N-acylated trifluoro-methylseleno bifunctionalization method for indole derivative

A technology of indole derivatives and acylated trifluoromethane, which is applied in the direction of organic chemistry, can solve the problems of application limitations, high toxicity, and corrosiveness, and achieve the effects of simple operation, mild conditions, and easy-to-obtain raw materials

Inactive Publication Date: 2019-10-25
WUHAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

These methods all involve trifluoromethylselenyl chloride, and trifluoromethylselenyl chloride is a highly toxic and corrosive gas, so its application is greatly restricted
[0004] Compared with trifluoromethaneselenoyl chloride, trifluoromethaneselenoammonium salt or metal salt ([M][SeCF 3 ]) high stability, easier to store, easy to synthesize and use, and so far, the use of nucleophilic trifluoromethyl selenide reagent [M][SeCF 3 ] to achieve difunctionalization has hardly been reported

Method used

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  • N-acylated trifluoro-methylseleno bifunctionalization method for indole derivative
  • N-acylated trifluoro-methylseleno bifunctionalization method for indole derivative
  • N-acylated trifluoro-methylseleno bifunctionalization method for indole derivative

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050] Under nitrogen protection, the [Me 4 N][SeCF 3 ] (133mg, 0.6mmol) and the oxidant 3,3'-dichlorobenzoyl peroxide (137mg, 0.44mmol) were dissolved in 1mL of acetonitrile, and 1mL of indole (23.4mg, 0.2mmol) was added dropwise at 25°C acetonitrile solution, and reacted at 25°C for 16 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 (20:1) were used as eluents to obtain the acylated trifluoromethylselenide product by column chromatography: N- m-Chlorobenzoyl-3-trifluoromethaneselenoindole (yellow solid 56.3 mg, yield 70%), 1 H NMR (500MHz, CDCl 3 )δ8.38(d, J=7.1Hz, 1H), 7.77-7.75(m, 2H), 7.66-7.62(m, 3H), 7.52(t, J=7.8Hz, 1H), 7.50-7.45(m ,2H); 19 FNMR (471MHz, CDCl 3 )δ-35.9(s,3F).

Embodiment 2

[0052] Under nitrogen protection, the AgSeCF 3 (38mg, 0.6mmol) and the oxidizing agent 3,3'-dichlorobenzoyl peroxide (124mg, 0.4mmol) were dissolved in 1mL of acetonitrile, cooled to -40°C and 1mL of 2-methylindole (26.2mg , 0.2 mmol) in acetonitrile solution, and reacted at -40°C for 48 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 (20:1) were used as eluents to obtain the acylated trifluoromethylselenide product by column chromatography: N- m-chlorobenzoyl-2-methyl-3-trifluoromethylselenoindole (yellow solid 25.8 mg, yield 31%), 1 H NMR (500MHz, CDCl 3 )δ7.77(t, J=1.7Hz,1H),7.70(d,J=7.9,1H),7.67-7.64(dm,J=7.9,1H),7.60-7.58(dt,J=7.8,1.2 ,1H),7.46(t,J=7.9,1H),7.29(t,J=7.8,1H),7.15(t,J=7.2,1H),7.00(d,J=8.4,1H),2.65( s,3H); 19 F NMR (471MHz, CDCl 3 )δ-35.9(s,3F).

Embodiment 3

[0054] Under nitrogen protection, the [Et 4 N][SeCF 3 ] (168mg, 0.6mmol) and the oxidant 3,3'-dichlorobenzoyl peroxide (124mg, 0.4mmol) were dissolved in 1mL DMF, and 1mL 4-fluoroindole (27.0mg, 0.2 mmol) in DMF and reacted at 25°C 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 (20:1) were used as eluents to obtain the acylated trifluoromethylselenide product by column chromatography: N- m-chlorobenzoyl-3-trifluoromethylselenyl-4-fluoroindole (yellow solid 43.1mg, yield 51%), 1 H NMR (500MHz, CDCl 3 )δ8.20(d, J=8.4Hz,1H),7.76(t,J=1.8,1H),7.67-7.65(dm,J=8.0,1H),7.63-7.61(dt,J=7.7,1.3 ,1H),7.55(s,1H),7.53(t,J=7.9,1H),7.43-7.39(m,1H),7.12-7.08(m,1H); 19 F NMR (471MHz, CDCl 3 ) δ-36.8(s, 3F), δ-123.7(m, 1F).

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Abstract

The invention discloses an N-acylated trifluoro-methylseleno bifunctionalization method for an indole derivative. The method comprises the following steps: dissolving a trifluoro-methylseleno ammoniumsalt or a metal salt and an oxidant into a solvent, adding an indole derivative one droplet by one droplet, performing a stirring reaction, adding water for quenching after the reaction is completed,and performing column chromatography, so as to obtain an N-acylated trifluoro-methylseleno product, wherein the oxidant is peroxy-acyl. The method provided by the invention is simple and convenient to operate, gentle in condition, easy in raw material obtaining and high in product yield, in addition, the trifluoro-methylseleno ammonium salt or the mtal salt with nucleophilicity is adopted as a trifluoro-methylseleno source, and N-acylated trifluoro-methylseleno bifunctionalization of electron-rich aromatic hydrocarbon (the indole derivative) is achieved for a first time.

Description

technical field [0001] The invention relates to organic synthesis, in particular to a method for N-acylated trifluoromethylselenyl difunctionalization of indole derivatives. Background technique [0002] Due to their unique properties, fluorine-containing organic compounds have great application value in the fields of medicine and pesticides, and have attracted widespread attention from chemists. Selenium is an essential trace element and has recently been found to be effective in the prevention and treatment of prostate and colorectal cancers. The trifluoromethylselenyl functional group formed by the connection of trifluoromethyl and selenium has unique stereoelectronic effect and fat solubility. It can be introduced into small organic molecules to adjust the physical and chemical properties of the target molecule, or further change the biological activity of the target molecule , making it possible for selenium supplementation products or anticancer drugs. [0003] In 20...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D209/30
CPCC07D209/30
Inventor 张成潘谭凯丽韩秋燕施进
Owner WUHAN UNIV OF TECH
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