CN104230975B - A kind of method preparing chlorosilane - Google Patents

Abstract

The invention discloses a method for preparing chlorosilane. In the method, arylamine hydrochloride is used as a chlorination reagent, and the hydrosilane can be chlorinated under normal temperature and pressure under the catalysis of Lewis acid. The invention has mild reaction conditions, the chlorination reagent used has little corrosion on equipment, the catalyst used does not contain heavy metal elements and does not have heavy metal pollution, and the chlorination reagent can be regenerated by introducing HCl gas into the reaction system after the reaction is completed and then recycled.

Description

A kind of method for preparing chlorosilane

technical field

The invention belongs to the technical field of synthesis of chlorosilanes, and in particular relates to a method for preparing chlorosilanes by using arylamine hydrochloride as a chlorination reagent and hydrosilane under the action of a catalyst.

Background technique

Chlorosilanes play an important role in organic synthesis as protective reagents for highly reactive hydroxyl or amine functional groups. At present, the preparation method of chlorosilane is to react hydrosilane with chlorination reagent under the catalysis of metal catalysts such as CuCl ₂ , NiCl ₂ , PdCl ₂ or Pd/C. However, these methods have certain limitations, such as higher reaction temperature, longer reaction time, and the use of expensive catalysts or toxic compounds as chlorination reagents. The method of preparing monochlorosilane by reacting HCl and silane catalyzed by aluminum trichloride also has problems such as volatility and disproportionation reaction of aluminum trichloride.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for chlorinating hydrosilane under mild conditions by using arylamine hydrochloride as the chlorination reagent and Lewis acid without heavy metal pollution as the catalyst.

The technical solution adopted to solve the above technical problems is: under the protection of an inert gas, using methylene chloride as a solvent, mix hydrosilane, arylamine hydrochloride and Lewis acid catalyst in a molar ratio of 1:1～3:0.01～0.2 Mix evenly, react at room temperature for 2-12 hours, and prepare chlorosilane.

The molar ratio of the above-mentioned hydrosilane to arylamine hydrochloride and the catalyst is preferably 1:1:0.01.

Above-mentioned arylamine hydrochloride is any one in diphenylamine hydrochloride, aniline hydrochloride, benzylamine hydrochloride, preferably diphenylamine hydrochloride or benzylamine hydrochloride; Described catalyst is Three (pentafluorophenyl) boron or triphenyl boron; Described hydrosilane is phenylsilane, diphenylsilane, triphenylsilane, triethylsilane, dichlorosilane, trichlorosilane, triethylsilane Any one of oxysilanes, preferably any one of phenylsilane, diphenylsilane, and triethylsilane.

In the present invention, arylamine hydrochloride, which is less corrosive to equipment, is used as a chlorination reagent, and Lewis acid, which does not contain heavy metal elements and has no heavy metal pollution, is used as a catalyst. The reaction conditions are mild, and hydrosilane chlorination can be realized under normal temperature and pressure. And the chlorination reagent can be regenerated and recycled by introducing HCl gas into the reaction system after the reaction is finished.

detailed description

The present invention will be further described in detail below in conjunction with the examples, but the protection scope of the present invention is not limited to these examples.

Example 1

Under the protection of argon, add 2.05g (10mmol) diphenylamine hydrochloride into 10mL dichloromethane, then add 51.2mg (0.1mmol) tris(pentafluorophenyl) boron, 1.08g (10mmol) phenylsilane, room temperature Stir the reaction for 2 hours. After the reaction is completed, HCl gas is introduced to convert diphenylamine into diphenylamine hydrochloride which is insoluble in dichloromethane. It is filtered, the solid is recovered and reused, and the filtrate is concentrated and separated by column chromatography to obtain monochlorobenzene. Silane, the yield of which is 75%, and the structural characterization data are: ¹ HNMR (400MHz, 298K, CDCl ₃ ): 5.24 (s, J=236Hz, Si-H).

Example 2

In Example 1, the amount of diphenylamine hydrochloride used was doubled, and other steps were the same as in Example 1 to obtain dichlorophenylsilane with a yield of 72%. The structural characterization data is: ¹ HNMR (400MHz, 298K, CDCl ₃ ): 5.97 (s, J=290Hz, Si-H).

Example 3

In Example 1, the phenylsilane used was replaced with equimolar diphenylsilane, and the reaction time was extended to 4 hours. Other steps were the same as in Example 1 to obtain monochlorodiphenylsilane with a yield of 77%. , the structural characterization data are: ¹ HNMR (400MHz, 298K, CDCl ₃ ): 5.75 (s, J=236Hz, Si-H).

Example 4

In Example 1, the amount of diphenylamine hydrochloride was doubled, phenylsilane was replaced with equimolar diphenylsilane, and the reaction time was extended to 12 hours. Other steps were the same as in Example 1 to obtain dichlorodiphenyl silane, the yield of which is 70%, and the structural characterization data are: ¹ HNMR (400MHz, 298K, CDCl ₃ ): 7.61 (d, o-Ph), 7.49 (t, p-Ph), 7.40 (t, m- Ph).

Example 5

In Example 1, the phenylsilane used was replaced with equimolar triphenylsilane, and the reaction time was extended to 12 hours. Other steps were the same as in Example 1 to obtain chlorotriphenylsilane with a yield of 66%. The structural characterization data are: ¹ HNMR (400MHz, 298K, CDCl ₃ ): 7.64 (d, o-Ph), 7.46 (t, p-Ph), 7.40 (t, m-Ph).

Example 6

In Example 1, the phenylsilane used was replaced with equimolar triethylsilane, and the reaction time was extended to 12 hours. Other steps were the same as in Example 1 to obtain chlorotriethylsilane with a yield of 80%. The structural characterization data are: ¹ HNMR (400MHz, 298K, CDCl ₃ ): 0.81 (t, CH ₃ ), 1.07 (m, CH ₂ ).

Example 7

In Example 1, the phenylsilane used was replaced with equimolar triethoxysilane, and the reaction time was extended to 12 hours. Other steps were the same as in Example 1 to obtain chlorotriethoxysilane with a yield of 72 %, structural characterization data: ¹ HNMR (400MHz, 298K, CDCl ₃ ): 1.26 (t, CH ₃ ), 3.91 (m, CH ₂ ).

Example 9

In Example 1, the phenylsilane used was replaced with equimolar trichlorosilane, and the reaction time was extended to 6 hours. Other steps were the same as in Example 1 to obtain silicon tetrachloride with a yield of 71%.

Example 10

In Example 1, the diphenylamine hydrochloride used was replaced with equimolar aniline hydrochloride, and other steps were the same as in Example 1 to obtain monochlorophenylsilane with a yield of 74%, and the structural characterization data were: ¹ HNMR (400MHz, 298K, CDCl ₃ ): 5.24 (s, J=236Hz, Si-H).

Example 11

In Example 1, the diphenylamine hydrochloride used was replaced with equimolar aniline hydrochloride, the phenylsilane used was replaced with equimolar diphenylsilane, and the reaction time was extended to 4 hours. Other steps were the same as in Example 1. Similarly, monochlorodiphenylsilane was obtained with a yield of 70%. The structural characterization data was: ¹ HNMR (400MHz, 298K, CDCl ₃ ): 5.75 (s, J=236Hz, Si-H).

Example 12

In Example 1, the diphenylamine hydrochloride used was replaced with equimolar aniline hydrochloride, the phenylsilane used was replaced with equimolar triethylsilane, and the reaction time was extended to 12 hours. Other steps were the same as in Example 1. Similarly, chlorotriethylsilane was obtained with a yield of 77% and structural characterization data: ¹ HNMR (400MHz, 298K, CDCl ₃ ): 0.81 (t, CH ₃ ), 1.07 (m, CH ₂ ).

Example 13

In Example 1, the diphenylamine hydrochloride used was replaced with equimolar aniline hydrochloride, and the phenylsilane used was replaced with equimolar trichlorosilane, and the reaction time was extended to 6 hours. Other steps were the same as in Example 1. Likewise, silicon tetrachloride was obtained in a yield of 73%.

Example 14

In Example 1, the diphenylamine hydrochloride used was replaced with an equimolar benzylamine hydrochloride, and the other steps were the same as in Example 1 to obtain monochlorophenylsilane with a yield of 71%. The structural characterization data For: ¹ HNMR (400MHz, 298K, CDCl ₃ ): 5.24 (s, J=236Hz, Si-H).

Example 15

In embodiment 1, the diphenylamine hydrochloride used is replaced with equimolar benzylamine hydrochloride, and the phenylsilane used is replaced with equimolar diphenylsilane, and the reaction time is extended to 4 hours. Other steps and implementation Same as Example 1, monochlorodiphenylsilane was obtained with a yield of 73%. The structural characterization data is: ¹ HNMR (400MHz, 298K, CDCl ₃ ): 5.75 (s, J=236Hz, Si-H).

Example 16

In Example 1, the diphenylamine hydrochloride used was replaced with equimolar benzylamine hydrochloride, the phenylsilane used was replaced with equimolar triethylsilane, and the reaction time was extended to 12 hours. Other steps and implementation Same as Example 1, chlorotriethylsilane was obtained with a yield of 70%, and the structural characterization data is: ¹ HNMR (400MHz, 298K, CDCl ₃ ): 0.81(t, CH ₃ ), 1.07(m, CH ₂ ) .

Example 17

In Example 1, the diphenylamine hydrochloride used was replaced with equimolar benzylamine hydrochloride, the phenylsilane used was replaced with equimolar trichlorosilane, and the reaction time was extended to 6 hours. Other steps and implementation Same as Example 1, silicon tetrachloride was obtained with a yield of 70%.

Example 18

In Example 1, the tris(pentafluorophenyl)boron used was replaced with equimolar triphenylboron, and the other steps were the same as in Example 1 to obtain monochlorophenylsilane with a yield of 73%, structural characterization The data are: ¹ HNMR (400MHz, 298K, CDCl ₃ ): 5.24 (s, J=236Hz, Si-H).

Example 19

In Example 1, the amount of diphenylamine hydrochloride used was increased by 2 times, the reaction time was extended to 8 hours, and other steps were the same as in Example 1 to obtain trichlorophenylsilane with a yield of 68%.

Example 20

In Example 1, the amount of diphenylamine hydrochloride used was increased by 2 times, the amount of tris(pentafluorophenyl) boron was increased by 19 times, and the reaction time was extended to 3 hours. Other steps were the same as in Example 1 to obtain trichloro phenylsilane, its yield was 80%.

Claims (4)

1. the method preparing chlorosilane; it is characterized in that: under inert gas shielding, with dichloromethane for solvent, hydrosilanes is mixed homogeneously for 1:1～3:0.01～0.2 in molar ratio with arylamin hydrochloric acid salt, catalyst; normal-temperature reaction 2～12 hours, prepares into chlorosilane；

Described arylamin hydrochloric acid salt is any one in diphenylamine hydrochloride, anilinechloride, and described catalyst is three (pentafluorophenyl group) boron or triphenyl borines；Described hydrosilanes is any one in phenylsilane, diphenyl silane, tri-phenyl-silane, triethyl silicane, dichloro hydrogen silicon, trichlorosilane, triethoxysilane.

2. the method preparing chlorosilane according to claim 1, it is characterised in that: the mol ratio of described hydrosilanes and arylamin hydrochloric acid salt, catalyst is 1:1:0.01.

3. the method preparing chlorosilane according to claim 1 and 2, it is characterised in that: described arylamin hydrochloric acid salt is diphenylamine hydrochloride.

4. the method preparing chlorosilane according to claim 1 and 2, it is characterised in that: described hydrosilanes is any one in phenylsilane, diphenyl silane, triethyl silicane.