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Preparation of biphenyl-4,4'-dicarboxylic acid through coupling of 4-chlorobenzoic acid in ionic liquid

A biphenyl dicarboxylic acid, ionic liquid technology, applied in the preparation of carboxylate, the preparation of organic compounds, organic chemistry and other directions, to achieve the effect of simplifying the process, the synthesis route is simple and efficient, and the post-processing process is simple

Active Publication Date: 2018-12-07
CHONGQING CHANGFENG CHEM IND
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Problems solved by technology

[0004] The invention discloses a method for preparing 4,4'-biphenyldicarboxylic acid by using metal samarium as a catalyst in a small amount of ionic liquid solvent to catalyze the one-step coupling reaction of p-chlorobenzoic acid to prepare 4,4'-biphenyldicarboxylic acid. to report

Method used

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  • Preparation of biphenyl-4,4'-dicarboxylic acid through coupling of 4-chlorobenzoic acid in ionic liquid

Examples

Experimental program
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Effect test

example 1

[0016] Add 3g of newly prepared metal samarium powder and 0.26g of anhydrous copper chloride successively to the dry reaction vessel, and stir with magnetic force. Then add 4g of p-chlorobenzoic acid, 10mL of chlorobutylmethylimidazole which was dehydrated and dried in advance, and 0.1mL of pyridine. The reaction was carried out at room temperature, the color of the reaction mixture became dark within 5 hours, and the reaction was continued for 12 hours. The reaction solution was extracted with ethyl acetate and post-processed to obtain a crude product of 4,4'-biphenyldicarboxylic acid. It was then further separated by column chromatography and purified by ethanol recrystallization to obtain 4,4'-biphenyldicarboxylic acid with a yield of 81%.

[0017] White solid, melting point >300°C (decomposition). 1 HNMR (500MHz, CDCl 3 )δppm 7.75(d, J=8.5Hz, 4H), 7.83(d, J=8.5Hz, 4H), 12.5(2H), 13 C NMR (62.5MHz, CDCl 3 ): 127.5, 128.1, 135.6, 149.7, 170.4.

[0018] Dichloromethane ...

example 2

[0020] According to the method of Example 1, copper bromide was used instead of copper chloride, and bromobutylmethylimidazole was used instead of chlorobutylmethylimidazole to obtain 4,4'-biphenyldicarboxylic acid with a yield of 80%.

example 3

[0022] According to the method of Example 1, after repeated use of [bmim]Cl for 5 times, the transformation of the substrate can still be achieved well, and 4,4′-biphenyldicarboxylic acid was obtained with a yield of 77%.

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Abstract

The invention discloses a method for preparing biphenyl-4,4'-dicarboxylic acid by promoting a coupled reaction of p-halobenzoic acid by utilizing samarium metal under catalysis of a bivalent copper salt in an ionic liquid. P-chlorobenzoic acid is mixed and dissolved in an ionic liquid [bmim]Cl(chlorobutyl methyl imidazole) under stirring, and then samarium metal powder, cupric chloride powder anda small amount of pyridine are sequentially added; a reaction system is performed under an anhydrous condition, and stirring is performed at a room temperature until the reaction reacts completely; and the obtained reaction mixture is subjected to ionic liquid recovery, a crude product is separated by column chromatography to obtain the biphenyl-4,4'-dicarboxylic acid, a pure product is obtained by recrystallization, and the yield is 70-90%.

Description

technical field [0001] The invention belongs to the field of organic chemical synthesis, and in particular relates to a method for synthesizing 4,4'-biphenyldicarboxylic acid by using divalent copper salt to catalyze p-chlorobenzoic acid. Background technique [0002] 4,4′-Biphenyldicarboxylic acid is an important intermediate in organic synthesis in the chemical industry, and is widely used in pharmaceuticals, polymer materials, and liquid crystal products [Document 1. Ruan Chao, Yang Rong, Zhong Haiyi, et al. Journal of the Chinese Academy of Sciences, 2012(10):1177-1182.]. In recent years, 4,4′-biphenyldicarboxylic acid has also been used in the field of metal-organic materials [Document 2. Zhang Ke. Zhejiang University, 2014.]. For its synthesis, it can be prepared from 4,4'-dialkylbiphenyl as raw material by oxidation reaction, but the reaction conditions are harsh, there are many by-products, the yield is low, and it is often accompanied by decarboxylation reaction [d...

Claims

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Application Information

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IPC IPC(8): C07C51/353C07C63/333
CPCC07C51/353C07C63/333
Inventor 刘永军刘树峰齐燕
Owner CHONGQING CHANGFENG CHEM IND
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