The invention relates to 3, 3apos; 4, 4 apos, 4, 4 apos; preparation method of 4-tetraaminobiphenyl

Abstract

The invention provides a preparation method of 3, 3 ', 4, 4'-tetraaminobiphenyl, which comprises the following step of: reacting o-phenylenediamine serving as a raw material in an inert gas atmosphere under the action of a catalyst and a ligand to obtain the 3, 3 ', 4, 4'-tetraaminobiphenyl. According to the invention, o-phenylenediamine is taken as a raw material, and 3, 3 ', 4, 4'-tetraaminobiphenyl is prepared through one-step coupling under the condition of metal catalysis, so that the reaction yield and selectivity are improved, the highest yield is up to 89%, the cost of reaction raw materials is reduced, processes of dangerous reactions such as diazotization and the like are avoided, the reaction safety is improved, the reaction conditions are simplified, and the method is more suitable for industrial production.

Description

Technical Field

[0001] The invention belongs to the field of organic synthesis, and specifically relates to a method for preparing 3,3',4,4'-tetraaminobiphenyl. Background Art

[0002] 3,3′,4,4′-Tetraaminobiphenyl (DAB) is one of the polymer monomers that has been focused on research and application in developed countries, especially those with developed high-tech industries, in recent years. It can be used to synthesize polymer resins and polymer fibers with excellent properties such as PBI. The polymer resin / fiber synthesized with DAB combines special properties such as ultra-high heat resistance, flame retardancy, chemical stability at high temperatures, resistance to sudden temperature changes, dimensional thermal stability, friction resistance, mechanical strength retention, and wearing comfort. It is the "perfect" material that the high-tech field dreams of.

[0003] In addition, 3,3′,4,4′-tetraaminobiphenyl can also be used as a chromogen for visualization of immunohistochemistry of chondrosarcoma slices, breast cancer and brain tissue slices; it can be used as a reagent for spectrophotometric determination of selenium; it can be used to detect peroxidase activity. In the peroxidase reaction, DAB is used as a hydrogen donor in the presence of peroxide, and the oxidized DAB forms an insoluble brown end product, which can be used for immunohistochemical and immunoblot staining analysis. In summary, 3,3′,4,4′-tetraaminobiphenyl can be widely used in aviation, aerospace, military industry, fire protection, fire prevention, new materials, new energy, IVD medical devices and other fields.

[0004] At present, there are few literature reports on the synthesis of 3,3′,4,4′-tetraaminobiphenyl, and 3,3′,4,4′-tetraaminobiphenyl is relatively expensive. Therefore, it is of great significance to seek a new optimized synthesis method for 3,3′,4,4′-tetraaminobiphenyl.

[0005] Publication No. CN119285474A and others provide a method of using 4,4'-diaminobiphenyl as a raw material, and carrying out a diazo coupling reaction with an aromatic diazonium salt under alkaline or neutral conditions to obtain an intermediate 4,4'-diaminobiphenyl diazo compound, and then undergoing a catalytic hydrogenation reduction reaction to obtain the finished product 3,3',4,4'-tetraaminobiphenyl. This method requires the use of diazotization and hydrogenation reactions, and has the disadvantages of poor reaction selectivity and low safety.

[0006] Publication No. CN115108918A and others provide a method of using 4,4′-biphenyldiphenol as a raw material, and reacting it with N,N-dimethylaminosulfonyl chloride in a specified solvent at 40-70°C to perform an esterification reaction to obtain a first intermediate 4,4′-biphenyl di(N,N-dimethylaminosulfonate); then chlorinating it and then performing aminolysis to obtain the product 3,3′,4,4′-tetraaminobiphenyl. This route has the disadvantages of long steps, high pollution, and poor atom economy.

[0007] Patents CN105111092A, CN102173994A, CA2073628A1, US3865876A, etc. disclose a method of obtaining 3,3′,4,4′-tetraaminobiphenyl by reacting 3,3′-dichlorobenzidine and ammonia in water in the presence of a catalyst, wherein the catalyst is cupric chloride, cuprous chloride, etc. This route is relatively simple, but the raw materials are relatively expensive.

[0008] In summary, developing a method for preparing 3,3′,4,4′-tetraaminobiphenyl with high conversion rate, convenient industrial production and safe reaction has become an urgent problem to be solved. Summary of the invention

[0009] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a method for preparing 3,3',4,4'-tetraaminobiphenyl. The method provided by the present invention improves the reaction yield and selectivity, reduces the cost of the reaction raw materials, avoids the process of dangerous reactions such as diazotization, increases the reaction safety, simplifies the reaction conditions, and is more suitable for industrial production.

[0010] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0011] The object of the present invention is to provide a method for preparing 3,3',4,4'-tetraaminobiphenyl, wherein o-phenylenediamine is used as a raw material, and the 3,3',4,4'-tetraaminobiphenyl is obtained by reaction under an inert gas atmosphere in the presence of a catalyst, a ligand and a base.

[0012] Specifically, the catalyst is one or more selected from palladium acetate, 1,1,1,5,5,5-hexafluoroacetylacetonate palladium, palladium chloride, and dichloro[bis(diphenylphosphinophenyl)ether]palladium.

[0013] Specifically, the ligand is one or more selected from glycine, triphenylphosphine, 2,2-bipyridine, tricyclohexylphosphine, and tri-tert-butylphosphine.

[0014] Specifically, the solvent is one or more selected from silver carbonate and silver acetate.

[0015] Specifically, the reaction further requires a solvent, which is one or more selected from N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, and N-methylpyrrolidone.

[0016] Preferably, the solvent, o-phenylenediamine, catalyst, ligand and base are added in sequence, mixed and then filled with inert gas to react.

[0017] Preferably, the volume ratio of the o-phenylenediamine to the solvent is 1:(7-15); more preferably, the volume ratio of the o-phenylenediamine to the solvent can be 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14 or 1:15, etc., but is not limited to the values listed above. Other unlisted values within the above numerical range are equally applicable.

[0018] Specifically, the temperature of the reaction is 110-150 °C, and the time of the reaction is 8-16 h; preferably, the temperature of the reaction can be 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 145 °C or 150 °C, etc., and the time of the reaction can be 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h or 16 h, etc., but is not limited to the values listed above. Other unlisted values within the above numerical range are equally applicable.

[0019] Specifically, the molar ratio of the o-phenylenediamine, the catalyst, the ligand and the base fed is 1:(0.05-0.1):(0.2-0.4):(1-3).

[0020] Specifically, after the reaction, post-treatment is required. The post-treatment is to add water to the reaction product, extract to obtain an aqueous phase, then wash the aqueous phase with ethyl acetate, and then perform vacuum distillation to obtain the 3,3′,4,4′-tetraaminobiphenyl.

[0021] Compared with the prior art, the present invention provides a method for preparing 3,3′,4,4′-tetraaminobiphenyl, which has the following beneficial effects: The present invention uses o-phenylenediamine as a raw material, and under the condition of metal catalysis, 3,3′,4,4′-tetraaminobiphenyl is prepared by one-step coupling, which improves the reaction yield and selectivity, reduces the reaction steps, the highest yield is up to 89%, reduces the cost of reaction raw materials, avoids the process of dangerous reactions such as diazotization, increases the reaction safety, simplifies the reaction conditions, and is more suitable for industrial production. Detailed implementation mode

[0022] To further elaborate on the technical means and effects adopted by the present invention, the following further illustrates the technical solution of the present invention in combination with the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.

[0023] Example 1

[0024] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which includes the following steps. In a reaction flask, first add 10 mL of N,N-dimethylformamide, then add 1.08 g of o-phenylenediamine, 0.224 g of palladium acetate, 0.15 g of glycine, and 5.5 g of silver carbonate. After mixing, stir under nitrogen protection and heat to 140 °C. React for 12 h and monitor the reaction by TLC until the raw materials are completely converted. After the reaction is completed, add 20 ml of water, wash the aqueous layer three times with 10 ml of ethyl acetate, and remove the organic phase solvent by vacuum distillation to obtain 0.96 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl. The reaction yield is 89% and the purity is 97%.

[0025] Example 2

[0026] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as Example 1, except that 0.52 g of palladium hexafluoroacetylacetonate, 0.15 g of glycine, and 5.5 g of silver carbonate are added. Finally, 0.87 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 81% and the purity is 95%.

[0027] Example 3

[0028] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as Example 1, except that 0.18 g of palladium chloride, 0.52 g of triphenylphosphine, and 3.34 g of silver acetate are added. Finally, 0.88 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 82% and the purity is 93%.

[0029] Example 4

[0030] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as Example 1, except that 0.72 g of dichloro[bis(diphenylphosphinophenyl)ether]palladium, 0.31 g of 2,2-bipyridine, and 5.52 g of silver carbonate are added. Finally, 0.82 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 76% and the purity is 94%.

[0031] Example 5

[0032] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as Example 1, except that 0.224 g of palladium acetate, 0.56 g of tricyclohexylphosphine, and 3.34 g of silver acetate are added. Finally, 0.86 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 80% and the purity is 93%.

[0033] Example 6

[0034] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that in Example 1. The difference is that 0.112 g of palladium acetate is added, and finally 0.84 g of white solid, that is, 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 78%, and the purity is 93%.

[0035] Example 7

[0036] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that in Example 1. The difference is that 0.168 g of palladium acetate is added, and finally 0.88 g of white solid, that is, 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 82%, and the purity is 94%.

[0037] Example 8

[0038] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that in Example 1. The difference is that 0.225 g of glycine is added, and finally 0.95 g of white solid, that is, 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 88%, and the purity is 95%.

[0039] Example 9

[0040] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that in Example 1. The difference is that 0.3 g of glycine is added, and finally 0.96 g of white solid, that is, 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 89%, and the purity is 97%.

[0041] Example 10

[0042] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that in Example 1. The difference is that 2.78 g of silver carbonate is added, and finally 0.85 g of white solid, that is, 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 79%, and the purity is 94%.

[0043] Example 11

[0044] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that in Example 1. The difference is that 8.34 g of silver carbonate is added, and finally 0.96 g of white solid, that is, 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 89%, and the purity is 96%.

[0045] Example 12

[0046] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that of Example 1. The difference is that 10 mL of N-methylpyrrolidone is added, and finally 0.93 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 86%, and the purity is 94%.

[0047] Example 13

[0048] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that of Example 1. The difference is that 12 mL of dimethyl sulfoxide is added, and finally 0.92 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 85%, and the purity is 93%.

[0049] Example 14

[0050] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that of Example 1. The difference is that the temperature is raised to 110 °C and the reaction is carried out for 16 h. Finally, 0.93 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 86%, and the purity is 94%.

[0051] Example 15

[0052] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that of Example 1. The difference is that the temperature is raised to 160 °C and the reaction is carried out for 8 h. Finally, 0.95 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 88%, and the purity is 96%.

[0053] Example 16

[0054] This example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that of Example 1. The difference is that the temperature is raised to 130 °C and the reaction is carried out for 14 h. Finally, 0.94 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl, is obtained. The reaction yield is 87%, and the purity is 95%.

[0055] Comparative Example 1

[0056] This comparative example provides a preparation method of 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that of Example 1. The difference is that 0.177 g of cobalt acetate is used as the catalyst and no reaction occurs.

[0057] Comparative Example 2

[0058] This comparative example provides a method for preparing 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that in Example 1, except that 1.06 g of Pd / C 10% is used as the catalyst, and finally 0.05 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl, is obtained, and the reaction yield is 5%.

[0059] Comparative Example 3

[0060] This comparative example provides a method for preparing 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that in Example 1, except that 2.76 g of potassium carbonate is used instead of the base, and finally 0.13 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl, is obtained, and the reaction yield is 12%.

[0061] Comparative Example 4

[0062] This comparative example provides a method for preparing 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that in Example 1, except that no base is added and no reaction occurs.

[0063] Comparative Example 5

[0064] This comparative example provides a method for preparing 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that in Example 1, except that no ligand is added and no reaction occurs.

[0065] Comparative Example 6

[0066] This comparative example provides a method for preparing 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that in Example 1, except that 0.056 g of palladium acetate and 0.075 g of glycine are added, and finally 0.32 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl, is obtained, and the reaction yield is 30% and the purity is 75%.

[0067] Comparative Example 7

[0068] This comparative example provides a method for preparing 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that in Example 1, except that the reaction temperature is 170 °C and the reaction time is 6 h, and finally 0.70 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl, is obtained, and the reaction yield is 65% and the purity is 79%.

[0069] Comparative Example 8

[0070] This comparative example provides a method for preparing 3,3′,4,4′-tetraaminobiphenyl, which is basically the same as that in Example 1, except that the reaction temperature is changed to 100 °C and the reaction time is 20 h, and finally 0.45 g of white solid, namely 3,3′,4,4′-tetraaminobiphenyl, is obtained, and the reaction yield is 42% and the purity is 65%.

[0071] The applicant declares that the present invention illustrates a preparation method of 3,3′,4,4′-tetraaminobiphenyl through the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

[0072] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept scope of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0073] In addition, it should be noted that in the above specific embodiments, the various specific technical features described can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

Claims

1. A preparation method of 3,3',4,4'-tetraaminobiphenyl, characterized in that, In an inert gas atmosphere, o-phenylenediamine is used as a raw material, and under the action of a catalyst, a ligand and a base, the 3,3',4,4'-tetraaminobiphenyl is reacted.

2. The preparation method according to claim 1, characterized in that, The catalyst is one or more selected from palladium acetate, 1,1,1,5,5,5-hexafluoroacetylacetonate palladium, palladium chloride, and dichloro[bis(diphenylphosphinophenyl)ether]palladium.

3. The preparation method according to claim 1, characterized in that, The ligand is one or more selected from glycine, triphenylphosphine, 2,2-bipyridine, tricyclohexylphosphine, and tri-tert-butylphosphine.

4. The preparation method according to claim 1, characterized in that, The alkali is one or more selected from silver carbonate and silver acetate.

5. The preparation method according to claim 1, characterized in that, The reaction further requires a solvent, which is one or more selected from N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, and N-methylpyrrolidone.

6. The preparation method according to claim 5, characterized in that The solvent, o-phenylenediamine, catalyst, ligand and base are added in sequence, mixed and then filled with inert gas to react.

7. The preparation method according to claim 5 or 6, characterized in that The volume ratio of the o-phenylenediamine to the solvent is 1:(7-15).

8. The preparation method according to claim 1, wherein, The reaction temperature is 110-150° C., and the reaction time is 8-16 hours.

9. According to the preparation method described in claim 1, characterized in that, The molar ratio of o-phenylenediamine, catalyst, ligand and base is 1:(0.05-0.1):(0.2-0.4):(1-3).

10. According to the preparation method described in claim 1, characterized in that, After the reaction, post-treatment is required. The post-treatment is to add water to the reaction product, extract to obtain a water phase, wash the water phase with ethyl acetate, and then perform reduced pressure distillation to obtain the 3,3',4,4'-tetraaminobiphenyl.