The invention relates to N, Napos; green synthesis method of-(carbonyl bis (4, 1-phenylene)) bis (3-nitrobenzamide)

Abstract

The invention belongs to the technical field of preparation of organic compounds, and particularly relates to a preparation method of N, N '-(carbonyl bis (4, 1-phenylene)) bis (3-nitrobenzamide). 4, 4 '-diaminodiphenyl ketone and m-nitrobenzoyl chloride are used as raw materials, the raw materials are respectively subjected to a mixed reaction in the presence of a strong-polarity organic alkali solvent, a polar eluate is added after the reaction, and high-purity N, N'-(carbonyl bis (4, 1-phenylene)) bis (3-nitrobenzamide) is obtained after filtration. The purity of the obtained product can reach 99.9% or above without purification, the use requirement of the purity of an electronic-grade product is met, a single reaction solvent can be repeatedly recycled and reused, the reaction condition is mild, the product can meet the purity requirement without secondary refining, and the product is environment-friendly, simple and convenient to operate, less in three wastes and suitable for industrial production.

Description

Technical Field

[0001] The invention relates to a green synthesis method of N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide), belonging to the technical field of organic synthesis. Background Art

[0002] Polyimide (PI) is an aromatic heterocyclic polymer compound with an imide chain link in its molecular structure. It is one of the most heat-resistant varieties of engineering plastics and is widely used in aviation, aerospace, microelectronics, nanotechnology, liquid crystal, laser and other fields. Polyimide is known as the top material of the pyramid of polymer materials and is also called "a problem-solver". Some industry insiders even believe that "without polyimide, there would be no microelectronics technology today." In recent years, countries have listed the research, development and utilization of PI as one of the development priorities of new chemical materials in the 21st century. Polyimide is an excellent functional material that can meet the performance requirements of LCD (liquid crystal display) due to its high temperature resistance, high strength, corrosion resistance, good insulation and simple film-forming process. Whether as a structural material or as a functional material, it has great application prospects.

[0003] N, N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) is one of the important raw materials for preparing photosensitive polyimide resins. Its synthesis route refers to patent document CN102549497.A. The existing method for synthesizing 2,2-bis[(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane is to obtain the product by amidation of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and m-nitrobenzoyl chloride. The amount of m-nitrobenzoyl chloride is large and it is highly corrosive, which can easily lead to rust of production equipment and cause serious safety hazards. Summary of the invention

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

[0005] The present invention uses non-corrosive raw materials, has low requirements on equipment, is highly safe, uses a single reaction solvent, ethylene glycol butyl ether, is repeatedly recycled and reused, and purity requirements can be met without secondary refining. The invention is simple to operate, has less three wastes, is environmentally friendly, and is suitable for industrial production.

[0006] The specific technical solutions of the present invention are as follows:

[0007] N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide), having the structure described in Formula I below:

[0008]

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

[0010] The preparation method of N, N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) is to use 4,4'-diaminobenzophenone and m-nitrobenzoyl chloride as raw materials, and to carry out condensation reaction in the presence of ethylene glycol butyl ether to obtain N, N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide), and the reaction formula is as follows:

[0011]

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

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

[0014] Preferably, according to the present invention, the post-treatment is to add a polar precipitate to the reaction solution within 0.5-1h after the reaction, and after the addition, the reaction solution is heated to 30-70°C, and stirred for 1-5h. After the precipitate is precipitated, the temperature is reduced to 0-10°C, and stirring is continued for 0.5-1h. The precipitate is filtered, washed with the polar precipitate, and dried at 60-100°C and vacuum -0.090-0.095Mpa to obtain pure N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide).

[0015] Preferably, according to the present invention, the purity of the obtained product can reach more than 99.9% without purification, which meets the purity requirements of electronic-grade products. In addition, the single reaction solvent ethylene glycol butyl ether can be repeatedly recycled and reused. The product does not need secondary refining to meet the purity requirements. The operation is simple and suitable for industrial production.

[0016] Preferably according to the present invention, the polar precipitate is one of methanol, ethanol, isopropanol, 1,4-dioxane and acetone.

[0017] Preferably according to the present invention, the mass ratio of the polar precipitate to ethylene glycol butyl ether is 2:1-10:1.

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

[0019] According to the preferred embodiment of the present invention, the mass of ethylene glycol butyl ether is the total mass of ethylene glycol butyl ether used for mixing with 4,4'-diaminobenzophenone and dissolving m-nitrobenzoyl chloride.

[0020] Preferably according to the present invention, the precipitate can be easily separated from the strong polar organic base solvent used in solvent recovery, which helps to improve the purity of the product, reduce the loss of the product and improve the yield.

[0021] Preferably according to the present invention, the molar ratio of 4,4'-diaminobenzophenone to m-nitrobenzoyl chloride is 1:2.0-2.5, preferably 1:2.1-2.2.

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

[0023] Preferably according to the present invention, the mass ratio of the 4,4'-diaminobenzophenone to ethylene glycol butyl ether is 1:2.0-5.0.

[0024] Preferably according to the present invention, the mass ratio of m-nitrobenzoyl chloride to ethylene glycol butyl ether is 1:0.2-1:2.0.

[0025] The beneficial effects of the present invention are:

[0026] 1. The ethylene glycol butyl ether of the present invention can not only be used as a reaction solvent to dissolve materials, 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 after the reaction is completed, a precipitate is added to obtain a target product with high yield and high purity, and no further improvement of the purity is required. The product purity can reach more than 99.9%, meeting the purity requirements of electronic-grade products, with high safety and more environmental friendliness. A single reaction solvent can be repeatedly recycled and reused, and the operation is simple. The product does not require secondary refining to meet the purity requirements, and is suitable for industrial production.

[0027] 2. The purity of the product obtained by the method of the present invention can reach more than 99.9% without purification, which meets the purity requirements of electronic-grade products. In addition, a single reaction solvent can be repeatedly recycled and reused. The product does not require secondary refining to meet the purity requirements. The operation is simple, the three wastes are less, it is environmentally friendly, and it is suitable for industrial production. DETAILED DESCRIPTION

[0028] The present invention is further described in detail below in conjunction with specific embodiments. The following description is only exemplary and does not limit the scope of protection thereof.

[0029] Unless otherwise specified, all raw materials used in the following examples are commercially available products.

[0030] Example 1

[0031] The preparation method of N, N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) comprises the following steps:

[0032] 1) Add 183.15 g (0.987 mol) of m-nitrobenzoyl chloride into a beaker containing 183.15 g of ethylene glycol butyl ether and stir evenly to obtain a m-nitrobenzoyl chloride solution;

[0033] 2) Add 99.76 g (0.47 mol) of 4,4'-diaminobenzophenone into a three-necked flask containing 199.52 g of ethylene glycol butyl ether, stir until completely dissolved, and cool to 20° C. after complete dissolution to obtain a 4,4'-diaminobenzophenone solution;

[0034] 3) The m-nitrobenzoyl chloride solution was added dropwise to the three-necked flask in step 2) by a peristaltic pump through a latex tube. The addition time was 0.5 h. The temperature during the reaction was less than 30° C. After the 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 to 1530.68 g of methanol for precipitation. After the addition was completed, the temperature was raised to 60° C. and stirred for 0.5 h. The temperature was lowered to 10° C. and stirred for 0.5 h. The mixture was filtered, washed with 300 ml of methanol, and dried at 85° C. under vacuum-0.095 MPa to obtain pure HFN. 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) comprises the following steps:

[0037] 1) Add 191.87 g (1.034 mol) of m-nitrobenzoyl chloride into a beaker containing 287.81 g of ethylene glycol butyl ether and stir evenly to obtain a m-nitrobenzoyl chloride solution;

[0038] 2) Add 99.76 g (0.47 mol) of 4,4'-diaminobenzophenone into a three-necked flask containing 199.52 g of ethylene glycol butyl ether, stir until completely dissolved, and cool to 20° C. after complete dissolution to obtain a 4,4'-diaminobenzophenone solution;

[0039] 3) The m-nitrobenzoyl chloride solution was added dropwise to the three-necked flask in step 2) through a latex tube using a peristaltic pump. The addition time was 0.5 h. The temperature during the reaction could not exceed 30° C. After the 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 to 1949.32 g of methanol for precipitation. After the addition was completed, the temperature was raised to 60° C. and stirred for 0.5 h. The temperature was lowered to 10° C. and continued to stir for 0.5 h. The mixture was filtered, washed with 300 ml of methanol, and dried at 85° C. under vacuum -0.095 MPa to obtain pure HFN with a yield of 96.6% and a product purity of 99.95%.

[0040] Example 3

[0041] The preparation method of N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) comprises the following steps:

[0042] 1) Add 191.87 g (1.034 mol) of m-nitrobenzoyl chloride into a beaker containing 249.43 g of ethylene glycol butyl ether and stir evenly to obtain a m-nitrobenzoyl chloride solution;

[0043] 2) Add 99.76 g (0.47 mol) of 4,4'-diaminobenzophenone into a three-necked flask containing 199.52 g of ethylene glycol butyl ether, stir until completely dissolved, and cool to 20° C. after complete dissolution to obtain a 4,4'-diaminobenzophenone solution;

[0044] 3) The m-nitrobenzoyl chloride solution was added dropwise to the three-necked flask in step 2) through a latex tube using a peristaltic pump. The addition time was 0.5 h. The temperature during the reaction could not exceed 30° C. After the 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 to 1795.8 g of methanol for precipitation. After the addition was completed, the temperature was raised to 60° C. and stirred for 0.5 h. The temperature was lowered to 10° C. and stirred for 0.5 h. The mixture was filtered, washed with 300 ml of methanol, and dried at 85° C. under vacuum-0.095 MPa to obtain pure HFN with a yield of 97.1% and a product purity of 99.93%.

[0045] Comparative Example 1

[0046] The preparation method of N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) comprises the following steps:

[0047] Add 226.75 g (1.222 mol) of m-nitrobenzoyl chloride into a beaker containing 226.75 g of pyridine, stir well, and set aside. 99.76g (0.47mol) of 4,4'-diaminobenzophenone was added to a three-necked flask containing 199.52g of pyridine, and the mixture was stirred until completely dissolved. After complete dissolution, the mixture was cooled to 40°C, and the prepared mixed solution was added dropwise to the three-necked flask through a latex tube using a peristaltic pump. The addition time was 0.5h, and the temperature during the reaction could not exceed 35°C. After the addition was completed, the temperature was adjusted to 30°C, and the reaction was continued for 2h. After the reaction was completed, the reaction solution was added dropwise to 1278.81g of methanol for precipitation. After the addition was completed, the mixture was heated to 60°C and stirred for 1h, cooled to 25°C and continued to stir for 0.5h, filtered, washed with 300ml of methanol, and dried at 85-90°C under vacuum -0.095Mpa to obtain pure HFN with a yield of 79.1% and a product purity of 92.85%.

[0048] Comparative Example 2

[0049] The method described in Example 1 is different in that:

[0050] In step (1), N-methylpyrrolidone was used instead of ethylene glycol butyl ether. The other steps were carried out as in Example 1. The reaction yield of the product was 75.3% and the purity was 88.6%.

[0051] Comparative Example 3

[0052] The method described in Example 1 is different in that:

[0053] In step (1), acetone was used instead of ethylene glycol butyl ether, and the rest was carried out as in Example 1. The reaction yield of the product was 76.8% and the purity was 89.3%.

[0054] Comparative Example 4

[0055] The method described in Example 1 is the same as that described in Example 1, except that

[0056] In step (1), methanol was used instead of ethylene glycol butyl ether, and the rest was carried out as in Example 1. The reaction yield of the product was 75.5% and the purity was 89.9%.

[0057] In summary, it can be seen from Comparative Examples 2-4 that when N-methylpyrrolidone, acetone, methanol, and ethanol are used instead of ethylene glycol butyl ether, the yield of the product is significantly reduced.

[0058] Experimental example

[0059] 1. The amount of ethylene glycol butyl ether in Example 1 was changed to 50g, 61g, 92g, 300g, and 360g respectively. The rest was carried out according to Example 1. After the reaction was completed, the reaction yield and purity were compared. The results are shown in Table 1.

[0060] Table 1

[0061] Dosage of Ethylene Glycol Butyl Ether 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] It can be seen from the data in Table 1 that when the dosage of ethylene glycol butyl ether is too small, the yield is low. As the dosage of ethylene glycol butyl ether increases, the yield gradually increases. However, when the dosage of ethylene glycol butyl ether is too large, the yield begins to show a downward trend. The excessive dosage of ethylene glycol butyl ether affects the product yield and produces side reactions that affect the product purity.

[0063] 2. The reaction time in Example 1 was changed to 5 h, 4 h, 3.5 h, 2 h, 1 h, and 0.5 h, respectively; the rest was carried out as in Example 1. After the reaction was completed, the reaction yield and purity were compared. 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] It can be seen from the data in Table 2 that if the reaction time is too short, the reaction is not complete, resulting in residual raw materials, resulting in relatively low yield and purity. If the reaction time is extended, the yield will increase. However, if the reaction time is too long, the reaction yield will decrease to a certain extent. This is because if the reaction time is too long, side reactions may occur, and the purity will also decrease.

Claims

1. N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide), having the structure described in Formula I below:

2. The method for preparing N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) according to claim 1, wherein 4,4'-diaminobenzophenone and m-nitrobenzoyl chloride are used as raw materials, and in the presence of ethylene glycol butyl ether, a condensation reaction is performed to obtain N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide), and the reaction formula is as follows:

3. The method for preparing N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) according to claim 1, comprising the following steps: The preparation method of N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) comprises the following steps: 4,4'-diaminobenzophenone and ethylene glycol butyl ether are mixed to form a homogeneous solution, and then m-nitrobenzoyl chloride dissolved in ethylene glycol butyl ether is added dropwise at 0-25°C, and the mixture is kept warm at 15-30°C for 1-2 hours. After the reaction, the product N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide) is obtained by post-treatment.

4. The preparation method according to claim 3, characterized in that: The post-treatment is to add a polar precipitate to the reaction solution within 0.5-1h after the reaction, and after the addition, the reaction solution is heated to 30-70°C, and stirred for 1-5h. After the precipitate is precipitated, the temperature is lowered to 0-10°C, and stirred for 0.5-1h. The solution is filtered, washed with the polar precipitate, and dried at 60-100°C under vacuum at -0.090-0.095Mpa to obtain pure N,N'-(carbonylbis(4,1-phenylene))bis(3-nitrobenzamide).

5. The preparation method according to claim 3, characterized in that: The polar precipitate is one of methanol, ethanol, isopropanol, 1,4-dioxane and acetone.

6. The preparation method according to claim 3, characterized in that: The mass ratio of the polar precipitate 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.

7. The preparation method according to claim 3, characterized in that: The mass ratio of the polar precipitate to ethylene glycol butyl ether is 4:1-5:

1.

8. The preparation method according to claim 3, characterized in that: The molar ratio of 4,4'-diaminobenzophenone to m-nitrobenzoyl chloride is 1:2.0-2.5, preferably 1:2.1-2.

2.

9. The preparation method according to claim 3, characterized in that: The mass ratio of the 4,4'-diaminobenzophenone to ethylene glycol butyl ether is 1:2.0-5.

0.

10. The preparation method according to claim 3, characterized in that: The mass ratio of the m-nitrobenzoyl chloride to ethylene glycol butyl ether is 1:0.2-1:2.0.

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