Method for synthesizing beta-fluoro-alpha,beta-unsaturated ketene compounds

An unsaturated compound technology, applied in the hydrolysis of carbonyl compounds, organic chemistry, oxime preparation, etc., to achieve the effect of high fluorination selectivity, good substrate adaptability and mild reaction conditions

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

Aryl sp has been involved in related studies reported so far 2 Fluorination of carbon-hydrogen bonds and sp3 carbon-hydrogen bonds, while for alkenyl sp 2 Activated fluorination of carbon-hydrogen bonds has not been reported

Method used

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  • Method for synthesizing beta-fluoro-alpha,beta-unsaturated ketene compounds
  • Method for synthesizing beta-fluoro-alpha,beta-unsaturated ketene compounds
  • Method for synthesizing beta-fluoro-alpha,beta-unsaturated ketene compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043]

[0044] [1] Mix 0.900g (5.0mmol) of 3-chloro-4-phenylbutenone, 0.835g (10.0mmol) of methoxyamino hydrochloride, 1.640g (20.0mmol) of anhydrous sodium acetate, 10ml of ethanol and 30ml of water was added to the 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 layer was dried and the solvent was removed under reduced pressure to obtain 0.867 g of 3-chloro-4-phenylbutenone oxime ether ( 83% yield).

[0045] [2] Add 3-chloro-4-phenylbutenone oxime ether (62.7mg, 0.3mmol) and tris(dibenzylideneacetone)dipalladium (13.7mg, 0.015mmol) into a closed reaction vessel, N-fluorobenzenesulfonimide (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 dichlor...

Embodiment 2

[0048]

[0049] [1] Mix 0.900g (5.0mmol) of 3-chloro-4-phenylbutenone, 0.835g (10.0mmol) of methoxyamino hydrochloride, 1.640g (20.0mmol) of anhydrous sodium acetate, 10ml of ethanol and 30ml of water was added to the 100ml flask. 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 0.867g of 3-chloro-4-phenylbutenone oxime ether ( 83% yield).

[0050] [2] Add 3-chloro-4-phenylbutenone oxime ether (62.7mg, 0.3mmol) and tris(dibenzylideneacetone)dipalladium (13.7mg, 0.015mmol) into a closed reaction vessel, N-fluorobenzenesulfonylimide (189.0mg, 0.6mmol), silver nitrate (15.2mg, 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 dichlorom...

Embodiment 3

[0053]

[0054] [1] Mix 0.900g (5.0mmol) of 3-chloro-4-phenylbutenone, 0.835g (10.0mmol) of methoxyamino hydrochloride, 1.640g (20.0mmol) of anhydrous sodium acetate, 10ml of ethanol and 30ml of water was added to the 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 layer was dried and the solvent was removed under reduced pressure to obtain 0.867 g of 3-chloro-4-phenylbutenone oxime ether ( 83% yield).

[0055] [2] Add 3-chloro-4-phenylbutenone oxime ether (62.7mg, 0.3mmol), palladium diacetate (6.7mg, 0.03mmol), N-fluorobenzenesulfonyl Imine (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 reduce...

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PUM

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Abstract

The invention provides a method for synthesizing beta-fluoro-alpha,beta-unsaturated ketene compounds, which comprises the following steps: converting alpha,beta-unsaturated ketene compounds into corresponding carbonyl oxime ether compounds, mildly implementing sp2 alkenyl hydrocarbon chain direct fluoridation of high-selectivity beta- 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 beta-fluoro-alpha,beta-unsaturated ketene 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 present invention relates to a method for synthesizing β-fluoro-α, β-unsaturated enone compounds. Background technique [0002] There are many types of α,β-unsaturated enones and they are widely used. Compounds containing α,β-unsaturated carbonyl structures in their molecules are usually used as substrates for a series of chemical reactions, including Michael addition, Morita–Baylis–Hillman reaction, Diels-Alder reaction and some organic catalytic reactions. However, the importance of α,β-unsaturated carbonyl compounds is not only reflected here, many of them have unique pharmacological properties, such as anticancer activity, cytotoxicity and can be used as anti-inflammatory drugs, analgesics and antipyretics, in addition Still others are considered as potential antibacterial and antifungal agents. In view of the important application of α,β-unsaturated enone in the field of organic synthesis and biomedicine, the selective introduction of fluori...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C49/235C07C45/42
CPCC07C45/42C07C49/235C07C249/04C07C249/12C07C251/40
Inventor 娄绍杰许丹倩徐振元
Owner ZHEJIANG UNIV OF TECH
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