JP2003119200A - Method for producing silanes - Google Patents

Abstract

(57) [Problem] To provide a method for industrially and advantageously producing silanes safely and economically. SOLUTION: A first reduction is performed on a silicon halide compound using sodium borohydride and / or a reaction product of sodium borohydride and aluminum chloride,
Further, the second reduction of a reducible compound such as a carboxylic acid, an olefin, a diene, an aldehyde, a ketone, a nitrile, an epoxide, an ester, and an acid chloride is performed using borane and / or diborane by-produced in the first reduction. Perform at the same time.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing silanes based on a novel method for reducing a silicon halide and a compound having a reducible bond with carbon by using borane and diborane by-produced in this reaction. Is further reduced to produce silanes and hydrocarbons and / or alcohols.

[0002]

2. Description of the Related Art As a method for producing silanes, for example, S.
N. Borisov et al., Dokl. Akad. Naulx. SSSR, Volume 114, p93,
The method disclosed in 1957, that is, the redistribution reaction of hydrosilane and chlorosilane with a Lewis acid such as aluminum chloride is known, but these reactions are generally complicated and the yield is low and the specific silane of interest is industrially produced. However, there is a cost problem in the method of manufacturing the same.

C. Eaborn et al., J. Organometal. Chem., 18
Vol. 3, p371, 1969 discloses a method for reducing the corresponding silicon halide with lithium aluminum hydride to produce silane. In addition, A. Berger, Fr. Patent 1429930
Discloses the production of silane using reduction with sodium hydride. Reduction with lithium aluminum hydride or sodium hydride is not a problem in small-scale synthesis, but lithium aluminum hydride and sodium hydride, and catalyst residues ignite when exposed to moisture, so raw material management and reduction Subsequent catalyst residue treatment is very difficult. Therefore, a reduction method that is safe and economical to handle has been desired as an industrial manufacturing method.

Further, sodium borohydride and a reaction product of sodium borohydride and anhydrous aluminum chloride are
It is used as a relatively safe and highly active reagent in industrial reduction reactions. However, when used as a reducing reagent for compounds such as silicon halides, only one of the four hydrogen (hydride) atoms in sodium borohydride is used for reduction and the remaining three hydrogen atoms are used. Produces borane and / or diborane upon reduction. Since one molecule of silicon halide requires one molecule of sodium borohydride, there is a problem that it is not an economical reducing reagent for industrial use. Furthermore, borane and / or diborane have a severe toxicity and have the property of paralyzing the olfactory sense, and if released outside the reaction system, there is a great risk. Sodium borohydride is an excellent reducing reagent, but it has a big problem for safe and economical use.

[0005]

An object of the present invention is to provide a method for producing silanes based on a novel method for reducing silicon halide.

Another object of the present invention is to reduce a silicon halide to produce silanes, and at the same time, to further provide a compound having a reducible bond with carbon by using borane and diborane which are by-produced during the reduction. Another object of the present invention is to provide a method for producing a hydrocarbon and / or alcohol by reduction with silanes.

Further objects and advantages of the present invention will be apparent from the following description.

[0008]

According to the present invention, the above objects and advantages of the present invention are as follows. First, a silicon compound having a silicon-halogen bond is reduced with sodium borohydride to obtain the silicon-halogen. This is achieved by a method for producing silanes (hereinafter referred to as the first method), which is characterized by converting the bond to a silicon-hydrogen bond.

According to the present invention, secondly, the above objects and advantages of the present invention are as follows. (1) A silicon compound having a silicon-halogen bond is reduced with sodium borohydride so that the silicon-halogen bond is converted into a silicon compound. -Borane and / or diborane which is converted into a hydrogen bond and (2) is by-produced by the reduction, and has at least one reducible bond selected from the group consisting of carbon-carbon, carbon-oxygen and carbon-nitrogen. This is accomplished by a method for producing silanes and hydrocarbons and / or alcohols (hereinafter referred to as a second method), which is characterized by reducing a compound.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The first method will be described below.

As the silicon compound having a silicon-halogen bond used in the first method, for example, the following formula (1): SiR _4-a X _a . ． ． (1) where R is a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, X is a halogen atom, and a
Is an integer of 1 to 4, a compound represented by the following formula (2): Si ₂ R _b X _c . ． ． (2) where R and X have the same definitions as above, and b is 0
Is an integer of 5 and c is an integer of 1 to 5, provided that b + c = 2 to 6, and a compound represented by the following formula (3): Si _{d Re} x _f . ． ． (3) Here, d is an integer of 3 or more, e is an integer of 0 or more, and f is an integer of 1 or more, provided that e + f =
The compounds represented by (2d-2) to (2d + 2) can be given.

In the above formulas (1), (2) and (3), R is a hydrogen atom, an alkyl group, an alkenyl group or an aryl group and X is a halogen atom. The alkyl group may be linear or branched and is preferably one having 1 to 20 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a butyl group, and an octyl group.

As the alkenyl group, for example, an allyl group,
Examples thereof include a 3-methyl-1-butenyl group.
Examples of the aryl group include a phenyl group and a naphthyl group. Preferable examples of the halogen atom include chlorine, bromine, and iodine.

In the above formulas (1), (2) and (3), a plurality of R's and a plurality of X's may be the same or different.

Examples of the silicon halide compounds represented by the above formulas (1) to (3) include trichlorosilane, tribromosilane, phenyltrichlorosilane, phenyltribromosilane, methyltrichlorosilane and methyltribromosilane. , Dimethyldichlorosilane, dimethyldibromosilane, diethyldichlorosilane, diethyldibromosilane, trimethylchlorosilane, trimethylbromosilane, methylphenyldichlorosilane, methylphenyldibromosilane, ethylphenyldichlorosilane, ethylphenyldibromosilane, diphenyl Phenyldichlorosilane, diphenyldibromosilane, dimethylpropylchlorosilane, methylpropyldichlorosilane, t-butyl-methyl-dichlorosilane, di-t-butyldichlorosilane, heptyltrisilane Roroshiran, 2-phenylalanine ethyl chromatography methyldichlorosilane, 1-phenylethyl - methyl dichlorosilane, 2- cyanoethyl trichlorosilane, 1
-Trichlorosilyl-3-methyl-1-butene, chloromethyldichlorosilane, allyltrichlorosilane, 1,
1-dichloro-1-silacyclobutane, 1,1-dichloro-1-silacyclopentane, 1-chloro-1-methyl-1-silacyclopentane, 1,1-dichloro-1-silacyclohexane, 1-chloro- 1-methyl-1-silacyclohexane, 1-t-butyl-1-chloro-1-silacyclohexane, 1-t-butoxy-1-chloro-1
-Silacyclohexane, 1-phenyl-1-chloro-1
Monosilanes such as silacyclohexane, 1-chloro-1-silabicyclo [2,2,1] heptane, 1-chloro-1-silabicyclo [2,2,2] octane; hexachlorodisilane, hexabromodisilane, pentamethylchlorodisilane , 1,2-dichloropentamethyldisilane,
1,1,2-trichlorotrimethyldisilane, 1,1,1,-
Disilanes such as trichlorodisilane; hexachlorocyclotrisilane, octachlorocyclotetrasilane, decachlorocyclopentasilane, trichlorosilylnonachlorocyclopentasilane, dodecachlorocyclohexasilane, tetradecachlorocycloheptasilane, hexadecachlorocyclooctasilane A halogenated cyclic silane compound such as; dodecachloro-n-pentasilane, dodecachloro-i-pentasilane, dodecachloro-neo-pentasilane, tetradecachloro-n-hexasilane, hexadecachloro-n-heptasilane, octadecachloro-n
-Halogenated chain silane compounds such as octasilane and docosachloro-n-nonasilane; dodecachloro-1,1'-
Bicyclobutasilane, hexadecachloro-1,1'-bicyclopentasilane, eicosachloro-1,1'-bicyclohexasilane, tetracosachloro-1,1'-bicycloheptasilane, tetradecachloro-1,1'- Cyclobutasilyl cyclopentasilane, hexadecachloro-1,1'-
Cyclobutasilylcyclohexasilane, octadecachloro-1,1'-cyclobutasilylcycloheptasilane, octadecachloro-1,1'-cyclopentasilylcyclohexasilylsilane, eicosachloro-1,1'-cyclopenta Silylcycloheptasilane, docosachloro-1,1 '
-Cyclohexasilylcycloheptasilane, octachlorosepyro [2,2] pentasilane, dodecachlorosepyro [3,3] heptasilane, hexadecachlorosepyro [4,4] nonasilane, octadecachlorosepyro [4, 5] Decasilane, eicosacralose pyro [4,
6] Undecasilane, eicosacralose pyro [5,
5] Undecasilane, docosachlorose pyro [5,6]
Undecasilane, tetracosachlorose pyro [6,6]
Examples thereof include halogenated silane compounds having a spiro structure such as tridecasilane; and halogenated polycyclic compounds such as hexachlorohexasil prismane and octachlorooctasilacubane. These compounds can be optionally used depending on the purpose of using the reduced compound.
Further, these compounds can be used alone or in combination of two or more kinds.

Sodium borohydride is preferably 1.0 to 10 moles, more preferably 1.0 to 10 moles per 1 product of the number of moles of the silicon halide compound and the number of silicon-halogen bonds in 1 mole of the compound. Used at 5 moles.

During the reduction with sodium borohydride, aluminum chloride can be additionally present.

The amounts of sodium borohydride and aluminum chloride used can be 0.5 to 5 mol of sodium borohydride per mol of aluminum chloride. It is more preferably 1 to 4 mol of sodium borohydride with respect to 1 mol of aluminum chloride, and particularly preferably 2 to 3.5 mol of sodium borohydride with respect to 1 mol of aluminum chloride. If the ratio of sodium borohydride to 1 mol of aluminum chloride is smaller than 1 or larger than 5, high activation by aluminum chloride for sodium borohydride cannot be obtained and it is difficult to obtain the combined effect of aluminum chloride.

A solvent may or may not be used for the reduction. It is preferred to use a solvent to properly control the reaction. Examples of the solvent include n-hexane, cyclohexane, n-heptane, n-octane,
Aliphatic hydrocarbons such as cyclooctane and n-decane; Alicyclic hydrocarbons such as indene, decalin and tetralin;
Benzene, toluene, xylene, ethylbenzene, t-
Aromatic hydrocarbons such as butylbenzene and trimethylbenzene; ethers such as ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and dioxane; active hydrogen such as hexamethylphosphomide and dimethyl sulfoxide There may be mentioned polar compounds having no. It is preferable to use soluble ethers and hydrocarbons in these solvents, in which borane and diborane produced as a by-product of the reduction do not react and are soluble. These solvents are
You may use individually or in mixture of 2 or more types.

The reduction reaction is preferably -50 to 200.
C., more preferably -20 to 150.degree. C., still more preferably 0 to 100.degree. If it is less than -50 ° C, the reaction rate is slow, and if it exceeds 200 ° C, a side reaction may occur.

The reaction time depends on the reactivity of the compound to be reduced. For example, it can be 0.5 to 48 hours, preferably 1 to 24 hours. When a solvent is used, the concentration of the compound to be reduced is preferably 1 to 80% by weight, more preferably 5 to 50% by weight.

According to the first method, silanes in which the silicon-halogen bond in the silicon halide compound is converted into a silicon-hydrogen bond can be obtained. And in the first method, borane and diborane are produced as byproducts.

Next, the second method will be described. As described above, the second method is a step (1) of reducing a silicon halide compound with sodium borohydride to produce silanes.
And borane and / or diborane by-produced in the step (1) to reduce a compound having a reducible bond with carbon to generate a hydrocarbon (2).

The step (1) is carried out in the same manner as the first method. The reduction of step (1) and the reduction of step (2) can be carried out in the same reaction system, and the reduction of step (1) and the reduction of step (2) can be carried out in the reaction system Borane and / or diborane produced as a by-product can be introduced into the reaction system in which the step (2) is carried out and carried out in another reaction system. The latter embodiment, which is carried out in another reaction system, is preferred.

Examples of the compound having a reducible bond used in the step (2) include diene, carboxylic acid, carboxylic acid chloride, carboxylic acid ester, aldehyde, ketone, nitrile and epoxy.

Examples of such compounds include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, capric acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, α-chloroacetic acid, α-bromo. Acetic acid, α-hydroxyacetic acid, 2-hydroxy-6-methylheptanoic acid, acetoacetic acid, α-cyanoacetic acid, α-phenylacetic acid, β-phenylpropionic acid, 2-ethylhexanoic acid, oleic acid, palmitic acid, fumaric acid Aliphatic carboxylic acids such as acids, maleic acid, succinic acid, 1,2-dimethylmaleic acid; aromatic carboxylic acids such as benzoic acid, p-methylbenzoic acid, p-nitrobenzoic acid, phthalic acid, terephthalic acid; 1 -Pentene, 2-pentene, 2-methyl-2
-Butene, 4-phenyl-2-pentene, 3-chloro-
3-hexene, 2,4-dimethyl-1-pentene, 2-
Olefins such as ethyl-1-butene, 1,4-dichloro-3 (2-chloroethyl) -2-pentene, 1-bromo-1,2-diphenylethene, cyclobutene, cyclohexene, cyclooctene; butadiene, isoprene,
Dienes such as chloroprene, 1,3-hexadiene, 1,3-cyclohexadiene, cyclopentadiene, cyclooctatetraene, vitamin A, retinal; acetone, 2-butanone, 2-pentanone, 2-hexanone,
2-octanone, 2-decanone, methyl isobutyl ketone, valerophenone, cyclobutanone, cyclohexanone, menthone, benzophenone, p-benzoxone, anthraquinone, acetophenone, α-bromomethylphenyl ketone, α-cyperone, acetylacetone, ethyl acetoacetate, camphor Such a ketone; acetaldehyde, propionaldehyde, butyraldehyde, valeric aldehyde, hexanal, octanal, decanal, undecanal, dodecanal, hexenal, heptenal, octenal, benzaldehyde, phenylacetaldehyde, p-methylbenzaldehyde, p
-Nitrobenzaldehyde, tolualdehyde, phthalic acid dialdehyde, terephthalic acid dialdehyde, retinal, glyoxal, malonaldehyde, succinic acid aldehyde, glutaraldehyde, phthalaldehyde, glycolaldehyde, salcylaldehyde, furfural,
Aldehydes such as indole-3-aldehyde, coumarin-3-aldehyde, acrolein, methacrolein, pentenal, allylacrolein, propargyl aldehyde; acetonitrile, ethylcyanide, propylcyanide, butylcyanide, amylcyanide, amylcyanide, hexylcyanide, decylcyanide, lauronitrile, dodecyl. Cyanide, myristonitrile, palmitonitrile, cetyl cyanide, stearonitrile, cyclopropyl nitrile, cyclopentyl nitrile, cyclohexyl nitrile, benzonitrile, benzyl cyanide, tolunitrile, β-phenylethyl cyanide, diphenylacetonitrile, α- Nitriles such as cyanotetrahydrofuran; ethylene oxide, propylene oxide, epichlorohydrin, Epibromohydrin, glycidol, epoxybutane, 1,2-epoxy-3-methoxypropane, pentamethylene oxide, epoxypentane, epoxybutane, epoxycyclopentane, epoxycyclohexane, styrene oxide, 2-phenyl-
Epoxides such as 1,2-epoxypropane, 1,2-epoxydecane; ethyl acetate, ethyl propionate, methyl propionate, methylbenzoate, methylphenylacetate, β-naphthyl acetate, dimethyl oxalate, dimethyl phthalate, dimethyl Esters derived from said aliphatic and aromatic carboxylic acids such as terephthalate, diethyl malonate, diethyl fumarate, ethyl acetoacetate, ethyl benzoate; said fats such as acetic acid chloride, acetic acid bromide, benzoic acid chloride, benzoic acid bromide Mention may be made of acid halides derived from group and aromatic carboxylic acids. Of these, it is preferable to use any one of carboxylic acid, olefin, diene, aldehyde, and ketone because of the ease of reduction or addition reaction with borane and / or diborane. These may be used alone or in combination of two or more.

A solvent may or may not be used in the reduction reaction of step (2). When these substances to be reduced are in a liquid state, it is preferable to reduce them without a solvent.

When the substance to be reduced has a high viscosity and is a gas or solid at room temperature, it can be dissolved in a solvent for reduction. As the solvent that can be used for dissolution, any solvent can be used as long as it does not react with borane and / or diborane. It is preferable to use hydrocarbons, ethers and alcohols. Examples of the hydrocarbons and ethers that can be used here include the same solvents as those mentioned in the first method of the present invention. Examples of alcohols include ethanol, isopropyl alcohol, butanol, hexanol and the like.

In the reduction in the step (2), the molar amount of sodium borohydride used in the reduction in the step (1) is equimolar or more, preferably 1.1 to 500 times by mole, more preferably 1.
A 2-300-fold molar amount of the reducible compound is used.

The reduction reaction in step (2) is preferably carried out at room temperature or lower, more preferably at -50 ° C to + 25 ° C. At room temperature or higher, borane and diborane easily dissipate,
If it is lower than -50 ° C, the reduction rate may be extremely slow. The reaction time depends on the reactivity of the compound to be reduced. It is preferably 0.5 to 48 hours, more preferably 1 to 24 hours.

The production container of the present invention is not particularly limited, but a specific production method will be described below. For the reduction in the step (1), a four-port container is prepared, and a dropping device, a condenser, a thermometer, and a three-way cock are attached to each of the four ports. Sodium borohydride and / or a mixture of sodium borohydride and aluminum chloride and a solvent were weighed in a 4-neck container, the silicon halide compound was weighed in a dropping device, and the silicon halide compound was placed in a 4-neck container. Drop and react. Sodium borohydride and / or a mixture of sodium borohydride and aluminum chloride and a silicon halide compound are weighed in a dropping apparatus and a 4-neck container, respectively, and sodium borohydride and / or sodium borohydride and aluminum chloride are weighed. You may make it react by dripping the solution of the mixture of these in a silicon halide compound. A three-way cock is attached to the top of the condenser attached to the four-necked container. As the reaction vessel used for the reduction in the step (2), a three-port container was prepared, and each of the two ports was equipped with a gas insertion device such as a capillary and a thermometer. The reducible compound used for the second reduction is, for example, at least one selected from the group of carboxylic acids, olefins, dienes, aldehydes, ketones, nitriles, epoxides, esters, and acid chlorides.
The class of compounds and optionally the solvent used are weighed into a three-necked container. One side of the three-way cock attached to the top of the condenser attached to the 4-port container is the second
It is connected to a gas insertion device such as a capillary attached to the reaction vessel used for the reduction of hydrogen, and is inert from almost one side of the three-way cock on the top of the condenser attached to the four-port vessel, which is dry and contains almost no oxygen. Gas is inserted. As the inert gas, nitrogen, argon, helium or the like can be used alone or in combination. The flow rate of the gas to be inserted is arbitrarily selected according to the reactivity of the halogenated compound used for the reduction in step (1) and is not particularly limited.

[0032]

The present invention will be described in detail below with reference to the following examples, but the present invention is not limited to these examples.

Example 1 37.8 g of sodium borohydride and 1 L of diethylene glycol dimethyl ether were weighed in a four-necked flask equipped with a dropping funnel, a condenser, a three-way cock, and a thermometer, and 126.6 g of diphtheria was added to the dropping funnel. The enyldichlorosilane was weighed. On the other hand, in a 3-neck flask,
00 ml of acetone was weighed and equipped with a gas insertion capillary and a thermometer. Connect one side of the 3-way cock attached to the upper part of the condenser attached to the 4-necked eggplant flask and the capillary of the 3-necked flask with a Teflon (registered trademark) tube, and attach it to the upper part of the condenser attached to the 4-necked eggplant flask. Dry nitrogen gas was allowed to slowly flow from the remaining one side of the attached three-way cock. Attach the 3-way cock to the remaining neck of the 3-neck flask, attach the Teflon (registered trademark) tube to one of the 3-way cocks, and insert the Teflon (registered trademark) tube into the alkaline aqueous solution bath at room temperature. The diphenyldichlorosilane in the dropping funnel was added dropwise with stirring for 10 hours. After the dropping was completed, the reaction was continued for 10 hours at room temperature.

After the reaction, the reaction solution in the 4-necked flask was set to 0.2.
Filtered through a μm membrane filter and dried with N _2.
The mixture was blown with gas and concentrated to obtain 91 g of product 1. This product has an absorption of Si-H at 4.9 ppm (single line, 2H) in the ¹ H-NMR spectrum and 7.4 and 7.6 p.
Since the absorption attributed to the phenyl group was observed in pm (both multiplex lines, 10H) and a single absorption was shown by gas chromatography, the product is diphenylsilane which is a reduced form of diphenyldichlorosilane. It was confirmed.

The reaction solution in the three-necked flask was directly concentrated under reduced pressure to obtain 175 g of liquid. ¹ H-NM of this liquid
R spectra are 1.2 ppm (doublet, 6H) and 4.
Absorptions attributed to a methyl group and a methine group were observed at 3 ppm (multiline, 1H), respectively. 90 this liquid
g in ice water, hydrolyzed, extracted with 1 L of diethyl ether, dried over anhydrous sodium sulfate, and distilled to yield 80 g of a fraction having a boiling point of 80 to 83 ° C. (Product 2)
Got This fraction was analyzed by ¹ H-NMR spectrum (1.2 p
pm, doublet, 6H and 3.9 ppm, multiplet, 1
From H), it was confirmed to be isopropyl alcohol, which is a reduced form of acetone. From the above, it was found that the liquid was isopropoxyboroxine.

Example 2 The reaction was carried out in the same manner as in Example 1 for 20 hours at room temperature except that 53.1 g of benzaldehyde and 1 L of tetrahydrofuran were used in place of the acetone of Example 1, and 90 g of the product was obtained from a 4-necked flask. 3 and the reaction solution in the 3-necked flask were concentrated and then hydrolyzed with ice water to give 98 g of the product 4
Got It was confirmed from the ¹ H-NMR spectrum and gas chromatography that the products 3 and 4 were diphenylsilane, which is a reduced form of diphenyldichlorosilane, and benzyl alcohol, which is a reduced form of benzaldehyde.

Example 3 The reaction was performed at room temperature for 20 hours in the same manner as in Example 1 except that 118 g of p-chlorobenzoic acid and 1 L of tetrahydrofuran were used in place of the acetone of Example 1, and 85 g of a 4-neck flask was used. The product 5 and the reaction solution in the three-necked flask were concentrated and then hydrolyzed with ice water to yield 87 g of the product 6.
Got The product 5 was analyzed by ¹ H-NMR spectrum and gas chromatography, and the product 6 was measured by ¹ H-NMR spectrum and melting point (71 to 73 ° C .; literature value, 72).
℃; J. Amer. Chem. Soc., 46, 1675, 1924)
From these, it was confirmed that they were diphenylsilane, which is a reduced form of diphenyldichlorosilane, and p-chlorobenzyl alcohol, which is a reduced form of p-chlorobenzoic acid.

Example 4 Instead of the diphenyldichlorosilane of Example 1, 248
g of decachlorocyclopentasilane and 2500 ml of acetone were used, except that the reaction was carried out at room temperature for 20 hours in the same manner as in Example 1 to yield 68 g of the product 7 from the 4-neck flask, and the reaction solution in the 3-neck flask was concentrated. Subsequent hydrolysis with ice water gave 720 g of product 8. The product 7 is ¹ H-NM
From the R spectrum, Si-NMR spectrum and gas chromatograph, the product 8 was analyzed by ¹ H-NMR spectrum and gas chromatograph, and cyclopentasilane which is the reduced form of decachlorocyclopentasilane and isopropyl which is the reduced form of acetone. It was confirmed to be alcohol.

Example 5 Instead of the diphenyldichlorosilane of Example 1, 148
The reaction was carried out at room temperature for 20 hours in the same manner as in Example 1 except that g of triphenylchlorosilane was used. 115 g of the product 9 was obtained from the 4-neck flask, and the reaction solution in the 3-neck flask was hydrolyzed with ice water after concentration. To give 75 g of product 10. The product 9 is ¹ H-NMR spectrum, Si-NM
From the R spectrum and the gas chromatograph, it was confirmed from the ¹ H-NMR spectrum and the gas chromatograph that the product 10 was triphenylsilane which is a reduced form of triphenylchlorosilane and isopropyl alcohol which is a reduced form of acetone. .

Example 6 95 g instead of the diphenyldichlorosilane of Example 1
Was reacted at room temperature for 20 hours in the same manner as in Example 1 except that the methylphenylphenylchlorosilane was used, and 54 g of the product 11 was obtained from the 4-neck flask, and the reaction solution in the 3-neck flask was hydrolyzed with ice water after concentration. To give 145 g of product 12. The product 11 is ¹ H-NMR spectrum, Si-
From the NMR spectrum and gas chromatography,
It was confirmed from the ¹ H-NMR spectrum and gas chromatography that the product 12 was methylphenylsilane which is a reduced form of methylphenyldichlorosilane and isopropyl alcohol which was a reduced form of acetone.

Example 7 Instead of the diphenyldichlorosilane of Example 1, 106
The reaction was carried out at room temperature for 20 hours in the same manner as in Example 1 except that g of phenyltrichlorosilane was used, and 48 g of the product 13 was obtained from the 4-neck flask, and the reaction solution in the 3-neck flask was hydrolyzed with ice water after concentration. Gave 235 g of product 14. The product 13 is ¹ H-NMR spectrum, Si-N
From the MR spectrum and the gas chromatograph, it was confirmed from the ¹ H-NMR spectrum and the gas chromatograph that the product 14 was phenylsilane which is the reduced form of phenyltrichlorosilane and isopropyl alcohol which was the reduced form of acetone.

Example 8 Instead of 37.8 g of sodium borohydride of Example 1, 37.8 g of sodium borohydride and 44.5
The reaction was carried out at room temperature for 10 hours in the same manner as in Example 1 except that g of anhydrous aluminum chloride was used.
g of the product 15 and the reaction solution in the three-necked flask were concentrated and then hydrolyzed with ice water to obtain 78 g of the product 16. The product 15 is ¹ H-NMR spectrum and gas chromatograph, and the product 16 is ¹ H-NMR spectrum and gas chromatograph, respectively, diphenyl silane which is a reduction product of diphenyl dichlorosilane and isopropyl which is a reduction product of acetone. It was confirmed to be alcohol.

[0043]

The silicon halide compound is subjected to the first reduction using sodium borohydride and / or a reaction product of sodium borohydride and aluminum chloride,
Further, by using borane and / or diborane by-produced in the first reduction, at least one compound selected from the group consisting of carboxylic acid, olefin, diene, aldehyde, ketone, nitrile, epoxide, ester, and acid chloride is used. By simultaneously performing the second reduction, silanes can be industrially produced safely and economically.

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Claims (8)

[Claims] 1. A method for producing silanes, which comprises reducing a silicon compound having a silicon-halogen bond with sodium borohydride to convert the silicon-halogen bond into a silicon-hydrogen bond. 2. A silicon compound having a silicon-halogen bond is represented by the following formula (1): SiR _4-a X _a . ． ． (1) where R is a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, X is a halogen atom, and a
Is an integer of 1 to 4, a compound represented by the following formula (2): Si ₂ R _b X _c . ． ． (2) where R and X have the same definitions as above, and b is 0
Is an integer of 5 and c is an integer of 1 to 5, provided that b + c = 2 to 6, and a compound represented by the following formula (3): Si _{d Re} x _f . ． ． (3) Here, d is an integer of 3 or more, e is an integer of 0 or more, and f is an integer of 1 or more, provided that e + f =
The method according to claim 1, which is at least one compound selected from the group consisting of compounds represented by the formulas (2d-2) to (2d + 2). 3. The method according to claim 1, wherein the reduction is carried out in the presence of aluminum chloride. 4. A silicon compound having (1) a silicon-halogen bond is reduced with sodium borohydride to convert the silicon-halogen bond into a silicon-hydrogen bond, and (2) borane by-produced by the reduction. And / or diborane is used to reduce a compound having at least one reducible bond selected from the group consisting of carbon-carbon, carbon-oxygen and carbon-nitrogen, and silanes and hydrocarbons and / or A method of producing alcohol. 5. The method according to claim 4, wherein the reduction in step (1) and the reduction in step (2) are carried out in the same reaction system. 6. The reduction of step (1) and the reduction of step (2) are conducted by introducing borane and / or diborane by-produced from the reaction system for carrying out step (1) to the reaction system for carrying out step (2). The method according to claim 4, which is carried out in another reaction system. 7. The method according to claim 4, wherein the compound having a reducible bond is selected from the group consisting of olefin, diene, carboxylic acid, carboxylic acid chloride, carboxylic acid ester, aldehyde, ketone, nitrile and epoxy. 8. The method according to claim 4, wherein the reduction in step (1) is carried out in the presence of aluminum chloride.