Method for preparing 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid

Abstract

The present invention relates to the technical field of organic synthesis, and in particular to a method for preparing 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid. The method comprises: mixing 4,4-dihydroxybiphenyl with an alkali metal carbonate and an alkali metal bicarbonate to obtain a mixture; mixing the mixture with a water-soluble high-boiling-point organic solvent, and reacting in a carbon dioxide environment to obtain a reaction product; and dissolving the reaction product in water, adjusting the pH value to 1.0-2.0, and then filtering to obtain 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid. In the present invention, carbon dioxide is used as a raw material, which reduces corrosion to the device, reduces the requirements for the reaction device, and reduces production costs. The crude product has a purity of 99.0% and a yield of 95%, and can be directly used in other reactions without further refining, thereby simplifying post-treatment operations, significantly reducing environmental pollution, improving production efficiency, effectively improving the yield of organic ligands, and meeting market requirements.

Description

A method for preparing 4,4'-dihydroxydiphenyl-3,3'-dicarboxylic acid TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, and particularly relates to a method for preparing 4,4'-dihydroxydiphenyl-3,3'-dicarboxylic acid. BACKGROUND

[0002] 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid is a very important organic intermediate and is a main raw material for the synthesis of metal organic frameworks (MOFs). MOFs are mainly used in gas storage and separation. Patent WO2023147354A1 discloses a method for preparing 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid. Dry 4,4-biphenyldiol and potassium bicarbonate are added to a glass tube, replaced with nitrogen, then filled with carbon dioxide to a pressure of 3.7 MPa, heated to 280°C, the pressure reaches 7.6 MPa, and the reaction continues for 24 hours. This method does not give the yield and purity of the product. The pressure and temperature are very high, and the reaction equipment requirements are high, which is not suitable for large-scale production. Chinese patent CN113999105 discloses a method for preparing 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid. 4,4'-biphenyldiol is mixed with potassium hydroxide, potassium carbonate, and potassium bicarbonate, then added to a 1L autoclave, the autoclave is replaced with carbon dioxide gas, then reacted at a temperature of 240°C and a pressure of 3.0 MPa for 24 hours. After treatment, 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid is obtained, with a purity of 99.1% and a yield of 70.7%. This method uses strong alkali potassium hydroxide, which corrodes the equipment and the reactants stick to the wall. The reaction time is 24 hours, which is too long and not suitable for large-scale production. Korean patent WO2019212233A1 discloses a method for preparing 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid. 4,4'-biphenyldiol and potassium bicarbonate are used as raw materials, and DMF is used as solvent. The reaction is carried out at 200°C for 72 hours, the initial reaction pressure is 20 bar, and the final reaction pressure is 50 bar. The highest yield is 95%, but the purity of the product is not mentioned. This method has a long reaction time and high reaction pressure. The addition of a large amount of solvent solves the problem of sticking to the wall, but reduces the yield of the product per unit volume, which is not suitable for large-scale production. Japanese patent JP2010173955A introduces a method for preparing 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid using 4,4'-biphenyldiol 9.00g (81.7mmol), potassium bicarbonate 19.3g (193mmol), lithium hydroxide 1.96g (81.7mmol), potassium carbonate 0.8g (5.8mmol) as raw materials, p-xylene 70ml, 200°C, pressure 1.9MPa, reaction for 3 hours. However, the test verification did not give the effect mentioned in the patent. Journal of the American Chemical Society, 134(16), 7056-7065; 2012 introduces a method for preparing 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid using 4,4'-biphenyldiol, potassium bicarbonate, and solid carbon dioxide as raw materials, and trichlorobenzene as solvent. The reaction is carried out at 255°C for 17 hours, and the product is obtained after treatment, with a yield of 40%, but the purity is not mentioned.This method has low yield, the addition of solvent reduces the yield per unit volume, solid carbon dioxide is not easy to obtain and weight is not easy to control, and thus is not suitable for large-scale production.

[0003] As an important organic ligand for synthesizing MOFs materials, 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid is applied more and more widely, and the market demand is gradually increasing. The existing preparation method has limitations for large-scale production, which limits the yield of 4,4-dihydroxybiphenyl-3,3-dicarboxylic acid and cannot meet the market demand.

[0004] SUMMARY

[0005] To solve the above problems, the application provides a preparation method of 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid, which solves the problems of high equipment requirement, long reaction time, high reaction temperature, high reaction pressure and low yield per unit volume.

[0006] To achieve the above purpose, the application provides the following technical scheme.

[0007] The application provides a preparation method of 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid, which includes the following steps.

[0008] 1) Mixing 4,4-dihydroxybiphenyl, alkali metal carbonate and alkali metal bicarbonate to obtain a mixture;

[0009] 2) Mixing the mixture obtained in step 1) with a water-soluble high-boiling organic solvent, and reacting under a carbon dioxide environment to obtain a reaction product;

[0010] The reaction conditions include a temperature of 200-280 DEG C, a pressure of 2-5 MPa and a time of 12-24 h;

[0011] 3) Dissolving the reaction product obtained in step 2) in water, adjusting the pH value to 1.0-2.0 and filtering to obtain 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid.

[0012] Preferably, the alkali metal carbonate in step 1) includes potassium carbonate and / or sodium carbonate.

[0013] Preferably, the alkali metal bicarbonate in step 1) includes potassium bicarbonate and / or sodium bicarbonate.

[0014] Preferably, the molar ratio of 4,4-dihydroxybiphenyl, alkali metal carbonate and alkali metal bicarbonate in step 1) is 1:1:1.

[0015] Preferably, the reaction conditions in step 2) include a temperature of 230 DEG C, a pressure of 3 MPa and a time of 15 h.

[0016] Preferably, the mass ratio of the mixture to the water-soluble high-boiling organic solvent in step 2) is 10:3.

[0017] The water-soluble high-boiling organic solvent includes one or more of N,N-diethylformamide, dimethyl sulfoxide and N-methyl pyrrolidone.

[0018] Preferably, step 3) uses a sulfuric acid solution and / or a hydrochloric acid solution to adjust the pH value.

[0019] Preferably, after step 3), a crude 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid is obtained, and the crude 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid is mixed with an acetic acid solution, beaten up, and filtered to obtain 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid.

[0020] Preferably, the mass ratio of the crude 4,4-dihydroxybiphenyl-3,3-dicarboxylic acid to the acetic acid is 1g:4-10ml.

[0021] The present application has the following beneficial effects:

[0022] The present application provides a preparation method of 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid, which uses carbon dioxide as a raw material without adding strong alkalis such as potassium hydroxide and sodium hydroxide, reduces the corrosion of equipment, reduces the requirements for reaction equipment, and reduces the production cost; the purity of the crude product reaches 99.0%, the yield is 95%, and the crude product can be directly used for other reactions without further refining, which simplifies the post-processing operation, significantly reduces the pollution to the environment, improves the production efficiency, effectively improves the yield of organic ligands, and meets the market demand.

[0023] The preparation method of the present application is simple, suitable for industrial expansion, and has a yield of 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid of more than 95% and a purity of more than 99.0%, which can be directly used for the synthesis of metal organic frameworks. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed in the embodiments will be briefly introduced as follows.

[0025] FIG. 1 is a nuclear magnetic hydrogen spectrum of the crude 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid prepared in Example 1. DETAILED DESCRIPTION

[0026] The present application provides a preparation method of 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid, which includes the following steps:

[0027] 1) mixing 4,4-dihydroxybiphenyl with alkali metal carbonate and alkali metal bicarbonate to obtain a mixture;

[0028] 2) mixing the mixture obtained in step 1) with a water-soluble high-boiling organic solvent, and performing reaction under a carbon dioxide environment to obtain a reaction product;

[0029] The reaction conditions include: temperature of 200-280℃, pressure of 2-5MPa, and time of 12-24h;

[0030] 3) dissolving the reaction product obtained in step 2) in water, adjusting the pH value to 1.0-2.0, and filtering to obtain 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid.

[0031] In the present application, the alkali metal carbonate preferably includes potassium carbonate and / or sodium carbonate. In the present application, the alkali metal bicarbonate preferably includes potassium bicarbonate and / or sodium bicarbonate. In the present application, the molar ratio of 4,4-dihydroxybiphenyl, alkali metal carbonate and alkali metal bicarbonate is preferably 1:1:1.

[0032] In the present application, the reaction conditions preferably include: temperature of 230℃, pressure of 3MPa, and time of 15h. In the present application, the mass ratio of the mixture to the water-soluble high-boiling organic solvent is preferably 10:3. In the present application, the water-soluble high-boiling organic solvent preferably includes one or more of N,N-diethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.

[0033] In the present application, the pH value is preferably adjusted using a sulfuric acid solution and / or a hydrochloric acid solution. In the present application, after the filtering, a 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid crude product is obtained, and the 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid crude product is preferably mixed with acetic acid, beaten, and filtered to obtain 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid. In the present application, the mass ratio of the 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid crude product to the volume of acetic acid is preferably 1g:4-10ml.

[0034] In order to further illustrate the present application, the present application is described in detail below in conjunction with examples, but they should not be understood as limiting the scope of protection of the present application.

[0035] Example 1

[0036] The embodiment provides a preparation method of 4,4'-dihydroxy-3,3'-biphenyl dicarboxylic acid.

[0037] 0.54 mol of 4,4-dihydroxybiphenyl is mixed with 0.54 mol of potassium carbonate and 0.54 mol of potassium bicarbonate, and then is added into a 1L autoclave, then 30% dimethyl sulfoxide by weight of the reactants is added, the air in the autoclave is replaced with carbon dioxide gas, then the carbon dioxide gas is continuously introduced, and stirring (30 rpm) is started, under the conditions that the temperature is 230 DEG C and the pressure is 3.0 MPa, reaction is carried out for 15 h, the crude product obtained by the reaction is dissolved in 800 ml of hot water at 80 DEG C, the pH value of the obtained solution is adjusted to 2 with hydrochloric acid, and the crude product is obtained by filtration under reduced pressure, the purity is 99.0%, and the yield is 95%, the obtained crude product is placed in 800 ml of acetic acid, the system is stirred uniformly under the condition that the room temperature is 25 DEG C, and then 4,4'-dihydroxy-3,3'-biphenyl dicarboxylic acid refined product is obtained by filtration under reduced pressure, the purity of the product is 99.8%, and the yield is 85%.

[0038] The nuclear magnetic hydrogen spectrum diagram of 4,4'-dihydroxy-3,3'-biphenyl dicarboxylic acid prepared in the embodiment is shown in Fig. 1; the nuclear magnetic hydrogen spectrum data is shown in the figure. 1 H-NMR (400MHz, DMSO) δ: 7.037-7.058 (s 2H), δ: 7.775-7.803 (s 2H), δ: 7.964-7.970 (s 2H).

[0039] Embodiment 2

[0040] The embodiment provides a preparation method of 4,4'-dihydroxy-3,3'-biphenyl dicarboxylic acid.

[0041] 0.54 mol of 4,4-dihydroxybiphenyl is mixed with 0.54 mol of potassium carbonate and 0.54 mol of potassium bicarbonate, and then is added into a 1L autoclave, then 30% dimethyl sulfoxide by weight of the reactants is added, the air in the autoclave is replaced with carbon dioxide gas, then the carbon dioxide gas is continuously introduced, and stirring (30 rpm) is started, under the conditions that the temperature is 230 DEG C and the pressure is 3.0 MPa, reaction is carried out for 15 h, the crude product obtained by the reaction is dissolved in 800 ml of hot water at 80 DEG C, the pH value of the obtained solution is adjusted to 2 with hydrochloric acid, and the crude product is obtained by filtration under reduced pressure, the purity is 99.0%, and the yield is 95%, the obtained crude product is placed in 800 ml of acetic acid, the system is stirred uniformly under the condition that the room temperature is 25 DEG C, and then 4,4'-dihydroxy-3,3'-biphenyl dicarboxylic acid refined product is obtained by filtration under reduced pressure, the purity of the product is 99.8%, and the yield is 85%.

[0042] Embodiment 3

[0043] The present embodiment provides a method for preparing 4,4'-dihydroxy-3,3'-biphenyl dicarboxylic acid:

[0044] 0.54 mol of 4,4-dihydroxybiphenyl and 0.54 mol of potassium carbonate, 0.54 mol of potassium bicarbonate were mixed and then added into a 1 L autoclave, then 30% of N-methyl pyrrolidone by weight of the reactants was added, the autoclave was replaced with carbon dioxide gas, then carbon dioxide gas was continuously introduced, stirring was started (30 rpm), and reaction was carried out at a temperature of 230°C and a pressure of 3.0 MPa for 15 h. The crude product obtained by the reaction was dissolved in 800 ml of hot water at 80°C, the pH of the obtained solution was adjusted to 2 with hydrochloric acid, and the crude product was obtained by filtration under reduced pressure, with a purity of 98.2% and a yield of 92%. The crude product obtained was placed in acetic acid, and the system was stirred uniformly under reduced pressure to obtain a refined product of 4,4'-dihydroxy-3,3'-biphenyl dicarboxylic acid, with a product purity of 99.5% and a yield of 78%.

[0045] Embodiment 4

[0046] The present embodiment provides a method for preparing 4,4'-dihydroxy-3,3'-biphenyl dicarboxylic acid:

[0047] 0.54 mol of 4,4-dihydroxybiphenyl and 0.54 mol of potassium carbonate, 0.54 mol of potassium bicarbonate were mixed and then added into a 1 L autoclave, then 30% of N-methyl pyrrolidone by weight of the reactants was added, the autoclave was replaced with carbon dioxide gas, then carbon dioxide gas was continuously introduced, stirring was started (30 rpm), and reaction was carried out at a temperature of 230°C and a pressure of 3.0 MPa for 15 h. The crude product obtained by the reaction was dissolved in 800 ml of hot water at 80°C, the pH of the obtained solution was adjusted to 2 with hydrochloric acid, and the crude product was obtained by filtration under reduced pressure, with a purity of 98.2% and a yield of 92%. The crude product obtained was placed in acetic acid, and the system was stirred uniformly under reduced pressure to obtain a refined product of 4,4'-dihydroxy-3,3'-biphenyl dicarboxylic acid, with a product purity of 99.5% and a yield of 78%.

[0048] Although the above embodiment has made a detailed description of the present application, it is only a part of the embodiments of the present application, but not all the embodiments, and other embodiments can be obtained according to the present embodiment without creativity, which are within the protection scope of the present application.

Claims

1. A method for preparing 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid, characterized in that, Includes the following steps: 1) Mix 4,4-dihydroxybiphenyl with alkali metal carbonate and alkali metal bicarbonate to obtain a mixture; 2) The mixture obtained in step 1) is mixed with a water-soluble high-boiling-point organic solvent and reacted in a carbon dioxide environment to obtain the reaction product; The reaction conditions include: a temperature of 200–280°C, a pressure of 2–5 MPa, and a time of 12–24 h; 3) Dissolve the reaction product obtained in step 2) in water, adjust the pH to 1.0-2.0, and then filter to obtain 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid.

2. The preparation method according to claim 1, characterized in that, Step 1) Alkali metal carbonates include potassium carbonate and / or sodium carbonate.

3. The preparation method according to claim 1, characterized in that, Step 1) Alkali metal bicarbonates include potassium bicarbonate and / or sodium bicarbonate.

4. The preparation method according to claim 1, characterized in that, In step 1), the molar ratio of 4,4-dihydroxybiphenyl to alkali metal carbonate and alkali metal bicarbonate is 1:1:

1.

5. The preparation method according to claim 1, characterized in that, The reaction conditions in step 2) include: a temperature of 230°C, a pressure of 3 MPa, and a time of 15 h.

6. The preparation method according to claim 1, characterized in that, The mass ratio of the mixture to the water-soluble high-boiling-point organic solvent in step 2) is 10:3; The water-soluble high-boiling-point organic solvent includes one or more of N,N-diethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.

7. The preparation method according to claim 1, characterized in that, Step 3) involves adjusting the pH value using sulfuric acid solution and / or hydrochloric acid solution.

8. The preparation method according to claim 1, characterized in that, After filtration in step 3), crude 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid is obtained. The crude 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid is mixed with acetic acid, pulped, and filtered to obtain 4,4'-dihydroxybiphenyl-3,3'-dicarboxylic acid.

9. The preparation method according to claim 8, characterized in that, The mass ratio of the crude 4,4-dihydroxybiphenyl-3,3-dicarboxylic acid to the volume ratio of acetic acid is 1 g: 4-10 ml.

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