CN115707682A - Method for preparing dicarboxylic acid with high selectivity by taking cyclic ether as raw material through carbonylation reaction - Google Patents
Method for preparing dicarboxylic acid with high selectivity by taking cyclic ether as raw material through carbonylation reaction Download PDFInfo
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Abstract
The invention discloses a method for preparing dicarboxylic acid with high selectivity by taking cyclic ether as a raw material through carbonylation reaction, and particularly relates to a method for synthesizing dicarboxylic acid by taking cyclic ether as a raw material through carbonylation under the atmosphere of hydrogen and carbon monoxide by using a noble metal catalyst, an iodine-containing promoter and a solvent at 80-280 ℃ for 2-45h. The invention provides a method for efficiently and selectively synthesizing dicarboxylic acid by carbonylation by using cyclic ether as a substrate. Overcomes the limitation that the cyclic ether can only synthesize the monocarboxylic acid in the existing carbonylation reaction.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for preparing dicarboxylic acid with high selectivity by taking cyclic ether as a raw material through carbonylation reaction.
Background
Dicarboxylic acid is a very important chemical substance and is widely applied to industries such as plastics, medicines and the like. Ethers are inexpensive and basic chemicals that can be obtained from a variety of sources, including biomass, but they are rarely used as substrates for the production of higher carboxylic acids by carbonylation. Generally, ethers are less reactive than olefins and/or alcohols. Buxing Han expressed as IrI 4 Is used as a catalyst, liI is used as an accelerating agent, acetic acid is used as a solvent at 170 DEG CThen, the tetrahydrofuran is used as a raw material to synthesize the valeric acid and the dimethylbutyric acid (the molar ratio is 6: 4). And the catalyst has good substrate adaptability, and can be effectively converted into corresponding high-carboxylic acid for various ethers, such as cycloalkyl ether, n-alkyl ether, iso-alkyl ether and aralkyl ether. (Nature Communications,10, 13463-13469). However, the carboxylic acid synthesized using a cyclic ether as a substrate is often a monocarboxylic acid, that is, a carboxylic acid is formed only at one end after the ether bond is broken, and there has been no report that a carboxylic acid is formed at both ends of the ether bond to produce a dicarboxylic acid having a higher value.
Disclosure of Invention
The invention provides a method for preparing dicarboxylic acid with high selectivity by taking cyclic ether as a raw material through carbonylation reaction, which comprises the following steps: the cyclic ether is reacted in the presence of carbon monoxide, hydrogen, catalyst, promoter and solvent at raised temperature to produce dicarboxylic acid. The present invention also provides the following more preferable embodiments, which have corresponding creativity based on the technical idea of preparing the dicarboxylic acid.
On the basis of the above scheme, preferably, the cyclic ether substrate may be various substituted and unsubstituted tetracyclic, pentacyclic, hexacyclic, heptacyclic, etc. cyclic ethers (tetrahydrofuran, 2-methyltetrahydrofuran, 2, 5-dimethyltetrahydrofuran, furan, tetrahydropyran, epoxyhexane, etc.);
on the basis of the scheme, preferably, the catalyst is one of rhodium-containing catalysts and iridium-containing catalysts;
on the basis of the scheme, preferably, the iodine-containing promoter can be one of iodine, organic iodine, hydroiodic acid and metal iodide;
on the basis of the scheme, the solvent is preferably organic acid such as acetic acid, propionic acid, trifluoroacetic acid and the like;
on the basis of the scheme, preferably, the hydrogen pressure is between 0.2 and 10 MPa;
on the basis of the above scheme, preferably, the carbon monoxide pressure is between 0.2 and 10 MPa;
on the basis of the scheme, preferably, the temperature rise is 80-280 ℃;
on the basis of the scheme, the reaction time is preferably 2-45h;
on the basis of the scheme, the molar ratio of the catalyst to the cyclic ether substrate is preferably 1: 5-1: 1000;
on the basis of the above scheme, preferably, the amount of the promoter iodine is 0.1 to 5mmol.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for preparing dicarboxylic acid with high selectivity by taking cyclic ether as a raw material through carbonylation reaction.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
A50 ml reaction vessel was charged with 1mmol of tetrahydrofuran, 0.06mmol of RhCl 3 ·3H 2 O,0.6mmol of iodine simple substance, 3ml of acetic acid and 2ml of water, and then sealing the reaction kettle. And (3) removing air in the reaction kettle, introducing 1MPa hydrogen and 2MPa carbon monoxide, heating the reaction kettle to 170 ℃, and stirring for reaction for 12 hours. After the reaction is finished, the reaction solution is subjected to constant volume, filtered and used for subsequent examination and analysis, and the yield of the adipic acid is 63%.
The apparatus for measuring the carboxylic acid concentration was a Watts H-Class series high performance liquid chromatograph (RID detector, alltech OA 1000 Organic Acids liquid chromatograph (300 mm. Times.6.5 mm), flow rate 0.6mL/min, column temperature 60 ℃, mobile phase 0.1g/L dilute sulfuric acid).
Yield of carboxylic acid calculation:
yield of carboxylic acid = (actual yield of carboxylic acid/theoretical yield of carboxylic acid) × 100%.
Example 2
At 5A0 ml reaction vessel was charged with 1mmol of tetrahydrofuran, 0.06mmol of RhCl 3 ·3H 2 O,0.6mmol of iodine simple substance, 4ml of acetic acid and 1ml of water, and then sealing the reaction kettle. And (3) after air in the reaction kettle is removed, introducing 0.5MPa hydrogen and 3MPa carbon monoxide, heating the reaction kettle to 170 ℃, and stirring for reaction for 10 hours. After the reaction is finished, the reaction solution is subjected to constant volume, filtered and used for subsequent examination and analysis, and the yield of the adipic acid is 57%.
Example 3
1mmol of tetrahydrofuran and 0.06mmol of RhCl were added in a 50ml reaction vessel 3 ·3H 2 O,0.6mmol of methyl iodide, 3ml of acetic acid and 2ml of water, and then sealing the reaction kettle. And (3) after air in the reaction kettle is removed, introducing 0.5MPa hydrogen and 3MPa carbon monoxide, heating the reaction kettle to 170 ℃, and stirring for reaction for 10 hours. After the reaction is finished, the reaction solution is subjected to constant volume, filtered and used for subsequent examination and analysis, and the yield of the adipic acid is 17%.
Example 4
In a 50ml reaction vessel were added 1mmol of tetrahydropyran, 0.06mmol of [ Rh (CO) ] 2 Cl] 2 1mmol hydriodic acid, 3ml acetic acid and 2ml water, and then the reaction kettle is sealed. And (3) introducing 3MPa hydrogen and 3MPa carbon monoxide after air in the reaction kettle is removed, heating the reaction kettle to 170 ℃, and stirring for reaction for 10 hours. After the reaction is finished, the reaction solution is subjected to constant volume, filtered and used for subsequent detection and analysis, and the yield of the pimelic acid is 73%.
Example 5
1mmol of tetrahydrofuran and 0.1mmol of IrCl are added into a 50ml reaction kettle 3 1mmol of I 2 3ml of acetic acid and 2ml of water, and then sealing the reaction kettle. And (3) introducing 3MPa hydrogen and 3MPa carbon monoxide after air in the reaction kettle is removed, heating the reaction kettle to 170 ℃, and stirring for reaction for 10 hours. After the reaction is finished, the reaction solution is subjected to constant volume, filtered and used for subsequent examination and analysis, and the yield of the adipic acid is 6%.
Example 6
A50 ml reaction vessel was charged with 1mmol tetrahydrofuran, 0.1mmol RhCl 3 2mmol of LiI,3ml of acetic acid and 2ml of water, and then sealing the reaction kettle. After the air in the reaction kettle is removed, 3MPa hydrogen is introduced into the reaction kettle3MPa of carbon monoxide, heating the reaction kettle to 170 ℃, and stirring for reaction for 10 hours. After the reaction is finished, the reaction solution is subjected to constant volume, filtered and used for subsequent examination and analysis, and the yield of the adipic acid is 12%.
Example 7
A50 ml reaction vessel was charged with 1mmol of tetrahydrofuran, 0.1mmol of RhCl3,1mmol of I 2 3ml of trifluoroacetic acid and 2ml of water, and then sealing the reaction kettle. And (3) introducing 3MPa hydrogen and 3MPa carbon monoxide after air in the reaction kettle is removed, heating the reaction kettle to 170 ℃, and stirring for reaction for 10 hours. After the reaction is finished, the reaction solution is subjected to constant volume and filtration for subsequent examination and analysis, and the yield of the adipic acid is 83%.
The foregoing description merely represents preferred embodiments of the present invention, which are described in some detail and detail, and should not be construed as limiting the scope of the present invention. It should be noted that, for those skilled in the art, various changes, modifications and substitutions can be made without departing from the spirit of the present invention, and these are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for preparing dicarboxylic acid with high selectivity by taking cyclic ether as a raw material through carbonylation reaction is characterized in that: the method comprises the following steps: adding cyclic ether as raw material into reactor, under the atmosphere of hydrogen and CO, using noble metal catalyst, iodine-containing promoter and solvent, under the condition of raising temp. and high-selectively synthesizing dicarboxylic acid by means of carbonylation.
2. The process according to claim 1 for the preparation of dicarboxylic acid by carbonylation reaction with high selectivity starting from cyclic ether, wherein: the catalyst is one of rhodium-containing and iridium-containing catalysts.
3. The process according to claim 1 for the preparation of dicarboxylic acids by carbonylation starting from cyclic ethers with high selectivity, characterized in that: the iodine-containing promoter is one of iodine, organic iodine, hydroiodic acid and metal iodides.
4. The process according to claim 1 for the preparation of dicarboxylic acid by carbonylation reaction with high selectivity starting from cyclic ether, wherein: the solvent is an organic acid.
5. The process according to claim 1 for the preparation of dicarboxylic acid by carbonylation reaction with high selectivity starting from cyclic ether, wherein: the hydrogen pressure is between 0.2 and 10 MPa.
6. The process according to claim 1 for the preparation of dicarboxylic acid by carbonylation reaction with high selectivity starting from cyclic ether, wherein: the pressure of the carbon monoxide is between 0.2 and 10 MPa.
7. The process according to claim 1 for the preparation of dicarboxylic acid by carbonylation reaction with high selectivity starting from cyclic ether, wherein: the temperature rise is 80-280 ℃.
8. The process according to claim 1 for the preparation of dicarboxylic acid by carbonylation reaction with high selectivity starting from cyclic ether, wherein: the reaction time is 2-45h.
9. The process according to claim 1 for the preparation of dicarboxylic acid by carbonylation reaction with high selectivity starting from cyclic ether, wherein: the molar ratio of the catalyst to the cyclic ether substrate is 1: 5-1: 1000.
10. The process according to claim 1 for the preparation of dicarboxylic acids by carbonylation starting from cyclic ethers with high selectivity, characterized in that: the iodine content of the promoter is 0.1-5mmol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211437357.7A CN115707682A (en) | 2022-11-16 | 2022-11-16 | Method for preparing dicarboxylic acid with high selectivity by taking cyclic ether as raw material through carbonylation reaction |
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| CN202211437357.7A CN115707682A (en) | 2022-11-16 | 2022-11-16 | Method for preparing dicarboxylic acid with high selectivity by taking cyclic ether as raw material through carbonylation reaction |
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