CN114524823B - Preparation method of tetracarboxylic dianhydride alicyclic compound - Google Patents
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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 of (I) Diels-Alder reaction: reacting maleic anhydride, cyclopentadiene, aniline and acetic anhydride in solvent chloroform to generate an intermediate (I); (II) carbonyl insertion reaction: carrying out carbonyl insertion 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, and although it has no aromatic skeleton, its alicyclic structure has a rigid structure, and it is polymerized with a diamine, and a polyimide solution and a film having characteristics of being colorless and transparent, high in heat resistance, low in expansion coefficient, and the like can be produced, and can be used 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 aminomethylation on cyclopentanone to generate 2,5-dimethylaminocyclopentanone, then eliminating in situ to generate 2,5-dimethylenecyclopentanone, then reacting with cyclopentadiene to generate norbornene-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornene, performing an insertion-carbonylation 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-catalyzed transesterification, and then dehydrating acetic anhydride to obtain an anhydride, thus 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 method for preparing a tetracarboxylic dianhydride alicyclic compound comprises the following steps:
(one) Diels-Alder reaction: dissolving maleic anhydride 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 after the reaction is finished to obtain an intermediate (I);
(II) carbonyl insertion reaction: adding cobaltosic carbonyl and chloroborane diethylaniline complex into tetrahydrofuran under the atmosphere of carbon monoxide, stirring for dissolving, adding tetrahydrofuran solution of the 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 value 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 in the fifth step of reaction, the Intermediate (IV) is dehydrated by 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.
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.
Preferably, in the step (ii), the molar ratio of the octacarbonyldicobalt, chloroborane diethylaniline complex, solute in hydrogen peroxide and intermediate (i) is 0.25 to 0.27.
Preferably, in the step (III), the molar ratio of the intermediate (II) to dibromoethane is 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.
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 starting materials used in the examples of the present application are commercially available, except as specifically noted below:
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 is shown in figure 1, and 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 and dissolving, dropwise adding tetrahydrofuran solution (12g, 50mmol intermediate (I) and dissolving in 50mL tetrahydrofuran) of the intermediate (I) at room temperature (25 ℃), stirring for 30h after dropwise adding, stopping carbon monoxide, dropwise adding 13.6g of 25 mass percent hydrogen peroxide under cooling in an ice water bath at 0-5 ℃, stirring for 30min after dropwise adding, adjusting the pH to 4-5 by using 20 mass percent dilute sulfuric acid, carrying out rotary evaporation at 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 salt 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 is 95.1%, and the yield is 79.7%;
(III) ring closure reaction: dissolving 7.6g (15 mmol) of intermediate (II) in 100mL of tetrahydrofuran under the protection of nitrogen, 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 the Intermediate (IV) to 20mL of acetic anhydride, refluxing at 110 ℃ for 5 hours, cooling to room temperature (25 ℃), filtering, and drying the filter cake to obtain 4.5g of norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5,5 ', 6,6' tetracarboxylic dianhydride 1 H NMR(400MHz,DMSO-d 6 )δ3.48(s,2H),3.17(q,J＝7.6Hz,4H),2.45(s,4H),2.04(d,J＝11.5Hz,2H),1.77–1.70(m,4H),1.36(d,J＝12.5Hz,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 'and 6,6' tetracarboxylic dianhydride is 205.3 ℃ through detection.
Example 2
A norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5,5 '6,6' tetracarboxylic dianhydride is shown in figure 1, and 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: in the same manner as in example 1, 4.4g of norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 "-norbornane-5,5", 6,6 "tetracarboxylic dianhydride [ alpha ], [ solution of 1 H NMR(400MHz,DMSO-d 6 )δ3.48(s,2H),3.17(q,J＝7.6Hz,4H),2.45(s,4H),2.04(d,J＝11.5Hz,2H),1.77–1.70(m,4H),1.36(d,J＝12.5Hz,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 205.4 ℃ by detection.
Example 3
A norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5,5 '6,6' tetracarboxylic dianhydride is shown in figure 1, and 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 (12g) of the intermediate (I) (50mmol intermediate (I) is dissolved in 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, drying and evaporating the tetrahydrofuran at the temperature of 50 ℃, dissolving the remainder by using ethyl acetate, washing by using pure water, a saturated sodium carbonate aqueous solution and a saturated salt solution in sequence, drying, filtering, and drying the filtrate until no solution remains to obtain 9.2g of the intermediate (II), the purity of 95.0% and the yield of 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 [ alpha ], [ solution of 1 H NMR(400MHz,DMSO-d 6 )δ3.48(s,2H),3.17(q,J＝7.6Hz,4H),2.45(s,4H),2.04(d,J＝11.5Hz,2H),1.77–1.70(m,4H),1.36(d,J＝12.5Hz,2H),1.15–1.05(m,2H).]Purity 98.0% and yield 88.7%.
The melting point of the obtained norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5,5 'and 6,6' tetracarboxylic dianhydride is 205.7 ℃ through detection.
Example 4
A norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5,5 '6,6' tetracarboxylic dianhydride is shown in figure 1, and 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: dissolving 7.6g (15 mmol) of intermediate (II) in 100mL of tetrahydrofuran under the protection of nitrogen, cooling liquid nitrogen to-60 ℃, slowly dropwise adding 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) 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, then dropwise adding 5mL of pure water to quench the reaction, spin-drying until no solvent remains, adding 50mL of pure water for pulping, and filtering to obtain 12.3g of intermediate (III) wet product;
(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 was obtained5 ", 6,6" tetracarboxylic dianhydride [ 2 ], [ solution ] 1 H NMR(400MHz,DMSO-d 6 )δ3.48(s,2H),3.17(q,J＝7.6Hz,4H),2.45(s,4H),2.04(d,J＝11.5Hz,2H),1.77–1.70(m,4H),1.36(d,J＝12.5Hz,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 'and 6,6' tetracarboxylic dianhydride is 205.6 ℃ through detection.
Comparative example
Comparative example 1
A synthesis route of norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornane-5,5 ', 6,6' tetracarboxylic dianhydride is shown in figure 2, and specifically comprises the following steps:
(one) mannich reaction and diels-alder reaction: dripping 8.19g of hydrochloric acid with the mass percentage concentration of 35% into 6.83g of dimethylamine aqueous solution with the mass percentage 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 3h, cooling to 50 ℃ after the reaction is finished, adding 50mL of methoxy ethanol, 1.12g of dimethylamine aqueous solution with the mass percentage concentration of 50% and 7.13g of cyclopentadiene, controlling the oil bath temperature to be 120 ℃ under the nitrogen atmosphere, reacting for 90min, cooling to room temperature (25 ℃), extracting for 2 times by using 80mL of n-heptane, combining organic phases, washing the organic phases with 25mL of 5% sodium hydroxide solution by mass, 25mL of 5% sodium bicarbonate solution by mass and 25mL of saturated sodium chloride in sequence, drying, and spin-drying the filtrate until no solvent remains to obtain 7.4g of a crude product of norbornene-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornene, and performing distillation purification (boiling point 105 ℃/0.1mm Hg) to obtain 4.5g of norbornene-2-spiro-alpha-cyclopentanone-alpha '-spiro-2' -norbornene with a yield of 61%;
(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 -cyclo- α' -spiro-2" -norbornane-5,5 ", 6,6" methyl tetracarboxylic acid ester with a yield of 98.5%;
(III) anhydride forming reaction: mixing 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, controlling the temperature of an oil bath at 120 ℃, carrying out reflux reaction for 6h, after the reaction, the reaction mixture was concentrated to 50% of the original volume, 7mL of formic acid was added, and the mixture was refluxed at 120 ℃ for 3 hours and dried to obtain 1.56g of norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 "-norbornane-5,5", 6,6 "tetracarboxylic dianhydride with a purity of 92.3% and a yield of 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 'and 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 synthetic 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 anhydride 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 after the reaction is finished to obtain an intermediate (I);
(II) carbonyl insertion reaction: adding cobaltosic carbonyl and chloroborane diethylaniline complex into tetrahydrofuran under the atmosphere of carbon monoxide, stirring for dissolving, adding tetrahydrofuran solution of the 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 value 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. a process for producing a tetracarboxylic dianhydride alicyclic compound according to claim 1, wherein in step (one), the molar ratio of maleic anhydride, cyclopentadiene, aniline and acetic anhydride is 1.1.
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 process 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.
5. A process for producing an alicyclic compound such as tetracarboxylic dianhydride according to claim 1, wherein in step (II), the molar ratio of octacarbonyldicobalt, chloroborane diethylaniline complex, solute in hydrogen peroxide, intermediate (I) is 0.25 to 0.27.
6. A process for producing a tetracarboxylic dianhydride alicyclic compound according to claim 1, wherein in step (III), the molar ratio of the intermediate (II) to dibromoethane is 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 process 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.
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