Synthesis method for 4,4'-biphenyldicarboxylic acid

A technology of biphenyl dicarboxylic acid and a synthesis method, which is applied in the field of synthesis of 4,4'-biphenyl dicarboxylic acid, can solve the problems of numerous synthesis steps, harsh reaction conditions, difficult separation and purification, etc. The effect of mild reaction conditions and high atom economy

Active Publication Date: 2014-01-01
SINOSTEEL ANSHAN RES INST OF THERMO ENERGY CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, the synthesis of 4,4′-biphenyldicarboxylic acid mainly has the following routes: (1) 4,4′-dialkylbiphenyl is used as raw material and prepared by oxidation under high temperature and pressure. This method not only The raw materials are expensive, and the reaction conditions are harsh, there are many by-products, separation and purification are difficult, and the yield is low (generally lower than 56%); (2) biphenyl is used as a raw material, and 4,4-ˊdi(chloro Methyl) biphenyl, and then undergo nucleophilic substitution reaction with hexamethylenetetramine to hydrolyze to 4,4′-biphenyldicarbaldehyde, and then oxidize with hydrogen peroxide to obtain 4,4′-biphenyldicarboxylic acid, which is synthesized by this method There are many steps, and the yield is only 38.2%; (3) Suzuki cross-coupling reaction is carried out using p-hydroxyphenylboronic acid and p-bromobenzoic acid as raw materials, but the reaction condition

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] A kind of synthetic method of 4,4'-biphenyl dicarboxylic acid, its reaction steps are as follows:

[0019] Step 1: Under the protection of nitrogen, add 53.5g (0.270mol) of 4-biphenylcarboxylic acid, 45g (0.337mol) of anhydrous aluminum trichloride and dichloroethane (solvent ) 250g, cool down to 15°C, add 41.2g (0.325mol) of oxalyl chloride dropwise, and the dropwise addition is completed within 2 hours. The hydrogen chloride gas generated during the dropwise addition is absorbed with lye. After layering in 800g of ice water, the oil layer was washed twice with water, and the solvent was recovered to obtain 60.3g of 4,4′-dicarboxybiphenylil, with a purity of 95% and a yield of 94.2%;

[0020] Step 2: In a 500ml four-necked glass reaction flask, add 60.3g (0.134mol) of 4,4′-dicarboxybiphenyl, 10.6g (0.188mol) of potassium hydroxide and 300g of dichlorobenzene (organic solvent) in sequence , control the temperature in the reaction bottle at 40-50°C and add 20.7g (0.161m...

Embodiment 2

[0022] A kind of synthetic method of 4,4'-biphenyl dicarboxylic acid, its reaction steps are as follows:

[0023] Step 1: Under the protection of nitrogen, add 53.5g (0.270mol) of 4-biphenylcarboxylic acid, 64.5g (0.484mol) of anhydrous aluminum trichloride and chloroform (solvent) into a 500ml dry four-necked reaction flask in sequence 350g, temperature controlled to 25°C, 55g (0.433mol) of oxalyl chloride was added dropwise, and the dropwise addition was completed within 2 hours, and the hydrogen chloride gas generated during the dropwise addition was absorbed with lye. After the reaction was completed, the material was slowly added to 1000g of ice water. After the layers were separated, the oil layer was washed twice with water, and the solvent was recovered to obtain 59g of 4,4'-dicarboxybiphenylil, with a purity of 96% and a yield of 93.2%. ;

[0024] Step 2: In a 500ml four-necked glass reaction flask, add 59g (0.131mol) of 4,4′-dicarboxybiphenyl, 14.6g (0.260mol) of po...

Embodiment 3

[0026] A kind of synthetic method of 4,4'-biphenyl dicarboxylic acid, its reaction steps are as follows:

[0027] Step 1: Under nitrogen protection, add 53.5g (0.270mol) of 4-biphenylcarboxylic acid, 57.8g (0.433mol) of anhydrous aluminum trichloride and dichloroethane (solvent ) 350g, the temperature was controlled to 20°C, 48g (0.378mol) of oxalyl chloride was added dropwise, and the dropwise addition was completed within 2 hours, and the hydrogen chloride gas generated during the dropwise addition was absorbed with lye. After the reaction was completed, the material was slowly added to 1000g of ice water. After the layers were separated, the oil layer was washed twice with water, and the solvent was recovered to obtain 60g of 4,4'-dicarboxybiphenylil, with a purity of 96% and a yield of 94.7%. ;

[0028] Step 2: In a 500ml four-necked glass reaction flask, add 60g (0.133mol) of 4,4′-dicarboxybiphenyl, 13.5g (0.241mol) of potassium hydroxide and 400g of chlorobenzene (organ...

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Abstract

The invention relates to the field of chemical synthesis, and in particular to a synthesis method for 4,4'-biphenyldicarboxylic acid. The synthesis method for 4,4'-biphenyldicarboxylic acid is characterized by comprising the following reaction steps of: step 1, reacting 4-diphenic acid, oxalyl chloride and aluminium trichloride in a molar ratio of 1: (1.1-1.8): (1.2-2.0) to obtain 4,4'-dicarboxylbibenzil, wherein the weight ratio of 4-diphenic acid to a solvent is 1: (3 to 10); and step 2, reacting 4,4'-dicarboxylbibenzil, an oxidant and potassium hydroxide in a molar ratio of 1: (1.2-2.0):(1.4-2.2), and then carrying out recrystallization by absolute methanol to obtain 4,4'-biphenyldicarboxylic acid, wherein the weight ratio of 4,4'-dicarboxylbibenzil to an organic solvent is 1: (3-10). Compared with the prior, the synthesis method for 4,4'-biphenyldicarboxylic acid disclosed by the invention has the beneficial effects of being reasonable and practicable in process flow, high in yield which is up to move than 93%, moderate in process reaction conditions, low in requirements on equipment, and suitable for industrialized production.

Description

technical field [0001] The invention relates to the field of chemical synthesis, in particular to a synthesis method of 4,4'-biphenyl dicarboxylic acid. Background technique [0002] 4,4'-biphenyldicarboxylic acid is the main organic synthesis intermediate, widely used in the synthesis of organic polymer materials, pharmaceuticals, coordination polymer supramolecular materials and liquid crystal products. At present, the synthesis of 4,4′-biphenyldicarboxylic acid mainly has the following routes: (1) 4,4′-dialkylbiphenyl is used as raw material and prepared by oxidation under high temperature and pressure. This method not only The raw materials are expensive, and the reaction conditions are harsh, there are many by-products, separation and purification are difficult, and the yield is low (generally lower than 56%); (2) biphenyl is used as a raw material, and 4,4-ˊdi(chloro Methyl) biphenyl, and then undergo nucleophilic substitution reaction with hexamethylenetetramine to h...

Claims

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Application Information

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IPC IPC(8): C07C63/333C07C51/285C07C51/347
CPCC07C51/16C07C51/285C07C51/373C07C63/333C07C65/34
Inventor 王海洋王守凯刘佳金丹陈兴王海波
Owner SINOSTEEL ANSHAN RES INST OF THERMO ENERGY CO LTD
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