CN114524823A - Preparation method of tetracarboxylic dianhydride alicyclic compound - Google Patents
Preparation method of tetracarboxylic dianhydride alicyclic compound Download PDFInfo
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Abstract
The application relates to the field of organic synthesis, and particularly discloses a preparation method of a tetracarboxylic dianhydride alicyclic compound, which comprises the following steps: reacting maleic acid glycoside, cyclopentadiene, aniline and acetic anhydride in solvent chloroform to generate an intermediate (I); (II) carbonyl insertion reaction: carrying out carbonylation reaction on the intermediate (I) in the atmosphere of carbon monoxide to generate an intermediate (II); (III) ring closure reaction: using dibromoethane to carry out ring-closing reaction to generate an intermediate (III); (IV) hydrolysis reaction: hydrolyzing the intermediate (III) to remove aniline to obtain an Intermediate (IV); (V) anhydride forming reaction: and (4) dehydrating the Intermediate (IV) in acetic anhydride to obtain a target product. The preparation method provided by the application has the advantages that the reaction is carried out step by step, the tracking and the purification are easy, the operation is simple, the purity and the yield of the target product are high, the noble metal palladium catalyst is avoided in the reaction process, and the cost is reduced.
Description
Technical Field
The application relates to the technical field of organic synthesis, in particular to a preparation method of a tetracarboxylic dianhydride alicyclic compound, and especially relates to a preparation method of norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' -tetracarboxylic dianhydride.
Background
Polyimide (PI) has a higher thermal decomposition temperature than other plastics, can reach 500 ℃ or even higher, is not only heat-resistant, but also is an excellent material in mechanical and electrical properties. In recent years, with the development of foldable smart phones, transparent polyimide (CPI) has attracted attention as a glass substitute material in liquid crystal displays and organic EL displays. The transparent polyimide (CPI) is required to be not only transparent but also have properties of high heat resistance, low expansion coefficient, and the like. Aliphatic dianhydrides and diamines are preferred for the synthesis of CPI, but aliphatic dianhydrides reduce the thermal properties of CPI. Norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "tetracarboxylic dianhydride (CpODA) is a dianhydride of alicyclic structure, which has no aromatic skeleton but has a rigid alicyclic structure, and which is polymerized with a diamine to produce a polyimide solution and film having characteristics of being colorless and transparent, high in heat resistance, low in expansion coefficient, and the like, and is useful for smart phone substrate materials, cover films, and the like.
In the related art, the synthesis route of norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic dianhydride is as follows: firstly, performing amine methylation on cyclopentanone to generate 2, 5-dimethylamino cyclopentanone, then performing in-situ elimination to generate 2, 5-dimethylene cyclopentanone, then reacting with cyclopentadiene to generate norbornene-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornene, performing an interposing reaction on the product to generate norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic acid methyl ester, performing acid catalytic ester exchange, and then dehydrating acetic anhydride to obtain an anhydride, thereby obtaining the target product.
Aiming at the related technologies, the first three steps of the synthesis process are combined together for reaction, each step is inconvenient for purification, so that the purity of an intermediate product is low, the yield is low, the effect of the subsequent reaction is not good, and the carbonylation insertion reaction process needs to be catalyzed by palladium chloride, so that the cost is high.
Disclosure of Invention
In order to improve the yield and purity of the synthesis reaction and reduce the reaction cost, the application provides a preparation method of a tetracarboxylic dianhydride alicyclic compound; the following technical scheme is adopted:
a preparation method of tetracarboxylic dianhydride alicyclic compound comprises the following steps:
(one) Diels-Alder reaction: dissolving maleic acid glycoside in chloroform under the condition of stirring, controlling the temperature to be 0 ℃, adding cyclopentadiene, carrying out heat preservation reaction for 28-32 min, adding aniline after the reaction is finished, controlling the adding temperature to be not more than 20 ℃, carrying out heat preservation reaction for 28-32 min, adding acetic anhydride and a catalyst, carrying out reflux reaction for 1.8-2.2 h, carrying out spin drying, pulping, filtering, washing a filter cake, and drying to obtain an intermediate (I);
(II) carbonyl insertion reaction: adding octacarbonyl cobaltic oxide and chloroborane diethylaniline complex into tetrahydrofuran under the atmosphere of carbon monoxide, stirring for dissolving, adding a tetrahydrofuran solution of an intermediate (I), keeping the temperature for reacting for 28-32 h, cooling, adding hydrogen peroxide with the mass percentage concentration of 25%, stirring for reacting for 28-32 min, adjusting the pH to 4-5 after the reaction is finished, carrying out spin-drying, adding ethyl acetate for dissolving, washing, drying, filtering, and spin-drying the filtrate to obtain an intermediate (II);
(III) ring closure reaction: dissolving the intermediate (II) in tetrahydrofuran under the protection of nitrogen, cooling to-60 ℃ by liquid nitrogen, adding a lithium reagent, carrying out heat preservation reaction for 18-22 min, adding dibromoethane after the reaction is finished, carrying out heat preservation reaction for 1.8-2.2 h, adding pure water after the reaction is finished, carrying out quenching reaction, spin-drying, pulping, and filtering to obtain an intermediate (III);
(IV) hydrolysis reaction: dissolving the intermediate (III) in 2mol/L sodium hydroxide solution under the condition of stirring, carrying out reflux reaction for 7.8-8.2 h, controlling the temperature to be 0 ℃ after the reaction is finished, adjusting the pH to 4-5, filtering, washing a filter cake, and drying to obtain an Intermediate (IV);
(V) anhydride forming reaction: dissolving the Intermediate (IV) in acetic anhydride under the condition of stirring, carrying out reflux reaction for 4.8-5.2 h, cooling, filtering, and drying a filter cake to obtain an aliphatic tetracarboxylic dianhydride compound (V);
the reaction formula is shown as follows:
in the preparation method, in the first step, maleic anhydride, cyclopentadiene, aniline and acetic anhydride are subjected to Diels-Alder reaction in chloroform solvent in the presence of a catalyst to generate an intermediate (I); the second step of reaction, the intermediate (I) is subjected to carbonyl insertion reaction in the carbon monoxide atmosphere to generate an intermediate (II); in the third step of reaction, under the condition that a lithium reagent and dibromoethane exist, the intermediate (II) is subjected to ring closure to generate an intermediate (III); in the fourth step of reaction, the intermediate (III) is subjected to hydrolysis reaction under the alkaline condition, aniline is removed, and an Intermediate (IV) is generated; and step five, dehydrating the Intermediate (IV) by using acetic anhydride to generate the target product of norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic dianhydride. According to the preparation method, the reaction process of each step is simple and easy to purify, and the reaction of each step has high purity and yield, so that the reaction is easy to track, and the final target product has high yield and purity. In addition, the preparation method avoids noble metal palladium as a catalyst in the process, and also reduces the cost.
Preferably, in the step (one), the molar ratio of the maleic anhydride, the cyclopentadiene, the aniline and the acetic anhydride is 1:1.1:1: 1.5.
Preferably, in step (one), the catalyst is sodium acetate or potassium acetate.
Preferably, in the step (one), the molar ratio of the catalyst to the maleic anhydride is 1: 0.190-0.200.
Preferably, in the step (II), the molar ratio of the cobaltosic octacarbonyl, the chloroborane diethylaniline complex, the solvent in hydrogen peroxide and the intermediate (I) is 0.25-0.27: 0.50-0.64: 2: 1.
Preferably, in the step (III), the molar ratio of the intermediate (II) to dibromoethane is 1: 1.1-1.2.
Preferably, in step (iii), the lithium reagent is butyllithium or lithium diisopropylamide.
Preferably, in the step (III), the molar ratio of the lithium reagent to the intermediate (II) is 1: 2.20-2.33.
In summary, the present application has the following beneficial effects:
1. according to the synthesis method, the reactions in each step are easy to track, and the purity of the intermediate product is high, so that the finally prepared norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic dianhydride has high yield and purity;
2. the synthesis method has the advantages of simple steps, low requirements on process conditions and convenience in implementation;
3. the synthesis method avoids the use of noble metal palladium as a catalyst, and is beneficial to reducing the synthesis reaction cost.
Drawings
FIG. 1 is a reaction scheme of the synthetic process provided in examples 1-4 herein;
FIG. 2 is a reaction scheme of the synthetic process provided in comparative example 1 of the present application.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples.
The raw materials used in the examples of the present application are commercially available, except for the following specific descriptions:
the chloroborane diethylaniline complex is self-made, and the preparation method comprises the following steps: dissolving 4.1g of borane diethylaniline complex in 50mL of tetrahydrofuran to obtain a tetrahydrofuran solution of borane diethylaniline complex; dissolving 3.2g of anhydrous cobalt chloride in 100mL of tetrahydrofuran to obtain a tetrahydrofuran solution of the anhydrous cobalt chloride; and (3) dripping the tetrahydrofuran solution of borane diethylaniline complex into the tetrahydrofuran solution of anhydrous cobalt chloride for 5min, controlling the temperature to be 25 ℃ in the dripping process, and then keeping the temperature and stirring for 2h to obtain the chloroborane diethylaniline complex.
Examples
Example 1
A norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic dianhydride, the synthetic route of which is shown in figure 1, specifically comprises the following steps:
(one) Diels-Alder reaction: taking 300mL of chloroform, adding 98g (1 mol) of maleic anhydride under the condition of stirring, cooling to 0 ℃ by using an ice-water bath after dissolving, slowly dropwise adding 73g (1.1 mol) of cyclopentadiene within 30min, keeping the temperature and stirring for 30min after dropwise adding, dropwise adding 93g (1 mol) of aniline, controlling the dropwise adding temperature to be not more than 20 ℃, keeping the temperature and stirring for 30min at 20 ℃ after dropwise adding, adding 153g (1.5 mol) of acetic anhydride and 16g (195 mmol) of sodium acetate, carrying out reflux reaction for 2h, carrying out spin drying at 40 ℃, then adding 1L of pure water, pulping, filtering, washing a filter cake, and drying to obtain 220g of an intermediate (I), wherein the purity is 98.0%, and the yield is 92.0%;
(II) carbonyl insertion reaction: taking 150mL tetrahydrofuran, adding 4.3g (12.5 mmol) of cobaltosic octacarbonyl and 4.9g (25 mmol) of chloroborane diethylaniline complex under the atmosphere of carbon monoxide, stirring for dissolving, dropwise adding a tetrahydrofuran solution (12 g, 50 mmol) of the intermediate (I) into 50mL tetrahydrofuran at room temperature (25 ℃), stirring for 30h after dropwise adding, stopping carbon monoxide, dropwise adding 13.6g of hydrogen peroxide with the mass percent concentration of 25% under the cooling of an ice water bath at the temperature of 0-5 ℃, stirring for 30min after dropwise adding, adjusting the pH to 4-5 by using 20% dilute sulfuric acid, carrying out rotary evaporation at the temperature of 50 ℃ to remove the tetrahydrofuran, dissolving the remainder by using ethyl acetate, washing by using pure water, a saturated sodium carbonate aqueous solution and a saturated saline solution in sequence, drying, filtering, and carrying out rotary drying on the filtrate until no solution remains to obtain 9g of the intermediate (II), the purity of 95.1%, the yield is 79.7%;
(III) ring closure reaction: under the protection of nitrogen, dissolving 7.6g (15 mmol) of intermediate (II) in 100mL of tetrahydrofuran, cooling to-60 ℃ by liquid nitrogen, slowly dropwise adding 13.2mL of butyl lithium n-hexane solution (the content of butyl lithium is 2.5 mol/L) within 10min, keeping the temperature and stirring for 20min after dropwise adding, slowly dropwise adding 3.1g (16.5 mmol) of dibromoethane within 8min, keeping the temperature and reacting for 2h after dropwise adding, dropwise adding 5mL of pure water to quench the reaction, spin-drying until no solvent remains, adding 50mL of pure water to pulp, and filtering to obtain 12g of wet intermediate (III);
(IV) hydrolysis reaction: adding 12g of wet intermediate (III) into 50mL of sodium hydroxide solution (the content of sodium hydroxide is 2 mol/L), carrying out reflux reaction at 100 ℃ for 8h, cooling to 0 ℃ after the reaction is finished, adjusting the pH to 4-5 by using hydrochloric acid with the mass percentage concentration of 35%, filtering, leaching a filter cake by using pure water, and drying to obtain 5.5g of Intermediate (IV), wherein the purity is 95.3%, and the total yield of the step (III) and the step (IV) is 88.0%;
(V) anhydride forming reaction: adding 5.5g of Intermediate (IV) into 20mL of acetic anhydride, refluxing and reacting at 110 ℃ for 5h, cooling to room temperature (25 ℃), filtering, and drying a filter cake to obtain 4.5g of norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6', andtetracarboxylic dianhydride [ 2 ]1H NMR (400 MHz, DMSO-d 6) δ 3.48 (s, 2H), 3.17 (q, J = 7.6 Hz, 4H), 2.45 (s, 4H), 2.04 (d, J = 11.5 Hz, 2H), 1.77 – 1.70 (m, 4H), 1.36 (d, J = 12.5 Hz, 2H), 1.15 – 1.05 (m, 2H).]Purity 98.2% and yield 89.5%.
The melting point of the obtained norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic dianhydride is detected to be 205.3 ℃.
Example 2
A norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic dianhydride, the synthetic route of which is shown in figure 1, specifically comprises the following steps:
(one) Diels-Alder reaction: taking 300mL of chloroform, adding 98g (1 mol) of maleic anhydride under the condition of stirring, cooling to 0 ℃ by using an ice-water bath after dissolving, slowly dropwise adding 73g (1.1 mol) of cyclopentadiene within 30min, keeping the temperature and stirring for 30min after dropwise adding, dropwise adding 93g (1 mol) of aniline, controlling the dropwise adding temperature to be not more than 20 ℃, keeping the temperature and stirring for 30min at 20 ℃ after dropwise adding, adding 153g (1.5 mol) of acetic anhydride and 19.6g (200 mmol) of potassium acetate, carrying out reflux reaction for 2h, carrying out spin-drying at 40 ℃, then adding 1L of pure water, pulping, filtering, washing a filter cake, and drying to obtain 223g of an intermediate (I), wherein the purity is 98.1%, and the yield is 93.2%.
(II) carbonyl insertion reaction: the same as example 1;
(III) ring closure reaction: the same as example 1;
(IV) hydrolysis reaction: the same as example 1;
(V) anhydride forming reaction: as in example 1, 4.4g of norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "tetracarboxylic dianhydride [ 2 ], [1H NMR (400 MHz, DMSO-d 6) δ 3.48 (s, 2H), 3.17 (q, J = 7.6 Hz, 4H), 2.45 (s, 4H), 2.04 (d, J = 11.5 Hz, 2H), 1.77 – 1.70 (m, 4H), 1.36 (d, J = 12.5 Hz, 2H), 1.15 – 1.05 (m, 2H).]Purity 98.1% and yield 87.5%.
The melting point of the obtained norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic dianhydride is detected to be 205.4 ℃.
Example 3
A norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic dianhydride, the synthetic route of which is shown in figure 1, specifically comprises the following steps:
(one) Diels-Alder reaction: the same as example 1;
(II) carbonyl insertion reaction: taking 150mL tetrahydrofuran, adding 4.6g (13.5 mmol) of cobaltosic octacarbonyl and 6.3g (32 mmol) of chloroborane diethylaniline complex under the atmosphere of carbon monoxide, stirring for dissolving, dropwise adding a tetrahydrofuran solution (12 g, 50 mmol) of the intermediate (I) into 50mL tetrahydrofuran at room temperature (25 ℃), stirring for 30h after dropwise adding, stopping carbon monoxide, dropwise adding 13.6g of hydrogen peroxide with the mass percent concentration of 25% under the cooling of an ice water bath at the temperature of 0-5 ℃, stirring for 30min after dropwise adding, adjusting the pH to 4-5 by using 20% dilute sulfuric acid, carrying out rotary evaporation at the temperature of 50 ℃ to remove the tetrahydrofuran, dissolving the remainder by using ethyl acetate, washing by using pure water, a saturated sodium carbonate aqueous solution and a saturated saline solution in sequence, drying, filtering, and carrying out rotary drying on the filtrate until no solution remains to obtain 9.2g and 95.0% purity of the intermediate (II), the yield is 81.5%;
(III) ring closure reaction: the same as example 1;
(IV) hydrolysis reaction: the same as example 1;
(V) anhydride forming reaction: in the same manner as in example 1, 4.46g of norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "tetracarboxylic dianhydride [ sic ], [1H NMR (400 MHz, DMSO-d 6) δ 3.48 (s, 2H), 3.17 (q, J= 7.6 Hz, 4H), 2.45 (s, 4H), 2.04 (d, J = 11.5 Hz, 2H), 1.77 – 1.70 (m, 4H), 1.36 (d, J = 12.5 Hz, 2H), 1.15 – 1.05 (m, 2H).]Purity 98.0%, yield 88.7%.
The melting point of the obtained norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic dianhydride is detected to be 205.7 ℃.
Example 4
A norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic dianhydride, the synthetic route of which is shown in figure 1, specifically comprises the following steps:
(one) Diels-Alder reaction: the same as example 1;
(II) carbonyl insertion reaction: the same as example 1;
(III) ring closure reaction: under the protection of nitrogen, 7.6g (15 mmol) of intermediate (II) is dissolved in 100mL of tetrahydrofuran, liquid nitrogen is cooled to-60 ℃, 17.5mL of lithium diisopropylamide n-hexane tetrahydrofuran mixed solution (the content of lithium diisopropylamide is 2.0mol/L, the volume ratio of n-hexane to tetrahydrofuran is 1: 1) is slowly dripped in within 10min, the mixture is kept warm and stirred for 20min after the dripping is finished, 3.1g (16.5 mmol) of dibromoethane is slowly dripped in within 8min, the mixture is kept warm and reacts for 2h after the dripping is finished, then 5mL of pure water is dripped to quench the reaction, the mixture is dried until no solvent remains, 50mL of pure water is added for pulping, and the wet product of intermediate (III) is obtained by filtering 12.3 g;
(IV) hydrolysis reaction: the same as example 1;
(V) anhydride forming reaction: in the same manner as in example 1, 4.48g of norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "tetracarboxylic dianhydride [ sic ], [1H NMR (400 MHz, DMSO-d 6) δ 3.48 (s, 2H), 3.17 (q, J= 7.6 Hz, 4H), 2.45 (s, 4H), 2.04 (d, J = 11.5 Hz, 2H), 1.77 – 1.70 (m, 4H), 1.36 (d, J = 12.5 Hz, 2H), 1.15 – 1.05 (m, 2H).]Purity 98.1% and yield 89.1%.
The melting point of the obtained norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic dianhydride is detected to be 205.6 ℃.
Comparative example
Comparative example 1
A norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic dianhydride, the synthetic route of which is shown in figure 2, comprises the following steps:
(one) mannich reaction and diels-alder reaction: dropwise adding 8.19g of hydrochloric acid with the mass percent concentration of 35% into 6.83g of dimethylamine aqueous solution with the mass percent concentration of 50%, adding 2.78g of formaldehyde and 2.59g of cyclopentanone, controlling the oil bath temperature to be 90 ℃ under the nitrogen atmosphere, stirring for reaction for 3 hours, cooling to 50 ℃ after the reaction is finished, adding 50mL of methoxyethanol, 1.12g of dimethylamine aqueous solution with the mass percent concentration of 50% and 7.13g of cyclopentadiene, controlling the oil bath temperature to be 120 ℃ under the nitrogen atmosphere, reacting for 90 minutes, cooling to room temperature (25 ℃), extracting for 2 times by using 80mL of n-heptane, combining organic phases, washing by using 25mL of sodium hydroxide solution with the mass percent concentration of 5%, 25mL of sodium bicarbonate solution with the mass percent concentration of 5% and 25mL of saturated sodium chloride water in sequence, drying, spin-drying the filtrate until no solvent remains, obtaining 7.4g of crude norbornene-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornene product, purification by distillation (boiling point 105 ℃ C./0.1 mm Hg) gave 4.5g of norbornene-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornene in 61% yield;
(II) carbonyl insertion reaction: reacting 2g of norbornene-2-spiro- α -cyclopentanone- α '-spiro-2 "-norbornene, 7.52g of sodium acetate, 8.95g of copper chloride and 34mL of palladium chloride under nitrogen atmosphere at 25 ℃ and 0.1MPa for 1h, introducing 3.2L of carbon monoxide, concentrating, removing carbon monoxide, adding the residue to 500mL of chloroform, filtering, washing with saturated sodium bicarbonate, collecting the organic phase, drying with anhydrous magnesium chloride, filtering, and spin-drying the filtrate until no solvent remains to obtain 3.93g of norbornane-2-pentanone- α -cyclopropan- α' -spiro-2" -norbornane-5, 5 ", 6, 6" methyl tetracarboxylic acid ester with a yield of 98.5%;
(III) anhydride forming reaction: 1.93g of norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic acid methyl ester, 14mL of formic acid and 0.1g of anhydrous p-toluenesulfonic acid are mixed, the temperature of an oil bath is controlled to be 120 ℃, reflux reaction is carried out for 6h, after the reaction is finished, the mixture is concentrated to 50% of the original volume, 7mL of formic acid is added, reflux reaction is carried out for 3h at 120 ℃, and rotary drying is carried out, so that 1.56g of norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic dianhydride is obtained, the purity is 92.3%, and the yield is 82.1%.
In summary, the norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "tetracarboxylic dianhydride prepared by the synthesis method of embodiments 1 to 4 of the present application has high purity and yield, the purity is not less than 98%, and the yield is not less than 87.5%. In contrast, in comparative example 1, the purity and yield of norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5, 5", 6,6 "tetracarboxylic dianhydride were reduced, with a purity of only 92.3% and a yield of only 82.1%. It is shown that the norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5, 5 ', 6, 6' tetracarboxylic dianhydride prepared by the synthesis method of the present application is not only easy to purify, but also has high yield. Further, compared with comparative example 1, in the synthesis routes of examples 1 to 4 of the present application, noble metal palladium is not used as a catalyst, so that the reaction cost is greatly reduced.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. A method for preparing a tetracarboxylic dianhydride alicyclic compound is characterized by comprising the following steps:
(one) Diels-Alder reaction: dissolving maleic acid glycoside in chloroform under the condition of stirring, controlling the temperature to be 0 ℃, adding cyclopentadiene, carrying out heat preservation reaction for 28-32 min, adding aniline after the reaction is finished, controlling the adding temperature to be not more than 20 ℃, carrying out heat preservation reaction for 28-32 min, adding acetic anhydride and a catalyst, carrying out reflux reaction for 1.8-2.2 h, carrying out spin drying, pulping, filtering, washing a filter cake, and drying to obtain an intermediate (I);
(II) carbonyl insertion reaction: adding octacarbonyl cobaltic oxide and chloroborane diethylaniline complex into tetrahydrofuran under the atmosphere of carbon monoxide, stirring for dissolving, adding a tetrahydrofuran solution of an intermediate (I), keeping the temperature for reacting for 28-32 h, cooling, adding hydrogen peroxide with the mass percentage concentration of 25%, stirring for reacting for 28-32 min, adjusting the pH to 4-5 after the reaction is finished, carrying out spin-drying, adding ethyl acetate for dissolving, washing, drying, filtering, and spin-drying the filtrate to obtain an intermediate (II);
(III) ring closure reaction: dissolving the intermediate (II) in tetrahydrofuran under the protection of nitrogen, cooling to-60 ℃ by liquid nitrogen, adding a lithium reagent, carrying out heat preservation reaction for 18-22 min, adding dibromoethane after the reaction is finished, carrying out heat preservation reaction for 1.8-2.2 h, adding pure water after the reaction is finished, carrying out quenching reaction, spin-drying, pulping, and filtering to obtain an intermediate (III);
(IV) hydrolysis reaction: dissolving the intermediate (III) in 2mol/L sodium hydroxide solution under the condition of stirring, carrying out reflux reaction for 7.8-8.2 h, controlling the temperature to be 0 ℃ after the reaction is finished, adjusting the pH to 4-5, filtering, washing a filter cake, and drying to obtain an Intermediate (IV);
(V) anhydride forming reaction: dissolving the Intermediate (IV) in acetic anhydride under the condition of stirring, carrying out reflux reaction for 4.8-5.2 h, cooling, filtering, and drying a filter cake to obtain an aliphatic tetracarboxylic dianhydride compound (V);
the reaction formula is shown as follows:
2. the method for producing a tetracarboxylic dianhydride alicyclic compound according to claim 1, wherein in the step (one), the molar ratio of maleic anhydride, cyclopentadiene, aniline, and acetic anhydride is 1:1.1:1: 1.5.
3. A process for producing a tetracarboxylic dianhydride alicyclic compound according to claim 1, wherein in the step (one), the catalyst is sodium acetate or potassium acetate.
4. A method for producing a tetracarboxylic dianhydride alicyclic compound according to claim 1 or 3, wherein in the step (one), the molar ratio of the catalyst to the maleic anhydride is 1:0.190 to 0.200.
5. A method for producing a tetracarboxylic dianhydride alicyclic compound according to claim 1, wherein in the step (II), the molar ratio of octacarbonyldicobalt, chloroborane diethylaniline complex, the solvent in hydrogen peroxide, and the intermediate (I) is 0.25 to 0.27:0.50 to 0.64:2: 1.
6. A process for producing a tetracarboxylic dianhydride alicyclic compound according to claim 1, wherein in the step (III), the molar ratio of the intermediate (II) to dibromoethane is 1:1.1 to 1.2.
7. The method for producing a tetracarboxylic dianhydride alicyclic compound according to claim 1, wherein in the step (iii), the lithium reagent is butyllithium or lithium diisopropylamide.
8. A method for producing a tetracarboxylic dianhydride alicyclic compound according to claim 1 or 7, wherein in the step (III), the molar ratio of the lithium reagent to the intermediate (II) is 1: 2.20 to 2.33.
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