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Method for synthesizing 2-fluoroarylcarbonyl compounds

A technology for aryl carbonyl compounds, which is applied in the field of synthesizing 2-fluoroaryl carbonyl compounds, can solve the problems of poor fluorination selectivity, complex directing groups, narrow substrate range, etc., and achieve mild reaction conditions and fluorination selectivity High performance and good substrate adaptability

Active Publication Date: 2014-07-16
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Nevertheless, there are always some unsatisfactory aspects in these systems that need to be improved, such as poor selectivity of fluorination, narrow substrate scope, complex directing groups, harsh conditions, etc.

Method used

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  • Method for synthesizing 2-fluoroarylcarbonyl compounds
  • Method for synthesizing 2-fluoroarylcarbonyl compounds
  • Method for synthesizing 2-fluoroarylcarbonyl compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0049]

[0050] [1] Add 0.600g (5.0mmol) of acetophenone, 0.835g (10.0mmol) of methoxylamine hydrochloride, 1.640g (20.0mmol) of anhydrous sodium acetate, 10ml of ethanol and 30ml of water into a 100ml flask. After the mixture was heated to reflux for 2 hours, TLC detected that the reaction was complete, and 30 ml of ethyl acetate was added for dilution and extraction. The organic phase was dried and the solvent was removed under reduced pressure to obtain 0.708 g of acetophenone oxime ether (95% yield).

[0051] [2] Add acetophenone oxime ether (44.7mg, 0.3mmol), tris(dibenzylideneacetone) dipalladium (13.7mg, 0.015mmol), N-fluorobenzenesulfonyl Amine (189.0mg, 0.6mmol), potassium nitrate (9.1mg, 0.09mmol), nitromethane (3.0mL), the reaction mixture was stirred at 25°C, followed by TLC detection, and the reaction was complete within 24 hours. Stop the reaction, dilute the mixture with dichloromethane, filter and remove the solvent under reduced pressure, and the residue is...

Embodiment 2

[0054]

[0055] [1] Add 0.690g (5.0mmol) of 4-fluoroacetophenone, 0.835g (10.0mmol) of methoxyamine hydrochloride, 1.640g (20.0mmol) of anhydrous sodium acetate, 10ml of ethanol and 30ml of water into a 100ml flask inside. After the mixture was heated to reflux for 2 hours, TLC detected that the reaction was complete, and 30ml of ethyl acetate was added for dilution and extraction. The organic phase was dried and the solvent was removed under reduced pressure to obtain 0.776g of 4-fluoroacetophenone oxime ether (93% yield). .

[0056] [2] Add 4-fluoroacetophenone oxime ether (50.1mg, 0.3mmol), tris(dibenzylideneacetone) dipalladium (13.7mg, 0.015mmol), N-fluorobenzene Sulfonimide (189.0mg, 0.6mmol), potassium nitrate (9.1mg, 0.09mmol), nitromethane (3.0mL), the reaction mixture was stirred at 40°C, followed by TLC detection, and the reaction was complete within 24 hours. Stop the reaction, dilute the mixture with dichloromethane, remove the solvent under reduced pressure ...

Embodiment 3

[0059]

[0060] [1] Add 0.750g (5.0mmol) of 4-methoxyacetophenone, 0.835g (10.0mmol) of methoxyamine hydrochloride, 1.640g (20.0mmol) of anhydrous sodium acetate, 10ml of ethanol and 30ml of water 100ml flask. After the mixture was heated to reflux for 2 hours, TLC detected that the reaction was complete, and 15 ml of ethyl acetate was added for dilution and extraction. The organic phase was dried and the solvent was removed under reduced pressure to obtain 0.841 g of 4-methoxyacetophenone oxime ether (94% yield). Rate).

[0061] [2] Add 4-methoxyacetophenone oxime ether (53.7mg, 0.3mmol), tris(dibenzylideneacetone) dipalladium (13.7mg, 0.015mmol), N-fluoro Phenylenesulfonylimide (189.0mg, 0.6mmol), potassium nitrate (9.1mg, 0.09mmol), nitromethane (3.0mL), the reaction mixture was stirred at 25°C, followed by TLC detection, and the reaction was complete within 24 hours. Stop the reaction, dilute the mixture with dichloromethane, remove the solvent under reduced pressure ...

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Abstract

The invention provides a method for synthesizing 2-fluoroarylcarbonyl compounds, which comprises the following steps: converting arylcarbonyl compounds into corresponding carbonyl oxime ether compounds, mildly implementing aryl hydrocarbon chain direct fluoridation of high-selectivity oximido substituent group ortho-position in the presence of a palladium catalyst, a fluoridation reagent and additives, and finally, rehydrolyzing oxime ethers under the action of acid to obtain the 2-fluoroarylcarbonyl compounds. The fluoridation method has the advantages of mild reaction conditions, high substrate adaptability, high fluoridation selectivity and the like, is simple to operate, and has higher application research value.

Description

technical field [0001] The invention relates to a method for synthesizing 2-fluoroaryl carbonyl compounds. Background technique [0002] The introduction of fluorine atoms into aromatic hydrocarbon compounds can significantly increase the stability of the compound, and at the same time improve its fat solubility and hydrophobicity, promote its absorption and delivery in the body, and change the physiological effects, so many fluorine-containing medicines and pesticides are in performance. Relatively, it has the characteristics of less dosage, low toxicity, high drug efficacy, and strong metabolism, which makes it account for an increasing proportion of new medicines and pesticides. In addition, fluorine-containing dyes, fluorine-containing surfactants, fluorine-containing fabric finishing agents, and fluorine-containing coatings have become high value-added and promising varieties in the field of fine chemicals. It is precisely because of the particularity of carbon-fluorin...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/42C07C49/807C07C49/35C07C49/80C07C49/813C07C47/55C07C317/22C07C315/04C07C205/45C07C201/12
CPCC07C45/42C07C47/55C07C49/35C07C49/80C07C49/807C07C49/813C07C201/12C07C205/45C07C315/04C07C317/22
Inventor 许丹倩娄绍杰徐振元
Owner ZHEJIANG UNIV OF TECH
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