A method for synthesizing dipropargyl carbonate

Abstract

The application discloses a synthesis method of carbonic acid dipropargyl ester, which comprises the following steps: mixing 2-propargyl 1H-imidazole-1-carboxylate and water, and stirring under temperature rising; and after reaction, the reaction liquid is separated, purified, and the target product is obtained. The application has the advantages that no organic solvent is needed in the reaction, environmental pollution is small, the reaction condition is mild, the whole synthesis process is very simple, and the method is suitable for large-scale industrial production.

Description

Technical Field

[0001] This invention relates to the field of carbonate synthesis technology, and particularly to a method for synthesizing diacetylene carbonate. Background Technology

[0002] With the continuous development of the new energy market, lithium-ion batteries are widely used in various industries. Carbonates, as the main solvents or additives in lithium-ion battery electrolytes, are widely used. Therefore, the continuous exploration of the synthesis of novel carbonate structures is of great significance. Diacetylene carbonate, as a carbonate, is widely used in the research of lithium-ion battery electrolytes.

[0003] Currently, there are two main methods for synthesizing propargyl carbonate: 1. Reacting phosgene or solid phosgene with propargyl alcohol. This method requires organic solvents and acid-binding agents, generates a lot of waste, and is not environmentally friendly. See US2018 / 66082; Justus Liebigs Annalen der Chemie, 1955, vol. 596, p. 65.

[0004] II. Preparation by reacting propargyl alcohol with carbon dioxide under certain pressure conditions. This method has harsh reaction conditions and low yield, which is not conducive to industrial production. See Advanced Synthesis and Catalysis, 2011, vol. 353, p. 133 for details.

[0005] Therefore, developing new synthetic methods is of particular importance. Summary of the Invention

[0006] To solve the above-mentioned technical problems, the present invention provides a method for synthesizing diacetylene carbonate. The method has mild reaction conditions, and the reaction process and post-processing are very simple and easy to operate, making it easy for industrial production.

[0007] To solve the above technical problems, the specific technical solution of the present invention is as follows: a method for synthesizing diacetylacetyl carbonate, comprising the following steps: mixing 2-propynyl 1-yl 1H-imidazol-1-carboxylic acid ester and water, heating and stirring; after the reaction is completed, separating the reaction solution, washing with water, collecting the organic layer, and distilling to obtain the target product.

[0008] Furthermore, in the aforementioned method for synthesizing diacetylacetyl carbonate, the mass ratio of 2-propynyl 1-yl 1H-imidazol-1-carboxylic acid ester to water is 1:1 to 1:4.

[0009] Furthermore, in the aforementioned method for synthesizing diacetylacetyl carbonate, 2-propynyl-1-yl-1H-imidazol-1-carboxylic acid ester is mixed with water and stirred for 1 to 6 hours.

[0010] Furthermore, in the aforementioned method for synthesizing diacetylacetyl carbonate, 2-propynyl-1-yl-1H-imidazol-1-carboxylic acid ester is mixed with water and stirred for 1.5 to 4 hours.

[0011] Furthermore, in the aforementioned method for synthesizing diacetylacetyl carbonate, the reaction temperature is 15℃~80℃.

[0012] Furthermore, in the aforementioned method for synthesizing diacetylene carbonate, the reaction temperature is 40℃~50℃.

[0013] Furthermore, in the aforementioned method for synthesizing diacetylene carbonate, after the reaction is completed, the reaction solution is cooled and separated, washed with water, the organic layer is collected, and the target product is obtained by distillation.

[0014] The advantages of this invention are: no organic solvents are required, resulting in less environmental pollution; the reaction conditions are mild; the post-processing is simple and easy to operate; the product has high purity and good yield, which is conducive to large-scale industrial production. Attached Figure Description

[0015] Figure 1 This is the 1H NMR spectrum of the product obtained in Example 1.

[0016] Figure 2 This is the carbon NMR spectrum of the product obtained in Example 1. Detailed Implementation

[0017] The method for synthesizing diacetylene carbonate according to the present invention will be further described in detail below with reference to preferred embodiments.

[0018] Example 1.

[0019] 2-propynyl-1-yl-1H-imidazolium-1-carboxylic acid ester (450 g, 3 mol) was mixed with 900 g of deionized water in a 2 L three-necked flask equipped with a stirrer and reflux condenser. The mixture was heated to 50 °C and stirred. After 4 h, the solid completely dissolved, the reaction was stopped, and the mixture was cooled and separated. The organic layer was washed three times with 200 g of deionized water. The organic layer was collected and distilled to obtain 172 g of the target product (theoretical yield: 207.2 g), with a purity of 99.7% and a yield of 83%. (The simplified 1H NMR spectrum of the target product is shown in the image.) Figure 1 As shown.

[0020] Example 2.

[0021] 2-propynyl-1-yl-1H-imidazolium-1-carboxylic acid ester (450 g, 3 mol) was mixed with 1350 g of deionized water in a 2 L three-necked flask equipped with a stirrer and reflux condenser. The mixture was heated to 50 °C and stirred. After 2.5 h, the solid completely dissolved, the reaction was stopped, and the mixture was cooled and separated. The organic layer was washed three times with 200 g of deionized water. The organic layer was collected and distilled to obtain 176 g of the target product (theoretical yield: 207.2 g), with a purity of 99.7% and a yield of 85%. A simplified 1H NMR spectrum of the target product was obtained. Figure 2 As shown.

[0022] Example 3.

[0023] Using a 2 L three-necked flask equipped with a stirrer and a reflux condenser, 450 g (3 mol) of 2-propynyl-1-yl 1H-imidazolium-1-carboxylic acid ester was mixed with 1350 g of deionized water. The mixture was heated to 40 °C and stirred. After 4 h, the solid was completely dissolved, the reaction was stopped, the mixture was cooled and separated, and the organic layer was washed with deionized water (3 times with 200 g of deionized water). The organic layer was collected and distilled to obtain 166 g of the target product (theoretical yield: 207.2 g), with a purity of 99.6% and a yield of 80%.

[0024] Example 4.

[0025] Using a 2L three-necked flask equipped with a stirrer and a reflux condenser, 450g (3mol) of 2-propynyl-1-yl-1H-imidazolium-1-carboxylic acid ester was mixed with 1800g of deionized water. The mixture was heated to 50℃ and stirred. After 1.5h, the solid was completely dissolved, the reaction was stopped, the mixture was cooled and separated, and the organic layer was washed with deionized water (200g of deionized water for three washes). The organic layer was collected and distilled to obtain 188.6g of the target product (theoretical yield: 207.2g), with a purity of 99.8% and a yield of 91%.

[0026] Example 5.

[0027] Using a 2L three-necked flask equipped with a stirrer and a reflux condenser, 450g (3mol) of 2-propynyl-1-yl-1H-imidazolium-1-carboxylic acid ester was mixed with 1350g of deionized water. The mixture was stirred at 15°C and kept at this temperature for 6 hours. After the solid had completely dissolved, the reaction was stopped, the mixture was cooled, and the liquid was separated. The organic layer was washed three times with 200g of deionized water. The organic layer was collected and distilled to obtain 163.7g of the target product (theoretical yield: 207.2g), with a purity of 99.6% and a yield of 79%.

[0028] Example 6.

[0029] Using a 2L three-necked flask equipped with a stirrer and a reflux condenser, 450g (3mol) of 2-propynyl-1-yl-1H-imidazolium-1-carboxylic acid ester was mixed with 1350g of deionized water. The mixture was heated to 80℃ and stirred. After 1 hour, the solid was completely dissolved, the reaction was stopped, and the mixture was cooled and separated. The organic layer was washed with deionized water (3 times with 200g of deionized water). The organic layer was collected and distilled to obtain 155.7g of the target product (theoretical yield: 207.2g), with a purity of 99.6% and a yield of 75%.

[0030] As can be seen from the above examples: 1. No organic solvents are required in the reaction, resulting in minimal environmental pollution. The reaction conditions are mild, and the entire synthesis process is very simple, making it suitable for large-scale industrial production. 2. Post-processing is easy, purity is high, reaching over 99.5%, and the yield is good. The reaction temperature is controlled at 40℃~50℃, and the reaction time is controlled at 1.5~4 hours, with a yield of over 80%, and even exceeding 90%.

Claims

1. A method for synthesizing diacetylene carbonate, comprising the following steps: 2-propynyl 1-yl 1H-imidazol-1-carboxylic acid ester and water were mixed and heated with stirring at a temperature of 40℃~80℃ for 1~6 hours. After the reaction is complete, the reaction solution is separated and purified to obtain the target product.

2. The method for synthesizing diacetyl carbonate according to claim 1, characterized in that: The mass ratio of 2-propynyl 1-yl 1H-imidazol-1-carboxylic acid ester to water is 1:1 to 1:

4.

3. The method for synthesizing diacetyl carbonate according to claim 1, characterized in that: After mixing 2-propynyl 1-yl 1H-imidazol-1-carboxylic acid ester with water, the reaction time is stirred for 1.5 to 4 hours.

4. A method for synthesizing diacetylene carbonate according to claim 1 or 3, characterized in that: The reaction temperature is 40℃~50℃.

5. A method for synthesizing diacetylene carbonate according to claim 1 or 2, characterized in that: After the reaction is complete, the reaction solution is cooled and separated. The organic layer is washed with water, collected, and then distilled to obtain the target product.

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