Preparation method for 9,9-diaryl thiophene xanthene-10,10-dioxide

A technology of dioxide and thiaxanthene, which is applied in the new preparation field, can solve the problems of human, environmental hazard, high production cost, long synthesis route and the like, and achieves the effects of easy industrialization, low cost and simple operation.

Inactive Publication Date: 2015-04-29
NANJING UNIV OF POSTS & TELECOMM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] This method has a long synthetic route, and uses thiophenol with high toxicity, which is harmful to humans and the environment. It needs to be strictly controlled in the synthetic process, and also uses the relatively expensive bromoiodobenzene substrate to produce higher cost

Method used

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  • Preparation method for 9,9-diaryl thiophene xanthene-10,10-dioxide
  • Preparation method for 9,9-diaryl thiophene xanthene-10,10-dioxide
  • Preparation method for 9,9-diaryl thiophene xanthene-10,10-dioxide

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0031] Example 1: Preparation of spirofluorenethiaxanthene-10,10-dioxide

[0032]

[0033] Weigh diphenyl sulfone (4.75g, 0.022mol, 1.05eq) and methyl 2-biphenylcarboxylate (4.4g, 0.021mol, 1eq) and put them into a two-necked flask and a constant pressure dropping funnel respectively, and use a dry Diphenylsulfone was dissolved in 120 mL of tetrahydrofuran. Under nitrogen protection and a dry ice-ethanol bath, slowly add 1.6M n-butyllithium hexane solution (28.5mL, 0.045mol, 2.2eq) dropwise, keep the reaction at low temperature for 3h, and quickly add methyl 2-biphenylcarboxylate in tetrahydrofuran solution; react at room temperature for 24 hours, after the reaction, add saturated ammonium chloride solution for hydrolysis, extract with dichloromethane, dry, and remove the solvent; put the obtained tertiary alcohol into a two-necked flask, add 100mL of glacial acetic acid, and heat Reflux to dissolve, take 0.5mL of concentrated sulfuric acid and add it to the reaction solut...

example 2

[0034] Example 2: Preparation of 2-bromospirofluorenethiaxanthene-10,10-dioxide

[0035]

[0036] Weigh diphenyl sulfone (3.93g, 0.018mol, 1.1eq) and ethyl 2-(4'-bromobiphenyl) formate (5.0g, 0.0164mol, 1eq) and put them into a two-necked flask and constant pressure drop solution respectively. In the funnel, dissolve diphenyl sulfone with 80 mL of dry tetrahydrofuran. Under nitrogen protection and a dry ice-ethanol bath, slowly add 1.6M n-butyllithium hexane solution (22.5mL, 0.036mol, 2.2eq) dropwise, maintain the low temperature reaction for 3h, and quickly add 2-(4'-bromobiphenyl ) tetrahydrofuran solution of ethyl formate; react at room temperature for 20h, after the reaction is over, add saturated ammonium chloride solution for hydrolysis, extract with dichloromethane, dry, and remove the solvent; put the obtained tertiary alcohol into a two-necked flask, add 80mL glacial acetic acid, and heated to reflux to dissolve, take 0.5mL of concentrated sulfuric acid and add t...

example 3

[0037] Example 3: Preparation of 2,7-dibromospirofluorenethiaxanthene-10,10-dioxide

[0038] There are many schemes for the synthesis of 2,7-dibromospirofluorenethiaxanthene-10,10-dioxide, and the most economical and convenient synthesis scheme is as follows:

[0039]

[0040] The specific process of spirofluorenethiaxanthene-10,10-dioxide is as in Example 1. Take spirofluorene sulfone xanthene (1.9g, 0.005mol) and a catalytic amount of iron powder (0.036g) into a two-necked flask, and dissolve it with 50mL of chloroform; take liquid bromine (1.84g, 0.0115mol) and inject it into the flask , reacted under reflux conditions for 14 hours; after the reaction, add sodium bisulfite solution to the reaction flask, and stir for 30 minutes, extract with dichloromethane, combine organic phases, dry over anhydrous magnesium sulfate, suction filter, spin dry and pass through the column After separation, 2.5 g of white solid product 2,7-dibromospirofluorene sulfone xanthene was obtaine...

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Abstract

The invention discloses a preparation method for 9,9-diaryl thiophene xanthene-10,10-dioxide, and belongs to the field of fine organic synthesis and organic semiconductor material preparation. The preparation method comprises the following steps: using diphenylsulphone as a starting material and tetrahydro furan as a solvent, conducting ortho metalation reaction on diphenylsulphone under the action of n-butyllithium within a temperature range of -78-0 DEG C to obtain a corresponding aryl lithium salt; allowing the aryl lithium salt to react with an added aryl formic ether ester derivative, and performing hydrolysis to obtain a corresponding tertiary alcohol; dissolving the tertiary alcohol and electron-rich aromatic with an acetate or methylene chloride solution, using Lewis acid as a catalyst, and carrying out friedel-crafts reaction to obtain the 9,9-diaryl thiophene xanthene-10,10-dioxide. The preparation method has the advantages that the reactions are easy to control, the operation is simple, the cost is low, the repeatability is good, the productivity is high, and the product quality is high; an organic modular unit and an organic functional semiconductor can be conveniently made; the 9,9-diaryl thiophene xanthene-10,10-dioxide is used in the fields of organic light emitting diodes, organic transistors, organic laser, and organic nonlinear optics, and the like.

Description

technical field [0001] The invention belongs to the fields of fine organic synthesis and preparation of organic semiconductor materials, and in particular relates to a new preparation method of 9,9-diarylthiaxanthene-10,10-dioxide. Background technique [0002] Information display and lighting are closely related to people's daily life and are indispensable, so people put forward higher and higher requirements to meet the needs of daily life. Since 1987, Deng Qingyun's research group of Kodak Company of the United States reported for the first time an efficient multilayer thin film organic light-emitting diode based on small molecule 8-hydroxyquinoline aluminum [C.W.Tang and S.A.VanSlyke, Appl.Phys.Lett.1987,51,913-915 ], and in 1990, the Bradley group of the University of Cambridge reported solution processing to prepare organic light-emitting diodes [J.H.Burroughes, D.D.C. Bradley, A.R.Brown, R.N.Marks, K.Mackay, R.H.Friend, et al., Nature, 1990, 347, 539-541 .], organic ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D335/04C07D335/20C07D495/10
CPCC07D335/04C07D335/20C07D495/10
Inventor 解令海黄维欧昌金
Owner NANJING UNIV OF POSTS & TELECOMM
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