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Synthesis method of 2-fluoroarylcarbonyl compound

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

Active Publication Date: 2014-07-09
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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  • Synthesis method of 2-fluoroarylcarbonyl compound
  • Synthesis method of 2-fluoroarylcarbonyl compound
  • Synthesis method of 2-fluoroarylcarbonyl compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044]

[0045] [1] Add 0.730g (5.0mmol) of tetralone, 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 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 0.753 g of tetralone oxime ether (86% yield).

[0046] [2] Add tetralone oxime ether (52.5mg, 0.3mmol), tris(dibenzylideneacetone) dipalladium (13.7mg, 0.015mmol), 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 reduced pressure, and the residue is subjecte...

Embodiment 2

[0049]

[0050] [1] Add 0.740g (5.0mmol) of chroman-4-one, 0.835g (10.0mmol) of methoxyamino hydrochloride, 1.640g (20.0mmol) of anhydrous sodium acetate, 10ml of ethanol and 30ml 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 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 0.761 g of chromanone oxime ether (86% yield ).

[0051] [2] Add chromanone oxime ether (53.1mg, 0.3mmol), tris(dibenzylideneacetone) dipalladium (13.7mg, 0.015mmol), N-fluoro Benzenesulfonylimide (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, filter and remove the solvent under reduced pressure, and the resi...

Embodiment 3

[0054]

[0055] [1] Add 0.800g (5.0mmol) of benzocycloheptanone, 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 . 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 0.803 g of benzocycloheptanone oxime ether (85% yield).

[0056] [2] Add benzocycloheptanone oxime ether (56.7mg, 0.3mmol), tris(dibenzylideneacetone) dipalladium (13.7mg, 0.015mmol), N-fluorobenzenesulfonate into a closed reaction vessel Imide (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, filter and remove t...

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Abstract

The invention provides a synthesis method of a 2-fluoroarylcarbonyl compound as shown in the formula IV. The synthesis method comprises the steps of converting an arylcarbonyl compound into a corresponding carbonyl oxime ether compound; then, mildly and directly fluorinating a high-selectivity aryl carbon hydrogen bond at the ortho-position of an oximido substituent in the existence of a palladium catalyst, a fluorinated reagent and an additive; finally, hydrolyzing oxime ether again under the action of acid to obtain the 2-fluoroarylcarbonyl compound. The fluorinating method has the advantages of mild reaction conditions, simplicity in operation, good substrate adaptability, high fluorination selectivity and the like, and has relatively high application and research values.

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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IPC IPC(8): C07C49/697C07C45/42C07D311/22
CPCC07C45/42C07C49/697C07D311/22
Inventor 娄绍杰许丹倩徐振元
Owner ZHEJIANG UNIV OF TECH
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