JP2011098939A - Completely condensed oligosilsesquioxane and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide the selective synthesis, isolation and nitration of POSS (polyhedral oligosilsesquioxane) having a trialkylsilyl group on a phenyl group. <P>SOLUTION: The completely condensed silsesquioxane represented by formula (1) and having a trialkylsilylphenyl group is synthesized and isolated from trialkoxysilane having the trialkylsilylphenyl group. Other functional groups can be introduced by converting the trialkylsilyl group into a nitro group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to fully condensed oligosilsesquioxanes and methods for their production.

Polysilsesquioxane is an intermediate substance between inorganic silica [SiO ₂ ] and organic silicone [(R ₂ SiO) _n ], and is represented by [RSiO _3/2 ] _n . The inorganic structural portion having a siloxane bond bears properties as an inorganic material such as excellent transparency, heat resistance, hardness, and insulation. On the other hand, the organic structure part consists of organic functional groups directly bonded to silicon atoms. Solubility and dispersion stability in organic materials, which tend to be insufficient only with an inorganic structure, adjustment of refractive index and dielectric constant, imparting photocurability It bears the characteristics such as. As described above, polysilsesquioxane having characteristics of an inorganic material and an organic material is attracting attention as an organic / inorganic hybrid material.

Polysilsesquioxane is known to have a random structure, a polyhedral structure, and a ladder structure depending on its structure. Among them, polyhedral oligosilsesquioxane (POSS) having a structure in which a Si—O bond is three-dimensionally closed has high heat resistance, oxidation resistance, chemical resistance and high mechanical properties because of its unique three-dimensional structure. It has many excellent features, such as mechanical strength and insulation, and is expected to be applied to electronic and optical materials. Among POSS, a T ₈ compound ([RSiO _3/2 ] ₈ ; T structure indicates RSiO _3/2 ), which is a fully condensed oligosilsesquioxane having a silicon atom at the top of a cube and an oxygen atom between them. Since it is easily available, many reports have been made so far, and it has been used for the study of expression of new functions and improvement of functionality.

These POSS synthesized not only _{T 8 structure,} have been reported in recent years also _{T 6, T 10, T 12} , T 14 structures, etc. (e.g., Non-Patent Documents 1 and 2).

As for the POSS derivative, a fully condensed POSS (fully condensed oligosilsesquioxane) whose side chain (corresponding to R of [RSiO _3/2 ] _n ) is a linear alkyl group can be obtained only in a low yield. The actual situation (for example, Non-Patent Document 3 and Non-Patent Document 4). In addition, it has been reported that fully condensed oligosilsesquioxane having a phenyl group as a side chain can be obtained in good yield by hydrolysis using phenyltrichlorosilane or phenyltrialkoxysilane as a raw material. Development into derivatives is difficult (Non-Patent Document 4).

As described above, when a functional group is introduced into POSS and applied to a material, the situation is that in a fully condensed oligosilsesquioxane, it is difficult to convert a functional group except for a side chain substituent other than hydrogen.

For example, Mr. Lane et al. Introduced Ph ₈ T ₈ with fuming nitric acid to introduce a nitro group at the para position of the phenyl group, but as far as the integration ratio of ¹ H-NMR in the examples was observed, it was selectively introduced at the para position. It is difficult to say that it is introduced, and it is suggested that it is introduced other than the para position of the phenyl group (Patent Document 1, Non-Patent Document 5). When such a compound is applied to the material, the original physical properties of the para-substituted Ph ₈ T ₈ cannot be obtained, and the physical properties necessary for the intended precision material cannot be obtained. In addition, since iron is used in this method, there are many problems in application to semiconductor materials and the like whose metal content requires the ppb order.

For all substituents in the side chain is the same or about half the same T ₈ compounds, relatively easy to synthesize, it has also been reported. In addition, a fully condensed oligosilsesquioxane ring-closed with incompletely condensed T ₇ lacking one apex of the T ₈ structure and chlorosilane or the like having a functional functional group has 7 of 8 substituents. There are also reports of synthesizing polymers by polymerizing the same type (for example, Non-Patent Document 6 and Non-Patent Document 7).

Among fully condensed oligosilsesquioxanes, compounds having a phenyl group represented by Ph ₈ T ₈ in the side chain can be synthesized in a relatively high yield, are readily available, and have been extensively studied (for example, Patent Document 4). If various functional groups can be introduced into the phenyl side chain of fully condensed oligosilsesquioxane, it is possible not only to synthesize materials without using incompletely condensed oligosilsesquioxane, but also to application to materials. Therefore, it is possible to expand the opportunity to put POSS materials on the market and to expect a significant industrial effect.

JP-T-2004-529984

Journal of American Chemical Society 1997, 119, 46, 11323-11324. Chemistry Letters 2007, No. 6, pp. 792-793 Journal of American Chemical Society 1989, 111, 18, 7288-7289 Journal of American Chemical Society 1964, 86, 6, 1120-1125 Journal of American Chemical Society 2001, 123, 49, 12416-12417 Macromolecules 1996, 29, 22, 7302-7304. Macromolecules 2006, 39, 10, pp. 3473-3475.

The present invention has been made in view of the above situation, and provides a fully condensed oligosilsesquioxane derivative and a novel production method.

That is, the present invention synthesizes and isolates a fully condensed oligosilsesquioxane having a T ₈ , T ₁₀ , T ₁₂ structure having a trialkylsilyl group in the phenyl group, and replaces the trialkylsilyl group with a nitro group. This is a featured manufacturing method.

で表される完全縮合オリゴシルセスキオキサンであり、Ｒはトリアルキルシリルフェニル基（ａ）又はニトロフェニル基（ｂ）

（式中、Ｘは夫々独立してアルキル基、アリールアルキル基またはシクロアルキル基である。このアルキル基における炭素数は１から１０であり、任意の水素原子はハロゲン原子または炭素数１から５のアルキル基で置き換えられてもよい。このアリールアルキル基における炭素数は７から１０であり、任意の水素原子はハロゲン原子または炭素数１から１０のアルキル基で置き換えられてもよい。このシクロアルキル基における炭素数は３から１０であり、任意の水素原子はハロゲン原子または炭素数１から１０のアルキル基で置き換えられてもよい。）
である事を特徴とする化合物（請求項１）。 That is, the present invention
General formula (1) or general formula (2)

Wherein R is a trialkylsilylphenyl group (a) or a nitrophenyl group (b)

(In the formula, each X is independently an alkyl group, an arylalkyl group or a cycloalkyl group. The alkyl group has 1 to 10 carbon atoms, and an arbitrary hydrogen atom is a halogen atom or a carbon atom having 1 to 5 carbon atoms. The arylalkyl group may have 7 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms. The number of carbon atoms in is from 3 to 10, and any hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 10 carbon atoms.)
(Claim 1).

The fully condensed oligosyl represented by the general formula (1) or the general formula (2) according to claim 1, wherein X in the formula (a) is a saturated aliphatic alkyl group having 1 to 4 carbon atoms. Sesquioxane (Claim 2).

The fully condensed oligosilsesquioxane represented by the general formula (1) or the general formula (2) according to claim 1, wherein X in the formula (a) is a methyl group (claim 3).

で示され、Ｒは式（ａ）

（式中、Ｘは、請求項１の定義と同じ意味を表す。）
で表される基である事を特徴とする完全縮合オリゴシルセスキオキサンの製造方法であって、炭素数１から３のハロゲン化炭化水素溶媒及び水存在下、第４級アンモニウム塩触媒下で一般式（４）

（式中、Ｘは前記と同様である。式中、Ｙは夫々独立してアルキル基、アリールアルキル基またはシクロアルキル基である。このアルキル基における炭素数は１から４であり、任意の水素原子はハロゲン原子または炭素数１から５のアルキル基で置き換えられてもよい。このアリールアルキル基における炭素数は７から１０であり、任意の水素原子はハロゲン原子または炭素数１から１０のアルキル基で置き換えられてもよい。このシクロアルキル基における炭素数は３から１０であり、任意の水素原子はハロゲン原子または炭素数１から１０のアルキル基で置き換えられてもよい。）
で表されるケイ素化合物を加水分解縮合させて得る製造方法（請求項４）。 General formula (1) or general formula (2) or general formula (3)

R is represented by the formula (a)

(Wherein X represents the same meaning as defined in claim 1)
In the presence of a halogenated hydrocarbon solvent having 1 to 3 carbon atoms and water, in the presence of a quaternary ammonium salt catalyst. General formula (4)

(In the formula, X is as defined above. In the formula, each Y is independently an alkyl group, an arylalkyl group, or a cycloalkyl group. The alkyl group has 1 to 4 carbon atoms, and any hydrogen atom. The atom may be replaced by a halogen atom or an alkyl group having 1 to 5 carbon atoms, wherein the arylalkyl group has 7 to 10 carbon atoms, and any hydrogen atom is a halogen atom or an alkyl group having 1 to 10 carbon atoms. This cycloalkyl group has 3 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms.)
A production method obtained by hydrolytic condensation of a silicon compound represented by (4).

The general formula (1), the general formula (2) or the general formula (3) according to claim 4, wherein X and Y in the general formula (4) are a saturated aliphatic alkyl group having 1 to 4 carbon atoms. A method for producing a fully condensed oligosilsesquioxane represented by (5).

The general formula (1) or the general formula (2) or the general formula according to any one of claims 4 to 5, wherein X in the general formula (4) is a methyl group, and Y is an ethyl group. A method for producing a fully condensed oligosilsesquioxane represented by (3) (Claim 6).

The quaternary ammonium salt is tetraalkylammonium fluoride, which is represented by the general formula (1), the general formula (2) or the general formula (3) according to any one of claims 4 to 6. A method for producing a fully condensed oligosilsesquioxane (claim 7).

The quaternary ammonium salt is tetrabutylammonium fluoride, which is represented by the general formula (1), the general formula (2) or the general formula (3) according to any one of claims 4 to 7. A method for producing a fully condensed oligosilsesquioxane (claim 8).

The halogenated hydrocarbon solvent is dichloromethane and / or chloroform, and is represented by the general formula (1), the general formula (2), or the general formula (3) according to any one of claims 4 to 8. The manufacturing method of the fully condensed oligosilsesquioxane represented (Claim 9).

で示され、Ｒは式（ａ）

（式中、Ｘは、請求項１の定義と同じ意味を表す。）
で表される完全縮合オリゴシルセスキオキサンの混合物を再結晶処理により、一般式（１）及び一般式（２）及び一般式（３）で表される完全縮合オリゴシルセスキオキサンに単離する事を特徴とする製造方法（請求項１０）。 General formula (1) or general formula (2) or general formula (3)

R is represented by the formula (a)

(Wherein X represents the same meaning as defined in claim 1)
The mixture of the fully condensed oligosilsesquioxane represented by the formula (1) is isolated by recrystallization treatment into the fully condensed oligosilsesquioxane represented by the general formula (1), the general formula (2) and the general formula (3). A manufacturing method characterized in that (10).

The solvent for the recrystallization treatment is a saturated aliphatic hydrocarbon having 5 to 10 carbon atoms, benzene, an aromatic hydrocarbon having 7 to 12 carbon atoms including a saturated alkyl group, a saturated aliphatic alcohol having 1 to 4 carbon atoms, or a carbon number. 11. The fully condensed oligosilsesquioxane according to claim 10, wherein at least one is selected from 1 to 3 saturated aliphatic nitriles and halogenated aliphatic hydrocarbons having 1 to 3 carbon atoms. (11).

The method for producing a fully condensed oligosilsesquioxane according to any one of claims 9 to 11, wherein the temperature for the recrystallization treatment is selected between minus 80 ° C and 30 ° C (claim 12).

で示され、Ｒは式（ａ）

（式中、Ｘは前記と同様である。）
で表される完全縮合オリゴシルセスキオキサンを硝酸でニトロ化し、Ｒを式（ａ）から式（ｂ）

に変換する事を特徴とする完全縮合オリゴシルセスキオキサンの製造方法（請求項１３）。 General formula (1) or general formula (2) or general formula (3)

R is represented by the formula (a)

(In the formula, X is the same as described above.)
The fully condensed oligosilsesquioxane represented by the formula (ii) is nitrated with nitric acid, and R is converted from formula (a) to formula (b).

A process for producing a fully condensed oligosilsesquioxane, characterized in that it is converted into a thiol (Claim 13).

The method for producing a fully condensed oligosilsesquioxane according to claim 13, wherein the reaction temperature is selected between minus 80 ° C and 0 ° C (claim 14).

According to the method of the present invention, the fully condensed silsesquioxane represented by the general formula (1), the general formula (2) and the general formula (3) having a trialkylsilylphenyl group has a trialkylsilylphenyl group. It is possible to synthesize and isolate from trialkoxysilane and convert the trialkylsilyl group to nitration.
The nitro group is a functional group that can be easily converted to other functional groups such as carbon-carbon bond formation when converted to an amino group, etc., which allows the introduction of functional functional groups such as polymerizable functional groups, and is incomplete It is possible to synthesize materials without using condensed POSS.

¹ H-NMR spectrum of octakis (p-trimethylsilylphenyl) silsesquioxane ²⁹ Si-NMR spectrum of octakis (p-trimethylsilylphenyl) silsesquioxane ¹ H-NMR spectrum of decaquis (p-trimethylsilylphenyl) silsesquioxane ²⁹ Si-NMR spectrum of decaquis (p-trimethylsilylphenyl) silsesquioxane ¹ H-NMR spectrum of dodecakis (p-trimethylsilylphenyl) silsesquioxane ²⁹ Si-NMR spectrum of dodecakis (p-trimethylsilylphenyl) silsesquioxane ¹ H-NMR spectrum of octakis (p-nitrophenyl) silsesquioxane ²⁹ Si-NMR spectrum of octakis (p-nitrophenyl) silsesquioxane ¹ H-NMR spectrum of decaquis (p-nitrophenyl) silsesquioxane ²⁹ Si-NMR spectrum of decaquis (p-nitrophenyl) silsesquioxane ¹ H-NMR spectrum of dodecakis (p-nitrophenyl) silsesquioxane ²⁹ Si-NMR spectrum of dodecakis (p-nitrophenyl) silsesquioxane

Hereinafter, the present invention will be described in detail.

で表される完全縮合オリゴシルセスキオキサンであり、Ｒはトリアルキルシリルフェニル基（ａ）又はニトロフェニル基（ｂ）

（式中、Ｘは夫々独立してアルキル基、アリールアルキル基またはシクロアルキル基である。このアルキル基における炭素数は１から１０であり、任意の水素原子はハロゲン原子または炭素数１から５のアルキル基で置き換えられてもよい。このアリールアルキル基における炭素数は７から１０であり、任意の水素原子はハロゲン原子または炭素数１から１０のアルキル基で置き換えられてもよい。このシクロアルキル基における炭素数は３から１０であり、任意の水素原子はハロゲン原子または炭素数１から１０のアルキル基で置き換えられてもよい。）
である事を特徴とする化合物である。 General formula (1) or general formula (2) or general formula (3)

Wherein R is a trialkylsilylphenyl group (a) or a nitrophenyl group (b)

(In the formula, each X is independently an alkyl group, an arylalkyl group or a cycloalkyl group. The alkyl group has 1 to 10 carbon atoms, and an arbitrary hydrogen atom is a halogen atom or a carbon atom having 1 to 5 carbon atoms. The arylalkyl group may have 7 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms. The number of carbon atoms in is from 3 to 10, and any hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 10 carbon atoms.)
It is a compound characterized by being.

X in general formula (1) or general formula (2) is an alkyl group, an arylalkyl group, or a cycloalkyl group. Examples of alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and other aliphatic alkyl groups and arylalkyl groups. Examples of the cycloalkyl group include, but are not limited to, a benzyl group, a phenethyl group, and the like, and examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.

及び、Ｒがｐ−ニトロフェニル基である一般式（８）又は一般式（９）又は一般式（１０）

である。 Specific examples of the compound include those represented by the general formula (5), the general formula (6), or the general formula (7), in which R is a p-trimethylsilylphenyl group.

And R is a p-nitrophenyl group (8), (9) or (10)

It is.

で表されるフェニル基にトリアルキルシリル基を有するトリアルコキシシランである。Ｘは、アルキル基、アリールアルキル基、シクロアルキル基である。アルキル基の例としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基等、アリールアルキル基の例としては、ベンジル基、フェネチル基等、シクロアルキル基の例としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等を挙げる事ができるが、これらに限定されるものではない。Ｙはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基等のアルキル基を挙げる事ができるが、これらに限定されるものではない。 The starting material in the present invention is represented by the general formula (4)

A trialkoxysilane having a trialkylsilyl group in the phenyl group represented by the formula: X is an alkyl group, an arylalkyl group, or a cycloalkyl group. Examples of alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Examples of cycloalkyl groups such as benzyl and phenethyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Examples of Y include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group, but are not limited thereto. is not.

のｐ−トリメチルシリルフェニルトリエトキシシランであり、これをハロゲン化炭化水素溶媒中、第４級アンモニウム塩触媒下で加水分解縮合をさせ、トリメチルシリル基を有する一般式（５）及び一般式（６）及び一般式（７）で表される完全縮合オリゴシルセスキオキサンを合成し、再結晶させて単離する事を特徴とする。 As a more preferred specific example of the general formula (4), the two substituents of the phenyl group have a para-position, the general formula (11) wherein X is a methyl group, and Y is an ethyl group

P-trimethylsilylphenyltriethoxysilane, which is hydrolyzed and condensed in a halogenated hydrocarbon solvent under a quaternary ammonium salt catalyst to give a general formula (5) and a general formula (6) having a trimethylsilyl group. A fully condensed oligosilsesquioxane represented by the general formula (7) is synthesized, recrystallized and isolated.

Examples of the quaternary ammonium salt used in the reaction include tetraalkylammonium halide, tetraalkylammonium hydroxide, and the like. Tetraammonium halide is preferable, and tetraalkylammonium fluoride is more preferable. Specific examples include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride and the like, but are not limited thereto. The amount of the quaternary ammonium salt used in the reaction can be appropriately selected, but is usually 0.1 to 20% by mole, preferably 0.5 to 10% with respect to 1 mole of the raw silicon compound. It is.

The solvent used for the reaction is a halogenated hydrocarbon solvent having 1 to 3 carbon atoms, and specific examples thereof include dichloromethane, chloroform and a mixture thereof, but are not limited thereto. Moreover, when using the said tetrahydrofuran (THF) solution of tetrabutylammonium fluoride, you may coexist. The amount of the solvent used is 10 to 200 times by weight, preferably 50 to 150 times by weight, with respect to the raw material p-trimethylsilylphenyltriethoxysilane.

There is no restriction | limiting in particular regarding the water used for reaction. The amount of water used is 1.0 to 2.0 times by weight, preferably 1.0 to 1.5 times by weight, more preferably 1.0 to 1 with respect to the starting material p-trimethylsilylphenyltriethoxysilane. .1 times the weight.

Although there is no restriction | limiting in particular about reaction temperature, 0 degreeC to 30 degreeC which is milder conditions are preferable, More preferably, it is 20 degreeC to 30 degreeC.

Specific conditions for the reaction include hydrolysis and condensation with p-trimethylsilylphenyltriethoxysilane represented by the general formula (11) and equimolar water in a THF solution of tetrabutylammonium fluoride in a dichloromethane solvent. Let The amount of tetrabutylammonium fluoride used is 5 mol% with respect to the raw material p-trimethylsilylphenyltriethoxysilane.

As described above, the present invention is characterized in that POSS is isolated by recrystallization treatment. Here, the solvent used for the recrystallization treatment is preferably a saturated aliphatic hydrocarbon having 5 to 10 carbon atoms, benzene, an aromatic hydrocarbon having 7 to 12 carbon atoms including a saturated alkyl group, or 1 carbon atom. 1 to 4 saturated aliphatic alcohols, C 1 to C 3 saturated aliphatic nitriles, and C 1 to C 3 halogenated aliphatic hydrocarbons. Specifically, hexane, ethanol, acetonitrile, THF and the like may be used alone or in combination of two or more.

The temperature for the recrystallization treatment is preferably selected from temperatures between minus 80 ° C. and 30 ° C. More preferably, it is minus 10 ° C. to 25 ° C.

Preferable specific examples of the recrystallization solvent include hexane, hexane / ethanol mixed solvent, and acetonitrile / THF mixed solvent, and the recrystallization temperature is around 25 ° C.

Next, the present invention relates to a fully condensed silsesquioxane represented by the general formula (1), the general formula (2) or the general formula (3) having a trialkylsilyl group. It is a manufacturing method characterized by converting into a base.

More preferable specific examples include converting the general formula (5) into the general formula (8), converting the general formula (6) into the general formula (9), and converting the general formula (7) into the general formula (10). Is a manufacturing method characterized by

An example of the nitrating agent used in the reaction is nitric acid, and more specifically, fuming nitric acid. Although the usage-amount of nitric acid can be selected suitably, it is 10-5000 mol normally with respect to 1 mol of silicon compounds of a raw material, Preferably it is 200-1500 mol.

The reaction temperature is preferably in the range of minus 80 ° C. to 0 ° C., more preferably minus 50 ° C. to minus 10 ° C., and further preferably minus 40 ° C. minus 20 ° C.

When the reaction temperature is higher than the above range, the target POSS yield decreases.

The POSS obtained by the present invention is expected as a synthetic element monomer for uses such as semiconductor encapsulants, various resists and pattern forming materials, oxygen absorbers and oxygen-absorbing resin compositions, and plasma display panels.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Example 1] Synthesis and isolation of cage silsesquioxane (T ₈ , T ₁₀ , T ₁₂ ) at room temperature, dichloromethane (230 ml), tetrabutylammonium fluoride (0.5 ml of 1M THF solution), water To a mixed solution of 0.15 g (10 mmol), 3.00 g (9.6 mmol) of p-trimethylsilylphenyltriethoxysilane was slowly added dropwise. After stirring for 24 hours at room temperature, the layers were separated, and the organic layer was dried over sodium sulfate. The solvent was distilled off to obtain white crystals. The white crystals were a mixture of POSS containing T ₈ , T ₁₀ , T ₁₂ structures.
This was recrystallized from hexane to give octakis of _{T 8} structure (p- trimethylsilyl phenyl) silsesquioxane 0.21 g (11% yield). It was recrystallized from hexane / ethanol (v / v.3 / 1) to the filtrate _to give Dodekakisu of _{T 12} structure (p- trimethylsilyl phenyl) silsesquioxane 0.14 g (7% yield). Recrystallization from acetonitrile /THF(v/v.1/3) to the filtrate _to give Dekakisu of _{T 10} structure (p- trimethylsilyl phenyl) silsesquioxane 0.58 g (30% yield).
(Identification result of octakis (p-trimethylsilylphenyl) silsesquioxane)
¹ H-NMR δ (CDCl ₃ , ppm): 0.25 (s, 9H), 7.52 (d, 2H), 7.73 (d, 2H)
²⁹ Si-NMR δ (CDCl ₃ , ppm): −78.4, −3.83
MALDI-TOF-MS (m / z): 1631 ([M + Na] ⁺ calc. 1608)
^{The 1} H-NMR spectrum is shown in FIG. 1, and the ²⁹ Si-NMR spectrum is shown in FIG.
(Identification result of decaquis (p-trimethylsilylphenyl) silsesquioxane)
¹ H-NMR δ (CDCl ₃ , ppm): 0.24 (s, 9H), 7.40 (d, 2H), 7.56 (d, 2H)
²⁹ Si-NMR δ (CDCl ₃ , ppm): −79.6, −3.98
MALDI-TOF-MS (m / z): 2033 ([M + Na] ⁺ , calc. 2010)
^{The 1} H-NMR spectrum is shown in FIG. 3, and the ²⁹ Si-NMR spectrum is shown in FIG.
(Identification result of dodecakis (p-trimethylsilylphenyl) silsesquioxane)
¹ H-NMR δ (CDCl ₃ , ppm): 0.22 (s, 9H), 7.32 (d, 2H), 7.40 (d, 2H), 7.46 (d, 2H), 7. 56 (d, 2H)
²⁹ Si-NMR δ (CDCl ₃ , ppm): −81.5, −79.4, −4.13, −4.06
MALDI-TOF-MS (m / z): 2438 ([M + Na] ⁺ , calc. 2412)
^{The 1} H-NMR spectrum is shown in FIG. 5, and the ²⁹ Si-NMR spectrum is shown in FIG.

[Example 2] Synthesis of octakis (p-nitrophenyl) silsesquioxane—fuming to 0.100 g (0.062 mmol) of octakis (p-trimethylsilylphenyl) silsesquioxane obtained in Example 1 at −30 ° C. 1.50 g (23 mmol) of nitric acid was slowly added dropwise. After dripping, after stirring at room temperature for 10 hours, the reaction solution was dripped slowly into ice water. The produced precipitate was filtered to obtain 0.081 g of the desired product (yield 94%).
¹ H-NMR δ (THF-d ₈ , ppm): 8.06 (d, 2H), 8.31 (d, 2H)
²⁹ Si-NMR δ (acetone-d ₆ , ppm): −79.2
^{The 1} H-NMR spectrum is shown in FIG. 7, and the ²⁹ Si-NMR spectrum is shown in FIG.

[Example 3] Synthesis of decakis (p-nitrophenyl) silsesquioxane -30.degree. C. to 0.040 g (0.020 mmol) of decakis (p-trimethylsilylphenyl) silsesquioxane obtained in Example 1 at 30.degree. 1.50 g (23 mmol) of nitric acid was slowly added dropwise. After dripping, after stirring at room temperature for 10 hours, the reaction solution was dripped slowly into ice water. The produced precipitate was filtered to obtain 0.028 g of the desired product (yield 80%).
¹ H-NMR δ (THF-d ₈ , ppm): 8.12 (d, 2H), 8.23 (d, 2H)
²⁹ Si-NMR δ (acetone-d ₆ , ppm): −80.9
^{The 1} H-NMR spectrum is shown in FIG. 9, and the ²⁹ Si-NMR spectrum is shown in FIG.

[Example 4] Synthesis of dodecakis (p-nitrophenyl) silsesquioxane-smoked 0.040 g (0.017 mmol) of dodecakis (p-trimethylsilylphenyl) silsesquioxane obtained in Example 1 at 30 ° C. 1.50 g (23 mmol) of nitric acid was slowly added dropwise. After dripping, after stirring at room temperature for 10 hours, the reaction solution was dripped slowly into ice water. The produced precipitate was filtered to obtain 0.012 g of the desired product (yield 34%).
¹ H-NMR δ (THF-d ₈ , ppm): 7.79 (d, 2H), 7.92 (d, 2H), 8.13 (d, 2H), 8.21 (d, 2H)
²⁹ Si-NMR δ (acetone-d ₆ , ppm): −82.2, −80.3
¹ H-NMR spectrum is shown in FIG. 11, and ²⁹ Si-NMR spectrum is shown in FIG.

As described above, in the present invention, the trialkylsilyl group bonded to the phenyl group can be selectively nitrated 100% in the present invention. Furthermore, if the nitro group is converted to an amino group or the like, it is a functional group that can be easily converted to other functional groups such as carbon-carbon bond formation, reflecting the physical properties of the molecular structure itself having the intended function, Application to can be expected.

Claims (14)

General formula (1) or general formula (2)

Wherein R is a trialkylsilylphenyl group (a) or a nitrophenyl group (b)

(In the formula, each X is independently an alkyl group, an arylalkyl group or a cycloalkyl group. The alkyl group has 1 to 10 carbon atoms, and an arbitrary hydrogen atom is a halogen atom or a carbon atom having 1 to 5 carbon atoms. The arylalkyl group may have 7 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms. The number of carbon atoms in is from 3 to 10, and any hydrogen atom may be replaced by a halogen atom or an alkyl group having 1 to 10 carbon atoms.)
A compound characterized by The fully condensed oligosyl represented by the general formula (1) or the general formula (2) according to claim 1, wherein X in the formula (a) is a saturated aliphatic alkyl group having 1 to 4 carbon atoms. Sesquioxane. The fully condensed oligosilsesquioxane represented by the general formula (1) or the general formula (2) according to claim 1, wherein X in the formula (a) is a methyl group. General formula (1) or general formula (2) or general formula (3)

R is represented by the formula (a)

(Wherein X represents the same meaning as defined in claim 1)
In the presence of a halogenated hydrocarbon solvent having 1 to 3 carbon atoms and water, in the presence of a quaternary ammonium salt catalyst. General formula (4)

(In the formula, X is as defined above. In the formula, each Y is independently an alkyl group, an arylalkyl group, or a cycloalkyl group. The alkyl group has 1 to 4 carbon atoms, and any hydrogen atom. The atom may be replaced by a halogen atom or an alkyl group having 1 to 5 carbon atoms, wherein the arylalkyl group has 7 to 10 carbon atoms, and any hydrogen atom is a halogen atom or an alkyl group having 1 to 10 carbon atoms. This cycloalkyl group has 3 to 10 carbon atoms, and any hydrogen atom may be replaced with a halogen atom or an alkyl group having 1 to 10 carbon atoms.)
The manufacturing method obtained by carrying out hydrolysis condensation of the silicon compound represented by these. The general formula (1), the general formula (2) or the general formula (3) according to claim 4, wherein X and Y in the general formula (4) are a saturated aliphatic alkyl group having 1 to 4 carbon atoms. The manufacturing method of the fully condensed oligosilsesquioxane represented by this. The general formula (1) or the general formula (2) or the general formula according to any one of claims 4 to 5, wherein X in the general formula (4) is a methyl group, and Y is an ethyl group. A method for producing a fully condensed oligosilsesquioxane represented by (3). The quaternary ammonium salt is tetraalkylammonium fluoride, which is represented by the general formula (1), the general formula (2) or the general formula (3) according to any one of claims 4 to 6. Process for producing a fully condensed oligosilsesquioxane. The quaternary ammonium salt is tetrabutylammonium fluoride, which is represented by the general formula (1), the general formula (2) or the general formula (3) according to any one of claims 4 to 7. Process for producing a fully condensed oligosilsesquioxane. The halogenated hydrocarbon solvent is dichloromethane and / or chloroform, and is represented by the general formula (1), the general formula (2), or the general formula (3) according to any one of claims 4 to 8. The manufacturing method of the fully condensed oligosilsesquioxane represented. General formula (1) or general formula (2) or general formula (3)

R is represented by the formula (a)

(Wherein X represents the same meaning as defined in claim 1)
The mixture of the fully condensed oligosilsesquioxane represented by the formula (1) is isolated by recrystallization treatment into the fully condensed oligosilsesquioxane represented by the general formula (1), the general formula (2) and the general formula (3). The manufacturing method characterized by doing. The solvent for the recrystallization treatment is a saturated aliphatic hydrocarbon having 5 to 10 carbon atoms, benzene, an aromatic hydrocarbon having 7 to 12 carbon atoms including a saturated alkyl group, a saturated aliphatic alcohol having 1 to 4 carbon atoms, or a carbon number. 11. The fully condensed oligosilsesquioxane according to claim 10, wherein at least one is selected from 1 to 3 saturated aliphatic nitriles and halogenated aliphatic hydrocarbons having 1 to 3 carbon atoms. Manufacturing method. The method for producing a fully condensed oligosilsesquioxane according to any one of claims 9 to 11, wherein the temperature of the recrystallization treatment is selected between minus 80 ° C and 30 ° C. General formula (1) or general formula (2) or general formula (3)

R is represented by the formula (a)

(In the formula, X is the same as described above.)
The fully condensed oligosilsesquioxane represented by the formula (ii) is nitrated with nitric acid, and R is converted from formula (a) to formula (b).

A process for producing a fully condensed oligosilsesquioxane, characterized in that it is converted to The process for producing a fully condensed oligosilsesquioxane according to claim 13, wherein the reaction temperature is selected between minus 80 ° C and 0 ° C.

Images