Preparation method of 2, 4, 6-tricyanoethoxy-1, 3, 5-s-triazine

Abstract

The invention discloses a preparation method of 2, 4, 6-tricyanoethoxy-1, 3, 5-s-triazine, which is characterized in that in an organic solvent, the 2, 4, 6-tricyanoethoxy-1, 3, 5-s-triazine is synthesized from cyanuric chloride and 3-hydroxypropionitrile under the action of alkali. The method has the advantages that the process route is simple, the reaction conditions are mild and easy to control, the reaction raw materials, namely the cyanuric chloride and the 3-hydroxypropionitrile can be purchased and obtained, and when strong bases such as sodium hydroxide, potassium hydroxide and tetramethylammonium hydroxide are used, the conversion rate is high, and the reaction time is short.

Description

Technical Field

[0001] The invention relates to the technical field of compound synthesis, and in particular to a method for preparing s-triazine compounds. Background Art

[0002] The addition of cyanoethoxy groups to lithium-ion battery electrolytes has the effect of inhibiting gas production and improving high voltage tolerance, and has little adverse effect on impedance. Therefore, the addition of cyanoethoxy groups to lithium-ion battery electrolytes is beneficial to improving battery performance.

[0003] s-Triazine is a six-membered heterocyclic ring with weak alkalinity, which can moderately inhibit the acidity of lithium-ion battery electrolyte.

[0004] 2,4,6-tricyanoethoxy-1,3,5-s-triazine has the above two groups, and has the advantages of both in lithium-ion battery electrolytes, and can reduce the amount of addition. Therefore, the research on the preparation method of 2,4,6-tricyanoethoxy-1,3,5-s-triazine is of relatively high value. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine, which has the advantages of easy-to-obtain raw materials, simple preparation process, mild and controllable conditions and high yield.

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

[0007] 2,4,6-Trichloro-1,3,5-s-triazine is also known as trichloronitrile. For the sake of simplicity, it is referred to as trichloronitrile in this article. Its structural formula is as follows: ; The structure of 3-hydroxypropionitrile is: .

[0008] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine, the base is selected from one of sodium carbonate, potassium carbonate, tetramethylammonium hydroxide, sodium hydroxide and potassium hydroxide.

[0009] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine, the molar amount of the base fed is 3 to 3.3 times the molar amount of tricyandiamide.

[0010] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine, the molar ratio of the trimerized cyanocyanate to 3-hydroxypropionitrile is 1:3 to 1:3.3.

[0011] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine, the organic solvent is selected from one or more of acetonitrile, acetone, N,N-dimethylformamide, dichloromethane, dichloroethane, tetrahydrofuran, benzene, toluene, dimethylethylbenzene, chloroform, carbon tetrachloride, trichloroethane, tetrachloroethane, 1,4-dioxane, and diethyl ether.

[0012] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine, the organic solvent is selected from one of acetonitrile, N,N-dimethylformamide and 1,4-dioxane.

[0013] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine, the amount of the organic solvent used is 5 to 10 times the mass of tricyanamide.

[0014] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine, the reaction temperature is 50-120°C.

[0015] Furthermore, in the aforementioned method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine, the reaction time is 3 to 12 hours.

[0016] The invention has the advantages of providing a preparation method of 2,4,6-tricyanoethoxy-1,3,5-s-triazine, the preparation method has a simple process route, mild reaction conditions, easy control, the reacting raw materials trichloronitrile and 3-hydroxypropionitrile can be purchased, the conversion rate is high and the reaction time is short when a strong base such as sodium hydroxide, potassium hydroxide and tetramethylammonium hydroxide is used, and the conversion rate reaches more than 80% when tetramethylammonium hydroxide is used. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is the liquid chromatogram of the product prepared in Example 1. Implementation

[0018] The preparation method of 2,4,6-tricyanoethoxy-1,3,5-s-triazine of the present invention is described in detail below through specific examples.

[0019] Example 1: In a 500mL three-necked flask equipped with a stirrer, condenser, and thermometer, add 200g acetonitrile, 37g trichloronitrile, and 46g 3-hydroxypropionitrile, stir and heat to 50°C, add 25g sodium hydroxide, react at 50°C for 4 hours, then cool down to terminate the reaction, filter the reaction solution, collect the precipitated crystals, wash the crystals with water and ether twice, and dry to obtain 42.6g 2,4,6-tricyanoethoxy-1,3,5-s-triazine, with a purity (liquid phase) of 99.67% and a reaction conversion rate of 74%. The liquid chromatogram of the product is shown in the figure below: Figure 1 As shown, Figure 1 The peak at 14.86' is the product peak.

[0020] Example 2: In a 500mL three-necked flask equipped with a stirrer, a condenser, and a thermometer, 300g of tetrahydrofuran, 37g of trichloronitrile, and 43g of 3-hydroxypropionitrile were added, the temperature was raised to 66°C with stirring, 33.6g of potassium hydroxide was added, and the reaction was allowed to proceed at 66°C for 3 hours before the temperature was lowered to terminate the reaction. The reaction solution was filtered, and the precipitated crystals were collected. The crystals were washed with water and ether twice, and then dried to obtain 44g of 2,4,6-tricyanoethoxy-1,3,5-s-triazine with a purity (liquid phase) of 99.73% and a reaction conversion rate of 76%.

[0021] Example 3: In a 500mL three-necked flask equipped with a stirrer, a condenser, and a thermometer, 250g of 1,4-dioxane, 37g of trichloronitrile, and 47g of 3-hydroxypropionitrile were added, stirred, and the temperature was raised to 90°C, 70g of sodium carbonate was added, and the reaction was carried out at 100°C for 12 hours, and then the temperature was lowered to terminate the reaction. The reaction solution was filtered, and the precipitated crystals were collected. The crystals were washed with water and ether twice, and then dried to obtain 33.5g of 2,4,6-tricyanoethoxy-1,3,5-s-triazine, with a purity (liquid phase) of 99.43% and a reaction conversion rate of 58%.

[0022] Example 4: In a 500mL three-necked flask equipped with a stirrer, a condenser, and a thermometer, 350g of toluene, 37g of trichloronitrile, and 47g of 3-hydroxypropionitrile were added, stirred, and the temperature was raised to 90°C, 91g of potassium carbonate was added, and the reaction was carried out at 120°C for 12 hours, and then the temperature was lowered to terminate the reaction. The reaction solution was filtered, and the precipitated crystals were collected. The crystals were washed with water and ether twice, and then dried to obtain 36g of 2,4,6-tricyanoethoxy-1,3,5-s-triazine, with a purity (liquid phase) of 99.51% and a reaction conversion rate of 63%.

[0023] Example 5: In a 500mL three-necked flask equipped with a stirrer, a condenser, and a thermometer, 370g of xylene, 37g of trichloronitrile, and 47g of 3-hydroxypropionitrile were added, stirred, and the temperature was raised to 90°C, 57g of tetramethylammonium hydroxide was added, and the reaction was allowed to proceed at 90°C for 3 hours, and then the temperature was lowered to terminate the reaction. The reaction solution was filtered, and the precipitated crystals were collected. The crystals were washed with water and ether twice, and then dried to obtain 46g of 2,4,6-tricyanoethoxy-1,3,5-s-triazine, with a purity (liquid phase) of 99.73% and a reaction conversion rate of 80%.

[0024] Example 6: In a 500mL three-necked flask equipped with a stirrer, a condenser, and a thermometer, 185g of N,N-dimethylformamide, 37g of trichloronitrile, and 47g of 3-hydroxypropionitrile were added, stirred, and the temperature was raised to 90°C. 57g of tetramethylammonium hydroxide was added, and the reaction was allowed to proceed at 90°C for 3 hours, and then the temperature was lowered to terminate the reaction. The reaction solution was filtered, and the precipitated crystals were collected. The crystals were washed with water and ether twice, and then dried to obtain 47.8g of 2,4,6-tricyanoethoxy-1,3,5-s-triazine, with a purity (liquid phase) of 99.72% and a reaction conversion rate of 83%.

[0025] The above examples show that trichloronitrile and 3-hydroxypropionitrile can react with alkali in an organic solvent to obtain 2,4,6-tricyanoethoxy-1,3,5-s-triazine, especially under the action of tetramethylammonium hydroxide, the reaction conversion rate reaches 83%.

[0026] In the above examples, only acetonitrile, tetrahydrofuran, 1,4-dioxane, toluene, xylene and N,N-dimethylformamide are given as examples of organic solvents for the reaction. The organic solvent for the reaction can also be selected from acetone, dichloromethane, dichloroethane, benzene, toluene, dimethylethylbenzene, chloroform, carbon tetrachloride, trichloroethane, tetrachloroethane, ether, etc., as long as the reactants trichloronitrile and 3-hydroxypropionitrile can be dissolved to form a homogeneous reaction system and the product can be easily precipitated after cooling.

[0027] The invention has the advantages of providing a preparation method of 2,4,6-tricyanoethoxy-1,3,5-s-triazine, wherein the preparation method has a simple process route, mild reaction conditions, and is easy to control; the reaction raw materials, trichloronitrile and 3-hydroxypropionitrile, can be purchased; when a strong base such as sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide is used, the conversion rate is high and the reaction time is short; in particular, when tetramethylammonium hydroxide is used, the conversion rate reaches more than 80%, and thus the method is suitable for industrial production.

Claims

1. Preparation method of 2,4,6-tricyanoethoxy-1,3,5-s-triazine. Trichloronitrile and 3-hydroxypropionitrile are dissolved in an organic solvent, and 2,4,6-tricyanoethoxy-1,3,5-s-triazine is synthesized under the action of a base. The structural formula of 2,4,6-tricyanoethoxy-1,3,5-s-triazine is as follows: 。 2. The method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine according to claim 1, Features: The alkali is selected from one of sodium carbonate, potassium carbonate, tetramethylammonium hydroxide, sodium hydroxide and potassium hydroxide.

3. The method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine according to claim 1, Features: The molar amount of the alkali added is 3 to 3.3 times the molar amount of trimerized cyanamide.

4. The method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine according to claim 1, Features: The molar ratio of trimerized chloronitrile to 3-hydroxypropionitrile is 1:3~1:3.

3.

5. The method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine according to claim 1, Features: The organic solvent is selected from one or more of acetonitrile, acetone, N,N-dimethylformamide, dichloromethane, dichloroethane, tetrahydrofuran, benzene, toluene, dimethylethylbenzene, chloroform, carbon tetrachloride, trichloroethane, tetrachloroethane, 1,4-dioxane, and diethyl ether.

6. The method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine according to claim 5, Features: The organic solvent is selected from one of acetonitrile, N,N-dimethylformamide and 1,4-dioxane.

7. The method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine according to claim 5 or 6, Features: The amount of organic solvent used is 5 to 10 times the mass of trimeronitrile.

8. The method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine according to claim 1, Features: The reaction temperature is between 50°C and 120°C.

9. The method for preparing 2,4,6-tricyanoethoxy-1,3,5-s-triazine according to claim 1, Features: The reaction time is 3 to 12 hours.

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