The synthetic method of 3-aminophenylboronic acid

A technology of aminophenylboronic acid and nitrobromobenzene, which is applied in the field of organic boric acid synthesis of pharmaceutical intermediates, can solve the problems of ineffective removal of color, poor reaction reproducibility, and insufficient yield in literature, so as to avoid ultra-low temperature reaction and synthesis Efficiency improvement and overall simple operation

Active Publication Date: 2021-01-05
CANGZHOU PURUI DONGFANG SCI & TECH
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  • Abstract
  • Description
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Problems solved by technology

When this method is repeatedly enlarged to a scale of more than 100 grams, the product will inevitably be carbonized during the nitration reaction, and dark brown 3-nitrophenylboronic acid will be obtained. The color cannot be effectively removed during purification, and the yield is less than half of the literature yield. poor reproducibility

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  • The synthetic method of 3-aminophenylboronic acid

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Experimental program
Comparison scheme
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Embodiment 1

[0023] Under the protection of nitrogen, 3-nitrobromobenzene (20.2 g, 0.1mol), catechol biborate (52.3g, 0.22mol) and anhydrous potassium acetate (29.4g, 0.3mol) were successively added into the reaction flask , then add 550mL of dioxane, stir evenly, then add PdCl2dppf (0.73g, 1mmol), then slowly raise the temperature to 90°C for reaction under stirring, and stir for 2 hours. At this time, the system is black, and the reaction is detected by TLC. After cooling down to room temperature, 120 mL of water was slowly added dropwise to quench, and after the dropwise addition was completed, the reaction was continued to stir for 4-5 hours. Cool the reaction solution to 0°C, add 10% aqueous hydrochloric acid dropwise to adjust pH=1, add 80 mL of dichloromethane to extract twice, add 20% sodium hydroxide to the aqueous layer to adjust pH=5-6, and extract three times with 120 mL ethyl acetate, Add activated carbon and silica gel to decolorize under reflux, filter and distill ethyl acet...

Embodiment 2

[0025] Under the protection of nitrogen, 3-nitrobromobenzene (20.2 g, 0.1mol), catechol biborate (52.3g, 0.22mol) and anhydrous potassium acetate (29.4g, 0.3mol) were successively added into the reaction flask , Then add 720mL of toluene, stir evenly, then add PdCl2dppf (0.73g, 1mmol), slowly heat up to 110°C under stirring to react, stir for 8-10 hours, the system is black at this time, TLC detects that the reaction is over. After cooling down to room temperature, 110 mL of water was slowly added dropwise to quench, and after the dropwise addition was completed, the reaction was continued to stir for 4-5 hours. Cool the reaction solution to 0°C, add 10% aqueous hydrochloric acid dropwise to adjust the pH=1, discard the organic layer after layering, add 30% potassium hydroxide to the aqueous layer to adjust the pH=5-6, extract three times with 120 mL of ethyl acetate, add Activated carbon and silica gel were refluxed for decolorization. After filtration, ethyl acetate was dist...

Embodiment 3

[0027] Under the protection of nitrogen, 3-nitrobromobenzene (20.2 g, 0.1mol), catechol biborate (59.4g, 0.25mol) and anhydrous potassium acetate (29.4g, 0.3mol) were successively added into the reaction flask , then add 720mL of toluene, stir evenly, then add Pd(PPh3)4 (0.92g, 0.8mmol), then slowly raise the temperature to 110°C under stirring to react, stir for 8-10 hours, the system is black at this time, TLC detection Reaction The reaction is complete. After cooling down to room temperature, 110 mL of water was slowly added dropwise to quench, and after the dropwise addition was completed, the reaction was continued to stir for 4-5 hours. Cool the reaction solution to 0°C, add 10% aqueous hydrochloric acid dropwise to adjust the pH=1, discard the organic layer after layering, add 30% potassium hydroxide to the aqueous layer to adjust the pH=5-6, extract three times with 120 mL of ethyl acetate, add Activated carbon and silica gel are refluxed for decolorization. After fil...

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Abstract

The invention discloses a method for synthesizing 3-aminobenzeneboronic acid, and belongs to the field of organic synthesis. The method comprises the following steps: performing coupling reaction on 3-nitrobromobenzene and catechol diboron under action of a palladium catalyst; adding water for quenching; adding an acid for salifying a product and entering a water layer; adding alkali into the separated water layer to adjust to near neutral; and extracting and desolventizing to obtain the 3-aminobenzeneboronic acid. The method is simple in operation, high in purity of the obtained product and suitable for industrialized scale-up production.

Description

technical field [0001] The invention relates to the synthesis of aminoboronic acid, in particular to a synthesis method of 3-aminophenylboronic acid, and belongs to the technical field of organic boric acid synthesis of pharmaceutical intermediates. Background technique [0002] 3-Aminophenylboronic acid, also known as m-aminophenylboronic acid, is an important coupling aid for Suzuki coupling. Since the coupling reaction won the Nobel Prize in Chemistry in 2010, the product has grown rapidly in the application of pharmaceutical synthesis and optoelectronic materials. . Existing synthetic method mainly comprises following two kinds of schemes: [0003] 1) EP2801577A1 (2014) reported the reaction of 3-aminobromobenzene with benzophenone in the presence of p-toluenesulfonic acid, followed by the reaction of butyllithium and triisopropyl borate to obtain 3-aminophenylboronic acid after treatment. This method has been scaled up on hundreds of kilograms of raw materials. When s...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F5/02
CPCC07F5/025
Inventor 刘宗伦申海兵田利国冷延国
Owner CANGZHOU PURUI DONGFANG SCI & TECH
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