WO2020003734A1 - Method for producing cyclic siloxane compound, and cyclic siloxane compound - Google Patents

Abstract

A method for producing a cyclic siloxane compound having at least one cyclic skeleton, which comprises a step wherein a compound represented by formula (1) is reacted with an alcohol compound or a silicon compound having at least two hydroxy groups or alkoxy groups in the presence of a boron catalyst and/or a transition metal hydride complex catalyst, thereby forming a cyclic skeleton by means of an -Si-O- bond. (In formula (1), each of RA1, RA2, RC1 and RC2 independently represents an atom or group selected from the group consisting of a hydrogen atom, an alkyl group and the like; and each of RB1 and RB2 independently represents a group selected from the group consisting of an alkyl group, an aryl group and the like. Incidentally, a combination of RA1 and RA2, and a combination of RC1 and RC2 are not the same as a combination of RB1 and RB2.)

Description

Method for producing cyclic siloxane compound and cyclic siloxane compound

<< The present invention relates to a method for producing a cyclic siloxane compound and a cyclic siloxane compound.

Siloxane compounds represented by polysiloxanes are functional chemicals and materials used in various industrial fields such as construction, electricity, automobiles, medical care, daily necessities and the like in the form of oil, rubber, resin and the like. . In order to improve the functionality and performance of such a siloxane compound, a method for efficiently producing a compound having a cyclic siloxane structure excellent in thermal stability and / or the like, and / or a method having a higher functionality and higher performance The development of cyclic siloxane compounds is also an important issue.

As a general method for producing a cyclic siloxane, (A) a method of hydrolyzing chlorosilanes (for example, Patent Documents 1 and 2 and Non-Patent Documents 1 and 2), and (B) a method of using chlorosilanes and silanols in the presence of a base The following reaction methods (for example, Patent Document 3 and Non-Patent Documents 3 and 4) are known.

On the other hand, a compound having a structure in which diagonal silicon atoms of cyclotetrasiloxane are bonded to each other by an oxysilyleneoxy group is a bicyclic pentamer having five silicon atoms (bicyclo [3.3.3] pentasiloxane ) Having two cyclotetrasiloxane skeletons in the molecule. Therefore, the bicyclic pentamer compound is expected to have properties such as thermal stability that are superior to a simple cyclotetrasiloxane compound. As such a bicyclic pentamer compound, a compound having a substituent such as a phenyl group and / or a methyl group is known. Examples of the production method include (C) a method of reacting chlorosilanes and silanols in the presence of a base (for example, Patent Document 4 and Non-Patent Documents 4 and 5), and (D) bicyclo [1] of a bicyclic oligosilane. 1.1.1] A method of reacting pentasilane with an oxidizing agent (m-chloroperbenzoic acid) (Non-Patent Document 6) and the like have been reported.

The method for producing a cyclic siloxane includes (E) reacting 1,1,3,3,5,5-hexamethyltrisiloxane with diphenylsilanediol in the presence of a tris (pentafluorophenyl) borate catalyst. There is known a method of obtaining a cyclic tetramer by performing the method (for example, Patent Document 5 and Non-Patent Document 7).

JP-B-63-28893 JP-A-07-285974 JP 08-157487 A U.S. Pat. No. 3,145,225 US 2013/79538

Chemistry of organosilicon compounds, p. 206, Doujin Kagaku (1972) Organosilicon Chemistry, p. 48, Walter de Gruyter (1986) Silicon, 6,21 (2014) J. Gen. Chem. USSR, 54, 306 (1984) Z. Anorg.Allg.Chem., 636, 1212 (2010) Chem. Commun., 54, 268 (2018) Angewandte Chemie International Edition, 56, 8706 (2017)

However, the above-mentioned conventional manufacturing method has problems in the following points.
(1) When chlorosilanes are used as the raw material, the hydrolysis of the chlorosilanes tends to generate hydrogen chloride having a corrosive action, and thus the raw material compound is not easily handled. When silanediol is reacted, corrosive hydrogen chloride and a salt thereof are generated, so that special care is required for storage of raw materials and / or containers for reaction, treatment of waste, and the like (methods A and B). , And C).
(2) When a bicyclic oligosilane is used as a raw material, production of a raw material compound is not easy, and an expensive oxidizing agent is required even in an oxidation reaction (method D). Further, a polymer compound containing a cyclic siloxane skeleton is expected to be applied to a functional material having excellent thermal stability and mechanical properties, but has not been produced so far.
(3) In the methods of Patent Document 5 and Non-Patent Document 7, hydrogen chloride is not generated and an expensive oxidizing agent is not required, but the yield of the target siloxane compound is low.
For these reasons, there has been a demand for an industrially more advantageous method capable of solving the problems of the prior art.

An object of the present invention is to provide a method for efficiently and selectively producing a siloxane compound having a cyclic skeleton.

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a cyclic siloxane compound can be efficiently produced by reacting a predetermined compound in the presence of a predetermined catalyst, and completed the present invention. It led to.

（式（１）中、Ｒ^A1、Ｒ^A2、Ｒ^C1及びＲ^C2は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
　Ｒ^B1及びＲ^B2は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基（Ｒ^X1及びＲ^X2は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかである。
　ただし、Ｒ^A1及びＲ^A2の組み合わせ並びにＲ^C1及びＲ^C2の組み合わせとＲ^B1及びＲ^B2の組み合わせとは、互いに同一でない。）
［２］
　Ｒ^A1、Ｒ^A2、Ｒ^C1及びＲ^C2が、それぞれ独立して、水素原子、アルキル基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
　Ｒ^B1及びＲ^B2が、それぞれ独立して、アリール基、及び、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基（Ｒ^X1及びＲ^X2は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかである、［１］に記載の製造方法。
［３］
　前記環状シロキサン化合物が、前記環骨格を１つ有する化合物である、［１］に記載の製造方法。
［４］
　前記環骨格を１つ有する化合物が、下記式（３）で表される化合物である、［３］に記載の製造方法。

（式（３）中、Ｒ^A1、Ｒ^A2、Ｒ^C1及びＲ^C2は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
　Ｒ^B1及びＲ^B2は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基（Ｒ^X1及びＲ^X2は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかであり、
　Ｒ^D1及びＲ^D2は、それぞれ独立して、アルキル基、アリール基、アルケニル基、アルコキシ基、及びシロキシ基からなる群より選ばれるいずれかであり、
　ｐ’は、０以上の整数である。
　ただし、Ｒ^A1及びＲ^A2の組み合わせ並びにＲ^C1及びＲ^C2の組み合わせとＲ^B1及びＲ^B2の組み合わせとは、互いに同一でない。）
［５］
　前記環状シロキサン化合物が、前記環骨格内のケイ素原子間で形成される架橋環を少なくとも１つ含む、２以上の環から構成される化合物であり、
　前記環骨格を形成する工程において、前記式（１）で表される化合物（式（１）中、Ｒ^B1及びＲ^B2の少なくとも一方は、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基である。）と、少なくとも３個のヒドロキシ基若しくはアルコキシ基を有するケイ素化合物とを反応させる、［１］に記載の製造方法。
［６］
　前記環骨格内のケイ素原子間で形成される架橋環を少なくとも１つ含む、２以上の環から構成される化合物が、下記式（４）で表される化合物であり、
　少なくとも３個のヒドロキシ基若しくはアルコキシ基を有するケイ素化合物が、式（Ａ１－１）で表される化合物である、［５］に記載の製造方法。

（式（４）中、Ｒ^A1、Ｒ^A2、Ｒ^C1及びＲ^C2は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
　Ｒ^B2は、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基（Ｒ^X1及びＲ^X2は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかであり、
　Ｒ^D2は、アルキル基、アリール基、アルケニル基、アルコキシ基、及びシロキシ基からなる群より選ばれるいずれかであり、

（式（Ａ１－１）中、Ｒ^D1は、アルコキシ基であり、
　Ｒ^D2は、アルキル基、アリール基、アルケニル基、アルコキシ基、及びシロキシ基からなる群より選ばれるいずれかであり、
　Ｒ^E1及びＲ^E2は、アルキル基である。）
［７］
　前記環状シロキサン化合物が、前記環骨格内のケイ素原子間で形成される架橋環を少なくとも１つ含む、２以上の環から構成される化合物であり、
　前記環骨格を形成する工程において、前記式（１）で表される化合物（式（１）中、Ｒ^B1及びＲ^B2は、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基である。）と、少なくとも４個のヒドロキシ基若しくはアルコキシ基を有するケイ素化合物とを反応させる、［１］に記載の製造方法。
［８］
　前記環骨格内のケイ素原子間で形成される架橋環を少なくとも１つ含む、２以上の環から構成される化合物が、下記式（５）で表される構造を有する化合物であり、
　少なくとも４個のヒドロキシ基若しくはアルコキシ基を有するケイ素化合物が、式（Ａ１－２）で表される化合物である、［７］に記載の製造方法。

（式（５）中、Ｒ^A1、Ｒ^A2、Ｒ^C1及びＲ^C2は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
　Ｒ^X1及びＲ^X2は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかであり、
　ｎは、２以上の整数である。）

（式（Ａ１－２）中、Ｒ^D1及びＲ^D2は、アルコキシ基であり、Ｒ^E1及びＲ^E2は、アルキル基である。）
［９］
　前記環状シロキサン化合物が、少なくとも１つのスピロ環を含む、２以上の環から構成される化合物であり、
　前記式（１）におけるＲ^A1、Ｒ^A2、Ｒ^C1及びＲ^C2は、それぞれ独立して、アルコキシ基であり、Ｒ^B1及びＲ^B2は、それぞれ独立して、アルキル基、アリール基、及び、アルケニル基からなる群より選ばれるいずれかであり、
　前記式（１）で表される化合物と、少なくとも２個のヒドロキシ基を有するシラン化合物とを、遷移金属ヒドリド錯体触媒の存在下で反応させ、さらに下記式（２）で表される化合物をホウ素触媒の存在下で反応させる工程を含む、
　［１］に記載の製造方法。

（式（２）中、Ｒ^A1'、Ｒ^A2'、Ｒ^C1'及びＲ^C2'は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
　Ｒ^B1'及びＲ^B2'は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1')(Ｒ^X2')Ｈ基（Ｒ^X1'及びＲ^X2'は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかであり、
　ｎは、１以上の整数である。
　ただし、Ｒ^A1'及びＲ^A2'の組み合わせ並びにＲ^C1'及びＲ^C2'の組み合わせとＲ^B1'及びＲ^B2'の組み合わせとは、互いに同一でない。）
［１０］
　前記少なくとも１つのスピロ環を含む、２以上の環から構成される化合物が、下記式（６）で表される構造を有する化合物である、［９］に記載の製造方法。

（式（６）中、Ｑ¹及びＱ²は、それぞれ独立して以下の構造：

（Ｒ^B1'、Ｒ^B2'は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1')(Ｒ^X2')Ｈ基（Ｒ^X1'及びＲ^X2'は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかであり、Ｒ^C1'、Ｒ^C2'は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、ｎは１以上の整数である。）で表され、
　Ｒ^B1及びＲ^B2は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基（Ｒ^X1及びＲ^X2は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかであり、
　Ｒ^D1及びＲ^D2は、それぞれ独立して、アルキル基、アリール基、アルケニル基、アルコキシ基、及びシロキシ基からなる群より選ばれるいずれかであり、
　Ｒ^A1'及びＲ^A2'は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
　ｐ及びＮは、１以上の整数である。）
［１１］
　前記式（６）で表される構造を有する化合物が、下記式（６－１）で表される化合物である、［１０］に記載の製造方法。

（式（６－１）中、Ｑ¹及びＱ²は、それぞれ独立して以下の構造：

で表され、
　Ｒ^B1及びＲ^B2は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1)(Ｒ^X2)Ｈ基（Ｒ^X1及びＲ^X2は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかであり、
　Ｒ^D1及びＲ^D2は、それぞれ独立して、アルキル基、アリール基、アルケニル基、アルコキシ基、及びシロキシ基からなる群より選ばれるいずれかであり、
　Ｒ^A1'及びＲ^A2'は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
　Ｒ^B1'及びＲ^B2'は、それぞれ独立して、アルキル基、アリール基、アルケニル基、及び、－ＯＳｉ(Ｒ^X1')(Ｒ^X2')Ｈ基（Ｒ^X1'及びＲ^X2'は、それぞれ独立して、アルキル基、アリール基、及びアルケニル基からなる群より選ばれるいずれかである。）からなる群より選ばれるいずれかであり、
　Ｒ^C1'及びＲ^C2'は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかであり、
　ｐ及びｎは、１以上の整数である。）
［１２］
　下記式（Ｉ）で表される、環状シロキサン化合物。

（式（Ｉ）中、Ｒ^a1、Ｒ^a2、Ｒ^c1及びＲ^c2は、それぞれ独立して、アルコキシ基であり、
　Ｒ^b1、Ｒ^b2、Ｒ^d1及びＲ^d2は、それぞれ独立して、アルキル基、アリール基、及び、アルケニル基からなる群より選ばれるいずれかであり、
　ｍは、０～２のいずれかの整数である。）
［１３］
　下記式（II）で表される、環状シロキサン化合物。

（式（II）中、Ｒ^eは、アルキル基、アリール基、アルケニル基、アルコキシ基、及び、シロキシ基からなる群より選ばれるいずれかであり、
　Ｒ^f、Ｒ^g1、Ｒ^g2、Ｒ^h1、Ｒ^h2、Ｒⁱ¹、及びＲⁱ²は、それぞれ独立して、アルキル基、アリール基、及び、アルケニル基からなる群より選ばれるいずれかである。）
［１４］
　下記式（III）で表される構造を有する、環状シロキサン化合物。

（式（III）中、Ｒ^j1、Ｒ^j2、Ｒ^k1、Ｒ^k2、Ｒ^l1、Ｒ^l2、Ｒ^m1、及びＲ^m2は、それぞれ独立して、アルキル基、アリール基、及び、アルケニル基からなる群より選ばれるいずれかであり、
　ｎは、２以上の整数である。）
［１５］
　下記式（IV）で表される構造を有する、環状シロキサン化合物。

（式（IV）中、Ｒⁿ¹、Ｒⁿ²、Ｒ^o1、Ｒ^o2、Ｒ^p1、Ｒ^p2、Ｒ^q1、Ｒ^q2、Ｒ^r1、Ｒ^r2、Ｒ^s1、及びＲ^s2は、それぞれ独立して、アルキル基、アリール基、及び、アルケニル基からなる群より選ばれるいずれかであり、
　ｍ１、ｍ２、ｍ３は、それぞれ独立して、１又は２の整数であり、
　ｎは、１以上の整数である。
　ただし、Ｒⁿ¹及びＲⁿ²の組み合わせ並びにＲ^r1及びＲ^r2の組み合わせと、Ｒ^p1及びＲ^p2の組み合わせとは、互いに同一でない。） That is, this application provides the following inventions.
[1]
Reacting a compound represented by the following formula (1) with an alcohol compound or a silicon compound having at least two hydroxy groups or alkoxy groups in the presence of a boron catalyst and / or a transition metal hydride complex catalyst; A method for producing a cyclic siloxane compound having at least one ring skeleton, comprising a step of forming a ring skeleton by an —O— bond.

(In the formula (1), R ^A1 , R ^A2 , R ^C1 and R ^C2 are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. Yes,
R ^B1 and R ^B2 each independently represent an alkyl group, an aryl group, an alkenyl group, and —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 each independently represent an alkyl group , An aryl group, and an alkenyl group.).
However, the combination of R ^A1 and R ^A2, the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other. )
[2]
R ^A1 , R ^A2 , R ^C1 and R ^C2 are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, and an alkoxy group;
R ^B1 and R ^B2 each independently represent an aryl group and —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 each independently represent an alkyl group, an aryl group, and an alkenyl The method according to [1], which is any one selected from the group consisting of:
[3]
The production method according to [1], wherein the cyclic siloxane compound is a compound having one of the ring skeletons.
[4]
The production method according to [3], wherein the compound having one ring skeleton is a compound represented by the following formula (3).

(In the formula (3), R ^A1 , R ^A2 , R ^C1 and R ^C2 are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. Yes,
R ^B1 and R ^B2 each independently represent an alkyl group, an aryl group, an alkenyl group, and —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 each independently represent an alkyl group , An aryl group, and an alkenyl group.)
R ^D1 and R ^D2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group;
p ′ is an integer of 0 or more.
However, the combination of R ^A1 and R ^A2, the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other. )
[5]
The cyclic siloxane compound is a compound composed of two or more rings including at least one crosslinked ring formed between silicon atoms in the ring skeleton,
In the step of forming the ring skeleton, the compound represented by the formula (1) (in the formula (1), at least one of R ^B1 and R ^B2 is a —OSi (R ^X1 ) (R ^X2 ) H group. ) And a silicon compound having at least three hydroxy groups or alkoxy groups.
[6]
A compound composed of two or more rings including at least one bridged ring formed between silicon atoms in the ring skeleton is a compound represented by the following formula (4):
The production method according to [5], wherein the silicon compound having at least three hydroxy groups or alkoxy groups is a compound represented by the formula (A1-1).

(In the formula (4), R ^A1 , R ^A2 , R ^C1 and R ^C2 are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. Yes,
R ^B2 represents an alkyl group, an aryl group, an alkenyl group, and a —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 each independently represent an alkyl group, an aryl group, and an alkenyl group. Any one selected from the group consisting of:
R ^D2 is any one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group;

(In the formula (A1-1), R ^D1 is an alkoxy group,
R ^D2 is any one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group;
R ^E1 and R ^E2 are alkyl groups. )
[7]
The cyclic siloxane compound is a compound composed of two or more rings including at least one crosslinked ring formed between silicon atoms in the ring skeleton,
In the step of forming the ring skeleton, a compound represented by the formula (1) (in the formula (1), R ^B1 and R ^B2 are —OSi (R ^X1 ) (R ^X2 ) H groups). The method according to [1], wherein the reaction is carried out with a silicon compound having at least four hydroxy groups or alkoxy groups.
[8]
A compound composed of two or more rings including at least one bridged ring formed between silicon atoms in the ring skeleton is a compound having a structure represented by the following formula (5):
The production method according to [7], wherein the silicon compound having at least four hydroxy groups or alkoxy groups is a compound represented by the formula (A1-2).

(In the formula (5), R ^A1 , R ^A2 , R ^C1 and R ^C2 are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. Yes,
R ^X1 and R ^X2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group;
n is an integer of 2 or more. )

(In the formula (A1-2), R ^D1 and R ^D2 are an alkoxy group, and R ^E1 and R ^E2 are an alkyl group.)
[9]
The cyclic siloxane compound is a compound composed of two or more rings including at least one spiro ring,
R ^A1 , R ^A2 , R ^C1 and R ^C2 in the formula (1) are each independently an alkoxy group, and R ^B1 and R ^B2 are each independently an alkyl group, an aryl group, and an alkenyl group. Any one selected from the group consisting of
The compound represented by the formula (1) is reacted with a silane compound having at least two hydroxy groups in the presence of a transition metal hydride complex catalyst. Comprising reacting in the presence of a catalyst,
The production method according to [1].

(In the formula (2), R ^{A1 ′} , R ^{A2 ′} , R ^{C1 ′} and R ^{C2 ′} are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. Is one of
R ^{B1 ′} and R ^{B2 ′} are each independently an alkyl group, an aryl group, an alkenyl group, and —OSi (R ^{X1 ′} ) (R ^{X2 ′} ) H group (R ^{X1 ′} and R ^{X2 ′} are Independently, any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.)
n is an integer of 1 or more.
However, the combination of R ^{A1 ′} and R ^{A2 ′ and} the combination of R ^{C1 ′} and R ^{C2 ′} are not the same as the combination of R ^{B1 ′} and R ^{B2 ′} . )
[10]
The production method according to [9], wherein the compound composed of two or more rings including the at least one spiro ring is a compound having a structure represented by the following formula (6).

(In the formula (6), Q ¹ and Q ² each independently have the following structure:

(R ^{B1 ′} and R ^{B2 ′} each independently represent an alkyl group, an aryl group, an alkenyl group, and a —OSi (R ^{X1 ′} ) (R ^{X2 ′} ) H group (R ^{X1 ′} and R ^{X2 ′} are Each independently is any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.), And R ^{C1 ′} and R ^{C2 ′} are each independently , A hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or an alkoxy group, and n is an integer of 1 or more.)
R ^B1 and R ^B2 each independently represent an alkyl group, an aryl group, an alkenyl group, and —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 each independently represent an alkyl group , An aryl group, and an alkenyl group.)
R ^D1 and R ^D2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group;
R ^{A1 ′} and R ^{A2 ′} are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group;
p and N are integers of 1 or more. )
[11]
The production method according to [10], wherein the compound having the structure represented by the formula (6) is a compound represented by the following formula (6-1).

(In the formula (6-1), Q ¹ and Q ² each independently have the following structure:

Represented by
R ^B1 and R ^B2 each independently represent an alkyl group, an aryl group, an alkenyl group, and —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 each independently represent an alkyl group , An aryl group, and an alkenyl group.)
R ^D1 and R ^D2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group;
R ^{A1 ′} and R ^{A2 ′} are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group;
R ^{B1 ′} and R ^{B2 ′} are each independently an alkyl group, an aryl group, an alkenyl group, and —OSi (R ^{X1 ′} ) (R ^{X2 ′} ) H group (R ^{X1 ′} and R ^{X2 ′} are Independently any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.)
R ^{C1 ′} and R ^{C2 ′} are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group;
p and n are integers of 1 or more. )
[12]
A cyclic siloxane compound represented by the following formula (I).

(In the formula (I), R ^a1 , R ^a2 , R ^c1 and R ^c2 are each independently an alkoxy group,
R ^b1 , R ^b2 , R ^d1 and R ^d2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group;
m is any integer from 0 to 2. )
[13]
A cyclic siloxane compound represented by the following formula (II):

(In the formula (II), R ^e is an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and, is either selected from the group consisting of siloxy groups,
R ^f , R ^g1 , R ^g2 , R ^h1 , R ^h2 , R ⁱ¹ , and R ⁱ² are each independently any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group. )
[14]
A cyclic siloxane compound having a structure represented by the following formula (III):

(In the formula ^{(III), R j1, R} j2, R k1, R k2, R l1, R l2, R m1, and R ^{m @ 2} are each independently an alkyl group, an aryl group and, consists of an alkenyl group One of a group,
n is an integer of 2 or more. )
[15]
A cyclic siloxane compound having a structure represented by the following formula (IV).

(In the formula (IV), R ⁿ¹ , R ⁿ² , R ^o1 , R ^o2 , R ^p1 , R ^p2 , R ^q1 , R ^q2 , R ^r1 , R ^r2 , R ^s1 , and R ^s2 are each independently An alkyl group, an aryl group, and any one selected from the group consisting of alkenyl groups;
m1, m2, and m3 are each independently an integer of 1 or 2,
n is an integer of 1 or more.
However, the combination of R ⁿ¹ and R ^{n2 and} the combination of R ^r1 and R ^r2 are not the same as the combination of R ^p1 and R ^p2 . )

According to the present invention, it is possible to provide a method for efficiently producing a cyclic siloxane compound, a novel cyclic siloxane compound obtained by the method, a composition containing the compound, and a heat-resistant material containing the composition. .

FIG. 3 is a diagram showing ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR spectrum data of compound 12. FIG. 3 is a diagram showing ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR spectrum data of compound 16. FIG. 4 is a view showing the result of measuring the thermophysical properties of compound 16 by differential scanning calorimetry under a nitrogen atmosphere. FIG. 3 is a view showing the results of measuring the thermophysical properties of compound 16 by differential scanning calorimetry under an air atmosphere.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from the gist of the present invention. In the present specification, when a numerical value or a property value is inserted before and after using “to”, it is used as including the values before and after. For example, the description of the numerical range of “1 to 100” includes both the upper limit value “100” and the lower limit value “1”. The same applies to the description of other numerical ranges.

[Method for producing cyclic siloxane compound]
The production method of the present invention relates to a method of preparing a compound represented by the following formula (1) and an alcohol compound or a silicon compound having at least two hydroxy groups or alkoxy groups by using a boron catalyst and / or a transition metal hydride complex catalyst. A method for producing a cyclic siloxane compound having at least one ring skeleton, comprising a step of forming a ring skeleton by a —Si—O— bond by reacting the compound under the following conditions.

(Compound represented by Formula (1))
The compound represented by the formula (1) in the production method of the present invention is represented by the following.

In the formula (1), R ^A1 , R ^A2 , R ^C1 and R ^C2 are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. ,
R ^B1 and R ^B2 each independently represent an alkyl group, an aryl group, an alkenyl group, and —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 each independently represent an alkyl group , An aryl group, and an alkenyl group.).
However, the combination of R ^A1 and R ^A2, the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other.

In the formula ^{(1), R A1, R} A2, R C1 and R ^C2 are independently a hydrogen atom, an alkyl group, an alkenyl group, and, is either selected from the group consisting of alkoxy group, R ^B1 And R ^B2 are each independently an aryl group or a —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 are each independently an alkyl group, an aryl group, and an alkenyl group. Is preferably selected from the group consisting of:

Examples of the alkyl group in the formula (1) include a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or a combination thereof. Group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, cyclopropylmethyl group, pentyl group, isopentyl group, sec-pentyl group, Examples include a neopentyl group, a tert-pentyl group, a cyclopentyl group, a hexyl group, and a cyclohexyl group. Among these, preferably, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group , A neopentyl group, and a hexyl group, more preferably a methyl group, an ethyl group, and a propyl group, and still more preferably a methyl group and an ethyl group.

Examples of the alkenyl group in the formula (1) include a linear or branched alkenyl group having 1 to 10 carbon atoms, and specific examples include a vinyl group, an allyl group, and a butenyl group. Can be Among these, a vinyl group is preferable.

Examples of the alkoxy group in the formula (1) include an alkoxy group having 1 to 10 carbon atoms. Specifically, a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, and an n-butyloxy group are exemplified. Group, sec-butyloxy group, tert-butyloxy group, isobutyloxy group, n-pentyloxy group, 2,2-dimethylpropyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, 2-methylpentyloxy And 2-ethylhexyloxy groups. Among these, preferably, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, sec-butyloxy group, tert-butyloxy group, and isobutyloxy group, more preferably methoxy group Group, ethoxy group, n-propyloxy group and isopropyloxy group, more preferably methoxy group and ethoxy group.

{Examples of the aryl group in the formula (1) include an aryl group having 6 to 10 carbon atoms, and specific examples include a phenyl group and a naphthyl group. Among these, a phenyl group is preferable.

The compound represented by the formula (1) can be obtained by synthesizing using an organic synthesis technique. For example, Patent Document 4: US Pat. No. 3,145,225, Non-Patent Document 4: J. Gen. Chem USSR, 54, 306 (1984), Non-Patent Document 5: Z. Anorg. Allg. Chem., 636, 1212 (2010), ACS Catal
, 7, 1836 (2017).
Specifically, it can be obtained by reacting silanediol and chlorosilane in the presence of a base as described below.

（シランジオールにおけるＲ^B1及びＲ^B2は、式（１）におけるＲ^B1及びＲ^B2と同義である。クロロシランにおけるＲ¹及びＲ²は、それぞれ独立して、水素原子、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかである。）

(R ^B1 and R ^B2 in silane diol has the same meaning as R ^B1 and R ^B2 in the formula ^(1). R 1 and R ² in the chlorosilane are each independently a hydrogen atom, an alkyl group, an aryl group, an alkenyl Group, or any one selected from the group consisting of alkoxy groups.)

Further, specifically, when at least one of R ^A1 and R ^A2 and at least one of R ^C1 and R ^C2 are a hydrogen atom, a silanediol and a silane are converted to a transition metal and It can also be obtained by reacting in the presence of a ligand accordingly.

（シランジオールにおけるＲ^B1及びＲ^B2は、式（１）におけるＲ^B1及びＲ^B2と同義である。シランにおけるＲ¹及びＲ²の少なくとも一方は、水素原子であり、もう一方は、アルキル基、アリール基、アルケニル基、及び、アルコキシ基からなる群より選ばれるいずれかである。）

(R ^B1 and R ^B2 in silane diol has the same meaning as R ^B1 and R ^B2 in the formula (1). At least one of R ¹ and R ² in the silane is hydrogen atom and the other, an alkyl group, Any one selected from the group consisting of an aryl group, an alkenyl group, and an alkoxy group.)

(Alcohol compound)
The alcohol compound in the production method of the present invention may be an alcohol having at least one hydroxy group, and may be a dihydric alcohol or a trihydric alcohol in addition to a monohydric alcohol. Examples of the alcohol compound include methanol, ethanol, n-propanol, n-butanol, methylcyclohexanol, cyclohexanol, and benzyl alcohol. Among these, benzyl alcohol is preferred.

(Silicon compound having at least two hydroxy groups or alkoxy groups)
The silicon compound having at least two hydroxy groups or alkoxy groups in the production method of the present invention includes at least two silicon compounds containing a bond between a silicon atom and a hydroxy group (Si—OH), or at least two silicon compounds. And a silicon compound having a bond (Si-OR) between a silicon atom and an alkoxy group.

ケ イ 素 The silicon compound having at least two hydroxy groups or alkoxy groups is preferably represented by the following formula (A1).

In the formula (A1), R ^D1 and R ^D2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group, and R ^E1 and R ^E2 are Are the same as each other, are a hydrogen atom or an alkyl group, and p is an integer of 1 or more.

The siloxy group is a linear or branched monovalent group containing at least one —O—Si— bond. Here, at least one —O—Si— contained in the siloxy group is bonded to a silicon atom in the formula (A1) via an oxygen atom in the —O—Si—.
As the siloxy group, specifically, a siloxy group (S) shown below (hereinafter, referred to as “siloxy group (S)”) is preferably exemplified.

In the siloxy group (S), R ^S1 and R ^S2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group (S); ¹ is any divalent organic group, and R ^S3 is any monovalent organic group. f is 0 or 1, and F is an integer of 1 or more. The upper limit of F is not particularly limited, but is usually 1,000, preferably 100, and more preferably 50.
Examples of the arbitrary divalent organic group for Z ¹ include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group, and a butylene group; and a carbon atom having 6 to 10 carbon atoms such as a phenylene group and a naphthylene group. 10 arylene groups; —Si (R ^{S1 ′} ) (R ^{S2 ′} ) — (R ^{S1 ′} and R ^{S2 ′} are each independently selected from the group consisting of alkyl groups, aryl groups, alkenyl groups, and alkoxy groups; And a group obtained by combining them.
Examples of the optional monovalent organic group for R ^S3 include a hydroxy group, an alkyl group, an aryl group, and an alkenyl group.

When R ^E1 and R ^E2 in the formula (A1) are both hydrogen atoms, R ^D1 and R ^D2 are preferably an alkyl group, an aryl group or an alkenyl group, and more preferably an alkyl group or an aryl group. Group.

P is preferably an integer of 1 to 2.

Examples of the alkyl group, aryl group, alkenyl group, and alkoxy group in the formula (A1) and the siloxy group (S) include the same groups as the alkyl group, the aryl group, the alkenyl group, and the alkoxy group in the formula (1). Examples thereof include the same preferred groups.

(Boron catalyst)
The boron catalyst used in the production method of the present invention is not particularly limited as long as it contains boron. For example, triphenylborane, tris (pentafluorophenyl) borane, tris (2,3,4,5) -Tetrafluorophenyl) borane, tris (2,4,6-trifluorophenyl) borane, tris (2,3-difluorophenyl) borane, tris (2-fluorophenyl) borane, tris [3,5-bis (tri Fluoromethyl) phenyl] borane, tris [4- (trifluoromethyl) phenyl] borane, trimethylborane, triethylborane, tris (trifluoromethyl) borane, diphenylfluoroborane, and bis (pentafluorophenyl) chloroborane. Among them, tris (pentafluorophenyl) borane is preferable.

(Transition metal hydride complex catalyst)
The transition metal hydride complex catalyst used in the production method of the present invention is not particularly limited as long as it has a bond between a transition metal atom and a hydrogen atom.
Transition metals include, for example, copper, iron, rhodium, iridium, rhenium, tungsten, platinum, palladium, manganese, cobalt, nickel, chromium, molybdenum, and ruthenium. Of these, copper and ruthenium are preferred.
A ligand other than hydride may be coordinated with the transition metal hydride complex. Examples of the ligand include 2,2′-bipyridine, 1,10-phenanthroline, N, N, N ′. , N'-tetramethylethylenediamine, triphenylphosphine, and 2- (dicyclohexylphosphino) biphenyl, carbon monoxide, cyclopentadiene.

In the production method of the present invention, a ligand may be separately added to the system in which the transition metal hydride complex exists. As the ligand to be separately added, in addition to the above-mentioned ligands, xantphos, 1,3-bisdiphenylphosphinopropane, 1,1,1-tris (diphenylphosphinomethylethane), and the like can be given.

The amount of the boron catalyst or the transition metal hydride complex catalyst used in the production method of the present invention is not particularly limited, but is usually 0.001 to 1.0 equivalent based on the amount of the compound represented by the formula (1). Yes, preferably 0.005 to 0.50 equivalents, more preferably 0.01 to 0.10 equivalents.

The production method of the present invention can be carried out with or without a solvent. When a solvent is used, nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran, diethyl ether, tert-butyl methyl ether and dibutyl ether; benzene Various solvents other than those that react with the raw materials can be used, for example, aromatic hydrocarbon solvents such as toluene, xylene, and the like. The solvents can be used alone or in combination of two or more.
When the reaction in the production method of the present invention is carried out in the gas phase, the reaction can be carried out by mixing an inert gas such as nitrogen with the raw material and the solvent.

When the reaction is carried out using a solvent, depending on the type of the target product, the solvent may be appropriately selected from the viewpoints of the type of the catalyst, the solubility of the raw material and / or the product, and the selectivity of the reaction. preferable.
In the production method of the present invention, it is preferable to carry out the reaction using a solvent from the viewpoint of smoothly proceeding the reaction of forming a ring skeleton by a -Si-O- bond.
When a boron catalyst is used as the catalyst, the solvent in the production method of the present invention is preferably a ketone-based solvent, an ether-based solvent, or an aromatic hydrocarbon-based solvent.
In addition, the solvent in the production method of the present invention is preferably an aromatic hydrocarbon solvent, and more preferably toluene, from the viewpoint of allowing the reaction to proceed smoothly.

The amount of the solvent used is such that the sum of the compound represented by the formula (1) and the alcohol compound or the silicon compound having at least two hydroxy groups or alkoxy groups is 0.01 to 5 mol / L. It is preferable that the concentration be 0.05 to 1 mol / L, more preferably 0.05 to 0.5 mol / L.

In the production method of the present invention, the substance ratio of the compound represented by the formula (1) to the alcohol compound or the silicon compound having at least two hydroxy groups or alkoxy groups is the compound represented by the formula (1). Is preferably 0.1 to 10 equivalents, more preferably 0.5 to 3 equivalents, and more preferably 0.5 to 3 equivalents to the alcohol compound or the silicon compound having at least two hydroxy groups or alkoxy groups. The equivalent is more preferably 7 to 1.5 equivalents, still more preferably 0.8 to 1.2 equivalents, and even more preferably 0.9 to 1.1 equivalents.

The reaction in the production method of the present invention can be carried out in a liquid phase or a gas phase depending on the reaction temperature and / or reaction pressure. In addition, as the form of the reaction apparatus, various known forms such as a batch type and a flow type can be used.
The reaction temperature is usually −30 ° C. or higher, preferably −20 to 300 ° C., more preferably −10 to 200 ° C., and still more preferably −10 to 150 ° C.
The reaction pressure is generally 0.1 to 100 atm, preferably 0.1 to 50 atm, more preferably 0.1 to 20 atm, still more preferably 0.1 to 10 atm.
The reaction time may be appropriately adjusted depending on the amounts of the raw materials and / or the catalyst, the reaction temperature, the type of the reaction apparatus, and the like, and is usually 0.1 to 1000 hours, preferably 0.1 to 800 hours, and more preferably 0 to 800 hours. It is about 1 to 500 hours.

Although the reaction in the production method of the present invention proceeds even in a closed reactor, the reaction proceeds more efficiently by opening the reactor and continuously removing reaction products outside the reaction system. It can also be done.

The cyclic siloxane compound produced by the production method of the present invention can be isolated by performing appropriate purification, and the purification is carried out by means commonly used in organic chemistry such as distillation, recrystallization, reprecipitation, and chromatography. Easily reached.

に お い て In the production method of the present invention, the step of forming a ring skeleton by a —Si—O— bond specifically refers to the step of forming the following ring skeleton.

The cyclic siloxane compound obtained by the production method of the present invention has at least one ring skeleton formed by a -Si-O- bond. The cyclic siloxane compound may include two or more ring skeletons by further forming a -Si-O- bond at the bond position indicated by the wavy line of the ring skeleton shown above.
Here, when the cyclic siloxane compound contains two or more ring skeletons, the cyclic siloxane compound is a compound having a bridged ring formed between silicon atoms in the ring skeleton, or at least one of silicon atoms in the ring skeleton. It is a compound having a spiro ring as a spiro atom.
That is, the cyclic siloxane compound obtained by the production method of the present invention includes: 1) a compound having one ring skeleton formed by a —Si—O— bond (hereinafter, also referred to as a cyclic siloxane compound A), 2) a ring skeleton. (Hereinafter, also referred to as cyclic siloxane compound B) containing at least one bridge formed by a —Si—O— bond between silicon atoms in the compound (hereinafter, also referred to as cyclic siloxane compound B), and 3) —Si A compound composed of two or more rings including at least one spiro ring formed by an —O— bond (hereinafter, also referred to as cyclic siloxane compound C).

<1) Compound having one ring skeleton formed by -Si-O- bond>
The cyclic siloxane compound A is preferably represented by the following formula (3).

In equation ^{(3), R A1, R} A2, R B1, R B2, R C1, R C2, R D1 and R ^D2 are in the formula (1) and ^{(A1), R A1, R} A2, R B1 , R ^B2 , R ^C1 , R ^C2 , R ^D1 and R ^D2 . p ′ is an integer of 0 or more. The upper limit of p 'is 10, preferably 5, and more preferably 2.

The compound in which p 'in formula (3) is 0 can be obtained by reacting the compound represented by formula (1) with an alcohol compound.
In the formula (3), the compound in which p ′ is 1 or more is a compound represented by the formula (1) and a silicon compound having at least two hydroxy groups or alkoxy groups, preferably represented by the formula (A1) It can be obtained by reacting with a compound.
At this time, it is preferable that R ^B1 and R ^B2 in the formula (1) each independently be any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.

<2) Compound composed of two or more rings containing at least one bridge formed by a —Si—O— bond between silicon atoms in the ring skeleton>
When producing the cyclic siloxane compound ^B , at least one of R ^B1 and R ^{B2 in} the compound represented by the formula (1) is a —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 are Each independently is any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.). The compound to be reacted with the compound represented by the formula (1) is a silicon compound having at least three hydroxy groups or alkoxy groups.

The cyclic siloxane compound B is preferably a compound represented by the following formula (4) or a compound having a structure represented by the following formula (5).

In the formula (4), R ^A1 , R ^A2 , R ^B2 , R ^C1 , R ^C2 , R ^D2 , R ^X1 and R ^X2 are R ^A1 , R ^A2 , R ^{B2 in the} formulas (1) and (A1). , R ^C1 , R ^C2 , R ^D2 , R ^X1 and R ^X2 .
When producing the compound represented by the formula (4), R ^B1 in the formula (1) is a —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 are each independently an alkyl Group, an aryl group, or an alkenyl group), R ^D1 in the formula (A1) is an alkoxy group, R ^E1 and R ^E2 are alkyl groups, and p Is preferably 1.

Wherein ^{(5), R A1, R} A2, R C1, R C2, R X1 and R ^X2 are, in the formula (1) and ^{(A1), R A1, R} A2, R C1, R C2, R X1 And R ^X2 , and n is an integer of 2 or more. The upper limit of n is not particularly limited, but is usually 10,000, preferably 5,000, and more preferably 1,000.
When producing a compound having a structure represented by the formula (5), R ^B1 and R ^B2 in the formula (1) are —OSi (R ^X1 ) (R ^X2 ) H groups, and in the formula (A1) In the ^formula , R ^D1 and R ^D2 are alkoxy groups, R ^E1 and R ^E2 are alkyl groups, and p is preferably 1.

It is preferable that the compound having the structure represented by the formula (5) is bonded at both ends to form a cyclic polymer having the structure represented by the formula (5) as a constituent unit.
The terminal of the compound having the structure represented by the formula (5) is hydrogen or R ^{E '} (R ^E' is an alkyl group) as represented by the following formula (5 '). Is also good.

Further, the terminal in the formula (5 ′), that is, Si—H and —ORE ^′ in —OSi (R ^X1 ) (R ^X2 ) H are modified, and an alkyl group, an aryl group, an alkenyl group, an alkoxy group, Or it may be modified to a siloxy group or the like.
Here, the alkyl group, the aryl group, the alkenyl group, the alkoxy group, and the siloxy group are the same as the alkyl group, the aryl group, the alkenyl group, the alkoxy group, and the siloxy group in Formula (1) and Formula (A1). And the same preferred groups can be mentioned.

<3) Compound composed of two or more rings including at least one spiro ring formed by -Si-O- bond>
When producing the cyclic siloxane compound C, R ^A1 , R ^A2 , R ^C1 and R ^C2 in the formula (1) are each independently an alkoxy group, and R ^B1 and R ^B2 are each independently It is any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.
When producing the cyclic siloxane compound C, the compound represented by the formula (1) is reacted with a silane compound having at least two hydroxy groups in the presence of a transition metal hydride complex catalyst. A step of reacting the compound represented by the formula (2) in the presence of a boron catalyst.

In formula (2), R ^{A1 ′} , R ^{A2 ′} , R ^{C1 ′} , and R ^{C2 ′} are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. One of
R ^{B1 ′} and R ^{B2 ′} are each independently an alkyl group, an aryl group, an alkenyl group, and —OSi (R ^{X1 ′} ) (R ^{X2 ′} ) H group (R ^{X1 ′} and R ^{X2 ′} are Independently, any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.)
n is an integer of 1 or more. The upper limit of n is 10, preferably 5, and more preferably 2.
However, the combination of R ^{A1 ′} and R ^{A2 ′ and} the combination of R ^{C1 ′} and R ^{C2 ′} are not the same as the combination of R ^{B1 ′} and R ^{B2 ′} .

Examples of the alkyl group, the aryl group, the alkenyl group, and the alkoxy group in the formula (2) include the same groups as the alkyl group, the aryl group, the alkenyl group, and the alkoxy group in the formula (1). Similar preferred groups can be mentioned.

The cyclic siloxane compound C preferably has a structure represented by the following formula (6).

In the formula (6), N is an integer of 1 or more, and Q ¹ and Q ² are each independently represented by the following structure.

In the formula (6), R ^B1 , R ^B2 , R ^D1 , R ^D2 , R ^{A1 ′} , R ^{A2 ′} , R ^{B1 ′} , R ^{B2 ′} , R ^{C1 ′} , R ^{C2 ′} , p and n are represented by the formula (1) ), R ^B1 , R ^B2 , R ^D1 , R ^D2 , R ^{A1 ′} , R ^{A2 ′} , R ^{B1 ′} , R ^{B2 ′} , R ^{C1 ′} , R ^{C2 ′} , p in formulas (A1) and (2) And n are synonymous.

When producing the compound represented by the formula (6), R ^E1 and R ^E2 in the formula (A1) are a hydrogen atom.

と き When N in the formula (6) is 1, the compound having the structure represented by the formula (6) is preferably represented by the formula (6-1).

In the formula (6-1), R ^B1 , R ^B2 , R ^D1 , R ^D2 , R ^{A1 ′} , R ^{A2 ′} , R ^{B1 ′} , R ^{B2 ′} , Q ¹ and Q ² are represented by the formulas (1) and ( A1), synonymous with R ^B1 , R ^B2 , R ^D1 , R ^D2 , R ^{A1 ′} , R ^{A2 ′} , R ^{B1 ′} , R ^{B2 ′} , Q ¹ and Q ² in the formulas (2) and (6). is there.

When N in the formula (6) is 2 or more, R ^{B1 ′} and R ^{B2 ′} in the formula (2) (where n is 2 or more, R ^{B1 ′} and R ^B1 in the formula (2) ^At least one combination of ^{B2 ′} ) are both —OSi (R ^{X1 ′} ) (R ^{X2 ′} ) H groups.

When N in the structure represented by the formula (6) is 2 or more, the both terminals have a structure represented by> Si (R ^{B1 ′} ) (R ^{B2 ′} ) as represented by the formula (6-1). And both ends may be combined to form a spiro ring. That is, when both ends are combined to form a spiro ring, a macro ring composed of a plurality of spiro rings is formed.

[Cyclic siloxane compound]
The cyclic siloxane compound can be provided by the production method of the present invention.
Examples of the cyclic siloxane compound of the present invention include compounds represented by the following formula (I).

In the formula (I), R ^a1 , R ^a2 , R ^c1 and R ^c2 are each independently an alkoxy group;
R ^b1 , R ^b2 , R ^d1 and R ^d2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group;
m is any integer from 0 to 2.

Examples of the alkoxy group, alkyl group, aryl group and alkenyl group in the formula (I) include the same groups as the alkoxy group, alkyl group, aryl group and alkenyl group in the formula (1), Similar preferred groups can be mentioned.

化合物 Specific examples of the compound represented by the formula (I) include compounds having a combination of substituents shown in Table 1 below.

環状 Examples of the cyclic siloxane compound of the present invention include compounds represented by the following formula (II).

Wherein (II), R ^e is an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and, is either selected from the group consisting of siloxy groups,
R ^f , R ^g1 , R ^g2 , R ^h1 , R ^h2 , R ⁱ¹ , and R ⁱ² are each independently any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.

The siloxy group is a chain or branched group containing at least one —O—Si— bond. Here, at least one —O—Si— contained in the siloxy group is bonded to a silicon atom in the formula (A1) via an oxygen atom in the —O—Si—.
As the siloxy group, specifically, a siloxy group (S) shown below is suitably mentioned.

In the siloxy group (S), R ^S1 and R ^S2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group (S); ¹ is any divalent organic group, and R ^S3 is any monovalent organic group. f is 0 or 1, and F is an integer of 1 or more. The upper limit of F is not particularly limited, but is usually 1,000, preferably 100, and more preferably 50.
Examples of the arbitrary divalent organic group for Z ¹ include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group, and a butylene group; and a carbon atom having 6 to 10 carbon atoms such as a phenylene group and a naphthylene group. 10 arylene groups; —Si (R ^{S1 ′} ) (R ^{S2 ′} ) — (R ^{S1 ′} and R ^{S2 ′} are each independently selected from the group consisting of alkyl groups, aryl groups, alkenyl groups, and alkoxy groups; And a group obtained by combining them.
Examples of the optional monovalent organic group for R ^S3 include a hydroxy group, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group.

Examples of the alkyl group, the aryl group, the alkenyl group, and the alkoxy group in the formula (II) include the same groups as the alkyl group, the aryl group, the alkenyl group, and the alkoxy group in the formula (1). Similar preferred groups can be mentioned.

化合物 Specific examples of the compound represented by the formula (II) include compounds having a combination of substituents shown in Table 2 below.

中 In the table, S-1, S-2, and S-3 are each represented by the following formulas.

S-1, S-2, and in S3, R ^S3 and F have the same meanings as R ^S3 and F in siloxy group (S).
The wavy line in S-3 represents a bond to another group represented by formula S-3.

環状 Examples of the cyclic siloxane compound of the present invention include compounds having a structure represented by the following formula (III).

Wherein ^{(III), R j1, R} j2, R k1, R k2, R l1, R l2, R m1, and R ^{m @ 2} are each independently an alkyl group, an aryl group, and the group consisting of an alkenyl group One of the
n is an integer of 2 or more.

Examples of the alkyl group, the aryl group, and the alkenyl group in the formula (III) include the same groups as the alkyl group, the aryl group, and the alkenyl group in the formula (1). be able to.

The compound having the structure represented by the formula (III) is preferably bonded at both ends to form a cyclic polymer having the structure represented by the formula (III) as a constituent unit.
The terminal of the compound having the structure represented by the formula (III) is hydrogen or R ^{E '} (R ^E' is an alkyl group) as represented by the following formula (III '). Is also good.

Further, the terminal in the formula (III ′), that is, Si—H and —ORE ^′ in —OSi (R ^m1 ) (R ^m2 ) H are modified, and an alkyl group, an aryl group, an alkenyl group, an alkoxy group, Alternatively, it may be modified to a siloxy group or the like.
Here, the alkyl group, the aryl group, the alkenyl group, the alkoxy group, and the siloxy group are the same as the alkyl group, the aryl group, the alkenyl group, the alkoxy group, and the siloxy group in Formula (1) and Formula (A1). And the same preferred groups can be mentioned.

化合物 Specific examples of the compound having the structure represented by the formula (III) include compounds having a combination of substituents shown in Table 3 below.

環状 Examples of the cyclic siloxane compound of the present invention include compounds having a structure represented by the following formula (IV).

In the formula (IV), R ⁿ¹ , R ⁿ² , R ^o1 , R ^o2 , R ^p1 , R ^p2 , R ^q1 , R ^q2 , R ^r1 , R ^r2 , R ^s1 , and R ^s2 are each independently an alkyl Group, an aryl group, and any one selected from the group consisting of alkenyl groups,
m1, m2, and m3 are each independently an integer of 1 or 2,
n is an integer of 1 or more.
However, the combination of R ⁿ¹ and R ^{n2 and} the combination of R ^r1 and R ^r2 are not the same as the combination of R ^p1 and R ^p2 .

と き When n in the formula (IV) is 1, the compound having the structure represented by the formula (IV) is preferably represented by the formula (IV-1).

In the formula (IV-1), R ⁿ¹ , R ⁿ² , R ^o1 , R ^o2 , R ^p1 , R ^p2 , R ^q1 , R ^q2 , R ^r1 , R ^r2 , R ^s1 , R ^s2 , R ^t1 , R ^t2 , R ^u1 and R ^u2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group;
m1, m2, and m3 are each independently an integer of 1 or 2,
n is an integer of 1 or more.
However, the combination of R ⁿ¹ and R ^{n2 and} the combination of R ^r1 and R ^r2 are not the same as the combination of R ^p1 and R ^p2 .
R ^t1 , R ^t2 , R ^u1 and R ^u2 are preferably an aryl group, more preferably a phenyl group.

Examples of the alkyl group, aryl group, and alkenyl group in Formula (IV) and Formula (IV-1) include the same groups as the alkyl group, aryl group, and alkenyl group in Formula (1). And the same preferred groups.

When n in the compound having the structure represented by the formula (IV) is 2 or more, both ends are> Si (R ^t1 ) (R ^t2 ) or> Si ( R ^u1 ) (R ^u2 ), and the two terminals may be joined together to form a spiro ring. That is, when both ends are combined to form a spiro ring, a macro ring composed of a plurality of spiro rings is formed.

化合物 Specific examples of the compound having the structure represented by the formula (IV) include compounds having combinations of substituents shown in Tables 4 to 6 below.

A novel cyclic siloxane compound and a high molecular compound are obtained by the production method of the present invention, and the high molecular compound is a material having excellent thermal stability and / or mechanical properties.
Since the cyclic siloxane compound of the present invention has a thermally stable cyclic skeleton, a material containing such a compound as a composition can be used as a heat-resistant material or the like. As the composition of the cyclic siloxane, not only one kind but also two or more kinds of cyclic siloxane compounds can be used simultaneously.

Specifically, the present invention has the following effects of the invention.
(1) Since alkoxysilanes, silanols, and hydrosilanes as raw materials do not generate corrosive compounds such as hydrogen chloride even when hydrolyzed, they are highly safe and easily available.
(2) Co-products of the reaction are hydrogen and / or hydrocarbons and do not produce strong corrosive compounds such as hydrogen chloride.
(3) The reaction proceeds under mild conditions at about room temperature, and a cyclic siloxane compound can be obtained in high yield.
(4) A novel cyclic siloxane compound can be produced.
(5) Not only low molecular compounds but also high molecular compounds can be produced.
(6) The polymer-based cyclic siloxane compound has high thermal stability, and a composition containing the cyclic siloxane compound can be used as a novel heat-resistant material.

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Trisiloxane compounds as raw materials are described in Patent Document 4: US Pat. No. 3,145,225, Non-Patent Document 4: J. Gen. Chem. USSR, 54, 306 (1984), Non-Patent Document 5: Z. Anorg. Allg. Chem. ., 636, 1212 (2010), ACS Catal., 7, 1836 (2017).
Other reagents were commercially available.

Example 1 Synthesis of Compound 1

Add bis (dimethylsiloxy) diphenylsilane (166 mg, 0.5 mmol), benzyl alcohol (54 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), and toluene (5 mL) to a test tube. The reaction was carried out at 25 ° C. for 16 hours in an argon atmosphere. After the completion of the reaction, the solvent was removed with an evaporator, and the compound 1 was purified using a recycling fractionator. Compound 1 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolation yield of compound 1 was 82%.

[Example 2] Examination of reaction conditions for synthesis of compound 1

The procedure was performed in the same manner as in Example 1 except that the type of the alcohol R ¹ OH and the type of the solvent shown in Table 1 were used. Table 7 shows the results. The yield is a yield determined from NMR, and compounds 2 and 3 other than compound 1 are as described above.

[Example 3]

Add bis (diethylsiloxy) diphenylsilane (194 mg, 0.5 mmol), benzyl alcohol (54 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), and toluene (5 mL) to a test tube. The reaction was carried out at 25 ° C. for 16 hours in an argon atmosphere. After the completion of the reaction, the solvent was removed with an evaporator, and the target compound 4 was purified using a recycling fractionator. Compound 4 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolation yield of compound 4 was 77%.

Example 4 Synthesis of Compound 5

Bis (diethylsiloxy) diphenylsilane (194 mg, 0.5 mmol), dimethoxydiphenylsilane (122 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), and toluene (5 mL) were placed in a test tube. In addition, the reaction was performed at 25 ° C. for 16 hours under an argon atmosphere. After completion of the reaction, the solvent was removed with an evaporator, and the target compound 5 was purified using silica gel column chromatography. Compound 5 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolation yield of compound 5 was 89%.

The peak positions of Compound 5 in the ¹ H NMR, ¹³ C NMR and ²⁹ Si NMR spectra were as follows.
¹ H NMR (600 MHz, benzene-d ₆ ): δ: 7.20-7.84, 0.96, 0.68.
¹³ C [ ¹ H] NMR (151 MHz, benzene-d ₆ ): δ: 136.5, 134.9, 130.8, 128.5, 7.9, 7.1.
²⁹ Si [ ¹ H] NMR (119 MHz, benzene-d ₆ ): δ -15.4, -45.0.

Example 5 Synthesis of Compound 6

Test tubes containing bis (diethylsiloxy) diphenylsilane (194 mg, 0.5 mmol), dimethoxymethylphenylsilane (91 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), and toluene (5 mL) And reacted at 25 ° C. for 16 hours under an argon atmosphere. After completion of the reaction, the solvent was removed with an evaporator, and the target compound 6 was purified using silica gel column chromatography. Compound 6 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolation yield of compound 6 was 89%.

Example 6 Synthesis of Compound 7

Test tubes containing bis (diethylsiloxy) diphenylsilane (194 mg, 0.5 mmol), dimethoxydicyclopentylsilane (114 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), and toluene (2.5 mL) And reacted at 25 ° C. for 12 hours under an argon atmosphere. After completion of the reaction, the solvent was removed with an evaporator, and the target compound 7 was purified using silica gel column chromatography. The compound was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolation yield of compound 7 was 93%.

The peak positions of Compound 7 in ¹ H NMR, ¹³ C NMR and ²⁹ Si NMR spectra were as follows.
¹ H NMR (600 MHz, benzene-d ₆ ): δ: 7.84-7.86 (m), 7.18-7.24 (m), 1.79-1.83 (m), 1.56-1.65 (m), 1.48-1.53 (m), 1.25 (t), 0.70 (q).
¹³ C [ ¹ H] NMR (151 MHz, benzene-d ₆ ): δ: 137.0, 134.9, 130.6, 128.7, 28.4, 27.8, 26.2, 8.1, 7.3.
²⁹ Si [ ¹ H] NMR (119 MHz, benzene-d ₆ ): δ -18.8, -22.6, -46.6.

Example 7 Synthesis of Compound 8

Bis (dimethylsiloxy) diphenylsilane (166 mg, 0.5 mmol), dimethylsilanediol (46 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), and toluene (2.5 mL) were placed in a test tube. In addition, the reaction was performed at 25 ° C. for 16 hours under an argon atmosphere. After completion of the reaction, the solvent was removed with an evaporator, and the target compound 8 was purified using silica gel column chromatography. Compound 8 was identified using ¹ H NMR, ¹³ C NMR and ²⁹ Si NMR. The isolation yield of compound 8 was 77%.

The peak positions of Compound 8 in ¹ H NMR, ¹³ C NMR and ²⁹ Si NMR spectra were as follows.
¹ H NMR (600 MHz, benzene-d ₆ ): δ: 7.83-7.84 (m), 7.19-7.23 (m), 0.21 (s), 0.17 (s).
¹³ C [ ¹ H] NMR (151 MHz, benzene-d ₆ ): δ: 136.6, 134.9, 130.7, 128.5, 1.31, 1.28.
²⁹ Si [ ¹ H] NMR (119 MHz, benzene-d ₆ ): δ -17.5, -18.5, -45.7.

Example 8 Synthesis of Compound 9

Test tubes containing bis (dimethylsiloxy) diphenylsilane (166 mg, 0.5 mmol), diethoxymethylvinylsilane (80 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), and toluene (2.5 mL) And reacted at 25 ° C. for 16 hours under an argon atmosphere. After completion of the reaction, the solvent was removed with an evaporator, and the target compound 9 was purified using silica gel column chromatography. Compound 9 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolation yield of compound 9 was 78%.

The peak positions of Compound 9 in ¹ H NMR, ¹³ C NMR and ²⁹ Si NMR spectra were as follows.
¹ H NMR (600 MHz, benzene-d ₆ ): δ: 7.81-7.84 (m), 7.16-7.23 (m), 6.08-6.14 (m), 5.86-5.91 (m), 0.25 (s), 0.21 ( d).
¹³ C [ ¹ H] NMR (151 MHz, benzene-d ₆ ): δ: 137.0, 136.5 (d), 134.9 (d), 134.0, 130.7 (d), 128.5 (d), 1.3, -0.3.
²⁹ Si [ ¹ H] NMR (119 MHz, benzene-d ₆ ): δ-16.9, -32.9, -45.6.

Example 9 Synthesis of Compound 10

Bis (hexylsiloxy) diphenylsilane (222 mg, 0.5 mmol), dimethoxydiphenylsilane (122 mg, 0.5 mmol), tris (pentafluorophenyl) borane (13 mg, 0.025 mmol), and toluene (2.5 mL) were placed in a test tube. In addition, the reaction was carried out at 40 ° C. for 48 hours under an argon atmosphere. After completion of the reaction, hexane (10 mL) and acetotrile (15 mL) were added to the reaction solution, the hexane layer was extracted, the solvent was removed with an evaporator, and the target compound 10 was purified using ODS silica gel column chromatography. Compound 10 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolation yield of compound 10 was 66%.

The peak positions of Compound 10 in ¹ H NMR, ¹³ C NMR and ²⁹ Si NMR spectra were as follows.
¹ H NMR (600 MHz, benzene-d ₆ ): δ: 7.81-7.83 (m), 7.17-7.21 (m), 5.29 (d), 1.36-1.45 (m), 1.07-1.24 (m), 0.82- 0.90 (m), 0.68-0.75 (m).
¹³ C [ ¹ H] NMR (151 MHz, benzene-d ₆ ): δ: 135.6, 135.5, 135.3, 135.0, 134.99, 134.95, 130.9, 128.6, 33.1 (d), 32.2 (d), 23.2 (d), 22.4 (d), 17.4 (d), 14.7 (d).
²⁹ Si [ ¹ H] NMR (119 MHz, benzene-d ₆ ): δ -30.8 (d), -42.8 (d).

Example 10 Synthesis of Compound 11

Triphenylsiloxytriethoxysilane (219 mg, 0.5 mmol), tris (dimethylsiloxy) phenylsilane (165 mg, 0.5 mmol), tris (pentafluorophenyl) borane (26 mg, 0.05 mmol), and toluene (15 mL) The reaction was performed at 60 ° C. for 24 hours in an argon atmosphere in addition to the test tube. After completion of the reaction, the solvent was removed with an evaporator, and the target compound 11 was purified using silica gel column chromatography. Compound 11 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolation yield of compound 11 was 30%.

¹ H NMR (600 MHz, benzene-d ₆ ): δ 7.86-7.88, 7.82-8.84, 7.18-7.20, 0.22.
¹³ C [ ¹ H] NMR (151 MHz, benzene-d ₆ ): δ 136.0, 135.98, 134.8, 132.4, 131.2, 130.6, 128.5, 128.4, 0.8.
²⁹ Si [ ¹ H] NMR (119 MHz, benzene-d ₆ ): δ -12.0, -17.5, -72.4, -101.3.

Example 11 Synthesis of Compound 12

Tetraisopropoxysilane (264 mg, 1 mmol), tetrakis (dimethylsiloxy) silane (329 mg, 1 mmol), tris (pentafluorophenyl) borane (51 mg, 0.1 mmol), and toluene (20 mL) were placed in a test tube. In addition, the reaction was performed at room temperature for 48 hours under an argon atmosphere. After completion of the reaction, the solvent was removed with an evaporator, and the target compound 12 was purified using alumina. Compound 12 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. GPC measurement of Compound 12 showed that the compound 12 was a polymer having a number average molecular weight (M _n ) of at least 8810, and that its thermophysical properties were measured by differential scanning calorimetry. ° C.
Figure 1 shows the spectral data of ^{1 H NMR, 13 C NMR,} 29 Si NMR.

Example 12 Synthesis of Compound 13

Bis (diethoxysiloxy) diphenylsilane (45 mg, 0.1 mmol), diphenylsilanediol (22 mg, 0.1 mmol), hydrogenated (triphenylphosphine) copper hexamer (2.5 mg, 0.00125 mmol), xantphos (xantphos, 4.3 mg , 0.0075 mmol) and toluene (2 mL) were added to the test tube, and reacted at 25 ° C. for 36 hours under an argon atmosphere. The yield of compound 13 was 86%.
The yield of compound 13 was determined by ²⁹ Si NMR using phenyltrimethylsilane (30 mg, 0.2 mmol) as an internal standard.
The peak positions in the ²⁹ Si NMR spectrum were as follows.
²⁹ Si [ ¹ H] NMR (119 MHz, benzene-d ₆ ): δ -44.2, -93.8.

Example 13 Synthesis of Compound 14

Bis (diethoxysiloxy) diphenylsilane (226.4 mg, 0.5 mmol), diphenylsilanediol (108.2 mg, 0.5 mmol), hydrogenated (triphenylphosphine) copper hexamer (12.3 mg, 0.00625 mmol), xantphos (xantphos, 21.7 mg , 0.0375 mmol) and toluene (10 mL) were added to the test tube, and reacted at 25 ° C. for 24 hours under an argon atmosphere. After the reaction, bis (dimethylsiloxy) diphenylsilane (332.6 mg, 1.0 mmol) and tris (pentafluorophenyl) borane (52 mg, 0.1 mmol) were added to a test tube, and reacted at 25 ° C. for 24 hours under an argon atmosphere. Was. After completion of the reaction, the solvent was removed with an evaporator, and the target compound 14 was purified using silica gel column chromatography. Compound 14 was identified using ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR. The isolation yield of compound 14 was 73%.

The peak positions of Compound 14 in ¹ H NMR, ¹³ C NMR and ²⁹ Si NMR spectra were as follows.
¹ H NMR (600 MHz, THF-d ₈ ): δ 7.39-7.42, 7.16-7.20, 7.06-7.11, -0.20.
¹³ C [ ¹ H] NMR (151 MHz, THF-d ₈ ): δ 136.98, 136.97, 135.8, 135.5, 131.5, 131.3, 129.1, 129.0, 1.0.
²⁹ Si [ ¹ H] NMR (119 MHz, THF-d ₈ ): δ -17.7, -46.4, -47.5, -108.8.

Example 14 Synthesis of Compound 15

Bis (diethoxysiloxy) diphenylsilane (226.4 mg, 0.5 mmol), tetramethyldisiloxanediol (83.2 mg, 0.5 mmol), hydrogenated (triphenylphosphine) copper hexamer (12.3 mg, 0.00625 mmol), xantphos (xantphos, 21.7 mg, 0.0375 mmol) and toluene (10 mL) were added to the test tube, and reacted at 25 ° C. for 16 hours under an argon atmosphere. After the reaction, bis (dimethylsiloxy) diphenylsilane (332.6 mg, 1.0 mmol) and tris (pentafluorophenyl) borane (52 mg, 0.1 mmol) were added to the test tube, and reacted at 25 ° C. for 24 hours under an argon atmosphere. . After completion of the reaction, the solvent was removed with an evaporator, and the target compound 15 was purified using silica gel column chromatography. Compound 15 was identified using ¹ H NMR, ¹³ C NMR and ²⁹ Si NMR. The isolation yield of compound 15 was 55%.

The peak positions of Compound 15 in ¹ H NMR, ¹³ C NMR and ²⁹ Si NMR spectra were as follows.
¹ H NMR (600 MHz, THF-d ₈ ): δ 7.92-7.94 (m), 7.78-7.82 (m), 7.16-7.22 (m), 0.21 (d), 0.13 (s).
¹³ C [ ¹ H] NMR (151 MHz, THF-d ₈ ): δ 136.98, 136.97, 135.8, 135.5, 131.5, 131.3, 129.1, 129.0, 1.1 (d), 0.9.
²⁹ Si [ ¹ H] NMR (119 MHz, THF-d ₈ ): δ -15.7, -19.1, -44.9, -46.0, -107.2.

Example 15 Synthesis of Compound 16

Bis (diethoxysiloxy) diphenylsilane (452.8 mg, 1 mmol), diphenylsilanediol (216.3 mg, 1 mmol), hydrogenated (triphenylphosphine) copper hexamer (24.6 mg, 0.0125 mmol), xantphos (xantphos, 43.4 mg , 0.075 mmol) and toluene (20 mL) were added to the test tube, and reacted at 25 ° C. for 16 hours under an argon atmosphere. After the reaction, tetrakis (dimethylsiloxy) silane (328.7 mg, 1.0 mmol) and tris (pentafluorophenyl) borane (52 mg, 0.1 mmol) were added to a test tube, and reacted at 25 ° C. for 24 hours under an argon atmosphere. After completion of the reaction, hexane (10 mL) was added to the reaction solution, which was filtered using a syringe filter. After the filtrate was concentrated, the solution diluted with toluene (10 mL) was filtered using alumina (2 g). The filtrate was concentrated to obtain Compound 16 (875 mg). Compound 16 was analyzed using ¹ H NMR, ¹³ C NMR, ²⁹ Si NMR, GPC, and DSC.H, C, and Si NMR indicated that the polymer had no Si (OEt) ₂ group at the growth end. A spirosiloxane polymer was suggested.
FIG. 2 shows ¹ H NMR, ¹³ C NMR, and ²⁹ Si NMR spectral data.
FIG. 3 shows the results of measuring thermophysical properties by differential scanning calorimetry under a nitrogen atmosphere. FIG. 4 shows the results of measuring thermophysical properties by differential scanning calorimetry under an air atmosphere.

According to the production method of the present invention, a cyclic siloxane compound useful as a functional chemical or a material can be produced more efficiently and safely, and a novel cyclic siloxane compound and its use can be provided. Its industrial significance is enormous.

Claims (15)

Reacting a compound represented by the following formula (1) with an alcohol compound or a silicon compound having at least two hydroxy groups or alkoxy groups in the presence of a boron catalyst and / or a transition metal hydride complex catalyst; A method for producing a cyclic siloxane compound having at least one ring skeleton, comprising a step of forming a ring skeleton by an —O— bond.

(In the formula (1), R ^A1 , R ^A2 , R ^C1 and R ^C2 are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. Yes,
R ^B1 and R ^B2 each independently represent an alkyl group, an aryl group, an alkenyl group, and —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 each independently represent an alkyl group , An aryl group, and an alkenyl group.).
However, the combination of R ^A1 and R ^A2, the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other. ) R ^A1 , R ^A2 , R ^C1 and R ^C2 are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, and an alkoxy group;
R ^B1 and R ^B2 each independently represent an aryl group and —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 each independently represent an alkyl group, an aryl group, and an alkenyl The method according to claim 1, which is any one selected from the group consisting of: The method according to claim 1, wherein the cyclic siloxane compound is a compound having one ring skeleton. The production method according to claim 3, wherein the compound having one ring skeleton is a compound represented by the following formula (3).

(In the formula (3), R ^A1 , R ^A2 , R ^C1 and R ^C2 are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. Yes,
R ^B1 and R ^B2 each independently represent an alkyl group, an aryl group, an alkenyl group, and —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 each independently represent an alkyl group , An aryl group, and an alkenyl group.)
R ^D1 and R ^D2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group;
p ′ is an integer of 0 or more.
However, the combination of R ^A1 and R ^A2, the combination of R ^C1 and R ^C2 , and the combination of R ^B1 and R ^B2 are not the same as each other. ) The cyclic siloxane compound is a compound composed of two or more rings including at least one crosslinked ring formed between silicon atoms in the ring skeleton,
In the step of forming the ring skeleton, the compound represented by the formula (1) (in the formula (1), at least one of R ^B1 and R ^B2 is a —OSi (R ^X1 ) (R ^X2 ) H group. ) And a silicon compound having at least three hydroxy groups or alkoxy groups. A compound composed of two or more rings including at least one bridged ring formed between silicon atoms in the ring skeleton is a compound represented by the following formula (4):
The production method according to claim 5, wherein the silicon compound having at least three hydroxy groups or alkoxy groups is a compound represented by the formula (A1-1).

(In the formula (4), R ^A1 , R ^A2 , R ^C1 and R ^C2 are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. Yes,
R ^B2 represents an alkyl group, an aryl group, an alkenyl group, and a —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 each independently represent an alkyl group, an aryl group, and an alkenyl group. Any one selected from the group consisting of:
R ^D2 is any one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group;

(In the formula (A1-1), R ^D1 is an alkoxy group,
R ^D2 is any one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group;
R ^E1 and R ^E2 are alkyl groups. ) The cyclic siloxane compound is a compound composed of two or more rings including at least one crosslinked ring formed between silicon atoms in the ring skeleton,
In the step of forming the ring skeleton, a compound represented by the formula (1) (in the formula (1), R ^B1 and R ^B2 are —OSi (R ^X1 ) (R ^X2 ) H groups). Reacting with a silicon compound having at least four hydroxy or alkoxy groups,
The method according to claim 1. A compound composed of two or more rings including at least one bridged ring formed between silicon atoms in the ring skeleton is a compound having a structure represented by the following formula (5):
The production method according to claim 7, wherein the silicon compound having at least four hydroxy groups or alkoxy groups is a compound represented by the formula (A1-2).

(In the formula (5), R ^A1 , R ^A2 , R ^C1 and R ^C2 are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. Yes,
R ^X1 and R ^X2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group;
n is an integer of 2 or more. )

(In the formula (A1-2), R ^D1 and R ^D2 are an alkoxy group, and R ^E1 and R ^E2 are an alkyl group.) The cyclic siloxane compound is a compound composed of two or more rings including at least one spiro ring,
R ^A1 , R ^A2 , R ^C1 and R ^C2 in the formula (1) are each independently an alkoxy group, and R ^B1 and R ^B2 are each independently an alkyl group, an aryl group, and an alkenyl group. Any one selected from the group consisting of
The compound represented by the formula (1) is reacted with a silane compound having at least two hydroxy groups in the presence of a transition metal hydride complex catalyst. Comprising reacting in the presence of a catalyst,
The method according to claim 1.

(In the formula (2), R ^{A1 ′} , R ^{A2 ′} , R ^{C1 ′} and R ^{C2 ′} are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group. Is one of
R ^{B1 ′} and R ^{B2 ′} are each independently an alkyl group, an aryl group, an alkenyl group, and —OSi (R ^{X1 ′} ) (R ^{X2 ′} ) H group (R ^{X1 ′} and R ^{X2 ′} are Independently, any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.)
n is an integer of 1 or more.
However, the combination of R ^{A1 ′} and R ^{A2 ′ and} the combination of R ^{C1 ′} and R ^{C2 ′} are not the same as the combination of R ^{B1 ′} and R ^{B2 ′} . ) The production method according to claim 9, wherein the compound composed of two or more rings including the at least one spiro ring is a compound having a structure represented by the following formula (6).

(In the formula (6), Q ¹ and Q ² each independently have the following structure:

(R ^{B1 ′} and R ^{B2 ′} each independently represent an alkyl group, an aryl group, an alkenyl group, and a —OSi (R ^{X1 ′} ) (R ^{X2 ′} ) H group (R ^{X1 ′} and R ^{X2 ′} are Each independently is any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.), And R ^{C1 ′} and R ^{C2 ′} are each independently , A hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or an alkoxy group, and n is an integer of 1 or more.)
R ^B1 and R ^B2 each independently represent an alkyl group, an aryl group, an alkenyl group, and —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 each independently represent an alkyl group , An aryl group, and an alkenyl group.)
R ^D1 and R ^D2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group;
R ^{A1 ′} and R ^{A2 ′} are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group;
p and N are integers of 1 or more. ) The production method according to claim 10, wherein the compound having a structure represented by the formula (6) is a compound represented by the following formula (6-1).

(In the formula (6-1), Q ¹ and Q ² each independently have the following structure:

Represented by
R ^B1 and R ^B2 each independently represent an alkyl group, an aryl group, an alkenyl group, and —OSi (R ^X1 ) (R ^X2 ) H group (R ^X1 and R ^X2 each independently represent an alkyl group , An aryl group, and an alkenyl group.)
R ^D1 and R ^D2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a siloxy group;
R ^{A1 ′} and R ^{A2 ′} are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group;
R ^{B1 ′} and R ^{B2 ′} are each independently an alkyl group, an aryl group, an alkenyl group, and —OSi (R ^{X1 ′} ) (R ^{X2 ′} ) H group (R ^{X1 ′} and R ^{X2 ′} are Independently any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group.)
R ^{C1 ′} and R ^{C2 ′} are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, and an alkoxy group;
p and n are integers of 1 or more. ) A cyclic siloxane compound represented by the following formula (I).

(In the formula (I), R ^a1 , R ^a2 , R ^c1 and R ^c2 are each independently an alkoxy group,
R ^b1 , R ^b2 , R ^d1 and R ^d2 are each independently any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group;
m is any integer from 0 to 2. ) A cyclic siloxane compound represented by the following formula (II):

(In the formula (II), R ^e is an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and, is either selected from the group consisting of siloxy groups,
R ^f , R ^g1 , R ^g2 , R ^h1 , R ^h2 , R ⁱ¹ , and R ⁱ² are each independently any one selected from the group consisting of an alkyl group, an aryl group, and an alkenyl group. ) A cyclic siloxane compound having a structure represented by the following formula (III):

(In the formula ^{(III), R j1, R} j2, R k1, R k2, R l1, R l2, R m1, and R ^{m @ 2} are each independently an alkyl group, an aryl group and, consists of an alkenyl group One of a group,
n is an integer of 2 or more. ) A cyclic siloxane compound having a structure represented by the following formula (IV).

(In the formula (IV), R ⁿ¹ , R ⁿ² , R ^o1 , R ^o2 , R ^p1 , R ^p2 , R ^q1 , R ^q2 , R ^r1 , R ^r2 , R ^s1 , and R ^s2 are each independently An alkyl group, an aryl group, and any one selected from the group consisting of alkenyl groups;
m1, m2, and m3 are each independently an integer of 1 or 2,
n is an integer of 1 or more.
However, the combination of R ⁿ¹ and R ^{n2 and} the combination of R ^r1 and R ^r2 are not the same as the combination of R ^p1 and R ^p2 . )

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