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Process for preparing polysubstituted silole

A polysubstituted and silole technology, which is applied in the field of organic synthesis intermediates and new functional materials synthesis, can solve the problems of lack of synthesis methods, and achieve the effects of wide application range, easy availability of raw materials and high separation yield.

Inactive Publication Date: 2008-10-15
PEKING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

At present, only a few documents provide some synthetic methods of polysubstituted siloles, and there is no general synthetic method

Method used

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  • Process for preparing polysubstituted silole
  • Process for preparing polysubstituted silole
  • Process for preparing polysubstituted silole

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048]One of the compounds of formula IIa (R 1 =TMS, R 2 =R 3 =Ph, E=H): Synthesis of 1,1-dimethyl-2-trimethylsilyl-3,4-diphenylsilole

[0049] Add 1mmol 1,4-diiodo-1,4-bis(trimethylsilyl)-2,3diphenyl-1,3-butadiene and 5mL ether solvent to a 20mL reaction tube under nitrogen protection , add tert-butyllithium dropwise at -78°C, react for one hour after the addition, add HMPA, raise the temperature to reflux, and react for one hour with magnetic stirring. Add water (as an electrophile) to react at zero temperature, extract the water phase with ether three times, combine the organic phases, wash with saturated sodium chloride solution, add anhydrous magnesium sulfate to the organic phase after liquid separation, dry for 30 minutes, and filter under normal pressure , the filtrate was concentrated, decolorized and separated on a silica gel column, and the eluent of petroleum ether was used to obtain 300 mg of pure product 2-trimethylsilyl-3,4-diphenylsilole (purity > 95%, color...

Embodiment 2

[0051] Formula IIa class compound two (R 1 =TMS,R 2 =R 3 =Ph, E=SiPh 3 ): Synthesis of 1,1-dimethyl-2-trimethylsilyl-3,4-diphenyl-5-triphenylsilylsilole

[0052] The raw materials and synthetic route are basically the same as above. The electrophilic reagent used is triphenylchlorosilane, which is quenched by adding saturated sodium bicarbonate solution after the reaction, and the aftertreatment is the same. 500 mg of pure product (purity>98%, colorless solid, melting point: 102-104°C) was obtained with an isolated yield of 85%. The NMR and high resolution mass spectrometry data of this compound are as follows: 1 H NMR (300MHz, CDCl 3 , Me 4 Si, 25°C): δ=-0.17(s, 9H, CH 3 ), -0.01(s, 6H, CH 3 ), 6.41-6.46 (m, 2H, CH), 6.51-6.56 (m, 2H, CH), 6.84-6.86 (m, 2H, CH), 6.97-6.99 (m, 3H, CH), 7.19-7.27 ( m, 10H, CH), 7.45-7.47 (m, 6H, CH); 13 C NMR (75MHz, CDCl 3 , Me 4 Si, 25°C): δ=-3.15 (2CH 3 ), 0.68 (3CH 3 ), 125.65(1CH), 126.01(1CH), 126.29(2CH), 126.85(2CH), 127....

Embodiment 3

[0054] One of the compounds of formula IIb (R 1 =TMS, R'=H, E=H): 4,5,6,7-tetrahydro-2,2-dimethyl-1-trimethylsilyl-2H-benzo[c]silole

[0055] The synthetic route is basically the same as above, using water as the electrophile, and the post-treatment is the same. The starting raw material dihalogen compound of this synthesis is 1,2-bis-(1'-iodo-1'-trimethylsilylmethylene)-cyclohexane. 0.201 g of pure product (purity>98%, colorless liquid) was obtained with an isolated yield of 86%. The NMR and high-resolution mass spectrometry data of this compound are as follows: 1 H NMR (300MHz, C 6 D. 6 , Me 4 Si, 25°C): δ = 0.25 (s, 9H, CH 3 ), 0.26(s, 6H, CH 3 ), 1.35-1.51 (m, 4H, CH 2 ), 2.47(t, J=6.0Hz, 2H, CH 2 ), 2.55(t, J=6.0Hz, 2H, CH 2 ), 5.82(s, 1H, CH); 13 C NMR (75MHz, C 6 D. 6 , Me 4 Si, 25°C): δ=-3.76 (2CH 3 ), 0.89 (3CH 3 ), 23.79 (1CH 2 ), 24.31 (1CH 2 )32.39 (2CH 2 ), 33.10 (1CH 2 ), 128.94(1CH), 135.35(1quat.C), 159.23(1quat.C), 165.65(1quat.C); HRMS cal...

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Abstract

The invention provides a general method for synthesizing silole derivate with a plurality of substituents. The general method comprises the following steps that: firstly, 1-trialkylated silicone base-1, 4-dihalo-1 and 3-butadiene derivate are reacted with lithium alkyl in ether solvent at a low temperature; secondly, quaternary amine or acylammonia ligand is added and the mixture is heated up to continue the reaction; thirdly, the mixture is cooled down and electrophilic reagent E+ is added; finally, polysubstituted silole derivate is obtained through the post treatment and the purification of reaction liquid. The method, being scientific and reasonable, has easily obtained raw material, wide application range, high separation yield and simple experimental equipment and operation, and is convenient for further development and application.

Description

technical field [0001] The invention relates to a general synthesis method of silole (silacyclopentadiene, transliteration of silole) derivatives with various substituents, and belongs to the field of organic synthesis intermediates and synthesis of new functional materials. Background technique [0002] Silole (silacyclopentadiene) derivatives with various substituents are important organic photoelectric materials, widely used in important fields such as conduction and light emission, and these compounds are also important organic synthetic molecules. Siloles containing carbon-metal bonds can be easily derivatized to introduce various substituents and functional groups, providing novel and important ideas for the design and development of new organic optoelectronic materials. At present, only a few documents provide some synthetic methods of polysubstituted siloles, and there is no general synthetic method. Contents of the invention [0003] The object of the present inv...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/18C07F7/20
Inventor 席振峰王超
Owner PEKING UNIV
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