A method for highly selectively preparing dicarboxylic acid from cyclic ether through carbonylation reaction

Abstract

The present invention discloses a method for highly selectively preparing dicarboxylic acids by carbonylation reaction using cyclic ethers as raw materials. Specifically, cyclic ethers are used as raw materials, and under a hydrogen and carbon monoxide atmosphere, with a noble metal catalyst, an iodine-containing promoter, and a solvent, dicarboxylic acids are synthesized by carbonylation at 80 - 280 °C for 2 - 45 h. The present invention provides a method for efficiently and highly selectively carbonylating cyclic ethers as substrates to synthesize dicarboxylic acids. It overcomes the limitation in the existing carbonylation reaction that cyclic ethers can only synthesize monocarboxylic acids.

Description

Technical Field

[0001] The present invention belongs to the technical field of chemical synthesis, and particularly relates to a method for highly selectively preparing dicarboxylic acids by carbonylation reaction using cyclic ethers as raw materials. Background Art

[0002] Dicarboxylic acids are a very important class of chemical substances and are widely used in industries such as plastics and medicine. Ethers are inexpensive and basic chemicals that can be obtained from various sources including biomass, but they are rarely used as substrates for the production of higher carboxylic acids through carbonylation. Generally, the reactivity of ethers is lower than that of olefins and / or alcohols. Buxing Han synthesized valeric acid and dimethylbutyric acid (molar ratio 6:4) using IrI4 as the catalyst, LiI as the promoter, and acetic acid as the solvent at 170 °C with tetrahydrofuran as the raw material. And this catalyst has good substrate adaptability and can effectively convert various ethers, such as cycloalkyl ethers, n-alkyl ethers, isoalkyl ethers, and aralkyl ethers, into the corresponding higher carboxylic acids. (Nature Communications, 10, 13463 - 13469). However, the carboxylic acids synthesized using cyclic ethers as substrates are often monocarboxylic acids, that is, only one end of the ether bond forms a carboxylic acid after cleavage, and there is currently no report of forming carboxylic acids at both ends of the ether bond to produce more valuable dicarboxylic acids. Summary of the Invention

[0003] The present invention provides a method for highly selectively preparing dicarboxylic acids by carbonylation reaction using cyclic ethers as raw materials, specifically: reacting the cyclic ether in one step under the conditions of carbon monoxide, hydrogen, a catalyst, a promoter, and a solvent while heating to generate dicarboxylic acids. The present invention also provides the following more preferred schemes, and the following preferred schemes also have corresponding creativity on the basis of the technical concept of preparing dicarboxylic acids described above.

[0004] On the basis of the above scheme, preferably, the cyclic ether substrate can be various substituted and unsubstituted four-ring, five-ring, six-ring, seven-ring, etc. cyclic ethers (tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, furan, tetrahydropyran, cyclohexene oxide, etc.);

[0005] On the basis of the above scheme, preferably, the catalyst is one of rhodium-containing and iridium-containing catalysts;

[0006] On the basis of the above scheme, preferably, the iodine-containing promoter can be one of iodine, organic iodine, hydroiodic acid, and metal iodides;

[0007] On the basis of the above scheme, preferably, the solvent is an organic acid such as acetic acid, propionic acid, trifluoroacetic acid, etc.;

[0008] On the basis of the above scheme, preferably, the hydrogen pressure is between 0.2 - 10 MPa;

[0009] Based on the above scheme, preferably, the carbon monoxide pressure is between 0.2 and 10 MPa;

[0010] Based on the above scheme, preferably, the temperature for temperature rise is 80 - 280 °C;

[0011] Based on the above scheme, preferably, the reaction time is 2 - 45 h;

[0012] Based on the above scheme, preferably, the molar ratio of the catalyst to the cyclic ether substrate is 1:5 to 1:1000;

[0013] Based on the above scheme, preferably, the amount of the promoter iodine is 0.1 - 5 mmol.

[0014] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0015] The present invention provides a method for highly selectively preparing dicarboxylic acid by carbonylation reaction using cyclic ether as a raw material. Different from the preparation of monocarboxylic acid by ether carbonylation reaction in the past, the present invention uses cyclic ether as a substrate and the final product of carbonylation is dicarboxylic acid. Specific Embodiments

[0016] The present invention will be described below through specific examples, but the present invention is not limited thereto.

[0017] In the following examples, the experimental methods are all conventional methods unless otherwise specified; the reagents and materials can be obtained from commercial channels unless otherwise specified.

[0018] Example 1

[0019] 1 mmol of tetrahydrofuran, 0.06 mmol of RhCl3·3H2O, 0.6 mmol of iodine, 3 ml of acetic acid, and 2 ml of water were added to a 50 ml reaction kettle, and then the reaction kettle was sealed. After purging the air in the reaction kettle, 1 MPa of hydrogen and 2 MPa of carbon monoxide were introduced. After the reaction kettle was heated to 170 °C, it was stirred and reacted for 12 h. After the reaction was completed, the reaction solution was fixed in volume, filtered, and used for subsequent inspection and analysis. The yield of adipic acid was 63%.

[0020] The detection instrument for carboxylic acid concentration is Waters H-Class series high performance liquid chromatograph (RID detector, Alltech OA1000 Organic Acids liquid chromatograph (300 mm × 6.5 mm), flow rate 0.6 mL / min, column temperature 60 °C, mobile phase is 0.1 g / L dilute sulfuric acid).

[0021] Calculation of the yield of carboxylic acid:

[0022] Yield of carboxylic acid = (Actual yield of carboxylic acid / Theoretical yield of carboxylic acid) × 100%.

[0023] Example 2

[0024] Add 1 mmol of tetrahydrofuran, 0.06 mmol of RhCl3·3H2O, 0.6 mmol of iodine, 4 ml of acetic acid, and 1 ml of water into a 50 ml reaction kettle, and then seal the reaction kettle. After removing the air in the reaction kettle, introduce 0.5 MPa of hydrogen and 3 MPa of carbon monoxide. Heat the reaction kettle to 170 °C and stir for 10 h. After the reaction is completed, make up the volume of the reaction solution, filter it, and use it for subsequent inspection and analysis. The yield of adipic acid is 57%.

[0025] Example 3

[0026] Add 1 mmol of tetrahydrofuran, 0.06 mmol of RhCl3·3H2O, 0.6 mmol of iodomethane, 3 ml of acetic acid, and 2 ml of water into a 50 ml reaction kettle, and then seal the reaction kettle. After removing the air in the reaction kettle, introduce 0.5 MPa of hydrogen and 3 MPa of carbon monoxide. Heat the reaction kettle to 170 °C and stir for 10 h. After the reaction is completed, make up the volume of the reaction solution, filter it, and use it for subsequent inspection and analysis. The yield of adipic acid is 17%.

[0027] Example 4

[0028] Add 1 mmol of tetrahydropyran, 0.06 mmol of [Rh(CO)2Cl]2, 1 mmol of hydroiodic acid, 3 ml of acetic acid, and 2 ml of water into a 50 ml reaction kettle, and then seal the reaction kettle. After removing the air in the reaction kettle, introduce 3 MPa of hydrogen and 3 MPa of carbon monoxide. Heat the reaction kettle to 170 °C and stir for 10 h. After the reaction is completed, make up the volume of the reaction solution, filter it, and use it for subsequent inspection and analysis. The yield of pimelic acid is 73%.

[0029] Example 5

[0030] Add 1 mmol of tetrahydrofuran, 0.1 mmol of IrCl3, 1 mmol of I2, 3 ml of acetic acid, and 2 ml of water into a 50 ml reaction kettle, and then seal the reaction kettle. After removing the air in the reaction kettle, introduce 3 MPa of hydrogen and 3 MPa of carbon monoxide. Heat the reaction kettle to 170 °C and stir for 10 h. After the reaction is completed, make up the volume of the reaction solution, filter it, and use it for subsequent inspection and analysis. The yield of adipic acid is 6%.

[0031] Example 6

[0032] Add 1 mmol of tetrahydrofuran, 0.1 mmol of RhCl3, 2 mmol of LiI, 3 ml of acetic acid, and 2 ml of water into a 50 ml reaction kettle, and then seal the reaction kettle. After evacuating the air in the reaction kettle, introduce 3 MPa of hydrogen and 3 MPa of carbon monoxide. Heat the reaction kettle to 170 °C, and then stir and react for 10 h. After the reaction is completed, make up the volume of the reaction solution, filter it, and use it for subsequent inspection and analysis. The yield of adipic acid is 12%.

[0033] Example 7

[0034] Add 1 mmol of tetrahydrofuran, 0.1 mmol of RhCl3, 1 mmol of I2, 3 ml of trifluoroacetic acid, and 2 ml of water into a 50 ml reaction kettle, and then seal the reaction kettle. After evacuating the air in the reaction kettle, introduce 3 MPa of hydrogen and 3 MPa of carbon monoxide. Heat the reaction kettle to 170 °C, and then stir and react for 10 h. After the reaction is completed, make up the volume of the reaction solution, filter it, and use it for subsequent inspection and analysis. The yield of adipic acid is 83%.

[0035] The above only expresses the preferred embodiments of the present invention, and the description is relatively specific and detailed. However, it should not be construed as a limitation on the scope of the patent for the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several variations, improvements, and substitutions can be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention shall be subject to the appended claims.

Claims

1. A method for highly selectively preparing dicarboxylic acid from cyclic ether through carbonylation reaction, characterized in that: Follow the steps below: Add cyclic ether as the raw material into a reaction kettle. Under a hydrogen and carbon monoxide atmosphere, use a noble metal catalyst, an iodine-containing promoter, and a solvent, and perform highly selective carbonylation synthesis of dicarboxylic acid under heating conditions; the noble metal catalyst is RhCl3 or [Rh(CO)2Cl]2, the iodine-containing promoter is iodine or hydroiodic acid, and the cyclic ether is one of tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, and tetrahydropyran; the solvent is acetic acid, propionic acid, or trifluoroacetic acid.

2. The method for highly selectively preparing dicarboxylic acid from cyclic ether as raw material through carbonylation reaction according to claim 1, characterized in that: The hydrogen pressure is between 0.2 - 10 MPa.

3. The method for highly selectively preparing dicarboxylic acid by carbonylation reaction using cyclic ether as raw material according to claim 1, characterized in that: The carbon monoxide pressure is between 0.2 - 10 MPa.

4. The method for highly selectively preparing dicarboxylic acid by carbonylation reaction using cyclic ether as raw material according to claim 1, characterized in that: The heating temperature is 80 - 280 °C.

5. The method for highly selectively preparing dicarboxylic acid from cyclic ether as a raw material through a carbonylation reaction according to claim 1, characterized in that: The reaction time is 2 - 45 h.

6. The method for highly selectively preparing dicarboxylic acid from cyclic ether as a raw material through carbonylation reaction according to claim 1, characterized in that: The molar ratio of the noble metal catalyst to the cyclic ether substrate is 1:5 to 1:1000.

7. The method for highly selectively preparing dicarboxylic acid by carbonylation reaction using cyclic ether as a raw material according to claim 1, characterized in that: The iodine amount of the iodine-containing promoter is 0.1 - 5 mmol.