Method for producing halosilanes

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

[Technical Field]

[0001] The present invention relates to an efficient method for producing halosilanes. [Background technology]

[0002] Halosilanes are functional chemicals that are used as raw materials for functional materials such as silicones and silane coupling agents, and as reagents for precision synthesis of pharmaceuticals, agricultural chemicals, electronic materials, etc. A known method for producing halosilanes is to convert the alkoxy group of alkoxysilanes into a chloro group using a carboxylic acid chloride, using a catalyst such as zinc chloride (Patent Documents 1 and 3), zinc oxide (Patent Document 2), or iron chloride (Non-Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-37303 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-155150 [Patent Document 3] International Publication No. 2018 / 173993 [Non-patent literature]

[0004] [Non-Patent Document 1] Macromolecules 1996, 29, 18, 5788-5796 [Non-patent document 2] Organometallics 2012, 31, 8, 3199-3206 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the above-mentioned methods using a catalyst, the catalyst is often dissolved in the reaction solution, and there remain problems such as the difficulty of separating and recovering the catalyst. For these reasons, there is a demand for a more industrially advantageous production method.

[0006] 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. [Means for solving the problem]

[0007] As a result of extensive research aimed at solving the above-mentioned problems, the present inventors discovered that halosilanes can be efficiently produced by using a specific solid acid catalyst as a catalyst in the reaction of alkoxysilanes with carboxylic acid halides, and thus completed the present invention. The manufacturing method of the present invention has the following features. (1) The raw materials and catalysts are easy to obtain and relatively easy to handle. (2) Because a solid catalyst is used as the catalyst, the catalyst can be easily separated and recovered by filtration, centrifugation, etc. (3) By adjusting the reaction conditions, it is possible to selectively convert only some of the alkoxy groups into halogeno groups. The manufacturing method of the present invention enables low-cost and highly efficient manufacturing processes, and has great advantages over conventional techniques in terms of economy and environmental impact.

[0008] That is, this application provides the following inventions. <1> The method includes a reaction step of reacting an alkoxysilane with a carboxylic acid halide in the presence of a catalyst, The method for producing halosilanes, wherein the catalyst is a solid acid catalyst. <2> The alkoxysilanes are those represented by the following general formula (I): The carboxylic acid halide is a carboxylic acid halide represented by the following general formula (II): The halosilane is a halosilane represented by the following general formula (III): <1> 1. A method for producing halosilanes according to claim 1. R 1 p R 2 q R 3 r Si(OR 4 ) 4-(p+q+r) (I) (In the formula, 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 carbon atoms of the hydrocarbon group may be substituted with groups that do not participate in the reaction; R 4 are each independently an alkyl group having 1 to 6 carbon atoms. R 5 COX (II) (In the formula, R 5 represents an alkyl group having 1 to 6 carbon atoms, and some or all of the hydrogen atoms bonded to carbon atoms of the alkyl group may be substituted with groups that do not participate in the reaction; and X represents a halogen atom. R 1 p R 2 q R 3 r Si(OR 4 ) 4-(p+q+r+s) X s (III) (In the formula, p, q, r, R 1 , R 2 , R 3 , R 4 and X are as defined above; and s is an integer of 1 or more and 4-(p+q+r) or less. <3> the solid acid catalyst is one or more solid acid catalysts selected from montmorillonite, zeolite, and cation exchange resin; <1> or <2> 1. A method for producing halosilanes according to claim 1. <4> The montmorillonite is a montmorillonite having one or more cations selected from lanthanum (III), cerium (III), titanium (IV), zirconium (IV), iron (III), aluminum (III), gallium (III), indium (III), and tin (IV), or a protic hydrogen atom. <3> 1. A method for producing halosilanes according to claim 1. [Effects of the Invention]

[0009] The production method of the present invention has the effect of enabling the production of halosilanes from alkoxysilanes as raw materials to be carried out more efficiently than conventional methods. DETAILED DESCRIPTION OF THE INVENTION

[0010] 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 an alkoxysilane with a carboxylic acid halide in the presence of a specific catalyst.

[0011] In this embodiment, the alkoxysilanes used as raw materials are represented by, for example, the following general formula (I). 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 to 3; p+q+r is an integer of 0 to 3. 1 , R 2 , and R 3 R 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 carbon atoms of the hydrocarbon group may be substituted with groups that do not participate in the reaction. 4 are each independently an alkyl group having 1 to 6 carbon atoms. In this specification, the term "group not involved in the reaction" refers to a group that does not directly participate in the target reaction as a reactive group and does not inhibit the reaction.

[0012] R 1 , R 2 , and R 3 Examples of the hydrocarbon group represented by the formula include an alkyl group, an aryl group, an aralkyl group, and an alkenyl group. When the hydrocarbon group is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 10, and particularly preferably 1 to 4. 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.

[0013] Examples of 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, halogen atoms, etc. More specifically, examples of alkoxy groups having 1 to 6 carbon atoms include methoxy groups, ethoxy groups, and hexoxy groups; examples of alkoxycarbonyl groups having 1 to 6 carbon atoms include methoxycarbonyl groups and propoxycarbonyl groups; examples of dialkylamino groups having 1 to 6 carbon atoms include dimethylamino groups and diethylamino groups; and examples of halogen atoms include fluorine atoms, chlorine atoms, and bromine atoms.

[0014] Specific examples of the alkyl group which may be substituted with a group which does not participate in the reaction include a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group, a decyl group, a 2-methoxyethyl group, a 3-ethoxypropyl group, a 2-methoxycarbonylethyl group, a 2-dimethylaminoethyl group, a 2-cyanoethyl group, a trifluoromethyl group, and a 3-chloropropyl group.

[0015] Furthermore, 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, the number of carbon atoms is preferably 6 to 22, more preferably 6 to 14, and even more preferably 6 to 10. Specific examples of monovalent aromatic organic groups of a hydrocarbon ring system include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, and a pentacenyl group. When the aryl group is a monovalent aromatic organic group of a heterocyclic ring system, the heteroatom in the heterocyclic ring is a sulfur atom, an oxygen atom, or the like. The number of carbon atoms in the monovalent aromatic organic group of a heterocyclic ring system is preferably 4 to 12, more preferably 4 to 8. Specific examples of monovalent aromatic organic groups of a heterocyclic ring system include a thienyl group, a benzothienyl group, a dibenzothienyl group, a furyl group, a benzofuryl group, and a dibenzofuryl group. 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 groups that do not participate in the reaction include those listed above as groups that may be substituted on the alkyl group. Other groups that do not participate in the reaction include oxyethylene groups and oxyethyleneoxy groups, which are divalent groups that bond two carbon atoms on a ring.

[0016] Specific examples of the aryl group which may be substituted with a group which does not participate in the reaction include a methylphenyl group, an ethylphenyl group, a hexylphenyl group, a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group, an octoxyphenyl group, a methyl(methoxy)phenyl group, a fluoro(methyl)phenyl group, a chloro(methoxy)phenyl group, a bromo(methoxy)phenyl group, a 2,3-dihydrobenzofuranyl group, and a 1,4-benzodioxanyl group.

[0017] Furthermore, when the hydrocarbon group is an aralkyl group, the number of carbon atoms in the aralkyl group is preferably 7 to 23, more preferably 7 to 16. In addition, 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 group that does not participate in the reaction include those groups that may be substituted on the alkyl group and do not participate in the reaction.

[0018] Specific examples of the aralkyl group which may be substituted with a group which does 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, and a 1-(4-methoxyphenyl)ethyl group.

[0019] When the hydrocarbon group is an alkenyl group, the number of carbon atoms in the alkenyl group is preferably 2 to 23, more preferably 2 to 20, and even more preferably 2 to 10. 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 group that does not participate in the reaction include the above-mentioned groups that may be substituted on the alkyl group and also the above-mentioned aryl groups.

[0020] Specific examples of the alkenyl group which may be substituted with a group which does not participate in the reaction include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 5-hexenyl group, a 9-decenyl group, a 2-phenylethenyl group, a 2-(methoxyphenyl)ethenyl group, a 2-naphthylethenyl group, and a 2-anthrylethenyl group.

[0021] R 4 The alkyl group having 1 to 6 carbon atoms represented by the formula (I) preferably has 1 to 4 carbon atoms, and more preferably has 1 to 3 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.

[0022] Specific examples of alkoxysilanes represented by general formula (I) include trimethyl(methoxy)silane (MeSiOMe), (ethoxy)trimethylsilane (MeSiOEt), di(methoxy)dimethylsilane (MeSi(OMe)), di(ethoxy)dimethylsilane (MeSi(OEt)), di(methoxy)(methyl)(phenyl)silane (MePhSi(OMe)), di(ethoxy)(phenyl)vinylsilane (PhViSi(OEt)), tri(methoxy)methylsilane (MeSi(OMe)), 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.

[0023] On the other hand, the carboxylic acid halide to be reacted with the alkoxysilane is represented by, for example, the following general formula (II). R 5 COX (II)

[0024] In general formula (II), R 5 represents 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; and X represents a halogen atom.

[0025] Specific examples of the group that does not participate in the reaction include R 1 , R 2 , and R 3 Examples of the groups that do not participate in the reaction include those shown in the explanation of the above. R 5 The alkyl group having 1 to 6 carbon atoms represented by the formula (I) preferably has 1 to 4 carbon atoms, and more preferably has 1 to 2 carbon atoms. Specific examples of the alkyl group which may be substituted with a group which does not participate in the reaction include R 1 , R 2 , and R 3 Examples of the above include those described in the above.

[0026] Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom or a bromine atom is preferred, and a chlorine atom is more preferred.

[0027] Specific examples of the carboxylic acid halide (II) represented by general formula (II) include acetyl fluoride (MeCOF), propionyl fluoride (EtCOF), butyryl fluoride (PrCF), acetyl chloride (MeCOCl), propionyl chloride (EtCOCl), butyryl chloride (PrCOCl), acetyl bromide (MeCOBr), propionyl bromide (EtCOBr), butyryl bromide (PrCOI), acetyl iodide (MeCOI), propionyl iodide (EtCOI), and butyryl iodide (PrCOI), and preferably acetyl chloride (MeCOCl).

[0028] The molar ratio of carboxylic acid halide to alkoxysilanes can be selected arbitrarily, but taking into consideration the yield of halosilanes based on alkoxysilanes, it is usually 0.4 or more and 20 or less, more preferably 0.5 or more and 10 or less, and even more preferably 0.5 or more and 6 or less.

[0029] According to this embodiment, halosilanes represented by the following general formula (III) can be produced by reacting alkoxysilanes represented by the general formula (I) with carboxylic acid halides represented by the general formula (II). R 1 p R 2 q R 3 r Si(OR 4 ) 4-(p+q+r+s) X s (III)

[0030] p, q, r, and R in general formula (III) 1 , R 2 , R 3 , R 4 and X are as defined above, and specific examples thereof include those shown in the general formulae (I) and (II). s is an integer of 1 or more and 4-(p+q+r) or less, and preferably an integer of 1 or more and 3-(p+q+r) or less.

[0031] Specific examples of halosilanes represented by general formula (III) include chlorosilanes such as chlorotrimethylsilane (MeSiCl), chlorotriethylsilane (EtSiCl), chlorodimethyl(phenyl)silane (MePhSiCl), chloromethyldi(phenyl)silane (MePhSiCl), chlorodimethyl(vinyl)silane (MeViSiCl), chloro(methoxy)dimethylsilane (MeSi(OMe)Cl), and chloro(ethoxy)di(methyl)silane (MeS i(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) 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)2Cl), dichloro(ethoxy)(phenyl)silane (PhSi(OEt)Cl2), trichloro(fu 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 (ViSiCl3), chlorotri(methoxy)silane (Si(OMe)3Cl), dichlorodi(methoxy)silane (Si(OMe )2Cl2), trichloro(methoxy)silane (Si(OMe)Cl3), chlorotri(ethoxy)silane (Si(OEt)3Cl), dichlorodi(ethoxy)silane (Si(OEt)2Cl2), trichloro(ethoxy)silane (Si(OEt)Cl3), tetrachlorosilane (SiCl4), etc. Furthermore, fluorosilanes, bromosilanes, and iodosilanes include compounds in which the chloro group of the compounds given as specific examples of chlorosilanes is replaced with a fluoro group, a bromo group, and an iodo group, respectively.

[0032] The reaction step in this 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 accompanied by elimination of a carboxylic acid ester. That is, in the reaction step of this embodiment, a cation (M m+ In the presence of a solid acid catalyst having the formula (II), the reaction is thought to proceed according to the reaction mechanism shown in the following reaction formula (Scheme 1).

[0033] [ka]

[0034] In this reaction mechanism, the cations of the elements of groups 3 to 15 of the solid acid catalyst (M m+ ) is thought to coordinate to the oxygen atom of the carboxylic acid halide, thereby increasing the nucleophilicity of the carbonyl group carbon atom and promoting the reaction.

[0035] In the reaction step, the alkoxysilanes used as raw materials are not limited to monoalkoxysilanes, but may also be dialkoxysilanes, trialkoxysilanes, tetraalkoxysilanes, and the like. That is, the halosilanes obtained in the reaction step of this embodiment are one type when monoalkoxysilane is used as the raw material, but are not limited to one type when dialkoxysilane, trialkoxysilane, or tetraalkoxysilane is used as the raw material. For example, when dialkoxysilane is used as the raw material, the halosilanes produced may be halosilanes in which one alkoxy group of alkoxysilanes is substituted, halosilanes in which two alkoxy groups of alkoxysilanes are substituted, or mixtures thereof. Furthermore, when trialkoxysilane is used as the raw material, the halosilanes produced may be halosilanes in which one alkoxy group of alkoxysilanes is substituted, halosilanes in which two alkoxy groups of alkoxysilanes are substituted, halosilanes in which three alkoxy groups of alkoxysilanes are substituted, or mixtures thereof. In addition, This means that when tetraalkoxysilane is used as the raw material, the halosilanes produced may be halosilanes in which one alkoxy group of alkoxysilanes has been substituted, halosilanes in which two alkoxy groups of alkoxysilanes have been substituted, halosilanes in which three alkoxy groups of alkoxysilanes have been substituted, halosilanes in which four alkoxy groups of alkoxysilanes have been substituted, or mixtures thereof.

[0036] 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.

[0037] Examples of inorganic solid acid catalysts include solid inorganic substances such as metal salts and metal oxides. More specifically, examples include zeolites, mesoporous silica, montmorillonite, etc., which have protic hydrogen atoms or cations of elements of Groups 3 to 15; inorganic solid acids supported on silica gel, heteropolyacids, carbon-based materials, etc. Of these, the inorganic solid acid catalyst is preferably selected from montmorillonite and zeolite.

[0038] Examples of cations of elements of Groups 3 to 15 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), and tin (IV). Among the cations of elements of Groups 3 to 15, cations selected from 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.

[0039] With regard to montmorillonite, montmorillonite having a cation selected from lanthanum (III), cerium (III), titanium (IV), zirconium (IV), iron (III), aluminum (III), gallium (III), indium (III), and tin (IV) as the cation of an element of Groups 3 to 15, or montmorillonite having a protic hydrogen atom is more preferably used, and montmorillonite having a cation selected from gallium (III), indium (III), and tin (IV) is even more preferably used.

[0040] Montmorillonite having cations of elements of Groups 3 to 15 can be easily prepared, for example, by treating commercially available montmorillonite having sodium (I) as the cation (for example, Kunipia (registered trademark) F, available from Kunimine Kogyo Co., Ltd.) with an aqueous solution containing cations of elements of Groups 3 to 15. Furthermore, commercially available montmorillonite having protic hydrogen atoms can be used, such as Montmorillonite K10 and Montmorillonite K30 (both available from Merck).

[0041] As for the zeolite, various types of zeolite having a basic skeleton such as Y type, beta type, ZSM-5 type, mordenite type, SAPO type, etc. can be used. In addition, SUSY type (Super Ultrastable Y), VUSY type (Very Ultrastable Y), and SDUSY type (Super Decontaminated Ultrastable Y) are obtained by secondary treatment of Y type zeolite (Na-Y). There are also USY type (Ultrastable Y) known as These are preferably used (for details of the USY type, see, for example, GT Kerr et al., "Molecular Sieves", Vol. 121, (USA), American Chemical Society, June 1, 1973, pp. 219-229 (Chapter 19)).

[0042] In terms of reaction rate, among these zeolites, it is preferable to select from USY type, beta type, ZSM-5 type, and mordenite type, and USY type and beta type are more preferable. As these zeolites, various types of zeolites can be used, such as Bronsted acid zeolites having protonic hydrogen atoms, and Lewis acid zeolites having cations of elements in Groups 3 to 15.

[0043] 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. Also, ammonium-type zeolites such as NH4-Y type, NH4-VUSY type, NH4-beta type, NH4-mordenite type, and NH4-ZSM-5 type zeolites can be calcined and converted into proton-type zeolites, which can be used as proton-type zeolites.

[0044] Furthermore, the silica / alumina ratio (ratio of substances) of the zeolite can be selected from various ratios depending on the reaction conditions, but is usually 3-1000, preferably 3-500, more preferably 5-300, and even more preferably 5-200.

[0045] Various types of zeolites, including commercially available products, can be used. Specific examples of commercially available USY zeolites include CBV760, CBV780, CBV720, CBV712, and CBV600, all of which are commercially available from Zeolite Co., Ltd. Examples of Y zeolites include HSZ-360HOA and HSZ-320HOA, all of which are commercially available from Tosoh Corporation. Examples of beta zeolites include CP811C, CP814N, CP7119, CP814E, CP7105, CP814CN, CP811TL, CP814T, CP814Q, CP811Q, CP811E-75, CP811E, and CP811C-300 commercially available from Zeolyst; HSZ-930HOA and HSZ-940HOA commercially available from Tosoh Corporation; and UOP-Beta commercially available from UOP.

[0046] On the other hand, in addition to the inorganic solid acid catalysts mentioned above, organic solid acid catalysts having acidic functional groups can also be used as catalysts. Examples of organic solid acid catalysts include cation exchange resins. Cation exchange resins are cation exchange resins containing protic hydrogen atoms. + Polymers having acidic functional groups, such as cation exchange resins, can be used, and may be of any of porous, gel, and macroporous types. Examples of the acidic functional groups include sulfo, carboxy, and phosphoryl groups, with sulfo and carboxy groups being preferred. Examples of the polymers include Teflon® backbone polymers with perfluoro side chains, styrene-divinylbenzene copolymers, and (meth)acrylic acid-divinylbenzene copolymers.

[0047] Specific examples of polymers having acidic functional groups include polymers having sulfo groups, such as Nafion (NAFION®, available from DuPont or Merck), Dowex (DOWEX®, available from Dow Chemical Company or Merck), Amberlite (AMBERLITE®, available from Rohm and Haas Company or Merck), Amberlyst (AMBERLYST®, available from Dow Chemical Company or Merck), and Purolite (PUROLITE®, available from Purolite). More specifically, examples of such materials include Nafion NR50, Dowex 50WX2, Dowex 50WX4, Dowex 50WX8, Amberlite IR120, Amberlite IRP-64, Amberlyst 15, Amberlyst 36, and Purolite CT175.

[0048] Among these organic solid acid catalysts, a solid acid selected from Amberlyst 15, Purolite CT175, and Nafion NR50 is preferably used, and a solid acid selected from Amberlyst 15 and Purolite CT175 is more preferably used.

[0049] The catalyst used in the production method according to this embodiment may be used alone or in any combination and ratio of a plurality of catalysts.

[0050] The amount of catalyst relative to the alkoxysilanes can be determined arbitrarily, but is usually about 0.0001 to 10, preferably about 0.001 to 8, more preferably about 0.001 to 6, and even more preferably about 0.01 to 1 in terms of molar ratio or weight ratio.

[0051] The reaction in the reaction step can be carried out in a liquid phase or a 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, and even more preferably 0 to 150°C. When the reaction is carried out at room temperature, the temperature range is usually 0 to 40°C, preferably 5 to 40°C, and more preferably 10 to 35°C.

[0052] 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 even 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 shape of the reaction apparatus, etc., but in consideration of productivity and efficiency, it is usually about 0.1 to 2400 minutes, preferably about 0.1 to 1200 minutes, more preferably about 0.1 to 600 minutes, and even more preferably about 0.1 to 300 minutes.

[0053] The reactor may be of any of various conventionally known types, such as a batch type, a flow type, etc. Since a solid acid catalyst is used in the reaction step of this embodiment, the production method of this embodiment can be suitably applied to a flow type reaction system that uses a column packed with a catalyst.

[0054] When the reaction is carried out in a liquid phase, it can be carried out with or without a solvent. Generally, the reaction proceeds more quickly without a solvent. However, when a solvent is used, various solvents that do not react with the raw materials and products can be used, such as hydrocarbons such as decahydronaphthalene (decalin) and decane, halogenated hydrocarbons such as chlorobenzene, 1,2- or 1,3-dichlorobenzene, 1,2,3- or 1,2,4-trichlorobenzene, and ethers such as tert-butyl methyl ether and dibutyl ether. Two or more solvents can also be used in combination. Deuterated solvents such as deuterated chloroform and deuterated benzene can also be used as reaction solvents to analyze the reaction products using a nuclear magnetic resonance spectrometer. When the reaction is carried out in a gas phase, the reaction can be carried out by mixing an inert gas such as nitrogen.

[0055] The reaction step can also be carried out under microwave irradiation. In this reaction system, the carboxylic acid halide, ionic acid catalyst, etc. are relatively highly polarized and efficiently absorb microwaves, so that the carboxylic acid halide, catalyst, etc. are activated under microwave irradiation, allowing the reaction to be carried out more efficiently.

[0056] In microwave irradiation reactions, various commercially available devices equipped with contact or non-contact temperature sensors can be used. The microwave irradiation output, cavity type (multimode, single mode), irradiation mode (continuous, intermittent), and other parameters can be determined as desired depending on the scale of the reaction, the types of raw materials, and the types of catalysts. The microwave frequency is typically 0.3 to 30 GHz. Among these, the IMS frequency band allocated for use in industrial, scientific, and medical fields is preferred, with the 2.45 GHz and 5.8 GHz bands being even more preferred.

[0057] In microwave irradiation reactions, a heating material (susceptor) that absorbs microwaves and generates heat can be added to the reaction system to heat the reaction system more efficiently. Various types of heating material can be used, including activated carbon, graphite, silicon carbide, and titanium carbide. A molded catalyst can also be used, which is prepared by mixing the catalyst powder with a heating material and calcining it using an appropriate binder such as sepiolite or holmite.

[0058] The reaction step in this embodiment can proceed in a closed-system reaction apparatus. However, the reaction can also proceed more efficiently by using an open-system reaction apparatus and continuously removing the reaction product from the reaction system.

[0059] In the production method according to this embodiment, since the catalyst is a solid catalyst, separation and recovery of the catalyst after the reaction step can be easily carried out by methods such as filtration and centrifugation. The resulting halosilanes can be easily purified by distillation, recrystallization, and other techniques commonly used in organic chemistry. [Example]

[0060] Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples. The main analytical devices used in the following examples are as follows: Nuclear magnetic resonance spectroscopy (hereinafter sometimes referred to as NMR): Bruker AVANCE III HD 600MHz (with cryoprobe) Gas chromatograph analysis (hereinafter sometimes referred to as GC): Shimadzu GC-2014 Gas chromatograph mass spectrometry (hereinafter sometimes referred to as GC-MS): Shimadzu GCMS-QP2010Plus

[0061] Example 1 (Ethoxy)trimethylsilane (Me3SiOEt) 0.5 mmol, acetyl chloride ( MeCOCl) 0.56 mmol, tin(IV)-containing montmorillonite (Sn 4+ Montmorillonite containing Mont-Sn 4+ 5 mg of methylsilane (Me3SiCl) and 0.4 mL of deuterated chloroform were placed in a reaction tube (NMR sample tube) and left to stand at approximately 25°C (room temperature) for 3 hours. The product was analyzed by NMR and the yield was calculated. It was found that chlorotrimethylsilane (Me3SiCl), a compound in which the methoxy group was converted to a chloro group, was produced in a yield of 78% (see Table 1-1).

[0062] (Examples 2 to 59) The 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 product yields were calculated by NMR. The results are shown in Tables 1-1 to 1-4.

[0063] The spectral data of the halosilanes obtained in the above examples are shown in Tables 2-1 to 2-3.

[0064] [Table 1-1]

[0065] [Table 1-2]

[0066] [Table 1-3]

[0067] [Table 1-4]

[0068] The notes in Tables 1-1 to 1-4 are as follows: 1) In Examples 1 to 57, deuterated chloroform (0.4 mL) was used as the solvent, and the reaction was carried out without stirring. In Examples 58 and 59, the reaction was carried out without a solvent, with a stirring bar placed in the solution and the solution being stirred using a magnetic stirrer. 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+ :Sn 4+Montmorillonite containing Mont-La 3+ :La 3+ Montmorillonite containing Mont-Ce 3+ :Ce 3+ Montmorillonite containing Mont-Ti 4+ :Ti 4+ Montmorillonite containing Mont-Zr 4+ :Zr 4+ Montmorillonite containing Mont-Fe 3+ :Fe 3+ Montmorillonite containing Mont-Al 3+ :Al 3+ Montmorillonite containing Mont-Ga 3+ :Ga 3+ Montmorillonite containing Mont-In 3+ :In 3+ Montmorillonite containing Mont-K10: Montmorillonite K10 (Merck) CBV780: USY-type zeolite CBV780 (manufactured by Zeolyst, calcined at 500°C) CP811E-75: Beta zeolite CP811-E75 (manufactured by Zeolyst, calcined at 500°C) Amberlyst15:H + Amberlyst 15 cation exchange resin (Merck) CT175:H + Purolite CT175 cation exchange resin (Purolite Co., Ltd.) NR50:H + Nafion NR50 cation exchange resin (manufactured by DuPont). 5) M n+ Montmorillonite containing Na + Montmorillonite (Na + Montmorillonite containing montmorillonite (Kunipia F manufactured by Kunimine Industries Co., Ltd.) was used. n+(LaCl3·7H2O, CeCl3·7H2O, TiCl4, ZrCl4, Fe(NO3)3·9H2O, Al(NO3)3·9H2O, Ga(NO3)3·8H2O, In(NO3)3·3H2O, or SnCl4·5H2O dissolved in water) + M n+ Cation exchange reaction It was prepared by 6) Me3SiCl: Chlorotrimethylsilane MePhSi(OMe)Cl: chloro(methoxy)(methyl)(phenyl)silane MePhSiCl2: Dichloro(methyl)(phenyl)silane Me2Si(OEt)Cl: chloro(ethoxy)di(methyl)silane Me2SiCl2: Dichlorodi(methyl)silane MeSi(OMe)2Cl: chlorodi(methoxy)(methyl)silane MeSi(OMe)Cl2: Dichloro(methoxy)(methyl)silane MeSi(OEt)2Cl: chlorodi(ethoxy)(methyl)silane MeSi(OEt)Cl2: Dichloro(ethoxy)(methyl)silane PhSi(OMe)2Cl: chlorodi(methoxy)(phenyl)silane PhSi(OMe)Cl2: Dichloro(methoxy)(phenyl)silane PhSi(OEt)2Cl: chlorodi(ethoxy)(phenyl)silane PhSi(OEt)Cl2: Dichloro(ethoxy)(phenyl)silane ViSi(OMe)2Cl: chlorodi(methoxy)(vinyl)silane ViSi(OMe)Cl2: Dichloro(methoxy)(vinyl)silane ViSi(OEt)2Cl: chlorodi(ethoxy)(vinyl)silane ViSi(OEt)Cl2: Dichloro(ethoxy)(vinyl)silane Si(OMe)3Cl: chlorotri(methoxy)silane Si(OMe)2Cl2: Dichlorodi(methoxy)silane Si(OMe)Cl3: Trichloro(methoxy)silane Si(OEt)3Cl: chlorotri(ethoxy)silane Si(OEt)2Cl2: Dichlorodi(ethoxy)silane 7) The yield was calculated by NMR. 8) The figures in parentheses indicate the ratio of halosilanes produced, and the yield is the ratio of halosilanes to alkoxysilanes. The total yield of the species is shown.

[0069] [Table 2-1]

[0070] [Table 2-2]

[0071] [Table 2-3]

[0072] The notes in Tables 2-1 to 2-3 are as follows: 1) For the names of halosilanes, see Note 6 in Tables 1-1 to 1-4. 2) Measurements in deuterated chloroform. 3) GC-MS (EI, 70 eV). + The m / z of 35 The values ​​for the most abundant isotopic compounds containing Cl are shown.

[0073] The halogenation reaction of alkoxysilanes using a solid acid catalyst is a reaction system that proceeds in a stepwise manner. Therefore, according to the present invention, when alkoxysilanes having multiple alkoxy groups are used as raw materials, it is possible to selectively convert only some of the alkoxy groups into halogeno groups by adjusting the reaction conditions.

[0074] For example, the reaction of tri(methoxy)vinylsilane (ViSi(OMe)3) with acetyl chloride (MeCOCl) uses Sn as a catalyst. 4+ Montmorillonite (Mont-Sn 4+ By using acetyl chloride at a molar ratio of 1.26 times relative to tri(methoxy)vinylsilane, chlorosilanes in which one or two of the three methoxy groups in tri(methoxy)vinylsilane were converted to chloro groups (ViSi(OMe)Cl or ViSi(OMe)Cl) were obtained in yields of 78% or 7%, respectively (Example 47). On the other hand, when acetyl chloride was used at a molar ratio of 2.2 times relative to tri(methoxy)vinylsilane, chlorosilanes in which one or two of the three methoxy groups in tri(methoxy)vinylsilane were converted to chloro groups were obtained in yields of 4% or 79%, respectively (Example 49).

[0075] In addition, the reaction of tetra(methoxy)silane (Si(OMe)4) with acetyl chloride (MeCOCl) also uses Sn as a catalyst. 4+ Montmorillonite (Mont-Sn 4+ By using acetyl chloride at a molar ratio of 1.12 times relative to tetra(methoxy)silane, chlorosilanes (Si(OMe)Cl or Si(OMe)Cl) in which one or two of the four methoxy groups in tetra(methoxy)silane were converted to chloro groups were obtained in yields of 85% or 3%, respectively (Example 54). On the other hand, when acetyl chloride was used at a molar ratio of 2.2 times relative to tetra(methoxy)silane, chlorosilanes in which one or two of the four methoxy groups in tetra(methoxy)silane were converted to chloro groups were obtained in yields of 4% or 88%, respectively (Example 56).

[0076] These results indicate that for a raw material having multiple alkoxy groups, the number of alkoxy groups converted to chloro groups can be easily controlled by adjusting the amount of acetyl chloride used. [Industrial Applicability]

[0077] The production method of the present invention makes it possible to efficiently and safely produce halosilanes, which are useful as functional chemicals, from alkoxysilanes, and therefore the present invention is highly useful and has great industrial significance.

Claims

1. The method includes a reaction step of reacting an alkoxysilane with a carboxylic acid halide in the presence of a catalyst, The alkoxysilanes are those represented by the following general formula (I): The carboxylic acid halide is a carboxylic acid halide represented by the following general formula (II): The halosilane is a halosilane represented by the following general formula (III): The method for producing halosilanes, wherein the catalyst is one or more solid acid catalysts selected from the group consisting of montmorillonite, zeolite, and cation exchange resins. R 1 p R 2 q R 3 r Si(OR 4 ) 4-(p+q+r) (I) (In the formula, p, q, and r each independently represent an integer of 0 to 3; p+q+r represents an integer of 0 to 3; R 1 , R 2 , and R 3 each independently represent a hydrocarbon group having 1 to 24 carbon atoms, in which some or all of the hydrogen atoms bonded to carbon atoms of the hydrocarbon group may be substituted with groups that do not participate in the reaction; and R 4 each independently represent an alkyl group having 1 to 6 carbon atoms.) R 5 COX (II) (wherein 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; and 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) (In the formula, p, q, r, R 1 , R 2 , R 3 , R 4 , and X are each defined as above; and s is an integer of 1 or more and 4-(p+q+r) or less.)

2. 2. The method for producing halosilanes according to claim 1, wherein the montmorillonite is a montmorillonite having one or more cations selected from lanthanum (III), cerium (III), titanium (IV), zirconium (IV), iron (III), aluminum (III), gallium (III), indium (III), and tin (IV), or a protic hydrogen atom.

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