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Method for carbonylation synthesis of diaryl ketones through iron catalysis

A technology for the synthesis of diaryl ketones, which is applied in the field of catalytic synthesis, can solve the problems of carbonyl sources being toxic, difficult to handle, and flammable, and achieve the effects of low toxicity, easy handling, and safe handling

Active Publication Date: 2016-11-16
NANJING NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Aiming at the problems that existing diaryl ketone synthesis methods have carbonyl sources that are toxic, flammable, difficult to handle, and serious safety hazards, the present invention provides a method for synthesizing diaryl ketones by iron-catalyzed carbonylation. Under the action of catalysts, aryl boron compounds, aromatic halide compounds and haloform or tetrahalogenated carbonyl sources are directly coupled to form diaryl ketones. This method has the advantages of safe, cheap and easy-to-handle carbonyl sources; the source of catalysts is wide, cheap and Low toxicity; the reaction does not require ligands and has good activity; the reaction conditions are mild and the selectivity is high; the source of the substrate is wide and stable; the functional group of the substrate is compatible and the substrate has a wide range of application; the reaction medium is green and can be recycled. Advantages

Method used

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  • Method for carbonylation synthesis of diaryl ketones through iron catalysis
  • Method for carbonylation synthesis of diaryl ketones through iron catalysis
  • Method for carbonylation synthesis of diaryl ketones through iron catalysis

Examples

Experimental program
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Effect test

Embodiment 1

[0038] Compound 1: Add ferrous chloride (0.05mmol), 4-iodophenylacetylene (0.5mmol), 4-fluorophenylboronic acid (0.75mmol), sodium carbonate (1.0mmol) and cesium hydroxide monohydrate to a 25mL reaction flask in sequence (2.5mmol), sodium iodide (0.25mmol), pivalic acid (0.75mmol), chloroform (1.5mmol) and polyethylene glycol-400 (2.0g), and react at 120°C for 6h. Cool to room temperature, extract, evaporate the solvent under reduced pressure, and separate by column chromatography to obtain a yield of 87%.

Embodiment 2

[0040] Compound 2: Add ferrous chloride (0.05mmol), 4-cyclopropyl iodobenzene (0.5mmol), 2-methylphenylboronic acid (0.75mmol), sodium tert-butoxide (1.0mmol) to a 25mL reaction flask in sequence, Sodium carbonate (1.0 mmol), cesium hydroxide monohydrate (2.5 mmol), sodium iodide (0.25 mmol), pivalic acid (0.75 mmol), chloroform (1.5 mmol) and polyethylene glycol-1000 (2.0 g), And react at 120°C for 16h. Cool to room temperature, extract, evaporate the solvent under reduced pressure, and separate by column chromatography to obtain a yield of 79%.

Embodiment 3

[0042] Compound 3: Add ferrous chloride (0.05mmol), 4-nitroiodobenzene (0.5mmol), 2-cyclohexylphenylboronic acid (0.75mmol), sodium carbonate (1.0mmol) and hydrogen monohydrate to a 25mL reaction flask in sequence Cesium oxide (2.5mmol), sodium iodide (0.25mmol), pivalic acid (0.75mmol), fluoroform (1.5mmol) and polyethylene glycol-400 (2.0g) were reacted at 120°C for 15h. Cool to room temperature, extract, evaporate the solvent under reduced pressure, and separate by column chromatography to obtain a yield of 81%.

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Abstract

The invention discloses a method for carbonylation synthesis of diaryl ketones through iron catalysis and belongs to the technical field of catalytic synthesis. According to the method, in a solvent alcohol or alcohol aqueous solution, and in the action of alkali, acid and iodide, an iron catalyst is added for catalyzing a direct cross-coupling reaction of an aryl halogenated compound, an aryl boron compound and a carbonyl source including haloform or carbon tetrahalide to prepare a diaryl ketone compound. The method for preparing a diaryl ketone compound through a coupling reaction is safe in carbonyl source and easy to treat and is cheap; the catalyst is available in sources and low in toxicity and is cheap; the reaction is free of ligand and good in activity; the reaction condition is mild and the selectivity is high; the substrates are available in sources and are stable; the functional groups of the substrates are good in compatibility and the substrates are wide in application range; and the reaction medium is green and can be reused. In an optimized reaction condition, the separation yield of a target product can reach 94%.

Description

technical field [0001] The invention belongs to the technical field of catalytic synthesis, more specifically, relates to a method for synthesizing diaryl ketone by iron-catalyzed carbonylation, which is a method for directly utilizing aromatic boron compounds, aryl halides and haloform or tetrahalogenated carbonyl Source cross-coupling to prepare diaryl ketones. Background technique [0002] The skeleton structure of diaryl ketones widely exists in natural products, medicines, photosensitizers and organic materials, and its synthetic methods have attracted extensive attention. 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 various structures of diaryl ketones , which has attracted extensive attention. At present, the catalytic system of the Suzuki reaction that catalyz...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/06C07C45/45C07C49/813C07C49/792C07C49/84C07C201/12C07C205/45C07C221/00C07C225/22C07D207/06C07C319/20C07C323/22C07D213/50C07D333/22C07D213/643C07D213/55C07C315/04C07C317/24C07D209/12C07D407/06C07D207/333C07D263/32C07D417/06C07D403/06C07D409/06
CPCC07B41/06C07C45/45C07C201/12C07C221/00C07C315/04C07C319/20C07D207/06C07D207/333C07D209/12C07D213/50C07D213/55C07D213/643C07D263/32C07D333/22C07D403/06C07D407/06C07D409/06C07D417/06C07C49/813C07C49/792C07C49/84C07C205/45C07C225/22C07C323/22C07C317/24
Inventor 韩维杜宏艳
Owner NANJING NORMAL UNIVERSITY
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