Synthesis method of polysubstituted silole derivative

A technology for the synthesis of silacyclopentadiene, applied in the direction of silicon organic compounds, etc., can solve the problems of inability to effectively realize multiple substituent groups, limit the diversity of substituent groups, and low tolerance of functional groups, so as to facilitate development The application and synthesis method are scientific and reasonable, and the effect of wide application range

Inactive Publication Date: 2013-08-14
INST OF CHEM CHINESE ACAD OF SCI +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The currently reported synthetic methods mostly use equivalent metal reagents, the reaction is relatively harsh, and the tolerance of functional groups is low, so it cannot effectively realize multiple substituent groups, and also limits the diversity of substituent groups.

Method used

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  • Synthesis method of polysubstituted silole derivative
  • Synthesis method of polysubstituted silole derivative
  • Synthesis method of polysubstituted silole derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Embodiment 1——preparation formula IVa (R 1 =H,R 2 =R 3 =Ph) compound:

[0031]

[0032] Under nitrogen protection, in a 50mL reaction tube, add 1mmol of 2-(trimethylsilyl)phenyltrifluoromethanesulfonate, 1.2mmol of tolan, 0.05mmol of allyl palladium chloride, 0.1mmol of Tri-tert-butylphosphine, 3 mmol of lithium ethoxide, 2 mmol of potassium bromide and 5 mL of toluene solvent. The reaction temperature was kept constant at 120° C. for 24 hours using an oil bath. After cooling and filtering, the filtrate was concentrated to obtain the crude product. The crude product was decolorized and separated on a silica gel column, and petroleum ether was used as the eluent to obtain 250 mg of 1,1-dimethyl-2,3-diphenylbenzosilole (purity>98%, colorless solid). The rate is 80%. The NMR data of this compound are as follows: 1 H NMR (400MHz, CDCl 3 )δ:0.47(s,6H,CH 3 ), 6.96-6.99 (m, 2H, CH), 7.04-7.07 (m, 2H, CH), 7.11-7.14 (m, 2H, CH), 7.18-7.21 (m, 2H, CH), 7.26-7.34 ( m...

Embodiment 2

[0033] Embodiment 2——preparation formula IVb (R 1 =OMe,R 2 =Ph,R 3 =TMS) compound:

[0034]

[0035] Under nitrogen protection, add 1mmol of 2-(trimethylsilyl)-3-methoxyphenyltrifluoromethanesulfonate, 1.2mmol of phenylethynyltrimethylsilane, 0.05mmol in a 50mL reaction tube Allylpalladium chloride, 0.1mmol of tri-tert-butylphosphine, 3mmol of lithium ethoxide, 2mmol of potassium bromide and 5mL of xylene solvent. The reaction temperature was kept constant at 120° C. for 24 hours using an oil bath. After cooling and filtering, the filtrate was concentrated to obtain the crude product. The crude product was decolorized and separated on a silica gel column, and petroleum ether was used as the eluent to obtain 220 mg of 1,1-dimethyl-2-(trimethylsilyl)-3-phenyl-7-methoxybenzosilole ( Purity>98%, colorless oily liquid), isolated yield 65%. The NMR data of this compound are as follows: 1 H NMR (400MHz, CDCl 3 )δ:0.49(s,6H,CH 3 ),3.85(s,3H,CH 3 ),6.69(d,J=7.5Hz,1H,CH),6....

Embodiment 3

[0036] Embodiment 3——preparation formula IVc (R 1 =2F,R 2 =R 3 =Ph) compound:

[0037]

[0038]Under nitrogen protection, add 1 mmol of 2-(trimethylsilyl)-4,5-difluorophenyltrifluoromethanesulfonate, 2 mmol of tolan, and 0.025 mmol of chlorinated alkenes into a 50 mL reaction tube Propyl palladium dimer, 0.1 mmol of tri-tert-butylphosphine, 2 mmol of lithium ethoxide, 1 mmol of tetramethylammonium bromide and 6 mL of 1,4-dioxane solvent. The reaction temperature was kept constant at 120° C. for 12 hours using an oil bath. After cooling and filtering, the filtrate was concentrated to obtain the crude product. The crude product was decolorized and separated on a silica gel column, and petroleum ether was used as the eluent to obtain 174 mg of 1,1-dimethyl-3,4-diphenyl-5,6-difluorobenzosilole (purity>98% , white solid), isolated in 50% yield. The NMR data of this compound are as follows: 1 H NMR(CDCl3,399.78MHz)δ:0.47(s,9H),6.85(dd,JH-F=11.8Hz,JH-F=7.6Hz),6.93-6.96(m,2H...

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Abstract

The invention provides a synthesis method of a polysubstituted silole derivative. The polysubstituted silole derivative is prepared by reacting a 2-(trimethylsilyl)aryl trifluoromethane sulfonate derivative with alkyne in the presence of a catalyst. The synthesis method is pretty high in yield rate, scientific, reasonable, accessible in raw materials, wide in application range, high in separation yield rate, simple in experiment equipment, simple and easy in operation implementation, and conductive to further development and application.

Description

technical field [0001] The invention belongs to the field of organic synthesis and relates to a general synthesis method of silacyclopentadiene derivatives with various substituents. Background technique [0002] Multi-substituted silacyclopentadiene (silole) derivatives have low reduction potential and lowest unoccupied orbital (LUMO), strong electron mobility and electron affinity, and strong ability to accept electrons. This unique electronic structure makes it have great application prospects in the field of optoelectronic materials, such as electroluminescent (EL) materials, light-emitting diode (LED) organic semiconductor materials, electron transport materials, nonlinear optical materials, etc. The currently reported synthetic methods mostly use equivalent metal reagents, the reaction is relatively harsh, and the tolerance of functional groups is low, so that it is impossible to effectively realize multiple substituent groups, and also limits the diversity of substitu...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/08
Inventor 孟天颢欧阳昆冰席振峰
Owner INST OF CHEM CHINESE ACAD OF SCI
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