Palladium-catalyzed N-H carbonylation reaction of N-phenylpyridine-2-amine by taking DMF (Dimethyl Formamide) as methyl source

A carbonylation reaction and phenylpyridine technology, applied in the field of medicinal chemistry, can solve the problems of harsh reaction conditions and limited applicability of substrates, and achieve the effects of easy availability of raw materials, excellent yield, simple and safe operation

Pending Publication Date: 2022-04-08
GUILIN UNIVERSITY OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The reaction conditions are harsh and the substrate applicability is limited

Method used

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  • Palladium-catalyzed N-H carbonylation reaction of N-phenylpyridine-2-amine by taking DMF (Dimethyl Formamide) as methyl source
  • Palladium-catalyzed N-H carbonylation reaction of N-phenylpyridine-2-amine by taking DMF (Dimethyl Formamide) as methyl source
  • Palladium-catalyzed N-H carbonylation reaction of N-phenylpyridine-2-amine by taking DMF (Dimethyl Formamide) as methyl source

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Add 0.2 mmol of N-phenylpyridin-2-amine, 0.03 mmol of palladium acetate, 0.22 mmol of copper acetate, and 0.04 mmol of potassium iodide into a 25 mL test tube, add N,N-dimethylformamide (DMF)3 mL as a solvent, put a balloon containing carbon monoxide gas as a carbonyl source, and stir at 100 degrees Celsius. After the TLC (thin layer chromatography) detection reaction, the reaction solution was cooled to room temperature, the balloon was removed, and the unreacted carbon monoxide was slowly vented. The reaction solution was filtered, and the filtrate was rotary evaporated under reduced pressure to remove the solvent, and then separated and purified by column chromatography to obtain the target product with a yield of 30%.

Embodiment 2

[0033] Add 0.2 mmol of N-phenylpyridin-2-amine, 0.03 mmol of palladium trifluoroacetate, 0.22 mmol of copper acetate, 0.04 mmol of potassium iodide into a 25 mL test tube, add N,N-dimethylformamide (DMF ) 3 ml as a solvent, put a balloon containing carbon monoxide gas as a carbonyl source, and stir at 100 degrees Celsius. After the TLC (thin layer chromatography) detection reaction, the reaction solution was cooled to room temperature, the balloon was removed, and the unreacted carbon monoxide was slowly vented. The reaction solution was filtered, and the filtrate was rotary evaporated under reduced pressure to remove the solvent, and then separated and purified by column chromatography to obtain the target product with a yield of 25%.

Embodiment 3

[0035] Add 0.2 millimoles of N-phenylpyridin-2-amine, 0.03 millimoles of palladium dichlorodiacetonitrile, 0.22 millimoles of copper acetate, 0.04 millimoles of potassium iodide, and add N,N-dimethylformamide ( DMF) 3 ml as a solvent, covered with a balloon containing carbon monoxide gas as a carbonyl source, stirred at 100 degrees Celsius. After the TLC (thin layer chromatography) detection reaction, the reaction solution was cooled to room temperature, the balloon was removed, and the unreacted carbon monoxide was slowly vented. The reaction solution was filtered, and the filtrate was rotary evaporated under reduced pressure to remove the solvent, and then separated and purified by column chromatography to obtain the target product with a yield of 32%.

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Abstract

The invention relates to a palladium-catalyzed N-H carbonylation reaction of N-phenylpyridine-2-amine by taking DMF (Dimethyl Formamide) as a methyl source. The method comprises the following steps: adding N-phenylpyridine-2-amine, a catalyst, an oxidant, an additive, a ligand and a solvent into a glass test tube, sleeving a reactor with a balloon filled with carbon monoxide, carrying out a stirring reaction at 40-150 DEG C for 1-40 h, cooling to room temperature after the reaction is finished, removing the balloon, filtering the reaction liquid, and carrying out reduced pressure evaporation to remove the solvent so as to obtain a crude product; and carrying out column chromatography purification to obtain the N-H carbonylation product of the N-phenylpyridine-2-amine. The N-H carbonylation process of N-phenylpyridine-2-amine is achieved through carbonylation reaction, and the method has the advantages that operation is simple, raw materials are easy to obtain, meanwhile, the method has good functional group tolerance, and the yield is excellent.

Description

technical field [0001] The invention relates to the technical fields of medicinal chemistry, pesticide science, dye chemistry, organic synthesis, etc., and specifically relates to a palladium-catalyzed N-H carbonylation reaction of N-phenylpyridin-2-amine using DMF as a methyl source. Background technique [0002] The acetylation of amines is one of the most fundamental transformations in organic chemistry. This reaction is widely used in the pharmaceutical industry and agriculture. Acetylation of amines usually occurs with acetic acid / acetic anhydride / acetyl chloride under basic or acidic conditions. The reaction conditions are harsh and the substrate applicability is limited. Carbonylation reaction, as the key reaction to introduce carbonyl groups, provides more synthetic routes for the acetylation reaction of amines. At the same time, the research work using the industrial solvent N,N-dimethylformamide (DMF) as a methyl source has also attracted widespread attention of...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D213/75
Inventor 及方华李璇徐嘉伟
Owner GUILIN UNIVERSITY OF TECHNOLOGY
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