JP2023110137A - Method for producing halosilane - Google Patents

Abstract

To provide a method to efficiently produce a halosilane suitable as a functional chemical.SOLUTION: A method for producing a halosilane includes a reaction step for reacting an alkoxysilane with a carboxylic acid halide in the presence of a catalyst, the catalyst being a solid acid catalyst.SELECTED DRAWING: None

Description

The present invention relates to an efficient method for producing halosilanes.

Halosilanes are functional chemicals used as raw materials for functional materials related to silicones, silane coupling agents, etc., and reagents for precision synthesis of pharmaceuticals, agricultural chemicals, electronic materials, and the like.
As a method for producing halosilanes, a method of converting an alkoxy group of an alkoxysilane to a chloro group using a carboxylic acid chloride is known. In this method, zinc chloride (Patent Documents 1 and 3), zinc oxide (Patent Document 2), iron chloride (Non-Patent Documents 1 and 2), and the like are used as catalysts.

Japanese Patent Application Laid-Open No. 2010-37303 JP 2013-155150 A WO2018/173993

Macromolecules 1996, 29, 18, 5788-5796 Organometallics 2012, 31, 8, 3199-3206

However, in the method using the catalyst, the catalyst is dissolved in the reaction solution in many cases, and there are problems such as difficulty in separating and recovering the catalyst. For these reasons, there is a demand for an industrially more advantageous production method.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for more efficiently producing halosilanes from alkoxysilanes.

The present inventors have made intensive studies to solve the above problems, and found that halosilanes can be efficiently produced by using a specific solid acid catalyst as a catalyst in the reaction between alkoxysilanes and carboxylic acid halides. The inventors have found that and completed the present invention.
The manufacturing method of the present invention has the following features.
(1) Raw materials and catalysts are readily available and relatively easy to handle.
(2) Since a solid catalyst is used as the catalyst, the catalyst can be easily separated and recovered by filtration, centrifugation, or the like.
(3) By adjusting the reaction conditions, only some of the multiple alkoxy groups can be selectively converted to halogeno groups.
The manufacturing method of the present invention enables cost reduction and high efficiency of the manufacturing process, and has great advantages in terms of economic efficiency, environmental burden, etc., as compared with conventional techniques.

That is, this application provides the following inventions.
<1>
A reaction step of reacting alkoxysilanes with a carboxylic acid halide in the presence of a catalyst,
A method for producing halosilanes, wherein the catalyst is a solid acid catalyst.
<2>
The alkoxysilanes are alkoxysilanes represented by the following general formula (I),
The carboxylic acid halide is a carboxylic acid halide represented by the following general formula (II),
The method for producing halosilanes according to <1>, wherein the halosilanes are represented by the following general formula (III).
R ¹ _p R ² _q R ³ _r Si(OR ⁴ ) _4-(p+q+r) (I)
(Wherein, p, q, and r are each independently an integer of 0 to 3; p+q+r is an integer of 0 to 3; R ¹ , R ² , and R ³ are each independently a hydrocarbon group having 1 to 24 carbon atoms or a hydrogen atom, and some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group may be substituted with groups that do not participate ⁱⁿ the reaction; Each independently represents an alkyl group having 1 to 6 carbon atoms.)
^R5COX (II)
(In the formula, R ⁵ is an alkyl group having 1 to 6 carbon atoms, and some or all of the hydrogen atoms bonded to the carbon atoms of the alkyl group may be substituted with groups that do not participate in the reaction; X is a halogen atom.)
R ¹ _p R ² _q R ³ _r Si(OR ⁴ ) _4-(p+q+r+s) X _s (III)
(Wherein, p, q, r, R ¹ , R ² , R ³ , R ⁴ , and X have the same definitions as above; s is an integer of 1 or more and 4-(p+q+r) or less.)
<3>
The method for producing halosilanes according to <1> or <2>, wherein the solid acid catalyst is one or more solid acid catalysts selected from montmorillonite, zeolite, and cation exchange resins.
<4>
said montmorillonite from lanthanum (III), cerium (III), titanium (IV), zirconium (IV), iron (III), aluminum (III), gallium (III), indium (III), and tin (IV) The method for producing halosilanes according to <3>, which is montmorillonite having one or more selected cations or protic hydrogen atoms.

By using the production method of the present invention, it is possible to produce halosilanes using alkoxysilanes as raw materials more efficiently than conventional methods.

The present invention will be described in detail below.
A method for producing halosilanes according to one embodiment of the present invention includes a reaction step of reacting alkoxysilanes with a carboxylic acid halide in the presence of a specific catalyst.

In this embodiment, the alkoxysilanes used as raw materials are represented by the following general formula (I), for example.
R ¹ _p R ² _q R ³ _r Si(OR ⁴ ) _4-(p+q+r) (I)
In general formula (I), p, q, and r are each independently an integer of 0 or more and 3 or less; p+q+r is an integer of 0 or more and 3 or less. R ¹ , R ² , and R ³ are each independently a hydrocarbon group having 1 to 24 carbon atoms or a hydrogen atom, and some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group react may be substituted with groups that do not participate in Each R ⁴ is independently an alkyl group having 1 to 6 carbon atoms.
As used herein, the term "group that does not participate in the reaction" means a group that does not directly participate in the target reaction as a reactive group and does not inhibit the reaction.

Examples of hydrocarbon groups represented by R ¹ , R ² and R ³ include alkyl groups, aryl groups, aralkyl groups and alkenyl groups.
When the hydrocarbon group is an alkyl group, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 4 carbon atoms. Some or all of the hydrogen atoms bonded to the carbon atoms of the alkyl group may be substituted with groups that do not participate in the reaction.

Groups that do not participate in the reaction include alkoxy groups having 1 to 6 carbon atoms, alkoxycarbonyl groups having 1 to 6 carbon atoms, dialkylamino groups having 1 to 6 carbon atoms, cyano groups, nitro groups, and halogen atoms. More specifically, alkoxy groups, alkoxycarbonyl groups, dialkylamino groups, and halogen atoms include alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, and hexoxy groups; and 1 to 6 carbon atoms. Examples of the alkoxycarbonyl group include methoxycarbonyl group and propoxycarbonyl group; examples of dialkylamino group having 1 to 6 carbon atoms include dimethylamino group and diethylamino group; examples of halogen atom include fluorine atom, A chlorine atom, a bromine atom, etc. are mentioned.

Specific examples of alkyl groups optionally substituted with groups that do not participate in the reaction include methyl, ethyl, propyl, butyl, sec-butyl, pentyl, hexyl, cyclohexyl, octyl and decyl. group, 2-methoxyethyl group, 3-ethoxypropyl group, 2-methoxycarbonylethyl group, 2-dimethylaminoethyl group, 2-cyanoethyl group, trifluoromethyl group, 3-chloropropyl group and the like.

When the hydrocarbon group is an aryl group, the aryl group can be a monovalent aromatic organic group of a hydrocarbon ring system or a heterocyclic ring system. When the aryl group is a monovalent aromatic organic group of a hydrocarbon ring system, it preferably has 6-22 carbon atoms, more preferably 6-14 carbon atoms, and still more preferably 6-10 carbon atoms. Specific examples of monovalent aromatic organic groups having a hydrocarbon ring system include phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, and pentacenyl groups. When the aryl group is a heterocyclic monovalent aromatic organic group, the heteroatom in the heterocyclic ring is sulfur, oxygen, or the like. The number of carbon atoms in the heterocyclic monovalent aromatic organic group is preferably 4-12, more preferably 4-8. Specific examples of heterocyclic monovalent aromatic organic groups include thienyl, benzothienyl, dibenzothienyl, furyl, benzofuryl and dibenzofuryl groups.
Some or all of the hydrogen atoms bonded to the carbon atoms of the aryl group may be substituted with groups that do not participate in the reaction. Examples of the non-reaction-involved group include those shown as the non-reaction-involved group which may be substituted on the alkyl group. Examples of other groups that do not participate in the reaction include an oxyethylene group, an oxyethyleneoxy group, etc., which are divalent groups that bond two carbon atoms on a ring.

Specific examples of the aryl group optionally substituted with groups that do not participate in the reaction include methylphenyl, ethylphenyl, hexylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, octoxyphenyl, methyl (Methoxy)phenyl group, fluoro(methyl)phenyl group, chloro(methoxy)phenyl group, bromo(methoxy)phenyl group, 2,3-dihydrobenzofuranyl group, 1,4-benzodioxanyl group and the like. .

Furthermore, when the hydrocarbon group is an aralkyl group, the aralkyl group preferably has 7 to 23 carbon atoms, more preferably 7 to 16 carbon atoms. Also, some or all of the hydrogen atoms bonded to the carbon atoms of the aralkyl group may be substituted with groups that do not participate in the reaction.
Examples of the non-reaction-involved group include those shown as the non-reaction-involved group which may be substituted on the alkyl group.

Specific examples of the aralkyl group optionally substituted with groups that do not participate in the reaction include a benzyl group, a phenethyl group, a 2-naphthylmethyl group, a 9-anthrylmethyl group, a (4-chlorophenyl)methyl group, a 1-( 4-methoxyphenyl)ethyl group and the like.

When the hydrocarbon group is an alkenyl group, the alkenyl group preferably has 2 to 23 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 10 carbon atoms. Also, some or all of the hydrogen atoms bonded to the carbon atoms of the alkenyl group may be substituted with groups that do not participate in the reaction.
Specific examples of the groups that do not participate in the reaction include the above-mentioned groups that may be substituted on the alkyl group and do not participate in the reaction, as well as the above-mentioned aryl groups.

Specific examples of the alkenyl group optionally substituted with groups that do not participate in the reaction include vinyl group, 2-propenyl group, 3-butenyl group, 5-hexenyl group, 9-decenyl group, 2-phenylethenyl group, 2-(methoxyphenyl)ethenyl group, 2-naphthylethenyl group, 2-anthrylethenyl group and the like.

The carbon number of the alkyl group having 1 to 6 carbon atoms represented by R ⁴ is preferably 1 to 4, more preferably 1 to 3.
Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, sec-butyl group, pentyl group, hexyl group and cyclohexyl group.

Specific examples of alkoxysilanes represented by formula (I) include trimethyl(methoxy)silane (Me ₃ SiOMe), (ethoxy)trimethylsilane (Me ₃ SiOEt), di(methoxy)dimethylsilane (Me ₂ Si (OMe) ₂ ), di(ethoxy)dimethylsilane (Me ₂ Si(OEt) ₂ ), di(methoxy)(methyl)(phenyl)silane (MePhSi(OMe) ₂ ), di(ethoxy)(phenyl)vinylsilane ( PhViSi(OEt) ₂ ), tri(methoxy)methylsilane (MeSi(OMe) ₃ ), tri(ethoxy)methylsilane (MeSi(OEt) ₃ ), tri(methoxy)phenylsilane (PhSi(OMe) ₃ ), tri(ethoxy ) phenylsilane (PhSi(OEt) ₃ ), tri(methoxy)vinylsilane (ViSi(OMe) ₃ ), tri(ethoxy)vinylsilane (ViSi(OEt) ₃ ), tri(methoxy)silane (HSi(OMe) ₃ ), tri(ethoxy)silane (HSi(OEt) ₃ ), tetramethoxysilane (Si(OMe) ₄ ), tetraethoxysilane (Si(OEt) ₄ ), tetrapropoxysilane (Si(OPr) ₄ ), tetrabutoxysilane ( Si(OBu) ₄ ) and the like.

On the other hand, the carboxylic acid halide to be reacted with the alkoxysilanes is represented, for example, by the following general formula (II).
^R5COX (II)

In general formula (II), R ⁵ is an alkyl group having 1 to 6 carbon atoms, and some or all of the hydrogen atoms bonded to the carbon atoms of the alkyl group are substituted with groups that do not participate in the reaction. also; X is a halogen atom.

Specific examples of groups that do not participate in the reaction include the groups that do not participate in the reaction shown in the explanation of R ¹ , R ² and R ³ in the general formula (I).
The carbon number of the alkyl group having 1 to 6 carbon atoms represented by R ⁵ is preferably 1 to 4, more preferably 1 to 2.
Specific examples of the alkyl group optionally substituted with groups that do not participate in the reaction include those shown in the explanation of R ¹ , R ² and R ³ in the general formula (I).

The halogen atom represented by X includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, preferably a chlorine atom or a bromine atom, more preferably a chlorine atom.

Specific examples of the carboxylic acid halide (II) represented by the general formula (II) include acetyl fluoride (MeCOF), propionyl fluoride (EtCOF), butyryl fluoride (PrCF), acetyl chloride (MeCOCl), and propionyl chloride. (EtCOCl), butyryl chloride (PrCOCl), acetyl bromide (MeCOBr), propionyl bromide (EtCOBr), butyryl bromide (PrCOI), acetyl iodide (MeCOI), propionyl iodide (EtCOI), butyryl iodide (PrCOI) ) and the like, preferably acetyl chloride (MeCOCl).

The molar ratio of the carboxylic acid halide to the alkoxysilanes can be arbitrarily selected, but considering the yield of the halosilanes based on the alkoxysilanes, it is usually 0.4 or more and 20 or less, more preferably 0. 0.5 or more and 10 or less, more preferably 0.5 or more and 6 or less.

According to this embodiment, the halosilanes represented by the following general formula (III) can be produced by reacting the alkoxysilanes of the general formula (I) with the carboxylic acid halide of the general formula (II).
R ¹ _p R ² _q R ³ _r Si(OR ⁴ ) _4-(p+q+r+s) X _s (III)

p, q, r, R ¹ , R ² , R ³ , R ⁴ and X in general formula (III) are as defined above, and specific examples thereof include ) can be mentioned. Further, s is an integer of 1 or more and 4-(p+q+r) or less, preferably 1 or more and 3-(p+q+r) or less.

Specific examples of halosilanes represented by formula (III) include chlorotrimethylsilane (Me ₃ SiCl), chlorotriethylsilane (Et ₃ SiCl), chlorodimethyl(phenyl)silane (Me ₂ PhSiCl), chloromethyldi(phenyl)silane ( _MePh2SiCl ), chlorodimethyl(vinyl)silane ( _Me2ViSiCl ), chloro(methoxy)dimethylsilane (Me2Si(OMe)Cl), chloro(ethoxy)di( _methyl ) silane ( _Me2Si (OEt)Cl), dichlorodi(methyl)silane ( _Me2SiCl2 ), chloro(methoxy)(methyl)(phenyl)silane (MePhSi(OMe)Cl ₎ , chloro(ethoxy)(methyl)( phenyl)silane (MePhSi(OEt)Cl), dichloro(methyl)(phenyl)silane (MePhSiCl2), _{chlorodi(methoxy)(methyl)silane (MeSi(OMe)2Cl )} , dichloro(methoxy)(methyl)silane ( MeSi(OMe) _Cl2 ), chlorodi(ethoxy)(methyl)silane (MeSi(OEt) _2Cl ), dichloro(ethoxy)(methyl)silane (MeSi(OEt) _Cl2 ), trichloro(methyl)silane ( _MeSiCl3) ), chlorodi(methoxy)(phenyl)silane (PhSi(OMe) _2Cl ), dichloro(methoxy)(phenyl)silane (PhSi(OMe) _Cl2 ), chlorodi(ethoxy)(phenyl)silane (PhSi(OEt) ₂ Cl), dichloro(ethoxy)(phenyl)silane (PhSi(OEt) _Cl2 ), trichloro(phenyl)silane ( _PhSiCl3 ), chlorodi(methoxy)(vinyl)silane (ViSi(OMe) _2Cl ), dichloro(methoxy ) (vinyl)silane (ViSi(OMe) _Cl2 ), chlorodi(ethoxy)(vinyl)silane (ViSi(OEt) _2Cl ), dichloro(ethoxy)(vinyl)silane (ViSi(OEt) _Cl2 ), trichloro( vinyl)silane (ViSiCl ₃ ), chlorotri(methoxy)silane (Si(OMe) ₃ Cl), dichlorodi(methoxy)silane (Si(OMe
) ₂ Cl ₂ ), trichloro(methoxy)silane (Si(OMe)Cl ₃ ), chlorotri(ethoxy)silane (Si(OEt) ₃ Cl), dichlorodi(ethoxy)silane (Si(OEt) ₂ Cl ₂ ), trichloro (ethoxy)silane (Si(OEt)Cl ₃ ), tetrachlorosilane (SiCl ₄ ), and the like. Fluorosilanes, bromosilanes, and iodosilanes include compounds in which the chloro group of the compounds shown as specific examples of chlorosilanes is replaced with a fluoro group, a bromo group, and an iodo group, respectively.

The reaction step in the present embodiment is a reaction step involving a nucleophilic substitution reaction of alkoxysilanes, which are raw materials having an alkoxy group, with a carboxylic acid halide.
For example, when a monoalkoxysilane is reacted with a carboxylic acid halide, the reaction in the reaction step is a reaction that accompanies elimination of the carboxylic acid ester. That is, in the reaction step of the present embodiment, in the presence of a solid acid catalyst having a cation (M ^m+ ) of an element of Groups 3 to 15, the reaction takes place according to the reaction mechanism shown in the following reaction formula (Scheme 1). is thought to proceed.

In this reaction mechanism, the cation (M ^m+ ) of the group 3 to group 15 element of the solid acid catalyst coordinates to the oxygen atom of the carboxylic acid halide, thereby increasing the nucleophilicity of the carbon atom of the carbonyl group. It is thought that it increases the reaction rate and accelerates the reaction.

In the reaction step, the raw material alkoxysilanes are not limited to monoalkoxysilanes, and may be dialkoxysilanes, trialkoxysilanes, tetraalkoxysilanes, and the like.
That is, the number of halosilanes obtained in the reaction step in the present embodiment is one when monoalkoxysilane is used as a raw material, but when dialkoxysilane, trialkoxysilane, or tetraalkoxysilane is used as raw material, one type is obtained. is not limited to halosilanes. For example, when dialkoxysilane is used as a raw material, halosilanes to be produced are halosilanes in which one alkoxy group of alkoxysilanes is substituted, halosilanes in which two alkoxy groups of alkoxysilanes are substituted, or these. It means that it may be a mixture of Furthermore, when trialkoxysilane is used as a raw material, halosilanes to be produced include halosilanes in which one alkoxy group of alkoxysilanes is substituted, halosilanes in which two alkoxy groups of alkoxysilanes are substituted, and alkoxysilanes. may be halosilanes substituted with three alkoxy groups, or a mixture thereof. In addition, when tetraalkoxysilane is used as a raw material, halosilanes to be produced include halosilanes in which one alkoxy group of alkoxysilanes is substituted, halosilanes in which two alkoxy groups of alkoxysilanes are substituted, and alkoxysilanes. It means that halosilanes in which three alkoxy groups of silanes are substituted, halosilanes in which four alkoxy groups of alkoxysilanes are substituted, or a mixture thereof may be used.

In the reaction step of this embodiment for producing halosilanes, a specific solid acid catalyst is used to promote the reaction. The solid acid catalyst may be an inorganic solid acid catalyst or an organic solid acid catalyst.

Examples of inorganic solid acid catalysts include solid inorganic substances such as metal salts and metal oxides. More specifically, zeolite, mesoporous silica, montmorillonite, etc. having protic hydrogen atoms or cations of elements of groups 3 to 15; inorganic solid acids with silica gel, heteropolyacid, carbon-based materials, etc. as carriers ; and the like.
Among these, the inorganic solid acid catalyst is preferably selected from montmorillonite and zeolite.

Examples of cations of Groups 3 to 15 elements include scandium (III), lanthanum (III), cerium (III), neodymium (III), samarium (III), titanium (IV), zirconium (IV), ), iron (III), ruthenium (II), nickel (II), palladium (II), copper (II), zinc (II), aluminum (III), gallium (III), indium (III), tin (IV ) and the like.
Among the cations of elements of groups 3 to 15, scandium (III), lanthanum (III), cerium (III), titanium (IV), zirconium (IV), iron (III), zinc (II) , aluminum(III), gallium(III), indium(III) and tin(IV) are preferred.

With respect to montmorillonite, cations of elements of groups 3 to 15 include lanthanum (III), cerium (III), titanium (IV), zirconium (IV), iron (III), aluminum (III), gallium ( III), indium (III) and tin (IV), or montmorillonite with protic hydrogen atoms are more preferably used, gallium (III), indium (III) and tin (IV) ) are more preferably used.

Montmorillonite having cations of elements of Groups 3 to 15 includes, for example, commercially available montmorillonite having sodium (I) as a cation (for example, Kunipia (registered trademark) F, available from Kunimine Industry Co., Ltd.). , by treatment with an aqueous solution containing cations of elements of groups 3 to 15.
As the montmorillonite having protonic hydrogen atoms, commercially available products can be used. Examples of commercial products of montmorillonite having protic hydrogen atoms include montmorillonite K10 and montmorillonite K30 (both available from Merck & Co.).

As for zeolites, various zeolites having basic skeletons such as Y-type, beta-type, ZSM-5-type, mordenite-type and SAPO-type can be used.
In addition, SUSY type (Super Ultrastable Y), VUSY type (Very Ultrastable Y), SDUSY type (Super dealuminated ultrastable) obtained by secondary treatment of Y type zeolite (Na—Y)
USY type (Ultrastable Y type) known as Y) etc. can also be preferably used (USY type, for example, GT KERR et al., "Molecular Sieves", Vol. 121, (US), American Chemical Society, June 1, 1973, p.219-229 (Chapter 19), etc.).

In terms of reaction rate, among these zeolites, USY type, beta type, ZSM-5 type and mordenite type are preferably selected, and USY type and beta type are more preferred.
As these zeolites, various zeolites such as Bronsted acid zeolites having protic hydrogen atoms and Lewis acid zeolites having cations of Groups 3 to 15 can be used.

Among these, proton-type zeolites having protic hydrogen atoms are represented by HY type, H-SDUSY type, H-SUSY type, H-beta type, H-mordenite type, H-ZSM-5 type, etc. be. In addition, zeolites such as NH ₄ -Y type, NH ₄ -VUSY type, NH ₄ -beta type, NH ₄ -Mordenite type, and NH ₄ -ZSM-5 type, which are ammonium type zeolites, are calcined into proton type. The converted product can be used as a proton-type zeolite.

Further, the silica/alumina ratio (substance amount ratio) of zeolite can be selected from various ratios depending on the reaction conditions. More preferably 5-200.

Various zeolites including commercially available zeolites can be used. Specific examples of commercially available zeolites include CBV760, CBV780, CBV720, CBV712, and CBV600 commercially available from Zeolyst. Examples of Y-type zeolites include HSZ-360HOA and HSZ-320HOA commercially available from Tosoh Corporation. Moreover, as the beta-type zeolite, CP811C, CP814N, CP7119, CP814E, CP7105, CP814CN, CP811TL, CP814T, CP814Q, CP811Q, CP811E-75, CP811E, CP811C-300, etc. commercially available from Zeolist; HSZ-930HOA, HSZ-940HOA, etc. available from UOP; UOP-Beta, etc. available from UOP;

On the other hand, as the catalyst, in addition to the above inorganic solid acid catalyst, an organic solid acid catalyst having an acidic functional group can also be used. Examples of organic solid acid catalysts include cation exchange resins. As the cation exchange resin, a polymer having an acidic functional group such as an H ⁺ type cation exchange resin having protic hydrogen atoms can be used. may Types of the acidic functional group include sulfo group, carboxy group, phosphoryl group and the like, preferably sulfo group or carboxy group. Further, examples of types of polymers include Teflon (registered trademark) backbone polymers having perfluoro side chains, styrene-divinylbenzene copolymers, (meth)acrylic acid-divinylbenzene copolymers, and the like.

Specific examples of polymers with acidic functional groups include Nafion (registered trademark), available from DuPont or Merck, Dowex (registered trademark), Dow Chemical or Merck, which have sulfo groups. ), AMBERLITE® (available from Rohm & Haas or Merck), AMBERLYST® (available from The Dow Chemical Company or Merck), PUROLITE ( (registered trademark), available from Purolite), and the like.
More specifically, they include Nafion NR50, Dowex 50WX2, Dowex 50WX4, Dowex 50WX8, Amberlite IR120, Amberlite IRP-64, Amberlyst 15, Amberlyst 36, Purolite CT175, and the like. .

Among these organic solid acid catalysts, solid acids selected from Amberlyst 15, Purolite CT175, and Nafion NR50 are preferably used, and solid acids selected from Amberlyst 15 and Purolite CT175 are more preferably used.

The catalyst used in the production method according to the present embodiment can be used not only singly, but also in any combination and ratio of multiple catalysts.

The amount of catalyst to alkoxysilanes can be determined arbitrarily, but in terms of molar ratio or weight ratio, it is usually about 0.0001 to 10, preferably about 0.001 to 8, more preferably about 0.001 to 6, and further It is preferably about 0.01 to 1.

The reaction in the reaction step can be carried out in liquid phase or gas phase, depending on the reaction temperature and reaction pressure.
The reaction temperature is usually -20°C or higher, preferably -10 to 300°C, more preferably -10 to 200°C, still more preferably 0 to 150°C. When the reaction is carried out at room temperature, the temperature range of room temperature is usually 0 to 40°C, preferably 5 to 40°C, more preferably 10 to 35°C.

Furthermore, the reaction pressure is usually 0.1 to 100 atmospheres, preferably 0.1 to 50 atmospheres, more preferably 0.1 to 10 atmospheres, and still more preferably 0.5 to 5 atmospheres.
The reaction time depends on the amount of raw materials, the amount of catalyst, the reaction temperature, the form of the reactor, etc., but in consideration of productivity and efficiency, it is usually 0.1 to 2400 minutes, preferably 0.1 to 1200 minutes. , more preferably 0.1 to 600 minutes, more preferably about 0.1 to 300 minutes.

In addition, as the form of the reaction apparatus, various conventionally known forms such as a batch system and a flow system can be used. Since a solid acid catalyst is used in the reaction step of the present embodiment, a flow reaction system using a column filled with a catalyst can be suitably applied to the production method of the present embodiment.

When the reaction is carried out in a liquid phase system, it can be carried out with or without a solvent. In general, the reaction proceeds faster in the absence of a solvent, but when a solvent is used, hydrocarbons such as decalin (decahydronaphthalene) and decane, Various solvents that do not react with the raw materials and products can be used, such as halogenated hydrocarbons such as 2,3- or 1,2,4-trichlorobenzene, and ethers such as tert-butyl methyl ether and dibutyl ether. Two or more kinds of solvents can be mixed and used. As the reaction solvent, deuterated solvents such as deuterated chloroform and deuterated benzene can be used in order to analyze the reaction product with a nuclear magnetic resonance spectrometer.
Further, when the reaction is carried out in the gas phase, the reaction can be carried out by mixing an inert gas such as nitrogen.

The reaction step can also be performed under microwave irradiation. In this reaction system, the carboxylic acid halide, the ionic acidic catalyst, etc. are relatively highly polarized and absorb microwaves efficiently. can be done more efficiently.

Various commercially available devices equipped with a contact or non-contact temperature sensor can be used in the microwave irradiation reaction. In addition, the power of microwave irradiation, the type of cavity (multimode, single mode), the mode of irradiation (continuous, intermittent), etc., can be arbitrarily determined according to the scale of the reaction, the type of raw material, the type of catalyst, etc. be able to. The frequency of microwaves is usually 0.3 to 30 GHz. Preferred among these are the IMS frequency bands allocated for use in the industrial, scientific, medical, and other fields, and more preferred are the 2.45 GHz band, the 5.8 GHz band, and the like.

In the microwave irradiation reaction, a heating material (susceptor) that generates heat by absorbing microwaves can be added to the reaction system in order to heat the reaction system more efficiently. As the type of heating material, various conventionally known ones such as activated carbon, graphite, silicon carbide, and titanium carbide can be used. Also, a molded catalyst obtained by mixing the above-described catalyst and heating material powder and firing the mixture using an appropriate binder such as sepiolite or formite can also be used.

The reaction process in the present embodiment proceeds even in a closed system reactor, but the reaction proceeds more efficiently by making the reactor an open system and continuously removing the reaction product out of the reaction system. can also

In the production method according to the present embodiment, since the catalyst is a solid catalyst, the separation and recovery of the catalyst after the reaction step can be easily performed by a method such as filtration or centrifugation.
Purification of the produced halosilanes can be easily accomplished by means commonly used in organic chemistry, such as distillation and recrystallization.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
The main analyzers and the like used in the following examples are as follows.
・Nuclear magnetic resonance spectrum analysis (hereinafter sometimes referred to as NMR): Bruker AVANCE III HD 600 MHz (with cryoprobe)
・ Gas chromatograph analysis (hereinafter sometimes referred to as GC): GC-2014 manufactured by Shimadzu Corporation
・ Gas chromatograph mass spectrometry (hereinafter sometimes referred to as GC-MS): GCMS-QP2010Plus manufactured by Shimadzu Corporation

(Example 1)
(ethoxy)trimethylsilane ( _Me3SiOEt ) 0.5 mmol, acetyl chloride (
MeCOCl) 0.56 mmol, montmorillonite containing tin (IV) (Sn ⁴⁺ -containing montmorillonite, Mont-Sn ⁴⁺ ) 5 mg, and deuterated chloroform 0.4 mL were placed in a reaction tube (NMR sample tube) and heated to about 25° C. (room temperature). and left for 3 hours. The product was analyzed by NMR, and the yield was calculated. As a result, it was found that chlorotrimethylsilane (Me ₃ SiCl), a compound in which the methoxy group was converted to a chloro group, was produced in a yield of 78%. (See Table 1-1).

(Examples 2 to 59)
A reaction was carried out in the same manner as in Example 1, except that the reaction conditions (catalyst, raw materials, reaction time, etc.) were changed as shown in Table 1. The products were analyzed by NMR, GC, and/or GC-MS, and the yields of the products were calculated by NMR, and the results are shown in Tables 1-1 to 1-4.

Tables 2-1 to 2-3 show spectral data of the halosilanes obtained in the above Examples.

Annotations in Tables 1-1 to 1-4 are shown below.
1) In Examples 1 to 57, deuterated chloroform (0.4 mL) was used as a solvent and the reaction was carried out without stirring. Further, in Examples 58 and 59, the reaction was carried out without using a solvent while stirring the solution with a magnetic stirrer by inserting a stirrer into the solution.
2) _Me3SiOEt : (ethoxy)trimethylsilane
MePhSi(OMe) ₂ : di(methoxy)(methyl)(phenyl)silane
_Me2Si (OEt) ₂ : Di(ethoxy)dimethylsilane
MeSi(OMe) ₃ : tri(methoxy)methylsilane
MeSi(OEt) ₃ : Tri(ethoxy)methylsilane
PhSi(OMe) ₃ : tri(methoxy)phenylsilane
PhSi(OEt) ₃ : tri(ethoxy)phenylsilane
ViSi(OMe) ₃ : Tri(methoxy)vinylsilane
ViSi(OEt) ₃ : Tri(ethoxy)vinylsilane
Si(OMe) ₄ : Tetramethoxysilane
Si(OEt) ₄ : Tetraethoxysilane
3) MeCOCl: acetyl chloride.
4) Mont-Sn ⁴⁺ : Montmorillonite containing Sn ⁴⁺
Mont-La ³⁺ : Montmorillonite containing La ³⁺
Mont-Ce ³⁺ : Montmorillonite containing Ce ³⁺
Mont-Ti ⁴⁺ : Montmorillonite containing Ti ⁴⁺
Mont-Zr ⁴⁺ : Montmorillonite containing Zr ⁴⁺
Mont-Fe ³⁺ : Montmorillonite containing Fe ³⁺
Mont-Al ³⁺ : Montmorillonite containing Al ³⁺
Mont-Ga ³⁺ : Montmorillonite containing Ga ³⁺
Mont-In ³⁺ : Montmorillonite containing In ³⁺
Mont-K10: Montmorillonite K10 (manufactured by Merck)
CBV780: USY type zeolite CBV780 (manufactured by Zeolyst, used after firing at 500°C)
CP811E-75: Beta zeolite CP811-E75 (manufactured by Zeorist, used after firing at 500°C)
Amberlyst15: H ⁺ type cation exchange resin Amberlyst 15 (manufactured by Merck)
CT175: H ⁺ type cation exchange resin Purolite CT175 (manufactured by Purolite)
NR50: H ⁺ type cation exchange resin Nafion NR50 (manufactured by DuPont).
5) The Mn ⁺ -containing montmorillonite is a Na ⁺ -containing montmorillonite (Na ⁺ -containing montmorillonite, Kunipia F manufactured by Kunimine Industries Co., Ltd.) and an aqueous solution containing Mn ⁺ (LaCl ₃ 7H ₂ O, CeCl ₃ 7H ₂ O, TiCl ₄ , _{ZrCl4 ,} Fe _{( NO3} )3.9H2O, Al( _{NO3 ) 3.9H2O} , Ga( _{NO3 ) 3.8H2O} , In _{( NO3} ) _3.3H2O , or SnCl ₄ ·5H ₂ O in water) to exchange Na ⁺ for M ^{n +} through a cation exchange reaction.
6) _Me3SiCl : chlorotrimethylsilane
MePhSi(OMe)Cl: chloro(methoxy)(methyl)(phenyl)silane
MePhSiCl ₂ : Dichloro(methyl)(phenyl)silane
_Me2Si (OEt)Cl: chloro(ethoxy)di(methyl)silane
_{Me2SiCl2 :} Dichlorodi(methyl)silane
MeSi(OMe) ₂ Cl: chlorodi(methoxy)(methyl)silane
MeSi(OMe) _Cl2 : Dichloro(methoxy)(methyl)silane
MeSi(OEt) ₂ Cl: chlorodi(ethoxy)(methyl)silane
MeSi(OEt) _Cl2 : Dichloro(ethoxy)(methyl)silane
PhSi(OMe) ₂ Cl: chlorodi(methoxy)(phenyl)silane
PhSi(OMe) _Cl2 : Dichloro(methoxy)(phenyl)silane
PhSi(OEt) ₂ Cl: chlorodi(ethoxy)(phenyl)silane
PhSi(OEt) _Cl2 : Dichloro(ethoxy)(phenyl)silane
ViSi(OMe) ₂ Cl: chlorodi(methoxy)(vinyl)silane
ViSi(OMe) _Cl2 : Dichloro(methoxy)(vinyl)silane
ViSi(OEt) ₂ Cl: chlorodi(ethoxy)(vinyl)silane
ViSi(OEt) _Cl2 : Dichloro(ethoxy)(vinyl)silane
Si(OMe) _3Cl : chlorotri(methoxy)silane
Si(OMe) ₂ Cl ₂ : Dichlorodi(methoxy)silane
Si(OMe)Cl ₃ : trichloro(methoxy)silane
Si(OEt) _3Cl : chlorotri(ethoxy)silane
Si(OEt) ₂ Cl ₂ : Dichlorodi(ethoxy)silane
7) The yield was calculated by NMR.
8) The figures in parentheses indicate the production ratio of halosilanes, and the yield indicates the total yield of halosilanes to alkoxysilanes.

Annotations in Tables 2-1 to 2-3 are shown below.
1) Refer to Note 6 in Tables 1-1 to 1-4 for the names of halosilanes.
2) Measured in deuterated chloroform.
3) GC-MS (EI, 70eV). The m/z of M ⁺ indicated the number of the most abundant isotopic compounds, including ³⁵ Cl.

Since the halogenation reaction of alkoxysilanes using a solid acid catalyst is a reaction system that progresses in stages, according to the present invention, when alkoxysilanes having a plurality of alkoxy groups are used as raw materials, the reaction conditions are can selectively convert only a portion of the alkoxy groups to halogeno groups.

For example, the reaction of tri(methoxy)vinylsilane (ViSi(OMe) ₃ ) with acetyl chloride (MeCOCl) uses Sn ⁴⁺ -containing montmorillonite (Mont-Sn ⁴⁺ ) as a catalyst, converting acetyl chloride to tri(methoxy)vinylsilane. chlorosilane (ViSi( OMe) ₂ Cl or ViSi(OMe)Cl ₂ ) could be obtained in yields of 78% or 7%, respectively (Example 47). On the other hand, when acetyl chloride is used at a molar ratio of 2.2 times that of tri(methoxy)vinylsilane, one or two of the three methoxy groups in tri(methoxy)vinylsilane are chloro groups. could be obtained in yields of 4% or 79%, respectively (Example 49).

Also, in the reaction between tetra(methoxy)silane (Si(OMe) ₄ ) and acetyl chloride (MeCOCl), Sn ⁴⁺ -containing montmorillonite (Mont-Sn ⁴⁺ ) was used as a catalyst, and acetyl chloride was converted to tetra(methoxy)silane. chlorosilane (Si( OMe) ₃ Cl or Si(OMe) ₂ Cl ₂ ) could be obtained in yields of 85% or 3%, respectively (Example 54). On the other hand, when acetyl chloride is used at a molar ratio of 2.2 times that of tetra(methoxy)silane, one or two of the four methoxy groups in tetra(methoxy)silane are chloro groups. could be obtained in yields of 4% or 88%, respectively (Example 56).

These results show that the number of alkoxy groups converted to chloro groups can be easily controlled by adjusting the amount of acetyl chloride used for a raw material having multiple alkoxy groups.

Halosilanes, which are useful as functional chemicals, can be efficiently and safely produced from alkoxysilanes by the production method of the present invention.

Claims (4)

A reaction step of reacting alkoxysilanes with a carboxylic acid halide in the presence of a catalyst,
A method for producing halosilanes, wherein the catalyst is a solid acid catalyst. The alkoxysilanes are alkoxysilanes represented by the following general formula (I),
The carboxylic acid halide is a carboxylic acid halide represented by the following general formula (II),
2. The method for producing halosilanes according to claim 1, wherein said halosilanes are represented by the following general formula (III).
R ¹ _p R ² _q R ³ _r Si(OR ⁴ ) _4-(p+q+r) (I)
(Wherein, p, q, and r are each independently an integer of 0 to 3; p+q+r is an integer of 0 to 3; R ¹ , R ² , and R ³ are each independently a hydrocarbon group having 1 to 24 carbon atoms or a hydrogen atom, and some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group may be substituted with groups that do not participate ⁱⁿ the reaction; Each independently represents an alkyl group having 1 to 6 carbon atoms.)
^R5COX (II)
(In the formula, R ⁵ is an alkyl group having 1 to 6 carbon atoms, and some or all of the hydrogen atoms bonded to the carbon atoms of the alkyl group may be substituted with groups that do not participate in the reaction; X is a halogen atom.)
R ¹ _p R ² _q R ³ _r Si(OR ⁴ ) _4-(p+q+r+s) X _s (III)
(Wherein, p, q, r, R ¹ , R ² , R ³ , R ⁴ , and X have the same definitions as above; s is an integer of 1 or more and 4-(p+q+r) or less.) 3. The method for producing halosilanes according to claim 1, wherein the solid acid catalyst is one or more solid acid catalysts selected from montmorillonite, zeolite, and cation exchange resins. said montmorillonite from lanthanum (III), cerium (III), titanium (IV), zirconium (IV), iron (III), aluminum (III), gallium (III), indium (III), and tin (IV) 4. The method for producing halosilanes according to claim 3, which is montmorillonite having one or more selected cations or protic hydrogen atoms.