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4-fluorine substituted arylamine compound and synthesis method thereof

A kind of technology of aniline compound and synthesis method, applied in the direction of amino compound preparation, amino hydroxyl compound preparation, chemical instrument and method, etc., can solve the problems of expensive reagents, unsuitable for scale-up production, etc., achieve low cost, widely popularize and use, increase lipophilic effect

Active Publication Date: 2021-09-21
江苏笃行致远新材料科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0013] Literature Nature 2015,524,208-211 reported the use of aryl bromide, AgF and KF as a fluorine source under the catalysis of palladium for fluorination. This method is not suitable for scale-up due to the use of an air- and water-sensitive catalytic system, and the reagent is expensive. Production

Method used

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  • 4-fluorine substituted arylamine compound and synthesis method thereof
  • 4-fluorine substituted arylamine compound and synthesis method thereof
  • 4-fluorine substituted arylamine compound and synthesis method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] Add N-acetylphenylhydroxylamine (151g, 1.0mol), KF (29g, 0.5mol) and dichloromethane (1.0L) to a stirred 2L reaction flask in turn, cool to 0°C, and pass through sulfonyl fluoride (202g, 2mol), seal the system, slowly warm up to room temperature, stir and react for 12h, add saturated brine (500mL) to wash after the reaction, the organic phase is concentrated under reduced pressure to distill dichloromethane (recycling), and the crude product is purified under reduced pressure. Distillation to obtain white solid N-acetyl 4-fluoroaniline (142g), N-acetyl 4-fluoroaniline was added to 2mol / L hydrochloric acid (500mL), heated to reflux for 12h, after the TLC detection reaction was completed, add Adjust the pH to alkaline (8-10) with NaOH (5mol / L), add the organic solvent dichloromethane (500mL) for extraction, wash the organic phase with saturated brine, dry over anhydrous sodium sulfate, and recover the solvent by distillation under reduced pressure. Distilled under reduced...

Embodiment 2

[0049] Add N-pivaloylphenylhydroxylamine (19.3g, 0.1mol), KF (2.9g, 0.05mol) and dichloromethane (200mL) into a stirred 500mL reaction flask in turn, cool to 0°C, and pass through Acyl fluoride (20g, 0.2mol), sealed system, slowly warming up to room temperature, stirring and reacting for 12h, adding saturated brine (50mL) to wash after the reaction, concentrating the organic phase under reduced pressure and distilling dichloromethane, the crude product was subjected to vacuum distillation , to obtain N-pivaloyl 4-fluoroaniline (18.5g), N-pivaloyl 4-fluoroaniline was added to 2mol / L hydrochloric acid (100mL), heated to reflux for 12h, after the reaction was detected by TLC, added Adjust the pH to alkaline (8-10) with NaOH (5mol / L), add the organic solvent dichloromethane (100mL) for extraction, wash the organic phase with saturated brine, dry over anhydrous sodium sulfate, recover the solvent by distillation under reduced pressure, and carry out the crude product Distillation u...

Embodiment 3

[0051] Add N-Boc-phenylhydroxylamine (2.09g, 0.01mol), KF (0.29g, 0.005mol) and dichloromethane (20mL) into a stirred 50mL reaction flask in turn, cool to 0°C, and pass through sulfonyl Fluorine (2g, 0.02mol), sealed system, slowly warming up to room temperature, stirring and reacting for 12h, adding saturated brine (25mL) to wash after the reaction, concentrating the organic phase under reduced pressure and distilling dichloromethane, the crude product was subjected to vacuum distillation, To obtain N-Boc-4-fluoroaniline (2.05g), N-Boc-4-fluoroaniline was added to 2mol / L hydrochloric acid (100mL), and reacted at room temperature for 2h. After the reaction was detected by TLC, NaOH (5mol / L L) adjust the pH to alkaline (8-10), add an organic solvent dichloromethane (100mL) for extraction, wash the organic phase with saturated brine, dry over anhydrous sodium sulfate, recover the solvent by distillation under reduced pressure, and carry out column chromatography on the crude prod...

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Abstract

The invention discloses a synthesis method of a 4-fluorine substituted arylamine compound, which comprises the following steps: 1) taking phenyl hydroxylamine protected by acyl as a substrate, taking sulfonyl fluoride as a fluorine source in a polar solvent, and generating a 4-fluorine substituted aniline compound under an alkaline condition; and 2) removing a protecting group under a dilute acid condition or Pd catalytic hydrogenation to obtain the 4-fluorine substituted arylamine compound. According to the 4-fluorine substituted aniline compound synthesized by the invention, the lipophilicity is greatly improved due to introduction of fluorine atoms, so that the 4-fluorine substituted aniline compound can be widely applied to preparation of fluorine-containing drugs, pesticides and dye intermediates; meanwhile, the adopted raw materials are all industrial products, are low in price and easy to obtain, and are commercially available; the 4-fluoroarylaniline prepared by the method is high in yield, and a product with the purity being greater than or equal to 99% can be obtained with the yield being greater than 90%; and the method is simple to operate, low in cost, very suitable for industrialization and capable of being widely popularized and used.

Description

technical field [0001] The invention belongs to the technical field of fine chemical industry, relates to the technical field of organic synthesis, in particular to a 4-fluoro substituted arylamine compound and a synthesis method thereof. Background technique [0002] Since fluorine is the most electronegative element, the introduction of fluorine atoms makes fluorine-containing organic compounds have unique physical properties, chemical properties and physiological activities, and makes fluorine-containing organic compounds have chemical stability, surface activity and excellent properties. Features such as temperature resistance. Therefore, fluorine-containing compounds have been widely and deeply researched and applied in many cutting-edge technologies and major industrial projects, as well as in pharmaceuticals, pesticides and other industries. [0003] The p-fluorine-substituted arylanilines are widely found in many drugs and pesticide molecules, and can also be transf...

Claims

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Application Information

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IPC IPC(8): C07C209/62C07C211/52C07C213/02C07C217/84C07C319/20C07C323/36C07C315/04C07C317/36
CPCC07C209/62C07C211/52C07C231/10C07C269/06C07C213/02C07C217/84C07C319/20C07C323/36C07C315/04C07C317/36C07C233/15C07C271/28C07C233/25C07C233/43C07C323/41C07C317/40Y02P20/55
Inventor 刘文娟刘智慧崔志鹏崔晓雷田瑞芳
Owner 江苏笃行致远新材料科技有限公司
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