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Method for preparing silylene by carbene-induced halogenated silane dehydrohalogenation

A technology of halosilane and dehydrohalogenation, applied in chemical instruments and methods, compounds of Group 4/14 elements of the periodic table, organic chemistry, etc., can solve problems such as danger, complex products, and many reaction by-products

Inactive Publication Date: 2009-12-16
NANKAI UNIV
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  • Abstract
  • Description
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  • Application Information

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Problems solved by technology

In addition to the use of dangerous highly active alkali metals, in some cases the reaction needs to be carried out at a higher temperature, and the reaction by-products are more
In addition, methods using photo- and pyrolysis of appropriate precursors of organosilicon such as cyclopropene and cyclobutacyclosilanes with ring structures have also been reported, in addition to the prior synthesis of substituted silicon dihalides by alkali-metal reductively coupled alkynes. In addition, photoreaction and high temperature reaction lead to complex products

Method used

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  • Method for preparing silylene by carbene-induced halogenated silane dehydrohalogenation
  • Method for preparing silylene by carbene-induced halogenated silane dehydrohalogenation
  • Method for preparing silylene by carbene-induced halogenated silane dehydrohalogenation

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Experimental program
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Effect test

Embodiment 1

[0028] Embodiment 1: the synthesis of compound 3:

[0029] Compound 1 (2.92g, 10mmol) was dissolved in 30mL of tetrahydrofuran, and 0.175g (25mmol) of lithium metal was added under the protection of argon. The reaction was stirred for two days and turned orange red. The unreacted lithium was filtered off, and the filtrate was cooled to -78 ℃, slowly added 10 mmol trichlorosilane dropwise with a syringe, warmed to room temperature and stirred for 12 hours, sucked dry, extracted with 50 ml n-hexane, concentrated the filtrate to obtain white crystal 3 (2.49 g, 70%). m.p.125-127℃. 1 HNMR (CDCl 3 ): δ=2.35(s, 6H, p-CH 3 ); 2.46(s, 12H, o-CH3); 5.78(s, 2H, olef.H); 6.41(s, 2H, Si-H); 6.99(s, 4H, Aryl-H). 13 C(CDCl 3 ): δ=18.65 (p-CH 3 ); 20.86 (o-CH3); 117.92 (HC=CH); 128.87, 129.41, 135.97, 136.71. (Aromaten-C).Elemental analysis (%) calcd for C 20 H2 4 N 2 Si: C, 67.29; H, 7.06; N, 7.85. Found: C, 66.93; H, 7.35; N, 7.42.

Embodiment 2

[0030] Embodiment 2: the synthesis of compound 4:

[0031] Dissolve 1.78g (5mmol) of compound 3 in 20mL of n-hexane, add I t Bu (0.9g, 5mmol) in n-hexane solution (20mL), stirred at room temperature for 10 hours, filtered, and the filtrate was concentrated and placed in a -40°C refrigerator to obtain yellow crystals 4 (1, 30g, 81.2%).m.p.110-112 ℃. 1 H NMR (C 6 D. 6 ): δ=2.17(s, 6H, p-CH 3 ); 2.25(s, 12H, o-CH3); 6.29(s, 2H, olef.H); 6.83(s, 4H, Aryl-H). 13 C{ 1 H}NMR (C 6 D. 6 ): δ=18.49 (p-CH 3 ); 20.96 (o-CH3); 124.41 (HC=CH); 129.30, 134.83, 135.78, 140.25 (Aromaten-C). 29 Si { 1 H}NMR (C 6 D. 6 ): 77.8. Elemental analysis (%) calcd for C 20 h 24 N 2 Si: C, 74.95; H, 7.55; N, 8.74. Found: C, 74.92; H, 7.41; N, 8.68.

Embodiment 3

[0032] Embodiment 3: the preparation of compound 6:

[0033] Lithium salt 5 (2.26g, 5.0mmol) was dissolved in 60mL of n-hexane, cooled to -78°C, and 1.1 equivalent of SiHCl was added dropwise to the solution 3 (0.75 g, 5.5 mmol). The solution gradually rose to room temperature, and white lithium chloride was produced. The solution was continuously stirred at room temperature for 12 hours, and then the lithium chloride was filtered off. The filtrate was concentrated in vacuo to 20 mL and then placed at -40°C for freezing and crystallization to obtain 2.1 g of white crystalline compound 6 with a yield of 83.5%.

[0034] Characterization:

[0035] Mp: 83-85°C. 1 H NMR (CDCl 3 , 300MHz): δ1.07 (d, 3H, J=6.82, dipp-iPr-CH 3 ), 1.12 (d, 3H, J=6.89, dipp-iPr-CH 3 ), 1.19 (d, 3H, J=6.89, dipp-iPr-CH 3 ), 1.35 (d, 3H, J=6.83, dipp-iPr-CH 3 ), 3.59 (sept, 1H, J = 6.84, dipp-iPr-CH), 3.91 (sept, 1H, J = 6.82, dipp-iPr-CH), 6.35 (s, 1H, Si-H), 6.71 (t , 2H, J=7.35, Ar-H), 6.87(t,...

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Abstract

The invention discloses a method for preparing silylene by carbene-induced halogenated silane dehydrohalogenation, and relates to a method for synthesizing silylene. Dilithium salt of [NN] bidentate ligand and halogenosilane or substituted halogenosilane organic silicon reagent react to form substituted halogenated silane; and the molar ratio of the substituted halogenated silane to stable carbene is 1:0.5-10, the reaction temperature is between 78 DEG C below zero and 100 DEG C, the substituted halogenated silane and the stable carbene are mixed in a common organic solvent to generate imidazole salt of silylene and carbene, the generated imidazole salt is separated from the solution of a product through filtration after the reaction is finished, and the silylene or derivatives of the silylene are obtained through recrystallization and chromatographic separation. Through the reaction of different organic halogenosilane hydrides and the carbene, the method discovers that the carbene can effectively reduce a silicon compound under the mild condition to generate bivalent silicon intermediate. The imidazole salt as the reaction product can be converted into the carbene more easily so as to realize recycle.

Description

technical field [0001] The invention relates to a synthesis method of silicene, in particular to a method for preparing silicene by dehydrohalogenation of halosilane induced by carbene. Background technique [0002] Organosilicenes are compounds of divalent silicon. Due to the wide application of divalent carbon carbene in organic synthesis and catalytic reactions, the synthesis and performance research of its congener silicene has also received extensive attention in recent years. However, stable divalent silicon (silicene and disilene) is relatively rare. In the past ten years, several kinds of silicenes have been reported, and many transition metal compounds have been studied, but due to the limitation of the types, the research on their catalytic reactions is very little. On the other hand, silicene can also be polymerized to produce high-performance silicon polymers, which can be used for both conductive materials and light-emitting devices. So far, the common method...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/10
Inventor 崔春明崔海燕邵延军李晓斐孔令兵张建颖
Owner NANKAI UNIV
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