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Preparation method of monohalogenated phenylboronic acid

A technology of monohalogenated phenylboronic acid and phenylboronic acid, which is applied in the field of preparation of monohalogenated phenylboronic acid, can solve the problems of harsh reaction conditions and low purity, and achieves low equipment requirements, high yield and purity, and mild reaction conditions. Effect

Active Publication Date: 2020-09-11
宁夏中星显示材料有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Aiming at the problems of low yield, low purity and harsh reaction conditions in the process for preparing monohalogenated phenylboronic acid in the prior art, the present invention provides a method for preparing monohalogenated phenylboronic acid

Method used

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  • Preparation method of monohalogenated phenylboronic acid

Examples

Experimental program
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Effect test

Embodiment 1

[0048] A kind of preparation method of 3-chlorophenylboronic acid:

[0049] Step 1. Add 47.1g (0.6mol) of isopropyl chloride to 150mL of tetrahydrofuran to obtain a solution of isopropyl chloride; put 12g (0.5mol) of magnesium chips in a 500ml three-necked flask, add 20mL of tetrahydrofuran, and set the water bath at 20°C under nitrogen Under protective conditions, stir and drop the above-mentioned isopropyl chloride solution, control the rate of addition so that the temperature does not exceed 30°C, start timing from the dropwise addition of the isopropyl chloride solution, and react for 1 hour to obtain a tetrahydrofuran solution of isopropylmagnesium chloride;

[0050] Step 2: Take 46.25g (0.25mol) of 1-butyl-3-methylimidazole formate, add 0.53g (0.0125mol) of anhydrous lithium chloride under stirring conditions, and stir until a transparent homogeneous system is obtained to obtain a catalyst; Take 4.678g of the above catalyst, add it to the tetrahydrofuran solution of isop...

Embodiment 2

[0055] A preparation method of 4-bromophenylboronic acid:

[0056] Step 1. Add 60.17g (0.65mol) of tert-butyl chloride into 150mL of methyl tert-butyl ether to obtain a tert-butyl chloride solution; put 12g (0.5mol) of magnesium chips in a 500ml three-necked flask, and add 35mL of methyl tert-butyl ether, in a water bath at 40°C, under the condition of nitrogen protection, stir and drop the above-mentioned tert-butyl chloride solution, control the rate of addition so that the temperature does not exceed 50°C, start timing from the dropwise addition of the tert-butyl chloride solution, and react for 2 hours to obtain tert-butyl ether Butyl magnesium chloride in methyl tert-butyl ether solution;

[0057] Step 2: Take 21.41g (0.125mol) of 1-butyl-2,3-dimethylimidazolium hydroxide salt, add 1.37g (0.0125mol) of anhydrous lithium sulfate under stirring conditions, stir and mix evenly to obtain a catalyst; Weigh 4.556g of the above-mentioned catalyst, add it in the methyl tert-buty...

Embodiment 3

[0061] A preparation method of 4-bromophenylboronic acid:

[0062] Step 1, 78.79g (0.7mol) chlorobenzene is added in the mixed solution of 350mL dioxane and toluene (the volume ratio of dioxane and toluene is 1:1, hereinafter referred to as mixed organic solution) to obtain chlorobenzene Solution: put 12g (0.5mol) of magnesium chips in a 500ml three-necked bottle, add 30mL of the above mixed organic solution, and put the above chlorobenzene solution in a water bath at 70°C under nitrogen protection, stirring and dropping the above chlorobenzene solution, and controlling the rate of addition so that the temperature does not exceed 80°C , start timing from the dropwise addition of chlorobenzene solution, and react for 1.5h to obtain the reaction solution of phenylmagnesium chloride;

[0063] Step 2: Take 18.52g (0.1mol) of 1-butyl-3 methylimidazole formate, add 1.74g (0.025mol) of lithium formate monohydrate under stirring conditions, and stir until a transparent homogeneous sys...

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Abstract

The invention relates to the technical field of chemical synthesis, and particularly discloses a preparation method of monohalogenated phenylboronic acid. The preparation method comprises the following steps of: by taking dihalogenated benzene as a raw material and a mixture of lithium salt and alkaline ionic liquid as a catalyst, carrying out Grignard exchange with R1MgCl to generate monohalogenated phenyl magnesium chloride, reacting with B (OR) 3 to generate monohalogenated phenyl borate, and hydrolyzing under acidic conditions to obtain monohalogenated phenylboronic acid. The HPLC (High Performance Liquid Chromatography) content of the monohalogenated phenylboronic acid prepared by the method is greater than 99.5%; the total yield of the product is greater than 80%, the contents of monohalogenated phenylboronic acid and phenyldiboronic acid impurities of another halogen are both less than 0.003%, the requirements of modern fine chemical synthesis are completely met, the raw materials are easily available, the operation is simple, the safety is high, and the industrial production of monohalogenated phenylboronic acid is realized.

Description

technical field [0001] The invention relates to the technical field of chemical synthesis, in particular to a preparation method of monohalogenated phenylboronic acid. Background technique [0002] Monohalogenated phenylboronic acid is an important pharmaceutical and organic light-emitting diode (OLED) intermediate. As an important intermediate containing both halogen and boronic acid groups, it has been widely used in Suzuki coupling and Sonogashira coupling reactions. [0003] Fluorophenylboronic acid can use dihalides due to the particularly low activity of fluorine (X is bromine or chlorine) as a raw material, and high-yield and high-purity fluorophenylboronic acid is prepared by directly preparing Grignard reagents. In addition, other dihalides are difficult to prepare monohalogenated phenylboronic acid with high yield and high purity (purity higher than 99.5%) by Grignard reagents. The technical bottleneck is that when the iodine-containing dihalide is used to prepa...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/02
CPCC07F5/025Y02P20/54
Inventor 岳刚王志强丁秋月禹凯王利民陈少华关登仕
Owner 宁夏中星显示材料有限公司
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