CN114933575A - Method for preparing alpha-acetyl-gamma-butyrolactone - Google Patents
Method for preparing alpha-acetyl-gamma-butyrolactone Download PDFInfo
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- CN114933575A CN114933575A CN202210277861.9A CN202210277861A CN114933575A CN 114933575 A CN114933575 A CN 114933575A CN 202210277861 A CN202210277861 A CN 202210277861A CN 114933575 A CN114933575 A CN 114933575A
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- butyrolactone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
A method for preparing alpha-acetyl-gamma-butyrolactone relates to the technical field of organic synthesis, and comprises the steps of taking gamma-butyrolactone and acetic anhydride as raw materials, carrying out catalytic reaction by using a co-catalytic system formed by DMAP and tripropylamine, and carrying out heat preservation reaction at 95-110 ℃ for 3-6h to obtain a product alpha-acetyl-gamma-butyrolactone. The invention has the beneficial effects that: compared with the prior art, the method has the advantages of mild reaction conditions, no use of a high-pressure container, simple reaction product treatment, no use of dangerous raw materials such as ethylene oxide and sodium methoxide and the like, more environmental protection and safety, and suitability for industrial production.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for preparing alpha-acetyl-gamma-butyrolactone.
Background
Alpha-acetyl-gamma-butyrolactone is a very important intermediate for synthesizing medicines and pesticides, has been industrially produced in large scale abroad, is developed in 30 years at home, and is mainly produced by several manufacturers in Zhejiang, Jiangsu, Shanxi, Hubei and the like. And the total production value in China is not high, and most of the products are produced by self and cannot be sold. Therefore, the research on the synthesis of the compound has very important significance.
The current preparation routes of the alpha-acetyl-gamma-butyrolactone mainly comprise the following two routes: US patent US 5789603 reports a Claisen condensation process using gamma-butyrolactone and acetate as raw materials, sodium alkoxide as a condensing agent, and the corresponding acetate or benzene compound as a solvent, which is carried out in a high pressure reactor, requires a higher reaction apparatus, has a lower safety factor for operation, and has a lower yield. Chinese patent CN101092407B mentions that the method uses a supported alkali fluoride catalyst and a fixed bed reactor, and adopts the continuous reaction of vaporized gamma-butyrolactone and ethyl acetate to prepare alpha-acetyl-gamma-butyrolactone, the reaction is a gas phase reaction, the energy consumption is large, and the solid alkali fluoride catalyst has a certain hidden trouble to environmental pollution.
U.S. Pat. No. 2443827 reports a condensation, closed-loop process of ethyl acetoacetate with ethylene oxide which requires reaction temperatures below 0 deg.C, at higher temperatures ethyl acetoacetate readily saponifies to form sodium acetoacetate salts which affects the reaction yield, and also uses flammable and explosive ethylene oxide as a starting material. In the existing patents or documents, as reported in Chinese patent CN 103360349A, gamma-butyrolactone and ethyl acetate are used as raw materials and react with calcium oxide; the method adopts gamma-butyrolactone and ethyl acetate as raw materials to react with liquid acetaldehyde reported by Chinese patent CN 108658902A; the method adopts gamma-butyrolactone and isopropyl acetate as raw materials to react with liquid acetaldehyde reported by Chinese patent CN 108299345A; the methods have the problems of multiple reaction steps, harsh reaction conditions, long reaction time, difficult product separation, great environmental pollution and the like. Therefore, a safe, green and convenient production process is imperative to find.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing alpha-acetyl-gamma-butyrolactone. The method has the advantages of mild reaction, no use of a high-pressure container, short reaction time, low separation difficulty, high yield and good industrial application prospect.
The invention provides a method for preparing alpha-acetyl-gamma-butyrolactone, which takes gamma-butyrolactone and acetic anhydride as raw materials, takes a co-catalytic system formed by DMAP and tripropylamine to perform catalytic reaction, and performs heat preservation reaction at 95-110 ℃ for 3-6h to obtain a product of alpha-acetyl-gamma-butyrolactone.
The preparation method comprises the steps of adding gamma-butyrolactone, tripropylamine and DMAP into a reaction container, heating to 45-50 ℃, dropwise adding acetic anhydride into the reaction container, keeping the temperature between 45 and 55 ℃ in the dropwise adding process, heating to 95-110 ℃ after dropwise adding, keeping the temperature at 95-110 ℃ for reaction for 3-6 hours, cooling to room temperature after the reaction is finished, filtering, washing a filter cake with gamma-butyrolactone, combining, and performing reduced pressure rectification to respectively obtain gamma-butyrolactone and alpha-acetyl-gamma-butyrolactone, wherein the gamma-butyrolactone can be recycled.
In the preparation method, the added gamma-butyrolactone is excessive, and the excessive part is used as a reaction solvent, namely, the gamma-butyrolactone is a reactant and a reaction solvent.
Preferably, the molar ratio of the gamma-butyrolactone to the acetic anhydride is: 3-5:1-2.
Preferably, the molar ratio of the acetic anhydride to the tripropylamine and the DMAP is as follows: 1:1:0.01-0.06.
Preferably, the molar ratio of the acetic anhydride to the tripropylamine and the DMAP is as follows: 1:1:0.03-0.05.
Preferably, the reaction time is 4-5h, and the temperature is 100-105 ℃.
The invention has the beneficial effects that: (1) DMAP is used as a catalyst and forms a co-catalytic system with tripropylamine, so that the reaction is mild, and dangerous containers such as high-pressure kettles and the like are avoided. (2) The reaction product is easy to process, does not use organic solvent for extraction, does not need secondary distillation, saves the cost and avoids environmental pollution. (3) The gamma-butyrolactone is used as the solvent, so that the cost is saved, and the environmental pollution caused by the introduction of the solvent is avoided.
Compared with the prior art, the method has the advantages of mild reaction conditions, no use of a high-pressure container, simple reaction product treatment, no use of dangerous raw materials such as ethylene oxide and sodium methoxide and the like, more environmental protection and safety, and suitability for industrial production.
Detailed Description
Example 1, 258.27g (3.0mol) of γ -butyrolactone, 143.27g (1.0mol) of tripropylamine, and 6.1g (0.05mol) of DMAP were added to a three-necked flask, the temperature was raised to 45 ℃ to 50 ℃, 102.1g (1mol) of acetic anhydride was added dropwise to the three-necked flask, the temperature was maintained between 45 ℃ and 55 ℃ during the dropwise addition, after the dropwise addition, the temperature was raised to 105 ℃, the temperature was maintained for reaction for 4.5 hours, after the reaction was completed, the reaction was cooled to room temperature, filtration was carried out, the filter cake was washed with γ -butyrolactone, and after the combination, the product with a boiling point of 253 ℃ was obtained, and γ -butyrolactone obtained during the rectification could be recycled. 104.57g of the obtained product had a gas phase purity of 99.3% and a reaction yield of 81.6%.
Example 2, 430.45g (5.0mol) of gamma-butyrolactone, 286.54g (2.0mol) of tripropylamine and 14.64g (0.12mol) of DMAP are added into a three-necked flask, the temperature is raised to 45-50 ℃, 204.18g (2.0mol) of acetic anhydride is added into the three-necked flask, the temperature is kept between 45-55 ℃ during the adding process, the temperature is raised to 110 ℃ after the adding process is finished, the reaction is kept for 4h, the reaction is cooled to room temperature after the reaction is finished, the filter cake is washed by gamma-butyrolactone, the mixture is rectified and decompressed to obtain a product with the boiling point of 253 ℃, and the gamma-butyrolactone obtained in the rectifying process can be recycled. 195.76g of the product was obtained, the gas phase purity was 99.1%, and the reaction yield was 76.4%.
Example 3, 258.27g (3.0mol) of gamma-butyrolactone, 143.27g (1.0mol) of tripropylamine and 3.66g (0.03mol) of DMAP are added into a three-necked flask, the temperature is raised to 45-50 ℃, 112.3g (1.1mol) of acetic anhydride is added into the three-necked flask, the temperature is kept between 45-55 ℃ during the adding process, the temperature is raised to 95 ℃ after the adding process is finished, the reaction is kept for 6h, the reaction is cooled to room temperature after the reaction is finished, the filtration is carried out, the filter cake is washed by gamma-butyrolactone, the combination and the reduced pressure rectification are carried out, the product with the boiling point of 253 ℃ is obtained, and the gamma-butyrolactone obtained in the rectification process can be recycled and reused. 110.52g of the obtained product had a gas phase purity of 99.5% and a reaction yield of 78.4%.
Claims (7)
1. A method for preparing alpha-acetyl-gamma-butyrolactone is characterized in that gamma-butyrolactone and acetic anhydride are used as raw materials, a co-catalytic system formed by DMAP and tripropylamine is used for catalytic reaction, and the alpha-acetyl-gamma-butyrolactone product is obtained after the reaction is carried out for 3-6h under the condition of heat preservation at 95-110 ℃.
2. The method for preparing alpha-acetyl-gamma-butyrolactone according to claim 1, characterized in that the preparation method of alpha-acetyl-gamma-butyrolactone comprises the steps of adding gamma-butyrolactone, tripropylamine and DMAP into a reaction vessel, heating to 45-50 ℃, adding acetic anhydride dropwise into the reaction vessel, keeping the temperature between 45-55 ℃ during the dropwise addition, heating to 95-110 ℃ after the dropwise addition, keeping the temperature at 95-110 ℃ for reaction for 3-6h, cooling to room temperature after the reaction is finished, filtering, washing filter cakes with gamma-butyrolactone, combining, and performing reduced pressure distillation to obtain gamma-butyrolactone and alpha-acetyl-gamma-butyrolactone respectively.
3. The method of claim 2, wherein the γ -butyrolactone is added in excess and the excess is used as a reaction solvent, i.e. γ -butyrolactone is both a reactant and a reaction solvent.
4. The method of claim 3, wherein the molar ratio of γ -butyrolactone to acetic anhydride is: 3-5:1-2.
5. The method for preparing α -acetyl- γ -butyrolactone according to claim 4, wherein the molar ratio of acetic anhydride to tripropylamine, DMAP is: 1:1:0.01-0.06.
6. The method for preparing α -acetyl- γ -butyrolactone according to claim 5, wherein the molar ratio of acetic anhydride to tripropylamine, DMAP is: 1:1:0.03-0.05.
7. The method as claimed in claim 6, wherein the reaction time is 4-5h and the temperature is 100-105 ℃.
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| CN202210277861.9A CN114933575B (en) | 2022-03-21 | 2022-03-21 | Method for preparing alpha-acetyl-gamma-butyrolactone |
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| CN202210277861.9A CN114933575B (en) | 2022-03-21 | 2022-03-21 | Method for preparing alpha-acetyl-gamma-butyrolactone |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5789603A (en) * | 1996-02-24 | 1998-08-04 | Huels Aktiengesellschaft | Method for preparing 2-acetyl-γ-butyrolactone |
| CN108129423A (en) * | 2018-02-09 | 2018-06-08 | 东北制药集团股份有限公司 | A kind of method for preparing α-acetyl-gamma-butyrolacton |
| CN114195745A (en) * | 2021-12-29 | 2022-03-18 | 江苏兄弟维生素有限公司 | Preparation method and application of alpha-acetyl-gamma-butyrolactone |
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- 2022-03-21 CN CN202210277861.9A patent/CN114933575B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5789603A (en) * | 1996-02-24 | 1998-08-04 | Huels Aktiengesellschaft | Method for preparing 2-acetyl-γ-butyrolactone |
| CN108129423A (en) * | 2018-02-09 | 2018-06-08 | 东北制药集团股份有限公司 | A kind of method for preparing α-acetyl-gamma-butyrolacton |
| CN114195745A (en) * | 2021-12-29 | 2022-03-18 | 江苏兄弟维生素有限公司 | Preparation method and application of alpha-acetyl-gamma-butyrolactone |
Non-Patent Citations (1)
| Title |
|---|
| 张莉: "α-乙酰基-γ-丁内酯的合成及进展" * |
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