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Method for synthesizing 9-trifluoromethyl-9,10-dihydrophenanthrene compound through copper photocatalysis

A technology of trifluoromethyl and 10-, which is applied in the field of synthesizing 9-trifluoromethyl-9,10-dihydrophenanthrene compounds, can solve the problems of unfavorable industrial production and large environmental impact, and achieve substrate adaptation Good performance, low operation risk, and mild reaction conditions

Active Publication Date: 2021-03-05
ZHEJIANG UNIV OF TECH
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  • Abstract
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  • Application Information

AI Technical Summary

Problems solved by technology

[0006] At present, there are many methods for synthesizing dihydrophenanthrene compounds. For example, in 2011, Daniela et al. reported (Org.Lett., 2011, 13, 12) to use 2-phenylethyl iodobenzene as a substrate and potassium tert-butoxide as a base , pyridine was used as a solvent, and the dihydrophenanthrene compound (scheme 1) was synthesized by free radical addition and cyclization under the high temperature condition of microwave at 160°C. However, this synthesis method has great limitations and needs to be It is carried out under high temperature conditions. At the same time, the use of pyridine, a highly toxic solvent, has a great impact on the environment and is not conducive to industrial production.

Method used

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  • Method for synthesizing 9-trifluoromethyl-9,10-dihydrophenanthrene compound through copper photocatalysis
  • Method for synthesizing 9-trifluoromethyl-9,10-dihydrophenanthrene compound through copper photocatalysis
  • Method for synthesizing 9-trifluoromethyl-9,10-dihydrophenanthrene compound through copper photocatalysis

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036]

[0037] Add α-trifluoromethyl-2-phenylstyrene (0.3mmol, 0.0744g), photosensitizer (III) (0.015mmol, 0.0167g), potassium phosphate (0.45mmol, 0.0954g) to 15mL lock reaction In the tube, 3 mL of tetrahydrofuran was added as a solvent. Then, under the irradiation of 15w Blue LED, react at 25°C and nitrogen atmosphere for 24h. After the reaction, add two spoons (0.5g) of column chromatography silica gel (100-200 mesh) to the reaction solution, and pass the decompression The solvent was distilled off, and the pure product shown in the structural formula was obtained by column chromatography (using petroleum ether / ethyl acetate=20:1 as eluent). The material was a yellow liquid, 77% yield.

[0038] Characterization data: 1 H NMR (500MHz, CDCl 3 )δ7.84(d, J=7Hz, 1H), 7.77(d, J=8Hz, 1H), 7.43(td, J 1 =7.6Hz,J 2 =1.4Hz,1H),7.37(d,J=7.4Hz,1H),7.34–7.28(m,2H),7.28–7.22(m,2H),3.61-3.54(m,1H),3.27(dd, J 1 =16.2,J 2 =6.5Hz,1H),3.20(dd,J 1 =16.2Hz,J 2 =3.2Hz,1H). 13 C NM...

Embodiment 2

[0040]

[0041] Add α-trifluoromethyl-2-phenylstyrene (0.3mmol, 0.0744g), photosensitizer (IV) (0.015mmol, 0.0172g), potassium phosphate (0.45mmol, 0.0954g) to 15mL lock reaction In the tube, 3 mL of tetrahydrofuran was added as a solvent. Then, under the irradiation of 15w Blue LED, under the condition of 25 ℃, under nitrogen atmosphere, react for 24h. After the reaction, add two tablespoons of column chromatography silica gel (100-200 mesh) to the reaction liquid, and remove the solvent by distillation under reduced pressure. The pure product shown in the structural formula was obtained by column chromatography (petroleum ether / ethyl acetate = 20:1 as eluent). The material was a yellow liquid and the yield was 67%.

[0042] Characterization data: 1 H NMR (500MHz, CDCl 3 )δ7.84(d, J=7Hz, 1H), 7.77(d, J=8Hz, 1H), 7.43(td, J 1 =7.6Hz,J 2 =1.4Hz,1H),7.37(d,J=7.4Hz,1H),7.34–7.28(m,2H),7.28–7.22(m,2H),3.61-3.54(m,1H),3.27(dd, J 1 =16.2,J 2 =6.5Hz,1H),3.20(dd,J 1 =16.2H...

Embodiment 3

[0044]

[0045] Add α-trifluoromethyl-2-phenylstyrene (0.3mmol, 0.0744g), photosensitizer (III) (0.003mmol, 0.0034g), potassium phosphate (0.45mmol, 0.0954g) to 15mL lock reaction In the tube, 3 mL of tetrahydrofuran was added as a solvent. Then, under the irradiation of 15w Blue LED, under the condition of 25°C, under nitrogen atmosphere, react for 24h. After the reaction, add two spoonfuls of column chromatography silica gel (100-200 mesh) to the reaction solution, and remove the solvent by distillation under reduced pressure. The pure product shown in the structural formula was obtained by column chromatography (petroleum ether / ethyl acetate = 20:1 as eluent). The material was a yellow liquid, 51% yield.

[0046] Characterization data: 1 H NMR (500MHz, CDCl 3 )δ7.84(d, J=7Hz, 1H), 7.77(d, J=8Hz, 1H), 7.43(td, J 1 =7.6Hz,J 2 =1.4Hz,1H),7.37(d,J=7.4Hz,1H),7.34–7.28(m,2H),7.28–7.22(m,2H),3.61-3.54(m,1H),3.27(dd, J 1 =16.2,J 2 =6.5Hz,1H),3.20(dd,J 1 =16.2Hz,J 2 =3....

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Abstract

The invention relates to a method for synthesizing a 9-trifluoromethyl-9,10-dihydrophenanthrene compound by copper photocatalysis. The method comprises the following steps: mixing a substrate (I), a photosensitizer, an alkaline substance and a solvent, performing reacting for 20-36 hours under the conditions of blue LED illumination, temperature of 15-40 DEG C and inert gas protection, and carrying out aftertreatment on a reaction solution to obtain a 9-trifluoromethyl-9,10-dihydrophenanthrene compound (II). The method is safe, environmentally friendly, free of waste gas and low in operation risk; the substrate adaptability is good, and cyclization of various substituent groups can be realized; reaction conditions are mild; and meanwhile, the reaction has certain innovativeness and high atom economy, a traditional heating mode is replaced with a photocatalysis mode, energy consumption is reduced, and the concept of modern green chemistry is better met.

Description

[0001] (1) Technical field [0002] The invention relates to a method for synthesizing 9-trifluoromethyl-9,10-dihydrophenanthrene compounds. [0003] (2) Background technology [0004] As the name suggests, fluorine-containing compounds are so-called compounds containing fluorine element. The research on fluorine-containing compounds has always been a huge field, which may involve various fields of society. Since the introduction of fluorine atoms will greatly change the steric, electrical, and lipophilic properties of the compound, fluorine-containing compounds play a vital role in pharmaceutical, veterinary, agrochemical, and material chemistry. Therefore, in the process of drug development, drug researchers often introduce one or more fluorine atoms to improve the activity of the drug. It is precisely because of the uniqueness of fluorine that researchers have devoted themselves to the study of fluorine-containing compounds, setting off a frenzy of research on organic fluor...

Claims

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Application Information

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IPC IPC(8): C07C17/358C07C41/18C07C23/44C07C25/22C07C43/225C07B35/08
CPCC07C17/358C07C41/18C07B35/08C07C2603/26C07C23/44C07C25/22C07C43/225
Inventor 刘运奎郑立孟周丙伟
Owner ZHEJIANG UNIV OF TECH
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