Method for preparing trimethylsilylcyanation

A technology of trimethylsilicon cyanide and halogenated trimethylsilane is applied in the field of preparation of high-efficiency trimethylsilicon cyanide, can solve problems such as environmental hazards, high cost, unfavorable operation, etc., achieves a green process method, reduces waste acid Hazard, operational hazard reduction effect

A technology of trimethylsilicon cyanide and halogenated trimethylsilane is applied in the field of preparation of high-efficiency trimethylsilicon cyanide, can solve problems such as environmental hazards, high cost, unfavorable operation, etc., achieves a green process method, reduces waste acid Hazard, operational hazard reduction effect

CN101250197AInactive Publication Date: 2008-08-27NANJING UNIV OF TECH
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  • Method for preparing trimethylsilylcyanation

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Experimental program
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Effect test

Embodiment 1

[0018] Embodiment 1: prepare trimethylsilyl cyanide by trimethylchlorosilane

[0019] Chlorotrimethylsilane (6.3 mL, 50 mmol), potassium ferrocyanide (19.15 g, 50 mmol), silver cyanide (0.67 g, 5 mmol), polyethylene glycol 200 (1.0 g, 5 mmol), potassium iodide (0.9 g , 5 mmol) was dissolved in N, N-dimethylformamide (250 ml), and reacted under reflux at 200° C. for 12 hours with stirring. Ethyl acetate (50-80 ml) was added, insolubles were removed by filtration, the organic phase (20 ml) was washed with water, dried over anhydrous magnesium sulfate, and 3.5 ml of trimethylsilylcyanide was obtained by rotary evaporation of the solvent.

Embodiment 2

[0020] Embodiment 2: prepare trimethylsilyl cyanide by bromotrimethylsilane

[0021] Bromotrimethylsilane (6.6 ml, 50 mmol), potassium ferrocyanide (3.83 g, 10 mmol), silver cyanide (0.2 g, 1.5 mmol), polyethylene glycol 400 (0.8 g, 2 mmol), potassium iodide (0.27 g, 1.5mmol) was dissolved in toluene (150ml), and stirred at reflux for 6 hours at 120°C. Ethyl acetate (60-90 ml) was added, insolubles were removed by filtration, the organic phase (20 ml) was washed with water, dried over anhydrous magnesium sulfate, and 5 ml of trimethylsilylcyanide was obtained by rotary evaporation of the solvent.

Embodiment 3

[0022] Embodiment 3: prepare trimethylsilyl cyanide by iodotrimethylsilane

[0023] Iodotrimethylsilane (7.1 mL, 50 mmol), potassium ferrocyanide (1.92 g, 5 mmol), silver cyanide (0.4 g, 3 mmol), polyethylene glycol 1000 (2.0 g, 2 mmol), potassium iodide (0.27 g , 1.5mmol) was dissolved in benzene (200ml), and stirred at reflux at 40°C for 2 hours. Ethyl acetate (70-100 ml) was added, insolubles were removed by filtration, the organic phase (20 ml) was washed with water, dried over anhydrous magnesium sulfate, and 6.5 ml of trimethylsilylcyanide was obtained by rotary evaporation of the solvent.

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Abstract

The invention discloses a preparation method of trimethyl silylcyanation (TMSCN), which comprises in organic solvent, using halogenated trimethyl silane and potassium ferrocyanide as raw materials and using silver cyanide-polyethylene-potassium iodide as catalyst to react for 2-12h at 40-200DEG C to prepare trimethyl silylcyanatio, wherein the mol ratio of halogenated trimethyl silane, potassium ferrocyanide, silver cyanide, polyethylene and potassium iodide is 1:0.1-1:0.01-0.1:0.01-0.1:0.01-0.1. The preparation method uses easily accessible potassium ferrocyanide as the resource of cyanide group, to avoid toxic cyanide as sodium cyanide and potassium cyanide or the like, reduce waste acid, dangerous operation and reduce the load on following treatment. The invention is simple, mild and green, which is suitable for preparing trimethyl silylcyanation in large scale.

Description

technical field [0001] The invention relates to a preparation method of high-efficiency trimethylsilyl cyanide (TMSCN). Background technique [0002] Trimethylsilylcyanide is an important intermediate in organic synthesis and an important chemical raw material, and it is widely used in many reactions, such as the corresponding selective addition reaction with aromatic aldehydes, the asymmetric addition reaction with aldehydes, especially , its nucleophilic addition to the C=O double bond is the main method to generate carbon-carbon bonds and obtain chiral cyanohydrins. As early as 1952, J.J.MCBRIDE, JR., etc. have reported the use of trimethylsilyl halide and silver cyanide as raw materials to prepare trimethylsilyl cyanide (J.J.MCBRIDE, JR.and H.C.BEACHE, J.Am.Chem.Soc, 1952, 5, 5247-5250.), this work and the similar work thereafter mostly adopt relatively expensive silver cyanide as the cyanide source, react for a long time under the condition of high temperature reflux, ...

Claims

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Application Information

Patent Timeline
27 Aug 2008
Publication
CN101250197A
IPC
C07F7/18
Inventors
李振江; 孙颖杰