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Method for removing by-product in a palladium-catalyzed coupling reaction in situ

A coupling reaction, palladium-catalyzed technology, used in organic chemistry methods, chemical instruments and methods, purification/separation/stabilization of organic compounds, etc. problem, to achieve the effect of reducing concentration, reducing precipitation, and low cost

Inactive Publication Date: 2013-07-10
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the palladium catalyzed coupling reaction will produce acid as a by-product during the reaction, which seriously affects the progress of the reaction and reduces the rate of the reaction. Therefore, people usually add alkaline acid-binding agents to neutralize the reaction process. acid, so that the reaction moves forward to increase the conversion rate of the reaction. Commonly used organic acid-binding agents mainly include basic organic compounds such as pyridine, triethylamine, and diethylamine.
However, often due to the presence of an organic acid-binding agent, the acid generated during the reaction is neutralized by the acid-binding agent to generate an ammonium salt. This ammonium salt is usually insoluble in the reaction solvent. When the concentration of the ammonium salt reaches a certain value, it will be removed from the reaction system. The ammonium salt is selectively precipitated on the surface of the catalyst to wrap the palladium carbon catalyst and deactivate the catalyst, resulting in a decrease in the conversion rate of the reaction

Method used

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  • Method for removing by-product in a palladium-catalyzed coupling reaction in situ
  • Method for removing by-product in a palladium-catalyzed coupling reaction in situ
  • Method for removing by-product in a palladium-catalyzed coupling reaction in situ

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Experimental program
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Effect test

Embodiment 1

[0027] Embodiment 1, remove by product in the Suzuki reaction

[0028] Two reaction systems were prepared: 5 mmol of iodobenzene and 10 mmol of phenylboronic acid were dissolved in 50 mL of toluene, 0.1 g of 5 wt % Pd / C catalyst was added, and the acid-binding agent was triethylamine.

[0029] In order to illustrate the impact of the inventive method on the Suzuki reaction, one part does not add any substance, which is recorded as the Suzuki-N system; the other part adds 2g of water content and is 80% wet activated carbon solid powder, which is recorded as the Suzuki-H system , in this system, the addition amount of wet activated carbon solid powder is 1 time of the total mass of iodobenzene and phenylboronic acid. Subsequently, the temperature of the two reaction systems was raised to 80° C., and 10 mmol of triethylamine was added to start the reaction. Sampling was performed at intervals of 15 minutes, and the conversion rate was analyzed by Shimadzu 10A-VP-PLUS liquid chrom...

Embodiment 2

[0031] Embodiment 2, remove the by product in the Suzuki reaction

[0032] Two reaction systems were prepared: 5 mmol of iodobenzene and 10 mmol of phenylboronic acid were dissolved in 50 ml of chloroform, and 0.1 g of 5 wt % Pd / C catalyst was added, and the acid-binding agent was ethylenediamine.

[0033] In order to illustrate the impact of the inventive method on the Suzuki reaction, one part does not add any substance, which is recorded as the Suzuki-N system; another part of the porous silicon oxide that adds 2g of water content is 100%, and is recorded as the Suzuki-H system. In the system, the amount of porous silicon oxide added is 1 time of the total mass of iodobenzene and phenylboronic acid. Subsequently, the temperature of the two reaction systems was raised to 60° C., and 10 mmol of triethylamine was added to start the reaction. Sampling was performed at intervals of 15 minutes. The conversion rate was analyzed by Shimadzu 10A-VP-PLUS liquid chromatography.

[00...

Embodiment 3

[0035] Embodiment 3, remove the by product in the Heck reaction

[0036] Prepare two reaction systems: dissolve 5mmol iodobenzene and 10mmol styrene into 30ml toluene, add 0.1g 5wt% Pd / C catalyst, and use pyridine as the acid-binding agent.

[0037] In order to illustrate the impact of the inventive method on the Heck reaction, one part does not add any substance, which is recorded as the Heck-N system; the other part adds 3g of gac with a water content of 100%, which is recorded as the Heck-H system, and in this system , the amount of activated carbon added is 3 times the total mass of iodobenzene and styrene. Subsequently, the temperature of the two reaction systems was raised to 90°C, 10 mmol of triethylamine was added to start the reaction, samples were taken at intervals of 0.5 h, and the conversion rate was analyzed by Shimadzu 10A-VP-PLUS liquid chromatography.

[0038] image 3 It is a comparison of the catalytic kinetic curves of the Heck reaction system. It can be ...

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Abstract

The invention discloses a method for removing by-product in a palladium-catalyzed coupling reaction in situ. The method disclosed by the invention comprises the following steps of: adding a water-containing porous medium into a reaction system of the palladium-catalyzed coupling reaction and instantly removing by-products in the palladium-catalyzed coupling reaction; and adding an acid-binding agent into the palladium-catalyzed coupling reaction. According to the method disclosed by the invention, by adding the water-containing porous medium into the coupling reaction system, ammonium salt formed in the reaction process is absorbed by the water-containing porous medium, the concentration of the by-product ammonium salt in the reaction system is effectively reduced and the precipitation of the ammonium salt is greatly reduced, so that a palladium carbon catalyst can stably play the role of catalyzing in an organic solution. The method disclosed by the invention is simple and effective, low in cost and easy for industrial production.

Description

technical field [0001] The invention relates to a method for removing by-products in a palladium-catalyzed coupling reaction in situ, and belongs to the technical field of organic synthesis. Background technique [0002] The construction of C-C bonds is an important technical field in organic synthesis. Palladium-catalyzed coupling reactions are a simple and practical chemical reaction for the construction of C-C bonds, including Suzuki reactions, Heck reactions, Negishi reactions, and Stille reactions. Using palladium-catalyzed coupling reactions, many drug intermediates and some natural products can be easily synthesized, thus opening up a commonly used organic reaction for C-C synthesis in synthetic chemistry. Palladium on carbon is widely used as a catalyst in palladium-catalyzed coupling reactions due to its high activity and easy preparation and recovery. However, the palladium catalyzed coupling reaction will produce acid as a by-product during the reaction, which se...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B63/00C07C1/32C07C15/14C07C17/275C07C22/04
Inventor 宋卫国刘华曹昌燕
Owner INST OF CHEM CHINESE ACAD OF SCI
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