Method for synthesizing benzofluorenone compound through photocatalysis

A technology for benzofluorenone and compounds, which is applied in the field of photocatalytic synthesis of benzofluorenone compounds, can solve the problems of high reaction temperature and poor functional group tolerance, and achieve mild reaction conditions, good substrate adaptability and high application prospects Effect

Active Publication Date: 2020-03-10
ZHEJIANG UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The traditional methods for the synthesis of benzofluorenones mainly include the oxidation reaction of benzofluorene, the Friedel-Crafts acylation reaction of aryl carboxylic acids and their derivatives, and the intramolecular Diels -Alder reaction, but these methods have various defects, such as the use of toxic or seriously polluting oxidants, high reaction temperature, poor tolerance of functional groups, etc.

Method used

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  • Method for synthesizing benzofluorenone compound through photocatalysis
  • Method for synthesizing benzofluorenone compound through photocatalysis
  • Method for synthesizing benzofluorenone compound through photocatalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034]

[0035] Add 0.3mmol of 1-(2-(phenylethynyl)phenyl)prop-2-en-1-one, 0.03mmol of copper photosensitizer (Ⅳ), and 0.9mmol of phenyltetrafluoroborate diazonium salt into a 15mL thick In a pressure-resistant reaction tube with a wall, under the irradiation of 15W blue LED light, react in 3mL solvent ethanol at 40°C for 2 hours. After cooling to room temperature, add two spoons (0.5 g, the same below) column chromatography silica gel (100-200 mesh) to the reaction solution, and remove the solvent by distillation under reduced pressure, and then obtain the structural formula (III- 1) The pure product shown (petroleum ether / ethyl acetate = 20:1 as eluent). The material was a yellow solid, 68% yield.

[0036] 1 H NMR (500MHz, CDCl3): δ = 8.26 (s, 1H), 7.97 (dd, J = 7.5, J = 1.5Hz, 1H), 7.76 (dd, J = 6.5, J = 0.9Hz, 1H), 7.65 –7.60(m,3H),7.51–7.42(m,5H),7.26–7.19(m,2H),6.35(d,J=7.5Hz,1H)ppm. 13 C NMR (125MHz, CDCl3): δ=193.2, 145.2, 137.4, 136.9, 136.5, 135.3, 134.70, 134...

Embodiment 2

[0038]

[0039] Add 0.3mmol 1-(2-(phenylethynyl)phenyl)prop-2-en-1-one, 0.03mmol copper photosensitizer (Ⅴ), and 0.9mmol p-methylphenyltetrafluoroborate diazonium salt Put it into a 15mL thick-walled pressure-resistant reaction tube, and react in 3mL solvent ethanol at 40°C for 2 hours under the irradiation of 15W blue LED light. After being cooled to room temperature, two spoons of column chromatography silica gel (100-200 mesh) were added to the reaction solution, and the solvent was removed by distillation under reduced pressure, and the pure product as shown in structural formula (III-2) was obtained by column chromatography separation. product (petroleum ether / ethyl acetate = 20:1 as eluent). The material was a yellow solid, 60% yield.

[0040] 1 H NMR (500MHz, CDCl3): δ = 8.21 (s, 1H), 7.85 (d, J = 8.5Hz, 1H), 7.74 (dd, J = 6.5, J = 1.0Hz, 1H), 7.65–7.61 (m ,3H),7.43–7.40(m,2H),7.32(dd,J=8.0,J=1.5Hz,1H),7.23–7.17 (m,3H),6.29(d,J=7.5Hz,1H), 2.40(s,3H)ppm. 13 C NMR...

Embodiment 3

[0042]

[0043] Add 0.3mmol 1-(2-(phenylethynyl)phenyl)prop-2-en-1-one, 0.015mmol copper photosensitizer (Ⅳ), and 0.9mmol p-chlorophenyltetrafluoroborate diazonium salt to In a 15mL thick-walled pressure-resistant reaction tube, under the irradiation of 15W blue LED light, react in 3mL solvent ethanol at 40°C for 2 hours. After cooling to room temperature, two spoonfuls of column chromatography silica gel (100-200 mesh) were added to the reaction solution, and the solvent was removed by distillation under reduced pressure, and then separated by column chromatography to obtain the pure product shown in structural formula (III-3). product (petroleum ether / ethyl acetate = 20:1 as eluent). The material was a yellow solid, 63% yield.

[0044] 1 H NMR (500MHz, CDCl3): δ = 8.21 (s, 1H), 7.89 (d, J = 9.0Hz, 1H), 7.75 (d, J = 7.0Hz, 1 H), 7.66–7.62 (m, 3H) ,7.45–7.39(m,4H),7.26–7.19(m,2H),6.33(d,J=7.5Hz,1H)ppm. 13 C NMR (125MHz, CDCl3): δ=192.8, 144.8, 137.8, 136.7, 136.53, 136....

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Abstract

The invention relates to a method for synthesizing a benzofluorenone compound through photocatalysis. The method comprises the following steps: mixing a compound represented by a formula (I), a compound represented by a formula (II), a photosensitizer and a solvent, reacting for 1-3 h at a temperature of 30-50 DEG C under the irradiation of 15 W blue LED light, and performing post-treatment on thereaction liquid to obtain a benzofluorenone compound represented by a formula III. According to the invention, the method is safe, environment-friendly, free of waste gas and low in operation risk; the substrate adaptability is good, and oxidative cyclization of various substituent groups can be realized; reaction conditions are mild; and the benzofluorenone is synthesized by adopting a photocatalysis mode in the reaction, so that the method is more environment-friendly and is closer to the concept of green chemistry.

Description

[0001] (1) Technical field [0002] The invention relates to a method for photocatalytically synthesizing benzofluorenone compounds. [0003] (2) Background technology [0004] Fluorenones and benzofluorenones are important and useful carbocycles that have attracted considerable attention for their unique biological and pharmaceutical activities as well as optical and electronic properties. For example, the fluorenone alkaloid cauliphine (shown in the following formula A), an alkaloid isolated from the natural product Caulophyllum robustum, has been tested to exhibit good anti-myocardial ischemia activity. And kinafluorenone (shown in the following formula B) is an intermediate for the synthesis of antibiotics prekinamycin and stealthin; the chiral compound Fluostatin B (shown in the following formula C) is a new inhibitor of dipeptidyl peptidase III from human placenta, etc. In addition, benzofluorenone is also widely used in the field of optoelectronic materials and dyes. ...

Claims

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Application Information

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IPC IPC(8): C07C45/76C07C49/665C07C49/697C07C49/755
CPCC07C45/76C07C2603/40C07C49/665C07C49/697C07C49/755
Inventor 刘运奎郑立孟鲍汉扬
Owner ZHEJIANG UNIV OF TECH
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