CN115745782B

CN115745782B - Preparation method and production method of phthalic acid derivative

Info

Publication number: CN115745782B
Application number: CN202211563570.2A
Authority: CN
Inventors: 张唐志; 匡逸; 陆茜; 陈快快; 高梓丰; 肖新强; 罗德智; 赵濬宇
Original assignee: Jiangxi Lingfu Biotechnology Co ltd
Current assignee: Jiangxi Lingfu Biotechnology Co ltd
Priority date: 2022-12-07
Filing date: 2022-12-07
Publication date: 2024-06-07
Anticipated expiration: 2042-12-07
Also published as: CN115745782A

Abstract

The invention provides a preparation method and a production method of a phthalic acid derivative, belonging to the field of organic chemistry. The preparation method of the 4-bromophthalic acid monoalkali metal salt comprises the following steps: phthalic anhydride, brominating agent bromine and reaction solvent bromination reaction. The preparation method of the 3,3', 4' -biphenyl tetracarboxylic acid comprises the following steps: b) Coupling and hydrolyzing the 4-bromophthalic acid monoalkali metal salt; c) And (5) filtering and acidifying. The preparation method of the 3,3', 4' -biphenyl tetracarboxylic dianhydride comprises the following steps: drying and dehydrating 3,3', 4' -biphenyl tetracarboxylic acid. The production method of 3,3', 4' -biphenyl tetracarboxylic acid comprises the following steps: a) Bromination reaction, crystallization and the like to obtain a wet product containing the 4-bromophthalic acid monoalkali metal salt and a first filtrate; b) Coupling and hydrolyzing; c) Filtering, crystallizing, acidifying, etc. to obtain 3,3', 4' -diphenyl tetracarboxylic acid, alkali metal bromide and alkali metal salt of acid. The method has high yield, high purity and low cost.

Description

Preparation method and production method of phthalic acid derivative

Technical Field

The invention relates to the field of organic chemistry, in particular to a preparation method and a production method of a phthalic acid derivative, wherein the phthalic acid derivative is 4-bromo-phthalic acid monoalkali metal salt, 3', 4' -biphenyl tetracarboxylic acid and 3,3', 4' -biphenyl tetracarboxylic dianhydride.

Background

3,3', 4' -Biphenyl tetracarboxylic dianhydride (BPDA) is one of main monomers for synthesizing high-performance polyimide, especially polyimide for electronic devices, and has high price. The polyimide synthesized by the polyimide and diamine such as 1,4 '-p-phenylenediamine, 4' -diaminodiphenyl ether and the like has excellent heat resistance, mechanical property and electrical insulation property, and is widely applied to the fields of aviation, aerospace, electronics, laser, new energy sources and the like.

Therefore, scientific researchers are continuously exploring the preparation method of the BPDA and developing a plurality of process routes with industrialized value. For example, chinese patent CN110563678a discloses a method for preparing BPDA from phthalic anhydride by chlorination, coupling and hydrolysis reactions.

The phthalate salt generated by the chlorination reaction in the above method is an important intermediate for preparing BPDA, however, the phthalate salt has low yield and more impurities, and is difficult to separate, so that it is necessary to develop a method for preparing a phthalate derivative with high yield and high purity to meet the wide market demands.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a method for preparing and a method for producing a phthalic acid derivative, wherein the phthalic acid derivative is a monoalkali metal salt of 4-bromophthalic acid, 3', 4' -biphenyltetracarboxylic dianhydride, and the method is high in yield, high in purity and low in cost, and is suitable for large-scale industrial production.

To achieve the above and other related objects, a first aspect of the present invention provides a method for preparing a monoalkali metal 4-bromophthalate, wherein phthalic anhydride, a brominating agent and a reaction solvent undergo bromination reaction to obtain the monoalkali metal 4-bromophthalate, wherein the brominating agent is bromine, and the reaction solvent is an aqueous solution of alkali metal hydroxide.

The second aspect of the invention provides a preparation method of 3,3', 4' -biphenyl tetracarboxylic acid, comprising the following steps:

b) The 4-bromo phthalic acid monoalkali metal salt is coupled and hydrolyzed under the conditions of catalyst, cocatalyst and alkaline solution to obtain a mixture containing 3,3', 4' -biphenyl tetracarboxylic acid alkali metal salt;

c) Filtering the mixture obtained in the step b) to obtain a second filtrate; and (3) acidizing the second filtrate to obtain 3,3', 4' -biphenyl tetracarboxylic acid.

The third aspect of the invention provides a method for preparing 3,3', 4' -biphenyl tetracarboxylic dianhydride, comprising the following steps:

1) The 3,3', 4' -biphenyl tetracarboxylic acid is obtained by adopting the preparation method of the 3,3', 4' -biphenyl tetracarboxylic acid;

2) Drying and dehydrating the 3,3', 4' -biphenyl tetracarboxylic acid to obtain the 3,3', 4' -biphenyl tetracarboxylic dianhydride.

In a fourth aspect, the present invention provides a method for producing 3,3', 4' -biphenyltetracarboxylic acid, comprising the steps of:

a) The phthalic anhydride, a brominating agent and a reaction solvent undergo bromination reaction, wherein the brominating agent is bromine, and the reaction solvent is an alkali metal hydroxide aqueous solution; cooling, preserving heat, crystallizing and filtering after the bromination reaction is finished to obtain a wet product containing the 4-bromophthalic acid monoalkali metal salt and a first filtrate;

b) Coupling and hydrolyzing wet products containing 4-bromo phthalic acid monoalkali metal salt under the conditions of catalyst, cocatalyst and alkaline solution to obtain a mixture containing 3,3', 4' -biphenyl tetracarboxylic acid alkali metal salt;

c) Filtering the mixture obtained in the step b) to obtain a second filtrate;

Cooling, preserving heat, crystallizing and filtering the second filtrate to obtain a third filtrate and a first solid; centrifuging the first solid to obtain wet by-product alkali metal bromide;

Acidifying the third filtrate, preserving heat for crystallization, and filtering to obtain a fourth filtrate and a second solid; concentrating the fourth filtrate under reduced pressure, cooling, filtering and centrifuging to obtain alkali metal salt of acid for acidification; and adding the second solid into water, and carrying out heat preservation crystallization to obtain the 3,3', 4' -biphenyl tetracarboxylic acid.

The technical scheme has at least one of the following beneficial effects:

1) The preparation method of the 4-bromo-phthalic acid monosodium salt has the advantages of high yield, high purity and low cost, still has the beneficial effects of high yield, high purity and low cost on the scale of hundred kilograms, and is suitable for large-scale industrial production.

2) The preparation method of the 3,3', 4' -biphenyl tetracarboxylic acid has the advantages of high yield, high purity and low cost, still has the advantages of high yield, high purity and low cost on the scale of hundreds of kilograms, and is suitable for large-scale industrial production.

3) The preparation method of the 3,3', 4' -biphenyl tetracarboxylic dianhydride has the advantages of high yield, high purity and low cost, still has the advantages of high yield, high purity and low cost on the scale of hundreds of kilograms, and is suitable for large-scale industrial production.

4) The preparation method of the 4-bromophthalic acid monosodium salt has high atom economy, can simultaneously prepare alkali metal bromides such as sodium bromide, has the beneficial effect of high yield on the scale of hundreds of kilograms, and is suitable for co-production of an amplifying process.

5) The preparation method of the 3,3', 4' -biphenyl tetracarboxylic acid has high atom economy, can simultaneously prepare high-purity alkali metal bromides such as sodium bromide and alkali metal salts of acids used for acidification such as sodium sulfate, still has the beneficial effect of high yield on the scale of hundred kilograms, and is suitable for co-production of the amplification process.

Detailed Description

The technical scheme of the invention is described below through specific examples. It is to be understood that the mention of one or more method steps of the present invention does not exclude the presence of other method steps before and after the combination step or that other method steps may be interposed between these explicitly mentioned steps; it should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.

A preparation method of 4-bromo-phthalic acid monoalkali metal salt comprises the steps of carrying out bromination reaction on phthalic anhydride, a brominating agent and a reaction solvent to obtain the 4-bromo-phthalic acid monoalkali metal salt, wherein the brominating agent is bromine, and the reaction solvent is alkali metal hydroxide aqueous solution.

Preferably, the molar ratio of phthalic anhydride to brominating agent is 1:1 to 1:1.3, such as 1:1 to 1:1.1 or 1:1.1 to 1:1.3.

Preferably, the molar ratio of phthalic anhydride to alkali metal hydroxide is 1: 2-1: 3.

Preferably, the aqueous alkali metal hydroxide solution has a mass percentage concentration of 7% to 11%, such as 7% to 8.5%, 8.5% to 8.8%, 8.8% to 9.7%, 9.7% to 10.4%, or 10.4% to 11%.

Preferably, the alkali metal is selected from at least one of sodium, potassium, rubidium and cesium.

Preferably, the temperature of the bromination reaction is from 80℃to 100℃such as from 80℃to 95℃or from 95℃to 100 ℃.

Preferably, the bromination reaction is carried out for a period of 8 to 12 hours, such as 8 to 10 hours or 10 to 12 hours.

Preferably, the preparation method further comprises: cooling, preserving heat, crystallizing and filtering after the bromination reaction is finished.

More preferably, the temperature is reduced to-10 ℃ to 5 ℃.

More preferably, the preparation method further comprises: the 4-bromo-phthalic acid monoalkali metal salt obtained after filtration is pulped in the presence of a pulping solvent.

Even more preferably, the beating solvent comprises at least one of ethyl acetate, methyl tert-butyl ether, n-heptane, methanol and dichloromethane.

Even more preferably, the mass ratio of the beating solvent to the mono-alkali metal salt of 4-bromophthalic acid is 4 to 6:1, such as 4 to 4.8:1 or 4.8 to 6:1.

Even more preferably, the beating time is 20 to 40 minutes, such as 20 to 30 minutes or 30 to 40 minutes.

More preferably, the preparation method further comprises: and carrying out post-treatment on the first filtrate obtained by filtering to obtain alkali metal bromide. Post-processing may include: heating, decolorizing, hot filtering, decompressing and concentrating, cooling, preserving heat and crystallizing, filtering, wherein active carbon can be adopted for decolorizing, the temperature is controlled to be 80-95 ℃ for hot filtering, and the temperature is reduced to minus 10-5 ℃ for preserving heat and crystallizing.

A preparation method of 3,3', 4' -biphenyl tetracarboxylic acid comprises the following steps:

Preferably, the preparation method further comprises step a) before step b): the preparation method of the 4-bromophthalic acid monoalkali metal salt is adopted to obtain the 4-bromophthalic acid monoalkali metal salt.

Preferably, in step b), the catalyst is Pd/C.

More preferably, the mass percentage of Pd in Pd/C is 5% -10%.

Preferably, in step b), the cocatalyst is hydroxylamine sulfate.

Preferably, in step b) the promoter is present as an aqueous solution at a concentration of 19% to 29% by mass, such as 19% to 19.4%, 19.4% to 21.3% or 21.3% to 29%.

Preferably, in step b), the alkaline solution is an aqueous sodium hydroxide solution.

Preferably, in step b), the alkaline solution has a mass percentage concentration of 4% to 15%, such as 4% to 5%, 5% to 5.7%, 5.7% to 8.1%, 8.1% to 11% or 11% to 15%.

More preferably, the concentration of the alkaline solution is 5-11% by mass.

Preferably, in step b), the mass ratio of the catalyst to the monoalkali metal 4-bromophthalate is from 0.009 to 0.015:1, such as 0.009-0.01: 1 or 0.01 to 0.015:1.

Preferably, in step b), the mass ratio of the cocatalyst to the monoalkali metal 4-bromophthalate is from 0.2 to 0.4:1, such as 0.2 to 0.27: 1. 0.27 to 0.31:1 or 0.31 to 0.4:1.

Preferably, in step b), the temperature of the coupling and hydrolysis reaction is from 50℃to 90 ℃.

Preferably, in step b), the coupling and hydrolysis reaction is carried out for a period of from 8 hours to 12 hours, such as from 8 hours to 10 hours or from 10 hours to 12 hours.

Preferably, in step c), the pH of the acidification reaction is 3 to 4, such as 3 to 3.5 or 3.5 to 4, and the acidification reaction may be carried out using acidic substances such as hydrochloric acid, sulfuric acid, etc.

Preferably, in step c), the acidification reaction is followed by a filtration wash to obtain 3,3', 4' -biphenyltetracarboxylic acid.

Preferably, in step c), the second filtrate is cooled, for example, to 25-30 ℃, and then is subjected to heat preservation and crystallization, and is filtered to obtain a third filtrate and a first solid;

Acidifying the third filtrate, preserving heat and crystallizing at 70-80 ℃, and filtering to obtain a fourth filtrate and a second solid;

And adding water into the second solid, and carrying out heat preservation crystallization at the temperature of 70-80 ℃ to obtain the 3,3', 4' -biphenyl tetracarboxylic acid.

More preferably, centrifuging the first solid to yield wet byproduct alkali metal bromide;

More preferably, the fourth filtrate is concentrated under reduced pressure, cooled to 20-30 ℃, filtered and centrifuged to obtain alkali metal salts of acids used for acidification, such as sodium sulfate, sodium chloride and the like.

A method for preparing 3,3', 4' -biphenyl tetracarboxylic dianhydride, comprising the following steps:

A method for producing 3,3', 4' -biphenyl tetracarboxylic acid comprises the following steps:

c) Filtering the mixture obtained in the step b) to obtain a second filtrate;

Preferably, in step a), the molar ratio of phthalic anhydride to brominating agent is 1:1 to 1:1.3, such as 1:1 to 1:1.1 or 1:1.1 to 1:1.3.

Preferably, in step a), the molar ratio of phthalic anhydride to alkali metal hydroxide is 1: 2-1: 3.

Preferably, in step a), the aqueous alkali metal hydroxide solution has a mass percentage concentration of 7% to 11%, such as 7% to 8.5%, 8.5% to 8.8%, 8.8% to 9.7%, 9.7% to 10.4% or 10.4% to 11%.

Preferably, in step a), the alkali metal is selected from at least one of sodium, potassium, rubidium and cesium.

Preferably, in step a), the temperature of the bromination reaction is from 80℃to 100℃such as from 80℃to 95℃or from 95℃to 100 ℃.

Preferably, in step a), the bromination reaction is carried out for a period of time ranging from 8 hours to 12 hours, such as from 8 hours to 10 hours or from 10 hours to 12 hours.

Preferably, in step a), the temperature is reduced to-10℃to 5 ℃.

Preferably, the first filtrate is subjected to a post-treatment to obtain alkali metal bromide. Post-processing may include: heating, decolorizing, hot filtering, decompressing and concentrating, cooling, preserving heat and crystallizing, filtering, wherein active carbon can be adopted for decolorizing, the temperature is controlled to be 80-95 ℃ for hot filtering, and the temperature is reduced to minus 10-5 ℃ for preserving heat and crystallizing.

Preferably, in step b), the catalyst is Pd/C.

Preferably, in step b), the cocatalyst is hydroxylamine sulfate;

Preferably, in step b), the alkaline solution has a mass percentage concentration of 25% to 35%.

Example 1]

Preparation of Compound 1a

This example provides a process for the preparation of compound 1a, having the following formula:

the method comprises the following reaction steps:

70mL of water and 5.40g of NaOH (135 mmol,2.0 eq) were added to the reaction vessel, the mixture was stirred and dissolved, then 10.00g of Compound 2a (67.5 mmol,1.0 eq) was added to the mixture after cooling to 40℃and the solution was stirred and dissolved in an oil bath at 40℃and 11.87g of bromine (74.3 mmol,1.1 eq) was added dropwise, and after the addition, the oil bath was heated to 100℃and reacted for 10 hours. After the reaction, the temperature is reduced to minus 10 ℃, the crystallization is carried out under the heat preservation, 14.70g of compound 1a is obtained, the yield is 81.6 percent, the purity is 85.6 percent, and the purity is 92.8 percent after 70g of ethyl acetate is pulped for 30 minutes.

Example 2]

Screening of brominating agents

This example screens brominating agents based on example 1.

(1) Dibromohydantoin: to the reaction vessel were added 25mL of methylene chloride, 1.16g of p-benzenesulfonic acid (6.7 mmol,0.2 eq), after stirring and dissolving, 5g of compound 2a (33.8 mmol,1.0 eq) was added after cooling to 40℃and stirring and dissolving at 40℃in an oil bath, 5.79g of bromine (36.2 mmol,1.1 eq) was added dropwise, and after the addition, the oil bath was warmed to 100℃and reacted overnight. The reaction is completed, the yield of the compound 1a is 5.13%, and the dibromohydantoin has poor bromine effect.

(2) Sodium bromate: 13.83mL of water and 34mL of sulfuric acid were added to the reaction vessel, 5g of Compound 2a (33.8 mmol,1.0 eq) was added, the solution was stirred at 40℃in an oil bath, 4.84g of sodium bromate (32.1 mmol,0.95 eq) was added dropwise, and after the addition, the oil bath was warmed to 100℃and reacted overnight. The reaction was completed, the yield of compound 1a was 46.6%, and the bromine addition effect of sodium bromate was general.

(3) Sodium hypobromite: to the reaction vessel was added 45mL of water, 10g of Compound 2a (67.5 mol,1.0 eq), the solution was stirred at 40℃in an oil bath, 8.0g of sodium hypobromite (67.2 mol,0.996 eq) was added dropwise, and after the addition, the oil bath was warmed to 100℃and reacted overnight. The reaction was completed, the yield of compound 1a was 6.8%, and the bromine addition effect of sodium hypobromite was poor.

Example 3 ]

Screening of bromine usage

In this example, the amount of bromine as a brominating agent was selected based on example 1, and the other experimental operations were the same as in example 1 except for the characteristics listed in the table, and the selection results are shown in table 1.

TABLE 1 screening of bromine dosages

Sequence number	Bromine amount (g)	Equivalent weight	Reaction yield (%)	Purity (%)
					1	10.78	1.0eq	54.6	76.6
2	11.87	1.1eq	81.6	85.6
					3	14.03	1.3eq	70.5	84.5

As shown in Table 1, the yield of 1.0eq bromine was low and the yield of 1.1eq was higher than 1.3eq, so that the reaction yield could not be improved by excessive bromine.

Example 4]

Screening of reaction solvents

In this example, the reaction solvent was screened on the basis of example 1, and the experimental operations were the same as in example 1 except for the features listed in the table, and the screening results are shown in table 2.

TABLE 2 screening of reaction solvents

Sequence number	Reaction solvent (V/V)	Reaction conditions
			1	Dichloromethane glacial acetic acid=1:1	Non-reaction
2	Sulfuric acid glacial acetic acid=1:1	Non-reaction

Example 5 ]

Screening of sodium hydroxide dosage and concentration

In this example, sodium hydroxide was used in the same amount and concentration as in example 1 except for the characteristics shown in the table, and the screening results are shown in table 3.

TABLE 3 screening of sodium hydroxide usage and concentration

As can be seen from table 3, both the concentration and the equivalent weight of sodium hydroxide affect the reaction yield and purity. Wherein in the case of the sodium hydroxide equivalent of 2.0eq, the reaction yield and purity were higher at the concentrations of 0.077g/mL and 0.108g/mL, and the reaction yield was greatly lowered as the sodium hydroxide concentration was increased to 0.135 g/mL.

Example 6]

Screening of beating conditions

This example was carried out by beating the compound 1a obtained in example 1 on the basis of example 1, and the beating conditions were selected, and the other experimental operations were the same as in example 1 except for the characteristics listed in the table, and the screening results are shown in table 4.

TABLE 4 screening of pulping conditions

As can be seen from Table 4, the beating effect was most excellent with ethyl acetate and methyl tert-butyl ether.

Example 7 ]

Preparation of Compound 4

This example provides a method for preparing compound 4, having the following reaction formula:

the method comprises the following reaction steps:

To the reaction vessel were added 50mL of water, 3.51g of sodium hydroxide (87.8 mmol,4.7 eq) and 5.0g of compound 1a (18.7 mmol,1.0 eq), within a controlled temperature of 50℃0.05g of wet palladium on carbon (mass fraction of palladium in palladium on carbon: 10%), 5mL of hydroxylamine sulfate aqueous solution (0.27 g/mL) was added, heated to 90℃and stirred for dissolution, and the reaction was continued for 10 hours. After the reaction, the mixture was filtered, the pH of the filtrate was adjusted to 3 to 4 with hydrochloric acid, and the mixture was washed with water to give 3.0g of Compound 4 in 97.2% yield and 98.6% purity.

The present example further provides a process for the preparation of compound 5, having the following formula:

the method comprises the following reaction steps:

1.0g of Compound 4 (3 mmol,1.0 eq) was placed in an oven and dried at about 120℃for 12 hours, then warmed to about 250℃and incubated for 12 hours to give 0.85g of Compound 5 in 96.3% yield and 100% purity.

Example 8 ]

Screening of solvent volumes

In this example, the solvent volume in the reaction system was selected based on example 7, and the other experimental operations were the same as in example 7 except for the characteristics listed in the table, and the selection results are shown in table 5.

TABLE 5 screening of solvent volumes

As can be seen from table 5, the reaction yield increased with increasing solvent volume. The reaction belongs to intermolecular reaction, and generally the higher the concentration of a reaction system is, the more favorable the reaction is, however, the results of examples show that the concentration of the reaction system is reduced, the solvent is increased, the yield is increased, and the unexpected technical effect is achieved.

Example 9 ]

Process for the preparation of Compound 4

The present example provides a process for the preparation of compound 4 comprising the following two steps:

the method comprises the following reaction steps:

2000kg of water and 900 liters of an aqueous sodium hydroxide solution (the mass concentration is 0.3kg/L, the density of the aqueous sodium hydroxide solution is 1.0g/cm ³) were added to the reaction vessel 1, after stirring and purging, 500kg of the compound 2a (3375.6 mol,1.0 eq) was added to the reaction vessel within 80℃of the temperature, the temperature was 80-95℃of the reaction vessel was controlled, 539kg of bromine (3373.0 mol,1.0 eq) was added dropwise to the reaction vessel under stirring and purging, and after completion of the purging, the reaction vessel was incubated for 10 hours. After the reaction is finished, cooling to-10-5 ℃, preserving heat, crystallizing, and filtering to obtain filtrate 1 and 883kg of wet compound 1 a;

Heating the filtrate 1 to 55 ℃, adding 10kg of active carbon for decoloring for 1h, thermally filtering, controlling the temperature to 80-95 ℃, concentrating under reduced pressure, cooling to-10-5 ℃, preserving heat and crystallizing for 3h, filtering to obtain 330kg of sodium bromide, and recovering rate to 95.1%;

Adding 3533kg of water and 882L of sodium hydroxide aqueous solution (the mass concentration is 0.3kg/L, the density of the sodium hydroxide aqueous solution is 1.0g/cm ³) into a reaction vessel 2, controlling the temperature within 50 ℃, adding 883kg of wet product of the compound 1a, controlling the temperature to 40 ℃, adding 9kg of 5% wet palladium carbon (the mass fraction of palladium in palladium carbon is 5%), adding 1158L of hydroxylamine sulfate aqueous solution (the mass concentration is 0.24 kg/L), heating to 50 ℃, stirring, dissolving, and reacting for 10 hours under reflux;

After the reaction is finished, hot filtering to remove palladium carbon to obtain filtrate 2, cooling to 25-30 ℃, crystallizing and preserving heat for 3 hours, filtering to obtain filtrate 3 and solid 1, and centrifuging the solid 1 to obtain 351kg of wet sodium bromide;

Adding 5000kg of water into a reaction vessel 3, dropwise adding concentrated sulfuric acid until the pH value is 3.5, controlling the temperature to be 70-80 ℃, dropwise adding filtrate 3, after the completion of dropwise adding, preserving the heat at 70-80 ℃ for crystallization for 2 hours, filtering to obtain filtrate 4 and solid 2, adding 5000kg of water into the solid 2, preserving the heat at 70-80 ℃ for crystallization for 2 hours, obtaining 524kg of wet compound 4, and drying to obtain 490kg of compound 4, wherein the yield is 87.9% and the purity is 98.5%.

Concentrating the filtrate 4 under reduced pressure, cooling to 20-30deg.C, filtering, and centrifuging to obtain 470kg wet sodium sulfate.

Comparative example 1 ]

Preparation of Compound 3

This example provides a method for preparing compound 3, having the following reaction formula:

the method comprises the following reaction steps:

70mL of water, 10.00g of Compound 2a (67.5 mol,1.0 eq) and 52mL of sodium hypochlorite solution (mass concentration: 0.1 g/mL) and 5.40g of sodium hydroxide (135 mol,2.0 eq) were added to the reaction vessel and, after the addition, the reaction was carried out at 30℃for 1 hour. After the reaction, the temperature is reduced to-10 ℃ and crystallization is carried out, 8.57g of compound 3 is obtained, and the yield is 57.0%.

Comparative example 2 ]

Preparation of Compound 5

This example provides a method for preparing compound 5, having the following reaction formula:

the method comprises the following reaction steps:

To a four-necked flask equipped with a thermometer, a stirrer, a dropping device and a reflux device, 300g of water and 380g of sodium hydroxide (mass concentration: 0.32 g/mL) were added, 185g of Compound 3 (0.83 mol,1.0 eq) and 1.5g of palladium on charcoal catalyst (dry basis) were added under stirring, the temperature was raised to reflux, 390g of hydroxylamine sulfate aqueous solution (mass concentration: 0.23 g/mL) was added dropwise, the dropping rate was controlled, the reflux state was maintained, and the dropping time was 6h. The temperature is kept for 1.5 hours after the dripping. Cooling to 85 ℃, filtering while the mixture is hot to obtain filtrate 5, and carrying out liquid phase analysis on the filtrate 5, wherein the conversion rate of the raw materials is less than 5% only with trace products.

Comparative example 3 ]

Preparation of Compound 5

the method comprises the following reaction steps:

1800g of water and 380g of sodium hydroxide (mass concentration: 0.32 g/mL) were added to a four-necked flask equipped with a thermometer, a stirrer, a dropping device and a reflux device, 185g of Compound 3 (0.83 mol,1.0 eq) and 1.5g of palladium on charcoal catalyst (dry basis) were added under stirring, the temperature was raised to reflux, 390g of hydroxylamine sulfate aqueous solution (mass concentration: 0.23 g/mL) was added dropwise, the dropping rate was controlled, the reflux state was maintained, and the dropping time was 6h. The temperature is kept for 1.5 hours after the dripping. Cooling to 85 ℃, filtering while the mixture is hot to obtain filtrate 6, and carrying out liquid phase analysis on the filtrate 6, wherein the conversion rate of the raw materials is less than 5% only with trace products.

Comparative example 4 ]

Preparation of Compound 5

the method comprises the following reaction steps:

1800g of water and 380g of sodium hydroxide (mass concentration is 0.32 g/mL) were added to a four-necked flask equipped with a thermometer, a stirrer, a dropping device and a reflux device, 185g of compound 3 (0.83 mol,1.0 eq) and 18g of palladium-carbon catalyst (dry basis) were added under stirring, the temperature was raised to reflux, 390g of hydroxylamine sulfate aqueous solution (mass concentration is 0.23 g/mL) was added dropwise, the dropping speed was controlled, the reflux state was maintained, and the dropping time was 6h. The temperature is kept for 1.5 hours after the dripping. Cooling to 85 ℃, filtering while the mixture is hot to obtain filtrate 7, and carrying out liquid phase analysis on the filtrate 7, wherein the conversion rate of the raw materials is less than 5% only with trace products.

Effects and effects of the examples

According to the method of the phthalic acid derivative according to the above-mentioned examples, since bromine is used as a brominating agent in the reaction and the amount of bromine is controlled, the product can be further purified by beating using a proper reaction system and controlling the equivalent and concentration of the reaction solvent, the present invention can produce the phthalic acid derivative in high yield and high purity.

Since it has been unexpectedly found that increasing the amount of the reaction solvent can increase the reaction yield, the present invention can provide a coupling route with high yield.

Because the post-reaction treatment utilizes the difference of the solubility of the products in water to effectively separate the products, alkali metal salts of acid such as sodium sulfate and alkali metal bromides such as sodium bromide used for the acidification of byproducts can be produced, and meanwhile, the cost is reduced because the dosage of the catalyst is controlled, so the invention can provide a high-yield and low-cost process co-production route.

The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.

Claims

1. A method for preparing 3,3', 4' -biphenyl tetracarboxylic acid, which is characterized by comprising the following steps:

a) Carrying out bromination reaction on phthalic anhydride, a brominating agent and a reaction solvent to obtain 4-bromo-phthalic acid monoalkali metal salt, wherein the brominating agent is bromine, and the reaction solvent is alkali metal hydroxide aqueous solution; the preparation method further comprises the following steps: cooling, preserving heat, crystallizing and filtering after the bromination reaction is finished; the preparation method further comprises the following steps: pulping the filtered 4-bromo-phthalic acid monoalkali metal salt in the presence of a pulping solvent; the beating solvent comprises at least one of ethyl acetate, methyl tertiary butyl ether and methanol;

c) Filtering the mixture obtained in the step b) to obtain a second filtrate; acidifying the second filtrate to obtain 3,3', 4' -biphenyl tetracarboxylic acid;

a1 In step a), the mass percentage concentration of the alkali metal hydroxide aqueous solution is 7-11%;

a2 In step a), the temperature of the bromination reaction is 80-100 ℃;

a3 The mass ratio of the beating solvent to the 4-bromophthalic acid monoalkali metal salt is 4-6: 1, a step of;

a4 The pulping time is 20 min-40 min;

b1 In step b), the catalyst is Pd/C;

b2 In step b), the cocatalyst is hydroxylamine sulfate;

b4 In step b), the alkaline solution is sodium hydroxide aqueous solution;

b5 In step b), the mass percentage concentration of the alkaline solution is 4-15%.

2. The method for preparing 3,3', 4' -biphenyltetracarboxylic acid as recited in claim 1, further comprising at least one of the following technical features:

a5 In step a), cooling to-10-5 ℃;

a6 In step a), the molar ratio of phthalic anhydride to brominating agent is 1:1 to 1:1.3;

a7 In step a), the molar ratio of phthalic anhydride to alkali metal hydroxide is 1: 2-1: 3, a step of;

a8 In step a), the alkali metal is at least one selected from sodium, potassium, rubidium and cesium;

a9 In step a), the bromination reaction time is 8-12 h;

a10 In step a), the preparation method further comprises: carrying out post-treatment on the first filtrate obtained by filtering to obtain alkali metal bromide;

b3 In the step b), the cocatalyst exists in a water solution mode, and the mass percentage concentration is 19% -29%;

b6 In step b), the mass ratio of the catalyst to the 4-bromophthalic acid monoalkali metal salt is 0.009-0.015: 1, a step of; b7 In step b), the mass ratio of the cocatalyst to the monoalkali metal 4-bromophthalate is 0.2-0.4: 1, a step of; b8 In step b), the temperature of the coupling and hydrolysis reaction is 50-90 ℃;

b9 In step b), the time of the coupling and hydrolysis reaction is 8-12 h;

c1 In step c), the pH of the acidification reaction is 3-4;

c2 In step c), filtering and washing are carried out after the acidification reaction to obtain 3,3', 4' -biphenyl tetracarboxylic acid;

c3 In step c), cooling, preserving heat and crystallizing the second filtrate, and filtering to obtain a third filtrate and a first solid;

Acidifying the third filtrate, preserving heat for crystallization, and filtering to obtain a fourth filtrate and a second solid;

And adding the second solid into water, and carrying out heat preservation crystallization to obtain the 3,3', 4' -biphenyl tetracarboxylic acid.

3. The process for preparing 3,3', 4' -biphenyltetracarboxylic acid as claimed in claim 1,

B11 In the characteristic b 1), the mass percentage of Pd in Pd/C is 5-10%.

4. The method for preparing 3,3', 4' -biphenyltetracarboxylic acid as claimed in claim 2, comprising at least one of the following technical features:

c31 In feature c 3), centrifuging the first solid to obtain wet by-product alkali metal bromide;

c32 In the feature c 3), the fourth filtrate is decompressed, concentrated, cooled, filtered and centrifuged to obtain the alkali metal salt of the acid used for acidification.

5. A method for preparing 3,3', 4' -biphenyl tetracarboxylic dianhydride, which is characterized by comprising the following steps:

1) Obtaining 3,3', 4' -biphenyltetracarboxylic acid using the method for producing 3,3', 4' -biphenyltetracarboxylic acid as defined in any one of claims 1 to 4;

6. A method for producing 3,3', 4' -biphenyl tetracarboxylic acid, comprising the following steps:

c) Filtering the mixture obtained in the step b) to obtain a second filtrate;

Acidifying the third filtrate, preserving heat for crystallization, and filtering to obtain a fourth filtrate and a second solid; concentrating the fourth filtrate under reduced pressure, cooling, filtering and centrifuging to obtain alkali metal salt of acid for acidification; adding the second solid into water, and carrying out heat preservation crystallization to obtain 3,3', 4' -biphenyl tetracarboxylic acid;

in the step a), the mass percentage concentration of the alkali metal hydroxide aqueous solution is 7-11%;

in step a), the bromination reaction temperature is 80-100 ℃.

7. The method for producing 3,3', 4' -biphenyltetracarboxylic acid as recited in claim 6, further comprising at least one of the following technical features:

a1 In step a), the molar ratio of phthalic anhydride to brominating agent is 1:1 to 1:1.3;

a2 In step a), the molar ratio of phthalic anhydride to alkali metal hydroxide is 1: 2-1: 3, a step of; a4 In step a), the alkali metal is at least one selected from sodium, potassium, rubidium and cesium;

a6 In step a), the bromination reaction time is 8-12 h;

a7 In step a), cooling to-10 ℃ to-5 ℃;

a8 In step a), the first filtrate is subjected to post-treatment to obtain alkali metal bromide;

b1 In step b), the catalyst is Pd/C;

b2 In step b), the cocatalyst is hydroxylamine sulfate;

b4 In step b), the alkaline solution is sodium hydroxide aqueous solution;

b5 In step b), the mass percentage concentration of the alkaline solution is 25% -35%;

b9 In step b), the time of the coupling and hydrolysis reaction is 8-12 h;

c1 In step c), the pH of the acidification reaction is 3-4.