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A method for copper photocatalytic synthesis of 9-trifluoromethyl-9,10-dihydrophenanthrene compounds

A technology of trifluoromethyl and 10-, which is applied in the field of synthesizing 9-trifluoromethyl-9,10-dihydrophenanthrene compounds, can solve problems such as unfavorable industrial production and large environmental impact, and achieve substrate adaptation. The effect of good performance, low operational risk, and high atomic economy

Active Publication Date: 2022-03-18
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] 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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  • A method for copper photocatalytic synthesis of 9-trifluoromethyl-9,10-dihydrophenanthrene compounds
  • A method for copper photocatalytic synthesis of 9-trifluoromethyl-9,10-dihydrophenanthrene compounds
  • A method for copper photocatalytic synthesis of 9-trifluoromethyl-9,10-dihydrophenanthrene compounds

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032]

[0033] 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 liquid, 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.

[0034] 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 NMR ...

Embodiment 2

[0036]

[0037] 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°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, 67% 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 =3.2...

Embodiment 3

[0040]

[0041] 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.

[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 =16.2Hz,J 2 =3.2H...

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Abstract

A method for copper photocatalytic synthesis of 9-trifluoromethyl-9,10-dihydrophenanthrene compounds, the method is as follows: substrate (I), photosensitizer, basic substance, solvent are mixed, and in blue LED illumination, temperature 15-40°C, reaction under the conditions of inert gas protection for 20-36h, and then the reaction solution is post-treated to obtain 9-trifluoromethyl-9,10-dihydrophenanthrene compound (II); the present invention It is safe and environmentally friendly, does not generate waste gas, and has low risk of operation; the substrate has good adaptability, and various substituents can be cyclized; the reaction conditions are mild; at the same time, the reaction has certain innovation, high atom economy, and photocatalysis The way to replace the traditional heating mode reduces energy consumption and is more in line with the concept of modern green chemistry;

Description

(1) Technical field [0001] The invention relates to a method for synthesizing 9-trifluoromethyl-9,10-dihydrophenanthrene compounds. (2) Background technology [0002] 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, pesticide chemistry, 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 fluorides. ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
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