CN114516882A - Preparation method of cycloalkane tetracarboxylic dianhydride - Google Patents
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Abstract
The embodiment of the application provides a preparation method of cycloalkane tetracarboxylic dianhydride, which comprises the following steps: (1) reacting a compound shown in a formula (I) with a compound shown in a formula (II) under an alkaline condition to generate a compound shown in a formula (III); (2) hydrolyzing the compound of the formula (III) to obtain a compound of a formula (IV); (3) dehydrating the compound of formula (IV) to obtain the compound of formula (V). The preparation method has the advantages of simple operation, short reaction steps, high yield, high purity and mild reaction conditions, and is suitable for industrial mass production.
Description
Technical Field
The application relates to the technical field of organic chemistry, in particular to a preparation method of cycloalkane tetracarboxylic dianhydride.
Background
With the development of the photoelectric technology, especially the development of the display device of the intelligent electronic equipment in a bendable way in recent years, on the basis of keeping the original good thermal property and mechanical property, the photoelectric property of the polyimide is required to be higher, and the unique aromatic ring conjugated structure in the traditional polyimide structure causes the formation of intramolecular and intermolecular Charge Transfer Complex (CTC), which greatly affects the light transmittance of the polyimide film, so that an aliphatic structure is introduced into the polyimide film, the conjugation of the molecular structure is damaged, and the photoelectric property of the polyimide film can be greatly improved.
The cycloalkane tetracarboxylic dianhydride compound is an important material for preparing the polyimide film with high light transmittance, 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride and the like are widely applied at present, the synthesis of the compounds is different, for example, the cyclobutane tetracarboxylic dianhydride is synthesized by adopting a photocatalytic [2+2] cycloaddition reaction, the yield and the efficiency are low, and the industrial scale production is difficult to carry out; the cyclopentane tetracarboxylic dianhydride needs an olefin oxidation process, and a large number of byproducts are generated; cyclohexane tetracarboxylic dianhydride needs high-pressure hydrogenation preparation; the synthesis of other more complex cycloalkanetetracarboxylic dianhydrides requires more steps.
Disclosure of Invention
The embodiment of the application aims to provide a novel preparation method of cycloalkane tetracarboxylic dianhydride.
The application provides a preparation method of cycloalkane tetracarboxylic dianhydride, which comprises the following steps:
(1) reacting a compound shown in a formula (I) with a compound shown in a formula (II) under an alkaline condition to generate a compound shown in a formula (III);
(2) hydrolyzing the compound of the formula (III) to obtain a compound of a formula (IV);
(3) dehydrating the compound of formula (IV) to obtain a compound of formula (V);
wherein Y is selected from CN or COOR2；
R1、R2、R3Each independently selected from C1-4An alkyl group;
x is selected from Cl, Br and I;
Z1and Z2Each independently selected from a chemical bond or C1-4An alkylene group.
In some embodiments of the present application, the molar ratio of the compound of formula (I) to the compound of formula (II) is (1-1.5): 1.
in some embodiments of the present application, R1、R2、R3May be the same or different.
In some embodiments of the present application, step (1) comprises: adding a solution of a compound shown in a formula (I) at the temperature of between 20 ℃ below zero and 60 ℃ under an alkaline condition, preserving the heat for 0.5 to 4 hours, adding a solution of a compound shown in a formula (II), and reacting at the temperature of between 0 and 80 ℃ for 1 to 12 hours to generate a compound shown in a formula (III); wherein the solvent of the solution is at least one selected from tetrahydrofuran, N-dimethylformamide, methanol and ethanol.
In some embodiments of the present application, the molar ratio of the compound of formula (I) to the compound of formula (II) is 1: 1.
In some embodiments of the present application, step (2) comprises: adding the compound shown in the formula (III) into a dilute acid aqueous solution, and carrying out hydrolysis reaction at 50-120 ℃ to obtain a compound shown in the formula (IV); the dilute acid aqueous solution is selected from any one of dilute nitric acid, dilute hydrochloric acid and dilute sulfuric acid.
The concentration of the dilute aqueous acid solution is not limited in the present application as long as the object of the present application can be achieved, and for example, the dilute aqueous acid solution may be 15 to 25 vol%.
In some embodiments of the present application, step (2) further comprises: after the compound of formula (III) is added, a solvent capable of promoting the reaction is also added; the solvent is selected from C7-10At least one of fatty alcohols.
In this application, C7-10The fatty alcohol is not limited to n-alkanol, nor to monohydric alcohol; c7-10The fatty alcohol mainly plays a role in dissolving raw materials and catalyzing phase transfer, and meanwhile, the boiling point of the fatty alcohol cannot be too high or too low, so that the fatty alcohol can be distilled out after reaction as a reference; preferably, C7-10The fatty alcohol can be at least one of n-octanol, n-nonanol, n-decanol, 2-nonanol, 2-ethyl ethanol or isodecanol.
In some embodiments of the present application, step (2) comprises: adding the compound of the formula (III) into a dilute alkali aqueous solution, and carrying out hydrolysis reaction at 20-100 ℃ to obtain a compound of a formula (IV); the dilute alkali solution is selected from any one of sodium hydroxide solution and potassium hydroxide solution.
The concentration of the dilute alkali aqueous solution is not limited in the present application as long as the object of the present application can be achieved, and may be, for example, a 5 to 15 vol% dilute alkali aqueous solution.
In some embodiments of the present application, step (3) comprises: adding the compound shown in the formula (IV) into acetic anhydride, and performing dehydration reaction at 40-120 ℃ for 2-24h to obtain a compound shown in the formula (V); wherein the mass ratio of the compound shown in the formula (IV) to acetic anhydride is 1: (2-20).
In some embodiments of the present application, the method comprises the steps of:
(1) adding a solution of a compound of formula (I) at-20 to 60 ℃ under an alkaline condition, preserving heat for 0.5 to 4 hours, adding a solution of a compound of formula (II), and reacting at 0 to 80 ℃ for 1 to 12 hours to generate a compound of formula (III);
(2) adding the compound shown in the formula (III) into a dilute acid aqueous solution, and carrying out hydrolysis reaction at 50-120 ℃ to obtain a compound shown in the formula (IV);
(3) adding the compound of the formula (IV) into acetic anhydride, and carrying out dehydration reaction at 40-120 ℃ for 2-24h to obtain the compound of the formula (V).
In some embodiments of the present application, the method comprises the steps of:
(1) adding a solution of a compound of formula (I) at-20 to 60 ℃ under an alkaline condition, preserving heat for 0.5 to 4 hours, adding a solution of a compound of formula (II), and reacting at 0 to 80 ℃ for 1 to 12 hours to generate a compound of formula (III);
(2) adding the compound of the formula (III) into a dilute alkali aqueous solution, and carrying out hydrolysis reaction at 20-100 ℃ to obtain a compound of a formula (IV);
(3) adding the compound of the formula (IV) into acetic anhydride, and carrying out dehydration reaction at 40-120 ℃ for 2-24h to obtain the compound of the formula (V).
The application provides a preparation method of cycloalkane tetracarboxylic dianhydride, which comprises the steps of forming dicarbanions by using a double-active methylene compound under an alkaline condition, reacting with a double-halogen ester compound to synthesize a cycloalkane ester compound, hydrolyzing and decarboxylating to obtain cycloalkane tetracarboxylic acid, and dehydrating to obtain cycloalkane tetracarboxylic dianhydride. The preparation method has the advantages of simple operation, short reaction steps, high yield, high purity and mild reaction conditions, and is suitable for industrial mass production.
Detailed Description
The technical solutions of the present application will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in this application are within the scope of protection of this application.
Example 1
Preparation of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride
(1) Dropwise adding a solution prepared from 1,1,2, 2-ethane tetracarboxylic acid methyl ester (31.4g, 0.12mol) and 100mL of tetrahydrofuran into a 10% sodium methoxide solution (129.6g, 0.24mol) at 20 ℃, preserving heat for reaction for 1h at 20 ℃ after adding, then dropwise adding a solution prepared from 2, 3-dibromo dimethyl succinate (30.4g, 0.1mol) and 100mL of tetrahydrofuran, heating to 60 ℃ after adding, preserving heat for reaction for 4h, adjusting the pH of a reaction solution to be 5 by hydrochloric acid, filtering to remove generated solids, removing a solvent from a filtrate to obtain a crude product of 1,1,2,2,3, 4-cyclobutane hexachloroformate, adding 160mL of methanol, heating to 70 ℃ until the solids are completely dissolved, cooling to 5 ℃, and filtering to obtain a refined product of 1,1,2,2,3, 4-cyclobutane hexachloroformate 34.7g, the yield is 86%, and the purity is 99.2%;
(2) adding 34.7g of 1,1,2,2,3, 4-cyclobutane hexa methyl hexamer obtained in the step (1) into 200mL of 18% diluted hydrochloric acid solution, adding 50mL of n-octanol, stirring and heating to 110 ℃, reacting for 16h, after the raw material reaction detected by Thin Layer Chromatography (TLC) is finished, decompressing and distilling out the n-octanol and 170mL of water, then cooling to 10 ℃, filtering, leaching the solid with 100mL of acetone, drying to obtain 19.0g of cyclobutane tetracarboxylic acid, wherein the yield is 95.2%, and the purity is 99.4% by silanization;
(3) adding 19.0g of the cyclobutane tetracarboxylic acid obtained in the step (2) into 190g of acetic anhydride, stirring and heating to 100 ℃ under the protection of nitrogen for reaction for 24 hours, cooling to 10 ℃ for filtration, adding 100mL of acetone into a filter cake, heating to reflux, boiling and washing for 2 hours, cooling to 10 ℃ for filtration, leaching with acetone, and drying to obtain 14.8g of cyclobutane tetracarboxylic dianhydride, wherein the yield is 92.5% and the purity is 99.3%.
Example 2
Preparation of 1,2,3, 4-cyclopentanetetracarboxylic dianhydride
(1) Dropwise adding a solution prepared from 1,1,2, 2-ethane tetracarboxylic acid methyl ester (31.4g, 0.12mol) and 100mL of tetrahydrofuran into a 10% sodium methoxide solution (129.6g, 0.24mol) at 20 ℃, carrying out heat preservation reaction for 1h after adding, then dropwise adding a solution prepared from 2, 4-dibromo dimethyl glutarate (31.8g, 0.1mol) and 100mL of tetrahydrofuran, heating to 50 ℃ after adding, carrying out heat preservation reaction for 4h, adjusting the pH of a reaction solution to be 5 by hydrochloric acid, filtering to remove generated solid, removing a solvent from a filtrate to obtain a crude product of 1,1,2,2,3, 5-cyclopentane hexachloroformate, adding 160mL of methanol, heating to 70 ℃ until the solid is completely dissolved, then cooling to 5 ℃, and filtering to obtain a refined product of 1,1,2,2,3, 5-cyclopentane hexachloroformate 32.6g, the yield is 78%, and the purity is 99.3%;
(2) adding 32.6g of 1,1,2,2,3, 5-cyclopentane hexa-methyl formate obtained in the step (1) into 200mL of 18% dilute sulfuric acid solution, adding 50mL of n-octanol, stirring and heating to 110 ℃, reacting for 16h, reducing pressure to evaporate the n-octanol after TLC detection raw material reaction is finished, then cooling to 10 ℃, filtering, leaching the solid with 100mL of acetone, drying to obtain 17.6g of cyclopentane tetracarboxylic acid with yield of 92%, and measuring purity of 99.5% by silanization;
(3) adding 17.6g of the cyclopentanetetracarboxylic acid obtained in the step (2) into 176g of acetic anhydride, stirring and heating to 90 ℃ under the protection of nitrogen, reacting for 24h, cooling to 10 ℃, filtering, adding 100mL of acetone into a filter cake, heating to reflux, boiling and washing for 2h, cooling to 10 ℃, filtering, leaching with acetone, and drying to obtain 14.0g of cyclopentanetetracarboxylic dianhydride, wherein the yield is 93% and the purity is 99.6%.
Example 3
Preparation of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride
(1) Dropwise adding a solution prepared from 1,1,3, 3-propane tetracarboxylic acid methyl ester (33.1g, 0.12mol) and 100mL of tetrahydrofuran into a 10% sodium methoxide solution (129.6g, 0.24mol) at 20 ℃, keeping the temperature for reaction for 1h after the addition is finished, then dropwise adding a solution prepared from 2, 4-dibromoglutaric acid dimethyl ester (31.8g, 0.1mol) and 100mL of tetrahydrofuran, heating to 50 ℃ after the addition is finished, keeping the temperature for reaction for 4h, regulating the pH of the reaction liquid to be 5 by using hydrochloric acid, filtering to remove generated solids, removing a solvent from the filtrate to obtain a 1,1,3,3,4, 6-cyclohexane hexachloroformate crude product, adding 160mL of methanol, heating to 70 ℃ until the solids are completely dissolved, then cooling to 5 ℃, and filtering to obtain 29.2g of 1,1,3,3,4, 6-cyclohexane hexachloroformate refined product, yield is 67.5%, and purity is 98.7%;
(2) adding 29.2g of 1,1,3,3,4, 6-cyclohexane hexa methyl formate obtained in the step (1) into 200mL of 18% diluted hydrochloric acid solution, adding 50mL of n-octanol, stirring and heating to 110 ℃, reacting for 16h, reducing pressure to evaporate the n-octanol after TLC detection raw material reaction is finished, then cooling to 10 ℃, filtering, leaching the solid with 100mL of acetone, drying to obtain 15.4g of cyclohexane tetracarboxylic acid with yield of 88%, and measuring purity of 99.1% by silanization;
(3) adding 15.4g of the cyclohexane tetracarboxylic acid obtained in the step (2) into 154g of acetic anhydride, stirring and heating to 90 ℃ under the protection of nitrogen, reacting for 24h, cooling to 10 ℃, filtering, adding 100mL of acetone into a filter cake, heating to reflux, boiling and washing for 2h, cooling to 10 ℃, filtering, leaching with acetone, and drying to obtain 12.1g of cyclohexane tetracarboxylic dianhydride, wherein the yield is 91% and the purity is 99.2%.
Example 4
Preparation of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride
(1) Adding 34.5g (0.25mol) of potassium carbonate into 100mL of N, N-Dimethylformamide (DMF), dropwise adding a solution prepared from 1,1,2, 2-ethane tetracarboxylic acid methyl ester (31.4g, 0.12mol) and 50mL of N, N-dimethylformamide at 20 ℃, preserving heat for reaction for 2h after the addition is finished, then dropwise adding a solution prepared from 2, 3-dibromo dimethyl succinate (30.4g, 0.1mol) and 50mL of N, N-dimethylformamide, heating to 60 ℃ after the addition is finished, preserving heat for reaction for 4h, adjusting the pH of the reaction solution to 5 by hydrochloric acid, adding 200mL of ethyl acetate and 200mL of water, stirring for 30min, standing, layering, extracting the aqueous phase once by using 100mL of ethyl acetate, combining organic phases, washing once by water, removing a solvent, then recrystallizing by using 160mL of methanol to obtain 30.8g of 1,1,2,2,3, 4-cyclobutane hexamethoxylate, the yield is 73.6 percent, and the purity is 99.1 percent;
the steps (2) and (3) are the same as in example 1.
Example 5
Preparation of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride
(1) Adding 10g (0.25mol) of 60% sodium hydride into 100mL of tetrahydrofuran, dropwise adding a solution prepared by 1,1,2, 2-ethanedicarboxylic acid methyl ester (31.4g, 0.12mol) and 50mL of tetrahydrofuran at 20 ℃, preserving heat for reacting for 2h after adding, dropwise adding a solution prepared by 2, 3-dibromo-succinic acid dimethyl ester (30.4g, 0.1mol) and 50mL of tetrahydrofuran, heating to 60 ℃ after adding, preserving heat for reacting for 4h, adjusting the pH of the reaction solution to 5 by hydrochloric acid, adding 200mL of ethyl acetate and 200mL of water, stirring for 30min, standing, layering, extracting an aqueous phase once by 100mL of ethyl acetate, combining an organic phase, washing once by water, removing a solvent, and then recrystallizing by 160mL of methanol to obtain 33.1g, 1,2,2,3, 4-cyclobutane-hexamethyl, wherein the yield is 82%, and the purity is 99.2%;
the steps (2) and (3) are the same as in example 1.
Example 6
Preparation of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride
(1) Adding 24g (0.25mol) of sodium tert-butoxide into 100mL of tetrahydrofuran, dropwise adding a solution prepared from 1,1,2, 2-ethanedicarboxylic acid methyl ester (31.4g, 0.12mol) and 50mL of tetrahydrofuran at 20 ℃, preserving heat for reaction for 2h after adding, dropwise adding a solution prepared from 2, 3-dibromo-succinic acid dimethyl ester (30.4g, 0.1mol) and 50mL of tetrahydrofuran, heating to 60 ℃ after adding, preserving heat for reaction for 4h, adjusting the pH of the reaction solution to 5 by hydrochloric acid, adding 200mL of ethyl acetate and 200mL of water, stirring for 30min, standing, layering, extracting an aqueous phase once by 100mL of ethyl acetate, combining an organic phase, washing once by water, removing a solvent, and then recrystallizing by 160mL of methanol to obtain 31.7g of 1,1,2,2,3, 4-cyclobutane-hexamethyl, wherein the yield is 78.1%, and the purity is 99.1%;
the steps (2) and (3) are the same as in example 1.
Example 7
Preparation of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride
(1) Dropwise adding a solution prepared from 1,1,2, 2-ethane tetracarboxylic acid methyl ester (26.2g, 0.1mol) and 100mL of tetrahydrofuran into a 10% sodium methoxide solution (108g, 0.2mol) at 20 ℃, preserving heat for reaction for 1h at 20 ℃ after the addition is finished, then dropwise adding a solution prepared from 2, 3-dibromo dimethyl succinate (30.4g, 0.1mol) and 100mL of tetrahydrofuran, heating to 60 ℃ after the addition is finished, preserving heat for reaction for 4h, adjusting the pH of a reaction solution to be 5 by hydrochloric acid, filtering to remove generated solid, removing a solvent from a filtrate to obtain a crude product of 1,1,2,2,3, 4-cyclobutane hexachloroformate, adding 160mL of methanol, heating to 70 ℃ until the solid is completely dissolved, then cooling to 5 ℃, and filtering to obtain a refined product of 1,1,2,2,3, 4-cyclobutane hexachloroformate 32.6g, the yield is 80.7%, and the purity is 99.2%;
the steps (2) and (3) are the same as in example 1.
Example 8
The steps (1) and (3) are the same as in example 1;
(2) and (2) adding 34.7g of 1,1,2,2,3, 4-cyclobutane hexa-methyl hexametaphosphate obtained in the step (1) into 200mL of 18% diluted hydrochloric acid solution, stirring and heating to 110 ℃, reacting for 36h, evaporating 170mL of water under reduced pressure after TLC detection raw material reaction is finished, then cooling to 10 ℃, filtering, leaching the solid with 100mL of acetone, drying to obtain 18.9g of cyclobutane tetracarboxylic acid, wherein the yield is 94.8%, and the purity is 99.3% through silanization.
Example 9
The steps (1) and (3) are the same as those in example 1;
(2) adding 33.1g of 1,1,2,2,3, 4-cyclobutane hexa-methyl hexametaphosphate obtained in the step (1) into 200mL of 10% sodium hydroxide solution, stirring and heating to 70 ℃, reacting for 6h, cooling to 50 ℃ after TLC detection raw material reaction is finished, dropwise adding hydrochloric acid to adjust the pH to 3, decompressing and removing 100mL of water, then cooling to 10 ℃ and filtering, leaching the solid with 100mL of acetone, drying to obtain 16.9g of cyclobutane tetracarboxylic acid, wherein the yield is 89%, and the purity is 99.2% through silanization.
Other cycloalkanetetracarboxylic dianhydride-based compounds can also be prepared by a method similar to the examples of the present application.
And (3) calculating yield:
yield ═ mass of actual synthesized product/mass of theoretical synthesized product × 100%
And (3) purity testing: the purity of the product was checked by High Performance Liquid Chromatography (HPLC).
The above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the scope of protection of the present application.
Claims (9)
1. A preparation method of cycloalkane tetracarboxylic dianhydride comprises the following steps:
(1) reacting a compound shown in a formula (I) with a compound shown in a formula (II) under alkaline conditions to generate a compound shown in a formula (III);
(2) hydrolyzing the compound of the formula (III) to obtain a compound of a formula (IV);
(3) dehydrating the compound of formula (IV) to obtain a compound of formula (V);
wherein Y is selected from CN or COOR2；
R1、R2、R3Each independently selected from C1-4An alkyl group;
x is selected from Cl, Br and I;
Z1and Z2Each independently selected from a chemical bond or C1-4An alkylene group.
2. The process according to claim 1, wherein the molar ratio of the compound of formula (I) to the compound of formula (II) is (1-1.5): 1.
3. the production method according to claim 1, wherein the step (1) includes: adding a solution of a compound shown in a formula (I) at the temperature of between 20 ℃ below zero and 60 ℃ under an alkaline condition, preserving the heat for 0.5 to 4 hours, adding a solution of a compound shown in a formula (II), and reacting at the temperature of between 0 and 80 ℃ for 1 to 12 hours to generate a compound shown in a formula (III); wherein the solvent of the solution is at least one selected from tetrahydrofuran, N-dimethylformamide, methanol and ethanol.
4. The production method according to claim 1, wherein the step (2) includes: adding the compound shown in the formula (III) into dilute acid aqueous solution, and performing hydrolysis reaction at 50-120 ℃ to obtain a compound shown in the formula (IV); the dilute acid aqueous solution is selected from any one of dilute nitric acid, dilute hydrochloric acid and dilute sulfuric acid.
5. The production method according to claim 4, wherein the step (2) further comprises: after the compound of formula (III) is added, a solvent capable of promoting the reaction is also added; the solvent is selected from C7-10At least one of fatty alcohols.
6. The production method according to claim 1, wherein the step (2) includes: adding the compound of the formula (III) into a dilute alkali aqueous solution, and carrying out hydrolysis reaction at 20-100 ℃ to obtain a compound of a formula (IV); the dilute alkali solution is selected from any one of sodium hydroxide solution and potassium hydroxide solution.
7. The production method according to claim 1, wherein the step (3) includes: adding the compound shown in the formula (IV) into acetic anhydride, and performing dehydration reaction at 40-120 ℃ for 2-24h to obtain a compound shown in the formula (V); wherein the mass ratio of the compound of formula (IV) to acetic anhydride is 1: (2-20).
8. The production method according to claim 1, comprising the steps of:
(1) adding a solution of a compound of formula (I) at-20 to 60 ℃ under an alkaline condition, preserving heat for 0.5 to 4 hours, adding a solution of a compound of formula (II), and reacting at 0 to 80 ℃ for 1 to 12 hours to generate a compound of formula (III);
(2) adding the compound shown in the formula (III) into a dilute acid aqueous solution, and carrying out hydrolysis reaction at 50-120 ℃ to obtain a compound shown in the formula (IV);
(3) adding the compound of the formula (IV) into acetic anhydride, and carrying out dehydration reaction at 40-120 ℃ for 2-24h to obtain the compound of the formula (V).
9. The production method according to claim 1, comprising the steps of:
(1) adding a solution of a compound of formula (I) at-20 to 60 ℃ under an alkaline condition, preserving heat for 0.5 to 4 hours, adding a solution of a compound of formula (II), and reacting at 0 to 80 ℃ for 1 to 12 hours to generate a compound of formula (III);
(2) adding the compound of the formula (III) into a dilute alkali aqueous solution, and carrying out hydrolysis reaction at 20-100 ℃ to obtain a compound of a formula (IV);
(3) adding the compound of the formula (IV) into acetic anhydride, and carrying out dehydration reaction at 40-120 ℃ for 2-24h to obtain the compound of the formula (V).
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