JPH0768250B2 - Method for producing alkylsilyl cyanide - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an alkylsilyl cyanide. More specifically, the present invention has the general formula R _4-n Si (CN) _n (1) [wherein R represents an alkyl group, an alkenyl group or an aryl group. n represents 1 or 2. ] It is related with the manufacturing method of the alkyl silyl cyanide represented by these.

2. Description of the Related Art Alkylsilyl cyanide represented by the above general formula (1) is an important compound as a reaction reagent in the synthesis of β-aminomethyl alcohol and the synthesis of aminonitriles.

Conventionally, an alkylsilyl cyanide is represented by the general formula R _4-n Si (Cl) _n (2) [wherein R and n are the same as described above]. ] The silyl halide represented by the above formula has been produced by reacting expensive silver cyanide or toxic hydrogen cyanide, but it has a drawback as an industrial production method. In recent years, as a method that does not use silver cyanide or hydrogen cyanide, for example, a method has been proposed in which potassium cyanide is allowed to act on a silyl halide in an N-methylpyrrolidone solvent. However, this method requires the reaction to be carried out at a high temperature of around the reflux temperature of the solvent used (usually 100 ° C. or higher), and for a long time of 20 hours or longer. It is an unsuitable method for the industrial production of lucyanide.

Means for Solving the Problems An object of the present invention is to provide a method capable of producing an alkylsilyl cyanide represented by the general formula (1) under mild temperature conditions and in a short time in good yield.

According to the method of the present invention, an alkali metal cyanide supported on a macroporous polymer is added to a silyl halide represented by the general formula (2) and at least one reaction solvent selected from the group consisting of N-methylpyrrolidone and acetonitrile. A method for producing an alkylsilyl cyanide, which comprises reacting the compound in the medium to obtain an alkylsilyl cyanide represented by the general formula (1).

In the above general formulas (1) and (2), the alkyl group represented by R includes a methyl group, an ethyl group, a butyl group and the like, the alkenyl group includes a vinyl group and the like, and the aryl group includes a phenyl group and the like. To be done.

In the present invention, it is essential to use an alkali metal cyanide supported on a macroporous polymer.

As the macroporous polymer, conventionally known ones can be widely used, and examples thereof include Amberlite XAD-2, Amberlite XAD-4 (all manufactured by Rohm and Haas Co.), and Diaion HP series (manufactured by Mitsubishi Kasei Co.). be able to. Further, examples of the alkali metal cyanide include potassium cyanide, sodium cyanide and the like. The amount of the alkali metal cyanide supported is not particularly limited and can be appropriately selected within a wide range, but is usually 0.1 per 100 g of the macroporous polymer.
It is about 1.0 mol, preferably about 0.2 to 0.5 mol. The macroporous polymer carrying the alkali metal cyanide is easily produced by, for example, immersing the macroporous polymer in a water-alcohol mixed solution of the alkali metal cyanide, distilling off water and alcohol, and then drying. obtain.

The amount of the macroporous polymer on which the alkali metal cyanide is supported is not particularly limited and may be appropriately selected within a wide range, but 1 mol of chlorine atom in the silyl halide of the general formula (2) which is a general raw material is used. It is preferable to use the above-mentioned polymer in a ratio such that the alkali metal cyanide is about 1 to 4 mol, preferably about 1 to 2 mol.

The reaction of the present invention is carried out in at least one reaction solvent selected from the group consisting of N-methylpyrrolidone and acetonitrile. The reaction of the present invention normally proceeds suitably at a low temperature of about 25 to 60 ° C., and generally the reaction is completed in a short time of about 0.5 to 6 hours.

After the completion of the above reaction, the target compound can be isolated and purified by passing the solid content, washing the solid with a solvent such as benzene or methylene chloride, and then distilling off the solvent and distilling or recrystallizing.

Effect of the Invention According to the method of the present invention, the desired alkylsilyl cyanide of the general formula (1) can be produced in good yield under a mild reaction temperature and in a short time.

Examples The present invention will be further clarified with reference to the following examples.

Reference Example 1 1.47 g (30 mmol) of sodium cyanide was dissolved in about 5 ml of water, and then about 50 ml of methanol was added. 7.5 g of Amberlite XAD-4 (manufactured by Organo Corporation) was added to this solution, water and methanol were distilled off at about 50 ° C under an aspirator, and further dried under reduced pressure (0.1 mmHg) at 90 ° C for 4 hours. Thus, 7.5 g of Amberlite XAD-4 carrying 1.47 g of sodium cyanide was obtained.

Example 1 A mixture of sodium cyanide (1.47 g, 30 mmol), trimethylsilyl chloride (2.60 g, 24 mmol) and N-methylpyrrolidone (20 ml) supported on Amberlite XAD-4 (7.5 g) at 25 ° C. Stir for 0.5 hours. After passing the solid content, thoroughly wash the solid content with methylene chloride,
Combined with liquid. Toluene was added to this solution as an internal standard and quantified by gas chromatography. As a result, the production rate of trimethylsilyl cyanide was 94%.

Reference Example 2 1.95 g (30 mmol) of potassium cyanide was dissolved in about 5 ml of water, and then about 50 ml of methanol was added. 7.5 g of Amberlite XAD-4 (manufactured by Organo Corporation) was added to this solution, water and methanol were distilled off at about 50 ° C under an aspirator, and further dried under reduced pressure (0.1 mmHg) at 90 ° C for 4 hours. Thus, 7.5 g of Amberlite XAD-4 carrying 1.95 g of sodium cyanide was obtained.

Example 2 A mixture of potassium cyanide (1.95 g, 30 mmol), tert-butyldimethylsilyl chloride (2.26 g, 15 mmol) and acetonitrile (40 ml) supported on Amberlite XAD-4 (7.5 g) at 60 ° C. Stir for hours. After passing the solid content, remove the solid content from methylene chloride-benzene (1: 2) 1
It was thoroughly washed with 00 ml and combined with the liquid. Toluene was added to this solution as an internal standard and quantified by gas chromatography. As a result, the production rate of tert-butyldimethylsilyl cyanide was 95%. After distilling off the solvent, the residue was distilled under reduced pressure to obtain 1.70 g (yield 80%) of tert-butyldimethylsilyl cyanide having a boiling point of 77 to 79 ° C./45 mmHg.

A corresponding alkylsilyl cyanide was obtained in the same manner as in Example 2 except that the silyl halides and alkali metal cyanides shown in Table 1 below were used and the reaction was performed at a predetermined temperature for a predetermined time. The production rate of alkylsilyl cyanide is also shown in Table 1.

Claims (1)

[Claims] 1. A general formula R _4-n Si (Cl) _n [wherein R represents an alkyl group, an alkenyl group or an aryl group]. n represents 1 or 2. ] The silyl halide represented by the following formula is reacted with an alkali metal cyanide supported on a macroporous polymer in at least one reaction solvent selected from the group consisting of N-methylpyrrolidone and acetonitrile to give a compound represented by the general formula R _{4- n} Si (CN) _n [wherein R and n are the same as defined above]. ] The manufacturing method of the alkyl silyl cyanide characterized by obtaining the alkyl silyl cyanide represented by these.