JPH07196670A - Trissilylmethane and its preparation - Google Patents

Abstract

PURPOSE: To provide new trissilylmethanes as starting substances useful in preparing silicon compounds having various organic functional groups by the addition reaction to organic compounds having an unsaturated bond.

CONSTITUTION: These compounds are represented by formula I (wherein R₁, R₂ and R₃ are each methyl or chlorine; and R₄ and R₅ are each -SiHCl₂ or -SiCl₃) and include, e.g. 1,1,3-tri-chloro-3-methy-2-(dichlorosilyl)-1,3-disilabutane. Further, the compound of formula I can be obtained, e.g. by reacting a compound of formula II and a compound of formula III (wherein R is H, a lower alkyl or -CH₂CH₂Cl) with a metallic silicon in the presence of a copper catalyst.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to trissilylmethanes and a method for producing the same.

[0002]

2. Description of the Related Art Since a method for reacting metallic silicon and an organic halogen compound in the presence of a copper catalyst to produce methylchlorosilanes was introduced in US Pat. No. 2,380,995, the silicon industry is in use today. Is based on this technology.

Si + 2CH ₃ Cl → (CH ₃ ) ₂ SiCl ₂

In the above reaction, not only dimethyldichlorosilane but also products such as methyltrichlorosilane, trimethylchlorosilane and tetrachlorosilane are obtained. In addition to these, a small amount of substances with high boiling points can be obtained, and since the composition of the product is a complicated reaction that varies depending on the reaction conditions,
In order to effectively obtain the main product, dimethyldichlorosilane, the reaction conditions such as the purity of the starting material, the type of catalyst, the amount used, the cocatalyst, the reaction temperature, the reaction pressure, the form of the reaction tank used, etc. are taken into consideration. Must.

In the direct reaction of metallic silicon and organic chloride, it is known that the reaction does not proceed well unless a catalyst is used, and copper is known as the best catalyst. In some cases, metals such as zinc, aluminum and cadmium may be used as cocatalysts. The co-catalyst shortens the reaction initiation time and enhances the selectivity of dimethyldichlorosilane formation in the product (EG Rachow, J. Am. Che.
m. Soc., 67, 963 (1945)). If the amount of copper catalyst used is increased, the reaction becomes faster, but the chlorine content in the product tends to increase. Therefore, in the reaction between silicon and methyl chloride, about 10% of copper based on the weight of silicon must be used as a catalyst.

Copper used as a catalyst includes metallic silicon and η
- shaped Cu ₃ to form a silicon-bonded Si, but this η- shaped Cu ₃ Si have been reported to react with an organic chloride (VS Fikhtengolts and AL Klebanskii, J. Ge
n. Chem. USSR, 27, 2535 (1957)), η-like Cu ₃
As a method for forming Si, a physical method of heating copper and silicon to 800 to 1,100 ° C. under an inert gas [P. Trambouze, and B. Imelik, J. Chim. Phys., 51,
505 (1954)] and a chemical method of reacting cuprous chloride with silicon [(RJH Voorhoeve and JC Ulugter,
J. Catalysis, 4,129 (1965)] is known.

NSi + CuCl → SiCl ₄ + Cu ₃
Si + Cu + (n-2) Si

The reaction between silicon and methyl chloride is 30
Since it is an exothermic reaction that occurs at high temperatures above 0 ° C, if the reaction heat cannot be effectively removed, the reactants will solidify and form a partial superheated state [AL Klibam Skii and VS
Fikhtengolts, J. Gen. Chem. USSR, 27, 2693 (19
57)]. If the reaction temperature is higher than the appropriate temperature, the amount of desired dimethyldichlorosilane produced decreases, side reactions occur frequently, and methyl chloride or a product as a starting material is decomposed to deposit carbon on the surface of silicon. This drastically reduces the activity of silicon [JC Vlugter, and RJH Voo
rhoeve, Conf.Accad, Lin cei, Alta Tech. Chim. 1961
P. 81 (1962)]. Therefore, in order to synthesize dimethyldichlorosilane by the direct method, it is extremely important to control the reaction temperature.

The form of the reaction vessel used in the direct method includes a fixed type, a stirring type and a flow type reaction vessel. The stirring type reaction tank has better reactivity than the fixed type reaction tank because the temperature can be controlled more easily and the solid particles collide with each other to renew the surface. Copper, which is used as a catalyst, has a density about 3 times higher than that of metallic silicon, which is a reactant, and it is very difficult to effectively mix two metals. In order to solve these difficulties, a method has been introduced in which a spiral stirrer is used, and the solid at the bottom is pumped up and the organic chloride is blown up in the gaseous state from below (JE Sellers a
nd JL Davis, U.S. Pat. No. 2,449,821).
However, this process requires the reaction of highly corrosive organic chlorides at a high temperature, making it difficult to find a corrosion-resistant stirrer suitable for this, and it is not suitable for mass production and continuous production. As a process for compensating for such drawbacks, a fluidized type reaction vessel has been developed in which methyl chloride is blown up from the bottom of the reaction vessel and reacted while fluidizing silicon and a copper catalyst (BA Bluestrin, US Pat. No. 2,887, 502
issue). This method is widely used in the production of methylchlorosilanes because it can effectively remove the heat of reaction.

[0010] In 1958, Petrov and his collaborators reported for the first time that silanes having a dichloromethyl group could be directly reacted with metallic silicon to synthesize various silaalkanes [AD Petrov, SI Sadykh-Z
ade, EA Chernyshev, and VF Mironov, Zh, Obshe
h. Khim, 26, 1248 (1956)]. However, reacting dichloromethyltrichlorosilane with silicon at 360 ° C. yields only 14% tris (trichlorosilyl) methane,
About 70% was a by-product generated by decomposition of the starting material. However, it is reported that when bis (trichlorosilyl) dichloromethane is reacted with silicon, the expected tetrakissilylmethane compound is not obtained, but only a compound or the like is obtained by decomposition of the starting material.

[0011] After that, Muller and his collaborators also showed that when bis (trichlorosilyl) dichloromethane was reacted with silicon, the expected tetrakissilylmethane compound was not obtained, and only the compound by decomposition of the starting material was obtained. Reported that [R. Muller and H. Beyer, Che
m. Ber., 92, 1957 (1959); 96, 2894 (1963)].

The present inventors use a fluidized reaction vessel or directly in a reaction vessel having a spiral stirrer to directly react silanes having a chloromethyl group with silicon. The reaction temperature was adjusted to 350 ° C. or lower, and the reaction was carried out while maintaining the copper catalyst so as not to exceed about 10% and 15% to obtain trissilylmethanes as a main product and some bissilylmethane as a by-product. It was When 5 to 50% of the spherical fine powdery acid clay is used to assist the fluidization, the fluidization is better and the reactivity of silicon and the selectivity of the product are better. Good results (IN Jung, G. -H. Lee, SH Yeon and M. -Y.
Suk, US Pat. No. 5,075,477).

[0013]

[Chemical 3]

In the above formula, R ₁ , R ₂ and R ₃ each represent a methyl group or a chlorine atom.

The present inventors, when hydrogen chloride is used together in the reaction of chlorosilanes (I) having a chloromethyl group with silicon metal, bis (silyl) methane having a dichlorosilyl group and trichloromethane are used. It was found that bis (silyl) methanes having a silyl group can be obtained at the same time. In this reaction, the same result could be obtained by using an alkyl chloride capable of decomposing at the reaction temperature to produce hydrogen chloride instead of hydrogen chloride. Examples of this alkyl chloride include 1,2-dichloroethane,
Propyl chloride, n-butyl chloride, t-butyl chloride, etc. are available (Korean Patent Application No. 91-2424).
3).

[0016]

[Chemical 4]

In the formula, R ₁ , R ₂ and R ₃ each represent a methyl group or a chlorine atom.

The inventors of the present invention, in the above reaction, use methylene chloride together with hydrogen chloride instead of reacting silanes having a chloromethyl group, and thus bis (silyl) having dichlorosilyl groups on both sides of the molecule. It was found that methane and bis (silyl) methane having a trichlorosilyl group and bis (silyl) methane having a trichlorosilyl group on one side and a dimethylsilyl group on a different side can be simultaneously obtained [Korean Patent Application No. 92-935 (9
2.1.23)].

[0019]

[Chemical 5]

[0020]

DISCLOSURE OF THE INVENTION The present inventor has made a compound of the general formula (II) a source of hydrogen chloride in reacting a silicon compound with a silane compound of the general formula (I) having a dichloromethyl group. When used together as general formula (IV),
We have found that tris (silyl) methanes of (V) and (VI) can be obtained.

That is, in the present invention, a mixture of a silane compound having a dichloromethyl group of the general formula (I) and hydrogen chloride of the general formula (II) or an alkyl chloride or the like which generates hydrogen chloride at a reaction temperature is treated with a copper catalyst. Directly reacts with metallic silicon in the presence of tris (silyl) methane having two dichlorosilyl groups of general formula (IV), having one dichlorosilyl group of general formula (V) and one trichlorosilyl group The present invention relates to a production method for simultaneously producing tris (silyl) methane and tris (silyl) methane having two trichlorosilyl groups of the general formula (VI).

[0022]

[Chemical 6]

In the formula, R is a hydrogen atom or an alkyl group (C _1-
C ₄₎ or a -CH ₂ CH ₂ Cl group, respectively R _1, R ₂ and R ₃ are a methyl group or a chlorine atom.

Examples of the compound represented by the general formula (II) include:
1,2-dichloroethane, propyl chloride, n-butyl chloride, t-butyl chloride and the like. Especially when hydrogen chloride is used or when an alkyl chloride such as butyl chloride which decomposes easily at the reaction temperature to generate hydrogen chloride is used together, tris (silyl) having two dichlorosilyl groups represented by the general formula (IV) is used. ) Obtaining methane as the main product,
When used together with an alkyl chloride such as 1,2-dichloroethane which easily decomposes to generate hydrogen chloride, tris (silyl) methane having two trichlorosilyl groups of the general formula (VI) is obtained as a main product. be able to.

The dichloromethylsilane compound of the general formula (I) and the hydrogen chloride or alkyl chloride of the general formula (II) are mixed in the gaseous state before reacting with the metal silicon, or the compound of the general formula (I) is mixed. General formula (I
It is also possible to spray into the compound of I) and mix. The two compounds can be mixed in any ratio by weight or by volume. However, the higher the proportion of general formula (II), the higher the proportion of general formula (IV) in the product.
If it is desired to increase the production ratio of the compound of the general formula (IV) having a bond of silicon and hydrogen, the number of moles of the general formula (II) to be mixed is 0.1 to 6. Although 0 mol can be used, 3 to 5 mol is suitable.

The reaction vessel used in the present invention is preferably a stirring type or fluidized type reaction vessel, and it is possible to carry out the reaction continuously even in a batch system.

As the metal silicon, industrial silicon can be used, but if its purity is 95% or more, it can be used.
It is preferably 98% or more. Suitable size of silicon powder suitable for the reaction is 1 to 200 micron powder, but the selection of suitable size and distribution of silicon powder can be varied according to the size and shape of the reaction vessel. 20 to 200 if a fluidized reactor is used
Powders up to micron are suitable.

The reaction temperature can be from 200 ° C to 360 ° C, preferably 250 to 350 ° C, more preferably 260 ° C to 320 ° C. The reaction pressure can be from atmospheric pressure to 5 atm, and the reaction rate can be increased by increasing the pressure.

The catalyst may be metallic copper or a copper compound capable of liberating copper under the reaction conditions. Copper usage is 1
% To 20% can be used, but 5 to 10% is preferable. Other than copper catalyst, 0.001 relative to the weight of copper
% To 5% co-catalyst can be used to speed up the reaction or increase the selectivity for specific products. Examples of suitable cocatalysts for this reaction include, but are not limited to: calcium,
It is possible to use metals such as zinc, cadmium, manganese, magnesium, silver and chromium, and metal compounds capable of producing this metal under reaction conditions.

[0030]

INDUSTRIAL APPLICABILITY The tris (silyl) methanes having a chlorohydrosilyl group of the present invention are useful for the addition reaction of an organic compound having an unsaturated bond to produce silicon compounds having various organic functional groups. It is a raw material.

[0031]

The following examples serve to explain the present invention in more detail, but the present invention is not limited thereto.

Example 1. Preparation of Si / Cu contact mixture (I) 360 g (100 to 325 mesh) of metallic silicon and 62.3 mg of cuprous chloride (CuCl) were placed in a reaction vessel, the temperature of the reaction vessel was raised to 250 ° C., and then dried nitrogen was added. About 2
Allowed to dry for hours. After drying, if the temperature of the reaction vessel is raised to 370 ° C., tetrachlorosilane is produced as the reaction product, and as a result, a highly active Si / Cu contact mixture is produced. After maintaining at this temperature for about 3 hours to form a contact mixture, the reaction product tetrachlorosilane was collected. When using cadmium, tin, zinc, etc. as a co-catalyst other than copper, which is the main catalyst, open the upper part of the reaction tank after the formation of the contact mixture is completed, add the necessary amount of co-catalyst, and stir. And mixed well and reacted.

Example 2. Preparation of Si / Cu contact mixture (II) 360 g (100-325 mesh) of metallic silicon and 40 of copper catalyst
g was placed in a reaction tank and dried under the conditions of Example 1. After drying, if the temperature of the reaction tank is raised to 350 ° C. and methyl chloride is blown through the preheating tube at the bottom of the reaction tank, some water will be generated in the initial stage, and after 40 to 70 minutes, the reaction will be generated. Dimethyldichlorosilane and methyltrichlorosilane start to form as a substance and are collected in a receiving flask.
These start to be produced, that is, evidence that a Si / Cu contact mixture has been produced. After reacting with methyl chloride for about 2 hours, the methyl chloride supply was interrupted and the reaction product in the receiving flask was taken out. It was When a cocatalyst was required for the reaction, it was charged by the method as described in Example 1 and reacted.

Si / Cu contact mixtures having different catalyst compounding ratios were prepared and used. Their compositions are shown in Table 1.

[0035]

[Table 1]

Example 3. Reaction of 1: 4 Mixed Gas of Dichloromethyldimethylchlorosilane and Hydrogen Chloride with Metallic Silicon In this example, Experiment No. 3 is a typical example. Example 2
Sample No. I-3 Si / Cu contact mixture 40 prepared in
2g was put in a stirred reaction tank, the temperature of the reaction tank was raised to 280 ° C, dichloromethyldimethylchlorosilane was put in the syringe pump at the bottom of the reaction tank, and while blowing nitrogen gas at a rate of 200ml / min, hydrogen chloride was simultaneously added. To 200 ml / min
And silane at a rate of 20.0 ml / hr. One minute after the start of the reaction, a temperature rise due to the exothermic reaction was observed, and reaction products began to collect in the receiving flask installed in the upper part of the reaction tank. While continuously maintaining such conditions, the reaction product was taken out every 30 minutes and the amount of dichloromethyldimethylchlorosilane used during 2 hours was 49.5 g, and the reaction product taken out was 78.6 g.
It was g. The reaction product generated here is a gas chromatograph (packed column, 5% SE-54, 0.9m × 1/8 ″ OD,
It analyzed by using SS, TCD) and each component was fractionally distilled and its structure was confirmed by the nuclear magnetic resonance spectroscopy.

The composition of the reaction product produced here is 1,
1,3-trichloro-3-methyl-2- (dichlorosilyl) -1,3-disilabutane (general formula IV) 43.3 g (5
5.1%) [NMR (CDCl ₃ ), δ, 5.81 (d, 2H, Si-H), 1.2
4 (s, 1H, -CH =), 0.75 (s, 6H, -CH ₃ )], 1,1,3
-Trichloro-3-methyl-2- (trichlorosilyl)
-1,3-disilabutane (general formula V) 14.5 g (18.
5%) [NMR (CDCl ₃ ), δ, 5.85 (s, 1H, Si-H), 1.53 (s,
1H, -CH =), 0.79 (s, 6H, -CH ₃ )]; and 1,1,
1.4 g of 1,3-tetrachloro-3-methyl-2- (trichlorosilyl) -1,3-disilabutane (general formula VI)
(1.8%) [NMR (CDCl ₃ ), δ, 1.74 (s, 1H, -CH =), 0.8
_{3 (s, 6H, -CH 3} ) ] was obtained. As these other by-products, chloromethyldimethylchlorosilane produced by reducing the starting silane with hydrogen chloride reacts,
1,3-trichloro-3-methyl-1,3-disilabutane and 1,1,1,3-tetrachloro-3-methyl-1,
3-disilabutane was also produced at 10.7% and 1.2%, respectively. In 12.7% of other by-products, trichlorosilane was 5.7%, tetrachlorosilane was 0.8%, and trimethylchlorosilane was 1.0%, and the rest was an unidentified substance.

The same reactants, reaction tanks, catalysts,
The composition of the reaction product obtained by changing only the reaction temperature in the presence of the cocatalyst is shown in Table 2.

[0039]

[Table 2]

Example 4. Reaction of mixed gas of dichloromethyldimethylchlorosilane and hydrogen chloride with metallic silicon The reaction mixture of Example 3 was used and reacted in the same form of reaction vessel, the same reaction conditions and a reaction temperature of 320 ° C., but with hydrogen chloride. The reaction was carried out with different molar ratios of dichloromethyldimethylchlorosilane. Table 3 shows the composition of the reaction products obtained with different molar ratios. In Table 3, experiment number 10 is 5 for acid clay to contact mixture.
It is the result of reaction using 20.0 g which is%.
In this reaction, when the contact mixture is consumed about 20%,
The same result was obtained when the exhausted amount of activated contact mixture was added and reacted.

[0041]

[Table 3]

Example 5. Reaction of Mixed Gas of Dichloromethyldimethylchlorosilane and Hydrogen Chloride with Metallic Silicon A contact mixture of Table 2 shown in Example 1 was prepared, and Example 3 was prepared.
No. 3 of Experiment No. 3 except for the type of the contact mixture, the other reaction conditions were all the same, and the composition of the obtained reaction product is shown in Table 4.

[0043]

[Table 4]

Example 6. Reaction of Mixed Gas of Dichloromethyldimethylchlorosilane and Alkyl Chloride with Metallic Silicon This example is a typical example of Experiment No. 26 in Table 5.
A contact mixture of Sample No. I-3 of Example 2 was prepared and the reaction starting material was dichloromethyldimethylchlorosilane 6
6.6 g (0.375 mole) and t-as hydrogen chloride source
Butyl chloride (138.7 g, 1.500 mole) was mixed to prepare a mixture having a molar ratio of 1: 4. These mixtures were reacted at a reaction temperature of 280 ° C. under nitrogen gas (200 ml / min).
The mixture was allowed to flow into the reaction vessel at a rate of 4 ml / hr and reacted for 2.0 hours to obtain 83.8 g of a reaction product.

The composition of this reaction product is 1,1,3-trichloro-3-methyl-2- (dichlorosilyl) -1,
3-Disilabutane (general formula IV) 36.2 g (43.2)
%); 1,1,3-dichloro-3-methyl-2- (trichlorosilyl) -1,3-disilabutane (general formula V)
9.1 g (10.8%); and 1,1,1,3-tetrachloro-3-methyl-2- (trichlorosilyl) -1,
The amount of 3-disilabutane (general formula VI) was 1.8 g (2.1%). Other by-products include 1,1,3-trichloro-3-methyl-1,3-disilabutane 9.8%, 1,
There were 2.1% 1,1,3-tetrachloro-3-methyl-1,3-disilabutane, 6.3% trichlorosilane and 0.8% tetrachlorosilane, and there was no unreacted starting material.

Further, in this reaction, the gas component that escaped to the outside without being condensed by the condenser during the reaction was isobutene produced by the decomposition of t-butyl chloride at a high temperature to generate hydrogen chloride. The same result was obtained by reducing the amount of t-butyl chloride used by half and using only that amount of hydrogen chloride.

Table 5 shows a mixed gas of dichloromethyldimethylchlorosilane and various alkyl chlorides and metallic silicon.
The composition of the reaction product obtained by reacting under different reaction conditions is shown.

[0048]

[Table 5]

Example 7. Reaction of mixed gas of dichloromethyldimethylchlorosilane with alkyl chloride or hydrogen chloride and metallic silicon using fluidized reactor Using the fluidized reactor mentioned above, contact of sample No. I-3 of Example 2 After 402 g of the mixture was put into the reaction vessel and the temperature of the reaction vessel was raised to 280 ° C., a mixture of silane and hydrogen chloride, which was a reaction starting material, in a molar ratio of 1: 4 was introduced into the reaction vessel through a preheating tube installed at the bottom of the reaction vessel. Let it flow. At this time, in order to help the fluidization of metallic silicon, dry nitrogen gas is added to about 2
Flowed with reactants at a rate of 00 ml / min. 2.
The amount of the reaction product obtained through the reaction for 0 hours was 55.
4 g, and the dichloromethyldimethylchlorosilane used in the reaction was 49.5 g. The results of confirming the compositions of these reaction products are as shown in Table 6, and it was found that a large amount of the starting material silane was also recovered. The experiments in Table 6 all used a fluidized reactor and the same reaction temperature,
The reaction was performed using the same contact mixture, the molar ratio of the hydrogen chloride source to the silane was 1: 4, and Experiment No. 33 was under the same conditions as Experiment No. 32, but the pressure in the reaction vessel was 3 kg. This is the result of increasing the reaction to / cm ² and reacting.

[0050]

[Table 6]

Example 8. Reaction of mixed gas of dichloromethylmethyldichlorosilane and hydrogen chloride with metallic silicon A contact mixture of sample No. I-3 of Example 2 was prepared, and 55.3 g of dichloromethylmethyldichlorosilane and hydrogen chloride were mixed at a 1: 4 molar ratio. To the reaction conditions of Example 3 and 28
The reaction was carried out at a reaction temperature of 0 ° C. for 2.0 hours to obtain 81.6 g of the reaction product.

As a result of confirming the composition of the reaction product, 1,
1,3,3-tetrachloro-2- (dichlorosilyl)-
1,3-disilabutane (general formula IV) 45.7 g (56%)
(NMR (CDCl ₃ ), δ, 5.84 (s, 2H, Si-H), 1.56 (s, 1H,-
CH =), 1.10 (s, 3H, -CH 3) ]; 1,1,1,3-tetrachloro-2- (trichlorosilyl) -1,3 disilabutane (Formula V) 14.3 g (17. 5%) [NMR (CDC
l ₃ ), δ, 5.88 (s, 1H, Si-H), 1.83 (s, 1H, -CH =), 1.1
3 (s, 3H, -CH ₃ )]; and 1,1,1,3,3-pentachloro-2- (trichlorosilyl) -1,3-disilabutane (general formula VI) 1.8 g (2.2%) ) [NMR (CDCl ₃ ),
δ, 2.10 (s, 1H, Si-H), 1.16 (s, 3H, -CH ₃ )] were obtained. Other by-products include 11.0% 1,1,3,3-tetrachloro-1,3-disilabutane, and 1,
1.3% of 1,1,3,3-pentachloro-1,3-disilabutane was produced. In addition to that, trichlorosilane is 2.
2%, and tetrachlorosilane 0.4%, the remaining 9.4% were various unidentified substances.

Example 9. Reaction of mixed gas of dichloromethyltrichlorosilane and hydrogen chloride with metallic silicon A contact mixture of Sample No. I-3 of Example 2 was prepared, and 60.8 g of dichloromethyltrichlorosilane and hydrogen chloride were mixed at a ratio of 1: 4. At 2.0 under the reaction conditions of Example 8.
After reacting for 8 hours, 82.4 g of the reaction product was obtained.

As a result of confirming the composition of the reaction product, 1,
3,9.6 g of 1,1,3,3-pentachloro-2- (dichlorosilyl) -1,3-disilapropane (general formula VI)
(48.0%) [NMR (CDCl ₃ ), δ, 5.87 (s, 2H, Si-H),
1.83 (s, 1H, -CH =)]; 1,1,1,3,3-pentachloro-2- (trichlorosilyl) -1,3-disilapropane (general formula V) 11.1 g (13.5%) (NMR (CDC
l ₃ ), δ, 5.89 (s, 1H, Si-H), 2.10 (s, 1H, -CH =)];
And 1,1,1,3,3,3-hexachloro-2-
2.1 g (2.6%) of (trichlorosilyl) -1,3-disilapropane (general formula VI) [NMR (CDCl ₃ ), δ, 2.37 (s,
1H, -CH =)] was obtained. 1, as other by-products
1,1,3,3-Pentachloro-1,3-disilapropane was produced at 13.6% and 1,1,1,3,3,3-hexachloro-1,3-disilapropane was produced at 3.3%. In addition, trichlorosilane was 7.1%, tetrachlorosilane was 0.9%, and the remaining 11.0% was various unidentified substances.

Example 10. Reaction of a mixed gas of dichloromethyltrimethylsilane and hydrogen chloride with metallic silicon A contact mixture of sample No. I-3 of Example 2 was prepared, and 41.6 g of dichloromethylmethyldichlorosilane and hydrogen chloride were mixed in a 1: 4 molar ratio. The mixture was stirred under the reaction conditions of Example 8.2.
After reacting for 0 hour, 72.1 g of the reaction product was obtained.

As a result of confirming the composition of the reaction product, 1,1
-Dichloro-3,3-dimethyl-2- (dichlorosilyl) -1,3-disilabutane (general formula VI) 38.3 g (5
3.1%) [NMR (CDCl ₃ ); δ, 5.74 (s, 2H, Si-H), 0.8
1 (s, 1H, -CH = ), 0.35 (s, 9H, -CH 3) ]; 1,1-dichloro-3,3-dimethyl-2- (trichlorosilyl) -
7.1 g (9.9%) of 1,3-dilabtan (general formula V)
(NMR (CDCl ₃ ), δ, 5.77 (s, 1H, Si-H), 1.10 (s, 1H,-
CH =), 0.39 (s, 9H, -CH 3) ]; and 1,1,1-trichloro-3,3-dimethyl-2- (trichlorosilyl)
-1,3-disilabutane (general formula VI) 0.6% [NMR (CD
Cl ₃ ), δ, 1.39 (s, -CH =), 0.43 (s, 9H, -CH ₃ )] were obtained. Other by-products include 2,2,4-trichloro-
7.5 g (10.4%) of 3- (dichlorosilyl) -4-methyl-2,4-disilapentane [NMR (CDCl ₃ ), δ, 5.84
(s, 1H, Si-H), 1.22 (s, 1H, -CH =), 1.06 (s, 3H, -C
_{H 3); 0.76 (s,} 6H, -CH 3) ]; 1,1-dichloro-3,3
12.3% dimethyl-1,3-disilabutane and 1,1,1-trichloro-3,3-dimethyl-1,3
-1.0% disilabutane was produced. Other than that, trichlorosilane is 3.0% and tetrachlorosilane is 0.
3% and the remaining 9.4% were various unidentified substances.

Claims (19)

[Claims] 1. A compound of general formula (III). [Chemical 1] In the above formula, R ₁ , R ₂ and R ₃ all represent a methyl group; R ₁ represents a methyl group and R ₂ and R ₃ represent a chlorine atom; or R ₁ represents a chlorine atom, R _{1 2} and R ³ represent a methyl group. R ₄ and R ₅ represent a —SiHCl ₂ group; R ₄ represents a —SiHCl ₂ group, and R ₅ represents —SiCl
₃ groups or R ₄ and R ₅ represent a —SiCl ₃ group. 2. A mixed gas of a compound represented by the general formula (I) and a compound represented by the general formula (II) is reacted with metallic silicon in the presence of a copper catalyst to give a compound represented by the general formula (IV), ( A method for producing the compounds represented by V) and (VI). [Chemical 2] In the above formula, R ₁ , R ₂ and R ₃ each represent a methyl group or a chlorine atom, and R represents a hydrogen atom, a lower alkyl group or-
A CH ₂ CH ₂ Cl group is shown. 3. The method according to claim 2, wherein R ₁ , R ₂ and R _{3 in the} general formula (I) are all methyl groups. 4. R _{1 of the} general formula (I) is a methyl group,
The method according to claim 2, wherein R ₂ and R ₃ are chlorine atoms. 5. The process according to claim _2, wherein R ₂ and R _{3 in} the general formula (I) are methyl groups and R ₁ is a chlorine atom. 6. The method according to claim 2, wherein R ₁ , R ₂ and R _{3 in the} general formula (I) are all chlorine atoms. 7. The method according to claim 2, wherein the compound of the general formula (II) is hydrogen chloride. 8. The method according to claim 2, wherein R in the general formula (II) is a propyl group. 9. The method according to claim 2, wherein R in the general formula (II) is an n-butyl group. 10. The method according to claim 2, wherein R in the general formula (II) is a t-butyl group. 11. The method according to claim 2, wherein R in the general formula (II) is a 2-chloroethyl group. 12. An alkyl chloride of the general formula (II)
The production method according to claim 2, wherein the silane having a dichloromethyl group of the general formula (I) is mixed and reacted at a molar ratio of 0.5 to 6 times. 13. The process according to claim 2, wherein the compound of general formula (II) is a mixture of hydrogen chloride and another compound of general formula (II) in a molar ratio of 1: 1. 14. The method according to claim 2, wherein the reaction is carried out in a fluidized reaction tank or a reaction tank equipped with a spiral stirrer. 15. The method according to claim 2, wherein the reactants are reacted under a pressure of 1 to 5 atmospheres. 16. A spherical fine powdery acid clay is added in an amount of 1 to 50% with respect to the weight of metallic silicon, and the mixture is reacted.
Manufacturing method. 17. A catalyst comprising, as a catalyst, metallic copper or a copper compound which produces copper under the reaction conditions in a weight ratio of 1 to the reaction substance.
20% is added and it is made to react at 250-350 degreeC.
Manufacturing method. 18. Calcium, titanium, cadmium,
18. The production method according to claim 17, wherein at least one promoter selected from tin, zinc, silver, magnesium, manganese, chromium and metal compounds thereof is added and reacted in an amount of 0.001 to 5% of the whole reaction solid. 19. The method according to claim 2, wherein when the Si / Cu contact mixture reacts and its amount is consumed, only the consumed amount of the Si / Cu contact mixture is additionally reacted.