Method for preparing alpha, beta-acetylenic ketone compounds through carbon monoxide-releasing molecular carbonylation carbon-carbon bond coupling

A molecular carbon carbonylation and carbon monoxide technology, which is applied in the preparation of carbon-based compounds, the preparation of organic compounds, chemical instruments and methods, etc., can solve the problems of harsh carbon monoxide release conditions, high requirements for reaction devices, and expensive reagents. Low requirements, good substrate applicability, and simple operation

Active Publication Date: 2017-06-20
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Metal carbonyl compounds with multiple carbonyl groups [Mo(CO) 6 ], [Cr(CO) 6 ], [W(CO) 5 ], etc. are potential non-gaseous CO sources, which can be used as new carbonylation reagents, but these reagents are expensive, and the conditions for carbon monoxide release are harsh, often requiring strong alkali, strong heat, and high requirements for reaction devices.

Method used

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  • Method for preparing alpha, beta-acetylenic ketone compounds through carbon monoxide-releasing molecular carbonylation carbon-carbon bond coupling
  • Method for preparing alpha, beta-acetylenic ketone compounds through carbon monoxide-releasing molecular carbonylation carbon-carbon bond coupling
  • Method for preparing alpha, beta-acetylenic ketone compounds through carbon monoxide-releasing molecular carbonylation carbon-carbon bond coupling

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0017] Preparation of 1-(4-methoxyphenyl)-3-phenyl-2-ethynyl-1-one of the following structural formula

[0018]

[0019] 0.1090g (0.5mmol) 4-methoxy iodobenzene, 0.0680g (0.5mmol) potassium carbonate, 0.0009g (0.005mmol) palladium chloride, 0.0058g (0.01mmol) 4,5-bisdiphenylphosphine- Add 9,9-dimethylxanthene, 3ml N,N-dimethylformamide, 55μl (0.5mmol) phenylacetylene, 67μl (0.5mmol) iron pentacarbonyl into the reaction flask, and react at 70°C for 12 hours , stop the reaction, cool down to room temperature naturally, after extraction with ethyl acetate, pickle with dilute hydrochloric acid for 3 times, then wash with water for 3 times, filter, and separate by column chromatography (the volume ratio of petroleum ether to ethyl acetate is 20:1) The mixture is the eluent) to obtain 1-(4-methoxyphenyl)-3-phenyl-2-ethynyl-1-one as a brown solid with a yield of 92%.

Embodiment 2

[0021] In Example 1, the 4-methoxy iodobenzene used was replaced with equimolar 4-methoxy bromobenzene, and the other steps were the same as in Example 1 to obtain a yellow solid 1-(4-methoxyphenyl)- 3-Phenyl-2-ethynyl-1-one in 70% yield.

Embodiment 3

[0023] Preparation of 1-(4-methylphenyl)-3-phenyl-2-ethynyl-1-one of the following structural formula

[0024]

[0025] In Example 1, the 4-methoxy iodobenzene used was replaced with equimolar 4-methyl iodobenzene, and the other steps were the same as in Example 1 to obtain a yellow solid 1-(4-methylphenyl)-3- Phenyl-2-ethynyl-1-one in 83% yield.

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Abstract

The invention discloses a method for preparing alpha, beta-acetylenic ketone compounds through carbon monoxide-releasing molecular carbonylation carbon-carbon bond coupling. According to the method, CO gas is not used, and the method comprises the following steps: by taking palladium chloride as a catalyst, taking 4,5-bis (diphenylphosphino)-9,9-dimethyl xanthenes as a ligand, taking N, N-dimethyl formamide as a solvent, taking pentacarbonyl iron as a CO supply source of a carbon monoxide-releasing molecule, coupling aryl halides and terminal alkyne under alkaline conditions, thereby obtaining the alpha, beta-acetylenic ketone compounds. According to the method disclosed by the invention, usage of high-pressure poisonous gas carbon monoxide is avoided, and the method is simple and safe in experimental operation, mild in conditions and high in substrate applicability and can be widely applied to preparing the alpha, beta-acetylenic ketone compounds.

Description

technical field [0001] The invention relates to a kind of 4,5-bisdiphenylphosphine-9,9-dimethyl with aryl halide and terminal alkyne as substrate, iron pentacarbonyl release molecule as CO supply source, palladium chloride as catalyst, A method for preparing α, β-ynone compounds using Xantphos as a ligand. Background technique [0002] α,β-ynones have very important structural variability and are widely used in the construction of natural compounds, as reaction intermediates, and play an important role in the rapid construction of complex structures in the synthesis of bioactive molecules. Various important intermediates of heterocyclic structures, such as pyrimidine, quinolone, furan, pyridine, flavone, etc., can be synthesized by using molecules directly connected to the carbonyl group with an alkynyl group. [0003] The traditional method for synthesizing acetylene ketones is to use transition metals to catalyze the cross-coupling reaction of acid chlorides and terminal ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/00C07C49/84C07C49/796C07C201/12C07C205/45
CPCC07C45/00C07C201/12C07C49/84C07C49/796C07C205/45
Inventor 张伟强王贤王振华宋成鑫谢遵园张国防高子伟
Owner SHAANXI NORMAL UNIV
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