Method for preparing 4-amino benzene boric acid hydrochloride

A technology of aminophenylboronic acid hydrochloride and nitrophenylboronic acid, which is applied in the field of preparing 4-aminophenylboronic acid hydrochloride, can solve the problems of cumbersome operation and harsh conditions, and achieve safe and reliable process, mild conditions and high yield. high rate effect

Inactive Publication Date: 2013-04-17
DALIAN NETCHEM CHIRAL TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This method has the following disadvantages: 1. The raw materials need to be protected and deprotected by the amino group, and the operation is cumbersome; 2. The reaction requires ultra-low temperature -78°C, and the conditions are harsh

Method used

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  • Method for preparing 4-amino benzene boric acid hydrochloride
  • Method for preparing 4-amino benzene boric acid hydrochloride

Examples

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Comparison scheme
Effect test

Embodiment 1

[0019] A method for preparing 4-aminophenyl borate hydrochloride with biscatechol borate:

[0020] In the first step, add 500.0g DMF, 101.0g 4-nitrobromobenzene (0.50mol, 1eq), 130.8g bis-catechol borate (0.55 mol, 1.2eq), 147.2g potassium acetate (1.5mol, 3eq), 18.3gPd(dppf)Cl 2 (0.025mol, 0.05eq), react at 80°C for 3h. Cool down to 20~25°C, filter, add the filtrate dropwise to 500.0g of water, stir for 1 hour, then raise the temperature to 20~25°C. Extracted twice with ethyl acetate (200mL×2), combined the organic layers and concentrated, slurred and filtered with 50.0g n-heptane at -5~0°C, and dried the filter cake to obtain 63.7g of white solid, GC: 97.6%, yield: 76.3 %.

[0021] In the second step, dissolve 63.7g of 4-nitrophenylboronic acid (0.38mol, 1eq) into 255g of ethyl acetate, add 2.0g of palladium carbon (10%, 0.005eq), hydrogenate at 0.8~1.0MPa, 70~80℃ React for 6h, after the reaction is over, filter with diatomaceous earth, cool the filtrate to 0°C, add 51.0...

Embodiment 2

[0023] A method for preparing 4-aminophenyl borate hydrochloride with biscatechol borate:

[0024] In the first step, add 500.0g DMSO, 101.0g 4-nitrobromobenzene (0.50mol, 1eq), 130.8g bis-catechol borate (0.55 mol, 1.2eq), 147.2g potassium acetate (1.5mol, 3eq), 18.3gPd(dppf)Cl 2 (0.025mol, 0.05eq), react at 90°C for 2.5h. Cool down to 20~25°C, filter, add the filtrate dropwise to 500.0g of water, stir for 1 hour, then raise the temperature to 20~25°C. Extracted twice with ethyl acetate (200 mL×2). The combined organic layers were concentrated, slurred and filtered with 50.0 g of n-heptane at -5~0°C, and the filter cake was dried to obtain 65.6 g of white solid, GC: 97.1%, yield: 78.6%.

[0025] In the second step, dissolve 65.6g of 4-nitrophenylboronic acid (0.39mol, 1eq) into 262g of ethyl acetate, add 2.1g of palladium carbon (10%, 0.005eq), hydrogenate at 0.8~1.0MPa, 70~80℃ React for 6 hours, the reaction is over, filter with diatomaceous earth, cool the filtrate to 0...

Embodiment 3

[0027] A method for preparing 4-aminophenyl borate hydrochloride with biscatechol borate:

[0028] In the first step, add 500.0g of 1,4-dioxane, 101.0g of 4-nitrobromobenzene (0.50mol, 1eq), and 130.8g of bis-phthalate to a magnetically stirred 1L four-neck flask under argon protection. Diphenol borate (0.55mol, 1.2eq), 147.2g potassium acetate (1.5mol, 3eq), 18.3gPd(dppf)Cl 2 (0.025mol, 0.05eq), react at 100°C for 2h. Cool down to 20~25°C, filter, add the filtrate dropwise to 500.0g of water, stir for 1 hour, then raise the temperature to 20~25°C. Extracted twice with ethyl acetate (200mL×2), the combined organic layers were concentrated, 50.0g of n-heptane was used to beat and filter at -5~0°C, and the filter cake was dried to obtain 60.4g of white solid, GC: 98.3%, yield: 72.4 %.

[0029] In the second step, dissolve 60.4g of 4-nitrophenylboronic acid (0.36mol, 1eq) into 241g of ethyl acetate, add 2.0g of palladium carbon (10%, 0.005eq), hydrogenate at 0.8~1.0MPa, 70~80℃...

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Abstract

The invention discloses a method for preparing 4-amino benzene boric acid hydrochloride. The method comprises the steps that 1), catechol and 4-nitrobromobenzene are subjected to a reaction for 2-3h in a polar solvent under the action of potassium acetate and Pd (dppf) C12, the temperature is lowered to a room temperature, filtering is performed, ethyl acetate is extracted, and a crude product is pulped and filtered through nonpolar varsol after an organic layer is concentrated, so that 4-nitrophenylboronic acid is obtained; and 2), the 4-nitrophenylboronic acid is subjected to palladium carbon catalytic hydrogenation in the ethyl acetate, hydrogenation is performed for 6-8h at the temperature ranging between 60 DEG C and 80 DEG C and under 0.8-1.0 MPa, filtering is performed at the temperature of 15-25 DEGC after the reaction, concentrated hydrochloric acid is added into the filtering liquid at the temperature of 0-10 DEG C, filtering is performed, and the crude product is obtained, then pulped with acetone, filtered and dried, so that the 4-amino benzene boric acid hydrochloride is obtained. According to the method, raw materials are low in toxicity and can be processed easily, copious cooling and low temperature are avoided simultaneously, the reaction temperature can be reached easily, the conditions are mild, the yield is high, the process is safe and reliable, and method is suitable for industrial production.

Description

technical field [0001] The invention relates to the technical field of chemical synthesis, in particular to a method for preparing 4-aminophenyl borate hydrochloride. Background technique [0002] For the known and reported 4-aminobenzene borate hydrochloride, 4-aminobromobenzene is usually used as a raw material. After the amino group is protected, n-butyllithium and borate are used to react at a low temperature of about -78°C. Acidification and purification give the product. This method has the following disadvantages: 1. The raw materials need to be protected and deprotected from the amino group, and the operation is cumbersome; 2. The reaction requires ultra-low temperature of -78°C, and the conditions are harsh. Contents of the invention [0003] The purpose of the present invention is in order to solve the above problems, and a kind of method for the preparation of 4-aminophenyl borate hydrochloride with simplified process is provided. [0004] The technical scheme...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/02
Inventor 孙靖劼刘经红国宏伟
Owner DALIAN NETCHEM CHIRAL TECH
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