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New method for synthesizing unsymmetrical dithieno silole derivative

A technology of dithiophene and derivatives, applied in the field of organic compound preparation, can solve problems such as preparation methods that have not yet been reported

Active Publication Date: 2012-07-18
HENAN UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0015] The above-mentioned methods can obtain dithienosilole and its derivatives with symmetrical molecular structure in high yield, but the molecular structure is asymmetrical dithieno[2,3-b:4′,3′-d] The preparation method of derivatives of silole has not been reported yet

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  • New method for synthesizing unsymmetrical dithieno silole derivative
  • New method for synthesizing unsymmetrical dithieno silole derivative
  • New method for synthesizing unsymmetrical dithieno silole derivative

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Embodiment 1

[0036] Preparation of compound 1

[0037] Add raw material 4,4'-dibromo-2,2,5,5'-tetrakis(trimethylsilyl)-3,3'-bithiophene (2.29g, 3.74mmol) into a 250mL Schlenk bottle, and add 80mL of anhydrous diethyl ether. Adjust the temperature to -78°C, slowly add t-BuLi (1.49M, 11.0mL, 16.44mmol, 4.4eq) dropwise, and react at -78°C for 1h. The reaction was slowly raised to -50°C, stirred for 1 h, and 10 mL of H 2 O quenching reaction, Et 2 O (3 × 40mL) extraction, the organic phase with H 2 O (3×50 mL) was washed, dried over anhydrous magnesium sulfate, filtered, the solvent was removed by spin, and separated by silica gel column chromatography (eluent: petroleum ether) to obtain 1.53 g of white solid. Yield: 93.4%. Mp: 128-129°C. 1 HNMR (400MHz, CDCl 3 ): δ7.54(s, 1H), 0.48(s, 6H), 0.45(s, 9H), 0.36(s, 9H), 0.35(s, 9H). 13 C NMR (100MHz, CDCl 3 ): δ155.8, 155.3, 153.9, 151.0, 151.0, 146.6, 131.8, 130.6, 0.8, 0.4, 0.0, -0.9. IR (KBr): 3093.2, 2957.0, 2893.4 (C-H) cm -1 .HRMS ...

Embodiment 2

[0039] Preparation of compound 2

[0040] Add raw material 4,4'-dibromo-2,2,5,5'-tetrakis(trimethylsilyl)-3,3'-bithiophene (6.91g, 11.3mmol) into a 500mL Schlenk bottle, and add 200mL of anhydrous ether. Adjust the temperature to -78°C, slowly add t-BuLi (1.37M, 36.2mL, 49.72mmol, 4.4eq) dropwise, slowly rise to 45°C, stir for 14h, add 10mL H 2 O quenching reaction, Et 2 O (3 × 40mL) extraction, the organic phase with H 2 O (3×50mL) was washed, dried over anhydrous magnesium sulfate, filtered, the solvent was removed by spin, and separated by silica gel column chromatography (eluent: petroleum ether) to obtain 3.86g of white solid, yield: 93.2%. Mp: 137-138°C. 1HNMR (400MHz, CDCl 3 ): δ7.62(d, J=4.8Hz, 1H), 7.44(d, J=4.8Hz, 1H), 0.50(s, 6H), 0.46(s, 9H), δ0.38(s, 9H) . 13 C NMR (100MHz, CDCl 3 ): δ156.0, 154.7, 152.3, 151.0, 140.5, 134.4, 132.1, 123.9, 0.8, 0.4, -1.0. IR (KBr): 2951.6, 2898.0 (C-H) cm -1 .HRMS (EI, 70eV): m / z calcd for [C 16 h 26 Si 3 S 2 ] 366.07...

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Abstract

The invention discloses a new method for synthesizing dithieno[2,3-b:4',3'-d] silole derivative with the characteristic of an unsymmetrical structure. The method comprises the following steps of: performing bromine and lithium exchange reaction of 4,4'-bromine-2,2,5,5'-tetra(trimethylsilyl)-3,3'-bithiophene serving as a raw material and tertiary butyl lithium in absolute ether, and quenching by using water at the temperature of -50 DEG C to obtain 7,7-dimethyl-2,4,6-tri(trimethylsilyl)-dithieno[2,3-b:4',3'-d]silole in high yield; and quenching by using the water at the temperature of 45 DEG C to obtain 7,7-dimethyl-4,6-bis(trimethylsilyl)-dithieno[2,3-b:4',3'-d]silole in high yield. The synthetic process has operability and is suitable for laboratory-scale preparation, and reaction is performed in the absence of water and oxygen at low temperature.

Description

technical field [0001] The invention belongs to the technical field of organic compound preparation Background technique [0002] Dithienosilole compounds due to their special σ * -π * Conjugation, with a lower lowest unoccupied orbital (LUMO), makes it widely used in the field of optoelectronic functional materials. Three dithienosilole isomers have been reported to have symmetrical molecular structures, namely: dithieno[3,4-b:4′,3′-c]silole, dithieno[2 , 3-b: 3′, 2′-d]silole, dithieno[3,2-b: 2′, 3′-d]silole, their molecular structural formulas are as follows: [0003] [0004] Dithieno[3,4-b:4',3'-c]siloledithieno[2,3-b:3',2'-d]siloledithieno[3,2-b: 2′,3′-d]silole [0005] At present, there are two methods for the synthesis of these three dithienosiloles with symmetrical molecular structures, which are listed as follows: method 1, dihalogenated dithiophenes react with organolithium reagents, and then use halosilanes to synthesize their silicon-based rings. Synthes...

Claims

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Application Information

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IPC IPC(8): C07F7/08
CPCY02P20/582
Inventor 王华赵金灿史建武李春丽
Owner HENAN UNIVERSITY