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Preparation method of p-carboxyphenylboronic acid

A technology of carboxyphenylboronic acid and p-bromobenzoic acid, applied in the field of chemistry, can solve problems such as low yield, low success rate, difficult post-processing, etc., and achieve the effects of high yield, low reaction cost, and easy operation

Active Publication Date: 2014-04-16
贵州威顿晶磷电子材料股份有限公司
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  • Abstract
  • Description
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  • Application Information

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Problems solved by technology

[0011] The above-mentioned process for preparing p-carboxyphenylboronic acid has many side reactions, difficult post-processing, and low yield; among them, the Grignard reaction requires relatively high conditions and must be absolutely anhydrous and oxygen-free, and the success rate is too low, so it is not suitable for industrial production.

Method used

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  • Preparation method of p-carboxyphenylboronic acid
  • Preparation method of p-carboxyphenylboronic acid
  • Preparation method of p-carboxyphenylboronic acid

Examples

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Embodiment 1

[0031] A preparation method for p-carboxyphenylboronic acid, comprising the steps of:

[0032] (1) Synthesis of 4-bromo-N,N-diisopropylbenzamide (Ⅲ)

[0033] Add 90 g of p-bromobenzoic acid into the reactor, add 450 g of thionyl chloride, heat and reflux for 2.5 hours, and detect that the reaction is complete by thin-layer chromatography, spin dry thionyl chloride with a dried rotary evaporator, add dichloromethane 320g to form A liquid; add 49.8g diisopropylamine and 350g dichloromethane to another reactor, under ice bath, drop into A liquid, after dropping, react at room temperature for 2 hours, the reaction is complete by thin layer chromatography, add 500g The aqueous phase was extracted once with 200 g of dichloromethane, the organic phases were combined, washed once with 410 g of saturated sodium bicarbonate, washed once with 400 g of saturated saline, dried with anhydrous sodium sulfate for 2 hours, filtered, and concentrated to obtain a yellow liquid 4 -Bromo-N,N-diis...

Embodiment 2

[0041] (1) Synthesis of 4-bromo-N,N-diisopropylbenzamide (Ⅲ)

[0042] Add 90 g of p-bromobenzoic acid into the reactor, add 620 g of thionyl chloride, heat and reflux for 2.3 hours, and detect that the reaction is complete by thin-layer chromatography, spin dry thionyl chloride with a dried rotary evaporator, add dichloromethane 400g to form A liquid; add 62.5g diisopropylamine and 460g dichloromethane to another reactor, drop into A liquid under ice bath, after dropping, react at room temperature for 1.8 hours, the reaction is complete by thin layer chromatography, add 570g The aqueous phase was extracted once with 270 g of dichloromethane, the organic phases were combined, washed once with 490 g of saturated sodium bicarbonate, washed once with 450 g of saturated brine, dried with anhydrous sodium sulfate for 2 hours, filtered, and concentrated to obtain a yellow liquid 4 -Bromo-N,N-diisopropylbenzamide 120.24g, yield 94.5%.

[0043] (2) Synthesis of (4-(diisopropylcarbamoy...

Embodiment 3

[0050] (1) Synthesis of 4-bromo-N,N-diisopropylbenzamide (Ⅲ)

[0051] Add 90 g of p-bromobenzoic acid into the reactor, add 710 g of thionyl chloride, heat and reflux for 2.2 hours, and detect that the reaction is complete by thin-layer chromatography, spin dry thionyl chloride with a dried rotary evaporator, add dichloromethane 450g to form A liquid; add 79.2g diisopropylamine and 520g dichloromethane to another reactor, under ice bath, drop into A liquid, after dropping, react at room temperature for 1.5 hours, the reaction is complete by thin layer chromatography, add 610g The aqueous phase was extracted once with 310 g of dichloromethane, the organic phases were combined, washed once with 530 g of saturated sodium bicarbonate, washed once with 500 g of saturated saline, dried with anhydrous sodium sulfate for 2 hours, filtered, and concentrated to obtain a yellow liquid 4 -Bromo-N,N-diisopropylbenzamide 122.66g, yield 96.4%.

[0052] (2) Synthesis of (4-(diisopropylcarbam...

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Abstract

The invention discloses a preparation method of p-carboxyphenylboronic acid. The preparation method comprises the steps of carrying out an amidation reaction on bromobenzoic acid and diisopropylamine to obtain a reaction intermediate 4-bromo-N,N-diisopropylbenzamide; carrying out the substitution reaction on the 4-bromo-N,N-diisopropylbenzamide at a reaction temperature ranging from -75 to -80 DEG C in a solvent which is dry tetrahydrofuran, thereby obtaining (4-(diisopropylcarbamyl)phenyl) boric acid; hydrolyzing (4-(diisopropylcarbamyl)phenyl) boric acid in the presence of lithium hydroxide monohydrate to obtain p-carboxyphenylboronic acid. The preparation method provided by the invention is high in product yield, simple and convenient to operate, low in reaction cost and applicable to industrial production.

Description

technical field [0001] The invention belongs to the technical field of chemistry and relates to a preparation method of p-carboxyphenylboronic acid. [0002] Background technique [0003] p-Carboxyphenylboronic acid is an important intermediate in drug synthesis and can be applied to the preparation of heterocyclic biphenyls [0004] Compounds as hepatitis C virus inhibitors (see patent 20130115194), preparation of bicyclic heterocyclic compounds as 11β-hydroxysteroid dehydrogenase type 1 inhibitors (see patent PCT Int.Appl., 2013058258), and preparation of novel thiophenes (See patent PCT Int. Appl., 2013036196), the literature reports on the synthesis route of p-carboxyphenylboronic acid are as follows: [0005] Li Wenjie, et al. "Journal of Organic Chemistry", 2002, 67(15): 5394-5397 published [0006] A kind of processing route of preparing p-carboxyphenylboronic acid is as follows: [0007] [0008] The above-mentioned preparation of p-carboxyphenylboronic acid i...

Claims

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Application Information

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IPC IPC(8): C07F5/02
Inventor 赵春深蒋飚吴郁林于海涛周小松周银宋吾燕余明
Owner 贵州威顿晶磷电子材料股份有限公司
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