Method for synthesizing 3,5-diphenyl phenol

A diphenylphenol and reactor technology, applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve the problem of limiting the synthesis of ortho-substituted derivatives, easy formation of isomers, and limited selection of raw materials and other problems, to achieve the effect of improving the total yield of the reaction, optimizing the reaction, and easily expanding the substrate

Inactive Publication Date: 2015-07-01
NANJING UNIV OF SCI & TECH
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Problems solved by technology

However, the strong electron-guiding effect in these reactions limits the synthesis of ortho-substituted derivatives, such as 3,5-disubstituted phenol series compounds
[0005] There are difficulties in the synthesis of 3,5-diarylphenol series compounds. Although this has attracted the investment and enthusiasm of a large number of scientific researchers, a

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  • Method for synthesizing 3,5-diphenyl phenol
  • Method for synthesizing 3,5-diphenyl phenol
  • Method for synthesizing 3,5-diphenyl phenol

Examples

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Embodiment 1

[0032] Add 130mg (1mmol) ethyl acetoacetate, 390mg (1.1mmol) Selectfluor TM , 2mL of acetonitrile, reflux at 85°C for 2h to obtain a yellow mixed solution; continue to add 208mg (1mmol) of chalcone and 652mg (2mmol) of cesium carbonate to the pressure tube, and react at 120°C for 2h to obtain a brownish yellow reaction solution. Add 2M dilute hydrochloric acid dropwise to adjust the pH of the reaction solution to 5-6, and the color of the reaction solution becomes lighter. Solvent acetonitrile was removed by distillation under reduced pressure, and the yellow organic phase was extracted with dichloromethane, dried over anhydrous sodium sulfate, and dichloromethane was removed by distillation under reduced pressure to obtain a crude product, which was subjected to column chromatography (ethyl acetate:petroleum ether). =1:4) separated and purified to obtain 204.5 mg of white solid, with a total yield of 83%. For its structural characterization, see figure 1 and figure 2 .

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Embodiment 2

[0035] Add 130mg (1mmol) ethyl acetoacetate, 390mg (1.1mmol) Selectfluor TM , 2mL of acetonitrile, reacted at 80°C for 3h to obtain a yellow mixed solution; continued to add 208mg (1mmol) of chalcone and 652mg (2mmol) of cesium carbonate to the pressure tube, and reacted at 110°C for 4h to obtain a brownish yellow reaction solution. Add 2M dilute hydrochloric acid dropwise to adjust the pH of the reaction solution to 5-6, and the color of the reaction solution becomes lighter. Solvent acetonitrile was removed by distillation under reduced pressure, and the yellow organic phase was extracted with dichloromethane, dried over anhydrous sodium sulfate, and dichloromethane was removed by distillation under reduced pressure to obtain a crude product, which was subjected to column chromatography (ethyl acetate:petroleum ether). =1:6) separated and purified to obtain 197.1 mg of white solid with a total yield of 80%.

Embodiment 3

[0037] Add 130mg (1mmol) ethyl acetoacetate, 390mg (1.1mmol) Selectfluor TM, 2 mL of acetonitrile, reacted at 90°C for 2 hours, and obtained a yellow mixed liquid; continued to add 208 mg (1 mmol) of chalcone and 652 mg (2 mmol) of cesium carbonate to the pressure tube, and reacted at 130° C. for 2 hours, to obtain a brownish yellow reaction liquid. Add 2M dilute hydrochloric acid dropwise to adjust the pH of the reaction solution to 5-6, and the color of the reaction solution becomes lighter. Solvent acetonitrile was removed by distillation under reduced pressure, the yellow organic phase was extracted with dichloromethane, dried over anhydrous sodium sulfate, and dichloromethane was removed by distillation under reduced pressure to obtain a crude product, which was subjected to column chromatography (ethyl acetate:petroleum ether) =1:5) separated and purified to obtain 199.6 mg of white solid with a total yield of 81%.

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Abstract

The invention discloses a method for synthesizing 3,5-diphenyl phenol in one pot by two steps. The method comprises the following steps: by taking ethyl acetoacetate as a raw material, fluorinating by using a fluorinating agent SelectfluorTM; cyclizing with chalcone Robinson to generate a fluorine-containing cyclohexenone midbody; subsequently continuously performing dehydrofluorination, aromatization and hydrolysis decarboxylation to generate a final product 3,5-diphenyl phenol. The method is simple to operate, capable of reducing the difficulty of after-treatment, high in reaction selectivity, cheap in raw material, good in substrate adaptability and capable of shortening the total reaction time of a traditional method from 30h to 4h and increasing the total yield from 20% to above 80%. A 3,5-diaryl phenol derivative is an important medicine midbody, and the special molecular structure thereof has quite important bioactivity and can be used for preparing 'Molecular Harpoon'.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a novel and efficient synthesis method for synthesizing 3,5-diphenylphenol in one pot by using acetoacetate and chalcone as raw materials, undergoing fluorination and dehydrofluorination processes. Background technique [0002] Whether it is in the field of medicine or polymer, phenol is the precursor or core structural unit of some commonly used industrial compounds, and it has always been a very challenging task to introduce some special functional groups at specific positions on the phenol ring. . Among all substituted derivatives of phenol, 3,5-diaryl substituted derivatives have very important biological activities and can be used to prepare "molecular harpoons". Some important such intermediates are listed in the following formula, such as 1a and 1b are intermediates of EGF-stimulated cell proliferation inhibitors and anti-cell proliferation drugs, 1c is CD40 function inhi...

Claims

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Application Information

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IPC IPC(8): C07C37/50C07C39/15
CPCC07C37/50C07C39/15
Inventor 缪勇波易文斌蔡春
Owner NANJING UNIV OF SCI & TECH
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