JP2021155337A - Production method of carbosilane - Google Patents

Abstract

To provide an efficient production method of a carbosilane which is useful as functional chemicals.SOLUTION: A production method of a carbosilane having an Si-R bond includes a decarboxylation reaction step in which decarboxylation from an acyloxysilane having an Si-OCOR bond is carried out in the presence of a base catalyst, satisfies any of following conditions (1)-(3), and may include a previous step to form the acyloxysilane. (1) The base catalyst is: a compound of which pKa of the conjugate acid is 8-50; a phosphazene compound; a bicyclic amine compound; a guanidine compound; an amidine compound; or an organic polymer or an inorganic compound having a group derived from those compounds. (2) The R of the Si-OCOR bond is an alkyl group or an aryl group, or an alkynyl group having a halogen atom, a nitro group, or a cyano group. (3) A calculated value ΔU of an energy difference of the reaction of the decarboxylation reaction step is 20 kcal/mol or less.SELECTED DRAWING: None

Description

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

Carbosilane having a Si—C bond is an important compound used as a reagent for precision synthesis, an intermediate, etc. for producing various functional chemicals such as pharmaceuticals, agricultural chemicals, optical materials, electronic materials, or various functional materials. Is.
As a general method for producing these carbosilanes, a method (method A) in which an organometallic compound such as a Grignard reagent or an organolithium reagent is reacted with chlorosilane, an alkoxysilane or the like is well known (Patent Document 1, non-patent). Document 1).
On the other hand, using a catalytic reaction accelerator, a specific Si-OCOR'bond (OCO indicates the OC (= O) of the oxycarbonyl group. R'is the trichloromethyl group (CCl ₃ ), pentafluoro. Decarbonation from asyloxysilane having a phenyl group (C ₆ F ₅ ) or a trifluoromethyl group (CF ₃ )) is performed (decarbonation indicates a CO ₂ desorption reaction). A method for producing a carbosilane having a Si—R'bond (method B) has been reported (Non-Patent Documents 2 and 3, Patent Documents 2 and 3).
In method (B), different reaction accelerators were known depending on the type of asyloxysilane. For example, when the _{asyloxysilane is Me 3} Si-OCOCl ₃ (Me indicates a methyl group), triethylamine and N-methylpyrrolidin are used (Non-Patent Document 1), and the asyloxysilane is R "Me ₂ Si. In the case of −OCOCl ₃ (R” is a methyl group, a chloromethyl group, a phenyl group, a trimethylsilyl group, or a hydrogen atom), a quaternary ammonium salt (Et ₃ (PhCH ₂ ) NCl, Bu ₄ NBr; Et. , Ph, Bu, respectively, an ethyl group, a phenyl group, a butyl group.), potassium salt / crown ether mixture system _{(K 2} CO 3/18-crown-6) is preferably used (non-patent Document 2). When the _{asyloxysilane is Me 3} Si-OCOC ₆ F ₅ , KF and CsF are preferably used in the dimethylformamide solvent (Patent Document 2), and when the _{asyloxysilane is Me 3} Si-OCOCF _3, , Potassium trifluoroacetate is preferably used in the dimethylformamide solvent (Patent Document 3).

U.S. Pat. No. 6,160,151 Russian Patent Application Publication No. 20130111741 French Patent Application Publication No. 2862972

4th Edition Experimental Chemistry Course, Vol. 24, p. 122, Maruzen (1992) H. H. Hergot, G.M. Simchen, Synthesis, 626-627 (1980) A. N. Kornev, O.D. S. Donnikova, V.I. V. Seminov, Yu. A. Kurskii, Russ. Chem. Bull. , 44,145-148 (1995)

However, with respect to the conventional method, in the method (A), it is necessary to use an organometallic compound which is not easy to handle and is dangerous because (1) it is highly reactive with water or moisture.
There are problems such as (2) the production cost of the organometallic compound is generally high, and (3) a large amount of metal chloride is produced as a by-product.
Further, in the method (B), (1) the activity of the previously known reaction accelerator is not sufficient, so that the applicable asyloxysilane is limited to a specific type, and (2) a product. (3) Since the reaction system is a uniform system, the reaction accelerator cannot be separated and recovered by a simple method such as filtration or centrifugation. (4) When a dimethylformamide solvent is used. Since dimethylformamide is a harmful substance, it is necessary to consider the impact on the environment and health (The Ministry of Health, Labor and Welfare of Japan has "controlled concentration" as an index for evaluating the state of the working environment for a specific harmful substance. The concentration of the harmful substance in the work place is required to be equal to or less than the control concentration. The control concentration of dimethylformamide is 10 ppm).
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 an object of the present invention is to provide a method for producing a carbosilane having a Si—C bond more safely and efficiently.

As a result of diligent research to solve the above problems, the present inventors have found that the formation of carbosilane having a Si—C bond by decarboxylation from asyloxysilane is (1) the pKa of the conjugate acid is in a specific range. Efficient progress in the presence of a base catalyst, (2) Efficient progress in asyloxysilane having a specific structure, (3) The calculated value of the energy difference between the original system and the production system is less than a certain value. We have found that the process proceeds efficiently in the reaction system of the above, and have completed the present invention.

That is, this application provides the following inventions.
<1>
Si-OCOR bond (OCO represents OC (= O) of oxycarbonyl group. R represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and a hydrogen atom bonded to the carbon atom of the hydrocarbon group. Part or all of the Si-R bond comprising a decarbonation reaction step of decarbonizing in the presence of a base catalyst from an acyloxysilane having (may be substituted with a group not involved in the reaction). A method for producing a carbosilane, which satisfies any of the following conditions (1) to (3) and may include a pre-step for forming an acyloxysilane.
(1) The base catalyst is an organic compound having a pKa of a conjugated acid in the range of 8 to 50; a phosphazene compound; a bicyclic amine compound; a guanidine compound; an amidin compound; or a group derived from those compounds. It is a polymer-based compound or an inorganic-based compound;
(2) The R of the Si-OCOR bond is an alkyl or aryl group in which a part or all of the hydrogen atom bonded to the carbon atom is substituted with a halogen atom, a nitro group, or a cyano group; or an alkynyl group; be.
(3) Calculated value ΔU of the energy difference of the reaction produced by carbosilane by decarbonation from the asyloxysilane (calculated value ΔU of the energy difference is the density general function method (calculation level of ^{B3LYP / 6-31G **).} The calculated value of the energy difference between the original system and the generated system (total internal energy of the generated system molecule-internal energy of the original molecule) is 20 kcal / mol or less.
<2>
The production method according to <1>, wherein the pre-step is any of the following steps (4) to (6), and the pre-step and the subsequent decarboxylation reaction step are continuously performed.
(4) The asyloxysilane having a Si-OCOR bond is added to an alkoxysilane having a Si-OR'bond (R'indicates a hydrocarbon group having 1 to 3 carbon atoms) to (RCO) ₂ O (R). Is synonymous with the above.) Is a step of reacting and forming a carboxylic acid anhydride represented by).
(5) The acyloxy having the Si-OCOR bond, the Si-R "bond (R" is. Showing the allyl group) allylsilane having, _RCO 2 H (R has the same meaning as defined above.) In A step of reacting and forming the represented carboxylic acid.
(6) an acyloxy having the Si-OCOR bonds, the chlorosilane having of Si-Cl bond, _RCO 2 H (R has the same meaning as defined above.) Is reacted with a carboxylic acid represented by formed Process.
<3>
The base catalyst is 1-tert-butyl-2,2,4,5,4-pentakis (dimethylamino) -2λ ⁵ , 4λ ⁵ -catenadi (phosphazene) (P2-t-Bu), 1-tert-butyl. 4,4,4-tris (dimethylamino) -2,2-bis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] -2λ ^5, 4λ ⁵ - Katenaji (phosphazene) (P4-t-Bu) , 2- tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorin (BEMP), tert-butylimino-tri (pyrrolidino) phosphorane (BTPP), 1-azabicyclo [2.2.2] Octane (ABCO), 1,4-diazabicyclo [2.2.2] Octane (DABCO), 7-Methyl-1,5,7-Triazabicyclo [4.4.0] Deca-5-ene (MTBD) , 1,8-Diazabicyclo [5.4.0] -7-undecene (DBU), 1,5-diazabicyclo [4.3.0] -5-nonen (DBN), or a group derived from them. The production method according to <1> or <2>, which is a base selected from organic polymers.
<4>
The production method according to any one of <1> to <3>, wherein the asyloxysilane having a Si-OCOR bond is an asyloxysilane selected from the following general formulas (IA) to (ID).
R ¹ _a R ² _b R ³ _c Si (OCOR) _d (IA)
RCO ₂ (SiR ⁴ R ⁵ ) _m1 OCOR (IB)
RCO ₂ (SiR ⁶ R ⁷ O) _m2 (COR) (IC)
(R ⁸ _e R ⁹ _f R ¹⁰ _g SiOCO) _h R ¹¹ (ID)
(In these equations, a, b, and c are independently 0 or 1; d is an integer greater than or equal to 1 and less than or equal to 3; a + b + c + d = 4; m1 and m2 are independently, respectively. It is an integer of 2 or more; R is synonymous with the above; R ^{1 to} R ¹⁰ are independently each of a hydrogen group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom. Yes, some or all of the hydrogen atoms attached to the carbon atoms of the hydrocarbon group or the alkoxy group may be substituted with groups that are not involved in the reaction; e, f, and g are independent of each other. 0 or 1; e + f + g = 3; h is an integer of 2-4; R ¹¹ is an h-valent hydrocarbon group having 1 to 20 carbon atoms, of the h-valent hydrocarbon group. Part or all of the hydrogen atom bonded to the carbon atom may be replaced with a group that does not participate in the reaction.)

INDUSTRIAL APPLICABILITY The present invention has an effect that a carbosilane having a Si—C bond can be produced more safely and efficiently than a conventional method.

Specifically, the method for producing a carbosilane having a Si—C bond, which is one embodiment of the present invention (hereinafter, may be abbreviated as “the production method according to the present embodiment”) has the following characteristics. ..
(1) The raw materials and bases are easy to handle and highly safe.
(2) A reaction system that does not generate a large amount of salt or other waste.
(3) When a solid base is used, the base can be easily separated and recovered.
The manufacturing method of the present invention makes it possible to improve the safety and efficiency of the manufacturing process, and is considered to have great advantages in terms of economy, low environmental load, etc. as compared with the prior art.

Hereinafter, the present invention will be described in detail. Unless otherwise specified, when a symbol in a certain formula in the present specification is also used in another formula, the same symbol has the same meaning.
In the production method according to this embodiment, a Si—OCOR bond (OCO indicates an OC (= O) of an oxycarbonyl group; R indicates a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. The hydrocarbon. A part or all of the hydrogen atom bonded to the carbon atom of the group may be substituted with a group that does not participate in the reaction), and decarbonation is performed in the presence of a base catalyst from the acyloxysilane. A method for producing a carbosilane having a Si—R bond, which comprises a reaction step.
In the present specification, the "group not involved in the reaction" does not show the reaction activity of the decarboxylation reaction or the reaction activity of the decarboxylation reaction and the asyloxysilane formation reaction described later, and adversely affects these reactions. Means a group that does not reach.

In this embodiment, examples of the asyloxysilane that can be used as a raw material include asyloxysilane represented by the following general formulas (IA) to (ID).
R ¹ _a R ² _b R ³ _c Si (OCOR) _d (IA)
RCO ₂ (SiR ⁴ R ⁵ ) _m1 OCOR (IB)
RCO ₂ (SiR ⁶ R ⁷ O) _m2 (COR) (IC)
(R ⁸ _e R ⁹ _f R ¹⁰ _g SiOCO) _h R ¹¹ (ID)

In these equations, a, b, and c are independently 0 or 1; d is an integer greater than or equal to 1 and less than or equal to 3; a + b + c + d = 4. Further, m1 and m2 are independently integers of 2 or more. R is synonymous with the above. R ^{1 to} R ¹⁰ 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 hydrocarbon group or the carbon atom of the alkoxy group. Some or all of the hydrogen atoms may be substituted with groups that are not involved in the reaction. e, f, and g are independently 0 or 1, respectively; e + f + g = 3. h is an integer of 2-4. R ¹¹ is an h-valent hydrocarbon group having 1 to 20 carbon atoms, and a part or all of the hydrogen atoms bonded to the carbon atoms of the h-valent hydrocarbon group are substituted with groups not involved in the reaction. You may.

Specific examples of the hydrocarbon group represented by R ^{1 to} R ¹⁰ include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group 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. A part or all of the hydrogen atom bonded to the carbon atom of the alkyl group may be substituted with a group not involved in the reaction.

Specific examples of the group not involved in the reaction include an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, a halogen atom and the like. More specifically, the alkoxy group, the alkoxycarbonyl group, and the halogen atom are represented by an alkoxy group such as a methoxy group, an ethoxy group, and a hexoxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a propoxycarbonyl group; and a fluorine atom and a chlorine atom. Halogen atoms such as;
Specific examples of the alkyl group which may be substituted with a group not involved 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 and a decyl group. Examples thereof include a group, a 2-methoxyethyl group, a 3-ethoxypropyl group, a 2-methoxycarbonylethyl group, a trifluoromethyl group, a 3-chloropropyl group and the like.

When the hydrocarbon group is an aryl group, a hydrocarbon ring-based or heterocyclic monovalent aromatic organic group can be used. When the aryl group is a hydrocarbon ring system, the number of carbon atoms in the hydrocarbon ring system is preferably 6 to 18, more preferably 6 to 14. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group and the like. When the aryl group is a heterocyclic system, the hetero atom in the heterocycle is sulfur, an oxygen atom, or the like. The aryl group preferably has 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms. Specific examples of the aryl group include a thienyl group, a benzothienyl group, a dibenzothienyl group, a frill group, a benzofuryl group, a dibenzofuryl group and the like.
Some of the hydrogen atoms of the aryl group may be substituted with a group that does not participate in the reaction. Specific examples of the group not involved in the reaction include those shown in the case of the above-mentioned alkyl group. Examples of the group that does not participate in other reactions include an oxyethylene group and an oxyethyleneoxy group, which are divalent groups that bond two carbon atoms on the ring.
Specific examples of the aryl group substituted with a group not involved 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, and a methyl (methoxy). Examples thereof include a phenyl group, a fluoro (methyl) phenyl group, a chloro (methoxy) phenyl group, a bromo (methoxy) phenyl group, a 2,3-dihydrobenzofuranyl group, a 1,4-benzodioxanyl group and the like.

Further, when the hydrocarbon group is an aralkyl group, the carbon number of the aralkyl group is preferably 7 to 19, more preferably 7 to 15. A part or all of the hydrogen atom bonded to the carbon atom of the aralkyl group may be substituted with a group not involved in the reaction. Specific examples of the group not involved in the reaction include those shown in the case of the above-mentioned alkyl group.
Specific examples of the aralkyl group which may be substituted with a group not involved 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-Methylphenyl) ethyl group and the like can be mentioned.

When the hydrocarbon group is an alkenyl group, the alkenyl group has preferably 2 to 18 carbon atoms, more preferably 2 to 14 carbon atoms. A part or all of the hydrogen atom bonded to the carbon atom of the alkenyl group may be substituted with a group not involved in the reaction. Specific examples of the group not involved in the reaction include those shown for the above-mentioned alkyl group and the above-mentioned aryl group.
Specific examples of the alkenyl group which may be substituted with a group not involved in the reaction include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 5-hexenyl group, a 9-decenyl group and a 2-phenylethenyl group. Examples thereof include 2- (methoxyphenyl) ethenyl group, 2-naphthyl ethenyl group, 2-anthryl ethenyl group and the like.

When the hydrocarbon group is an alkynyl group, the alkynyl group has preferably 2 to 18 carbon atoms, more preferably 2 to 16 carbon atoms. A part or all of the hydrogen atom bonded to the carbon atom of the alkynyl group may be substituted with a group not involved in the reaction. Specific examples of the group not involved in the reaction include those shown for the above-mentioned alkyl group and the above-mentioned aryl group.
Specific examples of the alkynyl group which may be substituted with a group not involved in the reaction include a phenylethynyl group, a 1-propynyl group, a 3-phenyl-1-propynyl group and the like.

On the other hand, when R ^{1 to} R ¹⁰ are alkoxy groups, the number of carbon atoms of the alkoxy group is preferably 1 to 16, and more preferably 1 to 12. A part or all of the hydrogen atom bonded to the carbon atom of the alkoxy group may be substituted with a group not involved in the reaction. Specific examples of the group not involved in the reaction include those shown in the case of the above-mentioned alkyl group.
Specific examples of the alkoxy group which may be substituted with a group not involved in the reaction include a methoxy group, an ethoxy group, a tert-butoxy group, a cyclohexoxy group and the like.

When R ^{1 to} R ¹⁰ are halogen atoms, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or the like, preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom.

R ¹¹ represents an h-valent hydrocarbon group having 1 to 20 carbon atoms. The h-valent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ is a linking group obtained by removing h hydrogen atoms from an alkane having 1 to 20 carbon atoms, an aromatic ring, or the like. The h-valent hydrocarbon group preferably has 1 to 16 carbon atoms, and more preferably 1 to 12 carbon atoms. The hydrogen atom bonded to the carbon atom of the h-valent hydrocarbon group may be substituted with a group not involved in the reaction.
Note that h is an integer of 2 to 4, preferably 2.

When the h-valent hydrocarbon group is an aliphatic linking group obtained by removing h hydrogen atoms from an alkane, the alkane has preferably 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms. A part or all of the hydrogen atoms bonded to the aliphatic linking group obtained by removing h hydrogen atoms from the alkane may be substituted with a group not involved in the reaction. Specific examples of the groups not involved in the reaction include those shown in the case of alkyl groups represented by ^{R 1 to} R ^10.
As specific aliphatic linking groups, h hydrogen atoms are removed from methane, ethane, propane, butane, pentane, hexane, cyclohexane, octane, decane, methoxyethane, ethoxypropane, methoxycarbonylethane, difluoromethane, chloropropane and the like. The group can be mentioned.

When the h-valent hydrocarbon group is an aromatic linking group obtained by removing h hydrogen atoms from the aromatic ring, the aromatic ring is an aromatic hydrocarbon ring or an aromatic heterocycle.
In the case of an aromatic hydrocarbon ring, the number of carbon atoms in the aromatic hydrocarbon ring is preferably 6 to 18, more preferably 6 to 14. Specific examples of the aromatic hydrocarbon ring include benzene, naphthalene, anthracene, phenanthrene, pyrene and the like.
When the aromatic ring is an aromatic heterocycle, the heteroatom in the aromatic heterocycle is sulfur, an oxygen atom, or the like. The carbon number of the aromatic heterocycle is preferably 4 to 12, more preferably 4 to 8. Specific examples of the aromatic heterocycle include thiophene, benzothiophene, dibenzothiophene, furan, benzofuran, dibenzofuran and the like.
A part or all of the hydrogen atoms bonded to the aromatic linking group obtained by removing h hydrogen atoms from the aromatic ring may be substituted with a group not involved in the reaction. Specific examples of the groups not involved in the reaction include those shown in the case of alkyl groups represented by ^{R 1 to} R ^10. Examples of the group that does not participate in other reactions include an oxyethylene group and an oxyethyleneoxy group, which are divalent groups that bond two carbon atoms on the aromatic ring.
Specific aromatic linking groups include benzene, methylbenzene, ethylbenzene, hexylbenzene, methoxybenzene, ethoxybenzene, butoxybenzene, octoxybenzene, methyl (methoxy) benzene, fluoro (methyl) benzene, and chloro (methoxy) benzene. , Bromo (methoxy) benzene, 2,3-dihydrobenzofuran, 1,4-benzodioxane and the like from which h hydrogen atoms have been removed.

Further, R represents a hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms, and when R is a hydrocarbon group, the hydrocarbon group has preferably 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms. .. The hydrogen atom bonded to the carbon atom of the hydrocarbon group may be substituted with a group that does not participate in the reaction.
Specific examples of the groups not involved in the reaction include those shown in the case of alkyl groups represented by ^{R 1 to} R ^10.
Examples of the hydrocarbon group represented by R include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group and the like. Specific examples of these groups include the above-mentioned R ^{1 to} R ¹⁰
Examples include those shown in the explanation of the basis of.

Among those groups, in terms of reactivity, R is an alkyl or aryl group in which the hydrogen atom bonded to the carbon atom is substituted with a halogen atom, a nitro group, or a cyano group, or an alkynyl group. Is preferable. As the halogen atom, a fluorine atom, a chlorine atom and a bromine atom are preferable, and a fluorine atom and a chlorine atom are more preferable.

Specific examples of these groups include trifluoromethyl group, difluoromethyl group, fluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, trichloromethyl group, dichloromethyl group and chloromethyl group. Pentachloroethyl group, nitromethyl group, cyanomethyl group, pentafluorophenyl group, tetrafluorophenyl group, trifluorophenyl group, difluorophenyl group, fluorophenyl group, pentachlorophenyl group, tetrachlorophenyl group, trichlorophenyl group, dichlorophenyl group, chlorophenyl Examples thereof include a group, a nitrophenyl group, a cyanophenyl group, an ethynyl group, a propynyl group and a phenylethynyl group.

m1 and m2 are independently integers of 2 or more, and the upper limit thereof is not particularly limited as long as the effect of the present invention is not impaired, but is usually 2000 or less, preferably 1000 or less. It is particularly preferable that m1 and m2 are 2, that is, the asyloxysilanes represented by the formulas (IB) and (IC) are disilane and disiloxane having two asyloxy groups, respectively. preferable.

Thus, specific examples of acyloxy of the general formula (IA) is trimethyl (pentafluorophenyl carbonyloxy) silane _{((C 6 F 5 CO 2} ) SiMe 3), dimethyl bis (pentafluorophenyl carbonyloxy) silane _{((C 6 F 5 CO 2} ) 2 SiMe 2), methyltris (pentafluorophenyl carbonyloxy) silane _{((C 6 F 5 CO 2} ) 3 SiMe), tetrakis (pentafluorophenyl carbonyloxy) silane _{((C 6 F 5 CO 2) 4 Si)} , tri (ethoxy) (pentafluorophenyl carbonyloxy) silane _{((C 6 F 5 CO 2} ) Si (OEt) 3), di (ethoxy) bis (pentafluorophenyl carbonyloxy) silane ((C ₆ F ₅ CO ₂ ) ₂ Si (OEt) ₂ ), Tri (methoxy) (Pentafluorophenylcarbonyloxy) Silane ((C ₆ F ₅ CO ₂ ) Si (OMe) ₃ ), Di (methoxy) bis (Pentafluorophenylcarbonyloxy) silane ((C ₆ F ₅ CO ₂ ) ₂ Si (OMe) ₂ ), trichloro (pentafluorophenyl carbonyloxy) silane ((C ₆ F ₅ CO ₂ ) SiCl ₃ ), dichlorobis (penta) fluorophenyl carbonyloxy) silane _{((C 6 F 5 CO 2} ) 2 SiCl 2), trimethyl (2,3,5,6-tetrafluoro-phenyl carbonyloxy) silane _((2,3,5,6-F 4 C ₆ HCO ₂₎ SiMe _3), trimethyl (2,4,6-trifluorophenyl carbonyloxy) silane _{((2,4,6-F 3 C 6} H 2 CO 2) SiMe 3), trimethyl (2,6 difluorophenyl carbonyloxy) silane _{((2,6-F 2 C 6} H 3 CO 2) SiMe 3), trimethyl (2-fluorophenyl carbonyloxy) silane _{((2-FC 6 H 4} CO 2) SiMe 3), trimethyl (2,4,6-trichlorophenyl carbonyloxy) silane _{((2,4,6-Cl 3 C 6} H 2 CO 2) SiMe 3), trimethyl (2,6-dichlorophenyl carbonyloxy) silane ((2, 6-Cl ₂ C ₆ H ₃ CO ₂ ) SiMe ₃ ), trimethyl (2-chlorophenylcarbonyloxy) silane ((2-ClC ₆ H ₄ CO ₂ ) SiMe ₃ ), trimethyl (3,4,5,6-tetrafluoro-2-nitrophenylcarbonyloxy) silane ([ 2- (O ₂ N) C ₆ F ₄ CO ₂ ] SiMe ₃ ), trimethyl (2-nitrophenylcarbonyloxy) silane ([2- (O ₂ N) C ₆ H ₄ CO ₂ ] SiMe ₃ ), trimethyl ( 2-Cyanophenylcarbonyloxy) silane ([2- (NC) C ₆ H ₄ CO ₂ ] SiMe ₃ ), dimethylphenyl (pentafluorophenylcarbonyloxy) silane ((C ₆ F ₅ CO ₂ ) S)
iMe ₂ Ph), dimethyl (pentafluorophenylcarbonyloxy) (vinyl) silane ((C ₆ F ₅ CO ₂ ) SiMe ₂ (CH = CH ₂ )), (3-cyanopropyl) dimethyl (pentafluorophenylcarbonyloxy) Silane ((C ₆ F ₅ CO ₂ ) SiMe ₂ [(CH ₂ ) ₃ CN]), trimethyl (trifluoroacetyloxy) silane ((CF ₃ CO ₂ ) SiMe ₃ ), dimethylbis (trifluoroacetyloxy) silane ((CF ₃ CO ₂ ) ₂ SiMe ₂ ), tri (ethoxy) (trifluoroacetyloxy) silane ((CF ₃ CO ₂ ) Si (OEt) ₃ ), di (methoxy) bis (trifluoroacetyloxy) silane ( (CF ₃ CO ₂ ) ₂ Si (OMe) ₂ ), trichloro (trifluoroacetyloxy) silane ((CF ₃ CO ₂ ) SiCl ₃ ), trimethyl (pentafluoropropionyloxy) silane ((CF ₃ CF ₂ CO ₂ )) SiMe ₃ ), trimethyl (trichloroacetyloxy) silane ((CCl ₃ CO ₂ ) SiMe ₃ ), (ethoxy) dimethyl (trichloroacetyloxy) silane ((CCl ₃ CO ₂ ) SiMe ₂ (OEt)), di (ethoxy) Methyl (trichloroacetyloxy) silane ((CCl ₃ CO ₂ ) SiMe (OEt) ₂ ), tri (ethoxy) (trichloroacetyloxy) silane ((CCl ₃ CO ₂ ) Si (OEt) ₃ ), trichloro (trichloroacetyloxy) ) Silane ((CCl ₃ CO ₂ ) SiCl ₃ ), dichlorobis (trichloroacetyloxy) silane ((CCl ₃ CO ₂ ) ₂ SiCl ₂ ), trimethyl (dichloroacetyloxy) silane ((CCL ₂ CO ₂ ) SiMe ₃ ), Trimethyl (chloroacetyloxy) silane ((CH ₂ ClCO ₂ ) SiMe ₃ ), trimethyl (chlorodifluoroacetyloxy) silane ((CClF ₂ CO ₂ ) SiMe ₃ ), trimethyl (tribromoacetyloxy) silane ((CBr ₃ CO)) ₂ ) SiMe ₃ ), trimethyl (phenylethynylcarbonyloxy) silane ((PhC≡C) CO ₂ SiMe ₃ ), trimethyl (1-propynylcal) Bonyloxy) silane ((MeC≡C) CO ₂ SiMe ₃ ) and the like can be mentioned.

On the other hand, specific examples of the asyloxysilane of the general formula (IB) include 1,1,2,2-tetramethyl-1,2-bis (pentafluorophenylcarbonyloxy) disilane ((C ₆ F ₅ CO _2). ) SiMe ₂ SiMe ₂ (OCOC ₆ F ₅ )), 1,1,2,2,3,3-hexamethyl-1,3-bis (pentafluorophenylcarbonyloxy) trisilane ((C ₆ F ₅ CO ₂ ) SiMe ₂ SiMe ₂ SiMe ₂ (OCOC ₆ F ₅ )) and the like can be mentioned.

Specific examples of the asyloxysilane of the general formula (IC) include 1,1,3,3-tetramethyl-1,3-bis (pentafluorophenylcarbonyloxy) disiloxane ((C ₆ F ₅ CO). ₂ ) SiMe ₂ OSiMe ₂ (OCOC ₆ F ₅ )), 1,1,3,3,5,5-hexamethyl-1,5-bis (pentafluorophenylcarbonyloxy) trisiloxane ((C ₆ F ₅ CO ₂₎ ) SiMe ₂ OSiMe ₂ OSiMe ₂ (OCOC ₆ F ₅ )) and the like.

Specific examples of the asyloxysilane of the general formula (ID) include 2,4,5,6-tetrafluoro-1,3-bis (trimethylsiloxycarbonyl) benzene (1,3-C ₆ F ₄ (CO _2). SiMe ₃ ) ₂ ), 2,3,5,6-tetrafluoro-1,4-bis (trimethylsiloxycarbonyl) benzene (1,4-C ₆ F ₄ (CO ₂ SiMe ₃ ) ₂ ), etc. can.

Further, as the asyloxysilane used in the production method according to the present embodiment, the calculated value ΔU of the energy difference of the reaction in which carbosilane is produced by decarboxylation from asyloxysilane is 20 kcal / mol or less. Is also preferably used. The upper limit of ΔU is preferably 18 kcal / mol or less, more preferably 16 kcal / mol or less, and the lower limit of ΔU is not particularly limited, but is usually 1 kcal / mol or more. The decarbonization reaction from asyloxysilane is thermodynamically endothermic because the total internal energy of the molecules of the production system is higher than the internal energy of the molecules of the original system, and energy is supplied from the outside by heating or the like. Is a necessary reaction. However, it is considered that when ΔU is within the above range, the energy required for the reaction becomes sufficiently small, and the decarboxylation reaction can proceed even at a heating temperature of about 300 ° C. or lower.
Here, the calculated value ΔU of the energy difference is the energy difference between the original system and the production system (inside of the _{generation system molecules carbosilane and CO 2} ^{) by the density general function method (calculation level of B3LYP / 6-31G **).} _{Calculated value of energy = U (internal energy of carbosilane) + U (internal energy of CO 2} ) -U (internal energy of asyloxysilane) obtained by subtracting the internal energy of the original molecule asyloxysilane from the total energy. show.

When the asyloxysilane is a monosilane having one or more asyloxy groups, specific examples thereof are shown (the calculated value of ΔU (kcal / mol) is shown in square brackets. When there are multiple asyloxy groups, the asyloxysilane is shown. The calculated values when one asyloxy group causes a decarbonation reaction are shown.), (Ethynylcarbonyloxy _{) trichlorosilane ((HC≡CCO 2} ) SiCl ₃ ) [0.67], (1,3-butadiini). Lucarbonyloxy) trimethylsilane ((HC≡CC≡CCO ₂ ) SiCl ₃ ) [4.81], (ethynylcarbonyloxy) trimethylsilane ((HC≡CCO ₂ ) SiMe ₃ ) [5.72], tetrakis (penta) Fluorophenylcarbonyloxy) silane ((C ₆ F ₅ CO ₂ ) ₄ Si) [6.18], dichlorobis (pentafluorophenyl carbonyloxy) silane ((C ₆ F ₅ CO ₂ ) ₂ SiCl ₂ ) [6.19] ], Bis (pentafluorophenyl) bis (pentafluorophenylcarbonyloxy) silane ((C ₆ F ₅ CO ₂ ) ₂ Si (C ₆ F ₅ ) ₂ ) [6.38], (dicyanomethylcarbonyloxy) trimethylsilane ([(NC) ₂ CHCO ₂ ] SiMe ₃ ) [6.47], trimethyl (1-propynylcarbonyloxy) silane ((MeC≡CCO ₂ ) SiMe ₃ ) [6.57], trichloro (cyanomethylcarbonyloxy) Silane ((NCCH ₂ CO ₂ ) SiCl ₃ ) [6.67], trimethyl (phenylethynylcarbonyloxy) silane ((PhC≡CCO ₂ ) SiMe ₃ ) [6.76], trichloro (pentafluorophenylcarbonyloxy) silane _{((C 6 F 5 CO 2} ) SiCl 3) [7.27], ( trichloromethyl carbonyloxy) trichlorosilane _{((CCl 3 CO 2) SiCl} 3) [7.28], acetoxy trichlorosilane ((Meco ₂₎ SiCl ₃₎ [7.79], methyltris (pentafluorophenyl carbonyloxy) silane _{((C 6 F 5 CO 2} ) SiMe) [7.96], ( benzylcarbonyloxy) trichlorosilane _{((PhCH 2} CO 2) SiCl ₃ ) [8.08], trichloro (nitromethylcarbonyloxy) silane ((O ₂ NCH ₂ C) O ₂ ) SiCl ₃ ) [8.17], trichloro (methoxycarbonylmethylcarbonyloxy) silane ((MeOCOCH ₂ CO ₂ ) SiCl ₃ ) [8.24], methyl (pentafluorophenyl) bis (pentafluorophenylcarbonyloxy) ) Silane ((C ₆ F ₅ CO ₂ ) ₂ SiMe (C ₆ F ₅ )) [8.55], diacetoxydichlorosilane ((MeCO ₂ ) SiCl ₂ ) [8.56], (allylcarbonyloxy) tri Chlorosilane ((CH ₂ = CHCH ₂ CO ₂ ) SiCl ₃ ) [8.58], (tribromomethylcarbonyloxy) trimethylsilane ((CBr ₃ CO ₂ ) SiMe ₃ ) [8.64], dimethylbis (pentafluoro) Phenylcarbonyloxy) Silane ((C ₆ F ₅ CO ₂ ) ₂ SiMe ₂ ) [8.73], (Pentafluorophenyl) Tris (Pentafluorophenylcarbonyloxy) Silane ((C ₆ F ₅ CO ₂ ) ₃ Si ( C ₆ F ₅ )) [8.92], triethyl (pentafluorophenylcarbonyloxy) silane ((C ₆ F ₅ CO ₂ ) SiEt ₃ ) [8.96], triethyl (pentafluorophenylcarbonyloxy) silane (((C 6 F 5 CO 2) SiEt 3) [8.96], triethyl (pentafluorophenylcarbonyloxy) silane C ₆ F ₅ CO ₂ ) SiEt ₃ ) [8.96], dichloro (pentafluorophenyl) (pentafluorophenylcarbonyloxy) silane ((C ₆ F ₅ CO ₂ ) SiCl ₂ (C ₆ F ₅ ) [8. 98], dimethyl (pentafluorophenyl carbonyloxy) vinylsilane _{((C 6 F 5 CO 2} ) SiMe 2 Vi) [8.99], chlorodimethyl (pentafluorophenyl carbonyloxy) silane _{((C 6 F 5 CO 2} ) SiClMe ₂ ) [9.00], trimethyl (trichloromethylcarbonyloxy) silane ((CCl ₃ CO ₂ ) SiMe ₃ ) [9.00], trichloro (chloromethylcarbonyloxy) silane ((ClCH ₂ CO ₂ ) SiCl ₃ ) [9.18], dimethyl (pentafluorophenyl) (pentafluorophenylcarbonyloxy) silane ((C ₆ F ₅ CO ₂ ) SiMe ₂ (C ₆ F ₅ )) [9.26], triacetoxy (trichloromethyl) Carbonyl Oxy) silane ((Cl ₃ CCO ₂ ) Si (OCOMe) ₃ ) [9.43], trimethyl (tetrafluoro-4- _{pyridylcarbonyloxy) silane ((4-C 5} F ₄ NCO ₂ ) SiMe ₃ ) [9 .44], acetoxy trifluorosilane _{((MeCO 2) SiF 3)} [9.82], (3- cyanopropyl) dimethyl (pentafluorophenyl carbonyloxy) silane _{((C 6 F 5 CO 2} ) SiMe 2 [( CH ₂ ) ₃ CN]) [10.01], Tris (pentafluorophenyl) (pentafluorophenylcarbonyloxy) silane ((C ₆ F ₅ CO ₂ ) Si (C ₆ F ₅ ) ₃ ) [10.01] , trichloro (trifluoromethyl carbonyloxy) silane _{((CF 3 CO 2) SiCl} 3) [10.03], dimethylphenyl (pentafluorophenyl carbonyloxy) silane _{((C 6 F 5 CO 2} ) SiMe 2 Ph) [ 10.10], trimethyl (pentafluorophenylcarbonyloxy) silane ((C ₆ F ₅ CO ₂ ) SiMe ₃ ) [10.10], trimethoxy (pentafluorophenyl carboyloxy) silane ((C ₆ F ₅ CO ₂₎ ) Si (OMe) ₃ ) [10.13], Methylbis (pentafluorophenyl) (pentafluorophenylcarbonyloxy) silane ((C ₆ F ₅ CO ₂ ) SiMe (C ₆ F ₅ ) ₂ ) [10.14] , Trimethyl (nitromethylcarbonyloxy) silane ([CH ₂ (NO ₂ ) CO ₂ ] SiMe ₃ ) [10.29], trimethyl (2,3,5,6-tetrafluorophenylcarbonyloxy) silane ((2,2) 3, 5, 6-C ₆ F ₄ HCO ₂ ) SiMe ₃ ) [10.34], trimethyl (trifluoromethylsulfonylmethylcarbonyloxy) silane ((CF ₃ SO ₂ CH ₂ CO ₂ ) SiMe ₃ ) [10. 36], Trichloro (propionyloxy) silane (( _{EtCO 2} ) SiCl ₃ ) [10.52], Trichloro (methoxymethylcarbonyloxy) silane ((MeOCH ₂ CO ₂ ) SiCl ₃ [10.70], Trimethoxy (trichloromethyl) Carbonyloxy) Silane ((CCl ₃ CO ₂ ) Si (O) Me) ₃ ) [10.78], trichloro (2-propylcarbonyloxy) silane ((2-PrCO ₂ ) SiCl ₃ ) [10.95], diacetoxydifluorosilane ((MeCO ₂ ) ₂ SiF ₂ ) [11 .07], methyl diphenyl (pentafluorophenyl carbonyloxy) silane _{((C 6 F 5 CO 2} ) SiMePh 2) [11.23], acetoxymethyl dichloromethylsilane _{((MeCO 2) SiCl 2 Me} ) [11.31] , Trimethyl (2,4,6-trifluorophenylcarbonyloxy) silane ((2,4,6-C ₆ F ₃ H ₂ CO ₂ ) SiMe ₃ ) [11.44], trimethyl (6-nitrotetrafluorophenyl) Carbonyloxy) silane ([6- (O ₂ N) C ₆ F ₄ CO ₂ ] SiMe ₃ ) [11.64], trimethyl (2,6-difluorophenylcarbonyloxy) silane ((2,6-C ₆ F) ₂ H ₃ CO ₂ ) SiMe ₃ ) [11.66], tetraacetoxysilane ((MeCO ₂ ) ₄ Si) [11.77], trimethyl (methylsulfonylmethylcarbonyloxy) silane ((MeSO ₂ CH ₂ CO ₂ )) SiMe ₃ ) [11.88], trimethyl (phenylsulfonylmethylcarbonyloxy) silane ((PhSO ₂ CH ₂ CO ₂ ) SiMe ₃ ) [11.94], trichloro ( _{formyloxy) silane ((HCO 2} ) SiCl ₃ ) [12.01], acetoxydichloromethylsilane ((MeCO ₂ ) SiCl ₂ Me) [12.04], trimethyl (cyanomethylcarbonyloxy) silane (NCCH ₂ CO ₂ ) SiMe ₃ ) [12.16], (tert -Butylcarbonyloxy) trichlorosilane ((tert-BuCO ₂ ) SiCl ₃ ) [12.29], ethoxydimethyl (trichloroacetyloxy) silane ((CCl ₃ CO ₂ ) SiMe ₂ (OEt)) [12.38], Trimethyl (dichloroacetoxy) silane ((CCl ₂ HCO ₂ ) SiMe ₃ ) [12.54], trimethyl (chlorodifluoroacetoxy) silane ((CClF ₂ CO ₂ ) SiMe ₃ ) [12.83], trimethyl (heptafluoropropyl) Carbonyloxy) silane ((CF) ₃ CF ₂ CF ₂ CO ₂ ) SiMe ₃ ) [12.84], trimethyl (tetrafluoro-2-pyridylcarbonyloxy) silane ((2-C ₅ F ₄ NCO ₂ ) SiMe ₃ ) [13.1
8], trimethyl (pentafluoroethylcarbonyloxy) silane ((CF ₃ CF ₂ CO ₂ ) SiMe ₃ ) [13.19], trichloro (4-pyridylcarbonyloxy) silane ((4-PyCO ₂ ) SiCl ₃ ) [ 13.22],
Trimethyl (nonafluorobutylcarbonyloxy) silane ((CF ₃ CF ₂ CF ₂ CF ₂ CO ₂ ) SiMe ₃ ) [13.22], dichlorobis (formyloxy) silane ((HCO ₂ ) SiCl ₂ ) [13.33] , Trichloro (vinylcarbonyloxy) silane ((CH ₂ = CHCO ₂ ) SiCl ₃ ) [13.40], trimethyl (trifluoroacetoxy) silane ((CF ₃ CO ₂ ) SiMe ₃ ) [13.56], trichloro ( Benzoyloxy) silane ((PhCO ₂ ) SiCl ₃ ) [13.84], trimethyl (2-nitrophenylcarbonyloxy) silane ([2- (O ₂ N) C ₆ H ₄ CO ₂ ] SiMe ₃ ) [13. 86], Trichloro (2-pyridylcarbonyloxy) silane ((2-PyCO ₂ ) SiCl ₃ ) [13.93], trimethyl (pentafluoro-2-propenylcarbonyloxy) silane ((CF ₂ = CFCF ₂ CO ₂ )) SiMe ₃ ) [14.13], dichloro (formyloxy) silane ((HCO ₂ ) SiHCl ₂ ) [14.30], dichloro ( _{formyloxy) methylsilane ((HCO 2} ) SiCl ₂ Me) [14.55], bis (benzoyloxy) dichlorosilane _{((PhCO 2) 2 SiCl 2} ) [14.97], ( acetoxy) chlorodimethylsilane _{((MeCO 2) SiClMe 2)} [15.10], acetoxymethyl difluoromethyl silane ((Meco ₂ ) SiF ₂ Me) [15.11], (benzoyloxy) trifluorosilane ((PhCO ₂ ) SiF ₃ ) [15.21], trimethyl (2,3,4,5-tetrafluorophenylcarbonyloxy) silane ( _{(2,3,4,5-C 6 F 4 HCO} 2) SiMe 3) [15.63], ( chloro acetoxymethyl) trimethylsilane _{((CClH 2 CO 2) SiMe} 3) [16.07], ( benzoyloxy ) Dichloromethylsilane ((PhCO ₂ ) SiCl ₂ Me) [16.79], (2-fluorophenylcarbonyloxy) trimethylsilane ((2-C ₆ FH ₄ CO ₂ ) SiMe ₃ ) [16.84], ( 2,4-Difluorophenylcarbonyloxy) trimethylsilane ((2,4-C ₆ F) ₂ H ₃ CO ₂ ) SiMe ₃ ) [16.88], ((2,6-dichloro-4-pyridylcarbonyloxy) trimethylsilane ([4- (2,6-C ₅ Cl ₂ H ₃ N) CO ₂ ] SiMe ₃ ) [17.03], chloro ( _{formyloxy) dimethylsilane ((HCO 2} ) SiClMe ₂ ) [17.19], (benzoyloxy) dichlorophenylsilane ((PhCO ₂ ) SiCl ₂ Ph) [17.40] ], Acetoxytrimethylsilane ((MeCO ₂ ) SiMe ₃ ) [18.12], (4-chlorophenylcarbonyloxy) trimethylsilane ((4-ClC ₆ H ₄ CO2) SiMe ₃ ) [18.17], (benzylcarbonyl) Oxy) Trimethylsilane ((PhCH ₂ CO ₂ ) SiMe ₃ ) [18.48], (2,6-dichlorophenylcarbonyloxy) Trimethylsilane ((2,6-Cl ₂ C ₆ H ₃ CO ₂ ) SiMe ₃ ) [ 18.50], trimethyl (pentachlorophenylcarbonyloxy) silane (C ₆ Cl ₅ CO ₂ ) SiMe ₃ ) [18.89], (formyloxy) trimethylsilane ((HCO ₂ ) SiMe ₃ ) [19.29], etc. Can be mentioned.

When the asyloxysilane is a compound having two silicon atoms, specific examples of the compound having ΔU of 20 kcal / mol or less are (the values in square brackets indicate the calculated value of ΔU (kcal / mol)). If there is an asyloxy group, the calculated value when one asyloxy group causes a decarbonation reaction is shown.), 1,1,2,2-tetramethyl-1,2-bis (pentafluorophenylcarbonyloxy) ) Disilane ((C ₆ F ₅ CO ₂ ) Me ₂ SiSiMe ₂ (OCOC ₆ F ₅ )) [7.01], 1,1,2,2-tetramethyl-1- (pentafluorophenyl) -2- ( Pentafluorophenylcarbonyloxy) disilane ((C ₆ F ₅ ) Me _{2 SiSiMe 2} (OCOC ₆ F ₅ )) [9.82], 2,3,5,6-tetrafluoro-1,4-bis (trimethylsiloxy) Carbonyl) benzene (1,4-C ₆ F ₄ (CO ₂ SiMe ₃ ) ₂ ) [9.94], 1,1,3,3-tetramethyl-1,3-bis (pentafluorophenylcarbonyloxy) di Siloxane ((C ₆ F ₅ CO ₂ ) Me ₂ SiOSiMe ₂ (OCOC ₆ F ₅ )) [10.16], 2,4,5,6-tetrafluoro-1,3-bis (trimethylsiloxycarbonyl) benzene ( 1,3-C ₆ F ₄ (CO ₂ SiMe ₃ ) ₂ ) [10.52], 2,3,5,6-tetrafluoro-1-trimethylsilyl-4- (trimethylsiloxycarbonyl) benzene (1-Me ₃₎ Si-4- (Me ₃ SiOCO) C ₆ F ₄ ) [10.69], 1,1,3,3-tetramethyl-1- (pentafluorophenyl) -3- (pentafluorophenylcarbonyloxy) disiloxane ((C ₆ F ₅ ) Me ₂ SiOSiMe ₂ (OCOC ₆ F ₅ )) [11.66], 2,4,5,6-tetrafluoro-1-trimethylsilyl-3- (trimethylsiloxycarbonyl) benzene (1- Me ₃ Si-3- (Me ₃ SiOCO) C ₆ F ₄ ) [11.73] and the like can be mentioned.

According to the production method according to the present embodiment, a carbosilane having a Si—C bond is obtained by carrying out a decarboxylation reaction in the presence of a specific base using asyloxysilane having at least one asyloxy group as a raw material. Can be manufactured.

The decarboxylation reaction step in this embodiment is a step of producing carbosilane having a Si—C bond by decarboxylation from the asyloxy group of asyloxysilane. The reaction when the asyloxysilane is monoacyloxysilane can be represented by, for example, Scheme 1 below.

When a compound having a plurality of asyloxy groups is used as the asyloxysilane, unreacted asyloxy groups remain in the carbosilane produced by the reaction of one asyloxy group, so that they further react. Carbosilane can be given.
For example, as shown in Scheme 2 below, in the reaction of asyloxysilane having two asyloxy groups (in Scheme 2, monosilane, disilane, disiloxane, and disyloxycarbonyl compounds are exemplified as asyloxysilane). , Carbosilane ((A), (C), (E), (G)) produced by the reaction of one asyloxy group or carbosilane ((B), (D)) produced by the reaction of two asyloxy groups. (F), (H)) can be produced.

That is, in the decarboxylation reaction step of the present embodiment, when a compound having a plurality of asyloxy groups is used as a raw material, carbosilane formed by reacting one or more asyloxy groups can be produced. Therefore, the decarboxylation reaction step may be a step of obtaining one kind of carbosilane alone, or a step of obtaining a mixture of a plurality of kinds of carbosilanes.

In addition, the production method according to the present embodiment may include a pre-step for forming asyloxysilane. The pre-step may be, for example, any of the following steps (4) to (6). In this embodiment, carbosilane can also be produced by continuously performing the previous step and the subsequent decarboxylation reaction step.
(4) Asiloxysilane having a Si-OCOR bond is added to an alkoxysilane having a Si-OR'bond (R'indicates a hydrocarbon group having 1 to 3 carbon atoms) to (RCO) ₂ O (R). Is synonymous with the above.) Is a step of reacting and forming a carboxylic acid anhydride represented by).
(5) the Si-OCOR acyloxy having binding, Si-R "bond (R" is. Showing the allyl group) in allylsilane having, _RCO 2 H (R has the same meaning as defined above.) In A step of reacting and forming the represented carboxylic acid.
(6) Si-OCOR acyloxy having binding, the chlorosilane having of Si-Cl bond, _RCO 2 H (R has the same meaning as defined above.) To form by reacting a carboxylic acid represented by ..

Examples of the hydrocarbon group having 1 to 3 carbon atoms represented by R'include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a vinyl group and the like.

For example, when the asyloxysilane is monoacyloxysilane, monoacyloxysilane can be formed from monoalkoxysilane, monoallylsilane, or monochlorosilane in the previous step, as shown in Scheme 3 below. Then, in the decarboxylation reaction step, carbosilane can be produced by decarboxylating the produced monoacyloxysilane.

The reaction in these previous steps does not necessarily require a reaction accelerator such as a catalyst, but the reaction can also be carried out using various reaction accelerators.
For example, in (a) the reaction between monoalkoxysilane and carboxylic acid anhydride or (b) the reaction between monoallylsilane and carboxylic acid, an acid catalyst such as an inorganic or organic solid acid or Lewis acid can be used.
Further, in (c) the reaction between chlorosilane and carboxylic acid, an organic or inorganic base can be used.

The prior steps of (4) to (6) can be performed according to conventionally known methods as shown in the following documents i to iii, respectively.
Reference i International Publication No. 2016/143835 Reference ii Tetrahedron Letter. , 892-895 (1983)
References iii Gmelin Handbook: Si: MVol. C, 69, 190-194
More specifically, a proton-type zeolite, a cation exchange resin, or the like can be used as the inorganic or organic solid acid in the previous steps of (4) and (5), and perchloric acid is used as the Lewis acid. Compounds such as iron (III), iron (III) chloride, and ruthenium chloride (III) (which may contain water of crystallization) can be used.
Further, as the organic or inorganic base in the previous step (6), triethylamine, N-methylpyrrolidine, pyridine, potassium carbonate, sodium carbonate and the like can be used.
The specific reaction temperature and reaction time in the previous steps (4) to (6) are about 0 to 200 ° C. and about 5 minutes to 6 hours.

In the pre-step of forming asyloxysilane, it is not necessary to isolate and purify asyloxysilane, and the reaction can be carried out in a one-pot step in combination with the decarboxylation reaction step. In this embodiment, it is also possible to efficiently produce carbosilane from alkoxysilane or the like by continuously performing the pre-process for producing asyloxysilane and the decarboxylation reaction step for decarboxylation. This is a feature of the manufacturing method.

In the decarboxylation reaction step from asyloxysilane, the structure of R may be isomerized depending on the type of the hydrocarbon group R of the asyloxy group (OCOR) or the type of the base used.
For example, when R is a phenyl group having 1 to 4 substituents such as a halogen atom, an isomer having a changed position on the phenyl group such as a halogen atom may be generated in the decarbonation reaction step.
That is, in the production method according to the present embodiment, when a carbosilane having a Si—R bond is produced from an isomeroxysilane having a Si—OCOR bond by a decarbonation reaction step, R has 1 substituent such as a halogen atom. In the case of a phenyl group having up to 4 groups, a mixture of structural isomers having different positions such as halogen atoms may be produced. However, the carbosilane obtained by the production method according to the present embodiment contains a mixture of these structural isomers. Is also included.

In the decarboxylation reaction step in this embodiment, a base catalyst is used to promote the reaction.
Examples of the base catalyst include compounds in which the pKa of the conjugate acid is in the range of 8 to 50. The pKa range of the compound is preferably 9 to 45, more preferably 10 to 42.

The pKa of the conjugate acid is basically based on the value measured in water, but the value measured in an organic solvent such as acetonitrile can also be used.
Examples of the compound having a pKa of the conjugate acid in the range of 8 to 50 include those shown in various conventionally known documents. Specific examples of these documents include the following references (A) to (E).
(A) Chemistry Handbook Basics II (Revised 4th Edition), II-317, Maruzen, 1993
(B) J. Am. Che. Soc. , 79,5441 (1957)
(C) Euro. J. Org. Chem. , 4852 (2006)
(D) J. Org. Chem. , 70, 1019 (2005)
(E) Product description of phosphazene base on Merck &Co.'s website (https://www.sigmaaldrich.com/chemistry/chemical-synthesis/technology-spotlighes/phosphazenes.html)

Therefore, specific examples of compounds in which the pKa of the conjugate acid is in the range of 8 to 50 (in parentheses, the numerical value of the pKa of the conjugate acid in water and the symbol of the above document are shown. In addition, * is in acetonitrile. The pKa value of the conjugate acid is shown.), Triethylamine (10.72, A), diethylamine (10.98, B), dipropylamine (11.00, B), dibutylamine (11.25, B), Diisopropylamine (11.05), diisobutylamine (10.50), tert-butylcyclohexylamine (11.23, B), benzylmethylamine (9.58, B), benzylethylamine (9.68, B), Di-sec-butylamine (11.01, B), dimethylethylamine (9.99, B), methyldiethylamine (10.29, B), dimethylpropylamine (9.99, B), dimethylbutylamine (10.02) , B), dimethylisobutylamine (9.91, B), dimethylisopropylamine (10.30, B), dimethyl-sec-butylamine (10.40, B), dimethyl-tert-butylamine (10.52, B) ), Tripropylamine (10.65, B), Tributylamine (10.89, B), benzyldimethylamine (8.93, B), benzyldiethylamine (9.48, B), N-ethylpiperidine (10) .40, B), N-methylpiperidin (10.08, B), N-methyltrimethyleneimine (10.40, B), N-methylpyrrolidin (10.46, B), 1-azabicyclo [2. 2.2] Octane (ABCO) (10.76, C), 1,4-diazabicyclo [2.2.2] Octane (DABCO) (8.72, C), N, N, N', N'- Tetramethylethylenediamine (TMEDA) (9.42, C), N, N, N', N'-tetramethyl-1,3-propanediamine (TMPDA) (9.81, C), 1,8-diazabicyclo [ 5.4.0] -7-Undecene (DBU) (24.34 *, D), 7-Methyl-1,5,7-Triazabicyclo [4.4.0] Deca-5-ene (MTBD) (25.49 *, D), 4-dimethylaminopyridine (DMAP) (17.95 *, D), tert-butylimino-tri (pyrrolidino) phosphorane (BTPP) (28.4 *, E), tert-butyl Imminotris (dimethylamino) phosphorane (P1-t-Bu) (26.9 *, E), 2-ter t-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorin (BEMP) (27.6 *, E), tert-octyliminotris (dimethylamino) phosphorane (P1-t-) oct) (26.5 *, E) , 1- ethyl -2,2,4,4,4- pentakis (dimethylamino) -2λ ^5, 4λ ⁵ - Katenaji (phosphazene) (P2-Et) (32.9 *, E), 1-tert-butyl-2,2,4,4,4-pentakis (dimethylamino) -2λ ⁵ , 4λ ⁵ -catenadi (phosphazene) (P2-t-Bu) (33.5 *, E), 1-tert-butyl-4,4,4-tris (dimethylamino) -2,2-bis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] -2λ ^5, 4λ ⁵ - Katenaji (phosphazene) (P4 -T-Bu) (41.9 *, E), 1-tert-octyl-4,4,4-tris (dimethylamino) -2,2-bis [tris (dimethylamino) phosphoranilideneamino] -2λ ⁵ , 4λ ⁵ -catenate (phosphazene) (P4-t-Oct) (42.7 *, E) and the like can be mentioned.

Further, as the base catalyst used in the production method according to the present embodiment, a base selected from a phosphazene compound, a bicyclic amine compound, a guanidine compound, or an amidine compound is preferably used.
Specific examples thereof include the above-mentioned compounds having a pKa of a conjugate acid in the range of 8 to 50, or other compounds. For example, the phosphazene compound is P2-t-Bu, P4-t-Bu, BTPP, BEMP, etc., the bicyclic amine compound is ABCO, DABCO, etc., the guanidine compound is MTBD, etc., and the amidine compound is Examples include DBU and DBN.
In terms of catalytic activity, among the above compounds, a phosphazene compound, a bicyclic amine compound, or a guanidine compound is more preferable, and a phosphazene compound or a bicyclic amine compound is further preferable.

Further, as the base catalyst used in the production method according to the present embodiment, a compound derived from a compound having a pKa of a conjugated acid in the range of 8 to 50, a phosphazene compound, a bicyclic amine compound, a guanidine compound, or an amidin compound. Examples thereof include organic polymer-based solid compounds and inorganic solid compounds having the above as a substituent or a constituent unit. These solid compounds may be produced according to a known production method, or may be various commercially available products.
Since these solid compounds are insoluble in general solvents, they can be easily separated and recovered from the reaction solution by a method such as centrifugation or filtration.
Specific examples of the above solid compound include polystyrene gels (of styrene and divinylbenzene) having a group derived from trimethylamine, diethylmethylamine, disopropylmethylamine, methylpiperidin, DBU, MTBD, BEMP, P2-t-Bu and the like. Copolymers), polyacrylic acid derivatives such as polyacrylic acid ester and polyacrylic acid amide; silica gel; zeolite; and the like.

Specific examples of commercially available organic polymer-based solid compounds include those having a group derived from trimethylamine, diethylmethylamine, diisopropylmethylamine, DBU, MTBD, BEMP, P2-t-Bu, and the like. , Product No. 39205, Product No. 31866, Product No. 538736, Product No. 595128, Product No. 358754, Product No. 536490, Product No. 71477, etc., which are commercially available from Merck.

In the production method according to the present embodiment, among the organic polymer-based solid compounds, those having a group derived from BEMP, P2-t-Bu, trimethylamine, diisopropylmethylamine, DBU, MTBD and the like are preferable, and BEMP, Those having a group derived from a phosphazene compound such as P2-t-Bu are more preferable.

Further, as the inorganic compound such as silica and alumina, an inorganic solid compound carrying a compound having a pKa of a conjugate acid in the range of 8 to 50, a phosphazene compound, a bicyclic amine compound, a guanidine compound, or an amidine compound is used. You can also do it.
Further, a plurality of organic polymer-based solid compounds and inorganic solid compounds can be used in combination, and these solid compounds can also be used in combination with the basic compound.

The amount of the base catalyst with respect to the raw material can be arbitrarily determined, but the molar ratio or weight ratio of the raw material to the acyloxysilane is usually about 0.001 to 50, preferably about 0.001 to 20, more preferably about 0.001 to 20. It is about 0.001 to 10.

The decarboxylation reaction in this embodiment can be carried out in a liquid phase or a gas phase state depending on the reaction temperature or reaction pressure. Further, as the form of the reaction device, various conventionally known forms such as a batch type and a flow type can be used.
The reaction temperature is usually 10 ° C. or higher, preferably 10 ° C. to 600 ° C., more preferably 10 ° C. to 400 ° C., still more preferably 50 ° C. to 300 ° C.
Further, the reaction pressure is usually 0.01 to 30 atm, preferably 0.01 to 10 atm, and more preferably 0.01 to 5 atm.
The reaction time depends on the amount of the raw material, the amount of the catalyst, the reaction temperature, the form of the reaction apparatus, etc., but in consideration of productivity and efficiency, it is usually 1 minute to 24 hours, preferably 1 minute to 20 hours. It is preferably about 1 minute to 16 hours.

When the reaction is carried out in a liquid phase system, it can be carried out with or without a solvent, but when a solvent is used, hydrocarbons such as decalin (decahydronaphthalene) and decane, chlorobenzene, 1,2-dichlorobenzene, 1, Halogenized hydrocarbons such as 3-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene; ethers such as anisole, tert-butylmethyl ether, dibutyl ether, tetrahydrofuran; acetonitrile, benzonitrile, A nitrile such as adiponitrile; an amide such as dimethylacetamide or methylacetamide; various solvents other than those that react with a raw material or a catalyst; and the like can be used. A base catalyst (eg, NMP) that exists as a liquid at the reaction temperature may be used as the solvent. Further, two or more kinds of solvents can be mixed and used.
When the reaction product is analyzed by nuclear magnetic resonance spectrum analysis, a deuterated compound such as deuterated acetonitrile, deuterated chloroform, deuterated chloroform, deuterated formamide, or deuterated tetrahydrofuran can be used as the reaction solvent.
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 decarboxylation reaction in this embodiment can also be carried out under microwave irradiation. In this reaction system, the dielectric loss coefficient of the raw materials asyloxysilane, silanol, etc. is relatively large, and microwaves are efficiently absorbed. Therefore, the raw materials, catalysts, etc. are activated under microwave irradiation, and the reaction is more efficient. Can be done.

In the microwave irradiation reaction, various commercially available devices equipped with a contact type or non-contact type temperature sensor can be used. Further, the output of microwave irradiation, the type of cavity (multi-mode, single mode), the form of irradiation (continuous, intermittent) and the like can be arbitrarily determined according to the scale and type of reaction. The frequency of the microwave is usually 0.3 GHz to 30 GHz. Among them, the IMS frequency band allocated for use in the industrial field, the scientific field, or the medical field is preferable, and among them, the 2.45 GHz band, the 5.8 GHz band, and the like are more preferable.

Further, in the microwave irradiation reaction, in order to heat the reaction system more efficiently, a heating material (susceptor) that absorbs microwaves and generates heat can be added to the reaction system. As the type of heating material, various conventionally known materials such as activated carbon, graphite, silicon carbide, and titanium carbide can be used. It is also possible to use a molding catalyst in which the above-mentioned catalyst and the powder of the heating material are mixed and fired using an appropriate binder such as sepiolite or formite.

The decarbonation reaction in the present embodiment also proceeds in a closed reactor, but the reactor is set to an open system or a reduced pressure system _{to continuously remove the co-product CO 2} or the reaction product from the reaction system. Thereby, the reaction can be made to proceed more efficiently.

When the above-mentioned solid compound is used as a base catalyst in the production method of the present embodiment, the separation and recovery of the base catalyst after the decarbonation reaction step can be easily performed by a method such as filtration or centrifugation.
Purification of the produced carbosilane can also be easily achieved by means commonly used in organic chemistry such as distillation, recrystallization and column chromatography.

Carbosilane produced by the production method according to this embodiment is used as a reagent for precision synthesis, an intermediate, etc. for producing various functional chemicals such as pharmaceuticals, agricultural chemicals, optical materials, electronic materials, or various functional materials. can.
When the asyloxy group remains in the carbosilane, the asyloxy group has high reactivity and can be used as a surface treatment agent for solid materials and the like.
Since the surface treatment using carbosilane having an acyloxy group has high reaction efficiency with the solid surface, it is possible to quickly perform the surface treatment on a solid material such as glass under mild conditions, and the carbosilane to be used. Depending on the type of solid material, the hydrophilicity or hydrophobicity of the surface of the solid material can be easily controlled.
When carbosilane having an asyloxy group is used as a surface treatment agent, it can be diluted with an organic solvent that does not react with carbosilane such as toluene, hexane, and acetone, if necessary.
As a method for surface treatment of a solid material, various conventionally known methods such as a dip method (immersion method), a casting method, a spin coating method, and a spray coating method can be used.

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 spectrum analysis (hereinafter sometimes referred to as NMR): Bruker's AVANCE III HD 600 MHz (with cryoprobe attached)
-Gas chromatograph analysis (hereinafter sometimes referred to as GC): GC-2014 manufactured by Shimadzu Corporation
-Gas chromatograph mass spectrometry (hereinafter, may be referred to as GC-MS): GCMS-QP2010Plus manufactured by Shimadzu Corporation.

(Example 1)
[pre-process]
To prepare asyloxysilane, a mixture of 0.8 mmol of pentafluorobenzoic acid (C ₆ F ₅ CO ₂ H) and 0.8 mL of anisole was stirred in a reaction vessel with chlorotrimethylsilane (Me ₃ SiCl). 0.8 mmol and 1.6 mmol of triethylamine were sequentially added at room temperature and stirred at room temperature for about 30 minutes. The salt was separated by centrifugation, and the supernatant and the washing solution in which the salt was washed with 0.8 mL of Anisol were combined and analyzed by NMR (Nuclear Magnetic Resonance Spectrometer) and GC-MS (Gas Chromatograph Mass Spectrometer). trimethyl (pentafluorophenyl carbonyloxy) silane siloxysilane _{((C 6 F 5 CO 2} ) SiMe 3) is 0.72 mmol (90% yield) was found to generated (see Table 1-1).
[Decarboxylation reaction process]
To the anisole solution of asyloxysilane (a solution of about 0.65 mL of anisole containing about 0.3 mmol of asyloxysilane) obtained in the previous step, 0.015 mmol of P2-t-Bu was added and heated at 100 ° C. for 20 minutes. bottom. When the reaction solution was analyzed by NMR and GC-MS, the conversion of acyloxysilane is 92%, trimethyl carbosilane (pentafluorophenyl) silane _{((C 6 F 5) SiMe} 3) is approximately 0.265mmol It was found that (yield 96% with respect to converted asyloxysilane) was produced (see Table 2-1).
Table 3-1 shows the measurement results of NMR and GC-MS of asyloxysilane obtained in the previous step and carbosilane obtained in the decarboxylation reaction step.

The notes in Table 1-1 and Table 1-2 are shown below.
1) Types of raw material silane
a: Alkoxysilane
b: Allylsilane
c: Chlorosilane
2) ClSiMe ₃ : Chlorotrimethylsilane
(EtO) SiMe ₃ : ethoxytrimethylsilane
(CH ₂ = CHCH ₂ ) SiMe ₃ : Allyltrimethylsilane
ClSiMe ₂ Ph: Chlorodimethylphenylsilane
ClSiMe ₂ (CH = CH ₂ ): Chlorodimethylvinylsilane
ClSiMe ₂ [(CH ₂ ) ₃ CN]: Chloro (3-cyanopropyl) dimethylsilane
(EtO) ₂ SiMe ₂ : Diethoxydimethylsilane
Cl ₂ SiMe ₂ : Dichlorodimethylsilane
ClSiMe ₂ SiMe ₂ Cl: 1,2-dichloro-1,1,2,2-tetramethyldisilane
ClSiMe ₂ OSiMe ₂ Cl: 1,3-dichloro-1,1,3,3-tetramethyldisiloxane.
3) C ₆ F ₅ CO ₂ H: Pentafluorobenzoic acid
(C ₆ F ₅ CO) ₂ O: Pentafluorobenzoic anhydride
2,3,5,6-F ₄ C ₆ HCO ₂ H: 2,3,5,6-tetrafluorobenzoic acid
2,4,6-F ₃ C ₆ H ₂ CO ₂ H: 2,4,6-trifluorobenzoic acid
2,6-F ₂ C ₆ H ₃ CO ₂ H: 2,6-difluorobenzoic acid
2,6-Cl ₂ C ₆ H ₃ CO ₂ H: 2,6-dichlorobenzoic acid
2- (O ₂ N) C ₆ F ₄ CO ₂ H: 3,4,5,6-tetrafluoro-2-nitrobenzoic acid
2- (O ₂ N) C ₆ H ₄ CO ₂ H: 2-nitrobenzoic acid
CF ₃ CF ₂ CO ₂ H: Pentafluoropropionic acid
(CCl ₃ CO) ₂ O: Trichloroacetic acid anhydride
1,3-C ₆ F ₄ (CO ₂ H) ₂ : Tetrafluoroisophthalic acid
1,4-C ₆ F ₄ (CO ₂ H) ₂ : Tetrafluoroterephthalic acid
(PhC≡C) CO ₂ H: 3-Phenylpropiolic acid
4) Et ₃ N: Triethylamine
NMP: N-methylpyrrolidine
_{Fe (ClO 4) 3 · 6H} 2 O: perchlorate (III) 6 hydrate
CBV780: USY-based zeolite CBV780 (manufactured by Zeolisto)
5) PhOMe: Anisole
DCB: When chlorosilane of b is used as the raw material silane of o-dichlorobenzene and Et ₃ N is used as the reaction accelerator, the salt produced by the reaction is separated by centrifugation, and the salt is washed with a solvent. The washing solution was combined with the reaction solution (supernatant solution) to prepare a solution of asyloxysilane. The numerical value in square brackets in the solvent amount is the total solvent amount of the cleaning liquid.
6) (C ₆ F ₅ CO ₂ ) SiMe ₃ : Trimethyl (pentafluorophenylcarbonyloxy) silane
(2,3,5,6-F ₄ C ₆ HCO ₂ ) SiMe ₃ : Trimethyl (2,3,5,6-tetrafluorophenylcarbonyloxy) silane
(2,4,6-F ₃ C ₆ H ₂ CO ₂ ) SiMe ₃ : Trimethyl (2,4,6-trifluorophenylcarbonyloxy) silane
(2,6-F ₂ C ₆ H ₃ CO ₂ ) SiMe ₃ : Trimethyl (2,6-difluorophenylcarbonyloxy) silane
(2,6-Cl ₂ C ₆ H ₃ CO ₂ ) SiMe ₃ : Trimethyl (2,6-dichlorophenylcarbonyloxy) silane
[2- (O ₂ N) C ₆ F ₄ CO ₂ ] SiMe ₃ : Trimethyl (3,4,5,6-tetrafluoro-2-nitrophenylcarbonyloxy) silane
[2- (O ₂ N) C ₆ H ₄ CO ₂ ] SiMe ₃ : Trimethyl (2-nitrophenylcarbonyloxy) silane
(C ₆ F ₅ CO ₂ ) SiMe ₂ Ph: Dimethylphenyl (pentafluorophenylcarbonyloxy) silane
(C ₆ F ₅ CO ₂ ) SiMe ₂ (CH = CH ₂ ): Dimethyl (pentafluorophenylcarbonyloxy) (vinyl) silane
(C ₆ F ₅ CO ₂ ) SiMe ₂ [(CH ₂ ) ₃ CN]: (3-cyanopropyl) dimethyl (pentafluorophenylcarbonyloxy) silane
(CF ₃ CF ₂ CO ₂ ) SiMe ₃ : Trimethyl (pentafluoropropionyloxy) silane
(CCl ₃ CO ₂ ) SiMe ₃ : Trimethyl (trichloroacetyloxy) silane
(CCl ₃ CO ₂ ) SiMe ₂ (OEt): (ethoxy) dimethyl (trichloroacetyloxy) silane
1,3-C ₆ F ₄ (CO ₂ SiMe ₃ ) ₂ : 2,4,5,6-tetrafluoro-1,3-bis (trimethylsiloxycarbonyl) benzene
1,4-C ₆ F ₄ (CO ₂ SiMe ₃ ) ₂ : 2,3,5,6-tetrafluoro-1,4-bis (trimethylsiloxycarbonyl) benzene
(C ₆ F ₅ CO ₂ ) ₂ SiMe ₂ : Dimethylbis (pentafluorophenylcarbonyloxy) silane
(C ₆ F ₅ CO ₂ ) SiMe ₂ SiMe ₂ (OCOC ₆ F ₅ ): 1,1,2,2-tetramethyl-1,2-bis (pentafluorophenylcarbonyloxy) disilane
(C ₆ F ₅ CO ₂ ) SiMe ₂ OSiMe ₂ (OCOC ₆ F ₅ ): 1,1,3,3-tetramethyl-1,3-bis (pentafluorophenylcarbonyloxy) disiloxane
(PhC≡C) CO ₂ SiMe ₃ : Trimethyl (phenylethynylcarbonyloxy) silane
7) Yield by NMR (yield of asyloxysilane product with respect to carboxylic acid derivative or raw material silane)

The notes in Tables 2-1 to 2-5 are shown below.
1) (C ₆ F ₅ CO ₂ ) SiMe ₃ : trimethyl (pentafluorophenylcarbonyloxy) silane, ΔU
= 10.10 kcal / mol
(2,3,5,6-F ₄ C ₆ HCO ₂ ) SiMe ₃ : Trimethyl (2,3,5,6-tetrafluorophenylcarbonyloxy) silane, ΔU = 10.34 kcal / mol
(2,4,6-F ₃ C ₆ H ₂ CO ₂ ) SiMe ₃ : Trimethyl (2,4,6-trifluorophenylcarbonyloxy) silane, ΔU = 11.44 kcal / mol
(2,6-F ₂ C ₆ H ₃ CO ₂ ) SiMe ₃ : trimethyl (2,6-difluorophenylcarbonyloxy) silane, ΔU = 11.66 kcal / mol
(2,6-Cl ₂ C ₆ H ₃ CO ₂ ) SiMe ₃ : trimethyl (2,6-dichlorophenylcarbonyloxy) silane, ΔU = 18.50 kcal / mol
[2- (O ₂ N) C ₆ F ₄ CO ₂ ] SiMe ₃ : Trimethyl (3,4,5,6-tetrafluoro-2-nitrophenylcarbonyloxy) silane, ΔU = 11.64 kcal / mol
[2- (O ₂ N) C ₆ H ₄ CO ₂ ] SiMe ₃ : trimethyl (2-nitrophenylcarbonyloxy) silane, ΔU = 13.86 kcal / mol
(C ₆ F ₅ CO ₂ ) SiMe ₂ Ph: Dimethylphenyl (pentafluorophenylcarbonyloxy) silane, ΔU = 10.10 kcal / mol
(C ₆ F ₅ CO ₂ ) SiMe ₂ (CH = CH ₂ ): Dimethyl (pentafluorophenylcarbonyloxy) (vinyl) silane, ΔU = 8.99 kcal / mol
(C ₆ F ₅ CO ₂ ) SiMe ₂ [(CH ₂ ) ₃ CN]: (3-cyanopropyl) dimethyl (pentafluorophenylcarbonyloxy) silane, ΔU = 10.01 kcal / mol
(CF ₃ CO ₂ ) SiMe ₃ : trimethyl (trifluoroacetyloxy) silane, ΔU = 13.56 kcal / mol
(CF ₃ CF ₂ CO ₂ ) SiMe ₃ : Trimethyl (pentafluoropropionyloxy) silane, ΔU = 13.19 kcal / mol
(CCl ₃ CO ₂ ) SiMe ₃ : trimethyl (trichloroacetyloxy) silane, ΔU = 9.00 kcal / mol
(CCl ₃ CO ₂ ) SiMe ₂ (OEt): (ethoxy) dimethyl (trichloroacetyloxy) silane, ΔU = 12.38 kcal / mol
1,3-C ₆ F ₄ (CO ₂ SiMe ₃ ) ₂ : 2,4,5,6-tetrafluoro-1,3-bis (trimethylsiloxycarbonyl) benzene, ΔU = 10.52 kcal / mol (1st asyloxy) Group decarboxylation), 11.73 kcal / mol (second asiloxy group decarboxylation)
1,4-C ₆ F ₄ (CO ₂ SiMe ₃ ) ₂ : 2,3,5,6-tetrafluoro-1,4-bis (trimethylsiloxycarbonyl) benzene, ΔU = 9.94 kcal / mol (1st asyloxy) Group decarboxylation), 10.69 kcal / mol (second asiloxy group decarboxylation)
(C ₆ F ₅ CO ₂ ) ₂ SiMe ₂ : Dimethylbis (pentafluorophenylcarbonyloxy) silane, ΔU = 8.73 kcal / mol (decarboxylation of the first asyloxy group), 9.26 kcal / mol (decarboxylation of the second asyloxy group) Carbon dioxide)
(C ₆ F ₅ CO ₂ ) SiMe ₂ SiMe ₂ (OCOC ₆ F ₅ ): 1,1,2,2-tetramethyl-1,2-bis (pentafluorophenylcarbonyloxy) disilane, ΔU = 7.01 kcal / mol (1st asyloxy group decarboxylation), 9.82 kcal / mol (2nd asyloxy group decarboxylation)
(C ₆ F ₅ CO ₂ ) SiMe ₂ OSiMe ₂ (OCOC ₆ F ₅ ): 1,1,3,3-tetramethyl-1,3-bis (pentafluorophenylcarbonyloxy) disiloxane, ΔU = 10.16 kcal / mol (1st asiloxy group decarboxylation), 11.66 kcal / mol (2nd asiloxy group decarboxylation)
(PhC≡C) CO ₂ SiMe ₃ : trimethyl (phenylethynylcarbonyloxy) silane, ΔU = 6.76 kcal / mol
In Examples 1 to 29 and 36 to 61, a pre-step for producing asyloxysilane and a decarboxylation reaction step for producing carbosilane from asyloxysilane were carried out in a continuous one-pot process.
2) The numbers in square brackets are the numbers of the previous process examples in Table 1. "-" Indicates that a commercially available asyloxysilane was used.
3) The number in parentheses is the number of moles of asyloxysilane in consideration of the yield in the previous process. When a commercially available asyloxysilane is used without the previous step, the number of moles thereof.
4) P2-t-Bu: 1-tert- butyl -2,2,4,4,4- pentakis (dimethylamino) -2λ ^5, 4λ ⁵ - Katenaji (phosphazenes)
BEMP: 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorin
BTPP: tert-butylimino-tri (pyrrolidino) phosphorane
ABCO: 1-azabicyclo [2.2.2] octane
DABCO: 1,4-diazabicyclo [2.2.2] octane
NMP: N-methylpyrrolidine
P4-t-Bu: 1- tert- butyl-4,4,4-tris (dimethylamino) -2,2-bis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] -2λ ^5, 4λ ⁵ - Katenaji (phosphazenes )
TMEDA: N, N, N', N'-Tetramethylethylenediamine
TMPDA: N, N, N', N'-tetramethyl-1,3-propanediamine
BEMP-Pol: Polymer containing BEMP unit (Merck, product number 536490)
ⁱ Pr ₂ N-Pol: Diisopropylamino group-containing polymer (Merck, product number 538736)
MTBD-Pol: Polymer containing MTBD unit (Merck, product number 358754)
DBU-Pol: Polymer containing DBU unit (Merck, product number 595128)
KF: Potassium fluoride The polymer compound used was dried at 80 ° C. under reduced pressure.
5) Number of moles when the catalyst is a small molecule. If the catalyst is a polymer, the number of moles of basic units.
6) PhOMe: Anisole
DCB: o-dichlorobenzene
NC (CH ₂ ) ₄ CN: Adiponitrile
PhCN: Benzonitrile
THF: tetrahydrofuran.
7) Conversion rate of asyloxysilane by NMR.
8) (C ₆ F ₅ ) SiMe ₃ : trimethyl (pentafluorophenyl) silane
(C ₆ F ₄ H) SiMe ₃ : Trimethyl (tetrafluorophenyl)silane
(C ₆ F ₃ H ₂ ) SiMe ₃ : Trimethyl (trifluorophenyl) silane
(C ₆ F ₂ H ₃ ) SiMe ₃ : Trimethyl (difluorophenyl) silane
(C ₆ Cl ₂ H ₃ ) SiMe ₃ : Trichlorophenyl silane
[2- (O ₂ N) C ₆ F ₄ ] SiMe ₃ : Trimethyl (tetrafluoronitrophenyl) silane
[C ₆ H ₄ (NO ₂ )] SiMe ₃ : Trimethyl (nitrophenyl) silane
(C ₆ F ₅ ) SiMe ₂ Ph: Dimethylphenyl (pentafluorophenyl) silane
(C ₆ F ₅ ) SiMe ₂ (CH = CH ₂ ): Dimethyl (pentafluorophenyl) (vinyl) silane
(C ₆ F ₅ ) SiMe ₂ [(CH ₂ ) ₃ CN]: (3-cyanopropyl) dimethyl (pentafluorophenyl) silane
(CF ₃ ) SiMe ₃ : Trimethyl (trifluoromethyl) silane
(CF ₃ CF ₂ ) SiMe ₃ : Trimethyl (pentafluoroethyl) silane
(CCl ₃ ) SiMe ₃ : Trimethyl (trichloromethyl) silane
(CCl ₃ ) SiMe ₂ (OEt): (ethoxy) dimethyl (trichloromethyl) silane
1- (Me ₃ Si) -3- (Me ₃ SiOCO) C ₆ F ₄ : 2,4,5,6-tetrafluoro-1-trimethylsilyl-3-trimethylsiloxycarbonylbenzene
1,3- (Me ₃ Si) ₂ C ₆ F ₄ : 2,4,5,6-tetrafluoro-1,3-bis (trimethylsilyl) benzene
1- (Me ₃ Si) -4- (Me ₃ SiOCO) C ₆ F ₄ : 2,3,5,6-tetrafluoro-1-trimethylsilyl-4-trimethylsiloxycarbonylbenzene
1,4- (Me ₃ Si) ₂ C ₆ F ₄ : 2,3,5,6-tetrafluoro-1,4-bis (trimethylsilyl) benzene
(C ₆ F ₅ ) ₂ SiMe ₂ : Dimethylbis (pentafluorophenyl) silane
(C ₆ F ₅ ) SiMe ₂ SiMe ₂ (OCOC ₆ F ₅ ): 1,1,2,2-tetramethyl-1-pentafluorophenyl-2-pentafluorophenylcarbonyloxydisilane
(C ₆ F ₅ ) SiMe ₂ SiMe ₂ (C ₆ F ₅ ): 1,1,2,2-tetramethyl-1,2-bis (pentafluorophenyl) disilane
(C ₆ F ₅ ) SiMe ₂ OSiMe ₂ (OCOC ₆ F ₅ ): 1,1,3,3-tetramethyl-1-pentafluorophenyl-3-pentafluorophenylcarbonyloxydisiloxane
(C ₆ F ₅ ) SiMe ₂ OSiMe ₂ (C ₆ F ₅ ): 1,1,3,3-tetramethyl-1,3-bis (pentafluorophenyl) disiloxane
(PhC≡C) SiMe ₃ : Trimethyl (phenylethynyl) silane
9) Yield by NMR (yield of carbosilane product relative to converted asyloxysilane).
10) Three types of isomers ((C ₆ F ₄ H) SiMe ₃ (P1) to (P3)) with different positions of fluorine atoms on the phenyl group were generated. The yields of (P1) to (P3) are shown in parentheses in order. (C ₆ F ₄ H) SiMe ₃ (P1) is considered to be trimethyl (2,3,5,6-tetrafluorophenyl)silane.
11) Six types of isomers ((C ₆ F ₃ H ₂ ) SiMe ₃ (P1) to (P6)) with different positions of fluorine atoms on the phenyl group were generated. The yields of (P1) to (P6) are shown in parentheses in order. (C ₆ F ₃ H ₂ ) SiMe ₃ (P1) is considered to be trimethyl (2,4,6-trifluorophenyl)silane.
12) Five types of isomers ((C ₆ F ₂ H ₄ ) SiMe ₃ (P1) to (P5)) with different positions of fluorine atoms on the phenyl group were generated. The yields of (P1) to (P5) are shown in parentheses in order. (C ₆ F ₂ H ₄ ) SiMe ₃ (P1) is considered to be trimethyl (2,6-difluorophenyl)silane.
13) Four types of isomers ((C ₆ Cl ₂ H ₄ ) SiMe ₃ (P1) to (P4)) with different positions of chlorine atoms on the phenyl group were generated. The yields of (P1) to (P4) are shown in parentheses in order. (C ₆ Cl ₂ H ₄ ) SiMe ₃ (P1) is considered to be a trimethyl (2,6-dichlorophenyl) silane.
14) Two types of isomers ([C ₆ H ₄ (NO ₂ )] SiMe ₃ (P1) to (P2)) with different positions of nitro groups on the phenyl group were generated. The yields of (P1) and (P2) are shown in parentheses in order. [C ₆ H ₄ (NO ₂ )] SiMe ₃ (P1) is considered to be trimethyl (2-nitrophenyl)silane.
15) Of the two asiloxy groups, one was decarboxylated and two were decarboxylated. The yields of one decarboxylated compound and two decarboxylated compounds are shown in parentheses in this order.

The notes in Tables 3-1 to 3-3 are shown below.
1) The name of each compound is described in Footnote 6 of Table 1-1 and Table 1-2, or Footnote 1 and Footnote 8 of Table 2-1 to Table 2-5.
2) ²⁹ Chemical shift value of Si NMR. _{C 6} D ₆ is used as the NMR solvent. Measured by adding the relaxation reagent Cr (acac) ₃ (chromium (III) acetylacetonate).
3) GC-MS: Gas chromatograph mass spectrometer, EI method: Electron impact ionization method (70eV).
4) When a soluble phosphazene compound was used as the base catalyst for decarbonation, silica gel was added to the reaction solution to adsorb and remove the phosphazene compound, and then the GC-MS of the reaction solution was measured.
_{5) CDCl 3} was used as the NMR solvent.

(Examples 2-62)
The reaction and analysis were carried out in the same manner as in Example 1 by changing the reaction conditions (raw material, base type, solvent, temperature, time, etc.), and the yield of the product was measured by NMR. 1-1 and Table 1-2, and the decarboxylation reaction steps are shown in Tables 2-1 to 2-5. The measurement results of NMR and GC-MS of these products are shown in Tables 3-1 to 3-3.

In the method for producing carbosilane of the present invention, the decarboxylation reaction from asyloxysilane proceeded efficiently by using a specific base catalyst.
For example, in _{the decarboxylation reaction of (C 6} F ₅ CO ₂ ) SiMe ₃ , when P2-t-Bu was used as the base catalyst, as shown in Example 1, the conditions were 100 ° C. and 20 minutes in anisole. The conversion rate of asyloxysilane was 92%, and the yield of carbosilane was 96% with respect to the converted asyloxysilane. Further, even under the conditions of 80 ° C. and 20 minutes, as shown in Example 2, the conversion rate was 70%, and the yield was 96% with respect to the converted asyloxysilane.
On the other hand, when KF, which was known as an effective catalyst for the decarboxylation reaction of asyloxysilane, was used, as shown in Comparative Example 1, the conversion rate of asyloxysilane was set at 100 ° C. for 20 minutes. Was 3%, the yield of carbosilane was 0%, no progress of the decarboxylation reaction was observed, and it was found that P2-t-Bu showed superior catalytic activity.
This result shows that the decarboxylation reaction proceeds more efficiently by using the base catalyst in the present invention as compared with the case of using the conventional catalyst.
Furthermore, if the base catalyst in the present invention is used, the reaction proceeds efficiently even in a less harmful solvent such as anisole (controlled concentration: not set). Therefore, it is not necessary to use a harmful substance such as dimethylformamide (controlled concentration: 10 ppm) which has been conventionally used, and there is a great merit in terms of safety.

Since various carbosilanes useful as functional chemicals or functional materials can be produced more efficiently and safely by the production method of the present invention, the utility value of the present invention is high and its industrial significance is great.

Claims (4)

Si-OCOR bond (OCO represents OC (= O) of oxycarbonyl group. R represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and a hydrogen atom bonded to the carbon atom of the hydrocarbon group. Part or all of the Si-R bond comprising a decarbonation reaction step of decarbonizing in the presence of a base catalyst from an acyloxysilane having (may be substituted with a group not involved in the reaction). A method for producing a carbosilane, which satisfies any of the following conditions (1) to (3) and may include a pre-step for forming an acyloxysilane.
(1) The base catalyst is an organic compound having a pKa of a conjugated acid in the range of 8 to 50; a phosphazene compound; a bicyclic amine compound; a guanidine compound; an amidin compound; or a group derived from those compounds. It is a polymer-based compound or an inorganic-based compound;
(2) The R of the Si-OCOR bond is an alkyl or aryl group in which a part or all of the hydrogen atom bonded to the carbon atom is substituted with a halogen atom, a nitro group, or a cyano group; or an alkynyl group; be.
(3) Calculated value ΔU of the energy difference of the reaction produced by carbosilane by decarbonation from the asyloxysilane (calculated value ΔU of the energy difference is the density general function method (calculation level of ^{B3LYP / 6-31G **).} The calculated value of the energy difference between the original system and the generated system (total internal energy of the generated system molecule-internal energy of the original molecule) is 20 kcal / mol or less. The production method according to claim 1, wherein the pre-step is any of the following steps (4) to (6), and the pre-step and the subsequent decarboxylation reaction step are continuously performed.
(4) The asyloxysilane having a Si-OCOR bond is added to an alkoxysilane having a Si-OR'bond (R'indicates a hydrocarbon group having 1 to 3 carbon atoms) to (RCO) ₂ O (R). Is synonymous with the above.) Is a step of reacting and forming a carboxylic acid anhydride represented by).
(5) The acyloxy having the Si-OCOR bond, the Si-R "bond (R" is. Showing the allyl group) allylsilane having, _RCO 2 H (R has the same meaning as defined above.) In A step of reacting and forming the represented carboxylic acid.
(6) an acyloxy having the Si-OCOR bonds, the chlorosilane having of Si-Cl bond, _RCO 2 H (R has the same meaning as defined above.) Is reacted with a carboxylic acid represented by formed Process. The base catalysts are 1-tert-butyl-2,2,4,4,4-pentakis (dimethylamino) -2λ ⁵ , 4λ ⁵ -catenadi (phosphazene) (P2-t-Bu), 1-tert-butyl. 4,4,4-tris (dimethylamino) -2,2-bis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] -2λ ^5, 4λ ⁵ - Katenaji (phosphazene) (P4-t-Bu) , 2- tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorin (BEMP), tert-butylimino-tri (pyrrolidino) phosphorane (BTPP), 1-azabicyclo [2.2.2] Octane (ABCO), 1,4-diazabicyclo [2.2.2] Octane (DABCO), 7-Methyl-1,5,7-Triazabicyclo [4.4.0] Deca-5-ene (MTBD) , 1,8-Diazabicyclo [5.4.0] -7-undecene (DBU), 1,5-diazabicyclo [4.3.0] -5-nonen (DBN), or a group derived from them. The production method according to claim 1 or 2, which is a base selected from organic polymers. The production method according to any one of claims 1 to 3, wherein the asyloxysilane having a Si-OCOR bond is an asyloxysilane selected from the following general formulas (IA) to (ID).
R ¹ _a R ² _b R ³ _c Si (OCOR) _d (IA)
RCO ₂ (SiR ⁴ R ⁵ ) _m1 OCOR (IB)
RCO ₂ (SiR ⁶ R ⁷ O) _m2 (COR) (IC)
(R ⁸ _e R ⁹ _f R ¹⁰ _g SiOCO) _h R ¹¹ (ID)
(In these equations, a, b, and c are independently 0 or 1; d is an integer greater than or equal to 1 and less than or equal to 3; a + b + c + d = 4; m1 and m2 are independently, respectively. It is an integer of 2 or more; R is synonymous with the above; R ^{1 to} R ¹⁰ are independently each of a hydrogen group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom. Yes, some or all of the hydrogen atoms attached to the carbon atoms of the hydrocarbon group or the alkoxy group may be substituted with groups that are not involved in the reaction; e, f, and g are independent of each other. 0 or 1; e + f + g = 3; h is an integer of 2-4; R ¹¹ is an h-valent hydrocarbon group having 1 to 20 carbon atoms, of the h-valent hydrocarbon group. Part or all of the hydrogen atom bonded to the carbon atom may be replaced with a group that does not participate in the reaction.)