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A kind of synthetic method of cyclopropyl boronic acid

A technology of cyclopropylboronic acid and aldehydeboronic acid, which is applied in the synthesis of alkylboronic acid and cyclopropylboronic acid, and can solve the problems of large amount of alkali and easy flushing.

Active Publication Date: 2021-01-05
CANGZHOU PURUI DONGFANG SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In this method, a large amount of alkali is required, and carbon dioxide gas is generated during the decarboxylation process, and the reaction is easy to flush if the dropwise addition is too fast

Method used

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  • A kind of synthetic method of cyclopropyl boronic acid
  • A kind of synthetic method of cyclopropyl boronic acid

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] In the reaction flask, add aldehyde boronic acid (7.75g, 0.105mol), absolute ethanol 65mL and 2,4-dinitro-p-toluenesulfonyl hydrazide (26.2g, 0.1mol), heat up to reflux reaction after adding, TLC After the detection reaction was completed, the absolute ethanol was distilled off under normal pressure, and then 220 mL of toluene was added and then refluxed to separate water until the detection reaction was completely transformed into a trimer. After cooling down, evaporate the toluene solvent to dryness, cool down to 0°C, add 160mL of 1,2-dichloroethane and catalyst FeCl(TPP)(0.15eq) (note: the equivalent is aldehyde boronic acid 0.15eq, the same below) and start to Continuously feed ethylene gas into the reaction solvent, replace the gas outlet of the reaction bottle with two layers of balloons, maintain a certain pressure in the reaction system until the system no longer absorbs, add 60mL sulfolane, and distill under reduced pressure to obtain cyclopropyl boric acid trim...

Embodiment 2

[0025] In the reaction flask, add aldehyde boronic acid (7.4g, 0.1mol), absolute ethanol 65mL and 2,4-dinitro-p-toluenesulfonyl hydrazide (26.2g, 0.1mol), after adding, heat up to reflux reaction, TLC After the detection reaction was completed, the absolute ethanol was distilled off under normal pressure, and then 220 mL of toluene was added and then refluxed to separate water until the detection reaction was completely transformed into a trimer. After cooling down, evaporate the toluene solvent to dryness, cool down to 0°C, add 120mL of tetrahydrofuran, then add 1.6M n-butyllithium (65mL, 0.104mol) dropwise, stir for 30 minutes, add catalyst FeCl(TPP) (0.05eq) , began to continuously feed ethylene gas into the reaction solvent, replaced the gas outlet of the reaction bottle with two layers of balloons, maintained a certain pressure in the reaction system until the system no longer absorbed, added 60mL sulfolane, and distilled under reduced pressure to obtain cyclopropyl Add 3...

Embodiment 3

[0027] In the reaction flask, add aldehydoboronic acid (7.4g, 0.1mol), anhydrous methanol 60mL and 3,5-dinitro-p-toluenesulfonyl hydrazide (26.2g, 0.1mol), heat up to reflux reaction after addition, TLC After the detection reaction was completed, the anhydrous methanol was distilled off under normal pressure, and then 220 mL of toluene was added, and then the water was refluxed until the detection reaction was completely transformed into a trimer. After cooling down, evaporate the toluene solvent to dryness, cool down to 0°C, add 120mL of tetrahydrofuran, then add 2.5M n-butyllithium (65mL, 0.104mol) dropwise, stir for 30 minutes, add the catalyst FeBr(TPP) (0.05eq) , began to continuously feed ethylene gas into the reaction solvent, replaced the gas outlet of the reaction bottle with two layers of balloons, maintained a certain pressure in the reaction system until the system no longer absorbed, added 60mL sulfolane, and distilled under reduced pressure to obtain cyclopropyl ...

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Abstract

The invention discloses a synthesis method of cyclopropyl boric acid, and belongs to the field of boric acid synthesis in organic chemistry. The synthesis method comprises the following steps: starting from formyl boric acid, enabling the formyl boric acid with strong electron-withdrawing sulfohydrazide to generate hydrazone, then introducing ethylene under the catalysis of ferriporphyrin, and reacting, thus obtaining the cyclopropyl boric acid. The synthesis method disclosed by the invention is simple in operation, the use of cyclopropyl bromide in a traditional technological method is avoided by adopting cyclopropanation reaction under metal catalysis, and a new synthesis path is provided for synthesis of the cyclopropyl boric acid.

Description

technical field [0001] The invention relates to the synthesis of alkyl boronic acid, in particular to a synthesis method of cyclopropyl boronic acid, and belongs to the technical field of organic boronic acid synthesis of pharmaceutical intermediates. Background technique [0002] Cyclopropylboronic acid, as an important coupling aid for Suzuki coupling, has been involved in more and more drug research since the coupling reaction won the Nobel Prize in Chemistry in 2010. Due to the special structure of cyclopropyl itself, it has become an indispensable raw material in drug synthesis, and it is difficult to replace it with other raw materials. [0003] The existing synthesis methods basically use cyclopropyl bromide as a raw material, first prepare Grignard reagent or metal lithium reagent, then react with trimethyl borate, and obtain cyclopropylboronic acid after acidification treatment. There are also patent publications reporting that after the reaction between cyclopropy...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F5/02
CPCC07F5/025
Inventor 冷延国张进张朋岳孙胜辉
Owner CANGZHOU PURUI DONGFANG SCI & TECH
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