CN106905127B - Method for synthesizing 2, 5-hexanedione by oxidative dehydrogenation coupling of acetone - Google Patents
Method for synthesizing 2, 5-hexanedione by oxidative dehydrogenation coupling of acetone Download PDFInfo
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- CN106905127B CN106905127B CN201710136838.7A CN201710136838A CN106905127B CN 106905127 B CN106905127 B CN 106905127B CN 201710136838 A CN201710136838 A CN 201710136838A CN 106905127 B CN106905127 B CN 106905127B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
Abstract
A process for synthesizing 2, 5-hexanedione by oxidative dehydrogenation and coupling of acetone includes such steps as adding hydrogen peroxide solution and photocatalyst to the reaction liquid of acetone-water, magnetically stirring while vacuumizing or introducing nitrogen to remove air from system, and photocatalyzing/photochemically decomposing hydrogen peroxide under ultraviolet lamp or visible light source to trigger the carbon-carbon coupling reaction of acetone to synthesize 2, 5-hexanedione. The method is a green synthetic route, is carried out at normal temperature and normal pressure, is easy to operate, has high economic benefit, and is suitable for industrial production.
Description
Technical Field
The invention relates to a method for synthesizing 2, 5-hexanedione by oxidative dehydrogenation coupling of acetone.
Technical Field
2, 5-hexanedione is also called acetonyl acetone, is used as a high boiling point solvent for synthetic resin, nitro spray paint, colorant, printing ink and the like, leather tanning agent, rubber vulcanization accelerator, pesticide, drug raw material, medical intermediate synthesis and other fields, and is an important raw material for synthesizing various organic intermediates.
The 2, 5-hexanedione is mainly synthesized by hydrolysis of 2, 5-dimethylfuran, coupling decarboxylation of ethyl acetoacetate and other methods. 2, 5-dimethyl furan hydrolysis method for preparing 2, 5-hexanedione is to heat 2, 5-dimethyl furan to 250 ℃ in acid aqueous solution, and then the 2, 5-hexanedione is obtained by hydrolytic ring opening. Or heating to 175 ℃ under an acidic condition by using a platinum carbon catalyst to catalyze the hydrolysis of the 2, 5-dimethylfuran to obtain the 2, 5-hexanedione. However, the catalyst and raw material cost of the method is too high, and the method needs to be carried out under acidic or alkaline conditions, so that the method has serious corrosion to equipment and certain safety problems.
The method for preparing 2, 5-hexanedione by coupling and decarboxylation of ethyl acetoacetate is to adopt sodium ethyl acetoacetate to react with pure iodine to generate diethyl diacetylsuccinate, and then hydrolyze the diethyl diacetylsuccinate and 10% sodium hydroxide solution. The reaction mixture was saturated with anhydrous potassium carbonate to precipitate 2, 5-hexanedione. Extracting with diethyl ether, distilling the residue after the diethyl ether is evaporated from the extracting solution, and collecting the 192-194 ℃ fraction to obtain a colorless product, namely the 2, 5-hexanedione. The method has high raw material cost and complex operation process, and is not beneficial to industrial expanded production.
The photocatalysis/photochemistry is a green synthetic route, and particularly provides a photocatalysis/photochemistry organic synthesis, which develops a brand new synthetic route, is carried out at normal temperature and normal pressure, is easy to operate, generally does not produce secondary pollution, is already applied to organic reactions such as polymerization, olefin epoxidation, carbonylation and the like, and obtains abundant results.
Disclosure of Invention
The invention aims to provide a method for synthesizing 2, 5-hexanedione by initiating acetone to carry out carbon-carbon coupling at α.
The invention is under the irradiation of ultraviolet light or visible light, H2O2The raw materials of the method are cheap and easy to obtain, the process is simple, the production cost is low, the method is environment-friendly and the like, the selectivity is high, the reaction rate is high, the product is easy to separate, and the method is a green and efficient 2, 5-hexanedione synthesis technology, and the chemical reaction expression is as follows:
1.
2.
3.
and (3) total reaction:
the invention is realized by the following technologies:
according to the reaction solution: hydrogen peroxide solution: the photocatalyst is 100-500 ml: 10ml-40 ml: adding hydrogen peroxide solution and photocatalyst into the acetone-water reaction solution according to the proportion of 0-3.5g, vacuumizing or introducing nitrogen under magnetic stirring, removing air in the system, starting an ultraviolet lamp or visible light source with the power of 100W-2000W, and carrying out photocatalytic/photochemical decomposition on the hydrogen peroxide to initiate the reaction of acetone for carbon-carbon coupling synthesis of 2, 5-hexanedione. The reaction temperature is between 5 and 55 ℃, the reaction time is between 0.5 and 30 hours, and after the reaction is finished, the solution is distilled or decompressed and distilled to separate out acetone and water, so that the product 2, 5-hexanedione is obtained.
The concentration of the hydrogen peroxide solution as described above is 5wt% to 50 wt%.
The volume content of acetone in the acetone-water reaction solution is 30-100%.
The mixing manner of the reaction solution and the hydrogen peroxide solution is disposable, intermittent or continuous.
The light source for the reaction requiring the light condition as described above is a mercury lamp, a xenon lamp, simulated sunlight or real sunlight.
The semiconductor photocatalyst is WO as described above3Graphite oxide and BiVO4CdS or C3N4。
Compared with the prior art, the invention has the following advantages:
1. the method for synthesizing the 2, 5-hexanedione by one step of photocatalytic/photochemical acetone oxidative dehydrogenation coupling is a green synthetic route, is carried out at normal temperature and normal pressure, is easy to operate, has high economic benefit, generally does not produce secondary pollution, and is suitable for industrial production.
2. In the reaction system, H2O2The decomposed OH abstracts α -H in acetone, and then acetone radical free radical generates carbon-carbon coupling reaction, the product is 2, 5-hexanedione and water, a small amount of by-products are generated, and the selectivity is high.
3. The reactants are cheap acetone and hydrogen peroxide, and the 2, 5-hexanedione product with high added value can be obtained.
4. The catalyst has single and stable component, does not need to load a noble metal catalyst, and is favorable for recycling and reusing.
Detailed Description
The invention is further illustrated by the following examples, which are intended only for a better understanding of the contents of the study and are not intended to limit the scope of the invention.
Example one
210mL of acetone is put into a reaction bottle, argon is introduced under magnetic stirring to remove air in the system, and the concentration of H in the reaction process is 30wt percent2O2The solution is continuously added into a reaction system by a peristaltic pump, the adding speed is 20mmol/h, a 300W mercury lamp is started to carry out photochemical initiation of the reaction of synthesizing the 2, 5-hexanedione by carbon-carbon coupling at the position α of acetone, the reaction temperature is 25 ℃, the reaction time is 8h, and after the reaction is finished, chromatographic analysis shows that the selectivity of the 2, 5-hexanedione is 68 percent, and the generation speed is 8.6 mmol/h.
Example two
500mL of acetone-water reaction solution with acetone volume fraction of 30% is put into a reaction bottle, argon is introduced under magnetic stirring to remove air in the system, and 40mLH with the concentration of 5wt% is added in the reaction process2O2The solution is added into a reaction system at one time, a 100W mercury lamp is started to carry out photochemical initiation of the reaction of synthesizing the 2, 5-hexanedione by carbon-carbon coupling at the position of α acetone, the reaction temperature is 25 ℃, the reaction time is 8h, and after the reaction is finished, chromatographic analysis shows that the selectivity of the 2, 5-hexanedione is 32 percent, and the generation rate is 2.4 mmol/h.
EXAMPLE III
210mL of acetone is put into a reaction bottle, argon is introduced under magnetic stirring, air in the system is removed, a 1000W mercury lamp is started, and the concentration is 50wt% 20mLH in the reaction process2O2Intermittently adding the solution into a reaction system for three times to perform photochemically-initiated reaction for synthesizing the 2, 5-hexanedione by carbon-carbon coupling at the α th site of the acetone, wherein the reaction temperature is 25 ℃, the reaction time is 8h, and after the reaction is finished, chromatographic analysis shows that the selectivity of the 2, 5-hexanedione is 51 percent, and the generation rate is 5.5 mmol/h.
Example four
210mL of acetone-water reaction liquid with acetone volume fraction of 50 percent is put into a reaction bottle, argon is introduced under magnetic stirring, and a drainage bodyAir in the system, concentration in reaction process is 40 wt% H2O2The solution is continuously added into a reaction system by a peristaltic pump, the adding speed is 20mmol/h, a 300W mercury lamp is started to carry out photochemical initiation of the reaction of synthesizing the 2, 5-hexanedione by carbon-carbon coupling at the position α of acetone, the reaction temperature is 5 ℃, the reaction time is 8h, and after the reaction is finished, chromatographic analysis shows that the selectivity of the 2, 5-hexanedione is 41 percent, and the generation speed is 2.5 mmol/h.
EXAMPLE five
Mixing sol-gel prepared 3.5gWO3Adding the photocatalyst into 500mL of acetone, introducing argon under magnetic stirring, removing air in the system, wherein the concentration of H in the reaction process is 30 wt%2O2The solution is continuously added into a reaction system by a peristaltic pump, the adding speed is 10mmol/h, a 2000W mercury lamp is started to carry out the reaction of synthesizing the 2, 5-hexanedione by photocatalytic acetone α -carbon coupling, the reaction temperature is 25 ℃, the reaction time is 8h, after the reaction is finished, reaction liquid is separated by standing and precipitating, and chromatographic analysis shows that the selectivity of the 2, 5-hexanedione is 64 percent, and the generation speed is 5.1 mmol/h.
EXAMPLE six
Adding 0.1g of graphite oxide photocatalyst prepared by a Hummer method into 210mL of acetone, introducing argon gas under magnetic stirring, removing air in a system, wherein the concentration of H in the reaction process is 30 wt%2O2The solution is continuously added into a reaction system by a peristaltic pump, the adding speed is 20mmol/h, a 300W xenon lamp is started to carry out the reaction of synthesizing the 2, 5-hexanedione by photocatalytic acetone α -carbon coupling, the reaction temperature is 25 ℃, the reaction time is 3h, after the reaction is finished, reaction liquid is separated by standing and precipitating, and chromatographic analysis shows that the selectivity of the 2, 5-hexanedione is 47% and the generation speed is 6.2 mmol/h.
EXAMPLE seven
Adding 1.5g of bismuth vanadate catalyst prepared by a hydrothermal method into 210mL of acetone, introducing argon under magnetic stirring, removing air in a system, wherein the concentration of H in the reaction process is 20 wt%2O2Continuously adding the solution into a reaction system by a peristaltic pump, wherein the adding speed is 5mmol/h, starting a 300W xenon lamp to carry out the reaction of synthesizing 2, 5-hexanedione by photocatalytic acetone α -site carbon-carbon coupling, and the reaction temperature isThe reaction time is 12h at 25 ℃. After the reaction, the reaction solution was separated by settling, and the chromatographic analysis showed that the selectivity of 2, 5-hexanedione was 54% and the formation rate was 6.8 mmol/h.
Example eight
Adding 1g CdS prepared by a hydrothermal method into 210mL acetone, introducing argon under magnetic stirring, removing air in a system, wherein the concentration of H in the reaction process is 30 wt%2O2The solution is continuously added into a reaction system by a peristaltic pump, the adding speed is 10mmol/h, a 100W xenon lamp is started to carry out the reaction of synthesizing the 2, 5-hexanedione by photocatalytic acetone α -carbon coupling, the reaction temperature is 55 ℃, the reaction time is 30h, after the reaction is finished, reaction liquid is separated by standing and precipitating, and chromatographic analysis shows that the selectivity of the 2, 5-hexanedione is 51 percent, and the generating speed is 2.2 mmol/h.
Example nine
1gC prepared by calcining urea at 600 DEG C3N4Adding into 210mL acetone, introducing argon under magnetic stirring, removing air in the system, wherein the concentration of H in the reaction process is 30 wt%2O2The solution is continuously added into a reaction system by a peristaltic pump, the adding speed is 20mmol/h, a 300W xenon lamp is started to carry out the reaction of synthesizing the 2, 5-hexanedione by photocatalytic acetone α -carbon coupling, the reaction temperature is 25 ℃, the reaction time is 0.5h, after the reaction is finished, reaction liquid is separated by standing and precipitating, and chromatographic analysis shows that the selectivity of the 2, 5-hexanedione is 43 percent, and the generation speed is 4.2 mmol/h.
Claims (5)
1. A method for synthesizing 2, 5-hexanedione by oxidative dehydrogenation coupling of acetone is characterized by comprising the following steps: according to the reaction solution: hydrogen peroxide solution: the photocatalyst is 100-500 ml: 10ml-40 ml: adding a hydrogen peroxide solution and a photocatalyst into an acetone-water reaction solution according to the proportion of 0-3.5g, vacuumizing or introducing nitrogen under magnetic stirring, removing air in a system, starting a mercury lamp or xenon lamp with the power of 100W-2000W, and carrying out photocatalytic/photochemical decomposition on hydrogen peroxide so as to initiate the reaction of synthesizing 2, 5-hexanedione by carbon-carbon coupling of acetone; the reaction temperature is between 5 and 55 ℃, the reaction time is between 0.5 and 30 hours, and after the reaction is finished, the solution is distilled or decompressed and distilled to separate out acetone and water, so that the product 2, 5-hexanedione is obtained.
2. The method for synthesizing 2, 5-hexanedione by oxidative dehydrogenation coupling of acetone as claimed in claim 1, wherein the concentration of the hydrogen peroxide solution is 5wt% to 50 wt%.
3. The method for synthesizing 2, 5-hexanedione by oxidative dehydrogenation coupling of acetone as claimed in claim 1, wherein the volume content of acetone in the acetone-water reaction solution is 30-100%.
4. The method for synthesizing 2, 5-hexanedione by oxidative dehydrogenation coupling of acetone as claimed in claim 1, wherein the reaction solution and the hydrogen peroxide solution are mixed in a disposable, intermittent or continuous manner.
5. The method for synthesizing 2, 5-hexanedione by oxidative dehydrogenation coupling of acetone as claimed in claim 1, wherein the photocatalyst is WO3Graphite oxide and BiVO4CdS or C3N4。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56169639A (en) * | 1980-06-03 | 1981-12-26 | Asahi Chem Ind Co Ltd | Preparation of 2,5-hexanedione |
| JPH0441447A (en) * | 1990-06-04 | 1992-02-12 | Japan Atom Energy Res Inst | Production of butanediol by irradiation of light |
| CN101723817A (en) * | 2009-11-23 | 2010-06-09 | 湖南师范大学 | Method for preparing 2, 3-butanedione |
| CN102070404A (en) * | 2011-01-25 | 2011-05-25 | 中国科学院山西煤炭化学研究所 | Method for synthesizing 3,4-hexanediol through photocatalysis |
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2017
- 2017-03-09 CN CN201710136838.7A patent/CN106905127B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56169639A (en) * | 1980-06-03 | 1981-12-26 | Asahi Chem Ind Co Ltd | Preparation of 2,5-hexanedione |
| JPH0441447A (en) * | 1990-06-04 | 1992-02-12 | Japan Atom Energy Res Inst | Production of butanediol by irradiation of light |
| CN101723817A (en) * | 2009-11-23 | 2010-06-09 | 湖南师范大学 | Method for preparing 2, 3-butanedione |
| CN102070404A (en) * | 2011-01-25 | 2011-05-25 | 中国科学院山西煤炭化学研究所 | Method for synthesizing 3,4-hexanediol through photocatalysis |
Non-Patent Citations (2)
| Title |
|---|
| The Radiolysis of Acetone in Air-Free Aqueous Solutions，Peter Riesz，Journal of Physical Chemistry;Peter Riesz;《Journal of Physical Chemistry》;19651231;第69卷;第1366-1373页 * |
| 绿色催化合成3,4-己二酮;梁立冬等;《上海应用技术学院学报(自然科学版)》;20110315;第11卷(第01期);第34-36、41页 * |
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