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Preparation method of tetracarboxylic dianhydride alicyclic compound

A technology of tetracarboxylic dianhydride and alicyclic compound is applied in the field of preparation of tetracarboxylic dianhydride type alicyclic compound, can solve the problems of low purity of intermediate product, poor reaction effect, inconvenient purification and the like, and achieves simple steps , The effect of low process condition requirements and reducing the cost of synthesis reaction

Active Publication Date: 2022-05-24
上海固创化工新材料有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] For the above-mentioned related technologies, the first three steps of the synthesis process are reacted together, and each step is not convenient for purification, so that the purity of the intermediate product is relatively low, and the yield The rate is also low, and the effect of continuing the reaction is not good, and the carbonyl insertion reaction process needs to be catalyzed by palladium chloride, and the cost is higher

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  • Preparation method of tetracarboxylic dianhydride alicyclic compound
  • Preparation method of tetracarboxylic dianhydride alicyclic compound

Examples

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Embodiment 1

[0033] A norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"tetracarboxylic dianhydride, the synthetic route of which is as follows figure 1 shown, and includes the following steps:

[0034] (1) Diels-Alder reaction: take 300 mL of chloroform, add 98 g (1 mol) of maleic anhydride under stirring conditions, cool it to 0°C with an ice-water bath after dissolving, and slowly add 73 g (1.1 mol) dropwise within 30 min Cyclopentadiene, keep stirring for 30min after the dropwise addition, add 93g (1mol) aniline dropwise, control the dropwise temperature not to exceed 20°C, after the dropwise addition, control the temperature to be 20°C, keep stirring for 30min, add 153g (1.5mol) vinegar Anhydride and 16g (195mmol) sodium acetate, refluxed for 2h, spin-dried at 40°C, then added 1L pure water to make slurry, filtered, washed with filter cake, and dried to obtain 220g of intermediate (I) with a purity of 98.0% and a yield of 92.0 %;

[0035] (2) Carbonyl intercalation...

Embodiment 2

[0041] A norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"tetracarboxylic dianhydride, the synthetic route of which is as follows figure 1 shown, and includes the following steps:

[0042] (1) Diels-Alder reaction: take 300 mL of chloroform, add 98 g (1 mol) of maleic anhydride under stirring conditions, cool it to 0°C with an ice-water bath after dissolving, and slowly add 73 g (1.1 mol) dropwise within 30 min Cyclopentadiene, keep stirring for 30min after the dropwise addition, add 93g (1mol) aniline dropwise, control the dropwise temperature not to exceed 20°C, after the dropwise addition, control the temperature to be 20°C, keep stirring for 30min, add 153g (1.5mol) vinegar Anhydride and 19.6g (200mmol) potassium acetate, refluxed for 2h, spin-dried at 40°C, then added 1L pure water to make slurry, filtered, washed with filter cake, and dried to obtain 223g of intermediate (I) with a purity of 98.1% and a yield of 93.2 %.

[0043] (2) carbonyl intercal...

Embodiment 3

[0049] A norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"tetracarboxylic dianhydride, the synthetic route of which is as follows figure 1 shown, and includes the following steps:

[0050] (1) Diels-Alder reaction: same as Example 1;

[0051] (2) Carbonyl intercalation reaction: take 150 mL of tetrahydrofuran, add 4.6 g (13.5 mmol) of dicobalt octacarbonyl and 6.3 g (32 mmol) of chloroborane diethylaniline complex under carbon monoxide atmosphere, stir to dissolve, and dissolve at room temperature (25 ℃), dropwise add the tetrahydrofuran solution of intermediate (I) (12g, 50 mmol of intermediate (I) dissolved in 50 mL of tetrahydrofuran), stir for 30h after the dropwise addition, stop carbon monoxide, cool down in an ice-water bath at 0-5 ℃ Add 13.6 g of hydrogen peroxide with a concentration of 25% by mass, stir for 30 min after the dropwise addition, adjust pH to 4-5 with dilute sulfuric acid with a concentration of 20% by mass, spin dry at 50 ° C and eva...

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Abstract

The invention relates to the field of organic synthesis, and particularly discloses a preparation method of a tetracarboxylic dianhydride alicyclic compound, which comprises the following steps: (I) Diels-Alder reaction: reacting maleic anhydride, cyclopentadiene, aniline and acetic anhydride in a solvent chloroform to generate an intermediate (I); (2) carbonyl insertion reaction: carrying out carbonyl insertion reaction on the intermediate (I) in a carbon monoxide atmosphere to generate an intermediate (II); (3) ring-closure reaction: carrying out ring-closure reaction on dibromoethane to generate an intermediate (III); (4) hydrolysis reaction: hydrolyzing the intermediate (III) to remove aniline so as to obtain an intermediate (IV); and (5) anhydride forming reaction: dehydrating the intermediate (IV) in acetic anhydride to obtain a target product. According to the preparation method disclosed by the invention, the reaction is carried out step by step, tracking and purification are easy, the operation is simple, the purity and yield of the target product are relatively high, a noble metal palladium catalyst is avoided in the reaction process, and the cost is also reduced.

Description

technical field [0001] The application relates to the technical field of organic synthesis, more specifically, it relates to a preparation method of a tetracarboxylic dianhydride alicyclic compound, in particular to a kind of norbornane-2-spiro-α-cyclopentanone-α The preparation method of '-spiro-2"-norbornane-5,5",6,6" tetracarboxylic dianhydride. Background technique [0002] Polyimide (PI) has a higher thermal decomposition temperature than other plastics, up to 500 ° C or even higher, not only heat-resistant, but also an excellent material in mechanical and electrical properties. In recent years, with the development of foldable smartphones, transparent polyimide (CPI) has attracted attention as a glass replacement material in liquid crystal displays and organic EL displays. Transparent polyimide (CPI) should not only be transparent, but also have properties such as high heat resistance and low expansion coefficient. Aliphatic dianhydrides and diamines are the preferre...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D493/08
CPCC07D493/08
Inventor 刘少华
Owner 上海固创化工新材料有限公司