JP5844520B2 - Method for producing hydrolyzable silicon-containing compound - Google Patents

Description

  The present invention relates to a method for producing a hydrolyzable silicon-containing compound. The present invention also relates to a hydrolyzable silicon-containing compound which is produced by the production method described above and substantially does not contain hydrogen halide or acyl halide.

  It is known to produce organooxysilane by reacting alcohol or acetic acid (or acetic anhydride) with chlorosilane. For example, JP-A-8-41077 describes the production of alkoxysilane by the reaction of ≡Si—Cl + ROH = SiOR + HCl (R is a monovalent hydrocarbon group). Japanese Unexamined Patent Publication No. 2000-63390 describes that acetoxysilane is produced by reacting acetic acid and acetic anhydride with chlorosilane. Further, JP-A-10-168083 describes that diacetoxy dialkoxysilane is produced by reacting alcohol and acetic anhydride with chlorosilane. In addition, a German patent (DE19670906) describes that trimethoxysilane can be obtained by directly reacting trichlorosilane and methanol in a xylene solvent. On the other hand, in J. Org. Chem., Vol. 42, No. 23, 1977, a trimethylsilylated alcohol corresponding to an alkyl ether is obtained by reacting iodotrimethylsilane and an alkyl ether at room temperature without using a catalyst. It is described that it is obtained. JCS Chem Commun, P. 874-875, 1978 describes that trimethylsilylated reactants corresponding to esters etc. can be obtained using trimethylchlorosilane, sodium iodide, esters, etc. Yes.

JP-A-8-41077 JP 2000-63390 A JP-A-10-168083 German patent application number DE19670906 (German patent number 1298972)

J. Org. Chem., Vol. 42, No. 23, 1977 J. C. S. Chem Commun, P. 874-875, 1978

  However, in the production reaction of organooxysilane with alcohol and chlorosilane, the hydrogen chloride released during the reaction reacts with the starting materials and products to produce unwanted by-products. There is a problem that decreases. For example, the released hydrogen chloride reacts with alcohol to produce chloride and water. This reaction results in considerable alcohol loss. In addition, the water produced by this side reaction hydrolyzes chlorosilane or organooxysilane to produce an undesired polysiloxane and generates more hydrogen chloride. Hydrogen chloride may also react with other functional groups present in chlorosilane, either alone or with alcohol. In particular, the production of diorganodialkoxysilane or triorganoalkoxysilane by the formation reaction of organooxysilane with alcohol and chlorosilane results in extremely low yield or no formation at all.

  In addition, there is a problem similar to the above in the formation reaction of organooxysilane by acetic anhydride and chlorosilane, and acetyl chloride is flammable and irritating. In addition, in order to react water and acetyl chloride to regenerate hydrogen chloride, it is necessary to remove by performing a special treatment to ensure safety, and the reaction is an exothermic reaction with water, It is extremely dangerous. Implementation of such treatment makes it difficult to produce organooxysilane by the above production reaction, and is disadvantageous in terms of production cost. Furthermore, in the production method using iodotrimethylsilane as a raw material, iodotrimethylsilane is extremely reactive to light and moisture, and is easily decomposed by moisture in the air to produce toxic and irritating hydrogen iodide. Therefore, there is a problem that it is difficult to handle and difficult to adopt as a method for industrial mass production. Similarly, in the reaction using sodium iodide, when chlorosilane is converted with sodium iodide, a large amount of sodium iodide is consumed in the reaction to generate iodinated hydrocarbons and the like. As a result, since a large amount of waste is generated, there is a problem that the environmental load is large.

  The present invention has been made in view of the current state of the prior art, and a method for producing a hydrolyzable silicon-containing compound such as organooxysilane in an excellent yield and safely and inexpensively. The purpose is to provide.

As a result of intensive studies aimed at achieving the above object, the present inventors have reached the present invention. That is, the object of the present invention is to
(A) General formula:

R ¹ —O—R ²

(Where
R ¹ represents a substituted or unsubstituted tertiary alkyl group or aralkyl group having 4 to 30 carbon atoms,
R ² represents a substituted or unsubstituted monovalent hydrocarbon group or acyl group having 1 to 30 carbon atoms)
And a compound represented by:
(B) General formula:

R ³ _m SiX _4-m

(Where
R ³ independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms,
X is independently bromine or chlorine;
m represents an integer of 0 to 3) and is achieved by a method for producing a hydrolyzable silicon-containing compound, in which a halosilane represented by the formula (1) is reacted in the presence of a Lewis acid catalyst.

  The Lewis acid catalyst can be a Lewis acid containing a metal. The kind of Lewis acid containing a metal is not particularly limited as long as it promotes the above reaction, but one or more Lewis acids selected from the group consisting of metal halides, metal oxides and metal sulfates. It is preferable that Specifically, gallium chloride (III), gallium bromide (III), indium chloride (III), indium bromide (III), bismuth chloride (III), aluminum chloride (III), iron chloride (II), chloride Iron (III), iron bromide (II), iron bromide (III), nickel chloride (II), cadmium (II) oxide, chromium oxide (III), molybdenum oxide (VI), iron (III) oxide, sulfuric acid Examples thereof include one or more Lewis acids selected from the group consisting of iron (II) and iron (III) sulfate. In particular, one or more Lewis acids selected from bismuth chloride (III), aluminum chloride (III), and iron chloride (III) are preferred.

  The compound (A) may be an ether. The ether is preferably one or more ethers selected from methyl tert-butyl ether, ethyl tert-butyl ether, methyl-diphenylmethyl ether and methyltriphenylmethyl ether.

  The compound (A) may be an ester. The ester is preferably tert-butyl acetate or diphenylmethyl acetate.

  The (B) halosilane is chlorosilane or bromosilane, and chlorosilane is particularly preferable. Specifically, it can be monochlorosilane, dichlorosilane, trichlorosilane, or tetrachlorosilane, and is any of organochlorosilanes having an organic group bonded to a silicon atom and hydrochlorosilanes having a hydrogen atom bonded to a silicon atom. There may be.

  The hydrolyzable silicon-containing compound is preferably alkoxysilane, phenoxysilane or acetoxysilane.

  The hydrolyzable silicon-containing compound produced by the above production method is substantially free of hydrogen halide or acyl halide.

  The production method of the present invention can efficiently produce a hydrolyzable silicon-containing compound with excellent yield, starting from chlorosilane or bromosilane, which is relatively easy to handle. In addition, the production method of the present invention has high reaction selectivity, and the by-product is substantially only tertiary alkyl halide or halogenated aralkyl, so that it can be carried out safely and at low cost. Furthermore, the amount of the neutralizing agent used for the purpose of completing the reaction in the conventional production method can be reduced. Therefore, the production method of the present invention is useful as an industrial production method for synthesizing a large amount of a hydrolyzable silicon-containing compound.

  When ether (especially methyl tert-butyl ether, ethyl tert-butyl ether, methyl-diphenylmethyl ether or methyltriphenylmethyl ether) is used as the compound (A), the stability and safety of the compound is high. Since it is inexpensive, alkoxysilane can be produced safely and at low cost.

  When an ester, particularly tert-butyl acetate or diphenylmethyl acetate is used as the compound (A), acetyl chloride is hardly produced as a by-product, so that it is not necessary to treat it. Therefore, acetoxysilane can be produced stably and inexpensively, and is particularly useful as an industrial production method.

  When a Lewis acid catalyst, particularly bismuth (III) chloride, aluminum (III) chloride or iron (III) chloride is used as the catalyst, the reaction is suitably carried out because the toxicity of the catalyst is low and the environmental load is small. be able to.

  Since the hydrolyzable silicon-containing compound obtained by the production method of the present invention does not substantially contain reactive hydrogen halide or acyl halide, inactivation treatment of the hydrogen halide or acyl halide is unnecessary. Therefore, the hydrolyzable silicon-containing compound is suitable, for example, as a raw material for a solar cell or a silicone for semiconductors, or as a raw material for various products such as sealants used for building materials.

2 is a ¹³ C-NMR chart of the reaction product of Example 1. FIG. 6 is a ¹³ C-NMR chart of the reaction product of Example 9. FIG. 3 is a ¹³ C-NMR chart of the reaction product of Comparative Example 1. FIG. It is a ²⁹ Si-NMR chart which shows the comparison of the reaction product of Example 9 and Comparative Example 1. 3 is a ¹³ C-NMR chart of the reaction product of Example 11. FIG. FIG. 14 is a ¹³ C-NMR chart of a reaction product of Example 14. It is a ¹³ C-NMR chart figure of the reference example 15 reaction product. FIG. ¹³ is a ¹³ C-NMR chart of Example 16 reaction product. FIG. ¹³ is a ¹³ C-NMR chart of Example 17 reaction product.

In the production method of the present invention,
(A) General formula:

R ¹ —O—R ²

(Where
R ¹ represents a substituted or unsubstituted tertiary alkyl group or aralkyl group having 4 to 30 carbon atoms,
R ² represents a substituted or unsubstituted monovalent hydrocarbon group or acyl group having 1 to 30 carbon atoms)
And a compound represented by:
(B) General formula:

R ³ _m SiX _4-m

(Where
R ³ independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms,
X is independently bromine or chlorine;
m represents an integer of 0 to 3) in the presence of a Lewis acid catalyst to prepare a hydrolyzable silicon-containing compound.

R ¹ in the above general formula representing the compound (A) is a tertiary alkyl group or an aralkyl group. Since these tertiary alkyl groups or aralkyl groups have high cation stability resulting from cleavage of the R ¹ —O bond, a hydrolyzable silicon-containing compound can be obtained in a high yield in the reaction of the present invention. . Here, the tertiary alkyl group as R ¹ is not particularly limited as long as it has 4 to 30 carbon atoms in total and contains at least one tertiary carbon atom, and includes branched and cyclic alkyl groups. The group is preferably exemplified. More specifically, tertiary alkyl groups such as tert-butyl group, tert-pentyl group, tert-hexyl group and tert-octyl group, and cycloalkyl groups such as 1-methylcyclopentyl and 1-methylcyclohexyl group can be mentioned. . The carbon atom bonded to the oxygen atom of the above general formula is preferably a tertiary carbon atom, particularly preferably a tert-butyl group. Similarly, the aralkyl group is preferably a secondary or tertiary aralkyl group from the viewpoint of reactivity, and particularly preferably has a secondary carbon atom in which at least one phenyl group is bonded to a carbon atom. . More preferably, two or more phenyl groups preferably have a secondary or tertiary carbon atom bonded to the carbon atom. As such a secondary or tertiary aralkyl group, a diphenylmethyl group (H (C ₆ H ₅ ) ₂ C—) or a triphenylmethyl group ((C ₆ H ₅ ) ₃ C—) is preferable. In addition, the hydrogen atom on these alkyl groups or aralkyl groups may be at least partially substituted with a halogen atom such as fluorine, particularly a chlorine atom.

R ² in the above general formula representing the compound (A) is not particularly limited as long as it is a monovalent hydrocarbon group or acyl group having 1 to 30 carbon atoms in total.

  Examples of the monovalent hydrocarbon group having 1 to 30 total carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, and a myristyl group. A linear or branched alkyl group having 1 to 30 carbon atoms such as a palmityl group, a stearyl group, an isostearyl group or a behenyl group; a cycloalkyl group having 3 to 30 carbon atoms such as a cyclopentyl group or a cyclohexyl group An alkenyl group having 2 to 30 carbon atoms such as a vinyl group, an allyl group or a butenyl group; an aryl group having 6 to 30 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group or a styryl; a carbon such as a benzyl group; The aralkyl group of several 7-30 is mentioned. A linear alkyl group having 1 to 6 carbon atoms or a phenyl group is preferable, and a methyl group, an ethyl group or a phenyl group is more preferable.

  Examples of the acyl group having 1 to 30 total carbon atoms include aliphatic monocarboxylic groups such as formyl group, acetyl group, propionyl group, butyryl group, valeryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group and the like. Examples include acid-based acyl groups and aromatic ring-containing acyl groups such as benzoyl groups and cinnamoyl groups. Aliphatic monocarboxylic acid acyl groups are preferred, and acetyl groups are more preferred.

  The hydrogen atom bonded to the carbon atom of these groups may be at least partially substituted with a halogen atom such as fluorine, but is preferably unsubstituted.

In particular, R ² is preferably a primary alkyl group, a secondary alkyl group, an aryl group or an acyl group.

Therefore, ether or ester can be suitably used as the compound (A). Examples of the ether include methyl tert-butyl ether, ethyl tert-butyl ether, propyl tert-butyl ether, methyl tert-pentyl ether, ethyl tert-pentyl ether, propyl tert-pentyl ether, methyl tert-hexyl ether, and ethyl tert-hexyl ether. , propyl tert- hexyl ether, methyl tert- octyl ether, ethyl tert- octyl ether, propyl tert- octyl ether, methyl (diphenylmethyl) ether _{(H (C 6 H 5)} 2 CO-CH 3), methyl (triphenyl Methyl) ether ((C ₆ H ₅ ) ₃ CO—CH ₃ ), benzyl methyl ether, benzyl phenyl ether and the like. In particular, methyl tert-butyl ether, ethyl tert-butyl ether methyl (diphenylmethyl) ether, and methyl (triphenylmethyl) ether are preferable. Esters include tert-butyl formate, tert-butyl acetate, tert-butyl propionate, tert-pentyl formate, tert-pentyl acetate, tert-pentyl propionate, tert-hexyl formate, tert-hexyl acetate, tert-propionate Examples include hexyl, tert-octyl formate, tert-octyl acetate, tert-octyl propionate, tert-butyl laurate, and diphenylmethyl acetate. In particular, tert-butyl acetate or diphenylmethyl acetate is preferred. These ethers or esters may be used in combination of two or more different types.

The component (B) has the general formula:

R ³ _m SiX _4-m

(Where
R ³ independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms,
X is independently bromine or chlorine;
m represents an integer of 0 to 3). Here, the monovalent hydrocarbon group is as described above, but the hydrogen atom bonded to the carbon atom of the monovalent hydrocarbon group contained in the halosilane is at least partially a halogen atom such as fluorine, or , An acyl group, a carboxyl group, an amino group, a methacryloxy group, an acryloxy group, a ureido group, a polysulfide group, a mercapto group, an isocyanate group and the like, may be substituted.

The (B) halosilane is preferably a chlorosilane in which X is chlorine, and is either an organochlorosilane having an organic group bonded to a silicon atom or a hydrochlorosilane having a hydrogen atom bonded to a silicon atom. May be. For example, dichlorosilane (H ₂ SiCl ₂ ), trichlorosilane (HSiCl ₃ ), tetrachlorosilane, methyldichlorosilane, dimethylmonochlorosilane ((CH ₃ ) ₂ H ₂ SiCl ₂ ), dimethyldichlorosilane, trimethylchlorosilane, ethyldichlorosilane , Vinyltrichlorosilane, methylvinyldichlorosilane, phenyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, cyclohexylmethyldichlorosilane, (chloropropyl) trichlorosilane, bis (3,3,3-trifluoropropyl) dichlorosilane, tris (3,3,3-trifluoropropyl) chlorosilane, 3-methacryloxypropylmethyldichlorosilane, 3-methacryloxypropyltrichlorolane, 3-acryloxy Propyl trichlorosilane, 3-aminopropyl trichlorosilane, 3-mercaptopropyl methyl dichlorosilane, 3-mercaptopropyl trichlorosilane, and the like. Further, (B) halosilane may be bromosilane in which X is bromine. As the bromosilane as the component (B), those in which some or all of the chlorine atoms in the chlorosilane are bromine atoms can be used without particular limitation.

  As long as a hydrolyzable silicon-containing compound is obtained, the amount of the (A) compound and the (B) halosilane used is not limited. For example, the molar ratio of the (A) compound / (B) halosilane Can be in the range of 50-300% of stoichiometric equivalence. The molar ratio is preferably in the range of 0.75 to 2, more preferably in the range of 0.95 to 1.3, and still more preferably in the range of 1.1 to 1.3. The stoichiometric equivalent is defined as 1 mol of the compound (A) with respect to 1 mol of the halogen atom bonded to silicon in the (B) halosilane added to the reaction system.

  The reaction between the compound (A) and the halosilane (B) is carried out in the presence of a Lewis acid catalyst. As long as the reaction is promoted, the type of Lewis acid catalyst is not limited, but a Lewis acid catalyst containing a metal is preferable.

  In the production method of the present invention, examples of the Lewis acid catalyst containing metal include metal halides, metal oxides, and metal sulfates. Metal halides include, for example, lithium chloride, bismuth (III) chloride, aluminum (III) chloride, iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, zinc chloride (II), beryllium chloride (II), antimony chloride (III), antimony chloride (V), boron chloride, cesium chloride, cobalt chloride (II), cobalt chloride (III), nickel chloride (II), titanium chloride (III ), Titanium chloride (IV), tin chloride (II), tin chloride (IV), rhodium (III) chloride, cadmium chloride (II), germanium chloride (IV), gallium chloride (III), gallium bromide (III) Indium (III) chloride, indium (III) bromide, lead (II) chloride, manganese (II) chloride, and palladium (II) chloride. Examples of metal oxides include beryllium oxide (II), vanadium oxide (V), chromium oxide (III), iron oxide (II), iron oxide (III), cobalt oxide (III), cadmium oxide (II), and oxide. Molybdenum (VI) is mentioned. Examples of the metal sulfate include iron (II) sulfate and iron (III) sulfate.

  Of these, gallium chloride (III), gallium bromide (III), indium chloride (III), indium bromide (III), bismuth chloride (III), aluminum chloride (III), iron chloride (II), iron chloride (III), iron (II) bromide, iron (III) bromide, nickel (II) chloride, cadmium (II) oxide, chromium (III) oxide, molybdenum (VI) oxide, iron (III) oxide, iron sulfate (II) and iron (III) sulfate are suitable Lewis acid catalysts in the present invention, and bismuth (III) chloride, aluminum (III) chloride, and iron (III) chloride are particularly preferably used. The metal halide can be used in either anhydrous or hydrated salt, but if water is present in the system, it causes hydrolysis reaction with the raw material chlorosilane or bromosilane, and the generated silanol group is polymerized. An anhydrous salt is preferred because it may cause a reaction. Depending on the reaction scale, the influence of crystal water may be almost negligible.

  The amount of the Lewis acid catalyst used is, for example, 0.0001 to 1.0 mol, preferably 0.05 to 0.5 mol, and 0.03 to 0.1 mol, per mol of (B) halosilane. More preferably, 0.01 to 0.05 mol is even more preferable. If the amount of the Lewis acid catalyst is too small, the reaction may be slowed or stopped in the middle of the reaction. If the amount is too large, (B) the halosilane may cause an undesirable reaction such as cleavage of the Si-C bond. There is a risk.

  The reaction between the compound (A) and the halosilane (B) can be performed in a homogeneous system or a heterogeneous system depending on whether the Lewis acid catalyst is dissolved in the component (B). When using a Lewis acid catalyst having low solubility in the component (B), such as bismuth chloride, the Lewis acid catalyst is added to the component (B), and then the compound (A) is added and stirred. Can be done by. In this case, the catalyst-derived residue (black tar-like substance in bismuth chloride) settles at the bottom of the reaction mixture at the time of completion of the reaction. It can be separated using means. On the other hand, when using a Lewis acid catalyst having high solubility in the component (B) such as iron (III) chloride, the catalyst is dissolved in the (B) halosilane, and then the compound (A) is added. This can be done by stirring. In this case, the reaction solution as a whole is transparent and uniform, and the catalyst-derived residue does not separate and settle at the time of completion of the reaction. Therefore, it is possible to easily avoid the problem that the residue accumulates in the equipment piping and the piping is blocked. There are advantages. When the Lewis acid catalyst is easily dissolved in the compound (A), the catalyst may be dissolved in the component (A), and then the halosilane (B) may be added.

  The temperature of the above reaction is preferably 0 to 150 ° C., and under 1 atmosphere, 0 to 90 ° C., more preferably 20 to 40 ° C. is more preferable, and the reaction is particularly preferably performed at a so-called room temperature (25 ° C.). On the other hand, depending on the selection of the catalyst and the raw material, the reaction can be promoted by selecting high temperature conditions of 50 to 90 ° C. Needless to say, a higher temperature condition can be selected under pressure. If the reaction temperature is too low, the reaction rate becomes slow and a long reaction time may be required. On the other hand, if the reaction temperature is too high, the hydrolyzable silicon-containing compound produced causes an undesirable reaction. There is a risk that. The reaction time varies depending on the reaction scale and temperature, and can be, for example, 10 minutes to 1 week, preferably 1 to 40 hours. In particular, when bismuth chloride or iron (III) chloride is used as the Lewis acid catalyst, it is preferably 4 to 36 hours at room temperature (25 ° C.) and 1 atmosphere.

  The above reaction is preferably performed in an inert gas atmosphere, and examples of the inert gas include nitrogen and argon. The above reaction can be performed under reduced pressure, normal pressure, or increased pressure, but it is preferably performed under normal pressure in terms of operability.

  The reaction between the compound (A) and the (B) halosilane may be performed in a solvent. The solvent used is preferably a solvent that does not react with the compound (A) and / or the (B) halosilane, and is an inert solvent that is liquid at room temperature and atmospheric pressure and has a boiling point of 150 ° C. or lower. Is preferred. Examples of such solvents include hydrocarbon solvents such as toluene, xylene, hexane, nonane, pentane, and octane; hydrogen tetrachloride, methylene chloride, dichloroethane, dichloroethylene, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, Examples include chlorinated hydrocarbon solvents such as tetrachloroethane, and acetonitrile.

  The reaction of the compound (A) and the (B) halosilane can be carried out batchwise or continuously. When the reaction is carried out continuously, the compound (A) and the (B) halosilane are reacted, and after the reaction reaches equilibrium, the system is reduced in pressure to react with the hydrolyzable silicon-containing compound produced. The reaction may be performed while being extracted from the system, or the reaction may be further performed while the halogenated hydrocarbon derived from the tertiary alkyl group or aralkyl group, which is a by-product, is extracted from the reaction system. In the above reaction, a substance other than the halogenated hydrocarbon is hardly generated as a by-product, so that the reaction selectivity is high. In the above reaction, hydrogen halide such as hydrogen chloride is hardly produced as a by-product, so it is safe, and it is hardly necessary to add a base such as an amine as a neutralizing agent for hydrogen halide. Can do. Further, in the above reaction, flammable / stimulant acyl halides such as acetyl chloride are hardly generated, so that the environmental load is low and the reaction can be carried out safely.

  When using a Lewis acid catalyst having low solubility in the component (B), such as bismuth chloride, the catalyst is difficult to dissolve in the system. It is particularly useful. In addition, a Lewis acid catalyst that is uniformly dissolved in the component (B), such as iron (III) chloride, is useful for batch-type processes. The Lewis acid catalyst such as iron (III) chloride after the reaction can be easily isolated from the product by deactivation and distillation as necessary.

  Since the solution after the reaction is almost neutral, the obtained hydrolyzable silicon compound can be taken out of the reaction solution as it is by distillation or the like. If necessary, in order to deactivate the Lewis acid catalyst remaining after the reaction of the compound (A) and the (B) halosilane, a small amount of a compound acting as a Lewis base is added, followed by water addition by distillation or the like. The decomposable silicon-containing compound can also be taken out from the reaction system. In addition, you may use the obtained hydrolysable silicon-containing compound for next reaction as it is, without isolating.

  The hydrolyzable silicon-containing compound obtained by the production method of the present invention has at least one silicon-bonded hydrolyzable group such as alkoxy, acetoxy group or phenoxy group. As the hydrolyzable silicon-containing compound, alkoxysilane, acetoxysilane or phenoxysilane is preferable. Examples of the alkoxysilane include methoxysilane, methoxytrimethylsilane, ethoxysilane, butoxysilane, dimethyldimethoxysilane, dimethylmethoxychlorosilane, trimethoxychlorosilane, trimethoxysilane, tetramethoxysilane, tert-butyltrimethoxysilane, isobutyltrimethoxy. Silane, isobutylmethoxysilane, octadecyltrimethoxysilane, dodecyltrimethoxysilane, cyclohexylmethyldimethoxysilane, triethoxysilane, vinyltrimethoxysilane, methylvinyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, phenyl Methoxychlorosilane, triphenylmethoxysilane, 2-phenylpropylmethyl Methoxysilane, methylhexanedienyldimethoxysilane, (chloropropyl) trimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, bis- (3,3,3-trifluoropropyl) dimethoxysilane, tris -(3,3,3-trifluoropropyl) methoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, Examples include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. Examples of acetoxysilane include vinyltriacetoxysilane and trimethylacetoxysilane. Phenoxysilanes include methyltriphenoxysilane, ethyltriphenoxysilane, vinyltriphenoxysilane, phenyltriphenoxysilane, dimethyldiphenoxysilane, methylvinyldiphenoxysilane, divinyldiphenoxysilane, methylphenyldiphenoxysilane, diphenyldiphenoxy Examples include silane. In the production method of the present invention, such a hydrolyzable silicon-containing compound can be obtained in a high yield.

  In the reaction of the compound (A) with the (B) halosilane, little or no reactive hydrogen halide or acyl halide is generated. Therefore, the hydrolyzable silicon-containing compound obtained by the production method of the present invention is a halogenated compound. Substantially free of hydrogen halide or acyl halide. Here, “substantially” means 5% or less, preferably 1% or less, more preferably 0.1% or less, and still more preferably 0.01% or less of the total mass (weight) of the hydrolyzable silicon-containing compound. % Or less. Therefore, the hydrolyzable silicon-containing compound obtained by the production method of the present invention can be used in the next step without performing inactivation treatment of hydrogen halide or acyl halide.

  Since the hydrolyzable silicon-containing compound obtained by the production method of the present invention contains little or no hydrogen halide or acyl halide, it is inherently low in impurities. Purification can be carried out by a known method such as lithography, and the purity can be further increased.

  The hydrolyzable silicon-containing compound obtained by the production method of the present invention can be used for known applications. For example, alkoxysilane is useful as a silane coupling agent, various organopolysiloxane synthesis raw materials, and the like. In particular, the alkoxysilane obtained by the production method of the present invention is a silicone for solar cells or semiconductors that requires high purity. It is useful as a raw material. On the other hand, acetoxysilane is useful as a silane coupling agent, silylating agent, cross-linking agent, etc., and in particular, acetoxysilane obtained by the production method of the present invention is useful as a raw material for sealants used for building materials and the like. is there. Similarly, the reaction described above hardly produces flammable / stimulating acyl halides such as acetyl chloride, and therefore has an advantage that a silane raw material having high purity and suitable for electronic materials can be obtained. ,

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. The products in Examples and Comparative Examples were identified using NMR for nuclides ²⁹ Si, ¹³ C, ¹ H. Specifically, JEOL JNM-ECX-500 manufactured by JEOL Ltd. was used for the NMR measurement apparatus. At the time of measurement, deuterated chloroform (CDCl ₃ ) is used as a solvent, a small amount of chromium acetyl acetate is added as a relaxation accelerator to a 5Φ measuring tube, tetramethylsilane (δ = 0, 1H-NMR, 13C-NMR, 29Si NMR) Was measured using as an internal standard. The yield of the reaction product was determined based on the ratio of the integral value of the signal corresponding to the reaction raw material and the product.

[Example 1]
Install a magnetic stir bar inside a round bottom flask (Schlenk tube) with a 30 ml capacity 2-way cock, charge 0.16 g (0.5 mmol) of bismuth chloride (BiCl ₃ ), seal the flask with a septum, and replace with nitrogen. Went. Next, 2.91 g (33 mmol) of methyl tert-butyl ether was charged into the flask with a syringe and placed in an ice bath (0 ° C.). In an ice bath (0 ° C), 2.11 g (10 mmol) of phenyltrichlorosilane was slowly dropped into the flask with a syringe. After completion of the dropping, the system was returned to room temperature (25 ° C), and a magnetic stirrer was used. The solution was allowed to react overnight (15 hours) with stirring. The solution after completion of the reaction was measured by ²⁹ Si-NMR, ¹³ C-NMR, and ¹ H-NMR, the product was identified from the measurement result, and the yield of the product was determined. The results are shown in Table 1. In addition, a small amount of black precipitate derived from the catalyst was precipitated in the solution after the reaction.

[Example 2]
The reaction was performed in the same manner as in Example 1 except that the same molar amount (= 1.70 g) of tetrachlorosilane was used instead of phenyltrichlorosilane. The results are shown in Table 1.

[Example 3]
The reaction was carried out in the same manner as in Example 1 except that the same molar amount (= 1.35 g) of hydrotrichlorosilane was used instead of phenyltrichlorotrisilane. The results are shown in Table 1.

[Example 4]
The reaction was performed in the same manner as in Example 1 except that the same molar amount (= 3.04 g) of dodecyltrichlorosilane was used instead of phenyltrichlorotrisilane. The results are shown in Table 1.

[Example 5]
The reaction was conducted in the same manner as in Example 1 except that instead of phenyltrichlorotrisilane, the same molar amount (= 1.62 g) of vinyltrichlorosilane was used. The results are shown in Table 1.

[Example 6]
The reaction was conducted in the same manner as in Example 1 except that the same molar amount (= 3.37 g) of ethyl tert-butyl ether was used instead of methyl tert-butyl ether. The results are shown in Table 1.

[Example 7]
The reaction was carried out in the same manner as in Example 2 except that both were used at a ratio of 3 mol of methyl tert-butyl ether to 1 mol of tetrachlorosilane. That is, the reaction was performed in the same manner as in Example 2 except that the amount of methyl tert-butyl ether used was 2.64 g (30 mmol). The results are shown in Table 1.

[Example 8]
The reaction was performed in the same manner as in Example 1 except that dimethyldichlorosilane was used instead of phenyltrichlorotrisilane, and the molar ratio of dimethyldichlorosilane: methyl tert-butyl ether was 1: 2.6. That is, the reaction was carried out in the same manner as in Example 1 except that 2.29 g (26 mmol) of methyl tert-butyl ether was used and 1.29 g (10 mmol) of dimethyldichlorosilane was used instead of phenyltrichlorotrisilane. The results are shown in Table 1.

[Example 9]
Cyclohexylmethyldichlorosilane is used in place of phenyltrichlorotrisilane, the molar ratio of cyclohexylmethyldichlorosilane: methyl tert-butyl ether is 1: 2.6, and the molar ratio of cyclohexylmethyldichlorosilane: bismuth chloride is 1: The reaction was performed in the same manner as in Example 1 except that the content was 0.01. That is, a magnetic stirrer was installed inside a round bottom flask with a 30 ml capacity and a two-way cock, charged with 0.03 g (0.1 mmol) of bismuth chloride (BiCl ₃ ), sealed with a septum, and purged with nitrogen. went. Next, 2.29 g (26 mmol) of methyl tert-butyl ether and 1.97 g (10 mmol) of cyclohexylmethyldichlorosilane were charged into the flask in the same manner as in Example 1, and then the reaction was carried out in the same manner as in Example 1. It was. The results are shown in Table 1.

[Example 10]
Other than using trimethylchlorosilane instead of phenyltrichlorotrisilane, the molar ratio of trimethylchlorosilane: methyl tert-butyl ether was 1: 1.3, and the molar ratio of trimethylchlorosilane: bismuth chloride was 1: 0.01. Was reacted in the same manner as in Example 1. In other words, a magnetic stirrer was installed inside a round bottom flask with a 30 ml capacity and a two-way cock, 0.03 g (0.1 mmol) of bismuth chloride (BiCl ₃ ) was charged, the flask was sealed with a septum, and then purged with nitrogen. It was. Next, 1.15 g (13 mmol) of methyl tert-butyl ether and 1.09 g (10 mmol) of trimethylchlorosilane were charged into the flask in the same manner as in Example 1, and then the reaction was carried out in the same manner as in Example 1. The results are shown in Table 1.

[Example 11]
The reaction was conducted in the same manner as in Example 5 except that the same molar amount (= 3.83 g) of tert-butyl acetate was used instead of methyl tert-butyl ether. The results are shown in Table 1. From the NMR chart, no by-product of acetyl chloride was confirmed, and the obtained vinyltriacetoxysilane was highly pure.

[Example 12]
The reaction was carried out in the same manner as in Example 10 except that the same molar amount (= 1.51 g) of tert-butyl acetate was used instead of methyl tert-butyl ether. The results are shown in Table 1. From the NMR chart, no by-product of acetyl chloride could be confirmed, and the obtained trimethylacetoxysilane was highly pure.

[Example 13]
The reaction was carried out in the same manner as in Example 1 except that the same molar amount (= 2.12 g) of chloropropyltrichlorosilane was used instead of phenyltrichlorotrisilane. The results are shown in Table 1.

[Comparative Example 1]
A magnetic stirring bar was placed inside a round bottom flask with a 30 ml capacity two-way cock, and the flask was sealed with a septum, and then purged with nitrogen. Next, 0.70 g (22 mmol) of methanol and 1.97 g (10 mmol) of cyclohexylmethyldichlorosilane were charged into the flask in the same manner as in Example 1. Thereafter, the reaction was carried out in the same manner as in Example 1. The reaction solution of Comparative Example 1 became a highly viscous liquid compared to the other examples. The results are shown in Table 1.

[Comparative Example 2]
The reaction was performed in the same manner as in Example 2 except that the reaction time was extended from 15 hours to 3 days without using bismuth chloride (BiCl ₃ ). The results are shown in Table 1. Under the condition where a Lewis acid catalyst is not present, even if the reaction time is extended to 3 days, a hydrolyzable silicon compound is not produced by the reaction of tetrachlorosilane and methyl tert-butyl ether. There was no change.

  As shown in Table 1, in the reactions of Examples 1 to 13, the products shown in Table 1 could be obtained with high yield.

On the other hand, in the reaction of Comparative Example 1, many kinds of complicated mixtures were formed, and all the products could not be identified. Hydrogen chloride which is a reaction by-product of Comparative Example 1 reacts with unreacted methanol to generate water by the reaction of MeOH + HCl → MeCl + H ₂ O, which further reacts with chlorosilane to form silanol, which is then polymerized. It seems that it became the high molecular weight by. The reaction system of Comparative Example 1 was a highly viscous liquid, and the hydrolyzable silane shown in the examples could not be obtained in high yield. For comparison, FIG. 4 shows a ²⁹ Si-NMR chart after the reaction in Example 9 and Comparative Example 1 using the same cyclohexylmethyldichlorosilane as a starting material.

  Further, in the reaction of Comparative Example 2, the reaction of tetrachlorosilane and methyl tert-butyl ether did not proceed. From the comparison with Example 2, it was confirmed that the Lewis acid catalyst was essential for this reaction.

＊）表中において、官能基の略号は以下の通りである。
Me：メチル基
Ph：フェニル基
cyc-Hex：シクロヘキシル基
tert-Bu：第３級ブチル基
Ac：アセチル基
＊＊）反応時間は３日間であったが、反応の進行はＮＭＲ上認められなかった。。

*) In the tables, functional group abbreviations are as follows.
Me: Methyl group
Ph: Phenyl group
cyc-Hex: cyclohexyl group
tert-Bu: Tertiary butyl group
Ac: acetyl group **) The reaction time was 3 days, but no progress of the reaction was observed on NMR. .

[Example 14]
Install a magnetic stir bar inside a round bottom flask (Schlenk tube) with a 50 ml capacity two-way cock, charge 16 mg (0.1 mmol) of iron (III) chloride (FeCl ₃ ), seal the flask with a septum, Nitrogen replacement was performed. Next, 2.90 g (33 mmol) of methyl tert-butyl ether and 2.11 g (10 mmol) of phenyltrichlorosilane were charged into the flask in the same manner as in Example 1, the system was returned to room temperature (25 ° C.), and a magnetic stirrer was added. The solution was allowed to react overnight (15 hours) with stirring.

The reaction solution containing iron (III) chloride was uniform as a whole and was a pale yellow transparent solution. Unlike the case of Example 1, no residue or precipitation occurred. A part of the solution after the reaction was collected and measured by ²⁹ Si-NMR, ¹³ C-NMR, and ¹ H-NMR, and as a result of identifying the product from the measurement result, as in Example 1, PhSi (OMe ) It was confirmed that ₃ was generated. The results are shown in Table 2.

[ Reference Example 15]
The reaction was carried out in the same manner as in Example 14 except that the same molar amount (= 13 mg) of aluminum chloride (AlCl ₃ ) was used instead of iron (III) chloride. The results are shown in Table 2.

After performing the reaction overnight (15 hours), the solution after the reaction containing aluminum chloride was uniform as a whole and was a milky white transparent solution. Unlike the case of Example 1, no residue or precipitation occurred. A part of the solution after the reaction was collected and measured by ²⁹ Si-NMR, ¹³ C-NMR, and ¹ H-NMR. As a result of identifying the product from the measurement result, PhSi (OMe) ₃ was produced. However, unlike Example 1 and Example 14, most of the phenyltrichlorosilane was unreacted at the reaction time of 15 hours.

On the other hand, when the reaction time was further extended and the reaction was continued for 3 days (72 hours) with stirring, the solution after the reaction containing aluminum chloride was uniform as a whole and became a light pink transparent solution. A part of the solution after the reaction was collected and measured by ²⁹ Si-NMR, ¹³ C-NMR, and ¹ H-NMR. As a result of identifying the product from the measurement results, PhSi (OMe) was obtained in the same manner as in Example 1. It was confirmed that ₃ was generated.

  From the above results, it was confirmed that the hydrolyzable silicon-containing compound of the present invention can be obtained even when a metal salt which is a Lewis acid catalyst other than bismuth chloride is used. In particular, by using iron (III) chloride, it was confirmed that the reaction proceeded quickly in a uniform reaction system.

[Example 16]
Install a magnetic stir bar inside a round bottom flask (Schlenk tube) with a 100 ml capacity 2-way cock, charge 0.24 g (0.75 mmol) of bismuth chloride (BiCl ₃ ), seal the flask with a septum, and replace with nitrogen. Went. Next, 21.9 g (248 mmol) of methyl tert-butyl ether and 19.62 g (75 mmol) of 3-methacryloxypropyltrichlorosilane were charged into the flask in the same manner as in Example 1, and the system was returned to room temperature (25 ° C.). The whole flask was shielded from light with aluminum foil, and the solution was reacted for 3 days (72 hours) while stirring the solution using a magnetic stirrer. Since bismuth chloride was precipitated in the solution after the reaction, the yield of the product was determined after removing bismuth chloride by Celite filtration. The results are shown in Table 2.

A part of the solution after the above reaction was collected, measured by ²⁹ Si-NMR, ¹³ C-NMR, and ¹ H-NMR, and as a result of identifying the product from the measurement results, 3-methacryloxypropyltrimethoxysilane was obtained. It was confirmed that (CH ₂ = C (CH ₃ ) COOC ₃ H ₆ -Si (OMe) ₃ ) was produced.

[Example 17]
Install a magnetic stirring bar inside a round bottom flask (Schlenk tube) with a capacity of 30 ml, charge 32 mg (0.10 mmol) of bismuth chloride (BiCl ₃ ), seal the flask with a septum, and replace with nitrogen. went. Next, 4.03 g (33 mmol) of methylbenzyl ether and 2.11 g (10 mmol) of phenyltrichlorosilane were charged into the flask in the same manner as in Example 1. The system was heated to 80 ° C., and the solution was prepared using a magnetic stirrer. The reaction was allowed to proceed overnight (15 hours) with stirring to determine the yield of the product. The results are shown in Table 2. The solution after the reaction turned black and bismuth chloride was precipitated.

A part of the solution after the above reaction was collected, measured by ²⁹ Si-NMR, ¹³ C-NMR, and ¹ H-NMR, and as a result of identifying the product from the measurement result, as in Example 1, PhSi ( It was confirmed that OMe) ₃ was formed.

[Example 18]
32 mg (0.10 mmol) of bismuth chloride (BiCl ₃ ) was charged into a 30 ml round bottom flask (Schlenk tube) equipped with a stirrer, and the flask was sealed with a septum and purged with nitrogen. Next, 6.08 g (33 mmol) of phenylbenzyl ether and 1.50 g (10 mmol) of methyltrichlorosilane were charged into the flask in the same manner as in Example 1, and the system was heated to 60 ° C. overnight (15 hours). And the yield of the product was determined. The results are shown in Table 2. In the solution after the reaction, bismuth chloride was precipitated.

A part of the solution after the above reaction was collected and measured by ²⁹ Si-NMR, ¹³ C-NMR, and ¹ H-NMR, and the product was identified from the measurement result. As a result, MeSi (OPh) ₃ is indicated. It was confirmed that phenoxysilane was produced.

[Example 19]
32 mg (0.10 mmol) of bismuth chloride (BiCl ₃ ) was charged into a 30-ml round bottom flask (Schlenk tube) equipped with a stirrer and purged with nitrogen, and the flask was sealed with a septum. Next, 6.54 g (33 mmol) of methyl (diphenylmethyl) ether (chemical formula: CH ₃ —O—CH (C ₆ H ₅ ) ₂ ) and 1.50 g (10 mmol) of methyltrichlorosilane were added in the same manner as in Example 1. The flask was charged and the system was returned to room temperature (25 ° C.) and reacted overnight (15 hours) to determine the yield of the product. The results are shown in Table 2. In the solution after the reaction, bismuth chloride was precipitated.

A part of the solution after the above reaction was collected and measured by ²⁹ Si-NMR, ¹³ C-NMR, and ¹ H-NMR. As a result of identifying the product from the measurement result, MeSi (OMe) ₃ was produced. It was confirmed that

＊）表中において、官能基の略号は以下の通りである。
Me：メチル基
Ph：フェニル基
tert-Bu：第３級ブチル基
Methacryloxypropyl：３−メタクリロキシプロピル基（CH₂=C(CH₃)COOC₃H₆- ）
＊＊）反応時間は３日間とした。

*) In the tables, functional group abbreviations are as follows.
Me: Methyl group
Ph: Phenyl group
tert-Bu: Tertiary butyl group
Methacryloxypropyl: 3-methacryloxypropyl group (CH ₂ = C (CH ₃ ) COOC ₃ H _6- )
**) The reaction time was 3 days.

The attribution of ¹³ C of each hydrolyzable silane is as shown in the figure. A sharp signal near σ = 34.5 ppm is a signal attributed to tert-BuCl to be generated, and a sharp signal near σ = 27.0 ppm is a signal attributed to an excess amount of tert-BuOMe. Further, as shown in the comparison between Comparative Example 1 and Example 9 shown in FIG. 4, in the direct reaction with methanol, the corresponding hydrolyzable silanes were hardly generated. Moreover, as shown in FIG. 5, the production | generation of acetyl chloride was not able to be confirmed at all on NMR.

<Explanation of NMR chart>
Abbreviations for functional groups are as follows.
Me: Methyl group
Ph: Phenyl group
cyc-Hex: cyclohexyl group
Ac: Acetyl group
Methacryloxypropyl: 3-methacryloxypropyl group (CH ₂ = C (CH ₃ ) COOC ₃ H _6- )

Figure 1: σ = 128.0-135.0ppm signals attributable to the phenyl group of PhSi (OMe) ₃ in the vicinity, and a signal attributed to methoxy groups PhSi (OMe) ₃ in the vicinity of σ = 50.5ppm exists.
Figure 2: σ = 50.3ppm signal assignable to a methoxy group cyc-HexMeSi (OMe) ₂ in the vicinity, and a signal attributed to a cyclohexyl group cyc-HexMeSi (OMe) ₂ in the vicinity of σ = 24-27.96ppm Exists.
Fig. 3: The signal shape is completely different from Fig. 2, and each signal cannot be assigned.
FIG. 4: In the upper stage (Example 9), the signal attributed to ²⁹ Si of cyc-HexMeSi (OMe) ₂ is around σ = −3.57 ppm, and in the lower stage (Comparative Example 1) is around σ = 32.6 ppm. There is a signal attributed to ²⁹ Si of the raw material cyc-HexMeSiCl ₂ .
FIG. 5: Signals attributed to CH ₂ = CHSi (OAc) ₃ exist in the vicinity of σ = 140.5, 125.5, 22.5 ppm, while signals around 33.68 ppm attributed to acetyl chloride were not observed.
FIG. 6: The signal shape is almost the same as FIG. 1, and the product is the same. There is a signal attributed to the phenyl group of PhSi (OMe) ₃ near σ = 128.0-134.9 ppm, and a signal attributed to the methoxy group of PhSi (OMe) ₃ near σ = 50.8 ppm.
FIG. 7: Although the signal of the unreacted raw material is seen, the signals are the same as those in FIGS. There is a signal attributed to the phenyl group of PhSi (OMe) ₃ around σ = 128.0-134.9 ppm, and a signal attributed to the methoxy group of PhSi (OMe) ₃ around σ = 50.8 ppm.
FIG. 8: Signals attributed to Methacryloxypropyl Si (OMe) ₃ are present around σ = 167.4, 136.6, 125.2, 66.6, 50.5, 22.2, 18.3, 5.8 ppm.
FIG. 9: For signals other than the raw material, the signal shape is almost the same as in FIG. 1, and the product is the same. There is a signal attributed to the phenyl group of PhSi (OMe) ₃ near σ = 127.6-134.8 ppm, and a signal attributed to the methoxy group of PhSi (OMe) ₃ near σ = 50.7 ppm.

Claims (6)

(A) General formula:

R ¹ —O—R ²

(Where
R ¹ represents a substituted or unsubstituted tertiary alkyl group or aralkyl group having 4 to 30 carbon atoms,
R ² represents a substituted or unsubstituted monovalent hydrocarbon group or acyl group having 1 to 30 carbon atoms)
And a compound represented by:
(B) General formula:

R ³ _m SiX _4-m

(Where
R ³ independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms,
X is independently bromine or chlorine;
m represents an integer of 0 to 3), and a hydrogen halide or halogenation is reacted in the presence of one or more Lewis acid catalysts selected from the group consisting of bismuth chloride and iron (III) chloride A method for producing a hydrolyzable silicon-containing compound which is an alkoxysilane, phenoxysilane or acetoxysilane substantially free of acyl. The production method according to claim 1, wherein (B) the halosilane is chlorosilane. The manufacturing method of Claim 1 or 2 whose said (A) compound is ether. The production method according to claim 3, wherein the ether is at least one ether selected from methyl tert-butyl ether, ethyl tert-butyl ether, methyl-diphenylmethyl ether and methyltriphenylmethyl ether. The manufacturing method of Claim 1 or 2 whose said (A) compound is ester. The production method according to claim 5, wherein the ester is tert-butyl acetate or diphenylmethyl acetate.

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