JP2017075128A - Cage silsesquioxane having 4 different substituents in confrontation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of silsesquioxane capable of manufacturing cage silsesquioxane having 4 different substituents in a confrontation.SOLUTION: Cage silsesquioxane having 4 different substituents in a confrontation can be manufactured in good efficiency by condensing cyclic siloxane represented by the following formula (B) and cyclic siloxane represented by the following formula (C). In the formulae (B), (C) and (D), Rand Reach represents a hydrocarbon group having 1 to 20 carbon atoms, A represents an alkali metal, each Ris the same hydrocarbon group, each Ris the same hydrocarbon group, and between Rand Rare different hydrocarbon groups.SELECTED DRAWING: None

Description

  The present invention relates to a cage-type silsesquioxane and a method for producing the same, and more particularly to a cage-type silsesquioxane having four different substituents on the face and a method for producing the same.

The structure-regulated silicon compounds are expected to be applied to material applications requiring high physical properties, and their synthesis has been actively studied in recent years. In particular, cage-type silsesquioxane is expected to have high heat resistance, oxidation resistance, and weather resistance due to its unique structure, and is attracting attention as a basic compound for various functional materials, especially organic-inorganic hybrid materials. I'm bathing.
There have been many reports on the synthesis of cage-type silsesquioxanes, which can be synthesized from cyclic silanols (see, for example, Non-Patent Documents 1 to 4), and various organic groups have been introduced so far. Type silsesquioxane has been reported.

M. Unno et al., Chem. Lett. 1998, 489. M. Unno et al., Bull. Chem. Soc. Jpn. 2000, 73, 215. S. Tateyama et al., J. Organomet. Chem. 2010, 695, 898. H. Seki et al., J. Organomet. Chem. 2010, 695, 1363.

Among cage-type silsesquioxanes, those having four different substituents on the opposite side are called Janus cubes, and their application is highly anticipated because they can impart heat resistance to silane coupling agents. However, it can be said that it is extremely difficult to introduce a plurality of types of substituents into the cage silsesquioxane, particularly to control the positional relationship.
An object of this invention is to provide the manufacturing method of the silsesquioxane which can manufacture the cage-type silsesquioxane which has four different substituents in a facing surface.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have condensed a fluorinated cyclic siloxane of “all-cis” type with a cyclic siloxane salt of “all-cis” type. The inventors have found that a cage-type silsesquioxane having four different substituents on the opposite side can be efficiently produced, and completed the present invention.

（式（Ｂ）、（Ｃ）、及び（Ｄ）中、Ｒ^１及びＲ^２はそれぞれ炭素数１〜２０の炭化水素基を、Ａはアルカリ金属を表し、Ｒ^１同士及びＲ^２同士はそれぞれ同一の炭化水素基であることを、Ｒ^１とＲ^２間はそれぞれ異なる炭化水素基であることを表す。）
＜２＞ 下記式（Ａ）で表される環状シロキサンと三フッ化ホウ素を反応させて下記式（
Ｂ）で表される環状シロキサンを生成するフッ素化工程を含む、＜１＞に記載のシルセスキオキサンの製造方法。

（式（Ａ）及び（Ｂ）中、Ｒ^１は炭素数１〜２０の炭化水素基を表し、Ｒ^１同士は同一の炭化水素基であることを表す。）
＜３＞ 下記式（Ｄ’）で表されるシルセスキオキサン。

（式（Ｄ’）中、Ｒ^３及びＲ^４はそれぞれ酸素原子及びハロゲン原子からなる群より選択される少なくとも１種の原子を含んでいてもよい炭素数１〜２０の炭化水素基、水素原子、ハロゲン原子、ヒドロキシル基、又は炭素数０〜６のシリル基を表し、Ｒ^３同士及びＲ^４同士はそれぞれ同一の置換基であることを、Ｒ^３とＲ^４間はそれぞれ異なる置換基であることを表す。）
＜４＞ 下記式（Ａ）で表される環状シロキサンと三フッ化ホウ素を反応させて下記式（
Ｂ）で表される環状シロキサンを生成するフッ素化工程を含む、環状シロキサン（Ｂ）の製造方法。

（式（Ａ）及び（Ｂ）中、Ｒ^１は炭素数１〜２０の炭化水素基を表し、Ｒ^１同士は同一の炭化水素基であることを表す。）
＜５＞ 下記式（Ｂ）で表される環状シロキサン。

（式（Ｂ）中、Ｒ^１は炭素数１〜２０の炭化水素基を表し、Ｒ^１同士は同一の炭化水素基であることを表す。） That is, the present invention is as follows.
<1> A condensation step of reacting a cyclic siloxane represented by the following formula (B) with a cyclic siloxane represented by the following formula (C) to produce a silsesquioxane represented by the following formula (D) is included. The manufacturing method of silsesquioxane.

(In formulas (B), (C), and (D), R ¹ and R ² each represent a hydrocarbon group having 1 to 20 carbon atoms, A represents an alkali metal, and R ¹ and R ² each represent (Indicating that they are the same hydrocarbon group, R ¹ and R ² are different hydrocarbon groups.)
<2> A cyclic siloxane represented by the following formula (A) and boron trifluoride are reacted to form the following formula (
The manufacturing method of the silsesquioxane as described in <1> including the fluorination process which produces | generates the cyclic siloxane represented by B).

(In formulas (A) and (B), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ represents the same hydrocarbon group.)
<3> Silsesquioxane represented by the following formula (D ′).

(In Formula (D ′), R ³ and R ⁴ are each a hydrocarbon group having 1 to 20 carbon atoms and a hydrogen atom, each of which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. , A halogen atom, a hydroxyl group, or a silyl group having 0 to 6 carbon atoms, R ³ and R ⁴ are the same substituents, and R ³ and R ⁴ are different substituents. Represents this.)
<4> A cyclic siloxane represented by the following formula (A) and boron trifluoride are reacted to form the following formula (
The manufacturing method of cyclic siloxane (B) including the fluorination process which produces | generates the cyclic siloxane represented by B).

(In formulas (A) and (B), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ represents the same hydrocarbon group.)
<5> Cyclic siloxane represented by the following formula (B).

(In formula (B), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ represents the same hydrocarbon group.)

  According to the present invention, a cage-type silsesquioxane having four different substituents on the opposite side can be produced.

  In describing the present invention, specific examples will be described. However, the present invention is not limited to the following contents without departing from the gist of the present invention, and can be implemented with appropriate modifications.

（式（Ｂ）、（Ｃ）、及び（Ｄ）中、Ｒ^１及びＲ^２はそれぞれ炭素数１〜２０の炭化水素基を、Ａはアルカリ金属を表し、Ｒ^１同士及びＲ^２同士はそれぞれ同一の炭化水素基であることを、Ｒ^１とＲ^２間はそれぞれ異なる炭化水素基であることを表す。）
前述のように、かご型シルセスキオキサンに複数種類の置換基を導入すること、特にその位置関係を制御することは極めて困難であった。本発明者らは、式（Ｂ）で表される「ａｌｌ−ｃｉｓ」型のフッ素化された環状シロキサンと、式（Ｃ）で表される「ａｌｌ−ｃｉｓ」型の環状シロキサン塩を縮合させることにより、異なる置換基を対面に４つずつ
有するかご型シルセスキオキサンを効率良く製造することができることを見出したのである。
以下、「式（Ｂ）で表される環状シロキサン」、「式（Ｃ）で表される環状シロキサン」、縮合工程の条件等について、詳細に説明する。 <Method for producing silsesquioxane>
The production method of silsesquioxane which is one embodiment of the present invention (hereinafter sometimes abbreviated as “production method of the present invention”) includes a cyclic siloxane represented by the following formula (B) and the following formula (C). It includes a condensation step (hereinafter sometimes abbreviated as “condensation step”) in which a silsesquioxane represented by the following formula (D) is produced by reacting a cyclic siloxane represented by formula (D).

(In formulas (B), (C), and (D), R ¹ and R ² each represent a hydrocarbon group having 1 to 20 carbon atoms, A represents an alkali metal, and R ¹ and R ² each represent (Indicating that they are the same hydrocarbon group, R ¹ and R ² are different hydrocarbon groups.)
As described above, it has been extremely difficult to introduce a plurality of types of substituents into the cage silsesquioxane, and in particular to control the positional relationship. The inventors condense the “all-cis” type fluorinated cyclic siloxane represented by the formula (B) with the “all-cis” type cyclic siloxane salt represented by the formula (C). Thus, it has been found that a cage-type silsesquioxane having four different substituents on the opposite side can be efficiently produced.
Hereinafter, “cyclic siloxane represented by the formula (B)”, “cyclic siloxane represented by the formula (C)”, conditions of the condensation step, and the like will be described in detail.

R ¹ of the cyclic siloxane represented by the formula (B) represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ is the same hydrocarbon group, but “hydrocarbon group” Is not limited to a linear saturated hydrocarbon group, and may have a branched structure, a cyclic structure, and a carbon-carbon unsaturated bond (branched structure, cyclic structure, and carbon-carbon unsaturated group). It may have at least one selected from the group consisting of saturated bonds.)
The carbon number of the hydrocarbon group for R ¹ is preferably 16 or less, more preferably 12 or less, and preferably 8 or less.
R ¹ includes a methyl group (—CH ₃ ), an ethyl group (—C ₂ H ₅ ), a vinyl group (—CH═CH ₂ ), an ethynyl group (—C≡CH), an n-propyl group ( ^—n C ₃ H _7), i- propyl _{^{(- i C 3 H 7)}} , n- butyl _{^{(- n C 4 H 9)}} , t- butyl _{^{(- t C 4 H 9)}} , n- pentyl (- ⁿ C ₅ H _11), n- hexyl group _{^{(- n C 6 H 13)}} , c- hexyl group _{^{(- c C 6 H 11)}} , phenyl group _{(-C 6 H} 5), naphthyl _{(-C 10} H ₇ ) and the like.

R ² of the cyclic siloxane represented by the formula (C) represents a hydrocarbon group having 1 to 20 carbon atoms, and R ² is the same hydrocarbon group, and between R ¹ and R ^2, respectively. Although it represents a different hydrocarbon group, the “hydrocarbon group” has the same meaning as in the case of R ¹ . Moreover, lithium, sodium, potassium etc. are mentioned as an alkali metal of A.
The carbon number of the hydrocarbon group for R ² is preferably 16 or less, more preferably 12 or less, and preferably 8 or less.
R ² includes a methyl group (—CH ₃ ), an ethyl group (—C ₂ H ₅ ), a vinyl group (—CH═CH ₂ ), an ethynyl group (—C≡CH), an n-propyl group ( ^—n C). ₃ H _7), i- propyl _{^{(- i C 3 H 7)}} , n- butyl _{^{(- n C 4 H 9)}} , t- butyl _{^{(- t C 4 H 9)}} , n- pentyl (- ⁿ C ₅ H _11), n- hexyl group _{^{(- n C 6 H 13)}} , c- hexyl group _{^{(- c C 6 H 11)}} , phenyl group _{(-C 6 H} 5), naphthyl _{(-C 10} H ₇ ) and the like.

As a combination of R ¹ and R ² , a methyl group (—CH ₃ ), a phenyl group (—C ₆ H ₅ ), an ethyl group (—C ₂ H ₅ ), a phenyl group (—C ₆ H ₅ ), a vinyl group (—CH═CH ₂ ), phenyl group (—C ₆ H ₅ ), ethynyl group (—C≡CH), phenyl group (—C ₆ H ₅ ), n-propyl group ( ^—n C ₃ H ₇ ) phenyl group _{(-C 6} H 5), i- propyl ^(- _i C 3 _{H 7)} and a phenyl group _{(-C 6} H 5), t- butyl ^(- _t C 4 _{H 9)} and phenyl group (- C ₆ H ₅ ) and the like. As will be described later, when ^one of R ¹ and R ² is a phenyl group, the phenyl group can be substituted with a chloro group (—Cl), so that various functional groups can be introduced.

なお、式（ｉ）で表される反応の詳細については、O. I. Shchegolikhinaet al.,Inorg. Chem., 2002, 41, 6892、R. Ito et al., Chem. Lett., 2009, 38, 364、Y. A. Pozdnyakova et al., Inorg. Chem., 2010, 49, 572等を参照することができる。 The cyclic siloxane represented by the formula (C) can be produced, for example, by a condensation reaction such as trialkoxy (alkyl) silane represented by the following formula (i).

For details of the reaction represented by the formula (i), OI Shchegolikhina et al., Inorg. Chem., 2002, 41, 6892, R. Ito et al., Chem. Lett., 2009, 38, 364, Reference can be made to YA Pozdnyakova et al., Inorg. Chem., 2010, 49, 572 and the like.

  The amount of the cyclic siloxane represented by the formula (C) used in the condensation step is usually 1 or more times, preferably 1.5 or more times, more in terms of the amount of the siloxane represented by the formula (B). Preferably it is 2 times or more, usually 10 times or less, preferably 5 times or less, more preferably 3 times or less. If it is in the said range, cage-type silsesquioxane can be manufactured more efficiently.

  In the condensation step, it is preferable to use a solvent. The type of the solvent is not particularly limited and can be appropriately selected according to the purpose. Specifically, hydrocarbon solvents such as hexane, benzene and toluene, diethyl ether, 1,4-dioxane, tetrahydrofuran ( THF) and the like, halogen solvents such as methylene chloride and chloroform, acetone, dimethylacetamide (DMA), N, N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO) and the like Aprotic polar solvents and the like. Of these, halogen solvents are preferred. In addition, the boiling point of a solvent is 25 degreeC or more normally, Preferably it is 40 degreeC or more, More preferably, it is 60 degreeC or more, and is 200 degrees C or less normally, Preferably it is 150 degrees C or less, More preferably, it is 100 degrees C or less. If it is in the said range, preferable reaction temperature can be maintained by recirculation | reflux.

The reaction temperature in the condensation step is usually 25 ° C or higher, preferably 40 ° C or higher, more preferably 60 ° C or higher, and usually 200 ° C or lower, preferably 150 ° C or lower, more preferably 100 ° C or lower.
The reaction time in the condensation step is usually 10 hours or longer, preferably 1 day or longer, more preferably 3 days or longer, and usually 10 days or shorter, preferably 7 days or shorter, more preferably 5 days or shorter.
The condensation step is usually performed under an inert atmosphere such as nitrogen or argon.
In addition, if it is in the said range, cage-type silsesquioxane can be manufactured more efficiently.

（式（Ａ）及び（Ｂ）中、Ｒ^１は炭素数１〜２０の炭化水素基を表し、Ｒ^１同士は同一の炭化水素基であることを表す。）
以下、以下、「式（Ａ）で表される環状シロキサン」、フッ素化工程の条件等について、詳細に説明する。 The production method of the present invention is not particularly limited as long as it includes the above-described condensation step, but the cyclic siloxane represented by the following formula (A) and boron trifluoride are reacted to form the following formula (B). A cyclic siloxane represented by the formula (B) may be used for the condensation step, including a fluorination step (hereinafter, may be abbreviated as “fluorination step”). preferable.

(In formulas (A) and (B), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ represents the same hydrocarbon group.)
Hereinafter, the “cyclic siloxane represented by the formula (A)”, conditions for the fluorination step, and the like will be described in detail.

なお、式（ｉｉ）で表される反応の詳細については、J. F. Brown et al., J. Am. Chem. Soc., 1965, 87, 4317、J. F. Brown, Jr. et al., J. Am. Chem. Soc., 1965, 87, 4313、F. J. Feher et al., Main Group Chem., 1997, 2, 123、M. Unno et al., Bull. Chem. Soc. Jpn., 2000, 73, 215等を参照することができ、式（ｉｉｉ）で表される反応
の詳細については、O. I. Shchegolikhina et al., Inorg. Chem., 2002, 41, 6892、R. Ito et al., Chem. Lett., 2009, 38, 364、Y. A. Pozdnyakovaet al.,Inorg. Chem., 2010, 49, 572等を参照することができる。 The cyclic siloxane represented by the formula (A) can be produced by a condensation reaction such as trichloro (alkyl) silane or trialkoxy (alkyl) silane represented by the following formula (ii) or (iii). .

For details of the reaction represented by the formula (ii), see JF Brown et al., J. Am. Chem. Soc., 1965, 87, 4317, JF Brown, Jr. et al., J. Am. Chem. Soc., 1965, 87, 4313, FJ Feher et al., Main Group Chem., 1997, 2, 123, M. Unno et al., Bull. Chem. Soc. Jpn., 2000, 73, 215, etc. For details of the reaction represented by formula (iii), see OI Shchegolikhina et al., Inorg. Chem., 2002, 41, 6892, R. Ito et al., Chem. Lett., 2009, 38, 364, YA Pozdnyakova et al., Inorg. Chem., 2010, 49, 572, etc. can be referred to.

The fluorination step is a step of reacting the cyclic siloxane represented by the formula (A) with boron trifluoride, but the boron trifluoride may be a complex formed with a Lewis base such as diethyl ether. .
The amount of boron trifluoride used in the fluorination step is usually 1 time or more, preferably 5 times or more, more preferably 10 times or more, in terms of the amount of the substance with respect to the cyclic siloxane represented by the formula (A). Usually, it is 50 times or less, preferably 25 times or less, more preferably 15 times or less. If it is in the said range, the cyclic siloxane represented by Formula (B) can be produced | generated more efficiently.

The fluorination step preferably uses a solvent. The type of the solvent is not particularly limited and can be appropriately selected according to the purpose. Specifically, hydrocarbon solvents such as hexane, benzene and toluene, diethyl ether, 1,4-dioxane, tetrahydrofuran ( THF) and the like, halogen solvents such as methylene chloride and chloroform, acetone, dimethylacetamide (DMA), N, N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO) and the like Aprotic polar solvents and the like. Of these, hydrocarbon solvents are preferred.

The reaction temperature in the fluorination step is usually −20 ° C. or higher, preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and usually 100 ° C. or lower, preferably 50 ° C. or lower, more preferably 30 ° C. or lower.
The reaction time of the fluorination step is usually 1 minute or more, preferably 3 minutes or more, more preferably 5 minutes or more, and usually 2 hours or less, preferably 1 hour or less, more preferably 30 minutes or less.
The fluorination step is usually performed under an inert atmosphere such as nitrogen or argon.
In addition, if it is in the said range, the cyclic siloxane represented by Formula (B) can be produced | generated more efficiently.

（式（Ｄ’）中、Ｒ^３及びＲ^４はそれぞれ酸素原子及びハロゲン原子からなる群より選択される少なくとも１種の原子を含んでいてもよい炭素数１〜２０の炭化水素基、水素原子、ハロゲン原子、ヒドロキシル基、又は炭素数０〜６のシリル基を表し、Ｒ^３同士及びＲ^４同士はそれぞれ同一の置換基であることを、Ｒ^３とＲ^４間はそれぞれ異なる置換基であることを表す。）
以下、「式（Ｄ’）で表されるシルセスキオキサン」について、詳細に説明する。 <Silsesquioxane>
As described above, the production method of the present invention can efficiently produce a cage-type silsesquioxane having four different substituents on the opposite side, but it can be produced using the production method of the present invention. Silsesquioxane represented by the following formula (D ′) is also an embodiment of the present invention.

(In Formula (D ′), R ³ and R ⁴ are each a hydrocarbon group having 1 to 20 carbon atoms and a hydrogen atom, each of which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. , A halogen atom, a hydroxyl group, or a silyl group having 0 to 6 carbon atoms, R ³ and R ⁴ are the same substituents, and R ³ and R ⁴ are different substituents. Represents this.)
Hereinafter, “silsesquioxane represented by the formula (D ′)” will be described in detail.

Ｒ^３が炭化水素基である場合の炭素数は、好ましくは１６以下、より好ましくは１２以下、好ましくは８以下である。
Ｒ^３としては、メチル基（−ＣＨ_３）、エチル基（−Ｃ_２Ｈ_５）、ビニル基（−ＣＨ＝ＣＨ_２）、エチニル基（−Ｃ≡ＣＨ）、ｎ−プロピル基（−^ｎＣ_３Ｈ_７）、ｉ−プロピル基（−^ｉＣ_３Ｈ_７）、ｎ−ブチル基（−^ｎＣ_４Ｈ_９）、ｔ−ブチル基（−^ｔＣ_４Ｈ_９）、ｎ−ペンチル基（−^ｎＣ_５Ｈ_１１）、ｎ−ヘキシル基（−^ｎＣ_６Ｈ_１３）、ｃ−ヘキシル基（−^ｃＣ_６Ｈ_１１）、フェニル基（−Ｃ_６Ｈ_５）、ナフチル基（−Ｃ_１０Ｈ_７）、メトキシ基（−ＯＣＨ_３）、エトキシ基（−ＯＣ_２Ｈ_５）、ｎ−プロポキシ基（−Ｏ^ｎＣ_３Ｈ_７）、ｉ−プロポキシ基（−Ｏ^ｉＣ_３Ｈ_７）、ｎ−ブトキシ基（−Ｏ^ｎＣ_４Ｈ_９）、ｔ−ブトキシ基（−Ｏ^ｔＣ_４Ｈ_９）、フェノキシ基（−ＯＣ_６Ｈ_５）、グリシジル基、水素原子（−Ｈ）、フルオロ原子（−Ｆ）、クロロ原子（−Ｃｌ）、ブロモ原子（−Ｂｒ）、ヒドロキシル基（―ＯＨ）、トリメチルシリル基（−Ｓｉ（ＣＨ_３）_３）、ｔ−ブチルジメチルシリル基（−Ｓｉ（^ｔＣ_４Ｈ_９）（ＣＨ_３）_２）等が挙げられる。 R ³ of silsesquioxane represented by the formula (D ′) is a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. , A hydrogen atom, a halogen atom, a hydroxyl group, or a silyl group having 0 to 6 carbon atoms, and R ³ are the same substituent, but the “hydrocarbon group” is the case of R ¹ It is synonymous and “may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom” means a hydroxyl group (—OH), an epoxy group, a fluoro group (—F), chloro This means that a functional group containing an oxygen atom or a halogen atom such as a group (—Cl) may be contained, and a linking group containing an oxygen atom or a halogen atom such as an ether group (—O—) is attached to the carbon skeleton. Including inside or at the end It means that it may be. In addition, the “silyl group having 0 to 6 carbon atoms” means, for example, a silyl group having 0 carbon atoms such as a trihydrosilyl group (—SiH ₃ ) or a carbon number such as trimethylsilyl groups (—Si (CH ₃ ) ₃ ). 3 silyl groups, t-butyldimethylsilyl groups (—Si ( ^t C ₄ H ₉ ) (CH ₃ ) ₂ ), and the like, mean silyl groups having 6 carbon atoms, and the like.
In the production method of the present invention, for example, silsesquioxane having a phenyl group can be produced. As shown in the following formula, the phenyl group can be easily substituted with a chloro group by reaction with hydrogen chloride or the like. Can do. Since the chloro group (Si-Cl) bonded to the silicon atom is very active, various functional groups can be introduced into the silsesquioxane using this. In addition, when introducing a new hydrocarbon group, a method of reacting with an organometallic reagent such as a Grignard reagent, or a method of reacting with a hydride reducing agent such as sodium borohydride when introducing a hydrogen atom is used. In the case of introducing a group, a method of hydrolysis is used, and in the case of introducing a silyl group, a method of reacting with a reagent such as silyllithium is exemplified.

The carbon number when R ³ is a hydrocarbon group is preferably 16 or less, more preferably 12 or less, and preferably 8 or less.
R ³ includes a methyl group (—CH ₃ ), an ethyl group (—C ₂ H ₅ ), a vinyl group (—CH═CH ₂ ), an ethynyl group (—C≡CH), an n-propyl group ( ^—n C ₃ H _7), i- propyl _{^{(- i C 3 H 7)}} , n- butyl _{^{(- n C 4 H 9)}} , t- butyl _{^{(- t C 4 H 9)}} , n- pentyl (- ⁿ C ₅ H _11), n- hexyl group _{^{(- n C 6 H 13)}} , c- hexyl group _{^{(- c C 6 H 11)}} , phenyl group _{(-C 6 H} 5), naphthyl _{(-C 10} H ₇ ), methoxy group (—OCH ₃ ), ethoxy group (—OC ₂ H ₅ ), n-propoxy group (—O ⁿ C ₃ H ₇ ), i-propoxy group (—O ⁱ C ₃ H ₇ ), n - butoxy _{^{(-O n C 4 H 9)}} , t- butoxy _{^{(-O t C 4 H 9)}} , phenoxy group (-O ₆ H _5), a glycidyl group, a hydrogen atom (-H), fluoro atom (-F), chloro atom (-Cl), bromo atom (-Br), hydroxyl (-OH), an trimethylsilyl (-Si (CH _{3) 3),} t- butyldimethylsilyl group _{^{(-Si (t C 4 H 9}} ) (CH 3) 2) , and the like.

R ⁴ of the silsesquioxane represented by the formula (D ′) is a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. , A hydrogen atom, a halogen atom, a hydroxyl group, or a silyl group having 0 to 6 carbon atoms, R ⁴ is the same substituent, and R ³ and R ⁴ are different substituents. Where “hydrocarbon group” and the like have the same meaning as in R ³ .
The carbon number when R ⁴ is a hydrocarbon group is preferably 16 or less, more preferably 12 or less, and preferably 8 or less.
R ⁴ includes a methyl group (—CH ₃ ), an ethyl group (—C ₂ H ₅ ), a vinyl group (—CH═CH ₂ ), an ethynyl group (—C≡CH), an n-propyl group ( ^—n C). ₃ H _7), i- propyl _{^{(- i C 3 H 7)}} , n- butyl _{^{(- n C 4 H 9)}} , t- butyl _{^{(- t C 4 H 9)}} , n- pentyl (- ⁿ C ₅ H _11), n- hexyl group _{^{(- n C 6 H 13)}} , c- hexyl group _{^{(- c C 6 H 11)}} , phenyl group _{(-C 6 H} 5), naphthyl _{(-C 10} H ₇ ), methoxy group (—OCH ₃ ), ethoxy group (—OC ₂ H ₅ ), n-propoxy group (—O ⁿ C ₃ H ₇ ), i-propoxy group (—O ⁱ C ₃ H ₇ ), n - butoxy _{^{(-O n C 4 H 9)}} , t- butoxy _{^{(-O t C 4 H 9)}} , phenoxy group (-O ₆ H _5), a glycidyl group, a hydrogen atom (-H), fluoro atom (-F), chloro atom (-Cl), bromo atom (-Br), hydroxyl (-OH), an trimethylsilyl (-Si (CH _{3) 3),} t- butyldimethylsilyl group _{^{(-Si (t C 4 H 9}} ) (CH 3) 2) , and the like.

（式（Ａ）及び（Ｂ）中、Ｒ^１は炭素数１〜２０の炭化水素基を表し、Ｒ^１同士は同一の炭化水素基であることを表す。） <Method for producing cyclic siloxane / cyclic siloxane>
As described above, the cyclic siloxane represented by the formula (B) can be generated by the above fluorination step. However, the fluorination step, that is, the cyclic siloxane represented by the following formula (A) and boron trifluoride A method for producing a cyclic siloxane comprising a step of reacting to produce a cyclic siloxane represented by the following formula (B) and a cyclic siloxane represented by the formula (B) produced using this production method are also included in the present invention. It is one mode.

(In formulas (A) and (B), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ represents the same hydrocarbon group.)

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.

三フッ化ホウ素ジエチルエーテル錯体（７．８ｍＬ，６３ｍｍｏｌ）を、ａｌｌ−ｃｉｓ−１，３，５，７−テトラヒドロキシ−１，３，５，７−テトライソブチルシクロテトラシロキサン（３．０ｇ，６．３ｍｍｏｌ）のヘキサン（３０ｍＬ）溶液の中に加えた結果、ヘキサン溶液の下部にすぐに黄色層が現れた。１０分後、ヘキサンとベンゼンの混合液を加え、上部の層を５回抽出した。この溶液から溶媒を留去し、減圧下で乾燥させて、粗生成物として無色の油分（３．２ｇ）を、さらにゲル浸透クロマトグラフィー（ＧＰＣ，ＣＨＣｌ_３）で精製して、無色の油分（１．７ｇ，３．５ｍｍｏｌ，５３％）を得た。¹H NMR (600.17 MHz, CDCl₃): δ 0.73 (dd, J_H-H = 6.8 Hz, J_H-F= 3.9 Hz, 8H), 0.97 (J_H-H= 6.8 Hz, 24H), 1.87 Hz (J_H-H= 6.8 Hz, 4H) ppm. ¹³C NMR (75.57 MHz, CDCl₃):
δ 20.73 (d, J_C-F = 22 Hz, CH₂), 23.48 (CH), 25.46 (CH₃) ppm. ¹⁹F NMR (564.72 MHz, CDCl₃): δ -128.95 ppm. ²⁹Si NMR (59.71 MHz, CDCl₃): δ -62.87 (d, J_Si-F = 272 Hz) ppm. IR (KBr): 900, 1122, 1232, 1369, 2956 cm^-1. DIMS (EI, 30eV): m/z (%) 423 ([M-Buⁱ]⁺, 90). Anal. Calcd for C₁₆H₃₆F₄O₄Si₄: C, 39.97; H, 7.55. Found: C
, 39.58; H, 7.69. <Example 1: Synthesis of 1,3,5,7-tetrafluoro-1,3,5,7-tetraisobutylcyclotetrasiloxane>

Boron trifluoride diethyl ether complex (7.8 mL, 63 mmol) was added to all-cis-1,3,5,7-tetrahydroxy-1,3,5,7-tetraisobutylcyclotetrasiloxane (3.0 g, 6 .3 mmol) in hexane (30 mL), a yellow layer immediately appeared at the bottom of the hexane solution. After 10 minutes, a mixture of hexane and benzene was added, and the upper layer was extracted five times. The solvent was distilled off from this solution, dried under reduced pressure, and a colorless oil (3.2 g) as a crude product was further purified by gel permeation chromatography (GPC, CHCl ₃ ) to obtain a colorless oil ( 1.7 g, 3.5 mmol, 53%). ¹ H NMR (600.17 MHz, CDCl ₃ ): δ 0.73 (dd, J _HH = 6.8 Hz, J _HF = 3.9 Hz, 8H), 0.97 (J _HH = 6.8 Hz, 24H), 1.87 Hz (J _HH = 6.8 Hz , 4H) ppm. ¹³ C NMR (75.57 MHz, CDCl ₃ ):
δ 20.73 (d, J _CF = 22 Hz, CH ₂ ), 23.48 (CH), 25.46 (CH ₃ ) ppm. ¹⁹ F NMR (564.72 MHz, CDCl ₃ ): δ -128.95 ppm. ²⁹ Si NMR (59.71 MHz, CDCl ₃ ): δ -62.87 (d, J _Si-F = 272 Hz) ppm. IR (KBr): 900, 1122, 1232, 1369, 2956 cm ^-1 . DIMS (EI, 30eV): m / z (% ) 423 ([M-Bu ⁱ ] ⁺ , 90). Anal. Calcd for C ₁₆ H ₃₆ F ₄ O ₄ Si ₄ : C, 39.97; H, 7.55. Found: C
, 39.58; H, 7.69.

<Example 2: Synthesis of 1,3,5,7-tetrafluoro-1,3,5,7-tetraphenylcyclotetrasiloxane>
Boron trifluoride diethyl ether complex (6.7 mL, 54 mmol) was added to all-cis-1,3,5,7-tetrahydroxy-1,3,5,7-tetraphenylcyclotetrasiloxane (3.0 g, 5 .4 mmol) in hexane (30 mL), a white layer immediately appeared at the bottom of the hexane solution. After 10 minutes, a mixture of hexane and benzene was added, and the upper layer was extracted five times. The solvent was distilled off from this solution, dried under reduced pressure, and a colorless oil (0.96 g) as a crude product was further purified by gel permeation chromatography (GPC, CHCl ₃ ) to obtain a colorless oil ( 0.61 g, 1.1 mmol, 20%).
¹ H NMR (399.78 MHz, CDCl ₃ ): δ 7.32 (t, J _HH = 7.6 Hz, 8H), 7.44-7.49 (m, 4H), 7.52-7.54 (m, 8H) ppm. ¹³ C NMR (75.57 MHz , CDCl ₃ ): δ 77.37 (d, J _CF = 26 Hz, C),
128.25 (CH), 131.95 (CH), 134.11 (CH) ppm. ¹⁹ F NMR (376.17 MHz, CDCl ₃ ): δ -133.45 (s, J _F-Si = 255 Hz) ppm. ²⁹ Si NMR (59.71 MHz, CDCl ₃ ): δ -74.71 (d, J _Si-F = 255 Hz) ppm. IR (KBr): 696, 741, 889, 1140, 1431, 1595, 3076 cm ^-1 . DIMS (EI, 30eV): m / z (%) 560 ([M] ⁺ , 50). Anal. Calcd for C ₂₄ H ₂₀ F ₄ O ₄ Si ₄ : C, 51.41; H, 3.59. Found: C, 51.44; H, 3.93.

１，３，５，７−テトラフェニルシクロシロキサンナトリウム塩（４．９１ｇ，７．６６ｍｍｏｌ）のクロロホルム懸濁液（５０ｍＬ）に１，３，５，７−テトラフルオロ−１，３，５，７−テトライソブチルテトラシクロシロキサン（７．３７ｇ）を加え、４日間加熱還流した。溶媒をロータリーエバポレーターにて除いたのち、クロロホルムにて抽出をし、脱塩処理を行った。その後、中圧分取液体カラムクロマトグラフィー（クロロホルム／ヘキサン展開溶媒）、分取型サイズ排除型液体カラムクロマトグラフィー（クロロホルム）、薄層クロマトグラフィー（クロロホルム／ヘキサン＝１／２）で精製することにより目的物を１７ｍｇ得た。
¹H-NMR (600.17 MHz, CDCl₃): δ 0.71 (d, J = 7.2 Hz, 8H), 0.97 (d, J = 6.6 Hz, 24H), 1.91 (m, J = 7.2 Hz, 4H), 7.32 (t, J = 7.2 Hz, 8H), 7.40 (m, 4H), 7.67 (m, 8H) ppm. ²⁹Si-NMR (119.24 MHz, CDCl₃): δ -66.96, -79.14 ppm. DIMS (EI, 30eV): m/z (%) 895 ([M-i-Bu]⁺, 25). <Example 3: Synthesis of Janus cube>

1,3,5,7-tetrafluoro-1,3,5,7 was added to a chloroform suspension (50 mL) of 1,3,5,7-tetraphenylcyclosiloxane sodium salt (4.91 g, 7.66 mmol). -Tetraisobutyltetracyclosiloxane (7.37 g) was added and heated to reflux for 4 days. After removing the solvent with a rotary evaporator, extraction with chloroform was performed for desalting. Then, by purifying by medium pressure preparative liquid column chromatography (chloroform / hexane developing solvent), preparative size exclusion liquid column chromatography (chloroform), and thin layer chromatography (chloroform / hexane = 1/2). 17 mg of the desired product was obtained.
¹ H-NMR (600.17 MHz, CDCl ₃ ): δ 0.71 (d, J = 7.2 Hz, 8H), 0.97 (d, J = 6.6 Hz, 24H), 1.91 (m, J = 7.2 Hz, 4H), 7.32 (t, J = 7.2 Hz, 8H), 7.40 (m, 4H), 7.67 (m, 8H) ppm. ²⁹ Si-NMR (119.24 MHz, CDCl ₃ ): δ -66.96, -79.14 ppm. DIMS (EI, 30 eV): m / z (%) 895 ([Mi-Bu] ⁺ , 25).

  The silsesquioxane obtained by the production method of the present invention can be used as a silane coupling agent having a siloxane or silsesquioxane skeleton as a silicone product.

Claims (5)

A silsesquid comprising a condensation step of reacting a cyclic siloxane represented by the following formula (B) with a cyclic siloxane represented by the following formula (C) to produce a silsesquioxane represented by the following formula (D): Oxane production method.

(In formulas (B), (C), and (D), R ¹ and R ² each represent a hydrocarbon group having 1 to 20 carbon atoms, A represents an alkali metal, and R ¹ and R ² each represent (Indicating that they are the same hydrocarbon group, R ¹ and R ² are different hydrocarbon groups.) The silsesquioxane of Claim 1 including the fluorination process which makes the cyclic siloxane represented by a following formula (A), and boron trifluoride react, and produces | generates the cyclic siloxane represented by a following formula (B). Manufacturing method.

(In formulas (A) and (B), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ represents the same hydrocarbon group.) Silsesquioxane represented by the following formula (D ′).

(In Formula (D ′), R ³ and R ⁴ are each a hydrocarbon group having 1 to 20 carbon atoms and a hydrogen atom, each of which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom. , A halogen atom, a hydroxyl group, or a silyl group having 0 to 6 carbon atoms, R ³ and R ⁴ are the same substituents, and R ³ and R ⁴ are different substituents. Represents this.) The manufacturing method of cyclic siloxane (B) including the fluorination process which makes the cyclic siloxane represented by following formula (A) and boron trifluoride react, and produces | generates the cyclic siloxane represented by following formula (B).

(In formulas (A) and (B), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ represents the same hydrocarbon group.) Cyclic siloxane represented by the following formula (B).

(In formula (B), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ represents the same hydrocarbon group.)