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

An acetoxy and 10-technology, applied in the field of copper photocatalytic synthesis of 9-acetoxy-9,10-dihydrophenanthrene compounds, can solve the problem that raw materials are not so easy to obtain, unfavorable for industrial production, large environmental impact, etc. problems, to achieve the effects of good substrate adaptability, reduced energy consumption, and low operational risk

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 dihydrophenanthrene compounds were synthesized by free radical addition and cyclization at a high temperature of 160 ° C. However, this synthesis method has great limitations and needs to be carried out under high temperature conditions. At the same time, the use of pyridine, a more toxic solvent, has a greater impact on the environment and is not conducive to industrial production
There are relatively many reports on the synthesis of dihydrophenanthrene compounds, but there are significantly fewer reports on the synthesis of dihydrophenanthrene compounds substituted at the 9th position, while the traditional synthesis of 9-acetoxy-9,10-dihydrophenanthrene compounds Generally, 9-hydroxy-9,10-dihydrophenanthrene and acetic anhydride are used as substrates, and pyridine is used as a solvent to form a reaction by heating. This method also uses unfriendly solvent pyridine, and it is necessary to prepare 9-hydroxy-9 in advance. 10-Dihydrophenanthrene, the raw material is not so easy to get

Method used

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

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Embodiment 1

[0031]

[0032] α-Acetoxy-2-phenylstyrene (0.3mmol, 0.0714g), photosensitizer (III) (0.015mmol, 0.0167g), K 3 PO 4 (0.45mmol, 0.0954g) was added to a 15mL sealed reaction tube, and then 3mL 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 and the yield was 87%.

[0033] Characterization data: 1 H NMR (500MHz, CDCl 3 )δ7.86(t, J=5.5Hz, 2H), 7.50(d, J=7.5Hz, 1H), 7.48-7.45(m, 1H), 7.39-7.37(m, 1H), 7.36-7.33(m ,1H),7.32-7.29(m,1H),6.09(t,J=5Hz,1H),3.23-3.16(m,2H),2.00(s,3H). 13 C NMR (125MHz, CDCl 3 )δ170.82, 135.94, 134.50, 134.32, 134.22, ...

Embodiment 2

[0035]

[0036] α-Acetoxy-2-phenylstyrene (0.3mmol, 0.0714g), photosensitizer (IV) (0.015mmol, 0.0172g), K 3 PO 4 (0.45mmol, 0.0954g) was added to a 15mL sealed reaction tube, and then 3mL 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, 77% yield.

[0037] Characterization data: 1 H NMR (500MHz, CDCl 3 )δ7.86(t, J=5.5Hz, 2H), 7.50(d, J=7.5Hz, 1H), 7.48-7.45(m, 1H), 7.39-7.37(m, 1H), 7.36-7.33(m ,1H),7.32-7.29(m,1H),6.09(t,J=5Hz,1H),3.23-3.16(m,2H),2.00(s,3H). 13 C NMR (125MHz, CDCl 3 )δ170.82, 135.94, 134.50, 134.32, 1...

Embodiment 3

[0039]

[0040] α-Acetoxy-2-phenylstyrene (0.3mmol, 0.0714g), photosensitizer (III) (0.015mmol, 0.0167g), K 3 PO 4(0.3mmol, 0.0636g) was added to a 15mL sealed reaction tube, and then 3mL 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, 67% yield.

[0041] Characterization data: 1 H NMR (500MHz, CDCl 3 )δ7.86(t, J=5.5Hz, 2H), 7.50(d, J=7.5Hz, 1H), 7.48-7.45(m, 1H), 7.39-7.37(m, 1H), 7.36-7.33(m ,1H),7.32-7.29(m,1H),6.09(t,J=5Hz,1H),3.23-3.16(m,2H),2.00(s,3H). 13 C NMR (125MHz, CDCl 3 )δ170.82, 135.94, 134.50, 134.32, 13...

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Abstract

A method for copper photocatalytic synthesis of 9-acetoxy-9,10-dihydrophenanthrene compounds, the method is as follows: substrate (I), photosensitizer, basic substance, solvent are mixed, and the blue LED Under the conditions of light irradiation, temperature 15-40°C, and inert gas protection, react for 20-36 hours, and then the reaction solution is post-treated to obtain 9-acetoxy-9,10-dihydrophenanthrene compounds (II); the invention is safe and environmentally friendly , no exhaust gas, low risk of operation; good substrate adaptability, various substituents can achieve cyclization; mild reaction conditions; at the same time, the reaction has a certain degree of innovation, high atom economy, using photocatalysis To replace the traditional heating mode, which 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-acetoxy-9,10-dihydrophenanthrene compounds by copper photocatalysis. (2) Background technology [0002] Dihydrophenanthrene compounds, also known as 9,10-dihydrophenanthrene compounds, widely exist in nature, and traces of such compounds can be found in many Chinese herbal medicines. Due to its special structure, it has unique application value in industry. At the same time, as an important pharmaceutical intermediate, dihydrophenanthrene compounds can effectively inhibit the production of inflammatory factors and can synthesize a series of anticancer drugs. It is the main framework of many anticancer drugs. In addition, substituted dihydrophenanthrenes have one or two chiral centers, and a series of chiral ligands can be designed and synthesized. For example, in 2002, Zeng et al reported the design, synthesis and application of a series of chiral ligands derived from 9,10-dihydrophenanthrene-9...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C67/293C07C69/157B01J31/24C07C1/20C07C15/30C07C17/35C07C25/22
CPCC07C67/293B01J31/2457C07C1/20C07C17/35C07C2603/26B01J2531/16B01J2231/324B01J35/39C07C69/157C07C15/30C07C25/22
Inventor 刘运奎郑立孟周丙伟
Owner ZHEJIANG UNIV OF TECH