Process for the preparation of 2,4,6-tricyanoethoxy-1,3,5-triazine

Abstract

The application discloses a preparation method of 2,4,6-tricyanoethoxy-1,3,5-s-triazine, and 2,4,6-tricyanoethoxy-1,3,5-s-triazine is synthesized from trichloroisonitrile and 3-hydroxypropionitrile in an organic solvent under the action of alkali. The method has the advantages of simple process route, mild reaction condition, easy operation, and high conversion rate when strong alkali such as sodium hydroxide, potassium hydroxide and tetramethylammonium hydroxide is used, and short reaction time.

Description

Technical Field

[0001] This invention relates to the field of compound synthesis technology, specifically to a method for preparing triazine compounds. Background Technology

[0002] The addition of cyanoethoxy groups to lithium-ion battery electrolytes can suppress gas generation and improve high-voltage withstand capability, with minimal adverse effects on impedance. Therefore, the addition of cyanoethoxy groups to lithium-ion battery electrolytes is beneficial for improving battery performance.

[0003] Triazine is a six-membered heterocyclic compound with weak basicity, which can moderately suppress the acidity of lithium-ion battery electrolytes.

[0004] 2,4,6-Tricyanoethoxy-1,3,5-homogeneous triazine possesses both of the aforementioned functional groups, combining the advantages of both in lithium-ion battery electrolytes while reducing the required dosage. Therefore, research on the preparation method of 2,4,6-tricyanoethoxy-1,3,5-homogeneous triazine is of considerable value. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing 2,4,6-tricyanethoxy-1,3,5-triazine, which uses readily available raw materials, has a simple preparation process, mild and controllable conditions, and a high yield.

[0006] To achieve the above objectives, the technical solution adopted in this invention is as follows: a method for preparing 2,4,6-tricyanoethoxy-1,3,5-triazine, wherein chloronitrile and 3-hydroxypropionitrile are dissolved in an organic solvent, and 2,4,6-tricyanoethoxy-1,3,5-triazine is synthesized under the action of an alkali. The structural formula of 2,4,6-tricyanoethoxy-1,3,5-triazine is as follows:

[0007] .

[0008] 2,4,6-Trichloro-1,3,5-triazine, also known as chloronitrile, will be referred to as chloronitrile in this article for simplicity. Its structural formula is as follows:

[0009] ;

[0010] The structure of 3-hydroxypropionitrile is:

[0011] .

[0012] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-triazine, the base is selected from one of sodium carbonate, potassium carbonate, tetramethylammonium hydroxide, sodium hydroxide, and potassium hydroxide.

[0013] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-triazine, the molar amount of the alkali is 3 to 3.3 times the molar amount of chloronitrile.

[0014] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-triazine, the molar ratio of the trichloronitrile to 3-hydroxypropionitrile is 1:3 to 1:3.3.

[0015] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-triazine, the organic solvent is selected from one or more of acetonitrile, acetone, N,N-dimethylformamide, dichloromethane, dichloroethane, tetrahydrofuran, benzene, toluene, dimethyl ethylbenzene, chloroform, carbon tetrachloride, trichloroethane, tetrachloroethane, 1,4-dioxane, and diethyl ether.

[0016] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-triazine, the organic solvent is selected from one of acetonitrile, N,N-dimethylformamide, and 1,4-dioxane.

[0017] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-triazine, the amount of the organic solvent used is 5 to 10 times the mass of chloronitrile.

[0018] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-triazine, the reaction temperature is between 50 and 120°C.

[0019] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-triazine, the reaction time is 3 to 12 hours.

[0020] The advantages of this invention are: it provides a method for preparing 2,4,6-tricyanoethoxy-1,3,5-triazine, which has a simple process route, mild reaction conditions, and is easy to control. The reactants, chloronitrile and 3-hydroxypropionitrile, are readily available. The conversion rate is high and the reaction time is short when using strong bases such as sodium hydroxide, potassium hydroxide, or tetramethylammonium hydroxide. In particular, the conversion rate reaches more than 80% when using tetramethylammonium hydroxide. Attached Figure Description

[0021] Figure 1 This is the liquid chromatogram of the product prepared in Example 1. Implementation

[0022] The preparation method of 2,4,6-tricyanethoxy-1,3,5-triazine according to the present invention will be described in detail below through specific embodiments.

[0023] Example 1: In a 500mL three-necked flask equipped with a stirrer, condenser, and thermometer, 200g of acetonitrile, 37g of chloroprene, and 46g of 3-hydroxypropionitrile were added. The mixture was stirred and heated to 50°C. 25g of sodium hydroxide was added, and the reaction was carried out at 50°C for 4 hours. The reaction was then cooled to stop the reaction. The reaction solution was filtered, and the precipitated crystals were collected. The crystals were washed twice with water and ether, and then dried to obtain 42.6g of 2,4,6-tricyanoethoxy-1,3,5-triazine with a purity (liquid phase) of 99.67% and a reaction conversion rate of 74%. The liquid chromatogram of the product is shown below. Figure 1 As shown, Figure 1 The peak value is 14.86'.

[0024] Example 2: In a 500mL three-necked flask equipped with a stirrer, condenser, and thermometer, 300g of tetrahydrofuran, 37g of chloronitrile, and 43g of 3-hydroxypropionitrile were added and stirred until the temperature reached 66°C. Then, 33.6g of potassium hydroxide was added, and the reaction was stopped after reacting at 66°C for 3 hours. The reaction solution was filtered, and the precipitated crystals were collected. The crystals were washed twice with water and then twice with diethyl ether. After drying, 44g of 2,4,6-tricyanoethoxy-1,3,5-triazine was obtained with a purity (liquid phase) of 99.73% and a reaction conversion rate of 76%.

[0025] Example 3: In a 500mL three-necked flask equipped with a stirrer, condenser, and thermometer, 250g of 1,4-dioxane, 37g of chloronitrile, and 47g of 3-hydroxypropionitrile were added. The mixture was stirred and heated to 90°C. 70g of sodium carbonate was added, and the reaction was carried out at 100°C for 12 hours. The reaction was then cooled to stop the reaction. The reaction solution was filtered, and the precipitated crystals were collected. The crystals were washed twice with water and ether, and then dried to obtain 33.5g of 2,4,6-tricyanoethoxy-1,3,5-triazine with a purity (liquid phase) of 99.43% and a reaction conversion rate of 58%.

[0026] Example 4: In a 500mL three-necked flask equipped with a stirrer, condenser, and thermometer, 350g of toluene, 37g of chloronitrile, and 47g of 3-hydroxypropionitrile were added. The mixture was stirred and heated to 90°C. 91g of potassium carbonate was added, and the reaction was carried out at 120°C for 12 hours. The reaction was then cooled to stop the reaction. The reaction solution was filtered, and the precipitated crystals were collected. The crystals were washed twice with water and ether, and then dried to obtain 36g of 2,4,6-tricyanoethoxy-1,3,5-triazine with a purity (liquid phase) of 99.51% and a reaction conversion rate of 63%.

[0027] Example 5: In a 500mL three-necked flask equipped with a stirrer, condenser, and thermometer, 370g of xylene, 37g of chloronitrile, and 47g of 3-hydroxypropionitrile were added. The mixture was stirred and heated to 90°C. Then, 57g of tetramethylammonium hydroxide was added. After reacting at 90°C for 3 hours, the reaction was stopped by cooling. The reaction solution was filtered, and the precipitated crystals were collected. The crystals were washed twice with water and then with diethyl ether. After drying, 46g of 2,4,6-tricyanoethoxy-1,3,5-triazine was obtained with a purity (liquid phase) of 99.73% and a reaction conversion rate of 80%.

[0028] Example 6: In a 500mL three-necked flask equipped with a stirrer, condenser, and thermometer, 185g of N,N-dimethylformamide, 37g of chloronitrile, and 47g of 3-hydroxypropionitrile were added. The mixture was stirred and heated to 90°C. Then, 57g of tetramethylammonium hydroxide was added. After reacting at 90°C for 3 hours, the reaction was stopped by cooling. The reaction solution was filtered, and the precipitated crystals were collected. The crystals were washed twice with water and then with diethyl ether. After drying, 47.8g of 2,4,6-tricyanoethoxy-1,3,5-triazine was obtained with a purity (liquid phase) of 99.72% and a reaction conversion rate of 83%.

[0029] The above examples show that, in an organic solvent, chloronitrile and 3-hydroxypropionitrile can react under alkaline conditions to produce 2,4,6-tricyanoethoxy-1,3,5-triazine, especially under the action of tetramethylammonium hydroxide, the reaction conversion rate reaches 83%.

[0030] The above examples only provide acetonitrile, tetrahydrofuran, 1,4-dioxane, toluene, xylene, and N,N-dimethylformamide as organic solvents for the reaction. Other organic solvents used for the reaction can include acetone, dichloromethane, dichloroethane, benzene, toluene, dimethyl ethylbenzene, chloroform, carbon tetrachloride, trichloroethane, tetrachloroethane, diethyl ether, etc., as long as they can dissolve the reactants chloronitrile and 3-hydroxypropionitrile to form a homogeneous reaction system and allow the product to precipitate easily after cooling.

[0031] The advantages of this invention are: it provides a method for preparing 2,4,6-tricyanoethoxy-1,3,5-triazine, which has a simple process route, mild reaction conditions, and is easy to control. The reaction raw materials, chloronitrile and 3-hydroxypropionitrile, are readily available. The conversion rate is high and the reaction time is short when using strong bases such as sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide. In particular, the conversion rate reaches more than 80% when using tetramethylammonium hydroxide, making it suitable for industrial production.

Claims

A method for preparing 1,2,4,6-tricyanoethoxy-1,3,5-homogeneous triazine involves dissolving chloronitrile and 3-hydroxypropionitrile in an organic solvent and synthesizing 2,4,6-tricyanoethoxy-1,3,5-homogeneous triazine under the action of a base. The base used is tetramethylammonium hydroxide; the organic solvent is selected from N,N-dimethylformamide and xylene; the reaction time is 3 hours. The structural formula of 2,4,6-tricyanoethoxy-1,3,5-triazine is as follows: 。 2. The method for preparing 2,4,6-tricyanethoxy-1,3,5-triazine according to claim 1, characterized in that: The molar amount of alkali added is 3 to 3.3 times the molar amount of chloronitrile.

3. The method for preparing 2,4,6-tricyanethoxy-1,3,5-triazine according to claim 1, characterized in that: The molar ratio of chloronitrile to 3-hydroxypropionitrile is 1:3 to 1:3.

3.

4. The method for preparing 2,4,6-tricyanethoxy-1,3,5-triazine according to claim 1, characterized in that: The amount of organic solvent used is 5 to 10 times the mass of chloronitrile.

5. The method for preparing 2,4,6-tricyanethoxy-1,3,5-triazine according to claim 1, characterized in that: The reaction temperature is between 50℃ and 120℃.

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