JP2004339200A - Method for synthesizing silyl ketene acetal and disilyl ketene acetal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a high purity silyl ketene acetal and disilyl ketene acetal in a high yield without having by-products such as a salt, etc. <P>SOLUTION: This method for producing silyl ketene acetal of formula (3) is provided by performing the reaction of an α,β-unsaturated carboxylic acid ester of formula (1) (wherein, R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each H or a monovalent hydrocarbon group; and R<SP>4</SP>is a monovalent hydrocarbon group or a silyl group without containing Si-H bond) with a hydrosilane or hydrosiloxane of formula (2) (wherein, R<SB>a</SB>, R<SB>b</SB>, R<SB>c</SB>are each a group selected from a monovalent hydrocarbon group, an organoxy, an organo(poly)siloxy and a halogen atom) in the presence of tris(pentafluorophenyl)borane. Thereby, it is possible to obtain a method for producing a high purity silylketene acetal and disilyl ketene acetal in a high yield without forming by-products such as the salt, etc. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing silyl ketene acetal and disilyl ketene acetal, which is useful as an initiator for group transfer polymerization and as a synthetic intermediate for various organic compounds such as pharmaceuticals and agricultural chemicals.

Silyl ketene acetal is a compound whose synthesis has been reported for the first time by Petrov et al. (Non-Patent Document 1: J. Gen. Chem. (USSR) 1959, Vol. 29, pp. 2896-2899). As an example of the application, it is known that it is used as a polymerization initiator in the polymerization of acrylates known as “group transfer polymerization” developed by Webster et al. (Patent Document 1: US Pat. No. 4,417,034) No., U.S. Pat. No. 4,508,880). Further, the compound is industrially extremely useful, for example, it is used as a nucleophilic reagent in the synthesis of a carboxylic acid derivative (for example, see Patent Document 3: JP-A-2001-247514).
Disilyl ketene acetal can be considered as a kind of silyl ketene acetal from the viewpoint of chemical structure. Therefore, many of its production methods follow the production method of silyl ketene acetal.

  So far, mainly four methods have been known as methods for producing silyl ketene acetal. That is, (1) a method in which a carboxylic acid ester having a hydrogen atom at the α-position is reacted with a base and a silylating agent; (3) a method of reacting a silylating agent such as chlorotrimethylsilane with a silylating agent such as chlorotrimethylsilane in the presence of sodium metal, (4) a method of reacting α, β- In this method, an unsaturated carboxylic acid ester is reacted with a hydrosilane or a hydrosiloxane in the presence of a transition metal catalyst.

  In the method (1), as a combination of a base and a silylating agent, lithium diisopropylamide / chlorotrimethylsilane (for example, see Patent Document 4: JP-A-9-222444), triethylamine / trimethylsilyl trifluoromethanesulfonate (for example, And U.S. Pat. No. 4,482,729). In each case, the reaction proceeds at a low temperature of room temperature or lower, but a large amount of salt is generated because it is necessary to use one or more equivalents of a base. This can be an obstacle, especially when performing large-scale reactions. Further, in the latter combination, in addition to the target silyl ketene acetal, a by-product in which the carbon at the α-position is silylated is generated, so that the yield may be low depending on the substrate.

  In the method (2) (for example, refer to JP-A-2-111780) and the method (3) (for example, refer to JP-A-64-85882), at least one equivalent is used. Since a metal such as sodium is used, a large amount of a metal salt is generated, and it is necessary to remove this in order to isolate silyl ketene acetal. Further, since these metals are usually used in excess, activated metals are mixed in the produced metal salt, and special care must be taken in handling. Therefore, it is not easy to implement these methods on a large scale.

  The method by hydrosilylation of (4) utilizes an addition reaction, unlike the methods of (1) to (3). Therefore, there is an advantage that waste such as the above-mentioned salt is not generated, which is preferable. In this method, it is known that a transition metal compound is used as a catalyst. For example, in the above-mentioned Petrov et al. Document, a platinum compound is used as a catalyst. Among them, rhodium catalysts are effective, for example, see Chem. Pharm. Bull. Chlorotris (triphenylphosphine) rhodium is disclosed in Japanese Patent Application Laid-Open No. 62-87594 in Japanese Patent Application Laid-Open No. 62-87594 in Vol. 2 of 1974, pages 2767 to 2769 (Non-Patent Document 2) and Japanese Patent Application Laid-Open No. 63-29087 (Patent Document 8). In 9), rhodium trichloride trihydrate is used. Also, US Pat. No. 5,208,358 (Patent Document 10) succeeds in obtaining silyl ketene acetal with a smaller amount of catalyst using chlorobis (di-tert-butylsulfide) rhodium. However, as described in JP-A-62-87594 (Patent Document 9), when a hydrosilylation reaction is carried out using a transition metal catalyst, in addition to the target silyl ketene acetal, the target substance and the boiling point are close to each other. In addition, carbonyl adducts and β-adducts which are difficult to separate by distillation were formed, and it was difficult to obtain high-purity silylketene acetal. In JP-A-62-87594 (Patent Document 9), high purity (95% or more) is obtained by converting a carbonyl adduct into a high-boiling compound by using rhodium trichloride trihydrate as a catalyst and using excess amount of hydrosilane. A) Silyl ketene acetal. However, in this method, the yield based on hydrosilane is reduced, and the distillation yield is reduced due to an increase in the amount of the residue when the target product is isolated by distillation, so that the silyl ketene acetal can be obtained at a high yield. It was difficult.

As described above, the method for producing a silyl ketene acetal by hydrosilylation of an α, β-unsaturated carboxylic acid ester is essentially free from by-products such as salts, but is excellent in the conventional transition metal catalyst. The hydrosilylation mode produces multiple compounds with low selectivity. Therefore, a method for producing a highly selective silyl ketene acetal with high selectivity and high yield has been desired.
In principle, any of the above methods can be applied to the production of disilylketene acetal.However, in the case of disilylketene acetal, the carboxylic acid silyl ester used as a raw material is not generally commercially available. There are many. Therefore, since a step of obtaining a silyl carboxylate by silylation of the carboxylic acid is first required, the production cost is further increased.

As a method for producing disilylketene acetal other than the above, there has been proposed a method of reacting α, β-unsaturated carboxylic acid allyl ester with hydrosilane in the presence of a rhodium catalyst (Patent Document 11: JP-A-64-71886). Publication). According to this method, a disilyl ketene acetal can be obtained in one step using an industrially available α, β-unsaturated carboxylic acid allyl ester such as allyl methacrylate as a raw material. However, although the reaction mixture obtained by this method is described as containing no carbonyl adduct, which is a typical by-product, the yield of the target product is high because other by-products are produced in large amounts. And purity were not satisfactory.
As described above, the existing method for producing disilylketene acetal has problems such as a large amount of by-products and difficulty in purifying the target product. Therefore, a method for producing higher yield and higher purity disilylketene acetal without by-products has been desired.

U.S. Pat. No. 4,417,034 U.S. Pat. No. 4,508,880 JP 2001-247514 A JP-A-9-222444 U.S. Pat. No. 4,482,729 JP-A-2-111780 JP-A-64-85882 JP-A-63-29087 JP-A-62-87594 U.S. Pat. No. 5,208,358 JP-A-64-71886 J. Gen. Chem. (USSR) 1959 Vol. 29, pages 2896-2899 Chem. Pharm. Bull. 1974, Vol. 22, pp. 2767-2767

  The present invention has been made to meet the above-mentioned demands, and has an object to provide a method for producing high-purity silylketene acetal and disilylketene acetal in high yield without by-products such as salts. And

  The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, reacted an α, β-unsaturated carboxylic acid ester with hydrosilane or hydrosiloxane in the presence of a catalytic amount of tris (pentafluorophenyl) borane. As a result, a method for producing a silyl ketene acetal or a disilyl ketene acetal with a high purity and a high yield according to the use ratio of an α, β-unsaturated carboxylic acid ester and a hydrosilane or a hydrosiloxane has been found.

（式中、Ｒ¹、Ｒ²、Ｒ³はそれぞれ独立に水素原子又は置換もしくは非置換の炭素数１〜６０の一価炭化水素基を表す。あるいは、Ｒ¹とＲ²又はＲ¹とＲ³は互いに結合してこれらが結合する炭素原子と共に炭素数３〜２０の環を形成してもよい。Ｒ⁴は置換もしくは非置換の炭素数１〜４０の一価炭化水素基、又は置換もしくは非置換の炭素数６０以下のＳｉ−Ｈ結合を含まないシリル基を表す。）

（式中、Ｒ^a、Ｒ^b、Ｒ^cはそれぞれ独立に置換もしくは非置換の炭素数１〜２０の一価炭化水素基、炭素数１〜２０のオルガノキシ基、ケイ素数１〜１，０００のオルガノ（ポリ）シロキシ基、及びハロゲン原子から選ばれる基を表す。あるいは、Ｒ^aとＲ^b、Ｒ^aとＲ^c又はＲ^bとＲ^cは互いに結合してこれらが結合するケイ素原子と共に、ケイ素数３〜５０のシロキサン環を形成するか又は炭素数１〜２０のケイ素含有環を形成してもよい。また、Ｒ^a、Ｒ^b、Ｒ^cは互いに結合してこれらが結合するケイ素原子と共にケイ素数６〜５０のかご状シロキサンを形成してもよい。）

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ^a、Ｒ^b、Ｒ^cはそれぞれ式（１）及び（２）で定義された基を表す。）
請求項２：
式（２）で表されるヒドロシラン又はヒドロシロキサンと触媒量のトリス（ペンタフルオロフェニル）ボランの混合物を含む反応器に、式（１）で表されるα，β−不飽和カルボン酸エステルを添加することを特徴とする、請求項１に記載のシリルケテンアセタールの製造方法。
請求項３：
触媒量のトリス（ペンタフルオロフェニル）ボランを含む反応器に、式（１）で表されるα，β−不飽和カルボン酸エステルと、式（２）で表されるヒドロシラン又はヒドロシロキサンを、式（１）の化合物１モルに対して式（２）の化合物のＳｉ−Ｈ結合のモル比を０．９〜１．１に調節しながら添加することを特徴とする、請求項１に記載のシリルケテンアセタールの製造方法。
請求項４：
下記一般式（４）で表されるα，β−不飽和カルボン酸エステルと、下記一般式（２）で表されるヒドロシラン又はヒドロシロキサンとを触媒量のトリス（ペンタフルオロフェニル）ボラン存在下に反応させることを特徴とする、下記一般式（５）で表されるジシリルケテンアセタールの製造方法。

（式中、Ｒ⁵、Ｒ⁶、Ｒ⁷はそれぞれ独立に水素原子又は置換もしくは非置換の炭素数１〜６０の一価炭化水素基を表す。あるいは、Ｒ⁵とＲ⁶又はＲ⁵とＲ⁷は互いに結合してこれらが結合する炭素原子と共に炭素数３〜２０の環を形成してもよい。Ｒ⁸は置換もしくは非置換の炭素数１〜４０の一価炭化水素基を表す。）

（式中、Ｒ^a、Ｒ^b、Ｒ^cはそれぞれ独立に置換もしくは非置換の炭素数１〜２０の一価炭化水素基、炭素数１〜２０のオルガノキシ基、ケイ素数１〜１，０００のオルガノ（ポリ）シロキシ基、及びハロゲン原子から選ばれる基を表す。あるいは、Ｒ^aとＲ^b、Ｒ^aとＲ^c又はＲ^bとＲ^cは互いに結合してこれらが結合するケイ素原子と共に、ケイ素数３〜５０のシロキサン環を形成するか又は炭素数１〜２０のケイ素含有環を形成してもよい。また、Ｒ^a、Ｒ^b、Ｒ^cは互いに結合してこれらが結合するケイ素原子と共にケイ素数６〜５０のかご状シロキサンを形成してもよい。）

（式中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ^a、Ｒ^b、Ｒ^cはそれぞれ式（４）及び（２）で定義された基を表す。）
請求項５：
式（２）で表されるヒドロシラン又はヒドロシロキサンと触媒量のトリス（ペンタフルオロフェニル）ボランの混合物を含む反応器に、式（２）の化合物のＳｉ−Ｈ結合１モルに対して０．５モル以下の式（４）で表されるα，β−不飽和カルボン酸エステルを添加することを特徴とする、請求項４に記載のジシリルケテンアセタールの製造方法。
請求項６：
下記一般式（６）で表されるシリルケテンアセタールと下記一般式（２）で表されるヒドロシラン又はヒドロシロキサンとを触媒量のトリス（ペンタフルオロフェニル）ボラン存在下に反応させることを特徴とする、下記一般式（７）で表されるジシリルケテンアセタールの製造方法。

（式中、Ｒ⁹、Ｒ¹⁰はそれぞれ独立に水素原子又は置換もしくは非置換の炭素数１〜６０の一価炭化水素基を表す。あるいは、Ｒ⁹とＲ¹⁰は互いに結合してこれらが結合する炭素原子と共に炭素数３〜２０の環を形成してもよい。Ｒ¹¹は置換もしくは非置換の炭素数１〜４０の一価炭化水素基を表す。Ｒ^d、Ｒ^e、Ｒ^fはそれぞれ独立に置換もしくは非置換の炭素数１〜２０の一価炭化水素基、炭素数１〜２０のオルガノキシ基、ケイ素数１〜１，０００のオルガノ（ポリ）シロキシ基、及びハロゲン原子から選ばれる基を表す。あるいは、Ｒ^dとＲ^e、Ｒ^dとＲ^f又はＲ^eとＲ^fは互いに結合してこれらが結合するケイ素原子と共に、ケイ素数３〜５０のシロキサン環を形成するか又は炭素数１〜２０のケイ素含有環を形成してもよい。また、Ｒ^d、Ｒ^e、Ｒ^fは互いに結合してこれらが結合するケイ素原子と共にケイ素数６〜５０のかご状シロキサンを形成してもよい。）

（式中、Ｒ^a、Ｒ^b、Ｒ^cはそれぞれ独立に置換もしくは非置換の炭素数１〜２０の一価炭化水素基、炭素数１〜２０のオルガノキシ基、ケイ素数１〜１，０００のオルガノ（ポリ）シロキシ基、及びハロゲン原子から選ばれる基を表す。あるいは、Ｒ^aとＲ^b、Ｒ^aとＲ^c又はＲ^bとＲ^cは互いに結合してこれらが結合するケイ素原子と共に、ケイ素数３〜５０のシロキサン環を形成するか又は炭素数１〜２０のケイ素含有環を形成してもよい。また、Ｒ^a、Ｒ^b、Ｒ^cは互いに結合してこれらが結合するケイ素原子と共にケイ素数６〜５０のかご状シロキサンを形成してもよい。）

（式中、Ｒ⁹、Ｒ¹⁰、Ｒ^a、Ｒ^b、Ｒ^c、Ｒ^d、Ｒ^e、Ｒ^fはそれぞれ式（２）及び（６）で定義された基を表す。） That is, the present invention provides the following methods for producing silyl ketene acetal and disilyl ketene acetal.
Claim 1:
An α, β-unsaturated carboxylic acid ester represented by the following general formula (1) and a hydrosilane or hydrosiloxane represented by the following general formula (2) are prepared in the presence of a catalytic amount of tris (pentafluorophenyl) borane. A method for producing a silyl ketene acetal represented by the following general formula (3), characterized by reacting:

(In the formula, R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having ¹ to 60 carbon atoms. Alternatively, R ¹ and R ² or R ¹ and R ³ may be bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and R ⁴ may be a substituted or unsubstituted monovalent hydrocarbon group having 1 to 40 carbon atoms, or It represents an unsubstituted silyl group having 60 or less carbon atoms and not containing a Si—H bond.)

(Wherein, R ^a , R ^b , and R ^c each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an organooxy group having 1 to 20 carbon atoms, and a silicon atom having 1 to 1,000 silicon atoms. Represents a group selected from an organo (poly) siloxy group and a halogen atom, or represents a silicon atom together with a silicon atom to which R ^a and R ^b , R ^a and R ^c or R ^b and R ^c are bonded to each other. It may form a siloxane ring having a number of 3 to 50 or a silicon-containing ring having 1 to 20 carbon atoms, and R ^a , R ^b and R ^c may be bonded to each other together with a silicon atom to which they are bonded. (A cage siloxane having 6 to 50 silicon atoms may be formed.)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ^a , R ^b , and R ^c represent groups defined by the formulas (1) and (2), respectively.)
Claim 2:
An α, β-unsaturated carboxylic acid ester represented by the formula (1) is added to a reactor containing a mixture of the hydrosilane or hydrosiloxane represented by the formula (2) and a catalytic amount of tris (pentafluorophenyl) borane. The method for producing a silyl ketene acetal according to claim 1, wherein:
Claim 3:
In a reactor containing a catalytic amount of tris (pentafluorophenyl) borane, an α, β-unsaturated carboxylic acid ester represented by the formula (1) and a hydrosilane or hydrosiloxane represented by the formula (2) are added to a reactor having the formula The compound according to claim 1, wherein the compound is added while adjusting the molar ratio of the Si-H bond of the compound of formula (2) to 0.9 to 1.1 with respect to 1 mole of the compound of (1). A method for producing a silyl ketene acetal.
Claim 4:
An α, β-unsaturated carboxylic acid ester represented by the following general formula (4) and a hydrosilane or hydrosiloxane represented by the following general formula (2) are prepared in the presence of a catalytic amount of tris (pentafluorophenyl) borane. A method for producing a disilylketene acetal represented by the following general formula (5), characterized by reacting:

(Wherein, R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 60 carbon atoms. Alternatively, R ⁵ and R ⁶ or R ⁵ and R ^{6 7} may be bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded. R ⁸ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 40 carbon atoms.)

(Wherein, R ^a , R ^b , and R ^c each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an organooxy group having 1 to 20 carbon atoms, and a silicon atom having 1 to 1,000 silicon atoms. Represents a group selected from an organo (poly) siloxy group and a halogen atom, or represents a silicon atom together with a silicon atom to which R ^a and R ^b , R ^a and R ^c or R ^b and R ^c are bonded to each other. It may form a siloxane ring having a number of 3 to 50 or a silicon-containing ring having 1 to 20 carbon atoms, and R ^a , R ^b and R ^c may be bonded to each other together with a silicon atom to which they are bonded. (A cage siloxane having 6 to 50 silicon atoms may be formed.)

(In the formula, R ⁵ , R ⁶ , R ⁷ , R ^a , R ^b , and R ^c each represent a group defined by the formulas (4) and (2).)
Claim 5:
In a reactor containing a mixture of a hydrosilane or hydrosiloxane represented by the formula (2) and a catalytic amount of tris (pentafluorophenyl) borane, 0.5 to 1 mol of Si—H bond of the compound of the formula (2) is added. The method for producing a disilylketene acetal according to claim 4, wherein an α, β-unsaturated carboxylic acid ester represented by the following formula (4) is added in a molar amount or less.
Claim 6:
A silyl ketene acetal represented by the following general formula (6) is reacted with a hydrosilane or hydrosiloxane represented by the following general formula (2) in the presence of a catalytic amount of tris (pentafluorophenyl) borane. And a method for producing a disilylketene acetal represented by the following general formula (7).

(Wherein, R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 60 carbon atoms. Alternatively, R ⁹ and R ¹⁰ are bonded to each other to form a bond. R ¹¹ may represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 40 carbon atoms, and R ^d , R ^e , and R ^f each represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 40 carbon atoms. A group independently selected from a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an organooxy group having 1 to 20 carbon atoms, an organo (poly) siloxy group having 1 to 1,000 silicon atoms, and a halogen atom Or R ^d and R ^e , R ^d and R ^f or R ^e and R ^f are bonded to each other to form a siloxane ring having 3 to 50 silicon atoms together with the silicon atom to which they are bonded, or It may form 1 to 20 silicon-containing rings. ^d, R ^e, R ^f may form a cage siloxane silicon atoms of 6 to 50 together with the silicon atom to which they are attached.)

(Wherein, R ^a , R ^b , and R ^c each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an organooxy group having 1 to 20 carbon atoms, and a silicon atom having 1 to 1,000 silicon atoms. Represents a group selected from an organo (poly) siloxy group and a halogen atom, or represents a silicon atom together with a silicon atom to which R ^a and R ^b , R ^a and R ^c or R ^b and R ^c are bonded to each other. It may form a siloxane ring having a number of 3 to 50 or a silicon-containing ring having 1 to 20 carbon atoms, and R ^a , R ^b and R ^c may be bonded to each other together with a silicon atom to which they are bonded. (A cage siloxane having 6 to 50 silicon atoms may be formed.)

(In the formula, R ⁹ , R ¹⁰ , R ^a , R ^b , R ^c , R ^d , R ^e , and R ^f represent groups defined by the formulas (2) and (6), respectively.)

  According to the present invention, it is possible to provide a method for producing high-purity silylketene acetal and disilylketene acetal in high yield without by-products such as salts. The obtained silyl ketene acetal is a very useful compound for polymer synthesis and organic synthesis. Further, in the method of the present invention, a disilylketene acetal industrially useful in the fields of polymer synthesis and organic synthesis can be obtained in one step by using raw materials available on an industrial scale.

Hereinafter, the present invention will be described in more detail.
In the method for producing a silyl ketene acetal of the present invention, the α, β-unsaturated carboxylic acid ester used as a starting material is represented by the following general formula (1).

In the general formula ^{(1), R 1, R} 2, R 3 each independently represents a hydrogen atom or a substituted or unsubstituted 1 to 60 carbon atoms, preferably a 1-20 monovalent hydrocarbon group. In this case, the unsubstituted monovalent hydrocarbon group is preferably a group having 1 to 20 carbon atoms, and a substituted monovalent hydrocarbon group which partially or entirely replaces a hydrogen atom bonded to a carbon atom of the unsubstituted monovalent hydrocarbon group. The substituent of the valent hydrocarbon group does not include a halogen atom, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkenyloxy group, an organo group such as an aryloxy group, or a Si-H bond having 60 or less carbon atoms. A silyl group, an organo (poly) siloxy group having 1 to 1,000, preferably 1 to 50, particularly preferably 1 to 10 silicon atoms are suitable.

Specific examples of the groups represented by R ¹ , R ² and R ³ include a methyl group, a chloromethyl group, a bromobutyl group, an iodomethyl group, a trifluoromethyl group, a trimethylsilylmethyl group, a tris (trimethylsiloxy) silylmethyl group, a tris (Trimethylsiloxy) siloxymethyl group, ethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-trimethylsiloxyethyl group, 2-triethylsiloxyethyl group, n-propyl group, 3- (trimethoxysilyl) propyl Group, 3- (triethoxysilyl) propyl group, 3-tris (trimethylsiloxy) silylpropyl group, 3- (3,5,7,9,11,13,15-heptacyclopentylcyclo [9.5.1. 1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) propyl group, (3,5,7,9,11 , 13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl-oxy dimethylsilyl) methyl group, 3- (3,5 , 7,9,11,13,15- hepta isobutyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) propyl, 3- ( Pentamethyldisiloxanyloxy) propyl group, 3- (ω-butylpolydimethylsiloxane-1-yloxy) propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, Hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, linear or branched, cyclic substituted or unsubstituted alkyl group such as stearyl group, vinyl group, propenyl group, isoprene group Linear, branched, or cyclic substituted or unsubstituted alkenyl, ethynyl, propynyl, butynyl, etc. linear groups such as a phenyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, a decenyl group, and an undecenyl group; , Branched or cyclic, substituted or unsubstituted alkynyl, phenyl, 4-fluorophenyl, 4-tert-butylphenyl, pentafluorophenyl, 2-tolyl, 3-tolyl, 4- Such as a tolyl group, a 2,6-dimethylphenyl group, a 2,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 3,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a naphthyl group, and a biphenylyl group. Substituted or unsubstituted aryl, benzyl, 2-chlorobenzyl, 4-bromobenzyl, 4-methoxybenzyl, Ruechiru group, and substituted or unsubstituted aralkyl groups such as phenylpropyl group.

In the above formula (1), R ¹ and R ² or R ¹ and R ³ may be bonded to each other to form a ring having 3 to 20 carbon atoms, particularly 5 to 12 carbon atoms, together with the carbon atom to which they are bonded. Examples of such a ring include a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclooctadiene ring, a norbornene ring, an indene ring, and the like.

In the above formula (1), R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 40, preferably 1 to 20 carbon atoms, or a substituted or unsubstituted Si—H having 60 or less carbon atoms. Indicates a silyl group containing no bond. In this case, the unsubstituted monovalent hydrocarbon group preferably has 1 to 20 carbon atoms, and the unsubstituted silyl group containing no Si-H bond particularly preferably has 40 or less carbon atoms. The unsubstituted monovalent hydrocarbon group and the substituent of the substituted monovalent hydrocarbon group or the substituted organosilyl group that partially or completely replaces the hydrogen atom bonded to the carbon atom of the unsubstituted organosilyl group include a halogen atom. Having 1 to 20 carbon atoms, preferably 1 to 10 alkoxy groups, alkenyloxy groups, organo groups such as aryloxy groups, silyl groups having 60 or less carbon atoms and containing no Si-H bond, 1 to 1,000 silicon atoms, preferably Is preferably 1 to 200 organo (poly) siloxy groups or the like. Examples of R ⁴ are in addition to the same groups as R ^1, R ^2, R ³ above, trimethylsilyl group, chloromethyl dimethylsilyl group, (trimethylsilylmethyl) dimethylsilyl group, ethyldimethylsilyl group, 3-chloropropyl Dimethylsilyl group, 3,3,3-trifluoropropyldimethylsilyl group, diethylmethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tributylsilyl group, triisobutylsilyl group, tert-butyldimethylsilyl Group, cyclopentyldimethylsilyl group, hexyldimethylsilyl group, cyclohexyldimethylsilyl group, texyldimethylsilyl group, texyldiisopropylsilyl group, decyldimethylsilyl group, octadecyldimethylsilyl group, benzyldimethylsilyl group, dimethyl Phenylsilyl group, methyldiphenylsilyl group, triphenylsilyl group, tri-p-tolylsilyl group, tri-o-tolylsilyl group, methoxydimethylsilyl group, dimethoxymethylsilyl group, trimethoxysilyl group, ethyldimethoxysilyl group, propyldimethoxy Silyl group, ethoxydimethylsilyl group, diethoxymethylsilyl group, triethoxysilyl group, isopropoxydimethylsilyl group, sec-butoxydimethylsilyl group, tert-butoxydimethylsilyl group, dimethylphenoxysilyl group, benzyloxydimethylsilyl group, Chlorodimethylsilyl, dichloromethylsilyl, trichlorosilyl, chlorodiethylsilyl, dichloroethylsilyl, chlorodiphenylsilyl, dichlorophenylsilyl, pentamethyldisil Xanyl group, 3-chloropropyl-1,1,3,3-tetramethyldisiloxanyl group, 1,1,3,3,5,5,5-heptamethyltrisiloxanyl group, 1,1,1 1,3,5,5,5-heptamethyltrisiloxanyl group, 1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane-1-yl group, tris (trimethylsiloxy) silyl group , 3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 . ^15.15 . 1 ^7,13 ] octasiloxane-1-yl group, 3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 . ^15.15 . [ ^1,7,13 ] octasiloxane-1- ^{yloxydimethylsilyl} group, .omega.-butylpolydimethylsiloxane-1-yl group and the like.

As the α, β-unsaturated carboxylic acid ester represented by the above formula (1), specifically, methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, butyl acrylate, Tert-butyl acrylate, cyclohexyl acrylate, 1,1,2-trimethylpropyl acrylate, vinyl acrylate, allyl acrylate, isopropenyl acrylate, 1-cyclohexenyl acrylate, 10-undecenyl acrylate, ethynyl acrylate , Trimethylsilyl acrylate, triethylsilyl acrylate, triisopropylsilyl acrylate, tert-butyldimethylsilyl acrylate, methyl methacrylate, ethyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, methacrylic acid 2-trimethylsiloxyethyl acrylate, 2-chloropropyl methacrylate, 3-triethylsilylpropyl methacrylate, 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, 3-tris methacrylate (trimethylsiloxy) silyl propyl methacrylate 3- (3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^{7, 13]} octasiloxane-1-yl) propyl methacrylate 3- (3,5,7,9,11,13,15- hepta isobutyl penta cyclo [9.5.1.1 ^3,9 .1 ^{5,15 .1,7,13} ] octasiloxane-1-yl) propyl, 3- (3,5,7,9,11,13,15-heptacyclopentylpentacyclo [methacrylate] 9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl-oxy dimethylsilyl) methyl methacrylate 3- (3,5,7,9,11,13, 15 hepta cyclopentyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl-oxy-butyldimethylsilyl) propyl, butyl methacrylate, isobutyl methacrylate, tert-butyl, cyclohexyl methacrylate, 1,1,2-trimethylpropyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, octadecyl methacrylate, vinyl methacrylate, allyl methacrylate, isopropenyl methacrylate, 1-cyclohexenyl methacrylate, 10-undecenyl methacrylate, methacrylic acid Ethynyl, benzyl methacrylate, phenyl methacrylate, trimethylsilyl methacrylate, methacrylic acid (3-chloropropyldimethylsilyl), methacrylic acid (dimethyl-3,3,3-trifluoropropylsilyl), triethylsilyl methacrylate, trimethyl methacrylate Isopropylsilyl, tert-butyldimethylsilyl methacrylate, methacrylic acid (1,1,3,3,3-pentamethyldisiloxane-1-yl), methacrylic acid (1,3,3,5,5,7,7 -Heptamethylcyclotetrasiloxane-1-yl), methacrylic acid (3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 . ^15.15 . 1 ^7,13] octasiloxane-1-yl), methacrylic acid (3,5,7,9,11,13,15- hepta isobutyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl), methacrylic acid (3,5,7,9,11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^{3, 9} .1 ^{5, 15.1 7,13]} octasiloxane-1-yl-oxy-butyldimethylsilyl), methyl crotonate, methyl cinnamate, 4-chloro-cinnamic acid ethyl 4-methoxycinnamate, methyl 1-cyclohexene-carboxylic acid methyl, cyclohexylidene Methyl acetate, 1,1,3,3,3-pentamethyl-1- [3-methacryloyloxy] propyl] disiloxane, α- [3- (methacryloyloxy) propyl] -ω-butyl-polydimethylsiloxane, etc. But It is below.

In the method for producing a silyl ketene acetal of the present invention, the α, β-unsaturated carboxylic acid ester of the above formula (1) is reacted with a hydrosilane or hydrosiloxane represented by the following general formula (2).

In the general formula (2), ^Ra , ^Rb , and ^Rc each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms, and 1 to 20 carbon atoms, preferably Represents a group selected from an organooxy group having 1 to 10, an organo (poly) siloxy group having 1 to 1,000 silicon atoms, and a halogen atom.

Specific examples of the groups represented by R ^a , R ^b , and R ^c include, for example, methyl, chloromethyl, trifluoromethyl, ethyl, propyl, 3-chloropropyl, 3,3,3-tri Straight chain such as fluoropropyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group and stearyl group , Branched, cyclic substituted or unsubstituted alkyl group, phenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 4-iodophenyl group, pentafluorophenyl group, tolyl group, Substituted or unsubstituted aryl groups such as xylyl group, naphthyl group, biphenylyl group, benzyl group, phenylethyl group, A substituted or unsubstituted aralkyl group such as nylpropyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, isobutoxy group, cyclopentyloxy group, cyclohexyloxy group, nor A substituted or unsubstituted aryloxy group such as a substituted or unsubstituted alkoxy group such as a bornyloxy group, a phenoxy group, a 3-chlorophenoxy group, and a naphthyloxy group, a benzyloxy group, a 2-chlorobenzyloxy group, Substituted or unsubstituted aralkyloxy groups such as chlorobenzyloxy group, 4-chlorobenzyloxy group, naphthylethyloxy group, dimethylsiloxy group, diethylsiloxy group, diphenylsiloxy group, trimethylsiloxy group, chloromethyldimethylsiloxy group, Triethylsiloxy group, phenyldimethylsiloxy group, diphenylmethylsiloxy group, 1,1,3,3,3-pentamethyldisiloxaniloxy group, 1,1,3,3-tetramethyldisiloxaniloxy group, bis (Trimethylsiloxy) siloxy group, methylbis (trimethylsiloxy) siloxy group, tris (trimethylsiloxy) siloxy group, 1,3,3,5,5-pentamethylcyclotrisiloxane-1-yloxy group, 1,3,5- Trimethyl-3,5-bis (3,3,3-trifluoropropyl) cyclotrisiloxane-1-yloxy group, 1,3,5,7-tetramethylcyclotetrasiloxane-1-yloxy group, ω-methylpoly Dimethylsiloxaniloxy group, ω-hydropolydimethylsiloxaniloxy group, polyhydromethylsiloxanillo Examples thereof include a linear, branched, or cyclic substituted or unsubstituted organo (poly) siloxy group such as an xy group.

R ^a and R ^b , R ^a and R ^c, or R ^b and R ^c are bonded to each other, and together with the silicon atom to which they are bonded, a siloxane ring having 3 to 50, particularly 3 to 20 silicon atoms, or a 1 to 20 carbon atoms. A silicon-containing ring may be formed. Further, R ^a , R ^b , and R ^c may be bonded to each other to form a cage siloxane having 6 to 50, particularly 6 to 20 silicon atoms together with the silicon atom to which they are bonded. Specific examples of the cage siloxane ring include, but are not limited to, the following.

Examples of the compound represented by the above formula (2) include, for example, trimethylsilane, chloromethyldimethylsilane, (trimethylsilylmethyl) dimethylsilane, ethyldimethylsilane, 3-chloropropyldimethylsilane, 3,3,3-trifluoropropyl Dimethylsilane, diethylmethylsilane, triethylsilane, tripropylsilane, triisopropylsilane, tributylsilane, triisobutylsilane, tert-butyldimethylsilane, cyclopentyldimethylsilane, hexyldimethylsilane, cyclohexyldimethylsilane, texyldimethylsilane, texyl Diisopropylsilane, decyldimethylsilane, octadecyldimethylsilane, benzyldimethylsilane, dimethylphenylsilane, methyldiphenylsilane, triphenyl Orchid, tri-p-tolylsilane, tri-o-tolylsilane, 1,4-bis (dimethylsilyl) benzene, methoxydimethylsilane, dimethoxymethylsilane, trimethoxysilane, ethyldimethoxysilane, propyldimethoxysilane, ethoxydimethylsilane, Ethoxymethylsilane, triethoxysilane, isopropoxydimethylsilane, sec-butoxydimethylsilane, tert-butoxydimethylsilane, dimethylphenoxysilane, benzyloxydimethylsilane, chlorodimethylsilane, dichloromethylsilane, trichlorosilane, chlorodiethylsilane, dichloro Organohydrosilanes such as ethylsilane, chlorodiphenylsilane, dichlorophenylsilane, pentamethyldisiloxane, 3-chloropropyl-1,1 3,3-tetramethyldisiloxane, 1,1,3,3,5,5,5-heptamethyltrisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetra Isopropyldisiloxane, 1,3-dimethyl-1,3-diphenyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,3,5,5,5-hepta Methyltrisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (trimethylsiloxy) silane, 1-hydrido- 3,5,7,9,11,13,15-Heptacyclopentylpentacyclo [9.5.1.1 ^3,9 . ^15.15 . 1 ^7,13 ] octasiloxane, 1- (hydridodimethylsiloxy) -3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 . ^15.15 . 1 ^7,13] octasiloxane, 1,3,5,7,9,11,13,15- octakis (dimethylsiloxy) pentacyclo [9.5.1.1 ^{3, 9. 15.15} . [ ^1,7,13 ] octasiloxane, α-hydro-ω-methylpolydimethylsiloxane, α, ω-dihydropolydimethylsiloxane, polymethylhydrosiloxane, and other linear, branched, cyclic, and cage-shaped organohydrosiloxanes And the like.

  The amount of the compound of the formula (2) used is such that the number of moles of the Si—H bond contained in the compound of the formula (2) is 0.9 to 1.1 per mole of the compound of the formula (1). The reaction is preferably performed in a molar ratio. If either of the compounds is used in a large excess, the yield of the compound may be reduced, the rate of side reactions may be increased, and the yield may be further reduced.

  In the method for producing a silyl ketene acetal of the present invention, the compound of the above formula (1) and the compound of the above formula (2) are reacted in the presence of a catalytic amount of tris (pentafluorophenyl) borane. The amount of tris (pentafluorophenyl) borane varies depending on the reaction substrate, but is usually 0.00001 to 10 mol%, preferably 0.0001 to 1 mol%, based on the compound of the above formula (1).

The reaction is generally carried out at normal pressure in an atmosphere of an inert gas such as nitrogen, but is not necessarily limited to this. The reaction temperature is usually -100 to 100 ° C, preferably -20 to 60 ° C. In the production of the silyl ketene acetal, in the compound of the above formula (1), R ⁴ is bonded via a primary or secondary sp ³ carbon. When the compound is bonded to an oxygen atom by the above method, the compound represented by the above formula (1) is placed in a reactor containing a mixture of the hydrosilane or hydrosiloxane represented by the above formula (2) and a catalytic amount of tris (pentafluorophenyl) borane. In the method of adding an α, β-unsaturated carboxylic acid ester, the reaction is preferably performed at a reaction temperature in the range of -100 to -20 ° C. On the other hand, in a reactor containing a catalytic amount of tris (pentafluorophenyl) borane, an α, β-unsaturated carboxylic acid ester represented by the above formula (1) and a hydrosilane or hydrosilane represented by the above formula (2) are added. In the method of adding siloxane while adjusting the molar ratio of the Si—H bond of the compound of the formula (2) to the compound of the formula (1) to 0.9 to 1.1, the reaction temperature is set to −50. It is preferable to carry out in the range of -30 ° C.

  The mixing method of the substrate and the catalyst is arbitrary, but it should be noted that the α, β-unsaturated carboxylic acid ester of the above formula (1) generally has polymerizability. In order to control the reaction conditions and reduce the possibility of polymerization, the compound of the above formula (1) is fed to the reactor containing the catalyst and the compound of the above formula (2), or the reactor containing the catalyst is fed to the reactor containing the catalyst. A method in which the reaction proceeds while feeding both the compounds of the above formulas (1) and (2) is preferable. In the latter case, it is preferable to feed while adjusting the molar ratio of the Si—H bond of the compound of the formula (2) to the compound of the formula (1) to 0.9 to 1.1.

The reaction solvent is not necessarily required. In particular, when both the reaction substrates (1) and (2) are liquid, the reaction can be performed without a solvent, but the reaction may be performed using a solvent. In this case, a hydrocarbon solvent such as hexane, isooctane, benzene, toluene and xylene, or a halogenated hydrocarbon solvent such as dichloromethane and dichloroethane can be used.
The addition of a polymerization inhibitor during the reaction is optional. When a polymerization inhibitor is used, for example, 2,6-di-tert-butyl-4-methylphenol (BHT), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Hindered phenols such as 2,4,6-trimethylbenzene are preferred.

上記一般式（３）中のＲ¹、Ｒ²、Ｒ³、Ｒ⁴及びＲ^a、Ｒ^b、Ｒ^cは上記した定義通りである。 By the method of the present invention described above, a silyl ketene acetal represented by the following general formula (3) is obtained.

In the general formula (3), R ¹ , R ² , R ³ , R ⁴ and R ^a , R ^b , and R ^c are as defined above.

In the method for producing disilylketene acetal of the present invention, the α, β-unsaturated carboxylic acid ester used as a starting material is represented by the following general formula (4).

In the above general formula (4), R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 60, preferably 1 to 20 carbon atoms. In this case, the unsubstituted monovalent hydrocarbon group is preferably a group having 1 to 20 carbon atoms, and a substituted monovalent hydrocarbon group which partially or entirely replaces a hydrogen atom bonded to a carbon atom of the unsubstituted monovalent hydrocarbon group. The substituent of the valent hydrocarbon group does not include a halogen atom, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkenyloxy group, an organo group such as an aryloxy group, or a Si-H bond having 60 or less carbon atoms. A silyl group, an organo (poly) siloxy group having 1 to 1,000, preferably 1 to 50, particularly preferably 1 to 10 silicon atoms are suitable.

Specific examples of the groups represented by R ⁵ , R ⁶ , and R ⁷ include the same groups as R ¹ , R ² , and R ³ in Formula (1).

In the general formula (4), R ⁵ and R ⁶ or R ⁵ and R ⁷ may be bonded to each other to form a ring having 3 to 20 carbon atoms, particularly 5 to 12 carbon atoms together with the carbon atom to which they are bonded. Examples of such a ring include a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclooctadiene ring, a norbornene ring, an indene ring, and the like.

In the above general formula (4), R ⁸ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 40 carbon atoms. Examples and specific examples of the substituent of R ⁸ include the groups exemplified as R ¹ , R ² and R ³ in the general formula (1).

Specific examples of the α, β-unsaturated carboxylic acid ester represented by the general formula (4) include methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, and butyl acrylate. Tert-butyl acrylate, cyclohexyl acrylate, 1,1,2-trimethylpropyl acrylate, vinyl acrylate, allyl acrylate, isopropenyl acrylate, 1-cyclohexenyl acrylate, 10-undecenyl acrylate, acrylic acid Ethynyl, methyl methacrylate, ethyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-trimethylsiloxyethyl methacrylate, 2-chloropropyl methacrylate, 3-triethylsilylpropyl methacrylate, 3 methacrylic acid − ( Trimethoxysilyl) propyl, 3- (triethoxysilyl) propyl methacrylate, 3-tris (trimethylsiloxy) silylpropyl methacrylate, 3- (3,5,7,9,11,13,15-heptacyclopentyl methacrylate) pentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) propyl methacrylate 3- (3,5,7,9,11,13, 15 hepta isobutyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) propyl methacrylate 3- (3, 5, 7, 9, 11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl-oxy dimethylsilyl) methyl methacrylate 3- (3 , 5,7,9,1 , 13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl-oxy-butyldimethylsilyl) propyl, butyl methacrylate, isobutyl methacrylate Tert-butyl methacrylate, cyclohexyl methacrylate, 1,1,2-trimethylpropyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, octadecyl methacrylate, vinyl methacrylate, allyl methacrylate, methacrylic acid Isopropenyl, 1-cyclohexenyl methacrylate, 10-undecenyl methacrylate, ethynyl methacrylate, benzyl methacrylate, phenyl methacrylate, methyl crotonate, methyl cinnamate, ethyl 4-chlorocinnamate, 4-methoxycinnamic acid Methyl, methyl 1-cyclohexenecarboxylate, methyl cyclohexylideneacetate, 1,1,3,3,3-pentamethyl-1- [3-methacryloyloxy] propyl] disiloxane, α- [3- (methacryloyloxy) ) Propyl] -ω-butyl-polydimethylsiloxane and the like.

上記一般式（２）中のＲ^a、Ｒ^b、Ｒ^cは上記した定義通りである。 In the method for producing disilylketene acetal of the present invention, the α, β-unsaturated carboxylic acid ester of the above formula (4) is reacted with a hydrosilane or hydrosiloxane represented by the following general formula (2).

R ^a , R ^b , and R ^c in the general formula (2) are as defined above.

  The molar ratio of the compound of the above formula (4) to the compound of the above formula (2) is such that the compound of the above formula (4) is 0.1 mol per mole of the Si—H bond contained in the compound of the above formula (2). It is preferably at most 5 mol. In consideration of the efficiency of the reaction, the amount of the compound of the above formula (4) is more preferably 0.45 to 0.5 mol.

  In the method for producing disilylketene acetal of the present invention, the compound of the above formula (4) and the compound of the above formula (2) are reacted in the presence of a catalytic amount of tris (pentafluorophenyl) borane. The amount of tris (pentafluorophenyl) borane varies depending on the reaction substrate, but is usually 0.00001 to 10 mol%, preferably 0.001 to 1 mol%, based on the compound of the above formula (4).

  The reaction is generally carried out at normal pressure in an atmosphere of an inert gas such as nitrogen, but is not necessarily limited to this. The reaction temperature is usually -100 to 100C, preferably 0 to 60C.

  The method of mixing the substrate and the catalyst is arbitrary, but the α, β-unsaturated carboxylic acid ester of the above formula (4) generally has polymerizability as in the case of the compound of the above formula (1). Therefore, in order to control the reaction conditions and reduce the possibility of polymerization, a method of feeding the compound of the above formula (4) to a reactor containing a catalyst and the compound of the above formula (2) is most preferable.

  The reaction solvent is not necessarily required. In particular, when both the reaction substrates (4) and (2) are liquids, the reaction can be performed without a solvent, but the reaction may be performed using a solvent. Examples of usable solvents include hydrocarbon solvents such as hexane, isooctane, benzene, toluene, and xylene, and halogenated hydrocarbon solvents such as dichloromethane and dichloroethane.

  The addition of a polymerization inhibitor during the reaction is optional. When a polymerization inhibitor is used, hindered phenols such as 2,6-di-tert-butyl-4-methylphenol (BHT) are preferred.

上記一般式（５）中のＲ⁵、Ｒ⁶、Ｒ⁷及びＲ^a、Ｒ^b、Ｒ^cは上記した定義通りである。 According to the method of the present invention described above, a disilylketene acetal represented by the following general formula (5) is obtained.

In the general formula (5), R ⁵ , R ⁶ , R ⁷ and R ^a , R ^b , and R ^c are as defined above.

The present invention also provides a method for producing disilylketene acetal using a silylketene acetal represented by the following general formula (6) as a starting material.

In the general formula (6), R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 60, preferably 1 to 20 carbon atoms. In this case, the unsubstituted monovalent hydrocarbon group is preferably a group having 1 to 20 carbon atoms, and a substituted monovalent hydrocarbon group which partially or entirely replaces a hydrogen atom bonded to a carbon atom of the unsubstituted monovalent hydrocarbon group. The substituent of the valent hydrocarbon group does not include a halogen atom, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkenyloxy group, an organo group such as an aryloxy group, or a Si-H bond having 60 or less carbon atoms. A silyl group, an organo (poly) siloxy group having 1 to 1,000, preferably 1 to 50, particularly preferably 1 to 10 silicon atoms are suitable. Specific examples of the groups represented by R ⁹ and R ¹⁰ include the same groups as R ¹ , R ² and R ³ in the general formula (1).

In the general formula (6), R ⁹ and R ¹⁰ may be bonded to each other to form a ring having 3 to 20 carbon atoms, particularly 5 to 12 carbon atoms, together with the carbon atom to which they are bonded. Examples of such a ring include a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclooctadiene ring, a norbornene ring, an indene ring, and the like.

In the above general formula (6), R ¹¹ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 40 carbon atoms. Examples and specific examples of the substituent of R ¹¹ include the groups exemplified as R ¹ , R ² and R ³ in the general formula (1).

  Specific examples of the compound of the general formula (6) include 1-methoxy-1-trimethylsiloxyethene, 1-ethoxy-1-trimethylsiloxyethene, 1-butoxy-1-trimethylsiloxyethene, and 1-methoxy-1- Triethylsiloxyethene, 1-methoxy-1-trimethylsiloxypropene, 1-ethoxy-1-trimethylsiloxypropene, 1-butoxy-1-trimethylsiloxypropene, 1- (2-ethylhexyloxy) -1-trimethylsiloxypropene, 1-methoxy-1-triethylsiloxypropene, 1-methoxy-1-triisobutylsiloxypropene, 1-methoxy-1- (tert-butyldimethylsiloxy) propene, 1-methoxy-1-triisopropylsiloxypropene, 1-methoxy -2-methyl-1-tri Tylsiloxypropene, 1-methoxy-2-methyl-1-triethylsiloxypropene, 1-methoxy-2-methyl-1-triisobutylsiloxypropene, 1- (tert-butyldimethylsiloxy) -1-methoxy-2-methyl Propene, 1-methoxy-2-methyl-1-triisopropylsiloxypropene, 1- (chlorodimethylsiloxy) -1-methoxy-2-methylpropene, 1- (3-chloropropyldimethylsiloxy) -1-methoxy-2 -Methylpropene, 1- (ethoxydimethylsiloxy) -1-methoxy-2-methylpropene, 1-methoxy-2-methyl-1-phenyldimethylsiloxypropene, 1-methoxy-2-methyl-1-triphenylsiloxypropene , 1-methoxy-2-methyl-1- (tert-butyi) Diphenyl) siloxypropene, 1-methoxy-2-methyl-1- (pentamethyldisiloxanyloxy) propene, 1-ethoxy-2-methyl-1-triethylsiloxypropene, 1-isopropoxy-2-methyl-1 -Triethylsiloxypropene, 1-butoxy-2-methyl-1-triethylsiloxypropene, 1-tert-butoxy-2-methyl-1-triethylsiloxypropene, 2-methyl-1-triethylsiloxy-1-vinyloxypropene, 1-benzyloxy-2-methyl-1-triethylsiloxypropene, 1-cyclohexyloxy-2-methyl-1-triethylsiloxypropene, 1- (2-ethylhexyloxy) -2-methyl-1-triethylsiloxypropene, 1- (2-trimethylsiloxyethoxy) -2- Methyl-1-trimethylsiloxypropene, 1- (2-triethylsiloxyethoxy) -2-methyl-1-triethylsiloxypropene, 1-methoxy-1-triethylsiloxybutene, 1-methoxy-3-phenyl-1-triethylsiloxy And propene.

上記一般式（２）中のＲ^a、Ｒ^b、Ｒ^cはそれぞれ上記の定義通りである。 In the method for producing disilylketene acetal of the present invention, a hydrosilane or a hydrosiloxane represented by the following general formula (2) is reacted with the silylketene acetal of the above formula (6).

R ^a , R ^b , and R ^c in the general formula (2) are each as defined above.

  The molar ratio of the compound of the above formula (6) to the compound of the above formula (2) is arbitrary, but considering the efficiency of the reaction, the compound of the above formula (2) is added to 1 mol of the compound of the above formula (6). Is preferably 1.0 to 1.5 moles.

  In the method for producing disilylketene acetal of the present invention, the compound of the above formula (6) and the compound of the above formula (2) are reacted in the presence of a catalytic amount of tris (pentafluorophenyl) borane. The amount of tris (pentafluorophenyl) borane to be used varies depending on the reaction substrate, but is usually from 0.00001 to 10 mol%, preferably from 0.001 to 1 mol%, based on the compound of the above formula (6).

  The reaction is generally carried out at normal pressure in an atmosphere of an inert gas such as nitrogen, but is not necessarily limited to this. The reaction temperature is usually -100 to 100C, preferably 0 to 60C.

  The method of mixing the substrate and the catalyst is optional.A method in which both substrates are mixed in a reactor and a catalyst is added.A method in which one substrate and a catalyst are mixed in a reactor and the other substrate is fed. Both are possible.

  Although a reaction solvent is not necessarily required, the reaction may be performed using a solvent. Examples of usable solvents include hydrocarbon solvents such as hexane, isooctane, benzene, toluene, and xylene, and halogenated hydrocarbon solvents such as dichloromethane and dichloroethane.

上記一般式（７）中のＲ⁹、Ｒ¹⁰、及びＲ^a、Ｒ^b、Ｒ^c、Ｒ^d、Ｒ^e、Ｒ^fは上記した定義通りである。 According to the method of the present invention described above, a disilylketene acetal represented by the following general formula (7) is obtained.

R ⁹ , R ¹⁰ , and R ^a , R ^b , R ^c , R ^d , R ^e , and R ^f in the general formula (7) are as defined above.

  The silyl ketene acetal of the above general formula (3) or the disilyl ketene acetal of the above general formulas (5) and (7) obtained by the production method of the present invention is isolated from the reaction mixture by a method such as distillation. can do. Since there are few by-products such as carbonyl adducts, it is easy to obtain high-purity silylketene acetal by distillation. Before the isolation operation, a Lewis basic compound such as triethylamine or tributylamine may be added to the reaction mixture to deactivate the catalyst.

  Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, all the reactions were performed in a nitrogen atmosphere.

[Example 1] Synthesis of 1-methoxy-2-methyl-1-triethylsiloxypropene by reaction of methyl methacrylate and triethylsilane Four 100 mL units equipped with a Dimroth reflux condenser, stirrer, thermometer, and dropping funnel The neck flask was purged with nitrogen. 5.1 mg (0.01 mmol) of tris (pentafluorophenyl) borane (manufactured by Acros, lot No. A015140801; the same applies hereinafter), 220 mg of BHT (manufactured by Sumitomo Chemical Co., Ltd.), and 11.6 g (0.10 mol) of triethylsilane It was charged and stirred at room temperature for 0.5 hour. The flask was cooled using a dry ice-methanol bath, and the internal temperature was adjusted to -40 to -35 ° C. 10.0 g (0.10 mol) of methyl methacrylate was dropped from the dropping funnel over 2 hours. During the dropwise addition, the internal temperature was adjusted so as to be kept at -30 to -40C. Five minutes after the completion of the dropwise addition, gas chromatography (GC) confirmed that methyl methacrylate had disappeared. No carbonyl adduct or β adduct shown below was detected (Me represents a methyl group, Et represents an ethyl group).

One hour after the completion of the dropping, the dry ice-methanol bath was removed and the temperature was returned to room temperature. Using a Claisen head with a Vigreux tube having an inner diameter of 10 mm and a length of 10 cm, the slightly yellow transparent reaction liquid was distilled under reduced pressure to obtain 17.4 g of a colorless transparent liquid having a boiling point of 77 to 78 ° C./0.8 kPa. From the results of the NMR spectrum and the GC / MS spectrum, this liquid was identified as the target 1-methoxy-2-methyl-1-triethylsiloxypropene. The yield was 80.4%. The purity of the obtained 1-methoxy-2-methyl-1-triethylsiloxypropene was 98.8%.
¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 3.51 (3H, s), 1.56 (3H, d, J = 0.4 Hz), 1.53 (3H, d, J = 0) .4 Hz), 0.99 (9H, dt, J = 0.7 Hz, 8.0 Hz), 0.69 (6H, dq, J = 1.1 Hz, 7.9 Hz)
¹³ C-NMR (CDCl ₃ , 75.6 MHz): δ (ppm) 149.8, 91.0, 57.1, 16.8, 16.1, 6.6, 4.9
²⁹ Si-NMR (CDCl ₃ , 59.7 MHz): δ (ppm) 20.1
MS (EI): m / z 216 (M ^<+> ), 173, 117, 115, 89, 87, 86, 70, 59.

Comparative Example 1 Synthesis of 1-methoxy-2-methyl-1-triethylsiloxypropene by reaction of methyl methacrylate and triethylsilane using rhodium trichloride trihydrate as a catalyst Jimroth type reflux condenser, stirrer, A 100 mL four-necked flask equipped with a thermometer and a dropping funnel was purged with nitrogen. 2.6 mg (0.01 mmol) of rhodium trichloride trihydrate, 22 mg of BHT, and 10.0 g (0.10 mol) of methyl methacrylate were charged into a flask, and the flask was heated in an oil bath while stirring the contents. The internal temperature was adjusted to 51 ° C. 11.6 g (0.10 mol) of triethylsilane was added dropwise from the dropping funnel over 3 hours. Heat generation was observed with the dropping, and the heating was adjusted so that the internal temperature was maintained at 54 to 60 ° C. After completion of the dropwise addition, the mixture was stirred at 56 to 59 ° C. for 1 hour and further stirred at 65 ° C. for 1 hour. As a result, methyl methacrylate disappeared. According to GC and GC / MS analysis of the reaction mixture, silyl ketene acetal was obtained as a main product, but other carbonyl adducts and β adducts were formed. The ratio of GC area% (TCD) of the product was silyl ketene acetal: carbonyl adduct: β adduct = 1: 0.081: 0.002. The reaction mixture was distilled under reduced pressure using the same apparatus as in Example 1. As a result, 18.1 g of a colorless transparent fraction having a boiling point of 79 to 79.5 ° C./0.85 kPa was obtained. When the fraction was analyzed by GC (TCD), the composition was as follows.
Silyl ketene acetal: 94.5%
Carbonyl adduct: 4.1%
β adduct: 0%
Others: 1.4%
This result indicates that it is difficult to purify the target product by distillation.

Example 2 1,3-bis (1-methoxy-2-methyl-1-propenyloxy) -1,1,3,3 by reaction of methyl methacrylate with 1,1,3,3-tetramethyldisiloxane Synthesis of 3-tetramethyldisiloxane A 100 mL four-necked flask equipped with a Dimroth reflux condenser, stirrer, thermometer, and dropping funnel was purged with nitrogen. 1,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene (hereinafter I-1330, manufactured by Ciba Specialty Chemicals) is placed in the flask. 258 mg, 5 mL of toluene and 0.5 mg (0.001 mmol) of tris (pentafluorophenyl) borane were charged, and the content was cooled to 2 ° C. in an ice-water bath while stirring. A mixture of 20.0 g (0.20 mol) of methyl methacrylate and 13.4 g (0.10 mol) of 1,1,3,3-tetramethyldisiloxane was dropped from the dropping funnel over 4 hours. The internal temperature rose to a maximum of 7.5 ° C. After completion of the dropping, stirring was continued at 2 to 4 ° C. for 1.5 hours. As a result, methyl methacrylate had disappeared. When the reaction mixture was distilled under reduced pressure, 26.5 g of a colorless transparent fraction having a boiling point of 96 to 97.5 ° C./0.2 kPa was obtained. According to the results of NMR and GC / MS, this liquid was the target 1,3-bis (1 -Methoxy-2-methyl-1-propenyloxy) -1,1,3,3-tetramethyldisiloxane. The yield was 79.1%.
¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 3.51 (6H, s), 1.56 (6H, d, J = 0.4 Hz), 1.52 (6H, d, J = 0) .4Hz), 0.20 (12H, s)
¹³ C-NMR (CDCl ₃ , 75.6 MHz): δ (ppm) 148.7, 91.0, 56.6, 16.8, 16.1, −0.7
²⁹ Si-NMR (CDCl ₃ , 59.7 MHz): δ (ppm) -12.2.
MS (EI): m / z 334 (M ^<+> ), 233, 217, 179, 163, 133.

Example 3 Synthesis of 2-Methyl-1-triethylsiloxy-1-vinyloxypropene by Reaction of Vinyl Methacrylate and Triethylsilane A 100 mL four-hole flask equipped with a Dimroth reflux condenser, stirrer, thermometer, and dropping funnel was used. The head flask was purged with nitrogen. A flask was charged with 258 mg of I-1330, 7.7 mg (0.015 mmol) of tris (pentafluorophenyl) borane, and 11.6 g (0.10 mol) of triethylsilane, and the contents were stirred at room temperature for 0.5 hour. . The flask was cooled in an ice water bath, and the internal temperature was adjusted to 1.5 ° C. 11.2 g (0.10 mol) of vinyl methacrylate was dropped from the dropping funnel over 2.5 hours. The internal temperature rose to a maximum of 6.5 ° C. After completion of the dropwise addition, stirring was continued at 2 ° C for 2 hours, and the ice water bath was removed, followed by stirring at 15 to 20 ° C for another 5 hours. The obtained reaction mixture was distilled under reduced pressure. 19.3 g of a colorless transparent fraction having a boiling point of 79.5 to 80 ° C./0.8 kPa was obtained. According to the result of NMR and GC / MS, this liquid was the target 2-methyl-1-triethylsiloxy-1-vinyloxy. It was identified as propene. The yield was 84.5%.
¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 6.34 (1H, dd, J = 6.3 Hz, 14.0 Hz), 4.49 (1H, dd, J = 1.8 Hz, 14.3). 0 Hz), 4.15 (1H, dd, J = 1.8 Hz, 6.3 Hz), 1.58 (3H, d, J = 0.4 Hz), 1.53 (3H, d, J = 0.4 Hz) ), 0.98 (9H, dt, J = 0.7 Hz, 7.9 Hz), 0.68 (6H, dq, J = 1.2 Hz, 7.9 Hz)
¹³ C-NMR (CDCl ₃ , 75.6 MHz): δ (ppm) 149.2, 146.3, 93.0, 90.7, 16.7, 16.1, 6.5, 5.0
²⁹ Si-NMR (CDCl ₃ , 59.7 MHz): δ (ppm) 21.9
MS (EI): m / z 228 (M ^<+> ), 213, 115, 87, 70, 59.

Example 4 Synthesis of 1-tert-butoxy-2-methyl-1-triethylsiloxypropene by reaction of tert-butyl methacrylate and triethylsilane A Dimroth-type reflux condenser, stirrer, thermometer, and dropping funnel were provided. The 100 mL four-necked flask was purged with nitrogen. A flask was charged with 258 mg of I-1330, 7.7 mg (0.015 mmol) of tris (pentafluorophenyl) borane, and 11.6 g (0.10 mol) of triethylsilane, and the contents were stirred at room temperature for 0.5 hours. The flask was cooled in an ice water bath to adjust the internal temperature to 3.5 ° C., and 13.5 g (0.095 mol) of tert-butyl methacrylate was added from the dropping funnel over 2.5 hours. During this time, the internal temperature rose to a maximum of 6 ° C. When the stirring was continued at 3 to 3.5 ° C. for 3 hours after the completion of the dropwise addition, it was found by GC analysis that triethylsilane had disappeared. A reaction mixture containing a small amount of white solid was obtained, which was distilled under reduced pressure. 24.8 g of a colorless and transparent fraction having a boiling point of 73 to 75 ° C./0.3 kPa was obtained. From the results of NMR and MS, this liquid was the target 1-tert-butoxy-2-methyl-1-triethylsiloxypropene. Was identified. The yield was 81.5% (vs. triethylsilane).
¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 1.55 (3H, d, J = 0.4 Hz), 1.54 (3H, d, J = 0.4 Hz), 1.27 (9H) , S), 0.98 (9H, dt, J = 0.6 Hz, 7.8 Hz), 0.69 (6H, dq, J = 1.1 Hz, 7.9 Hz)
¹³ C-NMR (CDCl ₃ , 75.6 MHz): δ (ppm) 146.7, 95.6, 78.9, 29.1, 18.2, 17.5, 6.7, 5.2
²⁹ Si-NMR (CDCl ₃ , 59.7 MHz): δ (ppm) 20.1
MS (EI): m / z 258 (M ^<+> ), 229, 202, 173, 157, 133, 115, 103, 87, 75, 70, 57, 41.

[Example 5] Synthesis of 2-methyl-1-triethylsiloxy-1-trimethylsiloxypropene by reaction of trimethylsilyl methacrylate and triethylsilane 200 mL of 4-mL equipped with a Dimroth reflux condenser, a stirrer, a thermometer, and a dropping funnel. The head flask was purged with nitrogen. A flask was charged with 258 mg of I-1330, 5.1 mg (0.01 mmol) of tris (pentafluorophenyl) borane and 11.6 g (0.10 mol) of triethylsilane, and the contents were stirred at room temperature for 15 minutes. The flask was cooled in an ice water bath to adjust the internal temperature to 4.5 ° C., and 11.1 g (0.07 mol) of trimethylsilyl methacrylate was added from a dropping funnel over 4 hours. During this time, the internal temperature rose to a maximum of 8 ° C. After 3 mg (0.006 mmol) of tris (pentafluorophenyl) borane was added as a toluene solution, 4.7 g (0.03 mol) of trimethylsilyl methacrylate was added from a dropping funnel in 1 hour. After completion of the dropwise addition, stirring was further continued at 5 ° C. for 9 hours. According to GC analysis, triethylsilane had disappeared. To the reaction mixture, 22 μL (0.16 mmol) of triethylamine was added, and the mixture was stirred for 0.5 hour, cooled, and returned to room temperature. The reaction mixture containing a small amount of white solid was distilled under reduced pressure. 13.5 g of a colorless transparent fraction having a boiling point of 69 to 71 ° C./0.4 kPa was obtained. From the results of NMR and MS, it was concluded that this liquid was the intended 2-methyl-1-triethylsiloxy-1-trimethylsiloxypropene. Identified. The yield was 49.2%.
¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 1.53 (3H, s), 1.49 (3H, s), 0.98 (9H, t, J = 7.9 Hz), 0. 68 (6H, q, J = 7.9 Hz), 0.18 (9H, s)
¹³ C-NMR (CDCl ₃ , 75.6 MHz): δ (ppm) 145.0, 87.7, 17.4, 17.2, 6.7, 5.1, 0.4
²⁹ Si-NMR (CDCl ₃ , 59.7 MHz): δ (ppm) 20.6, 19.6
MS (EI): m / z 274 (M ⁺ ), 259, 231, 175, 147, 119, 115, 87, 86, 73, 59.

Example 6 Synthesis of 1,1-bis (triethylsiloxy) -2-methylpropene by the reaction of methyl methacrylate and triethylsilane A 200 mL four-hole flask equipped with a Dimroth reflux condenser, stirrer, thermometer, and dropping funnel was used. The head flask was purged with nitrogen. 1.9 mg (0.00375 mmol) of tris (pentafluorophenyl) borane, 17.4 g (0.15 mol) of triethylsilane and 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) 581 mg of -2,4,6-trimethylbenzene was charged into the flask and stirred at room temperature for 15 minutes. The flask was cooled using an ice bath, and the internal temperature was adjusted to 1.5 ° C. 7.5 g (0.075 mol) of methyl methacrylate was dropped from the dropping funnel over 2.5 hours. Heat generation was observed with the dropping, and the internal temperature rose to a maximum of 7 ° C. Five minutes after the completion of the dropwise addition, gas chromatography (GC) confirmed that methyl methacrylate had disappeared. After 2 hours, the ice bath was removed, and the reaction mixture was stirred at room temperature for 18 hours, and then 10.5 μL (0.075 mmol) of triethylamine was added. By GC / MS analysis of the reaction mixture, it was found that the main product was the target product, and the carbonyl adducts and β adducts shown below and by-products derived from these were not produced (Me was methyl Group, Et represents an ethyl group).

This mixture was distilled under reduced pressure using a Claisen head equipped with a Vigreux tube having an inner diameter of 10 mm and a length of 10 cm to obtain 17.9 g of a colorless transparent liquid having a boiling point of 108.5 to 109 ° C./0.2 kPa. From the measurement results of the NMR spectrum and the GC / MS spectrum, this liquid was identified as the target 1,1-bis (triethylsiloxy) -2-methylpropene. GC purity was> 99.9% and yield was 75.4%.
¹ H-NMR (CDCl ₃ , 300 MHz): δ (ppm) 1.50 (6H, s), 0.98 (18H, t, J = 7.9 Hz), 0.67 (12H, q, J = 7) .9Hz)
¹³ C-NMR (CDCl ₃ , 75.6 MHz): δ (ppm) 145.2, 87.1, 17.4, 6.7, 5.1
²⁹ Si-NMR (CDCl ₃ , 59.7 MHz): δ (ppm) 20.6
MS (EI): m / z 316 (M ^<+> ), 259, 217, 189, 173, 115, 87, 59.

Example 7 Synthesis of 1,1-bis (triethylsiloxy) -2-methylpropene by reaction of 1-methoxy-2-methyl-1-triethylsiloxypropene and triethylsilane Jimroth-type reflux condenser, stirrer, temperature A 200 mL four-necked flask equipped with a total and a dropping funnel was purged with nitrogen. A flask was charged with 388 mg of I-1330, 1.28 mg (0.0025 mmol) of tris (pentafluorophenyl) borane, and 5.8 g (0.05 mol) of triethylsilane, and the contents were stirred at room temperature for 15 minutes. The flask was cooled in an ice-water bath to adjust the internal temperature to 5 ° C., and 10.8 g (0.050 mol) of 1-methoxy-2-methyl-1-triethylsiloxypropene was added from the dropping funnel over 3 hours. During this time, the internal temperature rose to a maximum of 9 ° C. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 4 hours, and the reaction was continued at room temperature for 12 hours. It was confirmed by GC / MS analysis that the target compound was produced. 9.8 μL (0.07 mmol) of triethylamine was added to the reaction mixture, and the mixture was stirred for 0.5 hour and then distilled under reduced pressure. 11.0 g of a colorless transparent fraction having a boiling point of 91 to 91.5 ° C./0.13 kPa was obtained. From the results of NMR and MS, this liquid was obtained using the objective 1,1-bis (triethylsiloxy) -2-methylpropene. Was identified. The yield was 69.5%.

Claims (6)

An α, β-unsaturated carboxylic acid ester represented by the following general formula (1) and a hydrosilane or hydrosiloxane represented by the following general formula (2) are prepared in the presence of a catalytic amount of tris (pentafluorophenyl) borane. A method for producing a silyl ketene acetal represented by the following general formula (3), characterized by reacting:

(In the formula, R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having ¹ to 60 carbon atoms. Alternatively, R ¹ and R ² or R ¹ and R ³ may be mutually bonded to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded, and R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 40 carbon atoms, or a substituted or unsubstituted monovalent hydrocarbon group. It represents an unsubstituted silyl group having 60 or less carbon atoms and not containing a Si—H bond.)

(Wherein, R ^a , R ^b , and R ^c each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an organooxy group having 1 to 20 carbon atoms, and a silicon atom having 1 to 1,000 silicon atoms. Represents a group selected from an organo (poly) siloxy group and a halogen atom, or represents a silicon atom together with a silicon atom to which R ^a and R ^b , R ^a and R ^c or R ^b and R ^c are bonded to each other. It may form a siloxane ring having a number of 3 to 50 or a silicon-containing ring having 1 to 20 carbon atoms, and R ^a , R ^b and R ^c may be bonded to each other together with a silicon atom to which they are bonded. (A cage siloxane having 6 to 50 silicon atoms may be formed.)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ^a , R ^b , and R ^c represent groups defined by the formulas (1) and (2), respectively.)   An α, β-unsaturated carboxylic acid ester represented by the formula (1) is added to a reactor containing a mixture of the hydrosilane or hydrosiloxane represented by the formula (2) and a catalytic amount of tris (pentafluorophenyl) borane. The method for producing a silyl ketene acetal according to claim 1, wherein:   In a reactor containing a catalytic amount of tris (pentafluorophenyl) borane, an α, β-unsaturated carboxylic acid ester represented by the formula (1) and a hydrosilane or hydrosiloxane represented by the formula (2) are added to a reactor represented by the formula: The compound according to claim 1, wherein the compound is added while adjusting the molar ratio of the Si-H bond of the compound of formula (2) to 0.9 to 1.1 with respect to 1 mole of the compound of (1). A method for producing a silyl ketene acetal. An α, β-unsaturated carboxylic acid ester represented by the following general formula (4) and a hydrosilane or hydrosiloxane represented by the following general formula (2) are prepared in the presence of a catalytic amount of tris (pentafluorophenyl) borane. A method for producing a disilylketene acetal represented by the following general formula (5), characterized by reacting:

(Wherein, R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 60 carbon atoms. Alternatively, R ⁵ and R ⁶ or R ⁵ and R ^{6 7} may be bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded. R ⁸ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 40 carbon atoms.)

(Wherein, R ^a , R ^b , and R ^c each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an organooxy group having 1 to 20 carbon atoms, and a silicon atom having 1 to 1,000 silicon atoms. Represents a group selected from an organo (poly) siloxy group and a halogen atom, or represents a silicon atom together with a silicon atom to which R ^a and R ^b , R ^a and R ^c or R ^b and R ^c are bonded to each other. It may form a siloxane ring having a number of 3 to 50 or a silicon-containing ring having 1 to 20 carbon atoms, and R ^a , R ^b and R ^c may be bonded to each other together with a silicon atom to which they are bonded. (A cage siloxane having 6 to 50 silicon atoms may be formed.)

(In the formula, R ⁵ , R ⁶ , R ⁷ , R ^a , R ^b , and R ^c each represent a group defined by the formulas (4) and (2).)   In a reactor containing a mixture of a hydrosilane or hydrosiloxane represented by the formula (2) and a catalytic amount of tris (pentafluorophenyl) borane, 0.5 to 1 mol of Si—H bond of the compound of the formula (2) is added. The method for producing a disilylketene acetal according to claim 4, wherein an α, β-unsaturated carboxylic acid ester represented by the following formula (4) is added in a molar amount or less. A silyl ketene acetal represented by the following general formula (6) is reacted with a hydrosilane or hydrosiloxane represented by the following general formula (2) in the presence of a catalytic amount of tris (pentafluorophenyl) borane. And a method for producing a disilylketene acetal represented by the following general formula (7).

(Wherein, R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 60 carbon atoms. Alternatively, R ⁹ and R ¹⁰ are bonded to each other to form a bond. R ¹¹ may represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 40 carbon atoms, and R ^d , R ^e , and R ^f each represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 40 carbon atoms. A group independently selected from a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an organooxy group having 1 to 20 carbon atoms, an organo (poly) siloxy group having 1 to 1,000 silicon atoms, and a halogen atom Or R ^d and R ^e , R ^d and R ^f or R ^e and R ^f are bonded to each other to form a siloxane ring having 3 to 50 silicon atoms together with the silicon atom to which they are bonded, or It may form 1 to 20 silicon-containing rings. ^d, R ^e, R ^f may form a cage siloxane silicon atoms of 6 to 50 together with the silicon atom to which they are attached.)

(Wherein, R ^a , R ^b , and R ^c each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an organooxy group having 1 to 20 carbon atoms, and a silicon atom having 1 to 1,000 silicon atoms. Represents a group selected from an organo (poly) siloxy group and a halogen atom, or represents a silicon atom together with a silicon atom to which R ^a and R ^b , R ^a and R ^c or R ^b and R ^c are bonded to each other. It may form a siloxane ring having a number of 3 to 50 or a silicon-containing ring having 1 to 20 carbon atoms, and R ^a , R ^b and R ^c may be bonded to each other together with a silicon atom to which they are bonded. (A cage siloxane having 6 to 50 silicon atoms may be formed.)

(In the formula, R ⁹ , R ¹⁰ , R ^a , R ^b , R ^c , R ^d , R ^e , and R ^f represent groups defined by the formulas (2) and (6), respectively.)