JPS6023385A - Production of silanol compound - Google Patents

Abstract

PURPOSE:To produce the titled compound in quantitative yield, with simple operation, without necessitating rigorous control of pH and temperature, by mixing a disilazane compound with a chlorosilane compound, and hydrolyzing the mixture. CONSTITUTION:(A) The compound of formula I (R<1>-R<3> are H, 1-7C alkyl, alkenyl or phenyl) (preferably 1,1,1,3,3,3-hexaalkyldisilazane) is mixed with (B) the chlorosilane compound of formula II (preferably trialkylsilyl chloride) preferably at a molar ratio of 1:1-1.5:1. The mixture is subjected to the hydrolysis reaction preferably at 10-40 deg.C, if necessary in the presence of an inert organic solvent to obtain the objective silanol compound of formula III (e.g. trialkylsilanol).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing silanol compounds, particularly triorganosilanol compounds.

Traditionally, trialkylsilanol has been produced by hydrolyzing trialkylsilyl chloride using buffer dissolution while controlling the pH [Science and Industry 29].
．． 70-3 (1955)) or 1.1.1.3
．． 3. Method for hydrolyzing 3-hexaalkyldisilazane using hydrochloric acid water (Zhur, Obshei, Kh
:1m, 24.2202-6 (19541,'] etc. are known Z).

But these million? In IE, it is necessary to strictly control the pH and temperature, and since hexaalkyldisiloxane is produced as a by-product, a decrease in yield is unavoidable, and the operation is difficult, so it cannot be said to be a good method.

The present inventors conducted intensive research to solve these conventional disadvantages and arrived at the present invention, which is based on the general formula % ((R, R, R are Mizuki atoms, alkyl having 1 to 7 carbon atoms). basis,
A disilazane compound represented by a group selected from an alkenyl group and a phenyl group) and a chlorosilane compound represented by the general formula Regarding the method for producing a silanol compound represented by the general formula % (R, R, R are the same as above), which is characterized by a decomposition reaction, especially triorganosilanol, especially trialkylsilanol, 7'l-!
! This provides a Q-building method.

According to the present invention, 1) Strict control of pH and temperature is not required, and production is possible with extremely simple operations; 2) Yield is quantitative; and disiloxane compounds such as hexaalkyldisiloxane can be produced! No by-products are generated; ■ The yield is quantitative, so the silanol compound can be used as it is by simply removing the aqueous phase from the reaction solution (no operations such as distillation are required); You can get a great effect.

For example, when manufacturing trialkylsilanol by the method of the present invention, 1.
1.1.3.3.3-Hexaalkyldisilazane and trialkylsilyl chloride are mixed in advance, and water is added to the mixture to react (hydrolysis reaction).

B According to this method, as can be seen from the reaction formula, the target trialkylsilanol is quantitatively produced in two layers. The amount of water required for this hydrolysis reaction is three times the amount of trialkylsilyl chloride, but since ammonium chloride is produced as a by-product, the amount of water needed to dissolve this ammonium chloride is The hydrolysis reaction can be carried out either by dropping the raw material mixture into water or by adding water to the raw material mixture. That's fine, but
The reaction temperature at this time is 0°C to reflux temperature, especially 10 to 40°C.
It is preferable to set it as °C.

Although the organic solvent may not be used, when the hydrolyzed product is used as it is in the next reaction C2, it is preferable to use an inert solvent such as dichloromethane, ethyl ether, toluene, hexane, etc.

The mixing molar ratio of hexaalkyldisilazane and trialkylsilyl chloride as reaction raw materials is preferably 1:1, but hexaalkyldisilazane may be in excess up to 1.5:1. However, if trialkylsilyl chloride is used in excess, the reaction system will become acidic with hydrochloric acid, resulting in significant side production of hexaalkyldisiloxane Y (- leading to a decrease in yield, so this should be avoided if trialkylsilyl chloride is used in excess. be.

As the disilazane compound represented by the general formula tl+, which is one of the reaction logs 9), all kinds of compounds can be used, including hexamethyldisilazane, hexamethyldisilazane, 1.1. 3.3-tetramethyl-1,
3-dihydrosilazane, 1.1°3.3-tetramethyl-1,3-? ) Vinylsilazane, 1,3-dimethyl-・
1.3-dihydro-1,3-i) vinylsilazane, 1.
Examples include 1.9.3-tetramethyl-1°3-diphenylsilazane.

Examples of the chlorosilane compound represented by the general formula (10) include trimethylsilyl chloride, triethylsilyl chloride, dimethylhydrosilyl chloride, dimethylvinylsilyl chloride, methylvinylhydrosilyl chloride, and dimethylphenylsilyl chloride.

Generally, the disilazane compound and the chlororane compound used in a mixture have the same R, R, and R, respectively, but if the silanol compound to be produced is desired to be obtained as a mixture of two or more types of silanol compounds, Use different combinations.

Next, examples of the present invention will be given.

Example 1 Hexamethyldisilazane 161? (1 mole) and 108.5y-(1 mole) of trimethylsilyl chloride were mixed at room temperature, and while stirring in 250% water, 20 to 40%
The dropwise reaction was carried out at ℃. After stirring for 30 minutes, the upper organic layer was separated, and trimethylene was analyzed by gas chromatography to find that it was almost 100% pure IW, and no hexamethyldisiloxane was detected.

Example 2 1,1.3.3-tetramethyl-1,3-divinylsilazane 22.2. P (0.12 mol) and dimethylvinylsilyl chloride (12.11+0.1 mol) were mixed at room temperature and reacted dropwise at 30° C. with stirring into a mixed solution of 30° of water and 30° of diethyl ether.

After stirring for 30 minutes, the two organic layers were separated and analyzed by gas chromatography, and it was confirmed that dimethylvinylsilanol was produced stationarily. No tetramethyldivinylsiloxane was detected.

Comparative Example Hexamethyldisilazane 70? , water 50- and ethyl ether 25[-] were mixed, and while cooling to 0 to 10°C, an IN-H0I aqueous solution 250- was added dropwise over 3 hours.
After the addition was completed, the mixture was stirred at this temperature for 30 minutes. When the upper organic layer was analyzed by gas chromatography, it was found that 87% of trimethylsilanol was produced, but at the same time 13% was produced.
Hexamethyldisilochitine was produced as a by-product.

Application example: 33 parts of hexamethyldisilazane and 22 parts of trimethylsilyl chloride are mixed in advance, and this is mixed with 5 parts of water.
The mixture was added dropwise to a mixed solution of 100 d of dichloromethane and 100 d of dichloromethane while stirring at 20 to 30°C. After stirring for 30 minutes, the lower dichloromethane layer was separated and dehydrated with anhydrous sodium sulfate.

This dichloromethane solution was added dropwise to a solution of 42 mm of triethylamine, 72 mm of allyl-methyl-dichlorosilane methacrylate, and 300 mm of dichloromethane while stirring at 10 to 30 DEG C. for reaction. After the addition, 500 d of water was added, the organic layer was separated, and the solvent was distilled off, followed by distillation under reduced pressure. As a result, 98 y of allyl-methyl-ditrimethylsiloxy methacrylate was obtained (yield: 94%). ).

patent applicant Shin-Etsu Chemical Co., Ltd. 12-

Claims (1)

[Claims] 1. General formula % ((R, R, R are hydrogen atoms, alkyl groups having 1 to 7 carbon atoms,
A disilazane compound represented by a group selected from alkenyl groups and phenyl groups) and a chlorosilane compound represented by the general formula Method 2 for producing a silanol compound represented by the general formula % (R1, R2, R11 are the same as above), characterized in that the silanol compound 3 represented by the general formula (Fl-8i-OH) Claims that are trialkylsilanol'@
The manufacturing method 3 according to claim 1, the silanol compound 3 represented by the general formula R-81-Of() The manufacturing method 4 according to claim 1, wherein the silanol compound 3 is a dialkyl vinyl silanol, a disilazane compound and a chlorosilane compound Claim 1, wherein the mixing molar ratio of is 1:1 to 1.5:1.
Manufacturing method 5 described in section 1.1. ], 3.3.
The manufacturing method 6 according to claim 1, wherein the chlorosilane compound is 3-hexaalkyldisilazane, and the manufacturing method according to claim 1, wherein the chlorosilane compound is trialkylsilyl chloride.