A green synthesis of N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide)

Abstract

The application belongs to the technical field of organic compound preparation, and particularly relates to a preparation method of N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide). 4,4'-diaminobenzophenone and m-nitrobenzoyl chloride are used as raw materials, the raw materials are mixed and reacted in the presence of a strong polar organic base solvent, a polar precipitant is added after the reaction, and high-purity N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) is obtained after filtration. The purity of the obtained product can reach more than 99.9% without purification, the purity meets the use requirements of electronic-grade products, a single reaction solvent can be repeatedly recovered and reused, the reaction condition is mild, the product does not need secondary refining, the purity requirement can be met, the product is environmentally friendly, the operation is simple, the three wastes are less, and the method is suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The application relates to a green synthesis method of N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide), and belongs to the technical field of organic synthesis. BACKGROUND

[0002] Polyimide (PI) is an aromatic heterocyclic polymer compound containing imide chain segments in a molecular structure, is one of the best heat-resistant varieties in engineering plastics at present, and is widely applied in the fields of aviation, aerospace, microelectronics, nanometer, liquid crystal, laser and the like. The polyimide is praised as a top material of a polymer material pyramid, and is also called an "able hand for solving problems", and even some people in the industry believe that "there will be no microelectronic technology today without polyimide. In recent years, the research, development and utilization of PI are listed as one of the development focuses of new chemical materials in the 21st century. The polyimide, due to the characteristics of high temperature resistance, high strength, corrosion resistance, good insulation, simple film forming process and the like, is an excellent functional material and can meet the performance requirements of LCD (liquid crystal display). Whether as a structural material or as a functional material, the polyimide has great application prospects.

[0003] N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) is one of important raw materials for preparing a photosensitive polyimide resin, and a synthesis route thereof is referred to patent literature CN102549497.A. An existing synthesis method of 2,2-bis[(3-amino benzamide)-4-hydroxyphenyl] hexafluoropropane is that 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane is amidated with m-nitrobenzoyl chloride to obtain the product, the m-nitrobenzoyl chloride has a large dosage and strong corrosion, and is extremely easy to cause rust of production equipment, thereby causing serious safety hazards. SUMMARY

[0004] In view of the deficiencies of the existing synthesis route, the application provides a green synthesis method of N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide).

[0005] The raw material used in the application is non-corrosive, the application has low requirements on equipment, high safety, uses a single reaction solvent ethylene glycol butyl ether for repeated recovery and reuse, does not need secondary refining, can meet the purity requirements, is simple to operate, has less waste, is friendly to the environment, and is suitable for industrial production.

[0006] The specific technical scheme of the application is as follows:

[0007] N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) has the structure shown in the following formula I:

[0008]

[0009] A second object of the present application is to provide a method for preparing N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) as described above.

[0010] The method for preparing N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) comprises the following steps: 4,4'-diaminobenzophenone is mixed with ethylene glycol butyl ether to form a homogeneous solution, and then m-nitrobenzoyl chloride dissolved in ethylene glycol butyl ether is added dropwise at 0-25°C. After the dropwise addition, the reaction is carried out at 15-30°C for 1-2 hours. After the reaction, the product N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) is obtained through post-treatment.

[0011]

[0012] The method for preparing N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) comprises the following steps:

[0013] 4,4'-diaminobenzophenone is mixed with ethylene glycol butyl ether to form a homogeneous solution, and then m-nitrobenzoyl chloride dissolved in ethylene glycol butyl ether is added dropwise at 0-25°C. After the dropwise addition, the reaction is carried out at 15-30°C for 1-2 hours. After the reaction, the product N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) is obtained through post-treatment.

[0014] According to the present application, preferably, the post-treatment is as follows: within 0.5-1 hours after the reaction, a polar precipitant is added to the reaction solution, after the addition, the reaction solution is heated to 30-70°C, and stirring is continued for 1-5 hours. After the precipitation, the temperature is lowered to 0-10°C, and stirring is continued for 0.5-1 hour. Filtration is performed, and the product is washed with the polar precipitant. The product is dried at 60-100°C under vacuum at 0.090-0.095 MPa to obtain pure N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide).

[0015] According to the present application, preferably, the purity of the obtained product can reach more than 99.9% without purification, which meets the purity requirement of electronic-grade products. The single reaction solvent ethylene glycol butyl ether can be repeatedly recovered and reused. The product does not need secondary refining, and the purity requirement can be met. The operation is simple, and the method is suitable for industrial production.

[0016] According to the present application, preferably, the polar precipitant is one of methanol, ethanol, isopropyl alcohol, 1,4-dioxane, and acetone.

[0017] According to the present application, preferably, the mass ratio of the polar precipitant to ethylene glycol butyl ether is 2:1-10:1.

[0018] More preferably, the mass ratio of the polar precipitant to ethylene glycol butyl ether is 4:1-5:1.

[0019] According to the application, the mass of the ethylene glycol butyl ether is preferably 1:2.0-5.0 of the mass of the 4,4'-diaminobenzophenone.

[0020] According to the application, the precipitating liquid can be easily separated from the strong polar organic base solvent used in the solvent recovery, which helps to improve the purity of the product and reduce the loss of the product to improve the yield.

[0021] According to the application, the molar ratio of the 4,4'-diaminobenzophenone to the m-nitrobenzoyl chloride is preferably 1:2.0-2.5, and more preferably 1:2.1-2.2.

[0022] The main purpose of the ethylene glycol butyl ether of the application is to provide a homogeneous medium for the reaction, to dissolve the raw materials and to absorb the hydrogen chloride acid gas generated in the reaction, to reduce the generation of impurities and to promote the reaction equilibrium to proceed to the right.

[0023] According to the application, the mass ratio of the 4,4'-diaminobenzophenone to the ethylene glycol butyl ether is preferably 1:2.0-5.0.

[0024] According to the application, the mass ratio of the m-nitrobenzoyl chloride to the ethylene glycol butyl ether is preferably 1:0.2-1:2.0.

[0025] The application has the following beneficial effects:

[0026] 1. The ethylene glycol butyl ether of the application not only can dissolve the raw materials as a reaction solvent, but also can be used as an acid-binding agent, which can greatly improve the rate and selectivity of the reaction system, thereby promoting the reaction to proceed in the direction of the desired product, reducing side reactions, and obtaining the target product with high yield and high purity after adding the precipitating liquid at the end of the reaction. The product does not need further improvement in purity, and the purity of the product can reach more than 99.9%, meeting the purity requirements of electronic-grade products. The application is safe, environmentally friendly, and suitable for industrial production.

[0027] 2. The product obtained by the method of the application has a purity of more than 99.9% without purification, meeting the purity requirements of electronic-grade products. The single reaction solvent can be repeatedly recovered and reused, and the product does not need secondary refining, meeting the purity requirements. The operation is simple, the amount of waste is less, the environment is friendly, and the application is suitable for industrial production. DETAILED DESCRIPTION

[0028] The application will be further described in detail below with reference to specific examples, which are only illustrative and do not limit the scope of protection.

[0029] Unless otherwise specified, each raw material used in the following examples is a commercially available product.

[0030] Example 1

[0031] The preparation method of N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) is as follows:

[0032] 1) 183.15 g (0.987 mol) of m-nitrobenzoyl chloride was added to a beaker containing 183.15 g of ethylene glycol butyl ether, and stirred to obtain a m-nitrobenzoyl chloride solution;

[0033] 2) 99.76 g (0.47 mol) of 4,4'-diaminobenzophenone was added to a three-necked flask containing 199.52 g of ethylene glycol butyl ether, and stirred until completely dissolved, and then cooled to 20°C to obtain a 4,4'-diaminobenzophenone solution;

[0034] 3) The m-nitrobenzoyl chloride solution was added dropwise to the three-necked flask of step 2) using a peristaltic pump through a latex tube, the dropwise addition time was 0.5 h, the temperature during the reaction was less than 30°C, after the dropwise addition was completed, the temperature was adjusted to 25°C, and the reaction was continued for 2 h, after the reaction was completed, the reaction liquid was added dropwise into 1530.68 g of methanol to precipitate, after the dropwise addition was completed, the temperature was increased to 60°C and stirred for 0.5 h, the temperature was then decreased to 10°C and continued to stir for 0.5 h, filtered, washed with 300 ml of methanol, and dried at 85°C under vacuum-0.095 MPa to obtain HFN pure product. The yield was 96.3%, and the product purity was 99.92%.

[0035] Example 2

[0036] The preparation method of N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) is as follows:

[0037] 1) 191.87 g (1.034 mol) of m-nitrobenzoyl chloride was added to a beaker containing 287.81 g of ethylene glycol butyl ether, and stirred to obtain a m-nitrobenzoyl chloride solution;

[0038] 2) 99.76 g (0.47 mol) of 4,4'-diaminobenzophenone was added to a three-necked flask containing 199.52 g of ethylene glycol butyl ether, and stirred until completely dissolved, and then cooled to 20°C to obtain a 4,4'-diaminobenzophenone solution;

[0039] 3) The m-nitrobenzoyl chloride solution was added dropwise into the three-neck flask of step 2) by using a peristaltic pump through a latex tube, the dropwise time was 0.5 h, the temperature during the reaction should not exceed 30 °C, after the dropwise addition was completed, the temperature was adjusted to 25 °C, and the reaction was continued for 2 h. After the reaction was completed, the reaction solution was added dropwise into 1949.32 g of methanol to precipitate, after the dropwise addition was completed, the temperature was increased to 60 °C and stirred for 0.5 h, then the temperature was decreased to 10 °C and stirred for another 0.5 h, then filtered, washed with 300 ml of methanol, and dried at 85 °C under vacuum-0.095 MPa to obtain the pure HFN product, the yield was 96.6%, and the product purity was 99.95%.

[0040] Example 3

[0041] The preparation method of N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) is as follows:

[0042] 1) 191.87 g (1.034 mol) of m-nitrobenzoyl chloride was added into a beaker containing 249.43 g of ethylene glycol butyl ether, and stirred until uniform to obtain a m-nitrobenzoyl chloride solution;

[0043] 2) 99.76 g (0.47 mol) of 4,4'-diaminobenzophenone was added into a three-neck flask containing 199.52 g of ethylene glycol butyl ether, and stirred until completely dissolved, then the temperature was decreased to 20 °C to obtain a 4,4'-diaminobenzophenone solution;

[0044] 3) The m-nitrobenzoyl chloride solution was added dropwise into the three-neck flask of step 2) by using a peristaltic pump through a latex tube, the dropwise time was 0.5 h, the temperature during the reaction should not exceed 30 °C, after the dropwise addition was completed, the temperature was adjusted to 25 °C, and the reaction was continued for 2 h. After the reaction was completed, the reaction solution was added dropwise into 1795.8 g of methanol to precipitate, after the dropwise addition was completed, the temperature was increased to 60 °C and stirred for 0.5 h, then the temperature was decreased to 10 °C and stirred for another 0.5 h, then filtered, washed with 300 ml of methanol, and dried at 85 °C under vacuum-0.095 MPa to obtain the pure HFN product, the yield was 97.1%, and the product purity was 99.93%.

[0045] Comparative Example 1

[0046] The preparation method of N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) is as follows:

[0047] Into a beaker containing 226.75 g of pyridine, 226.75 g (1.222 mol) of m-nitrobenzoyl chloride was added and stirred to homogeneity and kept ready for use. Into a three-necked flask containing 199.52 g of pyridine, 99.76 g (0.47 mol) of 4,4'-diaminobenzophenone was added and stirred to complete dissolution. After complete dissolution, the temperature was lowered to 40°C and the ready prepared mixture was added dropwise into the three-necked flask using a peristaltic pump through a rubber tube. The dropwise addition was carried out for 0.5 h and the temperature was not allowed to exceed 35°C during the reaction. After completion of the dropwise addition, the temperature was adjusted to 30°C and the reaction was continued for 2 h. After completion of the reaction, the reaction mixture was added dropwise into 1278.81 g of methanol to precipitate. After completion of the dropwise addition, the temperature was raised to 60°C and stirred for 1 h. The temperature was lowered to 25°C and stirring was continued for 0.5 h. The product was filtered, washed with 300 ml of methanol and dried at 85-90°C under vacuum at 0.095 MPa to obtain the pure product HFN. The yield was 79.1% and the purity was 92.85%.

[0048] Comparative Example 2

[0049] The procedure described in Example 1 was followed except that,

[0050] Step (1) N-methyl pyrrolidone was used instead of ethylene glycol butyl ether and the procedure described in Example 1 was followed. The yield of the product was 75.3% and the purity was 88.6%.

[0051] Comparative Example 3

[0052] The procedure described in Example 1 was followed except that,

[0053] Step (1) acetone was used instead of ethylene glycol butyl ether and the procedure described in Example 1 was followed. The yield of the product was 76.8% and the purity was 89.3%.

[0054] Comparative Example 4

[0055] The procedure described in Example 1 was followed except that,

[0056] Step (1) methanol was used instead of ethylene glycol butyl ether and the procedure described in Example 1 was followed. The yield of the product was 75.5% and the purity was 89.9%.

[0057] From the above, it can be seen from Comparative Examples 2 to 4 that the use of N-methyl pyrrolidone, acetone, methanol and ethanol instead of ethylene glycol butyl ether resulted in a significant decrease in the yield of the product.

[0058] Experimental Example

[0059] 1. The amount of ethylene glycol butyl ether used in Example 1 was varied and was 50 g, 61 g, 92 g, 300 g and 360 g respectively. The procedure described in Example 1 was followed and the yield and purity of the product were compared after completion of the reaction. The results are given in Table 1.

[0060] Table 1

[0061] Amount of ethylene glycol butyl ether used % Yield % Purity 50g 78.4 76.5 61g 83.5 82.8 92g 84.4 84.8 183.6g 96.3 99.92 300g 92.5 92 360g 88.9 91

[0062] From the data in Table 1, it can be seen that the yield is low when the amount of ethylene glycol butyl ether is too small. With the increase of the amount of ethylene glycol butyl ether, the yield gradually increases, but when the amount of ethylene glycol butyl ether is too large, the yield begins to decline. Too large amount of ethylene glycol butyl ether affects the yield of the product and causes side reactions, which affects the purity of the product.

[0063] 2. The reaction time in Example 1 was changed, and the reaction time was 5 h, 4 h, 3.5 h, 2 h, 1 h, and 0.5 h, respectively. Other conditions were the same as in Example 1. After the reaction, the yield and purity were compared, and the results are shown in Table 2.

[0064] Table 2

[0065] Reaction time % Yield % Purity 5h 96.2 98.8 4h 96.4 98.9 3.5h 96.3 98.8 2h 96.3 99.92 1h 95.8 98.5 0.5h 93.0 95

[0066] From the data in Table 2, it can be seen that the reaction is not complete when the reaction time is too short, resulting in residual raw materials, low yield, and low purity. With the extension of the reaction time, the yield increases, but when the reaction time is too long, the yield will decrease to some extent. This is because the reaction time is too long, which may cause side reactions and result in a decrease in purity.

Claims

1. A method for preparing N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide), which comprises the following steps: 4,4'-diaminobenzophenone and m-nitrobenzoyl chloride are mixed into a homogeneous solution in the presence of ethylene glycol butyl ether, and then m-nitrobenzoyl chloride dissolved in ethylene glycol butyl ether is added dropwise at 0-25°C, and the reaction is carried out at 15-30°C for 1-2 hours after the dropwise addition, and then the product N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) is obtained by post-treatment after the reaction. 。 2. The production method according to claim 1, characterized by, The method for preparing N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) comprises the following steps: 4,4'-diaminobenzophenone is mixed into a homogeneous solution with ethylene glycol butyl ether, and then m-nitrobenzoyl chloride dissolved in ethylene glycol butyl ether is added dropwise at 0-25°C, and the reaction is carried out at 15-30°C for 1-2 hours after the dropwise addition, and then the product N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) is obtained by post-treatment after the reaction.

3. The method according to claim 2, wherein the post-treatment comprises the following steps: a polar precipitant is added to the reaction solution within 0.5-1 hours after the reaction, the reaction solution is heated to 30-70°C after the addition, and stirring is continued for 1-5 hours, the precipitate is separated after the stirring, the temperature is lowered to 0-10°C, and stirring is continued for 0.5-1 hours, the precipitate is filtered, washed with the polar precipitant, and dried at 60-100°C under vacuum at -0.090-0.095 MPa to obtain the pure product N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide).

4. The method according to claim 3, wherein the polar precipitant is one of methanol, ethanol, isopropanol, 1,4-dioxane, and acetone.

5. The method according to claim 3, wherein the mass ratio of the polar precipitant to ethylene glycol butyl ether is 2:1-10:1, and the mass of ethylene glycol butyl ether is the total mass of ethylene glycol butyl ether used for 4,4'-diaminobenzophenone and m-nitrobenzoyl chloride.

6. The method according to claim 3, wherein the mass ratio of the polar precipitant to ethylene glycol butyl ether is 4:1-5:

1.

7. The method according to claim 2, wherein the molar ratio of 4,4'-diaminobenzophenone to m-nitrobenzoyl chloride is 1:2.0-2.

5.

8. The method according to claim 2, wherein the mass ratio of 4,4'-diaminobenzophenone to ethylene glycol butyl ether is 1:2.0-5.

0.

9. The method according to claim 2, wherein the mass ratio of m-nitrobenzoyl chloride to ethylene glycol butyl ether is 1:0.2-1:2.

0. ​ ​ ​ ​ ​ ​ ​

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