JP2023121429A - Method for producing carbosilane and/or hydrosilane - Google Patents

Abstract

To provide an efficient method for the production of carbosilane and/or hydrosilane.SOLUTION: There is provided a method for producing carbosilane having an Si-R bond and/or hydrosilane having an Si-H bond, which comprises a step of reacting acyloxysilane having an Si-OCOR (wherein, OCO represents O-C(=O) of an oxycarbonyl group; R is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom in which part or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group may be substituted with a group not involved in the reaction) in the presence of a carbon-based catalyst, wherein the carbon-based catalyst is a carbon-based compound containing 90 mass% or more carbon.SELECTED DRAWING: None

Description

The present invention relates to an efficient method for producing carbosilane and/or hydrosilane.

Carbosilanes with Si—C bonds and hydrosilanes with Si—H bonds are used as precision synthesis reagents and intermediates for the production of various functional chemicals such as pharmaceuticals, agricultural chemicals, and optoelectronic materials, and functional materials. It is an important compound that is utilized.

As a general method for producing carbosilane or hydrosilane, a method of producing carbosilane by reacting chlorosilane, alkoxysilane, or the like with an organometallic compound such as a Grignard reagent or an organolithium reagent (Patent Document 1, Non-Patent Document 1); , alkoxysilane and the like are reacted with a metal hydride such as lithium aluminum hydride (Non-Patent Document 1), and the like (Method A).

On the other hand, using a catalytic reaction accelerator, a specific Si-OCOR' bond (hereinafter, OCO represents OC (=O) of an oxycarbonyl group. R' represents a trichloromethyl group (CCl ₃ ), a pentafluorophenyl group (C ₆ F ₅ ), a trifluoromethyl group (CF ₃ ), an alkynyl group (R″C≡C), etc.; R″ is a siloxycarbonyl group or an aryl group). A method (Method B) of producing a carbosilane having a Si—R′ bond by decarboxylating from acyloxysilane (hereinafter, decarboxylation indicates the elimination reaction of carbon dioxide (CO ₂ )) has been reported. (Non-Patent Documents 2-4, Patent Documents 2-4). In these methods, as catalytic reaction promoters, organic bases (Non-Patent Documents 2 and 3, Patent Document 4), quaternary ammonium salts (Non-Patent Document 4), alkali metal salts (Patent Documents 2 and 3), Alternatively, copper salts (Non-Patent Document 5) have been used.

U.S. Pat. No. 6,160,151 Russian Patent Application Publication No. 2013111741 FR-A-2862972 JP 2021-155337 A

The Chemical Society of Japan, “Experimental Chemistry Course (Volume 24) Organic Synthesis VI”, 4th edition, Maruzen Publishing, September 1992, p.122, p.157 Synthesis, 1980, 8, 626-627 Chimia, 1985, 39, 53 Russ. Chem. Bull., 1995, 44, 145-148 Organometallics, 2020, 39, 16, 2947-2950

However, Method A (1) requires the use of organometallic compounds that are not easy to handle and are dangerous due to their high reactivity to water and moisture, and (2) the production cost of organometallic compounds is generally high. , and (3) a large amount of metal chloride is produced as a by-product.
In addition, in method B, (1) the activity of the reaction accelerators known so far is not sufficient, so acyloxysilanes that can be used as raw materials are limited to specific types, and reaction accelerators such as acetoxysilane are limited to specific types. (2) Since the reaction accelerator is homogeneous, it is difficult to separate and recover the reaction accelerator.
For these reasons, there is a demand for an industrially more advantageous method that can solve the problems of the prior art.

The present invention has been made in view of the above circumstances, and is capable of producing carbosilane having a Si—C bond and/or hydrosilane having a Si—H bond more safely and efficiently than conventional methods. It is intended to provide a method.

The present inventors have made intensive studies to solve the above problems, and found that even in the case of acyloxysilane, which has low reactivity such as acetoxysilane, in the presence of a carbon-based catalyst containing 90% by mass or more of carbon, The inventors have found that a carbosilane having an Si—C bond and/or a hydrosilane having an Si—H bond can be efficiently produced by the reaction, and have completed the present invention.

That is, this application provides the following inventions.
<1>
Si—OCOR bond (hereinafter, OCO represents OC (=O) of an oxycarbonyl group; R is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and is bonded to the carbon atom of the hydrocarbon group some or all of the hydrogen atoms may be substituted with groups that do not participate in the reaction) in the presence of a carbon-based catalyst,
A method for producing a carbosilane having a Si—R bond and/or a hydrosilane having a Si—H bond, wherein the carbon-based catalyst is a carbon-based compound containing 90% by mass or more of carbon.
<2>
The production method according to <1>, wherein the carbon-based compound is a porous carbon-based compound.
<3>
The production method according to <2>, wherein the porous carbon-based compound is one or more selected from activated carbon, graphene, mesoporous carbon, carbon nanotubes, and carbon black.
<4>
The production method according to any one of <1> to <3>, wherein the reaction step is performed at a temperature of 100 to 800°C.
<5>
The production method according to any one of <1> to <4>, wherein the acyloxysilane having the Si—OCOR bond is an acyloxysilane represented by the following general formula (I).
R ¹ _a R ² _b R ³ _c Si(OCOR) _d (I)
(Wherein, a, b, and c are each independently 0 or 1; d is an integer of 1 or more and 3 or less; a + b + c + d = 4; R is as defined above; R ¹ , R ² and R ³ are each independently a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom, and hydrogen bonded to the carbon atoms of the hydrocarbon group and alkoxy group Some or all of the atoms may be substituted with groups that do not participate in the reaction.)
<6>
Prior to the reaction step, including a pre-step of producing the acyloxysilane having the Si—OCOR bond,
The manufacturing method according to any one of <1> to <5>, wherein the preceding step is any one of the following (1) to (3).
(1) An alkoxysilane having a Si—OR ⁴ bond (R ⁴ is a hydrocarbon group having 1 to 3 carbon atoms) is treated with (RCO) ₂ O (R is as defined above). a step of producing the acyloxysilane having the Si—OCOR bond by reacting the carboxylic acid anhydride to be obtained.
(2) by reacting an allylsilane having a Si—R ⁵ bond (R ⁵ is an allyl group) with a carboxylic acid represented by RCO ₂ H (R is as defined above), a step of producing the acyloxysilane having the Si—OCOR bond;
(3) Si—OCOR by reacting a halosilane having a Si—X bond with a carboxylic acid represented by RCO ₂ H (R is as defined above; X is a halogen atom); A step of producing an acyloxysilane having a bond.

According to the present invention, it is possible to provide a method for producing carbosilane having Si--C bonds and/or hydrosilane having Si--H bonds more safely and efficiently than conventional methods.

The present invention will be described in detail below.
One embodiment of the present invention is a Si-OCOR bond (hereinafter, OCO represents OC (=O) of an oxycarbonyl group; R is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, 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.) in the presence of a carbon-based catalyst. A method for producing a carbosilane having a Si—R bond (where R is as defined above) and/or a hydrosilane having a Si—H bond.
Hereinafter, alkoxysilanes having Si—OCOR bonds, carbosilanes having Si—R bonds, and hydrosilanes having Si—H bonds may be simply referred to as “acyloxysilanes,” “carbosilanes,” and “hydrosilanes,” respectively. be.

Specifically, the method for producing carbosilane and/or hydrosilane according to this embodiment has the following characteristics.
(1) High safety because there is no need to use an organometallic compound that is difficult to handle and dangerous.
(2) The catalyst is readily available, inexpensive, and easy to separate and recover.
(3) It is a reaction system that does not produce a large amount of waste such as salts.
The manufacturing method according to the present embodiment makes it possible to improve the safety and efficiency of the manufacturing process, and has great advantages over the conventional technology in terms of economic efficiency, low environmental impact, and the like.

1. Reaction process <Acyloxysilane>
In this embodiment, acyloxysilanes used in the reaction step include, for example, acyloxysilanes represented by the following general formula (I).
R ¹ _a R ² _b R ³ _c Si(OCOR) _d (I)

(R ¹ , R ² and R ³ )
R ¹ , R ² and R ³ are each independently a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom, and are bonded to the carbon atoms of the above hydrocarbon group and alkoxy group. Some or all of the hydrogen atoms in the above may be substituted with groups that do not participate in the reaction.
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.

Hydrocarbon groups represented by R ¹ , R ² and R ³ include alkyl groups, aryl groups, aralkyl groups, alkenyl groups and the like.

When the hydrocarbon group is an alkyl group, the alkyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 12 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, and halogen atoms. More specifically, alkoxy groups, alkoxycarbonyl groups, and halogen atoms include alkoxy groups having 1 to 6 carbon atoms, such as methoxy groups, ethoxy groups, and hexoxy groups; alkoxycarbonyl groups having 1 to 6 carbon atoms. Examples include methoxycarbonyl group, propoxycarbonyl group and the like; Halogen atoms include fluorine atom, chlorine atom and the like.

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, 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 6-18 carbon atoms, more preferably 6-14 carbon atoms. Specific examples of monovalent aromatic organic groups having a hydrocarbon ring system include phenyl, naphthyl, anthryl, phenanthryl, and pyrenyl 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 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 the non-reaction-involved group include those shown as the non-reaction-involved group which may be substituted on the above-mentioned alkyl group. 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 19 carbon atoms, more preferably 7 to 15 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 above-mentioned 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 18 carbon atoms, more preferably 2 to 14 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. Examples of the non-reaction-involved group include the above-mentioned non-reaction-involved groups which may be substituted on the alkyl group, 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.

When R ¹ , R ² or R ³ is an alkoxy group, the alkoxy group preferably has 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms. Some or all of the hydrogen atoms bonded to the carbon atoms of the alkoxy 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 alkoxy group optionally substituted with a group that does not participate in the reaction include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a tert-butoxy group, a cyclohexoxy group and the like.

Further, when R ¹ , R ² or R ³ is a halogen atom, the halogen atom is a fluorine atom, a chlorine atom or a bromine atom.

(R)
R is a hydrocarbon group having 1 to 20 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. When R is a hydrocarbon group, the hydrocarbon group preferably has 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 4 carbon atoms. A hydrogen atom may be substituted with a group that does not participate in the reaction.
Specific examples of groups that do not participate in the reaction include those shown as groups that do not participate in the reaction that may be substituted on the alkyl groups represented by R ¹ , R ² and R ³ .

Specific examples of when R is a hydrocarbon group include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, etc. Specific examples of these groups include R ¹ , R ² and R ³ and the like shown in the description of .

(a, b, c, and d)
a, b, and c are each independently 0 or 1;
d is an integer of 1 or more and 3 or less, preferably 1 or 2, more preferably 1;
Also, a, b, c, and d satisfy a+b+c+d=4.

Specific examples of acyloxysilanes represented by formula (I) include acetoxytrimethylsilane ((MeCO ₂ )SiMe ₃ ), diacetoxydimethylsilane ((MeCO ₂ ) ₂ SiMe ₂ ), and triacetoxy(methyl)silane. (( _MeCO2 ) _3SiMe ), acetoxytriethylsilane (( _MeCO2 ) _SiEt3 ), acetoxytributylsilane (( _MeCO2 ) _SiBu3 ), acetoxytrimethoxysilane (( _MeCO2 )Si(OMe
) ₃ ), diacetoxydimethoxysilane ((MeCO ₂ ) ₂ Si(OMe) ₂ ), acetoxytriethoxysilane ((MeCO ₂ )Si(OEt) ₃ ), diacetoxydiethoxysilane ((MeCO ₂ ) ₂ Si( OEt) ₂ ), acetoxytripropoxysilane ((MeCO ₂ )Si(OPr) ₃ ), acetoxytributoxysilane ((MeCO ₂ )Si(OBu) ₃ ), acetoxytrichlorosilane ((MeCO ₂ )SiCl ₃ ), di Acetoxydichlorosilane (( _MeCO2 ) _2SiCl2 ), triacetoxychlorosilane (( _MeCO2 ) _3SiCl ), (benzoyloxy)trimethylsilane (( _PhCO2 ) _SiMe3 ), _bis (benzoyloxy)dimethylsilane ((PhCO ₂ ) _{2SiMe2 )} , (benzoyloxy)trimethoxysilane (( _PhCO2 )Si(OMe) ₃ ), bis(benzoyloxy)dimethoxysilane (( _PhCO2 ) _2Si (OMe) ₂ ), (benzoyloxy) trichlorosilane (( _PhCO2 ) _SiCl3 ), bis(benzoyloxy ₎ dichlorosilane (( _PhCO2 ) _2SiCl2 ), acetoxydi(methyl)(vinyl)silane (( _MeCO2 ) _SiMe2 (CH= _CH2 )) , diacetoxy(methyl)(vinyl)silane ((MeCO ₂ ) ₂ SiMe(CH=CH ₂ )), triacetoxy(vinyl)silane ((MeCO ₂ ) ₃ Si(CH=CH ₂ )), trimethyl[(2- phenylethenyl)carbonyloxy _] silane ((PhCH= _CHCO2 ) _SiMe3 ), tetraacetoxysilane ( _{( MeCO2} ) _4Si ), trimethyl(pentafluorophenylcarbonyloxy)silane (( _C6F5CO2 )SiMe ₃ ), dimethylbis(pentafluorophenylcarbonyloxy ₎ silane ₍ (C6F5CO2)2SiMe2) _, methyltris _{( pentafluorophenylcarbonyloxy )} silane ((C6F5CO2 _{) 3SiMe )} , triethoxy (pentafluorophenylcarbonyloxy)silane ₍ (C6F5CO2 ₎ Si( _OEt ) ₃ ), diethoxybis( _{pentafluorophenylcarbonyloxy)silane ((C6F5CO2 ) 2Si} (OEt _{) 2} ), _trimethoxy (pentafluorophenylcarbonyloxy)silane (( _{C6F5CO2)Si(OMe)3 ) ,} dimethoxybis( _{pentafluorophenylcarbonyloxy)silane ((C6F5CO2 ) 2Si (} OMe) ₂ ), trichloro(pentafluorophenylcarbonyloxy ₎ silane ((C6F5CO2) _SiCl3 ) _, dichlorobis(pentafluorophenylcarbonyloxy _{) silane} (( _{C6F5CO2 ) 2SiCl2 )} , dimethylphenyl ( pentafluorophenylcarbonyloxy)silane (( _C6F5CO2 ) _SiMe2Ph ), dimethyl(pentafluorophenylcarbonyloxy)(vinyl) _silane (( _{C6F5CO2 ) SiMe2} (CH _{= CH2 )} ), trimethyl(trifluoroacetyloxy)silane ( _{( CF3CO2 )} SiMe3), dimethylbis(trifluoroacetyloxy)silane (( _{CF3CO2 ) 2SiMe2 )} , triethoxy(trifluoroacetyloxy)silane (( _{CF3CO2 )} Si(OEt) ₃ ), dimethoxybis(trifluoroacetyloxy)silane (( _{CF3CO2 ) 2Si} (OMe) ₂ ), trichloro(trifluoroacetyloxy)silane (( _{CF3 CO2 ) SiCl3} ), trimethyl(pentafluoropropionyloxy)trimethylsilane ( _{( CF3CF2CO2} )SiMe3 ₎ , _trimethyl (trichloroacetyloxy)silane (( _CCl3CO2 ) _SiMe3 ), ethoxydimethyl ( trichloroacetyloxy)silane (( _{CCl3CO2 ) SiMe2} (OEt)), diethoxymethyl(trichloroacetyloxy)silane (( _{CCl3CO2 )} SiMe(OEt) ₂ ), triethoxy(trichloroacetyloxy)silane ( ( _{CCl3CO2 )} Si(OEt) ₃ ), trichloro ₍ trichloroacetyloxy)silane (( _{CCl3CO2 ) SiCl3} ), dichlorobis(trichloroacetyloxy)silane (( _CCl3CO2 ) _{2SiCl2 )} , trimethyl(phenylethynylcarbonyloxy)silane ((PhC≡CCO ₂ )SiMe ₃ ), triethoxy(phenylethynylcarbonyloxy)silane ((PhC≡CCO ₂ )Si(OEt) ₃ ), trimethyl(1-propynylcarbonyloxy)silane ((MeC≡CCO ₂ )SiMe ₃ ), formyloxytrimethylsilane ((HCO ₂ )SiMe ₃ ), formyloxytrimethoxysilane ((HCO ₂ )Si(OMe) ₃ ), formyloxytrichlorosilane ((HCO ₂ ) SiCl ₃ ) and the like.

<Carbosilane and hydrosilane>
According to the production method of the present embodiment, carbosilane and/or Si—C bond-containing carbosilane and/or Si— Hydrosilanes with H-bonds can be produced.

The reaction step in this embodiment is a step of producing carbosilane and/or hydrosilane by reaction of acyloxy groups of acyloxysilane. When the acyloxysilane is monoacetoxysilane, for example, the reaction mechanism shown in Scheme 1 or 2 below can be considered as the reaction mechanism.

In Scheme 1, which gives carbosilane, the methyl group of the acetoxy group migrates onto a silicon atom and _CO2 is eliminated to form methylsilane.
On the other hand, in Scheme 2, which gives hydrosilane, the hydrogen atom of the acetoxy group moves onto the silicon atom and the CH ₂ CO ₂ unit is eliminated to form hydrosilane. The route to hydrosilane according to Scheme 2 is a possible route not only for acetoxy groups but also for other acyloxy groups having a hydrogen atom on the carbon atom adjacent to the carbonyl group.
Also, in Scheme 1, when the acetoxy group ( _OCOCH3 group) is replaced with a formyloxy group (OCOH group), the hydrogen atom of the formyloxy group moves onto the silicon atom, and _CO2 is eliminated, resulting in hydrosilane A route generated by

It is believed that the substituents R ¹ , R ² and R ³ on the silicon atom, the reaction conditions, etc. have a great effect on the reaction pathways of Schemes 1 and 2. For example, in monoacetoxysilane, if the substituent on the silicon atom is relatively bulky, the hydrogen atom tends to move more easily than the methyl group, which is sterically larger than the hydrogen atom. .
It is also possible that these reaction pathways proceed radically, and carbon-based catalysts such as activated carbon are involved in the formation of radical intermediates from acyloxysilane and promotion of the reaction. It is possible.

When the acyloxysilane has a plurality of acyloxy groups, the carbosilane and/or hydrosilane obtained by the production method according to the present embodiment contains carbosilane and/or hydrosilane produced by the reaction of some or all of the plurality of acyloxy groups. or hydrosilanes.

In the reaction step of the present embodiment, side reactions may produce silanol, disiloxane, and the like. When the acyloxysilane is monoacetoxysilane, for example, it is possible that silanol and ketene are generated from monoacetoxysilane and disiloxane is generated from silanol by the reaction mechanism shown in Scheme 3 below. be done.

According to the production method according to the present embodiment, for example, acetoxytrimethylsilane ((MeCO ₂ )SiMe ₃ ) is converted to tetramethylsilane (Me ₄ Si) and/or trimethylsilane (Me ₃ SiH); acetoxytriethylsilane (( MeCO ₂ )SiEt ₃ ) to triethyl(methyl)silane (Et ₃ SiMe) and/or triethylsilane (Et ₃ SiH); acetoxytrimethoxysilane ((MeCO ₂ )Si(OMe) ₃ ) to trimethoxy(methyl) Silane (MeSi(OMe) ₃ ) and/or trimethoxysilane (HSi(OMe) ₃ ); acetoxytriethoxysilane (( _MeCO2 )Si(OEt) ₃ ) to triethoxy(methyl)silane (MeSi(OEt) ₃ ) and/or triethoxysilane (HSi(OEt) ₃ ); acetoxytrichlorosilane ((MeCO ₂ )SiCl ₃ ) to trichloro(methyl)silane (MeSiCl ₃ ) and/or trichlorosilane (HSiCl ₃ ); ) from trimethylsilane ((PhCO ₂ )SiMe ₃ ) to trimethyl(phenyl)silane (Me ₃ SiPh) and/or trimethylsilane (Me ₃ SiH); from diacetoxydimethylsilane ((MeCO ₂ ) ₂ SiMe ₂ ) to ( acetoxy)trimethylsilane (( _MeCO2 ) _SiMe3 ), tetramethylsilane ( _Me4Si ), acetoxydimethylsilane (( _MeCO2 ) _SiMe2H ), dimethylsilane ( _Me2SiH2 ), and/or trimethylsilane ₍ Me ₃ SiH); from diacetoxydimethoxysilane ((MeCO ₂ ) ₂ Si(OMe) ₂ ) to (acetoxy)dimethoxy(methyl)silane ((MeCO ₂ )Si(OMe) ₂ Me), dimethoxydi(methyl)silane ( _Me2Si (OMe) ₂ ), (acetoxy)dimethoxysilane (( _MeCO2 )Si(OMe) _2H ), dimethoxysilane ( _H2Si (OMe) ₂ ), and/or dimethoxy(methyl)silane (HMeSi( OMe) ₂ );

In the reaction step, in the resulting carbosilane and/or hydrosilane, depending on the type of R in the acyloxy group (OCOR), the reaction conditions, etc., isomerization of the structure of R or disproportionation of the substituent on the silicon atom may occur. There is
The carbosilane and/or hydrosilane obtained by the production method according to the present embodiment also include mixtures of isomers and/or disproportionate thereof.
For example, in Scheme 1, carbosilane R ¹ R ² R ³ SiCH ₃ is produced, and its disproportionated products, R ¹ R ² Si(CH ₃ ) ₂ and R ² R ³ Si(CH ₃ ) ₂ , R ¹ R ³ Si(CH ₃ ) ₂ and other compounds are also included in the carbosilane obtained by the production method according to the present embodiment.
In Scheme 2 above, hydrosilane R ¹ R ² R ³ SiH is produced, and its disproportionated products, R ¹ R ² SiH ₂ , R ² R ³ SiH ₂ and R ¹ R ³ SiH Compounds such as ₂ are also included in the hydrosilanes obtained by the production method according to the present embodiment.

<Carbon catalyst>
In the reaction step of the present embodiment, a carbon-based compound containing 90% by mass or more of carbon is used as a carbon-based catalyst in order to promote the reaction.
As such a carbon-based compound, for example, a porous carbon-based compound is preferably exemplified.
As the porous carbon-based compound, various conventionally known compounds can be used, and activated carbon and the like are typical.

As the activated carbon, various methods known in the art (for example, "New Edition Activated Carbon Fundamentals and Applications" (edited by Yuzo Sanada, Motoyuki Suzuki and Kaoru Fujimoto, Kodansha, 1997), the method described in Chapter 2, "Applied Technology of Activated Carbon" (Supervised by Hideki Tachimoto and Ikuo Abe, Techno System, 2000), the method described in Chapter 2 of Basics, etc.) can be used.
Examples of raw materials for activated carbon include plant-based, mineral-based, and polymer-based materials. Plant-based raw materials include rice husks, coconut husks, wood, charcoal, and the like. Mineral raw materials include peat coal, peat, lignite, coke, and the like. Examples of polymeric materials include rayon, acrylic polymers, and phenolic compounds.
Methods for activating activated carbon by increasing its specific surface area include gas activation, chemical activation, and the like. Examples of the gas activation method include methods using water vapor, carbon dioxide gas, oxygen, and the like. Examples of chemical activation methods include methods using zinc chloride, phosphoric acid, or salts thereof; alkali metal hydroxides; alkali metal carbonates;
Regarding the properties of activated carbon, any of basic, neutral and acidic can be used, but basic or neutral activated carbon is preferably used.
As for the shape of the activated carbon, various shapes such as powder, granules, and fibrous can be used.

Examples of carbon-based compounds other than activated carbon include graphene, carbon nanotubes, mesoporous carbon, and carbon black.
Among these, the carbon-based compound is preferably selected from graphene, carbon nanotubes, and mesoporous carbon, which have relatively large specific surface areas.

The carbon-based compound may contain or carry other elements in an amount of less than 10% by mass in addition to carbon.
Examples of the other elements include Group 1 to Group 14 elements, and more specifically lithium, sodium, potassium, calcium, magnesium, iron, ruthenium, rhodium, nickel, palladium, platinum, and copper. , zinc, aluminum, silicon and the like. Among these, the other element is preferably selected from ruthenium, rhodium, palladium, platinum and copper.

Also, the specific surface area of the carbon-based compound is generally 50 to 4000 m ² /g, preferably 100 to 3000 m ² /g, more preferably 150 to 2500 m ² /g.
On the other hand, the porous carbon-based compound has various pore sizes such as macropores (pore diameter >50 nm), mesopores (pore diameter 2 to 50 nm), and micropores (pore diameter <2 nm). Porous carbon-based compounds can be used. Specifically, the average pore diameter of the porous carbon-based compound is usually 0.5 to 100 nm, preferably 1 to 50 nm, more preferably 1 to 10 nm.
The carbon-based compounds may be used singly, or two or more may be used in any combination and ratio.

Examples of commercially available carbon-based compounds that can be used in the present embodiment include activated carbon (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product number 032-18091, powder), activated carbon (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product number 037- 02115, powder), activated carbon (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product number 034-02125, granular), activated carbon (manufactured by Merck, product number 242276, powder), graphene (manufactured by Merck, product number 900407, nano platelet, powder), 5% palladium-supported activated carbon (manufactured by Merck, product number 205680, powder), 5% platinum-supported activated carbon (manufactured by Merck, product number 205931, powder), 3% copper-supported activated carbon (manufactured by Merck, product number 709107, powder), 5% ruthenium-supported activated carbon (Merck, product number 206180, powder), 5% platinum-supported activated carbon (Merck, product number 206164, powder), and the like.

The amount of carbon-based catalyst to acyloxysilane can be determined arbitrarily, but the weight ratio of carbon-based catalyst to acyloxysilane is usually 0.001 to 100, preferably 0.01 to 50, more preferably 0. .01 to 20.

<Reaction conditions>
The reaction of the present invention can be carried out in a liquid phase system or a gas phase system depending on the reaction temperature and reaction pressure. 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.
The reaction temperature is usually 100 to 300° C. in a liquid phase system. The reaction temperature is generally 100 to 800°C, preferably 300 to 800°C, more preferably 500 to 750°C in a gas phase system.
Considering reaction efficiency, productivity, etc., the production method according to the present embodiment is preferably carried out in a flow system. The reaction temperature in that case is preferably 300 to 750°C, more preferably 350 to 750°C.
Furthermore, the reaction pressure is generally 0.001 to 10 atmospheres, preferably 0.001 to 5 atmospheres, more preferably 0.001 to 3 atmospheres.
The reaction time depends on the amount of raw materials, the amount of catalyst, the reaction temperature, the form of the reaction apparatus, etc., but when efficiency, productivity, etc. are considered, it is usually 1 minute to 12 hours, preferably 1 minute to 6 hours, or more. It is preferably 1 minute to 3 hours, more preferably 5 minutes to 1 hour, particularly preferably 5 minutes to 30 minutes.

In the reaction step of the present embodiment, the reaction apparatus is set to an open system or a reduced pressure system, and the reaction product, co-product carbon dioxide, etc. are continuously released out of the reaction system, so that the reaction proceeds more efficiently. can be made

When the reaction is carried out in a liquid phase system, it can be carried out with or without a solvent. When a solvent is used, the solvent includes hydrocarbons such as decalin (decahydronaphthalene) and decane; chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,2,3-trichlorobenzene, Halogenated hydrocarbons such as ,4-trichlorobenzene; ethers such as tert-butyl methyl ether, dibutyl ether, tetrahydrofuran; and the like. A solvent may be used individually by 1 type, and may use 2 or more types by arbitrary combinations and ratios.

When the reaction is carried out in a gas phase system, the carrier gas can be mixed with the acyloxysilane gas to carry out the reaction. Inert gases such as nitrogen, argon, and helium can be used as the carrier gas.
The amount of carrier gas used can be determined arbitrarily, but the volume ratio of carrier gas to the volume of vaporized acyloxysilane is usually 0.1 to 200, preferably 0.1 to 100, more preferably 0.1 to 50.
Further, in a gas-phase system flow reaction, liquid acyloxysilane is injected with a syringe pump or the like, and when the injection rate is 1 to 1000 μL/min, the flow rate of the carrier gas is usually 0.1 to 100 mL/min. , preferably 0.5-70 mL/min, more preferably 0.5-40 mL/min.
In the gas-phase flow-type reaction, the liquid acyloxysilane is vaporized in the vaporization unit and then reacted. It can also be carried out by a simple reaction method.
When the reaction is carried out in a gas-phase flow system, in order to collect the product, the collection vessel is cooled to room temperature or lower, and the carrier gas containing the product is bubbled through an appropriate solvent in order to increase the collection efficiency. An operation such as dissolving the product in a solvent and collecting the product may be performed. As the type of solvent, various solvents other than acyloxysilane and those that react with the product can be used. heavy solvent) may be used.

2. Pre-process The production method according to the present embodiment may include a pre-process for producing acyloxysilane. Suitable pre-processes include the following (1) to (3). Carbosilane and/or hydrosilane can be produced more efficiently by continuously performing any one of the pre-steps (1) to (3) and the subsequent reaction step.
(1) An alkoxysilane having a Si—OR ⁴ bond (R ⁴ is a hydrocarbon group having 1 to 3 carbon atoms) is treated with (RCO) ₂ O (R is as defined above). a step of producing the acyloxysilane having the Si—OCOR bond by reacting the carboxylic acid anhydride to be obtained.
(2) by reacting an allylsilane having a Si—R ⁵ bond (R ⁵ is an allyl group) with a carboxylic acid represented by RCO ₂ H (R is as defined above), a step of producing the acyloxysilane having the Si—OCOR bond;
(3) Si—OCOR by reacting a halosilane having a Si—X bond with a carboxylic acid represented by RCO ₂ H (R is as defined above; X is a halogen atom); A step of producing an acyloxysilane having a bond. The halogen atom represented by X includes a chlorine atom, a bromine atom, an iodine atom and the like, preferably a chlorine atom.

For example, when the acyloxysilane is monoacyloxysilane, the monoacyloxysilane can be produced from monoalkoxysilane, monoallylsilane, or monohalosilane by a preceding step, as shown in Scheme 4 below. Monoacyloxysilane produced in the previous step can be converted to carbosilane and/or hydrosilane in the subsequent reaction step.

These pre-step reactions do not necessarily require a reaction accelerator such as a catalyst, but various reaction accelerators may be used to carry out the reaction.
For example, in the reaction of monoalkoxysilane and carboxylic acid anhydride in the preceding step (1) and the reaction of monoallylsilane and carboxylic acid in the preceding step (2), inorganic or organic solid acids; Lewis acids; Acid catalysts can be used.
An organic or inorganic base catalyst can be used in the reaction between the halosilane and the carboxylic acid in the previous step (3).

In the preceding step, it is not necessary to isolate and purify the acyloxysilane, and the preceding step and the subsequent reaction step can be combined and carried out in one pot.
Another feature of the production method according to the present embodiment is that carbosilane and/or hydrosilane can be efficiently produced from alkoxysilane or the like by continuously performing the preceding step and the subsequent reaction step.

3. Other Steps The manufacturing method according to the present embodiment may include other steps in addition to the pre-step. Other steps include a catalyst recovery step for separating and recovering the carbon-based catalyst used in the reaction step from the reaction system. In a flow-type reaction system, the catalyst recovery step may be performed by simply separating the column or reaction tube packed with the carbonaceous catalyst. Also, even in a batch-type reaction system, the catalyst can be easily separated and recovered by a method such as filtration or centrifugation.

Other steps include a purification step for purifying the produced carbosilane and/or hydrosilane. The resulting carbosilane and/or hydrosilane can be easily purified by means commonly used in organic chemistry, such as distillation, recrystallization, and column chromatography.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to those examples.
The main analyzers and the like used in the following examples are as follows.
・ Nuclear magnetic resonance spectroscopy (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)
A quartz tube (inner diameter 7 mmφ, length 40 cm) was filled with 100 mg of activated carbon (manufactured by Fuji Film Wako, product number 032-18091, lot number PTE1918, powder) as a carbon-based catalyst (50 mg of quartz wool was placed on each side of the activated carbon). Filling) and placed in a vertical small electric furnace (FT-01P manufactured by Furutec Co., Ltd., modified model with holes of 10 mm each at the top and bottom). Subsequently, the carbon-based catalyst was calcined at 700° C. for about 1 hour while flowing nitrogen as a carrier gas from the upper portion of the quartz tube at a rate of 8 mL/min. Thereafter, the flow rate of the carrier gas was changed to 4 mL/min, and the raw material acetoxytrimethylsilane ((MeCO ₂ )SiMe ₃ ) was passed through the stainless needle from the upper end of the quartz tube at a rate of 10 µL/min using a syringe pump. It was introduced into the upper part of the electric furnace and reacted. The reaction mixture (unreacted raw materials and reaction products) was collected in a collection glass container (cooled to −40° C. by an aluminum block cryostat (PSL-2500 manufactured by Tokyo Rika Co., Ltd.)) installed at the bottom of the quartz tube. In order to increase the collection efficiency, a solvent (1 mL of deuterated chloroform) was placed in the glass container for collection, and the carrier gas containing the reaction mixture flowing out from the end of the quartz tube was bubbled through the solvent to obtain the product. were collected. After 5, 6, 8, and 10 minutes from the beginning of the acetoxytrimethylsilane flow, a portion of the solution in which the reaction mixture was dissolved was sampled and analyzed by NMR, GC, and GC-MS.

As a result, tetramethylsilane (Me ₄ Si), trimethylsilane (Me ₃ SiH), trimethylsilanol (Me ₃ SiOH), hexamethyldisiloxane (Me ₃ SiOSiMe ₃ ), octamethyltrisiloxane (Me ₃ SiOSiMe ₂ OSiMe ₃ ) and hexamethylcyclotrisiloxane ((SiMe ₂ O) ₃ ) were identified. The raw material conversion rate and the yield of the above product (calculated based on the composition ratio at each sampling time) were 100%, 66%, 4%, 0%, 23%, 2%, and 2% at 5 minutes, respectively. Yes; 100%, 58%, 3%, 0%, 30%, 4%, and 3% at 6 minutes; 100%, 43%, 3%, 0%, 40%, 6%, at 8 minutes; and 4%; and 100%, 33%, 3%, 1%, 47%, 6%, and 5% at 10 minutes (see Table 1-1). Among the products, Me ₄ Si and Me ₃ SiH correspond to carbosilane and hydrosilane, respectively, which are objects to be produced by the production method according to the present invention.
Table 2 shows the NMR and GC-MS measurement results of the obtained product.

(Examples 2 to 21)
Reaction and analysis were carried out in the same manner as in Example 1 by changing the reaction conditions (catalyst, reaction temperature, etc.). The results are shown in Tables 1-1 to 1-3 and Table 2.
Note that the temperature for calcining the catalyst before starting the flow of acetoxytrimethylsilane was the same as the reaction temperature. Further, in Examples 17 to 21, cooling of the glass container for collection was performed with ice water.

The production method of the present invention may include a pre-process for producing acyloxysilane, as shown in the following examples.

(Example 22)
[pre-process]
A mixture of 10 mmol of ethoxytrimethylsilane ( _Me3SiOEt ), 10 mmol of acetic anhydride ((MeCO) _2O ), and 25 mg of H ⁺ type cation exchange resin (Amberlyst 15) as a catalyst was stirred in a closed reaction vessel. while heating at 110° C. for 30 minutes. After the catalyst was removed by centrifugation, the reaction solution was analyzed by NMR. As a result, it was found that 9.6 mmol (96% yield) of acetoxytrimethylsilane ((MeCO ₂ )SiMe ₃ ), which is an acyloxysilane, was produced. Ta.

[Reaction step]
Using the acetoxytrimethylsilane solution obtained in the preceding step as it is, reaction and analysis were carried out under the same reaction conditions as in Example 2.

As a result, tetramethylsilane (Me ₄ Si), trimethylsilane (Me ₃ SiH), trimethylsilanol (Me ₃ SiOH), hexamethyldisiloxane (Me ₃ SiOSiMe ₃ ), octamethyltrisiloxane (Me ₃ SiOSiMe ₂ OSiMe ₃ ) and hexamethylcyclotrisiloxane ((SiMe ₂ O) ₃ ) were identified. The raw material conversion rate and the yield of the product (calculated based on the composition ratio at each sampling time) are 100%, 26%, 4%, 13%, 42%, 4%, and 7%, respectively, at 5 minutes; 100%, 25%, 4%, 14%, 41%, 5% and 7% at 6 minutes; 100%, 23%, 2%, 18%, 41%, 4% and 7% at 8 minutes; 99%, 21%, 3%, 19%, 41%, 6%, and 7% at 10 minutes (see Table 1-3).

(Example 23)
Using the solution of acetoxytrimethylsilane ((MeCO ₂ )SiMe ₃ ) obtained in the previous step under the same reaction conditions as in Example 22, the injection rate by a syringe pump was set at 5 μL/min, and the reaction mixture was collected. The reaction and analysis were carried out in the same manner as in Example 2, except that the sampling times were 8, 12, 16, and 20 minutes after the start of flowing acetoxytrimethylsilane.

As a result, tetramethylsilane (Me ₄ Si), trimethylsilane (Me ₃ SiH), trimethylsilanol (Me ₃ SiOH), hexamethyldisiloxane (Me ₃ SiOSiMe ₃ ), octamethyltrisiloxane (Me ₃ SiOSiMe ₂ OSiMe ₃ ) and hexamethylcyclotrisiloxane ((SiMe ₂ O) ₃ ) were identified. The raw material conversion rate and the yield of the product (calculated based on the composition ratio at each sampling time) are 100%, 48%, 0%, 6%, 46%, 0%, and 0%, respectively, at 8 minutes; 100%, 41%, 0%, 8%, 48%, 0%, and 2% at 12 minutes; 100%, 37%, 0%, 11%, 48%, 0%, and 4% at 16 minutes; 100%, 32%, 2%, 12%, 46%, 3%, and 3% at 20 minutes (see Table 1-3).

In the production method of the present invention, when the carbon-based catalyst was not used in the reaction step, the yields of carbosilane and hydrosilane were greatly reduced as shown in the following comparative examples.

(Comparative example 1)
Instead of 100 mg of activated carbon, the quartz tube was filled with 100 mg of quartz wool, and reaction and analysis were performed in the same manner as in Example 1.

As a result, the yield of tetramethylsilane (calculated based on the composition ratio at each time) after 5, 6, 8, and 10 minutes from the start of flowing acetoxytrimethylsilane was all 1%. Moreover, the yield of trimethylsilane after 5, 6, 8, and 10 minutes from the start of flowing acetoxytrimethylsilane was 0% (see Table 1-3).

Example 1, which used a carbon-based catalyst, contained 66-33% carbosilane and 4% hydrosilane.
~3% was generated. On the other hand, in Comparative Example 1 in which no carbon-based catalyst was used, the yields of carbosilane and hydrosilane were 1% and 0%, respectively, which were significantly lower than in Example 1.
This result indicates that the carbon-based catalyst is involved in the formation of carbosilane and hydrosilane.

Annotations in Tables 1-1 to 1-3 are shown below.
1) In Examples 22 and 23, the pre-process and the reaction process were carried out continuously.
2) (MeCO ₂ )SiMe ₃ : acetoxytrimethylsilane
( _MeCO2 ) _SiEt3 : acetoxytriethylsilane.
3) AC1: Activated carbon (product number 032-18091, lot number PTE1918, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., powder)
AC2: Activated carbon (product number 037-02115, lot number LEK0442, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., powder)
AC3: Activated carbon (product number 037-02115, lot number PAM0181, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., powder)
AC4: Activated carbon (product number 037-02115 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., lot number WTK0788,
powder)
AC5: Activated carbon (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product number 034-02125, lot number LEM6266, used after pulverizing granules)
AC6: Activated carbon (manufactured by Merck, product number 242276, lot number SHBM8130, powder)
GR1: Graphene (manufactured by Merck, product number 900407, lot number MKCP4989, nanoplatelet, powder)
Pd/C: 5% palladium-supported activated carbon (manufactured by Merck, product number 205680, lot number MKCN6878
, powder)
Pt/C: 5% platinum-supported activated carbon (manufactured by Merck, product number 205931, lot number MKCN3581, powder)
Cu/C: 3% copper-supported activated carbon (manufactured by Merck, product number 709107, lot number SHBC9181V, powder)
Ru/C: 5% ruthenium-supported activated carbon (manufactured by Merck, product number 206180, lot number MKCN4206
, powder)
Rh/C: 5% rhodium-supported activated carbon (manufactured by Merck, product number 206164, lot number MKCH2780,
powder).
4) Nitrogen gas was used as carrier gas.
5) Conversion rate of acyloxysilane and yield of each product calculated from the composition ratio of the components (unreacted acyloxysilane and product) collected during the time from the start of flowing acyloxysilane to sampling. When the acyloxysilane is (MeCO ₂ )SiMe ₃ , the composition ratio of the collected components is calculated from the integrated intensity ratio of each component peak in ¹ H NMR, and when the acyloxysilane is (MeCO ₂ )SiEt ₃ was calculated from the area ratio of each component peak in GC and the integrated intensity ratio of each component peak in ²⁹ Si NMR.
6) Si--R and Si--H are carbosilane and hydrosilane, respectively, obtained by the production method of the present invention.
When the acyloxysilane is Me ₃ Si(OCOMe), the various products are as follows.
Si-R: _Me4Si (tetramethylsilane)
Si-H: _Me3SiH (trimethylsilane)
Si-OH: _Me3SiOH (trimethylsilanol)
Si-O-Si: _{Me3SiOSiMe3 (} hexamethyldisiloxane)
Si _- O- _Si -O-Si: _{Me3SiOSiMe2OSiMe3} (octamethyltrisiloxane)
(SiO) ₃ : (SiMe ₂ O) ₃ (hexamethylcyclotrisiloxane)
When the acyloxysilane is Et ₃ Si(OCOMe), the various products are as follows.
Si-R: Et ₃ SiMe (triethyl(methyl)silane)
Si-H: _Et3SiH (triethylsilane)
Si-OH: _Et3SiOH (triethylsilanol)
Si-O-Si: _{Et3SiOSiEt3 (} hexaethyldisiloxane)
_Si -O-Si-O-Si: _{Et3SiOSiEt2OSiEt3} ( _{octaethyltrisiloxane} )
(SiO) ₃ : (SiEt ₂ O) ₃ (hexaethylcyclotrisiloxane)
7) Place 50 mg of quartz wool for fixing on each side of 100 mg of quartz wool, and fill the quartz tube.

Notes in Table 2 are shown below.
1) For the names of reaction products, see Note 6 in Tables 1-1 to 1-3.
2) Measured in deuterated chloroform. The relaxation reagent Cr(acac) ₃ (chromium (III) acetylacetonate) was added and measured. The numbers in parentheses indicate the integrated intensity ratio of each peak.
3) GC-MS (EI, 70eV).
4) Since the amount of product was small and the peak intensity was weak in ²⁹ Si NMR, the position of the peak could not be clearly confirmed.

By the production method of the present invention, carbosilane and/or hydrosilane, which are useful as functional chemicals, functional materials, etc., can be produced more efficiently and safely. is.

Claims (6)

Si—OCOR bond (hereinafter, OCO represents OC (=O) of an oxycarbonyl group; R is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and is bonded to the carbon atom of the hydrocarbon group some or all of the hydrogen atoms may be substituted with groups that do not participate in the reaction) in the presence of a carbon-based catalyst,
A method for producing a carbosilane having a Si—R bond and/or a hydrosilane having a Si—H bond, wherein the carbon-based catalyst is a carbon-based compound containing 90% by mass or more of carbon. The production method according to claim 1, wherein the carbon-based compound is a porous carbon-based compound. 3. The production method according to claim 2, wherein the porous carbon-based compound is one or more selected from activated carbon, graphene, mesoporous carbon, carbon nanotubes, and carbon black. The production method according to any one of claims 1 to 3, wherein the reaction step is a step performed at a temperature of 100 to 800°C. The production method according to any one of claims 1 to 4, wherein the acyloxysilane having the Si-OCOR bond is an acyloxysilane represented by the following general formula (I).
R ¹ _a R ² _b R ³ _c Si(OCOR) _d (I)
(Wherein, a, b, and c are each independently 0 or 1; d is an integer of 1 or more and 3 or less; a + b + c + d = 4; R is as defined above; R ¹ , R ² and R ³ are each independently a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom, and hydrogen bonded to the carbon atoms of the hydrocarbon group and alkoxy group Some or all of the atoms may be substituted with groups that do not participate in the reaction.) Prior to the reaction step, including a pre-step of producing the acyloxysilane having the Si—OCOR bond,
The production method according to any one of claims 1 to 5, wherein the pre-process is any one of the following (1) to (3).
(1) An alkoxysilane having a Si—OR ⁴ bond (R ⁴ is a hydrocarbon group having 1 to 3 carbon atoms) is treated with (RCO) ₂ O (R is as defined above). a step of producing the acyloxysilane having the Si—OCOR bond by reacting the carboxylic acid anhydride to be obtained.
(2) by reacting an allylsilane having a Si—R ⁵ bond (R ⁵ is an allyl group) with a carboxylic acid represented by RCO ₂ H (R is as defined above), a step of producing the acyloxysilane having the Si—OCOR bond;
(3) Si—OCOR by reacting a halosilane having a Si—X bond with a carboxylic acid represented by RCO ₂ H (R is as defined above; X is a halogen atom); A step of producing an acyloxysilane having a bond.