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Method for synthesizing 5, 5-spirosilafluorene through C-H arylation cyclization reaction

A synthesis method and a technology of cyclization reaction, which are applied in the field of organic synthesis of spirobifluorene derivatives, can solve problems such as high cost of starting materials, harsh reaction conditions, and complicated synthesis steps, and avoid lithium reagents and halosilanes. The use, production cost is easy to control, and the effect of high reactivity

Pending Publication Date: 2022-01-21
SINOSTEEL NANJING NEW MATERIALS RES INST CO LTD
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  • Application Information

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Problems solved by technology

[0016] The purpose of the present invention is to provide a synthesis method of 5,5-spirosilafluorene, which can solve the technical problems of high cost of starting raw materials, complicated synthesis steps, harsh reaction conditions and difficult post-processing existing in the prior art

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  • Method for synthesizing 5, 5-spirosilafluorene through C-H arylation cyclization reaction
  • Method for synthesizing 5, 5-spirosilafluorene through C-H arylation cyclization reaction
  • Method for synthesizing 5, 5-spirosilafluorene through C-H arylation cyclization reaction

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Experimental program
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Embodiment 1

[0039] Embodiment 1: A kind of synthetic method of 5,5-spirosilafluorene

[0040] The synthesis steps include: under nitrogen protection, add 43.3g of diphenyldihydroxysilane (98%, 0.2mol), 131.3g of 2-(trimethylsilyl)phenyltrifluoromethanesulfonic acid into a 1000mL reaction flask Salt (97%, 0.44mol), 1.85g of Rh (PPh 3 ) 3 Cl (98%, 2.0mmol), 3.0g of ligand L3 (98%, 2.0mmol), 63.6g of sodium carbonate (99%, 0.6mol) and 500mL of o-dichlorobenzene; after feeding, heat up to 120°C , stirring speed 500rpm, heat preservation reaction for 18 hours, carry out C-H arylation and cyclization reaction, thin layer chromatography (TLC) monitors the progress of the reaction; after the reaction is completely completed, heat, cool to room temperature for filtration, washing, extraction, and solvent recovery of the organic layer , the crude product was crystallized from petroleum ether to obtain 53.1 g of 5,5-spirosilafluorene product, with a content of 99.1% and a yield of 83.2%; wherein t...

Embodiment 2

[0042] Embodiment 2: A kind of synthetic method of 5,5-spirosilafluorene

[0043] The synthesis steps include: under nitrogen protection, add 43.3g of diphenyldihydroxysilane (98%, 0.2mol), 131.3g of 2-(trimethylsilyl)phenyltrifluoromethanesulfonic acid into a 1000mL reaction flask Salt (97%, 0.44mol), 1.23g of [Cp * RhCl 2 ] 2 (98%, 2.0mmol), the ligand L1 (98%, 2.0mmol) of 1.25g, the sodium tert-butoxide (98%, 0.6mol) of 57.7g and the o-dichlorobenzene of 500mL; Feed intake finishes, be warming up to 140 ℃, stirring speed 500rpm, heat preservation reaction for 18 hours, carry out C-H arylation and cyclization reaction, and monitor the progress of the reaction by thin layer chromatography (TLC); after the reaction is completely completed, heat, cool to room temperature for filtration, washing, extraction, and the organic layer is precipitated and recovered Solvent, the crude product was crystallized from a petroleum ether / ethyl acetate mixed solution to obtain 46.8g of 5,5...

Embodiment 3

[0045] Embodiment 3: A kind of synthetic method of 5,5-spirosilafluorene

[0046] The synthesis steps include: under nitrogen protection, add 43.3g of diphenyldihydroxysilane (98%, 0.2mol), 179.0g of 2-(trimethylsilyl)phenyltrifluoromethanesulfonic acid into a 1000mL reaction flask salt (97%, 0.6mol), 0.93g of Rh (PPh 3 ) 3 Cl (98%, 1.0mmol), 1.3g of ligand L4 (98%, 1.0mmol), 162.9g of cesium carbonate (99%, 0.5mol) and 600mL of mesitylene; after feeding, the temperature was raised to 140°C, The stirring speed is 500rpm, the heat preservation reaction is carried out for 24 hours, and the C-H arylation and cyclization reaction is carried out, and the reaction progress is monitored by thin layer chromatography (TLC); after the reaction is completely completed, the heating is cooled to room temperature, filtered, washed, extracted, and the organic layer is desolvated to recover the solvent. The crude product was crystallized from a petroleum ether / ethyl acetate mixed solution t...

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Abstract

The invention discloses a method for synthesizing 5, 5-spirosilafluorene. The method comprises the following steps: taking 2-(trimethylsilyl)phenyl trifluoromethanesulfonate and diphenyldihydroxysilane as initial raw materials, in the presence of a solvent and under the action of a catalyst, a ligand and an alkali, carrying out C-H arylation cyclization reaction, and synthesizing the 5, 5-spirosilafluorene by a one-pot method. According to the synthesis method, the adopted ligand is an aryl phosphine derivative, the aryl phosphine derivative and rhodium salt can generate a rhodium intermediate, the reaction efficiency of the catalyst is effectively improved, continuous and rapid reaction is achieved, the reaction condition is mild, a one-pot two-step coupling cyclization mode is adopted, and through the C-H arylation cyclization process, a spirosilafluorene structure containing two five-membered silicon heterocycles is constructed, reaction steps are shortened, expensive 2-bromodiphenyl or 2, 2 '-dibromodiphenyl is prevented from being used as a reaction raw material, and a new synthesis route is provided for 5, 5-spirosilafluorene.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis of a class of spirobifluorene derivatives, in particular to a synthesis method of 5,5-spirosilafluorene through C-H arylation and cyclization reaction. Background technique [0002] Because organic light-emitting semiconductors (OLEDs) have the characteristics of lightness, thinness, wide viewing angle, high contrast, low energy consumption, high response speed, full-color curved surface and bendability, etc., their applications in full-color displays and portable electronic devices have attracted much attention. . An organic light-emitting device generally consists of an anode, an organic layer, and a metal cathode, wherein the organic layer includes a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer. In the prior art, carbazole groups are mostly used as ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/08
CPCC07F7/0807C07F7/0827Y02P20/584
Inventor 杨修光裴晓东骆艳华吴忠凯朱叶峰申保金张玲张倩倩
Owner SINOSTEEL NANJING NEW MATERIALS RES INST CO LTD
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