CN116813486A - Preparation method of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane - Google Patents

Abstract

The invention provides a method for preparing 2,2-bis[4-(4-aminophenoxy)phenyl]propanes, which includes the following steps: S1: Dissolve p-chloroaniline and organic base in a solvent, and cool down , add p-toluenesulfonyl chloride, react for a period of time, close the reaction, filter with suction, evaporate the solvent, and obtain N-(4-chlorophenyl)-4-methyl-benzenesulfonamide after post-treatment; S2: N-( 4-chlorophenyl)-4-methyl-benzenesulfonamide, phenol, inorganic base, and solvent are heated to react. After a period of time, they are cooled and filtered to obtain 4-methyl-N-(4-phenoxyphenyl). ) benzene sulfonamide; S3: Mix 4-methyl-N-(4-phenoxyphenyl) benzenesulfonamide, ketone compounds, acidic substances, and solvents, react at high pressure for a period of time, cool, and then post-process 2,2-bis[4-(4-aminophenoxy)phenyl]propane compounds were obtained. The invention has the advantages of easy purchase of raw materials and low cost, simple post-processing operation, high yield, high product purity and less environmental pollution.

Description

A kind of preparation method of 2,2-bis[4-(4-aminophenoxy)phenyl]propanes

Technical field

The invention belongs to the field of raw material preparation, and in particular relates to a preparation method of 2,2-bis[4-(4-aminophenoxy)phenyl]propanes.

Background technique

2,2-bis[4-(4-aminophenoxy)phenyl]propane and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane are synthetic highly branched polyamides. One of the important raw materials of imine resin, therefore, it can be used not only in the field of FCCL, but also in high-temperature resistant polyimide carbon fiber reinforced advanced composite materials. In addition, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane is also a raw material for the synthesis of polymaleimide resin.

Although there are many literatures on the synthesis of 2,2-bis[4-(4-aminophenoxy)phenyl]propane compounds, there are few methods suitable for production:

Gao Yufeng, Wang Tao. Synthesis process of 2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane:, CN112341348A[P].2021.

This article discloses that using hexafluorobisphenol A and 4-nitrochlorobenzene as raw materials, 2,2-bis[4-(4-nitrophenoxy)phenyl]hexafluoropropane is obtained after high-temperature reaction, and then 2,2-bis[4-(4-nitrophenoxy)phenyl]hexafluoropropane is reduced by ferric chloride and hydrazine hydrate to obtain 2,2-bis[4-(4-aminophenoxy) phenyl]hexafluoropropane. The overall yield of this route is ideal, but the reaction temperature in the first step of coupling is too high, the reaction operation in the second step of reduction is more complicated, and the reaction time of the two steps is long.

Jiang Xudong, Wang Zhanqi. A method for rapidly preparing 2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and its intermediates at low temperature, CN105001092A[P].2015.

This article discloses the catalytic coupling of hexafluorobisphenol A and p-nitrochlorobenzene with a metal palladium catalyst to obtain 2,2-bis[4-(4-nitrophenoxy)phenyl]hexafluoro Propane is then subjected to palladium-carbon hydrogenation reduction to obtain 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. Although this route shortens the reaction time and lowers the temperature, both steps require a palladium catalyst, which increases the cost.

In the existing technology that discloses the synthesis process of 2,2-bis[4-(4-aminophenoxy)phenyl]propane compounds, although the overall yield is ideal, it requires a higher temperature reaction, a large amount of metal as a catalyst, and generates waste. liquid, so the production cost is higher. These methods have varying degrees of limitations in the application of industrial production. Therefore, it is urgent to find a more suitable industrial method for preparing 2,2-bis[4-(4-aminophenoxy)phenyl]propane compounds. .

Contents of the invention

In view of this, the present invention aims to propose a preparation method of 2,2-bis[4-(4-aminophenoxy)phenyl]propanes. The raw materials are easy to purchase and the cost is low. The post-processing operation is simple and the harvest High efficiency, high product purity and less environmental pollution, etc.

In order to achieve the above objects, the technical solution of the present invention is implemented as follows:

A preparation method of 2,2-bis[4-(4-aminophenoxy)phenyl]propanes, including the following steps:

S1: Dissolve p-chloroaniline and organic base in the solvent, cool down, add p-toluenesulfonyl chloride, react for a period of time, close the reaction, filter with suction, evaporate the solvent, and obtain N-(4-chlorophenyl)- after post-treatment. 4-methyl-benzenesulfonamide;

S2: Heat N-(4-chlorophenyl)-4-methyl-benzenesulfonamide, phenol, inorganic base and solvent to react. After a period of time, cool and filter to obtain 4-methyl-N-(4 -phenoxyphenyl)benzenesulfonamide;

S3: Mix 4-methyl-N-(4-phenoxyphenyl)benzenesulfonamide, ketone compounds, acidic substances, and solvents, react at high pressure for a period of time, cool, and post-process to obtain 2,2- Bis[4-(4-aminophenoxy)phenyl]propane compounds.

The reaction structural formula is as follows:

Further, the organic base in step S1 includes one or more of triethylamine, N,N-diisopropylethylamine, pyridine, and N,N-dimethylformamide;

Preferably, the organic base is pyridine;

The solvent in step S1 is an aprotic solvent. Preferably, the solvent includes one or more of methylene chloride, 1,2-dichloroethane, and tetrahydrofuran, preferably methylene chloride.

Further, the molar ratio of p-chloroaniline, p-toluenesulfonyl chloride, organic base and solvent in step S1 is 1:1.05:1.0~1.3:5~11, preferably: p-chloroaniline, p-toluenesulfonyl chloride, The molar ratio of organic base and aprotic solvent is 1:1.05:1.2:6.4

Preferably, the cooling temperature in step S1 is 0-25°C, and preferably, the cooling temperature is 8-12°C.

Further, the inorganic base in step S2 is: one of sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium carbonate, and potassium carbonate. Preferably, the inorganic base is cesium carbonate;

The solvent is an aprotic solvent. Preferably, the solvent includes one or more of N,N-dimethylacetamide, dimethylacetamide, 1,4-dioxane, and dimethyl sulfoxide. Preferably, the solvent is N,N-dimethylformamide.

Further, the molar ratio of N-(4-chlorophenyl)-4-methyl-benzenesulfonamide, phenol, inorganic base and solvent is 1:1.1:1.1~2.8:5~11; preferably: N- The molar ratio of (4-hydroxyphenyl)-4-methyl-benzenesulfonamide 4-hydroxyphthalic anhydride, chlorobenzene, inorganic base, and aprotic solvent is 1:1.1:1.4:6.4.

In the step S2, the heating reaction temperature is: 80-110°C. Preferably, the heating reaction temperature is 100-105°C.

Further, the ketone compound in step S3 includes one of acetone and hexafluoroacetone;

The acidic substance is one or more of hydrochloric acid, sulfuric acid, and acetic acid. Preferably, the acidic substance is hydrochloric acid;

The solvent is an aprotic solvent. Preferably, the solvent is one or more of toluene, dioxane, and water. More preferably, the solvent is water.

The ketone compound is acetone, and the prepared 2,2-bis[4-(4-aminophenoxy)phenyl]propane compound is 2,2-bis[4-(4-aminophenoxy) phenyl]propane;

The molar ratio of 4-methyl-N-(4-phenoxyphenyl)benzenesulfonamide, acetone, acidic substance, and solvent is 1:0.49:1.1~2.1:5~35. Preferably, 4-methyl- The molar ratio of N-(4-phenoxyphenyl)benzenesulfonamide, acetone, hydrochloric acid and water is 1:0.49:1.7:28.

Further, the ketone compound is hexafluoroacetone; the prepared 2,2-bis[4-(4-aminophenoxy)phenyl]propane compound is 2,2-bis[4-(4- Aminophenoxy)phenyl]hexafluoropropane;

The molar ratio of 4-methyl-N-(4-phenoxyphenyl)benzenesulfonamide, hexafluoroacetone, acidic substance, and solvent is 1:0.55:1.1~2.0:7~30;

Preferably, the molar ratio of 4-methyl-N-(4-phenoxyphenyl)benzenesulfonamide, hexafluoroacetone, hydrochloric acid and water is 1:0.55:1.5:26.3.

Compared with the existing technology, the preparation method of 2,2-bis[4-(4-aminophenoxy)phenyl]propanes according to the present invention has the following advantages:

The raw materials are easy to purchase and the cost is low, the post-processing operation is simple, the yield is high, the product purity is high and the environmental pollution is small, etc.

Detailed ways

It should be noted that, as long as there is no conflict, the embodiments and features in the embodiments of the present invention can be combined with each other.

The present invention will be described in detail below with reference to examples.

Synthesis of 4-methyl-N-(4-phenoxyphenyl)benzenesulfonamide

Example 1

Add 200.00g (1.57mol) p-chloroaniline, 148.82g (1.88mol) pyridine, 750g (8.83mol) methylene chloride to the reaction bottle, cool to 8°C, add 313.82g (1.65mol) p-toluenesulfonyl chloride, react After 5 hours, the reaction was shut down, suction filtered, and the methylene chloride in the filtrate was evaporated to obtain a crude product. The crude product was added to 200 ml of dioxane for recrystallization, and suction filtration was performed to obtain 434.25g of white solid, with a yield of 98.31% and a purity of 98.25%.

Add 150.00g (0.53mol) N-(4-chlorophenyl)-4-methyl-benzenesulfonamide, 55.11g (0.59mol) phenol, 242.84g (0.74mol) cesium carbonate, 250.00g ( 3.42 mol) DMF, heated to 90-100°C, reacted for 5 hours, turned off the heating, cooled to room temperature, added 150 ml of methanol, solid precipitated, filtered to obtain 171.94 g of white solid, yield 95.16%, purity 99.65%.

Example 2

Add 80.00g (0.63mol) p-chloroaniline, 70.12g (1.88mol) triethylamine, 600g (6.06mol) 1,2-dichloroethane into the reaction bottle, cool to 10°C, add 125.53g (0.66mol) ) p-toluenesulfonyl chloride, react for 5 hours, close the reaction, add water to extract the reaction solution, and evaporate the organic phase to dryness to obtain 141.23g of white solid, with a yield of 79.93% and a purity of 96.97%.

Add 100.00g (0.35mol) N-(4-chlorophenyl)-4-methyl-benzenesulfonamide, 36.74g (0.39mol) phenol, 20.07g (0.70mol) sodium hydroxide, 130.00g to the reaction bottle. (1.49mol) N,N-dimethylacetamide, heat up to 90-100°C, react for 5 hours, turn off the heating, cool to room temperature, add 300ml of water, solid will precipitate, filter with suction, and obtain 106.47g of white solid, yield 88.39%, purity 97.17%.

Example 3

Add 65.00g (0.51mol) p-chloroaniline, 48.45g (0.66mol) DMF, 300g (4.16mol) tetrahydrofuran to the reaction bottle, cool to 12°C, add 101.99g (0.54mol) p-toluenesulfonyl chloride, and close the reaction after 5 hours After the reaction, tetrahydrofuran was evaporated, extracted with ethyl acetate and water, and the organic phase was evaporated to dryness to obtain 109.48g of white solid, with a yield of 76.26% and a purity of 97.41%.

Add 60.00g (0.21mol) N-(4-chlorophenyl)-4-methyl-benzenesulfonamide, 22.05g (0.23mol) phenol, 10.06g (0.42mol) lithium hydroxide, 100g ( 1.14mol) dioxane, raise the temperature to 80-90°C, react for 12 hours, turn off the heating, cool to 70°C, filter with suction, cool the filtrate to room temperature, and filter with suction to obtain 51.41g of white solid, yield 71.12%, purity 93.55 %.

Synthesis of 2,2-bis[4-(4-aminophenoxy)phenyl]propane

Example 1

Add 100.00g (0.30mol) 4-methyl-N-(4-phenoxyphenyl)benzenesulfonamide, 8.38g (0.145mol) acetone, 150g (8.33mol) water, 42g (0.51mol) into the autoclave. ) hydrochloric acid, raise the temperature to 80-90°C under high pressure and sealed conditions, react for 10 hours, turn off the heating, cool to room temperature, exhaust, add 20% sodium hydroxide aqueous solution to adjust to pH=8, suction filter, add 150ml tetrahydrofuran to the filter cake Recrystallize and filter to obtain 53.81g of white solid, with a yield of 90.79% and a purity of 99.76%.

Example 2

Add 110.00g (0.32mol) 4-methyl-N-(4-phenoxyphenyl) benzene sulfonamide, 9.22g (0.16mol) acetone, 300g (3.26mol) toluene, 31.38g (0.32mol) to the autoclave. mol) sulfuric acid, raise the temperature to 90-100°C under high pressure and sealed conditions, react for 8 hours, turn off the heating, cool to room temperature, exhaust, filter to obtain a filter cake, add 150ml of water to the filter cake, and then adjust to pH= with 20% sodium hydroxide aqueous solution 8. Perform suction filtration, add 150 ml of tetrahydrofuran to the filter cake for recrystallization, and obtain 55.60g of white solid by suction filtration, with a yield of 85.23% and a purity of 99.57%.

Example 3

Add 95.00g (0.28mol) 4-methyl-N-(4-phenoxyphenyl) benzenesulfonamide, 7.97g (0.16mol) acetone, 200g (2.27mol) dioxane, 33.63 g (0.56 mol) acetic acid, raise the temperature to 115-120°C under high pressure and sealed conditions, react for 15 hours, turn off the heating, cool to room temperature, exhaust, steam out the dioxane, add 100ml of water, then add 20% hydroxide Adjust the sodium aqueous solution to pH=8, filter with suction, add 100 ml of tetrahydrofuran to the filter cake for recrystallization, and obtain 45.02g of white solid by suction filtration with a yield of 79.91% and a purity of 98.12%.

Synthesis of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane

Example 1

Add 150.00g (0.44mol) 4-methyl-N-(4-phenoxyphenyl) benzenesulfonamide, 210g (11.66mol) water, 55g (0.66mol) hydrochloric acid into the autoclave, and pass in 40.35g ( 0.24mol) hexafluoroacetone, raise the temperature to 90-100°C under high pressure and sealed conditions, react for 12 hours, turn off the heating, cool to room temperature, exhaust, add 20% sodium hydroxide aqueous solution to adjust to pH=8, suction filter, and add to the filter cake Add 150 ml of tetrahydrofuran to recrystallize and filter with suction to obtain 105.80 g of white solid, with a yield of 92.35% and a purity of 99.27%.

Example 2

Add 90.00g (0.26mol) 4-methyl-N-(4-phenoxyphenyl) benzene sulfonamide, 150g (1.63mol) toluene, 13g (0.13mol) sulfuric acid into the autoclave, and pass in 24.21g ( 0.15mol) hexafluoroacetone, raise the temperature to 90-100°C under high pressure and sealed conditions, react for 8 hours, turn off the heating, cool to room temperature, exhaust, filter to obtain a filter cake, add 150ml of water to the filter cake, and adjust with 20% sodium hydroxide aqueous solution to pH=8, perform suction filtration, add 150 ml of tetrahydrofuran to the filter cake for recrystallization, and obtain 60.32g of white solid by suction filtration with a yield of 87.76% and a purity of 98.91%.

Example 3

Add 60.00g (0.18mol) 4-methyl-N-(4-phenoxyphenyl)benzenesulfonamide, 100g (1.14mol) dioxane, and 21.6g (0.36mol) acetic acid to the autoclave. Add 16.14g (0.10mol) hexafluoroacetone, raise the temperature to 115-120°C under high pressure and sealed conditions, react for 15 hours, turn off the heating, cool to room temperature, exhaust, steam out dioxane, add 100ml water, and then add 20 % sodium hydroxide aqueous solution was adjusted to pH=8, filtered with suction, added 100 ml of tetrahydrofuran to the filter cake for recrystallization, and obtained 35.02g of white solid by suction filtration with a yield of 76.43% and a purity of 97.49%.

The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the present invention. within the scope of protection.

Claims (9)

1. A preparation method of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane is characterized by comprising the following steps: the method comprises the following steps:

s1: dissolving p-chloroaniline and organic alkali in a solvent, cooling, adding p-toluenesulfonyl chloride, reacting for a period of time, closing the reaction, carrying out suction filtration, evaporating the solvent, and carrying out post-treatment to obtain N- (4-chlorophenyl) -4-methyl-benzenesulfonamide;

s2: heating N- (4-chlorophenyl) -4-methyl-benzenesulfonamide, phenol, inorganic base and solvent for reaction, cooling after a period of time, and suction-filtering to obtain 4-methyl-N- (4-phenoxyphenyl) benzenesulfonamide;

s3: mixing 4-methyl-N- (4-phenoxyphenyl) benzenesulfonamide, ketone compounds, acidic substances and a solvent, reacting for a period of time at high pressure and temperature, cooling, and post-treating to obtain 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane compounds.

2. The process for producing 2, 2-bis [4- (4-aminophenoxy) phenyl ] propanes according to claim 1, wherein: the organic base in the step S1 comprises one or more of triethylamine, N-diisopropylethylamine, pyridine and N, N-dimethylformamide;

preferably, the organic base is pyridine;

the solvent in the step S1 is an aprotic solvent, preferably, the solvent comprises one or more of dichloromethane, 1, 2-dichloroethane and tetrahydrofuran, preferably dichloromethane.

3. The process for producing 2, 2-bis [4- (4-aminophenoxy) phenyl ] propanes according to claim 1, wherein: the molar ratio of the p-chloroaniline, the p-toluenesulfonyl chloride, the organic base and the solvent in the step S1 is 1:1.05:1.0-1.3:5-11, and is preferably: the molar ratio of the p-chloroaniline to the p-toluenesulfonyl chloride to the organic base to the aprotic solvent is 1:1.05:1.2:6.4

Preferably, the temperature of the cooling in the step S1 is 0-25 ℃, and preferably, the temperature of the cooling is 8-12 ℃.

4. The process for producing 2, 2-bis [4- (4-aminophenoxy) phenyl ] propanes according to claim 1, wherein: the inorganic base in the step S2 is as follows: one of sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium carbonate and potassium carbonate, and preferably, the inorganic base is cesium carbonate;

the solvent is aprotic solvent, preferably, the solvent comprises one or more of N, N-dimethylformamide, dimethylacetamide, 1, 4-dioxane and dimethyl sulfoxide, and preferably, the solvent is N, N-dimethylformamide.

5. The process for producing 2, 2-bis [4- (4-aminophenoxy) phenyl ] propanes according to claim 1, wherein: the molar ratio of N- (4-chlorphenyl) -4-methyl-benzenesulfonamide, phenol, inorganic base and solvent is 1:1.1:1.1-2.8:5-11; preferably, it is: the molar ratio of the N- (4-hydroxyphenyl) -4-methyl-benzenesulfonamide 4-hydroxy phthalic anhydride, chlorobenzene, inorganic base and aprotic solvent is 1:1.1:1.4:6.4;

the temperature rise reaction temperature in the step S2 is as follows: the temperature of 80-110 ℃, preferably the temperature of the rising reaction is 100-105 ℃.

6. The process for producing 2, 2-bis [4- (4-aminophenoxy) phenyl ] propanes according to claim 1, wherein: the ketone compound in the step S3 comprises one of acetone and hexafluoroacetone;

the acidic substance is one or more of hydrochloric acid, sulfuric acid and acetic acid, and preferably, the acidic substance is hydrochloric acid;

the solvent is aprotic, preferably, one or more of toluene, dioxane, and water, more preferably, water.

7. The process for producing 2, 2-bis [4- (4-aminophenoxy) phenyl ] propanes according to claim 1, wherein: the ketone compound is acetone, and the prepared 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane compound is 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane;

the mole ratio of the 4-methyl-N- (4-phenoxyphenyl) benzenesulfonamide, the acetone, the acidic substance and the solvent is 1:0.49:1.1-2.1:5-35, and the mole ratio of the 4-methyl-N- (4-phenoxyphenyl) benzenesulfonamide, the acetone, the hydrochloric acid and the water is 1:0.49:1.7:28.

8. The process for producing 2, 2-bis [4- (4-aminophenoxy) phenyl ] propanes according to claim 1, wherein: the ketone compound is hexafluoroacetone; the prepared 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane compound is 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane;

the molar ratio of the 4-methyl-N- (4-phenoxyphenyl) benzenesulfonamide, hexafluoroacetone, acidic substances and solvents is 1:0.55:1.1-2.0:7-30;

preferably, the molar ratio of 4-methyl-N- (4-phenoxyphenyl) benzenesulfonamide, hexafluoroacetone, hydrochloric acid and water is 1:0.55:1.5:26.3.

9. The process for producing 2, 2-bis [4- (4-aminophenoxy) phenyl ] propanes according to claim 1, wherein: the 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane compound comprises one of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane and 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane.