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Method for synthesizing biaryl ketone compounds through carbonylation by taking chloroform as carbonyl source without transition metal participation

A technology of diaryl ketones and compounds, which is applied in the field of catalytic synthesis, can solve the problems of carbonyl sources such as toxicity, safety hazards, and difficult handling, and achieve the effects of easy handling, avoiding flammability, and stable treatment

Active Publication Date: 2018-11-09
NANJING NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] Purpose of the invention: In view of the shortcomings of the existing methods for carbonylation of diaryl ketones, which usually require expensive transition metal catalysts and metal residues produced by the use of transition metals, and the carbonyl source is toxic, flammable, and difficult to handle, there are serious potential safety hazards etc., the present invention provides a method for synthesizing diaryl ketones by carbonylation of chloroform as a carbonyl source without the participation of transition metals. Carbonyl sources are directly coupled to synthesize diaryl ketones. This method has the advantages of low cost and no metal residues without transition metal catalysts; carbonyl sources are safe, cheap and easy to handle; reaction conditions are mild and selective; substrates Extensive and stable sources; good compatibility of substrate functional groups and wide application range of substrates

Method used

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  • Method for synthesizing biaryl ketone compounds through carbonylation by taking chloroform as carbonyl source without transition metal participation
  • Method for synthesizing biaryl ketone compounds through carbonylation by taking chloroform as carbonyl source without transition metal participation
  • Method for synthesizing biaryl ketone compounds through carbonylation by taking chloroform as carbonyl source without transition metal participation

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Experimental program
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Embodiment 1

[0031] Compound 1: Add 4-fluorophenylboronic acid (0.75mmol), sodium carbonate (1.0mmol), cesium hydroxide monohydrate (2.5mmol), sodium iodide (0.25mmol), pivalic acid (0.75mmol) ), 4-iodophenylacetylene (0.5mmol), chloroform (1.5mmol) and ethylene glycol (2.0g), and reacted at 120°C for 24h. Cool to room temperature, extract, evaporate the solvent under reduced pressure, and separate by column chromatography to obtain a yield of 86%.

Embodiment 2

[0033] Compound 1: Add 4-fluorophenylboronic acid (0.75mmol), sodium carbonate (1.0mmol), cesium hydroxide monohydrate (2.5mmol), sodium iodide (0.25mmol), pivalic acid (0.75mmol) ), 4-iodophenylacetylene (0.5mmol), chloroform (1.5mmol) and ethylene glycol (2.0g), and reacted at 50°C for 72h. Cool to room temperature, extract, evaporate the solvent under reduced pressure, and separate by column chromatography to obtain a yield of 25%.

Embodiment 3

[0035] Compound 1: Add 4-fluorophenylboronic acid (0.75mmol), sodium carbonate (1.0mmol), cesium hydroxide monohydrate (2.5mmol), sodium iodide (0.25mmol), pivalic acid (0.75mmol) ), 4-iodophenylacetylene (0.5mmol), chloroform (1.5mmol) and ethylene glycol (2.0g), and reacted at 200°C for 0.5h. Cool to room temperature, extract, evaporate the solvent under reduced pressure, and separate by column chromatography to obtain a yield of 90%.

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Abstract

The invention discloses a method for synthesizing biaryl ketone compounds through carbonylation by taking chloroform as a carbonyl source without transition metal participation. The method disclosed by the invention comprises the following steps: carrying out a cross coupling reaction on aryl halides, aromatic boron compounds and chloroform serving as the carbonyl source in an aqueous solution ofsolvent alcohol or alcohol in the presence of alkali, acids and iodides without transition metal participation, thereby obtaining the biaryl ketone compounds. According to the method for preparing thebiaryl ketone compounds through the cross coupling reaction, disclosed by the invention, the most obvious advantage is that no transition metal catalyst is used and the chloroform serves as the carbonyl source; the method has the advantages such as low cost and zero metal residue caused by no need of the transition metal catalyst; the carbonyl source is safe, cheap and easy to treat; the reactioncondition is mild, and the selectivity is high; the substrate source is wide and stable; and the compatibility of functional groups of the substrate is excellent, the application range of the substrate is wide, and under the optimized reaction conditions, the separation yield of the target product reaches 95%.

Description

technical field [0001] The invention belongs to the technical field of catalytic synthesis, and more specifically relates to a method for synthesizing diaryl ketones by carbonylation of chloroform as a carbonyl source without the participation of transition metals. A method for preparing diaryl ketone compounds through cross-coupling reaction of halides, aryl boron compounds and chloroform as carbonyl sources. Background technique [0002] The Suzuki reaction of carbonylation has the advantages of good reaction selectivity, high yield, wide range of substrate sources and good stability, wide substrate application range and good functional group compatibility, and can be used to synthesize high value-added diaryl ketones compounds, which have attracted extensive attention. At present, the catalytic system of the Suzuki reaction that catalyzes carbonylation generally uses expensive palladium catalysts and phosphine ligands, but the phosphine ligands are toxic, unstable to air...

Claims

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Application Information

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IPC IPC(8): C07C49/813C07C49/792C07C49/84C07C49/788C07C45/00C07C205/45C07C201/12C07C225/22C07C221/00C07D295/192C07C323/22C07C319/12C07D213/50C07D333/22C07D213/643C07C317/24C07C315/04C07D207/333C07D263/32C07D277/24C07D403/06C07D209/08C07D409/06C07D307/80C07D417/06
CPCC07C49/788C07C49/792C07C49/813C07C49/84C07C205/45C07C225/22C07C317/24C07C323/22C07D207/333C07D209/08C07D213/50C07D213/643C07D263/32C07D277/24C07D295/192C07D307/80C07D333/22C07D403/06C07D409/06C07D417/06
Inventor 韩维徐方宁
Owner NANJING NORMAL UNIVERSITY