JP3052841B2 - Texyl dimethylchlorosilane and triorganochlorosilane co-production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for co-producing and producing texyldimethylchlorosilane and triorganochlorosilane.

[0002]

2. Description of the Related Art Texyldimethylchlorosilane is a silylating agent for protecting a protic functional group such as a hydroxyl group, an amino group, a carboxyl group, an amide group or a mercapto group in various organic syntheses. It is a compound that is useful in organic synthesis under severe reaction conditions, especially since it has a very bulky texyl group.

On the other hand, triorganochlorosilane compounds,
For example, trimethylchlorosilane, triethylchlorosilane, tert-butyldimethylchlorosilane and the like are also used in a wide range of fields as silylating agents, and are also used for hydrophobicizing inorganic substances and for introducing end block units into organopolysiloxane chains. I have.

Conventionally, as a method for producing texyldimethylchlorosilane, only a method of reacting dimethylchlorosilane with tetramethylethylene in the presence of an aluminum catalyst (see Japanese Patent Publication No. 3-22880) is known.

However, in this reaction, dimethylchlorosilane used as a raw material is not only very expensive, but also has a low boiling point of 35 ° C. and a very high reactivity, so that it is difficult to handle. there were.

Conventionally, as a method of obtaining trimethylchlorosilane by a method other than the direct method, a method of synthesizing by reacting with dimethyldichlorosilane, methyltrichlorosilane, or tetrachlorosilane using a Grignard reagent is generally used. In this method, by-products of tetramethylsilane are large, and it is impossible to almost selectively obtain only trimethylchlorosilane. Therefore, a complicated operation of separating and purifying from various methylsilanes after completion of the reaction was required.

Further, Z. Anorg. Allgem. C
hem. In 287.273 (1956), the methylation reaction of tetrachlorosilane or methyltrichlorosilane is attempted using methylaluminum sesquichloride. However, since this method can be obtained as a mixture of various methylsilanes, various methylsilanes can be obtained after the reaction. A complicated operation of separating and purifying trimethylchlorosilane from methane was required.

In Japanese Patent Publication No. 57-30114, trimethylchlorosilane is obtained at a composition ratio of 81.7% by passing methylhydrogenchlorosilane and methylchloride at 180 to 450 ° C. in metallic aluminum. However, this method has a serious danger that high-temperature conditions are required and aluminum chloride as a by-product is easily clogged in a flow system.

Further, a method for obtaining trimethylchlorosilane from tetramethylsilane as a raw material by passing hydrogen chloride gas in the presence of a Friedel-Crafts catalyst (JP-A-56-92)
895) and a method of obtaining trimethylchlorosilane by a partition reaction between tetramethylsilane and dimethyldichlorosilane in the presence of a Friedel-Crafts catalyst (JP-A-55-61195). In order to obtain methylsilane, a previous-stage synthesis reaction was required, and a combination of two-stage synthesis processes was required, resulting in poor efficiency.

On the other hand, triethylchlorosilane and t-butyldimethylchlorosilane are synthesized by chlorinating triethylsilane and t-butyldimethylsilane with chlorine. However, in this case, the hydrogen atoms are lost as hydrogen chloride and are not effectively used at present.

Accordingly, texyldimethylchlorosilane,
It is desired to develop an industrially advantageous method for producing triorganochlorosilane.

The present invention has been made in view of the above circumstances,
It is an object of the present invention to provide a method for co-production of dimethylchlorosilane and triorganochlorosilane, which can simultaneously synthesize texyldimethylchlorosilane and triorganochlorosilane at low cost, easily and without risk.

[0013]

Means for Solving the Problems and Embodiments of the Invention As a result of intensive studies to achieve the above object, the present inventor has found that dimethyldichlorosilane, tetramethylethylene and A triorganohydrogensilane compound represented by the general formula (1) R ¹ R ² R ³ SiH (1) (wherein, R ^{1 to} R ³ are the same or different monovalent hydrocarbon groups). By reacting, texyldimethylchlorosilane and the following general formula (2) R ¹ R ² R ³ SiCl (2) (wherein, R ^{1 to} R ³ are the same as above).
Can be obtained in good yield, inexpensively, easily and safely with a triorganochlorosilane compound represented by
In particular, this method is effective as a method for simultaneously producing texyldimethyldichlorosilane and trimethylchlorosilane, and at the same time, effectively utilizing the hydrogen atoms of t-butyldimethylsilane and texyldimethylchlorosilane and t-methyldimethylsilane.
The inventors have found that simultaneous provision with butyldimethylchlorosilane is possible, and have accomplished the present invention.

Accordingly, the present invention provides a texturing method comprising reacting dimethyldichlorosilane, tetramethylethylene and a triorganohydrogensilane compound represented by the above general formula (1) in the presence of a catalytic amount of an aluminum compound. Provided is a method for co-production of sildimethylchlorosilane and a triorganochlorosilane compound represented by the general formula (2).

Now, the present invention will be described in further detail. The method of co-production of texyl dimethylchlorosilane and a triorganochlorosilane compound according to the present invention uses dimethyldichlorosilane, tetramethylethylene and a specific triorganohydrogensilane compound. Used as raw material,
These are reacted in the presence of a catalytic amount of an aluminum compound.

The triorganohydrogensilane compound used in the present invention is represented by the following general formula (1): R ¹ R ² R ³ SiH (1) (where R ^{1 to} R ³ are the same as or different from each other) A different kind of monovalent hydrocarbon group).

In the above formula (1), R ^{1 to} R ³ are, for example, methyl, ethyl, propyl, isopropyl,
Monovalent carbon atoms having 1 to 20 carbon atoms, such as alkyl groups such as n-butyl group, t-butyl group, cyclohexyl group, cyclopentyl group and n-octyl group, and aryl groups such as phenyl group, more preferably 1 to 10 Hydrogen groups may be mentioned, and these may be the same or different.

Specific examples of the triorganohydrogensilane compound of the above formula (1) include trimethylsilane,
Triethylsilane, t-butyldimethylsilane, isopropyldimethylsilane, triisopropylsilane, normal butyldimethylsilane, cyclopentyldimethylsilane, dicyclohexylmethylsilane, normal octyldimethylsilane, phenyldimethylsilane, benzyldimethylsilane, (α, α-dimethylbenzyl) ) Dimethylsilane and the like.

The amount of the triorganohydrogensilane compound used is preferably 0.1 to 1.5 mol, particularly 0.5 to 1 mol, per 1 mol of dimethyldichlorosilane. The amount of tetramethylethylene used is 0.1 mol per mol of the triorganohydrogensilane compound.
~ 2 mol, especially 0.5-1 mol is preferred.

Examples of the aluminum compound used as the catalyst include aluminum chloride, aluminum bromide, aluminum oxychloride, aluminum oxybromide, ethyldichloroaluminum, and isopropyldichloroaluminum. Preferably, aluminum is used.

The amount of the aluminum compound (Lewis acid) to be used is a catalytic amount, which is 0.001 to 0.5 mol, especially 0.1 mol, per mol of dimethyldichlorosilane.
When the amount of the aluminum compound is less than 0.001 mol, the reaction rate may be remarkably reduced.
Undesirable disproportionation reactions such as bond cleavage may occur.

The above reaction can be carried out usually by dissolving or suspending a Lewis acid catalyst in dimethyldichlorosilane, and adding the triorganohydrogensilane compound and tetramethylethylene sequentially or simultaneously thereto and stirring them. In some cases, it can be carried out by dissolving or suspending a Lewis acid catalyst in a triorganohydrogensilane compound, adding dimethyldichlorosilane and tetramethylethylene sequentially or simultaneously thereto, and stirring. The reaction temperature in this case is -20 to 20
It is preferably 100 ° C, particularly preferably 0 to 40 ° C. The reaction time is usually 10 minutes to 10 hours.

The present invention is preferably carried out without a solvent, but may be carried out using an organic solvent such as hexane, octane or decane in some cases. The amount of the organic solvent used can be a usual amount.

The products obtained in the reaction of the present invention are texyldimethylchlorosilane and the following general formula (2) R ¹ R ² R ³ SiCl (2) (wherein R ^{1 to} R ³ are each Same as above.)
And a triorganochlorosilane compound represented by the formula:

Specific examples of the triorganochlorosilane compound of the above formula (2) include trimethylchlorosilane, triethylchlorosilane, t-butyldimethylchlorosilane, isopropyldimethylchlorosilane, triisopropylchlorosilane, normalbutyldimethylchlorosilane, cyclopentyldimethylchlorosilane, dicyclohexylmethyl Chlorosilane, normal octyldimethylchlorosilane, phenyldimethylchlorosilane, benzyldimethylchlorosilane, (α, α-dimethylbenzyl) dimethylchlorosilane and the like can be mentioned.

Further, when the target substances texyldimethylchlorosilane and triorganochlorosilane compound are isolated by distillation from the reaction solution, it is desirable to deactivate the contained Lewis acid. Specifically, a method of adding an ether such as anisole, diphenyl ether, o-dimethoxybenzene, p-dimethoxybenzene, and the like in an amount of 1 to 5 moles with respect to the number of moles of the used Lewis acid may be mentioned.

[0027]

According to the method of the present invention for co-production of texyldimethyldichlorosilane and triorganochlorosilane, texyldimethyldichlorosilane and triorganochlorosilane can be simultaneously produced in a low-cost and simple method, with high yield and high safety. It can be obtained and is industrially very advantageous.

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

Example 1 193.7 g (1.5 mol) of dimethyldichlorosilane and 4.0 g (0.03 mol) of aluminum chloride were placed in a 500 ml flask equipped with a stirrer, reflux condenser, thermometer and gas feed tube. , And trimethylsilane from a gas feed tube.
2 g (1.0 mol) was fed, and the gas feed tube was changed to a dropping funnel.
4.2 g (1.0 mol) was allowed to react dropwise at 5 to 15 ° C., and after aging for 2 hours, 10.2 g of diphenyl ether was added to the reaction solution to inactivate aluminum chloride. This reaction solution was distilled, and a fraction at 57 to 58 ° C. was collected to obtain 95.6 g of trimethylchlorosilane (88% yield). Subsequently, vacuum distillation was performed to obtain 54
By separating a fraction of ~ 56 ° C / 10 mmHg,
150.1 g of texyl dimethylchlorosilane was obtained (yield 84%).

Example 2 193.7 g (1.5 mol) of dimethyldichlorosilane and 4.0 g (0.03 mol) of aluminum chloride were placed in a 500 ml flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel. Preparation,
Here, 116.3 g of triethylsilane (1.0 mol)
1) followed by 84.2 g (1.0%) of tetramethylethylene.
mol) was added dropwise at 5 to 15 ° C., and the mixture was aged for 2 hours. Then, 10.2 g of diphenyl ether was added to the reaction solution to inactivate aluminum chloride. This reaction solution was distilled, and a fraction at 144 to 146 ° C was collected to obtain 140.2 g of triethylchlorosilane (yield: 93%). Subsequently, vacuum distillation was performed, and the temperature was 54 to 56 ° C /
By fractionating a fraction of 10 mmHg, 152.0 g of texyldimethylchlorosilane was obtained (yield: 85
%).

Example 3 Triethylsilane 116.3
g (1.0 mol) in t-butyldimethylsilane 11
Example 1 except that the amount was changed to 6.3 g (1.0 mol).
The reaction was carried out in the same manner as described above. The reaction solution is distilled and 12
By fractionating the fraction at 4-126 ° C., 136.2 g of t-butyldimethylchlorosilane was obtained (yield 90).
%). Subsequently, vacuum distillation is carried out, and the temperature is reduced to 54 to 56 ° C / 10
By fractionating the fraction of mmHg, 144.8 g of texyldimethylchlorosilane was obtained (81% yield).

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-56-92895 (JP, A) JP-B-57-30114 (JP, B2) JP-B-3-22880 (JP, B2) (58) Field (Int.Cl. ⁷ , DB name) C07F 7/12 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. In the presence of a catalytic amount of an aluminum compound,
Dimethyldichlorosilane, tetramethylethylene and the following general formula (1) R ¹ R ² R ³ SiH (1) (where R ^{1 to} R ³ are the same or different monovalent hydrocarbon groups). The following general formula (2) R ¹ R ² R ³ SiCl (2) (wherein R ^{1 to} R ³ are the same as defined above, respectively) is characterized by reacting a triorganohydrogensilane compound represented by the formula: Same as.)
And a method for co-production with a triorganochlorosilane compound.