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Dithieno[2,3-b:2',3'-d]thiophene preparation methods

A technology of dithiophene and 3-b, applied in the field of organic compound preparation, can solve the problems of increasing the difficulty of preparation process, instability, dimerization and the like

Active Publication Date: 2013-09-25
HENAN UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0011] Although this route prepares dithieno[2,3-b:2',3'-d]thiophene in high yield, the elemental sulfur used in the route needs to be sublimated and dried, which is difficult to handle
Compound 6 is unstable and prone to oxidation and dimerization, which increases the difficulty of the preparation process

Method used

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  • Dithieno[2,3-b:2',3'-d]thiophene preparation methods

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Experimental program
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Embodiment 1

[0052] Preparation of compound 1a

[0053] Compound 3a (1.39g, 4.28mmol) was dissolved in 100mL of anhydrous ether and stirred to dissolve. Cool to -78°C, add tert-butyllithium (1.048M, 16.78mL, 4.1eq) dropwise, keep at -78°C for 2h, add di-benzenesulfonylsulfide (1.36g, 4.29mmol, 1.01 eq), keep the reaction at -78°C for 1h, raise the temperature to -55°C, keep the reaction at -55°C for 2h, naturally warm to room temperature and stir overnight. The reaction solution was extracted with chloroform (3×15 mL), the organic phases were combined and washed with 20 mL of saturated sodium bicarbonate solution and 20 mL of water, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed to obtain 920 mg of crude product, which was separated by column chromatography Compound 1a (0.42 g, 50.2%) was obtained. Repeated reaction: compound 3a was charged at 2.72g to obtain compound 1a (0.96g, 55%), the product was a white solid, M.p.:53-54°C, MS (EI + ,70eV):m / z=195.91(...

Embodiment 2

[0055] Preparation of compound 1b

[0056] Compound 3b (4.3390 g, 9.2 mmol) was added to 500 mL of Schlenk, dried in vacuum, and 220 mL of anhydrous diethyl ether was added under the protection of argon, and stirred to dissolve it. Under the protection of argon, add n-butyllithium (2.4105M, 8.4mL, 2.2eq) dropwise, react at -78°C for two hours, then add di-benzenesulfonyl sulfide (2.93g, 9.25mmol, 1.01eq), -78°C The reaction was maintained at low temperature for 1 h, the temperature was raised to -55° C., the reaction was maintained for 2 h, the temperature was naturally raised to room temperature, and stirred overnight. Add a few drops of water to quench the reaction, transfer the reaction solution into a 500mL separatory funnel, add 100mL water to wash, oscillate, stand still, separate the liquid, extract the aqueous phase with 30×2mL ether, combine the organic phase, and use 50mL water for the organic phase , saturated sodium chloride solution, washed with water, dried over...

Embodiment 3

[0058] Preparation of 1a from compound 1b

[0059] Compound 1b (0.16g, 0.47mmol) was added to 15mL of chloroform, stirred and dissolved. Add trifluoroacetic acid (1 mL) and stir at room temperature for about 1 h. The reaction process is monitored by TLC until the starting material disappears. Add water (10mL) to the reaction solution, extract with chloroform (2×10mL), wash the organic phase with saturated sodium bicarbonate solution (10mL) and water (10mL) respectively, dry over anhydrous magnesium sulfate, and perform silica gel column chromatography (leaching Washing solution: petroleum ether) to obtain white solid 1a (0.09g, 97.5%). The reaction was repeated: compound 1b was fed at 0.26 g to obtain compound 1a (0.148 g, 98.6%), and the product was a white solid.

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Abstract

The present invention discloses two dithieno[2,3-b:2',3'-d]thiophene preparation methods. The method 1 comprises: adopting 2,3'-dibromo-3,2'-bithiophene as a raw material, and carrying out t-BuLi double bromine lithium exchange and thiolizing reagent (PhSO2)2S ring closure to prepare the dithieno[2,3-b:2',3'-d]thiophene; or adopting 5,5'-bis(trimethylsilyl)-2,3'-dibromo-3,2'-bithiophene as a raw material, carrying out double bromine lithium exchange through n-BuLi, and thiolizing reagent (PhSO2)2S ring closure, and removing trimethylsilyl through trifluoroacetic acid to prepare the dithieno[2,3-b:2',3'-d]thiophene. The method 2 comprises: adopting 3-bromo-2,3'-bithiophene as a raw material, carrying out n-BuLi bromine lithium exchange while carrying out selective competition of protons, and carrying out thiolizing reagent (PhSO2)2S ring closure to prepare the dithieno[2,3-b:2',3'-d]thiophene; or adopting 3-bromo-5-(trimethylsilyl)-2,3'-bithiophene as a raw material, carrying out n-BuLi bromine lithium exchange while carrying out selective competition of protons, carrying out thiolizing reagent (PhSO2)2S ring closure and removing trimethylsilyl through trifluoroacetic acid to prepare the dithieno[2,3-b:2',3'-d]thiophene. According to the present invention, the synthesis process has operability, reaction conditions relate to no water, no oxygen and low temperature, and the method is suitable for laboratory scale preparation.

Description

technical field [0001] The invention belongs to the technical field of organic compound preparation Background technique [0002] There are six isomers of trithiophene compounds, such as figure 1 shown. [0003] [0004] figure 1 .Six isomers of trithiophene [0005] These trithiophene compounds have unique properties in organic conductors, organic semiconductors, organic electroluminescent materials, organic nonlinear optical materials, and organic thin film field-effect transistors due to their high charge mobility and good conjugation. It has a good application prospect and has been favored by organic chemists and material scientists in recent years. [0006] What we are interested in is the preparation of dithieno[2,3-b:2′,3′-d]thiophene (1a). At present, there are only two reports on its synthesis method, and there has been a lack of effective preparation method, which affects The application of this compound in the field of organic functional materials. The pr...

Claims

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Application Information

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IPC IPC(8): C07D495/14
Inventor 王华孙会靓刘新明李春丽万世胜
Owner HENAN UNIVERSITY
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