Electrochemical synthesis method of trifluoromethylated aryl amide derivative

A technology of trifluoromethylated arylamide and fluoromethylated arylamide, which is applied in the field of electrochemical synthesis of trifluoromethylated arylamide derivatives, can solve the problems of non-compliance with green chemistry, and reach the bottom line wide applicability, mild reaction conditions and high product yield

Active Publication Date: 2020-09-22
ZHEJIANG UNIV OF TECH
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  • Abstract
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AI Technical Summary

Problems solved by technology

However, these methods may use toxic and harmful reagents, a large number of oxidants and metal catalysts, which do not meet the requirements of green chemistry

Method used

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  • Electrochemical synthesis method of trifluoromethylated aryl amide derivative
  • Electrochemical synthesis method of trifluoromethylated aryl amide derivative
  • Electrochemical synthesis method of trifluoromethylated aryl amide derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027]

[0028] In a 10mL three-neck flask equipped with a carbon anode (d=6mm) and a platinum plate (1cm x 1cm) cathode, add N-phenylpyridinamide (0.3mmol, 59.5mg), sodium trifluoromethylsulfinate (0.45mmol , 70.2mg), tetrabutylammonium bromide (0.3eq, 29.0mg). Acetonitrile (3.0 mL) was added. The reaction mixture was stirred at 50° C. for 120 min at a constant current of 15 mA. After the reaction, TLC detection, the reaction mixture was concentrated under reduced pressure. Purification was carried out by silica gel column chromatography to obtain 54.3 mg of the target product a as a white solid, with a yield of 68%.

[0029] 1 H NMR (400MHz, CDCl 3 )δ10.60(s,1H),8.60(d,J=4.7Hz,1H),8.53(d,J=8.3Hz,1H),8.24(d,J=7.8Hz,1H),7.86(td, J=7.7,1.7Hz,1H),7.61(d,J=7.7Hz,1H),7.55(t,J=7.7Hz,1H),7.44(ddd,J=7.6,4.8,1.1Hz,1H), 7.18(d,J=7.7Hz,1H). 13 C NMR (100MHz, CDCl 3 )δ161.18, 148.09, 147.08, 136.42, 134.28 (q, J=2.5Hz), 131.69, 126.15 (q, J=5.0Hz), 125.48, 123.98 (q, J=273.4Hz...

Embodiment 2

[0031]

[0032] In a 10mL three-neck flask equipped with a carbon anode (d=6mm) and a platinum plate (1cm x 1cm) cathode, add N-(p-tolyl)pyridinamide (0.3mmol, 63.7mg), sodium trifluoromethylsulfinate (0.45mmol, 70.2mg), tetrabutylammonium bromide (0.3eq, 29.0mg). Acetonitrile (3.0 mL) was added. The reaction mixture was stirred at 50° C. for 120 min at a constant current of 15 mA. After the reaction, TLC detection, the reaction mixture was concentrated under reduced pressure. Purification was carried out by silica gel column chromatography to obtain 54.6 mg of the target product b as a white solid, with a yield of 65%.

[0033] 1 H NMR (400MHz, CDCl 3 )δ10.57(s,1H),8.68(d,J=4.4Hz,1H),8.43(d,J=8.4Hz,1H),8.31(d,J=7.8Hz,1H),7.93(td, J=7.7,1.7Hz,1H),7.52(ddd,J=7.6,4.8,1.1Hz,1H),7.48(s,1H),7.43(d,J=8.4Hz,1H),2.42(s,3H ). 13 C NMR (100MHz, CDCl 3)δ162.36, 149.46, 148.29, 137.66, 134.09, 133.41(q, J=1.3Hz),, 132.89(q, J=1.3Hz), 126.64, 126.55(q, J=5.0Hz), 124.43(q, J= 27...

Embodiment 3

[0035]

[0036] In a 10mL three-necked flask equipped with a carbon anode (d=6mm) and a platinum plate (1cm x 1cm) cathode, add N-(4-bromophenyl)pyridineamide (0.3mmol, 83.2mg), trifluoromethylsulfin Sodium Acetate (0.45mmol, 70.2mg), Tetrabutylammonium Bromide (0.3eq, 29.0mg). Acetonitrile (3.0 mL) was added. The reaction mixture was stirred at 50° C. for 120 min at a constant current of 15 mA. After the reaction, TLC detection, the reaction mixture was concentrated under reduced pressure. Purification was carried out by silica gel column chromatography to obtain 62.1 mg of the target product c as a white solid, with a yield of 60%.

[0037] 1 H NMR (400MHz, CDCl 3 )δ10.69(s,1H),8.67(d,J=4.2Hz,1H),8.57(d,J=8.9Hz,1H),8.29(d,J=7.8Hz,1H),7.93(td, J=7.7,1.6Hz,1H),7.79(d,J=1.9Hz,1H),7.73(d,J=8.9Hz,1H),7.53(ddd,J=7.6,4.8,1.1Hz,1H). 13 C NMR (101MHz, CDCl 3 )δ161.35, 148.05, 147.34, 136.72, 134.86, 133.75(q, J=1.0Hz), 130.14(q, J=5.0Hz), 125.87, 123.34, 122.18(q, J=274.2Hz...

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Abstract

The invention discloses an electrochemical synthesis method of a trifluoromethylated aryl amide derivative. The method comprises the steps: adding a substrate aryl amide, a trifluoromethylation reagent, an electrolyte and a solvent into a reaction container equipped with an electrode, carrying out a constant-current stirring reaction on the reaction mixture at the temperature of 25-75 DEG C for 30-180 min at a constant current of 5-20 mA, and carrying out post-treatment on the reaction solution to obtain the product trifluoromethylated aryl amide derivative. The structural formula of the substrate aryl amide is represented by a formula (Ia) or a formula (Ib), and correspondingly, the structural formula of the obtained product trifluoromethylated aryl amide derivative is represented by a formula (IIa) or a formula (IIb); the method is environment-friendly, simple, convenient and efficient; the structural formula of the substrate is described in the specification, the structural formulaof the product is described in the specification.

Description

technical field [0001] The invention relates to an electrochemical synthesis method of trifluoromethylated arylamide derivatives, belonging to the field of organic synthesis. Background technique [0002] The trifluoromethyl group has a significant effect on the lipophilicity, permeability, metabolic stability and other properties of the compound. Therefore, the efficient introduction of trifluoromethyl groups into pharmaceutical and agrochemical products, as well as functional organic materials, has become an important research field in the field of chemistry. Trifluoromethyl also exists in many drugs, which is the key structure for the construction of drugs and active intermediates, such as the drug Demigran (flumexidone acetate) for the treatment of migraine, the anti-AIDS drug Efavirenz (favirenz), the treatment Celebrex (celecoxib), a drug for arthritis, Januvia (sitagliptin), a drug for treating type II diabetes, and Trifluridine (trifluridine), an antiviral drug, all...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C25B3/08C07D213/81C07D215/40C07D409/12C25B3/28
CPCC07D213/81C07D215/40C07D409/12
Inventor 谢媛媛王凯侯加浩吕杨静
Owner ZHEJIANG UNIV OF TECH
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