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Trifluoromethylselenolation method of electron-rich arene or aza-arene

A technology for electron-rich aromatic hydrocarbons and trifluoromethanes, which is applied in the field of trifluoromethylselenylation of electron-rich aromatic hydrocarbons or aromatic heterohydrocarbons, can solve problems such as corrosiveness and high toxicity, and achieves good functional group tolerance and easy operation. , the effect of cheap and easy-to-obtain raw materials

Active Publication Date: 2018-12-21
WUHAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, trifluoromethylselenyl chloride is a highly toxic and corrosive gas, which limits the application of this method.

Method used

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  • Trifluoromethylselenolation method of electron-rich arene or aza-arene
  • Trifluoromethylselenolation method of electron-rich arene or aza-arene
  • Trifluoromethylselenolation method of electron-rich arene or aza-arene

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Under nitrogen protection, the [Me 4 N][SeCF 3 ] (67mg, 0.3mmol) and the oxidant m-CPBA (45mg, 85%, 0.22mmol) were dissolved in 1mL acetonitrile, cooled to 0°C, and then 1mL of indole (23.4mg, 0.2mmol) in acetonitrile was added dropwise, And react at 0° C. for 8 hours. After the reaction was completed, two drops of water were dropped to quench, and then the solvent was removed by rotary evaporation, and petroleum ether and ethyl acetate (10:1) were used as eluents to obtain trifluoromethylselenide product: 3-trifluoromethyl selenide by column chromatography Methylselenoindole (brown solid 49.3mg, yield 93%), 1 H NMR (500MHz, CDCl 3 )δ8.49(brs,1H),7.81-7.79(m,1H),7.51(d,J=2.7Hz,1H),7.45-7.43(m,1H),7.31(m,2H); 19 F NMR (471MHz, CDCl 3 )δ-35.9(s,3F); 13 CNMR (126MHz, CDCl 3)δ136.1, 132.9, 130.0, 123.4, 122.3 (q, J = 335.4Hz), 121.5, 120.1, 111.5, 93.3 (q, J = 1.5Hz).

Embodiment 2

[0032] Under nitrogen protection, the AgSeCF 3 (77mg, 0.3mmol) and oxidant m-CPBA (45mg, 85%, 0.22mmol) were dissolved in 1mL of acetonitrile, cooled to 0 ° C, and then added dropwise to 1mL of 2-methylindole (26.2mg, 0.2mmol) acetonitrile solution, and reacted at 0°C for 8 hours. After the reaction was completed, two drops of water were dropped to quench, and then the solvent was removed by rotary evaporation, and petroleum ether and ethyl acetate (10:1) were used as eluents to obtain trifluoromethylselenide product: 3-trifluoromethyl selenide by column chromatography Methylselenyl-2-methylindole (white solid 54.1mg, yield 97%), 1 HNMR (500MHz, CDCl 3 )δ8.30(brs,1H),7.70-7.69(m,1H),7.33-7.31(m,1H),7.25-7.22(m,2H),2.60(s,3H); 19 F NMR (471MHz, CDCl 3 )δ-37.4(s,3F); 13 C NMR (126MHz, CDCl 3 )δ142.8, 135.5, 131.3, 122.7 (q, J = 336.1Hz), 122.6, 121.2, 119.5, 110.7, 91.7 (q, J = 1.1Hz), 13.0.

Embodiment 3

[0034] Under nitrogen protection, the CuSeCF 3 (63mg, 0.3mmol) and oxidant m-CPBA (45mg, 85%, 0.22mmol) were dissolved in 1mL of acetonitrile, then 1mL of 4-fluoroindole (27.0mg, 0.2mmol) in acetonitrile was added dropwise, and at 80°C Under reaction for 24 hours. After the reaction was completed, two drops of water were dropped to quench, and then the solvent was removed by rotary evaporation, and petroleum ether and ethyl acetate (10:1) were used as eluents to obtain trifluoromethylselenide product: 3-trifluoromethyl selenide by column chromatography Methylselenyl-4-fluoroindole (white solid 50.2mg, yield 89%). 1 H NMR (500MHz, CDCl 3 )δ8.67(brs,1H),7.47(s,1H),7.24-7.21(m,2H),6.93-6.89(m,1H); 19 F NMR (471MHz, CDCl 3 )δ-38.5(d,J=3.3Hz,3F),-124.7(m,1F); 13 CNMR (126MHz, CDCl 3 )δ156.8(d, J=250.7Hz), 139.0(d, J=9.5Hz), 133.7, 123.9(d, J=7.9Hz), 122.1(q, J=335.4Hz), 118.5(d, J =18.1Hz), 107.8(d, J=3.8Hz), 106.9(d, J=19.1Hz), 89.3(q, J=2.3Hz).

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Abstract

The invention discloses a trifluoromethylselenolation method of electron-rich arene or aza-arene. The method comprises the following steps: adding trifluoromethylseleno ammonium salt or metal salt andan oxidizing agent into a solvent; adding electron-rich arene or aza-arene at -80 to 100 DEG C; stirring and reacting for 0.1-48h; adding water for quenching; performing column chromatography to obtain a trifluoromethylselenolation product. By adopting trifluoromethylseleno ammonium salt or metal salt as a trifluoromethylseleno source, the invention proposes a new trifluoromethylselenolation method of electron-rich arene or aza-arene, wherein oxidation trifluoromethylselenolation of electron-rich arene or aza-arene is realized in quite mild conditions, and a C-SeCF3 bond is directly constructed from aC-H bond; the method has the advantages of easiness in operation, mild conditions, relatively high yield, perfect tolerance of functional group and cheap and easily available raw materials.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a trifluoromethylselenylation method of electron-rich aromatic hydrocarbons or aromatic heterohydrocarbons. Background technique [0002] Fluorine-containing organic compounds have great application research value in the fields of medicine, pesticides and materials due to their unique properties. Introducing fluorine atoms or fluorine-containing groups into the molecular structure of drugs is one of the most effective methods to change the biological activity of parent drugs. Therefore, the method of constructing fluorine-containing compounds has attracted extensive attention from chemists. The -SeCF 3 Introducing it into the substrate can make it a potential more effective selenium supplement product or a new type of anticancer drug. At present, the methods for introducing trifluoromethylselenyl into organic molecules are mainly divided into two categories...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D209/30C07D495/04C07D249/10C07D233/90C07D207/44C07D317/62C07C391/02
CPCC07C391/02C07D207/44C07D209/30C07D233/90C07D249/10C07D317/62C07D495/04
Inventor 张成潘韩周洲董涛施进
Owner WUHAN UNIV OF TECH
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