherein the yield is 81%.
Example 4
Adding biomass furan and methanol into a three-neck round-bottom flask with a stirrer according to a molar ratio of 1:4, and adding Ru (bpy) with the mass of 0.3wt% of furan 3 Cl 2 The ruthenium photocatalyst is placed under visible light to react in oxygen atmosphere at room temperature and normal pressure, the reaction process is monitored by adopting a thin-layer chromatography plate, the catalyst is removed by filtration after the reaction is finished, and the filtrate is subjected to reduced pressure distillation to separate 2,5-dimethoxy-2,5-dihydrofuran, wherein the yield is 82%.
Example 5
Adding biomass furan and methanol into a three-neck round-bottom flask with a stirrer according to a molar ratio of 1:4, and adding Ru (bpy) with the mass of 0.3wt% of furan 3 Cl 2 The ruthenium photocatalyst is placed under visible light to react in the air atmosphere at room temperature and normal pressure, the reaction process is monitored by adopting a thin-layer chromatography plate, the catalyst is removed by filtration after the reaction is finished, and the filtrate is subjected to reduced pressure distillation to separate 2,5-dimethoxy-2,5-dihydrofuran with the yield of 81 percent.
Example 6
Adding biomass furan and methanol into a three-neck round-bottom flask with a stirrer according to a molar ratio of 1:4, and adding fac-Ir (ppy) with the mass of 0.5wt% of furan 3 The iridium photocatalyst is placed under visible light to react in oxygen atmosphere at room temperature and normal pressure, the reaction process is monitored by adopting a thin-layer chromatography plate, the catalyst is removed by filtration after the reaction is finished, and 2,5-dimethoxy-2,5-dihydrofuran is separated from filtrate by reduced pressure distillation, wherein the yield is 78%.
Example 7
Adding biomass furan and methanol into a three-neck round-bottom flask with a stirrer according to a molar ratio of 1:4, and adding Ir (tBupyy) with the mass of 0.5wt% of furan 3 An iridium photocatalyst is prepared by reacting an iridium compound,reacting in oxygen atmosphere at room temperature and normal pressure under visible light, monitoring the reaction process by using a thin layer chromatography plate, filtering to remove the catalyst after the reaction is finished, and separating 2,5-dimethoxy-2,5-dihydrofuran from the filtrate by reduced pressure distillation, wherein the yield is 77%.
Example 8
Adding biomass furan and methanol into a three-neck round-bottom flask with a stirrer according to a molar ratio of 1:6, adding an eosin Y photocatalyst with the mass of 1.0wt% of furan, placing the mixture in a visible light environment to react in an oxygen atmosphere at room temperature and normal pressure, monitoring the reaction process by using a thin layer chromatography plate, filtering to remove the catalyst after the reaction is finished, and separating 2,5-dimethoxy-2,5-dihydrofuran from the filtrate by reduced pressure distillation, wherein the yield is 30%.
Example 9
Adding biomass furan and methanol into a three-neck round-bottom flask with a stirrer according to a molar ratio of 1:8, adding a rose-red Bengal catalyst accounting for 1.5wt% of the mass of the furan, placing the mixture in a visible light environment to react in an oxygen atmosphere at room temperature and normal pressure, monitoring the reaction process by using a thin-layer chromatography plate, filtering to remove the catalyst after the reaction is finished, and separating 2,5-dimethoxy-2,5-dihydrofuran from the filtrate by reduced pressure distillation, wherein the yield is 15%.
Example 10
Adding biomass furan and methanol into a three-neck round-bottom flask with a stirrer according to a molar ratio of 1 3 Cl 2 The ruthenium photocatalyst is reacted in oxygen atmosphere at room temperature and normal pressure in the dark, the reaction process is monitored by adopting a thin layer chromatography plate, and 2,5-dimethoxy-2,5-dihydrofuran derivatives are not produced in the reaction.
Claims (3)
1. A method for preparing 2,5-dimethoxy-2,5-dihydrofuran by photocatalysis of biomass furan is characterized in that under the irradiation of visible light, the wavelength range of the visible light is 380 to 780nm, the biomass furan and methanol are used for synthesizing 2,5-dimethoxy-2,5-dihydrofuran under the action of a photocatalyst at room temperature and normal pressure in an air atmosphere, the catalyst is removed by filtration after the reaction is finished, and the filtrate is separated by reduced pressure distillation, wherein the reaction formula is as follows:
the catalyst is one or more of organic ruthenium (II) complex and organic iridium (III) complex.
2. The method for preparing 2,5-dimethoxy-2,5-dihydrofuran from photocatalytic biomass furan according to claim 1, wherein: in the above reaction, biomass furan, methanol, catalyst were added to a three-neck round bottom flask equipped with a stirrer.
3. The method for preparing 2,5-dimethoxy-2,5-dihydrofuran from photocatalytic biomass furan according to claim 2, wherein the method comprises the following steps: the molar ratio of the biomass furan to the biomass methanol is 1 to 2 to 1, and the photocatalyst is 0.3 to 1.5wt% of furan mass.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03161482A (en) * | 1989-11-21 | 1991-07-11 | Mitsui Petrochem Ind Ltd | Production of alkoxytetrahydrofuranone derivative |
| CN104592175A (en) * | 2014-12-29 | 2015-05-06 | 江苏清泉化学股份有限公司 | Preparation method of 2,5-dialkoxyl dihydrofuran compound |
| CN107793384A (en) * | 2016-08-31 | 2018-03-13 | 浙江医药股份有限公司新昌制药厂 | A kind of method for preparing the dihydrofuran of 2,5 dimethoxy 2,5 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03161482A (en) * | 1989-11-21 | 1991-07-11 | Mitsui Petrochem Ind Ltd | Production of alkoxytetrahydrofuranone derivative |
| CN104592175A (en) * | 2014-12-29 | 2015-05-06 | 江苏清泉化学股份有限公司 | Preparation method of 2,5-dialkoxyl dihydrofuran compound |
| CN107793384A (en) * | 2016-08-31 | 2018-03-13 | 浙江医药股份有限公司新昌制药厂 | A kind of method for preparing the dihydrofuran of 2,5 dimethoxy 2,5 |
Non-Patent Citations (3)
| Title |
|---|
| A PHOTO-OXIDATIVE ANALOGUE OF THE CLAUSON-KAAS REACTION;Ben L. Feringa等;《Tetrahedron Letters》;19821231;第23卷(第18期);第1941-1942页 * |
| New Baeyer-Villiger-like rearrangement products from sensitized photooxidation of acetylfuran, methyl-and ethylfuroate;Kuo, Yueh Hsiung;《Chemistry Express》;19861231;第1卷(第8期);说明书第2页第15段实施例1 * |
| 固定床电化学反应器内电化学氧化法制备2，5-二甲氧基二氢呋喃;许文林等;《化学反应工程与工艺》;20010630;第17卷(第2期);第185-188页 * |
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